ADVANCES IN MATERIALS SCIENCE AND

ENGINEERING
This is a series of Pergamon scientific reference works, each volume providing comprehensive,
self-contained and up-to-date coverage of a selected area in the field of materials science and
engineering. T h e series is being developed primarily from the highly acclaimed Encyclopedia
of Materials Science and Engineering, published in 1986. Other titles in the series are listed
below.

B E V E R t (ed.)
Concise Encyclopedia

of Materials

Economics,

B R O O K (ed.)
Concise Encyclopedia of Advanced
C A R R & H E R Z (eds.)
Concise Encyclopedia of Mineral

Policy &

Ceramic

Management

Materials

Resources

C O R I S H (ed.)
Concise Encyclopedia

of Polymer Processing

&

Applications

E V E T T S (ed.)
Concise Encyclopedia

of Magnetic

& Superconducting

Materials

K E L L Y (ed.)
Concise Encyclopedia

of Composite

Materials

M A H A J A N & K I M E R L I N G (eds.)
Concise Encyclopedia

of Semiconducting

Materials

& Related

Technologies

M O A V E N Z A D E H (ed.)
Concise Encyclopedia

of Building & Construction

Materials

S C H N I E W I N D (ed.)
Concise Encyclopedia

of Wood & Wood-Based

W I L L I A M S (ed.)
Concise Encyclopedia

of Medical

& Dental

Materials

Materials

NOTICE TO READERS

Dear Reader
If your library is not already a standing order/continuation order customer to the series
A d v a n c e s in M a t e r i a l s Science a n d E n g i n e e r i n g , m a y w e r e c o m m e n d that you place a
standing/continuation order to receive immediately upon publication all new volumes. Should
you find that these volumes no longer serve your needs, your order can be cancelled at any time
without notice.

ADVANCES IN MATERIALS SCIENCE AND

ENGINEERING
This is a series of Pergamon scientific reference works, each volume providing comprehensive,
self-contained and up-to-date coverage of a selected area in the field of materials science and
engineering. T h e series is being developed primarily from the highly acclaimed Encyclopedia
of Materials Science and Engineering, published in 1986. Other titles in the series are listed
below.

B E V E R t (ed.)
Concise Encyclopedia

of Materials

Economics,

B R O O K (ed.)
Concise Encyclopedia of Advanced
C A R R & H E R Z (eds.)
Concise Encyclopedia of Mineral

Policy &

Ceramic

Management

Materials

Resources

C O R I S H (ed.)
Concise Encyclopedia

of Polymer Processing

&

Applications

E V E T T S (ed.)
Concise Encyclopedia

of Magnetic

& Superconducting

Materials

K E L L Y (ed.)
Concise Encyclopedia

of Composite

Materials

M A H A J A N & K I M E R L I N G (eds.)
Concise Encyclopedia

of Semiconducting

Materials

& Related

Technologies

M O A V E N Z A D E H (ed.)
Concise Encyclopedia

of Building & Construction

Materials

S C H N I E W I N D (ed.)
Concise Encyclopedia

of Wood & Wood-Based

W I L L I A M S (ed.)
Concise Encyclopedia

of Medical

& Dental

Materials

Materials

NOTICE TO READERS

Dear Reader
If your library is not already a standing order/continuation order customer to the series
A d v a n c e s in M a t e r i a l s Science a n d E n g i n e e r i n g , m a y w e r e c o m m e n d that you place a
standing/continuation order to receive immediately upon publication all new volumes. Should
you find that these volumes no longer serve your needs, your order can be cancelled at any time
without notice.

CONCISE ENCYCLOPEDIA OF

MATERIALS CHARACTERIZATION

Editors

ROBERT W CAHN FRS

University

of Cambridge,

UK

ERIC LIFSHIN
General

Electric

Corporate Research and

Schenectady,
NY, USA

Development,

Series Executive Editor

ROBERT W CAHN FRS

University of Cambridge,

UK

Series Senior Advisory Editor

MICHAEL BEVER*
MIT, Cambridge, MA, USA

PERGAMON PRESS
OXFORD NEW YORK SEOUL TOKYO

UK

Pergamon Press Ltd, Headington Hill Hall, Oxford 0X3 OBW,

England

USA

Pergamon Press, Inc., 660 White Plains Road, Tarrytown,

New York 10591-5153, USA

KOREA

Pergamon Press Korea, KPO Box 315, Seoul 110-603, Korea

JAPAN

Pergamon Press Japan, Tsunashima Building Annex,

3-20-12 Yushima, Bunkyo-ku, Tokyo 113, Japan

Copyright 1993 Pergamon Press Ltd

All rights reserved. No part of this publication may be reproduced,
stored in any retrieval system or transmitted in any form or by
any means: electronic, electrostatic, magnetic tape, mechanical,
photocopying, recording or otherwise, without permission in
writing from the publishers.
First edition 1993
Library of Congress Cataloging in Publication Data
Concise encyclopedia of materials characterization / editors,
Robert W. Cahn, Eric Lifshin. 1st ed.
p. cm. (Advances in materials science and engineering)
Includes index.
1. MaterialsEncyclopedias. I. Cahn, R. W. (Robert W.),
1924. II. Lifshin, Eric. III. Series.
TA402.C659 1993
620.03dc20
92-10673
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British
Library.
ISBN 0-08-040603-3

(~) The paper used in this publication meets the minimum requirements of the
American National Standard for Information S c i e n c e s P e r m a n e n c e of Paper for
Printed Library Materials, A N S I Z 3 9 . 4 8 - 1 9 8 4 .

Printed and bound in Great Britain by Butler & Tanner Ltd, Frome

HONORARY EDITORIAL ADVISORY BOARD

Chairman
Walter S Owen

MIT, Cambridge,

MA, USA

Senior Advisory Editor

Michael Bever *

MIT, Cambridge,

Kent Bowen

MIT, Cambridge,
Gilbert Y

Jack W Christian F R S

MA, USA
Chin

AT&T Bell
Laboratories
Murray Hill, NJ, USA

vi

MA, USA

University

of Oxford,

UK

Derek Hull F R S

University

of Cambridge,

Sir Peter Hirsch F R S

University

of Oxford,

Anthony Kelly C B E

UK

UK
FRS

University of Surrey
Guildford, UK

MICHAEL BERLINER BEVER

P r o f e s s o r M i c h a e l B e v e r , E d i t o r - i n - C h i e f of t h e Encyclopedia
of Materials Science and
Engineering
a n d S e n i o r A d v i s o r y E d i t o r of t h e S u p p l e m e n t a r y V o l u m e s a n d t h e C o n c i s e
E n c y c l o p e d i a s , d i e d in C a m b r i d g e , M a s s a c h u s e t t s , on 17 J u l y , 1992.
H e w a s b o r n in B e r l i n in 1911 a n d r e c e i v e d a d e g r e e of D o c t o r of J u r i s p r u d e n c e from
the U n i v e r s i t y of H e i d e l b e r g in 1934, t h e y e a r in w h i c h h e e m i g r a t e d to t h e U S A . In 1937
h e w a s a w a r d e d a m a s t e r ' s d e g r e e in b u s i n e s s a d m i n i s t r a t i o n by H a r v a r d U n i v e r s i t y . H e
then s t u d i e d m e t a l l u r g y at the M a s s a c h u s e t t s Institute of T e c h n o l o g y a n d r e c e i v e d his
d o c t o r a t e in 1944. S o o n a f t e r w a r d s , h e w a s a p p o i n t e d to t h e faculty of the D e p a r t m e n t of
M e t a l l u r g y ( n o w t h e d e p a r t m e n t of M a t e r i a l s S c i e n c e a n d E n g i n e e r i n g ) at M I T , w h e r e his
p r o f o u n d k n o w l e d g e a n d d i v e r s e i n t e r e s t s , r a n g i n g from p h y s i c a l m e t a l l u r g y to m a t e r i a l s
e c o n o m i c s a n d m a n a g e m e n t , s u s t a i n e d his r e s e a r c h a n d t e a c h i n g for n e a r l y half a c e n t u r y .
P r o f e s s o r B e v e r w a s o n e of a s m a l l g r o u p of p e o p l e w h o d i s c u s s e d the c o n c e p t of an
e n c y c l o p e d i a of m a t e r i a l s in the 1950s, b u t t h e project did not get u n d e r w a y until 1974
w h e n P e r g a m o n P r e s s d e c i d e d to c o m m i t the n e c e s s a r y r e s o u r c e s a n d to a p p o i n t M i c h a e l
B e v e r as Editor-in-Chief. H e d e v o t e d t h e r e m a i n i n g y e a r s of his life to the E n c y c l o p e d i a .
It is a fitting m e m o r i a l to his s c h o l a r s h i p a n d to the c e n t r a l role w h i c h h e p l a y e d in the
e v o l u t i o n of m a t e r i a l s s c i e n c e a n d e n g i n e e r i n g .

Chairman,

Walter S Owen
Honorary
Editorial
Advisory
Board
Robert W Cahn
Executive
Editor

Publishing

Director,

Peter Shepherd
Pergamon
Press

vii

FOREWORD

In t h e t i m e s i n c e its p u b l i c a t i o n , t h e Encyclopedia of Materials Science and Engineering

h a s b e e n a c c e p t e d t h r o u g h o u t t h e w o r l d a s t h e s t a n d a r d r e f e r e n c e a b o u t all a s p e c t s of
m a t e r i a l s . T h i s is a w e l l - d e s e r v e d t r i b u t e t o t h e s c h o l a r s h i p a n d d e d i c a t i o n of t h e late
Editor-in-Chief, P r o f e s s o r M i c h a e l B e v e r , t o t h e S u b j e c t E d i t o r s a n d t o t h e n u m e r o u s
contributors.
D u r i n g its p r e p a r a t i o n , it s o o n b e c a m e c l e a r that c h a n g e in s o m e a r e a s is s o r a p i d that
p u b l i c a t i o n w o u l d h a v e t o b e a c o n t i n u i n g activity if t h e E n c y c l o p e d i a w e r e t o r e t a i n its
p o s i t i o n a s an a u t h o r i t a t i v e a n d u p - t o - d a t e s y s t e m a t i c c o m p i l a t i o n of o u r k n o w l e d g e a n d
u n d e r s t a n d i n g of m a t e r i a l s in all t h e i r d i v e r s i t y a n d c o m p l e x i t y . T h u s , t h e n e e d for s o m e
form of s u p p l e m e n t a r y p u b l i c a t i o n w a s r e c o g n i z e d at t h e o u t s e t . T h e P u b l i s h e r h a s m e t
this c h a l l e n g e m o s t h a n d s o m e l y : b o t h a c o n t i n u i n g series of S u p p l e m e n t a r y V o l u m e s t o
t h e m a i n w o r k a n d a n u m b e r of s m a l l e r e n c y c l o p e d i a s , e a c h c o v e r i n g a s e l e c t e d a r e a of
m a t e r i a l s s c i e n c e a n d e n g i n e e r i n g , a r e in t h e p r o c e s s of p u b l i c a t i o n .
P r o f e s s o r R o b e r t C a h n , t h e E x e c u t i v e E d i t o r , w a s p r e v i o u s l y t h e e d i t o r of a n i m p o r t a n t
subject a r e a of t h e m a i n w o r k a n d m a n y o t h e r p e o p l e a s s o c i a t e d w i t h t h e E n c y c l o p e d i a
h a v e c o n t r i b u t e d o r will c o n t r i b u t e t o its S u p p l e m e n t a r y V o l u m e s a n d d e r i v e d C o n c i s e
E n c y c l o p e d i a s . T h u s , c o n t i n u i t y of style a n d r e s p e c t for t h e h i g h s t a n d a r d s set b y t h e
Encyclopedia of Materials Science and Engineering a r e a s s u r e d . T h e y h a v e b e e n j o i n e d
b y s o m e n e w e d i t o r s a n d c o n t r i b u t o r s w i t h k n o w l e d g e a n d e x p e r i e n c e of i m p o r t a n t
subject a r e a s of p a r t i c u l a r interest at t h e p r e s e n t t i m e . T h u s , t h e A d v i s o r y B o a r d is
confident that t h e n e w p u b l i c a t i o n s will significantly a d d t o t h e u n d e r s t a n d i n g of e m e r g i n g
t o p i c s w h e r e v e r t h e y m a y a p p e a r in t h e vast t a p e s t r y of k n o w l e d g e a b o u t m a t e r i a l s .
T h e a p p e a r a n c e of t h e S u p p l e m e n t a r y V o l u m e s a n d t h e series Advances in Materials
Science and Engineering is a n e v e n t w h i c h will b e w e l c o m e d b y s c i e n t i s t s a n d e n g i n e e r s
t h r o u g h o u t t h e w o r l d . W e a r e sure that it will a d d still m o r e l u s t e r t o a m o s t i m p o r t a n t
enterprise.
Walter S Owen

Honorary

Editorial

Chairman
Advisory
Board

ix

EDITORS' PREFACE

T h e Concise Encyclopedia
of Materials
Characterization
is f o u n d e d o n t h e l a r g e g r o u p
of articles on c h a r a c t e r i z a t i o n a n d i n v e s t i g a t i o n of m a t e r i a l s in t h e o r i g i n a l
Encyclopedia
of Materials
Science and Engineering,
p u b l i s h e d in 1 9 8 6 , for w h i c h E r i c L i f s h i n w a s
r e s p o n s i b l e at t h e t i m e . T h e s e a r t i c l e s w e r e s u p p l e m e n t e d w i t h a n u m b e r of a d d i t i o n a l
o n e s w h i c h h a d b e e n c o m m i s s i o n e d b y R o b e r t C a h n for Supplementary
Volume 1 a n d
Supplementary
Volume 2 , p u b l i s h e d in 1988 a n d 1 9 9 0 r e s p e c t i v e l y , w i t h f u r t h e r a r t i c l e s
that w e r e s p e c i f i c a l l y c o m m i s s i o n e d b y b o t h of u s for t h e p r e s e n t v o l u m e . W e b e l i e v e
that t h i s g r a d u a l a c c r e t i o n of e s s a y s o n w h a t h a s e v e n t u a l l y b e c o m e an e x t r e m e l y w i d e
r a n g e of t e c h n i q u e s h a s p r o v e d to b e an e f f e c t i v e w a y of c o v e r i n g t h i s e n o r m o u s field.
T h e t e x t b e g i n s w i t h an i n t r o d u c t i o n to t h e w h o l e field, w r i t t e n b y E r i c L i f s h i n . T h e
m a j o r i t y of t h e 116 a l p h a b e t i c a l a r t i c l e s c o v e r a r a n g e of t e c h n i q u e s of c h a r a c t e r i z a t i o n
w h i c h a r e n o t s p e c i f i c t o a n y o n e g r o u p of m a t e r i a l s , a l t h o u g h n o f e w e r t h a n 12 are
specific to p o l y m e r s a n d s e v e r a l m o r e are specific to m e t a l s , c e r a m i c s o r s e m i c o n d u c t o r s .
A g a i n , a m a j o r i t y of t h e t e c h n i q u e s c o v e r e d a r e i n t r i n s i c a l l y b u l k m e t h o d s , b u t a
s u b s t a n t i a l m i n o r i t y a r e s p e c i f i c to t h e s t u d y of t h e t o p o g r a p h y a n d c o m p o s i t i o n of
surfaces and near-surface regions. S o m e are venerable techniques (though even these
a r e r e g u l a r l y m o d e r n i z e d ) a n d o t h e r s a r e of v e r y r e c e n t v i n t a g e : t h i s l a t t e r i n c l u d e s , by
w a y of e x a m p l e , articles such as Atomic Force Microscopy,
Confocal Optical
Microscopy,
Gamma-Ray
Diffrac tome try; Thermal Wave Imaging;
a n d X-Ray Diffraction,
TimeResolved.
T h e a r t i c l e t i t l e s g u i d e t h e r e a d e r to a r t i c l e s c o v e r i n g s p e c i f i c t e c h n i q u e s ,
b u t as t e c h n i q u e s m a y b e d i s c u s s e d e l s e w h e r e o t h e r t h a n in an a r t i c l e d e v o t e d to t h e m ,
t h e d e t a i l e d i n d e x w i l l aid t h e r e a d e r t o find all t h e v a r i o u s p l a c e s w h e r e a p a r t i c u l a r
t o p i c is t r e a t e d .
L i k e all e d i t o r s , w e h a v e b e e n c o n s t r a i n e d b y t h e a v a i l a b l e s p a c e to m a k e s o m e
difficult c h o i c e s c o n c e r n i n g w h a t t o i n c l u d e a n d w h a t to l e a v e o u t . In p a r t i c u l a r , t h e
shadowy borderland between characterization and nondestructive evaluation posed
s o m e p r o b l e m s : in g e n e r a l , w e o m i t t e d t e c h n i q u e s w h i c h are c l o s e r to t h e w o r l d of
i n s p e c t i o n t h a n to t h a t of r e s e a r c h .
W e w i s h to e x p r e s s o u r g r a t i t u d e for t h e h a r d w o r k , a n d f o r b e a r a n c e , of t h e m a n y
a u t h o r s w h o h a v e w r i t t e n a r t i c l e s for u s , s o m e t i m e s a g a i n s t d e m a n d i n g d e a d l i n e s . W e
a r e a l s o g r e a t l y i n d e b t e d t o t h e p r o f e s s i o n a l s at P e r g a m o n P r e s s i n p a r t i c u l a r , P e t e r
F r a n k a n d H e l e n M c P h e r s o n f o r all t h e y h a v e d o n e to b r i n g this v o l u m e i n t o e x i s t e n c e .
Robert W Cahn
Eric Lifshin
Editors

GUIDE TO USE OF THE ENCYCLOPEDIA

T h i s C o n c i s e E n c y c l o p e d i a is a c o m p r e h e n s i v e
r e f e r e n c e w o r k c o v e r i n g all a s p e c t s of m a t e r i a l s
c h a r a c t e r i z a t i o n . I n f o r m a t i o n is p r e s e n t e d in
a s e r i e s of a l p h a b e t i c a l l y a r r a n g e d a r t i c l e s
w h i c h d e a l c o n c i s e l y w i t h i n d i v i d u a l t o p i c s in a
self-contained manner. This guide outlines the
main
features
and
organization
of
the
E n c y c l o p e d i a , a n d is i n t e n d e d to h e l p t h e r e a d e r
to l o c a t e t h e m a x i m u m a m o u n t of i n f o r m a t i o n
on a g i v e n t o p i c .
A c c e s s i b i l i t y of m a t e r i a l is of vital i m p o r t a n c e in
a r e f e r e n c e w o r k of t h i s k i n d a n d a r t i c l e titles h a v e
t h e r e f o r e b e e n s e l e c t e d not o n l y o n t h e b a s i s of
article c o n t e n t b u t a l s o w i t h t h e m o s t p r o b a b l e n e e d s
of the r e a d e r in m i n d . A n a l p h a b e t i c a l list of all t h e
articles c o n t a i n e d in t h i s E n c y c l o p e d i a is to b e f o u n d
on p p . xvii a n d x v i i i .
Articles are linked by an e x t e n s i v e cross-referencing
s y s t e m . C r o s s - r e f e r e n c e s t o o t h e r a r t i c l e s in t h e
E n c y c l o p e d i a a r e of t w o t y p e s : in t e x t a n d e n d of
text. T h o s e in t h e b o d y of t h e text are d e s i g n e d t o
refer t h e r e a d e r to a r t i c l e s that p r e s e n t in g r e a t e r
detail m a t e r i a l o n t h e s p e c i f i c t o p i c u n d e r d i s c u s s i o n
at that point. T h e y g e n e r a l l y take o n e of the f o l l o w i n g
forms:
...which is fully described in the article Field-Ion
Microscopy:
Observation
of Radiation
Effects.
...other applications of this technique (see
Sampling
Inductively
Coupled
Plasma
Spectrometry).

Laser
Mass

T h e c r o s s - r e f e r e n c e s listed at t h e e n d of an a r t i c l e
s e r v e to identify b r o a d b a c k g r o u n d r e a d i n g a n d to
direct the r e a d e r to articles that c o v e r different a s p e c t s
of t h e s a m e t o p i c .

T h e n a t u r e of an e n c y c l o p e d i a d e m a n d s a h i g h e r
d e g r e e of u n i f o r m i t y in t e r m i n o l o g y a n d n o t a t i o n
than many other scientific works. The widespread
u s e of t h e SI s y s t e m of u n i t s h a s d e t e r m i n e d that
s u c h u n i t s b e u s e d in t h i s E n c y c l o p e d i a . It h a s b e e n
r e c o g n i z e d , h o w e v e r , that in s o m e fields I m p e r i a l
u n i t s a r e m o r e g e n e r a l l y u s e d . W h e r e this is the
c a s e , I m p e r i a l u n i t s are g i v e n with their SI e q u i v a l e n t
q u a n t i t y a n d u n i t f o l l o w i n g in p a r e n t h e s e s . W h e r e
p o s s i b l e , t h e s y m b o l s d e f i n e d in Quantities,
Units,
and Symbols,
p u b l i s h e d b y t h e R o y a l S o c i e t y of
London, have been used.
A l l a r t i c l e s in t h e E n c y c l o p e d i a i n c l u d e a
b i b l i o g r a p h y g i v i n g s o u r c e s of further i n f o r m a t i o n .
E a c h b i b l i o g r a p h y consists of general i t e m s for further
r e a d i n g and/or references w h i c h c o v e r specific aspects
of t h e t e x t . W h e r e a p p r o p r i a t e , a u t h o r s are c i t e d in
t h e t e x t u s i n g a n a m e / d a t e s y s t e m as f o l l o w s :
...as was recently reported (Smith 1988).
Jones (1984) describes...
T h e c o n t r i b u t o r s ' n a m e s a n d t h e o r g a n i z a t i o n s to
w h i c h t h e y a r e affiliated a p p e a r at t h e e n d of all
articles.
A l l c o n t r i b u t o r s c a n b e f o u n d in t h e
a l p h a b e t i c a l L i s t of C o n t r i b u t o r s , a l o n g w i t h t h e i r
full p o s t a l a d d r e s s e s a n d t h e titles of t h e a r t i c l e s of
w h i c h t h e y are a u t h o r s or c o a u t h o r s .
T h e a r t i c l e An Introduction
to Investigation
and
Characterization
of Materials
p r o v i d e s an o v e r v i e w
of t h e s u b j e c t a r e a a n d d i s c u s s e s in b r i e f t h e i s s u e s
c o v e r e d in d e t a i l b y t h e a r t i c l e s in t h e b o d y of the
work.
T h e m o s t i m p o r t a n t i n f o r m a t i o n s o u r c e for locating
a p a r t i c u l a r topic in the E n c y c l o p e d i a is the multilevel
S u b j e c t I n d e x , w h i c h h a s b e e n m a d e as c o m p l e t e
a n d fully s e l f - c o n s i s t e n t as p o s s i b l e .

xv

ALPHABETICAL LIST OF ARTICLES

Acoustic Emission
Acoustic Microscopy
A d h e s i v e s : T e s t s for M e c h a n i c a l P r o p e r t i e s
Anodization Spectroscopy
Art F o r g e r i e s : Scientific D e t e c t i o n
Atomic Force Microscopy
Auger Electron Spectroscopy
Auger Microscopy, Angular Distribution
Ceramic Materials: Cathodoluminescence Analysis
Ceramic Powders: Packing Characterization
Channelling-Enhanced Microanalysis
C h e m i c a l A n a l y s i s of Solid Surfaces
Composite Materials: Nondestructive Evaluation
Compton Scattering
Confocal O p t i c a l M i c r o s c o p y
Corrosion and Oxidation Study Techniques
Corrosion: Test Methods
D e p t h Profiling
Diffusion: N o v e l M e a s u r e m e n t M e t h o d s
Elastomers: Spectroscopic Characterization
E l a s t o m e r s : T e s t s for M e c h a n i c a l P r o p e r t i e s
E l e c t r o n Diffraction
E l e c t r o n Diffraction, L o w - E n e r g y
Electron Energy-Loss Spectrometry
Electron Microprobe Analysis
E l e c t r o n M i c r o s c o p e A n a l y s i s of Defect C l u s t e r s ,
Voids and Bubbles
Electron Microscopy, Analytical
Electron Microscopy, High-Resolution
Electron Microscopy, High-Voltage
E l e c t r o n S p e c t r o s c o p y for C h e m i c a l A n a l y s i s
E l e c t r o n Spin R e s o n a n c e
Electron Tunnelling Spectroscopy
Field-Ion Microscopy: Atom-Probe Microanalysis
F i e l d - I o n M i c r o s c o p y : O b s e r v a t i o n of R a d i a t i o n
Effects
Fractals
Gamma Radiography
G a m m a - R a y Diffractometry
G a s and L i q u i d C h r o m a t o g r a p h y
Gas Sensors, Solid-State
Grain S i z e : N o n d e s t r u c t i v e E v a l u a t i o n
Hardness Characterization
H y d r o g e n as a M e t a l l u r g i c a l P r o b e
Infrared S p e c t r o s c o p y
Ion B a c k s c a t t e r i n g A n a l y s i s
Junction Transient Spectroscopy
Laser Microprobe Mass Spectrometry
Laser Sampling Inductively Coupled Plasma Mass
Spectrometry
Liquid Chromatography Mass Spectroscopy
Magnetic Materials: Measurements
Mechanical Properties Microprobe
M i c r o e n g i n e e r i n g of M a t e r i a l s : C h a r a c t e r i z a t i o n

Microstructural Evolution: Computer Simulation

Microtextural Analysis
Mossbauer Spectroscopy
Neutron Radiography
Nuclear Magnetic Resonance Spectroscopy
N u c l e a r M a g n e t i c R e s o n a n c e S p e c t r o s c o p y of
Solids
Optical Calorimetry
Optical Emission Spectroscopy
Optical Microscopy
Organic Mass Spectrometry
P a p e r and P a p e r b o a r d : D e s t r u c t i v e M e c h a n i c a l
Testing
Paper and Paperboard: Nondestructive Evaluation
Particle-Induced X-Ray Emission
P h a s e D i a g r a m s a n d P h a s e Stability: C a l c u l a t i o n s
P o l e F i g u r e s and O r i e n t a t i o n D i s t r i b u t i o n F u n c t i o n s
Polymer Dielectric Properties: Test Methods
Polymers: Electron Microscopy
Polymers: Light Microscopy
P o l y m e r s : M o l e c u l a r W e i g h t a n d its D i s t r i b u t i o n
Polymers: Neutron Scattering
Polymers: Raman Spectroscopy
P o l y m e r s : T e s t s for D e g r a d a t i o n a n d Stabilization
P o l y m e r s : T e s t s for F l a m m a b i l i t y
P o l y m e r s : T e s t s for M e c h a n i c a l P r o p e r t i e s
P o l y m e r s : T e s t s for T h e r m a l P r o p e r t i e s
Polymers: Thermal Analysis
Polymers: X-Ray Scattering
Porosity: Characterization and Investigation
P o s i t r o n A n n i h i l a t i o n S p e c t r o s c o p y of Defects in
Metals
Powder Characterization
Powder Mechanics
Raman Spectroscopy
Reflection Electron Microscopy
Residual Stresses: Measurement Using Neutron
Diffraction
Residual Stresses: Nondestructive Evaluation
Scanning Electron Microscopy
Scanning Tunnelling Microscopy and Spectroscopy
Secondary-Ion Mass Spectrometry
S e m i c o n d u c t i n g M a t e r i a l s : C h a r a c t e r i z a t i o n by
Etching
Semiconducting Materials: Electron Microscopy
S i n g l e - C r y s t a l X - R a y Diffraction
S m a l l - A n g l e N e u t r o n S c a t t e r i n g in M e t a l l u r g y
Solid-State Nuclear Track Detectors: Applications
Solid State: S t u d y U s i n g M u o n B e a m s
Spark-Source Mass Spectrography
Stress D i s t r i b u t i o n : A n a l y s i s U s i n g T h e r m o e l a s t i c
Effect
Superconducting Materials: Measurements
Texture: Nondestructive Characterization

Alphabetical

Thermal Analysis: An Overview

Thermal Analysis: Recent Developments
Thermal Wave Imaging
Thermodynamic Activity: Measurement
Thermoluminescence
Thermophysical Measurements, Subsecond
T h i n F i l m s : C h a r a c t e r i z a t i o n by X R a y s
Transmission Electron Microscopy: ConvergentB e a m and Microdiffraction T e c h n i q u e s
Vibrothermography
W o o d : A c o u s t i c E m i s s i o n and A c o u s t o - U l t r a s o n i c

xviii

List of

Articles

Characteristics
X - R a y A b s o r p t i o n S p e c t r o s c o p y : E X A F S and
XANES Techniques
X - R a y a n d N e u t r o n Diffraction S t u d i e s of
Amorphous Solids
X - R a y a n d N e u t r o n Diffuse S c a t t e r i n g of R a d i a t i o n Induced Defects
X - R a y Diffraction, T i m e - R e s o l v e d
X-Ray Fluorescence Spectrometry
X-Ray Microanalysis, Quantitative
X - R a y P o w d e r Diffraction

AN INTRODUCTION TO INVESTIGATION
AND CHARACTERIZATION OF MATERIALS
by Eric Lifshin
P r e s e n t - d a y m a t e r i a l s science d e p e n d s heavily o n
u n d e r s t a n d i n g h o w t h e p r o p e r t i e s of a m a t e r i a l relate
to its c o m p o s i t i o n a n d m i c r o s t r u c t u r e . H o w e v e r , this
a p p r o a c h is relatively recent a n d for centuries before
B o h r ' s m o d e l of t h e a t o m , skilled craftsmen a n d
builders p r o d u c e d m a n y objects of r e m a r k a b l e utility
a n d b e a u t y w i t h o u t a n y k n o w l e d g e of w h a t is n o w
considered basic c h e m i s t r y o r m e t a l l u r g y . T h e y
started with m a t e r i a l s f o u n d in their native s t a t e o r
those r e q u i r i n g m i n i m a l processing. D e s i r e d p r o p e r
ties were achieved b y trial a n d e r r o r e x p e r i m e n t a t i o n
or the utilization of experience p a s s e d d o w n t h r o u g h
generations.
F o r t h o u s a n d s of y e a r s certain m e t a l s were
extracted from their ores b y smelting, with v a r i a t i o n s
in the resulting p r o p e r t i e s often being a t t r i b u t e d t o
s u p e r n a t u r a l i n t e r v e n t i o n r a t h e r t h a n t o subtle dif
ferences in t h e m a t e r i a l s o r processes used. A s time
passed a n d p r i n t i n g d e v e l o p e d , practical experience
w a s written d o w n . F o r e x a m p l e , in the sixteenth
c e n t u r y A g r i c o l a ' s De re metallica described m a n y of
the m e t h o d s used for t h e e x t r a c t i o n , m e a s u r e m e n t
a n d classification of m e t a l s . A t a b o u t t h e s a m e t i m e
empirical k n o w l e d g e existed of h o w t o use distillation
to p r e p a r e a variety of simple c o m p o u n d s including
v a r i o u s a l c o h o l s a n d oils.
U n t i l t h e e i g h t e e n t h c e n t u r y only a small n u m b e r of
elements were k n o w n , a n d physical a t t r i b u t e s like
density, c o l o r a n d h a r d n e s s were sufficient t o tell o n e
from a n o t h e r . A s c h e m i s t r y a n d physics d e v e l o p e d in
the n i n e t e e n t h c e n t u r y , t h e g r o w t h of m o r e basic
u n d e r s t a n d i n g led t o t h e discovery of a n u m b e r of
elements a n d t h e e x t r a c t i o n o r synthesis of t h o u s a n d s
of c o m p o u n d s . T h e s e n e w s u b s t a n c e s were a p p l i e d
to m a n y a r e a s i n c l u d i n g m e d i c i n e , c o n s t r u c t i o n ,
t r a n s p o r t a t i o n , w e a p o n r y a n d a g r i c u l t u r e . By t h e
m i d - n i n e t e e n t h c e n t u r y t h e a m o u n t of scientific infor
m a t i o n available h a d g r o w n so large t h a t v a r i o u s
scientific disciplines b e g a n t o split i n t o specialties. I n
chemistry, general chemists w e r e r e p l a c e d b y o r g a n i c ,
i n o r g a n i c , physical, physiological, a g r i c u l t u r a l a n d
analytical chemists. I n 1848 F r e s e n i u s f o u n d e d t h e
first analytical l a b o r a t o r y w h i c h , in a d d i t i o n t o teach
ing, p r o v i d e d g o v e r n m e n t agencies a n d i n d u s t r y w i t h
checks o n m a t e r i a l specifications a n d t h e analysis of
water, food a n d physiological specimens. T h e idea
c a u g h t o n a n d t o d a y t h e r e a r e h u n d r e d s of i n d e p e n
d e n t analytical l a b o r a t o r i e s , as well a s t h o s e associ
ated with h o s p i t a l s , i n d u s t r i a l c o n c e r n s , universities
a n d g o v e r n m e n t agencies. F o l l o w i n g t h e specializa
tion of analytical c h e m i s t r y t h e r e h a s r e m a i n e d a
s t r o n g interplay b e t w e e n t h e analysis a n d d e v e l o p
m e n t of m a t e r i a l s . Better analytical m e t h o d s lead t o a

m o r e systematic a n d c o m p l e t e classification of exist

ing m a t e r i a l s a n d p r o v i d e the insight required for the
d e v e l o p m e n t of new o n e s .

1. Historical

Background

T h e m o s t significant event in laying t h e f o u n d a t i o n

for all p h a s e s of m o d e r n m a t e r i a l s science t o o k place
a t t h e very b e g i n n i n g of the n i n e t e e n t h c e n t u r y w h e n
D a l t o n p o s t u l a t e d t h a t m a t t e r consisted of aggregates
of " u l t i m a t e p a r t i c l e s , " o r a t o m s . A t o m s of a n y
given element were indistinguishable from o t h e r
a t o m s of t h e s a m e element with respect to m a s s a n d
all p r o p e r t i e s , while a t o m s of different s u b s t a n c e s
c o u l d c o m b i n e to f o r m " a t o m s " (molecules) of a third
s u b s t a n c e . D a l t o n further recognized t h a t elemental
a t o m s c o m b i n e only in certain r a t i o s , so as t o form
p r o d u c t s with u n i q u e s t o i c h i o m e t r y . K n o w i n g t h a t he
c o u l d n o t weigh individual a t o m s , h e used this c o n
cept t o d e t e r m i n e t h e relative weights of a t o m s a n d
molecules b a s e d o n h y d r o g e n . T h u s , t h e f o r m a t i o n of
a given a m o u n t of w a t e r ( a s s u m e d t o be H O ) with a n
a t o m i c weight of 6.5 r e q u i r e d t h e c o m b i n a t i o n of
oxygen with a n a t o m i c weight of 5.5 with h y d r o g e n
with a n a t o m i c weight of 1.0. A l t h o u g h D a l t o n did
n o t recognize t h a t t w o a t o m s of h y d r o g e n c o m b i n e
with o n e a t o m of oxygen t o f o r m o n e molecule of
w a t e r (a p o i n t w h i c h w a s later clarified by A v o g a d r o )
a n d his a t o m i c weights were n o t p a r t i c u l a r l y a c c u r a t e ,
his ideas a r e of f u n d a m e n t a l i m p o r t a n c e t o m o d e r n
chemistry.
T h e c o n c e p t of definite p r o p o r t i o n s a n d a t o m i c
weights c o m b i n e d with a fairly consistent symbolic
n o m e n c l a t u r e for t h e elements, i n t r o d u c e d by Berzelius, led t o the description of m a t t e r a n d chemical
r e a c t i o n s in the f o r m with w h i c h we a r e n o w familiar.
T h i s a p p r o a c h also led t o t h e e m e r g e n c e of analysis
t e c h n i q u e s b a s e d o n chemical b e h a v i o r r a t h e r t h a n
physical p r o p e r t y d e t e r m i n a t i o n s . F o r e x a m p l e , the
m e t h o d k n o w n as gravimetric analysis w a s widely
used in t h e n i n e t e e n t h c e n t u r y . A chemical reaction
b e t w e e n a s o l u t i o n of t h e m a t e r i a l t o be analyzed a n d
a s e c o n d r e a g e n t results in t h e f o r m a t i o n of a n
insoluble c o m p o u n d c o n t a i n i n g t h e element of inter
est. T h e p r e c i p i t a t e is isolated, d r i e d a n d weighed, a n d
t h e q u a n t i t y of t h e e l e m e n t is d e t e r m i n e d from its
s t o i c h i o m e t r i c fraction.
A s e c o n d t e c h n i q u e , k n o w n as v o l u m e t r i c analysis
( t i t r a t i o n ) , w a s d e v e l o p e d a t a b o u t t h e s a m e time. It
involves m e a s u r i n g t h e v o l u m e of a r e a g e n t necessary
t o react c o m p l e t e l y with a fixed q u a n t i t y of a s a m p l e
in a p r e d e t e r m i n e d chemical r e a c t i o n . A t first it w a s
n o t a s c o m m o n l y used as gravimetric analysis,

xix

Introduction
because of difficulty in m e a s u r i n g r e a c t i o n e n d p o i n t s ,
b u t as m o r e i n d i c a t o r s b e c a m e available t h e m e t h o d
grew in p o p u l a r i t y . A t h i r d t e c h n i q u e , k n o w n as
c o l o r i m e t r y , w a s also k n o w n in t h e n i n e t e e n t h cen
tury. Selected r e a c t i o n s a r e p e r f o r m e d t o p r o d u c e
colored c o m p o u n d s c o n t a i n i n g t h e e l e m e n t of inter
est. C o l o r intensity is t h e n m e a s u r e d , relative t o
s t a n d a r d s o l u t i o n s , t o e s t i m a t e t h e a m o u n t of t h a t
element present. A l t h o u g h this a p p r o a c h w a s initially
limited t o a few elements a n d q u a n t i t a t i v e analysis
w a s fairly subjective, its use increased as m o r e c o l o n metric reagents were identified a n d i n s t r u m e n t a t i o n
was developed to m a k e measurements m o r e accurate.
T h e n i n e t e e n t h c e n t u r y also saw t h e initial d e v e l o p
m e n t of electroanalytical c h e m i s t r y a n d t h e use of
polarized light t o discriminate b e t w e e n m a t e r i a l s , b u t
t h e m o s t significant i n s t r u m e n t a l m e t h o d d e v e l o p e d
w a s t h e s p e c t r o s c o p e . Its o p e r a t i o n is b a s e d o n t h e
ability of a p r i s m t o disperse w h i t e light i n t o its
v a r i o u s c o n s t i t u e n t s , a fact d e m o n s t r a t e d b y N e w t o n
in the seventeenth c e n t u r y . I n 1814 F r a u n h o f e r , a lens
m a n u f a c t u r e r , recognized t h a t a n u m b e r of b o t h
bright a n d d a r k lines c o u l d b e o b s e r v e d in b o t h
sunlight a n d t h e flames p r o d u c e d b y b u r n i n g different
fuels. T h e idea of using a b s o r p t i o n spectra for m o r e
general chemical analysis w a s p r o p o s e d b y Brewster a
few years later. I n t h e 1850s B u n s e n a n d Kirchhoff
developed a s p e c t r o s c o p e w i t h a n i m p r o v e d s o u r c e
a n d viewing optics which is t h e f o r e r u n n e r of instru
m e n t s used t o d a y . W i t h it they discovered b o t h t h e
elements cesium a n d r u b i d i u m .
A t t h e beginning of t h e n i n e t e e n t h c e n t u r y only
a b o u t 30 elements were k n o w n ; b y t h e e n d this
n u m b e r h a d m o r e t h a n d o u b l e d . D u r i n g this p e r i o d it
also b e c a m e a p p a r e n t t h a t s o m e t y p e of systematic
classification of t h e elements w a s n e e d e d . T h e c o n c e p t
of t h e periodic table w a s i n d e p e n d e n t l y d e v e l o p e d b y
M e n d e l e e v in R u s s i a a n d M e y e r in G e r m a n y using
schemes b a s e d o n a t o m i c weights a n d v a r i o u s o t h e r
physical p r o p e r t i e s . A l t h o u g h o r d e r i n g of t h e ele
m e n t s is n o w related t o a t o m i c n u m b e r a n d t h e
electronic s t r u c t u r e of t h e elements, m o s t of t h e
c h a n g e s m a d e over t h e years h a v e b e e n t o a d d n e w
elements r a t h e r t h a n t o r e o r d e r k n o w n elements.
A t the e n d of t h e n i n e t e e n t h c e n t u r y a n d t h e
beginning of t h e twentieth c e n t u r y a series of m a j o r
events t o o k place w h i c h revolutionized u n d e r s t a n d i n g
of b o t h t h e a t o m a n d t h e e l e t r o m a g n e t i c r a d i a t i o n .
Studies of t h e electrical c o n d u c t i v i t y of gases a t
r e d u c e d pressure led t o t h e discovery of c a t h o d e r a y s
by H i t t o r f in 1869, confirmed by G o l d s t e i n in 1876.
A l t h o u g h initially t h e n a t u r e of these rays w a s
unclear, w o r k b y T h o m s o n , p u b l i s h e d in 1897,
s h o w e d t h a t they consisted of negatively c h a r g e d
particles, from their deflection in m a g n e t i c a n d
electrostatic fields. H e also d e m o n s t r a t e d t h a t these
particles (later called electrons) h a d t h e s a m e c h a r g e t o - m a s s r a t i o as t h o s e given off from h o t filaments o r
released d u r i n g t h e e x p o s u r e of certain m e t a l s t o

xx

e l e c t r o m a g n e t i c r a d i a t i o n (the p h o t o e l e c t r i c effect,
discovered b y H e r t z in 1887). T h u s they a p p e a r e d t o
b e a key c o m p o n e n t of all m a t t e r , a n d w h e n r e m o v e d
w o u l d leave a t o m s as positive ions.
T h e n a t u r e of this positive ion c o r e w a s studied in
t h e first d e c a d e of t h e t w e n t i e t h c e n t u r y b y R u t h e r
ford, w h o e x p e r i m e n t e d o n t h e scattering of p a r t i
cles from thin m e t a l foils. F r o m this w o r k c a m e a
m o d e l of t h e a t o m in w h i c h electrons revolve a r o u n d
a positively c h a r g e d n u c l e u s . A l t h o u g h this m o d e l w a s
consistent w i t h his o b s e r v a t i o n s , it w a s u n a c c e p t a b l e
from t h e p o i n t of view of classical physics, since t h e
electrons w o u l d c o n t i n u o u s l y r a d i a t e energy a n d
s h o u l d , therefore, spiral i n t o t h e nucleus. H o w e v e r ,
this d i l e m m a w a s s o o n reconciled by B o h r , w h o
p o s t u l a t e d t h a t t h e electron o r b i t s c o r r e s p o n d e d t o
discrete energy states a n d as l o n g as a n electron
r e m a i n e d in its o r b i t n o r a d i a t i o n w o u l d occur. T h e
idea of discrete energy states w a s b a s e d o n t h e p r i n
ciples of q u a n t u m m e c h a n i c s i n t r o d u c e d b y P l a n c k in
1900 t o describe r a d i a t i o n e m i t t e d from a black b o d y .
U s i n g these states, B o h r w a s able t o describe correctly
t h e line s p e c t r a of h y d r o g e n o b s e r v e d in t h e 1880s b y
B a l m e r a n d m a t h e m a t i c a l l y f o r m u l a t e d by R y d b e r g
in 1890. A l t h o u g h t h e B o h r m o d e l w a s significantly
modified b y S o m m e r f e l d a n d S c h r o d i n g e r t o describe
m u l t i e l e c t r o n a t o m s m o r e accurately, t h e c o n c e p t of
electron t r a n s i t i o n s b e t w e e n discrete levels a n d t h e
a c c o m p a n y i n g release o r a b s o r p t i o n of energy is of
central i m p o r t a n c e t o m a n y of t h e different types of
p h o t o n a n d electron s p e c t r o m e t r i e s used t o d a y .
T h o m p s o n ' s use of m a g n e t i c a n d electric fields t o
d e t e r m i n e c h a r g e - t o - m a s s r a t i o s w a s also applied t o
t h e c h a r a c t e r i z a t i o n of positive ion b e a m s (called
K a n a l s t r a h l e n b y G o l d s t e i n ) , w h i c h were also k n o w n
t o exist a l o n g with c a t h o d e r a y s , as s h o w n in
e x p e r i m e n t s o n t h e electrical c o n d u c t i v i t y of gases.
T h o m s o n ' s apparatus, k n o w n as a parabolic mass
s p e c t r o m e t e r , p r o d u c e d a series of p h o t o g r a p h i c a l l y
r e c o r d e d p a r a b o l a s , o n e for e a c h c h a r g e - t o - m a s s
r a t i o . T h e system lacked m a s s r e s o l u t i o n , h o w e v e r ,
because it h a d n o energy selectivity. This difficulty
w a s o v e r c o m e several years later (1919) w h e n A s t o n
d e v e l o p e d a velocity focusing i n s t r u m e n t w h i c h
s h o w e d t h a t t h e s p e c t r u m of n e o n actually c o n t a i n e d
t w p p e a k s , o n e a t m a s s 20 a n d t h e o t h e r a t m a s s 22.
T h i s d e m o n s t r a t e d t h a t a n e l e m e n t of a given n u m b e r
c a n h a v e m o r e t h a n o n e f o r m (isotopes) a n d t h u s
revealed t h e p o w e r of t h e m a s s s p e c t r o m e t e r as a n
i m p o r t a n t analytical i n s t r u m e n t . I n t h e d e c a d e s t h a t
followed, r e s o l u t i o n a n d sensitivity c o n t i n u e d t o im
p r o v e as a result of t h e efforts of D e m p s t e r , M a t t a u c h
and Herzog, and Nier and Johnson. Some commer
cially available i n s t r u m e n t s t o d a y h a v e m a s s resolu
tions of 1 p a r t in 100 000, c o m p a r e d w i t h t h e 1 p a r t in
12 of t h e first p a r a b o l i c s p e c t r o m e t e r s .
E x p e r i m e n t s o n t h e electrical c o n d u c t i v i t y of gases
also led t o t h e accidental discovery of r a y s b y
R o e n t g e n in 1896. H e recognized t h a t their u n u s u a l

Introduction
p e n e t r a t i n g p o w e r w a s influenced by t h e t u b e o p e r a t
ing voltage as well as by t h e thickness a n d t y p e of
a b s o r b e r s used. Since r a y s were n o t deflected b y
m a g n e t i c o r electrostatic fields, it w a s believed t h a t
they were p a r t of t h e e l e c t r o m a g n e t i c s p e c t r u m , b u t
t h a t they m u s t h a v e a very s h o r t w a v e l e n g t h . D e t e r
m i n i n g their w a v e l e n g t h d i s t r i b u t i o n p r e s e n t e d s o m e
thing of a p r o b l e m , b e c a u s e a l t h o u g h diffraction
gratings h a d previously b e e n d e v e l o p e d for dispersing
visible spectra, they were n o t fine e n o u g h t o s e p a r a t e
rays. T h e s o l u t i o n w a s p r o p o s e d b y L a u e in 1912,
w h o believed t h a t t h e i n t e r a t o m i c s p a c i n g of crystals
should be of t h e right o r d e r of m a g n i t u d e t o act a s
suitable diffraction g r a t i n g s . H e p r o v e d this h y p o t h e
sis by p a s s i n g a b e a m of r a y s t h r o u g h a crystal of
zinc sulfide a n d o b t a i n i n g a p a t t e r n of s p o t s o n a
photographic plate.
This w o r k s t i m u l a t e d further studies b y W . H .
Bragg a n d W . L. B r a g g (father a n d s o n ) , w h o built t h e
first crystal diffraction s p e c t r o m e t e r . U s i n g a crystal
of r o c k salt with a k n o w n i n t e r p l a n a r spacing, t h e y
were able t o c h a r a c t e r i z e t h e spectral d i s t r i b u t i o n of a
p l a t i n u m x-ray t a r g e t a n d also d e v e l o p t h e simple
e q u a t i o n w h i c h relates i n t e r p l a n a r spacing, x-ray
wavelength a n d diffraction angle. T h e s p e c t r a t h e y
observed consisted of b o t h a b r o a d b a n d of general
r a d i a t i o n (the x-ray c o n t i n u u m ) a n d discrete lines
characteristic of t h e t u b e a n o d e . I n v e s t i g a t i o n s b y
Moseley described in 1913 s h o w e d t h a t t h e r e also
existed a simple r e l a t i o n s h i p b e t w e e n t h e w a v e l e n g t h s
of the characteristic lines e m i t t e d from a n e l e m e n t a n d
its a t o m i c n u m b e r . T h i s u n i q u e r e l a t i o n s h i p f o r m s t h e
basis for e l e m e n t a l analysis by a variety of x-ray,
electron a n d i o n - i n d u c e d x-ray spectroscopies. T h e
w o r k of t h e B r a g g s also p r o v i d e d t h e key t o crystal
s t r u c t u r e d e t e r m i n a t i o n b y u s i n g a selected c h a r a c t e r
istic x-ray w a v e l e n g t h t o d e t e r m i n e a set of i n t e r p l a
n a r spacings for a single crystal.
T h e n u m e r o u s scientific discoveries t h a t t o o k place
at the b e g i n n i n g of t h e t w e n t i e t h c e n t u r y p r o v i d e d t h e
physical f o u n d a t i o n for t h e h u n d r e d s of i n s t r u m e n
t a l o r i e n t e d analytical m e t h o d s w h i c h a r e widely
used t o d a y . It is a s t o n i s h i n g t h a t m o s t of w h a t we n o w
consider s t a n d a r d l a b o r a t o r y i n s t r u m e n t s were d e
veloped after 1930. T h e following t e c h n i q u e s a n d key
contributors are examples:
transmission electron microscopy, Ruska (1934)
scanning electron microscopy, von Ardenne (1938)
liquid chromatography, Martin and Synge (1941)
carbon-14 dating, Libby (1946)
nuclear magnetic resonance, Block and Purcell (1946)
electron microprobe analysis, Castaing (1951)
gas chromatography, Martin and James (1952)
secondary-ion mass spectrometry, Castaing and Slodzian
(1960)
T h e n a m e s , events a n d d a t e s m e n t i o n e d so far tell
only a small p a r t of t h e c h r o n o l o g i c a l d e v e l o p m e n t of
s o m e of t h e m e t h o d s described. Practical refinement

of m a n y of these i n s t r u m e n t a l m e t h o d s often t o o k
m a n y y e a r s a n d c o n s i d e r a b l e ingenuity o n t h e p a r t of
o t h e r key c o n t r i b u t o r s . F o r e x a m p l e , t h e first c o m
mercially available s c a n n i n g electron m i s c r o s c o p e did
n o t a p p e a r until 27 years (1965) after v o n A r d e n n e ' s
first i n s t r u m e n t , a n d it h a s b e e n only d u r i n g t h e last
few y e a r s t h a t relatively easy-to-use c o m p u t e r i z e d
complete
single-crystal
structure
determination
e q u i p m e n t h a s been readily available. A t p r e s e n t o n e
of t h e m o s t active a r e a s of analysis is t h e s t u d y of
surfaces b y x-ray p h o t o e l e c t r o n s p e c t r o s c o p y b u t , as
m e n t i o n e d previously, t h e p h o t o e l e c t r i c effect w a s
k n o w n before t h e e n d of t h e n i n e t e e n t h c e n t u r y .
Relatively recent d e v e l o p m e n t s in electronics, c o m
p u t e r s a n d h i g h - v a c u u m systems h a v e all h a d a n
e n o r m o u s i m p a c t o n analytical i n s t r u m e n t a t i o n in
t e r m s of ease of o p e r a t i o n , s o p h i s t i c a t i o n of the
analysis, q u a l i t y of results a n d speed. I n d u s t r i a l l a b o r
a t o r i e s n o w r o u t i n e l y u n d e r t a k e types of analysis t h a t
w o u l d formerly h a v e r e q u i r e d t h e effort for a P h . D .
thesis.
W i t h t h e great diversity of i n s t r u m e n t a t i o n avail
able, t h e role of t h e t r a d i t i o n a l analytical l a b o r a t o r y
h a s n o w b e e n e x p a n d e d t o include d e t e r m i n a t i o n s of
morphology, microstructure, crystallography and a
variety of physical p r o p e r t i e s . T h e t e r m often associ
a t e d with t h e c o m b i n a t i o n of analytical chemistry a n d
these o t h e r m e t h o d s of analysis is m a t e r i a l s c h a r a c t e r
ization. T h e c o n c e p t of a m a t e r i a l s c h a r a c t e r i z a t i o n
g r o u p goes h a n d in h a n d with t h e e v o l u t i o n of
interdisciplinary m a t e r i a l s science a n d engineering
centers w h i c h b r i n g t o g e t h e r e x p e r t s in such a r e a s as
m e t a l l u r g y , electronic m a t e r i a l s , ceramics, solid-state
physics, p o l y m e r s a n d surface chemistry. N o t only
h a v e t h e variety of m a t e r i a l s a n d t h e types of instru
m e n t a t i o n available increased, b u t t h e r e a s o n s for
l o o k i n g a t these m a t e r i a l s h a v e also multiplied.
M a t e r i a l s c h a r a c t e r i z a t i o n specialists m u s t n o w be
c o n c e r n e d with basic research, p r o d u c t a n d process
d e v e l o p m e n t , failure analysis, r e g u l a t o r y c o m p l i a n c e ,
p a t e n t issues, q u a l i t y c o n t r o l , m a n u f a c t u r i n g p r o d u c
tivity a n d t h e e x a m i n a t i o n of c o m p e t i t i v e p r o d u c t s .
It is also i m p o r t a n t t o recognize t h e degree of
analytical specialization w h i c h h a s b e e n t a k i n g place.
I n d i v i d u a l s w h o a r e e x p e r t s in n u c l e a r m a g n e t i c reso
n a n c e s p e c t r o s c o p y m a y n o t h a v e expertise in singlecrystal x-ray s t r u c t u r e d e t e r m i n a t i o n , even t h o u g h
i n f o r m a t i o n gained b y t h e t w o t e c h n i q u e s m a y be
highly c o m p l e m e n t a r y a n d i m p o r t a n t t o a p o l y m e r
chemist. A n e x p e r t in t r a n s m i s s i o n electron m i c r o
s c o p y m a y h a v e only a n incidental k n o w l e d g e of
s e c o n d a r y - i o n m a s s s p e c t r o m e t r y , even t h o u g h b o t h
chemical a n d s t r u c t u r a l i n f o r m a t i o n m a y be t h e
key t o u n d e r s t a n d i n g t h e b e h a v i o u r of a n electronic
device. A s t h e d e m a n d for m a t e r i a l s with u n i q u e
p r o p e r t i e s g r o w s , so also d o e s t h e c o m p l e x i t y of t h e
m a t e r i a l s themselves a n d t h e m e t h o d s n e e d e d t o a n a
lyze t h e m . E x a m p l e s a r e t h e chemical identification of
s u b m i c r o m e t e r s e c o n d - p h a s e particles w h i c h c a n sig-

xxi

Introduction

DPS

Ions
^/^r

Electrons

Electrons
N

Photons

N ^ P h o t o n s

Secondary-ion mass spectrometry (SIMS)

Auger electron spectrometry (AES)

Rutherford backscattering spectrometry (RBS)

Analytical electron microscopy (AEM)

Proton-induced x-ray emission (PIXE)

Photons

Electrons

^^^^^^Photons

X - r a y photoelectron spectrometry (XPS and ESCA)

X-ray diffraction (XRD)

Scanning electron microscopy (SEM)

X - r a y fluorescence (XRF)

Electron probe microanalyzer (EPM)

Infrared spectrometry (IR)

Low-energy electron diffraction (LEED)

Light microscopy (LM)

Figure 1
Analytical methods: probes and responses

nificantly influence t h e p r o p e r t i e s of h i g h - t e m p e r a t u r e
alloys, t h e d e t e r m i n a t i o n of p o l l u t a n t s a t t h e p a r t s p e r
billion level a n d t h e c h a r a c t e r i z a t i o n of a few a t o m i c
layers o n the surface of a catalyst. Clearly, scientists
a n d engineers h a v e e n o u g h difficulty in k e e p i n g u p
with a d v a n c e s in their o w n fields w i t h o u t h a v i n g t o be
materials c h a r a c t e r i z a t i o n experts. H o w e v e r , it is es
sential t o h a v e e n o u g h basic u n d e r s t a n d i n g of cur
rently used analytical m e t h o d s t o be able t o i n t e r a c t
effectively with such experts.

2. Methods Available in the Modern

Characterization
Laboratory

Materials

This Concise E n c y c l o p e d i a c o n t a i n s a series of articles

describing v a r i o u s m e t h o d s for t h e investigation a n d
c h a r a c t e r i z a t i o n of m a t e r i a l s . W h i l e n o t every o n e is
covered, m o s t of t h e m a i n o n e s in use t o d a y a r e
represented. E a c h article includes a description of t h e
u n d e r l y i n g physical principles, the type of s a m p l e s
required a n d typical d a t a o u t p u t a n d s o m e discussion
of strengths a n d weaknesses. A s described a b o v e , t h e
s t r u c t u r e a n d c o m p o s i t i o n of m a t t e r c a n be studied b y
e x a m i n i n g h o w it interacts with r a d i a t i o n , electrons
a n d ions. A s u m m a r y of s o m e of these i n t e r a c t i o n s
a n d the related analytical t e c h n i q u e s is given in F i g . 1.
T h e a p p r o a c h t h a t is best suited for a p a r t i c u l a r
p r o b l e m d e p e n d s o n a variety of factors, m a n y of
which a r e strongly interrelated.
C h e m i c a l o r m i c r o s t r u c t u r a l analysis in m o s t l a b o r
atories of a n y size c a n be carried o u t by a centralized
analytical facility which m a i n t a i n s c o r e analytical
i n s t r u m e n t s staffed by p e r s o n n e l w h o a r e experts in
each area. T h e following m e t h o d s a r e fairly essential
in a n y type of multidisciplinary research o r engineer
ing l a b o r a t o r y :
classical chemical analysis techniques
thermal analysis techniques
optical microscopy and metallography
ultraviolet, visible and infrared spectroscopy
xxii

mass spectrometry
gas and liquid chromatography
scanning and transmission electron microscopy
nuclear magnetic resonance spectrometry
optical emission and absorption spectrometry
x-ray diffraction and fluorescence spectrometry
Auger and x-ray photoelectron spectrometry
scanning tunnelling and scanning force microscopy
O t h e r t e c h n i q u e s e m p l o y i n g c o m m e r c i a l l y available
e q u i p m e n t w h i c h a r e s o m e w h a t less c o m m o n l y used
a l t h o u g h often i m p o r t a n t include:
low-energy electron diffraction
secondary-ion mass spectrometry
Raman spectrometry
low-energy ion scattering spectrometry
field-ion microscopy and atom-probe analysis
electron spin resonance spectrometry
Mossbauer spectrometry
laser microprobe analysis
acoustic microscopy
quantititave image analysis
W h a t m u s t be recognized also is t h a t even if a welle q u i p p e d analytical l a b o r a t o r y h a s all t h e specialties
listed in t h e first c a t e g o r y , e a c h of t h e m e t h o d s c a n b e
substantially s u b d i v i d e d , r e q u i r i n g s e p a r a t e instru
m e n t s a n d often s e p a r a t e skills. T a k i n g x-ray diffrac
tion as a n e x a m p l e , t h e following subdivision c a n
easily b e m a d e :
conventional diffractometry
high- and low-temperature diffractometry
back-reflection and transmission Laue photography
residual stress measurement
single-crystal structure determination
pole figure determination
double-crystal diffractometry
microdiffraction
Debye-Scherrer and Guinier powder photography
Berg-Barrett and Lang topography measurements
Services n o t readily available i n - h o u s e c a n often b e
p u r c h a s e d externally from general analytical l a b o r a
tories o r specialists in s o m e of t h e a b o v e m e t h o d s .

Introduction
This a p p r o a c h is p a r t i c u l a r l y useful w h e n t h e n u m b e r
of samples d o e s n o t justify setting u p a n i n - h o u s e
facility o r if i n - h o u s e facilities a r e severely over
loaded. N o single l a b o r a t o r y c a n possess e v e r y t h i n g
a n d the use of external a n a l y s t s often p r o v i d e s a n
effective w a y of p r o v i d i n g n e e d e d resources. I n s o m e
cases, t h e use of e x t e r n a l l a b o r a t o r i e s is t h e only
a p p r o a c h w h e n t h e i n s t r u m e n t a t i o n r e q u i r e d is in t h e
multimillion d o l l a r price r a n g e a n d large s u p p o r t
staffs a r e needed. E x a m p l e s of such specialized facili
ties include:
extended x-ray absorption fine structure measurements
(using synchrotron radiation)
neutron activation analysis
carbon-14 dating
picosecond laser fluorescence spectrometry
neutron activation spectrometry
high-voltage transmission electron microscopy
Rutherford backscattering and ion-channelling spec
trometry
proton-excited x-ray fluorescence
T h e r e a r e o t h e r factors in a d d i t i o n t o cost a n d
speed of analysis t h a t s h o u l d b e c o n s i d e r e d in t h e
decision t o use i n - h o u s e o r external facilities. I n a n
industrial e n v i r o n m e n t , p r o p r i e t a r y c o n c e r n s often
limit s a m p l e d i s t r i b u t i o n . A n o t h e r i m p o r t a n t factor is
the n a t u r e of t h e i n t e r a c t i o n b e t w e e n t h e a n a l y s t a n d
the research scientist o r engineer. I n t h o s e cases w h e r e
the specific t y p e of analysis n e e d e d is k n o w n a n d t h e
right s a m p l e h a s been selected, it m a y be q u i t e satis
factory t o send a s a m p l e several t h o u s a n d k i l o m e t e r s
a n d receive t h e results in a few weeks. H o w e v e r , in
o t h e r cases a m u c h h i g h e r degree of i n t e r a c t i o n m a y
lead m o r e r a p i d l y t o m e a n i n g f u l results. T h i s is p a r
ticularly t r u e if t h e t e c h n i q u e o r t h e s a m p l e selected
h a s t o be c h a n g e d b e c a u s e t h e initial a p p r o a c h is
unsuccessful. It c a n also b e t r u e if detailed d a t a
i n t e r p r e t a t i o n relative t o t h e objectives of t h e overall
investigation is r e q u i r e d .
S o m e t i m e s t h e q u e s t i o n of w h o s h o u l d d o t h e
analysis b e c o m e s a n i n t e r n a l o n e . S h o u l d scientists o r
engineers h a v e their o w n c h a r a c t e r i z a t i o n tools o r
s h o u l d they use a centralized service? W h i l e t h e r e is n o
single a n s w e r t o this q u e s t i o n , it is clearly a n issue of
optimizing t h e utilization of resources. It is n o t
u n c o m m o n for every chemist in a l a b o r a t o r y t o h a v e
his o w n gas o r liquid c h r o m a t o g r a p h a n d every
metallurgist t o h a v e his o w n light optical m i c r o s c o p e .
In such cases a n i n v e s t m e n t of a few t h o u s a n d d o l l a r s
could i m p r o v e research p r o d u c t i v i t y b y p r o v i d i n g
quick a n s w e r s expediting t h e next e x p e r i m e n t . It is
highly unlikely, h o w e v e r , t h a t e a c h chemist w o u l d
have a p r i v a t e n u c l e a r m a g n e t i c r e s o n a n c e spec
t r o m e t e r a n d e a c h metallurgist a s e p a r a t e t r a n s m i s
sion electron m i c r o s c o p e . T h e s e r e q u i r e very large
initial capital as well as t h e e x p e n d i t u r e of b o t h
m o n e y a n d time t o a c q u i r e t h e n e e d e d expertise a n d
to m a i n t a i n a piece of e q u i p m e n t t h a t m a y n o t even
h a v e a l o n g - t e r m use. O b v i o u s l y t h e overall i m p a c t

c o u l d be a serious decrease in research p r o d u c t i v i t y .

O c c a s i o n s d o arise, h o w e v e r , w h e n it is i m p o r t a n t
t o h a v e fairly sophisticated analytical i n s t r u m e n t s
closely i n t e g r a t e d with o t h e r types of e x p e r i m e n t a l
a p p a r a t u s . F o r e x a m p l e , s a m p l e s m a y b e altered b y
being transferred t o s e p a r a t e i n s t r u m e n t a t i o n , as in
the c h a r a c t e r i z a t i o n of thin films f o r m e d b y m o l e c u l a r
b e a m epitaxy b y t h e use of integral low-energy elec
t r o n diffraction, A u g e r s p e c t r o m e t r y a n d residual gas
analysis i n s t r u m e n t a t i o n . I n a m a n u f a c t u r i n g en
v i r o n m e n t a process m a y require r a p i d on-line m o n i
toring to maintain quality control. Chemical reactors
frequently h a v e in-line gas c h r o m a t o g r a p h s a n d
infrared a n a l y z e r s . D e d i c a t e d analytical e q u i p m e n t
o u t s i d e a centralized facility m a y also be r e q u i r e d if it
serves only t h e objectives of a single individual's
research interest a n d b o t h t h e degree of i n t e r a c t i o n
n e e d e d a n d t h e d u r a t i o n of t h e project justify t h e
associated cost. A n e x a m p l e w o u l d be a laser R a m a n
s p e c t r o m e t e r u n i q u e l y set u p t o s t u d y c o m b u s t i o n
chemistry and dynamics.

3. Interaction

with the

Analyst

G i v e n h u n d r e d s of analytical m e t h o d s , it is o b v i o u s t o
a s k h o w is a n a p p r o p r i a t e m e t h o d selected for solving
a given p r o b l e m ? Before t h e recent proliferation of so
m a n y n e w types of analytical i n s t r u m e n t s , a scientist
o r engineer w o u l d g o t o a d e s i g n a t e d analytical
chemist in his o r g a n i z a t i o n a n d describe the i n f o r m a
tion n e e d e d . T h e analytical chemist w o u l d either g o t o
suitable references o r k n o w i m m e d i a t e l y from per
s o n a l experience w h i c h t e c h n i q u e t o use. T o d a y this
d i a l o g u e c o u l d be c o n s i d e r a b l y e x t e n d e d a n d w o u l d
u n d o u b t e d l y involve experts in several fields. T h e
scientist o r engineer initiating t h e s t u d y s h o u l d b e
p r e p a r e d t o a n s w e r a n u m b e r of q u e s t i o n s which will
aid in establishing t h e m e t h o d o r m e t h o d s m o s t
suitable for solving t h e p r o b l e m . T h e following is a
list of representative q u e s t i o n s frequently a s k e d ,
s e p a r a t e d i n t o t h r e e general categories. I n a d d i t i o n
s o m e c o m m e n t s a r e a d d e d which s h o u l d h e l p t o
u n d e r s t a n d t h e role of these categories in establishing
a n analytical strategy. If t h e scientist o r engineer a n d
t h e m a t e r i a l s a n a l y s t a r e , in fact, t h e s a m e p e r s o n , the
discussion is replaced b y i n t r o s p e c t i o n b u t t h e q u e s
tions remain the same.
(a)

Q u e s t i o n s relating t o t h e t y p e a n d detail of
information sought:
Is t h e r e a need t o k n o w w h a t elements a r e p r e s e n t
a n d / o r h o w m u c h of each?
Is t h e r e a need t o k n o w all the elements o r only
s o m e of t h e m ?
D o w n t o w h a t level?
W h a t degree of a c c u r a c y is r e q u i r e d in the
results?
Is crystal s t r u c t u r e o r m i c r o s t r u c t u r a l i n f o r m a
tion n e e d e d ?

xxiii

Introduction
(b)

Q u e s t i o n s relating t o w h a t is a l r e a d y k n o w n
a b o u t the s a m p l e :
W h a t is the physical state of the sample?
Is the s a m p l e a m e t a l , c e r a m i c , s e m i c o n d u c t o r ,
chemical c o m p o u n d s o r p o l y m e r ?
D o e s t h e s a m p l e consist of o n e o r m o r e t h a n o n e
phase?
Is the s a m p l e a m o r p h o u s o r crystalline?
Is s a m p l e h a n d l i n g of t h e s a m p l e r e q u i r e d , either
because of toxicity o r because t h e s a m p l e m i g h t
t r a n s f o r m t o s o m e t h i n g different before o r d u r
ing analysis?
W a s t h e s a m p l e (or its source) e x p o s e d t o a n y
u n u s u a l physical o r chemical c o n d i t i o n s w h i c h
m i g h t h a v e altered its c o m p o s i t i o n o r m i c r o structure?
D o e s t h e s a m p l e consist of layers a n d , if it d o e s ,
h o w m a n y a r e there a n d h o w thick a r e they?
H o w m u c h of each s a m p l e is t h e r e a n d h o w m a n y
samples a r e t o be r u n ?

(c)

Q u e s t i o n s relating t o the w o r k i n g r e l a t i o n s h i p
between t h e analyst a n d t h e scientist o r engineer:
H o w s o o n a r e results needed?
H o w m u c h c a n be spent t o o b t a i n t h e results?
Is y o u r presence n e e d e d d u r i n g the analysis?
Is a detailed r e p o r t o n t h e results needed?
A r e the samples p r o p r i e t a r y ?

These three categories of q u e s t i o n s c a n be t h o u g h t of

as screens which help t o identify o n e o r m o r e m e t h o d s
of a p p r o a c h i n g a given p r o b l e m . T h e y c a n easily b e
related to three general classes of analysis requests as
follows.
(i)

(ii)

xxiv

In the simplest case, the analysis is merely t o

repeat a particular type of m e a s u r e m e n t m a d e
earlier o n a similar sample. Therefore, the m e t h o d
h a s been preselected a n d the only issues to be
resolved are associated with the questions of cat
egory (c). T h e answers are determined by l a b o r a
tory policy, backlogs, urgency of the w o r k a n d
availability of people a n d e q u i p m e n t . A n example
of this class of p r o b l e m w o u l d be a request for
mercury analysis in w a t e r by a t o m i c a b s o r p t i o n
as p a r t of periodic sampling of a b o d y of water.
M o r e frequently, a suitable m e t h o d m a y b e sug
gested b a s e d o n earlier w o r k , b u t the c h a r a c t e r i s
tics of the s a m p l e m a y be sufficiently different
t h a t t h e q u e s t i o n s a s k e d in c a t e g o r y (b) also
b e c o m e i m p o r t a n t . T h e n e w s a m p l e m a y be of a
different size o r s h a p e . It m a y also c o n t a i n o t h e r
elements o r c o m p o u n d s t h a t c o u l d c o m p l i c a t e
the analysis if t h e s a m e analytical m e t h o d is used.
A s a n e x a m p l e , a researcher develops a new
p o l y m e r c o n t a i n i n g a c h l o r i n a t e d flame retard a n t . H e / s h e w a n t s a chlorine analysis in t h e
5 0 p p m region b u t h a s only a 5 m g s a m p l e .
Previously, successful results w o u l d be o b t a i n e d
by x-ray
fluorescence.

(iii) S a m p l e s t h a t c a n b e classified as totally u n k n o w n

o c c u r rarely, since m a t e r i a l s a r e usually n o t
picked a t r a n d o m for analysis. T h e s i t u a t i o n d o e s
arise, h o w e v e r , w h e n o n e m a t e r i a l b e h a v e s differ
ently from a n o t h e r a n d t h e r e a s o n s for t h e dif
ferences a r e s o u g h t . S u c h samples m a y b e t h e
result of l a b o r a t o r y e x p e r i m e n t s o r m a y b e a s s o
ciated with a device o r process t h a t h a s c h a n g e d
o r even failed for s o m e u n k n o w n r e a s o n . T h e
individual initiating t h e w o r k m a y n o t even b e
a w a r e of t h e right q u e s t i o n s t o ask in c a t e g o r y (a)
a n d m u s t therefore w o r k w i t h t h e a n a l y s t t o
define a set of u n i q u e m a t e r i a l characteristics
w h i c h c a n b e used b o t h t o classify t h e specimen
a n d also t o c o n t r i b u t e t o a n e x p l a n a t i o n o f its
b e h a v i o r . A l t h o u g h p r o b l e m s in this class a r e
s o m e t i m e s a m e n a b l e t o quick s o l u t i o n s , t h e y
t e n d m o r e generally t o b e t h e m o s t challenging
a n d expensive o n e s t o deal with, since t h e y
frequently involve t h e use of multiple t e c h n i q u e s
a n d often t h e s a m p l e s a r e n o t o p t i m i z e d for t h o s e
t e c h n i q u e s . A n e x a m p l e of this class of analysis
w o u l d b e a r e q u e s t t o a n a l y z e a catalytic m a t e r i a l
o b t a i n e d from a n e w v e n d o r which, a l t h o u g h
n o m i n a l l y of t h e s a m e c o m p o s i t i o n as t h e p r e
viously used m a t e r i a l , d r a m a t i c a l l y c h a n g e s t h e
r a t e of a chemical r e a c t i o n . A l s o included in this
class a r e p r o b l e m s in failure analysis such a s
d e t e r m i n i n g w h y a t u r b i n e b l a d e h a s failed p r e
m a t u r e l y . I n this s i t u a t i o n q u e s t i o n s in c a t e g o r y
(b) relating t o t h e s a m p l e e n v i r o n m e n t c a n be
extremely i m p o r t a n t .
4. Choosing

a Sample

and a

Method

T h e q u a l i t y of a n analysis c a n be n o b e t t e r t h a n t h a t
d e t e r m i n e d b y t h e s a m p l e o n w h i c h t h e analysis is
p e r f o r m e d . I n t r a c e level d e t e r m i n a t i o n , a s a m p l e c a n
easily b e c o n t a m i n a t e d b y h a n d l i n g o r b y t h e use of
u n c l e a n glassware o r o t h e r l a b o r a t o r y supplies. S a m
ples c a n also b e affected b y e x p o s u r e t o t h e a t m o s
p h e r e , a s in t h e case of h y g r o s c o p i c m a t e r i a l s o r
h y d r o c a r b o n b u i l d u p o n a s a m p l e t o be studied b y
surface analysis t e c h n i q u e s . M a t e r i a l s a r e also n o t
always as h o m o g e n e o u s as expected. If a m e t h o d is
used with a precision of 1 % b u t the c o m p o s i t i o n
of a r a n d o m l y picked s a m p l e varies b y 1 0 % ,
obviously t h e s a m p l i n g e r r o r will d o m i n a t e . T h i s
effect c a n t a k e place a t either the m a c r o s c a l e o r t h e
microscale. I n o t h e r w o r d s , a 1 k g s a m p l e t a k e n from
a single l o c a t i o n in a t a n k c a r c a n lead t o t h e s a m e
m a g n i t u d e of e r r o r in assessing t h e overall c o n t e n t s of
t h e c a r as using a 1 n g m i c r o p r o b e m e a s u r e m e n t t o
d e t e r m i n e t h e c o m p o s i t i o n of a highly segregated
alloy ingot.
Collecting s a m p l e s from e n o u g h regions of t h e
m a t e r i a l t o be a n a l y z e d t o d e t e r m i n e its h o m o g e n e i t y
a n d / o r a v e r a g e c o m p o s i t i o n is a n essential p a r t of
c h a r a c t e r i z a t i o n m e a s u r e m e n t s . If t h e m e t h o d of

Introduction
analysis t o b e used in a p a r t i c u l a r p r o b l e m is k n o w n
in a d v a n c e , as in t h e case of a research e x p e r i m e n t ,
samples s h o u l d b e p r e p a r e d so t h a t t h e y a r e truly
representative of t h e p r o b l e m a n d also of t h e p r o p e r
size a n d g e o m e t r y t o b e c o m p a t i b l e w i t h t h e m e t h o d
to b e used. F o r m o s t m e t h o d s t h e r e is s o m e c o r r e l a
tion b e t w e e n s a m p l e size, sensitivity, a c c u r a c y a n d
precision. S i t u a t i o n s w h e r e t h e a m o u n t of s a m p l e is
limited a r e frequently e n c o u n t e r e d , h o w e v e r , a n d in
these cases t h e q u a n t i t y of s a m p l e m a y strongly
influence t h e analytical m e t h o d selected a n d m i n i
m u m detectability limits. C o n s i d e r t h e following:
a geologist working in an inaccessible location gathering
samples to map out its mineral content
a forensic scientist working with only a small piece of
evidence
a metallurgical failure analysis expert working with a
fragment of a broken device
a research chemist or metallurgist developing a new
material in which it is important to explore hundreds of
variations of composition and/or phase distribution
T h e r e a r e also times w h e n a n a b u n d a n t a m o u n t of
s a m p l e is available b u t either t h e c o n c e n t r a t i o n levels
sought by a particular instrumental method are too
low t o detect b e c a u s e of m a x i m u m a c c e p t a b l e s a m p l e
size limitations, o r interferences from o t h e r c o n s t i
t u e n t s c a n i n t r o d u c e serious e r r o r s in t h e analysis. I n
such s i t u a t i o n s , d e t e r m i n i n g w h e t h e r t h e c o m p o n e n t
of interest ( p h a s e o r e l e m e n t ) is dispersed h o m o g e
neously t h r o u g h o u t t h e s a m p l e o r is n o n u n i f o r m l y
d i s t r i b u t e d is i m p o r t a n t n o t o n l y from t h e s a m p l i n g
p o i n t of view b u t also a s a m e a n s of selecting a
t e c h n i q u e t o give e n h a n c e d localized analysis for
i n h o m o g e n e o u s s a m p l e s . Being able t o detect 1 n g of
m a t e r i a l in a 1 g s a m p l e is a real challenge for a n y
b u l k analysis t e c h n i q u e b u t is very simple b y electron
m i c r o p r o b e analysis if t h e relevant l o c a t i o n is k n o w n .
In t h e case of solids, this c a n often b e d o n e b y
m i c r o s c o p i c e x a m i n a t i o n of t h e s a m p l e either a s it is
o r specially p r e p a r e d t o e n h a n c e p h a s e differences.
W h e n possible, c o n v e n t i o n a l light m i c r o s c o p y s h o u l d
always b e tried first. L o w - m a g n i f i c a t i o n o b s e r v a t i o n
of a n unmodified s a m p l e often reveals w h e t h e r a
s a m p l e is n o n u n i f o r m . If t h e s a m p l e consists of p a r t i
cles o b s e r v a b l e u n d e r a l o w - p o w e r b i n o c u l a r m i c r o
scope, they c a n often b e s e p a r a t e d for easier analysis
by a variety of m e t h o d s i n c l u d i n g s e d i m e n t a t i o n ,
m a g n e t i c s e p a r a t i o n o r even h a n d selection w i t h
tweezers.
If magnifications a b o v e ~ 100 a r e n e e d e d a n d t h e
s a m p l e consists of discrete particles, s c a n n i n g electron
m i c r o s c o p y is usually a b e t t e r a p p r o a c h . H o w e v e r ,
since t h e a t t r i b u t e of c o l o r is n o t available, differences
between particles t e n d t o b e b a s e d o n m o r p h o l o g y
a n d , in s o m e cases, o n a t o m i c - n u m b e r - d e p e n d e n t
electron b a c k s c a t t e r i n g . F u r t h e r m o r e , since particles
smaller t h a n a few tens of 1 a r e difficult t o h a n d l e ,
the analysis m a y h a v e t o be d o n e in situ u s i n g energydispersive x-ray s p e c t r o s c o p y . T h i s m e t h o d p r i m a r i l y

p r o v i d e s q u a l i t i t a v e elemental analysis a n d c a n be
a p p l i e d t o p a r t i c u l a t e s u s i n g magnifications u p t o
a b o u t 5000 if t h e particles a r e well s e p a r a t e d . Light
m i c r o s c o p y is used in t h e magnification r a n g e of
~ 100-2000 x p r i m a r i l y t o e x a m i n e polished sections
b y reflection for o p a q u e m a t e r i a l s o r t r a n s m i s s i o n for
transparent materials.
W h i l e s o m e chemical i n f o r m a t i o n is o b t a i n a b l e b y
p o l a r i z e d light a n d refractive index m e a s u r e m e n t s , the
presence of multiple p h a s e s m a y indicate t h a t t h e
s a m p l e s h o u l d be a n a l y z e d either b y a high-spatialr e s o l u t i o n i n s t r u m e n t a l m e t h o d , like electron m i c r o p r o b e analysis, o r infrared m i c r o s c o p y . Alternatively,
it m a y be necessary t o dissolve t h e s a m p l e m a t r i x so as
t o isolate s e c o n d - p h a s e particles for analysis b y o t h e r
t e c h n i q u e s . T h e t r a n s m i s s i o n electron m i c r o s c o p e
e x t e n d s t h e ability t o p e r f o r m c o m b i n e d m i c r o s t r u c t u r a l a n d m i c r o c h e m i c a l analysis t o magnifications
well a b o v e 5000 , b u t t h e complexities of specimen
p r e p a r a t i o n a n d t h e relatively high cost a n d inaccessi
bility o f this m e t h o d in m o s t l a b o r a t o r i e s , c o m p a r e d
with light a n d s c a n n i n g electron m i c r o s c o p y , t e n d t o
m a k e it a m e t h o d w h i c h is c h o s e n only w h e n the o t h e r
m e t h o d s a r e unsuccessful.
If b y m i c r o s c o p i c e x a m i n a t i o n t h e s a m p l e a p p e a r s
t o b e fairly h o m o g e n e o u s , t h e a d v a n t a g e s associated
with t h e spatial selectivity of m i c r o a n a l y s i s c a n n o t be
realized a n d v a r i o u s m e t h o d s of b u l k analysis a r e
p r o b a b l y m o r e suitable. I n a d d i t i o n t o t r a d i t i o n a l wet
c h e m i c a l analysis, these m e t h o d s i n c l u d e s p a r k - s o u r c e
m a s s s p e c t r o m e t r y , optical emission a n d a b s o r p t i o n
s p e c t r o m e t r y a n d x-ray fluorescence spectroscopy.
E a c h h a s a sensitivity e x t e n d i n g d o w n t o t h e p a r t s p e r
million level a n d , in s o m e cases, well below. In
a d d i t i o n , t h e optical a n d x-ray t e c h n i q u e s c a n b o t h be
m a d e q u a n t i t a t i v e w i t h relative ease. T h e s e techniques
c a n often be applied t o i n h o m o g e n e o u s samples,
p r o v i d e d t h a t n o b r e a k d o w n b y p h a s e s is r e q u i r e d .
F i g u r e s 2, 3 a n d 4 give a n a p p r o x i m a t e s u m m a r y of
t h e p e r f o r m a n c e of s o m e of t h e m e t h o d s described,
with r e g a r d t o their ability t o d e t e r m i n e p h a s e m o r
p h o l o g y , crystal s t r u c t u r e a n d elemental c o m p o s i t i o n ,
respectively.
T h e preceding comments about determining sam
ple h o m o g e n e i t y refer principally t o solid i n o r g a n i c
s a m p l e s , a l t h o u g h all t h e t e c h n i q u e s m e n t i o n e d c a n
b e used o n p o l y m e r s as well, w i t h i n certain limitations
associated with v a c u u m a n d electron b e a m c o m p a t i
bility r e q u i r e m e n t s o f t h e electron m i c r o s c o p i c m e t h
o d s . F u r t h e r m o r e , x-ray fluorescence m e a s u r e m e n t s
a r e p r i m a r i l y c o n c e r n e d with elemental analysis
r a t h e r t h a n c o m p o u n d identification. Since c a r b o n ,
h y d r o g e n , n i t r o g e n a n d oxygen a r e u b i q u i t o u s in
o r g a n i c m a t e r i a l s , q u a l i t a t i v e e l e m e n t a l analysis by xr a y t e c h n i q u e s ( h y d r o g e n is u n d e t e c t a b l e by these
m e t h o d s ) d o e s little t o aid in t h e identification of t h e
m a t e r i a l o t h e r t h a n t o s h o w t h a t it is o r g a n i c . D e t e r
m i n i n g w h e t h e r a n o r g a n i c s a m p l e consists o f o n e o r
m o r e p h a s e s o r c o m p o u n d s is also a n i m p o r t a n t issue,

XXV

introduction

XRF

100 /xm

+3

">
g>

IR
xray
SEM

XRD~|

EPM
I

QL

LM

AEM

&

AEM

||

/iRBS

RBS

RBS
SIMS
STM/AFM

S T M / A F M "! A E S
0.1 n m '

10 n m

I \
100 \
Lateral resolution

I cm

0.1 n m

ESCA

10 n m

I /xm

100 ,

Lateral resolution

Figure 2
Lateral and depth resolution comparison for the methods
indicated in Fig. 1 used for studying morphology

Figure 4
Lateral and depth resolution comparison for the methods
indicated in Fig. 1 used for elemental analysis

however, b u t t h e types of s a m p l e s , t h e s e p a r a t i o n
techniques used a n d t h e k i n d s of i n f o r m a t i o n r e q u i r e d
c a n differ c o n s i d e r a b l y from t h o s e associated with t h e
e x a m i n a t i o n of i n o r g a n i c samples. First of all, m o s t
samples a r e either s u b m i t t e d as s o l u t i o n s o r a r e t a k e n
u p i n t o s o l u t i o n before analysis. S e p a r a t i o n s a r e
usually achieved b y s o l u t i o n chemistry, solvent
extraction o r c h r o m a t o g r a p h y (gas o r liquid). Separ
ated fractions a r e either a n a l y z e d b y direct i n t r o d u c
tion i n t o a physically c o u p l e d i n s t r u m e n t like a m a s s
o r infrared s p e c t r o m e t e r o r a r e collected a n d t r a n s
ferred t o a n o t h e r location for analysis. If t h e s a m p l e is
a p o l y m e r of only o n e type, t h e i n f o r m a t i o n s o u g h t
m a y be m o l e c u l a r weight d i s t r i b u t i o n a n d c h r o m a t o
g r a p h y (gel p e r m e a t i o n ) m a y be all t h a t is required. I n

o t h e r cases t h e i n f o r m a t i o n n e e d e d is t h e s t r u c t u r a l
f o r m u l a . T h i s c o u l d be d e t e r m i n e d from i n f o r m a t i o n
o b t a i n e d b y a variety of m e t h o d s including m a s s
s p e c t r o m e t r y , infrared s p e c t r o s c o p y a n d n u c l e a r m a g
netic r e s o n a n c e , as well as b y t r a d i t i o n a l c a r b o n ,
h y d r o g e n a n d o x y g e n analysis b a s e d o n c o m b u s t i o n
a n d gas a b s o r p t i o n . T h e s a m p l e size a n d c o n c e n t r a
tion r e q u i r e d a g a i n b e c o m e a n issue, b e c a u s e t h e
characteristics of t h e v a r i o u s t e c h n i q u e s differ
b r o a d l y . W h i l e n u c l e a r m a g n e t i c r e s o n a n c e is excel
lent for s t r u c t u r e d e t e r m i n a t i o n , it requires larger
samples than the other methods mentioned and can
rarely detect c o m p o u n d s o r functional g r o u p s a t a
c o n c e n t r a t i o n level less t h a n 0 . 1 % . O r g a n i c m a s s
s p e c t r o m e t r y , o n t h e o t h e r h a n d , c a n w o r k with m u c h
smaller s a m p l e s a n d detect c o m p o u n d s even below
t h e p a r t s p e r billion level in a well-separated s a m p l e .
S t r u c t u r a l i n f o r m a t i o n is h a r d e r t o o b t a i n , h o w e v e r ,
a n d c o m p o u n d s w i t h h i g h m o l e c u l a r weights ( > 2000)
a r e difficult t o a n a l y z e b y c o n v e n t i o n a l m e a n s . W i t h
systems of sufficiently high r e s o l u t i o n a n d soft ioniza
tion sources, it is possible t o o b t a i n m o l e c u l a r i o n s
a n d d e t e r m i n e s t o i c h i o m e t r y b a s e d o n direct p a c k i n g
fraction m e a s u r e m e n t s . I n s o m e cases, s t r u c t u r e c a n
also b e d e t e r m i n e d using c o n v e n t i o n a l electron
impact ionization and comparing fragmentation pat
tern spectra with t h o s e of k n o w n c o m p o u n d s .
Infrared s p e c t r o s c o p y c a n also h a v e relatively high
sensitivity t o specific functional g r o u p s a n d c a n b e
used t o e x a m i n e relatively small s a m p l e s , a l t h o u g h
larger o n e s a r e preferred for higher sensitivity. It is
used m o r e effectively in relating t h e s p e c t r u m of a n
u n k n o w n s a m p l e t o a reference s p e c t r u m r a t h e r t h a n
as a m e a n s of d e t e r m i n i n g t h e s t r u c t u r e of a c o m p l e t e
u n k n o w n . O f p a r t i c u l a r value is t h e fact t h a t it c a n be
r o u t i n e l y used t o e x a m i n e solid s a m p l e s s u c h a s
crosslinked insoluble p o l y m e r s .

XRD
100

SEM

\ |

XRD

AEM

RBS
I LEED

STM/AFM
0.1 n m

10 n m

I ,

100

I cm

Lateral resolution

Figure 3
Lateral and depth resolution comparison for the methods
indicated in Fig. 1 used for obtaining crystal structure
information

xxvi

Introduction
5. Cost and

Complexity

T h e r e c a n b e a n e n o r m o u s r a n g e in t h e costs associ
ated with m a t e r i a l s c h a r a c t e r i z a t i o n , d e p e n d i n g o n
the complexity of t h e p r o b l e m , t h e a m o u n t of infor
m a t i o n s o u g h t , t h e n u m b e r of s a m p l e s t o b e r u n , h o w
quickly t h e analysis h a s t o b e d o n e a n d t h e i n v e s t m e n t
in e q u i p m e n t a n d m a n p o w e r . M u l t i e l e m e n t analysis
for large n u m b e r s of r o u t i n e s a m p l e s c a n b e effected
for less t h a n U S $ 2 5 p e r s a m p l e , while c o m p l e x surface
analysis c a n exceed U S $ 1 0 0 0 p e r s a m p l e . Access t o a
p a r t i c u l a r t y p e of i n s t r u m e n t a t i o n of t h e types d e
scribed so far d o e s n o t p r o v i d e all t h e i n f o r m a t i o n
needed a b o u t w h e t h e r a given t e c h n i q u e will h a v e t h e
sensitivity, r e s o l u t i o n o r s a m p l e h a n d l i n g c a p a b i l i t y
t o d o a given j o b . It is possible t o p u r c h a s e c o m p l e t e
m a s s s p e c t r o m e t e r systems for u n d e r U S $ 5 0 0 0 o r
over U S $ 5 0 0 000. W h i l e t h e f o r m e r m a y b e perfectly
a d e q u a t e as a residual g a s a n a l y z e r w h e r e u n i t m a s s
resolution is sufficient, it w o u l d b e totally unsatisfac
t o r y for t h e analysis of h i g h - m o l e c u l a r - w e i g h t o r g a n i c
c o m p o u n d s . E v e n if t h e larger s u m of m o n e y w e r e
available, a h i g h - r e s o l u t i o n m a s s s p e c t r o m e t e r for
isotopic analysis w o u l d b e decidedly different from
o n e used for c o m b i n e d gas c h r o m a t o g r a p h y m a s s
spectrometry.
T h e trade-off b e t w e e n cost a n d p e r f o r m a n c e
features is characteristic of all m a j o r pieces of a n a l y t i
cal i n s t r u m e n t a t i o n . T o deal effectively w i t h this issue
w h e n selecting a n i n s t r u m e n t t o p u r c h a s e o r use for a
given a p p l i c a t i o n r e q u i r e s t h e d e v e l o p m e n t of a speci
fication
for i n s t r u m e n t p e r f o r m a n c e relative t o
i n t e n d e d use. A g a i n t a k i n g m a s s s p e c t r o m e t r y a s a n
e x a m p l e , if t h e need is for high-sensitivity, h i g h resolution analysis of g a s c h r o m a t o g r a p h effluents, a n
i n s t r u m e n t m i g h t b e specified w i t h a highly efficient
electron i m p a c t s o u r c e c o u p l e d t o a fast-switching,
double-focusing a n a l y z e r w i t h high-sensitivity electri
cal detection. F u r t h e r m o r e , it s h o u l d also b e possible
t o specify a generally a c c e p t e d p e r f o r m a n c e s t a n d a r d .
F o r e x a m p l e , t h e i n s t r u m e n t s h o u l d be able t o detect
9
1 0 ~ C of i o n p e r g of m e t h y l s t e a r a t e a t a m a s s
resolution of 1 p a r t in 10 000 a n d a s o u r c e v o l t a g e of
8 k V . G e n e r a l l y , w h e n selecting a n i n s t r u m e n t of a n y
type, cost rises w i t h p e r f o r m a n c e . It is therefore
i n c u m b e n t o n t h e b u y e r t o b e realistic a b o u t h o w
m a n y special features a n d w h a t level of p e r f o r m a n c e
are n e e d e d for a given r a n g e of a p p l i c a t i o n s . It m a k e s
little sense t o p a y t h e a d d e d cost for a s c a n n i n g
electron m i c r o s c o p e c a p a b l e of 1 0 0 0 0 0 magnifica
tion relative t o a lower r e s o l u t i o n m o d e l if t h e details
of interest a r e clearly o b s e r v a b l e a t 5000 o r if t h e
n a t u r e of t h e s a m p l e is such t h a t p i c t u r e s a t h i g h e r
magnifications a r e n o t possible.

6.

Trends

T h e m a j o r i m p a c t of c o m p u t e r s a n d m i c r o e l e c t r o n i c s
on materials characterization techniques, already

a l l u d e d t o , will u n d o u b t e d l y c o n t i n u e for a n u m b e r of
years. I n a d d i t i o n t o i n s t r u m e n t c o n t r o l , d a t a collec
t i o n a n d t h e p r o c e s s i n g of results, c o m p u t e r s will p l a y
a m o r e i m p o r t a n t role in m e t h o d selection a n d the
m a n a g e m e n t of l a b o r a t o r y i n f o r m a t i o n . It c a n be
expected t h a t m o r e general spectral d a t a b a s e s a n d
efficient m e a n s for s e a r c h i n g t h e m will lead b o t h t o
faster a n d t o m o r e c o m p l e t e results. Since specimen
p r e p a r a t i o n is often a rate-limiting step in m a n y
f o r m s of analysis, l a b o r a t o r y r o b o t s a r e n o w being
used m o r e extensively t o also i m p r o v e q u a l i t y a n d
productivity.
I n very general t e r m s , m o s t analytical i n s t r u m e n t s
c a n b e t h o u g h t of as consisting of a source, a n
a n a l y z e r a n d a d e t e c t o r . A s w a s s h o w n in Fig. 1, the
s o u r c e c a n b e used o n t h e i n t e r a c t i o n of the s a m p l e
w i t h p r o b i n g r a d i a t i o n of a n y w a v e l e n g t h o r particles
of different types a n d energies. It m a y even be the
specimen itself, as in t h e case of the analysis of
r a d i o a c t i v e s a m p l e s . T h e a n a l y z e r serves as a m e a n s
of s e p a r a t i n g t h e signals e m i t t e d o r scattered b y t h e
s a m p l e , b a s e d o n differences in their physical o r
chemical p r o p e r t i e s , a n d finally t h e d e t e c t o r c o n v e r t s
t h e s e p a r a t e d signals i n t o a c o m p r e h e n s i b l e form. A
m a j o r t r e n d , w h i c h e m e r g e d d u r i n g t h e 1980s, is t o try
all m a n n e r of c o m b i n a t i o n s of sources, analyzers a n d
d e t e c t o r s a n d t h e r e b y c r e a t e i n s t r u m e n t s which a r e
o p t i m i z e d for p a r t i c u l a r a p p l i c a t i o n s . I n o r g a n i c m a s s
s p e c t r o m e t r y , for e x a m p l e , ion sources a r e b a s e d o n
e l e c t r o n i m p a c t , field i o n i z a t i o n , field d e s o r p t i o n ,
laser i o n i z a t i o n a n d b o t h ion a n d n e u t r a l particle
b e a m s . I n gas c h r o m a t o g r a p h y , d e t e c t o r s include
flame i o n i z a t i o n , electron c a p t u r e , t h e r m a l c o n d u c
tivity a n d infrared s p e c t r o m e t r y .
If t h e s a m p l e is o n l y p a r t l y c o n s u m e d o r n o t
c o n s u m e d a t all b y a given d e t e c t i o n process, multiple
d e t e c t o r s c a n b e u s e d in series t o p r o v i d e c o m p l e m e n
t a r y i n f o r m a t i o n . T h i s h a s b e e n d o n e in b o t h gas a n d
liquid c h r o m a t o g r a p h y . S o m e t i m e s t h e d e t e c t o r is
itself a s p e c t r o m e t e r a n d t h u s allows s e p a r a t e d species
t o b e c h a r a c t e r i z e d m o r e fully. E x a m p l e s include gas
a n d liquid c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y a n d
b o t h g a s a n d liquid c h r o m a t o g r a p h y - i n f r a r e d spec
t r o m e t r y . A n i m p o r t a n t c h a r a c t e r i s t i c of s p e c t r o m e t r i c d e t e c t o r s used in c o m b i n a t i o n m e t h o d s is t h a t
they m u s t either b e very fast o r function in a parallel
d e t e c t i o n m o d e . T h u s , in t h e e x a m p l e s j u s t m e n
t i o n e d , a m a s s s p e c t r o m e t e r c a p a b l e of s c a n n i n g its
c o m p l e t e m a s s r a n g e in a few s e c o n d s is used in o n e
case a n d F o u r i e r t r a n s f o r m infrared s p e c t r o m e t r y in
t h e o t h e r . If s e p a r a t i o n t e c h n i q u e s a r e t o b e used with
a t o m i c emission t e c h n i q u e s , s o m e of t h e newly
d e v e l o p e d types of parallel d e t e c t i o n optical spec
t r o m e t e r s will p r o v e very v a l u a b l e . I n o t h e r analytical
s i t u a t i o n s , several d e t e c t o r s c a p a b l e of m o n i t o r i n g a
variety of signals a r e used a t t h e s a m e time. F o r
e x a m p l e , s i m u l t a n e o u s x-ray a n d electron d e t e c t i o n in
s c a n n i n g electron m i c r o s c o p e s a n d analytical t r a n s
mission electron m i c r o s c o p e s m a k e s it possible t o

xxvii

Introduction
relate chemical t o m i c r o s t r u c t u r a l i n f o r m a t i o n easily.
It is always difficult t o predict w h e r e a n y field will
go in t h e future, b u t clearly defined needs c o u p l e d
with active technologies c a n p r o v i d e s o m e h i n t s . All
analytical m e t h o d s s h a r e the c o m m o n goals of h i g h e r
speed, lower cost, g r e a t e r sensitivity, m o r e flexibility
a n d increased a c c u r a c y . Since t h e early 1970s, re
m a r k a b l e p r o g r e s s h a s b e e n m a d e in a d v a n c i n g loca
lized elemental analysis capability t o t h e limit of
single-atom detection by a t o m - m i c r o p r o b e analysis
a n d u l t r a h i g h - r e s o l u t i o n s c a n n i n g t r a n s m i s s i o n elec
t r o n m i c r o s c o p y , a l t h o u g h only limited k i n d s of s a m
ple are suitable for these m e t h o d s . A t o m i c r e s o l u t i o n
c h a r a c t e r i z a t i o n of surfaces is n o w possible as a result
of recent d e v e l o p m e n t of t h e s c a n n i n g tunnelling a n d
s c a n n i n g force m i c r o s c o p e s ( S T M a n d A F M ) . T h e s e
i n s t r u m e n t s p r o v i d e a relatively low-cost w a y of
i m a g i n g m a n y surfaces directly with a t o m i c resolu
tion. U n l i k e electron m i c r o s c o p e s they utilize very
fine physical p r o b e s a n d d o n o t need t o o p e r a t e
in a v a c u u m e n v i r o n m e n t . I n a d d i t i o n t o surface
m o r p h o l o g y c h a r a c t e r i z a t i o n , v a r i a t i o n s of t h e tech
n i q u e offer p r o m i s e in t h e m e a s u r e m e n t of localized
physical a n d chemical p r o p e r t i e s . T h e p o s i t i o n of
S T M / A F M t e c h n i q u e s in t h e lower left of Figs. 2 - 4 is
indicative of their high p o t e n t i a l t o e x p a n d t h e fron
tiers of m a t e r i a l s c h a r a c t e r i z a t o n . T h e r e is still a need,
however, for higher spatial resolution t e c h n i q u e s t h a t
can identify c o m p o u n d s , p a r t i c u l a r l y o r g a n i c s , since a
k n o w l e d g e of elemental c o n s t i t u e n t s is usually of little
value in distinguishing o n e m a t e r i a l from a n o t h e r .
Selected a r e a diffraction a n d , m o r e recently, m i c r o diffraction a r e routinely used t o identify i n o r g a n i c
c o m p o u n d s in t r a n s m i s s i o n electron m i c r o s c o p e s .
T h e newer m e t h o d h a s even given results from a r e a s
less t h a t 5 n m in d i a m e t e r . H o w e v e r , these a p p r o a c h e s
are of very limited value in t h e e x a m i n a t i o n of o r g a n i c
materials, because of electron b e a m d a m a g e a n d the
fact t h a t m a n y o r g a n i c s of interest a r e in a n o n c r y s t a l
line form.
T h e full c h a r a c t e r i z a t i o n of thin o r g a n i c films even
w h e n lateral spatial r e s o l u t i o n is n o t a n issue is
c o m p l i c a t e d for o t h e r r e a s o n s . X - r a y p h o t o e l e c t r o n

xxviii

s p e c t r o s c o p y h a s a l r e a d y p r o v e d itself t o b e a p o w e r
ful t o o l , b u t t h e chemical shift i n f o r m a t i o n c o n t a i n e d
in a s p e c t r u m is often difficult t o e x t r a c t b e c a u s e of
t h e i n h e r e n t energy r e s o l u t i o n limits of t h e t e c h n i q u e .
P e r h a p s o n e of t h e m o s t interesting a n d challenging
p r o b l e m s is t h e a t o m i c level c h a r a c t e r i z a t i o n of inter
faces w i t h i n m a t e r i a l s , w h e r e a n y a t t e m p t t o r e a c h
t h e interfaces by m a t e r i a l r e m o v a l , as is d o n e in
s e c o n d a r y - i o n m a s s s p e c t r o m e t r y a n d A u g e r electron
analysis, so alters t h e m as t o m a k e t h e i n f o r m a t i o n
o b t a i n e d useless. F o r these k i n d s of p r o b l e m s , n o n
destructive t e c h n i q u e s like solid-state n u c l e a r m a g
netic r e s o n a n c e a n d s o m e f o r m s of laser s p e c t r o s c o p y
may provide valuable solutions.

Bibliography
Briggs D, Seah 1983 Practical Surface Analysis. Wiley,
Chichester, UK
Casper L A, Powell C J (eds.) 1982 Industrial Applications of
Surface Analysis. American Chemical Society, Wash
ington, DC
Czandema A W (ed.) 1975 Methods of Surface Analysis.
Elsevier, Amsterdam
Ewing G W 1975 Instrumental Methods of Chemical Analy
sis, 4th edn. McGraw-Hill, New York
Friend J 1951 Man and the Chemical Elements. Griffin,
London
Ihde A J 1964 The Development of Modern Chemistry.
Harper and Row, New York
Kane P K , Larrabee G B (eds.) 1974 Characterization of
Solid Surfaces. Plenum, New York
Mulvey T, Webster R (eds.) 1974 Modern Physical Tech
niques in Materials Science. Oxford University Press,
Oxford
Partington J R 1962 A History of Chemistry, Vols. 1-4.
Macmillan, London
Peters P G et al. 1976 A Brief Introduction to Modern
Chemical Analysis. Saunders, Philadelphia, PA
Skoog D A , West D M 1982 Fundamentals of Analytical
Chemistry, 4th edn. CBS College Publishing, New York
Voreso Louise (ed.) 1992 Instrumentation in Analytical
Chemistry, 1988-1991. American Chemical Society,
Washington, DC

A
Acoustic Emission
A c o u s t i c emission ( A E ) is t h e t r a n s i e n t m e c h a n i c a l
v i b r a t i o n a c c o m p a n y i n g a s u d d e n release of s t o r e d
elastic energy o r chemical free energy. It o c c u r s a s a
c o n s e q u e n c e of t h e i m p o s i t i o n of e n v i r o n m e n t a l stress
o n m a t e r i a l s . T h e A E r e s p o n s e of a large n u m b e r of
m a t e r i a l s h a s been studied as a function of m e c h
anically, t h e r m a l l y o r chemically i n d u c e d stresses.
D e t e c t i o n , analysis a n d i n t e r p r e t a t i o n of A E from
m a t e r i a l s , p a r t s a n d s t r u c t u r e s forms t h e basis of
this n o n d e s t r u c t i v e e v a l u a t i o n ( N D E ) m e t h o d .
A E originates from a variety of s o u r c e s in m a t e r
ials. T h e s e include localized, r a p i d m o v e m e n t s of
m a t e r i a l , such a s initiation a n d p r o p a g a t i o n of c r a c k s ,
twinning, slip, m a r t e n s i t i c p h a s e t r a n s f o r m a t i o n s a n d
void coalescence. A n y similar d y n a m i c a n d localized
m o v e m e n t of m a t e r i a l will also act a s a n A E s o u r c e .
Processes t h a t o c c u r via a t o m - b y - a t o m diffusion a r e
n o t u s a b l e A E s o u r c e s . D i s l o c a t i o n m o t i o n s , except
for c o o p e r a t i v e m o t i o n of m a n y d i s l o c a t i o n s , a r e n o t
usable A E sources. M a t r i x c r a z i n g , fiber-matrix disb o n d i n g , fiber fracture a n d d e l a m i n a t i o n a r e sources
of A E in fiber c o m p o s i t e s .
A E sources t e n d t o be localized events in m a t e r i a l s .
A E precedes gross failure of t h e m a t e r i a l w h e n it is
used in a p a r t , c o m p o n e n t o r s t r u c t u r e a n d t h u s A E
c a n be a n effective N D E t o o l w h e n p r o p e r l y detected
and analyzed.

1. General

Features

of AE

Signals

A E signals a r e s t i m u l a t e d in m a t e r i a l s b y m e c h a n i c a l ,
t h e r m a l o r chemically i n d u c e d stresses. E a c h m a t e r i a l
exhibits its o w n u n i q u e A E r e s p o n s e characteristics.
H o w e v e r , t w o b r o a d types of A E r e s p o n s e c a n b e
described w h i c h serve as useful q u a l i t a t i v e descrip
tions: c o n t i n u o u s A E a n d b u r s t A E . C o n t i n u o u s A E
h a s w a v e f o r m s similar t o G a u s s i a n noise a n d is
generally associated w i t h t h e m o r e ductile m a t e r i a l s .
It c h a n g e s in a v e r a g e a m p l i t u d e , b u t n o t in general
a p p e a r a n c e , as t h e s t i m u l a t i o n p a r a m e t e r s of t h e
w o r k p i e c e being studied a r e c h a n g e d . It t e n d s t o s h o w
a large increase in a v e r a g e a m p l i t u d e w h e n a m a t e r i a l
yields, either locally o r in a gross fashion. C o n t i n u o u s
A E is believed t o b e m a d e u p of a large n u m b e r of
very small v i b r a t o r y t r a n s i e n t s , r a n d o m l y d i s t r i b u t e d
in time. B u r s t A E h a s larger a m p l i t u d e s a n d t h e b u r s t
events a r e sufficiently s e p a r a t e d in time t h a t they
a p p e a r t o b e discrete events. B u r s t A E is usually
observed w h e n brittle m a t e r i a l s o r m a t e r i a l s w i t h
brittle c o m p o n e n t s a r e b e i n g s t u d i e d . Stable c r a c k
g r o w t h in h i g h - s t r e n g t h steel a n d fiber fracture in

c o m p o s i t e s g e n e r a t e b u r s t A E . B u r s t A E is t h e m o r e
useful t y p e for N D E a p p l i c a t i o n s because it is m o r e
closely associated with processes t h a t c a n lead t o local
o r c a t a s t r o p h i c failure.
M a t e r i a l s in t h e m i d - r a n g e of ductility frequently
s h o w p r e d o m i n a n t l y c o n t i n u o u s A E a t low values of
s t i m u l a t i o n , t h e n b u r s t A E a p p e a r s as t h e s t i m u l a t i o n
increases a n d failure of t h e w o r k p i e c e a p p r o a c h e s .
M a t r i x crazing in c o m p o s i t e s frequently h a s the
a p p e a r a n c e of c o n t i n u o u s A E , w h e r e a s fiber fracture
produces burst A E .

2. Unique Features

of Acoustic-Emission

NDE

M o s t N D E m e t h o d s d e p e n d o n injecting a directed
b e a m of energy i n t o a m a t e r i a l . T h i s is t h e case, for
e x a m p l e , in t h e x-ray, u l t r a s o n i c , e d d y - c u r r e n t a n d
m i c r o w a v e m e t h o d s . A n analysis of t h e scattering,
a t t e n u a t i o n o r a b s o r p t i o n of t h e injected b e a m as it
interacts with a d i s c o n t i n u i t y in t h e m a t e r i a l is t h e n
r e q u i r e d in o r d e r t o describe t h e discontinuity, the
o u t p u t b e a m b e i n g received b y a n a p p r o p r i a t e sensor.
T h e m a t e r i a l of t h e w o r k p i e c e being studied plays a n
entirely passive role in this process, a l t h o u g h the
m a t e r i a l a n d its characteristic defect d i s t r i b u t i o n sig
nificantly influence t h e choice of N D E m e t h o d . T h e
s a m e f o r m of energy is received in e a c h of these cases
as is injected.
A E is s t i m u l a t e d by a n entirely different form of
energy t h a n is received a t t h e sensor for analysis. T h e
w o r k p i e c e m u s t h a v e m e c h a n i c a l stresses i n d u c e d i n t o
it either by m e c h a n i c a l , t h e r m a l o r chemical m e a n s .
A E , a n a c o u s t i c (usually u l t r a s o n i c ) t r a n s i e n t vibra
tion, is g e n e r a t e d w h e n a d i s c o n t i n u i t y s u d d e n l y re
leases all o r a p o r t i o n of t h e stress i n d u c e d i n t o it. T h e
m a t e r i a l , its d i s c o n t i n u i t y a n d t h e w o r k p i e c e geo
m e t r y d e t e r m i n e w h a t t h e o u t p u t signal will be. T h e
A E generated by a particular discontinuity under a
given set of s t i m u l a t i o n c o n d i t i o n s c o n t a i n s u n i q u e
information concerning the changes that occurred at
t h e d i s c o n t i n u i t y . N o t e t h a t it is only c h a n g e s t h a t c a n
be discerned with A E , t h u s it is a d y n a m i c N D E
m e t h o d , as well as being a m e t h o d t h a t is intensively
related t o t h e specific m a t e r i a l being tested.
A E h a s serious d i s a d v a n t a g e s as well as distinct
advantages when compared with other N D E meth
o d s . It c a n only detect discontinuities t h a t cause
a b r u p t c h a n g e s in their s u r r o u n d i n g stress fields as a
result of s t i m u l a t i o n . T h e s e discontinuities a r e very
likely t o be t h e m o s t serious o n e s in a p a r t i c u l a r
w o r k p i e c e , b u t large discontinuities t h a t a r e n o t
revealed b y a n A E test need t o be considered ser
iously, especially in t h e case of fatigue service. T h e
1

Acoustic

Emission

s t i m u l a t i o n r e q u i r e d m u s t be g r e a t e r t h a n t h a t
expected in service, t o e n s u r e t h a t existing disconti
nuities a r e n o t serious, even for static service. If
m e c h a n i c a l l o a d i n g is t h e s t i m u l a t i o n , for e x a m p l e ,
e q u i p m e n t foreign t o , a n d s o m e t i m e s u n a v a i l a b l e t o
N D E g r o u p s will b e r e q u i r e d . F u r t h e r m o r e , A E is
inferior t o o t h e r N D E m e t h o d s in its ability t o
describe t h e size a n d s h a p e of a discontinuity; x-ray
and ultrasonic methods are superior. However, A E
has the advantage that a discontinuity can be located
by using multiple sensors (as described in Sect. 4)
w i t h o u t a long, detailed a n d expensive search, if t h e
discontinuity is a n A E s o u r c e . A E c a n also detect
discontinuities t h a t a r e below t h e d e t e c t i o n limit of
o t h e r N D E m e t h o d s b y a t least a n o r d e r of m a g n i
t u d e ; a n e x a m p l e is t h e f o r m a t i o n of a c r a c k e m b r y o
d u e t o a b r e a k a w a y of a dislocation p i l e u p .

3. Analog-Instrumentation

Methods

A E is m o s t frequently detected using a piezoelectric

sensor ( t r a n s d u c e r ) w h i c h is a t t a c h e d t o t h e w o r k p i e c e
via a g o o d u l t r a s o n i c c o u p l a n t . Its p u r p o s e is t o
convert the A E , a transient mechanical vibration, into
a c o r r e s p o n d i n g electrical signal. Amplification of t h e
sensor o u t p u t is n o r m a l l y p e r f o r m e d in t w o stages.
T h e o u t p u t first goes t o a preamplifier of high q u a l i t y
(low noise i n p u t ) , w h e r e t h e signal is amplified b y a
factor of 10-100. T h e preamplifier o u t p u t s h o u l d b e
c a p a b l e of driving a l o n g cable a n d s h o u l d b e m a t c h e d
t o a second amplifier w h e r e further amplification is
p e r f o r m e d . T h e amplified signal m a y t h e n b e p r o
cessed in a variety of w a y s t o p r o d u c e a r e c o r d u p o n
which a q u a l i t y e v a l u a t i o n of t h e w o r k p i e c e u n d e r
s t u d y c a n be m a d e .
A classical w a y of p r o d u c i n g a n A E r e c o r d is t o
simply g e n e r a t e a r e c o r d of t h e t o t a l A E c o u n t s a s a
function of t h e s t i m u l a t i o n p a r a m e t e r . T o d o this, t h e
amplified signal is fed t o a n electronic c o u n t e r w i t h a n
adjustable trigger. T h e trigger is set a t a value slightly
a b o v e , usually twice, t h e a m b i e n t electronic noise
level of t h e amplification system. A p l o t m a y t h e n b e
p r o d u c e d t h a t s h o w s A E c o u n t s u m m a t i o n as a
function of t h e s t i m u l a t i o n p a r a m e t e r . A v a r i a t i o n of
this m e t h o d is t o reset t h e c o u n t e r after a p r e d e t e r
m i n e d s h o r t p e r i o d of time. It is t h e n possible t o
g e n e r a t e a r e c o r d of t h e A E c o u n t r a t e as a function of
the stimulation parameter.
A simple w a y of p r o d u c i n g a n A E r e c o r d is t o feed
the amplified signal t o a r o o t - m e a n - s q u a r e ( R M S )
meter. T h e a v e r a g e R M S level is indicative of t h e
a m o u n t of c o n t i n u o u s A E ; spikes o n t h e R M S o u t p u t
a r e indicative of b u r s t A E . A g a i n , t h e A E r e c o r d is
c o r r e l a t e d with t h e s t i m u l a t i o n p a r a m e t e r t o p r o d u c e
a test r e c o r d .
T h e d y n a m i c r a n g e of signals from a n A E test
c a n b e very h i g h , a n d s o m e t i m e s exceeds 60 d B . F o r
this r e a s o n , l o g a r i t h m i c amplifiers, r a t h e r t h a n

linear amplifiers, a r e s o m e t i m e s c h o s e n . T h e d a t a acquisition p r o c e d u r e s described m a y all b e u s e d in

either t h e linear o r l o g a r i t h m i c m o d e .

4. Digital-Instrumentation

Methods

T h e increased availability a n d versatility of m i c r o

computer, minicomputer and computer components
h a v e led t o a significantly e n h a n c e d capability for
e x t r a c t i n g i n f o r m a t i o n from A E signals. H o w e v e r ,
since a single A E test m a y involve millions of signals,
i n n o v a t i v e m e t h o d s of e x t r a c t i n g t h e m o s t signifi
c a n t i n f o r m a t i o n from i n d i v i d u a l A E signals a r e still
necessary.
C o m m e r c i a l l y available systems c a n r e c o r d signal
features s u c h a s t i m e of o c c u r r e n c e , rise t i m e ,
d u r a t i o n , p e a k a m p l i t u d e , p e a k dwell time, fall t i m e
a n d s t i m u l a t i o n - p a r a m e t e r i n f o r m a t i o n . T h i s infor
m a t i o n c a n b e s t o r e d digitally a n d t h e i n f o r m a t i o n
c a n t h e n b e used for b o t h in-process a n d p o s t - p r o c e s s
analysis of A E d a t a .
A m p l i t u d e - d i s t r i b u t i o n analysis h a s p r o v e d t o b e
effective in a n u m b e r of c i r c u m s t a n c e s . I n this tech
n i q u e , t h e n u m b e r of signals w h o s e a m p l i t u d e exceeds
a prescribed value is p l o t t e d a g a i n s t a m p l i t u d e . Alter
natively, t h e a b s o l u t e v a l u e of t h e derivative of this
c u r v e c a n b e p l o t t e d . F o r e x a m p l e , a m p l i t u d e distri
b u t i o n s h a v e b e e n used t o reveal m u l t i p l e A E sources
in m a t e r i a l s a n d t o detect t h e o p e r a t i o n of a n e w A E
s o u r c e , p e r h a p s t h e o n e t h a t m a y lead t o m a t e r i a l
failure, as t h e s t i m u l a t i o n p a r a m e t e r is increased.
B o t h rise t i m e a n d p e a k dwell time c a n b e used t o
s e p a r a t e real A E from e x t r a n e o u s signals of similar
a p p e a r a n c e . Electrical t r a n s i e n t s t e n d t o h a v e very
fast rise times a n d s h o r t dwell times, w h e r e a s frac
t i o n a l r u b b i n g p h e n o m e n a t e n d t o h a v e slow rise
times a n d l o n g dwell times. T h u s , ability t o m a n i p u
late d a t a with respect t o these t w o p a r a m e t e r s is a
distinct a d v a n t a g e .
F l a w l o c a t i o n , if t h e flaw is a s o u r c e of A E , c a n b e
a c c o m p l i s h e d b y a c o m p u t e r - a i d e d multiple-sensor
a r r a y . A s s u m p t i o n s implicit in a s t r a i g h t f o r w a r d a p
p l i c a t i o n o f l o c a t i o n t h e o r y a r e t h a t t h e A E signal
travels from t h e s o u r c e t o e a c h sensor in t h e d e t e c t i o n
a r r a y w i t h o u t c h a n g e in w a v e f o r m o r p r o p a g a t i o n
speed. T h e s e c o n d i t i o n s a r e s e l d o m m e t exactly, b u t
a r e a p p r o x i m a t e d closely e n o u g h in m a n y a p p l i c a
tions t o m a k e A E flaw l o c a t i o n a powerful N D E t o o l .
AE
flaw-location
techniques have become m o r e
sophisticated rapidly, a d v a n c i n g in step with a d
vances in c o m p u t e r t e c h n o l o g y .
Ability t o t u r n a n A E d a t a - a c q u i s i t i o n system o n
a n d off is a distinct a d v a n t a g e in s o m e tests. I n fatigue
tests, g a t i n g t h e system o n d u r i n g only t h e m o s t
significant p o r t i o n of e a c h l o a d i n g cycle p r e v e n t s
m i x i n g A E c r a c k - g r o w t h signals w i t h e x t r a n e o u s
noise. T i m e g a t i n g is useful in m o n i t o r i n g p e r c u s s i o n welding o r electric-resistance-welding (spot-welding)

Acoustic

processes, since it p e r m i t s t h e isolation of t h e m o s t

i m p o r t a n t A E processes d u r i n g t h e welding sequence.
M a n y a t t e m p t s h a v e been m a d e t o p e r f o r m fast
F o u r i e r t r a n s f o r m s of A E signals, a n d t o a n a l y z e t h e
signals in t h e frequency d o m a i n . W h i l e s o m e a t t e m p t s
h a v e been successful, m o s t h a v e n o t . T h i s t e c h n i q u e is
c o m p l i c a t e d b y t h e fact t h a t t h e A E signal is severely
modified as it passes from s o u r c e t o sensor. W o r k piece g e o m e t r y seriously modifies t h e signal, as d o
a t t e n u a t i o n characteristics of t h e m a t e r i a l .

5. Unique Capabilities
Method

of the

Acoustic-Emission

A E inspection m e t h o d s c a n b e used in a n u m b e r of
situations w h e r e o t h e r N D E m e t h o d s w o u l d be p r o h i
bitively expensive o r totally impossible. I n these in
spection a p p l i c a t i o n s , t h e i n f o r m a t i o n w h i c h c a n b e
a c q u i r e d is n o t likely t o fulfill r e q u i r e m e n t s of existing
codes. In s o m e cases, n o such g u i d a n c e exists for a n y
N D E inspection m e t h o d . T h u s , n e w goals need t o be
set for t h e inspection a n d n e w p r o c e d u r e s need t o b e
established for i n t e r p r e t i n g t h e d a t a in m a n y cases.
A E c a n b e used t o m o n i t o r s t r u c t u r e s a n d m a c h i n e s
c o n t i n u o u s l y while they a r e in o p e r a t i o n a sig
nificant a d v a n t a g e for N D E . E x a m p l e s a r e s t e a m
turbines, electric g e n e r a t o r s , circulating p u m p s , p i p e
lines, valves, chemical p l a n t s , aircraft a n d offshore
p l a t f o r m s . Studies a r e in p r o g r e s s t o define p r o
cedures for c o m p r e h e n s i v e m o n i t o r i n g of n u c l e a r
reactors.
In-process m o n i t o r i n g of welds h a s also been per
fected as a n inspection m e t h o d . Electric-resistance,
percussion a n d t u b i n g - p i n c h welds c a n be q u a l i t y
assured a s they a r e m a d e . L a s e r welds c a n b e success
fully inspected as they a r e m a d e , a n d t h e t e c h n i q u e is
highly d e v e l o p e d for welding cables t o c o n n e c t o r s .
Successful m e t h o d s h a v e been d e v e l o p e d for inprocess inspection of welds in heavy-section steel,
w h e r e multiple passes of weld m a t e r i a l a r e laid d o w n .
T h e r e is a large cost a d v a n t a g e in detecting a b a d weld
u n d e r these c o n d i t i o n s , since t h e cost of r e m o v i n g
large a m o u n t s of m a t e r i a l t o r e p a i r t h e b a d weld p a s s
is saved.
In-process inspection of o t h e r m a n u f a c t u r i n g p r o
cesses, such as p u n c h i n g , m e t a l f o r m i n g a n d casting,
is u n d e r d e v e l o p m e n t .

Acknowledgement
T h e w o r k of t h e a u t h o r is p e r f o r m e d u n d e r t h e
auspices of t h e U S D e p a r t m e n t of E n e r g y , C o n t r a c t
No. W-7405-ENG-48.
See also: Wood: Acoustic Emission and Acousto-Ultrasonic
Characteristics

Emission

Bibliography
American Society for Testing and Materials 1981 Standard
definition of terms relating to acoustic emission, E610-77.
1981 Annual Book of AST Standards, Pt. 11: Metallo
graphy; Nondestructive Testing. ASTM, Philadelphia,
PA, pp. 603-5
American Society for Testing and Materials 1981 Standard
practice for acoustic emission monitoring during continu
ous welding, E749-80. 1981 Annual Book of ASTM Stan
dards, Pt. 11: Metallography; Nondestructive Testing,
ASTM, Philadelphia, PA, pp. 698-704
American Society for Testing and Materials 1981 Standard
practice for acoustic emission monitoring during resist
ance spot welding, E751-80. 1981 Annual Book of ASTM
Standards, Pt. 11: Metallography; Nondestructive Testing.
ASTM, Philadelphia, PA, pp. 716-24
American Society for Testing and Materials 1981 Standard
practice for measuring the operating characteristics of
acoustic emission instrumentation, E750-80. 1981 Annual
Book of ASTM Standards, Pt. 11: Metallography; Non
destructive Testing. ASTM, Philadelphia, PA, pp. 705-15
American Society for Testing and Materials 1981 Standard
practice for mounting piezoelectric acoustic emission con
tact sensors, E650-78. 1981 Annual Book of ASTM Stan
dards, Pt. 11: Metallography; Nondestructive Testing.
ASTM, Philadelphia, PA, pp. 606-8
American Society for Testing and Materials 1981 Standard
recommended practice for acoustic emission monitoring
of structures during controlled stimulation, E569-76.
1981 Annual Book of ASTM Standards, Pt. 11: Metallo
graphy; Nondestructive Testing. ASTM, Philadelphia,
PA, pp. 5 5 1 ^
Drouillard F, Laner F J 1979 Acoustic Emission: A
Bibliography with Abstracts. IFI Plenum Data Company,
New York
Dunegan L, Hartman W F (eds.) 1981 Advances in
Acoustic Emission. Dunhart, Knoxville, TN
Dunegan L, Tatro C A 1971 Acoustic emission effects
during mechanical deformation. In: Bunshah R F (ed.)
1981 Techniques of Metals Research, Vol. 5, Pt. 2. Interscience, New York, pp. 273-312
Hartman W F, McElroy J W (eds.) 1979 Acoustic Emission
Monitoring of Pressurized Systems, ASTM Special Tech
nical Publication 697. American Society for Testing and
Materials, Philadelphia, PA
Liptai R G, Harris D O, Tatro C A (eds.) 1972 Acoustic
Emission, ASTM Special Technical Publication 505. Am
erican Society for Testing and Materials, Philadelphia,
PA
Liptai R G, Tatro C A 1976 Acoustic emission inspection.
Metals Handbook, 8th edn., Vol. 11. ASM International,
Materials Park, OH
Nichols R W (ed.) 1976 Acoustic Emission. Applied Science,
Barking, UK
Spanner J C 1974 Acoustic Emission Techniques and Applica
tions. Intex, Evanston, IL
Spanner J C, McElroy J W (eds.) 1975 Monitoring Structural
Integrity by Acoustic Emission, ASTM Special Technical
Publication 571. American Society for Testing and
Materials, Philadelphia, PA
C. A . T a t r o
[Lawrence Livermore Laboratory,
L i v e r m o r e , California, U S A ]

Acoustic

Microscopy

Acoustic Microscopy
I n acoustic m i c r o s c o p y , magnified a c o u s t i c i m a g e s of
t h e elastic s t r u c t u r e of t h e surface o r interior of a solid
a r e p r o d u c e d b y p a s s i n g high-frequency focused
acoustic pulses t h r o u g h t h e m a t e r i a l a n d displaying
the received signals in i m a g e f o r m as s h a d e s of gray.
Usually, m u c h higher frequencies a r e used t h a n in
o t h e r k i n d s of a c o u s t i c i m a g i n g . T h e a c o u s t i c pulses
are focused directly, o r t h e energy used t o p r o d u c e t h e
pulses is focused i n t o a very small region. W h e n a
small a r e a of a specimen is s c a n n e d with a series of
focused pulses a n d t h e t r a n s m i t t e d o r reflected signals
are viewed o n a n i m a g i n g system (a television p i c t u r e
t u b e , a gray-scale r e c o r d e r o r s o m e o t h e r s c a n n e d
display), t h e magnification of t h e resulting i m a g e is
e q u a l t o t h e r a t i o of t h e d i a m e t e r of t h e display t o t h e
d i a m e t e r of t h e a r e a s c a n n e d . T h i s p r o c e d u r e is also
used in electron m i c r o s c o p y a n d s c a n n i n g electron
m i c r o s c o p y t o p r o d u c e magnified i m a g e s by s c a n n i n g
a finely focused b e a m of electrons.
A c o u s t i c m i c r o s c o p y h a s b e e n used successfully in
materials c h a r a c t e r i z a t i o n a n d d e v e l o p m e n t a s well as
in b i o m e d i c a l a p p l i c a t i o n s ( L e m o n s a n d Q u a t e 1979).
Because t h e d i s p l a c e m e n t a m p l i t u d e associated w i t h
p r o p a g a t i o n of high-frequency s o u n d waves is a t m o s t
a fraction of a n a n g s t r o m , a p o o r chemical b o n d
between t w o m a t e r i a l s is readily detected b y m o n i t o r
ing the reflectivity o r t r a n s m i s s i o n of signals a t t h e
interface. T h e cleanliness of h o m o g e n e o u s m a t e r i a l s ,
the integrity of large-scale i n t e g r a t e d circuits, t h e
a t t a c h m e n t of very t h i n films t o s u p p o r t i n g s u b
strates, a n d t h e integrity of s e m i c o n d u c t o r - h e a t - s i n k
b o n d s a r e also being e v a l u a t e d w i t h b o t h reflection
a n d t r a n s m i s s i o n acoustic m i c r o g r a p h s . A c o u s t i c sur
face w a v e interference i m a g e s a r e u s e d t o e x a m i n e
surface d e f o r m a t i o n c a u s e d , for e x a m p l e , b y a b r a
sion, w e a r a n d m a c h i n i n g a s well a s t h e g r a i n size of
m a t e r i a l s t h a t a r e difficult t o e x a m i n e optically. T h e
capability of a c o u s t i c m i c r o s c o p y t o i m a g e small
regions in w h i c h near-surface residual stresses h a v e
c h a n g e d t h e elastic p r o p e r t i e s of m a t e r i a l s h a s led t o
w o r k o n visualizing microstress fields. Because t h e
acoustic c o n t r a s t in biological specimens is often far
greater t h a n t h e optical c o n t r a s t , a c o n s i d e r a b l e b o d y
of w o r k h a s been directed t o w a r d t h e i m a g i n g of
cellular s t r u c t u r e , collagen a n d o t h e r biological
materials.
A t present, a c o u s t i c m i c r o s c o p y includes several
m e t h o d s for t h e f o r m a t i o n of magnified a c o u s t i c
images. T h e four discussed here a r e s c a n n i n g a c o u s t i c
m i c r o s c o p y , p h o t o a c o u s t i c m i c r o s c o p y , electron
acoustic m i c r o s c o p y a n d s c a n n i n g laser a c o u s t i c
microscopy.

1.

Background

I n 1936, t h e R u s s i a n physicist S o k o l o v i n t r o d u c e d a n
acoustic i m a g i n g device (the S o k o l o v t u b e ) w h i c h

allows a c o u s t i c signals t r a n s m i t t e d t h r o u g h a n object

t o b e displayed in real t i m e o n a television screen. T h e
S o k o l o v t u b e is a n i m a g e c o n v e r t e r . T h e s h a d o w
g r a p h i m a g e is projected o n a piezoelectric c r o s s c u t
q u a r t z p l a t e o n e - h a l f a n a c o u s t i c w a v e l e n g t h in thick
ness. T h e b a c k of t h e p l a t e develops a n electric c h a r g e
i m a g e p r o p o r t i o n a l t o t h e a c o u s t i c a m p l i t u d e incident
o n its front surface. A s in all s t a n d a r d v i d e o - c o n v e r t e r
systems, t h e c h a r g e d surface is s c a n n e d b y a s y n c h r o
nized electron b e a m t o p r o v i d e t h e television d i s p l a y
signals. S u p p o r t i n g t h e q u a r t z p l a t e b e t w e e n t h e
w a t e r c o u p l i n g m e d i u m a n d a high v a c u u m , h o w e v e r ,
is very difficult. T h e stress i m p o s e d b y t h e a t m o s p h e r e
requires thick q u a r t z plates w i t h small surface a r e a s .
T h e thickness r e q u i r e m e n t limits t h e o p e r a t i n g fre
quencies t o less t h a n 5 M H z . U n l i k e later m i c r o
g r a p h s , these unmagnified s h a d o w g r a p h i m a g e s w e r e
f o r m e d b y near-field u n f o c u s e d b e a m s a n d s h o w e d
very p o o r r e s o l u t i o n . Because of t h e p o o r sensitivity
of t h e original S o k o l o v t u b e s b o t h t h e acoustic s o u r c e
a n d t h e object b e i n g i m a g e d h a d t o b e placed very
close t o t h e i m a g i n g screen. I n his original p r o p o s i
tion, h o w e v e r , S o k o l o v h a d n o t e d t h a t t h e w a v e l e n g t h
of s o u n d in w a t e r a t frequencies in t h e vicinity o f
3 G H z w o u l d b e c o m p a r a b l e t o t h e w a v e l e n g t h of
light in t h e visible s p e c t r u m . Since t h e r e s o l u t i o n of a n
i m a g i n g system is directly p r o p o r t i o n a l t o t h e w a v e
length of t h e i l l u m i n a t i o n (or, in this case, insonification), he concluded that acoustic images could be
f o r m e d e q u i v a l e n t in r e s o l u t i o n t o optical images. I n
fact, h o w e v e r , several d e c a d e s of t e c h n o l o g y d e v e l o p
m e n t w e r e necessary before a c o u s t i c images c o u l d b e
p r o d u c e d w i t h resolved detail e q u a l t o images f o r m e d
w i t h visible light.
T h e early 1970s w e r e of critical i m p o r t a n c e t o t h e
d e v e l o p m e n t of a c o u s t i c m i c r o s c o p y . O f p a r t i c u l a r
n o t e w a s t h e f o r m a t i o n of a research g r o u p a t S t a n
ford U n i v e r s i t y u n d e r t h e direction of Q u a t e . By 1974,
t h e S t a n f o r d g r o u p h a d m a d e S o k o l o v ' s speculation a
reality ( L e m o n s a n d Q u a t e 1974). T h e images p r o
d u c e d b y t h e S t a n f o r d devices, later called s c a n n i n g
a c o u s t i c m i c r o s c o p e s , w e r e clearly c o m p e t i t i v e in
r e s o l u t i o n with optical m i c r o s c o p y images.

2. Scanning

Acoustic

Microscopy

Systems b a s e d o n t h e S t a n f o r d design were being

offered c o m m e r c i a l l y b y t h e early 1980s. I n these
devices, a highly focused s o u n d s o u r c e is s c a n n e d
a l o n g a series of closely spaced lines a n d s y n c h r o n i z e d
with t h e line-by-line s c a n n i n g r a t e of a n i m a g i n g
system, usually a c a t h o d e - r a y t u b e o r a gray-scale
r e c o r d e r . O p e r a t i n g in either t h e p u l s e - e c h o o r pulse
t r a n s m i s s i o n m o d e , t h e S t a n f o r d systems (see F i g . 1)
use s p u t t e r e d zinc o x i d e t r a n s d u c e r s t o g e n e r a t e
a c o u s t i c signals t h a t a r e focused b y s a p p h i r e lenses t o
focal s p o t s 1 o r less in d i a m e t e r . Magnification is
achieved b y m a k i n g t h e lines s c a n n e d b y t h e focused

Acoustic

Sapphire
transmitter x
lens
Oscil lator

Microscopy

* +

,
Ps P uo tr smP | e
Receiving
transducer

Synchronization

(b)

Figure 1
Scanning acoustic microscopes: (a) pulse transmission and
(b) pulse-echo modes (courtesy of C. Quate and L. Lam,
Stanford University)

t r a n s d u c e r s h o r t e r a n d closer t o g e t h e r t h a n t h e lines
t h a t m a k e u p t h e i m a g e . C o n s i d e r , for e x a m p l e , a
1 m m x 1 m m a r e a t h a t is s c a n n e d b y m o v i n g a c o m
bined acoustic s o u r c e a n d receiver, e a c h focused t o
2 in d i a m e t e r over 500 lines t h a t a r e 1 m m l o n g
a n d spaced 2 a p a r t . W h e n t h e received sonic
signal is displayed in 500 equally spaced lines o n a
100 c m x 100 c m i m a g i n g screen, the result is a n
acoustic m i c r o g r a p h with a magnification of 1000 x .
A 5 cm x 5 c m s c a n n e d a r e a displayed o n the s a m e
100 c m x 100 c m screen generates a n acoustic m i c r o
g r a p h with a magnification of 20 x .
T h e p r i m a r y s t r e n g t h of t h e s c a n n i n g a c o u s t i c
m i c r o s c o p e design is its r e m a r k a b l e versatility. M i c r o
scopes c a n be c o n s t r u c t e d for use at a wide r a n g e of
frequencies for s c a n n i n g objects over a wide r a n g e of
sizes. A c o u s t i c images g e n e r a t e d by focused pulses
from 1 G H z t o 3 G H z typically scan a specimen a r e a
of 0.25 m m x 0.25 m m . T h e y p e n e t r a t e n o d e e p e r
t h a n 150 a n d t h e typical magnification is a p p r o x
imately 1000 x . F o r industrial acoustic images, it is
n o t u n u s u a l t o scan a n a r e a 15 c m x 15 c m with
10 M H z focused pulses, p e n e t r a t i n g t o a d e p t h of
5 cm o r m o r e a n d displaying t h e received signals a t
magnifications of 2 - 3 x .
Since the mid-1970s, m o s t of t h e S t a n f o r d w o r k h a s
been directed a t frequencies b e t w e e n 1 G H z a n d

Figure 2
Images of grain structure in Inconel: (a) optical image,
(b) optical image etched, and (c) 2.7 GHz acoustic image
of the same region (courtesy of L. Lam, Stanford
University)

5 G H z . A t University College L o n d o n w o r k h a s been

d o n e at 150 M H z - 1 G H z (Ash 1980), a n d industrially
o r i e n t e d w o r k at H u g h e s Aircraft C o m p a n y (Weglin
1979), the G e n e r a l Electric C o m p a n y a n d elsewhere
h a s been d o n e a t 1-450 M H z .

Acoustic

Microscopy

Sample

Mechanical
scan

Scan-control
and CRT-drive
circuitry

Synchronization
(a)

Figure 3
Longitudinal acoustic wave (50 MHz) image of Lincoln's
head on the obverse surface of a US penny (courtesy of
E. Lynk, General Electric Company)

F i g u r e 2 s h o w s etched a n d u n e t c h e d optical i m a g e s
a n d a n u n e t c h e d 2.7 G H z acoustic surface w a v e inter
ference i m a g e of I n c o n e l g r a i n s . Because surface
waves p e n e t r a t e at m o s t 1-2 i n t o t h e specimen a t
these frequencies, essentially t h e s a m e m a t e r i a l is
s h o w n in all t h r e e images.
F i g u r e 3 s h o w s a 50 M H z p u l s e - e c h o i m a g e of the
Lincoln h e a d (obverse) surface of a p e n n y viewed
from t h e reverse side of t h e c o i n . T h e reverse side h a s
been l a p p e d s m o o t h t o p r o v i d e a distortion-free e n t r y
surface for the focused acoustic b e a m .

3. Photoacoustic

Microscopy

T h e discovery t h a t acoustic pulses a r e p r o d u c e d in a

solid m a t e r i a l by t h e a b s o r p t i o n of light pulses a t the
surface of a specimen w a s m a d e originally by Bell in
1880. If the pulsed light s o u r c e is focused t o a small
spot a n d s c a n n e d over a specimen surface, a n d the
resulting acoustic pulses a r e received a n d their a m p l i
t u d e displayed o n a magnified gray-scale i m a g e , t h e n
a p h o t o a c o u s t i c m i c r o g r a p h is p r o d u c e d .
T w o typical p h o t o a c o u s t i c m i c r o s c o p e s a r e s h o w n
in Fig. 4. In b o t h systems, a light pulse from a laser is
focused o n a specimen surface, w h e r e it is p a r t l y
reflected a n d p a r t l y a b s o r b e d . T h e result is a b r u p t
localized h e a t i n g , w h i c h causes a t h e r m a l l y i n d u c e d
e x p a n s i o n of the near-surface m a t e r i a l . T h e m a t e r i a l

Figure 4
Schematic diagrams of photoacoustic microscope systems:
(a) after C. C. Williams, Stanford University; (b) after Y.
Martins and E. A. Ash, University College London

e x p a n s i o n causes a n u p w a r d d i s p l a c e m e n t of t h e
surface a n d a d o w n w a r d - p r o p a g a t i n g acoustic pulse.
T h e size of t h e h e a t e d s p o t t h a t c o n t r o l s t h e p h o t o
acoustic i m a g e r e s o l u t i o n is directly p r o p o r t i o n a l t o
the size of t h e light s p o t , t h e d u r a t i o n of the light pulse
a n d the specimen t h e r m a l diffusion (i.e., the r a t e at
which h e a t s p r e a d s t h r o u g h o u t the m a t e r i a l ) . T h e
distinguishing features of t h e p h o t o a c o u s t i c m i c r o
scopes discussed in this section a r e the m e t h o d s of
detecting acoustic pulse a m p l i t u d e s a n d the s c a n n i n g
m e t h o d s used t o c h a n g e the p o s i t i o n of t h e pulses in
the specimen.
T h e p h o t o a c o u s t i c m i c r o s c o p e system s h o w n in
Fig. 4a o r i g i n a t e d a t S t a n f o r d University ( W i c k r a m a s i n g h e et al. 1978) a n d utilizes the S t a n f o r d scan
ning acoustic m i c r o s c o p e t o receive a n d display the
signals a n d scan the specimen, b u t replaces t h e t r a n s
m i t t i n g t r a n s d u c e r with a n a r g o n laser m o d u l a t e d a t
940 M H z . T h i s system generates a t h e r m a l s p o t a b o u t
8 in d i a m e t e r . F i g u r e 5a s h o w s a n optical i m a g e
a n d Fig. 5b s h o w s a p h o t o a c o u s t i c i m a g e , p r o d u c e d
by t h e S t a n f o r d system, of a p a t t e r n e d gold film o n

Acoustic

Microscopy

Modified
scanning
electron microscope

Piezoelectric
transducer
receiver

Figure 6
Schematic diagram of an electron acoustic microscope
(after Cargill 1980)

this system h a s been a c c u r a t e l y n a m e d a " p h o t o d i s p l a c e m e n t m i c r o s c o p e . " A t h i r d type of p h o t o a c o u s t i c system utilizes a configuration similar t o the
electron acoustic system s h o w n in Fig. 6, with a
s c a n n e d laser in place of t h e s c a n n e d electron b e a m .

4. Electron

Figure 5
Images of gold foil attached to a glass substrate:
(a) optical image and (b) acoustic image with a resolution
size of about 8 (courtesy of C. C. Williams, Stanford
University)

glass. T h e sensitivity of p h o t o a c o u s t i c m i c r o s c o p y t o
the a d h e s i o n of films t o u n d e r l y i n g s u b s t r a t e s is
d e m o n s t r a t e d b y t h e c o n t r a s t o f t h e b u b b l e s in t h e
p h o t o a c o u s t i c i m a g e even t h o u g h the 8 focal s p o t
d e g r a d e s t h e r e s o l u t i o n slightly.
T h e alternative configuration (Fig. 4b) uses a
second laser t o m e a s u r e t h e u p w a r d surface displace
m e n t c a u s e d b y t h e h e a t i n g laser. Originally i n t r o
duced by researchers at U n i v e r s i t y College L o n d o n ,
u n d e r the direction of A s h ( M a r t i n s a n d A s h 1982),

Acoustic

Microscopy

S o m e t i m e s c o n s i d e r e d to be a n o t h e r device for p h o t o
a c o u s t i c m i c r o s c o p y , a n electron acoustic m i c r o s c o p e
differs in t h a t it uses a pulsed electron b e a m , usually
p r o v i d e d by a modified s c a n n i n g electron m i c r o s c o p e
t o p r o d u c e the ( t h e r m a l l y i n d u c e d ) s o u n d pulses. F o r
the electron b e a m t o be o p e r a t i v e , however, the
s a m p l e m u s t be in a high v a c u u m . T h e typical c o n
figuration
this system t a k e s is s h o w n in Fig. 6. T h e
s a m p l e is a t t a c h e d t o a stage by a n o n v o l a t i l e fluid
such as v a c u u m grease o r silicone oil. T h e stage is in
t u r n a t t a c h e d t o a piezoelectric t r a n s d u c e r configured
to receive all the pulses from the specimen a r e a at
a p p r o x i m a t e l y e q u a l sensitivity.
A l t h o u g h a typical focused s p o t d i a m e t e r for the
electron b e a m is a b o u t 0.1 , o r five times smaller
t h a n the smallest laser s p o t d i a m e t e r , until recently
the lateral r e s o l u t i o n of electron a c o u s t i c m i c r o s c o p e s
h a s n o t been a p p r e c i a b l y b e t t e r t h a n t h a t of the laserdriven m i c r o s c o p e s b e c a u s e of t h e d o m i n a n c e of the
t h e r m a l diffusivity of t h e i m a g e d m a t e r i a l . B o t h sys
t e m s seem t o p r o d u c e h e a t e d s p o t sizes b e t w e e n 5
a n d 10 , d e p e n d i n g o n the t h e r m a l diffusivity.
H o w e v e r , careful c o n t r o l of the p r i m a r y electron

Acoustic

Microscopy

energy of the incident b e a m (Balk a n d K u l t s c h e r

1983) h a s been s h o w n t o p r o d u c e s u b m i c r o m e t e r
resolution images.
Like p h o t o a c o u s t i c m i c r o s c o p e s , electron acoustic
m i c r o s c o p e s h a v e h a d c o n s i d e r a b l e success in d e n n i n g
b o t h surface a n d near-surface s t r u c t u r e s (Cargill
1980) such as g r a i n b o u n d a r i e s , plastic d e f o r m a t i o n ,
slip lines a n d near-surface flaws.

5. Scanning

Laser

Acoustic

Microscopy

In t h e early 1970s, t h e s c a n n i n g laser a c o u s t i c m i c r o

scope w a s developed ( K o r p e l et al. 1971). T h i s w a s t h e
first acoustic i m a g i n g system c a p a b l e of p r o d u c i n g
magnified images t o be offered c o m m e r c i a l l y (Fig. 7).
This system utilizes a focused laser b e a m t o scan t h e
ripple p a t t e r n p r o d u c e d o n t h e reflective surface of a
p a r t t h a t is insonified by a c o n t i n u o u s a c o u s t i c w a v e .
T h e frequency of t h e u l t r a s o n i c signal is usually
between 100 M H z a n d 500 M H z . Because t h e a m p l i
t u d e of the surface ripples is m o d u l a t e d b y the inter
nal elastic s t r u c t u r e of the m a t e r i a l , a gray-scale
p r e s e n t a t i o n of t h e ripple p a t t e r n a m p l i t u d e in fact
represents a t r a n s m i s s i o n acoustic s h a d o w g r a p h of
t h e interior. T h e r e s o l u t i o n of t h e ripple p a t t e r n i m a g e
is d e p e n d e n t o n t h e l o c a t i o n of t h e i n h o m o g e n e i t y
a n d the thickness, s t r u c t u r e a n d a t t e n u a t i o n of t h e
m a t e r i a l being s c a n n e d as well as t h e w a v e l e n g t h of
the i n t e r r o g a t i n g a c o u s t i c signal. T h e closer i n h o m o geneities a r e t o t h e surface, t h e m o r e s h a r p l y m o d u
lated the ripple p a t t e r n . T h e reflective surface s c a n n e d

Scan - control
and
CRT-drive
circuitry

Piezoelectric
transducer

I n c i d e n t sound

Figure 7
Schematic diagram of a scanning laser acoustic
microscope (courtesy of L. W. Kessler, Sonoscan)

Figure 8
Scanning laser acoustic microscope transmission images at
100 MHz of ribbon leads on a metallized A1 20 3 substrate.
The bonded region, circled, has an area of 125 2
(courtesy of L. W. Kessler, Sonoscan)

by t h e laser c a n be either t h e polished surface of t h e

specimen itself or, in t h e case of n o n m e t a l s , a reflec
tive cover slip o r metallized p o l y m e r film t h a t is
w e t t e d t o t h e specimen b y a thin layer of w a t e r o r oil.
F i g u r e 8 s h o w s a t r a n s m i s s i o n i m a g e of metallized
r i b b o n leads t o a n A 1 2 0 3 s u b s t r a t e . T h e b o n d e d region
shows good transmission whereas the remaining part
of t h e r i b b o n , w h i c h is n o t b o n d e d , s h o w s p o o r
transmission.
Since i m a g e s c a n be f o r m e d as fast as t h e laser c a n
be s c a n n e d , a s c a n n i n g laser acoustic m i c r o s c o p e d o e s
h a v e a real-time i m a g i n g capability. Its d i s a d v a n t a g e
is t h a t t h e ripple p a t t e r n s c a n n e d by t h e laser is
affected by e v e r y t h i n g t h e a c o u s t i c w a v e e n c o u n t e r s
t h r o u g h o u t the entire d e p t h of t h e s a m p l e . T h e r e f o r e
flaws, g r a i n size a n d surface blemishes c a n b e super
p o s e d o n o n e a n o t h e r . It h a s been suggested ( C h o u et

Adhesives:

al. 1980), h o w e v e r , t h a t these features of t h e i m a g e

can be s e p a r a t e d by a h o l o g r a p h i c type of p r o c e s s i n g
which w o u l d form t h r e e - d i m e n s i o n a l i m a g e s .

6. Future

Developments

Acoustic m i c r o s c o p y c o n t i n u e s t o h o l d c o n s i d e r a b l e
p r o m i s e for m a t e r i a l s c h a r a c t e r i z a t i o n a n d q u a l i t y
a s s u r a n c e in research a n d i n d u s t r y . T h e future direc
tions for a c o u s t i c m i c r o s c o p y a r e a l m o s t w i t h o u t
limit. A t S t a n f o r d , s c a n n i n g a c o u s t i c m i c r o s c o p y is
n o w being d o n e in cryogenic e n v i r o n m e n t s . A t liquidhelium t e m p e r a t u r e s , w a v e l e n g t h s as s h o r t as 80 n m
h a v e been p r o d u c e d . Extensive m a t e r i a l s c h a r a c t e r i
zation w o r k is u n d e r w a y at O x f o r d , U n i v e r s i t y
College L o n d o n , S t a n f o r d , C a r n e g i e M e l l o n a n d else
where. In i n d u s t r y , H u g h e s Aircraft, G e n e r a l Electric,
I n t e r n a t i o n a l Business M a c h i n e s , Bell L a b o r a t o r i e s ,
S o n o s c a n , Leitz a n d O l y m p u s a r e using a c o u s t i c
m i c r o s c o p y for m a t e r i a l s c h a r a c t e r i z a t i o n a n d p r o
duct testing. T h e last three firms a r e m a r k e t i n g a c o u s
tic m i c r o s c o p e s .

Bibliography
Ash A (ed.) 1980 Scanned Image Microscopy. Academic
Press, London
Balk L J, Kultscher 1983 Scanning electron acoustic
microscopy. Beitr.
Elektronemikroskop.
Direktabb.
Oberfl. BEDO-16
Briggs G A D 1992 Acoustic Microscopy. Oxford University
Press, Oxford
Cargill G S 1980 Electron acoustic microscopy. In: Ash
1980, pp. 319-31
Chou C H, Khuri-Yakub , Kino G S 1980 Transmission
imaging: forward scattering and scatter reconstruction.
In: Wang Y (ed.) 1980 Acoustical Imaging: Visualiza
tion and Characterization, Vol. 9. Plenum, New York,
pp. 357-77
Korpel A, Kessler L W, Palermo R 1971 Acoustic
microscope operating at 100 MHz. Nature (London) 232:
110-11
Lemons R A, Quate C F 1974 Acoustic microscope: scan
ning version. Appl. Phys. Lett. 24: 163-5
Lemons R A, Quate C F 1979 Acoustic microscopy. In:
Mason W P, Thurston R (eds.) 1979 Physical Acous
tics: Principles and Methods, Vol. 14. Academic Press,
London, pp. 1-92
Martins Y, Ash A 1982 Photodisplacement microscopy
using a semiconductor laser. Electron. Lett. 18: 763-4
Weglin R D 1979 A model for predicting acoustic material
signatures. Appl. Phys. Lett. 34: 179-81
Wickramasinghe , Bray R C, Jipson V, Quate C F,
Sakedo J R 1978 Photoacoustics on a microscopic scale.
Appl. Phys. Lett. 33: 923-5
R. G i l m o r e
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]

Tests for Mechanical

Properties

Adhesives: Tests for Mechanical

Properties
A d h e s i v e b o n d i n g for j o i n i n g m a t e r i a l s b e g a n w h e n
t h e E g y p t i a n s used casein adhesives in fabricating
m u m m y cases. H o w e v e r , adhesive b o n d i n g for loadb e a r i n g s t r u c t u r e s w a s d e v e l o p e d only several d e c a d e s
a g o ; b o n d i n g of t h e p l y w o o d l a m i n a e of t h e British
w o o d e n M o s q u i t o b o m b e r of W o r l d W a r II m a y h a v e
been t h e first a v i a t i o n a p p l i c a t i o n . In t h e U S A , a d h e s
ives were d e v e l o p e d in t h e early 1940s for t h e C o n s o l i
d a t e d Vultee B-36 b o m b e r ( V i n s o n 1980). Since t h a t
time, t h e use of adhesive b o n d i n g h a s increased
steadily.
Since t h e early u s a g e of adhesives for j o i n i n g struc
t u r a l c o m p o n e n t s , research h a s c o n c e n t r a t e d o n the
i m p r o v e m e n t of a d h e r e n d surface p r e p a r a t i o n s a n d
t o u g h e r / s t r o n g e r adhesives. Significant a c h i e v e m e n t s
h a v e been a c c o m p l i s h e d in these a r e a s , with processes
a n d b o n d i n g m a t e r i a l s n o w available t h a t p r o v i d e
b o n d e d j o i n t s w h i c h e q u a l o r exceed (on a j o i n t
o v e r l a p p e r u n i t a r e a basis) t h e s h e a r l o a d i n g s t r e n g t h
of c o m m o n l y used m e c h a n i c a l fasteners. In recent
years, there h a s b e e n t h e d e v e l o p m e n t of c o m p u t e r
r o u t i n e s which a r e used t o analyze, design a n d opti
mize j o i n t s of m a n y c o n f i g u r a t i o n s , subject t o m e c h a
nical, t h e r m a l a n d h y g r o s c o p i c l o a d s . H o w e v e r ,
utilization of these i m p r o v e d m a t e r i a l s , processes a n d
n e w analytical tools is limited since t h e s t r e s s - s t r a i n
p r o p e r t i e s of adhesives u n d e r e n v i r o n m e n t a l a n d l o a d
c o n d i t i o n s a r e generally ill defined. T h i s technological
g a p exists b e c a u s e suitable test t e c h n i q u e s for generat
ing this type of d a t a h a v e n o t been developed.
C u r r e n t test-specimen c o n f i g u r a t i o n s either (a) in
t r o d u c e strain c o n c e n t r a t i o n s w h i c h a r e n o t c h a r a c
teristic of t h e b o n d a p p l i c a t i o n s , (b) require extremely
precise m e a s u r e m e n t s of very small strains o r (c)
a t t e m p t t o solve p o i n t s (a) a n d (b) by testing thick
adhesive castings, w h i c h h a v e p r o p e r t i e s significantly
different from t h o s e of t h e adhesive as a thin film
( H u g h e s a n d R u t h e r f o r d 1968, Z a b o r a et al. 1971).
T h i s is especially t r u e in relation t o t h e surface
c h e m i s t r y at t h e a d h e s i v e - a d h e r e n d interface, d u e t o
t h e residual strains locked in a b o n d e d j o i n t d u r i n g a n
e l e v a t e d - t e m p e r a t u r e c u r e a n d t h e c o n s t r a i n i n g Poiss o n ' s effect of t h e stiffer a d h e r e n d o n t h e relatively
soft adhesive. T h u s , these b u l k adhesive specimens
c a n b e excluded from c o n s i d e r a t i o n as c a n d i d a t e test
specimens, being u n r e p r e s e n t a t i v e of real s t r u c t u r a l
application environments.

1. Adhesive

Characterization

T h e c o m p l e t e c h a r a c t e r i z a t i o n of a n adhesive re
quires t h a t its r e s p o n s e t o v a r i o u s l o a d , time a n d
e n v i r o n m e n t a l c o n d i t i o n s be a s c e r t a i n e d . T h e specific
a d h e s i v e - p r o p e r t y d a t a r e q u i r e d t o predict the re-

Adhesives:

Tests for Mechanical

Properties

sponse of the adhesive in a b o n d e d j o i n t u n d e r typical

structural loads and environments are

o b t a i n fatigue a n d viscoelastic p r o p e r t i e s of t h e
adhesive. A brief s u m m a r y of their i m p o r t a n c e in
t h e design process follows.

(a)

shear a n d tensile m o d u l i ;

(b)

u l t i m a t e shear, tensile a n d c o m b i n e d s h e a r a n d
tensile strength;

(c)

u l t i m a t e s h e a r a n d tensile strain;

3. Fatigue

(d)

c r e e p - c o m p l i a n c e m a s t e r curves in s h e a r
tension;

(e)

fatigue s h e a r a n d tensile m o d u l i t h a t reflect the

w e a r o u t a n d / o r stability of t h e adhesive j u s t
p r i o r t o c a t a s t r o p h i c failure;

(f)

fatigue tensile a n d s h e a r s t r e n g t h (strain) versus

cycles of failure; a n d

(g)

coefficients of t h e r m a l a n d h y g r o s c o p i c e x p a n
sion.

Adhesives fail in fatigue. T h e y d o so, by a n a l o g y with

the better-studied m e t a l s , because of a cycle-by-cycle
a c c u m u l a t i o n of d a m a g e resulting from r e p e a t e d
nonelastic strain. T h i s strain c a n be further influenced
by frequency of l o a d i n g , t e m p e r a t u r e , h u m i d i t y a n d
s t r a i n - r a t e (viscoelastic) effects. O n e of t h e items
required in t h e design process is t h e s t r e s s - s t r a i n
b e h a v i o r of t h e adhesive d u r i n g its lifetime, a t a
prescribed fatigue l o a d , frequency a n d in a c o n t r o l l e d
e n v i r o n m e n t . M a s t e r curves a r e c o n s t r u c t e d of t h e
fatigue s t r e s s - s t r a i n r e l a t i o n s h i p for a p a r t i c u l a r a d
hesive, for a definite strain r a t i o a n d v a r i o u s c o m
b i n a t i o n s of e n v i r o n m e n t a n d l o a d frequency.

and

F o r a n isotropic, h o m o g e n e o u s adhesive layer, t h e

P o i s s o n ' s r a t i o m a y be d e t e r m i n e d in place of the
shear or tensile m o d u l u s .

2. Criteria

for

Test-Specimen

Evaluation

T o evaluate objectively t h e a d e q u a c y of the v a r i o u s

test specimens available, from which adhesive static-,
creep- o r fatigue-property d a t a c a n be o b t a i n e d for
use in design of b o n d e d s t r u c t u r e s , the following
criteria need t o be considered:
(a)

T h e specimen l o a d i n g m o d e m u s t be d o m i n a n t
a n d c o n t r o l l a b l e t e n s i o n a n d shear m o d e s
s h o u l d be s e p a r a b l e a n d their m a g n i t u d e easily
controlled. A biaxial o r triaxial stress state
s h o u l d be p r e s e n t in the adhesive.

(b)

T h e specimen m u s t be c a p a b l e of p r o v i d i n g
quantitative resultsmodulus and strength data
in representative e n v i r o n m e n t s s h o u l d be o b t a i n
able.

(c)

T h e test specimen m u s t be r e p r e s e n t a t i v e of
m a t e r i a l s a n d processing in p r o d u c t i o n i t
s h o u l d reflect the chemical, physical a n d m e c h a
nical r e s p o n s e of a n adhesive b o n d e d b e t w e e n
t w o relatively rigid a d h e r e n d s .

(d)

A realistic analysis of t h e biaxial o r triaxial stress

state in t h e a d h e s i v e - b o n d e d test specimen m u s t
be possiblein closed form o r by
finite-element
analysis.

(e)

Multiple-specimen p r e p a r a t i o n s h o u l d be rela
tively easy a n d of n o m i n a l c o s t u n i f o r m c o n
trol of a d h e s i v e - b o n d l i n e thickness is necessary
for p r o p e r t e s t - d a t a i n t e r p r e t a t i o n .

(f)

T h e b o n d l i n e of the specimen s h o u l d be easily

inspectable by n o n d e s t r u c t i v e e v a l u a t i o n ( N D E )
m e a n s for d e b o n d s , voids a n d air b u b b l e s .

(g)

O t h e r c o n s i d e r a t i o n s i n a d d i t i o n t o the a b o v e
criteria, t h e specimen s h o u l d be readily usable t o

10

4.

Response

Viscoelastic

Response

U n d e r sufficiently high strain rates a n d / o r elevated

t e m p e r a t u r e a n d relative-humidity levels, m o s t a d h e
sives exhibit a viscoelastic r e s p o n s e . T h i s c a n result in
a c r e e p - r u p t u r e failure of t h e b o n d e d s t r u c t u r e , so it is
necessary t o o b t a i n viscoelastic-response d a t a . This
requires a j o i n t g e o m e t r y within which the adhesive
sees a n a p p r o x i m a t e l y u n i f o r m stress state.

5. Candidate

Test

Specimens

A s u m m a r y of the v a r i o u s candidate-test-specimen
geometries a l r e a d y in existence versus t h e e v a l u a t i o n
criteria is given in T a b l e 1. F r o m this table c a n be
o b t a i n e d t h e list of test specimens best suited t o
o b t a i n desired adhesive m e c h a n i c a l p r o p e r t i e s s h o w n
in T a b l e 2.

6. Single

Lap

Joint

It is u n f o r t u n a t e t h a t t h e p r i m a r y s t a n d a r d for a d
hesive s t r e n g t h is t h e A S T M Test
Standard
D 1 0 0 2 - 7 2 , " S t r e n g t h P r o p e r t i e s of Adhesives in S h e a r
T e n s i o n L o a d i n g . " T h e specimen is a single l a p j o i n t
(see Fig. 1), c o m p r i s e d of t w o t h i n a d h e r e n d s , usually
steel o r a l u m i n u m , b o n d e d t o g e t h e r b y a n adhesive
layer. T h e specimen is pulled in tension a n d the m e a n
value of s h e a r s t r e n g t h is c o m p u t e d t o be the m a x i
m u m tensile l o a d divided by t h e shear a r e a
(L x unit width).
Because of t h e thin a d h e r e n d s , t h e tensile in-plane
l o a d causes c o n s i d e r a b l e b e n d i n g in the j o i n t , as seen
in Fig. 1. T h i s results in shear-stress p e a k s n e a r the

Adhesives:

Tests for Mechanical

Properties

Table 1
Candidate test specimens

Evaluation criteria
Loading mode
Specimen can provide
quantitative results
Representative of real
strutural
applications
Biaxial or triaxial
stress state in
adhesive
Specimen analysis
performed
Adhesive thickness
controllable
measurable
Specimen fabrication
ease of replicating
specimen
relative cost
NDE inspectability

Thickadherend
specimen

Scarf
joint

Butt
joint

tension
tension, shear
tension
static
static
static
visoelastic
viscoelastic viscoelastic
fatigue
fatigue
fatigue

shear
none

Napkin-ring
specimen

Iosipescu
specimen

tension, shear
shear
static
static
viscoelastic viscoelastic
fatigue

Double
lap joint

Peel
specimen

shear
none

tension
none

yes

yes

yes

yes

no

yes

yes

yes

yes

yes

yes

yes

yes

yes

yes

yes

yes

yes

yes

yes

no

yes

yes

no

easy

difficult

easy

easy

easy

yes

modestly
difficult
yes

yes

yes

yes

easy

easy

easy

easy

low

low

low

low

easy

difficult

modestly
difficult
modestly
expensive
modestly
difficult

easy

easy

yes

e n d s of t h e o v e r l a p , w h i c h g o t o z e r o a t t h e free
surfaces. It is also n o t e d t h a t the n o r m a l o r peel
stresses p e a k at t h e e n d s a n d a r e compressive over a
sizeable region in t h e j o i n t interior.
T h e adhesive shear stress of the A S T M test speci
m e n is far from c o n s t a n t , t h u s n e g a t i n g t h e d e t e r m i
n a t i o n of a t r u e s h e a r s t r e n g t h . E v e n w o r s e is t h e fact
t h a t t h e m a x i m u m tensile o r peel stress in the adhesive
c a n be g r e a t e r t h a n t h e m a x i m u m s h e a r stress. S o ,
failure m a y o c c u r in tensile r u p t u r e r a t h e r t h a n in
shear. T h u s , t h e specimen is n o t r e c o m m e n d e d for
d e t e r m i n i n g adhesive m e c h a n i c a l p r o p e r t i e s .

Table 2
Test specimens suited to obtain desired adhesive properties
Specimen

Type load

Thick-adherend lap
joint
Butt joint napkin ring

shear

Scarf joint

Single
lap joint

tension
tension plus
shear

Mechanical properties
obtainable
static, viscoelastic,
fatigue
static, viscoelastic,
fatigue
static, viscoelastic,
fatigue

modestly
modestly
difficult
difficult
yes
yesone side
only
easy

difficult

low

high

easy

modestly
difficult

modestly
difficult
modestly
expensive
modestly
difficult

7. Thick-Adherend

Symmetric

Lap

Joint

T h e t h i c k - a d h e r e n d s y m m e t r i c l a p j o i n t (see Fig. 2)
h a s been p r o p o s e d ( R e n t o n 1976, 1978) as a viable
specimen with w h i c h t o o b t a i n t h e effective thin-filmadhesive s h e a r m o d u l u s , p r o p o r t i o n a l limit stress a n d
u l t i m a t e s h e a r s t r e n g t h , as well as viscoelastic a n d
fatigue s h e a r p r o p e r t i e s . A d h e s i v e p r o p e r t i e s from
this specimen p r o v i d e d a t a readily u s a b l e in t h e
n u m e r o u s m e t h o d s of analysis c u r r e n t l y in use for
d e t e r m i n i n g stresses a n d d e f o r m a t i o n s in b o t h the
adhesive a n d t h e a d h e r e n d s . A d d i t i o n a l l y , it c a n be
used t o d e t e r m i n e t h e effect of adhesive thickness,
surface r o u g h n e s s , t e m p e r a t u r e , strain r a t e , residual
strains, c o r r o s i v e e n v i r o n m e n t a n d cyclic loading.
A c c u r a t e m e a s u r e m e n t of adhesive d e f o r m a t i o n is a
challenge w h i c h c a n be m e t b y a t t a c h i n g a m e a s u r e
m e n t device a t t h e adhesive b o n d l i n e ( H u g h e s a n d
R u t h e r f o r d 1968, R e n t o n 1976, 1978). T h e cost of
specimen fabrication a n d testing is q u i t e r e a s o n a b l e .

Figure 1
Deflections induced in a thin adherend lap joint

11

Adhesives:

Tests for Mechanical

Properties

- 0 . 9 c m j lT~

'

Adherends
LG
h2--

h2/2
,/2 -

Optimum
/2

dimensions:

Figure 2
Geometry of thick adherend optimum adhesive test
specimen

>

A t t a c h m e n t point
for strain
measurement

hi

> 8
1-2 ~

F i g u r e 2 presents the o p t i m u m d i m e n s i o n s of the

a d h e r e n d r e c o m m e n d e d to o b t a i n a n e a r - u n i f o r m
adhesive shear stress over the b o n d length a n d as
sumes t h a t adhesive d e f o r m a t i o n is m e a s u r e d n e a r the
b o n d - a d h e r e n d interface at the centerline (points A
a n d B).

8. Butt

Joint

T h e b u t t j o i n t specimen illustrated in Fig. 3 h a s been

used to o b t a i n adhesive tensile p r o p e r t i e s u n d e r static,
fatigue a n d viscoelastic loadings. T h e specimen h a s
been rigorously analyzed using elastic a n d p h o t o e l a s tic m e t h o d s a n d h a s been verified by
finite-element
analysis ( R e n t o n 1978). A triaxial stress field is
a p p r o x i m a t e d in the center of the specimen w h e n
b e n d i n g of the rigid a d h e r e n d s is negligible, a n aspect
ratio () ^ 4 0 is m a i n t a i n e d a n d the P o i s s o n ' s r a t i o
of the adhesive is a p p r o x i m a t e l y 0.50. O p t i m u m speci
m e n d i m e n s i o n s a r e s h o w n in Fig. 3.
Overall, the p o t e n t i a l p r o b l e m s in using this speci
m e n are adhesive thickness c o n t r o l , a c c u r a t e adhesive
d e f o r m a t i o n m e a s u r e m e n t of the b o n d l i n e u n d e r load
a n d the significance of eccentric l o a d o n the adhesive
stress d i s t r i b u t i o n . T h e cost is m o d e s t .

9. Scarf

Joint

T h e scarf j o i n t (see Fig. 4) h a s been p r o p o s e d ( R e n t o n

1978) as a viable specimen with which to o b t a i n the
effective thin-film biaxial p r o p e r t i e s of adhesives, as it
can p r o v i d e a c o n t r o l l a b l e tension a n d s h e a r - l o a d i n g
m o d e for static, viscoelastic a n d fatigue testing. T h i s
c o n t r o l is achieved by t h e scarf angle. W h i l e this j o i n t
is relatively easy to fabricate a n d of m o d e s t cost, there
are p o t e n t i a l p r o b l e m s in m e a s u r i n g adhesive b o n d line d e f o r m a t i o n accurately, a n d in b o n d l i n e inspectability. H o w e v e r , the relatively new N D E t e c h n i q u e of

12

Figure 3
Geometry of tensile specimen optimum adhesive test
specimen

n e u t r o n r a d i o g r a p h y offers a realistic a p p r o a c h t o
resolving this p r o b l e m . T h e s e specimens c a n also p o s e
b o n d l i n e thickness c o n t r o l a n d a l i g n m e n t p r o b l e m s .
Analytical a n d p h o t o e l a s t i c studies ( R e n t o n 1978)
h a v e s h o w n t h a t t h e stress in the m i d d l e p l a n e of t h e
specimen is triaxial, with a s u p e r i m p o s e d shear stress.
In s u m m a r y , by careful selection of t h e testspecimen g e o m e t r y , o n e c a n o b t a i n a n e a r - u n i f o r m
triaxial tensile-stress s t a t e a n d i m p a r t t o t h e adhesive
a c o n t r o l l e d s h e a r stress. A n aspect r a t i o of 40 ( u p t o
100 if the P o i s s o n ' s r a t i o of the adhesive is
0.480) is
suggested to k e e p the edge effect to within o n e o r t w o
adhesive thicknesses of t h e b o n d edge. A s t h e m e c h a
nical p r o p e r t i e s o b t a i n e d a r e a v e r a g e p r o p e r t i e s of the
adhesive c o n s t r a i n e d between the m u c h stiffer elastic
a d h e r e n d s , this m i n o r edge effect s h o u l d n o t a p p r e c i a
bly affect the test results. T h u s , the uniformity of the

Figure 4
Scarf joint

Adhesives:

Adhesive

bondline

specimen

Figure 5
Napkin-ring test specimen

stress d i s t r i b u t i o n over t h e b o n d e d surface will e n a b l e

the c h a r a c t e r i z a t i o n of the linear a n d n o n l i n e a r viscoelastic a n d fatigue r e s p o n s e of the adhesive.

10. Napkin-Ring

Specimen

M a n y of t h e i n s t r u m e n t e d adhesive c h a r a c t e r i z a t i o n
tests p e r f o r m e d t o d a t e h a v e used t h e n a p k i n - r i n g
specimen (see Fig. 5). O n e of its p r i n c i p a l a t t r i b u t e s is
t h a t it c a n be used t o d e t e r m i n e t h e s t r e s s - s t r a i n
response of a n adhesive m a t e r i a l in shear, tension o r a
c o m b i n a t i o n thereof, for static, fatigue a n d viscoelastic l o a d s . T h e use of t h e n a p k i n - r i n g test piece c a n
p r o v i d e a d h e s i v e - s h e a r - p r o p e r t y d a t a for typical
b o n d e d - j o i n t thicknesses, b u t requires e x t r e m e c a r e in
l o a d i n g t o e n s u r e p u r e t o r q u e . A d d i t i o n a l l y , the cost
per test item is q u i t e high a n d the specimen configur
a t i o n is n o t a b l y different from t h e g e o m e t r i c a l c o n
figuration
( H u g h e s a n d R u t h e r f o r d 1968) in w h i c h
structural adhesives a r e n o r m a l l y used. A n a c c u r a t e
analysis of the stress (strain) d i s t r i b u t i o n in the a d
hesive of this specimen h a s n o t been r e p o r t e d ; it is
believed t o be biaxial o r triaxial.

Load transfer
rod

(typical)

Properties

T h e specimen itself suffers from being difficult t o

fabricate t o prescribed adhesive thicknesses, adhesive
d e f o r m a t i o n m e a s u r e m e n t is difficult a n d c o n t r o l of
t h e biaxial l o a d i n t o the specimen requires e x t r e m e
care.

11.
Napkin-ring

Tests for Mechanical

Iosipescu

Specimen

T h e Iosipescu specimen (see Fig. 6) c a n be used t o

m e a s u r e adhesive s h e a r s t r e n g t h ( K u t s c h a a n d H o f e r
1969). T h e specimen h a d been a n a l y z e d by finiteelement m e t h o d s a n d t h e adhesive is in a l m o s t p u r e
shear. H o w e v e r , t o d a t e d i s p l a c e m e n t s h a v e n o t been
m e a s u r e d ; hence, it h a s n o t been used t o m e a s u r e the
elastic m o d u l u s , the p r o p o r t i o n a l limit o r t h e strain t o
failure. K u t s c h a a n d H o f e r recognized t h e p o t e n t i a l
of the Iosipescu specimen for m e a s u r i n g t h e shear
s t r e n g t h of adhesives. T h e y n o t e d the difficulty in
fabrication, b u t r e m a r k e d t h a t the difficulty is less
t h a n fabricating t u b u l a r t o r s i o n (i.e., n a p k i n - r i n g )
specimens a n d , with p r o p e r i n s t r u m e n t a t i o n , the spe
cimen c o u l d be used t o m e a s u r e t h e s h e a r m o d u l u s .

12.

Other

Specimens

In principle, t h e b a l a n c e d d o u b l e lap j o i n t c o u l d be
used in a s h e a r m o d e with m o d e s t l y thick a d h e r e n d s ,
b u t w i t h relatively high fabrication a n d N D E inspec
tion costs. T h e selection of t h e g e o m e t r y of t h e j o i n t
w o u l d be extremely i m p o r t a n t in o b t a i n i n g a u n i f o r m shear-stress c o n d i t i o n .
Several o t h e r test specimens t o c h a r a c t e r i z e the
s t r u c t u r a l r e s p o n s e of adhesives a r e available. T h e
i n a d e q u a c i e s of t h e b l o c k s h e a r ( A S T M - D 9 0 5 ) , cross
t a b t e n s i o n a n d glueline cleavage tests h a v e been
r e p o r t e d ( R e n t o n 1978). It is i m p o r t a n t t o n o t e t h a t
t h e v a r i o u s peel tests t h a t presently exist a r e represen
tative of gross c o m b i n a t i o n s of s h e a r a n d tension. T h e
m a i n difficulty w i t h these peel tests is t h a t the adhesive
p r o p e r t i e s u n d e r shear p l u s t e n s i o n a r e grossly affec
ted by t h e a d h e r e n d . T h i s factor m a k e s the p r e s e n t
peel tests u n u s a b l e from the s t a n d p o i n t of o b t a i n i n g
precise q u a n t i t a t i v e m e c h a n i c a l - p r o p e r t y d a t a appli
cable t o b o n d e d - j o i n t analysis.

////////////////
/#/////////////\
-

(TV-

13.

Figure 6
Iosipescu shear-test specimen

Test-Methodology

Criteria

O n c e t h e test specimen h a s been selected, it is m a n d a

t o r y t h a t simple, reliable test p r o c e d u r e s be e m p l o y e d
t o m i n i m i z e d a t a scatter a n d cost. M o r e o v e r , p r o p e r
c o n d i t i o n i n g of test specimens s h o u l d e n s u r e equi
l i b r i u m of t h e b o n d l i n e adhesive with t h e e n v i r o n
m e n t . M e a n s t o m e a s u r e t e m p e r a t u r e s from - 15 C
t o 175 C a n d relative h u m i d i t i e s from 1 0 % t o 1 0 0 %
accurately before a n d d u r i n g the p e r f o r m a n c e of

13

Adhesives:

Tests for Mechanical

Properties

m e c h a n i c a l tests s h o u l d be available. Sensitivity re

q u i r e m e n t s for t h e adhesive d e f o r m a t i o n m e a s u r e
m e n t device s h o u l d be established, t o d e t e r m i n e the
adhesive p r o p e r t i e s to within a c c e p t a b l e a c c u r a c y
limits. M o r e o v e r , t h e d e f o r m a t i o n m e a s u r e m e n t de
vice s h o u l d be easy t o a t t a c h t o t h e test specimen,
simple, stable with respect to time a n d e n v i r o n m e n t ,
d u r a b l e a n d relatively inexpensive.

14.

Test-Data

Reporting

A m a j o r deficiency in adhesive c h a r a c t e r i z a t i o n re
sults from the a r b i t r a r y test a n d r e p o r t p r o c e d u r e s
followed by m a n y investigators. I n c o m p l e t e i n f o r m a
tion m a k e s d a t a difficult to interpret a n d d a t a c o m
p a r i s o n s impossible. T h i s m a y be d u e in p a r t to the
lack of A S T M test specifications in this a r e a .

75. Adhesive

Deformation

Measurement

Renton W J 1976 The symmetric lap jointwhat good is it?

Exp. Mech. November: 409-16
Renton W J 1978 Structural Properties of Adhesives, Vol. 1,
Final Report AFML-TR-78-127. US Air Force Materials
Laboratory, Dayton, OH
Rose J L 1986 Adhesive bonds: nondestructive evaluation.
In: Bever (ed.) 1986 Encyclopedia of Materials
Science and Engineering. Pergamon, Oxford, pp. 70-3
Vinson J R 1980 State of technology in adhesively bonded
joints in composite structures. Emerging Technologies in
Aerospace Structures Design, Structural Dynamics and
Materials. American Society of Mechanical Engineers,
New York.
Zabora R F, Clinton W W, Bell J 1971 Adhesive Property
Phenomena and Test Techniques, AFFDL Report No.
AD-729873. US Air Force Flight Dynamics Laboratory,
Wright-Patterson Air Force Base, Dayton, OH
W . J. R e n t o n
[Vought C o r p o r a t i o n , D a l l a s ,
Texas, USA]

Anodization Spectroscopy

T h e small d i m e n s i o n a l c h a n g e s t h a t occur m a k e the

m e a s u r e m e n t of adhesive d e f o r m a t i o n d u r i n g l o a d i n g
very difficult. F o r e x a m p l e , in a tensile test, 1 % strain
in a 125 b o n d l i n e is 1.25 . Careful w o r k e r s in
the field ( R e n t o n 1978) express the need for a mini
m u m accuracy in m e a s u r e m e n t of b o n d l i n e d i m e n
sional c h a n g e s of 25 ( 0 . 2 % ) . T h i s a c c u r a c y m u s t
be m a i n t a i n e d over a very wide t e m p e r a t u r e a n d
h u m i d i t y r a n g e a n d for long p e r i o d s of time. T h e s e
c o n d i t i o n s i m p o s e very strict r e q u i r e m e n t s o n the
stability of the strain sensor.
Studies to d a t e indicate t h a t L V D T s , extensometers, T u c k e r m a n gauges, a i r - g a p c a p a c i t a n c e
gauges a n d strain gauges are the sensors m o s t c o m
m o n l y used; of these, L V D T s a n d a i r - g a p c a p a c i t a n c e
gauges show the m o s t p r o m i s e .

A n o d i z a t i o n s p e c t r o m e t r y is a d e p t h profiling tech
n i q u e which c a n p r o v i d e i n f o r m a t i o n a b o u t the c h e m
ical c o m p o s i t i o n a n d m i c r o s t r u c t u r e of a thin-film
specimen by r e c o r d i n g the voltage required t o m a i n
tain a c o n s t a n t c u r r e n t d u r i n g the electrolytic g r o w t h
of a n oxide film o n its surface. T h e t e c h n i q u e relies o n
the difference in the rates of oxide g r o w t h a n d varia
tions in ionic mobility between m a t e r i a l s ; these dif
ferences result in a characteristic r a t e of voltage rise
(dV/dt) with time for each element or c o m p o u n d .
C o n s e q u e n t l y , c h a n g e s in dV/dt c a n be a t t r i b u t e d t o
s t r u c t u r a l c h a n g e s in the specimen a n d the voltage a t
which they o c c u r t o the thickness of the preceding
layer. A n o d i z a t i o n s p e c t r o s c o p y h a s been applied t o a
variety of m a t e r i a l s a n d h a s been d e m o n s t r a t e d t o
h a v e very high resolution.

See also: Composite Materials: Nondestructive Evalu

ation; Wood: Acoustic Emission and Acousto-Ultrasonic
Characteristics

1.

Bibliography
Brown R 1986 Adhesion corrosion and staining. Physical
Testing of Rubber, 2nd edn. Elsevier, Amsterdam, Chap.
18
Hughes J, Rutherford J L 1968 Study of Micromechanical
Properties of Adhesive Bonded Joints, Technical Report
No. 3744. General Precision, Little Falls, NJ
Kutscha D, Hofer Jr 1969 Feasibility of Joining
Advanced Composite Flight Vehicles, Report AFML-TR68-391. US Air Force Materials Laboratory, Dayton, OH
Lehman G M, Hawley A V 1969 Investigation of Joints in
Advanced Fibrous Composites for Aircraft Structures, Vol.
1, AFFDL Report No. TR-69-43. US Air Force Flight
Dynamics Laboratory, Wright-Patterson Air Force Base,
Dayton, OH
14

Theory

A l t h o u g h t h e t h e o r y of the g r o w t h of a n o d i c oxides is
n o t completely clarified, all m o d e l s include s o m e
a s s u m p t i o n of t h e r m a l l y activated ionic h o p p i n g c o n
d u c t i o n . T h i s leads t o the a n o d i z a t i o n c u r r e n t density
J being g o v e r n e d by a r e l a t i o n s h i p of the form
J = A cxp(BE) in which the electric field E, is the
d o m i n a n t driving force a n d A a n d a r e c o n s t a n t s .
T h i s e q u a t i o n therefore predicts a linear r e l a t i o n s h i p
between voltage a n d oxide thickness. P r o v i d e d t h a t
the oxide is h o m o g e n e o u s this also leads t o a direct
p r o p o r t i o n a l i t y between thickness of c o n s u m e d speci
m e n m a t e r i a l a n d m o n i t o r e d voltage V; so t h a t
V=Rt

(1)

w h e r e t is the thickness of m a t e r i a l c o n s u m e d a n d R is
a material-dependent constant.

Anodization

Spectroscopy

Electrolyte

Specimen

Figure 1
Schematic diagram of the anodization system: the defined
anodization area is normally smaller than the electrolyte
drop

2. Sample

Preparation

and

Time (scaled)

Measurement

Procedure
Since q u a n t i t a t i v e c o m p o s i t i o n i n f o r m a t i o n c a n only
be extracted from t h e voltage u n d e r c o n s t a n t c u r r e n t
density c o n d i t i o n s , t h e p r i m a r y r e q u i r e m e n t in s a m p l e
p r e p a r a t i o n is t h a t t h e a r e a of t h e specimen e x p o s e d
t o the a n o d i z a t i o n cell s h o u l d r e m a i n c o n s t a n t
t h r o u g h o u t t h e m e a s u r e m e n t . If this a r e a varies t h e n
n o t only will t h e c u r r e n t density be altered, t h u s
modifying the p r o p o r t i o n a l i t y b e t w e e n thickness a n d
voltage, b u t c o n s i d e r a b l e noise c a n be g e n e r a t e d even
by very small increases in a n o d i z a t i o n a r e a . T h e
s t a n d a r d s a m p l e p r e p a r a t i o n t e c h n i q u e is t h e p a t t e r n
ing of a small w i n d o w in a resistant, electrically
insulating layer c o v e r i n g t h e surface of t h e specimen.
A Z p h o t o r e s i s t o r i n o r g a n i c resists, such as v a p o r deposited S i 0 2 , are the usual m a s k i n g m a t e r i a l s .
A typical e x p e r i m e n t a l a r r a n g e m e n t is illustrated in
Fig. 1. A d r o p of electrolyte is placed over t h e e x p o s e d
a n o d i z a t i o n region a n d electrical c o n t a c t is m a d e t o
the specimen in a region n o t e x p o s e d t o electrolyte,
usually by m e a n s of a s p r i n g p r o b e . A p l a t i n u m o r
gold c a t h o d e is c o n v e n t i o n a l l y e m p l o y e d . T h e s t a n
d a r d electrolyte for metallic specimens is a 0.4
solution of a m m o n i u m p e n t a b o r a t e in a 3:2 ethylene
g l y c o l - w a t e r m i x t u r e . A n o d i z a t i o n s p e c t r o s c o p y in
G a A s a n d o t h e r I I I - V s e m i c o n d u c t o r s h a s been
achieved using a q u e o u s 3 % ( + )-tartaric acid in a 1:2
v o l u m e r a t i o with ethylene glycol.
T h e voltage thickness c o n s t a n t R for e a c h element
(see E q n . (1)) m u s t generally be c a l i b r a t e d from a
series of m e a s u r e m e n t s . G i v e n a k n o w l e d g e of t h e
v o l u m e e x p a n s i o n coefficient of t h e oxide, a m e a s u r e
m e n t of t h e increase in thickness p o s t a n o d i z a t i o n will
p r o v i d e t h e r e q u i r e d i n f o r m a t i o n . If this factor is n o t
k n o w n t h e n o n e of t w o o t h e r t e c h n i q u e s m u s t be
e m p l o y e d : c o m p l e t e a n o d i z a t i o n of a film w h o s e
thickness is k n o w n or which c a n be m e a s u r e d , o r by

Figure 2
Anodization plots of (110) niobium-tantalum multilayers
showing (a) the differential voltage and (b) the direct
voltage vs time. Multilayer wavelength = 7.5 nm (1) and
= 3.4 nm (2). Atomic layers are represented by the ripple
structure on the dV/dt plots

r e m o v a l of the a n o d i z e d oxide. If high-quality m u l t i

layer s t r u c t u r e s a r e available t h e n t h e c a l i b r a t i o n
c o n s t a n t s for e a c h element m a y be o b t a i n e d using
c o m p o s i t i o n d a t a in c o n j u n c t i o n with the multilayer
p e r i o d o b t a i n e d from x-ray diffraction.

3.

Applications

E v e n d u r i n g its initial d e v e l o p m e n t it w a s clear t h a t

anodization spectroscopy h a d a remarkable depth
resolution. T h i n ( < 5 n m ) layers of silicon a n d a l u m i
n u m in n i o b i u m t u n n e l j u n c t i o n s t r u c t u r e s c o u l d
easily be o b s e r v e d ( K r o g e r et al. 1981) a n d t h e use of a
differential voltage o u t p u t h a s allowed t h e detection
of individual t u n n e l b a r r i e r s t r u c t u r e s of t h e o r d e r of
1-2 n m . H i g h - q u a l i t y artificial multilayers h a v e p r o
vided t h e best test of t h e resolution: K a d i n et al.
(1986) c o m p a r e a n o d i z a t i o n d e p t h profiles with x-ray
diffraction d a t a for a variety of s t r u c t u r e s a n d c o n
clude t h a t t h e limiting r e s o l u t i o n is below 1 n m . A
m u c h higher r e s o l u t i o n is evident in the d a t a r e p r o
d u c e d as F i g . 2: this s h o w s t h e direct o b s e r v a t i o n of
a t o m i c p l a n e s in t w o n i o b i u m - t a n t a l u m epitaxial
superlattice s t r u c t u r e s (Blamire et al. 1989). Barrier
layer d e t e c t i o n in s e m i c o n d u c t o r s such as the G a A s A l G a A s system h a s been r e p o r t e d ( F i s h e r a n d T e a r e
1989) with results w h i c h c o m p a r e favorably with
o t h e r depth-profiling t e c h n i q u e s .

15

Anodization

Spectroscopy

A n o d i z a t i o n s p e c t r o s c o p y h a s been successfully
d e m o n s t r a t e d o n a n u m b e r of systems. A p p l i c a t i o n s
of the t e c h n i q u e fall n a t u r a l l y i n t o t w o classes, which
will n o w be discussed.
3.1 Structure

Determination

A n o d i z a t i o n s p e c t r o s c o p y is of p a r t i c u l a r relevance t o
m a t e r i a l s which c o n t a i n a thin b u r i e d layer w h o s e
d e p t h from the surface is critical t o a n aspect of
s u b s e q u e n t device processing. A s a n e x a m p l e , a n o d i
z a t i o n s p e c t r o s c o p y h a s been used t o d e t e r m i n e the
s e p a r a t i o n of A 1 2 0 3 t u n n e l b a r r i e r s in n i o b i u m super
c o n d u c t i n g devices as a stage in their processing i n t o
three t e r m i n a l devices a n d for the direct m e a s u r e m e n t
of 1-2 n m A 1 0 x t u n n e l b a r r i e r thicknesses. T h i s p r o
filing t e c h n i q u e is p a r t i c u l a r l y a t t r a c t i v e in t h a t it c a n
be achieved as p a r t of a p r o c e s s i n g stage in its o w n
right, a n d the r o u t i n e m e a s u r e m e n t of a l u m i n u m
layer thicknesses in N b - A l O ^ - N b t u n n e l j u n c t i o n
structures is n o w s t a n d a r d in m a n y l a b o r a t o r i e s .
3.2 Layer

Uniformity

Measurement

T h e c h a r a c t e r i z a t i o n of highly r e g u l a r m u l t i l a y e r
s t r u c t u r e s is of p a r t i c u l a r interest, in t h a t m a n y of the
results o b t a i n e d from such s t r u c t u r e s d e p e n d o n the
regularity a n d s h a r p n e s s of t h e interfaces b e t w e e n
layers. C o m p l e m e n t a r y d a t a o n these aspects c a n be
o b t a i n e d from x-ray diffraction a n d A u g e r electron
s p e c t r o s c o p y ( A E S ) . K a d i n et al. (1986) a r g u e t h a t the
resolution o b t a i n a b l e from a n o d i z a t i o n s p e c t r o s c o p y
is higher t h a n t h a t o b t a i n a b l e from m o s t o t h e r d e p t h
profiling t e c h n i q u e s .

4. Comparison

with Other

Depth

entire multilayer; diffraction d a t a c a n p r o v i d e n o

i n f o r m a t i o n a b o u t isolated layers in a h e t e r o s t r u c t u r e . A n o d i z a t i o n p r o c e e d s o n a front w h i c h is a
u n i f o r m d i s t a n c e from t h e n e a r e s t e x p o s e d surface.
T h u s h i g h - r e s o l u t i o n i n f o r m a t i o n o n the s t r u c t u r e of
a m u l t i l a y e r thin film is o b t a i n e d even if the s u b s t r a t e
s h o w s imperfections in overall flatness o r finish. Dif
fraction m e t h o d s a n d scattering t e c h n i q u e s such as
low-angle R u t h e r f o r d b a c k scattering ( R B S ) a r e b o t h
sensitive t o such imperfections, with a resulting r e d u c
t i o n in r e s o l u t i o n .
R B S results a r e p r o b a b l y the closest t o a n o d i z a t i o n
s p e c t r o s c o p y in t e r m s of r e s o l u t i o n a n d sensitivity,
b u t t h e cost of t h e e q u i p m e n t a n d t h e c o m p l e x i t y of
t h e d a t a from w h i c h i n f o r m a t i o n m u s t be e x t r a c t e d
are i m p o r t a n t considerations. Transmission electron
m i c r o s c o p y ( T E M ) p r o v i d e s the best m e a n s by w h i c h
t o e v a l u a t e a n o d i z a t i o n s p e c t r o s c o p y as a t e c h n i q u e ,
b u t t h e complexities of T E M specimen p r e p a r a t i o n
m a k e a n o d i z a t i o n s p e c t r o s c o p y a useful r o u t i n e test
ing t e c h n i q u e .
A t its p r e s e n t stage of d e v e l o p m e n t a n o d i z a t i o n
s p e c t r o s c o p y is best viewed as a relatively inexpensive
r o u t i n e c h a r a c t e r i z a t i o n t o o l for t h e analysis of
d e p o s i t e d thin-film h e t e r o s t r u c t u r e s . U s e d in c o n
j u n c t i o n w i t h x-ray diffraction, c o m p l e m e n t a r y infor
m a t i o n m a y b e o b t a i n e d o n m u l t i l a y e r specimens,
while used o n its o w n it c a n a c c u r a t e l y d e t e r m i n e t h e
thickness of i n d i v i d u a l layers in c o m p l e x h e t e r o
s t r u c t u r e s w i t h a r a p i d i t y a n d t h r o u g h p u t w h i c h it is
hard to match.
See also: Auger Electron Spectroscopy; Depth Profiling; Ion
Backscattering Analysis; Secondary-Ion Mass Spectrometry

Profiling

Techniques

Bibliography

P r o b a b l y the greatest limit t o the w i d e s p r e a d applica

tion of a n o d i z a t i o n s p e c t r o s c o p y is the limited
n u m b e r of m a t e r i a l s for w h i c h suitable electrolytes
h a v e been found. H o w e v e r , for m a t e r i a l s w h e r e t h e
t e c h n i q u e h a s been d e m o n s t r a t e d it h a s a n u m b e r of
a d v a n t a g e s over c o m p e t i n g c h a r a c t e r i z a t i o n m e t h o d s ,
in p a r t i c u l a r the very low relative cost of a n o d i z a t i o n
a p p a r a t u s c o m p a r e d with c o m p e t i n g t e c h n i q u e s .
A n o d i z a t i o n s p e c t r o s c o p y c a n p r o v i d e detailed
c o m p o s i t i o n a l d a t a a b o u t t h e first few h u n d r e d n a n o
m e t e r s of thin-film h e t e r o s t r u c t u r e s . T h e a t o m i c - l a y e r
resolution h a s a g r e a t e r precision t h a n c a n be
o b t a i n e d with s p u t t e r r e m o v a l processes such as A E S
and secondary-ion mass spectrometry (SIMS), princi
pally b e c a u s e these m e t h o d s a r e f u n d a m e n t a l l y
limited by the escape d e p t h of t h e detected species
( 2 - 1 0 a t o m i c layers for b o t h A E S a n d S I M S ) a n d
also t h r o u g h u n c e r t a i n t i e s a s s o c i a t e d w i t h the s p u t t e r
etching process which is usually topologically d e p e n
d e n t a n d therefore inherently u n s t a b l e . X - r a y a n d
n e u t r o n diffraction d a t a c a n p r o v i d e m u c h g r e a t e r
resolution, b u t o n the basis of a n a v e r a g e over a n

Blamire G, Huang , Somekh R E, Kirk C G,

Morris G W, Evetts J 1989 Direct observation of
atomic planes in epitaxial multilayers by anodization
spectroscopy. Appl. Phys. Lett. 55: 732-4
Fisher C W, Teare S W 1989 Anodic oxidation of AlGaAs
and detection of the AlGaAs heterojunction interface.
J. Appl. Phys. 67: 2608-12
Kadin A M, Burkhardt R W, Keem J 1986 Multilayer
anodization profile (MEP): a novel depth profile tech
nique for metallic-based layered structures. Mater. Res.
Soc. Symp. Proc. 56: 473-8
Kroger H, Smith L N, Jillie D W 1981 Selective niobium
anodization process for fabricating Josephson junctions.
Appl. Phys. Lett. 39: 280-2

16

M . G. Blamire
[University of C a m b r i d g e ,
Cambridge, U K ]

Art Forgeries: Scientific Detection

T o a large extent, forgers succeed by a u d a c i t y r a t h e r
t h a n by the possession of a n y o u t s t a n d i n g artistic o r

Art Forgeries:

technical talents: tactically p l a n n e d , h i g h - p r e s s u r e

s a l e s m a n s h i p in the a r t m a r k e t is used t o c a m o u f l a g e a
lack of skill. L o o k i n g b a c k t h r o u g h history, h o w e v e r ,
there h a v e been s o m e n o t a b l e exceptions t o this
generalization. T h e V e r m e e r forger, H a n v a n M e e geren, is p e r h a p s t h e b e s t - k n o w n a l t h o u g h t h e m i d nineteeth-century sculptor, G i o v a n n i Bastianini, a n d
the early n i n e t e e n t h - c e n t u r y coin counterfeiter, C a r l
Wilhelm Becker, were his technical e q u a l s . S o m e
scholars believe t h a t t h e sculptor, Alceo D o s s e n a ,
w o u l d h a v e escaped d e t e c t i o n a l t o g e t h e r if only he
h a d persevered with his forteMadonna figures in the
style of the f o u r t e e n t h - c e n t u r y T u s c a n s c h o o l i n
stead of trying t o m i m i c t h e e n i g m a t i c smiles of
E t r u s c a n figurative s t a t u a r y .
T h e d e c e p t i o n of A l b e r t o d e la M a r m o r a is, h o w
ever, m o r e typical of the incidents t h a t m a k e u p the
history of forgery overall. In t h e 1840s, after several
years of a m a t e u r e x p l o r a t i o n of S a r d i n i a , this Italian
general h a d a m a s s e d a h u g e collection of g r o t e s q u e
(and totally s p u r i o u s ) sticklike b r o n z e
figurines.
W h e n r u m o r of fakery b e g a n t o s p r e a d , his suppliers
fabricated a fifteenth-century s k e t c h b o o k by a certain
Michele Gili ( n o t a r y of the s o u t h e r n S a r d i n i a n p o r t of
Cagliari) t o s u b s t a n t i a t e their p r o v e n a n c e . W o r s e w a s
to follow, b e c a u s e this e x t r a d o c u m e n t a r y evidence
w a s e n o u g h t o d r a w several of d e la M a r m o r a ' s
friends i n t o a search for parallels t o t h e b r o n z e s a m i d
the m y t h o l o g y of s o m e truly o b s c u r e cultures. I n t r i g u
ing links were established with idols from a n a n c i e n t
Slavonic tribe k n o w n as t h e O b o t r i t e s ; intriguing, in
t h a t t h o s e idols were also i n g e n i o u s forgeries p r o
duced only a c e n t u r y before.
T w o effects, it seems, h a v e either t o g e t h e r o r i n d e
p e n d e n t l y led t o gross e r r o r s in visual a p p r a i s a l of
s o m e of the m o r e n o t o r i o u s fakes. T h e first c a n be
labelled " c o n t e m p o r a r y b l i n d n e s s , " a fault t h a t is well
illustrated by s t u d y of The Montefeltro
Family, a
p o r t r a i t g r o u p p r o d u c e d by t h e versatile Siennese
forger, F r e d e r i c o J o n i . T h i s p a i n t i n g w a s late
fifteenth-century
F l o r e n t i n e in c o n c e p t i o n , b u t c o n
tained the glaringly a n a c h r o n i s t i c element of a k i n d of
c h e q u e r e d c a p w h i c h w a s highly fashionable in P a r i s ,
c. 1920, in t h e w a k e of t h e designer Bakst. Y e t it w a s
only a d e c a d e after t h e w o r k w a s b o u g h t by t h e
N a t i o n a l G a l l e r y in L o n d o n t h a t this failing w a s
noticed.
T h e o t h e r effect a m o u n t s to " p r e s s u r i z e d misjudgm e n t . " It is typified by t h e incident in 1965, w h e r e
several leading m u s e u m s e a c h p u r c h a s e d a d o u b l e h e a d e d a n t h r o p o m o r p h i c vase with inlaid o b s i d i a n
eyes, accepting the alleged p r o v e n a n c e of a n o b s c u r e
cemetery close t o the official e x c a v a t i o n s at t h e T u r
kish site of H a c i l a r . A l m o s t all were fake, a fact t h a t
b e c a m e only t o o o b v i o u s w h e n t h e d a t a b a n k for
c o m p a r a t i v e m a t e r i a l t h e site's formal p u b l i c a
t i o n w a s available five years later.
It is these effects, a l o n g with t h e interest of certain
a u c t i o n h o u s e s in h o l d i n g d o w n i n s u r a n c e p r e m i u m s

Scientific

Detection

o n t h e accepted m a r k e t p r o m i s e t o refund m o n e y s
gained by e r r o n e o u s a t t r i b u t i o n , t h a t h a v e been the
s t i m u l u s for a c u r r e n t g r o w t h in the involvement of
science in a r t analysis. T h a t i n v o l v e m e n t is n o t always
p a r t i c u l a r l y d e e p p e r h a p s j u s t the identification of a
m o d e r n industrial c o m p o n e n t in the p a p e r of a n
illuminated m a n u s c r i p t , o r of a resin vehicle in the
false p a t i n a t i o n o n a b r o n z e . O t h e r times, however,
t h e analytical a p p r o a c h h a s been m o r e sophisticated,
t a p p i n g resources of m o d e r n t e c h n o l o g y t h a t , in
m a n y instances, a r e scarcely a d e c a d e old.
T h e sheer diversity of m e d i a used in a r t over the
p a s t c o u p l e of millennia h a s e n s u r e d t h a t the field of
scientific fake detection is a very active o n e , t h o u g h
there a r e several m a t e r i a l s ( n o t a b l y Classical gold
jewelry a n d m a r b l e sculpture) t h a t still defy reliable
m e t h o d s of a u t h e n t i c i t y analysis. H o w e v e r , four areas
of forgery r e s e a r c h t h e d a t i n g of the clay fabric of
c e r a m i c s , the i n t e r p r e t a t i o n of the v a r i o u s s t r u c t u r a l
c o m p o n e n t s of p a i n t i n g s a n d the alloy analysis of
coins a n d of m e t a l s t a t u a r y h a v e each p r o d u c e d a n
extensive " r o g u e s ' g a l l e r y , " t o g e t h e r with a very ex
tensive ( s o m e t i m e s c o n t r o v e r s i a l ) literature. T h e case
histories included in the following general discussion
d r a w o n t h a t literature a n d typify the k i n d s of p r o b
lems t h a t a r t forgery h a s p o s e d a n d their technical
solution.

1.

Ceramics

W o r l d w i d e a n d a t all levels of s o p h i s t i c a t i o n of the

w a r e type, from d o m e s t i c p o t t e r y t o lifesize t e r r a c o t t a
s t a t u a r y , t h e c e r a m i c m e d i u m h a s b o r n e the b r u n t of
t h e forgers' assault o n t h e a r c h a e o l o g i c a l record.
A m o n g t w o g r o u p s of collectibles (delicate Hellenistic
figurines t h a t were in a v o g u e a c r o s s the Classical
w o r l d in the t h i r d c e n t u r y BC a n d the Chinese funer
ary s t a t u a r y of the T ' a n g D y n a s t y (AD 618-906))
forgery h a s t a k e n the u n u s u a l c o u r s e of exploiting
original casting m o l d s recovered d u r i n g illicit excava
tion of p r o d u c t i o n sites, t o create objects t h a t a r e
aesthetically indistinguishable from their ancient
prototypes.
T h e c u r r e n t g r o w t h a r e a in forgery is E t r u s c a n art.
T h i s h a s its r o o t s in the second q u a r t e r of the nine
t e e n t h c e n t u r y , w h e n official e x c a v a t i o n in the region
of Cerveteri ( a b o u t 30 k m n o r t h w e s t of R o m e ) first
d r e w a t t e n t i o n t o the mystical a n d s o m b e r civilization
t h a t thrived in western Italy in t h e mid-first millen
n i u m B C . Jewelry w a s the initial focus of a t t e n t i o n ,
after F o r t u n a t o Castellani revived the a n c i e n t tech
n i q u e of g r a n u l a t e d d e c o r a t i o n in gold, b u t interest
s o o n t u r n e d t o t e r r a c o t t a w h e n t h e C a m p a n a collec
tion of wall p a i n t i n g s w a s exhibited in the L o u v r e .
( T h e restorer of t h o s e wall p a i n t i n g s t u r n e d his o w n
h a n d t o forgery w h e n he used o n e scene as a m o d e l for
a s a r c o p h a g u s which the British M u s e u m b o u g h t in
1873.) L o o t e r s , locally called tombaroli, h a v e c o n -

17

Art Forgeries:

Scientific

Detection

Figure 1
The Ambush of Troilus and Polyxena, a detail from a fake painting on terracotta in the Etruscan style (courtesy of
S. J. Fleming)

tinued to strip the E t r u s c a n necropoleis l o n g before

archaeologists learn of their w h e r e a b o u t s , a n d forgers
have h a d little difficulty m i x i n g their p r o d u c t s i n t o t h e
stock of genuine pieces circulating in the s h a d o w y
p a r t s of t h e a r t m a r k e t .
The thermoluminescence dating method, though
only fully developed in the early 1970s, h a s a l r e a d y
p r o v e n the m o s t powerful tool in the s t e m m i n g of a
new w a v e of E t r u s c a n forgery. In its physical process,
t h e effectiveness of the m e t h o d hinges o n t h e fact t h a t
all m a t e r i a l s c o n t a i n a t least traces of n a t u r a l r a d i o
activity ( 4 0K , a n d the decay series for 2 3U8 , 2 3U5
a n d 2 3T2 h ) t h a t release energy as they decay. Q u a r t z
a n d feldspars in a t e r r a c o t t a fabric c a n a b s o r b this
energy a n d store a fraction of it by electron t r a p
p i n g at i m p u r i t y ions a n d lattice defects. A s u b s e q u e n t
h e a t i n g to 500 C causes this energy t o be released
in the form of light, t h a t is, as t h e r m o l u m i n e s c e n c e
(TL).

18

T h e r a w m a t e r i a l s of t h e t e r r a c o t t a will h a v e s t o r e d
a great deal of T L energy d u r i n g their geological
history, b u t all t h a t energy will h a v e been erased by
kiln firing a t 700 C o r m o r e d u r i n g its m a n u f a c t u r e .
In o t h e r w o r d s , a time-zero is set for further T L
energy a c c u m u l a t i o n d u r i n g archaeological time. T h e
T L intensity m e a s u r e d t o d a y p r o v i d e s a n e s t i m a t e of
the t o t a l r a d i a t i o n d o s a g e received by the t e r r a c o t t a ,
a n d t h a t d o s a g e reflects t h e age of t h e t e r r a c o t t a . A
forgery will h a v e a relatively low d o s a g e c o m p a r e d
with its a n c i e n t c o u n t e r p a r t .
T h e t e r r a c o t t a w a l l - p a i n t i n g illustrated in Fig. 1,
depicting t h e m y t h i c a l t h e m e of The Ambush of Troi
lus and Polyxena, is o n e of a g r o u p of such artifacts
w h i c h a p p e a r e d in M u n i c h s o m e t i m e after 1963. It
w a s s u p p o s e d l y from a wall-niche in a n illicitly
o p e n e d t o m b which h a d been lavishly d e c o r a t e d in
h o n o r of a deceased E t r u s c a n n o b l e s o m e 2500 years
a g o . H o w e v e r , T L d a t a revealed t h a t it h a d been

Art Forgeries:

m a d e s o m e t i m e within the five years before its

marketing.
T h e scene w a s later recognized as a pastiche
modelled after a fresco from the Tomb of Bulls at
T a r q u i n i a , e x t r a c t i n g its c o m p o n e n t s from a wall
p a i n t i n g found at B a n d i t a c c i a (with the t w o figures
facing the o t h e r w a y ) , a scene depicting a p a i r of
wrestlers in the Tomb of the Augurs at T a r q u i n i a (for
the bird) a n d the G r e e k Onesimos Bowl n o w in
Brussels (for the large w a t e r pitcher). Several features
of this g r o u p of fake wall p a i n t i n g s suggest t h a t they
were transferred by s o m e m e c h a n i c a l m e a n s from
p h o t o g r a p h s in leading a r t b o o k s .

2.

Paintings

T h e process of c a p t u r i n g the distinctive use of light,

form a n d i c o n o g r a p h y t h a t characterizes t h e p a i n t i n g
style of the better k n o w n p a i n t e r s o r p a i n t i n g schools,
raises m a n y p r o b l e m s for t h e forgers. M o s t of t h e m
o p t j u s t to tag the s i g n a t u r e of s o m e o n e f a m o u s o n t o
the w o r k of a lesser artist w h o w o r k e d in a similar
style. F o r this r e a s o n , s o m e of the familiar p a i n t i n g s
by Vermeer, w h o s e o w n artistic skill w e n t largely
u n n o t i c e d until the 1920s, c a r r y s p u r i o u s a t t r i b u t i o n
to his c o n t e m p o r a r y , Pieter de H o o c h , w h o w a s
p o p u l a r in his o w n lifetime a n d t h r o u g h o u t the eight
eenth a n d n i n e t e e n t h centuries. T h e r e h a v e , h o w e v e r ,
been s o m e a t t e m p t s a t " i n - s t y l e " pastiches, c o a g u l a
tions of v a r i o u s elements b o r r o w e d from different
w o r k s by t h e s a m e p a i n t e r so t h a t t h e viewer is set a t
ease by familiar features. In this respect, H a n v a n
Meegeren w a s p a r t i c u l a r l y successful in the w a y t h a t
he r e p r o d u c e d a white " w a t e r - b e a d " t e c h n i q u e which
V e r m e e r e m p l o y e d t o highlight c u r v e d surfaces of
b r e a d a n d fruit.
W h e r e the need h a s arisen for scientific a r b i t r a t i o n
of conflicting a r t historical o p i n i o n , t w o technical
a p p r o a c h e s h a v e p r o v e n m o s t effective in a u t h e n t i c i t y
assessment r a d i o g r a p h y a n d individual p i g m e n t
analysis. X r a d i o g r a p h y d r a w s its strength from the
fact t h a t forgers, even if they h a v e t a k e n t h e t r o u b l e t o
seek o u t old c a n v a s e s or w o o d e n panels of r o u g h l y the
a p p r o p r i a t e a n t i q u i t y , will rarely g o so far as t o
painstakingly strip a w a y all the p a i n t layers applied
previously. P r o v i d e d the p a l e t t e used for u n d e r l y i n g
w o r k includes the r a d i o p a q u e p i g m e n t lead white
(which w a s the only white used in E u r o p e a n oil
p a i n t i n g until the 1840s) a n x-ray i m a g e will readily
reveal its presence. If the u n d e r l y i n g w o r k actually
p o s t d a t e s the overlying o n e in style, a n a c h r o n i s m will
be clear evidence of forgery. F o r e x a m p l e , o n e version
of Picasso's Absinthe Drinker which w a s for s o m e
time a t t r i b u t e d t o t h e m o d e r n m a s t e r ' s " b l u e p e r i o d "
(which e n d e d c. 1905) w a s s u b s e q u e n t l y f o u n d to h a v e
as an u n d e r p a i n t i n g a n a b s t r a c t which d a t e d c. 1915.
T h e search for a n a c h r o n i s m s is also the key to the
use of p i g m e n t analysis as a n a u t h e n t i c i t y tool. A

Scientific

Detection

g r o u p of scalpel-thin sections at v a r i o u s strategic

p o i n t s across the surface of the p a i n t i n g , once
m o u n t e d in a resin a n d surface polished, provides a
s t r a t i g r a p h y of color, each layer c o m p r i s i n g clusters
of p i g m e n t grains of varying size e m b e d d e d in a n o w
a g e - h a r d e n e d m a t r i x of the original vehicle for the
a p p l i c a t i o n of the p a i n t (for e x a m p l e , linseed o r
w a l n u t oil). A t m i c r o s c o p i c magnifications of
a b o u t x 100, the p i g m e n t grains exhibit such c h a r a c
teristic optical p r o p e r t i e s t h a t p i g m e n t identification
is r a p i d a n d rarely a m b i g u o u s . F o r e x a m p l e , a m o n g
the t r a d i t i o n a l blue p i g m e n t s , the splintered-glass
edges of smalt c o n t r a s t sharply with the cleanly
fractured edges of n a t u r a l u l t r a m a r i n e crystals, while
the lack of optical birefringence in the latter sets it
a p a r t from azurite. P i g m e n t s p r o d u c e d in relatively
m o d e r n times by the c o n t r o l l e d chemistry of precipi
t a t i o n s t a n d o u t by virtue of their r o u n d n e s s a n d
uniformity of particle size.
F a i l i n g confident identification at this stage, indi
vidual particles of p i g m e n t c a n be s e p a r a t e d o u t for
m i c r o c h e m i c a l analysis, each p i g m e n t h a v i n g a c h a r
acteristic reaction t o certain sequences of chemical
study. F o r e x a m p l e , the m e r c u r y in vermilion red
( H g S ) forms m e r c u r y c h l o r i d e needles w h e n a d r o p l e t
of the nitric a c i d - h y d r o c h l o r i c acid m i x t u r e aqua
regia is applied. T h e s e needles c o n v e r t t o d e e p blue
p r i s m s of c o b a l t m e r c u r i c t h i o c y a n a t e w h e n a d r o p l e t
from a s o l u t i o n of c o b a l t a c e t a t e a n d p o t a s s i u m
t h i o c y a n a t e is a d d e d . Vermilion c a n n o t therefore be

Table 1
A comparison between the main colors of the traditional
artist's palette and those introduced in the wake of the
eighteenth century chemical revolution: the data for the first
use of each new color in European oil painting is given in
parentheses
Traditional

Artificial

lead white

zinc white (1844)

titanium oxide white (1919 - h )

vermilion
red/brown ocher
red lead
madder

cadmium red (1910 + )

various organic reds (1905 + )

lapis lazuli blue

azurite
smalt

Prussian blue (1709)

cobalt blue (1777 + )
French ultramarine (1828 + )
cerulean blue (1863 + )

yellow ocher
litharge
Naples yellow

chromium yellow (1823)

cadmium yellow (1834)

verdigris
malachite
green earth

Scheele's green (1778 + )

emerald green (1844)
cobalt green (1848)
viridian (1862)

19

Art Forgeries:

Scientific

Detection

Figure 2
Detail from Still Life in the style of the Spanish master, Francisco de Zurbaran: it is now recognized as a post-1830 work,
because cadmium yellow was used to paint the skin of the lemons (courtesy of the St. Louis Art Museum: inv. 114.42)

confused with its m o d e r n substitute, c a d m i u m red

(CdS:Se) which r e s p o n d s quite differently to these
chemical t r e a t m e n t s . ( T h e identification of its c a d
m i u m c o n t e n t calls for o b s e r v a t i o n of a c o m p l e x
reaction involving /?-nitrophenylcarbazide as the acti
vating reagent.)
T h e chemical revolution of the eighteenth a n d
nineteenth centuries (which, in t e r m s of the history of
color, b e g a n with the c h a n c e p r o d u c t i o n of P r u s s i a n
blue by F r a n z D i e s b a c h in Berlin, c. 1705) resulted in
the t r a d i t i o n a l palette being a l m o s t completely super
seded by a n artificial o n e (see T a b l e 1). T h u s , n o
p a i n t i n g claiming a t t r i b u t i o n t o t h e seventeenth cen
tury o r earlier s h o u l d ever (except in a r e a s of resto
r a t i o n ) b e a r a n y of the colors from the artificial
palette. If it d o e s , the evidence of forgery is clearcut
(see Fig. 2).
Scientific a u t h e n t i c i t y analysis of p a i n t i n g s is, h o w
ever, m u c h c o m p l i c a t e d by t h e fact t h a t m a n y of the
m a j o r p a i n t e r s of the p a s t (including R u b e n s a n d

20

R e m b r a n d t ) r a n schools of p a i n t i n g , p r o d u c t s of
which often beg for higher a t t r i b u t i o n t h a n " a p u p i l
of
" S o m e of t h o s e schools c o n t i n u e d t o flourish
m a n y d e c a d e s after t h e o r i g i n a t o r h a d died. P i g m e n t
analysis, a n d indeed m a n y of t h e n e w e r t e c h n i q u e s
b e g i n n i n g t o be applied t o a u t h e n t i c i t y analysis of
p a i n t i n g s (lead i s o t o p e analysis, a u t o r a d i o g r a p h y ,
infrared reflectometry, etc.) lack t h e t e m p o r a l resolu
tion r e q u i r e d t o u n r a v e l t h e scope of w o r k s h o p activi
ties of this k i n d .

3. Counterfeiting

of Silver

Coinage

W h e n the A m e r i c a n C h i n a T r a d e r Rapid s a n k off the

c o a s t of W e s t e r n A u s t r a l i a in 1811, its c a r g o b e c a m e a
" t i m e c a p s u l e " of p r e v a l e n t t r a d i n g practices. W h e n
t h e ship w a s raised in 1981, its c a r g o w a s f o u n d t o
c o n t a i n w h a t a p p e a r e d t o be a S p a n i s h silver d o l l a r
(an 8 real) d a t e d 1796 a n d b e a r i n g the m i n t m a r k of

Art Forgeries:

Scientific

Detection

Figure 3
A debased Mexican 8 real piece (obverse and reverse) recovered from the wreck of the American China Trader Rapid
(courtesy of I. MacLeod)

M e x i c o a n d t h e assayer's initials FM (see Fig. 3). B u t

it h a d a n o d d l a m i n a t e d s t r u c t u r e , a n d this s t i m u l a t e d
a s t r u c t u r a l investigation, using c o r r o s i o n p o t e n t i a l
p o l a r o g r a p h y , w h i c h represents o n e of the latest a d
vances in a u t h e n t i c i t y research.
W h e n a m e t a l is e x p o s e d over a long p e r i o d t o a n
a e r a t e d electrolyte such as seawater, a n electrical
p o t e n t i a l develops within t h e metallic s t r u c t u r e as a
c o m b i n e d result of localized oxygen r e d u c t i o n a n d the
g r a d u a l o x i d a t i o n of t h e m e t a l . F o r silver t h e o x i d a
tion reaction leads t o t h e f o r m a t i o n of a thin film of
silver chloride. T h e presence of a m e t a l less n o b l e t h a n
silver will result in a depression of the c o r r o s i o n
p o t e n t i a l . In the case of t h e 1796 d o l l a r this d e p r e s
sion w a s observed b e c a u s e t h e c o i n ' s c o r e c o m p r i s e d a
c o p p e r alloy. T h e coin a p p e a r s t o h a v e been fabri
cated by a t t a c h i n g a silver-rich sheet 0.25 m m thick t o
the core, using a silver solder ( a p p r o x . 7 2 % silver,
2 8 % c o p p e r ) p r i o r to rolling a n d s t a m p i n g .
T h e r e a s o n for this incident of counterfeiting is
obscure, b u t t h e silver c o a t i n g of b r o n z e coins w a s
o n e of the m o s t c o m m o n forgery practices in a n
tiquity. It h a s been d o c u m e n t e d in R o m a n Britain a n d
the Gallic R h i n e l a n d in t h e m i d - t h i r d c e n t u r y A D (just
before t h e official m i n t s of R o m e did it, c. 260) a n d it
h a s been identified in a f r a g m e n t e d 1620
Rijksdaalder
recovered from the wreck of t h e D u t c h E a s t I n d i a m a n
Batavia t h a t w e n t d o w n off t h e c o a s t of W e s t e r n
A u s t r a l i a in 1629.
Direct silver d e b a s e m e n t by alloying with excessive
a m o u n t s of c o p p e r also h a s a l o n g h i s t o r y , t h e c o u n
terfeiting often h a v i n g a political m o t i v a t i o n . F o r

e x a m p l e , in 1124, at the e n d of a year of failed c r o p s

a n d a n a t i o n a l crime w a v e , H e n r y I of E n g l a n d t o o k
t h e u n p r e c e d e n t e d step of m u t i l a t i n g all of E n g l a n d ' s
m o n e y e r s (by c u t t i n g off their right h a n d s a n d testi
cles), ostensibly b e c a u s e the silver c o i n a g e being
set as p a y m e n t t o his t r o o p s in N o r m a n d y w a s n e a r w o r t h l e s s . ( M o r e realistically, t h e act w a s i n t e n d e d t o
c a l m t h e c o m m o n folk w h o , a m i d their o w n p o v e r t y ,
were only t o o eager t o find a s c a p e g o a t o t h e r t h a n the
k i n g for E n g l a n d ' s fiscal plight, even t h o u g h its cause
w a s assuredly the b u r d e n of his warlike p o s t u r e in
E u r o p e . ) I n t h e late sixteenth c e n t u r y , there is g o o d
r e a s o n t o believe L o r d Burghley's c o m p l a i n t in his
letters t o t h e E a r l of Leicester t h a t t h e D u t c h were
p a s s i n g vast q u a n t i t i e s of i m i t a t i o n , heavily-debased
E l i z a b e t h a n shillings a m o n g t h e English t r o o p s in the
Netherlands.

4. Bronze

Statuary

In historical t e r m s , a r t forgery received t w o of its

s t r o n g e s t stimuli w h e n the M u m m i u s sacked C o r i n t h
in 146 BC, a n d w h e n Sulla c a p t u r e d A t h e n s 60 years
later. Spoils of w a r included s o m e of t h e finest Classi
cal s t o n e a n d b r o n z e s t a t u a r y , a n d the m o r e timid
b u r e a u c r a t s in R o m e w h o w a n t e d t o m a i n t a i n
fashionable h o m e s a n d h a v e artistic talking p o i n t s
d u r i n g politically i m p o r t a n t b a n q u e t s were left with
little choice b u t t o e m p l o y G r e e k a r t i s a n s as copyists.
T h e distinction b e t w e e n G r e e k originals a n d R o m a n
imitations became quite blurred when Renaissance

21

Art Forgeries:

Scientific

Detection

U S $ 0 . 3 million. All were s h o w n t o be fakes, their

m e t a l being b r a s s (a c o p p e r - z i n c alloy, with a zinc
c o n t e n t of m o r e t h a n 3 0 % ) n o t b r o n z e . ( T h e tech
n o l o g y of b r a s s m a k i n g w a s u n k n o w n in the T h a i
p e n i n s u l a until the late fifteenth c e n t u r y , at the ear
liest.) M e t a l l o g r a p h i c s t u d y indicated t h a t a n a t t e m p t
h a d b e e n m a d e t o create a n artificial green p a t i n a t i o n
o n the m e t a l surface b y pickling t h e piece in s o m e
t h i n g a k i n t o sulfuric acid.
5. Future

Hazards

D e s p i t e the great strides m a d e in scientific a u t h e n t i

city analysis over the p a s t t w o decades, this is n o t a n
a r e a of research w h e r e there is a n y r o o m for c o m
placency. Red Figure vases a r e a p p a r e n t l y n o w being
m a d e in w o r k s h o p s n e a r R o m e by exactly the s a m e
firing t e c h n i q u e s as used in G r e e c e d u r i n g the fifth
c e n t u r y BC; g e n u i n e coins a r e being faithfully r e p r o
d u c e d by p r e s s u r e - m o l d i n g ; a n d laser-measuring de
vices a r e helping forgers recreate the finest detail o n
sculpture. Several m o d e r n forgers seem t o be as
sophisticated in their t e c h n o l o g y as the scientists w h o
a r e trving to limit their activity.
See also: Ceramic Materials: Cathodoluminescence Analy
sis; Chemical Analysis of Solid Surfaces; Thermoluminescence
Bibliography

Figure 4
Bodhisattva, a fake casting in the style of pre-Khmer
(c. seventh century) bronze statutary from the Thai
temple site of Pra Kon Chai (courtesy of S. J. Fleming)

sculptors, in search of their ideal to c a p t u r e a n d

surpass the Classical spirit, plagiarized everything
a n t i q u e t h a t they c o u l d find. B e n v e n u t o Cellini, with
typical i m m o d e s t y , is k n o w n to h a v e felt t h a t the
quality of s o m e of his m e t a l w o r k surpassed Classical
p r o t o t y p e s a n d is suspected of indulging in s o m e
fakery himself.
Recently, T h a i l a n d h a s b e c o m e o n e of the centers
of a r t forgery, with the city of B a n g k o k as its e n t r e p o t
to western m a r k e t s . F a k e s a r e mingled with the
n u m e r o u s g e n u i n e artifacts t h a t h a v e been systemati
cally p l u n d e r e d from the ancient t e m p l e complexes
t h a t lie h i d d e n in the tangled u n d e r g r o w t h of the
eastern forests. T h e half lifesize Bodhisattva
illus
t r a t e d in Fig. 4 w a s said t o h a v e been p a r t of a c a c h e
of b r o n z e s t a t u a r y found, by c h a n c e , in the ruins of a
seventh-century t e m p l e situated n e a r P r a K o n C h a i ,
o n the T h a i - K a m p u c h e a n b o r d e r . Its form o c c u r r e d
several times in t h e c a c h e , with a p p r e c i a b l e size r a n g e .
T h r e e of these pieces r e a c h e d the L o n d o n a r t m a r k e t
a n d were r u m o r e d t o h a v e been valued at m o r e t h a n

22

Ainsworth W, Brealey J, Haverkamp-Begemann E,

Meyers 1982 Art and Autoradiography. Museum of
Modern Art, New York
Aitken J, Moorey R S, Ucko J 1971 The authenticity
of vessels and figurines in the Hacilar style. Archaeometry
13: 89-141
Boon G C 1974 Counterfeiting in Roman Britain. Sci. Am.
231(6): 120-30
Boone 1982 Falsifications and Misreconstructions of
Pre-Columbian Art. Center for Byzantine Studies, Dum
barton Oaks, Washington, DC
Fleming S J 1974 Thermoluminescent authenticity studies of
unglazed T'ang Dynasty ceramic tomb goods. Archaeo
metry 16: 91-5
Fleming S J 1975 Authenticity in Art. Institute of Physics,
Bristol, UK
Fleming S J 1979 An evaluation of physico-chemical
approaches to authentication. In: Jaffe H L C , Storm van
Leeuwen J, van der Tweel L (eds.) 1979 Authentication
in the Visual Arts. . M. Israel BV, Amsterdam, pp. 103
39
Fleming S J, Jucker H, Riederer J 1971 Etruscan wallpaintings on terracotta: a study in authenticity. Archaeo
metry 13: 143-67
Gettens R J, Feller R L, Chase W 1972 Vermilion and
cinnabar. Stud. Conserv. 17: 45-69
Gilardoni A, Orsini R A, Taccani S 1977 X-Rays in Art.
Gilardoni, Como, Italy
Harley R D 1982 Artists' Pigments, c. 1600-1835, 2nd edn.
Butterworth, London.
Hill G F 1924 Becker, The Counterfeiter, Vols. 1 and 2.
Spink, London

Atomic

Houtman J W, Turkstra J 1965 Neutron activation

analysis of trace elements in white lead and its possible
application for age determination of paintings. Radioche
mical Methods of Analysis, Vol. 1. IAEA, Vienna, pp. 85102
Jeppson L 1977 Fabulous Frauds. Arlington Books, London
Keck S 1948 The laboratory detection of fraud. Mag. Art
41: 172-83
Keisch B, Callahan R C 1976 Lead isotope ratios in artists'
lead white: progress report. Archaeometry 18: 181-93
Kuhn 1973 In: Young W J (ed.) 1973 Application of
Science in Examination of Works of Art, Vol. 2. Museum
of Fine Arts, Boston, MA
Kurz 1967 Fakes, 2nd edn. Dover, New York
Lux F, Braunstein L, Strauss R 1969 Investigations on the
age and place of origin of paintings by neutron activation
analysis. In: National Bureau of Standards 1969 Modern
Trends in Activation Analysis, NBS Spec. Pub. 312, Vol. 1.
NBS, Washington, DC, pp. 216-25
MacLeod I D 1982 A study of some forged silver coins
recovered from 17th century and 19th century ship
wrecks. Chem. Austral. 49: 317-20
Plesters J 1956 Cross-sections and chemical analysis of paint
samples. Stud. Conserv. 2: 110-57
Pope-Hennessy J 1964 Catalogue of Italian Sculpture in the
Victoria and Albert Museum, Vol. 2. Her Majesty's
Stationery Office, London
Rees-Jones S 1960 Physics and painting. Bull. Inst. Phys. 11:
157-65
Rieth A 1970 Archaeological Fakes. Barrie & Jenkins,
London
Sads S II, Johnson C 1973 Fakes and Forgeries. Minnea
polis Institute of Arts, Minneapolis, MN
Van Asperen de Boer J R J 1970 Infrared Reflectography.
Central Research Laboratory for Objects of Art and
Science, Amsterdam
Werner 1972 Spectroanalytical and Metalurgical Tests
on Indian Bronzes (in German). Brill, Leiden, The
Netherlands
S. J. F l e m i n g
[University of P e n n s y l v a n i a , P h i l a d e l p h i a ,
Pennsylvania, USA]

Atomic Force Microscopy

T h e a t o m i c force m i c r o s c o p e ( A F M ) p r o v i d e s q u a n t i
tative t o p o g r a p h i c i m a g e s of surfaces. A l s o referred t o
as a surface force m i c r o s c o p e o r a s c a n n i n g force
m i c r o s c o p e ( S F M ) , it uses a s h a r p tip s c a n n e d over
the specimen t o sense surface forces. In principle,
either a t t r a c t i v e o r repulsive forces b e t w e e n the tip
a n d surface c a n be detected; in practice, the repulsive
force m o d e is p r e d o m i n a n t l y used b e c a u s e it is m o r e
stable. T h e m i c r o s c o p i c i m a g e p r o d u c e d is t h a t of a
surface, r e p r e s e n t i n g t h e locus of p o i n t s of c o n s t a n t
force b e t w e e n t h e tip a n d t h e specimen. A l t h o u g h
functionally similar t o a stylus surface profilometer,
the A F M utilizes m u c h smaller forces b e t w e e n tip a n d
surface (typically 0.1 ) a n d t h e small r a d i u s of
c u r v a t u r e of t h e tip (0.03 ) gives better spatial
resolution. T h e tip is usually held s t a t i o n a r y a n d t h e

Force

Microscopy

s a m p l e is s c a n n e d using piezoelectric t r a n s d u c e r s .
M u c h of the t e c h n o l o g y used in the A F M h a s been
derived from the s c a n n i n g tunnelling m i c r o s c o p e
( S T M ) . A n i m p o r t a n t feature of the A F M is its ability
to i m a g e n o n c o n d u c t i n g surfaces, w h e r e a s the S T M
requires a c o n d u c t i n g surface c a p a b l e of sustaining a
stable tunnelling c u r r e n t . Several c o m m e r c i a l instru
m e n t s p r o v i d e b o t h S T M a n d A F M capabilities by
simply switching types of surface detector.
3
T h e useful magnification r a n g e is from 10 to
7
g r e a t e r t h a n 10 . A t o m i c resolution, of the o r d e r of
0.1-0.2 n m , h a s been achieved o n s m o o t h surfaces.
E q u a l l y i m p o r t a n t , vertical distances can be m e a s u r e d
to a resolution of less t h a n 1 n m . T h e i n s t r u m e n t
typically o p e r a t e s in air, b u t c a n easily be set u p with
the tip a n d specimen s u r r o u n d e d by a liquid. O p e r a
tion in a v a c u u m is possible b u t n o t c o m m o n . T h e
A F M is n o t well suited t o e x a m i n i n g r o u g h surfaces
o r surfaces inclined with respect to the tip.
T h e i n f o r m a t i o n collected d u r i n g a scan of the
surface is q u a n t i t a t i v e in three d i m e n s i o n s . W h e n
p r e s e n t e d as a t o p o g r a p h i c i m a g e , the elevation of
e a c h p o i n t in t h e p i c t u r e is e n c o d e d a c c o r d i n g to a
g r a y scale o r a false c o l o r scale. T h i s is a n a l o g o u s t o a
t o p o g r a p h i c m a p of a piece of l a n d . By g e n e r a t i n g a
r e n d e r e d t h r e e - d i m e n s i o n a l perspective, it is possible
t o r e c o n s t r u c t a n i m a g e of the surface features from
different v i e w p o i n t s . Profiles, o r cross sections,
t h r o u g h the surface c a n be p l o t t e d a n d q u a n t i t a t i v e
h o r i z o n t a l a n d vertical distances m e a s u r e d . R o o t m e a n - s q u a r e surface r o u g h n e s s c a n be c o m p u t e d
a l o n g lines o r over p l a n e s .
A p p l i c a t i o n s of the A F M to m a t e r i a l s science are
g r o w i n g very rapidly. It is well suited t o e x a m i n i n g
s m o o t h surfaces which c o n t a i n features o r defects less
t h a n 1 in size. O n surfaces which a r e atomically
s m o o t h , it is frequently possible t o observe a t o m
l o c a t i o n s . A t o m i c r e s o l u t i o n h a s been achieved for
m a t e r i a l s such as gold, N a C l , mica a n d T e S e 2 . Ledges,
g r o w t h steps a n d spiral features e m a n a t i n g from
screw dislocations h a v e been observed. Cleaved sur
faces of single crystals c a n be i m a g i n e d . O n a polished
a n d etched cross section of a m e t a l o r ceramic, grain
b o u n d a r i e s , precipitates, inclusions, voids a n d o t h e r
features a r e visible. Because the A F M h a s very g o o d
vertical r e s o l u t i o n , relief polishing will delineate
p h a s e s with even slight differences in a b r a s i o n resist
a n c e . Scratches a n d w e a r m a r k s h a v e been observed
a n d m e a s u r e d . P o l y m e r surfaces c a n be imaged,
a l t h o u g h very soft p h a s e s c a n interact with the tip to
p r o d u c e artifacts.
/.

Measurement

of Surface

Forces

W h e n the tip a n d specimen a r e s e p a r a t e d by a large

d i s t a n c e ( h u n d r e d s o r t h o u s a n d s of i n t e r a t o m i c spacings), the force exerted o n o n e by the o t h e r
a p p r o a c h e s z e r o . A s this distance is decreased, a n
a t t r a c t i v e force a p p e a r s , increasing in m a g n i t u d e with

23

Atomic

Force

Microscopy

decreasing distance. A t a few i n t e r a t o m i c spacings,

the attractive force reaches a m a x i m u m , t h e n d e
creases as the d i s t a n c e c o n t i n u e s t o decrease. It
reaches zero a n d c h a n g e s sign a t t h e e q u i l i b r i u m
p o s i t i o n a n d further decreases in d i s t a n c e a r e a c c o m
p a n i e d by a rapidly increasing repulsive force. T h e
n a t u r e of the attractive forces involved is the subject
of m u c h o n g o i n g research, a l t h o u g h they are
generally considered t o be of t h e v a n d e r W a a l s type.
A t zero force, t h e tip a n d specimen a r e c o n s i d e r e d t o
be in c o n t a c t in a n e q u i l i b r i u m configuration. If a
force is applied t o p u s h the tip i n t o t h e specimen
( p u s h i n g against t h e repulsive force), elastic d e f o r m a
tion of b o t h the tip a n d specimen will occur. H i g h
forces m a y cause plastic d e f o r m a t i o n , c r a c k i n g
or, possibly, transfer of m a t e r i a l b e t w e e n tip a n d
specimen.
In the vicinity of c o n t a c t , t h e force field reflects the
a t o m i c s t r u c t u r e o n each surface. A t o m i c resolution
h a s been achieved by s c a n n i n g a tip with o n e d o m i n
a n t a t o m over a relatively flat specimen, t h e r e b y
sensing the a t o m i c level v a r i a t i o n s in t h e force field of
the specimen.
T e c h n i q u e s for m e a s u r i n g very small forces h a v e
a d v a n c e d rapidly in recent years. T h e m o s t c o m m o n
is to use a silicon nitride cantilever b e a m , with a n
integral silicon nitride p y r i m i d a l tip, fabricated o n a
silicon wafer using m o d e r n m i c r o l i t h o g r a p h i c tech
niques. A silicon nitride cantilever 10 wide, 0.6
thick a n d 100 long h a s a force c o n s t a n t of
1
0.08 m " . D i s p l a c e m e n t s of 1 n m are easily
m e a s u r e d using laser reflection off t h e tip, laser interferometry, detection of tunnelling c u r r e n t s o r c a p a c i
tance probes.
U n d e r a m b i e n t c o n d i t i o n s , a thin liquidlike layer
will form o n m o s t surfaces a n d strongly influence t h e
i n t e r a c t i o n between tip a n d specimen. T h e tip c a n be
held in c o n t a c t with t h e specimen by the surface
tension. A t t h e p o i n t of c o n t a c t , with a film covering
b o t h t h e tip a n d specimen, t h e forces d u e t o surface
tension a r e of the o r d e r of 1 . A repulsive t i p specimen force b a l a n c e s the surface tension, so t h a t
the tip is a l m o s t always in the repulsive force m o d e
w h e n o p e r a t i n g in air. If the liquid molecules r e m a i n
between the tip a n d specimen, they c a n alter the force
field a n d affect the i m a g e features. L i q u i d cells a r e
used to totally i m m e r s e the tip a n d specimen in a
liquid, so t h a t the l i q u i d - a i r surface tension forces are
eliminated.

2. Scanning

the

Surface

M e c h a n i c a l s c a n n i n g is a c c o m p l i s h e d by using a
piezoelectric t r a n s d u c e r . If fabricated in t h e f o r m of a
hollow cylinder with o n e electrode o n t h e interior wall
a n d four s e p a r a t e electrodes o n each q u a d r a n t of t h e
exterior wall, m o t i o n in three d i m e n s i o n s c a n be
achieved. O n e e n d of t h e cylinder is fixed to t h e

24

Figure 1
Surface scanning: small vertical displacements of the
specimen surface will cause a deflection of the laser beam
as it reflects off the cantilever surface. Displacements less
than 1 nm can be detected in the A-B signal. If negative
feedback is used to couple the detector signal to the
displacement of the piezoscanner, then a greater range
in specimen height can be measured

m i c r o s c o p e b a s e a n d t h e specimen is m o u n t e d o n t h e
o p p o s i t e e n d . A voltage applied b e t w e e n t h e interior
electrode a n d all of t h e o u t e r electrodes will c a u s e a
d i m e n s i o n a l c h a n g e a l o n g t h e axis of t h e cylinder, o r
direction. P o t e n t i a l s applied b e t w e e n o p p o s i t e q u a d
r a n t s of the o u t e r electrodes will cause b e n d i n g of t h e
t u b e a n d s u b s e q u e n t deflection of t h e free e n d of t h e
t u b e in t h e o r y direction. Typical r a n g e s a r e 10
in a n d 100 in a n d y. F o r a t o m i c resolution,
a c t u a t o r s with smaller r a n g e s in a n d y a r e preferred,
b e c a u s e the scan m a y cover only a few n a n o m e t e r s .
A critical p r o c e d u r e in a c t u a l o p e r a t i o n is t h e
a p p r o a c h of t h e tip t o t h e specimen. W i t h the aid of a
light m i c r o s c o p e , t h e t i p - s p e c i m e n s e p a r a t i o n is
mechanically r e d u c e d t o a few m i c r o m e t e r s a n d t h e
specimen is t h e n a d v a n c e d using the p i e z o a c t u a t o r
m o t i o n until c o n t a c t is m a d e . In Fig. 1, t h e specimen
is in c o n t a c t with the tip in the repulsive force m o d e
a n d is held a t a p o s i t i o n w h e r e the reflected light from
t h e laser is evenly split b e t w e e n segments A a n d of
t h e position-sensitive d e t e c t o r . If the specimen is
t r a n s l a t e d so t h a t a higher region p u s h e s t h e c a n t i
lever slightly u p w a r d s , t h e n m o r e of the light will fall
o n d e t e c t o r A a n d the A - B signal will increase. T h u s ,
t h e d e t e c t o r o u t p u t signal is a m e a s u r e of specimen
height a n d c a n be sensitive t o d i s p l a c e m e n t s of less
than 1 nm.
W h i l e this d e t e c t o r a r r a n g e m e n t is very sensitive, it
h a s a r a n g e limited by t h e physical p r o p e r t i e s of t h e
cantilever as well as by t h e p h o t o d e t e c t o r . If t h e
circuit is switched t o a negative feedback m o d e , with a

Atomic

Force

Microscopy

Computer

Control
signal
output

Data
signal
input

Laser and
photodetector
Cantilever
Specimen
position

y scan

Piezotube
scanner

Figure 2
The essential components for computer control and data
collection in a surface force microscope

high-gain amplifier using the p h o t o d e t e c t o r o u t p u t t o

c o n t r o l t h e p i e z o a c t u a t o r , t h e n t h e d i s p l a c e m e n t of
the specimen will be such t h a t a c o n s t a n t a n d u n v a r y
ing deflection of t h e cantilever is achieved. D u r i n g a n
xy raster scan, t h e c o n t r o l voltage will b e directly
related t o t h e elevation c h a n g e s o n t h e surface of t h e
specimen a n d this signal c a n be used t o f o r m t h e
topographic image.
T h e essential c o m p o n e n t s of a surface force m i c r o
scope a r e illustrated in Fig. 2. T h e a n d y scan
g e n e r a t o r s p r o v i d e for t h e raster s c a n n i n g of t h e
specimen, with typical line scan rates of 0 . 1 - 4 0 H z
a n d 100-500 lines p e r frame. T h e elevation signal,
either directly from the p h o t o d e t e c t o r o r from t h e
feedback amplifier, is digitized a n d s t o r e d in c o m
p u t e r m e m o r y . A 256 x 256 pixel i m a g e with 12-bit
resolution will r e q u i r e a b o u t 100 k b y t e s of m e m o r y .

3. Images

Displaying

Qualitative

Information

T h e processing a n d p r e s e n t a t i o n of t h e t o p o g r a p h i c
i n f o r m a t i o n in t h e f o r m of a n i m a g e requires a
c o m p u t e r . A single line of d a t a c a n be p l o t t e d as
height vs distance, depicting t h e elevation a l o n g t h a t
line. Early i m a g e s were f o r m e d by p l o t t i n g all the
lines of d a t a with a slight vertical a n d h o r i z o n t a l
offset for successive lines, in o r d e r to give a c r u d e
t h r e e - d i m e n s i o n a l aspect t o the display. W i t h c o m
p u t e r s a n d m o n i t o r s c a p a b l e of displaying s h a d e s of
gray o r a m u l t i t u d e of c o l o r s , it is possible t o g e n e r a t e
m u c h better i m a g e s . T h e basic p r o b l e m is t o t a k e the
t h r e e - d i m e n s i o n a l i n f o r m a t i o n describing p o i n t s o n a
surface a n d project t h e m o n t o a t w o - d i m e n s i o n a l
p l a n e for viewing.
T h e t o p view, o r gray-scale i m a g e , is a n a l o g o u s t o a
t o p o g r a p h i c m a p , with a view l o o k i n g directly d o w n
o n t o the surface. F i g u r e 3 is t h e surface of a c o m p a c t
disk, w h e r e t h e m o l d e d d e p r e s s i o n s c o n t a i n i n g the

Figure 3
The surface topography of a compact disk obtained with
an AFM. The molded depressions used to digitally encode
the signal are clearly visible. The black regions can be
thought of as being at "sea level" and the gray level of
other regions represent their height above sea level. The
gray-level bar to the right of the image calibrates the
height scale

digitized a u d i o signal c a n be seen. T h e h o r i z o n t a l axis

is x, t h e vertical axis is y a n d the g r a y level represents
o r t h e surface height. H i g h e r p o i n t s are whiter, lower
p o i n t s a r e blacker. T h e g r a y scale is q u a n t i t a t i v e a n d
is displayed t o the right of the i m a g e . T h e black a r e a s
in a n i m a g e c a n b e t h o u g h t of as being a t " s e a level"
a n d t h e gray level associated with o t h e r p o i n t s indic
ates their " e l e v a t i o n a b o v e sea level." T h e m a x i m u m
value is s h o w n o n t o p of the scale b a r . T h e m a x i m u m
value of t h e gray scale c a n be c h a n g e d , which in t u r n
will c h a n g e the c o n t r a s t of t h e i m a g e , b u t it d o e s n o t
actually c h a n g e the q u a n t i t a t i v e height i n f o r m a t i o n .
T h e g r a y scale c a n be set t o o p t i m i z e the c o n t a s t in
each individual i m a g e , m a k i n g m o s t of t h e details
visible while m i n i m i z i n g regions of s a t u r a t e d black o r
white. Alternatively, it is easier t o c o m p a r e images if
they a r e displayed with t h e s a m e m a x i m u m gray-scale
values. O n a given specimen, wide-area scans will
frequently require a larger m a x i m u m gray-scale value
t h a n small-area scans. A scale b a r for is displayed
under the image.
Since t h e i m a g e d a t a a r e inherently threed i m e n s i o n a l , display c a n be as a t h r e e - d i m e n s i o n a l
r e n d i t i o n o r perspective view (see Fig. 4). C o m p u t e r
processing c a n display t h e r e n d e r e d i m a g e from a n y
angle a n d the height scale is frequently e x p a n d e d with
respect t o t h e lateral scales. T h i s h a s the effect of
magnifying surface features of interest, b u t it will also
d i s t o r t s h a p e s . A s h a p e which a p p e a r s as a s h a r p

25

Atomic

Force

Microscopy

Figure 4
The data used in Fig. 3 can also be displayed in a
three-dimensional rendered image. The shape of the
depressions can be clearly seen at the edge of the image

spike o n the surface m a y actually be n o t h i n g m o r e

t h a n a hemispherical m o u n d .
T h e i m a g e m a y also be e n h a n c e d a n d colored in
various ways. C u r v a t u r e , o r second-derivative, en
h a n c e m e n t m a y be a d d e d t o the gray-scale i m a g e to
clarify edges. S h a d o w s c a n be a d d e d as if the surface
were illuminated by a light source at a specified
location. T h e s e e n h a n c e m e n t s usually yield images
which the h u m a n b r a i n c a n m o r e quickly interpret
t h a n the top-view gray-scale images. C o l o r i n g c a n be
a d d e d which m a p s colors t o different elevations.
S o m e color p r i n t e r s used t o g e n e r a t e h a r d c o p y fail to
a d e q u a t e l y r e p r o d u c e a plain gray scale. A relatively
simple blue or gold height scale is frequently better.
Mixed colors c a n give s o m e very d r a m a t i c effects, b u t
m a y e n d u p c o m p l i c a t i n g i n t e r p r e t a t i o n of the i m a g e .

4. Extracting

Quantitative

Information

T h e d a t a a r e frequently s t o r e d digitally as a t w o d i m e n s i o n a l a r r a y of heights a b o v e a reference p l a n e .

T h e accuracy of c a l i b r a t i o n c a n limit the a c c u r a c y of
a n y q u a n t i t a t i v e i n f o r m a t i o n extracted from the d a t a
file. O n e c a l i b r a t i o n m e t h o d is t o scan a g r a t i n g o r
mesh which h a s a 1 periodicity in b o t h a n d y a n d
a peak-to-valley distance of 0.2 . A n a d e q u a t e
calibration is usually o b t a i n e d with three i n d e p e n d e n t
functions relating a d i s p l a c e m e n t to the c o n t r o l vol
tage applied to the c o r r e s p o n d i n g piezoelectrode:
=f[vX y = g(Vx), = h(V:). P o l y n o m i a l s a r e c o m
m o n l y used for the functions a n d inclusion of only the
first-order t e r m m a y be a d e q u a t e for s o m e applica
tions. F o r wide-area scans, h o w e v e r , second- a n d
t h i r d - o r d e r coefficients m a y be needed. C o r r e c t i o n for
barrel or p i n c u s h i o n d i s t o r t i o n a d d s complexity a n d ,
in general, will be a function of Vx9 VY a n d V:.
T h e simplest q u a n t i t a t i v e display is the height p r o
file, which s h o w s the elevation of the features a l o n g a

26

line. T h e line need n o t coincide with a n original scan

line, b u t c a n be a n a r b i t r a r y line o n the i m a g e .
C o m p u t e r s with a m o u s e for c u r s o r c o n t r o l p e r m i t
this selection t o b e easily carried o u t directly from a
displayed i m a g e a n d i n t e r p o l a t e d height values c a n be
c o m p u t e d as a p p r o p r i a t e . If the displayed vertical a n d
h o r i z o n t a l scales a r e significantly different, s h a p e s will
be d i s t o r t e d . M e a s u r e m e n t s of differences in surface
elevation, h o r i z o n t a l distance b e t w e e n p o i n t s , a n d
slopes are readily available features of m o s t i m a g e
processing p r o g r a m s .
T h e analysis of surface r o u g h n e s s c a n b e c a r r i e d
o u t a l o n g a line o r over a n a r e a selected with t h e aid of
a c u r s o r o n t h e display screen. T h e height d a t a a r e
least s q u a r e s fit t o a line o r p l a n e , as a p p r o p r i a t e , a n d
t h e d e v i a t i o n s of e a c h d a t a p o i n t from this reference
a r e c o m p u t e d . T h e r o u g h n e s s c a n b e expressed as
either a n r m s value o r a n a v e r a g e of a b s o l u t e values.
H e i g h t h i s t o g r a m s display the n u m b e r of d a t a
p o i n t s w h i c h fall within height intervals. T h e integral
curve of t h e h i s t o g r a m curve, s t a r t i n g with the highest
p o i n t a n d n o r m a l i z e d t o t h e t o t a l a r e a , gives the
b e a r i n g r a t i o . T h e s e p a r a m e t e r s a r e typically used in
studies of surface w e a r a n d friction.
T h e F o u r i e r t r a n s f o r m of the height profile is useful
for d e t e r m i n i n g t h e periodicity (spatial frequency) of
surface features. Similarly, the F o u r i e r t r a n s f o r m of
a n a r e a of t h e i m a g e will indicate t w o - d i m e n s i o n a l
periodicities a n d axes of s y m m e t r y . N o i s y images,
p a r t i c u l a r l y t a k e n at a t o m i c scales, c a n be F o u r i e r
t r a n s f o r m e d , filtered a n d s m o o t h e d , a n d t h e n inverse
F o u r i e r t r a n s f o r m e d t o yield a less noisy i m a g e which
still illustrates t h e d o m i n a n t features.

5.

Limitations

T h e surface force m i c r o s c o p e h a s a high sensitivity for

small c h a n g e s in vertical elevation, b u t this is a c c o m
p a n i e d by a limited vertical r a n g e . In practical t e r m s ,
t h e m i c r o s c o p e w o r k s best o n surfaces w h i c h a p p e a r
to be very s m o o t h w h e n e x a m i n e d with o t h e r tech
niques. S t r u c t u r e at a n a t o m i c level h a s been seen o n
several crystalline m a t e r i a l s using either the amplified
signal from t h e d e t e c t o r o r the feedback signal to the
piezoscanner. H o w e v e r , i m a g i n g a fracture interface
w h e r e height v a r i a t i o n s exceed 5 is generally n o t
possible.
T h e m a x i m u m field of view is also limited by the
lateral scan r a n g e of t h e p i e z o s c a n n e r . N e w e r piezodrivers h a v e b e e n d e v e l o p e d w h i c h p e r m i t scans u p t o
250 , b u t wider scans a r e usually a c c o m p a n i e d by
greater c u r v a t u r e d i s t o r t i o n s in the i m a g e . M e c h a n i
cal xy stages p e r m i t the c a n t i l e v e r - d e t e c t o r assembly
to be p o s i t i o n e d within a 5 m m s q u a r e a r e a , so t h a t
large a r e a s c a n be covered with adjoining multiple
images w h e n needed.
T h e s a m p l e size m u s t b e such t h a t it c a n b e
m o u n t e d o n t h e p i e z o s c a n n e r a n d fit between the

Atomic

scanner a n d the c a n t i l e v e r - d e t e c t o r assembly. A c o m

m o n s a m p l e size is a rectangle a b o u t 10 m m by 10 m m
a n d 1-2 m m thick. T h e limited r a n g e o n the piezoscanner also requires t h a t the surface of interest be
nearly parallel t o the scan p l a n e . P o r t i o n s of convex
surfaces m a y a d e q u a t e l y m e e t these r e q u i r e m e n t s ; t h e
surface s t r u c t u r e s of fibers a n d ball b e a r i n g s h a v e
been successfully i m a g e d . C o n c a v e surfaces m a y h a v e
insufficient clearance for t h e edge of t h e cantilever
assembly as the tip a p p r o a c h e s the specimen surface.
T h e s h a p e a n d d i m e n s i o n s of the p y r a m i d a l tip o n
the cantilever will influence h o w well it t r a c k s surface
features. If t h e p o i n t of c o n t a c t with the specimen
surface shifts t o the sides of t h e p y r a m i d , t h e edges of
the p y r a m i d o r t h e u n d e r s i d e of the cantilever, t h e n
the i m a g e represents a c o m b i n a t i o n of several effects
a n d is p r o b a b l y r e n d e r e d u n i n t e r p r e t a b l e . F o r ex
a m p l e , a surface c r a c k 1 wide a n d several m i c r o
meters d e e p will a p p e a r t o h a v e walls with t h e s a m e
slope as the sides (or edges) of t h e p y r a m i d a n d a
d e p t h limited by t h e p e n e t r a t i o n of the p y r a m i d i n t o
the crack. T e c h n i q u e s are being d e v e l o p e d for the
fabrication of tips with high l e n g t h - t o - d i a m e t e r
ratios.
It s h o u l d be n o t e d t h a t the i m a g e is actually a
c o n v o l u t i o n of the tip s h a p e with the surface s h a p e .
M o s t tips h a v e a r a d i u s of c u r v a t u r e of a b o u t 30 n m
at the apex of the p y r a m i d a n d this is a d e q u a t e l y small
for the vast m a j o r i t y of a p p l i c a t i o n s . H o w e v e r ,
extended use of a tip c a n w e a r a flat region o n it, so
t h a t a n i m a g e m a y reveal n u m e r o u s s q u a r e features
the s a m e size as the flat. It is also possible t o transfer
material from the specimen t o the tip, t h e r e b y modify
ing its s h a p e . A n o t h e r defect occasionally seen o n new
tips is multiple asperities, which give rise t o d o u b l e
images, o r g h o s t images.
F r i c t i o n a l forces b e t w e e n t h e tip a n d specimen a r e
usually considered t o be negligible, because the a p
plied n o r m a l force is very low t o begin with. H o w e v e r ,
s o m e m a t e r i a l s , such as p o l y m e r s , c a n exhibit local
ized a n d m o m e n t a r y a d h e s i o n . T h e tip will give t h e
a p p e a r a n c e of sticking a t the b e g i n n i n g of a line scan,
then b r e a k i n g loose a n d t r a c k i n g n o r m a l l y .
T h e force b e t w e e n the tip a n d t h e specimen c a n be
altered by electrostatic forces or capillary forces. In
the case of n o n c o n d u c t i v e samples in a d r y e n v i r o n
m e n t , a c c u m u l a t e d electrostatic c h a r g e s c a n g e n e r a t e
forces m u c h larger t h a n expected. U n d e r c o n d i t i o n s
of n o r m a l o r high relative h u m i d i t y , a n a d s o r b e d
layer of w a t e r o n the surface c a n rise u p a r o u n d the
p y r a m i d tip a n d t h e a d d e d force d u e t o surface
tension t e n d s to h o l d the tip o n t o t h e specimen
surface. In general, the surface force m i c r o s c o p e is n o t
the best i n s t r u m e n t t o q u a n t i t a t i v e l y m e a s u r e surface
forces, b u t simple a n d c o m p a r a t i v e m e a s u r e m e n t s c a n
be m a d e if u n u s u a l forces seem t o be affecting a n
image.

6. Applications

to Materials

Force

Science

Microscopy

and

Engineering
A p p l i c a t i o n s of the A F M a r e rapidly g r o w i n g in the
field of m a t e r i a l s science a n d engineering. A t the
a t o m i c level, it is useful for o b s e r v i n g surface v a c a n
cies, s u b s t i t u t i o n a l impurities a n d a d a t o m s . T h e re
c o n s t r u c t i o n of clean surfaces, a n d c h a n g e s o c c u r r i n g
d u r i n g a d s o r p t i o n , c a n be studied. W i t h liquid o r
electrochemical cells, r e a c t i o n s at the solid-liquid
interface c a n be followed in detail. I m a g e s for these
a p p l i c a t i o n s a r e t a k e n a t very high magnifications,
typically a r o u n d 20 000 000.
3
6
A t lower magnifications ( 10 to 10 ) the c a p a
bility of the A F M for q u a n t i t a t i v e t o p o g r a p h i c
m e a s u r e m e n t s c o m p l e m e n t s the capabilities of o t h e r
microscopies very well. F o r e x a m p l e , a light m i c r o
scope e q u i p p e d for N o r m a r s k i differential interfer
ence c o n t r a s t is highly sensitive for detecting small
c h a n g e s in surface elevation (a few n a n o m e t e r s ) .
H o w e v e r , lateral r e s o l u t i o n is limited by the wave
length of light t o several h u n d r e d n a n o m e t e r s a n d
differences in height c a n n o t be m e a s u r e d q u a n t i t a t i
vely. If it is first used t o rapidly e x a m i n e a specimen in
o r d e r t o identify a n d locate features of interest, then
the specimen c a n be transferred t o a n A F M for m o r e
detailed a n d q u a n t i t a t i v e m e a s u r e m e n t s of the
features.
A metallurgical a p p l i c a t i o n is the e x a m i n a t i o n of
the surface of a polished ball b e a r i n g . T h e d i a m e t e r is
a b o u t 5 m m , so t h a t surface c u r v a t u r e limits the use of
a n optical m i c r o s c o p e . T h e S E M c a n i m a g e p h a s e s in
the m i c r o s t r u c t u r e as well as use energy dispersive
analysis to m e a s u r e their chemical c o m p o s i t i o n , b u t
its large d e p t h of field p r o v i d e s relatively p o o r d e p t h
p e r c e p t i o n . T h e A F M c a n a d e q u a t e l y c o m p e n s a t e for
the c u r v a t u r e w h e n used in the feedback m o d e a n d
gives a d d i t i o n a l i n f o r m a t i o n a b o u t surface finish.
F i g u r e 5 illustrates the surface of a ball b e a r i n g , with
the i m a g e processed to r e m o v e surface c u r v a t u r e . T h e
surface is quite s m o o t h , with a m e a s u r e d r m s r o u g h
ness of 12 n m . T h e lighter s h a d e of t h e M 6 C carbides
indicates relief polishing; because they are h a r d e r t h a n
t h e s u r r o u n d i n g steel m a t r i x , they polish less rapidly
a n d p r o t r u d e a b o v e the surface by a b o u t 20 n m .
T h e surfaces of m e t a l s a n d alloys a r e frequently
etched to reveal m i c r o s t r u c t u r e w h e n using light
m i c r o s c o p y . T h e precipitate size in m a n y m o d e r n
alloys is s u b m i c r o m e t e r , r e q u i r i n g magnifications
higher t h a n t h o s e achievable in the light m i c r o s c o p e .
T h e etched surface of a nickel-base superalloy (N-18)
is s h o w n in Fig. 6. T h e m a t r i x h a s been etched t o
r e m o v e a b o u t 30 n m , leaving t h e y particles s t a n d i n g
in relief.
In general, fracture surfaces a r e t o o irregular t o be
i m a g e d with the A F M . H o w e v e r , brittle m a t e r i a l s
m a y cleave a l o n g well-defined
crystallographic
p l a n e s , giving a suitable surface. E x a m i n a t i o n of a
cleaved surface of calcite d e m o n s t r a t e s t h a t the c r a c k

27

Atomic

Force

Microscopy

T h e surface of a synthetic d i a m o n d h a s been success

fully e x a m i n e d .
T h e surfaces of p o l y m e r s e x a m i n e d using a n S E M
are typically c o a t e d with a c o n d u c t i v e film, o r low
b e a m energies are used, t o avoid c h a r g i n g . T h e A F M
c a n i m a g e these surfaces directly, as well as giving
quantitative topographic information.
S p u t t e r e d films, such as are used for c o a t i n g S E M
specimens, h a v e their o w n t o p o g r a p h i c characteristics
w h i c h s h o u l d b e considered. T h e surface r o u g h n e s s of
a gold film, deposited o n a s m o o t h silicon wafer,
m e a s u r e s a b o u t 15 n m p e a k t o valley, indicating t h a t
the overall surface texture of the film c a n be expected
t o o b s c u r e u n d e r l y i n g specimen features less t h a n
20 n m in size.

7. Future
Figure 5
Surface of a ball bearing made from tool steel. The
surface has been flattened electronically to remove the
curvature. The large particles are M 6C carbides which rise
about 20 nm above the surrounding matrix. The average
rms surface roughness is 12nm

front occasionally j u m p s t o different elevations o n

adjoining regions, giving rise to small steps.
Surface s t r u c t u r e formed d u r i n g t h e g r o w t h of
single crystals is useful in s t u d y i n g g r o w t h processes.

Developments

A F M s a r e developing very rapidly a n d significant

a d v a n c e s c a n be expected in the n e a r future. A l t h o u g h
the A F M evolved from the S T M , t h e A F M is likely t o
find a m u c h b r o a d e r r a n g e of a p p l i c a t i o n s in m a t e r i a l s
science a n d engineering. S h a r p e r tips which will be
able to t r a c k steeper walls are being developed.
I m p r o v e d feedback systems will be better able t o
r e s p o n d to r a p i d c h a n g e s in surface elevation. A
variety of electrochemical techniques are a p p e a r i n g
for s t u d y i n g reactions u n d e r p o t e n t i a l c o n t r o l at
s o l i d - l i q u i d interfaces.
See also: Mechanical Properties Microprobe; Scanning
Electron Microscopy; Scanning Tunnelling Microscopy
and Spectroscopy

Bibliography
Altshuler L 1991 Atomic-scale materials characterization.
Adv. Mater. Process. 140(3): 18
Binnig G, Quate C F, Gerber Ch 1986 Atomic force
microscope. Phys. Rev. Lett. 56: 930-3
Journal of Vacuum Science and Technology 9(2) 1991 Pro
ceedings of the Fifth International Conference on Scan
ning Tunnelling Microscopy/Spectroscopy
Sarid D 1991 Scanning Force Microscopy with Applications
to Electric, Magnetic and Atomic Forces. Oxford Univer
sity Press, New York
W. G. Morris
[General Electric C o r p o r a t e R e s e a r c h
a n d D e v e l o p m e n t , Schenectady,
New York, USA]

Figure 6
Etched surface of a nickel-base superalloy. The etchant
has preferentially attacked the matrix, leaving ' particles
clearly visible

28

Auger Electron Spectroscopy

In A u g e r electron s p e c t r o s c o p y ( A E S ) a n electron
b e a m is used t o excite the electronic states of the

Auger

surface a t o m s of a solid. W h e n t h e a t o m s d e c a y from

the excited electronic state, A u g e r electrons a r e emit
ted c a r r y i n g b a n d s t r u c t u r e i n f o r m a t i o n which m a k e s
it possible t o d e t e r m i n e the c h e m i s t r y of the surface.
T h e c o m b i n e d excitation a n d d e c a y processes a r e
s h o w n schematically in Fig. 1 for a n element exhibit
ing a K-level t r a n s i t i o n . T o p e r f o r m the chemical
identification t h e A u g e r electrons a r e energy a n a
lyzed. T h e e m i t t e d A u g e r electron h a s a n energy
associated with the b a n d s t r u c t u r e of the a t o m in t h e
solid e m i t t i n g t h e electron; this A u g e r energy, K L L, is
i n d e p e n d e n t of t h e energy of t h e incident electron
b e a m . It w a s this i n d e p e n d e n c e of t h e incident excita
tion energy t h a t led t o its discovery by A u g e r (1925)
d u r i n g c l o u d - c h a m b e r e x p e r i m e n t s : t h e t r a c k lengths
associated with t h e A u g e r electrons were f o u n d t o be
i n d e p e n d e n t of incident particle energy. T h e A u g e r
process c a n also be s t i m u l a t e d with p h o t o n s (electron
spectroscopy for chemical analysis, E S C A ) o r ions,
b u t electron excitation is presently used for d e d i c a t e d
Auger spectrometers.

1. Probability

of an Auger

Decay

Process

T h e energy released by t h e electron d e c a y i n g from t h e

L shell to t h e shell c a n either be e m i t t e d as a p h o t o n
(x ray) or a n A u g e r electron (Fig. 1). T h e p r o b a b i l i t i e s
for the t w o t r a n s i t i o n s a r e discussed by B a m b y n e k et
al. (1972). T h e m o s t i m p o r t a n t fact is t h a t , for the
A u g e r electron kinetic energies of interest in A E S ( 0 -

shell
electron

Spectroscopy

Figure 2
X-ray yield as a function of atomic number

2500 eV, c o r r e s p o n d i n g t o a t o m i c n u m b e r < 15), as

defined by t h e escape d e p t h (see Sect. 2), the d o m i n a n t
d e c a y p r o c e s s is the emission of A u g e r electrons. This
is s h o w n schematically in Fig. 2 for t h e vacancy
w h e r e WK +
AK=\, with WK a n d AK being the
p r o b a b i l i t i e s of x-ray a n d A u g e r electron emissions,
respectively.
W h e n the energy of the EKLL A u g e r electron is
g r e a t e r t h a n the energy of interest for A E S , the
energies of t h e higher-level t r a n s i t i o n s ( L M M , M N N ,
N O O ) a r e m e a s u r e d . F i g u r e 3 s h o w s the energy of the
A u g e r electron as a function of a t o m i c n u m b e r . T h e
systematic r e l a t i o n s h i p b e t w e e n t h e energy a n d the
a t o m i c n u m b e r s within a given t y p e of t r a n s i t i o n is
readily a p p a r e n t .

Auger
electron

2. Escape

\
v.

Primary
electron

Electron

\
\

Figure 1
Schematic showing the competitive processes of x-ray and
Auger electron emission. The measured energy of the
emitted Auger electron is given by EKLL = EK(Z) - EL
( + ) - , where is the atomic number, EK(Z) is
the binding energy of the K-level electron, EL(Z) is the
binding energy of the L-level electron, E(Z + ) is
the binding energy of the L-level electron in the singly
ionized atom ( is a correction factor to account for the
ionized state of the atom and is approximately 0.5-0.75),
and is the work function of the analyzer

Depth

T h e factor t h a t is m o s t i m p o r t a n t in A E S , a n d which
m a k e s it a n i m p o r t a n t e x p e r i m e n t a l m e t h o d for sur
face c h a r a c t e r i z a t i o n , is t h e escape d e p t h of the
A u g e r electrons from the solid. T h e escape d e p t h is
the characteristic distance below the surface from
which the A u g e r electron c a n reach the surface with
o u t h a v i n g a n inelastic i n t e r a c t i o n with the m a t r i x .
F i g u r e 4 s h o w s the escape d e p t h as a function of the
electron kinetic energy. F o r 2 0 - 1 0 0 0 eV electrons the
escape d e p t h is less t h a n 2.0 n m , falling as low as
a b o u t 0.5 n m in t h e 5 0 - 2 0 0 eV energy r a n g e . T h e
escape d e p t h is defined as t h e distance from the
surface t h a t t h e electron c a n originate at a n d still h a v e
a p r o b a b i l i t y of 1/e (i.e., 0.37) of escaping w i t h o u t a n
inelastic i n t e r a c t i o n with the m a t r i x . T h e n u m b e r of
A u g e r electrons TV t h a t reach t h e surface from a d e p t h
below the surface w h e r e N0 electrons originate is
z/S
given by = N0e~ . T h i s s h o w s t h a t the majority of
the A u g e r electrons o r i g i n a t e m u c h closer t o the
surface t h a n the characteristic escape d e p t h , a n d t h a t
a large n u m b e r also o r i g i n a t e below the escape d e p t h .
A c o m p a r i s o n b e t w e e n A E S a n d electron m i c r o p r o b e

29

Auger

Electron

Spectroscopy

Pi

Th

Ac ,U

Fr

A l Rn

Po

Bi

m.
Tl
|H
Au
lr

Pi

0*

""Mi
T. "
Hf
Lu
Yh
Tm
im
Ho
M
n
Tb
Gd
Eu
m

VINTVI

$
""

Pr

La

Cs
P

Ce

Bi
X.
T*

"
A9

Rh
Tc

Pri
Ru

M
Nh
l
Y 7r

Sc
r
Rh

Vli
I

MM

Br

Kr

Se

As

P..
Lu

2n
Ni
Fe
r

Mil
v

;
'
a C

U ftr
PI
c

VI 1
-r\LL-

*S

'

Ma
a
F

N
"

L
li

0
r

R.
"

' Urn

U
-H

Electron energy (eV)

Figure 3
Characteristic Auger electron energies: dots indicate the electron energies of the principal Auger peaks for each element;
large dots represent predominant peaks for each element

Ag

Au

Mo

SocE^

Ag

Fe
Ag

Mo

W
-

^.

Ag

Mo

analysis, in which characteristic rays c a r r y t h e b a n d

s t r u c t u r e a n d chemical i n f o r m a t i o n , s h o w s t h a t t h e
d e p t h e x a m i n e d with t h e m i c r o p r o b e ( ~ 0 . 5
characteristic x-ray electron escape d e p t h ) is a b o u t
500 times t h a t of A E S ( ~ 1 n m ) . T h i s clearly shows
the a d v a n t a g e s of A E S in m a k i n g m e a s u r e m e n t s
w h e r e local surface chemistries vary from t h e b u l k
chemistry.

Ag

3. Auger
Electron energy (eV)

Figure 4
Escape depth as a function of the Auger electron energy

30

Signal

M a n y factors a r e involved in d e t e r m i n i n g t h e A u g e r
c u r r e n t from a given t r a n s i t i o n . F o r t h e /th t r a n s i t i o n
the A u g e r c u r r e n t /, c a n be given b y

Auger

Electron

Spectroscopy

> hjlnAt ~ 6 e V w h i c h is a p p r o x i m a t e l y the n a t u

ral A u g e r line w i d t h . A d d i t i o n a l line b r o a d e n i n g
results from t h e w i d t h of t h e o u t e r o r valence b a n d s ,
from c o m p l i c a t e d b a n d s t r u c t u r e , a n d from instru
m e n t a l b r o a d e n i n g which o c c u r s because of the c o n
v o l u t i o n of the i n s t r u m e n t function a n d the n a t u r a l
line s h a p e .
broadening
W h e n A i n s t r u mt e>n , i n s t r u m e n t a l
o c c u r s , b u t w h e n A i n s t r u mt e <n , the effect o n p e a k
w i d t h by t h e i n s t r u m e n t is small.

Figure 5
Schematic of ionization cross section (arbitrary units) as a
function of the ratio of the primary energy to the
ionization energy

/, =

^^^

(1)

where A is t h e surface a r e a i r r a d i a t e d ; Ip is the

incident c u r r e n t density; Xi is t h e c o n c e n t r a t i o n of
element / in t h e i r r a d i a t e d v o l u m e ; is t h e a t o m i c
density; is t h e escape d e p t h ( m e a n free p a t h ) ; is the
b a c k s c a t t e r i n g factor ( > 1); is t h e i o n i z a t i o n cross
section; , is t h e A u g e r t r a n s i t i o n p r o b a b i l i t y ; R is a
surface r o u g h n e s s factor; a n d is t h e i n s t r u m e n t
t r a n s m i s s i o n . T h e s e factors a r e n o t necessarily inde
pendent.

4. Ionization

and Backscattering

Cross

Sections

T h e i o n i z a t i o n cross section is s h o w n schematically

in Fig. 5. T h e incident energy E0 of t h e electron m u s t
be at least e q u a l t o t h e i o n i z a t i o n energy Ew t o create a
hole in the w b a n d (where w = K , L, , N , . . .). T h e
cross section increases u p to a n incident electron
energy of a b o u t three times t h e i o n i z a t i o n energy a n d
slowly falls off after a b o u t six t o eight times the
ionization energy. T h e slow falloff in cross section
with increasing incident energy is influenced by t h e
backscattered
electrons.
These
electrons
also
influence t h e spatial r e s o l u t i o n of the electron b e a m
since they diverge as they exit t h e specimen. T h i s
enlarges the region of surface t h a t is a n a l y z e d . In
a d d i t i o n , the b a c k s c a t t e r i n g factor will v a r y with
the s u b s t r a t e : h i g h - Z elements will b a c k s c a t t e r a
larger fraction of t h e incident electrons. T h i s leads t o
modification of t h e signal intensity in thin layered
structures.

5. Auger

Peak

6. Measurement

of Auger

Electron

Energy

T h e r e a r e several m e t h o d s used t o energy analyze the

A u g e r electron. T h e y are: (a) a retarding-grid system,
often used in c o n j u n c t i o n with low-energy electron
diffraction ( L E E D ) ; a n d (b) velocity analyzers, which
include 2 7 0 sectors, cylindrical m i r r o r analyzers
( C M A s ) a n d spherical analyzers. T h e C M A is the
m o s t c o m m o n l y used electron energy analyzer. F i g u r e
6 is a s c h e m a t i c of a C M A s h o w i n g t h e o r i e n t a t i o n of
t h e s a m p l e relative t o the a n a l y z e r a n d t h e scanning
electron g u n coaxial with t h e C M A . T h e focused
s c a n n i n g electron b e a m leads t o a useful spatial
resolution of A E S of a b o u t 200 n m . T h i s allows
localized chemical surface analysis. T h e voltage Vm
applied t o the o u t e r cylinder selectively b e n d s the
electrons t o be c o u n t e d o n the electron multiplier.
R a m p i n g the voltage sweeps the electron energy a n a
lyzed a c r o s s the energies of interest in A E S . T h e
c u r r e n t m e a s u r e m e n t is directly p r o p o r t i o n a l t o the
electron energy d i s t r i b u t i o n N(E). S u p e r i m p o s i n g a
high-frequency l o w - a m p l i t u d e signal o n the r a m p i n g
v o l t a g e a n d electronically locking in o n t h a t fre
q u e n c y to select t h a t F o u r i e r c o m p o n e n t of the a n a
lyzed electron signal gives a c u r r e n t t h a t is related t o
dN(E)/dE.
T h i s t e c h n i q u e , d e v e l o p e d by H a r r i s
(1968), strongly e n h a n c e s t h e signal-to-noise r a t i o of
t h e A u g e r s p e c t r u m . N(E) a n d the c o r r e s p o n d i n g
dN(E)/dE a r e s h o w n in Fig. 7 for t h e M N N A E S
p e a k s of silver.

Exit s l i t
: =

^ - ( I n n e r cylinder)

C M A symmetry
axis \
Scanning

Specimen\ -n/f
C M A / v >
focal'
point

electron gun

Electron
multiplier
Exit
aperture

Widths

T h e H e i s e n b e r g u n c e r t a i n t y principle c a n
be
expressed as AEAt ^ h/2n, w h e r e h is P l a n c k ' s c o n
1 5
1 6
stant ( ~ 4 x l ( T e V s ) a n d At^z^ ( ~ 1 0 ~ S ) is t h e
half-life of t h e initial i o n i z a t i o n state. T h e r e f o r e ,

Cathode

Vm (Outer cylinder)

Figure 6
Schematic of a cylindrical mirror analyzer

31

Auger

Electron

Spectroscopy

200

400

600

E0

800

1000

(eV)

Figure 7
AES spectrum of silver: (a) derivative mode, (b) energy
distribution mode

7. Chemical

Effects

in

to analyze these near-surface regions, M a r c u s a n d

P a l m b e r g (1969) c o m b i n e d inert-ion s p u t t e r i n g with
A E S . T h i s e n a b l e d the chemical profiles n o r m a l t o the
surface of interest t o be d e t e r m i n e d a n d is s t a n d a r d
practice in A E S . C o m b i n e d A E S a n d inert-ion s p u t
tering h a s been used to s h o w the localized n a t u r e of
surface a n d interface e q u i l i b r i u m segregation as well
as t o analyze m o r e diffuse chemical d i s t r i b u t i o n s . T h e
e x p e r i m e n t a l a p p r o a c h is to b o m b a r d the surface with
a n ionized gas, usually a r g o n , in the kinetic energy
r a n g e 5 0 0 - 5 0 0 0 eV. T h e s p u t t e r e d surface is c o n
t i n u o u s l y o r " i n t e r m i t t e n t l y " analyzed with A E S . In
s o m e systems, s e c o n d a r y - i o n m a s s s p e c t r o s c o p y
( S I M S ) (see Secondary-Ion
Mass Spectrometry)
may
be carried o u t s i m u l t a n e o u s l y with the A E S analysis
to give c o m p l e m e n t a r y i n f o r m a t i o n .
I o n s p u t t e r i n g c a n i n t r o d u c e artifacts i n t o t h e sur
face region a n d the p o t e n t i a l for such artifacts m u s t
be carefully c o n s i d e r e d in a n y m e a s u r e m e n t . Preferen
tial s p u t t e r i n g of o n e a t o m species over a n o t h e r , in
p a r t i c u l a r a t low ion voltage, occurs very often,
p r o d u c i n g artificial chemical profiles. T h e ion b e a m
d o e s s t r u c t u r a l d a m a g e to t h e surface, c h a n g i n g the
local chemical b o n d i n g . F o r e x a m p l e , carbides from
free g r a p h i t e h a v e been f o r m e d u n d e r the influence of
the inert-ion b e a m .

AES

T h e integrated A u g e r p e a k s give direct i n f o r m a t i o n

a b o u t h o w m u c h of each element is p r e s e n t in the
v o l u m e analyzed. In a d d i t i o n , t h e A u g e r p e a k s h a p e s
a n d locations c a r r y i n f o r m a t i o n a b o u t the chemical
state of the a t o m s (see Chemical Analysis of Solid
Surfaces). F i g u r e 8 shows the dN(E)/dE p e a k s h a p e s
for c a r b o n , in g r a p h i t e form a n d in A 1 4C 3. Similar
peak s h a p e c h a n g e s a r e seen for oxides, sulfides,
borides a n d m a n y o t h e r b o n d i n g states of t h e a t o m s .

8. Quantitative

Auger

Analysis

T h e simplest form of q u a n t i t a t i v e A E S is t o use p e a k

heights for elemental s t a n d a r d s u n d e r the s a m e oper
ating c o n d i t i o n s ; this gives a r e a s o n a b l e m e a s u r e of
each element present. T h e second m e t h o d is to use
s t a n d a r d s of the a p p r o x i m a t e chemistry expected; the
difficulty is in p r e p a r i n g a s t a n d a r d surface chemistry
even if the bulk chemistry is defined. O t h e r p r o b l e m s
in q u a n t i t a t i v e A E S are related to the presence of thin
layered structures a n d the i n t e r a c t i o n between layers.
200

9. AES

Depth

Profiling

M u c h of the i n f o r m a t i o n of interest in A E S studies is

n o t only a t t h e surface b u t is present in thin layered
regions in the near-surface region. T o m a k e it possible

32

250
Electron energy (eV)

Figure 8
Characteristic carbon peaks for (a) carbide and
(b) graphite

Auger

A n o t h e r m a j o r p r o b l e m with inert-ion s p u t t e r i n g is
the very difficult task of q u a n t i f y i n g the d e p t h s p u t
tered. S t a n d a r d s p u t t e r i n g rates for h o m o g e n e o u s
materials c a n be m e a s u r e d b u t m a y n o t be directly
related t o s p u t t e r i n g of sequential thin layer s t r u c
tures. A great deal of a d d i t i o n a l effort is r e q u i r e d in
this a r e a of m e a s u r a b l e inert-ion s p u t t e r i n g rates. T o
o v e r c o m e edge effects associated with the i o n - b e a m
shape, the ion b e a m is rastered a n d A E S is p e r f o r m e d
only in the m i d d l e , uniformly s p u t t e r e d area.

10.

Vacuum Requirements

for

of

Spectroscopy

^ S on AISI 5140
S on Fe-0.6 Sb
on AISI 5140
0 Sb on AISI 3 3 4 0
* S b on Fe-2.2 Sb
Sb on Fe - 0.6 Sb
PonFe-Ni-Cr-C-P
Sn on F e - N i - C r - C -

AES

T h e e x t r e m e surface sensitivity of A E S m a k e s it a
m a n d a t o r y r e q u i r e m e n t t h a t in o r d e r t o get g o o d
i n f o r m a t i o n t h e surface m u s t be k e p t clean. T h i s is
particularly t r u e for the case of very thin layers of
m a t e r i a l . F o r this r e a s o n A E S m u s t be d o n e in a
v a c u u m system with a very low p a r t i a l p r e s s u r e of
active gases, in p a r t i c u l a r H 2 0 . T o h a v e m i n i m a l
interference with t h e electron optics, a v a c u u m of
2
better t h a n 10 P a is r e q u i r e d . If the p r i m a r y consti
t u e n t s of the v a c u u m a r e inert gases a n d the p a r t i a l
pressure of the active gases in t h e c h a m b e r is below
7
10~ P a , t h e n clean surfaces c a n be m a i n t a i n e d d u r i n g
the m e a s u r e m e n t time. It s h o u l d be n o t e d t h a t a n
active gas with a sticking coefficient of u n i t y will cover
the surface with a m o n o l a y e r for ~ 1 s e x p o s u r e at
4
10 Pa.
Therefore, there is a need for high v a c u u m with
m i n i m a l active gases. T o o b t a i n this, all-metal systems
are preferred. In certain cases, limited a m o u n t s of
l o w - v a p o r - p r e s s u r e n o n m e t a l l i c O-ring seals c a n be
used. G o o d v a c u u m p r a c t i c e m u s t be followed t o
avoid virtual leaks in t h e system.
T o o b t a i n the v a c u u m , m o s t systems avoid oil
p u m p i n g systems b u t use a c o m b i n a t i o n of zeolites o r p t i o n p u m p s t o r o u g h p u m p t h e system a n d ion
p u m p s c o m b i n e d with t i t a n i u m s u b l i m a t i o n p u m p s t o
o b t a i n the best u l t i m a t e pressure. W h e r e quick t u r n
a r o u n d time is r e q u i r e d , heavily t r a p p e d t u r b o m o l ecular p u m p s a r e c o m i n g i n t o usage.
It s h o u l d be n o t e d t h a t the n a t u r e of t h e surface will
have a significant influence o n h o w g o o d a v a c u u m is
required. F o r s e m i c o n d u c t o r a n d oxide m a t e r i a l s t h e
r e q u i r e m e n t s a r e m u c h less stringent t h a n for clean
surface active m e t a l s , such as a l u m i n u m , t i t a n i u m a n d
iron. F o r t h e surface-active m a t e r i a l s , it is a d v i s a b l e
to p r e b a k e t h e system a t a b o u t 200 C t o d e s o r b t h e
w a t e r v a p o r from t h e walls of t h e c h a m b e r . T h e
b a k i n g greatly reduces t h e relative p a r t i a l p r e s s u r e of
w a t e r v a p o r p r e s e n t a n d lowers t h e a b s o l u t e p r e s s u r e
_ 8
of the system t o t h e low 1 0 P a r a n g e .

11. Applications

Electron

AES

T h e interest in A E S is very w i d e s p r e a d a c r o s s the

scientific a n d engineering disciplines. M a n y of the

z (nm)
Figure 9
Sputter profile from intergranular fracture surfaces of
steel: C(z) is the concentration of the element at a depth
below the surface; C(0) is the concentration at the surface,
C" is the concentration in the bulk material

m a j o r uses of m a t e r i a l s a r e c o n t r o l l e d by surface o r
interface p r o p e r t i e s as well as by thin layered struc
tures. In m e t a l l u r g y , the a r e a s of fracture a n d fatigue,
w h e r e new surfaces a r e created, bulk a n d grainb o u n d a r y diffusion, c o a t i n g s , a d h e s i o n , surface p r e p
arations, hydrogen embrittlement,
solidification,
p o w d e r m e t a l l u r g y , c o m p o s i t e s , diffusion b o n d i n g
a n d o t h e r s all h a v e p r o b l e m s related to surfaces a n d
interfaces a n d h a v e gained insights from A E S studies.
A p r o m i n e n t e x a m p l e of this h a s been the extensive
studies o n g r a i n - b o u n d a r y a n d interface fracture in
steels; Fig. 9 is a n inert-ion s p u t t e r i n g profile s h o w i n g
t h e local n a t u r e of g r a i n - b o u n d a r y segregation associ
a t e d with e q u i l i b r i u m segregation.
Similar types of results a r e o b t a i n e d in s e m i c o n d u c
t o r studies. T h e thin layered s t r u c t u r e s of high-devicedensity M O S m a t e r i a l s lead t o t h e r e q u i r e m e n t of
A E S as a q u a l i t y - c o n t r o l system. Localized elements
t h a t influence the electrical p r o p e r t i e s of the materials
c a n be identified using t h e surface-sensitive A E S . A n
e x a m p l e of a s e m i c o n d u c t o r layered s t r u c t u r e is given
in Fig. 10.
A n o t h e r a r e a w h e r e A E S is a d y n a m i c p r o b e is the
s t u d y of catalytic b e h a v i o r of m a t e r i a l s . In this case

33

Auger

Electron

Spectroscopy

See also: Auger Microscopy, Angular Distribution; Chem

ical Analysis of Solid Surfaces; Depth Profiling; Electron
Spectroscopy for Chemical Analysis

Bibliography

10
15
20
25
30
Sputtering t i m e ( m i n )

35

Figure 10
Sputter profile through a semiconductor layered structure

m o s t of the catalytic p r o p e r t i e s are established by the

surface chemistry a n d b o n d i n g . A E S chemical a n d
b o n d i n g i n f o r m a t i o n h a s p r o v e d extremely v a l u a b l e
in o b t a i n i n g u n d e r s t a n d i n g of the catalytic b e h a v i o r
a n d in leading t h e w a y to i m p r o v e the catalysts.
A n o t h e r a r e a w h e r e A E S h a s been applied is in
lubrication, friction a n d wear, a n d the general a r e a of
tribology. A E S h a s identified the transfer a n d residual
films associated with these processes.
C e r a m i c s h a v e also been studied in s o m e detail.
B o t h interface chemistry a n d its relation t o densification as well as surface segregation h a v e been evalu
ated. F i g u r e 11 shows a d e p t h profile from a surface
2+
of M g O . T h e profiles s h o w t h a t the segregated C a
3+
ions are very n e a r the surface b u t S c ions are m o r e
diffusely distributed because of the need for c h a r g e
neutrality in the bulk.

Distance from surface

Figure 11
2+
Sputter
profile of segregation to free surface of C a and
3+
Sc in MgO

34

Auger 1925 Sur 1'effet photoelectrique compose. J. Phys.

Radium 6: 205-6
Bambynek W, Crasemann B, Fink R W, Freund H - U ,
Mark H, Swift C D, Price R E, Rao V 1972 X-ray
fluorescence yields, Auger, and Coster-Kronig transition
probabilities. Rev. Mod. Phys. 44: 716-813
Harris L A 1968 Analysis of materials by electron excited
Auger electrons. J. Appl. Phys. 39: 141927
Marcus L, Palmberg W 1969 Auger fracture surface
analysis of a temper embrittled 3340 steel. Trans. Me tall.
Soc. AIM 245: 1664^6
. L. M a r c u s
[University of T e x a s , A u s t i n ,
Texas, USA]

Auger Microscopy, Angular

Distribution
A n g u l a r d i s t r i b u t i o n A u g e r m i c r o s c o p y ( A D A M ) is
a n e x p e r i m e n t a l m e t h o d for d e t e r m i n a t i o n of the
s t r u c t u r e of crystalline surfaces, m o n o l a y e r s a n d thin
films. In the A D A M e x p e r i m e n t , t h e a n g u l a r distribu
tion of A u g e r electrons e m i t t e d from a s a m p l e surface
is m e a s u r e d by excitation of t h e s a m p l e with a n
electron b e a m at a fixed angle of incidence, while a
moving analyzer measures the angular distribution
for a specific A u g e r electron kinetic energy. D i s t r i b u
tions a r e m e a s u r e d over the full r a n g e of angles of
emission a n d a r e displayed in spherical c o o r d i n a t e s
so t h a t t h e results a r e readily visualized. Such distri
b u t i o n s are f o u n d t o c o n t a i n t h e " s i l h o u e t t e s " of
near-surface a t o m s " b a c k lit" by A u g e r emission
o r i g i n a t i n g from a t o m s l o c a t e d d e e p e r in t h e solid.
C o n s e q u e n t l y , t h e l o c a t i o n s of silhouettes in the dis
t r i b u t i o n directly reveal, in real space, t h e relative
p o s i t i o n s of a t o m s n e a r a solid surface.
A u g e r electron a n g u l a r d i s t r i b u t i o n s from solid
samples were first r e p o r t e d by L. A . H a r r i s in 1969,
giving rise t o a series of investigations in which the
A u g e r signal w a s typically m e a s u r e d a l o n g a few
a z i m u t h a l directions. A u g e r signals were f o u n d t o
vary substantially with t h e direction of emission,
a l t h o u g h from the limited d a t a t h e n available it w a s
difficult t o explain the origin of the v a r i a t i o n s . M o r e
recently, m e a s u r e m e n t s of t h e c o m p l e t e a n g u l a r dis
t r i b u t i o n s from single-crystal surfaces h a v e led t o the
realization t h a t the d i s t r i b u t i o n s c o n t a i n t h e sil
h o u e t t e s of near-surface a t o m s , except w h e n they a r e
o b s c u r e d by electron c h a n n e l l i n g effects u n d e r s o m e
c o n d i t i o n s . A few w o r k e r s initially expressed surprise

Auger

at this result which c o n t r a d i c t s s o m e previously

p r o p o s e d i n t e r p r e t a t i o n s of electron emission a n d
scattering. A c c o r d i n g l y , A D A M e x p e r i m e n t s were
p e r f o r m e d with a series of s t a n d a r d s a m p l e s , t h e
surface s t r u c t u r e s of w h i c h h a d been i n d e p e n d e n t l y
d e t e r m i n e d by use of multiple surface s t r u c t u r e p r o b
ing techniques, including s c a n n i n g tunnelling m i c r o
scopy ( S T M ) a n d low-energy electron diffraction
( L E E D ) . W i t h o u t exception, intensity m i n i m a (sil
houettes) were o b s e r v e d a l o n g i n t e r a t o m i c directions;
t h a t is, the l o c a t i o n s of t h e m i n i m a are directly related
to the relative p o s i t i o n s of a t o m s . T h u s , A D A M
m e a s u r e m e n t s a r e useful for t h e real-space p r o b i n g of
surface s t r u c t u r e , as well as for f u n d a m e n t a l investi
g a t i o n s of t h e i n t e r a c t i o n s of electrons with m a t t e r .
A D A M d a t a a r e also suitable for surface elemental
analysis a n d d e p t h profiling in view of the direct
relationship b e t w e e n the surface c o m p o s i t i o n vs d e p t h
a n d the A u g e r electron a n g u l a r d i s t r i b u t i o n .

7. Auger

Emission

Angular

Distribution

Energy analyzer

Phenomenon

Core-level i o n i z a t i o n of a n a t o m by a fast m o v i n g
electron o r a n r a y c a n result in a r e l a x a t i o n p r o c e s s
in which a n o u t e r electron fills t h e c o r e v a c a n c y a n d a
third electron, a n " A u g e r e l e c t r o n , " is ejected from
the a t o m . A u g e r electrons were first identified by
Pierre A u g e r in c l o u d c h a m b e r e x p e r i m e n t s a n d were
found t o h a v e discrete energies characteristic of the
emitting elements. R e c e n t d a t a suggest t h a t t h e A u g e r
emission process is inherently isotropic a n d t h a t the
observed a n g u l a r v a r i a t i o n s of signal intensity a r e d u e
to scattering by a t o m s n e i g h b o r i n g the emitter. T h u s ,
the a n g u l a r d i s t r i b u t i o n s c a n be m o d e l l e d in t e r m s of
p o i n t emitters a n d spherical scatterers of A u g e r elec
t r o n s . T h e emission of e a c h A u g e r electron is c o n
sidered to be a n isolated event. A u g e r t r a n s i t i o n s
exhibit relatively large b a n d w i d t h s (typically g r e a t e r
t h a n 10 eV) d u e to u n c e r t a i n t y - b r o a d e n i n g effects a n d
are often further b r o a d e n e d d u e t o p a r t i c i p a t i o n by
multiple t r a n s i t i o n s of slightly differing energy. T h i s is
in c o n t r a s t t o t h e n a r r o w linewidths of p h o t o e l e c t r o n
emission processes. It is i m p o r t a n t t o n o t e t h a t A u g e r
electron a n g u l a r d i s t r i b u t i o n s h a v e been r e p o r t e d t o
be p r o f o u n d l y different from p h o t o e l e c t r o n distribu
tions at the s a m e kinetic energy. T h e origins of this
difference a r e u n d e r investigation.

2. Measurement

Microscopy,

of Auger

Distributions

A p p a r a t u s e m p l o y e d for the m e a s u r e m e n t of a n g u l a r
d i s t r i b u t i o n s is illustrated in Fig. 1. M e a s u r e m e n t s a r e
p e r f o r m e d in a n u l t r a h i g h v a c u u m ( U H V ) c h a m b e r to
preserve s a m p l e cleanliness a n d t o p e r m i t u n o b
structed travel of the electrons. T o s t i m u l a t e A u g e r
emission, a p o r t i o n of the s a m p l e is i r r a d i a t e d with a n
electron b e a m at a fixed angle of incidence. T h e use of
near-grazing angles of incidence e n h a n c e s surface

(b)
Figure 1
(a) ADAM angular distributions are measured vs the
angular coordinates (a and ) of the detector. Auger
electron emission is stimulated by an incident electron
beam impinging on the sample at a fixed angle (11 from
the surface plane in this instance). An Auger electron
travelling along the selected trajectory (, ) must pass
through the angle resolving collimator and an energy
resolving analyzer before being amplifed and counted.
(b) Data are displayed in spherical coordinates

sensitivity a n d minimizes interference between the

analyzer a n d the incident b e a m . It is i m p o r t a n t for
this type of m e a s u r e m e n t t h a t the s a m p l e a n d incident
b e a m r e m a i n s t a t i o n a r y while t h e m o v i n g analyzer
scans the a n g u l a r d i s t r i b u t i o n , since even m i n o r varia
tions in the angle of incidence c a n lead to c h a n g e s in
A u g e r intensity which a r e s u b s t a n t i a l a n d c o m p l i
cated. T h u s , a small p o r t i o n of the a n g u l a r distribu
tion is inaccessible in the vicinity of the incident b e a m ,
a l t h o u g h this d o e s n o t usually p o s e a p r o b l e m because
the s y m m e t r y which often exists in the d i s t r i b u t i o n s
p e r m i t s t h e o b s e r v a t i o n of equivalent features else
w h e r e in the d i s t r i b u t i o n . A n g u l a r resolution,
r e q u i r e d to be b e t t e r t h a n a b o u t , is a c c o m p l i s h e d
by m e a n s of m e c h a n i c a l c o l l i m a t o r s . E n e r g y resolu
tion is a c c o m p l i s h e d by m e a n s of a n electrostatic
analyzer; a resolving p o w e r of a t least 50 is desirable.
E l e c t r o n s p a s s i n g t h r o u g h t h e energy analyzer are

35

Auger Microscopy,

Angular

Distribution

e l e c t r o m o d u l a t e d , amplified, c o u n t e d a n d s y n c h r o
nously amplified by m e a n s of a lock-in amplifier; the
resulting signal is digitized a n d s t o r e d by a c o m p u t e r .
F o r o p t i m a l excitation efficiency, t h e kinetic energy of
the incident electron b e a m s h o u l d be at least four
times larger t h a n t h e b i n d i n g energy of t h e c o r e level
being ionized. Because t h e energy d i s t r i b u t i o n of a n
A u g e r process is n a r r o w e r t h a n t h a t of t h e b a c k
g r o u n d signals, h a r m o n i c o r digital differentiation is
c o m m o n l y e m p l o y e d t o e m p h a s i z e t h e A u g e r signal.
Since the a m p l i t u d e of the derivative is p r o p o r t i o n a l
t o the A u g e r signal a m p l i t u d e , the a n g u l a r distribu
tion can be o b t a i n e d b y t u n i n g t o a p r o m i n e n t feature
of the derivative s p e c t r u m , typically the negative
inflection. A typical a n g u l a r d i s t r i b u t i o n c o n t a i n s
27 000 d a t a p o i n t s , o n e p o i n t p e r degree of solid
angle. T h e m e a s u r e m e n t time for a c o m p l e t e distribu
tion is typically 2 h, b u t d e p e n d s o n the incident b e a m
c u r r e n t , the strength of the A u g e r t r a n s i t i o n a n d
signal-to-noise c o n s i d e r a t i o n s .
While metallic a n d s e m i c o n d u c t i n g samples are
generally found to be a m p l y stable, d a m a g e d u e t o the
incident b e a m is possible for s o m e s a m p l e s a n d c a n be
detected by r e p e a t e d o b s e r v a t i o n a l o n g a few trajec
tories. S a m p l e s susceptible to b e a m d a m a g e c a n be
studied by averaging multiple fast scans o b t a i n e d for
individual, freshly p r e p a r e d samples.
M u l t i p l e A u g e r t r a n s i t i o n s are detectable for all b u t
the highest elements: h y d r o g e n a n d helium are n o t
detected; lithium t h r o u g h n e o n exhibit a single s t r o n g
A u g e r b a n d ; heavier elements h a v e b o t h low- a n d
high-energy A u g e r processes. N a t u r a l l y , the strongest
A u g e r t r a n s i t i o n s p r o d u c e the m o s t distinct distribu
tions. L o w - e n e r g y A u g e r electrons (below a b o u t
100 eV) necessarily originate in the o u t e r m o s t few
a t o m i c layers a n d t h u s offer a d v a n t a g e s in t e r m s of
surface sensitivity a n d simplicity for the investigation
of crystalline solid samples a n d thin films. H i g h e r
energies p e r m i t deeper p r o b i n g of b u l k s t r u c t u r e a n d
are also useful for the investigation of m o n o l a y e r s a n d
thin films.
Angle-and-energy-resolving analyzers are also use
ful for a variety of o t h e r m e a s u r e m e n t s . F o r instance,
quantitative
low-energy
electron
diffraction
( Q L E E D ) is a c c o m p l i s h e d rapidly a n d with high
accuracy. Reflection high-energy electron diffraction
( H E E D o r R H E E D ) e x p e r i m e n t s a r e readily per
formed. W i t h the a d d i t i o n of x-ray o r ion sources,
angle-resolved x-ray p h o t o e l e c t r o n spectra ( A R X P )
a n d ion a n g u l a r d i s t r i b u t i o n s ( I A D ) c a n also be
measured.

3. Specimen

Requirements

S t r u c t u r a l i n f o r m a t i o n revealed by A D A M
the average s t r u c t u r e over t h e surface a r e a
by the incident b e a m . A c c o r d i n g l y , use of
incident b e a m samples the s t r u c t u r e of a

36

d a t a is for
stimulated
a focused
region as

small as 1 in d i a m e t e r . M o s t of the results

r e p o r t e d t o d a t e were o b t a i n e d with incident b e a m s of
a b o u t 1 m m in d i a m e t e r . In general, surfaces for
which the region s a m p l e d by the incident b e a m is a
single crystal will yield a distinct d i s t r i b u t i o n . C o n v e r
sely, a m o r p h o u s surfaces will give diffuse distribu
tions. Polycrystalline samples c a n be m i c r o p r o b e d t o
yield simple o r c o n v o l u t e d a n g u l a r d i s t r i b u t i o n s
d e p e n d i n g o n w h e t h e r the incident b e a m is smaller o r
larger t h a n the s t r u c t u r a l features.
L a y e r e d s a m p l e s c a n be d e p t h profiled by m e a s u r e
m e n t of the A u g e r signals as a function of angle with
respect t o the surface p l a n e ; w h e n the A u g e r signals
from v a r i o u s elements a r e c o m p a r e d , the r a t i o of
signal from the m a i n c o n s t i t u e n t of the o u t e r m o s t
layer increasingly p r e d o m i n a t e s as grazing angles of
detection a r e a p p r o a c h e d . C o n v e n i e n t l y , the r e q u i r e d
d a t a a r e available from the c o m p l e t e a n g u l a r d i s t r i b u
tions for e a c h c o n s t i t u e n t element. Crystalline
m o n o a t o m i c layers a n d thin films consisting of a few
a t o m i c layers yield p a r t i c u l a r l y s h a r p images because
only a few symmetrically n o n e q u i v a l e n t types of
emitters a n d scatterers of A u g e r electrons a r e
involved.
A D A M o b s e r v a t i o n s of m u l t i e l e m e n t a l samples are
of p a r t i c u l a r interest. M a t e r i a l s in this category in
clude alloys, intermetallic c o m p o u n d s , type I I I - V a n d
IV-VI semiconductors, high-temperature supercon
d u c t o r s , ionic c o m p o u n d s a n d m o l e c u l a r crystals. T h e
presence of multiple elements within the crystal lattice
p r o v i d e s the o p p o r t u n i t y t o d e t e r m i n e the surface a n d
b u l k s t r u c t u r a l e n v i r o n m e n t of each element by t u n
ing t o the A u g e r signal from each element.
A n g u l a r d i s t r i b u t i o n s from p o o r l y c o n d u c t i n g s a m
ples are o b t a i n e d relatively s t r a i g h t f o r w a r d l y by the
x-ray excitation of A u g e r emission. A s the r a t e of
emission of A u g e r electrons r e q u i r e d to o b t a i n satis
factorily a n g u l a r d i s t r i b u t i o n s is relatively small (less
6
_1
t h a n 10 electrons s )> c o r r e s p o n d i n g t o c u r r e n t s less
13
t h a n 1 0 " A , the level of s a m p l e c o n d u c t i v i t y
required for A D A M m e a s u r e m e n t s is relatively low.

4. Information

Available

from

ADAM

A D A M images consist of a large a r r a y of precise

A u g e r signal intensity m e a s u r e m e n t s s p a n n i n g nearly
the entire r a n g e of angles a b o v e a solid surface.
M o d e r n i n s t r u m e n t s a r e e q u i p p e d such t h a t these
d a t a are readily accessed, processed a n d displayed in a
variety of useful f o r m a t s . This flexibility allows use of
t h e d a t a for a wide variety of p u r p o s e s , including
c r y s t a l l o g r a p h y , elemental analysis a n d f u n d a m e n t a l
investigations of electrons a n d a t o m s . W h i l e A D A M
is a useful s t a n d - a l o n e t e c h n i q u e for real-space struc
t u r a l imaging, it is especially v a l u a b l e w h e n c o m b i n e d
with o t h e r surface analysis t e c h n i q u e s , such as L E E D
a n d S T M . W h i l e L E E D yields t h e crystal lattice in
reciprocal space a n d requires l o n g - r a n g e periodicity,

Auger

Microscopy,

Angular

Distribution

Figure 2
(a) ADAM image from silver Auger electrons at 355 eV in a monolayer of silver atoms containing an overlayer of iodine
atoms, all resting on a Pt(l 11) surface. Bright regions denote large Auger signals, (b) Structure corresponding to the
ADAM image in (a)

A D A M r e s p o n d s t o the local e n v i r o n m e n t of e a c h
emitting a t o m a n d gives a real-space projection of
average a t o m i c s t r u c t u r e . T h u s , A D A M d o e s n o t
require for its effectiveness t h e s a m e degree of longr a n g e o r d e r necessary for efficient diffraction. L o n g r a n g e o r d e r is likewise n o t absolutely necessary for
S T M o b s e r v a t i o n s , which p r o v i d e t h e spatially
resolved t o p o g r a p h y of a surface. A D A M is n o t
restricted t o c h a r a c t e r i z a t i o n of the o u t e r m o s t layer,
however, a n d p r o v i d e s s t r u c t u r a l i n f o r m a t i o n r e g a r d
ing b u r i e d interfaces a n d layered s t r u c t u r e s n o t
readily accessible t o S T M .

5.

Applications

A l t h o u g h A D A M is a new t e c h n i q u e , a variety of
useful a p p l i c a t i o n s h a v e a l r e a d y been r e p o r t e d a n d
n u m e r o u s future a p p l i c a t i o n s a r e envisioned.
5.7 Thin Films
F i g u r e 2a is t h e A D A M i m a g e from silver A u g e r
electrons (355 eV) in a m o n o l a y e r of silver a t o m s
c o n t a i n i n g a n overlayer of iodine a t o m s , all resting
o n a P t ( l l l ) surface. Bright regions of the i m a g e
d e n o t e large A u g e r signals a n d d a r k r e g i o n s a r e low
signals as defined b y t h e g r a y - s c a l e b a r . C l e a r l y
evident is a h e x a g o n a l a r r a y of s i l h o u e t t e s in t h e
silver signal i n t e n s i t y (^ = 50, 0 = 0, 60, 120,
180, 240 a n d 300) p r o d u c e d b y i o d i n e a t o m s
resting a t o p n e i g h b o r i n g silver a t o m s . T h e s t r u c t u r e
c o r r e s p o n d i n g t o this i m a g e is i l l u s t r a t e d in F i g . 2 b .

Silhouettes produced by m o r e distant neighbors are

also e v i d e n t a t v a l u e s of g r e a t e r t h a n 70. A
s i l h o u e t t e is also o b s e r v e d a l o n g t h e surface n o r m a l
( = 0), d u e t o i o d i n e a t o m s s i t u a t e d directly a t o p
every t h i r d silver a t o m . A s e x p e c t e d , for a n a t o p
species, t h e d i s t r i b u t i o n from i o d i n e a t o m s is essen
tially featureless.
A s i m u l a t i o n of the silver A u g e r electron distribu
tion b a s e d o n the s t r u c t u r e s h o w n in Fig. 2 b a p p e a r s
in Fig. 3. Close a g r e e m e n t with e x p e r i m e n t occurs
w h e n iodine a t o m s a r e assigned a b l o c k i n g r a d i u s
r = 0 . 1 0 n m ( 7 5 % as large as the a t o m i c radius), a
u n i f o r m t r a n s p a r e n c y of 2 0 % a n d a silver-iodine
distance of 0.22 n m . T h e c o r r e l a t i o n coefficient,
defined later in E q n . (3), is R = 0.95. A l t h o u g h the
a g r e e m e n t between m e a s u r e d a n d calculated intensit
ies is q u i t e g o o d , the relative p o s i t i o n s of a t o m s are
revealed by the locations of features in the image
r a t h e r t h a n by t h e a b s o l u t e intensities.
T o facilitate t h e analysis process leading to the
recognition of a s t r u c t u r e , the a l g o r i t h m e m p l o y e d in
this discussion h a s been d e v e l o p e d for digital simula
tion of a n g u l a r d i s t r i b u t i o n s b a s e d o n p o i n t emitters
a n d spherical scatterers of electrons. A c c o r d i n g to this
c o m p u t a t i o n a l p r o c e d u r e , the simulated intensity
o b s e r v e d a l o n g each direction is given by

(,) =

-'

>(')
"

i=

(1)

w h e r e TV is t h e n u m b e r of e m i t t i n g a t o m s in the m o d e l ,
is t h e t r a n s p a r e n c y of the a t o m , ra,(0, ) is the

37

Auger Microscopy,

Angular

Distribution

|
[

Figure 3
Simulated angular distribution for silver Auger electrons
(355 eV) based on the structure shown in Fig. 2b

n u m b e r of a t o m s e n c o u n t e r e d by the A u g e r electron
a l o n g the p a t h (, ) a n d 7 a is a n o r m a l i z a t i o n function
which describes the s m o o t h a n d g r a d u a l increase of
the analyzer field of view with increasing p o l a r angle
of detection:
_ I expMsin(2g> + 2 7 0 ) ] - e x p ( - ^ ) \

where () was empirically d e t e r m i n e d using t h e

featureless center region of the d i s t r i b u t i o n for t h e
iodine m o n o l a y e r ( < 50) a n d kj n o r m a l i z e s the
a m p l i t u d e of the analyzer function. Best a g r e e m e n t
with e x p e r i m e n t w a s f o u n d for A = 0.4; for e x a m p l e ,
the field of view of the analyzer increased by a b o u t
5 0 % as increased from 0 (the surface n o r m a l ) t o
50. Accordingly, the A u g e r intensity a l o n g a given
direction is d e t e r m i n e d by the a t o m i c g e o m e t r y n e a r
the surface of t h e solid r a t h e r t h a n simply by the
distance travelled t h r o u g h the solid, a l t h o u g h this
distance is a useful p a r a m e t e r w h e n e s t i m a t i n g t h e
m e a n free p a t h s of electrons in a m o r p h o u s o r b u l k
samples.
A s i m u l a t i o n calculated as described yields features
which are s h a r p e r t h a n t h o s e observed in the d a t a .
T h e relative indistinctness of the e x p e r i m e n t a l i m a g e
is p r o b a b l y d u e to a c o m b i n a t i o n of a t o m i c v i b r a t i o n
a n d v a r i a t i o n s of electron density within t h e b l o c k i n g
a t o m . T h e s e issues will be e x p l o r e d further in future
work.
In a d d i t i o n t o the o b v i o u s similarity of the
observed a n d calculated images, t o be illustrated in
the following, the a g r e e m e n t is nearly q u a n t i t a t i v e .
C o m p a r i s o n of t h e c o m p l e t e e x p e r i m e n t a l , (,), a n d
theoretical, 1{(,), a n g u l a r d i s t r i b u t i o n s is a c c o m
plished by m e a n s of the s t a n d a r d statistical correla
tion coefficient d e n n e d as

38

^,) - (,)]2 \
[(,) ~ (,)]2

1 2/

( 3

5.2 Single
Crystals
Several single crystals h a v e been characterized by
A D A M a n d h a v e been f o u n d t o b e h a v e similarly.
Results for P t ( l l l ) a r e typical.
F i g u r e 4 gives the e x p e r i m e n t a l a n g u l a r distribu
tions of A u g e r electrons e m i t t e d from a P t ( l l l )
surface with kinetic energies of 65 eV a n d 1968 eV.
Clearly visible in the center of the 65 eV d i s t r i b u t i o n is
a Y - s h a p e d region of high intensity, c o r r e s p o n d i n g t o
the g a p s b e t w e e n a t o m s in the a t o m i c layer located
i m m e d i a t e l y a b o v e each e m i t t i n g p l a t i n u m a t o m . T h e
highest intensity is observed a l o n g the surface n o r m a l .
In c o n t r a s t , the 1968 eV d i s t r i b u t i o n displays highest
intensities a l o n g directions c o r r e s p o n d i n g t o the clear
est c h a n n e l s t h r o u g h the face-centered-cubic (fee)
crystal. T h a t is, the m o r e energetic A u g e r electrons
(1968 eV) p r o b e the near-surface b u l k s t r u c t u r e of the
crystal (10 n m ) , while the lower energy A u g e r elec
t r o n s (65 eV) p r o b e the o u t e r m o s t few a t o m i c layers.
A s i m u l a t i o n w h i c h relates the 65 eV d a t a t o a
m o d e l s t r u c t u r e is s h o w n in Fig. 5a. T h e best agree
m e n t b e t w e e n this g e o m e t r i c calculation a n d the d a t a
occurs w h e n p l a t i n u m a t o m s are t a k e n t o be
uniformly 4 0 % t r a n s p a r e n t with a r a d i u s e q u a l t o
9 0 % of t h e a t o m i c r a d i u s . A l t h o u g h t h e q u a n t i t a t i v e
a g r e e m e n t of intensities is g o o d , it is the locations of
the features which reveal t h e relative p o s i t i o n of
a t o m s . F o r instance, t h e Y - s h a p e d m a x i m u m in the
d a t a c o r r e s p o n d s precisely t o the g a p between a t o m s
in t h e layer i m m e d i a t e l y a b o v e e a c h e m i t t i n g a t o m .
T h e o t h e r features of the d a t a also correlate with t h e
features of the calculation: t h e d a r k e r regions n e a r t h e
p e r i m e t e r c o r r e s p o n d t o regions of t h e s t r u c t u r e a l o n g
which a n A u g e r electron e n c o u n t e r s m o r e t h a n o n e
a t o m in t h e overlying layer; features d u e to adjacent
emitters a n d scatterers a r e p r o m i n e n t because these
a r e t h e m o s t frequently o c c u r r i n g c o n t r i b u t i o n s .
D e e p e r layers also c o n t r i b u t e as is seen from a
detailed c o m p a r i s o n of the d a t a a n d the digital calcu
lation. A t o m i c v i b r a t i o n is expected to affect a n g u l a r
d i s t r i b u t i o n s b e c a u s e the a m p l i t u d e of t h e r m a l vibra
tion a t r o o m t e m p e r a t u r e is a b o u t 9 % of t h e a t o m i c
r a d i u s , a l t h o u g h the calculation depicted in Fig. 5a
d o e s n o t include a t o m i c v i b r a t i o n . T h e effect of
a t o m i c v i b r a t i o n h a s been i n t r o d u c e d i n t o calcula
tions described in t h e b i b l i o g r a p h y .
T h e near-surface a n d b u l k crystalline s t r u c t u r e s a r e
p r o b e d by the higher kinetic energy (1968 eV) A u g e r
electron d i s t r i b u t i o n . T o identify the s t r u c t u r e , a
c o m p a r i s o n is m a d e between the d i s t r i b u t i o n a n d
geometric projections as s h o w n in Fig. 5b. Projections
a r e g e n e r a t e d by calculating the trajectories b e t w e e n
all t h e a t o m s in a s s u m e d crystal m o d e l s . L a r g e r s p o t s
a r e e m p l o y e d t o represent trajectories a l o n g which the
closer i n t e r a t o m i c spacings a r e e n c o u n t e r e d . F i g u r e

Auger

Microscopy,

Angular

Distribution

Figure 4
Experimental angular distributions of Auger electrons emitted from a Pt(l 11) surface with kinetic energies of (a) 65 eV
and (b) 1968 eV. Highest intensities in (a) correspond to the gaps between atoms in the atomic layer immediately above
each emitting platinum atom. Highest intensities in (b) are observed along the trajectories corresponding to the clearest
channels through the face-centred-cubic platinum crystal
5b w a s calculated for t h e o u t e r m o s t eight
layers of the fee s t r u c t u r e of P t ( l 11).

atomic

5.3
Monolayers
Since a m o n o a t o m i c layer c o n t a i n s a t o m s l o c a t e d
between t h e e m i t t i n g a t o m s a n d the d e t e c t o r only
a l o n g trajectories n e a r g r a z i n g emission, the a n g u l a r
d i s t r i b u t i o n from a m o n o a t o m i c layer is essentially

featureless except n e a r g r a z i n g angles. Intensity

m i n i m a a r e p r e s e n t n e a r t h e edge of the d i s t r i b u t i o n ,
c o r r e s p o n d i n g t o trajectories which pass t h r o u g h
n e i g h b o r i n g a t o m s in the m o n o a t o m i c layer. W h e n
t h e a t o m s of a m o n o a t o m i c layer a r e essentially
c o p l a n a r , t h e intensity m i n i m a a r e typically located
within 15-20 of grazing. Intensity m i n i m a extend
closer t o t h e center of t h e d i s t r i b u t i o n w h e n the

Figure 5
(a) Simulated distribution of 65 eV Auger electrons from Pt(l 11). (b) Geometric projection of the interatomic directions in
the first eight atomic layers of an fee crystal. Larger spots correspond to closer interatomic spacings and the clearest
channels through the crystal
39

Auger

Microscopy,

Angular

Distribution

Figure 6
(a) Adsorption of iodine vapor at Pt(111) produces an adlattice Pt(l 11)(V? x y/l)Rl9.\-l,
consisting of a hexagonal
layer of iodine atoms containing three iodine atoms per unit cell. One iodine atom occupies an atop site (no. 1) while the
other two iodine atoms occupy threefold hollows (nos. 2, 3). (b) Two mirror image domains of the iodine (shaded circles)
adlattice are present. Each unit cell is rotated 19. relative to the P t ( l l l ) substrate and spans seven surface platinum
atoms (grid intersections), (c, d) Auger electrons emitted from adsorbed iodine atoms (circles) are blocked by neighboring
iodine atoms, producing silhouettes in the angular distribution: (c) one domain, (d) two domains, (e) The measured
angular distribution of 507-518 eV Auger electrons emitted from the iodine monolayer displays the silhouettes of
neighboring iodine atoms. Brighter colors represent stronger Auger signals (see scale at lower left). The center of the
image corresponds to emission normal to the surface ( = 0) and the edge of the main corresponds to grazing emission
( = 90). The gaps between neighboring iodine atoms give rise to intensity maxima ( = 70, = 30, 90, . . . , 330), while
minima occur along iodine-iodine internuclear direction ( = 70, = 0, 60, . . . , 300). The data have been averaged by
use of the observed threefold symmetry, (f) A digital simulation of the ADAM image for this known structure in which
iodine atoms are treated as isotropic point emitters and spherical scatterers of Auger electrons. The simulation includes 50
unit cells of each domain and predicts the data to a correlation coefficient of better than 0.98

40

Auger

m o n o a t o m i c layer is c o r r u g a t e d , such a s w h e n t h e
a t o m s o c c u p y n o n e q u i v a l e n t sites o n t h e s u b s t r a t e .
Several e x a m p l e s of flat a n d c o r r u g a t e d m o n o a t o m i c
layers h a v e been c h a r a c t e r i z e d t o d a t e b y A D A M ,
yielding structures w h i c h c o r r o b o r a t e t h o s e i n d i c a t e d
by S T M a n d L E E D .
T h e b e h a v i o r of a c o r r u g a t e d m o n o l a y e r is illus
t r a t e d by t h e following results. F i g u r e s 6a, b s h o w
m o d e l s o f t h e P t ( l 11)(V7 x V7)tfl9.1-I a d l a t t i c e
s t r u c t u r e b a s e d o n findings from L E E D a n d S T M .
Figures 6c, d aid in t h e visualization a n d c o m p a r i s o n
of the simulated (Fig. 6e) a n d e x p e r i m e n t a l ( F i g . 6f)
a n g u l a r d i s t r i b u t i o n s from t h e i o d i n e m o n o l a y e r
(518 eV). T h e features of t h e s i m u l a t i o n a c c u r a t e l y
predict t h o s e of t h e e x p e r i m e n t a l image: b r i g h t c h a n
nels a l o n g t h e 0 = 30, 90, . . . , 300 directions. T h e
best a g r e e m e n t with e x p e r i m e n t w a s f o u n d w h e n
iodine a t o m s in threefold h o l l o w s were t a k e n t o b e
closer t o t h e p l a t i n u m surface b y 0.06 n m a n d 0.08 n m
c o m p a r e d t o iodine a t o m s in onefold sites, reflecting
the influence of second-layer p l a t i n u m a t o m s . T h e s e
height differences a r e r e a s o n a b l e for onefold a n d
threefold sites a n d a r e in g o o d a g r e e m e n t with t h e
S T M results. I n a d d i t i o n t o t h e o b v i o u s q u a l i t a t i v e
similarity of t h e theoretical a n d e x p e r i m e n t a l d i s t r i b u
tions, a q u a n t i t a t i v e c o m p a r i s o n yields a c o r r e l a t i o n
coefficient R g r e a t e r t h a n 0.98. A faint c h a n n e l l i n g

Microscopy,

Angular

Distribution

p a t t e r n from t h e P t ( l 11) crystal s u b s t r a t e is also seen

n e a r t h e center of t h e d i s t r i b u t i o n . T h e s e results
vividly illustrate t h e simplicity a n d applicability of
A D A M for t h e investigation of a t o m i c s t r u c t u r e a t
solid surfaces.
See also: Auger Electron Spectroscopy, Depth Profiling,
Electron Diffraction, Low-Energy, Scanning Tunnelling
Microscopy and Spectroscopy
Bibliography
Frank D G, Batina N, Golden T, Lu F, Hubbard A 1990
Imaging surface atomic structure by means of Auger
electrons. Science 247:182-8
Frank D G, Golden T, Chyan O M R , Hubbard A 1991
Direct imaging of thin film atomic structure by angular
distribution Auger microscopy (ADAM). Appl. Surf. Sci.
48/49:166-172
Frank D G, Golden T, Chyan O M R , Hubbard A 1991
Direct imaging of monolayer and surface atomic struc
ture by angular distribution Auger microscopy (ADAM).
J. Vac. Sci. Technol. A 9:1254-60
Hubbard A T, Frank D G, Chyan O M R , Golden 1990
Imaging surface atomic structure by means of Auger
electrons. J. Vac. Sci. Technol. 8:1329-34
D. G. Frank and A. T. H u b b a r d
[University of C i n c i n n a t i , C i n c i n n a t i ,
Ohio, USA]

41

c
Ceramic Materials:
Cathodoluminescence Analysis
C a t h o d o l u m i n e s c e n c e ( C L ) is the emission of light
in response t o electron r a d i a t i o n . Essentially, t h e
m e c h a n i s m is the r a d i a t i v e r e c o m b i n a t i o n of elec
t r o n - h o l e p a i r s c r e a t e d in a s a m p l e by incident
electrons a n d is t h u s m o s t c o m m o n l y o b s e r v e d in
materials with discrete b a n d g a p s in their electron
energy d i s t r i b u t i o n s : ceramics (including m i n e r a l s a n d
semiconducting materials), some organic polymers
a n d biological m a t e r i a l s a n d , u n d e r special c i r c u m
stances, s o m e m e t a l s . A s a p h e n o m e n o n , C L is widely
exploited in p h o s p h o r s for the fluorescent screens of
televisions, V D U s a n d such like.
T h e wavelength of the e m i t t e d r a d i a t i o n is related
to the energy of the electronic t r a n s i t i o n s via t h e d e
Broglie r e l a t i o n s h i p , such t h a t

where h is P l a n c k ' s c o n s t a n t , c is the speed of light,

a n d E( a n d Ex a r e t h e final a n d initial electron e n e r g y
states, respectively. F o r m a n y ceramics, the electronic
b a n d s t r u c t u r e of t h e m a t e r i a l is such t h a t b a n d g a p
transitions lie in the energy r a n g e 1.8-3.1 eV, yielding
r a d i a t i o n in the visible r a n g e ( 7 0 0 - 4 0 0 n m ) . F u r t h e r ,
the b o n d i n g d i s r u p t i o n c a u s e d b y t h e presence o f
i m p u r i t y a t o m s o r defects such as dislocations m a y
i n t r o d u c e localized defect states i n t o the b a n d g a p ,
causing o t h e r w a v e l e n g t h s t o occur. T h e d e t e c t i o n
a n d c h a r a c t e r i z a t i o n of this e m i t t e d light forms t h e
basis for t h e use of C L a s a m i c r o s t r u c t u r a l t e c h n i q u e
to identify p a r t i c u l a r p h a s e s in m i n e r a l s a n d ceramics
a n d t o m a p their d i s t r i b u t i o n . In t h e s a m e w a y ,
the o c c u r r e n c e a n d d i s t r i b u t i o n of defects a n d
trace impurities within specific p h a s e s c a n also be
investigated.
T h e o c c u r r e n c e of C L as o n e of t h e p r o d u c t s of
electron b e a m - s a m p l e i n t e r a c t i o n s in s c a n n i n g elec
t r o n m i c r o s c o p e s ( S E M s ) (see Scanning
Electron
Microscopy)
a n d s c a n n i n g t r a n s m i s s i o n electron
microscopes ( S T E M s ) (see Electron Microscopy,
Ana
lytical) n o t only allows C L i m a g e s a n d s p e c t r a t o be
gained at high spatial r e s o l u t i o n s , b u t also e n a b l e s
rapid c o m p a r i s o n s t o be m a d e with t h e m i c r o s t r u c
tural a n d m i c r o c h e m i c a l i n f o r m a t i o n available from
o t h e r signals (e.g., b a c k s c a t t e r e d electron i m a g e s ,
x-ray spectra a n d x-ray elemental d i s t r i b u t i o n m a p s ) .
C o n s e q u e n t l y , C L h a s b e c o m e a n i n v a l u a b l e tech
n i q u e for t h e c h a r a c t e r i z a t i o n ( " b a n d s t r u c t u r e m a p
p i n g " ) of s e m i c o n d u c t i n g m a t e r i a l s w h e r e it is closely
allied to c h a r g e collection m i c r o s c o p y (i.e., i m a g i n g
with the i n d u c e d e l e c t r o n - h o l e signal itself). A t the

s a m e time, C L is p r o v i n g t o be a powerful m e a n s of
c h a r a c t e r i z i n g t h e m i c r o s t r u c t u r e s of minerals a n d
m o d e r n ceramic materials.

1. Origins,

Sensitivity

and

Applicability

T h e m e c h a n i s m s of t h e p h o t o n emission observed in
C L a r e similar t o t h o s e o c c u r r i n g by o t h e r m e t h o d s of
electronic excitation a n d t h u s there a r e m a n y parallels
with p h e n o m e n a such as p h o t o l u m i n e s c e n c e (PL).
H o w e v e r , in P L the a c t i v a t i o n of luminescent centers
c a n be very sensitive t o the w a v e l e n g t h of the (light)
excitation r a d i a t i o n , w h e r e a s the electron b e a m exci
t a t i o n used for C L analysis usually allows all possible
luminescence m e c h a n i s m s t o o p e r a t e simultaneously.
P h o t o n emission by e l e c t r o n - h o l e r e c o m b i n a t i o n
c a n be assigned t o o n e of t w o basic categories d e p e n d
ing o n t h e n a t u r e of the energy states involved. If the
t r a n s i t i o n occurs a c r o s s a f u n d a m e n t a l b a n d g a p in
t h e m a t e r i a l , t h a t is, a b a n d g a p arising as a conse
q u e n c e of the native a t o m i c s t r u c t u r e a n d b o n d i n g ,
t h e n t h e emission is said t o b e intrinsic. If, however,
t h e electron t r a n s i t i o n involves energy states t h a t only
exist, for e x a m p l e , o n a c c o u n t of i m p u r i t y a t o m s o r
o t h e r defect s t r u c t u r e s , t h e n the emission is t e r m e d
extrinsic. T h e r e f o r e , v a r i a t i o n s in b a n d s t r u c t u r e d u e
to crystal s t r u c t u r e , i m p u r i t y species a n d defects cause
v a r i a t i o n s in the w a v e l e n g t h of the C L emission.
C h a n g e s in the local density of radiative r e c o m b i n a
tion centers m a y c a u s e v a r i a t i o n s in t h e C L intensity
a n d t h u s allow m a p p i n g of b a n d s t r u c t u r e c h a n g e s ,
defect densities a n d i m p u r i t y levels. In this w a y , C L
c a n p r o v i d e i n v a l u a b l e i n f o r m a t i o n for characterizing
m a t e r i a l s which is n o t easily accessible in o t h e r ways.
In a d d i t i o n , t h e t e c h n i q u e is n o n c o n t a c t i n g a n d
generally n o n d e s t r u c t i v e ( t h o u g h s o m e m a t e r i a l s m a y
suffer electron r a d i a t i o n d a m a g e ) . Sensitivity is such
t h a t d e t e c t i o n of individual dislocations is possible
a n d impurities c a n be detected a t typical s e m i c o n d u c
20
3
t o r d o p i n g levels (e.g., ^ 1 0 a t o m s m ~ ) which a r e
t o o dilute for detection b y x-ray m i c r o a n a l y s i s . H o w
ever, significant densities of defects m a y create such a
c o n t i n u u m of defect electron states t h a t radiative
r e c o m b i n a t i o n n o longer occurs a n d the C L emission
is " q u e n c h e d . "
S o m e t i m e s , the origin of C L is readily ascribable
(e.g., t o trace i m p u r i t y v a r i a t i o n s in otherwise defectfree, h i g h - p u r i t y s e m i c o n d u c t i n g materials). H o w
ever, in m o s t cases, t h e t w o categories of C L emission
a r e indistinguishable a n d t h u s it m a y be u n c e r t a i n
w h e t h e r a p a r t i c u l a r p h a s e exhibits C L intrinsically o r
by virtue of s o m e defect o r i m p u r i t y c o n t e n t . W h i l e
this m a y affect q u a n t i t a t i v e i n t e r p r e t a t i o n , it d o e s n o t

43

Ceramic

Materials:

Cathodoluminescence

Analysis

diminish the ability of the t e c h n i q u e t o characterize

the p h a s e d i s t r i b u t i o n within ceramic m i c r o s t r u c t u r e s .
Such effects m a k e it difficult to predict which p h a s e s
m a y exhibit C L a n d t h u s m a n y e x p e r i m e n t s often
proceed empirically, at least at first. H o w e v e r , a n
increasing v o l u m e of b o t h g o o d e x p e r i m e n t a l d a t a
a n d theoretical calculations are e n a b l i n g the lumines
cence signatures of a variety of defect types in a r a n g e
of materials t o be established.
N o t all electron energy t r a n s i t i o n s lead to radiative
emission; n o n r a d i a t i v e processes such as multiple
p h o n o n g e n e r a t i o n a n d A u g e r excitations are c o m p e
titive a n d generally favored. A l s o , m u c h of the light
generated can be effectively lost within t h e m a t e r i a l
t h r o u g h a b s o r p t i o n or total internal reflection. C o n
sequently, t h e signal levels of C L emission are r a t h e r
low a n d require the use of highly efficient detection
systems a n d / o r high electron b e a m c u r r e n t s .
2. Instrumentation

and

Techniques

Essentially there are t w o basic

experimental
a p p r o a c h e s for C L studies. T h e first a p p r o a c h is to
use a light optical C L m i c r o s c o p e in which a simple
electron g u n " f l o o d s " a specimen (held u n d e r v a c u u m
in a special t r a n s p a r e n t cell) with electrons of energies
between 3 keV a n d 30 keV. T h e C L emission is
observed via c o n v e n t i o n a l i m a g e - f o r m i n g light optics.
While these systems are widely used for mineralogical
studies, they are rarely used for basic studies of
ceramics.
A n alternative, a n d m o r e c o m m o n l y used, m e t h o d
of o b s e r v a t i o n for ceramic m a t e r i a l s is to include a
C L detection system within S E M s o r S T E M s . H o w
ever, the design of high-efficiency light-collection sys
tems for use in such i n s t r u m e n t s is highly challenging,
particularly w h e n space in the vicinity of p r o b e forming lenses is very limited. A n i m p o r t a n t c o n
sideration in their design is t h a t they m u s t p r e v e n t
e x t r a n e o u s light from entering the collection system
from such potential sources as the electron g u n , the
p h o s p h o r scintillators of s e c o n d a r y electron d e t e c t o r s
a n d even the m a t e r i a l s of the C L d e t e c t o r (which m a y
itself luminesce w h e n struck by electrons). W i n d o w s
a n d light guides are often used to t r a n s m i t the light
signal t o d e t e c t o r s outside the v a c u u m c h a m b e r a n d
should be selected a n d characterized for their a b s o r p
tion p r o p e r t i e s . G l a s s w i n d o w s in p a r t i c u l a r t e n d t o
strongly a t t e n u a t e wavelengths in the infrared r a n g e .
F o r m a n y studies, a c o m m o n design for the light
collector is a t h r e e - d i m e n s i o n a l elliptical o r p a r a b o l i c
metal m i r r o r inside which the specimen is p o s i t i o n e d
at o n e of the foci. T h e light t h u s collected is directed
into a p h o t o m u l t i p l i e r t u b e of k n o w n spectral re
sponse, the o u t p u t of which is d e p e n d e n t o n the light
intensity. Simple silicon o r g e r m a n i u m solid-state
detectors can be c a p a b l e of detecting p h o t o n emission
a n d are also effective for infrared wavelengths. H o w
ever, at the simplest level, satisfactory images c a n

44

often be o b t a i n e d from s t r o n g C L emitters using

simple p r o x i m i t y light guides, lenses o r m i r r o r s t o
extract t h e C L signal.
A d d i t i o n a l l y s o m e form of filter device c a n be
inserted s o m e w h e r e in the light p a t h a n d used t o
discriminate t h e detected light by its w a v e l e n g t h . T h i s
c a n t a k e the form of either a simple filter a r r a n g e m e n t
o r a g r a t i n g m o n o c h r o m a t o r system a n d allows either
C L spectra to be r e c o r d e d a n d / o r " m o n o c h r o m a t i c "
i m a g i n g t o be u n d e r t a k e n to m a p the d i s t r i b u t i o n of
p a r t i c u l a r t r a n s i t i o n energies. T h u s , there a r e essen
tially t w o distinct m o d e s of o p e r a t i o n for s t r u c t u r a l
analysis using C L , n a m e l y , i m a g i n g a n d s p e c t r o s c o p y .
2.1 CL

Imaging

In the C L i m a g i n g m o d e , a direct i m a g e of t h e C L
emission from the surface region of the m a t e r i a l is
formed. F o r i n s t r u m e n t s o p e r a t i n g with a s c a n n i n g
electron b e a m , this is simply achieved by s y n c h r o n
ously s c a n n i n g a n d m o d u l a t i n g a c a t h o d e r a y t u b e
( C R T ) with the (amplified) o u t p u t from the detection
device. By use of the filter system, the images c a n be
wavelength selected.
2.2 Spectroscopic
Studies
In the C L s p e c t r o s c o p y m o d e t h e light emission c a n
be analyzed for its wavelength intensity s p e c t r u m a n d
a t t e m p t s m a d e t o c o r r e l a t e the o c c u r r e n c e of given
w a v e l e n g t h with the emission from k n o w n types of
defects.
Such studies benefit greatly from the use of low
s a m p l e t e m p e r a t u r e s (particularly t h a t of liquid he
lium) since this reduces t h e r m a l b r o a d e n i n g of the
p e a k s , c a n increase the intensity of C L emission b y
certain m e c h a n i s m s a n d c a n also help reduce m a t e r i a l
d a m a g e d u e t o h i g h - d o s e electron i r r a d i a t i o n . H o w
ever, such e x p e r i m e n t a l a r r a n g e m e n t s are b o t h costly
and complex.

3. Sample

Preparation

O n e of the a t t r a c t i o n s of the C L techniques is t h a t n o

further specimen p r e p a r a t i o n is required b e y o n d t h a t
used to r e n d e r t h e s a m p l e m a t e r i a l suitable for the
h o s t i n s t r u m e n t (e.g., reflected light m i c r o s c o p e ,
S E M , S T E M ) . T h u s , fracture surfaces a n d p o w d e r s ,
for e x a m p l e , are suitable as well as polished samples
a n d thin sections. A thin c a r b o n c o a t i n g m a y be
required if gross c h a r g i n g of t h e s a m p l e occurs in the
incident electron b e a m a n d care m u s t be t a k e n to
e n s u r e t h a t such c o a t i n g s d o n o t unnecessarily inter
fere with t h e light o u t p u t .

4. Spatial

Resolution

T h e typical a t t a i n a b l e spatial resolution o n b u l k s a m

ples in S E M i n s t r u m e n t s is a b o u t 1 a n d is gov
erned by the electron p r o b e size necessary t o o b t a i n a

Ceramic

Materials:

Cathodoluminescence

Analysis

r e a s o n a b l e signal-to-noise r a t i o in t h e detected C L
emission, t h e electron b e a m - s a m p l e i n t e r a c t i o n
v o l u m e , the optical p r o p e r t i e s of t h e s a m p l e (e.g.,
a b s o r p t i o n a n d refractive index w h i c h d e t e r m i n e sig
nal escape d e p t h s ) a n d t h e e l e c t r o n - h o l e m i g r a t i o n
characteristics. H i g h - b r i g h t n e s s electron sources such
as L a B 6 a n d field e m i t t e r s h e l p t o i m p r o v e r e s o l u t i o n
by minimizing t h e incident p r o b e size necessary for a
given b e a m c u r r e n t . T h e size of t h e e l e c t r o n - s a m p l e
interaction v o l u m e c a n be e s t i m a t e d using M o n t e
C a r l o s i m u l a t i o n s a n d t h e v a r i a t i o n of electron p e n e
t r a t i o n with incident electron energy (typically oc E1)
allows c r u d e d e p t h profiling t o be u n d e r t a k e n as a
function of b e a m voltage E. H o w e v e r , a t higher b e a m
energies, the light g e n e r a t e d far below t h e surface
m i g h t be strongly a t t e n u a t e d o r m a y be scattered o r
diffused p r i o r t o escape. I n all cases, t h e d e p t h from
which C L i n f o r m a t i o n c a n be retrieved is typically
^ 20 a n d is d e p e n d e n t o n the s a m p l e m a t e r i a l a n d
the energy of t h e incident electron.
T h e use of thin specimens in S E M o r S T E M
p e r m i t s the size of t h e electron i n t e r a c t i o n v o l u m e
within the specimen t o be greatly r e d u c e d a n d c a n
offer potentially higher r e s o l u t i o n s a t t h e expense of
decreased e l e c t r o n - h o l e p a i r g e n e r a t i o n events.
After g e n e r a t i o n , the e l e c t r o n - h o l e p a i r s m i g r a t e
until they reach a r e c o m b i n a t i o n center. T h i s c a n be
quite d i s t a n t from t h e carrier g e n e r a t i o n site a n d , for
radiative t r a n s i t i o n s , serves t o d e g r a d e the r e s o l u t i o n .
In t h i n n e r specimens, n o n r a d i a t i v e surface r e c o m b i
n a t i o n b e c o m e s m o r e likely a n d while r e d u c i n g t h e
overall r a d i a t e d intensity also limits l o n g m i n o r i t y
carrier diffusion p a t h s a n d c a n e n h a n c e resolution.
Spatial r e s o l u t i o n c a n also be i m p r o v e d by the use of
time-resolved t e c h n i q u e s w h e r e t h e C L o b s e r v a t i o n s
are m a d e in s h o r t time intervals ( ~ 1 ns) t h a t limit t h e
d e g r a d a t i o n of r e s o l u t i o n d u e t o carrier diffusion.
H o w e v e r , t h e i n s t r u m e n t a t i o n for such studies is
sophisticated a n d usually limited t o t h e e v a l u a t i o n of
device m a t e r i a l s .
T h e r a d i a t i v e r e c o m b i n a t i o n time (i.e., t h e interval
between carrier excitation a n d r e c o m b i n a t i o n ) c a n be
r a t h e r l o n g (e.g., in long-persistence p h o s p h o r m a t e r
ials) a n d , for s c a n n i n g p r o b e t e c h n i q u e s , often re
quires the use of slow line speeds a n d frame times in
o r d e r t o avoid " s m e a r i n g " of t h e i m a g e .
5. Examples

of CL Characterization

of

Ceramics

5.1 Phase
Distributions
Figures l a , b s h o w t h e d i s t r i b u t i o n of p h a s e s in
c u r r e n t engineering c e r a m i c m a t e r i a l s as revealed by
C L in a S E M using a p a r a b o l i c m i r r o r d e t e c t i o n
a r r a n g e m e n t . In Fig. l a , the m i c r o s t r u c t u r e of a n
A l 2 0 3 - Z r 0 2 c e r a m i c c u t t i n g t o o l insert is revealed
to c o n t a i n a p p r o x i m a t e l y 1 Z r 0 2 particles (light
imaging), - 1 2 0 3 (mid-gray) a n d a p p r o x i m a t e l y
5-10 laths of a n u n e x p e c t e d , i m p u r e , a l u m i n a
p h a s e ( d a r k i m a g i n g ) . W i t h o u t C L , these laths c a n -

Figure 1
Examples of the use of panchromatic CL images (SEM) to
both distinguish and reveal the distribution of the phases
present in engineering ceramics: (a) three phases revealed
in an A l 2 0 3 - Z r 0 2 alloy; and (b) Grain-boundary films of
monoclinic Z r 0 2 delineated in a cubic/tetragonal (partially
stabilized) Zr0 2-4wt%CaO alloy

n o t be detected except by lengthy p o i n t - t o - p o i n t

x-ray m i c r o a n a l y s i s . H o w e v e r , o n c e revealed b y C L ,
these l a t h s a r e readily investigated by x-ray m i c r o
analysis. In Fig. l b , the d i s t r i b u t i o n of m o n o c l i n i c
Z r 0 2 a r o u n d the grain b o u n d a r i e s of a n otherwise
c u b i c / t e t r a g o n a l Z r 0 2 s a m p l e is clearly delineated.
T h u s , d i s t r i b u t i o n is impossible t o reveal with x-ray
diffraction m e t h o d s a n d w o u l d otherwise require
lengthy T E M investigations. T h e clear c o n t r a s t in
such i m a g e s r e n d e r s t h e m readily a m e n a b l e t o i m a g e
analysis.
5.2 Defect
Distributions
F i g u r e 2 s h o w s t h e luminescence from the dislocation
a r r a y a r o u n d a m i c r o h a r d n e s s i n d e n t a t i o n in a b u l k
s a m p l e of M g O ; the i n d e n t a t i o n center is d a r k
b e c a u s e of q u e n c h i n g . A significant b a c k g r o u n d dis
location density a w a y from the i n d e n t a t i o n is also
clearly revealed. In large s a m p l e s , dislocation a r r a y s
of this type c a n o t h e r w i s e o n l y be revealed b y etch
pitting o r x-ray t o p o g r a p h i c techniques.

45

Ceramic Materials:

Cathodoluminescence

Analysis

Figure 2
The dislocation array around a 1 kg hardness indentation
in the (100) face of a large MgO single crystal revealed by
panchromatic CL imaging

5.3 Possibilities for New

Materials
Since m a n y new i n o r g a n i c m a t e r i a l s a r e being p r o
duced in increasingly p u r e r form for v a r i o u s appli
cations, C L is a potentially powerful investigative
technique. F i g u r e 3a s h o w s the luminescence varia
tion across the chemical v a p o r d e p o s i t i o n ( C V D )
" g r o w t h r i n g s " in a c o m m e r c i a l SiC fiber used t o
reinforce v a r i o u s c o m p o s i t e s . W h e t h e r this arises
from v a r i a t i o n s in i m p u r i t y c o n t e n t o r p o i n t defects
(i.e., a c h a n g e in s t o i c h i o m e t r y ) is, as yet, u n k n o w n ,
b u t b o t h the ring s t r u c t u r e a n d the c h a n g e s with
successive ring g r o w t h are clearly delineated. Such
structural o b s e r v a t i o n s rival t h e i n f o r m a t i o n avail
able by T E M b u t w i t h o u t the lengthy specimen p r e
p a r a t i o n . H o w e v e r , n o o t h e r simple m e a n s of observ
ing the impurity/defect d i s t r i b u t i o n a t this spatial
resolution is yet k n o w n .
Figures 3b,c show o b s e r v a t i o n s from individual
a p p r o x i m a t e l y 1 d i a m o n d crystals in a partially
g r o w n film of the type being developed for surface
engineering. T h e C L image of Fig. 3c is n e a r m o n o
c h r o m a t i c ( ~ 4 2 0 n m ) , is p r o b a b l y associated with
p a r t i c u l a r defects a n d s h o w s the e n h a n c e d spatial
resolution ( < 1 ) o b t a i n e d by o p e r a t i n g o n t h i n
samples at low incident energies (5 k V ) .

6.

Conclusions

C L is a powerful t e c h n i q u e for detecting a n d m a p p i n g

p h a s e s , trace impurities a n d defect d i s t r i b u t i o n s in
ceramic materials. C o m b i n e d with parallel i m a g e
m o d e s in electron m i c r o s c o p e s , it c a n p r o v i d e u n i q u e
a n d readily accessible i n f o r m a t i o n . While its use for
characterizing ceramics h a s largely been centered o n
minerals a n d s e m i c o n d u c t i n g m a t e r i a l s , i m p r o v e
m e n t s in detection systems, a c o n s t a n t l y developing
u n d e r s t a n d i n g of the origins of the C L signal (es-

46

Figure 3
CL (SEM) images from new ceramic materials: (a) changing
levels of impurities/defects revealed in the growth rings of
a SiC fiber deposited on a (nonluminescent) metal wire
core (15 kV); and (b, c) 5 kV secondary electron and CL
images of individual diamond crystals early in the growth
of a diamond film for surface engineering

pecially the luminescence " s i g n a t u r e " of p a r t i c u l a r

defect types) a n d its applicability t o m a n y new m a t e r
ials imply t h a t it is a t e c h n i q u e ripe for b o t h r e a p p r a i
sal a n d w i d e s p r e a d use.
See also: Scanning Electron Microscopy; Thermoluminescence

Ceramic

Bibliography
Brown L M, Younis Khan M, Chaudhri 1988 Quench
ing of cathodoluminescence at the centre of hardness
indentations on a (100) face of MgO. Philos. Mag. A 57:
187-96
Czernuszka J T, Page F 1985 Cathodoluminescence: a
microstructural technique for exploring phase distribu
tions and deformation structures in zirconia ceramics. J.
Am. Ceram. Soc. 68: C196-9
Marshall D J 1988 Cathodoluminescence of Geological
Materials. Unwin Hyman, London
Newbury D E, Joy D C, Echlin P, Fiori C E, Goldstein J I
1986 Advanced Scanning Electron Microscopy and X-Ray
Microanalysis. Plenum, New York
Pennycook S J, Brown L M, Craven A J 1980 Observation
of cathodoluminescence at single dislocation by STEM.
Philos. Mag. AAV. 589-600
Petroff , Lang D V, Strudel J L, Logan R A 1978
Scanning transmission electron microscopy techniques
for simultaneous electronic analysis and observation of
defects in semiconductors. In: Johari O, Becker R (eds.)
1978 Scanning Electron Microscopy, Pt. 1. Scanning
Electron Microscopy, Chicago, IL, pp. 325-32
Warwick C A 1989 Scanning cathodoluminescence of semi
conducting materials. Inst. Phys. Conf. Ser. 98: 447-70
Yacobi G, Holt D 1990 Cathodoluminescence Micros
copy of Inorganic Solids. Plenum, New York
T. F . P a g e
[University of N e w c a s t l e u p o n T y n e ,
Newcastle u p o n Tyne, U K ]
R. B a r r e t t
[CNRS, Grenoble, France]

Ceramic Powders: Packing

Characterization
T h e u n i f o r m p a c k i n g of particles with a n overall
desired s h a p e is t h e goal of t h e v a r i o u s c e r a m i c
forming o p e r a t i o n s . P a c k i n g density a n d its vari
a t i o n t h r o u g h o u t a b o d y d e t e r m i n e t h e a m o u n t of
s h r i n k a g e o c c u r r i n g d u r i n g firing. P a c k i n g density
v a r i a t i o n s c a n also c a u s e w a r p i n g a n d c r a c k i n g by
differential s h r i n k a g e o n firing. C h a r a c t e r i z a t i o n of
p o w d e r p a c k i n g is, therefore, i m p o r t a n t w h e n q u a l i t y
a n d d i m e n s i o n a l c o n t r o l a r e of c o n c e r n .

7. Constituents

of a Particulate

Powders:

Packing

Characterization

tice, c o m p o s i t i o n s a r e given o n a weight fraction

basis. T w o c o n v e n t i o n s exist, o n e relative t o the
weight of p a r t i c u l a t e m a t e r i a l a n d the o t h e r relative to
the t o t a l weight of t h e system. W e i g h t fractions o n the
latter basis c a n be calculated from t h o s e o n the former
basis b y m u l t i p l y i n g by t h e r a t i o of the solid weight t o
the t o t a l weight. In this article, c o m p o s i t i o n s are
expressed o n a t o t a l weight basis.

2. Known

and Measurable

Quantities

T h e weights a n d weight fractions of t h e c o n s t i t u e n t s

a r e usually k n o w n (since they serve as the basis for the
original f o r m u l a t i o n ) o r c a n be easily d e t e r m i n e d . In
a d d i t i o n , the v o l u m e of a system c a n be m e a s u r e d by
a variety of m e t h o d s . F o r b o d i e s with simple g e o m e t
ric s h a p e s (e.g., right circular cylinders o r bars), the
v o l u m e c a n be calculated by a few linear m e a s u r e
m e n t s , as with a ruler o r calipers. F o r m o r e c o m p l e x
s h a p e s , the v o l u m e c a n be d e t e r m i n e d by a m e r c u r y
p y c n o m e t e r if t h e b o d y is small. M e r c u r y is n o n w e t ting a n d d o e s n o t enter the voids of the green b o d y .
T h e d i s p l a c e m e n t v o l u m e in m e r c u r y c a n therefore be
d e t e r m i n e d . F o r larger b o d i e s , t h e o u t e r surface c a n
be covered with a w a t e r - i m p e r v i o u s c o a t i n g o r film
a n d t h e d i s p l a c e m e n t v o l u m e in w a t e r t h e n m e a s u r e d .
T h e v o l u m e of i m p e r v i o u s b o d i e s c a n also be
m e a s u r e d by t h e A r c h i m e d e s m e t h o d , in which the
weight of t h e b o d y is m e a s u r e d in air a n d s u b m e r s e d
in a liquid. T h e v o l u m e is t h e difference b e t w e e n these
t w o weights divided by t h e density of the liquid. T h e
v o l u m e m e a s u r e d by a gas p y c n o m e t e r represents t h a t
v o l u m e of t h e b o d y w h i c h c a n n o t be p e n e t r a t e d by the
gas. T h e r e f o r e , the v o l u m e of o p e n p o r e s is excluded.
F o r d r y p o w d e r s , h a v i n g only gas in the voids, the gas
p y c n o m e t e r m e a s u r e s the v o l u m e of solids. If the
b o d y is totally i m p e r v i o u s t o gas, the overall v o l u m e
is m e a s u r e d .
O t h e r useful i n f o r m a t i o n includes t h e t r u e densities
pi of t h e solids, liquids a n d solutions t h a t m a y form
b e t w e e n c o n s t i t u e n t s . S o l u t i o n s m a y form, for ex
a m p l e , by the dissolution of o r g a n i c b i n d e r in water.
S o l u t i o n densities a r e often k n o w n o r c a n be
m e a s u r e d separately. F o r systems c o n t a i n i n g solu
t i o n s , the n u m b e r of p h a s e s m a y be less t h a n the
n u m b e r of c o n s t i t u e n t s .

System

C e r a m i c green (unfired) b o d i e s c o n t a i n n o t only cera

mic p a r t i c u l a t e m a t t e r b u t also o t h e r s u b s t a n c e s such
as liquids, solutes in t h e liquid, gas a n d p o l y m e r i c
resins (e.g., binders). T h e s e o t h e r m a t e r i a l s reside in
the void spaces b e t w e e n t h e particles. T h e entire
c o m b i n a t i o n of m a t e r i a l s c o n s t i t u t e s a p a r t i c u l a t e
system.
T h e relative a m o u n t s of t h e v a r i o u s s u b s t a n c e s in a
green b o d y a r e expressed as a c o m p o s i t i o n . In p r a c -

3. Densities

and Specific

Volumes

A density function is a r a t i o of weight t o v o l u m e for a

given q u a n t i t y . A specific v o l u m e is a r a t i o of v o l u m e
t o weight (the inverse of density). E a c h of t h e i p h a s e s
in a p a r t i c u l a t e system is c h a r a c t e r i z e d b y its o w n
density /?,. In a d d i t i o n , o t h e r density functions can be
defined in relation t o the t o t a l system. T h e b u l k
density of t h e b o d y is t h e r a t i o of t h e t o t a l weight t o
the t o t a l v o l u m e . T h e p a c k i n g density pp is the r a t i o of

47

Ceramic Powders: Packing

Characterization

the weight of solid to the t o t a l b o d y v o l u m e . T h e

c o r r e s p o n d i n g specific v o l u m e s for these densities a r e
,., a n d v p.

4. Volumetric Compositions

of Phases

Since p a c k i n g is space filling, it c a n be described in

t e r m s of volume-related q u a n t i t i e s . P r o p o r t i o n s a r e
represented by the v o l u m e fractions of p h a s e s
present. T h e s e c a n be calculated from weight fractions
w, of the c o n d e n s e d p h a s e s (not necessarily the consti
tuents), the densities p{ of the p h a s e s a n d the b u l k
density of the system. F o r c o n d e n s e d p h a s e s ,

iPlPi

T h e v o l u m e fraction % of t h e gas p h a s e is e q u a l to
1 - ,. T h e s u m of % a n d the values for all
c o n d e n s e d p h a s e s is e q u a l to unity.
T w o c o m m o n l y used p a r a m e t e r s a r e the p e r c e n t of
theoretical density a n d the percent p o r o s i t y . T h e
former is 100 times the v o l u m e fraction of solids
a n d the latter is 100 times the v o l u m e fraction of the
gas p h a s e (pr If the t e r m " v o i d s " is used to describe all
the space n o t occupied by solid, the v o l u m e fraction
of voids is 1 - (ps.
T h e b e h a v i o r of p a r t i c u l a t e systems d e p e n d s in
m a n y instances o n the space-filling characteristics of
the system. F o r different systems, c o n t a i n i n g different
c o n s t i t u t e n t s , c o m p a r i s o n s are meaningful only in
terms of v o l u m e fractions ( n o t weight fractions). F o r
e x a m p l e , consider a system of u n i f o r m spheres which
form a dense r a n d o m p a c k i n g at a v o l u m e fraction of
0.63. W h e n the voids a r e filled with water, the weight
fraction of solids in the system d e p e n d s o n the density
of the solid p h a s e . If t w o systems of u n i f o r m spheres
h a v i n g particles of different densities are c o m p a r e d ,
the weight fractions are different; h o w e v e r , the geo
metric a n d space-filling characteristics a r e the s a m e .

5, Specific Volumes of

Mixtures

W h e n dealing with systems c o n t a i n i n g t w o o r m o r e

c o n d e n s e d p h a s e s (e.g., solid a n d liquid), in which o n e
c o m p o s i t i o n a l p a r a m e t e r at a time is systematically
varied, it is c o n v e n i e n t t o utilize a specific v o l u m e
d i a g r a m . T h i s is a plot of the specific v o l u m e of the
system as a function of the c o m p o s i t i o n a l variable.
T h e value of a specific v o l u m e d i a g r a m is illustrated
schematically for the case of a m i x t u r e of a l u m i n a
p o w d e r a n d w a t e r (see Fig. 1). T h e weight fraction of
w a t e r is represented by the abscissa a n d specific
v o l u m e q u a n t i t i e s a r e given by t h e o r d i n a t e . T h e
specific v o l u m e s of p u r e a l u m i n a a n d p u r e w a t e r a r e
designated at p o i n t s A a n d B. E x p e r i m e n t a l l y
m e a s u r e d values of the specific v o l u m e at a given
w a t e r c o n t e n t c a n b e p l o t t e d o n the s a m e g r a p h (e.g.,

48

Weight fraction of water

Figure 1
Specific volume diagram

p o i n t O ) . F r o m the p o s i t i o n of t h e d a t a o n the g r a p h ,
several useful c o n c l u s i o n s c a n be d e d u c e d , as follows
in this section.
T h e straight line j o i n i n g p o i n t s A a n d describes
h o w the specific v o l u m e of t h e system varies with
c o m p o s i t i o n if n o gas p h a s e is present. T h e left-hand
side of this line is d a s h e d , since at lower w a t e r
c o n t e n t s t h e c o n d i t i o n of n o gas p h a s e is physically
unrealistic; since there is a limit t o h o w tightly the
particles c a n p a c k , t h e void v o l u m e c a n n o t c o n
t i n u o u s l y d i m i n i s h with the w a t e r v o l u m e .
T h e specific v o l u m e of a m i x t u r e c a n n o t fall b e l o w
line A B unless a chemical r e a c t i o n takes place, such as
the p a r t i a l dissolution of the solid in water. In the
absence of r e a c t i o n s , t h e d a t a m u s t fall o n o r a b o v e
line A B . W h e n a b o v e the line, t h e system c o n t a i n s a
gas p h a s e . T h e v o l u m e fractions of t h e three p h a s e s
c a n be d e t e r m i n e d by c o n s t r u c t i n g a vertical line
t h r o u g h the d a t a p o i n t O , a n d a n o t h e r line between
p o i n t s A a n d F . T h e v o l u m e fractions of solid, liquid
a n d gas a r e given b y the r a t i o of line lengths E D - E O ,
C D - E O a n d C O - E O , respectively.
In special cases, t h e p a c k i n g density of the particles
m a y r e m a i n c o n s t a n t as w a t e r is a d d e d to fill t h e
voids. F o r these cases, t h e v a r i a t i o n in specific v o l u m e
is represented by a straight line d r a w n from p o i n t G ,
the p a c k i n g specific v o l u m e of the d r y p o w d e r , t o
p o i n t H , w h e r e e x t r a p o l a t i o n of t h e line goes t o p o i n t
F . F r o m p o i n t G t o p o i n t H , t h e voids a r e being filled
with liquid, w i t h c o m p l e t e filling o c c u r r i n g a t p o i n t H .
T h e c o m p o s i t i o n at is t h e a m o u n t of w a t e r n e e d e d
to fill the void space completely for a given particle
packing.
A h y p o t h e t i c a l v a r i a t i o n in specific v o l u m e with
c o m p o s i t i o n for the a l u m i n a - w a t e r system is given as
the curve I J K L B . C o m p a r i n g the curve with the lines

Ceramic

Powders:

Packing

Characterization

A B a n d G F , it c a n be d e d u c e d h o w the space-filling
relations c h a n g e as w a t e r is a d d e d t o t h e d r y p o w d e r .
P o i n t I is t h e p a c k i n g specific v o l u m e of the d r y
p o w d e r . A s small q u a n t i t i e s of w a t e r a r e a d d e d , the
p a c k i n g density decreases (e.g., o w i n g t o capillary
effects) until p o i n t J is r e a c h e d . F r o m p o i n t J t o p o i n t
K, the p a c k i n g specific v o l u m e r e m a i n s c o n s t a n t
(equal t o t h e value at p o i n t G ) while w a t e r c o n t i n u e s
to fill the voids. B e y o n d p o i n t K , the p a c k i n g begins
to e x p a n d s o m e w h a t while t h e last a m o u n t s of gas in
the voids a r e being replaced by w a t e r . T h i s c o u l d
result, for e x a m p l e , b e c a u s e of n o n u n i f o r m d i s t r i b u
tion of w a t e r t h r o u g h o u t t h e voids. A t p o i n t L, all the
gas p h a s e is g o n e (since t h e d a t a fall o n line A B ) .
F r o m p o i n t L t o p o i n t B, a gas-free m i x t u r e of
a l u m i n a a n d w a t e r exists.
This m e t h o d o l o g y c a n be applied to a n y system in
which o n e i n d e p e n d e n t c o m p o s i t i o n a l v a r i a t i o n is
occurring. It c a n be a p p l i e d t o m u l t i c o m p o n e n t sys
tems if the r a t i o of certain p h a s e s r e m a i n s fixed. F o r
example, a system m a y b e c o m p r i s e d of solid 1, solid
2, liquid 1 a n d liquid 2 (the liquids a r e immiscible). If
b o t h the weight r a t i o s of solid 1 t o solid 2 a n d of
liquid 1 t o liquid 2 r e m a i n c o n s t a n t , a specific v o l u m e
d i a g r a m c a n be c o n s t r u c t e d in t e r m s of the weight
fractions of t o t a l solid a n d t h e weight fractions of
total liquid.

6. Packing

Inhomogeneities

T h e u n i f o r m i t y o f p a c k i n g t h r o u g h o u t a green b o d y is
i m p o r t a n t for u n i f o r m s h r i n k a g e a n d e l i m i n a t i o n of
p o r o s i t y d u r i n g firing. T w o scales of i n h o m o g e n e i t y
are the microscale a n d t h e m a c r o s c a l e . T h e microscale
involves d i m e n s i o n s of t h e o r d e r of m a g n i t u d e of
those of the particles. T h e m a c r o s c a l e involves d i m e n
sions c o m p a r a b l e t o t h e size of t h e b o d y (e.g., m m o r
cm). O n a microscale, voids t h a t a r e larger t h a n t h e
sizes of t h e particles a r e a p r o b l e m b e c a u s e they
c o m m o n l y r e m a i n after firing. A s a n e x a m p l e , Fig. 2
illustrates for a n a l u m i n a c o m p a c t h o w a local region
of higher p o r o s i t y results in t h e f o r m a t i o n of large
voids d u r i n g sintering.
T h e d i s t r i b u t i o n of void sizes c a n be e s t i m a t e d b y
m e r c u r y p o r o s i m e t r y . W h e n m e r c u r y is forced u n d e r
pressure t o fill t h e voids of a system, large p o r e s a r e
filled a t lower pressures t h a n small p o r e s . A c u r v e of
m e r c u r y v o l u m e i n t r u s i o n vs p r e s s u r e p r o v i d e s infor
m a t i o n o n void-size d i s t r i b u t i o n . D e n s i t y v a r i a t i o n s
o n a m a c r o s c a l e c a n be assessed by dividing the
sample i n t o small u n i t s (e.g., by cutting) a n d m e a s u r
ing the density of e a c h unit. I n s o m e cases, it is
possible t o i m p r e g n a t e t h e v o i d s with a resin o r sulfur
so t h a t m e t a l l o g r a p h i c cross sections c a n be o b t a i n e d
by c u t t i n g a n d polishing. U s i n g m i c r o s c o p y , v o l u m e
fractions of p h a s e s a n d d i s t r i b u t i o n characteristics
c a n be e s t i m a t e d . A n o t h e r m e t h o d is t o use a n x-ray
r a d i o g r a p h (Broese v a n G r o e n o u a n d K n a a p e n 1980)

Figure 2
Retention of low-density region in alumina during
sintering: (a) initial compact, (b) after 1 min at 1700C
(after Kingery et al. 1976 p. 482)

t h r o u g h a sectioned slice of m a t e r i a l after light sinter

ing. T h e intensities of t h e r a d i o g r a p h are calibrated
with m a t e r i a l s of k n o w n density.
See also: Powder Characterization

49

Ceramic

Powders:

Packing

Characterization

Bibliography
Detector

Broese van Groenou A, Knaapen A C 1980 Density varia

tions in die-compacted powders. Sci. Ceram. 10: 93-9
Jones J T, Bernard F 1972 Ceramics: Industrial Process
ing and Testing. Iowa State University Press, Ames, IA
Kingery W D, Bowen Uhlmann D R 1976 Introduction
to Ceramics, 2nd edn. Wiley, New York

Incident
electron
beam

Bloch wave

X rays

G. Y. O n o d a
[University of F l o r i d a , Gainesville,
Florida, USA]

Channelling-Enhanced Microanalysis
T h e p r o d u c t s of i n t e r a c t i o n events b e t w e e n a n elec
t r o n b e a m a n d a m a t e r i a l , such as the characteristic
rays representative of t h e c o n s t i t u e n t elements of the
m a t e r i a l o r the electron energy loss c o r r e s p o n d i n g t o
x-ray p r o d u c t i o n , a r e c o m m o n l y used for chemical
analysis. In a m o d e r n t r a n s m i s s i o n electron m i c r o
scope e q u i p p e d with a n energy dispersive x-ray detec
t o r ( E D X S ) or a n electron energy loss s p e c t r o m e t e r
( E E L S ) , the ability t o p r o d u c e incident electron
p r o b e s with d i a m e t e r s of the o r d e r of 10 n m easily
(with a routinely available i m a g e r e s o l u t i o n of 2 5 n m ) results in a m i c r o a n a l y t i c a l t e c h n i q u e of high
spatial resolution, limited by t h e i n t e r a c t i o n v o l u m e
of the electron p r o b e a n d t h e electron t r a n s p a r e n t
s a m p l e ( a p p r o x i m a t e l y 5 0 - 2 0 0 n m thick). T h e tech
n i q u e of c h a n n e l l i n g - e n h a n c e d m i c r o a n a l y s i s further
refines the spatial resolution t o t h e level of specific
crystallographic site chemistry, with n o a t t e n d a n t
r e q u i r e m e n t of increased i n s t r u m e n t
capability
(Spence a n d T a f t o 1983, K r i s h n a n 1988).

1.

Principles

T h e principles of c h a n n e l l i n g - e n h a n c e d m i c r o a n a l y s i s
m a y be u n d e r s t o o d by e x a m i n i n g the s o l u t i o n s for the
e q u a t i o n s of d y n a m i c scattering describing the p r o p a
g a t i o n of a n electron b e a m t h r o u g h a m a t e r i a l . If a
thin crystal is o r i e n t e d in such a w a y t h a t only o n e
diffracted b e a m is excited, t h e s o l u t i o n h a s t w o r o o t s
leading t o the t w o Bloch w a v e functions (Hirsch et al.
1965). T h e physical implication of these s o l u t i o n s is
t h a t the electron c u r r e n t flow in t h e direction parallel
to the reflecting p l a n e s (i.e., parallel t o the incident
2
2
b e a m ) is m o d u l a t e d laterally as sin ng o r c o s ng t o
form s t a n d i n g waves with the periodicity of the set of
planes t h a t give rise t o t h e diffracted b e a m (see Fig. 1).
A t t h e exact B r a g g c o n d i t i o n b o t h w a v e s a r e excited
equally, while for positive o r negative d e v i a t i o n s from
the B r a g g o r i e n t a t i o n either of the t w o waves m a y be
preferentially excited. Since the w a v e function is t w o
d i m e n s i o n a l for the t w o - b e a m case, t h a t is, c o n s t a n t
in the direction n o r m a l to the p l a n e of Fig. 1, a

50

B l o c h wave 2

O9

Figure 1
The standing wave pattern of the primary electron beam
in relation to the atomic planes giving rise to a single
diffracted beam

selective s a m p l i n g of the chemistry of specific crystal

l o g r a p h i c p l a n e s is possible by exciting either of the
t w o waves, p r o v i d e d t h a t the energy loss process a n d
the c o n s e q u e n t x-ray g e n e r a t i o n associated with the
e l e c t r o n - a t o m i n t e r a c t i o n o n each set of p l a n e s is
sufficiently localized. T h i s i n t e r a c t i o n distance is
believed t o be of the o r d e r of the B o h r r a d i u s for x-ray
p r o d u c t i o n even for very light elements, while elec
t r o n energy loss processes a r e sufficiently localized for
losses of greater t h a n 2 keV.
It is clear from Fig. 1 t h a t if t h e electron w a v e fields
c a n be theoretically calculated it is possible t o q u a n
tify in a b s o l u t e t e r m s t h e x-ray yield for selected a t o m
layers. H o w e v e r , simple t w o - b e a m t h e o r y d o e s n o t
suffice a n d c o m p l e x m a n y - b e a m calculations a r e
required since the e l i m i n a t i o n of multiple scattering is
e x p e r i m e n t a l l y difficult t o a t t a i n even in t h e thinnest
of crystals for electrons accelerated t h r o u g h high
p o t e n t i a l s ( 1 0 0 - 3 0 0 k V ) . It m u s t be n o t e d t h a t calcu
lation involves t h e a s s u m p t i o n of a delta function for
the e l e c t r o n - a t o m i n t e r a c t i o n distance w h i c h m a y n o t
always be justified ( R o u s s o u w et al. 1988).

2.

Applications

2.1 Planar

Channelling

T h e need for calculating t h e electron wavefield is

o b v i a t e d if a reference x-ray signal from a n element
w h o s e d i s t r i b u t i o n in t h e lattice is k n o w n c a n be

Channelling-Enhanced

utilized. This is usually possible for s t r u c t u r e s t h a t are

chemically layered o n specific planes. T h i s m e t h o d ,
A L C H E M I ( a t o m location by c h a n n e l l i n g - e n h a n c e d
microanalysis), is illustrated using the B2 s t r u c t u r e
( b o d y centered cubic with t w o sublattices) in Figs. 2a,
b. T h e (002) planes c o n t a i n a l t e r n a t e layers of only A
or only a t o m type sublattices while the (110) p l a n e s
are chemically identical. A p l a n a r c h a n n e l l i n g experi
m e n t for this s t r u c t u r e w o u l d therefore consist of
orienting the thin crystal of the p h a s e to be analyzed
so t h a t the t r a n s m i t t e d b e a m a n d the (100) b e a m are
excited. T h e c o r r e s p o n d i n g Bloch waves h a v e the
periodicity of the (100) p l a n e s with c u r r e n t density
p e a k s on the A o r a t o m type layers. If the p r o b l e m
is n o w t o d e t e r m i n e t h e site o c c u p a t i o n of a t h i r d
alloying a d d i t i o n ( a t o m C) to this p h a s e , x-ray spectra
are collected with a positive o r negative d e v i a t i o n
from the exact Bragg c o n d i t i o n for the (100) p l a n e
a n d the intensity ratios IA/IC a n d IQ/IC of the c h a r a c
teristic p e a k s of these elements a r e c o m p a r e d for the
t w o incident b e a m o r i e n t a t i o n s . C a t o m s o c c u p y A
a t o m sites if IJIC d o e s n o t vary with o r i e n t a t i o n a n d
they o c c u p y a t o m sites if IB/IC d o e s n o t vary with
orientation.

Microanalysis

o r i e n t a t i o n (no diffracted b e a m strongly excited)

which yields the average c o m p o s i t i o n .
T h e t e c h n i q u e described d o e s n o t distinguish
b e t w e e n different sites in the s a m e crystallographic
p l a n e . A definite d e t e r m i n a t i o n of each specific site
o c c u p a n c y c a n be achieved if three different sets of
parallel planes with linearly i n d e p e n d e n t diffraction
vectors c a n be found so as t o allow s e p a r a t e experi
m e n t s for each set to be p e r f o r m e d (Banerjee et al.
1988). F u r t h e r , a n e x a m i n a t i o n of Fig. 1 suggests t h a t
interstitial o c c u p a n c i e s c a n also be assessed. Figure 2b
exemplifies the use of this t e c h n i q u e .
2.2 Axial

Channelling

T h e site o c c u p a t i o n c a n be quantified if a n a s s u m p
tion is m a d e t h a t either A or a t o m s o c c u p y only o n e
of the sublattices a n d the p h a s e c o m p o s i t i o n is
k n o w n . In general the characteristic x-ray intensity /
for a n y element Xi (/ elements in the p h a s e ) for a given
o r i e n t a t i o n of the electron b e a m c a n be expressed as
a linear s u m of the c o n t r i b u t i o n s from each of the
parallel planes (, , A , ...)

F o r very small c o n c e n t r a t i o n s of solute, the c o u n t i n g

times required to o b t a i n statistically significant inten
sity values m a y be p r o h i b i t i v e . It h a s been found t h a t
the o r i e n t a t i o n d e p e n d e n c e of the x-ray signal is
increased by at least a factor of t w o u n d e r axial
c h a n n e l l i n g c o n d i t i o n s as c o m p a r e d to p l a n a r c h a n
nelling; t h a t is, w h e n the incident b e a m is oriented
a l o n g or close to a p r o m i n e n t l o w - o r d e r z o n e axis for
the crystal. U n d e r these c o n d i t i o n s the Bloch wave
function is n o t t w o d i m e n s i o n a l a n d reaches a m a x i
m u m o n a t o m positions for the exact z o n e axis
c o n d i t i o n . L a r g e c h a n g e s in the a m p l i t u d e occur for
small tilts. T h u s , even small d i s p l a c e m e n t s in p r o
jected a t o m p o s i t i o n s c a n yield m e a s u r a b l e x-ray
emission effects as o p p o s e d t o the p l a n a r channelling
c o n d i t i o n w h e r e it is necessary to orient the b e a m
a l o n g p l a n e s t h a t clearly s e p a r a t e the projected posi
tions of the a t o m s of interest ( R o u s s o u w et al. 1988).

= PXMX/XCXI\

2.3 Site Occupation

Spectroscopy

+ PxMxfx{\

- Cx)l\

(1)

H e r e , fxf is the fraction of the t o t a l n u m b e r of sites

available for element Xi o n p l a n e A or per unit cell,
x is the t o t a l n u m b e r of available sites per unit cell,
Px.'is a scaling factor including the fluorescence yield,
Cx is the fraction of Xt o n A sites a n d I\ B a r e the
effective Bloch w a v e intensities a v e r a g e d over t h e
thickness of t h e crystal.
F u r t h e r , a n o c c u p a n c y b a l a n c e m a y be w r i t t e n as

"=/

(2)

where Nx. is the n u m b e r of a t o m s of X{ per unit cell

a n d the expression o n the r i g h t - h a n d side yields the
n u m b e r of sites o n the A sublattice p e r unit cell.
If fx. for a n y o n e / is k n o w n , t h a t is, either A o r
a t o m s c a n be a s s u m e d t o o c c u p y only o n e of the
sublattices, t h e n the u n k n o w n s PXj, I\ a n d IB m a y be
eliminated to yield CXj, the r e q u i r e d i n f o r m a t i o n
( K r i s h n a n a n d T h o m a s ' 1 9 8 4 ) . T h e n u m b e r of inci
d e n t b e a m o r i e n t a t i o n s r e q u i r e d t o set u p a n a d e q u a t e
n u m b e r of instances of E q n . (1) to eliminate the
u n k n o w n s d e p e n d s o n the n u m b e r of c o n s t i t u e n t
elements a n d generally includes a n o n c h a n n e l l i n g

by Electron

Energy

Loss

T h e principles of c h a n n e l l i n g a r e applicable to the

p r i m a r y energy loss event in the electron b e a m (which
leads to x-ray emission) a n d therefore the a d v a n t a g e s
of a n electron energy-loss s p e c t r o m e t e r ( E E L S ) over
an energy dispersive x-ray d e t e c t o r ( E D X S ) in access
ing signals from light elements a n d also specific
valence states m a y be utilized t o d e t e r m i n e their
c r y s t a l l o g r a p h i c site d e p e n d e n c e . T w o o t h e r factors
a r e i m p o r t a n t in a n E E L S c h a n n e l l i n g e x p e r i m e n t .
First, for single scattering with a n incident electron
energy of 100-300 k V , the principle of reciprocity
applies so t h a t the source a n d d e t e c t o r c a n be c o n
sidered i n t e r c h a n g e a b l e in p o s i t i o n . T h i s implies t h a t
the d e t e c t o r a p e r t u r e p o s i t i o n in relation to the dif
fraction p a t t e r n influences the c h a n n e l l i n g effect in the
s a m e m a n n e r as the incident b e a m o r i e n t a t i o n a n d
therefore the sensitivity of E E L S to channelling m a y
be s q u a r e d by o p t i m i z i n g b o t h of these p a r a m e t e r s .
Second, for low-energy losses w h e r e the localization
effects referred t o in Sect. 1 b e c o m e i m p o r t a n t , the
d e t e c t o r a p e r t u r e p o s i t i o n m a y be set t o collect elec
t r o n s which a r e scattered t h r o u g h larger angles ( a n d
as a c o n s e q u e n c e u n d e r g o a greater m o m e n t u m
transfer).

51

Channelling-Enhanced

Microanalysis

XB

XB

Figure 2
(a) The channelling technique applied to the B2 structure shown in a [001] projection. The standing wave pattern with
g = 100 has intensity peaks on A planes or planes. The standing wave pattern with g = 110 has intensity peaks on
planes which are chemically identical, (b) Experimental spectra from a Ti-Al-Nb alloy with a B2 structure obtained with
a negative excitation error (S<0) and a positive excitation error ( S > 0 ) for g= 100. The spectra are normalized to the
titanium peak (not shown) and therefore indicate large changes in / T i/ / Nb but little change in / A, / / Nb for the two
orientations. Aluminum and niobium atoms therefore occupy the same sublattice. Note that g = 200 is also excited
illustrating the difficulty of attaining a strictly two-beam condition, and therefore the standing pattern in (a) will include
contributions from other Bloch waves. (For further details see Banerjee et al. 1988)

52

Chemical

3. Experimental

Requirements

T h e e x p e r i m e n t a l r e q u i r e m e n t s for c h a n n e l l i n g e n h a n c e d m i c r o a n a l y s i s a n d the associated e r r o r s a r e

similar to t h o s e for c o n v e n t i o n a l thin-film x-ray mic
roanalysis (Williams 1984). T h e thickness of the elec
t r o n t r a n s p a r e n t s a m p l e s m u s t be greater t h a n the
extinction d i s t a n c e for the o p e r a t i n g reflection, so t h a t
the scattering is d y n a m i c in n a t u r e , b u t less t h a n the
distance at which extensive a t t e n u a t i o n o c c u r s
through absorption. Absorption corrections are not
required since for t h e small c h a n g e s in incident b e a m
o r i e n t a t i o n r e q u i r e d in t h e e x p e r i m e n t the a b s o r p t i o n
p a t h s are effectively c o n s t a n t . S o m e special c o n s i d e r a
tions for the c h a n n e l l i n g e x p e r i m e n t a r e described in
the following.
3.1 Probe Size and Beam
Convergence
T h e p r o b e size is r e q u i r e d to be small e n o u g h t o
sample a perfect region of the crystal, a n d the b e a m
convergence is limited t o a semi-illumination angle
smaller t h a n t h e B r a g g angle so t h a t diffracted disks
d o n o t o v e r l a p . T h e s e p r e c a u t i o n s a r e a d e q u a t e for a
qualitative assessment of site o c c u p a t i o n . F o r situa
tions w h e r e quantification is r e q u i r e d o r w h e r e sensiti
vity to c h a n n e l l i n g is f o u n d to be i n a d e q u a t e a m o r e
careful o p t i m i z a t i o n is r e q u i r e d . T h e r e q u i r e m e n t of
parallel i l l u m i n a t i o n is implicit in the t e c h n i q u e ; h o w
ever, since electrons follow a helical trajectory in the
m a g n e t i c field of t h e objective lens t w o c o m p o n e n t s of
parallelism exista r a d i a l c o m p o n e n t a n d a t a n g e n
tial c o m p o n e n t . I n c r e a s i n g t h e b e a m c o n v e r g e n c e
i m p r o v e s the t a n g e n t i a l parallelism b u t results in a
p o o r e r radial c o m p o n e n t . T h e a p p r o p r i a t e experi
m e n t a l c o n d i t i o n s vary with t h e s t r u c t u r e , s a m p l e a n d
m i c r o s c o p e , a n d m a y be o p t i m i z e d t h r o u g h a simple
set of e x p e r i m e n t s ( K r i s h n a n 1987).
3.2 Orientation and Voltage
T h e precise value of the positive a n d negative excita
tion e r r o r s (deviations from the Bragg c o n d i t i o n ) used
for t h e c h a n n e l l i n g c o n d i t i o n a r e n o t critical a n d will
yield the s a m e fractional o c c u p a n c y for different sets
of o r i e n t a t i o n s since the Bloch c u r r e n t s / A a n d IB a r e
eliminated in t h e f o r m u l a t i o n in Sect. 2 . 1 . H o w e v e r ,
the sensitivity of the e x p e r i m e n t , t h a t is, the dif
ferences in x-ray emission o r energy loss edge height
d u e t o c h a n n e l l i n g at different o r i e n t a t i o n s , is a func
tion of the exact values of excitation used in b o t h
p l a n a r a n d axial channelling. In general, the sensiti
vity increases with increased positive a n d negative
deviation in p l a n a r channelling. A limit t o t h e devi
a t i o n from t h e B r a g g c o n d i t i o n exists d u e to t h e
possible excitation of t h e next diffracted s p o t in t h e
systematic r o w used in p l a n a r c h a n n e l l i n g a n d will
d e p e n d o n b o t h the i n t e r p l a n a r spacing a n d the
extinction distance. E x p e r i m e n t s reveal n o significant
effects d u e t o t h e accelerating voltage except for a
possible inversion in the c h a r a c t e r of o r i e n t a t i o n

Analysis

of Solid

Surfaces

d e p e n d e n c e in the z o n e axis c o n d i t i o n a b o v e a critical

voltage.
It m u s t be p o i n t e d o u t t h a t the r e a s o n s t h a t p e r m i t
the c h a n n e l l i n g c o n d i t i o n to be utilized in d e t e r m i n i n g
site o c c u p a t i o n are precisely t h o s e for which the
excitation of diffracted b e a m s are a v o i d e d in c o n v e n
tional x-ray microanalysis. P l a n a r channelling a n d
axial c h a n n e l l i n g in E D X S a n d E E L S h a v e n o w been
applied to d e t e r m i n e , qualitatively a n d quantitatively,
site o c c u p a t i o n s in a very wide variety of materials
such as alloying a d d i t i o n s to intermetallics, v a r i o u s
m i n e r a l s , nuclear w a s t e ceramics, d o p a n t s in semicon
d u c t o r s a n d m a g n e t i c alloys.
See also: Electron Energy-Loss Spectrometry; Electron
Microprobe Analysis; X-Ray Microanalysis, Quantitative

Bibliography
Banerjee D, Gogia A K, Nandi , Joshi V A 1988 A new
ordered orthorhombic phase in a Ti 3Al-Nb alloy. Acta
Metall. 36: 871-82
Hirsch A, Howie A, Nicholson R B, Pashley D W,
Whelan J 1965 Electron Microscopy of Thin Crystals.
Butterworth, London
Krishnan 1987 When is parallel illumination best for
ALCHEMI? Ultramicroscopy 23: 199-204
Krishnan 1988 Atomic site and species determinations
using channelling and related effects in analytical electron
microscopy. Ultramicroscopy 24: 125-42
Krishnan , Thomas G 1984 A generalisation of atom
location by channelling enhanced microanalysis. J.
Microscopy 136: 97-101
Roussouw C J, Turner S, White J 1988 Axial electron
channelling analysis of perovskite. Philos. Mag. 57:
209^7
Spence J C H, Tafto J 1983 ALCHEMI: a new technique for
locating atoms in small crystals. J. Microscopy 130: 14754
Williams D 1984 Practical Analytical Electron Microscopy
in Materials Science. Philips Electron Optics Publishing,
Mahwah, NJ
D . Banerjee
[Defence Metallurgical R e s e a r c h
L a b o r a t o r y , H y d e r a b a d , India]

Chemical Analysis of Solid Surfaces

Since the early 1970s, the analysis of the elemental
c o m p o s i t i o n of the very n e a r surface region of a solid
h a s b e c o m e r o u t i n e . H o w e v e r , in o r d e r to u n d e r s t a n d
the rich variety of r e a c t i o n s t h a t t a k e place in this
region it is critically i m p o r t a n t t o k n o w n o t only the
surface c o m p o s i t i o n b u t also the n a t u r e of the physi
cal a n d chemical state of the v a r i o u s surface species.
C o n s i d e r a b l e p r o g r e s s h a s been m a d e in recent years

53

Chemical

Analysis

of Solid

Surfaces

in developing techniques to s t u d y the physical struc

tures of species interacting with surfaces; these
techniques include diffraction a n d a n g u l a r - r e s o l v e d
electron spectroscopy.
In the present article, a brief discussion is given of
recent p r o g r e s s in a p p l y i n g surface-sensitive tech
niques t o t h e p r o b l e m of d e t e r m i n i n g t h e chemical
state of surfaces a n d their a d s o r b e d species. Since the
q u e s t i o n of the chemical state is m o r e c o m p l e x a n d
varied t h a n t h a t of physical s t r u c t u r e ( a l t h o u g h the
t w o are interrelated), a c o m m o n t h r e a d a m o n g all the
chemical techniques is a s t r o n g d e p e n d e n c e o n the
i n t e r p r e t a t i o n of c o m p a r a b l e s t a n d a r d s d a t a for m o l
ecules of k n o w n chemical s t r u c t u r e . T o illustrate the
various techniques, a t t e n t i o n will be c o n c e n t r a t e d o n
their a p p l i c a t i o n t o a well-characterized single-surface
a d s o r b a t e system, t h a t is, c a r b o n m o n o x i d e interact
ing with a m e t a l s u b s t r a t e . W i t h only a single excep
tion, the techniques utilize the s h o r t m e a n free p a t h
for energy loss of low-energy electrons in solids t o
achieve surface sensitivity. T h e principle of each tech
n i q u e is illustrated in Fig. 1.

7.

Vibrational

e~(E')

(a)

Spectroscopies

O n e of the oldest m e t h o d s for o b t a i n i n g surface

chemical i n f o r m a t i o n involves m e a s u r e m e n t s of the
s p e c t r u m of v i b r a t i o n a l m o d e s using infrared (ir)
r a d i a t i o n ( ~ 4 0 0 - 3 0 0 0 c m " '). T h e a p p l i c a t i o n of ir
v i b r a t i o n a l s p e c t r o s c o p y (Little 1966, H a i r 1967)
involves detection of t h e a b s o r p t i o n of ir r a d i a t i o n
characteristic of these v i b r a t i o n a l m o d e s . S t r o n g
characteristic s u b s t r a t e a b s o r p t i o n , c o u p l e d with rela
tively weak signals per a d s o r b e d species, h a s led t o
sample p r e p a r a t i o n being the limiting factor in
o b t a i n i n g surface-related ir spectra. E x c e p t for special
multiple-reflection techniques, ir studies of a d s o r b e d
species n o r m a l l y e m p l o y samples with high surfaceto-bulk ratios such as p o w d e r s , o r catalytic-type
materials in which small metallic particles are s u p
p o r t e d a n d dispersed o n a high-surface-area relatively
t r a n s p a r e n t m a t e r i a l such as silica.
Infrared spectral m e a s u r e m e n t s , which involve
detecting the a b s o r p t i o n of r a d i a t i o n as a function
of wavelength, p r o b e the b o n d i n g characteristics of
the a d s o r b e d c o m p l e x (specifically, the s p e c t r u m of
i n t e r a t o m i c - b o n d i n g force c o n s t a n t s ) a n d yield infor
m a t i o n o n the strength of the b o n d s between v a r i o u s
c o m p o n e n t s of the c o m p l e x (e.g., C H , C C ,
C O , C = 0 bonds). Characteristic group and band
ir a b s o r p t i o n frequencies for m o l e c u l a r species h a v e
been extensively t a b u l a t e d a n d i n t e r p r e t a t i o n of the
spectra of a d s o r b e d species h a s d e p e n d e d heavily o n a
detailed c o m p a r i s o n with s t a n d a r d spectra o b t a i n e d
from well-defined m o l e c u l a r systems of k n o w n c h e m
ical s t r u c t u r e .
T h e s t u d y of C O c h e m i s o r p t i o n represents a p a r
ticularly successful a p p l i c a t i o n of ir spectroscopy.

54

e(E)

Solid

vacuum
(b)

Figure 1
(a) A schematic view of the vibrational techniques,
infrared (ir) and low-energy-electron loss spectroscopies
(LEELS), probing a simple molecule adsorbed on a solid
surface, (b) A schematic representation of x-ray and
ultraviolet photoelectron spectroscopies (XPS and UPS,
respectively) and Auger electron spectroscopy (AES)
probing a solid surface. Energy is plotted on the vertical
axis with electrons bound to the solid being positioned
below the vacuum level and the kinetic energy of ejected
electrons is given by their position above the vacuum level

T h i s is largely d u e t o the wide a r r a y of wellc h a r a c t e r i z e d m e t a l c a r b o n y l molecules available as

m o d e l s for i n t e r p r e t a t i o n . A s a n e x a m p l e , Fig. 2a
s h o w s the ir s p e c t r u m of t h e m o l e c u l a r c o m p l e x
F e 2 ( C O ) 9 . F r o m the analysis of a large n u m b e r of such
m e t a l c a r b o n y l s , it is k n o w n t h a t the C O g r o u p in
these molecules is b o u n d in t w o structurally distinct
forms. T h e s e differ, as s h o w n in Fig. 2a, in t h a t the
linear form is b o u n d t o a single m e t a l a t o m , w h e r e a s
the b r i d g e d form is s h a r e d by t w o m e t a l a t o m s . T h e
1
linear f o r m is f o u n d t o a b s o r b ir a b o v e 2000 c m " a n d
1
the bridged form a b s o r b s below 2000 c m " . T h u s , for
F e 2 ( C O ) 9 , which c o n t a i n s three b r i d g i n g a n d six linear
1
C O g r o u p s , t h e a b s o r p t i o n p e a k s a b o v e 2000 c m " are
assigned t o v i b r a t i o n s involving the linear c o m
1
p o n e n t s a n d t h e s t r u c t u r e at 1850 c m " is associated
with the bridged c o m p o n e n t s .

Chemical

1700

1800

240

780

1900

2000

2100

2200

1320

I860

2400

2940

Wavenumber

( c m ')

Figure 2
Carbon monoxide vibrational spectra: classical ir
absorption spectra for (a) the molecular complex Fe 2(CO) 9
(Cotton 1960) and (b) CO adsorbed on high-surface-area
nickel supported on S i 0 2 (Eischens et al. 1956); (c) the
electron-energy-loss spectrum for CO adsorbed on the
(100) crystal face of nickel (Andersson 1977)

A s a n e x a m p l e of t h e c h e m i s o r p t i o n a n a l o g u e , the
ir s p e c t r u m of C O c h e m i s o r b e d o n S i 0 2 - s u p p o r t e d
nickel is s h o w n in Fig. 2 b . H e r e a g a i n , there is a n
1
a b s o r p t i o n p e a k a b o v e 2000 c m " which is assigned t o
the linearly b o u n d C O molecule a n d a n a b s o r p t i o n
-1
p e a k below 2000 c m
ascribed t o the b r i d g e d form.
H o w e v e r , t h e b e h a v i o r of the spectra is c o m p l e x with
varying a m o u n t s of c h e m i s o r b e d C O , p e r h a p s as a
result of lateral i n t e r a c t i o n s b e t w e e n a d s o r b e d C O
molecules, C O being b o u n d t o a n a r r a y of surface
sites, o r d u e t o s u p p o r t i n t e r a c t i o n s .
T h e difficulty in o b t a i n i n g a detailed i n t e r p r e t a t i o n
of such e x p e r i m e n t s , as i n d i c a t e d earlier, stems largely
from t h e f o r m of the s a m p l e s r e q u i r e d , which are n o t
a m e n a b l e t o a d e q u a t e surface c h a r a c t e r i z a t i o n . H o w
ever, a n a l t e r n a t i v e t e c h n i q u e for s t u d y i n g the v i b r a
tional s t r u c t u r e of surfaces a n d a d s o r b e d species h a s
b e c o m e available which largely c i r c u m v e n t s this diffi
culty. T h e t e c h n i q u e t a k e s a d v a n t a g e of t h e energy
losses suffered b y very-low-energy electrons in scatter
ing from surfaces a n d a d s o r b e d species, a n d c a n be

Analysis

of Solid

Surfaces

applied t o well-characterized single-crystal surfaces of

very low surface a r e a . T h e scheme is n o r m a l l y
referred t o as low-energy-electron loss spectroscopy
( L E E L S ) a n d h a s b e c o m e very p o p u l a r in surface
studies ( I b a c h et al. 1977). A l t h o u g h the resolution of
the t e c h n i q u e is c o n s i d e r a b l y lower t h a n t h a t found in
1
n o r m a l ir m e a s u r e m e n t s ( a b o u t 80 c m for L E E L S
1
c o m p a r e d with 1 c m " for ir), the s u r f a c e - a d s o r b a t e
system c a n be simplified a n d characterized to a degree
w h i c h t e n d s to c o m p e n s a t e for the lack of detail in the
spectral results. In a d d i t i o n , the energy r a n g e which
c a n be conveniently covered is c o n s i d e r a b l y b r o a d e r
-1
t h a n with ir ( a b o u t 8 0 - 8 0 0 0 c m
for L E E L S c o m
1
p a r e d to 2 0 0 - 4 0 0 0 c m " for ir) a n d i n f o r m a t i o n con
cerning the a n g u l a r b e h a v i o r of the inelastic loss is
readily available.
A n e x a m p l e of the L E E L S results for C O a d s o r b e d
o n a nickel (100) single-crystal surface is s h o w n in Fig.
2c. N o t e t h a t these results s h o w the s a m e differentia
tion in the C O stretching frequency a b o v e a n d below
1
2000 c m
between the linear a n d bridge b o n d i n g
sites. T h i s mixed linear a n d b r i d g e b o n d i n g situation
c o r r e s p o n d s , however, to low c o v e r a g e (estimated to
be less t h a n ~ 0 . 1 % of the surface) at 293 K. Similar
e x p o s u r e at 173 yields, essentially, only the bridge
1
b o n d e d a r r a n g e m e n t (at ~ 1924 c m " ) . T h e structure
1
at 476 c m " c o r r e s p o n d s to t h e N i - ( C O ) stretching
v i b r a t i o n . T h e c o n d i t i o n s h o w n in Fig. 2c is seen to be
in r a t h e r close a g r e e m e n t with t h e dispersed-metal ir
d a t a s h o w n in Fig. 2b.

2. Photoelectron

Spectroscopy

T h e v i b r a t i o n a l spectroscopies p r o v i d e i n f o r m a t i o n
c o n c e r n i n g local b o n d i n g , which ultimately h a s its
source in the electronic s t r u c t u r e of the system. T h e
p h o t o e l e c t r o n t e c h n i q u e s , o n the o t h e r h a n d , p r o b e
b o n d i n g in t e r m s of the electronic characteristics of
the system. T h i s is a c c o m p l i s h e d by exciting electrons
from their b o u n d states with nearly m o n o c h r o m a t i c
light (in the uv a n d x-ray p o r t i o n s of the e l e c t r o m a g
netic s p e c t r u m ) a n d energy a n a l y z i n g the resulting
p h o t o e l e c t r o n s . Historically, the energy r a n g e of the
r a d i a t i o n h a s been b r o k e n i n t o regions a c c o r d i n g to
the m o d e of p r o d u c t i o n a n d these h a v e been referred
to as ultraviolet ( U P S ) a n d x-ray ( X P S ) p h o t o e l e c t r o n
spectroscopies (for the m o s t p a r t , U P S h a s involved
valence-level a n d X P S core-level studies).
T h e core-level w o r k p r o b e s the local chemical en
v i r o n m e n t by l o o k i n g for c h a n g e s in core-level bind
ing energies as the chemical e n v i r o n m e n t is altered.
T h e s e chemical shifts result from valence-level c h a r g e
transfer a n d e n v i r o n m e n t a l electron-screening effects
( S i e g b a h n 1974). T h e a d v a n t a g e of the core-level
p h o t o e l e c t r o n t e c h i q u e is t h a t , since core-level bind
ing energies are characteristic of the p a r t i c u l a r a t o m
being excited, the results a r e a t o m specific (the overall
energy p o s i t i o n s p r o v i d i n g an elemental analysis

55

Chemical Analysis of Solid

Surfaces

while the detailed lineshapes give i n f o r m a t i o n o n the

local a t o m i c e n v i r o n m e n t ) . A l t h o u g h a large a m o u n t
of w o r k h a s been d o n e with r e g a r d to m o l e c u l a r
systems, the d e v e l o p m e n t of the core-level p h o t o e l e c t r o n t e c h n i q u e h a s n o t a t t a i n e d a p o s i t i o n , as yet,
w h e r e chemical shifts in surface m e a s u r e m e n t s c a n be
associated directly with local e n v i r o n m e n t a l effects.
This is p e r h a p s principally d u e to the limited u n d e r
s t a n d i n g presently available r e g a r d i n g electron
screening in these systems, a l t h o u g h the necessary
d e p e n d e n c e in t h e e x p e r i m e n t a l d a t a o n small energy
shifts (only a few eV) of a single level is certainly a n
i m p o r t a n t factor.
In valence-level p h o t o e l e c t r o n s p e c t r o s c o p y ( B r a d s h a w et al. 1975), the energy d i s t r i b u t i o n of p h o t o e l e c t r o n s excited from occupied valence levels within
p e r h a p s 2 0 - 3 0 eV of the F e r m i level (or the highest
occupied m o l e c u l a r orbital) is detected. A n e x a m p l e
of this k i n d of d a t a is s h o w n in Fig. 3a for the
a d s o r p t i o n system C O o n p a l l a d i u m ( l 11). A spec
t r u m similar to this, t a k e n w i t h o u t the a d s o r b e d C O ,
s h o w s t h a t the s t r u c t u r e below a b o u t 6 e V is d u e t o
p h o t o e m i s s i o n from the m e t a l d electrons a n d d o e s
n o t s h o w the t w o p e a k s a t a p p r o x i m a t e l y 8 e V a n d
11 eV. T h u s , the C O a d s o r p t i o n is viewed as a d d i n g t o
the overall s u r f a c e - a d s o r b a t e electronic states at these
energies. F i g u r e 3b s h o w s similar d a t a for the m e t a l
c a r b o n y l R h 6 ( C O ) 1 6, which c o n t a i n s a central cluster
of six m e t a l a t o m s s u r r o u n d e d by sixteen C O g r o u p s
a n d is a typical m o d e l molecule for C O - m e t a l i n t e r a c
tions. T h e similarity between these t w o spectra leads
to the conclusion t h a t C O a d s o r p t i o n is indeed closely
related to the c a r b o n y l - b o n d i n g s i t u a t i o n . N o t e the
decreased ^/-electron c o n t r i b u t i o n below 6 e V in the
m o l e c u l a r case. F i g u r e 3c s h o w s the p h o t o e l e c t r o n
result from a n isolated C O molecule, which indicates
three m o l e c u l a r orbital c o n t r i b u t i o n s in a g r e e m e n t
with theoretical calculations. T h e s e a r e indicated in
the figure a c c o r d i n g t o their s y m m e t r y as t h e 5, 1
a n d 4 m o l e c u l a r orbitals. T h e multiple s t r u c t u r e in
the n e i g h b o r h o o d of each line is d u e t o m o l e c u l a r
v i b r a t i o n s excited d u r i n g the p h o t o e m i s s i o n process.
It is f o u n d in p h o t o e l e c t r o n s p e c t r o s c o p y t h a t the
v a r i a t i o n in intensity of a given p h o t o e m i s s i o n struc
t u r e with the w a v e l e n g t h o r energy of the incident
light is dictated by the detailed c h a r a c t e r of t h e o r b i t a l
involved in t h e emission. Such w o r k with respect t o
the P d - C O a d s o r p t i o n system ( G u s t a f s s o n et al. 1975)
h a s led t o the c o n c l u s i o n t h a t the p e a k at a p p r o x i m
ately 8 eV in Figs. 3a a n d 3b is d u e t o p h o t o e m i s s i o n
from b o t h the 5 a n d In levels, t h e 5 h a v i n g been
driven to a deeper b i n d i n g energy relative t o the \n
d u e to the C O - m e t a l b o n d i n g . T h e 11 eV p e a k is
identified with the 4 orbitals. T h u s , for either C O
c h e m i s o r p t i o n o r C O c a r b o n y l b o n d i n g , the m a j o r
p e r t u r b a t i o n involves only the C O 5 m o l e c u l a r
orbital.
O n e difficulty with the valence level p h o t o e m i s s i o n
t e c h n i q u e , however, is the fact t h a t it is n o t a t o m

56

4
8
12
Relative electron energy (eV)

Figure 3
Ultraviolet photoelectron spectra for (a) CO adsorbed on
the (111) crystal face of palladium, (b) the molecular
complex Rh 6(CO) 16 and (c) the gas phase CO molecule
(Conrad et al. 1976). The energy scale is referred to the
Fermi energy

specific. R a t h e r , it t e n d s t o a v e r a g e c o n t r i b u t i o n s
from the system as a w h o l e . T h u s , m e a s u r e m e n t s o n
small coverages of C O o n p a l l a d i u m a r e m a d e with
difficulty b e c a u s e of t h e lack of c o n t r a s t with respect
t o the m e t a l d-level c o n t r i b u t i o n . T h i s lack of c o n t r a s t
is certainly evident from the fact t h a t n o indication is
given in Figs. 3a a n d 3b t h a t the bridged o r linear
b o n d i n g sites p r o d u c e spectral differences ( R h 6 ( C O ) 1 6
h a s four b r i d g e d a n d 12 linear b o n d i n g sites for C O ) .
F u r t h e r m o r e , there is n o i n d i c a t i o n of b a c k d o n a t i o n
of m e t a l d electrons i n t o t h e n o r m a l l y e m p t y 2n
a n t i b o n d i n g level of t h e C O as a result of the b o n d i n g .
T h e b a c k - b o n d i n g m o d e l , s h o w n in Fig. 4, h a s
b e c o m e very i m p o r t a n t in c o n c e p t u a l i z i n g the C O m e t a l i n t e r a c t i o n . Back d o n a t i o n i n t o the C O In
a n t i b o n d i n g state from the m e t a l d electrons helps t o
explain w h y the b o n d b e t w e e n c a r b o n a n d oxygen is
w e a k e n e d (as evidenced by the v i b r a t i o n a l results
discussed in Sect. 1) as a result of the m e t a l i n t e r a c t i o n
a n d is i m p o r t a n t in u n d e r s t a n d i n g the a d s o r p t i o n as
being the first step t o w a r d surface dissociation. T h i s
c o n c e p t h a s n o t been verified b e y o n d the v i b r a t i o n a l

Chemical

Figure 4
The back-bonding model for CO interactions. Relevant
metal d orbitals are shown to the left, CO orbitals to the
right and complex orbitals in the center. The primary
interaction results from the overlap of the filled 5
molecular orbital of CO with the empty metal d orbital.
The resulting charge transfer is partially compensated by
back donation from the filled metal d orbitals into the
normally empty antibonding CO In molecular orbital

results, h o w e v e r , a n d is n o t e n c o u r a g e d by t h e p h o t o electron d a t a s h o w n in Fig. 3, a l t h o u g h this a g a i n m a y

be d u e simply t o t h e lack of c o n t r a s t in the spectral
results o r t h e difficulty of i n t e r p r e t i n g d - b a n d
emission in the presence of a b s o r b e d overlayers
(Engel a n d Ertl 1979).

3. Auger

Electron

Spectroscopy

A u g e r electron s p e c t r o s c o p y ( A E S ) , w h i c h h a s
received r e n e w e d a t t e n t i o n as a p r o b e of valence
electronic s t r u c t u r e ( R y e et al. 1979), s h o w s p r o m i s e
for yielding i n f o r m a t i o n w h i c h c o m p l e m e n t s a n d
extends t h a t o b t a i n e d from t h e p h o t o e l e c t r o n tech
niques. P h o t o e l e c t r o n s o r i g i n a t e from valence states
of the c o m p l e t e system a n d for c h e m i s o r p t i o n this c a n
involve electrons from the s u b s t r a t e as well as from
c h e m i s o r b e d species. In c o n t r a s t , A E S yields i n f o r m a
tion a b o u t the valence electronic s t r u c t u r e in t h e
i m m e d i a t e n e i g h b o r h o o d of a n a t o m i c p o s i t i o n . T h i s
localization results from t h e fact t h a t t h e initial step in
A E S is the ejection of a c o r e electron by either p h o t o n
or electron i m p a c t . T h u s , t h e initial state in A E S is t h e
final state in X P S . T h e system c a n t h e n relax by
h a v i n g this c o r e h o l e filled by a higher lying electron
with t h e excess energy being given to t h e ejection of a
second electron, t h e A u g e r electron. T h e chemical

Analysis

of Solid

Surfaces

sensitivity c o m e s in w h e n o n e o r b o t h of these elec

t r o n s o r i g i n a t e from valence states. T h e kinetic energy
Ek of t h e ejected A u g e r electron is d e t e r m i n e d by the
b i n d i n g energies of the c o r e (Ic) a n d valence electrons
(Ijk) involved, as well as t h e repulsion (t/ e f f) between
t h e t w o holes in t h e final state, Ek = Ic- l} - Ik - Ueff.
T h e localization involved in A E S , however, is m o s t
p r o n o u n c e d in the intensity m o d u l a t i o n of the spec
t r u m of t r a n s i t i o n s t o t h e different final states j a n d k.
Since t h e intensity of a n A u g e r t r a n s i t i o n is directly
related t o t h e electron density in the i m m e d i a t e neigh
b o r h o o d of t h e a t o m c o n t a i n i n g the initial core hole,
the relative A u g e r intensities t o the s a m e final state
b u t from different a t o m i c species in t h e system are a
direct m e a s u r e of t h e v a r i a t i o n in orbital electron
density a t these different a t o m i c sites.
T h e C O molecule is a g o o d e x a m p l e of this intensity
v a r i a t i o n . T h e c a r b o n s p e c t r u m from C O is given in
Fig. 5a o n a t w o - h o l e b i n d i n g - e n e r g y scale o b t a i n e d
by s u b t r a c t i n g t h e o b s e r v e d core-hole b i n d i n g energy
from the e x p e r i m e n t a l A u g e r electron kinetic energy
(Ek Q. T h e t w o large p e a k s slightly below - 40 eV
involve t h e 5 a n d 1 m o l e c u l a r orbitals of C O . T h e
5 m o l e c u l a r o r b i t a l is a lone-pair type with its
electron density c o n c e n t r a t e d at t h e c a r b o n site. A s
a result these t r a n s i t i o n s a r e intense in the c a r b o n
s p e c t r u m , b u t barely discernible in the oxygen spec
t r u m ( J e n n i s o n et al. 1981). T h e m o l e c u l a r - o r b i t a l
s t r u c t u r e s of N O a n d C O are nearly identical a n d
differ only in the electron o c c u p a t i o n of t h e In orbital.
In C O , this o r b i t a l is e m p t y a n d a n t i b o n d i n g , w h e r e a s
in N O it is b o n d i n g a n d c o n t a i n s o n e electron. A s is
seen from c o m p a r i s o n of Figs. 5a a n d 5b, the o c c u p a
tion of this level in N O leads t o a new e x p e r i m e n t a l
p e a k o n the high-energy side of t h e N ( K V V ) s p e c t r u m
of N O w h i c h is a b s e n t in t h e C ( K V V ) s p e c t r u m of
CO.
T h e o c c u p a t i o n of the In level in N O c o m p a r e d to
C O is equivalent t o t h e process t h a t occurs in the
b a c k - b o n d i n g m e c h a n i s m for c h e m i s o r b e d C O a n d
m e t a l c a r b o n y l s , except t h a t t h e s o u r c e of electrons in
this latter case is t h e m e t a l d orbitals. T h e C ( K V V )
spectra of the t w o m e t a l c a r b o n y l s M o ( C O ) 6 a n d
C o ( C O ) 3 N O a r e s h o w n in Fig. 5, t o g e t h e r with the
spectra of N O a n d C O . T h e m a j o r difference between
t h e C ( K V V ) spectra of C O a n d t h e m e t a l c a r b o n y l s is
t h e a p p e a r a n c e of a new p e a k o n t h e high-energy side
of t h e spectra at a p p r o x i m a t e l y t h e s a m e relative
energy as in the case of N O . U s i n g t h e localized
c h a r a c t e r of A E S as a valence p r o b e , a n d the m o r e
c o m p l e x C o ( C O ) 3 N O molecule, which c o n t a i n s o n e
N O g r o u p a n d three C O g r o u p s , o n e o b t a i n s a d d i
t i o n a l c o n f i r m a t i o n of the b a c k - b o n d i n g m o d e l . A
direct c o m p a r i s o n of the N ( K V V ) a n d C ( K V V ) spec
t r a for C o ( C O ) 3 N O s h o w s the b a c k - b o n d i n g p e a k t o
be m o r e intense in t h e N ( K V V ) s p e c t r u m consistent
with a n o n z e r o initial p o p u l a t i o n of the In level in the

57

Chemical

Analysis

of Solid

Surfaces

A ckno

wledgement

T h e w o r k of t h e a u t h o r s is s p o n s o r e d by t h e U S
D e p a r t m e n t of E n e r g y u n d e r C o n t r a c t N o . D E AC04-76-DP00789.
See also: Auger Electron Spectroscopy; Depth Profiling;
Electron Spectroscopy for Chemical Analysis; Infrared
Spectroscopy

Bibliography

-100

-80

-60
( F k- I c)

-40

-20

(eV)

Figure 5
Auger electron spectra for (a) C(KVV) of CO,
(b) N(KVV) of NO, (c) C(KVV) of Co(CO) 3NO and
(d) Mo(CO) 6. The notation C(KVV) refers to an initial
carbon K(ls) core hole and both final-state holes in the
valence levels

N O molecule. This a p p e a r s to be the first direct

evidence of back d o n a t i o n into n o r m a l l y e m p t y m o l e
cular orbitals for the C O - m e t a l system.

4.

Summary

T h e further d e v e l o p m e n t a n d e x p l o i t a t i o n of these
techniques, which are sensitive to chemical e n v i r o n
m e n t , offer great p o t e n t i a l for o b t a i n i n g a n u n d e r
s t a n d i n g of the n a t u r e of surface chemical reactivity.
U n f o r t u n a t e l y , n o n e of the t e c h n i q u e s presently avail
able are c a p a b l e of i n d e p e n d e n t l y p r o v i d i n g sufficient
i n f o r m a t i o n to achieve this u n d e r s t a n d i n g a n d a
concerted a p p r o a c h involving several of the m e t h o d s
is n o r m a l l y required. In a d d i t i o n , w o r k with wellcharacterized s u r f a c e - a d s o r b a t e systems a n d stan
d a r d m o l e c u l a r species is a n a b s o l u t e necessity. T h e
all pervasive influence of surface chemical effects in
m a t e r i a l s p r o p e r t i e s a n d processing, h o w e v e r , m a k e s
the c o m p l i c a t i o n s of m o d e r n surface research well
w o r t h the extra effort.

58

Andersson S 1977 Vibrational excitations and structure of

CO absorbed on Ni(100). Solid State Commun. 21: 75-81
Bradshaw A M, Cederbaum L S, Domcke W 1975 Ultra
violet photoelectron spectroscopy of gases absorbed on
metal surfaces. Struct. Bonding (Berlin) 24: 133-69
Conrad H, Ertl G, Knozinger H, Kuppers J, Latta 1976
Polynuclear metal carbonyl compounds and chemisorption of CO on transition metal surfaces. Chem. Phys.
Lett. 42: 115-18
Cotton F A 1960 The infra-red spectra of transitional metal
complexes. In: Lewis J, Wilkins R G (eds.) 1960 Modern
Coordination Chemistry. Wiley, New York
Eischens R P, Francis S A, Pliskin W A 1956 The effect of
surface coverage on the spectra of chemisorbed CO. J.
Phys. Chem. 60: 194-201
Engel T, Ertl G 1979 Elementary steps in the catalytic
oxidation of carbon monoxide on platinum metals. Adv.
Catal. 28: 1-78
Gustafsson T, Plummer W, Eastman D E, Freeouf J L
1975 Interpretation of the photoelectron spectra of molecularly absorbed CO. Solid State Commun. 17: 391-6
Hair L 1967 Infrared Spectroscopy in Surface Chemistry.
Dekker, New York
Ibach H, Hopster H, Sexton 1977 Analysis of surface
reactions by spectroscopy of surface vibrations. Appl.
Surf Sci. 1: 1-24
Jennison D R, Stucky G D, Rye R R, Kelber J A 1981
Analysis of transition metal carbonyl Auger line shapes.
Phys. Rev. Lett. 46: 911-14
Little L 1966 Infrared Spectra of Absorbed Species.
Academic Press, New York
Rye R R, Houston J E, Jennison D R, Madey ,
Holloway 1979 Chemical information in Auger
spectroscopy. Ind. Eng. Chem., Prod. Res. Dev. 18: 2-7
Siegbahn 1974 Electron spectroscopy: an outlook. J.
Electron Spectrosc. Relat. Phenom. 5: 3-97
J. E. H o u s t o n a n d R. R. R y e
[Sandia N a t i o n a l L a b o r a t o r i e s , A l b u q u e r q u e ,
New Mexico, USA]

Composite Materials: Nondestructive

Evaluation
T h e c o m p l e x i t y of c o m p o s i t e c o m p o n e n t s c a n vary
very widely, from a simple glass-reinforced plastic
( G R P ) s t o r a g e t a n k to a sophisticated a e r o s p a c e
c o m p o n e n t fabricated from a variety of m a t e r i a l s a n d
exhibiting a very c o m p l i c a t e d l a y u p . E q u a l l y there
c a n be a n e n o r m o u s v a r i a t i o n in t h e thickness a n d
overall size of the c o m p o n e n t s , from small c a r b o n -

Composite

fiber c o m p o s i t e ( C F C ) p a n e l s o n satellite s t r u c t u r e s ,
which m i g h t be only 0.25 m m thick, to t h e 30 m long,
25 m m thick, G R P hull of a n a v a l m i n e h u n t e r . T h e
r e q u i r e m e n t s for n o n d e s t r u c t i v e e v a l u a t i o n ( N D E )
will therefore also vary widely a n d it is only possible
to give here a s h o r t guide t o t h e principles involved
a n d an i n t r o d u c t i o n to t h e t e c h n i q u e s available. F o r
simplicity the discussion will largely be limited t o
materials h a v i n g o r g a n i c m a t r i c e s . M e t a l - m a t r i x c o m
posites are of g r o w i n g i m p o r t a n c e a n d a significant
a m o u n t of N D E h a s been e m p l o y e d o n t h e m , b u t the
N D E r e q u i r e m e n t s a r e as yet far from clear ( R e y n o l d s
1986).

7. Nondestructive

Evaluation

Policy

T h e principal objective of n o n d e s t r u c t i v e e v a l u a t i o n
is to p r o v i d e a s s u r a n c e o n the q u a l i t y a n d s t r u c t u r a l
integrity of a p a r t i c u l a r c o m p o n e n t . T h i s m a y be
achieved either directly by using n o n d e s t r u c t i v e in
spection t e c h n i q u e s t o detect specific defects, o r in
directly by m o n i t o r i n g o r c o n t r o l l i n g the fabrication
process. T h e latter a p p r o a c h is, h o w e v e r , really only
an extension of t h e u s u a l process c o n t r o l p r o c e d u r e s
which a r e necessary in o r d e r t o achieve a consistent
p r o d u c t . A d d i t i o n a l N D E m i g h t be p r o v i d e d t o assist
in optimizing the fabrication p r o c e d u r e by, for ex
a m p l e , the a d d i t i o n of a device t o m o n i t o r t h e local
state of c u r e . T h e m a j o r i t y of N D E is, h o w e v e r ,
c o n c e r n e d with the d e t e c t i o n a n d c h a r a c t e r i z a t i o n of
defects o r a n o m a l i e s .
In o r d e r t o illustrate the types of defects t h a t
m i g h t be s o u g h t , consider, for e x a m p l e , a c a r b o n fiber c o m p o s i t e a e r o s p a c e c o m p o n e n t fabricated in a n
autoclave. T h e following defects are likely t o be of
importance: delaminations (separations
between
plies), d i s b o n d s , p o r o s i t y in the l a m i n a t e s o r b o n d
line, fiber m i s o r i e n t a t i o n , missing plies, v a r i a t i o n s in
fiber v o l u m e fraction (resin-rich o r resin-starved
areas), foreign inclusions a n d h o n e y c o m b c o r e misfit
(gaps a n d splices).
Clearly, in o r d e r t o decide which defects m u s t be
detected, a n d t o set defect-acceptance s t a n d a r d s , it is
necessary t o u n d e r s t a n d t h e effect t h a t a specific
defect h a s o n t h e p e r f o r m a n c e of a given c o m p o n e n t .
Inspection p r o c e d u r e s c a n be b o t h expensive a n d time
consuming and many composite components have
p r o v e d t o be surprisingly t o l e r a n t t o defects, so care
should be t a k e n t o e n s u r e t h a t t h e r e q u i r e m e n t s for
inspection a r e n o t unnecessarily r i g o r o u s ( S t o n e a n d
C l a r k e 1987).
A s a general guide it m a y be said t h a t there a r e t w o
m a i n a p p r o a c h e s t o t h e use of N D E t o assess quality.
T h e first a p p r o a c h a i m s t o p r o v i d e a q u a l i t a t i v e
assessment a n d is typified by t h e w a y t h a t r a d i o g r a
p h y is used t o assess w h e t h e r the level of p o r o s i t y is
acceptable. R a d i o g r a p h s of p r o d u c t i o n c o m p o n e n t s
are c o m p a r e d with t h o s e of d e v e l o p m e n t c o m p o n e n t s .

Materials:

Nondestructive

Evaluation

Physical tests of these c o m p o n e n t s against the design

criteria e n a b l e e x a m p l e s of a c c e p t a b l e a n d u n a c c e p
table q u a l i t y t o be identified. T h e second a p p r o a c h is
less subjective a n d e m p l o y s q u a n t i t a t i v e a c c e p t a n c e
s t a n d a r d s , such as a rejection of a n y c o m p o n e n t
c o n t a i n i n g a n a r e a of d e l a m i n a t i o n greater t h a n , say,
2
500 m m .

2.

Visual

Inspection

T h e value of simple visual inspection s h o u l d n o t be

u n d e r e s t i m a t e d . It is, for e x a m p l e , possible to o b t a i n
useful i n f o r m a t i o n a b o u t t h e q u a l i t y of even quite
thick G R P c o m p o n e n t s by e x a m i n i n g t h e m visually
against a brightly lit b a c k g r o u n d . Even with o p a q u e
m a t e r i a l s , such as C F C , it is often informative to
p e r f o r m a p r e l i m i n a r y visual e x a m i n a t i o n of the sur
faces. P o o r l a m i n a t e s are s o m e t i m e s revealed by the
presence of p o r o s i t y or resin-starved areas o n the
surface, a n d light polishing of t h e edges of l a m i n a t e s
is often sufficient to reveal edge d e l a m i n a t i o n s . Visual
inspection m a y be e n h a n c e d by the use of c o n v e n
t i o n a l dye p e n e t r a n t s . Such p e n e t r a n t s m a y , however,
be difficult to r e m o v e a n d s h o u l d be used with c a u t i o n
if a s u b s e q u e n t repair is i n t e n d e d .

3. Ultrasonic

Inspection

T h i s is by far the m o s t widely used inspection m e t h o d

for l a m i n a t e d c o m p o s i t e m a t e r i a l s , being particularly
suited t o t h e detection of defects n o r m a l to the
i n t e r r o g a t i n g b e a m . A large r a n g e of techniques is
available using frequencies of 1-50 M H z to meet
r e q u i r e m e n t s r a n g i n g from c o a r s e defect (e.g., disb o n d ) d e t e c t i o n , t h r o u g h void c o n t e n t d e t e r m i n a t i o n ,
t o detailed defect c h a r a c t e r i z a t i o n . F o r e x a m p l e , a t
o n e e x t r e m e there is m a n u a l c o n t a c t s c a n n i n g using a
d i g i t a l - r e a d o u t u l t r a s o n i c thickness g a u g e , while at
t h e o t h e r there c o u l d be a c o m p u t e r - c o n t r o l l e d
multiaxis i m m e r s i o n s c a n n i n g system.
A c o m m o n feature of all u l t r a s o n i c techniques is
t h e r e q u i r e m e n t t o c o u p l e t h e t r a n s d u c e r t o the speci
m e n in such a w a y t h a t t h e transfer of energy i n t o a n d
o u t of t h e specimen is m a x i m i z e d . T h e efficiency of
this c o u p l i n g d e p e n d s o n t h e acoustic p r o p e r t i e s of
t h e v a r i o u s m a t e r i a l s involved. If y o u t a k e , for ex
a m p l e , a w a t e r - C F C (or C F C - w a t e r ) interface, t h e n
s o m e 7 3 % of the incident energy is t r a n s m i t t e d . It is
often c o n v e n i e n t , therefore, t o i m m e r s e b o t h the
specimen a n d t h e t r a n s d u c e r in a w a t e r b a t h . W h e n
using m a n u a l s c a n n i n g , however, it is usually m o r e
practical t o use a grease o r gel c o u p l a n t ; this is quite
satisfactory a l t h o u g h the c o u p l i n g is m o r e variable.
C o n s i d e r n o w a C F C - a i r interface. T h i s time only
0 . 0 3 % of t h e energy is t r a n s m i t t e d a n d 9 9 . 9 7 % is
reflected. Because of this, air-filled d e l a m i n a t i o n s ,
p o r o s i t y a n d d i s b o n d s give rise t o s t r o n g echoes.

59

Composite

Materials:

Nondestructive

Evaluation

tions will be small a n d will usually n o t be detected.

T h e result is t h a t t h e m a t e r i a l in t h e s h a d o w region
b e h i n d t h e first defect will n o t be inspected a n d
a d d i t i o n a l defects will n o t be f o u n d . This effect is
especially noticeable with i m p a c t d a m a g e which
causes m u l t i p l e d e l a m i n a t i o n s .
3.3 Ultrasonic

Figure 1
-scan showing front and back surface reflections from a
ten-ply composite

F u r t h e r m o r e the fact t h a t there is a s t r o n g e c h o from

the rear face of a n a i r - b a c k e d l a m i n a t e m e a n s t h a t it
can readily be inspected from o n e side.
3.1 Immersion

Testing

In s o m e cases the use of a gel-coupled c o n t a c t t r a n s

ducer is u n a v o i d a b l e b u t i m m e r s i o n systems d o h a v e a
n u m b e r of a d v a n t a g e s . N o t only is the c o u p l i n g
c o n s t a n t , b u t the fact t h a t the t r a n s d u c e r m a y be
located s o m e distance a w a y from the surface of the
specimen p e r m i t s the use of t r a n s d u c e r s p r o d u c i n g
focused o r collimated b e a m s . T h e t r a n s d u c e r is held
in a m a n i p u l a t o r so t h a t its o r i e n t a t i o n a n d distance
from the specimen can be adjusted. T h e t r a n s d u c e r
c a n t h e n be used t o scan in a prescribed p l a n e relative
to the specimen surface. I n f o r m a t i o n c a n be o b t a i n e d
a b o u t the c o n d i t i o n of the specimen a n d presented in
a n u m b e r of ways, the m o s t usual being the so-called
-, B- a n d C-scan displays. T h e s e p r e s e n t a t i o n s are
also applicable to n o n i m m e r s i o n systems, b u t are
m o r e difficult t o achieve in practice.
3.2 Ultrasonic

3.4 Ultrasonic

C-Scan

In this type of p r e s e n t a t i o n a m o r e c o m p l e x s c a n n i n g
system is used such t h a t the t r a n s d u c e r is s c a n n e d in a
p l a n e parallel t o the surface of the specimen in a
rectilinear raster p a t t e r n . A r e c o r d e r p e n is c o u p l e d to
t h e t r a n s d u c e r m a n i p u l a t o r so t h a t t h e p e n m o v e m e n t
accurately r e p r o d u c e s the s c a n n i n g p a t t e r n . In this
w a y a p l a n view of the a t t e n u a t i o n d i s t r i b u t i o n is
o b t a i n e d , allowing, for e x a m p l e , a n assessment of the
lateral extent of d a m a g e . It is usual t o use a n i m m e r
sion system in which the t r a n s d u c e r is s c a n n e d in the

A-Scan

T h e simplest p r e s e n t a t i o n , t h e - s c a n , displays t h e
ultrasonic i n f o r m a t i o n a c q u i r e d at a single p o i n t in a
specimen. It is usually displayed o n a n oscilloscope, as
in Fig. 1, a n d consists of a series of echoes w h o s e
position a l o n g the h o r i z o n t a l axis c a n be calibrated in
t e r m s of d e p t h in t h e s a m p l e u n d e r test so t h a t t h e
position of a reflector c a n be m e a s u r e d . T h e a m p l i
t u d e of each e c h o will give s o m e i n d i c a t i o n of t h e size
a n d n a t u r e of the reflector.
It is i m p o r t a n t to n o t e t h a t , if a defect is present a n d
is of a type t h a t reflects a large fraction of the incident
s o u n d w a v e , then only a very small p r o p o r t i o n will
p r o p a g a t e b e y o n d the defect. A n y a d d i t i o n a l reflec

60

B-Scan

If the s a m e t r a n s d u c e r is m o v e d linearly (usually by a

m o t o r drive) in a p l a n e parallel t o t h e surface of the
specimen then a n u m b e r of - s c a n s c a n be r e c o r d e d ,
c o r r e s p o n d i n g t o different positions across t h e speci
m e n . It is, however, m o r e c o n v e n i e n t to extract the
essential features of the - s c a n s , n a m e l y the t h r o u g h thickness position a n d a m p l i t u d e of the m a j o r p e a k s ,
a n d to c o m b i n e t h e m in a single display which c o r r e s
p o n d s t o a slice t a k e n t h r o u g h t h e s a m p l e , n o r m a l t o
the surface. U s i n g this type of p r e s e n t a t i o n , k n o w n as
a B-scan, it is possible t o estimate b o t h the d e p t h of
reflectors a n d their lateral extent a l o n g the axis of
t r a n s d u c e r m o v e m e n t . T h i s c a n b e particularly help
ful in p r e s e n t i n g the d i s t r i b u t i o n of i m p a c t d a m a g e .
A n e x a m p l e is s h o w n in Fig. 2 of i m p a c t d a m a g e in a
C F C test specimen w h e r e the thickness t a p e r s from
4 m m to 3 m m .

Figure 2
B-scan showing depth of impact damage in a CFC test
specimen where thickness tapers from 4 mm to 3 mm

Composite

Materials:

Nondestructive

Evaluation

of t h e p r o b e assembly, t h a t the w a t e r flow is l a m i n a r .

Because t h e s o u n d is guided d o w n t h e w a t e r jet,
a w k w a r d s t r u c t u r a l g e o m e t r i e s c a n be inspected b y
e m p l o y i n g suitably s h a p e d guide t u b e s . This tech
n i q u e is generally used in t h r o u g h t r a n s m i s s i o n a n d a t
frequencies below a b o u t 10 M H z . A l t h o u g h a jetp r o b e system l o o k s q u i t e different from a n i m m e r s i o n
system, the basic c o n s i d e r a t i o n s a r e the s a m e . In
fact it is c u r r e n t l y the m o s t widely used t e c h n i q u e
in t h e a e r o s p a c e i n d u s t r y for p r o d u c i n g t h r o u g h t r a n s m i s s i o n C-scans of large c o m p o n e n t s .
3.6 Roller

Figure 3
C-scan showing area of impact damage of specimen in
Fig. 2

w a t e r t a n k a b o v e t h e specimen. If a single t r a n s d u c e r
is e m p l o y e d in a " p u l s e - e c h o " configuration, a glass
reflector plate placed b e h i n d t h e specimen is often
used. T h e received signal e c h o from t h e glass p l a t e is
m o n i t o r e d using a time-gate m o d u l e , which c o n v e r t s
the a m p l i t u d e of t h e largest reflection within a preset
time interval to a voltage. In simple systems this is
used t o p r o d u c e a gray-scale p r e s e n t a t i o n o n c u r r e n t sensitive p a p e r s h o w i n g t h e v a r i a t i o n in a t t e n u a t i o n .
F i g u r e 3 s h o w s a C-scan of t h e specimen used as a n
e x a m p l e of B-scanning in Fig. 2.
Alternatively this d a t a m a y be stored in a c o m
p u t e r , allowing t h e use of v a r i o u s c o l o r p r e s e n t a t i o n s .
Simple displays require t h e a r b i t r a r y selection of a
limited r a n g e of colors a n d a r e n o t always easy t o
interpret, b u t m o r e sophisticated systems c a n offer a
significant increase in the d y n a m i c r a n g e displayed.
T h e big a d v a n t a g e of c o m p u t e r s t o r a g e , h o w e v e r , lies
in its ability t o p r o d u c e , from a single scan, p r e s e n t a
tions c o r r e s p o n d i n g to different a t t e n u a t i o n t h r e s h
olds. W h e t h e r o r n o t c o m p u t e r s t o r a g e is used it is
i m p o r t a n t t o n o t e t h a t the t h r e s h o l d settings a r e
a r b i t r a r y a n d c o m p a r a t i v e l y small c h a n g e s c a n result
in quite different C-scans being p r o d u c e d . T h e C-scan
will only be meaningful if t h e r e l a t i o n s h i p b e t w e e n
the settings a n d t h e p a r a m e t e r p l o t t e d is k n o w n b y
calibration.
T h e r e a r e s o m e d i s a d v a n t a g e s in using i m m e r s i o n
testing e q u i p m e n t ( S t o n e a n d C l a r k e 1987); a l t e r n a
tive techniques are therefore s o m e t i m e s used.
3.5 Ultrasonic Jet Probes
A c o m m o n l y used t e c h n i q u e , which still uses w a t e r as
a c o u p l a n t , is the jet (or squirter) p r o b e t e c h n i q u e .
H e r e the c o m p o n e n t is n o t i m m e r s e d ; instead, the
coupling w a t e r impinges o n t o t h e surface of the
c o m p o n e n t in a jet a l o n g which the u l t r a s o u n d t r a
vels. T h e w a t e r jet acts as a w a v e g u i d e to t h e s o u n d .
T h e m a i n difficulty is t o m a k e sure, by correct design

Probes

In a p p l i c a t i o n s w h e r e t h e c o m p o s i t e m u s t n o t c o m e
i n t o c o n t a c t w i t h w a t e r , roller p r o b e s c a n be used.
T h e u l t r a s o n i c t r a n s d u c e r element is held inside a
wheel a n d the s o u n d p r o p a g a t e d i n t o the specimen
t h r o u g h a soft r u b b e r tire. T h i s t e c h n i q u e is generally
used a t low frequencies a n d c a n b e used for t h e r a p i d
d e t e c t i o n of in-service d a m a g e b u t is n o t really suit
able for its detailed c h a r a c t e r i z a t i o n .
3.7 Imaging

Systems

A c o n s i d e r a b l e a m o u n t of w o r k is being carried o u t in
t h e field of u l t r a s o n i c i m a g i n g systems, s o m e of which
is a i m e d a t i m a g i n g d a m a g e in c o m p o s i t e s . D e l a m i n a t i o n s a r e of p r i m e i m p o r t a n c e w h e n c o n s i d e r i n g
d a m a g e m e c h a n i s m s in C F C a e r o s p a c e structures,
a n d a n u l t r a s o n i c i m a g i n g system h a s recently been
d e v e l o p e d (Lloyd a n d W r i g h t 1986) specifically a i m e d
a t p r o v i d i n g a pictorial p r e s e n t a t i o n of t h e distribu
tion of d e l a m i n a t i o n s . Essentially such a system uses a
c o m b i n a t i o n of the B- a n d C-scan m e t h o d s to gener
ate isometrically projected images of defects as
p s e u d o - t h r e e - d i m e n s i o n a l displays. T h e software
p a c k a g e within this system e n a b l e s the viewer to select
viewing angle a n d r o t a t i o n a l p o s i t i o n of the object as
well as a n o p t i o n t o magnify. B o t h the a r e a a n d
t h r o u g h - t h i c k n e s s p o s i t i o n of t h e d a m a g e c a n there
fore be viewed with a clarity n o t possible by c o n v e n
tional u l t r a s o n i c t e c h n i q u e s (see Fig. 4.)

4. Radiographic

Methods

4.1 X- Radiography
R a d i o g r a p h y is b a s e d o n t h e differential a b s o r p t i o n
of p e n e t r a t i n g r a d i a t i o n . Because of v a r i a t i o n s in
thickness o r differences in a b s o r p t i o n characteristics
c a u s e d by v a r i a t i o n s in c o m p o s i t i o n , different p a r t s of
a c o m p o n e n t a b s o r b different a m o u n t s of r a d i a t i o n .
U n a b s o r b e d radiation passing through the compon
e n t m a y be r e c o r d e d o n film, viewed o n a fluorescent
screen o r m o n i t o r e d by a r a d i a t i o n d e t e c t o r . Access t o
t h e r e a r surface is therefore necessary, a n d this m a y
limit t h e a p p l i c a t i o n s for which r a d i o g r a p h y is suit
able. It is generally used t o reveal h i d d e n c h a n g e s in
thickness o r a r e a s h a v i n g a different density from the
s u r r o u n d i n g m a t e r i a l . It is therefore widely used t o

61

Composite

Materials:

Nondestructive

Evaluation

n o r m a l to the x-ray b e a m a n d a n o t h e r inclined a t a n

angle of a b o u t 15. F o r small c o m p o n e n t s this is m o s t
easily achieved b y k e e p i n g t h e film in c o n t a c t with the
c o m p o n e n t a n d r o t a t i n g t h e m t o g e t h e r relative t o t h e
x-ray b e a m .

Figure 4
Ultrasonic image of impact damage of specimen in Fig. 2

reveal significant a r e a s of p o r o s i t y , the presence of

foreign bodies a n d the a l i g n m e n t of s u b s t r u c t u r e .
C o m p o s i t e m a t e r i a l s are, however, relatively p o o r
a b s o r b e r s of r a d i a t i o n so it is necessary to use low
voltage levels (say 20 kV) in o r d e r to o b t a i n sufficient
c o n t r a s t . F u r t h e r m o r e , it c a n only detect t h o s e
features t h a t h a v e a n a p p r e c i a b l e d i m e n s i o n parallel
to the r a d i a t i o n b e a m so t h a t its ability t o detect
p l a n a r defects, such as c r a c k s , is strongly d e p e n d e n t
o n the o r i e n t a t i o n of the defect. F o r this r e a s o n
d e l a m i n a t i o n s a r e very difficult to detect by c o n v e n
tional r a d i o g r a p h y .
It is, however, possible to p r o d u c e a m a r k e d in
crease in c o n t r a s t by i n t r o d u c i n g a r a d i o p a q u e p e n e
t r a n t i n t o the defective area. T h i s m e t h o d , often called
p e n e t r a n t e n h a n c e d r a d i o g r a p h y ( P E X R ) , is p a r
ticularly v a l u a b l e in d e t e r m i n i n g the extent a n d
n a t u r e of i m p a c t d a m a g e . F i g u r e 5 is the e n h a n c e d
r a d i o g r a p h of the i m p a c t d a m a g e previously ex
a m i n e d ultrasonically.
T h e d a m a g e m u s t , however, b r e a k the surface at
s o m e p o i n t in o r d e r to allow access for the p e n e t r a n t .
T r a n s l a m i n a r c r a c k s , which a r e difficult to detect by
o t h e r m e t h o d s , are readily revealed by P E X R . Selec
tion of the m o s t suitable p e n e t r a n t d e p e n d s o n a
n u m b e r of factors (Stone a n d C l a r k e 1987), including
the degree of opacity required. If the d a m a g e is gross
then a p e n e t r a n t exhibiting low a t t e n u a t i o n s h o u l d be
used in o r d e r to reveal fine detail w i t h o u t s a t u r a t i n g
the picture. Lesser degrees of d a m a g e will require a
more opaque penetrant.
In o r d e r to t a k e full a d v a n t a g e of the ability of
P E X R to give a detailed picture of d a m a g e a stereo
t e c h n i q u e s h o u l d be e m p l o y e d . T h i s requires t h a t t w o
s e p a r a t e r a d i o g r a p h s are t a k e n of a single object, o n e

62

4.2 Computer-Aided
Tomography
A c o n v e n t i o n a l r a d i o g r a p h is a t w o - d i m e n s i o n a l pres
e n t a t i o n of a t h r e e - d i m e n s i o n a l object, the density of
the i m a g e at each p o i n t in the r a d i o g r a p h being
g o v e r n e d by the t o t a l a t t e n u a t i o n experienced by t h a t
p a r t of t h e x-ray b e a m . T h e r e is n o i n f o r m a t i o n o n the
c o n t r i b u t i o n t h a t each element of the object m a k e s t o
the t o t a l a t t e n u a t i o n . C o m p u t e r - a i d e d t o m o g r a p h y
( C A T ) , o n the o t h e r h a n d , m e a s u r e s the intensity of xray t r a n s m i s s i o n a l o n g m a n y p a t h s in a single p l a n e ,
a n d uses a c o m p u t e r t o calculate the a t t e n u a t i o n
c o n t r i b u t e d by each element in the p l a n e ( G i l b o y a n d
F o s t e r 1982). Because industrial versions of such
systems a r e expensive, a p p l i c a t i o n s to c o m p o s i t e s
h a v e been s o m e w h a t limited b u t they are n o w being
used extensively for the inspection of rocket m o t o r s
a n d cases. E v e n units designed for medical use are
p r o v i n g v a l u a b l e for c o m p o n e n t s such as helicopter
r o t o r blades, an e x a m p l e of which is s h o w n in Fig. 6.
4.3 Neutron
Radiography
N e u t r o n r a d i o g r a p h y is often r e g a r d e d as a c o m p l e
m e n t a r y t e c h n i q u e to r a d i o g r a p h y ; in p a r t i c u l a r this
is because n e u t r o n s are strongly a b s o r b e d by the
lightest elements (including h y d r o g e n ) , w h e r e a s heavy
elements such as lead a r e relatively t r a n s p a r e n t t o
n e u t r o n s . N o n r e a c t o r sources of n e u t r o n s a r e avail
able b u t they a r e at present b o t h expensive a n d
s o m e w h a t c u m b e r s o m e ; f u r t h e r m o r e , the source size
is m u c h g r e a t e r t h a n t h a t available in r a d i o g r a p h y ,
t h u s r e d u c i n g the resolution a t t a i n a b l e . F o r these a n d
o t h e r r e a s o n s there h a v e been relatively few applica
tions of n e u t r o n r a d i o g r a p h y to c o m p o s i t e s . O n l y for

Figure 5
Penetrant enhanced ray of impact damage

Composite

Materials:

Nondestructive

Evaluation

p e r m i t s u b s e q u e n t viewing in real time, or at s o m e

o t h e r r a t e , b u t it also allows i m a g e processing tech
n i q u e s t o be applied if r e q u i r e d .
T h e p e r f o r m a n c e of t h e r m o g r a p h i c systems is, of
c o u r s e , strongly affected by t h e t h e r m a l conductivity
of t h e p a r t i c u l a r c o m p o s i t e . In C F C , for e x a m p l e , the
c o n d u c t i v i t y in t h e p l a n e of t h e l a m i n a t e is a b o u t nine
times t h a t in the t h r o u g h - t h i c k n e s s direction. T h i s
t r a n s v e r s e diffusion t e n d s t o o b s c u r e defects t h a t are
n o t close to the surface. H o w e v e r , t h e usual t h r o u g h thickness d i s t r i b u t i o n of i m p a c t d a m a g e is such t h a t a
d a m a g e d a r e a t h a t is large e n o u g h t o be structurally
significant will c o n t a i n limited b u t m e a s u r a b l e
d a m a g e close t o t h e surface. T h e r m o g r a p h y is c a p a b l e
of detecting t h e presence of i m p a c t d a m a g e in C F C
m a t e r i a l a n d d i s b o n d s in b o n d e d c o m p o s i t e s t r u c t u r e s
( M c L a u g h l i n et al. 1987).
Figure 6
X-ray CAT showing voids in the leading edge of a
composite blade

specialized p r o b l e m s , such as d e t e r m i n a t i o n of the

quality of a c o m p o s i t e h i d d e n inside a thick m e t a l
casing, h a s its use p r o v e d w o r t h w h i l e .

5. Thermographic

Methods

T h e s e m a y be conveniently divided i n t o t w o m a i n
types: p a s s i v e w h e r e there is a n externally applied
h e a t i n g or c o o l i n g s o u r c e a n d a c t i v e w h e r e there
are internally g e n e r a t e d h e a t i n g o r c o o l i n g effects. I n
b o t h cases t h e surface t e m p e r a t u r e d i s t r i b u t i o n is
m o n i t o r e d a n d e x a m i n e d for a n o m a l i e s t h a t indicate
the presence of defects. T h e active m e t h o d , h o w e v e r ,
h a s only really f o u n d a p p l i c a t i o n in t h e m o n i t o r i n g of
fatigue tests w h e r e h e a t is g e n e r a t e d by fretting effects
at sites of internal d a m a g e .
In the passive m e t h o d , which h a s been m u c h m o r e
widely e m p l o y e d , t h e surface of a c o m p o n e n t is
subjected to a r a p i d t e m p e r a t u r e c h a n g e a n d t h e
s u b s e q u e n t h e a t flow m o n i t o r e d . A variety of h e a t
sources h a v e been investigated, v a r y i n g from simple
h o t - a i r g u n s t o b a n k s of flash t u b e s . T h e w a y in w h i c h
the h e a t is dissipated d e p e n d s o n t h e t h e r m a l c o n d u c
tivity of the c o m p o s i t e a n d o n the n a t u r e a n d l o c a t i o n
of a n y defects. If there is a d e l a m i n a t i o n in a l a m i n a t e ,
for e x a m p l e , t h e n less h e a t will be t r a n s m i t t e d
t h r o u g h t h e defective a r e a resulting in a h o t s p o t o n
the h e a t e d surface a n d a cold s p o t o n t h e b a c k
surface. It is possible t o m o n i t o r either t h e front o r the
b a c k surface ( p r o v i d e d t h a t this is accessible). By
a n a l o g y with u l t r a s o n i c s t e r m i n o l o g y t h e f o r m e r is
often called a p u l s e - e c h o t e c h n i q u e a n d t h e latter,
t h r o u g h t r a n s m i s s i o n . It is u s u a l for s o m e k i n d of
infrared-sensitive c a m e r a to be used a n d for the
o u t p u t t o be stored o n video t a p e . N o t only d o e s this

6.

Vibration

and Mechanical

Impedance

Methods

A l t h o u g h v i b r a t i o n t e c h n i q u e s f o r m e d t h e basis of
s o m e of t h e m o s t a n c i e n t m e t h o d s of N D T it is only
c o m p a r a t i v e l y recently t h a t they h a v e gained a scien
tific basis ( A d a m s a n d C a w l e y 1985). F o r convenience
these t e c h n i q u e s m a y be divided i n t o global a n d local
m e t h o d s . I n t h e former a w h o l e c o m p o n e n t is excited
by a pulse o r by c o n t i n u o u s excitation, a n d n a t u r a l
frequencies
and
damping
characteristics
are
m e a s u r e d . T h i s a p p r o a c h h a s been used t o p r o v i d e a
r a p i d m e t h o d of p r o d u c t i o n inspection for c o m
p o n e n t s of simple g e o m e t r y such as small missilel a u n c h e r t u b e s . W i t h local m e t h o d s only a small a r e a
is excited a n d its m e c h a n i c a l r e s p o n s e m e a s u r e d . Such
m e t h o d s h a v e t h e a d v a n t a g e of only r e q u i r i n g access
t o o n e surface a n d d o n o t need a c o u p l a n t . T h e y are
p a r t i c u l a r l y suited t o t h e d e t e c t i o n of d i s b o n d s
b e t w e e n thin c o m p o s i t e skins a n d a f o a m o r h o n e y
comb substructure.

7. Optical

Methods

A n u m b e r of optical m e t h o d s h a v e been developed to

m e a s u r e the a b s o l u t e t h r e e - d i m e n s i o n a l s h a p e of a
c o m p o n e n t , a n d hence t o detect c h a n g e s in this s h a p e
o r t o m e a s u r e in-plane o r n o r m a l d i s p l a c e m e n t s . T h e
presence of a n o m a l i e s in the s h a p e or d i s p l a c e m e n t
p a t t e r n s m a y b e used t o reveal t h e presence of defects
( W a l k e r a n d M c K e l v i e 1987). S o m e m e t h o d s m a y
require M o i r e grids o r p h o t o e l a s t i c c o a t i n g s to be
applied t o the surface being inspected. M o s t m e t h o d s ,
h o w e v e r , d o n o t require special surface p r e p a r a t i o n ,
a l t h o u g h a thin c o a t of w h i t e n e r is necessary in o r d e r
t o get sufficient reflection of light from C F C . M e t h o d s
such as h o l o g r a p h y a n d electronic speckle p a t t e r n
i n t e r f e r o m e t r y ( E S P I ) detect very small d i s p l a c e m e n t s
a n d so require a vibration-free e n v i r o n m e n t .
A p r o b l e m c o m m o n t o all of t h e optical m e t h o d s
lies in t h e fact t h a t t h e c o m p o n e n t h a s t o be lightly

63

Composite

Materials:

Nondestructive

Evaluation

stressed in s o m e w a y in o r d e r t o g e n e r a t e t h e b a c k
g r o u n d d i s p l a c e m e n t p a t t e r n s against which t h e
a n o m a l i e s a r e revealed. T h e w a y in which these dis
placements are generated m a y govern whether or not
a p a r t i c u l a r defect is revealed. Very simple m e t h o d s
are, however, often sufficient. F o r e x a m p l e , gentle
heating with a h o t - a i r g u n h a s p r o v e d a very effective
w a y of revealing d i s b o n d s between a c o m p o s i t e skin
a n d a h o n e y c o m b core.

8. Eddy

Current

Inspection

E d d y c u r r e n t m e t h o d s a r e widely used t o inspect

metallic m a t e r i a l s a n d they c a n also be applied t o
o r g a n i c - m a t r i x c o m p o s i t e s c o n t a i n i n g electrically
c o n d u c t i n g fibers. H o w e v e r , because t h e resistivity of
even a carbon-fiber c o m p o s i t e is very high relative t o
t h a t of m o s t m e t a l s , t h e techniques e m p l o y e d d o
differ.
In t h e e d d y c u r r e n t m e t h o d , if a c u r r e n t - c a r r y i n g
coil is placed adjacent t o a c o n d u c t i n g m a t e r i a l , e d d y
c u r r e n t s a r e i n d u c e d i n t o t h e m a t e r i a l affecting t h e
i m p e d a n c e of the driving coil. Local c h a n g e s in resisti
vity o r i n t e r r u p t i o n of t h e e d d y c u r r e n t field by defects
will further alter t h e i m p e d a n c e . This r e s p o n s e is
usually characterized in t e r m s of b o t h a m p l i t u d e a n d
p h a s e angle. A critical factor is t h e selection of
frequency; high frequencies result in better resolution
b u t a decreased d e p t h of p e n e t r a t i o n . F o r C F C ,
however, t h e resistivity is very high a n d p e n e t r a t i o n
d e p t h is n o t usually a p r o b l e m .
E d d y c u r r e n t m e t h o d s h a v e n o t been used very
widely o n c o m p o s i t e s despite t h e fact t h a t they a r e
c o m p a r a t i v e l y simple t o use a n d t h e p r o b e d o e s n o t
need t o m a k e c o n t a c t with t h e surface. T h e r e a s o n for
this lies in t h e a m b i g u i t y of the response. A l t h o u g h it
provides a simple a n d effective w a y of detecting
i m p a c t d a m a g e ( S p r o a t a n d Lewis 1986), it is also
sensitive t o o t h e r factors such as v o l u m e fraction a n d
l a m i n a t e thickness.

9. Acoustic

Emission

In t h e acoustic emission ( A E ) t e c h n i q u e , a stress of a

representative p a t t e r n , b u t of a m o d e s t level, is a p
plied t o a c o m p o n e n t , a n d sensitive t r a n s d u c e r s a r e
used t o m o n i t o r the o c c u r r e n c e of stress waves gener
ated by small local failure events. D e p e n d i n g o n t h e
degree of sophistication of t h e i n s t r u m e n t a t i o n
e m p l o y e d , i n f o r m a t i o n c a n be o b t a i n e d o n t h e loca
tion a n d severity of these events, a n d s o m e t i m e s o n
their n a t u r e . T h e use of A E t o distinguish between
various types of failure event is, however, far from
easy, even o n simple l a b o r a t o r y specimens, a n d is
extremely difficult t o achieve o n m o s t s t r u c t u r a l c o m
p o n e n t s . T h e r e is a wide choice of e q u i p m e n t a n d

64

signal processing p r o c e d u r e s , a n d care m u s t b e t a k e n

to select t h o s e m o s t suitable for a specific a p p l i c a t i o n
( A r r i n g t o n 1987). S o m e of t h e m o s t successful
a p p l i c a t i o n s h a v e been w h e n p r o o f tests h a v e been
p e r f o r m e d o n a significant n u m b e r of similar c o m
p o n e n t s allowing p a t t e r n s of emission b e h a v i o r t o b e
established. H o w e v e r , t h e stage at which emission
restarts d u r i n g a r e p e a t e d l o a d i n g (the Felicity effect)
h a s also been s h o w n t o p r o v i d e v a l u a b l e i n f o r m a t i o n
o n individual c o m p o n e n t s .
A n interesting alternative is p r o v i d e d by t h e v i b r o acoustic emission t e c h n i q u e in which t h e c o m p o n e n t
is excited b y a v i b r a t i o n a n d similar e q u i p m e n t is used
t o m o n i t o r fretting noise e m a n a t i n g from d a m a g e .

10. Adhesive-Bonded

Joints

C o m p o s i t e c o m p o n e n t s a r e frequently fabricated b y
adhesively b o n d i n g t o g e t h e r pre-cured elements. P o o r
b o n d i n g c a n easily result in p l a n e s of w e a k n e s s so t h e
inspection of b o n d lines is often necessary. H o w e v e r ,
a l t h o u g h t h e d e t e c t i o n of b o n d - l i n e defects is perfectly
feasible, n o n d e s t r u c t i v e m e a s u r e m e n t
of b o n d
strength is extremely difficult. A l s o , a clear distinction
m u s t b e d r a w n b e t w e e n t h e adhesive s t r e n g t h of t h e
interface b e t w e e n t h e a d h e r e n d a n d t h e adhesive
layer, a n d t h e cohesive strength of t h e adhesive itself.
Discrete defects, such as d i s b o n d s o r a r e a s of p o r o s
ity, a r e detectable in m u c h t h e s a m e w a y as they a r e
in t h e c o m p o s i t e itself. T h e presence of release film
c a n , however, cause a p r o b l e m . Small isolated a r e a s
of film a r e usually f o u n d w i t h o u t difficulty, b u t a
c o m p l e t e sheet of thin (0.07 m m ) polyester film is
m u c h h a r d e r t o find. T h i s is, in fact, very similar t o t h e
s i t u a t i o n e n c o u n t e r e d with a " s t u c k b o n d , " w h e r e t h e
t w o surfaces a r e in i n t i m a t e c o n t a c t b u t t h e b o n d h a s
n o s t r e n g t h . C o n t a m i n a t i o n of t h e a d h e r e n d surfaces
p r i o r t o b o n d i n g c a n b e highly d e t r i m e n t a l a n d diffi
cult t o detect ( S t o n e 1986).

11.

Conclusion

T h e multiplicity of possible defect types in c o m p o s i t e s

a n d t h e c u r r e n t u n c e r t a i n t y as t o their effect o n t h e
physical p r o p e r t i e s a n d s t r u c t u r a l p e r f o r m a n c e m e a n s
t h a t t h e N D E of c o m p o s i t e s is a challenging field.
A l t h o u g h t h e p r e s e n t g e n e r a t i o n of c o m p o s i t e s is
p r o v i n g t o b e surprisingly defect t o l e r a n t , a n d cur
rently available N D E m e t h o d s c a n d o m u c h of w h a t is
r e q u i r e d , t h e cost of inspection is u n a c c e p t a b l y high.
A l s o s o m e a r e a s , such as repair, h a v e so far received
little a t t e n t i o n . E q u a l l y t h e i n t r o d u c t i o n of n e w
m a t e r i a l s will p r o b a b l y b r i n g with it n e w p r o b l e m s for
N D E . H o w e v e r , q u a n t i t a t i v e N D E is a rapidly
a d v a n c i n g field a n d d e v e l o p m e n t s in areas such as

Compton

a u t o m a t i o n a n d signal processing a r e likely t o lead t o

m a r k e d increases in capability.

120

Scattering

60

90
8

See also: Acoustic Emission; Adhesives: Tests for Mechani

cal Properties; Stress Distribution: Analysis Using
Thermoelastic Effect

6
150

30

_4

10 k e y

Bibliography
Adams R D, Cawley 1985 Vibration techniques in nondes
tructive testing. In: Sharpe R S (ed.) 1985 Research
Techniques in Nondestructive Testing, Vol. 7. Elsevier,
London.
Arrington 1987 Acoustic emission. In: Summerscales J
(ed.) 1987 Non-destructive Testing of Fibre Reinforced
Plastics Composites, Vol. 1. Elsevier, London
Gilboy W B, Foster J 1982 Industrial applications of
computerised tomography with and gamma radiation.
In: Sharpe R S (ed.) 1982 Research Techniques in Nondes
tructive Testing, Vol. 6. Elsevier, London
Lloyd A, Wright A 1986 An introductory investigation
into the performance of an ultrasonic imaging system.
Royal Aircraft Establishment Report TR 86063. RAE,
Farnborough, UK
McLaughlin V, Mirchand G, Ciekurs V 1987
Infrared thermographic flaw detection in composite lami
nates. J. Eng. Mater. Technol. 109: 146-50
Reynolds W 1986 Nondestructive testing techniques for
metal matrix composites. Harwell Report AERE R
13040. Harwell Laboratory, Didcot, UK
Sproat W H, Lewis W 1986 Barely visible impact damage
(BVID) detection in aircraft composites. Proc. AIAA/
SOLE 2nd Aerospace Maintenance Conf. American Insti
tute of Aeronautics, New York
Stone D E W 1986 Non-destructive methods of characteris
ing the strength of adhesive-bonded jointsa review.
Royal Aircraft Establishment Report TR 86058. RAE,
Farnborough, UK
Stone D E W , Clarke 1987 Non-destructive evaluation of
compositesan overview. Proc. 6th Int. Conf. Composite
Materials, 2nd European Conf. Composite Materials. Else
vier, London
Walker C A, McKelvie J 1987 Optical methods. In: Sum
merscales J (ed.) 1987 Non-destructive Testing of Fibre
Reinforced Plastics Composites, Vol. 1. Elsevier, London
D . E. W . S t o n e a n d B. C l a r k e
[Royal Aerospace Establishment,
Farnborough, UK]

180

i f
8

I
6

1
4

T h e C o m p t o n effect describes t h e inelastic scattering

of rays o r rays from t h e electrons in a t a r g e t
m a t e r i a l . It h a s t w o a p p l i c a t i o n s within t h e a r e a o f
materials investigation. A t a f u n d a m e n t a l level, t h e
spectral d i s t r i b u t i o n of t h e scattered r a d i a t i o n reveals
information a b o u t the m o m e n t u m distribution of the
electrons in t h e target. A less p r o f o u n d use follows

1 /
2

1
0

1
4

Compton cross section ( I 0

_ 3 02

e" sr" )

Figure 1
The Klein-Nishina cross section for Compton scattering
(as given by Eqn. (3)) plotted as a polar diagram for
incident photon energies Ex of 10 keV, 60 keV and
600 keV. The energy of the scattered photon E2 varies with
the angle of scattering according to Eqn. (2)

from t h e p r o p o r t i o n a l i t y b e t w e e n t h e intensity of t h e
scattered signal a n d t h e density of electrons from
w h i c h they a r e scattered. It results in d e n s i t o m e t r y
a n d i m a g i n g from t h e b a c k s c a t t e r e d signal in situa
tions w h e r e t r a n s m i s s i o n t e c h n i q u e s a r e ineffective for
nondestructive examinations.

1. Basic

Theory

T h e s c a t t e r i n g i n t e r a c t i o n is s h o w n schematically in
the inset t o F i g . 1. C o m p t o n ' s shift f o r m u l a
= (1 - c o s )
(1)
mirelates t h e w a v e l e n g t h shift t o t h e scattering angle
w h e r e h is P l a n c k ' s c o n s t a n t , m is t h e electron m a s s
a n d c is t h e velocity of light. It c a n also be written
m o r e usefully, if less economically, in t e r m s of the
p h o t o n energies a s

= EX

Compton Scattering

^ 6 0 0 k e V

\
1 + 4 ( 1 - cos )

(2)

mc

T h e differential scattering cross section for a n

u n p o l a r i z e d b e a m is given b y t h e K l e i n - N i s h i n a for
m u l a , w h i c h c a n be w r i t t e n as

IH(^)W(t t- '"1) >

+

<3

65

Compton

Scattering

p r o b a b i l i t y of observing t h a t c o m p o n e n t of m o m e n
t u m . T h i s is k n o w n as the C o m p t o n profile J(p:)
which c a n be expressed by t h e e q u a t i o n
APZ)=

Scattering angle (degrees)

Figure 2
The energy of Compton scattered radiation as a function
of the angle of scattering for different incident photon
energies. Large energy losses occur for high-energy
photons at high angles of scattering

This preserves the s y m m e t r y b e t w e e n f o r w a r d scatter

ing a n d b a c k s c a t t e r i n g predicted by the classical
T h o m s o n cross section at low energies, a l t h o u g h a t
higher energies the scattering b e c o m e s p e a k e d in the
forward direction, as is evident from Fig. 1. T h e
energy loss, given by E q n . (2), b e c o m e s progressively
greater as is illustrated in Fig. 2 for a selection of
incident energies u p t o 1 M e V . In t h e high energy
limit, t h a t is, as E{->co, the b a c k s c a t t e r e d p h o t o n will
2
h a v e a n energy of only \mc , which is 256 keV. T h e s e
f u n d a m e n t a l f o r m u l a e , a n d o t h e r s , a r e detailed by
E v a n s (1958).
T h e C o m p t o n shift f o r m u l a ( E q n . (1) o r (2)) a p
p e a r s to be devoid of interest b e c a u s e it c o n t a i n s n o
i n f o r m a t i o n a b o u t the target m a t e r i a l . T h i s is because
the derivation is based o n the a s s u m p t i o n of s t a t i o n
ary electrons. In reality, electron m o t i o n b r o a d e n s the
spectral d i s t r i b u t i o n of t h e scattered b e a m a p p r e c i a
bly; c o n d u c t i o n electrons in a m e t a l travel with speeds
6
-1
of a p p r o x i m a t e l y 10 m s a n d inner shell electrons in
heavy elements a r e relativistic. T h i s is a k i n t o the
D o p p l e r effect, t h e c o m p o n e n t of m o m e n t u m a l o n g
the x-ray scattering vector ( t a k e n as the axis)
causing the a d d i t i o n a l energy shift. E q u a t i o n (2) t h e n
h a s a n a d d i t i o n a l t e r m p r o p o r t i o n a l t o this c o m
p o n e n t of m o m e n t u m pz. T h e r e f o r e , at a n y p a r t i c u l a r
scattered b e a m energy, t h e line s h a p e is described by
the projection of t h e electron m o m e n t u m d i s t r i b u t i o n
n(p) a l o n g the x-ray scattering vector, t h a t is, t h e

66

n(p) dpx

dpy

(4)

It is related in this simple w a y to the m e a s u r e d

spectral d i s t r i b u t i o n w h e n the energy transfer E{ E2
clearly exceeds the electron b i n d i n g energies in the
target. T h i s so-called impulse a p p r o x i m a t i o n is cer
tainly valid w h e n rays with energies greater t h a n
100 keV are b a c k s c a t t e r e d from c o m m o n elements,
b u t its use is q u e s t i o n a b l e w h e n rays from c o n v e n
tional t u b e sources o r s y n c h r o t r o n s (energies less t h a n
30 keV) a r e used.
T h e validity of the impulse a p p r o x i m a t i o n h a s
rarely been given a t t e n t i o n by e x p e r i m e n t e r s since
there a r e m o r e pressing practical p r o b l e m s with softer
r a d i a t i o n . T h e s e arise from the p r o h i b i t i v e p h o t o e l e c
tric a b s o r p t i o n in all b u t t h e lightest elements (i.e., the
first 14 elements) c o u p l e d with the fact t h a t the
inelastic scattering cross section, described by E q n . (3)
a n d depicted in Fig. 1, only a m o u n t s to a few b a r n s
2 8
2
p e r a t o m (1 b a r n = 1 0 " m ) w h e r e a s the p h o t o e l e c
tric a b s o r p t i o n cross section m a y be several o r d e r s of
m a g n i t u d e larger a t c o n v e n t i o n a l x-ray energies in all
b u t the lightest m a t e r i a l s . In a diffraction e x p e r i m e n t ,
the c o h e r e n c e of t h e Bragg-scattered b e a m leads t o
large signals, b u t in the i n c o h e r e n t C o m p t o n scatter
ing process the intensities a r e m u c h lower; this is the
m a i n r e a s o n for the c o m p a r a t i v e neglect of t h e tech
n i q u e after the p i o n e e r i n g d a y s of D u M o n d a n d his
c o - w o r k e r s ( D u M o n d 1933). T h e i r m e a s u r e m e n t of
the C o m p t o n profile of beryllium p r o v i d e d t h e first
direct evidence for the F e r m i - D i r a c statistics in a n
electron gas, b u t there w a s little further activity until
the 1960s w h e n the w o r k w a s revived. Recently, line
s h a p e analysis h a s received a fillip from t w o d e v e l o p
m e n t s with s y n c h r o t r o n sources. First, high r e s o l u t i o n
e x p e r i m e n t s with dispersive crystal s p e c t r o m e t e r s
h a v e b e c o m e p r a c t i c a b l e as a c o n s e q u e n c e of i m p r o v
ing flux a n d brightness a n d , second, m a g n e t i c p r o p e r
ties c a n n o w be studied b e c a u s e of p o l a r i z a t i o n of the
beam.
D e s p i t e t h e w e a k n e s s of the C o m p t o n cross section,
the fact r e m a i n s t h a t it is the d o m i n a n t i n t e r a c t i o n in
light m a t e r i a l s (including biological tissue) at t h e
energies traditionally used for x-ray r a d i o g r a p h y ,
which a r e typically a n o r d e r of m a g n i t u d e higher t h a n
the energies of t h e characteristic emissions used in
c r y s t a l l o g r a p h i c studies. T h i s p o i n t is e m p h a s i z e d in
Fig. 3 w h e r e t h e c o n t r i b u t i o n s t o the m a s s a t t e n u a t i o n
coefficient for c o n c r e t e a r e p l o t t e d . Scattering as well
as a b s o r p t i o n processes a t t e n u a t e the t r a n s m i t t e d
b e a m . B o t h p h o t o e l e c t r i c a b s o r p t i o n a n d elastic scat
tering rapidly d i m i n i s h in i m p o r t a n c e a t higher p h o
t o n energies; t h e C o m p t o n scattering cross section
d o e s n o t a n d it b e c o m e s the d o m i n a n t i n t e r a c t i o n at

Compton

1000

500

E n e r g y (keV)

Figure 3
The mass attenuation coefficients for photoelectric
absorption, elastic scattering and Compton scattering in
concrete as a function of the photon energy (source: J
Hubbell (1969) National Bureau of Standards,
NSRDS-NBS 29)

typical r a d i o g r a p h i c energies. T h u s , C o m p t o n scatter

ing is responsible for c o n t r a s t in m a n y typical r a d i o
g r a p h i c s i t u a t i o n s a n d this suggests the direct use of
the signal for i m a g i n g / d e n s i t o m e t r y , instead of its
indirect use, by virtue of its m a j o r c o n t r i b u t i o n t o the
p h o t o n a t t e n u a t i o n coefficient.

2. Line Profile

Analysis

This is a i m e d a t p r o v i d i n g i n f o r m a t i o n a b o u t elec
tronic b e h a v i o r in t h e b u l k m a t e r i a l . Defects, inclus
ions, grain b o u n d a r i e s , i m p u r i t i e s a n d so o n h a v e n o
m e a s u r a b l e effect a t their n o r m a l c o n c e n t r a t i o n s . Al
t h o u g h the C o m p t o n line s h a p e is a projection of the
total electron d i s t r i b u t i o n (as s h o w n by E q n . (4)) it
retains a surprising sensitivity t o t h e b e h a v i o r of t h e
outer, s l o w - m o v i n g electrons involved in solid-state
b o n d i n g . T h i s research t o p i c h a s been c o v e r e d by
Williams (1977) a n d h a s been u p d a t e d in review
articles (see, for e x a m p l e , C o o p e r 1985).
G o o d resolution of the C o m p t o n line s h a p e m i g h t
be t h o u g h t of as, for e x a m p l e , 1 0 % of t h e F e r m i
m o m e n t u m in a m e t a l . Such resolution h a s only
recently b e c o m e available from the use of focusing xray optics. W h i l e the characteristic emission from a n
x-ray t u b e a n o d e r e m a i n e d as the source, the flux w a s
t o o low to m a k e such m e a s u r e m e n t s viable. I n s t e a d ,
the bulk of the w o r k of t h e 1980s t r a d e d r e s o l u t i o n
for statistical precision by replacing t h e crystal spec
t r o m e t e r with a s e m i c o n d u c t o r d e t e c t o r a n d t h e x-ray
source with a y-ray i s o t o p e e m i t t e r of generally higher
energy (i.e., greater t h a n 50 keV). In practice this h a s

Scattering

m e a n t m o m e n t u m resolution four o r five times worse

t h a n t h e target figure previously m e n t i o n e d , b u t at
6
a c c e p t a b l e c o u n t r a t e s (greater t h a n 10 c o u n t s p e r
198
d a y ) . T h e favored i s o t o p e used h a s been A u with a n
emission line at 412 keV b u t with a half-life of less
t h a n three d a y s , which p e r h a p s indicates the difficulty
of o p t i m i z i n g these e x p e r i m e n t s . T h e m e t h o d h a s
p r o v e d a critical test of theories of electrons in solids
a n d h a s , for e x a m p l e , been used to investigate the
b e h a v i o r of h y d r o g e n in m e t a l s a n d the C o u l o m b
c o r r e l a t i o n s b e t w e e n t h e electrons in t r a n s i t i o n
metals.
A s sensitivity h a s been c o m p r o m i s e d by such p o o r
resolution, great e m p h a s i s h a s been placed o n the
a c c u r a c y of t h e d a t a processing. F o r t u n a t e l y , this will
n o longer be the case d u e to the arrival of brighter xray s y n c h r o t r o n sources; these m a k e the crystal
s p e c t r o m e t e r a practical p r o p o s i t i o n at a respectable
r e s o l u t i o n t h a t begins t o c o m p e t e with the allied
p o s i t r o n a n n i h i l a t i o n t e c h n i q u e (see West 1973 for an
introduction).

3. Densitometry

and

Imaging

C o m p t o n scattering offers an alternative to x-ray

t r a n s m i s s i o n m e t h o d s . Its a d v a n t a g e s are a p p a r e n t
from Fig. 4. First, the i n f o r m a t i o n is essentially three
d i m e n s i o n a l ; t o m o g r a p h i c r e c o n s t r u c t i o n is n o t
necessary. Second, a n e m b e d d e d defect can p r o d u c e
g r e a t e r c o n t r a s t in the scattered signal as o p p o s e d to
the t r a n s m i t t e d signal if collimated b e a m s are used.
F o r e x a m p l e , for the detection of a void the c o n t r a s t
C c a n a p p r o a c h 1 0 0 % if the size of the void m a t c h e s
the b e a m size, w h e r e a s in t r a n s m i s s i o n it d e p e n d s o n
the void size as C = for a small void. If sensitivity S
is defined as the m o d u l a t i o n of the signal (scattered o r
t r a n s m i t t e d ) by the defect, divided by the statistical
noise in the m e a s u r e m e n t , it c a n be s h o w n t h a t SJ
S^(jiL)~^
which implies t h a t the m e t h o d is c o m p e t i
tive for the inspection of thin m a t e r i a l s or of nearsurface regions of thick objects.
T h e s e a d v a n t a g e s , which h a v e been s u m m a r i z e d by
H a r d i n g (1985) a n d H o l t (1985), h a v e t o be set against
adverse c o n s i d e r a t i o n s of flux; for e x a m p l e , the in
spection time for collimated b e a m i m a g i n g is inversely
p r o p o r t i o n a l to the s q u a r e of t h e v o l u m e defined by
t h e incident a n d scattered b e a m s . Nevertheless, it is
a n a l t e r n a t i v e w h e n the object to be inspected is so
large o r so c o m p l e x t h a t t r a n s m i s s i o n m e t h o d s c a n n o t
be used.
T h e d e n s i t o m e t r y of light m a t e r i a l enclosed in
dense m a t e r i a l a n d the i m a g i n g of near-surface defects
a r e well suited to a scattering a p p r o a c h . In this
c a t e g o r y , the c h a r a c t e r i z a t i o n of o s t e o p o r o t i c b o n e
a n d t h e inspection of explosive fillers in m u n i t i o n s
offer t w o diverse illustrations of the s a m e principle:
t h a t real-time m e a s u r e m e n t s c a n be c o m p e t i t i v e with,
o r s u p e r i o r t o , the t r a d i t i o n a l a p p r o a c h e s . T h e use of

67

Compton

Scattering

DuMond J W 1933 The determination of electron

momentum. Rev. Mod. Phys. 5: 1-33
Evans R D 1958 The Compton effect. In: Corpuscles and
Radiation in Matter II, Handbuch der Physik, Vol. 34.
Springer, Berlin, pp. 218-97
Harding G 1985 X-ray scatter imaging in NDT. Int. Adv.
NDTW: 271-95
Harding G, Kosanetzky J 1987 Status and outlook of
coherent x-ray scatter imaging. J. Opt. Soc. Am. 933-44
Harding G, Kosanetzky J 1989 Scattered x-ray beam NDT.
Proc. ISRP-4. Nucl. Instrum. Methods A280: 517-28
Holt R S 1985 Compton imaging. Endeavour 9: 97-106
Stokes J A, Alvar R, Corey R L, Costello D G, John J,
Kocimski S, Lurie A, Thayer D D, Tripe A P, Young J
C 1982 Some new applications of collimated photon
scattering for nondestructive examination. Nucl. Instrum.
Methods 193: 261-7
West R 1973 Positron annihilation. Adv. Phys. 22: 263382
Williams G 1977 (ed.) Compton Scattering. McGraw-Hill,
New York

Figure 4
A comparison of scattering (detector at S) and
transmission (detector at T) geometries for the detection
of a void or inclusion of linear dimension / and
attenuation coefficient 0 embedded to a distance L in a
matrix characterized by an attenuation coefficient

intense w h i t e - b e a m b r e m s s t r a h l u n g sources such as

L I N A C S or high-voltage x-ray units c o u p l e d with
m u l t i d e t e c t o r configurations h a s led to the d e v e l o p
m e n t of practical systems for b a c k s c a t t e r i m a g i n g of
near-surface defects in alloy castings (Stokes et al.
1982),
fiber-reinforced
c o m p o s i t e s , airframe c o m
p o n e n t s a n d fastenings. R e c e n t d e v e l o p m e n t s h a v e
s h o w n t h a t high-voltage x-ray systems with s c a n n i n g
c o l l i m a t o r s a n d multiple d e t e c t o r s c a n b e used t o
4
2
inspect a r e a s of a p p r o x i m a t e l y 1 0 m m d o w n t o
d e p t h s of a p p r o x i m a t e l y 5-10 m m in scan times of
a r o u n d a m i n u t e with a spatial defect resolution
a p p r o a c h i n g 0.5 m m . T h e effective d e p t h of p e n e t r a
tion d e p e n d s o n the t u b e voltage a n d the target
m a t e r i a l , b u t typical figures of merit indicate t h a t the
t e c h n i q u e c a n be applied effectively t o a wide r a n g e of
p r o b l e m s in n o n d e s t r u c t i v e e v a l u a t i o n ( H a r d i n g a n d
K o s a n e t z k y 1987, 1989) a n d s o m e c o m m e r c i a l d e
v e l o p m e n t is u n d e r way. In m a n y of these cases o t h e r
superficial t e c h n i q u e s ( u l t r a s o u n d , e d d y c u r r e n t s , etc.)
are n o t viable.
See also: Composite Materials: Nondestructive Evaluation

Bibliography
Cooper J 1985 Compton scattering and electron momen
tum. Rep. Prog. Phys. 48: 415-81

68

M . J. C o o p e r
[University of W a r w i c k ,
Coventry, U K ]

Confocal Optical Microscopy

T h e confocal optical m i c r o s c o p e is a practical a n d
c o n c e p t u a l a d v a n c e in optical m i c r o s c o p y t h a t m a k e s
possible i m p r o v e d resolution a n d t h r e e - d i m e n s i o n a l
i m a g i n g . T h e c o n c e p t of confocal imaging, first des
cribed a n d p a t e n t e d by M i n s k y (1961, 1988), is b a s e d
o n a s c a n n i n g a p p r o a c h to i m a g e f o r m a t i o n . A s is
t r u e with m o s t c o n c e p t u a l a d v a n c e s the basic idea is
simple b u t , in this case, practical i m p l e m e n t a t i o n h a d
to wait for b r i g h t e r light sources, frame store b o a r d s
a n d powerful inexpensive c o m p u t e r s to b e c o m e c o m
m o n l y available. Since the object is illuminated a n d
the i m a g e detected p o i n t - b y - p o i n t , digitization a n d
c o m p u t e r s t o r a g e of images is relatively easy. T h u s ,
t h e associated c o m p u t e r system is as i m p o r t a n t as
the m i c r o s c o p e a n d is often the limiting p o r t i o n of
the system. A t h r e e - d i m e n s i o n a l graphics w o r k s t a t i o n
is usually needed to efficiently display the threed i m e n s i o n a l results.
T h e basic principle of confocal i m a g i n g is s h o w n in
Fig. l a . A p o i n t source of light e x p a n d s to fill the b a c k
focal p l a n e of t h e objective lens a n d is focused by the
objective o n t o the specimen. All b u t a few e x p e r i m e n
tal systems o p e r a t e in this " e p i - i l l u m i n a t i o n " m o d e .
L i g h t is reflected from t h e object b a c k i n t o t h e objec
tive lens, a n d the object p o i n t is i m a g e d in the p l a n e of
the d e t e c t o r p i n h o l e . T h e light p a s s i n g t h r o u g h the
p i n h o l e is detected b y a p h o t o m u l t i p l i e r . S o m e of the
incident light c a n , of c o u r s e , be reflected from objects
in the specimen t h a t a r e located in p l a n e s closer t o o r
further from t h e objective lens. Light from planes
closer t o t h e objective is r e p r e s e n t e d by a d o t t e d line
in Fig. l b . T h e focal p o i n t for this light is located

Confocal

Detector

()

(b)

Figure 1
Schematic diagram of the confocal imaging mode: (a) the
basic principle of confocal illumination and imaging for
the in-focus plane; and (b) the rejection of out-of-focus
light in the imaging portion of the system for light
originating above and below the in-focus plane

b e h i n d the p l a n e of t h e d e t e c t o r p i n h o l e . T h u s , t h e
light is c o n v e r g i n g a t t h e p l a n e of t h e p i n h o l e a n d only
a small a m o u n t goes t h r o u g h the p i n h o l e t o be
detected b y t h e p h o t o m u l t i p l i e r . Light o r i g i n a t i n g
from p l a n e s d e e p e r in t h e specimen is indicated in
Fig. l b b y the d a s h e d line a n d is focused in front of
the p l a n e of t h e p i n h o l e . T h i s light is diverging at t h e
p i n h o l e a n d , a g a i n , very little passes t h r o u g h t o t h e
p h o t o m u l t i p l i e r . A t w o - d i m e n s i o n a l i m a g e is col
lected by s c a n n i n g either t h e b e a m o r t h e specimen.
Since light from object p l a n e s a b o v e a n d below t h e
p l a n e of focus is rejected from t h e i m a g e , this t w o d i m e n s i o n a l i m a g e is a n " o p t i c a l s e c t i o n " t h r o u g h the
specimen. A s such it c a n be a w a y of n o n d e s t r u c t i v e l y
imaging three-dimensional or internal structure.
Beam scanning instruments are the most c o m m o n
a n d are of t w o types. T h e first uses a laser as its light
source a n d g a l v a n o m i c m i r r o r s o r a c o u s t o o p t i c a l
devices t o scan t h e b e a m ( W h i t e et al. 1987, Pawley
1990). T h e a c o u s t o o p t i c a l device is used for t h e line
scan (i.e., t h e fast scan d i r e c t i o n ) a n d a g a l v a n o m i c
m i r r o r is used t o scan t h e lines t o form a frame (i.e.,
the slower direction). T h e a d v a n t a g e s of these instru
m e n t s is t h a t they scan a t video rates with laser light
sources. H o w e v e r , m o s t of t h e b e a m s c a n n e d instru
m e n t s use t w o g a l v a n o m i c m i r r o r s a n d a r e limited t o
frame rates of 0.25 s o r longer. T h e second b e a m
scanned type uses a r a p i d l y s p i n n i n g disk with a large
n u m b e r of p i n h o l e s a n d b r o a d b a n d light sources such
as m e r c u r y o r x e n o n l a m p s ( B o y d e et al. 1990, Pawley
1990). I n these i n s t r u m e n t s , t h e holes in t h e disk act as
b o t h illuminating a n d detecting p i n h o l e s ( B o y d e et al.
1990, Pawley 1990). A n a d v a n t a g e of this a p p r o a c h is
t h a t a large n u m b e r of object p o i n t s a r e i m a g e d a t t h e
s a m e time a n d t h e disk c a n be r o t a t e d very rapidly.
A n a r e a detector, such as a c h a r g e d c o u p l e d device

Optical

Microscopy

( C C D ) c a m e r a , m u s t be used, b u t the system c a n

r e c o r d a n d allow direct visualization of images at
video r a t e s .
T h e o t h e r i n s t r u m e n t type scans t h e specimen
(Brakenhoff et al. 1979). T h e s e i n s t r u m e n t s h a v e the
highest i m a g e r e s o l u t i o n , b e c a u s e all c o m p o n e n t s in
the optical system a r e s t a t i o n a r y a n d the cones of light
t r a v e r s i n g the i n s t r u m e n t c a n always be o p t i m u m . In
the b e a m s c a n n i n g systems, it is n o t possible to
m a i n t a i n this c o n s t a n c y as a function of scan angle
(i.e., the optics a r e c o m p r o m i s e d for off-axis points).
T h u s , it is n o surprise t h a t the only r e p o r t of image
r e s o l u t i o n e q u a l to t h e theoretically predicted 4 0 %
i m p r o v e m e n t b e y o n d t h e Rayleigh limit utilized a
specimen s c a n n e d system (Brakenhoff et al. 1979).
Specimen s c a n n e d systems, h o w e v e r , are slower t h a n
the o t h e r systems, since they rely o n mechanically
s c a n n i n g a relatively large m a s s .
A c o m p i l a t i o n of articles describing m o s t practical
designs including their a d v a n t a g e s a n d limitations h a s
been edited by Pawley (1990) a n d a t h o r o u g h theoret
ical t r e a t m e n t of confocal systems h a s been presented
by W i l s o n a n d S h e p p a r d (1984).
C o n f o c a l reflection m o d e images are
often
d e g r a d e d by internal reflections which c a n s a t u r a t e
the d e t e c t o r a n d o b s c u r e i m a g e detail. P o l a r i z a t i o n
c o m p o n e n t s c a n be a d d e d t o t h e i n s t r u m e n t to mini
mize these artifactual signals a n d t o optimize the
i m a g e signal-to-noise r a t i o (Szarowski et al. 1992).
T h e s e c o m p o n e n t s a n d a r o t a t i o n stage also m a k e it
possible t o s t u d y birefringent m a t e r i a l s . In this case,
care m u s t be t a k e n to d e t e r m i n e w h e t h e r the s c a n n i n g
m i r r o r s t e n d t o r a n d o m i z e t h e p o l a r i z a t i o n vector
a n d , if so, w h e t h e r the effect d e p e n d s o n the angle of
incidence at the m i r r o r . T h e m i r r o r s t e n d t o alter the
degree of p o l a r i z a t i o n of t h e b e a m a n d t h e effect is
larger further from t h e center of the scan. T h u s ,
a c c u r a t e m e a s u r e s of birefringence m a y h a v e to be
restricted t o t h e center of the scan. Alternatively, a
specimen s c a n n e d system c o u l d be used. A polariza
tion filter at the light s o u r c e c a n be helpful even if the
s o u r c e is a p l a n e - p o l a r i z e d laser. Polarized confocal
optical m i c r o s c o p y h a s been used t o s t u d y semicon
d u c t o r s ( F e i l i n g - W a n g et al. 1990) a n d p h o t o r e s i s t s
(Hell a n d W i j n a e n d t s - v a n - R e s a n d t 1989).
T h e confocal m i c r o s c o p e is also a n excellent fluor
escence m i c r o s c o p e ; m o s t biological a p p l i c a t i o n s
utilize this i m a g e m o d e . F l u o r e s c e n c e o p e r a t i o n is
achieved b y merely inserting a filter in t h e illumina
tion light p a t h of F i g . l a b e t w e e n t h e source a n d
t h e d i c h r o i c m i r r o r , as well as a b a r r i e r filter in the
d e t e c t o r light p a t h b e t w e e n t h e dichroic a n d the
d e t e c t o r . F e w a p p l i c a t i o n s in m a t e r i a l s science are
expected t o utilize this i m a g e m o d e . T h u s , this article
will c o n c e n t r a t e o n reflection m o d e i m a g i n g .
T h e t h r e e - d i m e n s i o n a l d a t a r e c o r d e d by the c o n
focal m i c r o s c o p e c a n be displayed in a n u m b e r of
f o r m a t s . T h e simplest is t o display t h e optical sections
as a m o n t a g e as a function of d e p t h in the specimen.
69

Confocal

Optical

Microscopy

T h e images a r e analyzed by sequentially viewing t h e

optical sections a n d m e n t a l l y i n t e g r a t i n g t h e m i n t o a
t h r e e - d i m e n s i o n a l impression. T h i s is difficult a n d
time c o n s u m i n g , b u t very useful for s t u d y i n g fine
detail a t specific d e p t h s . Stereo p a i r s of t h e images c a n
be easily f o r m e d a n d a r e a c o n v e n i e n t w a y t o p r e s e n t
a t h r e e - d i m e n s i o n a l impression ( B o y d e 1985). T h e
m o s t flexible a n d powerful w a y of displaying the d a t a
is t o calculate a t h r e e - d i m e n s i o n a l r e c o n s t r u c t i o n
using t h e optical sections as i n p u t d a t a a n d p e r f o r m
ing either surface o r v o l u m e r e n d e r i n g (van d e r V o o r t
et al. 1989, T u r n e r et al. 1991, W r i g h t a n d S c h a t t o n
1991). T h e s e r e c o n s t r u c t i o n s c a n be viewed from a n y
perspective a n d r o t a t e d in real time t o reinforce t h e
impression of three d i m e n s i o n s a n d to p r o v i d e a
convenient a n d impressive visualization tool.

1. Three-Dimensional
Surfaces

Visualization

of

Complex

T h e surfaces of m a t e r i a l s a r e often very i m p o r t a n t t o

o u r u n d e r s t a n d i n g of their m e c h a n i c a l a n d chemical
p r o p e r t i e s a n d their i n t e r a c t i o n w i t h t h e o p e r a t i o n a l
e n v i r o n m e n t . F o r e x a m p l e , detailed k n o w l e d g e of
failure surfaces c a n be critical t o o u r u n d e r s t a n d i n g of
w h y t h e m a t e r i a l failed a n d h o w t o i m p r o v e its
p e r f o r m a n c e . S u c h surfaces a r e often c o m p l e x a n d
highly t h r e e d i m e n s i o n a l a t t h e m i c r o s c o p i c level.
S o m e surface structures resulting from t w o m o d e s of
failure are s h o w n in Figs. 2 a n d 3.
F i g u r e 2a is a series of images of t h e fracture
surface of a plastic d r i n k i n g c u p r e c o r d e d as a func
tion of d e p t h . Such a set of images is referred t o as a
series since it is r e c o r d e d a l o n g t h e o r optical axis of
t h e m i c r o s c o p e . A t o t a l of 20 images were collected
a n d each is s e p a r a t e d from the p r e v i o u s o n e by 50
a l o n g t h e axis. A subset of these i m a g e s s e p a r a t e d in
by 100 is s h o w n in Fig. 2a. Ideally, t h e distance
between images is e q u a l t o t h e d e p t h of field of the
objective lens. T h i s insures t h a t all s t r u c t u r e s within
the object c o n t r i b u t e t o the i m a g e a n d t h a t e a c h
c o n t r i b u t e s only once, b u t useful images c a n be
r e c o r d e d a t larger intervals, especially if a n e x t e n d e d
object is being observed.
T h e optical sections of a series c a n be s u p e r i m
p o s e d t o p r o d u c e a projection i m a g e which is in focus
t h r o u g h the entire d e p t h . T h i s h a s t h e practical effect
of e x t e n d i n g the d e p t h of field t o e q u a l t h e d e p t h of
the series w i t h o u t the s u p e r i m p o s i t i o n of out-offocus light. Projection i m a g e s a r e f o r m e d b y s u p e r i m
p o s i n g t h e c o r r e s p o n d i n g (x, y) pixels from all of t h e
optical sections. E a c h pixel in the projection i m a g e
c a n be t h e s u m m a t i o n of all t h e c o r r e s p o n d i n g pixels
with t h e s a m e (x, y) p o s i t i o n , o r it c a n be set e q u a l
to the m a x i m u m value of the c o r r e s p o n d i n g pixels
( m a x i m u m projection).
If t h e optical section furthest from the o b s e r v e r is
projected as a b o v e a n d e a c h section closer t o t h e

70

Figure 2
A set of optical sections and a stereo pair of the fracture
surface of a plastic drinking cup. The eight optical
sections in (a) are separated by 100 in the direction.
The same field is shown in stereo in (b), but comprises 20
superimposed optical sections, each separated by 50 .
The width of the field in both (a) and (b) is 1500 . A
x 4 objective lens with a numerical aperture (NA) of 0.13
was used

observer is shifted t o t h e left o n e pixel relative t o the

o n e further a w a y , a projection is p r o d u c e d t h a t cor
r e s p o n d s t o viewing t h e object with the left eye. T h e
s a m e process t o the right p r o d u c e s the perspective as
viewed from t h e right eye. W h e n the t w o images a r e
m o u n t e d side by side as in Fig. 2 b , a stereo p a i r is
f o r m e d ( B o y d e 1985). A qualitative t h r e e - d i m e n s i o n a l
i m a g e is f o r m e d in t h e b r a i n if each i m a g e is o b s e r v e d
by o n l y o n e eye. T h i s c a n b e achieved b y using a
stereo viewer, which h a s t w o lenses a n d restricts the
left eye t o view only t h e left i m a g e a n d the right eye t o
view only the right i m a g e . Alternatively, o n e c a n
diverge t h e eyes w i t h o u t the aid of a viewer t o p r o d u c e
t h e s a m e effect. If the o b s e r v e r ' s eyes a r e crossed, a
stereo view is also observed, b u t its perspective is
often reversed (i.e., the t o p a n d b o t t o m a r e reversed)
since t h e left eye will view t h e right i m a g e a n d right

Confocal

Optical

Microscopy

m a t e r i a l . Fissures in m i n e r a l specimens h a v e been

studied in a similar m a n n e r (Petford a n d Miller 1990).
F i g u r e s 3 a , b s h o w t h e tensile failure of t h e s a m e
specimen a s in F i g . 2. T h e m a t e r i a l w a s stressed in t h e
d i r e c t i o n p e r p e n d i c u l a r t o t h e p l a n e of Fig. 3a. T h e
stereo p a i r in F i g . 3a s h o w s t h e entire w i d t h of the
fractured surface a n d e x t e n d s from a p l a n e at which
t h e m a t e r i a l h a s its original w i d t h ( b o t t o m of the
stereo i m a g e ) 370 t o w a r d t h e observer. T h e nearly
vertical surface t o t h e left of t h e field is c o n t i n u o u s
w i t h o n e of t h e original surfaces. T h e m a t e r i a l frag
m e n t e d a n d s h e a r e d a l o n g t h e o u t s i d e surface a n d in
t h e p e r p e n d i c u l a r direction t h r o u g h t h e m a t e r i a l . A
view p e r p e n d i c u l a r t o t h e surface is s h o w n in Fig. 3b.
T h e t o r n f r a g m e n t e d surface a n d small fibers extend
ing a b o v e t h e surface a r e clearly visualized.

2. Three-Dimensional
Inside Transparent

Figure 3
A fracture surface of a plastic material that failed under
tension. The stereo image in (a) shows the perspective
looking down on the surface from above, and is composed
of 37 superimposed optical sections each spaced 10
apart along the direction. A similar field is imaged from
the side in (b), and this stereo pair is composed of 24
superimposed optical sections each separated by 10 .
The field width is 600 in both (a) and (b). A x 10 0.3
NA lens was used for both images

eye t h e left i m a g e . T h i s is d u e t o a reversal of t h e

image p a r a l l a x , b u t if s t r o n g d e p t h cues a r e p r e s e n t ,
the stereo i m a g e m a y n o t b e reversed. O b s e r v a t i o n of
these stereo effects is o b s e r v e r d e p e n d e n t .
T h e stereo p a i r of F i g . 2 b is t h e s a m e field s h o w n in
Fig. 2a a n d is c o m p o s e d from a series of 20 optical
sections r e c o r d e d a t intervals of 50 . T h e t h r e e d i m e n s i o n a l s t r u c t u r e of t h e fracture surface is clearly
s h o w n . T h e surface c h e c k i n g , p r o p a g a t i n g from t h e
u p p e r surface, p e n e t r a t e s a p p r o x i m a t e l y half t h e
thickness of t h e m a t e r i a l . A w a v y p a t t e r n of d e f o r m a
tion c o n t i n u e s t h r o u g h t h e m a t e r i a l a n d is c h a r a c t e r
ized by shallower fissures o r i g i n a t i n g from t h e c h e c k s
a n d p r o p a g a t i n g t o t h e o p p o s i t e surface. T h e s e fis
sures a r e clearly i m p o r t a n t t o t h e failure o f t h e

Visualization
Materials

of

Surfaces

S t r u c t u r e s inside t r a n s p a r e n t m a t e r i a l s c a n be visual
ized in three d i m e n s i o n s b y merely focusing i n t o the
m a t e r i a l . T h r e e factors influence t h e d e p t h t o which
i m a g e s c a n b e f o r m e d . T h e first is t h e w o r k i n g dis
t a n c e of t h e lens. T h e s e c o n d is t h e l i g h t - a b s o r b i n g
p r o p e r t i e s of t h e m a t e r i a l . T h e light m u s t traverse t h e
m a t e r i a l twice, o n c e w h e n i l l u m i n a t i n g t h e object a n d
a g a i n after it is reflected from t h e i n t e r n a l s t r u c t u r e .
H i g h l y a b s o r b i n g m a t e r i a l s will r a p i d l y decrease the
i m a g e signal-to-noise r a t i o as a function of d e p t h . T h e
t h i r d is t h e o p a c i t y of the i n t e r n a l s t r u c t u r e s . If a large
p e r c e n t a g e of t h e incident light is reflected from the
i n t e r n a l surface being i m a g e d , it m a y m a s k s t r u c t u r e s
d e e p e r in t h e m a t e r i a l .
A b l o c k of plexiglass t h a t h a s b e e n subjected t o a
m i c r o w a v e field is s h o w n in Fig. 4. T h e t o p surface of
t h e stereo i m a g e is 2500 b e l o w t h e surface of t h e
m a t e r i a l a n d e x t e n d s a n a d d i t i o n a l 1250 i n t o t h e
b l o c k . C a v i t a t i o n spheres a r e clearly s h o w n in a wide
r a n g e of sizes a n d a p p e a r t o b u d from e a c h o t h e r . T h e
larger spheres a r e c o m p o s e d of m a n y small b u b b l e s ,
w h i c h h a v e a large v a r i a t i o n in density within t h e
material. The dense areas appear to mask structures
t h a t m a y b e p r e s e n t d e e p e r in t h e m a t e r i a l . C a b l e
m a t e r i a l s for p o w e r lines a n d t h e interfaces b e t w e e n
s e m i c o n d u c t i v e a n d i n s u l a t i n g layers h a v e been
studied using these m e t h o d s ( H a r i d o s s et al. 1990).

3. Three-Dimensional

Visualization

of

Fibers

F i b e r s a r e increasingly i m p o r t a n t in a wide r a n g e of
m a t e r i a l s b o t h as t h e sole c o m p o n e n t a n d in c o m p o
sites. T w o p o l y e t h y l e n e fibers a r e s h o w n in stereo in
Fig. 5. T h e y were d r a w n in different w a y s , a n d s h o w
m a r k e d l y different s t r u c t u r e . T h e fiber in Fig. 5a is 40
times t h e size of t h o s e in Fig. 5b. B o t h fiber types
s h o w lines c o r r e s p o n d i n g t o surface s t r u c t u r e t h a t r u n

71

Confocal

Optical

Microscopy

Figure 4
Internal cavitation caused by a microwave field in a piece
of plexiglass. This stereo pair is composed of 25
superimposed optical sections each separated by 50
and represents a volume from 2500 to 3750 into
the material. The field width is 1500 . A x 4 0.13 N A
objective lens was used

parallel t o t h e l o n g axis of t h e fiber. T h e larger fibers

s h o w a checklike p a t t e r n t h a t p r o p a g a t e s i n t o t h e
fiber a n d is always a t a b o u t plus o r m i n u s 10 relative
to the transverse axis. F r o m t h e p r e s e n t i m a g e s , it is
n o t possible t o d e t e r m i n e w h e t h e r these s t r u c t u r e s a r e
fissures o r discontinuities in t h e index of refraction of
the fiber. H o w e v e r , t h e former e x p l a n a t i o n is s o m e
w h a t easier t o u n d e r s t a n d . T h e s m a l l e r - d i a m e t e r
fibers in Fig. 5b were d r a w n from a gel a n d also s h o w
transverse s t r u c t u r e . I n this case, t h e s t r u c t u r e s a r e
repetitive a l o n g t h e l o n g axis of t h e fiber a n d a r e
present t h r o u g h t h e entire fiber. T h e y a r e r o u g h l y 410 times smaller t h a n t h e s t r u c t u r e s in F i g . 5a a n d a r e
often t w i n n e d as in t h e lower right. A g a i n it is n o t
possible t o say with certainty w h e t h e r these s t r u c t u r e s
are fissures o r refractive index discontinuities. Inter
face regions in fiber-reinforced c o m p o s i t e s h a v e been
studied inside the c o m p o s i t e b y confocal optical
m i c r o s c o p y ( T h o m a s o n a n d K n o e s t e r 1990).

4. Three-Dimensional
Circuits

Visualization

of

Integrated

T h e inspection a n d analysis of p h o t o r e s i s t s a n d inte

g r a t e d circuits m a y benefit from t h r e e - d i m e n s i o n a l
i m a g i n g since b o t h a r e often c o m p o s e d of c o m p l e x
multilayered structures (Hell a n d W i j n a e n d t s - v a n R e s a n d t 1989, F e i l i n g - W a n g et al. 1990, M o n a h a n
a n d B e n s c h o p 1990, T o y 1990). T h e circuit in F i g . 6a
is a p o r t i o n of a n I B M m i c r o p r o c e s s o r c h i p a n d
shows a r a n d o m access m e m o r y a r e a . T h e lines a r e
w o r d a n d bit lines a n d t h e u n d e r l y i n g s t r u c t u r e s a r e
t r a n s i s t o r s . F i g u r e 6 b is a n i n p u t - o u t p u t a r e a o n t h e
p e r i p h e r y of a n I B M 4 M b y t e m e m o r y c h i p . T h e

72

Figure 5
Stereo images of polyethylene fibers. The fiber in (a) was
supplied by Dr Roger Porter, Polymer Sciences,
University of Massachusetts at Amherst. The field width is
600 and was recorded with a 10 0.3 objective
lens. The fiber in (b) was drawn from a gel and was
provided by Dr Richard Stein, Department of Chemistry,
University of Massachusetts at Amherst. The field width is
150 and was recorded with a 20 0.7 objective
lens and an electronic zoom of 2

t h i n n e r lines a r e circuit lines leading t o t h e c o n t r o l l e d

collapse c h i p c o n n e c t i o n p a d s , which is a n I B M
p a t e n t e d m e t h o d for h a n d l i n g t h e large n u m b e r of
i n p u t s a n d o u t p u t s o n high-density chips. T h e p a d
a r e a t o t h e right c o n n e c t s t o t h e next level. T h e t o t a l
o r d e p t h e x c u r s i o n is 8.4 in F i g . 6a a n d 11 in
Fig. 6 b .
G r a p h i c s w o r k s t a t i o n s c a n b e u s e d t o calculate a n d
display t h r e e - d i m e n s i o n a l r e c o n s t r u c t i o n s using a
series as t h e i n p u t d a t a . S u c h r e c o n s t r u c t i o n s p r o v i d e
a c o n v e n i e n t w a y of a n a l y z i n g t h e s t r u c t u r e of a n
object from all perspectives as t h e w o r k s t a t i o n cal
culates a n d displays a n y selected view of t h e re
constructed volume. Image-processing methods can
e n h a n c e p a r t i c u l a r features, while p s e u d o c o l o r is

Confocal

Optical

Microscopy

often used t o distinguish s t r u c t u r e s o r intensity levels,

o r b o t h . In a d d i t i o n , surfaces c a n be s h a d e d a n d m a d e
to a p p e a r with a n y o p a c i t y , t h e r e b y b l o c k i n g features
behind them or m a k i n g them m o r e prominent. T h e
integrated circuit i m a g e s of Figs. 6 a , b a r e r e c o n
structed in F i g . 7. T h e r e c o n s t r u c t i o n in F i g . 7a h a s
been c o n t r a s t e d t o s h o w t h e w o r d a n d bit lines
overlying t h e t r a n s i s t o r region. T h e b a c k g r o u n d h a s
been m a d e d a r k t o e n h a n c e t h e higher-level s t r u c
tures. T h e m i c r o p r o c e s s o r c h i p of F i g . 6 b h a s b e e n
r e c o n s t r u c t e d in F i g . 7 b a n d t h e c o n t r a s t o p t i m i z e d t o
e n h a n c e t h e surface t e x t u r e . T h e large b a s e a r e a t o t h e
left s h o w s small t h r e e - d i m e n s i o n a l s t r u c t u r e t h a t

Figure 7
Volume rendered images of the fields in Figs. 6a,b. Voxel
View software from Vital Images (Deerfield, IA) was used
on an IBM RISC 6000 320 Power Graphics Workstation
to volume render the images of the IBM chips: (a) is a
reconstruction of the microprocessor chip shown in stereo
in Fig. 6a; and (b) is a reconstruction of the memory chip
shown in stereo in Fig. 6b that has been optimized to
demonstrate surface texture, particularly that of the base
area to the left

a p p e a r s a s density v a r i a t i o n s even in t h e stereo p a i r

of F i g . 6 b . B o t h r e c o n s t r u c t i o n s a r e s h o w n after a
45 r o t a t i o n of t h e r e c o n s t r u c t e d field.
Figure 6
Integrated circuit stereo images, (a) Portion of an IBM
microprocessor chip: the image is composed of 14 optical
sections recorded at 0.6 intervals with a 60 1.4
objective lens and an electronic zoom of x 1.5; field width
equals 67 . (b) Input-output area of a 4 Mbyte memory
chip: the image is composed of 11 optical sections
recorded at 1 intervals with a 40 1.0 objective
lens and electronic zoom of x 1.2; field width equals
125 . The integrated circuits were made available by Mr
Robert E. Donlan of IBM, Burlington, VT and Mr
Willard McCoy of IBM, Albany, N Y

cknowledgements

T h i s w o r k w a s partially s u p p o r t e d b y U S Public
H e a l t h Service g r a n t s R R 02984 a n d R R 01219
a w a r d e d b y t h e N a t i o n a l C e n t e r for R e s e a r c h R e
s o u r c e s a n d N S F g r a n t D I R 9108492 s u p p o r t i n g t h e
c o n f o c a l facility a n d t h e Biological M i c r o s c o p y a n d
Image Reconstruction Resource.
See also: Acoustic Microscopy; Optical Microscopy; Scan
ning Electron Microscopy

73

Confocal

Optical

Microscopy

Bibliography
Boyde A 1985 Stereoscopic images in confocal (tandem
scanning) microscopy. Science 230: 1270-2
Boyde A, Xiao T, Corle F, Watson F, Kino G S 1990
An evaluation of unilateral TSM for biological applica
tions. Scanning 12: 273-9
Brakenhoff G J, Blom P, Barends 1979 Confocal scanning
light microscope with high aperture immersion lenses.
/. Microsc. 117: 219-32
Feiling-Wang, Ching-Bo-Juang, Bustamante C, Wu A Y
1990 Electrooptic properties of (Pb, La) (Zr, Ti)0/sub 3/,
BaTio/sub 3/(Sb, Ba)Nb/sub 2/O/sub 6/ and Ba/sub 2/
NaNb/sub 5/O/sub 15/ thin films by a confocal scanning
differential polarization microscope. Proc. 4th Int. SAMPE
Electronics Conf. SAMPE, Covina, CA, pp. 712-21
Haridoss S, Shinozaki D M, Cheng C 1990 Laser scanning
confocal light microscopy of cable materials. IEEE Int.
Symp. Electrical Insulation. Institute of Electrical and
Electronics Engineers, Toronto, Canada
Hell S, Wijnaendts-van-Resandt R W 1989 The application
of polarized confocal microscopy for the size measure
ment of resist structures. Proc. SPIE 1139: 92-8
Minsky 1961 Microscopy apparatus. US Patent No.
3,013,467
Minsky 1988 Memoir on inventing the confocal scanning
microscope. Scanning 10: 128-38
Monahan V, Benschop J 1990 Object contrast in the
confocal microscope and applications to lithographic
metrology. Proc. SPIE 1261: 72-8
Pawley J (ed.) 1990 Handbook of Biological Confocal
Microscopy. Plenum, New York
Petford N, Miller J A 1990 SLM confocal microscopy: an
improved way of viewing fission tracks. J. Geol. Soc,
London 147: 217-18
Szarowski D H, Smith L, Herchenroder A, Matuszek G,
Swann J W, Turner J 1992 Optimized reflection
imaging in laser scanning confocal microscopy: applica
tions to neurobiology. Scanning 14: 104-11
Thomason J L, Knoester A 1990 Application of confocal
scanning optical microscopy to the study of fibrereinforced polymer composites. J. Mater. Sci. Lett. 9:
258-62
Toy D A 1990 Confocal microscopy: the ups and downs of
3-D profiling. Semicond. Int. 13: 120-3
Turner J N, Szarowski D H, Smith L, Marko M, Leith A,
Swann J W 1991 Confocal microscopy and threedimensional reconstruction of electrophysiologically
identified neurons in thick brain slices. J. Electron
Microsc. Tech. 18: 11-23
van der Voort H T M , Brakenhoff G J, Baarslag W 1989
Three-dimensional visualization methods for confocal
microscopy. / . Microsc. 153: 123-32
White J G, Amos W B, Fordham 1987 An evaluation of
confocal versus conventional imaging of biological struc
tures by fluorescent light microscopy. / . Cell Biol. 105:
41-8
Wilson T, Sheppard C J R 1984 Theory and Practice of
Scanning Optical Microscopy. Academic Press, London
Wright S J, Schatten G 1991 Confocal fluorescence micros
copy and three-dimensional reconstruction. J. Electron
Microsc. Tech. 18: 2-10
J. N . T u r n e r a n d D . H . S z a r o w s k i
[New Y o r k S t a t e D e p a r t m e n t of H e a l t h ,
Albany, New York, USA]
74

Corrosion and Oxidation Study

Techniques
T e x t b o o k s a n d j o u r n a l s reveal such a p l e t h o r a of
m e t h o d s for t h e s t u d y of c o r r o s i o n t h a t s o m e guid
a n c e is necessary for t h e u n i n i t i a t e d t o discover t h e
o p t i m u m m e t h o d for their needs. T h i s article is
i n t e n d e d t o f o r m such a g u i d e a n d for this r e a s o n a
classification h a s b e e n a d o p t e d (see T a b l e 1) which
groups methods according to purpose rather than
a c c o r d i n g t o c o m m o n features in t h e m e t h o d s . T h i s
article is c o n c e r n e d with m e c h a n i s t i c studies. Test
m e t h o d s a n d m o n i t o r i n g techiques a r e covered else
w h e r e (see Corrosion:
Test Methods).
Mechanistic
studies i m p l y t h e ability t o distinguish t r a n s p o r t p r o
cesses o r p h a s e b o u n d a r y r e a c t i o n s d o w n t o t h e
a t o m i c scale. H o w e v e r , m e a s u r e m e n t s a r e m a d e with
all t h e benefits of a l a b o r a t o r y setting a n d e q u i p m e n t
m a y b e very sophisticated.
T h e first choice w h i c h m u s t be m a d e is b e t w e e n
e n v i r o n m e n t s , especially w h e t h e r it is a q u e o u s o r
g a s e o u s . W h e n m e t a l s c o r r o d e in t h e gas p h a s e it is
r a r e for significant losses of m a t e r i a l t o arise from
v a p o r i z a t i o n . T h u s it is usually possible t o assess the
extent of c o r r o s i o n b y t h e m a s s o r thickness of
c o r r o s i o n p r o d u c t f o r m e d . M a n y m e t h o d s in t h e
literature a r e v a r i a t i o n s o n this basic m e a s u r e m e n t .
S a m p l e s m a y also b e transferred readily t o the elec
t r o n m i c r o s c o p e o r s p e c t r o m e t e r for identification of
composition or morphology. In contrast, when metals
c o r r o d e in a n a q u e o u s m e d i a , t r a n s p o r t o r loss of
m a t e r i a l in soluble f o r m m u s t be expected a n d it is
usually impossible t o g a u g e t h e extent of r e a c t i o n by
t h e m a s s of p r o d u c t s o n t h e surface. M o r e o v e r , it is
usually difficult t o i n t e r p r e t t h e results of electron
m i c r o s c o p y o r of s p e c t r o m e t r y b e c a u s e of t h e effects
of v a c u u m o n t h e n o r m a l l y i m m e r s e d surface. R e
a c t i o n r a t e s m u s t be m e a s u r e d directly from m e t a l
losses o r inferred from t h e use of t h e electrochemical
p a r a m e t e r s of e l e c t r o p o t e n t i a l o r e x c h a n g e c u r r e n t
density. T h e different w a y s in which these c a n be
d e t e r m i n e d give rise t o t h e variety of electrochemical
m e t h o d s listed for c o r r o s i o n studies in a q u e o u s
environments.
T h e investigator m u s t secondly decide w h e t h e r t h e
need is for kinetic, chemical o r m o r p h o l o g i c a l d a t a
a n d which thickness r a n g e ( n m , o r m m ) is a
significant r a t e of w a s t a g e in t h e given situation. I n
s o m e c o r r o s i o n p r o b l e m s , such as pitting, b r e a k a w a y
o r stress-corrosion c r a c k i n g , t h e thickness is irrele
v a n t as t h e p h e n o m e n o n is purely local; m e t h o d s for
such studies a r e highlighted separately.

7. Gaseous
1.1

Corrosion

Kinetics

In t h e l a b o r a t o r y , t h e r a t e of c o r r o s i o n o r o x i d a t i o n
of a m e t a l o r alloy is m o s t simply m e a s u r e d in t e r m s

Corrosion

and Oxidation

Study

Techniques

Table 1
3
Classification of corrosion and oxidation study techniques
Type
Kinetics

Thickness
(m)
10"
10"

10-

Scratching electrode

Linear polarization resistance

Weight loss
AC impedance
Rotating disk
Artificial pits and crevices
Constant strain

Local
Chemistry

Differential reflectance
Ellipsometry

EXAFS
Mossbauer
Raman

Infrared
Coulometric reduction
Microelectrode

"
10~

"

Local
Morphology

10
10"

Aqueous

Ellipsometry

Light microscopy

Flexure
SEM

"
Local

Gaseous
Quartz piezobalance
XPS/AES
Microbalance
Volumetric measurement
AES depth profile
Thermobalance
Metallographic examination
SIMS
Electron diffraction
AES/XPS
XRD

STEM
Laser optical and Raman spectroscopy
Taper sections XRF
Spark source mass spectrometry
AES
Analytical TEM
Holography
TEM
Markers
RBS/RNR
SEM
Flexure and vibration
SEM

a AES, Auger electron spectroscopy; , electron probe microanalysis; EXAFS, extended x-ray absorption fine structure spectroscopy; RBS,
Rutherford backscattering; RNR, resonant nuclear reactions; SEM, scanning electron microscopy; SIMS, secondary-ion mass spectroscopy; STEM,
scanning transmission electron microscopy; TEM, transmission electron microscopy; XPS, x-ray photoelectron spectroscopy; XRD, x-ray diffraction;
XRF, x-ray fluorescence

of its weight gain in a given interval of time. A n a l y t i

cal balances with a sensitivity of 0.1 m g a r e readily
available a n d this c o r r e s p o n d s t o a n oxide thickness
2
of a b o u t 1 n m o n a s a m p l e of 1 c m in a r e a . T h u s ,
gravimetric m e t h o d s c a n be used t h r o u g h o u t t h e
entire thickness r a n g e . T o a v o i d u n i n t e n d e d t h e r m a l
cycles it is usual t o s u s p e n d t h e s a m p l e in t h e r e a c t i o n
c h a m b e r from a n external b a l a n c e so t h a t a c o n t i n u
o u s r e a d o u t of s a m p l e weight is available u n d e r
i s o t h e r m a l c o n d i t i o n s . Such devices a r e t e r m e d thermobalances. Traditionally, thermobalances are open
to the e n v i r o n m e n t a n d only the a t m o s p h e r e within
the reaction c h a m b e r is c o n t r o l l e d . T h e need for a
free-moving s u s p e n s i o n t o p a s s t h r o u g h a n orifice in
this c h a m b e r m a k e s it i m p r a c t i c a b l e t o e v a c u a t e t h e
c h a m b e r . C a r e m u s t be t a k e n t o c o m p e n s a t e for
b u o y a n c y a n d h e a t i n g - u p times which m a y give a
significant zero p o i n t e r r o r . T h u s , for w o r k in t h e
n a n o m e t e r r a n g e a small b a l a n c e totally enclosed
within the e n v e l o p e of t h e r e a c t i o n vessel is used. T h e

e n c l o s u r e c a n t h e n b e e v a c u a t e d as a s t a n d a r d state a t
t h e c o m m e n c e m e n t a n d e n d of t h e test e x p o s u r e . Such
a b a l a n c e is usually t e r m e d a m i c r o b a l a n c e a n d is
useful also in w o r k i n g with toxic a n d high- o r lowp r e s s u r e e n v i r o n m e n t s o r w i t h a t m o s p h e r e s which
w o u l d c o n d e n s e at r o o m t e m p e r a t u r e . A t a s u b n a n o m e t e r level of thickness, a q u a r t z p i e z o b a l a n c e m a y
be used. A t such trivial levels of r e a c t i o n t h e investi
g a t o r is likely t o be interested less in c o r r o s i o n t h a n in
adsorption phenomena. One problem with complex
gas a t m o s p h e r e s c o n t a i n i n g several p o t e n t i a l react a n t s (e.g., 0 2 , C , C l 2 o r S 4) is t h a t of d e t e r m i n i n g their
reacting p r o p o r t i o n s . A n a l y s i s of t h e p r o d u c t after
e x p o s u r e yields t h e gross u p t a k e s , b u t o n a c o n t i n u
o u s o r s e m i c o n t i n u o u s basis, analysis of t h e a t m o s
p h e r e m u s t b e used. T h i s m e a s u r e m e n t gives rise t o a
series of v o l u m e t r i c m e t h o d s in w h i c h t h e c h a n g e in
p a r t i a l p r e s s u r e of a c o m p o n e n t in a k n o w n isother
m a l v o l u m e of gas is m o n i t o r e d .
Position-sensitive m e a s u r e m e n t s of t h e extent of

75

Corrosion

and Oxidation

Study

Techniques

o x i d a t i o n can be m a d e by d e t e r m i n a t i o n of the c o r r o
sion p r o d u c t thickness. T h i s m e a s u r e m e n t is often
m a d e intermittently by t a k i n g m e t a l l o g r a p h i c s a m
ples, b u t in the case of s u b m i c r o m e t e r films c a n be
m o n i t o r e d c o n t i n u o u s l y by c h a n g e s in interference
colors. In t h e l a b o r a t o r y , m e a s u r e m e n t of shifts in
p h a s e angle a n d intensity b e t w e e n incident a n d re
flected light p e r m i t s the i n f o r m a t i o n available t o be
e x p a n d e d b y the t e c h n i q u e s of ellipsometry.
T h e results of thickness m e a s u r e m e n t s m a y be
e x t r a p o l a t e d in time t by use of a n a p p r o p r i a t e r a t e
2
law. I m p o r t a n t e x a m p l e s are (a) p a r a b o l i c , x = k{t,
which applies w h e n diffusion across the c o r r o s i o n
p r o d u c t is r a t e controlling; (b) linear, = k2t, which
applies w h e n the c o r r o s i o n p r o d u c t offers n o
impedance
to
reaction;
and
(c)
logarithmic,
x = k3\n(\ + ct), w h e n a passive layer of limiting
thickness is reached. T h e coefficients kl9 k2, k3 a n d c
are all c o n s t a n t at a given t e m p e r a t u r e . T h e d a t a
can be i n t e r p o l a t e d a n d , with care, e x t r a p o l a t e d
in t e m p e r a t u r e by the A r r h e n i u s r e l a t i o n s h i p , k =
kx exp( Q/RT). T h e value of the a c t i v a t i o n energy Q
m a y indicate the n a t u r e of the c o n t r o l l i n g t r a n s p o r t
-1
step; for e x a m p l e , ~ 2 0 0 kJ m o l indicates solid-state
diffusion. T h e value is r e d u c e d by s h o r t circuit diffu
sion, a l o n g grain b o u n d a r i e s for e x a m p l e , or surface
diffusion.
1.2

Chemistry

T h e chemical n a t u r e of the c o r r o s i o n p r o d u c t is fixed

by b o t h t h e r m o d y n a m i c a n d kinetic c o n s t r a i n t s . T h e
c o m p o s i t i o n of t h e o u t e r m o s t surface t e n d s t o w a r d s
t h e r m o d y n a m i c e q u i l i b r i u m with the gas p h a s e , while
the inner surface is in e q u i l i b r i u m with elements in the
alloy. It is the activity g r a d i e n t s between these equi
librium positions which give rise t o diffusion across
the layer a n d hence to the segregation of distinct
phases between t h e m . T h e relative stabilities of the
oxides, sulfides o r chlorides c o m m o n l y of c o n c e r n in
gaseous c o r r o s i o n a r e d e t e r m i n e d by their free ener
gies of f o r m a t i o n a n d m a y be predicted for a given
t e m p e r a t u r e by t h e use of a n E l l i n g h a m d i a g r a m .
T h e r e is n o w a n excellent r a n g e of m e t h o d s avail
able for investigation of the chemical s t r u c t u r e of t h e
c o r r o s i o n p r o d u c t . T h e y a r e all v a c u u m t e c h n i q u e s
involving large fixed e q u i p m e n t . F o r t h e earliest
stages of film g r o w t h v a r i o u s forms of ion spectros
c o p y m a y be used, such as s e c o n d a r y - i o n m a s s spec
t r o s c o p y ( S I M S ) which is available in s c a n n i n g o r
i m a g i n g forms, or ion scattering s p e c t r o s c o p y (ISS).
This g r o u p of techniques h a s sensitivity t o m o n o
layers of m a t e r i a l a n d c a n be especially v a l u a b l e
because of the ability t o detect h y d r o g e n . T h e y a r e
reflection techniques a n d hence the surface film c a n be
e x a m i n e d in place o n the m e t a l , b u t the m a s s spectra
m a y need specialist i n t e r p r e t a t i o n a n d q u a n t i t a t i v e
e v a l u a t i o n is still difficult t o achieve.
T h e m o s t useful m e t h o d available for analysis of
films in t h e n a n o m e t e r r a n g e of thickness is x-ray
76

excited p h o t o e l e c t r o n s p e c t r o s c o p y ( X P S o r E S C A ) ,
which yields a c o m p o s i t i o n within 5 % t o g e t h e r w i t h
firm a s s i g n a t i o n of the b o n d i n g state of m o s t species,
including oxygen a n d c a r b o n . Analysis for h y d r o g e n
is n o t possible a n d spatial resolution t o a r o u n d
200 is only j u s t b e c o m i n g available. T h i s is, h o w
ever, a n a r e a of c u r r e n t d e v e l o p m e n t a n d localized
analysis of thin films is best u n d e r t a k e n by A u g e r
electron analysis ( A E S ) , which is often c o m b i n e d with
s c a n n i n g electron m i c r o s c o p y ( S E M ) for g o o d visual
c o n t r o l of t h e a r e a analyzed. Identification of crystal
s t r u c t u r e in this thin-film region m u s t be b y electron
diffraction. O n very flat single-crystal surfaces, lowenergy electron diffraction ( L E E D ) is useful, b u t
generally reflection high-energy electron diffraction
( R H E E D ) w o u l d be used. C o n v e n t i o n a l t r a n s m i s s i o n
p a t t e r n s from films r e m o v e d from the surface, b y
m e t h a n o l i c iodine solution for e x a m p l e , m a y still be
the best m e t h o d .
F o r films of several m i c r o m e t e r s in thickness, t h e xr a y electron p r o b e m i c r o a n a l y z e r ( ) is of excep
t i o n a l value a n d widely available in the form of a n
energy-dispersive x-ray d e t e c t o r ( E D X A ) m o u n t e d o n
a n S E M . Special facilities a r e n e e d e d for elements
below s o d i u m in t h e periodic table, a n d c a r b o n is the
practical limit. Valence states a r e n o t available by
E D X A a n d X P S c a n be used o n fractured o r spalled
interfaces within thick scales, often t o great effect.
S t r u c t u r a l i n f o r m a t i o n within this r a n g e c a n be
o b t a i n e d by x-ray diffraction ( X R D ) in a d d i t i o n t o
E D methods.
Very thick films c a n be e x a m i n e d in scans across
m e t a l l o g r a p h i c sections by , o r in t o t a l by t h e
m e t h o d s of b u l k analysis, x-ray fluorescence ( X R F )
or s p a r k s o u r c e m a s s spectroscopy.
Investigation of local c o m p o s i t i o n a l v a r i a t i o n s in
thin films a n d p a r t i c u l a r l y for light elements (below
s o d i u m ) is best achieved by A E S a n d c o m p o s i t i o n a l
v a r i a t i o n s in thick films c a n be followed by a m e t h o d
in which A E S is o p e r a t e d in sequence with oxide
r e m o v a l by a n energetic ion b e a m t o yield a d e p t h
profile. A c o m p l e m e n t a r y m e t h o d for this f o r m of
analysis is t h e e x a m i n a t i o n of thin sections of oxide
scale in the analytical t r a n s m i s s i o n electron m i c r o
scope ( A T E M ) . Special p r o v i s i o n c a n be m a d e with
s o m e of these v a c u u m m e t h o d s for c o r r o s i o n p r o
cesses t o be studied in situ using h e a t e d gas cells.
Alternatively laser-excited optical s p e c t r o s c o p y o r
R a m a n s p e c t r o s c o p y , which d o n o t require a v a c u u m ,
c a n be used.
1.3

Morphology

M o r p h o l o g i c a l c h a n g e s d u r i n g g r o w t h of a n oxide
scale a r e i m p o r t a n t t o b o t h t h e c o r r o s i o n scientist a n d
the engineer. T h e s e a r e s h a p e a n d profile c h a n g e s
i n d u c e d by preferred crystallinity, directional g r o w t h
o r locally accelerated a t t a c k . S u c h p h e n o m e n a fre
q u e n t l y give rise t o stress. T h u s , i m p o r t a n t experi
m e n t s in which inert m a r k e r s are placed o n the

Corrosion

surface indicate t h a t o x i d a t i o n of elements in t h e first

half of t h e periodic table (below gallium) o c c u r s b y
diffusion of m e t a l i o n s a c r o s s t h e c o r r o s i o n p r o d u c t .
T h e s u b s e q u e n t drift of t h e oxides t o w a r d s t h e m e t a l
surface creates stress in t h e film, d e p e n d i n g o n t h e
local g e o m e t r y . T h i s m a y c a u s e t h e o x i d a t i o n r a t e of
small c o u p o n s t o differ from t h a t of large fabrica
tions. T h e u p t a k e of o x y g e n o r t h e d i s t r i b u t i o n of
d o p a n t elements a r e c o n v e n i e n t l y m e a s u r e d u s i n g
high-energy ion b e a m s b y R u t h e r f o r d b a c k s c a t t e r i n g
( R B S ) o r r e s o n a n t n u c l e a r r e a c t i o n s . Stress is
m e a s u r e d b y u n i l a t e r a l o x i d a t i o n of s t r i p o r disk
specimens followed b y m e a s u r e m e n t of
flexure.
Young's moduli are measured during oxidation by
frequency c h a n g e s in a v i b r a t i n g strip; they m a y differ
from t h o s e of n o n g r o w i n g oxide. T h e m o r p h o l o g i c a l
structure of scales c a n b e o b s e r v e d o n m e t a l l o graphically p r e p a r e d specimens u s i n g optical o r S E M
methods.

2. Aqueous

Corrosion

2.1 Kinetics
W h i l e electrochemical m e a s u r e m e n t s f o r m t h e basis
for t h e s t u d y of a q u e o u s c o r r o s i o n , t h e e m p h a s i s
d e p e n d s o n t h e kinetic region of i m p o r t a n c e . T h e
initial p e r i o d of r e a c t i o n is i m p o r t a n t for t h e light it
t h r o w s o n the r a t e of p a s s i v a t i o n of n e w surface a s it
w o u l d be e x p o s e d d u r i n g t h e fracture of m e t a l s . T h i s
rate, in t u r n , d e t e r m i n e s w h e t h e r a c r a c k c o n t i n u e s t o
p r o p a g a t e o r w h e t h e r , instead, t h e c r a c k b e c o m e s
b l u n t u n d e r t h e a c t i o n of electrochemical dissolution.
T h e p r o b l e m of i n s t r u m e n t a t i o n for w o r k in this
region is t h a t of r e s p o n s e r a t e , since r e c o r d s of events
o c c u r r i n g over millisecond p e r i o d s a r e r e q u i r e d . T h e
m a j o r design feature is t h e m e a n s p r o v i d e d t o e x p o s e
new surface w i t h i n t h e electrolyte a t a c o n t r o l l e d
m o m e n t . I n p o l a r o g r a p h y this is d o n e b y d r o p p i n g a
liquid m e t a l , m e r c u r y , from a n orifice; in t h e case of
n o r m a l m e t a l s it c a n only b e d o n e m e c h a n i c a l l y , for
e x a m p l e b y s t r a i n i n g o r s c r a t c h i n g t h e electrode. T h e
p o t e n t i a l of t h e surface relative t o a s t a n d a r d cell t h e n
indicates t h e p e r i o d d u r i n g w h i c h m e t a l is e x p o s e d ,
the c u r r e n t flow t h r o u g h t h e electrode gives t h e in
s t a n t a n e o u s r a t e of r e a c t i o n , w h i c h diminishes a s t h e
film heals, a n d t h e c h a r g e transferred indicates t h e
thickness of t h e film f o r m e d . I n a useful v a r i a n t of t h e
t e c h n i q u e a circular scratch is described b y a stylus o n
a r o t a t i n g disk.
T h e vast b o d y of studies o n a q u e o u s c o r r o s i o n is
c o n c e r n e d n o t with t h e p a s s i v a t i o n stage b u t w i t h
either t h e steady loss of m e t a l from unfilmed o r p a r t l y
filmed surfaces o r t h e loss of passivity of a surface
u n d e r chemical o r electrochemical a c t i o n . I n t h e s t a n
d a r d three-electrode test cell, t h e p o t e n t i a l of t h e
testpiece o r w o r k i n g electrode relative t o t h e s t a n d a r d
electrode is m e a s u r e d b y a very h i g h - i m p e d a n c e
electrometer as a function of t h e c u r r e n t flow b e t w e e n

and Oxidation

Study

Techniques

t h e w o r k i n g electrode a n d a c o u n t e r electrode. W h e n
a p o t e n t i o s t a t i c circuit is used, t h e c u r r e n t flow is
varied a u t o m a t i c a l l y until a preset p o t e n t i a l is reached
a n d held, w h e r e a s in a g a l v a n o s t a t i c circuit it is the
p o t e n t i a l w h i c h is varied. C o m m e r c i a l electronic de
vices a r e available t o p e r f o r m these functions a n d
m a k e it possible t o scan t h e p o t e n t i a l of the s a m p l e in
a stepwise, c o n t i n u o u s o r repetitive p a t t e r n .
W h e n t h e external c u r r e n t is p a s s e d t h r o u g h the
electrode, its p o t e n t i a l c h a n g e s as a n e w b a l a n c e
b e t w e e n the a n o d i c a n d c a t h o d i c r e a c t i o n s is e s t a b
lished. A t high c u r r e n t s (100 o r 1000 times t h e c o r r o
sion c u r r e n t ) , t h e r e a c t i o n a p p r o p r i a t e t o t h e direction
of t h e c u r r e n t is sufficiently d o m i n a n t for the testpiece
t o b e h a v e as a single electrode. Its p o t e n t i a l t h e n
varies logarithmically with t h e m e a s u r e d c u r r e n t I
a c c o r d i n g t o t h e Tafel e q u a t i o n
V = log

I/I0

T h i s relation gives a basis for t h e e x t r a p o l a t i o n of

t h e electrode c u r r e n t t h r o u g h t h e m i x e d p o t e n t i a l
r a n g e t o t h e rest p o t e n t i a l a n d h e n c e for d e t e r m i n i n g
t h e c o r r o s i o n c u r r e n t . U n f o r t u n a t e l y , p o l a r i z a t i o n of
t h e testpiece b y c u r r e n t s great e n o u g h t o reach the
Tafel region m a y c a u s e side r e a c t i o n s i n a p p r o p r i a t e t o
t h e c o r r o s i o n p r o c e s s being studied. H e n c e m e t h o d s
h a v e been i n t r o d u c e d t o p e r m i t e s t i m a t i o n of c o r r o
sion r a t e s using m e a s u r e m e n t s within t h e mixed elec
t r o d e region. I n t h e linear p o l a r i z a t i o n m e t h o d , use is
m a d e of t h e p r o p o r t i o n a l i t y b e t w e e n c u r r e n t a n d
p o t e n t i a l close t o t h e rest p o t e n t i a l ( 2 0 m V ) . T h e
slope of this line is k n o w n as t h e p o l a r i z a t i o n resist
a n c e Rp a n d
Rp=-(/4.6

I0)

T h e a s s u m p t i o n of linearity over t h e r a n g e allows I0

t o be d e t e r m i n e d u s i n g t h r e e o r four p o i n t m e a s u r e
m e n t s , w h i c h c a n be ideal for m o n i t o r i n g . M o r e
recently, c o m p u t e r - b a s e d iterative m e t h o d s h a v e been
i n t r o d u c e d w h i c h p e r m i t t h e c o r r o s i o n c u r r e n t to be
d e t e r m i n e d from t h e n o n l i n e a r regions either side of
t h e rest p o t e n t i a l ; these will b e c o m e powerful tools in
laboratory work.
A s t h e c o r r o s i o n r a t e increases, a c c u m u l a t i o n of
c o r r o s i o n p r o d u c t s as surface layers b e c o m e s increas
ingly evident a n d t h e r e a c t i o n r a t e is c o n t r o l l e d b y
m a s s t r a n s p o r t r a t h e r t h a n b y electron transfer. E a c h
t r a n s p o r t step h a s its o w n characteristics of p a t h
resistance a n d r e l a x a t i o n time a n d these c a n b e separ
a t e d b y t h e t e c h n i q u e s of a c electrochemistry. In these
m e t h o d s a n a c ripple is i m p o s e d o n t h e d c c u r r e n t
flowing t h r o u g h t h e testpiece so t h a t t h e c u r r e n t frequency s p e c t r u m c a n b e a n a l y z e d a n d h e n c e t h e
transfer p a t h s described b y a "circuit d i a g r a m " of
resistors a n d c a p a c i t o r s . T h e m e t h o d s a r e of especial
value for studies o n t h e m e c h a n i s m of failure of
p a i n t e d a n d c o a t e d surfaces.
T h e c o r r o s i o n r a t e of i m m e r s e d surfaces frequently
77

Corrosion

and Oxidation

Study

Techniques

d e p e n d s o n h y d r o d y n a m i c p a r a m e t e r s because of the
i m p o r t a n c e of m a s s transfer t h r o u g h the b o u n d a r y
layer. Such s i t u a t i o n s c a n be m o d e l l e d a n d c o n t r o l l e d
in the l a b o r a t o r y b y m e a n s of electrodes in the f o r m
of r o t a t i n g disks o r cylinders, using e q u a t i o n s for
b o u n d a r y layer thickness d e v e l o p e d originally by
Levich.
Locally high c o r r o s i o n rates, as in crevices o r in
pits, a r e of p a r t i c u l a r c o n c e r n in a q u e o u s c o r r o s i o n
a n d in this situation t h e overall c u r r e n t flow t h r o u g h
the electrode c a n b e irrelevant o r even misleading.
S t a n d a r d forms of crevice a r e p r o d u c e d b y tightening
testpieces t o g e t h e r a t a c o n t r o l l e d t o r q u e while pits
c a n be simulated using t h e relevant m e t a l as t h e lead
in a pencil-type electrode. In t h e latter instance, p r i o r
dissolution of t h e m e t a l c o r e p r o d u c e s t h e artificial
pits a n d charges t h e m with t h e a p p r o p r i a t e s o l u t i o n .
Special m e t h o d s a r e used t o p r e v e n t salt precipitates
in the pits, b u t thereafter pitting c o r r o s i o n rates c a n
be studied in isolation from general c o r r o s i o n . T h e
m o s t serious form of local c o r r o s i o n is t h a t which
occurs conjointly with applied stress which m a y be
static (stress-corrosion cracking) o r cyclic ( c o r r o s i o n
fatigue). Early m e t h o d s for t h e s t u d y of stressc o r r o s i o n c r a c k i n g utilized a static strain, i m p o s e d b y
c o n s t r a i n i n g the test pieces in a " C " jig for e x a m p l e ,
b u t m o r e m o d e r n m e t h o d s use a c o n s t a n t strain r a t e
applied by m e a n s of a t e n s o m e t e r , which is f o u n d t o
predict a c t u a l failure m o r e closely.
2.2

Chemistry

Surfaces a r e c a p a b l e of being e x a m i n e d in a m u l t i t u d e
of w a y s o n c e they a r e r e m o v e d from t h e test m e d i u m
b u t the validity of this a p p r o a c h m u s t be checked
against conclusions d r a w n from in situ e x a m i n a t i o n
by specialist m e t h o d s . F o r the earliest p h a s e of
g r o w t h , ellipsometry a n d differential reflectometry
h a v e been e m p l o y e d . T h i n (5 n m ) passive films c a n be
e x a m i n e d by E X A F S (extended x-ray a b s o r p t i o n fine
structure), by M o s s b a u e r s p e c t r o s c o p y , o r by laser
R a m a n s p e c t r o s c o p y in t h e presence of a t least thin
films of w a t e r . T h i c k e r films c a n be e x a m i n e d in situ
by infrared s p e c t r o s c o p y o r electrochemically by ex
a m i n a t i o n of the c o u l o m e t r i c r e d u c t i o n s p e c t r u m .
T h e s t u d y of t h e chemistry of local c o r r o s i o n b y in situ
m e t h o d s is very difficult, b u t m i c r o e l e c t r o d e s c a n be
inserted i n t o crevices a n d pits using the techniques
traditionally e m p l o y e d b y microbiologists.
2.3
Morphology
T h e thickness a n d texture of deposits f o r m e d in a n
a q u e o u s e n v i r o n m e n t c a n be very i m p o r t a n t in o p e r
ating p l a n t , because of their effect o n h e a t transfer
a n d , t h r o u g h friction factors, o n pressure d r o p . Such
overall effects m a y be easier t o m o n i t o r in situ t h a n
they are to e x a m i n e in detail. E a r l y stages of r o u g h e n
ing c a n be studied by ellipsometry o r h o l o g r a p h y , a n d
light m i c r o s c o p y c a n be e m p l o y e d for the s t u d y of
surface t e x t u r e o n t h e m i c r o m e t e r scale. T h e flexure

78

m e t h o d s e m p l o y e d in d r y o x i d a t i o n to m e a s u r e stress
a r e valid, b u t h y d r o d y n a m i c d i s t u r b a n c e associated
with t h e cyclic m e t h o d s m a y m a k e these u n a c c e p
table.

3.

Conclusion

T h e r e a d e r will h a v e discovered t h a t c o r r o s i o n m e t h
o d s cover t h e w h o l e b r e a d t h of techniques for c h e m
ical a n d physical analysis. It is h o p e d t h a t this review
will h a v e placed t h e g r o u p s of techniques i n t o their
c o n v e n t i o n a l c o n t e x t a n d will t h u s h a v e helped the
r e a d e r t o m a k e a n efficient literature search. N o
scientist s h o u l d , h o w e v e r , be d i s s u a d e d by this review
from c o m b i n i n g techniques with i m a g i n a t i o n in o r d e r
t o best suit their o w n needs.
See also: Corrosion: Test Methods; X-Ray Absorption
Spectroscopy: EXAFS and XANES Techniques

Bibliography
Azzam R M, Bashara 1977 Ellipsometry and Polarised
Light. North-Holland, Amsterdam
Birks N, Meier G 1983 Introduction to High Temperature
Oxidation of Metals. Edward Arnold, London
Frankenthal R P, Kruger J (eds.) 1978 Passivity of Metals.
Electrochemical Society, Princeton, NJ
Hearle J W S, Sparrow J T, Cross (eds.) 1972 The Use of
the Scanning Electron Microscope. Pergamon, Oxford
Mansfeld F 1976 The polarization resistance technique for
measuring corrosion currents. In: Fontana G, Staehle
R W (eds.) 1976 Advances in Corrosion Science and
Technology, Vol. 6. Plenum, New York, pp. 163-262
Mulvey T, Webster R 1974 Modern Physical Techniques
in Materials Technology. Oxford University Press, Oxford
Parkins R 1979 Development of strain-rate testing and its
implications. In: Ugianski G M, Payer J (eds.) 1979
SCCThe Slow Strain Rate Technique, STP 665. Amer
ican Society for Testing and Materials, Philadelphia, PA,
pp. 5-25
Rapp R A (ed.) 1970 Techniques of Metals Research, Vol. 4,
Pt. 2. Interscience, New York
Seah , Briggs D (eds.) 1983 Practical Surface Analysis by
Auger and X-Ray Photoelectron Spectroscopy. Wiley,
Chichester, UK
Shreir L L (ed.) 1976 Corrosion, 2nd edn. NewnesButterworths, London
J. E. Castle
[University of Surrey,
Guildford, U K ]

Corrosion: Test Methods

C o r r o s i o n testing h a s b e c o m e a n i m p o r t a n t activity,
b o t h in d e v e l o p i n g m a t e r i a l s for engineering applica
tions a n d in e v a l u a t i n g m a t e r i a l s a n d p r o d u c t s for use
in n e w processes, a p p l i c a t i o n s a n d o t h e r types of
service. C o r r o s i o n tests a r e used t o select m a t e r i a l s for
the c o n s t r u c t i o n of buildings, vehicles a n d e q u i p m e n t

Corrosion:

used in a variety of industries. C o r r o s i o n tests a r e also

used for q u a l i t y a s s u r a n c e b y m a t e r i a l s suppliers a n d
their c u s t o m e r s t o e n s u r e t h a t m a t e r i a l s will m e e t
their u l t i m a t e service r e q u i r e m e n t s . M a n y testing p r o
g r a m s c o n c e r n e d with b o t h n e w m a t e r i a l s a n d n e w
processes e m p l o y c o r r o s i o n tests. T h e results of these
tests a r e i m p o r t a n t in m a k i n g a variety of m a t e r i a l s related decisions.

1. Corrosion

Test

Methods

Table 1
Recommended guidelines for field tests
Type of test

Standard

Atmosopheric exposure
Process industries test in plants
Surface sea water
Oil production test

ASTM
ASTM
ASTM
NACE

G50
G4
G52
RP-07-75

Objectives

In general, c o r r o s i o n tests a r e designed either t o

m e a s u r e t h e c o r r o s i o n resistance of a m a t e r i a l t o a
specific e n v i r o n m e n t o r t o m e a s u r e t h e corrosivity of
a n e n v i r o n m e n t relative t o a specific m a t e r i a l o r g r o u p
of m a t e r i a l s . It is frequently necessary t o k n o w h o w a
specific m a t e r i a l will b e h a v e in a specific e n v i r o n m e n t .
In o t h e r s i t u a t i o n s it m i g h t b e necessary t o d e t e r m i n e
the best m a t e r i a l for service in a specific e n v i r o n m e n t .
In this case, a n u m b e r of m a t e r i a l s w o u l d be e x p o s e d
in the c o r r o s i o n test a n d t h e results e v a l u a t e d , b a s e d
o n t h e m a s s loss, cost p e r f o r m a n c e o r o t h e r r a t i n g
system.
C o r r o s i o n tests c a n b e used t o d e t e r m i n e t h e q u a l i t y
or acceptability of a m a t e r i a l , such as stainless steel in
a specific a p p l i c a t i o n , for e x a m p l e , a t a n k t o c o n t a i n
h o t nitric acid. In this case, b o t h t h e c o m p o s i t i o n of
t h e m a t e r i a l a n d its t h e r m a l h i s t o r y affect t h e per
f o r m a n c e of t h e alloy a n d so a c o r r o s i o n test p r o v i d e s
a n effective w a y t o m e a s u r e t h e suitability of a specific
lot of m a t e r i a l .
C o r r o s i o n tests a r e also used t o m o n i t o r t h e c o r r o
sivity of e n v i r o n m e n t s . S t a n d a r d m a t e r i a l s , s u c h a s
h i g h - p u r i t y zinc, for e x a m p l e , h a v e b e e n used t o
m e a s u r e t h e corrosivity of a t m o s p h e r e s a t v a r i o u s
locations. T h e results of these tests c a n be used t o
specify galvanized c o a t i n g s o n steel s t r u c t u r a l c o m
p o n e n t s . T h i s t y p e of test is especially v a l u a b l e in
e n v i r o n m e n t s w h i c h a r e c h a n g e a b l e o r n o t well c o n
trolled, for e x a m p l e , t h e a t m o s p h e r e , soils a n d
various water streams.
C o r r o s i o n tests c a n be used t o h e l p identify c o r r o
sive c o n d i t i o n s in e n v i r o n m e n t s w h i c h v a r y in c o r r o s i
vity. T h e o b s e r v a t i o n of a high c o r r o s i o n r a t e c a n b e
used as a signal t o o b t a i n s a m p l e s for analyses t o
d e t e r m i n e w h a t c o m p o s i t i o n a l variables a r e c h a n g i n g
t o p r o d u c e t h e high c o r r o s i o n r a t e . C o r r o s i o n tests
are also used t o d e t e r m i n e w h e n p r o d u c t s t r e a m s ,
such as gasoline o r fuel oil, a r e c o r r o s i v e t o s t o r a g e
vessels. Results of these tests assist p r o d u c e r s in
adding inhibitors or modifying the process conditions
in the m a n u f a c t u r e of such p r o d u c t s .

2. Service

Test

d e t e r m i n e suitable m a t e r i a l s o r t h e best m a t e r i a l for

use in this service. S u c h tests usually involve placing a
specimen o r c o u p o n of k n o w n d i m e n s i o n s a n d m a s s
i n t o t h e e n v i r o n m e n t for a specific length of time a n d
t h e n retrieving it a n d m e a s u r i n g its final c o n d i t i o n
relative t o its s t a r t i n g c o n d i t i o n . If a n u m b e r of
m a t e r i a l s a r e tested a t t h e s a m e t i m e , t h e n r a n k i n g s
a n d relative p e r f o r m a n c e r a t i n g s c a n b e d e t e r m i n e d .
If s t a n d a r d m a t e r i a l s a r e i n c l u d e d in t h e test, t h e n
t h e relative corrosivity of t h e e n v i r o n m e n t m a y be
established a t t h e s a m e t i m e b y c o m p a r i n g the per
f o r m a n c e of t h e s t a n d a r d m a t e r i a l with its p e r f o r m
a n c e in o t h e r e n v i r o n m e n t s . It is i m p o r t a n t t o design
t h e test t o o b t a i n t h e i n f o r m a t i o n which is desired.
M a n y pitfalls a n d p r o b l e m s c a n o c c u r in field testing
w h i c h c a n lead t o e r r o n e o u s c o n c l u s i o n s . T h e use of
specimen h o l d e r s w h i c h a v o i d crevice a n d galvanic
c o r r o s i o n is often r e q u i r e d . Stressed o r welded
c o u p o n s a r e also frequently e m p l o y e d t o e v a l u a t e
t h e possibility of stress-corrosion c r a c k i n g a n d weld
attack.
Field tests a r e also used t o m o n i t o r t h e corrosivity
of e n v i r o n m e n t s such as c o o l i n g w a t e r so t h a t inhibi
t o r levels c a n b e k e p t a t a p r o p e r value. S t a n d a r d i z e d
c o u p o n s a r e frequently used for this p u r p o s e , al
t h o u g h s o m e t i m e s m o r e sophisticated a p p r o a c h e s a r e
desirable.
E l e c t r o c h e m i c a l a n d electrical resistance m e a s u r i n g
i n s t r u m e n t s a r e available w h i c h c a n simplify t h e m e a
s u r i n g process a n d p r o d u c e results in a s h o r t p e r i o d of
time. T h e electrical resistance m e t h o d is b a s e d o n t h e
principle t h a t t h e resistance of a wire is inversely
p r o p o r t i o n a l t o t h e cross-sectional a r e a of t h e wire.
C o r r o s i o n reduces t h e cross section of t h e wire a n d
c o n s e q u e n t l y increases its electrical resistance. Elec
t r o c h e m i c a l t e c h n i q u e s a r e b a s e d o n t h e fact t h a t
m a t e r i a l s w h i c h c o r r o d e m o r e r a p i d l y also require
m o r e c u r r e n t t o c a u s e a small shift in their electro
chemical p o t e n t i a l .
G u i d e l i n e s for c a r r y i n g o u t field tests of different
types h a v e b e e n p u b l i s h e d a n d a listing of s o m e of
these is p r o v i d e d in T a b l e 1.

Tests

Service tests a r e usually carried o u t for t h e p u r p o s e of

e v a l u a t i n g specific m a t e r i a l s in a service c o n d i t i o n .
T h e m a i n p u r p o s e of such tests is usually either t o

3. Laboratory

Tests

L a b o r a t o r y c o r r o s i o n tests m a y b e divided i n t o a
n u m b e r of categories, including i m m e r s i o n tests,

79

Corrosion:

Test

Methods

Table 2
Recommended guidelines for laboratory immersion tests
Type of test
Atmospheric pressure test
Vibratory cavitation erosion test
Process industries immersion test
Autoclave testing in high-temperature
water
Dynamic testing in high-temperature
water
Zirconium alloys in high-temperature
water

Method
specification
ASTM G31
ASTM G32
NACE TM-01-69
NACE TM-01-71
NACE TM-02-74
ASTM G2

simulated a t m o s p h e r e tests, accelerated tests a n d elec

t r o c h e m i c a l tests. I m m e r s i o n tests a r e usually set u p
to c o n t r o l t h e t e m p e r a t u r e , a g i t a t i o n , presence of
dissolved gases, solution c o m p o s i t i o n a n d time of
e x p o s u r e in liquid m e d i a . Specimens a r e usually
evaluated for loss of m a s s , o r o t h e r characteristics
such as d e v e l o p m e n t of stress-corrosion c r a c k s , pit
ting a n d crevice c o r r o s i o n . S u c h tests a r e especially
useful in the process industries w h e r e m i x t u r e s of
chemicals a n d solutions t h a t h a v e n o t been e v a l u a t e d
before are e n c o u n t e r e d . W h e n it is necessary t o r u n
i m m e r s i o n tests a t higher pressures, a variety of
a p p r o a c h e s h a v e been used involving either a u t o
claves o r high-pressure circulating l o o p s .
Guidelines h a v e been p r e p a r e d for r u n n i n g i m m e r
sion tests by t h e A m e r i c a n Society for T e s t i n g a n d
M a t e r i a l s ( A S T M ) a n d the N a t i o n a l A s s o c i a t i o n of
C o r r o s i o n Engineers ( N A C E ) . A list of applicable
d o c u m e n t s is given in T a b l e 2.
Simulated a t m o s p h e r i c tests were devised for the
p u r p o s e of o b t a i n i n g c o r r o s i o n p e r f o r m a n c e results
o n m a t e r i a l s which w o u l d n o r m a l l y be e x p o s e d to the
a t m o s p h e r e a n d a r e relatively c o r r o s i o n resistant t o
the a t m o s p h e r e in relatively s h o r t p e r i o d s of time. T h e
c o n c e p t of such testing is t o m a x i m i z e the time w h e n
corrosive c o n d i t i o n s occur. T h i s eliminates the long
p e r i o d s of time which n o r m a l l y o c c u r d u r i n g a t m o s
pheric e x p o s u r e w h e n there is little o r n o corrosive
action. Such tests usually try to simulate a specific
type of corrosive a t m o s p h e r e , for e x a m p l e , m a r i n e
a t m o s p h e r e (the Salt S p r a y test ( A S T M BI 17)) w h e r e
the presence of a i r b o r n e chloride is t h e m o s t i m p o r t
a n t c o r r o d a n t . O t h e r tests, such as the H u m i d i t y
C a b i n e t test ( A S T M D 1 7 4 8 ) , simply use the presence
of c o n d e n s i n g m o i s t u r e t o accelerate the c o r r o s i o n
process. T h e K e s t e r n i c h test e m p l o y s sulfur dioxide
plus high h u m i d i t y in t h e e n v i r o n m e n t to s i m u l a t e t h e
effects of u r b a n a t m o s p h e r e s c o n t a i n i n g high sulfur
dioxide levels. A l t h o u g h simulated service tests, such
as those a l r e a d y m e n t i o n e d , a r e designed t o p r o d u c e
results similar t o w h a t occurs in the a t m o s p h e r e , it h a s
long been recognized t h a t they often fall s h o r t of this

80

goal, b o t h in t e r m s of p r o d u c i n g c o r r o s i o n similar t o
t h a t which o c c u r s in t h e a t m o s p h e r e a n d in p r o d u c i n g
results in a timely m a n n e r . H o w e v e r , they h a v e been
useful in d e v e l o p i n g m o r e resistant c o a t i n g s , such as
p a i n t s a n d e l e c t r o d e p o s i t e d c o a t i n g s for o u t d o o r use.
T h e so-called accelerated tests h a v e been devised t o
speed u p the c o r r o s i o n process even further. T h e y a r e
used p r i m a r i l y as q u a l i t y a s s u r a n c e tests carried o u t
o n lots of m a t e r i a l for a c c e p t a n c e in specific a p p l i c a
tions. In these tests, significant c h a n g e s a r e m a d e in
the corrosive e n v i r o n m e n t in o r d e r t o accelerate t h e
c o r r o s i o n process. T h i s a p p r o a c h h a s b e e n widely
used t o d e v e l o p e l e c t r o d e p o s i t i o n systems for a u t o
m o t i v e a n d o t h e r d e c o r a t i v e a p p l i c a t i o n s . I n this case,
acceleration of t h e c o r r o s i o n process is achieved b y
a d d i n g , for e x a m p l e , acetic acid a n d c u p r i c ions. T h i s
is t h e basis of t h e C o p p e r Accelerated Acetic A c i d Salt
S p r a y ( C A S S ) test ( A S T M B368). T h e C o r r o d k o t e
test ( A S T M B380) e m p l o y s b o t h cupric a n d ferric ion
a d d i t i o n s . T h i s a p p r o a c h h a s also been used in evalu
a t i n g t h e stress-corrosion c r a c k i n g of v a r i o u s alloys
a n d a n u m b e r of specific test e n v i r o n m e n t s h a v e
evolved for this p u r p o s e . Accelerated tests a r e usually
specific for a m a t e r i a l system a n d c a n n o t be used
generally with a n y a s s u r a n c e t h a t t h e results will be
meaningful except for t h e specific m a t e r i a l for which
the test w a s developed.
T h e r e c o g n i t i o n t h a t t h e c o r r o s i o n process in
a q u e o u s systems is electrochemical in n a t u r e h a s led
m a n y investigators t o e x a m i n e the possibility of using
electrochemical t e c h n i q u e s in c o r r o s i o n testing. Elec
t r o c h e m i c a l testing t e c h n i q u e s h a v e t h e a d v a n t a g e of
o p e r a t i n g directly o n t h e c o r r o s i o n m e c h a n i s m a n d as
a result c a n yield a variety of i n f o r m a t i o n n o t readily
available from o t h e r types of testing. Electrochemical
tests c a n be used t o m e a s u r e t h e c o r r o s i o n r a t e
i n s t a n t a n e o u s l y t h r o u g h t h e p o l a r i z a t i o n resistance
a p p r o a c h (see Corrosion and Oxidation Study Tech
niques). T h u s , results c a n be o b t a i n e d in situ a n d very
quickly. Electrochemical t e c h n i q u e s c a n be used t o
vary t h e oxidizing p o w e r of the e n v i r o n m e n t a n d a t
t h e s a m e time t o m e a s u r e the r e s p o n s e of m a t e r i a l s t o
this v a r i a t i o n . S u c h tests h a v e given us a m u c h b e t t e r
u n d e r s t a n d i n g of t h e p e r f o r m a n c e of passive m a t e r
ials such as stainless steels. S o m e s t a n d a r d electro
chemical test m e t h o d s a r e listed in T a b l e 3.

4. Standardized

Test

Methods

T h e use of s t a n d a r d m e t h o d s in c o r r o s i o n testing h a s
b e c o m e m o r e i m p o r t a n t in recent years b e c a u s e of the
recognition t h a t there a r e m a n y pitfalls for investi
g a t o r s w h o use c o r r o s i o n tests. A n u m b e r of s t a n
d a r d s h a v e been referred t o in the p r e c e d i n g section
a n d a d d i t i o n a l s t a n d a r d s a r e being d e v e l o p e d b y a
n u m b e r of o r g a n i z a t i o n s , i n c l u d i n g t h e A m e r i c a n
Society for T e s t i n g a n d M a t e r i a l s , t h e British

Corrosion:

Table 3
Electrochemical test standards
Title
Reference method for potentiostatic and
potentiodynamic polarization
measurements
Potentiodynamic polarization resistance
measurements
Conventions applicable to
electrochemical measurements on
corrosion testing
Measurement of impedance of anodic
coatings on aluminum
FACT (Ford Anodized Aluminum
Corrosion Test)

Test

Methods

Bibliography
Designation

ASTM G5
ASTM G59
ASTM G3
ASTM B457
ASTM B538

S t a n d a r d s I n s t i t u t i o n , t h e N a t i o n a l A s s o c i a t i o n of
Corrosion Engineers and the International Standards
Organization.
See also: Corrosion and Oxidation Study Techniques

Ailor W (ed.) 1971 Handbook on Corrosion Testing and

Evaluation. Wiley, New York
American Society for Testing and Materials 1984 Annual
Book of ASTM Standards, Vol. 03.02. ASTM, Philadel
phia, PA
Cocks F (ed.) 1973 Manual of Industrial Corrosion
Standards and Control, STP 534. American Society for
Testing and Materials, Philadelphia, PA
Fink F W 1972 Corrosion testing. In: Hampel C A (ed.)
1972 Encyclopedia of Electrochemistry. Krieger, Mel
bourne, FL, pp. 295-7
Fontana G, Greene D 1967 Corrosion Engineering.
McGraw-Hill, New York, pp. 116-56
Shreir L L (ed.) 1976 Corrosion, 2nd edn., Vols. 1, 2.
Newnes-Butterworths, London, Chaps. 8, 20
Uhlig (ed.) 1948 Corrosion Handbook. Wiley, New
York, pp. 953-1083
S. W . D e a n Jr.
[Air P r o d u c t s a n d C h e m i c a l s , A l l e n t o w n ,
Pennsylvania, USA]

81

D
Depth Profiling
A d v a n c e d m a t e r i a l s science a n d t e c h n o l o g y c a n b e
characterized b y a n increasing i m p o r t a n c e of surfaces,
interfaces a n d thin films. F o r e x a m p l e , thin-film s t r u c
tures for microelectronic devices, optical, w e a r - a n d
corrosion-resistant c o a t i n g s , surfaces modified by ion
i m p l a n t a t i o n , electron o r laser b e a m r a d i a t i o n , a n d so
o n a r e b a s e d o n t h e u n d e r s t a n d i n g a n d c o n t r o l of
processes a n d p h e n o m e n a a t t h e a t o m i c scale. T h e
resulting p r o p e r t i e s as well as r e a c t i o n s a t surfaces
a n d interfaces, such as o x i d a t i o n a n d c o r r o s i o n , segre
gation a n d interdiffusion c a n only be u n d e r s t o o d if
the relevant c h a n g e s of t h e chemical c o m p o s i t i o n at
a n d n e a r interfaces a r e k n o w n . T h i s requires a q u a n t i
tative spatially resolved chemical a n d s t r u c t u r a l
analysis. In view of t h e p l a n a r s t r u c t u r e of thin films,
analysis of the i n - d e p t h d i s t r i b u t i o n of chemical c o m
position with high r e s o l u t i o n is of p r i m a r y i m p o r t
ance. T h e r e f o r e it is n o t surprising t h a t n u m e r o u s
m e t h o d s h a v e been d e v e l o p e d for this p u r p o s e , for
e x a m p l e , t h e n o n d e s t r u c t i v e m e t h o d s of R u t h e r f o r d
backscattering spectrometry (RBS), nuclear reaction
analysis ( N R A ) a n d p r o t o n - i n d u c e d x-ray emission
( P I X E ) , a n d t h e destructive m e t h o d s of m i c r o s e c t i o n ing the s a m p l e followed b y chemical analysis (for a
survey, see W e r n e r a n d G a r t e n 1984). A m o n g these,
the c o m b i n a t i o n of m i c r o s e c t i o n i n g b y i o n s p u t t e r i n g
with surface analysis t e c h n i q u e s is m o s t frequently
applied, because these depth-profiling m e t h o d s a r e
applicable t o practically a n y k i n d of m a t e r i a l a n d
allow the a t t a i n m e n t of o p t i m u m d e p t h r e s o l u t i o n
over a wide d e p t h r a n g e from a t o m i c m o n o l a y e r s u p
to several m i c r o m e t e r s .
T h e a i m of this article is t o s u m m a r i z e t h e funda
m e n t a l aspects a n d t h e p r e s e n t state of u n d e r s t a n d i n g
a n d o p t i m i z a t i o n of d e p t h profiling by s p u t t e r i n g in
materials research. F o r t h e physical principles of the
analysis m e t h o d s a n d for further details, see t h e
a p p r o p r i a t e review articles by O e c h s n e r (1984),
W e r n e r a n d G a r t e n (1984) a n d H o f m a n n (1990).

7. Principles

of Depth

Profiling

by

Sputtering

B o m b a r d m e n t of a solid surface with energetic p r i m

ary particles (usually ions b e t w e e n 0.5 K e V a n d 5 keV
energy) leads t o surface e r o s i o n b y emission of
s e c o n d a r y particles from t h e surface. By c o n t i n u o u s
sputtering, layers b e n e a t h t h e original surface a r e
subsequently exposed. T h e r e f o r e , there a r e t w o w a y s
to o b t a i n t h e i n - d e p t h d i s t r i b u t i o n of c o m p o s i t i o n as
a function of the s p u t t e r e d d e p t h : by analysis of either
the s p u t t e r e d m a t t e r o r of the r e m a i n i n g surface as a
function of the s p u t t e r i n g time.

T h e m o s t frequently a p p l i e d m e t h o d s of surface
analysis a r e s e c o n d a r y ion m a s s s p e c t r o m e t r y ( S I M S ) ,
s e c o n d a r y n e u t r a l s m a s s s p e c t r o m e t r y ( S N M S ) , ion
scattering s p e c t r o m e t r y (ISS), A u g e r electron s p e c t r o
m e t r y ( A E S ) a n d x-ray p h o t o e l e c t r o n s p e c t r o m e t r y
( X P S o r E S C A , electron s p e c t r o m e t r y for chemical
analysis) (see, for e x a m p l e , W e r n e r a n d G a r t e n 1984).
W h e r e a s S I M S a n d S N M S a n a l y z e t h e sputtered
m a t t e r , A E S , X P S a n d ISS analyze the r e m a i n i n g
surface. T h e d e p t h of i n f o r m a t i o n of these techniques
is of t h e o r d e r of 1 n m o r below, which is a p r e r e q u i
site for o b t a i n i n g high i n - d e p t h resolution. H o w e v e r ,
they differ m a r k e d l y with respect t o e l e m e n t a l specifity a n d sensitivity, chemical i n f o r m a t i o n , b a c k
g r o u n d , d y n a m i c r a n g e , lateral r e s o l u t i o n a n d d e p t h
of i n f o r m a t i o n . T h e s p u t t e r i n g p r o c e s s is i n d e p e n d e n t
of t h e analysis m e t h o d a n d c a n therefore be c o n
sidered separately.
H i g h spatial r e s o l u t i o n m e t h o d s like s c a n n i n g
A u g e r m i c r o s c o p y ( S A M ) c a n be used in a n a l t e r n a t
ive w a y t o reveal t h e i n - d e p t h d i s t r i b u t i o n by lateral
s c a n n i n g over a bevelled section of a s a m p l e . H i g h
r e s o l u t i o n is o b t a i n e d with t h e t e c h n i q u e of c r a t e r
edge profiling ( H o f m a n n 1990, 1991a) a t t h e rim of a
s p u t t e r c r a t e r with slope angle a, because the magnifi
3
c a t i o n factor 1 / t a n a typically is a b o u t 10 , t h a t is,
1 laterally c o r r e s p o n d s t o 1 n m in d e p t h . T h e m a i n
a d v a n t a g e of this t e c h n i q u e is t h a t a d e p t h profile c a n
be o b t a i n e d after s p u t t e r i n g , i n f o r m a t i o n lost d u r i n g
s p u t t e r i n g c a n be retrieved a n d t h e signal-to-noise
figure c a n be i m p r o v e d .
C o m m e r c i a l i n s t r u m e n t s for d e p t h profiling consist
of a n ion g u n , a s a m p l e stage a n d a m a s s analyzer
( S I M S ) , ion energy analyzer (ISS) o r electron energy
a n a l y z e r ( A E S , X P S ) . A E S a n d X P S need a n electron
g u n o r a n x-ray s o u r c e , respectively. All these facilities
a r e a s s e m b l e d in a stainless steel c h a m b e r with a n ion,
t u r b o m o l e c u l a r o r c r y o p u m p t o m a i n t a i n a base
p r e s s u r e of reactive gases in the u l t r a h i g h v a c u u m
8
( U H V , ^ 1 0 " P a ) r a n g e . T h i s is necessary t o avoid
d i s t o r t i o n s c a u s e d by surface r e a c t i o n s of reactive
species such as C O , H 2 0 a n d h y d r o c a r b o n s . O f
c o u r s e , inert a r g o n which is m o s t often used as
b o m b a r d m e n t gas supply for t h e ion g u n m a y be
p r e s e n t with a higher p a r t i a l p r e s s u r e u p to a b o u t
2
10- Pa.
S p u t t e r e r o s i o n p r o c e e d s o n a n a t o m i c scale ( C a r t e r
et al. 1982). T h e r e f o r e , a d e p t h resolution in the
m o n o l a y e r regime s h o u l d be achievable. H o w e v e r ,
s p u t t e r i n g is n o t a n ideal layer-by-layer erosion b u t is
the result of a c o m p l e x ion b e a m - s a m p l e i n t e r a c t i o n
process. T h i s process i n d u c e s a variety of d i s t o r t i o n a l
effects o n b o t h surface m o r p h o l o g y a n d c o m p o s i t i o n ,

83

Depth

Profiling

I-fit)

Quantitative
s u r f a c e analysis

Sputtering
removal rate

X ' f i z )

Sputtering-induced
alterations of surface
composition and morphology

Figure 1
Principles of sputtering profile evaluation; conversion of a
measured profile, I=f(t)
to a true concentration profile

which generally cause b r o a d e n i n g of the m e a s u r e d

profile with respect t o the original o n e .
T h e m a i n t a s k in q u a n t i t a t i v e d e p t h profiling is t o
d e t e r m i n e t h e local c o m p o s i t i o n A"as a function of t h e
d e p t h below t h e original surface, X=fiz).
The
e x p e r i m e n t a l i n f o r m a t i o n , h o w e v e r , consists of signal
intensities / as a function of t h e s p u t t e r i n g time t,
I =fij). If b o t h t h e relation b e t w e e n X a n d / a n d t h a t
between a n d t a r e linear, I=fiJ) p r o v i d e s a q u a l i t a
tive, a p p r o x i m a t e i m a g e of the elemental i n - d e p t h
d i s t r i b u t i o n . Q u a n t i t a t i v e d e p t h profiling requires
c a l i b r a t i o n of b o t h t h e analysis signal a n d t h e s p u t t e r
ing r a t e , as schematically s h o w n in Fig. 1. A s s u m i n g
t h a t such a c a l i b r a t i o n h a s been achieved, t h e result
ing profile will still deviate from t h e original i n - d e p t h
d i s t r i b u t i o n o w i n g t o i o n - b e a m - i n d u c e d c h a n g e s of
surface c o m p o s i t i o n a n d t o p o g r a p h y (Fig. 1). T h i s
deviation generally is a certain b r o a d e n i n g a n d is
characterized by t h e d e p t h r e s o l u t i o n Az (i.e., t h e
resolved d e p t h ) which is a figure of m e r i t for t h e
precision of a profile ( H o f m a n n 1990). T h e r e f o r e ,
o p t i m i z a t i o n of Az is indispensable for the achieve
m e n t of high-quality d e p t h profiles.
1.1 Depth Scale
Calibration
In practice, t w o w a y s t o d e t e r m i n e t h e s p u t t e r i n g r a t e
are often applied. T h e first is t o s p u t t e r for a suffi
ciently long time /, t o o b t a i n a c r a t e r , the d e p t h dx of
which c a n be d e t e r m i n e d by a profilometer. T h e
second is t o s p u t t e r profile with the s a m e c o n d i t i o n s a
T a 2 0 5 - T a s a m p l e of k n o w n oxide thickness dx a n d
d e t e r m i n e t h e time tx t o r e a c h t h e o x i d e - m e t a l inter
face. T h e s p u t t e r i n g r a t e i is t h e n = dz/dt =
djtv
N o t e t h a t in the second case, t h e s p u t t e r i n g r a t e is for
T a 2 O s a n d s h o u l d be c o n v e r t e d t o t h e t r u e s p u t t e r i n g
r a t e by c o m p a r i s o n with the respective s p u t t e r i n g
yield of the s a m p l e m a t e r i a l , for e x a m p l e , from litera
t u r e d a t a . I n b o t h cases, only a n a v e r a g e s p u t t e r i n g
r a t e is o b t a i n e d . T h e i n s t a n t a n e o u s s p u t t e r i n g r a t e
generally d e p e n d s o n the c o m p o s i t i o n . T h i s m a y
84

c a u s e a n o n l i n e a r i t y in t h e d e p t h - t i m e relation w h i c h
w o u l d r e q u i r e auxiliary t e c h n i q u e s of in situ m e a s u r e
m e n t of t h e i n s t a n t a n e o u s s p u t t e r i n g r a t e ( O e c h s n e r
1984), which a r e generally t o o c o m p l i c a t e d for p r a c t i
cal profiling.
1.2 Calibration of
Composition
T h e general p r o b l e m of quantification of surface
analysis m e t h o d s is b e y o n d t h e scope of this article
a n d is t h e subject of special p u b l i c a t i o n s ( W e r n e r a n d
G a r t e n 1984, B e n n i n g h o v e n et al. 1987). W h e r e a s in
A E S a n d X P S quantification is i n d e p e n d e n t of s p u t t e r
e r o s i o n , b o t h a r e directly c o u p l e d in S I M S a n d
S N M S . T h e m a i n a d v a n t a g e of the latter m e t h o d s is
their low b a c k g r o u n d a n d large c o n c e n t r a t i o n r a n g e
(see Sect. 3), w h i c h allows trace analysis, a n d their
capability of h y d r o g e n detection. W h e r e a s A E S a n d
X P S s h o w only a w e a k m a t r i x d e p e n d e n c e of their
sensitivity, S I M S is difficult t o quantify b e c a u s e t h e
i o n i z a t i o n p r o b a b i l i t y strongly varies with c o m p o s i
tion. S p u t t e r i n g with O J i o n s in S I M S is a m e t h o d t o
r e d u c e t h e m a t r i x effect, while p o s t i o n i z a t i o n of s p u t
tered n e u t r a l s as in S N M S allows a practically m a t r i x i n d e p e n d e n t c a l i b r a t i o n . A first-order quantification
in A E S a n d X P S c a n be achieved by the use of
elemental sensitivity factors.
Q u a n t i t a t i v e analysis d e p e n d s o n t h e chemical
b o n d i n g state of t h e elements w h i c h is directly
observed in X P S . In A E S , p e a k s h a p e a l t e r a t i o n s d u e
to chemical b o n d i n g m a y c h a n g e t h e p e a k - t o - p e a k
height values of t h e spectra in t h e u s u a l derivative
m o d e . Recently, least-squares fitting of s t a n d a r d spec
t r a as well a s factor analysis h a s been i n t r o d u c e d t o
e x t r a c t q u a n t i t a t i v e l y t h e chemical i n f o r m a t i o n in
d e p t h profiling ( N e l s o n 1984, H o f m a n n a n d Steffen
1989) (see Sect. 3).

2. Distortional
Effects
Profiling
Conditions

and Optimized

Sputter

A m e a s u r e d d e p t h profile generally differs from t h e

t r u e i n - d e p t h d i s t r i b u t i o n of c o m p o s i t i o n o w i n g t o a
large n u m b e r of d i s t o r t i o n a l effects ( H o f m a n n 1990).
T h e y c a n b e r o u g h l y categorized as i n s t r u m e n t a l
factors, effects d e p e n d i n g o n s a m p l e c o m p o s i t i o n a n d
m o r p h o l o g y a n d t h e f u n d a m e n t a l effects of ion
b e a m - s a m p l e i n t e r a c t i o n s . A c o m p i l a t i o n of t h e m o s t
i m p o r t a n t causes of profile d i s t o r t i o n s is given in
T a b l e 1. I n general, their influence results in b r o a d e n
ing of t h e m e a s u r e d profile w i t h respect t o t h e original
i n - d e p t h d i s t r i b u t i o n . It is c h a r a c t e r i z e d b y the d e p t h
r e s o l u t i o n Az w h i c h c a n be directly d e t e r m i n e d in t h e
s p u t t e r i n g profile of a s h a r p interface A - B as s h o w n
schematically in F i g . 2. U s i n g this principle, t h e Az
c a n be o b t a i n e d from t h e relative a m p l i t u d e of thin
m u l t i l a y e r profiling ( H o f m a n n 1986) (see F i g . 3).
I n s t r u m e n t a l factors d e p e n d o n t h e p r o p e r s e t u p of
t h e i n s t r u m e n t . A n o n u n i f o r m ion b e a m intensity

Depth
Table 1
Survey of the main distortional effects in sputter profiling
Effect

Category
Instrumental
factors

Ion-beaminduced effects

Sample
characteristics

adsorption from residual gas atmosphere

redeposition of sputtered species
impurities in ion beam
nonuniform ion beam intensity
information depth of analysis method
primary ion implantation
atomic mixing
sputtering-induced roughness
preferential sputtering and decomposition
of compounds
enhanced diffusion and segregation
original surface roughness
crystalline structure and defects
alloys, compounds, second phases
insulators

gives a c o n t r i b u t i o n t o Az p r o p o r t i o n a l t o t h e s p u t
tered d e p t h ; this m e a n s it is p r e p o n d e r a n t for large
d e p t h s (Sean a n d H u n t 1983). T h e d e p t h of i n f o r m a
tion d e p e n d s o n t h e analysis m e t h o d a n d o n t h e
sample c o m p o s i t i o n . It is o p t i m u m in I S S , w h e r e only
the first m o n o l a y e r is detected, a n d in S I M S o r S N M S
with low i o n energy w h e r e it is of t h e o r d e r of 1-2
m o n o l a y e r s given by t h e origin of t h e s p u t t e r e d
particles. I n electron spectroscopies ( A E S a n d X P S ) ,
the electron escape d e p t h p e r p e n d i c u l a r t o t h e
surface d e t e r m i n e s t h e d e p t h of i n f o r m a t i o n . It is of
the o r d e r of 0 . 3 - 3 n m , d e p e n d i n g o n t h e kinetic
energy of t h e respective A u g e r o r p h o t o e l e c t r o n line
a n d o n t h e angle o f emission t o t h e surface n o r m a l
(Seah a n d D e n c h 1979). F o r very thin layers
of < 5 n m thickness, t h e latter p r o p e r t y p r o v i d e s a

A
true

profile

\
\
measured profile~\X

\
^

y'

y'\

/
/
/
1

\
\

- resolution function
\
\
\

-\

2 = - ^
Sputtered

depth

(z)

Figure 2
Definition of the depth resolution (84%-16%) = 2 for
a Gaussian resolution function at a sharp interface A-B

Profiling

n o n d e s t r u c t i v e profiling t e c h n i q u e using v a r i a t i o n s of
the angle of emission, for e x a m p l e , by tilting the
s a m p l e . Angle-resolved X P S h a s b e c o m e particularly
p o p u l a r for t h e d e t e r m i n a t i o n of overlayer thick
nesses a n d of elemental d i s t r i b u t i o n in t h e altered
layer in s p u t t e r i n g (Bussing a n d H o l l o w a y 1985).
Most fundamental are ion-bombardment-induced
effects resulting from a l t e r a t i o n s of s a m p l e c o m p o s i
tion a n d m o r p h o l o g y o n a n a t o m i c scale. Surface
m i c r o r o u g h e n i n g d u e t o t h e statistical n a t u r e of the
s p u t t e r i n g p r o c e s s (Seah et al. 1981) a n d a t o m i c
mixing in t h e collisional c a s c a d e ( A n d e r s e n 1979) are
inevitable ( C a r t e r et al. 1982). B o t h effects result in a n
initial increase of Az with the s q u a r e r o o t of d e p t h (Az
1/2
oc z ) a n d t e n d t o s a t u r a t e a t a d e p t h of the o r d e r of
the projected ion r a n g e . W h e r e a s the surface m i c r o r o u g h e n i n g c o n t r i b u t i o n Azs results in a b o u t 2 - 5
m o n o l a y e r s d e p e n d i n g o n surface t r a n s p o r t a n d sur
face b i n d i n g energy, t h e a t o m i c mixing c o n t r i b u t i o n
Azk d e p e n d s m a i n l y o n projectile a n d b u l k m a t e r i a l s
p a r a m e t e r s . Similar t o t h e ion r a n g e , Azk increases
with t h e ion energy a n d decreases with the angle of
incidence ( A n d e r s e n 1979). T h i s is seen in Fig. 3,
w h e r e t h e results of Az for t a n t a l u m - s i l i c o n m u l t i
+
layers at different A r ion energies a n d incidence
angles a r e depicted ( H o f m a n n 1991a). O b v i o u s l y , low
ion energy a n d / o r high incidence angle a r e required
for o p t i m i z e d d e p t h resolution. A s a n e x a m p l e , Fig. 4
+
s h o w s the i m p r o v e m e n t o b t a i n e d b y using 1 keV A r
+
at a n incidence angle of = 80 instead of 3 keV A r
a t = 50, in o r d e r t o disclose a 7 n m thick TiSi
interlayer o n a silicon s u b s t r a t e a t a t o t a l s p u t t e r e d
d e p t h of 200 n m ( P a m l e r et al. 1990a).
I o n b o m b a r d m e n t frequently causes preferential
s p u t t e r i n g of o n e c o m p o n e n t a n d results in a further
profile d i s t o r t i o n , as recognized, for instance, in the
d r o p of the oxygen signal in A E S profiling of a T a 2 O s
layer ( H u n t a n d Seah 1983). A n a c c o m p a n y i n g
c h a n g e in t h e t o t a l s p u t t e r i n g yield m a y lead t o a
c h a n g e in the t i m e - d e p t h relation, a n d a n increased
a s y m m e t r y is o b s e r v e d w h e n s p u t t e r i n g t h r o u g h a n
interface of m a t e r i a l s with different s p u t t e r i n g yields
( H o f m a n n 1991a). In s o m e m a t e r i a l s , segregationa n d r a d i a t i o n - e n h a n c e d diffusion lead t o further p r o
file d i s t o r t i o n s . C h a r g i n g of i n s u l a t o r s m a y cause
e l e c t r o t r a n s p o r t of m o b i l e ions. In A E S , electron
s t i m u l a t e d d e s o r p t i o n m a y act like a n a d d i t i o n a l
selective s p u t t e r i n g , while s a m p l e h e a t i n g by a n in
tense, focused electron b e a m leads t o e n h a n c e d interdiffusion d u r i n g profiling. C o n e a n d ripple f o r m a t i o n
a r e p r o b a b l y d u e t o r a d i a t i o n - i n d u c e d diffusion a n d
r e d e p o s i t i o n a n d a r e frequently o b s e r v e d in unidirec
t i o n a l s p u t t e r i n g a t larger s p u t t e r e d d e p t h , leading to
a d e g r a d a t i o n of d e p t h r e s o l u t i o n (Cirlin et al. 1991).
S a m p l e characteristics a r e of c o n s i d e r a b l e influence
in d e p t h profiling. T h e original surface r o u g h n e s s
causes a n a d d i t i o n a l profile b r o a d e n i n g d e p e n d i n g
m a i n l y o n t h e ion b e a m angle of incidence a n d o n the
s p u t t e r e d d e p t h ( Z a l a r a n d H o f m a n n 1987). Because

85

Depth

Profiling

Sputter time (min)

Sputter time (min)

Figure 3
AES depth profiling results
of a tantalum-silicon multilayer structure of 20 nm alternating silicon (d = 7 nm) and tantalum
+
(d= 3 nm) layers: (a) Ar ion energy Epl = 1 keV, incidence angle = 68; (b) Epl = 3 keV, = 56; (c,d) depth resolution
A determined from the amplitude as a function of Epl (c) and of (d) (after Hofmann 1991a)

of the d e p e n d e n c e of t h e s p u t t e r i n g yield o n crystal

o r i e n t a t i o n , polycrystalline metallic m a t e r i a l s d e v e l o p
a surface r o u g h n e s s d u r i n g u n i d i r e c t i o n a l s p u t t e r i n g
w h i c h is p r o p o r t i o n a l t o t h e s p u t t e r e d d e p t h if t h e
m e a n grain size is larger t h a n ( P a m l e r et al. 1990b).
A m o r p h o u s m a t e r i a l s as well as oxides a n d s e m i c o n
d u c t o r s which t e n d t o a m o r p h i z e u n d e r ion b o m b a r d
m e n t generally s h o w a better d e p t h r e s o l u t i o n as
c o m p a r e d with crystalline m e t a l s ( c o m p a r e , for ex
a m p l e , Figs. 3 a n d 5).
A high incidence angle ( > 60) is d e t r i m e n t a l in
case of r o u g h surfaces, as s h o w n in Fig. 5. T h e
m a x i m u m Az for t h e n i c k e l - c h r o m i u m m u l t i l a y e r
with a s m o o t h surface a t a b o u t 35 is d u e t o t h e
preferred < 111 > o r i e n t a t i o n of t h e s p u t t e r - d e p o s i t e d
layers ( P a m l e r et al. 1990b). T h i s crystallinity effect is
86

m a r k e d l y r e d u c e d a t high incidence angles ( > 45).

F o r s a m p l e s w i t h r o u g h surfaces, h o w e v e r , it is d o m i
n a t e d b y r e d e p o s i t i o n a n d s h a d o w i n g effects which
increase with a n d d e t e r m i n e Az for > 60 (Fig. 5).
T o a lesser extent, this is also t h e case for T a 2 O s - T a
interfaces, which s h o w a lower Az of a b o u t 2 n m for
< 60 d u e t o t h e absence of crystallinity effects.
All t h e d i s t o r t i o n a l effects m e n t i o n e d so far c o n
t r i b u t e t o profile b r o a d e n i n g . If these c o n t r i b u t i o n s
Azj a r e i n d e p e n d e n t , their s u p e r p o s i t i o n c a n be d e
scribed by a n a d d i t i o n in q u a d r a t u r e t o t h e t o t a l
e x p e r i m e n t a l l y d e t e r m i n e d Az, given by

A z = [Z(^,)J

1 / 2

0)

Depth

Q_

10

f(bf~

20

30

40

N + Ti

/
y

/"

10

50

20

Ti
1
1
30 40

1
50 60

Si

/ \

70 80 \.l
90 1
100
.-/.

Sputter time (min)

Figure 4
Depth profiles of a TiN layer on top of silicon with a
titanium interlayer, sputter
profiled with different
+
+
conditions: (a) 3 keV A r , = 50 and (b) 1 keV A r ,
= 80 (after Pamler et al. 1990a, Wiley, Chichester,
UK, reproduced with permission)

E q u a t i o n (1) c a n be used t o e x t r a c t the relative

m a g n i t u d e of t h e different c o n t r i b u t i o n s t o the
m e a s u r e d , for e x a m p l e , with respect t o their
d e p e n d e n c e o n ion energy, incidence angle a n d sput
tered d e p t h . A s a general p r e d i c t i o n , the influence of
t h e d e p t h of i n f o r m a t i o n ( ), s p u t t e r i n g statistics
( 5) a n d a t o m i c m i x i n g ( A z k ) a r e p r e p o n d e r a n t for
thin surface layers ( ^ 5 n m ) , w h e r e a s with increasing
layer thickness the a d d i t i o n a l effects of original sur
face r o u g h n e s s a n d s p u t t e r i n g - i n d u c e d r o u g h n e s s , for
e x a m p l e , d u e t o crystallinity a n d n o n u n i f o r m ion
b e a m intensity, b e c o m e increasingly i m p o r t a n t (Hof
m a n n 1990) (see, for e x a m p l e , F i g . 6a).
C h a n g e s of t h e local s p u t t e r i n g r a t e within the
a n a l y z e d a r e a a r e c o n s i d e r a b l y r e d u c e d by multidirec
t i o n a l ion b o m b a r d m e n t . U s i n g t w o ion g u n s o p e r a t
ing in different d i r e c t i o n s relative t o t h e s a m p l e is the
simplest p r o c e d u r e a n d gives i m p r o v e d . A s s h o w n
for A E S d e p t h profiling of n i c k e l - c h r o m i u m m u l t i
layers b y Z a l a r (1985) r o t a t i o n of t h e s a m p l e d u r i n g
ion b o m b a r d m e n t is m o s t effective for optimized
d e p t h r e s o l u t i o n a n d results in a low a n d d e p t h i n d e p e n d e n t value of ( Z a l a r 1985, Cirlin et al.
1990). R e c e n t results b y Cirlin et al. (1991) h a v e
d e m o n s t r a t e d t h a t s a m p l e r o t a t i o n reduces surface
r o u g h n e s s also in S I M S profiles. X P S d e p t h profiles
yield a c o n s i d e r a b l e i m p r o v e m e n t w h e n t h e s a m p l e is
r o t a t e d as s h o w n in F i g . 6 for n i c k e l - c h r o m i u m
m u l t i l a y e r s . O b v i o u s l y , s a m p l e r o t a t i o n results in
r e d u c e d r o u g h n e s s of t h e c r a t e r b o t t o m a n d therefore
in h i g h - r e s o l u t i o n d e p t h profiles a t larger d e p t h .
A survey of o p t i m i z e d s p u t t e r profiling c o n d i t i o n s
is given in T a b l e 2. T h e s a m p l e characteristics refer t o
a s a m p l e for w h i c h o p t i m u m profiling results c a n be
p r e d i c t e d , e m p h a s i z i n g their d e p e n d e n c e o n t h e re
spective t y p e of s a m p l e .

3. Quantitative

10

20

60

70

Ion incidence angle,

30

40

50

()

Figure 5
Depth resolution as a function of the ion incidence
angle for smooth ( ) (i? a = 0.012 ) and rough ( O )
(Ra = 0.06 ) Ni-Cr+ multilayers at = 25 nm depth
(1 keV and 3 keV A r bombardment, respectively) and for
anodic
Ta 2O s-Ta layers ( , ) at = 30 nm depth (1 keV
+
Ar bombardment) (after Hofmann 1990)

Profiling

Evaluation

of Sputtering

Profiles

T h e degree of similarity of m e a s u r e d d e p t h profile

w i t h t h e t r u e i n - d e p t h d i s t r i b u t i o n of c o m p o s i t i o n
d e p e n d s m a i n l y o n t h e a t t a i n m e n t of o p t i m i z e d s p u t
tering c o n d i t i o n s as c o m p i l e d in T a b l e 2. In m a n y
cases, t h e precision o b t a i n e d is g o o d e n o u g h for the
p u r p o s e of t h e analysis. C a l i b r a t i o n of b o t h the
intensity scale in t e r m s of c o n c e n t r a t i o n a n d the
s p u t t e r i n g time scale in u n i t s of d e p t h is a first step t o
quantification, as discussed in Sect. 1. T h e latter
p r o c e d u r e is often difficult if t h e r e is a m a r k e d c o m p o
sition d e p e n d e n c e of t h e s p u t t e r i n g r a t e . In a second
step, t h e influence of t h e d i s t o r t i o n a l effects (Sect. 2)
must be taken into account. A n estimated depth
r e s o l u t i o n (e.g., from s h a r p interfaces of similar
m a t e r i a l s a t similar d e p t h ) gives a n i n d i c a t i o n of the
d e v i a t i o n b e t w e e n t h e m e a s u r e d a n d t h e t r u e profile.
M a t h e m a t i c a l l y , t h e c o n t r i b u t i o n s t o profile b r o a d e n
ing c a n b e described b y a r e s o l u t i o n function g(z z')
a n d t h e m e a s u r e d n o r m a l i z e d intensity I(z) is given b y

87

Depth

Profiling

/(z)=

100

200
300
400
Sputter time (min)

(\

Ni

Cr

100

200
300
Sputter time (min)

400

X(z)g(z-z')dz'

(2)

K n o w l e d g e of the r e s o l u t i o n function allows d e c o n v o l u t i o n of E q n . (2) t o o b t a i n t h e c o m p o s i t i o n a l ind e p t h d i s t r i b u t i o n X(z). In m a n y cases, g(z - z)

is k n o w n o r p r e d i c t a b l e , for e x a m p l e , for t h e influ
ence of a n a t o m i c mixing z o n e of w i d t h w ( L i a u
et al. 1979). T h e expected a s y m m e t r i c s h a p e of
the m e a s u r e d profile of a single s a n d w i c h layer
with thickness d= z 2 - zx is p r o p o r t i o n a l t o 1 exp[ - (z - zx + w)/w] a n d to exp[ - (z - z 2 + w)/w]
at t h e front a n d r e a r side, respectively ( H o f m a n n
1991a, b). A typical result of S I M S profiling of a
delta-spike d o p a n t layer of silicon (one m o n o l a y e r ) in
a G a A s m a t r i x o b t a i n e d b y B a d h e k a et al. 1990 is
s h o w n in Fig. 7, w h i c h c a n be fitted with E q n . (2)
using a r e s o l u t i o n function represented b y a super
p o s i t i o n of a t o m i c mixing ( a s y m m e t r i c ) e x p o n e n t i a l s
a n d of surface m i c r o r o u g h e n i n g ( G a u s s i a n ) (Hof
m a n n 1991c).
T h e effect of electron escape d e p t h in A E S a n d X P S

500

Figure 6
XPS depth profiling of multilayer structure of Ni-Cr with
16 alternating layers of 30 nm thickness
on a silicon
+
substrate, sputtering with 3 keV A r ions, = 45:
(a) with stationary sample and (b) with rotating sample
(1 rpm)

1.2 keV 0 : silicon marker in GaAs

Table 2
Survey of optimized sputter depth profiling conditions
Category
Sample ambient

Ion beam

Analyzing
conditions

Sample
characteristics

88

Condition
low residual
reactive gas pressure
8
(<10~ Pa)
"free" sample mount to prevent
redeposition
constant uniform intensity (scanning)
low beam energy (^ 1 keV)
high-mass ion species (or reactive species)
large incidence angle for smooth sample
(>60)
low incidence angle for rough sample
(<60)
two differently inclined beams
small analysis area relative to crater size
at the center of the crater (AES, XPS)
gating of analysis signal from the center
of the crater (SIMS, ISS)
sample rotation
smooth, polished surface
noncrystalline, no second phases
oxides, semiconductors
components with similar sputtering yields,
negligible diffusion and segregation and
good electrical and thermal
conductivities

Figure 7
Measured SIMS profile of +a silicon delta marker in GaAs
at z = 50 nm for 1.2 keV 0 ion bombardment at = 2
incidence angle, adapted from Badheka et al. (1990). The
full drawn curve shows a fit of the measured data using
superposition of an atomic mixing term (w = 1.5 nm) and
a Gaussian roughness broadening (cr = 1.5 nm). The
leading and trailing edges are approximated by
exponential functions with A L = 1.3 nm and = 3.4 nm
over one decade (after Hofmann 1991c)

Depth

to

exp. data

0(5IOeV)

calc. profile
true profile

10

Depth

15

20

25

(monolayers)

Figure 8
Example of the true, normalized in-depth distribution
evaluation with Eqn. (3). Measured data ( ) are from
the
+
oxygen (510eV) AES sputtering profile (1 keV A r ) of a
passive layer on a Fe-18%Cr-8%Ni stainless steel. The
full drawn line is the optimum fit calculated from the true
in-depth distribution (
) with (0) = 5.5 monolayers.
The missing oxygen in the first layer is due to
carbohydride contamination; the nonvanishing oxygen
content at larger depth can be explained by ion beam
shadowing due to surface roughness (after Sanz and
Hofmann 1986)

Profiling

is described b y g(z - z') = exp[ - ( - ')/] a n d E q n .

(2) c a n be solved giving t h e s o l u t i o n X(z) = I - dl/dz
w h e r e is t h e electron escape d e p t h . Such a c o r r e c t i o n
generally results in steeper g r a d i e n t s at interfaces
( H o f m a n n 1990). T h e r e m a i n i n g b r o a d e n i n g d u e t o
a t o m i c m i x i n g a n d surface r o u g h n e s s c a n be c o r r e c t e d
in s u b s e q u e n t steps b a s e d o n m o r e detailed estima
tions of t h e respective r e s o l u t i o n function. A s a firsto r d e r a p p r o x i m a t i o n , t h e c o n v o l u t i o n integral E q n .
(2) c a n b e solved a s s u m i n g a G a u s s i a n resolution
function by t h e u s u a l d e c o n v o l u t i o n m e t h o d s (Hof
m a n n a n d S a n z 1980). I n practice, t h e m e t h o d of t r u e
profile a s s u m p t i o n a n d c a l c u l a t i o n of t h e m e a s u r e d
profile is often a p p l i e d (see F i g . 8).
I n A E S d e p t h profiling of t h e first m o n o l a y e r of t h e
surface, as, for e x a m p l e , for segregation o r passive
layer studies, t h e r e s o l u t i o n function m a i n l y d e p e n d s
o n t h e f u n d a m e n t a l effects of a t o m i c mixing a n d
m i c r o r o u g h e n i n g as described b y t h e so-called se
q u e n t i a l layer s p u t t e r i n g (SLS) m o d e l a n d is repre
sented b y a P o i s s o n d i s t r i b u t i o n (Seah et al. 1981).
I n c l u d i n g t h e electron escape d e p t h , t h e n o r m a l i z e d
A E S o r X P S intensity is given b y (Sanz a n d H o f m a n n
1986)

GBN = < 5 I I >

= 970

sputtering rate = 0 . 6 nm min

:

2 monolayers min"

Sputtering time (min)

=III9K

Monolayers

Monolayers

Figure 9
AES depth profiles of the segregation layer on indium at a grain boundary of bicrystals of a Ni-1.2 at.% In alloy,
quenched from 970 K, 1119 and 1311 K. The in-depth distributions (b-d) result from the analysis of the sputtering
profiles in (a) using Eqn. (3) (after Muschik et al. 1989)
89

Depth

Profiling

/() =

( -

/
0

1)

-fv

+
"

exp( - )exp( ra/,)

(3)
with the d e p t h scale in a t o m i c m o n o l a y e r s . 7 0 is
a n o r m a l i z a t i o n factor, Xn+m is the m o l a r fraction
of the detected element in t h e layer n + m,
(w_1)
[z
/ ( - l)!]exp( - z) is the P o i s s o n d i s t r i b u t i o n
term representing t h e surface fraction of layer a t
d e p t h z, a n d t h e t e r m exp( - mjX) r e p r e s e n t s t h e A E S
o r X P S intensity a t t h e i n s t a n t a n e o u s surface (m = 0)
a n d below (m > 0). ( N o t e t h a t this factor is u n i t y for
S I M S profiling.) E q u a t i o n (3) h a s been successfully
applied in m a n y i n - d e p t h d i s t r i b u t i o n studies of t h i n
surface layers (Sanz a n d H o f m a n n 1986). A n e x a m p l e
is s h o w n in Fig. 8 for the oxygen profile of a passive
layer o n a stainless steel surface. E q u a t i o n (3) c a n be
modified t o include, for e x a m p l e , preferential s p u t t e r
ing ( H o f m a n n a n d Sanz 1984).
A n o t h e r e x a m p l e for t h e a p p l i c a t i o n of E q n . (3) in
g r a i n - b o u n d a r y segregation studies with A E S d e p t h
profiling is s h o w n in Fig. 9 ( M u s c h i k et al. 1989). T h e
m e a s u r e d profiles are r e p r e s e n t e d b y t h e calculated
true profiles for t h e segregated i n d i u m in a N i 1 . 2 a t . % I n alloy. E q u i l i b r i u m c o n c e n t r a t i o n in the
m o n o l a y e r regime is observed for low a n n e a l i n g
t e m p e r a t u r e , w h e r e a s q u e n c h i n g from h i g h e r t e m p e r
a t u r e s (1311 K ) generates a n o n e q u i l i b r i u m segrega
tion state, as disclosed by the i n d i u m e n r i c h m e n t a t
larger d e p t h s .
I n A E S o r X P S , t h e chemical b o n d i n g s t a t e of a n
element causes characteristic p e a k shifts a n d p e a k
s h a p e a l t e r a t i o n s . U s i n g s t a n d a r d A E S s p e c t r a of
oxides a n d p u r e m e t a l s , the elemental i n - d e p t h c o m
p o s i t i o n c a n be s e p a r a t e d in oxide a n d p u r e m e t a l
c o n t r i b u t i o n s by least-squares fitting m e t h o d s . T h i s
w a s d e m o n s t r a t e d in l o w - t e m p e r a t u r e o x i d a t i o n s t u d
ies of N i C r F e alloys a n d for passive layers o n F e 1 8 % C r as s h o w n in Fig. 10 (Steffen a n d H o f m a n n
1989).
E q u a t i o n (3) is a p p r o p r i a t e for thin layers ( ^ 2 0
m o n o l a y e r s ) o r for layers w h e r e t h e r e s o l u t i o n func
tion increases with the s q u a r e r o o t of d e p t h , as given
by t h e P o i s s o n d i s t r i b u t i o n . F o r c o n s t a n t (as in
r o t a t i o n a l d e p t h profiling), E q n . (3) h a s t o be m o d i
fied, t h a t is, specifically m e a s u r e d o r predicted resolu
tion functions h a v e t o be used in E q n . (2) t o p r o v i d e
a d e c o n v o l u t e d profile as discussed previously (see
Fig. 7).
4. Concluding

Remarks

D e p t h profiling of thin films by ion s p u t t e r i n g a n d

surface analysis h a s b e c o m e a s t a n d a r d t e c h n i q u e t o
disclose the true i n - d e p t h c o m p o s i t i o n of thin layers
(particularly a t surfaces a n d interfaces) in m a n y fields
of m a t e r i a l s science a n d t e c h n o l o g y . W h e r e a s q u a l i t a
tive i n f o r m a t i o n is easily o b t a i n e d , h i g h - r e s o l u t i o n

90

Sputtering time ( s )

10

12

14

16

18

20

Depth (monolayers)

Figure 10
(a) Depth profile of the chemical composition of a passive
layer on Fe-18%Cr (24 h in 0.5n H 2 S 0 4 at 1 V (NHE)).
Normalized fractions of the metallic (Cr(met),Fe(met))
and oxidic (Cr(ox),Fe(ox)) standard components in the
Auger spectra between 20 eV and 70 eV are plotted as a
function of the sputtering time, (b) Concentrations of the
alloy elements in metallic and oxidic states after fitting all
fractions of the respective components from (a) with Eqn.
(3) (after Steffen and Hofmann 1989)

profiling a n d quantification is often c o m p l i c a t e d a n d

requires c a l i b r a t i o n of b o t h t h e m e a s u r e d signal
intensities a n d t h e s p u t t e r i n g timescale. T h e quantifi
c a t i o n p a r a m e t e r s of A E S a n d X P S a r e c o m p a r a t i v e l y
well k n o w n . S I M S , h o w e v e r , often suffers from s t r o n g
m a t r i x effects, w h i c h c a n b e c o n s i d e r a b l y r e d u c e d b y
p o s t i o n i z a t i o n t e c h n i q u e s as in S N M S . C o m p o s i t i o n d e p e n d e n t s p u t t e r i n g rates, preferential s p u t t e r i n g ,
r a d i a t i o n - e n h a n c e d diffusion a n d segregation m a y
c a u s e n o n l i n e a r d i s t o r t i o n s in t h e profile s h a p e . T h e
large n u m b e r of d i s t o r t i o n a l factors d e p e n d i n g o n
s a m p l e characteristics, i n s t r u m e n t a l p a r a m e t e r s a n d
i o n b e a m - s a m p l e i n t e r a c t i o n s generally c a u s e a
b r o a d e n i n g of t h e m e a s u r e d profile. It c a n b e r e p r e
sented by a n a p p r o p r i a t e r e s o l u t i o n function w h i c h is
approximately characterized by the depth resolution
o b t a i n e d as the m e a s u r e d interface w i d t h a t a b r u p t
composition changes.

Depth

Extensive studies of t h e d e p e n d e n c e of t h e d e p t h
resolution o n v a r i o u s e x p e r i m e n t a l p a r a m e t e r s h a v e
s h o w n t h a t o p t i m u m profiling c o n d i t i o n s a r e m e t b y
using h i g h - m a s s , low-energy i o n s for b o m b a r d m e n t a t
high incidence angles. S a m p l e r o t a t i o n d u r i n g profil
ing is increasingly e m p l o y e d t o a v o i d extensive s a m p l e
r o u g h e n i n g d u r i n g s p u t t e r i n g . T h e f u n d a m e n t a l limits
of d e p t h r e s o l u t i o n u n d e r o p t i m i z e d profiling c o n
ditions a r e surface m i c r o r o u g h e n i n g a n d a t o m i c mix
ing w h i c h ultimately limit t h e o b t a i n a b l e r e s o l u t i o n t o
a few n a n o m e t e r s .
A k n o w l e d g e of t h e d e p t h r e s o l u t i o n function
allows d e c o n v o l u t i o n of n o r m a l i z e d m e a s u r e d p r o
files t o o b t a i n t h e original i n - d e p t h d i s t r i b u t i o n o f
c o m p o s i t i o n . F o r t h i n films of several n a n o m e t e r s
thickness, a precision in t h e a t o m i c m o n o l a y e r r a n g e
can be o b t a i n e d .
See also: Auger Electron Spectroscopy; Chemical Analysis
of Solid Surfaces; Electron Spectroscopy for Chemical
Analysis; Ion Backscattering Analysis; Particle-Induced XRay Emission

Bibliography
Andersen 1979 The depth resolution of sputter profil
ing. Appl. Phys. 18: 131-6
Badheka R, Wadsworth M, Armour D G, van den Berg J,
Clegg J 1990 Theoretical and experimental study of the
broadening of dilute delta-doped Si spikes in GaAs
during SIMS depth profiling. Surf. Interface Anal. 15:
550-8
Benninghoven A, Rudenauer F G, Werner W 1987
Secondary Ion Mass Spectrometry. Wiley, New York
Bussing T, Holloway 1985 Deconvolution of concentra
tion depth profiles from angle resolved XPS data. / . Vac.
Sci. Technol. 13: 1973-81
Carter G, Gras-Marti A, Nobes J 1982 Theoretical
assessments of major physical processes involved in the
depth resolution in sputter profiling. Radiat. Eff. 62: 11952
Cirlin , Cheng T, Ireland P, Clemens 1990 Influence
of ion mixing, ion beam-induced roughness and temperat
ure on the depth resolution of sputter depth profiling of
metallic bilayer interfaces. Surf. Interface Anal. 15: 33743
Cirlin , Vajo J J, Doty R E, Hasenberg C 1991 Ioninduced topography, depth resolution and ion yield dur
ing SIMS depth profiling of a GaAs/AlGaAs superlattice:
effects of sample rotation. / . Vac. Sci. Technol. A 8: 1395401
Hofmann S 1986 Determination of depth resolution from
measured sputtering profiles of multilayer structures:
equations and approximations. Surf. Interface Anal. 8:
87-9
Hofmann S 1990 Depth profiling in AES and XPS. In:
Briggs D, Seah (eds.) 1990 Practical Surface Analy
sis, 2nd edn., Vol. 1. Wiley, Chichester, UK, pp. 143-99
Hofmann S 1991a Compositional depth profiling by sputter
ing. Prog. Surf. Sci. 36: 35-87
Hofmann S 1991b High resolution compositional depth
profiling. J. Vac. Sci. Technol. A 9: 1466-76

Profiling

Hofmann S 1992 Cascade mixing limitation in sputter

profiling. / . Vac. Sci. Technol. 10: 316-22
Hofmann S, Sanz J 1980 Deconvolution procedures
applied to depth profiling. In: Abeles F, Croset (eds.)
1980 Proc. 8th Int. Vacuum Congr., Vol. 1 (Thin Films).
Societe Francaise du Vide, Paris, pp. 90-3
Hofmann S, Sanz J 1984 Quantification of preferential
sputtering and contamination overlayer effects in AES
sputter profiling. Surf. Interface Anal. 6: 78-81
Hofmann S, Steffen J 1989 Factor analysis and superposi
tion of Auger electron spectra applied to room temperat
ure oxidation of Ni and NiCr 2 1Fe 1 2. Surf. Interface Anal.
14: 59-65
Hunt C P, Seah 1983 Characterization of a high depthresolution tantalum pentoxide sputter profiling reference.
Surf. Interface Anal. 5: 199-209
Liau L, Tsaur Y, Mayer J W 1979 Influence of atomic
mixing and preferential sputtering on depth profiles and
interfaces. J. Vac. Sci. Technol. 16: 121-7
Muschik T, Gust W, Hofmann S, Predel 1989 The
temperature dependence of grain boundary segregation in
Ni-In bicrystals studied with AES. Acta Metall. 37: 291785
Nelson G C 1984 Quantitative determination of the intensit
ies of known components in spectra obtained from sur
face analytical techniques. J. Vac. Sci. Technol. A 2:
1141-5
Oechsner (ed.) 1984 Thin Film and Depth Profile Analysis,
Topics in Current Physics, Vol. 37. Springer, Berlin
Pamler W, Wangemann K, Kampermann S, Hosier W
1990b Depth resolution in Auger depth profile analysis of
aluminium metallization in microelectronics: the effect of
crystalline texture. Nucl. Instr. Meth. Phys. Res. 54: 3 4 40
Pamler W, Wildenauer E, Mitwalsky A 1990a Improved
depth resolution in Auger depth profiles of TiN thin films
by optimized sputtering parameters. Surf. Interface Anal.
15: 621-6
Sanz J M, Hofmann S 1986 Quantitative AES depth profil
ing of very thin overlayers. Surf. Interface Anal. 8: 147-57
Seah , Dench W 1979 Quantitative electron spectros
copy of surfacesa standard data base for electron
inelastic mean free paths in solids. Surf. Interface Anal. 1:
2-11
Seah , Hunt C P 1983 The depth dependence of the
depth resolution in composition-depth profiling with
AES. Surf. Interface Anal. 5: 33-7
Seah , Sanz J M, Hofmann S 1981 The statistical
sputtering contribution to resolution in concentrationdepth profiling. Thin Solid Films 81: 2 3 9 ^ 6
Steffen J, Hofmann S 1989 Quantitative depth profiling with
AES: application to oxide layers on NiCrFe alloys. Fresenius Z. Anal. Chem. 333: 408-9
Werner W, Garten R 1984 A comparative study of
methods for thin-film and surface analysis. Rep. Prog.
Phys. 47: 221-344
Zalar A 1985 Improved depth resolution by sample rotation
during AES depth profiling. Thin Solid Films 124: 223-30
Zalar A, Hofmann S 1987 Influence of ion energy, incidence
angle and surface roughness on depth resolution in AES
sputter profiling of multilayer Cr/Ni thin films. Nucl.
Instr. Meth. Phys. Res. 18: 655-8
S. H o f m a n n
[ M a x - P l a n c k - I n s t i t u t fur M e t a l l f o r s c h u n g ,
Stuttgart, Germany]
91

Diffusion:

Novel

Measurement

Methods

Diffusion: Novel Measurement Methods

T h e availability of m a n y r e a c t o r - p r o d u c e d r a d i o i s o
topes of high p u r i t y a n d specific activity s o o n after
W o r l d W a r II gave great i m p e t u s to diffusion re
search. R a d i o t r a c e r techniques in diffusion h a v e n o w
b e c o m e quite highly developed with t h e result t h a t
m e a s u r e m e n t s of diffusion coefficients a r e possible
with a precision of a l m o s t 1 % . A p a r t from p r o v i d i n g
the m e a n s of o b t a i n i n g a b s o l u t e values of diffusion
coefficients, tracer m e t h o d s h a v e also p r o v i d e d infor
m a t i o n o n the m e c h a n i s m of diffusion by such m e a n s
as the i s o t o p e effect a n d , in c o n j u n c t i o n with ionic
conductivity, the H a v e n r a t i o . T r a c e r diffusion tech
niques h a v e also been used t o o b t a i n detailed infor
m a t i o n o n i m p u r i t y diffusion a n d the relative solvent
a t o m j u m p frequencies in t h e vicinity of a n i m p u r i t y defect pair. F o r a m o d e r n , a u t h o r i t a t i v e exposition of
r a d i o t r a c e r techniques for diffusion in solids, see
R o t h m a n (1984).
A l t h o u g h there is n o d o u b t t h a t tracer diffusion will
c o n t i n u e t o be t h e p r i m a r y t e c h n i q u e for a d d r e s s i n g
diffusion p r o b l e m s in solids, since t h e early 1970s
there h a s been a t e n d e n c y for w o r k in the diffusion
area to e n c o m p a s s n o t j u s t the t r a d i t i o n a l m e t h o d of
r a d i o t r a c e r s b u t also a wide s p e c t r u m of o t h e r m e t h
ods. S o m e of these novel, " n o n t r a d i t i o n a l " m e t h o d s
h a v e c o m e a b o u t t h r o u g h a d e e p e r u n d e r s t a n d i n g of
the diffusive process itself a n d h o w it w o u l d affect
o t h e r physical p h e n o m e n a , for e x a m p l e quasielastic
n e u t r o n scattering. O t h e r s h a v e c o m e a b o u t t h r o u g h
a search for o t h e r " t r a c e r " m e t h o d s w h e n n o c o n v e n
ient r a d i o i s o t o p e exists, for e x a m p l e oxygen profiled
by s e c o n d a r y - i o n m a s s s p e c t r o m e t r y . S o m e h a v e n o w
b e c o m e viable only t h r o u g h t h e a p p l i c a t i o n of a d
vanced technology. T h e list of novel m e t h o d s dis
cussed in the following is by n o m e a n s c o m p l e t e in a
general sense. It h a s been limited t o t h o s e t e c h n i q u e s
which c o n t i n u e t o be b a s e d o n the n o t i o n of a t o m s
which diffuse a n d c a n be " t r a c e d . " T h e t e c h n i q u e s
dealt with were explored in greater d e p t h , a l o n g with
theoretical d e v e l o p m e n t s in diffusion, in a special
s y m p o s i u m in 1983, the p r o c e e d i n g s of which h a v e
been published ( M u r c h et al. 1984).

1. Quasielastic

Neutron

1.1 Incoherent Scattering Function and Diffusion

If c o n t i n u o u s diffusion as in a simple liquid is
a s s u m e d , it is possible t o express Sinc(K, ) in t e r m s of
t h e diffusion coefficient D:

w h e r e h is the P l a n c k c o n s t a n t divided by In. T h i s

m e a n s t h a t t h e quasielastic line is L o r e n t z i a n in s h a p e
a n d t h e full w i d t h a t h a l f - m a x i m u m of t h e p e a k is
given by
Tmc

= 2hDK

(2)

This b e h a v i o r h a s been f o u n d in such liquids as a r g o n .

Diffusion in solids is n o t usually c o n t i n u o u s b u t is
c h a r a c t e r i z e d by a h o p p i n g m o t i o n from o n e site t o
a n o t h e r , w h e r e t h e residence time is l o n g c o m p a r e d
with t h e flight time t o a n e i g h b o r i n g site, usually a
nearest n e i g h b o r . W i t h this c o n d i t i o n a n d the as
s u m p t i o n s t h a t j u m p s a r e r a n d o m a n d t h e sites form a
Bravais lattice, C h u d l e y a n d Elliott (1960) s h o w e d
t h a t Sinc(K, ) is L o r e n t z i a n a n d is given by

^,)

= .(

f ( K )T

)22

nh \ ( / ( ) / ) + /

(3)

w h i c h h a s a similar form t o E q n . (1). T h e full w i d t h a t

h a l f - m a x i m u m is given by
RI

NC

= 2hf{K)h

(4)

All t h e i n f o r m a t i o n a b o u t t h e j u m p diffusion is c o n
tained in the a v e r a g e residence time a n d the w i d t h
function f(K) which is d e t e r m i n e d solely by the geo
m e t r y of the lattice sites.

Scattering

Quasielastic n e u t r o n scattering ( Q E N S ) is n o w fairly

routinely used in the s t u d y of diffusion in liquids a n d
solids. F o r a detailed discussion of the subject the
reader is referred to Z a b e l (1984). M o s t solid-state
a p p l i c a t i o n s h a v e been t o h y d r o g e n in metals, superionic o r fast ion c o n d u c t o r s a n d diffusion of alkali
a t o m s in g r a p h i t e intercalation c o m p o u n d s . R e q u i r e
m e n t s are diffusion coefficients greater t h a n a b o u t
n
2
_1
10~ m S
a n d elements t h a t exhibit r e a s o n a b l y
high scattering cross sections.
In n e u t r o n scattering e x p e r i m e n t s , the d o u b l e dif-

92

ferential cross section d o/dildE'

is m e a s u r e d w i t h
respect t o the solid angle i n t o which the n e u t r o n s
a r e scattered after leaving the s a m p l e a n d the energy
2
E' of t h e n e u t r o n s ; see Fig. 1. T h e q u a n t i t y
d o/dQdlt
is expressible in t e r m s of i n c o h e r e n t a n d c o h e r e n t
scattering functions Sinc(K, ) a n d Scoh(K, ) , respect
ively, w h e r e is t h e scattering vector a n d is the
frequency. B o t h scattering functions c a n be used t o
analyze diffusion in solids.

(a)

(b)

Figure 1
Neutron scattering geometry: (a) in real space, (b) in
momentum space. k0, E0, k' and E' are the wave vectors
and energy of the neutrons before and after the scattering
process; is the scattering vector (after Zabel 1984)

Diffusion:

F o r Bravais lattices, f{K) c a n easily b e w o r k e d o u t ,

leading t o t h e following oscillatory function expres
sion for r inc:
%h

(KJ,\

where /, is a n e a r e s t - n e i g h b o r lattice vector a n d is the

n u m b e r o f nearest n e i g h b o r s . A c c o r d i n g l y (if o n e
chooses a p p r o p r i a t e scattering vectors K), it is p o s
sible, with single crystal samples, t o distinguish
between v a r i o u s diffusion m o d e l s , for e x a m p l e
between t e t r a h e d r a l a n d o c t a h e d r a l interstitials.
F o r small scattering vectors o n e c a n m a k e direct
c o n n e c t i o n with the diffusion coefficient for h o p p i n g
m o t i o n . F o r e x a m p l e , for ( o c t a h e d r a l ) h y d r o g e n
interstitials in the face-centered-cubic (fee) lattice a n d
the scattering vector A' in a [100] direction o n e finds
t h a t the full w i d t h a t h a l f - m a x i m u m is given b y
2

= 2 /\2

(6)

which c a n b e expressed using D a s

2

T i nc = 2hDK

(7)

This h a p p e n s also t o b e the s a m e expression a s E q n .

(2) for c o n t i n u o u s diffusion.
T h e t e m p e r a t u r e d e p e n d e n c e o f T i nc c a n b e used t o
d e t e r m i n e the a c t i v a t i o n energy since D h a s the A r r henius form
D = D0exp(-EJkT)

(8)

where D0 is t h e p r e e x p o n e n t i a l , is t h e a c t i v a t i o n
energy, k is t h e B o l t z m a n n c o n s t a n t a n d is t h e
temperature.
In the preceding discussion, v i b r a t i o n o f the a t o m s
w a s neglected. P r o v i d e d it c a n b e a s s u m e d t h a t this
m o t i o n is u n c o u p l e d from the j u m p m o t i o n , it c a n b e
included in the analysis by m u l t i p l y i n g SiDC(K, ) by a
2
2
2
D e b y e - W a l l e r factor e x p ( - A T < w w h e r e <w > is
the m e a n s q u a r e a m p l i t u d e o f t h e v i b r a t i o n .
1.2 Coherent Scattering Function and Diffusion
C o h e r e n t quasielastic n e u t r o n scattering is m u c h
m o r e c o m p l e x t h a n t h e i n c o h e r e n t case b e c a u s e o f
pari c o r r e l a t i o n s in a t o m i c m o t i o n . A p p r o x i m a t e
expressions h a v e been d e v e l o p e d b e t w e e n .S'coh(A', )
a n d D\ see especially d e G e n n e s (1959).

2. Nuclear

Magnetic

Resonance

F o r a discussion o f the general principles o f n u c l e a r

m a g n e t i c r e s o n a n c e ( N M R ) the r e a d e r is referred t o
the article Nuclear Magnetic Resonance
Spectroscopy.
N M R is especially sensitive t o i n t e r a c t i o n s o f t h e
nuclear m o m e n t s with fields p r o d u c e d b y their local
e n v i r o n m e n t s . Diffusion o f a n u c l e a r m o m e n t c a n
cause v a r i a t i o n s in these fields a n d c a n significantly

Novel

Measurement

Methods

affect the observed r e s o n a n c e . I n p a r t i c u l a r , diffusion

affects a n u m b e r o f r e l a x a t i o n times in N M R . T h e s e
will b e dealt with in t h e following sections. F o r a
detailed review o f the subject, see Stokes (1984).
2.1 Spin-Spin Relaxation and Diffusion
Systems o f nuclear spins a r e usually p a r a m a g n e t i c ,
t h a t is, in zero external field the n u c l e a r m a g n e t i z a t i o n
is z e r o . If the s a m p l e is placed in a n external field H0 it
a c q u i r e s a m a g n e t i z a t i o n given by C u r i e ' s law. T h e
time e v o l u t i o n o f is usually e x p o n e n t i a l :
M = M 0( l - e x p ( - A / / r l) )

(9)

w h e r e At is the elapsed time. W h e n a m a g n e t i c field

pulse Hl o f specified d u r a t i o n is also applied a l o n g a
p e r p e n d i c u l a r axis, the m a g n e t i z a t i o n precesses a b o u t
H0 with the L a r m o r frequency 0 a n d decays t o zero.
0
T h i s pulse is called a 9 0 pulse a n d t h e characteristic
time for decay is called t h e s p i n - s p i n relaxation time
T2. T h e resulting N M R signal is called a freei n d u c t i o n decay ( F I D ) . T h e F I D refers t o the loss o f
c o h e r e n c e in t h e precession o f t h e n u c l e a r m o m e n t s
a b o u t t h e applied m a g n e t i c field H0 after t h e pulse.
T h e loss o f c o h e r e n c e leading t o d e c a y c o m e s a b o u t
b e c a u s e each m o m e n t " s e e s " slightly different local
fields. Diffusion o f a m o m e n t results in its local fields
being effectively smaller because they will v a r y in
direction a n d m a g n i t u d e . T h e m o m e n t s will precess
longer a n d , a s a result, T2 is longer. T h e m o r e r a p i d
the diffusion is, t h e longer will be T2. I t t u r n s o u t t h a t
T2 h a s a n A r r h e n i u s t e m p e r a t u r e d e p e n d e n c e , t h e
a c t i v a t i o n energy for diffusion being t h e activation
energy for 2 , t h a t is,
In T2 = - Ea/kT+

constant

(10)

A t very low t e m p e r a t u r e s w h e n diffusion is very slow

t h e F I D is unaffected b y diffusion a n d T2 is indepen
dent of temperature.
2.2 Spin-Lattice
Relaxation and Diffusion
T h e s p i n - l a t t i c e relaxation time Tl p r o v i d e s a n o t h e r
N M R m e t h o d for extracting t h e activation energy for
diffusion. After the "90 p u l s e " o f Hl a s described in
t h e p r e v i o u s section, t h e m a g n e t i z a t i o n decays t o zero
d u r i n g the F I D . If a n o t h e r 90 pulse is applied a very
s h o r t time later there is n o F I D . H o w e v e r , if a longer
time is allowed t o elapse (At^T^,
a n F I D will b e
observed. T h e a m p l i t u d e o f this second F I D is p r o
p o r t i o n a l t o M , the time e v o l u t i o n o f which is given
by C u r i e ' s law, E q n . (9). By r e p e a t i n g this two-pulse
sequence for v a r i o u s values o f At, it is possible t o
e x t r a c t Tl from E q n . (9). Diffusion i n f o r m a t i o n c a n
be e x t r a c t e d from t h e t e m p e r a t u r e d e p e n d e n c e of Tx
w h i c h is V - s h a p e d .
In Tx=EJkT

+ constant,

In , = Ea/kT+

7 > Tmin

(10a)

c o n s t a n t , T< Tmin (10b)

93

Diffusion:

Novel

Measurement

Methods

Tmin is the t e m p e r a t u r e w h e r e Tx h a s a m i n i m u m value.

This t u r n s o u t t o be w h e n t h e residence time a t a
_ 1
site is e q u a l t o 0 t h e reciprocal of the L a r m o r
frequency.
2.3 Spin-Lattice
Relaxation in the Rotating
Reference Frame and Diffusion
In the r o t a t i n g reference frame case, r a t h e r t h a n
switching the "90 p u l s e " Hx off as before, is
suddenly shifted by 90 a n d held for time At. T h e
m a g n e t i z a t i o n d o e s n o t decay as in F I D b u t r e m a i n s
aligned with Hx. W e n o w observe the p h e n o m e n o n of
" s p i n - l o c k i n g " in t h e r o t a t i n g reference frame a n d a
situation similar to Tx r e l a x a t i o n in t h e l a b o r a t o r y
frame of reference. T h e m a g n e t i z a t i o n will relax t o
w a r d s the e q u i l i b r i u m value in t h e field Hl from its
equilibrium value in H0. Since HJHX ~ 1000, it c a n be
considered t h a t decays a p p r o x i m a t e l y t o zero. A s
with Tx processes, the decay is usually e x p o n e n t i a l ,
and
M=M0exp(-At/T]p)

(11)

2000

3000

4000

5000

/-')
where M0 is the e q u i l i b r i u m value in H0 a n d TXp
is the s p i n - l a t t i c e r e l a x a t i o n time in the r o t a t i n g
reference frame. T h i s r e l a x a t i o n c a n be observed by
spin-locking the m a g n e t i z a t i o n for s o m e time At, t h e n
suddenly t u r n i n g off this field a n d o b s e r v i n g the F I D .
T h e a m p l i t u d e of the F I D is p r o p o r t i o n a l t o M. By
repeating this shift of pulse sequence for v a r i o u s
values of At, it is possible to extract TXp from E q n . (11)
a n d a from e q u a t i o n s similar t o E q n s . (10a, b).
2.4 Concluding
Remarks
T h e c o m b i n a t i o n of T2, Tx a n d TXp d a t a c a n extend the
d e t e r m i n a t i o n of Ea over a wide r a n g e of t e m p e r a t u r e s
a n d diffusion coefficients. F o r e x a m p l e , in the case of
lithium m e t a l , N M R d a t a h a v e p e r m i t t e d d e t e r m i
n a t i o n of the self-diffusion coefficient over eight o r d
ers of m a g n i t u d e ; see Fig. 2. F o r a n e x a m p l e of a m o r e
detailed analysis of , a n d Tx d a t a , refer to Messer
a n d N o a c k (1975).

3. Mossbauer

Effect

T h e M o s s b a u e r effect h a s been exploited to r a t h e r a

small extent for diffusion in solids. T h i s is m a i n l y a
result of e x p e r i m e n t a l difficulties e n c o u n t e r e d with
p e r f o r m i n g the m e a s u r e m e n t s at high t e m p e r a t u r e s .
This is a pity because the m e t h o d s h o w s c o n s i d e r a b l e
p r o m i s e for u n d e r s t a n d i n g diffusion processes in
solids. G e n e r a l r e q u i r e m e n t s a r e t h a t the diffusion
coefficient of the M o s s b a u e r active i s o t o p e s h o u l d be
1 3
2 _ 1
greater t h a n a b o u t 1 0 ~ m s . M o s t a p p l i c a t i o n s
have been t o solids i n c o r p o r a t i n g the r a t h e r ideal
57
isotope F e .

94

Figure 2
Temperature dependence of T]p and T2 in solid lithium;
all variables are described fully in text (after Stokes 1984)

3.1 Mossbauer

and

Diffusion

F o r a full description of t h e M o s s b a u e r effect refer t o

W e r t h e i m (1964) a n d to M u l l e n (1984) for a detailed
discussion of the M o s s b a u e r effect a n d a t o m i c diffu
sion (see Mossbauer Spectroscopy).
One can picture
the M o s s b a u e r effect as a r e s o n a n t filter. T h e s o u r c e
emits g a m m a r a d i a t i o n of the p l a n e w a v e f o r m
exp[i(ur. r - co0t)]. If the s o u r c e is oscillated sinusoidally a t a n a n g u l a r frequency t h e a b s o r b e r (sample)
will act as F o u r i e r analyzer which sees a r e d u c e d
intensity at t h e r e s o n a n t frequency 0 with the lost
intensity r e a p p e a r i n g as s i d e b a n d s a t frequencies
0 , 0 + 2co, a n d so o n . T h e a c t u a l o b s e r v a t i o n s
of t h e s i d e b a n d s is achieved b y m o v i n g t h e a b s o r b e r
at a fixed velocity, c a u s i n g a D o p p l e r shift in the
incoming radiation.
W h e n a n e m i t t i n g nucleus in t h e s a m p l e j u m p s
p e r p e n d i c u l a r l y to t h e direction of m o t i o n of the
emitted g a m m a ray, there is n o c h a n g e of p h a s e
c o h e r e n c e a n d c o n s e q u e n t l y this d o e s n o t result in
b r o a d e n i n g of t h e line. H o w e v e r , if t h e e m i t t i n g
nucleus j u m p s in the direction of the emission this will
result in a c o m p l e t e loss of c o h e r e n c e a n d a conse
q u e n t b r o a d e n i n g of t h e M o s s b a u e r line (see Fig. 3).
T h e characteristic time which d e t e r m i n e s the line
w i d t h is n o longer t h e usual n u c l e a r lifetime b u t is
instead the residence time 0 as 0 b e c o m e s small
c o m p a r e d with .

Diffusion:

Novel

Measurement

Methods

(b)

Figure 3
Schematic representation of (a) a translational jump in the
direction of emission causing a loss of coherence and a
resulting broadening of the Mossbauer line, and (b) a
jump perpendicular to the direction of emission which
preserves phase coherence and results in no broadening
(after Mullen 1984)

In a w a y q u i t e reminiscent of Q E N S a n d i n c o h e r e n t
scattering, it is possible t o associate t h e b r o a d e n i n g of
the r e s o n a n c e line with diffusion. Singwi a n d Sjolander (1960) h a v e t r e a t e d t w o m o d e l s : c o n t i n u o u s
diffusion as in a liquid, a n d h o p p i n g m o t i o n w i t h a
long residence time a s in m o s t solid-state diffusion
situations. I n b o t h cases, t h e b r o a d e n i n g c a n be
expressed as
=

IhDK

W h e n t h e net b r o a d e n i n g d u e t o diffusion e q u a l s t h a t
d u e t o t h e n u c l e a r lifetime , this leads t o a lower
1 3
2
_1
limit in diffusion coefficient of 1 0 " m s (in solids)
5 7
for F e .

4. Secondary-Ion

Mass

Spectroscopy

T h e use of s e c o n d a r y - i o n m a s s s p e c t r o s c o p y ( S I M S )
c a m e a b o u t b e c a u s e of t h e lack of s u i t a b l e r a d i o i s o
t o p e s for oxygen, n i t r o g e n a n d o t h e r light elements.
T h e s e light elements were first a n a l y z e d directly u s i n g
nuclear r e a c t i o n s (see Sect. 5) a n d indirectly using t h e
i s o t o p e e x c h a n g e m e t h o d (e.g., A u s k e r n a n d Belle
1961). I n recent y e a r s , h o w e v e r , S I M S i n s t r u m e n t s
h a v e b e c o m e sufficiently w i d e s p r e a d t h a t t o a large
extent S I M S h a s p u s h e d aside t h e n u c l e a r r e a c t i o n s a s
t h e m e t h o d of choice. Several reviews of S I M S a s
applied t o diffusion h a v e been p u b l i s h e d (e.g., P e t u s key 1984, K i l n e r 1986).
4.1

0 2~ a n d C s , a n d their kinetic energies o n arrival a t

t h e t a r g e t a r e c h o s e n t o be b e t w e e n 0.5 keV a n d
2 5 k e V . T h e p r i m a r y i o n s quickly decelerate o n
i m p a c t w i t h t h e s a m p l e surface b y m e a n s of a series of
collisions w i t h a t o m s in t h e s a m p l e . A collision cas
c a d e is initiated b y e a c h p r i m a r y ion w h i c h leads t o
t h e possible s p u t t e r i n g o r ejection of t a r g e t a t o m s .
T y p i c a l s p u t t e r i n g yields v a r y b e t w e e n 0.1 a t o m s a n d
10 a t o m s p e r p r i m a r y ion. M o s t of the s p u t t e r e d
species a r e n e u t r a l . M a n y of these a r e s u b s e q u e n t l y
c o n v e r t e d t o i o n s b y chemical r e a c t i o n s with the
residual a t m o s p h e r e , t h e p r i m a r y b e a m o r t h e s a m p l e .
T h e s e c o n d a r y i o n s a r e e x t r a c t e d from the surface
a n d its vicinity by i m p o s i n g a n electrical bias. T h e
i o n s a r e t h e n t r a n s f e r r e d t o a s p e c t r o m e t e r which
filters o u t i o n s w i t h o u t a c h o s e n m a s s - t o - c h a r g e r a t i o .
T h e remainder are counted by the detector.
4.2 Application

to

Diffusion

I n a typical t r a c e r diffusion e x p e r i m e n t the tracer

diffusant is d e p o s i t e d o n t o t h e surface of the s a m p l e
a n d is p e r m i t t e d t o diffuse in for a specified time. If
t h e tracers a r e r a d i o a c t i v e , t h e m a t e r i a l is sectioned
parallel t o t h e diffusion direction a n d each section is
c o u n t e d . T h e c o n c e n t r a t i o n profile is s u b s e q u e n t l y
a n a l y z e d t o o b t a i n t h e diffusion coefficient ( R o t h m a n
1984). W i t h S I M S there a r e t w o possibilities. In the
first, after diffusion t h e s a m p l e c a n be bevelled a t a n
angle t o " e x p a n d " t h e c o n c e n t r a t i o n profile. T h e
s a m p l e is t h e n analyzed for t h e diffusant in a stepwise
m a n n e r t o build u p the c o n c e n t r a t i o n profile. O t h e r
lateral diffusion analyses a r e also possible. In the
s e c o n d possibility, S I M S is used t o p e r f o r m d e p t h
profiling by progressively e r o d i n g a c r a t e r i n t o the
surface. D e p t h profiling is simply t h e c o n t i n u o u s
s p u t t e r i n g of surface a t o m s from o n e a r e a r o u g h l y
250 in d i a m e t e r . It is this case t h a t is the m o s t
c o m m o n b e c a u s e of t h e very high d e p t h resolution
possible with S I M S .
T h e p r o b l e m s e n c o u n t e r e d in S I M S t e n d to be
d i c t a t e d by t h e design of t h e i n s t r u m e n t . Typical
p r o b l e m s , t h o u g h , a r e t h e c h a r g i n g u p of insulating
s a m p l e s (partially o v e r c o m e b y electron flooding of
t h e s a m p l e ) a n d t h e a c c u r a c y of t h e d e p t h m e a s u r e
m e n t of t h e e r o d e d c r a t e r ( o v e r c o m e principally b y
c a l i b r a t i o n ) . T h e m a i n a d v a n t a g e of S I M S is the
impressive d e p t h r e s o l u t i o n possible, of the o r d e r of
n a n o m e t e r s , a n d t h e d e m o n s t r a t e d capability t o ex
a m i n e g r a i n - b o u n d a r y a n d d i s l o c a t i o n - e n h a n c e d dif
fusion as well as very slow diffusion processes o r
short-term experiments.

Description

A S I M S i n s t r u m e n t c a n b e called a n ion m i c r o p r o b e o r ion m i c r o s c o p e (see Secondary-Ion

Mass
Spectrometry).
T h e essential features b o t h for surface
analysis a n d d e p t h profiling a r e as follows. I o n s a r e
p r o d u c e d , accelerated a n d focused o n t o t h e t a r g e t
+
+
(sample). T y p i c a l p r i m a r y i o n s used include A r , 0 ,

5. Nuclear

Reaction

Analysis

T h e analysis of m a n y light elements w i t h o u t suitable

r a d i o i s o t o p e s first b e c a m e possible with the develop
m e n t of n u c l e a r r e a c t i o n analysis. N u c l e a r reactions
h a v e b e e n used t o m e a s u r e t h e c o n c e n t r a t i o n of all

95

Diffusion:

Novel

Measurement

Methods

elements lighter t h a n chlorine. T h e r e a r e a n u m b e r of

different types of nuclear reactions t o m e a s u r e the
c o n c e n t r a t i o n profiles described in Sect. 4.2. T h e s e
will be described in the next t w o sections. F o r a
detailed discussion see L a n f o r d et al. (1984).
5.7 Application
Diffusion

of Resonant

Nuclear Reactions

to

W i t h r e s o n a n t nuclear reactions, the reaction occurs

only within a n a r r o w energy r a n g e centered at the
, 8
1 9
r e s o n a n c e energy. W e use the 0 ( p , y) F reaction as
an e x a m p l e . W i t h this reaction there is a useful
r e s o n a n c e a t a p r o t o n energy of 1.9 M e V . T h e p r o t o n
b e a m is p r o d u c e d by a n accelerator. A t t h e r e s o n a n c e
l s
energy, o n e c a n analyze for the presence of O at o r
very n e a r the surface of the s a m p l e by c o u n t i n g the
emitted r a d i a t i o n . If the p r o t o n energy is raised,
there will be n o reactions with surface oxygen, b u t the
p r o t o n s lose energy by p e n e t r a t i n g t h e s a m p l e a n d at
s o m e d e p t h the p r o t o n energy d r o p s to the r e s o n a n t
1 8
energy, a n d n o w
0 a t o m s at t h a t d e p t h c a n be
activated. In this way, the s a m p l e c a n be d e p t h profiled w i t h o u t d e s t r u c t i o n of p a r t of t h e s a m p l e as
in S I M S (Sect. 4). H o w e v e r , the d e p t h t h a t c a n be
analyzed is r a t h e r limited b e c a u s e of o t h e r r e s o n a n c e s
a n d the s t o p p i n g p o w e r of the s a m p l e . Typical d e p t h s
are < 10 .
O n e v a r i a n t of this m e t h o d is its c o m b i n a t i o n with
s t a n d a r d serial sectioning to analyze at greater
d e p t h s . A n o t h e r v a r i a n t is the bevelling t e c h n i q u e
(Sect. 4.2) a n d the use of a r e s o n a n t nuclear reaction
which leaves a radioactive i s o t o p e which c a n be
detected by a u t o r a d i o g r a p h y . A n e x a m p l e of this is
, 8
1 8
the nuclear reaction 0 ( p , n) F a n d the s u b s e q u e n t
1 8
analysis of F (which h a s a half-life of 112 m i n ) .
5.2 Application
Diffusion

of Nome sonant Nuclear

Reactions

to

In a n o n r e s o n a n t nuclear reaction the p r o b a b i l i t y of

nuclear reaction, a n d hence t h e yield, varies only
slowly with energy. A c c o r d i n g l y , unlike r e s o n a n t
reactions which always occur at the s a m e energy (the
r e s o n a n c e energy), the d e t e r m i n a t i o n of c o n c e n t r a
tion profiles is m u c h m o r e c o m p l i c a t e d . A s a result,
r e s o n a n t reactions h a v e been preferred. Occasionally,
the s t o p p i n g p o w e r of t h e s a m p l e is sufficiently high
t h a t the n o n r e s o n a n t reaction c a n be used to activate
only surface layers a n d c a n be used in conjuction with
sectioning.

6. Rutherford

Backscattering

Analysis

R u t h e r f o r d b a c k s c a t t e r i n g ( R B S ) analysis a g a i n
m a k e s use of nuclear i n t e r a c t i o n s b u t the incident
b e a m particles reemerge u n c h a n g e d except for a
r e d u c t i o n in energy (see Ion Backscattering
Analysis).
T h e loss in energy is d u e in p a r t t o elastic recoil of the
nuclei in the target (sample). T h e m a g n i t u d e of the

96

recoil energy loss is a m o n o t o n i c a l l y decreasing func

tion of t h e n u c l e a r m a s s in the target. T h i s forms the
basis for element identification.
6.1 Rutherford Backscattering
and Diffusion
A l t h o u g h R B S is useful for a wide r a n g e of diffusion
p r o b l e m s a n d s o m e t i m e s is t o be preferred to t h e use
of r a d i o t r a c e r s , there are t w o limitations of t h e
m e t h o d . O n e is t h a t the a t o m i c m a s s of t h e element of
interest m u s t exceed by at least several a t o m i c m a s s
units the m a s s e s of o t h e r c o m p o n e n t s in the system.
T h e o t h e r is t h a t t h e sensitivity for dilute species is
achieved only if they are heavier t h a n the m a j o r i t y
c o n s t i t u e n t s in the system. Since the e x p e r i m e n t a l
s e t u p is very similar t o t h a t used in n u c l e a r r e a c t i o n
analysis, it is possible to c h a n g e from o n e t o t h e o t h e r
if the s i t u a t i o n so dictates.
D e p t h r e s o l u t i o n is possible with R B S b e c a u s e t h e
c h a r g e d particles lose energy in a k n o w n w a y as t h e y
p e n e t r a t e t h e specimen. W h e n t h e particle is detected,
the a c c u m u l a t e d energy r e d u c t i o n is s u p e r i m p o s e d o n
t h e recoil loss itself. H e n c e , t h e m e a s u r e d energy
decreases m o n o t o n i c a l l y with t h e d e p t h of t h e n u c
leus. T h e a c t u a l e x t r a c t i o n of t h e c o n c e n t r a t i o n p r o
file requires i n f o r m a t i o n o n t h e energy loss p e r d e p t h
i n c r e m e n t , t h e energy transferred t o t h e target d u r i n g
t h e b a c k s c a t t e r i n g event a n d t h e n u c l e a r cross section.
A s with t h e n u c l e a r r e a c t i o n s , d e p t h profiling is
limited t o a b o u t 10 in m a n y m a t e r i a l s . T h e R B S
t e c h n i q u e is also s o m e t i m e s c o m b i n e d with serial
sectioning t o o b t a i n i n f o r m a t i o n a t g r e a t e r d e p t h s . It
is t h e high d e p t h r e s o l u t i o n t h a t m a k e s R B S very
2 1
2 _1
v a l u a b l e . Diffusion coefficients as low as 1 0 ~ m s
h a v e been d e t e r m i n e d . T h i s is a n impressive achieve
ment.
See also: Nuclear Magnetic Resonance Spectroscopy of
Solids

Bibliography
Auskern A B, Belle J 1961 Oxygen ion self-diffusion in
uranium dioxide. / . Nucl. Mater. 3: 267-76
Chudley C T, Elliott R J 1960 Neutron scattering from a
liquid on a jump diffusion model. Proc. Physc. Soc. 77:
353-61
de Gennes G 1959 Liquid dynamics and inelastic scatter
ing of neutrons. Physica 25: 825-39
Kilner J A 1986 New techniques for studying mass transport
in oxides. Mater. Sci. Forum 7: 205-22
Landford W A, Benenson R, Burman C, Wielunski L 1984
Nuclear-reaction analysis for diffusion studies. In: Murch
et al. 1984, pp. 155-77
Messer R, Noack F 1975 Nuclear magnetic relaxation by
self diffusion in solid lithium: ,-frequency dependence.
Appl. Phys. 6: 79-88
Mullen J C 1984 Mossbauer diffusion studies. In: Murch et
al. 1984, pp. 59-81
Murch G E, Birnbaum Cost J R (eds.) 1984 Nontraditional Methods in Diffusion. Metallurgical Society of
AIME, Warrendale, PA

Diffusion:

Petuskey W 1984 Diffusion analysis using secondary ion

mass-specroscopy (SIMS). In: Murch et al. 1984, pp. 179
202
Rothman S J 1984 The measurement of tracer diffusion
coefficients in solids. In: Murch G E, Nowick A S (eds.)
1984 Diffusion in Crystalline Solids. Academic Press,
Orlando, FL, pp. 1-61
Singwi S, Sjolander A 1960 Resonance absorption of
nuclear gamma rays and the dynamics of atomic motions.
Phys. Rev. 120: 1093-102
Stokes 1984 Study of diffusion in solids by pulsed

Novel

Measurement

Methods

nuclear magnetic resonance. In: Murch et al. 1984, pp.

39-58
Wertheim G 1964 Mossbauer Effect: Principles and Appli
cations. Academic Press, New York
Zabel 1984 Quasi-electric neutron scattering: a powerful
tool for investigating diffusion in solids. In: Murch et al.
1984, pp. 1-37
G . E. M u r c h
[University of N e w c a s t l e , Newcastle,
N e w S o u t h W a l e s , Australia]

97


Elastomers: Spectroscopic
Characterization
I s o p r e n e a n d 1,3-butadiene c a n be linearly p o l y m e r
ized t o p o l y m e r s h a v i n g cis-1,4, /raws-1,4, vinyl-1,2
a n d , in the case of p o l y i s o p r e n e , vinyl-3,4 isomeric
structures. T h e m i c r o s t r u c t u r e s of p o l y b u t a d i e n e a n d
p o l y i s o p r e n e a r e k n o w n t o h a v e a p r o f o u n d effect o n
their e n d - u s e p r o p e r t i e s . T h e r e f o r e , t h e m i c r o s t r u c t u r e m u s t be d e t e r m i n e d in o r d e r t o e v a l u a t e these
relationships. In t h e early years low m o l e c u l a r weight
model c o m p o u n d s a n d model elastomeric samples
with varying a m o u n t s of t h e m i c r o s t r u c t u r e s were
used as s t a n d a r d s , since t h e p u r e c o m p o n e n t m a t e r i a l s
were n o t available; h o w e v e r , these m o d e l c o m p o u n d s
are n o t a d e q u a t e in this respect. W i t h the discovery of
stereospecific catalysts, it is n o w possible t o synthesize
p o l y b u t a d i e n e s a n d p o l y i s o p r e n e s with m i c r o s t r u c
tures a p p r o a c h i n g 1 0 0 % regularity, w h i c h serve as
ideal s t a n d a r d s . T h e s p e c t r o s c o p i c t e c h n i q u e s m o s t
often used t o c h a r a c t e r i z e this u n s a t u r a t i o n m i c r o s t r u c t u r e of e l a s t o m e r s a r e infrared s p e c t r o s c o p y ,
high-field ( > 270 M H z ) p r o t o n n u c l e a r m a g n e t i c
resonance spectroscopy ( - N M R ) and carbon-13
1 3
nuclear m a g n e t i c r e s o n a n c e s p e c t r o s c o p y ( C - N M R ) .

1. Infrared

Analysis

of

frequency w i t h a new m a x i m u m a t 724 c m " . T h e

d i s s y m m e t r y of the cis b a n d is t h o u g h t t o be caused
by t r i a d i n t e r a c t i o n s of t h e t h r e e possible b a s e units,
1
cis (c), trans (t) a n d vinyl (v). T h e p e a k at 740 c m " is
1
believed t o be of ccc t r i a d s while t h e p e a k a t 724 c m "
is believed p r e d o m i n a t e d b y tct a n d tcv triads. T h e
1
vinyl b a n d at 9 1 1 c m " a n d t h e trans b a n d which
1
o c c u r s a t 967 c m " a r e n o t as sensitive t o t h e m o l e c u
lar e n v i r o n m e n t as t h e cis b a n d ( H a m p t o n 1972).
T h e a b s o r p t i o n is m e a s u r e d at the t h r e e selected
characteristic frequencies of the three different base
u n i t s . If the p o l y m e r s t a n d a r d s a r e n o t greater t h a n
9 9 % p u r i t y , the a b s o r p t i o n coefficients c a n be deter
m i n e d by a n i t e r a t i o n process ( M o r e r o et al. 1959). If
p o l y b u t a d i e n e is c o n s i d e r e d t o b e a t h r e e - c o m p o n e n t
m i x t u r e of trans-\,4,
cis-\,4 a n d vinyl-1,2, t h e n the
u n s a t u r a t i o n m i c r o s t r u c t u r e c a n b e o b t a i n e d b y solv
ing a set of t h r e e s i m u l t a n e o u s e q u a t i o n s of the form

Polybutadiene

Infrared s p e c t r o s c o p y (see Infrared Spectroscopy)

can
be used t o d e t e r m i n e t h e e l a s t o m e r c o m p o s i t i o n a n d
m o l e c u l a r s t r u c t u r e , i n c l u d i n g tacticity a n d s e q u e n c e
distribution ( H a m p t o n
1972). F i g u r e 1 s h o w s
the infrared spectra of c o m m e r c i a l p o l y b u t a d i e n e ,
vinyl-1,2-polybutadiene, cis-1,4-polybutadiene
and
/ra/2s-l,4-polybutadiene. W i t h t h e e x c e p t i o n of t h e
c o m m e r c i a l p o l y b u t a d i e n e , all s a m p l e s a r e > 9 7 %
-1
p u r e . T h e s e spectra cover only t h e 1150-600 c m
region, w h i c h is best suited for these p o l y m e r s . T h e
vinyl p o l y m e r s h o w s t h r e e distinct b a n d s a t 996, 910
1
1
a n d 675 c m " . T h e b a n d a t 910 c m " is usually t a k e n
as the a b s o r p t i o n b a n d for d e t e r m i n a t i o n of the vinyl
sequences ( H a m p t o n 1949, Silas et al. 1959, B i n d e r
1
1954, M o r e r o et al. 1959). T h e vinyl b a n d a t 680 c m "
w a s initially assigned t o cis u n s a t u r a t i o n b y B i n d e r
(1954), b u t this a s s i g n m e n t h a s since been p r o v e n t o
1
be incorrect. T h e vinyl b a n d a r o u n d 680 c m " is
a s y m m e t r i c , t h e a s y m m e t r y being c a u s e d by t h e
a b s o r p t i o n of t h e s y n d i o t a c t i c a n d isotactic d i a d s of
1
high-vinyl p o l y m e r s a t 670 a n d 695 c m " , respectively
( H a m p t o n 1972). T h e a b s o r p t i o n b a n d for t h e high
cis-\, 4 p o l y m e r is f o u n d t o give a b r o a d d i s s y m m e t r i
l
cal b a n d with a p e a k a t 740 c m " . A s the cis c o n t e n t of
the r u b b e r decreases t h e p e a k t e n d s t o shift t o a h i g h e r

U
1150

IOOO

800
Wavelength

(cm

- 1

600

Figure 1
Out-of-plane C-H bending bands of CH and CH 2 for
(a) commercial polybutadiene, (b) vinyl-1,2-polybutadiene,
(c) cis-1,4-polybutadiene and (d) iras-l,4-polybutadiene

99

Elastomers:

Spectroscopic

D
D

= CxE\

Characterization

+ C2E\
2

= Cl E + C2E 2 +
3

= Cl E\ + C2E 2

1.5% of e a c h o t h e r . T h e v a r i a t i o n in t h e cis a n d trans

c o m p o n e n t s w a s a little greater. I n c o m p a r i s o n with
the least-squares m e t h o d , t h e cis c o m p o n e n t w a s
f o u n d t o b e lower b y a p p r o x i m a t e l y 5 - 7 % . T h i s is d u e
t o t h e fact t h a t t h e least-squares m e t h o d corrects for
t h e vinyl c o m p o n e n t t h a t lies u n d e r t h e cis b a n d . T h e
trans a n d vinyl c o m p o n e n t s a r e adjusted accordingly.

CiE\
2

C3E 3
C3E]

w h e r e D is t h e a b s o r b a n c e a t t h e frequency i p e r u n i t
s a m p l e length, is t h e a b s o r p t i v i t y , a n d C is t h e
c o n c e n t r a t i o n of t h e c o m p o n e n t s . T h e subscripts refer
to t h e c o m p o n e n t s . values c a n b e o b t a i n e d b y
p l o t t i n g t h e a b s o r b a n c e a t each w a v e l e n g t h versus
c o n c e n t r a t i o n . T h e a b o v e e q u a t i o n s c a n b e inverted
by reciprocal m a t r i x m e t h o d s a n d solved with t h e
aid of a c o m p u t e r by s u b s t i t u t i n g t h e a b s o r b a n c e
readings.
A least-squares curve-fit m e t h o d h a d been applied
to each p u r e p o l y m e r s t a n d a r d over t h e entire r a n g e
- 1
of 1150-645 c m . T h e c o m m e r c i a l s a m p l e s were fit
ted in t h e s a m e spectral region. T h e m e t h o d s d e
veloped b y H a m p t o n , Silas, Binder a n d M o r e r o gave
results in which t h e vinyl c o n c e n t r a t i o n s were within

2. High-Resolution

NMR

of

Polybutadiene

H i g h - r e s o l u t i o n - N M R h a s n o t p r o v e d suitable for
t h e d e t e r m i n a t i o n of cis-trans
ratios in p o l y b u t a
diene, since t h e r e s o n a n c e s a r e n o t resolvable a t 60
a n d 100 M H z . T h e d e v e l o p m e n t of high-field N M R
s p e c t r o m e t e r s o p e r a t i n g a t 270 M H z o r g r e a t e r h a s
m a d e it possible t o d e t e r m i n e t h e a s - 1 , 4 , trans-1,4 a n d
vinyl-1,2 c o n t e n t of p o l y b u t a d i e n e (Santee et al.
1973). T h e r e s o n a n c e s in t h e s p e c t r u m o c c u r a s fol
lows: 1.3, 2.0, 4 . 8 , 5.4 a n d 5.6 p p m a n d h a v e been

( C H 2 - C = CH - C H 2 )

Ail

JUU

"T~

"
120

IOO

80

Chemical shift

60

40

20

( ppm ]

Figure 2
13
C-NMR spectra of solid rubbers (a) cw-polyisoprene and (b) ira/w-polyisoprene. Spectra were obtained on a solid-state
NMR operating at 37.7 MHz (carbon frequency). Conditions: single-pulse experiment with proton decoupling during
acquisition and magic angle spinning at 1.8 kHz

100

Elastomers:

assigned t o t h e 1,2 m e t h y l e n e , 1,4 m e t h y l e n e , 1,2

terminal, 1,4 olefinic a n d n o n t e r m i n a l vinyl p r o t o n s ,
respectively. T h e p e a k s a t 2.0 a n d 5.4 p p m a r e
observed as d o u b l e t s w h i c h c o r r e s p o n d t o t h e cistrans units. T h e c o m p o s i t i o n c a n be d e t e r m i n e d by
i n t e g r a t i o n of t h e olefinic o r a l i p h a t i c p r o t o n r e g i o n s .
C a r b o n - 1 3 N M R h a s also b e e n used to investigate
the m i c r o s t r u c t u r e of p o l y b u t a d i e n e ( D u c h a n d G r a n t
1970, M o c h e l 1972). T h e c a r b o n r e s o n a n c e in t h e
trans isomer w a s f o u n d 5.4 p p m downfleld from the
cis isomer a n d , similarly, t h e olefinic c a r b o n in
the trans i s o m e r w a s f o u n d 0.7 p p m upfleld from t h e
cis isomer. In - N M R , t h e m e t h y l e n e p e a k s of t h e cis
1 3
a n d trans isomers a r e essentially u n r e s o l v a b l e . In C N M R , the m e t h y l e n e a n d olefinic p e a k s were f o u n d t o
be s e p a r a t e d b y a p p r o x i m a t e l y 100 p p m . T h e q u a n t i
tative analysis h a s n o t p r o v e n t o b e s t r a i g h t f o r w a r d
because of t h e differences in the n u c l e a r O v e r h a u s e r
effect a n d spin-lattice r e l a x a t i o n times. H o w e v e r , b y
waiting for over five times t h e spin-lattice r e l a x a t i o n
times a n d e m p l o y i n g g a t e d d e c o u p l i n g , q u a n t i t a t i v e
d a t a c a n be o b t a i n e d .

3. Infrared

Analysis

of

Polyisoprene

Polyisoprene is c o m p o s e d of four isomeric u n s a t u r

ated structures: d s - l , 4 - p o l y i s o p r e n e , trans-\
,4-po\yisoprene, vinyl-1,2-polyisoprene a n d vinyl-3,4-polyisoprene. T h e analysis of p o l y i s o p r e n e is difficult;
like p o l y b u t a d i e n e , t h e o u t - o f - p l a n e C H - d e f o r m a t i o n
m o d e s a r e satisfactory for use in d e t e r m i n i n g vinyl-1
- 1
a n d vinyl-1,2 at 908 c m , b u t t h e
3,4 at 888 c m
-1
cw-1,4 b a n d a t 8 3 9 c m
a n d t h e trans-\,4 b a n d a t
-1
842 c m
a r e relatively w e a k a n d o v e r l a p b a d l y .
T h o u g h t h e analysis of p o l y i s o p r e n e b y infrared spec
t r o s c o p y h a s been r e p o r t e d (Binder a n d R a n s h a w
1957), N M R m e t h o d s of analysis a r e preferable.

4. High-Resolution

NMR

of

Polyisoprene

H i g h - r e s o l u t i o n - N M R c a n be used t o distinguish
1,4-polyisoprene from 3,4-polyisoprene b y t h e reso
n a n c e lines o b s e r v e d a t 5.02 a n d 4.73 p p m , respect
ively. T h e chemical shifts of t h e m e t h y l p r o t o n s in
trans- a n d cw-polyisoprene h a v e been f o u n d t o differ
by 0.07 p p m (1.67 p p m for t h e cis a d d u c t a n d
1.60 p p m for t h e trans a d d u c t ) . I n synthetic p o l y i s o
p r e n e w h i c h c o n t a i n s s o m e 3,4 u n i t s , t h e m e t h y l
p r o t o n r e s o n a n c e of t h e trans a d d u c t a n d t h e 3,4
a d d u c t a r e u n r e s o l v a b l e . T h e m e t h y l e n e p r o t o n reso
nances for cis a n d trans n a t u r a l r u b b e r a r e a l s o
1 3
u n r e s o l v a b l e (Stehling a n d B a r t z 1966). W i t h C N M R the individual c a r b o n r e s o n a n c e lines a r e dis
tinguishable (Fig. 2). T h e cw-polyisoprene c a r b o n
chemical shifts a r e as follows: - c a r b o n , 135.7 p p m ;
^-carbon, ~ 1 2 6 ppm; y-carbon, ~ 3 4 p p m ; d-carbon,
28 p p m ;
and
-carbon,
25 p p m .
For
trans-

Tests for Mechanical

Properties

p o l y i s o p r e n e t h e chemical shifts are: - c a r b o n ,

~ 135.2 p p m ; ^ - c a r b o n , 125 p p m ; y-carbon, 41 p p m ;
^ - c a r b o n , 28 p p m ; a n d - c a r b o n , 17 p p m . It h a s been
s h o w n t h a t the y-methylene chemical shifts differ by
7.0 p p m , t h e ^ - m e t h y l e n e chemical shifts differ
by 0.2 p p m a n d t h e m e t h y l chemical shift differs by
7.6 p p m for the cis- a n d /rww-polyisoprenes ( D u c h
a n d G r a n t 1970). Q u a n t i t a t i v e d a t a c a n be o b t a i n e d
by t h e m e t h o d given for p o l y b u t a d i e n e .
See also: Nuclear Magnetic Resonance Spectroscopy of
Solids

Bibliography
Binder J L 1954 Analysis of polybutadienes and butadienestyrene copolymers by infrared spectroscopy. Anal.
Chem. 26: 1877-82
Binder J L, Ransaw C 1957 Analysis of polyisoprenes by
infrared spectroscopy. Anal. Chem. 29: 503-8
Duch W, Grant D M 1970 Carbon-13 chemical shift
studies of the 1,4-polybutadienes and the 1,4-polyisoprenes. Macromolecules 3: 165-74
Hampton R R 1949 Infrared analysis of low temperature
polymers. Anal. Chem. 21: 923-6
Hampton R R 1972 Applied infrared spectroscopy in the
rubber industry. Rubber Chem. Technol. 45: 546-626
Hatada K, Kitayama T, Terawaki Y, Tanaka Y, Sato
1980 Structural dependence of carbon-13 NMR spinlattice relaxation times of 1,4-polyisoprenes. Polym. Bull.
2: 791-7
Mochel V D 1972 Carbon-13 NMR of polymers. J. Macromol. Sci., Rev. Macromol. Chem. 8: 289-347
Morero D, Santambrogio A, Porri L, Ciampelli F 1959
Infrared analysis of polybutadienes obtained by stereospecific synthesis. Chim. Ind. (Milan) 41: 758-62
Santee R Jr, Chang R, Morton 1973 300 MHz proton
NMR of polybutadiene measurement of cis-trans iso
meric content. J. Polym. Sci., Polym. Lett. Ed.U: 449-52
Silas R S, Yates J, Thornton V 1959 Determination of
unsaturation distribution in polybutadienes by infrared
spectrometry. Anal. Chem. 31: 529-32
Stehling F C, Bartz W 1966 Determination of molecular
structure of hydrocarbon olefins by high resolution nu
clear magnetic resonance. Anal. Chem. 38: 1467-79
J. L. K o e n i g a n d D . J. P a t t e r s o n
[Case W e s t e r n Reserve University,
Cleveland, O h i o , U S A ]

Elastomers: Tests for Mechanical

Properties
T h e scope of m a t e r i a l s science involved a n d t h e types
of tests m a d e t o d e t e r m i n e physical p r o p e r t i e s of
e l a s t o m e r s are illustrated by the following general
topics ( B r o w n 1986): density a n d d i m e n s i o n s ; s h o r t t e r m stress a n d strain p r o p e r t i e s ; friction a n d wear;
creep, r e l a x a t i o n a n d set; fatigue; electrical tests;

101

Elastomers:

Tests for Mechanical

Properties

t h e r m a l p r o p e r t i e s ; effect of t e m p e r a t u r e ; e n v i r o n
m e n t a l resistance; permeability; a n d a d h e s i o n , c o r r o
sion a n d staining. T h i s article presents a r a t i o n a l e for
these varied tests r a t h e r t h a n a t t e m p t i n g t o s u m m a r
ize such a large field.

1. Reasons for Mechanical

Property

Tests

on

Elastomers
Physical p r o p e r t i e s of e l a s t o m e r s are d e t e r m i n e d for
quality c o n t r o l , for c o m p l i a n c e with specifications o r
for research a n d d e v e l o p m e n t .
Tests used for o t h e r solid m a t e r i a l s a r e seldom
directly applicable t o e l a s t o m e r s because of their
m a n y u n i q u e p r o p e r t i e s . Stresses, for e x a m p l e , are
very d e p e n d e n t o n time a n d t e m p e r a t u r e a n d a r e
n o n l i n e a r with strain. Because of the u l t r a h i g h deformability a n d low m o d u l i of e l a s t o m e r s , their test
e q u i p m e n t m u s t be a c c u r a t e a t higher d i s p l a c e m e n t s
a n d lower forces t h a n a r e n e e d e d for m o s t engineering
m a t e r i a l s . G o o d reproducibility of results c a n be
o b t a i n e d only from t h o r o u g h l y d e v e l o p e d m e t h o d s ,
which is o n e of t h e r e a s o n s for t h e m a n y s t a n d a r d i z e d
tests t h a t exist. E l a s t o m e r s m a y also h a v e u n i q u e
values of P o i s s o n ' s r a t i o , frictional p r o p e r t i e s a n d t h e
G o u g h - J o u l e effect, a n d h a v e very high energy stor
age. Hysteresis is also high a n d there is n o metallictype yield p o i n t . M a n y of these differences from o t h e r
engineering m a t e r i a l s relate directly t o the n a t u r e of
the force of r e t r a c t i o n from a d e f o r m a t i o n , which is
m o s t l y d u e t o e n t r o p y in e l a s t o m e r s b u t t o internal
energy in m o r e rigid m a t e r i a l s ( B r o w n a n d R e a d
1984).

2. Nature

of

Tests

E l a s t o m e r s a n d their p r o d u c t s a r e tested for initial

a n d c o n t i n u e d p e r f o r m a n c e in t h e u n i q u e a p p l i c a t i o n s
t h a t are e n a b l e d by their viscoelastic p r o p e r t i e s . Spe
cimens a r e , therefore, a l m o s t a l w a y s d e f o r m e d either
statically o r d y n a m i c a l l y , o r b o t h , in the test p r o c e d
ures ( C o n a n t 1985).
Static o r l o w - d e f o r m a t i o n - r a t e tests for t h e c o m
m o n s t r e s s - s t r a i n p r o p e r t i e s of m o d u l u s , tensile
strength a n d e l o n g a t i o n a r e usually m a d e only for
quality c o n t r o l since e l a s t o m e r s a r e s e l d o m e l o n g a t e d
in service. L o w - r a t e tests for creep, stress r e l a x a t i o n
a n d set, h o w e v e r , reflect c o n c e r n for limitations of
service b e c a u s e of t h e t i m e - d e p e n d e n t p r o p e r t i e s t h a t
a r e peculiar t o e l a s t o m e r s . E x a m p l e s a r e m o t o r
m o u n t s , g a s k e t seals a n d bridge bearings. T h e
a m o u n t of static d e f o r m a t i o n also affects o t h e r
p r o p e r t i e s such as gas permeability, friction, electrical
characteristics a n d crystallization t h a t a r e i m p o r t a n t ,
for e x a m p l e t o tire inner liners, tire t r e a d s , a n t i s t a t i c
a p p l i c a t i o n s a n d t o s o m e p o l y m e r s w h e n used u n d e r
arctic c o n d i t i o n s . Flexibility r a t h e r t h a n c o n t i n u o u s

102

d e f o r m a t i o n is involved directly o r indirectly in such

a p p l i c a t i o n s as c o a t i n g s , d i a p h r a g m s a n d w e a r i n g
a p p a r e l . H a r d n e s s (the resistance t o i n d e n t a t i o n with
o u t p u n c t u r e ) is largely a function of m o d u l u s a n d
requires different i n s t r u m e n t s for each of three ranges
of h a r d n e s s .
E l a s t o m e r s a r e usually d e f o r m e d d y n a m i c a l l y in
service, t h e r e b y t r a n s f o r m i n g m e c h a n i c a l i n t o h e a t
energy. D e f o r m a t i o n is t h u s resisted by b o t h elastic
a n d d a m p i n g forces. T h e principal p u r p o s e s of dy
n a m i c m e c h a n i c a l tests a r e t o e v a l u a t e these forces
a n d t h e a t t e n d a n t loss of useful energy. A bewildering
n u m b e r of tests for s t o r a g e , loss a n d c o m b i n a t i o n
p r o p e r t i e s h a s b e e n d e v e l o p e d from t h e v i e w p o i n t s of
m a t e r i a l p r o p e r t i e s , engineering p r o p e r t i e s a n d tech
nological p r o p e r t i e s . T h i s relation of physical test t o
t h e p r o p e r t y involved h a s been t r e a t e d in detail by
F r e a k l e y a n d P a y n e (1978) a n d by H e p b u r n a n d
R e y n o l d s (1979).

3. Quality

Control

Tests for c o n t r o l l i n g t h e q u a l i t y of elastomeric m a t e r

ials a n d p r o d u c t s start with t h o s e m a d e by the m a n u
facturer o n t h e r a w m a t e r i a l s . B o t h physical a n d
chemical p r o p e r t i e s of even the n o n p o l y m e r i c c o m
p o n e n t s m u s t m e e t such specifications as t h o s e for
particle size, density, viscosity, p u r i t y , surface a r e a ,
p H a n d stability. Tests for elastomeric p r o p e r t i e s ,
h o w e v e r , s t a r t with t h e p o l y m e r a n d c o n t i n u e t h r o u g h
t h e v a r i o u s stages of p r e p a r a t i o n of first the u n c u r e d
c o m p o u n d , t h e n of t h e vulcanizate. T h e p r i m a r y
r e q u i r e m e n t d u r i n g fabrication is t h a t of h a v i n g a n d
m a i n t a i n i n g suitable plasticity, which is the case of
producing nonrecoverable deformation. F o r example,
if t h e p r o d u c t is o b t a i n e d by e x t r u s i o n , it m u s t also be
well formed. Plasticity c a n be quantified by c o m p r e s
sion, r o t a t i o n o r e x t r u s i o n plastimeters, which a r e
often simplified versions of processing e q u i p m e n t .
A l t h o u g h plasticity of t h e u n c u r e d m a t e r i a l c a n affect
p r o d u c t p e r f o r m a n c e , its m o s t i m p o r t a n t effect is o n
processibility in such o p e r a t i o n s as extrusion, milling,
i n c o r p o r a t i o n of c o m p o u n d i n g ingredients a n d s h a p
ing of p r o d u c t s . P o w e r c o n s u m p t i o n in e a c h of these
o p e r a t i o n s c a n be e s t i m a t e d from t o r q u e m e a s u r e
m e n t s o n i n t e r n a l mixers.
Processibility is c h a n g e d by m a s t i c a t i o n , a d d i t i o n
of c o m p o u n d i n g ingredients, t e m p e r a t u r e , s t o r a g e
time a n d scorch. Scorch, which is a p r e v u l c a n i z a t i o n ,
is m e a s u r e d b y c u r e m e t e r s o r viscometers which c a n
also be used for c o n t i n u o u s e v a l u a t i o n of t h e state
a n d r a t e of c u r e while v u l c a n i z a t i o n p r o c e e d s .
F a c t o r y b a t c h e s a r e s a m p l e d a t critical stages of
their fabrication a n d their processing t h e n c o m p l e t e d
in a l a b o r a t o r y . Q u a l i t y c o n t r o l tests o n the resulting
p r o d u c t often merely d e t e r m i n e w h e t h e r o r n o t ten
sile, m o d u l u s a n d e l o n g a t i o n a r e within prescribed
limits. S u c h tests a r e m a d e t o e n s u r e t h a t c o m p o n e n t s

Elastomers:

h a v i n g correct p r o p e r t i e s h a v e been a d d e d in t h e
correct p r o p o r t i o n s a n d t h a t t h e specified m i x i n g
p r o c e d u r e h a s been followed. M o r e tests o n elas
t o m e r s a r e p r o b a b l y m a d e for c o n t r o l t h a n for a n y
o t h e r r e a s o n . H o w e v e r , q u a l i t y c o n t r o l a t o n e stage,
say p o l y m e r m a n u f a c t u r e , b e c o m e s a c c e p t a n c e cri
teria a t a n o t h e r stage, say t h e m a n u f a c t u r e of r u b b e r
sheeting.

4.

Specifications

Specifications state t h e r e q u i r e m e n t s t h a t m u s t b e m e t
by a m a t e r i a l o r p r o d u c t . T h e y d i c t a t e t h e tests t o be
m a d e a n d a c c e p t a b l e test results. Specifications m a y
be m a d e b y a design engineer w h o requires c e r t a i n
performances, by a customer to ensure a uniform
product or adequate quality, by the manufacturer to
detect irregularities d u r i n g fabrication o r by a regula
tory agency t o m a i n t a i n safety s t a n d a r d s . D u p l i c a t e
tests a r e often m a d e by t h e final inspection d e p a r t
m e n t of a p r o d u c e r a n d b y t h e a c c e p t a n c e l a b o r a t o r y
of a c o n s u m e r o r m e r c h a n d i s e r . T h i s requires t h a t t h e
e q u i p m e n t a n d p r o c e d u r e s used b y e a c h g r o u p s h o u l d
give results t h a t differ b y n o m o r e t h a n a n agreed
a m o u n t . Systems for classifying r u b b e r s b y line call
o u t given in A S T M S t a n d a r d s D 2 0 0 0 a n d D 1 2 0 7 a r e
useful in writing specifications, especially for a u t o m o
tive a p p l i c a t i o n s .
Tests m a d e for c o n f o r m a n c e t o specifications, like
t h o s e for q u a l i t y c o n t r o l , h a v e results t h a t either
p e r m i t o r d o n o t p e r m i t a c c e p t a n c e . Tests discussed in
t h e following sections a r e m o r e c o m p r e h e n s i v e in t h a t
they c a n be used t o c h a r a c t e r i z e t h e subject m a t e r
ials a n d a r e useful for research a n d d e v e l o p m e n t
purposes.

5. Suitability

for Particular

Applications

C o m p r e h e n s i v e tests o n e l a s t o m e r s a r e r e q u i r e d for
c o m p o u n d d e v e l o p m e n t , for e n g i n e e r i n g a p p l i c a t i o n s
a n d for v a l i d a t i o n of theoretical studies. Often s t a n
d a r d i z e d , such tests m a y r a n g e in c o m p l e x i t y from
simple d e t e r m i n a t i o n of t r e n d s in t h e level of s o m e
p r o p e r t y t o t h o r o u g h , designed e x p e r i m e n t s for deter
m i n i n g p r a c t i c a l levels o f m a n u f a c t u r i n g variables for
o p t i m u m c o m b i n a t i o n s of p r o p e r t i e s .
A designed e x p e r i m e n t consists of a statistical p r o
c e d u r e t h a t requires systematic d e t e r m i n a t i o n of m u l
tiple p r o p e r t i e s (responses) o n a m u l t i v a r i e d system. It
usually requires c o m p u t e r - a i d e d analysis. E l a s t o m e r s
a r e p a r t i c u l a r l y suited t o this t y p e of o p t i m i z a t i o n of
t h e wide r a n g e of p r o p e r t i e s a n d c o m b i n a t i o n s t h e r e o f
t h a t c a n be achieved. A m o t o r m o u n t , for e x a m p l e ,
m a y require t h a t static m o d u l u s , d y n a m i c m o d u l u s
a n d energy a b s o r p t i o n r e m a i n w i t h i n s t a t e d limits
over a stated r a n g e of t e m p e r a t u r e , l o a d , frequency,
a m p l i t u d e a n d c o n c e n t r a t i o n of o z o n e a n d c e r t a i n

Tests for Mechanical

Properties

oils. T h e p r o p e r t y profile specified by the engineer

m u s t t a k e i n t o a c c o u n t t h e effects of v a r i a b l e c o m
p o n e n t levels a n d their i n t e r a c t i o n s . Since a p a r t i c u l a r
profile m a y be achievable by m o r e t h a n o n e c o m
b i n a t i o n of m a n u f a c t u r i n g variables, the test system
m u s t also p r o v i d e for e v a l u a t i o n s of varied c o m
p o n e n t levels a n d p r o c e s s i n g m e t h o d s a n d of all
possible i n t e r a c t i o n s .
T h e s e c o m p l e x r e q u i r e m e n t s , s u p p l e m e n t e d by
t h o s e for theoretical studies, h a v e led t o t h e devel
o p m e n t of very versatile test e q u i p m e n t . N o t only c a n
a given p r o p e r t y , say d y n a m i c m o d u l u s , be evalu
a t e d o n a single specimen o v e r a wide r a n g e of
test c o n d i t i o n s in a single a p p a r a t u s , b u t the s a m e a p
p a r a t u s c a n often be used for related p r o p e r t i e s ,
for e x a m p l e , energy a b s o r p t i o n , stress r e l a x a t i o n
o r failure c o n d i t i o n s . S u c h versatility is p a r t i c u l a r l y
i m p o r t a n t for testing e l a s t o m e r s w h i c h , because of
high a n d often n o n u n i f o r m deformability, h a v e
u n c e r t a i n s h a p e factors. T h u s , t h e results o b t a i n e d
from different i n s t r u m e n t s , w h i c h usually h a v e
differently s h a p e d specimens, a r e generally very
inconsistent.

6. Special

Considerations

for

Testing

Elastomers

R e p r o d u c i b i l i t y of results, especially b e t w e e n l a b o r a
tories, is very p o o r for e l a s t o m e r s unless detailed
i n s t r u c t i o n s a r e given a n d followed. T h o s e for pretest
p r o c e d u r e s m u s t include s a m p l i n g , mixing, t y p e of
m o l d , m o l d g e o m e t r y , vulcanizing time a n d t e m p e r a
t u r e a n d rest time before testing; f o r m i n g test pieces
by c u t t i n g , buffing o r plying; t h e r m a l a n d m e c h a n i c a l
c o n d i t i o n i n g ; a n d a v o i d a n c e of specific interferences
such a s surface c o n t a m i n a t i o n , i r r a d i a t i o n , o z o n e o r
o t h e r c h e m i c a l a t t a c k , strains, high t e m p e r a t u r e , crys
tallization o r u n d u e aging time.
E q u a l l y detailed i n s t r u c t i o n s a r e necessary for the
i n t e r p r e t a t i o n of test results. T h e s e include scope,
significance a n d applicability of results, precision a n d
validity, a c c u r a c y c h e c k s , c a l c u l a t i o n a n d p r e s e n t a
tion of results. Tests o n e l a s t o m e r s a r e often macfe t o
r a n k a series of sainples; t h e results a r e relative with
n o necessity t o m e e t specified values. C o r r e c t i o n s for
d a y - t o - d a y variability a r e often m a d e b y inclusion of
a c o n t r o l c o m p o u n d with e a c h of a series of experi
mental compounds.
S o m e tests yield basic p r o p e r t i e s such a s t h e r m a l
c o n d u c t i v i t y , specific h e a t , t h e r m a l e x p a n s i o n , density
a n d refractive index. T h e s e a r e i n d e p e n d e n t of t h e
m e a s u r i n g i n s t r u m e n t a n d m e t h o d . Values of these
c o n s t a n t s for typical vulcanizates of s o m e c o m m o n
p o l y m e r s h a v e b e e n p u b l i s h e d by W o o d (1975).
U s u a l l y , h o w e v e r , results a r e highly d e p e n d e n t o n
b o t h t h e test m e t h o d a n d t h e c h o s e n c o n d i t i o n s within
that method. F o r example, the statement that a
2
v u l c a n i z a t e h a s a m o d u l u s of 5.0 M N m " is m e a n i n g
less unless t h e state a n d r a t e of d e f o r m a t i o n a r e given

103

Elastomers:

Tests for Mechanical

Properties

a l o n g with t h e t e m p e r a t u r e . F u r t h e r m o r e , t h e value
m u s t b e identified as Y o u n g ' s m o d u l u s o r rigidity
m o d u l u s , as e q u i l i b r i u m o r t r a n s i e n t , a s t a n g e n t o r
secant, w h e t h e r b a s e d o n original o r a t t a i n e d cross
section a n d w h e t h e r d e t e r m i n e d o n t h e first o r subse
q u e n t d e f o r m a t i o n s . T h e s e a r e s o m e of t h e m a n y
i m p o r t a n t details t h a t a r e included in s t a n d a r d i z e d
tests.

Wood L A 1975 Tables of physical constants of rubber. In:

Brandrup J, Immergut (eds.) 1975 Polymer Hand
book, 2nd edn., Pt. V. Interscience, New York, pp. 7-12

7.

T h e c o h e r e n t scattering of electrons b y m a t e r i a l s is
t e r m e d diffraction. F o r crystalline solids, c o n s t r u c t i v e
interference of diffracted electrons only o c c u r s in
specific directions with respect t o t h e incident w a v e .
T h e resulting diffraction p a t t e r n s c a n b e used t o
a n a l y z e t h e a t o m i c s t r u c t u r e of a specimen in several
w a y s , d e p e n d i n g o n t h e specific diffraction t e c h n i q u e s
used.
E l e c t r o n s c a n b e r e g a r d e d a s waves h a v i n g a w a v e
length g o v e r n e d b y their energy. T o a g o o d a p p r o x i
m a t i o n a t nonrelativistic energies,

F . S. C o n a n t
[Firestone Tire a n d R u b b e r C o m p a n y ,
Akron, Ohio, USA]

Electron Diffraction
Standards

Tests m a y be s t a n d a r d i z e d a t i n t e r n a t i o n a l , n a t i o n a l
o r industrial level. T h e y r e p r e s e n t a c o n s e n s u s of
interested p a r t i e s including p r o d u c e r , c o n s u m e r , sales
m a n a g e r , r e g u l a t o r a n d theoretician. T h e y a r e usually
o u t g r o w t h s of tests d e v e l o p e d for c o m p a n y u s e ,
agreement between producer a n d consumer, or m a d e t o - o r d e r tests for p a r t i c u l a r research o r d e v e l o p m e n t
w o r k . O n l y b y such b r o a d - b a s e d i n p u t c a n t h e inclu
sion of all necessary c o n s i d e r a t i o n s b e a s s u r e d .
S o m e 300 s t a n d a r d s o r r e c o m m e n d a t i o n s o n r u b
ber h a v e been d e v e l o p e d b y t h e I n t e r n a t i o n a l S t a n
dards Organization (ISO). Various national bodies
such as A N S I in t h e U S A , BSI in t h e U K , G O S T in
Russia, A F N O R in F r a n c e a n d D I N in G e r m a n y c a n
supply I S O s t a n d a r d s o n request. T h e s e g r o u p s also
h a v e c o m p r e h e n s i v e s t a n d a r d s of their o w n w h i c h
usually c o n f o r m essentially t o c o r r e s p o n d i n g I S O
s t a n d a r d s if they exist. M o s t of t h e A N S I s t a n d a r d s
a r e included in t h e A S T M Annual Book of Standards.
A widely accepted list of s t a n d a r d test t e m p e r a t u r e s
a n d o t h e r i n t r a s t a n d a r d a g r e e m e n t s such a s rest t i m e
between c u r i n g a n d testing a r e very helpful for o p e r a
tional efficiency a n d for c o r r e l a t i n g results from dif
ferent tests.
T h e v a r i o u s types of s t a n d a r d s include test m e t h
o d s , specifications, t e r m i n o l o g y , classification, p r a c
tice, guide a n d i n f o r m a t i o n . All o f these c o n t r i b u t e
to c o m m u n i c a t i o n a m o n g interested p a r t i e s , w h i c h
includes t h o s e t h a t m a k e o r d i n a n c e s a n d set tariff
rates.

= (\.5/

/2

(1)

w h e r e V is in electron volts a n d is in n a n o m e t e r s .
Since electrons i n t e r a c t very efficiently with b o t h t h e
nucleus a n d t h e electron c l o u d a s they p e n e t r a t e a
solid, they r a p i d l y lose energy, a n d c o h e r e n t scatter is
impossible. T h e r e f o r e electron diffraction is only use
ful for s t u d y i n g t h e surfaces o f b u l k m a t e r i a l s o r t h e
i n t e r n a l s t r u c t u r e of very thin (<^ 0.5 ) specimens.
T h e s t u d y of surfaces is p e r f o r m e d using low-energy
electron diffraction ( L E E D ) w h e r e V is 5 - 5 0 0 eV (see
Electron
Diffraction,
Low-Energy),
a n d reflection
high-energy electron diffraction ( R H E E D ) w h e r e is
5-500 k e V . T h e s t u d y o f t h i n foils is a l m o s t i n v a r i a b l y
p e r f o r m e d w i t h a t r a n s m i s s i o n electron m i c r o s c o p e
( T E M ) , in w h i c h electron i m a g e s c a n b e f o r m e d
c o n c u r r e n t l y from t h e a r e a t h a t is diffracting. T h i s
latter t e c h n i q u e r e p r e s e n t s a m a j o r a p p l i c a t i o n o f
electron diffraction t o t h e s t u d y of m a t e r i a l s , a n d is
e m p h a s i z e d in this article.

Bibliography

7. Theory

American Society for Testing and Materials Annual Book of

Standards, Pts. 9.01, 9.02. American Society for Testing
and Materials, Philadelphia, PA
Brown R 1986 Physical Testing of Rubbers, 2nd edn.
Applied Science, London
Brown R P, Read (eds.) 1984 Measurement Techniques
for Polymeric Solids. Elsevier, New York
Conant F S 1985 Physical testing of vulcanizates. In: Mor
ton (ed.) 1985 Rubber Technology, 3rd edn. Van
Nostrand Reinhold, New York
Freakley , Payne A R 1978 Theory and Practice of
Engineering with Rubber. Applied Science, London
Hepburn C, Reynolds R J W 1979 Elastomers: Criteria for
Engineering Design. Applied Science, London

C o n s i d e r i n g crystalline m a t e r i a l s only, electron dif

fraction occurs w h e n t h e p a t h difference b e t w e e n
incident a n d diffracted electron w a v e s is a n integral
n u m b e r of w a v e l e n g t h s . F o r a crystal w i t h u n i t cell
lattice p a r a m e t e r s a, b a n d c, this c o n d i t i o n is d e
scribed b y t h e L a u e e q u a t i o n s in three d i m e n s i o n s :

104

of Electron

Diffraction

hk = tf(cos OLX - cos a 2 )

(2)

kk = b(cosfix

(3)

-cosfi2)

Ik = c(cos yx - c o s y2)

(4)

w h e r e h, k a n d / a r e integers w h i c h c o r r e s p o n d t o t h e

Electron

Diffraction

factors a r e k n o w n as t h e a t o m i c scattering f a c t o r / ( )
a n d t h e s t r u c t u r e factor F(6), respectively. T h e value
off () is given b y
/()

Figure 1
(a) The coherent scattering of electron waves by a row of
atoms as described by the Laue equations, (b) The
reflection of electron waves by parallel atomic planes of
spacing d as described by the Bragg equation. Reflection
of electrons from the dotted plane spacing d/2 would
result in destructive interference and no diffracted
intensity (assuming all planes are identical)

Miller indices for a specific diffracting p l a n e . T h e

cosines of t h e angles define t h e incident (,,/,,)^) a n d
diffracted (a 2,/? 2,y 2) b e a m d i r e c t i o n s w i t h respect t o t h e
r o w s of scattering a t o m s of s p a c i n g a, b a n d c,
respectively, a s s h o w n in o n e d i m e n s i o n in F i g . l a . ( I n
this d i a g r a m A B - C D is t h e p a t h difference given b y
E q n . (2).) T h e e q u a t i o n s e a c h describe a c o n e o f
coherently scattered electrons e m a n a t i n g from e a c h
r o w of scattering a t o m s , a n d in t h r e e d i m e n s i o n s
c o h e r e n t scattering only o c c u r s a l o n g t h e d i r e c t i o n in
which all three c o n e s coincide. T h u s , d e p e n d i n g o n
the crystal s t r u c t u r e , scattering will o c c u r in specific
directions. A m o r e s t r a i g h t f o r w a r d a n d m a t h e m a t i
cally e q u i v a l e n t d e s c r i p t i o n h a s b e e n given b y B r a g g ,
w h o used t h e (physically incorrect) a n a l o g y of elec
t r o n reflection (see F i g . l b ) t o d e d u c e t h a t c o h e r e n t
scatter from a t o m i c p l a n e s o f s p a c i n g d o c c u r s w h e n
= 2d sin

(5)

w h e r e is t h e angle o f incidence a n d reflection, a n d

is a n integer. T h u s t h e p a t h difference b e t w e e n elec
t r o n s reflected from different p l a n e s (distance A B C in
Fig. l b ) is a g a i n a n integral n u m b e r of w a v e l e n g t h s if
diffraction is t o occur. It is u s u a l t o r e g a r d highero r d e r diffracted b e a m s (n = 2, 3 , . . . ) from a specific
(hkl) p l a n e of s p a c i n g d a s e q u i v a l e n t t o
first-order
diffraction from a parallel p l a n e o f indices (nh nk nl)
a n d spacing d/n.
T h e diffracted intensity in a n y p a r t i c u l a r direction
is a function of t h e a t o m i c species t h a t is scattering,
a n d of t h e a t o m i c d i s t r i b u t i o n in t h e crystal. T h e s e

= [(m0e )/2h ](X/sm

) (-/)

(6)

w h e r e m0 is t h e rest m a s s o f t h e electron, e is t h e
electronic c h a r g e , h is P l a n c k ' s c o n s t a n t , is t h e
a t o m i c n u m b e r a n d fx is t h e a t o m i c scattering factor
for r a y s . E q u a t i o n (6) is a c o m b i n a t i o n of R u t h e r
ford scattering effects from t h e nucleus a n d scattering
f r o m t h e electron c l o u d . F r o m E q n . (6) it c a n b e seen
t h a t diffracted intensity is strongly p e a k e d in t h e
f o r w a r d d i r e c t i o n ( small), a n d h i g h e r - Z a t o m s scat
ter m o r e strongly.
T h e a m p l i t u d e scattered b y a u n i t cell F(0) c a n b e
c a l c u l a t e d b y s u m m i n g t h e values /()
for e a c h of
a t o m s in t h e u n i t cell, t a k i n g i n t o a c c o u n t t h e p h a s e
difference b e t w e e n e a c h scattering p o i n t . T h u s , t h e
scattering from a p a r t i c u l a r (hkl) p l a n e is given b y
n0)hkl

= Z/(0)exp[ " 2ni{hxn

+ kyn + lzn)]

(7)

w h e r e xn9 yn, zn a r e t h e a t o m i c c o o r d i n a t e s of t h e t h
a t o m a n d the exponential term represents the phase
2
difference. T h e a c t u a l intensity is given b y F(0)hkl
.
Clearly for different crystal s t r u c t u r e s different
intensities will arise from t h e s a m e (hkl) p l a n e , a n d
u n d e r specific g e o m e t r i c a l c o n d i t i o n s F(6) a n d t h e
s c a t t e r e d intensity will b e z e r o . F o r e x a m p l e , in F i g .
l b , t h e d o t t e d line represents a p l a n e o f a t o m s spacing
d/2, from w h i c h scattered electrons w o u l d destructi
vely interfere with electrons diffracted from t h e p l a n e s
of s p a c i n g d, giving z e r o diffracted intensity. S u c h s o called systematic absences a r e characteristic of speci
fic s t r u c t u r e s (e.g., w h e n h + k + / is o d d , F(6) = 0 in
b o d y - c e n t e r e d - c u b i c s t r u c t u r e s ) . Similarly, if m o r e
t h a n o n e a t o m t y p e is p r e s e n t (e.g., in alloys), t h e n
differences in f(9) b e t w e e n different a t o m s c a n give
rise t o large c h a n g e s in diffracted intensity, such a s t h e
presence of intensity w h e r e systematic absences a r e
expected.

2. Indexing

Diffraction

Patterns

T o d e t e r m i n e w h i c h (hkl) p l a n e is responsible for

w h i c h diffracted b e a m , it is u s u a l t o e m p l o y t h e
c o n s t r u c t i o n of a reciprocal lattice of t h e specimen, in
w h i c h a set o f parallel (hkl) a t o m i c p l a n e s a r e repre
sented b y p o i n t s a d i s t a n c e \/dm from t h e origin.
T h e s e p o i n t s c a n b e c o n s i d e r e d t o r e p r e s e n t t h e dif
fracted intensity, since if t h e B r a g g law ( E q n . (5)) is
rewritten as
sm0

= (dhkly /(2/X)

(8)

a n d if a s p h e r e of d i a m e t e r 2/ ( t e r m e d t h e E w a l d
sphere) is inscribed within t h e reciprocal lattice a n d
g o i n g t h r o u g h t h e origin, t h e n a n y p o i n t s in t h e lattice

105

Electron

Diffraction
R a t h e r t h a n c a r r y o u t this exercise for every situa
tion, it is c o m m o n practice t o orient t h e specimen
such t h a t a low-index z o n e (e.g., a l o n g b e a m direction
[01 ] a s in F i g . 3) of p l a n e s is diffracting, a n d t h e n t o
compare the observed pattern with standard ones.
T h e fact t h a t it is possible t o o b t a i n diffraction from
several p l a n e s in a z o n e a t o n c e is also d u e t o t h e effect
of t h e specimen s h a p e o n t h e diffracted intensity
d i s t r i b u t i o n . T h e diffraction s p o t is only a m a t h e m a t i
cal p o i n t if t h e specimen is infinite in all directions.
F o r e x a m p l e , a T E M specimen is effectively infinite
( ~ 3 m m ) in t h e p l a n e of t h e specimen, a n d very thin
( < 0 . 5 ) parallel t o t h e electron b e a m . T h i s m e a n s
t h a t t h e diffracted intensity c a n b e represented in t h e
reciprocal lattice a s a r o d stretched parallel t o t h e
electron b e a m in reciprocal space, r a t h e r t h a n as a
p o i n t . T h e r e f o r e , over a r a n g e of angles, t h e E w a l d
s p h e r e will still intercept t h e r o d a n d diffracted inten
sity will still exist, a s s h o w n in F i g . 4. T h i s is equiva
lent t o saying t h a t t h e L a u e c o n d i t i o n is relaxed in o n e
d i m e n s i o n in t h e T E M o w i n g t o t h e specimen s h a p e ;

Reciprocal
spacing

lattice

\/dhkl

* 3

nm

-1

Figure 2
(a) The Ewald sphere-reciprocal lattice construction,
showing how Bragg's law is only satisfied by atomic
planes whose reciprocal lattice spots lie on the surface of
the sphere. If the specimen or beam orientation is
changed, as can be done routinely in the TEM, then
different planes will diffract and the diffraction pattern will
change, (b) Relative magnitudes of the Ewald sphere and
reciprocal lattice in the TEM showing that the surface of
the sphere is almost planar with respect to the reciprocal
lattice

t h a t intersect t h e surface of t h e s p h e r e will satisfy t h e

Bragg e q u a t i o n a n d hence t h e p l a n e s they represent
will b e diffracting strongly. T h i s is s h o w n in t w o
d i m e n s i o n s in F i g . 2a. C o n s i d e r i n g t h e relative d i m e n
sions of dm a n d X, it c a n b e seen t h a t for r a y s w h e r e
is ~ 0 . 2 n m a n d 2/ is ~ 1 0 n . n i " 1 , t h e c h a n c e of
m a n y diffraction m a x i m a o c c u r r i n g from a crystal
w h e r e \/dis ~ 3 n m " 1 is very small. T h i s explains w h y
it is necessary t o use white r a d i a t i o n (wide r a n g e of
) o r t o oscillate, r o t a t e o r p o w d e r t h e specimen
( m a n y v a r i a t i o n s of d a n d ) in o r d e r t o get e n o u g h
diffraction s p o t s t o analyze t h e s t r u c t u r e (see X-Ray
Powder Diffraction). F o r 100 k V electrons, h o w e v e r ,
is 0.0037 n m a n d 2/ is 540 n m " 1 , a n d t h u s t h e surface
of t h e E w a l d s p h e r e is a l m o s t p l a n a r in c o m p a r i s o n
with t h e a r r a y of reciprocal lattice s p o t s ( F i g . 2 b ) .
T h u s , with a n electron m i c r o s c o p e several diffraction
spots a r e o b s e r v e d from a thin-foil specimen ( F i g . 3)
c o r r e s p o n d i n g t o a section t h r o u g h t h e reciprocal
lattice.

106

Figure 3
Electron diffraction pattern of an Al-Li-Cu-Mg alloy.
The intense fundamental spots correspond to a section
through the reciprocal lattice of the face-centered-cubic
aluminum structure, normal to <0lT>. The area from
which the pattern was obtained is shown in the inset.
Small precipitates of Al 2CuMg are visible in the
background and platelike precipitates of ASl 2CuLi can be
clearly seen. These precipitates give rise to the faint
diffraction spots and the streaks normal to the plane of
the Al 2CuLi plates (courtesy of S. F. Baumann)

Electron

as a r o d o r s t r e a k n o r m a l t o t h e p l a n e of t h e plate. I n
this m a n n e r , i n f o r m a t i o n c o n c e r n i n g t h e s h a p e a n d
v o l u m e fraction of t h e diffracting species c a n b e
o b t a i n e d from t h e p a t t e r n .

Incident

4. Convergent-Beam

lattice

rods

Figure 4
Schematic diagram showing the effect of the shape of the
diffracting volume (in this case the thin foil specimen) on
the reciprocal lattice spot

t h a t is, E q n s . (2) a n d (3) r e m a i n b u t E q n . (4) is

eliminated. F o r this r e a s o n , a c c u r a t e s t r u c t u r a l a n a l y
sis of u n k n o w n specimens is very difficult in c o n v e n
tional T E M diffraction, a n d rays a r e still t h e best
m e t h o d for this.
By p r o p e r c a l i b r a t i o n a n d analysis of t h e diffrac
tion p a t t e r n , such as in F i g . 3, (hkl) indices m a y
be assigned t o e a c h diffraction s p o t in t h e t w o dimensional pattern.
5. Further

Information

in Electron

Diffraction

Electron

Diffraction

Patterns

C o n v e n t i o n a l electron diffraction uses a parallel

c o h e r e n t b e a m of electrons, so t h a t the r e s u l t a n t
p a t t e r n is s h a r p l y defined (see F i g . 3). M o r e recently
t h e d e v e l o p m e n t of s c a n n i n g t r a n s m i s s i o n electron
m i c r o s c o p y h a s led t o t h e use of fine ( < 5 0 n m )
c o n v e r g e n t p r o b e s , w h i c h , as well as p e r m i t t i n g dif
fraction i n f o r m a t i o n t o b e o b t a i n e d from regions of
t h e o r d e r of t h e p r o b e size, also p e r m i t a d d i t i o n a l
c r y s t a l l o g r a p h i c i n f o r m a t i o n t o be o b t a i n e d . I n
m o d e r n electron m i c r o s c o p e s , t h e electron optics a r e
sufficiently flexible t o p e r m i t t h e o b s e r v a t i o n of high
angles of scatter, a n d , as c a n b e seen in F i g . 4, a t high
e n o u g h angles, reciprocal lattice r o d s from highero r d e r L a u e zones ( H O L Z ) will intercept t h e E w a l d
s p h e r e . T h e d i a m e t e r of t h e r e s u l t a n t intensity rings
gives s t r u c t u r a l i n f o r m a t i o n a b o u t t h e d i m e n s i o n of
t h e specimen parallel t o t h e electron b e a m . A typical
c o n v e r g e n t b e a m p a t t e r n is s h o w n in Fig. 5, in which
H O L Z rings a r e p r e s e n t . By s u p e r p o s i t i o n of t h e z e r o o r d e r z o n e o n t h e first-order z o n e , it is possible t o
d e t e r m i n e t h e lattice type from a single p a t t e r n .

Diffraction

Patterns
A s well as the c r y s t a l l o g r a p h i c i n f o r m a t i o n p r e s e n t in
the d i s t r i b u t i o n of f u n d a m e n t a l s p o t s in t h e diffrac
tion p a t t e r n , such as in F i g . 3, o t h e r k i n d s of i n f o r m a
tion c a n often be o b t a i n e d from diffraction p a t t e r n s .
First, t h e c o m b i n a t i o n of electron i m a g i n g w i t h
diffraction i n f o r m a t i o n p e r m i t s identification o f
the c r y s t a l l o g r a p h i c characteristics of s e c o n d - p h a s e
particles, dislocations a n d p l a n a r defects. Secondly,
because all periodic s t r u c t u r e s c a n diffract, such p h e
n o m e n a as dislocation a r r a y s in interfaces, a r r a y s of
a n t i p h a s e b o u n d a r i e s in o r d e r e d m a t e r i a l a n d peri
odic a r r a y s of precipitates, as in s p i n o d a l m i c r o s t r u c tures, all give rise t o diffraction effects in t h e p a t t e r n
which c a n be discerned a n d often q u a n t i t a t i v e l y
interpreted.
E x a m p l e s of these effects c a n b e seen in F i g u r e 3.
T h e specimen is a c o m p l e x a l u m i n u m alloy with a
face-centered-cubic crystal s t r u c t u r e , a n d t h e intense
s p o t s represent diffraction m a x i m a from t h e crystal
planes of t h e {200} a n d {111} type, characteristic of
planes in the [OlT] z o n e axis, d o w n w h i c h t h e b e a m is
travelling. T h e r o w s of less intense s p o t s arise from
s e c o n d - p h a s e precipitates of A l 2 C u M g a n d A l 2 C u L i .
T h e A l 2 C u L i p h a s e is p r e s e n t as very thin plates in t h e
p l a n e parallel t o the b e a m , a n d a c c o r d i n g l y t h e L a u e
c o n d i t i o n is relaxed for diffraction b y these p l a t e s (see
inset, Fig. 3), such t h a t t h e diffracted intensity a p p e a r s

Figure 5
Convergent beam [001] electron diffraction pattern for
garnet; two HOLZ rings are clearly visible as well as
HOLZ lines within the diffracted intensity disks (courtesy
of M. Raghaven)

107

Electron

Diffraction

to t h e distance of a p p r o a c h t h a t w o u l d be expected if
t h e m a t e r i a l were t o crystallize.
See also: Electron Diffraction, Low-Energy; Transmission
Electron Microscopy: Convergent-Beam and Microdiffraction Techniques; X-Ray and Neutron Diffraction Studies of
Amorphous Solids

Bibliography

Figure 6
Central (000) disk in convergent beam pattern from < 111 >
oriented pure copper showing HOLZ lines crossing the
concentric extinction fringes. The HOLZ lines show the
true triad symmetry down < 111 > (courtesy of K. S.
Vecchio)

A l t h o u g h Fig. 5 is o v e r e x p o s e d d u e to the high

intensity of t h e z e r o - o r d e r L a u e z o n e (central intense
region) there is m o r e i n f o r m a t i o n in e a c h of t h e
diffraction m a x i m a . I n p a r t i c u l a r , in m a n y c o n v e r g e n t
b e a m p a t t e r n s , if the specimen is of c o n s t a n t thick
ness, a n d thick e n o u g h for d y n a m i c a l diffraction t o
occur ( > 50 n m ) , t h e n a n a r r a y of d a r k lines ( t e r m e d
H O L Z lines) is often visible in a magnified view of the
central (000) diffraction disk (see Fig. 6). F r o m these
H O L Z lines it is possible to p e r f o r m very a c c u r a t e (2
p a r t s in 10 4) lattice p a r a m e t e r m e a s u r e m e n t s a n d also
o b t a i n direct t h r e e - d i m e n s i o n a l crystal s y m m e t r y
information.
T h e parallel intensity lines r a d i a t i n g from t h e z e r o o r d e r L a u e z o n e in Fig. 5 a r e t e r m e d K i k u c h i lines
a n d are d u e t o diffraction of inelastically scattered
electrons t h a t h a v e lost energy d u r i n g i n t e r a c t i o n s
within t h e specimen. T h e s e lines, w h i c h o c c u r in all
electron diffraction p a t t e r n s from r e a s o n a b l y thick,
u n d e f o r m e d specimens, p e r m i t very a c c u r a t e orien
t a t i o n of t h e crystal lattice with respect t o the electron
b e a m t o be d e t e r m i n e d , a n d t h u s a r e a n invaluable aid
in diffraction analysis.

5. Diffraction

from

Amorphous

Materials

By their n a t u r e , a m o r p h o u s m a t e r i a l s d o n o t give rise

t o well-defined diffraction p a t t e r n s . Nevertheless,
m a t e r i a l s such as glass a n d p o l y m e r s often d o n o t
possess a truly r a n d o m a m o r p h o u s s t r u c t u r e , a n d
their diffraction p a t t e r n s consist of diffuse m a x i m a
which c a n be related t o the a p p r o x i m a t e p o s i t i o n of
n e a r e s t - n e i g h b o r a t o m s . T h i s distance is usually close

108

Amelinckx S, Gevers R, Van Landuyt J 1978 Diffraction and

Imaging Techniques in Material Science, 2nd edn. NorthHolland, Amsterdam
Andrews W, Dyson D J, Keown S R 1967 Interpretation
of Electron Diffraction Patterns, 1st edn. Hilger, Bristol,
UK
Edington J W 1976 Practical Electron Microscopy in Mater
ials Science. Van Nostrand Reinhold, New York
Mansfield J, Steeds J W (eds.) 1984 Convergent Beam
Electron Diffraction of Alloy Phases. Hilger, Bristol, UK
Steeds J W 1979 Convergent beam electron diffraction. In:
Hren J J, Goldstein J I, Joy D C (eds.) 1979 Introduction
to Analytical Electron Microscopy. Plenum, New York,
pp. 387^22
D . B. Williams
[Lehigh University, Bethlehem,
Pennsylvania, USA]

Electron Diffraction, Low-Energy

Surface-sensitive electron scattering e x p e r i m e n t s
usually involve electrons in t h e energy r a n g e 0 200 eV, w h e r e electrons h a v e restricted p e n e t r a t i o n of
less t h a n 1 n m . H i g h e r energies c a n b e used, u p t o
50 keV, a n d surface sensitivity c a n b e m a i n t a i n e d b y
using glancing incidence c o n d i t i o n s . I n t h e lower
energy r a n g e t h e electrons a r e m o n o c h r o m a t i c t o
within typically 0.1 eV a n d collimated t o b e t t e r
t h a n 1 . Very low-energy e x p e r i m e n t s in t h e r a n g e
0 - 1 0 eV m a y use special analyzers t o m o n o c h r o m a t e
the b e a m further, 5 m e V being t h e best r e s o l u t i o n
attainable.
Because of surface sensitivity t h e s a m p l e itself m u s t
always b e carefully p r e p a r e d in a n u l t r a h i g h v a c u u m
a n d m o n i t o r e d with A u g e r techniques t o detect
impurities. Diffraction e x p e r i m e n t s in p a r t i c u l a r need
carefully c u t a n d oriented single-crystal specimens.
T h e s a m p l e reflects a b o u t 1 % of t h e incident elec
t r o n s ; this fraction is increased a t very low energies.
T h e simplest d e t e c t o r is a fluorescent screen p l a c e d
n e a r t h e s a m p l e a n d e q u i p p e d w i t h grids t o filter
inelastically scattered electrons a n d t h e n t o p o s t accelerate t h e electrons o n t o the screen w h e r e a dif
fraction p a t t e r n of s p o t s , characteristic of t h e surface,
is displayed (see F i g . 1). A l t e r n a t i v e a r r a n g e m e n t s use
F a r a d a y c u p s t o collect t h e e l e c t r o n s p e r h a p s the
m o s t precise m e t h o d of m e a s u r e m e n t . If very low
c u r r e n t s a r e used t o avoid surface d a m a g e , a c h a n n e l t r o n d e t e c t o r c a n be used in a c o u n t i n g m o d e .

Electron

Diffraction,

Low-Energy

w h e r e m is t h e electron m a s s , V is t h e scattering
p o t e n t i a l a n d is t h e e l e c t r o n energy. F o r a m o n o
c h r o m a t i c c o l l i m a t e d b e a m in v a c u o (V=0),
the
+
s o l u t i o n is a p l a n e w a v e of w a v e v e c t o r k described
b y t h e w a v e function
= exp(i

.r)

I n m o s t t h e o r e t i c a l w o r k u n i t s a r e used in which
h = m = e = 1, t h e u n i t of l e n g t h is the B o h r r a d i u s
a n d t h e u n i t of energy is t h e H a r t r e e (27.2 eV).
T h e s y m m e t r y of t h e surface d i c t a t e s t h a t m o m e n
t u m parallel t o t h e surface c a n o n l y b e c h a n g e d by
discrete a m o u n t s :
g = IA + mB
w h e r e / a n d m a r e integers. T h e v e c t o r s g define t h e
reciprocal lattice a n d t h e v e c t o r s A a n d a r e given by

Figure 1
(a) The diffraction of an incident beam into a series of
discrete beams, and (b) a plan view of a typical pattern
made on the fluorescent screen

A n o r d e r e d surface gives rise t o a diffraction p a t

tern h a v i n g t h e s y m m e t r y of t h e surface. D i s o r d e r of
v a r i o u s k i n d s r e m o v e s intensity f r o m t h e c o h e r e n t
b e a m s t o o t h e r r e g i o n s of t h e screen. Inelastically
scattered electrons, even t h o s e f r o m a n o r d e r e d sur
face, will give rise t o intensity b e t w e e n diffraction
p a t t e r n s p o t s if n o t filtered o u t . A diffraction
m e a s u r e m e n t a l w a y s includes a p h o t o g r a p h of t h e
diffraction p a t t e r n .
M o r e sophisticated experiments measure the
intensities of t h e diffracted b e a m s usually as a func
tion of incident energy. It is necessary t o specify n o t
only t h e p o l a r a n d a z i m u t h a l angles of incidence a n d
the energy, b u t also t h e p a r t i c u l a r diffracted b e a m
m e a s u r e d . I n a n o t h e r t y p e of e x p e r i m e n t t h e inelastic
s p e c t r u m c a n b e m e a s u r e d . Losses of a few e l e c t r o n
volts o r m o r e c o r r e s p o n d t o electronic e x c i t a t i o n s of
the solid a n d a r e t h e m o s t c o m m o n loss events. Losses
o n a finer scale, u p t o a few h u n d r e d millielectron
volts c a n b e c a u s e d b y v i b r a t i o n a l e x c i t a t i o n s . T h e
latter m e a s u r e m e n t s a r e p a r t i c u l a r l y helpful in a n a
lyzing v i b r a t i o n a l m o d e s of a d s o r b e d a t o m s a n d
molecules.

1. The Diffraction

Pattern

Electron wavefunctions obey the Schrodinger equa

tion

A = (Ax,Ay)

= 2n(byt

= (Bx,By)

= 2 ( - ay,ax)/(axby

- bx)/(axby

bxay)

bxay)

w h e r e t h e v e c t o r s a a n d b define t h e sides of t h e u n i t
m e s h of t h e surface in real s p a c e . T h e s e e q u a t i o n s c a n
readily be inverted t o find a a n d b:
a = (ax,ay)

= 2n(By9

b = (bx,by)

= 2TT(- Ay9 - Ax)/(AxBy

- Bx)/(AxBy

BxAy)
-

BxAy)

T h u s , t h e diffraction p a t t e r n fixes t h e size a n d s h a p e

of t h e surface u n i t m e s h .
C o m p l e x effects in t h e diffraction p a t t e r n c a n be
p r o d u c e d b y v a r i o u s s o r t s of d i s o r d e r . D i s o r d e r in the
s t r u c t u r e a l o n g t h e axis p r o d u c e s s t r e a k i n g of the
s p o t s in t h e d i r e c t i o n . S p o t splitting c a n be c a u s e d
b y t h e p r e s e n c e of small d o m a i n s (say less t h a n 10 n m )
of o r d e r e d overlayer. T h e s t a t e of t h e diffraction s p o t s
c a n in this w a y give clues t o t h e l o n g e r - r a n g e o r d e r i n g
in t h e surface.

2. Calculation

of Diffracted

Intensities
+

G i v e n a n incident w a v e e x p ( i * . r ) , t h e a m p l i t u d e s of
t h e reflected w a v e s a r e r e q u i r e d . T h e reflected w a v e s
h a v e w a v e functions of t h e f o r m
Rg Qxp(ik~
where

.r)

is t h e a m p l i t u d e a n d
= [ * , + gX*ky

+ gy> ~

|*|| + f | )

1 / 2

It is c u s t o m a r y t o m o d e l t h e surface a s c o m p r i s i n g a
step d o w n in p o t e n t i a l ( k n o w n as t h e surface b a r r i e r ) ,
a series of spherically s y m m e t r i c a l p o t e n t i a l s r e p r e
senting t h e a t o m s a n d a c o n s t a n t p o t e n t i a l V0 b e t w e e n
atoms. Neglecting backscattering by the barrier, the
+
incident w a v e is t r a n s m i t t e d i n t o t h e crystal ^~

109

Electron

Diffraction,

Low-Energy

exp(iAo . r ) , w h e r e
is t h e a m p l i t u d e a n d w h e r e t h e
w a v e vector Kq h a s c o m p o n e n t s given by
kx,ky,

l 2

(2E-2V0) l

T h e t r a n s m i t t e d w a v e e n c o u n t e r s successive layers of
a t o m s , e a c h layer scattering t h e electrons. If multiple
+
scattering is neglected, a b e a m (1^ .r) is incident
o n a layer located a t Rj a n d w a v e s a r e scattered
f o r w a r d s a n d b a c k w a r d s with w a v e functions

w h e r e t h e a m p l i t u d e s a r e given by
2

1 1

-8

gg

lm
I'm'

w h e r e tr = exp(i<5 r) sin(or), A is t h e a r e a of t h e t w o d i m e n s i o n a l u n i t m e s h , Sr is a n a t o m i c p h a s e shift a n d

t(Kp, K^) is t h e a t o m i c scattering factor. It h a s been
a s s u m e d for simplicity t h a t only o n e type of spheri
cally s y m m e t r i c a t o m occurs in t h e layer. T h e layer is
therefore s y m m e t r i c a l t o waves incident from o p
posite sides.
I n t h e a p p r o x i m a t i o n t h a t only single-scattering
events a r e included, t h e reflected a m p l i t u d e c a n b e
written as a s u m over individual layer scatterings. F o r
layers stacked with e q u a l spacing c, Rj = nc a n d t h e
total scattered w a v e in t h e single scattering a p p r o x i
{ ]
m a t i o n is R g cxp(iK~.r),
where
R = r ; < r + K'o~

exp[i(*0

p r o p e r t i e s of solids, a n d a brief outline is given here.

T w o sorts of multiple scattering a r e i m p o r t a n t .
W i t h i n t h e layer electrons w h i c h h a v e collided with
o n e a t o m usually g o o n t o collide with several m o r e .
This can be regarded as introducing more complex
s t r u c t u r e i n t o t h e basic a t o m i c scattering a n d c a n b e
c o r r e c t e d for b y t h e s u b s t i t u t i o n
mm'^ll'

^Iml'm'h'

w h e r e t h e m a t r i x X c o n t a i n s s u m s over t h e t w o d i m e n s i o n a l lattice scattering events.

F u r t h e r multiple scattering occurs b e t w e e n t h e
layers. V a r i o u s t r e a t m e n t s a r e available. P e r t u r b a t i v e
t r e a t m e n t s t a k e a c c o u n t of t h e s t r o n g f o r w a r d scatter
ing exactly; this c a n easily b e d o n e b y multiplying
+
a m p l i t u d e s b y (1 + M ) for t r a n s m i s s i o n t h r o u g h
each layer. B a c k s c a t t e r i n g is t h e n t r e a t e d p e r t u r b a t i vely. Alternatively, layers c a n b e a d d e d t o t h e calcula
tion o n e a t a time. First t h e reflectivity of a p a i r of
layers is calculated allowing for t h e b a c k a n d forth
reflection of electrons between t h e layers. T h e n a third
layer is a d d e d , t h e original p a i r being t r e a t e d as a
single entity, a n d so o n . C o n v e r g e n c e is achieved after
a b o u t four layers, a typical p e n e t r a t i o n d e p t h .
T e m p e r a t u r e affects t h e diffracted
intensities.
M a i n l y , t h e p e a k heights follow a D e b y e - W a l l e r type
of b e h a v i o r :

, D =
(

r - o ^ ( ^ M l )

w h e r e K' is t h e c h a n g e in m o m e n t u m o n scatter
ing, is t h e t e m p e r a t u r e in K , m is t h e a t o m i c m a s s in
units of t h e electron m a s s , KB is B o l t z m a n ' s c o n s t a n t
1
6
in H a r t r e e s K (3.169 x 10~ ) a n d is t h e D e b y e
t e m p e r a t u r e in K . U n f o r t u n a t e l y , multiple scattering
interferes severely with t h e simple t h e o r y of in t e r m s
of t h e r m a l v i b r a t i o n s a n d e a c h p e a k h a s its o w n
effective d e t e r m i n e d b y t h e multiple scattering c o n
ditions. O n l y a p a r t i a l t h e o r y is available.

-K~).nc]

,i = 0

= -

er^ M-

/[l - e x p i ( t f 0

- -

).c]

A n o t h e r n a m e for this single scattering f o r m u l a is

the k i n e m a t i c a p p r o x i m a t i o n . If were purely real,
R$ w o u l d b e infinitely large w h e n t h e layers scatter in
p h a s e ; t h a t is, w h e n
(*o

).c = 2nm

w h e r e m is a n integer. F o r t u n a t e l y , V0 in t h e expres
+
sion for K 0 is c o m p l e x a n d therefore Rg0 h a s only
m a x i m a b u t even s o , t h e k i n e m a t i c a p p r o x i m a t i o n h a s
severe deficiencies in practice. Scattering, especially
f o r w a r d scattering, is n o t w e a k a n d multiple scatter
ing m a k e s a large c o n t r i b u t i o n t o R^. T h e s o l u t i o n of
the multiple scattering p r o b l e m for low-energy elec
t r o n s is o n e of t h e m i n o r t r i u m p h s of t h e electronic

110

3. The Scattering

Potential

In discussing scattering, a m o d e l h a s been implicitly

a s s u m e d in w h i c h t h e surface p o t e n t i a l c o m p r i s e s a
s m o o t h step d o w n in p o t e n t i a l from V = 0 in t h e
v a c u u m t o a value V0 which is a p p r o x i m a t e l y c o n s t a n t
in t h e region b e t w e e n a t o m s . T h e a t o m s a r e a s s u m e d
t o b e spherically s y m m e t r i c a n d t o b e c o n t a i n e d with
n o n o v e r l a p p i n g spheres (often called "muffin t i n s " )
which usually h a v e t o b e c h o s e n t o h a v e m a x i m u m
r a d i u s (i.e., they j u s t t o u c h ) . T h i s a p p r o x i m a t i o n is
g o o d for close-packed m e t a l s b u t c a n be quite b a d in
c o v a l e n t systems c o m p r i s i n g several very different
atoms.
T h e c o n s t a n t p o t e n t i a l is usually d e t e r m i n e d e m p i r
ically a n d typically h a s a real p a r t V0r of between
10 eV a n d - 1 5 e V . T h e i m a g i n a r y p a r t V0i t a k e s

Electron

care of loss of flux d u e t o inelastic scattering a n d

typically h a s a value o f - 4 e V ( - 0 . 1 5 H a r t r e e s ) ,
t h o u g h for energies b e l o w 2 0 - 3 0 e V Voi c a n b e m u c h
smaller. It is
t h a t leads t o t h e d e c a y of w a v e s a s c a n
be seen b y solving t h e S c h r o d i n g e r e q u a t i o n :
2

(-

+ 0) =

T h e solution is a p l a n e w a v e with

kT^J(2E),

/l(atomic units) = -

Low-Energy

T o assist in t h e c o m p a r i s o n of t h e o r y a n d experi
m e n t v a r i o u s a u t o m a t e d criteria of a g r e e m e n t h a v e
b e e n devised (by Z a n a z z i a n d J o n a a n d b y P e n d r y t o
n a m e only t w o ) . T h e R factor m u s t stress t h e i m p o r t
a n c e of p e a k p o s i t i o n s , d e - e m p h a s i z e t h e difficult t o
r e p r o d u c e a b s o l u t e intensities a n d give s o m e n o r m a
lized i n d i c a t i o n of g o o d n e s s of fit. I n t h e latter scheme
referred t o , a function of 1(E) is defined:
l

y(E) =

k^-V0i/J(2E)

for which t h e w a v e intensity d e c a y s t o e " in a length

Diffraction,

L- /(L- +V 0i)

where

L(E) =

V ( 2 ) / ( 2 K 0 i)

r\dI/dE)

where a n d Voi a r e in H a r t r e e s . Typically = 10

a t o m i c units for a r o u n d 100 eV.
O n e further c o n s e q u e n c e of t h e finite lifetime of t h e
electron is t h a t n o p e a k s c a n b e m o r e n a r r o w t h a n t h e
limits dictated b y t h e u n c e r t a i n t y principle; t h a t is,

w h i c h eliminates t h e a b s o l u t e scale completely. T h e

reliability factor is t h e n defined t o b e

> 2 | 0 |

w h e r e t h e i n t e g r a t i o n is over all energy r a n g e s a n d t h e

s u m m a t i o n is over all b e a m s a n d angles. R is a u t o
matically n o r m a l i z e d t o u n i t y for u n c o r r e l a t e d d a t a .
T h e expected v a r i a n c e of R d e p e n d s o n t h e size of t h e
database a n d can be estimated to be

a n expression t h a t is useful in e s t i m a t i n g V^.

T h e a t o m i c p o t e n t i a l is c o n s t r u c t e d from over
l a p p i n g a t o m i c c h a r g e densities; t h e electrostatic p a r t
is o b t a i n e d b y solving P o i s s o n ' s e q u a t i o n a n d t h e
exchange a n d c o r r e l a t i o n p a r t b y m a k i n g use of o n e
of several local density a p p r o x i m a t i o n s . Typically a t
lOOeV these p o t e n t i a l s give rise t o p h a s e shifts u p t o
/ = 4 w h i c h differ significantly from z e r o .

4. Surface

Structure

Determination

L o w - e n e r g y electrons p r o b e t o j u s t t h e right d e p t h in
a solid t o d e t e r m i n e t h e c r y s t a l l o g r a p h y a s s o c i a t e d
with t h e surface region o n a n a t o m i c scale. L o w energy electron diffraction ( L E E D ) h a s p r o v e d t o b e
by far t h e m o s t effective t o o l a n d of t h e several
h u n d r e d o r so s t r u c t u r e s k n o w n a l m o s t all were
d e t e r m i n e d b y L E E D . T h e first step in surface struc
t u r e d e t e r m i n a t i o n is t o find t h e t w o - d i m e n s i o n a l u n i t
m e s h of t h e surface. T h i s c a n b e d o n e b y m e a s u r e
m e n t of t h e diffraction p a t t e r n . L o c a t i o n of a t o m s
within t h e cell affects t h e intensities of diffracted
b e a m s ; t h e u s u a l p r o c e d u r e is t o guess a trial s t r u c t u r e
a n d refine it until t h e o b s e r v e d intensity/energy spec
t r a c o r r e s p o n d t o t h e calculated o n e s . D i r e c t inver
sion p r o c e d u r e s a r e n o t available for L E E D .
Needless t o say, a g r e e m e n t with e x p e r i m e n t is never
perfect. L o c a t i o n s of p e a k s a n d their relative inten
sities c a n b e r e p r o d u c e d q u i t e well, b u t a b s o l u t e
intensities a r e r a t h e r sensitive t o a n u m b e r o f
difficult-to-determine p a r a m e t e r s a n d fare less well.
F o r reliable structure d e t e r m i n a t i o n s a large d a t a b a s e
is needed. F o u r b e a m s m e a s u r e d at four different
angles of incidence in t h e r a n g e 2 0 - 1 5 0 eV a r e r e g a r d e d
as a g o o d d a t a set for a simple surface structure.
Naturally the m o r e i n f o r m a t i o n there is t o b e extracted
from the curves t h e larger t h e base m u s t be.

_my -y Y dE

ih

em

w h e r e SE is t h e t o t a l r a n g e of d a t a s u m m e d over t h e
s e p a r a t e r a n g e s for e a c h b e a m a n d e a c h angle. W h e n
R differs for u n i t y by m o r e t h a n RR t h e deviation is
significant. Typically RR m i g h t b e 0.2. T y p i c a l mini
m u m values of R a r e 0.2 for a very g o o d s t r u c t u r e , 0.3
for a g o o d o n e a n d 0.4 for a n only satisfactory
d e t e r m i n a t i o n . T h e p r o b l e m is t o scan t h r o u g h t h e
p a r a m e t e r s m i n i m i z i n g R b u t checking for false
m i n i m a a n d for c o r r e l a t e d variables w h i c h result in
r e d u c e d a c c u r a c y for t h o s e p a r a m e t e r s .

5. Other Applications

of LEED

Theory

T h e r e a r e m a n y e x p e r i m e n t s in w h i c h t h e basic L E E D
state o c c u r s c o u p l e d t o s o m e o t h e r process in t h e
surface. T h e m o s t c o m m o n e x a m p l e is in a p h o t o emission e x p e r i m e n t in w h i c h t h e e m i t t e d electron is
t r a n s m i t t e d o u t of t h e surface b y a time-reversed
L E E D s t a t e t h e so-called "final s t a t e " of p h o t o emission t h e o r y . Diffraction in t h e final state c a n lead
t o s u b s t a n t i a l r e d i s t r i b u t i o n of flux b e t w e e n different
angles of emission, a n d a n y q u a n t i t a t i v e t h e o r y of
p h o t o e m i s s i o n m u s t include a p r o p e r L E E D calcula
tion. O t h e r emission processes such a s A u g e r a n d
x-ray excited p h o t o e m i s s i o n also c o u p l e t o L E E D
states. E l e c t r o n energy loss s p e c t r o s c o p y , in which t h e
reflected b e a m is energy a n a l y z e d for its inelastic
s p e c t r u m , involves t w o L E E D states: t h e incident
b e a m a n d t h e e m i t t e d b e a m w h i c h is a time-reversed
L E E D state.

Ill

Electron

Diffraction,

Low-Energy

T h e e x t e n d e d x-ray a b s o r p t i o n fine s t r u c t u r e h a s
sometimes been called " i n t e r n a l L E E D " because the
electron kicked o u t of t h e shell of o n e a t o m is
s u b s e q u e n t l y reflected b a c k t o s o m e degree by the
s u r r o u n d i n g a t o m s . T h i s reflection coefficient m o d u
lates the a b s o r p t i o n coefficient as t h e e m i t t e d electron
energy varies with the incident x-ray energy, j u s t as
the electron c u r r e n t t o a crystal in a L E E D experi
m e n t is m o d u l a t e d by t h e reflection coefficient.
See also: Auger Electron Spectroscopy; Electron Diffrac
tion; X-Ray Absorption Spectroscopy: EXAFS and
XANES Techniques

Transmitted
electrons

Raised T E M
viewing screen
Ramping coil

Magnetic prism" \
spectrometer

//*<^J

To scintillator
" p h o t o m u l t i p l i e r system

No - loss electron'
paths (energy E)
Selecting slit in
back - focal plane
(dispersion plane)

Energy - loss electron

paths (energy
E-AE)

Bibliography
Dobson J, Pendry J B, Humphreys C J (eds.) 1978
Electron Diffraction 1927-77. Institute of Physics, Bristol,
UK
Feuerbacher B, Fitton B, Willis R F 1978 Photoemission and
the Electronic Properties of Surfaces. Wiley, Chichester,
UK
Heinz K, Miiller 1982 Structural Studies of Surfaces,
Springer Tracts in Modern Physics, Vol. 91. Springer,
Berlin
McRae G 1979 Electronic surface resonances of crystals.
Rev. Mod. Phys. 51: 541-68
Pendry J 1974 Low Energy Electron Diffraction. Academic
Press, London
van Hove A, Tong S Y 1979 Surface Crystallography by
LEED. Springer, Berlin
Webb , Lagally G 1973 Elastic scattering of low
energy electrons from surfaces. Solid State Phys. 28: 301405
J. B. P e n d r y
[Imperial College of Science, T e c h n o l o g y
and Medicine, London, U K ]

Electron Energy-Loss Spectrometry

Electron energy-loss s p e c t r o m e t r y ( E E L S ) is t h e
m e a s u r e m e n t of t h e energy d i s t r i b u t i o n of fast elec
t r o n s t h a t h a v e interacted with a m a t e r i a l . A p r i m a r y
r e a s o n for t h e interest in E E L S in m a t e r i a l s science is
t h a t it c a n be used as a m i c r o a n a l y t i c a l t e c h n i q u e .
W h e n so used it is c o m p l e m e n t a r y t o x-ray analysis
b e c a u s e it is m o r e sensitive t o t h e lighter e l e m e n t s
( Z < 10). X rays from these elements a r e of low
energy a n d so a r e strongly a b s o r b e d . A l s o , their low
fluorescence yield m a k e s x-ray s p e c t r o m e t r y very in
efficient. I n a d d i t i o n t o t h e basic elemental i n f o r m a
tion p r e s e n t in t h e energy-loss s p e c t r u m , there a r e
detailed d a t a c o n c e r n i n g t h e electronic p r o p e r t i e s , t h e
a t o m i c b o n d i n g a n d t h e e n v i r o n m e n t of p a r t i c u l a r
a t o m i c species in the specimen. L o w - e n e r g y E E L S
( < 50 eV) is used t o give surface chemistry a n d b o n d
ing i n f o r m a t i o n , b u t this article considers only E E L S
p e r f o r m e d with high-energy ( > ~ 100 keV) electrons
t r a n s m i t t e d t h r o u g h a thin foil s a m p l e . T h e energyloss s p e c t r u m (with a n energy r e s o l u t i o n of ~ 1 eV) is

112

Spectrometer
collection
semiangle -

Figure 1
Schematic diagram of a magnetic prism spectrometer

characteristic of t h e elemental, m o l e c u l a r a n d electro

nic s t r u c t u r e of t h e interior of t h e s a m p l e . H i g h energy E E L S is a l m o s t invariably carried o u t in a
t r a n s m i s s i o n ( T E M ) o r analytical ( A E M ) electron
m i c r o s c o p e b e c a u s e t h e i m a g e - f o r m i n g capabilities of
these i n s t r u m e n t s p e r m i t t h e spectra t o be related t o
features in t h e m i c r o s t r u c t u r e . A t t h e s a m e time,
electron diffraction, x-ray analysis a n d o t h e r T E M /
A E M d a t a a r e available from t h e s a m e region selected
for E E L S .

Instrumentation

E E L S is usually p e r f o r m e d using a m a g n e t i c - p r i s m
s p e c t r o m e t e r placed below t h e T E M viewing screen.
A s s h o w n in F i g . 1, t h e s p e c t r o m e t e r e n t r a n c e a p e r
t u r e selects electrons t r a n s m i t t e d t h r o u g h a specific
region of t h e specimen w i t h a collection semiangle
w h i c h is usually < 100 m r a d . D e s p i t e this small collec
tion angle, a l m o s t all t h e energy-loss electrons a r e
g a t h e r e d b y t h e s p e c t r o m e t e r , b e c a u s e they a r e
strongly f o r w a r d scattered. T h e electrons a r e separ
a t e d b y t h e m a g n e t i c field of t h e s p e c t r o m e t e r a n d
focused i n t o a dispersion p l a n e w h e r e their p o s i t i o n is
a function of their energy loss (). T h i s s p e c t r u m is
displayed b y r a m p i n g t h e electron dispersion a c r o s s
a n e n t r a n c e slit t o a s c i n t i l l a t o r - p h o t o m u l t i p l i e r sys
tem coupled to a computer-controlled multichannel
analyzer ( M C A ) .

2. The Energy-Loss

Spectrum

T h e s p e c t r u m in Fig. 2 is a p l o t of intensity I a g a i n s t
energy loss AE for 1 2 0 k e V electrons t r a n s m i t t e d
t h r o u g h a thin foil of p u r e lithium (which is a n
element t h a t is n o t d e t e c t a b l e b y x-ray s p e c t r o m e t r y in
the electron m i c r o s c o p e ) . T h e m a j o r p e a k 7 0 c o n t a i n s
t h o s e electrons t r a n s m i t t e d t h r o u g h t h e s a m p l e with
n o m e a s u r a b l e loss of energy c o m p r i s i n g :

Electron

48000

40000

L i ionization edge

32000

J p( l )
24000

16000

8000

7(

)2

16

J\
0

1
20

40

60

80

100

Energy loss (eV)

Figure 2
Energy-loss spectrum from a thin foil of pure lithium. The
Li ionization edge at 55 eV is magnified 16 (courtesy
of D-R. Liu)

(a)

t h o s e electrons t h a t d i d n o t i n t e r a c t with t h e
s a m p l e a t all,

(b)

t h o s e elastically scattered in t h e f o r w a r d direc

tion, a n d

(c)

t h o s e suffering losses less t h a n t h e r e s o l u t i o n of

t h e s p e c t r o m e t e r ( < ~ 1 eV).

In m a t e r i a l s a p p r o x i m a t i n g t o free-electron solids, t h e
low-loss s p e c t r u m s h o w s o n e o r m o r e G a u s s i a n
p e a k s , c o r r e s p o n d i n g t o q u a n t i z e d oscillations of t h e
free-electron g a s , t e r m e d " p l a s m o n s . " T w o s u c h
p e a k s , (Ip (1) a n d / p (2)), a r e visible in F i g . 2. I n n o n free-electron m a t e r i a l s , t h e low-loss region o f t h e
s p e c t r u m usually c o n t a i n s a single, b r o a d , p l a s m o n type p e a k a t a r o u n d 2 0 - 2 5 eV modified s u b s t a n t i a l l y
by t h e presence of single-electron (inter a n d i n t r a b a n d ) t r a n s i t i o n s . It is possible t o infer c o m p o s i t i o n a l
i n f o r m a t i o n from p l a s m o n p e a k shifts, b u t this tech
n i q u e is limited t o free-electron m e t a l s such a s a l u m i
n u m a n d m a g n e s i u m a n d their alloys. T h e specimen
thickness c a n also b e d e t e r m i n e d if t h e p l a s m o n m e a n
free p a t h is k n o w n . It is also possible t o e x t r a c t t h e
real a n d i m a g i n a r y p a r t s of t h e dielectric c o n s t a n t of
the s a m p l e b y p e r f o r m i n g a K r a m e r s - K r o n i g analysis
o n t h e low-loss s p e c t r u m . W h i l e this a p p r o a c h h a s
lower energy r e s o l u t i o n t h a n o t h e r t e c h n i q u e s for
dielectric c o n s t a n t m e a s u r e m e n t it h a s t h e a d v a n t a g e s
of high spatial r e s o l u t i o n (see Sect. 3) a n d a relatively
1 2
1 4
b r o a d frequency r a n g e from a r o u n d 1 0 - 1 0 H z .
I n t h e high-loss region of t h e s p e c t r u m b e y o n d a n y
p l a s m o n p e a k s , t h e intensity falls off r a p i d l y w i t h

Energy-Loss

Spectrometry

increasing energy loss, o w i n g t o t h e decreasing value

of t h e v a r i o u s inelastic cross sections. T h e intensity in
this region of t h e s p e c t r u m arises from multiplescattering processes, a n d c o n s t i t u t e s a " b a c k g r o u n d "
a b o v e which i o n i z a t i o n edges, arising from inner-shell
i n t e r a c t i o n s , m a y b e visible. T h e i o n i z a t i o n edges
a p p e a r a t values of AE characteristic of specific
i o n i z a t i o n s a n d therefore their presence c a n be used
for q u a l i t a t i v e m i c r o a n a l y s i s . F o r e x a m p l e , in Fig. 2,
the Li edge s t a r t s a t a b o u t 55 eV, rises rapidly to a
m a x i m u m , t h e n d r o p s off in intensity. Quantification
c a n be achieved b y s u b t r a c t i n g t h e b a c k g r o u n d inten
sity below t h e edge a n d r a t i o i n g t h e i n t e g r a t e d inten
sity in t h e edge t o t h a t in a n o t h e r edge (for relative
quantification) o r t o t h e zero-loss intensity (for a b s o
lute quantification). T h e c a l c u l a t i o n h a s t o be m o d i
fied by i n c o r p o r a t i n g values of t h e i o n i z a t i o n cross
section for t h e c o n d i t i o n s of t h e e x p e r i m e n t (specifi
cally, t a k i n g i n t o a c c o u n t t h e s p e c t r o m e t e r collection
semiangle ( in F i g . 1) a n d t h e n u m b e r of c h a n n e l s in
t h e M C A over w h i c h t h e i n t e r g r a t i o n w a s p e r f o r m e d ) .
Since i o n i z a t i o n cross sections a r e n o t well k n o w n for
m a n y m a t e r i a l s a t T E M o p e r a t i n g voltages, this is a
m a j o r s o u r c e of e r r o r , limiting quantification t o
around 15-20%.

3. Spatial

Resolution

and Detectability

Limit

In E E L S , signal localization is limited b y t h e scale of

t h e energy-loss i n t e r a c t i o n . I n t h e case of b o t h ioniza
t i o n a n d p l a s m o n - l o s s processes, this i s < 1 0 n m ,
w h i c h r e p r e s e n t s a m i n i m u m spatial r e s o l u t i o n for t h e
t e c h n i q u e . I n principle, E E L S is m o r e sensitive t h a n
x-ray analysis a n d d e t e c t i o n o f a few a t o m s is t h e
calculated limit. I n p r a c t i c e , t h e high b a c k g r o u n d
intensity, o v e r l a p of i o n i z a t i o n edges a n d b e a m
d a m a g e restrict r o u t i n e detectability limits t o a b o u t
0.1-1.0 w t % .

4.

Deconvolution

I n f o r m a t i o n in t h e s p e c t r u m c a n b e e x t r a c t e d with
m o r e c e r t a i n t y if m u l t i p l e - s c a t t e r i n g effects a r e
r e m o v e d . T h i s c a n b e c a r r i e d o u t using a variety of
d e c o n v o l u t i o n t e c h n i q u e s such a s F o u r i e r - r a t i o ,
F o u r i e r - l o g a n d digital filtering. F i g u r e 3 s h o w s spec
t r a from p u r e a l u m i n u m in b o t h t h e a s - r e c o r d e d state
a n d after F o u r i e r - l o g d e c o n v o l u t i o n . T h e d e c o n v o
l v e d s p e c t r u m s h o w s t h e first p l a s m o n p e a k b u t t h e
s e c o n d (multiple scattering) p l a s m o n p e a k (/ p(2)) h a s
been r e m o v e d (except for a m i n o r d o u b l e - p l a s m o n
p e a k ) leaving t h e t r u e " s i n g l e - s c a t t e r i n g " s p e c t r u m .
In a d d i t i o n , it c a n be seen t h a t t h e s h a p e of t h e
i o n i z a t i o n edge c h a n g e s significantly after d e c o n v o l u
tion. T h e r e f o r e , it is essential t o r e m o v e multiplescattering effects before a t t e m p t i n g t o interpret t h e
fine s t r u c t u r e (see Sect. 5) associated with t h e edge.

113

Electron

Energy-Loss

Spectrometry

using x-rays. H o w e v e r , t h e i m p r o v e d spatial resolu

tion is g a i n e d a t t h e expense of decreased signal
intensity.
Al L

23

ionization edge

6.
deconvolved

f as recorded

40

80

120

160

Energy loss (eV)

Figure 3
Energy-loss spectrum from pure aluminum shown as
recorded and after deconvolution. The Al L 2 3 ionization
edge at 73 eV is magnified 16 in both spectra (courtesy
of D-R. Liu)

D e c o n v o l u t i o n is i m p o r t a n t b o t h for t h e best q u a n t i
fication a n d for t h e K r a m e r s - K r o n i g analysis a l r e a d y
discussed. Alternatively, very t h i n ( < ~ 20 n m ) speci
m e n s w h i c h m i n i m i z e multiple scattering m a y b e used,
a l t h o u g h surface effects (such as surface p l a s m o n s
a n d oxide films) m a y modify t h e spectra.

5. Fine-Structure

7. Limitations

and Future

Development

M a j o r l i m i t a t i o n s t o E E L S arise b e c a u s e of t h e u s u a l
(serial) m e t h o d of d a t a collection. T h i s m e a n s t h a t
spectral acquisition m a y t a k e several m i n u t e s t o
satisfy statistical r e q u i r e m e n t s for analysis. D u r i n g

Effects

I n t h e low-loss region, d e c o n v o l u t i o n c a n be used t o

reveal details d u e t o single-electron i n t e r a c t i o n s . F i n e
s t r u c t u r e in t h e high-energy-loss region is confined t o
the vicinity of i o n i z a t i o n edges. W i t h i n a b o u t 50 eV of
t h e edge, energy-loss n e a r - e d g e s t r u c t u r e ( E L N E S ) is
often p r e s e n t w h i c h c a n , in principle, be used t o
d e t e r m i n e local a t o m i c c o o r d i n a t i o n a n d b o n d i n g
effects. T h i s t y p e of fine s t r u c t u r e is visible in t h e A l
L 2 3 edge s h o w n in F i g . 3. C h a r a c t e r i s t i c differences in
E L N E S occur, for e x a m p l e , b e t w e e n m e t a l s ( M ) a n d
oxides (MxOy) a n d b e t w e e n different forms of o n e
element such as g r a p h i t e a n d d i a m o n d . E x t e n d e d energy-loss fine s t r u c t u r e ( E X E L F S ) a p p e a r s as small
( ~ 2 % ) intensity m o d u l a t i o n s e x t e n d i n g several
h u n d r e d electron volts after t h e i o n i z a t i o n edge. T h i s
p h e n o m e n o n is a n a l o g o u s t o t h e x-ray a b s o r p t i o n fine
s t r u c t u r e ( E X A F S ) often s o u g h t in s y n c h r o t r o n x-ray
e x p e r i m e n t s . E X E L F S , like E X A F S , gives s h o r t r a n g e - o r d e r i n f o r m a t i o n , i n t e r a t o m i c distances a n d ,
p e r h a p s , directional b o n d i n g effects, b u t E X E L F S
has the advantage that the information can be
o b t a i n e d from m u c h smaller v o l u m e s t h a n is possible

114

Imaging

It is possible t o use t h e electrons c o n t r i b u t i n g

t o a selected region of t h e s p e c t r u m t o m o d u l a t e a
c a t h o d e - r a y t u b e , t h u s p r o d u c i n g a s c a n n i n g i m a g e in
w h i c h intensity v a r i a t i o n s c o r r e s p o n d , for e x a m p l e , t o
t h e presence of a t o m s c o n t r i b u t i n g t o t h e selected
i o n i z a t i o n edge. If t h e original spectral intensity is
c o r r e c t e d for b a c k g r o u n d c o n t r i b u t i o n s , t h e n direct,
q u a n t i t a t i v e e l e m e n t a l m a p p i n g b e c o m e s feasible a n d
a n e x a m p l e is s h o w n in Fig. 4. O t h e r features of t h e
s p e c t r u m c a n be selected giving p l a s m o n i m a g e s , p u r e
elastic i m a g e s ( n o c h r o m a t i c a b e r r a t i o n effects) a n d
a t o m i c n u m b e r ( Z ) c o n t r a s t i m a g e s (elastic-inelastic
r a t i o ) . E a c h of these i m a g e s gives detailed i n f o r m a
tion a b o u t t h e specimen n o t e v i d e n t in c o n v e n t i o n a l
T E M o r S T E M i m a g e s of t h i n foils.

Figure 4
Images of an Al/SiC composite: (a) STEM bright field;
(b) chemical image from Al edge; (c) chemical image
from Si edge (after Leapman et al. 1984.
Ultramicroscopy. North-Holland, Amsterdam.
Reproduced with permission)

Electron

Microprobe

Analysis

Electron Microprobe Analysis

180

200
220
Energy loss (eV)

Figure 5
Portion of energy-loss spectrum showing the boron
edge; the spectrum was acquired in 0.1 s using parallel
collection (courtesy of O. Krivanek)

this time, b e a m d a m a g e o r specimen drift m a y occur,

limiting t h e a c c u r a c y of m i c r o a n a l y s i s . Parallel
r e c o r d i n g t e c h n i q u e s using d i o d e a r r a y s h a v e n o w
b e c o m e available c o m m e r c i a l l y , a n d c a n o v e r c o m e
these limitations. F i g u r e 5 s h o w s a s p e c t r u m o b t a i n e d
from b o r o n nitride b y parallel collection in ~ 0 . 1 s
which c o m p a r e s with a p p r o x i m a t e l y five m i n u t e s
required to g a t h e r t h e spectra in Figs. 2, 3. U n d e r
these c i r c u m s t a n c e s , E E L S is far m o r e efficient t h a n xr a y m i c r o a n a l y s i s . Nevertheless, t o m a k e analysis of
E E L S spectra as simple a n d a c c u r a t e as x-ray a n a l y
sis, d e c o n v o l u t i o n t e c h n i q u e s m u s t b e i n c o r p o r a t e d
i n t o c o m m e r c i a l software. I n a d d i t i o n , o u r u n d e r
s t a n d i n g of multiple scattering m u s t i m p r o v e t o m a k e
the b a c k g r o u n d s u b t r a c t i o n p r o c e s s less empirical,
a n d m o r e a c c u r a t e k n o w l e d g e of t h e values of ioniza
tion cross sections a t T E M voltages is r e q u i r e d .
See also: Electron Diffraction; Electron Diffraction, LowEnergy; Electron Microscopy, Analytical; Electron Micros
copy, High-Voltage; X-Ray Microanalysis, Quantitative

T h e electron m i c r o p r o b e analyzer ( E M A ) w a s d e
veloped in t h e early 1950s by C a s t a i n g a t t h e U n i v e r
sity of Paris. T h e i n s t r u m e n t uses a focused b e a m of
electrons t o locally excite rays from a region as small
as a few m i c r o m e t e r s o r less o n a specimen. T h e
w a v e l e n g t h d i s t r i b u t i o n of the e m i t t e d rays is
m e a s u r e d by m e a n s of o n e o r m o r e crystal-diffraction
s p e c t r o m e t e r s . E l e m e n t a l c o n s t i t u e n t s c a n t h e n be
identified with the aid of M o s e l e y ' s law which
u n i q u e l y relates t h e w a v e l e n g t h of each observed
spectral line t o a specific element t h r o u g h the
relationship
\lk =

k(Z-a)

0)

w h e r e is t h e x-ray w a v e l e n g t h , A: is a c o n s t a n t for
e a c h spectral-line series, is t h e a t o m i c n u m b e r of the
element from which t h e rays o r i g i n a t e a n d is a
c o n s t a n t associated with the a t o m i c screening effects.
I n a d d i t i o n t o qualitative analysis, q u a n t i t a t i v e analy
sis is also possible. T h i s is d o n e by c o n v e r t i n g
m e a s u r e d x-ray line intensities, n o r m a l i z e d by p u r e
e l e m e n t a l - s t a n d a r d intensities, t o c o m p o s i t i o n s using
a variety of r e a s o n a b l y well-developed f u n d a m e n t a l
p a r a m e t e r q u a n t i t a t i o n schemes. S a m p l e s for E M A
analysis a r e n o r m a l l y well-polished m e t a l l o g r a p h i c
sections. T h e regions t o be a n a l y z e d a r e selected by
m e a n s of a light m i c r o s c o p e m o u n t e d coaxially with
the electron optical system. In a d d i t i o n , a l m o s t all
E M A s h a v e s e c o n d a r y - e l e c t r o n d e t e c t o r s , electrondeflection systems a n d c a t h o d e - r a y - t u b e ( C R T ) dis
plays which allow t h e m t o be o p e r a t e d as s c a n n i n g
electron m i c r o s c o p e s ( S E M s ) (see Scanning
Electron
Microscopy).
T h i s feature is n o t only useful in identi
fying regions t o be a n a l y z e d b u t also m a k e s it possible
t o o b t a i n e l e m e n t a l - d i s t r i b u t i o n i n f o r m a t i o n in either
o n e d i m e n s i o n (line scans) o r in t w o d i m e n s i o n s (xray distribution maps).

Bibliography
Colliex C 1985 An illustrated review of the various factors
governing the high spatial resolution capabilities in EELS
microanalysis. Ultramicroscopy 18: 131-50
Egerton R F 1986 Electron Energy-Loss Spectroscopy in the
Electron Microscope. Plenum, New York
Isaacson 1987 Microcharacterization. Plenum, New York
Joy D C, Romig A D Jr, Goldstein J I (eds.) 1986 Principles
of Analytical Electron Microscopy. Plenum, New York
Leapman R D 1984 Electron energy loss microspectroscopy
and the characterization of solids. In: Kyser D F, Niedrig
H, Newbury D E, Shimizu R (eds.) 1984 Electron Beam
Interactions with Solids for Microscopy, Microanalysis and
Microlithography: Proc. 1st Pfefferkorn Conf Scanning
Electron Microscopy Inc., O'Hare, IL, pp. 217-33
Williams D 1984 Practical Analytical Electron Microscopy
in Materials Science. VCH, Deerfield Beach, FL
D . B. W i l l i a m s
[Lehigh University, B e t h l e h e m ,
Pennsylvania, USA]

1. General

Operating

Principles

F i g u r e 1 schematically illustrates t h e basic o p e r a t i o n

of t h e E M A . T h e h e a t e d t u n g s t e n filament of a n
electron g u n serves as a s o u r c e of electrons. T h e y are
given a n energy of typically 5 - 3 0 k e V b y a p p l y i n g a
p o t e n t i a l difference b e t w e e n t h e filament ( c a t h o d e )
a n d t h e a n o d e w h i c h is g r o u n d e d . T h e grid c a p of the
electron g u n is c o n n e c t e d t o t h e filament by m e a n s of
a v a r i a b l e - b i a s resistor. By m a k i n g it m o r e negative
t h a n t h e filament, t h e electron g u n acts as a lens,
f o r m i n g a n i m a g e of t h e filament w h i c h is t h e n
demagnified b y t w o o r m o r e m a g n e t i c lenses t o f o r m
t h e final p r o b e . F o r E M A a p p l i c a t i o n s , t h e p r o b e size
is in t h e r a n g e of 0 . 1 - 1 . 0 with c o r r e s p o n d i n g
p r o b e c u r r e n t s in t h e r a n g e of a b o u t 10-1000 n A .
A l t h o u g h finer p r o b e s a r e possible with t h e electron
optical systems o f m o s t c o m m e r c i a l l y available

115

Electron

Microprobe

Scanning coils

Analysis

^ \

Specimen

Figure 1
Electron microprobe analyzer

E M A s , their use is p r i m a r i l y limited t o i m a g e f o r m a

tion in a n S E M m o d e r a t h e r t h a n for x-ray analysis
using crystal-diffraction s p e c t r o m e t e r s . T h e r e a s o n is
the need t o o b t a i n statistically significant x-ray d a t a in
a r e a s o n a b l e time. T h i s is n o t possible with smaller
p r o b e sizes because t h e x-ray signal is directly p r o p o r
tional t o the p r o b e c u r r e n t which d r o p s off d r a m a t i
cally with t h e p r o b e size (as t h e eight-thirds p o w e r of
the p r o b e d i a m e t e r ) . F u r t h e r m o r e , in t h e e x a m i n a t i o n
of polished b u l k specimens t h e resolution is deter
m i n e d b y e l e c t r o n - b e a m p e n e t r a t i o n a n d scattering in
the s a m p l e , which for the voltages used is rarely less
t h a n 1 even if t h e b e a m d i a m e t e r is 1000 n m o r
less.
W h e n the electron b e a m strikes t h e s a m p l e the vast
majority of t h e energy is dissipated t h e r m a l l y . In fact,
only a b o u t o n e incident electron in ten t h o u s a n d will
eject a core-shell electron from a n a t o m it e n c o u n t e r s .
T h e resulting v a c a n c y is rapidly filled by t h e relaxa
tion of a n outer-shell electron, a t w h i c h time a n
a m o u n t of energy e q u a l t o the difference in t h e energy
levels is released either in t h e f o r m of characteristic xr a y emission o r t h e ejection of a n A u g e r electron (see
Auger Electron Spectroscopy).
T h e t r a n s i t i o n s of p r i n
cipal interest in x-ray s p e c t r o s c o p y involve the inner
m o s t a t o m i c levels o r c o r e shells. Since these levels d o
n o t shift with chemical b o n d i n g , t h e i n f o r m a t i o n
o b t a i n e d from spectral analysis is a t o m i c r a t h e r t h a n
molecular. A l s o , since there a r e fewer subshells in t h e
inner levels, t h e c o r r e s p o n d i n g x-ray spectra t e n d t o
be c o n s i d e r a b l y simpler t h a n optical emission spectra
which involve t r a n s i t i o n s in t h e o u t e r levels. E l e m e n t s
c a n , therefore, often be identified o n t h e basis of only
o n e o r t w o lines. F i g u r e 2 s h o w s a simplified energylevel d i a g r a m illustrating s o m e of t h e m a j o r spectral
t r a n s i t i o n s . F o r e x a m p l e , a t r a n s i t i o n from t h e L shell
to the shell c o r r e s p o n d s to t h e emission of a Koc
p h o t o n w h e r e a s a t r a n s i t i o n from t h e shell t o t h e
shell results in t h e emission of a p h o t o n . I n
a d d i t i o n t o t h e characteristic lines, t h e deceleration of
the electrons striking t h e s a m p l e also give rise t o a

116

c o n t i n u o u s s p e c t r u m o r " c o n t i n u u m " w h i c h is t h e
principal s o u r c e of b a c k g r o u n d r a d i a t i o n .
I n t h e E M A , x-ray spectral m e a s u r e m e n t s a r e
principally p e r f o r m e d using crystal-diffraction spec
t r o m e t e r s ( C D S s ) . Energy-dispersive s p e c t r o m e t e r s
(widely used in s c a n n i n g electron m i c r o s c o p y ) a r e also
used (see Sect. 2). T h e basic c o m p o n e n t s of t h e C D S
as s h o w n in F i g . 1 include a n a n a l y z i n g crystal, a
d e t e c t o r a n d r e a d o u t electronics. T h e region of x-ray
excitation is essentially a p o i n t source with rays
travelling o u t in all directions. A small fraction of
these rays exit t h e electron optical c o l u m n a n d e n t e r
t h e s p e c t r o m e t e r w h e r e they i m p i n g e o n t h e a n a l y z i n g
crystal. T h i s is a thin r e c t a n g u l a r wafer w h i c h is c u t
such t h a t crystal p l a n e s of a preselected i n t e r p l a n a r
spacing a r e parallel t o its surface. A s t h e incident
angle is varied, a m a x i m u m in x-ray intensity o c c u r s
a t t h e d e t e c t o r w h e n B r a g g ' s law
= 2d sin

(2)

is o b e y e d . H e r e is a n integer (1 for first o r d e r , a n d so

o n ) a n d d is t h e i n t e r p l a n a r spacing of t h e analyzing
crystal. A c o n s t a n t value of a c r o s s t h e crystal is
r e q u i r e d for o b t a i n i n g m a x i m u m x-ray collection ef
ficiency w i t h o u t a serious loss of resolution. It is
a c c o m p l i s h e d b y designing t h e s p e c t r o m e t e r such t h a t
t h e x-ray s o u r c e , t h e crystal a n d t h e d e t e c t o r all lie o n
a circle. T h e a n a l y z i n g crystal is also b e n t such t h a t its
r a d i u s of c u r v a t u r e is fixed a t twice t h e r a d i u s of this
focusing circle. I n a d d i t i o n , in o r d e r t o m a i n t a i n a
c o n s t a n t x-ray e m e r g e n t angle relative t o t h e s a m p l e
surface as t h e a n a l y z i n g crystal is r o t a t e d , it is m o v e d
linearly o u t w a r d from t h e s a m p l e while a m e c h a n i c a l
a r m keeps t h e d e t e c t o r o n the focusing circle. T h e use

electron
removed

Ka

emission

- L electron
removed
La

Ma

M electron
removed
- electron
removed

Normal -

-^Valence
electron
removed

Figure 2
Simplified energy-level diagram illustrating some of the
major spectral transitions

Electron

" / /

Thin
window

Preamplifier

High
voltage (+ )

X rays

Figure 3
Flow proportional counter

of this l i n e a r - s p e c t r o m e t e r design m a k e s it possible t o

express B r a g g ' s law as
=

dL/R

(3)

w h e r e R is t h e r a d i u s of c u r v a t u r e of t h e s p e c t r o m e t e r
a n d L is t h e d i s t a n c e from t h e specimen t o t h e
analyzing crystal. I n practice, s p e c t r o m e t e r s a r e
usually e q u i p p e d with multiple crystal h o l d e r s
because a series of i n t e r p l a n a r spacings a r e r e q u i r e d
to cover t h e w a v e l e n g t h r a n g e of interest. E x a m i n a
tion of E q n . (2) s h o w s t h a t since sin c a n never b e
greater t h a n o n e , t h e n for first-order reflections t h e
wavelengths m e a s u r e d c a n never exceed twice t h e
i n t e r p l a n a r spacing of t h e crystal. T h u s , a L i F crystal
with a 2d spacing of 0.4028 n m is n o t suitable for
m e a s u r i n g a l u m i n u m Ka, w i t h a w a v e l e n g t h of
0.8339 n m , b u t is well suited t o m e a s u r i n g c o p p e r KOL
at 0.1541 n m . A n a p p r o p r i a t e crystal for a l u m i n u m is
p e n t a e r y t h r i t o l ( P E T ) w i t h a 2d s p a c i n g of 0.8472 n m .
T h e m i n i m u m w a v e l e n g t h m e a s u r a b l e with a crystal
c a n be o b t a i n e d from E q n . (3) since there is a m i n i
m u m value of L d e t e r m i n e d b y physical c o n s t r a i n t s
o n the s p e c t r o m e t e r .
T h e x-ray d e t e c t o r m o s t c o m m o n l y used o n t h e
C D S is a p r o p o r t i o n a l c o u n t e r of t h e t y p e illustrated
in Fig. 3. It consists of a g r o u n d e d m e t a l cylinder with
a n electrically isolated thin m e t a l wire r u n n i n g u p t h e
center. T h e wire is c o n n e c t e d t o a h i g h - v o l t a g e p o w e r
supply ( 1 - 3 k V ) t h r o u g h a large c u r r e n t - l i m i t i n g resis
tor. It is also ac c o u p l e d t o a preamplifier m o u n t e d
close b y t o r e d u c e electrical-noise p i c k u p . T h e detec
t o r is filled with a m i x t u r e of a n inert gas a n d a small
p e r c e n t a g e of m e t h a n e . X rays from t h e a n a l y z i n g
crystal enter t h r o u g h a t h i n w i n d o w m o u n t e d o n the
side o r e n d of t h e m e t a l t u b e . T h e w i n d o w is c h o s e n t o
be thin e n o u g h t o r e d u c e x-ray a b s o r p t i o n , b u t it m u s t
be s t r o n g e n o u g h t o w i t h s t a n d a v a c u u m since t h e
s p e c t r o m e t e r m a y be e v a c u a t e d t o m i n i m i z e x-ray
a b s o r p t i o n in t h e p a t h from t h e s a m p l e t o t h e detec
tor. If a thin-film p o l y m e r w i n d o w is used so as t o
further r e d u c e x-ray a b s o r p t i o n , as is necessary in t h e
m e a s u r e m e n t of soft r a y s , t h e n a r g o n is t h e m o s t

Microprobe

Analysis

c o m m o n l y used inert-gas fill. M i x e d with the m e t h

ane, it is supplied c o n t i n u o u s l y t o c o m p e n s a t e for a n y
l e a k a g e a n d t h e r e b y m a i n t a i n a c o n s t a n t pressure in
the d e t e c t o r . O n the o t h e r h a n d , a sealed berylliumw i n d o w p r o p o r t i o n a l c o u n t e r c o n t a i n i n g either k r y p
t o n o r x e n o n is used for t h e d e t e c t i o n of h a r d e r rays.
W h e n a n individual x-ray p h o t o n enters t h e t u b e , it
causes t h e ejection of a p h o t o e l e c t r o n from a n inertgas a t o m . T h i s p h o t o e l e c t r o n t h e n ionizes o t h e r gas
a t o m s a n d all of t h e electrons p r o d u c e d a r e a t t r a c t e d
t o the central a n o d e wire. T h e s e electrons a r e t h e n
accelerated by the high voltage a n d they in t u r n
p r o d u c e s e c o n d a r y i o n i z a t i o n . T h e result is a n a m p l i
fication of the initial c h a r g e p r o d u c e d by several
o r d e r s of m a g n i t u d e . T h e t o t a l c h a r g e is then c o n
verted t o a voltage pulse by a charge-sensitive p r e a m
plifier. T h e o u t p u t of t h e preamplifier is further
increased by the m a i n amplifier t o pulse sizes of a
m o r e m a n a g e a b l e level. T h e n a m e p r o p o r t i o n a l c o u n
ter derives from t h e fact t h a t the m a g n i t u d e of the
o u t p u t pulse is p r o p o r t i o n a l t o the energy of the
incoming photon.
T h e signal from t h e m a i n amplifier is passed t o a
single-channel analyzer. It c o n v e r t s pulses of different
sizes a n d time d u r a t i o n t o s t a n d a r d pulses which c a n
be processed by s u b s e q u e n t electronic c o m p o n e n t s .
D i s c r i m i n a t i o n c o n t r o l s o n the front e n d allow the
user t o r e m o v e noise a n d u n w a n t e d h i g h e r - o r d e r
reflections. Pulses from t h e single-channel analyzer
a r e t h e n either c o u n t e d with a scaler a n d t r a n s m i t t e d
t o a r a t e m e t e r - d r i v e n s t r i p - c h a r t recorder, o r dis
p l a y e d o n a n i m a g i n g C R T as line scans or a r e a m a p s .
Q u a l i t a t i v e analysis n o r m a l l y involves s c a n n i n g o n e
o r m o r e crystals t h r o u g h their r a n g e a n d displaying
x-ray intensity as a function of angle (or L value) o n a
s t r i p - c h a r t recorder. T h e l o c a t i o n of p e a k s c a n be
c o n v e r t e d t o a w a v e l e n g t h t h r o u g h B r a g g ' s law ( E q n .
(3)) a n d t h e w a v e l e n g t h c a n t h e n be associated with a
specific element t h r o u g h M o s e l e y ' s law ( E q n . (1)). In
practice, direct c o n v e r s i o n of p e a k p o s i t i o n s t o speci
fic elemental spectral lines is readily a c c o m p l i s h e d
t h r o u g h t h e use of tables o r c o m p u t e r i z e d d a t a b a s e s .

2. Energy-Dispersive

X-Ray

Detectors

In t h e 1960s, a n a l t e r n a t i v e a p p r o a c h t o p e r f o r m i n g xr a y chemical analysis in e l e c t r o n - b e a m i n s t r u m e n t s

w a s d e v e l o p e d . It is t h e energy-dispersive x-ray detec
t o r ( E D S ) , illustrated in Fig. 4. E D S s are used t o d a y
with S E M s , analytical t r a n s m i s s i o n electron m i c r o
scopes a n d even A u g e r m i c r o s c o p e s in a d d i t i o n t o
E M A s . It is the solid-state a n a l o g u e t o t h e p r o p o r
t i o n a l c o u n t e r . X rays from the specimen enter the
intrinsic region of a reverse-biased single-crystal sili
c o n p-i-n device c a u s i n g t h e ejection of a p h o t o e l e c
t r o n . T h e p h o t o e l e c t r o n t h e n p r o d u c e s a n u m b e r of
e l e c t r o n - h o l e p a i r s t h a t a r e swept a w a y by t h e applied
bias a n d t h e t o t a l c h a r g e is c o n v e r t e d t o a voltage

117

Electron

Microprobe

Analysis

Dataoutput
device

Pileup
rejector

Electron
Cryostat

Computer

I Bios suppl7

LAL
Display

Specimen
X - ray signal

energy a r e n o t i g n o r e d while the s p e c t r o m e t e r is t u n e d

t o a different energy (wavelength). T h e s e t w o factors
m a k e it possible t o rapidly collect x-ray spectra even
with the l o w - b e a m c u r r e n t s typical of S E M - i m a g i n g
c o n d i t i o n s . C o m b i n i n g this speed with s o m e of the
c o m p u t e r - b a s e d M C A features a l r e a d y m e n t i o n e d
m e a n s t h a t it is often possible t o p e r f o r m a survey
qualitative analysis in a m a t t e r of a few m i n u t e s . A n
e x a m p l e is given in Figs. 5 a n d 6. T h e a d v a n t a g e s of
t h e C D S a r e t h a t it is m o r e sensitive, the spectral d a t a
a r e less a m b i g u o u s a n d it is m u c h better suited t o
elements with a low a t o m i c n u m b e r . T h e techniques,
therefore, c o m p l e m e n t e a c h o t h e r a n d b o t h d e t e c t o r s
a r e often f o u n d o n E M A s .

Figure 4
Energy-dispersive x-ray detector

pulse b y a low-noise preamplifier. T h e voltage pulse is

further amplified b y a m a i n amplifier a n d t h e n p r o
cessed by a m u l t i c h a n n e l analyzer ( M C A ) . Since t h e
voltage of e a c h pulse is p r o p o r t i o n a l t o the initial xray energy, over t h e c o u r s e of t h e data-collection time
a p l o t of x-ray intensity versus energy a p p e a r s o n the
C R T display of the M C A . P e a k identification c a n
then be p e r f o r m e d r a t h e r simply using specially dis
played elemental-spectral-line m a r k e r s which a r e
readily available o n a l m o s t all c o m p u t e r - b a s e d
M C A s . T h e s e systems also include software p a c k a g e s
for p e a k i n t e g r a t i o n , b a c k g r o u n d s u b t r a c t i o n a n d
even full q u a n t i t a t i v e analysis.
T h e r e a s o n w h y a p r o p o r t i o n a l c o u n t e r c a n n o t be
used like a n E D S , as a free-standing detector, is t h a t it
lacks the necessary level of energy r e s o l u t i o n t o easily
distinguish spectral lines of adjacent elements. F o r
e x a m p l e , a t 6.4 keV t h e energy r e s o l u t i o n of a s t a n d
a l o n e p r o p o r t i o n a l c o u n t e r is a b o u t lOOOeV c o m
p a r e d with a n E D S which h a s a r e s o l u t i o n of a b o u t
1 5 0 e V . T h e r e s o l u t i o n of the full C D S is, h o w e v e r ,
vastly s u p e r i o r t o b o t h a p p r o a c h e s with a value a t t h e
s a m e energy of a few electron volts. It s h o u l d also be
m e n t i o n e d , in c o m p a r i n g the t w o a p p r o a c h e s , t h a t n o
s e c o n d a r y - i o n i z a t i o n processes t a k e place in t h e sili
c o n detector. W i t h n o c h a r g e amplification, t h e t o t a l
c h a r g e collected is extremely small. C o n s e q u e n t l y ,
b o t h the d e t e c t o r itself a n d the first stage of the
preamplifier a r e k e p t a t cryogenic t e m p e r a t u r e s a n d
the electronic amplification system used is c o n s i d e r a
bly m o r e sophisticated t h a n t h a t used with t h e C D S .
T h e p o o r e r energy r e s o l u t i o n of t h e E D S relative t o
the C D S leads t o inferior p e a k - t o - b a c k g r o u n d ratios
and sometimes to peak-overlap problems; neverthe
less, the E D S h a s been b r o a d l y accepted o n electronb e a m i n s t r u m e n t s . T h e r e a s o n s center a r o u n d speed
a n d convenience. W i t h virtually n o m o v i n g p a r t s a n d
n o special focusing r e q u i r e m e n t s t h e d e t e c t o r crystal
can be located very close t o t h e s a m p l e , resulting in a
m u c h higher collection efficiency. F u r t h e r m o r e , since
each pulse is processed as it is received, pulses of o n e

118

3.

Applications

T h e E M A c a n be used t o p r o v i d e m i c r o s c o p i c elemen
tal c h a r a c t e r i z a t i o n of a wide variety of samples
e n c o u n t e r e d in m a n y disciplines including metallurgy,
ceramics, m i n e r a l o g y , biology, geology a n d medicine.
In a d d i t i o n t o qualitative analysis, which h a s a l r e a d y
been discussed, it is possible t o use q u a n t i t a t i v e p r o
c e d u r e s t o o b t a i n elemental c o m p o s i t i o n s with 2 - 5 %
relative a c c u r a c y for elements p r e s e n t a b o v e a level of
a few percent. M a t h e m a t i c a l m e t h o d s m a k e it p o s
sible t o p e r f o r m such analyses with a b a r e m i n i m u m
of s t a n d a r d s (for e x a m p l e , only p u r e elemental stan
d a r d s for e a c h c o m p o n e n t ) . A n e x a m p l e of a q u a n t i
tative step scan is given in F i g . 7. T h e s a m p l e is a
diffusion c o u p l e of C u - 1 0 w t % N i b o n d e d t o C u 80 w t % N i a n d a n n e a l e d a t 900 C for 100 h. T h e d a t a

Epoxy mount
Matrix

Carbides

Figure 5
Scanning electron micrograph of the cross section of a
high-temperature alloy. The sample sheet was etched for
5 min in a mixture of bromine and methanol to reveal
carbides

Electron

Microprobe

Analysis

90

80

70

ic

60

50

40

9
*-

/\

Ni + Ta

50

100

150

200

250

Distance in microns

300

350

40<

(/*m)

Figure 7
Diffusion-profile scans of Cu-10wt%Ni bonded to
Cu-80wt%Ni annealed for 100 h at 900 C: , copper;
, nitrogen (courtesy of N. Lewis, General Electric
Corporate Research and Development)

Br

Cr

Energy

Ni

(keV)

(b)

Figure 6
Energy-dispersive spectra obtained from matrix and
carbides in the treated temperature alloy of Fig. 5:
(a) spectrum from the matrix; and (b) spectrum from a
carbide (note that carbon is not seen because of
absorption in the beryllium window of the detector)
(courtesy of C. D. Robertson, General Electric Corporate
Research and Development)

were collected b y a u t o m a t i c a l l y step s c a n n i n g t h e

s a m p l e u n d e r a static electron b e a m while x-ray
intensity d a t a were collected a t e a c h p o i n t w i t h t w o
C D S s t u n e d t o c o p p e r a n d nickel, respectively. Lessquantitative information can be obtained by the
m e t h o d of line s c a n n i n g in w h i c h t h e s p e c i m e n is

d r i v e n c o n t i n u o u s l y u n d e r a static p r o b e while t h e
v a r i a t i o n in intensity of o n e o r m o r e elements is
m o n i t o r e d with t h e r a t e m e t e r s t r i p - r e c o r d e r c o m
b i n a t i o n . Line-scan i n f o r m a t i o n of a similar t y p e c a n
also be displayed o n the C R T i m a g i n g system b y
m a k i n g a c o m p o s i t e p i c t u r e of t h e s c a n n i n g electron
m i c r o g r a p h of t h e t a r g e t a r e a a n d t h e line of the
a c t u a l scan, a n d t h e n s u p e r i m p o s i n g the r a t e m e t e r
output.
X - r a y m a p s c a n be used t o s h o w t h e t w o - d i m e n
sional d i s t r i b u t i o n of o n e o r m o r e elements a n d t h e
c o r r e s p o n d i n g m i c r o s t r u c t u r e as seen b y t h e S E M .
F i g u r e 8 c o n t a i n s a n S E M i m a g e of a particle of B N
in a m a t r i x of d i a m o n d a n d t h e c o r r e s p o n d i n g d o t
m a p s for c a r b o n , n i t r o g e n a n d b o r o n . T h e m a p s a r e
o b t a i n e d b y c o u p l i n g t h e o u t p u t from t h e singlec h a n n e l a n a l y z e r t o t h e " Z " i n p u t (brightness) of the
C R T display. E a c h time a pulse is detected, it is
displayed as a d o t o n t h e C R T . A r e a s of high c o n c e n
t r a t i o n of a p a r t i c u l a r e l e m e n t a r e s h o w n as a n
increase in d o t density r a t h e r t h a n a c h a n g e in g r a y
scale. T h i s b i n a r y - m a p m o d e of p r e s e n t a t i o n is
r e q u i r e d b e c a u s e t h e x-ray signal level is m a n y o r d e r s
of m a g n i t u d e less t h a n t h a t of t h e c o r r e s p o n d i n g
s e c o n d a r y - e l e c t r o n signal. T h e e x a m p l e s h o w n in Fig.
8 also illustrates t h e ability of t h e C D S t o collect d a t a
f r o m l o w - a t o m i c - n u m b e r elements. W i n d o w l e s s E D S
systems a r e also b e i n g d e v e l o p e d , b u t their p o o r e r
energy r e s o l u t i o n will greatly restrict their use for xr a y m a p p i n g of these e l e m e n t s .
See also: Chemical Analysis of Solid Surfaces; Electron
Microscopy, Analytical; X-Ray Fluorescence Spectrometry

119

Electron

Microprobe

Analysis

Figure 8
X-ray maps of a BN crystal in diamond: (a) scanning electron micrograph, and the corresponding dot maps for
(b) carbon, (c) nitrogen and (d) oxygen (courtesy of M. D. McConnell, General Electric Corporate Research and
Development)

Bibliography
Goldstein J I et al. 1992 Scanning Electron Microscopy and
X-Ray Microanalysis: A Text for Biologists, Materials
Scientists, and Geologists. Plenum, New York
Heinrich F J 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Heinrich F J et al. (eds.) 1981 Energy Dispersive Spec
trometry, NBS Special Publication 604. National Bureau
of Standards, Washington, DC
Maurice F, Meny L, Tixier R (eds.) 1978 Microanalysis and
Scanning Electron Microscopy. Editions De Physique,
Orsay, France
Reed S J 1975 Electron Microprobe Analysis. Cambridge
University Press, Cambridge
Wells C 1974 Scanning Electron Microscopy. McGrawHill, New York
E. Lifshin
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]

120

Electron Microscope Analysis of Defect

Clusters, Voids and Bubbles
T h e m i c r o s t r u c t u r a l c h a n g e s p r o d u c e d in crystalline
m a t e r i a l s b y i r r a d i a t i o n o c c u r o n such a scale t h a t
they a r e best a n a l y z e d with a t r a n s m i s s i o n electron
m i c r o s c o p e ( T E M ) . T h e principal m i c r o s t r u c t u r a l
features c a n be classed as defect clusters, v o i d s a n d
b u b b l e s . Since it is t h e presence of these features t h a t
a c c o u n t s for m a n y of t h e r a d i a t i o n - i n d u c e d p r o p e r t y
c h a n g e s , a c o m p l e t e analysis of the m i c r o s t r u c t u r e is
necessary for a full u n d e r s t a n d i n g of t h e r a d i a t i o n
damage.

/.

Defect

Clusters

Defect clusters a r e c h a r a c t e r i z e d in t h e electron

m i c r o s c o p e as small s p o t s w i t h a d a r k e r c o n t r a s t t h a n

Electron

Microscope

Analysis

of Defect

Clusters,

Voids and

Bubbles

s o m e m a t e r i a l s , clusters h a v e b e e n directly associated

with d i s p l a c e m e n t spikes. I n this case, t h e cluster
s h a p e is indefinable, b u t p r o b a b l y closer t o threed i m e n s i o n a l in n a t u r e .
C l u s t e r f o r m a t i o n is a l o w - t e m p e r a t u r e p h e n o m e
n o n o c c u r r i n g w h e n a t o m i c m o b i l i t y is limited. A s t h e
i r r a d i a t i o n t e m p e r a t u r e increases, clusters c a n g r o w
i n t o m o r e definable s t r u c t u r e s . T h e interstitial clusters
g r o w i n t o large l o o p s a n d eventually a dislocation
n e t w o r k . T h e t h r e e - d i m e n s i o n a l v a c a n c y clusters
g r o w i n t o voids a n d , in s o m e cases, b u b b l e s .

2.

Voids

V o i d s a r e gas-free cavities in a n i r r a d i a t e d m a t e r i a l
a n d a p p e a r a s light regions a g a i n s t a d a r k e r b a c k
g r o u n d in t h e electron m i c r o s c o p e i m a g e (see F i g . 2).
T h e s e large voids a r e o b s e r v e d t h r o u g h a b s o r p t i o n
c o n t r a s t , a s there is less electron a b s o r p t i o n w h e n t h e
electron b e a m passes t h r o u g h t h e void. Smaller voids
a r e n o r m a l l y i m a g e d in a n u n d e r - f o c u s c o n d i t i o n , in
w h i c h t h e b r i g h t Fresnel fringe a c c e n t u a t e s t h e void.

Figure 1
Transmission electron micrograph of defect clusters in
nickel irradiated with neutrons at ~ 330 to a dose of
5 x 10 23 neutrons m 2 (E> 1 MeV); the arrow indicates a
dislocation loop

the s u r r o u n d i n g m a t r i x (see F i g . 1). T h e s h a p e o f t h e

clusters is indefinable, m o s t l y b e c a u s e of their small
size which c a n b e a t o r below t h e r e s o l u t i o n limit of
the m i c r o s c o p e (i.e., a b o u t 1.5-2.0 n m ) . T h e c o n t r a s t
is generally d u e t o s t r a i n i n g o f t h e m a t r i x , b u t o t h e r
c o n t r a s t effects m a y also b e involved, p a r t i c u l a r l y in
alloys w h e r e a t o m s of a specific alloying element m a y
cluster.
T h e s e clusters r e p r e s e n t t h e initial state o f a g g l o m
e r a t i o n of t h e r a d i a t i o n - p r o d u c e d defects, t h a t is, t h e
interstitials, vacancies, d i s p l a c e m e n t spikes a n d / o r
t r a n s m u t e d a t o m s . T h e interstitials a n d vacancies c a n
cluster o n a p l a n e a n d eventually collapse a n d g r o w
i n t o a dislocation l o o p . S u c h a l o o p is i n d i c a t e d in
Fig. 1. F r o m o b s e r v a t i o n s of small l o o p s , it c a n b e
inferred t h a t m a n y of t h e smaller s p o t s in F i g . 1 a r e ,
in fact, dislocation l o o p s t h a t a r e n o t resolved in
the m i c r o s c o p e i m a g e . C l u s t e r s c a n also b e t h r e e d i m e n s i o n a l , w h i c h r e p r e s e n t s t h e initial stages o f
vacancy a g g l o m e r a t i o n o r a g g l o m e r a t i o n of s o m e
p a r t i c u l a r elements in a n alloy. Because of t h e dif
ference in strain field of a t h r e e - d i m e n s i o n a l cluster
c o m p a r e d with a p l a n a r cluster, T E M t e c h n i q u e s a r e
available w h i c h will distinguish b e t w e e n t h e t w o . I n

Figure 2
Transmission electron micrograph of voids in nickel
neutron-irradiated at 800 to a dose of 5 x 10 23 neutrons
m - 2( > l M e V )

121

Electron

Microscope

Analysis

of Defect

Clusters,

Voids and

Bubbles

Figure 3
Transmission electron micrograph of a void lattice in
niobium irradiated with 7.5 MeV tantalum ions at 1070
to a dose of 5 10 20 ions m 2

Figure 4
Transmission electron micrograpoh of helium gas bubbles
in molybdenum bombarded with 200 keV particles at
1470

Very small voids c a n also give rise t o strain c o n t r a s t .

L a r g e voids generally a s s u m e a c r y s t a l l o g r a p h i c s h a p e
(Fig. 2). T h e final o r e q u i l i b r i u m s h a p e of t h e voids is
different in b o d y - c e n t e r e d - c u b i c , face-centered-cubic
a n d h e x a g o n a l - c l o s e - p a c k e d m a t e r i a l s , a n d is deter
m i n e d b y the relative values of t h e interfacial energies
of the crystal planes.
V o i d s a r e f o r m e d from t h e a g g l o m e r a t i o n of
r a d i a t i o n - p r o d u c e d vacancies a n d a r e o b s e r v e d in
m a t e r i a l s i r r a d i a t e d a t o n e - t h i r d t o o n e - h a l f of t h e
melting t e m p e r a t u r e Tm. Vacancies b e c o m e suffi
ciently m o b i l e a t a b o u t \Tm, allowing void g r o w t h .
V o i d s c a n be h e t e r o g e n e o u s l y o r h o m o g e n e o u s l y dis
t r i b u t e d in a m a t e r i a l . Typical e x a m p l e s of h e t e r o g e n
e o u s d i s t r i b u t i o n a r e t h e d e n u d i n g of voids n e a r g r a i n
b o u n d a r i e s o r free surfaces, a n d t h e a t t a c h m e n t of
voids t o precipitate particles. A n e x a m p l e of a very
h o m o g e n e o u s d i s t r i b u t i o n is t h e void lattice. I n a void
lattice, the voids a r r a n g e themselves in a p e r i o d i c
a r r a y similar t o a n a t o m i c lattice (see Fig. 3).
T h e t o t a l void v o l u m e c a n be d e t e r m i n e d from
electron m i c r o g r a p h s by m e a s u r i n g the void size a n d
n u m b e r of voids p e r u n i t v o l u m e . T h i s v o l u m e m u s t
be a c c o u n t e d for by a n equivalent a m o u n t of m a t e r i a l

swelling. T h e r e h a v e been extensive T E M investiga

tions of t h e void m i c r o s t r u c t u r e because of t h e tech
nological i m p o r t a n c e of swelling. M o d e l s of void
swelling h a v e b e e n e v a l u a t e d t h r o u g h use of T E M
analysis.

122

3.

Bubbles

B u b b l e s a r e i n t e r n a l cavities t h a t c o n t a i n gas a t o m s
such as h e l i u m o r k r y p t o n . A n e q u i l i b r i u m b u b b l e
c o n t a i n s e n o u g h gas t h a t t h e internal gas p r e s s u r e j u s t
b a l a n c e s t h e surface tension of t h e cavity. B u b b l e s
give t h e s a m e c o n t r a s t in t h e electron m i c r o s c o p e as
voids a n d , in this sense, voids a n d b u b b l e s a r e indis
tinguishable. T h e m a i n distinctive feature is t h a t
b u b b l e s form preferentially a t grain b o u n d a r i e s , dislo
c a t i o n s a n d o t h e r i n t e r n a l defects, w h e r e a s voids d o
n o t . Preferential f o r m a t i o n of h e l i u m b u b b l e s a t dislo
c a t i o n s in - b o m b a r d e d m o l y b d e n u m is illustrated in
Fig. 4. B u b b l e s c a n also a s s u m e a c r y s t a l l o g r a p h i c
s h a p e similar t o voids.
B u b b l e s result from t h e coalescence of gas f o r m e d
by transmutation reactions during neutron irradia-

Electron

tion. Fission p r o d u c t s (e.g., k r y p t o n a n d x e n o n ) ,

p r o t o n s ( h y d r o g e n ) a n d particles (helium) a r e t h e
m a i n sources of g a s d u r i n g i r r a d i a t i o n . V o i d s a n d
bubbles form at approximately the same temperature,
so t h a t in a n y i r r a d i a t i o n in w h i c h g a s e o u s p r o d u c t s
are formed t h e voids will b e a t least partially filled
with g a s .
Bubbles filled with inert g a s , such as h e l i u m , a r e
very resistant t o h i g h - t e m p e r a t u r e a n n e a l i n g , w h e r e a s
voids a n n e a l o u t readily a t t e m p e r a t u r e s ^ 0 . 6 Tm.
This is d u e t o t h e e x t r e m e lattice insolubility of t h e
inert g a s a t o m s . V o i d s , partially filled with g a s , h a v e
been observed t o s h r i n k b y v a c a n c y emission d u r i n g
a n n e a l i n g t o a size a t w h i c h they b e c o m e e q u i l i b r i u m
gas b u b b l e s . N o further s h r i n k a g e t h e n o c c u r s .
B u b b l e g r o w t h a t high t e m p e r a t u r e s t h r o u g h m i
g r a t i o n a n d coalescence of smaller b u b b l e s h a s b e e n
observed directly in t h e electron m i c r o s c o p e . I n this
m a n n e r , r a t h e r large b u b b l e s c a n f o r m b o t h in t h e
grain b o u n d a r i e s a n d in t h e grain interior. G r a i n b o u n d a r y b u b b l e s c a n result in severe e m b r i t t l e m e n t
of t h e m a t e r i a l .
See also: Field-Ion Microscopy: Observation of Radiation
Effects

Bibliography
Brager R, Perrin J S 1982 Effects of Radiation on
Materials, ASTM STP 782. American Society for Testing
and Materials, Philadelphia, PA
Corbett J W, Ianiello L C (eds.) 1971 Int. Conf. RadiationInduced Voids in Metals. National Technical Information
Service, Springfield, VA
Gittus J 1978 Irradiation Effects in Crystalline Solids.
Applied Science, London, Chaps. 2-4, pp. 37-166
Goodhew J 1988 Migration of bubbles, voids and inclu
sions in crystals. In: Cahn R W (ed.) 1988 Encyclopedia
of Materials Science and Engineering, Suppl. Vol. 1.
Pergamon, Oxford, pp. 318-22
Makin J (ed.) 1966 Report of Consultants Symposium on
the Nature of Small Defect Clusters, AERE Report N o .
R-5269. HMSO, London
Makin J 1971 The application of electron microscopy to
radiation damage studies. In: Valdre U (ed.) 1971 Elec
tron Microscopy in Materials Science. Academic Press,
London, pp. 388-461
Merkle L 1975 Defect production by energetic particle
bombardment. In: Peterson L, Harkness S D (eds.)
1975 Radiation Damage in Metals. ASM International,
Materials Park, OH
Nelson R S (ed.) 1975 Proc. Symposium Physics of Irradia
tion Produced Voids, AERE Report No. R-7934. HMSO,
London
Norris D I R 1972 Voids in irradiated metals. Radiat. Eff.
14: 1-37; 15: 1-35
Wiffen F W, Spitznagel J A (eds.) 1982 Advanced Techniques
for Characterizing Microstructures. Metallurgical Society
of AIME, Warrendale, PA
J. L. B r i m h a l l
[Battelle-Pacific N o r t h w e s t L a b o r a t o r i e s ,
Richland, Washington, U S A ]

Microscopy,

Analytical

Electron Microscopy, Analytical

T h e analytical electron m i c r o s c o p e ( A E M ) is a t r a n s
mission electron m i c r o s c o p e ( T E M ) in w h i c h q u a n t i
tative chemical d a t a c a n b e o b t a i n e d in a d d i t i o n t o t h e
c o n v e n t i o n a l diffraction a n d i m a g i n g i n f o r m a t i o n
t h a t is r o u t i n e l y available (see Electron Diffraction).
T h e A E M gives access t o m a n y of t h e signals
g e n e r a t e d w h e n a high-energy electron b e a m traverses
a thin-foil specimen. T h e signals m o s t c o m m o n l y used
a r e s u m m a r i z e d in F i g . 1. I n a c o n v e n t i o n a l T E M
only t h e t r a n s m i t t e d a n d elastically scattered electrons
a r e used t o f o r m i m a g e s a n d diffraction p a t t e r n s ,
w h e r e a s in a s c a n n i n g electron m i c r o s c o p e ( S E M )
only t h e b a c k s c a t t e r e d a n d s e c o n d a r y electrons a r e
used (see Scanning Electron Microscopy). I n a n A E M
all these electron signals a r e m a d e available a n d c a n
be used t o f o r m i m a g e s . Diffraction i n f o r m a t i o n c a n
also be o b t a i n e d a t t h e s a m e t i m e in t h e A E M , using
c o n v e r g e n t b e a m diffraction t e c h n i q u e s (see Electron
Diffraction). M o s t i m p o r t a n t l y , h o w e v e r , t h e t w o
r e m a i n i n g signals, n a m e l y , inelastically scattered
(energy-loss) electrons a n d characteristic rays, c a n
be used t o o b t a i n chemical i n f o r m a t i o n a b o u t t h e
specimen. T h i s is t h e c o r n e r s t o n e of analytical m i c r o s
c o p y , since t h e c o m p o s i t i o n a l i n f o r m a t i o n c a n b e
related t o t h e m i c r o s t r u c t u r e of t h e specimen o n a
scale of ~ l O n m a n d a b o v e . T h u s , a high degree of
c h a r a c t e r i z a t i o n of a m a t e r i a l c a n be p e r f o r m e d
a l m o s t s i m u l t a n e o u s l y o n a single i n s t r u m e n t ( H r e n et
al. 1979, Williams 1984).

1.

Instrumentation

T h e A E M is usually b a s e d o n t h e s c a n n i n g t r a n s m i s
sion electron m i c r o s c o p e ( S T E M ) , which scans a fine
p r o b e of electrons a c r o s s a thin-foil specimen. T w o
f o r m s exist: t h e so-called d e d i c a t e d S T E M s , which
c a n only o p e r a t e in s c a n n i n g m o d e a n d a r e similar in

Incident
electron probe
Primary
backscattered
electrons
Characteristic
rays
Thin specimen

Inelastically
scattered electrons

Figure 1
Schematic representation of the most common signals
available to the analytical electron microscopist

123

Electron

Microscopy,

Analytical

principle t o S E M s , a n d c o n v e r t e d T E M s ( T E M /
S T E M s ) . T h e latter form a r e c o n s i d e r a b l y m o r e
n u m e r o u s a n d in m a n y respects a r e m o r e versatile
i n s t r u m e n t s (see Fig. 2). W h e n the b e a m scans over
the desired a r e a of the specimen, a n y of the signals
generated in Fig. 1 c a n be detected, as s h o w n in Fig. 2,
a n d used t o m o d u l a t e a c a t h o d e r a y t u b e display, t h u s
forming a n i m a g e . It is u s u a l t o m a k e use of the
t r a n s m i t t e d a n d scattered electrons t o form images
equivalent t o bright-field a n d dark-field images in a
T E M . T o o b t a i n chemical i n f o r m a t i o n from a desired
region, it is necessary t o s t o p t h e s c a n n i n g p r o b e a n d
position it o n t h e region of interest, a n d t h e n switch
o n the x-ray o r electron energy-loss detector. T h e
c o m b i n a t i o n of a very fine ( < 10 n m ) electron p r o b e
a n d thin-foil specimen h a s t h e specific a d v a n t a g e t h a t
a n y i n f o r m a t i o n o b t a i n e d is from a very small v o l u m e
of the specimen, since b e a m - s p r e a d i n g t h r o u g h thin
foils is n o t very significant. Spatial r e s o l u t i o n of
chemical analysis is generally c o n s i d e r e d t o b e
< 50 n m in m o s t e l e c t r o n - t r a n s p a r e n t
material
specimens.

Electron source

Condenser I

Condenser

Double deflection
scan coils

Secondary electron

Backscattered
electron detection
X-rav detection

2. X-Ray

Microanalysis

in the A EM

W h e n high-energy electrons ionize single a t o m s in the

specimen, t h e s u b s e q u e n t r e t u r n t o the g r o u n d state
results in the emission of a characteristic ray.
C o n t i n u u m rays (or b r e m s s t r a h l u n g ) a r e also p r o
d u c e d w h e n the high-energy electrons slow d o w n a n d
lose energy c o n t i n u o u s l y t h r o u g h multiple, n o n c h a r acteristic interactions. B o t h types of r a y s a r e
detected, b u t only t h e characteristic o n e s a r e used for
quantification in m a t e r i a l s science.
T h e rays a r e detected using a n energy-dispersive
s p e c t r o m e t e r ( E D S ) consisting of a liquid-nitrogencooled crystal of silicon d o p e d with lithium ( S t a t h a m
1981). X - r a y p h o t o n s g e n e r a t e e l e c t r o n - h o l e p a i r s in
the crystal in p r o p o r t i o n t o their energy a n d t h e
resulting c h a r g e pulses a r e d i s c r i m i n a t e d a n d dis
played a s a s p e c t r u m of x-ray intensity versus energy
(see Fig. 3). T h e principal limitation of this t e c h n i q u e
is t h a t elements with a n a t o m i c n u m b e r < 10 c a n n o t
be detected using c o n v e n t i o n a l s p e c t r o m e t e r s p r o
tected b y beryllium w i n d o w s . Recently, h o w e v e r ,
" w i n d o w l e s s " E D S systems h a v e b e c o m e available
commercially, c a p a b l e of detecting elements with
^ 5 ( T h o m a s 1983). T h e relative a c c u r a c y of the
quantification in t h e A E M is p o o r ( a b o u t 5 % )
c o m p a r e d with the c o n v e n t i o n a l electron m i c r o p r o b e
( a b o u t 1-2%). H o w e v e r , the a c t u a l m a s s analyzed
1 9
with this a c c u r a c y c a n be very small ( ~ 1 0 " g ) .
T h e x-ray s p e c t r u m in Fig. 3 c a n b e identified a s
c o m i n g from a very specific region of t h e thin-foil
specimen i m a g e d in the A E M a n d c a n be quantified in
a s t r a i g h t f o r w a r d m a n n e r . T h e thin-foil n a t u r e of the
specimen m e a n s t h a t a b s o r p t i o n a n d fluorescence of
the x-ray signal c a n often be neglected a n d t h u s the

124

^
^2^**

rV////A

Projector lens to
control detector
collection angle

Transmitted electron
detection (bright field]

Annular detector for

scattered electrons
(dark field)
3 Electron
energy - loss
spectrometry

Energy
analysis
or image
display

Figure 2
The electron optics of a TEM/STEM used as an analytical
microscope. The various signals generated at the specimen
(Fig. 1) are detected and displayed as shown. Diffraction
information is available in the back focal plane of the
objective lens (courtesy of Philips Electronics Instruments
Inc.)

Electron

Microscopy,

Analytical

Ni

looo
Cr

wy.u..

Ni

Ni

Cr

Energy

(keV)

Figure 3
Typical energy-dispersive x-ray spectrum obtained from an alloy of nickel-chromium-iron showing the principal
characteristic K a and K p peaks for these elements. The nickel L line is also present at ~ 1 keV. The presence of a small
amount of silicon is also indicated.

intensity of t h e characteristic elemental x-ray p e a k

a b o v e t h e c o n t i n u u m b a c k g r o u n d is p r o p o r t i o n a l t o
the a m o u n t of t h e e l e m e n t p r e s e n t in t h e a n a l y z e d
v o l u m e . Q u a n t i f i c a t i o n is usually achieved using t h e
Cliff-Lorimer e q u a t i o n (Cliff a n d L o r i m e r 1975)
which for a b i n a r y system is
CJCB

= kABIJIB

(1)

w h e r e t h e c o n c e n t r a t i o n C of elements A a n d is
directly related t o t h e characteristic x-ray intensity I,
t h r o u g h a factor A: AB w h i c h c a n b e either e x p e r i m e n
tally d e t e r m i n e d o r calculated from first principles.
U n d e r situations where absorption and
fluorescence
are n o t negligible, simple e q u a t i o n s exist t o a c c o u n t
for t h e effect ( G o l d s t e i n et al. 1977). A n e x a m p l e of
the use of E q n . (1) t o d e t e r m i n e t h e v a r i a t i o n in silver
c o m p o s i t i o n a c r o s s a g r a i n - b o u n d a r y precipitate-free
z o n e in a l u m i n u m - s i l v e r is s h o w n in Fig. 4.
T h e c o m b i n a t i o n of a fine p r o b e p r o d u c e d in
S T E M a n d limited electron scattering d u e t o t h e use
of thin specimens m e a n s t h a t t h e spatial r e s o l u t i o n of
microanalysis is m u c h b e t t e r t h a n t h e limit of x-ray
microanalysis of b u l k specimens, a r o u n d 1 (see
Electron Microprobe
Analysis).
Several theoretical
a n d e x p e r i m e n t a l t e c h n i q u e s exist t o e s t i m a t e t h e
a c t u a l spatial r e s o l u t i o n of m i c r o a n a l y s i s . T h e m o s t
sophisticated m e t h o d s use M o n t e C a r l o c o m p u t e r
s i m u l a t i o n s of electron trajectories ( K y s e r 1979), b u t
a simple e q u a t i o n d e v e l o p e d b y R e e d serves for m o s t
p u r p o s e s ( G o l d s t e i n et al. 1977). T h e b e a m s p r e a d i n g
b of a p o i n t s o u r c e of electrons of incident e n e r g y E0
in a specimen of a t o m i c n u m b e r Z , a t o m i c weight A,
density a n d thickness t is given b y

a n d therefore t h e highest spatial r e s o l u t i o n is expected

in thin foils of l o w - Z m a t e r i a l using high-energy
i n s t r u m e n t s . P r o b e sizes of < 1 n m c a n be g e n e r a t e d
using field-emission electron g u n s , a l t h o u g h these a r e
usually available o n l y in u l t r a h i g h - v a c u u m d e d i c a t e d
S T E M s . I n practice, t h e spatial r e s o l u t i o n for q u a n t i
tative analysis is usually g o v e r n e d b y the specimen
thickness in t h e region of interest a n d t h e n u m b e r of
x-ray c o u n t s g e n e r a t e d in a r e a s o n a b l e time.

3. Microanalysis
Electrons

Using Inelastically

Scattered

T h e r e a r e several m e c h a n i s m s b y w h i c h electrons lose

energy w h e n t r a v e r s i n g t h e thin-foil specimen, b u t
only t w o c o n t a i n u s a b l e chemical i n f o r m a t i o n a n d a r e
a m e n a b l e t o electron energy-loss
spectroscopy
(EELS).
First, b e a m electrons w h i c h h a v e r e m o v e d innershell electrons from specimen a t o m s lose a c h a r a c t e r
istic a m o u n t of energy d e p e n d i n g o n which electron
shell w a s ionized a n d this is t h e m a j o r energy loss
p r o c e s s used for m i c r o a n a l y s i s in t h e A E M . Secondly,
in a few m e t a l s such as a l u m i n u m a n d m a g n e s i u m , the
free-electron density is high a n d varies with alloying
a d d i t i o n s . E n e r g y lost t h r o u g h i n t e r a c t i o n s of t h e fast
electrons a n d t h e free-electron gas is p r o p o r t i o n a l t o
a n d therefore t o c o m p o s i t i o n . S u c h p l a s m o n losses
a r e rarely used for m i c r o a n a l y s i s p u r p o s e s t h e few

125

Electron

Microscopy,

Analytical

(b)

stem

valves

extrapolated
G composition
I

I
-2

IPFZI
Distance

from gram boundary

(10

nm )

Figure 4
(a) TEM image of a precipitate-free zone (PFZ) in Al-16 at.%Ag aged for 75 min at 250 C. Coarse equilibrium -phase
precipitates are present along the boundary which depletes the surrounding region of silver thus preventing precipitation
of either metastable GP zones (small spherical precipitates) or metastable y' (larger platelike particles), (b) Silver
composition profile across a precipitate-free zone (PFZ) in Fig. 4a obtained by quantification of EDS spectra from many
points on either side of the grain boundary (GB). Silver depletion within the PFZ is clearly visible and extrapolation to
the grain-boundary composition gives information about the phase diagram at 250 C (courtesy of S. Merchant)

cases h a v e been reviewed by W i l l i a m s a n d E d i n g t o n

(1976).
T h e s t u d y of ionization-loss electrons is achieved by
the insertion of a m a g n e t i c p r i s m s p e c t r o m e t e r b e l o w
the viewing screen of t h e A E M (Joy 1979). T h e
electrons e n t e r i n g t h e s p e c t r o m e t e r a r e dispersed
a c c o r d i n g t o their energy a n d t h e resulting e n e r g y
s p e c t r u m is s c a n n e d a c r o s s a selecting slit. T h e signal
t h r o u g h t h e slit is detected using a s c i n t i l l a t o r - p h o t o multiplier system, amplified a n d t h e n displayed as a
plot of intensity versus energy loss (Fig. 5). Quantifi
c a t i o n is achieved by i n t e g r a t i n g t h e intensity in t h e
s h a r p l y defined edges a b o v e t h e r a p i d l y falling b a c k
g r o u n d (Joy 1979). T h e a d v a n t a g e of this E E L S
t e c h n i q u e is t h a t it is sensitive t o t h e presence of
elements t h a t c a n n o t be detected using c o n v e n t i o n a l
E D S ( Z < 10). T h e limitations a r e t h a t t h e specimens
h a v e t o be very thin ( < 3 0 n m ) for r e a s o n a b l e d a t a
acquisition a n d existing q u a n t i f i c a t i o n p r o c e d u r e s a r e
relatively primitive in c o m p a r i s o n with E D S tech
n i q u e s , giving accuracies of > 2 0 % relative (Egert o n 1984). F i g u r e 5 illustrates t h e use of E E L S for
m i c r o a n a l y s i s of t i t a n i u m nitride in t h e A E M . It is
often impossible t o distinguish t i t a n i u m nitride a n d

126

c a r b i d e inclusions in steel by o t h e r less direct tech

n i q u e s , such as diffraction, b e c a u s e of t h e similarity of
their crystal s t r u c t u r e s .
A s well a s m i c r o c h e m i c a l i n f o r m a t i o n , E E L s p e c t r a
often c o n t a i n i n f o r m a t i o n in t h e so-called fines t r u c t u r e regions e x t e n d i n g b o t h before a n d after t h e
discrete i o n i z a t i o n edge. E x t e n d e d - a b s o r p t i o n finestructure spectra contain bonding information and
a t o m i c s t r u c t u r e detail n o t o t h e r w i s e o b t a i n a b l e ( T e o
a n d J o y 1981).

4. Future

Developments

A E M h a s e x p a n d e d r a p i d l y i n t o all fields of m a t e r i a l s
science a n d will be t h e m a j o r m o d e of electron m i c r o
scope d e v e l o p m e n t in t h e foreseeable future. T h e use
of s c a n n i n g b e a m s a n d , therefore, electron d e t e c t o r s
a n d digital signals gives t h e user electronic access t o
all t h e d a t a . T h u s , on-line d a t a m a n i p u l a t i o n is n o w
possible w h i c h , c o m b i n e d w i t h c o m p u t e r h a n d l i n g of
d a t a a n d feedback c o n t r o l of t h e m i c r o s c o p e , p r o
mises t o revolutionize t h e a c q u i s i t i o n of s t r u c t u r a l
a n d chemical i n f o r m a t i o n from m a t e r i a l s ( R e z a n d
W i l l i a m s 1982). E D S t e c h n i q u e s in A E M a r e a l m o s t

Electron

Microscopy,

High-Resolution

Bibliography

Energy l<

Figure 5
TEM micrograph of a small precipitate particle in
stainless steel. The energy-loss spectrum below shows
peaks corresponding to ionization of the nitrogen shell
and titanium L shells, indicating that the precipitate is
TiN (courtesy of N. J. Zaluzec)

s t a n d a r d i z e d a n d future d e v e l o p m e n t will involve

i m p r o v i n g t h e a c c u r a c y of t h e available d a t a . Q u a n t i
fication p r o c e d u r e s for E E L S will h a v e t o i m p r o v e
before it is a t e c h n i q u e directly useful t o t h e m a t e r i a l s
engineer. H o w e v e r , t h e d e v e l o p m e n t of d e c o n v o l u
tion p r o c e d u r e s a n d t h e a d v e n t of h i g h e r v o l t a g e
i n s t r u m e n t s s h o u l d m a k e it possible t o a n a l y z e thicker
specimens.
B o t h E D S a n d E E L S a r e limited in their sensitivity
by t h e signal-to-noise r a t i o in t h e s p e c t r u m . T h e o r e t
ically, this r a t i o s h o u l d i m p r o v e w i t h increasing acce
lerating voltage, a n d i n t e r m e d i a t e v o l t a g e ( 3 0 0 400 k V ) A E M s a r e b e i n g d e v e l o p e d . W h e n , in t h e
future, these i n s t r u m e n t s a r e designed w i t h chemical
analysis r a t h e r t h a n h i g h - r e s o l u t i o n i m a g i n g as their
p r i m a r y role, t h e n analytical electron m i c r o s c o p y will
be a m a t u r e t e c h n i q u e . D e v e l o p m e n t s in t h e field a r e
r e p o r t e d in t h e p r o c e e d i n g s of t h e A E M conferences
p u b l i s h e d every three years (Geiss 1981, W i l l i a m s a n d
J o y 1984).
See also: Electron Energy-Loss Spectrometry; Electron
Microprobe Analysis

Cliff G, Lorimer G W 1975 The quantitative analysis of thin

specimens. J. Microsc. 103: 203-7
Egerton R F 1984 Quantitative microanalysis by electron
energy loss spectroscopy: the current status. In: Johari
(ed.) 1984 Scanning Electron Microscopy, Vol. 2. SEM
Inc., O'Hare, IL, pp. 505-12
Geiss R (ed.) 1981 Analytical Electron Microscopy1981.
San Francisco Press, San Francisco, CA
Goldstein J I, Costley J L, Lorimer G W, Reed S J 1977
Quantitative x-ray analysis in the electron microscope. In:
Johari (ed.) 1977 Scanning Electron Microscopy, Vol. 1.
IIT Research Institute, Chicago, IL, pp. 315-24
Hren J J, Goldstein J I, Joy D C (eds.) 1979 Introduction to
Analytical Electron Microscopy. Plenum, New York
Joy D C 1979 The basic principles of electron energy-loss
spectroscopy. In: Hren et al. 1979, pp. 223-44
Kyser D F 1979 Monte Carlo simulation in analytical
electron microscopy. In: Hren et al. 1979, pp. 199-221
Rez P, Williams D 1982 Electron microscope/computer
interactions: a general introduction. Ultramicroscopy 8:
247-52
Statham J 1981 X-ray microanalysis with Si(Li) detectors.
J. Microsc. 123: 1-23
Teo , Joy D C 1981 EXAFS Spectroscopy. Plenum, New
York
Thomas L 1983 Simultaneous electron and x-ray spectro
metry in a scanning transmission electron microscope. In:
Gooley R (ed.) 1983 Microbeam Analysis1983. San
Francisco Press, San Francisco, CA
Williams D 1984 Practical Analytical Electron Microscopy
in Materials Science. VCH, Deerfield Beach, FL
Williams D B, Edington J W 1976 High resolution micro
analysis in materials science using electron energy loss
measurements. J. Microsc. 108: 113-45
Williams D B, Joy D C (eds.) 1984 Analytical Electron
Microscopy1984. San Francisco Press, San Francisco,
CA
D . B. Williams
[Lehigh University, Bethlehem,
Pennsylvania, USA]

Electron Microscopy, High-Resolution

I n t h e t e c h n i q u e of h i g h - r e s o l u t i o n t r a n s m i s s i o n elec
t r o n m i c r o s c o p y t w o o r m o r e b e a m s of t h e electron
diffraction p a t t e r n located in t h e b a c k focal p l a n e of
t h e objective lens of a t r a n s m i s s i o n electron m i c r o
scope r e c o m b i n e t o f o r m a n i m a g e in which there is
fine detail a t a n a t o m i c level. I n certain favorable
c i r c u m s t a n c e s such i m a g e s c a n b e i n t e r p r e t e d directly
in t e r m s of t h e projected p o t e n t i a l of t h e m a t e r i a l
u n d e r investigation, b u t a m b i g u i t i e s in t h e interpre
t a t i o n of h i g h - r e s o l u t i o n i m a g e s c a n arise if t h e m a t e r
ial is t o o thick o r if it c o n t a i n s defects, even if the
i n t e r p r e t a t i o n is b a c k e d u p with detailed i m a g e simu
l a t i o n s b a s e d o n t h e d y n a m i c scattering b e h a v i o r of
high-energy electrons. T h e t e c h n i q u e h a s wide appli
c a t i o n s in m a t e r i a l s science a n d , for e x a m p l e , h a s
been used t o o b t a i n v a l u a b l e i n f o r m a t i o n a b o u t the

127

Electron

Microscopy,

High-Resolution

a t o m i c scale s t r u c t u r e of i n t e r p h a s e interfaces, the

surface structures of catalytic particles, the layered
structures of c e r a m i c s u p e r c o n d u c t o r s a n d the crystal
structures of microcrystalline zeolite m o l e c u l a r sieves.
T h e c u r r e n t g e n e r a t i o n of c o m m e r c i a l highresolution electron m i c r o s c o p e s use high-energy elec
t r o n s accelerated t h r o u g h p o t e n t i a l differences of
2 0 0 - 1 0 0 0 keV a n d h a v e i n t e r p r e t a b l e r e s o l u t i o n s
a p p r o a c h i n g 0.15 n m which, a l t h o u g h far s u p e r i o r t o
the resolution limit of visible light, is nevertheless
o r d e r s of m a g n i t u d e greater t h a n t h e w a v e l e n g t h of
the electrons. T h i s is b e c a u s e the r e s o l u t i o n is limited
by a b e r r a t i o n s in t h e electron lenses, t h e t w o m o s t
i m p o r t a n t of which a r e spherical a b e r r a t i o n a n d c h r o
m a t i c a b e r r a t i o n . A l t h o u g h there a r e still s o m e gains
t o be m a d e in i m p r o v i n g voltage a n d c u r r e n t stabili
ties a n d in using sophisticated electron lens designs, it
is likely t h a t the m o s t i m p o r t a n t a d v a n c e s in highresolution electron m i c r o s c o p y will c o m e from im
p r o v e m e n t s in the specimen e n v i r o n m e n t a n d in t h e
r a n g e of auxiliary e q u i p m e n t t h a t c a n be used t o
extract chemical i n f o r m a t i o n a t t h e a t o m i c level.

I.

Instrumentation

C o m m e r c i a l high-resolution electron m i c r o s c o p e s
( H R E M s ) in t h e 2 0 0 - 4 0 0 k e V p o t e n t i a l difference
r a n g e h a v e t h e s a m e external a p p e a r a n c e as c o n v e n
tional t r a n s m i s s i o n electron m i c r o s c o p e s a n d it is t h e
differences in their internal i n s t r u m e n t a t i o n t h a t allow
high resolutions t o be a t t a i n e d . E l e c t r o n sources in
H R E M s t e n d t o be either p o i n t e d t u n g s t e n filaments
or l a n t h a n u m h e x a b o r i d e ( L a B 6 ) filaments, b o t h of
which give high brightness a n d e n a b l e direct magnifi
c a t i o n s of over x 500 000 t o be usefully e m p l o y e d . A n
alternative to these t w o electron sources is the field
emission g u n with a t u n g s t e n c a t h o d e . T h i s c o m b i n e s
a low energy s p r e a d with a high brightness, b o t h of
which are very desirable characteristics, b u t the d r a w
b a c k s of a field emission g u n a r e t h a t it needs a high
10
v a c c u m of the o r d e r of 1 0 ~ t o r r a n d t h a t it is difficult
for it to p r o v i d e a u n i f o r m illumination of samples
over r e a s o n a b l y sized a r e a s .
T h e o t h e r m a i n difference in the i n s t r u m e n t a t i o n
between c o n v e n t i o n a l a n d high-resolution t r a n s m i s
sion electron m i c r o s c o p e s is in the design of the
objective lenses. In H R E M s the focal length of the
objective lens is k e p t as s h o r t as possible (typically less
t h a n 2 m m ) to minimize lens a b e r r a t i o n s (see Sect. 2).
In practice this m e a n s t h a t there is little r o o m in which
to p u t the specimen a n d , in the effort to a t t a i n high
resolution, c o m p r o m i s e s a r e usually m a d e in the
design of electron lenses t h a t limit t h e r a n g e of
specimen tilting t o typically 15. It is also vitally
i m p o r t a n t in a n H R E M t o m a i n t a i n a clean e n v i r o n
m e n t a r o u n d t h e specimen t o minimize specimen
c o n t a m i n a t i o n over p r o l o n g e d p e r i o d s of m i c r o s c o p e
usage. T h i s m e a n s t h a t effective a n t i c o n t a m i n a t i o n

128

shields a r e n e e d e d close t o t h e s a m p l e , w h i c h also

places limitations o n t h e design of t h e objective lens.
It is also n o t u n c o m m o n t o h a v e a t o p e n t r y stage
r a t h e r t h a n a side e n t r y stage (possibly even with a
2.3 m m d i a m e t e r specimen h o l d e r r a t h e r t h a n a 3 m m
d i a m e t e r specimen h o l d e r ) a n d it is n o t u n u s u a l t o
dispense with m i c r o a n a l y t i c a l facilities if there is a
need t o place d e t e c t o r s n e a r t h e specimen. H o w e v e r ,
i n s t r u m e n t a t i o n of all t r a n s m i s s i o n electron m i c r o
scopes h a s i m p r o v e d over t h e years a n d t h e c u r r e n t
400 keV m i c r o s c o p e s available c o m m e r c i a l l y t e n d t o
be either a n H R E M version with a n i n t e r p r e t a b l e
r e s o l u t i o n of a r o u n d 0.18 n m , possibly with m i c r o analytical facilities b u t with limited tilting facilities, o r
a version with a n i n t e r p r e t a b l e r e s o l u t i o n of a r o u n d
0.25 n m with large-scale tilting of 45 a n d with t h e
o p t i o n of i n c o r p o r a t i n g extensive m i c r o a n a l y t i c a l
facilities.
It h a s also been increasingly c o m m o n t o a t t a c h a n
i m a g e intensifier t o the b a s e of t h e lens c o l u m n a n d t o
send t h e i m a g e t o a T V screen, so t h a t t h e m i c r o s c o p e
user is able t o c a r r y o u t a l i g n m e n t p r o c e d u r e s a n d
a s t i g m a t i s m c o r r e c t i o n s o n i m a g e s a t magnifications
of t h e o r d e r of x 20 000 000. F u r t h e r i n s t r u m e n t a t i o n
d e v e l o p m e n t s in this a r e a h a v e also m e a n t t h a t
H R E M i m a g e s c a n b e fed t o a c o m p u t e r while the
user is still a t t h e m i c r o s c o p e , a n d this h a s led t o t h e
d e v e l o p m e n t of systems for correcting specimen align
m e n t a n d a s t i g m a t i s m on-line. H o w e v e r , it is still the
case for t h e m o s t p a r t t h a t H R E M images a r e
r e c o r d e d o n c o n v e n t i o n a l electron m i c r o s c o p e fast
film a n d it is t h e skill of t h e o p e r a t o r t h a t d e t e r m i n e s
the q u a l i t y of e x p e r i m e n t a l w o r k p r o d u c e d from highr e s o l u t i o n electron m i c r o s c o p e s .

2. Image

Formation

T h e r e a r e t w o principal i m a g i n g m o d e s which a r e
used t o f o r m H R E M images: t h e m a n y - b e a m axiali l l u m i n a t i o n m o d e , in w h i c h t h e undiffracted electron
b e a m is coincident with t h e o p t i c axis of t h e m i c r o
scope, a n d the t w o - b e a m tilted-illumination m o d e , in
which the undiffracted electron b e a m a n d a diffracted
b e a m a r e symmetrically disposed either side of t h e
o p t i c axis (see Fig. 1). In general, t h e axial m o d e of
high-resolution i m a g i n g is t h e o n e used o n the c u r r e n t
g e n e r a t i o n of H R E M s . T h e t i l t e d - b e a m m o d e , w h i c h
w a s used in t h e d e v e l o p m e n t of t h e t e c h n i q u e of highresolution electron m i c r o s c o p y , is n o w s e l d o m used,
a l t h o u g h if care is t a k e n this m o d e c a n give consider
able success.
I m a g e f o r m a t i o n in the H R E M c a n b e t r e a t e d
conveniently by s e p a r a t i n g t h e physical process of
forming a n i m a g e i n t o t w o s e p a r a t e stages m a t h e m a
tically. T h e first stage is t h e scattering b y t h e specimen
of t h e high-energy e l e c t r o n s p r o d u c e d by t h e electron
source. T h i s c a n be described b y t h e d y n a m i c a l t h e o r y
of electron diffraction in which the w a v e function of

Electron

Microscopy,

High-Resolution

T(u) = exp[iX(u)]E(u)

(2)

where
3

= ^ 4

x optic

(4)

a n electron is divided i n t o a linear s u m of Bloch

waves, b u t it is m o r e u s u a l in H R E M i m a g e simula
tion c o m p u t e r p r o g r a m s for t h e scattering of the highenergy electrons t o b e described using t h e multiscale
t h e o r y of electron diffraction. I n t h e multislice a p
p r o a c h , t h e specimen is divided i n t o slices, e a c h of
which modifies t h e w a v e function of t h e electron b y
acting a s a p h a s e object, a n d t h e electron w a v e
p r o p a g a t e s from o n e slice t o t h e next b y Fresnel
diffraction. T h e a m p l i t u d e d i s t r i b u t i o n , F(u) = F(u, ),
in t h e diffraction p a t t e r n of t h e specimen is t h e n t h e
F o u r i e r t r a n s f o r m &\?(x,y)] of t h e a m p l i t u d e distri
b u t i o n of t h e w a v e function (,>>) of electrons after
they h a v e been t r a n s m i t t e d t h r o u g h t h e specimen:
3?[(,)]

= J jV(jc,j>)exp[27n(wx + vy)] dx dy

(3)

(w) = e x p ( - i 7 d A V )

beam

Figure 1
Imaging modes in an HREM: (a) the axial-illumination
mode and (b) the two-beam tilted-illumination mode. In
both (a) and (b) the outline of a suitable objective
aperture is shown

F(u) = F(u, ) =

a n d t h e envelope function E(u) is given by a n expres

sion such a s

axis

transmitted

+ /*

w h e r e C s is t h e spherical a b e r r a t i o n coefficient, is the

w a v e l e n g t h of t h e electrons, AF is t h e defocus of the
objective lens a n d is t e r m e d t h e w i d t h of spread of
defocus which is a c o n s e q u e n c e of t h e c h r o m a t i c
a b e r r a t i o n of t h e objective lens a n d t h e c u r r e n t a n d
voltage instabilities. T o t a k e a c c o u n t of t h e b e a m
divergence a, E(u) c a n be multiplied further b y a
2
function Jx ()/, w h e r e = 2nocu(AF + C%X ) a n d Jl is
the first-order Bessel function. T(u) c a n be multiplied
by a suitable a p e r t u r e function if a n objective a p e r t u r e
is used t o select b e a m s within t h e diffraction p a t t e r n
a n d c a n b e further modified t o t a k e a c c o u n t of
residual a s t i g m a t i s m in t h e objective lens which h a s
n o t been corrected b y t h e m i c r o s c o p e user. T h e ampli
t u d e d i s t r i b u t i o n within t h e i m a g e c a n t h e n be d e
scribed as t h e F o u r i e r t r a n s f o r m of F(u)T(u)\
Vl(x,y)

= nF(u)T(u)]

(5)

U n d e r certain suitable c i r c u m s t a n c e s E q n . (5) c a n be

c o n s i d e r a b l y simplified. If t h e specimen u n d e r obser
v a t i o n is very thin it c a n b e considered t o b e simply a
p h a s e object, modifying t h e w a v e function 0 ( , y) of
a n electron incident o n t h e specimen, so t h a t the wave
function ( , y) o n exit from t h e specimen is of the
form

(1)
( ^ ) =

w h e r e u is t h e spatial frequency in t h e specimen in t h e

p l a n e n o r m a l t o t h e o p t i c axis a n d h a s t h e d i m e n s i o n s
of reciprocal space. T h e s e c o n d stage in t h e i m a g e
f o r m a t i o n process is t h e transfer of i n f o r m a t i o n from
the b a c k focal p l a n e of the objective lens, in w h i c h t h e
diffraction p a t t e r n of the specimen is located, t h r o u g h
t o t h e final i m a g e . It is a t this stage t h a t t h e imperfec
tions of t h e i m a g i n g system a r e t a k e n i n t o a c c o u n t .
T h e function F(u) is multiplied b y a function T(u), so
t h a t t h e a m p l i t u d e d i s t r i b u t i o n in t h e b a c k focal p l a n e
of t h e objective lens is n o t F(u), b u t F(u)T(u). T(u)
m o d u l a t e s t h e a m p l i t u d e s a n d p h a s e s within t h e elec
t r o n diffraction p a t t e r n , t a k i n g i n t o a c c o u n t t h e p h a s e
shifts c a u s e d b y t h e spherical a b e r r a t i o n C s o f t h e
objective lens, t h e defocus AFoi the objective lens a n d
the a t t e n u a t i o n of high spatial frequencies in t h e
a m p l i t u d e d i s t r i b u t i o n c a u s e d b y finite b e a m diver
gence, b y c h r o m a t i c a b e r r a t i o n s in t h e objective lens
a n d b y instabilities in t h e high voltage a n d in t h e lens
c u r r e n t s . A f o r m of T(u) c o m m o n l y used in H R E M
calculations is:

( , ^ ) [ - ^ ( ^ ) ]

= V0(x,y)[l

- ia<p(x,y)]

(6)

w h e r e (p(x,y) is t h e projected p o t e n t i a l of the specimen

a n d E, t o a g o o d a p p r o x i m a t i o n , is t h e accelerating
voltage of the m i c r o s c o p e . If the a m p l i t u d e 0(,y) is
t a k e n t o b e unity, t h e intensity d i s t r i b u t i o n within
a h i g h - r e s o l u t i o n i m a g e I(x,y) =
^^x^y^fix^y)
becomes
I(x,y)

~ 1 + 2(^)*&{(
2

T(u)]}

(7)

neglecting t e r m s of t h e o r d e r of (x,y), a n d where

* in E q n . (7) d e n o t e s a c o n v o l u t i o n o p e r a t i o n . T h e r e
fore, if sin[71(w)] c a n be r e g a r d e d as a c o n s t a n t ( u p t o
t h e limiting resolution of t h e m i c r o s c o p e ) , t h e image
intensity I(x,y) will b e p r o p o r t i o n a l t o t h e projected
p o t e n t i a l (p(x,y) t o t h a t resolution. T h i s simple result
is k n o w n a s t h e w e a k p h a s e object a p p r o x i m a t i o n .
T h u s , u n d e r these c i r c u m s t a n c e s , t h e regions where
a t o m s a r e p r e s e n t a r e i m a g e d a s d a r k c o n t r a s t regions

129

Electron

Microscopy,

High-Resolution

a n d regions b e t w e e n a t o m c o l u m n s a r e i m a g e d as
bright c o n t r a s t regions.
In practice, h o w e v e r , t h e w e a k p h a s e object
a p p r o x i m a t i o n is of limited use. A l t h o u g h there is a
great t e m p t a t i o n t o interpret h i g h - r e s o l u t i o n images
intuitively in t e r m s of projected p o t e n t i a l s a n d u n d e r
circumstances of c o n t r a s t reversal (where a t o m s a r e
i m a g e d as b r i g h t regions) there is n o real s u b s t i t u t e
for detailed i m a g e s i m u l a t i o n s as a function of thick
ness a n d lens defocus. E v e n u n d e r such c o n d i t i o n s
ambiguities c a n still arise in t h e i n t e r p r e t a t i o n of highresolution images if t h e m a t e r i a l is t o o thick (in w h i c h
case inelastic scattering events m a y significantly affect
the form of t h e image) o r if the m a t e r i a l c o n t a i n s
n o n p e r i o d i c detail.

3. Microscope

Resolution

F r o m c o n s i d e r a t i o n of h o w the i m a g e is f o r m e d in a
t r a n s m i s s i o n electron m i c r o s c o p e it is clear t h a t the
function T(u) will c o n t a i n t e r m s t h a t a r e d e p e n d e n t o n
the electron optical p e r f o r m a n c e of a n R E M . H e n c e
the b e h a v i o r of T(u) as a function of u for different
defocus values c a n be used t o c h a r a c t e r i z e t h e electron
optical p e r f o r m a n c e of a p a r t i c u l a r R E M . I n p r a c
tice, it is c o m m o n t o p l o t t h e function ()
as a
function of u for different defocus values AF, with o r
w i t h o u t the envelope function E{u). T h e curves p r o
d u c e d in this m a n n e r a r e t e r m e d c o n t r a s t transfer
functions ( C T F s ) . T h e o p t i m u m o p e r a t i n g c o n d i t i o n s
for a p a r t i c u l a r H R E M are usually t a k e n t o be a t
values of defocus w h e r e the C T F h a s a r e a s o n a b l y
c o n s t a n t value over a wide r a n g e of spatial frequen
cies. Of p a r t i c u l a r i m p o r t a n c e a r e t h e values of defo
cus k n o w n as " e x t e n d e d Scherzer d e f o c u s , " a t w h i c h
AF = - 1.5*CSU*, a n d " e x t e n d e d s e c o n d b r o a d b a n d
d e f o c u s , " a t which AF= - 3.5*C SU*. T h e t e r m
" S c h e r z e r d e f o c u s " d e n o t e s a value of defocus AF
o f - C s U . Typical C T F s for a state-of-the-art
400 keV H R E M are s h o w n in Fig. 2.
T h e r e is n o simple definition of t h e " p o i n t - t o p o i n t " resolution of a n H R E M . T h e
instrumental
resolution c a n b e t a k e n t o be t h e inverse of t h e spatial
frequency a t w h i c h t h e value of t h e envelope function
2
E(u) falls t o e~ . T h i s i n s t r u m e n t a l r e s o l u t i o n will
often be far s u p e r i o r to 3^0.64 C SU*, the inverse of
the spatial frequency a t which t h e C T F crosses t h e
h o r i z o n t a l axis a t e x t e n d e d Scherzer defocus which is
often t a k e n as a m e a s u r e of t h e interpretable
resolu
tion of a m i c r o s c o p e , b e c a u s e of t h e difficulty of
interpreting accurately i n f o r m a t i o n within t h e s t r o n g
oscillations of t h e C T F a t high spatial frequencies.
O t h e r definitions of i n t e r p r e t a b l e r e s o l u t i o n use the
value ( 5 ~ 0 . 7 0 7 C S U * a t which t h e C T F crosses t h e
h o r i z o n t a l axis a t Scherzer defocus o r the value
(5 ~ 0.67 C SU* c o r r e s p o n d i n g t o t h e higher spatial fre
q u e n c y of the " p a s s b a n d " a t e x t e n d e d Scherzer defo
cus a t which sin h a s a value of 1 /yjl.

130

Figure 2
CTFs for a 400 keV microscope: (a) at extended Scherzer
defocus and (b) at a defocus of - 114 nm. The microscope
parameters used were a C $ of 1 mm. of 3 nm and of
20 mrad, for which extended Scherzer defocus is
-49.6nm

4. Experimental

Conditions

T h e c o n d i t i o n s c u r r e n t l y used in m o s t H R E M experi
m e n t s a r e t h o s e of axial i l l u m i n a t i o n . I n this m o d e t h e
specimen is tilted in such a w a y t h a t t h e a r e a u n d e r
investigation is o r i e n t e d so t h a t t h e incident electron
b e a m is a c c u r a t e l y aligned a l o n g a low index direc
tion. T h e b e a m tilt is t h e n adjusted t o m a k e t h e
incident electron b e a m c o m e d o w n t h e o p t i c axis of
t h e m i c r o s c o p e . F a i l u r e t o d o this a d j u s t m e n t a s
precisely as possible will h a v e t h e effect of i n t r o d u c i n g
a n t i s y m m e t r i c p h a s e shifts i n t o t h e diffracted b e a m s

Electron

a n d this c a n i n t r o d u c e c o n s i d e r a b l e s p u r i o u s detail
i n t o a n H R E M i m a g e as well as lowering t h e expected
s y m m e t r y of t h e i m a g e . It is u s u a l t o d o t h e b e a m
a l i g n m e n t in c o n j u n c t i o n w i t h t h e a s t i g m a t i s m c o r r e c
tion for the objective lens so t h a t w h e n these h a v e
been d o n e correctly the c o n t r a s t from a n y thin layers
of a m o r p h o u s c o n t a m i n a t i o n is extremely h a r d t o
observe a t G a u s s i a n focus (for w h i c h AF= 0), even if
a n i m a g e is seen o n a T V screen t h r o u g h a n i m a g e
intensifier system. It is also s t a n d a r d practice, p a r t i c u
larly for beam-sensitive m a t e r i a l s , t o d o these tilt a n d
astigmatism corrections on an area somewhat away
from the a r e a t o b e p h o t o g r a p h e d to m i n i m i z e speci
m e n c o n t a m i n a t i o n a n d d e g r a d a t i o n . Specimens used
for H R E M e x a m i n a t i o n h a v e t o be thin, even b y
t r a n s m i s s i o n electron m i c r o s c o p y s t a n d a r d s , a n d al
t h o u g h it is often possible t o o b t a i n g o o d q u a l i t y
H R E M i m a g e s from specimens 100 n m thick, it is
m o r e u s u a l to try a n d e x a m i n e specimens less t h a n
20 n m thick, if only b e c a u s e of t h e difficulties in
interpreting H R E M i m a g e s from thicker specimens.
In practice, this m e a n s t h a t t h e edges of specimens a r e
used for H R E M e x a m i n a t i o n a n d hence c a r e m u s t b e
t a k e n n o t t o i n t r o d u c e artifacts from specimen p r e p
a r a t i o n o r specimen e x a m i n a t i o n i n t o these a r e a s .

5.

Applications

F r o m t h e p r e c e d i n g discussion it is a p p a r e n t t h a t
t r a n s m i s s i o n electron m i c r o s c o p e s c a n readily p r o
duce images t h a t c o n t a i n i n f o r m a t i o n a t t h e a t o m i c
level, t h a t is, of t h e o r d e r of a t o m i c spacings within
b o t h crystalline a n d a m o r p h o u s m a t e r i a l . H o w e v e r , it
is also a p p a r e n t t h a t this i n f o r m a t i o n need n o t be
readily i n t e r p r e t a b l e in t e r m s of projected p o t e n t i a l s
of crystal s t r u c t u r e s , b e c a u s e of t h e w a y in w h i c h the
i n s t r u m e n t a l p a r a m e t e r s of t h e m i c r o s c o p e affect t h e
intensity d i s t r i b u t i o n within t h e H R E M i m a g e .
A g o o d e x a m p l e of this difficulty is t h e i n t e r p r e
t a t i o n of H R E M i m a g e s from [110] z o n e s in silicon.
Silicon h a s t h e d i a m o n d c u b i c s t r u c t u r e , in w h i c h
a t o m s a t (0,0,0) a n d (i,i,i) a r e 0.235 n m a p a r t . In a
[110] z o n e this m e a n s t h a t t h e m o s t closely spaced
a t o m c o l u m n s a r e 0.136 n m a p a r t . In the m a j o r i t y of
published [110] H R E M i m a g e s of silicon these a t o m
c o l u m n p a i r s a p p e a r t o g e t h e r either as b r i g h t b l o b s
( u n d e r c o n d i t i o n s of reversed c o n t r a s t ) o r as t h e d a r k
regions between b r i g h t b l o b s . H o w e v e r , in t h e late
1970s [110] images from silicon were published in
which these white blobs a p p e a r e d as d u m b b e l l s a n d
since the distance between the centers of the t w o p a r t s
of the d u m b b e l l s a p p e a r e d t o b e 0 . 1 3 6 n m , these im
ages were interpreted as being true " a t o m i c " images of
silicon in the [110] direction, even t h o u g h they were
p r o d u c e d in microscopes t h a t h a d interpretable p o i n t to-point resolutions of between 0.2 n m a n d 0.3 n m . It
was s o o n realized t h a t the distance between the centers
of the d u m b b e l l s varied as a function of specimen

Microscopy,

High-Resolution

thickness a n d objective lens defocus a n d t h a t the

distances seen in the published m i c r o g r a p h s were
actually significantly larger t h a n 0.136 n m . T h e d u m b
bells were therefore the result of a n imaging artifact.
However, with the a d v e n t of 400 keV H R E M s with
resolutions at Scherzer defocus of the o r d e r of 0.16 n m ,
it h a s been possible t o o b t a i n true " a t o m i c " images
from silicon in the [110] direction by carefully selecting
defocus values in which the i m p o r t a n t reflections in the
H R E M image all h a v e sin / positive, in which case the
d u m b b e l l s can indeed c o r r e s p o n d to a t o m i c c o l u m n s
u n d e r conditions of reversed c o n t r a s t . A n example of
such image is s h o w n in Fig. 3.
T h i s relatively simple e x a m p l e therefore d e m o n
strates the p o w e r of t h e H R E M in o b t a i n i n g images
with a t o m i c level i n f o r m a t i o n , b u t also s h o w s the
limitations of t h e i n t e r p r e t a t i o n of these images in
t e r m s of projected p o t e n t i a l s of even perfect crystal
line m a t e r i a l s u n d e r c o n d i t i o n s of perfect axial illumi
n a t i o n . H o w e v e r , if d u e c a u t i o n is t a k e n in image
i n t e r p r e t a t i o n , H R E M s c a n be used t o great a d v a n
tage t o o b t a i n s t r u c t u r a l i n f o r m a t i o n which is a l m o s t
impossible t o o b t a i n directly b y o t h e r m e a n s . A g o o d
e x a m p l e of this is t h e w a y in w h i c h H R E M s h a v e been
used in c o n j u n c t i o n with t e c h n i q u e s such as nuclear
m a g n e t i c r e s o n a n c e s p e c t r o s c o p y a n d s y c h r o t r o n xr a y diffraction t o investigate t h e a t o m i c s t r u c t u r e of
zeolites. T h e s e a r e a family of m a t e r i a l s t h a t c a n
s e p a r a t e c o m p l e x m o l e c u l a r m i x t u r e s by acting as
sieves t h r o u g h w h i c h molecules below a certain size
c a n p a s s by diffusing d o w n o p e n c h a n n e l s in the
zeolite s t r u c t u r e . T h e size of these c h a n n e l s is there
fore of critical i m p o r t a n c e in allowing t h e zeolites t o
s e p a r a t e p a r t i c u l a r m o l e c u l a r m i x t u r e s a n d , since the
size a n d frequency of these c h a n n e l s c a n b e m a r k e d l y
affected b y defects a n d i n t e r g r o w t h s in the zeolites, it
is vitally i m p o r t a n t t o be able t o characterize fully
n e w synthetic m o l e c u l a r sieves d e v e l o p e d by inor
g a n i c chemists. In this a r e a t h e use of H R E M s is a
v a l u a b l e t e c h n i q u e for establishing t h e size of c h a n
nels a n d t h e effect of i n t e r g r o w t h s o n t h e catalytic
ability of a p a r t i c u l a r zeolite.
F u r t h e r e x a m p l e s of the use of H R E M s c a n be
illustrated by c o n s i d e r i n g t h e i n f o r m a t i o n which c a n
be usefully o b t a i n e d from m i c r o g r a p h s such as t h o s e
in Figs. 4 a n d 5. T h i n platelike precipitates o n {111}
p l a n e s of t h e m a t r i x a l u m i n u m in a l u m i n u m - c o p p e r
alloys w i t h t r a c e elements m a g n e s i u m a n d silver cause
s t r o n g s t r e a k i n g in electron diffraction p a t t e r n s from
these alloys, similar t o the s t r e a k i n g f o u n d from
platelike p r e c i p i t a t e s of A l 2 C u L i in A l - L i - C u - M g
alloys (see Electron Diffraction). A l 2 C u L i h a s a hex
a g o n a l crystal s t r u c t u r e a n d this gives rise t o four
distinct p r e c i p i t a t e v a r i a n t s in A l - L i - C u - M g alloys,
o n e v a r i a n t o n e a c h set of {111} p l a n e s . T h u s , from the
electron diffraction i n f o r m a t i o n a l o n e it is t e m p t i n g t o
assign a h e x a g o n a l crystal s t r u c t u r e t o t h e precipi
tates. H o w e v e r , use of a n H R E M s h o w s u n a m b i
g u o u s l y t h a t t h e precipitates c a n n o t be h e x a g o n a l

131

Electron

Microscopy,

High-Resolution

Figure 3
[110] "atomic" image from silicon taken with a 400 keV HREM. This photograph has been enhanced by photographic
averaging in order to eliminate random noise from the image. The specimen thickness was 15 nm and the objective lens
defocus - 114 nm with a C s of 1 mm, of - 3 nm and of 20 mrad (courtesy of J. L. Hutchinson)

because of the distinct forms of i m a g e which c a n

occur from different precipitates o n the s a m e set of
{111} p l a n e s (see Fig. 4). Simple i m a g e s i m u l a t i o n s
confirm t h a t t h e precipitates h a v e a n o r t h o r h o m b i c
s t r u c t u r e which is a d i s t o r t e d f o r m of t h e crystal
s t r u c t u r e of A l 2 C u . H o w e v e r , t o be able t o assess the
role of b o t h m a g n e s i u m a n d silver in d e t e r m i n i n g
precipitation of precipitates a n d t o be able t o fully
characterize t h e p r e c i p i t a t e - m a t r i x interfacial struc
t u r e is m u c h m o r e of a challenge. T h e use of H R E M s
is n o t sufficiently chemically sensitive to be able t o
t a k e a c c o u n t of trace a t o m c o n c e n t r a t i o n s , a n d t h e
very existence of a n interface a n d its associated struc
t u r a l relaxations i n t r o d u c e s a d d i t i o n a l i n f o r m a t i o n in
reciprocal space w h i c h will m o d u l a t e each diffraction
s p o t present. A s a result, it is a l m o s t impossible t o
interpret the i n f o r m a t i o n p r e s e n t in a t h r o u g h - f o c a l

132

sequence of H R E M i m a g e s in t e r m s of a u n i q u e
s t r u c t u r a l m o d e l of t h e interface.
T h e s t r u c t u r e of m o d u l a t e d m a t e r i a l s c a n be use
fully o b s e r v e d in a n H R E M b y deliberately u s i n g
n o n a x i a l b r i g h t field i m a g i n g c o n d i t i o n s , in which t h e
b e a m s used t o f o r m t h e i m a g e a r e symmetrically
d i s p o s e d a b o u t t h e o p t i c axis. I n t h e e x a m p l e s h o w n
in F i g . 5, t h e 000, 002, 020 a n d 022 b e a m s from C u N i P d m u l t i l a y e r s of 4.4 n m w a v e l e n g t h h a v e b e e n
symmetrically disposed a b o u t t h e o p t i c axis. T h i s
results in a sequence of m i c r o g r a p h s in which there
a r e clear m o d u l a t e d fringe spacings in t h e [001] direc
tion, w h e r e a s for axial i l l u m i n a t i o n t h e periodicity of
t h e m o d u l a t i o n s is h i d d e n in t h e r a p i d oscillations of
t h e C T F . Intensity profiles from n o n a x i a l m i c r o
g r a p h s such as Fig. 5 c a n b e used t o assess t h e
variability of fringe spacings parallel a n d p e r p e n d i c u -

Electron

Microscopy,

Fringe

High-Resolution

number

mean spacing = 6.57 pixels

(a)

1.5
a

(020)

Figure 4
High-resolution electron micrograph of two platelike
precipitates on (111) planes of the matrix aluminum in an
Al-Cu-Mg-Ag alloy. The electron beam is parallel to
[311] of the face-centered-cubic aluminum

lar t o the [001] g r o w t h direction in these m u l t i l a y e r s

(see Fig. 6). By e x a m i n i n g e x p e r i m e n t a l l y o b s e r v e d
fringe spacings from m u l t i l a y e r s of different w a v e
lengths a n d c o r r e l a t i n g these spacings with spacings
inferred from i m a g e s i m u l a t i o n s it is possible t o
d e d u c e t h e existence of w a v e l e n g t h - d e p e n d e n t s t r u c
t u r a l c h a n g e s in these m a t e r i a l s . A g a i n , it is necessary
t o d o detailed i m a g e s i m u l a t i o n s , b e c a u s e there is n o t
a o n e - t o - o n e c o r r e l a t i o n b e t w e e n t h e fringe spacings
m e a s u r e d o n H R E M m i c r o g r a p h s a n d t r u e interplan a r spacings, b u t w h e n this h a s been d o n e , as in this

Fringe

pixels

(b)

Figure 6
Deviations from the line of least-squares fit of fringe
positions measured from intensity profiles of the specimen
shown in Fig. 5: (a) parallel to the [001] growth direction
and (b) perpendicular to the [001] growth direction. The
mean spacings given in pixels are those of the (002) and
(020) lattice planes and would correspond to
approximately 0.18 nm in pure copper (courtesy of
C. S. Baxter)

e x a m p l e , t h e i n t e r p r e t a t i o n c a n b e used with confi

dence.
T h e s e e x a m p l e s therefore d e m o n s t r a t e t h e w a y in
w h i c h h i g h - r e s o l u t i o n electron m i c r o s c o p y c a n be
used for m a t e r i a l s p r o b l e m s , b u t they also reinforce
t h e need t o d o detailed i m a g e s i m u l a t i o n s t o s u p p o r t
any image interpretation. M o s t image simulation
p a c k a g e s c u r r e n t l y available c a t e r only for periodic
b o u n d a r y c o n d i t i o n s a n d so they c a n n o t readily t a k e
a c c o u n t of n o n p e r i o d i c detail, such as t h a t f o u n d in
a m o r p h o u s m a t e r i a l s a n d in t h e vicinity of interfaces
a n d line defects, w i t h o u t lengthy c a l c u l a t i o n s t o a v o i d
" e d g e effects" in t h e s i m u l a t i o n s . F u r t h e r m o r e , they
d o n o t deal a d e q u a t e l y with t h e effect of inelastic
s c a t t e r i n g o n H R E M i m a g e s a n d this m e a n s in p a r
ticular t h a t H R E M images from thicker crystals t e n d
t o c o n t a i n i n f o r m a t i o n t h a t is u n i n t e r p r e t a b l e .

6. Future
Figure 5
A nonaxial high-resolution image of a Cu-NiPd
multilayer sample showing modulated fringe spacings
(courtesy of C. S. Baxter)

number

mean spacing = 6.63

Developments

It is likely t h a t t h e m o s t i m p o r t a n t a d v a n c e s in highr e s o l u t i o n electron m i c r o s c o p y will c o m e n o t from

i m p r o v e m e n t s in v o l t a g e a n d c u r r e n t stabilities, n o r
from i m p r o v e m e n t s in electron lens designs because
t h e designs of lenses a r e a l r e a d y very sophisticated.

133

Electron

Microscopy,

High-Resolution

Instead, i m p r o v e m e n t s will c o m e from the d e v e l o p

m e n t of u l t r a h i g h - v a c u u m specimen e n v i r o n m e n t s
a n d from t h e increased r a n g e of auxiliary e q u i p m e n t
t h a t c a n be used, such as t h e r o u t i n e use of on-line
i m a g e processing a n d t h e use of s p e c t r o m e t e r s for
energy filtering of h i g h - r e s o l u t i o n i m a g e s so t h a t t h e
resultant i m a g e only includes c o n t r i b u t i o n s from elastically scattered electrons. F u r t h e r d e v e l o p m e n t s c a n
also be a n t i c i p a t e d in t h e u n d e r s t a n d i n g of h o w
inelastically scattered electrons c a n b e used profitably
t o o b t a i n chemical i n f o r m a t i o n a t a n a t o m i c level; a t
present such electrons c o n t r i b u t e t o the b l u r r i n g of
detail in H R E M images, b u t their precise c o n t r i b u
tion is still p o o r l y u n d e r s t o o d .
See also: Electron Diffraction; Electron Microscopy, HighVoltage; Transmission Electron Microscopy: ConvergentBeam and Microdiffraction Techniques

Bibliography
Baxter C S, Stobbs W 1986 High-resolution lattice
imaging reveals a "phase transition" in Cu/NiPd multi
layers. Nature (London) 322: 814-16
Bovin J-O, Wallenberg R, Smith D J 1985 Imaging of
atomic clouds outside the surface of gold crystals by
electron microscopy. Nature (London) 317: 47-9
Clarke D R 1979 High-resolution techniques and applica
tions to nonoxide ceramics. / . Am. Ceram. Soc. 62: 23646
Cowley J M, Smith D J 1987 The present and future of highresolution electron microscopy. Acta Crystallogr. Sect. A
43: 737-51
Fujita F E, Hirabayashi 1986 High-resolution electron
microscopy. In: Gonser U (ed.) 1986 Microscopic Meth
ods in Metals. Springer, Berlin, pp. 29-74
Goodman P, Moodie A F 1974 Numerical evaluation of Nbeam wave functions in electron scattering by the multislice method. Acta Crystallogr. Sect. A 30: 280-90
Kilaas R, Gronsky R 1985 The effect of amorphous surface
layers on images of crystals in high-resolution electron
microscopy. Ultramicroscopy 16: 193-202
Self G, O'Keefe A, Buseck R, Spargo A C 1983
Practical computation of amplitudes and phases in elec
tron diffraction. Ultramicroscopy 11: 35-52
Smith D J 1989 Instrumentation and operation for highresolution electron microscopy. In: Mulvey T, Sheppard
C J R (eds.) 1989 Advances in Optical and Electron
Microscopy, Vol. 11. Academic Press, London, pp. 1-55
Smith D J, Saxton W O, O'Keefe A, Wood G J, Stobbs
W 1983 The importance of beam alignment and crystal
tilt in high-resolution electron microscopy. Ultramicros
copy 11: 263-82
Spence J C 1988 Experimental High-Resolution Electron
Microscopy, 2nd edn. Oxford University Press, Oxford
Stobbs W M, Saxton W 1988 Quantitative highresolution transmission electron microscopy: the need
for energy filtering and the advantages of energy-loss
imaging. J. Microsc. (Oxford) 151: 171-84
Stobbs W M, Wood G J, Smith D J 1985 The measurement
of boundary displacements in metals. Ultramicroscopy 14:
145-54

134

Thomas J M, Vaughan D W 1989 Methodologies to

establish the structure and composition of new zeolitic
molecular sieves. J. Phys. Chem. Solids 50: 449-67
Ultramicroscopy 18 1985 Proceedings of the Arizona State
University Centennial Symposium on High-Resolution
Electron Microscopy
. M. Knowles
[University of C a m b r i d g e ,
Cambridge, UK]

Electron Microscopy, High-Voltage

T h e electron m i c r o s c o p y of m a t e r i a l s using a m u c h
higher accelerating p o t e n t i a l t h a n t h a t e m p l o y e d in
c o n v e n t i o n a l electron m i c r o s c o p y is t e r m e d highvoltage electron m i c r o s c o p y . T h e r e is n o u n i q u e
t r a n s i t i o n b e t w e e n the t w o ; indeed the " s t a n d a r d "
o p e r a t i n g voltage in t r a n s m i s s i o n electron m i c r o s
c o p y ( T E M ) h a s risen t o include 200 k V i n s t r u m e n t s
a n d , in recent years, a new class of " m e d i u m v o l t a g e "
m i c r o s c o p e s h a s been d e v e l o p e d , e m p l o y i n g acceler
a t i n g p o t e n t i a l s in t h e r a n g e 3 0 0 - 4 0 0 k V . " H i g h vol
t a g e " in this c o n t e x t is therefore generally t a k e n t o
refer t o accelerating voltages of a b o u t 500 k V a n d
above.
T h e incentives t o m o v e t o high o p e r a t i n g voltages
a r e twofold. First, t h e p e n e t r a t i n g p o w e r of t h e elec
t r o n b e a m is increased: the effect is greatest for low
a t o m i c n u m b e r m a t e r i a l s , a n d between 100 k V a n d
1000 k V there is a threefold t o sixfold increase in
p e n e t r a t i o n . Specimen p r e p a r a t i o n is r e n d e r e d less
critical a n d m o r e representative m i c r o s t r u c t u r e s c a n
be studied, especially in m a t e r i a l s c o n t a i n i n g large
s e c o n d - p h a s e particles which m a y either n o t thin o r
d r o p o u t of foils t r a n s p a r e n t t o 100 k V electrons, a n d
in m a t e r i a l s with s t r u c t u r a l features of b r o a d spatial
extent such as electronic devices. T h e v o l u m e - t o surface r a t i o of the s a m p l e is also increased. T h e latter
p o i n t is very i m p o r t a n t since the surfaces often d o m
inate t h e p r o p e r t i e s of very thin foils a n d it is n o t
possible t o o b t a i n b u l k typical b e h a v i o r in experi
m e n t s c o n d u c t e d in situ: in t h e high-voltage m i c r o
scope such e x p e r i m e n t s b e c o m e feasible.
Second, t h e electron w a v e l e n g t h d e p e n d s o n
accelerating voltage: a t 100 k V t h e wavelength is
0.0037 n m while at 1000 k V it is only 0.00087 n m . If
the coefficient of spherical a b e r r a t i o n of the objective
lens of t h e m i c r o s c o p e cs is c o n s t a n t , the u l t i m a t e
r e s o l u t i o n defined b y t h e e q u a t i o n

is increased b y a factor of a b o u t three. T h e a t t a i n a b l e

increase is, in practice, r a t h e r smaller b u t c a n be
exploited in very thin s a m p l e s a n d is the basis for
high-resolution, high-voltage m i c r o s c o p y .
I n foils thick e n o u g h for in situ e x p e r i m e n t s the
practical r e s o l u t i o n is lower as a result of o v e r l a p of

Electron

i m a g e i n f o r m a t i o n t h r o u g h t h e thickness of t h e s a m
ple. In very thick specimens t h e r e s o l u t i o n is l o w e r a s
a c o n s e q u e n c e , principally, of t h e loss in i m a g e c o n
trast i n t r o d u c e d b y electron-energy-loss processes
a l o n g t h e electron p a t h t h r o u g h t h e s a m p l e . A d d i t i o n
ally, a large (several centimeters) objective-lens p o l e piece g a p is desirable t o a c c o m m o d a t e t h e specimen
stages, a n d c o n s e q u e n t l y t h e coefficient of spherical
a b e r r a t i o n is increased a n d r e s o l u t i o n is decreased.
A t h i r d c o n s i d e r a t i o n is t h a t of r a d i a t i o n d a m a g e .
In n o n c o n d u c t i n g m a t e r i a l s , i o n i z a t i o n d a m a g e a t
low accelerating voltages c a n be severe; crystallinity
a n d m i c r o s t r u c t u r e c a n b e d e s t r o y e d so r a p i d l y t h a t
their s t u d y is extremely difficult. T h e severity of t h e
d a m a g e decreases as t h e i o n i z a t i o n cross sections of
the a t o m s in t h e s a m p l e decrease with increasing
e l e c t r o n - b e a m v o l t a g e . H o w e v e r , as t h e accelerating
voltage rises t h e increasing electron energy eventually
reaches a value w h e r e a n e l e c t r o n - a t o m collision c a n
result in t h e d i s p l a c e m e n t of t h e a t o m from its e q u i
librium site. T h i s f o r m of r a d i a t i o n d a m a g e is d i s a d
v a n t a g e o u s t o t h e s t u d y of m i c r o s t r u c t u r e a n d t o in
situ e x p e r i m e n t s b u t o p e n s u p t h e direct s t u d y of
displacement d a m a g e processes w h i c h c a n s i m u l a t e ,
for e x a m p l e , t h e processes w h i c h o c c u r in n u c l e a r
reactors.

1. The

Instrument

T h e m o s t o b v i o u s d i s t i n g u i s h i n g feature of a highvoltage electron m i c r o s c o p e is its sheer physical size.

U s u a l l y t h e entire m a c h i n e is m o r e t h a n twice t h e
height of a typical r o o m a n d is similarly scaled u p
from 100 k V i n s t r u m e n t s in its o t h e r d i m e n s i o n s . T h e
r e a s o n s for this a r e discussed below.
T h e optical system of a h i g h - v o l t a g e electron
m i c r o s c o p e ( H V E M ) is essentially t h e s a m e as t h a t of
a c o n v e n t i o n a l T E M a l t h o u g h t h e lenses a r e larger.
T h i s is a necessary c o n s e q u e n c e of t h e fact t h a t t h e
field s t r e n g t h in a lens is limited b y t h e s a t u r a t i o n
m a g n e t i z a t i o n of t h e soft-iron p o l e pieces e m p l o y e d .
A longer p a t h t h r o u g h t h e field m u s t be e m p l o y e d t o
p r o v i d e sufficient focusing p o w e r t o c o p e with t h e
very-high-energy electrons a n d a physically larger lens
is t h u s r e q u i r e d . C o l u m n d i a m e t e r is further increased
by t h e need for m u c h g r e a t e r x-ray shielding t o
p r o t e c t t h e o p e r a t o r , a s t h e h i g h - e n e r g y b e a m excites
c o r r e s p o n d i n g l y h i g h e r energy ( a n d h e n c e m o r e p e n e
trating) r a y s via inelastic collisions with t h e s a m p l e
a n d t h e i n t e r i o r of t h e m i c r o s c o p e .
A m a j o r difference from c o n v e n t i o n a l T E M is t h e
electron s o u r c e . U p t o a b o u t 300 k V a simple cable
feed from t h e h i g h - v o l t a g e g e n e r a t o r c a n b e
e m p l o y e d . A b o v e this, i n s u l a t i o n b r e a k d o w n b e c o m e s
a m a j o r p r o b l e m a n d a cable s u p p l y is n o t practical.
I n s t e a d , a c o n v e n t i o n a l electron g u n o p e r a t i n g a t
a b o u t 100 k V is directly c o n n e c t e d t o a n a c c e l e r a t o r
t u b e in w h i c h t h e p o t e n t i a l is s t e p p e d in, typically,

Microscopy,

High-

Voltage

100 k V i n c r e m e n t s . T h e facility t o v a r y o n e step

c o n t i n u o u s l y from 0 t o 100 k V is generally i n c o r p o r
a t e d so t h a t a n y accelerating p o t e n t i a l from zero t o
t h e m a x i m u m a t t a i n a b l e c a n be selected. T h i s facility
is very i m p o r t a n t in c o n t r o l l i n g t h e r a d i a t i o n - d a m a g e
processes w h i c h c a n o c c u r in t h e specimen (see Sect.
5). T h e h i g h - v o l t a g e g e n e r a t o r a n d accelerator sys
t e m s a r e usually electrically insulated from t h e en
v i r o n m e n t b y sealing t h e m in t a n k s c o n t a i n i n g a n
i n s u l a t i n g gas (sulfur hexafluoride).
T h e use of a n a c c e l e r a t o r t u b e results in a very tall
s t r u c t u r e w h i c h requires c o n s t r u c t i o n of l a b o r a t o r y
s p a c e w i t h greatly increased h e a d r o o m . T h e m e c h a n i
cal stability of such a s t r u c t u r e is of great i m p o r t a n c e ,
p a r t i c u l a r l y in t h e case of h i g h - r e s o l u t i o n instru
m e n t s , a n d e n s u r i n g f r e e d o m from m e c h a n i c a l
v i b r a t i o n g e n e r a t e d either externally o r within the
m i c r o s c o p e a n d its p u m p i n g system is essential. T h i s
c a n be a serious m e c h a n i c a l engineering p r o b l e m .
T h e s e factors a d d greatly t o t h e cost of the H V E M
w h i c h typically increases in direct p r o p o r t i o n t o the
accelerating p o t e n t i a l . A s a result, t h e n u m b e r of
these m a c h i n e s installed w o r l d w i d e is small ( < 50).

2. Image

and Diffraction-Pattern

Formation

A g a i n t h e H V E M is essentially similar t o t h e c o n v e n
t i o n a l T E M in its f o r m a t i o n of i m a g e s a n d diffraction
p a t t e r n s . Because of the smaller electron wavelength,
t h e B r a g g angles for diffraction of t h e electrons from
crystal lattices a r e greatly r e d u c e d . T h i s h a s several
important consequences.
First, it is unlikely t h a t " t w o - b e a m " c o n d i t i o n s c a n
b e established. T h i s is t h e s i t u a t i o n w h e r e only o n e
diffracted b e a m is strongly excited in a d d i t i o n t o t h e
t r a n s m i t t e d electron b e a m . I n 100 k V i n s t r u m e n t s
w h e r e t h e B r a g g angles a r e m u c h larger this c o n d i t i o n
c a n readily b e achieved b y tilting t h e specimen t o set a
single set of p l a n e s t o t h e B r a g g angle a n d i n t e r p r e
t a t i o n of i m a g e c o n t r a s t is m a d e relatively straightfor
w a r d . I n h i g h - v o l t a g e m a c h i n e s t h e best t h a t c a n
usually b e m a n a g e d is t o set t h e tilt so t h a t a " s y s t e m
atic r o w " of diffraction m a x i m a a r e o b t a i n e d (i.e.
diffraction is s t r o n g l y excited from h k I, 2h 2k 21,
..., nhnknl p l a n e s ) . Diffraction c o n t r a s t is neces
sarily m o r e c o m p l e x a n d c o m p u t e r calculation of
c o n t r a s t is a d v i s a b l e for detailed i m a g e i n t e r p r e t a t i o n .
S e c o n d , diffracted intensities v a r y with t h e acceler
a t i n g p o t e n t i a l e m p l o y e d so t h a t t h e o r i e n t a t i o n s
yielding greatest t r a n s m i s s i o n ( a n d h e n c e p e n e t r a t i o n )
alter so t h a t t h e o r i e n t a t i o n c h o s e n for o p t i m u m
o b s e r v a t i o n m u s t be adjusted. A t s o m e "critical vol
t a g e " t h e diffracted intensity of a c h o s e n reflection
falls t o a m i n i m u m . T h i s critical voltage c a n be
a c c u r a t e l y m e a s u r e d a n d t h e value e m p l o y e d t o calcu
late t h e electron density in t h e specimen a n d hence,
for e x a m p l e , t h e electron scattering factors, a n d in
b i n a r y systems, t h e local chemical c o m p o s i t i o n .

135

Electron

Microscopy,

High-

Voltage

T h i r d , a n d of lesser i m p o r t a n c e , t h e diffracted
electron b e a m s m a k e smaller angles t o t h e m i c r o s c o p e
optical axis t h a n is t h e case a t lower voltages. T h u s
dark-field i m a g e s o b t a i n e d using these n o n a x i a l
b e a m s suffer m u c h r e d u c e d spherical a b e r r a t i o n a n d
c a n often be e m p l o y e d r a t h e r t h a n t h e " h i g h r e s o l u t i o n " dark-field i m a g e s o b t a i n e d b y tilting t h e
incident electron b e a m t o p r o d u c e a n axial diffracted
b e a m . Diffraction p a t t e r n s a r e physically smaller for a
given c a m e r a length in t h e m i c r o s c o p e , so p r o v i s i o n is
m a d e via t h e p r o j e c t o r lens system for increasing this
p a r a m e t e r a t high accelerating voltages t o p e r m i t
easier o b s e r v a t i o n .

3. High-Resolution

Electron

Microscopy

H i g h - r e s o l u t i o n h i g h - v o l t a g e electron m i c r o s c o p e s
a r e d e d i c a t e d i n s t r u m e n t s serving this function a l o n e .
T h e objective lens is a critical c o m p o n e n t of t h e
m i c r o s c o p e a n d is designed t o h a v e t h e m i n i m u m
pole-piece g a p a n d h e n c e m i n i m u m coefficient of
spherical a b e r r a t i o n c o n s i s t e n t w i t h t h e need t o
p r o v i d e space for t h e specimen a n d its tilting (the
latter facility is n e e d e d t o adjust t h e diffraction c o n
ditions u n d e r w h i c h t h e s a m p l e is i m a g e d ) . T h i s d o e s
n o t allow sufficient space for c o m p l e x e x p e r i m e n t a l
stages r e q u i r e d for in situ e x p e r i m e n t s a n d , in a n y
case, t h e specimen thickness r e q u i r e d for m a n y in situ
e x p e r i m e n t s w o u l d p r e c l u d e t h e a t t a i n m e n t of t h e
u l t i m a t e resolution.
T h e a d v a n t a g e , with r e g a r d t o r e s o l u t i o n , of d e
creasing electron w a v e l e n g t h w i t h increasing p o t e n t i a l
is b a l a n c e d against t h e p r o b l e m s of e n s u r i n g electron
source stability, t h e m e c h a n i c a l stability of t h e m i c r o
scope a n d t h e p r o b l e m s c a u s e d b y a t o m i c displace
m e n t s t a k i n g place as a result of e l e c t r o n - a t o m colli
sions. F o r these r e a s o n s , voltages u n d e r 1 M e V a r e
generally e m p l o y e d for t h e h i g h - r e s o l u t i o n studies.
R e s o l u t i o n b e t t e r t h a n 0.2 n m h a s b e e n achieved in
u l t r a t h i n specimens (less t h a n 20 n m thick). E l e c t r o n i c
stability of t h e electron s o u r c e a n d m e c h a n i c a l stabi
lity of the s a m p l e stage a n d t h e m i c r o s c o p e h a v e b e e n
i m p r o v e d t o t h e p o i n t w h e r e d y n a m i c events involv
ing small n u m b e r s of a t o m s c a n be i m a g e d a n d
r e c o r d e d . T h u s , for e x a m p l e , r e s t r u c t u r i n g of crystal
surfaces c a n be directly o b s e r v e d in t h e elec
t r o n m i c r o s c o p e (see Electron Microscopy,
HighResolution).

4. Examination

of Thick

Samples

T h e increased p e n e t r a t i n g p o w e r of high-voltage elec

t r o n m i c r o s c o p e s is utilized, a t lower r e s o l u t i o n , t o
e x a m i n e relatively thick sections of m a t e r i a l . T h i s is a
very s t r a i g h t f o r w a r d a p p l i c a t i o n of t h e H V E M b u t it
is nonetheless a n i m p o r t a n t o n e . Inclusions a n d
s e c o n d - p h a s e particles of m i c r o m e t e r size h a v e a n

136

Figure 1
In situ recrystallization r at a second-phase particle in a
deformed aluminum-silicon alloy; this representative
microstructure could only be observed in foils too thick
for examination by conventional TEM (courtesy of F. J.
Humphreys)

i m p o r t a n t influence o n t h e m e c h a n i c a l p r o p e r t i e s of
engineering m a t e r i a l s , a n d it is necessary t o b e able t o
identify t h e m a n d their m i c r o s t r u c t u r a l s u r r o u n d i n g s ,
including fine-scale features such as local dislocation
s u b s t r u c t u r e . T h e latter m a y be substantially altered
in foils t h i n e n o u g h for s t u d y a t 100 k V a s a result of
d i s l o c a t i o n r e a r r a n g e m e n t a n d loss t o t h e foil sur
faces. F i g u r e 1 illustrates t h e use of t h e H V E M for t h e
s t u d y of b o t h c o a r s e particles a n d dislocation s t r u c
tures. It s h o w s a d e f o r m e d alloy of a l u m i n u m w h e r e
t h e locally increased m i s o r i e n t a t i o n of t h e m a t r i x a t a
s e c o n d - p h a s e particle h a s c r e a t e d t h e c o n d i t i o n s for
t h e n u c l e a t i o n of recrystallization u p o n s u b s e q u e n t
annealing.

5. Radiation

Damage

Processes

and

Experiments

A s n o t e d earlier, t h e d e c r e a s e d i o n i z a t i o n cross sec

tions a s s o c i a t e d with increased electron energies per
m i t longer o b s e r v a t i o n s t o b e m a d e of m a t e r i a l s w h i c h
a r e sensitive t o i o n i z a t i o n d a m a g e , s u c h as m i n e r a l s
a n d p o l y m e r s . O n a v e r a g e t h e o b s e r v a t i o n t i m e is
a b o u t t h r e e times g r e a t e r a t 1 M e V t h a n a t 100 k e V
for t h e s a m e incident electron flux, a l t h o u g h in s o m e
cases m u c h g r e a t e r increases a r e r e p o r t e d . H o w e v e r ,
for t h e s a m e r e a s o n s t h a t longer o b s e r v a t i o n s c a n be
m a d e , t h e p h o t o g r a p h i c r e c o r d i n g of t h e i m a g e also
requires a l o n g e r e x p o s u r e t i m e a n d , in o r d e r t o
m i n i m i z e this, faster a n d thicker p h o t o g r a p h i c e m u l
sions m a y b e utilized. T h e H V E M h a s p r o v e d ex
tremely v a l u a b l e in geological studies a n d in t h e

Electron

Figure 2
Time-lapse sequence of a diffraction pattern of Ni 3Al
showing the fading of {110} superlattice reflections
(arrowed) as electron-displacement damage destroys the
long-range order: (a) 0 s, (b) 50 s and (c) 250 s exposure to
the 1 MeV electron beam (courtesy of J. F. Waiting)

e x a m i n a t i o n of c e r a m i c a n d p o l y m e r i c engineering
m a t e r i a l s . I n metallic systems, t h e i o n i z a t i o n d a m a g e
is rapidly h e a l e d b y t h e s u p p l y of electrons f r o m t h e
c o n d u c t i o n b a n d a n d t h e a d v a n t a g e s of t h e V E M lie
in t h e ability t o e x a m i n e thick sections a n d t o c a r r y
o u t in situ e x p e r i m e n t s . I n t h e latter case (see Sect. 6)
c o n s i d e r a t i o n m u s t b e given t o t h e effects of a s e c o n d
electron i r r a d i a t i o n d a m a g e p r o c e s s t h a t of a t o m i c
displacement.
C o n s i d e r a t i o n of t h e R u t h e r f o r d collision p r o c e s s
involved leads t o t h e following e q u a t i o n for t h e
m a x i m u m energy transfer, Emax (eV), from a n incident
electron t o a t a r g e t a t o m :

m ax

= 2.148 x \03E(E

Microscopy,

High-

Voltage

p e r i o d s in n u c l e a r r e a c t o r s . T h e t w o processes a r e n o t
identical, h o w e v e r , a n d t h e differences m u s t b e c o n
sidered in e x t r a p o l a t i n g f r o m H V E M e x p e r i m e n t s t o
p r e d i c t i o n s for r e a c t o r b e h a v i o r . F o r e x a m p l e , colli
sion d a m a g e c a s c a d e s involving m u l t i p l e k n o c k - o n
events from o n e initial collision d o n o t o c c u r for
electron d a m a g e since t h e displaced a t o m h a s insuf
ficient e n e r g y t o c a u s e this a n d even t h e p r i m a r y
electron h a s a low p r o b a b i l i t y of p r o d u c i n g multiple
d i s p l a c e m e n t s ( a l t h o u g h this increases w i t h increasing
e l e c t r o n energy a b o v e t h e t h r e s h o l d for displace
m e n t ) . A l s o , t h e relative p r o x i m i t y of free surfaces
w h i c h a c t a s point-defect sinks m u s t b e t a k e n i n t o
a c c o u n t , since it will affect t h e m a g n i t u d e of t h e p o i n t defect c o n c e n t r a t i o n d e v e l o p e d d u r i n g i r r a d i a t i o n
a n d t h e p r o d u c t i o n of s e c o n d a r y defects such as
dislocation loops.
T h e temperature at which the experiments are
c o n d u c t e d is also critical since t h e m o b i l i t y of p o i n t
defects varies e x p o n e n t i a l l y w i t h t e m p e r a t u r e : p o i n t defect a n n i h i l a t i o n b y r e c o m b i n a t i o n a n d loss t o sinks
eventually reduces t h e c o n c e n t r a t i o n t o t h e t h e r m a l
e q u i l i b r i u m v a l u e a t a t e m p e r a t u r e w h i c h is a function
of t h e e l e c t r o n - b e a m flux density. T h i s is of consider
able i m p o r t a n c e in t h e i n t e r p r e t a t i o n of in situ experi
ments on phase transformations where displacement
d a m a g e itself a n d e n h a n c e d diffusivity p r o d u c e d b y it
c a n influence t h e stability of s e c o n d - p h a s e particles
a n d their rates of g r o w t h o r d i s s o l u t i o n .

+ 1.022)/M

w h e r e is t h e e l e c t r o n e n e r g y in M e V a n d is t h e
a t o m i c weight of t h e t a r g e t a t o m . A b o v e a critical
value of E, Emax will exceed t h e energy r e q u i r e d t o
displace a n a t o m from its e q u i l i b r i u m site. I n crystal
line m a t e r i a l s this e n e r g y will b e a function of crystall o g r a p h i c direction, a n d t h e o r i e n t a t i o n d e p e n d e n c e
c a n be m e a s u r e d b y in situ i r r a d i a t i o n e x p e r i m e n t s
involving v a r i a t i o n of t h e incident electron energy a n d
the crystal o r i e n t a t i o n relative t o t h e electron b e a m
a n d observing t h e p r o d u c t i o n of point-defect clusters.
A s a result of d i s p l a c e m e n t d a m a g e , large v a c a n c y
a n d interstitial c o n c e n t r a t i o n s c a n d e v e l o p a n d result
in t h e i n f o r m a t i o n of defect clusters a n d d i s l o c a t i o n
l o o p s , t h e degree of l o n g - r a n g e o r d e r c a n b e a l t e r e d
(see F i g . 2, for e x a m p l e ) , modification t o p r e c i p i t a t i o n
reactions c a n o c c u r a n d in e x t r e m e cases crystalline
material can be rendered a m o r p h o u s .
Because very high d i s p l a c e m e n t r a t e s c a n b e
achieved with relatively m o d e s t electron fluxes, t h e
H V E M c a n be used t o investigate t h e d i s p l a c e m e n t
d a m a g e processes w h i c h o c c u r o v e r m u c h l o n g e r t i m e

Figure 3
Time-lapse sequence showing the dissolution of '
particles (arrowed) in an aluminum-copper alloy at
370 C: (a) as the sample reaches temperature, (b) after
1250 s at temperature. Climbing dislocations (for example
at X) visible in the micrographs assist the dissolution
process. The interaction between the dissolution and climb
processes can only be determined by such in situ
experiments in the HVEM (courtesy of P. Hewitt)

137

Electron

Microscopy,

6. In Situ

High-

Voltage

Experiments

In the case of d e f o r m a t i o n studies a n d m a r t e n s i t i c a n d

diffusional p h a s e t r a n s f o r m a t i o n s , the foil thickness
required t o o b t a i n b e h a v i o r w h i c h is essentially typi
cal of b u l k is generally less t h a n t h e practical p e n e t r a
tion limit of the electron b e a m . It is o n e of t h e m a j o r
a d v a n t a g e s of t h e H V E M in m a t e r i a l s science t h a t , as
a c o n s e q u e n c e of this, representative in situ experi
m e n t s c a n be carried o u t . H o w e v e r , care m u s t b e
t a k e n t o m i n i m i z e t h e effects of d i s p l a c e m e n t d a m a g e
which will be greatest at low h o m o l o g o u s t e m p e r a
tures w h e r e the point-defect c o n c e n t r a t i o n s d e v e l o p e d
c a n be m a n y o r d e r s of m a g n i t u d e g r e a t e r t h a n t h e
t h e r m a l e q u i l i b r i u m c o n c e n t r a t i o n . T h u s , processes
such as dislocation climb a n d p r e c i p i t a t e n u c l e a t i o n
a n d g r o w t h c a n be radically altered. U n f o r t u n a t e l y ,
the need for b e a m p e n e t r a t i o n usually r e n d e r s it
impossible t o w o r k below t h e t h r e s h o l d voltage for
d i s p l a c e m e n t d a m a g e a n d o p e r a t i o n a t t h e lowest
possible b e a m intensity a n d highest possible h o m o
logous temperature are required to minimize the
effects of d i s p l a c e m e n t d a m a g e . F i g u r e 3 illustrates
the use of t h e H V E M t o s t u d y p h a s e t r a n s f o r m a t i o n s .
It shows a time lapse sequence of t h e d i s s o l u t i o n of '
particles in a n a l u m i n u m - c o p p e r alloy; from such
sequences, direct m e a s u r e m e n t of kinetics c a n be
m a d e a n d the r a t e - c o n t r o l l i n g step c a n be d e t e r m i n e d .
T h e H V E M is also the ideal i n s t r u m e n t in which t o
c a r r y o u t studies of g a s - s o l i d r e a c t i o n s . T h e large
space available in t h e objective lens pole-piece g a p c a n
be utilized t o create a n e n v i r o n m e n t a l cell such as t h a t
s h o w n in Fig. 4. I n this design, gas is passed i n t o t h e
pole-piece g a p which acts as a large gas reservoir
directly linked t o the specimen a r e a . G a s leaks o u t
from this via t w o small ( ~ 100 ) a p e r t u r e s , aligned
with the o p t i c axis of t h e m i c r o s c o p e , i n t o a small
"differential" c h a m b e r which is separately p u m p e d

Lower pole

piece

Figure 4
Gas reaction cell designed for use in an HVEM: it fits in
the 20 mm objective lens pole-piece gap: in the illustration
a sample holder with a heating stage is shown in the cell
(courtesy of P. R. Swann)

138

Figure 5
Reduction of magnetite to iron, in situ, in an H 2-He
atmosphere in a gas reaction cell in an HVEM. The
porous iron is growing into the oxide along an irregular
growth front. The kinetics of the process can be
determined from time-lapse sequences. The porous iron
product is used as a catalyst in the synthesis of ammonia
(courtesy of G. M. Pennock)

from t h e m i c r o s c o p e c o l u m n . T h i s c h a m b e r is c o n
nected b y t w o further a p e r t u r e s t o t h e m i c r o s c o p e
v a c u u m itself. T h i s differential p u m p i n g system per
m i t s a p r e s s u r e u p t o a t m o s p h e r i c t o b e m a i n t a i n e d in
t h e specimen a r e a w i t h o u t significantly d e g r a d i n g the
microscope vacuum.
T h e specimen stage c a n be e q u i p p e d for tilting,
h e a t i n g , c o o l i n g o r straining t h e specimen a n d t h e
integral objective a p e r t u r e assembly p e r m i t s the use of
all s t a n d a r d i m a g i n g a n d diffraction t e c h n i q u e s . T h e
availability of this e n v i r o n m e n t a l cell h a s p e r m i t t e d a
wide r a n g e of h i g h - t e m p e r a t u r e o x i d a t i o n a n d r e d u c
tion r e a c t i o n s , including t h o s e which o c c u r d u r i n g t h e
p r o d u c t i o n a n d use of catalysts, t o b e studied directly
(Fig. 5).
A s with o t h e r in situ e x p e r i m e n t s , r a d i a t i o n d a m a g e
c a n affect t h e results a n d , since b o t h c o n d u c t o r s a n d
n o n c o n d u c t o r s a r e likely t o be p r e s e n t in these reac
tions, b o t h i o n i z a t i o n a n d d i s p l a c e m e n t d a m a g e m a y
be significant. A t low h o m o l o g o u s t e m p e r a t u r e s this
c a n be exploited t o e n h a n c e r e a c t i o n s w h i c h w o u l d
otherwise be very slow, such as t h o s e b e t w e e n m e t a l s
a n d w a t e r v a p o r . F i g u r e 6 illustrates the use of
e l e c t r o n - b e a m - e n h a n c e d reactivity t o aid the s t u d y of
h y d r o g e n e m b r i t t l e m e n t in a l u m i n u m alloys.
See also: Corrosion and Oxidation Study Techniques
Bibliography
Butler , Hale F 1981 Dynamic experiments in the
electron microscope. In: Glauert A (ed.) 1981 Practical

Electron

Spectroscopy

for Chemical

Analysis

s a m p l e s t h e first 5-20 a t o m i c layers below a surface

a n d is c a p a b l e of detecting s u b m o n o l a y e r q u a n t i t i e s
of all elements except h y d r o g e n a n d helium. Its speci
ficity is g o o d a n d for m o s t m a t e r i a l s of practical
interest t h e r e a r e few spectral o v e r l a p s w h i c h c a u s e
a m b i g u i t y a b o u t elemental c o m p o s i t i o n .
A s a scientific t o o l , E S C A h a s been used t o s t u d y
n u m e r o u s solid-state p r o b l e m s s u c h a s m e c h a n i s m s of
t h e p h o t o a b s o r p t i o n p r o c e s s itself, electron energyloss m e c h a n i s m s in solids, b a n d s t r u c t u r e , surfacerelated b a n d b e n d i n g , a d s o r p t i o n processes a n d a
b r o a d r a n g e of o t h e r p h e n o m e n a . A s a n analytical
t e c h n i q u e , it is r o u t i n e l y used t o c h a r a c t e r i z e surface
constituents on almost any material to determine
wetting, b o n d i n g , w a s h i n g o r electrical p r o p e r t i e s .
Figure 6
In situ sequence showing the nucleation and growth of
hydrogen bubbles at precipitates on the grain boundary in
an age-hardened aluminum alloy. The hydrogen is
produced by the electron-beam-stimulated reaction
between the alloy and water vapor (courtesy of
L. Christodoulou)

Methods in Electron Microscopy, Vol. 9. North-Holland,

Amsterdam
Laidler J J, Mastel 1975 Application of high voltage
electron microscopy to the study of radiation damage in
metals. In: Siegel , Beaman D R (eds.) 1975 Physical
Aspects of Electron Microscopy and Microbeam Analysis.
Wiley, New York, Chap. 7
Swann R 1972 High voltage electron microscope studies of
environmental reactions. In: Thomas G (ed.) 1972 Elec
tron Microscopy and Structures of Materials: Proc. 5th
Ann. Symp. Structure & Properties of Materials. Univer
sity of California Press, San Francisco, CA, pp. 878-904
Thomas G, Goringe J 1979 Transmission Electron
Microscopy of Materials. Wiley, New York
. M . Flower
[Imperial College of Science, T e c h n o l o g y
and Medicine, London, U K ]

Electron Spectroscopy for Chemical

Analysis
Electron s p e c t r o s c o p y for chemical analysis ( E S C A ) ,
o r x-ray p h o t o e l e c t r o n s p e c t r o s c o p y ( X P S ) , as it is
also k n o w n , is a t e c h n i q u e for d e t e r m i n i n g t h e ele
m e n t a l a n d chemical c o m p o s i t i o n of m a t e r i a l sur
faces. T h e m a t e r i a l t o be a n a l y z e d is b o m b a r d e d b y
soft rays ( 1 - 5 keV) a n d electrons p h o t o e m i t t e d b y
the s a m p l e a r e energy-analyzed; s o m e of these elec
t r o n s h a v e discrete energies w h i c h p r o v i d e i n f o r m a
tion a b o u t t h e a t o m s from which they c a m e . T h e
t e c h n i q u e h a s been extensively applied t o solids, al
though liquid-phase a n d gas-phase measurements
h a v e also been m a d e . It h a s b e c o m e a n i m p o r t a n t t o o l
in m a n y scientific a n d technical disciplines. E S C A

1. Characteristics
Technique

of ESCA

as an

Analytical

T a b l e 1 lists a n u m b e r of t h e characteristics of E S C A
a s a n analytical t e c h n i q u e . A n u m b e r of these consti
t u t e p a r t i c u l a r s t r e n g t h s of t h e t e c h n i q u e , in t h a t
E S C A is r e g a r d e d b y m a n y as t h e m e t h o d of choice
for a p p l i c a t i o n s r e q u i r i n g t h o s e features, while o t h e r s
c o n s t i t u t e weaknesses.
M o r e specifically, t h e ability t o o b t a i n chemical
b o n d i n g i n f o r m a t i o n , t o a n a l y z e electrically insulat
ing m a t e r i a l s a s well as c o n d u c t o r s , t o p r o v i d e r e a s o n -

Table 1
Characteristics of ESCA as an analytical technique
Mean analysis depth (nm)
Elemental sensitivity (at.%)

Probe size (mm 2)

Elements detected
Power illuminating sample
(W)
Sample environment
Quantitative accuracy
Measurement precision (%)
Survey analysis time (min)
Sample limitations

Special features

1-4
0.01-0.1 (homogeneous
samples)
10" M 0 " 2 monolayers
(surface segregated
constituents)
0.02-100 (instrument
dependent)
all except hydrogen
~10"8
vacuum (pressure
<10" 5torr)
10-20% of relative
abundance
<5
-10
vapor pressure < 10" 5 ton*;
otherwise any solid (e.g.,
insulator, conductor,
powder, organic)
chemical information (i.e.,
chemical valence) can be
determined for many
elements
thickness of layers <10nm
can be determined

139

Electron

Spectroscopy

for Chemical

Analysis

ably g o o d q u a n t i t a t i v e i n f o r m a t i o n a n d t o d a m a g e
minimally t h e s a m p l e being studied a r e c o n s i d e r e d
strengths of t h e t e c h n i q u e . O n t h e o t h e r h a n d , its
relatively p o o r spatial resolution (as c o m p a r e d with
o t h e r surface t e c h n i q u e s such as A u g e r s p e c t r o s c o p y
o r s e c o n d a r y - i o n m a s s s p e c t r o m e t r y ( S I M S ) , which
h a v e s u b m i c r o m e t e r p r o b e sizes), its relatively low
d a t a o u t p u t r a t e a n d its limited sensitivity ( c o m p a r e d
with S I M S ) a r e u n d e s i r a b l e characteristics.
O n e a d d i t i o n a l a t t r i b u t e of the t e c h n i q u e , w h i c h it
shares with A u g e r spectroscopy, is t h e p r o p e r t y of
" c l o s u r e . " Since t h e detection limits for all elements
(except h y d r o g e n a n d helium) a r e within a b o u t a
d e c a d e of e a c h o t h e r , it is usually possible t o deter
m i n e w h a t elements a r e not p r e s e n t o n a surface,
hence p r o v i d i n g a c o m p l e t e (or closed) specification
of surface c o m p o s i t i o n .

2. History

of ESC A

T h e theoretical f o u n d a t i o n of E S C A b e g a n with
Einstein's i n t e r p r e t a t i o n of t h e p h o t o e l e c t r i c effect in
1905. T h i s w o r k describes t h e basic p r o c e s s b y w h i c h
a n x-ray p h o t o n is a b s o r b e d b y a n a t o m , leading t o
the s u b s e q u e n t emission of a n electron. Between 1915
a n d 1935 several e x p e r i m e n t a l investigations of t h e xray photoeffect were c o n d u c t e d , n o t a b l y b y R o b i n s o n
a n d c o w o r k e r s . T h e s e studies succeeded in s h o w i n g
t h a t p h o t o e m i s s i o n did o c c u r from inner-shell elec
t r o n s in solids, b u t t h a t m o s t electrons so p r o d u c e d
which escaped t h e surface h a d lost different a m o u n t s
of energy a n d therefore h a d n o analytical i m p o r t a n c e .
Little a d d i t i o n a l w o r k w a s d o n e o n t h e subject until
the 1950s, w h e n a g r o u p of investigators u n d e r the
direction of S i e g b a h n in Sweden b e g a n a systematic
s t u d y of the x-ray photoeffect using a h i g h - r e s o l u t i o n
s p e c t r o m e t e r t o energy-analyze t h e p h o t o e m i t t e d
electrons. T h e y f o u n d , c o n t r a r y t o t h e earlier lowresolution studies, t h a t a surprising n u m b e r of t h e
electrons e m i t t e d from near-surface a t o m s lost n o
energy a n d hence reflected accurately i n f o r m a t i o n
a b o u t t h e a t o m s from which they o r i g i n a t e d . T h e
g r o u p p r o d u c e d a b o o k describing their extensive
studies (Siegbahn et al. 1967) a n d coined the a c r o n y m
ESCA.
Since then, t h e field h a s been explored extensively,
b o t h as a tool for basic investigation of solids a n d as
a n analytical t e c h n i q u e . C o m m e r c i a l x-ray p h o t o e l e c
t r o n s p e c t r o m e t e r s b e c a m e available in 1969 a n d there
h a v e been n u m e r o u s s y m p o s i a a n d j o u r n a l s d e v o t e d
t o the basic a n d applied uses of E S C A . In 1983,
S i e g b a h n w o n t h e N o b e l Prize in physics for his
p i o n e e r i n g w o r k in this field.

t h e m a t e r i a l t o be studied a n d the energy s p e c t r u m of

the resulting p h o t o e m i t t e d electrons is m e a s u r e d b y a
suitable s p e c t r o m e t e r . E a c h x-ray p h o t o n is usually
completely a b s o r b e d b y a single electron in the s a m
ple, p r o v i d i n g e n o u g h energy for it t o escape from its
orbital. T h e energy of t h e escaping electron is
Ee = hv-Eh

w h e r e Ee is t h e kinetic energy of t h e escaping electron,

hv is t h e x-ray p h o t o n energy a n d Eh is t h e b i n d i n g
energy of the electron in t h e m a t e r i a l .
If t h e incident x-ray energy is k n o w n a n d t h e
escaping electron energy is m e a s u r e d , t h e original
b i n d i n g energy of the electron c a n be calculated. Since
each element h a s a u n i q u e set of b i n d i n g energies, t h e
b i n d i n g energy in t u r n d e t e r m i n e s t h e element from
which the electron c a m e . T h e s e b i n d i n g energies c a n
be calculated with r e a s o n a b l e accuracy from singlea t o m m o d e l s o r d e t e r m i n e d experimentally from
x-ray a b s o r p t i o n o r emission m e a s u r e m e n t s . T h e
p h o t o e l e c t r o n cross section (i.e., the p r o b a b i l i t y t h a t a
given r a y will be a b s o r b e d by a n electron in a
p a r t i c u l a r a t o m i c orbital) d e p e n d s o n the p o l a r i z a b i lity of the o r b i t a l a n d c a n also be calculated with
useful a c c u r a c y from a single-atom m o d e l . T a b u l a
tions of b o t h the b i n d i n g energies a n d t h e cross
sections for specific elements h a v e been m a d e . P a r t of
such a t a b u l a t i o n is s h o w n in T a b l e 2. Since nearly all
elements h a v e lines below a b o u t 15 eV, these lowerbinding-energy lines a r e n o t useful for element identi
fication, b u t they d o p r o v i d e i n f o r m a t i o n a b o u t t h e
b a n d s t r u c t u r e of the m a t e r i a l .
T h e w i d t h s of t h e spectral lines in a n E S C A spec
t r u m , which limit the specificity of the t e c h n i q u e , are
typically in t h e region of 0 . 5 - 2 eV for solids a n d m u c h
n a r r o w e r (of t h e o r d e r of energy kT) for gases. W h i l e
t h e u n c e r t a i n t y principle w o u l d suggest t h a t the lines
s h o u l d be very n a r r o w , since the energy of b o t h t h e
initial a n d final state of t h e emitting a t o m c a n in
principle be well defined, there a r e a n u m b e r of
b r o a d e n i n g m e c h a n i s m s which act in solids. First,
there a r e final-state i n t e r a c t i o n s caused by relaxation
processes in t h e resulting ion as t h e electron is leaving.
Second, there a r e i n h o m o g e n e o u s
broadening
m e c h a n i s m s d u e t o n o n e q u i v a l e n c e in t h e e n v i r o n
m e n t of t h e e m i t t i n g a t o m s . T h e linewidths a r e
sufficiently n a r r o w in m o s t m a t e r i a l s t o p e r m i t u n a m
b i g u o u s elemental a s s i g n m e n t s , b u t they limit s o m e
w h a t t h e ability t o distinguish subtle differences in
t h e a t o m i c e n v i r o n m e n t d u e , for e x a m p l e , t o n o n equivalent b o n d i n g sites.

4. Chemical

3. Basic

Theory

In E S C A , a b e a m of soft rays ( 1 - 5 keV) illuminates

140

(1)

Shift

Information

O n e of t h e m o s t v a l u a b l e features of E S C A from a n
analytical p o i n t of view is its ability t o distinguish
different chemical b o n d i n g configurations as well as
different elements. It is possible, for e x a m p l e , t o

Electron

Spectroscopy

for Chemical

Analysis

Table 2
Binding energies (eV) (larger figures) and theoretical cross sections (smaller figures, line intensities, normalized to the carbon \s
line) of the ESCA lines for the first 30 elements of the periodic table, arranged by atomic orbital (courtesy of R. N. King,
University of Utah)
Atomic orbital
1*1/2 2*1/2

2 / V 2/>3/2 3*1/2 3Pi/2 3/>3/2

Atomic orbital
3d3/2

14

0.0002

He

25
55
111
188
284
399
532
686
867
1072

CI
Ar

0.486

1.00

1.80

5
7
9
24
7
31
9
45
18
63
31
89
52
118 74 73
149 100 99
189 136 135

4.43

Ne

6.30

Na

8.52

Mg

202
247
297
350
407
461
520
584
652
723
794
872
951
1044

200
245
294
347
402
455
513
575
641
710
779
855
931
1021

2.91

Ti

3.24
3.57

Cr

3.91

0.0478

0.296

Mn

4.23

0.103

0.1941

0.422

1.18

0.0193

0.210

0.955

Sc

0.0065

1
2
1
8
16

Fe

0.0064

4.57

Co

4.88

0.3335 0.0285

0.753 0.1811

Si

270
320
377
438
500
564
628
695
769
846
926
1008
1096
1194

2.59

0.0015

0.575

Al

Ca

0.0002

2.93 0.1405

1.11

2.27

0.1947

0.567

1.97

0.0568

Be

0.276

0.403

Ni

5.16

0.356 0.0535
0.541

0.0808

3
10

Cu

0.014

0.789 0.1116 0.0368

distinguish silicon in its e l e m e n t a l f o r m from its oxide

( S i 0 2 ) o r t o distinguish c a r b o n p r e s e n t a s a h y d r o c a r
b o n from c a r b o n b o u n d t o o x y g e n a s C o r C = 0 .
F i g u r e 1 s h o w s a s p e c t r u m illustrating t h e latter
e x a m p l e . H e r e t h e relative a r e a s o f t h e t h r e e p e a k s
reflect t h e s t o i c h i o m e t r y o f t h e p o l y m e r (three C C
bonds to one each of the C a n d C = 0 bonds).
T h e r e a s o n t h a t this is possible is b e c a u s e t h e
b i n d i n g energies o f electrons in a n a t o m (even c o r e
electrons) a r e affected b y t h e a t o m ' s chemical e n
v i r o n m e n t . T h e extent t o w h i c h t h e b i n d i n g energy o f
a p a r t i c u l a r line differs from s o m e reference value is
t e r m e d its chemical shift. T h i s shift is r o u g h l y p r o p o r
tional t o t h e electronegativity o r valence o f t h e a t o m .
T h e m o r e electronegative t h e e n v i r o n m e n t , t h e lower
the b i n d i n g energy.
This is n o t a l w a y s t h e case, b e c a u s e
final-state
interactions often modify o r o b s c u r e t h e chemical
shift, s o t h a t s o m e elements exhibit little o r n o c h e m
ical shift. Nevertheless, t h e effect exists a n d is signific
a n t for m a n y elements: c a r b o n , oxygen, n i t r o g e n ,

5.46

Zn

/2

1.43
1.69

0.0082

Li

2/>,
229 165 164

1*1/2 2*1/2

3d5/2

5.76

0.775
1.03

1.35
1.72

2.17
2.69
3.29
3.98

4.74
5.60

6.54
7.57

8.66

0.80

2/>3/2 3*1/2

16

0.1465

0.0774

18
25
34
44
54
59
66
74
84
95
101
112
120
137

7
12
18
26
32
34
38
43
49
56
60
68
74
87

3/7, i2

3/>32
3</3/2
/

1.51

0.1852 0.1433

2.01

0.227 0.2418

2.62

0.286 0.3619

3.35

0.351

0.507

4.21

0.411

0.650

0.0042

5.22

0.473

0.813

0.0136

6.37

0.538

0.996

0.0309

7.69

0.596

1.173

0.0651

9.17

0.674

1.423

0.1046

10.82

0.745

1.669

0.1711

12.62

0.818

1.930

0.2664

14.61

0.892

2.217

0.3979

16.73

0.957

2.478

0.589

18.92

1.04

2.828

0.81

3d5/2

5
1

3
2
2
4
6
3
4
2
9

c=o
I

C 0

Binding energy ( e V )

Figure 1
ESCA carbon spectrum of Mylar polymer with three
different carbon bonds

141

Electron

Spectroscopy

for Chemical

Analysis

sulfur, a l u m i n u m a n d silicon, t o n a m e b u t a few. T h e

shift between n i t r o g e n in a r e d u c e d form (e.g., N H 2 ,
N H 3 ) a n d the n i t r a t e form is a b o u t 4 e V , w h i c h is
easily m e a s u r a b l e in m o s t m a t e r i a l s . O n t h e o t h e r
h a n d , t h e shift in the i r o n lines b e t w e e n ferric a n d
ferrous c o m p o u n d s is only a b o u t 0.5 eV, which is
often difficult to m e a s u r e .
Because of the chemical shifts of c a r b o n c o m
p o u n d s , E S C A h a s b e c o m e p a r t i c u l a r l y v a l u a b l e in
studying p o l y m e r s . C F 3 is shifted a l m o s t 9 e V from
C H 3 , so t h a t often the s t o i c h i o m e t r y of oxygen- o r
fluorine-containing c o m p o u n d s c a n be directly in
ferred from their E S C A spectra. A n excellent t a b u l a
tion of chemical shifts for m o s t elements h a s been
given by W a g n e r et al. (1979).

5. Quantitative

Characteristics

of

ESCA

O n e of the m o s t i m p o r t a n t aspects of E S C A from the

s t a n d p o i n t of a n analytical t e c h n i q u e is the ability t o
quantify the spectra o b t a i n e d . It is possible t o deter
m i n e the relative a b u n d a n c e of t h e c o n s t i t u e n t s p r e
sent o n a surface t o a n a c c u r a c y of 1 0 - 2 0 % using only
theoretical values for the p h o t o e l e c t r o n cross sections
involved. W i t h empirical s t a n d a r d s this a c c u r a c y c a n
be i m p r o v e d t o better t h a n 5 % in m a n y cases.
Q u a n t i t a t i o n of E S C A spectra is a p p r o a c h e d by
considering t h e general r e l a t i o n s h i p between the
n u m b e r of a t o m s of s o m e element p r e s e n t in the
sample a n d the n u m b e r of electrons detected from
t h a t element. In general, the d i s t r i b u t i o n of a given
element is a function of d e p t h within t h e s a m p l e , so
that
D, = ,,

{){)

dz

(2)
1

dz

100ff,/Z,#,

(5)

w h e r e C, is t h e c o n c e n t r a t i o n of element / in a t . % .
T h i s simplifies t o
(6)
w h e r e k{= l/,,,,, a c o n s t a n t for a n y given a t o m i c
line.
T h u s , t o d e t e r m i n e t h e relative c o n c e n t r a t i o n s of
t h e surface c o n s t i t u e n t s of a s a m p l e , it is necessary
only t o m e a s u r e t h e n u m b e r of p h o t o e l e c t r o n s
detected in a n E S C A line of each element, multiply by
the a p p r o p r i a t e fc, for t h a t line (a c o n s t a n t which
includes t h e p h o t o e l e c t r o n cross section, escape d e p t h
a n d s p e c t r o m e t e r t r a n s m i s s i o n for t h e line in q u e s
tion) a n d t h e n n o r m a l i z e t o 1 0 0 % for all elements.
T h i s w o r k s very well in practice, for several rea
sons. First, there a r e few m a t r i x effects in E S C A , so
t h e k{ values a r e a function of t h e element involved
a n d t h e b i n d i n g energy of the line used, b u t n o t of the
chemical c o m p o s i t i o n of t h e s a m p l e . Second, since
E S C A c a n detect all elements except h y d r o g e n , t h e
n o r m a l i z a t i o n is meaningful if it is u n d e r s t o o d t h a t
h y d r o g e n is excluded. T h i r d , t h e values of kt c a n be
e s t i m a t e d r a t h e r accurately ( 1 0 - 2 0 % ) from theoret
ical c o n s i d e r a t i o n s o r c a n be d e t e r m i n e d empirically
from m o d e l c o m p o u n d s . F i g u r e 2 s h o w s a typical
E S C A survey s p e c t r u m of a piece of clean q u a r t z . I n
this spectral region, all elements in t h e periodic table
h a v e at least o n e line, so such a s p e c t r u m gives a
c o m p l e t e elemental c h a r a c t e r i z a t i o n of t h e surface
(except for h y d r o g e n ) . U s i n g t h e q u a n t i t a t i o n p r o c e d
u r e described, t h e relative a b u n d a n c e s of silicon,
c a r b o n a n d oxygen c a n be calculated: oxygen,
65 a t . % ; silicon, 33 a t . % ; c a r b o n , 2 a t . % . T h e silicon:
oxygen a t o m i c r a t i o is a b o u t 2 as expected; t h e c a r b o n
represents a s u b m o n o l a y e r c a r b o n a c e o u s surface c o n -

- 2

where >, is the n u m b e r of electrons detected s " c m ,

, is t h e p h o t o e m i s s i o n cross section for t h e a t o m i c
2
level in c m , Tt is the analyzer t r a n s m i s s i o n function,
1
- 2
is the x-ray flux in p h o t o n s s " c m , Nt(z) is the
3
density of a t o m s of element i in a t o m s c m " a n d ()
is the escape p r o b a b i l i t y .
This e q u a t i o n is n o t in general solvable, because the
d i s t r i b u t i o n of a t o m s within the s a m p l e is usually
u n k n o w n . H o w e v e r , if a m e a n c o n c e n t r a t i o n is
defined:
()!()

C,=

O(ls)

(3)
C(ls)

Eqn.(2) c a n be solved for this value:

^,/,^

(4)

If it is a s s u m e d t h a t all the elements p r e s e n t o n the

sample surface c a n be detected by E S C A (true except
for h y d r o g e n ) , it is possible to n o r m a l i z e this expres
sion to o b t a i n relative c o n c e n t r a t i o n s by a s s u m i n g

142

Binding energy

(eV)

Figure 2
ESCA survey spectrum of clean quartz

Si (2/?)
S i ( 2s ) |

Electron

t a m i n a n t . N o r m a l l y , surfaces e x p o s e d t o t h e e n v i r o n
m e n t h a v e several m o n o l a y e r s of such c o n t a m i n a t i o n .
T h e p e a k a t t h e e x t r e m e left is a n o x y g e n A u g e r line
which is excited by t h e x-ray b e a m .
Q u a n t i t a t i o n in E S C A h a s b e e n a p p l i e d m o s t suc
cessfully t o p o l y m e r s , i n s u l a t o r s a n d s e m i c o n d u c t o r
m a t e r i a l s , in w h i c h effects of c o n d u c t i o n electrons a r e
small. Q u a n t i t a t i o n is p a r t i c u l a r l y difficult in t r a n s i
tion m e t a l systems.

6.

Spectroscopy

for Chemical

Monochromator
-'crystal

Analysis

Hemispherical
analyzer

Electron
gun\

Instrumentation

T h e basic E S C A s p e c t r o m e t e r consists of a n x-ray

source for s a m p l e excitation, a n electron s p e c t r o m e t e r
t o discriminate electron energies a n d a d e t e c t i o n
system which p r o d u c e s t h e E S C A s p e c t r u m , all
m o u n t e d in a single v a c u u m e n c l o s u r e as d e p i c t e d in
Fig. 3.
6.1 X-Ray

Source

Since the incident x-ray energy m u s t b e k n o w n in

o r d e r to infer b i n d i n g energies from t h e E S C A tech
nique, a source of k n o w n energy is needed. C o n s e
quently, t h e simplest s o u r c e , a n d o n e still used in
c o m m e r c i a l s p e c t r o m e t e r s t o d a y , is o n e e m i t t i n g t h e
characteristic s p e c t r u m of a n element, usually either
a l u m i n u m (Kol) ( 1 4 8 6 e V ) o r m a g n e s i u m
(Kql)
(1253 eV). T h e s e sources consist o f a simple filament
emitting electrons, a n accelerating voltage of 1 0 20 k V a n d a n a n o d e of t h e a p p r o p r i a t e m a t e r i a l t o
p r o d u c e t h e characteristic rays. T h e s e sources h a v e
high b r i g h t n e s s if l o c a t e d n e a r t h e s a m p l e t o b e
studied, b u t h a v e s o m e u n w a n t e d r a d i a t i o n ( o t h e r xr a y lines, B r e m s s t r a h l u n g ) a n d linewidths in t h e
region of 0.6-0.9 eV.
M o r e recently, c o m m e r c i a l s p e c t r o m e t e r s h a v e
b e c o m e available w i t h spherically b e n t crystal
m o n o c h r o m a t o r s interspersed b e t w e e n a source of t h e
type j u s t described a n d t h e s a m p l e (see Fig. 4). T h i s

Vacuum enclosure

Detector

Figure 3
Schematic of a simple ESCA spectrometer

Figure 4
Schematic of an improved ESCA spectrometer

m o n o c h r o m a t o r reflects only a n a r r o w b a n d of rays

o n t o t h e s a m p l e (in t h e r e g i o n of 0 . 2 - 0 . 3 eV), t h u s
eliminating the unwanted radiation and improving
t h e r e s o l u t i o n , a n d focuses t h e r a y s so t h a t relatively
small a r e a s ( ~ 150 ) c a n be a n a l y z e d .
6.2 Electron

Spectrometer

W h i l e a wide variety of electron s p e c t r o m e t e r s h a v e

been used for E S C A , b y far t h e m o s t widely used t y p e
is t h e h e m i s p h e r i c a l a n a l y z e r (also called t h e spherical
c a p a c i t o r a n a l y z e r ) . T h i s a n a l y z e r consists of t w o
c o n c e n t r i c spherical surfaces ( h e m i s p h e r e s usually)
2
w h i c h establish a 1/r electric field b e t w e e n t h e m ,
w h e r e r is t h e d i s t a n c e from their center. Trajectories
t h r o u g h this a n a l y z e r follow K e p l e r ' s laws of p l a n e t
a r y m o t i o n . T h i s a n a l y z e r is " d o u b l e focusing"; t h a t
is, electrons e n t e r i n g t h e spherical field a t a p o i n t t e n d
t o be refocused a t a n o t h e r p o i n t o n t h e o p p o s i t e side
of t h e e n t r a n c e , a t a r a d i u s p r o p o r t i o n a l t o their
energy. T h u s , this s p e c t r o m e t e r spatially disperses
electrons of different energies.
T h e h e m i s p h e r i c a l a n a l y z e r is generally o p e r a t e d in
a " c o n s t a n t - r e s o l u t i o n " m o d e in E S C A (i.e., electrons
a r e r e t a r d e d t o s o m e fixed energy before e n t e r i n g the
analyzer); t h e E S C A s p e c t r u m is t a k e n by sweeping
t h e a m o u n t of r e t a r d a t i o n a p p l i e d so t h a t t h e desired
energy r a n g e of p h o t o e l e c t r o n s is s c a n n e d .
6.3 Detector/Signal-Processing
System
W h i l e h u n d r e d s of w a t t s a r e usually used t o excite the
x-ray s o u r c e in a n E S C A s p e c t r o m e t e r , t h e detected
6
l
e l e c t r o n flux is usually in t h e r a n g e 1 0 M 0 s ~ . C o n s e
q u e n t l y , electron c o u n t i n g d e t e c t o r s a r e a l m o s t
universally used t o achieve t h e lowest noise p e r f o r m -

143

Electron

Spectroscopy

for Chemical

Analysis

ance. Single-channel d e t e c t o r s (using c h a n n e l t r o n s o r

discrete d y n o d e multipliers) a r e used with two-slit
analyzers. I m a g i n g d e t e c t o r s , which collect electrons
of m a n y energies, a r e also used w i t h o u t a s e c o n d slit
t o increase t h e speed a n d sensitivity of t h e spec
t r o m e t e r . M o d e r n digital signal h a n d l i n g systems a r e
used a l m o s t universally t o a c c u m u l a t e , display a n d
store the spectra.

7. Use of ESC A as an Analytical

Technique

Wagner et al. 1979 Handbook of X-Ray Photoelectron Spec

troscopy. Perkin-Elmer Corporation
Windawi H, Ho F F-L 1982 Applied Electron Spectroscopy
for Chemical Analysis, Vol. 63. Wiley, New York
M . A . Kelly
[Surface Science L a b o r a t o r i e s , M o u n t a i n
View, California, U S A ]

Electron Spin Resonance

A s m e n t i o n e d earlier, for m e a s u r e m e n t s r e q u i r i n g
extremely low detection limits, S I M S is usually the
surface analysis m e t h o d of choice; for t h o s e r e q u i r i n g
extremely g o o d spatial resolution, A u g e r spectros
c o p y is generally used. E S C A is often the m e t h o d of
choice for insulating o r easily d a m a g e d m a t e r i a l s as
well as w h e r e chemical i n f o r m a t i o n o r g o o d q u a n t i
t a t i o n is desired. S o m e specific a p p l i c a t i o n s include a
study of p l a s m a - t r e a t e d p o l y m e r surfaces, t h e stoic h i o m e t r y of S i - N - O - c o n t a i n i n g ceramics, t h e evalu
a t i o n of processes used for w a s h i n g glassware, t h e
w e a t h e r i n g of m i n e r a l s , studies of active sites o n
catalysts, adhesive failures in c o m p o s i t e m a t e r i a l s a n d
passivation processes o n m e t a l surfaces. A n u m b e r of
j o u r n a l s currently r e p o r t o n such w o r k , n o t a b l y the
Journal of Electron Spectroscopy
a n d t h e Journal of
Vacuum Science and
Technology.
T o generalize a b o u t these a p p l i c a t i o n a r e a s , E S C A
h a s been used successfully in three m o d e s :

E l e c t r o n spin r e s o n a n c e ( E S R ) is a generic t e r m for a

variety of r e s o n a n c e p h e n o m e n a in t h e r e s p o n s e of
systems c o n t a i n i n g p a r a m a g n e t i c centers t o a highfrequency external m a g n e t i c field w h e n t h e frequency
of t h e field coincides with the frequency of allowed
t r a n s i t i o n s b e t w e e n t h e Z e e m a n levels of t h e system in
t h e m a g n e t i c field.
P a r a m a g n e t i c centers a r e associated with:

(a)
(b)

(a)

all a t o m s h a v i n g a n o d d n u m b e r of electrons;

(b)

free radicals ( v a r i o u s chemical c o m p o u n d s h a v

ing a n u n p a i r e d electron);

(c)

ions h a v i n g a n i n c o m p l e t e inner electron shell

( t r a n s i t i o n m e t a l ions);

(d)

systems with even n u m b e r s of electrons h a v i n g

n o n v a n i s h i n g a n g u l a r m o m e n t u m (basically sys
t e m s with a triplet spin state);

(e)

s o m e solids possessing p o i n t defects with either a

surplus electron o r hole;

as a t r o u b l e s h o o t i n g tool which is used t o find

clues t o solve a specific p r o b l e m ;

(f)

d a n g l i n g b o n d s of dislocations in crystals t h a t
a r e covalently b o n d e d ;

as a m o n i t o r i n g t e c h n i q u e t o m e a s u r e the devi
a t i o n of s o m e well-defined p a r a m e t e r from a
norm; and

(g)

c o n d u c t i o n electrons in m e t a l s a n d s e m i c o n d u c
tors.

(c)

as a research tool t o p r o v i d e e x p e r i m e n t a l d a t a
used for c o m p a r i s o n with theories.
Since t h e mid-1970s, t h e a p p l i c a t i o n s in t h e first
t w o of these categories h a v e g r o w n t r e m e n d o u s l y .
Because of its generality, E S C A s h o u l d r e m a i n a
m a j o r analytical surface t e c h n i q u e for t h e foreseeable
future.
See also: Auger Electron Spectroscopy; Chemical Analysis
of Solid Surfaces; Secondary-Ion Mass Spectrometry

Bibliography
Briggs D, Seah 1983 Practical Surface Analysis. Wiley,
New York
Brundle C R, Baker A D 1981 Electron Spectroscopy:
Theory, Technique and Applications, Vol. 4. Academic
Press, London
Ghosh 1983 Introduction to Photoelectron Spectroscopy.
Wiley, New York
Siegbahn G et al. 1967 ESCA, Nova Acta Regiae
Societatis Scientiarum, Ser. IV, Vol. 20. Almqvist and
Wiksell, Boktryckeri, Uppsala, Sweden

144

In a simplified case of a free q u a n t u m - m e c h a n i c a l

particle of a n g u l a r m o m e n t u m h[J(J+ 1)]* in a n
external m a g n e t i c field t h e relative p o s i t i o n s of t h e
Z e e m a n levels a r e given b y
WMj

gpBHMj

H e r e M3 is the m a g n e t i c q u a n t u m n u m b e r , Mj = /,
J+ 1, ..., J; a n d g is the L a n d e factor given b y
=

/ ( / + !) + ( + 1 ) - L ( L + 1)

2J(J+\)

w h e r e S a n d L a r e t h e spin a n d o r b i t a l m o m e n t u m
quantum numbers.
T h e m a g n e t i c field of e l e c t r o m a g n e t i c r a d i a t i o n
induces t h e m a g n e t i c dipole t r a n s i t i o n s o b e y i n g t h e
selection rule AM = 1. T h e c o n d i t i o n of equality of
t h e energy of t h e e l e c t r o m a g n e t i c q u a n t u m t o t h e
m a g n e t i c level splitting is
hco =

gpBH

F o r a free electron h a v i n g only t h e intrinsic a n g u l a r

m o m e n t u m (i.e., spin), t h e value of g is 2.0023193.

Electron
T h e b e h a v i o r of p a r a m a g n e t i c centers in c o n
densed m a t t e r is m o r e c o m p l i c a t e d . First, t h e e x t e r n a l
field of t h e m e d i u m c o n t a i n i n g t h e particles as a rule
lifts t h e a n g u l a r m o m e n t u m d e g e n e r a c y , so t h a t t h e
simple expression s h o w n a b o v e for t h e g factor n o
longer h o l d s . S e c o n d , t h e m a g n e t i c m o m e n t of t h e
p a r a m a g n e t i c center interacts with t h e n u c l e a r m a g
netic m o m e n t of t h e p a r e n t a n d n e i g h b o r i n g nuclei.
A l t h o u g h this latter, hyperfine i n t e r a c t i o n is a w e a k
o n e , it greatly e x t e n d s t h e r a n g e of a p p l i c a t i o n s of
ESR.

7. Methods

of Observation

of ESR and

Relaxation

T h e r e s o n a n c e c o n d i t i o n s c a n b e m e t in t w o w a y s :
either by v a r y i n g t h e r a d i a t i o n frequency u n d e r a
c o n s t a n t external m a g n e t i c field o r by v a r y i n g t h e
m a g n e t i c field a t t h e fixed frequency. In t h e m e d i u m 6
l
strength m a g n e t i c field, 10 A m " , t h e r e s o n a n c e
condition corresponds to the microwave or superhigh
frequency ( S H F ) b a n d , 2& 40 G H z . K l y s t r o n s ,
usually used as S H F g e n e r a t o r s , c a n be t u n e d only
within a 10 % b a n d a r o u n d t h e n o m i n a l frequency. I n
view of this l i m i t a t i o n , w h i c h is d u e t o certain specific
features of w a v e g u i d e s a n d wide use of h i g h - Q S H F
cavities as a b s o r p t i o n cells, it is c o n v e n t i o n a l in t h e
o b s e r v a t i o n of E S R t o use a fixed-frequency regime
with a v a r y i n g m a g n e t i c field.
T h e simplest s e t u p of t h e E S R d e t e c t o r is d e p i c t e d
in Fig. 1. T h e a r r a n g e m e n t c o n t a i n s t h e m i c r o w a v e
generator supplemented by an attenuator to tune the
S H F power output and the frequency/wavelength
meter, t h e a b s o r p t i o n cell with t h e s a m p l e (usually a
cavity), t h e S H F receiver a n d t h e r e c o r d i n g system.
T h e a b s o r p t i o n cell is p l a c e d b e t w e e n t h e poles of t h e
e l e c t r o m a g n e t , w h i c h is s u p p l e m e n t e d by field sweep
a n d m o d u l a t i o n systems. W h e n t h e m a g n e t i c field
reaches t h e r e s o n a n c e value, t h e p a r a m a g n e t i c s a m p l e

Frequency modulator
of the magnetic field

Klystron

Receiver

Recorder
Wavemeter

Figure 1
Schematic layout of a simple electron spin resonance
spectrometer

Spin

Resonance

a b s o r b s energy from t h e e l e c t r o m a g n e t i c field, t h u s

c h a n g i n g t h e o u t p u t signal from t h e a b s o r p t i o n cell,
w h i c h is r e c o r d e d by t h e receiver a n d recorder. T h e
m e a s u r e m e n t s s h o w t h e d e p e n d e n c e of the S H F
p o w e r p a s s e d t h r o u g h t h e a b s o r p t i o n cell o r its deri
vative o n the m a g n e t i c field s t r e n g t h . M o r e c o m p l i
c a t e d b r i d g e circuits e n a b l e b o t h t h e a b s o r p t i o n a n d
dispersion of E S R t o b e r e c o r d e d .
I n m o s t of the a p p l i c a t i o n s of E S R , high sensitivity
a n d high r e s o l u t i o n of t h e m a g n e t i c field a r e needed.
T h e signal-to-noise r a t i o d e p e n d s o n t h e t o t a l n u m b e r
of p a r a m a g n e t i c centers, t h e difference in p o p u l a t i o n s
of t h e Z e e m a n levels b e t w e e n w h i c h t h e t r a n s i t i o n
t a k e s place, t h e fraction of t h e cavity v o l u m e occupied
by the sample and the spectrometer bandwidth. The
a b s o l u t e n u m b e r of p a r a m a g n e t i c centers d e p e n d s o n
their c o n c e n t r a t i o n a n d t h e s a m p l e v o l u m e . If the
s a m p l e is g a s e o u s , it occupies t h e w h o l e a b s o r p t i o n
cell. In t h e case of s o l u t i o n s o r liquid s a m p l e s , t h e
p r o b l e m of s u b s t a n t i a l dielectric losses in t h e s a m p l e
is usually e n c o u n t e r e d . T o m i n i m i z e these losses the
s a m p l e s h o u l d b e p l a c e d in t h e n o d e of t h e electric
field a n d t h e crest of t h e m a g n e t i c field, t h u s c o n
s t r a i n i n g t h e s a m p l e size. T h e size of the m o n o c r y s t a l
s a m p l e s is usually limited b y t h e difficulty of g r o w i n g
large perfect crystals.
T h e r a t i o of level p o p u l a t i o n s is given b y a c o n v e n
w h e r e is
t i o n a l B o l t z m a n n factor, exp(-gpBH/kT),
t h e a b s o l u t e t e m p e r a t u r e . T o increase t h e difference in
p o p u l a t i o n s , either t h e m a g n e t i c field s h o u l d b e
increased, t h u s raising t h e frequency a t which E S R
c a n be o b s e r v e d , o r t h e s a m p l e t e m p e r a t u r e s h o u l d be
lowered. In liquid s a m p l e s , dielectric losses increase
steeply w i t h frequency, p u t t i n g a n u p p e r limit o n the
o b s e r v a t i o n frequency of a b o u t 10 G H z , w h e r e a s in
crystalline s a m p l e s dielectric losses a r e low a n d higher
r e s o n a n c e frequencies, usually a r o u n d 40 G H z , a r e
preferable.
A b s o r p t i o n of energy is c a u s e d by the flip of spins
originally o r i e n t e d a l o n g t h e m a g n e t i c field. T h e re
verse processes a r e called i n d u c e d t r a n s i t i o n s . B o t h
t r a n s i t i o n s h a v e e q u a l p r o b a b i l i t i e s b u t , u n d e r ther
m a l e q u i l i b r i u m , t h e lower state is m o r e highly p o p u
lated, so t h a t a b s o r p t i o n o c c u r s in preference t o
emission. H o w e v e r , c o n t i n u e d a b s o r p t i o n w o u l d
eventually equalize t h e p o p u l a t i o n s so, for a b s o r p
tion t o persist in t h e s t a t i o n a r y state, a m e c h a n i s m
m u s t exist w h i c h drives t h e system t o t h e r m a l equi
librium. Such a m e c h a n i s m is t h e so-called s p i n lattice r e l a x a t i o n , w h i c h d e t e r m i n e s t h e lifetime , of
t h e p a r a m a g n e t i c system in t h e excited state. It is o n e
of t h e m e c h a n i s m s c o n t r i b u t i n g t o t h e w i d t h of the
E S R line. U s u a l l y t h e s p i n - l a t t i c e r e l a x a t i o n c o n t r i
b u t i o n t o t h e E S R linewidth is very small. O t h e r
b r o a d e n i n g m e c h a n i s m s c a n be divided i n t o t w o
groups.
Effective m a g n e t i c fields m a y be n o n u n i f o r m over
t h e s a m p l e v o l u m e , so t h a t a t e a c h frequency only a
small fraction of p a r a m a g n e t i c centers a r e a t the

145

Electron

Spin

Resonance

r e s o n a n c e c o n d i t i o n . A s a result t h e o b s e r v e d E S R
line w o u l d be a s u p e r p o s i t i o n of a large n u m b e r of
c o m p o n e n t s ( " s p i n - p a c k e t s " ) , slightly shifted relative
t o each o t h e r . T h e final signal c o r r e s p o n d s t o t h e
envelope of this s u p e r p o s i t i o n . If t h e static a n d aver
aged m a g n e t i c fields acting o n different centers d o n o t
coincide, t h e b r o a d e n i n g is t e r m e d n o n u n i f o r m .
U n d e r u n i f o r m b r o a d e n i n g , t h e a v e r a g e d field o n
different centers coincides with t h e static o n e , b u t
local fields vary with time. U n i f o r m b r o a d e n i n g is
usually c h a r a c t e r i z e d b y t h e so-called s p i n - s p i n relax
a t i o n time T2.
T h e m a i n s o u r c e of u n i f o r m b r o a d e n i n g is t h e
d i p o l e - d i p o l e i n t e r a c t i o n s of t h e m a g n e t i c m o m e n t s
of p a r a m a g n e t i c centers. R e l a x a t i o n processes, c h a r
acterized by r e l a x a t i o n times Tx a n d T2, involve a n
i n t e r a c t i o n of p a r a m a g n e t i c centers with e a c h o t h e r
a n d also with o t h e r c o m p o n e n t s of t h e c o n d e n s e d
state, so t h a t a s t u d y of t h e p a r a m a g n e t i c r e l a x a t i o n
a n d of its d e p e n d e n c e o n external c o n d i t i o n s p r o v i d e s
a w e a l t h of i n f o r m a t i o n o n t h e n a t u r e of m a t e r i a l s
studied.
It m a y h a p p e n t h a t despite t h e r e l a x a t i o n processes
the high S H F field in t h e cavity equalizes t h e p o p u l a
tions of t h e energy levels, t h u s r e d u c i n g a b s o r p t i o n b y
t h e p a r a m a g n e t i c s a m p l e . T h i s is t h e so-called reso
n a n c e s a t u r a t i o n effect, w h i c h p u t s a n u p p e r b o u n d
o n t h e S H F p o w e r used in E S R studies. F o r the
n a r r o w lines these limitations m a y p r o v e essential. O n
the o t h e r h a n d , t h e s a t u r a t i o n effect e n a b l e s the
a m p l i t u d e of S H F m a g n e t i c field a t t h e s a m p l e loca
tion t o b e d e t e r m i n e d .

2. ESR in Free Radicals:

Interaction

The

Hyperfine

E S R h a s played a m a j o r role in studies of o r g a n i c

substances, w h e r e it h a s been used t o o b s e r v e free
radicals. A l t h o u g h they c o n s t i t u t e only a limited
specific class of o r g a n i c s u b s t a n c e s (i.e., t h o s e w i t h
u n p a i r e d electrons), free radicals possess all the typi
cal structures of o r g a n i c molecules. I n a d d i t i o n , or
ganic radicals a r e in themselves i m p o r t a n t in a n
o r g a n i c w o r l d . R e s o n a n c e s p e c t r a of free radicals m a y
p r o v i d e a w e a l t h o f i n f o r m a t i o n o n the d e r e a l i z a t i o n
of u n p a i r e d electrons in the skeleton of t h e molecule,
o n the n a t u r e of a chemical b o n d a n d o n t h e a t o m s
t h a t c o n s t i t u t e a molecule. All this i n f o r m a t i o n is
c o n t a i n e d in t h e very c o m p l e x E S R spectra of these
compounds.
Nowadays,
there
exist
different
a p p r o a c h e s t o d e c o d i n g these spectra; c o m p i l a t i o n s of
the spectra of different free radicals h a v e been p u b
lished, e n a b l i n g easy identification of k n o w n radicals.
It is hyperfine i n t e r a c t i o n ( H F I ) which enriches a n y
information provided by E S R on organic substances.
T h e H F I m a k e s certain relative o r i e n t a t i o n s of t h e
electron a n d n u c l e a r spins m o r e preferable.
T h e H F I includes a m a g n e t i c i n t e r a c t i o n b e t w e e n

146

the nuclear magnetic m o m e n t and the magnetic

m o m e n t of a n electron system. T h i s i n t e r a c t i o n is
a n i s o t r o p i c . M o r e i m p o r t a n t is t h e H F I t e r m c o r r e s
ponding to the Fermi contact interaction. This com
p o n e n t of H F I results from t h e m a g n e t i z a t i o n of s
electrons by t h e u n p a i r e d electron of t h e relevant shell
o r o r b i t a l . T h e i n t e r a c t i o n energy is p r o p o r t i o n a l t o
t h e density of u n p a i r e d electrons of t h e a t o m s which
f o r m t h e m o l e c u l e . T h e effective field acting o n the
electrons a n d giving rise t o t h e F e r m i c o n t a c t inter
a c t i o n is
#eff

= g*M* ( 8 * / 3 ) | V ( 0 ) | M 7 + H0 = AMj + H0

w h e r e M 7 is t h e n u c l e a r m a g n e t i c q u a n t u m n u m b e r ,
r u n n i n g from / t o + / . N u c l e a r m a g n e t i c m o m e n t s
m o v e m u c h slower t h a n t h e electron m o m e n t s ,
as t h e r e s o n a n c e frequencies of p r o t o n s a n d elec
t r o n s in t h e s a m e m a g n e t i c field a r e related b y
l
3
opDe~ = 1.5193 = 1 0 " . H e n c e , a n y s e p a r a t e electron
is in a n effective m a g n e t i c field H0 + AM,, w h e r e M 7
retains its value, e q u a l t o o n e of 21+ 1 possible
values, for a p e r i o d of time w h i c h exceeds t h e inverse
frequency of E S R b y a large factor. I n this case, t h e
E S R s p e c t r u m of a large system will be split i n t o
21 + 1 e q u i d i s t a n t c o m p o n e n t s .
In free radicals, u n p a i r e d electrons a r e only in r a r e
cases in o r b i t a l s (i.e., in p r a c t i c e they a r e localized in
t h a t p a r t of t h e molecule w h e r e t h e electrons needed
t o s a t u r a t e valency a r e missing). - O r b i t a l u n p a i r e d
electrons a r e strongly delocalized in the skeleton of
the molecule. I n this case, the density of u n p a i r e d
electrons o n e q u i v a l e n t a t o m s s h o u l d be identical, a n d
therefore a n identical H F I o c c u r s with equivalent
atoms. F o r nonequivalent atoms, the H F I constants
w o u l d be different.
T h e energy levels of a n u n p a i r e d electron o n t w o
e q u i v a l e n t a t o m s with n u c l e a r spin / = \ a r e s h o w n in
Fig. 2. T h e Z e e m a n splitting in t h e field is s h o w n in
(a); there a r e t w o levels c o r r e s p o n d i n g t o Ms = \. A
s t r u c t u r e of energy levels for H F I with o n e a t o m is
s h o w n in (b); every level splits i n t o t w o , c o r r e s p o n d
ing t o t h e n u c l e a r m a g n e t i c q u a n t u m n u m b e r
Mj= %. T h e effect of t h e second e q u i v a l e n t nucleus
is s h o w n in (c). E a c h of t h e four levels of (b) splits i n t o
t w o . A s hyperfine splitting is t h e s a m e for b o t h a t o m s ,
o n e o b t a i n s six levels, t h e c e n t r a l line in e a c h of t h e
triplets c o m p r i s i n g t w o states. T h e E S R t r a n s i t i o n s
1, AMj= 0) b e t w e e n levels a r e s h o w n b y
(AMS=
arrows.
T h e resulting s p e c t r u m consists of three lines, t h e
central o n e h a v i n g d o u b l e intensity. I n t h e general
case of e q u i v a l e n t nuclei of spin / , o n e o b t a i n s
2nl+ 1 lines in t h e E S R s p e c t r u m , with relative
intensities c o r r e s p o n d i n g t o P a s c a l ' s triangle. T h i s
e n a b l e s o n e t o d i s e n t a n g l e from t h e c o m p l e x E S R
spectra t h e sequence c o r r e s p o n d i n g t o e q u i v a l e n t
a t o m s . T h e n u m b e r of such sequences allows t h e
d e t e r m i n a t i o n of t h e n u m b e r of n o n e q u i v a l e n t a t o m s .

Electron

Spin

Resonance

aBA ^

Figure 2
A sequential picture of the formation of hyperfine splitting
in the case of an unpaired electron on two equivalent
atoms with nuclear spin / = \
Figure 3
Spectrum of energy levels of the triplet system
T h e a b s o l u t e value of hyperfine splitting e n a b l e s o n e
to d e t e r m i n e the relative density of u n p a i r e d electrons
o n g r o u p s of different a t o m s a n d , c o n s e q u e n t l y , t h e
orbital in w h i c h t h e electron is located.
T h e s i t u a t i o n is s o m e w h a t m o r e c o m p l i c a t e d in
crystalline s u b s t a n c e s c o n t a i n i n g free radicals. C o r
r e s p o n d i n g l y , even m o r e i n f o r m a t i o n is c o n t a i n e d in
their E S R spectra. I n m o n o c r y s t a l s i n t e r a c t i o n s a r e
usually a n i s o t r o p i c . A s a result t h e g factor (it is m o r e
precise t o s p e a k of a g t e n s o r ) a n d the hyperfine
splitting d e p e n d o n t h e relative o r i e n t a t i o n of t h e
crystal a n d t h e m a g n e t i c field.
A p a r t from free radicals, E S R is exhibited b y
molecules with a triplet spin state. If t w o electrons
o c c u p y different orbitals b u t still h a v e t h e d i p o l e dipole i n t e r a c t i o n , there c a n exist b o t h singlet S = 0
a n d t h e triplet S = 1 states. T h e triplet s t a t e is q u i t e a
general case; a p a r t from o r g a n i c s u b s t a n c e s , it is
possessed, for i n s t a n c e , b y m o l e c u l a r oxygen. N o t
only t h e g r o u n d - s t a t e triplets, b u t longlived excited
states also c o n t r i b u t e t o t h e E S R s p e c t r u m . T h i s
excitation m a y be either t h e r m a l w h e n t h e s i n g l e t triplet splitting is small, o r via i r r a d i a t i o n b y electro
m a g n e t i c q u a n t a if t h e splitting is larger.
A peculiar feature of E S R in t h e triplet s t a t e is a
s t r o n g a n i s o t r o p y of level p o s i t i o n s as a function of
o r i e n t a t i o n of the m a g n e t i c field with respect t o t h e
m o l e c u l a r axes a n d t h e persistence of splitting a t t h e
zero m a g n e t i c field. T h i s is d e m o n s t r a t e d b y t h e E S R
s p e c t r u m of the triplet system s h o w n in Fig. 3. I n
chaotically o r i e n t e d systems, this s t r o n g a n i s o t r o p y of
level p o s i t i o n s results in lines of a very c o m p l e x form.
In a w e a k m a g n e t i c field, c o n v e n t i o n a l | + 1>, |0> a n d
I - 1 > states of t h e triplet system a r e m i x e d b y t h e
s p i n - s p i n i n t e r a c t i o n . T h e c o n v e n t i o n a l selection rule
AM = 1 n o longer h o l d s , since o n e c a n n o t ascribe
definite values of t o the energy levels. I n a n S H F
m a g n e t i c field parallel t o t h e external u n i f o r m field,
the AM = 2 t r a n s i t i o n s b e c o m e allowed.

T h e p a r a m a g n e t i c o r g a n i c f o r m a t i o n s a r e of great
i m p o r t a n c e in biological processes, a n d it is therefore
n o t surprising t h a t E S R m e t h o d s h a v e a b r o a d spec
t r u m of a p p l i c a t i o n s in studies of these processes. O n e
of t h e p r o b l e m s e n c o u n t e r e d in these a p p l i c a t i o n s is
t h a t biological systems consist m o s t l y of w a t e r . T h i s
i m p o s e s severe c o n s t r a i n t s o n t h e s h a p e a n d size of
s a m p l e s a n d enforces the use of high-sensitivity E S R
spectrometers.

3. Transition

Metal

Ions:

The

Spin-Orbit

Interaction
S u b s t a n c e s c o n t a i n i n g t r a n s i t i o n m e t a l ions are
a m o n g t h o s e m o s t frequently studied b y E S R m e t h
o d s . A peculiar feature of these ions is the presence of
a n i n c o m p l e t e d o r / shell. In this case, E S R d a t a
e n a b l e o n e t o d e d u c e i n f o r m a t i o n o n t h e intracrystalline field, s p i n - o r b i t a l a n d hyperfine i n t e r a c t i o n s .
W i t h r e g a r d t o their s p i n - o r b i t i n t e r a c t i o n , t h e intracrystalline fields a r e classified as s t r o n g , m e d i u m a n d
weak.
A w e a k crystalline field is o b s e r v e d in the ions of
r a r e - e a r t h m e t a l s . H e r e / electrons a r e well screened
by o t h e r electrons a n d their i n t e r a c t i o n with the
s u r r o u n d i n g crystal is a w e a k o n e . T h e relevant level
2
_1
splitting energy is of t h e o r d e r of 1 0 c m
compared
with a s p i n - o r b i t a l i n t e r a c t i o n of t h e o r d e r of
4
- 1
1 0 c m . T h a n k s to the strong spin-orbit interaction
t h e m a g n e t i c b e h a v i o u r of the system is c o n t r o l l e d by
t h e t o t a l m o m e n t u m / . I n t h e crystalline field definite
j levels split i n t o d o u b l e t s 7 ( a n d singlet M3 = 0,
if J is a n integer). A s t h e influence of the crystalline
field is w e a k , t h e m a g n e t i c p r o p e r t i e s of r a r e - e a r t h
ions in different a g g r e g a t e states d o n o t differ m a r
kedly.
T h e d shell forms t h e o u t e r shells of these ions, so

147

Electron

Spin

Resonance

t h a t they a r e strongly affected b y t h e crystalline field.

S o m e of the d shell electrons interact strongly with
this field, resulting in the splitting of t h e energy levels
of t h e ion. T h e splitting c a u s e d by t h e crystalline field
is so large in this case t h a t only t h e lowest levels a r e
p o p u l a t e d a t a m b i e n t t e m p e r a t u r e s . F o r t h e orbitally
n o n d e g e n e r a t e lowest level, the m a g n e t i c susceptibi
lity is wholly c o n t r o l l e d b y the spin. F o r d ions a
2
-1
(up to
typical s p i n - o r b i t a l i n t e r a c t i o n is 1 0 c m
1
850 c m " ) , w h e r e a s t h e crystalline field i n d u c e d split
4
_ 1
ting is of t h e o r d e r of 1 0 c m . T h i s is a typical case
for a m e d i u m crystalline field.
If a n i n t e r a c t i o n b e t w e e n d electrons is w e a k e r t h a n
a n i n t e r a c t i o n of electrons with s u r r o u n d i n g ligands,
t h e n t h e single-electron p r o b l e m in a crystalline field is
n o longer a d e q u a t e . A correct description s h o u l d
explicitly include electrons of s u r r o u n d i n g i o n s t o o .
T h i s is t h e strong-field case.
I n the m e d i u m crystalline field case, w h i c h is a fairly
g o o d a p p r o x i m a t i o n t o m o s t d i o n s , o n e considers a n
ion in t h e field with cubic s y m m e t r y with a n o c t a h e d
ral o r t e t r a h e d r a l p e r t u r b a t i o n (a typical d-ion en
v i r o n m e n t ) . All the o t h e r i n t e r a c t i o n s c a n be t r e a t e d
as w e a k p e r t u r b a t i o n s of this s t r u c t u r e .
If the a n g u l a r m o m e n t u m of a particle is entirely
d u e t o spin, t h e n t h e g factor s h o u l d be i s o t r o p i c a n d
e q u a l t o 2.00232. A n y a n i s o t r o p y o r d e v i a t i o n of t h e g
factor from this value is d u e t o a c o n t r i b u t i o n from
the orbital m o m e n t u m . A d e v i a t i o n of t h e g factor
from t h e free-electron value is often o b s e r v e d even in
cases w h e n t h e naively expected g r o u n d state is a
purely spin state. T h i s d e v i a t i o n is d u e t o i n t e r a c t i o n
of t h e w o u l d - b e p u r e - s p i n state w i t h a certain excited
state which induces a small a d m i x t u r e of o r b i t a l
m o m e n t u m in t h e g r o u n d state. A n a c c u r a t e t h e o r
etical analysis of t h e energy s p e c t r u m of t h e system is
called u p o n for a successful utilization of E S R spec
trum measurements.
W i t h a l l o w a n c e for a s p i n - o r b i t a l i n t e r a c t i o n with
excited states t h e effective spin H a m i l t o n i a n of t h e
system t a k e s t h e f o r m
*=MBHgS+S\\D\\
where
S = * e| | l | |

2A||A||and||D|| = A ||A||

H e r e 1111 is a t e n s o r a c c o u n t i n g for c o n t r i b u t i o n s of
the orbital m o m e n t a of d e g e n e r a t e states a n d is t h e
s p i n - o r b i t a l i n t e r a c t i o n c o n s t a n t . F o r spins S ^ 1 the
second t e r m is real. A similar c o n t r i b u t i o n c o m e s
from t h e s p i n - s p i n i n t e r a c t i o n . E x p e r i m e n t a l l y , it is
impossible t o decide which c o n t r i b u t i o n t o \\D\\ is
d u e t o the s p i n - s p i n i n t e r a c t i o n a n d which is d u e t o
the s p i n - o r b i t a l i n t e r a c t i o n . O n e often d e c o m p o s e s
S\ID\\S
singling o u t the t e r m
2

D[S z-iS(S+l)]

148

E(S x-S y)

where
D = DZZ-

Dxx

+ D

and E =

Dxx

Dyy
^

is a certain c o m b i n a t i o n of d i a g o n a l c o m p o n e n t s of
O n e uses t h e spin H a m i l t o n i a n as follows. First, t h e
q u a n t i t i e s like t h e g t e n s o r , zero-field splitting a n d
hyperfine s t r u c t u r e c o n s t a n t s a r e experimentally
m e a s u r e d . T h e n , o n e tries t o guess the m o d e l of a
crystalline field which w o u l d c o r r e s p o n d t o t h e spin
H a m i l t o n i a n w h i c h fits t h e observed p a r a m e t e r s .

4. Electron-Nuclear

Double

Resonance

In this a p p l i c a t i o n , E S R is e m p l o y e d t o s t u d y n u c l e a r
m a g n e t i s m . A s w a s m e n t i o n e d a b o v e , t h e E S R signal
d e p e n d s o n t h e difference of p o p u l a t i o n s of levels, a
t r a n s i t i o n b e t w e e n which c o r r e s p o n d s t o the o b s e r v e d
line. If t h e S H F i r r a d i a t i o n intensity is sufficiently
high, p o p u l a t i o n s b e c o m e e q u a l a n d t h e E S R signal
v a n i s h e s in a s t a t i o n a r y state. H o w e v e r , if a hyperfine
splitting o c c u r s , o n e c a n i n d u c e t h e radio-frequency
t r a n s i t i o n s b e t w e e n o n e of t h e levels c o r r e s p o n d i n g t o
E S R , a n d s o m e o t h e r H F I level, t h u s c h a n g i n g t h e
p o p u l a t i o n . T h i s induces a n a b s o r p t i o n a n d the rele
v a n t E S R signal. O n e c a n m a t c h t h e E S R s a t u r a t i o n
level so a s t o m a x i m i z e t h e influence of t h e r a d i o frequency field o n t h e E S R signal. T h e r e c o r d e d E S R
a b s o r p t i o n versus t h e frequency of t h e r a d i o frequency field g e n e r a t o r is called t h e s p e c t r u m of a n
e l e c t r o n - n u c l e a r d o u b l e r e s o n a n c e . T h e m e t h o d of
d o u b l e r e s o n a n c e is used in cases w h e n t h e sensitivity
of c o n v e n t i o n a l n u c l e a r m a g n e t i c r e s o n a n c e is n o t
sufficient t o o b s e r v e t h e desired signal.
T h e great versatility of E S R h a s gained for it a
b r o a d s p e c t r u m of a p p l i c a t i o n s in studies of objects
c o n t a i n i n g p a r a m a g n e t i c centers. T h e r e h a v e been
n u m e r o u s a p p l i c a t i o n s of t h e m e t h o d in studies of
i m p u r i t y centers in s e m i c o n d u c t o r s ; it h a s p r o v e d
possible t o o b s e r v e E S R signals from c o n d u c t i o n
electrons in certain m e t a l s , t h u s e n a b l i n g t h e s t u d y of
the spin-flip scattering of electrons. E S R is widely
used as a t o o l for the analysis of o r g a n i c s u b s t a n c e s
a n d in searches for i m p u r i t i e s .
See also: Nuclear Magnetic Resonance Spectroscopy; Nu
clear Magnetic Resonance Spectroscopy of Solids

Bibliography
Abragam A, Bleaney 1970 Electron Paramagnetic Reso
nance of Transition Ions. Clarendon, Oxford
Algers R S 1968 Electron Paramagnetic Resonance. Tech
niques and Application. Wiley, New York
Atkins W, Symons C R 1967 The Structure of Inorganic
Radicals. An Application of Electron Spin Resonance to the
Study of Molecular Structure. Elsevier, New York

Electron

Low W 1960 Paramagnetic Resonance in Solids. Academic

Press, New York
Low W (ed.) 1963 Paramagnetic Resonance. Academic
Press, New York
McGlynn S P, Asumi T, Kinoshita 1969 Molecular
Spectroscopy of the Triplet State. Prentice-Hall, Englewood Cliffs, NJ
Memory J D 1968 Quantum Theory of Magnetic Resonance
Parameters. McGraw-Hill, New York
Pool C Jr 1967 Electron Spin Resonance, Comprehensive
Treatise on Experimental Techniques. Wiley, New York
Smarts , Bolton J R, Borg D C (eds.) 1972 Biological
Application of Electron Spin Resonance. Wiley, New York
Wertz J E, Bolton J R 1972 Electron Spin Resonance:
Elementary Theory and Practical Applications. McGrawHill, New York
Winter J 1971 Magnetic Resonance in Metals. Clarendon,
Oxford, Chap. 10
V. A . T u l i n
[Institute of Solid State Physics,
M o s c o w , Russia]

Tunnelling

Spectroscopy

electrode will lead t o c h a n g e s in slope of the m e a s u r e d

c u r r e n t - v o l t a g e relation. Specifically, if a s u p e r c o n
d u c t o r energy g a p exists a r o u n d the F e r m i level, n o
c u r r e n t ( o t h e r t h a n t h a t p r o d u c e d by e l e m e n t a r y
excitations a t finite t e m p e r a t u r e s ) will flow until the
applied voltage is g r e a t e r t h a n t h e g a p w i d t h . T h u s ,
the g a p a n d excitation characteristics m a y be
m e a s u r e d . In n o r m a l m e t a l s a n d s e m i c o n d u c t o r s ,
effects of density of states v a r i a t i o n s a r e only usually
seen in thin-film ( t w o - d i m e n s i o n a l ) electrodes (Wolf
1984).
Inelastic processes m a y also o c c u r in the t u n n e l
c u r r e n t (Fig. 1). A n energy loss Ex m a y occur in o r at
t h e edge of the b a r r i e r a n d t h u s lead t o a t h r e s h o l d
The
increase in t u n n e l c o n d u c t a n c e w h e n eV^Ev
energy loss m a y be c a u s e d by excitation of p h o n o n s ,
plasmons, magnons or molecular vibrational and
electronic t r a n s i t i o n s . T h e s e characteristic energies
m a y b e m e a s u r e d with very g o o d resolution a n d
sensitivity ( K h a n n a a n d L a m b e 1983, A d k i n s a n d
Phillips 1985).

Electron Tunnelling Spectroscopy

2. Experimental

If t w o c o n d u c t o r s a r e s e p a r a t e d by a thin i n s u l a t o r ,
typically 3 n m o r less in thickness, c u r r e n t m a y flow
by q u a n t u m - m e c h a n i c a l tunnelling of electrons. Elec
t r o n tunnelling s p e c t r o s c o p y studies v a r i a t i o n s in t h e
t u n n e l c u r r e n t as a function of applied v o l t a g e , t o
d e t e r m i n e b a n d s t r u c t u r e a n d excitation c h a r a c t e r i s
tics of t h e c o n d u c t o r s a n d t h e m a t e r i a l s in t h e insulat
ing g a p . Since t h e energy r e s o l u t i o n is limited only b y
t h e r m a l b r o a d e n i n g of the F e r m i level, m o s t m e a s u r e
m e n t s a r e carried o u t a t liquid h e l i u m t e m p e r a t u r e s .
A m a j o r use of the t e c h n i q u e is in c h a r a c t e r i z i n g
s u p e r c o n d u c t o r s . T h e m a i n a p p l i c a t i o n in n o r m a l
m a t e r i a l s is inelastic tunnelling s p e c t r o s c o p y , w h e r e
the characteristic energies of m o l e c u l a r v i b r a t i o n a l o r
electronic states, o r t h e energies of collective excita
tions ( p h o n o n s o r m a g n o n s for e x a m p l e ) m a y be
determined.

M o s t practical t u n n e l b a r r i e r s c o m p r i s e a m e t a l o x i d e - m e t a l s a n d w i c h , usually m a d e by oxidizing o n e

of t h e m e t a l s a n d t h e n e v a p o r a t i n g the second m e t a l
electrode. M e t a l s such as lead, a l u m i n u m , t a n t a l u m
a n d n i o b i u m a r e c o m m o n l y used b e c a u s e of the ease
with w h i c h u n i f o r m , defect-free oxides m a y be p r o
d u c e d . M o l e c u l e s t o be studied by inelastic tunnelling
spectroscopy (IETS) may be added during barrier
m a n u f a c t u r e o r diffused in a f t e r w a r d s . I n t e r n a l t u n n e l
b a r r i e r s m a y be p r o d u c e d in s e m i c o n d u c t o r s by s h a r p
g r a d i e n t d o p i n g profiles; the t u n n e l d i o d e is the c o m
m o n e s t such device (Sze 1981). Reverse biased
S c h o t t k y b a r r i e r s also c o n s t i t u t e t u n n e l devices.
Recently (Binnig et al. 1982) it h a s been possible to

L Physical

Techniques

Basis

F i g u r e 1 s h o w s a n idealized t u n n e l b a r r i e r with volt

age V applied. E l e c t r o n s m a y t u n n e l directly a c r o s s
(elastic c u r r e n t ) in w h i c h case the c o n d u c t a n c e p e r
unit a r e a for small values of is given b y ( W o l f 1984)

<7xexp(-^)j "

N(E)j^(f(E+eV))dE

T h e need for a thin b a r r i e r , typically 1-3 n m is seen

from t h e e x p o n e n t i a l d e p e n d e n c e of o n thickness t
a n d the m e a n b a r r i e r height . T h e d e r i v a t i o n of t h e
F e r m i function / l e a d s t o a s p e c t r o s c o p y r e s o l u t i o n
d e p e n d e n t o n t e m p e r a t u r e . V a r i a t i o n s in t h e density
of states N(E) d u e t o m a t e r i a l p r o p e r t i e s of t h e

Separation

Figure 1
Schematic of an ideal tunnel barrier between two metals

149

Electron

Tunnelling

Spectroscopy

p r o d u c e tunnelling across a v a c u u m g a p , t h u s avoid

ing uncertainties in t h e b a r r i e r s t r u c t u r e . Since t h e
g a p w i d t h is easily variable, b a r r i e r height c a n be
m e a s u r e d directly. V a c u u m tunnelling occurs over a
very small area; high spatial r e s o l u t i o n ( ^ 2 n m ) m a y
be achieved. T h e m a x i m u m voltage t h a t m a y n o r
mally be applied t o s a n d w i c h s t r u c t u r e s w i t h o u t
b r e a k d o w n is a r o u n d 2 V, limiting the ability t o s t u d y
electronic t r a n s i t i o n s . In c o n t r a s t , v a c u u m tunnelling
m a y be studied a t voltages great e n o u g h t o cause field
emission.
T u n n e l spectra m a y be o b t a i n e d directly from the
c u r r e n t - v o l t a g e (I-V) relation. In t a k i n g inelastic
2
2
directly,
spectra it is c u s t o m a r y t o m e a s u r e d I/dV
the inelastic t h r e s h o l d s t h e n a p p e a r as p e a k s . T h i s is
achieved by m o d u l a t i n g the applied voltage a n d
detecting t h e second h a r m o n i c in the c u r r e n t using a
phase-sensitive detector. T h e signal-to-noise r a t i o is
greatly i m p r o v e d b y this m e t h o d a n d c o n c e n t r a t i o n s
1 0
2
of m o l e c u l a r species as low as 1 0 m m ~ m a y be
detected in t h e barrier.

3.

Applications

C h a r a c t e r i z a t i o n of s u p e r c o n d u c t o r s a n d s t u d y of t h e
J o s e p h s o n (two-electron tunnelling) effect h a v e been
m a j o r a p p l i c a t i o n s . D e s p i t e t h e need t o w o r k a t low
t e m p e r a t u r e s , inelastic tunnelling s p e c t r o s c o p y s h o w s
c o n s i d e r a b l e p r o m i s e . Characteristics of thin insulat
ing films such as silicon dioxide a n d L a n g m u i r Blodgett layers m a y b e d e t e r m i n e d . A s i d e from t h e
high resolution s p e c t r o s c o p y of a d s o r b e d molecules,

150

with relevance t o catalysis, the great sensitivity m a y

lead t o a p p l i c a t i o n s in solid-state electronic chemical
sensing. L i g h t - e m i t t i n g t u n n e l j u n c t i o n s h a v e been
developed ( L a m b e a n d M c C a r t h y 1976); these are
furthering u n d e r s t a n d i n g of t h e c o u p l i n g of r a d i a t i o n
t o r o u g h surfaces. V a c u u m tunnelling h a s allowed the
first real space i m a g i n g of surface a t o m i c structure.
W h e n t h e t e c h n i q u e is fully e x t e n d e d t o t u n n e l spec
t r o s c o p y of b o t h elastic a n d inelastic c u r r e n t s , it will
be p a r t i c u l a r l y powerful d u e t o its very high spatial
resolution.
See also: Scanning Tunnelling Microscopy and Spectros
copy

Bibliography
Adkins C J, Phillips W A 1985 Inelastic electron tunnelling
spectroscopy. J. Phys. C 18: 1313-46
Binnig G, Rohrer H, Gerber Ch, Weibel 1982 Surface
studies by scanning tunnelling microscopy. Phys. Rev.
Lett. 49: 57-61
Khanna S K, Lambe J 1983 Inelastic electron tunnelling
spectroscopy. Science 220: 1345-51
Lambe J, McCarthy S 1976 Light emission from inelastic
electron tunnelling. Phys. Rev. Lett. 37: 923-5
Sze S 1981 Physics of Semiconductor Devices, 2nd edn.
Wiley, New York
Wolf L 1984 Principles of Electron Tunnelling Spectros
copy. Oxford University Press, Oxford

J. B. Pethica
[University of O x f o r d , O x f o r d , U K ]

F
Field-Ion Microscopy: Atom-Probe
Microanalysis
T h e field-ion m i c r o s c o p e ( F I M ) is o n e of t h e few
t e c h n i q u e s t h a t r o u t i n e l y allows t h e i m a g i n g of indi
vidual a t o m s in direct lattice space. T h e F I M is a
p o i n t - p r o j e c t i o n m i c r o s c o p e a n d h e n c e n o lenses a r e
required for t h e f o r m a t i o n of a n i m a g e . T h e i m a g e is a
projection of t h e a t o m s w h i c h reside in the surface of
a sharply p o i n t e d specimen. W h e n a n F I M is c o m
bined with a m a s s s p e c t r o m e t e r (to f o r m a n " a t o m
p r o b e " ) , it is possible t o d e t e r m i n e t h e m a s s - t o - c h a r g e
r a t i o of individual a t o m s , o n e a t a time. I n v e n t e d by
E. W . Muller, t h e F I M a n d a t o m p r o b e h a v e b e e n
used extensively t o s t u d y , for e x a m p l e , p r e c i p i t a t i o n
p h e n o m e n a ( B r e n n e r 1978), surface diffusion of a d a t o m s ( a t o m s a d s o r b e d o n a surface) (Ehrlich 1980,
T s o n g 1980), r a d i a t i o n d a m a g e ( S e i d m a n 1978,
Herschitz a n d S e i d m a n 1984), p h a s e t r a n s f o r m a t i o n s
in steels (Miller et al. 1981), o r d e r - d i s o r d e r alloys
( Y a m a m o t o et al. 1972) a n d segregation ( H e r s c h i t z
a n d S e i d m a n 1985).

1. The Field-Ion

Microscope

A basic m o d e r n F I M consists of a v a c u u m system

(high t o u l t r a h i g h v a c u u m s a r e e m p l o y e d ) , a liquidhelium c r y o s t a t for c o o l i n g t h e specimen t o t e m
p e r a t u r e s in t h e r a n g e 4 . 2 - 3 0 0 K , a well-stabilized
high-voltage supply ( 0 - 3 0 k V ) , a n i n t e r n a l i m a g e intensification system (a 7.5 c m d i a m e t e r c h a n n e l elec
t r o n multiplier a r r a y ( C E M A ) a n d a p h o s p h o r screen)
a n d a gas t r a i n t o s u p p l y t h e r e q u i r e d i m a g i n g gas
(typically h e l i u m o r n e o n ) . A single C E M A h a s a gain
4
of 1 0 M 0 , t h u s very little a d a p t a t i o n t o a d a r k e n e d
r o o m is r e q u i r e d t o o b s e r v e a n F I M i m a g e . T h e F I M
specimen is m o u n t e d p o i n t i n g t o w a r d s the C E M A ; it
is electrically, b u t n o t t h e r m a l l y isolated from t h e
cryostat. T h e d i s t a n c e b e t w e e n t h e specimen a n d the
C E M A is typically 2 . 5 - 8 c m . A wire with a length of
a b o u t 1 c m a n d a d i a m e t e r of 0.1-0.2 m m serves as a
specimen. Before it is inserted i n t o the F I M , t h e wire
is electroetched o r electropolished t o a very fine p o i n t
with a n a v e r a g e r a d i u s of only 5-10 n m . T h e o p e r a t
ing p r o c e d u r e consists of first o b t a i n i n g a b a c k g r o u n d
8
pressure of a t least 1 0 " t o r r , t h e n c o o l i n g t h e speci
m e n with liquid h e l i u m t o a t e m p e r a t u r e b e t w e e n
10 a n d 70 K , backfilling t h e F I M with a n i m a g i n g
5
4
gas t o a p r e s s u r e b e t w e e n 1 0 " t o r r a n d 1 0 " t o r r a n d
finally a p p l y i n g a v o l t a g e t o t h e specimen.

2. Field

Ionization

W i t h t h e aid of a h i g h - v o l t a g e s u p p l y t h e specimen

c a n b e placed a t a positive p o t e n t i a l with respect t o

t h e front surface of the C E M A . Since the average
r a d i u s of t h e tip is quite small, a local electric field of
1
1 0
_ 1
50 V n m
(5 x 1 0 V m ) c a n easily be g e n e r a t e d
with t h e a p p l i c a t i o n of only a few t h o u s a n d volts t o
t h e tip.
1
In a local electric field of 4 5 - 5 0 V n m ' , helium
a t o m s a r e ionized as a result of the tunnelling of a n
electron from a h e l i u m a t o m i n t o the m e t a l (field
i o n i z a t i o n ) . T h e electron t u n n e l s t h r o u g h
the
d e f o r m e d electron p o t e n t i a l energy b a r r i e r in a time
9
of < 10 s. T h e positively c h a r g e d helium ion created
by this process is t h e n accelerated a l o n g a n electric
field line t o t h e internal image-intensification system,
w h e r e its energy is eventually c o n v e r t e d i n t o visible
light. T h e a c t u a l field-ionization events occur over the
sites of individual a t o m s , w h e r e t h e local electric
fieldas o p p o s e d t o t h e a v e r a g e value of the electric
fieldis greatest. A simple physical m o d e l of the
surface of a m e t a l in a high electric field is called the
ionic m o d e l . In this m o d e l , t h e free-electron gas is
p u s h e d b a c k slightly by t h e field i n t o the b u l k of the
m e t a l t o c r e a t e a series of positively c h a r g e d ions o n
t h e surface. T h u s , e a c h individual m e t a l ion is the
s o u r c e of a small pencil of gas ions. T h e helium (or
n e o n ) ion c u r r e n t from e a c h m e t a l ion is a r o u n d
12
1 0 " A a n d t h e t o t a l c u r r e n t from t h e tip is a r o u n d
8
10" A.

3. Field

Evaporation

T h e p r o c e s s of field e v a p o r a t i o n is basic t o t h e use of

t h e F I M as a m e t a l l o g r a p h i c i n s t r u m e n t . Field
e v a p o r a t i o n is the c o n t r o l l e d s u b l i m a t i o n of a t o m s
from a specimen u n d e r the influence of a n electric
field. If t h e voltage o n a specimen is increased to a
critical value, t h e a t o m s o n t h e surface begin t o
sublime, even t h o u g h t h e specimen m a y be as cold as
4.2 K . T h e exact value of t h e electric field a t which
field e v a p o r a t i o n c o m m e n c e s is a function of the
m e t a l being e x a m i n e d . F o r e x a m p l e , t h e e v a p o r a t i o n
1
and
fields of t u n g s t e n a n d gold a r e ~ 5 7 V n m "
- 1
~ 35 V n m , respectively. Since t h e i o n i z a t i o n field of
t h e i m a g i n g gas is i n d e p e n d e n t of t h e m e t a l being
studied, a gas with a n i o n i z a t i o n field t h a t is less t h a n
o r e q u a l t o t h e e v a p o r a t i o n field of t h e m e t a l u n d e r
e x a m i n a t i o n m u s t be used. T h e m i c r o g r a p h of gold
s h o w n in F i g . 1 w a s o b t a i n e d using n e o n as the
i m a g i n g g a s a n e o n a t o m requires a field of
- 1
~35 V n m
for field i o n i z a t i o n t o o c c u r ( A v e r b a c k
a n d S e i d m a n 1973).
The
field-evaporation
p r o c e s s c a n be c o n t r o l l e d
with g r e a t precision b y a p p l y i n g the positive p o t e n t i a l
in t h e f o r m of s h o r t ( 1 - 1 0 m s in w i d t h ) high-voltage

151

Field-Ion

Microscopy:

Atom-Probe

Microanalysis

Figure 1
An FIM image of gold: the (001) plane is in the center of
the image (note the fourfold symmetry about this plane);
specimen termperature 23 K; imaging gas, neon

a t o m a n d h e n c e t h e i o n t h e r e b y r e d u c i n g t h e dia
m e t e r of t h e pencil of i m a g i n g - g a s i o n s . I n practical
t e r m s this m e a n s t h a t t h e effective d i a m e t e r of the
i m a g e of a n a t o m is a function of t h e t e m p e r a t u r e of
t h e tip. T h e r e f o r e , t h e r e s o l u t i o n of t h e F I M is
t e m p e r a t u r e d e p e n d e n t (Chen a n d S e i d m a n 1971).
T h e r e s o l u t i o n of t h e F I M is also a function o f t h e
r a d i u s of t h e tip; t h e b l u n t e r t h e tip the p o o r e r is
t h e r e s o l u t i o n . T h e physical origin of this effect is t h e
a n g u l a r m o m e n t u m of t h e gas a t o m a t t h e i n s t a n t of
its i o n i z a t i o n . I n t h e central-field a p p r o x i m a t i o n t h e
a n g u l a r m o m e n t u m is p r o p o r t i o n a l t o t h e s q u a r e of
t h e r a d i u s of t h e tip. H e n c e , t h e d i a m e t e r of t h e pencil
of i m a g i n g gas i o n s increases with increasing r a d i u s
a n d c o n c o m i t a n t l y t h e r e s o l u t i o n decreases ( G o m e r
1961).
F r o m t h e p r e c e d i n g it is clear t h a t t h e best a t o m i c
r e s o l u t i o n is achieved e m p l o y i n g s h a r p tips ( < 20 n m )
a n d low t e m p e r a t u r e s ( < 20 K ) . T h u s , it is possible in
practice t o o b s e r v e individual a t o m s with i n t e r a t o m i c
distances a p p r o a c h i n g 0.2 n m ( M u l l e r a n d T s o n g
1969).

5. Atom-Probe
pulses. T h i s t e c h n i q u e , called pulse-field e v a p o r a t i o n ,
enables dissection o f a n a t o m i c p l a n e a t a r a t e o f o n e
to three a t o m s p e r pulse. T h u s , t h e a t o m s c o n t a i n e d
within the interior of the specimen c a n be i m a g e d
albeit a t t h e surfaceat a d e t e r m i n e d r a t e . T h e a r e a
of surface e x a m i n e d a t a n y i n s t a n t is a r o u n d 1 0 " 1 4 m 2 .
In practice, a r o u n d 1 0 ~ 23 m 3 of m e t a l c a n be e x a m i n e d
d u r i n g the c o u r s e of o n e d a y e m p l o y i n g t h e pulsefield-evaporation
t e c h n i q u e ; this c o r r e s p o n d s t o
- 6 x 10 5 a t o m s .
A simple physical picture of t h e process of field
e v a p o r a t i o n is o b t a i n e d with t h e aid of t h e ionic
m o d e l . In this m o d e l the applied electric field d e f o r m s
the p o t e n t i a l - e n e r g y c u r v e for a n ion o n t h e surface o f
the specimen a n d i n t r o d u c e s a S c h o t t k y barrier. T h e
ions t h e n e v a p o r a t e b y either j u m p i n g over a small
S c h o t t k y b a r r i e r a s a result of a t h e r m a l l y activated
s t e p o r b y tunnelling t h r o u g h t h e b a r r i e r ( M u l l e r
a n d T s o n g 1969, 1973).

4.

Resolution

T h e d i a m e t e r of t h e pencil of i m a g i n g ions e m a n a t i n g
from e a c h a t o m is a function of t h e t e m p e r a t u r e of t h e
tip. T h e p u r p o s e of cooling t h e specimen t o cryogenic
t e m p e r a t u r e s is to a c c o m m o d a t e thermally the imaginggas a t o m s t o t h e t e m p e r a t u r e of t h e tip, p r i o r t o t h e
field-ionization
event. T h i s t e m p e r a t u r e a c c o m m o d a
tion p r o c e s s reduces t h e transverse velocity of a gas

152

Field-Ion

Microscope

T h e time-of-flight ( T O F ) a t o m - p r o b e F I M consists of
a n F I M c o m b i n e d with a special T O F m a s s spec
t r o m e t e r (see F i g . 2). T h e a t o m p r o b e p e r m i t s t h e
identification of t h e c h e m i s t r y of a n y a t o m t h a t
a p p e a r s in a n F I M i m a g e . T h u s , it is possible t o
o b t a i n a n a t o m i c r e s o l u t i o n i m a g e of m i c r o s t r u c t u r a l
features a n d t o m e a s u r e t h e m a s s - t o - c h a r g e r a t i o
(m/q) of single a t o m s from preselected regions of a
specimen, with a lateral spatial r e s o l u t i o n (i.e., within
t h e surface) of a few t e n t h s of a n a n o m e t e r a n d a
d e p t h spatial r e s o l u t i o n t h a t is d e t e r m i n e d by t h e
i n t e r p l a n a r s p a c i n g of t h e region; the latter q u a n t i t y
c a n be h u n d r e d t h s of a n a n o m e t e r for a high-index
p l a n e . A n a t o m p r o b e with a straight T O F t u b e (Fig.
2) h a s a m a s s r e s o l u t i o n (m/Am) of a r o u n d 200,
w h e r e a s a n a t o m p r o b e with a P o s c h e n r i e d e r lens h a s
a n m/Am value of > 1000. A m a g n e t i c - s e c t o r a t o m
p r o b e h a s been c o n s t r u c t e d t o analyze t h e p r o d u c t s of
the field-evaporation p r o c e s s t h i s i n s t r u m e n t h a s a n
m/Am of a r o u n d 2000 ( M u l l e r a n d S a k u r a i 1974). Its
m a i n d i s a d v a n t a g e a t p r e s e n t is t h a t only a small
p o r t i o n of t h e p e r i o d i c table c a n b e e x a m i n e d a t o n e
time.
T h e o p e r a t i o n of a n a t o m p r o b e c a n be u n d e r s t o o d
with reference t o F i g . 2. W h e n a s h o r t ( < 25 ns) highvoltage pulse ( K p u l s)e is s u p e r p o s e d o n t h e s t e a d y - s t a t e
i m a g i n g v o l t a g e (Vdc), a t o m s o n t h e surface of t h e
specimen a r e field e v a p o r a t e d in t h e f o r m of ions. T h e
ions t h a t a r e projected i n t o t h e p r o b e hole, a t t h e
center of t h e i n t e r n a l image-intensification system,
pass d o w n t h e flight t u b e t o t h e c h e v r o n i o n d e t e c t o r .
T h i s d e t e c t o r consists of t w o C E M A s in series a n d h a s

Field-Ion

Chevron
detector

4-

Front - surfaced
glass mirror

Specimen
voltage
system

Nova 1220
computer

Start

TOF
data

Stop
Digital timer

Figure 2
Schematic diagram of a time-of-flight atom-probe field-ion
microscope

a gain of > 10 . E a c h ion p r o d u c e s a single v o l t a g e

pulse, which s t o p s a clock in t h e digital timer. A
p o r t i o n of t h e h i g h - v o l t a g e e v a p o r a t i o n pulse is used
to start t h e clock. A m i n i c o m p u t e r is used t o c o n t r o l
the specimen v o l t a g e system a n d a n a l y z e t h e d a t a .
T h e T O F s of t h e i o n s a n d t h e voltages a p p l i e d t o t h e
specimen a r e s t o r e d in t h e m i n i c o m p u t e r after e a c h
e v a p o r a t i o n pulse. T h e m/q r a t i o s a r e calculated
according to
m/q = 2e(Vdc

aFp

)(/ -

u l s e

t0) /d

w h e r e e is the c h a r g e o n a n electron, is t h e pulse

factor, d t h e flight d i s t a n c e ( > 2 m ) a n d / - t0 is t h e
a c t u a l T O F of t h e ion. T h e q u a n t i t y / is t h e o b s e r v e d
T O F a n d t0 is t h e t o t a l delay t i m e for t h e system. I n
practice, t h e F I M specimen is p u l s e d a t a frequency of
60 H z .

6. Imaging

Atom-Probe

Mass

Spectroscopy

It is also possible t o p r o d u c e a n i m a g e of t h e a t o m s o n
the surface of a tip b y using t h e field-desorbed i o n s t o
create the i m a g e . T h i s c a n n o w be achieved r o u t i n e l y
e m p l o y i n g a c h e v r o n t o detect t h e individual fieldd e s o r b e d i o n s , w i t h a flight d i s t a n c e of 0.12 m
between t h e specimen a n d t h e c h e v r o n (the s h o r t
flight distance is necessary t o observe t h e entire sur
face a r e a of a tip). T o f o r m a field-desorption i m a g e of
a n ion with a specific m/q r a t i o , t h e c h e v r o n d e t e c t o r
is time-gated, so only t h a t r a t i o is detected. T o
o p e r a t e in this m o d e it is necessary t o e m p l o y a
c h e v r o n d e t e c t o r w i t h a spherical g e o m e t r y . T h i s
g e o m e t r y g u a r a n t e e s t h a t e a c h ion will h a v e t h e s a m e
flight distance, i n d e p e n d e n t of its p o s i t i o n o n t h e
surface of t h e specimen. A n i m a g i n g a t o m - p r o b e m a s s
s p e c t r o m e t e r c a n be used, for e x a m p l e , t o d e t e r m i n e
elemental m a p s of t h e d i s t r i b u t i o n of alloying ele
m e n t s in the vicinity of grain b o u n d a r i e s ( W a u g h a n d
S o u t h o n 1979).

Microscopy:

7. Pulsed-Laser

Atom-Probe

Atom-Probe

Field-Ion

Microanalysis

Microscope

K e l l o g g a n d T s o n g (1980) s h o w e d t h a t it is possible to
field-evaporate
a silicon specimen in a highly c o n
trolled m a n n e r b y i l l u m i n a t i n g it with 6 n s - w i d e
pulses of laser light, while m a i n t a i n i n g t h e specimen
a t a s t e a d y - s t a t e d c voltage. T h i s w o r k built o n the
earlier e x p e r i m e n t s of M e l m e d a n d c o w o r k e r s w h o
d e m o n s t r a t e d t h a t specimens of silicon, g e r m a n i u m
and G a A s had an enhanced
field-evaporation
rate
w h e n they were i r r a d i a t e d w i t h w h i t e light. Kellogg
a n d T s o n g m e a s u r e d t h e m a s s - t o - c h a r g e r a t i o s of the
silicon i s o t o p e s in a c o n v e n t i o n a l time-of-flight a t o m
p r o b e a n d d e m o n s t r a t e d t h a t t h e pulsed-laser a t o m
p r o b e achieved a m a s s r e s o l u t i o n t h a t is c o m p a r a b l e
t o t h a t for m e t a l s e m p l o y i n g h i g h - v o l t a g e pulses.
T h u s , t h e pulsed-laser a t o m - p r o b e field-ion m i c r o
scope c a n be useful for chemically a n a l y z i n g semicon
ducting materials.
See also: Field-Ion Microscopy: Observation of Radiation
Effects

Bibliography
Averback R S, Seidman D 1973 Neon gas imaging of gold
in the field-ion microscope. Surf. Sci. 40: 249-63
Brenner S S 1978 Application of field-ion microscopy
techniques to metallurgical problems. Surf. Sci. 70: 42757
Chen Y C, Seidman D 1971 On the atomic resolution of a
field-ion microscope. Surf. Sci. 26: 61-84
Ehrlich G 1980 Quantitative examination of individ
ual atomic events on solids. / . Vac. Sci. Technol. 17: 9 14
Gomer R 1961 Field Emission and Field Ionization. Harvard
University Press, Cambridge, MA
Herschitz R, Seidman D 1984 An atomic resolution study
of homogeneous radiation-induced precipitation in a neu
tron irradiated W-10at.%Re alloy. Acta Metall. 32:
1141-54
Herschitz R, Seidman D 1985 Atomic resolution observa
tions of solute atom segregation effects and twodimensional phase transitions in stacking faults in dilute
cobalt alloys. Acta Metall. 33: 1547-76
Hochman R F, Muller W, Ralph (eds.) 1969 Applica
tions of Field-ion Microscopy in Physical Metallurgy and
Corrosion. Georgia Institute of Technology Foundation,
Atlanta, GA
Hren J J, Ranganthan S (eds.) 1968 Field-Ion Microscopy.
Plenum, New York
Kellogg G L, Tsong 1980 Pulsed-laser atom-probe field
ion microscopy. J. Appl. Phys. 51:1184
Miller , Beavan A, Smith G D W 1981 A study of the
early stages of tempering of iron-carbon martensites by
atom probe field ion microscopy. Metall. Trans., A 12:
1197-204
Miller , Cerezo A, Hetherington G, Smith G D W
1992 Atom Probe Field-Ion Microscopy. Oxford Univer
sity Press, Oxford
Muller W, Sakurai 1974 A magnetic sector atom-probe
FIM. J. Vac. Sci. Technol. 11: 878-82

153

Field-Ion

Microscopy:

Atom-Probe

Microanalysis

Muller W, Tsong 1969 Field Ion Microscopy: Prin

ciples and Applications. Elsevier, New York
Muller W, Tsong 1973 Field ion microscopy, field
ionization and field evaporation. Prog. Surf. Sci. 4: 1-139
Seidman D 1978 The study of radiation damage in metals
with the field-ion and atom-probe microscopes. Surf. Sci.
70: 532-65
Surface Science (Vol. 23, 1970): issue devoted to Field-ion,
Field Emission Microscopy and Related Topics
Surface Science (Vol. 70, 1978): issue devoted to Field
Emission and Related Topics
Tsong 1980 Quantitative investigations of atomic
processes on metal surfaces at atomic resolution. Prog.
Surf Sci. 10: 165-248
Wagner R 1982 Field-Ion Microscopy. Springer, Berlin
Waugh A R, Southon J 1979 Surface analysis and grainboundary segregation measurements using atom-probe
techniques. Surf Sci. 89: 718-24
Yamamoto M, Neno S, Futamoto M, Nakamura S 1972
Field-ion microscope study of early stages of ordering in
Ni 4MO alloys. Jpn. J. Appl. Phys. 11: 4 3 7 ^ 4
D. N . Seidman
[Hebrew University of J e r u s a l e m ,
J e r u s a l e m , Israel]

2. Capabilities
FIM

Defects in m e t a l s p r o d u c e c o n t r a s t effects in field-ion

m i c r o s c o p e i m a g e s which e n a b l e useful s t u d y of t h e
effects of r a d i a t i o n o n m e t a l s . A s a c o n s e q u e n c e , t h e
field-ion m i c r o s c o p e ( F I M ) a n d a v a r i a n t of this, t h e
a t o m - p r o b e F I M (see Field-Ion Microscopy:
AtomProbe Microanalysis),
a r e widely used in such studies.

7. Capabilities

and Advantages

of the FIM

T h e principal capabilities a n d a d v a n t a g e s of t h e F I M
technique are:
(a)

t h e resolution of individual vacancies with selfinterstitial a t o m s (SIAs) as well as clusters of

these p o i n t defects;

(b)

t h e c o n t r o l l e d dissection of a n i r r a d i a t e d F I M
specimen o n a n a t o m - b y - a t o m basis e m p l o y i n g
the pulse-field-evaporation t e c h n i q u e ;

(c)

t h e ability t o i r r a d i a t e F I M specimens in situ

with atomically clean s u r f a c e s u n d e r u l t r a h i g h v a c u u m c o n d i t i o n s e m p l o y i n g a magnetically
analyzed i o n b e a m ;

(d)

t h e o b s e r v a t i o n a n d i r r a d i a t i o n of specimens a t
cryogenic t e m p e r a t u r e s a s l o w a s 4.2 K w h i c h
a r e below t h e onset of t h e l o n g - r a n g e m i g r a t i o n
of SIAs; a n d

(e)

t h e in situ i r r a d i a t i o n of F I M specimens a t
elevated t e m p e r a t u r e s ( u p t o at least 400 C
seems practical).

154

of the

Atom-Probe

T h e a t o m - p r o b e F I M h a s t h e following features
which m a k e it suitable for t h e s t u d y of t h e chemical
c h a n g e s associated with t h e effects of r a d i a t i o n :
(a)
(b)

(c)

(d)

(e)

(f)

Field-Ion Microscopy: Observation of

Radiation Effects

and Advantages

t h e ability t o d e t e r m i n e t h e m a s s - t o - c h a r g e r a t i o
of a single a t o m t h a t a p p e a r s in a n F I M image;
t h e possibility of chemical identification of all t h e
elements in t h e periodic table, a s t h e m a s s - t o c h a r g e r a t i o is d e t e r m i n e d b y a time-of-flight
technique;
t h e easy identification of elements of low a t o m i c
n u m b e r ( Z < 11)in p a r t i c u l a r , t h e gases h y d r o
gen a n d helium c a n b e analyzed;
a m a s s r e s o l u t i o n m/Am of ~ 200 for a c o n v e n
tional a t o m - p r o b e F I M a n d ^ 1500 for o n e
e q u i p p e d with a P o s c h e n r i e d e r lens;
a spatial r e s o l u t i o n in t h e surface of ~ 0 . 3 0.5 n m t h a t is, t h e chemical identity of t w o
a t o m s s e p a r a t e d b y this d i s t a n c e c a n be deter
mined; a n d
a d e p t h r e s o l u t i o n , in t e r m s of chemistry, t h a t is
d e t e r m i n e d b y t h e i n t e r p l a n a r spacing of t h e
specific (hkl) p l a n e being analyzed (this c a n
c o r r e s p o n d t o < 0.1 n m ) .

T h e analytical c h e m i s t r y features of t h e a t o m - p r o b e
F I M c a n be c o m b i n e d with t h e i m a g i n g capability of
the F I M t o o b t a i n a c o m p o s i t i o n profile t h a t is
associated with a s t r u c t u r a l defect, for e x a m p l e , a
void in a n e u t r o n - i r r a d i a t e d alloy.

3. Some
Induced

Contrast
Defects

Effects

Caused

by

Radiation-

T h e simplest c o n t r a s t effect is t h a t c a u s e d b y a m o n o v a c a n c y . A m o n o v a c a n c y is a lattice site t h a t is

missing its a t o m , a n d its local region is deficient in
positive c h a r g e . Its i m a g e in a n F I M m i c r o g r a p h is
simply a b l a c k s p o t o n a positive p r i n t ; a n a t o m
usually gives rise t o a white s p o t o n a positive p r i n t .
A n a t o m i c site c a n b e s h o w n t o b e v a c a n t b y t h e
careful pulse field e v a p o r a t i o n of e a c h p l a n e . I n
practice, this m e a n s o n e t o three a t o m s r e m o v e d p e r
field-evaporation
pulse ( S e i d m a n 1973).
A n S I A gives rise t o a c o n t r a s t p a t t e r n t h a t is a
result of t h e large n u m b e r of a t o m s displaced from
their e q u i l i b r i u m p o s i t i o n s b y its presence. T h u s , t h e
S I A is sensed a t t h e surface o f t h e F I M specimen
w h e n it lies several a t o m i c layers below t h e surface
( B e a v a n et al. 1971, S e i d m a n a n d Lie 1972).
A d i s p l a c e m e n t c a s c a d e consists of a threed i m e n s i o n a l spatial d i s t r i b u t i o n of vacancies with a
local c o n c e n t r a t i o n of 1-20 at. % . T h e individual
vacancies w i t h i n t h e d i s p l a c e m e n t c a s c a d e c a n b e
detected
b y pulse-field-evaporation
experiments

Field-Ion

( S e i d m a n 1973, 1976, 1978, P r a m a n i k a n d S e i d m a n

1983).
A void detected in f a s t - n e u t r o n - i r r a d i a t e d m e t a l s o r
alloys p r o d u c e s a r a n g e of c o n t r a s t effects t h a t a r e a
function of t h e c r y s t a l l o g r a p h i c region of t h e surface
which it intersects ( B r e n n e r a n d S e i d m a n 1975). T h e
simplest c o n t r a s t effect is a " b l a c k h o l e " t h a t h a s a
d i a m e t e r e q u a l t o t h e d i a m e t e r of t h e void.

4. Examples

of

Studies

T h e t h r e e - d i m e n s i o n a l spatial d i s t r i b u t i o n o f v a c a n
cies c o n t a i n e d within d i s p l a c e m e n t c a s c a d e s , c r e a t e d
by a wide r a n g e of different energetic c h a r g e d p a r t i
cles, h a s b e e n studied in t u n g s t e n a n d p l a t i n u m
(Beavan et al. 1971, S e i d m a n 1973, 1976, 1978). I n all
cases, each d i s p l a c e m e n t c a s c a d e w a s p r o d u c e d b y a
single projectile i o n , so t h e e x p e r i m e n t a l o b s e r v a t i o n s
were a direct reflection o f t h e m a n n e r in w h i c h a single
ion dissipated its energy elastically. S o m e of t h e
properties of each displacement cascade determined
were:
(a)

the a b s o l u t e n u m b e r o f vacancies;

(b)

the average diameter;

(c)

the average vacancy concentration;

(d)

the distribution of first-nearest-neighbor vacancy

clusters;

(e)

t h e r a d i a l d i s t r i b u t i o n function o u t t o t h e n i n t h
nearest n e i g h b o r ; a n d

(f)

t h e direction of m a j o r e l o n g a t i o n .

T h e spatial d i s t r i b u t i o n of S I A s with respect t o t h e

d i s p l a c e m e n t c a s c a d e s w a s m e a s u r e d in i o n - i r r a d i a t e d
tungsten. It w a s s h o w n t h a t t h e S I A s were m o s t
p r o b a b l y c r e a t e d a s a result of focused r e p l a c e m e n t
collision sequences. T h e i s o c h r o n a l recovery b e h a v i o r
of a n u m b e r of in situ i o n - i r r a d i a t e d m e t a l s a n d alloys
w a s studied in detail, for e x a m p l e , t u n g s t e n , t u n g s t e n rhenium, tungsten-carbon, platinum, platinum-gold,
P t 3C o a n d m o l y b d e n u m . T h e t e m p e r a t u r e a t w h i c h
uncorrelated long-range migration occurred was
d e t e r m i n e d b y directly o b s e r v i n g t h e flux o f S I A s t o
the surface of a n F I M specimen; this t e m p e r a t u r e
c o r r e s p o n d e d t o t h e so-called stage IE p e a k . T h e
c o n t r a s t effect p r o d u c e d b y a n S I A w h e n it arrived a t
the surface of a n F I M specimen w a s a n e x t r a - b r i g h t
spot which w a s f o u n d t o b e m e t a s t a b l e over a wide
t e m p e r a t u r e r a n g e ( S e i d m a n et al. 1975).
Direct evidence w a s o b t a i n e d , using t h e F I M , for
the t h e r m a l l y activated release of S I A s from gold
a t o m s in i o n - i r r a d i a t e d specimens o f dilute p l a t i n u m gold alloys. It w a s s h o w n t h a t there were a t least t w o
t r a p p i n g levels associated with each gold a t o m . A n
analysis of t h e i s o c h r o n a l recovery s p e c t r a yielded
values of t h e b i n d i n g e n t h a l p y for e a c h t r a p p i n g level.
The atom-probe F I M was employed to determine the
r a n g e profiles of low-energy (0.1-1.5 k e V ) i m p l a n t e d

Microscopy:

Observation

of Radiation

Effects

H e a n d H e a t o m s in t u n g s t e n , a t 60 K , w h e r e t h e
helium atoms h a d n o atomic mobility (Wagner a n d
S e i d m a n 1979a). T h e diffusive b e h a v i o r of i m p l a n t e d
3
4
H e a n d H e a t o m s w a s m e a s u r e d in t h e a b s e n c e of
p o i n t o r line defects a n d it w a s s h o w n t h a t t h e en
t h a l p y c h a n g e of m i g r a t i o n for b o t h isotopes w a s a p
-1
p r o x i m a t e l y 24 k J m o l ( A m a n o a n d S e i d m a n 1984).
T h e a t o m - p r o b e F I M w a s also used t o o b t a i n direct
evidence of t h e presence of c a r b o n inside a void
detected in a m o l y b d e n u m - t i t a n i u m alloy i r r a d i a t e d
2 6
2
t o a fluence of a p p r o x i m a t e l y 6 x 1 0 m " a t a b o u t
713 ( W a g n e r a n d S e i d m a n 1979b).
O t h e r a p p l i c a t i o n s include studies of sputtering,
reflection coefficients of light gas a t o m s , d i s o r d e r i n g
of o r d e r - d i s o r d e r alloys a n d d i s p l a c e m e n t cascades
p r o d u c e d b y i o n s a t several h u n d r e d k e V .
See also: Field-Ion Microscopy: Atom-Probe Microanalysis

Bibliography
3

Amano J, Seidman D 1984 Diffusivity of He atoms in

perfect tungsten crystals. J. Appl. Phys. 56: 983
Beavan L A, Scanlan R M, Seidman D 1971 The defect
structure of depleted zones in irradiated tungsten. Acta
MetalL 19: 1339-50
Brenner S S, Seidman D 1975 Field ion microscope
observations of voids in neutron irradiated molybdenum.
Radiat. Eff. 24: 73-8
Pramanik D, Seidman D 1983 Atomic resolution observa
tions of nonlinear depleted zones in tungsten irradiated
with metallic diatomic molecular ions. J. Appl. Phys. 54:
6352
Seidman D 1973 The direct observation of point defects in
irradiated or quenched metals by quantitative field ion
microscopy. / . Phys. F. 3: 393-421
Seidman D 1976 Field-ion microscope studies of the
defect structure of the primary state of damage of
irradiated metals. In: Peterson L, Harkness S D (eds.)
1976 Radiation Damage in Metals. ASM International,
Materials Park, OH, pp. 28-57
Seidman D 1978 The study of radiation damage in metals
with the field-ion and atom-probe microscopes. Surf. Sci.
70: 532-65
Seidman D N, Lie 1972 On contrast patterns produced
by self-interstitial atoms in field ion microscope images of
a B.C.C. metal. Acta Metall. 20: 1045-59
Seidman D N, Wilson L, Nielsen C 1975 The study of
stages I to IV of irradiated or quenched tungsten and
tungsten alloys by field ion microscopy. In: Robinson
, Young F W (eds.) 1975 Int. Conf. Fundamental Aspects
of Radiation in Metals, Vol. 1. National Technical Infor
mation Service, Springfield, VA, pp. 373-96
Wagner A,4 Seidman
D 1979a Range profiles
of 300- and
+
4
475-eV H e ions and the diffusivity of He in tungsten.
Phys. Rev. Lett. 42: 515-18
Wagner A, Seidman D 1979b Direct observation of solute
segregation to voids in a fast-neutron irradiated Mo/
1.0at.%Ti alloy. J. Nucl. Mater. 83: 48-58
D . N . Seidman
[ H e b r e w University of J e r u s a l e m ,
J e r u s a l e m , Israel]

155

Fractals

Fractals

Australian coast

S h a p e is o n e of t h e m o s t difficult characteristics of
real objects t o describe a n d quantify. Simple Euclid
ean shapes (squares a n d circles in t w o d i m e n s i o n s , o r
cubes a n d spheres in three) rarely occur. In fact m o s t
assemblages of real objects such as grains in a m e t a l ,
p o r e s in a ceramic, individual p a r t i c u l a t e s in a p o w d e r
or surface m a r k i n g s o n a fracture, are each u n i q u e , so
t h a t even t h e c o n c e p t of a n " a v e r a g e " s h a p e m a y b e
of d o u b t f u l utility. Y e t it is also o b v i o u s t h a t m a n y
aspects of m a t e r i a l s b e h a v i o r , such as the effect of
p r i o r history a n d processing o n p r o p e r t i e s , act
t h r o u g h the shape(s) of individual objects a n d their
interfaces.

1. Methods

of Shape

Analysis:

Fractals

Efforts to describe s h a p e s by c o m b i n a t i o n s of m e t r i c
p a r a m e t e r s , such as t h e aspect r a t i o (length divided by
2
b r e a d t h ) o r form factor (4 a r e a / p e r i m e t e r ) , i g n o r e
the o r g a n i z a t i o n of the irregularities o n the surface o r
outline of the object. In principle a c o m p l e t e descrip
tion of the s h a p e (at least for a t w o - d i m e n s i o n a l
profile) is c o n t a i n e d in the coefficients of a F o u r i e r
analysis of the " u n r o l l e d " s h a p e . H o w e v e r , r e e n t r a n t
shapes a r e n o t easily h a n d l e d with this t e c h n i q u e , a n d
in general the fact t h a t different classes of objects m a y
be m a t h e m a t i c a l l y distinguishable by t h e values of
p a r t i c u l a r h i g h - o r d e r coefficients seems to hide, r a t h e r
t h a n m a k e clear, the real differences in s h a p e which
are often visually evident t o t h e h u m a n observer.
W e desire tools t h a t deal m o r e directly with t h o s e
aspects of s h a p e t h a t we see a n d which m o r e m e a n i n g
fully describe the s h a p e of real lines, b o u n d a r i e s a n d
surfaces. A n i m p o r t a n t aspect of these is the fact t h a t
the a m o u n t of r o u g h n e s s a n d irregularity we c a n see is
generally limited by o u r resolution, which is n o t the
case for a Euclidean line o r surface. W e will consider a
line to be a b o u n d a r y between regions, which h a s n o
internal tension a n d d o e s n o t strive to be straight. T h e
c o n s t r a i n t t h a t the line be " s m o o t h " (that is, h a v e
derivatives a t every p o i n t ) is specifically relaxed, so
t h a t the line c a n be " c r i n k l e d . "
T h e extension of this a p p r o a c h to surfaces is
s t r a i g h t f o r w a r d . I n s t e a d of flat c o n t i n u o u s " E u c l i
d e a n " surfaces, we will be p a r t i c u l a r l y interested in
things t h a t c a n be crinkled u p in w a y s t h a t m a y b e t t e r
describe m a n y " r e a l " surfaces. T h e p a r t i c u l a r type of
crinkled-up b e h a v i o r t h a t is of m o s t interest t o us here
h a s a peculiar form called self-similarity. T h i s simply
m e a n s t h a t at a n y magnification at which we c h o o s e
to view the line o r surface, it l o o k s the s a m e . W h a t
ever m e a s u r e m e n t s we c a n m a k e t o describe t h e
r o u g h n e s s will be i n d e p e n d e n t of the scale. Interest
ingly, these k i n d s of s h a p e s are actually quite c o m
m o n in n a t u r e .
Of course, there a r e s o m e n a t u r a l surfaces t h a t
really a r e s m o o t h a n d Euclidean, particularly facets

156

o3

circle
South African coast
-

German land
"frontier (1900)

west coast of Britain

PortugaMand frontier
1.5

2.5

log l0 (Length of side in kilometers)

Figure 1
Richardson's plots of the lengths of various geographical
boundaries versus the distance used for measurement
(the length of the side of -the polygon used to fit the
boundaries)

t h a t d e v e l o p b e c a u s e of t h e c r y s t a l l o g r a p h i c a t o m i c
lattice, o r m e m b r a n e s t h a t a s s u m e a least-energy
configuration in r e s p o n s e t o surface tension. T h e r e
a r e also n a t u r a l surfaces t h a t a r e r o u g h a n d r a n d o m ,
b u t n o t in the p a r t i c u l a r self-similar w a y we describe
as " f r a c t a l . " In t h e limits as we a p p r o a c h a t o m i c
d i m e n s i o n s o r m a c r o s c o p i c o n e s , t h e n a t u r e of b o u n
daries will c h a n g e , b u t over a b r o a d r a n g e of sizes,
m a n y " r e a l " b o u n d a r i e s c a n be described in this w a y .

2. Richardson

Plots

and Fractal

Dimension

T h i s effect w a s first n o t e d in t w o d i m e n s i o n s , b y a
British m a t h e m a t i c i a n
named Richardson.
He
m e a s u r e d t h e b o r d e r s of several c o u n t r i e s a n d l a n d
masses, b u t the b e s t - k n o w n e x a m p l e is t h e west c o a s t
of Britain. If the length of t h e b o u n d a r y (the coast
line) w a s d e t e r m i n e d b y swinging a l o n g a m a p of t h e
c o u n t r y with dividers set a t s o m e a r b i t r a r y distance,
say 100 k m , a t o t a l length w a s o b t a i n e d . T h e n if t h e
divider distance, o r stride length, w a s reduced, a n d
the s a m e o p e r a t i o n r e p e a t e d , t h e m e a s u r e d length w a s
greater because the m e a s u r e m e n t w a s able t o follow
m o r e of the irregularities of t h e coastline. R e p e a t i n g
the o p e r a t i o n with finer a n d finer steps ( a n d m a p s of
a p p r o p r i a t e scale) w o u l d c a u s e t h e length t o c o n
tinuously increase so t h a t , in effect, the length of t h e
coastline w o u l d b e expected to b e c o m e infinite a t a
fine e n o u g h scale. F u r t h e r m o r e , R i c h a r d s o n n o t e d
t h a t over a c o n s i d e r a b l e r a n g e of stride lengths, a n d
for a variety of b o r d e r s , b o t h n a t u r a l a n d artificial,
the slope of the p l o t of m e a s u r e d length against stride
length w a s c o n s t a n t (see Fig. 1) o n a log scale.
A n e x a m p l e of increasing p e r i m e t e r w i t h o u t
increasing a r e a is s h o w n in Fig. 2. T h i s type of feature
is called a K o c h island, after the m a t h e m a t i c i a n w h o
p r o p o s e d t h e m . All the features a r e d r a w n with t h e
s a m e area; i m a g i n e t h a t in each of the different i m a g e s

Fractals

Figure 2
A Koch island with a perimeter whose fractal dimension is
1.5

y o u r i m a g e r e s o l u t i o n h a s i m p r o v e d by a factor of
four t o distinguish smaller details. T h e p e r i m e t e r o n
each successive feature is increased b e c a u s e of t h e
p a t t e r n e d irregularities i n t r o d u c e d o n e a c h straightline s e g m e n t of t h e b o u n d a r y . T h e a m o u n t of peri
m e t e r increases b y a factor of 1.5 from e a c h feature t o
t h e next a n d there is n o limit t o h o w far we m i g h t
extend this p r o c e s s , so t h e length of t h e p e r i m e t e r is
undefined. T h e m a t h e m a t i c i a n s w h o c o n s i d e r e d
shapes like these w e r e horrified a t t h e b e h a v i o r of
such lines a n d s h a p e s b e c a u s e w i t h o u t s m o o t h , c o n
t i n u o u s derivatives they c o u l d n o t easily b e h a n d l e d
by c o n v e n t i o n a l t e c h n i q u e s .
If t h e increase in m e a s u r e d length w i t h i m p r o v e
m e n t in m e a s u r i n g r e s o l u t i o n is u n i f o r m (a s t r a i g h t
line o n a log p l o t , a s s h o w n in R i c h a r d s o n ' s d a t a ) , t h e
feature is said t o b e self-similar. T h e c o n s e q u e n c e is
t h a t it is n o t really possible t o s t a t e w h a t t h e a m o u n t
of b o u n d a r y o r surface a r e a is. F o r t h e K o c h island
s h o w n in t h e figure, t h e fact t h a t t h e p e r i m e t e r in
creases b y a factor of 1.5 for e a c h h a l v i n g of t h e
m e a s u r e m e n t d i s t a n c e h a s led M a n d e l b r o t (1982) t o
describe this p a r t i c u l a r b o u n d a r y line as h a v i n g a
d i m e n s i o n n o t of 1 (a s t r a i g h t line) o r 2 (a p l a n e ) b u t
1.5. I n o t h e r w o r d s , t h e line h a s a fractional d i m e n
sion which reflects its t e n d e n c y t o fill a p l a n e , a n d
hence it is called a fractal.
D e p e n d i n g o n t h e n a t u r e of t h e irregularity i n t r o
d u c e d o n t h e K o c h island, t h e r a t e a t w h i c h t h e
p e r i m e t e r increases w i t h e a c h step c a n vary. F i g u r e 3
shows several possibilities. I n e a c h case, t h e a r e a of
the feature is u n c h a n g e d as e a c h straight-line s e g m e n t
in the feature b o u n d a r y is replaced, a n d t h e n t h e
sequence r e p e a t e d a t a finer scale, b u t t h e r a t e a t
which t h e p e r i m e t e r increases is given b y t h e v a l u e
s h o w n . T h e s e values a r e related t o t h e slopes of t h e
R i c h a r d s o n p l o t t h a t o n e w o u l d o b t a i n for these
features. H i g h e r fractal d i m e n s i o n s reflect t h e fact
t h a t as t h e s u b s t i t u t i o n s of finer scale irregularities a r e

m a d e , t h e line s p r e a d s o u t faster over t h e p l a n e . F o r

real objects, it is a m e a s u r e of t h e u n c e r t a i n t y a b o u t
j u s t w h e r e t h e b o u n d a r y line lies. A fractal d i m e n s i o n
a p p r o a c h i n g 2.0 w o u l d cover t h e entire p l a n e , while
o n e close t o 1.0 w o u l d r e m a i n n e a r l y a E u c l i d e a n line.
O f c o u r s e , in real features t h e irregularity is n o t so
regular. It is possible t o a p p l y a r a n d o m p a t t e r n t o
increase t h e p e r i m e t e r a l o n g edges with a m e a n fractal
dimension a n d M a n d e l b r o t has shown some examples
of this t e c h n i q u e t h a t p r o d u c e features with s t u n n i n g
realism. T h e Lucasfilm c o m p a n y h a s extensively d e
veloped a n d utilized these m e t h o d s t o p r o d u c e realis
tic b u t u n e a r t h l y l a n d s c a p e s for m o v i e s . T h e fact t h a t
they l o o k c o n v i n c i n g is a further t e s t i m o n y t o their
utility as d e s c r i p t o r s of t h e real w o r l d .
T h e c o n c e p t of self-similarity simply m e a n s t h a t o n
a v e r a g e t h e increase in b o u n d a r y length is u n i f o r m as
r e s o l u t i o n is increased (for i n s t a n c e b y w o r k i n g a t
progressively higher magnifications). G e n e r a t i n g a
fractal b o u n d a r y t h a t is " r a n d o m " c a n b e a c c o m
plished r a t h e r s t r a i g h t f o r w a r d l y b y using t h e first type
of g e n e r a t o r s h o w n in F i g . 3, while v a r y i n g t h e
d i s t a n c e b y which t h e n e w p o i n t s o n t h e line a r e
offset. T h e outlines s h o w n in F i g . 4 b e g a n with
p o l y g o n s f o r m e d b y g e n e r a t i n g a r a n d o m series of
p o i n t s o n a circle. E a c h side w a s t h e n divided i n t o t w o
p a r t s a n d t h e m i d p o i n t displaced either in o r o u t by a
r a n d o m d i s t a n c e , p r o p o r t i o n a l t o t h e length of the
side. T h i s p r o c e s s w a s r e p e a t e d six times, t o m a k e
e a c h side a series of 128 s h o r t s e g m e n t s .
E a c h figure h a s a fractal d i m e n s i o n t h a t is easily
d e t e r m i n e d b y c o n s t r u c t i n g a R i c h a r d s o n p l o t (by
s u m m i n g t h e length of t h e p e r i m e t e r for e a c h of the
h a l v i n g steps). T h e m e a n d i s p l a c e m e n t of t h e m i d
p o i n t s c a n b e varied t o p r o d u c e fractal d i m e n s i o n s
f r o m 1.0 (a E u c l i d e a n p o l y g o n ) t o a b o u t 1.25 a n d the
s h a p e s c r e a t e d a r e very similar in a p p e a r a n c e t o t h o s e
of s o m e real objects (cornflakes, d u s t particles o r
islands, for e x a m p l e ) .

3. Practical

Measurement

of Fractal

Dimension

T o m e a s u r e t h e fractal d i m e n s i o n of real s t r u c t u r e s ,
such as p a r t i c u l a t e s w h o s e surface a r e a m a y be im
p o r t a n t (as a s u b s t r a t e for chemical r e a c t i o n s o r a site

1.5

1.661

Figure 3
Irregularities that can be used on the Koch island with
different fractal dimensions

157

Fractals

slope m-

-D

log [ / m a x i m u m Feret's d i a m e t e r ]

Figure 5
Schematic Richardson plot for a closed outline

Figure 4
Random fractal outlines generated as described in the
text, with varying fractal dimensions

for chemical diffusion, for instance) or profiles

t h r o u g h fracture surfaces, m e a s u r e m e n t s a r e m a d e
using a series of stride lengths a n d the t o t a l d i m e n s i o n
is plotted. Usually, t h e p e r i m e t e r t h u s m e a s u r e d is n o t
a perfect integral multiple of t h e stride length a n d
s o m e p a r t i a l length is left over a t the e n d . T h e
resulting real n u m b e r (integral n u m b e r of strides plus
a fraction) times the length is t h e n the b o u n d a r y
length or perimeter. If this is p l o t t e d against the stride
length , we o b t a i n a R i c h a r d s o n p l o t as s h o w n in
Fig. 5. T h e p l o t deviates from ideal b e h a v i o r at s h o r t
stride lengths because of t h e finite resolution of the
image being m e a s u r e d , a n d at large stride lengths
which b e c o m e a significant fraction of the size of t h e
profile.
It is c u s t o m a r y t o n o r m a l i z e b o t h m e a s u r e m e n t s as
ratios to a characteristic length for the feature, usually
the m a x i m u m F e r e t ' s d i a m e t e r of a closed outline, o r
t h e projected length of a line. ( T h e m a x i m u m F e r e t ' s
d i a m e t e r is the length of the longest s h a d o w the
feature w o u l d cast in a n y direction.) T h i s is n o t
necessary t o d e t e r m i n e t h e fractal d i m e n s i o n itself,
b u t is useful t o c o m p a r e p l o t s of features of different
a b s o l u t e size. It is also necessary t o a d o p t a c o n v e n
tion for dealing with cases a l o n g the p e r i p h e r y w h e n
swinging t h e dividers from o n e p o i n t c a n intersect
several p o i n t s a l o n g the b o u n d a r y . F o r instance, we
m i g h t decide in t h a t case t o use t h e p o i n t farthest
from the original a n d c o n t i n u e the process from there.

158

O n c e the p l o t h a s been o b t a i n e d , t h e fractal d i m e n

sion of t h e b o u n d a r y is o b t a i n e d from m, the slope of
the linear p o r t i o n of t h e p l o t , as: d i m e n s i o n = 1 m.
Because we also a p p l y t h e c o n c e p t of fractal d i m e n
sions t o surfaces (which h a v e a d i m e n s i o n between 2
a n d 3) it is m o s t useful t o deal with the fractional p a r t
separately from t h e integer. F o r a R i c h a r d s o n p l o t of
t h e log of t o t a l surface a r e a against t h e log of the a r e a
element used t o m e a s u r e it, t h e slope will still be - m,
b u t the d i m e n s i o n will be 2 - m. T h i s is h a n d l e d m o s t
simply by writing t h e d i m e n s i o n as 1 .D o r 2.D w h e r e
the value of D (equal t o m) is the decimal fraction,
b e t w e e n 0 (the E u c l i d e a n limit) a n d 0.999 . . . D
c a n n o t actually exceed 1; for t h e K o c h islands s h o w n ,
if t h e g e n e r a t i n g element h a d a n increase in length so
great t h a t t h e fractal d i m e n s i o n w a s 2.0 t h e n t h e
resulting s h a p e w o u l d s p r e a d w i t h o u t limit across
the p l a n e . A l s o , the c u r v e w o u l d h a v e t o be selfintersecting, a n d the b o u n d a r y w o u l d n o longer
u n e q u i v o c a l l y s e p a r a t e t h e inside (feature) from
outside (surroundings).
T h e value of D from the R i c h a r d s o n p l o t is
o b t a i n e d by p e r f o r m i n g a linear least-squares fit t o the
d a t a p o i n t s a n d p r o v i d e s a q u a n t i t a t i v e m e t h o d for
c o m p a r i s o n of different s h a p e s . T h e m e a s u r e m e n t of
p e r i m e t e r by h a n d is very t e d i o u s . C o m p u t e r - a s s i s t e d
d e t e r m i n a t i o n of t h e fractal d i m e n s i o n of a n outline
m a y be carried o u t in several w a y s . T h e m o s t straight
f o r w a r d is available w h e n the feature outlines are
available as a series of p o i n t c o o r d i n a t e s a r o u n d t h e
perimeter, as w o u l d n o r m a l l y be o b t a i n e d if the
feature were outlined using a tablet digitizer t o delin
eate the b o u n d a r y m a n u a l l y . T h i s outline is a m a n y sided p o l y g o n a n d with m o s t types of e q u i p m e n t the
spacing of t h e p o i n t s is fairly u n i f o r m ( d e p e n d i n g
p e r h a p s o n t h e speed of m o t i o n of the o p e r a t o r ' s h a n d
in m o v i n g t h e stylus a r o u n d t h e outline, o r o n a
sensitivity setting in the software). It is easy t o s u m the
p e r i m e t e r of t h e p o l y g o n using all of t h e p o i n t s , a n d
t h e n t o r e p e a t this with every second p o i n t , a n d t h e n
every t h i r d , a n d so forth. W h e n this a p p r o a c h is used,
it is best t o a v e r a g e the p e r i m e t e r d e t e r m i n e d with

Fractals

each p o i n t spacing using all possible s t a r t i n g p o s i

tions, t o m i n i m i z e bias d u e t o s h a r p fissures o r
projections o n t h e outline.
T h e line length will in general decrease a s t h e
p o l y g o n is m a d e c o a r s e r (in t h e E u c l i d e a n limit it
w o u l d n o t c h a n g e ) . P l o t t i n g t h e log of p e r i m e t e r
against t h e log of t h e side length of t h e p o l y g o n
(which is a d e q u a t e l y a p p r o x i m a t e d b y t h e p e r i m e t e r
divided by t h e n u m b e r of p o i n t s used) p r o d u c e s a
R i c h a r d s o n p l o t , from w h i c h t h e fractal d i m e n s i o n D
c a n be d e t e r m i n e d . N o t e t h a t t h e p l o t p r o c e e d s from
the finest r e s o l u t i o n available, n a m e l y t h a t of t h e
original o u t l i n e , u p w a r d s t o a limit i m p o s e d b y t h e
feature size. It is n o t possible t o p r o c e e d t o finer
d i m e n s i o n s for t h e stride length, b e c a u s e there is
simply n o i n f o r m a t i o n available a t a smaller scale
t h a n t h e original p o i n t spacing, w h i c h d e p e n d s o n t h e
resolution of t h e i m a g e e m p l o y e d .
It is possible t o p e r f o r m t h e s a m e o p e r a t i o n w i t h
raster-scanned images by summing the perimeter as
the distances b e t w e e n p o i n t s a t t h e e n d of e a c h r a s t e r
intercept. If this is d o n e as t h e pixel i m a g e is repetiti
vely c o a r s e n e d , a R i c h a r d s o n p l o t c a n a g a i n b e c o n
structed. T h e c o a r s e n i n g c a n be a c c o m p l i s h e d b y
replacing e a c h b l o c k of pixels, initially 2 x 2 a n d of
increasing size, w i t h a single pixel d e p e n d i n g o n t h e
n u m b e r of original pixels in t h e feature. T h e result is
an image with a m o r e " b l o c k y " appearance, and a
shorter perimeter (but, on average, the same area). A n
alternative a p p r o a c h is b y d i l a t i o n of t h e i m a g e
( a d d i n g pixels t h a t h a v e m o r e t h a n a t h r e s h o l d
n u m b e r of n e i g h b o r s ) a n d m e a s u r i n g t h e r a t e a t w h i c h
the n u m b e r of pixels in t h e object increases.

4. Extension

to

Surfaces

T h e s a m e principles a p p l y t o surfaces a s t o outlines.

G e n e r a t e d r a n d o m fractal surfaces c a n b e easily p r o
d u c e d b y b e g i n n i n g w i t h a triangle a n d t h e n displac
ing the m i d p o i n t s of e a c h side u p o r d o w n by a
r a n d o m distance. T h i s creates four smaller triangles
replacing t h e original, a n d t h e y h a v e a g r e a t e r t o t a l
surface a r e a . T h e s e triangles c a n t h e n be further
subdivided t o p r o d u c e a m o d e l of r o u g h surface.
V a r y i n g t h e a m o u n t of d i s p l a c e m e n t c o n t r o l s t h e r a t e
of increase in surface a r e a as t h e triangles b e c o m e
smaller, exactly a n a l o g o u s t o t h e outlines s h o w n
before. T h e result is a surface profile w i t h a fractal
d i m e n s i o n , as s h o w n in F i g . 6.
M e a s u r i n g t h e a r e a of a surface is m u c h m o r e
difficult t h a n m e a s u r i n g t h e length of a n o u t l i n e . T o
d e t e r m i n e t h e fractal d i m e n s i o n of a surface, it is
necessary t o h a v e surface a r e a s d e t e r m i n e d u s i n g a
r a n g e of m e a s u r i n g elements of different sizes. It is
possible t o d o this with triangles, b u t for real surfaces
this is extremely t e d i o u s even with c o m p u t e r assist
ance. T h e r e a r e a few cases in w h i c h a l t o g e t h e r
different m e t h o d s c a n b e used, such as B r u n a u e r -

Figure 6
A generated fractal surface (dimension 2.18) intersected by
a plane; the intersection contour has a fractal dimension
of 1.18

E m m e t t - T e l l e r ( B E T ) m e a s u r e m e n t s of surface a r e a
u s i n g different m o l e c u l a r species (with v a r y i n g sizes).
H o w e v e r , for t h e general case, n o direct m e t h o d for
m e a s u r i n g surface a r e a is really suitable.
A s for m a n y stereological r e l a t i o n s h i p s , it is p o s
sible t o p e r f o r m m e a s u r e m e n t s o n t w o - d i m e n s i o n a l
intersections t h r o u g h solids from w h i c h i n f o r m a t i o n
a b o u t t h e t h r e e - d i m e n s i o n a l s h a p e s c a n be o b t a i n e d .
F o r i n s t a n c e , t h e surface a r e a p e r u n i t v o l u m e 5 V m a y
be d e t e r m i n e d from t h e length of b o u n d a r i e s p e r u n i t
a r e a 2? A, o r even t h e n u m b e r of intersection p o i n t s p e r
length of line PL. It is similarly possible t o relate the
fractal d i m e n s i o n of a surface (a value b e t w e e n 2 a n d
3) t o t h a t of its intersection w i t h a p l a n e (an outline
with a fractal d i m e n s i o n b e t w e e n 1 a n d 2). C o n s i d e r
as a familiar case t h e shoreline a r o u n d a n island.
I s l a n d s t h a t a r e generally r a t h e r r o u g h a n d hilly
w o u l d b e expected t o h a v e a shoreline t h a t is m o r e
irregular t h a n islands t h a t h a v e m o r e g r a d u a l
topography.
F o r t h e ideal case, M a n d e l b r o t h a s s h o w n t h a t for
surfaces g e n e r a t e d using r a n d o m i z e d self-similar frac
tals with a d i m e n s i o n of t h e f o r m 2.D ( O ^ D ^ l ) ,
p l a n e sections t h r o u g h t h e surface p r o d u c e outlines
with a fractal d i m e n s i o n 1 .D. I n F i g . 6 t h e g e n e r a t e d
r a n d o m fractal surface is intersected with a p l a n e
("sea level"), p r o d u c i n g a n outline ( " s h o r e l i n e " )
w h o s e fractal d i m e n s i o n c a n b e m e a s u r e d . T h i s m e a n s
t h a t m e a s u r e m e n t s o n p l a n a r sections using t h e
m e t h o d s a l r e a d y described c a n be applied directly
t o describe surfaces. N o t e t h a t this applies only t o
sections t h r o u g h t h r e e - d i m e n s i o n a l features a n d n o t
projected o r s h a d o w i m a g e s a s a r e often viewed in t h e
t r a n s m i s s i o n light o r electron m i c r o s c o p e . F o r t h a t
case, t h e o u t l i n e will h a v e a value of D t h a t sets a
lower limit t o t h e value for t h e surface.
D i m e n s i o n a l analysis of t h e relationships between
surface a r e a , v o l u m e a n d length a r e s o m e w h a t dif
ferent with these n o n - E u c l i d e a n b o u n d a r i e s t h a n
t h o s e w i t h w h i c h w e a r e generally familiar. In general,

159

Fractals
1/3

1 /2

we w o u l d expect a n y r a t i o of v o l u m e , a r e a
and
length t o be dimensionless. F o r E u c l i d e a n s h a p e s , this
1 /3
m i g h t t a k e the f o r m of expecting v o l u m e
to be
1 /2
p r o p o r t i o n a l t o (surface a r e a )
for a series of
features. H o w e v e r , very different relationships a r e
actually observed in the real w o r l d .

5. Real-World

Examples
1 /3

F o r m a m m a l i a n b r a i n s , v o l u m e is p r o p o r t i o n a l t o
1 / 2 1 6
surface a r e a
. T h i s is a n o t h e r w a y of saying t h a t the
surface of t h e b r a i n h a s a fractal d i m e n s i o n of 2.76,
which w o u l d be revealed by section outlines with a
fractal d i m e n s i o n of 1.76. M a n y o t h e r similar rela
tionships h a v e been quantified for living things,
usually by m a k i n g l o g - l o g plots of p a r a m e t e r s with
very different d i m e n s i o n s a n d units a n d finding
straight-line relationships. S o m e d o n o t fit t h e simple
slopes expected from E u c l i d e a n g e o m e t r y , which in
this c i r c u m s t a n c e is described a s t h e ideal allometric
behavior. T h e d e v i a n t cases m a y involve fractal b e h a
vior for such things as b e n d i n g b e h a v i o r of trees
(which h a v e fractal b r a n c h i n g p a t t e r n s ) a n d speed
against size for s w i m m i n g fish (the b o u n d a r y layer,
which c o n t r i b u t e s m o s t of t h e resistance, m a y h a v e a
fractal n a t u r e ) .
E x a m p l e s from o t h e r fields a r e also available. F o r
instance, consider the r e l a t i o n s h i p between the length
of a river system (which will d e p e n d o n the length of
the yardstick used t o m e a s u r e it) a n d t h e a r e a of t h e
d r a i n a g e basin (which h a s c o n v e n t i o n a l units of a r e a
a n d is n o t sensitive t o the scale of m e a s u r e m e n t ) . It
h a s been s h o w n t h a t t h e s q u a r e r o o t of the basin a r e a
is p r o p o r t i o n a l t o the straight-line distance from
source to m o u t h , b u t t h a t t h e length of t h e river is
p r o p o r t i o n a l t o t h e a r e a raised t o t h e p o w e r 0.6
( r a t h e r t h a n t h e expected 0.5). T h i s is equivalent t o
stating t h a t t h e fractal d i m e n s i o n of typical rivers
is 1.2.
T h e similar use of a r e a versus v o l u m e relationships
for particles viewed in the m i c r o s c o p e is often a m o r e
efficient w a y t o d e t e r m i n e the fractal d i m e n s i o n of the
surface t h a n direct m e a s u r e m e n t of section profiles.
A s a practical e x a m p l e of alternative w a y s t o deter
m i n e t h e fractal d i m e n s i o n of objects, Fig. 7 s h o w s a
plot of the m e a s u r e d m a s s (weight) of clusters of
aggregate particles against the m a x i m u m d i m e n s i o n
of the a g g r e g a t e . B o t h axes a r e n o r m a l i z e d t o a n
individual particle (which m e a n s t h a t the vertical axis
is actually the n u m b e r of particles in t h e aggregate),
b u t this d o e s n o t c h a n g e the overall i n t e r p r e t a t i o n .
D e p e n d i n g o n the c o n d i t i o n s u n d e r which t h e
aggregates form (e.g., t h r e e - d i m e n s i o n a l clusters as
o p p o s e d to t w o - d i m e n s i o n a l g r o w t h o n a s u b s t r a t e )
a n d possible c o n s t r a i n t s o n the w a y t h a t individual
particles c a n m i g r a t e t o w a r d o r a t t a c h t o the aggre
gate, t h e surface ruggedness c a n vary widely (consider
b r a n c h i n g , dendritic s t r u c t u r e s a n d perfectly faceted

160

mox Feret of cluster

particle size

Figure 7
Plot of number of identical particles in an aggregate
against its maximum dimension has a slope equal to the
fractal dimension of the aggregate surface

crystals as extremes). In t h e l o g - l o g p l o t of Fig. 7 the

slope gives t h e fractal d i m e n s i o n of t h e surface of the
a g g r e g a t e directly a n d will be e q u a l t o 2 for cases in
which ideal E u c l i d e a n objects (such as perfect crys
tals) form. M a n y g r o w t h processes w h i c h c a n be
m o d e l l e d as a diffusion-limited a g g r e g a t e , including
s o o t s , d e n d r i t i c trees in t w o o r three d i m e n s i o n s a n d
dielectric b r e a k d o w n , h a v e b e e n s h o w n t o h a v e a
fractal n a t u r e w h i c h c a n be used in modelling, c o m
p a r i s o n a n d i n t e r p r e t a t i o n ( S a n d e r 1986).
M a n d e l b r o t h a s cited e x a m p l e s of fractal b e h a v i o r
in t h e c o n d e n s a t i o n of d r o p l e t s of liquid from v a p o r ,
t h e a r e a - p e r i m e t e r r e l a t i o n s h i p for rain c l o u d s , a n d
for m e m b r a n e s in t h e lung (fractal d i m e n s i o n 2.17).
A p p l i c a t i o n s t o t h e description of p a r t i c u l a t e s r a n g
ing from soils t o aerosols h a v e been a n especially
fertile g r o u n d for the use of fractals. So h a v e p h a s e
t r a n s f o r m a t i o n s , including t h e f o r m a t i o n of gels a n d
p o l y m e r s . It h a s been s h o w n t h a t t h e p a t t e r n of
brightness v a r i a t i o n o n a n i m a g e of a surface ( p r o
d u c e d with either light i l l u m i n a t i o n o r t h e s c a n n i n g
electron m i c r o s c o p e ) c a n also be c o r r e l a t e d directly t o
the surface fractal d i m e n s i o n a n d t h a t scattering of
light o r x-ray p h o t o n s c a n be used t o s t u d y fractal
s t r u c t u r e s . K a y e (1984) h a s p o i n t e d o u t t h a t real
objects often exhibit ideal fractal b e h a v i o r only over a
finite r a n g e of d i s t a n c e a n d in fact t h a t there m a y b e
different slopes in different size r a n g e s . T h e s e m a y
c o r r e s p o n d t o real s t r u c t u r e s in m a t e r i a l s , r a n g i n g
from t h e scale of t h e crystalline s t r u c t u r e t o t h e size of
grains, p o r e s t r u c t u r e s o r m a c r o s c o p i c m a c h i n i n g
m a r k s in c o m p o n e n t s .
C o r r e l a t i o n of fractal d i m e n s i o n s of fracture sur
faces with m e c h a n i c a l p r o p e r t i e s , o r of particle sur
faces with a d h e s i o n , a n d so o n , m a y offer v a l u a b l e
insights i n t o m a t e r i a l s c h a r a c t e r i z a t i o n a n d b e h a v i o r .

Fractals

F r a c t a l analysis h a s been a p p l i e d t o t h e d e s c r i p t i o n of
fracture surfaces in t w o different w a y s . U n d e r w o o d
a n d Banerji (1986) h a v e sectioned p e r p e n d i c u l a r l y
t h r o u g h t h e p l a n e of fracture t o digitize a n d m e a s u r e
the line profile of t h e r o u g h surface. M e c h o l s k y a n d
Passoja (1985) h a v e p l a t e d t h e surface w i t h a c o n t r a s t
ing m a t e r i a l a n d polished parallel t o t h e m a j o r orien
t a t i o n . I n t h e latter case, islands a r e p r o d u c e d (similar
t o F i g . 6) w h o s e outlines c a n be m e a s u r e d . I n b o t h
cases, t h e fractal d i m e n s i o n is of t h e f o r m 1 .D a n d is
a s s u m e d t o be related t o t h e surface 2.D value.
C o r r e l a t i o n s of surface r o u g h n e s s with t e m p e r a t u r e
e m b r i t t l e m e n t in steels a n d with m e a s u r e d fracture
r o u g h n e s s in glass c e r a m i c s a n d a l u m i n a h a v e been
d e m o n s t r a t e d . A t t e m p t s t o m o d e l fracture p r o p a g a
tion a n d t h e g r o w t h of d e p o s i t e d aggregates u s i n g
r a n d o m fractals ( L a i b o w i t z et al. 1985) a r e n o w being
performed.
W o r k with fractals is q u i t e n e w a n d t h e r e is s o m e
tendency a t t h e p r e s e n t time t o a p p l y fractal i n t e r p r e
t a t i o n s t o t o o m a n y real p h e n o m e n a . H o w e v e r , this
will be self-correcting a s m o r e w o r k is d o n e . F u r t h e r

d e v e l o p m e n t s in b o t h t h e o r y a n d i n t e r p r e t a t i o n m a y
be a n t i c i p a t e d .

Bibliography
Kaye 1984 Multifractal description of a rugged fineparticle profile. Part. Characteriz. 1: 14-21
Laibowitz R B, Mandelbrot , Passoja D 1985 Fractal
Aspects of Materials (extended abstracts). Materials
Research Society, Pittsburgh, PA
Mandelbrot 1982 The Fractal Geometry of Nature.
Freeman, New York
Mecholsky J J, Passoja D 1985 Fractals and brittle
fracture. In: Laibowitz et al. 1985, pp. 117-20
Sander L 1986 Fractal growth processes. Nature (Lon
don) 322: 789-93
Underwood , Banerji 1986 Fractals in fractography.
Mater. Sci. Eng. 80: 1-14
J. C. R u s s
[ N o r t h C a r o l i n a State University,
Raleigh, N o r t h C a r o l i n a , U S A ]

161

G
Gamma Radiography
G a m m a r a d i o g r a p h y is a p r o c e d u r e for t h e n o n
destructive e x a m i n a t i o n of industrial m a t e r i a l s , utiliz
ing t h e p e n e t r a t i n g r a d i a t i o n e m i t t e d by r a d i o a c t i v e
sources. G a m m a rays a n d rays of a n y given energy,
b o t h being e l e c t r o m a g n e t i c r a d i a t i o n , a r e indis
tinguishable except for their origin; g a m m a rays
represent t h e release of energy from t h e a t o m i c n u c
leus, while rays result from t h e r e a r r a n g e m e n t of t h e
electron s t r u c t u r e s u r r o u n d i n g t h e nucleus. M o s t
g a m m a r a d i o g r a p h y is c o n d u c t e d with g a m m a rays
h a v i n g energies in t h e m e g a v o l t r a n g e , p r i m a r i l y
because m o s t r a d i o a c t i v e sources e m i t c o p i o u s r a d i
a t i o n at these energies. By c o n t r a s t , m o s t r a d i o g
r a p h y is p e r f o r m e d a t x-ray t u b e p o t e n t i a l s u p t o
h u n d r e d s of kilovolts.
G a m m a r a d i o g r a p h y is used principally for t h e
inspection of welds a n d castings in s t r u c t u r e s such as
steel t a n k s a n d pipelines w h e r e sections a r e thick
e n o u g h to r e q u i r e m e g a v o l t r a d i a t i o n t o p e n e t r a t e
t h e m , o r w h e r e it is a d v a n t a g e o u s t o m a k e use of t h e
p o r t a b i l i t y offered by g a m m a r a d i o g r a p h y e q u i p
m e n t . A n u m b e r of a p p l i c a t i o n s t a k e a d v a n t a g e of the
small size of r a d i o a c t i v e sources t o r a d i o g r a p h objects
from t h e inside, such as t h e walls of s m a l l - d i a m e t e r
pipes. T h i s t e c h n i q u e p e r m i t s a single e x p o s u r e t o
p r o d u c e a r a d i o g r a p h of a n entire circumferential
weld a n d often c o n s i d e r a b l y simplifies t h e i n t e r p r e
t a t i o n of r a d i o g r a p h s of c o m p l i c a t e d s t r u c t u r e s such
as aircraft jet engines w h e r e film w r a p p e d a r o u n d t h e

engine is e x p o s e d by a s o u r c e inserted d o w n the

engine shaft.
H u n d r e d s of artificially r a d i o a c t i v e isotopes a r e
available, offering a wide choice of characteristics.
N a t u r a l l y o c c u r r i n g r a d i u m is n o longer used for
r a d i o g r a p h y , h a v i n g been entirely s u p p l a n t e d by
the c h e a p e r , higher-intensity i s o t o p e ^ C o . W i t h the
g r o w t h of n u c l e a r r e a c t o r s a n d t h e d e v e l o p m e n t of
h a n d l i n g t e c h n i q u e s , practical g a m m a - r a y source
intensities h a v e increased by a factor of a h u n d r e d
since the 1940s, resulting in c o r r e s p o n d i n g l y s h o r t e r
e x p o s u r e times necessary t o p r o d u c e satisfactory
radiographs.

7. Radiographic

Sources

T h e decay of a n y r a d i o a c t i v e nucleus is characterized

by the ejection of a n a l p h a particle o r a b e t a particle
(positive o r negative electron) o r t h e c a p t u r e of a n
external electron, a n y of which usually leave the
nucleus in a n excited state. T h i s is followed a l m o s t
i m m e d i a t e l y by emission of o n e o r m o r e g a m m a rays
( p h o t o n s ) until the nucleus arrives a t a stable g r o u n d
state. Because the excited nucleus c a n exist only at
p a r t i c u l a r energy levels, t h e energies of these g a m m a
rays a n d the r a t e of d e c a y a r e characteristic of the
p a r t i c u l a r i s o t o p e . T h u s , ^ C o always decays by emis
sion of a negative electron followed by t w o equally
a b u n d a n t g a m m a rays of 1.17 M e V a n d 1.33 M e V
energy, a t a r a t e described by a half-life of 5.26 years.

Table 1
Gamma radiography isotopes

Isotope

Half-life

^Co
,37
Cs

5.26 y
30.2 y
74.0 d

1 9 2 I cr

,70

Tm

1 6 9 Y cb

125 d
30.7 d

Effective
gamma
energies (keV)
1250
662
310
457
603
53 (x ray)
84
52 (x ray)
117
191
302

Gamma
intensities a
(rhm per Ci)
1.30
0.32
0.249 |
0.144 =0.46
0.063 J
0.015 |
0 30
0.012 I
0.090 \
0.018
Uy i
0.056
0.022 J

Typical
maximum
source
strength (Ci)

Minimum
thickness ofb
steel (mm)

1000
10

25
18

200

12

50

50

192

a rhm = roentgens per hour at 1 meter b For 2% radiography c The 30 gamma rays of Ir can be represented by
3 monoenergic radiations. For
,70
historical reasons, US industry uses 0.55 rhm per Ci d Because of the low yield of rays and gamma rays from Tm the lcontinuous
radiation
69
generated by the 1 MeV beta rays is an appreciable contaminant that hardens the emitted spectrum e The 24 gamma rays of Yb can be represented
by 3 monoenergetic radiations

163

Gamma

Radiography

Projector

( )

Expose

Drive
Hand

cable

crank

tig

-Source

Snout

I 7
Guide t u b e s

(b)
Source
/

Control

cable

Retra

(c:
Source

\-

Snout
(radiographic
focal p o i n t )

Figure 1
Principle of operation of a typical radiographic exposure device: (a) the source in its stored position, (b) the source in
transit and (c) the source at the radiographic site

N o t all r a d i o a c t i v e isotopes d e c a y by g a m m a - r a y
emission a n d n o t all t h a t d o so a r e useful for g a m m a
r a d i o g r a p h y . I m p o r t a n t factors a r e t h e efficiency of
p r o d u c t i o n of t h e i s o t o p e , its r a t e of d e c a y a n d t h e
a m o u n t of g a m m a r a d i a t i o n t h a t it releases. O n l y five
isotopes (excluding r a d i u m ) h a v e f o u n d m u c h utility
in g a m m a r a d i o g r a p h y (see T a b l e 1), a n d of these,
only c o b a l t , iridium a n d y t t e r b i u m a r e in a p p r e c i a b l e
use t o d a y . O n c e , cesium w a s e m p l o y e d extensively,
particularly in E u r o p e , b u t its low specific activity
_1
(25Cig
m a x i m u m ) severely limits t h e achievable
resolution. W i t h i m p r o v e d m e t h o d s for r e p l a c e m e n t
of spent sources, y t t e r b i u m h a s effectively t a k e n over
the role o n c e played b y t h u l i u m as a low-energy
emitter, since y t t e r b i u m c a n b e p r o d u c e d in consider
ably greater s t r e n g t h s .
137
Except for C s , a fission p r o d u c t , all r a d i o g r a p h i c
isotopes a r e m a d e b y i r r a d i a t i n g t h e element with
t h e r m a l n e u t r o n s in high-flux n u c l e a r r e a c t o r s . Pellets
of metallic c o b a l t o r iridium o r sintered t h u l i u m o r
y t t e r b i u m oxide a r e installed in capsules specially
designed t o avoid excessive self-absorption in t h e
target m a t e r i a l a n d subjected t o fluxes of t h e o r d e r of
15
-2
1
c m s " for times t h a t will m a x i m i z e t h e yield.
Because s o m e of t h e desired r a d i o a c t i v e a t o m s a r e lost
by d e c a y a n d by c a p t u r e of further n e u t r o n s d u r i n g
i r r a d i a t i o n , t h e o p t i m u m times in t h e r e a c t o r a r e
generally less t h a n a half-life of t h e i s o t o p e .
R a d i o g r a p h i c sources a r e m a n u f a c t u r e d b y l o a d i n g
the r a d i o a c t i v e m a t e r i a l i n t o stainless steel capsules
t h a t a r e hermetically sealed b y welding. F o r metallic

164

isotopes, t h e use of a n u m b e r of pellets, e a c h c o n t a i n

ing a small fraction of t h e t o t a l activity, n o t only
a v o i d s n e u t r o n self-absorption a n d c o n s e q u e n t dilu
tion of t h e activity t h a t w o u l d t a k e place if t h e s o u r c e
were i r r a d i a t e d a s a w h o l e , b u t also p e r m i t s t h e
m a n u f a c t u r e of sources of p r e d e t e r m i n e d s t r e n g t h s
regardless of t h e age of t h e r a w m a t e r i a l . R a d i o
graphic resolution considerations dictate that the
physical length of t h e active m a t e r i a l a p p r o x i m a t e its
diameter.

2. Exposure

Devices

T h e c o m m o n e s t f o r m of e x p o s u r e device in t h e U S A
t o d a y consists of a f o o t b a l l - s h a p e d lead o r depletedu r a n i u m shield c o n t a i n i n g a n S-shaped t u b e . A s
s h o w n in F i g . 1, t h e sealed s o u r c e , a t t a c h e d t o a s h o r t
" p i g t a i l , " n o r m a l l y resides a t the center of t h e shield;
after a t t a c h i n g a cable drive system t o the pigtail a t
t h e r e a r of t h e shield, t h e r e m o t e l y located o p e r a t o r
c a n drive t h e s o u r c e o u t of t h e shield a n d a l o n g t h e
guide tube to a prepositioned radiography location by
m e a n s of a h a n d c r a n k . T h e source is later w i t h d r a w n
t o its s t o r a g e p o s i t i o n a t t h e e n d of t h e r a d i o g r a p h i c
e x p o s u r e . R a d i a t i o n from t h e s t o r e d s o u r c e is c o n
fined t o t h e shield by t h e S c u r v e of the internal t u b e .
3
T h e high a t o m i c n u m b e r , high density (18.7 g c m " )
a n d r e a d y availability of depleted u r a n i u m h a s led t o
its a l m o s t exclusive use as a p r i m a r y shielding m a t e r
192
ial in e x p o s u r e devices a n d s o u r c e c h a n g e r s . A n
Ir

Gamma-Ray

e x p o s u r e device shielded with depleted u r a n i u m is

half the weight of a n e q u i v a l e n t lead-shielded unit.
T u n g s t e n - c o p p e r alloy is also used for shielding,
particularly w h e r e t h e design calls for m a c h i n e d p a r t s .

Diffractometry

Pullen D, Hayward 1979 Gamma radiography of welds in

small diameter steel pipes using enriched ytterbium-169
sources. Br. J. Non-Destr. Test. 21: 179-84
. T . C l a r k e
[Technical O p e r a t i o n s Inc., B o s t o n ,
Massachusetts, USA]

3. Exposure

Techniques

E x p o s u r e t e c h n i q u e s for g a m m a r a d i o g r a p h y a r e
similar t o t h o s e for r a d i o g r a p h y , except t h a t e x p o
sure times a r e generally m e a s u r e d in m i n u t e s r a t h e r
t h a n seconds a n d t h e energy a n d hence p e n e t r a b i l i t y
of t h e r a d i a t i o n c a n be varied only by using different
isotopic sources. T h e variables affecting e x p o s u r e
include, besides t h e e x p o s u r e time, t h e s o u r c e s t r e n g t h
a n d distance from t h e film, t h e thickness of t h e section
t o be p e n e t r a t e d a n d t h e sensitivity of t h e d e t e c t o r
system. T h e r a d i o g r a p h e r usually w o r k s with a m i n i
m u m source-film d i s t a n c e consistent with a c c e p t a b l e
geometric d i s t o r t i o n a n d r e s o l u t i o n in o r d e r t o m i n i
mize e x p o s u r e time.
M i n i m u m thicknesses of steel for w h i c h flaw detec
tion c a n be carried o u t successfully a r e given in
T a b l e 1. G a m m a r a d i o g r a p h y is nevertheless useful in
t h i n n e r sections w h e r e t h e p u r p o s e is t o display t h e
presence of relatively large objects, such as reinforcing
b a r s in c o n c r e t e slabs o r h i d d e n i n t e r n a l p a r t s in
c o m p l i c a t e d assemblies.
I n general, e x p o s u r e t e c h n i q u e s for g a m m a r a d i o g
r a p h y a r e similar t o t h o s e for high-energy r a y s
g e n e r a t e d a t p e a k voltages a p p r o x i m a t e l y d o u b l e t h e
p h o t o n energies. T h u s , a b s o r p t i o n curves for ^ C o
r a d i a t i o n in steel a r e similar t o t h o s e for 2.5 M V p
radiation.
See also: Neutron Radiography

Gamma-Ray Diffractometry
T h e very low a t t e n u a t i o n of g a m m a rays in m a t t e r
allows their use t o s t u d y t h e lattice perfection of thick
crystals. A n e x a m i n a t i o n of s a m p l e s in a furnace,
c r y o s t a t o r u l t r a h i g h - v a c u u m ( U H V ) device is also
possible a n d c a n p r o v i d e i n f o r m a t i o n a b o u t b u l k
p h a s e t r a n s i t i o n s . W h e n u s i n g t h e 468 k e V r a d i a t i o n
192
of I r t h e a t t e n u a t i o n coefficient of nickel a m o u n t s t o
1
only " ~ 0 . 8 c m . T h e B r a g g angles a r e of the o r d e r
of . T h u s t h e m e a s u r e d r o c k i n g curves a r e only
affected by lattice tilts a n d small-angle grain b o u n d
aries. T h e i n t e g r a t e d B r a g g diffraction intensity of
nearly perfect crystals is c o r r e l a t e d with t h e disloca
tion density in these crystals.

1. The Gamma-Ray

Diffractometer

T h e essential c o m p o n e n t s of t h e g a m m a - r a y diffract
o m e t e r a r e s h o w n in Fig. 1. T h e s e a r e g a m m a - r a y
s o u r c e , a c o l l i m a t o r for p r e p a r i n g a b e a m with small
a n g u l a r divergence, a s a m p l e fixed o n a g o n i o m e t e r
a n d a n N a l scintillation c o u n t e r for detecting
t h e direct a n d diffracted b e a m s . T h e g a m m a - r a y
source
consists
of
a
small
iridium
sheet
(0.2 m m x 4 m m x 10 m m ) shielded by a u r a n i u m b o x
a n d m a d e r a d i o a c t i v e by n e u t r o n a c t i v a t i o n t o a n
activity of a b o u t 1 T B q (100 Ci). T h e r a d i o i s o t o p e
*^Ir t h u s g e n e r a t e d decays w i t h a half-life of 74 d a y s

Bibliography
Clarke 1959 Isotope radiation sources. In: McMaster R
C (ed.) 1959 Nondestructive Testing Handbook. Ronald
Press, New York, Sect. 15
Clarke 1976 Radiographing the Liberty Bell. Foundry
Trade J. 141 (Aug): 223-8
Clarke 1980 Radiography of the Cape Hatteras light
house. Technol. Conserv. 5(1): 20-4
Clarke , Coenraads C 1967 Radiographic Characteris
tics of Ytterbium 169, Report ORNL-IIC-10. Oak
Ridge National Laboratory, Oak Ridge, TN
Evans R D 1955 The Atomic Nucleus. McGraw-Hill, New
York
Glasgow G P, Dillman L 1979 Specific gamma ray
constant and exposure rate constant of iridium-192. Med.
Phys. 6(1): 49-52
Graham R L, Wolfson J L, Bell R 1952 The disintegration
of thulium-170. Can. J. Phys. 30: 459-75
Hatziandreou L, Ladopoulos G 1980 Use of radiography
for solution of diagnostic problems existing in marble
monuments. Materialprufung 22: 298-300

-2m-

Detector

--r

'

i
ill .
jl I

j-fe "
1

Source
Collimator
Furnace
Sample space

Figure 1
Experimental setup of a gamma-ray diffractometer

165

Gamma-Ray

Diffractometry

i n t o excited levels of ^fPt, w h i c h emits g a m m a rays

of several energies. O n e of these p r o d u c e s t h e 468 keV
6
line. Because of a n energy r e s o l u t i o n /= 1 0 "
a m o n o c h r o m a t o r system is n o t necessary. T h e
b e a m divergence in t h e g e o m e t r y of Fig. 1 is a b o u t
12 a r c sec.
T h e d e t e c t o r is set o n t h e Bragg-angle p o s i t i o n
before t h e m e a s u r e m e n t starts. T h e crystal is r o t a t e d
in steps a r o u n d a n axis oriented vertically t o t h e
diffraction vector. T h e p l o t of B r a g g intensity 7 B
against r o c k i n g angle , t h e " r o c k i n g c u r v e , " reflects
t h e d i s t r i b u t i o n function W () o f the lattice tilts. A
(x, z)-translation facility allows t h e e x a m i n a t i o n o f
a n y v o l u m e element o f a crystal.
T h e m e a s u r e d reflectivity d i s t r i b u t i o n function
r m(co) is given b y

where 7 U is t h e b a c k g r o u n d intensity a n d IT is t h e
intensity of the t r a n s m i t t e d b e a m . T h e integral Rm =
J rjjco) dco, called t h e m e a s u r e d i n t e g r a t e d reflecting
p o w e r , d e p e n d s only o n t h e p r o p e r t i e s of t h e crystal
a n d n o t o n t h e incident intensity. O w i n g t o t h e high
energy of t h e g a m m a r a y s , s a m p l e s a r e always ex
a m i n e d in t r a n s m i s s i o n g e o m e t r y ( L a u e case). Small
4
v a r i a t i o n s of t h e lattice p a r a m e t e r (1 in 10 ) a r e
usually negligible.

2. Gamma-Ray

Diffraction

Theory

In t h e t h e o r y of x-ray a n d g a m m a - r a y diffraction t w o
limiting cases h a v e t o b e considered: t h e k i n e m a t i c a l
a n d t h e d y n a m i c a l regimes ( Z a c h a r i a s e n 1945).
W h i c h case is t o b e applied d e p e n d s o n t h e w a v e
length of t h e r a d i a t i o n used, t h e diffraction angle a n d
the crystal perfection (dislocation density) ( F r e u n d
1973). W h e n w o r k i n g with small w a v e l e n g t h s a n d
imperfect crystals t h e k i n e m a t i c a l a p p r o a c h , which
will b e discussed in t h e following, is valid.
T h e basic a s s u m p t i o n of t h e k i n e m a t i c a l t h e o r y is
D a r w i n ' s m o s a i c m o d e l ( D a r w i n 1922) in which t h e
crystal is a s s u m e d t o b e divided i n t o m a n y , slightly
misoriented, small perfect crystal blocks (see Fig. 2).
T h e t o t a l diffracted intensity is t h e s u m o f t h e intensit
ies t h a t e a c h block diffracts. T h e lattice tilts b e t w e e n
the blocks a r e described b y t h e m o s a i c d i s t r i b u t i o n
function W(co), which in t h e ideal case will b e a
G a u s s i a n function (Schneider 1981). I t s full w i d t h a t
half m a x i m u m ( F W H M ) is t h e m o s a i c angle . T h e
reflectivity d i s t r i b u t i o n function r k i n(a>) is given b y

Figure 2
Schematic representation of the diffraction process in a
mosaic crystal

integrated reflecting power

obtained with J W(a>) da> = 1:
tL sin

k m

e xt

3.1 Crystal
Growth

166

r0X\FH]

cos

is

0BJ

exp(-M)

w h e r e r 0 is t h e classical electron r a d i u s , FH is t h e
s t r u c t u r e factor, exp( - M) is t h e D e b y e - W a l l e r fac
t o r , V is t h e v o l u m e of t h e e l e m e n t a r y cell a n d / e xt is
t h e " e x t i n c t i o n l e n g t h . " Rkin represents a n u p p e r limit
for t h e i n t e g r a t e d reflecting p o w e r . If Rm = Rkin a
crystal is called ideally imperfect. I n m o s t cases t h e
relation Rdya < Rm< R^ is valid, w h e r e Rdyn is deter
m i n e d from d y n a m i c a l t h e o r y .
W h e t h e r t h e crystals diffract in a d y n a m i c a l o r
k i n e m a t i c a l m a n n e r d e p e n d s o n t h e extinction length
text defined in E q n . (3) a n d o n t h e size t0 of the defectfree d o m a i n s s h o w n in F i g . 2. F o r t0 > i e xt (perfect
crystal) d y n a m i c a l t h e o r y is applied, a n d for t0 < text
k i n e m a t i c a l t h e o r y is applied. O n e o b t a i n s , for in
stance, a value of / e xt = 73 for t h e diffraction o f
2.65 p m g a m m a r a d i a t i o n a t a (222) reflection o f a
c o p p e r crystal. W i t h dislocation densities larger t h a n
2
- 2
1 0 m m , t h e a v e r a g e m o s a i c block w i d t h c o r r e s
p o n d i n g t o t h e a v e r a g e d i s t a n c e b e t w e e n dislocations
is m u c h smaller t h a n t h e extinction length, resulting in
k i n e m a t i c a l diffraction b e h a v i o u r .

3. Applications

w h e r e T0 is t h e thickness of the crystal, is t h e linear

a b s o r p t i o n coefficient, is t h e w a v e l e n g t h of t h e
g a m m a r a d i a t i o n a n d is t h e B r a g g angle. T h e

20R

Rkin = $ rkin(co)dco

of Gamma-Ray

Perfection

Analysis

Diffractometry
During

Crystal

A vertical S t o b e r - t y p e crystal g r o w t h u n i t w a s
designed a n d placed in t h e g a m m a - r a y b e a m . C o p p e r
crystals (6 m m in d i a m e t e r b y 120 m m ) were g r o w n in

Gamma-Ray

Diffractometry

Figure 3
(a) Time dependence of the integrated intensity of the (111) reflection; (b) growing crystal in the gamma-ray beam

a g r a p h i t e crucible with (110) o r i e n t a t i o n . T h e t e m

p e r a t u r e g r a d i e n t w a s m e a s u r e d in t h e crucible wall
with four t h e r m o c o u p l e s . T h e crucible w a s placed o n
a w a t e r - c o o l e d finger a n d c o v e r e d with a silica t u b e ,
4
which w a s e v a c u a t e d t o a p r e s s u r e of 1 0 " P a . T h e
w h o l e a r r a n g e m e n t c o u l d be r o t a t e d a r o u n d t h e crys
tal axis for r o c k i n g - c u r v e m e a s u r e m e n t s a n d t r a n s
lated vertically a n d h o r i z o n t a l l y for s c a n n i n g . T h e
g r o w t h u n i t a b s o r b e d a b o u t 6 6 % of t h e b e a m i n t e n
sity. F i g u r e 3b s h o w s t h e g r o w i n g c o p p e r single
crystal o b s e r v e d by t h e g a m m a - r a y b e a m (Welter et
al. 1983). I n o r d e r t o d e t e r m i n e t h e speed of solidifica
tion, t h e s o l i d - l i q u i d interface is first p o s i t i o n e d
slightly below t h e b e a m . T h e n t h e t e m p e r a t u r e of t h e
furnace is lowered a t a c o n s t a n t r a t e t { t o initiate
m o v e m e n t s of t h e interface. R o c k i n g curves w e r e
m e a s u r e d w h e n t h e interface r e a c h e d t h e lower level
of the incident b e a m . In F i g . 3a t h e i n t e g r a t e d inten
sity Rm is p l o t t e d a g a i n s t solidification time. W h e n t h e
interface reaches t h e u p p e r level of t h e g a m m a b e a m ,
Rm r e m a i n s c o n s t a n t . T h e i n t e g r a t e d reflecting p o w e r
c o r r e s p o n d s t o k i n e m a t i c a l c o n d i t i o n s in w h i c h t h e
intensity of t h e diffracted b e a m is p r o p o r t i o n a l t o t h e
diffracting v o l u m e , E q n . (2), a n d h e n c e t o t h e p o s i t i o n
of the interface. I n this case t h e speed of solidifi
c a t i o n is d e t e r m i n e d w i t h a n a c c u r a c y of 5 % b y
= 1 c m / (height of g a m m a - r a y b e a m , 1 c m ; At
from Fig. 3). T h e t e m p e r a t u r e g r a d i e n t in t h e solid a t
the s o l i d - l i q u i d interface c a n b e o b t a i n e d from
g r a d Ts =

tr/v

By d e t e r m i n i n g a t different p o s i t i o n s in t h e
growing crystal, t h e t e m p e r a t u r e field T{z) c a n b e
estimated.

S u c h m e a s u r e m e n t s also allow a direct analysis of

crystal perfection d u r i n g g r o w t h . I n F i g . 4 r o c k i n g
curves of a g r o w i n g crystal a r e s h o w n m e a s u r e d a t
different heights (z axis). C u r v e 1 indicates t h e m o s a i c
s p r e a d of t h e seed crystal. After g r o w t h t h r o u g h a
n a r r o w neck (2->3) a m i s o r i e n t e d s u b g r a i n h a s
disappeared.
3.2 Order-Disorder
Transition in Ni3Al
T h e u n u s u a l m e c h a n i c a l s t r e n g t h of t h e intermetallic
c o m p o u n d N i 3 A l ( L l 2 s t r u c t u r e ) is c a u s e d by the
a t o m i c l o n g - r a n g e o r d e r . T h e intensity of a superlattice reflection is c o r r e l a t e d with t h e l o n g - r a n g e
o r d e r p a r a m e t e r 5 , defined as (Cullity 1978)
r

_ A\ ~ * A 1

w h e r e r A1 is t h e p r o b a b i l i t y t h a t a n Al a t o m site is
filled b y a n Al a t o m a n d FM is t h e a t o m i c fraction of
Al in t h e alloy. S varies b e t w e e n 0 ( c o m p l e t e d i s o r d e r )
a n d 1 ( c o m p l e t e o r d e r ) . I n t h e case of g a m m a - r a y
diffraction t h e v a l u e for S c a n be o b t a i n e d from the
relationship

_* > ex

( -

2MP>)

flJTl/A.

3 / N i|

R^exp(-2M^)e^\fM-fNi\'
w h e r e e x p ( - M) is the D e b y e - W a l l e r factor a n d y j is
t h e a t o m i c scattering factor. T h e v a r i a t i o n of the
i n t e g r a t e d intensity with t e m p e r a t u r e for a nearly
s t o i c h i o m e t r i c N i 3 A l single crystal is s h o w n in Fig. 5.
T h e (200) reflection intensity decreases o w i n g t o t h e
D e b y e - W a l l e r factor. T h e (100) B r a g g diffraction

167

Gamma-Ray

Diffractometry

Figure 4
Series of gamma-ray rocking curves measured along growth direction (z axis) during a crystal growth experiment

intensity is n e a r l y i n d e p e n d e n t of t e m p e r a t u r e b e l o w
1300 C, b u t t h e n declines a t 1 3 3 0 C i n d i c a t i n g t h e
existence of a n o r d e r - d i s o r d e r t r a n s i t i o n a t a t e m p e r
a t u r e slightly below t h e m e l t i n g p o i n t .

(200) fundamental

3.3 Determination of Stress in Tantalum Silicide

Thin Films on Crystalline Silicon Substrates
T h i n T a S i 2 films (of thickness ~ 1 0 0 n m ) were p r e
p a r e d b y sequential e v a p o r a t i o n o n t o (100) silicon
single-crystal s u b s t r a t e s . T h e size of t h e s u b s t r a t e s
w a s 25 m m x 10 m m 0.15 m m . After d e p o s i t i o n , a n
a n n e a l i n g step a t 900 C for o n e h o u r in a v a c u u m of
6
1 0 " P a w a s c a r r i e d o u t t o crystallize t h e a m o r p h o u s
T a - S i m u l t i l a y e r m i x t u r e . X - r a y diffraction analysis
of these films s h o w e d polycrystalline T a S i 2 with a
preferred (001) o r i e n t a t i o n . D u r i n g t h e f o r m a t i o n of
t h e silicide t h e v o l u m e of t h e layer s h r i n k s b y a b o u t
2 5 % . After c o o l i n g , a b u c k l i n g of t h e s u b s t r a t e crystal
is o b s e r v e d . T h e c o r r e s p o n d i n g b e n d i n g of t h e lattice
p l a n e s c a n b e m e a s u r e d b y g a m m a - r a y diffractom
etry. F i g u r e 6 s h o w s t h e e x p e r i m e n t a l s e t u p . A t

ray
-0.03 A
Temperature *0

Figure 5
Temperature dependence of the (200)-fundamental and
(lOO)-superlattice reflections of a nearly stoichiometric
Ni 3Al single crystal indicating an order-disorder transition
at 1330 C
168

Si substrate'

^ TaSi2 film

Figure 6
Experimental setup for determining the radius of
curvature

Gas and Liquid

Hoffmann R W 1966 The mechanical properties of thin

condensed films. Phys. Thin Films 3: 211-73
Retajczyk F Jr, Sinha A 1980 Elastic stiffness and
thermal expansion coefficients of various refractory sui
cides and silicon nitride films. Thin Solid Films 70: 241-7
Schneider J R 1981 Applications of gamma-ray diffractometry. Nucl. Sci. Appl. 1: 227-76
Welter J M, Bremer F J, Wenzl 1983 Gamma-ray
diffractometry in crystal growth studies. J. Crysi. Growth
63: 171-3
Zachariasen W 1945 Theory of X-ray Diffraction. Wiley,
New York

5001-

-*

Chromatography

30

F . J. B r e m e r a n d H . Bleichert
[ K F A Julich, Julich, G e r m a n y ]

Figure 7
Radius of curvature for different film conditions:
(a) substrate without film; (b) multilayer tantalum 1.1 nm,
silicon 2.4 nm; (c) TaSi 2 after annealing at 900 C

p o s i t i o n (1) t h e r o c k i n g c u r v e of t h e silicon s u b s t r a t e
is m e a s u r e d . T h e n t h e s a m p l e is t r a n s l a t e d b y a n d
the r o c k i n g c u r v e is m e a s u r e d a g a i n a t t h e n e w
p o s i t i o n (2). A n y b e n d i n g o f lattice p l a n e s b e t w e e n
t h e t w o p o s i t i o n s s h o w s u p a s a shift of t h e a n g u l a r
p o s i t i o n o f t h e crystal a t t h e B r a g g p e a k . T h e r a d i u s
of c u r v a t u r e c a n b e c a l c u l a t e d b y r = / , w h e r e
is t h e a n g u l a r shift. If t h e s u b s t r a t e thickness ts is
m u c h smaller t h a n t h e r a d i u s o f c u r v a t u r e r o f t h e
s u b s t r a t e a n d m u c h larger t h a n t h e film thickness t{,
t h e film stress c a n b e c a l c u l a t e d from t h e e q u a t i o n
I

Gas and Liquid Chromatography

G a s c h r o m a t o g r a p h y ( G C ) has been a revolutionary
force in t h e g r o w t h of o r g a n i c c h e m i s t r y b e c a u s e of
t h e g r e a t simplification in t h e analysis of volatile
s a m p l e s t h a t it offers. L i q u i d c h r o m a t o g r a p h y ( L C ) is
c o m p l e m e n t a r y t o G C in t h a t it is effective for n o n
volatile m a t e r i a l s . L C h a s h a d a similar i m p a c t o n
o r g a n i c c h e m i s t r y a n d b o t h t e c h n i q u e s h a v e h a d wide
influence, with a p p l i c a t i o n s in b i o c h e m i s t r y , inor
g a n i c c h e m i s t r y a n d p o l y m e r science. B o t h a r e rela
tively recent t e c h n i q u e s a n d i n s t r u m e n t a t i o n a n d
m e t h o d s h a v e b e e n d e v e l o p e d a t a r a p i d r a t e in t h e
recent d e c a d e s . I n this article t h e t w o a r e a s of c h r o
m a t o g r a p h y a r e i n t r o d u c e d a n d their c u r r e n t states of
d e v e l o p m e n t described.

*U

6 1 - tf r
where a n d are Y o u n g ' s modulus a n d Poisson's
r a t i o for t h e s u b s t r a t e ( H o f f m a n n 1966). F r o m F i g . 7
9
we o b t a i n , for e x a m p l e , = 1.68 10 P a , w h i c h
is in g o o d a g r e e m e n t w i t h results o f o t h e r a u t h o r s
(Retajczyk a n d S i n h a 1980). T h e b e n d i n g a n d t h e
residual high stress is d u e t o t h e difference in t h e r m a l
s h r i n k a g e o f s u b s t r a t e a n d film d u r i n g c o o l i n g .
W i t h t h e m e t h o d described, o n e c a n m e a s u r e radii o f
c u r v a t u r e u p t o 500 m , d e p e n d i n g o n t h e s u b s t r a t e
quality.
See also: X-Ray Powder Diffraction

7. Gas

(a)

a s o u r c e of clean c a r r i e r g a s (helium, h y d r o g e n ,
n i t r o g e n o r o t h e r s ) t h a t h a s a precisely regulated
flow r a t e ;

(b)

a heated zone containing a rubber-septum-sealed

injection p o r t t h r o u g h w h i c h t h e s a m p l e is i n t r o
d u c e d i n t o t h e flowing carrier-gas s t r e a m with a
syringe;

(c)

a s e p a r a t i n g c o l u m n (generally i o r i in. (0.32 o r

0.64 m m ) d i a m e t e r stainless steel o r glass tube)

Bibliography
Cullity D 1978 Elements of X-ray Diffraction, 2nd edn.
Addison-Wesley, Reading, MA
Darwin C G 1922 The reflexion of x-rays from imperfect
crystals. Philos. Mag. 43: 800-29
Freund A 1973 Untersuchung des Einflusses von Versetzungen auf die Beugung von Rontgen- und Gammastrahlen
an Kupfereinkristallen. Dissertation, Technische Universitat Munchen

Chromatography

T h e g a s c h r o m a t o g r a p h offers a m e t h o d of s e p a r a t i n g
t h e volatile c o m p o n e n t s of a m i x t u r e . T h e p r i m a r y
result is t h e c h r o m a t o g r a m , w h i c h is a p l o t of t h e
intensity of d e t e c t o r r e s p o n s e a g a i n s t time. T h e time
from injecting t h e s a m p l e t o w h e n a s e p a r a t e d c o m
p o n e n t of t h e m i x t u r e a p p e a r s a t t h e d e t e c t o r is called
t h e r e t e n t i o n t i m e . T h i s t i m e is characteristic of a
p a r t i c u l a r c o m p o u n d ( u n d e r fixed i n s t r u m e n t a l c o n
d i t i o n s ) a n d c a n b e used t o infer t h e presence o r
a b s e n c e of a p a r t i c u l a r c o m p o u n d in a m i x t u r e .
R e t e n t i o n times generally increase w i t h increasing
boiling p o i n t of t h e c o m p o n e n t . A typical c h r o m a t o
g r a p h (See F i g . 1) consists o f several p a r t s :

169

Gas and Liquid

Chromatography

Regulated carriergas supply

Flow control
Detector (s)

Strip-chart

Figure 1
Block diagram of a typical gas chromatograph

c o n t a i n i n g t h e p a c k i n g m a t e r i a l a n d m o u n t e d in
a t e m p e r a t u r e - c o n t r o l l e d c o l u m n oven;
(d)

o n e o r m o r e d e t e c t o r s t o sense t h e a p p e a r a n c e of
t h e s e p a r a t e d c o m p o n e n t s a t t h e outlet of t h e
column; and

(e)

a n electronic i n t e g r a t o r , o r strip-chart r e c o r d e r ,
t o display the c h r o m a t o g r a m as a n i n t e n s i t y time plot.

T h e i n s t r u m e n t s available t o d a y r a n g e from fairly

simple devices t h a t a r e frequently set u p for o n e
specific
analysis
to
complex
microprocessorc o n t r o l l e d i n s t r u m e n t s with several types of inlet
systems a n d multiple d e t e c t o r s . I n s t r u m e n t s of a
m o d e r a t e level of s o p h i s t i c a t i o n h a v e t h e capability of
r a m p i n g t h e c o l u m n oven t e m p e r a t u r e in a c o n t r o l l e d
m a n n e r ( t e m p e r a t u r e p r o g r a m m i n g ) t o allow for elution of m i x t u r e s of a wide r a n g e of volatilities. A low
c o l u m n t e m p e r a t u r e a t t h e s t a r t of t h e analysis
resolves low-boiling c o m p o n e n t s w h e r e a s increasing
the t e m p e r a t u r e elutes the higher-boiling m a t e r i a l s
with satisfactory p e a k w i d t h s ( a n d t h u s g o o d sensiti
vity). T h e ability t o cool t h e c o l u m n oven below
a m b i e n t t e m p e r a t u r e s with t h e aid of liquid c a r b o n
dioxide o r liquid n i t r o g e n is occasionally p r o v i d e d for
the analysis of gases o r low-boiling species.
G a s c h r o m a t o g r a p h y c a n involve t w o different
s e p a r a t i o n m e c h a n i s m s . In g a s - l i q u i d c h r o m a t o
g r a p h y ( G L C ) t h e s a m p l e is p a r t i t i o n e d b e t w e e n a
liquid p h a s e held i m m o b i l e by a solid s u p p o r t a n d t h e
m o v i n g carrier-gas s t r e a m . T h i s t e c h n i q u e is used for
the majority of o r g a n i c s e p a r a t i o n s . In t h e second
t e c h n i q u e , g a s - s o l i d c h r o m a t o g r a p h y ( G S C ) , the
s a m p l e is p a r t i t i o n e d between a solid a d s o r b a n t
(which is often a specially p r e p a r e d p o r o u s p o l y m e r )

170

a n d the carrier-gas s t r e a m . T h i s is usually used for t h e

s e p a r a t i o n of i n o r g a n i c volatiles, gases a n d light
hydrocarbons.
1.1 Columns
T h e r e is a n e n o r m o u s variety of liquid p h a s e s t h a t
h a v e been p r e p a r e d for G L C . T h e s e r a n g e in t e m p e r a
t u r e stability t o a b o v e 350 C a n d cover a n extremely
broad polarity range. However, most separations can
be carried o u t u s i n g fewer t h a n ten different liquid
p h a s e s . A r a n g e of polarities for t h e s t a t i o n a r y p h a s e
is n e e d e d in o r d e r t o o p t i m i z e t h e s e p a r a t i o n as well as
t o a c c o m m o d a t e special s a m p l e s such as a m i n e s .
T h e choice of w h i c h liquid p h a s e t o use t o effect a
s e p a r a t i o n is the m o s t difficult aspect of gas c h r o m a
t o g r a p h y . F r e q u e n t l y , h o w e v e r , a suitable liquid
p h a s e c a n be c h o s e n b y c o n s u l t i n g e x a m p l e s in t h e
literature p u b l i s h e d b y suppliers of c o l u m n s o r s u p
p o r t m a t e r i a l s . N e w d e v e l o p m e n t s include b o n d e d p h a s e c o l u m n s in w h i c h t h e liquid p h a s e is chemically
b o n d e d t o t h e s u p p o r t , giving e n h a n c e d stability a t
higher t e m p e r a t u r e s . T h i s t e c h n o l o g y h a s been
e x t e n d e d t o fused-silica capillary c o l u m n s in w h i c h a
limited n u m b e r of liquid p h a s e s a r e available w h i c h
a r e b o n d e d directly t o t h e capillary surface. T a b l e 1
lists c o m m o n liquid p h a s e s a n d their characteristics as
well as a few c o l u m n p a c k i n g s for G S C . T h e s e cover a
wide r a n g e of polarities a n d a p p l i c a t i o n s .
A typical n o n p o l a r c o l u m n p a c k i n g for G L C c o n
sists of d i a t o m a c e o u s e a r t h t h a t h a s b e e n acid w a s h e d ,
t h e n t r e a t e d w i t h a silylating r e a g e n t such as h e x a m e t h y l d i s i l a z a n e t o d e a c t i v a t e t h e active surface sites
a n d finally c o a t e d w i t h 1-10 w t % of a silicone fluid
such as O V - 1 0 1 . T h i s is t h e n sieved t o give a n a r r o w
particle-size d i s t r i b u t i o n . Typically, t h e particle-size
r a n g e c h o s e n is 100-120 m e s h ( 1 2 5 - 1 4 9 ). T h i s
p a c k i n g m a t e r i a l is l o a d e d i n t o carefully cleaned
c h r o m a t o g r a p h i c t u b i n g . C o l u m n s a r e usually | o r
i in. d i a m e t e r b u t larger d i a m e t e r s h a v e been used for
p r e p a r a t i v e G C , albeit with a n a t t e n d a n t loss in
resolution. A l u m i n u m a n d c o p p e r h a v e been used in
t h e p a s t b u t stainless steel is t h e m o s t c o m m o n
c o l u m n m a t e r i a l . E v e n with stainless steel t h e m e t a l
walls c a n c a u s e d e c o m p o s i t i o n of s o m e m a t e r i a l s o r
a d s o r p t i o n c a n c a u s e p e a k tailing. G l a s s is a m u c h
m o r e inert m a t e r i a l b u t s h o u l d be t r e a t e d with silicone
r e a g e n t s t o r e m o v e p o l a r sites. G l a s s c o l u m n s a r e
q u i t e fragile a n d r e q u i r e great c a r e d u r i n g installation
a n d r e m o v a l from t h e c h r o m a t o g r a p h . S o m e w o r k e r s
h a v e suggested t h a t nickel is a n a p p r o p r i a t e s u b s t i t u t e
for glass in certain a p p l i c a t i o n s . A typical c h r o m a t o
g r a m u s i n g a n o n p o l a r c o l u m n is s h o w n in F i g . 2.
W i t h i n a h o m o l o g o u s series t h e increased r e t e n t i o n
times will be in o r d e r of increased boiling p o i n t s .
A s m i g h t be expected, n a r r o w e r c o l u m n b o r e s , finer
a n d m o r e u n i f o r m particle sizes of p a c k i n g , a n d
c o n n e c t i o n s free of v o l u m e s w h e r e mixing c a n o c c u r
( d e a d v o l u m e ) will i m p r o v e resolution. T h e highest

Gas and Liquid

Chromatography

Table 1
Gas-chromatography packing materials
Stationary
phase
Apiezon L
OV-17
Dexsil-300
Carbowax 20M
FFAP
DEGS
OV-275
Carbowax
20M + KOH
Tenax-GC
Molecular Sieve 5A
Porapak Q

Temperature
limit
Composition

Application

hydrocarbon
50% phenyl, methyl silicone
carboranemethylsilicone
polyethylene glycol
carbowax +
nitroterephthalic
diethylene glycol succinate
dicyanoallyl silicone

general nonpolar
general medium polar
high-temperature phase

275
350
450

general-purpose polar
free fatty acids, polar

225
250

fatty-acid esters
highly polar, pesticides
amines

200
250
225

2,6-diphenyl phenylene oxide polar, water tolerant

zeolite
gas analysis, oxygen/
hydrogen
vinyl benzene polymer
medium polar, water
tolerant

resolution ( u p t o 3000 p l a t e s p e r m e t e r ) c a n be
o b t a i n e d u s i n g capillary c o l u m n s of stainless steel,
glass o r fused silica. C a p i l l a r y c o l u m n s a r e of t w o
general types: (a) w a l l - c o a t e d o p e n t u b u l a r ( W C O T )
c o l u m n s with a n i n t e r n a l d i a m e t e r r a n g e of 0 . 2 0.3 m m with t h e inside wall c o a t e d with a 0 . 1 - 1 . 0
layer of a liquid p h a s e , a n d (b) s u p p o r t - c o a t e d o p e n
t u b u l a r ( S C O T ) c o l u m n s w h e r e a t h i n layer of a solid
s u p p o r t is c o a t e d o n t h e walls of t h e capillary a n d
followed with t h e l i q u i d - p h a s e l o a d i n g . T h e S C O T
c o l u m n s h a v e a higher level of liquid p h a s e a n d
c o n s e q u e n t l y a higher s a m p l e c a p a c i t y (0.011 g)
w h e r e a s t h e W C O T c o l u m n s c a n h a n d l e efficiently
only very small a m o u n t s of s a m p l e ( 1 0 - 1 0 0 ng) a n d
t h u s require t h e use of m o r e sensitive d e t e c t o r s . B o t h
types of c o l u m n r e q u i r e special injection t e c h n i q u e s
o r e q u i p m e n t such a s o n - c o l u m n m i c r o s y r i n g e injec
t o r s o r splitters t h a t divert t h e g r e a t e r p a r t of t h e
injected s a m p l e t o w a s t e . C a p i l l a r y c o l u m n s of fused
silica h a v e f o u n d increasing use b e c a u s e of their
chemical inertness a n d i n h e r e n t r u g g e d n e s s a n d ease
of h a n d l i n g . H o w e v e r , they a r e limited in t h a t they a r e
n o t c u r r e n t l y available w i t h s o m e of t h e m o r e p o l a r
liquid-phase m a t e r i a l s . A typical capillary s e p a r a t i o n
using a fused-silica c o l u m n is s h o w n in Fig. 2. T h i s is
the s a m e m i x t u r e used for t h e e x a m p l e in F i g . 3. N o t e
the increased r e s o l u t i o n possible with capillary
c o l u m n s with n o increase in t h e analysis time.

1.2
Detectors
G a s c h r o m a t o g r a p h y utilizes a wide a r r a y of general
a n d specific d e t e c t o r s . Specific d e t e c t o r s t e n d t o b e
very sensitive a n d their selectivity for p a r t i c u l a r types
of molecules (e.g., t h o s e c o n t a i n i n g h a l o g e n s , sulfur,

CO

375
350
250

n i t r o g e n o r p h o s p h o r u s ) m a k e s t h e m especially useful
in s i t u a t i o n s w h e r e t h e s a m p l e molecules a r e in a
c o m p l e x m i x t u r e of h y d r o c a r b o n s . T h e m o s t c o m m o n
detectors are the thermal-conductivity
detector
( T C D ) a n d t h e flame-ionization d e t e c t o r ( F I D o r
H F I D ) . T h e T C D senses t h e s a m p l e b y c o m p a r i n g t h e
t h e r m a l loss from a h o t filament in t h e effluent from
t h e c o l u m n with t h e loss from a n identical filament in
t h e effluent from a b a l a n c i n g c o l u m n c a r r y i n g only
t h e carrier gas. T h i s d e t e c t o r is a l m o s t universal
(detecting fixed gases a n d i n o r g a n i c s as well as or
g a n i c molecules) b u t h a s only m o d e r a t e sensitivity.
T h e F I D b u r n s t h e s a m p l e in a h y d r o g e n flame
b e t w e e n t w o electrodes, o n e of w h i c h is t h e flame
s u p p o r t . A high p o t e n t i a l difference is a p p l i e d t o t h e
electrodes a n d t h e sensor electronics detect c u r r e n t
flow w h e n t h e b u r n i n g of c a r b o n - c o n t a i n i n g species
increases t h e c o n d u c t i v i t y of t h e flame. T h i s d e t e c t o r
is a n excellent choice for o r g a n i c c o m p o u n d s , for
w h i c h it h a s high sensitivity. T h e F I D h a s n o r e s p o n s e
t o fixed gases a n d is useful for c a r b o n m o n o x i d e only
w h e n t h a t g a s is catalytically c o n v e r t e d t o m e t h a n e in
a m e t h a n i z e r . T h e e l e c t r o n - c a p t u r e d e t e c t o r (used for
t h e e x a m p l e s in Figs. 2 a n d 3) is p a r t i c u l a r l y sensitive
t o h a l o g e n a t e d o r g a n i c s a n d h a s f o u n d extensive use
in pesticide analysis.
Less c o m m o n l y u s e d d e t e c t o r s include t h e flame
p h o t o m e t r i c d e t e c t o r ( F P D ) , t h e H a l l electrolyticc o n d u c t i v i t y d e t e c t o r ( H E C D ) , infrared d e t e c t o r s a n d
t h e m a s s s p e c t r o m e t e r . I n t h e F P D , t h e s a m p l e is
b u r n e d in a h y d r o g e n flame a n d emission from excited
sulfur o r p h o s p h o r u s species is detected b y a p h o t o
multiplier after being a p p r o p r i a t e l y filtered. T h i s is
a very specific d e t e c t o r with a r e s p o n s e r a t i o for
6
c a r b o n : sulfur o r c a r b o n : p h o s p h o r u s of a b o u t 10 .

171

Gas and Liquid

Chromatography

10

15

20

25

30

35

40

45

Time

(min)

L
50

Figure 3
Packed column gas chromatogram of a polychlorinated
biphenyl mixture. Column: 2.0 m 4 mm internal
diameter glass packed with 1.5% OV-17 and 1.95% QF-1
on 60/80 mesh Gas-Chrom
Q. Temperature program:
1
150-250 C at 2 C m i n . Detector: electron capture.
1
Carrier gas: 5% methane in argon ,at 60 ml m i n .
Sample: Aroclor 1260 at 1 0 g m , 1 injection

Figure 2
Capillary gas chromatogram of a polychlorinated biphenyl
mixture. Column: 30 m fused silica with bonded liquid1
phase. Temperature program:
40-80 C at 10 C m i n ,
1
80-225 C at 1 " C m i n . Detection: electron capture.
Carrier gas: helium (make-up, with nitrogen).
Sample: Aroclor at 1 g m , splitless injection

m a s s s p e c t r u m of e a c h c o m p o n e n t as it elutes from
t h e G C c o l u m n . T h e m a s s s p e c t r u m is a p l o t of the
m a s s : c h a r g e r a t i o (usually t h e c h a r g e is unity) for t h e
s a m p l e m o l e c u l a r ion a n d t h e characteristic fragments
it p r o d u c e s in t h e ion source. T h e i n f o r m a t i o n is
s t o r e d in c o m p u t e r files for s u b s e q u e n t analysis a n d
g r a p h i c display. T h e m a s s s p e c t r u m defines t h e m o l e
c u l a r weight a n d p r o b a b l e f o r m u l a s of the u n k n o w n
p e a k s o r enables c o m p a r i s o n with t h e m a s s spectra of
k n o w n s t a n d a r d s s t o r e d in c o m p u t e r files. T h e G C /
M S h a s f o u n d extensive use in t h e analysis of e n v i r o n
m e n t a l s a m p l e s w h e r e its sensitivity a n d specificity a r e
a great a d v a n t a g e .

T h e H E C D c a n be configured so as t o b e h a l o g e n ,
n i t r o g e n o r sulfur specific. I n this detector, the col
u m n effluent is mixed with oxygen (for sulfur) o r
h y d r o g e n (for h a l o g e n s a n d n i t r o g e n ) a n d passed
t h r o u g h a r e a c t o r t u b e a t 7 0 0 - 9 0 0 C. After p a s s i n g
t h r o u g h s c r u b b e r s t o r e m o v e interfering c o m p o u n d s ,
the p r o d u c t s a r e detected as they c h a n g e the c o n d u c t i
vity of a circulating electrolyte. T h e c a r b o n : (halogen,
6
n i t r o g e n , sulfur) r a t i o s a r e also a r o u n d 10 . T h i s
quality is particularly useful w h e n a n a l y z i n g for
heteroatom-containing
compounds
in
complex
hydrocarbon mixtures.
Infrared d e t e c t o r s c a n be either simple single-beam
single-wavelength i n s t r u m e n t s set t o m o n i t o r a p a r
ticular functional g r o u p as t h e c o l u m n effluent passes
t h r o u g h a h e a t e d cell, o r sophisticated F o u r i e r t r a n s f o r m i n s t r u m e n t s t h a t c a n r e c o r d the entire
infrared s p e c t r u m as a p e a k elutes.
T h e m a s s s p e c t r o m e t e r is a very specific a n d sensi
tive detector. It is usually configured as a s t a n d - a l o n e
i n s t r u m e n t ( G C / M S ) a n d o p e r a t e s b y analyzing t h e

1.3 Sample
Introduction
T h e m o s t c o m m o n type of injector, t h e h e a t e d injec
tion p o r t , allows for the injection of s a m p l e solutions
via a syringe t h r o u g h a r u b b e r s e p t u m . R a p i d v a p o r i
z a t i o n of t h e solvent a n d s a m p l e at t e m p e r a t u r e s u p t o
300 C p r o v i d e for efficient t r a n s p o r t t o t h e s e p a r a t i n g
c o l u m n . T h i s p r o c e d u r e c a n be a u t o m a t e d a n d a u t o s a m p l e r s a r e available t h a t a r e c a p a b l e of h a n d l i n g as
m a n y as 100 s a m p l e s a n d injecting t h e m with g r e a t e r
precision t h a n is possible with m a n u a l injection. T h e
c o u p l i n g of a u t o s a m p l e r s with m i c r o p r o c e s s o r i n s t r u m e n t c o n t r o l s a n d data-collection devices p r o
vides for essentially c o m p l e t e a u t o m a t i o n of the G C
analysis. O t h e r types of specialized devices include
h e a d s p a c e s a m p l e r s t o analyze t h e v a p o r c o n t e n t s in
c o n t a i n e r s , p u r g e - a n d - t r a p s a m p l e r s w h i c h collect
a n d c o n c e n t r a t e o r g a n i c volatiles from w a t e r for
p o l l u t a n t analysis, a n d pyrolytic devices t h a t flashpyrolyze solid s a m p l e s from a p l a t i n u m coil o r r i b
b o n . T h i s latter device allows analysis of n o n v o l a t i l e
m a t e r i a l s such as p o l y m e r s a n d geological m a t e r i a l s
by the s t u d y of their t h e r m a l - f r a g m e n t a t i o n p r o d u c t s .

30

35
Time

172

40

45

(min)

Gas and Liquid

Figure 4
Block diagram of a typical liquid chromatograph

F o r gas s a m p l e s , t h e g a s - s a m p l i n g valve w i t h fixedv o l u m e s a m p l i n g l o o p s allows for a c c u r a t e , precise

a n d c o n t a m i n a t i o n - f r e e analysis.

2. Liquid

Chromatography

L i q u i d c h r o m a t o g r a p h y is a p p l i c a b l e t o m o s t types
of s a m p l e t h a t c a n b e s e p a r a t e d b y G C b u t , in
a d d i t i o n , h a s special a d v a n t a g e s in t h e h a n d l i n g of
n o n v o l a t i l e , t h e r m a l l y labile o r ionic m a t e r i a l s . A
block d i a g r a m of a typical liquid c h r o m a t o g r a p h is
s h o w n in F i g . 4. T h e single p u m p is fed b y a m i c r o
p r o c e s s o r - c o n t r o l l e d m i x i n g valve t o p r o d u c e solvent
m i x t u r e s o r c o n t i n u o u s l y v a r y i n g solvent c o m p o s i
tions (e.g., c h a n g i n g f r o m 5 0 % m e t h a n o l in w a t e r t o
1 0 0 % m e t h a n o l over a 3 0 m i n p e r i o d ) . O n s o m e
i n s t r u m e n t s , t w o o r m o r e p u m p s e a c h with its o w n
solvent supply m a y b e c o n t r o l l e d t o p r o d u c e solvent
g r a d i e n t s . Solvent p r o g r a m m i n g h a s similar effects in
L C t o t e m p e r a t u r e p r o g r a m m i n g in G C in t h a t it
s h o r t e n s analysis time a n d increases d e t e c t i o n limits
by s h a r p e n i n g p e a k s . T h e p u m p s a r e c o m m o n l y pis
t o n p u m p s a n d a r e c a p a b l e of p r o d u c i n g a c o n s t a n t
1
flow r a t e of 0 . 1 - 1 0 m l m i n ~ a t b a c k pressures of u p t o
400 a t m . Because of t h e p r e s s u r e s e n c o u n t e r e d , t h e
m a n u a l injectors a n d a u t o s a m p l e r s a r e b a s e d o n highpressure valve systems t h a t isolate t h e s a m p l e from
the system p r e s s u r e until t h e m o m e n t of injection.
2.1
Detectors
T h e d e t e c t o r s used for L C a r e very d e p e n d e n t o n t h e
characteristics of t h e s a m p l e t o b e a n a l y z e d . T w o of
the m o s t c o m m o n a r e t h e u l t r a v i o l e t - a b s o r b a n c e d e
tector a n d t h e differential-refractive-index d e t e c t o r
( D R I ) . T h e u v d e t e c t o r is usually a m i n i a t u r e d o u b l e -

Chromatography

b e a m filter s p e c t r o m e t e r with a flow cell of 410

v o l u m e . T h i s d e t e c t o r is used only for u v - a b s o r b i n g
s a m p l e s a n d , of c o u r s e , w i t h u v - t r a n s p a r e n t solvents.
T h e D R I d e t e c t o r m e a s u r e s t h e difference b e t w e e n
t h e refractive index of t h e c o l u m n effluent a n d a
reference v o l u m e of t h e eluting solvent. T h i s d e t e c t o r
is a m o r e general d e t e c t o r b u t h a s r a t h e r low sensi
tivity, is sensitive t o t e m p e r a t u r e v a r i a t i o n s a n d , of
c o u r s e , c a n n o t b e used in g r a d i e n t - e l u t i o n systems.
O t h e r L C d e t e c t o r s include fluorescence, infrared,
electrochemical a n d derivitization d e t e c t o r s . F l u o r e s
cence d e t e c t o r s i r r a d i a t e t h e c o l u m n effluent with
m o n o c h r o m a t i c light a n d o b s e r v e t h e emission a t
longer w a v e l e n g t h . T h e d e t e c t o r is extremely sensitive
a n d specific b u t requires either a n a t u r a l l y fluorescent
m o l e c u l e o r o n e t h a t c a n b e tagged w i t h a fluorescent
label.
Infrared d e t e c t o r s for L C a r e t h e s a m e as for G C
(Sect. 1.2) b u t a r e m o r e limited b e c a u s e of solvent
absorbance.
E l e c t r o c h e m i c a l d e t e c t o r s a r e available in several
f o r m s b u t t h e m o s t p o p u l a r is t h e a m p e r o m e t r i c type.
T h e r e is also a p o l a r o g r a p h i c d e t e c t o r available t h a t
uses a h a n g i n g m e r c u r y - d r o p electrode. T h e electro
chemical d e t e c t o r s r e q u i r e electroactive s a m p l e c o m
p o n e n t s a n d a r e limited t o c o n d u c t i v e - s o l v e n t systems
such as buffers. T h e s e d e t e c t o r s a r e as a class ex
t r e m e l y sensitive. C o m m o n functional g r o u p s t h a t
a r e electroactive a r e p h e n o l s , a r o m a t i c a m i n e s a n d
sulfur- a n d h a l o g e n - c o n t a i n i n g molecules.
D e r i v i t i z a t i o n d e t e c t o r s a r e low d e a d - v o l u m e
chemical r e a c t o r s t h a t a r e u s e d t o modify t h e c o l u m n
effluent t o confer detectability o r e n h a n c e t h e sensi
tivity of a n y of t h e d e t e c t o r s described in t h e preced
ing. T h e y usually h a v e t h e facility for a d d i n g r e a g e n t s
a n d m i x i n g a n d h e a t i n g t h e c o l u m n effluent w i t h o u t
reducing the chromatographic resolution.
2.2

Columns

T h e r e a r e several basic m a c r o s c o p i c classes of sepa

r a t i o n in L C : l i q u i d - l i q u i d ( L L C ) , l i q u i d - s o l i d ( L S C ) ,
ion-exchange (IEC) and gel-permeation (GPC) or
size-exclusion ( S E C ) c h r o m a t o g r a p h y . E a c h of these
uses a different t y p e of c o l u m n p a c k i n g . L L C uses a
p o r o u s s u p p o r t c o a t e d w i t h a liquid p h a s e t h a t is
immiscible w i t h t h e m o b i l e p h a s e (solvent). C o l u m n
p a c k i n g s t h a t consist of physically a d s o r b e d c o a t i n g s
r e q u i r e c a r e in t h e choice of solvent a n d t e n d t o be
m o r e difficult t o w o r k with. F o r r o u t i n e L C , the
physically a d s o r b e d p h a s e s h a v e been a l m o s t c o m
pletely replaced b y chemically b o n d e d p h a s e s in
w h i c h silica s u b s t r a t e s a r e r e a c t e d w i t h , for e x a m p l e , a
s i l o x a n e - t e r m i n a t e d 18-carbon h y d r o c a r b o n c h a i n .
O t h e r functionalized g r o u p s a r e similarly a t t a c h e d t o
give liquid c o a t i n g s with a r a n g e of h y d r o p h o b i c
c h a r a c t e r . L S C , also called a d s o r p t i o n c h r o m a t o
g r a p h y , c o m m o n l y uses silica gel b u t m a y also use
a l u m i n a , m o l e c u l a r sieves, p o r o u s glass o r c a r b o n as a
stationary phase.

173

Gas and Liquid

Chromatography

In L S C , s a m p l e p o l a r i t y is of m a j o r i m p o r t a n c e in
d e t e r m i n i n g t h e o r d e r of elution. S a m p l e elution t a k e s
place m o r e rapidly as the p o l a r i t y of the m o b i l e p h a s e
is increased. L S C is related t o thin-layer c h r o m a t o g r a
p h y ( T L C ) in which the a d s o r b a n t is c o a t e d as a thin
layer o n a rigid s u b s t r a t e such as glass, a l u m i n u m o r
polyester.
I E C t a k e s place o n c o l u m n s p a c k e d with resin
particles t h a t h a v e ionic functional g r o u p s such as
q u a t e r n a r y a m m o n i u m salts o r sulfonic-acid g r o u p s
a t t a c h e d . T h e m o b i l e p h a s e c a n be acids, bases o r
buffer solutions. T h e s e p a r a t i o n m e c h a n i s m involves
v a r i a t i o n s in affinity of m o b i l e i o n s in solution t o the
b o u n d ions o n the s t a t i o n a r y p h a s e . I E C h a s been
extensively used in a m i n o - a c i d analysis a n d for the
s e p a r a t i o n of m e t a l i o n s , sugars a n d m a n y biological
molecules.
A v a r i a n t of I E C is ion c h r o m a t o g r a p h y (IC) in
which a n i o n - e x c h a n g e s e p a r a t i o n of a n i o n s o r
c a t i o n s is carried o u t o n a low-capacity i o n - e x c h a n g e
s e p a r a t i n g c o l u m n , followed b y a s u p p r e s s o r c o l u m n
t h a t neutralizes t h e acidic (for cations) o r basic (for
a n i o n s ) m o b i l e p h a s e . T h i s allows t h e s a m p l e i o n s of
interest to be detected by a c o n d u c t i v i t y d e t e c t o r
against a b a c k g r o u n d of deionized w a t e r . D e t e c t i o n
levels in t h e p p b r a n g e h a v e been d e m o n s t r a t e d for
chloride, fluoride a n d sulfate as well as for alkali a n d
alkaline-earth c a t i o n s . T h i s t e c h n i q u e is of p a r t i c u l a r
i m p o r t a n c e for a n i o n analysis since classical m e t h o d s
for these t e n d t o be t e d i o u s a n d limited in sensitivity.
In a d d i t i o n , I C c a n distinguish b e t w e e n different
o x i d a t i o n states of s o m e a n i o n s such as sulfate-sulfite
a n d n i t r a t e - n i t r i t e . C a t i o n analysis by ion c h r o m a t o
g r a p h y is n o t as frequently used as it c o m p e t e s with
a t o m i c a b s o r p t i o n ( A A ) which is a relatively sensitive
technique.
G P C c a n be carried o u t o n the s a m e i n s t r u m e n t s
as o t h e r L C techniques b u t differs from t h e m in
t h a t the s t a t i o n a r y p h a s e consists of a c o n t r o l l e d p o r o s i t y p o l y m e r n e t w o r k , a solvent-swelled gel o r a
c o n t r o l l e d - p o r o s i t y glass. T h e solvent carries t h e s a m
ple molecules a l o n g a n d they d i s t r i b u t e a c c o r d i n g t o
their size between t h e s t a t i o n a r y p h a s e a n d t h e m o b i l e
p h a s e . L a r g e r molecules such as h i g h - m o l e c u l a r weight p o l y m e r s t e n d n o t to p e n e t r a t e the p o r e s o r gel
a n d elute first. P r o p o r t i o n a t e l y smaller molecules
elute later. T h e c o l u m n s c a n be c a l i b r a t e d in t e r m s of
a certain r e t e n t i o n v o l u m e (retention time flow rate)
by using k n o w n - m o l e c u l a r - w e i g h t s t a n d a r d s . S t a n
d a r d i z a t i o n s by this m e t h o d give m o l e c u l a r weights
referenced t o t h e s t a n d a r d i z i n g p o l y m e r (usually
n a r r o w - d i s t r i b u t i o n polystyrene). O t h e r structurally
different p o l y m e r s m a y deviate significantly in reten
tion v o l u m e from polystyrenes of equivalent m o l e c u
lar weights. F i g u r e 5 s h o w s a c o m p o s i t e of t w o G P C
traces. T h e trace in the b a c k g r o u n d is from a n ex
p e r i m e n t a l p o l y m e r a n d s h o w s a fairly b r o a d
molecular-weight d i s t r i b u t i o n as well as the presence
of residual m o n o m e r a n d s o m e oligomeric m a t e r i a l .
174

10.93

15.41

19.89

Retention t i m e ( m i n )

Figure 5
Gel-permeation (size-exclusion) chromatogram. The upper
trace is from an experimental polymer, the lower
(superimposed) trace is from an analysis of a mixture of
narrow-molecular-weight-distribution polystyrene
standards (the molecular weights are labelled). The
chromatograph utilized four micro-Styragel columns.1
The solvent was chloroform at a rate of 2.0 ml m i n ,
uv detection was at 254 nm

T h e s u p e r i m p o s e d trace is of a m i x t u r e of p o l y s t y r e n e
s t a n d a r d s labelled with their m o l e c u l a r weights. M o s t
of t h e d e t e c t o r s useful for L C a r e also applicable t o
G P C . T h e low-angle laser-light-scattering ( L A L L S )
d e t e c t o r is specific to G P C . T h i s d e t e c t o r m e a s u r e s
the i n s t a n t a n e o u s weight-average m o l e c u l a r weight of
t h e c o l u m n eluent a n d calculates the d i s t r i b u t i o n
b a s e d o n a c o m b i n a t i o n of the L A L L S a n d a m a s s sensitive d e t e c t o r such as D R I . T h e use of this detec
t o r eliminates t h e need for c a l i b r a t i o n s for e a c h
specific p o l y m e r analyzed.
See also: Liquid Chromatography Mass Spectroscopy

Bibliography
Cazes J (ed.) 1977, 1980, 1981 Liquid Chromatography of
Polymers and Related Materials, Vols. 1-3. Dekker, New
York
Grob R L (ed.) 1977 Modern Practice of Gas Chromatog
raphy. Wiley, New York
Hagnauer G L 1982 Size exclusion chromatography. Anal.
Chem. 53: 265R-76R
Risby , Field L R, Yang F Y, Cram S 1982 Gas
chromatography. Anal. Chem. 53: 410R-28R
Simpson C F (ed.) 1976 Practical High Performance Liquid
Chromatography. Hey den, London

Gas Sensors,

Solid-State

EMF

Snyder L R, Kirkland J J 1979 Introduction to Modern

Liquid Chromatography, 2nd edn. Wiley, New York
Yau W W, Kirkland J J, Bly D D 1979 Modern SizeExclusion Liquid Chromatography: Practice of Gel
Permeation and Gel Filtration Chromatography. Wiley,
New York

h2h

C. C a r n a h a n J r
[ G e n e r a l Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]

Gas Sensors, Solid-State

I n recent years, there h a s b e e n a n e x p l o s i o n in t h e
a p p l i c a t i o n of c o m p u t i n g a n d microelectronics with
the overall a i m of m o n i t o r i n g , c o n t r o l l i n g , o p t i m i z i n g
a n d a u t o m a t i n g i n d u s t r i a l processes. T h e latter a p p l i
c a t i o n c a n be of p a r t i c u l a r i m p o r t a n c e t o industries
w h e r e w o r k i n g c o n d i t i o n s a r e either h a z a r d o u s o r
e n v i r o n m e n t a l l y u n a c c e p t a b l e . H o w e v e r , in m a n y
cases, t h e c o m p u t e r a p p l i c a t i o n s a r e restricted b y t h e
lack of reliable sensors t o detect c h a n g e s in t h e
processes a n d their e n v i r o n m e n t , p a r t i c u l a r l y w i t h
gases. C o n v e n t i o n a l gas analysis using c h r o m a t o
g r a p h i c o r s p e c t r o s c o p i c m e t h o d s is n o t always
suitable d u e t o expense, t h e need for c o n t i n u o u s
m o n i t o r i n g a n d p o o r sensitivity a t low c o n c e n t r a
tions. T h e d e v e l o p m e n t of n e w a n d m o r e reliable
sensors is, therefore, of p a r a m o u n t i m p o r t a n c e for t h e
future c o n t r o l of m a n y processes, especially t h o s e
o p e r a t i n g a t high t e m p e r a t u r e s .
T h e d e v e l o p m e n t of chemical sensors t o m o n i t o r
g a s e o u s species falls i n t o t w o m a i n categories. First,
a t elevated t e m p e r a t u r e s , sensors a r e generally b a s e d
u p o n ionically c o n d u c t i n g ceramics. T h e s e devices
m a y b e o p e r a t e d in t h e p o t e n t i o m e t r i c o r c o u l o m e t r i c
m o d e s . Second, sensors c a n b e b a s e d u p o n m a t e r i a l s
which rely u p o n c h a n g e s in physical effects such a s t h e
C u r i e p o i n t for piezoelectric-based a n d Hall-effect
devices, a d s o r p t i o n b a n d s for optical devices a n d
c o n d u c t i o n b a n d s a t u r a t i o n for s e m i c o n d u c t i n g
m a t e r i a l s . T h i s article reviews these t w o m a j o r g r o u p s
of sensors w h i c h , if successfully a p p l i e d , allow t h e
c o n t r o l of a diverse r a n g e of processes, from gas
c o m b u s t i o n in t h e i n t e r n a l c o m b u s t i o n engine
t h r o u g h p y r o m e t a l l u r g i c a l processes t o m i c r o w a v e
cooking.

/.

Solid Electrolyte

Sensors

Solid electrolyte sensors a r e b a s e d u p o n c e r a m i c

m a t e r i a l s w h i c h a r e , a l m o s t exclusively, ionic c o n d u c
tors. M o s t ceramics a r e i n s u l a t o r s , b o t h electronically
a n d ionically, b u t there a r e several g r o u p s w h i c h
c o n d u c t ions b e c a u s e of d o p i n g of t h e m a t e r i a l w h i c h
induces defects in t h e s t r u c t u r e ( C a O , Z r 0 2 ) , b e c a u s e
of o r d e r - d i s o r d e r p h a s e t r a n s f o r m a t i o n s w h i c h c a u s e

Inner electrode

Figure 1
Gas sensor to monitor oxygen content of exhaust gases
from car engines

t h e c a t i o n lattice t o d i s o r d e r ( R b A g J j ) , o r because
there a r e p l a n e s o r t u n n e l s in t h e m a t e r i a l t h r o u g h
w h i c h ionic species m a y m o v e ( N a 2 0 . 1 1 A l 2 0 3 o r
N a 1 + xZ r 2 S i j rP 3 _ J f0 1 2) . O t h e r solid electrolytes a r e
b a s e d u p o n p o l y m e r i c m a t e r i a l s (polyethylene oxide
a n d perfluorosulfonic acid). I n t h e p o t e n t i o m e t r i c
m o d e these sensors a r e b a s e d u p o n t h e very simple
thermodynamic concept that a concentration gradient
of a species a c r o s s a n ionic c o n d u c t o r results in a
p o t e n t i a l w h i c h c a n be detected b y a high i m p e d a n c e
v o l t m e t e r . A n oxygen sensor c a n be r e p r e s e n t e d b y
2

Pt, 0 2 | 0 ~ c o n d u c t o r IO2, P t
2

w h e r e " 0 ~ c o n d u c t o r " is a n ionic c o n d u c t o r of

o x y g e n i o n s , a n d 0 2 a n d O " d e n o t e different p a r t i a l
p r e s s u r e s of o x y g e n . T h e physical a r r a n g e m e n t for
m e a s u r i n g t h e c o n c e n t r a t i o n of o x y g e n is s h o w n in
Fig. 1. T h e p o t e n t i a l is given b y t h e N e r n s t e q u a t i o n

- ZEF=

P'
RT I n

(1)

p"

w h e r e '2, PQ 2 refer t o t h e p a r t i a l pressures of oxygen

o n either side of t h e electrolyte, is t e m p e r a t u r e , R is
t h e gas c o n s t a n t , F is F a r a d a y ' s c o n s t a n t a n d is t h e
u n i t of c h a r g e carried. T h e m a i n r e q u i r e m e n t s for
d e v e l o p i n g a successful sensor a r e a n ionic c o n d u c t o r
for t h e species of interest a n d a reference m a t e r i a l
w h i c h gives a c o n s t a n t p a r t i a l p r e s s u r e of t h e species.
E x a m i n a t i o n of E q n . (1) s h o w s t h a t t h e p o t e n t i a l
c h a n g e is t h e s a m e for a c o n c e n t r a t i o n c h a n g e of
1 p p m t o 10 p p m as it is for a c o n c e n t r a t i o n c h a n g e of
10 000 p p m t o 100 000 p p m . Sensors b a s e d u p o n the
N e r n s t e q u a t i o n a r e p a r t i c u l a r l y sensitive a t low c o n
c e n t r a t i o n s b u t they a r e relatively insensitive a t high
c o n c e n t r a t i o n s . If, instead of m e a s u r i n g the p o t e n t i a l ,

175

Gas Sensors,

Solid-State

a p o t e n t i a l is applied across t h e electrolyte, t h e cur

rent flow will b e directly related t o the flux of i o n s
t h r o u g h t h e electrolyte a n d this, in t u r n , will d e p e n d
u p o n the r a t e of arrival of the species a t t h e surface of
the electrolyte. T h e c u r r e n t flow is, therefore, directly
p r o p o r t i o n a l t o the diffusional flux of t h e species a n d
is linearly d e p e n d e n t u p o n the c o n c e n t r a t i o n of
species in the gas p h a s e r a t h e r t h a n logarithmically
d e p e n d e n t as in t h e case of the p o t e n t i o m e t r i c m o d e .
Overall, solid-state electrochemical sensors h a v e
several a d v a n t a g e s in t h a t t h e p o t e n t i a l s a n d c u r r e n t s
c a n be m e a s u r e d with high a c c u r a c y , the p o t e n t i a l s
a r e i n d e p e n d e n t of the d i m e n s i o n s of the m a t e r i a l
allowing m i n i a t u r i z a t i o n a n d i n t e g r a t i o n i n t o m i c r o
electronic devices a n d , if a solid reference is used, t h e
cells c a n be m a d e entirely in t h e solid state, h a v e low
energy c o n s u m p t i o n a n d c a n be m a d e rugged a n d
reliable.

2. Oxygen

Sensors

M o s t oxygen sensors use t h e cubic form of zirconia

which h a s been stabilized with calcium oxide o r yttria.
In s o m e cases, it is possible t o use air o r a m i x t u r e of
gases as t h e reference b u t , frequently, t h e reference is
a m i x t u r e of a m e t a l a n d its oxide which gives a fixed
oxygen p a r t i a l pressure a t a given t e m p e r a t u r e
t h r o u g h t h e following equilibrium:
2

2;=2 + 0 2 ,

K=

P<
2

(2)

Sensors

T h e q u a n t i t a t i v e d e t e c t i o n of h y d r o g e n is of consider
able i m p o r t a n c e in a variety of industrial s i t u a t i o n s ,

176

electrolyte

Hole

Anode

Figure 2
Limiting-current-type oxygen sensor

such as t h e synthesis of a m m o n i a , m e t h a n o l a n d o t h e r
chemicals, p e t r o l e u m refining, s e m i c o n d u c t o r m a n u
facture, chemical r e d u c t i o n a n d c o r r o s i o n c o n t r o l .
U n f o r t u n a t e l y , there a r e n o satisfactory hight e m p e r a t u r e p r o t o n c o n d u c t o r s a n d the m a i n a p
p r o a c h h a s been t o use m a t e r i a l s such as N a f i o n
(perfluorosulfonic acid) a n d H U P ( h y d r o g e n u r a n y l
phosphate) which become proton conductors when
h y d r a t e d . T h e reference m a t e r i a l used h a s been either
h y d r o g e n gas, a m i x t u r e of h y d r i d e s o r a r e d o x
m i x t u r e . T h e s e sensors h a v e been used t o m e a s u r e
h y d r o g e n in gases a n d h y d r o g e n in solid steel gener
ated by corrosion reactions.

x 2

w h e r e is the e q u i l i b r i u m c o n s t a n t , P0l is the p a r t i a l

pressure of t h e oxygen a n d aM a n d aMO a r e the
activities of the m e t a l a n d m e t a l oxide, respectively.
A s t h e m e t a l a n d m e t a l oxide a r e p r e s e n t as p u r e
p h a s e s , the activities a r e unity, is c o n s t a n t a n d ,
therefore, the p a r t i a l pressure of t h e oxygen is fixed.
Sensors b a s e d o n this c o n c e p t a r e used t o m e a s u r e t h e
oxygen c o n t e n t of gases, c o n t r o l furnace a t m o s
pheres, m e a s u r e dissolved oxygen in m o l t e n c o p p e r
a n d steel, a n d c o n t r o l t h e fuel-to-air r a t i o in internal
c o m b u s t i o n engines, especially w h e r e catalytic c o n
verters are fitted. C h a n g i n g from a fuel-rich t o a n airrich gas causes t h e oxygen p a r t i a l p r e s s u r e t o c h a n g e
d r a m a t i c a l l y resulting in a p o t e n t i a l c h a n g e of a b o u t
0.8 V, which is m o r e t h a n sufficient for a m i c r o p r o c e s
sor t o m o n i t o r a n d m a k e t h e necessary a d j u s t m e n t s t o
the c a r b u r e t o r . In the case of l e a n - b u r n engines, t h e
gas is always oxidizing a n d , therefore, m e a s u r e m e n t s
of p o t e n t i a l a r e n o t sensitive t o c h a n g e s in t h e oxygen
c o n t e n t . In this case, limiting-current devices a r e used,
a n e x a m p l e of which is s h o w n in Fig. 2.

3. Hydrogen

Cathode

4. Sulfur and Sulfur-Containing

Gases

T h e electrochemical d e t e r m i n a t i o n of sulfur a n d sul

fur dioxide is n o t as s t r a i g h t f o r w a r d as t h e d e t e c t i o n
of oxygen o r h y d r o g e n , since t h e electrolytes a r e
neither as stable n o r as c o n d u c t i n g . C a l c i u m sulfide
h a s b e e n used as a n electrolyte in t h e following cell:
Fe, FeS | C a S ( C a

2 +

conductor) | H 2 , H 2S

Since t h e electrolyte is a calcium ion c o n d u c t o r , t h e

c h a n g e s in sulfur p o t e n t i a l a r e related t o a c h a n g e in
t h e calcium activity t h r o u g h t h e r e l a t i o n s h i p
Ca + i S 2^ C a S ,

=~^2

(3)

M o r e recently, in o r d e r t o c o m b a t t h e p o o r ionic
c o n d u c t i v i t y of calcium sulfide, m i x e d electrolytes of
calcium sulfide a n d stabilized zirconia h a v e been used
in w h i c h t h e r e a c t i o n o f t h e w o r k i n g electrode is
CaS + i O ^ C a O ( Z r 0 2) + i S 2 ,

K=

a
a

C Qa

P
^

CaS^0

l/2

(4)

A s t h e activities of t h e solid p h a s e s a r e fixed, t h e

oxygen p r e s s u r e m u s t be p r o p o r t i o n a l t o t h e sulfur
pressure. U n f o r t u n a t e l y , these sensors only function
in r e d u c i n g a t m o s p h e r e s o w i n g t o t h e instability of
calcium sulfide. A t higher oxygen p r e s s u r e s , sulfates
a r e t h e r m o d y n a m i c a l l y stable a n d m a y be used t o

Gas Sensors,

detect sulfur dioxide. T h e overall reaction is

SO^"^S0

+ 0

+ 2e"

(5)

a n d the p o t e n t i a l c a n be expressed by

=^ l n ^ +^ l n ^
ZF

P0i

ZF

(6)

Pso;

a n d if the oxygen p o t e n t i a l is fixed at b o t h electrodes

t h e p o t e n t i a l is given by t h e r a t i o of t h e p a r t i a l
pressures of t h e sulfur dioxide.

a r e a e x p o s e d t o t h e gas. T h e resistance c h a n g e with

o x y g e n p r e s s u r e c a n be a c c u r a t e l y d e t e r m i n e d by, in
essence, s u b t r a c t i n g t h e v a r i a t i o n of resistance for the
d e n s e pellet from t h a t of t h e p o r o u s pellet.
F o r a p p l i c a t i o n in l e a n - b u r n engines, t h e q u a r t e r
p o w e r d e p e n d e n c e of t h e c o n d u c t i v i t y o n oxygen
p a r t i a l p r e s s u r e gives a low sensitivity. H o w e v e r ,
o t h e r s e m i c o n d u c t i n g oxides, such as C o O . C O j _ x
M g ^ O a n d S r M g ^ T i ^ O j a r e being investigated t o
o v e r c o m e this p r o b l e m .

6. Humidity
5. Gas Sensors
Electrical

Dependent

upon Changes

in

Conductivity

T h e s e sensors d e p e n d u p o n t h e electronic c o n d u c
tivity of certain s e m i c o n d u c t i n g oxides, such as T i 0 2 ,
N b 2 0 5 a n d C e 0 2 , c h a n g i n g with t h e o x y g e n p a r t i a l
pressure. In t h e case of T i 0 2 , t h e intrinsic electrical
c o n d u c t i v i t y is m a i n l y d u e t o o x y g e n lattice defects
a n d c a n be r e p r e s e n t e d b y t h e following e q u a t i o n :
x

O0

i 0

+ F

- 2 e "

(7)

w h e r e O* is a n o x y g e n ion o n a n a n i o n i c site of t h e
crystal, V0 is a positive v a c a n c y in t h e a n i o n sublattice
a n d e " r e p r e s e n t s a n electron d o n a t e d t o t h e c o n d u c
tion b a n d . F r o m E q n . (7), it c a n be seen t h a t d e c r e a s
ing t h e oxygen p a r t i a l p r e s s u r e leads t o a n increase in
vacancies a n d electrons. U s i n g the e l e c t r o n e u t r a l i t y
relationship and assuming thermodynamic equi
librium, t h e following e q u a t i o n c a n be o b t a i n e d :
n = Pol

/6

expi-E/kT)

(8)

w h e r e is t h e n u m b e r of free electrons g e n e r a t e d
a c c o r d i n g t o E q n . (7), is t h e energy of f o r m a t i o n of
a n oxygen v a c a n c y a n d k is t h e B o l t z m a n n c o n s t a n t .
1/4
I n fact, e x p e r i m e n t a l results s h o w a PQ2
relationship
with the c o n d u c t i v i t y o w i n g t o t h e presence of i m p u r i
ties in t h e crystal w h i c h c a u s e a relatively high c o n c e n
t r a t i o n of o x y g e n vacancies. A s a c o n s e q u e n c e , t h e
v a c a n c y c o n c e n t r a t i o n is virtually i n d e p e n d e n t of t h e
oxygen p a r t i a l p r e s s u r e a n d t h e d e p e n d e n c e of t h e
electrical c o n d u c t i v i t y is p r o p o r t i o n a l t o P\.
A c c o r d i n g t o E q n . (8), it c a n be e s t i m a t e d t h a t a
T i 0 2 resistor will exhibit a c h a n g e in c o n d u c t i v i t y of
four o r d e r s of m a g n i t u d e as t h e air-to-fuel r a t i o in a n
internal c o m b u s t i o n engine passes from being r e d u c
ing t o oxidizing. S u p e r i m p o s e d u p o n this c o n d u c t i v i t y
c h a n g e , there is also a c o n d u c t i v i t y c h a n g e d u e t o t h e
v a r i a t i o n in t e m p e r a t u r e , w h i c h c a n b e o v e r c o m e
either b y m a i n t a i n i n g t h e resistor a t a c o n s t a n t t e m
p e r a t u r e b y m e a n s of a h e a t e r o r b y interfacing a very
p o r o u s T i 0 2 pellet with a d e n s e T i 0 2 pellet. T h e
resistivity of b o t h pellets c h a n g e s with t e m p e r a t u r e
b u t only t h e resistance of t h e p o r o u s pellet c h a n g e s
with oxygen p r e s s u r e d u e t o t h e m u c h larger surface

Solid-State

Sensors

T h e r e is a n increasing d e m a n d for h u m i d i t y sensors in

a u t o m a t i c c o o k i n g b y m i c r o w a v e ovens, in fridges, in
air c o n d i t i o n e r s , in driers a n d in d e w sensing o n the
cylinder h e a d s of v i d e o t a p e r e c o r d e r s . H u m i d i t y sen
sors a r e also m a d e from s e m i c o n d u c t o r s , b u t the
m e c h a n i s m b y w h i c h t h e sensor functions is n o t
related t o t h e s t r u c t u r e of t h e b u l k m a t e r i a l , b u t is d u e
m o r e t o unsatisfied b o n d s a t t h e surface of t h e m a t e r
ial w h i c h p r o m o t e t h e a d s o r p t i o n of h y d r o x y l g r o u p s
w h i c h t h e n b o n d t o f o r m w a t e r molecules. T h e sur
face c o n d u c t i v i t y increases as t h e h u m i d i t y increases.
F o r M g C r 20 4- T i 0 2 materials, the adsorbed water
molecules a r e easily d e s o r b e d by either decreased
p r e s s u r e o r by t e m p e r a t u r e s slightly h i g h e r t h a n t h e
a m b i e n t t e m p e r a t u r e . T h e s e sensors a r e used in t h e
c o n t r o l of m i c r o w a v e c o o k i n g .

7. Gas-Sensitive

Resistors

Similar sensors h a v e been d e v e l o p e d t o detect o t h e r

gases b u t t h e exact m e c h a n i s m of o p e r a t i o n is n o t
fully u n d e r s t o o d t h o u g h it is t h o u g h t t h a t chemiso r b e d oxygen m u s t be p r e s e n t . I n t h e case of tin oxide
s p u t t e r e d o n t o a n a l u m i n a s u b s t r a t e , oxygen is
t h o u g h t t o deplete t h e valence b a n d , which lowers t h e
c o n d u c t i v i t y . W h e n c a r b o n m o n o x i d e is present, this
is also a d s o r b e d , increasing t h e c o n d u c t i v i t y of t h e tin
oxide. H o w e v e r , t h e r e l a t i o n s h i p b e t w e e n the gas
c o n c e n t r a t i o n a n d t h e resistance is n o n l i n e a r a n d t h e
selectivity is p o o r . I n spite of these d i s a d v a n t a g e s ,
h o w e v e r , m e t a l oxide gas sensors h a v e been used for
m o n i t o r i n g c o m b u s t i b l e gases a n d as gas leakage
d e t e c t o r s , as t h e c o n s t r u c t i o n a n d electronic circuitry
is relatively simple.

8. Surface

Acoustic

Wave

Sensors

T h e s t r o n g piezoelectricity a n d low a c o u s t i c losses of

lithium n i o b a t e ( L i N b 0 3 ) h a v e laid t h e basis of sur
face a c o u s t i c w a v e sensors. A set of electrodes gener
ates a n a c o u s t i c w a v e w h i c h p r o p a g a t e s a l o n g the
surface a n d is detected by a s e c o n d set of electrodes.
T h e velocity of t h e surface a c o u s t i c c a n be influenced
by a d e p o s i t e d c o a t i n g w h i c h , in t u r n , c a n be altered

177

Gas Sensors,

Solid-State

Platinum wire

Support
Catalyst

Figure 3
Catalytic gas sensor bead

by a b s o r b e d
can absorb
detected b y
larly, a lead
detect nitric

9. Catalytic

gases. F o r e x a m p l e , a thin p a l l a d i u m film

a n d d e s o r b h y d r o g e n a n d this c a n b e
p h a s e shifts in t h e a c o u s t i c w a v e . Simi
p h t h a l o c y a n a t e c o a t i n g h a s been used t o
oxide.

Gas

Detectors

I n f l a m m a b l e gases c a n b e m o n i t o r e d by catalytic g a s
d e t e c t o r s which a r e m a d e from a p l a t i n u m coil u p o n
w h i c h is d e p o s i t e d a p o r o u s oxide m a t e r i a l , such as
a l u m i n a o r t h o r i a . A catalytic gas sensor b e a d is
s h o w n in F i g . 3. T h e a c t u a l d e t e c t o r consists of t w o
s u c h b e a d s , o n e of w h i c h is a c t i v a t e d w i t h catalyst
while t h e o t h e r h a s n o catalytic activity. I n t h e p r e s
ence of i n f l a m m a b l e gases a n d a t a t e m p e r a t u r e of
a p p r o x i m a t e l y 600 C, t h e catalytic b e a d causes t h e
inflammable gases t o react with t h e oxygen in air a n d
this raises t h e t e m p e r a t u r e a n d , t h u s , t h e resistance of
t h e p l a t i n u m coil. T h e inert b e a d , h a v i n g n o catalytic
activity, d o e s n o t increase in t e m p e r a t u r e a n d , t h e r e
fore, t h e coil resistance of this b e a d r e m a i n s c o n s t a n t .
T h e difference b e t w e e n t h e resistances of t h e t w o
b e a d s is related t o t h e c o n c e n t r a t i o n of t h e inflam
m a b l e gases present.

10. Semiconductor

Junction

Devices

Thes<e sensors rely o n t h e a d s o r p t i o n of a gas t h a t

modifies t h e electron d i s t r i b u t i o n in t h e surface region
of a s e m i c o n d u c t o r . T h i s c a n o c c u r either b y direct
i n t e r a c t i o n w i t h t h e g a s o r b y indirect i n t e r a c t i o n with
oxygen w h i c h will b e displaced b y t h e gas b e i n g
m e a s u r e d . I n s t e a d of m e a s u r i n g t h e surface c o n d u c t i
vity, t h e c o n d u c t i o n a c r o s s t h e interface o r t h e c a p a c i
t a n c e of t h e surface s p a c e - c h a r g e layer is m e a s u r e d . A
typical m e t a l - o x i d e - s e m i c o n d u c t o r field-effect t r a n
sistor ( M O S F E T ) is s h o w n in F i g . 4.

178

Initial a t t e m p t s t o d e v e l o p a hydrogen-sensitive
p a l l a d i u m - s i l i c o n S c h o t t k y d i o d e failed b e c a u s e of
t h e f o r m a t i o n of a n i n t e r m e d i a t e silicide layer of
P d 2 S i . T h i s p r o b l e m w a s solved b y deliberately g r o w
ing a very t h i n layer of silica p r i o r t o t h e d e p o s i t i o n of
the p a l l a d i u m . T h i s very thin layer d o e s n o t affect
either t h e d i o d e characteristics of t h e s t r u c t u r e o r t h e
h y d r o g e n sensitivity. It is likely t h a t as well as the
f o r m a t i o n of a d i p o l e layer a t t h e p a l l a d i u m - s i l i c a
interface, t h e m o d u l a t i o n of t h e surface states a t t h e
silicon-silica interface a n d t h e c o r r e s p o n d i n g t u n n e l
ling of electrons b e t w e e n these surface states a n d t h e
p a l l a d i u m m a y also p l a y a n i m p o r t a n t role.
H y d r o g e n a t o m s diffuse t h r o u g h the thin p a l l a d i u m
layer a n d a r e a d s o r b e d a t t h e m e t a l - i n s u l a t o r inter
face. T h e h y d r o g e n a t o m s a r e p o l a r i z e d a n d give rise
t o a d i p o l e layer resulting in a voltage d r o p w h i c h is
a d d e d t o t h e externally a p p l i e d voltage. T h i s voltage
d r o p is d e p e n d e n t u p o n t h e c o n c e n t r a t i o n a n d it
s h o u l d b e n o t e d t h a t this c o n c e n t r a t i o n is n o t only a
function of t h e h y d r o g e n p r e s s u r e , b u t c a n also b e
influenced b y t h e presence of oxidizing gases w h i c h
can remove absorbed hydrogen. F o r n o n p o r o u s pal
l a d i u m films, t h e devices only r e s p o n d t o gases which
c a n dissociate i n t o h y d r o g e n .
L a n g m u i r - B l o d g e t t films, w h i c h a r e h o m o g e n e o u s
o r g a n i c films, o n e m o l e c u l e thick, c a n be used as a n
insulating layer b e t w e e n t h e g a t e a n d t h e c h a n n e l of a
silicon M O S F E T o r b e t w e e n t h e electrodes of a M O S
d i o d e . R e d o x o r c o m p l e x a t i o n r e a c t i o n s with t h e
active molecules of t h e L a n g m u i r - B l o d g e t t film
result in a shift of t h e flat b a n d v o l t a g e a n d a c h a n g e
in t h e low-frequency dielectric losses of t h e device.
It h a s b e e n f o u n d t h a t M O S s t r u c t u r e s c o n t a i n i n g a
L a n g m u i r - B l o d g e t t film of p h t h a l o c y a n i n e r e s p o n d
quickly t o a few p a r t s p e r million of N O x a t r o o m
temperature.

11.

Conclusions

F r o m a n i n d u s t r i a l viewpoint, there is a c o n s i d e r a b l e

Source
Q

Gate
9

Drain
Q

Metal
Oxide ( S i 0 2)
Channel
p- silicon

Figure 4
Metal-oxide-semiconductor field-effect transistor
(MOSFET)

Grain Size:

need for c o n t r o l in o r d e r t o m a i n t a i n a p e r m a n e n t
analysis of t h e p h y s i c o c h e m i c a l p a r a m e t e r s of m a n y
processes with t h e a i m of achieving q u a l i t y a n d r e p r o
ducibility. F u r t h e r m o r e , with t h e ever-increasing
pressure t o m i n i m i z e a t m o s p h e r i c p o l l u t i o n , t h e
m o n i t o r i n g of effluents is b e c o m i n g of p a r a m o u n t
i m p o r t a n c e . T h e increase in c o n s u m e r g o o d s , such as
cars a n d air c o n d i t i o n e r s , is responsible n o t only for
direct p o l l u t i o n of t h e e n v i r o n m e n t b u t also for
indirect p o l l u t i o n b y c o n s u m i n g electricity p r o d u c e d
by the c o m b u s t i o n of fossil fuels. A n y i m p r o v e m e n t s
in efficiency m a d e possible b y c o n t r o l will p a y divi
d e n d s b o t h in t e r m s of i m p r o v e d p r o d u c t i o n values
a n d decreased a t m o s p h e r i c p o l l u t i o n .
I n this article it h a s been d e m o n s t r a t e d t h a t there is
a wide variety of sensors b a s e d o n different physical
a n d chemical effects. T h e i n t e g r a t i o n of chemical
sensors, such as h u m i d i t y sensors, is m u c h m o r e
difficult t h a n with physical sensors b e c a u s e chemical
sensors m u s t be directly e x p o s e d t o t h e v a r i o u s en
v i r o n m e n t s a n d , therefore, they c a n n o t be totally
sealed.
A n o t h e r p r o b l e m for t h e i n t e g r a t i o n of chemical
sensors is t h e i n c o m p a t i b i l i t y of t h e m a t e r i a l s of t h e
sensing element a n d t h e i n t e g r a t e d circuits. H o w e v e r ,
c o n s i d e r a b l e effort is being p u t i n t o d e v e l o p i n g thin
film devices u s i n g s p u t t e r i n g , v a p o r d e p o s i t i o n a n d
silicon t e c h n o l o g y with a view t o i m p r o v i n g sensor
characteristics a n d lowering t h e overall cost.
Finally, it c a n be confidently s t a t e d t h a t t h e d e
m a n d for gas sensors will g r o w a n d t h a t research will
d e v e l o p n e w sensors a n d m a k e existing sensors m o r e
reliable.
See also: Gas and Liquid Chromatography

Nondestructive

Evaluation

Grain Size: Nondestructive Evaluation

U l t r a s o n i c a n d m a g n e t i c m e t h o d s h a v e been used t o
e v a l u a t e g r a i n size in single-phase polycrystalline
solids. T h e u l t r a s o n i c m e t h o d is b a s e d o n t h e scatter
ing of a c o u s t i c energy from a n i s o t r o p i c grains. T h e
m a g n e t i c m e t h o d , restricted t o f e r r o m a g n e t i c m a t e r
ials, is b a s e d o n the i n t e r a c t i o n of m a g n e t i c - d o m a i n wall m o t i o n with grain b o u n d a r i e s . T h e use of these
m e t h o d s c a n lead t o t h e d e t e r m i n a t i o n of grain size to
within a p p r o x i m a t e l y 1-2 A S T M grain sizes.

1. Principle

of Ultrasonic

Techniques

In polycrystalline m a t e r i a l , t h e p r o p a g a t i o n of ultra
sonic waves is affected b y discontinuities in the c h a r
acteristic acoustic i m p e d a n c e pc (p is the density a n d c
is t h e p h a s e velocity) a t t h e g r a i n b o u n d a r i e s d u e t o
the c r y s t a l l o g r a p h i c a n i s o t r o p y of c. A t each grain
b o u n d a r y , the w a v e is p a r t l y reflected a n d p a r t l y
m o d e c o n v e r t e d b e t w e e n l o n g i t u d i n a l (L) a n d t r a n s
verse (T) waves. T h e c o n t r i b u t i o n t o a t t e n u a t i o n d u e
to g r a i n - b o u n d a r y scattering is t h e s u m of these
scattering e n c o u n t e r s over t h e m a n y grains traversed
d u r i n g p r o p a g a t i o n . T h i s subject h a s been reviewed
b y P a p a d a k i s (1968) a n d by G o e b b e l s (1980).
T h e u l t r a s o n i c a t t e n u a t i o n is t h e a m p l i t u d e decre
a
m e n t coefficient in waves of t h e form e~ *, w h e r e is
t h e space c o o r d i n a t e . T h e L a n d c o n t r i b u t i o n s to
s
a t t e n u a t i o n d u e t o grain scattering (a L a n d ca\) h a v e
b e e n calculated for t h e case w h e n a n i s o t r o p y is small,
m u l t i p l e scattering c a n b e i g n o r e d , grains are
e q u i a x e d a n d of single p h a s e , a n d texture c a n be
i g n o r e d . F o r Rayleigh scattering of b u l k waves in
cubic crystals, t h a t is, w h e n t h e w a v e l e n g t h
2
w h e r e D is t h e a v e r a g e grain d i a m e t e r ,

Bibliography
Aucouturier J-L, Cauhape J-S, Destriau M, Hagenmuller P,
Lucat C, Menil F, Portier J, Salardenne J (eds.) 1986
Proc. 2nd Int. Meeting Chemical Sensors, Bordeaux,
France
Edmonds (ed.) 1988 Chemical Sensors. Blackie, Glas
gow, UK
Fisher G 1986 Ceramic sensors: providing control through
chemical reactions. Ceram. Bull. 65: 622-9
Goto S 1988 Solid State Electrochemistry and its Applica
tions to Sensors and Electronic Devices. Elsevier, Amster
dam
Moseley , Tofield C (eds.) 1987 Solid State Gas
Sensors. Hilger, Bristol, UK
Williams D E, McGeehin 1984 Solid state sensors and
monitors. In: Pletcher D (ed.) 1984 Electrochemistry,
Vol. 9. The Royal Society of Chemistry, London,
pp. 246-90
D . J. F r a y
[University of C a m b r i d g e ,
Cambridge, UK]

, 2>

H e r e , / is the frequency, cL a n d c T a r e the u l t r a s o n i c

p h a s e velocities for L a n d waves, respectively, a n d
t h e elastic a n i s o t r o p y factor = cn - cn 2cwhere
cnm a r e c r y s t a l l o g r a p h i c elasticity c o n s t a n t s . T h e
6
3
q u a n t i t y V = \n R > / < R is a characteristic grain
v o l u m e calculated from t h e g r a i n size d i s t r i b u t i o n
N(R) using m o m e n t s
/ 00

< / O =

Jo

0 /0

R"N(R)

dRI

Jo

N(R)

dR

a n d <> is % D. Similar f o r m u l a e exist for h e x a g o n a l

s
a n d o r t h o r h o m b i c crystallites. E x p r e s s i o n s for a in
t h e i n t e r m e d i a t e w a v e l e n g t h (stochastic) region w h e r e

179

Grain Size:

Nondestructive

Evaluation

&2
a n d t h e s h o r t w a v e l e n g t h (diffuse) region
w h e r e < 2nD a r e also k n o w n .
P a p a d a k i s ' s analysis indicates t h a t E q n s . (1) a n d (2)
a r e qualitatively c o r r e c t in s o far a s t h e a t t e n u a t i o n
4
follows a Vf l a w a n d t h a t they yield q u a n t i t a t i v e l y
a c c u r a t e results for t h e r a t i o [/. H o w e v e r , q u a n t i
s
tative a g r e e m e n t b e t w e e n a c t u a l values o f a L o r
predicted b y E q n s . (1) a n d (2) a n d e x p e r i m e n t a l
results is a t best w i t h i n a factor of 2. O w i n g t o this
lack of q u a n t i t a t i v e a g r e e m e n t , generalized e q u a t i o n s
34
s
3
s
((x L = kLd f
a n d oc j = k T d f \ w h e r e k L a n d kT a r e
empirically d e t e r m i n e d grain s c a t t e r i n g coefficients)
a r e used t o a n a l y z e e x p e r i m e n t a l results. I n m o s t
studies t h e statistical n a t u r e of t h e g r a i n size is s u p
pressed with V o r D simply being r e p l a c e d b y t h e c u b e
o r value, respectively, o f a n y o n e o f t h e m e t a l l o graphically d e t e r m i n e d a v e r a g e g r a i n d i a m e t e r s d.
Goebbels determined that measurements of grain
size s h o u l d b e m a d e in t h e region 0 . 0 3 < d j k < 0 . 3 .
F r e q u e n c i e s b e l o w 20 M H z h a v e been used o n m a t e r
ials with grain d i a m e t e r s o v e r 10 . A c c u r a c i e s o f n o
better t h a n 1 5 % , c o r r e s p o n d i n g t o 2 A S T M g r a i n
sizes, a r e claimed. M e a s u r e m e n t e r r o r arises from
factors such a s diffraction effects, s a m p l e g e o m e t r y ,
the presence of large isolated scatterers (inclusions),
the effects of t h e a c t u a l g r a i n size d i s t r i b u t i o n a n d ,
especially, t h e presence o f t h e small n u m b e r of rela
tively large g r a i n s .
F o r either L o r w a v e s , e x p e r i m e n t a l m e a s u r e
s
m e n t s d e t e r m i n e t h e t o t a l a t t e n u a t i o n a , o f w h i c h a is
only a p a r t . T h e r e m a i n d e r , referred t o a s t h e a b s o r p
a
tion a , is a t t r i b u t e d t o t h e excitation o f lattice defects
a n d t o t h e r m a l a n d m a g n e t i c d i s s i p a t i o n effects
a m o n g o t h e r m e c h a n i s m s . A b s o r p t i o n is m o d e l l e d b y
8

= / , w h e r e usually n= 1, 2 a n d t h e an a r e
phenomenological constants.
T h e r e a r e a t least t h r e e distinct t e c h n i q u e s for
d e t e r m i n i n g g r a i n size from m e a s u r e m e n t s o f t o t a l
attenuation,

a R = oc (f)

+ oc (d, / ) , in t h e

Rayleigh

region.

2. Single-Frequency

Ultrasonic

Technique

T h e a t t e n u a t i o n a R is d e t e r m i n e d a t a single frequency
for s a m p l e s identical except for g r a i n size. A leasts q u a r e s analysis o f t h e results of m e a s u r e m e n t s o n
s a m p l e s with k n o w n g r a i n size allows t h e d e t e r m i
a
n a t i o n of a a n d kL o r kT. W i t h these q u a n t i t i e s k n o w n
d c a n b e d e d u c e d from m e a s u r e m e n t s of a R in similar
a
samples. N o a s s u m p t i o n o n t h e f o r m of a is r e q u i r e d ,
a
b u t t h e t e c h n i q u e is sensitive t o differences in a
a m o n g the samples.

3.

Two-Frequency

Ultrasonic

Technique

T h e a t t e n u a t i o n a R is m e a s u r e d a t t w o frequencies,
a R 1 a t / j n e a r t h e l o n g a n d a R 2 a t f2 n e a r t h e s h o r t

180

w a v e l e n g t h p o r t i o n s of t h e R a y l e i g h region, a n d t h e
results a r e a n a l y z e d a c c o r d i n g t o E q n s . (1) a n d (2).
a
M o s t c o m m o n l y t h e a s s u m p t i o n a = axf is m a d e
3
4
leading t o k L Td = [ a R1 - a R 2/ 2 / / ; ] / [ / - / / ] ] , w h e r e
kLT r e p r e s e n t s either kL o r kT. R e g r e s s i o n analysis o f
m e a s u r e m e n t s from s a m p l e s o f k n o w n g r a i n size is
used t o d e t e r m i n e kLT a n d thereafter d for similar
s a m p l e s . T h i s t e c h n i q u e requires careful a t t e n t i o n t o
diffraction effects a n d , o w i n g t o t h e high o r d e r s in / ,
a c c u r a t e frequency d e t e r m i n a t i o n s . I t is also sensitive
4
t o d e v i a t i o n from t h e ( f \ f ) empirical m o d e l .

4. Backscatter

Ultrasonic

Technique

Since a polycrystalline g r a i n s t r u c t u r e scatters u l t r a

sonic waves, t h e conventional m e a s u r e m e n t of
a t t e n u a t i o n , o r f o r w a r d scattering, is c o m p l e m e n t e d
by t h e u l t r a s o n i c s c a t t e r i n g in o t h e r directions. F o r
t h e b a c k s c a t t e r case in h o m o g e n e o u s m a t e r i a l , t h e
received a m p l i t u d e AX) a s a function o f p r o p a g a t i o n
d i s t a n c e is
\n[A,(x)}

= b + i l n [ a ] - ( a + oc )X

A n a l y s i s o f b a c k s c a t t e r signals in c o m b i n a t i o n with
t e c h n i q u e s described in Sects. 2 a n d 3 p e r m i t s deter
s
mining a independent of sample geometry. This
c o m b i n e d t e c h n i q u e requires spatial a v e r a g i n g o v e r
large n u m b e r s of b a c k s c a t t e r w a v e f o r m s ( G o e b b e l s
1980).
W h i l e t h e p r e c e d i n g discussion deals with b u l k
w a v e s , it is also a p p l i c a b l e t o m e a s u r e m e n t s w i t h
surface w a v e s in t h e case of b o t h direct a t t e n u a t i o n
m e a s u r e m e n t s ( K e t t l e r et al. 1974) a n d b a c k s c a t t e r
m e a s u r e m e n t s ( H e c h t et al. 1981). T h e a b o v e m e n t i o n e d t e c h n i q u e s h a v e also b e e n used w i t h
m e a s u r e m e n t s in t h e diffuse region b y using a p p r o p r i
s
a
a t e f o r m s of a a n d a ( K e t t l e r et al. 1974). I n a d d i t i o n
t o grain-size m e a s u r e m e n t in b o t h b u l k a n d sheet
m e t a l s , a p p l i c a t i o n s h a v e been m a d e t o t h e d e t e r m i
n a t i o n of g r a i n - s i z e - d e p e n d e n t p r o p e r t i e s s u c h a s t h e
degree o f h e a t t r e a t m e n t o r s t a t e o f a n n e a l ( P a p a d a k i s
1968) a n d m e c h a n i c a l p r o p e r t i e s s u c h a s yield
s t r e n g t h ( K l i n m a n et a l . 1980).

5. Magnetic

Methods

E x p e r i m e n t a l evidence p o i n t s t o t h e influence o f g r a i n
size o n t h e m a g n e t i c p r o p e r t i e s o f steels ( L i t t m a n
1971). H o w e v e r , t h e f u n d a m e n t a l p h e n o m e n o l o g i c a l
r e l a t i o n s h i p s h a v e n o t been d e v e l o p e d . E m p i r i c a l
a p p r o a c h e s b a s e d o n linear regression analysis w i t h
coercive field, r e m a n e n t m a g n e t i z a t i o n , d e m a g n e t i z
ing field o r m a x i m u m p e r m e a b i l i t y a s i n d e p e n d e n t
v a r i a b l e s a n d either grain size o r a grain-size-related
p r o p e r t y a s d e p e n d e n t v a r i a b l e , h a v e achieved 1 5 %
accuracies in special cases. F a c t o r s such a s c h e m i c a l

Grain Size:

c o m p o s i t i o n , microstress state a n d the presence a n d

m o r p h o l o g y of s e c o n d a r y p h a s e s c a n severely
influence the results o b t a i n e d b y this a p p r o a c h .

6. Barkhausen

Technique

T h e d i s c o n t i n u o u s m o v e m e n t of Bloch walls d u r i n g
d o m a i n g r o w t h g e n e r a t e s B a r k h a u s e n noise. Since
d o m a i n g r o w t h is influenced b y grain b o u n d a r y pin
ning sites, statistical analysis of B a r k h a u s e n noise
m u s t include g r a i n size as a p a r a m e t e r ( O t a l o a n d
S a y n a j a k a n g a s 1972). Because of t h e shielding of t h e
skin effect, i n t e r r o g a t i o n d e p t h is limited a n d a p p l i c a
tion is p r i m a r i l y t o sheet geometries for w h i c h g r a i n
size h a s been d e t e r m i n e d t o b e t t e r t h a n 1 A S T M
u n i t t o a s a m p l e d e p t h of a p p r o x i m a t e l y 0 . 4 m m .
A c c u r a c y is s t r o n g l y affected b y c r y s t a l l o g r a p h i c
texture, strain state, c h e m i s t r y a n d sheet thickness.

Bibliography
American Society for Testing and Materials 1980 Standard
method for estimating the average grain size of metals,

Nondestructive

Evaluation

ANSI/ASTM Standard El 12-80. Annual Book of ASTM

Standards, Pt. II, Metallography, Nondestructive Testing.
American Society for Testing and Materials, Philadel
phia, PA, pp. 186-220
Goebbels 1980 Structure analysis by scattered ultrasonic
radiation. In: Sharpe R S (ed.) 1980 Research Techniques
in Nondestructive Testing, Vol. 4. Academic Press, Lon
don, pp. 88-157
Hecht A, Thiel R, Neumann E, Mundry 1981 Non
destructive determination of grain size in austenitic sheet
by ultrasonic backscatter. Mater. Eval. 39(10): 934-8
Kettler R, Latiff R, Fiore F 1974 Surface ultrasonic
measurement of grain size of silicon iron sheet. Metall.
Trans. 5: 952-3
Klinman R, Webster G R, Marsh F J, Stephenson 1980
Ultrasonic prediction of grain size, strength and tough
ness in plain carbon steel. Mater. Eval. 38(10): 26-32
Littman F 1971 Iron and silicon-iron alloys. IEEE Trans.
Magn. 1: 48-60
Otalo M, Saynajakangas S 1972 A new electronic grain-size
analysis for technical steel. J. Phys. 5: 669-72
Papadakis 1968 Ultrasonic attenuation caused by
scattering in polycrystalline media. In: Mason W (ed.)
1968 Physical Acoustics, Vol. IV, Pt. B. Academic Press,
New York, pp. 269-328
R. K l i n m a n
[Bethlehem Steel C o r p o r a t i o n , Bethlehem,
Pennsylvania, USA]

181


Hardness Characterization
H a r d n e s s d e t e r m i n a t i o n s a r e a m o n g t h e m o s t fre
q u e n t l y used tests for t h e assessment of m e c h a n i c a l
p r o p e r t i e s . T h e value of t h e test d e p e n d s o n t h e fact
t h a t it affords a n inexpensive, n o n d e s t r u c t i v e m e a n s
of e v a l u a t i n g a n u m b e r of useful engineering p r o p e r
ties, such as tensile s t r e n g t h , h e a t t r e a t m e n t o r t h e
state of cold w o r k i n g in s t r u c t u r a l m e t a l s . T h e rela
t i o n s h i p b e t w e e n these p r o p e r t i e s a n d h a r d n e s s , while
n o t a n exact o n e , is close e n o u g h for a wide r a n g e of
industrial c o n t r o l s .
H a r d n e s s h a s been loosely defined as resistance t o
p e r m a n e n t i n d e n t a t i o n , b u t it is well k n o w n t h a t t h e
resistance is significantly affected by t h e s h a p e of t h e
tool used t o p r o d u c e t h e i n d e n t a t i o n ( T u c k e r m a n
1925). T h i s d e p e n d e n c e strongly suggests t h a t h a r d
ness is n o t a distinct p r o p e r t y b u t a c o m b i n a t i o n of a
n u m b e r of p r o p e r t i e s , such as yield s t r e n g t h in s h e a r
a n d b u l k m o d u l u s . T h e p e n e t r a t i o n of a n i n d e n t i n g
tool i n t o the surface of a m a t e r i a l is influenced by
these p r o p e r t i e s a c c o r d i n g t o t h e s h a p e of the tool. A
h a r d n e s s n u m b e r , a r a t i o of l o a d t o i m p r e s s i o n a r e a ,
is n o t a simple c o m p r e s s i o n stress, b u t a highly
c o m p l e x value in w h i c h a n u m b e r of basic p r o p e r t i e s
are s u m m e d in p r o p o r t i o n s d e p e n d e n t o n t h e s h a p e of
the i n d e n t i n g tool.
A l t h o u g h there is p r o b a b l y n o such p r o p e r t y as
" h a r d n e s s , " it is a c o n v e n i e n t generic t e r m . P r o p e r l y ,
the t e r m h a r d n e s s h a s m e a n i n g only in t e r m s of a
specific test. O n e m a y s p e a k of Brinell h a r d n e s s o r
Rockwell h a r d n e s s , b u t they s h o u l d n o t be c o n s i d e r e d
c o m m o n m e a s u r e s of t h e s a m e t h i n g .
A n u m b e r of different tests h a v e been d e v e l o p e d .
T h e y r a n g e from t h e simple M o h s scratch test, p r o
p o s e d in 1822 a n d still used as a basic, practical test
for the field m i n e r a l o g i s t , t o t h e highly s o p h i s t i c a t e d
m i c r o h a r d n e s s tests t h a t c a n e v a l u a t e individual crys
tal c o n s t i t u e n t s of a m e t a l m a t r i x . N e a r l y all of these
tests involve s o m e k i n d of i m p r e s s i o n m a d e in t h e
surface of a specimen. T h e i m p r e s s i o n m a y be in t h e
form of a scratch, a n i n d e n t a t i o n m a d e by a steel o r
d i a m o n d t o o l u n d e r static forces o r a d y n a m i c re
b o u n d test. A m o n g s u b s t a n c e s tested, m e t a l s h a v e
p r o b a b l y received t h e m o s t a t t e n t i o n , b u t r u b b e r a n d
m a n u f a c t u r e d plastics a r e also i m p o r t a n t a r e a s of
a p p l i c a t i o n . M e t h o d s a r e available t o test m i n e r a l s ,
glass, h a r d c a r b i d e s a n d c e r a m i c m a t e r i a l s . Tests o n
such diverse m a t e r i a l s as p a i n t a n d v a r n i s h c o a t i n g s
have proved valuable.
T h e following sections describe specific tests t h a t
h a v e gained general a c c e p t a n c e . F o r m o s t , s t a n d a r d
m e t h o d s a n d p r o c e d u r e s h a v e been a d o p t e d b y
various n a t i o n a l s t a n d a r d i z i n g o r g a n i z a t i o n s a n d b y

o r g a n i z a t i o n s such as the I n t e r n a t i o n a l O r g a n i z a t i o n
for S t a n d a r d i z a t i o n (ISO) a n d t h e I n t e r n a t i o n a l
O r g a n i z a t i o n for Legal M e t r o l o g y ( O I M L ) .

7. The Brinell

Hardness

Test

T h e Brinell test, i n t r o d u c e d in 1900 in Sweden by J A

Brinell, is t h e oldest of the m o d e r n h a r d n e s s tests. It
consists of forcing a steel o r h a r d - m e t a l ball into the
surface of the specimen u n d e r load. After r e m o v a l of
t h e l o a d , t h e d i a m e t e r of the circular impression left in
t h e specimen is m e a s u r e d with a l o w - p o w e r e d m i c r o
scope a n d the surface a r e a of the impression calcu
lated o n the a s s u m p t i o n t h a t it h a s the s h a p e of the
u n d e f o r m e d ball. A h a r d n e s s n u m b e r is calculated as
the i n d e n t i n g l o a d in kilograms-force (kgf) divided by
the surface a r e a of t h e i m p r e s s i o n in s q u a r e milli
m e t e r s . T h e Brinell h a r d n e s s n u m b e r , like o t h e r h a r d
ness n u m b e r s , is always q u o t e d w i t h o u t units of
measurement.
A ball d i a m e t e r of 10 m m a n d a n i n d e n t i n g load of
3000 kgf a r e a c c e p t e d as s t a n d a r d for tests of m a t e r
ials such as steels a n d similarly h a r d alloys. F o r softer
c o p p e r a n d a l u m i n u m alloys, a l o a d of 500 kgf is
generally used with the 10 m m ball. Brinell h a r d n e s s
n u m b e r s r a n g e from values as low as 1 o r 2 for very
soft m e t a l s a n d s o m e plastics u p t o a b o u t 600 for
h a r d e n e d steels. Steel balls a r e n o t r e c o m m e n d e d for
m a t e r i a l s a b o v e a b o u t Brinell 450, b u t h a r d - m e t a l
balls such as t u n g s t e n c a r b i d e c a n be used u p to a b o u t
Brinell 600. Tests a b o v e Brinell 630 a r e n o t r e c o m
m e n d e d b e c a u s e of t h e difficulty of m e a s u r i n g the very
small a n d shallow i m p r e s s i o n . T h i s value is less t h a n
t h e m a x i m u m h a r d e n a b i l i t y of h i g h - c a r b o n steels.
T h e Brinell h a r d n e s s n u m b e r is calculated from the
formula

2 ]l2

nD[D-(D -d ) ]
w h e r e H B is t h e Brinell h a r d n e s s n u m b e r , F is the
i n d e n t i n g l o a d in kgf, D is the ball d i a m e t e r in m m
a n d d is the i m p r e s s i o n d i a m e t e r in m m . C o n v e n i e n t
tables c o n v e r t i n g i m p r e s s i o n d i a m e t e r s directly t o
Brinell n u m b e r s a r e available from m a n y sources, for
e x a m p l e the Standard Test Method for Brinell Hard
ness of Metallic Materials ( A S T M 10), issued by the
A m e r i c a n Society for T e s t i n g a n d M a t e r i a l s .
T h e r e q u i r e m e n t for t h e u n i q u e use of the milli
m e t e r a n d the k i l o g r a m - f o r c e i n t r o d u c e s a p r o b l e m
w h e n a c h a n g e is m a d e t o SI u n i t s . H e r e , the unit of
force b e c o m e s the n e w t o n a n d in s o m e jurisdictions
its use in preference t o the kilogram-force is m a n d a
t o r y . T h e t e n d e n c y in i n t e r n a t i o n a l s t a n d a r d s h a s

183

Hardness

Characterization

been t o express F in n e w t o n s a l o n g with a multiply

ing factor in the f o r m u l a c o n v e r t i n g t h e force i n t o
kilogram-force units.
T h e sensitivity of the Brinell test t o l o a d is a factor
of i m p o r t a n c e in test p r o c e d u r e s . Since the Brinell
n u m b e r is essentially a stress o r pressure value (i.e.,
load p e r unit area) o n e m i g h t expect to o b t a i n t h e
s a m e result in tests m a d e at different l o a d s o n a
h o m o g e n e o u s piece of m a t e r i a l . I n practice the results
are n o t the s a m e . Tests m a d e at l o a d s of 3000 kgf a n d
500 kgf with a 10 m m ball d o n o t agree a n d , further
m o r e , t h e a m o u n t of d i s a g r e e m e n t , even at t h e s a m e
h a r d n e s s level, is different for different m a t e r i a l s . T h e
discrepancy arises because i m p r e s s i o n s m a d e a t t w o
different l o a d s a r e n o t geometrically similar. A verti
cal section t h r o u g h i m p r e s s i o n s at 500 kgf a n d
3000 kgf w o u l d s h o w t h a t t h e heavier l o a d p e n e t r a t e d
m o r e deeply in relation t o the d i a m e t e r of t h e i m p r e s
sion t h a n did the 500 kgf l o a d . In effect, the t w o
impressions were m a d e with different
shaped
indenters even t h o u g h t h e s a m e ball w a s used for
b o t h . A s p o i n t e d o u t earlier, the s a m p l i n g of basic
p r o p e r t i e s will be different a n d t h e c o m p o s i t e value
t h a t forms t h e h a r d n e s s n u m b e r will, c o n s e q u e n t l y , be
different. Because of this effect, it is i m p o r t a n t t h a t in
r e p o r t i n g the results of a Brinell test t h e l o a d a n d size
of the i n d e n t i n g ball b e clearly stated. T h e u s u a l
practice is t o a n n o t a t e t h e l o a d a n d ball d i a m e t e r if
they differ from t h e s t a n d a r d values of 3000 kgf a n d
10 m m .
A solution t o the l o a d sensitivity p r o b l e m is t o
c h a n g e b o t h l o a d a n d ball d i a m e t e r in such p r o p o r
tions t h a t impressions will be geometrically similar. If
the r a t i o of l o a d to t h e s q u a r e of the ball d i a m e t e r is
k e p t u n c h a n g e d , this c o n d i t i o n will be achieved. F o r
e x a m p l e , the 3000 kgf l o a d a n d 10 m m ball h a v e a
2
F/D r a t i o of 30, as d o e s the c o m b i n a t i o n of a
750 kgf l o a d a n d 5 m m ball. T h u s , if a h o m o g e n e o u s
m a t e r i a l is tested, t h e results will be c o m p a r a b l e for
b o t h c o m b i n a t i o n s . T h i s a p p r o a c h p e r m i t s tests o n
m a t e r i a l t o o thin for the s t a n d a r d test l o a d .
T h e Brinell h a r d n e s s test is widely used ( a l t h o u g h it
is s o m e w h a t slow a n d leaves a n i m p r e s s i o n readily
a p p a r e n t t o the u n a i d e d eye) p a r t i c u l a r l y in testing
large forgings a n d m a t e r i a l s h a v i n g a c o a r s e grain
structure. T h e test e q u i p m e n t is rugged a n d well
suited t o use in the o p e n mill area. Ball i n d e n t e r s a r e
readily available from ball b e a r i n g m a n u f a c t u r e r s a n d
a r e p r o d u c e d in d i m e n s i o n a l tolerances far closer t h a n
needed for t h e test.
T h e a c c u r a c y of a Brinell tester c a n be verified b y
checking its readings o n a s t a n d a r d i z e d test block.
Such b l o c k s c a n be o b t a i n e d from t h e m a c h i n e m a n u
facturer o r from special s t a n d a r d i z i n g l a b o r a t o r i e s .
A n o t h e r m e t h o d is s e p a r a t e verification of the i n d e n t
ing l o a d b y m e a n s of elastic p r o v i n g devices a n d
m e a s u r e m e n t of i m p r e s s i o n d i a m e t e r s by a highprecision m e a s u r i n g m i c r o s c o p e .

184

2. The Rockwell

Hardness

Test

T h e R o c k w e l l test w a s d e v e l o p e d a b o u t 1922 by
Stanley R o c k w e l l , a metallurgist, w h o saw t h e need
for a n i n s t r u m e n t c a p a b l e of testing the very h a r d
steels used in ball b e a r i n g races. T h e test is p e r f o r m e d
by a m a c h i n e t h a t initially forces a p e n e t r a t o r i n t o the
surface of t h e specimen u n d e r a light l o a d called t h e
minor load. A d e p t h - m e a s u r i n g i n d i c a t o r c o u p l e d t o
t h e p e n e t r a t o r is set t o a null reference a n d t h e l o a d o n
t h e p e n e t r a t o r is increased s m o o t h l y t o a higher value,
called t h e major load, a n d t h e n r e d u c e d a g a i n t o t h e
m i n o r l o a d value. T h e d e p t h m e a s u r i n g device t h e n
s h o w s t h e increased d e p t h of i n d e n t a t i o n c a u s e d b y
t h e a p p l i c a t i o n of the m a j o r l o a d . T h e scale is g r a d u
a t e d t o r e a d the h a r d n e s s n u m b e r directly.
T h e m i n o r l o a d is 10 kgf a n d the m a j o r l o a d m a y b e
either 60, 100 o r 150 kgf. T h e p e n e t r a t o r is a d i a m o n d
c o n e h a v i n g a n included angle of 120 with a spherical
p o i n t of 0.2 m m r a d i u s . F o r testing softer m e t a l s a n d
plastics a series of ball p e n e t r a t o r s of
--, i a n d \ in.
d i a m e t e r is available. E a c h c o m b i n a t i o n of p e n e t r a t o r
a n d m a j o r l o a d c o n s t i t u t e s a s e p a r a t e scale a n d a
R o c k w e l l h a r d n e s s n u m b e r is always q u o t e d with a
letter s y m b o l t o indicate t h e scale. O n e R o c k w e l l
n u m b e r , t h e smallest g r a d u a t i o n o n t h e i n d i c a t o r dial,
represents a n increase in d e p t h of 0.002 m m .
T h e R o c k w e l l test is extremely useful in the c o n t r o l
of sheet m a t e r i a l such as a l u m i n u m , b r a s s o r steel.
Because of the e c o n o m i c i m p o r t a n c e of very thin
sheet, a special tester k n o w n as t h e R o c k w e l l Super
ficial Tester w a s developed. I n this m a c h i n e , the
m i n o r l o a d is r e d u c e d from 10 kgf t o 3 kgf. T h e m a j o r
l o a d s a r e 15, 30 a n d 45 kgf. T h e sensitivity of the
d e p t h - m e a s u r i n g device is increased t o 0.001 m m p e r
division.
T h e Superficial T e s t e r uses t h e s a m e series of
i n d e n t e r s as t h e s t a n d a r d m a c h i n e a n d c a n success
fully test h a r d sheet m a t e r i a l s as thin as 0.125 m m .
T h e d e e p e r i m p r e s s i o n s in soft sheet require a g r e a t e r
thickness. M o s t p r o c e d u r a l s t a n d a r d s p r o v i d e tables
s h o w i n g m i n i m u m thickness limits for v a r i o u s scales
a n d h a r d n e s s e s . T h e general rule is t h a t n o bulge o r
o t h e r m a r k i n g s h o w i n g t h e effect of l o a d s h o u l d
be visible o n t h e side of t h e piece o p p o s i t e t h e
impression.
T h e R o c k w e l l test is r a p i d a n d d o e s n o t require
a skilled o p e r a t o r . T h e e q u i p m e n t c a n b e a d a p t e d
readily t o a u t o m a t i o n a n d use with d a t a acquisition
systems. D a i l y verification of t h e a c c u r a c y of t h e
tester is a c c o m p l i s h e d by c a l i b r a t e d test blocks avail
able from t h e m a n u f a c t u r e r s of t h e m a c h i n e s . I n t h e
U K a n d in s o m e E u r o p e a n c o u n t r i e s , test b l o c k s
certified b y official g o v e r n m e n t b o d i e s a r e available.

3. The Vickers

Hardness

Test

T h e Vickers test, n a m e d after t h e original m a n u f a c

t u r e r b u t s o m e t i m e s called t h e d i a m o n d p y r a m i d

Hardness

h a r d n e s s test, w a s designed in E n g l a n d in 1922 b y

R S m i t h a n d G S a n d l u n d . T h e use of a s q u a r e - b a s e d
p y r a m i d as t h e i n d e n t e r i n s u r e d t h a t i m p r e s s i o n s
m a d e a t different d e p t h s w o u l d all b e geometrically
similar. T o s i m u l a t e t h e Brinell test, a n included face
angle of 136 w a s selected. T h i s angle is t h e angle of
t a n g e n c y a t t h e edge of a Brinell i m p r e s s i o n h a v i n g a
d i a m e t e r of 3.75 m m m a d e w i t h t h e s t a n d a r d 10 m m
ball, t h e m i d p o i n t of t h e r e c o m m e n d e d r a n g e of
impression d i a m e t e r s . A s a result of this design,
Vickers tests m a d e in a h o m o g e n e o u s m a t e r i a l o v e r a
r a n g e of l o a d s from less t h a n 1 kgf t o 120 kgf all give
essentially t h e s a m e h a r d n e s s n u m b e r .
I n t h e test, t h e i n d e n t e r is forced i n t o t h e surface of
the specimen, t h e resulting s q u a r e i m p r e s s i o n , after
r e m o v a l of t h e i n d e n t e r , is viewed in a m e a s u r i n g
microscope and the two diagonals measured. A hard
ness n u m b e r , defined as t h e i n d e n t i n g l o a d in
kilograms-force divided b y t h e surface a r e a of t h e
impression, is calculated from t h e f o r m u l a
H V = 1.854

F/D

tion of t h e specimen. T h e h a m m e r is quite light a n d

leaves only a barely perceptible m a r k .
T h e Scleroscope offers a c o n s i d e r a b l e a d v a n t a g e in
testing large objects such as t h e rolls used in steel a n d
p a p e r mills b e c a u s e it need n o t be rigidly c l a m p e d t o
t h e test piece as in t h e case of t h e c o n v e n t i o n a l
i n d e n t a t i o n testers. V a r i o u s f o r m s of s u p p o r t are
offered so t h a t t h e tester c a n be s u p p o r t e d in a vertical
p o s i t i o n d u r i n g a test. T h e m a r k left is so slight t h a t
there is little likelihood t h a t t h e i n d e n t a t i o n will affect
a n o p p o s i t e roll while t h e t w o a r e r u n n i n g t o g e t h e r in
service.
Scleroscopes a r e m a n u f a c t u r e d in t w o m o d e l s . In
b o t h , t h e h a m m e r falls within a closed t u b e , b u t in o n e
t h e r e b o u n d is r e a d by eye a g a i n s t a scale in the t u b e .
In t h e o t h e r , t h e height of r e b o u n d is indicated by a
m a x i m u m pointer.
A special Scleroscope tester, k n o w n as t h e F o r g e d
R o l l tester, h a s b e e n d e v e l o p e d t o c o m p e n s a t e for t h e
a n o m a l o u s l y high r e a d i n g s o b t a i n e d o n a chilled cast
i r o n roll w h e n c o m p a r e d t o a forged steel roll.

w h e r e H V is t h e Vickers h a r d n e s s n u m b e r , F is t h e
i n d e n t i n g l o a d in kgf a n d D is t h e a v e r a g e d i a g o n a l
length in m m .
T h e Vickers test is well a d a p t e d t o testing very h a r d
steels a n d covers t h e r a n g e d o w n t o very soft m e t a l s in
a single scale of n u m b e r s . T h e i m p r e s s i o n s a r e small,
typically less t h a n 0.5 m m o n t h e d i a g o n a l , a n d n o t
readily a p p a r e n t t o t h e u n a i d e d eye. Because of this, a
m o r e e l a b o r a t e r e a d i n g m i c r o s c o p e is r e q u i r e d t h a n
for t h e Brinell test. U s u a l l y t h e m i c r o s c o p e is built
i n t o t h e testing m a c h i n e a n d a r r a n g e d so t h a t t h e
impression is a u t o m a t i c a l l y c e n t e r e d in t h e viewing
field for m e a s u r e m e n t . T h e m i c r o s c o p e h a s a magnifi
c a t i o n of t h e o r d e r of 100 a n d is usually e q u i p p e d w i t h
a m i c r o m e t e r eyepiece g r a d u a t e d t o r e a d directly t o
the nearest 0.001 m m . Because of t h e h i g h e r magnifi
c a t i o n , a m o r e careful p r e p a r a t i o n of t h e specimen
surface is r e q u i r e d t h a n for t h e Brinell o r R o c k w e l l
tests.
T h e test is c a p a b l e of resolving small differences in
h a r d n e s s a n d its a c c u r a c y is easily c o n t r o l l e d either b y
p r i m a r y s t a n d a r d i z a t i o n of l o a d a n d i n d e n t e r s h a p e
o r b y s t a n d a r d test b l o c k s . T h e test is widely used in
the U K a n d o n t h e C o n t i n e n t b u t h a s h a d less
p o p u l a r i t y in t h e U S A .

4. The Scleroscope

Characterization

Test

T h e Scleroscope test differs from t h e u s u a l i n d e n

t a t i o n h a r d n e s s tests in t h a t it is a r e b o u n d test. A
d i a m o n d t i p p e d r o d , called t h e hammer, is d r o p p e d
from a fixed elevation t o t h e surface of t h e specimen
a n d the height of t h e r e b o u n d n o t e d . T h e difference in
elevation b e t w e e n t h e release p o i n t a n d t h e t o p of t h e
r e b o u n d is a m e a s u r e of t h e energy lost in d e f o r m a

5. Microhardness

Tests

M i c r o h a r d n e s s tests a r e i n d e n t a t i o n h a r d n e s s tests
m a d e u n d e r u n u s u a l l y low i n d e n t i n g forces, usually in
t h e r a n g e from o n e g r a m - f o r c e t o o n e kilogram-force.
T h e resulting i n d e n t a t i o n is of m i c r o s c o p i c size, in the
r a n g e of 0.01 m m t o 0.10 m m , a n d h a r d l y visible to
t h e u n a i d e d eye. It is possible t o test such objects as
small w a t c h p i n i o n s , needle p o i n t s a n d even indi
v i d u a l crystals in a m e t a l m a t r i x .
Because of t h e p r o b l e m s of m a k i n g , locating a n d
m e a s u r i n g these small i m p r e s s i o n s , special testing
machines have been developed that permit the opera
t o r t o locate u n d e r t h e m i c r o s c o p e t h e p a r t i c u l a r a r e a
w h e r e t h e i n d e n t a t i o n is t o be m a d e , transfer it
automatically under the indenter, m a k e the impres
sion a n d r e t u r n it t o t h e center of t h e m i c r o s c o p e field
for m e a s u r e m e n t . T h e m e a s u r e m e n t s a r e usually
m a d e b y a m i c r o s c o p e e q u i p p e d with a vertical illumi
n a t o r a n d a filar m e a s u r i n g eyepiece. Very careful
p r e p a r a t i o n of t h e specimen is r e q u i r e d .
T h e i n d e n t e r is a d i a m o n d p y r a m i d , either t h e 136
Vickers i n d e n t e r o r t h e K n o o p i n d e n t e r . T h e Vickers
i n d e n t e r is preferred for testing m e t a l s since t h e test is
a l m o s t i n d e p e n d e n t of l o a d a n d t h e results a r e c o m
p a r a b l e t o Vickers tests m a d e u n d e r heavier l o a d s .
T h e K n o o p i n d e n t e r p e r m i t s tests t o b e m a d e o n
frangible m a t e r i a l s such as glass, g e m s t o n e s a n d h a r d
c a r b i d e s , w h i c h c o u l d n o t b e tested by o t h e r forms of
indenter.
T h e K n o o p i n d e n t e r w a s d e v e l o p e d a t the N a t i o n a l
B u r e a u of S t a n d a r d s in t h e U S A ( K n o o p et al. 1939).
It is a four-sided d i a m o n d p y r a m i d of e l o n g a t e d s h a p e
in w h i c h t h e angle b e t w e e n t w o o p p o s i t e edges is 172
30' a n d b e t w e e n t h e o t h e r t w o edges 130 0 \ T h e
i m p r e s s i o n left b y t h e i n d e n t e r is a r h o m b u s with o n e

185

Hardness

Characterization

d i a g o n a l a b o u t seven times t h e length of the o t h e r .

T h e d e p t h of the impression is a b o u t ^ of t h e long
d i a g o n a l . In practice, only the long d i a g o n a l is
m e a s u r e d . T h e K n o o p h a r d n e s s n u m b e r is defined as
the i n d e n t i n g l o a d in kilograms-force divided by the
projected a r e a of the impression in s q u a r e millimeters.
T h e K n o o p n u m b e r c a n be calculated from the
formula
H K = 14.229

F/D

where H K is the K n o o p h a r d n e s s n u m b e r , F is the

i n d e n t i n g l o a d in kgf a n d D is the length of the l o n g
d i a g o n a l in m m .
K n o o p h a r d n e s s values are u n f o r t u n a t e l y n o t inde
p e n d e n t of the value of the i n d e n t i n g l o a d as m i g h t be
expected from the e x a m p l e of the Vickers indenter. If
a h o m o g e n e o u s specimen is tested at successively
lower l o a d s , the K n o o p n u m b e r increases m a r k e d l y .
This reaction h a s been a t t r i b u t e d t o elastic recovery at
the e n d s of the long a n d shallow i m p r e s s i o n a n d t o the
inability of the m i c r o s c o p e to resolve the fine tip of t h e
impression. O b s e r v e r s h a v e disagreed o n w h e t h e r o r
n o t the Vickers test suffers from a similar effect a t very
low l o a d s . W h a t e v e r the result, a Vickers o r K n o o p
test r e p o r t s h o u l d always cite the value of the i n d e n t
ing l o a d used.

6. Portable

Hardness

Testers

A n u m b e r of small, lightweight testers h a v e been

developed for soft m e t a l s a n d n o n m e t a l l i c m a t e r i a l s .
A simple m e c h a n i c a l principle used in m a n y of these
testers is a s p r i n g - l o a d e d indenter, usually a t r u n c a t e d
c o n e or a spherical s h a p e with a flattened tip,
m o u n t e d within a c o m p a c t h o u s i n g with a dial indi
c a t o r a r r a n g e d t o s h o w the travel of t h e i n d e n t e r . T h e
h o u s i n g , with its slightly p r o t r u d i n g i n d e n t e r , is
pressed d o w n by h a n d against the surface of a speci
m e n until the base of the h o u s i n g is firmly in c o n t a c t
with the specimen. T h e dial i n d i c a t o r t h e n s h o w s a
value d e p e n d e n t u p o n the distance the i n d e n t e r h a s
p e n e t r a t e d i n t o the specimen surface. U s u a l l y the dial
is g r a d u a t e d i n t o a scale t h a t s h o w s higher n u m b e r s
for h a r d e r m a t e r i a l s .
A n excellent e x a m p l e of such a tester is the S h o r e
D u r o m e t e r , a n i n s t r u m e n t widely used for testing
r u b b e r . It c o m e s in several m o d e l s to cover the wide
r a n g e of r u b b e r h a r d n e s s e s . T h e D u r o m e t e r s h a v e
their o w n scale of h a r d n e s s n u m b e r s . O t h e r testers
o p e r a t i n g o n the principle of the s p r i n g - l o a d e d
i n d e n t e r a r e used for the softer m e t a l alloys a n d
afford a r a p i d , c o n v e n i e n t m e a n s for identifying
m a t e r i a l in stock bins a n d similar s i t u a t i o n s w h e r e the
use of a larger tester w o u l d be i m p r a c t i c a l . S o m e of
these testers h a v e u n i q u e scales of their o w n b u t
o t h e r s a r e g r a d u a t e d t o r e a d Brinell, Rockwell o r
Vickers n u m b e r s . S o m e of the latter actually a p p l y the

186

s t a n d a r d l o a d s a n d use the s t a n d a r d i n d e n t e r s b u t
o t h e r s d o n o t . T h e user is w a r n e d t h a t even t h o u g h a
n o n s t a n d a r d m a c h i n e m a y r e a d correctly o n a test
block, it m a y give a n incorrect result w h e n used with
a n o t h e r m a t e r i a l , p a r t i c u l a r l y if there is a h a r d n e s s
g r a d i e n t from t h e surface t o t h e interior.
O t h e r types of p o r t a b l e testers o p e r a t e o n principles
t h a t seem a t first t o be far r e m o v e d from the c o n v e n
tional i n d e n t a t i o n test. T h e e d d y c u r r e n t test, which
r e s p o n d s t o a c o m b i n a t i o n of the m a g n e t i c a n d elec
trical p r o p e r t i e s of the specimen, t h e S o n a d u r tester in
which a r o d t i p p e d by a d i a m o n d i n d e n t e r is l o a d e d
against t h e specimen a n d driven i n t o a n a t u r a l reso
n a n t frequency responsive t o t h e a r e a of c o n t a c t
b e t w e e n i n d e n t e r a n d specimen, a n d the E s e w a y tester
in which a n i n d e n t e r i m p a c t s the specimen surface a t a
fixed speed a n d t h e deceleration of the i n d e n t e r is
m e a s u r e d by a piezoelectric sensor are all examples of
n e w t e c h n i q u e s in t h e field. W h e t h e r o r n o t they will
be accepted in time as formal h a r d n e s s testing devices
r e m a i n s t o be seen, b u t they d o fulfill the basic
p r e m i s e b e h i n d all h a r d n e s s t e s t i n g t h e y s e p a r a t e
m a t e r i a l s b y a m e a n s t h a t correlates with a variety of
useful engineering p r o p e r t i e s .

7. Hardness

Conversion

Tables

Because h a r d n e s s is extensively used in p r o c u r e m e n t

specifications, there is inevitably a d e m a n d for a n
authorized conversion relationship a m o n g the major
types of test. T h e c o n c e p t persists t h a t there m u s t be a
fixed r e l a t i o n s h i p a m o n g t h e m . T h e factual situation,
o u t l i n e d earlier, t h a t each test m e a s u r e s a different
s a m p l i n g of a n u m b e r of different f u n d a m e n t a l
p r o p e r t i e s , is often i g n o r e d o r rejected u n d e r pressure
for a s o l u t i o n t o a p r o b l e m .
O b v i o u s l y , o n e c a n select a specific m a t e r i a l , such
as a tool steel, h e a t treat specimens to a series of
g r a d u a t e d h a r d n e s s e s a n d test each specimen with
Brinell, R o c k w e l l a n d Vickers tests t o derive a welldefined c o n v e r s i o n r e l a t i o n s h i p a m o n g t h e three tests.
If t h e e x p e r i m e n t is t h e n r e p e a t e d with a steel of
different alloying type, such as a h i g h - s t r e n g t h aircraft
steel, t h e results, while close, will differ from the first
e x p e r i m e n t by significant a m o u n t s . T h e fact t h a t the
a g r e e m e n t is so close gives the impression t h a t a
universal c o n v e r s i o n table is j u s t a m a t t e r of a little
m o r e care in t h e l a b o r a t o r y m e a s u r e m e n t s .
C o n v e r s i o n tables h a v e been w o r k e d o u t for s o m e
specific m a t e r i a l s . T h e A m e r i c a n Society for T e s t i n g
a n d M a t e r i a l s p r o v i d e s tables for c a r t r i d g e b r a s s ,
c o p p e r , austenitic stainless steel, nickel a n d highnickel alloys, a n d a general table for n o n a u s t e n i t i c
steel. O t h e r n a t i o n a l s t a n d a r d i z i n g o r g a n i z a t i o n s
h a v e issued similar tables, all with t h e w a r n i n g t h a t
they a r e a t best only a p p r o x i m a t i o n s a n d m a y i n t r o
d u c e s u b s t a n t i a l e r r o r if used o u t s i d e of t h e stated
scope. T h e m y t h of the a c c u r a t e h a r d n e s s c o n v e r s i o n

Hydrogen

table is n o t easily dispelled, h o w e v e r , despite these

warnings.
See also: Mechanical Properties Microprobe

as a Metallurgical

Probe

p r o p e r t i e s of s o m e m e t a l s as well, this being t e r m e d

h y d r o g e n e m b r i t t l e m e n t (Bernstein a n d T h o m p s o n
1981). O n t h e o t h e r h a n d , its high solubility m a y be
beneficial t o using m e t a l s for h y d r o g e n s t o r a g e
(Alefeld a n d Volkl 1980).

Bibliography
American Society for Testing and Materials 1984 Annual
Book of ASTM Standards, Pt. 3. American Society for
Testing and Materials, Philadelphia, PA, pp. 16474.
Knoop F, Peters C G, Emerson W 1939 A sensitive
pyramidal diamond tool for indentation measurements.
J. Res. Natl. Bur. Stand. 23: 39-61
Lysaght V 1949 Indentation Hardness Testing. Reinhold,
New York
Lysaght V E, DeBellis A 1969 Hardness Testing Handbook.
American Chain and Cable Company, Bridgeport, CT
Mott W 1956 Micro-Indentation Hardness Testing. Butterworths, London
O'Neill 1967 Hardness Measurement of Metals and Alloys,
2nd edn. Chapman and Hall, London
Tabor D 1951 The Hardness of Metals. Clarendon Press,
Oxford
Tuckerman L 1925 Hardness and hardness testing. Mech.
Eng. 47: 53-5
Williams S R 1942 Hardness and Hardness Measurements.
American Society for Metals, Cleveland, OH
D . R. T a t e
[Rockville, M a r y l a n d , U S A ]

Hydrogen as a Metallurgical Probe

H y d r o g e n h a s t h e smallest a t o m s of all t h e elements,
which gives rise t o a variety of p r o p e r t i e s t h a t m a k e it
especially favorable for use as a metallurgical p r o b e .
First, its diffusivity is very high. T h u s special struc
t u r a l units o r a r e a s (very often defects) in t h e m e t a l
can be r e a c h e d b y t h e p r o b e within r e a s o n a b l e times
a n d at t e m p e r a t u r e s at w h i c h these units a r e still
stable. Second, h y d r o g e n is dissolved as a n a t o m
within interstices of t h e m e t a l lattice w i t h o u t c h a n g i n g
the m e t a l s t r u c t u r e . E v e n after t h e f o r m a t i o n of a
h y d r i d e t h e m e t a l lattice r e m a i n s a l m o s t exactly t h e
s a m e , being e x p a n d e d b y only a few percent. T h i r d , its
solubility in m a n y m e t a l s is high a n d , therefore,
defects strongly i n t e r a c t i n g with h y d r o g e n c a n be
s a t u r a t e d first. O t h e r s t r u c t u r a l entities with a lower
b i n d i n g energy c a n t h e n be studied b y a d d i n g m o r e
h y d r o g e n . T h e latter p r o p e r t y is peculiar t o h y d r o g e n ,
w h e r e a s t h e first t w o p r o p e r t i e s a r e even m o r e p r o
n o u n c e d for o t h e r light particles such as p o s i t r o n s a n d
m u o n s which a r e frequently used as p r o b e s . T h e
ability of h y d r o g e n t o p r o b e different interstices
a c c o r d i n g t o their b i n d i n g energies m a y be described
by t h e t e r m h y d r o g e n s p e c t r o m e t r y ( F e e n s t r a et al.
1988). T h e s t r o n g i n t e r a c t i o n of h y d r o g e n with d e
fects in m e t a l s , n a m e l y d i s l o c a t i o n s , g r a i n b o u n d a r i e s
a n d c r a c k s , h a s deleterious effects o n t h e m e c h a n i c a l

1. Density

of Sites

and Hydrogen

Distribution

E v e n in a perfect lattice a discrete s p e c t r u m of intersti

tial sites (i.e., t e t r a h e d r a l a n d o c t a h e d r a l sites) is
available t o b e o c c u p i e d b y h y d r o g e n . H o w e v e r , the
difference in site energy is usually very large c o m p a r e d
t o t h e t h e r m a l energy kT a n d , therefore, only o n e of
these sites is filled with h y d r o g e n a t o m s . T h i s degener
acy of site energies vanishes w h e n e v e r a local c h a n g e
of a t o m i c distances (strain) o r a c h a n g e of chemical
c o m p o s i t i o n o c c u r s . F o l l o w i n g the c o n c e p t s of statist
ical t h e r m o d y n a m i c s , a density of sites ( D O S ) func
tion c a n be i n t r o d u c e d ( K i r c h h e i m 1982) t h a t gives
the fraction of sites n(E) within a n energy interval dE
at energy E. By m e a s u r i n g t h e p r o p e r t i e s of h y d r o g e n
being dissolved in a m a t e r i a l , r e a s o n a b l y detailed
i n f o r m a t i o n o n t h e D O S c a n be o b t a i n e d w h i c h h a s t o
be t r a n s f o r m e d i n t o s t r u c t u r a l a n d / o r chemical infor
m a t i o n a b o u t the c o r r e s p o n d i n g sites. T h e c o r r e s
p o n d e n c e b e t w e e n t h e D O S for h y d r o g e n a n d special
s t r u c t u r a l o r chemical features of t h e interstices in a
m a t e r i a l is often u n a m b i g u o u s , especially if t h e D O S
c o n t a i n s p r o n o u n c e d p e a k s b e l o n g i n g t o special
g r o u p s of interstitial sites.
A s e a c h of t h e sites c a n be o c c u p i e d by only o n e
h y d r o g e n a t o m , t h e rules of F e r m i - D i r a c statistics
h a v e to be applied yielding t h e t o t a l c o n c e n t r a t i o n of
h y d r o g e n c at a given t e m p e r a t u r e T:

-r.

n(E)

dE

,1 + exp[(E -

p)/kT]

(1)

w h e r e is t h e chemical p o t e n t i a l of h y d r o g e n , also
called t h e F e r m i level of h y d r o g e n . T h u s b y m e a s u r
ing t h e chemical p o t e n t i a l of h y d r o g e n at different
h y d r o g e n c o n c e n t r a t i o n s the D O S c a n be e v a l u a t e d
from E q n . (1). O w i n g t o t h e steplike b e h a v i o r of the
F e r m i - D i r a c function (the reciprocal of t h e d e n o m i
n a t o r in E q n . (1)) h y d r o g e n a t o m s a r e usually filled in
sites below t h e F e r m i level ( < ) a n d E q n . (1) is
simplified t o

-r -

(E) dE

or

= ()

(2)

00

H o w e v e r , the a p p l i c a t i o n of E q n . (2) is subject t o

conditions on temperature, concentration and D O S ,
n(E) ( K i r c h h e i m a n d Stolz 1985). I n m o s t cases t h e
sites a r e filled a c c o r d i n g t o their energy beginning
with t h e sites of lowest energy. H o w e v e r , if there is
only a very small fraction of low-energy sites, h y d r o
gen a t o m s p o p u l a t e m o s t l y n o r m a l sites, t h u s decreas
ing t h e free energy by a n increase of configurational
187

Hydrogen

as a Metallurgical

Probe

e n t r o p y . It t h e n requires m o r e time for the h y d r o g e n

a t o m s to find the t r a p s c o m p a r e d t o their residence
time within t h e t r a p s . T h e p a r t i t i o n i n g of h y d r o g e n
a t o m s is described totally by E q n . (1) a n d the inte
g r a n d in E q n . (1) d e t e r m i n e s the o c c u p a n c y in dif
ferent energy intervals of the D O S .
D u r i n g a g r a d u a l filling of sites of different energies
o t h e r p r o p e r t i e s such as s a m p l e v o l u m e , resistivity
a n d h y d r o g e n diffusivity m a y also c h a n g e , p r o v i d i n g
useful i n f o r m a t i o n o n the n a t u r e of t h e sites.

2. Interaction

with Vacancies

and

Dislocations

Vacancies in metals interact strongly with dissolved

h y d r o g e n a t o m s m a i n l y d u e to a release of the elastic
energy t h a t builds u p d u r i n g the squeezing of the
h y d r o g e n a t o m s i n t o the interstices of the m e t a l
lattice. Theoretical calculations s h o w t h a t t h e distance
between h y d r o g e n a n d m e t a l a t o m s in n o r m a l intersti
tial sites is so small t h a t they repel each o t h e r , w h e r e a s
this distance in a v a c a n c y is large a n d leads t o a n
a t t r a c t i o n . Therefore, a positive v o l u m e c h a n g e oc
curs d u r i n g dissolution of h y d r o g e n in n o r m a l sites
a n d a negative v o l u m e c h a n g e h a s been observed for
the first 50 a t . p p m of h y d r o g e n in a m o r p h o u s P d 8 0S i 2 0
(Stolz et al. 1984). In the latter case h y d r o g e n w a s
used as a p r o b e t o detect the presence a n d n u m b e r of
vacancylike defects in a metallic glass. This w a s
especially helpful as o t h e r techniques developed for
crystalline m e t a l s c a n n o t be applied to a m o r p h o u s
metals. T h e negative v o l u m e c h a n g e w a s also f o u n d in
heavily cold-rolled crystalline p a l l a d i u m , w h e r e it is
well k n o w n t h a t vacancies a r e p r o d u c e d by disloca
tion climb.
T h e attractive i n t e r a c t i o n between dislocations a n d
h y d r o g e n is also m a i n l y d u e t o the elastic strain
a r o u n d the h y d r o g e n a t o m , because the t o t a l elastic
energy can be reduced by m o v i n g the h y d r o g e n a t o m
in a n a p p r o p r i a t e p a r t of the stress field of a disloca
tion. T h e r e is e x p e r i m e n t a l evidence t h a t the strain
field of h y d r o g e n a t o m s in m e t a l s h a s cubic s y m m e t r y
a n d , therefore, the interaction is strongest w h e n there
are tensile stresses of a n edge dislocation variety.
In a well-annealed m e t a l the density of dislocations
7
- 2
is a b o u t 1 0 c m , w h e r e the n u m b e r of sites in the
dislocation c o r e is very small a n d c o r r e s p o n d s t o
c o n c e n t r a t i o n s of a b o u t 0.01 a t . p p m . In o r d e r t o
study the i n t e r a c t i o n with h y d r o g e n , higher disloca
tion densities a r e required. In cold-rolled m e t a l s the
11
2
dislocation densities a r e as high as 1 0 M 0 c m " a n d
the c o n c e n t r a t i o n of t r a p sites p r o v i d e d by the cores is
of the o r d e r of 10 a t . p p m . Very sensitive t e c h n i q u e s ,
such as electrochemical m e t h o d s a n d the m e a s u r e
m e n t of internal friction a n d resistivity, are necessary
to detect these small a m o u n t s of t r a p p e d h y d r o g e n .
In the case of iron a n d p a l l a d i u m , site energies
1
1
of - 50 kJ m o l "
of h y d r o g e n t o - 60 k J m o l "
of
h y d r o g e n , with respect to n o r m a l sites far a w a y from

188

the dislocation, h a v e been d e t e r m i n e d for sites in the

dislocation cores.
I n c r e a s i n g the h y d r o g e n c o n c e n t r a t i o n results in a n
o c c u p a t i o n of sites below t h e glide p l a n e of edge
dislocations. T h e chemical p o t e n t i a l of h y d r o g e n t h e n
d e p e n d s linearly o n the s q u a r e r o o t of t h e h y d r o g e n
c o n c e n t r a t i o n ( K i r c h h e i m 1982) which is a direct
c o n s e q u e n c e of t h e decrease of h y d r o s t a t i c tension by
1/r, w h e r e r is t h e d i s t a n c e from t h e dislocation core.
U s i n g this, h y d r o g e n h a s been used t o p r o b e p a r t s of
the stress field a r o u n d t h e dislocations.
Sites of c o n s t a n t h y d r o s t a t i c pressure a r e o n cylin
drical loci which a r e a t t a n g e n t s t o t h e glide p l a n e .
W i t h respect t o h y d r o g e n these sites h a v e t h e s a m e
site energy a n d , u n d e r special c o n d i t i o n s (i.e., low
c o n c e n t r a t i o n s a n d / o r low t e m p e r a t u r e s ) , E q n . (2)
c a n be used instead of E q n . (1), which c o r r e s p o n d s t o
a n o c c u p a t i o n of all t h e sites within the cylinder b y
h y d r o g e n a t o m s . T h e d i a m e t e r of this cylinder c a n be
calculated from the t o t a l a m o u n t of h y d r o g e n , a n d
the site energy o n the c u r v e d cylindrical surface is
e q u a l t o t h e chemical p o t e n t i a l of h y d r o g e n (besides
a n a d d i t i o n a l c o n s t a n t t e r m ) . Therefore, a n increase
of the chemical p o t e n t i a l causes a n increase of the
d i a m e t e r of t h e cylinder. A s t h e site energies o n the
cylindrical surfaces decrease with increasing d i a m e t e r ,
a p o i n t will be r e a c h e d w h e r e p a r t i t i o n i n g between
sites in t h e cylinder a n d n o r m a l lattice sites far a w a y
from t h e dislocation occurs, t h a t is, a d d i t i o n a l h y d r o
gen a t o m s a r e used in p a r t t o increase t h e size of the
cylinders a n d in p a r t t o fill n o r m a l sites. T h i s p a r t i
t i o n i n g c a n be easily o b s e r v e d by m e a s u r i n g resis
tivity, b e c a u s e the resistivity i n c r e m e n t of h y d r o g e n
a t o m s in the cylinder is small c o m p a r e d t o a n isolated
h y d r o g e n a t o m in a n o r m a l site. T h e results of such
m e a s u r e m e n t s as well as e m f results ( K i r c h h e i m 1982)
a n d small-angle n e u t r o n scattering ( K i r c h h e i m et al.
1987) a r e in a g r e e m e n t with the c o n c e p t of s o l u t e dislocation i n t e r a c t i o n previously described. A g a i n ,
the exceptional p r o p e r t i e s of h y d r o g e n h a v e e n a b l e d
the s t u d y of this solute-defect i n t e r a c t i o n in m o r e
detail t h a n w o u l d h a v e been possible with o t h e r solute
atoms.
So far it h a s been tacitly a s s u m e d t h a t t h e n a t u r e of
the i n t e r a c t i o n energy is purely elastic. H o w e v e r , it
c a n be s h o w n ( K i r c h h e i m 1982) t h a t the negative
h y d r o g e n - h y d r o g e n i n t e r a c t i o n energy plays a n im
p o r t a n t role, because t h e elastic energy a l o n e w o u l d
n o t lead t o the observed e x t e n d e d segregation of
h y d r o g e n a t dislocations.

5. Interaction

with Internal

Interfaces

G r a i n b o u n d a r i e s in p u r e m e t a l s d o n o t i n t e r a c t very
strongly with dissolved h y d r o g e n . H o w e v e r , in t h e
presence of o t h e r segregated impurities (e.g., p h o s
p h o r u s in iron) a s t r o n g i n t e r a c t i o n will occur,
because the e m b r i t t l e m e n t effect of s o m e elements is

Hydrogen

e n h a n c e d r e m a r k a b l y in t h e presence of h y d r o g e n .
The usual procedure to measure grain b o u n d a r y
segregation b y surface analytical t e c h n i q u e s after
i n t e r g r a n u l a r fracture fails for h y d r o g e n b e c a u s e
c o m m o n t e c h n i q u e s such as A u g e r electron s p e c t r o s
c o p y , electron s p e c t r o s c o p y for chemical analysis a n d
x-ray p h o t o e l e c t r o n s p e c t r o s c o p y d o n o t detect
hydrogen or because the previous grain b o u n d a r y
coverage by h y d r o g e n will be c h a n g e d after t h e e x p o
sure of t h e b o u n d a r y t o t h e high v a c u u m d u e t o t h e
a t t a i n m e n t of a n e w e q u i l i b r i u m c o r r e s p o n d i n g t o
surface segregation.
N a n o c r y s t a l l i n e m e t a l s (i.e., polycrystalline m e t a l s
with grain d i a m e t e r s of t h e o r d e r of n a n o m e t e r s )
c o n t a i n a large fraction of g r a i n b o u n d a r i e s a n d they
are, therefore, m o s t suitable for s t u d y i n g t h e i n t e r a c
tion of h y d r o g e n w i t h g r a i n b o u n d a r i e s . It h a s b e e n
s h o w n for n a n o c r y s t a l l i n e p a l l a d i u m ( M u t s c h e l e a n d
K i r c h h e i m 1987) t h a t t h e g r a i n b o u n d a r i e s p r o v i d e a
b r o a d s p e c t r u m of segregation energies ( D O S ) a s o n e
w o u l d expect from simple g e o m e t r i c a l c o n s i d e r a t i o n s .
T h e diffusion b e h a v i o r is peculiar b e c a u s e t h e diffu
sion coefficient in g r a i n b o u n d a r i e s is l o w e r t h a n t h a t
within t h e g r a i n s d u e t o a preferred o c c u p a t i o n of
low-energy sites a t low h y d r o g e n c o n c e n t r a t i o n s . T h e
diffusivity increases as sites of higher energy h a v e t o
be occupied by increasing t h e h y d r o g e n c o n c e n t r a
tion. A l t h o u g h t h e w i d t h of t h e D O S is a b o u t t h e
s a m e as in metallic glasses (see Sect. 4), t h e a v e r a g e
activation energy, calculated as t h e difference b e t w e e n
average site a n d s a d d l e - p o i n t energies, is r a t h e r small
in n a n o c r y s t a l l i n e p a l l a d i u m w h e n c o m p a r e d w i t h
metallic glasses, i n d i c a t i n g a m o r e o p e n s t r u c t u r e of
the grain b o u n d a r i e s in n a n o c r y s t a l l i n e m a t e r i a l s .
T h e (- p h a s e t r a n s f o r m a t i o n in t h e system of
h y d r o g e n a n d n a n o c r y s t a l l i n e p a l l a d i u m differs re
m a r k a b l y from t h a t in n o r m a l polycrystalline palla
d i u m (20 grain d i a m e t e r ) a n d it c a n be used t o
d e t e r m i n e t h e a v e r a g e thickness of g r a i n b o u n d a r i e s .
In polycrystalline p a l l a d i u m t h e v o l u m e fraction of
grain b o u n d a r i e s a n d its influence o n t h e p h a s e t r a n s
f o r m a t i o n is negligible. I n n a n o c r y s t a l l i n e p a l l a d i u m
the s a m e p h a s e is f o r m e d w i t h i n t h e grains b u t m u c h
less h y d r o g e n is n e e d e d for t h e c o m p l e t i o n of t h e
phase to phase transformation because the grain
b o u n d a r i e s d o n o t p a r t i c i p a t e in t h e p h a s e f o r m a t i o n .
F r o m t h e difference b e t w e e n t h e a m o u n t of h y d r o g e n
used for t h e p h a s e f o r m a t i o n in polycrystalline a n d
n a n o c r y s t a l l i n e p a l l a d i u m t h e v o l u m e fraction of t h e
grain b o u n d a r i e s is calculated s t r a i g h t f o r w a r d l y .
T h u s a v o l u m e fraction of 0.27 in a n a n o c r y s t a l l i n e
p a l l a d i u m s a m p l e w i t h a n a v e r a g e g r a i n d i a m e t e r d of
8 n m (from t r a n s m i s s i o n electron m i c r o g r a p h s ) w a s
d e t e r m i n e d w h i c h yields a n a v e r a g e thickness of t h e
grain b o u n d a r i e s = vd/3 = 0.7 n m . T h i s r e l a t i o n s h i p
is valid for grains of spherical o r cubic s h a p e w h i c h
a p p r o x i m a t e s well t o t h e case of n a n o c r y s t a l l i n e
palladium.
F r o m the i n t e r a c t i o n of h y d r o g e n w i t h P d - A l 2 0 3

as a Metallurgical

Probe

-6.0i-

-7.0

-7.5 -

-e.ol
-4.0

I
-3.5

I
-3.0

Log

I
-2.5

I
-2.0

Figure 1
Diffusion coefficient of hydrogen in palladium with A1 20 3
precipitates D as a function of hydrogen concentration c:
saturation of irreversible traps (free oxygen bonds at the
P d - A l 2 0 3 interface) and reversible traps (strained
interstices of palladium at the interface) (O), only
reversible trapping occurs ( ) , after annealing in
aluminum vapor the oxygen bonds at the interface are
saturated with aluminum and no irreversible trapping is
observed (-I-), and after a final annealing treatment in air
the oxygen atoms saturate the free aluminum bonds at the
interfaces but still have free bonds to cause irreversible
trapping of hydrogen ( ) . After saturation of all kinds
of traps the diffusivity of hydrogen in pure palladium
(log D = 6.4) is measured

(or P d - Z n O ) interfaces i n f o r m a t i o n o n t h e p h a s e
b o u n d a r y itself c a n b e e x t r a c t e d . T h e interfaces a r e
p r e p a r e d b y i n t e r n a l o x i d a t i o n of p a l l a d i u m - a l u m i
n u m ( p a l l a d i u m - z i n c ) alloys a t 1000 C in air with
leads t o t h e f o r m a t i o n of p r i s m a t i c precipitates of
A 1 2 0 3 ( Z n O ) h a v i n g edge lengths w i t h i n t h e s u b m i c r o m e t e r r a n g e . T h e diffusion coefficients of h y d r o
gen a t 295 a r e s h o w n in F i g . 1 as a function of
h y d r o g e n c o n c e n t r a t i o n . D u r i n g t h e first r u n a larger
t r a p c o n c e n t r a t i o n is o b s e r v e d c o m p a r e d t o t h e fol
lowing r u n s . Between e a c h r u n h y d r o g e n is r e m o v e d
b y a n o d i c p o l a r i z a t i o n . T h e difference in t r a p c o n c e n
t r a t i o n s is a t t r i b u t e d t o irreversible t r a p p i n g of h y d r o
gen a t t h e p a l l a d i u m - o x i d e p h a s e b o u n d a r y , w h e r e
t h e n u m b e r of irreversible t r a p sites c o r r e s p o n d s t o a
15
-2
(about
c o v e r a g e of 1.5 1 0 h y d r o g e n a t o m s c m
o n e m o n o l a y e r ) of t h e b o u n d a r y . T h e s e h y d r o g e n
a t o m s c a n n o t b e r e m o v e d either b y a n o d i c p o l a r i z a
tion o r b y a n n e a l i n g a t 800 C in high v a c u u m . T h u s ,
d u r i n g t h e first r u n of d o p i n g t h e s a m p l e s , b o t h k i n d s
of t r a p sites a r e s a t u r a t e d while, in t h e following r u n s ,
only reversible sites a r e filled.
T h e irreversible t r a p p i n g w a s a t t r i b u t e d t o t h e
f o r m a t i o n of o x y g e n - h y d r o g e n b o n d s a t t h e palla
d i u m - o x i d e interface a s s u m i n g t h a t u n s a t u r a t e d oxy
gen a t o m s from t h e t e r m i n a t i n g layer of the oxide

189

Hydrogen

as a Metallurgical

Probe

precipitates. T h i s a s s u m p t i o n is s u p p o r t e d b y direct
o b s e r v a t i o n s in a high-resolution electron m i c r o s c o p e
(Necker a n d M a d e r 1988). By a n n e a l i n g t r e a t m e n t s in
zinc o r a l u m i n u m v a p o r these oxygen a t o m s a r e
s a t u r a t e d with t h e c o r r e s p o n d i n g m e t a l a t o m s . T h e s e
form t h e t e r m i n a t i n g layer of t h e oxide a n d h a v e a
lower affinity t o h y d r o g e n ; therefore, t h e irreversible
t r a p p i n g of h y d r o g e n vanishes (see F i g . 1). T h e irre
versible t r a p s recover if t h e samples a r e r e a n n e a l e d in
air. T h e reversible t r a p p i n g of t h e h y d r o g e n c a n b e
described q u a n t i t a t i v e l y b y a two-level t r a p p i n g
m o d e l ( K i r c h h e i m 1982) with a free energy of t r a p
1
of h y d r o g e n .
p i n g AG = - 44 000 + 50rkJ m o l "
This t r a p p i n g m a y b e d u e t o t h e strain field a r o u n d
the precipitates because of misfit dislocations a n d / o r
the different t h e r m a l e x p a n s i o n coefficients of t h e
p a l l a d i u m a n d t h e oxides.
D u r i n g t h e internal o x i d a t i o n of P d - 3 a t . % A l
alloys a t 700 C in air, n o precipitates were detected
by c o n v e n t i o n a l t r a n s m i s s i o n electron m i c r o s c o p y
a n d only streaks were observed in t h e diffraction
p a t t e r n . A c c o r d i n g t o chemical analysis t h e s a m p l e
contained
3.0 0.05 a t . %
of
aluminum
and
4.9 0 . 1 5 at. % of oxygen, which c o r r e s p o n d s t o a n
excess of 0.4 0 . 2 a t . % of oxygen. T h i s value is in
g o o d a g r e e m e n t with t h e 0.5 a t . % of irreversible t r a p s
t h a t w a s d e t e r m i n e d for h y d r o g e n in this alloy. T h e
c o n c e n t r a t i o n of irreversible t r a p s is larger w h e n
c o m p a r e d with t h e samples oxidized a t 1000 C
because t h e interfacial a r e a is larger for t h e small
precipitates formed a t 700 C. T h u s , h y d r o g e n p r o
vides i n f o r m a t i o n o n t h e interfacial a r e a o r t h e
n u m b e r of u n s a t u r a t e d oxygen b o n d s . T h e interfacial
area c a n b e calculated, a s s u m i n g t h e s a m e coverage
15
as for irreversible t r a p p i n g of 1.5 10 h y d r o g e n
2
atoms c m " .

4. Behavior

in Crystalline

and Amorphous

Alloys

F o r a n alloy , _ , which is either a m o r p h o u s o r

crystalline a n d w h e r e h y d r o g e n occupies t e t r a h e d r a l
sites, a n a p p r o p r i a t e D O S function is
()=/

(^--^-,)

(3)

where the f a c t o r / i s theoretically e q u a l t o t h e n u m b e r

of t e t r a h e d r a l sites p e r m e t a l a t o m which c a n b e
occupied by h y d r o g e n . H o w e v e r , d u e t o t h e repulsive
interaction between h y d r o g e n a t o m s s o m e of t h e sites
remain e m p t y a n d , therefore, a c t u a l values of / a r e
less t h a n t h e total n u m b e r of t e t r a h e d r a l sites p e r
metal a t o m . T h e five different types of t e t r a h e d r a l
sites ( A 4 , A 3 B , A 2 B 2 , A B 3 a n d B 4) a r e p r e s e n t in
l
c o n c e n t r a t i o n s o f / ( - ) x ' ( l - xf~ a n d their site energies
for h y d r o g e n m a y b e distributed a r o u n d a n average
energy Et a c c o r d i n g t o t h e functions , ( - Et), which
m a y be D i r a c delta functions in t h e case of d i s o r d e r e d

190

crystalline alloys o r G a u s s i a n functions in t h e case of

a m o r p h o u s alloys. T h e e x p e r i m e n t a l d e t e r m i n a t i o n of
n(E) (e.g., b y m e a s u r e m e n t s of t h e chemical p o t e n t i a l
p(c)) a n d a c o m p a r i s o n with E q n . (3) allows t h e
assessment of w h e t h e r A a n d a t o m s a r e r a n d o m l y
distributed o r w h e t h e r a chemical s h o r t - r a n g e o r d e r
causes deviations from t h e b i n o m i a l d i s t r i b u t i o n . T h e
d i s t r i b u t i o n functions n^E-E^
a n d / o r t h e average
energies E{ c a n p r o v i d e i n f o r m a t i o n o n t h e s t r u c t u r a l
s h o r t - r a n g e o r d e r ( K i r c h h e i m 1982, R i c h a r d s 1983,
F e e n s t r a et al. 1988).
T h e c o n c e p t of e v a l u a t i n g t h e D O S from m e a s u r e
m e n t s of h y d r o g e n solubility a n d d r a w i n g conclusions
o n t h e p r o p e r t i e s of t h e alloy itself h a s been suc
cessfully applied t o d i s o r d e r e d , crystalline n i o b i u m v a n a d i u m alloys ( F e e n s t r a et al. 1988) a n d v a r i o u s
a m o r p h o u s alloys c o n t a i n i n g a n early a n d a late
transition m e t a l ( H a r r i s et al. 1987). F o r t h e crystal
line N b j _ x V x alloys t h e results were analyzed (Feen
stra et al. 1988) with respect t o t h e site energies
of
the different t e t r a h e d r a as a function of t h e alloy
c o m p o s i t i o n . Ei c h a n g e s with because t h e enthalpies
of h y d r o g e n dissolution d e p e n d o n t h e a t o m i c v o l u m e
of t h e alloy, which also c h a n g e s as a function of in
the case of n i o b i u m - v a n a d i u m alloys. Different from
a n ideal lattice of a p u r e m e t a l , t h e a t o m i c distances in
a n A - B alloy a r e d i s t r i b u t e d a r o u n d a n average value,
t h a t is, for t h o s e cases w h e r e A a n d h a v e different
a t o m i c radii. T h u s a n N b 4 t e t r a h e d r o n in t h e alloy h a s
a smaller v o l u m e t h a n p u r e n i o b i u m w h e r e a s a V 4
t e t r a h e d r o n in t h e n i o b i u m - v a n a d i u m alloy h a s a
larger v o l u m e t h a n p u r e v a n a d i u m . Therefore, V 4
sites in t h e alloy a r e m o r e favorable for h y d r o g e n t h a n
t h e c o r r e s p o n d i n g sites in p u r e v a n a d i u m . F r o m
analysis of t h e site energies t h e a v e r a g e a t o m i c dis
tances of A - A , A - B a n d B - B p a i r s c a n be calculated.
M e a s u r e m e n t s of t h e chemical p o t e n t i a l of h y d r o
gen in a m o r p h o u s n i c k e l - z i r c o n i u m alloys h a v e
s h o w n ( H a r r i s et al. 1987) t h a t t h e d i s t r i b u t i o n of
nickel a n d z i r c o n i u m a t o m s over t h e c o r n e r s of t h e
t e t r a h e d r a l sites follows t h e b i n o m i a l d i s t r i b u t i o n as
given b y E q n . (3) w i t h / d e t e r m i n e d as h a v i n g a value
of 1.9. T h i s is in a g r e e m e n t with theoretical c o n s i d e r a
tions a s s u m i n g a n infinitely s t r o n g repulsion for
h y d r o g e n - h y d r o g e n distances less t h a n 0.21 n m a n d a
r e a s o n a b l e s t r u c t u r e for t h e a m o r p h o u s alloy.
By replacing t h e n a t u r a l oxide films o n a n a m o r
p h o u s s a m p l e e m f m e a s u r e m e n t s a r e possible a t low
c o n c e n t r a t i o n s a n d using E q n . (2) this yields t h e
d i s t r i b u t i o n of site energies D O S ( K i m a n d Stevenson
1988) a s s h o w n for a m o r p h o u s n i c k e l - t i t a n i u m a n d
n i c k e l - z i r c o n i u m alloys in F i g . 2. T h e m e a s u r e d D O S
shows two separated peaks caused by the "chemical
d i s o r d e r " w h i c h gives rise t o t h e a p p e a r a n c e of inter
stices with a variety of different chemical e n v i r o n
m e n t s . C o n t r a r y t o t h e crystalline m e t a l s , t h e energies
for each t y p e of t e t r a h e d r o n a r e d i s t r i b u t e d d u e t o t h e
s t r u c t u r a l d i s o r d e r in a m o r p h o u s m e t a l s . U s i n g G a u s
a n d / = 1.3 in E q n . (3)
sian d i s t r i b u t i o n s for nt(E-,)

I.Op

()
T i 3 Ni tetrahedra
I

T i 2 N i 2tetrahedra

Log

Figure 3
Diffusion coefficient of hydrogen in amorphous Pd^S^
prepared by melt spinning ( ) , sputtering ( ) and the
double piston technique (O). The lines were calculated
from the DOS
-50

-40

-30

-20

-10

Site energy (kJ mol Of hydrogen)

Figure 2
Measured density of sites dc/ for (a) amorphous Ni 3 5Ti 65
and (b) ^^, revealing the concentration and binding
energies of different tetrahedral sites

yields t h e solid line s h o w n in F i g . 2. T h e w i d t h of t h e

-1
s e p a r a t e G a u s s i a n f u n c t i o n s is a b o u t l O k J m o l
of
hydrogen.
T h e w i d t h of t h e e n e r g y d i s t r i b u t i o n for a special
interstice c o n t a i n s i n f o r m a t i o n o n t h e s t r u c t u r a l d i s
o r d e r . N e g l e c t i n g t o p o l o g i c a l s h o r t - r a n g e o r d e r leads
t o a simple r e l a t i o n s h i p b e t w e e n t h e site e n e r g y distri
b u t i o n for h y d r o g e n a n d t h e d i s t r i b u t i o n of a t o m i c
distances for t h e m a t r i x a t o m s ( K i r c h h e i m 1982,
R i c h a r d s 1983). T h e m e a s u r e d w i d t h s of t h e D O S for
h y d r o g e n a r e usually smaller w h i c h m a y b e d u e t o
topological short-range order.
A m o n g t h e a m o r p h o u s alloys t h e p a l l a d i u m silicon alloys a r e m o s t l y used t o m e a s u r e h y d r o g e n
solubility a n d diffusivity. T h e n o n m e t a l seems n o t t o
p l a y a n i m p o r t a n t role a n d t h e D O S for h y d r o g e n c a n
be described b y a single G a u s s i a n d i s t r i b u t i o n , w h i c h
c a n explain t h e c o n c e n t r a t i o n d e p e n d e n c e of t h e
chemical p o t e n t i a l a n d of t h e diffusion coefficient
( K i r c h h e i m a n d Stolz 1985). I n m o d e l l i n g t h e l o n g r a n g e diffusion b e h a v i o r t h e a s s u m p t i o n is m a d e t h a t
t h e s a d d l e - p o i n t energies a r e c o n s t a n t w h i c h is suffi
cient t o give t h e c o r r e c t d e p e n d e n c e of t h e diffusion

coefficient o n c o n c e n t r a t i o n (see F i g . 3). H o w e v e r , t h e

m a g n i t u d e s of t h e l o n g - r a n g e diffusion a n d especially
t h e s h o r t - r a n g e diffusion of h y d r o g e n a r e s t r o n g l y
d e t e r m i n e d b y t h e d i s t r i b u t i o n of s a d d l e - p o i n t ener
gies a s c a n b e s h o w n b y M o n t e C a r l o s i m u l a t i o n s
( K i r c h h e i m a n d Stolz 1987). H o w e v e r , t h e t h e o r y o n
diffusion in d i s o r d e r e d m e d i a h a s t o b e i m p r o v e d
c o n s i d e r a b l y in o r d e r t o use d a t a o n t h e s h o r t - a n d
l o n g - r a n g e diffusion of h y d r o g e n for p r o b i n g s a d d l e p o i n t c o n f i g u r a t i o n s . A n e x a m p l e of t h e sensitivity of
this diffusivity o n s t r u c t u r a l differences is p r e s e n t e d in
Fig. 3, w h e r e t h e diffusion coefficient of h y d r o g e n in
a m o r p h o u s P d 8 0S i 2 0 is s h o w n as a function of h y d r o
gen c o n c e n t r a t i o n (Stolz et al. 1984). T h e values differ
b y u p t o t w o o r d e r s of m a g n i t u d e for s a m p l e s p r e
p a r e d b y different t e c h n i q u e s , a l t h o u g h t h e r a d i a l
d i s t r i b u t i o n function as m e a s u r e d w i t h r a y s reveals
n o differences. T h e results of F i g . 3 c a n b e e x p l a i n e d
p a r t l y b y different D O S b u t they a r e also affected b y
t h e d i s t r i b u t i o n of s a d d l e - p o i n t energies ( K i r c h h e i m
a n d Stolz 1987).
T h e p r o p e r t i e s of h y d r o g e n (chemical p o t e n t i a l ,
diffusivity, resistivity i n c r e m e n t ) were also d e t e r m i n e d
in c o l d - r o l l e d a m o r p h o u s P d 8 0S i 2 0 ( 5 0 % r e d u c t i o n of
cross section). N o c h a n g e s h a v e b e e n o b s e r v e d c o m
p a r e d t o t h e a s - q u e n c h e d s a m p l e s ( K i r c h h e i m et al.
1985), a l t h o u g h all q u a n t i t i e s a r e c h a n g e d r e m a r k a b l y
in t h e p r e s e n c e of e d g e d i s l o c a t i o n s . T h u s h y d r o g e n is
n o t a b l e t o detect e d g e t y p e d i s l o c a t i o n s in plastically
d e f o r m e d , a m o r p h o u s p a l l a d i u m - s i l i c o n alloys.
See also: Diffusion: Novel Measurement Methods

191

Hydrogen

as a Metallurgical

Probe

Bibliography
Alefeld G, Volkl J 1980 Hydrogen in Metals, Topics in
Applied Physics, Vol. 29. Springer, Berlin, pp. 20142
Bernstein I M, Thomson A W (eds.) 1981 Proc. 3rd Int.
Conf. Effects of Hydrogen on Behavior of Materials.
Metallurgical Society of AIME, New York
Feenstra R, Brower R, Griessen R 1988 Hydrogen as a local
probe of alloys: Nb^V,. Europhys. Lett. 7(5): 425-30
Harris J H, Curtin W A, Tenhover A 1987 Universal
features of hydrogen absorption in amorphous transition
metal alloys. Phys. Rev. 36: 5784^97
Kim J J, Stevenson D A 1988 Hydrogen permeation studies
of amorphous and crystallized Ni-Ti alloys. J. Non-Cryst.
Solids 101: 187-97
Kirchheim R 1982 Solubility, diffusivity and trapping of
hydrogen in dilute alloys, deformed and amorphous
metals. Acta Metall. 30: 1069
Kirchheim R, Huang X Y, Carstanjen H - D , Rush J J 1987
Inelastic neutron scattering and resistivity of hydrogen in
cold-worked palladium. In: Latanison R M, Jones R
(eds.) 1987 Chemistry and Physics of Fracture, NATO
ASI series. NATO, Brussels, p. 580
Kirchheim R, Stolz U 1985 Modelling tracer diffusion and
mobility of interstitials in disordered materials. J. NonCryst. Solids 70: 323

192

Kirchheim R, Stolz U 1987 Monte-Carlo simulations of

interstitial diffusion and trapping II. Amorphous metals.
Acta Metall. 35: 281
Kirchheim R, Szokefalvi-Nagy A, Stolz U, Speitling A 1985
Hydrogen in deformed and amorphous Pd 8 0Si 20 compared
to hydrogen in deformed and crystalline palladium.
Scripta Metall. 19: 843
Mutschele T, Kirchheim R 1987 Hydrogen as a probe for
the average thickness of a grain boundary. Scripta Metall.
21: 1101
Necker G, Mader W 1988 Characterization of Ag/CdO
interfaces. Philos. Mag. Lett. 58(4): 205-12
Richards 1983 Distribution of activation energies for
impurity hopping in amorphous metals. Phys. Rev. 27:
2059
Stolz U, Kirchheim R, Wildermuth A 1984 Hydrogen as a
probe in amorphous metals. Proc. 5th Int. Conf. Rapidly
Quenched Metals, Wurzburg, p. 1537
Stolz U, Nagorny U, Kirchheim R 1984 Volume changes
during dissolution of hydrogen in metallic glasses. Scripta
Metall. 18: 347
R. K i r c h h e i m
[ M a x - P l a n c k - I n s t i t u t fur M e t a l l f o r s c h u n g ,
Stuttgart, Germany]


Infrared Spectroscopy

$avdv

T h e principal uses of infrared (ir) s p e c t r o s c o p y in

m a t e r i a l s science a r e for identification of u n k n o w n
s u b s t a n c e s o r their c h a r a c t e r i z a t i o n as t o chemical
s t r u c t u r e ; identification a n d quantification of consti
t u e n t s in m i x t u r e s ; a n d following chemical r e a c t i o n s
either in t h e b u l k o r o n t h e surface of m a t e r i a l s . It is
often used in p r o b l e m solving, frequently in c o m
b i n a t i o n with o t h e r analytical t e c h n i q u e s .
M o s t liquids a n d gases a n d m a n y solids a r e a m e n
able t o ir analysis. T h e e x c e p t i o n s a r e m o n a t o m i c a n d
h o m o n u c l e a r gases (e.g., H e , H 2 , N 2 a n d 0 2 ) , m e t a l s
a n d dilute a q u e o u s s o l u t i o n s . T h e ir s p e c t r u m of a
m a t e r i a l is its " f i n g e r p r i n t , " a n d a n u n k n o w n m a t e r i a l
m a y be positively identified b y m a t c h i n g its s p e c t r u m
t o t h a t of a n a u t h e n t i c s t a n d a r d . E v e n lacking s t a n
d a r d s , h o w e v e r , t h e presence o r a b s e n c e of c e r t a i n
g r o u p s c a n be c o r r e l a t e d with t h e presence o r a b s e n c e
of a b s o r p t i o n s a t specific w a v e l e n g t h s .

1. Basic

Principles

Infrared s p e c t r a a r e usually p r e s e n t e d as a p l o t of
a b s o r p t i o n (in p e r c e n t t r a n s m i s s i o n ) as a function of
1
w a v e l e n g t h (in ) o r w a v e n u m b e r (in c m " ) . T h e
units a r e related as follows:
4

1 0 M v ac = v/n

(1)

w h e r e is the w a v e l e n g t h , is t h e w a v e n u m b e r a n d
is t h e refractive index of air.
Molecules in a n y s t a t e of m a t t e r c a n b e viewed
from a m e c h a n i c a l perspective as consisting of m a s s e s
( a t o m s ) c o n n e c t e d by springs (chemical b o n d s ) . A s in
a n y m e c h a n i c a l system, energy c a n be a b s o r b e d with
the result t h a t certain frequencies a r e excited. T h e
exact frequencies d e p e n d o n t h e m a s s e s of t h e a t o m s ,
the force c o n s t a n t s of t h e chemical b o n d s c o n n e c t i n g
t h e m a n d t o a lesser extent o n i n t e r a c t i o n s b e t w e e n
n o n b o n d e d atoms. In the simple-harmonic-oscillator
a p p r o x i m a t i o n , t h e frequency of v i b r a t i o n / of a
d i a t o m i c molecule with a t o m s of m a s s e s m a n d is
f=(2ny\k/Myi

(2)

w h e r e k is t h e force c o n s t a n t a n d is t h e r e d u c e d m a s s
(i.e., = mM/(m + M ) ) .
T h e v i b r a t i o n a l frequencies of a t o m s in molecules
c o r r e s p o n d t o t h e frequencies f o u n d in t h e ir region of
the e l e c t r o m a g n e t i c s p e c t r u m . In o r d e r for i n t e r a c t i o n
to occur, h o w e v e r , t h e v i b r a t i o n m u s t involve a n
oscillation in electric dipole m o m e n t . O n l y u n d e r
these c i r c u m s t a n c e s is ir r a d i a t i o n of t h e s a m e fre
q u e n c y a b s o r b e d a n d t h e v i b r a t i o n excited. T h e
a b s o r p t i o n intensity is

= (Nn/3c )(d7t/dQ)

(3)

w h e r e av is t h e a b s o r p t i o n coefficient a t frequency v, TV
3
is t h e n u m b e r of molecules p e r c m , Jt is the b o n d
m o m e n t a n d Q is the n o r m a l c o o r d i n a t e for the
vibration.
T h u s , m e t a l s a n d h o m o n u c l e a r gases d o n o t s h o w ir
a b s o r p t i o n p a t t e r n s because the v i b r a t i n g a t o m s d o
n o t give rise t o dipole oscillations. Strongly p o l a r
s u b s t a n c e s , such as w a t e r , a r e very s t r o n g a b s o r b e r s
of ir r a d i a t i o n w h e r e a s n o n p o l a r molecules, such as
h y d r o c a r b o n s , s h o w r a t h e r w e a k a b s o r p t i o n for m a n y
of their skeletal v i b r a t i o n s .
A n y defined a g g r e g a t i o n of a t o m s (i.e., a molecule)
h a s a finite n u m b e r of f u n d a m e n t a l v i b r a t i o n a l
a b s o r p t i o n s , e q u a l t o 37V 6 w h e r e is the n u m b e r
of a t o m s in t h e molecule (3 - 5 for linear m o l
ecules). O v e r t o n e a n d c o m b i n a t i o n b a n d s c a n also
a p p e a r , a n d the ir a b s o r p t i o n p a t t e r n for each m o l
ecular species is u n i q u e . A s m i g h t be expected, h o w
ever, structurally identical g r o u p s h a v e the s a m e o r
similar frequencies in different molecules. T h u s , the
1
a l i p h a t i c C H g r o u p always a b s o r b s n e a r 2960 c m " .
1
T h e c a r b o n y l ( C = 0 ) g r o u p a b s o r b s n e a r 1710 c m "
1
in o r g a n i c acids; n e a r 1720 c m " in k e t o n e s ; a n d
1
n e a r 1740 c m " in esters. ( E x a m p l e s of o t h e r " g r o u p
f r e q u e n c i e s " a r e given in T a b l e 1.) D e v i a t i o n s of
t h e a b s o r p t i o n s from their " n o r m a l " positions
c a n be utilized t o gain m o r e sophisticated s t r u c t u r a l
information.

2. The IR

Spectrometer

S p e c t r o s c o p y in t h e ir region p r e s e n t s several u n i q u e
difficulties. T h e region is intrinsically of low energy,
a n d t h u s the energy t r a n s m i s s i o n of the s p e c t r o m e t e r
must be maximized. M a n y materials that are trans
p a r e n t t o visible r a d i a t i o n d o n o t t r a n s m i t ir; optical
glass, for e x a m p l e , is i r - o p a q u e a n d so special m a t e r
ials such as single crystals of N a C l , K B r o r A g C l m u s t
be used for w i n d o w m a t e r i a l s . P r o p e r t i e s of s o m e
c o m m o n i r - t r a n s m i t t i n g m a t e r i a l s a r e given in T a b l e
2. W a t e r is strongly a b s o r b i n g a n d t h u s u n s u i t a b l e as
a solvent. Finally, b l a c k b o d y r a d i a t i o n originating
from the s p e c t r o m e t e r c o m p o n e n t s is a t its p e a k in the
m o s t c o m m o n l y used region a n d is responsible for a
high b a c k g r o u n d of stray r a d i a t i o n .
Dispersive
spectrometers
are the most c o m m o n
type. A typical optical system is s h o w n in Fig. 1.
Infrared r a d i a t i o n from t h e s o u r c e (a h o t ceramic r o d
o r N i c h r o m e coil) is directed by front-surface optics
t h r o u g h t h e s a m p l e c o m p a r t m e n t . A r o t a t i n g sector
m i r r o r alternately allows the s a m p l e a n d reference
b e a m s t o p a s s t h r o u g h t h e e n t r a n c e slit i n t o the

193

Infrared

Spectroscopy

Table 1
1
8
Some typical group frequencies (cm' ) in the infrared region
The N H - O H region
3460-3620 alcohol (solution)
3620-3590 phenol (solution)
3550-3330 primary amine (solution)
3450-3250 primary amine (solution)

3500-3300 secondary amine

3520-3200 alcohol (H-bonded)
3350-3330 primary amide

3200-3180 primary amide

3460-3490 C = 0 overtone
3100-2500 carboxylic acid

2900-2800 aldehyde
2900-2865 - O C H ,

2805-2780 - N C H 3

2260-2100 acetylenes
2175-2160 thiocyanates

2150-2050 isothiocyanates
2150-2110 isonitriles

The double-bond region

1870-1845 cyclic anhydride
1825-1780 aliphatic anhydride
1755-1745 aliphatic anhydride
1810-1760 acid halide

1750-1735
1740-1715
1740-1720
1735-1690

aliphatic ester
aromatic ester
aldehyde
carbamates

1725-1705
1690-1630
1680-1630
1660-1620

The fingerprint region

1650-1590 primary amines
1600-1450 aromatic ring
1550-1510 secondary amide
1556-1545 nitro
1390-1368 nitro

1415-1390
1200-1187
1210-1100
1150-1075
1075-1000

sulfate
sulfate
tertiary alcohol
secondary alcohol
primary alcohol

The CH stretching region

3100-3010 aromatic CH
2970-2910 aliphatic CH
The "window" region
2275-2263 isocyanates
2260-2220 nitriles
2260-2090 SiH

995-985
910-905
765-735
710-685

ketone
alkenes
secondary amide
primary amide (2 bands)
vinyl
vinyl
monosubstituted aromatic
monosubstituted aromatic

a For a more complete listing and discussion, see Colthup et al. (1975)

m o n o c h r o m a t o r , w h e r e t h e r a d i a t i o n is dispersed b y a
grating. (Older s p e c t r o m e t e r s m a y use a rock-salt
p r i s m instead of a grating.) T h e s p e c t r u m is s c a n n e d
by r o t a t i n g the g r a t i n g . T h e dispersed r a d i a t i o n scans
across a n exit slit, t h r o u g h a b a n d p a s s filter (to
eliminate o v e r l a p p i n g o r d e r s a n d stray light), a n d is
focused o n a detector, usually a tiny t h e r m o c o u p l e
Table 2
Properties of some ir-transmitting materials
Window
material

Transmission Refractive Reflection

b
range* ()
index
loss (%)

Quartz (Si0 2)
LiF
Sapphire (A1 20 3)
Fluorite (CaF 2)
Irtran I (MgF 2)
Servofrax (As 2S 3)
BaF 2
Rock salt (NaCl)
Irtran II (Zn2S)
Sylvite (KC1)
Irtran III (CaF 2)
Irtran IV (Zn2Se)
KBr
AgCl
Ge
Si
KRS-5 (Tl2BrI)
CsBr
Csl

0.2-3.6 (10)
0.2-6.2 (12)
0.2-5 (8)
0.2-7.8 (10)
2-6.4 (12)
1-11.1 (5)
0.2-11.5(9)
0.2-17(10)
1-10.7 (12)
0.3-2.1 (10)
0.2-8.7 (12)
1-15.2(12)
0.2-32 (4)
0.6-24 (5)
2-20
1.5-150
0.7-38 (5)
0.3^*0 (10)
0.3-55 (5)

a Thickness in mm in parenthesis

194

1.43
1.37
1.70
1.41
1.35
2.59
1.45
1.52
2.24
1.49
1.40
2.4
1.53
2.0
4.0
3.4
2.4
1.66
1.74

6
5
13
6
4
35
7
8
27
8
5
31
9
21
59
51
31
12
14

b Two surfaces

with a b l a c k e n e d t a r g e t a r e a . T h e t h e r m o c o u p l e is
e v a c u a t e d for g r e a t e r sensitivity.
T h e s a m p l e a n d reference b e a m s fall alternately o n
t h e d e t e c t o r (the r o t a t i o n a l frequency of t h e sector
m i r r o r is usually 10-15 H z ) a n d a n y difference in the
intensities of t h e t w o b e a m s (caused, for e x a m p l e , by
s a m p l e a b s o r p t i o n a t t h a t w a v e l e n g t h ) results in a n
a l t e r n a t i n g signal a t t h e d e t e c t o r . I n t h e c o m m o n
optical-null s p e c t r o m e t e r , this a l t e r n a t i n g signal a c
tivates a servosystem t h a t m o v e s a c o m b - s h a p e d

Remarks

brittle
hygroscopic
reacts with metal
brittle
brittle
toxic
soft
soft

Figure 1
Optical system of an optical-null grating spectrometer
(courtesy of Perkin-Elmer Corporation)

Infrared
optical w e d g e in o r o u t of t h e reference b e a m in such a
w a y as t o cancel t h e difference in t h e b e a m s . T h e
m o t i o n of t h e c o m b is r e c o r d e d as a function of
wavelength o r w a v e n u m b e r t o p r o d u c e t h e ir spec
t r u m of t h e s a m p l e .
T h e o p e r a t i n g p a r a m e t e r s m a y b e varied t o suit t h e
p u r p o s e of the s p e c t r u m d e t e r m i n a t i o n . T h e o p e r a t o r
can vary the slit w i d t h ; t h e s c a n n i n g speed of t h e
s p e c t r o m e t e r , w h i c h m u s t be c o m p a t i b l e with t h e
response speed of t h e p e n (the electrical signal is
filtered t o r e d u c e t h e noise o r r a n d o m p e n fluctua
tions); a n d t h e gain of t h e s e r v o l o o p driving the p e n .
T h u s , the three basic variables a r e r e s o l u t i o n (slit
width), scan speed (response time) a n d noise level
(gain). A n y t w o of these p a r a m e t e r s m a y be a r b i
trarily chosen; t h e t h i r d is t h e n fixed by t h a t choice.
T h e r e l a t i o n s h i p between these variables is:
1

r e s o l u t i o n = ct '\S/N)

11 2

= 1/w

(4)

w h e r e / is t h e r e s p o n s e time of t h e p e n , S/N is the

signal-to-noise r a t i o , w is t h e slit w i d t h a n d c is a
c o n s t a n t . This e q u a t i o n is t h e basis of " t r a d i n g r u l e s "
which a r e useful in setting t h e s p e c t r o m e t e r c o n t r o l s
for special-purpose spectra. N o t e , for e x a m p l e , t h a t
the signal-to-noise r a t i o i m p r o v e s as the s q u a r e of t h e
slit width; for q u a n t i t a t i v e analysis, the noise c a n be
reduced by a factor of four ( a n d precision t h u s
i m p r o v e d ) by d o u b l i n g t h e slit. T o d o u b l e t h e resolu
tion b y halving t h e slit, h o w e v e r , t h e scan time m u s t
be increased b y a factor of sixteen. It is i m p o r t a n t t h a t
the gain be p r o p e r l y set t o give a " l i v e " p e n t h a t s h o w s
a small a m o u n t of noise ( 0 . 2 % ) in t h e spectral
record. S p e c t r o m e t e r r e s p o n s e s h o u l d be tested b y
s c a n n i n g a m a t e r i a l h a v i n g a variety of s h a r p a n d
b r o a d b a n d s (such as indene) a t n o r m a l a n d t h e n a t
q u a r t e r - n o r m a l scan s p e e d t h e t w o r e c o r d i n g s
s h o u l d be identical. W a v e l e n g t h a c c u r a c y s h o u l d be
periodically c h e c k e d by s c a n n i n g a s t a n d a r d m a t e r i a l
such as i n d e n e o r p o l y s t y r e n e (see T a b l e 3 a n d Fig. 2).
Ratio-recording
ir spectrometers
are m o r e complex
electronically b u t h a v e s o m e distinct a d v a n t a g e s over
opitical-null s p e c t r o m e t e r s . I n s t e a d of utilizing a n
optical
attenuator,
the
instrument
accurately
m e a s u r e s the intensities of t h e s a m p l e a n d reference
b e a m s . T h e r a t i o of t h e t w o b e a m s is c o m p a r e d
electronically a n d r e c o r d e d t o give t h e s p e c t r u m .
Fourier-transform
(FT)
ir spectrometers
utilize
a different optical principle from dispersive spec
t r o m e t e r s . S o u r c e r a d i a t i o n is directed t h r o u g h a n
interferometer as s h o w n in Fig. 3, in w h i c h t h e
position of the m o v i n g m i r r o r is c o d e d by m e a n s of a
laser a n d a white-light reference. In effect, all frequen
cies a r e m e a s u r e d s i m u l t a n e o u s l y d u r i n g t h e scan time
of t h e m o v i n g m i r r o r . T h e resulting i n t e r f e r o g r a m is
t r a n s f o r m e d t o t h e frequency d o m a i n by t h e F o u r i e r
m e t h o d , using a c o m p u t e r . T h e resulting ir s p e c t r u m
is, in principle, identical t o t h a t o b t a i n e d from a
dispersive s p e c t r o m e t e r . F o u r i e r - t r a n s f o r m ir spec
t r o s c o p y h a s significant energy a d v a n t a g e s ; since all

Spectroscopy

Table 3
1
Absorption maxima (cm" ) for spectrometer calibration
Indene (undiluted)
(0.2 mm cell)
(1) 3927.2 0.5
(2) 3139.5 0 . 4
(3) 2770.9 0.4
(4) 1915.3 0.3
(5) 1553.2 0.2
Polystyrene (solid film)
(1) 3027.1 0.3
(2) 2850.7 0.3
(3) 1944.0 1
(4) 1801.6 0.3
(5) 1601.4 0.3

(0.025 mm cell)
(6) 1361.1 0.2
(7) 1205.1 0.2
(8) 1018.5 0.3
(9) 830.5 0.3
(10) 590.8
(11) 381.4
(6)
(7)
(8)
(9)

1583.1
1154.3
1028.0
906.7

0.3
0.3
0.3
0.3

frequencies a r e o b s e r v e d c o n t i n u o u s l y d u r i n g the scan

instead of as a small b u n d l e of adjacent frequencies as
in dispersive s p e c t r o m e t e r s , m u c h m o r e energy per
u n i t time is available (Felgett's a d v a n t a g e ) . A n o t h e r
energy gain results from t h e use of a circular e n t r a n c e
a p e r t u r e r a t h e r t h a n a n e n t r a n c e slit ( J a c q u i n o t ' s
a d v a n t a g e ) . T h i s energy a d v a n t a g e enables reduced
scan time o r increased resolution.
Because of their need for fast r e s p o n s e a n d wide
d y n a m i c r a n g e , F o u r i e r - t r a n s f o r m ir s p e c t r o m e t e r s
d o n o t use t h e r m o c o u p l e d e t e c t o r s , b u t instead use
pyroelectric (e.g., triglycine sulfate) o r cooled semi
conductor ( H g - C d - T e ) detectors. Other important
d e t e c t o r p a r a m e t e r s a r e sensitivity a n d wavelength
r a n g e . A wide choice of d e t e c t o r s is available, b u t all
h a v e limitations, a n d s o m e c o m p r o m i s e s a r e neces
sary in o r d e r t o best m a t c h the r e q u i r e m e n t s of the
s p e c t r o m e t e r a n d t h e user.
S p e c i a l - p u r p o s e s p e c t r o m e t e r s t h a t utilize t u n a b l e laser r a d i a t i o n a r e also available. T h e y offer m u c h
6
1
higher r e s o l u t i o n ( 1 - 1 0 " c m "
bandwidth) and
g r e a t e r intensity. A l t h o u g h they d o n o t h a v e the
capability for c o n t i n u o u s s c a n n i n g over a b r o a d
w a v e l e n g t h r a n g e , they a r e useful for special p r o b
lems, such as q u a n t i t a t i v e m e a s u r e m e n t s a t very high
a b s o r b a n c e s , a n d h i g h - r e s o l u t i o n s c a n n i n g of limited
spectral r a n g e s , as for gas analysis.
T h e m o s t c o m m o n type of t u n a b l e ir lasers are
s e m i c o n d u c t o r d i o d e lasers, p r e p a r e d from alloy
crystals of P b - S n - T e , P b - S - S e a n d P b - C d - S . T h e
frequency a t w h i c h they emit r a d i a t i o n d e p e n d s
o n chemical c o m p o s i t i o n a n d t e m p e r a t u r e . T h e y a r e
used a t cryogenic t e m p e r a t u r e s a n d m a y be t u n e d
1
over a r a n g e of a b o u t 1 c m " b y varying the d i o d e
current.
3.

Sampling

Rather
thin
layers
of
sampleapproximately
0.01 m m for liquids a n d s o l i d s a r e o p t i m u m for
g o o d q u a l i t y ir spectra. O p t i m u m s a m p l e thickness is

195

Infrared

Spectroscopy

lOOh-

40

,000

3500

3000

2500

2000

1800

1600

1400

1200

1000

400

800

200

Wovenumber (cm" )

4000

3500

3000

2000

1800

1600

Wovenumber

1400

1200 1000

800

600

400

(cm" )

Figure 2
Spectra showing calibration bands for infrared spectrometers: top, indene; bottom, polystyrene film. Numbered
absorption maxima correspond to those given in Table 3 (courtesy of Perkin-Elmer Corporation)
a t t a i n e d w h e n several b a n d s h a v e t r a n s m i s s i o n o f less
t h a n 3 0 - 4 0 % , b u t n o b a n d h a s less t h a n 5 - 1 0 %
transmission. T h e background in nonabsorbing re
gions s h o u l d b e relatively flat a t a b o u t t h e 9 0 - 9 5 %

Figure 3
Optical schematic for an interferometer spectrometer:
A, ir source; B, laser; C, white light; D , white-light
detector; E, laser detector; F, sample chamber; and G, ir
detector (reproduced with permission from IBM
Instruments, Inc.)

196

t r a n s m i s s i o n level. T h e s a m p l e s h o u l d b e u n i f o r m
over t h e a r e a t h a t intercepts t h e s a m p l e b e a m ; t h a t is,
it s h o u l d n o t b e w e d g e d o r s h o w holes. G a s e s a r e
usually s a m p l e d in cells 2 - 1 0 c m in length, a l t h o u g h
multireflection cells o f over 1 k m i n p a t h length h a v e
been used for t r a c e analysis. M a n y s a m p l i n g m e t h o d s
a r e available, o f w h i c h t h e m o s t p o p u l a r a r e : for
liquids, s o l u t i o n in a n inert solvent a n d liquid film; f o r
solids, s o l u t i o n in a n inert solvent, as a p o w d e r mulled
with m i n e r a l oil ( t o r e d u c e scattering o f t h e r a d i a
tion), p o w d e r s u s p e n d e d in a K B r m a t r i x t h a t h a s
been pressed i n t o a t r a n s p a r e n t pellet, a n d a t t e n u a t e d
t o t a l reflectance. E a c h s a m p l i n g m e t h o d h a s a d v a n
tages a n d d r a w b a c k s ; t h e m e t h o d s h o u l d b e m a t c h e d
to the problem.
L i q u i d films a r e p r e p a r e d b y placing a d r o p o f
liquid o n t h e salt w i n d o w a n d " w i p i n g " t h e w i n d o w
against a flat surface. Alternatively, a n o t h e r w i n d o w
m a y b e pressed o n t h e s a m p l e t o form a s a n d w i c h .
S o m e trial a n d e r r o r will b e necessary t o achieve a
s p e c t r u m h a v i n g t h e p r o p e r intensities.
Soluble liquids a n d solids (except a m i n e s ) m a y b e
dissolved in i r - t r a n s m i t t i n g solvents, such a s C C 1 4 o r
1
C 2 C 1 4 (used in t h e 4 0 0 0 - 1 3 4 0 c m " region) a n d C S 2

Infrared
-1

(used in the 1340-600 c m

region). T h e s e solvents
should be m a n i p u l a t e d only in a chemical fume h o o d ,
however, as their v a p o r s a r e toxic. A s a m p l e c o n c e n
t r a t i o n of 1 0 % (wt/vol) in a 0.1 m m cell usually gives
o p t i m u m intensities. M o r e p o l a r solvents c a n be used
in limited w a v e l e n g t h regions w h e r e their t r a n s m i s
sion exceeds 5 0 % .
G r i n d a b l e solids c a n be s a m p l e d as m i n e r a l oil o r
alkali halide mulls. T h e objective is t o s u s p e n d the
finely g r o u n d s a m p l e in a m a t r i x of similar refractive
index in o r d e r t o r e d u c e scattering of t h e r a d i a t i o n .
M i n e r a l oil mulls a r e p r e p a r e d by vigorously grind
ing 10-50 m g of s a m p l e t o a finely divided state, using
a large m o r t a r a n d pestle. M i n e r a l oil is a d d e d d r o p wise a n d light g r i n d i n g is c o n t i n u e d until t h e s a m p l e
h a s t h e a p p e a r a n c e a n d consistency of cold c r e a m . It
is t h e n g a t h e r e d with a r u b b e r w i p e r a n d s a n d w i c h e d
between t w o ir w i n d o w s . A b s o r p t i o n s from t h e
m i n e r a l oil o b s c u r e t h e C H stretching a n d b e n d i n g
1
1
regions ( 2 8 5 0 - 2 9 5 0 c m " , 1450-1480 c m " a n d 1 4 0 0 1
1420 c m " ) b u t t h e r e m a i n d e r of the s p e c t r u m is
relatively clear. A s e c o n d m u l l t h a t uses a perfluorin a t e d o r p e r c h l o r i n a t e d oil c a n b e p r e p a r e d if it is
necessary t o e x a m i n e t h e C H regions.
Alkali halide mulls a r e usually m a d e from K B r
p o w d e r , i n t o w h i c h a b o u t 1 m g of t h e finely g r o u n d
s a m p l e is t h o r o u g h l y m i x e d . T h e p o w d e r is pressed
i n t o a t r a n s p a r e n t pellet, u s i n g a c o m m e r c i a l die
(usually e v a c u a t e d before pressing). T h i s t e c h n i q u e
s h o u l d n o t be used with s a m p l e s t h a t c o n t a i n ex
c h a n g e a b l e halides (such as a m i n e h y d r o c h l o r i d e s ) o r
t h o s e t h a t display p o l y m o r p h i s m , as it will b e very
difficult t o o b t a i n r e p r o d u c i b l e spectra.
P o w d e r e d solids c a n also be e x a m i n e d b y diffuse
reflectance, in w h i c h t h e s a m p l e b e a m is directed o n t o
the p o w d e r . T h e diffusely scattered r a d i a t i o n is col
lected by a m i r r o r system a n d r o u t e d b a c k i n t o t h e
optical p a t h of t h e s p e c t r o m e t e r .
A t t e n u a t e d t o t a l reflectance ( A T R ) is a t e c h n i q u e
in which t h e s a m p l e (usually a solid) is simply pressed
against a n internal-reflection e l e m e n t (see Fig. 4). T h e
r a d i a t i o n is internally reflected from t h e interior sur
face of t h e element, b u t also p e n e t r a t e s slightly (of t h e
o r d e r of o n e w a v e l e n g t h ) i n t o t h e adjacent m e d i u m

(in this case, t h e s a m p l e ) . Multireflection elements a r e

used t o increase a b s o r p t i o n intensities.
Special t e c h n i q u e s a r e used for m i c r o s a m p l e s .
A b s o r p t i o n o r reflection s p e c t r a c a n be o b t a i n e d o n
particles as small as 20 in d i a m e t e r using a m i c r o
scope with reflecting optics. T h i n films ( m o n o l a y e r s o r
less) of o r g a n i c m a t e r i a l s o n reflecting m e t a l surfaces
c a n be s a m p l e d b y setting t h e ir b e a m a t glancing
incidence t o t h e surface ( r e f l e c t i o n - a b s o r p t i o n spec
troscopy).
Pyrolysis is usually c o n s i d e r e d t o be a t e c h n i q u e of
last resort. It is often a p p l i e d t o insoluble o r heavily
filled p o l y m e r s a n d t o i n o r g a n i c p o w d e r s t r e a t e d with
unextractable organic material. The fragmented sam
ple ( 0 . 1 - 0 . 5 g) is placed in a test t u b e a n d h e a t e d
strongly over a flame with t h e t u b e h o r i z o n t a l . T h e
volatile p o l y m e r fragments c o n d e n s e n e a r t h e neck of
t h e t u b e a n d c a n easily b e transferred t o a salt plate.
Since t h e s p e c t r u m of t h e p y r o l y s a t e m a y be s o m e
w h a t different from t h a t of t h e p a r e n t c o m p o u n d , a
reference library of p y r o l y s a t e spectra c a n be very
helpful.
W h e n c o m b i n e d with gas c h r o m a t o g r a p h y ( G C ) , ir
s p e c t r o s c o p y p r o v i d e s a powerful m e t h o d of identify
ing t h e c o m p o n e n t s of c o m p l e x m i x t u r e s . T h e
F o u r i e r - t r a n s f o r m ir s p e c t r o m e t e r , b e c a u s e of its fast
scan capability, is well suited t o o b t a i n i n g " o n - t h e fly" s p e c t r a of fractions as they a r e eluted. Specially
designed gas cells, o r " l i g h t p i p e s , " a n d sensitive
d e t e c t o r s p e r m i t t h e use of capillary G C c o l u m n s
(Griffiths et al. 1983). D e t e c t i o n limits of less t h a n
40 n g h a v e been r e p o r t e d . T h e G C / i r c o m b i n a t i o n is
often preferred t o G C / m a s s s p e c t r o m e t r y for p o l a r
s a m p l e s , w h e r e a s t h e reverse is t r u e for n o n p o l a r
materials.
A m a t r i x isolation system, in w h i c h t h e c h r o m a t o
g r a p h effluent is m i x e d with a r g o n gas a n d frozen a t
14 o n a reflecting s u b s t r a t e , is claimed t o give even
b e t t e r sensitivity. G o o d spectra o n fractions of 5 n g o r
less h a v e b e e n d e m o n s t r a t e d .
Infrared s p e c t r o s c o p y h a s also been c o m b i n e d with
liquid c h r o m a t o g r a p h y for c h a r a c t e r i z a t i o n of n o n
volatile s a m p l e s such as p o l y m e r s . P r o b l e m s of sol
vent o p a c i t y often p r e c l u d e direct s c a n n i n g of the
eluent s o l u t i o n , b u t i n g e n i o u s s o l v e n t - r e m o v a l sys
t e m s h a v e been devised t h a t allow unrestricted s a m
pling of t h e eluted fractions.

4. Qualitative
Sample

Figure 4
Schematic representation of the radiation path in a
single-reflection internal-reflection element (after Smith
1979. John Wiley and Sons, New York. Reproduced
with permission)

Spectroscopy

Analysis

A n ir s p e c t r u m c o n t a i n s a n e n o r m o u s a m o u n t of
i n f o r m a t i o n , b u t m u c h of it is n o t readily e x t r a c t a b l e .
W i t h s o m e experience, it is possible t o recognize
certain w e l l - k n o w n g r o u p frequencies ( T a b l e 1). C o r
relation c h a r t s t h a t s h o w b a n d locations for the m a j o r
chemical g r o u p s a r e often used t o suggest structures
for further s t u d y a n d c o r r o b o r a t i o n . Existence of a
chemical g r o u p is usually verified a t several places in

197

Infrared

Spectroscopy

Table 4
Specific materials applications of ir spectroscopy
Area of application

Specific uses

Air pollution

Determination of ppm S0 2, S 0 3 and H 2S 0 4

Studies of the chemistry of smog formation in a laboratory reactor
Detection of hazardous vapors in the ppm and ppb range
Analysis of urinary stones or calculi
Detection of allergenic substances on skin
Analysis of anesthetic gases
Characterization of intermediates in the CO/H 2 reaction on Si02-supported Ru
Studies of coking on zeolites
Studies of chemisorption of H 2 0 and CO on Fe-Cr catalysts
Quality control of intermediates
On-line process stream analysis
Identification of impurities in products
Identification of polymers, pigments and solvents
Quantitation of coating components
Study of weathering effects on chemical structure
Quality control of products
Analysis of competitive products
Identification of antibiotics
Analysis of cotton-polyester fiber blends
Characterization of flame retardants, lubricants and softeners
Determination of crystallinity, orientation and polymorphic form in fibers
Characterization of soils
Identification of pigments
Study of hydration reactions in portland cement
Determination of boron nitride in transformer steel
Determination of oxygen in sodium metal
Characterization of coatings on metals
Tracing crude oil spills as to origin
Determination of additives in lubricants
Analysis of crude oil fractions
Identification of polymers, blends and plasticizers
Characterization of stereoregularity of isotactic and syndiotactic polypropylene
Determination of hydroxyl groups in epoxy resins
Analysis of silicon for ppb oxygen, boron, carbon and phosphorus
Determination of epitaxial layer thickness
Analysis of silicon halides used to produce silicon
Analysis of paper for groundwood content
Determination of lignin in birchwood pulp
Determination of silicone release coating on paper

Biomedical materials
Catalysts
Chemicals
Coatings, paints, varnishes and
resins
Drugs and pharmaceuticals
Fibers and textiles
Inorganic materials
Metals
Petroleum
Polymers and elastomers
Semiconductors
Wood and paper

the s p e c t r u m . A priori s t r u c t u r e d e t e r m i n a t i o n from

c o r r e l a t i o n c h a r t s is n o t feasible, however; c o m p a r i
son of the u n k n o w n s p e c t r u m with a n a u t h e n t i c
reference s p e c t r u m of the suspected s u b s t a n c e is es
sential. T h e s a m e s a m p l e p r e p a r a t i o n t e c h n i q u e
should be used for b o t h u n k n o w n a n d reference, as
details of t h e s p e c t r u m d e p e n d o n t h e physical state of
the sample. Reference spectra m a y be p r e p a r e d by t h e
user from carefully r u n p u r e s a m p l e s , o r p u r c h a s e d in
a c o m m e r c i a l collection.
Infrared s p e c t r o s c o p y is often t e a m e d with o t h e r
s t r u c t u r a l t e c h n i q u e s such as N M R (see Nuclear
Magnetic Resonance Spectroscopy)
to obtain more
complete structural information about a material.
C o m p u t e r i z e d search r o u t i n e s a r e often used t o
identify spectra of u n k n o w n s . I n o n e system, refer
ence spectra a r e c o d e d by t h e p o s i t i o n s of their

198

strongest b a n d s . A search b a s e d o n b a n d p o s i t i o n will

usually retrieve a s p e c t r u m t h a t m a t c h e s the
u n k n o w n , if it is p r e s e n t in the library. A n o t h e r
c o m p u t e r i z e d system utilizes a logical i n t e r p r e t a t i o n
a p p r o a c h , b a s e d o n g r o u p frequencies. In a n y case,
identification is n o t c o m p l e t e until t h e u n k n o w n spec
t r u m h a s been m a t c h e d t o a n a u t h e n t i c reference
spectrum.
5. Quantitative

Analysis

Q u a n t i t a t i v e analysis is also possible u s i n g ir spectros

c o p y , a n d indeed w a s o n e of the earliest practical uses
of the t e c h n i q u e . S a m p l i n g is usually carried o u t u s i n g
solutions so t h a t t h e a n a l y t e c o n c e n t r a t i o n a n d the
p a t h length c a n be c o n t r o l l e d . If I0 is t h e intensity of
t h e r a d i a t i o n incident o n the s a m p l e cell, / is t h e

Ion Backscattering

intensity of t h e t r a n s m i t t e d r a d i a t i o n a n d is t h e
t r a n s m i t t a n c e , t h e B o u g u e r - B e e r l a w states t h a t t h e
a b s o r b a n c e A is
A = log 1 0 0 / % = log / 0 / / = abc

(5)

H e r e is a p r o p o r t i o n a l i t y c o n s t a n t related t o t h e
a b s o r p t i v e p o w e r of t h e a n a l y t e , b is t h e s a m p l e
thickness a n d c is t h e a n a l y t e c o n c e n t r a t i o n . It s h o u l d
be n o t e d t h a t m o s t ir s p e c t r o m e t e r s r e c o r d b a n d
intensities linearly in p e r c e n t t r a n s m i s s i o n , w h i c h
is a l o g a r i t h m i c function of c o n c e n t r a t i o n . T h u s ,
m e a s u r e m e n t s in % m u s t be c o n v e r t e d t o a b s o r b
ance before c a l c u l a t i o n s of c o n c e n t r a t i o n c a n b e
done.
Analysis of m i x t u r e s is carried o u t by m e a s u r i n g
a s t r o n g a n d preferably isolated b a n d of e a c h c o m
ponent. Either peak absorbance or integrated b a n d
a r e a (on a linear a b s o r b a n c e o r d i n a t e ) m a y b e used,
with t h e latter giving b e t t e r precision. If m u t u a l
interference o c c u r s (i.e., o v e r l a p p i n g a b s o r p t i o n s ) ,
c o r r e c t i o n s c a n be m a d e for t h e interference as
follows.
T h e a b s o r b a n c e Av a t a n y frequency is t h e s u m o f
t h e a b s o r b a n c e s of t h e /th species a t t h a t frequency, o r
Av = axbxcx

+ a2b2c2

+ ... + aibici

(6)

T h e a b s o r p t i o n coefficients a{ a r e d e t e r m i n e d b y
m e a s u r e m e n t s o n t h e p u r e c o m p o n e n t s , a t frequencies
c h o s e n t o give m a x i m u m a b s o r b a n c e for o n e c o m
p o n e n t a n d m i n i m u m a b s o r b a n c e for t h e o t h e r s .
Mixtures are analyzed by making absorbance
m e a s u r e m e n t s a t t h e selected frequencies a n d u s i n g
t h e results in a set of s i m u l t a n e o u s e q u a t i o n s , w h i c h
c a n b e solved b y m a t r i x inversion t o give t h e indi
vidual c o n c e n t r a t i o n s :

c, = IZ*/vA
I

(7)

Multivariate least-squares calibration methods,

which use m i x t u r e s i n s t e a d of p u r e c o m p o n e n t s for
c a l i b r a t i o n , h a v e s o m e a d v a n t a g e s ( H a a l a n d et al.
1985). Precision is s o m e t i m e s i m p r o v e d b y t h e overd e t e r m i n a t i o n m e t h o d ; t h a t is, m e a s u r i n g several
wavelengths for e a c h c o m p o n e n t .
F o r best q u a n t i t a t i v e a c c u r a c y , b a n d intensities
s h o u l d fall in t h e r a n g e of 2 0 - 7 0 % T. M e a s u r e m e n t s
s h o u l d never b e m a d e b e l o w 1 0 % (A = 1) b e c a u s e of
the large effect of small e r r o r s in establishing t h e
T= 0 p o i n t a n d in m e a s u r i n g A.
Q u a n t i t a t i v e analysis for solids such as p o l y m e r
blends c a n s o m e t i m e s be a c c o m p l i s h e d b y using b a n d
ratios. F o r b i n a r y m i x t u r e s , m e a s u r e m e n t of o n e b a n d
from e a c h c o m p o n e n t is used t o calculate a n a b s o r b
ance r a t i o t h a t c a n be related graphically t o t h e
c o n c e n t r a t i o n r a t i o . O r , if o n e c o m p o n e n t of a mix
t u r e is c o n s t a n t in c o n c e n t r a t i o n o r is t h e m a j o r
constituent, the ratio of an analyte b a n d to a b a n d of
the m a j o r c o n s t i t u e n t c a n be p l o t t e d a g a i n s t a n a l y t e

Analysis

c o n c e n t r a t i o n . It is g o o d p r a c t i c e t o derive statistical
m e a s u r e s of a c c u r a c y a n d precision by repetitively
a n a l y z i n g i n d e p e n d e n t s t a n d a r d s over a p e r i o d of
several d a y s .

6.

Applications

Applications to numerous nonmetallic (and some

metallic) m a t e r i a l s h a v e been d o c u m e n t e d . R e p o r t s of
studies c o n c e r n e d with chemical c o m p o s i t i o n , kine
tics, s t r u c t u r e a n d surfaces a r e n u m e r o u s . S o m e
specific m a t e r i a l s a p p l i c a t i o n s a r e listed in T a b l e 4.
T h e listing is n o t c o m p r e h e n s i v e ; it is i n t e n d e d only
t o illustrate t h e r a n g e of possible a p p l i c a t i o n s .
See also: Optical Emission Spectroscopy; Raman Spectros
copy.

Bibliography
American Society for Testing and Materials, Committee
E-13 1979 Manual on Practices in Molecular Spectros
copy. American Society for Testing and Materials, Phila
delphia, PA
Colthup , Daly L H, Wiberley S 1975 Introduction to
Infrared and Raman Spectroscopy. Academic Press, New
York
Craver C D (ed.) 1977 The Coblentz Society Deskbook of
Infrared Spectra. Coblentz Society, Kirkwood, MO
Griffiths R 1975 Chemical Infrared Fourier Transform
Spectroscopy. Wiley, New York
Griffiths R, Dehaseth J A, Azzaraga L V 1983 Capillary
GC/FT-IR. Analyt. Chem. 55A: 1361-87
Haaland D M, Easterling R G, Vopicka D A 1985 Multi
variate least-squares methods applied to the quantitative
spectral analysis of multicomponent samples. Appl. Spectrosc. 39: 73-84
Harrick J 1967 Internal Reflection Spectroscopy. Interscience, New York
Haslam J, Willis A, Squirrell D C 1979 Identification
and Analysis of Plastics, 2nd edn. Heyden, London
Infrared Spectroscopic Committee of the Chicago Society
for Coatings Technology 1979 An Infrared Spectroscopic
Atlas for the Coatings Industry. Federation of Societies
for Coating Technology, Philadelphia, PA
Koenig J L 1980 Chemical Microstructure of Polymer
Chains. Wiley, New York
Pouchert C J 1975 The Aldrich Library of Infrared Spectra,
2nd edn. Aldrich Chemical Company, Milwaukee, WI
Smith A L 1979 Applied Infrared Spectroscopy: Fundamen
tals, Techniques and Analytical Problem-Solving. Wiley,
New York
A . L. S m i t h
[Dow Corning, Midland, Michigan, USA]

Ion Backscattering Analysis

I o n b a c k s c a t t e r i n g p r o v i d e s a very simple direct a n d
n o n d e s t r u c t i v e m e t h o d for m i c r o a n a l y s i s of m a t e r
ials. It utilizes t h e d e t e c t i o n of particles b a c k s c a t t e r e d

199

Ion Backscattering

Analysis

from a given d e p t h w h e n a n incident ion ( M e V energy

r a n g e ) p e n e t r a t e s a target. It is best suited t o t h e
detection of h e a v y elements o n light s u b s t r a t e s , a n d
h a s been applied t o t h e d e t e r m i n a t i o n of c o m p o
sitional v a r i a t i o n o r i m p u r i t y d i s t r i b u t i o n as a func
tion of d e p t h b e l o w t h e surface of a s a m p l e . A s a n ion
b e a m h a s a finite r a n g e , this t e c h n i q u e is m o s t a p p r o
p r i a t e for t h e analysis of layered s t r u c t u r e s such a s
t h o s e e n c o u n t e r e d in thin films a n d thick solid sur
faces. T h e t e c h n i q u e h a s t h e ability t o d e t e r m i n e t h e
c o n c e n t r a t i o n of a t o m s with high sensitivity as a
function of d e p t h a n d with a d e p t h r e s o l u t i o n of a few
tens of n a n o m e t e r s over a d e p t h of h u n d r e d s of
nanometers without recourse to sample erosion or
layer r e m o v a l . H e n c e , t h e t e c h n i q u e is a n i n v a l u a b l e
analytical t o o l for the investigation of solid-state
p h e n o m e n a a n d h a s been extensively utilized in a r e a s
of m a t e r i a l s t e c h n o l o g y such as electronics a n d n u
clear energy. I n electronic m a t e r i a l s , t h e a p p l i c a t i o n s
r a n g e from r o u t i n e o n e s such as q u a l i t y c o n t r o l in t h e
fabrication of s e m i c o n d u c t o r devices t o specialized
investigations of ion i m p l a n t a t i o n ( d o p a n t profiles,
thin-film d e p o s i t i o n ) , i m p u r i t y solubility, diffusion
a n d r e a c t i o n s , c o n t a c t f o r m a t i o n , epitaxial layers,
thermal and anodic oxidation, a n d metallization. In
nuclear energy t e c h n o l o g y , t h e t e c h n i q u e is used t o
investigate o x i d a t i o n c o r r o s i o n a n d c l a d d i n g of
m a t e r i a l s . By c o m b i n i n g c h a n n e l l i n g with b a c k scattering m e a s u r e m e n t s , c r y s t a l l o g r a p h i c i n f o r m a
tion such as lattice site l o c a t i o n of impurities o r lattice
d i s o r d e r c a n b e d e t e r m i n e d . T h e s e topics h a v e b e e n
covered extensively in t h e literature ( M a y e r a n d T u
1974, Ziegler et al. 1975a, F o t i et al. 1977, C h u et al.
1978).

1. Rutherford

Backscattering

W h e n a projectile p e n e t r a t e s a t a r g e t , it loses energy

t h r o u g h o u t its trajectory t o t h e electrons of t h e t a r g e t
a t o m s b y i o n i z a t i o n a n d b y excitation, a n d it also
loses energy b y n u c l e a r collisions. W h e n this projectile
e n c o u n t e r s a h a r d collision, it c a n c h a n g e its trajec
t o r y i n t o a n o u t w a r d direction in a straight-line
p a t h t h i s is b a c k s c a t t e r i n g . D u r i n g its o u t w a r d p a t h
it also loses energy t o t h e t a r g e t a t o m s until t h e
particle emerges from t h e target. T h e b a c k s c a t t e r e d
particles c a n t h u s be i n t e r p r e t e d as single-collision
events a n d t h e simplicity of t w o - b o d y k i n e m a t i c s c a n
be exploited. T h e energy loss suffered d u r i n g t h e
inward and outward paths provides the depth to
which t h e projectile h a s p e n e t r a t e d . T h i s analysis
t e c h n i q u e is k n o w n as R u t h e r f o r d b a c k s c a t t e r i n g
( R B S ) . A s c h e m a t i c d i a g r a m of a typical e x p e r i m e n t a l
setup is s h o w n in F i g . 1. I o n b e a m s of 0.1-1 M e V
h y d r o g e n a n d 1-4 M e V h e l i u m ions a r e c o m m o n l y
used because they a r e readily available using small
accelerators, they i n c u r least d a m a g e a m o n g ions of
c o m p a r a b l e velocity a n d their s t o p p i n g p o w e r (dE/dx)

200

Detector

Figure 1
Schematic representation of the experimental geometry for
the backscattering technique

h a s been extensively investigated (Ziegler a n d C h u

1974, A n d e r s e n a n d Ziegler 1977, Ziegler 1977). A l s o ,
t h e R u t h e r f o r d cross section is well k n o w n for these
ions. I n practice, a m o m e n t u m - a n a l y z e d a n d well4
+
collimated b e a m of 2 M e V H e from a n accelerator
is directed t o w a r d t h e t a r g e t a t angle relative t o the
surface n o r m a l , a n d t h e elastically scattered yield
e m e r g i n g a t angle 2 is r e c o r d e d b y a c h a r g e d - p a r t i c l e
d e t e c t o r . T h e 2 M e V h e l i u m ion is c h o s e n as a projec
tile b e c a u s e it p r o v i d e s g o o d m a s s r e s o l u t i o n a n d is
involved in n o k n o w n n u c l e a r r e a c t i o n s below
1 2
7
2300 k e V . I n special cases, C a n d L i i o n s h a v e b e e n
used as projectiles. A l t h o u g h heavier ions p r o v i d e
b e t t e r m a s s r e s o l u t i o n for t h e h i g h - m a s s elements,
they h a v e n o t b e e n used o w i n g t o p o o r d e t e c t o r
r e s o l u t i o n a n d t h e large d a m a g e p r o d u c e d in t h e
target by heavy ions. Increased depth resolution has
been achieved u s i n g g r a z i n g incidence. Solid-state
d e t e c t o r s a r e c o m m o n l y e m p l o y e d b e c a u s e they a r e
relatively inexpensive a n d c a n be used in a n energydispersive m o d e with a r e a s o n a b l e energy r e s o l u t i o n
(SE 1 5 k e V ) . D i s t o r t i o n s in t h e energy s p e c t r u m
d u e t o pile-up c a n b e m i n i m i z e d b y using either a
lower c o u n t i n g r a t e o r s t a n d a r d pile-up rejection
circuits. I m p r o v e d energy r e s o l u t i o n c a n be achieved
b y u s i n g t h e b u l k i e r electrostatic o r m a g n e t i c spect
r o m e t e r s , b u t this m u s t b e weighed a g a i n s t a longer
d a t a a c c u m u l a t i o n t i m e since e a c h p o i n t in t h e energy
s p e c t r u m m u s t be r e c o r d e d sequentially. A l s o , t h e
higher a c c u m u l a t e d b e a m d o s e c o n t r i b u t e s t o
increased r a d i a t i o n d a m a g e in t h e s a m p l e .
T h e r e a r e t h r e e basic c o n c e p t s in b a c k s c a t t e r i n g ,
a n d e a c h p r o v i d e s a n analytical capability: (a) the
k i n e m a t i c factor allows m a s s analysis; (b) t h e differ
ential scattering cross section enables q u a n t i t a t i v e
analysis; a n d (c) t h e energy loss m a k e s possible d e p t h
analysis. I n o r d e r t o illustrate t h e principles a n d
limitations of t h e t e c h n i q u e , c o n s i d e r t h e b a c k s c a t t e r
ing analysis of a well-polished e l e m e n t a l t a r g e t of
a t o m i c density N. F i g u r e 2 gives t h e n o t a t i o n a n d
s c h e m a t i c b a c k s c a t t e r i n g energy s p e c t r u m for a fixed
b o m b a r d i n g energy a n d g e o m e t r y . T h e edge o c c u r
ring a t a n energy E' c o r r e s p o n d s t o t h e scattering
from t h e a t o m s a t t h e surface layer a n d is g o v e r n e d b y

Ion Backscattering

incident

beam

Analysis

t h e r a t e of c h a n g e of loss p e r u n i t p a t h d o e s n o t
c h a n g e a p p r e c i a b l y , there is a linear relation between
energy loss AE a n d d e p t h t t h a t c a n be expressed as

E0

AE=[S]t

(2)

w h e r e [S\ is called t h e b a c k s c a t t e r i n g energy-loss

factor, w h i c h c h a n g e s slowly as a function of a n d t.
T h i s factor d e p e n d s o n KM a n d dE/dx for the ingoing
a n d o u t g o i n g p a t h in t h e m a t e r i a l , a n d c a n be calcu
lated as
[S] = (KM/cos

9x){dEldx)Em
+ (\/cose2)(dE/dx)Eoax

Scattered

energy

Figure 2
Schematic representation of the Rutherford backscattering
yield from a thick target with surface impurities

the t w o - b o d y k i n e m a t i c s of elastic scattering. F o r t h e

energies of interest here, relativistic effects m a y b e
neglected. I n t e r m s of t h e incident-particle m a s s m
a n d energy E0, t a r g e t m a s s a n d l a b o r a t o r y scatter
ing angle 0, k i n e m a t i c factor m a y b e defined as

&

m cos 9 + (M -m

E' =
~E^

t0

(3)

w h e r e Ein = E0- (AE/4) a n d o ut = Ex + (AE/4) ( C h u

et al. 1978). Values of dE/dx a r e given in t e r m s of the
s t o p p i n g cross section = (\/N)(dE/dx),
w h e r e is
t h e a t o m i c density. F o r n o r m a l incidence, = 0,
0 2 = - 0. H e n c e ,

s i n 0 ) 1/22

L
0)

H e r e , the n o t a t i o n K= KM is applicable t o a given

b a c k s c a t t e r i n g e x p e r i m e n t in w h i c h m a n d 0 a r e
p r e d e t e r m i n e d . T h e yield at energies b e l o w t h e step
(Fig. 2) therefore c o r r e s p o n d s t o t h e scattering from
deeper layers b e c a u s e the scattered particle suffers
energy loss in b o t h t h e i n w a r d a n d o u t w a r d p a t h s . It
c a n be seen t h a t t h e presence of surface i m p u r i t i e s
shows u p as a p e a k a t a n energy a b o v e t h e edge if their
m a s s is greater a n d b e l o w if lower. T h i s allows
elements, a n d even i s o t o p e s u p t o a b o u t m a s s 4 0 , t o
be distinguished. F o r elements of m u c h g r e a t e r m a s s ,
the s e p a r a t i o n b e c o m e s less a n d less, a n d close h e a v y
elements c a n n o t b e s e p a r a t e d . O n t h e o t h e r h a n d , for
light elements such as c a r b o n , oxygen o r n i t r o g e n t h e
p r o b l e m is often t h a t of interference d u e t o a signal
from the s u b s t r a t e . F r o m t h e a b o v e e q u a t i o n it is seen
t h a t the best m a s s s e p a r a t i o n is o b t a i n e d w h e n
0 = 1 8 0 . I n practice, 0 = 160-179 c a n easily b e
achieved using a n n u l a r solid-state d e t e c t o r s . T h e
energy difference r e p r e s e n t s t h e energy loss from
the b e a m particles o n i n w a r d a n d o u t w a r d p a s s a g e
t h r o u g h the layer. T h e r e is a direct relation b e t w e e n
the total thickness of the layer a n d the t o t a l w i d t h AE
of the signal. I n general, for small energy loss, w h e r e

[S] = NKMe(Em)

+ (7V7|cos 0 | ) e ( E o u )t

(4)

Values of s t o p p i n g cross sections h a v e been t a b u l a t e d

( C h u et al. 1978). K n o w i n g t h e value of AE a n d S,
s a m p l e thickness t c a n b e d e t e r m i n e d . I n the case of a
t h i n h e a v y i m p u r i t y layer o n t o p of a light s u b s t r a t e ,
t h e h e a v y i m p u r i t y c o r r e s p o n d s t o t h e p e a k a b o v e the
edge. If t h e overall system r e s o l u t i o n is small c o m
p a r e d w i t h the w i d t h of p e a k , this w i d t h gives a direct
m e a s u r e of t h e film thickness if t h e s t o p p i n g p o w e r is
known.
I n b a c k s c a t t e r i n g analysis, t h e n u m b e r of a t o m s Nt
p e r u n i t a r e a of t h e t a r g e t is d e t e r m i n e d . T h e a r e a A
u n d e r e a c h of t h e p e a k s in Fig. 2 is p r o p o r t i o n a l t o the
t o t a l n u m b e r of a t o m s p e r u n i t a r e a of each type a n d
t o t h e differential scattering cross section of each
a t o m (i.e., A oc oNt). T o d e t e r m i n e a n a b s o l u t e value
for Nt from the i n t e g r a t e d n u m b e r of c o u n t s requires
careful d e t e r m i n a t i o n of the scattering g e o m e t r y ,
b e a m - c u r r e n t i n t e g r a t i o n a n d m e a s u r e m e n t of the
active a r e a of t h e solid-state d e t e c t o r . F o r a t o t a l
n u m b e r of incident h e l i u m ions Q a n d a d e t e c t o r solid
angle , t h e t o t a l a r e a A in c o u n t s u n d e r the p e a k is
given by
A =

QQaNt

(5)

T h e R u t h e r f o r d differential scattering cross section

4
for 1 M e V H e ions h a s b e e n t a b u l a t e d ( C h u et al.
1978). T h e scattering cross section oc 7?/?^ w h e r e
is t h e a t o m i c n u m b e r ; c o n s e q u e n t l y , the t o t a l a r e a
u n d e r the p e a k is larger for heavier elements a n d for
smaller projectile energy.
B a c k s c a t t e r i n g analysis h a s been used t o s t u d y
c o m p o u n d o r m i x t u r e targets. If t h e c o m p o u n d c o n
t a i n s t w o elements A a n d with a m o l e c u l a r c o m p o
sition A mB , w h e r e m a n d a r e fractions a n d
m + n = 1, a n d if t h e r a t i o of the energy w i d t h s for the
t w o e l e m e n t s is unity, t h e n from the b a c k s c a t t e r e d
s p e c t r u m the r a t i o of the c o r r e s p o n d i n g heights is
HJHB ~ (oJo^(m/n).
T h e analysis for thick targets
201

Ion Backscattering

Analysis

a n d t h e detailed formalism a n d a n u m e r i c a l m e t h o d
h a s been d e v e l o p e d b y Brice (1973). C o m p u t e r a n a l y
sis of c o m p l e x b a c k s c a t t e r i n g spectra h a s been
developed b y Ziegler et al. (1975b).
T h e r e a r e limitations t o b a c k s c a t t e r i n g s p e c t r o m
etry which m u s t b e b o r n e in m i n d w h e n c o n s i d e r i n g
t h e a p p l i c a t i o n o f t h e t e c h n i q u e t o specific p r o b l e m s .
T h e s a m p l e d e p t h t h a t c a n b e a n a l y z e d with 2 M e V
4
+
H e ions is a b o u t 1-2 . A l s o , t h e b a c k s c a t t e r i n g
t e c h n i q u e is n o t highly element specific, a n d for
h e a v y - m a s s e l e m e n t s it is difficult t o o b t a i n g o o d m a s s
resolution. I n this case, i o n - i n d u c e d rays c a n b e used
for element identification. A n o t h e r limitation is t h a t it
is n o t always possible t o completely identify t h e
chemical p h a s e s t h a t a r e p r e s e n t in a c o m p o u n d .
C o m p l e m e n t a r y t e c h n i q u e s like s e c o n d a r y - i o n m a s s
s p e c t r o s c o p y ( S I M S ) a n d x-ray diffraction in c o n j u n c
tion with b a c k s c a t t e r i n g studies p r o v i d e i n f o r m a t i o n
o n p h a s e f o r m a t i o n a n d r e a c t i o n kinetics. T h e sensi
tivity of t h e b a c k s c a t t e r i n g t e c h n i q u e for d e t e c t i o n of
low-mass elements o n a h i g h - m a s s s u b s t r a t e is p o o r ,
and nuclear reactions or resonance techniques must
be used t o o b t a i n q u a n t i t a t i v e i n f o r m a t i o n o n trace
a m o u n t s of these elements. T h e s e t e c h n i q u e s h a v e
been reviewed b y W o l i c k i (1975) a n d C h u et al.
(1978).

Energy ( M e V )

Channel number

Figure 3
4
+
Backscattered energy spectra for 2 MeV H e ions from
(a) lOOnm platinum sputter deposited on a silicon
substrate and (b) sintered at 375 C for 25 nm in an argon
atmosphere to form a Pt-Si layer 140 nm thick on a
silicon substrate

(^pJNsi)
2.

Applications

A s only a s h o r t time is r e q u i r e d for d a t a acquisition,

b a c k s c a t t e r i n g s p e c t r o m e t r y h a s been preferred for
e x p l o r a t o r y studies over t h e m o r e lengthy a n d d e
structive analysis t e c h n i q u e s involving s p u t t e r i n g for
layer r e m o v a l . T h e m o s t s t r a i g h t f o r w a r d a p p l i c a t i o n
2
is t h e m e a s u r e m e n t of t h e thickness in a t o m s p e r c m
of deposited m e t a l films. T h e c o n c e p t of relating AE
to layer thickness h a s been used in t h e d e t e r m i n a t i o n
of surface i m p u r i t y c o n c e n t r a t i o n profiles (Ziegler
a n d Baglin 1971). I n general, systems a r e c h o s e n
w h e r e near-surface analysis is i m p o r t a n t ; e x a m p l e s
are thin films, layered s t r u c t u r e s , diffusion profiles,
i o n - i m p l a n t e d layers a n d dielectric layers. T o t a k e
a d v a n t a g e of t h e capabilities of b a c k s c a t t e r i n g , there
s h o u l d b e a c h a n g e in t h e c o m p o s i t i o n d u r i n g t h e
process t r e a t m e n t such a s interdiffusion b e t w e e n thinfilm elements o r g r o w t h of oxide layers. T h i s tech
n i q u e h a s been used t o m e a s u r e t h e c o m p o s i t i o n of
dielectric layers a n d t h e f o r m a t i o n of suicides. F i g u r e
4
+
3 shows a 2 M e V H e b a c k s c a t t e r i n g s p e c t r u m for a
P t - S i layer 140 n m thick o n a silicon s u b s t r a t e . F o r
c o m p a r i s o n , a b a c k s c a t t e r i n g s p e c t r u m of p u r e plati
n u m 100 n m film s p u t t e r d e p o s i t e d o n a silicon s u b
strate is also s h o w n . T h e silicon p a r t of t h e s p e c t r u m
is enlarged b y a factor of five for clarity. T h e r a t i o of
the s h a d e d a r e a of p l a t i n u m t o t h a t of silicon is 3 2 : 1 .
T h e cross section r a t i o aPt/aSi is e q u a l t o 3 2 : 1 . T h e r e
fore, t h e r a t i o of p l a t i n u m t o silicon a t o m s p e r u n i t
v o l u m e , given b y

202

= (APt/Asi)(aPilasi)

(6)

is e q u a l t o u n i t y ( t o within 1%). A n o t h e r a d v a n t a g e
of these m e a s u r e m e n t s is t h a t t h e s t o i c h i o m e t r y c a n
generally b e d e t e r m i n e d directly from t h e spectra.
T h e c o m p o s i t i o n c a n also b e d e t e r m i n e d from t h e
heights of t h e p l a t i n u m a n d silicon p l a t e a u s in t h e
b a c k s c a t t e r i n g spectra a s

= ^sJoPt)(HPi/HSi)(AEPi/AEsi)

(7)

In F i g . 3 , t h e r a t i o AEPJAESi is 1.15 a n d t h e m e a s u r e d
r a t i o HPt/Hsi is 27.5. Inserting values of , AE a n d
in t h e a b o v e e q u a t i o n gives NPJNsi = 1 ( t o within
2 % ) . H e n c e , if t h e surface i m p u r i t y is of high m a s s o n
a l o w - m a s s s u b s t r a t e , t h e precise values of Q a n d
need n o t b e k n o w n .
M e t a l l i z a t i o n plays a large role in t h e success o r
failure of integrated-circuit t e c h n o l o g y . I n o r d e r t o
m a k e electrical c o n n e c t i o n s b e t w e e n t h e devices a n d
the o u t s i d e w o r l d , it is necessary t o d e p o s i t thin m e t a l
layers for c o n d u c t i n g p a t h s . T h e r e a r e a h o s t of
p r o b l e m s associated with t h e metallization process,
all of which stem from t h e fact t h a t thin-film r e a c t i o n s
o c c u r a t relatively low t e m p e r a t u r e s . T o p r e v e n t c o m
p o u n d f o r m a t i o n a n i n t e r m e d i a t e layer is d e p o s i t e d a s
a b a r r i e r layer. F o r e x a m p l e , a thin layer of S i 0 2 h a s
been d e p o s i t e d in b e t w e e n N b S i 2 a n d a silicon s u b
s t r a t e ( C h o w et al. 1982). F i g u r e 4 a s h o w s t h e 2 M e V
4
+
H e s p e c t r u m for a n N b S i 2 thin film (406.4 n m ) o n
a n S i 0 2 - S i s u b s t r a t e . T h e silicide films were s p u t t e r e d
from a h o t - p r e s s e d alloy target of stoichiometric
c o m p o s i t i o n S i : N b = 2 o n t o h e a t e d (350 C) s u b
strates. O x i d a t i o n w a s carried o u t in d r y oxygen

Ion Backscattering

Energy (MeV)
0.8
cn

Si0 2

.0 in S i 0 2

X *
\

0 in Nb205 Si
i

~SiO,+
*

Energy (MeV)
S

1.0

1.2
i

-Hr^-NboO.-SiO,
2

2^5
4

uS b s et r a t

140 nm

oxidized NbSi 2 film

BF2 implanted15 in Si2

dose: 2 cm" at 2 5 keV

2 MeV H e ^ .

ft\ 7^ ,

Nb at
i ? ? S i i ^ surface

(C)

-.. 0 at surface
', I Si in NbSi,

I I

Si in Nb205-Si0,

'"""w^

1 Si

surface
"

BF2

(b)

.
5
m

^ channelling
peak corresponds to ionimplanted damage zone

0
i.o

'**V l
^4*^:
S ii

IOO

()

200

Si surface

Channel number

Figure 4
4
+
Backscattered energy spectra for 2 MeV H e ions from
(a) 406.4 nm NbSi 2 polycrystalline film deposited on
Si0 2-Si substrate; (b) thermal oxidation of NbSi 2 layer
carried out in dry oxygen at 600 C for 15 min; (c) thermal
oxidation of NbSi 2 layer carried out in dry oxygen at
650 C for 15 min. NbSi 2 layer is not completely oxidized
(after Chow et al. 1982)

b e t w e e n 550 C a n d 850 C. ( N b S i 2 films c a n b e oxi

dized a t lower t e m p e r a t u r e s t h a n o t h e r refractory
m e t a l suicides, such a s M o S i 2 , W S i 2 a n d T a S i 2. )
F i g u r e s 4 b a n d 4c s h o w t h e g r o w t h of oxide layers.
F r o m b a c k s c a t t e r i n g m e a s u r e m e n t s , t h e o x i d e films
exhibited t h e s a m e S i : N b r a t i o a s t h e initial silicide
layer. A l t h o u g h o n l y N b 2 O s h a s b e e n clearly identi
fied, density c o n s i d e r a t i o n s a n d e x p e r i m e n t a l values
of oxide thickness suggest t h a t n i o b i u m a n d silicon
oxides coexist. T h e b a c k s c a t t e r i n g t e c h n i q u e n o t o n l y
p r o v i d e s t h e t h i c k n e s s a n d s t o i c h i o m e t r y of n e w
layers b u t also t h e c o m p o s i t i o n o f t h e r e m a i n i n g
silicide layer.

Channelling

Axial o r p l a n a r c h a n n e l l i n g o c c u r s w h e n a c o l l i m a t e d
energetic b e a m o f i o n s (e.g., 2 M e V h e l i u m ions) is
incident o n a single crystal a l o n g a n axial o r p l a n a r
direction. T h e r o w s o r p l a n e s o f a t o m s a c t a s p o t e n t i a l
b a r r i e r s such t h a t t h e i o n s u n d e r g o a series o f c o r r e
lated screened C o u l o m b i c collisions. T h e s e smallangle collisions result in t h e c h a n n e l l e d i o n s b e i n g
steered b y t h e r o w s a n d p l a n e s t o w a r d s t h e c e n t r a l

300

400

500

600

Channel number

Si in NbSi 2

3.

Analysis

Figure 5
Random and (lOO)-aligned backscattering
spectra
for a
l5
2
silicon
crystal implanted with (2 1 0 c m ~ at +25 keV)
+
BF 2 ions. The amorphous zone created by BF 2 implant is
seen in the channelling spectrum

c h a n n e l region b e t w e e n t h e r o w s o r p l a n e s . H e n c e , in
terms of backscattering spectrometry, channelling
effects p r o d u c e strikingly large c h a n g e s in t h e yield o f
b a c k s c a t t e r e d particles a s t h e o r i e n t a t i o n of t h e single
crystal is c h a n g e d w i t h respect t o t h e incident b e a m .
C h a n n e l l i n g of energetic i o n s is well described in t h e
l i t e r a t u r e ( M a y e r et al. 1970, D e a r n a l e y 1973, M o r
g a n 1973, G e m m e l l 1974, P i c r a u x 1975). By c o m b i n
ing c h a n n e l l i n g with b a c k s c a t t e r i n g m e a s u r e m e n t s ,
c r y s t a l l o g r a p h i c i n f o r m a t i o n s u c h a s lattice site loca
t i o n o f i m p u r i t i e s o r lattice d i s o r d e r c a n b e deter
m i n e d ( M o r g a n 1973). F i g u r e 5 s h o w s a c h a n n e l l i n g
+
b a c k s c a t t e r i n g s p e c t r u m from a B F 2 - i m p l a n t e d sili
c o n crystal. F i g u r e 6 s h o w s t h e effect o f t h e r m a l a n d
+
laser a n n e a l i n g o n t h e d a m a g e c r e a t e d b y a B F 2
implant. T h e a m o r p h o u s portion of the as-implanted
layer is a n n e a l e d t h e r m a l l y o r b y laser.

4. Microprobe

Analysis

A recent a p p l i c a t i o n of t h e b a c k s c a t t e r i n g t e c h n i q u e
h a s b e e n in t h e n o n d e s t r u c t i v e analysis o f microelec
t r o n i c circuits. T h e utility of these i o n - b e a m tech
n i q u e s h a s b e e n greatly increased b y t h e i n v e n t i o n o f
lenses c a p a b l e o f focusing h i g h - e n e r g y h e a v y - i o n
beams to micrometer dimensions. The combination of
i o n - b e a m analysis a n d m i c r o m e t e r - d i m e n s i o n i o n
b e a m s yields a powerful, n o n d e s t r u c t i v e m e t h o d for
m a t e r i a l s analysis. F i g u r e 7 s h o w s a line-scan b a c k s c a t t e r i n g s p e c t r u m t a k e n w i t h a recently c o n s t r u c t e d
m i c r o b e a m system a t t h e S a n d i a N a t i o n a l L a b o r a t o r
4
+
ies, N e w M e x i c o ( D o y l e et al. 1981). A 3 M e V H e

203

Ion Backscattering

Analysis

Energy

0 8

nuclear m i c r o p r o b e s in microelectronics a p p e a r s t o be
especially attractive.

(MeV)

i.O

See also: Depth Profiling; Secondary-Ion Mass Spectro

metry

*>'.".

random

Bibliography

>.>....

t h e r m a l l ye annealed
C , 15 min
/ 9 5 0

r^ :*^....
:

^^iSJii*...-laser annealed

300

400

reduction in damage by
t h e r m a l a n d laser
annealing

C h a n n e l number

Figure 6
Random and (lOO)-aligned backscattering
spectra for a
+
silicon crystal implanted with BF 2

b e a m of 2 - 5 w a s used t o analyze a n 80 n m thick

(30 wide) gold grid o n a silicon s u b s t r a t e .
Micrometer-size b e a m d i a m e t e r s are particularly
i m p o r t a n t in experiments in which the s a m p l e is very
small, as in the case of s o m e biological studies, for
studies of electronic circuits, o r in m e t a l l u r g y w h e n
individual grains are t o be e x a m i n e d . T h e use of

64

channels

Figure 7
A line-scan
backscattering
spectra produced by analysis of
4
+
a 3 MeV H e beam of 2-5 from 80 nm thick (30
wide) gold grid on a silicon substrate
204

Andersen , Ziegler J F 1977 Hydrogen: Stopping Powers

and Ranges in All Elements. Pergamon, Oxford
Brice D 1973 Theoretical analysis of the energy spectra of
backscattered ions. Thin Solid Films 19: 121-35
Chow , Hamzeh , Steckl A J 1982 Thermal oxidation
of niobium suicide thin films. J. Appl. Phys. 54: 2716-19
Chu W-K, Mayer J W, Nicolet M-A 1978 Backscattering
Spectrometry. Academic Press, New York
Dearnaley G 1973 Ion penetration and channeling. In:
Dearnaley G, Freeman J H, Nelson R S, Stephen J (eds.)
1973 Ion Implantation. North-Holland, Amsterdam
Doyle L, Wing D, Peercy S 1981 Nuclear microprobe
analysis. In: Geiss R (ed.) 1981 Proc. Annual Conf.
Microbeam Analysis. San Francisco Press, San Francisco,
CA, pp. 79-86
Foti G, Mayer J W, Rimini 1977 Backscattering spectro
metry. In: Mayer J W, Rimini (eds.) 1977 Ion Beam
Handbook for Material Analysis. Academic Press, New
York, pp. 21-65
Gemmell D S 1974 Channeling and related effects in the
motion of charged particles through crystals. Rev. Mod.
Phys. 46: 129-227
Mayer J W, Eriksson L, Davies J A 1970 Ion Implantation in
Semiconductors, Silicon and Germanium. Academic Press,
New York
Mayer J W, Tu 1974 Analysis of thin-film structures
with nuclear backscattering and x-ray diffraction. J. Vac.
Sci. Technol. 11: 86-93
Morgan D V (ed.) 1973 Channeling: Theory, Observation
and Applications. Wiley, New York
Picraux S 1975 Lattice location of impurities in metals and
semiconductors. In: Ziegler J F (ed.) 1975 New Uses of Ion
Accelerators. Plenum, New York, pp. 229-81
Wolicki A 1975 Material analysis by means of nuclear
reactions. In: Ziegler J F (ed.) 1975 New Uses of Ion
Accelerators. Plenum, New York, pp. 159-228
Ziegler J F 1977 Helium: Stopping Powers and Ranges in All
Elemental Matter. Pergamon, Oxford
Ziegler J F, Baglin J 1971 Determination of surface
impurity concentration profiles by nuclear backscatter
ing. J. Appl. Phys. 42: 2031-40
Ziegler J F, Chu W 19744 Stopping cross sections and
backscattering factors for He ions in matter. At. Data
Nucl. Data Tables 13: 463-89
Ziegler J F, Lever R F, Hirvonen J 1975b Computer
analysis of nuclear backscattering. In: Meyer O, Linker
G, Kappeler F (eds.) 1975 Ion Beam Surface Layer
Analysis, Vol. 1. Plenum, New York, pp. 163-83
Ziegler J F, Mayer J W, Ullrich , Chu W 1975a
Material analysis by nuclear backscattering. In: Ziegler J
F (ed.) 1975 New Uses of Ion Accelerators. Plenum, New
York, pp. 75-158
H. Bakhru
[State University of N e w Y o r k ,
Albany, New York, USA]

J
Junction Transient Spectroscopy
T h e necessity of m o n i t o r i n g electrically active defects
in crystalline s e m i c o n d u c t o r m a t e r i a l s h a s led t o t h e
d e v e l o p m e n t of j u n c t i o n t r a n s i e n t m e a s u r e m e n t tech
niques. T h e m o s t i m p o r t a n t of t h e v a r i o u s m e t h o d s is
deep-level t r a n s i e n t s p e c t r o s c o p y ( D L T S ) w h i c h h a s
p r o v e n t o b e a powerful research tool for c h a r a c t e r i z
ing t h e electrical p r o p e r t i e s of p o i n t defects in b o t h
elemental a n d c o m p o u n d s e m i c o n d u c t o r s . T h i s sensi
tive s p e c t r o s c o p y m e a s u r e s deep-level defect c o n c e n
9
3
t r a t i o n s as low as 10 c m " in t h e j u n c t i o n region of a
s e m i c o n d u c t o r device. Since t h e processed device g e o
m e t r y c a n often be used a s a s a m p l e configuration,
D L T S can be a nondestructive measurement. In addi
tion t o the c o n c e n t r a t i o n of deep-level defects in t h e
depletion region, D L T S c a n r o u t i n e l y d e t e r m i n e t h e
spatial profile of t r a p s , t h e energy level for carrier
emission from the defect a n d t h e m a j o r i t y carrier
c a p t u r e cross section. T h e s p e c t r o s c o p i c n a t u r e of
j u n c t i o n t r a n s i e n t m e a s u r e m e n t s h a s b e e n exploited
in e x p e r i m e n t s t h a t h a v e led t o t h e discovery of
r e c o m b i n a t i o n - e n h a n c e d defect diffusion, t h e first
o b s e r v a t i o n of m e t a s t a b l e defect r e a c t i o n s , a n d t h e
c o r r e l a t i o n of energy levels with impurities a n d
r a d i a t i o n - p r o d u c e d p o i n t defects.

1. Junction

Transient

Measurements

J u n c t i o n t r a n s i e n t spectroscopies m o n i t o r t h e electri
cal effects of defects w i t h i n t h e d e p l e t i o n region of a
s e m i c o n d u c t o r j u n c t i o n . A lattice defect (such a s a
vacancy, a n interstitial o r a dislocation), a n i m p u r i t y
(either s u b s t i t u t i o n a l o r interstitial) o r a c o m p l e x of
these simple defects in a crystal c a n i n t r o d u c e electro
nic energy states o r levels i n t o t h e f o r b i d d e n g a p of a
s e m i c o n d u c t o r . I n t e n t i o n a l l y p r o c e s s e d d o p a n t s such
as arsenic o r b o r o n p r o d u c e shallow states in t h e
energy g a p , a p p r o x i m a t e l y 0.03-0.06 eV from their
related b a n d edges. T h e d e e p states, w h i c h a r e
m e a s u r e d b y these spectroscopies, a r e t h o s e w h o s e
energy levels fall d e e p e r in t h e b a n d g a p t h a n
the d o p a n t levels. E v e n small
concentrations
of d e e p levels c a n c o n t r o l t h e carrier lifetime in
semiconductors.
T h e a p p l i c a t i o n of a reverse bias t o a s e m i c o n d u c
t o r j u n c t i o n s t r u c t u r e creates a d e p l e t i o n region free
of m o b i l e carriers. T h e j u n c t i o n c a p a c i t a n c e is a n a l o
g o u s t o t h a t of a parallel-plate c a p a c i t o r w i t h t h e p l a t e
s e p a r a t i o n e q u i v a l e n t t o t h e w i d t h of t h e depleted
region. T h e presence of o c c u p i e d d e e p levels in t h e
m a t e r i a l c h a n g e s this j u n c t i o n c a p a c i t a n c e . All t r a n
sient spectroscopies e m p l o y s o m e m e t h o d t o p e r t u r b

t h e carrier o c c u p a t i o n of defect states a n d t h e n a n a

lyze t h e t r a n s i e n t signals w h i c h a r e a result of the
r e t u r n of t h e j u n c t i o n t o s t e a d y state. Specifically
D L T S s u p e r i m p o s e s a f o r w a r d voltage pulse o n a
reverse-biased d i o d e . T h i s collapses t h e depletion
region, filling t h e t r a p s with carriers. W h e n t h e pulse
is r e m o v e d t h e carriers a r e t h e r m a l l y excited from t h e
t r a p t o t h e related b a n d a n d a r e swept o u t of the
d e p l e t i o n region b y t h e a p p l i e d p o t e n t i a l . T h e result
ing j u n c t i o n c a p a c i t a n c e exhibits a t r a n s i e n t r e s p o n s e
with a characteristic time c o n s t a n t inversely p r o p o r
t i o n a l t o t h e carrier emission r a t e of each defect level.
A s p e c t r u m is g e n e r a t e d b y r e p e a t e d l y pulsing the
s a m p l e a n d c o r r e l a t i n g t h e resulting t r a n s i e n t s with
selected i n s t r u m e n t t i m e c o n s t a n t s , t h u s p r o d u c i n g a
u n i q u e p e a k for e a c h defect a s t h e s a m p l e t e m p e r a t u r e
is r a m p e d from carrier freeze-out ( ~ 50 K ) t o r o o m
t e m p e r a t u r e . L o c k - i n amplifiers, d o u b l e b o x - c a r inte
g r a t o r s a n d e x p o n e n t i a l c o r r e l a t o r s a r e typically
e m p l o y e d t o p r o c e s s a n a l o g t r a n s i e n t signals. A block
d i a g r a m for a system t h a t e m p l o y s a lock-in amplifier
t o m o n i t o r c a p a c i t a n c e t r a n s i e n t s is s h o w n in Fig. 1.
Alternatively, t h e t r a n s i e n t c a n b e digitized a n d a n a
lyzed with software t o p r o d u c e a s p e c t r u m . T h e r e
a r e n u m e r o u s v a r i a t i o n s of j u n c t i o n spectroscopies.
C a r r i e r o c c u p a t i o n c a n also b e p e r t u r b e d with s u b b a n d g a p light o r electron b e a m s , a n d often j u n c t i o n
c u r r e n t o r c h a r g e t r a n s i e n t s a r e a n a l y z e d . Spectra c a n
b e g e n e r a t e d as a function of incident light o r instru
ment rate window. In admittance spectroscopy, the
bias varies sinusoidally a n d a phase-sensitive d e t e c t o r
is used.
R e p r e s e n t a t i v e D L T S spectra t a k e n o n highe n e r g y - p r o t o n - i r r a d i a t e d p h o s p h o r u s - d o p e d silicon
a r e s h o w n in F i g . 2. E a c h p e a k is identified b y a
t h e r m a l a c t i v a t i o n energy w i t h indicating electron
emission from t h e defect t o t h e c o n d u c t i o n b a n d a n d

Bias
supply

Capacitance
meter

:4:s

(out)

Pulse
Itransformerl

Pulse
generator
Ref

X-Y

recorder
7"(mV)

Scope
Lock-In output

Lock-in
amplifier
Mixer

Figure 1
Block diagram of a DLTS system employing a capacitance
meter and lock-in amplifier

205

Junction

Transient

Spectroscopy
b a n d edge. A similar expression c a n be w r i t t e n for
hole emission from a defect t o t h e valence b a n d .
E x p e r i m e n t a l l y , the a c t i v a t i o n energy for carrier
emission from a defect t o t h e nearest b a n d edge ET is
o b t a i n e d from t h e slope of a n A r r h e n i u s p l o t of In
2
!
T en~ vs 1 0 0 0 / using E q n . (1). T h e emission r a t e en is
the inverse of t h e time c o n s t a n t of t h e m e a s u r e d
t r a n s i e n t a n d m u s t be d e t e r m i n e d i n d e p e n d e n t l y for
each e x p e r i m e n t a l D L T S system. T h e value of is the
t e m p e r a t u r e of t h e spectral p e a k m a x i m u m .
T h e s e c o n d process i m p o r t a n t in analyzing j u n c t i o n
t r a n s i e n t m e a s u r e m e n t s is the c a p t u r e of carriers at a
- 1
defect. Defect c a p t u r e of majority carriers c ( s ) fol
lows t h e r e l a t i o n s h i p

E,(O.I8eV)

c = <>

(2)
- 3

w h e r e is t h e m a j o r i t y carrier c o n c e n t r a t i o n ( c m ) ,
<v> is t h e t h e r m a l velocity of t h e carriers a n d is the
2
m a j o r i t y carrier c a p t u r e cross section ( c m ) . T h e de
fect c a p t u r e r a t e c is d e t e r m i n e d experimentally a n d
t h e calculated defect c a p t u r e cross section is used with
t h e defect a c t i v a t i o n energy ET t o identify the spectral
feature.

3. Semiconductor

Temperature (K)

Figure 2
DLTS spectra of radiation-induced defects in
phosphorus-doped silicon

indicating h o l e emission t o the valence b a n d . T h e

p e a k height is a direct m e a s u r e of t h e defect c o n c e n
t r a t i o n . T h e i n s t r u m e n t time c o n s t a n t used t o p r o d u c e
the spectra w a s 1.8 m s .

2. DLTS

Theory

A n u n d e r s t a n d i n g of carrier emission a n d c a p t u r e a t a
defect in a s e m i c o n d u c t o r j u n c t i o n d e p l e t i o n region is
necessary t o a n a l y z e the o u t p u t of j u n c t i o n spectros
copies.
T h e r m a l carrier emission from a d e e p level follows
- 1
B o l t z m a n n statistics. T h e emission r a t e en ( s ) of a n
electron from a defect of energy ET (eV) is given by
en ~ JJLi-

[ - (Ec - ET)/kT]

e x p

(1)

w h e r e is t h e defect state c a p t u r e cross section

2
for electrons ( c m ) , <vM> is t h e a v e r a g e t h e r m a l
- 1
velocity for electrons ( c m s ) , Ec is the c o n d u c
tion b a n d energy (eV), k is B o l t z m a n n ' s c o n s t a n t
1
(8.61 x l O ^ e V K ' ) , is t h e a b s o l u t e t e m p e r a t u r e
(K), g is t h e d e g e n e r a c y of t h e level a n d Nc is the
- 3
effective density of states ( c m ) a t t h e c o n d u c t i o n

206

Materials

Characterization

T r a n s i e n t s p e c t r o s c o p y requires t h e filling a n d e m p t y
ing of t r a p s w i t h i n a j u n c t i o n d e p l e t i o n region. T h e r e
fore, devices such a s S c h o t t k y b a r r i e r s , p-n j u n c t i o n s ,
metal-oxide semiconductor structures,
field-effect
t r a n s i s t o r s , light-emitting d i o d e s a n d s e m i c o n d u c t o r
lasers a r e p r o p e r test s t r u c t u r e s . S c h o t t k y barriers
a n d p-n j u n c t i o n s a r e easily fabricated in a l a b o r a
t o r y e n v i r o n m e n t a n d a r e used t o characterize b u l k
materials.
T h e spectroscopic detection limit is a p p r o x i m a t e l y
5
1 0 " times t h e b u l k free carrier c o n c e n t r a t i o n . T h e r e
fore, these m e t h o d s a r e least effective w h e n applied t o
heavily d o p e d s e m i c o n d u c t o r s .
D L T S d o e s n o t p r o v i d e s t r u c t u r a l o r chemical
i n f o r m a t i o n a b o u t a defect. H o w e v e r , extensive
m a t e r i a l s studies o n defects in silicon, in c o n j u n c t i o n
with chemically specific m e a s u r e m e n t s such as p h o t o luminescence, infrared s p e c t r o s c o p y a n d electron
p a r a m a g n e t i c r e s o n a n c e h a v e resulted in t h e identifi
c a t i o n of over 200 D L T S p e a k s . A representative
library is given in T a b l e 1. T h e defect identity (i m e a n s
interstitial, s indicates s u b s t i t u t i o n a l a n d V refers t o
v a c a n c y ) , t h e t e m p e r a t u r e of t h e spectral p e a k m a x i
m u m (at a n i n s t r u m e n t time c o n s t a n t of 1.8 ms) ( ) ,
t h e t h e r m a l a c t i v a t i o n energy for carrier emission t o
the b a n d edge ET (eV) a n d the majority carrier c a p t u r e
2
cross section ( c m ) a r e listed. C o m p a r i s o n s o f
u n k n o w n spectra with this table d o n o t a u t o m a t i c a l l y
g u a r a n t e e firm defect identifications. K n o w l e d g e of
t h e s a m p l e m a t e r i a l a n d c o n s i d e r a t i o n of its p r o c e s s
ing history is crucial. Often, a d d i t i o n a l e x p e r i m e n t s
a r e required for u n a m b i g u o u s defect identification.

Junction

Transient

Spectroscopy

Table 1
DLTS library of defects in silicon

Defect

()

Ag
Ag
Au
Au
Au-Fe
Cr rB c

184
286
288
173
170
123
108
112
243
267
59

C r

CU;BS
Cu
F e
F

ie B
r s

Fe rAl s
Fe rAl s
Fej-Ga,
Fe-In s
Fe rIn s
Mn rB s
Miij
Mn;
Mnj
Mo
N i rB s
Ni
Pds
Pd-V
Pts
Disloc
Disloc
Disloc

oD
oD

4. DLTS

251
207
68
216
191
88
257
174
225
206
288
58

(eV)

18

(10 cm )

H(0.36)
400
E(0.51)
100
E(0.53)
100
H(0.35)
1000
E(0.35)
6000
H(0.28)
>5000
E(0.22)
2000
H(0.22)
>60000
H(0.41)
80000
H(0.45)
>4000
H(0.10)
10000
MH(0.13)
MH(0.20)
MH(0.14)
MH(0.23)
MH(0.15)
MH(0.27)
H(0.55)
H(0.25)
E(0.11)
E(0.42)
H(0.28)
1000
H(0.14)
500
E(0.43)
100
E(0.22)
5000
E(0.18)
5000
H(0.32)
800
E(0.38)
4000
H(0.35)
50
E(0.63)
>1000
E(0.07)
E(0.15)

Applications

D L T S research h a s m a d e a n e x t r a o r d i n a r y c o n t r i b u
tion to the current u n d e r s t a n d i n g of defect reactions in
semiconductors. T h e p h e n o m e n o n of r e c o m b i n a t i o n e n h a n c e d defect reactions w a s first discovered in G a A s
a n d analyzed by j u n c t i o n spectroscopy. T h e localized
energy available at a defect as the result of the re
c o m b i n a t i o n of electrons a n d holes can cause en
hanced defect diffusion a n d h a s p r o v e d t o be t h e
reason for e n h a n c e d d e g r a d a t i o n of injection m o d e
semiconductor devices such as G a A s lasers.
C h a r g e - s t a t e - c o n t r o l l e d defect m e t a s t a b i l i t y w a s
first investigated by D L T S . T h e M - c e n t e r in I n P w a s
the first r e p o r t e d m e t a s t a b l e defect a n d it exhibited
different s t r u c t u r a l c o n f i g u r a t i o n s d e p e n d i n g o n t h e
c h a r g e state of t h e defect. S p e c t r o s c o p i c investiga
tions of silicon, G a A s a n d A l G a A s h a v e u n c o v e r e d
a d d i t i o n a l e x a m p l e s of defect m e t a s t a b i l i t y , a n d these
studies h a v e led t o a n u n d e r s t a n d i n g of configura t i o n a l t r a n s f o r m a t i o n s in t e r m s of b o n d i n g c h a n g e s
at the defect site.
T h e i n t r o d u c t i o n of a t o m i c h y d r o g e n w a s initially
s h o w n by D L T S t o p a s s i v a t e t h e electrical activity
p o i n t defects in silicon resulting from laser a n n e a l i n g .
S u b s e q u e n t t r a n s i e n t s p e c t r o s c o p y h a s revealed
h y d r o g e n p a s s i v a t i o n of d e e p a n d shallow levels in
G a A s , G a P , G a A l A s a n d silicon.

Defect

()

V
V

76
79
131
241
142
98
215
235
224
192
69
282
203

v-v
v-v
v-v
v

~i

P-V
As-V
Sb-V
Sn-V
Sn-V
Al-V
Al,
Al rAl s
Bj
B
i
B-V
B rB s
B.-C.
Bj-O;
Cj
Cj
C sSi-C s
C,-Cs

Ps-Ci
Ps-Ci

87
223
190

64
165
206

(eV)

,8

(10 cm )

E(0.09)
H(0.14)
30
H(0.21)
200
E(0.40)
2000
E(0.23)
400
E(0.17)
1000
E(0.44)
4000
E(0.47)
E(0.44)
40
H(0.32)
9
H(0.07)
20
H(0.52)
> 100
H(0.25)
7
H(0.23)
E(0.13)
>100
E(0.45)
700
H(0.32)
H(0.30)
800 000
H(0.29)
E(0.26)
E(0.12)
H(0.27)
70
H(0.36)
70
ME(0.17)
40
ME(0.10)
MH(0.09)
MH(0.05)
ME(0.30)
10
ME(0.21)
ME(0.23)
ME(0.29)

Recently, engineers h a v e b e g u n t o a p p l y j u n c t i o n
t r a n s i e n t t e c h n i q u e s t o t h e e x a m i n a t i o n of t r a c e c o n
t a m i n a t i o n a n d p r o c e s s - i n d u c e d defects in semicon
d u c t o r device m a n u f a c t u r e . D L T S h a s been e m p l o y e d
t o investigate c o n t a m i n a t i o n i n t r o d u c e d b y process
ing furnaces a n d epitaxial r e a c t o r s . D L T S feasibility
studies h a v e e v a l u a t e d n e w p r o c e s s i n g t e c h n i q u e s
such as l o w - t e m p e r a t u r e , h i g h - p r e s s u r e o x i d a t i o n a n d
rapid thermal annealing. Ion-implantation-induced
t r a p s h a v e also been c h a r a c t e r i z e d b y D L T S .
D L T S is also used t o a n a l y z e t h e effect of d e e p
levels o n device p e r f o r m a n c e . D L T S research h a s
c o r r e l a t e d t h e c o n c e n t r a t i o n of gold levels as well as
v a c a n c y o x y g e n a n d d i v a c a n c y defects with t h e
r e d u c t i o n of majority-carrier lifetime in silicon d e
vices. T h e presence of defects related t o silver a n d
nickel w a s s h o w n t o c a u s e excessive l e a k a g e c u r r e n t in
silicon p l a n a r d i o d e s . Devices t h a t exhibited c h a n g e s
in resistivity a n d m i n o r i t y - c a r r i e r lifetime d u r i n g
p r o c e s s i n g were investigated b y j u n c t i o n t r a n s i e n t
m e t h o d s revealing interstitial i r o n a s t h e c a u s e .
D L T S h a s m a t u r e d as a s e m i c o n d u c t o r c h a r a c t e r
ization t e c h n i q u e a n d c o m m e r c i a l l y m a n u f a c t u r e d
s p e c t r o m e t e r s a r e n o w available. It a p p e a r s , there
fore, t h a t D L T S will s o o n b e utilized regularly in
s e m i c o n d u c t o r device m a n u f a c t u r i n g facilities as a
p r o c e s s m o n i t o r . R e s e a r c h is increasing the n u m b e r of

207

Junction

Transient

Spectroscopy

chemically identified defect levels, which a d d s t o the

p o t e n t i a l effectiveness of D L T S in this a r e a .
See also: Semiconducting Materials: Characterization by
Etching; Semiconducting Materials: Electron Microscopy

Bibliography
Benton J L, Kimerling L C 1982 Capacitance transient
spectroscopy of trace contamination in silicon. J. Electrochem. Soc. 129(9): 2098-102

208

Johnson 1986 Deep level transient spectroscopy: defect

characterization in semiconductor devices. Proc. Symp.
Materials Research Society, Vol. 69. Materials Research
Society, Pittsburgh, PA, pp. 75-94
Lang D V 1974 Deep level transient spectroscopy: a new
method to characterize traps in semiconductors. J. Appl.
Phys. 45: 3023-32
Miller G L, Lang D V, Kimerling L C 1977 Capacitance
transient spectroscopy. Annu. Rev. Mater. Sci. 7: 377-448
J. L. B e n t o n
[ A T & T Bell L a b o r a t o r i e s , M u r r a y Hill,
N e w Jersey, U S A ]

L
Laser Microprobe Mass Spectrometry

a r e s h o w n in F i g . 1 a l t h o u g h t h e precise a r r a n g e m e n t
is d e p e n d e n t o n t h e p a r t i c u l a r i n s t r u m e n t used.
G e n e r a l l y , o p e r a t i o n c a n be either in t r a n s m i s s i o n
m o d e , with laser i r r a d i a t i o n of o n e side of a thin
( ~ 1 ) s a m p l e a n d ion e x t r a c t i o n from t h e o p p o s i t e
side, o r in reflection m o d e . T h e reflection m o d e is n o t
only essential for the analysis of b u l k s a m p l e s b u t also
a p p e a r s t o be satisfactory for thin s a m p l e s which are
p e r f o r a t e d by t h e laser pulse.
T h e s a m p l e is viewed t h r o u g h a high-resolution
optical m i c r o s c o p e system w h i c h also serves t o focus
t h e laser pulse o n t o t h e s a m p l e surface. T h e specific
a r e a for analysis is identified a n d defined by the
focused s p o t of a n auxiliary c o n t i n u o u s - w a v e h e l i u m n e o n laser.
In t h e i n s t r u m e n t illustrated in Fig. 1, s a m p l e
viewing, laser i r r a d i a t i o n a n d ion e x t r a c t i o n a r e all
p e r f o r m e d n o r m a l t o the s a m p l e surface by extracting
ions for analysis t h r o u g h a series of axial a p e r t u r e s in
t h e reflecting (Cassegrain) e l e m e n t s of t h e m i c r o s c o p e
objective lens. O t h e r i n s t r u m e n t s use n o n - n o r m a l
incidence of t h e laser b e a m a n d so avoid the Casse
g r a i n lens. A high-stability, precision s a m p l e m a n i p u
l a t o r p r o v i d e s x, y a n d t r a n s l a t i o n s , with o n e axis of
360 r o t a t i o n , a n d p o s i t i o n s t h e s a m p l e with a n accur
acy b e t t e r t h a n 1 . T h e m a x i m u m s a m p l e size is
i n s t r u m e n t d e p e n d e n t b u t specimen c h a m b e r s h a v e
been m a d e t o h a n d l e several s e m i - c o n d u c t o r wafers
200 m m s q u a r e a n d 10 m m in d e p t h , for e x a m p l e .
Although instruments are m a d e to ultrahigh vacuum
s t a n d a r d s , such c o n d i t i o n s generally a r e n o t required

T h e c o m b i n a t i o n of a pulsed, m i c r o f o c u s e d laser
b e a m with a time-of-flight m a s s s p e c t r o m e t e r h a s
allowed t h e d e v e l o p m e n t of c o m m e r c i a l l y available
laser m i c r o p r o b e s ( H i l l e n k a m p et al. 1975, D i n g l e et
al. 1981) w h i c h c a n aid t h e c h a r a c t e r i z a t i o n of m a t e r
ials. In such i n s t r u m e n t s ( k n o w n as L A M M S ) , a s h o r t
pulse of h i g h - e n e r g y laser r a d i a t i o n is focused o n t o
the surface of t h e s a m p l e . T h e very high p o w e r density
in the focused s p o t results in e v a p o r a t i o n a n d p a r t i a l
3
i o n i z a t i o n of a small v o l u m e (a few ) of m a t e r i a l
from t h e s a m p l e surface. A n a l y s i s of t h e resulting i o n s
(either positive o r negative) is effected b y m e a s u r i n g ,
using a time-of-flight m a s s s p e c t r o m e t e r , t h e m a s s - t o c h a r g e r a t i o of either t h e positive o r negative i o n s .
A l t h o u g h a t p r e s e n t t h e t e c h n i q u e is only semi
q u a n t i t a t i v e , it h a s m a n y features w h i c h c a n b e used
with a d v a n t a g e . T h e s e include t h e d e t e c t i o n of i o n s
from all elements (with i s o t o p e d i s c r i m i n a t i o n ) a n d
from m o l e c u l a r species; r e a s o n a b l e trace sensitivity
(to p p m levels); ability t o a n a l y z e a wide r a n g e of
s a m p l e m a t e r i a l s ( c o n d u c t o r s , i n s u l a t o r s a n d organics); m i n i m a l s a m p l e p r e p a r a t i o n ; a n d speed a n d
simplicity of analysis. O f p a r t i c u l a r interest is its role
as a m i c r o p r o b e for d e t e c t i n g o r g a n i c species a n d t h e
light elements, including h y d r o g e n .

1.

Instrumentation

T h e essential features of a typical laser m i c r o p r o b e

Eyepiece

Pilot

laser

He:Ne

-4s

Pulsed laser
-switched

N d : YAG
Frequency

Transmission
mode optics

converter

Ion

deflector
Specimen
Light
objective
ens
(transmission

Ion

detector

mode)
Ion-extraction
optics

and

objective

light
lens

(reflection
Transient

recorder

Preamplifer

mode)

Figure 1
Schematic diagram of a typical laser microprobe mass spectrometer (Cambridge Mass Spectrometry Ltd. LIMA III)

209

Laser Microprobe

Mass

Spectrometry

for r o u t i n e analyses a n d a v a c u u m of a b o u t 1 0 " 4 P a is

typically used.
T o effect analysis, a laser pulse is p r o v i d e d by a Q switched n e o d y m i u m - Y A G laser, t h e f u n d a m e n t a l
wavelength of which is 1064 n m . T h i s pulse is usually
f r e q u e n c y - q u a d r u p l e d (wavelength of 266 n m ) in
o r d e r t o e n h a n c e p e r f o r m a n c e a n d , as a n e x a m p l e ,
this will give a m a x i m u m pulse energy of a p p r o x i
mately 20 m J a n d a pulse length of 4 - 8 ns. T h e
resulting p o w e r density in the diffraction-limited
b e a m focused a t the surface of the s a m p l e c a n be
varied a n d typically lies in t h e r a n g e 10 1 110 15 W m ~ 2 .
This p o w e r density is sufficient t o e v a p o r a t e a n d
partially ionize a small v o l u m e of t h e s a m p l e w h i c h
forms a p l a s m a j u s t a b o v e t h e surface of t h e s a m p l e .
By m e a n s of a p o t e n t i a l difference V b e t w e e n t h e
s a m p l e a n d e n t r y t o the time-of-flight m a s s spectr
o m e t e r , either the positive o r negative ions (of c h a r g e
ne w h e r e e is the m a g n i t u d e of t h e c h a r g e o n a n
electron a n d is a n integer) c a n be accelerated i n t o
the m a s s s p e c t r o m e t e r a n d in d o i n g so gain kinetic
energy w h e r e
E=neV

(1)

T h e velocity t h a t is r e a c h e d b y a particle of m a s s
m is related t o t h e a b o v e kinetic energy by t h e classical
equation
E = $mv2

(2)

By c o m b i n i n g the a b o v e e q u a t i o n s a n d r e a r r a n g i n g ,

Figure 2
Scanning electron micrograph of laser crater made at
relatively high input laser energy
s p e c t r o m e t e r drift t u b e using either a venetian-blind
electron multiplier o r m i c r o c h a n n e l plates. A fast
(e.g., 60 M H z ) t r a n s i e n t r e c o r d e r a c q u i r e s t h e result
ing amplified signals t o p r o v i d e a s p e c t r u m of ion
a b u n d a n c e versus time. D a t a a r e usually transferred
to a m i c r o c o m p u t e r for c o n v e r s i o n t o ion a b u n d a n c e
versus m a s s - t o - c h a r g e r a t i o , for further d a t a analysis
o r m a n i p u l a t i o n , a n d / o r for o u t p u t as a video display,
h a r d c o p y o r p e r m a n e n t s t o r a g e o n m a g n e t i c disk.

(3)
T h u s , ions of different m a s s - t o - c h a r g e r a t i o s will
a t t a i n different t e r m i n a l velocities a n d , if allowed t o
drift in a field-free region of length / (the drift t u b e ) ,
will be s e p a r a t e d in time t. A c c o r d i n g l y , a n ion
d e t e c t o r a t t h e e n d of t h e drift t u b e s h o u l d receive a
series of precise p a c k e t s of i o n s , e a c h c o r r e s p o n d i n g
t o a specific m a s s - t o - c h a r g e r a t i o .
In fact, the ions f o r m e d b y laser a b l a t i o n d o n o t all
h a v e zero kinetic energy a n d so the time-of-flight m a s s
s p e c t r o m e t e r generally includes s o m e w a y of m a k i n g
a s e c o n d - o r d e r c o r r e c t i o n of t h e relatively large
s p r e a d in initial ion energies. In essence, t h e a i m is t o
give the higher-energy ions a slightly longer flightpath
so t h a t all t h e i o n s of a given m a s s - t o - c h a r g e r a t i o
arrive a t t h e e n d of t h e flight t u b e t o g e t h e r . T h i s is
a c c o m p l i s h e d either b y using a folded drift t u b e (as
s h o w n in F i g . 1) in o r d e r t o i n c o r p o r a t e a n electrosta
tic reflecting element ( M a m y r i n et al. 1973) o r b y a
curved flight t u b e i n c o r p o r a t i n g a t o r o i d a l electrosta
tic field ( P o s c h e n r i e d e r 1972). I n b o t h cases, t h e i o n s
of h i g h e r energy (which a r e travelling faster) p e n
e t r a t e further i n t o t h e electrostatic field before being
repelled b y t h e field t h a n t h o s e of lower energy ( b u t
s a m e m a s s - t o - c h a r g e r a t i o ) ; hence a longer
flightpath
is t a k e n b y t h e higher-energy i o n s .
I o n s a r e detected a t the e n d of the m a s s -

210

2.

Performance

T h e spatial r e s o l u t i o n of t h e t e c h n i q u e is related t o
the d i m e n s i o n s of t h e laser-induced crater, c o m m o n l y
from 3 t o < 1 in d i a m e t e r a n d s o m e t e n t h s of a
m i c r o m e t e r in d e p t h a t a typical p o w e r density of
1 0 14 W m ~ 2 (see Fig. 2). C r a t e r characteristics d e p e n d
strongly o n s a m p l e m a t e r i a l a n d o n laser p o w e r
density. I n p a r t i c u l a r , the d e p t h r e m o v e d p e r pulse
h a s been varied from < 0.1 for a silicon nitride
layer o n a microcircuit t o ~ 30 in polyvinyl
chloride) ( P V C ) . T h e u l t i m a t e limit of lateral resolu
tion is g o v e r n e d by t h e need t o focus the laser b e a m
o n t o t h e surface of t h e s a m p l e a n d so it is unlikely t o
fall m u c h below 1 . H o w e v e r , there is scope for t h e
t e c h n i q u e t o b e c o m e m o r e surface specific by r e m o v
ing a few n a n o m e t e r s in d e p t h , o r even a surface
m o n o l a y e r . A t present, relatively high laser p o w e r s
a r e used in o r d e r n o t only t o r e m o v e m a t e r i a l from
t h e surface of a s a m p l e , b u t also t o c a u s e e n o u g h
i o n i z a t i o n so t h a t a signal c a n be collected. Interest is
g r o w i n g in t h e use of " p o s t - i o n i z a t i o n " which is a
process t h a t uses a second energy source t o ionize
n e u t r a l s (which a r e m o r e a b u n d a n t t h a n ions) f o r m e d
by t h e original laser pulse. If this is successful, for
instance, by m e a n s of a second laser with a n optical
p a t h p e r p e n d i c u l a r t o t h e original laser p a t h a n d

Laser

focused j u s t a b o v e t h e surface of t h e s a m p l e , t h e n it
m i g h t be possible t o r e d u c e t h e p r i m a r y laser p o w e r
sufficiently so t h a t only surface layers a r e r e m o v e d
from the s a m p l e .
M a s s r e s o l u t i o n for L A M M S i n s t r u m e n t s is
generally expressed by t h e r a t i o of p e a k p o s i t i o n m t o
p e a k w i d t h 8m for a single p e a k . O w i n g t o t h e s p r e a d
in ion energies arising from t h e l a s e r - s a m p l e i n t e r a c
tion, t h e ions a r e n o t all accelerated from t h e s a m e
initial energy a n d so m a s s p e a k s h a v e finite w i d t h s .
While the use of either t h e M a m y r i n o r P o s c h e n r i e d e r
s p e c t r o m e t e r design c a n c o m p e n s a t e for s o m e of t h e
energy s p r e a d s , values of m/8m in t h e r a n g e 5 0 0 - 8 0 0
at m a s s 208 (lead) a r e r e p o r t e d ; these values a r e
c o n s i d e r a b l y lower t h a n t h e theoretical figure of 5 0 0 10 000 for such a m a s s s p e c t r o m e t e r . N o n e t h e l e s s , t h e
time-of-flight a p p r o a c h h a s t h e i m p o r t a n t ability of
being able to detect q u a n t i t a t i v e l y all ion species
resulting from a single laser pulse of s h o r t d u r a t i o n
( 4 - 8 ns). Positive o r negative i o n s c a n be selected (by
switching p o l a r i t y of t h e s a m p l e relative t o t h e timeof-flight t u b e ) . T h e s e c a n o r i g i n a t e from all e l e m e n t s
(including h y d r o g e n a n d o t h e r light elements, unlike
x-ray microanalysis) with d i s c r i m i n a t i o n b e t w e n iso
topes as well as from molecules. T h e relative sensi
tivity t o different e l e m e n t s a p p e a r s t o lie w i t h i n a
factor of ten a t m o s t ; it is m o r e u n i f o r m a t a w a v e
length of 266 n m t h a n 532 n m a n d is n e a r u n i t y for
elements of similar i o n i z a t i o n energy. T h e d e t e c t i o n
limit for trace e l e m e n t s is n o r m a l l y ~ 10 p p m for a
single laser pulse a n d ~ 1 p p m h a s been achieved for
b o r o n in silicon. It m a y b e n o t e d t h a t 1 p p m in a n
analyzed d e p t h of ~ 0 . 5 c o r r e s p o n d s t o a few
percent of t h e a t o m s p r e s e n t in a surface m o n o l a y e r .
T h u s , while n o t specifically i n t e n d e d as a surfacesensitive analysis t e c h n i q u e such as s e c o n d a r y - i o n
m a s s s p e c t r o s c o p y ( S I M S ) , A u g e r electron s p e c t r o s
c o p y o r electron s p e c t r o s c o p y for chemical analysis,
L A M M S c a n p r o v i d e surface i n f o r m a t i o n .
U n l i k e m a n y analysis t e c h n i q u e s , L A M M S is a p
plicable t o a wide r a n g e of m a t e r i a l s , including n o t
only c o n d u c t o r s b u t s e m i c o n d u c t o r s , glasses a n d cer
amics, p o l y m e r s a n d c o m p o s i t e s , c o a t i n g s a n d
p o w d e r s , a n d o r g a n i c a n d biological s a m p l e s .
T h e t e c h n i q u e also h a s been r e g a r d e d as t h e first
organic microprobe analyzer although the interpre
t a t i o n of t h e resulting m a s s s p e c t r u m c a n b e m o r e
involved for o r g a n i c s t h a n for m e t a l s since t h e p o s
sible c o m b i n a t i o n s of m o l e c u l a r a n d / o r f r a g m e n t i o n s
b e c o m e s m u c h greater. F o r e x a m p l e , m o l e c u l a r i o n s
m a y form in a n u m b e r of w a y s (Hercules 1983)
including:
(a) i o n - m o l e c u l a r r e a c t i o n s (e.g., molecule p l u s
fragment ion);

(b) gain o r loss of a p r o t o n ; a n d

(c) gain o r loss of a n electron.
I n a d d i t i o n , high laser energies m a y c a u s e a m o l e c u l e

Microprobe

Mass

Spectrometry

o r m o l e c u l a r ion t o f r a g m e n t i n t o a n u m b e r of ions of
lower m a s s - t o - c h a r g e r a t i o . N o n e t h e l e s s , the frag
m e n t ion p a t t e r n often c a n be distinctive for a p a r t i c u
lar m o l e c u l e a n d this allows r a p i d identification of
molecules with m i c r o m e t e r - s c a l e spatial resolution.
Very high m a s s (e.g., several t h o u s a n d ) ions c a n also
be detected.
F o r r o u t i n e use, t h e t e c h n i q u e is very quick a n d
simple: s a m p l e p r e p a r a t i o n is s t r a i g h t f o r w a r d ; the
time t a k e n t o l o a d a n e w s a m p l e t h r o u g h t o o b t a i n i n g
a m i c r o a n a l y s i s of a selected region is of t h e o r d e r of
m i n u t e s ; a n d further m i c r o a n a l y s e s m a y t h e n be per
f o r m e d a t intervals of s e c o n d s . S a m p l e s m a y be
p r e c l e a n e d in situ by use of a defocused laser pulse,
a n d r e p e a t e d m i c r o a n a l y s e s a t t h e s a m e p o i n t give the
possbility of c o a r s e depth-profiling, r a p i d l y p e n e t r a t
ing several m i c r o m e t e r s i n t o a s a m p l e .

3.

Applications

T h e r a n g e of m a t e r i a l s a n d analytical p r o b l e m s t o
w h i c h l a s e r - p r o b e m i c r o a n a l y s i s m a y usefully be a p
plied a p p e a r s t o be very wide a n d h a s certainly n o t yet
been fully e x p l o r e d , still less c h a r a c t e r i z e d in a n y
detail. V a r i o u s a p p l i c a t i o n s of t h e L A M M S t e c h n i q u e
t o p r o b l e m s in m a t e r i a l s science h a v e been reviewed
( C o n z e m i u s et al. 1983, Michiels et al. 1984, S o u t h o n
et al. 1985). S o m e a p p l i c a t i o n s of t h e t e c h n i q u e ,
necessarily u n r e p r e s e n t a t i v e of t h e full scope of the
t e c h n i q u e , a r e i n d i c a t e d below.
3.1 Microanalysis
of Borides in a Nickel-Base
Superalloy
N i c k e l - b a s e superalloys a r e h i g h - p e r f o r m a n c e m a t e r
ials used principally for c o m p o n e n t s in t h e h o t z o n e of
g a s - t u r b i n e a e r o e n g i n e s . T h e m i c r o s t r u c t u r e s of these
alloys a r e extremely c o m p l e x . A m o n g their m o r e
interesting features a r e s e c o n d - p h a s e particles c o n
t a i n i n g b o r o n , usually of c o m p o s i t i o n M 3 B 2 w h e r e
is a m e t a l . It is i m p o r t a n t t o identify t h e metallic
c o n s t i t u e n t s a n d t o establish w h e t h e r the particles
c o n t a i n c a r b o n , w h i c h c a n b e difficult t o m e a s u r e
a c c u r a t e l y by c o n v e n t i o n a l e l e c t r o n - m i c r o p r o b e tech
n i q u e s . F i g u r e 3 is a typical m a s s s p e c t r u m , resulting
from a f r e q u e n c y - d o u b l e d (wavelength of 532 n m )
laser pulse a t relatively low intensity, from t h e m a t r i x
p h a s e of t h e alloy. All of t h e expected metallic consti
t u e n t s of t h e alloy a r e clearly seen, w i t h t h e a d d i t i o n
of a trace of ^ C a p r o b a b l y p r e s e n t as a surface
c o n t a m i n a n t . Q u a n t i t a t i v e l y , t h e relative isotopic
a b u n d a n c e s of a given element a r e correctly repre
sented (typically t o b e t t e r t h a n 1 % o f the t o t a l
elemental c o n c e n t r a t i o n ) a n d elements of low o r
c o m p a r a b l e i o n i z a t i o n energy a p p e a r in t h e expected
p r o p o r t i o n s . H o w e v e r , there is s o m e d i s c r i m i n a t i o n
a g a i n s t e l e m e n t s of h i g h e r i o n i z a t i o n energy, the
c o b a l t a n d nickel p e a k s ( , = 7.86, 7.62 eV) being
lower t h a n expected relative t o c h r o m i u m , t i t a n i u m

211

Laser Microprobe

Mass

Spectrometry

Al
Nii

xlO

"Co
6 0

Ni

Cg

20

30

40
Mass

Zrf

M(

'"Ni
62 Ni
fi

*Ni

T T T T W
I

50
number

Figure 3
LAMMS positive-ion mass spectrum from a single laser pulse of relatively low intensity incident on the matrix phase of a
nickel-base superalloy. Note the change of scale at the high-mass end of the spectrum

a n d a l u m i n u m (is, = 6.76, 6.82, 5.98 eV, respectively).

T h i s d i s c r i m i n a t i o n is less m a r k e d a t higher laser
intensities a n d with f r e q u e n c y - q u a d r u p l e d
laser
pulses (wavelength of 266 n m r a t h e r t h a n 532 n m ) .
M
A s r e g a r d s detection sensitivity,
N i and ^ Z r
(is, = 6 . 8 4 e V ) , expected t o be p r e s e n t at ~ 0 . 5 a t . %
a n d < 1 0 0 p p m , respectively, a r e clearly visible even
at this low laser intensity. I n fact, a section of t h e m a s s
s p e c t r u m from t h e m a t r i x p h a s e of t h e alloy a t a high
laser intensity s h o w s a significant p e a k o w i n g t o
h y d r o g e n a d s o r b e d from the v a c u u m e n v i r o n m e n t
U
a n d , i m p o r t a n t l y , a p e a k o w i n g t o B visible a b o v e
the noise level. B o r o n is expected t o b e p r e s e n t in t h e
m a t r i x p h a s e of t h e alloy at < 5 p p m c o n c e n t r a t i o n ,
so this result suggests a detection limit of a few p a r t s
p e r million even for a n element of relatively high
ionization energy. I n Fig. 4, a s p e c t r u m from a b o r i d e
particle a t high laser intensity, t h e r a t i o of t h e p e a k
1 0
n
1 2
a r e a s of B : B : C is 2 1 . 2 0 : 7 8 . 5 5 : 0 . 2 5 ; a c a r b o n - t o b o r o n r a t i o of 1:400. T h i s implies, after allowing for
t h e relative sensitivity of the t e c h n i q u e to the t w o
elements, the i m p o r t a n t result t h a t t h e c a r b o n - t o b o r o n r a t i o in the b o r i d e particles is a few p e r c e n t a t
m o s t , c o n t r a r y t o s o m e p r e v i o u s suggestions.
3.2 Identification of an Inclusion in a Polymer Film
A film of P V C 250 thick c o n t a i n e d a n u n k n o w n
particle of r o u g h l y circular cross section a n d
212

~ 200 d i a m e t e r w h e n viewed n o r m a l t o t h e p l a n e
of t h e film. P r i o r t o analysis of t h e particle, a series of
spectra were o b t a i n e d from the p o l y m e r a t relatively
high laser p o w e r . All of these s p e c t r a were similar a n d

"B

iob

10
Moss

15

20

25

30

number

Figure 4
Section of the positive-ion spectrum at high laser intensity
from a boride particle in the nickel-base superalloy,
showing the low carbon-to-boron ratio in the boride phase

Laser Microprobe

c 3x

c
I .
!
10

1
20

lul
1
30

c 5x *

C 6X

U
40

Moss

50

60

70

80

number

(a)

Mass

lil

lie:

number

(b)

Figure 5
Positive-ion spectra of poly (vinyl chloride):
(a) characteristic positive-ion LAMMS spectrum of
polyvinyl chloride) at relatively high laser intensity;
(b) positive-ion spectrum obtained during depth profiling
by repeated laser pulsing at the same point on a polyvinyl
chloride) film containing
an inclusion.
The groups
of
+
+
+
+
peaks designated C 3 X , C 4 X , C 5 X and C 6 X in (a) are
greatly diminished,
and groups
of peaks due to the
+
+
isotopes of Ti and to TiO have become prominent

served t o establish t h e " s t a n d a r d " s p e c t r u m of t h e

P V C , illustrated in Fig. 5a. T h e positive-ion s p e c t r u m
of the P V C is c o m p l e x : it clearly c o n t a i n s s o d i u m a n d
p o t a s s i u m , C a n d C H m f r a g m e n t s , b u t t h e identities
of s o m e of these p e a k s a r e n o t o b v i o u s . It is p r o b a b l e
t h a t s o m e p e a k s a r e d u e t o c h l o r i d e ions a l t h o u g h
m o s t of t h e c h l o r i n e a p p e a r s in the negative-ion
s p e c t r u m ; all p e a k s a b o v e m a s s 80 c o u l d be a t t r i b u t e d
to Cn a n d C H m. T h e laser p r o b e w a s t h e n p o s i t i o n e d
a b o v e the u n k n o w n particle a n d a series of laser
pulses were directed a t t h e s a m e s p o t . T h e first three
of these gave t h e " s t a n d a r d " P V C s p e c t r u m . T h e
fourth pulse gave t h e s p e c t r u m of Fig. 5b, in w h i c h

Mass

Spectrometry

the characteristic P V C p e a k s a r e m a r k e d l y diminished

b u t characteristic sets of p e a k s d u e to the t i t a n i u m
i s o t o p e s a t m a s s e s 4 6 - 5 0 a n d to T i O a t 6 2 - 6 6 are
+
evident, a n d T i C i also a p p e a r . O n the fifth laser
pulse, t h e t i t a n i u m - c o n t a i n i n g s p e c t r u m was even
m o r e intense, t h e n w e a k e r o n the sixth pulse, a n d the
seventh pulse a g a i n r e p r o d u c e d the s t a n d a r d P V C
s p e c t r u m . T h i s L A M M S analysis clearly s h o w e d the
particle t o be T i 0 2 o r s o m e t i t a n i u m - o x y g e n c o n t a i n
ing species.
S u b s e q u e n t light m i c r o s c o p y s h o w e d t h a t the
single-pulse laser c r a t e r s in t h e P V C were ~ 20
d i a m e t e r . E x a m i n a t i o n of a section t h r o u g h t h e film
s h o w e d t h a t the particle w a s n o t spherical b u t flat
tened n o r m a l t o the film, ~ 50 in thickness a n d
lying ~ 100 from b o t h t o p a n d b o t t o m surfaces of
the film. T h e laser-pulse sequence h a d n o t p e n e t r a t e d
the particle a t its thickest p o i n t a n d each laser pulse
h a d r e m o v e d ~ 30 of P V C o r ~ 10 of T i 0 2 at
the relatively high intensity which w a s e m p l o y e d for
such a thick film. T h e d e p t h resolution of the
L A M M S d e p t h profiling d e m o n s t r a t e d here o n a
relatively gross scale h a s been s h o w n t o be better t h a n
0.1 a n d c a n p r o b a b l y be r e d u c e d further by a p p r o
p r i a t e modifications of e x p e r i m e n t a l p r o c e d u r e , for
e x a m p l e , by the use of p o s t - i o n i z a t i o n (see Sect. 2).
3.3 Organic
Materials
L a s e r m i c r o p r o b e m a s s s p e c t r o m e t r y h a s been carried
o u t o n a variety of thin sections of o r g a n i c samples
m u c h of t h e early w o r k being o n such m a t e r i a l s using
t h e t r a n s m i s s i o n m o d e . Laser p o w e r density clearly
h a s a d o m i n a n t influence o n t h e c h a r a c t e r of o r g a n i c
m a s s spectra. N o n e t h e l e s s , readily i n t e r p r e t a b l e or
ganic spectra m a y be o b t a i n e d especially if low p o w e r
densities a r e e m p l o y e d . T h i s effect is graphically illus
t r a t e d by Figs. 6a, b , which s h o w L A M M S spectra of
t h e dye r h o d a m i n e - B . A t a relatively low laser inten
sity (Fig. 6a), a s t r o n g m o l e c u l a r - i o n p e a k is observed
at m / ~ 4 4 3 with a series of fragment p e a k s of m a s s
d o w n t o ~ 200 which a r e i n t e r p r e t a b l e in t e r m s of loss
of f r a g m e n t s of t h e molecule. A t higher laser intensit
ies, h o w e v e r (Fig. 6b), while traces of the s a m e p e a k s
r e m a i n , the s p e c t r u m is d o m i n a t e d by a series of
p e a k s a t m a s s < 200 which w o u l d clearly be of little
help in identifying a n u n k n o w n o r g a n i c sample. A t
sufficiently low laser intensities, h o w e v e r , very useful
results c a n be achieved. T h e s p e c t r u m of 1,4-diphen o x y b e n z e n e at a low laser intensity in Fig. 6c shows
essentially only t h e m o l e c u l a r - i o n p e a k at m/n = 262
a n d is c o m p a r a b l e in simplicity with a field d e s o r p t i o n
m a s s s p e c t r u m . A t slightly increased laser intensity,
s o m e fragment p e a k s a p p e a r (Fig. 6d), of which the
m o s t p r o m i n e n t c a n readily be related t o the m o l e c u
lar s t r u c t u r e ; t h e u n a s s i g n e d p e a k s in the s p e c t r u m are
o w i n g t o f r a g m e n t a t i o n of t h e a r o m a t i c ring.
T h u s , a t a low laser intensity, L A M M S clearly h a s
t h e p o t e n t i a l for m i c r o a n a l y s i s a n d identification of
trace a m o u n t s of o r g a n i c m a t e r i a l s , while at the o t h e r

213

Laser

Microprobe

Mass

Spectrometry

COOH

molecular weight W 4 4 2 . 5 7

200

100

\U

300

400

500

200

100

Mass number
(a)

300

400

500

Mass number
(b)
M

V
*
molecular

weight

262

-
50

100

150
Mass

200

250

300

number

(c)

100

150

Mass

200

number

(d)

Figure 6
Examples of LAMMS spectra from organic materials: (a) positive-ion spectrum of rhodamine-B at low laser intensity
showing a strong molecular-ion peak and a series of peaks at lower mass due to loss of fragments of the parent molecule;
(b) positive-ion spectrum of rhodamine-B at a higher laser intensity showing a diminished molecular-ion peak and a
prominent series of noncharacteristic fragments at low molecular weights; (c) positive-ion spectrum and
1,4-diphenoxybenzene at low laser intensity, showing a strong molecular-ion peak and very little fragmentation;
(d) spectrum from diphenoxybenzene at a slightly higher laser intensity than (c), showing the development of a
characteristic fragmentation pattern

e x t r e m e (at high laser intensities) t h e c o m p l e t e disso

ciation i n t o a t o m i c ions of t h e o r g a n i c c o n s t i t u e n t s of
p a i n t films h a s usefully been exploited ( E v a n s et al.
1983) in m e a s u r e m e n t s of t h e metallic c o n s t i t u e n t s of
p a i n t s for forensic a p p l i c a t i o n s a n d as a n aid t o p a i n t
d e v e l o p m e n t a n d quality c o n t r o l .

4.

Quantification

A t present, t h e L A M M S t e c h n i q u e is essentially
s e m i q u a n t i t a t i v e . T h e possibility of o b t a i n i n g fully
q u a n t i t a t i v e L A M M S analyses h a s been discussed for
i n o r g a n i c ( K a u f m a n n 1982, M a u n e y 1985, S o u t h o n et
al. 1985) a n d o r g a n i c ( V e r b u e k e n et al. 1985) m a t e r
ials. O n e p r o b l e m is t h a t t h e t o t a l ion yields in spectra
o b t a i n e d u n d e r n o m i n a l l y identical c o n d i t i o n s s h o w a
significant scatter (e.g., H a r r i s a n d W a l l a c h 1986).

214

T h i s c a n arise from variability of the a c t u a l laser

p o w e r delivered from c h a n g e s in energy density d u e t o
small differences in focusing c o n d i t i o n s o r from shott o - s h o t v a r i a t i o n s in t h e p r o p o r t i o n of laser p o w e r
a b s o r b e d b y t h e specimen o r by t h e p l a s m a as well as
from c h a n g e s in t h e e x t r a c t i o n efficiency of ions from
t h e p l a s m a f o r m e d in t h e region j u s t a b o v e t h e
s a m p l e . T h e scatter c a n be r e d u c e d substantially b y
c o n s i d e r i n g relative ion yields of different elements o r
isotopes, a n d also experimentally by o p t i m i z a t i o n of
p a r a m e t e r s such as laser p o w e r .
K a u f m a n n (1982) h a s suggested t w o possible
a p p r o a c h e s t o quantification; t h e use of w o r k i n g
curves (as used in S I M S ) a n d a m o r e theoretical
m e t h o d . T h e f o r m e r utilizes s t a n d a r d s of k n o w n
c o m p o s i t i o n s t o g e n e r a t e d a t a from w h i c h g r a p h s of
c o r r e c t i o n factors c a n b e p l o t t e d ( a c c o u n t i n g either
for v a r i a t i o n s in c o m p o s i t i o n o r in e x p e r i m e n t a l vari-

Laser

Sampling

ables such as laser p o w e r ) . T h e latter theoretical

a p p r o a c h a t t e m p t s t o m o d e l t h e i o n i z a t i o n p r o c e s s in
the l a s e r - p r o d u c e d p l a s m a a b o v e t h e surface of t h e
s a m p l e , for e x a m p l e , b y u s i n g t h e local t h e r m o
d y n a m i c e q u i l i b r i u m ( L T E ) m o d e l (see S o u t h o n et al.
1985). A t this time, t h e m o r e l a b o r i o u s a p p r o a c h of
g e n e r a t i n g w o r k i n g curves a p p e a r s m o r e reliable.
H o w e v e r , this is a t o p i c of interest n o t only in
L A M M S b u t also in t e c h n i q u e s such a s S I M S . Better
c h a r a c t e r i z a t i o n of t h e t e c h n i q u e , t o g e t h e r with
d e v e l o p m e n t s such as p o s t - i o n i z a t i o n (which m a y
e n s u r e a higher degree of a n d m o r e r e p r o d u c i b l e
ionization of m a t e r i a l from t h e s a m p l e ) , s h o u l d lead
to i m p r o v e m e n t s in quantification.

5.

Conclusion

It is evident t h a t L A M M S h a s great p o t e n t i a l a s a
versatile, quick a n d relatively simple m i c r o a n a l y t i c a l
m e t h o d applicable t o a very wide r a n g e of s a m p l e
materials a n d analytical s i t u a t i o n s . A special feature
is its p o t e n t i a l a s t h e first o r g a n i c m i c r o p r o b e . E v e n
so, it is unlikely t h a t L A M M S in its p r e s e n t semi
q u a n t i t a t i v e f o r m will replace existing m i c r o a n a l y t i c a l
techniques, m a n y of w h i c h h a v e p e r f o r m a n c e s u p e r i o r
to L A M M S in s o m e respects b u t inferior in o t h e r s .
R a t h e r , it is envisaged t h a t t h e versatility, speed a n d
simplicity of L A M M S t o g e t h e r w i t h t h e c o m b i n a t i o n
of capabilities o u t l i n e d a b o v e i n c l u d i n g m i c r o m e t e r
lateral r e s o l u t i o n , s u b m i c r o m e t e r d e p t h r e s o l u t i o n ,
r o u g h l y u n i f o r m sensitivity t o all elements of t h e
periodic table, p p m d e t e c t i o n sensitivity, d e t e c t i o n of
isotopes a n d m o l e c u l a r i o n s , a n d applicability t o a
wide r a n g e of materialswill e n s u r e L A M M S h a s a
place as a c o m p l e m e n t t o existing t e c h n i q u e s , a n d
m a y well m a k e it in future t h e first m e t h o d w h i c h t h e
m i c r o a n a l y s t will a p p l y t o a n e w p r o b l e m before
t u r n i n g t o o t h e r m o r e specialized, b u t less versatile,
m e t h o d s for m o r e detailed c h a r a c t e r i z a t i o n of p a r
ticular features o r p a r a m e t e r s .

Acknowledgement
T h i s article uses e x a m p l e s w h i c h a p p e a r e d previously
in a p a p e r b y S o u t h o n et al. (1984).
See also: Auger Electron Spectroscopy; Electron Microprobe Analysis; Electron Spectroscopy for Chemical Analy
sis; Laser Sampling Inductively Coupled Plasma Mass Spec
trometry; Organic Mass Spectrometry; Secondary-Ion Mass
Spectrometry; Spark-Source Mass Spectrography

Bibliography
Armstrong J (ed.) 1985 Proc. 20th Int. Conf. Microbeam
Analysis Society. San Francisco Press, San Francisco, CA
Conzemius RJ, Simons D S , Shankai Z, Byrd G D 1983

Inductively

Coupled

Plasma

Mass

Spectrometry

Laser mass spectrometry of solids: a bibliography 1963

1982. In: Gooley 1983, pp. 301-32
Dingle T, Griffiths W, Ruckman J C 1981 L I M A - a laser
induced ion mass analyser. Vacuum 31: 571-7
Evans C A Jr, Griffiths W, Dingle T, Southon J, Ninham A J 1983 Microanalysis of bulk samples by laserinduced ion mass analysis. In: Gooley 1983, pp. 101-5
Gooley R (ed.) 1983 Proc. 18th Int. Conf. Microbeam
Analysis Society. San Francisco Press, San Francisco, CA
Harris A, Wallach R 1986 LIMA analysis: quantification
of binary metallic systems. In: Romig A D Jr, Chambers
W F (eds.) 1986 Proc. 21st Int. Conf Microbeam Analysis
Society. San Francisco Press, San Francisco, CA,
pp. 464-6
Hercules D 1983 Organic mass spectrometry using the
laser microprobe. Pure Appl. Chem. 55: 1969-85
Hillenkamp F, Unsold E, Kaufmann R, Nitsche R 1975 A
high-sensitivity laser microprobe mass analyser. Appl.
Phys. 8: 341-8
Kaufmann R 1982 Laser microprobe mass analysis: current
state of the art with special emphasis on bio-medical
applications. In: Heinrich F J (ed.) 1982 Proc. 17th Int.
Conf. Microbeam Analysis Society. San Francisco Press,
San Francisco, CA, pp. 341-58
Mamyrin A, Karataev V I , Schmikk D V , Zagulin V A
1973 The mass-reflectron, a new nonmagnetic time-offlight mass spectrometer with high resolution. Sov. Phys.
JETP (Engl. Transl.) 37: 45-8
Mauney 1985 Quantitative laser microprobe mass spec
trometry: potential and constraints. In: Armstrong 1985,
pp. 299-309
Michiels E, Van Vaeck L, Gijbels R 1984 The use of the laser
microprobe mass analyzer for particle characterization
and as a molecular microprobe. Scanning Electron
Microsc. Pt. 3: 1111-28
Poschenrieder W P 1972 Multiple-focusing time-of-flight
mass spectrometers. Part II TOFMS with equal energy
acceleration. Int. J. Mass Spectrom. Ion Phys. 9: 357-73
Southon J, Harris A, Kohler V L, Mullock S J, Wallach
E R 1985 Quantification and application of laser-probe
microanalysis. In: Armstrong 1985, pp. 310-14
Southon J, Witt C, Harris A, Wallach R, Myatt J
1984 Laser-microprobe mass-analysis of surface-layers
and bulk solids. Vacuum 34: 903-9
Verbueken A H , Bruynseels FJ, Van Grieken R E 1985
Laser microprobe mass analysis: a review of applications
in the life sciences. Biomed. Mass Spectrom. 12: 438-63
E. R. W a l l a c h a n d J. A . L e a k e
[University of C a m b r i d g e ,
Cambridge, U K ]

Laser Sampling Inductively Coupled

Plasma Mass Spectrometry
L a s e r s a m p l i n g inductively c o u p l e d p l a s m a m a s s
s p e c t r o m e t r y ( L S I C P M S ) is a t e c h n i q u e which c a n
be used for t r a c e element analysis of solid materials.
It is a h y b r i d t e c h n i q u e w h i c h c o m b i n e s a highp o w e r laser for s a m p l i n g a solid specimen, a hight e m p e r a t u r e inductively c o u p l e d p l a s m a for ioniza
tion a n d a m a s s s p e c t r o m e t e r for m a s s s e p a r a t i o n

215

Laser Sampling

System

Inductively

Coupled

Plasma

Mass

Spectrometry

computer

Figure 1
Schematic diagram showing the component instruments of an LSICPMS
a n d detection. Laser s a m p l i n g allows a solid specimen
to be s a m p l e d w i t h o u t the need for dissolving t h e
specimen. Because the laser c a n be focused o n a single
spot o r rastered over t h e surface of t h e specimen, the
c o m p o s i t i o n of the b u l k a n d of localized features
(i.e., inclusions, defects) can be studied a n d c o m p a r e d .
In L S I C P M S a h i g h - p o w e r pulsed laser is focused
o n t o a solid specimen held in a n enclosed cell. M a t e r
ial v a p o r i z e d as a result of t h e l a s e r - s o l i d i n t e r a c t i o n
recondenses a n d is swept i n t o the high-energy p l a s m a
of the I C P m a s s s p e c t r o m e t e r . T h e r e it is r e v a p o r i z e d ,
a t o m i z e d a n d ionized a n d is s a m p l e d i n t o a m a s s
spectrometer. T h e ion signal w h i c h is m e a s u r e d is
representative of t h e c o m p o s i t i o n of t h e original
specimen.
W h i l e laser s a m p l i n g is b y n o m e a n s limited t o use
with I C P M S , the c o m b i n a t i o n h a s several a d v a n
tages. T h e I C P M S t e c h n i q u e h a s sufficiently high
sensitivity t o detect trace impurities in m a t e r i a l s s a m
pled by t h e laser, even t h o u g h only 1-10 n g of s a m p l e
a r e t a k e n p e r laser pulse. S p e c t r a r e c o r d e d using
I C P M S a r e less c o m p l e x t h a n t h o s e of emission
spectroscopic techniques. Because spectral interfer
ences a r e fewer, the spectra a r e readily i n t e r p r e t e d a n d
calibrated for either q u a n t i t a t i v e o r s e m i q u a n t i t a t i v e
analysis. T h e ability t o m e a s u r e isotopes m a k e s iso
t o p e r a t i o , dilution a n d t r a c e r studies possible. A
review of I C P M S is given by H o u k (1986).

/.

Instrumentation

F i g u r e 1 is a s c h e m a t i c of the c o m p o n e n t i n s t r u m e n t s
used in L S I C P M S . T h e N d : Y A G laser h a s p r o v e n

216

very useful in this s e t u p because it is relatively low in

10
2
cost a n d p r o v i d e s high i r r a d i a n c e ( > 1 0 W c m " )
a n d g o o d o u t p u t stability, a l t h o u g h o t h e r lasers c o u l d
be used. T h e laser c a n be o p e r a t e d in either the single
o r c o n t i n u o u s pulse m o d e ( 1 0 - 2 0 H z ) resulting in
t r a n s i e n t o r steady-state analytical signals. A n o u t p u t
energy in t h e r a n g e 5 0 - 2 5 0 m J is generally sufficient
t o s a m p l e b o t h highly reflective a n d t r a n s p a r e n t
specimens.
T h e laser is focused o n t o t h e specimen which is held
inside a n enclosed cell. A flow of carrier gas, typically
a r g o n , sweeps t h e laser-vaporized s a m p l e o u t of
the cell a n d i n t o t h e p l a s m a . T h e stage o n which t h e
s a m p l e cell is m o u n t e d c a n be m o v e d t o select t h e
s a m p l i n g p o i n t o n t h e specimen. If t h e stage is m o v e d
d u r i n g i r r a d i a t i o n , a larger a r e a of t h e specimen c a n
be s a m p l e d , p r o v i d i n g a m o r e representative d e t e r m i
n a t i o n of the b u l k c o m p o s i t i o n .
T h e I C P i o n i z a t i o n s o u r c e is sustained by a r a d i o frequency g e n e r a t o r typically o p e r a t e d b e t w e e n
700 W a n d 1 5 0 0 W . A r g o n gas is usually used as t h e
p l a s m a m e d i u m , a l t h o u g h m i x t u r e s c o n t a i n i n g a few
p e r c e n t of n i t r o g e n a r e also used. T h e a r g o n I C P h a s a
gas kinetic t e m p e r a t u r e r a n g e of 6 0 0 0 - 7 0 0 0 a n d ,
for m o s t elements w h i c h h a v e a first i o n i z a t i o n p o t e n
tial below 9 eV, g r e a t e r t h a n 9 0 % i o n i z a t i o n efficiency
is achieved. I o n s a r e e x t r a c t e d from t h e p l a s m a using
a w a t e r - c o o l e d nickel o r p l a t i n u m c o n e with a n orifice
a p p r o x i m a t e l y 1 m m in d i a m e t e r . T h i s c o n e acts as
the front e n d of a differentially p u m p e d s u p e r s o n i c
gas e x p a n s i o n interface consisting of o n e o r m o r e
a d d i t i o n a l c o n e s b e h i n d it. T h e interface is designed
to d i s c r i m i n a t e a g a i n s t n e u t r a l species a n d collect t h e
ions from the p l a s m a for m e a s u r e m e n t .

Laser

Sampling

H a v i n g traversed t h e I C P - M S interface, t h e i o n s
are t h e n directed i n t o t h e m a s s s p e c t r o m e t e r b y m e a n s
of o n e o r m o r e i o n o p t i c elements. T h e q u a d r u p o l e
m a s s s p e c t r o m e t e r is especially suited for L S I C P M S
as it c a n be swept r a p i d l y a c r o s s t h e full m a s s r a n g e of
the p e r i o d i c table. T h i s r a p i d s c a n n i n g allows t r a n
sient signal profiles t o b e a c c u r a t e l y defined for t h e
quantification of m a n y e l e m e n t s , even in a single
signal pulse. I o n s a r e typically detected using a c h a n
8
nel electron multiplier w i t h a gain of u p t o 10 w h i c h is
o p e r a t e d in t h e pulse c o u n t i n g m o d e for m a x i m u m
sensitivity.

2. Laser-Solid

Interaction

T h e m e c h a n i s m s involved in t h e i n t e r a c t i o n of a
focused h i g h - p o w e r laser a n d a solid specimen a r e
c o m p l e x a n d n o t fully u n d e r s t o o d . It is generally
accepted t h a t b o t h a b l a t i o n a n d v a p o r i z a t i o n occur,
b u t the relative i m p o r t a n c e of either m e c h a n i s m
d e p e n d s o n t h e m o d e of laser o p e r a t i o n a n d t h e
c o m p o s i t i o n of t h e s a m p l e itself. H e a t is initially
transferred from t h e laser i n t o t h e solid b y a b s o r p t i o n
of the laser light b y t h e specimen. A t t h e focal p o i n t ,
local t e m p e r a t u r e s rise very r a p i d l y c a u s i n g v a p o r i z a
tion a n d t h e initiation of a t h e r m a l s h o c k front
r a d i a t i n g from t h e s a m p l e surface. A p l a s m a is often
formed in t h e gas j u s t a b o v e t h e s a m p l e surface as a
result of electron emission a n d m u l t i p h o t o n ioniza
tion c a u s e d b y t h e high e n e r g y density at t h e focus of
the laser b e a m . T h i s p l a s m a c a n b e f o r m e d early in t h e
laser pulse a n d c a n a b s o r b a significant p o r t i o n of t h e
r e m a i n i n g laser pulse. T h e energy in t h e p l a s m a c a n
then be transferred b a c k i n t o t h e s a m p l e . T h i s second
ary h e a t i n g c a n result in s a m p l e r e m o v a l b y v a p o r i z a
tion, ion b o m b a r d m e n t a n d physical a b l a t i o n from
the local p r e s s u r e s h o c k .
T w o different m o d e s a r e available for o p e r a t i n g the
N d : Y A G laser. I n t h e free-running m o d e , pulses of
relatively l o n g d u r a t i o n ( 1 5 0 - 2 5 0 \xs) a r e e m i t t e d from
the laser, e a c h actually c o m p r i s i n g a n e n v e l o p e of
m a n y individual s h o r t e r pulse spikes. Because t h e
i n t e r a c t i o n time of t h e pulse e n v e l o p e w i t h t h e solid
specimen is l o n g c o m p a r e d with t h e r a t e of t h e r m a l
transfer within t h e solid, h e a t is c o n d u c t e d relatively
d e e p i n t o t h e specimen u s i n g t h e free-running m o d e .
This establishes a t h e r m a l g r a d i e n t in t h e b u l k of t h e
specimen resulting in t h e fusion a n d v a p o r i z a t i o n of
s a m p l e d m a t e r i a l . R a p i d e x p a n s i o n of t h e h e a t e d
m a t e r i a l causes t h e ejection of m o l t e n particles from
the crater. S o m e of this m a t e r i a l redeposits as a
s h o u l d e r a r o u n d t h e c r a t e r while a q u a n t i t y is ejected
with great force a w a y from t h e s a m p l e d s p o t . V a p o r
ised m a t e r i a l is also released from t h e h e a t e d a r e a a n d
c a n r e c o n d e n s e o n p a r t i c u l a t e nuclei j u s t a b o v e t h e
crater z o n e .
A n alternative m o d e is Q-switched o p e r a t i o n .
U s i n g a n o p t o e l e c t r o n i c gate ( Q switch), t h e efficiency

Inductively

Coupled

Plasma

Mass

Spectrometry

o r q u a l i t y factor Q of t h e laser cavity is m a i n t a i n e d a t

a very low level for a few h u n d r e d m i c r o s e c o n d s . T h i s
inhibits light amplification in t h e cavity a n d m a i n t a i n s
a m a x i m u m p o p u l a t i o n inversion. W h e n t h e ef
ficiency of t h e cavity is " s w i t c h e d " from low to high,
light is allowed t o r e s o n a t e in t h e cavity a n d the
m a x i m u m energy available in t h e laser m e d i u m c a n be
t a p p e d in a very s h o r t p e r i o d of time. T h i s results in
t h e emission of a single, very s h o r t laser pulse c o n t a i n
ing n e a r l y all of t h e laser energy available. In t e r m s of
10
12
2
o u t p u t p o w e r delivered, m o r e t h a n 1 0 - 1 0 W c m
7
a r e available with Q switching while typically 1 0 8
2
10 W c m a r e achieved in free r u n n i n g . A p l a s m a a t
t h e s a m p l e surface is easily p r o d u c e d as a result of the
high energy density of a Q-switched pulse unless very
low laser energy is used.

3. Analytical

Considerations

M a n y i n s t r u m e n t a l o p e r a t i n g p a r a m e t e r s a r e avail
able with w h i c h t o c u s t o m i z e t h e analysis t o a specific
a p p l i c a t i o n . T h e N d : Y A G laser is typically fired a t
10-20 H z b u t c a n also b e activated in single o r m u l t i
ple pulses. C o n t i n u o u s p u l s i n g (typically > 200 pulses
p e r s a m p l i n g ) results in a steady r e m o v a l of s a m p l e
from t h e specimen a n d a s t e a d y - s t a t e signal, while a
single pulse results in discrete s a m p l i n g a n d a t r a n
sient signal. A single laser pulse minimizes t h e i m p a c t
of t h e laser o n t h e s a m p l e p r o v i d i n g the best spatial
r e s o l u t i o n , b u t it also results in t h e smallest analytical
signal (see Fig. 2). S t e a d y - s t a t e pulsing results in the
p o o r e s t spatial r e s o l u t i o n b u t p r o v i d e s t h e best a n a l y
tical sensitivity, a l t h o u g h t h e s p e c t r o m e t e r interface
c a n b e c o m e o v e r l o a d e d b y t h e large a m o u n t of s a m
ple r e m o v e d . Discrete s a m p l i n g b y pulsing the laser
5 0 - 2 0 0 times is a g o o d a l t e r n a t i v e b e c a u s e it p r o v i d e s
relatively high spatial r e s o l u t i o n a n d high sensitivity
b u t only m o d e s t s a m p l e l o a d i n g o n t h e interface.
M o n i t o r i n g a c o n t i n u o u s signal c a n p r o v i d e infor
m a t i o n a b o u t c o m p o s i t i o n a l g r a d i e n t s in t h e s a m p l e .
If a single p o i n t is i r r a d i a t e d , a d e p t h profile m a y be
i n d i c a t e d b y v a r i a t i o n in t h e signal with time. If the
b e a m is swept a c r o s s t h e specimen surface, lateral
c o m p o s i t i o n a l g r a d i e n t s c a n be reflected by v a r i a t i o n s
in signal as a function of t r a n s l a t i o n . If t h e c o m p o s i
tion of t h e b u l k of t h e specimen is t o be d e t e r m i n e d ,
t h e b e a m is usually s c a n n e d a c r o s s t h e s a m p l e . O t h e r
wise, several individual p o i n t analyses c a n be inte
g r a t e d . T h e degree t o w h i c h t h e a n a l y t e s of interest
a r e d i s t r i b u t e d h e t e r o g e n e o u s l y in t h e s a m p l e c a n
limit t h e precision of t h e m e a s u r e m e n t . F o r b u l k
analysis, a larger laser b e a m s p o t size is generally
desirable for a m o r e representative s a m p l i n g of the
specimen. Q-switched o p e r a t i o n usually results in a
larger surface c r a t e r as a result of t h e p l a s m a induced
a b o v e t h e specimen surface. F r e e - r u n n i n g o p e r a t i o n
n o r m a l l y results in s a m p l i n g s p o t s with a m u c h
smaller d i a m e t e r , a l t h o u g h m u c h d e e p e r t h a n those

217

Laser Sampling

Inductively

Coupled

Plasma

Mass

I0

/
4

--/-
V
/
/

i<-

10

Number

10*

of

laser

I0

pulses

Figure 2
LSICPMS signal generated as a function of the number of
discrete laser pulses (strontium analyte in glass specimen;
Q-switched Nd: YAG laser operation)

achieved in Q-switched o p e r a t i o n . T h i s characteristic

is m o r e desirable w h e n m a x i m u m lateral spatial reso
lution is required.
S a m p l i n g s p o t or c r a t e r size is also affected by the
energy of t h e i r r a d i a t i n g b e a m a n d the degree t o
which it is focused (see Fig. 3a, b ) . T h e smallest s p o t
size (highest spatial resolution) is achieved a t the laser
focus a n d with lower laser energy. W i t h t h e N d : Y A G
laser o p e r a t e d a t its f u n d a m e n t a l
wavelength
(1064 n m ) , c r a t e r size increases with laser energy, b u t
the signal m e a s u r e d eventually levels off a b o v e a b o u t
2 0 0 - 3 0 0 m J (Fig. 3c). Less signal is m e a s u r e d for
smaller s a m p l e craters (Fig. 3d); therefore, increased
spatial resolution (smaller craters) is often t r a d e d for
increased sensitivity (larger craters). H o w e v e r , the
high s a m p l e r e m o v a l rates achieved by o p e r a t i n g the
laser at higher energy c a n o v e r l o a d the I C P - M S
interface. Refractory m a t e r i a l s such as ceramics c a n
clog the interface orifices t h e r e b y reducing ion t r a n s
mission efficiency a n d analytical sensitivity. F o r these
r e a s o n s , the lowest laser energy which p r o v i d e s suffi
cient analytical sensitivity is usually c h o s e n .
T h e relative sensitivity factors of the I C P m a s s
s p e c t r o m e t e r are r e p r o d u c i b l e . Slight d a y - t o - d a y vari
a t i o n s in the s h a p e of t h e empirically d e t e r m i n e d
response function ( s p e c t r o m e t e r sensitivity vs m a s s )
c a n be corrected by n o r m a l i z a t i o n t o t h e sensitivity of
between three a n d five c a l i b r a t i o n elements evenly
distributed in m a s s across the periodic table ( 5 240 D a ) . T h e responses for all r e m a i n i n g elements c a n
then be calculated from the relative sensitivity factors.
W h e n s u r r o g a t e elements are used in this w a y t o
calibrate t h e s p e c t r o m e t e r for o t h e r a n a l y t e elements,
c a l i b r a t i o n is c o n s i d e r e d s e m i q u a n t i t a t i v e . R i g o r o u s
q u a n t i t a t i v e analysis c a n also be carried o u t by e s t a b -

218

Spectrometry

lishing a c a l i b r a t i o n curve (signal vs c o n c e n t r a t i o n ) b y

m e a s u r i n g t h e r e s p o n s e for each individual a n a l y t e
element in o n e o r m o r e c a l i b r a t i o n s t a n d a r d s . If such
s t a n d a r d s are available, a c c u r a c y c a n be very high
( 5 - 1 5 % ) ; h o w e v e r , it is n o t always possible t o
p r e p a r e o r p u r c h a s e s t a n d a r d s c o n t a i n i n g suitable
levels of each element of interest.
W h e r e c a l i b r a t i o n s t a n d a r d s a r e n o t available for
each a n a l y t e , s e m i q u a n t i t a t i v e analysis c a n be a n
effective alternative. A n a l y t i c a l e r r o r c a n be as low as
2 0 - 3 0 % , a l t h o u g h results falling within a factor of
t w o of the t r u e value a r e also c o m m o n . T h i s degree of
a c c u r a c y is often a c c e p t a b l e c o n s i d e r i n g t h e low c o n
c e n t r a t i o n s w h i c h c a n be m e a s u r e d ; lower limits of
1
detection a r e typically 0.001-0.1 g g " . A l t h o u g h ac
c u r a c y m a y be p o o r e r , s e m i q u a n t i t a t i v e L S I C P M S
analysis is a powerful screening tool for rapidly
c h a r a c t e r i s i n g s a m p l e s of completely u n k n o w n c o m
p o s i t i o n a n d for identifying t h e presence of u n e x p e c
ted s a m p l e c o n s t i t u e n t s . T h i s characteristic of the
t e c h n i q u e is especially useful for engineering, m a n u
facturing a n d process p r o b l e m solving.

4.

Applications

Laser s a m p l i n g c a n be used t o s a m p l e a l m o s t a n y
solid m a t e r i a l , w h e t h e r r o u g h o r s m o o t h , c o m p o s i t e
o r h o m o g e n e o u s , reflective o r a b s o r p t i v e . Because t h e
q u a d r u p o l e c a n be s c a n n e d rapidly, a c o m p l e t e m a s s
s p e c t r u m of a m a t e r i a l of u n k n o w n c o m p o s i t i o n c a n
be r e c o r d e d in milliseconds. T h e L S I C P M S s p e c t r u m
of a glass m a t e r i a l in Fig. 4 illustrates t h e a m o u n t of
i n f o r m a t i o n c o n t a i n e d in a single L S I C P M S spec
t r u m . T h o u g h relatively new, t h e t e c h n i q u e h a s
a l r e a d y f o u n d a p p l i c a t i o n in t h e analysis of alloys,
glasses, ceramics, m i n e r a l s , plastics, s e m i c o n d u c t o r s
and environmental materials.
A r r o w s m i t h (1987) r e p o r t e d t h e analysis of lowalloy steels, c o p p e r alloys, A l 2 0 3 - T i C - Z r 0 2 ceramics
a n d c o b a l t - p l a t i n u m thin films o n a l u m i n a . H a g e r
(1990) analyzed zircon, d e m o n s t r a t i n g q u a n t i t a t i v e
analysis of impurities r a n g i n g in c o n c e n t r a t i o n from
1
2 4 g g ~ to 10.5 w t % . D e p t h - c o n c e n t r a t i o n profiles
in a n a n c i e n t C h i n e s e m i r r o r were also m e a s u r e d t o
s t u d y the surface finishes of H a n d y n a s t y m i r r o r s . In
a d d i t i o n , the ability of L S I C P M S t o p r o v i d e isotopic
a b u n d a n c e i n f o r m a t i o n w a s illustrated for lead in
zircon. T y e et al. (1989) also used L S I C P M S t o
identify r a d i o g e n i c lead in g y p s u m .
Abell et al. (1990) a n d M o c h i z u k i et al. (1991)
r e p o r t e d t h e analysis of impurities in silicon nitride
a n d o t h e r ceramics. T h e possibility of analyzing trace
impurities w i t h o u t dissolving c e r a m i c m a t e r i a l s is a n
especially a t t r a c t i v e feature of t h e t e c h n i q u e a n d
reduces t h e c h a n c e of c o n t a m i n a t i o n associated with
the lengthy dissolution p r o c e d u r e s c o m m o n l y used in
t h e analysis of refractory m a t e r i a l s . D e n o y e r a n d

Laser

-0.5

0.5

Relative focal

1.5

position

Sampling

Inductively

Plasma

200

(mm)

(c)

Coupled

400

Laser energy

Mass

Spectrometry

600

(mj)

"(d)

.7
150
250
Laser energy

350
(mj)

50
Crater

100
diameter

150
(//m)

Figure 3
(a-d) The interrelationships of laser beam focus, laser energy, sample crater size and signal intensity in LSICPMS (cobalt
analyte in steel specimen; free-running Nd: YAG laser operation)

Transition metals

100

Mass

Rare e a r t h s

150

(amu)

Figure 4
LSICPMS spectrum of trace elements present at 50 gg~
(nominal) in glass showing the high information content
of a single spectrum; isotopes of gadolinium are
highlighted (Q-switched Nd: YAG laser operation)

W a l l a c e (1989) e x a m i n e d h i g h - p u r i t y q u a r t z used in
silicon wafer m a n u f a c t u r e . T h e p r o b i n g capabilities of
L S I C P M S were used t o establish c o m p o s i t i o n a l dif
ferences b e t w e e n b u l k q u a r t z a n d localized i m p u r i t y
inclusions. M a r s h a l l et al. (1991) a n a l y z e d plastics
directly, e m p l o y i n g b o t h q u a n t i t a t i v e a n d s e m i q u a n t i
tative c a l i b r a t i o n . T h e results of t h e s e m i q u a n t i t a t i v e
analysis agreed t o within a factor of t w o o r better with
results from x-ray fluorescence ( X R F ) analysis a n d
a d d i t i o n a l e l e m e n t s w h i c h c o u l d n o t be detected by
X R F were readily identified.
Because of t h e sensitivity of t h e t e c h n i q u e a n d the
fact t h a t t h e q u a d r u p o l e c a n scan t h e full periodic
t a b l e rapidly, a c o m p l e t e s e m i q u a n t i t a t i v e analysis of
h i g h - p u r i t y m a t e r i a l s c a n be carried o u t within 1-2
m i n a n d t h e presence of u n s u s p e c t e d trace i m p u r i
ties revealed. C a l i b r a t i o n s t a n d a r d s a p p r o p r i a t e
for t h e q u a n t i t a t i v e analysis of m a n y n e w hight e c h n o l o g y a n d u l t r a p u r e m a t e r i a l s a r e n o t avail
able. T h e r e f o r e , t h e possibility of s e m i q u a n t i t a t i v e

219

Laser Sampling

Inductively

Coupled

Plasma

Mass

c a l i b r a t i o n with L S I C P M S b e c o m e s m o r e a n d m o r e
attractive as new exotic m a t e r i a l s a r e discovered.
See also: Chemical Analysis of Solid Surfaces; Laser Microprobe Mass Spectrometry

Bibliography
Abell I D, Gregson D, Shuttleworth S 1990 Laser ablation
ICP-MS analysis of ceramic materials. In: Freer R (ed.)
1990 The Physics and Chemistry of Carbides, Nitrides and
Borides. Kluwer, Dordrecht, The Netherlands, pp. 12130
Arrowsmith A 1987 Laser alblation of solids for elemental
analysis by inductively coupled plasma mass spectrom
etry. Anal Chem. 59: 1437-44
Arrowsmith A 1990 Applications of laser ablation: ele
mental analysis of solids by secondary plasma source
mass spectrometry. In: Lubman D (ed.) 1990 Lasers
and Mass Spectrometry. Oxford University Press, New
York
Denoyer R, Wallace G 1989 The analysis of high purity
quartz by laser sampling ICP-MS. 16th Annual Meeting
Federation of Analytical Chemistry and Spectroscopy
Societies., Chicago, IL, Paper 742, Meeting Abstract
Hager J W 1989 Relative elemental responses for laser
ablation inductively coupled plasma mass spectrometry.
Anal. Chem. 61: 1243-8
Hager J W 1990 Elemental analysis of solids using laser
sampling inductively coupled plasma mass spectrometry.
In: Lerner J M, McNamara J (eds.) 1990 SPIE Optical
Spectroscopic Instrumentation and Techniques for the
1990s, Vol. 1318. Society of Photo-Optical Instrumen
tation Engineers, Bellingham, WA, pp. 166-77
Houk R S 1986 Mass spectrometry of inductively coupled
plasmas. Anal. Chem. 58: 97A
Marshall J, Franks J, Abell I, Tye C 1991 Determination of
trace-elements in solid plastic materials by laser ablation
inductively coupled plasma mass-spectrometry. J. Anal.
At. Spectrom. 6: 145-50
Mochizuki T, Sakashita A, Iwata H, Ishibashi Y, Gunji
1991 Direct analysis of silicon nitride powders by induc
tively coupled plasma mass spectrometry with a laser
ablation technique. Anal. Sci. 7: 151-3
Moenke-Blankenburg L 1989 Laser Microanalysis. Wiley,
New York
Tye C T, Henry R, Abell I D, Gregson D 1989 Analyze the
elements without dissolving the solid. Res. Dev. 31: 76-9
E. R. D e n o y e r
[The P e r k i n - E l m e r C o r p o r a t i o n , N o r w a l k ,
Connecticut, USA]

Liquid Chromatography Mass

Spectrometry
Liquid c h r o m a t o g r a p h y m a s s s p e c t r o m e t r y is a n a n a
lytical t e c h n i q u e e m p l o y e d in the identification of
c o m p o n e n t s in m i x t u r e s . In its simplest form, a mix
t u r e is i n t r o d u c e d i n t o a liquid c h r o m a t o g r a p h w h e r e

220

Spectrometry

it is s e p a r a t e d (partially o r completely) i n t o its c o m

p o n e n t p a r t s . T h e s e v a r i o u s c o m p o n e n t s elute from
the liquid c h r o m a t o g r a p h in sequence s e p a r a t e d in
time. T h e effluent of t h e liquid c h r o m a t o g r a p h is
introduced into a mass spectrometer where mass
spectra a r e a c q u i r e d of the s e p a r a t e d c o m p o n e n t s .
T h e m a s s spectra a c q u i r e d in this w a y m a y be inter
p r e t e d t o p r o v i d e m o l e c u l a r weights a n d m o l e c u l a r
s t r u c t u r e s for t h e v a r i o u s c o m p o n e n t s .
A l t h o u g h , in principle, this process seems simple,
in practice it is q u i t e c o m p l e x . T h e p r o p e r o p e r a t i o n
of a m a s s s p e c t r o m e t e r requires t h a t a g o o d v a c u u m
5
(typically ^ 1 0 " t o r r ) be m a i n t a i n e d within t h e
i n s t r u m e n t . H o w e v e r , t h e effluent of a liquid c h r o m a
t o g r a p h consists of very tiny a m o u n t s of s e p a r a t e d
c o m p o n e n t s dissolved in large a m o u n t s of o r g a n i c
solvent. T h e solvent flow o u t of a liquid c h r o m a t o
1
g r a p h typically r a n g e s between 0.5 m l m i n "
and
1
3 ml m i n " . T h e c o n c e n t r a t i o n s of s e p a r a t e d c o m
p o n e n t s in this solvent a r e s e l d o m m o r e t h a n a few
h u n d r e d p a r t s p e r million a n d a r e frequently m u c h
lower. W h e n this very large a m o u n t of solvent reaches
the m a s s s p e c t r o m e t e r , it is i m m e d i a t e l y c o n v e r t e d
i n t o v a p o r . T h i s v a p o r c o n s t i t u t e s a gas l o a d o n t h e
v a c u u m system of t h e m a s s s p e c t r o m e t e r which is far
in excess of the p u m p i n g capacities typically p r o v i d e d .
T h e essence of liquid c h r o m a t o g r a p h y m a s s spec
t r o m e t r y b e c o m e s , therefore, t h e a r r a y of strategies
w h i c h h a v e been devised t o a t t e n u a t e t h e effects of the
solvent w i t h o u t losing t h e dissolved a n a l y t e a n d with
o u t d e g r a d i n g t h e s e p a r a t i o n s t h a t h a v e been p r o
d u c e d b y t h e liquid c h r o m a t o g r a p h i c process.

i . Direct Liquid
Injection
T h e earliest a t t e m p t s a t liquid c h r o m a t o g r a p h y m a s s
s p e c t r o m e t r y involved either the use of micro-liquidc h r o m a t o g r a p h y c o l u m n s with very low flows o r
s t a n d a r d c o l u m n s with splitting of the effluent so t h a t
only very small q u a n t i t i e s r e a c h t h e m a s s spec
t r o m e t e r . T h i s m e t h o d of interfacing is by far t h e
simplest since it involves only the use of a t u b e t o
c o n d u c t the flowing solvent from the liquid c h r o m a t o
g r a p h t o t h e m a s s s p e c t r o m e t e r . H o w e v e r , this
m e t h o d h a s m a n y limitations. First, t h e q u a n t i t i e s of
a n a l y t e which reach t h e m a s s s p e c t r o m e t e r a r e very
small. M i c r o - l i q u i d - c h r o m a t o g r a p h y c o l u m n s h a v e
small capacities for s a m p l e a n d splitting of effluent
reduces t h e s a m p l e r e a c h i n g t h e m a s s s p e c t r o m e t e r in
direct p r o p o r t i o n t o t h e split. T h i s m e a n s t h a t t h e
sensitivities of detection for this a p p r o a c h a r e p o o r .
F u r t h e r , it is still necessary t o i n t r o d u c e a t least
several t e n t h s of a milliliter of solvent p e r m i n u t e i n t o
the m a s s s p e c t r o m e t e r . Even this a m o u n t of solvent
p r o d u c e s so m u c h pressure t h a t c o n v e n t i o n a l electron
i o n i z a t i o n is n o t possible a n d instead only c h e m i c a l
i o n i z a t i o n m a s s spectra m a y be o b t a i n e d . I n this

Liquid

Chromatography

Liquid

Mass

Spectrometry

chromatograph

effluent
Infrared reflector
Split
Flash
vaporizer

option
Vacuum

locks

JTl_Am_\^_iTL

Scrubber
solvent

Ion
source-*

-Spring-loaded
idler w h e e l

Kb)fja1

(C)

Pump

Pump

Drive wheels

Waste

Figure 1
Moving belt interface: scrubbing solution enters at (a), salt deposits are extracted at (b) and waste leaves at (c) (after
Kelley 1981 Proc. 29th ASMS Conf. Mass Spectrometry and Allied Topics. American Society of Mass Spectrometry,
East Lansing, MI. Reproduced with permission)

m e t h o d , t h e liquid c h r o m a t o g r a p h y solvent serves a s

the chemical i o n i z a t i o n r e a g e n t g a s . F o r this r e a s o n ,
m a n y liquid c h r o m a t o g r a p h y s e p a r a t i o n s a r e n o t
practical with direct c o n n e c t i o n . F o r e x a m p l e , a
g r a d i e n t elution w o u l d i m p l y a c h a n g e in solvent
which w o u l d i m p l y a c h a n g e in chemical i o n i z a t i o n
conditions within the mass spectrometer. Such
c h a n g e s m a k e a n y m a s s s p e c t r a o b t a i n e d very diffi
cult t o interpret.
T h e f u n d a m e n t a l s h o r t c o m i n g of this m e t h o d is
t h a t n o t h i n g h a s b e e n d o n e t o enrich t h e a n a l y t e w i t h
respect t o t h e solvent.

2. Moving

Belt

Interface

T h e first a t t e m p t s t o selectively r e m o v e solvent w i t h

o u t losing a n a l y t e involved t h e u s e of a m o v i n g belt.
In this case, t h e effluent from t h e liquid c h r o m a t o
g r a p h is d e p o s i t e d o n a m o v i n g belt. T h e speed of t h e
belt a n d t h e m e t h o d of d e p o s i t i o n a r e critical in o r d e r
t h a t t h e liquid is p r e v e n t e d from flowing a l o n g t h e
belt a n d t h e r e b y d e g r a d i n g t h e c h r o m a t o g r a p h i c reso
lution. T h i s is usually a c c o m p l i s h e d b y a s p r a y i n g
t e c h n i q u e . After d e p o s i t i o n of t h e liquid, t h e belt
moves
through
several
independent
pumping
c h a m b e r s w h e r e t h e solvent is r e m o v e d b y t h e c o m
bined a c t i o n of h e a t e r s a n d v a c u u m p u m p s . T h e
degree of h e a t i n g m u s t b e carefully c o n t r o l l e d in o r d e r
t o r e m o v e solvent w i t h o u t e v a p o r a t i n g a n a l y t e .
Finally t h e belt m o v e s t o a p o i n t inside t h e m a s s
s p e c t r o m e t e r w h e r e it is strongly h e a t e d t o e v a p o r a t e
the a n a l y t e w h i c h exists a s a residue o n its surface.
After e v a p o r a t i o n , t h e a n a l y t e c a n b e ionized a n d
detected using a n y of t h e c o m m o n l y available m a s s

s p e c t r o m e t r y t e c h n i q u e s . N e x t , t h e belt exits t h e m a s s
s p e c t r o m e t e r i n t o a final p u m p i n g c h a m b e r w h e r e it is
very strongly h e a t e d t o r e m o v e a n y r e m a i n i n g traces
of s a m p l e . I n s o m e designs t h e belt m a y also b e rinsed
with solvent. T h e n in a c o n t i n u o u s l o o p process, t h e
belt r e t u r n s t o t h e b e g i n n i n g w h e r e it picks u p a d d i
t i o n a l effluent from t h e liquid c h r o m a t o g r a p h a n d
repeats the process.
A l t h o u g h this m e t h o d represents a m a j o r i m p r o v e
m e n t with respect t o direct injection, there a r e a
n u m b e r of serious p r o b l e m s . First, consider, for ex
a m p l e , t h a t t h e degree of h e a t i n g r e q u i r e d t o e v a p o r
a t e solvent d e p e n d s o n t h e n a t u r e of t h e solvent. If t h e
liquid c h r o m a t o g r a p h y m e t h o d utilizes g r a d i e n t elu
tion t e c h n i q u e s , t h e n t h e n a t u r e of t h e solvent is
c o n t i n u o u s l y c h a n g i n g a n d t h e a m o u n t of h e a t a p
plied m u s t b e c o n t i n u o u s l y adjusted. Second, consider
t h a t d e p o s i t i o n o n t h e belt w i t h o u t b a n d s p r e a d i n g is
very difficult. T h e w e t t i n g characteristics of v a r i o u s
solvents o n a given belt c o m p o s i t i o n varies a n d there
fore, in a g r a d i e n t e l u t i o n , t h e w e t t i n g b e h a v i o r c a n
v a r y as t h e c h r o m a t o g r a p h y progresses. A l s o , c o n
sider t h a t m a n y a n a l y t e s m a y b e difficult t o r e m o v e
from t h e belt a n d m a y slowly build u p as a partially
volatile residue. Finally, a n d p e r h a p s m o s t f u n d a m e n
tally, c o n s i d e r t h a t m o s t often liquid c h r o m a t o g r a p h y
m e t h o d s a r e selected for t h o s e m a t e r i a l s which h a v e
limited volatility. Volatile m a t e r i a l s a r e usually r u n b y
gas c h r o m a t o g r a p h y b e c a u s e of t h e vastly i m p r o v e d
r e s o l u t i o n afforded b y this t e c h n i q u e . H o w e v e r , using
t h e m o v i n g belt t e c h n i q u e , a n a l y t e s w h i c h m a y b e
only slightly volatile a r e r e q u i r e d t o e v a p o r a t e i n t o
t h e m a s s s p e c t r o m e t e r . T h i s aspect a l o n e d r a m a t i c a l l y
limits t h e r a n g e o f m a t e r i a l s which c a n b e e x a m i n e d .
F i g u r e 1 s h o w s a n e x a m p l e of a typical m o v i n g belt
interface.

221

Liquid

Chromatography

3. Thermospray
Spectrometry

Liquid

Mass

Spectrometry

Chromatography-Mass

T h e t h e r m o s p r a y m e t h o d of liquid c h r o m a t o g r a p h y m a s s s p e c t r o m e t r y interfacing relies o n a n entirely

different principle. In this case, t h e effluent from the
liquid c h r o m a t o g r a p h is nebulized by h e a t i n g as it
passes t h r o u g h a small-diameter capillary. T h e exact
t e m p e r a t u r e r e q u i r e d for efficient n e b u l i z a t i o n varies
with solvent. T h e a e r o s o l particles of a n a l y t e b e a r i n g
solvent p r o d u c e d in this w a y a r e k n o w n t o be electri
cally c h a r g e d . T h e c h a r g i n g of such aerosols w a s first
recognized in t h e mid-1800s. After f o r m a t i o n , t h e
aerosol particles a r e allowed t o drift in a p a r t i a l
v a c u u m w h e r e they rapidly lose solvent by e v a p o r a
tion. Such loss of solvent results in a c o n c e n t r a t i o n of
c h a r g e as the r a d i u s of the d r o p l e t s falls. Eventually, a
p o i n t is reached a t which d r o p l e t s begin t o expel
c h a r g e d species in o r d e r t o p r e v e n t t h e local c h a r g e
density from increasing further. A t this stage, t h e
aerosol s t r e a m is directed across a small orifice which
extracts a n d focuses the c h a r g e d species i n t o a m a s s
s p e c t r o m e t e r w h e r e they a r e a n a l y z e d . In s o m e instru
m e n t s , t h e p o t e n t i a l applied t o extract t h e ions i n t o
the m a s s s p e c t r o m e t e r m a y be adjusted a n d these
a d j u s t m e n t s m a y influence t h e degree of fragmen
t a t i o n observed. M o s t of the solvent d o e s n o t enter
the m a s s s p e c t r o m e t e r , b u t r a t h e r is p u m p e d a w a y b y
a n auxiliary m e c h a n i c a l p u m p after p a s s i n g a c r o s s t h e
ion e x t r a c t i o n orifice.
T h e t h e r m o s p r a y m e t h o d relies entirely o n t h e ions
p r o d u c e d in the aerosol e v a p o r a t i o n process. A l t e r n
ative i o n i z a t i o n m e t h o d s such as electron i o n i z a t i o n
or chemical i o n i z a t i o n a r e n o t used a n d a r e n o t
generally possible. In s o m e cases it h a s p r o v e d useful
to create a glow discharge in t h e a e r o s o l e v a p o r a t i o n
region. A d d i t i o n of electrons to t h e aerosol region
using a n electron g u n h a s also been described.
Because the ionization m e t h o d generally d e p e n d s
solely o n t h e " s p o n t a n e o u s " expulsion of ions from
solution, the species observed a n d their relative a b u n
d a n c e s d e p e n d very heavily o n m o l e c u l a r s t r u c t u r e .
M a t e r i a l s which exist as ions in solution a r e likely t o
be ejected as ions from aerosol particles. M a t e r i a l s
which are n e u t r a l in solution a r e very unlikely t o be
ejected as ions in t h e t h e r m o s p r a y process a n d will
p r o b a b l y give n o signal a t all. A s a result, this
interfacing m e t h o d is n o t general in its applicability
b u t r a t h e r is suitable only for p a r t i c u l a r classes of
materials. M o s t w o r k h a s been d o n e with m a t e r i a l s
which a r e very p o l a r a n d w a t e r soluble. F o r m a t e r i a l s
of this type, sensitivities c a n be exceptionally g o o d . I n
a d d i t i o n , this is a very mild i o n i z a t i o n m e t h o d c h a r a c
terized b y the p r o d u c t i o n of m o l e c u l a r ions with
minimal fragmentation.
T h e t h e r m o s p r a y process h a s been s h o w n t o be
generally limited t o solvent systems with a high
a q u e o u s c o n t e n t a n d t h e sensitivity of the m e t h o d

222

Quadrupole and lens system

Liquid vaporizer

Electron filament
Thermospray ion
source body

Discharge electrode
" Adjustable fragmentor electrode

Figure 2
Thermospray liquid chromatography-mass spectrometry
interface (after Goodley 1990 Proc. 38th ASMS Conf.
Mass Spectrometry and Allied Topics. American Society of
Mass Spectrometry, East Lansing, MI. Reproduced with
permission)

is i m p r o v e d b y the presence of buffers such as

a m m o n i u m acetate.
F i g u r e 2 s h o w s a n e x a m p l e of a typical t h e r m o
s p r a y liquid c h r o m a t o g r a p h y - m a s s
spectrometry
interface.

4. Particle Beam Liquid

Spectrometry

Chromatography-Mass

In a m a n n e r similar t o t h e t h e r m o s p r a y interface, the

particle b e a m interface begins b y nebulizing the
effluent from t h e liquid c h r o m a t o g r a p h . A n y of a
wide r a n g e of nebulizers m a y b e used including ultra
sonic, p n e u m a t i c a n d t h e r m o s p r a y nebulizers. H o w
ever, o n c e t h e a e r o s o l is f o r m e d t h e process is quite
different from t h e r m o s p r a y . First t h e aerosol is dis
p e r s e d with a h e l i u m s t r e a m t o p r e v e n t a g g l o m
e r a t i o n . N e x t it is allowed t o drift t h r o u g h a
" d e s o l v a t i o n c h a m b e r " in w h i c h t h e solvents e v a p o r
ate. After t h e d e s o l v a t i o n c h a m b e r , the effluent from
the liquid c h r o m a t o g r a p h h a s been c o n v e r t e d in a
s u s p e n s i o n of s u b m i c r o m e t e r - s i z e d solute particles
dispersed in a m i x t u r e of helium a n d solvent v a p o r .
T h i s s u s p e n s i o n of particles is pulled t h r o u g h a capill
a r y nozzle h a v i n g a d i a m e t e r of a b o u t 0.5 m m . T h i s
nozzle forms t h e solute particles i n t o a b e a m with
n e a r sonic velocities. T h i s particle b e a m is directed a t
a series of s k i m m e r s which serve t o allow the particle
b e a m t o travel directly t o w a r d the m a s s s p e c t r o m e t e r
while r e m o v i n g helium a n d solvent v a p o r a t right
angles via high-capacity m e c h a n i c a l v a c u u m p u m p s .
T h i s process successfully discriminates against solvent
v a p o r a n d h e l i u m b e c a u s e these species a r e m u c h less
massive t h a n t h e solute particles a n d therefore a c q u i r e
m u c h less m o m e n t u m in the nozzle. Particle b e a m
interfaces designed for use w i t h m a g n e t i c m a s s spec
trometers a n d h a v i n g as m a n y as three stages of p u m p
ing in t h e m o m e n t u m s e p a r a t o r h a v e r o u t i n e l y

Liquid

Chromatography

Mass

Spectrometry

Figure 3
Particle beam liquid chromatography-mass spectrometry interface

p r o d u c e d ion s o u r c e p r e s s u r e s lower t h a n t h o s e typi

cal of gas c h r o m a t o g r a p h y m a s s s p e c t r o m e t r y .
T h e particle b e a m travels in a straight line from t h e
nozzle t o t h e i o n s o u r c e of t h e m a s s s p e c t r o m e t e r . A t
the ion s o u r c e , t h e solute particles a r e m a d e t o
e v a p o r a t e b y hitting a specially designed t a r g e t o r b y
hitting t h e walls of t h e ion v o l u m e itself. I n either
case, t e m p e r a t u r e s of 2 5 0 - 3 5 0 C a r e typically used in
t h e e v a p o r a t i o n p r o c e s s . E v a p o r a t i o n of such small
particles h a s b e e n f o u n d t o b e m u c h m o r e efficient
t h a n e v a p o r a t i o n of b u l k residues from surfaces as is
p e r f o r m e d in t h e m o v i n g belt interface. F o r e x a m p l e ,
it h a s been s h o w n t h a t p o l y s t y r e n e o l i g o m e r s as large
as 1800 a m u e v a p o r a t e i n t a c t a n d p r o v i d e useful m a s s
spectra. E v a p o r a t i o n of this s a m e m a t e r i a l w i t h o u t
t h e r m a l d e c o m p o s i t i o n from a m o v i n g belt is n o t
possible.
A n y of a wide variety of i o n i z a t i o n t e c h n i q u e s m a y
be e m p l o y e d in c o m b i n a t i o n w i t h t h e particle b e a m
interface. E l e c t r o n i o n i z a t i o n , chemical i o n i z a t i o n ,
field i o n i z a t i o n a n d o r g a n i c s e c o n d a r y - i o n m a s s spec
t r o m e t r y ( S I M S ) t e c h n i q u e s h a v e all b e e n r e p o r t e d .
Electron i o n i z a t i o n s p e c t r a a r e p a r t i c u l a r l y useful
because of t h e wide availability of library spectra.
D e p e n d i n g o n t h e nebulizer t y p e used a n d t h e
n u m b e r of stages of p u m p i n g in t h e m o m e n t u m
s e p a r a t o r , the particle b e a m interface is c a p a b l e of
a c c o m m o d a t i n g liquid c h r o m a t o g r a p h y flow r a t e s as
_ 1
high as 3 m l m i n . I n a d d i t i o n , a l m o s t a n y volatile
solvent m a y b e used. T h e m a j o r l i m i t a t i o n s include
t h e fact t h a t n o n v o l a t i l e buffers m a y n o t be u s e d a n d
t h a t m a t e r i a l s w i t h extremely high p o l a r i t y m a y n o t
e v a p o r a t e in t h e i o n s o u r c e . I n this respect, t h e
particle b e a m interface a n d t h e t h e r m o s p r a y interface
are c o m p l e m e n t a r y b e c a u s e t h e latter w o r k s best with
materials of u n u s u a l l y high p o l a r i t y .

F i g u r e 3 s h o w s a n e x a m p l e of a typical particleb e a m - t y p e liquid c h r o m a t o g r a p h y - m a s s s p e c t r o m

etry interface.

5. Electrospray
Spectrometry

Liquid
Interface

Chromatography-Mass

E l e c t r o s p r a y c o n s t i t u t e s yet a n o t h e r a p p r o a c h t o
liquid c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y interfac
ing. I n this case, a very small flow of liquid c h r o m a t o g r a p h effluent is m a d e t o p a s s t h r o u g h a h o l l o w
c o n d u c t i v e needle held a t a b o u t 10 000 V relative t o a
c o u n t e r electrode a s h o r t d i s t a n c e a w a y . D e p e n d i n g
o n t h e c o m p o s i t i o n of t h e effluent from t h e liquid
c h r o m a t o g r a p h , such a n a r r a n g e m e n t c a n cause a
stable p h e n o m e n o n in which t h e effluent is ejected as a
s t r e a m i n g s p r a y from t h e tip of t h e needle. S k i m m i n g
c o n e s facing t h e needle collect t h e ionic c o m p o n e n t of
t h e ejected m a t e r i a l a n d i n t r o d u c e it i n t o a m a s s
s p e c t r o m e t e r . T h e i o n s p r o d u c e d in this w a y a r e often
very highly c h a r g e d . T h e e l e c t r o s p r a y liquid c h r o m a
t o g r a p h y - m a s s s p e c t r o m e t r y interface h a s been f o u n d
m o s t useful for biological species such as p e p t i d e s .
F o r this class of m a t e r i a l s , m a s s spectra h a v e been
o b t a i n e d in t h e lOOOOOdalton r a n g e .
Because t h e p e p t i d e s m a y b e very highly c h a r g e d ,
their m a s s - t o - c h a r g e r a t i o c a n fall within the r a n g e of
c o n v e n t i o n a l m a s s s p e c t r o m e t e r s . Often a series of
c h a r g e d states is o b s e r v e d . T h e o b s e r v e d m a s s of e a c h
of t h e c o m p o n e n t s of such a series in c o m b i n a t i o n
with t h e s e p a r a t i o n b e t w e e n c o m p o n e n t s differing by
o n e positive c h a r g e m a y be used t o calculate t h e true
m a s s . T h e sensitivity of this t e c h n i q u e for m a t e r i a l s
like p e p t i d e s c a n be exceptionally g o o d . M a n y ex
a m p l e s of picomole-level analyses h a v e been r e p o r t e d .

223

Liquid

Chromatography

Mass

Spectrometry

Figure 4
Electrospray liquid chromatography-mass spectrometry
interface (after Lee 1990 Proc. 38th ASMS Conf. Mass
Spectrometry and Allied Topics. American Society of Mass
Spectrometry, East Lansing, ML Reproduced with
permission)

F i g u r e 4 s h o w s a n e x a m p l e of a typical electros p r a y - t y p e liquid c h r o m a t o g r a p h y - m a s s s p e c t r o m

etry interface. F i g u r e 5 s h o w s a m a s s s p e c t r u m of
h u m a n transferrin o b t a i n e d by electrospray. Clearly,
because of the complexity of t h e s p e c t r u m o b t a i n e d
for a single m o l e c u l a r species, t h e spectra of m i x t u r e s
of m o l e c u l a r species c a n be difficult t o d e c o n v o l u t e .

b a r d m e n t ( F A B ) m e t h o d of i o n i z a t i o n . I n this case,
t h e c o n v e n t i o n a l F A B target is replaced with a m o d i
fied target w h e r e t h e effluent from t h e liquid c h r o m a
t o g r a p h c a n be c o n t i n u o u s l y p u m p e d o n t o t h e surface
of the target. A s in e l e c t r o s p r a y i o n i z a t i o n , very low
liquid c h r o m a t o g r a p h y flows a r e used. I n a typical
e x p e r i m e n t , a second s t r e a m of solvent c o n t a i n i n g a n
a p p r o p r i a t e F A B m a t r i x such as glycerol is m i x e d
with t h e effluent from t h e liquid c h r o m a t o g r a p h a n d
t h e c o m b i n e d s t r e a m is p u m p e d o n t o t h e t a r g e t of the
mass spectrometer. The mass spectrometer vacuum
r e m o v e s t h e solvent leaving t h e a n a l y t e dissolved in
the F A B m a t r i x . T h e r e m o v a l of s a m p l e a n d m a t r i x
by t h e s p u t t e r i n g of t h e p r i m a r y ion b e a m , p r o v i d e s
a c o n t i n u o u s l y refreshed target which preserves
c h r o m a t o g r a p h i c resolution.
T h e classes of s a m p l e a p p r o p r i a t e for liquid c h r o m a t o g r a p h y - F A B analyses a r e very similar t o t h o s e
w h i c h w o r k well with t h e r m o s p r a y a n d with electro
spray. T h i s is t h e highly p o l a r , water-soluble class
of m a t e r i a l s often associated with d r u g s a n d n a t u r a l
p r o d u c t s . F r e e fatty acids a n d q u a t e r n a r y a m m o n i u m
salts also w o r k well. F o r m a t e r i a l s which ionize well
by F A B , t h e sensitivity of this a p p r o a c h t o liquid
c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y c a n be quite
good.
See also: Gas and Liquid Chromatography

Bibliography
6. Fast-Atom-Bombardment-Based
Chromatography-Mass
Spectrometry

Liquid
Interfaces

A final type of liquid c h r o m a t o g r a p h y - m a s s spec

t r o m e t r y interface is b a s e d o n t h e fast a t o m b o m -

pl

2000

'

2200

2400

2600

2800

3000

11

3200

3400

3600

3800

4000

Figure 5
Mass spectrum of human transferrin (molecular weight
79 754) obtained by electrospray (after JEOL Sales
Brochure 1990 JEOL, Tokyo. Reproduced with
permission)

224

Caprioli R (ed.) 1990 Continuous Flow Fast Atom Bom

bardment Mass Spectrometry. Wiley, New York
Ligon W V, Dorn S 1990 Particle beam interface for liquid
chromatography/mass spectrometry. Anal. Chem. 62:
2573-80
Meng C K, McEwen C N, Larsen S, Whitehouse C M,
Fenn J 1990 Electrospray on magnetic sector instru
ment. In: Burlingame A L, McCloskey J A (eds.) 1990
Biological Mass Spectrometry, Proc. 2nd. Int. Symp. Mass
Spectrometry in the Health and Life Sciences. Elsevier,
Amsterdam, pp. 147-57
Niessen W M, Tjaden U R, Van Der Greef 1991 Strategies
in developing interfaces for coupling liquid chromatog
raphy and mass spectrometry. J. Chromatogr. 554: 3-26
Tomer J B, Parker C 1989 Biochemical applications of
liquid chromatography-mass spectrometry. / . Chroma
togr. 492: 189-221
White F A, Wood G 1986 Mass Spectrometry: Applica
tions in Science and Engineering. Wiley, New York,
pp. 222-3
W . V. L i g o n
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]


Magnetic Materials: Measurements
T h e investigation, u n d e r s t a n d i n g a n d use of m a g n e t i c
m a t e r i a l s requires t h e m e a s u r e m e n t of m a g n e t i c
p r o p e r t i e s . S u p e r c o n d u c t o r s also possess i m p o r t a n t
m a g n e t i c p r o p e r t i e s , as a c o n s e q u e n c e of t h e exclu
sion of m a g n e t i c flux from fully s u p e r c o n d u c t i n g
m a t e r i a l s (the M e i s s n e r effect). T h i s article describes
the m e a s u r e m e n t of basic m a g n e t i c p r o p e r t i e s a n d of
i m p o r t a n t engineering m a g n e t i c p r o p e r t i e s , e m p h a
sizing m a i n l y t e c h n i q u e s used a t very low frequency
(dc), p o w e r frequencies a n d a u d i o frequencies ( u p t o
a b o u t 20 k H z ) .

7.

Magnetization

T h e f u n d a m e n t a l e x p e r i m e n t a l q u a n t i t y in m a g n e t i c
m a t e r i a l s is t h e m a g n e t i z a t i o n , defined as the m a g
netic m o m e n t p e r u n i t v o l u m e . I n SI u n i t s , m a g n e t i z a
2
3
_ 1
tion is m e a s u r e d in A m m " = A m . Alternatively,
2
m a g n e t i z a t i o n c a n b e m e a s u r e d in tesla ( W b m ~ ) , in
which case it is called m a g n e t i c p o l a r i z a t i o n . In cgs
(electromagnetic) u n i t s , using t h e c o n v e n t i o n t h a t
m a g n e t i c m o m e n t is m e a s u r e d in e m u ( e l e c t r o m a g n e
1
3
tic units, erg O e " ) , m a g n e t i z a t i o n is in e m u c m .
W h e n the v o l u m e of t h e s a m p l e m a y c h a n g e , as with
t e m p e r a t u r e , it is c o n v e n i e n t t o m e a s u r e t h e m o m e n t
p e r u n i t m a s s r a t h e r t h a n p e r u n i t v o l u m e ; this
q u a n t i t y is usually given t h e s y m b o l a n d is e q u a l t o
the m a g n e t i z a t i o n p e r u n i t v o l u m e multiplied b y t h e
density, in a p p r o p r i a t e u n i t s . Values of a r e n u m e r i
cally e q u a l in SI a n d cgs u n i t s .
M a g n e t i z a t i o n is in general a strongly n o n l i n e a r
function of t h e a p p l i e d field a n d , in sufficiently high
field, reaches a limiting value called t h e s a t u r a t i o n
m a g n e t i z a t i o n , Ms. T h e s a t u r a t i o n m a g n e t i z a t i o n is
t e m p e r a t u r e d e p e n d e n t , in general decreasing from a
m a x i m u m value a t 0 t o a z e r o value a t t h e C u r i e
t e m p e r a t u r e . A t fixed t e m p e r a t u r e , m a g n e t i z a t i o n vs
field is b o t h n o n l i n e a r a n d hysteretic; a p l o t of vs
for a cycle of field from + H->0-+
H-+0-*
+ is
called a m a g n e t i c hysteresis l o o p a n d c o n t a i n s m u c h
of the i n f o r m a t i o n n e e d e d t o c h a r a c t e r i z e a m a g n e t i c
material.
1.1 Force
Methods
A m a g n e t i c m o m e n t m in a g r a d i e n t field VH experi
ences a force F = mVH. A g r a d i e n t field c a n be
p r o d u c e d b y t a p e r i n g t h e p o l e pieces of a n electro
m a g n e t ; a s a m p l e is s u s p e n d e d in t h e g a p of the
m a g n e t , w h e r e it is subject t o a n a v e r a g e field a n d
a field g r a d i e n t VH. T h e s a m p l e is s u s p e n d e d from
a force-measuring device, c o m m o n l y a chemical
b a l a n c e o r a n e l e c t r o b a l a n c e , a n d t h e m e a s u r e d force

gives directly t h e m a g n e t i c m o m e n t if the field g r a d i

e n t is k n o w n (see Fig. 1). T h i s m e t h o d is variously
k n o w n as t h e F a r a d a y o r t h e C u r i e m e t h o d ; the
a p p a r a t u s is often called a m a g n e t i c b a l a n c e . It is
c a p a b l e of m e a s u r i n g small m o m e n t s a n d , since the
only c o n n e c t i o n t o t h e s a m p l e is a s u p p o r t wire, the
m e t h o d is well suited t o m e a s u r e m e n t s at low a n d
especially a t high t e m p e r a t u r e s . It is often used for the
d e t e r m i n a t i o n of C u r i e t e m p e r a t u r e s (see Sect. 5) a n d
for m e a s u r e m e n t s of susceptibility (the slope of the
vs curve) as a function of t e m p e r a t u r e . U s i n g a
b a l a n c e with a sensitivity of 0.1 m g a n d a field g r a d i
2
e n t o f 4 0 0 k A m " (typical for t a p e r e d pole pieces), the
6
2
3
limiting sensitivity is a b o u t 1 0 A m ( 1 0 ~ e m u ) . T h e
system is usually c a l i b r a t e d by m e a s u r i n g a s a m p l e of
k n o w n m a g n e t i c p r o p e r t i e s , frequently p u r e nickel.
A c c u r a c y is limited b y t h e fact t h a t it is difficult t o
m a k e t h e field g r a d i e n t u n i f o r m over a large v o l u m e
a n d c o n s t a n t over a r a n g e of field a n d it is also
difficult t o m e a s u r e the field g r a d i e n t accurately.
T h e s e p r o b l e m s a r e a v o i d e d if t h e s a m p l e is m a d e
large e n o u g h so t h a t a u n i f o r m cylinder of s a m p l e
e x t e n d s from t h e p o i n t of m a x i m u m field t o a region
of essentially zero field. I n this case (called the G o u y
m e t h o d ) , the force o n the s a m p l e d o e s n o t d e p e n d o n
the s h a p e of t h e field g r a d i e n t .
T h e field g r a d i e n t in t h e a r r a n g e m e n t of Fig. 1
vanishes as the field a p p r o a c h e s z e r o , so this m e t h o d
is n o t useful for low field m e a s u r e m e n t s . If waterc o o l e d field g r a d i e n t coils a r e used instead of t a p e r e d
p o l e pieces, t h e field g r a d i e n t b e c o m e s i n d e p e n d e n t of

Figure 1
Magnetic balance: P, electromagnet pole piece with
tapered gap; S, sample and B, balance or other
force-measuring device

225

Magnetic

Materials:

Measurements

Figure 2
Alternating-gradient magnetometer: P, electromagnet pole
piece; C, drive coil to create alternating-field gradient in
horizontal direction; S, sample; R, support rod;
Pz, piezoelectric crystal motion detector;
V, vibration-damping support table; and M, meter
(usually lock-in amplifier)

the average field, c a n be varied o r reversed a n d the

v o l u m e of u n i f o r m g r a d i e n t c a n b e m a d e larger.
F u r t h e r m o r e , t h e g r a d i e n t a n d therefore t h e sensiti
vity c a n be increased b y a b o u t a factor of ten.
H o w e v e r , t h e g r a d i e n t coils require a n increase in t h e
magnet gap and, consequently, reduce the m a x i m u m
average field.
If the g r a d i e n t field is p r o d u c e d b y coils in t h e
m a g n e t g a p a n d is m a d e ac instead of d c , t h e s a m p l e is
subjected t o a n a l t e r n a t i n g force, w h i c h c a n be m a d e
either parallel o r p e r p e n d i c u l a r t o t h e d c field of t h e
m a g n e t . T h e d i s p l a c e m e n t c a u s e d by this force c a n b e
detected b y m o u n t i n g t h e s a m p l e o n a thin s u p p o r t
a r m which is a t t a c h e d t o a piezoelectric crystal; t h e a c
voltage o u t p u t of t h e piezoelectric is detected a n d
amplified b y a lock-in amplifier (see Fig. 2). If t h e
frequency of t h e g r a d i e n t field is t u n e d t o t h e m e c h
anical r e s o n a n t frequency of t h e s u p p o r t a r m a n d t h e
s a m p l e , t h e a m p l i t u d e of t h e v i b r a t i o n is increased b y
the Q of t h e r e s o n a n t system, which is of o r d e r 100.
This device h a s been called t h e a l t e r n a t i n g - g r a d i e n t
10
m a g n e t o m e t e r , a n d c a n h a v e a sensitivity of 1 0 "
2
A m ( F l a n d e r s 1988, F r e y et al. 1988); a c o m m e r c i a l
version is available for r o o m - t e m p e r a t u r e use.
1.2 Induction
Methods
If t h e
magnetic
flux
density
( = + 4 in cgs units) t h r e a d i n g
a n d a r e a A is c h a n g e d by a n a m o u n t
g e n e r a t e d in t h e coil of m a g n i t u d e

226

= 0( + )
a coil of t u r n s
dB, a voltage is
E = kNA(dB/

dt), w h e r e k d e p e n d s o n t h e system of u n i t s in use. A

device c a p a b l e of i n t e g r a t i n g this voltage gives a n
o u t p u t signal p r o p o r t i o n a l t o t h e c h a n g e in B. Before
electronic i n s t r u m e n t a t i o n w a s available, the integ
r a t i o n w a s d o n e by a ballistic g a l v a n o m e t e r o r b y a
related e l e c t r o m e c h a n i c a l i n s t r u m e n t called a fluxm e t e r ; with t h e availability of electronic i n s t r u m e n
t a t i o n t h e i n t e g r a t i o n is d o n e b y a n o p e r a t i o n a l
amplifier circuit a n d t h e c o m p l e t e i n s t r u m e n t is called
a n electronic fluxmeter o r simply a fluxmeter. N o t e
t h a t t h e fluxmeter m e a s u r e s B, n o t . F o r m a n y
engineering p u r p o s e s , is actually t h e m o r e useful
q u a n t i t y a n d c a n always be f o u n d from if the
field is k n o w n . Alternatively, t w o identical coils c a n
b e c o n n e c t e d in series o p p o s i t i o n a n d p l a c e d in identi
cal fields. O n e coil c o n t a i n s t h e s a m p l e a n d m e a s u r e s
(H + M ) ; t h e o t h e r c o n t a i n s n o s a m p l e a n d m e a s u r e s
only H. T h e difference is t h e n t h e m a g n e t i z a t i o n M.
N o t e also t h a t t h e fluxmeter m e a s u r e s only changes
in B, so t h a t in o r d e r t o m a k e a m e a s u r e m e n t , the flux
density t h r e a d i n g t h e coil m u s t be c h a n g e d , either
by c h a n g i n g o r b y m o v i n g t h e s a m p l e relative t o t h e
coil. T h e sensitivity of t h e fluxmeter is limited by drift
6
in t h e o u t p u t , a n d is a b o u t 1 0 ~ W b t u r n s (100
maxwell t u r n s ) , c o r r e s p o n d i n g t o 0.01 m T (0.1 G )
2
with a coil of 1000 t u r n s a n d 1 c m a r e a . F l u x m e t e r s
a r e m o s t often used w h e n t h e s a m p l e is in a closed
m a g n e t i c circuit, either in t h e f o r m of a c o m p l e t e ring
o r as a p a r t of a ring with t h e rest of t h e m a g n e t i c p a t h
c o m p r i s i n g a y o k e of h i g h - p e r m e a b i l i t y m a g n e t i c
m a t e r i a l . I n t h e latter case, t h e m e a s u r e m e n t of t h e
field p r e s e n t s certain difficulties (see Sect. 3).
I n s t e a d of electronic a n a l o g i n t e g r a t i o n of t h e in
d u c t i o n v o l t a g e , t h e voltage signal c a n be digitized,
s t o r e d a n d digitally i n t e g r a t e d . W h e n t h e s a m p l e s a r e
large a n d strongly m a g n e t i c , either m e t h o d will serve;
h o w e v e r , a n a l o g i n t e g r a t i o n is b e t t e r for small o r
weakly magnetic samples.
If t h e s a m p l e is m a g n e t i z e d w i t h a n a c field a n d t h e
i n d u c t i o n voltage is simply amplified r a t h e r t h a n
i n t e g r a t e d , t h e ac i n c r e m e n t a l susceptibility (AM/AH)
is m e a s u r e d directly. T h i s m e t h o d is limited t o rela
tively low fields (since high fields c a n n o t b e cycled
rapidly), b u t is useful for d e t e r m i n i n g C u r i e t e m p e r a
tures of f e r r o m a g n e t i c a n d ferrimagnetic m a t e r i a l s
a n d t h e t e m p e r a t u r e d e p e n d e n c e of susceptibility of
weakly magnetic materials and superconductors. A
lock-in amplifier is usually used t o detect t h e a c
i n d u c t i o n signal a t t h e drive frequency; it c a n b e used
t o give b o t h t h e real a n d i m a g i n a r y p a r t s of t h e
susceptibility. A d c field s u p e r i m p o s e d o n t h e a c drive
field c a n give a d d i t i o n a l useful i n f o r m a t i o n in
m e a s u r e m e n t s o n s u p e r c o n d u c t i n g s a m p l e s (see
Superconducting
Materials:
Measurements).
1.3 Measurement of Field Produced by Sample
A m a g n e t i z e d s a m p l e n o t in a closed m a g n e t i c circuit
p r o d u c e s a field in t h e s u r r o u n d i n g space. T h e m a g n i
t u d e of this field a t a n y p o i n t is p r o p o r t i o n a l t o t h e

Magnetic

Materials:

Measurements

>)

()

Figure 3
(a) VSM and (b) alternate version in which the signal from sample S is balanced against a signal from a reference sample
(Ref) of fixed magnetic moment: P, electromagnet pole piece; R, sample support rod; C, sensing or pickup coils
(orientation and location may vary); D, sample motion (mechanism not shown); and M, meter (usually lock-in amplifier)

m a g n e t i z a t i o n of t h e s a m p l e . V a r i o u s m e t h o d s h a v e
been used t o m e a s u r e this field; t h e principal difficulty
is to s e p a r a t e the field p r o d u c e d b y t h e s a m p l e from
the applied field c a u s i n g t h e m a g n e t i z a t i o n of t h e
sample. O n e m e t h o d is t o c h o o s e a m e a s u r i n g p o i n t
w h e r e the field from t h e s a m p l e h a s a large c o m
p o n e n t p e r p e n d i c u l a r t o t h e a p p l i e d field a n d m e a s u r e
the p e r p e n d i c u l a r field, usually with a Hall-effect
sensor. Since t h e applied field is usually large c o m
p a r e d with t h e s a m p l e field, careful o r i e n t a t i o n of t h e
field sensor is r e q u i r e d .
T h e m o s t c o m m o n s o l u t i o n is t o oscillate o r v i b r a t e
the s a m p l e a t a fixed frequency. T h e s a m p l e field is
then ac, n o t d c , a n d c a n b e easily s e p a r a t e d from t h e
dc applied field. T h e i n s t r u m e n t b a s e d o n this p r i n
ciple is the v i b r a t i n g - s a m p l e m a g n e t o m e t e r , o r V S M
(also s o m e t i m e s called a F o n e r m a g n e t o m e t e r after its
inventor). It is widely used for m e a s u r e m e n t s o n small
samples a t high fields. T h e s a m p l e is usually oscillated
p e r p e n d i c u l a r t o t h e applied field, either b y a l o u d
speaker c o n e o r b y a m e c h a n i c a l c a m (see F i g . 3). I n
the former case t h e frequency is a b o u t 100 H z a n d t h e
a m p l i t u d e is a b o u t 0.1 m m ; in t h e latter case t h e
frequency is a b o u t 20 H z a n d t h e a m p l i t u d e a b o u t
2 m m . T h e l o u d s p e a k e r system needs s o m e k i n d of
feedback c o n t r o l t o m a i n t a i n t h e v i b r a t i o n a m p l i t u d e
c o n s t a n t a n d , generally, is limited t o s a m p l e s of less

t h a n a b o u t 100 m g . I n b o t h cases, t h e a c field p r o

d u c e d by t h e s a m p l e m o t i o n is sensed by symmetrical
sets of coils placed in t h e g a p of t h e m a g n e t a n d the
signal is amplified b y a lock-in amplifier locked t o the
frequency of s a m p l e v i b r a t i o n . B o t h types of V S M a r e
available c o m m e r c i a l l y , with accessories t o p e r m i t
m e a s u r e m e n t s from 4 t o a b o u t 1000 K .
T h e limiting sensitivity of t h e V S M is usually
8
2
5
q u o t e d as 1 0 " A m ( 1 0 ~ e m u ) ; t h e practical limit in
n o r m a l o p e r a t i o n is a b o u t ten times larger.
1.4 SQUID

Measurements

T h e highest available sensitivity for t h e m e a s u r e

m e n t of m a g n e t i z a t i o n is p r o v i d e d by the S Q U I D
( s u p e r c o n d u c t i n g q u a n t u m interference device) m a g
n e t o m e t e r . T h e S Q U I D itself, i n c o r p o r a t i n g a super
c o n d u c t i n g J o s e p h s o n j u n c t i o n , usually o p e r a t e s in
liquid h e l i u m , so a S Q U I D m a g n e t o m e t e r is often
used in c o n j u n c t i o n with a s u p e r c o n d u c t i n g m a g n e t .
T h i s m e a n s t h a t a p p l i e d fields below a few h u n d r e d
a m p e r e s p e r m e t e r a r e n o t easily available. T h e s a m
ple is p a s s e d slowly t h r o u g h a set of coils w o u n d from
superconducting material, which are connected to the
S Q U I D . T h e t o t a l flux p a s s i n g t h r o u g h the coils is
p r o p o r t i o n a l t o t h e S Q U I D o u t p u t voltage. T h e field
m u s t be a c c u r a t e l y c o n s t a n t d u r i n g t h e m e a s u r e m e n t
a n d , in practice, several m i n u t e s elapse between

227

Magnetic

Materials:

Measurements

m e a s u r e m e n t s if either the field o r t h e t e m p e r a t u r e is

c h a n g e d . A c o m p l e t e hysteresis l o o p o r a t e m p e r a t u r e
sweep from 4 t o 300 t h e n requires several h o u r s
a n d c o m m e r c i a l systems a r e set u p for a u t o m a t i c
u n a t t e n d e d o p e r a t i o n . T h e claimed limiting sensitivity
12
2
-9
is 1 0 " A m ( 1 0 e m u ) ; as in t h e case of t h e V S M , a
practical limit is a b o u t a factor of ten higher. S Q U I D
systems a r e beginning t o b e c o m e available with super
conducting junctions based on high-temperature
oxide s u p e r c o n d u c t o r s which c a n o p e r a t e a t liquid
n i t r o g e n t e m p e r a t u r e s (77 K ) . T h e limiting sensi
tivity a t 77 is less t h a n in liquid h e l i u m (4 K ) .

2. Measurement

of Magnetic

Field

T h e s t a n d a r d g e n e r a l - p u r p o s e field-measuring instru
m e n t uses the H a l l effect in a small p l a t e of a
s e m i c o n d u c t i n g m a t e r i a l . U s u a l l y k n o w n as a g a u s s meter, this i n s t r u m e n t c a n m e a s u r e fields from levels
1
c o m p a r a b l e with t h e e a r t h ' s field ( ~ 10 A m " ) u p t o
_1
1
at least 5 M A m
a n d often 15 M A m
with a c c u r a
cies of a b o u t 1 % . T h e sensing element c a n b e as small
2
as 1 m m a n d b o t h d c a n d a c fields c a n be m e a s u r e d .
Special H a l l elements a r e m a d e for use a t cryogenic
t e m p e r a t u r e s a n d c a n be repeatedly cycled t o low
temperatures without damage (Rubin and Sample
1980).
A simple c o p p e r coil c o n n e c t e d t o a fluxmeter c a n
be used t o m e a s u r e c h a n g e s in t h e flux t h r o u g h t h e
coil, which is equivalent t o t h e a v e r a g e field in t h e coil.
Because of drift in t h e i n t e g r a t o r o u t p u t , this system is
useful primarily w h e n t h e field is cycled fairly rapidly,
as in the m e a s u r e m e n t of hysteresis l o o p s . H o w e v e r , if
the signal is large (a big coil with m a n y t u r n s in a
s t r o n g field), drift m a y n o t be a p r o b l e m . Coils of
special geometries c a n be used t o m i n i m i z e t h e e r r o r s
d u e t o fields t h a t a r e n o n u n i f o r m over d i m e n s i o n s
c o m p a r a b l e with t h e size of the coil (Zijlstra 1967 P t .
2, p p . 3-7). If the coil is oscillated o r r o t a t e d in t h e
field, a n ac voltage is g e n e r a t e d w h o s e m a g n i t u d e is
p r o p o r t i o n a l t o the field. C o m m e r c i a l i n s t r u m e n t s
called rotating-coil g a u s s m e t e r s h a v e been built using
this principle, b u t a r e less c o n v e n i e n t t o use t h a n H a l l effect i n s t r u m e n t s .
T h e r e s o n a n c e frequency of v a r i o u s a t o m i c nuclei
d e p e n d s linearly o n the applied m a g n e t i c field, w i t h a
p r o p o r t i o n a l i t y c o n s t a n t k n o w n t o high a c c u r a c y .
T h e m e a s u r e d r e s o n a n c e frequency t h e n establishes
the value of t h e applied field. F o r successful n u c l e a r
m a g n e t i c r e s o n a n c e ( N M R ) m e a s u r e m e n t s , t h e field
m u s t be highly u n i f o r m b o t h in s p a c e a n d time
( a l t h o u g h in m o d e r n i n s t r u m e n t s t h e size of t h e p r o b e
h a s been m u c h r e d u c e d ) ; c o n s e q u e n t l y this m e t h o d is
used m a i n l y t o calibrate o t h e r sensors.
F o r fields lower t h a n the e a r t h ' s field, the m o s t
c o m m o n field-measuring i n s t r u m e n t is t h e fluxgate
m a g n e t o m e t e r , which m e a s u r e s the applied d c field
required t o m a k e t h e ac hysteresis l o o p of a high-

228

p e r m e a b i l i t y m a g n e t i c strip exactly s y m m e t r i c . A t this

p o i n t , the net d c field o n t h e m a t e r i a l is zero, so t h e
applied d c field is e q u a l a n d o p p o s i t e t o t h e (preexist
ing) field t o b e m e a s u r e d . Fields of this level a r e rarely
used in t h e m e a s u r e m e n t of m a g n e t i c m a t e r i a l s .

3. Demagnetizing

Fields

A s n o t e d , a n y m a g n e t i z e d s a m p l e n o t in a closed
m a g n e t i c circuit creates a field in t h e s u r r o u n d i n g
space. T h i s field exists within t h e s a m p l e itself, as well
as in t h e s u r r o u n d i n g space, a n d inside t h e s a m p l e is
a l w a y s o p p o s i t e in d i r e c t i o n t o t h e s a m p l e m a g n e t i z a
tion. It is therefore called t h e d e m a g n e t i z i n g field.
T h i s is a perfectly real field, n o t a m a t h e m a t i c a l
a b s t r a c t i o n , a n d is often far from negligible. P r o p e r
a n d a c c u r a t e c o r r e c t i o n for t h e d e m a g n e t i z i n g field is
a persistent p r o b l e m in m a n y m a g n e t i c m e a s u r e
ments.
If t h e s a m p l e is a n ellipsoid a n d is u n i f o r m l y
m a g n e t i z e d , t h e d e m a g n e t i z i n g field is u n i f o r m
t h r o u g h o u t t h e s a m p l e a n d is linearly related t o t h e
m a g n e t i z a t i o n of t h e s a m p l e b y a p r o p o r t i o n a l i t y
c o n s t a n t k n o w n as t h e d e m a g n e t i z i n g factor (D in SI,
in cgs), w h i c h d e p e n d s o n t h e s a m p l e s h a p e . T h e
d e m a g n e t i z i n g factor c a n be calculated from f o r m u l a e
given in t e x t b o o k s , a n d t a b u l a t e d values a n d g r a p h s
a r e also widely available. T h e m a x i m u m v a l u e of t h e
d e m a g n e t i z i n g field, for a n infinite p l a t e m a g n e t i z e d
p e r p e n d i c u l a r t o its surface, is u n i t y in SI o r 4 in cgs.
T h e m a x i m u m possible d e m a g n e t i z i n g field is t h e r e
fore numerically e q u a l t o M s (SI) o r 4nMs (cgs); this
1
c o r r e s p o n d s t o over 1.6 M A m
( 2 0 k O e ) for iron
samples.
Ellipsoidal s a m p l e s a r e difficult t o m a k e a n d t o
m o u n t in e x p e r i m e n t a l e q u i p m e n t a n d a r e n o t used as
often as they s h o u l d be. T h e d e m a g n e t i z i n g factor
parallel t o t h e axis of a r o d decreases w i t h increasing
l e n g t h / d i a m e t e r a n d , for a disk s a m p l e a l o n g a dia
m e t e r , decreases with increasing d i a m e t e r / t h i c k n e s s ,
so l o n g thin r o d s o r thin disks a r e often used as
s a m p l e s with t h e d e m a g n e t i z i n g factor a s s u m e d e q u a l
t o t h a t of t h e e q u i v a l e n t ellipsoid. T h e " e q u i v a l e n t "
ellipsoid is usually t a k e n t o be t h e ellipsoid of t h e
s a m e aspect r a t i o as t h e s a m p l e , a l t h o u g h this is n o t
strictly correct.
If t h e d e m a g n e t i z i n g c o r r e c t i o n needs t o be m a d e
with high a c c u r a c y , t w o general m e t h o d s a r e avail
able. Since t h e t a n g e n t i a l fields j u s t o u t s i d e a n d j u s t
inside t h e surface of a s a m p l e a r e e q u a l , a direct
m e a s u r e m e n t of t h e parallel field at t h e surface of t h e
s a m p l e gives t h e t r u e field acting inside t h e s a m p l e :
t h a t is, t h e a p p l i e d field m i n u s t h e d e m a g n e t i z i n g
field. T h i s field c a n b e m e a s u r e d w i t h a H a l l p r o b e , o r
with a coil a n d fluxmeter. Since t h e field c a n n o t b e
m e a s u r e d exactly a t t h e s a m p l e surface, a n d is usually
c h a n g i n g r a p i d l y with d i s t a n c e from the surface, it
m a y b e necessary t o m e a s u r e a t several p o i n t s , e a c h a

Magnetic

k n o w n distance from t h e surface, a n d e x t r a p o l a t e t o

the surface. O f c o u r s e , t h e d e m a g n e t i z i n g field m a y
n o t be u n i f o r m within t h e s a m p l e .
Alternatively, use c a n be m a d e of t h e fact t h a t for a
high-permeability, low-coercive-field m a t e r i a l , t h e
slope of the m a g n e t i z a t i o n c u r v e a t low fields is
g o v e r n e d a l m o s t entirely by t h e d e m a g n e t i z i n g field.
In such a m a t e r i a l , t h e m a g n e t i z a t i o n adjusts itself t o
a value such t h a t t h e d e m a g n e t i z i n g field is e q u a l a n d
o p p o s i t e t o t h e a p p l i e d field, m a k i n g the t r u e i n t e r n a l
field zero. T h e n t h e slope of t h e curve of m a g n e t i z a
tion vs applied field a t low fields is numerically e q u a l
t o t h e reciprocal of t h e d e m a g n e t i z i n g factor. T h e
d e m a g n e t i z i n g factor t h u s d e t e r m i n e d for a highp e r m e a b i l i t y s a m p l e s h o u l d a p p l y t o o t h e r s a m p l e s of
t h e s a m e s h a p e m e a s u r e d in t h e s a m e a p p a r a t u s .
T o eliminate t h e d e m a g n e t i z i n g field, a h o m o
g e n e o u s ring s a m p l e c a n be used. T h e field is a p p l i e d
b y a coil w o u n d o n t o t h e r i n g a n d c a n b e c a l c u l a t e d
exactly from t h e circumference of t h e ring, t h e
n u m b e r of t u r n s a n d t h e c u r r e n t . N o t e t h a t t h e field is
higher a t t h e inside d i a m e t e r t h a n a t t h e o u t s i d e
d i a m e t e r , b e c a u s e of t h e difference in circumferences;
for m i n i m u m u n c e r t a i n t y in field, t h e r a d i a l thickness
of the ring s h o u l d be small c o m p a r e d with t h e ring
diameter. T h e m a x i m u m field is limited by h e a t gener
- 1
(100 O e ) . I n a
a t e d in t h e w i n d i n g s t o a b o u t 8 k A m
c o m p o s i t e ring s a m p l e , c o m p r i s i n g a s a m p l e t o be
m e a s u r e d c l a m p e d in a h i g h - p e r m e a b i l i t y y o k e , t h e
y o k e m a t e r i a l ideally h a s m u c h higher p e r m e a b i l i t y
a n d cross-sectional a r e a t h a n t h e s a m p l e , so t h a t all
the a m p e r e t u r n s of m a g n e t o m o t i v e force act o n t h e
sample a n d t h e field c a n be calculated from t h e k n o w n
a m p e r e t u r n s a n d t h e length of t h e s a m p l e . I n p r a c
tice, this is often a n i n a d e q u a t e a p p r o x i m a t i o n a n d
o n e of t h e e x p e r i m e n t a l m e t h o d s described previously
m u s t be used t o d e t e r m i n e t h e t r u e a p p l i e d field.

Effect

W h e n m e a s u r e m e n t s a r e m a d e in t h e g a p of a n
e l e c t r o m a g n e t , t h e presence of large v o l u m e s of highpermeability m a g n e t i c m a t e r i a l in t h e p o l e pieces acts
to d i s t o r t t h e field s u r r o u n d i n g t h e s a m p l e . I n t h e
limiting case of semi-infinite slabs of u n i f o r m l y per
m e a b l e m a t e r i a l , t h e effect c a n b e described m a t h e m a
tically b y m a g n e t i c " i m a g e s " of t h e s a m p l e existing in
the pole pieces a t t h e m i r r o r i m a g e p o s i t i o n s . A t high
fields, the m a t e r i a l of t h e p o l e pieces a p p r o a c h e s
m a g n e t i c s a t u r a t i o n , t h e p e r m e a b i l i t y decreases t o
wards unity and the images tend to disappear. The
c a l i b r a t i o n c o n s t a n t relating t h e m a g n e t i z a t i o n of t h e
sample t o t h e o u t p u t signal of t h e m a g n e t o m e t e r t h e n
changes with field. T h i s usually results in a n a p p a r e n t
decrease in m a g n e t i z a t i o n with increasing field a t high
fields; this p h e n o m e n o n is w h a t is usually m e a n t b y
the image effect. T h e i m a g e effect m a y be m i n i m i z e d
by increasing t h e m a g n e t g a p , a t t h e cost of lower

Measurements

m a x i m u m field, o r simply b y limiting t h e m a x i m u m

field t o values w h e r e t h e i m a g e effect r e m a i n s sensibly
c o n s t a n t . P l a c i n g t h e m a g n e t i z a t i o n sensor a s far as
possible from t h e p o l e pieces is also helpful, b u t is
often i n c o m p a t i b l e with placing a furnace o r lowt e m p e r a t u r e vessel in t h e m a g n e t g a p .
A field-dependent c a l i b r a t i o n c a n be m a d e using a
s a m p l e w h o s e m a g n e t i z a t i o n is i n d e p e n d e n t of field
(or varies with field in a k n o w n w a y ) over a r a n g e of
fields a t h i g h field. A b e t t e r s o l u t i o n in principle is t o
use a c o p p e r coil c a r r y i n g a k n o w n c u r r e n t , which acts
like a cylindrical s a m p l e of fixed m a g n e t i c m o m e n t .
H o w e v e r , t h e m a g n e t i c m o m e n t p r o d u c e d by such a
coil is small c o m p a r e d w i t h t h e m o m e n t of a strongly
m a g n e t i z e d s a m p l e of t h e s a m e size a n d s h a p e .

5. Curie

Temperature

T h e C u r i e t e m p e r a t u r e is t h e t e m p e r a t u r e a t which
a f e r r o m a g n e t i c o r ferrimagnetic m a t e r i a l loses its
m a g n e t i z a t i o n a n d b e c o m e s p a r a m a g n e t i c . T h e equiv
alent t e m p e r a t u r e in a n a n t i f e r r o m a g n e t is called the
Neel t e m p e r a t u r e . A n a p p r o x i m a t e value for the
C u r i e t e m p e r a t u r e c a n be o b t a i n e d b y m e a s u r i n g t h e
m a g n e t i z a t i o n (by a n y m e t h o d ) as a function of
t e m p e r a t u r e . H o w e v e r , in high fields t h e t r a n s i t i o n
from f e r r o m a g n e t i c t o p a r a m a g n e t i c b e h a v i o u r is
often n o t s h a r p l y defined, so t h a t either a low-field
m e a s u r e m e n t o r a n e x t r a p o l a t i o n t o low field is
- 1
necessary. T h e low-field susceptibility ( 0 . 1 - 1 0 A m )
often s h o w s a m a x i m u m a t o r n e a r t h e C u r i e t e m
p e r a t u r e ; this is k n o w n as t h e H o p k i n s o n effect
( H o p k i n s o n 1889) a n d is strongly d e p e n d e n t o n t h e
sample microstructure.

6. Magnetocrystalline
4. Image

Materials:

Anisotropy

M a g n e t o c r y s t a l l i n e a n i s o t r o p y describes t h e fact t h a t
t h e energy of a m a g n e t i c crystal d e p e n d s o n the
direction of t h e s a t u r a t i o n m a g n e t i z a t i o n relative t o
t h e c r y s t a l l o g r a p h i c axes. O t h e r m a g n e t i c a n i s o t r o
pics, d u e t o s h a p e , stress a n d so o n , c a n also exist.
A c c u r a t e m e a s u r e m e n t of t h e crystal a n i s o t r o p y re
quires a single-crystal s a m p l e , a l t h o u g h s o m e infor
m a t i o n c a n be e x t r a c t e d from m e a s u r e m e n t s o n a n
aligned p o w d e r s a m p l e o r a t e x t u r e d polycrystal.
A n i s o t r o p y is expressed as a series of t r i g o n o m e t r i c
t e r m s , e a c h multiplied b y a c o n s t a n t called a n a n i s o
tropy constant.
T h e m o s t satisfactory e x p e r i m e n t a l m e t h o d for t h e
d e t e r m i n a t i o n of a n i s o t r o p y is t h e m e a s u r e m e n t of
t h e t o r q u e a c t i n g o n a n ellipsoidal (or d i s k - s h a p e d )
s a m p l e as t h e s a m p l e is r o t a t e d a b o u t its axis of
s y m m e t r y in a s a t u r a t i n g a p p l i e d field p e r p e n d i c u l a r
t o this axis. A n i n s t r u m e n t m a d e for this p u r p o s e is
called a t o r q u e m a g n e t o m e t e r o r simply a t o r q u e m e t e r . T h e s h a p e of t h e t o r q u e c u r v e reflects t h e

229

Magnetic

Materials:

Measurements

crystallographic s y m m e t r y of t h e s a m p l e a n d t h e
m a g n i t u d e of t h e t o r q u e is related t o t h e m a g n i t u d e of
the a n i s o t r o p y . A difficulty is t h a t t h e direction of t h e
m a g n e t i z a t i o n relative t o the field a n d t h e crystal axes
is n o t k n o w n directly, b u t m u s t b e d e d u c e d from t h e
value of t h e s a t u r a t i o n m a g n e t i z a t i o n ( a s s u m e d c o n
s t a n t a t high fields) a n d t h e m e a s u r e d t o r q u e .
Generally, t h e a p p a r e n t a n i s o t r o p y increases slightly
with field a n d s o m e k i n d of e x t r a p o l a t i o n is r e q u i r e d .
Details of t h e m e t h o d a n d the m a t h e m a t i c s t h a t a p p l y
to v a r i o u s crystal s t r u c t u r e s a n d t o different crystallo
g r a p h i c p l a n e s in the p l a n e of t h e disk s a m p l e a r e
given by C h i k a z u m i (1964), Cullity (1972) a n d
P e a r s o n (1979).
A variety of t o r q u e - m e a s u r i n g m e t h o d s c a n be used
( P e a r s o n 1979). If the samples a n d t o r q u e s a r e large,
rigid systems with deflections m e a s u r e d b y strain
gauges c a n be used. Small t o r q u e s associated with
small samples o r small values of t h e a n i s o t r o p y re
quire sensitive t o r q u e - m e a s u r i n g systems using fine
filaments. T h e wide r a n g e of t o r q u e values t h a t m a y
be e n c o u n t e r e d m a k e s t h e d e v e l o p m e n t of c o m m e r
cial i n s t r u m e n t s difficult a n d m o s t i n s t r u m e n t s a r e
p u r p o s e built.
If a m a g n e t i c field p r o d u c e s a t o r q u e o n a disks h a p e d s a m p l e , there m u s t be a c o m p o n e n t of m a g n e
tization p e r p e n d i c u l a r t o the applied field a n d a
m e a s u r e m e n t of this p e r p e n d i c u l a r m a g n e t i z a t i o n is
equivalent t o t h e m e a s u r e m e n t of t h e t o r q u e . V a r i o u s
schemes for the m e a s u r e m e n t of p e r p e n d i c u l a r m a g
netization h a v e been used ( P e a r s o n 1979); they c a n
h a v e the a d v a n t a g e of being able t o be c o n t i n u o u s l y
read, which is c o n v e n i e n t for following t h e c h a n g e s in
a n i s o t r o p y with t e m p e r a t u r e o r field. T h e y h a v e t h e
d i s a d v a n t a g e t h a t the m e a s u r e d signal decreases with
increasing field, so t h a t e x t r a p o l a t i o n t o high fields is
somewhat uncertain.
Values of the a n i s o t r o p y c o n s t a n t s c a n also be
o b t a i n e d by m e a s u r i n g t h e m a g n e t i z a t i o n curves (M
vs H) in v a r i o u s c r y s t a l l o g r a p h i c directions, a n d c o m
p a r i n g the energy r e q u i r e d t o reach m a g n e t i c s a t u
r a t i o n . Physically, this is n o t strictly e q u i v a l e n t t o
r o t a t i n g the s a t u r a t i o n m a g n e t i z a t i o n from o n e crys
t a l l o g r a p h i c direction t o a n o t h e r b u t , in practice, t h e
difference is n o t usually significant.
T h e d e p e n d e n c e of t h e f e r r o m a g n e t i c r e s o n a n c e
frequency o r field o n c r y s t a l l o g r a p h i c direction c a n
also be i n t e r p r e t e d t o give a n i s o t r o p y c o n s t a n t s .
S o m e r a r e - e a r t h elements a n d c o m p o u n d s h a v e
very s t r o n g a n i s o t r o p y , so t h a t fields higher t h a n
t h o s e available from l a b o r a t o r y e l e c t r o m a g n e t s
1
o r 2 0 k O e ) a r e necessary for their
( ~ 1.6 A m
m e a s u r e m e n t . S u p e r c o n d u c t i n g m a g n e t s o r Bitter
m a g n e t s (see Sect. 8) m a y be used, except their u s u a l
configuration m a k e s t o r q u e m e a s u r e m e n t s difficult.
Very high pulsed fields with pulse w i d t h s of m a n y
milliseconds c a n be p r o d u c e d b y d i s c h a r g i n g a large
c a p a c i t o r b a n k t h r o u g h a reinforced coil; e q u i p m e n t
of this k i n d is m a d e c o m m e r c i a l l y for m a g n e t i z i n g
230

p e r m a n e n t m a g n e t s a n d c a n also be used with a p p r o

p r i a t e i n s t r u m e n t a t i o n for s o m e k i n d s of high-field
measurements.

7.

Magnetostriction

M a g n e t o s t r i c t i o n describes t h e c h a n g e in d i m e n s i o n s
of a m a g n e t i c s a m p l e with c h a n g e s in t h e state o r
direction of m a g n e t i z a t i o n . F r o m a n engineering
p o i n t of view, t h e q u a n t i t y of interest is the c h a n g e in
length of a s a m p l e w h e n its m a g n e t i z a t i o n is c h a n g e d ,
typically from p l u s t o m i n u s s a t u r a t i o n o r n e a r satu
r a t i o n . Scientifically, t h e m e a s u r e d values a r e the
c h a n g e s in d i m e n s i o n of a single crystal as the satu
r a t i o n m a g n e t i z a t i o n is r o t a t e d t o v a r i o u s crystallo
g r a p h i c directions. T h e e x p e r i m e n t a l c o n s i d e r a t i o n s
a r e similar in b o t h cases (Lee 1979).
M a g n e t o s t r i c t i v e strains a r e generally small, of the
5
o r d e r of 1 0 " . If the available s a m p l e s a r e large
e n o u g h , electric resistance strain gauges p r o v i d e t h e
simplest m e a s u r e m e n t t e c h n i q u e . T h e y c a n be driven
with either ac o r d c c u r r e n t s , a n d the m a n u f a c t u r e r ' s
c a l i b r a t i o n c o n s t a n t s a r e sufficient for a c c u r a c y of
a b o u t 1 % . M o s t strain g a u g e alloys s h o w significant
m a g n e t o r e s i s t a n c e , w h i c h m u s t b e b a l a n c e d with a
d u m m y g a u g e n o t a t t a c h e d t o t h e s a m p l e b u t in the
s a m e field, o r o t h e r w i s e c o r r e c t e d for.
L i n e a r variable differential t r a n s f o r m e r s ( L V D T s )
a r e p o s i t i o n sensors with sufficient sensitivity for
m a g n e t o s t r i c t i o n m e a s u r e m e n t s a n d a r e useful for
r i b b o n o r wire s a m p l e s t h a t a r e t o o thin o r t o o n a r r o w
for strain gauges. L V D T s h a v e t h e a d v a n t a g e t h a t the
m e a s u r i n g i n s t r u m e n t c a n b e held a t r o o m t e m p e r a
t u r e w h e n t h e s a m p l e is h e a t e d o r cooled. Very small
s a m p l e s m a y be m e a s u r e d using c a p a c i t a n c e m e t h o d s ,
w h e r e c h a n g e s in t h e length of t h e s a m p l e v a r y t h e
spacing of a p a i r of c a p a c i t o r plates.
If l o n g s a m p l e s (1 m ) a r e t o be m e a s u r e d , as o n steel
t r a n s f o r m e r sheets, c o m m e r c i a l p h o n o g r a p h p i c k u p s
h a v e sufficient sensitivity a n d a r e easy a n d c o n v e n i e n t
to use.

8. Use of Superconducting
Magnets

Solenoids

or

Bitter

T h e t r a d i t i o n a l sources of m a g n e t i c fields a r e simple

_ 1
or
c o p p e r coils for low fields (0.01 T , 8 k A m
100 Oe) a n d i r o n - c o r e e l e c t r o m a g n e t s for high fields
1
( 2 T , 1.6 M A m " o r 2 0 k O e ) . M u c h higher fields a r e
a t t a i n a b l e in w a t e r - c o o l e d reinforced c o p p e r coils
(Bitter m a g n e t s , available a t only a few locations in
t h e w o r l d ) , high-field s u p e r c o n d u c t i n g solenoids o r
pulsed coils. S u p e r c o n d u c t i n g m a g n e t s a r e c o m
mercially available in t h e r a n g e 7 - 2 0 T . Bitter m a g
nets c a n r e a c h 25 a n d Bitter m a g n e t s c o m b i n e d
with s u p e r c o n d u c t i n g m a g n e t s ( " h y b r i d m a g n e t s " )
c a n r e a c h 35 T . (Practical s u p e r c o n d u c t i n g m a g n e t s

Magnetic
currently r e q u i r e o p e r a t i o n in liquid h e l i u m a l t h o u g h
the a p p l i c a t i o n of h i g h - t e m p e r a t u r e s u p e r c o n d u c t o r s
in small coils h a s a l r e a d y b e e n d e m o n s t r a t e d . ) T h e r e
are n o f u n d a m e n t a l differences b e t w e e n m a g n e t i c
m e a s u r e m e n t s in e l e c t r o m a g n e t s a n d in solenoids o r
coils, b e y o n d t h e o b v i o u s fact t h a t access t o t h e
s a m p l e a n d a n y s a m p l e m o t i o n a r e generally parallel
t o the applied field in a solenoid a n d p e r p e n d i c u l a r t o
the field in a n e l e c t r o m a g n e t . T h i s g e o m e t r y m a k e s
t o r q u e m e a s u r e m e n t s difficult, b u t n o t impossible.
(Both s u p e r c o n d u c t i n g a n d w a t e r - c o o l e d solenoids
c a n be built a s split coils t o p e r m i t r a d i a l o r t r a n s v e r s e
access t o t h e highest-field region, a t t h e cost of lower
m a x i m u m field.) Pulsed fields m a y r e q u i r e special
m e a s u r e m e n t t e c h n i q u e s , especially if t h e pulse time is
very s h o r t .
T h e fact t h a t s u p e r c o n d u c t o r s exclude m a g n e t i c
flux a t low fields b u t n o t c o m p l e t e l y a t high fields
gives rise t o a n i m a g e effect in s u p e r c o n d u c t i n g m a g
nets a n a l o g o u s t o t h a t in e l e c t r o m a g n e t s .

9. Magnetic

Measurements

on

Superconductors

S u p e r c o n d u c t o r s in low fields exclude all m a g n e t i c

flux a n d , therefore, h a v e a relative susceptibility
of - 1 in SI units o r a susceptibility of - 1/4 in cgs
units. M a g n e t i c m e a s u r e m e n t s o n s u p e r c o n d u c t i n g
samples c a n p r o v i d e useful i n f o r m a t i o n o n critical
fields, flux t r a p p i n g a n d p i n n i n g , a n d so o n (see
Superconducting
Materials: Measurements',
Goldfarb
a n d S p o m e r 1990). All t h e basic m e a s u r e m e n t
techniques for m a g n e t i c m a t e r i a l s c a n be used for
superconducting materials, remembering that the
m a g n e t i z a t i o n is frequently negative ( o p p o s i t e t o t h e
applied field) a n d therefore t h e d e m a g n e t i z i n g field is
positive (in t h e s a m e sense as t h e a p p l i e d field).
A s n o t e d previously, a c susceptibility m e a s u r e
m e n t s a r e useful in d e d u c i n g t h e p r o p e r t i e s of
inhomogeneous
superconducting
samples.
For
m e a s u r e m e n t s o n s u p e r c o n d u c t i n g cables, it m a y be
desirable t o h a v e s u b s t a n t i a l t r a n s p o r t c u r r e n t flow
ing t h r o u g h t h e s a m p l e d u r i n g t h e m e a s u r e m e n t of
m a g n e t i c p r o p e r t i e s ; this m a k e s t h e V S M a n d force
m e t h o d s generally u n s a t i s f a c t o r y , a n d s o m e system in
which t h e s a m p l e r e m a i n s s t a t i o n a r y m u s t be used.

10. Soft Magnetic

Materials:

Measurements

a s q u a r e frame w h i c h is t h e n o p e r a t e d as a t r a n s
f o r m e r u n d e r n o - l o a d c o n d i t i o n s . T h e p o w e r loss in
t h e t r a n s f o r m e r is m e a s u r e d , usually with a sensitive
a n d a c c u r a t e w a t t m e t e r , with a c o r r e c t i o n applied (if
necessary) for t h e J o u l e h e a t i n g in t h e w i n d i n g s . T h i s
is k n o w n as t h e E p s t e i n test; t h e results a r e q u o t e d in
w a t t s p e r k i l o g r a m (or w a t t s p e r p o u n d ) at a specified
m a x i m u m flux density, usually I T , 1.5 o r 1.8
(10 k G , 1 5 k G o r 18 k G ) , a n d a specified frequency,
n o r m a l l y 50 H z o r 60 H z . T h e o u t p u t voltage w a v e
f o r m of t h e E p s t e i n frame s h o u l d be sinusoidal, which
m e a n s t h a t the flux c h a n g e with t i m e in t h e m a t e r i a l is
sinusoidal; this c o n d i t i o n requires a very n o n s i n u s o i d a l i n p u t c u r r e n t , a c o n d i t i o n t h a t is increasingly
difficult t o m e e t as the m a x i m u m flux density is
increased.
Because the E p s t e i n test uses a relatively large
a m o u n t of m a t e r i a l , a n d a s s e m b l i n g t h e test frame is a
slow m a n u a l o p e r a t i o n , there is a s t r o n g t e n d e n c y t o
s u p p l e m e n t o r replace t h e E p s t e i n test with s o m e form
of single-strip test, using a single strip of test m a t e r i a l
a n d a h i g h - p e r m e a b i l i t y y o k e . H o w e v e r , n o generally
a c c e p t e d single-strip test h a s been d e v e l o p e d .
S o m e t i m e s , t h e i r o n loss ( o r c o r e loss) is " s e p a r
a t e d " i n t o hysteresis loss, m e a s u r e d a t very low fre
q u e n c y o r " d c , " a n d a s s u m e d t o be i n d e p e n d e n t of
frequency; a n d e d d y c u r r e n t loss, a s s u m e d t o vary as
t h e s q u a r e of t h e frequency a n d inversely as the
electrical resistivity. If t h e m e a s u r e d hysteresis loss
p l u s t h e c a l c u l a t e d e d d y c u r r e n t loss is less t h a n the
m e a s u r e d t o t a l a c loss (as is a l w a y s t h e case), t h e
difference is called t h e a n o m a l o u s loss. T h i s simple
linear s e p a r a t i o n of losses is a l m o s t entirely w i t h o u t
physical m e a n i n g .
A n o t h e r c o m m o n specification for high-quality
t r a n s f o r m e r m a t e r i a l is t h e p e a k flux density at a n
1
a p p l i e d field of 800 A m " ( 1 0 O e ) . T h i s is n o r m a l l y
m e a s u r e d a t 50 H z o r 60 H z a n d is a m e a s u r e of the
c r y s t a l l o g r a p h i c o r i e n t a t i o n of t h e steel; h i g h e r values
a r e better.
F o r m a n y a p p l i c a t i o n s , either t h e initial p e r m e a b i
lity o r t h e m a x i m u m p e r m e a b i l i t y / / m ax is i m p o r t a n t ;
p e r m e a b i l i t y is defined as B/H. O t h e r tests a r e used o n
h i g h - p e r m e a b i l i t y m a t e r i a l s t h a t a r e m o r e o r less
directly related t o their i n t e n d e d a p p l i c a t i o n as relays,
high-frequency t r a n s f o r m e r s , shielding m a t e r i a l s , a n d
so o n .

Materials

Sheet o r strip m a t e r i a l s for use in p o w e r - f r e q u e n c y

devices such as t r a n s f o r m e r s a n d m o t o r s a r e usually
specified p r i m a r i l y o n t h e basis o f p o w e r loss, o r t h e
i n p u t electrical energy lost as h e a t w h e n t h e m a t e r i a l
is magnetically cycled t h r o u g h a s y m m e t r i c a l h y s
teresis l o o p of specified m a x i m u m flux density a n d
frequency. T h e s t a n d a r d test p r o c e d u r e for loss
m e a s u r e m e n t s h a s b e e n t h e s a m e for m a n y years: a
g r o u p of identical r e c t a n g u l a r strips is a s s e m b l e d i n t o

11.

Permanent

Magnet

Materials

P e r m a n e n t m a g n e t s a r e always used t o c r e a t e a m a g
netic field in space a n d so a l w a y s o p e r a t e in their o w n
d e m a g n e t i z i n g field. T h e i r b e h a v i o r in t h e second
q u a d r a n t of t h e hysteresis l o o p (H < 0, > 0) is
therefore of p r i m a r y interest. Since high fields a r e
r e q u i r e d for m e a s u r e m e n t s , ring s a m p l e s c a n n o t be
used; s a m p l e s a r e either c l a m p e d in t h e g a p of a n
e l e c t r o m a g n e t , w h i c h o p e r a t e s as a y o k e , o r a r e

231

Magnetic

Materials:

Measurements

m e a s u r e d as isolated samples in a V S M o r similar

device, with a c o r r e c t i o n for t h e d e m a g n e t i z i n g field.
T h e c o m m o n m e a s u r e of q u a l i t y of a p e r m a n e n t
m a g n e t is t h e m a x i m u m energy p r o d u c t
(BH)max,
which is the m a x i m u m value of t h e p r o d u c t of t h e flux
density multiplied by t h e (true) field H, m e a s u r e d in
the second q u a d r a n t of t h e hysteresis l o o p a n d t a k e n
as a positive value. T h e units a r e j o u l e s p e r cubic
m e t e r in SI (gauss oersteds, usually M G O e , in cgs).
T h e v o l u m e of p e r m a n e n t m a g n e t m a t e r i a l r e q u i r e d
t o p r o d u c e a specified level of field in a specified
v o l u m e of s p a c e is inversely p r o p o r t i o n a l t o t h e
m a x i m u m energy p r o d u c t (if the g e o m e t r y of t h e
m a g n e t is correctly c h o s e n ) .
In p e r m a n e n t m a g n e t m a t e r i a l s , t h e distinction
between the o r d i n a r y coercive field (or coercive force)
a n d t h e intrinsic coercive field b e c o m e s i m p o r t a n t .
T h e o r d i n a r y coercive field Hc is t h e (negative) field
required t o r e d u c e t h e flux density from positive
s a t u r a t i o n t o zero; t h e intrinsic coercive field Hci is t h e
field r e q u i r e d t o r e d u c e t h e m a g n e t i z a t i o n t o z e r o .
In a q u a l i t y m o d e r n p e r m a n e n t m a g n e t , r e m a i n s
6
_1
3
almost constant at a b o u t 1 0 A m
(1000 e m u c m )
_ 1
in negative fields u p t o 2 M A m
(24kOe) or
m o r e . U n d e r these c i r c u m s t a n c e s , Hci is twice as
large as Hc.
T h e r e m a n e n t i n d u c t i o n BT a t = 0 is a n o t h e r
i m p o r t a n t q u a n t i t y for p e r m a n e n t m a g n e t m a t e r i a l s .
F o r s o m e a p p l i c a t i o n s , t h e reversible a n d irreversible
c h a n g e s in m a g n e t i c p r o p e r t i e s with t e m p e r a t u r e need
to be m e a s u r e d , usually in t h e t e m p e r a t u r e r a n g e from
room temperature to 150C.
See also: Superconducting Materials: Measurements

Bibliography
American Society for Testing and Materials 1964 Magnetic
TestingTheory and Nomenclature. ASTM Technical
Publication 371. ASTM, Philadelphia. PA
American Society for Testing and Materials 1970 Direct
Current Measurements of Soft Magnetic
Materials.
ASTM Technical Publication 371 SI. ASTM, Philadel
phia, PA
American Society for Testing and Materials 1991 Annual
Book of ASTM Standards, Pt. 44. ASTM, Philadelphia,
PA
Chikazumi S 1964 Physics of Magnetism. Wiley, New York,
pp. 15-37; 128^7
Cullity D 1972 Introduction to Magnetic
Materials.
Addison-Wesley, Reading, MA, Chaps. 1,2; pp. 215-33
Flanders J 1988 An alternating gradient magnetometer.
J. Appl. Phys. 63: 3940-6
Foner S 1967 Special magnetic measurement techniques.
J. Appl. Phys. 38: 1510-19
Frey Th, Jantz W, Stibal R 1988 Compensated vibrating
reed magnetometer. / . Appl. Phys. 64: 6002-8
Goldfarb R, Spomer R L 1990 Magnetic characteristics and
measurements of filamentary Nb-Ti wire for the super
conducting supercollider. Adv. Cryog. Eng. (Mater.) 36:
215-22

232

Hopkinson J 1889 Magnetisation of iron at high temperat

ure. Proc. R. Soc. (London) 45: 318-21
Lee W 1979 Magnetostriction. In: Kalvius G M, Tebble
Robert S (eds.) 1979 Experimental Magnetism. Wiley,
New York, pp. 137-222
McGuire R, Flanders J 1969 Direct current magnetic
measurements. In: Berkowitz A I, Kneller (eds.) 1969
Magnetism and Metallurgy. Academic Press, New York
Oguey J 1969 Alternating current magnetic measure
ments. In: Berkowitz A I, Kneller (eds.) 1969 Magnet
ism and Metallurgy. Academic Press, New York
Pearson R F 1979 Magnetic anisotropy. In: Kalvius G M,
Tebble Robert S (eds.) 1979 Experimental Magnetism.
Wiley, New York, pp. 225-65
Rubin L G, Sample 1980 Hall effect magnetometers for
high magnetic fields and temperatures between 1.5 and
300 K. In: Chien C L, Westgate C R (eds.) 1980 The Hall
Effect and its Applications. Plenum, New York, p. 463
Zijlstra 1967 Experimental Methods in Magnetism. NorthHolland-Wiley, New York
C. D . G r a h a m J r
[University of P e n n s y l v a n i a , P h i l a d e l p h i a ,
Pennsylvania, USA]

Mechanical Properties Microprobe

T h e r e l a t i o n s h i p s b e t w e e n t h e r e s p o n s e of m a t e r i a l s t o
i m p o s e d forces a n d d i s p l a c e m e n t s define t h e m e c h a n i
cal p r o p e r t i e s of t h a t m a t e r i a l . Tests t o quantify these
p r o p e r t i e s so t h a t m a t e r i a l s m a y b e c o m p a r e d a r e
n u m e r o u s a n d varied. T h e m e c h a n i c a l p r o p e r t i e s m i c
r o p r o b e ( M P M ) is a testing system t h a t c a n m e a s u r e
s o m e of t h e m e c h a n i c a l p r o p e r t i e s of a very small
v o l u m e of m a t e r i a l . T h e key t o a system being desig
n a t e d as a n M P M is t h e spatial r e s o l u t i o n of the test.
T o qualify a s a n M P M t h e m i n i m u m v o l u m e of
m a t e r i a l t h a t c a n be tested s h o u l d be n o g r e a t e r t h a n
1 in all t h r e e d i m e n s i o n s . T h u s , systems t h a t test
large a r e a s of t h i n films o r l o n g lengths of small
d i a m e t e r filaments a r e n o t M P M s .
I n t e r m s of t h e v o l u m e of m a t e r i a l tested, t h e M P M
lies b e t w e e n t w o o t h e r devices used t o d e t e r m i n e
m e c h a n i c a l p r o p e r t i e s . T h e m i c r o h a r d n e s s tester is
used t o test v o l u m e s larger t h a n t h o s e accessed b y t h e
M P M . S m a l l e r c o n t a c t s , s o m e t i m e s consisting o f o n l y
a few a t o m s , a r e p r o b e d b y t h e a t o m i c force m i c r o
scope ( A F M ) .

1. Physical

Capabilities

A n M P M is a n exciting c o n c e p t . A system w i t h t h e
ability t o s a m p l e t h e m e c h a n i c a l r e s p o n s e of a speci
m e n w i t h s u b m i c r o m e t e r spatial r e s o l u t i o n h a s a n
extremely wide r a n g e of a p p l i c a t i o n s . R e c e n t d e v e l o p
m e n t s in h a r d w a r e a n d u n d e r s t a n d i n g h a v e m a d e this
goal a reality.
T h e m e c h a n i c a l p r o p e r t i e s m i c r o p r o b e will a d v a n c e
o u r u n d e r s t a n d i n g of m a c r o s c o p i c p r o p e r t i e s in t h e

Mechanical

s a m e w a y t h a t t h e chemical m i c r o p r o b e h a s i m p r o v e d
o u r u n d e r s t a n d i n g of t h e c h e m i s t r y of t h e m a t e r i a l s
a n d t h e t r a n s m i s s i o n electron m i c r o s c o p e ( T E M ) h a s
i m p r o v e d o u r u n d e r s t a n d i n g of s t r u c t u r e s .
O n l y o n e t y p e of m e c h a n i c a l test c a n b e used a s a n
M P M . G i l m a n (1973) s h o w e d t h a t a m i c r o i n d e n t a t i o n test, if p r o p e r l y i n s t r u m e n t e d a n d c o n t r o l l e d ,
c a n p e r f o r m as a n M P M . D u r i n g a n i n d e n t a t i o n test
b o t h elastic a n d plastic s t r a i n s a r e g e n e r a t e d . F o r
m a n y m a t e r i a l s t h e s t r a i n s from b o t h fields a r e of
sufficient m a g n i t u d e t o b e m e a s u r e d . T h e test c a n b e
scaled d o w n so t h a t s u b m i c r o m e t e r v o l u m e s of m a t e r
ial a r e s a m p l e d .
M i c r o i n d e n t a t i o n tests h a v e b e e n used t o m e a s u r e
a n extremely w i d e variety of m a t e r i a l p r o p e r t i e s .
Yield s t r e n g t h ( T a b o r 1951), c r e e p resistance (Westb r o o k 1957, C h u a n d Li 1977), stress r e l a x a t i o n ( C h u
a n d Li 1980), m o d u l u s (Bulychev et al. 1975), fracture
t o u g h n e s s ( L a w n a n d W i l s h a w 1975, L a w n a n d E v a n s
1977) a n d even fatigue tests (Li a n d C h u 1979) h a v e
been p e r f o r m e d u s i n g v a r i o u s types of i n d e n t a t i o n
tests. In a d d i t i o n , b e c a u s e t h e m a t e r i a l being tested is
close t o a surface, e n v i r o n m e n t a l effects c a n b e
m e a s u r e d ( W e s t w o o d a n d M a c m i l l a n 1973). W i t h t h e
p r o p e r c o m b i n a t i o n of m i c r o i n d e n t a t i o n tests a
nearly c o m p l e t e c o n s t i t u t i v e e q u a t i o n of t h e m e c h a n i
cal r e s p o n s e of t h e s a m p l e c a n b e m a p p e d o u t .
Strength (Pethica et al. 1983, Oliver et al. 1984) a n d
m o d u l u s ( D o e r n e r a n d N i x 1986) a r e t w o p r o p e r t i e s
t h a t a r e n o w r o u t i n e l y d e t e r m i n e d from s u b m i c r o
meter volumes.
T h e e x p e r i m e n t a l p a r a m e t e r s a s s o c i a t e d with a n
i n d e n t a t i o n test t h a t relate t o t h e m e c h a n i c a l p r o p e r
ties j u s t m e n t i o n e d include t h e force o n t h e i n d e n t e r ,
the g e o m e t r y of t h e i n d e n t e r , t h e t e m p e r a t u r e ( a n d
other important environmental parameters), the
m e c h a n i c a l p r o p e r t i e s of t h e i n d e n t e r a n d t h e t i m e
d e p e n d e n c e of all t h e p a r a m e t e r s . I n a d d i t i o n , for
special a p p l i c a t i o n s , o t h e r p a r a m e t e r s m u s t b e a d d e d
to this list (e.g., t h e stiffness o r electrical p r o p e r t i e s of
the c o n t a c t ) .
O n e of t h e m o r e difficult p a r a m e t e r s t o m e a s u r e is
the g e o m e t r y of t h e i n d e n t . T h e c o n t a c t a r e a b e t w e e n
the s a m p l e a n d i n d e n t e r u n d e r l o a d is t h e m o s t
i m p o r t a n t g e o m e t r i c aspect of a n i n d e n t a t i o n test.
T h e final a r e a of a s t a n d a r d m i c r o h a r d n e s s test is
m e a s u r e d optically after t h e i n d e n t e r is r e m o v e d , a n d
the a s s u m p t i o n is m a d e t h a t t h e a r e a d o e s n o t c h a n g e
o n u n l o a d i n g . A l t h o u g h i m a g i n g i n d e n t s d o e s give a
direct m e a s u r e of t h e m o s t i m p o r t a n t aspect of t h e
g e o m e t r y , it b e c o m e s m o r e difficult as t h e size of t h e
indent is r e d u c e d . S u b m i c r o m e t e r - s i z e d i n d e n t s c a n
only be i m a g e d u s i n g electron m i c r o s c o p y . T h e tech
niques used a r e t i m e c o n s u m i n g a n d o n l y yield t h e
final size of t h e i n d e n t .
O n e geometric characteristic of t h e i n d e n t t h a t is
m o r e easily m e a s u r e d a n d c a n b e m e a s u r e d c o n t i
n u o u s l y d u r i n g t h e entire i n d e n t a t i o n p r o c e s s is t h e
displacement of t h e i n d e n t e r after c o n t a c t . T h i s

Properties

Microprobe

Current
Digitize

source

Coil

Displacement
detecting
electronics

Table c o n t r o l

V
x-y

table

lOOnm/step

Micro
computer

Figure 1
Schematic diagram of the Nanoindenter

m e a s u r e m e n t p r o v i d e s several o t h e r distinct a d v a n
tages o v e r direct a r e a m e a s u r e m e n t . T h e s e include t h e
ability t o s a m p l e b o t h elastic a n d plastic strains, t h e
ability t o c o n t r o l a n d m o n i t o r stress a n d strain rates
a n d , finally, t h e e l i m i n a t i o n of t h e n e e d for c o m p l i
c a t e d , t i m e - c o n s u m i n g i m a g i n g t e c h n i q u e s . T h e dis
p l a c e m e n t c a n b e m e a s u r e d w i t h sufficient r e s o l u t i o n
t o c h a r a c t e r i z e extremely small i n d e n t s ; h o w e v e r ,
m o d e l s of t h e i n d e n t a t i o n p r o c e s s m u s t b e e m p l o y e d
t o allow t h e c o n t a c t a r e a t o b e calculated. T h e s e
m o d e l s h a v e b e e n d e v e l o p e d a n d used successfully
(Bulychev et al. 1975, Oliver et al. 1984).

2.

Mechanics

A s c h e m a t i c of a n M P M is s h o w n in F i g . 1. T h e force
is a p p l i e d t o t h e i n d e n t e r electromagnetically. T h e
d i s p l a c e m e n t - s e n s i n g system consists of a capacitive
d i s p l a c e m e n t g a u g e . I n this case, t h e m o v a b l e p o r t i o n
of t h e g a u g e is fixed t o t h e shaft c o n n e c t i n g t h e forcea p p l i c a t i o n system t o t h e i n d e n t e r . T h e w h o l e as
sembly is s u p p o r t e d b y leaf springs ( n o t s h o w n ) . T h e
s a m p l e is m o v e d b y a m o t o r i z e d x-y table. All aspects
of t h e system a r e c o n t r o l l e d b y a m i c r o c o m p u t e r . T h e
entire p r o c e s s is a u t o m a t e d so t h a t a set of i n d e n
t a t i o n e x p e r i m e n t s is p e r f o r m e d from initiation t o
c o m p l e t i o n w i t h o u t o p e r a t o r supervision.
T h e r e s o l u t i o n s of t h e v a r i o u s c o m p o n e n t s of the
system d e p i c t e d a r e carefully m a t c h e d t o p e r f o r m as
a n M P M . T h e force a p p l i c a t i o n of this p a r t i c u l a r

233

Mechanical

Properties

Microprobe

Figure 2
TEM image of a replica of a 200 nm deep indent in nickel

system h a s t w o r a n g e s , 0 - 2 0 m N a n d 0 - 1 2 0 m N , with
resolutions of 300 n N a n d 1.5 , respectively. T h e
d i s p l a c e m e n t sensing system h a s a r e s o l u t i o n of
0.2 n m . T h e x-y t a b l e h a s a precision of 0.1 .
F i g u r e s 2 a n d 3 s h o w t h e scale of m i c r o i n d e n t a t i o n s
m a d e w i t h s u c h a system. T h e i m a g e in F i g . 2 is
200 n m d e e p in nickel. T h i s i n d e n t is a factor of ten
larger t h a n t h e smallest i n d e n t s from which r e a s o n
ably precise d a t a c a n b e o b t a i n e d . T h e scale of the
e x p e r i m e n t relative t o t h e scale of a microcircuit is
s h o w n in Fig. 3. T h e i n d e n t s a r e clearly visible a t the
highest magnification.
A l t h o u g h a variety of i n d e n t a t i o n tests a r e useful,
there a r e s o m e e x p e r i m e n t a l similarities c o m m o n t o
all tests p e r f o r m e d with such a system. First, the
p o s i t i o n of e a c h i n d e n t o n t h e surface of t h e specimen
m u s t be established. A c o m b i n a t i o n of a n optical
m i c r o s c o p e a n d t h e high a c c u r a c y x-y table allows

Figure 3
Two indents in a microcircuit demonstrating the fine scale of the experiment

234

Mechanical

this t o be d o n e with a n a c c u r a c y of 250 n m . T h e

next step is t o a p p r o a c h a n d c o n t a c t t h e s a m p l e
surface. T h i s m u s t b e d o n e with s o m e c a r e so t h a t t h e
kinetic energy of t h e i n d e n t a t i o n c o l u m n d o e s n o t
create a significant i n d e n t w h e n its m o t i o n is s t o p p e d
by the surface. O n c e t h e i n d e n t e r is o n t h e surface,
a n y sequence of l o a d i n g a n d u n l o a d i n g steps c a n be
t a k e n d u r i n g which t h e l o a d , d i s p l a c e m e n t , t i m e a n d
a n y o t h e r variables of interest a r e r e c o r d e d . Finally,
the i n d e n t e r is u n l o a d e d a n d lifted from t h e surface.
T h e x-y table is t h e n m o v e d a n d t h e p r o c e s s is
repeated until t h e desired n u m b e r of i n d e n t a t i o n s a r e
p e r f o r m e d . F i g u r e 4 s h o w s a typical set of d a t a from a
relatively simple i n d e n t a t i o n test.

Properties

Microprobe

Q_

20

3.

Applications

S o m e e x a m p l e s of h o w t h e M P M h a s been a p p l i e d t o
material research p r o b l e m s a r e s h o w n in Figs. 5 - 1 1 .
F i g u r e 5 s h o w s t h e c h a n g e in h a r d n e s s a s a function of
d e p t h associated with a n a m o r p h o u s surface layer o n
s a p p h i r e caused b y ion b o m b a r d m e n t . Surface t r e a t
m e n t s such as ion b o m b a r d m e n t a r e being c o n s i d e r e d
for high-wear a p p l i c a t i o n s . F r a c t u r e a n d w e a r rates
associated with p i n - o n - d i s k w e a r tests a r e r e d u c e d
b y t h e presence o f these layers ( M c H a r g u e 1987).
T h e s e t r e a t m e n t s e x t e n d in d e p t h only a few h u n d r e d
n a n o m e t e r s ; h e n c e , it is very difficult t o s a m p l e t h e
m e c h a n i c a l p r o p e r t i e s of t h e t r e a t e d layer. B o t h t h e
h a r d n e s s a n d m o d u l u s c a n b e d e t e r m i n e d in such t h i n
layers as s h o w n in F i g . 6 (Oliver et al. 1987a). T h e
decreased m o d u l u s s h o w n in F i g . 6 a n d t h e decreased
h a r d n e s s s h o w n in F i g . 5 h e l p t o explain t h e w e a r
p r o p e r t i e s of this m a t e r i a l . T h e s e d a t a s h o w h o w
m i c r o i n d e n t a t i o n tests c a n b e used t o c h a r a c t e r i z e
thin films.
A n o t h e r a r e a w h e r e t h e M P M will h a v e a n i m p a c t
is rapidly solidified m a t e r i a l s . T h e p r o d u c t of r a p i d solidification processing (i.e., p o w d e r , ribbon o r
splats) h a s a t least o n e small d i m e n s i o n . N o r m a l l y , t o
test t h e p r o p e r t i e s o f these m a t e r i a l s t h e y m u s t first b e
c o n s o l i d a t e d i n t o large e n o u g h p r o d u c t s t o allow
m a c r o s c o p i c tests t o b e a c c o m p l i s h e d . T h e c o n s o l i d a
tion step often involves s o m e h e a t i n g ; h e n c e , t h e a s solidified m i c r o s t r u c t u r e c a n b e d i s t u r b e d . F i g u r e 7
shows a series of i n d e n t a t i o n s m a d e in t h e edge of a
ribbon of rapidly solidified A l - L i - B e alloy (Oliver et
al. 1987b). T h e r i b b o n w a s a p p r o x i m a t e l y 50
thick. A s t u d y of t h e p r o p e r t i e s of this alloy after
v a r i o u s a n n e a l i n g t r e a t m e n t s indicates a 3 0 % d r o p in
strength after a 1 h a n n e a l a t 200 C. T h e ability t o
characterize t h e m e c h a n i c a l p r o p e r t i e s of this alloy in
the as-solidified s t a t e h a s g e n e r a t e d further interest in
processing t e c h n i q u e s a n d alloy d e v e l o p m e n t .
I n t h e a r e a of welding, t h e M P M is being used t o
a d d r e s s t h e p r o b l e m o f weld e m b r i t t l e m e n t in d u p l e x
stainless steels. F i g u r e 8 ( D a v i d et al. 1987) s h o w s
s o m e relatively large i n d e n t s m a d e in a specimen from

I2H

*>

200

400

Depth (nm)

Figure 4
Typical load vs displacement and hardness vs
displacement curves for electropolished nickel

5Qr-

40

Q2 30

unimplanted
implanted
150

200

250

350

Plastic depth (nm)

Figure 5
The change in hardness of a sapphire surface associated
with an amorphous surface layer caused by ion
implantation

235

Mechanical

Properties

Microprobe

a 308 austenitic stainless steel weld. T h e m i c r o s t r u c t u r e consists of a n austenite m a t r i x with ferrite islands
a few m i c r o m e t e r s in d i m e n s i o n . By s t u d y i n g the
c h a n g e s in t h e p r o p e r t i e s of b o t h t h e a u s t e n i t e a n d
ferrite as a function of aging t r e a t m e n t , t h e causes of
the e m b r i t t l i n g processes will be b e t t e r u n d e r s t o o d .
A n o t h e r e x a m p l e of h o w t h e M P M is applied t o
m a t e r i a l s d e v e l o p m e n t p r o b l e m s involves r a d i a t i o n d a m a g e d m a t e r i a l s . H e a v y ion b o m b a r d m e n t h a s
long been used t o simulate d a m a g e s t r u c t u r e s associ
a t e d with n e u t r o n i r r a d i a t i o n . S u c h t r e a t m e n t s only
affect m a t e r i a l within a few m i c r o m e t e r s of t h e surface
a n d h a v e been extremely useful for s t r u c t u r a l studies.
H o w e v e r , for m e c h a n i c a l - p r o p e r t i e s studies, m a c r o
scopic n e u t r o n - d a m a g e d specimens a r e typically
required a n d a r e extremely expensive. F i g u r e s 9-11
(Zinkle a n d Oliver 1986) s h o w h o w t h e M P M c a n b e
used t o c h a r a c t e r i z e t h e less expensive i o n b o m b a r d e d
m a t e r i a l . F i g u r e 9 s h o w s the result of i n d e n t i n g the
d a m a g e d surface directly a n d c o m p a r i n g t h e resulting
l o a d - d i s p l a c e m e n t curve with t h a t s a m e d a t a o b t a i n e d
from a n u n d a m a g e d section of t h e specimen. Clearly,
the effects of t h e d a m a g e a r e evident as a h a r d n e s s
increase n e a r the surface. C u r v e s of t h e t y p e s h o w n in
Fig. 9 a r e very sensitive t o surface p r o p e r t i e s ; h o w
ever, their i n t e r p r e t a t i o n is challenging o w i n g t o t h e
u n c e r t a i n t y as t o which region of m a t e r i a l below t h e
i n d e n t e r is c o n t r i b u t i n g m o s t t o t h e h a r d n e s s a t a n y
given d e p t h of p e n e t r a t i o n . F i g u r e s 10 a n d 11 a r e t h e
result of using cross-sectional t e c h n i q u e s t o s a m p l e
the surface layer of interest. T h e s a m p l e is p r e p a r e d
by p l a t i n g t h e surface s u b s e q u e n t t o the i r r a d i a t i o n
a n d then cross sectioning t h e resulting s a n d w i c h . A
series of m i c r o i n d e n t a t i o n tests t h a t a r e spatially
progressed across t h e original interface a r e used t o
sample t h e m a t e r i a l of interest in cross section. F i g u r e
10 shows such a series, a n d Fig. 11 s h o w s t h e resulting
d a t a . T h e e x p e r i m e n t resulting in F i g . 9 is m u c h
simpler t o p e r f o r m h o w e v e r , t h e results of t h e crosssectional t e c h n i q u e a r e m o r e easily i n t e r p r e t e d .
M o d e l s a n d n u m e r i c a l c a l c u l a t i o n s t o relate t h e t w o
are being p u r s u e d . If such s a m p l e s a n d tests c a n b e
used as a n initial sorting tool for c h a r a c t e r i z i n g
resistance t o r a d i a t i o n d a m a g e , t h e cost of such
research could be r e d u c e d by a t least a n o r d e r of
magnitude.

4. Descriptive

4 0 0 '

unimplanted
implanted
100

150

200

J250

3 0I0

Plastic depth (nm)

Figure 6
The change in modulus of the same ion-implanted
sapphire surface shown in Fig. 5

a function of d e p t h from l o a d - d i s p l a c e m e n t d a t a
r e q u i r e careful c o n s i d e r a t i o n . T h e d a t a r e q u i r e d a r e
o b t a i n e d from a n i n d e n t a t i o n test consisting of a
series of l o a d i n g a n d u n l o a d i n g sequences going t o
progressively higher m a x i m u m l o a d s . T h e displace
m e n t m e a s u r e m e n t s m a d e d u r i n g l o a d i n g sequences,
in w h i c h the size of t h e i n d e n t is increased plastically,
c o n t a i n i n f o r m a t i o n a b o u t b o t h t h e elastic a n d plastic
strain fields. T h e u n l o a d i n g d a t a represents t h e re
s p o n s e of t h e elastic field only. U s i n g i n f o r m a t i o n
from b o t h sequences of d a t a the plastic a n d elastic
c o m p o n e n t s c a n be s e p a r a t e d ; hence, the h a r d n e s s
a n d m o d u l u s c a n be calculated for each p o i n t a t
w h i c h a n u n l o a d i n g sequence begins ( D o e r n e r a n d
N i x 1986).

Models

A p p l i c a t i o n s like t h e o n e s j u s t discussed p r o v i d e t h e
driving force for t h e second a r e a of research related t o
M P M s . T h i s is t h e d e v e l o p m e n t of m o d e l s t o allow
researchers t o d e c o n v o l u t e t h e c o m p l i c a t e d g e o m e t r y
of i n d e n t a t i o n tests a n d extract useful m e c h a n i c a l
properties.
O n e e x a m p l e of such a n effort is d e m o n s t r a t e d b y
Figs. 5 a n d 6 w h i c h h a v e a l r e a d y been discussed. T h e
m o d e l s necessary t o retrieve m o d u l u s a n d s t r e n g t h as

236

500

Figure 7
Indents in the edge of a rapidly solidified Al-Li-Be alloy
ribbon

Mechanical

Properties

Microprobe

Figure 8
SEM image of indents traversing a ferrite island in a weld
in a duplex stainless steel

O n e m a j o r effort t o i m p r o v e t h e physical capabilit

ies of t h e system is t o a d d t e m p e r a t u r e t o t h e list of
variables t h a t c a n be c o n t r o l l e d . T h e M P M s n o w
available a r e limited t o a m b i e n t t e m p e r a t u r e s b e c a u s e
the d i s p l a c e m e n t m e a s u r e d is sensitive t o t h e t h e r m a l
e x p a n s i o n of t h e l o a d a p p l i c a t i o n system. T h i s is
particularly i m p o r t a n t w h e n d i s p l a c e m e n t s a r e being
m e a s u r e d t o a fraction o f a n a n o m e t e r . Clearly t h e
interest in v a r y i n g t h e t e m p e r a t u r e of t h e i n d e n t a t i o n

Figure 10
Series of indents approaching the original surface of a
heavy ion damaged specimen that has been cross sectioned

test is high. T h e technical difficulties involved in

a c c o m p l i s h i n g this g o a l a r e significant if t h e resolu
t i o n of t h e e x p e r i m e n t is t o b e m a i n t a i n e d .

5. The
0

200

400

600

Indent

800

1000

1200

1400

depth (nm)

Figure 9
Hardness changes in copper due to radiation damage
associated with heavy ion bombardment sampled by direct
indentation of the treated surface
(4 MeV F e + + + 50 at.ppm, peak.damage = 15 dpa,
r i rr = 220C)

Future

I n t e r e s t in t h e M P M is high. T h e d u r a t i o n of t h a t
interest will d e p e n d o n t h e success such systems h a v e
in c o n t r i b u t i n g t o t h e s o l u t i o n of i m p o r t a n t t e c h n o l o
gical q u e s t i o n s . T h e e x a m p l e s o u t l i n e d h e r e s h o w t h e
diversity of industries t h a t c a n m a k e use of the
i n f o r m a t i o n t h e M P M g e n e r a t e s . If a fraction of such
cases result in real p r o g r e s s , t h e future of M P M s is
a s s u r e d . S u c h systems will b e c o m e a n o t h e r i m p o r t a n t
t o o l available t o all m a t e r i a l scientists.

237

Mechanical

Properties

Microprobe

mechanical
u sn
P

\i /

..

electropolish

2
3
4
Depth from interface (/zm)

Figure 11
Results of the series of indents shown in Fig. 10:
cross-section hardness of copper following 14 MeV
copper-ion irradiation (indent depth = 150 nm, peak
damage = 40 dpa, TiTI = 100 C)

Acknowledgements
T h e a u t h o r w o u l d like t o a c k n o w l e d g e t h e s p o n s o r i n g
of this w o r k by t h e Division of M a t e r i a l s Sciences, U S
D e p a r t m e n t of E n e r g y , u n d e r c o n t r a c t D E - A C 0 5 840R21400 with M a r t i n M a r i e t t a E n e r g y Systems,
Inc.

Oliver W C, Hutchings R, Pethica J 1984 Microindentation techniques in materials science. In: Blau J, Lawn
R (eds.) 1984 American Society for Testing and Mater
ials Special Technical Publication 889. ASTM Philadel
phia, PA, p. 303
Oliver W C, McHargue C J, Zinkle S J 1987a Thin film
characterization using a mechanical properties micro
probe. Thin Solid Films 153: 185-6
Oliver W C, Wadsworth J, Nieh G 1987b Characteriza
tion of rapidly solidified Al-Be-Li and Al-Be ribbons.
Scr. Metall. 21: 1429-33
Pethica J B, Hutchings R, Oliver W C 1983 Hardness
measurement at penetration depths as small as 20 nm.
Philos. Mag. A 48(A): 593-606
Tabor D 1951 The Hardness of Metals. Clarendon Press,
Oxford
Westbrook J 1957 Microhardness testing at high tempera
tures. Proc. Am. Soc. Test. Mater. 57: 873-95
Westwood A R C , Macmillan 1973 Environmentsensitive hardness of nonmetals. In: Conrad H, West
brook J (eds.) 1973 American Society for Metals. ASM,
Materials Park, OH, pp. 377-417
Zinkle S J, Oliver W C 1986 Mechanical property measure
ments on ion-irradiated copper and Cu-Zr. J. Nucl.
Mater. 143 (Nov): 548-52
W . C. Oliver
[Oak R i d g e N a t i o n a l L a b o r a t o r y ,
O a k R i d g e , Tennessee, U S A ]

See also: Hardness Characterization

Microengineering of Materials:
Characterization

Bibliography

T a r g e t s for inertial-confinement fusion ( I C F ) m u s t

m e e t stringent r e q u i r e m e n t s of d i m e n s i o n a n d c o m
p o s i t i o n . T h e m e t h o d s used d u r i n g a n d after the
m a n u f a c t u r e of these targets t o d e t e r m i n e their size,
thickness, feature a n d defect l o c a t i o n , a n d c o m p o s i
tion a r e described in this article.
T a r g e t s for I C F a r e c o m p r e s s e d u p t o 1000 times b y
the rocketlike a b l a t i o n of t h e o u t e r layer of the target.
T h e a b l a t o r layer is h e a t e d , a n d s u b s e q u e n t l y b l o w n
off, by a laser o r a particle b e a m driver. T h e a b l a t i o n
layer m u s t be of u n i f o r m thickness a n d density o r it
will b u r n t h r o u g h in t h e thin a r e a s , drive the fuel
a s y m m e t r i c a l l y a n d t h u s r e d u c e the a m o u n t of fuel
b u r n e d . T h e r e q u i r e m e n t is t h a t fractional thickness
v a r i a t i o n be less t h a n 0 . 1 % (Weinstein 1982). Sym
m e t r i c drive also requires h o m o g e n e o u s c o m p o s i t i o n ,
because the a b s o r p t i o n of t h e driver energy is highly
d e p e n d e n t o n t h e a t o m i c n u m b e r of t h e i r r a d i a t e d
m a t e r i a l . Defects as small as 10 n m high a n d 1
a c r o s s c a n seed i m p l o s i o n instabilities t h a t will g r o w
a n d spoil t h e i m p l o s i o n s y m m e t r y . T h e fuel c o n t e n t of
t h e target m u s t be k n o w n a n d , if t h e fuel is either
liquid o r solid, t h e layer u n i f o r m i t y m u s t be diag
nosed. T h e techniques used t o d e t e r m i n e these a n d
o t h e r t a r g e t characteristics fall u n d e r t h e b r o a d c a t
egory of target c h a r a c t e r i z a t i o n . C h a r a c t e r i z a t i o n
m e t h o d s in general b e l o n g t o three categories: optical

Bulychev S I, Alekhin V P, Shorshorov , Ternovskii

A , Shnyrev G D 1975 Determining Young's modulus
from the indentor penetration diagram. Zavod. Lab.
41(9): 1137-9
Chu S G, Li J C 1977 Impression creep: a new creep
test. J. Mater. Sci. 12: 2200-8
Chu S G, Li J C 1980 Localized stress relaxation by
impression testing. Mater. Sci. Eng. 45: 167-71
David S A, Vitek J M, Keiser J R, Oliver W C 1987
Nanoindentation
microhardness
study
of
lowtemperature ferrite decomposition in austenitic stainless
steel welds. Weld. J. 66(8): s235-40
Doerner F, Nix W D 1986 A method for interpreting
the data from depth-sensing indentation instruments.
J. Mater. Res. 1(4): 601-9
Gilman J J 1973 Hardnessa strength microprobe. In:
Conrad H, Westbrook J (eds.) 1973 American Society
for Metals. ASM, Materials Park, OH, pp. 51-72
Lawn R, Evans A G 1977 A model for crack initiation in
elastic plastic indentation fields. / . Mater. Sci. 12: 2195-9
Lawn R, Wilshaw R 1975 Fracture of Brittle Solids.
Cambridge University Press, London
Li J C M, Chu S G 1979 Impression fatigue. Scr. Metall.
13: 1021-6
McHargue C J 1987 The mechanical and tribological
properties of ion implanted ceramics. In: Mazzoldi P,
Arnolds G W (eds.) 1987 Ion Beam Modification of
Insulators. Elsevier, New York, pp. 223-44

238

Microengineering

m e t h o d s for t r a n s p a r e n t m a t e r i a l s , a n d electron
b e a m c h a r a c t e r i z a t i o n a n d x-ray t e c h n i q u e s for b o t h
opaque and transparent materials.

1. Optical

Methods

1.1
Microscopes
T h e w o r k h o r s e of t h e I C F target i n d u s t r y is t h e
optical m i c r o s c o p e used for a s s e m b l y of I C F t a r g e t s .
T a r g e t builders use stereo m i c r o s c o p e s with a w o r k i n g
distance of a t least 0.1 m t o allow for free m a n i p u l a
tion of t h e t a r g e t w i t h o u t t h e risk of d a m a g e . A
c o n t i n u o u s z o o m from a p p r o x i m a t e l y x 3 t o x 60
allows t h e f a b r i c a t o r t o k e e p all t h e aspects of t h e
assembly in view a n d t o focus closely o n details w h e n
necessary.
P r e l i m i n a r y selection of t a r g e t m a t e r i a l s is generally
accomplished o n a b i n o c u l a r m i c r o s c o p e , usually a
higher q u a l i t y i n s t r u m e n t t h a n a n assembly m i c r o
scope. A m o v a b l e cross-hair o r filar eyepiece is useful
in sizing the target c o m p o n e n t s . Alternatively a s t a n
d a r d eyepiece c a n m e a s u r e t h e shell d i a m e t e r t o a b o u t
0.5 . T h e target surface c a n b e inspected with t h e
s a m e i n s t r u m e n t b y r o t a t i n g it u n d e r t h e objective.
Dark-field i l l u m i n a t i o n using stain-free optics will
detect surface defects a n d r o u g h s p o t s . F i n e focus a n d
a shallow d e p t h of field allow inspection of t h e
interior surfaces of t r a n s p a r e n t shells.
1.2

Interferometry

Interferometric t e c h n i q u e s split light from a single

source i n t o t w o p a t h s ; o n e acts as a reference a n d t h e
o t h e r interacts with t h e t a r g e t u n d e r inspection. U p o n
r e c o m b i n a t i o n , t h e t w o b e a m s of light n o l o n g e r h a v e
the s a m e p h a s e b e c a u s e e a c h b e a m h a s t r a v e r s e d a
different optical p a t h . (Optical p a t h is defined as t h e
p r o d u c t of t h e thickness a n d refractive index for e a c h
m a t e r i a l t h a t the light h a s p a s s e d t h r o u g h . ) If t h e
optical p a t h difference of t h e t w o b e a m s is w i t h i n the
c o h e r e n c e length of t h e s o u r c e , t h e viewer o r d e t e c t o r
n o t e s interference fringes t h a t c a n be c o l o r e d in t h e
case of white-light i n t e r f e r o m e t r y o r b a n d s of high
a n d low intensity in t h e case of a m o n o c h r o m a t i c
source. T h e fringes a r e d u e t o t h e c o h e r e n t a d d i t i o n of
the reference a n d t a r g e t - a l t e r e d w a v e fronts. E a c h
fringe is a c o n t o u r of p o i n t s w i t h e q u a l p h a s e dif
ference b e t w e e n t h e t w o b e a m s . Between successive
fringes of t h e s a m e c o l o r t h e r e is a w a v e l e n g t h of
optical p a t h difference. E l e c t r o n i c d e t e c t i o n tech
niques c a n detect o n e - h u n d r e d t h of a fringe in a n
interferogram. T h u s the t e c h n i q u e is extremely sensi
tive ( 5 - 5 0 n m ) t o optical p a t h differences. C o m b i n i n g
interferometry with m i c r o s c o p y c a n p r o d u c e a d e p t h
resolution of a b o u t 500 n m .
(a) White-light interferometry.
T h i s h a s several im
portant applications to I C F target characterization
(Weinstein 1982). Its m a j o r use is in the m e a s u r e m e n t
of the thickness a n d u n i f o r m i t y of t r a n s p a r e n t - t a r g e t

of Materials:

Characterization

shell walls. T h e J a m i n - L e b e v e d e v interferometer is

o n e of several t h a t fit this c a t e g o r y . U s u a l l y a m i c r o
scope a t t a c h m e n t , this i n t e r f e r o m e t e r displaces t w o
i m a g e s of t h e t a r g e t a n d allows t h e o p e r a t o r t o adjust
t h e p h a s e of o n e of t h e i m a g e s relative t o the o t h e r .
T h e interference fringes t h a t result w h e n t h e p a t h
lengths a r e nearly e q u a l a r e c o l o r e d save for o n e , t h e
black fringe of z e r o o r d e r . T h e u n i q u e black z e r o t h o r d e r fringe allows a b s o l u t e m e a s u r e m e n t of t h e
optical p a t h , which c a n n o t be d o n e as conveniently
with m o n o c h r o m a t i c i n t e r f e r o m e t r y . T o m e a s u r e t h e
thickness of a shell wall, t h e o p e r a t o r m o v e s t h e black
fringe from the b a c k g r o u n d of t h e target i m a g e t o the
c e n t e r of t h e target i m a g e u s i n g t h e p h a s e c o n t r o l . I n
this w a y , t h e p h a s e difference b e t w e e n rays traced
t h r o u g h t h e t a r g e t walls c a n be d e t e r m i n e d t o 0.1
if t h e refractive index of t h e target-wall m a t e r i a l is
k n o w n . T h e c o m p l e x general p r o b l e m of t h e l o c a t i o n
of t h e fringes for light refracted a t b o t h t h e inner a n d
o u t e r surfaces of a t r a n s p a r e n t shell is r e p o r t e d b y
S t o n e et al. (1975).
A t t h e s a m e t i m e t h a t thickness is m e a s u r e d , wallthickness u n i f o r m i t y c a n be j u d g e d b y assessing t h e
concentricity of t h e c o l o r e d fringe system with the
t a r g e t surface. T h e eye c a n detect n o n u n i f o r m i t i e s of
a b o u t 3 % by this m e t h o d . A c o m p l e t e d e t e r m i n a t i o n
of t h e wall n o n u n i f o r m i t y requires m e a s u r e m e n t in
three o r t h o g o n a l views. T w o o r t h o g o n a l views c a n b e
examined under the microscope without moving the
t a r g e t shell, b y tilting t h e stage.
B u b b l e s o r voids in t h e shell wall b e c o m e centers of
c o l o r e d fringe systems a n d a r e easily detected with
magnified white-light i n t e r f e r o m e t r y . Finally, t h e a d
d i t i o n a l p h a s e difference resulting from a fuel o r
d i a g n o s t i c gas fill c a n be d e t e r m i n e d b y c o m p a r i n g t h e
optical p a t h t h r o u g h t h e center of a filled t a r g e t with
t h e optical p a t h t h r o u g h t h e s a m e t a r g e t before gas
filling. T h e presence of t h e gas a d d s a t e r m p r o p o r
t i o n a l t o (&& - 1) t o t h e optical p a t h difference
( P o w e r s 1982), w h e r e is t h e g a s p r e s s u r e a n d 7 g as is
t h e refractive index of t h e gas. H e n c e , t h e pressure of
t h e fill g a s c a n b e d e t e r m i n e d analytically.
(b) Laser interferometry.
T h i s c a n d i a g n o s e t h e sym
m e t r y of a liquid o r frozen fuel layer inside a n I C F
target. I n a simple a r r a n g e m e n t , laser light illuminates
t h e t a r g e t from t h e b a c k a n d passes t h r o u g h a wedge,
o r s h e a r i n g c u b e ( T a r v i n et al. 1979), t h a t displaces a
p a i r of t a r g e t i m a g e s from o n e a n o t h e r . Light t h r o u g h
t h e t a r g e t in o n e i m a g e t h e n interferes with light
p a s s i n g n e a r t h e t a r g e t in t h e o t h e r i m a g e . T h e
reference field c a n be m a d e flat t o a q u a r t e r of a w a v e
w i t h o u t m u c h difficulty. T h e interference p a t t e r n
s h o w s circular fringes t h a t a r e more-or-less c o n c e n t r i c
w i t h t h e t a r g e t i m a g e itself, d e p e n d i n g o n t h e sym
m e t r y of t h e fuel layer. T h e t e c h n i q u e is similar t o t h e
white-light thickness m e a s u r e m e n t described a b o v e
except t h a t cryogenic t a r g e t s r e q u i r e m u c h longer

239

Microengineering

of Materials:

Characterization

w o r k i n g - d i s t a n c e optics. T h e t h e r m a l shields sur

r o u n d i n g the cryogenic e n v i r o n m e n t p r e v e n t placing
i n s t r u m e n t s close t o t h e target, m a k i n g c o n v e n t i o n a l
d o u b l e - a r m interferometry difficult. Splitting the
b e a m c o n t a i n i n g the target i m a g e with the shearing
c u b e w o r k s well for this a p p l i c a t i o n .
T e m p l a t e s c a n be c o n s t r u c t e d b y a c o m p u t e r s h o w
ing the fringe system c o r r e s p o n d i n g t o specific fuellayer n o n u n i f o r m i t i e s (Miller a n d Sollid 1978). T h e
target-chamber operator can compare the computed
fringes with the physical ones t o d e t e r m i n e w h e t h e r
the cryogenic layer is acceptable for " s h o o t i n g " o r
needs to be reprocessed. F o r m o r e precision, the
interferogram c a n be digitized a n d a n a l y z e d by c o m
p u t e r t o extract t h e defect i n f o r m a t i o n (see W h i t m a n
1982).
H o l o g r a p h i c interferometry offers a m o r e precise
m e a s u r e m e n t of cryogenic layer u n i f o r m i t y ( B e r n a t et
al. 1982). W i t h this m e t h o d , a h o l o g r a m of t h e target
with the fuel in the g a s e o u s state is m a d e a n d c o m
p a r e d with t h e liquid- or solid-layer target. S u p e r p o s i
tion of the real cold system with t h e h o l o g r a m of the
w a r m e r s y m m e t r i c system c a n be d o n e with a d o u b l e
e x p o s u r e o r by viewing the cold system t h r o u g h the
h o l o g r a m in real time. T h e fringes p r o d u c e d a r e d u e
to c h a n g e s in t h e system b e t w e e n e x p o s u r e s . If m o t i o n
can be eliminated b e t w e e n e x p o s u r e s , t h e fringes a r e
d u e only t o the c h a n g e of state of t h e fuel. T h e only
effect of the shell is t o refract light o u t of t h e e n t r a n c e
pupil of the optical system; t h u s , a thick shell h a s a n
a n n u l u s inside the wall w h e r e there a r e n o fringes.
W i t h thin shells, this m e t h o d c a n s h o w fuel-layer
n o n u n i f o r m i t i e s as small as 50 n m .
T h e o u t e r surface of laser fusion targets h a s been
completely characterized using sensitive interfero
m e t r y a n d a m e t h o d of m a n i p u l a t i n g the s p h e r e
t h r o u g h An r o t a t i o n . C o m p u t e r c o n t r o l of the
r o t a t i o n a n d d a t a acquisition is essential so t h a t the
i n f o r m a t i o n c a n be g a t h e r e d quickly. T w o closely
related i n s t r u m e n t s of this n a t u r e h a v e been described
( C o o p e r 1982, M o n j e s et al. 1982); a l t h o u g h neither
instrument m a d e the transition to a production tool,
b o t h succeeded in their design goals of m a p p i n g a
microsphere.
T h e m a n i p u l a t o r c o n c e p t developed by W e i n stein et al. (1978) places the t a r g e t t o be e x a m i n e d
between t w o soft tips t h a t a r e driven in precisely
o p p o s i t e directions. T h e tips c a n be c o u p l e d either b y
a m i c r o p r o c e s s o r o r mechanically by captive m a s t e r
spheres. T h u s , w h e n o n e tip m o v e s , it rolls t h e spheres
in c o n t a c t with it. T h e o t h e r tip is driven by t h e
o p p o s i t e surface of the m a s t e r spheres a n d m o v e s in
exactly t h e o p p o s i t e direction. T h e target c a p t u r e d
between t h e tips also rolls w i t h o u t t r a n s l a t i n g . In this
w a y the sphere c a n p r e s e n t 4 of surface t o t h e
i n t e r r o g a t i o n b e a m of the interferometer. F i g u r e 1
shows the 4 m a n i p u l a t o r .
T h e interferometers for s p h e r e surface c h a r a c t e r i
zation ( C o o p e r 1982, M o n j e s et al. 1982) require

240

Microsphere

target

motion
motion

Figure 1
Schematic showing detail of An manipulator design:
(a) magnetic loading, (b) driven plate and (c) captive
master spheres

sensitivity of b e t t e r t h a n A/50 ( ~ 1 0 n m ) . T o detect

fringe shifts t o this precision requires p h a s e m o d u l a
tion. T h e p h a s e of t h e reference b e a m of t h e interfer
o m e t e r is m o d u l a t e d a t s o m e frequency 0 , a n d t h e
i n t e r r o g a t i n g b e a m h a s s o m e a d d i t i o n a l p h a s e dif
ference b e t w e e n the t w o b e a m s . T h e c o n v e r s i o n of t h e
phase measurement to an amplitude measurement
a c c o u n t s for t h e high sensitivity. It is e s t i m a t e d t h a t
with a m a n i p u l a t o r a n d interferometer of this type, a
c o m p l e t e m a p of t h e surface of a 500 d i a m e t e r
sphere s h o w i n g defects of l O n m a m p l i t u d e o n a
spatial scale of 1-10 t a k e s 5 m i n .

2. Electron

Beam

Characterization

of ICF

Targets

Highly d e m a n d i n g r e q u i r e m e n t s for c o m p o s i t i o n ,
g e o m e t r y a n d surface finish a r e c o m m o n t o t h e crea
tion of t a r g e t s for I C F . T h e s e r e q u i r e m e n t s generally
stem from t h e need t o m a i n t a i n s y m m e t r y a n d stabi
lity d u r i n g t h e i m p l o s i o n - c o m p r e s s i o n p h a s e of e a c h
test. T a r g e t s for these e x p e r i m e n t s typically h a v e
overall d i m e n s i o n s less t h a n 1 m m , i n t e n t i o n a l struc
tures in t h e m i c r o m e t e r r a n g e a n d u n w e l c o m e features
in t h e n a n o m e t e r r a n g e . S u c h small scales r e q u i r e d t h e
use early o n of t h e s c a n n i n g electron m i c r o s c o p e
( S E M ) a n d related electron b e a m t e c h n i q u e s t o c h a r
acterize I C F t a r g e t s .
2.1 Signals and Detector
Types
T h e i m p a c t of accelerated electrons with m a t t e r re
sults in a variety of e m i t t e d signals as e n u m e r a t e d in
T a b l e 1. M a n y S E M s h a v e d e t e c t o r s c a p a b l e of
m e a s u r i n g these signals a n d r e a c h i n g a c o m p l e t e
a n s w e r t o a n analytical q u e s t i o n usually involves
m a k i n g full use of these signals a n d d e t e c t o r s . T h e

Microengineering
Table 1
Types of signals available in SEM and methods of detection
Emitted signal

Detector

Secondary
electrons
Backscattered
electrons

Scintillator/
photomultiplier
Silicon diode

Absorbed current
electrons
Auger electrons

Current amplifier

Characteristic and
bremsstrahlung
rays

Solid state
detector or
curved crystal
spectrometer
Film

Kossel diffraction
rays
Cathodoluminescence
Heat

Electron energy

Monochromator/
photomultiplier
Piezoelectric
transducer

Information
conveyed
Topography,
dimensions
Topography,
dimensions,
atomic number
Dimensions,
atomic number
Elemental
analysis
Elemental
analysis

Crystallography
Chemistry, carrier
lifetimes
Subsurface
mechanical
defects

m o s t c o m m o n use of t h e S E M is t o p r o d u c e i m a g e s
using t h e first three signals listed in T a b l e 1. S e c o n d
ary electrons a r e c o n v e n t i o n a l l y defined as t h o s e
electrons e m i t t e d from t h e s a m p l e surface t h a t h a v e
energies less t h a n 50 eV. S u c h low energies i m p l y t h a t
these electrons o r i g i n a t e w i t h i n a few n a n o m e t e r s of
t h e surface. A s a c o n s e q u e n c e , this signal h a s t h e
highest spatial r e s o l u t i o n of all t h e e m i t t e d signals.
B a c k s c a t t e r e d electrons a r e t h o s e incident e l e c t r o n s
t h a t u n d e r g o elastic collisions in t h e s a m p l e a n d t h u s
retain energy n e a r t h a t of t h e original b e a m . T h e
b a c k s c a t t e r e d electron intensity d e p e n d s o n t h e aver
age a t o m i c n u m b e r of t h e s a m p l e . T h i s signal t h u s
m a p s t h e c o m p o s i t i o n of t h e surface. R e s o l u t i o n for
elements from r o w f o u r o f t h e p e r i o d i c table is
a p p r o x i m a t e l y o n e - t h i r d of a n a t o m i c n u m b e r .
A b s o r b e d c u r r e n t consists of t h o s e e l e c t r o n s t h a t
a r e n o t e m i t t e d from t h e s a m p l e a n d a r e n o r m a l l y
c o n d u c t e d t o g r o u n d . T h e c o n t r a s t in t h e a b s o r b e d
c u r r e n t i m a g e is similar t o t h e b a c k s c a t t e r e d signal
except inverted; b r i g h t a r e a s in the b a c k s c a t t e r e d
i m a g e a p p e a r d a r k in a b s o r b e d c u r r e n t i m a g e s .
T h e p o p u l a r i t y of S E M i m a g e s c a n b e a t t r i b u t e d t o
three basic characteristics. First, t h e i m a g e s possess
e x t r a o r d i n a r y d e p t h of field. T h i s is t h e result of t h e
very small divergence of t h e electron b e a m in t h e
S E M , typically less t h a n 50 m r a d . S e c o n d , high reso
lution results from t h e s h o r t w a v e l e n g t h of t h e
e l e c t r o n s r o u g h l y 100 000 times less t h a n t h a t of

of Materials:

Characterization

visible light. T h i r d , t h e i m a g e s h a v e a lifelike threed i m e n s i o n a l q u a l i t y leading t o easy i n t e r p r e t a t i o n .

A n a p p l i c a t i o n d e m o n s t r a t i n g t h e use of i m a g i n g is
t h e origin of " c o n e - t y p e defects." I r r e g u l a r features
h a v e l o n g b e e n o b s e r v e d o n t h e surfaces of b o t h
plastic a n d metallic c o a t i n g s o n glass s u b s t r a t e s . T h e
origin of these defects w a s expected t o be c o n t a m i n a
t i o n o n t h e s u b s t r a t e t h a t w a s replicated a n d g r o w n in
t h e d e p o s i t e d c o a t i n g . T h e cross section of a metallic
c o a t i n g in Fig. 2 s h o w s a defect of this type. F u r t h e r
e x a m i n a t i o n s h o w e d a small surface defect o n the
s u b s t r a t e a t t h e b a s e of t h e c o n e defect.
2.2 Thickness
Measurement
A k n o w n c o a t i n g thickness is a c o m m o n r e q u i r e m e n t
of m a n y m u l t i c o m p o n e n t I C F targets, a n d several
t e c h n i q u e s a r e used with t h e S E M for d e t e r m i n i n g
thickness. F i g u r e 3 s h o w s t h e direct m e a s u r e m e n t of
layers in t h e S E M i m a g e of a fractured specimen. T h e
magnification c a n be d e t e r m i n e d w h e n t h e specimen is
m o u n t e d o n a c a l i b r a t i o n s t a n d a r d t h a t is t h e n p h o t o
g r a p h e d u n d e r t h e s a m e c o n d i t i o n s as t h e specimen.
T h i s m e t h o d is a p p r o p r i a t e for films m o r e t h a n
100 n m thick.
M a n y n o n d e s t r u c t i v e m e t h o d s for d e t e r m i n i n g
thickness a r e b a s e d o n m e a s u r i n g the d e p t h distribu
tion of rays within t h e specimen ( Y a k o w i t z a n d
N e w b u r y 1976, H e i n r i c h 1981, Elliott et al. 1982).
T h e s e m e t h o d s typically involve m e a s u r i n g the emit
ted x-ray signal from t h e film a n d dividing b y the
s a m e signal m e a s u r e d from a b u l k s t a n d a r d of the
s a m e c o m p o s i t i o n as t h e film. T h i s r a t i o is t h e n
c o n v e r t e d t o a m a s s thickness b y t h e use of empirical
o r theoretical m o d e l s describing t h e p r o d u c t i o n of
r a y s w i t h d e p t h below t h e specimen surface. T h e s e

Figure 2
Magnified fracture cross section of a glass microballoon
coated with gold; "cone defect" originated from
contamination on glass microballoon

241

Microengineering

of Materials:

Characterization

h a s resulted in the d e v e l o p m e n t of c o m m e r c i a l
m a c h i n e s designed specifically for this use, b a s e d o n
electron c o l u m n s from S E M s (see Sect. 3.1).

Figure 3
Measurement of coating thickness; glass microballoon
coated with plastic and gold

m e t h o d s cover t h e r a n g e from a p p r o x i m a t e l y
00 n m .

2.3 Surface Roughness

Measurement
T h e surface r o u g h n e s s of targets h a s received g r e a t
a t t e n t i o n . A c o m m o n l y s t a t e d goal for I C F t a r g e t s is a
surface r o u g h n e s s v a r i a t i o n less t h a n 10 n m . T h e
c u r r e n t from the b a c k s c a t t e r e d electron d e t e c t o r c a n
be used t o d e t e r m i n e surface r o u g h n e s s .
T h e b a c k s c a t t e r e d electron signal is e m i t t e d a n i s o tropically. T h u s , as t h e electron b e a m scans a speci
m e n , the signal r e c o r d e d b y fixed d e t e c t o r will v a r y
a c c o r d i n g t o t h e local surface t o p o g r a p h y as well as
the average a t o m i c n u m b e r of t h e s a m p l e . E m p l o y i n g
t w o d e t e c t o r s , o n e o n either side of t h e s a m p l e a n d
observing the a n a l o g difference, eliminates t h e a t o m i c
n u m b e r effect. T h u s a signal p r o p o r t i o n a l t o t h e
surface t o p o g r a p h y c a n b e m e a s u r e d (Lebiedzick
1979). Such a system developed a t L a w r e n c e Liverm o r e N a t i o n a l L a b o r a t o r y specifically for I C F t a r g e t s
s h o w e d spatial r e s o l u t i o n of r o u g h l y 50 n m a n d
height resolution of 10 n m .
2.4
Microradiography
T h e p r o d u c t i o n of r a y s allows specimens t o be
r a d i o g r a p h e d in t h e S E M , a n d t h e use of t h e electron
b e a m t o p r o d u c e a p o i n t s o u r c e of r a y s in a thin
m e t a l foil allows magnification in t h e final r a d i o g r a p h
as s h o w n in F i g . 4. T h e magnification is d e t e r m i n e d
by the specimen p o s i t i o n b e t w e e n t h e x-ray s o u r c e
a n d the film. T h i s t e c h n i q u e h a s b e e n used b o t h t o
observe fine s t r u c t u r e in c o a t i n g s a n d t o resolve small
density differences in low-density m a t e r i a l s . T h e a b i
lity of this t e c h n i q u e t o resolve small spatial features
as well as t h e ease of o p t i m i z i n g for density r e s o l u t i o n

242

2.5 Quantitative
Analysis
T h e a d v e n t of low-cost lithium-drifted silicon x-ray
d e t e c t o r s h a s afforded a l m o s t all electron m i c r o s c o p e s
s o m e c a p a b i l i t y in m e a s u r i n g e l e m e n t a l c o m p o s i t i o n .
T h e real utility of these d e t e c t o r s lies in c o n v e r t i n g
m e a s u r e d x-ray intensity t o elemental c o n c e n t r a t i o n .
T h r e e factors m u s t be c o n s i d e r e d in this p r o c e d u r e
( B e a m a n a n d Isasi 1972). T h e a t o m i c n u m b e r effect
describes t h e g e n e r a t i o n of rays in t h e s a m p l e b y
i n t e g r a t i n g t h e d e p t h d i s t r i b u t i o n function from the
surface t o t h e m e a n d e p t h a t which t h e a v e r a g e
electron energy e q u a l s t h e excitation energy of the
element being m e a s u r e d . T h e a b s o r p t i o n factor A
c o r r e c t s t h e g e n e r a t e d intensity for t h e a b s o r p t i o n
p a t h length b e t w e e n t h e specimen a n d the d e t e c t o r .
Finally, t h e fluorescence c o r r e c t i o n F a c c o u n t s for
s e c o n d a r y rays g e n e r a t e d from t h e c o n t i n u u m
a n d characteristic r a y s from o t h e r elements in t h e
sample.
T h e p r o d u c t ZAF of these c o r r e c t i o n s gives t h e
t e c h n i q u e its a c r o n y m as well as a n u m e r i c a l value
used t o c o n v e r t m e a s u r e d intensities t o c o n c e n t r a
tions. M a n y c o m p u t e r c o d e s use empirical a n d / o r
a n a l y t i c m o d e l s t o i m p l e m e n t this p r o c e d u r e . T h i s
m e t h o d c a n p r o v i d e a c c u r a c y within 1-2% relative
for m a j o r c o n s t i t u e n t s in a v o l u m e of a b o u t 10 3.
T h e ZAF m e t h o d m a k e s several a s s u m p t i o n s a b o u t
s a m p l e g e o m e t r y t h a t I C F t a r g e t s d o n o t meet. I n
p a r t i c u l a r , t h e small spherical g e o m e t r y of m a n y
t a r g e t s c a n grossly affect t h e a b s o r p t i o n p a t h length
of e m i t t e d r a y s . U n f o r t u n a t e l y , m o s t ZAF r o u t i n e s
p r o v i d e d b y e q u i p m e n t m a n u f a c t u r e r s a r e n o t flexible
e n o u g h t o allow c o r r e c t i o n for g e o m e t r y , so c o d e s
w r i t t e n i n - h o u s e a r e generally preferred. T h i s aspect

Thin metallic foil

Film

Figure 4
Schematic showing technique for producing magnified
radiograph in the SEM

Microengineering

does n o t receive sufficient a t t e n t i o n a n d usually leads

to unidentified e r r o r s in final results.
A v a r i a n t of t h e ZAF t e c h n i q u e t e r m e d () been
developed m o r e recently (Scott a n d L o v e 1983). T h i s
t e c h n i q u e is significant for fusion targets in t h a t it
allows m o r e a c c u r a t e quantification of particles a n d
thin films p e n e t r a t e d by t h e electron b e a m . T h e
m e t h o d a t t e m p t s t o describe m a t h e m a t i c a l l y t h e
g e n e r a t e d x-ray intensity vs m a s s d e p t h from t h e
specimen surface. T h e d e s c r i p t i o n of the x-ray d e p t h
d i s t r i b u t i o n allows a n alternative m e t h o d t o deter
m i n e the a b s o r p t i o n c o r r e c t i o n , typically t h e m o s t
significant of t h e three c o r r e c t i o n factors.
2.6
Computers
(a) Data acquisition.
O p e r a t o r s of e l e c t r o n - b e a m
i n s t r u m e n t s were q u i c k t o a p p l y c o m p u t e r s t o the
a u t o m a t i o n of their i n s t r u m e n t s . M o s t m o d e r n
i n s t r u m e n t s use m i c r o p r o c e s s o r s t o c o n t r o l i n s t r u
m e n t functions with i n p u t from f r o n t - p a n e l o p e r a t o r
c o n t r o l s . E v e n at m o d e s t installations t h e r e a r e
usually a d d i t i o n a l c o m p u t e r s c o n t r o l l i n g such func
tions as b e a m p o s i t i o n , c o u n t i n g electronics, s t e p p e r
m o t o r s for stage m o t i o n a n d s p e c t r o m e t e r s e t u p , a n d
d a t a display. I m a g e - a c q u i s i t i o n systems a r e n o w
being a d d e d t o m a n y m i c r o s c o p e s .
(b) Data reduction. T h e r a p i d a d v a n c e in c o m p u t i n g
p o w e r n o w allows m a n y t a s k s t h a t were formerly r u n
o n m a i n f r a m e s to be p e r f o r m e d o n small d e d i c a t e d
systems in t h e electron m i c r o s c o p e l a b o r a t o r y . T h e
m o s t o b v i o u s is t h e r e d u c t i o n of x-ray d a t a , b u t o t h e r
a p p l i c a t i o n s such as c r y s t a l l o g r a p h y , i m a g e simula
tion a n d lens design a r e also used. O n e n a t i o n a l
bulletin b o a r d system exists solely for the dissemina
tion of software for electron m i c r o s c o p y a n d a n o t h e r
is p l a n n e d .
(c) Monte Carlo technique. A p i c t u r e of a n analytical
situation c a n be m a d e b y s i m u l a t i n g t h e scattering
events a n electron u n d e r g o e s in p a s s i n g t h r o u g h a
m a t e r i a l . T h e use of r a n d o m n u m b e r s t o s i m u l a t e
individual scattering events is referred t o as t h e M o n t e
C a r l o t e c h n i q u e . T h i s m e t h o d h a s p r o v e d beneficial in
the solution t o several q u e s t i o n s r e g a r d i n g I C F t a r g e t
analysis. A c o m m o n a p p l i c a t i o n is t h e analysis of t h i n
films. If t h e film thickness is less t h a n t h e electron
r a n g e in t h a t m a t e r i a l , q u a n t i t a t i v e analysis b e c o m e s
difficult. C o m p u t e r s i m u l a t i o n s of this s i t u a t i o n per
mit i n p u t t o ZAF r o u t i n e s t o b e c o r r e c t e d . A n o t h e r
use is t h e e s t i m a t i o n of spatial r e s o l u t i o n of x-ray
analysis, which is difficult t o d e t e r m i n e e x p e r i m e n
tally. A p p l i c a t i o n s involving surface effects, b e a m
energy a n d i m a g i n g c o n t r a s t h a v e also been p u b l i s h e d
(Heinrich 1981, Scott a n d L o v e 1983).

3. X-Ray

Inspection

Techniques

X - r a y t e c h n i q u e s a r e used o n I C F t a r g e t s t o m e a s u r e
(a) c o a t i n g a n d wall thicknesses, (b) v a r i a t i o n s in

of Materials:

Characterization

c o a t i n g a n d wall thicknesses, (c) gas fill pressures a n d

(d) e l e m e n t a l c o m p o s i t i o n . T h e s e t e c h n i q u e s a r e also
used t o m e a s u r e density a n d thickness uniformities of
b u l k m a t e r i a l s from which smaller I C F target p a r t s
a r e m a d e a n d a r e equally useful for b o t h t r a n s p a r e n t
a n d o p a q u e m a t e r i a l s . R a d i o g r a p h i c g a u g i n g , which
w a s d e v e l o p e d specifically for I C F target characteri
z a t i o n , m e a s u r e s thicknesses a n d v a r i a t i o n s in c o a t
ings. S t a n d a r d x-ray fluorescence techniques detect
gas fill pressures a n d elemental c o m p o s i t i o n . S t a n
d a r d x-ray a n d y-ray g a u g i n g techniques p r o v i d e
m a p s of t h e density a n d thickness b u l k samples.
A n I C F t a r g e t c a n b e p i c t u r e d as a n o n i o n with
several layers o r skins s u r r o u n d i n g a h o l l o w center
filled with gas. T h e thickness of e a c h layer is m e a s u r e d
t o 1 0 % a c c u r a c y a n d t h e v a r i a t i o n s in thicknesss
(deviation from t h e m e a n ) of e a c h layer t o 1 % accur
acy. H e n c e , for c o a t i n g s 1 thick, v a r i a t i o n s in
thickness as small as 10 n m (100 A ) a r e routinely
detected o n a n object t h e size of a grain of s a n d . W i t h
filmless r a d i o g r a p h y a n d m i c r o f o c u s x-ray sources,
sensitivity will s o o n b e 100 times better.
3.1 Characterization
of Walls and Coatings
Radiographic
Gauging

Using

T h e wall of t h e g a s - c o n t a i n i n g vessel a n d its c o a t i n g s

a r e i m a g e d o n film by m e a n s of c o n t a c t m i c r o r a d i o
g r a p h y . T h e t e r m " c o n t a c t " h e r e m e a n s t h a t the
t a r g e t s a r e in c o n t a c t o r nearly in c o n t a c t with the
p h o t o g r a p h i c e m u l s i o n . T h e y a r e a r r a n g e d in a r r a y s
as large as 150 x 150 t a r g e t s o n a very thin (2.5
thick) sheet of M y l a r t h a t lies directly o n t h e e m u l
sion. T h e t e r m m i c r o in m i c r o r a d i o g r a p h y indicates
t h a t t h e i m a g e s a r e as small as t h e targets. Such sizes
r e q u i r e t h a t individual i m a g e s in t h e a r r a y be enlarged
b y a m i c r o s c o p e before t h e q u a l i t y of the targets c a n
be d e t e r m i n e d .
F i g u r e 5 s h o w s a d i a g r a m of a u n i f o r m spherical
c o a t i n g w i t h a p l o t of t h e x-ray t r a n s m i s s i o n a l o n g a
d i a m e t e r of t h e sphere. Parallel rays illuminate the
vessel from t h e t o p . T h e m i n i m u m x-ray a b s o r p t i o n
o c c u r s a t the center a n d increases b y a p p r o x i m a t e l y
8000 a t t h e edge. H e n c e , a n e x p o s u r e t h a t is o p t i m a l l y
e x p o s e d for t h e center c o n t a i n s m u c h less i n f o r m a t i o n
a b o u t t h e edges a n d vice versa. F o r t u n a t e l y , the
e x p o n e n t i a l a b s o r p t i o n of t h e r a y s is m o d e r a t e d b y
t h e r e s p o n s e of the p h o t o g r a p h i c films so t h a t , o n a n
o p t i m a l l y e x p o s e d r a d i o g r a p h , t h e optical density is
linearly p r o p o r t i o n a l t o t h e m a t e r i a l thickness.
By o p t i m i z i n g t h e e x p o s u r e for t h e center, H e n d e r
s o n et al. (1977) s h o w e d t h a t a trace of t h e optical
density in t h e central region of t h e i m a g e m a t c h e s a
theoretical m o d e l a n d t h a t t h e m a t c h is very sensitive
t o c o a t i n g thickness a n d uniformity. T h i s m e t h o d is
a n x-ray g a u g i n g t e c h n i q u e t h a t uses p h o t o g r a p h i c
film r a t h e r t h a n a n electronic d e t e c t o r . S u b s e q u e n t
w o r k ( W h i t m a n a n d D a y 1980, W h i t m a n 1982) h a s

243

Microengineering

of Materials:

Characterization
Void

(a)

(b)

Dimple

(C)

Figure 6
Three types of defects found in coatings on ICF targets:
(a) concentric, (b) elliptical and (c) warts and dimples

Transmitted
rays
(In s c a l e )

0 %

Figure 5
X-ray transmission along a diameter of a uniform
spherical coating

s h o w n t h a t t h e s y m m e t r y of t h e optical density effecti

vely discerns u n i f o r m i t y in t h e thickness of the wall o r
coating.
T h e s e results m e a n t h a t 3 5 % of t h e entire t a r g e t c a n
be characterized in a single view a n d t h a t only three
o r t h o g o n a l views a r e r e q u i r e d t o completely c h a r a c
terize c o a t i n g s . S o m e t i m e s t h e o u t e r m o s t layers of the
target c a n interfere with t h e analysis of t h e inner o n e s .
In such cases, as t h e target is built, e a c h layer o r shell
is characterized before t h e next o n e is applied. V a r i a
tions as small as 1 % a r e detected in all c o a t i n g s
including t h o s e t h i n n e r t h a n 1 . H e n c e , l O n m
v a r i a t i o n s a r e easily detected in c o a t i n g s only 1
thick.
T w o m e t h o d s h a v e evolved for c o m p u t e r analysis
of r a d i o g r a p h i c g a u g i n g . B o t h m e t h o d s digitize t h e
p h o t o g r a p h i c i m a g e a n d store it in c o m p u t e r m e m o r y .
O n e m e t h o d uses o r t h o g o n a l d i a m e t r i c a l scans
(Singleton a n d W e i r 1981) a n d t h e o t h e r uses a fast
F o u r i e r t r a n s f o r m of t h e optical-density d a t a t o
extract c o n c e n t r i c a n d elliptical defects ( S t u p i n
1987a). A statistical test finds small w a r t s a n d d i m
ples. T h e s e defects a r e s h o w n in Fig. 6. C o n c e n t r i c
defects o c c u r w h e n t h e inner a n d o u t e r surfaces of the
shell a r e spherical b u t a r e n o t c o n c e n t r i c . Elliptical
defects o c c u r w h e n o n e o r b o t h of t h e surfaces a r e
elliptical. C o n c e n t r i c a n d elliptical defects with thick
ness v a r i a t i o n s larger t h a n 1 % a r e expected t o d e s t r o y
t h e i m p l o s i o n s y m m e t r y (Weinstein 1982) a n d so a r e
n o t allowable. H o w e v e r , defects of this m a g n i t u d e c a n
be detected.
W a r t a n d d i m p l e defects include surface blemishes
a n d voids inside t h e c o a t i n g ; thickness v a r i a t i o n s
m u s t be less t h a n 0 . 1 % . C u r r e n t x-ray t e c h n i q u e s d o
n o t detect defects this small, b u t a d v a n c e d t e c h n i q u e s
are expected t o d o so. R a d i o g r a p h y is m o r e versatile

244

t h a n , for e x a m p l e , S E M c h a r a c t e r i z a t i o n b e c a u s e it
n o n d e s t r u c t i v e l y detects w a r t s a n d d i m p l e s o n b o t h
surfaces of t h e c o a t i n g s a n d d o e s n o t require t h e
s a m p l e s t o be c o n d u c t i n g . I m a g e analysis systems t h a t
a r e sensitive t o thickness v a r i a t i o n s of 5 - 1 0 % a r e u s e d
t o p r e s o r t i m a g e s for gross c o n c e n t r i c a n d elliptical
defects a n d r e d u c e c o m p u t e r processing times.
R a d i o g r a p h i c g a u g i n g relies o n a step w e d g e (penet r a m e t e r ) t o m e a s u r e t h e a b s o l u t e c o a t i n g thickness
b y c o m p a r i n g t h e optical density in t h e center of the
target i m a g e with t h a t of k n o w n thicknesses of the
c o a t i n g m a t e r i a l in t h e step w e d g e . T h e i m a g e of t h e
p e n e t r a m e t e r m u s t a p p e a r o n t h e s a m e r a d i o g r a p h as
t h e targets. I n this w a y a b s o l u t e thicknesses a r e
d e t e r m i n e d w i t h a b o u t 1 0 % a c c u r a c y , a l t h o u g h with
e x t r e m e c a r e m e a s u r e m e n t s c a n be as a c c u r a t e as 1 % .
H o w e v e r , in either case, v a r i a t i o n s as small as 1 % a r e
detected.
X - r a y sources with energies b e t w e e n 1 k V a n d
50 k V a r e used t o r a d i o g r a p h the thinnest free
s t a n d i n g shells. W h e n possible, these sources use the
characteristic o r L x-ray r a d i a t i o n of the a n o d e s t o
p r o d u c e nearly m o n o e n e r g e t i c x-ray fluxes t o i m p r o v e
c o n t r a s t . H i g h - e n e r g y b r e m s s t r a h l u n g sources a r e
used for thicker shells. X rays from l a s e r - p r o d u c e d
p l a s m a s give extremely fine r e s o l u t i o n using p h o t o
resists r a t h e r t h a n film ( K i m a n d W h i t m a n 1987).
Advanced techniques: microfocus digital
radiography
and microtomography.
Microfocal radiography and
m i c r o t o m o g r a p h y a r e a d v a n c e d t e c h n i q u e s t h a t will
i m p r o v e o u r ability t o m e a s u r e wall thickness a n d
v a r i a t i o n s in wall thickness. M i c r o f o c u s x-ray sources
with energies of 10-30 k V a n d focal s p o t s of
detect thickness v a r i a t i o n s a s small as 0 . 1 % ( S t u p i n
1987b, 1988, S t u p i n et al. 1989), a n d i m p r o v e m e n t s in
this t e c h n i q u e a r e p r e d i c t e d t o detect v a r i a t i o n s as
small as 0 . 0 1 % . M i c r o t o m o g r a p h y using s y n c h r o t r o n
x-ray light sources images s t r u c t u r e s only 1 across
( F l a n n e r y et al. 1987, K i n n e y et al. 1988). B o t h
m e t h o d s use digital i m a g i n g ; t h a t is, images stored in
c o m p u t e r m e m o r y , r a t h e r t h a n p h o t o g r a p h i c films.
3.2 Gas Fill Pressures
T a r g e t s a r e filled with gas either b y diffusion o r b y
c o n s t r u c t i n g t h e shells in a c h a m b e r c o n t a i n i n g t h e fill

Microengineering

gas. T h e p r e s s u r e inside the shell is d e t e r m i n e d n o n destructively b y x-ray fluorescence. T a r g e t s filled w i t h

tritium p r o d u c e b r e m s s t r a h l u n g r a d i a t i o n w i t h a n
intensity p r o p o r t i o n a l t o t h e fill gas p r e s s u r e a n d
v o l u m e ( J o r g e n s e n 1982). T h e b r e m s s t r a h l u n g r a d i a
tion is p r o d u c e d w h e n electrons from t h e d e c a y of
the tritium slow d o w n in t h e gas. T h e electrons excite
the characteristic x-ray lines of o t h e r gases in t h e
target, a n d t h e intensities of these characteristic lines
a r e p r o p o r t i o n a l t o t h e p a r t i a l pressures of their
respective gases. If t r i t i u m is a b s e n t from t h e fill gas,
characteristic lines a r e p r o p o r t i o n a l t o t h e p a r t i a l
pressures of their respective gases. If tritium is a b s e n t
from the fill gas, characteristic x-ray lines c a n b e
excited b y such e x t e r n a l sources as a n x-ray g e n e r a t o r
o r r a d i o a c t i v e source. T h e fluorescence m e t h o d is
restricted t o elements w i t h a t o m i c n u m b e r s g r e a t e r
t h a n five (beryllium), a n d this m e t h o d m e a s u r e s g a s
fill pressures with a n a c c u r a c y of 1 0 % .

Bibliography
Beaman D R, Isasi J A 1972 Electron Beam Microanalysis.
American Society for Testing and Materials, Philadel
phia, PA
Bernat , Darling D H, Sanchez J J 1982 Applications of
holographic interferometry to cryogenic ICF target char
acterization. / . Vac. Sci. Technol. 20: 1362-5
Clement X, Coudeville A, Eyharts P, Perrine J P, Rouillard
R 1983 X-ray absorption in characterization of laser
fusion targets. / . Vac. Sci. Technol. A 1(2): 949-51
Cooper D 1982 A phase modulation interferometer for
ICF target characterization. J. Vac. Sci. Technol. 20:
1075-8
Elliott , Anderson W E, Archuleta A, Stupin D
1982 Thin film thickness measurement using x-ray peak
ratioing in the scanning electron microscope. J. Vac. Sci.
Technol. 20(4): 1372-3
Feldkamp L A, Kubinski D J, Jesion G 1988 Application of
high magnification to 3D x-ray computed tomography.
In: Thomson D O, Chimenti D (eds.) 1988 Review of
Progress in Quantitative Nondestructive Evaluation, Vol.
7. Plenum, New York, pp. 381-8
Flannery B P , Deckman W, Roberge W, Roberge W G,
D'Amico A 1987 Three-dimensional x-ray microtomography. Science 237: 1439-44
Goldstein J I, Newbury D E, Echlin P, Joy D C, Fiori G,
Lipshin 1981 Scanning Electron Microscopy and X-Ray
Microanalysis: A Text for Biologists, Materials Scientists,
& Geologists. Plenum, New York
Heinrich F 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Henderson , Cielaszyk D E, Simms R J 1977 Microra
diography characterization of laser fusion pellets. Rev.
Sci. Instrum. 48: 835-40
Johns W D 1967 Measurement of film thickness. In: Kaeble
F (ed.) 1967 Handbook of X-Rays. McGraw-Hill, New
York, pp. 44-4 to 44^12
Jorgensen S 1982 A technique for calculating DT content

of Materials:

Characterization

in glass microballoons from ray counts. J. Vac. Sci.

Technol. 20: 1118-19
Kim G, Whitman D 1987 X-ray microscopy of inertial
fusion targets using a laser produced plasma as an x-ray
source. J. Vac. Sci. Technol. A 5(4): 2 7 8 1 ^
Kinney J H, Johnson Q C, Saroyan R A, Nichols C,
Bonse U, Nusshardt R, Pahl R 1988 Energy-modulated
x-ray microtomography. Rev. Sci. Instrum 59: 196-7
Kohl J, Zentner R D, Lukens R 1961 Radioisotope
Applications Engineering. D. Van Nostrand, Princeton,
NJ, pp. 484^5
Lambert C 1967 Absorptiometry with polychromatic
x-rays. In: Kaeble F (ed.) 1967 Handbook of X-Rays.
McGraw-Hill, New York, pp. 41-3 to 41-24
Lebiedzick J 1979 An automatic topographical surface
reconstruction in the SEM. Scanning 2(4): 230-7
Miller J R, Sollid J 1978 Interferometric measurement of
cryogenic laser fusion target uniformity. Appl. Opt. 18:
2971-3
Monjes J A, Weinstein W, Willenborg D L 1982
Reflection-transmission phase shift interferometer and
viewing optics. Appl. Opt. 21: 1732-7
Powers F 1982 Improved nonconcentricity characteriza
tion of transparent laser fusion targets by interferometry.
J. Vac. Sci. Technol. 20: 1355-8
Scott V D, Love G 1983 Quantitative Electron- robe
Microanalysis. Wiley, New York
Singleton R M, Weir J 1981 Microradiographic character
ization of metal and polymer coated microspheres.
J. Vac. Sci. Technol. 18: 1264^7
Stone R R, Gregg D W, Souers P C 1975 Nondestructive
inspection of transparent microtargets for laser fusion.
J. Appl. Phys. 17: 852-3
Stupin D 1985 X-ray gauge measures areal density
variations as small as 0.1%. J. Vac. Sci. Technol. A. 3(3):
1266-8
Stupin D 1987a Radiographic detection of 100 A thick
ness variations in 1 -thick coatings on submillimeterdiameter laser fusion targets. In: Thompson D O,
Chimenti D (eds.) 1987 Review of Progress in Quanti
tative Nondestructive Evaluation, Vol. 6B. Plenum, New
York, pp. 1485-94
Stupin D 1987b Filmless radiographic detection of micro
scopic wires and very small areal density variations.
Mater. Eval. 45: 1315-19
Stupin D 1988 Near-real-time radiography detects 0.1%
changes in x-ray absorption with 2 mm spatial resolution.
In: Thompson D O, Chimenti D (eds.) 1988 Review of
Progress in Quantitative Nondestructive Evaluation, Vol.
7. Plenum, New York, pp. 1323-30
Stupin D Moore R, Thomas G D, Whitman R L 1982
Automated computer analysis of x-ray radiographs
greatly facilitates measurements of coating thickness
variations in laser fusion targets. J. Vac. Sci. Technol.
20: 1 0 7 1 ^
Stupin D M, Stokes G H, Steven-Setchell J 1989 Near-real
time radiography detects very small wires and thickness
variations. In: McGonnagle W J (ed.) 1989 International
Advances in Nondestructive Testing. Gordon and Breach,
London, pp. 323-33
Tarvin J A, Sigler R D, Busch G 1979 Wavefront shearing
interferometer for cryogenic laser-fusion targets. Appl.
Opt. 18: 2971-3
Weinstein W 1982 Physical measurements of inertial
fusion targets. / . Vac. Sci. Technol. 20: 1349-54

245

Microengineering

of Materials:

Characterization

Weinstein W, Hendricks C D, Ward C M, Willenborg D L

1978 Simple manipulator for rotating spheres. Rev. Sci.
Instrum. 49: 870-1
Whitman R L 1982 An efficient method to characterize laser
fusion target defects more complex than concentricity.
J. Vac. Sci. Technol. 20: 1359-61
Whitman R L, Day R 1980 X-ray microradiographs of
laser fusion targets: Improved image analysis techniques.
Appl. Opt. 19: 1718-22
Yakowitz H, Newbury D 1976 A simple analytical
method for thin film analysis with massive pure element
standards. Scanning Electron Microsc. 1: 150-60
L. R. F o r e m a n , . E. Elliott a n d D . M . S t u p i n
[Los A l a m o s N a t i o n a l L a b o r a t o r y ,
Los Alamos, New Mexico, USA]

Microstructural Evolution: Computer

Simulation
Prediction of the m i c r o s t r u c t u r e of a m a t e r i a l as a
function of processing c o n d i t i o n s is a m a j o r objective
of m a t e r i a l s science. Since m i c r o s t r u c t u r e m a y be
defined as t h e spatial a r r a n g e m e n t of defects, t h e
existence of m i c r o s t r u c t u r e (e.g., t h e presence a n d
a r r a n g e m e n t of grain b o u n d a r i e s , dislocations, etc.) is
a c o n s e q u e n c e of t h e n o n e q u i l i b r i u m n a t u r e of tech
nologically interesting m a t e r i a l s . T h i s n o n e q u i l i b r i u m
feature of m i c r o s t r u c t u r e leads n a t u r a l l y t o t h e wellk n o w n d e p e n d e n c e o n processing history. T h e r e f o r e ,
the u n d e r s t a n d i n g of m i c r o s t r u c t u r e a n d processing
c o n d i t i o n s a r e , b y necessity, intimately e n t w i n e d .
A further difficulty in describing the f o r m a t i o n a n d
evolution of m i c r o s t r u c t u r e is t h e c o m p l e x i t y of t h e
a r r a n g e m e n t s of, a n d i n t e r a c t i o n s b e t w e e n , t h e m i c
r o s t r u c t u r a l s u b c o n s t i t u e n t s (the g r a i n s t r u c t u r e of a
polycrystalline m a t e r i a l is a g o o d e x a m p l e of this type
of complexity). I n all b u t t h e simplest m i c r o s t r u c
tures, grain b o u n d a r i e s j o i n t o g e t h e r t o f o r m a n
intricate, topologically c o n n e c t e d n e t w o r k . T h e s e
n e t w o r k s a r e far from r a n d o m : in a d d i t i o n t o fulfill
ing simple topological rules (e.g., Euler relations),
such a n e t w o r k h a s a well-defined grain-size distribu
tion, a d i s t r i b u t i o n of g r a i n faces a n d edges, angles a t
which p a i r s of b o u n d a r i e s m e e t , a n d so o n , t h a t
d e p e n d o n the physics of t h e process c o n t r o l l i n g t h e
d y n a m i c s of g r a i n - b o u n d a r y m o t i o n . T w o very simi
lar classes of m i c r o s t r u c t u r e s g r a i n s a n d s o a p
b u b b l e s h a v e r a t h e r different n e t w o r k p r o p e r t i e s .
Historically, m a n y of t h e difficulties in u n d e r s t a n d
ing such m i c r o s t r u c t u r e s a n d their e v o l u t i o n m a y
be t r a c e d t o p r o b l e m s in visualizing a n d describing
such c o m p l e x s t r u c t u r e s .
U n t i l recently, m e t h o d s w h i c h a t t e m p t e d t o d e
scribe such simple processes as n o r m a l grain g r o w t h
h a d to simplify greatly either t h e c o m p l e x i t y of t h e

246

m i c r o s t r u c t u r e o r the physics w h i c h led t o its evolu

tion. T h e first class of simplifications consists of t h o s e
a p p r o a c h e s w h i c h m a y be collectively referred t o as
mean-field; t h a t is, t h e a c t u a l m i c r o s t r u c t u r e is re
placed by a single " t y p i c a l " grain r e s p o n d i n g t o the
a v e r a g e i n t e r a c t i o n s of all o t h e r grains in t h e system.
W h i l e such a p p r o a c h e s h a v e h a d s o m e limited success
in describing a p r o p o r t i o n of t h e c r u d e r features of
t h e m i c r o s t r u c t u r e , in general they d o n o t lead t o
realistic m i c r o s t r u c t u r e s o r accurately predict the dis
t r i b u t i o n s of t h e grain size o r t o p o l o g i c a l p a r a m e t e r s .
T h e s e c o n d class of simplifications consists of t h o s e
w h i c h a t t e m p t t o describe m i c r o s t r u c t u r e s in t e r m s of
simple g e o m e t r i c a l m o d e l s . T h e s e include t h e use of
Dirichilet cells o r V o r o n o i p o l y h e d r a b a s e d o n a
r a n d o m d i s t r i b u t i o n of p o i n t s t o create grain struc
tures. S u c h m e t h o d s a r e limited t o describing special
types of s t r u c t u r e s a n d processes (e.g., p r i m a r y recrystallization in t h e a b s e n c e of a n y grain g r o w t h ) a n d
h a v e only a m i n i m a l physical basis.
I n principle, c o m p u t e r s i m u l a t i o n p r o v i d e s a n ideal
m e t h o d for a t t a c k i n g t h e c o m p l e x i t y i n h e r e n t in m i c
r o s t r u c t u r a l p r o b l e m s . T h e m a j o r uses of c o m p u t e r
s i m u l a t i o n in m a t e r i a l s science m a y be divided i n t o
three general classes: c o n t i n u u m , a t o m i s t i c a n d elec
t r o n i c . E l e c t r o n i c s t r u c t u r e c a l c u l a t i o n s a r e either
p e r f o r m e d for small clusters of a t o m s ( < 100) o r for
perfect crystals w h e r e t h e n u m b e r of a t o m s e m p l o y e d
in t h e c a l c u l a t i o n is e q u a l t o t h e n u m b e r of a t o m s in a
u n i t cell. A t o m i s t i c c a l c u l a t i o n s typically e m p l o y
2
4
b e t w e e n 10 a n d 10 a t o m s . W h i l e these n u m b e r s are
increasing with i m p r o v e m e n t s in available c o m p u t a
t i o n a l t e c h n i q u e s a n d c o m p u t e r t e c h n o l o g y , such
s i m u l a t i o n s c a n n o t be p e r f o r m e d o n a scale suffi
ciently large t o include m u c h m o r e t h a n a single
isolated m i c r o s t r u c t u r a l feature such as grain b o u n
daries o r dislocations. F o r e x a m p l e , in o r d e r t o simu
late o n e cubic millimeter of a m a t e r i a l (a typical
20
m i c r o s t r u c t u r a l scale) o n e m u s t a c c o u n t for ~ 1 0
a t o m s . T h i s is b e y o n d t h e c u r r e n t state of the a r t by
a p p r o x i m a t e l y sixteen o r d e r s of m a g n i t u d e . Similarly,
d y n a m i c a l a t o m i s t i c s i m u l a t i o n s (e.g., m o l e c u l a r
d y n a m i c s ) a r e typically p e r f o r m e d for n a n o s e c o n d s
while m i c r o s t r u c t u r a l events o c c u r o n time scales
r a n g i n g from m i c r o s e c o n d s t o h o u r s . T h i s discre
1 3
p a n c y is in t h e r a n g e of 1 0 M 0 . Because of the
d i s p a r i t y b e t w e e n t h e size a n d time scales o n w h i c h
significant m i c r o s t r u c t u r a l c o m p l e x i t y exists a n d t h e
i n h e r e n t size-time limitations of a t o m i s t i c simula
tions, m i c r o s t r u c t u r a l s i m u l a t i o n m u s t o p e r a t e o n a
n o n a t o m i s t i c basis.
M o s t s i m u l a t i o n s of m i c r o s t r u c t u r a l e v o l u t i o n a r e
b a s e d o n c o n t i n u u m m o d e l s (see Srolovitz 1986).
T h e s e c o n t i n u u m m o d e l s a r e generally solved by
either (a) n u m e r i c a l i n t e g r a t i o n of t h e e q u a t i o n s of
m o t i o n describing the e v o l u t i o n of individual defects
o r defect segments, o r (b) M o n t e C a r l o m e t h o d s

Microstructural

which a r e b a s e d o n kinetic r a t e t h e o r y a n d a descrip

tion of the energy of t h e m i c r o s t r u c t u r e in t e r m s of t h e
location o f the defects.

1. The Monte
1.1 General

Carlo

Method

Features

T h e M o n t e C a r l o m e t h o d (see Binder 1979) e m p l o y s

r a n d o m numbers t o evaluate t h e probability with
which the v a r i o u s c o n f i g u r a t i o n s o f t h e system o c c u r .
T h e physics o f a n y p r o b l e m u n d e r c o n s i d e r a t i o n is
c o n t a i n e d in t h e expression for this p r o b a b i l i t y a n d
the variables o n which it d e p e n d s . Since t h e e q u i
librium configuration o f t h e system is generally
u n k n o w n , t h e p r o b a b i l i t y is c o m m o n l y w r i t t e n in
t e r m s o f a t r a n s i t i o n p r o b a b i l i t y W(a^>fi)
from o n e
configuration o f t h e system, a , t o a n o t h e r , . If t h e
transition p r o b a b i l i t y b e t w e e n states c a n be identified
with a m i c r o s c o p i c m o d e l , t h e n (with a p p r o p r i a t e
averaging) t h e d e v e l o p m e n t o f t h e system from its
initial configuration t o its final state c o r r e s p o n d s t o
the t i m e - d e p e n d e n t a p p r o a c h t o e q u i l i b r i u m . I n this
w a y the kinetic e v o l u t i o n o f c o m p l e x systems c a n b e
modelled.
T w o types o f t r a n s i t i o n rates a r e c o m m o n l y
employed:

- e x p ( - AH/kT)

if

AH>0

(<^>) =

(1)
otherwise

and

1 + exp( -

AH/kT)

^{exp( -

Evolution:

Q/kT)

Computer

exp[ -

(AH

w h e r e A is a positive c o n s t a n t ,
frequency a n d Q is t h e a c t i v a t i o n
t h e b a c k j u m p r a t e (i.e., from
subtracted out. Normalizing Eqn.
tion p r o b a b i l i t y
W(oc--

'

+ Q)/kT\}

(3)

l / is t h e a t t e m p t
energy. I n E q n . (3)
t o a ) h a s been
(3) yields t h e transi

e x p ( - AH/kT)

Simulation

L l +cxp(-AH/kT)J

(4)

w h e r e a n effective a t t e m p t r a t e ' h a s been defined a s

z[exp(Q/kT)]/A.
T h e final expression o f E q n . (4) is
equivalent t o the conserved-dynamics M o n t e Carlo
t r a n s i t i o n r a t e o f E q n (2). T h i s equivalence establishes
t h e similarity b e t w e e n t h e M o n t e C a r l o a n d r a t e
theory approaches.
Q h a s been a s s u m e d t o be a c o n s t a n t . T h i s is clearly
n o t t r u e for cases w h e r e t h e diffusing v a c a n c y samples
different a t o m i c c o n f i g u r a t i o n s (e.g., regions adjacent
t o defects, s t r a i n e d regions, etc.). F o r a t o m i c systems
in general, Q will n o t b e a c o n s t a n t a n d hence t h e
kinetic (rate t h e o r y ) view o f t h e M o n t e C a r l o m e t h o d
is i n a p p r o p r i a t e . H o w e v e r , t h e s i m u l a t i o n s described
in t h e following a r e n o t a t o m i s t i c , b u t a r e instead
a p p l i c a t i o n s o f t h e M o n t e C a r l o t e c h n i q u e t o conti
n u u m systems. T h i s system is r e p r e s e n t e d in a discrete
form in which all sites a r e equivalent, hence t h e
a s s u m p t i o n o f a c o n s t a n t Q is a p p r o p r i a t e . A s in t h e
r a t e t h e o r y d e s c r i p t i o n o f t h e diffusion process,
scales t h e t i m e in t h e M o n t e C a r l o s i m u l a t i o n s ( t h e
n u m b e r o f M o n t e C a r l o t r a n s i t i o n a t t e m p t s is p r o
p o r t i o n a l t o time). T h e r e f o r e , p r o v i d e d t h a t Q is
known, the relationship between the number of
M o n t e C a r l o a t t e m p t s a n d real time is specified.

(2)

w h e r e is a positive c o n s t a n t w i t h d i m e n s i o n s of t i m e ,
AH = Ha is t h e difference in energy b e t w e e n
configurations a n d a , a n d kT is t h e t h e r m a l energy.
E q u a t i o n (2) is generally e m p l o y e d with c o n s e r v e d
( K a w a s a k i ) d y n a m i c s a n d is used in cases s u c h a s
diffusion, w h e r e t h e t o t a l n u m b e r o f e a c h species is
conserved. E q u a t i o n (1) is used with n o n c o n s e r v e d
( G l a u b e r ) d y n a m i c s a n d is e m p l o y e d in cases such a s
grain g r o w t h , w h e r e t h e c r y s t a l l o g r a p h i c o r i e n t a t i o n
of a p a r t o f t h e solid m a y c h a n g e . T h e c o n f i g u r a t i o n
of t h e system a p p r o a c h e s e q u i l i b r i u m a s t h e n u m b e r
of t r a n s i t i o n a t t e m p t s (using E q n . (1) o r (2)) b e c o m e s
large.
The connection between the M o n t e Carlo m e t h o d
a n d real kinetic processes c a n b e d e m o n s t r a t e d b y
simple r a t e t h e o r y . F o r e x a m p l e , in t h e case o f
vacancy diffusion, t h e n e t flux o f vacancies J from site
t o site is given b y

1.2 Grain

Growth

In o r d e r t o s i m u l a t e m i c r o s t r u c t u r a l e v o l u t i o n , a
m o d e l m u s t b e identified t h a t describes the a p p r o p r i
a t e m i c r o s t r u c t u r a l features. A s a simple e x a m p l e ,
c o n s i d e r t h e case o f n o r m a l g r a i n g r o w t h (i.e., grainsize e v o l u t i o n driven b y g r a i n - b o u n d a r y c u r v a t u r e )
( A n d e r s o n e t al. 1984). T o i n c o r p o r a t e t h e complexity
of g r a i n - b o u n d a r y t o p o l o g y , t h e m i c r o s t r u c t u r e is
m a p p e d o n t o a discrete lattice (see F i g . 1). E a c h
lattice site is assigned a n u m b e r b e t w e e n 1 a n d Q
c o r r e s p o n d i n g t o t h e o r i e n t a t i o n o f t h e grain in which
it is e m b e d d e d . T h e value o f Q m u s t b e c h o s e n t o b e
sufficiently large t h a t i m p i n g e m e n t o f grains with like
o r i e n t a t i o n is infrequent. A g r a i n - b o u n d a r y segment
is defined t o lie b e t w e e n t w o sites o f unlike orien
t a t i o n . A site w h i c h is s u r r o u n d e d b y o t h e r s o f like
o r i e n t a t i o n is in t h e i n t e r i o r o f a grain. T h e H a m i l t o n i a n describing t h e i n t e r a c t i o n b e t w e e n t h e lattice
sites is

247

Microstructural

Evolution:

Computer

2/ 4

14

8
8

8
8

4
4

4
8

8
8

4 /

4 / 9

4
4

4
4

4
8

4
4

4 4

5X4^

4
4

5/8

2 74

Simulation

4
8

19

4\
4

4 / 6
6

6
6

9-9

9
9

9 9

/6

&X4/

/9

6
6

9
9

9^

3 3

61 3 3

3 3 3 3

\ 3

6
6

6 \ 3
6

6\3

3 3 3
3

3
3

8 8 8 8 8 8 8\ 6 6 6 6 6 6/7 7
8 8 8 8 8 8 8
\ 6 6 6 6 6 / 7
7 7
8 8 8 8 8 8 8
\ 6 6 6 6 / 7
7 7
8 8 8 8 8 8 8 8
\ 6 6 6 / 7 7 7 7
8 8 8 8 8 8 8 8/ l \ 7 7 7
Figure 1
Sample microstructure on a triangular lattice where the integers denote local crystallographic orientation and the lines
represent grain boundaries

H=

-/Z(<W,-0

(5)

w h e r e St is o n e of t h e Q possible g r a i n o r i e n t a t i o n s
associated with site i a n d Sab is t h e K r o n e c k e r delta.
T h e s u m is t a k e n over all n e a r e s t - n e i g h b o r ( n n ) p a i r s
of sites. T h u s , n e a r e s t - n e i g h b o r p a i r s c o n t r i b u t e J t o
the system energy w h e n they a r e of unlike o r i e n t a t i o n ,
a n d zero otherwise. Therefore, t h e grain b o u n d a r y
energy is p r o p o r t i o n a l t o J. T h i s m o d e l is k n o w n a s
the g - s t a t e P o t t s m o d e l in statistical-mechanics litera
ture.
T h e kinetics of b o u n d a r y m o t i o n a r e s i m u l a t e d b y
e m p l o y i n g t h e M o n t e C a r l o m e t h o d described a b o v e .
Since grain o r i e n t a t i o n s a r e n o t c o n s e r v e d d u r i n g t h e
process of grain g r o w t h , n o n c o n s e r v e d d y n a m i c s a r e
employed. In the standard M o n t e Carlo method, a
lattice site a n d a n e w trial o r i e n t a t i o n a r e c h o s e n a t
r a n d o m , t h e latter from o n e of t h e o t h e r Q 1
possible o r i e n t a t i o n s . T h e c h a n g e in t h e energy of t h e
system d u e t o t h e r e o r i e n t a t i o n of t h e site is calculated
via E q n . (5). T h e p r o b a b i l i t y t h a t t h e n e w trial
o r i e n t a t i o n is accepted is xW, w h e r e W i s defined a s in
E q n . (1). Successful t r a n s i t i o n s of sites a t grain
b o u n d a r i e s t o o r i e n t a t i o n s of n e a r e s t - n e i g h b o r grains
c o r r e s p o n d t o grain b o u n d a r y m i g r a t i o n . T h i s leads
to a description of b o u n d a r y m o t i o n which is e q u i v a
lent t o t h a t derived from classical r e a c t i o n - r a t e
theory.

248

I n t h e s i m u l a t i o n s described in t h e following, t h e
system is s t a r t e d a t a t e m p e r a t u r e well in excess of t h e
melting o r critical t e m p e r a t u r e Tc a n d rapidly
q u e n c h e d t o < Tc. T o r e d u c e finite size effects, very
large systems with p e r i o d i c b o u n d a r y c o n d i t i o n s a r e
usually e m p l o y e d : 40 000 sites o n t r i a n g u l a r lattices o r
6
10 sites o n a cubic lattice a r e typical. T h e u n i t of time
is defined as 1 M o n t e C a r l o step ( M C S ) which c o r r e s
p o n d s to microtrials or reorientation attempts,
w h e r e TV is t h e t o t a l n u m b e r of sites in t h e system.
V a r i a t i o n s of t h e p r o c e d u r e a r e often e m p l o y e d t o
increase t h e efficiency of t h e s i m u l a t i o n m e t h o d .
T h e m a i n result of a n y s t u d y of m i c r o s t r u c t u r a l
e v o l u t i o n is t h e a c t u a l m i c r o s t r u c t u r e : all o t h e r infor
m a t i o n m a y b e e x t r a c t e d from this a n d its d e v e l o p
m e n t over time. F i g u r e 2 s h o w s a representative series
of m i c r o g r a p h s r e p r e s e n t i n g different times in a t w o dimensional normal grain-growth simulation. T h e
general a p p e a r a n c e of t h e m i c r o s t r u c t u r e s h o w s g o o d
c o r r e s p o n d e n c e with t h o s e in polished sections of
samples h a v i n g u n d e r g o n e n o r m a l grain g r o w t h .
M o r e detailed e x a m i n a t i o n s h o w s t h a t
grain
b o u n d a r i e s t e n d t o m e e t a t 120; small grains t e n d t o
h a v e fewer t h a n six sides a n d u n d e r g o s h r i n k a g e ; large
grains t e n d t o h a v e m o r e t h a n six sides a n d u n d e r g o
g r o w t h . All of these results a r e in a g r e e m e n t with
experimental observations.
O n e of t h e p o t e n t i a l p r o b l e m s of c o m p a r i n g t h e
s i m u l a t i o n results with e x p e r i m e n t a l o b s e r v a t i o n s is
t h a t t h e s i m u l a t i o n s a r e p e r f o r m e d in t w o d i m e n s i o n s

Microstructural

= 1000

=5000

Evolution:

Computer

Simulation

=3000

=7000

Figure 2
The temporal evolution of a typical microstructure undergoing normal grain growth

while the e x p e r i m e n t a l o b s e r v a t i o n s a r e m a d e o n
cross sections of t h r e e - d i m e n s i o n a l s a m p l e s . I n o r d e r
to test t h e validity of r e p r e s e n t i n g cross sections of
real m a t e r i a l s b y t w o - d i m e n s i o n a l s i m u l a t i o n s , a d d i
tional s i m u l a t i o n s of n o r m a l g r a i n g r o w t h were per
formed in three spatial d i m e n s i o n s ( A n d e r s o n et al.
1989). C o m p a r i s o n of t h e g r a i n size (RA) d i s t r i b u t i o n
d e t e r m i n e d from cross sections of t h e t h r e e d i m e n s i o n a l s i m u l a t i o n w i t h t h a t for p u r e i r o n a n d
the t w o - d i m e n s i o n a l s i m u l a t i o n s s h o w excellent
a g r e e m e n t . A similar c o m p a r i s o n of t h e n o r m a l i z e d
grain size versus t h e n u m b e r of edges p e r g r a i n (Fig.
3) for M g O a n d tin, d e t e r m i n e d e x p e r i m e n t a l l y in
two-dimensional and three-dimensional simulations,
also shows a n excellent c o r r e s p o n d e n c e . R e c e n t s i m u
lation results s h o w t h a t for later times t h e m e a n g r a i n
112
size g r o w s as R = At
in t w o - a n d t h r e e - d i m e n s i o n a l
simulations, a n d with a slightly smaller e x p o n e n t a t
earlier times. T h e o r e t i c a l analyses of g r a i n - g r o w t h
m
kinetics typically s h o w t g r o w t h laws, b u t experi
m e n t a l w o r k usually yields a smaller e x p o n e n t ( p r e

l/2

s u m a b l y d u e t o i m p u r i t y effects) a l t h o u g h t g r o w t h
has been observed.
O n e of t h e m a j o r benefits of this class of s i m u l a t i o n
studies is t h e ability t o test theoretical ideas. Simula
tion often p r o v i d e s a b e t t e r test t h a n e x p e r i m e n t since
s i m u l a t i o n s c a n b e p e r f o r m e d t o e x a m i n e t h e effects
of different a s s u m p t i o n s directly w i t h o u t t h e inevi
t a b l e c o m p l i c a t i o n s associated with impurities, m i c
r o s t r u c t u r a l features o t h e r t h a n t h o s e being studied
a n d destructive e v a l u a t i o n t e c h n i q u e s . A n e x a m p l e of
w h e r e s i m u l a t i o n h a s d e m o n s t r a t e d t h e p o o r state of
theoretical u n d e r s t a n d i n g is in t h e a r e a of a b n o r m a l
g r a i n g r o w t h (also k n o w n as s e c o n d a r y recrystallization a n d e x a g g e r a t e d g r a i n g r o w t h ) . It is generally
believed t h a t a b n o r m a l g r o w t h is associated with the
presence a n d t h e n d i s s o l u t i o n of s e c o n d - p h a s e p a r t i
cles. S i m u l a t i o n s h a v e s h o w n , h o w e v e r , t h a t texture
effects a n d t h e related g r a i n - b o u n d a r y mobility a n i s o
t r o p y c a n lead t o a b n o r m a l g r o w t h (Rollett et al.
1989). A relatively s t r o n g t e x t u r e is a c o m m o n by
p r o d u c t of processing m a t e r i a l c o n t a i n i n g particles.

249

Microstructural

Evolution:

Computer

Simulation

MgO

OSn
2 - d simulation
3 - d simulation

Y
V
A

Number of sides

Figure 3
Relationship between the number of sides exhibited by
grains when viewed in cross section and the average grain
radius determined from the cross-sectional area for the
given number of sides

T h e s e texture-controlled s i m u l a t i o n s lead t o m i c r o structures a n d the presence of a t e x t u r e c h a n g e c o n

sistent with e x p e r i m e n t a l o b s e r v a t i o n s . A theoretical
f r a m e w o r k for a b n o r m a l g r o w t h h a s evolved from the
k n o w l e d g e derived from these s i m u l a t i o n s .
G e n e r a l i z a t i o n s of t h e grain g r o w t h m o d e l t o in
clude p r i m a r y recrystallization are m a d e by a d d i n g a
n u c l e a t i o n m e c h a n i s m a n d by the a d d i t i o n of a n
energetic t e r m which a c c o u n t s for t h e energy s t o r e d in
a m a t e r i a l in the form of dislocations (Srolovitz et al.
1986). P r i m a r y recrystallization h a s been simulated as
a function of the degree of s t o r e d energy, t h e density
of nuclei, the m o d e of n u c l e a t i o n (site s a t u r a t e d o r
c o n s t a n t rate), i n h o m o g e n e o u s l y s t o r e d energy (e.g.,
d u e t o i n h o m o g e n e o u s d e f o r m a t i o n ) a n d t h e density
of s e c o n d - p h a s e particles. In a d d i t i o n t o m i c r o s t r u c tures a n d their t e m p o r a l e v o l u t i o n , such s i m u l a t i o n s
yield recrystallized fraction as a function of time,
J o h n s o n - M e h l - A v r a m i ( J M A ) e x p o n e n t s (which in
dicate t h e n u c l e a t i o n a n d g r o w t h m o d e ) , grain size
versus time, grain-size d i s t r i b u t i o n s , a n d so o n . In the
simplest cases ( u n i f o r m s t o r e d energy, n o particles)
the s i m u l a t i o n s yield results t h a t a r e consistent with
theory. H o w e v e r , w h e n t h e s t o r e d energy is n o n uniformly d i s t r i b u t e d t h r o u g h t h e m a t e r i a l (varies
o n a grain by grain basis) t h e J M A e x p o n e n t s a r e
m u c h lower t h a n t h e theoretical values. Such low
e x p o n e n t s a r e the rule in e x p e r i m e n t a l studies of
p r i m a r y recrystallization.
A p p l i c a t i o n s of this type of m o d e l t o o t h e r types of
m i c r o s t r u c t u r e s a n d their e v o l u t i o n require suitable
modification of the energetics expression, as in E q n .

250

Figure 4
A late stage sintering microstructure: the black regions are
voids, the white ones are grains and the lines represent
grain boundaries

(5), t o a c c o u n t for t h e different possible driving

forces, a n d also a suitable discretization of t h e m i c r o s t r u c t u r e . T o d a t e , this t y p e of m o d e l h a s been applied
t o n o r m a l g r a i n g r o w t h , g r a i n g r o w t h in t h e presence
of a dispersed s e c o n d p h a s e , a b n o r m a l g r a i n g r o w t h ,
p r i m a r y recrystallization, recrystallization in t h e p r e s
ence of a dispersed second p h a s e including particle
s t i m u l a t e d n u c l e a t i o n , a n d d y n a m i c recrystallization.
C o m b i n i n g this s i m u l a t i o n m e t h o d with a M o n t e
C a r l o diffusion t e c h n i q u e (based o n K a w a s a k i d y n a
mics a n d E q n . (2)) yields a m e t h o d a p p r o p r i a t e for
diffusion-limited p r o b l e m s . T h i s h y b r i d t e c h n i q u e h a s
been applied t o t h e s t u d y of b o u n d a r y m i g r a t i o n a n d
sintering c o n t r o l l e d b y a diffusing i m p u r i t y . F i g u r e 4
s h o w s a late-stage sintering m i c r o s t r u c t u r e p r o d u c e d
using such a t e c h n i q u e . If t h e M o n t e C a r l o diffusion
m e c h a n i s m is c o u p l e d with a n energy expression
w h i c h a c c o u n t s for b o t h elastic a n d surface energy,
the c o a r s e n i n g of precipitates in a stress field c a n b e
s i m u l a t e d . F i g u r e 5 s h o w s t h e m i c r o s t r u c t u r a l evolu
tion of t h e t w o - p h a s e s t r u c t u r e ( a n d / ) typical of
nickel-based superalloys u n d e r t h e influence of a n
applied stress (see G a y d a a n d Srolovitz 1989). S u c h a
stress field biased -' m o r p h o l o g y is typically
observed.
1.3 Ostwald
Ripening
O s t w a l d r i p e n i n g is t h e p r o c e s s of diffusional c o a r s e n
ing of s e c o n d - p h a s e particles. A p p l i c a t i o n of t h e
M o n t e C a r l o m e t h o d t o O s t w a l d ripening is a c c o m
plished b y assigning 5, = 1 t o e a c h site o n a lattice;
St = 1 c o r r e s p o n d s t o m a t r i x sites a n d S, = 1 c o r r e s
p o n d s t o sites o c c u p i e d b y t h e s e c o n d p h a s e . A
H a m i l t o n i a n similar t o t h a t given in E q n . (5) is
e m p l o y e d . T h i s m o d e l c o r r e s p o n d s t o t h e classical
Ising m o d e l . Since t h e t o t a l a m o u n t of b o t h m a t r i x
a n d second p h a s e is conserved d u r i n g t h e diffusional

Microstructural

Evolution:

Computer

Simulation

MCS

5 0 MCS

b
C

2 0 0 MCS

Figure 5
The temporal evolution of a two-phase (misfitting, coherent) microstructure under the influence of a tensile stress applied
vertically

coarsening, conserved or Kawasaki dynamics (Eqn.

(1)) are employed. Rao et al. (1976) studied Ostwald
ripening in this type of model at a few different
second-phase concentrations following quenches
from the high-temperature disordered state (i.e., solid
solution) into lower-temperature two-phase regions.
These simulations were analyzed in terms of the timedependent structure factor S(k,t), the size distribution
of second-phase particles and the surface-to-volume
ratio of these particles (actually the two-dimensional
analog perimeter-to-area ratio).
The microstructure resulting from these simula
tions consists of both well-defined second-phase parti
cles containing many S= 1 sites and a large
number of isolated S= - 1 sites (i.e., surrounded by
S = 1 sites). These small "particles" are the main

diffusing species. The densities of these single sites

agree with calculations of the "vapor pressure" of the
larger second-phase particles which have a finite
radius. In addition to the diffusion of single secondphase sites, the larger particles were also seen to
migrate, although at a much slower rate than the
single sites, as expected. Due to the limited simulation
statistics, it was not possible to make an accurate
comparison between the simulation and predicted
particle size distribution functions. Analysis of the
simulated coarsening kinetics showed that the mean
particle size increased in time as /*, where ~ 0 . 2 . This
contrasts with the classical Lifshitz-Slyozov-Wagner
prediction of = 1/3. However, more recent calcula
tions on a variant of this model (Sadiq and Binder
1983) yielded = 0.35. Recent experience with Monte
251

Microstructural

Evolution:

Computer

Simulation

C a r l o m o d e l s of this general class h a v e s h o w n t h a t

power-law kinetics with e x p o n e n t s smaller t h a n
theoretically predicted are c o m m o n , b u t a crossover
to the theoretical e x p o n e n t s eventually o c c u r s .

of t h e s a m p l e t o t h a t of t h e interface. A p p l i c a t i o n of
this m o d e l t o d e n d r i t i c g r o w t h in t w o d i m e n s i o n s
yields
. dx
(

2. Equation

of Motion

Methods

T h e e q u a t i o n of m o t i o n m e t h o d s for simulating mic

r o s t r u c t u r a l evolution c a n be divided i n t o t w o classes:
front t r a c k i n g m e t h o d s a n d particle m e t h o d s . U n l i k e
the M o n t e C a r l o m e t h o d , which simulates the evolu
tion of the entire solid b o d y , the e q u a t i o n of m o t i o n
m e t h o d s focus o n only t h o s e p a r t s of the m i c r o s t r u c ture t h a t are evolving. By d o i n g this, these m e t h o d s
are able to simulate m i c r o s t r u c t u r a l evolution far
m o r e efficiently.
2.1 Front

Tracking

F r o n t t r a c k i n g m e t h o d s h a v e f o u n d wide a p p l i c a t i o n
in the physical sciences, including studies of flame
fronts, chemical reaction fronts, c l o u d s , fluid flow,
shocks, solidification fronts a n d p l a s m a s (see B i s h o p
et al. 1984). T h e s e m e t h o d s r e d u c e t h e physical p r o b
lem to o n e which m a y be solved strictly o n a front o r
interface. T h e t r u e ^/-dimensional (where d is t h e
d i m e n s i o n of the b o d y ) d y n a m i c a l p r o b l e m is
generally t r a n s f o r m e d i n t o a set of p a r t i a l differential
or integrodifferential e q u a t i o n s which a r e numerically
solved at a finite set of p o i n t s o n the front o r interface.
A s the interface d e f o r m s , e x p a n d s o r c o n t r a c t s , the
n u m b e r of p o i n t s describing the interface is often
c h a n g e d in o r d e r t o g u a r a n t e e n u m e r i c a l a c c u r a c y .
T h e a c t u a l i m p l e m e n t a t i o n of this m e t h o d varies
widely: the c o m p u t a t i o n a l t e c h n i q u e s involved a r e
described by Wilson et al. (1978). T h i s section de
scribes the a p p l i c a t i o n of such m e t h o d s t o t w o p r o b
lems in m i c r o s t r u c t u r a l e v o l u t i o n , n a m e l y t o the
f o r m a t i o n of d e n d r i t e s d u r i n g solidification, a n d t o
grain g r o w t h .
(a) Dendritic growth. This h a s received a great deal of
a t t e n t i o n in recent years, d u e , in p a r t , to the rich
p a t t e r n s formed d u r i n g t h e g r o w t h process a n d o u r
inability t o describe theoretically t h e c o m p l e t e d y n a
mic evolution of these structures. W h e n t h e melt is
u n d e r c o o l e d (i.e., below the melting p o i n t Tm), the
solid-liquid interface is u n s t a b l e a n d d e n d r i t e s form.
T h e rate-limiting step in such a process is t h e diffusion
of the (latent) h e a t a w a y from the solidification front.
Such a process m a y be m o d e l l e d by t h e ( t h e r m a l )
diffusion e q u a t i o n in the entire b o d y plus a n equi
librium c o n d i t i o n for the interface. T h i s c o n d i t i o n
a c c o u n t s for the melting t e m p e r a t u r e a n d its varia
tions with c u r v a t u r e (i.e., the G i b b s - T h o m p s o n
effect).
Recent p h e n o m e n o l o g i c a l w o r k o n d e n d r i t i c
g r o w t h (see B r o w e r et al. 1984) b a s e d o n a set of
simplistic a s s u m p t i o n s k n o w n as the " g e o m e t r i c a l
m o d e l , " reduces the p r o b l e m from the d i m e n s i o n a l i t y

252

ds

) [1 + cos(m0)]

(6)

I n this e q u a t i o n , t h e interface is r e p r e s e n t e d by the

time e v o l u t i o n of t h e p o i n t s o n the surface which is
p a r a m e t e r i z e d in t e r m s of its n o r m a l #i, a r c l e n g t h s,
c u r v a t u r e , a n d o r i e n t a t i o n angle (with respect t o
t h e u n d e r l y i n g crystal structure). A a n d a r e physical
p a r a m e t e r s g o v e r n i n g t h e g r o w t h , m is t h e d e g e n e r a c y
of t h e u n d e r l y i n g crystal s y m m e t r y a n d is a m e a s u r e
of t h e a n i s o t r o p y of t h e interfacial p r o p e r t i e s . T h e
linear t e r m in a c c o u n t s for the G i b b s - T h o m p s o n
2
effect, t h e t e r m for t h e u n d e r c o o l i n g of t h e melt,
3
the AC t e r m for the finite solid n u c l e a t i o n b a r r i e r a n d
the surface L a p l a c i a n t e r m a c c o u n t s for diffusion. T h e
s q u a r e b r a c k e t e d t e r m allows for v a r i a t i o n s in t h e
interfacial p r o p e r t i e s with t h e interface o r i e n t a t i o n ,
with respect t o t h e u n d e r l y i n g crystal s t r u c t u r e .
If t h e right h a n d side of E q n . (6) is d e n o t e d b y F(G),
t h e n this e q u a t i o n b e c o m e s

(7)
) J W ) ]

ds'

Jo

where both and s depend on some time-independent

p a r a m e t e r i z a t i o n of t h e interface (which is a s s u m e d t o
be a closed curve). It is c o n v e n i e n t t o i n t r o d u c e a
relative a r c l e n g t h p a r a m e t e r i z a t i o n = s/sT w h e r e sT
is t h e t o t a l length of t h e interface. E q u a t i o n s (7) c a n
t h e n b e rewritten as
dfl(q) _ _ 1 dF(0)
dt

doc
* ( "()

doc' - a^KF(e)

dot' ) /

(8)

dsT
f
- = s T \ <xF(6) doc
ot
JQ
1

w h e r e = (\/sT)d6/doi.
D i s c r e t i z a t i o n of E q n s . (8)
yields a c o u p l e d set of o r d i n a r y differential e q u a t i o n s
which c a n t h e n be i n t e g r a t e d using a p r e d i c t o r c o r r e c t o r o r d i n a r y differential e q u a t i o n
solver.
Finally, t h e physical interface is r e c o n s t r u c t e d b y
integrating
x(oc)=

I c o s [ 0 ( a ' ) ] doc'
J 0

(9)
y(*) = y

- i s i n [ 0 ( a ' ) ] doc'
Jo

Microstructural

Evolution:

Computer

Simulation

good agreement with experiment a n d with those

f o u n d in t h e M o n t e C a r l o s i m u l a t i o n s . H o w e v e r ,
since this m e t h o d only requires p o i n t s o n t h e grain
b o u n d a r i e s , t h e n u m b e r of p o i n t s n e e d e d in t h e integ
r a t i o n is m u c h less t h a n t h a t r e q u i r e d in t h e M o n t e
C a r l o s i m u l a t i o n s a n d so it is, in principle, m o r e
efficient.

Figure 6
A two-dimensional dendrite simulated within the
framework of the geometrical model
F i g u r e 6 s h o w s a typical d e n d r i t e s i m u l a t e d using this
m e t h o d with 300 p o i n t s a n d t h e p a r a m e t e r s m = 4,
A = 4, B = 2 a n d = 0.15. T h e r e s u l t a n t d e n d r i t i c
s t r u c t u r e exhibits a fourfold s y m m e t r y , s i d e - b r a n c h e s
a n d overall s h o w s a n excellent c o r r e s p o n d e n c e w i t h
experimentally o b s e r v e d d e n d r i t i c m o r p h o l o g i e s .
F u r t h e r m o r e , this class of s i m u l a t i o n s h a s led t o a
theoretical u n d e r s t a n d i n g of o p e n q u e s t i o n s such a s
w h a t d e t e r m i n e s t h e g r o w t h velocity.
(b) Grain growth.
F r o n t tracking methods have
recently been a p p l i e d t o t h e s t u d y of g r a i n g r o w t h (see
C e p p i a n d N a s e l l o 1984, F r o s t et al. 1988). I n this case
the p a r t i a l differential e q u a t i o n describing t h e t e m
p o r a l e v o l u t i o n of t h e g r a i n b o u n d a r i e s is q u i t e sim
ple. G r a i n b o u n d a r i e s a r e a s s u m e d t o m o v e a c c o r d i n g
to v n = , w h e r e v n is t h e velocity of a b o u n d a r y
segment n o r m a l t o itself, is t h e local b o u n d a r y
c u r v a t u r e a n d is a c o n s t a n t " m o b i l i t y . " A n initial
t w o - d i m e n s i o n a l s t r u c t u r e is c o n s t r u c t e d , i n t e g r a t i o n
points are distributed along the grain boundaries and
each p o i n t is m o v e d a l o n g t h e local b o u n d a r y n o r m a l
by d u r i n g e a c h i n t e g r a t i o n t i m e step /. Since
three b o u n d a r i e s t e n d t o m e e t a t 120 triple p o i n t s , t h e
positions of t h e triple p o i n t s m u s t also b e u p d a t e d .
T h i s is a c c o m p l i s h e d b y m o v i n g t h e m t o s u c h a
position, w i t h respect t o t h e t h r e e b o u n d a r i e s , t h a t t h e
120 c o n d i t i o n is satisfied. T h e b o u n d a r y - m i g r a t i o n
a n d triple-point u p d a t e steps a r e i t e r a t e d alternately.
T o p o l o g i c a l c h a n g e s , such as t h e s h r i n k i n g a w a y of a
small grain o r c h a n g e s in t h e n u m b e r of edges of a
grain by vertex i m p i n g e m e n t , a r e a c c o u n t e d for b y
reconnecting t h e local n e t w o r k in t h e vicinity of t h e
a p p r o p r i a t e vertex.
This method has been applied to b o t h n o r m a l a n d
a b n o r m a l g r a i n g r o w t h . I n b o t h cases c a l c u l a t i o n s
yield r e a s o n a b l e m i c r o s t r u c t u r e s a n d kinetics a r e in

(c) Ostwald ripening. F r o n t t r a c k i n g m e t h o d s h a v e

also been a p p l i e d t o O s t w a l d ripening. V o o r h e e s et al.
(1988) h a v e d e v e l o p e d a theoretical f r a m e w o r k which
results in a n e q u a t i o n of m o t i o n for t h e surfaces of
diffusionally i n t e r a c t i n g s e c o n d - p h a s e particles. T h e i r
m e t h o d is b a s e d o n a b o u n d a r y - i n t e g r a l t e c h n i q u e for
t h e s o l u t i o n of t h e diffusion p r o b l e m for a r b i t r a r y
particle s h a p e s . T h e r e s u l t a n t integral e q u a t i o n s were
discretized in t e r m s of m e s h p o i n t s o n t h e particle
surfaces a n d i n t e g r a t e d using a geometrically conver
g e n t iterative p r o c e d u r e . T h e t i m e e v o l u t i o n of t h e
O s t w a l d r i p e n i n g particle s h a p e s w a s s i m u l a t e d for
2 - 1 6 initially circular particles.
T h e s e s i m u l a t i o n s s h o w e d a n u m b e r of interesting
features. First, diffusional i n t e r a c t i o n s led t o signific
a n t d i s t o r t i o n of particle s h a p e s , s o m e t i m e s resulting
in t h e relatively flat particle surfaces often o b s e r v e d in
liquid p h a s e sintering. S e c o n d , particle m i g r a t i o n w a s
o b s e r v e d over distances larger t h a n t h e initial particle
r a d i u s . T h i r d , particles t h a t s h r i n k o n o n e side b u t
g r o w o n a n o t h e r were o b s e r v e d (this leads t o b o t h
particle m i g r a t i o n a n d s h a p e c h a n g e ) . R e l a t e d m o d e l s
w h i c h a c c o u n t for stress effects h a v e b e e n s h o w n t o
lead t o t h e d e v e l o p m e n t of spatial c o r r e l a t i o n s
b e t w e e n particles d u r i n g O s t w a l d ripening ( V o o r h e e s
a n d J o h n s o n 1988).
2.2 Particle
Methods
Particle m e t h o d s a r e very similar t o t h e front t r a c k i n g
m e t h o d s described in Sect. 2 . 1 . I n s t e a d of c o n c e n t r a t
ing o n interfaces, h o w e v e r , they focus o n t h e evolu
tion of special p o i n t s in t h e m i c r o s t r u c t u r e such as the
triple p o i n t s a l o n g w h i c h g r a i n b o u n d a r i e s m e e t , o r
i n d i v i d u a l defects. T h e e v o l u t i o n of such p o i n t s is
d e t e r m i n e d b y t h e s o l u t i o n of their local e q u a t i o n s of
m o t i o n . T h i s section describes t h e a p p l i c a t i o n of such
m e t h o d s t o t w o p r o b l e m s in m i c r o s t r u c t u r a l evolu
tion; n a m e l y , t o t h e e v o l u t i o n of dislocation s u b s t r u c
ture and to grain growth.
(a) Dislocation substructure. D i s l o c a t i o n s interact b y
w a y of their elastic stress fields. Since t h e force o n e
d i s l o c a t i o n exerts o n a n o t h e r is well k n o w n , it is
possible t o s i m u l a t e t h e e v o l u t i o n of a large n u m b e r
of i n t e r a c t i n g d i s l o c a t i o n s (see G h o n i e m a n d A m o d e o
1988). H o w e v e r , in o r d e r t o m a k e t h e m o d e l t r a c t a b l e ,
it is necessary t o restrict a t t e n t i o n t o t h e relatively
simple case of s t r a i g h t parallel dislocations (i.e., t w o
d i m e n s i o n s w i t h z e r o - d i m e n s i o n a l dislocation lines).
T h e e q u a t i o n s of m o t i o n of such dislocations a r e
d o m i n a t e d b y t h e o b s e r v e d linear d e p e n d e n c e of
d i s l o c a t i o n velocity o n driving force; however, for

253

Microstructural

Evolution:

Computer

Simulation

Figure 7
3
The evolution of a microstructure containing 10 dislocations distributed on parallel slip planes: the _L and symbols
indicate edge dislocations with Burgers vectors of opposite signs

fast-moving dislocations, dislocation m o m e n t u m m a y

be i m p o r t a n t . T h e r e s u l t a n t e q u a t i o n of m o t i o n m a y
be written as
m*5r, = F

- r i , +

e x t

(10)

w h e r e x, is the c o o r d i n a t e of dislocation /, d o t s
indicate differentiation with respect t o time, w * is t h e
effective dislocation m a s s , F e xt is t h e force o n disloca
tion i in t h e direction d u e t o a n external stress, is
the d a m p i n g factor a n d t h e last t e r m a c c o u n t s for t h e
i n t e r a c t i o n of dislocation / with all o t h e r dislocations.
S e p a r a t e e q u a t i o n s m u s t b e w r i t t e n for glide a n d
climb, a n d a p p r o p r i a t e d a m p i n g factors m u s t b e
d e t e r m i n e d for each. All of t h e t e r m s in E q n . (10) c a n
be calculated directly from t h e elastic t h e o r y of dislo
cations.
E q u a t i o n (1) c a n be i n t e g r a t e d for e a c h dislocation
by t a k i n g small finite time-steps. If dislocations of
o p p o s i t e sign b e c o m e closer t h a n a cutoff d i s t a n c e
(defined in t e r m s of the size of the time-step At), they
are annihilated. T h e i n t e g r a t i o n of E q n . (10) is carried
o u t in the s a m e w a y as the i n t e g r a t i o n of N e w t o n ' s
e q u a t i o n of m o t i o n in n o r m a l m o l e c u l a r d y n a m i c s
calculations. H o w e v e r , unlike m o l e c u l a r d y n a m i c s ,
the particles a r e n o t a t o m s b u t d i s l o c a t i o n s . F i g u r e 7
3
shows the t e m p o r a l e v o l u t i o n of 10 dislocations o n
t h e s a m e slip system w i t h either positively o r negati
vely signed B u r g e r s vectors. T h e initial s t r u c t u r e is
r a n d o m , b u t after a s h o r t time it f o r m s oppositely
signed dislocation walls. T h e dislocation density, t h e
s t r e n g t h a n d density of s e c o n d - p h a s e particles, the
applied stress, the t e m p e r a t u r e ( t h r o u g h t h e relative
values of the glide a n d climb d a m p i n g ) a n d t h e
available slip systems c a n be varied i n d e p e n d e n t l y in
these s i m u l a t i o n s . V a r i a t i o n s of this type of m o d e l
b a s e d o n different e q u a t i o n s of m o t i o n a n d m e t h o d s

254

of s o l u t i o n h a v e been developed: for e x a m p l e , cellular

a u t o m a t a (see L e p i n o u x a n d K u b i n 1987).
(b) Grain growth. T h e particle m e t h o d a p p r o a c h t o
g r a i n g r o w t h focuses o n t h e d y n a m i c a l e v o l u t i o n of
t h e p o s i t i o n s of t h e vertices a t w h i c h three grain
b o u n d a r i e s m e e t in t w o d i m e n s i o n s . S o a r e s et al.
(1985) a n d N a g a i et al. (1988) i n d e p e n d e n t l y p r o
p o s e d t o write t h e e q u a t i o n of m o t i o n of a vertex
(grain b o u n d a r i e s a r e a s s u m e d t o b e straight a n d
c o n n e c t t w o vertices) in t w o d i m e n s i o n s as
v, = M X ^
j=

(11)

w h e r e v, is t h e velocity of vertex , is a c o n s t a n t
" m o b i l i t y , " etj is t h e line tension of t h e grain b o u n d a r y
c o n n e c t i n g sites / a n d j , a n d t h e s u m is t a k e n over t h e
three g r a i n b o u n d a r i e s m e e t i n g a t vertex i. E q u a t i o n
(11) is t h e n i n t e g r a t e d with a small time-step At. A s in
t h e front t r a c k i n g m e t h o d , special h a n d l i n g is
r e q u i r e d t o deal with t h e t o p o l o g i c a l c h a n g e s t h a t
o c c u r w h e n vertices meet.
T h i s m o d e l yields m i c r o s t r u c t u r e s a n d g r o w t h kin
etics w h i c h a r e in a g r e e m e n t with t h o s e f o u n d b y t h e
front t r a c k i n g a n d M o n t e C a r l o m e t h o d s a n d in cross
sections of e x p e r i m e n t a l g r a i n - g r o w t h s a m p l e s . Since
this m e t h o d focuses o n vertices r a t h e r t h a n g r a i n
b o u n d a r i e s (as is d o n e in t h e front t r a c k i n g m e t h o d s )
o r g r a i n s (as is d o n e in t h e M o n t e C a r l o m o d e l ) it is in
principle m o r e efficient.

3.

Conclusions

W h i l e grain g r o w t h is n o t necessarily t h e m o s t im
p o r t a n t a r e a of m i c r o s t r u c t u r a l e v o l u t i o n , it h a s b e e n
e m p h a s i z e d b e c a u s e of t h e wide variety of t e c h n i q u e s

Microtextural

t h a t h a v e b e e n a p p l i e d in its s i m u l a t i o n s t u d y . A s t h e
s i m u l a t i o n m e t h o d s b e c o m e increasingly efficient b y
c o n c e n t r a t i n g o n smaller a n d smaller c o m p o n e n t s of
the microstructure, m o r e assumptions are required
a n d a certain degree of simplicity is lost. T h i s is clearly
evident as t h e s i m u l a t i o n of g r a i n g r o w t h h a s evolved
from (least t o m o s t efficient) M o n t e C a r l o m e t h o d s
(which focus o n t h e g r a i n ) via front t r a c k i n g m e t h o d s
(which focus o n t h e g r a i n b o u n d a r i e s ) t o t h e particle
m e t h o d s (which focus o n t h e g r a i n b o u n d a r y ver
tices). I n cases w h e r e t h e identical s i m u l a t i o n is t o b e
r u n m a n y times (with different p a r a m e t e r s ) , as in a
p r o d u c t i o n e n v i r o n m e n t , t h e m o s t efficient m e t h o d s
should b e used even t h o u g h they e m p l o y t h e m o s t
a s s u m p t i o n s a n d a r e n o t easily generalizable. I n a
research e n v i r o n m e n t , h o w e v e r , generalizability, sim
plicity a n d t h e m i n i m u m n u m b e r of a s s u m p t i o n s a r e
necessities a n d clearly favor t h e m o r e
basic
approaches.
The computer simulation methods and applications
described represent o n l y a s a m p l i n g of t h e s i m u l a t i o n
methods currently applied to microstructure-related
p r o b l e m s in m a t e r i a l s science. O t h e r a r e a s t o w h i c h
m i c r o s t r u c t u r a l s i m u l a t i o n s h a v e been a p p l i e d in
clude directional solidification, film g r o w t h , particle
coarsening and texture development during deforma
tion. T o d a t e , m o s t of t h e interest in t h e s i m u l a t i o n of
m i c r o s t r u c t u r a l e v o l u t i o n h a s c o m e f r o m t h e basic
research a r e a of m a t e r i a l s science a n d engineering.
H o w e v e r , as t h e p o w e r a n d availability of c o m p u t e r s
continues to grow a n d new simulation m e t h o d s are
developed, c o m p u t e r s i m u l a t i o n of m i c r o s t r u c t u r a l
e v o l u t i o n will m o v e increasingly from t h e h a n d s of
researchers t o t h o s e of engineers.

Analysis

dislocation pattern formation. In: Kubin L P, Martin G

(eds.) 1988 Non-Linear Phenomena in Materials Science.
Trans Tech, Switzerland, pp. 377-88
Lepinoux J, Kubin L 1987 The dynamic organization
of dislocation structures. A simulation. Scr. Metall. 21:
833-8
Nagai T, Kawasaki K, Nakamura 1988 Vertex dynamics
of two-dimensional domain growth. In: Komura S,
Furukawa (eds.) 1988 Dynamics of Ordering Process
in Condensed Matter. Plenum, New York, pp. 121-5
Rao M, Kalos , Lebowitz J L, Marro J 1976 Time
evolution of a quenched binary alloy: III. Computer
simulation of a two-dimensional model system. Phys.
Rev. 13: 4328-35
Rollett A D, Srolovitz D J, Anderson 1989 Simulation
and theory of abnormal grain-growth anisotropic grainboundary energies and mobilities. Acta Metall. 37(4):
1227^0
Sadiq A, Binder 1983 Kinetics of domain growth in two
dimensions. Phys. Rev. Lett. 51: 674-8
Soares A, Ferro A C, Fortes M A 1985 Computer simula
tion of grain growth in a bidimensional polycrystal. Scr.
Metall. 19: 1491-6
Srolovitz D J (ed.) 1986 Computer Simulation of Microstruc
tural Evolution. Metallurgical Society, Warrendale, PA
Srolovitz D J, Grest G S, Anderson 1986 Computer
simulation of recrystallization. 1. Homogeneous nucleation and growth. Acta Metall. 34: 1833-45
Voorhees W, Johnson W C 1988 Development of spatial
correlation during diffusional late-stage phase transfor
mations in stressed solids. Phys. Rev. Lett. 61: 2225-8
Voorhees W, McFadden G B, Boisvert R F, Meiron D I
1988 Numerical simulation of morphological develop
ment during Ostwald ripening. Acta Metall. 36: 207-22
Wilson D G, Solomon A D, Boggs 1978 Moving
Boundary Problems. Academic Press, New York
D . J. Srolovitz
[University of M i c h i g a n , A n n A r b o r ,
Michigan, USA]

Bibliography
Anderson , Grest G S, Srolovitz D J 1989 Computer
simulation of normal grain growth in 3 dimensions.
Philos. Mag. 59 (3): 293-329
Anderson , Srolovitz D J, Grest G S, Sahni P S 1984
Computer simulation of grain growth. 1. Kinetics. Acta
Metall 32: 783-91
Binder 1979 Monte Carlo Methods in Statistical Physics.
Springer, Berlin
Bishop A R, Campbell L J, Channell J 1984 Fronts,
Interfaces and Patterns. North-Holland, Amsterdam
Brower R C, Kessler D A, Koplik J, Levine 1984
Geometrical models of interface evolution. Phys. Rev. A
29: 1335-42
Ceppi A, Nasello 1984 Computer simulation of
bidimensional grain growth. Scr. Metall. 18: 1221-5
Frost J, Thompson C V, Howe C L, Whang J 1988 A twodimensional computer simulation of capillarity-driven
grain growth: preliminary results. Scr. Metall. 22: 65-70
Gayda J, Srolovitz D J 1989 A Monte-Carlo finite element
model for strain-energy controlled microstructural evolu
tionrafting in superalloys. Acta Metall. 37 (2): 641-50
Ghoniem , Amodeo R 1988 Computer simulation of

Microtextural Analysis
A polycrystalline m a t e r i a l is said t o be t e x t u r e d if its
c o n s t i t u e n t g r a i n s h a v e a preferred o r i e n t a t i o n : t h a t is
t o say, t h e crystal axes a r e statistically oriented in a
n o n r a n d o m w a y . U n t i l recently, a t e x t u r e h a s always
been d e t e r m i n e d a n d d e p i c t e d m a c r o s c o p i c a l l y , in the
sense t h a t t h e o r i e n t a t i o n s of millions of grains a r e
collectively s h o w n in a p o l e figure ( t w o d i m e n s i o n a l )
o r a n o r i e n t a t i o n d i s t r i b u t i o n function (three d i m e n
sional) (see Texture:
Nondestructive
Characteriza
tion). A n y s u c h d e p i c t i o n leaves o u t o n e i m p o r t a n t
piece of i n f o r m a t i o n , t h a t is, t h e d i s t r i b u t i o n of m i s o r i e n t a t i o n s b e t w e e n all p a i r s of adjacent grains in
t h e polycrystal. S u c h a d i s t r i b u t i o n is called a microtexture o r a mesotexture;
o t h e r t e r m s which h a v e
b e e n used include grain misorientation
texture, grainboundary
character
distribution
and
misorientation
distribution', t h e t e r m " m i c r o t e x t u r e " will be used

255

Microtextural

Analysis

Figure 1
Stereographic unit triangle for a statistically random
assemblage of cubic grains, showing the percentages of
axes of misorientation lying within the various regions
bounded by solid curves. The regions are bounded, in
part, by small circles at 5, 10, 15, 30 and 45 from [100]
and by small circles at 5 and 9.7 from [111] (after
Mackenzie 1964)

exclusively here. M u c h a t t e n t i o n h a s been p a i d d u r i n g

the 1980s t o t h e m e t h o d s of d e t e r m i n a t i o n of such a
d i s t r i b u t i o n a n d t o the c o n s e q u e n c e of m i c r o t e x t u r a l
v a r i a t i o n s for physical a n d , especially, m e c h a n i c a l
p r o p e r t i e s , of m e t a l s a n d alloys in p a r t i c u l a r . T h i s is
t h e subject m a t t e r of this brief overview. M o s t w o r k
in this field h a s referred t o m e t a l s crystallizing in t h e
cubic system a n d this is a s s u m e d in w h a t follows.

1. Representation

of

Microtextures

T h e relative o r i e n t a t i o n of t w o adjacent cubic grains

c a n be described as a m u t u a l r o t a t i o n in m a n y dif
ferent w a y s , because of t h e equivalence of all three
c u b e axes, so t h a t a n y o n e c u b e axis of o n e grain c a n
be related t o a n y of t h e t h r e e c u b e axes of t h e o t h e r
grain. T h e u s u a l c o n v e n t i o n h a s been t o c h o o s e t h a t
r o t a t i o n which requires t h e smallest possible r o t a t i o n
angle. M a n y years a g o , t h e p r o c e d u r e s for finding this
m i n i m u m angle a n d t h e c o r r e s p o n d i n g ( m i n i m u m )
r o t a t i o n axis a n d for calculating t h e d i s t r i b u t i o n of
m i s o r i e n t a t i o n axes in a cubic u n i t triangle for a
r a n d o m l y oriented d i s t r i b u t i o n of grains were set o u t
by M a c k e n z i e (1964) a n d references therein. F i g u r e 1
s h o w s M a c k e n z i e ' s theoretical p l o t for t h e p r o p o r t i o n
of m i n i m u m m i s o r i e n t a t i o n axes lying in different
p a r t s of t h e u n i t triangle for a r a n d o m a g g r e g a t e ,
while F i g . 2 s h o w s a n e x p e r i m e n t a l d i s t r i b u t i o n of
such axes for c o n t i g u o u s g r a i n p a i r s in a n austenitic
stainless steel following p r i m a r y recrystallization a n d
a subsequent prolonged grain-growth anneal (Randle
a n d B r o w n 1989). It is very clear, c o m p a r i n g t h e t w o
figures, t h a t t h e m i c r o t e x t u r e is far from r a n d o m after

256

this t r e a t m e n t . R a n d l e a n d B r o w n w e n t o n t o e s t i m a t e
t h e p r o p o r t i o n of c o n t i g u o u s grain p a i r s t h a t a r e in a
C S L r e l a t i o n s h i p t o each other; t h e a b b r e v i a t i o n
refers t o coincidence lattice site t h e o r y a n d d e n o t e s a
family of " s p e c i a l " o r i e n t a t i o n relationships, of which
the m o s t familiar is t h e simple twin pair. T h e b e t t e r
t h e "fit" of t h e c o n t i g u o u s lattices at t h e b o u n d a r y
p l a n e , t h e lower t h e integer w h i c h defines t h e C S L
r e l a t i o n s h i p a n d (generally) t h e lower t h e specific
b o u n d a r y energy; is t h e reciprocal of t h e fraction of
lattice n o d e s of o n e grain t h a t coincide with lattice
n o d e s of t h e n e i g h b o r i n g grain. R a n d l e a n d B r o w n
f o u n d t h a t t h e p r o p o r t i o n of C S L p a i r s increased
steadily d u r i n g grain g r o w t h .
F r a n k (1988) h a s resurrected a n i n e t e e n t h c e n t u r y
g r a p h i c a l m e t h o d d u e t o O . R o d r i g u e s of r e p r e s e n t i n g
grain r o t a t i o n s , n o w t e r m e d the
Rodrigues-Frank
method: t h e o r i e n t a t i o n of t h e r o t a t i o n axis relative t o
t h e crystal axes of o n e of t h e grains is d e n o t e d b y a
line from t h e origin, while the length of t h a t line is
p r o p o r t i o n a l t o t h e r o t a t i o n angle. T h e loci of t h e
e n d s of such lines for t h e m a x i m u m feasible r o t a t i o n
angles for e a c h o r i e n t a t i o n of r o t a t i o n axis m a p s o u t a
p o l y g o n o r z o n e , l o o k i n g r a t h e r like a Brillouin z o n e .
T h e details of t h e m e t h o d , a n d its utility for a n a l y z i n g
t h e m i c r o t e x t u r a l c h a n g e s t h a t a c c o m p a n y recrystalli
z a t i o n of stainless steel with a n initial rolling t e x t u r e ,
h a v e been set o u t b y R a n d l e (1990a, b) I n t h e second
of t h e cited p a p e r s , R a n d l e g e n e r a t e d m e s o t e x t u r e s b y
c o m p u t e r o n the h y p o t h e s i s t h a t m u l t i p l e g e n e r a t i o n s
of t w i n n i n g d e t e r m i n e recrystallized o r i e n t a t i o n s , dis
p l a y e d these b y t h e R o d r i g u e s - F r a n k m e t h o d a n d
c o m p a r e d t h e m with o b s e r v e d m i c r o t e x t u r e s as a
m e a n s of v a l i d a t i n g t h e initial h y p o t h e s i s as t o t h e
origin of a n n e a l i n g textures.

Figure 2
Microtexture figure for the axes of (minimum)
misorientation corresponding to pairs of contiguous grains
in a recrystallized stainless steel specimen annealed for
11 h at 950 C, which has undergone extensive grain
growth (after Randle and Brown 1989)

Microtextural

Analysis

Table 1
Microtextural examination: pros and cons of available methods

Pattern
Transmission (electrons)
SAD (selected-area diffraction)
SAD
microdiffraction
microdiffraction
Kikuchi (electrons)
SAD
microdiffraction
SACP
EBSP
Kossel (x rays)
Laue (x rays)

2. Determination

of

Instrument

Highest
spatial
resolution

Angular
resolution
()

Usable for
very
imperfect
grains?

HVEM
TEM
TEM/STEM
FEG/STEM

0.4
1.5
10 nm
1 nm

2
2
2
5

yes
yes
yes
yes

TEM
TEM/STEM
SEM
SEM/STEM
SEM
SEM
synchrotron
source

1.5
20 nm
10
1-2
0.5
10
5

0.2
0.2
>0.5
0.5
<0.5
0.5
<0.5

no
no
no
no
no
yes
yes

Microtextures

A r a n g e of e x p e r i m e n t a l m e t h o d s h a s b e e n used t o
d e t e r m i n e m i c r o t e x t u r e s . W h i c h e v e r is used, t h e
o r i e n t a t i o n s of i n d i v i d u a l g r a i n s h a v e t o be s e p a r a t e l y
d e t e r m i n e d , so there is a g r e a t p r e m i u m o n r a p i d
m e t h o d s . T a b l e 1, slightly modified from o n e p u b
lished b y H u m p h r e y s (1988), sets o u t t h e available
m e t h o d s a n d their p r o s a n d c o n s . M o s t of t h e m e t h
o d s d e p e n d o n diffraction. T h e o r d i n a r y Laue method
h a s h i t h e r t o been t o o slow w h e n a n x-ray m i c r o b e a m
is used, b u t t h e availability of s y n c h r o t r o n sources h a s
n o w r e d u c e d t h e n e e d e d e x p o s u r e time from h o u r s t o
seconds. T h e Kossel method, in w h i c h a n electron
b e a m is focused o n a m e t a l grain t o g e n e r a t e a p o i n t
source of characteristic rays w h i c h s p r e a d o u t a n d
p r o d u c e diffraction p a t t e r n s in t h e f o r m of c o n i c
sections ( F e r r a n et al. 1971), h a s been extensively
used a n d requires e x p o s u r e s of a few m i n u t e s . Inter
p r e t a t i o n of K o s s e l p a t t e r n s h a s b e e n c o m p u t e r i z e d .
Diffraction of electrons is widely used (the first six
entries in T a b l e 1), b u t t h e a n g u l a r r e s o l u t i o n for m o s t
such m e t h o d s is n o t impressive. T w o o t h e r m e t h o d s ,
electron back scattering patterns ( E B S P ) a n d selectedarea channelling patterns ( S A C P ) , b o t h r e q u i r i n g t h e
use of a s c a n n i n g electron m i c r o s c o p e a n d o p e r a t i n g
with s h o r t e x p o s u r e s , h a v e n o w largely replaced t h e
Kossel m e t h o d .
I n o k u t i a n d his c o - w o r k e r s ( I n o k u t i et al. 1987a, b)
h a v e long used t h e K o s s e l m e t h o d intensively t o s t u d y
m i c r o t e x t u r e s in silicon steel used for t r a n s f o r m e r
l a m i n a t i o n s ; such studies h a v e p r o v e d essential for t h e
u n d e r s t a n d i n g a n d c o n t r o l of t e x t u r e f o r m a t i o n in
these sheets. T h e y d e v e l o p e d a m e t h o d of d i s p l a y i n g
t h e results of a large n u m b e r of such o r i e n t a t i o n

d e t e r m i n a t i o n s , in which e a c h g r a i n is s h o w n o n a
c o m p u t e r screen in its c o r r e c t m i c r o s t r u c t u r a l loca
tion, with a c o l o r t h a t directly defines its o r i e n t a t i o n ,
as s t a n d a r d i z e d o n a r a i n b o w - c o l o r e d u n i t stereog r a p h i c triangle. T h e thickness of a g r a i n b o u n d a r y in
such a display is g r a d e d a c c o r d i n g t o the m a g n i t u d e of
t h e m i s o r i e n t a t i o n b e t w e e n t h e adjacent grains. A n
e x a m p l e of o n e of I n o k u t i ' s displays in color is
r e p r i n t e d in a recent overview of textures by C a h n
(1991).

3. Microtextures

and

Properties

A polycrystal with a l a r g e r - t h a n - r a n d o m p o p u l a t i o n
of special ( C S L ) b o u n d a r i e s is expected t o h a v e
u n u s u a l m e c h a n i c a l p r o p e r t i e s ; o t h e r p r o p e r t i e s , such
as resistance t o g r a i n - b o u n d a r y c o r r o s i o n a n d grainb o u n d a r y mobility, a r e t h e n also likely t o be a b n o r
mal. Where mechanical properties are concerned, a
J a p a n e s e investigator, W a t a n a b e , h a s been a s t r o n g
p r o p o n e n t of t h e c o n c e p t of grain-boundary design, by
w h i c h h e m e a n s t h e processing of a polycrystal with
t h e objective of g e n e r a t i n g a desirable d i s t r i b u t i o n of
special b o u n d a r i e s , so as t o achieve g r e a t e r - t h a n n o r m a l s t r e n g t h o r ductility.
A g o o d e x a m p l e of this a p p r o a c h is p r o v i d e d b y a
recent s t u d y by W a t a n a b e et al. (1989) of a specially
t r e a t e d f o r m of c o n c e n t r a t e d ( 6 . 5 w t % S i ) silicon
steel w h i c h h a s t u r n e d o u t t o be a serious c o m p e t i
t o r in t r a n s f o r m e r l a m i n a t i o n s b o t h for s t a n d a r d
(3.5 w t % S i ) silicon steel a n d for metallic glasses. T h e y
d e t e r m i n e d g r a i n o r i e n t a t i o n s b y electron channelling
( S A C P ) a n d identified special b o u n d a r i e s , classified

257

Microtextural

Analysis

29 13
81 27
9

aries generally, a n d low- b o u n d a r i e s o n a statistical

basis, were m o r e resistant t o c o r r o s i o n t h a n largeangle b o u n d a r i e s generally; n o t only t h e value b u t
also t h e o r i e n t a t i o n of t h e b o u n d a r y p l a n e (a q u a n t i t y
n o t h i t h e r t o m e a s u r e d in m i c r o t e x t u r a l studies) plays
a role.

3
^42.5%
4 1 %

304

30 h

steel

Fe-6.5

0 nickel

wt%Si

See also: Pole Figures and Orientation Distribution Func

tions; Texture: Nondestructive Characterization

rapidly solidified
and

annealed

I363K

I h

Bibliography
20

Fe-3wt%Si
7 4 % rolled and
annealed, 1333

10

p u r e Fe
rolled annealed
9 7 3 K, 100 h
random orientn
distribution

Q5

1.0

1.5

Figure 3
The frequency of special boundaries, as a function of , in
a rapidly solidified and annealed ribbon of Fe-6.5 wt%Si
transformer steel, heat-treated for optimum ductility. Data
for other alloys also shown (after Watanabe et al. 1989)

by their characteristic n u m b e r s . F i g u r e 3 s h o w s
their results ( o p e n circles), c o m p a r e d with d a t a for a
differently t r e a t e d silicon steel as well as o t h e r alloys,
a n d also with a line c o r r e s p o n d i n g t o a texture-free
m a t e r i a l . T h e t o p abscissa o n this g r a p h m a r k s
n u m b e r s , t h e b o t t o m abscissa is c a l i b r a t e d in t e r m s of
1/3
~ , because t h e a u t h o r s f o u n d empirically t h a t t h e
frequencies of special b o u n d a r i e s varied linearly w i t h
this function of . T h e r a p i d l y solidified a n d a n n e a l e d
6.5 w t % silicon steel ( t h a t is, t h e f o r m of this alloy
with exceptional p r o p e r t i e s ) h a s a high p r o p o r t i o n
( a b o u t 5 0 % ) of low- grain b o u n d a r i e s .
T h e high ductility of t h e specially t r e a t e d silicon
steel w a s a t t r i b u t e d b y W a t a n a b e t o t h e high resis
t a n c e of special b o u n d a r i e s t o i n t e r g r a n u l a r fracture.
In a recent s t u d y , L i m a n d W a t a n a b e (1990) h a v e
d e m o n s t r a t e d a m e c h a n i s m b y w h i c h a high fraction
of fracture-resistant special (low-energy) b o u n d a r i e s
c a n e n h a n c e t h e overall fracture t o u g h n e s s of a polycrystal.
O r t n e r a n d R a n d l e (1989) h a v e d e m o n s t r a t e d t h a t
individual g r a i n b o u n d a r i e s in a stainless steel p a r
tially sensitized t o c o r r o s i o n b e h a v e differently
a c c o r d i n g t o their c r y s t a l l o g r a p h y . L o w - a n g l e b o u n d
258

Cahn R W 1991 Measurement and control of texture. In:

Cahn R W (ed.) 1991 Processing of Metals and Alloys,
Materials Science and Technology, Vol. 9. VCH, Weinheim, Germany, pp. 429-80
Ferran G, Doherty R D, Cahn R W 1971 The Kossel line
determination of the orientation of new grains formed by
recrystallization of aluminium. Acta Metall. 19: 101928
Frank F C 1988 Orientation mapping. MRS Bull. 13(3):
24-30
Humphreys F J 1988 Experimental techniques for microtexture determination. In: Kallend S S, Gottstein G (eds.)
1988 ICOTOMProc.
8th Int. Conf Textures of
Materials.
Metallurgical Society, Warrendale, PA,
pp. 171-82
Inokuti Y, Maeda C, Ito Y 1987a Computer color mapping
of configuration of Goss grains after an intermediate
annealing in grain oriented silicon steel. Trans. Iron Steel
Inst. Jpn. 27: 139-44
Inokuti Y, Maeda C, Ito Y 1987b Computer color mapping
of configuration of Goss grains after transverse cold
rolling in grain oriented silicon sheet. Trans. Iron Steel
Inst. Jpn. 27: 302-11
Lim L C, Watanabe 1990 Fracture toughness and brittleductile transition controlled by grain boundary character
distribution (GBCD) in polycrystals. Acta Metall. Mater.
38: 2507-16
Mackenzie J 1964 The distribution of rotation axes in
a random aggregate of cubic crystals. Acta Metall. 12:
223-5
Ortner S R, Randle V 1989 A study of the relation between
grain boundary type and sensitisation in a partially
sensitised AISI 304 stainless steel using electron backscattering patterns. Scr. Metall. 23: 1903-8
Randle V 1990a Representation of grain misorientations
(mesotexture) in Rodrigues-Frank space. Proc. R. Soc.
London, Ser. A 431: 61-9
Randle V 1990b Simulation of mesotexture between
deformed and recrystallized microstructures. Mater. Sci.
Tech. 6: 1231-5
Randle V, Brown A 1989 Development of grain misorientation texture, in terms of coincident site lattice struc
tures, as a function of thermomechanical treatments.
Philos. Mag. A 59: 1075-89
Watanabe T, Fujii H, Oikawa H, Arai I 1989 Grain
boundaries in rapidly solidified and annealed Fe-6.5
mass % Si polycrystalline ribbons with high ductility. Acta
Metall. 37: 941-52
R. W . C a h n
[University of C a m b r i d g e ,
Cambridge, U K ]

Mossbauer

Mossbauer Spectroscopy
T h e history of t h e M o s s b a u e r effect is u n i q u e in t h e
field of s p e c t r o s c o p y a n d in writing a general i n t r o
d u c t i o n , it is necessary t o c o n s i d e r a few facts a b o u t
such a significant discovery. M o s s b a u e r w a s a s t u d e n t
w h e n he m a d e a n u n e x p e c t e d o b s e r v a t i o n . W o r k i n g
conscientiously a n d skilfully he f o u n d t h e origin of
the s t r a n g e effect ( M o s s b a u e r 1958a, b ) , b u t w h e n h e
published his findings in 1958, surprisingly n o o n e
seemed t o notice, c a r e a b o u t o r believe t h e m . W h e n
the greatness of t h e discovery w a s finally a p p r e c i a t e d ,
fascination g r i p p e d t h e scientific c o m m u n i t y , a n d
m a n y scientists i m m e d i a t e l y s t a r t e d researching t h e
p h e n o m e n o n . I m p o r t a n t e x p e r i m e n t s were initiated
a n d significant discoveries were m a d e s u c h as t h e
g r a v i t a t i o n a l red shift a n d hyperfine i n t e r a c t i o n s with
v a r i o u s i s o t o p e s a n d m a n y a p p l i c a t i o n s in physics,
chemistry, biology a n d m a t e r i a l s science were f o u n d .
Suddenly t h e n u m b e r of p a p e r s dealing with the n e w
m e t h o d b e c a m e so large t h a t the e d i t o r of Physical
Review Letters h a d t o b r i n g it t o a s t o p (April 1960).
T h e N o b e l Prize w a s a w a r d e d t o M o s s b a u e r in 1961,
de facto for his first p u b l i c a t i o n a u n i q u e achieve
m e n t in t h e h i s t o r y of this distinction ( M o s s b a u e r
1962).
I n the following years, m o r e a n d m o r e i s o t o p e s
( a b o u t 100) were f o u n d t o be useful for t h e n e w
m e t h o d ( M u i r et al. 1966, Stevens a n d Stevens 1966
5 7
76, 1977-87), with F e (the m o s t i m p o r t a n t e l e m e n t
in physical m e t a l l u r g y ) p r o v i d i n g the m o s t f a v o u r a b l e
nuclear p a r a m e t e r s for M o s s b a u e r studies ( G o n s e r
1975, 1981, 1986).

7.

Principles

T h e p h e n o m e n o n of r e s o n a n c e m a y o c c u r b e t w e e n
t w o bodies. In t h e case of t h e M o s s b a u e r effect, these
t w o bodies a r e nuclei of t h e s a m e i s o t o p e . R e s o n a n c e
is a c c o m p l i s h e d b y e l e c t r o m a g n e t i c r a d i a t i o n : y r a y s
emitted a n d a b s o r b e d b e t w e e n t h e excited a n d g r o u n d
state. H o w e v e r , y-ray r e s o n a n c e fluorescence h a d
already been realized a n d p e r f o r m e d earlier. T h e n e w
i m p o r t a n t o b s e r v a t i o n t h a t M o s s b a u e r m a d e in
cluded t h e p r o p e r t y of "recoil-free" y-ray r e s o n a n c e
fluorescence. I n o r d e r t o explain t h e n e w effect, t h e
q u a n t u m m e c h a n i c s of t h e system m u s t b e c o n s i d e r e d .
In a c o n d e n s e d system (a solid) t h e t h e r m a l p r o p e r t i e s
of a lattice a r e described b y v i b r a t i o n a l oscillations of
the a t o m s with frequencies v. T h e energy of t h e
oscillations is q u a n t i z e d in discrete u n i t s of hv
(h = 2nh = P l a n c k ' s c o n s t a n t ) . T h e v i b r a t i o n a l m o d e s
constitute the p h o n o n s . The Debye model represents
v i b r a t i o n a l states with a certain d i s t r i b u t i o n of fre
quencies a n d a characteristic m a x i m u m v i b r a t i o n a l
1 2
1 3
frequency v D typically in t h e r a n g e of 1 0 - 1 0 H z .
W i t h B o l t z m a n n ' s c o n s t a n t KB t h e D e b y e t e m p e r a
ture is defined:

Spectroscopy

hvO = kB0O

(1)
2

T a k i n g ~ 300 K , D e b y e energies kB6D ~ 1 0 " e V

c a n be o b t a i n e d .
T h e y-ray emission a n d a b s o r p t i o n of a n a t o m i c
nucleus m u s t n o w be considered. If t h e a t o m is free,
t h e recoil energy for a n a t o m with m a s s t a k i n g i n t o
a c c o u n t m o m e n t u m c o n s e r v a t i o n , is
2

ER = E /2Mc

(2)

w h e r e c is t h e velocity of light. F o r a y ray with

4
1 0 e V a n d a t o m s with M= 100, t h e recoil energies
3
a r e of o r d e r 1 0 " e V . T h u s this energy is lower t h a n ,
o r c o m p a r a b l e with, t h e D e b y e energy of a n a t o m in a
b o u n d state o r a solid with a typical D e b y e t e m p e r a
t u r e ~ 300 K . Because t h e recoil energy ER is of the
o r d e r of t h e D e b y e energy kB0D, there is a certain
p r o b a b i l i t y t h a t t r a n s i t i o n s o c c u r w i t h o u t recoil; in
o t h e r w o r d s , t r a n s i t i o n s exist w h e r e n o p h o n o n is
c r e a t e d o r a n n i h i l a t e d . T h e p r o b a b i l i t y of recoil-free
events c a n be expressed q u a n t i t a t i v e l y by t h e D e b y e W a l l e r factor w h i c h w a s a l r e a d y k n o w n in the a n a l y
sis of rays scattered from crystals before M o s s b a u e r ' s discovery:
2

/=exp(-A: <x

(3)

w h e r e k is t h e m a g n i t u d e of t h e w a v e vector of the y
2
r a y a n d <x > is t h e m e a n - s q u a r e v i b r a t i o n a l a m p l i
t u d e of t h e r e s o n a t i n g a t o m in t h e direction of obser
v a t i o n . T w o i m p o r t a n t results a r e o b t a i n e d from this
e q u a t i o n . T h e recoil-free fraction / increases with
d e c r e a s i n g y-ray energy k a n d increasing D e b y e t e m
p e r a t u r e .
In the recoil-free t r a n s i t i o n b e t w e e n the excited a n d
t h e g r o u n d state n o energy is e x c h a n g e d with the
s u r r o u n d i n g s , t h a t is, t h e y r a y carries the t o t a l
energy. W i t h t h e m e a n lifetime of t h e excited state
(the g r o u n d state is stable o r h a s a l o n g lifetime),
H e i s e n b e r g ' s u n c e r t a i n t y principle applies:
= /

(4)

w h e r e designates t h e n a t u r a l line w i d t h of L o r e n t zian s h a p e of t h e source emission o r a b s o r b e r line,

defined as t h e full w i d t h a t half m a x i m u m . It s h o u l d
be n o t e d t h a t t h e r e is n o b r o a d e n i n g by t h e r m a l
v i b r a t i o n s a t higher t e m p e r a t u r e s , as is s o m e t i m e s
claimed, b e c a u s e t h e n u c l e a r lifetime is very long
c o m p a r e d t o t h e s h o r t a t o m i c oscillation p e r i o d .
5 7
T h e first excited state of F e (14.4 keV) h a s a half7
life of a b o u t 1 0 " s. T h u s t h e n a t u r a l line w i d t h is ~
9
5 x 1 0 ~ e V . T h e r a t i o of t h e n a t u r a l line w i d t h a n d
t h e y-ray energy / is a m e a s u r e of t h e resolution o r
t h e a c c u r a c y in t h e d e t e r m i n a t i o n of relative energy o r
5 7
frequency c h a n g e s . F o r
F e this r a t i o is a b o u t
13
3 x 1 0 " . It s h o u l d be p o i n t e d o u t t h a t only relative
energy o r frequency c h a n g e s b e t w e e n t w o r e s o n a t i n g
nuclei c a n be m e a s u r e d with such a c c u r a c y . I n s u m
m a r y , for t h e existence of t h e M o s s b a u e r effect, the
following energy r e l a t i o n s h i p is relevant: t h e D e b y e

259

Mossbauer

Spectroscopy

-excited

state -

^ j O y s ^

-ground

state-

t h e y-ray intensity arriving a t t h e d e t e c t o r is p l o t t e d as

5 7
a function of v. T o trace t h e r e s o n a n c e line for F e ,
velocities of t h e o r d e r of millimeters p e r second a r e
required.

fa)

drive

3. Hyperfine
Absorber

Source

counter

system

(b)

multichannel

analyzer

Figure 1
(a) Relevant transitions between the nuclear excited and
the ground state; (b) combined experimental setup of y-ray
absorption and conversion electron emission geometry

energy kB0O of typical solids a n d the recoil energy of

the free a t o m EK a r e of similar m a g n i t u d e , while for
the significance a n d relative a c c u r a c y of the effect, t h e
large difference b e t w e e n t h e energy of t h e y-ray Ey a n d
line w i d t h is decisive.

2. Experimental

Details

In general, five c o m p o n e n t s a r e r e q u i r e d for a M o s s

b a u e r experiment: a s o u r c e , a n a b s o r b e r , a drive
system, d e t e c t o r s a n d a c o u n t i n g system, including
computer-fitting p r o c e d u r e s . I n m o s t cases a singleline source is used a n d t h e a b s o r b e r c o n s t i t u t e s t h e
s a m p l e u n d e r investigation. E m i s s i o n in t h e s o u r c e
a n d in t h e a b s o r b e r m u s t o c c u r in a recoil-free
fashion, indicated b y the b o l d a r r o w s in F i g . 1. In
the t r a n s m i s s i o n g e o m e t r y , t h e y rays a r e m e a s u r e d
b e h i n d the a b s o r b e r with a y-ray d e t e c t o r (a p r o
p o r t i o n a l c o u n t e r , p h o t o m u l t i p l i e r o r solid-state
detector).
T h e decisive step from a n e x p e r i m e n t a l effect t o a
useful m e t h o d in s p e c t r o s c o p y w a s t a k e n b y M o s s
b a u e r himself. H e realized t h a t t h e energy of the
r e s o n a n c e lines c a n be easily a n d accurately m o d u
lated by a relative D o p p l e r velocity b e t w e e n the
source a n d t h e a b s o r b e r :
(5)
F o r his first e x p e r i m e n t , M o s s b a u e r used a simple t o y
to a c c o m p l i s h t h e m o v e m e n t b e t w e e n the source a n d
the a b s o r b e r . A c c o r d i n g l y , in a M o s s b a u e r s p e c t r u m ,

260

Interactions

T h e b r e a k t h r o u g h for M o s s b a u e r s p e c t r o s c o p y oc
c u r r e d w h e n it w a s realized t h a t for t h e first time t h e
hyperfine i n t e r a c t i o n c o u l d be resolved b e c a u s e of t h e
high r e s o l u t i o n of t h e r e s o n a n c e lines ( H a n n a et al.
1960, K i s t n e r a n d S u n y a r 1960). T h e hyperfine inter
a c t i o n consists of t h e i n t e r a c t i o n b e t w e e n t h e n u c l e u s
a n d its associated electric a n d m a g n e t i c m o m e n t s , a n d
t h o s e of t h e electrons in t h e i m m e d i a t e s u r r o u n d i n g s .
T h e hyperfine c o u p l i n g m e c h a n i s m s a r e of great signi
ficance, yielding electron a n d spin density distribu
tions. T h e r e a r e three m a i n hyperfine i n t e r a c t i o n s
c o r r e s p o n d i n g t o t h e n u c l e a r m o m e n t s w h i c h deter
m i n e t h e n u c l e a r levels.
3.1 Isomer Shift (Electric Monopole
Interaction)
T h e i s o m e r shift originates from t h e C o u l o m b i n t e r a c
tion of t h e c h a r g e d i s t r i b u t i o n s over a finite n u c l e a r
r a d i u s R in t h e excited a n d g r o u n d states a n d t h e
electron c h a r g e density a t the nucleus, effectively t h e s
electrons ( K i s t n e r a n d S u n y a r 1960, W a l k e r et al.
1961, Shirley 1964). T h e t o t a l s-electron density eva
2
l u a t e d a t t h e r e s o n a t i n g nuclei in t h e source, | y/s(0) | ,
2
a n d in t h e a b s o r b e r , | ^ A ( 0 ) | , c a n v a r y if t h e chemical
e n v i r o n m e n t influences t h e t r a n s i t i o n energies in t h e
source a n d t h e a b s o r b e r . T h e resulting isomer shift
c a n be expressed (in t h e nonrelativistic a p p r o x i m a
tion) by
2

( 5 = C ( | ^ A( 0 ) | - | ^ S( 0 ) | ) ^

(6)

w h e r e C is t h e c o n s t a n t c o n t a i n i n g n u c l e a r p a r a m e t e r s
of a given i s o t o p e a n d SR/R is t h e relative c h a n g e of
n u c l e a r r a d i u s b e t w e e n t h e excited state a n d t h e
g r o u n d state. T h e " c h e m i c a l " n a t u r e of t h e i s o m e r
shift led t o t h e occasional use of the t e r m " c h e m i c a l
shift." Because M o s s b a u e r s p e c t r o s c o p y is a relative
m e t h o d t h e s o u r c e s p e c t r u m is related t o t h e
a b s o r b e r s p e c t r u m b y a D o p p l e r m o t i o n o n e of t h e
t w o h a s t o be fixed t o d e t e r m i n e the o t h e r . F o r e a c h
M o s s b a u e r i s o t o p e a reference s t a n d a r d is needed.
5 7
-Fe h a s b e e n selected for t h e i s o t o p e F e .
3.2 Nuclear Zeeman Effect (Magnetic
Dipole
Interaction)
T h e i n t e r a c t i o n of t h e n u c l e a r m a g n e t i c dipole m o
m e n t in a m a g n e t i c field a t t h e site of t h e n u c l e u s
splits t h e n u c l e a r state with spin / i n t o sublevels w i t h
eigenvalues Em as s h o w n in Fig. 2. T h e negative sign
indicates t h a t t h e n u c l e a r m a g n e t i c m o m e n t a n d t h e
5 7
a t o m i c m a g n e t i c m o m e n t in F e a r e o p p o s i t e l y
oriented. C o n s i d e r i n g t h e m u l t i p o l a r i t y of t h e
14.4 k e V y-ray t r a n s i t i o n we h a v e t h e selection rule

Mossbauer

Spectroscopy

I n general, M o s s b a u e r s p e c t r o s c o p y exhibits a
c o m b i n a t i o n of hyperfine i n t e r a c t i o n s . T h e m a g n i
t u d e of these i n t e r a c t i o n s is d e t e r m i n e d by t h e posi
tions of t h e lines a n d t h e relative intensities give
i n f o r m a t i o n o n t h e o r i e n t a t i o n s . T h e exact e v a l u a t i o n
of m i x e d i n t e r a c t i o n s a n d o v e r l a p p i n g spectra is
s o m e t i m e s difficult a n d requires c o m p u t e r analysis.

4.

Applications

M o s s b a u e r s p e c t r o s c o p y is a typical m i c r o s c o p i c tool:
the p o i n t of o b s e r v a t i o n s is a r e s o n a t i n g nucleus. W e
c a n learn s o m e t h i n g a b o u t t h e electronic a n d m a g
netic e n v i r o n m e n t t h r o u g h t h e hyperfine i n t e r a c t i o n s
a n d a b o u t t h e v i b r a t i o n a l states of t h e a t o m s t h r o u g h
t h e D e b y e - W a l l e r factor. I n this section, typical ex
a m p l e s a r e discussed, i n d i c a t i n g t h e success, b u t also
t h e limitations, of the m e t h o d .
4.1 Electronegativity:

(b)

Figure 2
Hyperfine interaction parameters and effects:
(a) interaction of the nuclear magnetic dipole moment
with a magnetic field at the nucleus (magnetic dipole
interaction or nuclear Zeeman effect); (b) interaction of
the nuclear quadrupole moment eQ with electric field
gradient V at the nucleus (electric quadrupole
interaction)

Am = 0, 1, leading t o the six-line p a t t e r n s h o w n in

Fig. 2a ( H a n n a et al. 1960). T h e a n g u l a r d e p e n d e n c e
( a n d p o l a r i z a t i o n ) associated with the allowed t r a n s i
tions is reflected in t h e relative line intensities s h o w n
in Fig. 2a for t h e first three t r a n s i t i o n s (the o t h e r three
are equivalent). Sm represents t h e angle b e t w e e n the
p r o p a g a t i o n direction of t h e r a d i a t i o n a n d t h e direc
tion of the m a g n e t i c field. I n all cases, the s u m of the
intensities of t h e six l i n e s t h a t is, t h e t o t a l inten
sityis isotropic, as indicated b y t h e circle (or
sphere).
3.3 Electric Quadrupole
Interaction
T h e i n t e r a c t i o n of t h e n u c l e a r electric q u a d r u p o l e
m o m e n t eQ with t h e principal c o m p o n e n t of the
electric field g r a d i e n t splits t h e n u c l e a r states i n t o
sublevels with eigenvalues EQ. T h e a n g u l a r d e p e n
dence of the r a d i a t i o n p a t t e r n p r o d u c e d b y a n electric
field g r a d i e n t with axial s y m m e t r y ( a s y m m e t r y p a r a
5 7
m e t e r = 0) at t h e F e nucleus is s h o w n in Fig. 2 b . Sq
represents t h e angle b e t w e e n the principal axis of t h e
electric field g r a d i e n t a n d the p r o p a g a t i o n direction of
the ray. A g a i n t h e s u m of t h e intensities of t h e t w o
lines is isotropic, as indicated by t h e circle (or sphere).

Volta

Potential

T h i s a p p l i c a t i o n d e m o n s t r a t e s the m a c r o s c o p i c a n d
m i c r o s c o p i c view of o n e a n d t h e s a m e p r o b l e m . This
p h e n o m e n o n c a n b e a p p r o a c h e d from t w o extremes.
In o n e case, t w o m a c r o s c o p i c pieces of m e t a l A a n d
a r e b r o u g h t i n t o close c o n t a c t . Because t h e chemical
p o t e n t i a l s t h e F e r m i e n e r g y m u s t be e q u a l , c h a r g e
will m o v e t o w a r d s t h e m o r e electronegative m e t a l . In
t h e o t h e r case, a " r e s o n a n c e m e t a l " a t o m A is
i m p l a n t e d o r i n c o r p o r a t e d i n t o m e t a l B. T h e r e will be
a c h a r g e transfer b e t w e e n t h e i m p u r i t y a t o m a n d the
s u r r o u n d i n g m a t r i x . T h e i s o m e r shift tells us the
direction, t h a t is, w h e t h e r a t o m A gains o r loses
electronic c h a r g e t o t h e s u r r o u n d i n g m a t r i x . In a n
1 9 7
e x p e r i m e n t , the r e s o n a n c e a t o m A u w a s placed i n t o
19 different metallic elements ( B a r r e t t et al. 1963). By
e v a l u a t i n g t h e i s o m e r shifts, a m o n o t o n i c c o r r e l a t i o n
with t h e electronegativity of t h e m a t r i x m e t a l w a s
established. M i e d e m a a n d V a n d e r W o u d e e x t e n d e d
this idea a n d p r e s e n t e d a cellular a t o m i c m o d e l (Mie
d e m a a n d V a n d e r W o u d e 1980). Besides t h e electro
negativity difference a n d a v o l u m e c o n t r i b u t i o n (size
effect), a t e r m reflecting t h e differences in electron
density a t t h e b o u n d a r i e s of t h e a t o m i c cells w a s
i n t r o d u c e d . T h e y were able t o a c c o u n t for the
1 97
o b s e r v e d i s o m e r shift of t h e A u in a large n u m b e r of
g o l d - c o n t a i n i n g alloys.
4.2 Monomer and Dimer
Close t o t h e m e l t i n g p o i n t , a b o u t 4 a t . % iron is
soluble in c o p p e r . A t r o o m t e m p e r a t u r e , t h e solubility
of i r o n in c o p p e r is i m m e a s u r a b l y small. By r a p i d
q u e n c h i n g t e c h n i q u e s , s u p e r s a t u r a t e d alloys c a n
be o b t a i n e d . T h e M o s s b a u e r s p e c t r u m of a C u - 0 . 2
a t . % F e alloy q u e n c h e d from 1243 in w a t e r is s h o w n
in Fig. 3. T h e s p e c t r u m c a n be d e c o m p o s e d i n t o t w o
c o m p o n e n t s : a single line c o r r e s p o n d i n g t o the iso
lated i r o n a t o m s with 12 n e a r e s t - n e i g h b o r c o p p e r
atoms (monomer) and a quadrupole component

261

Mossbauer

Spectroscopy

-I

0
Velocity

(mm

s" )

Figure 3
Mossbauer spectrum of Cu-0.2at.%Fe alloy at room
temperature

representing m a i n l y i r o n n e i g h b o r i n g p a i r s (dimer)
(Krischel et al. 1980). T h e relative a r e a s of the t w o
spectral c o m p o n e n t s a r e r o u g h l y p r o p o r t i o n a l t o the
fraction of m o n o m e r s ( 8 8 % ) a n d d i m e r s ( 1 2 % ) . T h e
latter m a y include a small n u m b e r of trimers. T h e s e
values d e p e n d t o s o m e extent o n t h e q u e n c h i n g c o n
ditions.
T h e existence of t h e q u a d r u p o l e splitting for the
dimers clearly establishes t h a t a n electric field
g r a d i e n t is p r e s e n t a t the i r o n n u c l e a r site, t h a t
is, the local cubic s y m m e t r y is r e m o v e d . C o n
sidering t h e m a g n i t u d e of t h e q u a d r u p o l e inter
1
action ( A Q = 0.639 m m s " ) a n d t h e i s o m e r shift
1
( = 0.189 m m s " with respect t o -Fe) a fairly
g o o d m o d e l of t h e electronic configuration involved
c a n be o b t a i n e d .
4.3 Phase

Analysis

I n physical m e t a l l u r g y , p h a s e d i a g r a m s play a signific

a n t role. T h e y give i n f o r m a t i o n o n t h e r a n g e of
existence of different c r y s t a l l o g r a p h i c p h a s e s , o r d e r e d
p h a s e s , m a g n e t i c o r d e r i n g a n d so o n . I n a d d i t i o n t o
the t h e r m o d y n a m i c a l l y stable p h a s e s of the p h a s e
d i a g r a m , o t h e r m e t a s t a b l e p h a s e s m i g h t exist.
In general, every p h a s e c o n t a i n i n g M o s s b a u e r iso
topes exhibits a s p e c t r u m with characteristic h y p e r
fine i n t e r a c t i o n p a r a m e t e r s w h i c h c a n b e described as
" f i n g e r p r i n t s " of t h e p h a s e . By m e a n s of these typical
spectra, certain p h a s e s c a n be identified a n d q u a n t i t a
tively d e t e r m i n e d . M o s s b a u e r s p e c t r o s c o p y will
h a r d l y ever be able t o c o m p e t e with chemical analysis,
b u t it is often s u p e r i o r w h e n interest is focused o n the
analysis of p h a s e s as distinct from c o m p o s i t i o n .
Precision p h a s e analysis h a s been carried o u t t o
d e t e r m i n e the solubility of iron in -Ti (Blasius a n d
G o n s e r 1976). Specimens with a s t a r t i n g c o m p o s i t i o n
C 0 of a b o u t 0.1 a t . % i r o n w i t h i n the t w o - p h a s e
(a 4- ) r e g i o n w e r e a n n e a l e d in t h e t e m p e r a t u r e

262

-I

+1

Velocity

( m m s ')

Figure 4
Mossbauer spectra of titanium-iron alloys annealed at
858

r a n g e of 8 5 0 - 1 0 8 0 a n d t h e n q u e n c h e d . T h e result
ing spectra are s h o w n in Fig. 4. O w i n g t o the dif
ferences in the i s o m e r shift, the spectra c a n be
d e c o m p o s e d i n t o a c o m p o n e n t representing iron dis
solved in -Ti ( h e x a g o n a l close-packed (hep)) (lowt e m p e r a t u r e p h a s e ) a n d o n e representing /?-Ti
( b o d y - c e n t r e d cubic (bec)) ( h i g h - t e m p e r a t u r e p h a s e ) .
T h e fraction of t h e c o m p o n e n t s d e p e n d s o n t h e
t e m p e r a t u r e . A s s u m i n g the s a m e D e b y e - W a l l e r fac
t o r for b o t h p h a s e s , the relative line intensities repre
sent t h e a m o u n t of iron in t h a t p a r t i c u l a r p h a s e . If the
intensities a r e r o u g h l y the s a m e , this indicates t h a t
iron a t o m s a r e evenly d i s t r i b u t e d in t h e t w o p h a s e s .
H o w e v e r , because the c o n c e n t r a t i o n of iron is c o m
paratively m u c h higher in t h e p h a s e , the n e a r
equality of t h e r e s o n a n c e intensities c o u l d be achieved
only by c h o o s i n g a s t a r t i n g c o m p o s i t i o n C 0 close t o
<\Cfi-C0\.
the e q u i l i b r i u m line Ca: \C0-C9\
A p p l y i n g t h e lever r e l a t i o n s h i p :
C 0 C

Mo
= l

(7)

it follows t h a t for the a m o u n t s of the t w o p h a s e s , Ma

> . F r o m the e x p e r i m e n t a l values t h e solubility
c u r v e w a s o b t a i n e d , as s h o w n in Fig. 5. T h e d a t a
indicate t h a t precision p h a s e analysis is possible in the
r a n g e d o w n t o a b o u t 0.001 a t . % .

Mossbauer

talline phase which is otherwise inaccessible by heat

treatment (Bauer et al. 1986).

1100 -

4.5 Scattering
000 r -

900r-

800

_1_L
d

\0~

10

10"
Fe

concentration

(at.%)

Figure 5
-phase boundary of titanium-rich iron alloys

4.4 Amorphous

Spectroscopy

Metals

The advent of amorphous metals in the 1950s had a

tremendous impact on physical metallurgy. With
these new materials, the principles of physical metal
lurgy and such well-known terms as lattice, defect,
Fermi surface and intermetallic phases acquired new
meanings or had to be redefined. Instead of unique
properties, one finds in the amorphous state very
broad Mossbauer lines and distributions in the spec
tral parameters.
Interpretation of Mossbauer spectra becomes
doubtful and controversial. It seems that the infinite
number of different atomic surroundings causes an
infinite number of spectral components: we are at the
limits of the method. With all the considerable efforts
made, it has not been possible to uniquely determine
even one single atomic structure. In this respect
Mossbauer spectroscopy shares the destiny of all the
other methods which have been applied in the hope of
establishing the short-range atomic order.
However, when it comes to crystallization, Moss
bauer spectroscopy is unsurpassed. Considering the
melt-spinning technique, the quenching rate can be
reduced by lowering the surface speed of the quench
ing wheel. When a critical range is reached, incipient
crystallization occurs. In Fig. 6 two spectra from an
Fe^Ni^BjQ alloy are shown. The upper one was
obtained in the as-quenched state (wheel velocity
1
vw = 13ms" ) and the lower one after subsequent
annealing. The lower spectrum is also obtained with
1
v w < 10 m s " . The spectra can be decomposed into
two phases: both have in common a subspectrum
corresponding to a face-centered cubic (fee) (Fe, Ni,
B) phase. However, the additional phases have similar
compositions (Fe, Ni) 3 B, but different crystallo
graphic structures: a tetragonal phase and an orthorhombic phase. In these structures iron is in two or
three distinguishable environments, respectively, as
indicated in Fig. 6. It is of interest that controlled
quenching generates the metastable tetragonal crys

Geometry,

Surfaces

After resonance has taken place, the absorber nucleus

is in the excited state, as seen in Fig. 1. The deexcitation by electron, x-ray or y-ray emission can be
used to obtain a spectrum. Particularly, conversion
electron Mossbauer spectroscopy (CEMS) is of inter
est because surface regions at a depth of about 100 nm
can be scanned (Nasu and Gonser 1980, Gonser et al.
1983). An advantageous arrangement is shown in
Fig. 1 where electron emission in scattering and y-ray
transmission are measured simultaneously. For this
purpose the sample is placed inside an electron coun
ter. The electrons which are emitted after the corres
ponding nuclei have experienced nuclear resonance
are registered in the first half of a multichannel
analyzer while the y rays from the source passing
through the electron counter and the absorber sample
are detected with a y-ray counter and registered in the
second half of the analyzer. As an example, Moss
bauer spectra of an amorphous Fe 7 8Mo 2 B 2 0 ribbon
after 3 h of heat treatment at 634 are exhibited in
Fig. 7. In the middle, a y-ray transmission spectrumscanning the bulkis seen, while at the top and the
bottom, electron emission spectra from the contact
surface (contact with the quenching wheel) and from
the free surface, respectively, are obtained. It is of
interest to determine where crystallization com
mences. Extra lines were first observed in the spec-

fcc(FeNiB)
tetragonal ( F e N i ) 3B

fee (FeNiB)
1

Velocity

} orthorhomboid (FeNi) 3B

(mm s )

Figure 6
Mossbauer spectra obtained
from Fe^Ni^B^: (a) in the
_ l
as-quenched ( v = 1 3 m s ) state; and (b) subsequently
annealed

263

Mossbauer

Spectroscopy

contact
I

surface

.02

I .00

L
a -

I .00

(Fe.Mo)

0.98
bulk
0

96

0.94

1 .03
Velocity
I . 02

( m m s ')

free
surface

I - 00

_i
-6

-4

L
-2
Velocity

I
0

u
2

1
4

( m m s" )

Figure 7
Mossbauer y-ray absorption and electron emission spectra
of amorphous Fe 7 8Mo 2B 20 after annealing for 3 h at 643

t r u m of the c o n t a c t surface, indicating t h e f o r m a t i o n

of -Fe (see Fig. 7). O n further a n n e a l i n g , -Fe also
a p p e a r s a t t h e free surface a n d finally in t h e b u l k
( W a g n e r et al. 1984).
U s i n g x-ray emission M o s s b a u e r s p e c t r o s c o p y , the
p h a s e t r a n s f o r m a t i o n b y laser i r r a d i a t i o n of a n
X 2 1 0 C r l 2 steel h a s been followed (Schaaf 1987). T h e
s p e c t r u m before t h e laser t r e a t m e n t is d o m i n a t e d b y a
six-line ferrite s p e c t r u m , as s h o w n in Fig. 8a. I n t h e
center, small c o n t r i b u t i o n s of r e t a i n e d a u s t e n i t e a n d
p r o b a b l y s o m e c a r b i d e p h a s e s c a n be distinguished.
T h e laser i r r a d i a t i o n causes a n a l m o s t t o t a l transfor
m a t i o n t o the p a r a m a g n e t i c a u s t e n i t e p h a s e , as seen in
Fig. 8b.
4.6 Texture,

Polarimetry

T h e a n g u l a r d e p e n d e n c e of t h e hyperfine i n t e r a c t i o n
as observed by t h e relative line intensities (see Fig. 2)
c a n be used t o m e a s u r e o r i e n t a t i o n s of spins (spin
texture) o r o r i e n t a t i o n s of principal axes of t h e elec
tric field g r a d i e n t (principal axes texture) ( G o n s e r a n d
P f a n n e s 1974). F i g u r e 7 s h o w s a b u l k s p e c t r u m of a n
a m o r p h o u s alloy. T h e lines a r e b r o a d , b u t it is f o u n d
t h a t the second a n d fifth lines (Am = 0) a r e strongest.
T h i s indicates t h a t t h e spins a r e o r i e n t e d preferen
tially p e r p e n d i c u l a r t o t h e p r o p a g a t i o n direction of
264

Figure 8
Mossbauer x-ray emission spectra of X210Crl2 steel:
(a) before; and (b) after laser irradiation

t h e y r a y s , t h a t is, in the p l a n e of t h e a m o r p h o u s
ribbon.
T h e a n g u l a r d e p e n d e n c e of t h e split spectra is
associated with p o l a r i z a t i o n of t h e r a d i a t i o n . A p o l a r imeter for linearly a n d circularly p o l a r i z e d y rays c a n
be c o n s t r u c t e d . T o o b s e r v e r e s o n a n c e , t h e line posi
tions must be matched not only by an appropriate
D o p p l e r velocity, b u t also b y a p p r o p r i a t e p o l a r i z a
tion. W i t h such a n a p p a r a t u s , t h e birefringence
r o t a t i o n of t h e F a r a d a y - M o s s b a u e r effect c a n b e
m e a s u r e d (Pfannes a n d G o n s e r 1974).
4.7 Dynamical Effects,
Diffusion
I n general, every m e t h o d h a s its characteristic time,
effectively t h e time in w h i c h t h e i n f o r m a t i o n o n a
certain p r o p e r t y is collected a n d m e a s u r e d . I n M o s s
b a u e r s p e c t r o s c o p y , t h e characteristic t i m e o r " c l o c k "
d e p e n d s o n t h e i s o t o p e a n d is r e p r e s e n t e d by t h e m e a n
lifetime of s p o n t a n e o u s t r a n s i t i o n from t h e excited
s t a t e t o t h e g r o u n d state. T h i s t i m e s t a r t s t h e i n s t a n t
t h e excited state is r e a c h e d from higher states in t h e
s o u r c e o r in t h e a b s o r b e r w h e n t h e leading edge of t h e
y r a y arrives a t t h e nucleus. C o n s i d e r i n g t h e i s o t o p e s
1 8 7
available, o n e h a s a wide r a n g e in half-life: R e h a s a
u
197
9
119
8
5 7
Au, 10" s; Sn, 10" s; Fe,
half-life of 1 0 - s ;
7
6 7
_ 5
1 0 ~ s ; a n d Z n , 1 0 s . Half-life d e t e r m i n e s in t h e
ideal case t h e L o r e n t z i a n line w i d t h s a c c o r d i n g t o t h e
u n c e r t a i n t y principle a n d t h e " t i m e w i n d o w " for
dynamical experiments. During the "time window,"
diffusion m a y o c c u r either by j u m p s of t h e r e s o n a t i n g
a t o m s themselves ( K n a u e r a n d M u l l e n 1968) o r b y
p a s s i n g of a small a t o m like h y d r o g e n t h r o u g h neigh
b o r i n g interstitial sites of t h e r e s o n a n c e a t o m a n d

Mossbauer

causing d i s p l a c e m e n t s (Blasius et al. 1979). A s a

c o n s e q u e n c e of these processes t h e r e s o n a n t q u a n t a
suffer p h a s e shifts, c a u s i n g line b r o a d e n i n g (Singwi
a n d Sjolander 1960). F r o m this b r o a d e n i n g , t h e j u m p
frequency c a n be e v a l u a t e d . It s h o u l d b e n o t e d t h a t a t
high j u m p - r a t e s " m o t i o n a l n a r r o w i n g , " as in N M R ,
m i g h t also occur.
W h e n e v e r a r e l a x a t i o n is c a u s e d b y a
fluctuating
hyperfine i n t e r a c t i o n , t h e c h a r a c t e r i s t i c t i m e r L is t h e
precession time of t h e c o r r e s p o n d i n g n u c l e a r m o
m e n t . T h e hyperfine splitting AE is t h e n given b y t h e
u n c e r t a i n t y principle as AE ~ h/zL. O f interest a r e t h e
v a r i o u s m e c h a n i s m s involved, such as s u p e r p a r a m a g netism, spin-glass b e h a v i o r , r e o r i e n t a t i o n of electric
field g r a d i e n t principal axis, a n d so o n .
See also: X-Ray Absorption Spectroscopy: EXAFS and
XANES Techniques

Bibliography
Barrett , Grant R W, Kaplan M, Keller D A, Shirley D
A 1963 Electron transfer in dilute gold alloys. J. Chem.
Phys. 39: 1035-40
Bauer J, Gonser U, Wagner G 1986 Magnetic and
structural behavior of Fe 4 0Ni 4 0B 20 alloys as a function of
the melt-spinning parameters. Hyperfine Interact. 27:
401^1
Blasius A, Gonser U 1976 Precision phase analysis. J. Phys.
(Paris) 37(C6): 397-9
Blasius A, Preston R S, Gonser U 19795 7Mossbauer study of
the diffusion of stored hydrogen in Fe-doped titanium.
Z. Phys. Chem. (Wiesbaden) 115: 187-99
Gonser U (ed.) 1975 Mossbauer Spectroscopy, Topics in
Applied Physics, Vol. 5. Springer, Berlin
Gonser U (ed.) 1981 Mossbauer Spectroscopy II: The Exotic
Side of the Methods, Topics in Current Physics, Vol. 25.
Springer, Berlin
Gonser U (ed.) 1986 Microscopic Methods in Metals, Topics
in Current Physics, Vol. 40. Springer, Berlin
Gonser U, Ackermann M, Wagner G 1983 Magnetoelastic effects in amorphous metals due to surface crystal
lization and oxidation. / . Magn. & Magn. Mater. 31-4:
1605-7
Gonser U, Pfannes D 1974 Texture problems. / . Phys.
(Paris) 35: 113-20
Hanna S S, Heberle J, Littlejohn C, Perlow G J, Preston R

Spectroscopy

S, Vincent D 57 1960 Polarized spectra and hyperfine

structure in Fe . Phys. Rev. Lett. 4: 177-80
Kistner C, Sunyar
A W 1960 Evidence for quadrupole
57
interaction of Fe , and influence of chemical binding on
nuclear gamma-ray energy. Phys. Rev. Lett. 4: 412-15
Knauer R C, Mullen J G 1968 Direct observation of solidstate diffusion using the Mossbauer effect. Phys. Rev. 174:
711-13
Krischel K, Nasu S, Gonser U, Keune W, Lauer J, William
son D L 1980 Fe dimers and defects in Cu. / . Phys.
(Paris) 41 (CI): 417-18
Miedema A R, Van der Woude F 1980 A cellular
atomic
197
model for the Mossbauer isomer shift of Au in alloys.
Physica B, C 100: 145-56
Mossbauer R L 1958a Nuclear
resonance absorption of
1 91
gamma radiation in Ir (in German). Naturwissenschaften 45: 538-9
Mossbauer R L 1958b Nuclear
resonance-fluorescence of
1 91
gamma radiation in Ir (in German). Z. Phys. 151: 1243
Mossbauer R L 1962 Recoilless nuclear resonance absorp
tion of gamma radiation. Science 137: 731-8
Muir A Jr, Ando J, Coogan 1966 Mossbauer
Effect Data Index 1958-65. Wiley, New York
Nasu S, Gonser U 1980 Simultaneous transmission and
scattering Mossbauer study on amorphous Fe^Ni^^B^
J. Phys. (Paris) 41 (C 8): 690-3
Pfannes D, Gonser U 1974 Mossbauer birefringence
rotation polarimeter. Nucl. Instrum. Methods 114: 297-9
Schaaf 1987 Untersuchung Laserbestrahlter Stahle mit
Hilfe der Mossbauerspektroskopie. M.Sc. thesis, Univer
sity of the Saar, Saarbriicken
Shirley D A 1964 Application and interpretation of isomer
shifts. Rev. Mod. Phys. 36: 339-52
Singwi S, Sjolander A 1960 Resonance absorption of
nuclear gamma rays and the dynamics of atomic motions.
Phys. Rev. 120: 1093-102
Stevens J G, Stevens V 1966-76 Mossbauer Effect Data
Index. Hilger, London
Stevens J G, Stevens V 1977-87 Mossbauer Effect Refer
ence and Data Journal. Mossbauer Effect Data Center,
Asheville, NC
Wagner G, Ackermann M, Gonser U 1984 Crystalliza
tion of amorphous metal-metalloid alloys. / . Non-Cryst.
Solids 61-2: 847-52
Walker L R, Wertheim
G K, Jaccarino V 1961 Interpre
57
tation of the Fe isomer shift. Phys. Rev. Lett. 6: 98-101
U. Gonser and F. Aubertin
[Universitat des S a a r l a n d e s ,
Saarbriicken, Germany]

265


Neutron Radiography
N e u t r o n r a d i o g r a p h y is o n e of several m e t h o d s
e m p l o y e d for t h e visualization of i n t e r n a l details of
materials a n d s t r u c t u r e s . T h i s t e c h n i q u e utilizes n e u
t r o n s , r a t h e r t h a n o r g a m m a rays, as t h e p e n e t r a t i n g
radiation to produce a radiographic image. Neutrons
replace p h o t o n r a d i a t i o n b e c a u s e of t h e d r a m a t i c
m a n n e r in which n e u t r o n i n t e r a c t i o n s with m a t t e r
differ from t h o s e o b s e r v e d with o r g a m m a r a y s .
N e u t r o n radiography provides a new dimension to
r a d i o g r a p h i c inspection which serves t o e x t e n d a n d
complement information provided by other radio
g r a p h i c m e a n s . I n m a n y cases, t h e m e t h o d p r o v i d e s
the only m e a n s b y w h i c h certain details such as plastic
or r u b b e r c o m p o n e n t s o r v a r i a t i o n s in r e a c t o r fuel
c a n be observed.

1.

The

Neutron

N e u t r o n s a n d p r o t o n s a r e t h e b u i l d i n g b l o c k s of t h e
a t o m i c nucleus. U n l i k e t h e p r o t o n , t h e n e u t r o n is a
n e u t r a l particle w h i c h possesses n o electric c h a r g e ,
a n d it weighs slightly m o r e t h a n t h e p r o t o n , t h a t is,
1.00867 a t o m i c m a s s u n i t s . N e u t r o n s a r e u n s t a b l e
particles, h a v i n g a half-life of a p p r o x i m a t e l y 12 m i n ,
a n d decay i n t o a p r o t o n , electron a n d a n e u t r i n o .
N e u t r o n s c a n v a r y in energy from essentially zero t o
energies in excess of 20 M e V .

2. Interaction

of Neutrons

with

Matter

Referring t o the slab g e o m e t r y of F i g . 1, o r g a m m a

rays interact with o r b i t a l e l e c t r o n s o f t h e a t o m s
c o m p r i s i n g t h e m a t e r i a l t h r o u g h w h i c h they p a s s .
N e u t r o n s , o n t h e o t h e r h a n d , p e n e t r a t e the electron
cloud a n d interact directly w i t h t h e a t o m i c nucleus.
T h e r a d i a t i o n b e a m scattering m e c h a n i s m is t h e s a m e
in b o t h cases, t h a t is, t h e incident r a d i a t i o n is either
scattered from t h e b e a m o r totally a b s o r b e d . In b o t h
cases, t h e e x p o n e n t i a l a t t e n u a t i o n law is o b e y e d :
/=/0exp[-/>(^)x]

t r o n s a r e heavily a t t e n u a t e d by t h e lighter a t o m i c
n u m b e r elements while experiencing low a t t e n u a t i o n
b y t h e heavier elements. T h i s is b e c a u s e t h e nuclei
with w h i c h t h e n e u t r o n s i n t e r a c t possess a c o m p l e x
energy-level s t r u c t u r e . T h e m a s s a t t e n u a t i o n coeffi
cients of t h e elements for o r g a m m a rays, interacting
with t h e optical electrons, a r e illustrated b y the solid
m o n o t o n i c a l l y increasing c u r v e in F i g . 2. T h i s is
b e c a u s e t h e n u m b e r of electrons o r b i t i n g t h e a t o m i c
nucleus b e a r s a direct r e l a t i o n s h i p t o m a t e r i a l density
a n d h e n c e t o x- a n d g a m m a - r a y a t t e n u a t i o n .

3. Neutron

Production

A typical n e u t r o n r a d i o g r a p h y facility consists of a

fast n e u t r o n source, n e u t r o n m o d e r a t o r , collimator,
specimen a n d s o m e f o r m of i m a g i n g system.
N e u t r o n s a r e p r o d u c e d b y t h e fission process in a
n u c l e a r r e a c t o r , t h e fission p r o c e s s in a subcritical
assembly, a c c e l e r a t o r - i n d u c e d r e a c t i o n s o r isotopic
sources. T o be m o s t effective for industrial r a d i o
g r a p h i c a p p l i c a t i o n s , t h e n e u t r o n s m u s t possess
energies of a p p r o x i m a t e l y 0.025 eV, t h a t is t h e r m a l
energies. I n all cases, t h e p r i m a r y n e u t r o n s p r o d u c e d
a r e fast, possessing energies m u c h in excess of
0.025 eV, a n d m u s t b e slowed d o w n ( m o d e r a t e d ) t o
t h e r m a l energies by t h e p r o c e s s of inelastic scattering
with m a t t e r : light m a t e r i a l s such as H 2 0 , D 2 0 , beryl
lium o r c a r b o n a r e used as m o d e r a t o r s .
Since t h e t h e r m a l i z e d n e u t r o n s a r e pervasive a n d
p r e s e n t a d i s t r i b u t e d s o u r c e h a v i n g finite d i m e n s i o n s ,
it is necessary t o collimate a n e u t r o n b e a m t o achieve
detail in t h e final i m a g e . T h i s c a n be a c c o m p l i s h e d b y
inserting a divergent r e e n t r a n t p o r t i n t o t h e m o d e r a
t o r . T h i s c o l l i m a t o r is lined with a t h e r m a l n e u t r o n
a b s o r b i n g m a t e r i a l a n d possesses a n a p e r t u r e for the

(1)
2

where / is the t r a n s m i t t e d r a d i a t i o n flux (n c m " s " ) ,

2 _ I
I0 is t h e incident r a d i a t i o n flux ( n c m " s ) , is t h e
- 3
m a t e r i a l density ( g e m ) , (/) is t h e m a s s a t t e n u a
2
_ 1
tion coefficient ( c m g ) , is t h e linear a t t e n u a t i o n
- 1
coefficient ( c m ) a n d is t h e m a t e r i a l thickness (cm).
T h e n e u t r o n m a s s a t t e n u a t i o n coefficients as func
tions of a t o m i c n u m b e r , illustrated in F i g . 2, exhibit
a n a l m o s t r a n d o m p a t t e r n . I n general, t h e r m a l n e u

Scattered radiation

Figure 1
Transmission of radiation through materials

267

Neutron

Radiography

* "

30

40

50

60

70

80

90

100

Atomic number
Figure 2
Mass attenuation coefficient as a function of atomic number of the elements

release of exiting n e u t r o n s . A m e a s u r e of t h e collimat i o n c a p a b i l i t y of a given facility is given by t h e r a t i o

LjD w h e r e L is t h e d i s t a n c e b e t w e e n t h e a p e r t u r e a n d
t h e i m a g e p l a n e a n d D is t h e a p e r t u r e d i a m e t e r . A
large LjD r a t i o is c o m p a r a b l e t o a small focal s p o t in
r a d i o g r a p h y ; g o o d spatial r e s o l u t i o n i m a g e s c a n b e
produced.
T h e i m p o r t a n t characteristics of a n e u t r o n b e a m
for r a d i o g r a p h y are: (a) t h e t h e r m a l n e u t r o n flux
available; (b) t h e c a d m i u m r a t i o , t h a t is, t h e r a t i o of
t h e r m a l t o fast n e u t r o n s ; (c) t h e degree of c o l l i m a t i o n ,
t h a t is, t h e LjD r a t i o ; a n d (d) t h e r a t i o of t h e r m a l
neutron content to beam gamma-ray content.

4. Neutron

Applications

O n e e x a m p l e of n e u t r o n r a d i o g r a p h y is illustrated in
Fig. 3 in w h i c h a n r a y a n d a n e u t r o n r a d i o g r a p h of
t h e s a m e specimen a r e c o m p a r e d . In t h e r a d i o g r a p h
in F i g . 3a, t h e p l a c e m e n t of t h e n e o p r e n e seal in a
stainless steel valve is n o t evident. H o w e v e r , t h e seal
c a n b e readily seen in t h e n e u t r o n r a d i o g r a p h of F i g .
3b. T h i s is d u e t o b e a m scattering by h y d r o g e n a t o m s .
O t h e r a p p l i c a t i o n s include t h e e x a m i n a t i o n of p l a s
tics, r u b b e r , adhesives, explosives o r w o o d in c o n t a i n
m e n t systems w h i c h a r e o p a q u e t o o r g a m m a r a y s .

Imaging

Being a n o n i o n i z i n g particle, t h e n e u t r o n d o e s n o t
i n t e r a c t with r a d i o g r a p h i c film t o f o r m a n i m a g e
directly, b u t m u s t be c o n v e r t e d t o s o m e t y p e of
r a d i a t i o n w h i c h will sensitize t h e film. Basically this is
a c c o m p l i s h e d in t h r e e w a y s : (a) in t h e direct i m a g i n g
m o d e in w h i c h r a d i a t i o n c a p a b l e of sensitizing t h e
film is p r o d u c e d o n n e u t r o n c a p t u r e by a c o n v e r t e r
foil; (b) t h e indirect i m a g i n g m o d e in w h i c h a n
a u t o r a d i o g r a p h is m a d e of a n i m a g e d c o n v e r t e r emit
ting delayed ionizing r a d i a t i o n t o e x p o s e t h e film; a n d
(c) t h e electronic m o d e in w h i c h a direct e x p o s u r e is
p r o d u c e d o n a n e u t r o n - s e n s i t i v e video system.

268

5.

(a)

(b)

Figure 3
Radiographs using (a) rays and (b) neutrons of a
stainless steel valve with neoprene seal

Nuclear

E x a m p l e s of such c o n t a i n m e n t systems include i r o n ,

steel, t u n g s t e n , lead a n d b i s m u t h .

Magnetic

Resonance

Spectroscopy

See also: Gamma Radiography

m a g n e t i c p r o p e r t i e s of t h e individual nucleus: spin

q u a n t u m n u m b e r , n a t u r a l a b u n d a n c e , electric q u a d rupole moment and magnetic moment.

Bibliography

1.

Berger 1965 Neutron Radiography. Elsevier, Amsterdam

Berger (ed.) 1977 Practical Applications of Neutron Radio
graphy and Gaging, STP 586. American Society for Test
ing and Materials, Philadelphia, PA
Sharpe R S (ed.) 1970 Research Techniques in Non-destruc
tive Testing, Vol. 1. Academic Press, London

A t o m i c nuclei m a y possess a n g u l a r m o m e n t u m , a n d
therefore a m a g n e t i c d i p o l e m o m e n t d e p e n d i n g
u p o n their spin q u a n t u m n u m b e r I. T h e spin q u a n t u m
n u m b e r m a y h a v e values of z e r o , half-integers a n d
w h o l e integers. Nuclei w i t h 1=0 h a v e n o m a g n e t i c
m o m e n t a n d therefore d o n o t exhibit t h e N M R
p h e n o m e n o n ; this includes all nuclei with a n even
m a s s a n d a t o m i c n u m b e r . Theoretically, all of the
r e m a i n i n g nuclei c a n be o b s e r v e d b y N M R .
I n t h e classical m e c h a n i c a l d e s c r i p t i o n of N M R , a
nucleus is c o n s i d e r e d t o b e precessing a b o u t the
a p p l i e d m a g n e t i c field with t h e frequency of preces
sion given b y t h e L a r m o r e q u a t i o n :

D. A. Garrett
[ N a t i o n a l B u r e a u of S t a n d a r d s ,
Washington, D C , USA]

Nuclear Magnetic Resonance

Spectroscopy
N u c l e a r m a g n e t i c r e s o n a n c e ( N M R ) s p e c t r o s c o p y is
a n analytical t e c h n i q u e e m p l o y e d in t h e identification
a n d s t r u c t u r a l e l u c i d a t i o n of o r g a n i c m a t e r i a l s . N M R
of b u l k m a t e r i a l s w a s first o b s e r v e d in 1946 i n d e p e n
dently by Bloch a t S t a n f o r d a n d Purcell a t H a r v a r d
(for which they received t h e 1952 N o b e l Prize). I n t h e
N M R e x p e r i m e n t , a s a m p l e is placed in a h o m o
g e n e o u s m a g n e t i c field a n d r a d i o - f r e q u e n c y (rf)
e l e c t r o m a g n e t i c energy is applied. P a r t i c u l a r nuclei
a b s o r b this energy a t s h a r p l y defined frequencies; this
signal is t h e n detected, amplified a n d p r e s e n t e d as a
frequency s p e c t r u m . T h e three m o s t i m p o r t a n t types
of i n f o r m a t i o n o b t a i n e d in t h e h i g h - r e s o l u t i o n N M R
s p e c t r u m are: frequency, a r e a a n d multiplicity of t h e
r e s o n a n c e line. T h e exact r e s o n a n c e frequency of a
nucleus is d e p e n d e n t o n its chemical e n v i r o n m e n t in
the molecule a n d is m e a s u r e d a g a i n s t a reference line.
T h e a r e a u n d e r t h e r e s o n a n c e line c a n b e i n t e g r a t e d
i n s t r u m e n t a l l y t o give q u a n t i t a t i v e i n f o r m a t i o n a b o u t
the relative n u m b e r of nuclei giving rise t o e a c h p e a k .
Multiplicity of a p e a k (resulting from spin c o u p
ling) indicates s t r u c t u r a l i n f o r m a t i o n a b o u t n e a r n e i g h b o r i n g nuclei.
R e c e n t a d v a n c e s in i n s t r u m e n t a t i o n a n d c o m p u t e r
capabilities, c o u p l e d with pulse t e c h n i q u e s a n d F o u r
ier t r a n s f o r m a t i o n h a v e greatly e n h a n c e d t h e sensi
tivity of N M R s p e c t r o s c o p y : spectra m a y b e o b t a i n e d
from solutions of very low c o n c e n t r a t i o n s , nuclei m a y
be o b s e r v e d t h a t h a v e very low n a t u r a l a b u n d a n c e ,
a n d resolution of spectral lines is greatly i m p r o v e d .
U n t i l recently, h i g h - r e s o l u t i o n N M R s p e c t r a c o u l d b e
o b t a i n e d only o n s a m p l e s in solution; h o w e v e r , n e w
s p e c t r o m e t e r s h a v e b e c o m e available w h i c h utilize
special techniques t o p r o v i d e solid-sample capability.
B r o a d b a n d e d o r t u n a b l e p r o b e s allow o b s e r v a t i o n of
a great n u m b e r of nuclei with ease. T h e utility of this
capability, h o w e v e r , is limited b y restrictions of t h e

The NMR

Phenomenon

v0 =

/20

w h e r e v 0 is called t h e L a r m o r frequency of a nucleus,

H0 is t h e applied m a g n e t i c field a n d is t h e m a g n e t o gyric r a t i o , w h i c h varies from o n e nucleus t o a n o t h e r .
If a small m a g n e t i c field l is applied p e r p e n d i c u l a r t o
H0, a n d m a d e t o r o t a t e a t a frequency of v 0, energy is
a b s o r b e d from t h e Hl field i n t o t h e spin system. If Hl
is r o t a t i n g a t a n y frequency o t h e r t h a n v 0, n o net
a b s o r p t i o n of energy o c c u r s . T h e L a r m o r frequency is
very different for individual nuclei; for e x a m p l e , in a
m a g n e t i c field of 1.8 t h e L a r m o r frequencies are
1 3
79.54 M H z for , 20 M H z for C a n d 8.06 M H z
1 5
for N .
T h e q u a n t u m m e c h a n i c a l description of N M R c o n
siders t h e i n t e r a c t i o n of a m a g n e t i c m o m e n t with a n
a p p l i e d field. A nucleus with 7 = 0 aligns itself in
different o r i e n t a t i o n s w i t h respect t o a n applied m a g
netic field p r o d u c i n g 21 + 1 energy levels. T r a n s i t i o n s
a r e i n d u c e d by a b s o r p t i o n of energy from a n applied
e l e c t r o m a g n e t i c field. I n t h e simplest case, / = i , there
a r e t w o energy levels w h o s e s e p a r a t i o n is linearly
d e p e n d e n t o n t h e m a g n i t u d e of H0. T h e s e p a r a t i o n of
t h e energy levels is small, a n d a t e q u i l i b r i u m there is
only a slight excess of nuclei in t h e lower energy spin
state as given b y t h e B o l t z m a n n p o p u l a t i o n distribu
tion. Since t h e N M R e x p e r i m e n t is d e p e n d e n t u p o n
this small p o p u l a t i o n t o p r o d u c e a signal, N M R is
relatively insensitive c o m p a r e d with o t h e r s p e c t r o
scopic t e c h n i q u e s . A t r e s o n a n c e , t h e p o p u l a t i o n s of
t h e t w o energy levels a r e equalized. T h e process by
w h i c h t h e nuclei reestablish a B o l t z m a n n p o p u l a t i o n
d i s t r i b u t i o n is called s p i n - l a t t i c e r e l a x a t i o n . Several
c o m m o n m e c h a n i s m s of s p i n - l a t t i c e r e l a x a t i o n in
clude i n t e r a c t i o n s with n e i g h b o r i n g m a g n e t i c nuclei,
free r o t a t i o n of a functional g r o u p o r molecule, the
presence of significant a n i s o t r o p y in t h e shielding (see
Sect. 2), a n d i n t e r a c t i o n s t h r o u g h s p i n - s p i n c o u p l i n g
(see Sect. 3) w i t h a n o t h e r r a p i d l y relaxing nucleus.

269

Nuclear

Magnetic

Resonance

Spectroscopy

C H ?- C H ,
\

2.6

1.2
- C H 2-

-CH,

mm

tutu

I
10

I
9

I
8

I
3

I
2

(ppm)

Figure 1
NMR spectrum of ethylbenzene showing a triplet and
quartet corresponding to the methyl and methylene
protons, respectively. Arrows indicate the possible
orientations of the protons of the neighboring group
resulting in the characteristic number and intensities of
lines

T h e spin-lattice relaxation time tx for m o s t c o m m o n

nuclei is 0 . 1 - 1 0 s, b u t m a y be as l o n g as several
h u n d r e d seconds for s o m e nuclei.

2. Chemical

Shift

In a c o n s t a n t h o m o g e n e o u s m a g n e t i c field, nuclei
c o m e i n t o r e s o n a n c e at a very specific frequency (
a t 79.5 M H z in a 1.8 field, for e x a m p l e ) . F o r t u n a
tely for the chemist, all p r o t o n s d o n o t r e s o n a t e a t
exactly 79.5 M H z . T h e very subtle differences in the
r e s o n a n c e frequency a r e d u e t o t h e differences in the
chemical e n v i r o n m e n t of t h e o b s e r v e d nuclei; t h e
difference in frequency is referred t o as the chemical
shift. F i g u r e 1 s h o w s t h e N M R s p e c t r u m of
ethylbenzene. It c o n t a i n s three sets of r e s o n a n c e lines:
a singlet ( a r o m a t i c p r o t o n s ) , a q u a r t e t (methylene
p r o t o n s ) a n d a triplet (methyl p r o t o n s ) . T h e different
positions t h a t these r e s o n a n c e lines o c c u p y in t h e
frequency s p e c t r u m relative t o a n internal s t a n d a r d
are referred t o as differences in their chemical shifts.
E a c h nucleus is s u r r o u n d e d b y a n electron cloud, the
m o t i o n of these electrons creating a s e c o n d a r y m a g
netic field which t e n d s t o o p p o s e the applied m a g n e t i c
field; chemical-shift differences arise b e c a u s e this elec
t r o n density varies, d e p e n d i n g u p o n t h e electronegati
vity of t h e a t o m s a t t a c h e d t o the nucleus a n d the type
of b o n d i n g in which it is involved. T h u s , t h e higher
t h e electron density a b o u t a nucleus, the greater the
s e c o n d a r y m a g n e t i c field (or " s h i e l d i n g " effect) a n d ,

270

therefore, t h e greater t h e applied m a g n e t i c field m u s t

be t o b r i n g t h a t nucleus i n t o r e s o n a n c e . If a functional
g r o u p w i t h d r a w s electrons (electronegative) from a
nucleus it p r o d u c e s a deshielding effect; if it p u s h e s
electrons (electropositive) t o w a r d s a nucleus it p r o
duces a shielding effect.
A l t h o u g h N M R d a t a a r e m e a s u r e d in frequency
u n i t s , they a r e usually r e p o r t e d in t h e dimensionless
u n i t of p a r t s p e r million ( p p m ) which is i n d e p e n d e n t
of t h e r a d i o frequency o r m a g n e t i c field strength. T h i s
dimensionless chemical shift is given t h e s y m b o l .
T h e t e r m s " u p f i e l d " a n d " d o w n f i e l d " a r e fre
q u e n t l y used t o describe the direction of chemical
shifts. T h e s e t e r m s refer t o the s t r e n g t h of t h e applied
m a g n e t i c field. F o r e x a m p l e , t h e N M R s p e c t r u m
of e t h y l b e n z e n e (Fig. 1) c o n t a i n s a singlet (7.2 p p m ) , a
q u a r t e t (2.6 p p m ) a n d a triplet (1.2 p p m ) . T h e singlet
( c o r r e s p o n d i n g t o t h e a r o m a t i c p r o t o n s ) is the furth
est downfield, t h e triplet ( c o r r e s p o n d i n g t o the m e t h y l
p r o t o n s ) is t h e furthest upfield. T h e signal a t t h e
e x t r e m e upfield edge of the s p e c t r u m is tetramethylsilane ( T M S ) , a n i n t e r n a l reference. I n T M S , t h e silicon
(a highly electropositive a t o m ) p r o d u c e s a very s t r o n g
shielding effect w h i c h causes it t o r e s o n a t e a t a higher
field s t r e n g t h t h a n m o s t p r o t o n s in o t h e r o r g a n i c
c o m p o u n d s . T h i s a n d t h e fact t h a t it c o n t a i n s twelve
equivalent p r o t o n s w h i c h p r o d u c e a very s h a r p singlet
m a k e T M S a n excellent i n t e r n a l reference. T h e c h e m
ical shift of T M S is assigned as zero b y c o n v e n t i o n ;
t h e shifts of o t h e r signals a r e calculated, o r r e a d off
c h a r t p a p e r , in a r a n g e of a p p r o x i m a t e l y 0 - 1 0 p p m
for with chemical shift increasing t o w a r d lower
field (higher values t o t h e left). T h i s c o n v e n t i o n h o l d s
1 3
t r u e w i t h o t h e r nuclei as well. In C N M R , for
e x a m p l e , T M S is also used as a n i n t e r n a l s t a n d a r d .
13
T h e chemical shift r a n g e of C is m u c h larger t h a n
t h a t for , r a n g i n g from T M S a t zero d o w n t o
c a r b o n y l c a r b o n s a t a b o u t 200 p p m . T M S is also used
29
as a n i n t e r n a l s t a n d a r d for S i N M R . In this case,
h o w e v e r , it a p p e a r s n e a r t h e low-field e n d of the
29
chemical-shift r a n g e so t h a t m a n y S i chemical shifts
a r e negative.

3.

NMR

C o n s i d e r t h e N M R s p e c t r u m of e t h y l b e n z e n e
s h o w n in Fig. 1. T h e d o m i n a n t features of t h e spec
t r u m a r e t h e presence of a triplet a t 1.2 p p m (methyl
p r o t o n s ) a n d a q u a r t e t at 2.6 p p m (methylene p r o
t o n s ) . Differences in m a g n e t i c e n v i r o n m e n t a r e re
sponsible for t h e differences in chemical shift, t h e
effect of the nearest n e i g h b o r i n g g r o u p usually being
m o s t i m p o r t a n t . I n t h e case of t h e m e t h y l g r o u p , for
e x a m p l e , t h e n e i g h b o r i n g m e t h y l e n e g r o u p n o t only
affects t h e p o s i t i o n of t h e r e s o n a n c e line b u t causes
t h e p e a k t o b e split i n t o a triplet as well. T h e e x p l a n a
tion for this p h e n o m e n o n , called s p i n - s p i n splitting,
lies in t h e fact t h a t t h e n e i g h b o r i n g p r o t o n s m a y also

Nuclear

Table 1
Relative intensities of the lines of a multiplet

Multiplicity

0
1
2
3
4
5

singlet
doublet
triplet
quartet
quintet
sextet

Intensity
1
11
1 2 1
13 3 1
1 4 6 4 1
1 5 10 10 5 1

be in different o r i e n t a t i o n s w i t h respect t o t h e a p p l i e d
m a g n e t i c field. Since t h e p r o t o n is a nucleus w i t h
=
t w
o
I h
possible spin states exist for e a c h p r o t o n .
Depending u p o n whether the neighboring nuclear
spin is aligned with (parallel) o r o p p o s e d t o (antiparallel) t h e p r o t o n a t r e s o n a n c e , it will either in
crease o r decrease t h e n e t m a g n e t i c field experienced
by the o b s e r v e d p r o t o n . T h i s gives rise t o different
energy levels a n d t h u s different r e s o n a n c e lines. In t h e
case of the m e t h y l e n e p r o t o n s of e t h y l b e n z e n e , t h r e e
c o m b i n a t i o n s a r e possible (see F i g . 1) p r o d u c i n g a
triplet for t h e m e t h y l p r o t o n s . Likewise, t h e m e t h y
lene p r o t o n s a r e affected b y t h e three m e t h y l p r o t o n s .
T h e possible o r i e n t a t i o n s of these t h r e e p r o t o n s are:
all three aligned, t w o aligned a n d o n e o p p o s e d ( a n d
there a r e three p e r m u t a t i o n s of this o r i e n t a t i o n ) , t w o
o p p o s e d a n d o n e aligned (also with three p e r m u t a
tions), a n d all t h r e e o p p o s e d . T h e effect of t h e m e t h y l
g r o u p , therefore, is t o p r o d u c e four r e s o n a n c e lines (a
q u a r t e t ) for t h e m e t h y l e n e p r o t o n s .
S p i n - s p i n splitting is a p r i m a r y characteristic of
N M R . T h e s e i n t e r a c t i o n s a r e said t o b e electron
c o u p l e d in t h a t they o p e r a t e t h r o u g h t h e b o n d i n g
n e t w o r k ; t h e effect is q u i t e s t r o n g over t h e first few
b o n d s b u t diminishes greatly thereafter. T h e n u m b e r
of lines p r o d u c e d b y s p i n - s p i n c o u p l i n g is given by:
multiplicity = 2nl + 1
w h e r e is t h e n u m b e r of p r o t o n s in t h e n e i g h b o r i n g
g r o u p a n d lis t h e spin q u a n t u m n u m b e r ( = i ) . T h e
relative intensities of t h e lines of a m u l t i p l e t a r e
predicted by P a s c a l ' s triangle ( T a b l e 1).
T h e s e p a r a t i o n b e t w e e n t h e lines of a m u l t i p l e t is
referred t o as t h e c o u p l i n g c o n s t a n t J. T h i s value,
expressed in h e r t z , reflects t h e m a g n i t u d e of t h e s p i n spin i n t e r a c t i o n a n d is i n d e p e n d e n t of t h e a p p l i e d
m a g n e t i c field. C h a r a c t e r i s t i c c o u p l i n g c o n s t a n t s a r e
of great value in s t r u c t u r e e l u c i d a t i o n .

4. Fourier

Transform

NMR

T h e c o n v e n t i o n a l m o d e of i n s t r u m e n t o p e r a t i o n
involves v a r y i n g either t h e m a g n e t i c field o r rf signal
while h o l d i n g t h e o t h e r c o n s t a n t (field o r frequency

Magnetic

Resonance

Spectroscopy

sweep, also called C W for c o n t i n u o u s w a v e N M R ) .

T h e s e s p e c t r a r e q u i r e several m i n u t e s t o r e c o r d , since
e a c h t r a n s i t i o n is i n d u c e d in succession a n d a t a n y
given m o m e n t only o n e frequency is being observed.
T h i s inefficiency is o v e r c o m e by t h e use of pulse
N M R ; a s h o r t rf pulse w h i c h c o n t a i n s a b a n d w i d t h of
frequencies sufficiently large t o cover t h e entire reso
n a n c e r a n g e of t h e n u c l e u s of interest is applied t o the
s a m p l e . F o r e x a m p l e , in a 2.3 m a g n e t i c field this
13
c o r r e s p o n d s t o 1000 H z for a n d 5000 H z for C .
I n d i v i d u a l frequency c o m p o n e n t s a r e a b s o r b e d by the
s a m p l e a n d t h e n r e e m i t t e d w h e n t h e pulse is t u r n e d
off. T h e p a t t e r n detected by t h e receiver is called a
free-induction d e c a y ( F I D ) a n d is s h o w n in t h e t o p
trace of F i g . 2. T h e F I D consists of o n e exponentially
d e c a y i n g sine w a v e for e a c h single frequency a b s o r b e d
from t h e pulse. T h e c o n v e r s i o n from t h e time-based
F I D t o t h e c o n v e n t i o n a l frequency-based N M R spec
t r u m (see F i g . 2) is carried o u t m a t h e m a t i c a l l y by
F o u r i e r t r a n s f o r m a t i o n ( F T ) . F o r this r e a s o n , F T N M R s p e c t r o m e t e r s h a v e c o m p u t e r s as a n integral
p a r t of t h e system.
T h e a d v a n t a g e of F T - N M R is t h a t spectra c a n be
a c q u i r e d in a few seconds; for e x a m p l e , with a repeti
tion time of 1 s, 300 s p e c t r a c a n be o b t a i n e d in the
5 m i n r e q u i r e d t o r e c o r d a single s p e c t r u m using C W
t e c h n i q u e s . T h i s is p a r t i c u l a r l y useful for very-lowsensitivity s a m p l e s for w h i c h time a v e r a g i n g b e c o m e s
necessary t o o b t a i n a s p e c t r u m . I n a d d i t i o n t o observ
ing s a m p l e s a t low c o n c e n t r a t i o n , t h e F T t e c h n i q u e
also p e r m i t s t h e o b s e r v a t i o n of nuclei p r e s e n t a t low
n a t u r a l a b u n d a n c e o r with small m a g n e t i c m o m e n t s
(or b o t h ) .

5.

13

CNMR

O n e of t h e low-sensitivity nuclei w h i c h h a s b e c o m e a
r o u t i n e analytical t o o l for o r g a n i c chemists since t h e
1 3
a d v e n t of F T - N M R is C . T h e m a g n e t i c m o m e n t of
1 3
C is a b o u t o n e q u a r t e r of t h a t of , b u t its n a t u r a l
a b u n d a n c e is only 1 . 1 % . T h e r a r e o c c u r r e n c e of t h e
1 3
i s o t o p e greatly simplifies C N M R spectra by elimi
1 3
1 3
n a t i n g t h e s p i n - s p i n c o u p l i n g ( C - C ) which is so
d o m i n a n t in N M R spectra. F u r t h e r simplification
1 3
of C spectra is achieved b y r e m o v i n g t h e scalar
1 3
coupling between C and by double-resonance
d e c o u p l i n g o v e r t h e chemical-shift r a n g e . I n the
r e s u l t a n t s p e c t r u m , e a c h line c o r r e s p o n d s t o a m a g
netically u n i q u e c a r b o n a t o m in t h e s a m p l e . T h e
1 3
relatively large C chemical-shift r a n g e , which is
a b o u t t w e n t y times t h a t for , affords g o o d resolu
tion of even structurally q u i t e similar a t o m s . T h e
ability t o differentiate a m o n g several s t r u c t u r e s is
facilitated b y t h e fact t h a t t h e m a j o r factors g o v e r n i n g
1 3
C n u c l e a r shieldings a r e well established. Experi
m e n t a l l y , it h a s b e e n f o u n d t h a t s u b s t i t u e n t effects o n
1 3
C chemical shifts a r e largely additive. Semiempirical
m e t h o d s , therefore, a r e usually successful in predict-

271

Nuclear

Magnetic

Resonance

Spectroscopy

Time domain

Figure 2
13
C NMR spectrum of ethylbenzene showing the time-based free-induction decay (upper trace) and corresponding
frequency spectrum (lower trace)

ing these shifts. It is p a r t i c u l a r l y useful, b u t n o t

necessary, t o h a v e t h e a p p r o p r i a t e m o d e l c o m p o u n d s
1 3
available for c o m p a r i s o n . T h e largest v a r i a t i o n in C
chemical shifts o c c u r s with direct s u b s t i t u t i o n by
highly electronegative e l e m e n t s (oxygen, n i t r o g e n ,
fluorine, chlorine). T h e h y b r i d i z a t i o n a t c a r b o n also
strongly affects t h e p o s i t i o n of t h e r e s o n a n c e line.
S o m e typical c a r b o n chemical shifts a r e s h o w n in
T a b l e 2. I n a d d i t i o n t o c h e m i c a l shift i n f o r m a t i o n ,
o t h e r e x p e r i m e n t s , such as off-resonance d e c o u
pling, c a n p r o v i d e s t r u c t u r a l i n f o r m a t i o n . I n t h e
off-resonance d e c o u p l i n g e x p e r i m e n t , t h e d e c o u p l e r
frequency, is slightly offset from t h e chemical-shift

region. T h e result is t h a t a small residual c o u p l i n g t o

e a c h c a r b o n is o b s e r v e d , t h e multiplicity of w h i c h
c o r r e s p o n d s t o t h e n u m b e r of directly a t t a c h e d p r o
tons plus one. F o r example, Fig. 3 shows a compari
s o n b e t w e e n t h e effect of c o m p l e t e d e c o u p l i n g a n d
1 3
off-resonance d e c o u p l i n g o n t h e C N M R s p e c t r u m
of e t h y l b e n z e n e . I n t h e off-resonance d e c o u p l i n g ex
periment, the methyl a n d methylene carbon reso
n a n c e s b e c o m e a q u a r t e t a n d triplet, respectively,
while t h e t h r e e p r o t o n a t e d a r o m a t i c - c a r b o n r e s o
nances become doublets. The quaternary aromaticc a r b o n r e s o n a n c e r e m a i n s a singlet since it h a s n o
directly a t t a c h e d p r o t o n s .

Table 2
8
C Chemical shifts for some common organic compounds

13

Compound

30.4

204.1

(a)

CH 3CCH
J
3
a

CH2

CH2C12
CH3OH
(CH 3CH 2) 2NH

54.0
49.3
15.4

44.1

CH 3CH 2CH 2CH 2CH 3

13.9

22.9

(b)

C 6H 6

CH3COH
J
a

32.0

160

128.5
20.6

LI
I
140

I
100

I
80

178.3

a Values in ppm downfield from internal tetramethylsilane reference

272

CH3

( ppm )

Figure 3
13
C N M R spectrum of ethylbenzene with (a) complete
proton decoupling, and (b) off-resonance decoupling. The
insert in (b) is an expansion of the region 123-130 ppm

Nuclear

6. Other

Nuclei

Before 1970, t h e b u l k of N M R studies c o n c e r n e d t h e

p r o t o n . T h e rest of t h e interest a t t h a t t i m e w a s
1 9
3 1
divided b e t w e e n t h e high-sensitivity nuclei F , P a n d
n
B . T h e i m p r o v e m e n t o f t h e N M R t e c h n i q u e led t o a
1 0
1 4
1 5
surge of interest in o t h e r i s o t o p e s such as B , N , N
13
a n d C which a r e n o w c o n s i d e r e d t o be c o m m o n
29
119
N M R nuclides. B o t h S i a n d
S n h a v e also b e e n
used extensively. M o r e recently, studies involving
virtually all o b s e r v a b l e N M R nuclei h a v e b e e n carried
out.
See also: Nuclear Magnetic Resonance Spectroscopy of
Solids

Bibliography
Becker D 1980 High Resolution NMR: Theory and Chem
ical Applications, 2nd edn. Academic Press, New York
Bovey F A 1968 Nuclear Magnetic Resonance Spectroscopy.
Academic Press, New York
Farrar C, Becker E D 1971 Pulse and Fourier Transform
NMR: Introduction to Theory and Methods. Academic
Press, New York
Harris R K, Mann (eds.) 1978 NMR and the Periodic
Table. Academic Press, New York
Levy G C, Nelson G L 1972 Carbon-13 Nuclear Magnetic
Resonance for Organic Chemists. Wiley, New York
Slichter C 1978 Principles of Magnetic Resonance, 2nd
edn. Springer, Berlin
Stothers J 1972 Carbon-13 NMR Spectroscopy. Academic
Press, New York
E. A . Williams a n d P. E. D o n a h u e
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]

Nuclear Magnetic Resonance

Spectroscopy of Solids
The nuclear magnetic resonance ( N M R ) phenome
n o n w a s discovered in t h e 1940s. A t a b o u t t h e s a m e
time, t w o different research g r o u p s s h o w e d t h a t w h e n
samples were p l a c e d in a s t r o n g , h o m o g e n e o u s m a g
netic (applied) field, t h e s a m p l e c o u l d a b s o r b a n d emit
radio-frequency (rf) e n e r g y (Purcell et al. 1946, Bloch
et al. 1947). A solid m a t e r i a l (paraffin) w a s o n e of t h e
first samples used in t h e m e a s u r e m e n t of N M R ;
however, a wide r e s o n a n c e line w i d t h p r e v e n t e d a n y
detailed i n t e r p r e t a t i o n of t h e spectra. R e s e a r c h e r s
quickly realized t h a t liquid s a m p l e s p r o v i d e s u b s t a n
tially i m p r o v e d spectral r e s o l u t i o n . W i t h liquid s a m
ples a n d i m p r o v e m e n t s in i n s t r u m e n t a t i o n t h a t
quickly followed, t h e chemical shift w a s discovered,
a l o n g with t h e discovery of scalar ( s p i n - s p i n o r
" t h r o u g h - b o n d " ) c o u p l i n g . C h e m i c a l shifts a r e small
p e r t u r b a t i o n s of t h e exact r e s o n a n c e frequency of a
given nucleus caused b y differences in t h e electronic

Magnetic

Resonance

Spectroscopy

of

Solids

e n v i r o n m e n t of the individual nuclei. U s u a l l y very

small, chemical shifts a r e typically m e a s u r e d in p a r t s
p e r million ( p p m ) relative t o t h e r e s o n a n c e p o s i t i o n of
s o m e s t a n d a r d . M a g n e t i c nuclei w h i c h s h a r e c o m m o n
electrons c a n c o u p l e with e a c h o t h e r , giving rise t o
scalar c o u p l i n g . T h i s s p i n - s p i n c o u p l i n g gives rise t o
fine-structure
(splittings) of t h e r e s o n a n c e s of the
nuclei involved. O f c o u r s e , t h e discovery of these t w o
N M R p e r t u r b a t i o n s p r o v i d e d chemists with a p o w e r
ful t e c h n i q u e for o b t a i n i n g s t r u c t u r a l i n f o r m a t i o n o n
liquid s a m p l e s . I n a s h o r t t i m e , c o m m e r c i a l instru
m e n t a t i o n w a s m a d e available t o chemists for the
s t u d y of liquid o r s o l u t i o n s a m p l e s . M a n y experi
m e n t s were d e v e l o p e d w h i c h exploited chemical shifts
a n d scalar c o u p l i n g t o o b t a i n detailed s t r u c t u r a l in
f o r m a t i o n . N M R of solids w a s left t o a relatively few
N M R research l a b o r a t o r i e s .
W o r k in this a r e a w a s difficult a n d slow going,
o w i n g t o e n o r m o u s sensitivity a n d r e s o l u t i o n p r o b
lems c a u s e d m a i n l y b y t w o factors. First, m a g n e t i c
nuclei in solid s a m p l e s i n t e r a c t with each o t h e r
t h r o u g h their m a g n e t i c dipole m o m e n t s . T h i s d i p o l a r ,
t h r o u g h - s p a c e i n t e r a c t i o n c a n be m u c h s t r o n g e r t h a n
the t h r o u g h - b o n d , scalar i n t e r a c t i o n s . T h e s t r e n g t h of
the d i p o l a r i n t e r a c t i o n is p r o p o r t i o n a l t o
2

3cos ~ 1
3

'

w h e r e is t h e angle b e t w e e n a vector c o n n e c t i n g the

t w o i n t e r a c t i n g nuclei a n d t h e a p p l i e d field, a n d r is
their i n t e r a t o m i c distance. T h u s , t h e exact r e s o n a n c e
p o s i t i o n of a n y nucleus d e p e n d s o n t h e p o s i t i o n of the
n e i g h b o r i n g m a g n e t i c nuclei relative t o t h e applied
field direction, so t h e exact m a g n e t i c field experienced
by a n y p a r t i c u l a r nucleus will v a r y from molecule t o
m o l e c u l e in a n y s a m p l e w h i c h is less t h a n a perfect
single crystal. T h e s e d i p o l e - d i p o l e i n t e r a c t i o n s m a k e
it impossible t o observe a b u n d a n t spins (like p r o t o n )
at h i g h r e s o l u t i o n in a solid b y c o n v e n t i o n a l N M R
t e c h n i q u e s . U s u a l l y , p r o t o n line w i d t h s a r e b r o a d e n e d
so all fine s t r u c t u r e is h i d d e n . In liquids, h o w e v e r ,
r a p i d t u m b l i n g quickly a v e r a g e s E q n . (1) over all
possible values of 0, effectively zeroing t h e d i p o l a r
effect.
A s e c o n d possible s o u r c e of b r o a d e n i n g in solids is
a n o t h e r o r i e n t a t i o n a l effect a n d is caused by the
electronic e n v i r o n m e n t of nuclei. E l e c t r o n s n e a r a
nucleus shield it from t h e a p p l i e d field, c a u s i n g slight
p e r t u r b a t i o n s in t h e r e s o n a n c e p o s i t i o n s . T h i s effect
gives rise t o t h e chemical shift, the m o s t i m p o r t a n t
p e r t u r b a t i o n of t h e m a g n e t i c r e s o n a n c e i n t e r a c t i o n .
E l e c t r o n density, h o w e v e r , m a y n o t be h o m o g e
neously d i s t r i b u t e d a b o u t a nucleus. In t h o s e cases
w h e r e t h e electron density is n o t h o m o g e n e o u s a b o u t
a n u c l e u s , t h e r e will be a n o r i e n t a t i o n a l d e p e n d e n c e of
t h e shielding. T h i s results in a n o t h e r b r o a d e n i n g
effect in r a n d o m l y o r i e n t e d solids, called chemical
shift a n i s o t r o p y ( C S A ) . S o , in a solid w h e r e the

273

Nuclear

Magnetic

Resonance

Spectroscopy

of

Solids

molecules are r a n d o m l y oriented, chemical shifts

( b o t h the isotropic a n d a n i s o t r o p i c p a r t s ) a n d d i p o l a r
interactions with o t h e r nuclei cause r e s o n a n c e lines t o
b r o a d e n a n d o v e r l a p . (This b r o a d e n e d s p e c t r u m is
actually m a d e u p of m a n y n a r r o w e r lines at slightly
different chemical shifts d u e t o these o r i e n t a t i o n a l
effects.) A m o r e formal discussion of these effects is
given by Y a n n o n i (1982).
Pines et al. (1973) discovered t h a t nuclear m a g n e t i
z a t i o n c o u l d be transferred from a n a b u n d a n t higher
spin / t o a r a r e lower spin S in solid samples t h r o u g h a
technique they called cross-polarization. A n initial 90
pulse on the a b u n d a n t spins is followed i m m e d i a t e l y
by a s t r o n g field parallel (or antiparallel) t o the
a b u n d a n t spin m a g n e t i z a t i o n . T h i s parallel rf field
prevents the s a m p l e m a g n e t i z a t i o n from r e t u r n i n g t o
its equilibrium p o s i t i o n a n d is called a " s p i n l o c k . "
M a g n e t i z a t i o n t h e n transfers t o the r a r e spins by
simultaneously a p p l y i n g a n rf field t o these r a r e
spins which meets the H a r t m a n n - H a h n c o n d i t i o n
( H a r t m a n n a n d H a h n 1962)
yjHj^ysHs

(2)

where is the m a g n e t o g y r i c r a t i o a n d is the applied

field strength of the spins. In the absence of a n y
relaxation, the m a g n e t i z a t i o n of the r a r e spins is
e n h a n c e d by a factor of yjys b e y o n d the m a g n e t i z a
tion expected for a c o n v e n t i o n a l N M R e x p e r i m e n t (a
simple 90 pulse). D u r i n g this c r o s s - p o l a r i z a t i o n c o n
tact time, the r a r e spin m a g n e t i z a t i o n g r o w s as
1 - Qxp(-t/TIS)
w h e r e t is the c o n t a c t time a n d TIS is
the time c o n s t a n t for the transfer of m a g n e t i z a t i o n
from the a b u n d a n t t o the r a r e spins (curve (a) of Fig.
1). R e l a x a t i o n effects will diminish this e n h a n c e m e n t
factor. A s cross-polarization progresses, m a g n e t i z a
tion is exponentially decaying in a time c h a r a c t e r i z e d
by Tlp (curve b in Fig. 1). T h u s , the observed e n h a n c e
m e n t as a function of c r o s s - p o l a r i z a t i o n time t is j u s t
^ [ l - e x p ( - / / r / 5) ] e x p ( - i / r l p)

(3)

(curve c of Fig. 1). A s Fig. 2 a n d T a b l e 1 illustrate, this

relaxation effect c a n h a v e a significant effect o n the
observed e n h a n c e m e n t . It follows from E q n . (3) t h a t
m a x i m u m e n h a n c e m e n t is at a c r o s s - p o l a r i z a t i o n time
of \n(TJTIS+
\)TI?. Besides this p o t e n t i a l e n h a n c e
m e n t in m a g n e t i z a t i o n , a n d therefore signal strength,
cross-polarization offers a n o t h e r benefit: the crossp o l a r i z a t i o n process c a n be r e p e a t e d after the a b u n
d a n t spin relaxes, irrespective of the state of the r a r e
spin m a g n e t i z a t i o n a n d / o r relaxation r a t e . O f c o u r s e ,
this is because the r a r e spin m a g n e t i z a t i o n is totally
derived from the a b u n d a n t spins.
In the s a m e w o r k , Pines a n d c o - w o r k e r s also
s h o w e d t h a t a significant i m p r o v e m e n t in resolution
could be achieved by d e c o u p l i n g the a b u n d a n t spin
d u r i n g the acquisition of the r a r e spin signal. T h i s
r e m o v e s the d i p o l a r effect of a b u n d a n t spins, leaving
only C S A as a source of b r o a d e n i n g . Schaefer et al.

274

Cross-polarization time

Figure 1
Theoretical cross-polarization dynamics: (a) the expected
rare spin magnetization as a function of cross-polarization
time in the absence of relaxation effects (the single
exponential curve is characterized by a time constant TIS);
(b) spin (either rare or abundant) relaxation (the
exponential curve is characterized by a time constant TXp
which, in this example, is eight times the
cross-polarization time TIS)\ and (c) the expected rare spin
magnetization as a function of cross-polarization time, is
the product of curves (a) and (b) with the time axis in
units of TIS and the enhancement axis in units of y,jys
(notice that for this example, maximum enhancement is
achieved at a cross-polarization time of about 2.2 TIS and
is about 67% of the theoretical maximum)

1.0

1.0

2.0

3.0

4.0

5.0

Cross-polarization time

Figure 2
A family of curves showing the cross-polarization
magnetization as a function of cross-polarization time; in
each curve, TIS is constant and Tx is varied; the ratio
TJTiS is (a) 1.0, (b) 2.0, (c) 4.0, (d) 8.0 and (e) 16.0; axis
units are as in Fig. 1

Nuclear

Table 1
The time of occurrence and the value of the maximum
enhancement of cross-polarization for various values of
TJTIS

Magnetic

Resonance

Spectroscopy

of

Solids

(a)

Enhancement
%

TJTa
1.0
2.0
4.0
8.0
16.0

0.69
1.10
1.61
2.20
2.83

25
38
53
68
79

a The enhancement is a percentage of the theoretical maximum ,/

(1975) s h o w e d t h a t if t h e c r o s s - p o l a r i z a t i o n experi
m e n t w a s p e r f o r m e d while t h e solid s a m p l e w a s
spinning a t a sufficiently high r a t e (several t h o u s a n d
revolutions p e r second) a t a n o r i e n t a t i o n w h e r e E q n .
(1) is zero (a state k n o w n as m a g i c - a n g l e s p i n n i n g ) ,
resolution a p p r o a c h i n g t h a t of liquid s a m p l e s c a n be
o b t a i n e d . S p i n n i n g a t a r a t e larger t h a n t h e C S A
causes the C S A of e a c h individual spin t o b e a v e r a g e d
to the i s o t r o p i c chemical shift value. If t h e s p i n n i n g
r a t e is less t h a n t h e C S A , s p i n n i n g s i d e b a n d s a r e
observed. F i g u r e 3 s h o w s t h e effect of s a m p l e s p i n n i n g
rate on the carbon-13 cross-polarization magic-angle
spinning ( C P M A S ) s p e c t r u m of G e n e r a l Electric
L e x a n (bisphenol A p o l y c a r b o n a t e ) resin. It c a n b e
seen from F i g . 3 b t h a t t h e intensities of t h e s p i n n i n g
s i d e b a n d s a p p r o x i m a t e l y m i m i c t h e s h a p e of t h e
n o n s p i n n i n g line s h a p e s .
T h e s e i m p o r t a n t discoveries of Pines a n d Schaefer,
a n d the w o r k o n w h i c h they a r e b a s e d , p r o v i d e t h e
f o u n d a t i o n for t h e m o s t p o p u l a r f o r m of highresolution solid-state N M R , t h e C P M A S e x p e r i m e n t .
C o n d i t i o n s for t h e h i g h - r e s o l u t i o n o b s e r v a t i o n of
a b u n d a n t spins (i.e., p r o t o n s ) were w o r k e d o u t later
and combined magic-angle spinning with multiple
pulses d u r i n g t h e acquisition of t h e signal ( h o m o n u c lear d e c o u p l i n g ) a n d will n o t b e discussed in this
article.
1. General

300

200

IOO

-100

Chemical shift (ppm)

Figure 3
Carbon-13 cross-polarization spectra of a sample of GE
Lexan resin are shown spining at (a) 7940 Hz, (b) 3460 Hz
and (c) not spinning. All spectra were obtained with a
2.5 m cross-polarization with ycHc = = 55 kHz.
Spectrum (a) shows only minor spinning sidebands, while
(b) shows many sidebands, especially from the aromatic
resonances, whose chemical shift anisotropics are expected
to be higher. Spectrum (c) is nonspinning, showing
overlapping resonances broadened by CSA

Instrumentation

While t h e r e q u i r e m e n t s for C P M A S N M R a r e similar

t o t h o s e for liquid N M R , there a r e several i m p o r t a n t
differences. S u p e r c o n d u c t i n g m a g n e t s p r o v i d e stable,
high-field, h i g h - h o m o g e n e i t y applied fields for t h e
N M R e x p e r i m e n t . In fact, t h e q u a l i t y of m o d e r n
s u p e r c o n d u c t i n g m a g n e t s is such t h a t
field/frequency
stabilization ( N M R lock) is n o t r e q u i r e d . R o o m t e m p e r a t u r e access for t h e C P M A S p r o b e is typically
larger t h a n for N M R of liquids b e c a u s e of t h e special
g e o m e t r y a n d t h e higher rf p o w e r h a n d l i n g r e q u i r e
m e n t s , n e e d i n g physically larger electronic c o m
p o n e n t s . A l s o , o w i n g t o t h e limited r e s o l u t i o n of t h e
typical C P M A S s p e c t r u m a n d t h e b u l k y a n d u n u s u a l

g e o m e t r y of t h e p r o b e , r o o m - t e m p e r a t u r e h o m o
geneity s h i m coils h a v e only a m o d e s t i m p a c t o n
s p e c t r u m q u a l i t y a n d h a v e been o m i t t e d o n s o m e
solids-only N M R s p e c t r o m e t e r s .
R a d i o - f r e q u e n c y field s t r e n g t h r e q u i r e m e n t s for
C P M A S N M R a r e typically 1-2 o r d e r s of m a g n i t u d e
higher t h a n for N M R of liquids, resulting in p o w e r
r e q u i r e m e n t s r a n g i n g from a l m o s t 100 W t o several
k i l o w a t t s , d e p e n d i n g o n t h e p r o b e efficiency. T h e
C P M A S p r o b e is t h e u n i q u e p a r t of a solids N M R
s p e c t r o m e t e r . Several different designs a r e c o m m e r
cially available a n d all s h a r e t h e following features:

275

Nuclear

Magnetic

Resonance

Spectroscopy

of

Solids

(a)

a s a m p l e s p i n n i n g system consisting of a r o t o r
(spinner) m a d e of a h i g h - s t r e n g t h m a t e r i a l t o
h o l d t h e s a m p l e t u r b i n e l i k e impellers a r e p a r t
of the r o t o r so t h a t it m a y be s p u n b y pressurized
gas flowing over these features;

(b)

a s t a t o r (spinner h o u s i n g ) which p r o v i d e s p r e s
surized gas t h r o u g h a b e a r i n g surface in w h i c h
the r o t o r will s p i n t h e s t a t o r is m o u n t e d in the
p r o b e so t h a t t h e s a m p l e spins a t the m a g i c angle
( ~ 54.7) relative t o t h e applied m a g n e t i c field;
and

(c)

a d o u b l e t u n e d rf coil (usually p a r t of the s t a t o r )

with suitable t u n i n g circuitry t o efficiently c o u p l e
the h i g h - p o w e r t r a n s m i t t e r s t o t h e coil, resulting
in the highest possible rf field s t r e n g t h s .

In a d d i t i o n , the p r o b e m a y h a v e o t h e r features such

as spin r a t e d e t e c t o r s ( a n a l o g o r digital), spin r a t e
controllers o r variable t e m p e r a t u r e c o n t r o l .

2. Sample

Requirements

Solid samples from a variety of sources c a n be

successfully o b s e r v e d by C P M A S N M R . O b v i o u s
choices are crystalline, polycrystalline a n d a m o r p h o u s
solids as well as plastics a n d liquid crystalline m a t e r
ials. It is also possible t o observe c l a t h r a t e s , inclusion
complexes, c o m p o s i t e s , m i x t u r e s , melts a n d o t h e r
compounded materials. Powdered or granular mater
ial is easiest t o spin, a l t h o u g h a n y t h i n g which fits i n t o
the r o t o r will usually w o r k . Physically large s a m p l e s
need t o b e r e d u c e d in size until particles a r e smaller
t h a n the inner d i m e n s i o n s of the r o t o r (internal
d i a m e t e r s a r e typically 2 - 2 0 m m ) . L a r g e particles a r e
usually m o r e difficult t o spin a n d s o m e t i m e s require
s o m e signal-free b a l a n c i n g m a t e r i a l . W i t h s o m e c o n
straints a n d care, highly viscous fluids a n d gels (i.e.,
c o n c e n t r a t e d biological fluids, solutions a n d suspen
sions a n d p e t r o p h y s i c a l fluids) c a n be r u n . I n cases
w h e r e spinning m i g h t eliminate liquid from t h e s a m
ple, they c a n be s p u n in a special sealed r o t o r .
M a t e r i a l s which c o n d u c t electricity a r e usually n o t
suitable for M A S . H o w e v e r , in s o m e cases these
samples c a n be s p u n b y diluting t h e m a t e r i a l with a n
a p p r o p r i a t e i n s u l a t o r . A l s o , s a m p l e s which efficiently
t u r n rf energy i n t o h e a t p r e s e n t special p r o b l e m s .
Because of t h e high rf p o w e r levels involved, a n
extremely low rf d u t y cycle is used, which usually
limits the resolution of t h e detected signal.

3.

Applications

In the simplest C P M A S e x p e r i m e n t , chemical shift

i n f o r m a t i o n of t h e r a r e spin nuclei is o b t a i n e d . Alem a n y et al. (1983a) h a v e s h o w n t h a t , for m o s t o r g a n i c
c o m p o u n d s , a 2.25 m s c r o s s - p o l a r i z a t i o n c o n t a c t time

276

1 3

will result in n e a r - q u a n t i t a t i v e C N M R intensities,

m a k i n g it r o u t i n e t o o b t a i n reliable i n t e g r a t i o n d a t a .
W h i l e the C P M A S resolution routinely o b t a i n e d is
still a c o u p l e of o r d e r s of m a g n i t u d e p o o r e r t h a n t h a t
o b t a i n e d in N M R of liquids, it is usually possible t o
identify m o s t chemical types of the r a r e spins. H o w
ever, it is usually impossible t o identify a u n i q u e
chemical type in t h e presence of o t h e r similar c h e m
ical types b e c a u s e of t h e limited r e s o l u t i o n . Successful
strategies for t h e analysis of chemical processes in
solids usually involve a c o m p a r i s o n of the C P M A S
spectra of related m a t e r i a l s . F o r e x a m p l e , Maciel
a n d c o - w o r k e r s h a v e been able t o d e d u c e t h e c h e m
ical m e c h a n i s m of t h e c u r i n g process of u r e a f o r m a l d e h y d e (Maciel et al. 1983) a n d p h e n o l i c
13
(Bryson et al. 1983) resins b y c o m p a r i n g C C P M A S
spectra of resin s a m p l e s subjected t o different c u r i n g
times. I n the case of p o l y m e r s , c r y s t a l l i n e - a m o r p h o u s
m o r p h o l o g y m a y b e distinguishable t h r o u g h a n
analysis of o b s e r v e d line s h a p e s . A variety of relax
a t i o n m e a s u r e m e n t s c a n b e p e r f o r m e d in o r d e r t o
obtain information about molecular motion, microstructure and macrostructure and morphology. The
a b u n d a n t spin as well as the r a r e spin d y n a m i c s c a n b e
o b s e r v e d t h r o u g h t h e r a r e spin m a g n e t i z a t i o n , a l o n g
with t h e d y n a m i c s of m a g n e t i z a t i o n transfer. E s
pecially sensitive t o lower frequency m o t i o n s ,
m e a s u r e m e n t of TXp h a s been useful in the s t u d y of
m a c r o m o l e c u l e s (Belfiore et al. 1983).
Homonuclear decoupling technology has m a d e
available special d e c o u p l i n g sequences which selecti
vely disable h o m o n u c l e a r d i p o l e - d i p o l e i n t e r a c t i o n s .
A p p l i e d t o the a b u n d a n t spins, several new solids
techniques were developed. If t h e a b u n d a n t spin
d i p o l e - d i p o l e i n t e r a c t i o n is sufficiently w e a k , applica
tion of h o m o n u c l e a r d e c o u p l i n g m a k e s it possible t o
observe ( a n d use) scalar c o u p l i n g b e t w e e n the r a r e
a n d a b u n d a n t spins. F o r e x a m p l e , Zilm a n d G r a n t
1 3
1
(1982) h a v e o b s e r v e d C - H scalar c o u p l i n g in a d a m a n t a n e a n d h e x a m e t h y l b e n z e n e . I n a n o t h e r ex
1 3
1
a m p l e , T e r a o et al. (1982) h a v e used C - H scalar
1 3
c o u p l i n g in c a m p h o r t o o b t a i n / - r e s o l v e d C spectra.
W h i l e these a n d o t h e r similar results a r e very interest
ing, m o s t solid samples d o n o t h a v e the r e q u i r e d w e a k
d i p o l e - d i p o l e i n t e r a c t i o n t o allow t h e scalar c o u p l i n g
t o be o b s e r v e d a n d / o r exploited.
In a n o t h e r m o r e useful a p p l i c a t i o n of h o m o n u c l e a r
decoupling, a two-dimensional experiment has been
d e v e l o p e d in w h i c h each r a r e spin b e c o m e s a sensitive
p r o b e of its local d i p o l a r e n v i r o n m e n t ( M u n o w i t z et
al. 1981, Schaefer et al. 1983). In this e x p e r i m e n t ,
multiple d a t a sets a r e collected. I n e a c h sequential
d a t a set a n evolving p e r i o d of h o m o n u c l e a r d e c o u
pling is applied t o t h e a b u n d a n t spins before t h e
detection of t h e r a r e spin signal. Projecting t h e p r o
cessed d a t a a l o n g the e v o l u t i o n axis s h o w s a n o r m a l
C P M A S s p e c t r u m . Slices a l o n g t h e e v o l u t i o n direc
tion s h o w the local d i p o l a r field for e a c h of t h e
resolved nuclei. Because of E q n . (1) a n d because

Nuclear

of t h e r a r e spin r e s o l u t i o n typically achievable,

these spectra c a n be rich in distance a n d g e o m e t r y
information.

4.

Magnetic

Resonance

Spectroscopy

of

Solids

Finally, in s o m e cases, c r o s s - p o l a r i z a t i o n spin

d y n a m i c s m a y n o t be suitable for a successful experi
is t o o
m e n t . A s s h o w n in Fig. 2, if t h e r a t i o TJTIS
small, c r o s s - p o l a r i z a t i o n m a y be difficult o r i m p o s
sible t o detect ( A l e m a n y et al. 1983b).

Limitations

While C P M A S N M R c a n a p p r o a c h the resolution of

the N M R of liquids, it is typical for a C P M A S
s p e c t r u m r e s o l u t i o n t o b e limited t o several p a r t s p e r
million ( p p m ) . A m o r p h o u s m a t e r i a l s a n d p o l y m e r s
m a y h a v e a d i s t r i b u t i o n of i s o t r o p i c chemical shifts
for individual c a r b o n s d u e t o a variety of c a r b o n
e n v i r o n m e n t s in t h e solid m a t r i x . It h a s been s h o w n
t h a t p o l y m e r s which h a v e u n d e r g o n e severe m e c h a n i
cal stress h a v e b r o a d e n e d C P M A S spectra. V a n d e r H a r t et al. (1981) h a v e p u b l i s h e d a c o m p r e h e n s i v e
s t u d y of resolution limitations of C P M A S N M R .
T h e C P M A S t e c h n i q u e relies o n the p r e m i s e t h a t
equilibrium m a g n e t i z a t i o n of t h e a b u n d a n t spins is
m a n y times larger t h a n t h a t of t h e r a r e spins a n d t h a t
r a r e spins d o n o t interact with each o t h e r . Systems
t h a t c o n t a i n r a r e spins which s h a r e a chemical b o n d
present new p r o b l e m s . F o r e x a m p l e , a s a m p l e w h i c h
c o n t a i n s a high e n r i c h m e n t of c a r b o n - 1 3 will s h o w
particularly b r o a d c a r b o n r e s o n a n c e s as they i n t e r a c t
with o n e a n o t h e r t h r o u g h their d i p o l a r fields. A n o t h e r
m o r e c o m m o n s i t u a t i o n which c a n limit resolution is
the presence of q u a d r u p o l a r nuclei. T h e s e nuclei
orient their q u a d r u p o l e m o m e n t s in their m o l e c u l a r
e n v i r o n m e n t a n d c a n g e n e r a t e a powerful m a g n e t i c
field a l o n g their q u a d r u p o l e m o m e n t s . T h i s a d d i t i o n a l
field a d d s t o t h e applied field a n d modifies o t h e r spins
i n t e r a c t i o n s , resulting in line b r o a d e n i n g ( N a i t o et al.
1981). T h i s effect c a n be m i n i m i z e d by increasing t h e
applied field s t r e n g t h , which decreases t h e relative
c o n t r i b u t i o n of the field g e n e r a t e d by t h e q u a d r u p o l a r
nucleus (Maciel et al. 1983). O f c o u r s e this s o l u t i o n is
n o t always available if n o higher-field N M R spec
t r o m e t e r with solids capability is accessible. E v e n if
higher-field i n s t r u m e n t s a r e available, o t h e r c o m p l i c a
tions c a n arise in very-high-field C P M A S N M R . A s
the applied field is increased, so d o e s C S A , r e q u i r i n g
higher s a m p l e s p i n n i n g rates t o o b t a i n p u r e i s o t r o p i c
r e s o n a n c e s a n d a m i n i m u m of s p i n n i n g side b a n d s ,
m a k i n g spectral i n t e r p r e t a t i o n m o r e difficult. W h e n
spinning rates begin t o a p p r o a c h the m a g n i t u d e of t h e
H a r t m a n n - H a h n rf field, this m e c h a n i c a l m o t i o n will
begin t o interfere with the c r o s s - p o l a r i z a t i o n d y n a
mics, resulting in lower c r o s s - p o l a r i z a t i o n efficiency,
until finally, n o signal c a n be o b s e r v e d ( W i n d et al.
1988). In t h o s e cases, o b t a i n i n g a s p e c t r u m with
sample s p i n n i n g s i d e b a n d s is usually preferred. Alter
natively, D i x o n (1981) h a s devised a C P M A S N M R
experiment t o s e p a r a t e s p i n n i n g s i d e b a n d s from iso
t r o p i c r e s o n a n c e s , a l t h o u g h this e x p e r i m e n t m a y n o t
always p r o d u c e t h e desired results, s o m e t i m e s d i s t o r t
ing intensities d u e t o r e l a x a t i o n effects.

5.

Summary
13

W h i l e C - * H c r o s s - p o l a r i z a t i o n w a s t h e focus of this
15
article o t h e r nuclei c a n be o b s e r v e d , including N ,
29
119
3 1
S i , S n a n d P . It is also possible t o generate crossp o l a r i z a t i o n intensity from nuclei o t h e r t h a n . F o r
1 3
l 9
e x a m p l e , C - F C P M A S s p e c t r a c a n be o b t a i n e d
o n fluorinated p o l y m e r s . In a n u m b e r of respects,
C P M A S N M R is e x p e r i m e n t a l l y m o r e d e m a n d i n g
t h a n c o n v e n t i o n a l N M R of liquids. H o w e v e r , like
N M R of liquids, C P M A S N M R is invaluable in the
s t u d y of solids, p r o v i d i n g b o t h static (structural) a n d
d y n a m i c ( m o t i o n a l ) i n f o r m a t i o n . While there are
s o m e s a m p l e s which c a n n o t be studied by C P M A S
N M R , this t e c h n i q u e c a n be applied t o a wide variety
of m a t e r i a l s , regardless of p u r i t y , crystallinity o r o t h e r
physical a t t r i b u t e s .

cknowledgements

T h e h e l p of E. A. Williams a n d J. S m i t h in p r e p a r i n g
this article is gratefully a c k n o w l e d g e d .
See also: Nuclear Magnetic Resonance Spectroscopy

Bibliography
Alemany L B, Grant D M, Pugmire R J, Alger D, Zilm
W 1983a Cross polarization and magic angle sample
spinning NMR spectra of model organic compounds, 1.
Highly protonated molecules. J. Am. Chem. Soc. 105:
2133-41
Alemany L B, Grant D M, Pugmire R J, Alger D, Zilm
W 1983b Cross polarization and magic angle sample
spinning NMR spectra of model organic compounds, 2.
molecules of low or remote protonation. J. Am. Chem.
Soc. 105: 2142-7
Belfiore L A, Henrichs , Massa D J, Zumbulyadis N,
Roth well W , Cooper S L 1983 Molecular dynamics of
polycarbonate-diluent systems: applications of highresolution carbon-13 solid-state NMR. Macromolecules
16: 1744-53
Bloch F, Hansen W W, Packard 1947 The nuclear
induction experiment. Phys. Rev. 70: 474-85
Bryson R L, , Hatfield
G R, Early A, Palmer A R, Maciel
3
G 1983 C NMR studies of solid phenolic resins using
cross polarization and magic-angle spinning. Macromol
ecules 16: 1669-72
Dixon W 1981 Spinning-sideband-free NMR spectra.
J. Magn. Reson. 44: 220-3

277

Nuclear

Magnetic

Resonance

Spectroscopy

of

Solids

Hartmann S R, Hahn L 1962 Nuclear double resonance in

the rotating frame. Phys. Rev. 128: 2042-53
Maciel G E, Szeverenyi , Early A, Myers G 1983
13
C NMR studies of solid urea-formaldehyde resins using
cross polarization and magic-angle spinning. Macromolecules 16: 598-604
Munowitz G, Griffin R G, Bodenhausen G, Huang
1981 Two-dimensional rotational spin-echo nuclear mag
netic resonance in solids: correlation of chemical shift and
dipolar interactions. J. Am. Chem. Soc. 103: 2529-33
Naito A, Ganapathy S, McDowell C A 1981 High resolu
13
tion solid state C NMR spectra of carbons bonded to
nitrogen in a sample spinning at the magic angle. / . Chem.
Phys. 74: 5393-7
Pines A, Gibby G, Waugh J S 1973 Proton-enhanced
NMR of dilute spins in solids. J. Chem. Phys. 59: 569-90
Purcell , Torrey HC, Pound R V 1946 Resonance
absorption by nuclear magnetic resonance. Phys. Rev. 69:
37-8
Schaefer J, McKay R A, Stejskal , Dixon W 1983
13
Dipolar rotational spin-echo C NMR of polymers.
J. Magn. Reson. 52: 123-9

278

Schaefer J, Stejskal , Buchdahl R 1975 High-resolution

carbon-13 nuclear magnetic resonance study of some
solid, glassy polymers. Macromolecules 8: 291-6
Terao T, Miura H, Saika A 1982 Simplification and assign
ment of carbon-13 spectra by using /-resolved NMR
spectroscopy in solids. / . Am. Chem. Soc. 104: 5229-30
VanderHart1 3 D L, Earl W L, Garroway A 1981 Resolu
tion in C NMR of organic solids using high-power
proton decoupling and magic-angle sample spinning.
J. Magn. Reson. 44: 361-401
13
Wind R A, Dec S F, Lock H, Maciel G 1988 C CP/MAS
and high-speed magic-angle spinning. / . Magn. Reson. 79:
136-9
Yannoni C S 1982 High-resolution NMR in solids: the
CPMAS experiment. Acc. Chem. Res. 15: 201-8
Zilm W, Grant D 1982 High-resolution NMR spectra
with J coupling in solids. / . Magn. Reson. 48: 524-6
T. A . Early
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]


Optical Calorimetry
Optical c a l o r i m e t r y is a n e x p e r i m e n t a l m e t h o d used
to d e t e r m i n e t h e optical a b s o r p t a n c e o r a b s o r p t i o n
coefficient in w e a k l y a b s o r b i n g m a t e r i a l s . W h i l e
gases, liquids a n d solids m a y be studied u s i n g this
t e c h n i q u e , in practice c a l o r i m e t r i c m e t h o d s a r e m o s t
often used t o m e a s u r e t h e a b s o r p t i o n in low-loss
w i n d o w s a n d m i r r o r s . F u r t h e r m o r e , since t h e m e t h o d
relies o n m e a s u r i n g t h e small t e m p e r a t u r e rise
b r o u g h t a b o u t by t h e a b s o r p t i o n of optical energy,
laser sources a r e usually r e q u i r e d t o e n s u r e sufficient
heating. In c a l o r i m e t r y , t h e a b s o r p t i o n is d e t e r m i n e d
by m e a s u r i n g in s o m e w a y t h e t e m p e r a t u r e rise c a u s e d
by the laser r a d i a t i o n striking t h e optical c o m p o n e n t
a n d relating this increase t o p o w e r a b s o r b e d in t h e
sample. G e n e r a l l y , t h e t e m p e r a t u r e rise is simply
m e a s u r e d with a t h e r m o c o u p l e a l t h o u g h a n interferometric t e c h n i q u e h a s b e e n used t o m e a s u r e this in
crease by o b s e r v i n g t h e c h a n g e in optical p a t h as t h e
c o m p o n e n t is h e a t e d .

/.

Adiabatic

Thermocouple

mC(dT/dt)

Calorimetry

A d i a b a t i c c a l o r i m e t r y , in w h i c h a t h e r m o c o u p l e o r
t h e r m i s t o r is used t o m e a s u r e t e m p e r a t u r e a n d a laser
is used as a h e a t s o u r c e , is b y far t h e m o s t c o m m o n
calorimetric t e c h n i q u e . S a m p l e s c a n b e i l l u m i n a t e d
with as little as a few h u n d r e d milliwatts of
c o n t i n u o u s - w a v e laser p o w e r t o o b t a i n a b s o r p t i o n
6
_ 1
coefficients as low as 1 0 ~ c m . L a s e r w a v e l e n g t h s
from the millimeter t o ultraviolet region h a v e been
used to o b t a i n values of t h e a b s o r p t i o n in h i g h - p o w e r
laser w i n d o w m a t e r i a l s , e n h a n c e d reflectors, thin-film
c o a t i n g s a n d low-loss fiber-optic w a v e g u i d e s . Since
the t e c h n i q u e p r o v i d e s a n a b s o l u t e m e a s u r e of
a b s o r p t i o n w i t h o u t the need for a n y reference o r
calibrated s t a n d a r d s , a n d b e c a u s e it is extremely
sensitive a n d simple t o use, it h a s w i d e s p r e a d u s a g e .
T h e basic features of a laser c a l o r i m e t e r a r e s h o w n
in Fig. 1. T h e s a m p l e is t h e r m a l l y isolated from t h e
s u r r o u n d i n g s b y insulating p i n s (e.g., n y l o n ) a n d a
differential t h e r m o c o u p l e is a t t a c h e d t o t h e s a m p l e
a n d a n e a r b y t h e r m a l m a s s (reference p o i n t ) .
Generally, t h e c a l o r i m e t e r is e v a c u a t e d b u t , since t h e
analysis includes t h e effects of c o n d u c t i o n a n d c o n
vection h e a t losses, the m e a s u r e m e n t s c a n , in m a n y
cases, be d o n e in air. T h e small t e m p e r a t u r e rise o n
laser h e a t i n g is m e a s u r e d with a n a n o v o l t m e t e r a n d
the t e m p e r a t u r e - t i m e c u r v e is r e c o r d e d o n a stripc h a r t recorder. F r o m this c u r v e , t h e t h e r m a l rise dT/dt
can be o b t a i n e d a n d related t o t h e a b s o r p t i o n coeffi
cient using a simple h e a t - b a l a n c e relation:

= Pa = (n

\)PLPJ2n

(1)

w h e r e m is the s a m p l e m a s s , C is the specific heat, Pa

a n d Pt a r e t h e a b s o r b e d a n d t r a n s m i t t e d (or reflected)
p o w e r s , respectively, a n d L is t h e length of the s a m
2
ple. T h e t e r m (n + \)/2n, w h e r e is t h e index of
refraction, a c c o u n t s for surface reflection losses in
t r a n s p a r e n t m a t e r i a l s ; for reflectors = 1.

2. Bulk and Surface

Absorption

A l t h o u g h E q n . (1) f o r m s t h e basis of the calorimetric

m e a s u r e m e n t s , a m o r e c o m p l e t e analysis of the
thermal-rise curves n o t only gives m o r e a c c u r a t e
values of b u t m a y also yield values of the bulk (fih)
a n d surface (S) a b s o r p t i o n as well. F i g u r e 2 s h o w s the
h e a t i n g - c o o l i n g curves o b t a i n e d for t w o different
sample geometries. Usually samples are disk-shaped
(Fig. 2a), a n d for these s a m p l e s t h e h e a t i n g c u r v e is
a p p r o x i m a t e l y linear. T h e d a t a a r e generally analyzed
using a three-slope m e t h o d in w h i c h the initial a n d
final c o o l i n g rates (regions 1 a n d 3 in Fig. 2a) a r e
t a k e n i n t o a c c o u n t . U s i n g the slopes T\, T2, a n d T\
(T' = dT/dt), a n d t e m p e r a t u r e s Tx, T2 a n d 3 (Fig. 2a),
a modification of E q n . (1) t h a t a c c o u n t s for h e a t
losses c a n be derived:
m

\ j '

- T \ - { T \ - T \ ) ( ^ ^ ^
2

= (n + \WLPJ2n

(2)

w h i c h is valid for a b s o r p t a n c e s /?L <^ 1.

T h e m e a s u r e d a b s o r p t i o n coefficient is the t o t a l
a b s o r p t i o n w h i c h m a y be s e p a r a t e d i n t o b u l k a n d
surface c o n t r i b u t i o n s :

Nylon pin
^Sample

Thermocouple

J^^^^^~^

Recorder

Figure 1
Experimental arrangement for laser calorimetry. The
sample is thermally isolated with nylon pins and the
calorimeter itself (with windows) is typically evacuated

279

Optical

Calorimetry

ptL

= p&L

+ 2S

(3)

F r o m E q n . (3) it c a n b e seen t h a t t h e m o s t direct

m e t h o d t o o b t a i n /? b a n d S is t o m e a s u r e fiTL as a
function of s a m p l e length ( c u t - b a c k m e t h o d ) a n d t h e n
to p l o t PTL a g a i n s t L. T h e slope of this p l o t is /? b a n d
t h e o r d i n a t e intercept is t h e t o t a l surface a b s o r p t a n c e
2S. A n o t h e r m e t h o d m a k e s use of a l o n g b a r - s h a p e d
s a m p l e g e o m e t r y (Fig. 2b). In this t e c h n i q u e t h e
t h e r m o c o u p l e is p l a c e d in t h e c e n t e r of a b a r o r r o d s h a p e d s a m p l e w h o s e aspect r a t i o (length t o d i a m e t e r )
is a p p r o x i m a t e l y 1 0 : 1 . Bulk a n d surface a b s o r p t i o n
a r e s e p a r a t e d b e c a u s e t h e t r a n s i t t i m e for surface h e a t
t o travel d o w n a l o n g r o d is g r e a t e r t h a n t h e t r a n s i t
time for b u l k h e a t t o arrive a t t h e center t h e r m o
c o u p l e . T h i s m e a n s t h a t t h e first h e a t i n g slope is a
m e a s u r e of b u l k a b s o r p t i o n only a n d t h a t t h e final
h e a t i n g slope c o n t a i n s t h e c o n t r i b u t i o n from b o t h
b u l k a n d surface a b s o r p t i o n (Fig. 2 b ) . T o use this
m e t h o d , t h e t r a n s i t t i m e for surface h e a t (given b y
2
w h e r e is t h e t h e r m a l diffusivity)
5 ~ (%L) /2K,
s h o u l d b e l o n g c o m p a r e d with t h e t r a n s i t t i m e for
2
b u l k h e a t i n g (given by r b ~
(\b) JK).
A s a n e x a m p l e of l o n g - b a r c a l o r i m e t r y , t h e
t h e r m a l - r i s e c u r v e for single-crystal K C 1 is s h o w n in
Fig. 3. T h e three-slope m e t h o d ( E q n . (2)) h a s b e e n
used t o a n a l y z e this d a t a t a k e n a t 10.6 using a
C 0 2 laser. T h e values o b t a i n e d for /? b a n d S
5
_1
5
a r e 9.0 x 1 0 ~ c m a n d 9.9 1 0 " , respectively. T h e
v a l u e of /? b is essentially intrinsic a n d t h e surface
a b s o r p t a n c e is r e p r e s e n t a t i v e of a very g o o d surface
finish.

3.

Thin-Film

Absorption

360

Figure 3
Experimental thermal-rise curve for KC1 at 10.6 . The
initial slope provides the bulk absorption /?b, and from the
final bulk plus surface slope the surface absorption S can
be obtained. The initial jump is associated with light
scattered directly onto the thermocouple

t a n c e m e a s u r e d in t h e film p l u s s u b s t r a t e At w i t h
t h e a b s o r p t a n c e of t h e s u b s t r a t e a l o n e As; t h a t
is, A{= At As. I n this w a y , t h e a b s o r p t a n c e s of
single-layer
or
multilayer
antireflection
and
enhanced-reflection films h a v e b e e n m e a s u r e d for
films d e p o s i t e d o n s t a n d a r d d i s k - s h a p e d w i n d o w s a n d
m i r r o r s . T h e l o n g - b a r t e c h n i q u e h a s also b e e n used t o
o b t a i n A{ b y d e p o s i t i n g a film o n o n e e n d of t h e b a r .
T h e r m o c o u p l e s p l a c e d a t b o t h e n d s of t h e b a r , a n d in
t h e m i d d l e , p r o v i d e different t h e r m a l - r i s e curves
w h i c h m a y be a n a l y z e d t o o b t a i n A{ directly w i t h o u t
the need to subtract the substrate absorption.

T h e a b s o r p t a n c e of a thin-film c o a t i n g A{ m a y b e
o b t a i n e d calorimetrically by c o m p a r i n g t h e a b s o r p 4. Other

laser
off

laser
on

3 L
bulk
] heating

laser
off

bulk and
surface
heating
!

Figure 2
Thermal-rise curves obtained for (a) typical disk-shaped
samples and (b) long-bar samples. Data are analyzed
using the temperatures and slopes from the three regions:
(1) initial cooling, (2) laser heating and (3) final cooling

280

Optical

Calorimetric

Methods

I n s t e a d of m e a s u r i n g laser h e a t i n g with t h e r m o
c o u p l e s , t h e t e m p e r a t u r e increase m a y b e d e t e r m i n e d
by m e a s u r i n g t h e c h a n g e in o p t i c a l p a t h length of t h e
s a m p l e . I n this m e t h o d t h e s a m p l e is p l a c e d in a n
interferometer a n d illuminated with a heating b e a m
a n d a p r o b e b e a m t o m o n i t o r t h e fringe c h a n g e s o n
h e a t i n g . F r o m t h e c o m p u t e d c h a n g e in optical p a t h
length, t h e coefficient of t h e r m a l e x p a n s i o n a n d t h e
t e m p e r a t u r e coefficient of t h e refractive index, t h e
s a m p l e h e a t i n g a n d h e n c e m a y be o b t a i n e d . T h e
m e t h o d h a s a d v a n t a g e s in t h a t n o s e n s o r t o u c h e s t h e
s a m p l e ( m i n i m i z i n g scattered-light p r o b l e m s ) , a n d
relatively low s o u r c e energies m a y b e used. I n a d d i
tion, path-length changes occur quicker than thermal
diffusion, so t h a t t h e m e t h o d is faster t h a n t h e r m o
couple calorimetry. However, experimental and com
p u t a t i o n a l complexities h a v e limited w i d e s p r e a d use
of this m e t h o d .
See also: Thermal Analysis: An Overview

Optical

= c/v

Bibliography
Harrington J A, Braunstein M, Rudisill J 1977 Measuring
the infrared absorption in thin film coatings. Appl. Opt.
16: 2843-6
Hass 1978 Measurement of very low optical absorption
coefficients in bulk materials. Opt. Eng. 17: 525-9
Hordvik A 1977 Measurement techniques for small absorp
tion coefficients: recent advances. Appl. Opt. 16: 2827-33
Klein 1981 Techniques for measuring absorption coeffi
cients in crystalline materials. Opt. Eng. 20: 790-4
Rosenstock H, Hass M, Gregory D A, Harrington J A 1977
Analysis of laser calorimetric data. Appl. Opt. 16: 2837-42
J. A . H a r r i n g t o n
[Hughes Research Laboratories,
M a l i b u , California, U S A ]

Optical Emission Spectroscopy

Optical emission s p e c t r o s c o p y is a t e c h n i q u e used for
elemental analysis of solids a n d liquids. W h e n s a m
ples a r e v a p o r i z e d a n d excited b y a suitable emission
source, t h e c o n s t i t u e n t a t o m s emit r a d i a t i o n in t h e
optical region of t h e e l e c t r o m a g n e t i c s p e c t r u m . T h e
optical region consists of t h e ultraviolet, visible a n d
near-infrared p o r t i o n s of t h e e l e c t r o m a g n e t i c spec
t r u m . Every excited e l e m e n t emits a characteristic line
s p e c t r u m t h a t c a n be used t o identify t h a t element.
U n d e r identical excitation c o n d i t i o n s a n d with identi
cal s a m p l e types, t h e intensity of t h e light e m i t t e d a t a
given w a v e l e n g t h d e p e n d s only u p o n c o n c e n t r a t i o n .
T h i s is the basis of t h e use of t h e t e c h n i q u e for
q u a n t i t a t i v e elemental analysis.
Analytically i m p o r t a n t sources include d c a r c , a c
s p a r k , flames a n d t h e inductively c o u p l e d p l a s m a .
O t h e r sources t h a t a r e g a i n i n g a t t e n t i o n as analytical
tools are t h e h o l l o w - c a t h o d e l a m p a n d t h e glowdischarge l a m p . T h e light e m i t t e d by t h e s o u r c e is
resolved i n t o its c o m p o n e n t w a v e l e n g t h s a n d detected
photoelectrically b y a s p e c t r o m e t e r .

Spectra

Line spectra arise from t r a n s i t i o n s b e t w e e n different

electronic energy levels of excited a t o m s o r ions in t h e
gaseous state. T r a n s i t i o n s involving t h e outer-shell
electrons of a n a t o m p r o d u c e optical spectra; t r a n s i
tions involving inner-shell electrons p r o d u c e x-ray
spectra. In a n emission s o u r c e , a t o m s a r e excited b y
inelastic collisions with electrons o r o t h e r a t o m s .
W h e n a n a t o m is excited a n electron is p r o m o t e d t o a
higher energy level a n d since t h e excited state is
u n s t a b l e the electron r e t u r n s t o a lower level a n d
energy is r a d i a t e d . T h e r e l a t i o n s h i p b e t w e e n energy,
frequency a n d w a v e l e n g t h is given b y
E2-

Ex=

hv

(1)

Spectroscopy

(2)

w h e r e E2 a n d Ex a r e t h e energies of the u p p e r a n d
lower energy levels, respectively, h is P l a n c k ' s c o n
s t a n t , c is t h e speed of light, is frequency a n d is
w a v e l e n g t h . T h e speed of light d e p e n d s u p o n the
refractive index of t h e m e d i u m ; c is greater in a
v a c u u m t h a n in air a n d c o n s e q u e n t l y so is .
E a c h element h a s a u n i q u e set of electronic energy
levels a n d h e n c e emits a line s p e c t r u m u n i q u e to t h a t
element. T h i s m e a n s t h a t line spectra c a n be used for
element identification. Several extensive t a b u l a t i o n s
of line s p e c t r a a r e available a n d a r e widely used for
identifying spectral lines.
2.

1. Origin of

Emission

Spectrometers

T h e m a j o r c o m p o n e n t s of a n emission s p e c t r o m e t e r
a r e t h e e n t r a n c e a n d exit slits, t h e light-dispersing
e l e m e n t (grating o r p r i s m ) a n d t h e d e t e c t o r . M o d e r n
spectrometers incorporate computers and/or micro
p r o c e s s o r s for i n s t r u m e n t c o n t r o l a n d d a t a h a n d l i n g .
In s p e c t r o m e t e r s used below a b o u t 200 n m , the
optical p a t h is u n d e r v a c u u m .
A n emission s p e c t r o m e t e r receives light from a
s o u r c e a n d spatially resolves it i n t o its c o m p o n e n t
w a v e l e n g t h s . W a v e l e n g t h r e s o l u t i o n c a n be a c c o m
plished either w i t h a p r i s m o r with a diffraction
g r a t i n g . Light travelling t h r o u g h a p r i s m is refracted,
t h a t is, its direction c h a n g e s a c c o r d i n g t o Snell's law
a n d is d e p e n d e n t u p o n its refractive index in t h e p r i s m
m a t e r i a l . Light of s h o r t e r w a v e l e n g t h s is refracted
m o r e t h a n l o n g e r - w a v e l e n g t h light, which results in
spatial s e p a r a t i o n of t h e w a v e l e n g t h c o m p o n e n t s . A t
long wavelengths, resolution becomes poor. Most
m o d e r n emission s p e c t r o m e t e r s use reflection gratings
instead of p r i s m s ; h o w e v e r , p r i s m s a r e used in s o m e
s p e c t r o m e t e r s in c o n j u n c t i o n with g r a t i n g s as o r d e r
sorters (the p r i s m a n d g r a t i n g disperse light in per
p e n d i c u l a r directions a n d f o r m a t w o - d i m e n s i o n a l
spectrum).
A reflection g r a t i n g is a set of parallel e q u i d i s t a n t
g r o o v e s o n a reflective surface, usually a m e t a l c o a t i n g
o n a glass b l a n k . B o t h m e c h a n i c a l l y ruled a n d
h o l o g r a p h i c a l l y r e c o r d e d g r a t i n g s a r e used in spec
t r o m e t e r s . T h e surface of t h e g r a t i n g b l a n k c a n be
either p l a n e o r spherical (concave).
L i g h t is diffracted by a g r a t i n g a c c o r d i n g to
= a(sin + sin )

(3)

w h e r e is t h e angle b e t w e e n t h e incident b e a m a n d
t h e g r a t i n g n o r m a l , is t h e angle b e t w e e n the dif
fracted b e a m a n d t h e g r a t i n g n o r m a l , a is the g r o o v e
s p a c i n g a n d is a n integer (the o r d e r of the s p e c t r u m ) .
Light of a given w a v e l e n g t h will be diffracted only in
t h o s e d i r e c t i o n s t h a t satisfy E q n . (3). Light of a n o t h e r
w a v e l e n g t h will a p p e a r a t a different set of angles;
t h u s t h e c o m p o n e n t s of light from t h e source are
spatially resolved.

281

Optical

Emission

Spectroscopy

Grating

Grating

normal

Figure 1
Paschen-Runge mounting of a concave grating:
A, primary slit; B, secondary slit

S p e c t r o m e t e r s c a n be classified as s i m u l t a n e o u s
(multichannel) o r sequential (single-channel, scan
ning). Sequential s p e c t r o m e t e r s a r e analytically useful
only with emission sources t h a t a r e stable over l o n g
p e r i o d s of time, such as flames a n d the inductively
c o u p l e d p l a s m a . M u l t i c h a n n e l i n s t r u m e n t s a r e used
with all emission sources. F i g u r e 1 s h o w s a simplified
optical d i a g r a m of t h e P a s c h e n - R u n g e m o u n t i n g , the
m o s t c o m m o n l y used a r r a n g e m e n t in m u l t i c h a n n e l
s p e c t r o m e t e r s : a c o n c a v e g r a t i n g is located with its
apex o n a circle (the R o w l a n d circle). T h e p r i m a r y slit
a n d s e c o n d a r y slits also lie o n t h e R o w l a n d circle.
Light from t h e emission source enters t h e spec
t r o m e t e r t h r o u g h the p r i m a r y slit A . T h e light is
dispersed by the g r a t i n g a n d focused a t the R o w l a n d
circle. E a c h diffracted w a v e l e n g t h forms a n i m a g e of
the p r i m a r y slit. A n a r r a y of s e c o n d a r y slits a l o n g
with a slit m a s k o r a set of baffles isolates t h o s e
wavelengths t h a t a r e desired for the analysis. Behind
e a c h s e c o n d a r y slit is a p h o t o m u l t i p l i e r t u b e t o c o n
vert light i n t o a n electrical signal, which is processed
by a m i n i c o m p u t e r o r a m i c r o p r o c e s s o r a n d c o n
verted i n t o c o n c e n t r a t i o n units.
F i g u r e 2 s h o w s a n optical d i a g r a m of a singlec h a n n e l s p e c t r o m e t e r b a s e d u p o n the C z e r n y - T u r n e r
m o u n t i n g , the m o s t p o p u l a r p l a n e - g r a t i n g m o u n t i n g .
W a v e l e n g t h s a r e selected by r o t a t i n g t h e g r a t i n g
a b o u t t h e axis A . I n m o d e r n m o n o c h r o m a t o r s , g r a t
ing r o t a t i o n is c o n t r o l l e d b y a c o m p u t e r . T h e sepa
r a t i o n b e t w e e n w a v e l e n g t h s (/dx), t h e reciprocal
linear dispersion, is given by
dk/dx = (a/nf)

282

cos

(4)

w h e r e / i s t h e focal length of t h e s p e c t r o m e t e r a n d is
t h e distance a l o n g t h e focal c u r v e . R e c i p r o c a l linear
- 1
1
dispersion is expressed in A m m
or n m m m ;
smaller values represent greater w a v e l e n g t h sepa
r a t i o n . E q u a t i o n (4) s h o w s t h a t larger values of
(higher spectral o r d e r s ) p r o d u c e greater w a v e l e n g t h
s e p a r a t i o n ; for this r e a s o n it is often a d v a n t a g e o u s t o
m a k e m e a s u r e m e n t s in higher o r d e r s to minimize the
interference c a u s e d by spectral lines close t o the
analysis line. T h e practical r e s o l u t i o n of a spec
t r o m e t e r is d e t e r m i n e d by t h e b a n d p a s s , which is
the p r o d u c t of the s e c o n d a r y slit w i d t h a n d dXjdx.
Light of a given w a v e l e n g t h m a y be diffracted i n t o
m o r e t h a n o n e o r d e r . Blazed gratings a r e gratings
w h o s e g r o o v e s a r e s h a p e d in such a w a y t h a t m o s t of
t h e light of a given w a v e l e n g t h is diffracted i n t o a
single o r d e r so t h a t t h e light is used m o s t efficiently. If
a g r a t i n g is blazed a t in t h e first o r d e r , it is blazed a t
/ in the nth o r d e r .
T h e m o s t c o m m o n l y used d e t e c t o r s in emission
spectrometers are photomultiplier tubes. These con
sist of a p h o t o c a t h o d e , a n electron multiplier section
( d y n o d e s ) a n d a n electron collector ( a n o d e ) , all
enclosed in a v a c u u m t u b e . In a m u l t i c h a n n e l spec
t r o m e t e r , different types of p h o t o m u l t i p l i e r t u b e s
c a n be used, o p t i m a l for e a c h spectral region. P h o t o
8
multiplier t u b e s h a v e a large d y n a m i c r a n g e (10 ), a
5
8
high amplification factor ( 1 0 - 1 0 ) a n d fast r e s p o n s e .
A l s o of interest, b u t n o t yet widely used, a r e
photodiode array detectors. A n array can contain u p
to 2000 d i o d e s in 10 m m a n d c a n be m o u n t e d in the

Figure 2
Czerny-Turner mounting of a plane grating: A, axis of
rotation of the grating perpendicular to the plane of the
figure; B, primary slit; C, secondary slit; D, collimating
mirror; E, focusing mirror

Optical

focal p l a n e of a s p e c t r o m e t e r . T h i s device allows

m e a s u r e m e n t s t o b e m a d e a t adjacent w a v e l e n g t h s ,
which is useful for p e r f o r m i n g b a c k g r o u n d c o r r e c
4
tions. T h e d y n a m i c r a n g e of p h o t o d i o d e s is a b o u t 10 ,
which is far inferior t o t h a t of p h o t o m u l t i p l i e r t u b e s .
T h e sensitivity of p h o t o d i o d e s is p o o r b e l o w 200 n m .
C o n s e q u e n t l y , p h o t o d i o d e a r r a y s a r e m o s t useful a t
longer w a v e l e n g t h s a n d w h e n low d e t e c t i o n limits a r e
n o t of p r i m a r y i m p o r t a n c e .

3. Emission
3.1

Sources

Flames

T h e oldest a n d simplest emission sources a r e flames.

C o m m o n gas m i x t u r e s ( a n d a v e r a g e flame t e m p e r a
tures) are: a i r - m e t h a n e (1900 C), a i r - p r o p a n e
(1900 C), a i r - h y d r o g e n (2000 C), a i r - a c e t y l e n e
(2300 C), n i t r o u s o x i d e - h y d r o g e n (2600 C), o x y g e n hydrogen
(2700 C), o x y g e n - p r o p a n e
(2800 C),
n i t r o u s o x i d e - a c e t y l e n e (3000 C) a n d o x y g e n - a c e t y
lene (3100 C). T h e liquid s a m p l e is a s p i r a t e d i n t o t h e
flame w h e r e it is e v a p o r a t e d , dissociated a n d excited.
T h e r e a r e t w o types of b u r n e r s used in flame spec
troscopy: t o t a l c o n s u m p t i o n b u r n e r s a n d b u r n e r s
used with a s p r a y c h a m b e r . T o t a l c o n s u m p t i o n
b u r n e r s a s p i r a t e all of t h e s a m p l e directly i n t o t h e
flame; they a r e , h o w e v e r , t u r b u l e n t a n d noisy a n d
hence give c o m p a r a t i v e l y p o o r d e t e c t i o n limits. T h e
o t h e r type of b u r n e r is used w i t h a s e p a r a t e nebulizer
a n d s p r a y c h a m b e r . T h e larger a e r o s o l d r o p l e t s settle
o u t in the s p r a y c h a m b e r a n d r u n i n t o a d r a i n ; only
the smaller d r o p l e t s r e a c h t h e flame. Since t h e d r o p
lets r e a c h i n g t h e flame h a v e a m o r e u n i f o r m size
d i s t r i b u t i o n , noise is lower a n d d e t e c t i o n limits a r e
better for this t y p e of b u r n e r t h a n for t o t a l c o n s u m p
tion b u r n e r s . O r g a n i c solvents as well as a q u e o u s
solutions c a n be used. W i t h o r g a n i c solvents, line
intensities a r e increased b e c a u s e t h e h e a t of c o m b u s
tion of the o r g a n i c m a t e r i a l raises t h e flame t e m p e r a
ture over w h a t it w o u l d b e w h e n w a t e r is a s p i r a t e d .
T h e t e m p e r a t u r e s of flames a r e low c o m p a r e d w i t h
those of o t h e r light sources such as t h e inductively
coupled p l a s m a a n d t h e d c a r c , h e n c e relatively few
lines are excited in flames. D e t e c t i o n limits a r e highly
d e p e n d e n t u p o n t h e t y p e of flame used. T h e best
detection limits for t h e alkali m e t a l s a r e o b t a i n e d w i t h
a cool flame. E l e m e n t s t h a t t e n d t o f o r m m o l e c u l a r
c o m p o u n d s require a h o t t e r flame.
F l a m e s a r e excellent sources for d e t e r m i n i n g t h e
alkali m e t a l s a n d alkaline e a r t h s ; typical d e t e c t i o n
limits for these elements a r e several t e n t h s of a
n a n o g r a m p e r milliliter. A b o u t 50 elements c a n b e
d e t e r m i n e d b y flame emission s p e c t r o s c o p y , w i t h d e
tection limits r a n g i n g from a fraction of a n a n o g r a m
p e r milliliter t o several m i c r o g r a m s p e r milliliter. L i n e
intensities a r e very susceptible t o m a t r i x effects;
1
m o d e r a t e c o n c e n t r a t i o n s (1000 g m l " ) of easily

Emission

Spectroscopy

ionizable elements lower t h e flame t e m p e r a t u r e . I o n i

z a t i o n s u p p r e s s i o n d u e t o easily ionizable m a t r i x
elements increases t h e intensities of n e u t r a l - a t o m a n a lyte lines a n d decreases the intensities of ionic lines of
t h e a n a l y t e elements. C h e m i c a l effects a r e i m p o r t a n t
in flames; for e x a m p l e , m o d e r a t e a m o u n t s of p h o s
p h o r u s o r a l u m i n u m s u p p r e s s c a l c i u m emission b y
f o r m i n g c o m p o u n d s with calcium. E l e m e n t s such as
m o l y b d e n u m , t i t a n i u m a n d t u n g s t e n which form
refractory oxides a r e difficult t o d e t e r m i n e in flames;
t h e use of fuel-rich flames i m p r o v e s the detection
limits. A m a j o r limitation of flames is t h a t m o l e c u l a r
b a n d s of C H , C 2 , a n d C N from t h e h y d r o c a r b o n fuel
as well as O H b a n d s m a k e it difficult t o use large
p o r t i o n s of the s p e c t r u m .
3.2 Electrical

Flames

Electrical flames, including d c p l a s m a s , capacitively

c o u p l e d m i c r o w a v e p l a s m a s a n d radio-frequency
inductively c o u p l e d p l a s m a s , p r o d u c e higher t e m p e r a
tures t h a n c o m b u s t i o n flames. A t p r e s e n t these
sources a r e used r o u t i n e l y only for t h e analysis of
liquids, b u t efforts a r e being m a d e in several l a b o r a
tories t o a d a p t these sources t o t h e analysis of
p o w d e r s a n d solids.
T h e inductively c o u p l e d p l a s m a ( I C P ) is t h e m o s t
p o p u l a r a n d analytically useful of t h e electrical
flames. A n I C P is a high-frequency electrodeless dis
c h a r g e s u p p o r t e d in a t u b u l a r q u a r t z t o r c h by a gas,
usually a r g o n . T h e t o r c h is located within t h e i n d u c
tion coil of a r a d i o - f r e q u e n c y g e n e r a t o r , which s u p
plies electrical energy t o sustain t h e p l a s m a . T h e
p l a s m a is ignited b y t h e s p a r k from a Tesla coil; o n c e
s o m e a r g o n h a s been ionized, t h e radio-frequency
energy from the i n d u c t i o n coil sustains the p l a s m a .
A r g o n is t h e gas m o s t frequently used, b u t n i t r o g e n
a n d n i t r o g e n - a r g o n m i x t u r e s a r e also used. Typical
o p e r a t i n g p o w e r s for a n a r g o n p l a s m a a r e 1 0 0 0 1 7 0 0 W ; t h e m o s t c o m m o n o p e r a t i n g frequency is
27.12 M H z .
S a m p l e s a r e usually i n t r o d u c e d i n t o t h e I C P as
aerosols. T h e a e r o s o l p r o d u c e d b y a nebulizer passes
t h r o u g h t h e s p r a y c h a m b e r a n d t h e I C P t o r c h , a n d is
injected by the carrier gas i n t o t h e I C P discharge
1
( s a m p l e c o n s u m p t i o n rates a r e 1-3 m l m i n " ) . Ele
m e n t s t h a t c a n be c o n v e r t e d t o volatile forms by
r e d u c t i o n with s o d i u m b o r o h y d r i d e , such as arsenic,
selenium a n d tin (hydrides) a n d m e r c u r y (metal
v a p o r ) , c a n be i n t r o d u c e d from t h e r e a c t i o n vessel
i n t o t h e p l a s m a t o r c h w i t h o u t using a nebulizer a n d
s p r a y c h a m b e r . D e t e c t i o n limits achieved with this
t e c h n i q u e a r e as m u c h as 100 times lower t h a n t h o s e
o b t a i n e d b y nebulizing t h e s a m p l e s .
T e m p e r a t u r e s in t h e region of t h e p l a s m a used for
o b s e r v a t i o n a r e 6 0 0 0 - 8 0 0 0 K . Because of its high
t e m p e r a t u r e , the I C P dissociates m o s t m o l e c u l a r spe
cies a n d h e n c e chemical interferences a r e insignificant
c o m p a r e d with t h o s e o b s e r v e d in c o m b u s t i o n flames.
T h e high t e m p e r a t u r e a n d inert a t m o s p h e r e p r e v e n t

283

Optical

Emission

Spectroscopy

the f o r m a t i o n of refractory oxides of, for e x a m p l e ,

t u n g s t e n , t i t a n i u m a n d m o l y b d e n u m ; t h u s these ele
m e n t s h a v e low detection limits in t h e I C P , w h e r e a s
their detection limits are p o o r in flames. I o n i z a t i o n
effects from m a t r i x elements, serious in flames, a r e
negligible o r a l t o g e t h e r n o n e x i s t e n t in the I C P
because the electron c o n c e n t r a t i o n in t h e p l a s m a is
very high c o m p a r e d with t h e electron c o n t r i b u t i o n
from easily ionizable m a t r i x elements. T h e I C P is
u n i q u e a m o n g spectroscopic sources in its freedom
from m a t r i x effects; for this r e a s o n careful m a t r i x
m a t c h i n g of samples a n d c a l i b r a t i o n s t a n d a r d s is n o t
nearly as i m p o r t a n t with t h e I C P as it is for all o t h e r
emission sources. It is often possible t o calibrate the
s p e c t r o m e t e r using solutions t h a t c o n t a i n only the
a n a l y t e elements a n d n o n e of the m a t r i x c o n s t i t u e n t s .
T h e I C P is optically thin; there are few a n a l y t e
a t o m s in the o u t e r regions of the p l a s m a , hence selfa b s o r p t i o n ( a b s o r p t i o n of r a d i a t i o n by unexcited
a t o m s ) of m o s t spectral lines is o b s e r v a b l e only a t
very high a n a l y t e c o n c e n t r a t i o n s . Because of this,
c a l i b r a t i o n curves a r e linear over five to six o r d e r s of
magnitude.
B o t h a t o m i c a n d ionic spectra are excited in t h e
I C P , a n d I C P spectra are c o m p l e x c o m p a r e d with
flame spectra. Spectral complexity gives the analyst a
greater choice of lines b u t also increases the n u m b e r
of spectral line interferences a n d , therefore, t h e w a v e
length resolution required for I C P is greater t h a n with
flames.
T h e I C P c a n be used t o d e t e r m i n e m o s t metallic
a n d n o n m e t a l l i c elements. Typical detection limits
o b t a i n e d with the m o s t sensitive spectral lines r a n g e
1
from a b o u t 0.05 n g m l " for calcium a n d m a g n e s i u m
1
t o a b o u t 8 0 n g m l " for p o t a s s i u m . T h e I C P is a n
excellent source for d e t e r m i n i n g trace, m i n o r a n d
m a j o r c o n s t i t u e n t s in m a n y types of samples in b o t h
a q u e o u s a n d n o n a q u e o u s solution. T h e types of
materials being analyzed routinely by the I C P include
waste water, soil, geological m a t e r i a l s , foodstuffs,
p l a n t s , alloys, p u r e metals a n d p e t r o l e u m p r o d u c t s .
3.3

Arcs

A d c a r c is a c o n t i n u o u s electrical discharge in a small

g a p ( ^ 5 m m ) between t w o vertical r o d electrodes.
G r a p h i t e is the m o s t c o m m o n electrode m a t e r i a l ;
a m o r p h o u s c a r b o n is used less often. Electrodes a r e
available in n u m e r o u s s h a p e s a n d sizes for different
a p p l i c a t i o n s . Typical supply voltages are 100-250 V,
with the voltage across the g a p being 2 5 - 5 0 V: cur
rents a r e in the r a n g e 5-30 A . A n a r c c a n b e o p e r a t e d
either in air o r in a n inert gas. T h e use of a n inert
a t m o s p h e r e (e.g., a r g o n ) eliminates the intense C N
b a n d s which m a k e a large p a r t of t h e s p e c t r u m
u n u s a b l e with a c a r b o n arc in air.
A l m o s t all types of p o w d e r e d i n o r g a n i c solids c a n
be analyzed with the dc arc. T h e s a m p l e is mixed with
spectroscopically p u r e g r a p h i t e a n d p a c k e d i n t o a
cavity in the lower electrode, which is usually the

284

a n o d e . I n m a n y a p p l i c a t i o n s a carrier such as A g C l o r
L i F is a d d e d t o t h e s a m p l e t o m a k e the v a p o r i z a t i o n
process s m o o t h e r a n d m o r e r e p r o d u c i b l e . T h e carrier
m a y facilitate t h e volatilization of t h e entire s a m p l e ,
o r it m a y p r o m o t e fractional volatilization of a n a l y t e
elements from a m a t r i x , in w h i c h case t h e t e c h n i q u e is
called carrier distillation.
A r c spectra consist p r i m a r i l y of n e u t r a l a t o m lines.
L a r g e a m o u n t s of s a m p l e a r e v a p o r i z e d , hence sensi
tivity is high, m a k i n g the a r c a useful s o u r c e for trace
analysis. Since arcs t e n d to w a n d e r a n d flicker, r e p r o
ducibilities are p o o r c o m p a r e d with t h o s e of o t h e r
light sources. T h e relative precision is s e l d o m b e t t e r
t h a n 5 % ; typical detection limits a r e 0.01-1 p p m .
Selective volatilization of a n a l y t e elements is a n
i m p o r t a n t p h e n o m e n o n in arcs. T h e spectra of m o r e
volatile elements a p p e a r s o o n e r t h a n t h o s e of less
volatile elements; therefore, i n t e g r a t i o n times m u s t be
carefully c h o s e n so t h a t t h e intensity of each a n a l y t e
element is m e a s u r e d w h e n it is greatest. Volatile
c o m p o u n d s such as c a r b o n a t e s a n d halides of t h e
alkalis, m e r c u r y , lead, zinc, c a d m i u m a n d t h a l l i u m
a p p e a r in t h e a r c s o o n after ignition; they b e c o m e
depleted from t h e s a m p l e a n d their spectra d i s a p p e a r .
N e x t a r e m e t a l s of i n t e r m e d i a t e volatility, such as
i r o n , nickel, m a n g a n e s e , c h r o m i u m a n d v a n a d i u m ,
which r e m a i n in t h e a r c c o l u m n longer. A t h i r d
g r o u p consists of refractory m e t a l s t h a t a r e c o m
pletely volatilized from t h e s a m p l e only w h e n they a r e
at low c o n c e n t r a t i o n s . T h i s g r o u p includes t h o r i u m ,
t u n g s t e n , u r a n i u m , n i o b i u m , t a n t a l u m , t i t a n i u m , zir
c o n i u m , h a f n i u m a n d m o l y b d e n u m , which form car
bides a n d c a n n o t be completely volatilized within
useful b u r n times.
A l t e r n a t i n g - c u r r e n t arcs a r e used occasionally.
Selective volatilization is lower a n d reproducibility is
better t h a n with d c arcs.
3.4 Electric
Spark
T h e a c s p a r k is t h e m o s t i m p o r t a n t source used for t h e
analysis of m e t a l s . In c o n t r a s t t o arcs, s p a r k s a r e
i n t e r m i t t e n t r a t h e r t h a n c o n t i n u o u s discharges. T h e
t e r m i n o l o g y for t h e v a r i o u s types of discharges is
confusing b u t , in general, s p a r k s a r e differentiated
from arcs by their m u c h higher c u r r e n t s a n d voltages
at b r e a k d o w n . H i g h - v o l t a g e s p a r k s initiate a t 10 0 0 0 50 000 V. N o w a d a y s , low-voltage s p a r k sources with
solid-state p o w e r supplies a r e m o r e c o m m o n ; these
sources o p e r a t e a t 3 0 0 - 1 0 0 0 V. ( T h e p e a k c u r r e n t a t
b r e a k d o w n m a y be several h u n d r e d a m p e r e s . ) T h e
high p o w e r c o n v e r s i o n in t h e s p a r k g a p causes a n
explosive v a p o r i z a t i o n of m a t e r i a l from the elec
t r o d e s . T h e a m o u n t of m a t e r i a l v a p o r i z e d is smaller
t h a n in a n arc. T h e electronic excitation is greater a n d
c o n s e q u e n t l y m o r e lines (ion lines as well as n e u t r a l a t o m lines) a p p e a r in s p a r k spectra. D e t e c t i o n limits
( 1 - 1 0 p p m ) a r e p o o r e r t h a n in t h e d c arc; o n the o t h e r
h a n d , t h e s p a r k is a better s o u r c e for d e t e r m i n i n g high
c o n c e n t r a t i o n s of elements. Typical precision (relative

Optical

s t a n d a r d d e v i a t i o n ) a t high c o n c e n t r a t i o n s is 0 . 5 - 1 % ,
which is far s u p e r i o r t o t h e best precision achievable
in a n a r c . Selective volatilization is n o t as g r e a t a
p r o b l e m in t h e s p a r k .
A s p a r k is p r o d u c e d b y c h a r g i n g a c a p a c i t o r t o the
b r e a k d o w n voltage of t h e analytical g a p . M o r e t h a n
o n e b r e a k d o w n c a n o c c u r p e r half-cycle of c h a r g i n g
c u r r e n t . In o r d e r t o o b t a i n m o r e u n i f o r m excitation
a n d better reproducibility, a c o n t r o l l e d s p a r k is used.
A c o n t r o l l e d - s p a r k circuit c o n t a i n s a device t h a t
allows only o n e b r e a k d o w n of t h e analytical g a p p e r
half-cycle, with t h e b r e a k d o w n o c c u r r i n g a t the s a m e
p o i n t in e a c h half-cycle. O n e such device is a n auxili
ary r o t a t i n g g a p driven b y a s y n c h r o n o u s m o t o r ; t h e
auxiliary g a p is closed only a t t h e p e a k of e a c h halfcycle. I n n e w e r i n s t r u m e n t s , pulse t r a n s f o r m e r s a n d
timing circuits c o n t r o l t h e b r e a k d o w n of t h e a n a l y t i
cal g a p .
A s p a r k s o u r c e is c o m m o n l y o p e r a t e d in a n i t r o g e n
or a n a r g o n a t m o s p h e r e b e c a u s e t h e exclusion of
oxygen i m p r o v e s reproducibility. I n a d d i t i o n , n i t r o
gen a n d a r g o n a r e t r a n s p a r e n t in t h e spectral region
below 200 n m t h a t includes sensitive lines of p h o s
p h o r u s , tin, selenium, arsenic a n d b o r o n .
M e t a l s a m p l e s for analysis b y s p a r k excitation c a n
be in the f o r m of r o d s o r disks cast in chill m o l d s .
S a m p l e s t a k e n from a melt m u s t be c o o l e d r a p i d l y t o
ensure h o m o g e n e i t y ; o t h e r w i s e segregation of p h a s e s
within t h e s a m p l e will c a u s e p o o r precision a n d p o o r
accuracy. R e m e l t i n g is s o m e t i m e s used t o h o m o g e n i z e
samples p r i o r t o analysis. Before m e a s u r i n g intensit
ies, p r e s p a r k i n g in t h e s p a r k s t a n d is used for m i c r o melting of t h e s a m p l e t o c o m p e n s a t e for differences in
metallurgical s t r u c t u r e .
A n interesting a p p l i c a t i o n of t h e s p a r k is on-site
m e t a l s identification with a m o b i l e s p e c t r o m e t e r in
salvage, s h i p p i n g o r s t o r a g e y a r d s , as well as o n
p r o d u c t i o n lines. A p o r t a b l e s p a r k pistol is held b y
the o p e r a t o r a g a i n s t t h e s a m p l e , w h i c h c a n be of a n y
size o r s h a p e . L i g h t from t h e s p a r k is transferred t o
the s p e c t r o m e t e r b y a fiber-optics cable several m e t e r s
long.
A device widely used for a n a l y z i n g liquids, b o t h
solutions a n d s u s p e n s i o n s , is t h e r o t a t i n g - d i s k g r a
phite electrode, o r r o t r o d e . T h e r o t a t i n g electrode
picks u p s a m p l e s from a c o n t a i n e r m o u n t e d b e n e a t h it
a n d t r a n s p o r t s t h e m i n t o the s p a r k g a p a b o v e t h e
r o t r o d e . T h i s is the m o s t i m p o r t a n t t e c h n i q u e for
d e t e r m i n i n g w e a r m e t a l s in used engine oils.
T h e s p a r k c a n also b e used t o analyze p o w d e r s .
N o n c o n d u c t i v e p o w d e r s a r e m i x e d with a c o n d u c t i v e
binder, usually g r a p h i t e , a n d pelletized in a press.
A n o t h e r w a y t o t r e a t n o n c o n d u c t i v e p o w d e r s is t o p u t
t h e m o n t o a t a p e t h a t is fed i n t o t h e s p a r k g a p .
3.5 Discharges in Gases Under Reduced
Pressure
T w o sources t h a t a r e n o t widely used in emission
spectroscopy, b u t which a r e receiving increasing at
tention, a r e the h o t h o l l o w - c a t h o d e l a m p ( H C L ) a n d

Emission

Spectroscopy

t h e glow-discharge l a m p ( G D L ) . B o t h of these devices

p r o d u c e d i r e c t - c u r r e n t discharges u n d e r r e d u c e d p r e s
sure. T h e fill gas is usually a r g o n , b u t helium is
s o m e t i m e s used in t h e H C L .
H C L s used for emission s p e c t r o s c o p y a r e c o n
structed so t h a t the h o l l o w c a t h o d e c a n b e d e m o u n t e d
from t h e l a m p b o d y t o p e r m i t l o a d i n g of t h e s a m p l e .
T h e c a t h o d e m a t e r i a l is either a m e t a l t h a t is difficult
t o s p u t t e r (e.g., stainless steel) o r a m a t e r i a l with a
simple s p e c t r u m (e.g., c o p p e r , silver, m a g n e s i u m o r
g r a p h i t e ) . T h e s a m p l e is in t h e f o r m of chips ( 1 0 30 m g ) , a n d t h e gas p r e s s u r e used is less t h a n 2 k P a . If
t h e c a t h o d e is intentionally cooled, t h e s a m p l e within
t h e h o l l o w c a t h o d e is v a p o r i z e d b y s p u t t e r i n g only;
o t h e r w i s e t h e r m a l v a p o r i z a t i o n o c c u r s in a d d i t i o n t o
s p u t t e r i n g . W i t h low c u r r e n t s , m o s t of t h e s a m p l e
enters t h e d i s c h a r g e b y s p u t t e r i n g . A t high c u r r e n t s
( 1 - 2 A ) t h e t e m p e r a t u r e of t h e h o l l o w c a t h o d e m a y
r e a c h 2000 C a n d t h e r m a l v a p o r i z a t i o n p r e d o m i
n a t e s . U n d e r these c o n d i t i o n s fractional volatilization
o c c u r s ; this allows t h e d e t e r m i n a t i o n of volatile
impurities in h i g h - m e l t i n g - p o i n t m e t a l s .
T h e h o t H C L h a s been used for t h e d e t e r m i n a t i o n
of t r a c e elements in p u r e nickel a n d h i g h - t e m p e r a t u r e
nickel alloys. Typical d e t e c t i o n limits r a n g e from less
t h a n 0.01 p p m t o 1 p p m , d e p e n d i n g u p o n t h e element.
A t t h e 10 p p m c o n c e n t r a t i o n level, the relative preci
sion is a p p r o x i m a t e l y 1 0 % .
W i t h a G D L , t h e s a m p l e is l o a d e d from o u t s i d e the
l a m p . T h e a n o d e is a h o l l o w cylinder close t o t h e flat
s a m p l e , w h i c h is t h e c a t h o d e . T h e discharge takes
place within t h e h o l l o w a n o d e , b u t it is the c a t h o d e
t h a t is s p u t t e r e d . T h e p r e s s u r e used is 0 . 6 7 - 2 k P a , the
p o w e r s u p p l y voltage is 6 0 0 - 1 8 0 0 V a n d the c u r r e n t
c a n b e as great as 300 m A .
S p e c t r a in t h e G D L h a v e little b a c k g r o u n d a n d the
lines a r e s h a r p . T h e best analytical lines in this
d i s c h a r g e a r e n e u t r a l - a t o m lines. Since t h e p l a s m a is
n o t very d e n s e , there is little self-absorption a n d high
concentrations can be determined. Interelement
effects in t h e G D L a r e m i n i m a l , w h i c h m a k e s calib
r a t i o n relatively simple.
I n spite of these i m p o r t a n t a d v a n t a g e s , several
p o i n t s h a v e k e p t t h e G D L from b e c o m i n g a routinely
used source. Since r e d u c e d p r e s s u r e is used, t h e s a m
ple m u s t b e very flat a n d s m o o t h so t h a t a n airtight
seal c a n b e f o r m e d with t h e l a m p b o d y . D e t e c t i o n
limits a r e generally n o t low e n o u g h for p e r f o r m i n g
trace analysis. C a r e m u s t be exercised w h e n analyzing
m e t a l s with a high affinity for oxygen b e c a u s e m e t a l
oxide layers c a u s e p r o b l e m s . T h e G D L is m o r e sensi
tive t h a n a s p a r k t o differences in s a m p l e structures;
b e c a u s e different p h a s e s a t t h e s a m p l e surface a r e
s p u t t e r e d a t different rates, t h e results m a y n o t reflect
the m e a n sample composition.
W i t h the G D L , b e t t e r analytical a c c u r a c y (com
p a r e d with t h a t of t h e s p a r k ) c a n be achieved o n cast
h y p o e u t e c t i c alloys with fine, well-distributed inclu
sions (e.g., lead in steel o r m a g n e s i u m in n o d u l a r

285

Optical

Emission

Spectroscopy

iron). T h e G D L is m o s t useful for t h e analysis of

high-alloy steels a n d alloys of nickel, c o b a l t a n d
c o p p e r . M a j o r element c o n c e n t r a t i o n s in these alloys
r a n g e u p w a r d of 5 0 % . D e t e c t i o n limits in these alloys
a r e 150 p p m for elements of significance. A t c o n c e n
t r a t i o n s typically of interest in alloys, t h e relative
precision r a n g e s from 0 . 5 % t o 5 % . Because the G D L
- 1
can s p u t t e r defined layers of a b o u t 1 m i n , the
l a m p h a s the p o t e n t i a l t o be used t o d e t e r m i n e the
thickness a n d c o m p o s i t i o n of surface layers a n d
coatings.
See also: Infrared Spectroscopy

a n d is limited t o a m a x i m u m magnification of a b o u t
t w e n t y times (20 x ) . T h e c o m p o u n d m i c r o s c o p e
with a useful magnification r a n g e of a few times t o
over 2000 x consists of four c o m p o n e n t s : a light
source, c o n d e n s e r lens, objective lens a n d eyepiece
(ocular) (Fig. 1). T h e c o n d e n s e r collects light rays
from t h e light s o u r c e which a r e focused o n t o the
specimen. T h e objective lens (the lens nearest the
object) forms a real, magnified aerial i m a g e of
t h e object in t h e i n t e r m e d i a t e i m a g e p l a n e . T h i s real
i m a g e is further magnified b y t h e eyepiece t o form t h e
final i m a g e , which c a n be (a) viewed directly in the
eyepiece, (b) projected o n t o a viewing screen o r
p h o t o g r a p h i c film, o r (c) o b s e r v e d b y w a y of a
television system.

Bibliography
Barnes R 1976 Emission Spectroscopy. Dowden, Hut
chinson and Ross, Stroudsburg, PA
Harrison G R (ed.) 1969 Massachusetts Institute of Tech
nology Wavelength Tables, 2nd edn. MIT Press, Cam
bridge, MA
Herzberg G 1944 Atomic Spectra and Atomic Structure, 2nd
edn. Dover Publications, New York
Mavrodineanu R (ed.) 1970 Analytical Flame Spectroscopy.
Macmillan, London
Meggers W F, Corliss C H, Scribner F (eds.) 1975 Tables
of Spectral Line Intensities, 2nd edn. US Department of
Commerce, Washington, DC
Sawyer R A 1963 Experimental Spectroscopy, 3rd edn.
Dover, New York
Slavin 1971 Emission Spectrochemical Analysis. Wiley,
New York
Slickers 1981 Automatic
Emission
Spectroscopy.
Bruhlsche Universitatsdruckerei, Giessen, Germany
Zaidel' A N, Prokof ev V K, Raiskii S M, Slavnyi V A,
Schreider Ya 1970 Tables of Spectral Lines. IFI/
Plenum, New York
H . R. Sobel
[Applied R e s e a r c h L a b o r a t o r i e s ,
S u n l a n d , California, U S A ]

Optical Microscopy
T h e optical (or light) m i c r o s c o p e is a n i n s t r u m e n t t h a t
magnifies a n d resolves the s t r u c t u r e of objects. O b
jects m a y be viewed by either t r a n s m i t t e d o r reflected
light a n d by a selection of i l l u m i n a t i o n m e t h o d s . T h e
optical m i c r o s c o p e is p r o b a b l y t h e single m o s t widely
used i n s t r u m e n t in scientific research, rinding applica
tions in diverse disciplines including m a t e r i a l s science,
m i n e r a l o g y , chemistry, biology, medicine, particle
analysis a n d forensic science.

2. Numerical

Aperture

and

Resolution

E a c h optical system h a s a m a x i m u m resolving

p o w e r o r r e s o l u t i o n t h a t is d e t e r m i n e d by a
n u m b e r of factors. T h e typical u n a i d e d h u m a n eye
h a s a resolving p o w e r of a p p r o x i m a t e l y 150 ; t h a t
is, t w o discrete object p o i n t s with a s e p a r a t i o n of
150 o r greater c a n be resolved as t w o s e p a r a t e a n d
distinct entities. A t closer spacing t h e object p o i n t s
c a n n o t be individually identified by the u n a i d e d eye.
T h e m a x i m u m resolving p o w e r of a c o m p o u n d light
m i c r o s c o p e is a p p r o x i m a t e l y 0.2 a n d is deter
m i n e d by the n u m e r i c a l a p e r t u r e of the objective lens
a n d t h e w a v e l e n g t h of i l l u m i n a t i o n .
N u m e r i c a l a p e r t u r e ( N A ) is defined as being e q u a l
to wsinf?, w h e r e is t h e refractive index of the
m e d i u m b e t w e e n t h e objective lens a n d the object (n
=" 1 for air) a n d is half the a n g u l a r a p e r t u r e (or
a c c e p t a n c e angle of i m a g e - f o r m i n g rays) of the objec
tive lens ( J e n k i n s a n d W h i t e 1957). T h e use of optical
i m m e r s i o n oil (n = 1.52) c a n raise the value of so
t h a t lenses with N A values as high as 1.40 c a n be
routinely offered by t h e lens m a n u f a c t u r e r s . A s
as high as 1.60 a r e a t t a i n a b l e with special lenses d e
signed t o be used with high-refractive-index liquids
such
as n a p h t h a l e n e
monobromide
(=1.66)
(Phillips 1971).
T h e N A values of individual objective lenses typi
cally v a r y from less t h a n 0.1 t o 1.40. Lenses labelled
with A s of 0.95 o r less a r e usually i n t e n d e d t o be
used in air only (i.e., d r y ) , w h e r e a s lenses of N A of 1.0
o r higher m u s t be i m m e r s e d , usually in a n optical oil
of = 1.52, as specified b y t h e m a n u f a c t u r e r . I m m e r
sion lenses a r e labelled with the i m m e r s i o n m e d i a with
which they a r e designed t o be used.
T h e resolution of a n optical m i c r o s c o p e is given b y
the relationship
d = 0 . 6 1 /A

1. The

Microscope

T h e m o s t e l e m e n t a r y m i c r o s c o p e is t h e simple m i c r o
scope which e m p l o y s a single lens (magnifying glass)

286

w h e r e d is the smallest resolvable d i s t a n c e in t h e i m a g e

( s e p a r a t i o n of t w o discrete object p o i n t s ) a n d is
t h e w a v e l e n g t h of i l l u m i n a t i o n (Jenkins a n d W h i t e

Optical

Microscopy

from 1 x to 100 x and are used in conjunction with

eyepieces that provide the second stage of magnifica
tion and are available in the range of 5 x to 25 x mag
nifications. Since the magnification of the final image
is the product of the primary magnifications of the
objective lens and the eyepiece, a final magnification
range of from 5 x to 2500 x is available. Each objec
tive lens is designed to have a combined magnifying
power and NA such that the object detail resolved by
the lens will be magnifiedin the final imageto at
least the value of the maximum resolving power of the
eye (150 ). For example, a 10 x objective lens with
a 0.22 NA would have a resolving power of
0.6

0.61(0.54 , green filter)

-~NA

0^2

mL

with 1.50 () = 150 (i.e., = 100), where

is the magnification of the final image. Therefore, this
particular objective lens with a primary magnifying
power of 10 x should be used with an eyepiece of
magnifying power of 10 x (or higher, for comfortable
viewing) to obtain a final magnification of at least
100 x so that object detail resolved by the lens can be
resolved by the observer's eye. Similarly, an upper
limit of total magnification for a given objective lens is
assigned to avoid what is known as "empty magnifi
cation," a condition in which no additional detail is
resolved as the magnification is increased. Since the
NA (and thus the corresponding resolving power) of
the lens is fixed, the maximum useful image enlarge
ment is about 1000 times the NA.

4. Objective-Lens

Figure 1
Ray paths and optical component locations for
(a) transmitted light, and (b) reflected light microscopes:
1, light source; 2, field diaphragm; 3, condenser lens;
4, substage condenser; 5, object (specimen); 6, objective
lens; 7, eyepiece (ocular); 8, coarse focus; 9, fine focus; and
10, aperture diaphragm (courtesy of E. Leitz)

1957). Thus, for an oil-immersion system (NA = 1.40)

employing white-light illumination with a blue filter
( = 0.45 ), the maximum resolution obtainable is
0.196 .

3.

Magnification

Each objective lens has a fixed magnification and NA,

the values of which are usually engraved on the lens
barrel. Objective-lens magnifications typically vary

Aberrations

A number of different types of aberrations occur in

glass lenses, resulting in loss of image quality if left
uncorrected. The most troublesome aberrations
include spherical and chromatic aberration, coma,
distortion, astigmatism and field curvature. These
aberrations are partially or completely corrected
in the three principal types of objective lenses, listed
in order of increasing correction: achromats, semiapochromats and apochromats.
The most commonly used and least expensive ob
jective lens is the achromat. The corrections for
chromatic and spherical aberration for this lens are
centered about the green wavelength of the spectrum
and, therefore, it is recommended that achromatic
objective lenses be used in conjunction with a green
filter. For a given magnification, achromats provide a
greater working distancethe separation distance
between the front surface of the lens and the focused
objectthan the other types of objective lenses. These
lenses are available in "flat-field" versions, which
produce a planeor "flat"intermediate image that
is particularly desirable for photomicrography
(photography of microstructures). Versions of these
287

Optical

Microscopy

lenses with e x t r a - l o n g w o r k i n g distances a r e available

from several l e n s m a k e r s .
A p o c h r o m a t i c objective lenses a r e t h e m o s t highly
corrected a n d a r e therefore r e c o m m e n d e d for color
p h o t o m i c r o g r a p h y , a s well as for high-magnification
w o r k since they also h a v e a high N A for a given
p r i m a r y magnification. T h i s c a t e g o r y of lenses is also
available in flat-field versions, which h a v e designa
tions such as p i a n o , p l a n , PI o r p l a n a p o c h r o m a t .
T h e s e c o n s t i t u t e t h e m o s t expensive i n v e s t m e n t t h a t
c a n b e m a d e for objectives.
S e m i a p o c h r o m a t s offer a b e r r a t i o n c o r r e c t i o n s N A
a n d price t h a t a r e i n t e r m e d i a t e b e t w e e n a c h r o m a t s
a n d a p o c h r o m a t s . T h e s e lenses a r e often referred t o as
fluorites
since they c o n t a i n o n e o r m o r e
fluorite
elements. T h e y a r e n o t available as flat-field objectives
a n d , as a c o n s e q u e n c e , p r o d u c e a slight c u r v a t u r e of
field. T h e y a r e , h o w e v e r , frequently considered t o b e a
g o o d c o m p r o m i s e in p e r f o r m a n c e a n d price b e t w e e n
the a c h r o m a t s a n d a p o c h r o m a t s . All objective lenses
s h o u l d b e only used with p r o p e r l y m a t c h e d eyepieces
recommended by the manufacturer.

5. Depth

of Field

A n o t h e r i m p o r t a n t p a r a m e t e r in a n y type of m i c r o s
copy is t h a t of d e p t h of field ( D O F ) , w h i c h c a n b e
d e n n e d as t h e axial d i s t a n c e in object space over
which object detail is in a c c e p t a b l e focus for a given
setting of the lens focus. T h e d e p t h of field of the light
m i c r o s c o p e is r a t h e r limited, p a r t i c u l a r l y a t t h e higher
magnifications ( N A s ) . T h e D O F ( p h o t o g r a p h i c ) is
related t o t h e N A of the objective lens, t h e w a v e l e n g t h
of i l l u m i n a t i o n a n d t h e refractive index of t h e m e d i u m
between t h e object a n d t h e front surface of t h e
objective lens b y t h e r e l a t i o n s h i p ( M c C r o n e et al.
1978):
2

D O F = ( -

NA )

1 / 2

/NA

Typical D O F values for green

wavelength
( = 0.54 ) i l l u m i n a t i o n a r e listed in T a b l e 1.

Table 1
Typical values of photographic depth of field for green
wavelength ( = 0.54 ) illumination
Numerical
aperture
0.25
0.40
0.65
0.95
1.0
1.40

288

Depth of field
()
8
3
1
0.18
0.62
0.16

Lens
system
dry objectives
oil-immersion objectives

6. Field Diaphragm,
Aperture
Kohler
Illumination

Diaphragm

and

A c o m p o u n d light m i c r o s c o p e is fitted w i t h t w o
adjustable iris d i a p h r a g m s , e a c h of which h a s a speci
fic function. T h e field d i a p h r a g m is p o s i t i o n e d in t h e
optical system such t h a t it is i m a g e d in t h e p l a n e of t h e
specimen. T h e r e f o r e , t h e silhouette of t h e d i a p h r a g m
c a n b e o b s e r v e d s i m u l t a n e o u s l y with t h e focused
object i m a g e . T h e principal role of t h e field d i a p h
r a g m is t o i m p r o v e i m a g e c o n t r a s t b y t h e r e d u c t i o n of
internal glare in t h e optical system. It s h o u l d b e
s t o p p e d d o w n t o confine t h e d i a m e t e r o f i r r a d i a t i o n
t o only t h a t a r e a of t h e object u n d e r o b s e r v a t i o n o r
t h a t w h i c h is t o b e p h o t o g r a p h e d . T h e setting of this
d i a p h r a g m h a s n o effect o n t h e b r i g h t n e s s of t h e
object i m a g e .
T h e a p e r t u r e d i a p h r a g m is i m a g e d in t h e b a c k focal
p l a n e of t h e objective lens a n d c o n t r o l s t h e d i a m e t e r
of t h e c o n e of light t h a t enters t h e lens. T h e p r o p e r
a d j u s t m e n t of this d i a p h r a g m is essential t o t h e a t t a i n
m e n t of o p t i m u m c o n t r a s t a n d resolution. T h e i m a g e
of this d i a p h r a g m a n d t h e b a c k focal p l a n e of t h e
objectivecan b e o b s e r v e d b y l o o k i n g i n t o t h e m i c r o
scope t u b e with t h e eyepiece r e m o v e d after t h e object
h a s been focused. T h e o p t i m u m setting of this d i a p h
r a g m is a c o m p r o m i s e ; h o w e v e r , it is generally r e c o m
mended that the aperture diaphragm be stopped
d o w n t o 8 0 - 9 0 % of t h e a p e r t u r e of t h e objective lens.
A l a r g e r - d i a m e t e r setting results in e x t r a n e o u s flare in
t h e system, w h e r e a s a smaller d i a m e t e r results in
r e d u c t i o n of t h e effective N A of t h e objective lens.
Since t h e d i a p h r a g m affects t h e brightness of t h e final
i m a g e , it is c o m m o n l y i m p r o p e r l y used t o adjust light
levels t o t h e d e t r i m e n t of i m a g e quality. B o t h t h e field
a n d a p e r t u r e d i a p h r a g m s h a v e p r o v i s i o n for centering
on most microscopes.
M o s t m i c r o s c o p e s a r e e q u i p p e d t o follow t h e
Kohler principle of i l l u m i n a t i o n , which p r o v i d e s a
very uniformly illuminated field of view even with a
n o n u n i f o r m light source such a s a coiled-filament
i n c a n d e s c e n t l a m p . Kohler i l l u m i n a t i o n is o b t a i n e d
by a d j u s t m e n t of t h e l a m p c o n d e n s e r t o focus t h e
i m a g e of t h e light source o n t o t h e p l a n e of t h e
aperture diaphragm.

7. Microscope

Types

T h e light m i c r o s c o p e is indeed a very versatile in

s t r u m e n t w h e n t h e variety of m o d e s in w h i c h it is
c o n s t r u c t e d a n d used is considered. T h e t w o m a i n
categories of m i c r o s c o p e s a r e (a) t r a n s m i s s i o n , in
w h i c h light is p a s s e d t h r o u g h t h e object u n d e r s t u d y
t o form a n image; a n d (b) reflection (incident), in
which a n i m a g e is f o r m e d from light reflected from
t h e surface of t h e object. B o t h types a r e m a n u f a c t u r e d
in m o n o c u l a r a n d b i n o c u l a r , a s well a s u p r i g h t - a n d

Optical

inverted-stage (Le C h a t e l i e r - t y p e ) m o d e l s . O f t h e
m a n y different k i n d s of l i g h t - m i c r o s c o p y i m a g i n g
techniques t h a t a r e available, discussion h e r e is
limited t o t h o s e t h a t h a v e significant a p p l i c a t i o n in
m a t e r i a l s science; n a m e l y , b r i g h t field, d a r k field,
polarized, interference c o n t r a s t , a n d t w o - b e a m a n d
m u l t i p l e - b e a m interference.
7.1 Bright-Field
Illumination
By far t h e m o s t c o m m o n l y used i m a g i n g t e c h n i q u e in
light m i c r o s c o p y is bright-field i l l u m i n a t i o n in which
the illuminating b e a m is a solid c o n e of light focused
o n t o t h e specimen b y a c o n d e n s e r - l e n s system either
in t r a n s m i s s i o n o r b y reflection. T h e light m a y be
unfiltered w h i t e light o r m o n o c h r o m a t i c . T h e
m e c h a n i s m of i m a g e c o n t r a s t is b y a b s o r p t i o n o r b y
scattering. In t r a n s m i s s i o n , bright-field light m i c r o s
c o p y is effective in t h e s t u d y of p a r t i c u l a t e m a t t e r
(dispersions) as well as t h e m i c r o s t r u c t u r a l c h a r a c t e r i
z a t i o n of glasses, c e r a m i c s a n d plastics in thin section.
Reflected bright-field i l l u m i n a t i o n is t h e m o s t c o m
m o n m e t h o d used t o s t u d y t h e m i c r o s t r u c t u r e of
polished a n d e t c h e d m e t a l s ( m e t a l l o g r a p h y ) a n d cera
mics ( c e r a m o g r a p h y ) a n d surface s t r u c t u r e s in
general.
7.2 Dark-Field (or Dark-Ground)
Illumination
In bright-field m i c r o s c o p y m o s t of t h e light from t h e
c o n d e n s e r lens enters t h e objective lensafter inter
acting with t h e o b j e c t t o p a r t i c i p a t e in i m a g e f o r m a
tion. T h i s system generally results in a n i m a g e w i t h a
b r i g h t field o r b a c k g r o u n d . T h e c o n d e n s i n g system
for dark-field i l l u m i n a t i o n utilizes a central circular
disk s t o p t h a t p r e v e n t s direct c o n d e n s e r r a y s from
entering t h e objective lens. O n l y t h o s e r a y s t h a t h a v e
been suitably scattered b y t h e object (by reflection,
refraction o r diffraction) e n t e r t h e objective lens t o
g e n e r a t e t h e final i m a g e . Object detail responsible for
the scattering a p p e a r s b r i g h t o n a d a r k b a c k g r o u n d o r
field. I n t h e t r a n s m i s s i o n m o d e , this system of illumi
n a t i o n finds useful a p p l i c a t i o n in t h e s t u d y of m a t e r
ials of low c o n t r a s t b u t w h i c h scatter l i g h t s u c h as
small particles o r i n t e r n a l inclusions a n d p o r e s in thin
sections. I n c i d e n t dark-field i l l u m i n a t i o n c a n often
p r o v i d e i m p r o v e d i m a g e c o n t r a s t over bright-field
m e t h o d s o n specimens with t o p o g r a p h i c a l irregulari
ties, such as etched m e t a l l o g r a p h i c a n d c e r a m o g r a p h i c specimens a n d i n t e g r a t e d circuits.
7.3 Polarized-Light
Illumination
Polarized-light m i c r o s c o p y is used in either t r a n s m i t
ted or reflected light for t h e q u a n t i t a t i v e o r q u a l i t a t i v e
c h a r a c t e r i z a t i o n a n d identification of optically a n i s o
t r o p i c m a t e r i a l s . A c o n v e n t i o n a l light m i c r o s c o p e c a n
be c o n v e r t e d i n t o a p o l a r i z i n g m i c r o s c o p e by placing
t w o p o l a r i z i n g elements in t h e optical system. T h e
first polarizer is l o c a t e d b e t w e e n t h e light s o u r c e a n d
the object p l a n e a n d c o n v e r t s u n p o l a r i z e d light i n t o

Microscopy

p l a n e o r linearly p o l a r i z e d light. T h e second polarizer

(the analyzer), which is usually r o t a t a b l e , is posi
t i o n e d b e t w e e n t h e objective a n d t h e eyepiece. F o r
m o s t a p p l i c a t i o n s , t h e t w o p o l a r i z i n g elements are
" c r o s s e d , " t h a t is, the p o l a r i z i n g direction of the
a n a l y z e r is p e r p e n d i c u l a r t o t h e direction of the
polarizer. A r o t a t a b l e object stage is necessary for
serious w o r k .
I n t r a n s m i s s i o n , the optical p r o p e r t i e s of optically
a n i s o t r o p i c m a t e r i a l s c a n be studied. A n auxiliary
o p t i c t h e B e r t r a n d l e n s p r o v i d e s a magnified im
age of the b a c k focal p l a n e of t h e objective lens a n d
p e r m i t s the o b s e r v a t i o n of characteristic interference
figures of uniaxial a n d biaxial crystals. T h i s type of
polarized-light m i c r o s c o p y is referred t o as c o n o scopic o b s e r v a t i o n , as o p p o s e d t o c o n v e n t i o n a l o r t h oscopic observation. Conoscopic observation, along
with t h e use of w a v e r e t a r d a t i o n a n d c o m p e n s a t o r
plates, c a n be used effectively by t h e sophisticated
m i c r o s c o p i s t for t h e c h a r a c t e r i z a t i o n a n d identifica
tion of a n i s o t r o p i c m a t e r i a l s a n d t h e s t u d y of their
optical p r o p e r t i e s .
A p p l i c a t i o n s of reflection polarized-light m i c r o s
c o p y include t h e s t u d y of m e t a l l o g r a p h i c sections of
opaque anisotropic and ferromagnetic materials.
G r a i n size a n d s h a p e , preferred o r i e n t a t i o n , t w i n n i n g
a n d p h a s e d i s t r i b u t i o n a r e all effectively delineated b y
polarized-light m i c r o s c o p y of u n e t c h e d a n i s o t r o p i c
metals.
A n o t h e r a p p l i c a t i o n of incident polarized-light
m i c r o s c o p y is in f e r r o m a g n e t i c - m a t e r i a l s investiga
tions. M a g n e t i c - d o m a i n s t r u c t u r e s in o p a q u e m e t a l l o graphically p r e p a r e d f e r r o m a g n e t i c m a t e r i a l s c a n b e
i m a g e d b y this i l l u m i n a t i o n m e t h o d . T h e o p e r a t i v e
c o n t r a s t m e c h a n i s m k n o w n as t h e K e r r m a g n e t o o p tic effectis t h a t incident p l a n e - p o l a r i z e d light u n d e r
goes r o t a t i o n u p o n reflection from ferromagnetic
surfaces.
7.4 Interference
Microscopy
T h e t e c h n i q u e s of interference m i c r o s c o p y h a v e been
widely applied t o t h e q u a n t i t a t i v e a n d qualitative
c h a r a c t e r i z a t i o n of m i c r o t o p o g r a p h i c a l features o n
t h e surface of o p a q u e m a t e r i a l s . T h e large n u m b e r of
types a n d designs of interference m i c r o s c o p e s t h a t a r e
useful in t h e c h a r a c t e r i z a t i o n of surface m o r p h o l o g y
c a n be divided i n t o t w o basic categories: interferencefringe m i c r o s c o p e s a n d interference-contrast m i c r o
scopes.
(a) Interference-fringe
microscopy.
One microscope
design in this c a t e g o r y is t h e M i c h e l s o n - t y p e d o u b l e b e a m interference m i c r o s c o p e , w h i c h is essentially a
c o m b i n e d c o m p o u n d - r e f l e c t i o n light m i c r o s c o p e a n d
M i c h e l s o n i n t e r f e r o m e t e r (Fig. 2). It p r o v i d e s a m a g
nified i m a g e of t h e object surface a n d e m p l o y s the
interference of t w o c o h e r e n t m o n o c h r o m a t i c light
b e a m s from a c o m m o n s o u r c e t o p r o d u c e interference
fringes w h i c h c a n b e visualized as a c o n t o u r m a p of

289

Optical

Microscopy

R e f e r e n c e mirror

Figure 2
Schematic arrangement of two-beam reflection interference
microscope. A condenser lens directs a parallel beam of
light from a monochromatic source onto a beam-splitting
prism where two coherent light beams are formed.
Separate images are formed of the specimen surface and a
reference mirror by matched objective lenses. These
images are then combined by the beam splitter, resulting
in a magnified interference pattern that is viewed through
the eyepiece

the surface. M e a s u r e m e n t s of t h e lateral displace

m e n t s of these fringes in the final i m a g e a r e used t o
o b t a i n vertical quantification of surface irregularities.
A p e r t u r b a t i o n o n the object surface causes a lateral
shift of the fringes t h a t fall o n t h a t region of the
specimen as is illustrated by the s c h e m a t i c represen
t a t i o n in Fig. 3. A shift of o n e full fringe spacing
represents a specimen height difference of /2. T h e r e
fore, the height difference of a surface irregularity in
relation t o t h e s u r r o u n d is given by the r e l a t i o n s h i p
h = (/2), w h e r e d is t h e fringe d i s p l a c e m e n t in units
of fringe spacing. T h e vertical r e s o l u t i o n of t w o - b e a m
interference m i c r o s c o p y is a b o u t 20 n m .
A n o t h e r type of interference-fringe m i c r o s c o p y
m u l t i p l e - b e a m in terferometryyields
significantly
superior vertical resolution, b u t is c o n s i d e r a b l y m o r e
difficult t o effect. M u l t i p l e - b e a m reflections of
m o n o c h r o m a t i c light o c c u r between t h e object surface
a n d a metallized optical flat placed in close c o n t a c t
with t h a t surface. T h e reflectivity of the optical flat

Figure 3
Schematic visualization of two-beam fringes arising from
intersection of a set of parallel, equispaced planes with the
specimen surface (courtesy of Carl Zeiss Inc.)

290

Figure 4
Comparison of fringe patterns obtained by: (a) two-beam,
and (b) multiple-beam interference microscopy; (a) shows
furrows on the surface of InSb resulting from parallel melt
traces made by a scanning laser, and (b) shows the surface
of a directionally solidified AlCu thin film

m u s t closely m a t c h the object reflectivity t o o b t a i n

s h a r p , n a r r o w fringes (Fig. 4). Vertical resolutions of
0.5-1 n m ( T o l a n s k y 1960, 1968) h a v e been achieved
by this m e t h o d .
A p p l i c a t i o n s of incident interference-fringe m i c r o s
c o p y a r e varied a n d include t h e quantification of
surface irregularities o n cleaved surfaces, crystals,
electronic m a t e r i a l s , etch pits, m a n u f a c t u r e d surfaces
a n d t h e r m a l l y etched surfaces, a n d t h e m e a s u r e m e n t
of thin-film thickness.

Figure 5
Schematic representation of double-beam reflection
differential interference contrast optical configuration
(courtesy of Carl Zeiss Inc.)

Optical
(b) Interference-contrast
microscopy.
A n u m b e r of
different interference-contrast systems a r e e x t a n t .
P r o b a b l y the m o s t widely used system is N o m a r s k i
differential interference-contrast ( D I C ) m i c r o s c o p y
( N o m a r s k i a n d Weill 1954, 1955). It is a n extremely
sensitive i m a g e - e n h a n c e m e n t t e c h n i q u e t h a t utilizes
the interference c o n d i t i o n s g e n e r a t e d by o p t i c a l - p a t h length differences of t w o b e a m s of c o h e r e n t p o l a r i z e d
light a n d r e n d e r s visible object detail t h a t is generally
n o t revealed by o t h e r light optical m e t h o d s . T h e
technique h a s n u m e r o u s diverse a p p l i c a t i o n s in reflec
tion a n d t r a n s m i s s i o n a n d c a n be used in b o t h blacka n d - w h i t e a n d c o l o r c o n t r a s t m o d e s ( H o l i k 1975).
In the reflection m o d e , i n c o m i n g p l a n e - p o l a r i z e d
light interacts with a birefringent p r i s m (modified
W o l l a s t o n p r i s m , after N o m a r s k i ) , which s e p a r a t e s
the polarized light i n t o t w o w a v e fronts of similar
intensities a n d v i b r a t i n g in m u t u a l l y p e r p e n d i c u l a r
planes (Fig. 5). T h e t w o c o h e r e n t p o l a r i z e d b e a m s a r e
in p h a s e a n d their lateral s e p a r a t i o n is s o m e w h a t less
t h a n the resolving p o w e r of t h e p a r t i c u l a r objective
lens used. T h e s e t w o parallel a n d p o l a r i z e d b e a m s a r e
reflected from t h e specimen surface, i m a g e d b y t h e
objective lens a n d r e c o m b i n e d b y the W o l l a s t o n p r i s m
a n d analyzer, t h e r e b y c r e a t i n g a n interference c o n
dition. P h a s e differentials b e t w e e n reflected w a v e
fronts arising from surface irregularities, o r reflection
p h a s e shifts, result in final-image interference c o n
trast. Interference-contrast i m a g e s o b t a i n e d by this
technique have a unique three-dimensional appear
ance d u e t o different light intensities o n o p p o s i t e sides
of t o p o g r a p h i c a l features. T h i s effect is often helpful
t o the m i c r o s c o p i s t in the i n t e r p r e t a t i o n of surface
structures. U n d e r favorable c o n d i t i o n s , the D I C tech
n i q u e is c a p a b l e of revealing surface irregularities of
the o r d e r of a few t e n t h s of a n a n o m e t e r , b u t , of

Microscopy

Figure 7
Mechanically polished, unetched, aluminum oxide
ceramic: (a) bright-field illumination, and
(b) differential-interference-contrast illumination

c o u r s e , is still limited in lateral resolution t o a p p r o x i

m a t e l y 0.2 .
D I C m i c r o s c o p y is basically a qualitative interfer
ence t e c h n i q u e t h a t c o n v e r t s o p t i c a l - p a t h - l e n g t h dif
ferences i n t o i m a g e c o n t r a s t . In t h e reflection m o d e ,
its chief utility is in revealing surface s t r u c t u r e s t h a t
a r e n o t seen by o t h e r optical m e t h o d s . E x a m p l e s of
such s t r u c t u r e s a r e e t c h e d detail in m e t a l l o g r a p h i c
specimens (Fig. 6), relief-polished s t r u c t u r e s in
as-polished s a m p l e s (Fig. 7), defects o n electronic
m a t e r i a l s , surface-wear t r a c k s , epitaxially d e p o s i t e d
s t r u c t u r e s a n d cleaved-surface s t r u c t u r e s .
See also: Confocal Optical Microscopy; Polymers: Light
Microscopy

Bibliography

Figure 6
Polished and chemically etched aluminum alloy
(hydrofluoric acid: water 1:99): (a) bright-field
illumination, and (b) differential-interference-contrast
illumination

Holik A S 1975 Surface characterization by interference

microscopy. In: French , Gray R J, McCall J L (eds.)
1975 Microstructural Science, Vol. 3, Pt. B. Elsevier, New
York, pp. 991-1010
Jenkins F A, White 1957 Fundamentals of Optics, 3rd
edn. McGraw-Hill, New York
McCrone W C, McCrone L B, Delly J G 1978 Polarized
Light Microscopy. Ann Arbor Science, Ann Arbor, MI
Nomarski G, Weill A R 1954 Observations of figures of
crystal growth by two wave interferometric methods.
Bull. Soc. Fr. Mineral. Cristallogr. 77: 840-68
Nomarski G, Weill A R 1955 Application to metallography
of two polarized wave interferometric methods. Rev.
Metall. (Paris) 52: 121-34
Phillips V A 1971 Modern Metallographic Techniques and
Their Applications. Wiley, New York
Richardson J 1971 Optical Microscopy for the Materials
Sciences. Dekker, New York
Tolansky S 1960 Surface Microtopography. Interscience,
New York

291

Optical

Microscopy

Tolansky S 1968 Microstructures of Surfaces Using Inter

ferometry. Elsevier, New York

Accelerating and
focusing region

A . S. H o l i k
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]

Organic Mass Spectrometry

M a s s s p e c t r o m e t r y is the single m o s t powerful a n a l y
tical t o o l available to the o r g a n i c chemist. It is widely
used for b o t h qualitative a n d q u a n t i t a t i v e d e t e r m i
n a t i o n s . Qualitatively, t h e m a s s s p e c t r o m e t e r gives
d a t a leading t o t h e identification of o r g a n i c chemicals
in the form of p u r e s u b s t a n c e s o r c o m p l e x m i x t u r e s .
T h e s a m e d a t a , with p r o p e r c a l i b r a t i o n , c a n also b e
used t o m e a s u r e the c o n c e n t r a t i o n of t h o s e chemicals.
T h e t e c h n i q u e is applicable t o a wide r a n g e of s u b
stances, from g a s e o u s m a t e r i a l s , such as m e t h a n e a n d
o t h e r volatile fuels a n d solvents, t o h i g h - m o l e c u l a r weight solids, such as c a r b o h y d r a t e s a n d p r o t e i n s .
M a s s s p e c t r o m e t r y is a p r o c e s s involving i o n i z a t i o n
a n d dissociation of molecules, a n d the m e a s u r e m e n t
of the masses a n d relative a b u n d a n c e s of t h e v a r i o u s
ions formed. T h e basic principles of m a s s s p e c t r o m
etry h a v e been recognized for m a n y years. A s early as
1898, W i e n d e m o n s t r a t e d t h a t positive i o n s c o u l d b e
deflected b y electric a n d m a g n e t i c fields. In 1911,
T h o m s o n d e m o n s t r a t e d t h a t n e o n n o t only consists of
a t o m s of m a s s 20, b u t is a m i x t u r e also c o n t a i n i n g a
small a m o u n t ( 9 % ) of a species with a m a s s of 22.
This finding, a n d s u b s e q u e n t discoveries of m u l t i isotopic elements, led t o t h e i m p o r t a n t realization
t h a t t h e chemical p r o p e r t i e s of a n element a r e d e p e n
d e n t n o t o n its a t o m i c weight, b u t o n its a t o m i c
n u m b e r . T h e ability of t h e m a s s s p e c t r o m e t e r t o
s e p a r a t e a n d identify isotopes h a s aided physicists
a n d chemists in achieving a better u n d e r s t a n d i n g
of a t o m i c a n d m o l e c u l a r s t r u c t u r e a n d p r o v i d e s
o r g a n i c chemists with a v a l u a b l e tool for s t r u c t u r e
elucidation.

7.

Instrumentation

F i g u r e 1 s h o w s a typical m a s s s p e c t r o m e t e r . T h e
r e a d e r s h o u l d be a w a r e , h o w e v e r , t h a t there a r e a
variety of i o n i z a t i o n , ion s e p a r a t i o n a n d r e c o r d i n g
m e t h o d s , each with its o w n u n i q u e a d v a n t a g e s . F o r
further insight, Kiser (1965) p r o v i d e s a c o m p r e h e n
sive discussion of the i n s t r u m e n t a t i o n a n d principles
of m a s s s p e c t r o m e t r y . Since the wide scope of o r g a n i c
m a s s s p e c t r o m e t r y is d u e in large p a r t t o t h e variety of
sample i n t r o d u c t i o n a n d ionization t e c h n i q u e s , t h e
m o r e i m p o r t a n t of these will be discussed in t h e
following.
I o n i z a t i o n of the s a m p l e is a c c o m p l i s h e d u n d e r
5
7
v a c u u m ( 1 0 " - 1 0 " m m H g ) , so t h a t the ions f o r m e d

292

Mill III
nil.
Mass (/77/e)

\
Mass spectrum

Figure 1
Simplified diagram of a mass spectrometer

h a v e relatively l o n g m e a n free p a t h s a n d c a n be
accelerated a n d m a n i p u l a t e d by electric a n d m a g n e t i c
fields to achieve t h e desired m a s s s e p a r a t i o n . T h e
simple m a s s s p e c t r o m e t e r depicted in Fig. 1 illustrates
a gaseous sample entering an electron-bombardment
ion source. H i g h - e n e r g y electrons strike the m o l
ecules, c a u s i n g the ejection of electrons to p r o d u c e
positively c h a r g e d m o l e c u l a r ions, s o m e of which
dissociate t o p r o d u c e fragment ions of lower m a s s (see
Fig. 2). T h e positively c h a r g e d ions a r e repelled from
the s o u r c e b y a small positive voltage, a n d a r e acceler
a t e d by p a s s i n g t h r o u g h a high-voltage field.
O n e n t e r i n g a m a g n e t i c field, t h e ions a r e deflected
in a circular p a t h w h i c h is d e p e n d e n t u p o n t h e m a s s of
t h e ion a n d t h e s t r e n g t h of t h e m a g n e t i c field. I o n s of
a n a p p r o p r i a t e m a s s follow t h e p a t h leading t o t h e
d e t e c t o r . A m a s s s p e c t r u m is o b t a i n e d by c h a n g i n g
the m a g n e t i c field s t r e n g t h t o successively focus ions
of high t o low m a s s o n the detector.
E l e c t r o n b o m b a r d m e n t is the m o s t c o m m o n l y used
m e t h o d of ionization. T h i s relatively h a r s h m e t h o d
yields a great deal of s t r u c t u r a l i n f o r m a t i o n in the
fragment ions f o r m e d b y dissociation of t h e m o l e c u l a r

Energy from

Figure 2
Production of molecular and fragment ions in a mass
spectrometer

Organic

ion. It suffers, h o w e v e r , b y yielding n o d e t e c t a b l e

m o l e c u l a r i o n s from s o m e less stable o r g a n i c c o m
p o u n d s . T w o c o m m o n soft-ionization m e t h o d s a r e
chemical i o n i z a t i o n a n d field i o n i z a t i o n , w h i c h yield
s t r o n g e r m o l e c u l a r ions b u t d o n o t give t h e s t r u c t u r a l
i n f o r m a t i o n f o u n d in t h e f r a g m e n t i o n s . It is n o t
u n c o m m o n t o o b t a i n m a s s s p e c t r a by b o t h electron
b o m b a r d m e n t a n d chemical i o n i z a t i o n , as c o m p l e
m e n t a r y tools, in t h e c o u r s e of identifying a n o r g a n i c
chemical.
T h e s e i o n i z a t i o n m e t h o d s r e q u i r e t h e s a m p l e t o be
in t h e gas p h a s e p r i o r t o i o n i z a t i o n . F o r gases o r
volatile liquids, it is a simple m a t t e r t o i n t r o d u c e t h e
sample through an expansion volume maintained at
3
slightly r e d u c e d p r e s s u r e (1.010~ m m H g ) . Solids
c a n be i n t r o d u c e d via a p r o b e which is either c o o l e d
or h e a t e d , as r e q u i r e d . M a n y solid o r g a n i c chemicals
h a v e sufficient v a p o r p r e s s u r e for analysis w h e n
h e a t e d to 2 0 0 - 4 0 0 C. H o w e v e r , there is a large a n d
i m p o r t a n t g r o u p of chemicals with insufficient vola
tility for analysis b y these m e t h o d s .
F a s t a t o m b o m b a r d m e n t p r o v i d e s a m e t h o d for
ionization of n o n v o l a t i l e m a t e r i a l s . T h e s a m p l e , i n t r o
d u c e d o n t h e surface of a p r o b e , is b o m b a r d e d by a
high-energy b e a m of n e u t r a l a t o m s , usually a r g o n
a t o m s with a t r a n s l a t i o n a l e n e r g y o f 4 - 8 k e V . A
s p u t t e r i n g p r o c e s s ensues, resulting in m o l e c u l a r a n d
fragment i o n s being p r o d u c e d from t h e s a m p l e w h i c h
are t h e n m a s s a n a l y z e d .
2. The Mass

Spectrum

A m a s s s p e c t r u m is a r e c o r d of t h e m a s s e s a n d relative
a b u n d a n c e s of t h e i o n s f o r m e d from a p a r t i c u l a r
c o m p o u n d . T h e m a s s s p e c t r u m m a y be p r e s e n t e d in
the form of a b a r g r a p h o r a m a s s a n d a b u n d a n c e
table. W h e n t h e general a p p e a r a n c e of a s p e c t r u m is
a n i m p o r t a n t factor in i n t e r p r e t a t i o n , o r w h e n c o m
p a r i n g spectra, t h e b a r g r a p h is preferred. T h e table
offers the a d v a n t a g e of a c c u r a t e i o n - a b u n d a n c e
presentation.
A s first o b s e r v e d b y T h o m s o n , m o s t e l e m e n t s a r e
m i x t u r e s of t w o o r m o r e stable i s o t o p e s differing b y
one or two atomic mass units. Table 1 contains the
elements c o m m o n l y f o u n d in o r g a n i c c o m p o u n d s
a n d t h e relative a b u n d a n c e s of their i s o t o p e s . O f
these, only fluorine, p h o s p h o r u s a n d i o d i n e a r e m o n o isotopic. Since t h e i o n s f o r m e d from a m o l e c u l e a r e
s e p a r a t e d a c c o r d i n g t o their m a s s e s , e a c h i s o t o p e
yields a separately identifiable ion. F o r e x a m p l e , t h e
m o l e c u l a r ion of ethyl c h l o r i d e is revealed as t w o
p e a k s s e p a r a t e d b y t w o a t o m i c m a s s u n i t s (Fig. 3a)
a n d with a n intensity r a t i o c o r r e s p o n d i n g t o t h e
relative a b u n d a n c e s of t h e t w o i s o t o p e s (3:1). T h e
higher-mass p e a k of this d o u b l e t is called t h e + 2
3 7
i s o t o p e p e a k , a n d c o r r e s p o n d s t o C 2H 5 C 1 . S u c h a
pair of p e a k s is therefore characteristic of o n e c h l o r
ine a t o m in a molecule. Likewise, a m o l e c u l a r ion
c o n t a i n i n g b r o m i n e a p p e a r s as t w o p e a k s s e p a r a t e d

Mass

Spectrometry

Table 1
Elements commonly found in organic compounds
Element
Hydrogen
Carbon
Nitrogen

Nuclide

D
C
13
C

Atomic
weight

Exact
mass

Relative
abundance

1.00797

1.00783
2.01410
12.00000
13.00336
14.0031
15.0001
15.9949
16.9991
17.9992
18.9984
27.9769
28.9765
29.9738
30.974
31.9721
32.9715
33.9679
34.9689
36.9659
78.9183
80.9163
126.904

99.99
0.01
98.90
1.10
99.60
0.40
99.76
0.04
0.20
100.00
92.20
4.70
3.10
100.00
95.02
0.76
4.22
75.77
24.23
50.50
49.50
100.00

12.01115
14.0067

1 5N

Oxygen

15.9994

1 8Q

Fluorine
Silicon
Phosphorus
Sulfur

F
Si
Si
30
Si

S
33
S
29

18.9984
28.086
30.974
32.064

3 4S

Chlorine
Bromine
Iodine

CI
C1
Br
81
Br
I
37

35.453
79.909
126.904

b y t w o m a s s units a n d with nearly e q u a l intensities

(Fig. 3b).
W h e n e v a l u a t i n g m a s s spectra, isotopic masses a n d
n o t chemical a t o m i c weights s h o u l d be used. T h e
chemical a t o m i c weights a r e t h e weighted averages of
the naturally occurring isotopes.
T h e m a j o r i t y of ions in a m a s s s p e c t r u m arise from
cleavage of b o n d s in t h e m o l e c u l a r ion a n d t h u s
c o n t a i n only a p o r t i o n of the a t o m s from the original
molecule. S o m e of these f r a g m e n t i o n s a r e formed by
r a n d o m b o n d cleavage a n d m a y even involve re
a r r a n g e m e n t of a t o m s within the m o l e c u l a r ion. T h e r e
is, h o w e v e r , a vast n u m b e r of c o m p o u n d s which
b e h a v e a c c o r d i n g t o a specific a n d predictable
c h e m i s t r y of e l e c t r o n - i m p a c t - i n d u c e d r e a c t i o n s . It is
a n u n d e r s t a n d i n g of t h a t c h e m i s t r y which enables
i n t e r p r e t a t i o n of m a s s spectral p a t t e r n s in t e r m s of
o r g a n i c m o l e c u l a r s t r u c t u r e s . A glimpse a t t h e dif
ferent types of p r o d u c t s (ions) f o r m e d from t h e reac
tions of m a s s s p e c t r o m e t r y is t h e first step t o w a r d
u n d e r s t a n d i n g this chemistry.
M o l e c u l a r i o n s , h a v i n g lost o n e electron from a full
c o m p l e m e n t of p a i r e d electrons, a r e o d d - e l e c t r o n
species a n d a r e d e s i g n a t e d by t h e s y m b o l t . In a d d i
tion t o the c h a r g e d sites, o d d - e l e c t r o n ions c o n t a i n a
radical site, as s h o w n b y t h e e x a m p l e s in Fig. 4.
F r a g m e n t i o n s a r e t h e p r o d u c t s of t h e electroni m p a c t - i n d u c e d c h e m i s t r y w h i c h occurs in t h e m a s s
s p e c t r o m e t e r . T h e s e p r o d u c t s a r e formed by simple
cleavage o r m u l t i c e n t e r f r a g m e n t a t i o n s .

293

Organic

Mass

Spectrometry

Table 2
Energy values for some bonds commonly found in organic
molecules at 25 C

29

100

80

"O
c
D
>

64

Bond energy
1
(kJg" )

60

Bond type

Single bonds

40

rr

C-H
C-C
C-N
C-O

20

c - s

50

C-Si
C-F
C-Cl
C-Br
C-I
O-H
O-Si
N-H
N-N
N-O
S-H
S-S

m /e
(a)
100

80

60

108
81

40

413
346
305
358
272
285
485
339
285
213
463
372
391
163
222
347
226

Double
bonds

Triple bonds

610
615
749
536

835
890

418
607

20

50

Simple cleavage is the f r a g m e n t a t i o n of a single

c o v a l e n t b o n d t o give a n ion a n d a n e u t r a l particle:

100

m/e

A - B - C - D t - A - B - C

(b)
Figure 3
Mass spectra of (a) ethyl chloride and (b) ethyl bromide

+
: C : C : CI :

CH3

CH

M * , Propylene

Ethyl chloride

C H 2^

+.

^CH

^CH

M * , Butadiene

Figure 4
Odd-electron ions

294

CH
M * f Benzene

CH2

0 + Dt

(1)

T h e three i m p o r t a n t factors t h a t d e t e r m i n e which

b o n d s in a c o m p l e x o r g a n i c molecule will b r e a k a n d
which i o n s will be f o r m e d in p r e d o m i n a n c e are: the
relative b o n d s t r e n g t h s , t h e stability of the ions a n d
the n e u t r a l fragment stabilities.
E n e r g y values for s o m e of the m o r e c o m m o n b o n d s
f o u n d in o r g a n i c molecules a r e given in T a b l e 2. T h e
strongest b o n d s a r e t h o s e of t h e d o u b l e a n d triple
variety a n d a r e s e l d o m f o u n d to f r a g m e n t w h e n there
a r e w e a k e r single b o n d s p r e s e n t in the m o l e c u l a r ion.
A m o n g the w e a k e s t b o n d s a r e t h o s e b e t w e e n c a r b o n
a n d t h e heavier h a l o g e n a t o m s , a n d loss of these
a t o m s from m o l e c u l a r ions is often observed.
F r a g m e n t - i o n stability is a n even m o r e i m p o r t a n t
factor in directing t h e f r a g m e n t a t i o n of a molecule.
Since t h e m a i n c o n c e r n is with positively c h a r g e d
ions, t h o s e factors t h a t p r o m o t e c a r b o n i u m - i o n reac
tions a r e of p r i m e i m p o r t a n c e . T h i s is d e m o n s t r a t e d
by t h e m a s s spectra of t w o isomers of b r o m o b u t a n e
(Fig. 5). F r o m t h e relative intensities it c a n be seen
t h a t cleavage of t h e c a r b o n - b r o m i n e b o n d in tertbutyl b r o m i d e occurs m o s t readily t o give the stable
terf-butyl
c a t i o n ( n o m o l e c u l a r ion is o b s e r v e d in
this s p e c t r u m ) . T h e c o r r e s p o n d i n g cleavages in 2b r o m o b u t a n e a n d 1 - b r o m o b u t a n e give progressively
w e a k e r f r a g m e n t i o n s (or s t r o n g e r m o l e c u l a r ions).

Organic

57

100

100

Mass

Spectrometry

43
r-

Q>

c 80

"
c
60
13
.O

>
>
^ 40

20

80 h -

60

"D
C
D

40

72

Li

20

136

_il

50

L
100

50
m/e

m/e

Figure 6
Mass spectrum of 2-butanone

(a)

100

57

15

57

c 60

R - C H - R - R - C H a n d / o r C H - R (4)

60

C H - R - R - C H and/or C H - R

40
+

NH,

: 20 h -

t 50i l

100
m/e

(b)
Figure 5
Mass spectra of (a) 2-bromobutane and (b) teri-butyl
cation

4H,

(5)

'

T h e s p e c t r u m of 2 - b u t a n o n e ( F i g . 6) is representa
tive of f r a g m e n t a t i o n directed b y t h e presence of a
heteroatom.
T h e r e a r e t w o c o m m o n r e a r r a n g e m e n t fragmen
t a t i o n s o b s e r v e d in t h e m a s s spectra of m a n y o r g a n i c
c o m p o u n d s ; b o t h involve t h e transfer of a h y d r o g e n
a t o m . E l i m i n a t i o n f r a g m e n t a t i o n s a r e c o m m o n from
alcohols, a m i n e s , esters, ethers, halides a n d sulfides:
RCH2CH2CH2CHX *

T h e stabilizing influence of d o u b l e b o n d s a n d a r o
m a t i c rings results in preferred cleavage of allylic a n d
benzylic b o n d s :

R.

R C H 2C H 2C H = C H 2* + HX

(6)

w h e r e X = O H , N H 2 , O R , S H o r S R . T h e second
f r a g m e n t a t i o n , k n o w n a s t h e McLafferty r e a r r a n g e
m e n t , o c c u r s from m a n y c o m p o u n d s c o n t a i n i n g
d o u b l e b o n d s a n d aliphatic h y d r o g e n a t o m s situated
in p o s i t i o n s t o give a s i x - m e m b e r e d transfer, a s s h o w n
in E q n . (7):

(2)

H/R'

XH

chr'
(7)

R.

(3)

T h e n o n b o n d i n g electrons of h e t e r o a t o m s a d d n o
table stability t o c a r b o n i u m i o n s , resulting in t h e
c o m m o n -cleavage:

CH

T h e spectra of 2 - h e x a m o n e a n d p h e n e t o l e (Figs. 7a
a n d 7b) d e m o n s t r a t e t h e McLafferty r e a r r a n g e m e n t .
N o t e t h a t 2 - h e x a n o n e also fragments b y simple
cleavage ( F i g . 8).

295

Organic

Mass

100

Spectrometry
43
CH,

CH,

CH

60
"
c

CHX

60
58

tOH

rr

C H

20

57

85

,vv
100

m/e

C = C H

m/e

100

50

C H

= C H

CH

58

85

m/e

(a)

"
C
D
-O

60

40

0)

m/e

94

100
80

122

m/e

94

Figure 8
Fragmentation of 2-hexanone and phenetole

1. J

50

100

m/e
(b)
Figure 7
Mass spectra of (a) 2-hexanone and (b) phenetole

3. Gas Chromatography-Mass

Spectrometry

T h e d e v e l o p m e n t of m a s s s p e c t r o m e t r y d u r i n g t h e
1960s revolutionized t h e field of o r g a n i c analysis, yet
w a s still limited t o the analysis of relatively p u r e
substances. I n t h e 1970s, h o w e v e r , t h e gas c h r o m a t o
g r a p h w a s a d d e d as a n inlet t o t h e m a s s s p e c t r o m e t e r
t o f o r m a n entirely n e w i n s t r u m e n t . W i t h this i n s t r u
m e n t , t h e qualitative p o w e r of t h e m a s s s p e c t r o m e t e r
is a d d e d t o t h e q u a n t i t a t i v e capabilities of t h e gas
chromatograph. Complex mixtures can now be
analyzed b o t h qualitatively a n d q u a n t i t a t i v e l y . G a s
c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y is a n indispens
able t o o l in t h e fields of forensic a n d e n v i r o n
m e n t a l chemistry, d r u g research, m e d i c i n e , industrial
hygiene, a n d flavors a n d fragrances.

4. High-Resolution

C H 2C H

H f

20 r -

Mass

Spectrometry

In 1923 A s t o n discovered t h a t every isotopic m a s s is

characterized b y a small m a s s defect; t h a t is, t h e

296

43

m a s s e s of nuclides a r e n o t simple multiples of a

f u n d a m e n t a l unit. Since this discovery, t h e masses of
all k n o w n stable nuclides h a v e been a c c u r a t e l y
m e a s u r e d . T h e m a s s e s for elements c o m m o n l y f o u n d
in o r g a n i c chemicals a r e given in T a b l e 1. T h e accep
ted a t o m i c weights for t h e elements a r e included t o
p o i n t o u t t h e difference b e t w e e n t h e c o n c e p t i o n s of
t h e chemist a n d t h e m a s s spectroscopist r e g a r d i n g t h e
m a s s of a n a t o m . Since t h e chemist is a c c u s t o m e d t o
using a t o m i c weights, w h i c h a r e a v e r a g e weights of all
t h e i s o t o p e s of a n element, confusion m a y arise as t o
w h a t is m e a n t b y a n a c c u r a t e m a s s as d e t e r m i n e d b y
m a s s s p e c t r o m e t r y . H e a v y isotopes d o n o t c o n t r i b u t e
t o t h e m a s s of a n i o n , b u t result in a l t o g e t h e r different
i o n s a t n o m i n a l l y different m a s s e s . F o r e x a m p l e , t h e
m o l e c u l a r weight of a c e t o n e ( C 3 H 6 0 ) is 58.0707, b u t
t h e m o l e c u l a r i o n h a s a n exact m a s s of 58.0419, with
1 3
a n a c c o m p a n y i n g C isotopic ion of m a s s 59.0453
1 8
a n d a n 0 i s o t o p i c ion of m a s s 60.0462.
B u t a n e is a n o m i n a l i s o b a r of a c e t o n e , b u t its
m o l e c u l a r i o n h a s a n exact m a s s of ( 4 x 1 2 ) +
(10 x 1.007825) = 58.0783 a n d c a n be completely
s e p a r a t e d ( < 1 0 % p e a k overlap) from t h e a c e t o n e
m o l e c u l a r ion b y a m a s s s p e c t r o m e t e r with a res
o l u t i o n of M/AM = 58/0.0364 = 1600. F u r t h e r , a
m a s s m e a s u r i n g a c c u r a c y of only 0.02 a t o m i c m a s s
units w o u l d be r e q u i r e d for u n a m b i g u o u s differentia
tion of t h e t w o m o l e c u l a r i o n s .

Organic

Mass

Spectrometry

E x a c t ion m a s s e s c a n b e used t o d e t e r m i n e elemen

tal c o m p o s i t i o n s of i o n s in t h e m a s s s p e c t r o m e t e r . T o
illustrate, a m o l e c u l a r i o n w i t h a c o m p o s i t i o n of
C 9 H 6 0 2 h a s a n exact m a s s of 146.0368, w h e r e a s t h e
exact m a s s for a c o m p o u n d of c o m p o s i t i o n C 1 0H 1 0O 3
is 146.0732. W h e n used in c o n j u n c t i o n with i s o t o p e
p e a k o b s e r v a t i o n s , exact m a s s m e a s u r e m e n t s b e c o m e
even m o r e useful. F o r e x a m p l e , t h e c o m p o s i t i o n
C 7 H 1 3N C 1 h a s a n exact m a s s of 146.0737. T h e c h a r a c
37
teristic C1 i s o t o p e p e a k easily differentiates this
c o m p o s i t i o n from C 1 0H 1 0O 2 , even t h o u g h t h e t w o
masses a r e nearly e q u a l .
E x a c t m a s s e s c a n n o t b e d e t e r m i n e d b y all m a s s
spectrometers. Double-focusing mass spectrometers
are generally u s e d for these a c c u r a t e m e a s u r e m e n t s .
T h e ion b e a m in such i n s t r u m e n t s passes t h r o u g h a n
electrostatic sector in a d d i t i o n t o t h e m a g n e t i c sector,
t h e r e b y giving a b e t t e r defined (or resolved) m a s s
spectrum. These high-resolution instruments can
generally resolve i o n s s e p a r a t e d b y only 0.001 m a s s
units. M o r e i m p o r t a n t l y , they c a n m e a s u r e t h e m a s s e s
of i o n s t o accuracies of 0 . 0 0 0 1 % .
H i g h - r e s o l u t i o n m a s s s p e c t r o m e t r y is c o m m o n l y
used t o identify u n k n o w n c o m p o u n d s in t h e p h a r m a
ceutical, synthetic c h e m i s t r y , m e d i c a l , e n v i r o n m e n t a l ,
a n d flavors a n d fragrance industries.

t e c h n i q u e c o m b i n i n g t h r e e distinct analytical m e t h o d s
i n t o o n e . T h e volatile pyrolysis p r o d u c t s a r e swept
o n t o a g a s c h r o m a t o g r a p h y c o l u m n t o be analtically
s e p a r a t e d , identified a n d m e a s u r e d by t h e m a s s
s p e c t r o m e t e r . T h i s t e c h n i q u e h a s its p r i m a r y applica
t i o n in t h e identification of t h e c o m b u s t i o n p r o d u c t s
of p o l y m e r s . I n this case, air is p a s s e d t h r o u g h the
pyrolysis c h a m b e r while t h e s a m p l e is h e a t e d t o 1 5 0 0 2000 C.

5. Pyrolysis-Mass

Bibliography

Spectrometry

A l t h o u g h generally limited t o t h e analysis o r c o m

p o u n d s with a t least s o m e volatility, m a s s s p e c t r o m
etry h a s been e x t e n d e d t o t h e field of p o l y m e r s b y t h e
d o u b l e t e c h n i q u e of p y r o l s i s - m a s s s p e c t r o m e t r y .
W h e n subjected t o high t e m p e r a t u r e s ( 3 0 0 - 1 0 0 0 C),
m o s t synthetic p o l y m e r s u n d e r g o d e g r a d a t i o n t o yield
low-molecular-weight, volatile p r o d u c t s . T h e m a s s
spectra of these p r o d u c t s a r e often c h a r a c t e r i s t i c of
the p o l y m e r u n i t s .
E v e n m o r e detailed analyses c a n b e p e r f o r m e d b y
pyrolysis-gas c h r o m a t o g r a p h y - m a s s spectrometry, a

6. Quantitative

Mass

Spectrometry

T h e m a s s s p e c t r o m e t e r c a n b e a very powerful q u a n t i
tative t o o l . Its i n h e r e n t function as a m a s s analyzer
offers t h e a n a l y s t t h e ability t o use stable-isotopelabelled i n t e r n a l s t a n d a r d s . Since c a r b o n is t h e p r e
1 3
d o m i n a n t element in o r g a n i c c o m p o u n d s , C is t h e
2
m o s t c o m m o n s t a b l e - i s o t o p e t a g . T h e use of H - a n d
18
0 - l a b e l l e d c o m p o u n d s is also c o m m o n . A n a l o g u e s
a n d h o m o l o g u e s a r e u s e d as i n t e r n a l s t a n d a r d s w h e n
t h e a p p r o p r i a t e stable-isotope-labelled c o m p o u n d s
a r e n o t available.
See also: Gas and Liquid Chromatography; Laser Micro
probe Mass Spectrometry; Laser Sampling Inductively
Coupled Plasma Mass Spectrometry

Gudzinowicz B, Gudzinowicz M, Martin F 1976 Funda

mentals of Integrated GC/MS. Elsevier, Amsterdam
Kiser R W 1965 Introduction to Mass Spectrometry and Its
Applications. Prentice-Hall, Englewood Cliffs, NJ
Millard J 1978 Quantitative Mass Spectrometry. Heyden,
London
Shrader S R 1971 Introductory Mass Spectrometry. Allyn
and Bacon, Boston, MA
S. R. S h r a d e r
[Shrader Analytical a n d Consulting Laboratories,
Detroit, Michigan, USA]

297


Paper and Paperboard: Destructive
Mechanical Testing
T h e p r i m a r y m e c h a n i c a l p r o p e r t i e s of p a p e r t h a t a r e
tested destructively a r e (a) its uniaxial l o a d - e l o n g a
tion ( L E ) characteristics; (b) its " b u r s t i n g s t r e n g t h , " a
kind of o m n i d i r e c t i o n a l tensile test; a n d (c) its " t e a r
ing s t r e n g t h , " a failure-line p r o p a g a t i o n test. T h e s e
three p r o p e r t i e s will be e x a m i n e d in this article in
t e r m s of the relevant fiber p r o p e r t i e s a n d p r o c e s s
variables. N o n d e s t r u c t i v e e v a l u a t i o n of p a p e r is
considered in t h e article Paper and Paperboard:
Non
destructive
Evaluation.

1. Load-Elongation

Characteristics

T h e uniaxial L E characteristics of a sheet reflect, t o a

large extent, t h e c o m p a r a b l e p r o p e r t i e s of its consti
t u e n t fibers set i n t o a specific a r r a n g e m e n t o r s t r u c
ture. T h e L E curves a, b a n d c in Fig. 1 a r e t h o s e of
fibers with different i n t e r n a l fibrillar o r i e n t a t i o n s
tested axially a n d as d r i e d u n d e r o r w i t h o u t restraint.
Because of their i n t e r n a l fibrillar s t r u c t u r e , fibers
h a v e significantly different L E characteristics in their
transverse directions, p e r p e n d i c u l a r t o the fiber axis.
A l t h o u g h transverse tests h a v e never been m a d e
because of e x p e r i m e n t a l difficulties, a theoretical
transverse L E c u r v e is s h o w n in Fig. 1 a t d. T h e
i m p o r t a n t p o i n t is t h a t fibers stretch far m o r e a n d a r e

w e a k e r in their transverse directions t h a n axially,

p r o b a b l y by a factor of 2 0 - 5 0 .
A n o t h e r m o s t i m p o r t a n t p r o p e r t y affecting the L E
c u r v e of p a p e r is t h e s h r i n k a g e b e h a v i o r of fibers as
they d r y from 60 t o 9 0 % solids (i.e., as w a t e r leaves
t h e i n t e r n a l p o r e s b e t w e e n t h e fibrils). Because the
fibrils themselves d o n o t s h r i n k b u t merely c o m e
closer t o g e t h e r d u r i n g t h e d r y i n g of t h e fibers indi
vidual fibers shrink only 1 - 5 % axially a n d 1 5 - 3 0 %
transversely over this m o i s t u r e r a n g e .
N o w c o n s i d e r t w o p a r t l y b o n d e d fibers oriented
p e r p e n d i c u l a r t o each o t h e r in a sheet being dried
from 60 t o 9 0 % solids (Fig. 2). A t 6 0 % solids m o s t of
t h e free interfiber w a t e r h a s b e e n r e m o v e d a n d the
b o n d b e t w e e n t h e fibers h a s c o n s i d e r a b l e strength. A s
t h e t w o fibers shrink transversely, they create a c o m
pressive axial force o n e a c h o t h e r over t h e b o n d e d
a r e a . If F i b e r a is o r i e n t e d in t h e m a c h i n e direction
( M D ) of t h e sheet (in w h i c h it is held u n d e r restraint
d u r i n g d r y i n g ) , a n d F i b e r b in t h e cross direction
( C D ) (where r e s t r a i n t is m i n i m a l ) , only F i b e r b will be
able t o s h r i n k axially.
T h e p o r t i o n of F i b e r b c o m p r e s s e d axially d u r i n g
d r y i n g is " m i c r o c o m p r e s s e d . " W h e n t h e m i c r o c o m pressed p o r t i o n of a fiber is strained axially, its L E
c u r v e (e in Fig. 1) first e x t e n d s significantly with little
l o a d d e v e l o p m e n t as the m i c r o c o m p r e s s i o n s a r e being
s t r a i g h t e n e d o u t . O n c e this h a s o c c u r r e d , t h e fiber
develops a l o a d in t h e n o r m a l m a n n e r .
Because p a p e r is held u n d e r r e s t r a i n t in the M D of
a p a p e r m a c h i n e a n d u n d e r relatively low C D tensions
(only as t h e sheet rides over t h e drier cans), the C D o r i e n t e d fibers h a v e a far g r e a t e r incidence of m i c r o c o m p r e s s e d zones t h a n t h e M D - o r i e n t e d fibers. In
fact, a n extremely well b o n d e d sheet such as glassine
typically s h r i n k s 8 % in t h e C D d u r i n g drying. T h i s
a m o u n t of s h r i n k a g e is close t o t h e theoretical level of
o n e t h i r d of t h e m a x i m u m 3 0 % transverse fiber
shrinkage.

CD

MD

Elongation

Figure 1
Fiber load-elongation curves: fibril
orientation
e
(a) "parallel" to fiber axis, (b)-( ) at large angle to
fiber axis; drying conditions: (a) free or restrained,
(b) restrained, (c) free, (d) and (e) microcompressions

A r e a of
bonding

Figure 2
Mutually perpendicular partly boned fibers; MD, machine
direction; CD, cross direction; shading denotes bonded
area

299

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Testing

T h e L E p r o p e r t i e s of a sheet a r e different from t h e

axial L E p r o p e r t i e s of its fibers a n d are a function of
the direction in which t h e test is being c o n d u c t e d . T h i s
occurs because:
(a)

fibers a r e oriented m o r e o r less r a n d o m l y in t h e

p l a n e of a sheet (there is usually a small bias in
the M D of c o m m e r c i a l p a p e r s ) ;

(b) fiber axial a n d transverse p r o p e r t i e s a r e signific

antly different; a n d
(c)

the L E c u r v e a n d its m i c r o c o m p r e s s i o n c o n t e n t
is a function of fiber o r i e n t a t i o n in a sheet.

C o n s i d e r first a sheet dried u n d e r restraint in all

directions t o p r e v e n t o r minimize the f o r m a t i o n of
m i c r o c o m p r e s s i o n s , for instance, a test sheet o r h a n d
sheet p r o d u c e d in t h e l a b o r a t o r y . It h a s been deter
m i n e d t h a t t h e c o n t r i b u t i o n t o t h e l o a d developed b y
a sheet of a fiber oriented a t a n angle t o the direction
4
of sheet strain is p r o p o r t i o n a l t o (sin 0), T h u s , in t h e
case of a h a n d s h e e t of r a n d o m l y o r i e n t e d fibers dried
uniformly u n d e r restraint a n d devoid of m i c r o c o m
pressions (Fig. 1, c u r v e a ) , t h e l o a d developed by the
sheet p e r u n i t strain is e q u a l t o o n e third of the
c o r r e s p o n d i n g fiber l o a d ( C o x 1952).
F i g u r e 3 s h o w s several typical l o a d - e l o n g a t i o n
curves of p a p e r . All exhibit three distinct c h a r a c t e r i s
tics: (a) a n " e l a s t i c " region E; (b) a " p l a s t i c " z o n e P;
a n d (c) a failure p o i n t F . T h e s e three regimes will n o w
be analyzed in t e r m s of the m e c h a n i s m s described
above.
T h e curve of Fig. 3a represents t h e h a n d s h e e t
described a b o v e . It h a s a relatively extensive "elastic
r e g i m e " which reflects only t h e elastic axial straining
of its fibers. If this sheet is strained to less t h a n its
elastic limit a n d is t h e n allowed t o relax, it will r e t u r n
to its original length.
T h e plastic regime is a n extension of t h e elastic o n e
with t w o a d d i t i o n a l m e c h a n i s m s c o m i n g i n t o play,
namely, b o n d failures a n d r e m o v a l of m i c r o c o m p r e s
sions. I n t h e first of these m e c h a n i s m s for failure,
b o n d e d a r e a s between fibers fail. Such failures a r e
m o s t l y p a r t i a l , a l t h o u g h there a r e s o m e failures of
c o m p l e t e b o n d e d a r e a s . E a c h b o n d e d a r e a failure is
a c c o m p a n i e d by a decrease in t h e l o a d in the p o r t i o n
of the t w o fibers which were originally b o n d e d . T h i s is
illustrated in Fig. 4.
T h e sheet w h o s e l o a d - e l o n g a t i o n curve is s h o w n in
Fig. 3b c o n t a i n s a c o n s i d e r a b l e fraction of m i c r o c o m pressed fibers. After a very s h o r t elastic extension
further straining results in p u l l o u t of m i c r o s c o m p r e s sion as well as b r e a k i n g of b o n d s . A s s h o w n in Fig.
Id, such straining is a c c o m p a n i e d by little o r n o l o a d
build u p . It is only after t h e m i c r o s c o m p r e s s i o n s a r e
r e m o v e d t h a t further extension of the fibers results in
load development.
It is p r o b a b l e t h a t in a n M D l o a d - e l o n g a t i o n test of
a sheet, the r a t i o of b o n d failure t o m i c r o c o m p r e s s i o n
r e m o v a l d u r i n g straining is greater t h a n in a C D test.
300

Elongation

Figure 3
Paper load-elongation curves: (a) sheet of randomly
oriented fibers dried uniformly under constraint, no
microcompressions; (b) sheet containing microcompressed
fibers, showing lines (arrowed) of relaxation and second
straining; (c) sheet with failure induced by bond failure;
(d) sheet with failure induced by fiber failure; "elastic"
region; "plastic" zone; F failure point

Figure 4
Diagram of failure of bonded area (shaded): broken lines
show orientation of fibers in relaxed condition after failure

Paper

However, to date, no quantitative measurements have

been m a d e of t h e relative c o n t r i b u t i o n s of t h e t w o
m e c h a n i s m s t o t h e plastic regime.
If a sheet t h a t h a s been s t r a i n e d i n t o t h e plastic
regime is allowed t o relax, its length in t h e u n l o a d e d
state will be g r e a t e r t h a n initially. Such " p e r m a n e n t
s e t " is related t o m i c r o c o m p r e s s i o n s a n d b o n d s w h i c h
h a v e n o t r e f o r m e d w h e n t h e strain h a s been r e m o v e d .
If this sheet is s u b s e q u e n t l y strained a g a i n , t h e elastic
z o n e will b e significantly greater. It is only w h e n t h e
sheet is strained t o t h e s a m e extent as in t h e initial
cycle t h a t t h e t w o l o a d - r e d u c i n g m e c h a n i s m s of t h e
plastic regime r e s u m e .
T h e final failure of t h e sheet is g o v e r n e d b y o n e of
t w o m e c h a n i s m s . I n w e a k l y b o n d e d sheets such as
tissue, towelling a n d n e w s p r i n t , a p o i n t is r e a c h e d in
the plastic regime w h e r e , for a given i n c r e m e n t of
sheet strain, t h e l o a d increase in t h e r e m a i n i n g l o a d b e a r i n g fibers is less t h a n t h e l o a d loss in t h e fibers
t h a t n o longer act as l o a d - b e a r i n g elements. T h u s , a
negative l o a d o r loss is experienced in t h a t strain
increment. F u r t h e r s t r a i n i n g of t h e sheet greatly a c
celerates t h e p r o c e s s a n d t h e sheet fails. T h i s m e c h a n
ism of sheet failure is referred to as " s h e e t failure
i n d u c e d b y b o n d failure."
A s l o n g as b o n d failure is t h e g o v e r n i n g m e c h a n
ism, t h e tensile s t r e n g t h a n d failure stretch of a sheet
will increase with increased degree of b o n d i n g a n d
increased fiber length (the longer a fiber, t h e m o r e
b o n d failures a r e r e q u i r e d t o r e m o v e it as a l o a d b e a r i n g element). T h e fiber s t r e n g t h per se d o e s n o t
enter i n t o c o n s i d e r a t i o n .
A different m e c h a n i s m g o v e r n s the tensile s t r e n g t h
of w e l l - b o n d e d sheets. I n this case, t h e sheets c a n b e
strained t o t h e p o i n t w h e r e a fiber o r i e n t e d in t h e
direction of s t r a i n i n g is e x t e n d e d t o its failure strain
2
(the strain of fibers is p r o p o r t i o n a l t o s i n 0, w h e r e is
the angle of o r i e n t a t i o n of t h e fibers relative t o t h e
strain direction). F a i l u r e of a fiber results in a n i m p a c t
l o a d o n its i m m e d i a t e n e i g h b o r s , p r e c i p i t a t i n g a n
instantaneous
catastrophic
sheet
failure.
This
m e c h a n i s m of sheet failure is referred t o as " s h e e t
failure i n d u c e d b y fiber f a i l u r e . "
T h e tensile s t r e n g t h of sheets in w h i c h failure is
i n d u c e d b y fiber failure increases with increased b o n d
ing (Fig. 3d). H o w e v e r , all o t h e r factors r e m a i n i n g
c o n s t a n t , the failure stretch of sheets r u p t u r e d by this
m e c h a n i s m is i n d e p e n d e n t of t h e degree of b o n d i n g .
O n c e failure of a sheet h a s been initiated b y either
fiber failure o r b o n d failure, its further c a t a s t r o p h i c
failure is essentially a n i n s t a n t a n e o u s t e a r i n g of t h e
sheet, which c o m p r i s e s t w o m e c h a n i s m s . A s t h e fail
u r e line a p p r o a c h e s a given fiber s t r a d d l i n g t h e m o v
ing r u p t u r e line (Fig. 5), t h e r a p i d l o a d b u i l d u p causes
b o t h b o n d s a n d fibers t o fail. Clearly, t h e longer t h e
fibers a n d t h e g r e a t e r t h e degree of b o n d i n g , t h e m o r e
fibers fail.

and Paperboard:

Destructive

Mechanical

Testing

Figure 5
Tearing by moving rupture line

2. Bursting

Strength

D e t e r m i n a t i o n of t h e b u r s t i n g s t r e n g t h of p a p e r is a
widely used test, p a r t i c u l a r l y in t h e p a c k a g i n g a n d
b o x industries. T h e test is, in effect, a n o m n i d i r e c
t i o n a l tensile test. T h e sheet is held in a 3.3 c m
d i a m e t e r c l a m p a n d is subjected t o a u n i f o r m pressure
from o n e side (Fig. 6). T h e results a r e related t o
v a r i o u s characteristics
of t h e
load-elongation
b e h a v i o r of the p a p e r .
It h a s been f o u n d t h a t t h e b u r s t i n g s t r e n g t h of
m a c h i n e - m a d e p a p e r s is related t o b o t h the tensile
s t r e n g t h a n d t h e failure stretch e of t h e p a p e r .
Principally, b u r s t i n g s t r e n g t h is related t o t h e M D
values of a n d e. T h i s c a n be seen from t h e following
expression for t h e b u r s t i n g s t r e n g t h :

V^CD /

L(l + % D )

T h i s e q u a t i o n states t h a t t h e tensile strength a n d

stretch of t h e first fibers t o fail in such a test (the M D o r i e n t e d fibers) a r e the g o v e r n i n g factors in b u r s t i n g
strength.

3. Tearing

Strength

or

Resistance

T h e tear test value of a sheet is a m e a s u r e of the

energy e x p e n d e d in t h e c o n t r o l l e d , relatively slow
p r o p a g a t i o n of a failure line. T w o types of test are
e m p l o y e d : t h e o u t - o f - p l a n e E l m e n d o r f tear test a n d
i n - p l a n e testers.
T h e t e a r test involves t w o m e c h a n i s m s : (a) b o n d
failures, resulting in t h e pulling of fibers o u t of the
sheet (Fig. 5); a n d (b) fiber failures. Clearly, t h e longer
t h e fibers of a sheet, t h e m o r e fiber p u l l o u t is involved
and the greater the tear strength.

Figure 6
Bursting strength test

301

Paper

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Mechanical

Testing
Seth R S, Page D 1980 The elastic modulus of paper: the
effects of dislocations, microcompressions, curl, crimps
and kinks. Tappi 63(10): 99-102
O. J. K a l l m e s
[ M / K Systems, D a n vers,
Massachusetts, USA]

Degree of bonding

Figure 7
Sheet tear strength as a function of degree of fiber-fiber
bonding

Increased b o n d i n g , h o w e v e r , plays a s o m e w h a t
different role. W h e n b o n d s are a d d e d t o a n u n b o n d e d
sheet, the tear s t r e n g t h initially increases with t h e
increased b o n d i n g . A t very low b o n d i n g , b o n d failure
a n d fiber p u l l o u t a r e the only m e c h a n i s m s o c c u r r i n g .
A t high levels of b o n d i n g , t h e fibers s t a r t to fail as
well, a n d the t o t a l n u m b e r of fibers involved in tear
resistance begins t o decrease. T h e energy required t o
r u p t u r e a fiber is far less t h a n t h a t r e q u i r e d to b r e a k a
large n u m b e r of b o n d s . T h u s , the tear s t r e n g t h
reaches a m a x i m u m value at a relatively low degree
of b o n d i n g a n d decreases with increased degree of
b o n d i n g (Fig. 7).
See also: Paper and Paperboard: Nondestructive Evaluation

Bibliography
Cox L 1952 The elasticity and strength of paper and other
materials. Br. J. Appl. Phys. 3: 72-9
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 1: uniform
strain theory for paper. Pap. Ind. Technol. 18: 222; 224-7
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 2: the charac
teristics of fibers taken into account. Pap. Ind. Technol.
18: 243-5
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 3: theory of the
tensile failure of Pap. Ind. Technol. 18: 283-5
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 4: experi
mental evaluation of the theory. Pap. Ind. Technol. 18:
328-31.
Page D H, Seth R S DeGrace J 1980 The elastic
modulus of paper: the controlling mechanisms. Tappi
62(9): 99-102.
Seth R S, Barbe C, Williams J C R, Page D 1982
Strength of wet webs: a new approach. Tappi 65(3): 135-8
Seth R S, Page D 1980 The elastic modulus of paper II:
the importance of fiber modulus, bonding and fiber
length. Tappi 63(6): 113-16

302

Paper and Paperboard: Nondestructive

Evaluation
T h e d e v e l o p m e n t of n o n d e s t r u c t i v e e v a l u a t i o n tech
niques for p a p e r a n d p a p e r b o a r d h a s r e a c h e d a high
degree of refinement since t h e a p p l i c a t i o n of c o m
p u t e r systems t o high-speed w e b m a n u f a c t u r i n g p r o
cesses in t h e mid-1960s. T h e r e l a t i o n s h i p between
d e v e l o p m e n t s in c o m p u t e r systems a n d t h o s e in n o n
destructive m e a s u r e m e n t s h a s b e e n b o t h causal a n d
casual: c o m p u t e r e v o l u t i o n h a s c a u s e d r e v o l u t i o n a r y
i m p r o v e m e n t s in signal processing a c c u r a c y a n d relia
bility a n d , in a casual sense, c o m p u t e r t e c h n o l o g y h a s
s p a w n e d d e v e l o p m e n t of n o n d e s t r u c t i v e sensors as
critical i n p u t s for sophisticated c o m p u t e r systems.
W i t h a few exceptions, m o d e r n sensors a r e b a s e d
o n physics principles a n d m a n u f a c t u r i n g techniques
t h a t a r e fifty o r m o r e years old; sensor e v o l u t i o n h a s
been the result of p r o g r e s s in a p p l i c a t i o n engineering.
A s e v o l u t i o n of a p a r t i c u l a r sensor p r o c e e d s , three
distinct stages a r e e n c o u n t e r e d . First, a n e x p l o r a t o r y
p e r i o d o c c u r s , d u r i n g w h i c h m a r k e t forces define a
m e a s u r e m e n t need, a n d c o m p e t i n g technologies a n d
a p p r o a c h e s a r e b r o u g h t t o b e a r o n t h e need. Second,
a m a t u r a t i o n p e r i o d o c c u r s , d u r i n g which the success
ful a p p r o a c h e s e m e r g e . Finally, a refinement p e r i o d
occurs, d u r i n g which i m p r o v e m e n t s a n d a d a p t a t i o n s
of t h e m a t u r e technologies a r e m a d e . T h e time for
sensor e v o l u t i o n is m e a s u r e d in d e c a d e s , reflecting the
time r e q u i r e d t o resolve a p p l i c a t i o n p r o b l e m s , a n d t o
a c c o m m o d a t e evolving e x p e c t a t i o n s for c o n t i n u e d
enhancements.
In contrast, measurement technology has under
g o n e r e v o l u t i o n a r y a d v a n c e s as digital c o m p u t e r a n d
m i c r o p r o c e s s o r technologies h a v e e x p a n d e d t h e
available real-time c o m p u t i n g p o w e r while s i m u l t a n e
ously r e d u c i n g the cost a n d increasing t h e reliability
of t h e signal processing. W h i l e early s e n s o r - c o m p u t e r
c o m b i n a t i o n s were limited b y real-time processing
r e q u i r e m e n t s of t h e sensors in a system, t h e i n t r o
d u c t i o n of m i c r o p r o c e s s o r s in t h e mid-1970s h a s
facilitated d i s t r i b u t i o n of signal processing t h r o u g h
o u t a system, a n d p e r m i t t e d extensive high-speed,
real-time processing of n u m e r o u s sensors within a
system.

/.

Nucleonic

Technology

sensors were first a p p l i e d for m e a s u r e m e n t of basis

weight (weight p e r u n i t a r e a ) in t h e p a p e r industries

Paper

in the late 1940s, following t h e c o m m e r c i a l avail

ability of artificially p r o d u c e d r a d i o i s o t o p e s . L a t e r ,
x - r a d i a t i o n sensors were d e v e l o p e d for a s h m e a s u r e
m e n t s , a n d x-ray fluorescence sensors were a p p l i e d for
t h e m e a s u r e m e n t of c a l c i u m a n d t i t a n i u m in c o a t i n g s
a n d fillers. G e n e r a l l y , a t r a n s m i s s i o n configuration
h a s been utilized o n a s c a n n i n g m e c h a n i s m , w h i c h
m o v e s t h e sensor a c r o s s t h e w e b .
D u r i n g t h e e x p l o r a t o r y p e r i o d of ^ - s e n s o r evolu
tion, n u m e r o u s r a d i o i s o t o p e s were utilized for specific
m e a s u r e m e n t s , a n d v a r i o u s geometrical configu
r a t i o n s were e m p l o y e d . A s t h e t e c h n o l o g y m a t u r e d ,
t w o r a d i o i s o t o p e s e m e r g e d as p r e d o m i n a n t in t h e
8 5
p a p e r industries: K r for light p r o d u c t s ( u p t o
2
1000 g m " ) a n d ^ S r for h e a v y p r o d u c t s .
Since t h e early a p p l i c a t i o n s of n u c l e o n i c t e c h n o l o g y
in t h e p a p e r industries, e m p h a s i s h a s been placed o n
o v e r c o m i n g v a r i o u s sensor limitations in o r d e r t o
achieve high a c c u r a c y in t h e on-line e n v i r o n m e n t .
During the maturation period, m a n y instrumental
limitations were resolved t h r o u g h d e v e l o p m e n t of
automatic standardization, which comprises periodic
m e a s u r e m e n t of t h e e m p t y g a p c o n d i t i o n off-line a n d
s u b s e q u e n t signal processing t o c o r r e c t for a p p a r e n t
n o n z e r o basis weight i n d i c a t i o n . A u t o m a t i c s t a n
d a r d i z a t i o n also c o r r e c t s for dirt a c c u m u l a t i o n o n
t h e sensor a n d for gross v a r i a t i o n s of air m a s s in
t h e m e a s u r e m e n t g a p which result from t e m p e r a t u r e
and barometric pressure changes.
D u r i n g the refinement stages, m e a s u r e m e n t of a n d
c o m p e n s a t i o n for g a p t e m p e r a t u r e a c r o s s the w e b
h a v e evolved. I n a d d i t i o n , c o r r e c t i o n for a n o m a l i e s of
a t t e n u a t i o n , d u e t o scattering p a t t e r n c h a n g e s
resulting from c h a n g e s in t h e p o s i t i o n of t h e w e b in
t h e g a p o r c h a n g e s in t h e a t o m i c c o m p o s i t i o n of t h e
w e b , h a s been i m p l e m e n t e d t h r o u g h t h e design of
c o m p e n s a t i n g scattering s t r u c t u r e s within t h e g e o
m e t r y of t h e g a u g e itself. M e a s u r e m e n t a c c u r a c y
achievable is 0 . 2 % of t h e basis weight of t h e w e b
2
(or 0.15 g m ~ ) in typical on-line a p p l i c a t i o n s in t h e
p a p e r industries. A s u m m a r y of g a u g e limitations a n d
c o u n t e r a c t i n g design a p p r o a c h e s is given in T a b l e 1.
C h a r a c t e r i s t i c a t t e n u a t i o n a n d fluorescence of lowenergy p h o t o n s (x o r rays) by metallic a t o m s in filler
a n d c o a t i n g m i n e r a l s p r o v i d e t h e m e c h a n i s m for
m e a s u r e m e n t of a s h in p a p e r . L o w - e n e r g y p h o t o n s
( 1 - 1 0 keV) interact with metallic a t o m s in t h e a s h
through photoelectric absorption, whereby a p h o t o n
transfers its energy t o a n a t o m i c electron, ejecting t h e
electron from its o r b i t a l shell. Since electrons in
different shells a r e b o u n d t o t h e a t o m with different
a n d q u a n t i z e d energies, t h e a t t e n u a t i o n coefficient
function exhibits discontinuities a t t h e specific ener
gies r e q u i r e d t o eject electrons from different shells.
W h e n a free electron fills a v a c a n c y t h u s c r e a t e d a
fluorescent r a y of q u a n t i z e d energy is e m i t t e d .
F i g u r e 1 indicates t h e a t t e n u a t i o n coefficients for
typical a s h m i n e r a l s , clay a n d T i 0 2 , as functions of
p h o t o n energy. T h e c u r v e for T i 0 2 exhibits a K - e d g e

and Paperboard:

Nondestructive

Evaluation

Table 1
/?-Sensor limitations
Type
Instrumental
radioactive decay
drift of detector and
electronics
sensitivity to
mechanical
displacements

statistical noise
External influences
dirt accumulation
variation of air mass
in gap

composition changes
movement of sheet in
gap (passline
effect)

Counteracting design approach

automatic standardization,
computer modelling
use of ion chamber, solid-state
electronics, automatic
standardization, sensor
temperature stabilization
precision scanner design,
compensation with
geometrical shielding
2
elements (anti-r disks),
displacement measurement
and compensation
efficient source design, efficient
gauge geometry, filtering
automatic standardization,
air wipes
design to minimize source/detector
distance, temperature
measurement and
compensation,
temperature-controlled air
wipes, sensor temperature
stabilization
compensation with scattering foils
restriction of movement with
guides, compensation with
collimating and scattering foils

d i s c o n t i n u i t y a t 4.96 keV, w h e r e incident p h o t o n

energy j u s t e q u a l s t h e energy r e q u i r e d to eject a n
a t o m i c electron from t h e shell. A b o v e this energy,
t h e a t t e n u a t i o n coefficient decreases as energy in
creases; t h e edges for metallic c o n s t i t u e n t s of clay
( M g , Al, Si) o c c u r a t energies below 2 k e V . T h e
t i t a n i u m fluorescent emission ( K a ) occurs j u s t below
t h e edge, a t 4.95 keV.
I n a t r a n s m i s s i o n configuration, t h e a b s o r p t i o n of
t h e t u b e - g e n e r a t e d r a y s p r o v i d e s t h e basis for a
composition-insensitive a s h m e a s u r e m e n t . T h e x-ray
s p e c t r u m s h o w n in F i g . 1 is shifted t h r o u g h adjust
m e n t of t h e a n o d e voltage t o s t r a d d l e t h e edge of
t h e highest a t o m i c n u m b e r element in t h e ash; this
equalizes t h e a v e r a g e a t t e n u a t i o n coefficients of a n y
two ash constituents and thus renders the measure
m e n t c o m p o s i t i o n insensitive. A s a result of refine
m e n t s in i n s t r u m e n t a l design, this t e c h n i q u e p r o v i d e s
accuracies b e t t e r t h a n 0 . 5 % t o t a l ash in typical
a p p l i c a t i o n s . T r a n s m i s s i o n m e a s u r e m e n t s utilizing
5 5
F e as a p h o t o n s o u r c e (5.9 keV) are also m a d e o n
line, b u t since a s h c o n s t i t u e n t s h a v e different a t t e n u a
tion coefficients, c o m p o s i t i o n c h a n g e s d e g r a d e sensor
c a l i b r a t i o n , a n d a c c u r a c y is seriously i m p a i r e d .

303

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T i K a line
4 . 9 5 keV
\
\

Ti edge
4 . 9 6 keV

x-ray
spectrum

average

Evaluation

\.

T1O2 a t t e n u a t i o n
coefficient

fcZ>
<<i
fcs^

clay attenuation
^/^coefficient
\

I
1

4
5
X-ray energy

6
(keV)

Figure 1
X-ray spectra and attenuation coefficients of typical ash
minerals (clay and T i 0 2 ) at low energies

T h r o u g h use of a n energy-sensitive detector, which

provides o u t p u t pulses p r o p o r t i o n a l t o t h e energy of
discrete detected p h o t o n s , t h e fluorescent rays emit
ted by calcium (3.69 keV) a n d t i t a n i u m (4.95 keV) in
the ash c a n be detected selectively a n d categorized by
electronic pulse-height analysis. E r r o r s c a u s e d by
i n t e r a c t i o n of fluorescent rays within the sheet itself
(matrix effect), o v e r l a p of detected fluorescent spectra
a n d i n h e r e n t slow detection rates limit on-line a c c u r a
cies to a b o u t 1 0 % of the c o m p o n e n t c o n c e n t r a t i o n .

2. Optical

Technology

Optical techniques for on-line m e a s u r e m e n t s h a v e

m a t u r e d in t h e early 1980s; w o r l d w i d e e c o n o m i c
c o n d i t i o n s a n d q u a l i t y e m p h a s i s h a v e s p a w n e d re
q u i r e m e n t s for c o n t i n u o u s n o n d e s t r u c t i v e e v a l u a t i o n
of optical p r o p e r t i e s of p a p e r .
Derived from off-line testing m e t h o d s , on-line
m e a s u r e m e n t s c a n be classified i n t o large- o r smallscale m e a s u r e m e n t s a c c o r d i n g t o t h e d i m e n s i o n s of
the light-fiber i n t e r a c t i o n characteristic of t h e
p r o p e r t y m e a s u r e d . T h e large-scale
properties
(color, brightness a n d opacity) a r e well d e n n e d as
reflectances characterized by specific w a v e l e n g t h s ,
geometries a n d b a c k i n g m a t e r i a l s . T h e small-scale
p r o p e r t i e s ( s m o o t h n e s s , gloss a n d f o r m a t i o n ) a r e less
well d e n n e d surface o r single-sheet characteristics.
T h e c r u x of d e v e l o p m e n t effort r e g a r d i n g t h e largescale optical p r o p e r t i e s h a s been the m e a n s of m e a s u r
ing a single free-sheet p a r a m e t e r a n d e x t r a p o l a t i n g t o
the d e n n e d c o n d i t i o n with specified b a c k i n g . T h e use
of a b a c k i n g p l a t e is n o t s t r a i g h t f o r w a r d , for the
required i n t i m a c y of c o n t a c t a n d resulting dirt build
u p r e n d e r t h e a p p r o a c h difficult. S o m e e x p e r i m e n t a l
gauges h a v e included a t r a n s m i s s i o n m e a s u r e m e n t
with the basic reflectance m e a s u r e m e n t in o r d e r t o

304

d e v e l o p t h e result, b u t m o s t on-line t e c h n i q u e s
e x t r a p o l a t e from a single free-sheet m e a s u r e m e n t b y
calibration.
F o r o p a c i t y m e a s u r e m e n t , t h e c o n t r a s t definition
b a s e d o n reflection from a sheet b a c k e d b y b l a c k a n d
white b a c k i n g s c a n be c o n v e r t e d i n t o a t r a n s m i s s i o n
a l g o r i t h m , a n d m e a s u r e m e n t of a single sheet c a n b e
m a d e in a t r a n s m i s s i o n m o d e in w h i c h t h e d e t e c t o r
is covered b y a p a r t i a l reflector. I n t h e case of color
and brightness measurements, where the property
definition involves t h e reflectance from a n infinite
stack of sheets, a w h i t e o r c o l o r e d b a c k i n g is typically
used t o r e d u c e t h e e r r o r s resulting from c h a n g e s in t h e
sheet t r a n s p a r e n c y . G e n e r a l limitations of on-line
m e a s u r i n g techniques for large-scale optical p a r a m
eters a r e indicated in T a b l e 2.
T w o i n s t r u m e n t a l a p p r o a c h e s h a v e evolved for
c o l o r m e a s u r e m e n t , t h e filter c o l o r i m e t e r a n d t h e
dispersive s p e c t r o p h o t o m e t e r . I n the filter colori
meter, t h r e e filters c o r r e s p o n d i n g t o C o m m i s i o n I n
t e r n a t i o n a l de l'Eclairage ( C I E ) tristimulus , Y a n d
functions a r e used, a n d reflected light is analyzed
with a single d e t e c t o r . I n t h e dispersive s p e c t r o p h o t
o m e t e r , reflected light is dispersed b y a g r a t i n g o n t o a
d e t e c t o r a r r a y , a n d t h e multiple d e t e c t o r signals a r e
analyzed. T h e resulting spectral reflectance i n f o r m a
tion c a n be a n a l y z e d as C I E , Y a n d values. In
a d d i t i o n , signal-processing a l g o r i t h m s c a n include the
spectral characteristics of t h e s o u r c e a n d t h u s p r o v i d e
m e t a m e r i s m i n f o r m a t i o n for v a r i o u s i l l u m i n a n t s . T h e
filter c o l o r i m e t e r h a s been e x t e n d e d t o include a
s c a n n i n g m o n o c h r o m a t o r interference filter which
develops c o m p r e h e n s i v e spectral i n f o r m a t i o n c o m
p a r a b l e t o t h a t of the dispersive s p e c t r o p h o t o m e t e r .
A s a result of p o o r s t a n d a r d s , t h e e v o l u t i o n of o n
line m e a s u r e m e n t of small-scale optical p r o p e r t i e s h a s
been slow. W h i l e m e a s u r e m e n t of gloss is relatively

Table 2
Large-scale optical property sensor limitations
Type
Instrumental
source intensity drift
source spectral drift
drift of detector and
electronics
External influences
dirt accumulation
composition changes
ambient light changes

Counteracting design approach

automatic standardization,
reference detector
stable source power,
xenon flash lamp
automatic standardization,
sensor temperature
stabilization
air wipes
optics geometries, backing
plates
xenon flash lamp, chopped
light beams

Paper

s t r a i g h t f o r w a r d , m e a s u r e m e n t of s m o o t h n e s s is inti
m a t e l y related t o t h e u l t i m a t e use of t h e p a p e r . F o r
p r i n t i n g p a p e r s , t h e q u a l i t y of t h e p a p e r surface m u s t
be c o n s i d e r e d in c o n j u n c t i o n with t h e specific p r i n t i n g
process. W h i l e off-line t e c h n i q u e s utilize air-leak
m e t h o d s for s m o o t h n e s s d e t e r m i n a t i o n , only opticalscattering t e c h n i q u e s a r e a p p r o p r i a t e on-line, a n d
c o r r e l a t i o n of these optical t e c h n i q u e s with p r i n t i n g
results is often p r o v i d e d t h r o u g h s t a n d a r d p r i n t i n g
tests.
F o r m a t i o n o r " l o o k - t h r o u g h " is a c o m p l e x , subjec
tive r e l a t i o n s h i p b e t w e e n small-scale optical density
a n d o p a c i t y (large-scale optical density). M o s t instru
m e n t s e m p l o y d e t e c t i o n of t r a n s m i t t e d light t h r o u g h a
2
small-scale a r e a of a p p r o x i m a t e l y 1 m m a n d p r o c e s s
the signal t o (a) n o r m a l i z e t h e small-scale signal with
a n o p a c i t y signal, (b) d e t e r m i n e t h e s t a n d a r d devi
a t i o n of t h e small-scale signal, a n d / o r (c) d e t e r m i n e
v a r i o u s derivatives of t h e small-scale signal.
On-line defect inspection of t h e p a p e r w e b c a n b e
p r o v i d e d with a s c a n n i n g l a s e r - b e a m device. D e t e c
tion of t h e light is p r o v i d e d t h r o u g h fiber o p t i c light
pipe t e c h n i q u e s in either t h e reflection o r t r a n s m i s s i o n
m o d e . T h e r e s o l u t i o n ( m i n i m u m defect detectable) of
2
such a n inspection system is a b o u t 1 m m t h r o u g h t h e
use of high-intensity laser b e a m s a n d fast s c a n n i n g
with r o t a t i n g multifaceted m i r r o r s .

3. Infrared

Technology

Infrared m e a s u r e m e n t t e c h n i q u e s h a v e been utilized

for on-line m o i s t u r e m e a s u r e m e n t of p a p e r since t h e
1960s. S o m e limited a p p l i c a t i o n of infrared tech
niques h a s also been m a d e t o m e a s u r e m e n t of plastic
c o a t i n g s a n d p a p e r fiber basis weight.
T h e f u n d a m e n t a l t e c h n i q u e involves t h e i n t e r a c t i o n
of light in t w o n a r r o w w a v e l e n g t h b a n d s with t h e w e b .
T h e w a v e l e n g t h s a r e selected such t h a t o n e is prefer
entially a b s o r b e d by t h e c o n s t i t u e n t being m e a s u r e d ,
a n d t h e o t h e r is n o m i n a l l y unaffected by t h a t c o n s t i
t u e n t (Fig. 2); t h u s t h e o u t p u t detected a t t h e a b s o r p
tion w a v e l e n g t h c a n be n o r m a l i z e d b y t h e o u t p u t a t
the o t h e r w a v e l e n g t h t o c o m p e n s a t e for gross o u t p u t
c h a n g e s . T h i s a p p r o a c h c o r r e c t s for t w o basic c h a r a c
teristics of t h e m e a s u r e m e n t t e c h n i q u e : (a) drift of
source intensity a n d d e t e c t o r sensitivity, a n d (b)
c h a n g e s in t h e gross transmissivity o r reflectivity of
the w e b . Typically, t h e w a t e r a b s o r p t i o n w a v e l e n g t h
at 1.95 a n d t h e n o r m a l i z a t i o n w a v e l e n g t h a t
1.80 a r e c h o s e n .
T h e a t t e n u a t i o n of light by p a p e r is c h a r a c t e r i z e d
by t w o distinctly different p h e n o m e n a , scattering a n d
a b s o r p t i o n . A s a result, even t h e n o r m a l i z e d o u t p u t
detected a t t h e a b s o r p t i o n w a v e l e n g t h is n o t inher
ently a simple function of t h e p a r a m e t e r being
m e a s u r e d , such as m o i s t u r e . T r a n s m i s s i o n of t h e
a b s o r p t i o n w a v e l e n g t h is described b y a n e x p o n e n t i a l
model:

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0%

Evaluation

moisture
10%

absorption
"band

normalization
band

V.

0.6

08

10

1.2

1.4

Wavelength

moisture

1.6

1.8

20

22

24

()

Figure 2
Transmission spectra of paper and pertinent infrared
moisture sensor filters

1= IQ exp( OLX)
w h e r e / is the detected signal, I0 is t h e signal with the
- 1
a b s o r b e r a b s e n t , is the a b s o r p t i o n coefficient ( c m )
a n d is t h e light p a t h length in t h e w e b (cm). T h i s
light p a t h length is a function of t h e scattering p o w e r
of t h e w e b , which is itself d e p e n d e n t o n t h e scattering
cross section a n d basis weight. T h e c u m u l a t i v e effect
of these factors c a n be expressed in t e r m s of the p a t h
extension r a t i o ( P E R ) a n d n o m i n a l thickness t:
= PER./
Schematically, t h e s i t u a t i o n is s h o w n in Fig. 3 for
drafting vellum a n d n e w s p r i n t , p a p e r s of e q u a l basis
weight b u t with very different scattering cross sec
tions. Clearly, t h e n e w s p r i n t w e b , with a high scatter
ing cross section, p r o v i d e s a m u c h longer p a t h length
for light t h a n t h e drafting vellum a n d , if b o t h c o n t a i n
e q u a l a m o u n t s of w a t e r , t h e a b s o r p t i o n of light a t the
1.95 w a v e l e n g t h will be m u c h g r e a t e r in the news
p r i n t t h a n in t h e vellum.
T h i s i n h e r e n t d e p e n d e n c e of t h e m o i s t u r e sensiti
vity o n t h e scattering p o w e r of t h e sheet h a s been the
c r u x of infrared sensor d e v e l o p m e n t d u r i n g the m a t u
r a t i o n p e r i o d . C o m p e n s a t i o n / c o r r e c t i o n for this
d e p e n d e n c e h a s been a c c o m p l i s h e d t h r o u g h partially
reflecting optical geometries a n d / o r t h r o u g h m e a s u r e
m e n t s a t a d d i t i o n a l w a v e l e n g t h s . C o m p e n s a t i o n for
v a r i a t i o n s in the p a t h length i n d u c e d by v a r i a t i o n s in
scattering p o w e r is a c c o m p l i s h e d b y redirecting a n
a p p r o p r i a t e fraction of t h e o u t - s c a t t e r e d a n d t r a n s
m i t t e d light b a c k i n t o t h e w e b with partially reflecting
m i r r o r s . T h u s , in a low-scattering t r a n s l u c e n t w e b
such as vellum in w h i c h t h e P E R is close t o unity, the
s h o r t i n h e r e n t p a t h length is a u g m e n t e d by multiple
p a s s a g e s t h r o u g h t h e w e b . P r o p e r selection of the
reflectivity of t h e m i r r o r s p r o v i d e s a n identical total
p a t h length t h r o u g h b o t h n e w s p r i n t a n d vellum, t h u s
r e n d e r i n g their m o i s t u r e sensitivities e q u a l . C o m m e r
cially available sensors utilize p l a n a r o r hemispherical

305

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V-

(a)

(b)

Figure 3
Representative trajectories of light in (a) vellum
(PER = 1.2), and (b) newsprint (PER = 3.0)

m i r r o r s o n b o t h sides of the w e b t o a c c o m p l i s h t h e
c o m p e n s a t i o n . A n alternative a p p r o a c h is t o e m p l o y
m e a s u r e m e n t s of a d d i t i o n a l w a v e l e n g t h s , o n e sensi
tive t o cellulose a n d a n o t h e r as a s e c o n d n o r m a l i z a
tion w a v e l e n g t h , in o r d e r t o p r o v i d e a n i n d e p e n d e n t
m e a s u r e m e n t of t h e P E R a n d c o r r e c t t h e m o i s t u r e
m e a s u r e m e n t accordingly.
D u r i n g t h e e x p l o r a t o r y p e r i o d of infrared m e a s u r e
m e n t d e v e l o p m e n t , i n s t r u m e n t a l p r o b l e m s associated
with the i n h e r e n t instability of t h e light s o u r c e a n d
P b S infrared d e t e c t o r were solved. F o l l o w i n g the
c o n c e p t u a l design of precision s p e c t r o m e t e r s , m o s t
on-line sensor designs evolved i n t o configurations
utilizing a single d e t e c t o r a n d chopper/filter wheel t o
p r o v i d e t h e different w a v e l e n g t h s a n d n o r m a l i z e for
drift in real time. A n alternative design i n c o r p o r a t e d a
b e a m splitter a n d multiple d e t e c t o r s , e a c h with a n
a p p r o p r i a t e filter a n d t e m p e r a t u r e controller.
D u r i n g t h e m a t u r a t i o n p e r i o d , t h e i n h e r e n t sensiti
vity t o scattering p o w e r w a s resolved. In t h e o n g o i n g
refinement p e r i o d , optical i m p r o v e m e n t s a n d c o m p u
terized signal processing h a v e increased a c c u r a c y ,
e x t e n d e d the r a n g e a n d p e r m i t t e d m e a s u r e m e n t of
p a p e r s c o n t a i n i n g interfering b r o a d - b a n d a b s o r b e r s
such as c a r b o n black. T h e r e s u l t a n t m e a s u r e m e n t
a c c u r a c y achievable for p a p e r a n d p a p e r b o a r d in
typical on-line a p p l i c a t i o n s is 0 . 2 % m o i s t u r e a t low
m o i s t u r e ( 0 - 1 0 % ) a n d 2 % of t h e m o i s t u r e level u p
to the practical limit for t r a n s m i s s i o n m e a s u r e m e n t s
of 2 5 % m o i s t u r e . M e a s u r e m e n t c a n be m a d e accur
2
ately for webs u p t o 500 g m . A s u m m a r y of sensor
limitations a n d c o u n t e r a c t i n g design a p p r o a c h e s is
given in T a b l e 3.
A d a p t a t i o n of t h e basic i n s t r u m e n t a l c o n c e p t t o
reflection geometries h a s also been successful. I n such
configurations, t h e m e a s u r e m e n t is m o s t sensitive t o
2
the m o i s t u r e c o n t a i n e d in t h e w e b t o 20 g m " from

306

t h e sheet surface. T h e m e a s u r e m e n t is relatively in

sensitive t o t h e scattering cross section b u t very
sensitive t o t h e basis weight of the w e b , p a r t i c u l a r l y
for lightweight p a p e r s . M o i s t u r e m e a s u r e m e n t s from
0 t o 7 0 % m o i s t u r e a r e achievable with a n a c c u r a c y
of 0 . 2 5 % m o i s t u r e in the l o w - m o i s t u r e region
( < 1 3 % ) a n d 2 % of t h e m o i s t u r e in t h e u p p e r
region ( > 1 3 % ) . T h e reflection t e c h n i q u e h a s been
used effectively for t h e m e a s u r e m e n t of c o a t i n g s o n
p a p e r , with t h e greatest success in the m e a s u r e m e n t of
plastic c o a t i n g s . M u l t i p l e c o n s t i t u e n t s h a v e been
effectively m e a s u r e d t h r o u g h the use of multiple
wavelengths.

4. Microwave

and Radio-Frequency

Technology

M i c r o w a v e a n d radio-frequency t e c h n i q u e s h a v e been
utilized for m e a s u r e m e n t of m o i s t u r e in p a p e r since
t h e 1960s. T h e s e t e c h n i q u e s a r e n o w less widely used
t h a n infrared t e c h n i q u e s , b u t a r e o p t i m a l for certain
heavyweight paper and paperboard applications.
T h e i n t e r a c t i o n of e l e c t r o m a g n e t i c r a d i a t i o n in the
11
1 0 M 0 H z r a n g e with w a t e r molecules is c o m p l i c a t e d
by t h e b o n d i n g of t h e w a t e r in the cellulose m a t r i x .
Basic i n t e r a c t i o n p h e n o m e n a b e t w e e n e l e c t r o m a g n e
tic r a d i a t i o n a n d w a t e r a r e indicated in Fig. 4. A t
infrared frequencies, a b s o r p t i o n t h r o u g h m o l e c u l a r
v i b r a t i o n occurs; a t m i c r o w a v e frequencies, a b s o r p
t i o n t h r o u g h m o l e c u l a r r o t a t i o n o c c u r s ; a t lower
frequencies, dielectric p o l a r i z a t i o n a n d c h a r g e t r a n s
p o r t m e c h a n i s m s o c c u r a t a m a c r o m o l e c u l e level. T h e
b o n d i n g of w a t e r a n d cellulose h a s little effect o n the

Table 3
Infrared sensor limitations
Type
Instrumental
detector drift

source drift
sensitivity to
mechanical
displacements
statistical noise
External influences
dirt accumulation
composition changes
movement of sheet in
gap (passline effect)

Counteracting design approach

multiplex all signals
through same detector,
temperature-control
multiple detectors
ratio multiple signals, control
intensity, automatic
standardization
optics design
efficient optics design
diffusing optics, air wipes,
automatic standardization
compensation with partial
reflectors, compensation
with multiple signals
optics design

Paper

Nondestructive

Evaluation

In general, m i c r o w a v e a n d radio-frequency tech

niques a r e applied w h e r e infrared techniques are
2
i n a d e q u a t e : (a) for h e a v y webs ( > 500 g m " ) , (b) for
wet webs ( > 4 0 % m o i s t u r e ) , a n d (c) for webs with
c o n s i d e r a b l e c a r b o n black. A c c u r a c y of the m e a s u r e
m e n t is typically 0 . 5 % m o i s t u r e o r 3 % of the
m o i s t u r e value.

O - H Bond vibration,
infrared

and Paperboard:

l 4

(IO Hz)

Dipole rotation,

1 0

microwave ( Hz)

Dipole orientation,
radio-frequency/ultrahigh
frequency ( I 0

Interfacial

-I0

Hz)

p o l a r i z a t i o3 n ,

radio-frequency ( I 0 - I 0

5. Mechanical,
Technologies
6

Hz)

Figure 4
Interactions of electromagnetic radiation with water

a b s o r p t i o n of infrared r a d i a t i o n , b u t h a s a s u b s t a n t i a l
impact on microwave a n d radio-frequency interac
tions. B o u n d w a t e r , p r e v a l e n t a t low m o i s t u r e levels,
is u n a b l e t o i n t e r a c t in r o t a t i o n a l m o d e s ; as a result,
microwave absorption techniques have inadequate
sensitivity a t low m o i s t u r e levels ( < 3 % m o i s t u r e ) ,
a n d a r e t e m p e r a t u r e sensitive a t i n t e r m e d i a t e levels
( 3 - 2 0 % moisture) where
temperature-dependent
h y d r o g e n - b o n d i n g equilibria c h a n g e t h e a b s o r p t i o n
coefficient. A t high m o i s t u r e levels, w h e r e free w a t e r is
prevalent, m i c r o w a v e a b s o r p t i o n is m o s t a p p r o p r i a t e ,
a n d m e a s u r e m e n t in t h e b r o a d r e s o n a n c e a t
1 0
2 x 1 0 H z is typical.
M i c r o w a v e a b s o r p t i o n sensors typically consist of
t r a n s m i t t e r a n d receiver h o r n s , l o c a t e d o n o p p o s i t e
sides of t h e w e b , with a d d i t i o n a l h o r n s utilized t o
measure and/or minimize geometry-dependent con
structive/destructive interference effects. C o n t a c t i n g
w a v e g u i d e geometries a r e also used.
9
A t frequencies b e l o w 2 10 H z , t h e dielectric
p r o p e r t i e s of w a t e r p r o v i d e t h e basis of a m o i s t u r e
m e a s u r e m e n t w h e r e b y t h e p a p e r sheet modifies the
r e s o n a n t frequency of a m i c r o w a v e cavity. Since t h e
interacting w a t e r molecules align with t h e electric
field ( r a t h e r t h a n r o t a t i n g , as h a p p e n s at t h e a b s o r p
tion r e s o n a n c e ) , t h e dielectric i n t e r a c t i o n is m o r e
sensitive t h a n t h e a b s o r p t i o n i n t e r a c t i o n a t inter
m e d i a t e ( a b o u t 5 % ) m o i s t u r e levels. N o n c o n t a c t i n g
double-sided a n d c o n t a c t i n g single-sided r e s o n a n t
cavities are used.
Radio-frequency moisture measurements are m a d e
6
in t h e 1 0 M 0 H z r a n g e . Typically, a n electrode struc
t u r e c o n t a c t s t h e sheet a n d p r o b e i m p e d a n c e is cali
b r a t e d in t e r m s of m o i s t u r e c o n t e n t . V a r i a t i o n s in w e b
c o m p o s i t i o n , including fiber p r o p e r t i e s a n d ionic c o n
tent, c h a n g e t h e c a l i b r a t i o n a n d limit t h e a c c u r a c y of
the m e a s u r e m e n t .

Pneumatic

and

Acoustic

V a r i o u s m e c h a n i c a l , p n e u m a t i c - f l u i d i c a n d acoustic
technologies h a v e been utilized o r a r e being developed
for on-line m e a s u r e m e n t s , with t h e greatest e m p h a s i s
being o n the m e a s u r e m e n t of p a p e r / p a p e r b o a r d
caliper. U l t r a s o n i c s a r e being developed t o p r o v i d e
i n d i c a t i o n s of s t r e n g t h - r e l a t e d p r o p e r t i e s inferred
from p r o p a g a t i o n velocities.
On-line caliper m e a s u r e m e n t systems a r e t w o sided,
consisting of a t r a n s d u c e r e n e r g y - c o u p l i n g subsystem
a n d a t r a n s d u c e r h e a d - p o s i t i o n i n g subsystem. T h e
h e a d - p o s i t i o n i n g s u b s y s t e m establishes a reference
g e o m e t r y in which w e b caliper v a r i a t i o n s c h a n g e the
s e p a r a t i o n b e t w e e n t h e elements of the energyc o u p l i n g s u b s y s t e m . V a r i o u s m o d e s of energy
c o u p l i n g a r e utilized, m o s t c o m m o n l y c o u p l i n g of
e l e c t r o m a g n e t i c r a d i a t i o n t h r o u g h t h e w e b , either
of m a g n e t i c fields w i t h a split-core t r a n s f o r m e r o r
of electric fields with a radio-frequency coil a n d e d d y c u r r e n t target.
W h i l e t h e e n e r g y - c o u p l i n g t e c h n o l o g y is refined,
t h e h e a d - p o s i t i o n i n g t e c h n o l o g y is q u i t e process inter
active a n d t h e a p p l i c a t i o n t e c h n o l o g y is still m a t u r i n g .
P o s i t i o n i n g m e t h o d s c a n b e classified as two-sided
c o n t a c t i n g , one-sided c o n t a c t i n g o r n o n c o n t a c t i n g ,
w h e r e p n e u m a t i c air b e a r i n g s a r e e m p l o y e d t o separ
ate o n e o r b o t h t r a n s d u c e r h e a d s from the w e b .
P r o b l e m s related t o w e b stability, sensor s t a n d a r d i z a
tion a n d h e a d a l i g n m e n t h a v e inhibited on-line appli
c a t i o n of a n o n c o n t a c t i n g design, b u t these p r o b l e m s
a r e o v e r c o m e with a one-sided c o n t a c t i n g design in
w h i c h t h e w e b c o n t a c t s a fixed p l a t e , a n d e l e c t r o m a g
netic c o u p l i n g b e t w e e n t h e p l a t e a n d a h e a d floating
o n a n air b e a r i n g a b o v e the w e b provides the
m e a s u r e m e n t . T h e two-sided c o n t a c t i n g design
generally includes s p r i n g - l o a d e d c o n t a c t i n g a r m s a n d
a p a i r of c o n t a c t i n g surfaces m a d e of s m o o t h , wearresistant m a t e r i a l .
C o n c e p t u a l l y , t h e two-sided c o n t a c t i n g design
m e a s u r e s the d i s t a n c e b e t w e e n the p e a k s of the p a p e r
included within t h e c o n t a c t i n g a r e a , a n d is affected by
sheet c o m p r e s s i o n related t o t h e l o a d i n g of the c o n
tacting a r m s a n d by the d y n a m i c residence time of the
sheet within t h e c o n t a c t a r e a . In c o n t r a s t , the o n e
sided c o n t a c t i n g design m e a s u r e s the distance
b e t w e e n a n a v e r a g e of p e a k s a n d valleys o n the airb e a r i n g s i d e . a n d t h e p e a k s o n t h e c o n t a c t i n g side
w i t h o u t c o m p r e s s i o n effects. A e r o d y n a m i c factors are

307

Paper

and Paperboard:

Nondestructive

Evaluation

involved in stabilization of the air b e a r i n g a n d m i n i

m i z a t i o n of p a p e r o r process p a r a m e t e r s which
c h a n g e t h e b o u n d a r y layer of air d r a g g e d i n t o the
sensor b y t h e sheet. Caliper m e a s u r e m e n t accuracies
of 1 for relative profile m e a s u r e m e n t s a n d
2 of t h e a b s o l u t e m e a s u r e m e n t h a v e been
achieved in typical fine writing p a p e r a p p l i c a t i o n s .
T h e m e c h a n i c a l p r o p e r t i e s of a p a p e r w e b c a n b e
p r o b e d b y m e a n s of t h e p r o p a g a t i o n of u l t r a s o n i c
waves in the w e b . S t r e n g t h p a r a m e t e r s of interest
(e.g., b u r s t a n d tensile s t r e n g t h ) describe failures a t
the inelastic extremities of s t r e s s - s t r a i n curves a n d a r e
destructive p r o p e r t i e s b y n a t u r e . H o w e v e r , b e h a v i o r
in the elastic regime c a n be m e a s u r e d , a n d such
m e a s u r e m e n t s h a v e been c o r r e l a t e d empirically with
the t r a d i t i o n a l strength p a r a m e t e r s ; c o r r e l a t i o n of
extensional stiffness with b u r s t a n d tensile s t r e n g t h s
h a s been d o c u m e n t e d . E x t e n s i o n a l stiffness is a func
tion of the velocity of u l t r a s o u n d p l a t e w a v e s t h r o u g h
p a p e r a n d of the basis weight. A d d i t i o n a l i n f o r m a t i o n
is available from m e a s u r e m e n t s of s h e a r waves.
A n on-line, m e c h a n i c a l sheet c o n t a c t with wheels is
utilized t o c o u p l e t h e u l t r a s o n i c energy i n t o the w e b .
Piezoelectric t r a n s d u c e r s , a p p r o p r i a t e timing circuitry
a n d a multiple-wheel c o n t a c t i n g device c o m p r i s e
the sensor. W h i l e u l t r a s o n i c m e a s u r e m e n t s of w e b
p r o p e r t i e s a r e in a n e x p l o r a t o r y stage, p r e l i m i n a r y
results with this e m e r g i n g t e c h n o l o g y a r e p r o m i s i n g
( B a u m a n d H a b e g e r 1980). F u t u r e efforts will
be directed t o i m p r o v e m e n t s in t h e m e t h o d s of c o u p
ling u l t r a s o u n d i n t o t h e w e b a n d e x t e n d i n g correla
tions of elastic p r o p e r t i e s with failure ( a n d o t h e r )
parameters.

6. Correlation

and

Verification

Historically, c o r r e l a t i o n of on-line n o n d e s t r u c t i v e
m e a s u r e m e n t s with off-line reference m e a s u r e m e n t s
w a s intimately related t o sensor c a l i b r a t i o n a n d w a s
necessary t o verify t h a t " c a l i b r a t i o n shifts" did n o t
d e g r a d e the on-line m e a s u r e m e n t . A s basic sensing
technologies h a v e m a t u r e d a n d been refined, sensiti
vity t o s p u r i o u s p r o c e s s factors h a s decreased greatly,
a n d sensors a r e far m o r e stable a n d t o l e r a n t of
e n v i r o n m e n t a l a n d process c o n d i t i o n s , t h u s eliminat
ing m a n y of the causes of c a l i b r a t i o n shifts. A s a
result, c o r r e l a t i o n t e c h n i q u e s h a v e b e c o m e m o r e
sophisticated a n d a r e used p r i m a r i l y t o verify t h a t
n o i n s t r u m e n t a l o r process effects i m p a i r sensor
performance.
C u r r e n t c o r r e l a t i o n techniques c a n be classified as
static o r d y n a m i c . Static t e c h n i q u e s consist of off-web
sensor m e a s u r e m e n t s of check s a m p l e s (with k n o w n
stable p a r a m e t e r s ) a n d c a l i b r a t i o n samples (for which
new c a l i b r a t i o n c o n s t a n t s a r e t o be d e t e r m i n e d ) .
D y n a m i c t e c h n i q u e s involve (a) acquisition of w e b
samples which h a v e been m e a s u r e d on-line b y a
sensor, (b) m e a s u r e m e n t of these d y n a m i c s a m p l e s

308

with a n off-line reference, a n d (c) c o m p a r i s o n of the

on-line a n d off-line results.
M e t h o d o l o g y p r o b l e m s r e n d e r d y n a m i c techniques
difficult. I n p a r t i c u l a r , d y n a m i c techniques a r e c h a r
acterized by s a m p l i n g e r r o r s of t w o distinct types:
correspondence errors and conditioning errors. Cor
r e s p o n d e n c e e r r o r s result from the fact t h a t t h e p o r
tions of the w e b m e a s u r e d on-line a r e n o t exactly the
s a m e as t h o s e m e a s u r e d off-line. C o n d i t i o n i n g e r r o r s
o c c u r because sheet p r o p e r t i e s c h a n g e from t h e p o i n t
of on-line m e a s u r e m e n t t o the p o i n t of off-line
measurement. The most widespread conditioning
e r r o r s a r e c a u s e d by c h a n g e s in s a m p l e m o i s t u r e
c o n t e n t from t h e p o i n t of on-line m e a s u r e m e n t t o the
p o i n t of l a b o r a t o r y m e a s u r e m e n t ; such m o i s t u r e
c h a n g e s affect basis weight, m o i s t u r e a n d caliper
c o r r e l a t i o n s . In a d d i t i o n , e r r o r s i n h e r e n t in t h e refer
ence m e a s u r e m e n t a n d l a b o r a t o r y m e t h o d o l o g y a r e
also involved. A s a result of these e r r o r sources,
d y n a m i c c o r r e l a t i o n e r r o r s a r e typically five times
w o r s e t h a n basic sensor e r r o r s .
D e s p i t e t h e e r r o r s i n h e r e n t in d y n a m i c t e c h n i q u e s ,
they a r e widely used, often in c o n j u n c t i o n with static
m e t h o d s , to verify t h a t sensor p e r f o r m a n c e is n o t
i m p a i r e d b y process c o n d i t i o n s . D u e t o m o i s t u r e
c o n d i t i o n i n g , off-web static m e a s u r e m e n t s of p a p e r
samples with a sensor a r e n o t stable. H e n c e check
samples a r e typically fabricated from m y l a r (or a n
equivalent stable, h o m o g e n e o u s m a t e r i a l ) a n d verifi
c a t i o n of on-line p e r f o r m a n c e by d y n a m i c c o r r e l a t i o n
is d o n e occasionally for t h e sensor. Static m o i s t u r e
m e a s u r e m e n t of p a p e r s a m p l e s hermetically sealed in
plastic b a g s h a s been refined, a n d is routinely d o n e t o
check t h e c a l i b r a t i o n of infrared m o i s t u r e gauges;
o t h e r m o i s t u r e m e a s u r e m e n t s c o n t i n u e t o need s o m e
c o m b i n a t i o n of off-sheet m e a s u r e m e n t s of check
s a m p l e s a n d d y n a m i c c o r r e l a t i o n . D y n a m i c correla
tion of caliper m e a s u r e m e n t s a p p e a r s t o be a necessity
d u e t o t h e i n t i m a c y of r e l a t i o n s h i p between process
p a r a m e t e r s a n d sensor p e r f o r m a n c e ; h o w e v e r , cor
respondence and conditioning errors are particularly
severe in caliper c o r r e l a t i o n . O p t i c a l m e a s u r e m e n t s
a r e typically c o r r e l a t e d statically.
T h e t r e n d in use of n o n d e s t r u c t i v e e v a l u a t i o n m e t h
o d s in the p a p e r i n d u s t r y is t o utilize t h e on-line
m e a s u r e m e n t s for q u a l i t y c o n t r o l as well as process
c o n t r o l . T h u s , c o r r e l a t i o n a n d verification of the o n
line m e a s u r e m e n t s will c o n t i n u e t o be a n i m p o r t a n t
o p e r a t i o n a l aspect; the shift t o r a p i d , a c c u r a t e static
t e c h n i q u e s for c o r r e l a t i o n a n d verification from slow,
error-prone dynamic techniques should continue.
See also: Paper and Paperboard: Destructive Mechanical
Testing

Bibliography
Baum G A, Habeger C C 1980 On-line measurement of
paper mechanical properties. Tappi 63(7): 63-6

Particle-Induced

Cameron J F 1965 The uses of radioisotope gauges in

industry. Industrial Radioisotope Economics: Findings of
the Study Group Meeting on Radioisotope Economics,
IAEA Technical Reports Series No. 40. International
Atomic Energy Authority, Vienna, pp. 303-27
Christie J S 1977 On-machine measurement of the chromatic
aspects of appearance. Tappi 60(2): 119-21
Chu F Y, Balls W 1979 Moisture measurement: infrared
vs microwave. Pulp Pap. Can. 80(5): 71-6
Clayton C G 1965 The use of ionization methods in indus
try. Industrial Radioisotope Economics: Findings of the
Study Group Meeting on Radioisotope Economics, IAEA
Technical Reports Series No. 40. International Atomic
Energy Authority, Vienna, pp. 359-93
Goss J 1979 On-line sensors for paper systems. South. Pulp.
Pap. Manuf. 42(3): 18-20; 42(4): 28-9
Kirbis R, Svenka 1980 Measurement and control with a
new optical smoothness meter. Paper 193(4): 17-22
Kishner S J 1981 An on-line spectrophotometer for color
measurement of moving samples. In: Cauwenberghe A R
van (ed.) 1981 Proc. 4th IF AC Conf. Instrumentation and
Automation in the Paper, Rubber, Plastics and Polymerisa
tion Industries. Pergamon, Oxford, pp. 55-60
McNelles L A, Buchnea A 1977 An on-line ash constituent
determination using x-ray fluorescence. Proc. Int. Symp.
Control. Canadian Pulp and Paper Association, Van
couver, pp. 1-5
Munn van 1970 On-line caliper measurement and
control. Tappi 53(5): 825-9
Newell J W 1973 Using the on-line basis weight and
moisture measuring system for quality control. Tappi
56(2): 60-3
Overhoff W 1973 Infrared gaugestheir use, deficiencies,
and applications for on-line control. Tappi 56(2): 70-3
Pfeifer R J 1981a A review of the development of on-line
paper machine sensors. Pulp. Pap. 55(2): 68-73
Pfeifer R J 1981b On-line paper machine sensorsreview of
current technology. Pulp. Pap. 55(9): 162-7
Walbaum 1981 On-line measurements of processes and
products in the pulp and paper industry. In: Cauwen
berghe A R van (ed.) 1981 Proc. 4th IF AC Conf. Instru
mentation and Automation in the Paper, Rubber, Plastics
and Polymerisation Industries. Pergamon, Oxford, pp. 128
Walbaum , Lisnyansky 1983 Review of process
control instruments for measuring paper quality vari
ables. Paper Trade J. July 15 & 30: 3 7 ^ 2 ; Aug. 15: 3 4 ^ 0

X-Ray

Emission

x-ray excitation. H e n c e , t h e characteristic x-ray p e a k s

s t a n d o u t m o r e clearly, giving a better sensitivity. T h e
P I X E t e c h n i q u e also h a s a n u m b e r of o t h e r a d v a n
tages which will b e discussed in t h e following.

/.

Principle

T h e principle of P I X E analysis is illustrated in F i g . 1.

T h e particle b e a m from t h e accelerator passes
t h r o u g h t h e s a m p l e , t h e r e b y c a u s i n g t h e emission of
rays which a r e detected b y m e a n s of a lithium-drifted
silicon (Si(Li)) d e t e c t o r . T h e pulses from t h e d e t e c t o r
a r e a n a l y z e d in a m u l t i c h a n n e l analyzer, which gives a
pulse height s p e c t r u m of t h e rays. A typical x-ray
s p e c t r u m is s h o w n in F i g . 2. T h e light a n d m e d i u m h e a v y elements in t h e s a m p l e give rise t o p e a k s
rays. T h e h e a v y
corresponding to the K a and
elements a r e d e t e r m i n e d by m e a n s of t h e L rays,
w h o s e energy is a b o u t t h e s a m e a s t h a t of t h e rays
of t h e m e d i u m - h e a v y elements. T h e characteristic
x-ray p e a k s a r e s u p e r i m p o s e d o n a c o n t i n u o u s
b a c k g r o u n d consisting m a i n l y of B r e m s s t r a h l u n g
p r o d u c e d b y s e c o n d a r y electrons.
T h e height of a given x-ray p e a k is a m e a s u r e of t h e
a m o u n t of t h e c o r r e s p o n d i n g element in t h e sample.
A n i m p o r t a n t p o i n t is t h a t t h e calculation of t h e x-ray
yield c a n b e m a d e q u a n t i t a t i v e l y . T h e x-ray p r o d u c
tion cross sections a r e k n o w n with g o o d a c c u r a c y a n d
t h e p a r a m e t e r s of t h e e x p e r i m e n t a l set u p , such as
solid angles, d e t e c t o r efficiency a n d so o n , a r e easily
d e t e r m i n e d . T h e b e a m c u r r e n t c a n be m e a s u r e d in
v a r i o u s w a y s , for e x a m p l e , as indicated in F i g . 1, b y a
F a r a d a y c u p . H e n c e , unlike m o s t o t h e r analytical
methods P I X E can determine the sample composition
in a b s o l u t e t e r m s . T h i s is a n i m p o r t a n t feature w h i c h
is exploited in practice.

2. Experimental

Arrangements

E x p e r i m e n t a l l y , P I X E analysis c a n b e carried o u t
using v a r i o u s a r r a n g e m e n t s . U s u a l l y , t h e s a m p l e t o b e

R. J. Pfeifer
[AccuRay Corporation, Columbus,
Ohio, USA]

Particle-Induced X-Ray Emission

Particle-induced x-ray emission ( P I X E ) is a novel
m e t h o d for elemental analysis a n d , a s t h e n a m e
implies, it is b a s e d o n x-ray emission. T h e c h a r a c t e r i s
tic feature is t h a t t h e excitation is p e r f o r m e d b y m e a n s
of c h a r g e d particles from a n accelerator, usually
p r o t o n s o r particles. T h e m a i n r e a s o n for using such
a c o m p l i c a t e d a n d expensive m e t h o d of excitation is
t h a t these h e a v y particles give rise t o less b a c k g r o u n d
in the r e c o r d e d spectra t h a n , for e x a m p l e , electron o r

Computer

Figure 1
Schematic diagram of a PIXE setup

309

Particle-Induced

X-Ray

Emission
n o w a n u m b e r of c o d e s t h a t m a k e it possible t o let a
c o m p u t e r c a r r y o u t t h e c o m p l e t e analysis of a P I X E
s p e c t r u m . It is c o n v e n i e n t t o i n t r o d u c e cross sections,
a b s o r p t i o n coefficients a n d t h e v a r i o u s e x p e r i m e n
tal p a r a m e t e r s i n t o the c o d e so t h a t t h e c o m p u t e r
p r i n t o u t consists of m a s s values of all elements
t h a t c a n be d e t e r m i n e d a n d u p p e r limits for t h o s e n o t
detected.

Ca

3. Combination

10

Energy

15

20

25

(keV)

Figure 2
A typical spectrum

analyzed is placed in a n i r r a d i a t i o n c h a m b e r which is

directly c o n n e c t e d t o the b e a m line of the accelerator.
H e n c e , the analysis takes place in v a c u u m . T h e s a m
ples are m o u n t e d in a s a m p l e c h a n g e r located inside
the c h a m b e r , so t h a t it is possible t o c h a n g e s a m p l e s
w i t h o u t b r e a k i n g the v a c u u m .
T h e samples c a n be of different types. A c o m m o n
type is the so-called thin sample. I n this c o n t e x t " t h i n "
m e a n s t h a t the particles in the b e a m only lose a small
p a r t of their energy w h e n p a s s i n g t h r o u g h the s a m p l e .
T h e a b s o r p t i o n of the rays in t h e s a m p l e is neglig
ible. H e n c e , the e x p e r i m e n t a l c o n d i t i o n s a r e well
defined a n d it is n o t necessary t o a p p l y a n y c o r r e c
tions for the slowing d o w n of the particles o r t h e
a b s o r p t i o n of t h e rays.
S o m e t i m e s it is n o t possible t o m a k e a thin s a m p l e
of the m a t e r i a l t o be analyzed. It is t h e n quite possible
to place a specimen directly in t h e i r r a d i a t i o n
c h a m b e r w i t h o u t a n y p r e p a r a t i o n , p r o d u c i n g w h a t is
called " t h i c k - s a m p l e " analysis. T h e particles a r e
slowed d o w n a n d eventually s t o p p e d in the s a m p l e . I n
this case, the calculation of the x-ray yield is m o r e
c o m p l i c a t e d . It h a s to be calculated for each energy
interval separately a n d then integrated over t h e p a t h
of the particles. T h e a b s o r p t i o n of the rays in the
s a m p l e m u s t also be t a k e n i n t o a c c o u n t .
F o r t h e analysis of large objects, which c a n n o t be
placed inside the i r r a d i a t i o n c h a m b e r , it is possible t o
use the so-called external b e a m t e c h n i q u e . T h e p a r t i
cle b e a m is t a k e n o u t i n t o t h e a m b i e n t air t h r o u g h a
thin w i n d o w a t t h e e n d of t h e b e a m line. I n this w a y it
is possible t o analyze a n y k i n d of object, for e x a m p l e
b o o k s , p a i n t i n g s a n d archaeological artifacts.
A P I X E s p e c t r u m is usually quite c o m p l i c a t e d , as
illustrated in Fig. 2. Interferences b e t w e e n different
elements a r e very likely to o c c u r a n d small p e a k s m a y
be h i d d e n b y larger o n e s or by t h e b a c k g r o u n d . It is
therefore a l m o s t impossible t o p e r f o r m the d e c o n v o lution of such a s p e c t r u m by h a n d . H o w e v e r , there a r e

310

with Other Nuclear

Methods

P I X E analysis c a n , in principle, cover t h e w h o l e

periodic table b u t for practical r e a s o n s it is difficult to
d e t e r m i n e the lightest elements. T h e i r characteristic
rays h a v e such a low energy t h a t they a r e easily
a b s o r b e d in t h e s a m p l e a n d in the w i n d o w s of the
i r r a d i a t i o n c h a m b e r a n d t h e detector, which m e a n s
t h a t the sensitivity d r o p s rapidly with decreasing
a t o m i c n u m b e r . It is possible t o solve this p r o b l e m t o
a certain degree by m o u n t i n g a windowless d e t e c t o r
inside t h e c h a m b e r , b u t t h e n o t h e r p r o b l e m s arise, for
e x a m p l e , scattering of the particles i n t o the detector.
F o r these r e a s o n s there is a practical limit a r o u n d
a l u m i n u m ( Z = 13) a n d lighter elements a r e usually
n o t d e t e r m i n e d by m e a n s of P I X E .
T h e best s o l u t i o n t o this p r o b l e m is t o exploit
v a r i o u s n u c l e a r r e a c t i o n s for t h e d e t e r m i n a t i o n of the
lightest elements. It w o u l d , of c o u r s e , be a great
a d v a n t a g e if the P I X E s e t u p c o u l d be used for this
p u r p o s e w i t h o u t t o o m a n y modifications a n d this is
actually possible. O n e suitable r e a c t i o n is p r o t o n
c a p t u r e leading t o g a m m a - r a y e m i s s i o n t h e (p,y)
reaction; in this c o n t e x t it is often called P I G E
(particle-induced g a r m m a - r a y emission). T h e g a m m a
r a d i a t i o n is detected b y a g e r m a n i u m detector. T h i s
c a n be placed o u t s i d e t h e i r r a d i a t i o n c h a m b e r b u t
s h o u l d , of c o u r s e , be as close as possible t o the
s a m p l e . T h e g a m m a - r a y s p e c t r u m is often quite c o m
plicated b u t , b e c a u s e of the g o o d energy resolution of
t h e g e r m a n i u m d e t e c t o r , it is n o t t o o difficult t o
identify t h e lines arising from the (p,y) reaction in t h e
v a r i o u s nuclides p r e s e n t in t h e s a m p l e . K n o w i n g
t h e cross sections a n d t h e efficiency of the detector,
the a m o u n t s of the v a r i o u s elements in the s a m p l e a r e
easily calculated. E l e m e n t s such as lithium, b o r o n ,
fluorine, m a g n e s i u m a n d a l u m i n u m are conveniently
d e t e r m i n e d in this way. A great a d v a n t a g e is t h a t the
s a m e particle b e a m as in P I X E c a n be used, for
example 2 M e V protons. This means that P I X E and
P I G E analyses c a n be p e r f o r m e d simultaneously.
A n o t h e r r e a c t i o n t h a t c a n be c o m b i n e d with P I X E
is p r o t o n elastic scattering ( , ' ) , in this c o n t e x t
s o m e t i m e s called P E S A ( p r o t o n elastic scattering
analysis). T h e energy of the elastically scattered p r o
t o n s is d e t e r m i n e d b y m e a n s of a surface b a r r i e r
d e t e c t o r w h i c h is placed inside t h e i r r a d i a t i o n
c h a m b e r . W h e n t h e p r o t o n s a r e scattered by the
nuclei in the s a m p l e , the energy loss d e p e n d s o n the

Particle-Induced

nuclear m a s s . H e n c e , in t h e energy s p e c t r u m t h e r e a r e
p e a k s for e a c h m a s s value a n d their height is a
m e a s u r e of t h e a b u n d a n c e of t h e c o r r e s p o n d i n g n u c
lides. F o r a g o o d m a s s r e s o l u t i o n r a t h e r high p r o t o n
energies a r e r e q u i r e d . H o w e v e r , even with a n energy
of 2 - 3 M e V t h e r e s o l u t i o n is sufficient t o resolve such
elements as c a r b o n , n i t r o g e n a n d oxygen, w h i c h a r e
t h o s e usually d e t e r m i n e d b y P E S A . H e n c e , P E S A c a n
also be p e r f o r m e d s i m u l t a n e o u s l y with P I X E .
A P I X E set u p w h i c h is p r o v i d e d with a r r a n g e
m e n t s for P I G E a n d P E S A is t h u s a very powerful
i n s t r u m e n t with a u n i q u e m u l t i e l e m e n t a l capability
t h a t m a k e s it possible t o d e t e r m i n e all elements from
h y d r o g e n t o u r a n i u m . T h i s is illustrated in F i g . 3
which s h o w s typical values of t h e m i n i m u m d e t e c t i o n
limits.

4. The PIXE

Microbeam

O n e a d v a n t a g e of P I X E analysis is t h a t t h e cross
section of t h e particle b e a m c a n be adjusted. It is
possible t o cover a large p a r t of t h e s a m p l e , b u t also
to select a smaller p a r t for closer e x a m i n a t i o n . W i t h
the c o n v e n t i o n a l focusing m a g n e t s of a n a c c e l e r a t o r
facility b e a m d i a m e t e r s as small as a few t e n t h s of a
millimeter c a n b e o b t a i n e d . H o w e v e r , in recent years
the m i c r o b e a m t e c h n i q u e h a s been i m p r o v e d a n d a
spatial r e s o l u t i o n of t h e o r d e r of 0.1-1 h a s b e e n
achieved. T h i s , of c o u r s e , requires a m o r e c o m p l i
cated focusing system, usually consisting of t w o t o
four q u a d r u p o l e m a g n e t i c lenses. S u c h a m i c r o b e a m
of c h a r g e d particles h a s f o u n d m a n y a p p l i c a t i o n s . F o r
analytical p u r p o s e s a c o m b i n a t i o n with P I X E , often
called - , is t h e m o s t c o m m o n o n e . T h e r e a s o n is
t h a t a m o n g t h e analytical t e c h n i q u e s t h a t c a n be
c o m b i n e d with a m i c r o b e a m , P I X E h a s t h e highest
sensitivity.

20

40
Atomic

60
number,

Figure 3
Typical detection limits for PIXE and the complementary
nuclear techniques elastic scattering (PESA) and
gamma-ray emission (PIGE)

X-Ray

Emission

Sample

Figure 4
Schematic diagram of a PIXE microbeam
T h e principle of a P I X E m i c r o b e a m is illustrated in
Fig. 4. T h e particle b e a m from t h e accelerator is
focused o n t o the h o l e of a d i a p h r a g m , which is the
object in the b e a m - o p t i c a l system. By m e a n s of the
m a g n e t i c lenses the b e a m is focused so t h a t it gives a
demagnified i m a g e of t h e d i a p h r a g m o n the s a m p l e to
be a n a l y z e d . T h e d i a m e t e r of t h e d i a p h r a g m hole is
a d j u s t a b l e in the r a n g e 10-100 . W i t h a demagnific a t i o n factor of ten, the b e a m s p o t o n the surface of
t h e s a m p l e h a s a d i a m e t e r in t h e r a n g e 1-10 . T h i s
m e a n s t h a t t h e P I X E analysis c a n be p e r f o r m e d with a
spatial r e s o l u t i o n of this o r d e r . W i t h s o m e sacrifice in
b e a m c u r r e n t , even s u b m i c r o m e t e r r e s o l u t i o n s h a v e
been achieved.
T h e - t e c h n i q u e e n a b l e s t h e s t u d y of the
spatial d i s t r i b u t i o n of elemental c o n c e n t r a t i o n s . By
m o v i n g t h e s a m p l e step b y step in t w o p e r p e n d i c u l a r
directions a n d p e r f o r m i n g P I X E analysis at each
p o s i t i o n a m a p of t h e elemental c o n c e n t r a t i o n s is
o b t a i n e d for e a c h element. A m o r e efficient t e c h n i q u e ,
h o w e v e r , is t o sweep the b e a m in t h e s a m e m a n n e r as
in a s c a n n i n g electron m i c r o s c o p e . T h i s c a n be d o n e
with electrostatic deflection p l a t e s , as indicated in Fig.
4, o r w i t h m a g n e t i c deflection. F o r each x-ray pulse
from t h e d e t e c t o r t h e pulse height a n d the a n d y
c o o r d i n a t e s of t h e b e a m a r e r e c o r d e d a n d s t o r e d in
t h e c o m p u t e r m e m o r y . T h i s d a t a set c a n t h e n be
a n a l y z e d off-line in v a r i o u s w a y s . C o n c e n t r a t i o n
values a t different p o i n t s o r c o n c e n t r a t i o n profiles for
selected elements c a n be d e t e r m i n e d . T h e m o s t effi
cient use of t h e d a t a is t o p l o t a c o n c e n t r a t i o n m a p for
e a c h element.
It is o b v i o u s t h a t t h e P I X E m i c r o b e a m , in prin
ciple, is similar t o the s c a n n i n g electron m i c r o p r o b e .
T h e m a i n difference is t h a t t h e electron g u n is replaced
by a n a c c e l e r a t o r for p r o t o n s . T h i s , of c o u r s e , m e a n s
increased c o m p l e x i t y a n d cost. A relevant q u e s t i o n is
w h e t h e r t h e a d v a n t a g e s of t h e P I X E m i c r o b e a m are
w o r t h these e x t r a costs. T h e a n s w e r is given by the
very m u c h increased analytical sensitivity. In the
electron case there is a s t r o n g B r e m s s t r a h l u n g b a c k
g r o u n d which t e n d s t o m a s k the characteristic x-ray

311

Particle-Induced

X-Ray

Emission

there is such a p l e t h o r a of g o o d m e t h o d s for elemental

analysis. T h e a n s w e r is t h a t P I X E h a s s o m e u n i q u e
characteristics which m a k e t h e e s t a b l i s h m e n t of a
P I X E facility w o r t h w h i l e .

I0

5.7
Sensitivity
P I X E h a s a c o m p a r a t i v e l y high relative sensitivity
which is, h o w e v e r , d e p e n d e n t o n t h e c o m p o s i t i o n of
t h e s a m p l e . T h e m o s t favorable case is t h e d e t e r m i
n a t i o n of trace elements in o r g a n i c tissue w h e r e
detection limits as low as 20 p p b h a v e been achieved.
A less favorable case is mineralogical a n d m e t a l l u r g i
cal s a m p l e s c o n t a i n i n g large a m o u n t s of h e a v y
elements, w h i c h c a n increase t h e detection limits t o
1-10 p p m .
In a b s o l u t e t e r m s the sensitivity of P I X E is very
g o o d . I n c o n v e n t i o n a l P I X E the b e a m d i a m e t e r is a
few millimeters, which gives detection limits of t h e
11
o r d e r of 1 0 " g. W i t h t h e m i c r o b e a m t e c h n i q u e a n d a
spatial r e s o l u t i o n of a b o u t 1 , d e t e c t i o n limits as
1 6
low as 1 0 " g c a n be achieved.
100

200

300

400

500

600

700

800

900

1000

Energy (keV)

Figure 5
X-ray spectrum of an organic tissue sample; excitation
with (a) 20 keV electrons and (b) 2.5 MeV protons.

p e a k s . P r o t o n s give a m u c h lower b a c k g r o u n d . T h i s is
illustrated in Fig. 5 which c o m p a r e s spectra from t h e
same o r g a n i c s a m p l e w h e n i r r a d i a t e d with 2 0 k e V
electrons a n d 2.5 M e V p r o t o n s . T h e r e is a striking
difference in sensitivity, which m e a n s t h a t in o r g a n i c
tissue the electron m i c r o p r o b e c a n n o t detect a n y trace
elements w h e r e a s this is possible with a P I X E m i c r o b e a m . In a c t u a l n u m b e r s , the d e t e c t i o n limits a r e of
the o r d e r of 0 . 1 % for the electron m i c r o p r o b e a n d
0 . 0 0 1 % for t h e P I X E m i c r o b e a m . T h i s factor of a
h u n d r e d in increased sensitivity is t h e m a i n r e a s o n for
using the - t e c h n i q u e .
T h e a d v e n t of t h e P I X E m i c r o b e a m h a s o p e n e d u p
a new field of trace element analysis o n t h e m i c r o
scopic scale. T h e greatest p o t e n t i a l is p e r h a p s in
biology a n d medicine w h e r e it is conceivable t o s t u d y
the d i s t r i b u t i o n of trace elements o n the cellular level.
H o w e v e r , this new t e c h n i q u e s h o u l d also be of im
p o r t a n c e in m a t e r i a l s science. F o r e x a m p l e , in m i c r o
electronics it is of interest t o s t u d y t h e elemental
c o m p o s i t i o n of microscopically small c o m p o n e n t s .

5.

Advantages

P I X E analysis requires access t o a suitable a c c e l e r a t o r

a n d this is certainly a serious limitation. It m i g h t even
be asked w h e t h e r it m a k e s sense to set u p such a
c o m p l i c a t e d a n d expensive e x p e r i m e n t a l facility w h e n

312

5.2 Multielemental
Capability
P I X E is a truly m u l t i e l e m e n t a l m e t h o d which c a n be
used over m o s t of the p e r i o d i c table. A n i m p o r t a n t
feature is t h a t the sensitivity varies only slightly
b e t w e e n different elements. T h i s is in c o n t r a s t t o
m a n y o t h e r analytical m e t h o d s for which there c a n b e
a very large difference in sensitivity b e t w e e n n e i g h b o r
ing elements.
5.3 Spatial

Resolution

T h e c o m b i n a t i o n of P I X E with the m i c r o b e a m tech

n i q u e m a k e s it possible t o s t u d y t h e spatial distribu
tion of trace elements with a r e s o l u t i o n of a b o u t 1 .
T h i s is a u n i q u e feature a n d there is practically n o
alternative for such studies. H e n c e , it c a n be expected
t h a t this will be o n e of t h e m a j o r a p p l i c a t i o n s of P I X E
in the future.
5.4

Versatility

P I X E c a n be used for t h e analysis of practically a n y

k i n d of object. Different t e c h n i q u e s ( m i c r o b e a m ,
external b e a m o r c o n v e n t i o n a l millimeter-sized b e a m )
c a n be used d e p e n d i n g o n the size of t h e s a m p l e . T h e
variety of s a m p l e s t h a t h a v e been analyzed is e n o r
m o u s a n d these r a n g e in size from a single b l o o d cell
t o a large p a i n t i n g .
5.5 Speed
P I X E is a relatively fast m e t h o d . A n o r m a l r o u t i n e
analysis t a k e s only a few m i n u t e s . I n view of t h e fact
t h a t it gives c o n c e n t r a t i o n values for 10-15 elements
with low d e t e c t i o n limits, this m u s t be r e g a r d e d as a
satisfactory speed. H e n c e , a P I X E facility o p e r a t i n g
full time h a s a high capacity.
5.6 Nondestructive
Analysis
P I X E analysis is n o r m a l l y n o n d e s t r u c t i v e . M o s t
m a t e r i a l s a r e n o t d a m a g e d a t all b y t h e particle b e a m ,

Particle-Induced

b u t in a n a l y z i n g m o r e delicate m a t e r i a l s , for e x a m p l e
p a p e r , it is advisable t o k e e p t h e b e a m c u r r e n t as low
as possible.
It is i m p o r t a n t t o p o i n t o u t t h a t P I X E is n o t u n i q u e
r e g a r d i n g a n y single o n e of these features. T h e r e a r e ,
for e x a m p l e , o t h e r analytical m e t h o d s t h a t a r e m o r e
sensitive a n d there a r e n o n d e s t r u c t i v e m e t h o d s with a
g o o d m u l t i e l e m e n t a l capability. T h e real s t r e n g t h of
P I X E lies in t h e c o m b i n a t i o n of so m a n y a d v a n t a
geous features.

6.

Applications

T h e characteristics of P I X E c a n also be illustrated b y

its a p p l i c a t i o n s . A difficulty is t h a t they a r e so n u m e r
o u s t h a t even a c o n d e n s e d list will b e prohibitively
long. H e r e , only a few typical a p p l i c a t i o n s will b e
briefly described.
A n ideal s a m p l e for P I X E analysis consists of a
m a t r i x of light e l e m e n t s , for e x a m p l e , plastic o r
o r g a n i c tissue, c o n t a i n i n g a large n u m b e r of t r a c e
elements. O n e e x a m p l e is air p o l l u t i o n s a m p l e s . T h e
p o l l u t i o n a e r o s o l is collected o n a thin plastic foil b y a
special s a m p l e r , often with size f r a c t i o n a t i o n . A b o u t
10-15 elements c a n usually b e d e t e r m i n e d . Extensive
m e a s u r i n g p r o g r a m s h a v e b e e n carried o u t , s o m e
times with a n e t w o r k of several m e a s u r i n g s t a t i o n s ,
e x t e n d e d over l o n g p e r i o d s of time. S u c h studies give
valuable information on h o w and where the pollution
is formed a n d a b o u t its l o n g - r a n g e t r a n s p o r t .
O t h e r m a j o r fields of a p p l i c a t i o n of P I X E a r e
biology a n d medicine. H e r e also, t h e s a m p l e s h a v e a n
ideal c o m p o s i t i o n for P I X E analysis with a large
n u m b e r of t r a c e elements in a n o r g a n i c m a t r i x . T h e
i m p o r t a n t role p l a y e d b y t r a c e elements in living
m a t t e r is well k n o w n , b u t m u c h research w o r k re
m a i n s t o be d o n e a n d P I X E c a n be a useful t o o l . It
h a s , for e x a m p l e , been a p p l i e d t o investigations of
h o w trace element c o n c e n t r a t i o n s a r e influenced b y
v a r i o u s diseases. T h e - t e c h n i q u e h a s b e e n
applied to studies of trace e l e m e n t d i s t r i b u t i o n s o n t h e
cellular level, b u t this w o r k h a s j u s t only b e g u n a n d it
is a w i d e - o p e n research field.
C h a r a c t e r i z a t i o n of v a r i o u s m a t e r i a l s is a n i m p o r t
a n t t a s k in elemental analysis. M o s t m a t e r i a l s c o n t a i n
several trace elements in m e a s u r a b l e q u a n t i t i e s . T h e
relative c o n c e n t r a t i o n s , t h e trace e l e m e n t s p e c t r u m ,
are characteristic for e a c h specimen of a certain
m a t e r i a l a n d they c o n s t i t u t e a k i n d of " f i n g e r p r i n t . " If
several specimens h a v e exactly t h e s a m e trace e l e m e n t
s p e c t r u m , they very likely h a v e t h e s a m e origin. A s a n
e x a m p l e consider ceramics. I n a r c h a e o l o g y , c e r a m i c s
play a n i m p o r t a n t role as a basis for t h e c h a r a c t e r i z a
tion of different cultures a n d t h e identification a n d
classification of this m a t e r i a l is therefore of g r e a t
i m p o r t a n c e . If a n u m b e r of trace elements a r e deter
m i n e d , their c o n c e n t r a t i o n c a n be used in o r d e r t o
distinguish v a r i o u s g r o u p s in t h e a r c h a e o l o g i c a l

X-Ray

Emission

m a t e r i a l . Often, statistical m e t h o d s t h a t h a v e been

d e v e l o p e d for p a t t e r n r e c o g n i t i o n c a n e n h a n c e the
c o n t r a s t b e t w e e n different g r o u p s . I n this w a y it is
possible t o s t u d y such q u e s t i o n s as p r o v e n a n c e a n d
t r a d e r o u t e s of t h e ceramics. O t h e r archaeological
artifacts such as coins a n d w e a p o n s c a n also be
studied in this w a y . T h e r e a s o n t h a t P I X E is such a
useful m e t h o d in this field is its high sensitivity,
m u l t i e l e m e n t a l capability a n d t h e possibility of per
f o r m i n g a n o n d e s t r u c t i v e analysis.
Similar p r o b l e m s a r e e n c o u n t e r e d in the a r t s . O n e
e x a m p l e is t h e analysis of t h e p i g m e n t s in p a i n t i n g s .
U s i n g a n external P I X E b e a m it is possible t o p e r f o r m
a n o n d e s t r u c t i v e analysis of p a i n t i n g s , including quite
large o n e s . A n o t h e r possibility is t o r e m o v e m i c r o
scopically small s a m p l e s w i t h o u t d a m a g i n g the p a i n t
ing. T h e high a b s o l u t e sensitivity of P I X E is t h e n a
prerequisite. T h e c o m p o s i t i o n of the p i g m e n t s is
characteristic for t h e p e r i o d of p a i n t i n g a n d even, in
s o m e cases, for the individual artist. A n elemental
analysis is therefore a v a l u a b l e t o o l in investigating
t h e a u t h e n t i c i t y of p a i n t i n g s . F o r g e r i e s c a n s o m e t i m e s
be revealed w h e n m o d e r n p i g m e n t s a r e f o u n d in old
paintings. F o r example, the white pigment titanium
oxide w a s n o t used before 1920 a n d , hence, if it is
f o u n d in a p a i n t i n g p u r p o r t e d t o be old, a forgery is
t h e only possible e x p l a n a t i o n .
P r i n t e d a n d w r i t t e n d o c u m e n t s of different k i n d s
a r e interesting objects for elemental analysis a n d also
in this case P I X E is a suitable m e t h o d o n a c c o u n t of
its high sensitivity a n d great versatility. It is possible
t o p e r f o r m a n o n d e s t r u c t i v e analysis of p a p e r , p a r c h
m e n t , p i g m e n t a n d ink a n d t h e results c a n be used t o
a d d r e s s such q u e s t i o n s as p r o v e n a n c e , age, a u t h e n t i
city a n d so o n . A s a n e x a m p l e , a s t u d y of t h e ink in a
G u t e n b e r g bible m a d e it possible t o elucidate h o w the
p r i n t i n g w a s carried o u t . In general, a n analysis of the
ink used in old p r i n t e d w o r k s gives v a l u a b l e i n f o r m a
tion a b o u t a u t h e n t i c i t y a n d p r o v e n a n c e . S o m e t i m e s ,
especially in t h e case of very old d o c u m e n t s , the ink
h a s faded so t h a t t h e writing is difficult o r impossible
t o r e a d . It h a s been s h o w n t h a t in these cases it is
possible t o r e c o n s t r u c t t h e writing b y m e a n s of ele
m e n t a l m a p s r e c o r d e d with a s c a n n i n g P I X E m i c r o b e a m . E v e n if t h e p i g m e n t h a s d i s a p p e a r e d , the
solvent of t h e ink will h a v e p e n e t r a t e d i n t o t h e p a p e r
o r t h e p a r c h m e n t a n d c a u s e d s o m e slight c h a n g e s in
t h e e l e m e n t a l c o m p o s i t i o n . T h e s e c h a n g e s m i g h t be
insignificant for a n y single element, b u t b y exploiting
t h e m u l t i e l e m e n t a l capability of P I X E a n d p e r f o r m
ing a statistical analysis of t h e elemental m a p s , it is
possible t o e n h a n c e t h e c o n t r a s t . T h e writing, which
m i g h t h a v e been lost for centuries, t h e n r e a p p e a r s o n
t h e c o m p u t e r screen.
S t a m p s a r e a n o t h e r k i n d of p r i n t e d m a t e r i a l of
interest for P I X E analysis. T h e p i g m e n t s used in the
p r i n t i n g of old s t a m p s a r e all i n o r g a n i c a n d it is
therefore easy t o identify a n d classify the s t a m p s by
e l e m e n t a l analysis. I n this w a y forgeries a n d e r r o r s

313

Particle-Induced

X-Ray

Emission

Figure 6
Elemental maps from a section of a spruce tree. The concentrations are shown in a grey tone scale with black denoting
the highest concentrations and white the lowest. The size of each map is about 2 mm 2 mm. The tree ring structure is
seen clearly for some elements (calcium and iron) which are characteristic of wood but not for pollution elements

c a n be detected a n d different s h a d e s classified in a n

objective way.
W o o d is a n interesting m a t e r i a l from the p o i n t of
view of elemental analysis. It c o n t a i n s m a n y elements
w h o s e relative c o n c e n t r a t i o n s give i n f o r m a t i o n a b o u t
h o w the tree h a s g r o w n a n d h o w it h a s been affected
by e n v i r o n m e n t a l factors. In recent years t h e interest
in investigations of the forest decline caused by air
p o l l u t i o n h a s increased. It is likely t h a t s o m e pollu
tion elements are t a k e n u p b y t h e tree t h r o u g h t h e
r o o t s a n d the leaves a n d t h e n stored in t h e w o o d . It
h a s even been suggested t h a t individual tree rings
c o u l d be used as i n d i c a t o r s of the time v a r i a t i o n of the
p o l l u t i o n . F o r studies of this k i n d P I X E is a n ideal
m e t h o d ( L o v e s t a m et al. 1990). By m e a n s of t h e
- t e c h n i q u e it is possible t o o b t a i n elemental
m a p s of a section of t h e tree a n d these s h o w very
clearly h o w t h e different elements are d i s t r i b u t e d in
the w o o d . F o r s o m e elements there is a clear tree ring
s t r u c t u r e w h e r e a s for o t h e r s t h e d i s t r i b u t i o n is m o r e
u n i f o r m . T h e r e a r e also s p o t s of very high c o n c e n t r a
tion (see Fig. 6). It is evident t h a t t h e p r o b l e m of h o w
different elements a r e t a k e n u p by the tree a n d distri
b u t e d in t h e w o o d is c o m p l i c a t e d . M u c h w o r k re
m a i n s t o be d o n e a n d P I X E s h o u l d be a suitable
m e t h o d for this p u r p o s e .
W a t e r is a m a t e r i a l t h a t c o n t a i n s a very large
n u m b e r of elements. In seawater, for e x a m p l e , there
are m o r e t h a n 50 elements with c o n c e n t r a t i o n s a b o v e
1 p p b . T h e r e a r e several analytical m e t h o d s suitable

314

for the d e t e r m i n a t i o n of the m a j o r a n d m i n o r ele

m e n t s . T h e use of P I X E is m a i n l y of interest for the
d e t e r m i n a t i o n of trace elements at very low c o n c e n
t r a t i o n s . T h e best results a r e o b t a i n e d w h e n P I X E is
c o m b i n e d with a suitable p r e c o n c e n t r a t i o n m e t h o d ,
for e x a m p l e the chelation of t h e m e t a l salts with
c a r b a m a t e a n d a d s o r p t i o n of t h e m e t a l complexes
o n t o a small a m o u n t of activated c a r b o n . A P I X E
analysis of the c a r b o n gives d e t e c t i o n limits of the
o r d e r of 0.1 l " 1 . E v e n lower d e t e c t i o n limits, of t h e
o r d e r of 1 n g l - 1, c a n be achieved if t h e m e t a l s a r e
e x t r a c t e d from t h e c a r b o n with a few d r o p s of nitric
acid which a r e t h e n d e p o s i t e d o n t o a thin plastic foil.
In this w a y 10-15 trace elements c a n b e d e t e r m i n e d in
s e a w a t e r a n d it is even possible t o detect such ele
m e n t s as silver a n d gold.
See also: Electron Microprobe Analysis; Ion Backscattering
Analysis; Organic Mass Spectrometry

Bibliography
Cohen D D, Clayton 1989 Ion induced x-ray emission. In:
Bird J R, Williams J S (eds.) 1989 Ion Beams for Materials
Analysis. Academic Press, Sydney, Australia, pp. 209-60
Johansson , Johansson S A , Malmqvist G, Wiman
I 1986 The feasibility of the PIXE technique in the
analysis of stamps and art objects. Nucl. Instrum. Meth
ods 14: 45-9

Phase
Johansson S A E, Campbell J L 1988 PIXE: A Novel
Technique for Elemental Analysis. Wiley, Chichester, UK
Johansson S A E, Johansson 1976 Analytical applica
tions of particle-induced x-ray emission. Nucl. Instrum.
Methods 137: 473-516
Kusko , Schwab R 1987 Historical analysis by PIXE,
Nucl. Instrum. Methods. 22: 401-6
Lovestam G, Johansson , Johansson S A , Pallon J
1990 Elemental micro patterns in tree ringsa feasibility
study using scanning proton microprobe analysis. Ambio
19:87-93.
Mitchell I V, Barfoot 1981 Particle-induced x-ray
emission analysis application to analytical problems.
Nucl. Sci. Appl. 1:99-162
Vis R D 1985 The Proton Microprobe. CRC, Boca Raton,
FL
Watt F, Grime G W (eds.) 1987 Principles and Applications
of High Energy Microbeams. Institute of Physics, Bristol,
UK
S. A . E . J o h a n s s o n
[Lund Institute of Technology,
L u n d , Sweden]

-20001
0

Diagrams

I
0 10

and Phase

Stability:

I
I
I
I
I
I
0.20 0.30 0.40 0.50 0.60 0 70
Mole fraction of chromium

Calculations

I
0 80

I
0.90

I
00

Figure 1
The effect of lattice stabilities and interaction coefficients
on the free energy curves for face-centered-cubic (fee) and
body-centered-cubic (bec) phases in the iron-chromium
system at 700

(*,-*,

Phase Diagrams and Phase Stability:

Calculations
P h a s e d i a g r a m s , in all their varied forms, a r e g r a p h i
cal illustrations o f t h o s e m i x t u r e s o f p h a s e s t h a t a r e
stable a t a given overall c o m p o s i t i o n in t h e presence
of specific external variables, such a s t e m p e r a t u r e a n d
pressure.
T h e formal t h e o r y r e q u i r e d t o calculate such equili
bria w a s established b y G i b b s in t h e n i n e t e e n t h cen
t u r y a n d involves t h e c o r r e s p o n d e n c e of such p h a s e
m i x t u r e s t o t h e e s t a b l i s h m e n t o f a m i n i m u m free
energy c o n d i t i o n . A s l o n g a g o a s 1910, w o r k b y V a n
L a a r established t h a t p h a s e d i a g r a m s o f m a r k e d l y
different t o p o l o g y reflect different m a g n i t u d e s a n d
signs for t h e i n t e r a c t i o n energies o f t h e c o m p o n e n t
species in e a c h p h a s e , t o g e t h e r with t h e t r a n s f o r m a
tion energy b e t w e e n different g e o m e t r i c a r r a n g e m e n t s
of t h e p u r e elements ( n o w c o m m o n l y referred t o a s
the lattice stabilities):
AGa(x,

T) = XiXjAG% +
+ RT(xt

AG^x,

In xt + Xj In Xj)
E

T) = xixjAG p
+ RT{xt

AG^Xj

(1)

AG^xi

In xt + Xj In Xj)

(2)

w h e r e AG^ a r e t h e i n t e r a c t i o n energies o f c o m
a a
p o n e n t s i a n d j in crystal s t r u c t u r e s a n d /?, A Gf ^ - ^
are t h e differences in energy different a l l o t r o p e s
(lattice stabilities) a n d R (x{ In xt + Xj In x) is t h e
e n t r o p y of mixing.
The temperature a n d composition dependence of
E
AG is c o m m o n l y expressed a s

T h e c a l c u l a t i o n o f p h a s e b o u n d a r y c o m p o s i t i o n is
t h u s r e d u c e d t o t h e m a t h e m a t i c a l p r o b l e m of finding
t h e free energy m i n i m u m for a n y p a r t i c u l a r c o m
b i n a t i o n o f t h e variables c o n c e r n e d , p r o v i d e d t h e
v a r i a t i o n o f free energy with t e m p e r a t u r e ( a n d a n y
o t h e r variables o f interest) c a n b e specified for each
phase. Some of the d a t a required t o evaluate the
necessary free energies (e.g., h e a t s of f o r m a t i o n ) c a n
be o b t a i n e d directly b y e x p e r i m e n t , given a p r o p e r
a p p r e c i a t i o n of t h e reference states. H o w e v e r , t o
p e r f o r m even this initial step requires a systematic
k n o w l e d g e of t h e relevant lattice stabilities, m a n y of
w h i c h will refer t o m e t a s t a b l e p h a s e s (see F i g . 1).
Since t h e r m o d y n a m i c d a t a a r e r e q u i r e d for p h a s e s
t h a t m a y b e e x p e r i m e n t a l l y inaccessible, p h a s e dia
g r a m c a l c u l a t i o n s of real systems r e m a i n e d largely a n
a l g e b r a i c c o n c e p t until a n o t a b l e b r e a k t h r o u g h w a s
achieved b y K a u f m a n a n d Bernstein (1970).
T h e y realized t h a t since t h e lattice stabilities of a n y
given element h a v e t o b e t h e s a m e in all p h a s e
d i a g r a m s t h a t c o n t a i n t h a t element, estimates of t h e
missing lattice stabilities m i g h t b e o b t a i n e d b y a p p l y
ing a n iterative p r o c e d u r e t o a series o f interrelated
p h a s e d i a g r a m s . O n c e this p r o c e d u r e w a s a d o p t e d , it
w a s f o u n d t h a t t h e t e m p e r a t u r e v a r i a t i o n of such
lattice stabilities c o u l d , in m a n y cases, b e a p p r o x i
m a t e d b y simple linear e q u a t i o n s . T h e s e lattice stabili
ties in t u r n acted a s reference states for the s u b s e q u e n t
e v a l u a t i o n o f missing i n t e r a c t i o n coefficients in m a n y
b i n a r y systems. W i t h t h e a c c u m u l a t i o n o f sufficient
d a t a , it b e c a m e possible t o g e n e r a t e empirical f o r m u
l a t i o n s t h a t allowed t h e e s t i m a t i o n o f missing p a r a m
eters, a n d t h e n u m b e r o f calculated d i a g r a m s
increased very rapidly. H o w e v e r , t h e absence of ab

315

Phase Diagrams

and Phase Stability:

Calculations

initio calculations often raised t h e criticism t h a t

the revelant free energy curves were being g e n e r a t e d
by a series of a r b i t r a r y p a r a m e t e r s . It t h u s b e c a m e
increasingly i m p o r t a n t to check all d a t a sets for selfconsistency, particularly in t e r m s of t h e internal
relationships t h a t m u s t exist b e t w e e n different
t h e r m o d y n a m i c p r o p e r t i e s . T h i s led t o t h e e v o l u t i o n
of o p t i m i z a t i o n p r o g r a m s , in which m a n y s e p a r a t e
sources of t h e r m o d y n a m i c i n f o r m a t i o n (such a s speci
fic h e a t s , melting p o i n t s , h e a t s of f o r m a t i o n a n d t h e
v o l u m e r a t i o of t h e phases) c o u l d b e c o m b i n e d t o give
statistically best-fit values for all t h e necessary i n p u t
p a r a m e t e r s ( L u k a s et al. 1977). Such self-consistency
also ensures t h a t there is a reliable d a t a b a s e t h a t c a n
regenerate all available t h e r m o d y n a m i c d a t a as well
as t h e p h a s e d i a g r a m (see F i g . 2). A l t h o u g h this article
c o n c e n t r a t e s o n metallic systems, a n a l o g o u s d a t a
bases a n d techniques exist for salts, slags a n d c e r a m
ics, a n d a d v a n c e s in p h a s e d i a g r a m calculations
s h o u l d be seen a s h a v i n g universal a p p l i c a t i o n .

1. Extension

to Metastable

Phases

T h e use of c o m m e r c i a l alloys often involves h e a t

t r e a t m e n t s g e n e r a t i n g m e t a s t a b l e p h a s e s t h a t , b y defi
nition, d o n o t a p p e a r in e q u i l i b r i u m p h a s e d i a g r a m s .
O n e of t h e great virtues of p h a s e d i a g r a m calculations
is t h e freedom t o insert o r o m i t p h a s e s , with t h e result
t h a t it is also possible t o calculate equilibria involving
m e t a s t a b l e p h a s e s ( S a u n d e r s 1989) (see Fig. 3). T h e
accuracy with which it is possible t o f o r m u l a t e t h e free
energy of m e t a s t a b l e p h a s e s m a y even b e greater t h a n
for s o m e of t h e stable p h a s e s , d e p e n d i n g o n t h e

0.05

0.10

0.15

0.20

0.25

Mole fraction of Lithium

Figure 3
Comparison of experimentally determined and calculated
phase boundaries between aluminum and the metastable
' Al 3Li phase in aluminum-lithium

relative c o m p l e x i t y of t h e crystal s t r u c t u r e s c o n c e r n e d
a n d t h e e x p e r i m e n t a l d a t a available. I n fact, calcula
tions c a n b e e x t e n d e d t o a m o r p h o u s p h a s e s a n d there
is m u c h m o r e scope for realistic predictions t h a n is
generally realized ( S a u n d e r s a n d M i o d o w n i k 1986).

2. Extension

to Multicomponent

Systems

Interest in calculated d i a g r a m s also increased consi

d e r a b l y w h e n it w a s f o u n d , o n c e v a r i o u s b i n a r y
d i a g r a m s h a d been calculated a n d h a d p r o d u c e d selfconsistent results, t h a t t h e s a m e c h a r a c t e r i z a t i o n p a r
a m e t e r s were c a p a b l e of g e n e r a t i n g m u l t i c o m p o n e n t
systems b y a simple e x p a n s i o n of t h e b i n a r y f o r m a
lism. I n t h e majority of cases, t e r n a r y systems c a n b e
calculated from p r o p e r l y characterized b i n a r y d a t a
with a m i n i m a l a d d i t i o n of p a r a m e t e r s u n i q u e t o t h e
specific t e r n a r y system (see F i g . 4):
AGa(xiXjxk9

E j

T) =

+
+ RT

E
Ejk

xixjAG J +xjxkAG 0L

"*
=

Eki

xkXiAGa

In + xiXjxkAG

kE i j

xt

(3)
Eijk

0.2

0.4

0.6

Mole fraction of

0.8

lithium

Figure 2
Calculated phase diagram of aluminum-lithium with
experimental data superimposed (Saunders 1989)
316

a r e t e r n a r y i n t e r a c t i o n t e r m s which a r e
where G
often relatively small o r zero.
T h i s p r o v i d e d t h e m a j o r s p u r t o t h e c r e a t i o n of a n
e x p a n d i n g d a t a b a s e , p a r t i c u l a r l y for c o m b i n a t i o n s of
3d t r a n s i t i o n elements of industrial interest ( K a u f m a n
a n d Bernstein 1970, K a u f m a n 1972). T e r n a r y sys
tems, h o w e v e r , b r i n g s o m e a d d i t i o n a l choice p a t t e r n s
for m o d e l l i n g h o w a b i n a r y c o m p o u n d with a given
crystal s t r u c t u r e e x t e n d s i n t o t h e t e r n a r y system. O n e

Phase

Diagrams

and Phase

Stability:

Calculations

suits b a s e d o n t h e r m o d y n a m i c d a t a a n d a r e c a p a b l e
of e x t e n s i o n t o m u l t i c o m p o n e n t systems. A c o n v e n
ient s u m m a r y of t h e c u r r e n t scope of p h a s e d i a g r a m
c a l c u l a t i o n s is given by t h e ten year index of the
C a l p h a d j o u r n a l for 1977-1986 ( B e r n a r d 1986).

3. Approaches

to

Modelling

A d v a n c e s in m o d e l l i n g h a v e t a k e n place in three
s e p a r a t e areas:

Figure 4
Comparison of calculated phase equilibria with
experimental data for the chromium-iron-silicon system
at 1173 (Chart et al. 1980)

way, is t o c o n s i d e r t h e c o r r e s p o n d i n g stability of
c o m p o u n d s with t h e s a m e crystal s t r u c t u r e in t h e
o t h e r t w o edge-binaries. W h e n three b i n a r y systems
c o m b i n e t o f o r m a t e r n a r y system, t h e stable c o m
p o u n d s t h a t o c c u r in o n e of t h e b i n a r y systems m a y
n o t h a v e i s o m o r p h o u s c o u n t e r p a r t s in the o t h e r edgebinaries. It t h e n b e c o m e s necessary t o h a v e a value for
the stability of t h e ( m e t a s t a b l e ) " c o u n t e r p h a s e " of t h e
s a m e crystal s t u c t u r e , a l t h o u g h this is b y definition
experimentally inaccessible.
T h i s p r o b l e m is in m a n y w a y s a n a l o g o u s t o t h a t of
e s t i m a t i n g missing lattice stabilities for t h e e l e m e n t s ,
b u t as there a r e m a n y m o r e subtle v a r i a t i o n s in crystal
s t r u c t u r e for intermetallic p h a s e s , there a r e c o r r e s
p o n d i n g l y fewer m e m b e r s of a p a r t i c u l a r crystal sym
m e t r y from which t o d r a w guidelines. Nevertheless as
d a t a b a s e s b e c a m e m o r e extensive, empirical rules
were evolved a n d utilized t o m a k e useful a p p r o x i m a
tions, even for t h e i n t r o d u c t i o n of p a r a m e t e r s for
t e r n a r y c o m p o u n d s t h a t h a v e n o c o u n t e r p a r t in t h e
c o m p o n e n t b i n a r y systems.
T h e e v o l u t i o n of meaningful empirical relation
ships a n d their r e p l a c e m e n t b y m o r e f u n d a m e n t a l
expressions clearly r e q u i r e d i n t e r n a t i o n a l c o l l a b o r a
tion. A c c o r d i n g l y t h e C a l p h a d (calculation of p h a s e
d i a g r a m s ) g r o u p w a s f o u n d e d in 1972 t o s h a r e t h e
i n f o r m a t i o n necessary t o t h e further d e v e l o p m e n t of
this r a p i d l y e x p a n d i n g t e c h n i q u e , b r i n g i n g t o g e t h e r
w o r k e r s using a variety of different m o d e l s a n d m e t h
odologies t o h a n d l e a n increasingly m u l t i d i m e n s i o n a l
problem. Whereas b o t h the Calphad G r o u p and the
C a l p h a d j o u r n a l a r e c o n c e r n e d w i t h all k n o w n m e t h
o d s (including first-principle calculations) relating t o
p h a s e stability, t h e label C a l p h a d m e t h o d refers t o a
subset of t e c h n i q u e s t h a t p r o d u c e self-consistent re-

(a)

v a r i a t i o n s in the p o l y n o m i a l expressions used

t o m o d e l k n o w n t h e r m o c h e m i c a l b e h a v i o u r of
b i n a r y systems,

(b)

t h e extension of such expressions t o c o p e with

m u l t i c o m p o n e n t systems, a n d

(c)

t h e i n c o r p o r a t i o n of expressions m o r e closely
related t o t h e u n d e r l y i n g physical reality of
bonding mechanisms.

T h e first of these is largely a m a t t e r of m a t h e m a t i c a l

m a n i p u l a t i o n , a n d m o s t of t h e systems in use a r e
c a p a b l e of m a t h e m a t i c a l t r a n s f o r m a t i o n i n t o each
o t h e r ( T o m i s k a 1986). H o w e v e r , t h e r e is obviously
m e r i t in using a system which is c a p a b l e of unlimited
e x p a n s i o n t o a n increasing n u m b e r of c o m p o n e n t s
(Hillert 1986).
T h e increasing capability of p e r f o r m i n g m u l t i c o m
p o n e n t p h a s e d i a g r a m c a l c u l a t i o n s routinely, h a n d
ling as m a n y as eight c o m p o n e n t s , t h e n clearly raises a
need for d a t a relating t o e x p e r i m e n t a l l y inaccessible
p h a s e s a n d for reliable p r e d i c t i o n s of these missing
d a t a from relevant chemical o r physical m o d e l s .
Chemical models incorporate well-known concepts
such as chemical a n d m a g n e t i c o r d e r i n g , nearest
n e i g h b o r i n t e r a c t i o n s , a t o m i c size r a t i o , electronega
tivity, g r o u p n u m b e r a n d b o n d s t r e n g t h . Such m o d e l s
h a v e led t o c o n s i d e r a b l e a d v a n c e s , b u t a r e clearly
b a s e d o n semiempirical generalizations, a n d involve
injecting a further set of p a r a m e t e r s from i n d e p e n d e n t
a n d n o t a l w a y s self-consistent sources.
Physical m o d e l s h a v e set themselves m u c h m o r e
stringent goals, with a r e q u i r e m e n t t h a t wherever
possible t h e t h e r m o d y n a m i c stability is consistent
with elastic c o n s t a n t s a n d t h e r m a l p r o p e r t i e s , the
u l t i m a t e goal being a m o d e l consistent with q u a n t u m
m e c h a n i c s a n d with n o adjustable c o n s t a n t s o t h e r
t h a n t h e a t o m i c n u m b e r . T h i s results in a n inevitable
clash b e t w e e n a c c u r a c y , in t e r m s of a relationship
with f u n d a m e n t a l physical p a r a m e t e r s , a n d the exten
sion of such a f o r m a l i s m t o t e r n a r y systems, let a l o n e
t o c o m p l e x m u l t i c o m p o n e n t systems. It is inherently
very difficult t o h a v e a simple e n o u g h overall f o r m a
lism, c a p a b l e of being easily differentiated t o yield free
energy m i n i m a in m u l t i c o m p o n e n t systems t h a t a t the
s a m e time c a n i n c o r p o r a t e q u a n t u m - m e c h a n i c a l cal
c u l a t i o n s . T h i s h a s led t o t h e availability of a spec
t r u m of t e c h n i q u e s t h a t c a n be selected a c c o r d i n g t o

317

Phase

Diagrams

and Phase

Stability:

Calculations

CaLphad method
5

I0

I0

cluster variation

band calculations

Monte CarLo
moLecuLar dynamics

associate
sublattice
quasichemical
regular solution

AG

10'

io|

of a c o n t i n u u m of p a r t i a l l y - o r d e r e d states. T h e
m e t h o d c a n be e x t e n d e d t o o r d e r i n g in t e r n a r y sys
t e m s , b u t a t p r e s e n t it is difficult t o e x t e n d t o m u l t i c o m p o n e n t systems b e c a u s e the c o m b i n a t i o n s of site
o c c u p a n c y b e c o m e excessive. T h e basic e q u a t i o n is
o rd

= Nxixj(AWx

3W2)

-^Wx-6W2)f]
pocket calculator
number of adjustable parameters
Empirical

First principles

Semiempirical
Physical soundness

W2(f\+fl)
L

NKT
+ ^ ( ^ 1

P A + P B^

P B)

(4)

Figure 5
Overview of models and methods used to represent and
calculate thermodynamic properties (Agren 1986)

user r e q u i r e m e n t s , time c o n s t r a i n t s a n d the a c c u r a c y

required in solving a p a r t i c u l a r p r o b l e m (see Fig. 5).
Historically, t h e d e v e l o p m e n t s first e x p l o r e d in
1970-1980 were largely b a s e d o n the q u a s i c h e m i c a l
a p p r o a c h a n d c o u l d be described as the a d d i t i o n of
s u b r o u t i n e s t o established p r o c e d u r e s .

4. The Inclusion

of Chemical

Ordering

O n e of the chief d e v e l o p m e n t s in t h e 1970-1980

p e r i o d included t h e a d d i t i o n of o r d e r i n g p a r a m e t e r s
t o s o l i d - s o l u t i o n p h a s e s , w h i c h u p until t h a t t i m e h a d
generally been a s s u m e d t o be fully d i s o r d e r e d . W i t h
fully d i s o r d e r e d s o l u t i o n s it is easy t o write a n explicit
expression for t h e e n t r o p y of m i x i n g of a n y n u m b e r of
c o m p o n e n t s , while a n y d e v i a t i o n s from t h e fully
d i s o r d e r e d m o d e l are i n c o r p o r a t e d i n t o t h e i n t e r a c
E
tion t e r m s (AG ) of E q n . (1).
By c o n t r a s t , the early a p p r o a c h e s t o c h a r a c t e r i z i n g
intermetallic p h a s e s a s s u m e d fully-ordered s t r u c t u r e s ,
with d i s o r d e r in t e r n a r y p h a s e s b e i n g confined t o
specific sublattices; this device also leads t o a simple
explicit expression for the e n t r o p y of m i x i n g for such
phases.
Clearly a m e t h o d of h a n d l i n g the c o n t i n u o u s t r a n
sition b e t w e e n o r d e r e d a n d d i s o r d e r e d s t r u c t u r e s is
needed. I n the simplest such t r e a t m e n t , the B r a g g Williams a p p r o a c h ( I n d e n 1974), a simple set of
i n t e r a c t i o n s b e t w e e n nearest a n d next n e a r e s t neigh
b o r s is a s s u m e d , a n d the r e q u i r e d i n t e r a c t i o n p a r a m
eters a r e related explicitly t o the h e a t of s o l u t i o n of
the d i s o r d e r e d p h a s e a n d t o the o r d e r i n g t e m p e r a t u r e .
It is t h u s possible t o derive these p a r a m e t e r s from
readily available e x p e r i m e n t a l i n f o r m a t i o n in m a n y
cases, a n d the i n t r o d u c t i o n of site o c c u p a t i o n p r o b a
bilities t h e n allows t h e c a l c u l a t i o n of t h e free energy

318

w h e r e Wx a n d W2 a r e first a n d s e c o n d n e i g h b o r
L
L
i n t e r a c t i o n coefficients, P A a n d P B are site o c c u p a t i o n
p r o b a b i l i t i e s o n sublattice L, a n d fx,f2,
a n d f3 a r e
L
functions of P A.
T h i s m o d e l also h a s n o p r o v i s i o n for s h o r t - r a n g e
chemical o r d e r a b o v e t h e critical o r d e r i n g t e m p e r a
t u r e , so t h a t a n u m b e r of a r b i t r a r y fitting c o n s t a n t s
h a v e t o be included t o m a t c h e x p e r i m e n t a l i n f o r m a
tion in real systems, w h e r e s h o r t - r a n g e o r d e r is
generally f o u n d t o be i n e s c a p a b l y p r e s e n t . C o n s e
q u e n t l y , a h i e r a r c h y of o t h e r t e c h n i q u e s h a s been
d e v e l o p e d t o include the effects of s h o r t - r a n g e o r d e r
( A c k e r m a n et al. 1989). A s the n a m e implies, the
cluster v a r i a t i o n m e t h o d ( C V M ) c o n s i d e r s i n t e r a c t i o n
p a t t e r n s in clusters of v a r i o u s sizes, w i t h the tetra
h e d r o n a p p r o x i m a t i o n c u r r e n t l y the m o s t p o p u l a r
m e t h o d b u t still r e q u i r i n g c o n s i d e r a b l e c o m p u t i n g
effort. I n c l u d i n g increasingly larger n u m b e r s of a t o m s
ultimately requires M o n t e C a r l o c a l c u l a t i o n s (Crusius
a n d I n d e n 1988), a c k n o w l e d g e d t o give t h e m o s t
definitive results, b u t r e q u i r i n g extensive c o m p u t i n g
time (see Fig. 5). It s h o u l d be n o t e d t h a t , despite their
m a t h e m a t i c a l rigor, all these m e t h o d s r e q u i r e s o m e
e x t e r n a l i n p u t in t h e f o r m of i n t e r a c t i o n p a r a m e t e r s
a n d c a n n o t be c o n s i d e r e d as first-principle calcula
tions unless t h e relevant i n t e r a c t i o n p a r a m e t e r s h a v e
b e e n supplied b y ab initio c a l c u l a t i o n s .

5. Incorporation

of Magnetic

Terms

T h e extensive effects of m a g n e t i s m were n o t generally

a p p r e c i a t e d until m a g n e t i c t e r m s were q u a n t i t a
tively i n c o r p o r a t e d i n t o p h a s e d i a g r a m c a l c u l a t i o n s
( M i o d o w n i k 1982). F o r e x a m p l e , t h e m a g n i t u d e
of t h e m a g n e t i c free energy b e t w e e n a n d i r o n is
nearly ten times g r e a t e r t h a n the n o n m a g n e t i c cornp o t e n t a n d of o p p o s i t e sign, a n d so h a s a d o m i n a n t
effect o n p h a s e t r a n s f o r m a t i o n s in all ferrous alloys.
C u r r e n t l y available m e t h o d s for p r e d i c t i n g t h e m a g n i
t u d e of possible m a g n e t i c effects r e q u i r e the i n s e r t i o n
of i n d e p e n d e n t l y available e x p e r i m e n t a l or e s t i m a t e d

Phase

i n p u t s for t h e B o h r m a g n e t o n n u m b e r () a n d t h e
C u r i e t e m p e r a t u r e (Tc), a n d a variety of p o l y n o m i a l
fitting functions a r e used t o r e p r o d u c e t h e e x p e r i m e n
tally observed c o n c e n t r a t i o n d e p e n d e n c e of these
t w o p a r a m e t e r s . M o s t of t h e available semiempirical
f o r m u l a t i o n s of m a g n e t i c free energy a r e b a s e d o n
q u a n t u m - m e c h a n i c a l f o r m u l a e of t h e e n t r o p y associ
ated with discrete m a g n e t i c spins, a n d all yield very
similar results ( M i o d o w n i k 1986). W h e r e a s p h a s e s
stabilized by chemical o r d e r i n g often h a v e very simple
stoichiometrics a n d o c c u r in s y m m e t r i c a l p o s i t i o n s in
the p h a s e d i a g r a m , t h e v a r i a t i o n of a n d Tc w i t h
c o m p o s i t i o n c a n be m a r k e d l y u n s y m m e t r i c a l , t h u s
a c c o u n t i n g for a n u m b e r o f w h a t m u s t o t h e r w i s e b e
considered highly a n o m a l o u s p h a s e d i a g r a m s . I n this
respect, the inclusion of m a g n e t i c t e r m s i n t o t h e r m o
d y n a m i c calculations h a s m u c h simplified t h e overall
classification of p h a s e d i a g r a m s from a p e d a g o g i c
p o i n t of view.
By treating m a g n e t i s m in t e r m s of localized spin, it
is possible t o c o m b i n e b o t h chemical a n d m a g n e t i c
o r d e r i n g p h e n o m e n a w i t h i n t h e B r a g g - W i l l i a m s for
m u l a t i o n ( I n d e n 1982), a l t h o u g h it is clear t h a t this is
a n even c r u d e r a p p r o x i m a t i o n t h a n w h e n this is used
for chemical o r d e r i n g a l o n e . I n c r e a s e d a c c u r a c y c a n
be p r o d u c e d by u s i n g m a t h e m a t i c a l fitting functions
t o describe t h e specific-heat a n o m a l i e s associated w i t h
o r d e r i n g effects, b u t such m e t h o d s h a v e t h e d i s a d v a n
tage t h a t they a r e u n c o n n e c t e d with a n y physical
m o d e l a n d c a n therefore n o t b e used t o m a k e p r e d i c
tions of m a g n e t i c effects in e x p e r i m e n t a l l y inaccess
ible m e t a s t a b l e p h a s e s .

6. Semiempirical

Prediction

of Heats

of

Formation

A n o t h e r a r e a in w h i c h p r o g r e s s h a s been m a d e in a
semiempirical m a n n e r is t h e a p p l i c a t i o n of p a i r p o t e n t i a l t h e o r y t o t h e relative stability of c o m p o u n d s
of t h e s a m e s t o i c h i o m e t r y in different crystal s t r u c
tures ( M a c h l i n 1977). T h i s h a s o b v i o u s a p p l i c a t i o n s
in relation t o t h e e s t i m a t i o n of t h e energies of c o u n terphases. T h e p a i r - p o t e n t i a l c a l c u l a t i o n s m a d e b y
M a c h l i n use t h e face-centered-cubic s t r u c t u r e as a
reference state a n d specifically exclude a n y d - b a n d o r
charge-transfer c o n t r i b u t i o n s . T h e results give excel
lent relative stability values for different g e o m e t r i c
v a r i a n t s of A B 3 c o m p o u n d s ( a n d o t h e r s t o i c h i o m e t
rics), n o t a b l y t h o s e t h a t o c c u r as m i x t u r e s b e t w e e n
G r o u p A a n d G r o u p elements from t h e p e r i o d i c
table. T h e s a m e t e c h n i q u e also p r o d u c e s a g o o d fit
with K a u f m a n ' s t h e r m o c h e m i c a l l y - d e r i v e d i n t e r a c
tion p a r a m e t e r s for solid s o l u t i o n s b e t w e e n t r a n s i t i o n
m e t a l s (Birnie et al. 1982), b u t this m u s t be c o n s i d e r e d
p a r t l y f o r t u i t o u s since t h e m e t h o d o l o g y specifically
excludes s t r o n g {/-electron b o n d i n g .
A different a p p r o a c h t o p r e d i c t i n g t h e stability of
intermetallic p h a s e s w a s initiated b y M i e d e m a et al.
(1975). T h i s is essentially a t w o - p a r a m e t e r m o d e l

Diagrams

and Phase

Stability:

Calculations

b a s e d o n t h e a t o m i c v o l u m e s a n d t h e w o r k function
of t h e p u r e elements in t h e form in which they
n a t u r a l l y exist u n d e r s t a n d a r d c o n d i t i o n s of t e m p e r a
t u r e a n d pressure. It is a s s u m e d t h a t t h e m a c r o s c o p i c
p r o p e r t i e s used t o define t h e t w o ruling p a r a m e t e r s
c a n be a p p l i e d o n the a t o m i c scale a t t h e b o u n d a r i e s
of modified W i g n e r - S e i t z cells. T h i s semiempirical
m e t h o d for predicting b o t h t h e degree of miscibility of
t w o e l e m e n t s a n d t h e stability of intermetallic c o m
p o u n d s is surprisingly successful, b u t d o e s n o t a priori
t a k e i n t o a c c o u n t v a r i a t i o n s in stability d u e t o crystal
s t r u c t u r e . (In this respect it is c o m p l e m e n t a r y t o
M a c h l i n ' s m o d e l , w h e r e t h e e m p h a s i s is o n t h e varia
tion of energy with crystal s t r u c t u r e a t c o n s t a n t
stoichiometry.)
T h e a p p a r e n t universality of M i e d e m a ' s m e t h o d
(de B o e r et al. 1988) h a s c a u s e d theoretical physicists
t o search for t h e f u n d a m e n t a l basis for its success.
Miedema's model extrapolates macroscopic proper
ties t o t h e a t o m i c scale w i t h o u t i n v o k i n g a n y
q u a n t u m - m e c h a n i c a l principles a n d relies strongly o n
c o n c e p t s such as a t o m i c v o l u m e a n d electronegativity.
U s i n g a b a n d s t r u c t u r e m o d e l , Pettifor (1979) h a s
s h o w n t h a t there is a s e c o n d - o r d e r a t t r a c t i v e t e r m
p r o p o r t i o n a l t o t h e s q u a r e of t h e difference in a t o m i c
energy levels, which resembles t h e electronegativity
factor used by M i e d e m a . H o w e v e r , it is n o t associated
with t h e flow of c h a r g e a n d n e i t h e r is it ionic in
c h a r a c t e r . R a t h e r it reflects t h e increase in b a n d w i d t h
c o m p a r e d t o t h e p u r e c o n s t i t u e n t s . A similar analysis
of M i e d e m a ' s second t e r m indicates t h a t the success
of his semiempirical t r e a t m e n t m a y be d u e t o a
j u d i c i o u s choice of p a r a m e t e r s t h a t reflect certain
d o m i n a n t t r e n d s in t h e p e r i o d i c table, b u t which a r e
n o t in themselves t h e real causes of t h e observed
changes. Both the methods developed by Machlin and
M i e d e m a h a v e nevertheless p r o v e d very useful in
estimating
stability
values
for
experimentally
inaccessible c o u n t e r p h a s e s , w i t h t h e p r o v i s o t h a t
t h e a c c u r a c y is n o t i n t e n d e d t o b e b e t t e r t h a n
1
2.5kJ mor .

7. Semiempirical
of

Methods

of Predicting

Entropies

Fusion

Whereas Machlin and Miedema have concentrated

exclusively o n t h e p r e d i c t i o n of h e a t s of f o r m a t i o n ,
t h e t r e a t m e n t s of chemical a n d m a g n e t i c o r d e r i n g
h a v e e m p h a s i z e d t h e i m p o r t a n c e of also c o n s i d e r i n g
t h e explicit c a l c u l a t i o n of e n t r o p y c o n t r i b u t i o n s .
A l t h o u g h t h e s t r u c t u r a l d i s o r d e r i n g t h a t occurs o n
m e l t i n g is often used as a simple a n a l o g for the
c o r r e s p o n d i n g c h a n g e s t h a t o c c u r a t chemical o r
magnetic transition temperatures, the understanding
of m e l t i n g p h e n o m e n a is still relatively p o o r , largely
b e c a u s e it is difficult t o c h a r a c t e r i z e t h e liquid state.
A l t h o u g h t h e solid-state p r o p e r t i e s of t h e elements a r e
b e g i n n i n g to be calculated t o a satisfactory level of

319

Phase Diagrams

and Phase Stability:

Calculations

accuracy in m a n y cases, n o calculations a r e available

to satisfactorily predict either t h e melting p o i n t o r the
e n t r o p y of fusion of the p u r e elements.
T h i s is p a r t i c u l a r l y u n f o r t u n a t e because o n e of t h e
few s t a n d a r d m e t h o d s available for t h e p r e d i c t i o n of
the lattice stabilities of m e t a s t a b l e a l l o t r o p e s (or
c o u n t e r phases) is t o c o m b i n e a n e x t r a p o l a t e d m e t a
stable melting p o i n t with a n a s s u m e d e n t r o p y of
melting for the s t r u c t u r e in q u e s t i o n ( M i o d o w n i k
1986). Recently, the experimentally d e t e r m i n e d values
of s o m e of t h e e n t r o p i e s of fusion of t h e higher
melting p o i n t t r a n s i t i o n m e t a l s h a v e been revised t o
substantially higher values, which h a s h a d a consider
able effect o n the e s t i m a t i o n of m e t a s t a b l e lattice
stabilities. Therefore it is still c u r r e n t l y necessary t o
rely o n semiempirical c o r r e l a t i o n s t o estimate t h e
e n t r o p i e s of fusion of m e t a s t a b l e p h a s e s ( S a u n d e r s et
al. 1988). (A h a r d - s p h e r e m o d e l c a n be used as a basis
for p e r t u r b a t i o n s involving s h o r t - r a n g e o r d e r s in
liquids a n d h a s achieved s o m e success in m a t c h i n g
e x p e r i m e n t a l x-ray intensity d a t a , b u t this m o d e l of
the liquid state a p p e a r s t o be t o o c r u d e as yet t o
p r o d u c e a sufficiently a c c u r a t e AG curve with respect
to the solid phases.)

8. First-Principle
Stabilities

Calculations

of

Lattice

In o r d e r t o calculate energy differences b e t w e e n dif

ferent crystal s t r u c t u r e s of the s a m e elements t o the
required degree of a c c u r a c y from first principles, it is
necessary t o m a k e a n u m b e r of simplifying a s s u m p
tions. F o r e x a m p l e , t h e n u m b e r of electrons t a k e n
i n t o a c c o u n t m a y be restricted t o the o u t e r shell a n d
the core electrons ignored (the "frozen c o r e " a p p r o x i
m a t i o n ) , o r t h e n u m b e r of i n t e r a c t i n g a t o m s m a y be
restricted.
A n o t h e r class of a p p r o x i m a t i o n s c o n c e r n s the w a y
the q u a n t u m - m e c h a n i c a l i n t e r a c t i o n s a r e h a n d l e d in
purely m a t h e m a t i c a l t e r m s , as for instance with t h e
plane-wave a p p r o x i m a t i o n . In t h e case of t h e transi
tion m e t a l s , t h e relative i m p o r t a n c e of t h e d electrons
c a n be used t o justify the omission of certain s-p
electron i n t e r a c t i o n s . W i t h such varied a p p r o a c h e s , it
is significant t h a t similar results h a v e been achieved
by a n u m b e r of different r o u t e s .
O n e of the first successful ab initio m i c r o s c o p i c
calculations of solid-phase t r a n s f o r m a t i o n s w a s p r o
d u c e d b y Y i n a n d C o h e n (1980), w h o achieved a
resolution of 1/1000 R y which is a p p r o x i m a t e l y e q u a l
_1
for silicon. T h e calculations d o n o t
to 1 . 4 k J m o l
a u t o m a t i c a l l y predict t h e m o s t stable s t r u c t u r e , b u t
they d o calculate the relative energy of a n y p a r t i c u l a r
a t o m i c a r r a n g e m e n t so t h a t specification of the crys
tal lattice is t h e only external i n p u t o t h e r t h a n the
atomic number.
W h i l e C o h e n a n d his c o - w o r k e r s h a v e c o n c e n t r a t e d
essentially o n n o n t r a n s i t i o n m e t a l s , m a n y o t h e r

320

g r o u p s h a v e specialized in t h e t r a n s i t i o n m e t a l s ,
w h e r e t h e b o n d i n g c a n n o t be described b y i n t e r a t o m i c
p a i r p o t e n t i a l s . T h e </-band c o n t r i b u t i o n t u r n s o u t t o
be b y far t h e m o s t d o m i n a n t factor, t h u s a c c o u n t i n g
for t h e success of initial a t t e m p t s to give t h e relative
energies of face-centered-cubic, b o d y - c e n t e r e d - c u b i c
a n d h e x a g o n a l - c l o s e - p a c k e d s t r u c t u r e s o n the basis of
d b a n d s a l o n e . M a n y different a p p r o a c h e s h a v e b e e n
tried (Pettifor 1983, Skriver 1985, W a t s o n et al. 1985)
a n d it is very satisfying t o find t h a t they lead t o very
similar results. In general, state-of-the-art calcula
tions confirm t h e lattice stabilities previously d e d u c e d
from p u r e l y t h e r m o c h e m i c a l techniques a n d therefore
give f u n d a m e n t a l s u p p o r t for t h e semiempirical m e t h
o d o l o g y d e v e l o p e d since t h e mid-1960s. H o w e v e r ,
there r e m a i n s o m e discrepancies, w h o s e r e s o l u t i o n is
the subject of m u c h c u r r e n t activity.

9. First-Principle

Calculations

of

Interaction

Energies
C o l i n e t et al. (1988) h a v e recently c o n c e n t r a t e d o n
first-principle
c a l c u l a t i o n s of t h e effect of alloying
elements t h a t h a v e t h e s a m e crystal s t r u c t u r e . T h i s
a v o i d s t h e necessity of calculating lattice stabilities. It
h a s b e c o m e evident t h a t , even w h e n c h o o s i n g c o m
b i n a t i o n s of elements such as c h r o m i u m , m o l y b d e
n u m a n d t u n g s t e n w h i c h a r e adjacent in t h e periodic
table, it is necessary t o t a k e i n t o a c c o u n t s h o r t - r a n g e
chemical o r d e r so as t o o b t a i n r e a s o n a b l e c o r r e l a t i o n
with k n o w n t h e r m o c h e m i c a l i n t e r a c t i o n energies.
T h e s e w o r k e r s h a v e therefore calculated the g r o u n d state energy of solid solutions b y a c o m b i n a t i o n of
t i g h t - b i n d i n g a n d t h e cluster Bethe lattice m e t h o d
with the cluster v a r i a t i o n m e t h o d ( C V M ) for t h e
e v a l u a t i o n of t h e configurational e n t r o p y . T h e only
i n p u t s a r e the b a n d w i d t h a n d a single site energy for
each c o m p o n e n t . F i g u r e 6 s h o w s t h a t t h e miscibility
g a p is correctly p r e d i c t e d from first principles. I n the
c o n v e n t i o n a l t h e r m o c h e m i c a l t r e a t m e n t this a s y m
m e t r y c a n b e easily r e p r o d u c e d by s u b r e g u l a r solution
m o d e l s p r o v i d e d e x p e r i m e n t a l d a t a exists for t h e
system, b u t this m e t h o d clearly b e c o m e s m o r e a r b i
t r a r y w h e n it c o m e s t o m o d e l l i n g m e t a s t a b l e p h a s e s .
T h e p o t e n t i a l predictive capabilities of c o m b i n i n g
first-principle
lattice stabilities a n d solid-solution in
t e r a c t i o n s in the future a r e self-evident.
T h e w o r k of M o h r i et al. (1988) a n d Sluiter et al.
(1988) is representative of t h o s e g r o u p s using a c o m
b i n a t i o n of b a n d calculations of a t o m i c i n t e r a c t i o n s
a n d C V M calculations of c o r r e l a t i o n b e t w e e n site
o c c u p a n c y t o o b t a i n a free energy using n o adjustable
p a r a m e t e r s . M o h r i et al. used a local density func
t i o n a l a p p r o a c h t o o b t a i n i n t e r a c t i o n energies for t h e
p u r e elements a n d for A 3 B a n d A B stoichiometrics,
a n d t h e n e x t r a c t e d t h e necessary p a i r p o t e n t i a l s t o
calculate t h e p r o p e r t i e s of the r a n d o m s o l u t i o n . T h i s
is a n interesting v a r i a n t from t h e c o n v e n t i o n a l

Phase

2000

-\

L/s**

11. First Principle

Parameters

1200

\l

lOOOf800

0.1

0.2

0.3

0.4

0.5

0.6

_L

0.7

0.8

LL

0.9

1.0

Mole fraction of tungsten

Figure 6
Predicted miscibility gap for the chromium-tungsten
system vs the experimental values (Colinet et al. 1988)

m e t h o d of s t a r t i n g with t h e p r o p e r t i e s of a r a n d o m
solution a n d e x t r a c t i n g t h e necessary p a r a m e t e r s t o
allow a C V M o r M o n t e C a r l o c a l c u l a t i o n of t h e
o r d e r i n g characteristics. Since it a s s u m e s a rigidlattice m o d e l , this m e t h o d averages o u t t h e size of t h e
c o n s t i t u e n t a t o m s a n d therefore only gives g o o d
q u a n t i t a t i v e a g r e e m e n t w h e r e size differences a r e
small. A p p l y i n g these principles t o o t h e r b i n a r y c o m
b i n a t i o n s of c o p p e r , silver a n d gold a n d o t h e r m o r e
c o m p l e x systems will r e q u i r e a refinement of this
m e t h o d o l o g y before t h e results a r e of t h e a c c u r a c y
a t t a i n a b l e from p u r e l y t h e r m o c h e m i c a l t e c h n i q u e s ,
b u t this s h o u l d n o t b e t o o difficult.
H o w e v e r , it s h o u l d b e stated t h a t b e c a u s e alloys of
t r a n s i t i o n elements a n d n o n t r a n s i t i o n elements h a v e
in general been t r e a t e d b y different m e t h o d s , i n t e r m e tallic c o m p o u n d s t h a t involve e l e m e n t s from b o t h
g r o u p s (e.g., c a r b i d e s a n d b o r i d e s ) h a v e n o t received
the theoretical a t t e n t i o n they deserve.

10. First-Principle

Stability:

Calculations

16001400

and Phase

q u a l i t a t i v e t r e n d s , b u t a g a i n it is e n c o u r a g i n g t h a t
these a r e consistent with w h a t h a s been d e d u c e d from
semiempirical t h e r m o c h e m i c a l r o u t e s .

2200.

1800-

Diagrams

Calculations

of

of

Magnetic

All c u r r e n t calculations of m a g n e t i c free energy rely

o n m a k i n g i n p u t s of experimentally d e t e r m i n e d
values of a n d Tc from t h e systems in q u e s t i o n . Since
such values a r e strongly c o m p o s i t i o n d e p e n d e n t , t h e
e x t r a p o l a t i o n o f m a g n e t i c effects i n t o m u l t i c o m p o n e n t systems is likely t o p r o v i d e s o m e exceptions t o
t h e rule t h a t p r o p e r l y c h a r a c t e r i z e d b i n a r y systems
will usually allow a g o o d p r e d i c t i o n of h i g h e r - o r d e r
systems. It h a s n o t been possible t o satisfactorily
predict Tc o r t o include s h o r t - r a n g e m a g n e t i c o r d e r
within a b a n d - t h e o r y c o n t e x t , b u t this is u n d e r active
investigation (Gyorffy et al. 1989). A s with t h e q u e s
tion o f s t r u c t u r a l e n t r o p y , it s h o u l d eventually be
possible t o o b t a i n m u c h b e t t e r i n p u t i n t o t h e m a g n e t i c
c o m p o n e n t of p h a s e d i a g r a m c a l c u l a t i o n s .

12. The Current

Calculations

Status

of Phase

Diagram

S u m m a r i z i n g these v a r i o u s s t r a n d s of i n f o r m a t i o n ,
t h e m o s t i m p o r t a n t features of m o d e r n p h a s e d i a g r a m
c a l c u l a t i o n s a p p e a r t o be:
(a)

t h e c o n v e r g e n c e of results b a s e d o n totally dif

ferent t e c h n i q u e s , so t h a t increasing confidence
c a n be placed o n t h e physical significance of the
p a r a m e t e r s used in m a k i n g calculations,

(b)

t h e use of o p t i m i z a t i o n t e c h n i q u e s t o m a x i m i z e
t h e self-consistency of available t h e r m o c h e m i c a l
d a t a with p h a s e d i a g r a m i n f o r m a t i o n ,

(c)

a n increasing capability t o e x t e n d t h e results

from b i n a r y a n d t e r n a r y alloys t o m u l t i c o m p o n e n t systems,

(d)

t h e availability of a s p e c t r u m of t e c h n i q u e s t h a t
allow t h e e s t i m a t i o n of selected features of p h a s e
equilibria with v a r y i n g c o m b i n a t i o n s of accur
acy, time a n d cost, a n d

(e)

a n increasing capability t o predict t h e free energy

r e l a t i o n s h i p s of m e t a s t a b l e p h a s e s , which feature
strongly in m a n y c o m m e r c i a l alloys.

Entropy

C a l c u l a t i o n s of t h e e n t r o p y of m i x i n g d e p e n d solely
o n a k n o w l e d g e of site o c c u p a n c y a n d , therefore, n o
i m p r o v e m e n t c a n b e expected from a m o r e funda
mental approach. However, a proper calculation of
v i b r a t i o n a l a n d electronic t e r m s is m o r e difficult. I n
principle it is certainly possible t o calculate b o t h
v i b r a t i o n a l a n d electronic e n t r o p y t e r m s given t h e
band structure and the vibrational spectrum, but
these will themselves b e a c o m p l e x function of t e m
p e r a t u r e ( W a t s o n a n d W e i n e r t 1984). T h e calcula
tions of e n t r o p y c o n t r i b u t i o n s from these v a r i o u s
sources utilize m o d e l s t h a t a r e n o t c a p a b l e of being
treated as i n d e p e n d e n t from e a c h o t h e r , a n d until a
self-consistent m o d e l is evolved it will n o t b e strictly
accurate to add the various contributions. Current
a t t e m p t s m u s t therefore b e c o n s i d e r e d a s giving o n l y

Calculations

T h e s e v a r i o u s aspects a r e so interrelated t h a t it is
difficult t o c o n s i d e r t h e m in isolation, o r place t h e m in
a p a r t i c u l a r o r d e r of i m p o r t a n c e . F r o m a theoretical
p o i n t of view, t h e m o s t satisfactory aspect is t h e
c o n v e r g e n c e of values o b t a i n e d from t h e r m o c h e m i c a l
a n d a priori c a l c u l a t i o n s . F r o m a practical p o i n t of
view, t h e possibility of m a k i n g c a l c u l a t i o n s o n real
m u l t i c o m p o n e n t systems is a d r a m a t i c b r e a k t h r o u g h .

321

Phase Diagrams

and Phase

Stability:

Calculations

T h e capacity t o h a n d l e m e t a s t a b l e p h a s e s is a n ines
c a p a b l e necessity in b o t h cases. T h e decision as t o
which c o m b i n a t i o n of t e c h n i q u e s will lead t o the
o p t i m u m degree of a c c u r a c y a n d cost is a m a j o r
challenge t o c u r r e n t p r a c t i t i o n e r s , b o t h in relation t o
i m p r o v e d m o d e l l i n g a n d t o t h e design of m o r e flexible
a n d user-friendly software.
See also: Thermodynamic Activity: Measurement

Bibliography
Ackerman H, Inden G, Kikuchi R 1989 Tetrahedron
approximation of CVM for BCC alloys. Acta Metall. 37:
1-7
Agren J 1986 Modelling of the solidification process. Mater.
Res. Soc. Bull. September/October: 32-5
Bernard C 1986 Subject index for computer coupling of
phase diagrams and thermochemistry (Vols 1 through 10
1977-86). Calphad 10(3/4): 255-92
Birnie D, Machlin S, Kaufman L, Taylor 1982 Com
parison of pair potentials and thermochemical models
of the heat of formation for BCC and FCC alloys.
Calphad 6(2): 43-126
Chart T, Putland F, Dinsdale A 1980 Calculated ternary
phase equilibria for the Cr-Fe-Ni-Si system. Calphad
4(1): 27-46
Colinet C, Bessoud A, Pasturel A 1988 Theoretical determi
nation of thermodynamic data and phase diagrams for
BCC binary transition metal alloys. J. Phys. F18: 903-21
Crusius S, Inden G 1988 Order-disorder transitions in
hexagonal binary alloys: a Monte-Carlo analysis. In:
Komura S, Furukawa (eds.) 1988 Dynamics of Order
ing Processes in Condensed Matter. Plenum, New York,
pp. 139-49
de Boer F R, Brown R, Mattens W C, Miedema A R,
Niessen A 1988 Cohesion in metals. In: de Boer F R,
Pettifor D G (eds.) 1988 Transition Metal Alloys, Co
hesion and Structure, Vol. 1. North-Holland, Amsterdam
Grimwall G 1986 Thermophysical Properties of Materials.
North-Holland, Amsterdam
Gyorffy L, Staunton J B, Johnson D D, Pinski F J, Stocks
G 1989 Local density theory of magnetism and its
interrelation with compositional order in alloys. NATO
Symp. Alloy Phase Stability. Kluwer, Dordrecht, The
Netherlands, pp. 421-68
Hillert 1986 A call for increased generality. In: Bennett L
(ed.) 1986 Computer Modelling of Phase Diagrams.
Metallurgical Society of AIME, Warrendale, PA, pp. 118
Inden G 1974 Ordering and segregation reactions in BCC
alloys. Acta Metall. 22: 945-51
Inden G 1982 Continuous transformations in phase dia
grams. Bull. Alloy Phase Diagrams 2(4): 412-18
Kaufman L 1972 Calculation of binary phase diagrams.
National Physical Laboratory
Symp.
Metallurgical
Chemistry. Her Majesty's Stationery Office, London,
pp. 373-96
Kaufman L, Bernstein 1970 Computer Calculations of
Phase Diagrams. Academic Press, New York
Lukas L, Henig Th, Zimmerman 1977 Optimisation
of thermodynamic data. Calphad 1: 225-36
Machlin S 1977 Modified pair-potentials and phase
stability. Calphad 1(4): 361-77
322

Miedema A R, Boone R, de Boer F R 1975 On the heat of

formation of solid alloys. J. Less Common Metals 41:
263-98
Miodownik A 1982 The effect of magnetic transforma
tions on phase diagrams. Bull. Alloy Phase Diagrams 2(4):
406-12
Miodownik A 1986 The phase stability of the elements. In:
Bennett L (ed.) 1986 Computer Modelling of Phase
Diagrams. Metallurgical Society of AIME, Warrendale,
PA, pp. 253-84
Mohri T, Terakura K, Oguchi T, Wanatabe 1988 First
principles calculation of the thermodynamic properties
and phase diagrams of noble metal alloys. In: Lorimer
G W (ed.) 1988 Symp. Phase Transformations. Institute of
Metals, London, pp. 433-7
Pettifor D G 1979 Theory of the heats of formation of
transition metal alloys. Phys. Rev. Lett. 42(13): 846-9
Pettifor D G 1983 Electron theory of metals. In: Cahn R W,
Haasen (eds.) 1983 Physical Metallurgy, 3rd edn.
Elsevier, Amsterdam, Chap. 7
Saunders 1989 Calculated and metastable phase equili
bria in Al-Li-Zr alloys. Z. Metallic. 80(12): 894-903
Saunders N, Miodownik A 1986 Thermodynamic aspects
of amorphous phase transformation. / . Mater. Res. 1: 3846
Saunders N, Miodownik A P, Dinsdale A T 1988 Meta
stable lattice stabilities for the elements. Calphad 12(4):
351-74
Skriver L 1985 Crystal structure from one-electron
theory. Phys. Rev. 31(4): 1909-23
Sluiter M, de Fontaine D, Turchi P, Fu Zezhong F 1988
Tight-binding calculations of Ti-Rh type phase diagram.
Phys. Rev. Lett. 60(8): 716-19
Tomiska J 1986 Interconversion of different formulations of
the excess free energy. Calphad 10(3/4): 239-52
Watson R E, Davenport J W, Weinert 1985 Slater orbital
method for the calculation of structural energies of 5d
elements. Phys. Rev. 32: 4885-91
Watson R E, Weinert 1984 Contribution to the entropy
of crystals. Phys. Rev. 30(4): 1641-5
Yin , Cohen L 1980 Microscopic theory of the phase
transformation and lattice dynamics of silicon. Phys. Rev.
Lett. 45(12): 1004-7
A. P. Miodownik
[University of Surrey, G u i l d f o r d , U K ]

Pole Figures and Orientation

Distribution Functions
T e x t u r e (or preferred o r i e n t a t i o n ) is said t o o c c u r in
polycrystalline aggregates of metallic o r n o n m e t a l l i c
m a t e r i a l s w h e n t h e d i s t r i b u t i o n of c r y s t a l l o g r a p h i c
o r i e n t a t i o n s of t h e individual grains is n o n r a n d o m .
T e x t u r e is n o r m a l l y described b y linking t o g e t h e r
c r y s t a l l o g r a p h i c specifications with features of t h e
specimen g e o m e t r y . F o r e x a m p l e , a t e x t u r e c o m
p o n e n t in a wire o r r o d c a n be described in t e r m s of a
fiber texture <wvw>. T h i s m e a n s t h a t c r y s t a l l o g r a p h i c
directions of t h e t y p e <wvw> lie parallel t o t h e wire o r

Pole Figures

and Orientation

Distribution

Functions

Rolling direction
Rolling direction

(lll)[TT2]

(100) [011]

Figure 1
Typical direct pole figures showing times-random intensities: (a) {111} pole figure for copper cold rolled to 96% reduction;
(b) incomplete {200} pole figure for low-carbon steel cold rolled to 80% reduction and annealed. Two ideal orientations
are shown

r o d axis. T e x t u r e c o m p o n e n t s in sheets c a n be d e
scribed as being of the t y p e {hkl} <wvw>. T h e {hkl}
planes c a n be c o n s i d e r e d t o lie in the rolling p l a n e ,
with <wvw> directions parallel t o t h e rolling direction.
T e x t u r e s a r e usually r e p r e s e n t e d by direct o r in
verse pole figures. A m o r e s o p h i s t i c a t e d m a t h e m a t i c a l
description is p r o v i d e d by t h e crystallite o r i e n t a t i o n
d i s t r i b u t i o n function.

1. Direct

Pole

Figures

Direct p o l e figures a r e s t e r e o g r a p h i c p r o j e c t i o n s
which s h o w t h e d i s t r i b u t i o n of p l a n e n o r m a l s (poles)
with respect t o reference directions in a specimen.
T h u s , for rolled sheet, t h e specimen is c o n s i d e r e d t o
sit at the center of the reference sphere, with its
o r t h o g o n a l axes (rolling direction, n o r m a l direction,
transverse direction) aligned with t h e principal axes of
the sphere. T h e o r i e n t a t i o n of a n individual g r a i n in a
specimen c a n t h e n be r e p r e s e n t e d by p l o t t i n g t h e
positions of t h e a p p r o p r i a t e {hkl} poles relative t o the
reference directions (see Fig. 1). T h u s , for each grain
c o n t r i b u t i n g t o , say, a {100} pole figure, three poles
w o u l d a p p e a r o n the projection. If t h e t e x t u r e is
r a n d o m a n d all grains a r e c o n s i d e r e d , there will be
e q u a l n u m b e r s of poles in e q u a l a r e a s o n t h e surface
of the reference s p h e r e (there will n o t , h o w e v e r , be

e q u a l n u m b e r s in e q u a l a r e a s of the projected pole

figure, since the s t e r e o g r a p h i c projection is n o t a r e a
true). Conversely, if texture exists, poles will tend to
cluster in p a r t i c u l a r p o s i t i o n s o n t h e reference sphere
a n d o n the projection. F o r e x a m p l e , a c o m m o n
t e x t u r e c o m p o n e n t in a n n e a l e d face-centered-cubic
m e t a l s is the c u b e t e x t u r e , {100}<001>. H e r e , grains
a r e o r i e n t e d with their c u b e axes nearly parallel t o the
specimen reference axes.
T h e simplest a p p r o a c h in principle t o c o n s t r u c t i n g
a p o l e figure is t o m a k e direct o r i e n t a t i o n m e a s u r e
m e n t s o n individual g r a i n s using x-ray o r electron
diffraction m e t h o d s . In practice, however, this is
rarely possible. T h e m o s t c o m m o n p r o c e d u r e is to use
x-ray t e x t u r e g o n i o m e t r y t o d e t e r m i n e pole figures
directly. T h e t e x t u r e is t h e n o b t a i n e d from d a t a o n
m a n y t h o u s a n d s of crystals. Pole densities a r e p l o t t e d
o n t h e s t e r e o g r a p h i c projection as multiples of the
intensity expected from a s a m p l e with r a n d o m l y
o r i e n t e d crystals, a n d the p o l e figure is c o n t o u r e d .
In m a k i n g p o l e figure m e a s u r e m e n t s , it is i m p o r t a n t
t o use p r o c e d u r e s which allow t h e r a n d o m intensity t o
be d e t e r m i n e d . M o s t c o m m o n l y , i n c o m p l e t e pole
figures a r e m e a s u r e d o n sheet a n d wire samples using
a back-reflection t e c h n i q u e . T h i s limits the d e t e r m i
n a t i o n of t h e p o l e figure t o ~ 6 5 from t h e center,
since a t higher angles significant levels of a b s o r p t i o n
occur. T o o b t a i n a c o m p l e t e p o l e figure, either a

323

Pole Figures

and Orientation

Distribution

Functions

c o m b i n e d transmissionreflection m e t h o d is neces
sary, o r s o m e form of c o m p o s i t e specimen is used. A
c o m p o s i t e specimen enables t h e w h o l e of the p o l e
figure t o be d e t e r m i n e d using t h e back-reflection
t e c h n i q u e . F o r i n c o m p l e t e p o l e figures, r a n d o m s a m
ples m a d e u p from p o w d e r s which h a v e been c o m
pressed a n d sintered t o p r o d u c e high density c a n be
used as a basis for n o r m a l i z a t i o n . Results o b t a i n e d
w i t h o u t using a r a n d o m s a m p l e c a n at best be c o n
sidered as s e m i q u a n t i t a t i v e . O n the o t h e r h a n d , w h e n
a c o m p l e t e pole figure h a s been d e t e r m i n e d , a p r o c e d
u r e for n o r m a l i z a t i o n with respect t o r a n d o m levels is
available which d o e s n o t require use of a r a n d o m
s a m p l e . This is because i n t r o d u c t i o n of a t e x t u r e d o e s
n o t a d d o r s u b t r a c t a n y poles from a c o m p l e t e p o l e
figure, b u t merely redistributes t h e m . T h e r e f o r e , a
s u m m a t i o n (or i n t e g r a t i o n ) of t h e intensities over the
w h o l e a r e a of t h e pole figure m u s t give t h e s a m e result
irrespective of w h e t h e r the m a t e r i a l is t e x t u r e d o r
r a n d o m . T h e s u m m a t i o n p r o c e d u r e c a n be used t o
define a n o r m a l i z a t i o n factor by which the m e a s u r e d

intensity values a r e divided t o correct t h e m t o timesr a n d o m values. T h i s m e t h o d of n o r m a l i z a t i o n m u s t

be used w h e n high a c c u r a c y is required.

2. Inverse

Pole

Figures

W h e n t h e specimen is in wire o r r o d f o r m with a single

reference axis, o r h a s a s t r o n g fiber t e x t u r e as a result
of t h e r m o m e c h a n i c a l t r e a t m e n t , t h e texture c a n be
described effectively using a n inverse p o l e figure. T h e
reference in such a figure is p r o v i d e d b y a crystallo
g r a p h i c u n i t triangle from a s t e r e o g r a p h i c projection
of the crystal lattice in s o m e s t a n d a r d o r i e n t a t i o n . T h e
density d i s t r i b u t i o n of t h e reference direction (e.g.,
t h e wire axis) is p l o t t e d in the u n i t triangle as m u l t i
ples of the intensity expected from a r a n d o m l y
o r i e n t e d s a m p l e . A s a c o n s e q u e n c e , inverse p o l e
figures a r e s o m e t i m e s referred t o as axis d i s t r i b u t i o n
charts.

Figure 2
Crystallite orientation distribution function plot for killed steel cold rolled to 70% reduction and annealed. The principal
feature is a fiber texture in the = 45 section. The random-intensity contour is shown dotted; other intensities are
multiples of the random intensity
324

Polymer

3. Interpretation

of Pole

Figures

This is usually d o n e by a t t e m p t i n g t o fit t h e direct

pole figure characteristics t o ideal o r i e n t a t i o n s , for
e x a m p l e , {100}<001> c u b e t e x t u r e for a n n e a l e d c o p
per, {110}< 112> for cold-rolled -brass. If the t e x t u r e
is n o t very severe, o r if there is c o n s i d e r a b l e s p r e a d
a b o u t the ideal o r i e n t a t i o n s , this type of description
can be quite a m b i g u o u s . T h i s is b e c a u s e it is necessary
to specify three angles in o r d e r t o u n a m b i g u o u s l y
relate t w o sets of o r t h o g o n a l reference axes (e.g., t h e
crystal axes a n d t h e specimen axes). T h e pole figure
only gives i n f o r m a t i o n a b o u t t h e d i s t r i b u t i o n of p l a n e
n o r m a l s a n d d o e s n o t give details of r o t a t i o n a b o u t
these n o r m a l s . T h u s , only t w o angles a r e specified.
D a t a from several p o l e figures, h o w e v e r , c a n be used
to p r o v i d e a c o m p l e t e description of the texture in the
form of t h e crystallite o r i e n t a t i o n d i s t r i b u t i o n .

4. Crystallite

Orientation

Distribution

Functions

T h e crystallite o r i e n t a t i o n d i s t r i b u t i o n
function
( C O D F ) expresses t h e p r o b a b i l i t y of a crystallite
h a v i n g a n o r i e n t a t i o n described by three a n g u l a r
r o t a t i o n s which relate the crystal axes t o t h e specimen
axes. T h e s e r o t a t i o n s a r e usually specified in t e r m s of
Euler angles a n d the different p r o c e d u r e s available for
calculating t h e C O D F use different a n g u l a r specifica
tions. T h e Euler angles c a n in t u r n be used t o deter
m i n e texture c o m p o n e n t s in the f o r m {hkl}(uvw}.
To
o b t a i n a C O D F , it is necessary t o c o m b i n e i n f o r m a
tion from several pole figures for different {hkl}; e a c h
p o i n t in the C O D F is o b t a i n e d by m e a n s of a series
e x p a n s i o n , each t e r m involving d a t a from t h e p o l e
figures.
T h e results of analyses of C O D F s a r e usually
represented graphically by p l o t t i n g the p r o b a b i l i t y of
a crystallite h a v i n g a given o r i e n t a t i o n in E u l e r i a n
space (an o r t h o g o n a l space, with the three Euler
angles as axes). T h e r e a r e difficulties in m a k i n g threed i m e n s i o n a l p l o t s , a n d t h u s t h e C O D F p l o t is c o n v e n
tionally p r e s e n t e d as a series of sections t a k e n n o r m a l
to o n e of the axes. A s with t h e pole figures, c o n t o u r
m a p p i n g is used, with t h e value u n i t y representing t h e
intensity of a r a n d o m s a m p l e . I n d e x i n g c h a r t s a r e
available for the identification of specific ideal orien
t a t i o n s . F i g u r e 2 s h o w s a representative e x a m p l e of a
C O D F plot. T h e C O D F is n o r m a l i z e d by s u m m i n g
the intensities over t h e w h o l e of o r i e n t a t i o n space a n d
setting the value o b t a i n e d e q u a l t o t h a t for a r a n d o m
sample.
T h e p a r a m o u n t a d v a n t a g e of t h e C O D F as a
description of t e x t u r e is t h a t it p r o v i d e s q u a n t i t a t i v e
i n f o r m a t i o n a b o u t t h e s p r e a d of o r i e n t a t i o n s in a
textured s a m p l e . A d d i t i o n a l l y , t h e severity of t e x t u r e
c a n be d e t e r m i n e d from t h e C O D F by calculating t h e
s t a n d a r d d e v i a t i o n of t h e function from t h a t of a
r a n d o m m a t e r i a l . T h e C O D F c a n also be used t o

Dielectric

Properties:

Test

Methods

calculate t h e v o l u m e fraction of crystallites within a

specified region of Euler space, by i n t e g r a t i o n
b e t w e e n suitable limits.
T h e C O D F is m u c h m o r e useful t h a n pole figure
d a t a in s t u d y i n g the d e v e l o p m e n t of textures d u r i n g
d e f o r m a t i o n a n d s u b s e q u e n t recrystallization a n d for
c o r r e l a t i n g the texture with a n i s o t r o p y of physical
and mechanical properties.
See also: Microtextural Analysis; Pole Figures and Orien
tation Distribution Functions

Bibliography
Barrett C S, Massalski 1966 Structure of Metals, 3rd
edn. McGraw-Hill, New York
Bunge J 1982 Texture Analysis in Materials Science.
Butterworth, London
Davies G J 1976 Texture analysis and anisotropy in metals.
J. Met. 28(7): 21-8
Grewen J, Huber J 1978 Annealing textures. In: Haessner F
(ed.) 1978 Recrystallization of Metallic Materials, 2nd
edn. Dr. Riederer Verlag, Stuttgart, Germany, pp. 111-36
Hatherly M, Hutchinson W 1979 An Introduction to
Textures in Metals, Institution of Metallurgists Mono
graph No. 5. Institution of Metallurgists, London
G . J. Davies
[University of Sheffield, Sheffield, U K ]

Polymer Dielectric Properties: Test

Methods
T r a d i t i o n a l l y , dielectric d a t a o n p o l y m e r s h a v e been
6
confined t o the r a n g e 5 0 - 1 0 H z . T h i s is because the
p r e d o m i n a n t uses of p o l y m e r s as insulating m e d i a a r e
in p o w e r , voice a n d d a t a t r a n s m i s s i o n , a n d experi
m e n t a l e q u i p m e n t a p p l i c a b l e t o this frequency r a n g e
is easy t o use, a c c u r a t e a n d relatively inexpensive.
Even w h e n dielectric studies a r e focused o n t h e u n d e r
s t a n d i n g of m o l e c u l a r m o t i o n s in p o l y m e r s , few
researchers g o b e y o n d this frequency r a n g e . In p r a c
tice, dielectric m e a s u r e m e n t s m a y be o b t a i n e d effecti
4
vely over a significantly larger frequency r a n g e ( 1 0 ~ n
1 0 H z ) . T h i s b r e a d t h of fifteen d e c a d e s c a n m a k e
dielectric studies p a r t i c u l a r l y useful for c h a r a c t e r i z i n g
m o l e c u l a r m o t i o n s in p o l y m e r s w h e r e t h e i s o t h e r m a l
b r e a d t h of a s e c o n d a r y t r a n s i t i o n m a y be several
d e c a d e s . T h i s r a n g e is large c o m p a r e d with the
b r e a d t h of a single r e l a x a t i o n time, which is in the
o r d e r of o n e d e c a d e .

7. Theoretical

Considerations
4

O v e r m o s t of the m e a s u r e m e n t r a n g e (i.e., 1 0 " 8

1 0 H z ) , t h e dielectric s a m p l e m a y be treated as

325

Polymer

Dielectric

Properties:

Test

Methods

l u m p e d circuit elements. T h e a d m i t t a n c e Ys of t h e
s a m p l e is t h u s s e p a r a t e d i n t o c a p a c i t a n c e C s a n d
conductance G *
r s = j o > C s + Gs

0)

w h e r e is t h e frequency. T h e c o m p l e x permittivity *
() is t h e n o b t a i n e d by dividing Ys b y t h e a d m i t t a n c e
Yv associated with t h e g e o m e t r i c ( v a c u u m ) c a p a c i
t a n c e C v of t h e s a m p l e :
Yv=)coC,=)coe0A/d
2

e'-)e"

( C s/ C v) - j ( G > C v)

(4)

GJcoCs

(5)

If t h e d i m e n s i o n s of t h e dielectric a p p r o a c h t h e
wavelength c o r r e s p o n d i n g t o t h e m e a s u r e m e n t fre
q u e n c y , l u m p e d circuit e l e m e n t analysis is i n a p p r o
p r i a t e . T h e s a m p l e is t h e n often i n c o r p o r a t e d i n t o a
t r a n s m i s s i o n line a n d t r e a t e d as a d i s t r i b u t e d element.
T h e s e m e a s u r e m e n t t e c h n i q u e s a r e c o m m o n in t h e
8
1 0
1 0 - 1 0 H z region. T h e p r o p a g a t i o n c o n s t a n t c o n
sists of b o t h a t t e n u a t i o n a n d p h a s e :
y=

(6)

(X+)b

F o r a coaxial line in which only t r a n s v e r s e electro

m a g n e t i c ( T E M ) m o d e p r o p a g a t i o n is c o n s i d e r e d , is
related t o t h e d i s t r i b u t e d t r a n s m i s s i o n line elements
(g9 c, r a n d I) b y t h e following e q u a t i o n :
2

= (g + Jo>c) x ( r +
dielectric

Teletype

))

conductors

(7)

T h e a t t e n u a t i o n includes a c o m p o n e n t d u e t o t h e
c o n d u c t o r s a n d a c o m p o n e n t d u e t o t h e dielectric.
T h e s e p a r a t i o n of these for a low-loss dielectric is
often difficult.

Transient

Methods

T r a n s i e n t t e c h n i q u e s a r e used t o o b t a i n c o m p l e x
permittivities a u t o m a t i c a l l y over w i d e - r a n g i n g fre
4
6
q u e n c y d o m a i n s . Systems from 1 0 ~ - 1 0 H z a r e b a s e d
o n collection of t h e dielectric's t i m e - d e p e n d e n t , inte
g r a t e d c u r r e n t r e s p o n s e t o a u n i t step pulse. T h e s e
discrete d a t a a r e t h e n t r a n s f o r m e d t o o b t a i n
f r e q u e n c y - d e p e n d e n t , c o m p l e x permittivities. T h i s

326

-^Capacitor

/(/)

Ll

Rotter
A/D
converter
I/O 14

Q{t)

Integrator
I/O 16

Figure 1
Schematic representation of a computer-controlled system
for determining complex permittivities by a transient
method

t e c h n i q u e is suited t o c o m p u t e r - c o n t r o l l e d o p e r a t i o n
(Fig. 1).
T o o b t a i n t h e frequency r e s p o n s e of t h e a d m i t t a n c e
Y]co) of a dielectric it is necessary t o t r a n s f o r m b o t h
t h e impressed v o l t a g e Vt) a n d t h e dielectric's c u r r e n t
r e s p o n s e 7S(/):

) = / )/ )

(8)

T h e t r a n s f o r m of t h e voltage c a n be f o u n d analyti
cally by a s s u m i n g t h e impressed voltage t o be a step
function:

)=0

(9)

w h e r e V0 is t h e m a g n i t u d e of t h e step pulse for all

time. Alternatively, the s a m e voltage pulse m a y be
impressed o n t h e s a m p l e a n d t h e s a m p l e ' s v a c u u m
c a p a c i t a n c e . T h e c u r r e n t r e s p o n s e s a r e t h u s Is(t) a n d
7 V(0, a n d these m a y be t r a n s f o r m e d . T h i s analysis
m a k e s n o a s s u m p t i o n s as t o pulse s h a p e . N o w ,
*()) = '-)"

5())/())

(10)

T o o b t a i n t h e t r a n s f o r m of a c u r r e n t , the t o t a l timedependent current behavior should be known:

/00

I(]co)=\

2.

Pulser
1/016

Computer

(3)

T h e dielectric loss t a n g e n t ( t a n J s ) is often used

as a m e a s u r e of t h e insulating q u a l i t y of a m a t e r i a l .
It is given b y t h e a b s o l u t e r a t i o of t h e c o n d u c
tive t o capacitive c o m p o n e n t s of t h e m a t e r i a l ' s
admittance:
t a n Ss =

Temperature
monitor

Disk

(2)

w h e r e A is s a m p l e a r e a ( c m ) , d is s a m p l e thickness
1
(cm) a n d 0 = 8.85 x l O ^ F c m " . T h e n ,
8*(co)=YJY,

Temperature
control

Time base
generator

J0

()->

()

T h i s b e h a v i o r c a n n o t , h o w e v e r , be m o n i t o r e d experi
m e n t a l l y , a n d in fact d a t a a r e o b t a i n e d periodically
a n d c h a r g e , n o t c u r r e n t , is followed.
T h e d a t a a r e n o r m a l l y collected as t h e i n t e g r a t e d
c u r r e n t responses Q(tJ, w h e r e t h e times tm a r e equally
spaced in log time (e.g., 1, 2, 4, 8, . . . ) . A discrete
F o u r i e r t r a n s f o r m is used. T h e first d a t a p o i n t Q(t^)
m a y be c o n s i d e r e d t o represent i n s t a n t a n e o u s p o l a r i
zation:

Polymer

Q(tx) = p / ( O e J

j a ,/

dt

Dielectric

(12)

Properties:

Test

Methods

T o o b t a i n the t o t a l discrete t r a n s f o r m , the direct

c o n d u c t i o n c u r r e n t 7 dc m u s t b e s u b t r a c t e d before
t r a n s f o r m a t i o n . T h e e q u a t i o n for 7(jco) is t h u s
+ [ 7 ( 0 - 7 d c]e"*>' dt
(13)
J
h
w h e r e tN is the time t h e last d a t a p o i n t w a s collected.
T h e integral in discrete t r a n s f o r m a t i o n b e c o m e s a
s u m m a t i o n . If 7 dc d o m i n a t e s 7 a c this t e c h n i q u e is n o t
useful.
IQco) = Q{tx)

3.

Bridges

Scheiber (1961) discusses a very a c c u r a t e b r i d g e for

2
use in the 1 0 M 0 H z region. Hill et al. (1969)
describe the o p e r a t i o n of this b r i d g e a n d its t w o position bridge b a l a n c e . A simple b r i d g e for use from
2
3
10 H z t o 1 0 " H z (Hill et al. 1969) is s h o w n in F i g . 2.
T h e voltages + V, V a n d - j a F m u s t b e available
a n d isolation of t h e voltages m u s t b e possible. T h e
d e t e c t o r circuit amplifies t h e i m b a l a n c e , a n d Cl a n d
C 2 a r e adjusted t o o b t a i n b a l a n c e . T h e voltage m a y
be applied t o t h e X i n p u t of a s t o r a g e oscilloscope
with the d e t e c t o r o u t p u t a p p l i e d t o t h e Y i n p u t . W h e n
the oscilloscope's Lissagous p a t t e r n is r e d u c e d t o a
h o r i z o n t a l line, t h e b r i d g e is in b a l a n c e . A t these low
frequencies it is n o t easy t o o b t a i n b a l a n c e , b u t t h e
precision a n d a c c u r a c y of bridges a r e s u p e r i o r t o
those of t r a n s i e n t m e t h o d s .
Since t h e early 1960s, o n e of t h e m o r e useful
dielectric i n s t r u m e n t s h a s been t h e G e n e r a l R a d i o
C o m p a n y G R - 1 6 1 5 A c a p a c i t a n c e b r i d g e . T h i s is a
sophisticated t r a n s f o r m e r - r a t i o - a r m b r i d g e w i t h t a p s
a t o n e - t e n t h intervals in the m e a s u r i n g a r m . W h e n a
t u n e d d e t e c t o r amplifier is used, d a t a m a y b e collected
from 50 H z t o 100 k H z . T o increase m e a s u r e m e n t
accuracy (especially n e a r p o w e r frequencies) a t u n a b l e
phase-sensitive d e t e c t o r m a y b e used. T h i s allows

Null
indicotor

Figure 2
Harris low-frequency bridge

Figure 3
Schematic representation of a meter

s e p a r a t i o n of resistive a n d capacitive c o m p o n e n t s of
t h e i m b a l a n c e signal. P h a s e s e p a r a t i o n is valuable
w h e n m e a s u r i n g low-loss m a t e r i a l s subject t o capaci
tive drifts.
T h e r e a r e m a n y o t h e r sensitive bridges covering
p a r t s of t h e frequency r a n g e from 10 H z t o 1 M H z .
T h e r e a r e also m a n y i m p e d a n c e m e t e r s available
w h i c h a r e often classed as vector v o l t m e t e r s instead of
bridges. T h e y a r e useful w h e n m e a s u r i n g m o d e r a t e - t o
high-loss dielectrics. T h e s e i m p e d a n c e m e t e r s h a v e
c o m p u t e r interfacing a n d c a n a u t o m a t i c a l l y collect
dielectric d a t a over a wide frequency r a n g e .

4. Resonant

Methods
5

Precise m e a s u r e m e n t s from 10 H z t o 10 H z m a y b e
o b t a i n e d by r e s o n a n t m e t h o d s using l u m p e d circuit
6
a p p r o x i m a t i o n s , a n d a b o v e 10 H z these m e t h o d s a r e
used for m o s t low-loss p o l y m e r m e a s u r e m e n t s . T h e
c a p a c i t a n c e v a r i a t i o n m e t h o d of H a r t s h o r n a n d W a r d
(1936) gives g o o d results, a n d e x p e r i m e n t a l systems
derived from this m e t h o d a r e in wide use for p o l y m e r
research a n d q u a l i t y c o n t r o l of, for e x a m p l e , o c e a n
cable dielectrics. O n e such system (the Q m e t e r ) is
s h o w n in Fig. 3. T h e Q of t h e circuit is m o n i t o r e d
directly a n d t h e c h a n g e in Q is related t o t a n S2:

tan S2 = (CJC2)[(Ql

- Q2)IQXQ1\

(14)

w h e r e C 0 is t h e t o t a l r e s o n a n t c a p a c i t a n c e , Qx is the
m e a s u r e m e n t w i t h o u t the s a m p l e a n d Q2 is the
m e a s u r e m e n t w i t h the s a m p l e . T h e lead i n d u c t a n c e
s h o u l d n o t be i g n o r e d in a n a l y z i n g d a t a a b o v e a few
M H z , a n d for t h e m o s t a c c u r a t e m e a s u r e m e n t s the
series resistance of the leads is also i m p o r t a n t .
8
9
A r e s o n a n t t e c h n i q u e for t h e 1 0 - 1 0 H z r a n g e is
t h e r e - e n t r a n t cavity; it is useful for m o d e r a t e - t o
low-loss m a t e r i a l s . W o r k s et al. (1944) describe a n
excellent system for precise m e a s u r e m e n t s by this
t e c h n i q u e . A simplified cavity is s h o w n in Fig. 4. T h e
half-width of t h e r e s o n a n c e is m e a s u r e d either by
capacitive d e t u n i n g o r frequency v a r i a t i o n . A u t o
m a t e d systems h a v e used frequency v a r i a t i o n t o fit the
r e s o n a n c e c u r v e t o its analytical form. T h e Q of the
circuit is defined a s t h e r e s o n a n t frequency fm divided
by t h e frequency difference / b e t w e e n half-power
327

Polymer

Dielectric

Properties:

Test

Methods

High

Sample

Figure 5
A three-terminal electrode system

Sample

V///

Figure 4
Schematic representation of a re-entrant cavity

p o i n t s . If a s a m p l e is r e s o n a t e d a n d t h e n replaced b y
a n air c a p a c i t a n c e which is equivalent ( i . e . , / m is the
s a m e ) t h e s a m p l e loss is
t a n S2 = ( C 0 / C 2 ) [ ( l / f t a
=

Low

"X"

Detector

Input -

m p

l/6air)]
I)e -

(15)

significant e r r o r s , a n d e v a p o r a t e d electrodes a g a i n
c a n be used t o eliminate this. Since fringing effects a r e
significant, disk s a m p l e s w h e r e t h e electrodes e x t e n d
to the edge of the s a m p l e are n o r m a l l y c h o s e n . T h e
fringing c a p a c i t a n c e (in p F ) is t h e n given by
C e = P(0.29 - 0.58 log d)

(16)

w h e r e is s a m p l e p e r i m e t e r (cm) a n d d is s a m p l e
thickness (cm). O t h e r configurations m a y be c h o s e n
a n d A S T M D - 1 5 0 defines fringing c o r r e c t i o n s .

^distributed

* associated with t h e r e s o n a t i n g i n d u c t a n c e
a n d is i n d e p e n d e n t of t h e s a m p l e g a p . It is d e t e r m i n e d
empirically for a given cavity. E x p e r i m e n t a l l y , the use
of a vernier c a p a c i t o r causes c o u p l i n g p r o b l e m s a n d
s h o u l d be a v o i d e d . A l s o , this m e t h o d is n o t strictly a
l u m p e d circuit r e s o n a n c e . E r r o r s in fringe field c o r r e c
tions lead t o a less a c c u r a t e d e t e r m i n a t i o n of ' t h a n in
Q meters.
Qistributed

6. Microwave
8

Measurements
11

In t h e 10 10 H z region, l u m p e d circuits are n o

longer useful a n d t r a n s m i s s i o n lines (waveguides) are
used instead. If the loss of the dielectric is significantly
greater t h a n t h e metallic losses of t h e guide, s a m p l e
permittivities a r e related t o p r o p a g a t i o n c o n s t a n t s as
follows:
,

5. Electrode

In the preceding sections all s a m p l e s were t r e a t e d as

l u m p e d circuits. T r a n s i e n t a n d b r i d g e techniques a r e
well suited t o t h r e e - t e r m i n a l configurations as s h o w n
in Fig. 5. If t h r e e - t e r m i n a l electrodes a r e placed o n a
dielectric a n a c c u r a t e assessment of the geometric
c a p a c i t a n c e of the s a m p l e c a n be m a d e . T h e electrode
a r r a n g e m e n t is, however, sensitive t o the d i m e n s i o n a l
c h a n g e s of t h e s a m p l e (e.g., in t e m p e r a t u r e r u n s ) .
F o u r - t e r m i n a l cells, w h i c h h a v e a g u a r d e d air c a p a c i
t o r m o n i t o r i n g s a m p l e thickness, eliminate this
problem.
In a significant n u m b e r of p o l y m e r studies, flat
samples a r e available a n d the electrodes a r e placed
directly o n t h e p o l y m e r . Foil electrodes are often
a d e q u a t e a n d are a t t a c h e d with small a m o u n t s of
p e t r o l a t u m . H o w e v e r , e v a p o r a t e d m e t a l electrodes
m a y be used t o e n s u r e greater a c c u r a c y .
W h e r e a three-terminal configuration is unneces
sary for the a c c u r a c y required, a t w o - t e r m i n a l cell,
using a m i c r o m e t e r electrode t o c o n t a c t the specimen,
m a y be used with bridges. T w o - t e r m i n a l cells are also
used with r e s o n a n c e m e t h o d s w h e r e t h r e e - t e r m i n a l
m e t h o d s a r e n o t valid. F l a t specimens are necessary
a n d a c c u r a t e d e t e r m i n a t i o n of m a t e r i a l thickness is
crucial. A i r in series with t h e specimen c a n lead t o

328

e =m) n +

Systems

rt )]
2

" =

(17)

2(/)\ / )

(18)

']

(19)

= ( +

w h e r e is a c o n s t a n t of the e m p t y guide.
T h e e x p e r i m e n t a l s e t u p c a n be either a slotted (Fig.
6) o r n o n s l o t t e d line. N o r m a l l y a t r a n s c e n d e n t a l
e q u a t i o n m u s t be solved t o o b t a i n t h e c o m p l e x s a m p l e
p r o p a g a t i o n c o n s t a n t . W i t h p o l y m e r s it is often p o s
sible t o c h o o s e a half-wave s a m p l e since ' is k n o w n
a d e q u a t e l y . T h e m e a s u r e m e n t frequency c a n be used
as a variable in o b t a i n i n g half-wave r e s o n a n c e ; t h e
loss " m a y t h e n be o b t a i n e d in a simpler fashion.

Source

Sample

Figure 6
Transmission line (waveguide) with slotted line detector

Polymers:

M i c r o w a v e r e s o n a t o r s a r e a n a l t e r n a t i v e w a y of
d e t e r m i n i n g t h e c o m p l e x permittivity in t h e m i c r o
wave region. F o r filled r e s o n a t o r s , ' is o b t a i n e d from
the difference in Q b e t w e e n a filled a n d e m p t y cavity.
F r e q u e n c y v a r i a t i o n defines t h e r e s o n a n c e of t h e
cavity as
Q ~~ ./resonance/A/half power

In a d d i t i o n t o s t a n d a r d m i c r o w a v e t e c h n i q u e s , pulse
techniques a r e b e c o m i n g m o r e useful in s t u d y i n g
p o l y m e r s . C o m p u t e r c o n t r o l a n d analysis a r e m a k i n g
t i m e - d o m a i n t e c h n i q u e s m o r e i m p o r t a n t (Suggett
1972), a n d i m p r o v e m e n t s t o t h e e x p e r i m e n t a l a p p a r a
tus a n d d a t a analysis h a v e been m a d e . A s w i t h
low-frequency t r a n s i e n t t e c h n i q u e s , t i m e - d o m a i n
techniques a r e useful for m o d e r a t e - t o high-loss
dielectrics b u t i n a p p r o p r i a t e for low-loss dielectrics.

Bibliography
Barrie I 1965 Measurement of very low dielectric losses at
radio frequencies: new experimental technique based on
method of Hartshorn and Ward. Proc. Inst. Electr. Eng.
112: 408-15
Hartshorn L, Ward W 1936 The measurement of permit
tivity
and8 power factor of dielectrics at frequencies from
4
10 to 10 cycles per second. Proc. Inst. Electr. Eng. 79:
597-609
Hill , Vaughan W E, Price A H, Davies 1969
Dielectric Properties and Molecular Behaviour. Van Nostrand Reinhold, London
King R W 1965 Transmission Line Theory. Dover, New
York
McCrum G, Read , Williams G 1969 Anelastic and
Dielectric Effects in Polymeric Solids. Wiley, New York
Scheiber D J 1961 An ultra low frequency bridge for
dielectric measurements. J. Res. Natl. Bur. Stand. C 65:
23-42
Scott A H, Curtis L 1939 Edge correction in the determi
nation of dielectric constant. / . Res. Natl. Bur. Stand. 22:
747-75
Suggett A 1972 Time domain methods. Dielectr. Relat. Mol.
Processes 1: 100-20
von Hippel A R (ed.) 1954 Dielectric Materials and Applica
tions. Wiley, New York
Works C N, Dakin W, Boggs F W 1944 A resonant cavity
method for measuring dielectric properties at ultra-high
frequencies. Trans. Am. Inst. Electr. Eng. 63: 1092-8
G . E. J o h n s o n
[ A T & T Bell L a b o r a t o r i e s , M u r r a y Hill,
N e w Jersey, U S A ]

Polymers: Electron Microscopy

F r o m the p o i n t of view of electron m i c r o s c o p y ,
p o l y m e r s h a v e p r o p e r t i e s which a r e t o s o m e extent
similar t o t h o s e of biological m a t e r i a l s , b u t p o l y m e r s
are simpler in s t r u c t u r e a n d chemical c o m p o s i t i o n .

Electron

Microscopy

T h e i n f o r m a t i o n r e q u i r e d b y a p o l y m e r scientist is n o t
a b o u t t h e s t r u c t u r e itself, b u t a b o u t t h e r e l a t i o n s h i p
b e t w e e n t h e s t r u c t u r e a n d p r o p e r t i e s . T h u s , the in
vestigation of t h e s t r u c t u r a l details d o w n t o a m o l e c u
lar level is often necessary. It is, h o w e v e r , extremely
difficult t o resolve m o l e c u l a r s t r u c t u r e s in c o m m e r c i a l
p o l y m e r s with t h e electron m i c r o s c o p e , n o t only
b e c a u s e of their highly d i s o r d e r e d a n d a t best semicrystalline n a t u r e , b u t m a i n l y b e c a u s e of p r o b l e m s
with specimen p r e p a r a t i o n
and
electron-beam
d a m a g e . T h i s limits t h e r e s o l u t i o n in m o s t cases t o
a b o u t 5 n m , which is n o t sufficient for lattice o r
a t o m i c r e s o l u t i o n . A n e x c e p t i o n t o this rule is the
h i g h - r e s o l u t i o n electron m i c r o s c o p y of specially p r e
p a r e d single crystals of p o l y e t h y l e n e a n d paraffins
w h e r e lattice r e s o l u t i o n of less t h a n 0.5 n m h a s been
achieved ( C h a n z y et al. 1986). T h e electron m i c r o s
c o p y of c o m m e r c i a l p o l y m e r s c a n nevertheless p r o
vide s o m e very useful i n f o r m a t i o n o n the a r r a n g e m e n t
of molecules i n t o larger g r o u p s , such as crystal units
in spherulite lamellae, p h a s e s in p o l y m e r blends o r
d i s p e r s i o n of additives. It is always beneficial t o utilize
s o m e o t h e r t e c h n i q u e s a n d t o o b t a i n as m u c h a d d i
tional information on the structure and composition
of t h e specimen as possible. T h e electron m i c r o s c o p y
of p o l y m e r s s h o u l d t h u s be seen as a s o u r c e of u n i q u e
but not unlimited information.
T h e r e a r e several electron m i c r o s c o p y techniques
available, e a c h h a v i n g its o w n specific a d v a n t a g e s a n d
l i m i t a t i o n s . T h e s e t e c h n i q u e s v a r y c o n s i d e r a b l y with
respect t o the degree of difficulty with which results
c a n b e o b t a i n e d a n d t h e different i n f o r m a t i o n a b o u t
t h e p o l y m e r m i c r o s t r u c t u r e t h a t they p r o v i d e .

1. Scanning

Electron

Microscopy

T h i s t e c h n i q u e is p e r h a p s t h e easiest t o use a n d t h e
specimen p r e p a r a t i o n least d e m a n d i n g . It utilizes
s e c o n d a r y a n d b a c k - s c a t t e r e d electrons t o f o r m im
ages of surface relief. S e c o n d a r y electrons c a n only
escape from a thin surface layer a n d for this r e a s o n
low-energy electrons, typically 5 - 1 0 k e V , a r e used for
p o l y m e r s . T h e b a c k - s c a t t e r e d electron images require
t h e use of higher accelerating voltages ( 2 0 - 4 0 keV)
a n d a r e of b e t t e r q u a l i t y for specimens c o n t a i n i n g
heavier elements t h a n for p o l y m e r s .
Surfaces of b u l k specimens c a n b e p r e p a r e d easily
b y c u t t i n g , e t c h i n g o r fracturing. T o r e d u c e t h e c h a r g
ing effect i n d u c e d b y t h e incident electron b e a m , a
thin layer of gold o r o t h e r m e t a l is s p u t t e r e d o n t o the
surface in o r d e r t o increase t h e c o n d u c t i v i t y of the
specimen. T h i s results in a grainy surface s t r u c t u r e
(see F i g . lb), w h i c h is visible only a t higher magnifica
tions. T h e magnifications available o n m o s t m i c r o
scopes a n d achieved routinely, a r e usually n o t higher
t h a n x 20 000. T h i s gives a r e s o l u t i o n of a b o u t 20 n m ,
w h i c h is sufficient for m o s t a p p l i c a t i o n s , such as
fracture surface analysis (Fig. la), p o l y m e r b l e n d s

329

Polymers:

Electron

Microscopy

Figure 2
Scanning electron micrograph of a polyethylenepolycarbonate blend. The dispersion of phases is clearly
visible. The surface damage due to cutting results in the
debonding of the polycarbonate phase from the matrix
(courtesy of S. Woodisse)

( F i g . 2) o r spherulite m o r p h o l o g y o n freely crystalized, u n c u t surfaces ( F i g . 3). It c a n b e clearly seen in

F i g . 3 t h a t t h e e l e c t r o n - b e a m d a m a g e rapidly c h a n g e s
t h e surface m o r p h o l o g y . T h i s is a result of t h e
decrease in m a s s a n d c a n in s o m e cases e n h a n c e
c o n t r a s t . T h e i n t e r p r e t a t i o n of t h e m o r p h o l o g y of
b e a m - d a m a g e d surfaces, especially t h o s e of semicrystalline p o l y m e r s , is n o t yet fully u n d e r s t o o d .

2. Replica

Figure 1
Scanning electron micrograph of a low-temperature
fracture surface of a polyethylene composite. The
distribution of the filler particles can be studied in
addition to the mode of crack propagation: (a), the
fibrillated structure of a ductile fracture; (b), the same area
showing the grainy structure of the conductive gold
coating

330

Techniques

A l t h o u g h t h e s c a n n i n g electron m i c r o s c o p e ( S E M )
t e c h n i q u e c a n p r o v i d e useful i n f o r m a t i o n o n larger
i n h o m o g e n e i t i e s in p o l y m e r m a t r i c e s , it h a s a rela
tively low r e s o l u t i o n , low c o n t r a s t o n small surface
steps a n d t h e specimen surface quickly c h a n g e s as a
result of t h e e l e c t r o n - b e a m d a m a g e . M a n y m i c r o s copists, therefore, prefer t o r e m o v e t h e p o l y m e r
a n d investigate only t h e c o n d u c t i v e c o a t i n g layer in
t h e t r a n s m i s s i o n m o d e . T h e c o n t r a s t a n d the t h r e e d i m e n s i o n a l effect is preserved by e v a p o r a t i n g a h e a v y
m e t a l ( g o l d - p a l l a d i u m alloy o r p l a t i n u m ) a t a small
angle t o t h e surface ( s h a d o w i n g ) . E v a p o r a t e d c a r b o n
is used exclusively as t h e s u p p o r t i n g m a t e r i a l b e c a u s e
of its s t r e n g t h a n d t r a n s p a r e n c y . It is n o t always easy
t o r e m o v e t h e t h i n c a r b o n film from t h e b u l k p o l y m e r

Polymers:

Electron

Microscopy

i n t e r p r e t a t i o n of t h e surface features difficult a n d n o

crystallographic information can be obtained. F o r
s o m e a p p l i c a t i o n s , therefore, direct t r a n s m i s s i o n
electron m i c r o s c o p y of p o l y m e r s is r e q u i r e d .

3. Transmission

Electron

Microscopy

of

Thin

Films
Specimen p r e p a r a t i o n a n d b e a m d a m a g e a r e t h e t w o
m a j o r p r o b l e m s w h e n a p p l y i n g this t e c h n i q u e t o
p o l y m e r s . M a n y excellent t e c h n i q u e s for specimen
p r e p a r a t i o n of biological m a t e r i a l s h a v e been d e
veloped, b u t u n f o r t u n a t e l y o n l y very few c a n b e
utilized for p o l y m e r s , m a i n l y b e c a u s e of their c h e m
ical resistance a n d t o u g h , r u b b e r y n a t u r e . Suitable
specimens for electron m i c r o s c o p y m u s t be of even
t h i c k n e s s , less t h a n 1 thick for 100 k e V , with
u n d a m a g e d surfaces a n d of a sufficient c o n t r a s t . T w o
t e c h n i q u e s a r e available: c u t t i n g a n d solvent casting.

Figure 3
Scanning electron micrograph of a surface of a rapidly
cooled polyethylene. The morphology in the center
is revealed by electron-beam damage (courtesy of
S. Woodisse)

by dissolving t h e p o l y m e r in solvents a n d a t w o - s t a g e
replica t e c h n i q u e is m o r e c o m m o n l y used. T h e surface
relief of t h e specimen is first " c a s t e d " o r " p r i n t e d "
o n t o a n easily soluble c o m p o u n d , such as polyacrylic
acid, gelatin o r F o r m v a r , w h i c h is t h e n peeled off t h e
p o l y m e r a n d used for t h e p r e p a r a t i o n of a c a r b o n
replica.
T h e surface relief c a n b e p r e p a r e d in t h e s a m e w a y
as for t h e S E M specimens, b u t b e c a u s e a h i g h e r
resolution a n d c o n t r a s t a r e available, s o m e o t h e r
techniques c a n b e utilized. P e r h a p s t h e m o s t i m p o r t
a n t of these alternatives is surface-etching w i t h a n
oxidizing agent, such as p o t a s s i u m p e r m a n g a n a t e , in
solution with sulfuric a n d p h o s p h o r i c acids (Olley et
al. 1979). It is believed t h a t t h e a m o r p h o u s m a t r i x is
r e m o v e d p r i o r t o t h e crystalline p h a s e , t h u s revealing
the spherulite lamellae. Alternatively, t h e lamellar
s t r u c t u r e c a n b e revealed b y c u t t i n g t h e specimen a t
low t e m p e r a t u r e . T h e c r a c k , p r o p a g a t i n g in front of
the c u t t i n g knife edge, follows t h e w e a k p r o b a b l y
interlamellar regions, leaving a surface relief w h i c h is
similar t o the etched surface (Fig. 4).
T h e replication t e c h n i q u e is very r e w a r d i n g , as it
provides h i g h - c o n t r a s t m i c r o g r a p h s a n d is relatively
easy t o use. T h e d i s a d v a n t a g e of this t e c h n i q u e is t h a t
the resolution is limited b y t h e g r a i n size of t h e
s h a d o w i n g m e t a l t o a b o u t 10 n m ; this m a k e s t h e

3.1 Specimen
Preparation
(a) Cutting. A m o r p h o u s p o l y m e r s c a n b e c u t o n a n
u l t r a m i c r o t o m e w i t h a glass o r d i a m o n d knife a t a
t e m p e r a t u r e w h i c h is lower t h a n t h e glass t r a n s i t i o n of
t h e p o l y m e r ( a b o v e r o o m t e m p e r a t u r e for m o s t a m o r
p h o u s p o l y m e r s ) . A n e x a m p l e of a n acrylonitrile
b u t a d i e n e styrene ( A B S ) p o l y m e r is s h o w n in F i g . 5.
T h e b u l k p o l y m e r h a s b e e n stained with o s m i u m

Figure 4
Transmission electron micrograph of a two-stage replica
prepared from a cut, unetched surface revealing the
spherulite morphology (courtesy of S. Woodisse)

331

Polymers:

Electron

Microscopy
in w a t e r . It is n o t very easy to p r o d u c e films of even
thickness a n d the t e m p e r a t u r e of the s u b s t r a t e , as well
as t h e c o n c e n t r a t i o n of the solution, m u s t be carefully
c o n t r o l l e d . T h i s is t h e m a j o r t e c h n i q u e which p r o
vides films suitable for c r y s t a l l o g r a p h i c studies.
A n o t h e r t e c h n i q u e which c a n b e used is derived
from the e t c h i n g a n d single-stage replica p r o c e d u r e , in
which t h e p o l y m e r s u b s t r a t e is only partially dis
solved, leaving small debris of t h e crystalline p o l y m e r
a t t a c h e d t o t h e c a r b o n film. T h i s c o m b i n e s the high
c o n t r a s t of t h e surface relief with a possibility of
o b t a i n i n g diffraction p a t t e r n s a n d t h u s s t r u c t u r e related c r y s t a l l o g r a p h i c i n f o r m a t i o n ( N o r t o n a n d
Keller 1985).
3.2 Electron-Beam

Figure 5
Transmission electron micrograph of a thin section cut
from ABS copolymer. The butadiene phase is stained with
osmium tetroxide

Damage

A fast electron p a s s i n g t h r o u g h a thin specimen c a n

lose s o m e of its energy b y i n t e r a c t i n g with a m o l e c u l a r
chain. T h e p r o b a b i l i t y of this energy loss is indirectly
d e p e n d e n t o n t h e speed (or o n t h e energy) of the
electron. Increase in the accelerating voltage will
result in r e d u c t i o n of b e a m d a m a g e . C o n t r a s t is,
h o w e v e r , also r e d u c e d , b u t this is usually less i m p o r t
a n t . T h e energy transferred t o the p o l y m e r from the
highly ionizing electron r a d i a t i o n quickly c h a n g e s the
chemical s t r u c t u r e of the p o l y m e r . T h e c h a n g e s are
c o m p l e x a n d a r e different for each p o l y m e r a n d its

tetroxide which is a t t a c h e d t o isolated d o u b l e b o n d s

of the b u t a d i e n e p h a s e , leaving t h e styrene m a t r i x
clear. T h i s n o t only i m p r o v e s c o n t r a s t , b u t also the
cutting p r o p e r t i e s .
Crystalline p o l y m e r s , h o w e v e r , a r e extremely
difficult t o c u t as they a r e very r u b b e r y a b o v e
their glass t r a n s i t i o n t e m p e r a t u r e (between 40 C
a n d 120 C) a n d very brittle below. T h e c u t t i n g
p r o p e r t i e s of polyethylene c a n be i m p r o v e d by c h e m
ical etching with chlorosulfonic acid followed by
staining with o s m i u m tetroxide ( K a n i g 1974). It is
believed t h a t the a m o r p h o u s m a t r i x is chlorosulfon a t e d p r i o r t o the crystalline p h a s e , t h u s revealing t h e
interlamellar regions by staining (Fig. 6). U n f o r t u
nately, the sections are still heavily d a m a g e d b y
cutting a n d hence i n f o r m a t i o n o n t h e a r r a n g e m e n t of
the lamellae i n t o a spherulitic s t r u c t u r e a n d s o m e
crystallinity a r e usually lost. Alternatively, isolated
d o u b l e b o n d s c a n be p r o d u c e d by i r r a d i a t i o n a n d
then t h e m a t e r i a l c a n be stained ( P a r k e r a n d Vesely
1983). T h e c u t t i n g of stained p o l y m e r is easier as the
m a t e r i a l is h a r d e r , b u t the crystallinity is also reduced.
(b) Solvent casting. P o l y m e r is dissolved in a suitable
solvent a n d cast o n t o a glass slide. After the solvent
e v a p o r a t e s , t h e film is c o a t e d with a thin layer of
c a r b o n (heat d a m a g e m u s t be p r e v e n t e d at this stage)
( F i n c h a n d Vesely 1985). T h e film c a n be melted a n d
recrystallized before it is stripped from the glass slide

332

Figure 6
Transmission electron micrograph of a cut section of
polyethylene, exposed to chlorosulfonic acid and stained
with osmium tetroxide. The dark lines probably
correspond to the amorphous interlamellar regions
(courtesy of S. Woodisse)

Polymers:

200

400

600

D(C

800

rrf )

Figure 7
Changes in chlorine content and specimen thickness with
exposure to the electron beam D measured by x-ray
analysis and mass loss, respectively

e n v i r o n m e n t . T h e m a j o r processes a r e loss of side

g r o u p s , crosslinking, c h a i n scission a n d f o r m a t i o n of
new c o m p o u n d s w h i c h a r e m o r e resistant t o t h e b e a m
d a m a g e t h a n w a s t h e original p o l y m e r .
T h e e l e c t r o n - b e a m d a m a g e c a n be m e a s u r e d by loss
of elements (using x-ray analysis o r energy-loss a n a l y
sis), by decrease in m a s s (best m e a s u r e d b y loss of
scattering p o w e r of t h e specimen) a n d by loss of
crystallinity ( m e a s u r e d b y t h e decrease in diffracted
intensity / ) . T h e c h a n g e of t h e initial intensity / 0 with
the e x p o s u r e D (Fig. 7) c a n b e described by t h e d o u b l e
e x p o n e n t i a l function (Vesely 1984):
I/IQ = (-

A)exp(-

kxD)

+ A exp(-

k2D)

w h e r e A, kx a n d k2 a r e t h e d e c a y c o n s t a n t s . T h i s
function c o r r e s p o n d s t o t w o i n d e p e n d e n t chemical
processes, w h i c h a r e different for e a c h p o l y m e r . T h e
m e a s u r e d curves (or t h e d e c a y c o n s t a n t s ) c a n t h u s be
utilized for p o l y m e r c h a r a c t e r i z a t i o n o r identification
( F i n c h a n d Vesely 1987).
It m a y be o b v i o u s from t h e e x p o n e n t i a l n a t u r e of
the decay t h a t it is n o t possible t o o b t a i n i m a g e s of
u n d a m a g e d m a t e r i a l . T h e e x p o s u r e of t h e specimen
m u s t m a t c h t h e e x p o s u r e of t h e p h o t o g r a p h i c e m u l
sion. T h i s m e a n s , for e x a m p l e , t h a t for a p o l y e t h y l e n e
specimen, 100 keV, x 10 000 magnification a n d t h e
m o s t sensitive film available, only o n e o r t w o e x p o
sures of t h e s a m e a r e a c a n be o b t a i n e d before t h e
crystallinity of the specimen is lost. T h i s is insufficient
for a n y serious c r y s t a l l o g r a p h i c s t u d y a n d new o r
i m p r o v e d t e c h n i q u e s a r e needed.
It is essential, p r i m a r i l y , t o avoid a n y u n n e c e s s a r y
p r e i r r a d i a t i o n of t h e specimen. F o r this r e a s o n focus
ing a n d a l i g n m e n t of t h e b e a m a r e often p e r f o r m e d o n
a n a r e a adjacent t o t h e a r e a of interest a n d t h e

Electron

Microscopy

electron b e a m is deflected b a c k for p h o t o g r a p h y only

(the m i n i m u m - d o s e t e c h n i q u e ) . Alternatively, a b e a m
s h u t t e r a b o v e t h e specimen c a n be used in c o n j u n c t i o n
with a lens-current m o n i t o r a n d c a l i b r a t i o n curves (or
with a c o m p u t e r ) , so t h a t t h e m i c r o s c o p e c a n be
aligned w i t h o u t t h e electron b e a m .
T h e loss of m a s s from a p o l y m e r c a n b e r e d u c e d
several times by c o o l i n g t h e specimen t o t e m p e r a t u r e s
below 10 ( K n a p e k a n d D u b o c h e t 1980), b u t unfor
t u n a t e l y , this t e c h n i q u e is n o t generally available.
C o a t i n g t h e specimen from b o t h sides with c a r b o n
will also r e d u c e the loss in m a s s (Vesely et al. 1976).
T h e s e t e c h n i q u e s a r e useful for c r y s t a l l o g r a p h i c stud
ies only w h e n t h e loss of crystallinity is d e p e n d e n t o n
the m a s s loss as well as o n t h e i r r a d i a t i o n ( F r y e r
1984).
T h e m o s t r e w a r d i n g t e c h n i q u e s a r e t h o s e which
i m p r o v e t h e efficiency of t h e r e c o r d i n g system. I m a g e
intensifiers h a v e been used for p o l y m e r s in the p a s t
( T h o m a s a n d A s t 1974), b u t only t h e recent d e v e l o p
m e n t s in c h a r g e - c o u p l e d devices, s t o r a g e t u b e s a n d
i m a g e - p r o c e s s i n g t e c h n i q u e s m a k e s their use a t t r a c t
ive. T h e s c a n n i n g system, which h a s been available o n
t r a n s m i s s i o n electron m i c r o s c o p e s since t h e early
1970s, is in principle a very efficient a n d flexible image
intensifier.

4. Scanning

Transmission

Electron

Microscope

T h e s c a n n i n g t r a n s m i s s i o n electron m i c r o s c o p e
( S T E M ) h a s facilities for s c a n n i n g t h e electron b e a m
a c r o s s t h e specimen. T h e b e a m is focused t o a small
p r o b e b y c o n d e n s e r lenses a n d a highly excited objec
tive lens. D e t e c t o r s for t r a n s m i t t e d , scattered ( d a r k field) a n d s e c o n d a r y electrons a r e of t h e scintillator/
p h o t o m u l t i p l i e r t y p e a n d h a v e a low noise level with a
g o o d signal amplification. T h e d e t e c t o r efficiency is
increased with t h e accelerating v o l t a g e , which is a n
i m p o r t a n t a d v a n t a g e . It is t h u s possible t o w o r k a t
very low b e a m - c u r r e n t densities for searching a n d
focusing, a n d t o switch t o a h i g h e r c u r r e n t density for
t h e i m a g e r e c o r d i n g only. T h e excellent c o n t r o l of the
b e a m , its a c c u r a t e l o c a t i o n o n t h e specimen w i t h o u t
a n y d a m a g e t o t h e s u r r o u n d i n g regions a n d r e c o r d i n g
of i m a g e s at low c u r r e n t densities m a k e this t e c h n i q u e
ideally suited for m i c r o s c o p y of beam-sensitive m a t e r
ials in the m e d i u m magnification r a n g e (Vesely 1977).
T h e lenses below t h e specimen a r e used t o converge
t h e b e a m o n t o t h e d e t e c t o r , so t h a t a m i n i m u m
a m o u n t of intensity is lost. T o i m p r o v e t h e c o n t r a s t of
t h e system, it is also i m p o r t a n t to d e s c a n the b e a m so
t h a t only t h e t r a n s m i t t e d b e a m (or for t h e dark-field,
the diffracted b e a m ) enters t h e d e t e c t o r t h r o u g h the
a p e r t u r e . T h e d a r k field c a n be o b t a i n e d simply by
deflecting t h e b e a m below t h e specimen. T h i s d o e s n o t
r e q u i r e tilting of t h e specimen, as in c o n v e n t i o n a l
m i c r o s c o p y . A n e x a m p l e of t h e a p p l i c a t i o n of this

333

Polymers:

Electron

Microscopy

Figure 8
Scanning transmission electron micrograph of a solvent-cast and slowly crystallized polyethylene. Bright-field (a) and
three dark-field images (b), (c), (d) of the same area, using the 020 reflection, show the segmental grouping of spherulite
lamellae

t e c h n i q u e is s h o w n in F i g . 8, w h e r e a bright-field
a n d three dark-field i m a g e s of the s a m e a r e a o n a
polyethylene spherulitic film a r e s h o w n .
334

T h e diffraction p a t t e r n s a r e best r e c o r d e d by the

microdiffraction t e c h n i q u e , also available o n t h e scanning t r a n s m i s s i o n m i c r o s c o p e s . T h e electron b e a m is

Polymers:

Electron

Microscopy

easy, w i t h well-developed t e c h n i q u e s for specimen

p r e p a r a t i o n a n d c o n t r a s t e n h a n c e m e n t . Crystalline
p o l y m e r s a r e m o r e difficult t o p r e p a r e a s thin films
a n d t h e c r y s t a l l o g r a p h i c i n f o r m a t i o n is quickly lost
o w i n g t o b e a m d a m a g e . T h e S T E M system h a s m a n y
a d v a n t a g e s for o b t a i n i n g this i n f o r m a t i o n efficiently
in t h e m e d i u m magnification r a n g e , b u t u l t r a h i g h r e s o l u t i o n electron m i c r o s c o p y ( o n a m o l e c u l a r level)
h a s n o t always in t h e p a s t b e e n successful. I n this
respect, p o l y m e r m i c r o s c o p y is less a d v a n c e d t h a n
m i c r o s c o p y o f m e t a l s o r even biological m a t e r i a l s .
See also: Polymers: Light Microscopy; Scanning Electron
Microscopy

Bibliography

Figure 9
Scanning transmission electron micrograph of a
polyethylene single crystal in 110 dark-field.
Microdiffraction patterns were taken from two points in
the central area. The dark circles (0.25 m diam) show that
the loss of crystallinity is confined only to the area of
microdiffraction. One microdiffraction pattern is inserted
for illustration
focused t o a p r o b e of a selected d i a m e t e r (between
30 n m a n d 10 ) a n d a parallel b e a m c a n b e f o r m e d ,
so t h a t t h e diffraction s p o t s a r e very s h a r p . T h e
c a m e r a length c a n b e altered b y a projective lens a n d
the p a t t e r n r e c o r d e d in t h e s a m e w a y a s for c o n v e n
tional m i c r o s c o p y . T h e p r o b e d i a m e t e r m u s t b e
selected for t h e best c o m p r o m i s e b e t w e e n t h e b e a m
d a m a g e t o t h e specimen a n d t h e sensitivity o f t h e
p h o t o g r a p h i c p l a t e . Typically, for highly sensitive
p o l y m e r s t h e diffraction a r e a c a n b e a s small a s
100 n m ( L o w et al. 1978, Vesely a n d R o n c a 1985).
This is illustrated in F i g . 9, w h e r e t h e dark-field i m a g e
s h o w s clearly t h e loss of crystallinity only in t h e a r e a s
exposed t o t h e b e a m . A diffraction p a t t e r n is also
s h o w n . T h e a d v a n t a g e s of t h e microdiffraction tech
n i q u e a r e t h e a c c u r a t e p o s i t i o n i n g o f t h e electron
b e a m o n t h e a r e a of interest with n o u n w a n t e d
i r r a d i a t i o n o f t h e adjacent r e g i o n s , a small selected
a r e a for t h e diffraction a n d t h e high q u a l i t y of t h e
diffraction p a t t e r n s .

5.

Conclusion

L o w - r e s o l u t i o n electron m i c r o s c o p y ( a b o v e 20 n m ) of
a m o r p h o u s p o l y m e r s a n d surface replicas is relatively

Chanzy L, Folda T, Smith P, Gardner K, Revol J-F 1986

Lattice imaging in polytetrafluoroethylene single crystals.
/. Mater. Sci. Lett. 5: 1045-7
Finch D S, Vesely D 1985 Carbon coating of heat sensitive
materials. Inst. Phys. Cont. Ser. 78: 151-4
Finch D S, Vesely D 1987 The evaluation of polymers for
electron resists by mass loss measurements. Polymer 28:
675-9
Fryer J R 1984 Radiation damage in organic crystalline
films. Ultramicroscopy 14: 227-36
Kanig G 1974 Electron microscopy of plastics as demon
strated on polyethylene (in German). Kunststoffe 64:
47(M
Knapek E, Dubochet J 1980 Beam damage to organic
material is considerably reduced in cryo-electron micros
copy. J. Mol. Biol. 141: 147-61
Low A, Vesely D, Allan P, Bevis 1978 An investigation
of the microstructure and mechanical properties of
high density polyethylene spherulites. J. Mater. Sci. 13:
711-21
Norton D R, Keller A 1985 The spherulitic and lamellar
morphology of melt-crystallized isotactic polypropylene.
Polymer 26: 704-16
OUey R H, Hodge A M, Bassett D C 1979 A permanganic
etchant for polyolefines. J. Polym. Sci. Polym. Phys. Ed.
17: 6 2 7 ^ 3
Parker A, Vesely D 1983 Polymer identification by the study
of formation of unsaturated bonds during electron beam
irradiation. Inst. Phys. Conf. Ser. 68: 11-14
Thomas L, Ast D G 1974 Image intensification and the
electron microscopy of radiation sensitive polymers.
Polymer 15: 3 7 ^ 1
Vesely D 1977 The electron beam damage of synthetic
polymers. Inst. Phys. Conf. Ser. 36: 389-94
Vesely D 1984 Electron beam damage of amorphous synthe
tic polymers. Ultramicroscopy 14: 279-90
Vesely D, Low A, Bevis 1976 The beam damage of
amorphous polymers. In: Venables J A (ed) 1976 Develop
ments in Electron Microscopy and Analysis. Academic
Press, London, pp. 333-6
Vesely D , Ronca G 1985 Electron diffraction studies of
polymer-substrate interfaces. Inst. Phys. Conf. Ser. 78:
423-6
D . Vesely
[Brunei University, U x b r i d g e , U K ]

335

Polymers:

Light

Microscopy

Polymers: Light Microscopy

scale sufficiently large t o be resolved with a light

m i c r o s c o p e a r e a b u n d a n t in p o l y m e r i c m a t e r i a l s a n d
c a n h a v e a p r o f o u n d influence u p o n their p r o p e r t i e s .
H e n c e , the s t r u c t u r a l features revealed by a light
m i c r o s c o p e a r e of interest w h e n a t t e m p t i n g t o c o r r e
late s t r u c t u r e a n d p r o p e r t i e s , investigating the effects
of processing a n d in d i a g n o s i n g the cause of p r o d u c t
failure.
A f u n d a m e n t a l r e q u i r e m e n t for i m a g e visibility in
the m i c r o s c o p e is t h a t t h e specimen exhibits c o n t r a s t .
T h i s is often lacking in b u l k p o l y m e r specimens,
principally b e c a u s e the p h a s e s present d o n o t a b s o r b
light significantly a n d s h o w only a n a r r o w r a n g e of
refractive indices. F o r t u n a t e l y , optical m e t h o d s of
c o n t r a s t e n h a n c e m e n t a n d p h a s e identification a r e
available. These include such m e t h o d s as interferencecontrast,
autofluorescence
and
phase-contrast
microscopy.

T h e light (or optical) m i c r o s c o p e h a s f o u n d extensive

use in the s t u d y of the m i c r o s t r u c t u r e of synthetic
p o l y m e r s . T h e r a n g e of m i c r o s c o p i c techniques t h a t
are used reflects the wide diversity of these m a t e r i a l s
a n d the relative ease with which specialized m i c r o
scopic m e t h o d s c a n be e m p l o y e d t o extract i n f o r m a
tion from t h e m . F i g u r e 1 outlines the variety of
techniques applicable t o p o l y m e r specimens. T h e fact
t h a t b o t h t r a n s m i t t e d - l i g h t a n d reflected-light m e t h
o d s are used, with great e m p h a s i s o n t h e former,
highlights the substantial differences between t h e
m i c r o s c o p y of p o l y m e r s a n d m o r e t r a d i t i o n a l m a t e r
ials such as m e t a l s o r ceramics. W i t h respect t o b o t h
specimen p r e p a r a t i o n a n d o b s e r v a t i o n , p o l y m e r s are
often closer t o biological specimens. T h i s is n o t t o o
surprising in view of the basic similarities between
t h e m at the m o l e c u l a r level. Often t h e literature o n
biological m i c r o s c o p y techniques is equally a p p r o p r i
ate to plastics a n d r u b b e r s .
T h e lateral resolution limit of the light m i c r o s c o p e
is wavelength-limited t o a r o u n d 0.2 . T o observe
structures below this size, o t h e r t e c h n i q u e s , such as
electron m i c r o s c o p y , a r e essential (see Polymers: Elec
tron Microscopy).
However, microstructures on a

1. Specimen

Polymer

Electron

Light

microscopy

C o m m o n light
microscopy

microscopy

microscopy

R e f l e c t e d light
microscopy

Preparation

Specimens such as latices, fine p o w d e r s , thin fibers

a n d thin films c a n often be e x a m i n e d w i t h o u t a n y
specimen p r e p a r a t i o n , except for s a m p l e selection
a n d its i m m e r s i o n in a suitable liquid t o c o n t r o l

Microradiography

Acoustic

microscopy

Transmitted light
microscopy

Polarized
light

Common light
microscopy

Polarized light
microscopy

Ultraviolet a n d infrared
microscopy

microscopy
Interference
methods
j

Ultraviolet
fluorescence
microscopy
1

Differential
methods

Qualitative
methods

Quantitative
methods

Dark-field
microscopy

Dispersion
staining

Quantitative
methods

Phase-sensitive
methods
1

Differential
interfence
contrast

Quantitative
interference
methods

Phase contrast

Modulation
contrast

Figure 1
Main light microscopy techniques applicable to polymers and their interrelationships

336

Schlieren
microscopy

Polymers:

edge-diffraction effects. Bulk specimens r e q u i r e m o r e

involved p r e p a r a t i o n , t h e details of which d e p e n d o n
the form of t h e specimen, t h e precise m i c r o s c o p i c
t e c h n i q u e to be used a n d the i n f o r m a t i o n t h a t is
required.
F o r the e x a m i n a t i o n of internal s t r u c t u r e , it is
c o m m o n t o use m i c r o t o m y t o o b t a i n thin sections,
usually between 1 a n d 20 thick, for e x a m i n a
tion with a n a p p r o p r i a t e t r a n s m i t t e d - l i g h t m e t h o d .
T h e r a n g e of p o l y m e r s t h a t c a n be sectioned is re
m a r k a b l y b r o a d a n d includes acrylics a n d p o l y s t y r e n e
t h r o u g h t o low-density polyethylene a n d r u b b e r s .
Ideally, sectioning is carried o u t j u s t below the g l a s s r u b b e r t r a n s i t i o n t e m p e r a t u r e of t h e m a t e r i a l , so t h a t
soft p o l y m e r s a n d m a n y r u b b e r s need c o o l i n g (cryom i c r o t o m y ) . H a r d m a t e r i a l s , such as p h e n o l , u r e a a n d
m e l a m i n e f o r m a l d e h y d e s o r p o l y i m i d e s , c a n n o t be
sectioned by m i c r o t o m y . In these cases, thin sections
m a y be p r o d u c e d by g r i n d i n g a n d polishing as in t h e
p r e p a r a t i o n of geological specimens. Alternatively,
o b s e r v a t i o n is restricted t o t h e reflected-light m i c r o s
c o p y of polished surfaces, as in m e t a l l o g r a p h y .
In practice, t h e c u t t i n g characteristics of a p o l y m e r
m a y be significantly modified, often adversely, by the
presence of additives. In p a r t i c u l a r , the p r e p a r a t i o n of
fiber-reinforced
c o m p o s i t e s is usually very different
from t h a t of t h e unfilled h o s t resin. O n the o t h e r
h a n d , additives such as c a r b o n black, which m i g h t
be imagined t o totally p r e c l u d e the a p p l i c a t i o n of
t r a n s m i t t e d - l i g h t m i c r o s c o p y , m a y in reality p r e s e n t
n o real p r o b l e m since the section thickness c a n be
reduced sufficiently t o allow light t r a n s m i s s i o n .
O t h e r aspects of specimen p r e p a r a t i o n include
specimen e n c a p s u l a t i o n , i m p r e g n a t i o n , replication
a n d m e t a l - c o a t i n g for reflected-light surface e x a m i n a
tion. T h e details of s o m e of these specialized tech
niques h a v e been reviewed by M a s o n (1983).
C o n t r a s t e n h a n c e m e n t a n d p h a s e identification b y
selective staining, m u c h utilized by biologists, is n o t
normally open to the polymer microscopist apart
from t h e use of certain f l u o r o c h r o m e s a n d o s m i u m
tetroxide. T h e latter is used frequently t o stain speci
m e n s for b o t h light a n d electron m i c r o s c o p y (see
Polymers: Electron
Microscopy).

2. Transmitted-Light

Methods

T h e t r a n s m i t t e d - l i g h t e x a m i n a t i o n of thin sections, o r
o t h e r thin specimens, represents t h e m a i n field of
a p p l i c a t i o n of the light m i c r o s c o p e . T h e choice of
t e c h n i q u e d e p e n d s o n t h e n a t u r e of the specimen a n d
w h e t h e r qualitative o r q u a n t i t a t i v e i n f o r m a t i o n is
needed. S o m e of the m o r e i m p o r t a n t t e c h n i q u e s
s h o w n in Fig. 1 a r e discussed in Sects. 2 a n d 3. Details
of the simpler t e c h n i q u e s , such as bright-field a n d
dark-field m i c r o s c o p y , a n d their a p p l i c a t i o n s , c a n be
found in the literature ( H e m s l e y 1984, Sawyer a n d
G r u b b 1987).

Light

Microscopy

Figure 2
Microstructure of a thin section of high-density
polyethylene cooled slowly from the melt, imaged using
crossed polars

2.1 Polarized-Light

Microscopy

Polarized-light m i c r o s c o p y is recognized as o n e of
the m a i n m e t h o d s of e x a m i n i n g p o l y m e r i c materials.
T h e t e c h n i q u e s used m a y be either qualitative o r
quantitative.
(a) Qualitative methods. T h e p o l a r i z i n g m i c r o s c o p e is
n o r m a l l y used in the " c r o s s e d p o l a r s " configuration.
T h e w i d e s p r e a d use of this t e c h n i q u e stems from the
fact t h a t a l m o s t all semicrystalline p o l y m e r s , a n d
a m o r p h o u s polymers showing molecular orientation,
exhibit d o u b l e refraction, o r birefringence, effects
w h i c h are m a n i f e s t a t i o n s of optical a n i s o t r o p y . A
birefringent specimen b e t w e e n crossed P o l a r o i d
sheets (inserted a b o v e a n d below it) in the m i c r o s c o p e
will generally a p p e a r b r i g h t o r c o l o r e d against a black
b a c k g r o u n d , t h u s giving high i m a g e c o n t r a s t .
The
crystalline
microstructure
of
synthetic
p o l y m e r s , often spherulitic, h a s been studied since the
1930s, in m a n y instances by using a polarizing m i c r o
scope. Spherulites o c c u r in m a n y p o l y m e r s which are
crystallized either from t h e melt o r from a concen
t r a t e d s o l u t i o n . T h e s t r u c t u r e is essentially radially
s y m m e t r i c , b u t d i s t o r t i o n from the idealized g r o w t h
p a t t e r n m a y be p r o d u c e d by n o n r a n d o m n u c l e a t i o n
o r a n u n f a v o r a b l e t h e r m a l history. In the polarizing
m i c r o s c o p e , the result is t h a t b u l k p o l y m e r s show
well-developed spherulitic s t r u c t u r e s or, alternatively,
a m o r e g r a n u l a r a p p e a r a n c e if g r o w t h c o n d i t i o n s
h a v e been less favorable. F i g u r e s 2 a n d 3 s h o w slowcooled a n d fast-cooled samples of high-density

337

Polymers:

Light

Microscopy

Figure 3
Same polymer as in Fig. 2, but cooled rapidly. Crossed
polars were used in imaging

polyethylene, respectively, a n d illustrate t h e r a n g e

of m i c r o s t r u c t u r e t h a t m a y be e n c o u n t e r e d in a poly
ethylene m o l d i n g o r e x t r u s i o n . F i g u r e 4 s h o w s t h e
spherulitic t e x t u r e of a slow-cooled isotactic p o l y p r o
pylene. T h e a p p e a r a n c e is very different from t h a t of

Figure 4
Microstructure of a thin section of slow-cooled
polypropylene imaged using crossed polars
338

t h e polyethylene. I n fact, polarized-light m i c r o s c o p y

c a n assist in p o l y m e r identification, since spherulite
characteristics differ a p p r e c i a b l y in t e r m s of t h e
sign a n d m a g n i t u d e of t h e birefringence a n d in
" p e r f e c t i o n " (the degree t o which t h e optical
p r o p e r t i e s a p p r o a c h t h e ideal).
S o m e p o l y m e r s c a n crystallize i n t o m o r e t h a n o n e
c r y s t a l l o g r a p h i c f o r m which s u b s e q u e n t l y influences
t h e optical c h a r a c t e r of t h e spherulites. T h e bright
spherulite visible in F i g . 4 h a s a different crystal form
t o t h a t of t h e s u r r o u n d i n g m a t e r i a l . N o t only is the
birefringence higher, b u t t h e insertion of a n accessory
p l a t e i n t o t h e m i c r o s c o p e w o u l d d e m o n s t r a t e a dif
ference in t h e optical sign.
Differences in i n t r a s p h e r u l i t i c m i c r o s t r u c t u r e a r e
also visible in t h e m i c r o s c o p e . F o r e x a m p l e , b a n d e d
s t r u c t u r e s m a y be seen, w h i c h result from a c o o r d i
n a t e d twisting of t h e s u b s t r u c t u r e of t h e spherulite
d u r i n g g r o w t h . T h i s feature, t o g e t h e r with t h e general
optical characteristics of spherulites a t the m i c r o
scopic level, h a s b e e n discussed by
Haudin
(1986). T h e i m p o r t a n c e of polarized-light m i c r o s
c o p y of p r o d u c t s m a n u f a c t u r e d from semicrystalline
p o l y m e r s is t h a t it is possible t o d e d u c e s o m e t h i n g of
t h e earlier t h e r m a l a n d s h e a r histories, as well as t o
predict aspects of in-service p e r f o r m a n c e . W i t h a n
increasing u n d e r s t a n d i n g of the factors d e t e r m i n i n g
t h e d i s t r i b u t i o n of spherulite size a n d types within a
p r o d u c t , it is p r o b a b l e t h a t t h e confidence a n d scope
of these p r e d i c t i o n s c a n be increased.
T h e p o l a r i z i n g m i c r o s c o p e c a n be modified t o view
t h e small-angle light-scattering ( S A L S ) p a t t e r n p r o
d u c e d b y spherulitic specimens. T o b e able t o d o this,
t h e light b e a m needs t o b e n a r r o w a n d highly collim a t e d . T h e S A L S p a t t e r n is viewed in t h e b a c k focal
p l a n e of t h e m i c r o s c o p e ' s objective lens b y r e m o v i n g
a n eyepiece a n d replacing it b y a telescope. T h e size of
t h e S A L S p a t t e r n is inversely related t o the a v e r a g e
size of t h e spherulites in t h e field of view of the
m i c r o s c o p e . T h i s m e t h o d is, therefore, p a r t i c u l a r l y
useful for m e a s u r i n g spherulite sizes close t o , o r even
below, t h e n o r m a l r e s o l u t i o n limit of t h e m i c r o s c o p e .
A small specimen h e a t i n g c h a m b e r (a " m i c r o h o t s t a g e " ) m a y be fitted t o a p o l a r i z i n g m i c r o s c o p e in
o r d e r t o facilitate t h e o b s e r v a t i o n of c h a n g e s in t h e
m i c r o s t r u c t u r e with t e m p e r a t u r e . I n p a r t i c u l a r , t h e
c h a n g e in birefringence c a n be m o n i t o r e d , p h o t o
metrically if necessary, a s t h e specimen t e m p e r a t u r e is
increased. T h e t e m p e r a t u r e a t w h i c h birefringence
finally d i s a p p e a r s c a n b e q u o t e d as a n " o p t i c a l melt
ing p o i n t . " H o w e v e r , t h e s h a p e of t h e g r a p h relating
birefringence a n d t e m p e r a t u r e reveals a d d i t i o n a l use
ful i n f o r m a t i o n , especially a b o u t p o l y m e r - b l e n d sys
t e m s a n d c o p o l y m e r s . T h i s t e c h n i q u e is very powerful
if used alongside differential s c a n n i n g c a l o r i m e t r y .
T h e crystallization processes of n u c l e a t i o n a n d
g r o w t h c a n also b e followed using t h e m i c r o h o t s t a g e
a n d t h e m e t h o d is r o u t i n e for d e t e r m i n i n g i s o t h e r m a l
spherulite g r o w t h rates from t h e melt.

Polymers:

Light

Microscopy

e x a m p l e s a r e p r e s e n t e d b y C h a p o y (1985) a n d t h e
basic i n t e r p r e t a t i o n of liquid-crystal i m a g e s is t r e a t e d
by H a r t s h o r n e (1974).

Figure 5
Complex pattern of birefringence associated with
molecular orientation in a molded polypropylene integral
hinge. A thin section was placed between crossed polars

(b) Quantitative
techniques. Birefringence (An) is t h e
n u m e r i c a l difference b e t w e e n t w o principal refractive
indices in t h e section o r specimen being e x a m i n e d .
M e t h o d s for m e a s u r i n g An u s i n g a polarized-light
m i c r o s c o p e h a v e been used t r a d i t i o n a l l y b y p e n o l o
gists a n d m i n e r a l o g i s t s a n d a r e well d o c u m e n t e d
( W a h l s t r o m 1979). A l m o s t identical t e c h n i q u e s m a y
be used o n p o l y m e r i c specimens t o c h a r a c t e r i z e spherulites o r to d e t e r m i n e t h e degree of m o l e c u l a r orien
t a t i o n in m a n u f a c t u r e d p r o d u c t s . I n t h e latter case,
b o t h o r t h o s c o p i c a n d c o n o s c o p i c ( c o n v e r g e n t light)
m o d e s of o b s e r v a t i o n a r e effective.
Typically, An is m e a s u r e d b y first d e t e r m i n i n g the
optical p a t h difference (P) for light p a s s i n g t h r o u g h
t h e specimen. T h i s is d o n e using m i c r o s c o p e " c o m
p e n s a t o r s " of w h i c h t h e r e a r e a variety, e a c h designed
t o o p e r a t e o p t i m a l l y over a p a r t i c u l a r r a n g e of P.
C o m p e n s a t o r s of t h e E h r i n g h a u s , Berek, B a b i n e t o r
B r a c e - K o h l e r (elliptic) t y p e a r e all applicable t o
p o l y m e r specimens. If t h e thickness of t h e specimen is
t, t h e n
An

M o l e c u l a r o r i e n t a t i o n a n d frozen-in stresses also

give rise t o birefringence a n d h e n c e t h e t r a n s m i s s i o n
of light t h r o u g h t h e p o l a r i z i n g m i c r o s c o p e fitted with
crossed p o l a r s . T h i s is t r u e of b o t h a m o r p h o u s a n d
semicrystalline p o l y m e r s . A t t e m p t s a t distinction
between t h e effects of o r i e n t a t i o n a n d stress a r e often
d u b i o u s , b o t h in t h e o r y a n d practice. C e r t a i n m a n u
factured p r o d u c t s , s u c h a s fibers a n d films, s h o w high
m o l e c u l a r o r i e n t a t i o n w h i c h c a n b e readily o b s e r v e d
a n d i n t e r p r e t e d w i t h t h e m i c r o s c o p e . In t h e case of
m o l d i n g s o r e x t r u d a t e s , t h e s i t u a t i o n is m o r e c o m p l i
cated. P a t t e r n s of birefringence, such a s t h a t s h o w n in
Fig. 5, m u s t b e i n t e r p r e t e d in t h r e e d i m e n s i o n s t o fully
describe t h e s t a t e of o r g a n i z a t i o n of t h e molecules.
T h i s is n o r m a l l y d o n e b y o b s e r v i n g sections c u t in a t
least t w o o r t h o g o n a l directions. I n a given specimen,
the birefringence displayed will usually fluctuate from
o n e p o s i t i o n t o a n o t h e r . It is in this s i t u a t i o n t h a t
microscopic measurements, rather than bulk determi
n a t i o n s of t h e optical p r o p e r t i e s , b e c o m e i m p o r t a n t .
Often, t h e analysis of t h e optical a n i s o t r o p y a n d its
d i s t r i b u t i o n is carried o u t q u a n t i t a t i v e l y a n d this is
outlined in Sect. 2A(b).
T h e c o m p l e t e analysis of birefringence effects in
semicrystalline m a t e r i a l s c a n involve s e p a r a t i o n of t h e
t o t a l birefringence i n t o t h e c o n t r i b u t i o n s of t h e a m o r
p h o u s a n d crystalline regions. T o be able t o d o this,
the i n p u t of e x t r a d a t a from a d d i t i o n a l t e c h n i q u e s
such as electron o r x-ray diffraction is necessary.
P o l a r i z a t i o n m i c r o s c o p y h a s recently been used t o
study liquid-crystal p o l y m e r systems. A n u m b e r of

Pit

In practice, An is a function of t h e w a v e l e n g t h of the

light used a n d a l l o w a n c e m u s t be m a d e for this in
measurement.
A p o l y m e r c a n b e assigned a m a x i m u m value of
birefringence A m a x. T h i s is usually d e t e r m i n e d from a
fully d r a w n fiber a n d used as a reference in the
c a l c u l a t i o n of o r i e n t a t i o n functions describing the
degree of o r i e n t a t i o n . T y p i c a l values of An for c o m
mercial fibers r a n g e from 1 x 1 0 " 3 - 3 0 0 x 10~ 3. Bire
fringence values a r e c o n v e n t i o n a l l y expressed in this
way.
S o m e p o l y m e r s exhibit " f o r m birefringence" aris
ing from a regularity of s t r u c t u r e o n a scale which is
large c o m p a r e d with m o l e c u l a r d i m e n s i o n s , b u t small
relative t o t h e w a v e l e n g t h of light. S t y r e n e - b u t a d i e n e - s t y r e n e block c o p o l y m e r exemplifies this type
of m i c r o s t r u c t u r e in t h a t d u r i n g processing, " d o
m a i n s " c a n be f o r m e d w h i c h satisfy t h e size criterion.
M e a s u r e m e n t of t h e birefringence s h o w n in the
m i c r o s c o p e gives i n f o r m a t i o n o n t h e type of d o m a i n
p r e s e n t ( r o d s o r plates) a n d t h e perfection of the
s t r u c t u r e . It is p e r h a p s r e m a r k a b l e t h a t t h e light
m i c r o s c o p e , w i t h its limited lateral resolution, c a n
give i n f o r m a t i o n of this k i n d .
T h e p o l a r i z i n g m i c r o s c o p e c a n be used t o m e a s u r e
t h e individual refractive indices of birefringent speci
m e n s b y t h e a p p l i c a t i o n of t h e Becke line test. I n this
case, only a single p o l a r i z e r is e m p l o y e d , with the
specimen p r o p e r l y aligned with respect t o t h e p e r m i t
ted v i b r a t i o n direction. S u b t r a c t i o n of t h e indices
s h o u l d give t h e birefringence, b u t t h e a c c u r a c y of the
t e c h n i q u e is lower t h a n t h e d i r e c t - m e a s u r e m e n t

339

Polymers:

Light

Microscopy

m e t h o d . T h e Becke line test is often used in fiber

identification.
2.2 Phase-Contrast
and
Interference-Contrast
Microscopy
P h a s e - c o n t r a s t a n d interference-contrast m i c r o s c o p y
techniques a r e applicable t o p o l y m e r s o r p o l y m e r
systems which s h o w p h a s e s e p a r a t i o n . T h e p h a s e s
m a y be i s o t r o p i c o r a n i s o t r o p i c in optical c h a r a c t e r .
T h e function of the techniques is t o e n h a n c e i m a g e
c o n t r a s t a n d hence visibility. T h i s c a n be readily
achieved if there are refractive-index fluctuations in
the specimen greater t h a n 10~ 4. Typical a p p l i c a t i o n s
include the e x a m i n a t i o n of thin sections of p o l y m e r
blends a n d c o m p o s i t e s as well as multilayered struc
tures such as l a m i n a t e s a n d c o e x t r u s i o n s .
F i g u r e 6a, b s h o w s a section of a n " i m p a c t m o d i
fied" polystyrene i m a g e d by these t w o t e c h n i q u e s .
T h e s h a p e , size d i s t r i b u t i o n a n d l o c a t i o n of t h e r u b b e r
particles influences the m e c h a n i c a l p r o p e r t i e s of this
blend, so t h a t images of this type c a r r y i n f o r m a t i o n of
practical significance. N o n r a n d o m c o p o l y m e r s m a y
also exhibit a m u l t i p h a s e d o m a i n s t r u c t u r e . F o r ex
a m p l e , p r o p y l e n e - e t h y l e n e block c o p o l y m e r s m a y
s h o w evidence of polyethylene-rich d o m a i n s in a
p o l y p r o p y l e n e - r i c h m a t r i x . In b o t h these e x a m p l e s ,
the visibility of t h e dispersed p h a s e is virtually zero
w i t h o u t the c o n t r a s t e n h a n c e m e n t system.
In practice, b o t h systems require special optical
c o m p o n e n t s which a r e a d d e d t o the n o r m a l
transmitted-light m i c r o s c o p e . In t h e case of p h a s e c o n t r a s t m i c r o s c o p y , special objective a n d c o n d e n s e r
lenses a r e necessary. In essence, t h e p h a s e - c o n t r a s t
m i c r o s c o p e c o n v e r t s " p h a s e o b j e c t s , " in which there
are only refractive-index v a r i a t i o n s , i n t o " a m p l i t u d e
objects," which s h o w c o n t r a s t by a b s o r p t i o n . T h i s
conversion is carried o u t by the m a n i p u l a t i o n of t h e
relative p h a s e of t h e light waves passing t h r o u g h , o r
diffracted by, the specimen.
A d i s a d v a n t a g e of the p h a s e - c o n t r a s t system is the
tendency for a " h a l o " t o s u r r o u n d t h e outline of
s t r u c t u r a l features. T h i s c a n confuse i m a g e i n t e r p r e
t a t i o n , especially w h e n such features a r e in close
p r o x i m i t y or even o v e r l a p .
Interference-contrast m e t h o d s s h o w n o h a l o effects
b u t p e r f o r m t h e s a m e function of c o n t r a s t e n h a n c e
m e n t , a l t h o u g h by a different r o u t e . T h e t e c h n i q u e is
usually, b u t n o t always, b a s e d o n a polarizing m i c r o
scope, a n d e x t r a c o m p o n e n t s p e r m i t the g e n e r a t i o n of
c o n t r a s t from g r a d i e n t s of optical p a t h length ( O P L )
in the specimen. Since O P L is the n u m e r i c a l p r o d u c t
of refractive index a n d geometrical thickness, this
m e a n s t h a t for a parallel-sided feature it is the
refractive-index g r a d i e n t s t h a t a r e revealed in the
image. T h e i m a g e itself h a s s o m e u n u s u a l c h a r a c
teristics which d e m a n d c a u t i o n in i n t e r p r e t a t i o n ,
especially if birefringent specimens a r e involved.
A c o m p a r i s o n of Figs. 6a, b s h o w s the r e m a r k a b l e
dissimilarity b e t w e e n the t w o images of t h e s a m e

340

Figure 6
(a) Thin section of high-impact polystyrene, showing
rubber phase, imaged by phase-contrast microscopy.
(b) Same thin section imaged using transmitted-light
differential interference-contrast microscopy

specimen a n d e m p h a s i z e s the fact t h a t w h a t is seen in

the m i c r o s c o p e m u s t be i n t e r p r e t e d with d u e a p p r e
ciation of t h e effect of t h e optical system e m p l o y e d .
T h e spherulitic t e x t u r e of p o l y m e r s discussed in
Sect. 2.1(a) is also well i m a g e d b y t h e p h a s e - c o n t r a s t
system. O n t h e o t h e r h a n d , polarized-light-based
interference-contrast t e c h n i q u e s s h o u l d be used with
c a u t i o n as the birefringence of the spherulite also

Polymers:

Light

Microscopy

c o n t r i b u t e s t o the i m a g e c o n t r a s t . H e n c e , there ceases

to be a o n e - t o - o n e c o r r e s p o n d e n c e between t h e i m a g e
a n d the characteristics of t h e specimen.
2.3 Quantitative
Systems

Transmitted-Light

Interference

Q u a n t i t a t i v e interference systems o p e r a t i n g in a
transmitted-light m o d e allow t h e precise m e a s u r e
m e n t of a n O P L . T h e precision d e p e n d s o n t h e
t e c h n i q u e used b u t c a n be as high as 1/200 of a
wavelength (i.e., a b o u t 2.5 n m ) u n d e r ideal c o n
ditions. T h e result is t h a t it is possible t o identify
p h a s e s in c o m p o s i t e s o n t h e basis of their refractive
indices a n d t o m e a s u r e the thickness of thin p o l y m e r
layers t o c o n s i d e r a b l e a c c u r a c y . T h e t e c h n i q u e h a s
f o u n d a p p l i c a t i o n in a d h e s i o n a n d m i x i n g studies,
w e a r - r a t e investigations a n d thin-film c o a t i n g o r
deposition-rate measurements.
T h e u n d e r l y i n g principle of o p e r a t i o n is t h a t t w o
c o h e r e n t waves a r e p r o d u c e d from a c o m m o n s o u r c e .
O n e is passed t h r o u g h t h e specimen o r feature of
interest a n d t h e o t h e r t h r o u g h a " r e f e r e n c e " region.
T h e relative p h a s e s of t h e w a v e s a r e t h e n c o m p a r e d by
interferometry.

3. Reflected-Light

Methods

All reflected-light m e t h o d s suffer from t h e basic diffi

culty t h a t t h e reflectivity of p o l y m e r specimens is low
(roughly 4 % ) relative t o t h a t of m e t a l s . T o i m p r o v e
i m a g e - c o n t r a s t , it is therefore c o m m o n t o c o a t the
surface with a thin m e t a l layer by e v a p o r a t i o n o r
sputtering. T h i s m u s t b e sufficiently thick t o signific
antly i m p r o v e reflectivity b u t n o t so thick as t o
s u b m e r g e surface s t r u c t u r a l features. A 100 n m thick
layer will usually be sufficient. A p o l y m e r of high
refractive index, such as p o l y s t y r e n e (1.6), suffers less
from this p r o b l e m t h a n , for e x a m p l e , a n acrylic (1.5).
D e s p i t e t h e p r o b l e m s , c o n s i d e r a b l e a m o u n t s of
i n f o r m a t i o n c a n be gleaned from t h e reflected-light
image. T h e surface m a y be t h e n a t u r a l o n e of a
m a n u f a c t u r e d p r o d u c t , a fracture surface, o r a surface
specially p r e p a r e d t o reveal t h e i n t e r n a l m i c r o s t r u c
t u r e of t h e p o l y m e r .
T h e r a n g e of r e s o l u t i o n a n d magnification of t h e
s c a n n i n g electron m i c r o s c o p e ( S E M ) includes t h a t of
the reflected-light m i c r o s c o p e . T h e r e f o r e , t h e useful
ness of the light i n s t r u m e n t is q u e s t i o n a b l e a n d indeed
the S E M c u r r e n t l y d o m i n a t e s surface m i c r o s c o p y .
H o w e v e r , a p a r t from t h e p r o b l e m s of e l e c t r o n - b e a m
d a m a g e a n d the necessity of e x a m i n i n g t h e specimen
while it is in a high v a c u u m , t h e S E M m a y be a n
u n a c c e p t a b l y costly s o l u t i o n t o a m i c r o s c o p y p r o b
lem. F u r t h e r m o r e , t h e specialized m o d e s of reflectedlight o p e r a t i o n o u t l i n e d in Sect. 3.1 h a v e n o direct
equivalent in the S E M . W h e n these t e c h n i q u e s a r e
used, the results t e n d t o s u p p l e m e n t t h o s e from the
S E M , not duplicate them.

Figure 7
Epoxy-resin fracture surface, imaged using the
reflected-light differential interference-contrast microscopy
technique

3.1 Differential Interference-Contrast

Microscopy
T h e differential interference-contrast ( D I C ) t e c h n i q u e
is t h e reflected-light a n a l o g u e of the t r a n s m i t t e d - l i g h t
interference-contrast system m e n t i o n e d in Sect. 2.2.
In reflected-light m e t h o d s surface r o u g h n e s s a l o n e is
responsible for i m a g e c o n t r a s t . A g a i n , it is the g r a d i
e n t of t h e O P L which is revealed, b u t in this m o d e it is
n o w equivalent to surface slope. T h e sensitivity is very
high a n d i n t e r p r e t a b l e c o n t r a s t is really p r o d u c e d
only by relatively s m o o t h surfaces. R o u g h surfaces
a r e best e x a m i n e d in t h e S E M , b u t p r o v i d e d the
lateral r e s o l u t i o n is a d e q u a t e , t h e D I C system per
forms b e t t e r o n s m o o t h surfaces t h a n the S E M .
Differential interference-contrast m i c r o s c o p y h a s
c o n t r i b u t e d substantially t o the s t u d y of p o l y m e r film
surfaces, which a r e a l m o s t ideal specimens. T h e sur
face features visible o n , for e x a m p l e , p a c k a g i n g film,
h a v e a s t r o n g influence o n t h e formal optical p r o p e r
ties such as h a z e a n d clarity, as well as o n frictional
properties.
S m o o t h , brittle fracture surfaces h a v e also been
extensively e x a m i n e d using this t e c h n i q u e . A typical
epoxy-resin surface of this type is s h o w n in Fig. 7.
M o s t of t h e features s h o w n a r e invisible unless optical
c o n t r a s t e n h a n c e m e n t is e m p l o y e d . W i t h such i m a g e
c o n t r a s t , t h e l o c a t i o n of a fracture focus, o r t h e
d e t e c t i o n of c o n c e n t r i c features indicating a fatigue
type of failure, is c o n s i d e r a b l y simplified.
3.2 Quantitative Interference
Microscopy
Surface r o u g h n e s s c a n be quantified by using o n e of a
variety of l i g h t - m i c r o s c o p e techniques which, in
effect, p r o v i d e c o n t o u r m a p s of t h e surface. T h e
i n f o r m a t i o n o b t a i n e d h a s been of value in friction a n d
w e a r investigations.
T h e surfaces of m o l d i n g s c a n be e x a m i n e d a n d the
r o u g h n e s s c o m p a r e d with t h a t of t h e c o r r e s p o n d i n g
m o l d s . T h e results indicate the degree to which the

341

Polymers:

Light

Microscopy

Figure 8
Spherulitic surface of molded polypropylene, showing
surface contours. The reflected-light two-beam
microinterferometry technique was used

p o l y m e r h a s replicated t h e inevitable fine-scale r o u g h

ness of even t h e m o s t highly polished m o l d . T h i s in
t u r n c a n b e related b o t h t o processing variables,
particularly m o l d i n g pressures, a n d t o surface gloss.
F i g u r e 8 s h o w s a m o l d i n g surface i m a g e d with a
reflected-light interference system. T h e c o n t o u r s
clearly delineate spherulitic t e x t u r e o n t h e surface.
T h e height a n d lateral extent of t h e spherulites c a n
easily be d e d u c e d from t h e m i c r o g r a p h , t h e f o r m e r
because t h e d a r k c o n t o u r lines h a v e a half-wavelength
vertical interval. I n this case, t h e c o n c l u s i o n w o u l d b e
t h a t c o n t a c t b e t w e e n t h e p o l y m e r a n d t h e m o l d wall
was almost nonexistent.
E q u i p m e n t t o c a r r y o u t this t y p e of investigation
c o m e s in t w o basic forms. T h e simpler t o use a r e t h e
t w o - b e a m systems giving interference c o n t o u r s o r
" f r i n g e s " with a c o s 2 intensity profile. M u l t i p l e - b e a m
systems give a set of s h a r p e r c o n t o u r s a n d therefore
better vertical r e s o l u t i o n . T h i s is, h o w e v e r , o b t a i n e d
at the cost of ease of use a n d a m o r e restricted r a n g e
of a p p l i c a t i o n s . F o r m o s t practical p u r p o s e s , t h e t w o b e a m systems a r e a d e q u a t e w h e n w o r k i n g with
polymers.
3.3 Fluorescence
Microscopy
I n fluorescence m i c r o s c o p y , t h e specimen is i r r a d i a t e d
with light of o n e w a v e l e n g t h a n d a n i m a g e is f o r m e d
using a different, usually longer, w a v e l e n g t h e m i t t e d
by the specimen. Autofluorescence describes t h e situa
tion in w h i c h t h e p o l y m e r itself fluoresces. T h i s is
usually i n d u c e d b y i r r a d i a t i o n w i t h ultraviolet light.
A l t h o u g h this m i g h t in t h e o r y be d o n e in either t h e
t r a n s m i t t e d - l i g h t o r reflected-light c o n f i g u r a t i o n s of

342

Figure 9
Cross-section of the wall of a polyester bottle externally
coated with poly(vinylidene chloride), imaged using
ultraviolet fluorescence microscopy: a, nonfluorescing
background; b, strongly autofluorescing PVDC layer;
c, weakly fluorescing polyester layer

t h e m i c r o s c o p e , it is n o w m o r e c o m m o n t o use t h e
latter, a s m o d e r n e q u i p m e n t designs in this m o d e
offer very high i r r a d i a t i o n a n d light collection
efficiencies.
A u t o f l u o r e s c e n c e m i c r o s c o p y h a s been used t o o b
serve d e g r a d a t i o n a n d its d i s t r i b u t i o n in p o l y m e r s ,
p a r t i c u l a r l y p o l y v i n y l chloride) a n d polystyrene. T h e
t e c h n i q u e c a n also be used as a m e c h a n i s m for i m a g e
contrast production. Figure 9 shows an example.
H e r e a poly(vinylidene chloride) ( P V D C ) layer h a s
been a p p l i e d t o t h e o u t e r surface of a polyester b o t t l e .
In cross-section a n d b y autofluorescence, t h e P V D C
layer is clearly distinguished as a thin, b r i g h t b a n d .
T h e p h e n o m e n o n m a y also b e used t o label individual
c o m p o n e n t s in b l e n d i n g studies, b y slightly d e g r a d i n g
t h e c o m p o n e n t w h i c h s u b s e q u e n t l y needs t o b e identi
fied. T h e d e g r a d a t i o n c a n be sufficiently mild t o leave
m o s t o t h e r p r o p e r t i e s virtually unaffected.
F l u o r e s c e n c e m i c r o s c o p y is also used in t h e identifi
c a t i o n of additives in p o l y m e r systems, either b y
autofluorescence o r b y t h e i n c o r p o r a t i o n of suitable
fluorochromes.
See also: Optical Microscopy; Polymers: Electron Micros
copy

Polymers:

Molecular

Weight

Chapoy L L 1985 Recent Advances in Liquid Crystalline

Polymers. Elsevier Applied Science, London
Hartshorne 1974 The Microscopy of Liquid Crystals.
Microscope Publications, London
Haudin J 1986 Optical studies of polymer morphology.
In: Meeten G (ed.) 1986 Optical Properties of Polymers.
Elsevier Applied Science, London, pp. 167-264.
Hemsley D 1984 The Light Microscopy of Synthetic
Polymers. Oxford University Press, Oxford
Mason C W 1983 Handbook of Chemical Microscopy, 4th
edn. Wiley, New York
Sawyer L C, Grubb D 1987 Polymer
Microscopy.
Chapman and Hall, London
Slayter E M 1969 Optical Methods in Biology. Wiley, New
York
Wahlstrom 1979 Optical Crystallography, 5th edn.
Wiley, New York

()

is used t o c o m p u t e t h e averages of the distribution:

In defining , s u m s m a y be t r u n c a t e d at zero since

F(n) is zero for < 1 for a M W D . T h e m o m e n t s $ of
N(n) a n d $ of W(ri) a r e related, for e x a m p l e ,
l)
= / 4 f lf$, a n d with F(n) a M W D , t h e ns a r e often
either directly given by a physical m e a s u r e m e n t o r
m a y be c o r r e l a t e d with the p r o p e r t y d e t e r m i n e d . T h e
s t ne
a v e r a g e nx = = *
m e a n of t h e distribu
tion.
T h e averages ns a p p e a r so frequently in c o n n e c t i o n
with the M W D t h a t a special t e r m i n o l o g y h a s long
since developed:
(a)

D. A. Hemsley
[ L o u g h b o r o u g h University of T e c h n o l o g y ,
Loughborough, UK]

T h e n u m b e r a v e r a g e (the m e a n of N(n)) is given

by
= ^/^

()

= ^/^^

Polymers: Molecular Weight and its

Distribution
Synthetic p o l y m e r s a r e polydisperse t o v a r y i n g d e
grees in a variety of w a y s . T h e c h a i n s in a s a m p l e m a y
differ in, for e x a m p l e , m o l e c u l a r weight, degree of
long- o r s h o r t - c h a i n b r a n c h i n g , s t e r e o s t r u c t u r e o r
c o m p o s i t i o n (either grossly, as w i t h c o p o l y m e r s , o r
slightly, as with e n d g r o u p o r foreign moieties incor
p o r a t e d in t h e c h a i n d u r i n g p o l y m e r i z a t i o n ) . T h i s
article deals with t h e d i s t r i b u t i o n of m o l e c u l a r weight.

1. General
Distribution

Features

of a Molecular

Weight

T h e m o l e c u l a r weight d i s t r i b u t i o n ( M W D ) is c o n v e
niently characterized b y either t h e n u m b e r N(n) o r
weight W(n) of c h a i n s with r e p e a t i n g units (e.g., a
chain with m o l e c u l a r weight = nm0 with m0 t h e
m o l a r weight of a r e p e a t i n g u n i t ) . T h e n o r m a l i z e d
functions
N(n) =
W(n)=

()/()
()()

respectively, a r e t h e n u m b e r a n d weight fraction of

chains with r e p e a t i n g units (() = W(n) = 1;
here, a n d in t h e following, unless n o t e d otherwise,
s u m s a r e over t h e r a n g e 1 t o oo). B o t h N(n) a n d W(n)
obey the well-studied m a t h e m a t i c a l p r o p e r t i e s of
p r o b a b i l i t y functions ( C r a m e r 1946, Zelen a n d Severs
1964), a few of which find frequent a p p l i c a t i o n in their
use. F o r e x a m p l e , the 5th m o m e n t of a n o r m a l i z e d
distribution F(n) (e.g., either N(n) o r W(n)) defined b y

Distribution

Bibliography

and its

(b)

(c)

[- ()

T h e weight a v e r a g e (the m e a n of W(n)) is

^^^

nw=Mtyfrty

()()
Ln1V(n)

T h e a v e r a g e is
= ^/^

(d)

^/^

T h e + 1 a v e r a g e is
n
z

+1

(4)/ ( 3 ) =

(3)/

(2)

w w

H i g h e r averages (z + 2, . . . ) m a y be defined by
o b v i o u s generalization. It c a n be s h o w n t h a t
"* ^ nw< nz ^ ...
T w o of these a v e r a g e s j i a v e simple physical signific
ance: nn, the m e a n of N(n), is t h e total n u m b e r of
r e p e a t u n i t s () divided by t h e n u m b e r of m o l
ecules () a n d d e t e r m i n e s colligative p r o p e r t i e s
(e.g., o s m o t i c pressure a n d v a p o r pressure lowering);
nw, the m e a n of W(n), is t h e weighted s u m )
divided by t h e t o t a l c o n c e n t r a t i o n Zc(), with c(n) the
c o n c e n t r a t i o n (weight p e r unit v o l u m e ) of c h a i n s with
u n i t s , a n d is given by m e a s u r e m e n t s sensitive t o the
masses of t h e molecules present (e.g., light scattering
and sedimentation).
T h e b r e a d t h of a M W D is characterized by the
v a r i a n c e \ (the positive r o o t of o% is called the
s t a n d a r d d e v i a t i o n ) . W i t h a M W D , the dimensionless
reduced variance

called t h e polydispersity index is used m o r e frequently

t h a n \. T h u s ,

343

Polymers:

Molecular

Weight

Dz =

Distribution
2

DN =
Dw

and its

(nJnn)-\=MW/(MW) -\
{ n J n

) - \ = ^ l ^ )

- \

(nJnz)-\

where DN a n d Dw are related t o the b r e a d t h of the

N(n) a n d W(n) d i s t r i b u t i o n s , respectively, a n d Dz is a
useful generalization.
M a n y M W D s of interest a r e a s y m m e t r i c a b o u t
their m e a n , t h a t is, skewed t o w a r d high o r low n. T h e
coefficient of skewness yF which involves provides
a q u a n t i t a t i v e m e a s u r e of the a s y m m e t r y of a distri
b u t i o n . A s with \, a dimensionless skewness index is
convenient in discussions of a M W D :

S = * ( = <?/( - *( + 2

So t h a t
SN = {Dw
Sw = (Dz

+ \){DN

+ l ) - 3(DN
2

+ \){DW

+ l ) - 3(DW

+ 1) + 2
+ 1) + 2

F o r a symmetric d i s t r i b u t i o n , SF = 0. Positive a n d
negative SF indicate a d i s t r i b u t i o n skewed t o w a r d
large a n d small n, respectively.
Indices involving higher m o m e n t s c a n be utilized t o
characterize o t h e r p r o p e r t i e s of a d i s t r i b u t i o n a n d , in
principle, a distribution is k n o w n completely if all of
its m o m e n t s are k n o w n . In practice, the e x p e r i m e n t a
list never h a s such luxury of d a t a a n d rarely h a s
i n f o r m a t i o n for indices b e y o n d Dz o r Sw.
In m a n y applications, the average of a function
() of is needed:

= ()

()/

+]

()

where lis a n integer. O f course, a n equivalent relation

with nN(n) replaced by nnW{n) c a n also be used. A
frequent objective is to express in t e r m s of the
averages nfr nw,...
In s o m e a p p l i c a t i o n s , () obeys a
p o w e r law () = \ with integer o r n o n i n t e g e r v, so
+1)
t h a t = % . W i t h integer , involves only nn,
nw, . . . , b u t with n o n i n t e g e r the q u a n t i t y

{) = \%

= [;

\ ()]
+

()]

which a p p e a r s c a n n o t be reduced t o nn, nw,...,

unless
the M W D is k n o w n . Since a n early a p p l i c a t i o n t o
p o l y m e r s in which n(a) a p p e a r e d involved the intrinsic
viscosity, n{a) is s o m e t i m e s called the "viscosity aver
a g e . " E x a m p l e s of with integral a n d n o n i n t e g r a l
p o w e r laws a n d m o r e general expressions are given in
the following.
In s o m e cases, it is useful t o e m p l o y the integral o r
c u m u l a t i v e d i s t r i b u t i o n lF(n) defined by
h(n)=

m =

F{m)
0

( N o t e t h a t the s u m m a t i o n r a n g e is limited in this

case.) T h u s , Iw(n) is the weight fraction of p o l y m e r
with or fewer r e p e a t i n g units.
344

2. Examples
Functions

of Molecular

Weight

Distribution

In b r o a d t e r m s , three types of M W D functions are of

interest: (a) those calculated theoretically using a
m o d e l for the p o l y m e r i z a t i o n process; (b) those deter
m i n e d empirically, usually in n u m e r i c a l form, for a
p a r t i c u l a r s a m p l e by suitable e x p e r i m e n t (e.g., sizeexclusion o r elution c h r o m a t o g r a p h y , fractionation
or s e d i m e n t a t i o n ) ; a n d (c) analytic expressions,
believed t o be r e a s o n a b l e (but n o t necessarily precise)
r e p r e s e n t a t i o n s of the M W D a n d h a v i n g s o m e aspects
of m a t h e m a t i c a l convenience. T h e second type of
M W D is of limited value for theoretical p u r p o s e s ,
such as the c o m p u t a t i o n of in t e r m s of nn, nw, ...,
b u t even if the M W D is available only in n u m e r i c a l
form, it is useful b o t h for a qualitative insight i n t o the
n a t u r e of the M W D a n d t o p r o v i d e e x p e r i m e n t a l
m e a s u r e s of nn, nw,...
by n u m e r i c a l analysis. It is t h e n
s o m e t i m e s possible t o represent the t r u e M W D by
o n e of the empirical o r theoretical functions. T h e
theoretical functions m a y be used t o predict the
M W D , given the p o l y m e r i z a t i o n c o n d i t i o n s , or m a y
serve, t o g e t h e r with a n experimental estimate of the
M W D , to p e r m i t assessment of a p o l y m e r i z a t i o n
process.
Several M W D functions frequently e n c o u n t e r e d in
the study of p o l y m e r s are given in T a b l e 1, t o g e t h e r
with expressions for nn, nw, nz a n d n{a,. In each case,
only N(n) is presented, since nn W(n) = nN(n). T h e
averages nn, nw, . . . are given in preference to the
equivalent q u a n t i t i e s \ %\ . . . o r \ DN, SN,...,
as
a m a t t e r of convenience a n d familiarity to specialists
a
(but n {a) is, in fact, p =
E x a m p l e s of several M W D functions are given in
Fig. 1 for a r a n g e of DN as bilogarithmic plots of
W(n)/W(nn)
versus n/nn. A l t h o u g h this p r e s e n t a t i o n
distorts the s h a p e of W(n), it is useful for the
wide r a n g e of variables of interest. T h e curves in
Fig. 1 were all calculated with nn = 100, b u t they m a y
be used t o o b t a i n W(n) for o t h e r nn as well, except in
s o m e cases at very low nn (e.g., substantial deviation
o b t a i n s for the F l o r y - S c h u l z M W D with nn = 2).
2.1 One-Parameter
Functions
T h e t h e o r y of s t e p - g r o w t h ( c o n d e n s a t i o n ) p o l y m e r i
z a t i o n for flexible chain p o l y m e r s led t o the F l o r y Schulz d i s t r i b u t i o n . In the t h e o r y , enters as the
extent of reaction; it c a n also be considered as a n
a r b i t r a r y p a r a m e t e r , chosen t o force N(n) t o give the
l
correct nn (i.e., = 1 - n~ ) or, alternatively, the cor
rect polydispersity index, for e x a m p l e DN = p. T h e
1
skewness index SN is + . T h e relation
5

"-

=-^( dp

n l]

p ~)

is useful in the s u m m a t i o n s e n c o u n t e r e d since, for

integral s, a n y such s u m c a n eventually be reduced t o

Polymers:

terms involving "~ = (1 - p ) ~ multiplied by func

tions of p.
T h e e x p o n e n t i a l function is a n a p p r o x i m a t e form
for the F l o r y - S c h u l t z d i s t r i b u t i o n w h e n nn is large. It
is s o m e t i m e s m o r e c o n v e n i e n t analytically, for ex
a m p l e , in the calculation of n{a)9 a n d s t a n d s in relation
to t w o - a n d t h r e e - p a r a m e t e r e x p o n e n t i a l functions
discussed in t h e following sections. F o r this d i s t r i b u
tion, DN = 1, Dw = \ a n d SN = 2.
T h e P o i s s o n d i s t r i b u t i o n is realistic for certain
types of p o l y m e r i z a t i o n s , such as a n i o n i c p o l y m e r i z a
tions for which t h e t e r m i n a t i o n r a t e is nil a n d t h e
initiation is m u c h faster t h a n p r o p a g a t i o n . Since
DN&n~\
the d i s t r i b u t i o n is very n a r r o w for realistic
values of nn. T h e relation
5

Molecular

Weight

exp[ - (a

In u/u0) ]

l,2 v

Functions

F o r s o m e a d d i t i o n p o l y m e r i z a t i o n s , the S c h u l z - Z i m m
d i s t r i b u t i o n is a realistic r e p r e s e n t a t i o n of N(n). M o r e
frequently, it is used as a m a t h e m a t i c a l l y c o n v e n i e n t ,
a n d often r e a s o n a b l e , r e p r e s e n t a t i o n of N(n), w i t h o u t
a t t e m p t t o relate t h e p a r a m e t e r s to p o l y m e r i z a t i o n
variables. T h e S c h u l z - Z i m m d i s t r i b u t i o n is a general
ized form of t h e o n e - p a r a m e t e r e x p o n e n t i a l relation,
to which it reduces if the p a r a m e t e r h is unity. Since
Dz={h
+ 2)-\
. . . , the
DN = h~\ Dw={h+\y\
S c h u l z - Z i m m d i s t r i b u t i o n is s h a r p e r o r b r o a d e r t h a n
the o n e - p a r a m e t e r e x p o n e n t i a l d i s t r i b u t i o n as h is
greater o r smaller t h a n unity, respectively. T h e skew2
ness index of N(n) is positive (SN = 2/h ). In m a n y
cases (including calculation of nn, nw, nz, . . . , a n d n{a))
use is m a d e of the s t a n d a r d form (after c o n v e r s i o n of
s u m s to integrals)
/00

t/'

- 1

exp(-ku)du

du

= ocn u 0

is useful in s u m m a t i o n s with t h e P o i s s o n d i s t r i b u t i o n ,
since by c o n t i n u e d differentiation, a n y such s u m with
1
integral s c a n be r e d u c e d t o t e r m s involving " /
( 1)! = exp multiplied by functions of v.

r(t)/k

where T(t) is t h e g a m m a function. T h e c o n v e n i e n c e of

this relation is, in fact, o n e of t h e principal r e a s o n s
t h a t the S c h u l z - Z i m m function finds w i d e s p r e a d use.
T h e n o r m a l (or G a u s s i a n ) function represents the
M W D as s y m m e t r i c a b o u t the m e d i a n nm, with halfwidth . It is n o t often used t o represent the M W D ,
despite the c o n s i d e r a b l e b o d y of w o r k o n its p r o p e r
ties in s t a n d a r d p r o b a b i l i t y t h e o r y , p a r t l y because its
m a t h e m a t i c a l convenience is lost unless its b r e a d t h is
n a r r o w e n o u g h t h a t t h e effects of t r u n c a t i o n for < 0
d o n o t substantially affect s u m m a t i o n s of interest.
(This h a s been a s s u m e d t o be the case for t h e entries in
T a b l e 1.) In such cases, it is s o m e t i m e s used as a
m a t h e m a t i c a l l y c o n v e n i e n t empirical alternative to
the Poisson d i s t r i b u t i o n . It h a s been used t o represent
either N(n) o r W(n), as c o n v e n i e n t to the p r o b l e m a t

Distribution

h a n d . W i t h the former, o n e h a s DN = /^
and
SH = 0.
T h e l o g a r i t h m i c n o r m a l d i s t r i b u t i o n is a v a r i a t i o n
of t h e n o r m a l d i s t r i b u t i o n designed to eliminate the
troublesome truncation mentioned above, and can
represent a d i s t r i b u t i o n with a l o n g high-molecularweight tail. M o s t frequently, f^(ln n) is represented as
being n o r m a l l y d i s t r i b u t e d , with the result for N(n)
given
in
Table
1.
For
this
distribution,
2
DN = DW = DZ = e x p / ? - 1, so t h a t SN is positive for
DN > 0. In using the l o g a r i t h m i c n o r m a l d i s t r i b u t i o n ,
t h e s t a n d a r d form

- /(-\)\=-^[ - "- /(-\)\]

2.2 Two-Parameter

and its

exp(v a /4)

is frequently e n c o u n t e r e d .
2.3 Three-Parameter

Function

A l t h o u g h n o t often used in its m o s t general form, a

t h r e e - p a r a m e t e r e x p o n e n t i a l function h a s been
a d o p t e d for s o m e p u r p o s e s . I n s p e c t i o n of t h e entries
in T a b l e 1 reveals the p r o g r e s s i o n in t h e one-, t w o - ,
a n d t h r e e - p a r a m e t e r family of e x p o n e n t i a l functions.
A special f o r m of t h e t h r e e - p a r a m e t e r e x p o n e n t i a l
function h a s been used, with h = m - 1 (h > 0), which
h a s t h e m e r i t t h a t the integral weight d i s t r i b u t i o n for
t h e r e s u l t a n t t w o - p a r a m e t e r relation is especially
simple:
r

Iw(n)=\-exp(-yr ")
2.4 Other Distribution

Functions

All of t h e N(n) given in T a b l e 1 a r e u n i m o d a l , t h a t

is, h a v e only o n e m a x i m u m . In s o m e cases, espe
cially with m i x t u r e s , it is useful t o c o n s t r u c t M W D
functions by c o m b i n a t i o n of t w o o r m o r e u n i m o d a l
functions.
3. Use of the Molecular
Function

Weight

Distribution

A p p l i c a t i o n s of M W D functions t o i n t e r p r e t physical
p r o p e r t i e s a b o u n d ; only a few illustrative e x a m p l e s
will be given, with e m p h a s i s o n results useful in the
next section. T h e s e will involve calculations of a
physically meaningful a v e r a g e of a function ()
t h a t d e p e n d s o n a n d t h e c o n c e n t r a t i o n c(n) (weight/
vol) of -mers. In a polydisperse m i x t u r e , c = lLc(n) is
the t o t a l c o n c e n t r a t i o n a n d W{n) = c(n)/c.
In t h e following, it is a s s u m e d t h a t the p o l y m e r is
h e t e r o d i s p e r s e only in c h a i n length. O t h e r w i s e , m u l t i
v a r i a t e d i s t r i b u t i o n s m a y be needed t o represent the
m a t e r i a l (e.g., t h e b i v a r i a t e n u m b e r fractions N(n, )
for c o m p o n e n t s with r e p e a t i n g units a n d p r o p e r t y ,
which c o u l d be the n u m b e r of long c h a i n b r a n c h e s ,
etc.).

345

Polymers:

Molecular

Weight

and its

Distribution

Table 1
Some frequency used molecular weight distribution functions
Parameter

Name

N(nY

Flory-Schulz

(1-/>)/>"

Exponential

yexp(-yn)

Poisson

[v"-7("-l)!]exp(-v)

Schulz-Zimm (two-parameter
exponential)

Normal (Gaussian)

h h

yn~

l-p

1+

exp(-yn)/T(h)

, 2

h,y

[ 2 * / J r e x p [ - ( - n M) / 2 / J ]

Logarithmic normal

K//?V^)exp[-(ln /^/ }

Three-parameter exponential

my

hlmnh-

nm exp

nm9

(-Qxp
yn>)ir(hlm)

, v,

rp+i)/m]
llm
y r(h/m)

a Number fraction: the weight fraction may be calculated as W(n) = (n/nn)n(n)

b See text, for definition of n(a) c n(a) may be calculated analytically
for any integer a (see text) d Y(x) is the gamma function; for integer . () = (- 1)! e As discussed in text, the entries for nn, etc., are only for /
1

3.1 Osmotic

Pressure

F o r a dilute solution, the o s m o t i c pressure involves

s u m s over the c o m p o n e n t s :
c
U = RT\~

it is c o n v e n i e n t t o let B(m, n) = [B(m9 m)B(n,n)]

and
y
B(n,n) = bn~ ( w i t h O < < ). T h e f o r m e r results in
n
m
2
B = \LB
(, n) W(n)] , a n d use of t h e latter in a
relation involving n(a), with a = /2:

W(n)

+ (>

n/RTc

= (nnmoy

n)W(m)W(n)
n

+ B c+

...

...

w h e r e the t e r m p r o p o r t i o n a l to c h a s been r e d u c e d t o
1
a s t a n d a r d a ve ra ge _(i.e., n; ),
but the average
n
B = YLB(m, n)W(m)W(n)
of the second virial coeffi
cient B(m, n) c a n n o t be e v a l u a t e d w i t h o u t represen
n
t a t i o n for B(m, n). T o illustrate t h e calculation of B ,

346

bn;?*

= ( " > ( - y, 2 ) )

With
the
Schulz-Zimm
distribution,
=

2
[(\ +h/2)/(1 + )] . O t h e r m o r e
realistic
m o d e l s h a v e been studied t o represent m o r e c o m p l e x
n
b e h a v i o r of B
3.2 Light

Scattering

F o r a dilute p o l y m e r s o l u t i o n , t h e Rayleigh r a t i o R0 a t
zero scattering angle involves s u m s over the c o m
ponents:

Polymers:

Molecular

Weight

and its

Distribution

One-parameter functions
2

\+p
l-p

l+4p+p
(\-p)(l+p)

2
y

1 + 11/? -h l i p +
2
(l-p)(\+4p+p )

3
y

1 + 3v + v
1 +

4
y
2

1 + 7v + + v
+ 3v + v2

l a

y- m2

1 + 15v + 25v + 10v + v

2
3
1 + 7v + + v

+ a)] '

Two-parameter functions
(h+\)

(h + 2)

(ft+ 3)

>>

1.

1 + 3Qg/Aim)

, 2l

\+(/)
2

l + 6Qg//i m) + 3 Q g / WJ

\ + 3(fi/nm)

nm exp 3 /2

y- \T(h+\+a)IT(h

exp 5 /2

+ \)f

nm exp(* + 2)/? /2

mexp 7^ /2
Three-parameter function

T[(h + 2)m]
l,m

y T[(h

/?0 =

[(6 + 3)m]
llm

+ \)/m]

y T[{h

+ 2)/m]

j>

- 2 m ^ Z Z 5 ( m , n)mnW(m)W(n)
1
l s
= K m 0) - + 2 5
c - . . .

...]

where t h e t e r m p r o p o r t i o n a l t o c is expressed a s a
s t a n d a r d a v e r a g e (e.g., nw), b u t w h e r e e v a l u a t i o n of
B

LS

= ~ (9

n)mnW(m)W(n)

requires a m o d e l for B(m, ). If t h e expression i n t r o

d u c e d a b o v e is e m p l o y e d , t h e n
B

LS

x/2

= n- \ZB (n,

n)nW{n)]

r p + 3)/m]

LS

=
=

Rq = R q(n)

Kcm^nP(u)W{n)

requires a m o d e l for P(w). H o w e v e r , for a n y (isotro

pic) scatterer, P(u) = 1 - u/3 + . . . , a n d
1

[1+(^ /3); /?

LS

bn~^

{nJn{X_yl2)Y-

in which
c o n t a i n s n{a) with a = 1 y/2. U s e
of
the
Schulz-Zimm
distribution
gives

2
= ( + 1)*[(2 + h - /2)/(2 + )] , so t h a t for

2
0

( ) ^ ( ) + ...]
v

W i t h several m o l e c u l a r m o d e l s , R^(n) = r , so t h a t
2

L S

this m o d e l , B /B
= [(1 + - y/2)/(l + )] , which
LS
n
d e m o n s t r a t e s t h e general result t h a t 2? ^ 2?
F o r d a t a e x t r a p o l a t e d t o infinite dilution, t h e
d e p e n d e n c e o n scattering angle is given b y
2
R%(n) = Knm0c(n) P(u), w h e r e u = R^{n)q d e p e n d s o n
t h r o u g h t h e r o o t - m e a n - s q u a r e r a d i u s of g y r a t i o n
=
Rg'> Q (4/) sin 0/2 is t h e m o d u l u s of t h e scattering
vector. E v a l u a t i o n of

tfc/tf^Kmo)-

and
B

r[(h+\+a)lm]
rp+l)/m]

llm

1 / m

LS

u : [ W 0C I ^ ( / I )
2

^/i?

[(/ + 4)/w]

R G = n- lR G

(n)nW(n)

= rn\ +

2+

w i t h = (njnw(ni2
)
w h e r e = 1 a n d
+e)/n
involves n{a) with = 2 + . F o r integral ,
m a y be
347

Polymers:

Molecular

Weight

and its

Distribution
3.3 Intrinsic
Viscosity
T h e specific viscosity &() of a very dilute solution is
given by &() = [n]nc(n\ w h e r e t h e intrinsic viscosity
a
[] usually o b e y s a p o w e r - l a w relation [] = kn , so
t h a t n{a) with a = oc a p p e a r s :
C =

fo] = V

M ^ ( " )

K )

T h e d a t a in T a b l e 1 relate n,a) to the s t a n d a r d averages

for several d i s t r i b u t i o n functions. F o r in the
u s u a l r a n g e 0.5-0.8 for
flexible-chain
polymers,
nn < n(a) < nw. F o r rodlike c h a i n s , is a b o u t 1.8, a n d
4

"()

/
-

w ( z / " h - )

3.4 Size-Exclusion
Figure 1
Examples of W(n) for logarithmic exponential ( ) and
Gaussian (- - ) and Schulz-Zimm (
) distribution
functions for the indicated DN = njnn - 1. The latter with
DN = 1 also represents the exponential and Flory-Schulz
functions. All curves were calculated with nn = 100, but are
essentially unchanged with other nn, except in some cases
for very small nn

expressed in t e r m s of s t a n d a r d averages. F o r e x a m p l e ,
with flexible coil c h a i n s u n d e r F l o r y - t h e t a c o n d i t i o n s
LS
n
2
(B
= B = 0), = 1 a n d R G = rnz a n d for rodlike
2
W i t h flexible c h a i n s
c h a i n s , v = 2 a n d R G = rnzn2+l.
LS
u n d e r c o n d i t i o n s with B > 0, will usually be n o n integral, with 0 < ^ 0.2. In this case, a specific W(n)
is needed t o e v a l u a t e , for e x a m p l e , with t h e S c h u l z Z i m m d i s t r i b u t i o n , = ( 3 + h + e)/(h + 2 ) T ( 3 + h).
O v e r a wider r a n g e of q, for the flexible coil
LS
2
u n d e r c o n d i t i o n s with B = 0, P(u) = (2/u )
[w - 1 + exp - u],
and
for
a
rodlike
chain,
2
2
2
P(u) = x~ [xSi(2x) sin x], w h e r e u = x /3 a n d Si is
the sine integral. E a c h of these c o n t a i n t e r m s t h a t
require e v a l u a t i o n of a function t h a t is n o t a p o w e r law relation. T h u s , for the coil, m a k i n g use of the
2
relation R G(n) = rn,
z
?o Rq = Kcnwm0[2/q
rnw 2/q*r nnnw
A 2

+ (2lq r nJLn-

exp(-

rq n)W(n)]

T h i s expression is m o r e useful if t h e final t e r m c a n be

represented in t e r m s of s t a n d a r d averages. W i t h the
S c h u l z - Z i m m d i s t r i b u t i o n , use c a n be m a d e of the
2
s t a n d a r d integral given a b o v e (with k = rq + y a n d
t = h) to give
Kc/R

( 5)

= ([]

W{n)

t h a t a r e available if t h e c a l i b r a t i o n b e t w e e n [] a n d
Ve is k n o w n . T h u s , a n a p p a r e n t njnn r a t i o w o u l d be
calculated as
(nJnn)App

A^A^s- i)

w h e r e 3 = (oc ocA)/(\ + ocA). W i t h the p o w e r - l a w

a
relation
[] = kn ,
this
calculation
gives
{
l)
+s
A PA
= [ n ( 1 + < 5 y V ( 1 + s)]Y > so t h a t for the S c h u l z Zimm distribution

l 2

(2m0y q r

K/"JAPP

- ( , ) - [ - ( ^ )
+

T h u s , for h = 1, Kc/Rq = (nwmoy (\

+ q rnJ3). A simi
lar t r e a t m e n t c a n be given for rodlike c h a i n s , or
molecules of o t h e r shapes, a n d for t h e scattering from
a n i s o t r o p i c molecules.

348

Chromatography

In size-exclusion c h r o m a t o g r a p h y , the relative c o n

c e n t r a t i o n H(Ve) is d e t e r m i n e d as a function of elu
tion v o l u m e Ve (e.g., m a y be a differential refractive
index, p r o p o r t i o n a l t o c). F r e q u e n t l y , Ve c a n be
r e p r e s e n t e d as a universal function of [] for a given
c o l u m n , i n d e p e n d e n t of the p o l y m e r . O f c o u r s e , if the
relation b e t w e e n [] a n d is k n o w n , then (after
c o r r e c t i o n for u n w a n t e d axial diffusional b r o a d e n i n g ,
see below) t h e c h r o m a t o g r a m c a n be used to c o m p u t e
W(n\
since W(n) = H( 6)/7/( K e), w h e r e the s u m
e x t e n d s over all Vc, each of which c o r r e s p o n d s to a n n
to be c o m p u t e d from []. W i t h a s a m p l e for which
t h e relation b e t w e e n [] a n d is u n k n o w n , r e a s o n
able estimates of DN, Dw a n d Dz m a y still be o b t a i n e d
by a r b i t r a r y a p p r o x i m a t i o n of t h e p o w e r - l a w e x p o
n e n t = d In []/ In by a n e s t i m a t e ocA a n d calcula
+ )
f rm
tion of ([]) *
o
the observed []. It is
often f o u n d t h a t estimates of DN, etc., d o n o t d e p e n d
strongly o n t h e e s t i m a t e for ocA ( F r e q u e n t l y , ocA is
e q u a t e d with a c , t h e value of for the p o l y m e r used t o
calibrate the c o l u m n , as is the case if o n e uses a
c o r r e l a t i o n for vs Ve for a s t a n d a r d p o l y m e r t o
analyze d a t a o n a n u n k n o w n m a t e r i a l . ) T h e n a t u r e of
this d e p e n d e n c e c a n be illustrated by calculation of
the e x p e r i m e n t a l q u a n t i t i e s

= (nJnn)T(h

+ 2 + S)T(h - ) / ( +

2)Y(h)

C o n s e q u e n t l y , (nJnn)App is close t o njnn with a r e a s o n

able estimate for ocA, for e x a m p l e , in e r r o r by 1 7 % for
h = 1 a n d = 0.1 (which represents a large d e v i a t i o n
of ocA from a ) .
In s o m e cases, in o r d e r t o o b t a i n s o m e estimate of
nn, etc., for a p o l y m e r with u n k n o w n p o w e r - l a w

Polymers:

p a r a m e t e r s ; t h e coefficient k is also a p p r o x i m a t e d
by a n estimate kA t o p e r m i t c a l c u l a t i o n o f t h e experi
m e n t a l q u a n t i t i e s B$ = (k^^+^Af*
and apparent
]
l)
averages (ns)A = B^ /B^~
(e.g., this o b t a i n s if t h e
c o r r e l a t i o n of Af vs Ve for a s t a n d a r d p o l y m e r is used
t o analyze t h e d a t a for the u n k n o w n p o l y m e r , so t h a t
kA a n d ola a r e p u t e q u a l t o t h e c o r r e s p o n d i n g p a r a
m e t e r s kc a n d a c for t h e s t a n d a r d ) . I n this case, with
the S c h u l z - Z i m m d i s t r i b u t i o n ,
+

to),
s'App

*A /nn
~h

h + s(\ +)
h+s

T[h + s{\ + )]
T[h-d

s(\+S)]

A s a n e x a m p l e , if d a t a o n b e n z e n e s o l u t i o n s o f poly
vinyl acetate) were a n a l y z e d with t h e Vt relation
for polystyrene (in benzene), t h e n for a p o l y m e r with
A = l , ( f l J A eP = 1.54(HW)~-X, illustrating t h e e r r o r
that can be introduced.
3.5 Photon Correlation Light
Scattering
Time-resolved light scattering using p h o t o n cor
relation m e t h o d s give t h e intensity a u t o c o r r e l a t i o n
(2)
functions # ( , ) o f t h e c o u n t r a t e in s a m p l i n g
intervals of d u r a t i o n . F o r a p p r o p r i a t e experi
m e n t a l c o n d i t i o n s (including e x t r a p o l a t i o n t o infinite
dilution):
[g

( 2 )

( r , ) - 1 ]

1 /2

= ^ ( H ) e x p ( -

/^))

with DT(n) t h e
where ~\) is given b y q DT(n),
t r a n s l a t i o n a l diffusion coefficient a n d Qq(n) is t h e
fraction of t h e scattering d u e t o the c o m p o n e n t with
c o h e r e n c e time rq{n). F o r i n d e p e n d e n t scatterers (i.e.,
infinite dilution), Q(n) = Rq(n)/Rq. T h u s , analysis o f
2
1 /2
[g 1 ] requires t h e extensive u s e o f m o d e l s (e.g.,
random-flight, rodlike) t o p e r m i t e v a l u a t i o n o f t h e
d e p e n d e n c e of Qq(n) a n d Jin) o n in d a t a i n t e r p r e
t a t i o n . F o r e x a m p l e , t h e first c u m u l a n t Kl e q u a l
(2)
to - (i)d 1[# () - \]/d In a s goes t o zero c a n b e
evaluated t o give
2

kTq

4nns(rnn) ^

- ( 1

^ / 3 ^}
"'

/?

21

( + 2)

if P(u) is a p p r o x i m a t e d b y t h e G u i n i e r relation
exp( w/3), a n d t h e expression DT(n) =
kT/4^sRG(n)
for t h e random-flight c h a i n is used, with Ro(n) rn.
T h e result reveals t h e effects o f i n t r a m o l e c u l a r inter
2
ference (e.g., t h e factor (1 + q rnn/3h), w h i c h is a p
2
p r o x i m a t e l y unity for q <^ rnn/3) a n d t h e c o m p l e x
d e p e n d e n c e o n polydispersity, even for t h e m o s t
(2)
primitive features of ( ) .
4. Determination
Distribution

of the Molecular

Weight

M e t h o d s of c h a r a c t e r i s i n g a M W D m a y involve
physical s e p a r a t i o n of c o m p o n e n t s , with s u b s e q u e n t

Molecular

Weight

and its

Distribution

analysis o f nn, nw, ... a n d t h e t o t a l c o n c e n t r a t i o n for

each a l i q u o t , o r m e a s u r e m e n t o f physical p r o p e r t i e s
(e.g., o s m o t i c pressure a n d light scattering) t h a t
d e p e n d o n g r a d i e n t s o f c(n) i n d u c e d b y B r o w n i a n
m o t i o n o r external fields t o give either W(n) or, m o r e
usually, , nw, ... for t h e entire s a m p l e .
Several e x a m p l e s o f t h e latter h a v e been cited in the
preceding: o s m o t i c p r e s s u r e a n d light scattering yield
Mn = nnm0 a n d Mw = njnQ9 respectively, a n d for a
r a n d o m - f l i g h t coil, RG = rnz p r o v i d e s a m e a n s t o
e s t i m a t e nz if r is k n o w n . I n principle, t h e s h a p e o f the
scattering function Kc/Rq a t infinite dilution c a n b e
used t o d e t e r m i n e nn a n d nw a n d n2 if it is k n o w n t h a t
the p o l y m e r is linear a n d o b e y s random-flight stat
istics (see Sect. 3.2)in practice, t h e r a n g e o f q
available (limited, since < ) is usually t o o small t o
p e r m i t necessary e v a l u a t i o n o f Kc/Rq, a n d in a n y case,
t h e d e p a r t u r e from r a n d o m - f l i g h t statistics m a y b e
severe for RGq > 1. A n o t h e r t r e a t m e n t o f this k i n d
involves t h e intensity a u t o c o r r e l a t i o n
function
(2)
(2)
# ( , ) . U n f o r t u n a t e l y , analysis o f ( , ) in
t e r m s o f W(n) is c o m p l e x , even with t h e infinite
dilution a p p r o x i m a t i o n , requires extensive u s e o f
m o d e l s (e.g., r a n d o m - f l i g h t a n d rodlike), a n d is n o t
well suited for a c c u r a t e e v a l u a t i o n o f W(n).
M e a s u r e m e n t s t h a t e m p l o y a n external field t o
c r e a t e c o n c e n t r a t i o n g r a d i e n t s t h a t a r e studied in situ
include e q u i l i b r i u m a n d velocity s e d i m e n t a t i o n ,
t h e r m a l diffusion a n d a few o t h e r m o r e specialized
techniques. In sedimentation equilibrium, under a p
p r o p r i a t e c o n d i t i o n s for a solute with m o l e c u l a r
weight = nm0, t h e c o n c e n t r a t i o n a t a p o s i t i o n r
a l o n g a centrifugal field with a n g u l a r velocity for a
s o l u t i o n confined b e t w e e n p o s i t i o n s b a n d m is
{r

c \n)

= c0AM

e x p ( - ABM)/[\

- e x p ( - BM)]
2

with c0 t h e initial c o n c e n t r a t i o n , A = (r m )/
2
2
2
2
(b - m ) a n d = (dpldc)w\b
- m )/RT w h e r e is
t h e s o l u t i o n density. F o r a h e t e r o d i s p e r s e solute
t h e a v e r a g e ( m e a s u r a b l e ) c o n c e n t r a t i o n a t r is
(r)
{r)
( ) s o t h a t analysis o f c a s a function of r
c(r) = c
p r o v i d e s a m e a n s t o s t u d y N(n), either by inversion o f
( r)
{r)
c t o o b t a i n N(n) o r by analysis o f c t o d e d u c e nw, nz,
(r)
etc. I n practice, d e v i a t i o n s from t h e idealized c (n)
given a b o v e c a u s e d b y s o l u t i o n compressibility (es
pecially with o r g a n i c solvents) a n d h y d r o d y n a m i c a n d
t h e r m o d y n a m i c i n t e r a c t i o n s a m o n g t h e solute m o l
ecule m a k e s the analysis less a t t r a c t i v e . M o r e o v e r , the
m e t h o d is inherently time c o n s u m i n g . C o n s e q u e n t l y ,
it is used m u c h less frequently t h a n size-exclusion
c h r o m a t o g r a p h y (see later).
S e d i m e n t a t i o n velocity affords a n alternative cen
trifugal coefficient s(n)9 e q u a l t o
M(dp/dc)DT(n)/RT
for a s o l u t i o n a t infinite dilution. T h e s p r e a d i n g o f the
b o u n d a r y b e t w e e n s o l u t i o n a n d solvent a s the b o u n d
a r y m o v e s down_the cell (for positive dp/dc) c o n t a i n s
i n f o r m a t i o n o n N(n). I n practice, c o n v e r s i o n o f t h e
(r)
e x p e r i m e n t a l d a t a dc /dr t o N(n) is h a m p e r e d b y t h e

349

Polymers:

Molecular

Weight

and its

Distribution

factors m e n t i o n e d a b o v e in c o n n e c t i o n with sedimen

t a t i o n equilibrium, a n d the p r o c e d u r e is seldom used
for q u a n t i t a t i v e estimate of N(n) o w i n g t o the m o r e
easily used size-exclusion c h r o m a t o g r a p h y .
M e t h o d s involving physical s e p a r a t i o n of c o m
p o n e n t s for s u b s e q u e n t analysis m a y be discrete o r
c o n t i n u o u s (as with c h r o m a t o g r a p h y ) . O f the discrete
m e t h o d s , s e p a r a t i o n of the c o m p o n e n t s of a p o l y m e r
in a dilute solution by successive a d j u s t m e n t s of the
t h e r m o d y n a m i c c o n d i t i o n s , with r e m o v a l a n d a n a
lyses at each step is frequently used. T h e t h e r m o
d y n a m i c c o n d i t i o n s m a y be altered by a d d i t i o n o r
r e m o v a l (e.g., by e v a p o r a t i o n ) of a reagent o r by
c h a n g e in the t e m p e r a t u r e .
T h e c h a n g e m a y cause successive p h a s e s e p a r a t i o n
from solution of c o m p o n e n t s with successively
smaller (fractional precipitation) o r dissolution of
c o m p o n e n t s with successively higher (fractional
solution). In either case, the recovered c o m p o n e n t c a n
be characterized by its weight fraction W a n d p r o p e r
ties, for e x a m p l e , nn, nw ... E l a b o r a t e m e t h o d s h a v e
been developed t o r e c o n s t r u c t N(n) from such d a t a , t o
t a k e a c c o u n t of the inevitable o v e r l a p of c o m p o n e n t s
in each fraction. F o r e x a m p l e , in o n e scheme, the
cumulative weight fraction Iw(n) is a p p r o x i m a t e d by
the experimental c u m u l a t i v e weight Mw = nwmQ:

* /,(* J = (iWi(nw)

+ "
j=

Wj(nw)

S(VC)=

S^ \Ve)g(Ve-u)

u=V\

w h e r e g(Ve u) is a s p r e a d i n g function a n d the s u m

r u n s over t h e entire elution v o l u m e r a n g e Vl to V2.
F r e q u e n t l y , a G a u s s i a n function with m e a n Ve a n d
l
v a r i a n c e (2H)~
is used for g(Vt-u),
so t h a t in
principle the F o u r i e r t r a n s f o r m
/
ic)

S (Ve)

00

1 2/

= (In)'

J-

exp(s /4//).S(.y)exp(- isVe)

ds

00
c)

c a n be used t o c o m p u t e S< (K e) from S(VC) if the

s p r e a d i n g p a r a m e t e r is k n o w n . R i g o r o u s evalu
c)
a t i o n of tf (Fe) from e x p e r i m e n t a l S(Ve) is seldom
easy, b u t a n a p p r o x i m a t i o n leads t o the useful result
(see T u n g 1977)
(c)

S (Ve)

x 2

[HI(H-bx)] l S(V^xV[b\lA(H-bx)]
i

w h e r e 2bi = - d In Sffl/dx ]^
.Ve G i v e n (which m a y
C)
v a r y with F e ) , & (VJ m a y be e s t i m a t e d for each S(Ve).
See also: Liquid Chromatography Mass Spectrometry;
Organic Mass Spectrometry

Differentiation of Iw(n) t h e n gives W(n) = dlw(n)/dn;

m o r e e l a b o r a t e schemes h a v e been used.
In m a n y cases, c h r o m a t o g r a p h i c m e t h o d s h a v e
s u p p l a n t e d discrete fractionations. C h r o m a t o g r a p h i c
m e t h o d s b a s e d o n solubility, m o l e c u l a r size, a d s o r p
tion, t h e r m a l diffusion, s e d i m e n t a t i o n a n d o t h e r
properties h a v e been developed. Space p r o h i b i t s dis
cussion of a n y b u t the presently m u c h used sizeexclusion c h r o m a t o g r a p h y ( S E C ) , which finds use in
b o t h p r e p a r a t i v e a n d analytical a p p l i c a t i o n s . N o n e
theless, o t h e r c h r o m a t o g r a p h i c m e t h o d s are fre
quently used, such as c o l u m n elution fractionation.
In s o m e cases, d u a l detectors are used with S E C t o
d e t e r m i n e the relative c o n c e n t r a t i o n (e.g., from the
difference in refractive indices b e t w e e n eluent a n d
solvent) a n d , say, the light scattering intensity Rq at
small scattering angle ( a n d low c o n c e n t r a t i o n ) as
functions of the elution v o l u m e Ve. In this case, after
correction for axial diffusion (see below), W(n) m a y
be d e t e r m i n e d directly. If only relative c o n c e n t r a t i o n s
are used, the correlation between [] a n d Ve will
p e r m i t c o n s t r u c t i o n of W(n) from the c h r o m a t o g r a m
e
( -g-> relative c o n c e n t r a t i o n as a function of Vc9
if the relation between [] a n d is k n o w n ) or, if n o t ,
the d a t a m a y b e used t o estimate DN, etc., a n d
a p p a r e n t averages (ns)App of the d i s t r i b u t i o n as dis
cussed a b o v e . D i r e c t m e a s u r e m e n t of R is especially
useful with b r a n c h e d p o l y m e r s , for which the relation
between [] a n d is c o m p l e x .
350

Axial diffusion o n the c o l u m n c a n b r o a d e n the

observed c h r o m a t o g r a m . In this case, the observed
c h r o m a t o g r a m S(Ve) is related t o the c h r o m a t o g r a m
c)
& (Ve) c o r r e c t e d for axial diffusion by
y2

Bibliography
Cramer 1946 Mathematical Methods of Statistics. Prince
ton University Press, Princeton, NJ, Chaps. 15-20, pp.
166-255
Fujita 1975 Foundations of Ultracentrifugal Analysis.
Wiley, New York
Giddings J C 1979 Field-flow fractionation of polymers:
one-phase chromatography. Pure Appl. Chem. 51: 145971
Guzman G 1961 Fractionation of high polymers.
In: Robb J C, Peaker F W (eds.) 1961 Progress in
High Polymers, Vol. 1. Academic Press, New York, pp.
113-93
Peebles L Jr 1971 Molecular Weight Distribution in
Polymers. Interscience, New York
Slade Jr (ed.) 1975 Polymer Molecular Weights. Dekker,
New York
Tung L (ed.) 1977 Fractionation of Synthetic Polymers,
Dekker, New York
Zelen M, Severs C 1964 Probability functions. In: Abramovitz M, Stegun I A (eds.) 1964 Handbook of Mathema
tical Functions, Applied Mathematical Series No. 55.
National Bureau of Standards, Washington, DC, Chap.
26, pp. 925-95

G . C. Berry
[Carnegie M e l l o n University, P i t t s b u r g h ,
Pennsylvania, U S A ]

Polymers:

Polymers: Neutron Scattering

Interest in n e u t r o n s c a t t e r i n g b y p o l y m e r s b e g a n in
t h e early 1950s w h e n paraffin b l o c k s w e r e u s e d t o slow
d o w n fast n e u t r o n s in c h a i n r e a c t i o n s . T h e s e m a t e r
ials w e r e selected for their large p r o t o n fraction,
p r o t o n s b e i n g useful h e r e b e c a u s e of their l o w m a s s
a n d large n e u t r o n cross section. I n t h e early 1960s
thermal-neutron scattering experiments were per
f o r m e d t o s t u d y t h e low-frequency m o t i o n s of
p o l y e t h y l e n e . T h e inelastic i n c o h e r e n t n e u t r o n cross
2
in t h e o n e - p h o n o n a p p r o x i m a
section, d a{Jdiidw
tion, is directly related t o t h e d e n s i t y of v i b r a t i o n a l
states # ( ) . H e r e a g a i n , t h e large value of t h e i n c o h e r
e n t n e u t r o n cross section of t h e p r o t o n is useful. B u t
t h e fact t h a t t h e p r o t o n s a r e b o u n d t o a m a c r o m o l e c u lar s t r u c t u r e is also of i m p o r t a n c e , b e i n g reflected in
t h e function g(co). I n 1967 t h e first d e u t e r a t e d p o l y
ethylene s a m p l e w a s investigated b y inelastic n e u t r o n
scattering ( F e l d k a m p et al. 1968). T h e m a j o r c o n t r i
b u t i o n t o t h e o b s e r v e d signal is t h e inelastic c o h e r e n t
2
f r o m w h i c h p h o n o n dis
cross section, d acoJdQda>,
p e r s i o n curves a r e d e t e r m i n e d .
I m p r o v e d k n o w l e d g e of t h e force field in p o l y m e r
crystals c a n b e o b t a i n e d b y this m e t h o d .
T h e first small-angle n e u t r o n s c a t t e r i n g experi
m e n t s o n p o l y m e r s w e r e m a d e in Saclay, F r a n c e
( C o t t o n et al. 1972), a n d s u b s e q u e n t l y a t t h e I n s t i t u t
L a u e L a n g e v i n ( I L L ) , G r e n o b l e ( K i r s t e et al. 1973).
T h e s e e x p e r i m e n t s w e r e m a d e possible b y t h e u s e of
cold n e u t r o n sources. T h e fact t h a t p o l y m e r m o l e c u l e s
a r e of large a n d v a r i a b l e size m a k e s t h e m ideal t a r g e t s
for small-angle s c a t t e r i n g a s t h e y c a n b e identified b y
t h e i n c o m i n g r a d i a t i o n . T h e p o l y m e r coil f o r m factor
P(q) a n d t h e p a i r c o r r e l a t i o n function S(q) a r e derived
from t h e elastic c o h e r e n t cross section:
dacoh/dQ

= b Kc[MP(q)

+ cS(q)]

w h e r e c is t h e p o l y m e r c o n c e n t r a t i o n , is its m o l e c u
lar weight, A' is a c o n v e r s i o n factor a n d b is t h e
c o n t r a s t length ( t h e difference b e t w e e n solvent a n d
solute scattering l e n g t h ) . T h i s l e n g t h c a n b e e n h a n c e d
by isotopic s u b s t i t u t i o n of t h e p r o t o n s ( d e u t e r a t i o n )
w i t h o u t m a j o r p e r t u r b a t i o n of t h e system. Selective
labelling (i.e., s u b s t i t u t i o n ) is also achieved b y
this m e t h o d . Small-angle n e u t r o n scattering m a d e
possible t h e e x p e r i m e n t a l investigation of m a n y situa
tions w h i c h w e r e p r e v i o u s l y o n l y discussed t h e o r e t i c
ally; a recent review of this subject is given b y Stein
a n d H a n (1985).

/.

Phonons

T h e density of v i b r a t i o n a l states g(d) reflects m a n y

p r o p e r t i e s of t h e m a t e r i a l . F o r a c o u s t i c v i b r a t i o n s ,
d l
g((o)ccco ~ , w h e r e d is t h e c h a r a c t e r i s t i c d i m e n s i o n o f
the v i b r a t i n g system. A s a result, a t l o w t e m p e r a t u r e
t h e h e a t c a p a c i t y C v o b e y s t h e D e b y e limiting l a w ,

Neutron

Scattering

CyozT .
V a l u e s of d less t h a n 3 were derived from
o b s e r v a t i o n s in r u b b e r s a n d p o l y e t h y l e n e . It w a s of
interest t o test t h e density of states directly b y inelastic
i n c o h e r e n t n e u t r o n scattering. T h e e x p e r i m e n t s w e r e
i n t e r p r e t e d , h o w e v e r , for large values of a n d t h e
q u e s t i o n of t h e c h a r a c t e r i s t i c d i m e n s i o n w a s left
u n a n s w e r e d . It h a s b e e n revived lately b y t h e sugges
t i o n t h a t t h e index d c o u l d reflect t h e fractal d i m e n
sion of p o l y m e r coils ( S t a p e l t o n et al. 1980). V a n
H o v e singularities were identified for v a r i o u s m o t i o n s
of t h e c h a i n : a n t i p a r a l l e l t r a n s l a t i o n s in t h e c a n d b
axial d i r e c t i o n s , a n d r o t a t i o n s a g a i n s t e a c h o t h e r
( T w i s l e t o n a n d W h i t e 1972). Crystalline stiffness c o n
s t a n t s w e r e d e t e r m i n e d from t h e d i s p e r s i o n curves.
T h e s e c o u l d b e m e a s u r e d for t h e first t i m e within t h e
Brillouin z o n e ; d a t a h a v e suggested t h e presence of a
soft m o d e ( F e l d k a m p et al. 1968).

2. Small-Angle

Scattering:

Amorphous

Polymers

T h i s section is c o n c e r n e d w i t h t h e g e o m e t r y of flexible
coils. F u n d a m e n t a l q u e s t i o n s a r e raised a b o u t t h e
a s y m p t o t i c s t a t e of such l o n g m o l e c u l e s .
Before small-angle n e u t r o n scattering b e c a m e
available, t h e r e w a s n o physical m e t h o d t o d e t e r m i n e
t h e size of a flexible p o l y m e r coil in t h e melt. T h e first
e x p e r i m e n t t o b e c a r r i e d o u t u s i n g small-angle n e u
t r o n s c a t t e r i n g consisted of m e a s u r i n g t h e a v e r a g e
as
a
s q u a r e r a d i u s of g y r a t i o n </?g>
function of t h e
m o l e c u l a r weight M w . Different g r o u p s of c o w o r k e r s
o b t a i n e d similar results for p o l y s t y r e n e , p o l y m e t h a crylate a n d p o l y e t h y l e n e , respectively. T h e o b s e r v e d
v a r i a t i o n of </g> w i t h M w indicates a r e l a t i o n s h i p
< / ? G > c c M w , typical o f a r a n d o m w a l k . T h e result h a d
b e e n p r e d i c t e d b y F l o r y , o n t h e basis of t h e r m o
d y n a m i c s ( t h e e n t r o p y p e r u n i t v o l u m e decreases as
t h e size of molecules increases). A n interesting struc
t u r a l p r o p e r t y of m e l t s w a s p o i n t e d o u t b y d e G e n n e s .
It is o b s e r v e d in t h e n e u t r o n s c a t t e r i n g p a t t e r n of a
m e l t m a d e of identically labelled coils t h a t t h e m a x i
m u m s c a t t e r e d intensity is smaller t h a n t h e c o r r e s
p o n d i n g theoretical intensity d u e t o t h e s a m e set of
n o n i n t e r a c t i n g c h a i n s . T h i s c o r r e l a t i o n hole is evid
ence of a n a m o r p h o u s p o l y m e r m e l t s t a t e , as o p p o s e d
to an ordered structure.
T h e m a n n e r in w h i c h flexible coils o c c u p y space in
a given e n v i r o n m e n t ( R a u m e r f u l l u n g ) is a p r o b l e m of
m a j o r interest w h i c h c a n b e s t u d i e d b y n e u t r o n scat
tering. T o a first a p p r o x i m a t i o n t h e following selfsimilar r e l a t i o n h o l d s t r u e for t h e a v e r a g e s q u a r e d
d i s t a n c e b e t w e e n a n y t w o m o n o m e r s /, j of a single
coil in a g o o d solvent:
<

= |/-;|

(/,;=1,...,>

w h e r e A is a c o n s t a n t a n d is t h e excluded v o l u m e
index. W e n o w d e p a r t f r o m t h e swollen state b y
l o w e r i n g t h e t e m p e r a t u r e T, b y increasing t h e c o n c e n
t r a t i o n c o r b y increasing t h e (linear) size of t h e

351

Polymers:

Neutron

Scattering

solvent molecules. T h r e e f u n d a m e n t a l scattering ex

p e r i m e n t s tested the following deswelling relations
( D a o u d et al. 1975, Kirste a n d L e h n e n 1976):
2/5

T
< * G > *

1/4

>- 2/5

light scattering,
n e u t r o n scattering,
n e u t r o n scattering,

c->0
Ty/N>\
c->0

It w a s observed t h a t b o t h the swollen a n d the u n s w o l len state coexist o n the s a m e coil. Such structures a r e
characterized by so-called " b l o b s " (de G e n n e s ) ; these
are the sequences of m o n o m e r s s e p a r a t i n g swollen
a n d unswollen states. Different types of b l o b s a r e
found d e p e n d i n g o n the p a r a m e t e r , the best k n o w n
being the " t h e r m a l " b l o b . T h e n e u t r o n scattering
e x p e r i m e n t is able t o detect " c o n c e n t r a t i o n " b l o b s .
M o r e detailed i n f o r m a t i o n o n the flexible coil c o n
figuration is o b t a i n e d from n e u t r o n scattering experi
m e n t s by studies o n partially labelled coils. W e are
n o w c o n c e r n e d with the uniformity of the coil
e x p a n s i o n a l o n g itself, in a g o o d solvent, at zero
c o n c e n t r a t i o n . It is generally agreed t h a t , b e y o n d a
first a p p r o x i m a t i o n , this e x p a n s i o n is n o t u n i f o r m
(the coefficient A d e p e n d s in fact o n /, j). T h e o r y
asserts t h a t a coil p o r t i o n is m o s t strongly pulled b y
excluded v o l u m e forces w h e n located in the m i d d l e of
the coil, in between t w o b r a n c h e s (des Cloizeaux
1980). F r o m t h e results of n e u t r o n scattering experi
m e n t s ( L o d g e et al. 1983), the issue w a s m a d e clear.
T h e size of a labelled coil p o r t i o n was m e a s u r e d
successively in the central p a r t of a large coil, at the
p e r i p h e r y a n d w h e n isolated. T h e values f o u n d were
59 A, 56 A a n d 50 A, respectively. A n o t h e r p r o m i s i n g
n e u t r o n scattering e x p e r i m e n t using partially labelled
m a t e r i a l is t h a t of R a w i s o a n d c o w o r k e r s of the C R M
(Centre de R e c h e r c h e s des M a c r o m o l e c u l e s ) , S t r a s
b o u r g . T h r e e different polystyrene s a m p l e s h a v e been
p r e p a r e d , the p r o t o n s being replaced by d e u t e r i u m ,
respectively o n the entire coil, o n the b a c k b o n e a n d
o n the p h e n y l side g r o u p s only. T h e t r u e a s y m p t o t i c
form factor of the coil b a c k b o n e c a n n o w be deter
m i n e d experimentally a n d c o m p a r e d with m o d e l cal
culations. A s a result, a new precise e v a l u a t i o n of the
persistence length (due to the local chemical structure)
c a n be o b t a i n e d .

3. Small-Angle
Scattering:
Poly
electrolytes

Copolymers,

Networks,

C o p o l y m e r s form c o m p o s i t e m a t e r i a l s with versatile

p r o p e r t i e s . A s t u d y of these molecules in dilute solu
tions by small-angle scattering b e g a n a r o u n d 1974
( D u v a l et al. 1976). T h e a p p a r e n t s q u a r e d r a d i u s of
2
g y r a t i o n , (R GA},
of p o l y s t y r e n e - p o l y i s o b u t y l e n e m o l
ecules w a s m e a s u r e d as a function of y, the r a t i o of
d e u t e r a t e d t o t o t a l a m o u n t of solvent. A p a r a b o l i c
d e p e n d e n c e {RCA}(y)
w a s found, characteristic of
molecules lacking central s y m m e t r y . H o w e v e r , only
the wings of the p a r a b o l a c o u l d be d e t e r m i n e d . C o r r e

352

lations of interest were derived from the central

p a r a b o l i c region. Limits a r e f o u n d here for t h e c o n
trast v a r i a t i o n m e t h o d with n e u t r o n r a d i a t i o n .
N e u t r o n scattering e x p e r i m e n t s o n n e t w o r k s (gels,
r u b b e r s ) h a v e p r o v i d e d t h e m o s t interesting obser
v a t i o n s o n t h e elastic r e s p o n s e of these m a t e r i a l s .
Bastide et al. (1982) noticed t h a t d u r i n g o s m o t i c
deswelling of a gel by a factor of four, the s q u a r e d
r a d i u s of g y r a t i o n of labelled c h a i n s in between
crosslinks r e m a i n e d u n c h a n g e d . ( H e r e , b o t h fluctua
tions in size a n d s q u a r e a v e r a g e size c o n t r i b u t e t o t h e
2
o b s e r v e d value of (R G}.) M o d e l s in which the overall
elastic d e f o r m a t i o n is affine t o G a u s s i a n coil d e f o r m a
tions m u s t n o w definitely be revised. D a t a a r e consis
tent with n e t w o r k r e a r r a n g e m e n t s o c c u r r i n g a t a scale
larger t h a n t h a t of c h a i n s in between crosslinks. T h e s e
c h a i n s a r e , in fact, widely interspersed. T h i s w a s n o t
a c c o u n t e d for in earlier i n t e r p r e t a t i o n s .
O n e of t h e m a j o r results o b t a i n e d by use of t h e
n e u t r o n scattering a n d isotopic labelling t e c h n i q u e is
the s e p a r a t e d e t e r m i n a t i o n of t h e p o l y m e r form factor
P(q) a n d s t r u c t u r e factor S(q) a t a n y p o l y m e r c o n c e n
t r a t i o n c. (In t h e absence of labelling, this s e p a r a t i o n
is only o b t a i n e d in t h e limit c->0.) T h e p r o c e d u r e w a s
applied t o t h e s t u d y of semidilute polyelectrolytes
(Williams et al. 1979). T h e q u e s t i o n w h e t h e r t h e
p o l y i o n s form a liquidlike s t r u c t u r e with a c o r r e l a t i o n
hole, o r a locally o r d e r e d s t r u c t u r e , is being e x a m i n e d .
R e c e n t d e t e r m i n a t i o n of partial p o l y i o n - c o u n t e r i o n
s t r u c t u r e factors (Nallet et al. 1983) suggests new
d e v e l o p m e n t s in t h e s t u d y of c h a r g e a n d c o n c e n
t r a t i o n fluctuations, a n d their c o r r e l a t i o n in these
systems.

4. Small-Angle

Scattering:

Crystalline

Polymers

I n t e r p r e t a t i o n s of n e u t r o n scattering results o b t a i n e d
in this field h a v e been eagerly d i s p u t e d . A t first, the
a p p l i c a t i o n of isotopic labelling revealed s o m e diffi
culties. D e u t e r a t e d a n d n o n d e u t e r a t e d coils segregate
d u r i n g crystallization, w h e n this process is long c o m
p a r e d with m o l e c u l a r diffusion times. Q u e n c h i n g ,
however, yields a h o m o g e n e o u s d i s t r i b u t i o n . N e u t r o n
scattering w a s used t o d e t e r m i n e t h e coil configu
r a t i o n s within a n d in b e t w e e n crystallites. D a t a s h o w
t w o different configurations ( Y o o n a n d F l o r y 1979).
W h e n crystallization occurs in the melt, r a n d o m
reentry prevails (Sadler a n d Keller 1976, Summerfield
et al. 1978). W h e n , h o w e v e r , crystallization occurs in
dilute solution, the coil r a d i u s of g y r a t i o n is f o u n d t o
be smaller t h a n t h e equivalent r a d i u s in m e l t - g r o w n
crystallites. T h i s o b s e r v a t i o n , t o g e t h e r with the
observed i n t e r m e d i a t e form factor, suggests m o d e r a t e
adjacent reentry a n d possible superfolding of t h e coil.
Scattering by crystallites m a d e of small linear m o l
ecules indicates a c o r r e l a t i o n hole a t large w a v e
vectors: reentry occurs at sites further r e m o v e d t h a n
nearest n e i g h b o u r s .

Polymers:

5. Polymer

Dynamics

A n i m p o r t a n t s t u d y at the I L L w a s m a d e using a
n e u t r o n spin e c h o s p e c t r o m e t e r t o d e t e r m i n e c h a r a c
teristic diffusive m o d e s of a p o l y m e r coil in dilute
solution ( R i c h t e r et al. 1978). T h e r e l a x a t i o n time x(q)
for the observed c o n c e n t r a t i o n fluctuation correla
tions w a s f o u n d t o be in a g r e e m e n t with t h e disper
sion relation p r e d i c t e d earlier by de G e n n e s ,

=
3
~\)
DRhq , characteristic of flexible coil m o t i o n s
in a solution with solvent backflow. T h i s relation w a s ,
however, first confirmed b y light scattering experi
m e n t s ( A d a m a n d D e l s a n t i 1977). T h e t w o results
m a y be c o m p l e m e n t a r y , b u t the q u e s t i o n is raised of
a n a p p r o p r i a t e use for the n e u t r o n scattering. T h e
n e u t r o n spin e c h o s p e c t r o m e t e r h a s been used t o
p r o v i d e a set of d a t a for diffusion coefficients in lowmolecular-weight melts, as a function of m o l e c u l a r
weight (Higgins 1982). T h e r e w a s s o m e h o p e of
detecting r e p t a t i o n m o d e s in t h e r m a l B r o w n i a n
m o t i o n , b u t t h e time scale h e r e is i n a p p r o p r i a t e .
R e a l - t i m e n e u t r o n scattering e x p e r i m e n t s were set
u p for t h e s t u d y of stress r e l a x a t i o n a t c o n s t a n t strain
in p o l y s t y r e n e melts ( B o u e et al. 1982). H e r e , the
r e t u r n t o e q u i l i b r i u m c a n be slowed d o w n by c o n t r o l l
ing the t e m p e r a t u r e n e a r (above) t h e glass-transition
t e m p e r a t u r e Tg. M o r e o v e r , q u e n c h i n g t h e s a m p l e
freezes the coil c o n f i g u r a t i o n a t given times t. Several
tests c o u l d be m a d e c o n c e r n i n g either t h e R o u s e
llA
r e p r e s e n t a t i o n of t h e d a t a as a function of qt
or
alternatively the i n d e p e n d e n c e of the relaxation times
with the w a v e vector q.
Results of a quasi-elastic i n c o h e r e n t scattering
e x p e r i m e n t b y c o u n t e r i o n diffusive m o t i o n s a r e
also w o r t h m e n t i o n i n g . T h e diffusion coefficient of
t e t r a m e t h y l a m m o n i u m in t h e presence of p o l y i o n s
(sulfonated
polystyrene)
is
found
to
be
1
Z) = 3 . 7 x l O ^ c n v V (Nallet et al. 1983). T h i s is
lower by a factor of four t h a n t h e m e a s u r e d value of
_ 5
2
_1
in t h e presence of B r " . T h i s
D= 1.5 x 1 0 c m s
reference reflects t h e larger electric field g r a d i e n t s
associated with p o l y i o n s .

6. Concluding

Note

T h e m a i n c o n t r i b u t i o n of the n e u t r o n scattering tech

n i q u e t o o u r k n o w l e d g e of p o l y m e r systems c o m e s
from its ability t o unfold the s u p e r p o s i t i o n of p a i r
c o r r e l a t i o n s . T h e d e t e r m i n a t i o n of such c o r r e l a t i o n s
h a s been fruitful b o t h in f u n d a m e n t a l a n d m a t e r i a l s
science. M a n y e x p e r i m e n t s a r e still being i n t e r p r e t e d ,
which reflects the infancy of n e u t r o n scattering as a
tool for e x a m i n i n g p o l y m e r s t r u c t u r e . F u r t h e r aspects
of p o l y m e r s t r u c t u r e w h i c h m a y be investigated by
n e u t r o n scattering a r e related to blends a n d b r a n c h e d
systems.
See also: Polymers: X-Ray Scattering

Neutron

Scattering

Bibliography
Adam M, Delsanti 1977 Photon beat study of internal
modes in large polymer coils. J. Phys. (Paris), Lett. 38:
271-3
Bastide J, Picot C, Candau S 1982 Some comments on the
swelling of polymeric networks in relation to their struc
ture. J. Macromol. Sci., Phys. 19: 13-34
Boue F, Nierlich M, Jannink G, Ball R C 1982 A real time
neutron scattering experiment for the study of polymer
dynamics. Interpretations of the real time scattering ex
periment for polystyrene melts during stress relaxation. J.
Phys. (Paris), Lett. 43: 585-91/592-600
Cotton J , Farnoux B, Jannink G, Mons J, Picot C 1972
Observation de la conformation de la chaine polymerique
dans le solide amorphe par diffusion des neutrons aux
petits angles. CR. Hebd. Seances Acad. Sci., Ser. C 175:
175-8
Daoud M, Cotton J , Farnoux B, Jannink G, Sarma G,
Benoit H, Duplessix R, Picot C, de Gennes G 1975
Solutions of flexible polymers. Neutron experiments and
interpretation. Macromolecules 8: 804-18
des Cloizeaux J 1980 Short range correlation between ele
ments of a long polymer in a good solvent. J. Phys.
(Paris) 41: 223-38
Duval M, Duplessix R, Picot C, Decker D, Rempp , Benoit
H, Cotton J , Jannink G, Farnoux B, Ober R 1976
Neutron small-angle scattering by copolymer solutions. J.
Polym. Sci., Polym. Lett. Ed. 14: 585-9
Feldkamp L A, Venkataraman G, King J S 1968 Dispersion
relation for skeletal vibrations in deuterated polyethylene.
Proc. 4th IAEA Symp. Neutron Inelastic Scattering, Vol.
2. International Atomic Energy Agency, Vienna, pp. 15965
Higgins J S 1982 Quasielastic and inelastic neutron scatter
ing. In: Pethrick R A, Richards R W (eds.) 1982 Static
and Dynamic Properties of the Polymeric Solid State,
NATO Advanced Study Institute Series C, pp. 374^8
Kirste R G, Kruse W A, Schelten J 1973 Die Bestimmung
des Tragheitsradius von Polymethylmethacrylat im Glaszustand durch Neutronbeugung. Makromol. Chem. 162:
299-303
Kirste R G, Lehnen R 1976 Die Bestimmung des chemischen Potentials und des Expansionskoeffizienten in Mischungen von Polydimethylsiloxanen unterschiedlichen
Molekulargewichts. Makromol. Chem. 177: 1137^43
Lodge , Amis J, Han C C, Glinka C J, Matsushita Y,
Noda I, Nagasawa 1983 Internal expansion from block
copolymers of h-styrene and d-styrene. Natl. Bur. Stand.
(U.S.) Rep. XX: 112-16
Nallet F, Jannink G, Hayter J B, Oberthur R, Picot C 1983
Observation of the dynamics of polyelectrolyte strong
solutions by quasi-elastic neutron scattering. J. Phys.
(Paris) 44: 87-99
Richter D, Hayter J B, Mezei F, Ewen 1978 Dynamical
scaling in polymer solutions investigated by neutron spin
echo techniques. Phys. Rev. Lett. 41: 1484-7
Sadler M, Keller A 1976 Trajectory of polyethylene chains
in single crystals by low angle neutron scattering. Polymer
17: 3 7 ^ 0
Stapleton J, Allen J , Flynn C , Stirson D G, Kurtz S R
1980 Fractal form of proteins. Phys. Rev. Lett. 45: 1456-9
Stein S, Han C 1985 Neutron scattering from polymers.
Phys. Today 38: 74^80

353

Polymers:

Neutron

Scattering

Summerfield G C, King J S, Ullman R 1978 Small angle

neutron scattering from solution-crystallized and meltcrystallized polyethylene. / . Appl. Crystallogr. 11: 548-51
Twisleton J F, White J W 1972 Interchain force field of
polyethylene by neutron scattering. Proc. 5th IAEA
Symp. Neutron Inelastic Scattering. International Atomic
Energy Agency, Vienna, pp. 301-14
Williams C, Nierlich M, Cotton J P, Jannink G, Boue F,
Daoud M, Farnoux B, Picot C, de Gennes G, Rinaudo
M, Moan M, Wolff C 1979 Polyelectrolyte solutions:
intrachain and interchain correlations observed by
SANS. J. Polym. Sci., Polym. Lett. Ed. 17: 379-84
Yoon D Y, Flory J 1979 Molecular morphology in semicrystalline polymers. Faraday Discuss. Chem. Soc. 68:
288-96
G. Jannink
[Centre d ' E t u d e s N u c l e a i r e s ,
Saclay, F r a n c e ]

Being a s c a t t e r i n g t e c h n i q u e , a R a m a n s p e c t r u m m a y
b e t a k e n from a n y s a m p l e of a r e a large e n o u g h t o
scatter a focused laser b e a m ( a p p r o x i m a t e l y 50
d i a m e t e r ) . F i b e r s , films, p o w d e r s , gels a n d crystalline
solids of p o l y m e r s h a v e b e e n e x a m i n e d w i t h success.
S o m e of t h e v i b r a t i o n a l b a n d s m o s t sensitive t o
c h a n g e s in p o l y m e r c o n f o r m a t i o n a r e w e a k in
infrared a b s o r p t i o n , b u t a r e t h e m o s t intense lines
in R a m a n . F u r t h e r m o r e , w a t e r , as t h e n a t u r a l solvent
in t h e b o d y a n d also a relatively w e a k s c a t t e r e r in
R a m a n , c a n b e u s e d in s o l u t i o n studies. T h i s aspect is
very i m p o r t a n t in s t r u c t u r a l studies of b i o p o l y m e r s .
T h e origin of t h e n o r m a l R a m a n effect c a n b e
u n d e r s t o o d in t e r m s of t h e classical t r e a t m e n t of
m o l e c u l a r v i b r a t i o n s . T h i s t h e o r y is b a s e d o n t h e idea
t h a t i n c i d e n t e l e c t r o m a g n e t i c r a d i a t i o n w i t h fre
q u e n c y v 0 i n d u c e s a v a r i a b l e d i p o l e m o m e n t given
by:
= <xE0 COS 2nVjt

Polymers: Raman Spectroscopy

T h e R a m a n effect is t h e inelastic s c a t t e r i n g of electro
m a g n e t i c r a d i a t i o n by m a t t e r . T h e m o s t c o m m o n l y
considered e x a m p l e is t h a t of m o n o c h r o m a t i c light of
frequency v 0 scattered by a molecule. T h e m o l e c u l e
c a n exist in o n e of t h e s t a t i o n a r y v i b r a t i o n a l states,
b u t u n d e r t h e influence of e l e c t r o m a g n e t i c w a v e s it
c a n u n d e r g o a t r a n s i t i o n from s t a t e m t o state n, a n d
t h e w a v e will b e scattered with a lower o r h i g h e r
frequency given by:
v = v0(En-EJ/h

(1)

w h e r e En a n d Em a r e t h e energies a s s o c i a t e d w i t h
v i b r a t i o n a l states a n d m, respectively. Since these
energy levels a r e c h a r a c t e r i s t i c of t h e chemical a n d
physical s t r u c t u r e s of p o l y m e r s , R a m a n s p e c t r o s c o p y
h a s been utilized as a c h a r a c t e r i z a t i o n m e t h o d for
these m a t e r i a l s .

(2)

w h e r e is t h e m o l e c u l a r polarizability, E0 is t h e
a m p l i t u d e of t h e i n c i d e n t electric field a n d v, is t h e
frequency of t h e ith n o r m a l v i b r a t i o n . T h e m o l e c u l a r
p o l a r i z a b i l i t y is n o t a c o n s t a n t , since it d e p e n d s o n t h e
m o l e c u l a r c o n f o r m a t i o n , w h i c h c h a n g e s w i t h displa
c e m e n t of t h e nuclei d u r i n g n o r m a l v i b r a t i o n s . T h e r e
fore, t h e p o l a r i z a b i l i t y is usually expressed as:
= 0 + ' c o s 2nvtt

(3)

w h e r e aj is t h e c h a n g e in t h e polarizability w i t h
respect t o t h e d i s p l a c e m e n t of t h e ith n o r m a l c o o r d i n
ate. T h e r e f o r e t h e i n d u c e d d i p o l e m o m e n t c a n b e
expressed as
p = (X0E0 c o s 2 0 /
+ 0 c o s 2 0 / c o s 2nvtt
= oc0E0 COS 2nv0t

(4)

+ a j i s 0 c o s 2 ( 0 + ,)/

+ ((0 c o s 2 ( 0 - v f ) i

1. Raman

Effect

and its Utility

in Polymer

Science

R a m a n first o b s e r v e d t h e inelastic s c a t t e r i n g p r o c e s s
of p h o t o n s from m a t t e r in 1928 a n d w a s a w a r d e d t h e
N o b e l Prize in 1930 for this discovery. I n t h e s u b s e
q u e n t y e a r s , i n s t r u m e n t a t i o n difficulties a n d s t r i n g e n t
sample requirements m e a n t that R a m a n spectroscopy
r e m a i n e d a fairly exotic t e c h n i q u e . W i t h a d v a n c e s in
i n s t r u m e n t a t i o n , p a r t i c u l a r l y after t h e a d v e n t of t h e
laser, R a m a n s p e c t r o s c o p y h a s d e v e l o p e d i n t o a p r o
m i n e n t b r a n c h of m o l e c u l a r s p e c t r o s c o p y . Since t h e
early 1970s, R a m a n s p e c t r o s c o p y (i.e., analysis) h a s
been used extensively in t h e investigations of p o l y m e r
structure and composition.
T h e i m p o r t a n c e of R a m a n s p e c t r o s c o p y in investig
ating polymer structures c a n n o t be overestimated.

354

(5)

F r o m classical e l e c t r o d y n a m i c s c a n oscillate n o t
only w i t h t h e frequency v 0, b u t also w i t h frequencies
v 0 v, a n d v 0 + v,.. T h e last t w o t e r m s a r e k n o w n as t h e
S t o k e s a n d a n t i - S t o k e s t r a n s i t i o n s in a R a m a n spec
t r u m . It s h o u l d b e e m p h a s i z e d t h a t c e r t a i n s y m m e t r i c
v i b r a t i o n s w i t h large c h a n g e s in t h e polarizability
t e n s o r a r e s t r o n g in R a m a n b u t m a y b e w e a k in
infrared. T h e s e v i b r a t i o n s i n c l u d e c o n f o r m a t i o n a l l y
sensitive skeletal v i b r a t i o n s w h i c h a r e i m p o r t a n t in
structural characterization.
I n strict t e r m s , a q u a n t u m m e c h a n i c a l t r e a t m e n t is
n e e d e d in o r d e r t o derive t h e full t h e o r y of R a m a n
scattering. R a m a n intensity a s s o c i a t e d w i t h t h e ith
v i b r a t i o n is often expressed as
2

h =

2 (0 -

vtfhN

*\[1-(-,/*)

(a') /0

(6)

Polymers:

Raman

Spectroscopy

Figure 1
Schematic diagram of a Raman spectrometer

H e r e t h e v i b r a t i o n a l p a r t of t h e t o t a l w a v e function of
the molecule is t a k e n a s t h a t of t h e h a r m o n i c oscil
l a t o r of frequency v, a n d r e d u c e d m a s s ; is t h e
n u m b e r of scatterers; I0 is t h e intensity of t h e incident
laser source; a n d ('), is t h e derivative of t h e c o m
p o n e n t of t h e polarizability t e n s o r associated with t h e
/th v i b r a t i o n a l t r a n s i t i o n .

2, Experimental

Aspects

T h e principal type of R a m a n i n s t r u m e n t a t i o n h a s
n o w b e c o m e fairly s t a n d a r d i z e d a n d is s h o w n s c h e m a
tically in Fig. 1. A n u m b e r of i n s t r u m e n t s w i t h
exceptional optical p e r f o r m a n c e a r e available c o m
mercially. T h e R a m a n s p e c t r o m e t e r s usually incor
p o r a t e a n a r g o n - i o n laser as t h e excitation s o u r c e .
This laser is c a p a b l e o f p r o v i d i n g lasing lines o f
sufficient p o w e r with w a v e l e n g t h s v a r y i n g from u l t r a
violet t o t h e green 5145 A line for i l l u m i n a t i o n . T h e
high fluorescent b a c k g r o u n d o b s e r v e d in s o m e
R a m a n spectra generally arises from i m p u r i t i e s in t h e
sample. I n these cases, t h e excitation w a v e l e n g t h s
should be shifted t o below t h e energy of t h e electronic
transition of t h e impurities. Y e l l o w o r red lasing lines
from k r y p t o n o r h e l i u m - n e o n gas lasers a r e available
for this p u r p o s e , a n d t h e g r a t i n g a n d p h o t o m u l t i p l i e r
are selected t o m a x i m i z e d e t e c t i o n efficiency.
D o u b l e o r triple m o n o c h r o m e t e r s a r e usually
e m p l o y e d in t a n d e m t o s e p a r a t e t h e scattered R a m a n

a n d R a y l e i g h r a d i a t i o n s collected a t 90 from the

incident laser b e a m . W i t h t h e use of a n iodine optical
filter o r in c o n j u n c t i o n with a n interferometer, the
elastically scattered Rayleigh light c a n be further
r e d u c e d relative t o t h e R a m a n scattered light in o r d e r
t o e n h a n c e t h e signal-to-noise r a t i o in t h e very low
- 1
frequency region ( < 10 c m ) .
T h e choice of t h e g r a t i n g s used for dispersion is
very i m p o r t a n t in o r d e r t o achieve a r e d u c t i o n of stray
light associated with t h e excitation frequency. A l m o s t
all t h e h i g h - p e r f o r m a n c e s p e c t r o m e t e r s a r e e q u i p p e d
with h o l o g r a p h i c g r a t i n g s , w h i c h h a v e low s t r a y light
a n d a r e entirely free of satellite lines n e a r s t r o n g lines.
T h i s c h a r a c t e r i s t i c is p a r t i c u l a r l y i m p o r t a n t for lowfrequency s p e c t r o s c o p i c w o r k .
T h e p h o t o m u l t i p l i e r is, a t p r e s e n t , t h e only efficient
a n d p r a c t i c a l p h o t o n c o u n t e r in t h e visible region.
R e q u i r e m e n t s for R a m a n s p e c t r o s c o p y a r e high
q u a n t u m efficiency, flat r e s p o n s e a n d low d a r k
c o u n t s . I T T F W - 1 3 0 o r R C A 31034 p h o t o m u l t i pliers h a v e p r o v e n t o be suitable in m o s t R a m a n
applications.
S o m e of t h e m a j o r d e v e l o p m e n t s in R a m a n instru
m e n t a t i o n in recent years h a v e dealt with d a t a a c q u i
sition a n d i n s t r u m e n t c o n t r o l b y c o m p u t e r s . T h e
m o t i v a t i o n for interfacing a c o m p u t e r t o a R a m a n
i n s t r u m e n t is t o simplify d a t a acquisition, t o increase
t h e signal-to-noise r a t i o a n d t o p e r f o r m d a t a analysis
and reduction. In most R a m a n experiments, the rate
of d a t a collection rarely exceeds a few p o i n t s p e r
s e c o n d . T h i s t y p e of o p e r a t i o n c a n be suitably

355

Polymers:

Raman

Spectroscopy

h a n d l e d by inexpensive m i c r o p r o c e s s o r systems.
T h e s e m i c r o p r o c e s s o r s are q u i t e powerful m a c h i n e s
offering versatile e x p e r i m e n t a l c o n t r o l a n d c o m p u t a
tional capabilities. H o w e v e r , if high precision is
needed, the c o m p u t a t i o n a l speed of m i c r o p r o c e s s o r s
is insufficient. F u r t h e r m o r e , even t h o u g h the h a r d
w a r e c a n be o b t a i n e d at quite r e a s o n a b l e prices,
software d e v e l o p m e n t c a n b e c o m e the single m o s t
costly item. T h e r e f o r e , a R a m a n d a t a collection sys
t e m designed a r o u n d the d a t a r e d u c t i o n or e v a l u a t i o n
p r o g r a m s available o n a higher level c o m p u t e r system
is usually desirable. D a t a transfer between v a r i o u s
c o m p u t e r s c a n usually be a c c o m p l i s h e d by c o n c u r r e n t
execution of linking p r o g r a m s with m i n i m a l h a n d
shaking.

3. New Applications

of Raman

Spectroscopy

C o m p a r e d to infrared s p e c t r o s c o p y , there a r e rela

tively few instances w h e r e R a m a n s p e c t r o s c o p y is the
principal t e c h n i q u e for s t r u c t u r a l c h a r a c t e r i z a t i o n of
p o l y m e r s . O n e of the m o r e i m p o r t a n t c o n t r i b u t i o n s of
R a m a n s p e c t r o s c o p y h a s been associated with t h e
detection a n d analysis of the low-frequency v i b r a t i o n
( < 200 w a v e n u m b e r s ) . T h e e x p e r i m e n t a l difficulties
associated with low-frequency infrared spectra are
considerable, b u t the i m p o r t a n c e of e x t e n d i n g
spectral o b s e r v a t i o n s i n t o this region in p o l y m e r
c h a r a c t e r i z a t i o n c a n n o t be o v e r e m p h a s i z e d as the
delocalized n o r m a l vibrations, such as skeletal tor
sional vibrations, longitudinal acoustic m o d e ( L A M )
a n d lattice m o d e s are sensitive to chain c o n f o r m a t i o n
or molecular packing, a n d are usually located in this
particular region. In R a m a n spectroscopy, however,
-1
region is accessible w i t h o u t
the entire 10-4000 c m
difficulty; this is particularly useful in the quantitative
description of the m o r p h o l o g i c a l aspects a n d their
changes in semicrystalline polymers.
A n o t h e r a r e a of p o l y m e r s t r u c t u r a l analysis w h e r e
R a m a n s p e c t r o s c o p y features p r o m i n e n t l y is in the
c h a r a c t e r i z a t i o n of the degree of regularity associated
with the t h r e e - d i m e n s i o n a l o r d e r in p o l y m e r s . W i t h
few exceptions, the v i b r a t i o n a l spectra o b t a i n e d re
flect the regular o r irregular s t r u c t u r e of a r e p e a t unit
of a single c h a i n . U s u a l l y R a m a n d a t a a r e c o m p l e
m e n t a r y t o infrared o b s e r v a t i o n s a n d because of the
different optical selection rules, completely sym
metric, infrared-inactive, higher o r d e r t r a n s i t i o n s m a y
be observed in R a m a n spectroscopy. F o r e x a m p l e , the
v i b r a t i o n a l spectra in the C stretching region
o b t a i n e d for polyethylene a n d p o l y b u t a d i e n e are
unexpectedly c o m p l i c a t e d . U n t i l recently it h a s been
a s s u m e d t h a t , since the C stretching m o d e s a r e
highly localized a n d involve nearly p u r e h y d r o g e n
m o t i o n , they a r e essentially insensitive t o m o l e c u l a r
c o n f o r m a t i o n a n d e n v i r o n m e n t , in s h a r p c o n t r a s t t o
skeletal m o t i o n s at lower frequencies. T h i s belief
a p p e a r e d intuitively s o u n d a n d w a s s u p p o r t e d by a

356

half-century of evidence from infrared spectroscopy.

It is therefore initially surprising t o find t h a t c h a n g e s
in the C stretching region of R a m a n s p e c t r o s c o p y
c a n be c o r r e l a t e d with t h e d i s r u p t i o n of t h e threed i m e n s i o n a l o r d e r a n d d i s o r d e r of chains in the
crystal. S o m e of the o b s e r v e d c o m p l e x spectral
c h a n g e s h a v e been explained by a q u a n t i t a t i v e a n d
qualitative analysis of the s t r o n g F e r m i r e s o n a n c e
i n t e r a c t i o n between the R a m a n active s y m m e t r i c
stretching f u n d a m e n t a l a n d t h e a p p r o p r i a t e b i n a r y
c o m b i n a t i o n s involving the b e n d i n g m o d e s in the
lower frequency region. T h e results of this type of
analysis a r e the basis for analytical t e c h n i q u e s for
investigating s t r u c t u r e a n d c h a n g e s in systems such as
liquid crystals a n d b i o m e m b r a n e s .
Lastly, R a m a n spectroscopy, in c o n j u n c t i o n with
theoretical n o r m a l v i b r a t i o n a l analysis a n d infrared
s p e c t r o s c o p y , allows p o l y m e r scientists t o definitively
assign observed v i b r a t i o n a l b a n d s in o r d e r t o eluci
d a t e p o l y m e r s e c o n d a r y s t r u c t u r e a n d tacticity.
U n i q u e s t r u c t u r a l i n f o r m a t i o n c a n be o b t a i n e d from
R a m a n spectroscopy through polarization measure
m e n t s . T h e form of the polarizability t e n s o r d e p e n d s
o n m o l e c u l a r s y m m e t r y . If all t h e molecules are well
defined in o r i e n t a t i o n , t h e individual t e n s o r element
c a n be m e a s u r e d by m a k i n g a p p r o p r i a t e choices of
the incident a n d scattered p o l a r i z a t i o n directions.
F e w p o l y m e r s a m p l e s c o n t a i n such high o r i e n t a t i o n
o r d e r . M o s t samples c o n t a i n i s o t r o p i c p a r t s in the
form of a m o r p h o u s sections a n d o r d e r e d crystalline
regions. F o r these partially o r d e r e d o r completely
d i s o r d e r e d systems, mixing of t e n s o r elements occurs.
U n l i k e the dipole associated with infrared spectros
c o p y h o w e v e r , the R a m a n scattering t e n s o r a v e r a g i n g
over possible m o l e c u l a r o r i e n t a t i o n consistent with
t h e degree of d i s o r d e r in the s a m p l e s being m e a s u r e d
c a n still be meaningful. Highly o r i e n t e d d r a w n o r
e x t r u d e d p o l y m e r s , such as polyethylene, p o l y p r o p y
lene, poly(vinylidene fluoride) a n d polystyrene, h a v e
yielded quite a c c e p t a b l e p o l a r i z e d R a m a n spectra for
detailed m o r p h o l o g i c a l c h a r a c t e r i z a t i o n . Even for t h e
case of c o m p l e t e loss of o r i e n t a t i o n , such as p o l y m e r
solutions o r melt, local c o n f o r m a t i o n c a n still be
d e d u c e d by the d e p o l a r i z a t i o n r a t i o which c a n be
expressed as t h e r a t i o of scattered intensity with
p o l a r i z a t i o n p e r p e n d i c u l a r t o t h e incident r a d i a t i o n t o
the scattered intensity with parallel p o l a r i z a t i o n .
See also: Elastomers:
Raman Spectroscopy

Spectroscopic

Characterization;

Bibliography
Koningstein J A 1972 Introduction to the Theory of the
Raman Effect. Reidel, Dordrecht, The Netherlands
Shepherd I W 1977 Raman polarization techniques in the
study of macromolecules. Adv. Infrared Raman Spectrosc.
3: 127-66

Polymers:

Tests for Degradation

and

Stabilization

Synder R G, Hsu S L, Krimm S 1978 Vibrational spectra in

the C stretching region and the structure of the
polymethylene chain. Spectrochim. Acta A 34: 395-406
S. L. H s u
[University of M a s s a c h u s e t t s , A m h e r s t ,
Massachusetts, USA]

Polymers: Tests for Degradation and

Stabilization
N u m e r o u s tests h a v e been d e v e l o p e d for m e a s u r i n g
the stability of p o l y m e r s , t a k i n g i n t o a c c o u n t the
m a n y different c o n d i t i o n s responsible for p o l y m e r
d e g r a d a t i o n . S o m e tests m e a s u r e t h e stability of
p o l y m e r s t o t h e r m a l d e g r a d a t i o n ; o t h e r s p r o v i d e for
e v a l u a t i o n of t h e a d v e r s e effects of w e a t h e r i n g . T h e r e
are also tests t o m e a s u r e t h e effect of specific chemical
r e a c t a n t s o r u n i q u e c o n d i t i o n s o n special classes of
p o l y m e r s (e.g., t h e test for o z o n e resistance of u n s a
t u r a t e d e l a s t o m e r s u n d e r stress). A s t h e stability of
p o l y m e r s increased, it b e c a m e necessary t o d e v e l o p
tests t h a t m e a s u r e stability over s h o r t e r time intervals.
T h e s e p r o c e d u r e s a r e referred t o as accelerated tests.
Accelerated tests for p o l y m e r stability p r o v i d e d a t a
which m u s t be e x t r a p o l a t e d d o w n t o c o n d i t i o n s t o be
e n c o u n t e r e d in service. It is necessary t o intensify test
c o n d i t i o n s in o r d e r t o accelerate d e g r a d a t i o n , b u t
e x t r a p o l a t i o n of t h e results from accelerated tests t o
service c o n d i t i o n s is n o t a l w a y s linear. C h a n g e s in
m o r p h o l o g y o r in the relative rates of individual
reactions in a n overall m e c h a n i s m c o u l d result in a
n o n l i n e a r r e l a t i o n s h i p as s h o w n schematically in
Fig. 1. A s a general principle, t h e closer accelerated
tests a p p r o x i m a t e service c o n d i t i o n s , the m o r e a c c u r
ate will be the p r e d i c t i o n of service life.
T h e r e are t w o different a p p r o a c h e s t o m e a s u r i n g
the stability of p o l y m e r s . In t h e d e v e l o p m e n t of a n e w
p o l y m e r o r in e v a l u a t i n g the effectiveness of stabi
lizers, a m a t e r i a l - o r i e n t e d test is used. A s t h e n a m e
implies, this type of test is i n t e n d e d t o m e a s u r e t h e
stability of a p o l y m e r o r p o l y m e r c o m p o s i t i o n a p a r t
from c o n t a c t with o t h e r m a t e r i a l s w h i c h m i g h t be
used in a final p r o d u c t . D e s i g n - o r i e n t e d tests, o n t h e
o t h e r h a n d , m e a s u r e p o l y m e r stability in a c o m p l e t e
device o r article. T h e time t o failure c a n be affected b y
o t h e r m a t e r i a l s with which t h e p o l y m e r is in c o n t a c t .
F o r e x a m p l e , stabilized polyolefins lose m o s t of their
stability w h e n e x t r u d e d as i n s u l a t i o n over c o p p e r
conductors. W h e n polymers are laminated o n t o
metals, similar loss of stability c a n occur. Stabilizers
m a y also be e x t r a c t e d from a stabilized p o l y m e r b y
o t h e r m a t e r i a l s p r e s e n t in t h e final p r o d u c t . D e s i g n oriented tests s h o u l d be used t o predict h o w l o n g a
p o l y m e r will retain its essential p r o p e r t i e s in e a c h
specific a p p l i c a t i o n . I m p r o v e m e n t s in t h e stability of

test
conditions

Intensity of t e s t

service
conditions

Figure 1
Schematic representation of the relationship between test
conditions and service life

p o l y m e r c o m p o s i t i o n s a r e usually e v a l u a t e d by
m a t e r i a l s - o r i e n t e d tests before i n c o r p o r a t i o n i n t o a
finished p r o d u c t .

7. Measurement

of Thermal

Stability

E a r l y in t h e d e v e l o p m e n t of synthetic p o l y m e r s , c o n
siderable research effort w a s directed t o w a r d s their
p y r o l y t i c b e h a v i o u r . Tests t o m e a s u r e the d e c o m p o s i
tion t e m p e r a t u r e were b a s e d o n weight loss d u r i n g
h e a t i n g , either in v a c u u m o r in a n inert a t m o s p h e r e .
In a n a l t e r n a t i v e p r o c e d u r e , the p r e s s u r e developed by
volatile f r a g m e n t s from t h e p o l y m e r w a s d e t e r m i n e d .
Test s a m p l e s in sealed, e v a c u a t e d t u b e s were h e a t e d a t
p r o g r a m m e d rates of t e m p e r a t u r e increase a n d
c h a n g e s in s a m p l e weight m e a s u r e d . A l t h o u g h these
tests m a d e i m p o r t a n t c o n t r i b u t i o n s t o t h e s t r u c t u r a l
analysis of p o l y m e r s , t h e c o n d i t i o n s used a r e n o t
e n c o u n t e r e d in m o s t a p p l i c a t i o n s . T h e r m a l d e g r a d a
tion of p o l y m e r s in t h e presence of oxygen, however,
is c o m m o n t o all p o l y m e r s a n d several i m p o r t a n t tests
h a v e b e e n used t o m e a s u r e this effect.
1.1 Milling
Tests
T h e earliest tests for stability t o t h e r m a l o x i d a t i o n
o r i g i n a t e d in t h e s t u d y of t h e a g i n g of n a t u r a l r u b b e r .
In milling tests, r u b b e r s a m p l e s were passed conti
n u o u s l y b e t w e e n h e a t e d rolls, held a t close clearance.
T h e c o m b i n a t i o n of m e c h a n i c a l energy a n d h e a t

357

Polymers:

Tests for Degradation

and

Stabilization

accelerate d e g r a d a t i o n . Sticking of the s a m p l e t o t h e

rolls w a s t a k e n as t h e onset of d e g r a d a t i o n . T h i s test
w a s never precise, b u t did h a v e t h e a d v a n t a g e
of resembling processes used in m a k i n g r u b b e r
formulations.
T h e t o r q u e r h e o m e t e r is a n a d a p t a t i o n of t h e
milling test. I n this device, test s a m p l e s a r e h e a t e d a n d
milled b e t w e e n r o t a t i n g b l a d e s while s i m u l t a n e o u s l y
r e c o r d i n g c h a n g e s in t h e t o r q u e d e v e l o p e d by t h e
r o t o r s . D e g r a d a t i o n of t h e p o l y m e r is indicated b y a
r a p i d c h a n g e in t o r q u e . P o l y m e r s w h i c h d e g r a d e by
c h a i n cleavage s h o w a decrease in t o r q u e , w h e r e a s
those in w h i c h crosslinking p r e d o m i n a t e s s h o w a n
increase.
1.2 Oven Aging Tests
A m o n g t h e m o s t widely used tests for m e a s u r i n g
oxidative stability a r e t h o s e b a s e d o n oven aging. I n
t h e simplest version of this test, s a m p l e s a r e e x p o s e d
t o air while h e a t e d isothermally. Static a n d circulating
ovens h a v e been used, b u t t h e latter m a y c a u s e
excessive loss of stabilizers b y volatilization. T h e
progress of d e g r a d a t i o n is o b s e r v e d by r e m o v i n g
samples a t selected intervals a n d o b s e r v i n g c h a n g e s in
a p p e a r a n c e such a s d i s c o l o r a t i o n o r surface c r a c k i n g .
M o r e precise d a t a a r e o b t a i n e d by m e a s u r i n g c h a n g e s
which o c c u r in m e c h a n i c a l o r electrical p r o p e r t i e s .
M o d u l u s , e l o n g a t i o n a n d tensile s t r e n g t h a r e a m o n g
the m o r e c o m m o n m e c h a n i c a l m e a s u r e m e n t s a n d
dielectric s t r e n g t h o r dissipation factor a r e often
m e a s u r e d t o detect c h a n g e s in electrical p r o p e r t i e s .
Since s o m e of these m e a s u r e m e n t s a r e destructive,
samples a r e r e q u i r e d for e a c h test interval. M u l t i p l e
samples m a y also be tested t o correct for t h e scatter in
s o m e of these results. Infrared s p e c t r o s c o p y c a n also
be used t o follow chemical c h a n g e s in a p o l y m e r
d u r i n g oven aging. M e a s u r e m e n t of the increase in
c o n c e n t r a t i o n of c a r b o n y l g r o u p s is often e m p l o y e d .
O v e n aging tests h a v e t h e a d v a n t a g e of simplicity,
varying with t h e t e c h n i q u e used for following d e g r a
d a t i o n . H o w e v e r , they d o n o t p r o v i d e a c o n t i n u o u s
m e a s u r e m e n t . A c c u r a c y of t h e m e t h o d d e p e n d s o n
the frequency with w h i c h s a m p l e s a r e r e m o v e d for
e v a l u a t i o n a n d e n o u g h s a m p l e s m u s t be used a t t h e
start for every a n t i c i p a t e d test interval. D e s p i t e this
d i s a d v a n t a g e , oven aging tests h a v e t h e a d v a n t a g e of
following d e g r a d a t i o n b y observing c h a n g e s in a
p r o p e r t y which c o u l d be critical in a p a r t i c u l a r
application.
1.3 Oxygen Uptake
Measurements
M e a s u r e m e n t of t h e r a t e a t which oxygen reacts with
a p o l y m e r is a n a d a p t a t i o n of oven aging, used
extensively t o follow t h e r m a l o x i d a t i o n . I n this test
each s a m p l e is enclosed in a s e p a r a t e test c h a m b e r ,
usually a glass t u b e . M e a s u r e m e n t s a r e c o n d u c t e d in
p u r e oxygen. T h i s eliminates t h e v a r i a b l e c o n c e n t r a
tions of w a t e r a n d trace catalysts which a r e usually
p r e s e n t in air. A desiccant is placed in t h e test

358

c h a m b e r t o a b s o r b a n y w a t e r evolved as the s a m p l e
oxidizes.
Small s a m p l e s c a n be used in oxygen u p t a k e
m e a s u r e m e n t s , b u t s a m p l e thickness m u s t be carefully
c o n t r o l l e d . If t h e s a m p l e s a r e t o o thick, diffusion of
oxygen i n t o t h e p o l y m e r b u l k m a y b e c o m e the c o n
trolling r a t e factor. R e p r o d u c i b l e results c a n be
o b t a i n e d a b o v e t h e m e l t i n g r a n g e of t h e p o l y m e r ,
p r o v i d e d t h a t s a m p l e thickness d o e s n o t c h a n g e
significantly.
Originally, o v e n s were used for this test b u t m o r e
u n i f o r m s a m p l e t e m p e r a t u r e s a r e o b t a i n e d in a n oil
b a t h o r in a m e t a l block drilled t o a c c o m m o d a t e
s a m p l e t u b e s a n d c o n t r o l devices a n d h e a t e d b y
external h e a t e r s . T h e r a t e of o x i d a t i o n is m e a s u r e d
either volumetrically o r m a n o m e t r i c a l l y . W i t h t h e
former method, sample tubes are connected to a
b u r e t t e w h i c h is fitted with a levelling b u l b t o m a i n
t a i n a t m o s p h e r i c p r e s s u r e . It is possible t o follow
oxygen u p t a k e m a n o m e t r i c a l l y , b u t t h e r a t e of reac
tion is p r e s s u r e d e p e n d e n t , decreasing s h a r p l y as the
p r e s s u r e falls in t h e r e a c t i o n vessel.
O x y g e n u p t a k e m e a s u r e m e n t s h a v e several a d v a n
tages over the basic o v e n aging test. T h e r a t e of
r e a c t i o n with o x y g e n is followed c o n t i n u o u s l y a n d
there is n o i n t e r r u p t i o n in t h e test t o w i t h d r a w s a m
ples. Since s a m p l e size is very small, m a n y tests c a n be
r u n s i m u l t a n e o u s l y . H o w e v e r , it is advisable t o r u n
e a c h s a m p l e in d u p l i c a t e to c o m p e n s a t e for v a r i a t i o n s
in t h e m a t e r i a l . T h i s m e t h o d is widely used in e v a l u a t
ing t h e relative effectiveness of stabilizers. T h e p o i n t
of failure is t a k e n as t h e time a t w h i c h o x i d a t i o n
b e c o m e s a u t o c a t a l y t i c a n d is usually r e p o r t e d as the
i n d u c t i o n p e r i o d (i.e., time interval b e t w e e n the start
of t h e test a n d t h e intercept of t h e steady-state r a t e
e x t r a p o l a t e d b a c k t o t h e time axis).
M e c h a n i c a l , dielectric o r aesthetic failure d o n o t
a l w a y s coincide w i t h t h e i n d u c t i o n p e r i o d . A b e t t e r
c o r r e l a t i o n with a c t u a l failure c a n be o b t a i n e d b y first
d e t e r m i n i n g t h e level of o x i d a t i o n a t which a critical
p r o p e r t y exceeds t h e a l l o w a b l e limit, a n d t h e n deter
m i n i n g the time r e q u i r e d t o react with this a m o u n t of
oxygen.
1.4 Thermal
Analysis
T h e r m o a n a l y t i c a l t e c h n i q u e s h a v e been a d a p t e d t o
t h e m e a s u r e m e n t of t h e r m a l d e g r a d a t i o n , b o t h in t h e
a b s e n c e a n d in t h e presence of oxygen. C o m m e r c i a l
e q u i p m e n t is available for t h e r m o g r a v i m e t r i c analysis
( T G A ) , differential t h e r m a l analysis ( D T A ) a n d dif
ferential s c a n n i n g c a l o r i m e t r y ( D S C ) . E a c h of these
m e t h o d s h a s been used in t h e m e a s u r e m e n t of o x i d a
tive d e g r a d a t i o n in p o l y m e r s .
M o d e r n T G A is a n a d a p t a t i o n of early m e t h o d s
used t o s t u d y t h e pyrolysis of p o l y m e r s . T h e a p p a r a
t u s consists of a highly sensitive b a l a n c e enclosed in a
glass vessel. T h e test c h a m b e r m a y b e e v a c u a t e d o r
filled w i t h a n inert gas for m e a s u r i n g t h e t e m p e r a t u r e
Tc a t w h i c h p o l y m e r d e c o m p o s i t i o n t a k e s place. T h e

Polymers:

Tests for Degradation

7.5 Chemiluminescence

200

300

400
500
Temperature (C)

600

700

Figure 2
TGA scans for the thermal degradation of typical
polymers: (a) polyvinyl chloride), (b) polyethylene, and
(c) a polyamide

test is p r o g r a m m e d t o a selected r a t e of t e m p e r a t u r e
increase a n d s a m p l e weight is m o n i t o r e d c o n t i
n u o u s l y . T y p i c a l T G A d a t a a r e s h o w n in F i g . 2 for
the t h e r m a l d e g r a d a t i o n of several different p o l y m e r s .
T G A is a l s o used t o m e a s u r e t h e r a t e o f t h e r m a l
o x i d a t i o n . F o r these m e a s u r e m e n t s t h e s a m p l e is
h e a t e d i s o t h e r m a l l y usually in t h e 2 0 0 - 2 6 0 C r a n g e .
A n inert a t m o s p h e r e is m a i n t a i n e d o v e r t h e s a m p l e
until t h e test t e m p e r a t u r e is r e a c h e d a n d t h e inert g a s
is r a p i d l y replaced w i t h oxygen a t this p o i n t . W e i g h t
c h a n g e s a r e p l o t t e d a g a i n s t time. F o r stabilized
p o l y m e r s , t h e r e is n o significant weight c h a n g e until
the stabilizer is e x h a u s t e d . O x i d a t i o n t h e n t a k e s place
a n d there is a r a p i d gain in weight. T h e p e r i o d
between t h e i n t r o d u c t i o n o f o x y g e n a n d t h e o n s e t o f
r a p i d o x i d a t i o n is t a k e n a s t h e i n d u c t i o n p e r i o d .
D T A is b a s e d o n t h e principle o f a difference in
temperature response between the polymer a n d a n
inert c o n t r o l d u r i n g h e a t i n g . T h e r m o c o u p l e s in c o n
tact with b o t h p o l y m e r a n d c o n t r o l detect t h e t e m p e r
a t u r e differential AT. A s t r o n g e x o t h e r m indicates t h e
onset o f t h e a u t o c a t a l y t i c r e a c t i o n a n d t h e t i m e
required t o r e a c h this p o i n t defines t h e i n d u c t i o n
p e r i o d (see F i g . 3).
D S C is a n a d a p t a t i o n o f c o n v e n t i o n a l a d i a b a t i c
calorimetry. T h e test is n o t a s a c c u r a t e a s c o n v e n
tional c a l o r i m e t r y , b u t is a d e q u a t e for m e a s u r i n g t h e
t h e r m a l d e g r a d a t i o n o r o x i d a t i o n of p o l y m e r s . O x i d a
tive d e g r a d a t i o n a p p e a r s a s a s t r o n g e x o t h e r m in t h e
D S C m e a s u r e m e n t . T h e r m o m e c h a n i c a l analysis is
used t o m e a s u r e c h a n g e s in a m e c h a n i c a l p r o p e r t y
d u r i n g h e a t i n g . T o r s i o n a l b r a i d a n d volatilization
analyses h a v e also b e e n used t o m e a s u r e t h e r m a l
degradation,
b u t these t e c h n i q u e s
have
had
only limited a p p l i c a t i o n in m e a s u r i n g p o l y m e r
degradation.

and

Stabilization

Measurements

L i g h t is e m i t t e d d u r i n g t h e o x i d a t i o n of m a n y
polymers producing the p h e n o m e n o n of chemilumi
nescence. L i g h t emission is a t t r i b u t e d t o radicali n d u c e d r e a c t i o n s in t h e p o l y m e r m a s s . T e s t samples
a r e h e a t e d a t c o n s t a n t t e m p e r a t u r e u n d e r a s t r e a m of
o x y g e n . A s d e g r a d a t i o n p r o c e e d s , e m i t t e d light is
focused b y a lens system o n t o a p h o t o m u l t i p l i e r . T h e
q u a n t i t y o f e m i t t e d light is p l o t t e d a g a i n s t time. T h i s
t e c h n i q u e h a s been used t o detect d e g r a d a t i o n in t h e
latter stages o f t h e r e a c t i o n , b u t it m a y also b e used t o
detect early r e a c t i o n s o c c u r r i n g d u r i n g t h e i n d u c t i o n
p e r i o d . Since t h e q u a n t i t y o f light e m i t t e d early in t h e
r e a c t i o n is very small, it is necessary t o magnify t h e
effect. T h i s m a y b e d o n e either b y r a p i d l y replacing a n
inert a t m o s p h e r e with o x y g e n o r b y briefly exposing
t h e s a m p l e t o ultraviolet (uv) r a d i a t i o n . T h i s modifi
c a t i o n of t h e m e t h o d c o u l d b e useful in t h e early
d e t e c t i o n of o x i d a t i v e d e g r a d a t i o n . C h e m i l u m i n e s
cence c a n b e used t o e v a l u a t e b o t h t h e r m a l a n d
p h o t o o x i d a t i o n in p o l y m e r s .

2. Test for Ozone

Resistance

E l a s t o m e r s w h i c h c o n t a i n ethylenic u n s a t u r a t i o n in
the backbone chain are degraded rapidly by ozone
w h e n held u n d e r stress. R e s i s t a n c e t o o z o n e a t t a c k is
usually m e a s u r e d b y l a b o r a t o r y tests. A s t a n d a r d
m e t h o d h a s b e e n established b y t h e A m e r i c a n Society
for T e s t i n g a n d M a t e r i a l s ( A S T M ) . I n this test, s a m
ples a r e p l a c e d in a n a l u m i n u m c h a m b e r a n d held a t a
p r e s c r i b e d level o f stress. T e m p e r a t u r e is m a i n t a i n e d
a t 4 0 - 5 0 C while a m i x t u r e o f 500 p p b of o z o n e in
o x y g e n is p a s s e d o v e r t h e s a m p l e s . C r a c k s , which
a l w a y s f o r m p e r p e n d i c u l a r t o t h e direction o f applied
stress, indicate t h e o n s e t of d e g r a d a t i o n . T h e s e c r a c k s

oxygen
introduced
I

- induction period

Temperature

Figure 3
Typical DTA scan for the thermal oxidation of a
stabilized polymer

359

Polymers:

Tests for Degradation

and

Stabilization

m a y eventually extend t h r o u g h t h e test s a m p l e s .

O z o n e c o n c e n t r a t i o n is m o n i t o r e d frequently by titra
tion. T h i s test is often used t o r a t e a n t i o z o n a n t s a n d
waxes for their ability to inhibit o z o n e a t t a c k o n
elastomers.

3.

Weather ability

Tests

T h e d e g r a d a t i o n w h i c h occurs in p o l y m e r s d u r i n g
o u t d o o r e x p o s u r e is m e a s u r e d by either o u t d o o r o r
i n d o o r tests. T h e simplest of t h e o u t d o o r tests consists
of exposing samples at locations selected for their
high intensity of solar r a d i a t i o n . S a m p l e s a r e ex
a m i n e d periodically for evidence of d e g r a d a t i o n such
as d i s c o l o r a t i o n o r surface c r a c k i n g . W h e n m o r e
precise d a t a a r e required, s a m p l e s c a n be r e m o v e d
from the e x p o s u r e r a c k s a n d c h a n g e s in m e c h a n i c a l ,
electrical o r chemical p r o p e r t i e s m e a s u r e d .
O u t d o o r e x p o s u r e c o n d i t i o n s h a v e been s t a n d a r d
ized by the A S T M . T h e angle at which s a m p l e s a r e
m o u n t e d h a s been established as 45 with s a m p l e s
facing d u e s o u t h . M a t e r i a l t o be used in c o n s t r u c t i n g
the e x p o s u r e r a c k s a n d the n a t u r e of t h e u n d e r l y i n g
surface a r e also specified. A p p l i c a t i o n of these s t a n
d a r d s p r o v i d e s a r e a s o n a b l e c o r r e l a t i o n b e t w e e n dif
ferent l o c a t i o n s , b u t t h e time t o failure is usually only
a b o u t half t h a t e n c o u n t e r e d in service. A s o m e w h a t
higher level of acceleration is o b t a i n e d by c o n t i
n u o u s l y r o t a t i n g samples to follow t h e s u n ' s p a t h .
T h e s e s o l a r - t r a c k i n g devices a r e c o m p l i c a t e d a n d re
q u i r e c o n s i d e r a b l e m a i n t e n a n c e . F u r t h e r m o r e , there
is little a d d i t i o n a l acceleration over
fixed-angle
exposure.
T h e highest level of acceleration in a n o u t d o o r test
h a s been r e p o r t e d for devices which, in a d d i t i o n t o
solar t r a c k i n g , use a series of polished m e t a l m i r r o r s
to a c c u m u l a t e solar r a d i a t i o n a n d t o direct it t o the
surface of test samples. In these devices, k n o w n as
E M M A ( e q u a t o r i a l m o u n t with m i r r o r s for accelera
tion) devices, samples m a y r e a c h fairly high t e m p e r a
tures. A n air s t r e a m or a w a t e r jet is used to c o n t r o l
the t e m p e r a t u r e , b u t the c o n t r i b u t i o n of t h e r m a l
d e g r a d a t i o n m a y still exceed t h a t which occurs o u t
d o o r s . H o w e v e r , test results c a n be o b t a i n e d in a b o u t
o n e - t e n t h the time r e q u i r e d for n o r m a l o u t d o o r
exposure.
Results o b t a i n e d with a n y o u t d o o r test a r e subject
to w e a t h e r variability. F u r t h e r m o r e , e x p o s u r e is
limited t o daylight h o u r s a n d this seriously restricts
the level of acceleration. T h e s e factors h a v e stimu
lated d e v e l o p m e n t of devices t o m e a s u r e w e a t h e r ability in a l a b o r a t o r y e n v i r o n m e n t . T h e devices for
i n d o o r testing a r e k n o w n as w e a t h e r o m e t e r s .
T h e basic c o m p o n e n t of a w e a t h e r o m e t e r is a n
artificial source for uv r a d i a t i o n . S a m p l e s , m o u n t e d
o n r a c k s , r o t a t e slowly a r o u n d t h e light source. It is
very i m p o r t a n t t o use a light source with a uv spec
t r u m closely resembling t h a t of the sun. C a r b o n a n d

360

m e r c u r y arcs were used originally, b u t the x e n o n a r c is

gaining in p o p u l a r i t y since its s p e c t r u m m o s t closely
resembles t h a t of sunlight. I n c a n d e s c e n t s u n l a m p s
a n d fluorescent uv t u b e s a r e also used. Filters screen
o u t u n d e s i r a b l e r a d i a t i o n p e a k s a n d c o m b i n a t i o n s of
l a m p s m a y be used t o p r o v i d e a closer m a t c h t o the
solar s p e c t r u m .
F l u o r e s c e n t t u b e s h a v e a n i m p o r t a n t a d v a n t a g e in
t h a t they g e n e r a t e m u c h less h e a t t h a n m o s t arcs o r
i n c a n d e s c e n t b u l b s . It is i m p o r t a n t t h a t excessive h e a t
is n o t g e n e r a t e d in a w e a t h e r o m e t e r in o r d e r t o
p r e v e n t t h e r m a l r e a c t i o n s from b e c o m i n g t h e p r i m a r y
factor responsible for d e g r a d a t i o n . S a m p l e t e m p e r a
t u r e c a n be lowered by increasing t h e d i s t a n c e from
the light s o u r c e , b u t this also decreases t h e a m o u n t of
uv r a d i a t i o n r e a c h i n g t h e test samples. Baffles h a v e
been used t o shield s a m p l e s from r a d i a t i o n for a
fraction of t h e r o t a t i o n cycle. W a t e r s p r a y s h a v e also
been used as a m e a n s of c o o l i n g as well as t o i n t r o d u c e
t h e effect of m o i s t u r e o n test s a m p l e s . T a p w a t e r ,
h o w e v e r , leaves a film o n t h e surface which reduces
t h e a m o u n t of u v r e a c h i n g t h e s a m p l e s . C o n d e n s a t i o n
of w a t e r v a p o r o n test s a m p l e s is used in s o m e
w e a t h e r o m e t e r s : this resembles d e w f o r m a t i o n with
o u t leaving a film o n t h e surface.
Reasonably accurate correlations to outdoor
w e a t h e r i n g a r e o b t a i n e d with m o d e r n w e a t h e r
o m e t e r s . T h e time r e q u i r e d to r e a c h p o l y m e r failure
c a n be of t h e o r d e r of o n e - t e n t h t h a t o b s e r v e d in
service. By using a n a c t i m e t e r m o u n t e d alongside the
s a m p l e s , t h e a c t u a l level of uv r a d i a t i o n c a n be
m e a s u r e d c o n t i n u o u s l y a n d accurately: these devices
c o r r e c t for a n y c h a n g e in o u t p u t from t h e light source.
W h e n a n a c t i m e t e r is used, failure is b a s e d o n energy
units a b s o r b e d r a t h e r t h a n o n elapsed time. T h e
a c t u a l time t o failure c a n t h e n be calculated from
w e a t h e r b u r e a u r e p o r t s which s h o w t h e time interval
over w h i c h t h e critical a m o u n t of r a d i a t i o n reaches
a n y specific l o c a t i o n .
See also: Corrosion and Oxidation Study Techniques;
Polymers: Tests for Thermal Properties

Bibliography
Brown R 1986 Effect of temperature and environmental
resistance. Physical Testing of Rubber, 2nd edn. Elsevier,
Amsterdam, Chaps. 15-16
George G A 1981 Use of chemiluminescence to study the
kinetics of solid polymers. In: Grassie (ed.) 1981
Developments in Polymer Degradation, Vol. 3. Applied
Science, Barking, UK
Gray V E, Cadoff C 1967 Survey of techniques for
evaluating effects of weathering on plastics. Appl. Polym.
Symp. 4: 85-96
Hawkins W L (ed.) 1972 Polymer Stabilization. Wiley, New
York
Hirt R C, Searle 1967 Energy characteristics of outdoor
and indoor exposure sources and their relation to the
weatherability of plastics. Appl. Polym. Symp. 4: 61-83

Polymers:

Kaufman F Jr 1967 A new technique for evaluating outdoor

weathering properties of high density polyethylene. Appl.
Polym. Symp. 4: 131-9
Madorsky S L 1964 Thermal Degradation of Organic
Polymers, Polymer Reviews, Vol. 7. Interscience, New
York
Quackenbos , Samuels 1967 Practical problems in
predicting weathering performance. Appl. Polym. Symp.
4: 155-65
Turi (ed.) 1981 Thermal Characterization of Polymeric
Materials. Academic Press, New York

Tests for

developing

Flammability

developed

W . L. H a w k i n s
[ M o n t c l a i r , N e w Jersey, U S A ]

Polymers: Tests for Flammability

All p o l y m e r s will b u r n , given sufficient h e a t a n d
oxygen. S o m e , such as p o l y e t h y l e n e a n d p o l y ( m e t h y l
m e t h a c r y l a t e ) , b u r n readily u n d e r n o r m a l a m b i e n t
c o n d i t i o n s , w h e r e a s o t h e r s (e.g., p o l y t e t r a f l u o r o e t h y lene) b u r n only u n d e r e x t r e m e c o n d i t i o n s of a p p l i e d
h e a t o r oxygen c o n t e n t .
Typical characteristics m e a s u r e d by flammability
tests a r e ignitability, surface flame s p r e a d , h e a t release r a t e a n d s m o k e e v o l u t i o n . All of these flam
mability characteristics a r e extrinsic p r o p e r t i e s of a
p o l y m e r . U n l i k e intrinsic p r o p e r t i e s , they a r e d e p e n
d e n t o n external factors such as g e o m e t r y a n d orien
t a t i o n , as well a s t h e a m o u n t o f oxygen available for
c o m b u s t i o n . Because of this d e p e n d e n c y o n e x t e r n a l
c o n d i t i o n s , it is difficult t o predict " r e a l fire" p e r f o r m
ance by e x t r a p o l a t i o n from fire test results.

1. Fire Development

Regimes

T h e stages of a fire from ignition t o inferno a r e

characterized in Fig. 1 w h e r e fire intensity is p l o t t e d vs
time. T h e intensity scale c o n c e p t u a l l y represents t h e
fire g r o w t h p a r a m e t e r s of m a s s b u r n i n g r a t e , r a t e of
heat release, t e m p e r a t u r e a n d degree of i n v o l v e m e n t
of c o m b u s t i b l e s . T h r e e regimes of fire intensity a r e
shown: incipient, d e v e l o p i n g a n d fully d e v e l o p e d .
In the incipient regime t h e fire is small with t h e
materials involved in t h e fire being subjected t o , a n d
p r o d u c i n g , relatively low levels of t h e r m a l energy.
W h e n t h e r a t e of h e a t e v o l u t i o n from t h e b u r n i n g
materials exceeds t h e r a t e of h e a t loss t o t h e e n v i r o n
m e n t , the t e m p e r a t u r e rises, c a u s i n g t h e p o l y m e r s t o
b u r n faster. I n t h e d e v e l o p i n g regime, t h e t e m p e r a t u r e
a n d the heat-release r a t e increase. E n e r g y feedback
(convective a n d radiative) accelerates the r a t e of
b u r n i n g until t h e fire b e c o m e s limited by t h e avail
ability of either fuel o r oxygen. T h e fire is t h e n in t h e
fully developed regime.
F l a m m a b i l i t y tests for p o l y m e r s o p e r a t e in o n e o r
m o r e of t h e three regimes. M o s t small-scale l a b o r a
tory tests which utilize small ignition sources such as a

Time

Figure 1
Idealized fire development curve showing the three regimes
of fire growth ( Underwriters Laboratories, Melville,
New York. Reproduced with permission)

B u n s e n b u r n e r o p e r a t e in t h e incipient regime. T h e
p e r f o r m a n c e of a p o l y m e r in small-scale tests m a y
relate t o its p e r f o r m a n c e in a n incipient fire, b u t such
tests a r e n o t reliable p r e d i c t o r s of p e r f o r m a n c e in
d e v e l o p i n g o r fully d e v e l o p e d fires b e c a u s e they d o
n o t s i m u l a t e t h e t h e r m a l e n v i r o n m e n t of these larger
fires.
F l a m m a b i l i t y tests t h a t o p e r a t e in t h e developing
regime typically h a v e higher-energy ignition sources
t h a n incipient tests, a r e usually larger in scale a n d
often p r o v i d e c o n t a i n m e n t so t h a t h e a t loss is res
tricted t o p r o v i d e a severe t h e r m a l e n v i r o n m e n t .
P e r h a p s t h e m o s t widely used test in this regime is the
A S T M E 8 4 surface flame s p r e a d test w h i c h utilizes a
1.4 m l o n g ignition flame a n d a test s a m p l e 7.6 m long.
F l a m m a b i l i t y tests t h a t o p e r a t e in t h e fully d e
veloped regime typically h a v e high-flux ignition
sources a n d p r o v i d e for c o n t a i n m e n t of energy a n d
full i n v o l v e m e n t of test s a m p l e s . G e n e r a l l y , they a r e
used t o m e a s u r e t h e fire e n d u r a n c e of s t r u c t u r a l
e l e m e n t s such as walls.
In t h e section t h a t follows, s o m e of t h e widely used
flammability
tests a p p l i c a b l e t o p o l y m e r s h a v e been
selected a n d g r o u p e d a c c o r d i n g t o t h e regime of fire
intensity w h e r e they a r e m o s t applicable.

2. Incipient

Regime

Tests

I n A S T M D 1 9 2 9 (Test for Ignition Properties

of
Plastics) a 3 g s a m p l e is e x p o s e d t o flowing air (see
Fig. 2), a n d t h e air t e m p e r a t u r e is increased until the
plastic ignites. W h e n tests a r e c o n d u c t e d with a pilot
flame, t h e flash-ignition t e m p e r a t u r e is m e a s u r e d .

361

Polymers:

Tests for

Flammability

Opening
(2.5

cm

Support

diameter)
rod

Pilot

flame

Figure 2
Apparatus for measuring ignition temperatures by ASTM
D1929

W i t h o u t a pilot light, t h e self-ignition t e m p e r a t u r e is

determined.
T h e A S T M D 2 8 6 3 oxygen index test (see F i g . 3)
d e t e r m i n e s t h e relative flammability of plastics b y
m e a s u r i n g t h e m i n i m u m a m o u n t of oxygen, in a

m i x t u r e of o x y g e n a n d n i t r o g e n , t h a t is r e q u i r e d t o
support combustion. Materials can then be rank
o r d e r e d w i t h t h e f l a m m a b l e m a t e r i a l s h a v i n g low
oxygen indices (below t h e 21 % 0 2 in t h e air) a n d fireresistant o n e s h a v i n g indices c o n s i d e r a b l y a b o v e 21 % .
It is c o m m o n p r a c t i c e t o specify a m i n i m u m oxygen
index of 2 8 % for fire-resistant m a t e r i a l s .
T h e o x y g e n index test is o n e of t h e m o s t widely
used flammability tests. I t is easy t o r u n , r e p r o d u c i b l e
a n d , m o s t i m p o r t a n t l y , yields a q u a n t i t a t i v e result
r a t h e r t h a n a pass/fail result for assessing t h e flamma
bility of m a t e r i a l s . It is a n excellent test for q u a l i t y
c o n t r o l a n d research, b u t p r o v i d e s insufficient infor
m a t i o n for p r e d i c t i n g t h e p e r f o r m a n c e of a m a t e r i a l in
a d e v e l o p i n g fire.
Several factors affecting t h e o x y g e n i n d e x test h e l p
explain t h e p o o r c o r r e l a t i o n b e t w e e n oxygen index
test results a n d d e v e l o p i n g fire p e r f o r m a n c e . U n l i k e a
d e v e l o p i n g fire, t h e r e is m i n i m a l energy feedback
f r o m t h e flame t o t h e p o l y m e r s u b s t r a t e t h e oxygen
level is adjusted so t h e flame is o n t h e verge of
extinguishing. T h i s s i t u a t i o n is in c o n t r a s t t o a large
fire w h e r e r a d i a t i v e feedback is t h e d o m i n a n t m o d e of
energy transfer.
T h e o x y g e n i n d e x decreases with increasing s a m p l e
t e m p e r a t u r e . F o r e x a m p l e , t h e oxygen index of a
p o l y c h l o r o p r e n e c o m p o u n d c o n t a i n i n g clay a n d car
b o n b l a c k a s t h e p r i n c i p a l additives is 3 3 % a t r o o m
t e m p e r a t u r e a n d 1 9 % a t 300 C ( J o h n s o n 1974). T h e
o x y g e n index also decreases w i t h decreasing s a m p l e
t h i c k n e s s . A n o t h e r factor is t h a t t h e r m o p l a s t i c m a t e r
ials often d r i p a n d flow a w a y from t h e flame. Since t h e
melted t h e r m o p l a s t i c carries h e a t a w a y , a higher
o x y g e n c o n c e n t r a t i o n is n e e d e d t o m a i n t a i n c o m b u s
t i o n a n d a h i g h e r o x y g e n i n d e x results. I n a real fire,
t h e r m o p l a s t i c s will often d r i p a n d b u r n in a m o l t e n
pool.
I n U L 9 4 , Tests for Flammability
of Plastic
Mater
ials for Parts in Devices and Appliances ( U n d e r w r i t e r s

Sample -

19 m m
Flame ^

Burner ~

2+

Figure 3
Apparatus for measuring oxygen index by ASTM D2863

362

Figure 4
The UL94 vertical test setup

Polymers:

mm

Specimen

Tests for

Flammability

I n t h e U L 9 4 h o r i z o n t a l test (see Fig. 5), a B u n s e n

b u r n e r w i t h a 25 m m flame is a p p l i e d t o test specimens
13 c m l o n g a n d 13 m m in w i d t h a n d t h e r a t e of flame
s p r e a d over t h e h o r i z o n t a l surface is m e a s u r e d .
M a t e r i a l s t h a t h a v e flame s p r e a d r a t e s less t h a n
specified m a x i m a a r e r a t e d 9 4 H B . T h i s test is nearly
identical t o A S T M D 6 3 5 (Test Method for Rate of
Burning and/or Extent of Time of Burning of SelfSupporting Plastics in a Horizontal
Position).

Figure 5

The UL94 horizontal test setup

L a b o r a t o r i e s 1980), m e t h o d s a r e p r o v i d e d for b o t h
vertical a n d h o r i z o n t a l testing. I n t h e vertical test (see
Fig. 4), a B u n s e n b u r n e r with a 19 m m flame is
applied t o test specimens 13 c m l o n g , 13 m m in w i d t h
a n d u p t o 13 m m in thickness. T h e b u r n e r is placed
u n d e r t h e s a m p l e for 10 s, t h e n w i t h d r a w n until
flaming ceases a n d reapplied for a n a d d i t i o n a l 10 s.
T h e d u r a t i o n of flaming c o m b u s t i o n after each flame
a p p l i c a t i o n is used t o r a t e m a t e r i a l s as 9 4 V - 0 if
flaming c o m b u s t i o n averages 5 s o r less w i t h o u t d r i p
p i n g flaming particles a n d 94 V - l if flaming c o m b u s
tion averages 25 s o r less w i t h o u t d r i p p i n g flaming
particles. M a t e r i a l s t h a t p r o d u c e d r i p p i n g flaming
particles t h a t ignite surgical c o t t o n a r e r a t e d 94 V-2.

3. Developing

Regime

Tests

A S T M E 8 4 (Test for Surface Burning

Characteristics
of Building Materials) is t h e s t a n d a r d test t o certify
b u i l d i n g m a t e r i a l s for c o m p l i a n c e with building
codes. It utilizes the Steiner t u n n e l furnace (see Fig. 6)
w h e r e a 7.3 m l o n g by 51 c m wide test specimen forms
t h e r o o f of the furnace. T h e lower surface of the
specimen is ignited by a large (1.4 m ) m e t h a n e flame.
1
A 1.22 m s " draft a n d a n e n c l o s u r e , w h i c h p r o v i d e s
for c o n s e r v a t i o n of h e a t energy, aid flame s p r e a d . T h e
fire is o b s e r v e d t h r o u g h w i n d o w s in t h e t u n n e l wall.
T h e t u n n e l is c a l i b r a t e d w i t h red o a k , which
s p r e a d s flame 5.9 m from t h e e n d of t h e ignition flame
t o t h e t u n n e l e n d in 15.5 m i n , a n d w i t h a s b e s t o s
cement board, which does not burn. Asbestos cement
b o a r d is assigned a flame s p r e a d classification of 0 a n d
red o a k 100.
A s m o k e value is d e t e r m i n e d b y m e a s u r i n g the
p e r c e n t a t t e n u a t i o n of a b e a m of light across the

Figure 6

The Steiner tunnel furnace for measuringflamespread and smoke developed by A S T M E84
363

Polymers:

Tests for

Flammability

Smoke detector
Combustion gas igniter
Plaque sample
Heating elements
Environmental
chamber
To gas supply
Pilot flame

Air inlet

Figure 7
The Ohio State University heat-release-rate calorimeter
(ASTM E906)

e x h a u s t d u c t of t h e tunnel. T h e a r e a u n d e r t h e p e r c e n t
a t t e n u a t i o n vs time curve for red o a k in a 10 m i n test
is assigned a value of 100. T h e s m o k e values of o t h e r
m a t e r i a l s a r e r e p o r t e d relative t o t h e red o a k value of
100.
T h e c o m b i n a t i o n of a large ignition flame, with a
heat-release r a t e of 88 k W , a n d a n insulated furnace
which r e r a d i a t e s h e a t o n c e it is h e a t e d u p p r o v i d e s a
severe test e n v i r o n m e n t . M e a s u r e m e n t s m a d e b y
P a r k e r (1977) indicate t h a t t h e s a m p l e in t h e flame

i m p i n g e m e n t a r e a is subjected t o 4 0 - 6 0 k W m "
incident h e a t flux.
M a t e r i a l s with a flame s p r e a d classification of 25 o r
less (less t h a n 1.5 m flame s p r e a d ) a r e generally
r e g a r d e d b y b u i l d i n g c o d e s a s p r o v i d i n g a high degree
of fire safety. T h e c o r r e l a t i o n of a low
flame-spread
classification w i t h g o o d fire p e r f o r m a n c e w a s e s t a b
lished for cellulosic ( w o o d ) m a t e r i a l s , b u t recent ex
periences w i t h t h e r m o p l a s t i c f o a m s s h o w t h a t A S T M
E 8 4 s h o u l d n o t b e e m p l o y e d a s t h e sole s o u r c e of fire
h a z a r d r a t i n g for p o l y m e r i c m a t e r i a l s .
T h e r a t e a t which a m a t e r i a l b u r n s (i.e., t h e r a t e a t
which it releases h e a t ) is a n i m p o r t a n t
flammability
p r o p e r t y since it is a m e a s u r e of fire intensity. R a t e of
h e a t release c a l o r i m e t e r s m e a s u r e rates of h e a t a n d
s m o k e release of a m a t e r i a l subjected t o a n externally
applied h e a t flux. U n l i k e m o s t o t h e r fire tests which
utilize only o n e e x p o s u r e c o n d i t i o n , heat-release-rate
c a l o r i m e t e r s allow t h e incident h e a t flux t o b e varied
from test t o test a n d , h e n c e , t h e influence of flux o n
release r a t e s c a n b e d e t e r m i n e d .
I n t h e O h i o State University ( O S U ) calorimeter (see
Fig. 7), w h i c h is used in A S T M E906 {Test Method for
Heat and Visible Smoke Release Rates of Materials
and Products), incident flux c a n be varied from a level
- 2
characteristic of a n incipient fire ( 0 - 1 0 k W m ) o n
t h r o u g h t h o s e characteristics of developing fires, u p t o
values associated w i t h fully d e v e l o p e d fires ( 8 0 2
l O O k W m " ) . R o w a n a n d L y o n s (1978) h a v e p u b
lished s o m e e x p e r i m e n t a l results t h a t d e m o n s t r a t e t h e
i m p o r t a n c e of externally i m p o s e d h e a t flux o n t h e
b u r n i n g b e h a v i o r of m a t e r i a l s . F i g u r e 8 s h o w s p e a k
heat-release rates vs incident applied flux for a series
of fire r e t a r d a n t p o l y u r e t h a n e a n d p o l y i s o c y a n u r a t e
f o a m s . T h e r a t e of b u r n i n g generally increases with
increasing incident flux a n d for flame r e t a r d a n t

250 r

!!"!!

11

The influence of externally applied flux on peak

heat-release rates for a series of polyurethane and
polyisocyanurate foams (after Rowan and Lyons 1978.
Technomic, Westport, Connecticut. Reproduced with
permission)

364

Incident heat flux (kW nrT )

Figure 9
The influence of externally applied flux on total smoke
emissions for various polymers (courtesy of Professor
. E. Smith, Ohio State University)

Polymers:

Tests for

Flammability

T h e m o s t widely used i n s t r u m e n t for m e a s u r i n g

s m o k e is t h e N a t i o n a l B u r e a u of S t a n d a r d s s m o k e
c h a m b e r (see F i g . 10). T e s t c o n d i t i o n s a r e specified in
A S T M E 6 2 2 {Standard Test Method for Specific Op
tical Density of Smoke Generated by Solid
Materials).
2
T h e specimen is subjected t o a 2 5 k W m
incident
flux. Tests a r e r u n either in t h e flaming m o d e w h e r e
t h e s a m p l e is ignited by a pilot flame o r in the
s m o l d e r i n g m o d e w h e r e t h e pilot flame is n o t used.
S m o k e is a c c u m u l a t e d w i t h i n t h e s m o k e c h a m b e r b o x
a n d t h e specific optical density of t h e s m o k e is
r e p o r t e d . Specific optical density Ds is defined by

Photodetector

Light
source

Z ) s^ ( F / L ^ ) l o g ( 1 0 0 / r )

Radiant
heater

Figure 10
National Bureau of Standards smoke chamber (ASTM
E662)

m a t e r i a l s there is a m i n i m u m flux r e q u i r e d t o sustain

c o m b u s t i o n . T h e r a n k o r d e r i n g of m a t e r i a l s c a n
c h a n g e w h e n flux is increased. T h e m a t e r i a l r e p r e
sented by the d a s h e d line is best (i.e., it h a s t h e lowest
2
heat-release rate) b e l o w 40 k W m incident flux, b u t
it is t h e w o r s t o r next t o w o r s t m a t e r i a l a t incident
2
fluxes a b o v e 45 k W m " .
S m o k e e v o l u t i o n is also d e p e n d e n t o n incident h e a t
flux. F i g u r e 9 s h o w s t h e v a r i a t i o n in t o t a l s m o k e
o u t p u t vs incident flux for several p o l y m e r s tested in
the O S U release r a t e c a l o r i m e t e r .

w h e r e V is t h e c h a m b e r v o l u m e , L is t h e optical p a t h
length, A is t h e e x p o s e d specimen a r e a a n d is the
p e r c e n t t r a n s m i t t a n c e of t h e light b e a m .
T h e r e a r e several differences b e t w e e n s m o k e
m e a s u r e m e n t s in t h e N B S c h a m b e r a n d in the O S U
release-rate c a l o r i m e t e r . T h e N B S c h a m b e r is n o r
mally r u n a t only o n e s t a n d a r d i z e d flux. T h u s it
c a n n o t be related t o a real fire s i t u a t i o n w h e r e m a t e r
ials a r e e x p o s e d t o a s p e c t r u m of fluxes. T h e N B S
c h a m b e r m e a s u r e s t o t a l s m o k e b y a c c u m u l a t i n g it
within t h e b o x w h e r e a s t h e O S U c a l o r i m e t e r o p e r a t e s
with a n air flow t h r o u g h t h e c o m b u s t i o n c h a m b e r a n d
t o t a l s m o k e is d e t e r m i n e d b y i n t e g r a t i o n of the in
s t a n t a n e o u s s m o k e values. B o t h test m e t h o d s r e p o r t
s m o k e in optical density, w h i c h is linearly related t o
h u m a n visibility t h r o u g h s m o k e . B o t h m e t h o d s differ
greatly from t h e A S T M E 8 4 s m o k e m e a s u r e m e n t ,
w h e r e t h e a m o u n t of s m o k e g e n e r a t e d is d e p e n d e n t
o n t h e flame s p r e a d value of t h e m a t e r i a l tested.

4. Fully Developed

Regime

Tests

A S T M E l 19 (Fire Tests of Building Construction

and
Materials)
is used for r a t i n g t h e fire e n d u r a n c e of
m a t e r i a l s a n d s t r u c t u r e s . L a r g e specimens, m i n i m u m
2
e x p o s e d a r e a 9.3 m , a r e e x p o s e d t o a s t a n d a r d fire
w h o s e t i m e - t e m p e r a t u r e c u r v e (see F i g . 11) is c h a r a c
teristic of a postflashover fire. Assemblies a r e r a t e d b y
t h e elapsed time t o failure. Several failure criteria are
p r o v i d e d , such as ignition of c o t t o n w a s t e o n t h e
u n e x p o s e d side of t h e specimen o r t e m p e r a t u r e s
exceeding 139 C o n t h e u n e x p o s e d side.
A S T M E 8 1 4 (Fire Test of Through Penetration Fire
Stops) is a p p l i c a b l e t o p o l y m e r i c m a t e r i a l s used in
p e n e t r a t i o n s (e.g., cables, plastic d u c t s a n d fire-stop
m a t e r i a l s ) . It utilizes t h e A S T M E l 19 t i m e - t e m p e r a
t u r e e x p o s u r e s with a fire-stop a n d p e n e t r a t i o n in
place t o test t h e e n d u r a n c e of a firestop assembly.

Time

(h)

Figure 11
The ASTM El 19 time-temperature curve for testing the
fire endurance of structures

Bibliography
American Society for Testing and Materials 1966 Sym
posium on Fire Test MethodsRestraint and Smoke 1966,

365

Polymers:

Tests for

Flammability

ASTM Special Technical Publication 422. ASTM, Phila

delphia, PA
American Society for Testing and Materials 1972 Ignition,
Heat Release and Noncombustibility of Materials, ASTM
Special Technical Publication 502. ASTM, Philadelphia,
PA
Hilado C J 1973 Flammability Test Method Handbook.
Technomic, Westport, CT
Hilado C J (ed.) 1974 Flammability Handbook for Plastics,
2nd edn. Technomic, Westport, CT
Johnson R 1974 A general correlation of the flammability
of natural and synthetic polymers. J. Appl. Polym. Sci. 18:
491-504
Kanury A M, Alvares J, Martin S 1977 Flammability
Testing of Polymers. Manufacturing Chemists Associ
ation, Washington, DC
National Materials Advisory Board 1979 Fire Safety
Aspects of Polymeric MaterialsII: Test Methods, Speci
fications and Standards, Publication NMAB 318-2.
National Academy of Sciences, Washington, DC
Parker W J 1977 An Investigation of the Fire Environment in
the ASTM E84 Tunnel Test, National Bureau of Stan
dards Technical Note 945. US Government Printing
Office, Washington, DC
Paul 1987 Fire testing in polymers. Prog. Rubber Plast.
Technol. 3(2): 23-43
Rowan J W, Lyons J W 1978 The importance of externally
imposed heat flux on the burning behavior of materials. J.
Cell. Plast. 14: 25-31
Smith , Harmathy (eds.) 1978 Design of Buildings for
Fire Safety, ASTM Special Technical Publication 685.
ASTM, Philadelphia, PA
Underwriters Laboratories 1980 Tests for Flammability of
Plastic Materials for Parts in Devices and Appliances,
UL94. Underwriters Laboratories, Melville, NY
S. K a u f m a n
[ A T & T Bell L a b o r a t o r i e s , N o r c r o s s ,
Georgia, USA]

p o l y m e r s a r e tensile, flexural, i m p a c t , creep a n d fati

gue stress r e l a x a t i o n as well as compressive a n d s h e a r
properties.
M o s t technical d a t a available t o the engineer t o
assist in m a k i n g a choice of m a t e r i a l s are f o u n d in
technical literature supplied by v e n d o r s . T h e s e a r e
generally useful for m a k i n g p r e l i m i n a r y selections of
p o t e n t i a l m a t e r i a l s b u t d o n o t h e l p w h e n several
different m a t e r i a l s a r e u n d e r c o n s i d e r a t i o n . T h i s is
b e c a u s e t h e test c o n d i t i o n s a n d s a m p l e g e o m e t r y
often v a r y from o n e m a t e r i a l t o a n o t h e r . A l s o , basic
m a t e r i a l p r o p e r t y d a t a of this t y p e d o n o t represent
c o n d i t i o n s of use.
T h i s article p r e s e n t s t h e basic steps in d e t e r m i n i n g
t h e m e c h a n i c a l p r o p e r t i e s of p o l y m e r s a n d suggested
t e c h n i q u e s for e v a l u a t i n g t h e p r o p e r t i e s in relation t o
t h e a p p l i c a t i o n . In the latter case, as m u c h i n f o r m a
tion as possible r e g a r d i n g t h e service c o n d i t i o n s of t h e
fabricated p a r t m u s t be c o n s i d e r e d w h e n selecting t h e
m a t e r i a l . C o n d i t i o n s of l o a d i n g , t e m p e r a t u r e , c h e m
ical e x p o s u r e (if a n y ) a n d expected service life m u s t all
be included.
Basic to a n y d e t e r m i n a t i o n of m e c h a n i c a l p r o p e r
ties is a review of t h e design p a r a m e t e r s t o establish
t h e r e q u i r e d p r o p e r t i e s . It m u s t also be established
w h e t h e r specific test p r o c e d u r e s a r e prescribed in t h e
p u r c h a s e specifications. If so, the p r o c e d u r e s will
m o s t p r o b a b l y be t h o s e laid d o w n by t h e v a r i o u s
s t a n d a r d s o r g a n i z a t i o n s . T h e s e p r o c e d u r e s define t h e
test c o n d i t i o n s , preferred s a m p l e g e o m e t r y a n d s a m
ple p r e p a r a t i o n a n d c o n d i t i o n i n g m e t h o d s , a n d also
specify the r e c o m m e n d e d p r o c e d u r e s t o be used w h e n
s a m p l e s a r e t a k e n from fabricated p a r t s .
T h e test p r o c e d u r e s described h e r e relate t o the
basic p r o p e r t i e s e m p l o y e d in design a n d use of
polymers.

Polymers: Tests for Mechanical

Properties

1.

P o l y m e r s a r e used t o a n increasing extent for a p p l i c a

tions in w h i c h they replace t r a d i t i o n a l m a t e r i a l s of
c o n s t r u c t i o n , such as m e t a l s a n d w o o d , w h e r e their
lower weight, resistance t o c o r r o s i o n , ease of fabrica
tion a n d potentially lower cost offer significant a d v a n
tages. In a d d i t i o n , n e w e r p o l y m e r s a r e replacing older
p o l y m e r i c systems; for e x a m p l e , engineering t h e r m o
plastics a r e replacing t h e r m o s e t t i n g p o l y m e r s , in a p
plications w h e r e e c o n o m y of m a n u f a c t u r e a n d design
latitude favor t h e r m o p l a s t i c p o l y m e r s .
Since there a r e m a n y a r e a s w h e r e p o l y m e r s a r e
being considered a n d there a r e literally h u n d r e d s of
p o l y m e r s t o c h o o s e from, including b l e n d s , alloys a n d
c o m p o s i t e s , it is necessary t o u n d e r s t a n d t h e m e c h a n i
cal p r o p e r t i e s of p o l y m e r s t o be able t o design func
tional items which c a n w i t h s t a n d t h e expected stresses
in use. Typical p r o p e r t i e s of interest t o the designer o r
engineer faced with selection a n d specification of

T h e tensile b e h a v i o u r of a p o l y m e r is p r o b a b l y t h e
m o s t f u n d a m e n t a l m e c h a n i c a l p r o p e r t y used in t h e
e v a l u a t i o n of p o l y m e r s . T h e basic m e t h o d is
e m p l o y e d t o d e t e r m i n e yield s t r e n g t h , u l t i m a t e
s t r e n g t h a n d e l o n g a t i o n p r o p e r t i e s as well as v a r i o u s
m o d u l i w h i c h a r e i m p o r t a n t in designing with
polymers. T h e stress-strain diagram obtained can
also be used t o m e a s u r e t h e ability of a p o l y m e r t o
a b s o r b energy. T h i s is p a r t i c u l a r l y useful w h e n testing
vulcanized e l a s t o m e r s .
T h e tensile s t r e n g t h of a m a t e r i a l is the r a t i o of the
force a p p l i e d t o t h e m a t e r i a l a t r u p t u r e t o its original
cross-sectional a r e a . T h i s p r o p e r t y is typically called
t h e u l t i m a t e tensile s t r e n g t h , t h a t is, t h e s t r e n g t h a t
b r e a k , a n d is usually expressed in m e g a p a s c a l s . T h e
c o r r e s p o n d i n g extension is called the u l t i m a t e strain
o r u l t i m a t e e l o n g a t i o n a n d is typically given as a
percentage.

366

Tensile

Properties

Polymers:

Load
cell
Moving
crosshead

Test
sample

Moving
crosshead

Direction
of t r a v e l

Tests for Mechanical

Properties

Direction
of travel

Test
_
sample
Loadcell
Stationary
crossheaa

Stationary
crosshead

(a )

Figure 1
Schematic arrangements for determination of mechanical
properties of polymers: (a) tensile and (b) flexural

T h e e q u i p m e n t r e q u i r e d consists of a m a c h i n e
h a v i n g a m o v i n g a n d a fixed c r o s s h e a d t o w h i c h
c l a m p i n g fixtures a r e affixed t o h o l d t h e specimen.
O n e of t h e c l a m p s is a t t a c h e d t o a l o a d cell w h i c h m a y
be m o u n t e d o n either c r o s s h e a d . T h e m o v a b l e c r o s s h e a d c a n b e driven a t a c o n s t a n t r a t e w h i c h c a n b e
-1
1
varied from 0.25 m m m i n
t o 1250 m m m i n " o r
1
s o m e t i m e s u p t o 25 000 m m m i n " . O t h e r types of
e q u i p m e n t a r e able t o a p p l y a c o n s t a n t r a t e of l o a d i n g
to a specimen.
T h e l o a d o r resistance of t h e specimen t o d e f o r m a
tion is c o n t i n u o u s l y r e c o r d e d a n d t h e extension deter
m i n e d by use of a n e x t e n s o m e t e r c o n n e c t e d directly t o
the specimen o r b y m e a s u r i n g t h e d i s t a n c e b e t w e e n
g a u g e m a r k s o n t h e specimen d u r i n g t h e p r o g r e s s of
the test. T o p r e v e n t failure of t h e s a m p l e in t h e grips,
the test specimens usually h a v e a r e d u c e d cross sec
tion a n d are s o m e t i m e s referred t o as " d u m b - b e l l " o r
" d o g - b o n e " specimens. F i g u r e la illustrates t h e speci
m e n l o a d e d in tension. T h e force is r e c o r d e d u p t o t h e
p o i n t of r u p t u r e . T h e s e r e a d i n g s a r e c o n v e r t e d t o
stresses a n d a r e p l o t t e d a g a i n s t strain. F i g u r e 2 illus
trates typical s t r e s s - s t r a i n d i a g r a m s for t h e m a j o r
types of p o l y m e r .
A s stated, t h e tensile s t r e n g t h is t h e r a t i o of force t o
unit a r e a a n d is expressed a s follows:

Strain, e

Strain, e

Figure 2
Tensile curves for polymeric materials: (a) semicrystalline
polymer (
stress-strain curve, tangent modulus
of elasticity); (b) amorphous ductile polymer (
stress-strain curve, secant modulus of elasticity);
(c) amorphous brittle polymer (
stress-strain curve,
offset modulus); and (d) crosslinked rubber
(
stress-strain curve, 300% modulus)

where force F is expressed in n e w t o n s a n d t h e crosssectional a r e a A is in s q u a r e m e t e r s . S t r a i n is given b y

the following expression:

F e a t u r e s t o b e n o t e d a r e yielding, n e c k i n g a n d
strain h a r d e n i n g . Semicrystalline p o l y m e r s such as
p o l y e t h y l e n e a n d p o l y p r o p y l e n e s h o w yielding, fol
l o w e d b y n e c k i n g , t h e n a n increase in s t r e n g t h before
r u p t u r e , as in F i g . 2a. F i g u r e 2 b s h o w s a ductile
p o l y m e r such as plasticized p o l y v i n y l chloride) w h i c h
s h o w s yielding a n d e l o n g a t i o n before failure. F i g u r e
2c s h o w s t h e b e h a v i o r of a brittle p o l y m e r such a s
p o l y s t y r e n e ; t h e s t r e s s - s t r a i n c u r v e s h o w s n o yield
p o i n t a n d low e l o n g a t i o n before failure. C r o s s l i n k e d
r u b b e r s b e h a v e as in F i g . 2d.
T h e m o d u l u s m a y also b e o b t a i n e d from t h e s t r e s s strain o r l o a d - d e f o r m a t i o n c u r v e . T h e m o d u l u s value
m o s t frequently used in design is Y o u n g ' s m o d u l u s E,
w h i c h is d e t e r m i n e d from t h e initial slope of the
s t r e s s - s t r a i n curve:

e = ( / - / 0) / / 0

= /

= F/A

0)

(2)

w h e r e / is the final length a n d / 0 is t h e original length.

Typically, strain is r e p o r t e d as p e r c e n t strain o r
percent e l o n g a t i o n , which is 100. T h e p r o p e r t i e s
calculated as s h o w n a r e referred t o as t h e engineering
stress a n d strain o r e l o n g a t i o n . T h e s e values a r e
s h o w n as t h e u l t i m a t e p r o p e r t i e s o r b r e a k i n g stress
a n d strain.

(3)

T h e d a s h e d line in F i g . 2a is a n e x t r a p o l a t i o n of t h e
initial linear p o r t i o n of t h e c u r v e for t h e c a l c u l a t i o n of

E.
O t h e r m o d u l u s values c o m m o n l y r e p o r t e d a r e t h e
secant m o d u l u s , t a n g e n t m o d u l u s a n d , in t h e case of
e l a s t o m e r s , t h e 3 0 0 % m o d u l u s ; t h e stress a t 3 0 0 %
e l o n g a t i o n is a c o m m o n l y r e p o r t e d p r o p e r t y . T h e s e

367

Polymers:

Tests for Mechanical

Properties

are s h o w n by a d a s h e d line in Figs. 2 b , 2c a n d 2d,

respectively. T h e relationship between the s h e a r
m o d u l u s a n d tensile ( Y o u n g ' s ) m o d u l u s is given by
=2G(l+v)

(4)

where is the tensile m o d u l u s , G is t h e shear m o d u l u s

a n d is P o i s s o n ' s r a t i o . T h i s relation c a n be used t o
d e t e r m i n e the shear m o d u l u s from tensile m e a s u r e
m e n t s w h e n P o i s s o n ' s r a t i o is k n o w n for the m a t e r i a l
u n d e r test.
M o d u l u s values a r e useful w h e n designing with
p o l y m e r s , b u t in using the d a t a o b t a i n e d by these
m e t h o d s , c a u t i o n m u s t be exercised t h a t they a r e n o t
e x t r a p o l a t e d t o e x t r e m e c o n d i t i o n s of service.

2. Flexural

Properties

M a n y uses of p o l y m e r s involve their subjection t o

b e n d i n g o r flexural stresses. In these cases, k n o w l e d g e
of the response of the m a t e r i a l t o such c o n d i t i o n s is
required. O n e of the m o s t useful m e t h o d s of deter
m i n i n g the flexural p r o p e r t i e s of p o l y m e r s e m p l o y s
the s a m e basic e q u i p m e n t as used t o d e t e r m i n e the
tensile p r o p e r t i e s . T h i s t e c h n i q u e m a k e s use of a
specially c o n s t r u c t e d fixture which substitutes the
flexural test fixture for the grips used in tensile testing.
A n o t h e r c o n v e n i e n t m e t h o d is to use the tensile
m a c h i n e in the c o m p r e s s i o n m o d e : the tensile l o a d cell
is replaced by a compressive l o a d cell a n d the m o v a b l e
crosshead is m o v e d t o w a r d s the s t a t i o n a r y c r o s s h e a d .
A schematic d i a g r a m of this test a r r a n g e m e n t is
s h o w n in Fig. l b in the t h r e e - p o i n t b e n d i n g configu
ration.
A typical l o a d - d e f o r m a t i o n c u r v e for a p o l y m e r
tested in flexure is similar t o the initial p o r t i o n of a
tensile test, as s h o w n in Fig. 2. T h e s e curves c a n be
used t o d e t e r m i n e flexural yield s t r e n g t h as well as the
t a n g e n t o r secant m o d u l u s , as illustrated in Figs. 2a,
b.
T h e r a t e of straining the o u t e r fibers is usually
- 1
0.01 s . T o o b t a i n this strain rate, the c r o s s h e a d
speed varies with t h e s u p p o r t s p a n L a n d t h e d e p t h o r
thickness of the s a m p l e d as given by
2

R = kL /6d

(5)

where is t h e strain r a t e a n d R is the c r o s s h e a d speed.

T h e load is applied until the s a m p l e fails or t h e strain
reaches 0.05 in the o u t e r fibers. T h e deflection at this
latter p o i n t is calculated as
2

D = 0.05 L /6d

(7)

w h e r e erB is the b e n d i n g stress (Pa), is t h e force ( N ) ,

L is the s p a n length (m), b is the s a m p l e w i d t h (m) a n d
d is the thickness (m).
T h e m o d u l u s of elasticity in b e n d i n g EB is calcu
lated, as stated, from the l o a d d e f o r m a t i o n curve b y
c o n s t r u c t i n g t h e t a n g e n t t o t h e initial straight p o r t i o n
of the c u r v e a n d d e t e r m i n i n g t h e slope m of the
1
tangent (N m " ) :
3

EB = L m/4bd

(8)

T h e secant m o d u l u s of elasticity in b e n d i n g m a y also

be calculated for a n y specified strain by c o n s t r u c t i n g a
secant from t h e origin t o the selected strain, d e t e r m i n
ing t h e slope m a n d a p p l y i n g E q n . (8).
In the case of high strain rates, s o m e slippage m a y
o c c u r a t t h e s u p p o r t s , r e q u i r i n g modified test p r o c e d
ures. Similarly, large s p a n - d e p t h ratios require cor
rection factors.
F l e x u r a l p r o p e r t i e s a r e often useful in the design
a n d selection of m a t e r i a l s , p a r t i c u l a r l y w h e n the fabri
c a t e d p a r t is subjected to b e n d i n g stresses. It s h o u l d
be n o t e d here t h a t t h e m o d u l u s of elasticity deter
m i n e d in tension is n o t equivalent t o the m o d u l u s of
elasticity EQ d e t e r m i n e d in flexure.

3. Compressive

Strength

C o m p r e s s i v e s t r e n g t h d a t a a r e useful for predicting

the service life of p o l y m e r i c devices which a r e used in
l o a d - b e a r i n g a p p l i c a t i o n s . T h e compressive yield
stress, strain a n d m o d u l u s of elasticity as well as
u l t i m a t e c o m p r e s s i v e s t r e n g t h m a y be d e t e r m i n e d for
m a t e r i a l s subject t o brittle failure.
T h e m a c h i n e used is a tensile testing m a c h i n e set u p
in t h e c o m p r e s s i o n m o d e . Special test fixtures a r e
r e q u i r e d t o p r o v i d e vertical s u p p o r t for thin speci
m e n s . T h e testing a r r a n g e m e n t is similar t o t h a t used
for flexural p r o p e r t i e s , as s h o w n in Fig. l b , with the
t h r e e - p o i n t b e n d i n g fixture replaced by a fixture t o
s u p p o r t the specimen for compressive loading. T h e
l o a d - d e f o r m a t i o n c u r v e from which the s t r e s s - s t r a i n
c u r v e is o b t a i n e d is similar t o t h a t for tensile a n d
flexural tests a t low levels of strain (Fig. 2). T h e
compressive stress, strain a n d m o d u l u s a r e calculated
as for t h e tensile p r o p e r t i e s , by E q n s . (1), (2) a n d (4),
respectively.

(6)

H i g h e r strain rates m a y be used t o cause r u p t u r e

before the 0.05 limit o r to d e t e r m i n e the flexural
properties under loading conditions approximating
those expected in use.
T h e m a x i m u m stress u n d e r t h r e e - p o i n t l o a d i n g
c o n d i t i o n s occurs a t the m i d p o i n t a n d c a n be calcu
lated as

368

= 3PL/2bd

4. Time-Dependent

Properties

C r e e p a n d stress r e l a x a t i o n a r e i m p o r t a n t p r o p e r t i e s
of p o l y m e r s , since they m u s t be c o n s i d e r e d in t h e
design of a n y fabricated p a r t subjected t o c o n s t a n t
l o a d o r d e f o r m a t i o n . T h e influence of the e n v i r o n
m e n t t o which t h e p a r t is e x p o s e d m u s t also be t a k e n
i n t o c o n s i d e r a t i o n , including n o t only t h e v a r i a t i o n s

Polymers:

(a)

(c )

-/

time^O

= /?

-/

Creep

time =

[+/

0
'h
time = h

Stress relaxation

Figure 3
Time-dependent properties: (a) creep curves, strain vs time
(log hours) under load (; (b) creep modulus time (log
hours) at temperatures Tt\ (c) stress relaxation, stress time
(log hours) under deformation ,; and (d) schematic
representations of creep and stress relaxation

in t e m p e r a t u r e b u t also p o t e n t i a l e x p o s u r e t o c h e m
ical agents w h i c h m i g h t accelerate fracture in service.
C r e e p occurs w h e n t h e p o l y m e r is subjected t o a
c o n s t a n t stress below t h e yield stress o r fracture stress
of a m a t e r i a l . After a n initial d e f o r m a t i o n 0 which is
p r o p o r t i o n a l t o the applied stress , the m a t e r i a l
c o n t i n u e s to e l o n g a t e o r d e f o r m u n d e r t h e a p p l i e d
load until fracture o c c u r s . F r a c t u r e m a y be either
ductile o r brittle. T h e strain a t a n y time is a function
of the original strain which o c c u r s u p o n l o a d i n g plus
the t i m e - d e p e n d e n t c o m p o n e n t of strain. T h e strain
d e p e n d s o n t h e level of stress a n d t h e t e m p e r a t u r e a t
which the test is carried o u t . A general expression for
t i m e - d e p e n d e n t strain is
e(t) = e0(o) +

F[t g(o)]

(9)

w h e r e ( is the strain a t t i m e t resulting from a p p l i e d

stress , 0 is t h e initial strain resulting from a p p l i c a
n
tion of er, a n d F[t g{a)] is t h e t i m e - d e p e n d e n t c o m
p o n e n t of strain w h i c h is t h e i n c r e m e n t a l increase in
strain at time t resulting from the applied stress .
This c o n c e p t is discussed by Levy (1979).
C r e e p m e a s u r e m e n t s a r e m a d e by a p p l y i n g a static
load t o the s a m p l e a n d r e c o r d i n g t h e d e f o r m a t i o n as a
function of time. T h e d a t a a r e t h e n used t o c o n s t r u c t a
creep curve. It is useful to c o n d u c t t h e test u n d e r
several different l o a d s a n d p l o t t h e d a t a for e a c h test
c o n d i t i o n . A typical series of creep curves is s h o w n in
Fig. 3a (5 > 4 > 3 > 2 > ). T h e s e d e t e r m i n a t i o n s

Tests for Mechanical

Properties

a r e m a d e at c o n s t a n t t e m p e r a t u r e so t h a t t h e strain is
a function of stress a n d time h ( h o u r s ) at the test
t e m p e r a t u r e T. M e a s u r e m e n t s m a d e at several tem
p e r a t u r e s , including t h o s e expected in practice, allow
service life to be p r e d i c t e d , t a k i n g i n t o a c c o u n t the
v a r i a t i o n of creep with t e m p e r a t u r e as well as load.
F o r design p u r p o s e s t h e m o d u l u s is used t o predict
d e f o r m a t i o n u n d e r applied stress; h o w e v e r , since it
h a s been s h o w n t h a t the strain increases with time, it
follows t h a t t h e m o d u l u s also c h a n g e s with time. T h i s
c h a n g e is d e t e r m i n e d by dividing the applied stress
by t h e strain a t time h a n d p l o t t i n g the m o d u l u s Ecr
a g a i n s t time. T h e m o d u l u s value is called the creep
m o d u l u s . F i g u r e 3b illustrates this p r o p e r t y for a
Tx.
series of t e m p e r a t u r e s , w h e r e T4> T3> T2>
Stress r e l a x a t i o n is the decrease in stress with time
for a m a t e r i a l subjected t o c o n s t a n t d e f o r m a t i o n . It is
related t o creep. In this case t h e s a m p l e is strained t o a
p r e d e t e r m i n e d level a n d the r e d u c t i o n in force is
m e a s u r e d as a function of time. A stress relaxation
c u r v e is s h o w n in F i g . 3c. I n this case t h e stress is
p l o t t e d against time (In h) for a series of strain levels ,
where 4 > 3 > 2 >
A s c h e m a t i c a r r a n g e m e n t for t h e d e t e r m i n a t i o n of
creep a n d stress r e l a x a t i o n is s h o w n in Fig. 3d. In this
e x a m p l e t h e c r e e p is t h e increase in length a t time h
c a u s e d b y force F0. T h e stress r e l a x a t i o n indicates a
decrease in stress, F0 > Fh, at time h resulting from a
c o n s t a n t deflection .
F u r t h e r discussion o n t i m e - d e p e n d e n t p r o p e r t i e s is
to be f o u n d in N e l s o n (1974a, b ) , T u r n e r (1974), Levy
(1979) a n d W a r d (1983).

5. Impact

Properties

T h e i m p a c t b e h a v i o r of p o l y m e r s is a c a u s e for
c o n c e r n a m o n g designers b e c a u s e t h e p e r f o r m a n c e of
fabricated p a r t s subjected t o i m p a c t l o a d s or t o
d e f o r m a t i o n at high strain rates is often difficult t o
predict. It is also a c o m p l i c a t e d m a t t e r to develop
tests w h i c h c a n a c c u r a t e l y m o d e l t h e a c t u a l use c o n
d i t i o n s for t h e m a t e r i a l u n d e r c o n s i d e r a t i o n . In m a n y
cases failure occurs a t i m p a c t l o a d s far below the
i n h e r e n t s t r e n g t h o r t o u g h n e s s of the m a t e r i a l . T h e s e
p r o b l e m s h a v e led t o a large n u m b e r of m e t h o d s for
d e t e r m i n i n g the i m p a c t p r o p e r t i e s of p o l y m e r s a n d
likewise a large n u m b e r of m a c h i n e s of increasing
s o p h i s t i c a t i o n t o m e a s u r e the b e h a v i o r of p o l y m e r s
subjected t o i m p a c t l o a d i n g c o n d i t i o n s . I n s t r u m e n t e d
i m p a c t testing m a c h i n e s h a v e b e c o m e p o p u l a r in
recent years b e c a u s e m o r e i n f o r m a t i o n is g e n e r a t e d
r e g a r d i n g t h e m o d e of failure. T h e s e techniques h a v e
been a p p l i e d t o tensile i m p a c t , C h a r p y i m p a c t a n d
falling weight i m p a c t tests, a m o n g o t h e r s .
In t h e i n s t r u m e n t e d i m p a c t tests, a l o a d - t i m e
( d e f o r m a t i o n ) c u r v e is g e n e r a t e d as well as a n indica
tion of t h e energy r e q u i r e d t o cause failure. A typical
c u r v e from a n i n s t r u m e n t e d C h a r p y test is s h o w n in

369

Polymers:

Tests for Mechanical

Properties

failure a n d failure height in m e t e r s for a specified d r o p

weight.
O t h e r p r o p e r t i e s of interest t o designers a r e t h e
b e h a v i o r of p o l y m e r s in friction, w e a r a n d fatigue, as
well a s t h e d y n a m i c m e c h a n i c a l b e h a v i o r . T e s t m e t h
o d s used t o d e t e r m i n e these p r o p e r t i e s a r e described
in t h e references cited in t h e b i b l i o g r a p h y .
6. Data

Figure 4
Impact properties and testing: (a) curves for force
(
) and energy ( ) from instrumented impact test;
(b) schematic of pendulum-type impact tester;
(c) specimen Charpy impact test; and (d) specimen
configuration and loading arrangement for tensile impact
test

Fig. 4a. T h e m a x i m u m force t o failure, which is

s h o w n a s Pm, c a n b e u s e d t o calculate t h e fracture
t o u g h n e s s Klc for t h e m a t e r i a l :
tflc=1.5

l/2

YPmLa /BW

(10)

w h e r e L , a, W a n d a r e the d i m e n s i o n s (m) of t h e
specimen s h o w n in Fig. 4c a n d Y is a g e o m e t r i c a l
factor related t o t h e n o t c h d e p t h - t h i c k n e s s r a t i o
1 / 2
a/W. T h e units of Kk a r e M P a m . T h e i m p a c t
2
strength (kJ m " ) is calculated from t h e failure energy
4 by
Is = EJB(W-a)

(11)

F i g u r e 4d s h o w s a tensile i m p a c t s a m p l e in a typical
test fixture. Tensile i m p a c t s t r e n g t h is also calculated
from t h e energy of failure a n d cross-sectional a r e a of
t h e specimen
h = EJWt

(12)

w h e r e W is the w i d t h a n d t t h e thickness of t h e
2
specimen. T h i s q u a n t i t y also h a s u n i t s of k J m ~ .
Tensile i m p a c t a n d C h a r p y i m p a c t s t r e n g t h s a r e
d e t e r m i n e d o n p e n d u l u m - t y p e i m p a c t m a c h i n e s with
test fixtures a p p r o p r i a t e for t h e specific m e t h o d . A
typical a r r a n g e m e n t for t h e C h a r p y test is s h o w n in
Fig. 4 b . M a n y types of falling weight i m p a c t tests a r e
also available, d e p e n d i n g o n t h e t y p e of specimen a n d
test d a t a r e q u i r e d . D a t a m a y b e r e p o r t e d in v a r i o u s
forms, such as kilojoules p e r m e t e r , kilojoules for 5 0 %

370

Handling

A d v a n c e s in c o m p u t e r t e c h n o l o g y , such as t h e wide
s p r e a d availability of m i n i c o m p u t e r s a n d m i c r o
c o m p u t e r s , h a v e led t o a r a p i d g r o w t h in a u t o m a t e d
d a t a h a n d l i n g in t h e l a b o r a t o r y . It is n o w possible
t o interface m a n y pieces of e q u i p m e n t t o a single
c o m p u t e r so t h a t d a t a is collected from e a c h simul
t a n e o u s l y . Software is available t o calculate such
p r o p e r t i e s as tensile s t r e n g t h , elastic m o d u l u s , flexural
modulus and impact properties, a m o n g others. The
d a t a c a n b e a n a l y z e d statistically a n d curves gener
a t e d t h r o u g h t h e use of p r i n t e r - p l o t t e r e q u i p m e n t .
T h e s e systems h a v e i m p r o v e d d a t a h a n d l i n g a n d
have reduced the materials characterization required.
F u r t h e r discussions of basic systems m a y be f o u n d in
C h u d z i c k i a n d P e a k e (1984) a n d H o l l a n d (1985).
See also: Elastomers: Tests for Mechanical Properties

Bibliography
American Society for Testing and Materials 1977 Standard
Test Method for Tensile, Compressive and Flexural Creep
and Creep-Rupture of Plastics, ASTM Designation D2990-77. ASTM, Philadelphia, PA
American Society for Testing and Materials 1979 Standard
Test Method for Tensile-Impact Energy to Break Plastics
and Electrical Insulating Materials, ASTM Designation
D-1822-79. ASTM, Philadelphia, PA
American Society for Testing and Materials 1980a Standard
Test Method for Compressive Properties of Rigid Plastics,
ASTM Designation D-695-80. ASTM, Philadelphia, PA
American Society for Testing and Materials 1980b Standard
Test Method for Rubber Properties in Tension, ASTM
Designation A-412-80. ASTM, Philadelphia, PA
American Society for Testing and Materials 1981a Standard
Test Methods for Flexural Properties of Unreinforced and
Reinforced Plastics and Electrical Insulating Materials,
ASTM Designation D-790-81. ASTM, Philadelphia, PA
American Society for Testing and Materials 1981b Standard
Test Methods for Impact Resistance of Plastics and Elec
trical Insulating Materials, ASTM Designation D-256-81.
ASTM, Philadelphia, PA
American Society for Testing and Materials 1982 Standard
Test Method for Tensile Properties of Plastics, ASTM,
Designation D-638-82a. ASTM, Philadelphia, PA
Brown R 1986 Physical Testing of Rubber, 2nd edn.
Elsevier, Amsterdam
Carlowtz 1972 Tabellarische Ubersicht uber die Prufung
von Kunststoffen, 4th edn. Umschau, Frankfurt, Ger
many, pp. 6-23; 26-31
Chudzicki J, Peake R J 1984 Unified approach to
computer-aided polymer characterization. Plastics in a

Polymers:

World Economy, Proc. SPE 42nd Annual Technical Conf.

Society of Plastics Engineers, Greenwich, CT, p. 342
Gent A 1978 Strength of elastomers. In: Eirich F R (ed.)
1978 Science and Technology of Rubber. Academic Press,
New York, Chap. 10
Holland L 1985 Materials evaluation laboratory automa
tion. Am. Lab. January: 42
Levy S 1979 Projecting short-term data into long-term
creep. Plastics Design Forum. Industry Media, Denver,
CO, pp. 38-45
Nelson L 1974a Mechanical Properties of Polymers and
Composites. Dekker, New York, Chaps. 1, 3
Nelson L 1974b Mechanical Properties of Polymers and
Composites. Dekker, New York, Chap. 5
Turner S 1973 Mechanical Testing of Plastics, 2nd edn.
Longman, New York
Turner S 1974 Deformational behaviour. In: Ogorkiewicz
R (ed.) 1974 Thermoplastics: Properties and Design.
Wiley, London, Chap. 3
Vincent I 1974 Short term strength and impact behaviour.
In: Ogorkiewicz R (ed.) 1974 Thermoplastics: Proper
ties and Design. Wiley, London, Chap. 5
Ward I 1983 Mechanical Properties of Solid Polymers,
2nd edn. Wiley, Chichester, UK, Chaps. 5-7
. V. L i n d
[ C o n t a i n e r C o r p o r a t i o n of A m e r i c a ,
Wilmington, Delaware, USA]

Tests for

Specific h e a t m e a s u r e m e n t s h a v e b e c o m e a c o m m o n
place t o o l for c h a r a c t e r i z i n g t h e b e h a v i o r of
p o l y m e r s . W i t h this k i n d of t h e r m a l d a t a t h e m a c r o
scopic b e h a v i o r of semicrystalline a n d
glassy
p o l y m e r s c a n b e s t u d i e d a n d often c o r r e l a t e d w i t h
o t h e r c o m p l e m e n t a r y m e t h o d s s u c h as d y n a m i c
m e c h a n i c a l , dielectric a n d n u c l e a r m a g n e t i c r e s o
n a n c e investigations of t h e s a m e p o l y m e r systems. I n
this m a n n e r it is often possible t o g a i n insight i n t o t h e
m i c r o s c o p i c origin of t h e o b s e r v e d t h e r m a l effects. A
n u m b e r of t h e r m a l m e t h o d s h a v e b e e n d e v e l o p e d t o
s t u d y n o t only p o l y m e r s b u t also t h e additives w h i c h
are usually b l e n d e d w i t h t h e m t o i m p r o v e t h e c h e m
ical a n d physical p r o p e r t i e s of t h e resin ( T u r i 1981).

1. Specific

Heat

Q=

T h e chief function of c a l o r i m e t r y in t h e a b s e n c e of
chemical c h a n g e is t h e d e t e r m i n a t i o n of t h e specific
h e a t C; this is m e a s u r e d as t h e h e a t Q a b s o r b e d b y a
system o n raising t h e t e m p e r a t u r e by 1 K :
C=Q/AT

CAT+

(1)

Since there a r e n o perfect i n s u l a t o r s for h e a t all

calorimetric m e a s u r e m e n t s m u s t be c o r r e c t e d for h e a t
losses. In a d i a b a t i c c a l o r i m e t r y these h e a t losses a r e
minimized b y enclosing the c a l o r i m e t e r w i t h i n a m e t a l

(2)

A n a d i a b a t i c c a l o r i m e t e r for p o l y m e r research h a s
b e e n described by K a r a s z a n d O'Reilly (1966). It
c o v e r s t h e r a n g e 1 5 - 6 0 0 w i t h a n a c c u r a c y of 0 . 1 0.2 % . T h i s t y p e of c a l o r i m e t e r , w h i c h h a s h e a t i n g
1
r a t e s of less t h a n T C m i n " a n d large e q u i l i b r a t i o n
times a t t h e e n d of e a c h h e a t i n g interval, is being
r e p l a c e d for p o l y m e r studies b y d y n a m i c c a l o r i m e t e r s
w i t h significantly faster h e a t i n g r a t e s .
T h e s e latter c a l o r i m e t e r s h a v e a b a n d o n e d the a d i a
b a t i c principle in favor of a h e a t leak w h i c h is the
s a m e for b o t h t h e s a m p l e a n d a reference. N u m e r o u s
i n s t r u m e n t s of this so-called heat-flux type calori
m e t e r a r e n o w c o m m e r c i a l l y available
A different a p p r o a c h t o d y n a m i c differential calori
m e t r y w a s r e p o r t e d by O ' N e i l l (1964), w h o described
a differential s c a n n i n g c a l o r i m e t e r ( D S C ) . T h i s differs
f r o m p r e v i o u s differential c a l o r i m e t e r s b y m a i n t a i n
ing t h e s a m p l e a n d reference a t identical t e m p e r a
t u r e s . T h e differential h e a t i n p u t p e r s e c o n d dq/dt
necessary t o achieve this c o n d i t i o n is m o n i t o r e d dir
ectly. T h i s differential, d u r i n g h e a t i n g with a r a t e
q = dT/dt, is p r o p o r t i o n a l t o t h e differential specific
heats:
m

XQ

- mCprc{t)q

(3)

E n d o t h e r m i c o r e x o t h e r m i c events a r e m e a s u r e d
directly as a function of t i m e . T h e e n t h a l p y of a
p r o c e s s is simply t h e a r e a a b o v e o r b e l o w t h e h e a t
c a p a c i t y o r i s o t h e r m a l baseline o n a p l o t of the
differential h e a t i n p u t p e r s e c o n d a g a i n s t time:
AH=j(dQ/dt)dt

(4)

In p r a c t i c e t h e specific h e a t a t c o n s t a n t p r e s s u r e Cp of
a n u n k n o w n b e t w e e n a lower t e m p e r a t u r e limit ,
a n d a n u p p e r t e m p e r a t u r e limit T2 c a n b e m e a s u r e d in
a D S C b y c o m p a r i n g t h e o r d i n a t e d i s p l a c e m e n t D% of
t h e u n k n o w n a n d t h a t of a s a m p l e of k n o w n specific
h e a t (usually a s a p p h i r e , A 1 2 0 3 , disk) w i t h t h e baseline
b e h a v i o r of t h e e m p t y D S C . T h e specific h e a t of the
s a m p l e c a n t h e n b e c a l c u l a t e d f r o m t h e following
expression:
Cps = ( ^ A h O , / ^ s ) ( ^ s / ^ A b O ) ) C M

Measurements

Properties

shield t h a t is m a i n t a i n e d a s close as possible t o the

c a l o r i m e t e r t e m p e r a t u r e . In this w a y t h e h e a t loss q
b e c o m e s a c o r r e c t i o n t e r m t o b e a d d e d t o E q n . (1):

dQ/dt = ( m C

Polymers: Tests for Thermal Properties

Thermal

h 30

(5)

w h e r e WMl0j a n d Ws refer t o t h e weight of t h e

s a p p h i r e s t a n d a r d a n d test s a m p l e , respectively. I n
this p r o c e d u r e c a r e m u s t be t a k e n t h r o u g h a p p r o p r i
a t e electronic m a n i p u l a t i o n t o e n s u r e t h a t t h e isother
m a l baselines a t Tx a n d T2 agree w i t h i n a t least 4 %
a n d t h e c a l o r i m e t e r h a s a linear baseline r e s p o n s e
(Fig. 1).
I n s t e a d of m a n u a l l y d e t e r m i n i n g Cp it is possible t o
interface a c o m p u t e r with a differential s c a n n i n g
c a l o r i m e t e r t o m e a s u r e specific h e a t . I n t h e s t a n d a r d
r o u t i n e t h e i n s t r u m e n t ' s baseline is r u n a n d s t o r e d ,

371

Polymers:

Tests for

Thermal

Properties

A l 20 3

//

//

empty sample container^

280

300

320

340

360

Temperature (K)

Figure 1
Comparative DSC scan of an unknown polymeric
material and a sapphire standard against an empty
sample
1
container produced by heating at 20 C min

a n d the u n k n o w n s a m p l e is t h e n p r o g r a m m e d
t h r o u g h t h e s a m e t e m p e r a t u r e s e q u e n c e . If t h e o r d i
n a t e displacement h a s been c a l i b r a t e d with a s t a n d a r d
such as i n d i u m with a k n o w n AHf value p r i o r t o t h e
Cp r u n , t h e s t a n d a r d s a p p h i r e r u n m a y be eliminated
or only carried o u t as a check of a c c u r a c y . By these
techniques C values with accuracies of b e t t e r t h a n
1 % c a n be o b t a i n e d from - 175 C t o 725 C.

2. Melting

Processes

and Equilibrium

Properties

It is difficult if n o t impossible t o g r o w p o l y m e r
crystals of sufficient size t h a t e x p e r i m e n t a l equi
librium p a r a m e t e r s c a n be o b t a i n e d b y direct
measurement. Thus, extrapolation techniques have
been developed t o give e q u i l i b r i u m d a t a from
m e a s u r e m e n t s o n small, m e t a s t a b l e crystals o r o n
equilibrium crystals of small molecules. A p p l i c a t i o n
of these m e t h o d s t o o b t a i n t h e e q u i l i b r i u m t h e r m o
d y n a m i c p r o p e r t i e s of polyethylene is described below
since its melting b e h a v i o r h a s been studied m o r e t h a n
t h a t of a n y o t h e r m a c r o m o l e c u l e .
T h e melting of b u l k crystallized p o l y m e r s usually
occurs over a b r o a d t e m p e r a t u r e r a n g e d u e t o a
d i s t r i b u t i o n of crystal sizes a n d defects. A linear
polyethylene s a m p l e w h i c h w a s c o o l e d slowly from
the melt before t h e s t a r t of t h e h e a t c a p a c i t y d e t e r m i
n a t i o n is s h o w n in Fig. 2 (solid line). Cp rises s h a r p l y
over a t e m p e r a t u r e r a n g e of 2 0 - 2 5 C t o a m a x i m u m
at 133 C, t h e n d r o p s a b r u p t l y a n d levels off. I n
c o n t r a s t t o this b e h a v i o r , t h e Cp of p o l y e t h y l e n e single
crystals p r e p a r e d from diluted h e x a d e c a n e s o l u t i o n is
p l o t t e d against t e m p e r a t u r e ( d a s h e d line, Fig. 2).
N e a r l y 90 % of t h e single crystals melt within a

372

100

120

Temperature

(C)

Figure 2
Melting curves of linear polyethylene:
bulk crystallized;
, solution crystallized

, annealed,

n a r r o w t w o - d e g r e e ( 1 2 6 - 1 2 8 C) interval. O n l y a trace
of m e l t i n g o c c u r s b e y o n d 128 C ( S o u t h e r n et al.
1972). T h i s n a r r o w m e l t i n g p e a k is a t t r i b u t e d t o
crystals with u n i f o r m thickness ( ~ 1 5 . 4 n m ) a n d t h e
a b s e n c e of a n y lamellar r e o r g a n i z a t i o n . T h e latter
process leads t o a n increase in t h e chain-folded lamel
lar thickness. U n d e r similar m e l t i n g c o n d i t i o n s crys
tals t h i n n e r t h a n 1 5 n m will thicken a n d exhibit
multiple m e l t i n g p e a k s . Bair et al. (1967) h a v e s h o w n
that radiation-induced
crosslinking c a n
retard
lamellar t h i c k e n i n g . T h e latter t e c h n i q u e c a n allow
m e a s u r e m e n t of a single m e l t i n g t e m p e r a t u r e w i t h o u t
reorganization.
A n a l t e r n a t i v e a p p r o a c h t o melting m e t a s t a b l e
p o l y m e r crystals w i t h o u t r e o r g a n i z a t i o n d u r i n g
fusion is t o seek a c o n s t a n t m e l t i n g t e m p e r a t u r e as
h e a t i n g rates a r e increased. T h i s process is referred t o
as t h e z e r o - e n t r o p y m e l t i n g m e t h o d ( W u n d e r l i c h
1980). U n f o r t u n a t e l y , in s o m e cases, h e a t i n g rates in
-1
excess of 1000 C m i n
m a y b e necessary t o arrest
r e o r g a n i z a t i o n a l effects.
T h e e q u i l i b r i u m m e l t i n g t e m p e r a t u r e Tm of a
p o l y m e r m a y be calculated from t h e T h o m s o n - G i b b s
e q u a t i o n b y s u b s t i t u t i n g t h e e x p e r i m e n t a l l y deter
m i n e d m e l t i n g t e m p e r a t u r e s Tm of small crystals
w h o s e lamellar thickness / h a s been d e t e r m i n e d from
low-angle x-ray p h o t o g r a p h s :

Polymers:

Tests for Thermal

Properties

yields AH{ of 293 J g " , a t 1.000 c m g , t h e specific

v o l u m e of t h e perfect polyethylene crystal a t r o o m
t e m p e r a t u r e . Similarly AH{ e x t r a p o l a t e s a t 1 // = 0 t o a
1
value of 284 J g " . In a d d i t i o n , t h e r a t i o of AQ{ t o
AH( gives a m e a s u r e of t h e level of crystallinity for a
partially crystalline s a m p l e .
D e t e r m i n a t i o n of t h e freezing-point lowering c a n
be used a s a n indirect m e a s u r e m e n t o f AH{. T h i s
diluent effect o n Tm is b a s e d o n t h e F l o r y expression:

= ( / ? / A / / f) [ ^ ( K 1- ^ . v ) ]

(7)

w h e r e a n d Vl a r e t h e m o l a r v o l u m e s of t h e r e p e a t
u n i t a n d diluent, a n d v, is t h e v o l u m e fraction diluent.
T h e h e a t of fusion is o b t a i n e d from t h e intercept a t
zero v o l u m e fraction diluent of a p l o t of ( 1 / 7 ^ - 1 / 7 ^ ) /
v, versus v,. Q u i n n a n d M a n d e l k e r n (1958) h a v e
1
r e p o r t e d AH{ values of 277, 2 7 8 , 295 a n d 289 J g " for
p o l y e t h y l e n e using four different solvents. Similar
e s t i m a t e s of AH{ for p o l y e t h y l e n e c a n be m a d e from a
detailed l o o k a t t h e c h a n g e of h e a t of fusion with
c h a i n length.
04

06

1000//

O.i

3. Glass

(nm )

Figure 3
Melting temperatures of polyethylene single crystals as a
function of reciprocal lamellar thickness: , crystal from
xylene solution; , crystal from hexadecane solution
Tm =

Tm[\-(2oJlAH()]

Transition

A t t h e glass-transition t e m p e r a t u r e Tg t h e h e a t c a p a
city of a c o m p l e t e l y a m o r p h o u s p o l y m e r increases b y

(6)

w h e r e ae is t h e crystal's t o p a n d b o t t o m specific
surface free energy a n d AHf t h e b u l k h e a t of fusion
per cubic centimeter.
A p p l i c a t i o n o f this t e c h n i q u e t o m e l t i n g o f lightly
crosslinked p o l y e t h y l e n e crystals, g r o w n from solu
tion, is s h o w n in F i g . 3. T h e intercept in F i g . 3
coincides well with t h e 7 ^ of 145 C e s t i m a t e d b y
F l o r y et al. (1963) a n d B r o a d h u r s t (1966). I n t h e latter
case a n a l t e r n a t i v e a p p r o a c h w a s used for finding t h e
melting t e m p e r a t u r e of l o w - m o l e c u l a r - w e i g h t h o m o logs of polyethylene, a n d t h e d a t a e x t r a p o l a t e d t o
infinite m o l e c u l a r weight.
T h e r e a r e n o a b s o l u t e values of t h e e n t h a l p y of
a m o r p h o u s o r crystalline p o l y m e r s . E v a l u a t i o n o f t h e
e q u i l i b r i u m h e a t of fusion is b y o n e of three e x t r a p o
lation techniques. T h e s e m e t h o d s involve t h e deter
m i n a t i o n of t h e h e a t o f fusion AH{ a s a function
of crystallinity, t h e m e a s u r e m e n t of m e l t i n g t e m
p e r a t u r e s in diluent m i x t u r e s a s a function of c o n
c e n t r a t i o n , o r t h e d e t e r m i n a t i o n of h e a t s of fusion of
low-molecular-weight a n a l o g s .
Integration of the area above the heat capacity
baseline ( d a s h e d line, F i g . 2) yields t h e a p p a r e n t h e a t
of fusion AQ{. A p l o t of AQf a g a i n s t specific v o l u m e
or reciprocal lamellar thickness for p o l y e t h y l e n e

Temperature

(b)

I
1

/ ^ ^ ^ ^

Temperature

Figure 4
Schematic diagrams of the specific heat (a) and enthalpy
(b) versus temperature for the quenched glass 1 and the
annealed glass 2
373

Polymers:

Tests for

Thermal

Properties

a b o u t 11 J k m o l of m o b i l e u n i t s ( W u n d e r l i c h 1960).
T h e r e is n o h e a t o f t r a n s i t i o n associated with this
p h e n o m e n o n . H o w e v e r , Petrie (1972) h a s s h o w n t h a t
m o l e c u l a r r e l a x a t i o n c a n o c c u r resulting in a n e n d o t h e r m s u p e r i m p o s e d u p o n this increase in Cp. T h e s e
e n d o t h e r m s c a n be related t o t h e p r i o r t h e r m o m e c h a nical history of t h e p o l y m e r .
I n o r d e r t o e v a l u a t e t h e e n t h a l p y difference AH
b e t w e e n t w o glassy states with different t h e r m a l his
tories, the net difference in t h e a r e a s u n d e r t h e C
versus curves s h o u l d b e d e t e r m i n e d ( M a t s u o k a a n d
Bair 1977). T h i s is schematically illustrated in F i g . 4.
First, a reference s a m p l e of t h e s a m e m a t e r i a l is m a d e
which c a n be b r o u g h t t o a certain glassy state r e p e a t
edly a n d r e p r o d u c i b l y . N o r m a l l y , this is d o n e b y
cooling t h e s a m p l e r a p i d l y from t h e liquid state a t t h e
s a m e r a t e t h a t will b e e m p l o y e d in all s u b s e q u e n t
- 1
h e a t i n g r u n s (a typical r a t e is 20 m i n , w h i c h p r o
d u c e s glass 1 in F i g . 4). G l a s s 2 c a n b e f o r m e d b y
simply h o l d i n g glass 1 below its glass-transition t e m
p e r a t u r e ( r g l) .
This annealing process occurs m o r e rapidly the
closer t h e a n n e a l i n g t e m p e r a t u r e is t o Tgl. T h e glass-

3.0

t r a n s i t i o n t e m p e r a t u r e of glass 1 s h o u l d be higher
t h a n t h a t of t h e l o w e r - e n t h a l p y glass 2, b u t b e c a u s e of
t h e longer r e l a x a t i o n time of t h e latter, t h e glassy state
persists t o t h e higher t e m p e r a t u r e T g 3, if t h e h e a t i n g
rates a r e t h e s a m e . I n o r d e r t o r e a c h t h e e q u i l i b r i u m
r u b b e r state a b o v e Tg3, a delayed b u t s u d d e n j u m p in
e n t h a l p y t a k e s place, a n d a p e a k in t h e specific h e a t Cp
is o b s e r v e d . T h e difference in t h e initial values of
e n t h a l p y for glass 1 a n d glass 2 s h o u l d be o b t a i n e d by
s u b t r a c t i n g a r e a A from a r e a B. T h i s o b v i o u s aspect
h a s often b e e n neglected, a n d only t h e p e a k a r e a h a s
been t a k e n as t h e difference in e n t h a l p y . T h i s p r o c e d
u r e results in o v e r e s t i m a t i n g t h e e n t h a l p y decrease
with time. A n e x a m p l e w h e r e specific h e a t versus
t e m p e r a t u r e d a t a h a v e been carefully collected follow
ing t h e a f o r e m e n t i o n e d c o n s i d e r a t i o n s is s h o w n in
F i g . 5 for p o l y s t y r e n e s a m p l e s .
T h e limiting e n t h a l p y difference b e t w e e n t h e
q u e n c h e d s a m p l e (glass 1) a n d t h e e q u i l i b r i u m glassy
s t r u c t u r e (glass 3) a t a n n e a l i n g t e m p e r a t u r e T* is
r e a c h e d after l o n g times. T h u s , m a y be o b t a i n e d by
p l o t t i n g at SL given a n n e a l i n g t e m p e r a t u r e against
t h e log of time. T h e limiting e n t h a l p y is t a k e n a t t h e
b r e a k in t h e c u r v e w h e r e is i n d e p e n d e n t of time. A n
a l t e r n a t i v e a p p r o a c h h a s b e e n a d v a n c e d b y Prest et al.
(1981) w h i c h utilizes t h e Active t e m p e r a t u r e defined
by t h e intersection of t h e e x t r a p o l a t e d liquid a n d
glassy e n t h a l p i e s .
See also: Polymers: Thermal Analysis

Bibliography

2.0

350

360

370

380

Temperature

390

400

410

(K)

Figure 5
Specific heat versus temperature for polystyrene samples
with different thermal histories

374

Bair , Salovey R, Huseby W 1967 Melting and

annealing of polyethyene single crystals. Polymer 8: 9-20
Broadhurst G 1966 The melting temperatures of the nparaffins and the convergence temperature for polyethy
lene. / . Res. Natl. Bur. Stand. Sect. A 70: 481-6
Flory J 1963 Principles of Polymer Chemistry. Cornell
University Press, Ithaca, NY
Flory J et al. 1963 Melting points of linear-chain homologs. The normal paraffin hydrocarbons. / . Am. Chem.
Soc. 85: 3548-53
Karasz F E, O'Reilly J 1966 Wide temperature range
adiabatic calorimeter. Rev. Sci. Instrum. 37: 255-60
Matsuoka S, Bair 1977 The temperature drop in glassy
polymers during deformation. / . Appl. Phys. 48: 4058-62
O'Neill J 1964 The analysis of a temperature-controlled
scanning calorimeter. Anal. Chem. 36: 1238^45
Petrie S 1972 Thermal behavior of annealed organic
glasses. J. Polym. Sci. A-2. 10: 1255-72
Prest W Jr, Luca D J, Roberts F J Jr 1981 The capabilities
and application of a computer controlled differential
scanning calorimeter. In: Turi A (ed.) 1981 Thermal
Analysis in Polymer Characterization. Heyden, Philadel
phia, PA, pp. 24-42
Quinn F A Jr, Mandelkern L 1958 Thermodynamics of
crystallization in high polymers: poly (ethylene). / . Am.
Chem. Soc. 80: 3178-82
Roe R J, Bair 1970 Thermodynamic study of fold
surfaces of polyethylene single crystals. Macromolecules
3: 454-8

Polymers:

Southern J H, Porter R S, Bair 1972 Melting behavior

of polyethylene crystallized in a pressure capillary visc
ometer.
Polym. Sol. A-2 10: 1135-^3
Turi A (ed.) 1981 Thermal Characterization of Polymeric
Materials. Academic Press. New York
Wunderlich 1960 Study of the change in specific heat of
monomeric and polymeric glasses during the glass transi
tion. J. Phys. Chem. 64: 1052-6
Wunderlich 1980 Irreversible melting. In: Wunderlich
1980 Crystal Melting, Macromolecular Physics, Vol. 3.
Academic Press, New York, pp. 128-253
Wunderlich B, Dole 1957 Specific heat of synthetic high
polymersVIII. Low pressure polyethylene. J. Polym.
Sci. 24: 201-13
. E. Bair
[ A T & T Bell L a b o r a t o r i e s , M u r r a y Hill,
N e w Jersey, U S A ]

Polymers: Thermal Analysis

M o d e r n t h e r m a l analysis p e r m i t s fast d e t e r m i n a t i o n
of the h e a t capacities, h e a t s of t r a n s i t i o n a n d m a s s of
a p o l y m e r i c m a t e r i a l as it u n d e r g o e s a physical o r
chemical process. T h e s e types of t h e r m a l m e a s u r e
m e n t s c a n yield q u a n t i t a t i v e i n f o r m a t i o n o n topics as
diverse as following t h e r e a c t i o n kinetics of a c u r i n g
t h e r m o s e t resin t o t r a c k i n g t h e diffusion of a n a n t i o x i
d a n t molecule t h r o u g h a p o l y m e r .
T h i s article surveys several practical a p p l i c a t i o n s of
t w o classical t h e r m a l analysis m e t h o d s , n a m e l y calori
m e t r y a n d t h e r m o g r a v i m e t r y , in a r e a s of p o l y m e r
science w h e r e they h a v e m a d e i m p o r t a n t c o n t r i b u
tions t o u n d e r s t a n d i n g t h e t h e r m a l b e h a v i o r of
polymers.
T h e m o s t c o m m o n c o m m e r c i a l i n s t r u m e n t s used t o
e v a l u a t e c h a n g e s in t h e h e a t c o n t e n t o r weight of a
s a m p l e are differential s c a n n i n g c a l o r i m e t e r s ( D S C s )
and thermobalances, or thermogravimetric (TG) de
vices, respectively. T h e use of t h e D S C to m a k e h e a t
capacity m e a s u r e m e n t s o n e q u i l i b r i u m a n d n o n e q u i l i b r i u m p r o p e r t i e s of semicrystalline a n d glassy
p o l y m e r s is described elsewhere (see Polymers:
Tests
for Thermal Properties).
H e r e , e x a m p l e s of s t u d y i n g
the solid state t r a n s i t i o n b e h a v i o u r of b l e n d s , e v a l u a t
ing the c u r i n g r e a c t i o n of a t h e r m o s e t a n d lastly
m e a s u r i n g t h e level a n d state of w a t e r a b s o r b e d b y a
p o l y m e r will be reviewed briefly. T h e T G section will
center o n diffusion studies in p o l y m e r s .

1. DSC

Measurements

on

Polyblends

1.1 Compatibility
of Polymer
Blends
Binary p o l y m e r b l e n d s s e l d o m f o r m h o m o g e n e o u s ,
o n e - p h a s e systems since t h e e n t r o p y of m i x i n g ASmix
in the free energy of m i x i n g expression
AGmix

= AHmix-TASmix

(1)

1001

02

04

06

Thermal

1
08

Analysis

.
10

Weight traction PPO

Figure 1
Phase diagram for a blend of /?-chlorostyrene/
o-chlorostyrene copolymer with PPO as a function of
weight fraction PPO (after Karasz and MacKnight 1977)
is usually t o o small t o o v e r c o m e t h e n o r m a l l y positive
h e a t of m i x i n g AHmix t h a t w o u l d p r o d u c e a negative
free energy of m i x i n g A G m i x. T h e latter is a necessary
c o n d i t i o n for p o l y m e r c o m p a t i b i l i t y . E x p e r i m e n t a l l y
t h e least a m b i g u o u s criterion of p o l y m e r c o m p a t i
bility is t h e detection of a single glass-transition
t e m p e r a t u r e Tg w h i c h is i n t e r m e d i a t e between those
c o r r e s p o n d i n g t o the t w o c o m p o n e n t p o l y m e r s . P h a s e
s e p a r a t i o n is j u d g e d by t h e existence of t w o distinct
glass t r a n s i t i o n t e m p e r a t u r e s ( K r a u s e 1978).
Below p h a s e s e p a r a t i o n is m e a s u r e d from the
h e a t s of s o l u t i o n of t h e p o l y m e r s a n d their blends by
Tian-Calvert
microcalorimetry.
Application
of
H e s s ' s law t o these values yields AHm[x ( R y a n et al.
1980). Positive levels of AHmix a r e a sufficient c o n
d i t i o n for p h a s e d e m i x i n g .
O n e of t h e best d o c u m e n t e d cases of c o m p a t i b l e
p o l y m e r b l e n d s is t h a t of p o l y s t y r e n e (PS) a n d
poly(2, 6 - m e t h y l - l , 4 - p h e n y l e n e oxide) ( P P O ) . A
single Tg h a s been detected for all b l e n d c o m p o s i t i o n s
by n u m e r o u s t h e r m a l t e c h n i q u e s . T h e effect of c h e m
ical modification of P P O a n d P S a n d their related
c o p o l y m e r s o n miscibility h a s been m u c h investigated
( M a c K n i g h t et al. 1978). K a r a s z a n d M a c K n i g h t
(1977) h a v e r e p o r t e d t h e p h a s e d i a g r a m for a blend of
/ 7 - c h l o r o s t y r e n e / o - c h l o r o s t y r e n e c o p o l y m e r with P P O
as a function of P P O c o n c e n t r a t i o n ( F i g . l ) . T h u s , if
t h e p h a s e b o u n d a r i e s a r e k n o w n , t h e processing c o n
d i t i o n s c a n be c o n t r o l l e d t o yield either a h o m o
geneous polyblend at r o o m temperature or a mixture
c o n t a i n i n g t w o discrete p h a s e s . A d d i t i o n a l tests m u s t
be c a r r i e d o u t t o d e t e r m i n e the m o s t desirable physi
cal state.
1.2 Quantitative

Analysis

M u l t i c o m p o n e n t p o l y m e r b l e n d s w h i c h c a n n o t be
a n a l y z e d by c o n v e n t i o n a l spectroscopic t e c h n i q u e s
d u e t o o v e r l a p p i n g a b s o r p t i o n b a n d s o r the screening
effects of additives c a n often be assayed b y D S C

375

Polymers:

Thermal

Analysis

indicates t h e a c t u a l c o n c e n t r a t i o n of r u b b e r w h i c h is
effective in m o d i f y i n g t h e d e f o r m a t i o n a l b e h a v i o r of
the S A N matrix.

2500k

2. Application

of DSC

to the Curing

of

Thermosets
All t h e r m o s e t t i n g resins liberate h e a t d u r i n g cure:
reactants

Temperature (C)

Figure 2
Specific heat capacity versus temperature for a commercial
ABS resin (after Bair 1974 Polym. Eng. Sci. 14: 202-5)

w i t h o u t r e s o r t i n g t o e x t r a c t i o n p r o c e d u r e s . If a
p o l y m e r o r a l o w - m o l e c u l a r - w e i g h t a d d i t i v e is i n c o m
patible with t h e b a s e resin, it c a n be detected in a
s e p a r a t e crystalline o r glassy p h a s e by either its melt
ing p o i n t Tm o r a n d m e a s u r e d q u a n t i t a t i v e l y from
heat of fusion AHf d e t e r m i n a t i o n s a t Tm o r i n c r e m e n
tal c h a n g e in h e a t c a p a c i t y AC m e a s u r e m e n t s a t Tg.
Conversely, in miscible a m o r p h o u s b l e n d s , t h e c o m
p o s i t i o n c a n b e e s t i m a t e d from Tg versus c o m p o s i t i o n
plots m e a s u r e d for t h a t system. Likewise, w h e n a n
additive is soluble in a p o l y m e r its c o n c e n t r a t i o n c a n
be e s t i m a t e d from shifts in t h e Tm o r Tg of t h e resin
(Bair 1981, S h a l a b y a n d Bair 1981).
T h e typical Cp b e h a v i o r of a c o m m e r c i a l a c r y l o n i t r i l e - b u t a d i e n e - s t y r e n e ( A B S ) resin is s h o w n in F i g .
2. A B S is a r u b b e r - t o u g h e n e d plastic w h e r e a brittle
c o p o l y m e r of s t y r e n e - a c r y l o n i t r i l e ( S A N ) is b l e n d e d
o r chemically b o n d e d t o s u b m i c r o n spheres of p o l y
b u t a d i e n e ( B D ) . In t h e l o w - t e m p e r a t u r e insert, t h e
discontinuity in Cp (ACp) n e a r - 9 0 C is identified
with B D in t h e c o m p o s i t e . T h e weight fraction of B D
(0.13) is e s t i m a t e d from t h e r a t i o of t h e o b s e r v e d ACp
t o the ACp m e a s u r e d in a s e p a r a t e e x p e r i m e n t o n
the u n b l e n d e d h o m o p o l y m e r . In t h e high t e m p e r a
t u r e r a n g e , t h e Tg n e a r 104 C is d u e t o t h e S A N
c o p o l y m e r ( 7 6 w t % ) while t h e t w o first-order t r a n s i
tions n e a r 70 C a n d 1 5 0 C a r e a t t r i b u t e d t o t h e
melting of 0.24 w t % fatty acid residue a n d 3.6 w t % of
a mold lubricant.
R e c e n t D S C studies h a v e s h o w n t h a t t h e m a g
n i t u d e of ACp at Tg for t h e B D p h a s e of a n A B S
c o m p o s i t e w a s r e d u c e d n o n l i n e a r l y as t h e r a t i o of
S A N grafted t o B D w a s increased (Bair et al. 1981).
T h e a t t e n u a t i o n s of ACp with increasing graft levels
a p p e a r t o be c a u s e d by t h e r e d u c e d n u m b e r of config u r a t i o n a l c h a n g e s t h a t c a n o c c u r in t h e grafted B D
molecules at Tg. T h u s , at high graft levels c a l o r i m e t r i c
d e t e r m i n a t i o n of t h e r u b b e r c o n t e n t of a n A B S resin
d o e s n o t give a m e a s u r e of the t o t a l r u b b e r b u t

376

products

(2)

w h e r e AHRXN is t h e e x o t h e r m i c h e a t p e r m o l e of
r e a c t i n g g r o u p s . Since t h e D S C m e a s u r e s h e a t flow
(dH/dt) directly it is ideally suited t o m e a s u r e n o t o n l y
t h e h e a t of r e a c t i o n b u t also t h e r a t e of h e a t e v o l u t i o n .
If t h e c u r e r e a c t i o n is t h e only t h e r m a l event in t h e
c u r i n g p r o c e s s , t h e r e a c t i o n r a t e do/L/dt is directly
p r o p o r t i o n a l t o dH/dt:
da/dt = (dH/dt)/AHRXN

(3)

D u r i n g i s o t h e r m a l D S C r u n s , t h e degree of c o n v e r
sion is:
, = # , / / /

(4)

w h e r e a, is t h e e x t e n t of r e a c t i o n a n d AHt t h e h e a t
evolved u p t o t i m e t ( P r i m e 1981).
A n e x a m p l e of t h e D S C m e t h o d for following t h e
c u r i n g of a n e p o x y resin is s h o w n in F i g . 3. If t h e
i s o t h e r m a l c u r e is c a r r i e d o u t a t c o m p a r a t i v e l y low
t e m p e r a t u r e s , t h e r e a c t i o n will be r e t a r d e d severely
w h e n r g, w h i c h increases as increases, reaches t h e
c u r e t e m p e r a t u r e . A t this p o i n t t h e r e a c t i o n b e c o m e s
diffusion c o n t r o l l e d . T h e residual h e a t of r e a c t i o n
AHifes a s s o c i a t e d with t h e h e a t liberated d u r i n g c o m
p l e t i o n of t h e cross-linking c a n be m e a s u r e d in a
d y n a m i c r u n a b o v e Tg.
W h e n Tg exceeds t h e c u r e t e m p e r a t u r e t h e g e n e r a
tion of t i m e - t e m p e r a t u r e - d e g r e e of c o n v e r s i o n curves
c a n b e a t t e m p t e d by residual h e a t .

20^

Time (min)

Figure 3
Isothermal DSC methods for curing epoxy 1 at 170C

Polymers:

3. Thermal

Analysis

of Water

in a

of Diffusion

in Polymers

by

Thermobalance

Ol

Time (h)

Figure 5
Typical desorption curve for water from high-density
polyethylene at 23 C (C 0 = 36 ppm) (after McCall et al.
1984)

w a t e r until they h a v e e q u i l i b r a t e d . T h e n , by following

t h e loss of w a t e r by weight as a function of time as the
w a t e r d e s o r b s t h e diffusion coefficient D a n d the
solubility C 0 m a y be e v a l u a t e d . W h e n D is i n d e p e n
d e n t of c o n c e n t r a t i o n t h e slope of a log C 0 CJC0
2
2
against time / p l o t is n D/2301
w h e r e / is the thick
ness of the p o l y m e r sheet a n d C, is t h e a m o u n t of
liquid w h i c h h a s escaped from the p o l y m e r at time /.
A l s o , D m a y be d e t e r m i n e d from t h e a m o u n t of time
tXj2 r e q u i r e d for half t h e liquid t o escape:
2

T h e o r y a n d e x p e r i m e n t s h a v e been described for t h e

d e t e r m i n a t i o n of diffusion coefficients of liquids in
polymeric solids from d e s o r p t i o n d a t a ( M c C a l l 1957).
This m e t h o d involves s o a k i n g thin p o l y m e r slabs in

50

Analysis

i.o?

Polymer

All p o l y m e r s c a n a b s o r b w a t e r from t h e a t m o s p h e r e
a n d its presence in a p o l y m e r c a n lead t o m a r k e d
changes in t h e m a t e r i a l ' s physical p r o p e r t i e s a n d , in
s o m e cases, its chemical state. T h e influence of w a t e r
o n the of poly(vinyl acetate), P V A c , as m e a s u r e d
by D S C is s h o w n in F i g . 4. N o t e the plastizing effect
of w a t e r a b s o r b e d a t 23 C until a c o n c e n t r a t i o n of
a b o u t 4 w t % is r e a c h e d . All a d d i t i o n a l w a t e r is f o u n d
to be in a freezable state. T h e difference b e t w e e n t h e
total w a t e r WT m e a s u r e d c o u l o m e t r i c a l l y a n d the
a m o u n t of freezable w a t e r WF e q u a l s t h e c o n c e n t r a
tion of b o u n d w a t e r WB in this system. WF c a n be
m e a s u r e d by D S C d o w n t o a b o u t 20 p p m . I n this
technique, the s a m p l e is c o o l e d t o a b o u t 70 C a n d
then h e a t e d t o r o o m t e m p e r a t u r e . T h e o b s e r v e d h e a t
of t r a n s i t i o n for the melting ice crystals is divided by
w a t e r ' s h e a t of fusion t o yield t h e fraction of WF (Bair
et al. 1978).
This freezing followed by fusion t e c h n i q u e c a n b e
used t o s t u d y t h e a t t a c k of w a t e r a t a resin-filler
interface. U s u a l l y a c o m p o s i t e is placed in w a t e r a t
t e m p e r a t u r e s below Tg w h e r e freezable w a t e r will n o t
form in the p u r e resin b u t will slowly a c c u m u l a t e in
the glass-filled m a t e r i a l . A n y freezable w a t e r is p r e
s u m e d t o be f o r m e d a t the resin-glass interface (Bair
a n d M i n e r 1982).

4. Measurements

Thermal

4
6
Concentration of water (wt %)

Figure 4
The influence of water on the glass transition1 temperature
of PVAc as measured by DSC at 20 C mm (after Bair
1981 Polym. Eng. Sci. 21: 930-5)

Z) = 0 . 0 4 9 2 ( / / / 1 / 2)
Conversely, from a p l o t of C 0 -CJC0
( C r a n k a n d P a r k 1968):
2 2

D = nl S /\6

(5)
against

(6)

A n a u t o m a t i c null-type e l e c t r o b a l a n c e is ideally
suited t o following the escape of a volatile liquid from
a solid with a m a s s sensitivity of 0.1 p p m . A typical
e x a m p l e of the d e s o r p t i o n of w a t e r from a 1.27 m m
thick slab of high-density polyethylene a t 23 C is
s h o w n in F i g . 5. C 0 is e q u a l t o t h e t o t a l weight loss
from / = 0 until the s a m p l e ' s weight is c o n s t a n t
( M c C a l l et al. 1984).
In a n interesting v a r i a t i o n of this T G t e c h n i q u e for
s t u d y i n g diffusion it h a s been s h o w n t h a t C 0 a n d D
c a n b e m e a s u r e d s i m u l t a n e o u s l y for a nonvolatile
a n t i o x i d a n t molecule in a p o l y m e r ( R o e et al. 1974).
T h i s m e t h o d is b a s e d o n a n a l y z i n g the c o n c e n t r a t i o n
profile a c r o s s a stack of p o l y e t h y l e n e sheets which the
a n t i o x i d a n t h a s been forced t o diffuse t h r o u g h . T h e
level of a n t i o x i d a n t in a p o l y m e r sheet is d e t e r m i n e d
by T G b a s e d u p o n a p l o t of oxidative i n d u c t i o n times
as a function of a n t i o x i d a n t c o n c e n t r a t i o n .
See also: Polymers: Tests for Thermal Properties; Thermal
Analysis: An Overview; Thermal Analysis: Recent Develop
ments

377

Polymers:

Thermal

Analysis

Bibliography
Bair 1981 Thermal analysis of additives in polymers. In:
Turi 1981, pp. 845-906
Bair , Johnson G E, Merriweather R 1978 Water
sorption of polycarbonate and its effect on the polymer's
dielectric behaviour J. Appl. Phys. 49: 4976-84
Bair , Miner R J 1982 The effect of water on the impact
strength of glass filled polyphenylene sulfide. Soc. last.
Eng. Tech. Pap. 28: 105
Bair , Shepherd L, Boyle D J 1981 The effective
butadiene content in a rubber toughened plastic as
measured by DSC. In: Turi 1981, pp. 114-23
Crank J, Park G S (eds.) 1968 Diffusion in Polymers.
Academic Press, New York
Karasz F E, MacKnight W J 1977 Problems in compatibility
studies. Contemp. Top. Polym. Sci 2: 143-56
Krause S 1978 Polymer-polymer compatibility. In: Paul D
R, Newman S (eds.) 1978 Polymer Blends, Vol. 1. Aca
demic Press, New York, pp. 16-106
McCall D W 1957 Diffusion in ethylene polymers. J. Polym.
Sci. 26: 151-69
McCall D W, Douglass D C, Blyler L L Jr, Johnson G
Jelinski L W, Bair 1984 Solubility and diffusion of
water in low-density polyethylene. Macromol. 17: 1644-9
MacKnight W J, Karasz F E, Fried J R 1978 Solid state
transition behaviour of blends. In: Paul D R, Newman S
(eds.) 1978 Polymer Blends, Vol. 1. Academic Press, New
York, pp. 186-238
Prime R 1981 Thermosets. In: Turi 1981, pp. 435-563
Roe R J, Bair , Gieniewski C 1974 Solubility and
diffusion coefficient of antioxidants in polyethylene.
J.Appl. Polym. Sci. 18: 843-56
Ryan C L, Karasz F E, MacKnight W J 1980 Thermal
analysis of miscible and immiscible blends of and
fluorostyrene copolymers. Proc. 16th AT AS Conf. 1:
15-18
Shalaby S W, Bair 1981 Block copolymers and polyblends. In: Turi 1981, pp. 365-434
Turi (ed.) 1981 Thermal Characterization of Polymeric
Materials. Academic Press, New York
. E. Bair
[ A T & T Bell L a b o r a t o r i e s , M u r r a y Hill,
N e w Jersey, U S A ]

(a) Continuous

( b ) Discrete
Isotropic

(c)

Arced

(d)2-point

(e)4-point

Oriented

Figure 1
Representative SAXS patterns of polymers. For the
oriented patterns, the orientation axis is vertical

spaced scattering centers is s h o w n in Fig. l b ; this is

typical of a n i s o t r o p i c semicrystalline p o l y m e r . P r e
ferred o r i e n t a t i o n of a s a m p l e such as this leads t o t h e
p a t t e r n in F i g . l c , while t h e p a t t e r n s of Figs. I d a n d
l e a r e seen with highly o r i e n t e d fibers of semicrystal
line p o l y m e r s .
S o m e general aspects of o b t a i n i n g a n d i n t e r p r e t i n g
S A X S p a t t e r n s a r e o u t l i n e d below, t o g e t h e r with
selected e x a m p l e s of S A X S studies of s t r u c t u r e - p r o p
erty relations in p o l y m e r s . T h e w o r k s discussed a r e
selected as b e i n g representative of types of study;
extensive reviews of S A X S b y p o l y m e r s a r e available
by H i g g i n s a n d Stein (1978) a n d by B r o w n a n d
W e t t o n (1978). C o m p r e h e n s i v e t r e a t m e n t s of S A X S
a r e given by G u i n i e r a n d F o u r n e t (1955), B r u m b e r g e r
(1967), a n d G l a t t e r a n d K r a t k y (1982).

Polymers: X-Ray Scattering

1. Experimental

Virtually all solid p o l y m e r s c o n t a i n fluctuations in

electron density which scatter rays a t small angles.
Structures which c a n be studied by small-angle x-ray
scattering ( S A X S ) , detected a t scattering angles 2
between 2 0 " a n d 2, h a v e d i m e n s i o n s in t h e r a n g e 2 1000 n m ; the features responsible for this scattering
m a y be c o m p o s i t i o n a l fluctuations (block c o p o l y m e r s
or blends), o r density fluctuations associated with
crystallites, voids o r additives. T h e types of S A X S
p a t t e r n s n o r m a l l y e n c o u n t e r e d a r e s u m m a r i z e d in
Fig. 1. C o n t i n u o u s scattering, in which the intensity
decreases m o n o t o n i c a l l y from a m a x i m u m a t t h e
origin (2 = 0), is depicted in Fig. l a . A n interference
m a x i m u m c o r r e s p o n d i n g to s o m e w h a t regularly

A well-defined incident b e a m is required for m e a s u r

ing scattering a t small angles. C a m e r a s e m p l o y i n g
p i n h o l e c o l l i m a t i o n a r e useful for w o r k a t 2 > 0.5.
T o m a i n t a i n r e a s o n a b l e intensities a t higher resolu
t i o n s , slits a r e n o r m a l l y e m p l o y e d , t h o u g h these c a u s e
a d i s t o r t i o n o r s m e a r i n g of t h e o b s e r v e d p a t t e r n . T h e
slit-smeared p a t t e r n s of isotropic, c o n t i n u o u s scat
t e r e d (Fig. l a ) m a y be a n a l y z e d directly ( G u i n i e r a n d
F o u r n e t 1955). Discrete p a t t e r n s of i s o t r o p i c s a m p l e s
(Fig. l b ) m u s t be c o r r e c t e d before i n t e r p r e t a t i o n . A
s u m m a r y of d e s m e a r i n g p r o c e d u r e s is p r e s e n t e d b y
Schelten a n d H e n d r i c k s (1978). It s h o u l d b e n o t e d
t h a t p a t t e r n s like t h o s e in Figs, l c a n d l e a r e u n s u i t
able for slit c a m e r a s .

378

Aspects

Polymers:

T h e p a t t e r n s a r e r e c o r d e d either o n p h o t o g r a p h i c
film o r by t h e use of electronic d e t e c t o r s . Q u a n t i t a t i v e
w o r k w i t h film d e t e c t i o n requires t h e use of a m i c r o d e n s i t o m e t e r t o o b t a i n t h e angle d e p e n d e n c e of t h e
scattered intensity. T h e d e v e l o p m e n t of p o s i t i o n sensitive p r o p o r t i o n a l c o u n t e r s h a s p r o v e d a b o o n for
S A X S e x p e r i m e n t s . P a r t i c u l a r l y significant a r e t w o dimensional detectors, which permit anisotropic pat
terns t o be r e c o r d e d quickly a n d a c c u r a t e l y . High-flux
s y n c h r o t r o n r a d i a t i o n sources a r e b e c o m i n g avail
able; these p e r m i t e x p e r i m e n t s w h i c h were previously
impractical b e c a u s e of t i m e c o n s t r a i n t s o r sample-size
r e q u i r e m e n t s . A review of these a n d o t h e r d e v e l o p
m e n t s is given by Schelten a n d H e n d r i c k s (1978).
Analysis of S A X S p a t t e r n s falls i n t o t w o categories:
those involving line s h a p e (or t h e intensity d i s t r i b u
tion), a n d t h o s e w h i c h utilize i n t e g r a t e d intensities.
T h e latter a r e frequently p u t o n a n a b s o l u t e basis b y
c o m p a r i s o n w i t h a s t a n d a r d s a m p l e of k n o w n scatter
ing p o w e r . F o r this m a n i p u l a t i o n , a n d also for t h e
s u b t r a c t i o n of p a r a s i t i c scattering, t h e linear a b s o r p
tion coefficient of t h e s a m p l e is r e q u i r e d . T h e s a m p l e
-1
for
s h o u l d be p r e p a r e d w i t h a thickness t
m a x i m u m intensity; this c o r r e s p o n d s t o a thickness of
a few t e n t h s of a millimeter for m o s t p o l y m e r s .

2. Structure

of Amorphous

Polymers

A l t h o u g h t h e r e h a s been m u c h interest in t h e q u e s t i o n
of s t r u c t u r e within n o n c r y s t a l l i n e h o m o p o l y m e r s ,
evidence by scattering t e c h n i q u e s h a s b e e n lacking.
A n a l m o s t a n g l e - i n d e p e n d e n t b a c k g r o u n d intensity
d u e t o t h e r m a l l y i n d u c e d density fluctuations is n o r
mally o b s e r v e d . T h i s c a n b e expressed as

m = plW

(1)

where pe is t h e a v e r a g e electron density w i t h i n t h e

s a m p l e , k is B o l t z m a n n ' s c o n s t a n t , is t h e a b s o l u t e
t e m p e r a t u r e a n d is t h e i s o t h e r m a l compressibility
(evaluated a t t h e glass-transition t e m p e r a t u r e Tg for
T< r g). D e n s i t y fluctuations m a n i f e s t e d in E q n . (1)
h a v e been used t o follow t h e a g i n g of p o l y m e r glasses
( C u r r o a n d R o e 1984). S u p e r i m p o s e d o n this intensity
m a y be a n a n g l e - d e p e n d e n t scattering d u e t o extrinsic
features such as d u s t o r additives ( W e n d o r f f a n d
Fischer 1973a). T h i s excess s c a t t e r i n g c a n b e used t o
characterize t h e size a n d c o n c e n t r a t i o n of such inclu
sions ( B r o w n a n d W e t t o n 1978).
Blends of c o m p a t i b l e p o l y m e r s give c o n t i n u o u s
S A X S p a t t e r n s c o r r e s p o n d i n g t o s o l u t i o n s of o n e
p o l y m e r in a n o t h e r ; i n c o m p a t i b l e p o l y m e r s f o r m
structures t o o large for e x a m i n a t i o n b y S A X S .
I o n o m e r s h a v e discrete p a t t e r n s i n d i c a t i n g a p e r i o d i
city of a b o u t 5 n m associated with s o m e t y p e of
s t r u c t u r e . Block c o p o l y m e r s also h a v e b e e n m u c h
studied b y S A X S . T h e s e topics a r e reviewed by H i g gins a n d Stein (1978), a n d B r o w n a n d W e t t o n (1978).

3. Structure

of Semicrystalline

X-Ray

Scattering

Polymers

The alternating crystalline-amorphous microstruc

t u r e of semicrystalline p o l y m e r s gives rise t o discrete
p a t t e r n s w i t h a characteristic spacing o r l o n g p e r i o d
in t h e r a n g e 10-50 n m . T h e l o n g p e r i o d L, w h i c h
c o r r e s p o n d s t o t h e a v e r a g e c e n t e r - t o - c e n t e r spacing of
a d j a c e n t lamellar crystals, is e v a l u a t e d a c c o r d i n g t o
B r a g g ' s law:

w h e r e 2 0 * is t h e angle of t h e scattering m a x i m u m a n d
is t h e w a v e l e n g t h of t h e r a d i a t i o n . 2 0 * is observed
directly in well-oriented p a t t e r n s (Figs. I d , e), t h o u g h
a radial Lorentz correction must be applied to isotro
pic o r a r c e d p a t t e r n s (Figs, l b , c). T h e c o r r e c t e d
intensity function IC is o b t a i n e d from t h e e x p e r i m e n t a l
profile / o bs a c c o r d i n g t o
2

/ C ( 2 0 ) = 0 / O b (s 2 0 )

(3)

A s t h e b r e a d t h of t h e p e a k is a p p r e c i a b l e , this c o r r e c
tion decreases t h e a p p a r e n t L b y 2 0 % o r m o r e .
It is usually o b s e r v e d t h a t L increases a n d t h e
b r e a d t h of t h e scattered p e a k decreases with m o r e
careful crystallization. N e v e r t h e l e s s , only o n e o r per
h a p s t w o reflection o r d e r s a r e n o r m a l l y o b s e r v e d ,
m a k i n g m o r e detailed analyses of t h e p a t t e r n very
u n c e r t a i n . T h e a p p a r e n t lack of l o n g - r a n g e o r d e r h a s
led t o t h e use of p a r a c r y s t a l l i n e t h e o r y t o describe
imperfect s t a c k s of lamellar crystals. T w o e q u i v a l e n t
m o d e l l i n g a p p r o a c h e s a r e used: o n e involves calcu
lated intensities of t h e t y p e
I{s) = CF\s)Z(s)

(4)

a n d t h e o t h e r utilizes t h e o n e - d i m e n s i o n a l c o r r e l a t i o n
function
I(s)cos(2nsx)

ds

(5)

In E q n . (4), C is a c o n s t a n t , F is t h e scattering factor

( d e p e n d e n t o n t h e crystallinity a n d crystal s h a p e ) a n d
is t h e lattice factor, w h i c h includes s t a c k i n g dis
o r d e r . T h e m a g n i t u d e of t h e s c a t t e r i n g v ect o r is given
1
b y s = 2 A " s i n 0 . T h e c o r r e l a t i o n function () is
simply t h e F o u r i e r t r a n s f o r m of t h e intensity, t h o u g h
it m a y b e c a l c u l a t e d directly. Recently, these
a p p r o a c h e s h a v e been e x p a n d e d t o t w o - d i m e n s i o n a l
p a t t e r n s such a s t h o s e in Figs. I d a n d l e ( B e u m e r a n d
H o s e m a n n 1978, V o n k 1979). A d d i t i o n a l s t r u c t u r e
analyses a r e reviewed b y B r o w n a n d W e t t o n (1978),
a n d H a l l a n d T o y (1984).
T h e a b s o l u t e intensity in t h e small-angle region is
o b t a i n e d b y i n t e g r a t i n g t h e S A X S p a t t e r n over all
r e c i p r o c a l space. T h e r e s u l t a n t q u a n t i t y , called the
i n v a r i a n t , is given b y
2

Q = (p2-pl) ^2-3z/L)

(6)

379

Polymers:

X-Ray

Scattering

w h e r e px a n d p2 a r e the electron densities of t h e t w o

p h a s e s a n d Oj a n d 2 , a r e the v o l u m e fractions. A l s o
included is a t r a n s i t i o n z o n e of thickness a t e a c h
p h a s e b o u n d a r y ; the m a g n i t u d e of m a y also be
e s t i m a t e d by the r a t e of decrease of (2) a t relatively
large angles.
4.

Deformation

S A X S is a powerful tool for m e a s u r i n g s t r u c t u r a l

changes occurring during polymer deformation. The
plastic d e f o r m a t i o n of a semicrystalline p o l y m e r
c h a n g e s the S A X S p a t t e r n from i s o t r o p i c (Fig. l b )
t h r o u g h the arced state (Fig. lc) t o t h e highly o r i e n t e d
f o u r - p o i n t type (Fig. l e ) . A n e x a m p l e of this type of
s t u d y is presented for N y l o n 6 by M a t y i a n d Crist
(1978). O t h e r detailed studies of d e f o r m a t i o n h a v e
been p e r f o r m e d o n oriented fibers a n d films d u r i n g
largely reversible stretching. Such e x p e r i m e n t s were
d o n e by P o p e a n d Keller (1975) o n specially p r e p a r e d
films of polyethylene. W h e n c o m b i n e d with crystallog r a p h i c o r i e n t a t i o n the c h a n g e s in t h e S A X S p a t t e r n
p e r m i t t e d s e p a r a t i o n of t h e tensile strain i n t o c o m
p o n e n t s involving intracrystalline shear, intercrystalline shear a n d stretching of a m o r p h o u s regions.
A related type of d e f o r m a t i o n s t u d y involves t h e
o b s e r v a t i o n of void o r m i c r o c r a c k scattering in
stressed semicrystalline p o l y m e r s . T h e r a t e of f o r m a
tion of the voids at c o n s t a n t stress h a s been f o u n d t o
be similar t o the r a t e of c o v a l e n t - b o n d r u p t u r e which
precedes m a c r o s c o p i c failure ( K u k s e n k o et al. 1968).
S A X S h a s recently been applied t o t h e s t u d y of
crazes in d e f o r m e d a m o r p h o u s p o l y m e r s ( B r o w n a n d
K r a m e r 1981). A discrete oriented p a t t e r n gives infor
m a t i o n o n the fibrils within the craze, including fibril
d i a m e t e r d i s t r i b u t i o n a n d the r a d i a l d i s t r i b u t i o n func
tion of fibrillar m a t e r i a l . A c o n t i n u o u s p a t t e r n arising
from the craze itself is a t t r i b u t e d t o reflection at t h e
c r a z e - a i r interface ( T a n g et al. 1984).
5. Phase

Transformations

Crystallization
and
melting
of
semicrystalline
p o l y m e r s h a v e a n u m b e r of features which a r e p r o
ductively studied by S A X S . T h e d e v e l o p m e n t of t h e
S A X S p a t t e r n with time d u r i n g i s o t h e r m a l crystalliza
tion of polyethylene h a s been a n a l y z e d (Schultz et al.
1978); the c o n t i n u o u s scattering from effectively iso
lated lamellar crystals or a m o r p h o u s g a p s is replaced
by a discrete p a t t e r n as t h e lamellar stacks g r o w .
C o p o l y m e r s h a v e very b r o a d reversible melting
ranges which a r e n o w u n d e r s t o o d from t h e s t u d y of
Strobl et al. (1980). It w a s s h o w n t h a t thin lamellae
a r e selectively melted a t t h e lowest t e m p e r a t u r e s ;
these thin crystals p r e s u m a b l y c o n t a i n a n excess of
c o m o n o m e r which restricts t h e crystal size.
T h e glass t r a n s i t i o n in a m o r p h o u s p o l y m e r s is
manifested by a c h a n g e in t h e t e m p e r a t u r e d e p e n
dence of the fluctuation scattering in E q n . (1) ( W e n -

380

dorff a n d Fischer 1973b). T h e S A X S t e c h n i q u e

s h o u l d also be applicable t o studies of the glass
t r a n s i t i o n in semicrystalline p o l y m e r s . N o n c r y s t a l l i n e
block c o p o l y m e r s u n d e r g o a p s e u d o m e l t i n g t r a n s i t i o n
which h a s been studied by t h e t e m p e r a t u r e d e p e n
dence of S A X S line s h a p e a n d intensities ( R o e et al.
1981). It w a s f o u n d t h a t t h e h o m o g e n i z a t i o n of t h e
initially p h a s e - s e p a r a t e d s t r u c t u r e is a g r a d u a l func
tion of t e m p e r a t u r e ; t h e m i x i n g of t h e b l o c k segments
is n o t a
first-order
t r a n s i t i o n . T h i s w o r k also
addresses t h e p r o b l e m s of d e t e r m i n i n g t h e thickness
of t h e i n t e r p h a s e b o u n d a r y (z in E q n . (6)) by S A X S
methods.
See also: Polymers: Neutron Scattering; X-Ray and Neu
tron Diffraction Studies of Amorphous Solids
Bibliography
Beumer H, Hosemann R 1978 Two-dimensional analysis of
hot-stretched polyethylene by computer. / . Macromol.
Sci., Phys. 15: 1-17
Brown D S, Wetton R 1978 Recent advances in the study
of polymers by small angle X-ray scattering. In: Dawkins
J V (ed.) 1978 Developments in Polymer Characterization.
Applied Science, London, pp. 157-203
Brown R, Kramer J 1981 Craze microstructure from
small angle X-ray scattering. J. Macromol. Sci., Phys. 19:
487-522
Brumberger (ed.) 1967 Small-Angle X-Ray Scattering.
Gordon and Breach, New York
Curro J J, Roe R-J 1984 Isothermal relaxation of specific
volume and density in poly(methyl methacrylate) and
polycarbonate. Polymer 25: 1424-30
Glatter O, Kratky (eds.) 1982 Small Angle X-Ray Scatter
ing. Academic Press, New York
Guinier A, Fournet G 1955 Small-Angle Scattering of XRays. Wiley, New York
Hall I H, Toy 1984 The ability of small-angle x-ray
scattering to distinguish between morphological models
of crystalline polymers. In: Hall I (ed.) 1984 Structure
of Crystalline Polymers. Applied Science, London, pp.
181-228
Higgins J S, Stein R S 1978 Recent developments in polymer
applications of small-angle neutron, x-ray and light scat
tering. J. Appl. Crystallogr. 11: 346-75
Kuksenko V S, Slutsker A I, Yastrebinskii 1 1968 Formation
of submicroscopic cracks in loaded oriented amorphouscrystalline polymers. Sov. Phys. Solid State {Engl. Transl.)
9: 1869-76
Matyi R, Crist 1978 Small-angle x-ray scattering by Nylon
6. / . Polym. Sci., Polym. Phys. Ed. 16: 1329-54
Pope D , Keller A 1975 Deformation of oriented polyethy
lene. J. Polym. Sci., Polym. Phys. Ed. 13: 5333-66
Roe R J, Fishkis M, Chang J C 1981 Small angle x-ray
diffraction study of thermal transitions in styrene-butadiene block copolymers. Macromolecules 14: 1091-1103
Schelten J, Hendricks R W 1978 Recent developments in xray and neutron small-angle scattering instrumentation
and data analysis. J. Appl. Crystallogr. 11: 297-324
Schultz J M, Lin J S, Hendricks R W 1978 A dynamic study
of crystallization of polyethylene from the melt. J. Appl.
Crystallogr. 11: 551-7
Strobl G R, Schneider J, Voigt-Martin I G 1980 Model of

Porosity:

partial crystallization and melting derived from small

angle x-ray scattering and electron microscopic studies of
low density polyethylene. J. Polym. Sci., Polym. Phys. Ed.
18: 1361-81
Tang M-Y, Fellers J F, Lin J S 1984 New treatment of the
theory for small-angle x-ray scattering with applications
to polystyrene crazes. J. Polym. Sci., Polym. Phys. Ed. 22:
2215-41
Vonk C G 1979 A small angle x-ray scattering study of
polyethylene fibers using the two dimensional correlation
function. Colloid Polym. Sci. 257: 1020-32
Wendorff J H, Fischer W 1973a Small-angle x-ray scatter
ing from amorphous polymers arising from heterogenei
ties. Kolloid-Z. Z. Polym. 251: 884-91
Wendorff J H, Fischer W 1973b Thermal density fluctua
tions in amorphous polymers as revealed by small angle
x-ray diffraction. Kolloid-Z. Z. Polym. 251: 876-83
B. Crist
[ N o r t h w e s t e r n University, E v a n s t o n ,
Illinois, U S A ]

Porosity: Characterization and

Investigation
Porous materials, both natural and m a n - m a d e , are
extremely w i d e s p r e a d in o c c u r r e n c e , diverse in
p r o p e r t i e s a n d i m p o r t a n t in use. T h e p o r o s i t y of
m a n y a n i m a l a n d p l a n t tissues is literally of vital
significance. T h e p o r o s i t y of soils is essential for their
function as a w a t e r reservoir for p l a n t g r o w t h . P o r o u s
r o c k s act as s u b t e r r a n e a n reservoirs for c r u d e oil;
such r o c k s a r e also q u a r r i e d for use as c o n s t r u c t i o n a l
materials a n d a r e s u p p l e m e n t e d with artificial p o r o u s
materials such as c o n c r e t e , bricks a n d m o r t a r . In t h e
field of chemical engineering, p o r o u s m a t e r i a l s find
m a n y a p p l i c a t i o n s , including filtration m e d i a , catalyst
s u p p o r t s a n d h e a t pipes. I n e v e r y d a y life, p o r o u s
m a t e r i a l s r a n g i n g from p a p e r t o leather a n d from
fabrics to foodstuffs a r e e n c o u n t e r e d .
In all these c o n t e x t s , t h e p r o p e r functioning of t h e
m a t e r i a l c o n c e r n e d is strongly d e t e r m i n e d b y its p o r e
structure. T h e p r e s e n t article deals with t h e defini
tions of p a r a m e t e r s c o m m o n l y used t o describe p o r e
structure, with t h e principles a n d t e c h n i q u e s of m e t h
o d s used for their m e a s u r e m e n t , a n d with t h e inter
p r e t a t i o n of t h e results so o b t a i n e d . F u r t h e r details
c a n be f o u n d in several recent reviews a n d conference
proceedings (Everett a n d S t o n e 1958, E v e r e t t a n d
Ottewill 1970, Everett a n d H a y n e s 1973, M o d r y a n d
Svata 173-4, B o u c h e r 1976, G r e g g et al. 1979, H a y n e s
a n d R o s s i - D o r i a 1985).

1. Structural

Parameters

T h r e e p a r a m e t e r s a r e used t o c h a r a c t e r i z e t h e s t r u c
t u r e of a p o r o u s m a t e r i a l ; these describe (a) t h e e x t e n t
of the p o r e space, (b) t h e d i s t r i b u t i o n of t h e p o r e
v o l u m e a c c o r d i n g t o p o r e size a n d (c) t h e extent of t h e

Characterization

and

Investigation

i n t e r n a l surface b e t w e e n t h e solid m a t r i x a n d the

pores. These are macroscopic average properties and
m u s t refer t o a s a m p l e of m a t e r i a l of v o l u m e several
o r d e r s of m a g n i t u d e g r e a t e r t h a n t h e v o l u m e of a
single p o r e .
P o r o s i t y is t h e r a t i o of p o r e v o l u m e Vp to the t o t a l
v o l u m e Vp + Vs, w h e r e Vs is t h e v o l u m e of solid.
S o m e p o r o u s m a t e r i a l s c o n t a i n a significant v o l u m e
of closed p o r e s , t h a t is, p o r e s which h a v e n o fluidp e r m e a b l e c o n n e c t i o n s b e t w e e n o n e a n o t h e r ; such
p o r e s , while affecting such p r o p e r t i e s as density a n d
m e c h a n i c a l s t r e n g t h , d o n o t influence t h e m a t e r i a l ' s
capillary a n d fluid flow b e h a v i o u r . M u c h m o r e c o m
m o n l y , p o r o s i t y in m a t e r i a l s is in t h e f o r m of o p e n
p o r e s , w h i c h a r e fully i n t e r c o n n e c t e d with o n e
a n o t h e r a n d with t h e o u t e r surface of t h e m a t e r i a l .
Such m a t e r i a l s a r e fully p e r m e a b l e t o fluids. T h e cross
section of a p o r e m u s t b e of a t least m o l e c u l a r
d i m e n s i o n s in o r d e r t o p e r m i t fluid flow. I n s o m e
m a t e r i a l s , such as zeolites, t h e ability t o c o n d u c t
fluids m a y d e p e n d o n t h e m o l e c u l a r sifce of t h e fluid
c o n c e r n e d . ( O t h e r types of p e r m e a t i o n process involv
ing s o l u t i o n a n d diffusion, for e x a m p l e b e n z e n e in
r u b b e r , a r e specifically excluded from t h e discussion
of p o r o s i t y here.)
S o m e special m a t e r i a l s , such as f o a m e d plastics,
h a v e a large p o r o s i t y c o m p r i s i n g n u m e r o u s large
b u b b l e s s e p a r a t e d b y walls w h i c h a r e p e n e t r a t e d by
very m u c h smaller p o r e s . I n such cases, t h e large p o r e s
m a y d o m i n a t e t h e m e c h a n i c a l p r o p e r t i e s while the
smaller p o r e s c o n t r o l t h e p e r m e a b i l i t y .
P o r e size d i s t r i b u t i o n is expressed as t h e functional
relationship
dV=f(r)dr

(1)

w h e r e dV is t h e fractional v o l u m e of p o r e s h a v i n g
radii b e t w e e n r a n d r + dr. T h e d i s t r i b u t i o n m a y be
r e p r e s e n t e d either as a c o n t i n u o u s function o r as a
h i s t o g r a m ; it m a y be b r o a d o r n a r r o w , a n d s h o w o n e
p e a k o r m o r e , a c c o r d i n g t o t h e c o m p l e x i t y of the p o r e
structure concerned.
T h i s definition of p o r e size d i s t r i b u t i o n a p p e a r s t o
p r e s u p p o s e t h a t t h e p o r e s a r e of such a s h a p e (cylin
drical, for instance) t h a t they h a v e identifiable radii;
familiarity with c o m m o n p o r o u s m a t e r i a l s s h o w s ,
h o w e v e r , t h a t this is practically never t h e case. In
deed, m o s t p o r e s t r u c t u r e s a r e of such e x t r e m e irregu
larity t h a t it is impossible, at t h e m i c r o s c o p i c level, t o
define a n y e l e m e n t of t h e p o r e space as c o n s t i t u t i n g a
single " p o r e , " let a l o n e t o specify its " r a d i u s " in t e r m s
of its real d i m e n s i o n s . W a y s in which this p r o b l e m is
resolved will be described later.
Specific surface s is t h e e x p o s e d a r e a of solid surface
in u n i t m a s s of m a t e r i a l . W h e t h e r o r n o t this includes
t h e surface of closed p o r e s d e p e n d s o n t h e m e t h o d of
m e a s u r e m e n t . M o r e rarely t h e specific surface m a y be
referred t o as u n i t v o l u m e of m a t e r i a l , a n d given the
s y m b o l . T h e r e l a t i o n s h i p b e t w e e n a n d s is

381

Porosity:

Characterization

and

= ( 1 -

Investigation

(2)

w h e r e ps is t h e density of t h e solid m a t r i x .
T h e three m a i n s t r u c t u r a l p a r a m e t e r s a r e related,
since specific surface is p r o p o r t i o n a l t o p o r o s i t y a n d
inversely p r o p o r t i o n a l t o p o r e size. T h e p r o p o r t i o n a
lity coefficient d e p e n d s o n t h e p o r e s h a p e . F o r ex
a m p l e , if t h e p o r e s a r e all e q u a l cylinders of r a d i u s r,
then
= 2e/r

(3)

If the p o r e s a r e d i s t r i b u t e d in size b u t a r e still cylindri

cal, then
^-^-dr

(4)

(the i n t e g r a t i o n being t a k e n over all r). F o r p o r e s of

shapes o t h e r t h a n cylindrical, t h e n u m e r i c a l coeffi
cient 2 m u s t be replaced b y a s h a p e factor, w h i c h
generally carwiot b e d e t e r m i n e d a priori except for
geometrically r e g u l a r s h a p e s .
I n p o r o u s m a t e r i a l s of practical i m p o r t a n c e , t h e
values of t h e three s t r u c t u r a l p a r a m e t e r s c a n v a r y
t h r o u g h several o r d e r s of m a g n i t u d e . T h u s , t h e p o r o
sity, which m u s t necessarily lie b e t w e e n 0 a n d 1, c a n
be as low as 0.001 in s o m e types of g r a n i t e rock, a n d
a p p r o a c h e s 1 in s o m e f o a m e d p o l y m e r s . Specific
2
_1
surface m a y r a n g e from a few c m g
t o several
2
1
h u n d r e d m g " . P o r e s m a y r a n g e in size from m a c r o
scopic holes (in p u m i c e ) t o m o l e c u l a r d i m e n s i o n s (in
zeolites). C h a n n e l s o u t s i d e certain size limits a r e n o t
considered t o be p o r e s , either b e c a u s e they a r e t o o big
t o exert significant capillary effects a n d c o n t r i b u t e
negligibly t o the surface a r e a , o r b e c a u s e they a r e t o o
small t o b e p e r m e a b l e . W i t h i n these limits, p o r e s a r e
conventionally divided i n t o three size r a n g e s : m i c r o
p o r e s r < 2 n m ; m e s o p o r e s 2 n m < r < 50 n m ; a n d
m a c r o p o r e s r > 50 n m . Because these t e r m s n o w
h a v e a n i n t e r n a t i o n a l l y agreed m e a n i n g (Everett
1972), it is better t o avoid their use except in t e r m s of
t h e definitions given a b o v e . T h e physical r a t i o n a l e
u n d e r l y i n g these definitions will b e c o m e a p p a r e n t
later.
F i g u r e 1 indicates t h e r a n g e s of values of p o r e size
a n d specific surface e n c o u n t e r e d in s o m e c o m m o n
p o r o u s m a t e r i a l s . T h e d i a g o n a l lines a r e c o n t o u r s of
c o n s t a n t p o r o s i t y , as given b y E q n . (3).
Available m e t h o d s for d e t e r m i n i n g t h e three struc
tural p a r a m e t e r s a r e either direct o r indirect. D i r e c t
m e t h o d s rely o n m i c r o s c o p i c o b s e r v a t i o n s of t h e p o r e
g e o m e t r y , as revealed in thin sections o r in p l a n e
intersections of t h e p o r e s t r u c t u r e . Indirect m e t h o d s
d e p e n d o n m e a s u r e m e n t s of m a c r o s c o p i c p r o p e r t i e s
which are strongly influenced by p o r e s t r u c t u r e (such
as permeability); these a r e t h e n i n t e r p r e t e d , in t e r m s
of s o m e k i n d of m o d e l , t o yield values of t h e struc
t u r a l p a r a m e t e r s . Because m a n y p r o p e r t i e s of m a t e r
ials a r e influenced by p o r e s t r u c t u r e , indirect m e t h o d s

382

Mean pore radius ( m )

Figure 1
Pore size and specific surface of some common porous
materials

a r e c o r r e s p o n d i n g l y n u m e r o u s . W h e r e a s direct m e t h
ods, w h e n p r o p e r l y a p p l i e d , m a y yield results of high
a b s o l u t e a c c u r a c y , their i n t e r p r e t a t i o n in t e r m s of t h e
practical p e r f o r m a n c e of m a t e r i a l s is often u n c e r t a i n .
Indirect m e t h o d s , o n t h e o t h e r h a n d , give results t h a t
a r e strongly m o d e l - d e p e n d e n t b u t m a y nevertheless
yield i n f o r m a t i o n of m o r e i m m e d i a t e practical value.
Indirect m e t h o d s a r e therefore m o r e widely used.
It s h o u l d be m e n t i o n e d t h a t reference samples of
c a l i b r a t e d s t a n d a r d surface a r e a m a t e r i a l s a r e avail
able, as a result of a n i n t e r l a b o r a t o r y c o l l a b o r a t i v e
project (Everett et al. 1974). T h e four m a t e r i a l s avail
2
1
able cover t h e r a n g e 10-300 m g " as d e t e r m i n e d b y
t h e B r u n a u e r - E m m e t t - T e l l e r ( B E T ) t e c h n i q u e using
n i t r o g e n (see below). S a m p l e s of lower specific surface
a n d m a t e r i a l s of c a l i b r a t e d s t a n d a r d p o r e size a r e also
being studied as p o t e n t i a l reference m a t e r i a l s .

2. Direct Methods
Characterization

of Pore

Structural

A p l a n e section t h r o u g h a p o r o u s m a t e r i a l , w h e n
e x a m i n e d b y a suitable optical- o r electronm i c r o s c o p e t e c h n i q u e , reveals the intersections of t h e
s a m p l i n g p l a n e with t h e b o u n d a r i e s b e t w e e n solid
matrix and pores. Contrast between pore a n d matrix
m a y be e n h a n c e d b y p r i o r i m p r e g n a t i o n of t h e p o r e s
by resin; this m a y also r e d u c e t h e possibility of
accidental d a m a g e t o t h e p o r e s t r u c t u r e d u r i n g
specimen p r e p a r a t i o n . T h e r e c o n s t r u c t i o n of t h r e e dimensional information a b o u t the pore structure

Porosity:

Characterization

and

Investigation

crosses t h e b o u n d a r i e s of p o r e s (the intersection

n u m b e r Xps) a n d t h e n u m b e r of times a n e n d of
t h e line lies within a p o r e (the t e r m i n a t i o n n u m b e r
) . T h e r a t i o XJTp eventually t e n d s t o a c o n s t a n t
value w h e n e n o u g h c o u n t s h a v e been m a d e . T h e
specific surface is t h e n given b y t h e C h a l k l e y
equation:
= 4*- /
(6)
or

s=

Figure 2
Stereological quantities revealed by a plane section
through a porous solid: (a) areal analysis; (b) lineal
analysis; (c) point counting; (d) intersect analysis
(O = termination, = intersection)

from o b s e r v a t i o n s in t w o , o n e o r z e r o d i m e n s i o n s is
c o n d u c t e d b y t h e m e t h o d s of stereology.
T h e definition of p o r o s i t y c a n b e e x t e n d e d i n t o
lower dimensionalities:
e=Vp/(Vp+Vs)
= Ap/(Ap

As)

( 2 D : areal analysis)

= L p/ ( L p + L s)

( I D : lineal analysis)

= Np/(Np

(OD: p o i n t c o u n t i n g )

+ Ns)

(5)

w h e r e subscripts a n d s refer t o p o r e a n d solid,

respectively. T h u s , Ap a n d As a r e t h e a r e a s of p o r e a n d
m a t r i x revealed b y a p l a n e section (Fig. 2a). If t h e
section is s c a n n e d b y a series of lines, Lp a n d L s a r e t h e
t o t a l lengths of lines lying in p o r e s a n d m a t r i x (Fig.
2b). If t h e lines a r e replaced b y a n a r r a y of p o i n t s , Np
a n d Ns a r e t h e c o r r e s p o n d i n g n u m b e r s of p o i n t s in
each p h a s e (Fig. 2c). I n F i g . 2 b a n d c, it is i m m a t e r i a l
w h e t h e r t h e lines a n d p o i n t s a r e regularly o r r a n
d o m l y d i s t r i b u t e d ; h o w e v e r , t h e r e g u l a r a r r a y s illus
t r a t e d a r e typical of t h e s c a n n i n g p a t t e r n s in m o d e r n
i n s t r u m e n t a l analysis. T h e s e r e l a t i o n s h i p s a r e inde
p e n d e n t of t h e o r i e n t a t i o n of t h e s a m p l i n g p l a n e
even if the p o r e s h a v e a preferred o r i e n t a t i o n , p r o
vided only t h a t t h e p l a n e s a r e r a n d o m l y spaced.
F u r t h e r m o r e , since t h e p o r o s i t y is a p u r e n u m b e r , its
d e t e r m i n a t i o n b y this m e t h o d is i n d e p e n d e n t of t h e
magnification a t w h i c h t h e s a m p l e is e x a m i n e d , p r o
vided t h a t this is sufficient t o resolve all t h e p o r e s .
T h e specific surface c a n b e d e t e r m i n e d stereologically by r e p e a t e d l y placing a s t r a i g h t line of length
in r a n d o m l y c h o s e n p o s i t i o n s o n t h e p l a n e surface a s
in Fig. 2d a n d c o u n t i n g t h e n u m b e r of times t h e line

4eXpJ(l-s)psXTp

(6a)

I n p r a c t i c e , such m e a s u r e m e n t s a r e m a d e o n a suit
ably magnified i m a g e of t h e p l a n e section a n d the
a c t u a l length of t h e test line m u s t b e divided b y the
magnification factor t o o b t a i n t h e a p p r o p r i a t e value
of .
Stereological d e t e r m i n a t i o n of p o r e size is m u c h
m o r e difficult, n o t only b e c a u s e of t h e e x t r e m e irregu
larity of p o r e s h a p e , b u t also b e c a u s e t h e cross section
of a given p o r e as revealed by sectioning d e p e n d s o n
t h e o r i e n t a t i o n of t h e p o r e axis relative t o t h e s a m
pling p l a n e . F o r e x a m p l e , a n elliptical outline m a y
indicate a n elliptical p o r e o r a n o b l i q u e section of a
cylinder. T h e d i s t a n c e b e t w e e n t w o parallel t a n g e n t s
t o a p o r e o u t l i n e m a y be t a k e n as a m e a s u r e of the
p o r e size, t h o u g h this will d e p e n d o n t h e o r i e n t a t i o n
of t h e t a n g e n t s . If t h e m a x i m u m a n d m i n i m u m of
such lengths c a n be m e a s u r e d , their m e a n m a y be a
b e t t e r m e a s u r e of d i a m e t e r , t h o u g h there m a y be
a m b i g u i t y if t h e p o r e h a s a r e e n t r a n t outline. Diffi
culties arise, h o w e v e r , w h e n this projected d i a m e t e r in
t h e s a m p l i n g p l a n e m u s t be related t o a t r u e p o r e size.
A m e a n p o r e size c a n b e defined in t e r m s of
h y d r a u l i c r a d i u s r h. F o r a p o r e of a r b i t r a r y s h a p e this
is defined a s twice t h e r a t i o of t h e p e r i m e t e r of a given
cross section t o its a r e a . I n t e r m s of q u a n t i t i e s a l r e a d y
defined, this leads t o

rh = 2s/L
=

(7)

/2

ps

(8)

F o r an isotropic structure, the experimental quantities

in E q n . (8) a r e i n d e p e n d e n t of t h e relative o r i e n t a t i o n s
of s a m p l i n g p l a n e a n d p o r e axes.
I n s t r u m e n t a l l y , stereological analysis is m o s t c o n
veniently p e r f o r m e d b y projecting a n i m a g e of t h e
s a m p l i n g p l a n e o n t o a vidicon o r television c a m e r a
t u b e , w h e r e a line scan of t h e i m a g e is g e n e r a t e d .
C o n t r a s t of b r i g h t n e s s b e t w e e n p o r e a n d m a t r i x gives
rise t o differences in signal intensity as t h e s c a n n i n g
line e n c o u n t e r s p o r e b o u n d a r i e s , w h i c h c a n be digi
tally a n a l y z e d t o p r o v i d e all t h e necessary stereologi
cal d a t a . I n this w a y , a large a m o u n t of detailed
i n f o r m a t i o n c a n be g e n e r a t e d very rapidly. Several
c o m m e r c i a l systems a r e available. F u l l e r theoretical
a n d p r a c t i c a l details a r e given, for e x a m p l e , b y
U n d e r w o o d (1970).

383

Porosity:

3. Indirect

Characterization

Methods

and

of Pore

Investigation

Structural

Characterization
M o s t m a c r o s c o p i c p r o p e r t i e s of p o r o u s m e d i a d e p e n d
strongly o n the p o r e s t r u c t u r e , a n d in a n u m b e r of
instances the influence of p o r e s t r u c t u r e o n a given
p r o p e r t y is described q u a n t i t a t i v e l y by theories in
which the real, c o m p l e x s t r u c t u r e is replaced by a
simple m o d e l . S t r u c t u r a l p a r a m e t e r s for t h e m o d e l a r e
then derived from e x p e r i m e n t a l m e a s u r e m e n t s of the
p r o p e r t i e s of t h e real m a t e r i a l a n d a p p l i c a t i o n of the
a p p r o p r i a t e t h e o r y . T h e r e l a t i o n s h i p (if a n y ) b e t w e e n
m o d e l a n d real structures is often o b s c u r e , a n d varies
from case t o case; this p r o b l e m is considered further
in Sect. 4.
M a t e r i a l p r o p e r t i e s c o m m o n l y used for indirect
p o r e s t r u c t u r a l c h a r a c t e r i z a t i o n include density, per
meability t o fluids, a d s o r p t i v e c a p a c i t y for gases a n d
v a p o u r s , a n d capillary b e h a v i o u r t o w a r d s liquids.
3.1 Density
T h e density of a p o r o u s m a t e r i a l m a y be expressed
either as ph, t h e b u l k density (i.e., the m a s s of u n i t
v o l u m e of m a t e r i a l including all p o r e s ) , o r as ps, t h e
solid density (i.e., t h e m a s s of u n i t v o l u m e of the solid
m a t r i x ) . If closed p o r e s a r e present, a further c o n c e p t
is p's, the a p p a r e n t solid density, which is the m a s s of
unit v o l u m e of m a t r i x including its closed p o r e s . It
then follows t h a t the p o r o s i t y is given by
e=\-ph/ps

(9)

If closed p o r e s are present, E q n . (9) gives the t o t a l

porosity; the o p e n a n d closed porosities a r e given by
e

9a

-PblP's

()

ec = Pb(Ps-p's)/PsPs

(9b)

and

Densities are usually m e a s u r e d by fluid d i s p l a c e m e n t

m e t h o d s d e p e n d i n g o n A r c h i m e d e s ' principle (al
t h o u g h for m a t e r i a l s which c a n be c u t i n t o large
pieces of regular s h a p e , such as m a n y p o r o u s building
materials, ph c a n be m e a s u r e d directly). O t h e r w i s e , pb
m u s t be d e t e r m i n e d from the d i s p l a c e m e n t v o l u m e in
a liquid which d o e s n o t p e n e t r a t e t h e p o r e s . F o r m a n y
materials, m e r c u r y is a suitable liquid: a t a t m o s p h e r i c
pressure, m e r c u r y is excluded from all p o r e s of e q u i
valent cylindrical d i a m e t e r below 14.7 (see Sect.
3.5). Alternatively, pb c a n be m e a s u r e d from t h e
displacement v o l u m e after all p o r e s h a v e been filled
with w a x o r resin. T h e m a t r i x density ps c a n be
o b t a i n e d from the d i s p l a c e m e n t v o l u m e in a liquid
which completely p e n e t r a t e s t h e o p e n p o r e s . F o r
m a n y solids, e v a c u a t i o n followed b y i m m e r s i o n in airfree w a t e r ( p e r h a p s with r e p e a t e d boiling a n d cooling)
will achieve this. Alternatively, gas p y c n o m e t r y m a y
be e m p l o y e d , using a n o n a d s o r b i n g gas such as d r y
helium. If closed p o r e s a r e present, these m e t h o d s give
/?s', a n d ps m u s t be d e t e r m i n e d o n a s a m p l e of m a t e r i a l
crushed t o a particle size smaller t h a n t h e smallest

384

closed p o r e s . S o m e t i m e s , if the solid is available in

n o n p o r o u s form, ps is a l r e a d y k n o w n .
It m u s t be a s s u m e d t h a t t h e density of t h e displaced
fluid is n o t significantly affected by p r o x i m i t y t o t h e
solid surface, a c o n d i t i o n w h i c h m a y n o t be m e t if t h e
solid is of exceptionally high specific surface. M o r e
over, if m i c r o p o r e s a r e present, the m e a s u r e d value of
ps m a y d e p e n d o n the m o l e c u l a r v o l u m e of the dis
placed fluid. A further source of u n c e r t a i n t y arises
with m a t e r i a l s h a v i n g a relatively large a n d r o u g h
external surface in relation t o their v o l u m e , such as
p a p e r a n d fabrics. In such cases, p o r o s i t y m e a s u r e
m e n t is h a m p e r e d by t h e difficulty of defining t h e
external surface of the m a t e r i a l . F u r t h e r details a r e
given by v a n K e u l e n in H a y n e s et al. (1973 p . 181).
3.2 Permeability
to Fluids
W h e n a n incompressible fluid of viscosity , s a t u r a t
ing t h e p o r e space of a s a m p l e of p o r o u s solid of cross
section A, is c a u s e d t o flow by t h e i m p o s i t i o n of a
p r e s s u r e g r a d i e n t AP/L, t h e v o l u m e flow r a t e Q is
given by D a r c y ' s law:
Q = kAAPfoL

(10)

T h e p r o p o r t i o n a l i t y c o n s t a n t k is k n o w n as t h e
specific p e r m e a b i l i t y coefficient, o r m o r e briefly t h e
permeability.
All the q u a n t i t i e s in D a r c y ' s law a r e directly m e a
surable, except for k. T h u s , by m e a s u r i n g t h e v o l u m e
flow r a t e of a liquid of k n o w n viscosity u n d e r a
k n o w n pressure t h r o u g h a s a t u r a t e d s a m p l e of a
p o r o u s m a t e r i a l of regular s h a p e a n d k n o w n d i m e n
sions, k m a y be d e t e r m i n e d experimentally. P r o v i d e d
t h a t t h e liquid is N e w t o n i a n , t h e flow r a t e s h o u l d b e
directly p r o p o r t i o n a l t o t h e applied p r e s s u r e a n d k
s h o u l d be i n d e p e n d e n t of flow r a t e . E x c e p t i o n s m a y
be e n c o u n t e r e d
(a)

if t h e solid c o n t a i n s loosely held particles of

small size (e.g., clay m i n e r a l s in s o m e s a n d
stones), which m a y b e c o m e d e t a c h e d a n d o b
struct flow a t high flow rates;

(b)

if electrokinetic effects (principally s t r e a m i n g

p o t e n t i a l ) a r e significant, as with electrolyte solu
tions flowing p a s t p o l a r surfaces; o r

(c)

if t h e flow r a t e is sufficiently high for the onset of

turbulence.
2

P e r m e a b i l i t y h a s d i m e n s i o n s of [length ]. A c o m
m o n practical u n i t of p e r m e a b i l i t y is t h e d a r c y , which
1 3
2
in SI units h a s t h e value 9.8 1 0 " m . A p o r o u s
m a t e r i a l h a s a permeability of o n e d a r c y w h e n a
p r e s s u r e difference of 1 a t m p r o d u c e s a flow of
3
1
1 c m s " of a fluid with viscosity 1 M P a s t h r o u g h a
c u b e of 1 c m edge. T h e p e r m e a b i l i t y is t h u s a m e a s u r e
of t h e ease of fluid flow t h r o u g h a p o r o u s solid a n d is
evidently p r o p o r t i o n a l b o t h t o the p o r o s i t y a n d t o
s o m e function of p o r e size (since smaller p o r e s , h a v
ing a g r e a t e r s u r f a c e - v o l u m e r a t i o , offer m o r e resis
t a n c e t o flow). A simple a p p l i c a t i o n of Poiseuille's law

Porosity:

for incompressible flow in a single cylindrical capill

ary of r a d i u s r leads t o
2

k = er /S

(11)

C o m b i n a t i o n with E q n s . (2) a n d (3) yields t h e expres

sion
3

: = /2(1

s) sYs

(12)

k n o w n as t h e K o z e n y e q u a t i o n .
E q u a t i o n (12) is b a s e d o n t h e a s s u m p t i o n t h a t t h e
pores a r e u n i f o r m cylinders aligned in t h e direction of
flow. It h a s been modified t o t a k e a c c o u n t of t h e fact
t h a t t h e p o r e cross section m a y b e noncylindrical a n d
t h a t flow m a y p u r s u e a m o r e t o r t u o u s p a t h t h r o u g h
the p o r o u s m e d i u m , t h u s s p r e a d i n g t h e p r e s s u r e d r o p
over a length greater t h a n L. T h e r e s u l t a n t K o z e n y Carman equation
k =

2 2 2

s /2(\-s) s p sTf

(12a)

c o n t a i n s t w o dimensionless empirical q u a n t i t i e s ,
(the t o r t u o s i t y factor) a n d / (the p o r e s h a p e factor),
which c a n n o t b e e v a l u a t e d a priori. F r o m e x p e r i m e n t s
with m a t e r i a l s of s u p p o s e d l y k n o w n p o r e g e o m e t r y ,
C a r m a n f o u n d t h a t t h e p r o d u c t Tf w a s a p p r o x i m a t e l y
equal t o 2.5. T h e K o z e n y - C a r m a n e q u a t i o n is often
used with this value of Tf t o e v a l u a t e t h e specific
surface of m a t e r i a l s from e x p e r i m e n t a l m e a s u r e m e n t s
of k, a n d ps
T h e flow of gases in p o r o u s m e d i a follows b r o a d l y
similar principles a n d t h e e q u a t i o n s given a b o v e c a n
easily be modified t o include t h e effects of c o m p r e s s i
bility, a s s u m i n g ideal-gas b e h a v i o u r . G a s t r a n s p o r t
b e c o m e s m o r e c o m p l i c a t e d in fine p o r e s (or a t low
pressures) w h e n t h e m e a n free p a t h of t h e g a s m o l
ecules is n o longer small c o m p a r e d with t h e d i a m e t e r
of t h e p o r e s . T h e i n t e r p r e t a t i o n m a y b e further c o m
plicated b y a d s o r p t i o n o n t h e p o r e walls o r even
capillary c o n d e n s a t i o n of c o n d e n s a b l e v a p o u r s (see
Sects. 3.3 a n d 3.5). Electrokinetic effects a r e , h o w e v e r ,
absent in t h e case of g a s flow.
E x p e r i m e n t a l t e c h n i q u e s for d e t e r m i n i n g t h e speci
fic permeability from either liquid o r gas flow a r e
relatively simple a n d several c o m m e r c i a l i n s t r u m e n t s
are available. T h e r e q u i r e m e n t is merely t o b e able t o
m e a s u r e t h e fluid flow r a t e across a s a m p l e of k n o w n
d i m e n s i o n s u n d e r a given i m p o s e d pressure; it is
possible either t o establish a c o n s t a n t flow r a t e b y
m e a n s of a p u m p a n d t o m e a s u r e t h e r e s u l t a n t p r e s
sure d r o p , o r conversely t o establish a c o n s t a n t p r e s
sure d r o p a n d t o m e a s u r e t h e flow. Alternatively, a
falling-head device m a y be used, in which t h e p r e s s u r e
decays as flow p r o c e e d s : this gives d a t a c o v e r i n g a
range of flow rates, from which t h e c o n s t a n c y of k
m a y b e tested.
F o r c o m p r e h e n s i v e discussions of t h e t h e o r y of
fluid flow in p o r o u s m e d i a , see Scheidegger (1974) a n d
Dullien (1979), a n d for useful e x p e r i m e n t a l details,

Characterization

and

Investigation

see t h e articles b y D a r r a n d L u d w i g a n d by Niesel in

H a y n e s et al. (1973).
3.3 Adsorption of Gases and Vapors
G a s molecules in t h e vicinity of a solid surface m a y
experience a n attractive force giving rise t o a n
e n h a n c e d c o n c e n t r a t i o n a t t h e surface; this is the
p h e n o m e n o n of a d s o r p t i o n a n d it is found quite
generally a t all k i n d s of interface. T h e q u a n t i t y of gas
a d s o r b e d b y a solid is a function of b o t h t e m p e r a t u r e
a n d pressure, a n d d e p e n d s also o n t h e extent of the
solid surface. Below t h e critical t e m p e r a t u r e , the
a d s o r b e d layer m a y resemble a liquid film, w h o s e
thickness m a y a p p r o a c h several m o l e c u l a r d i a m e t e r s
as t h e p r e s s u r e a p p r o a c h e s t h e s a t u r a t i o n v a p o r pres
sure (where b u l k c o n d e n s a t i o n sets in). T h e specific
surface of t h e solid m a y be e s t i m a t e d if it is possible t o
d e t e r m i n e t h e q u a n t i t y of a d s o r b e d v a p o r which
w o u l d b e sufficient t o form a close-packed layer o n e
molecule thick (the m o n o l a y e r capacity) a n d if a n
a r e a c a n b e assigned t o a single a d s o r b e d molecule.
The Brunauer-Emmett-Teller (BET) equation
gives t h e v o l u m e a d s o r b e d F a s a function of the
v a p o r p r e s s u r e p:
V =

Vmcx
(l-*)[l + (c-l)x]

(13)

w h e r e = p/p0 is t h e relative v a p o r p r e s s u r e (p0 is the

s a t u r a t i o n v a p o r p r e s s u r e a t t h e t e m p e r a t u r e of t h e
e x p e r i m e n t ) , Vm is t h e m o n o l a y e r c a p a c i t y expressed
3
in t h e s a m e units a s V (usually c m g a s ( S T P ) p e r g r a m
of solid) a n d c is a p a r a m e t e r r a t h e r loosely related t o
t h e s t r e n g t h of t h e a d s o r p t i o n forces. E q u a t i o n (13)
c a n b e recast in t h e linearized form:

V(\-x)

Vmc

Vmc

(13a)

a n d t h e e x p e r i m e n t a l d a t a (V as a function of x) c a n
be p l o t t e d as x/ V( 1 x) a g a i n s t x. T h e slope a n d
intercept of t h e r e s u l t a n t straight line c a n t h e n be
solved t o give Vm a n d c. In practice, r e a s o n a b l e
linearity is often f o u n d in t h e r a n g e 0.05 < < 0.30,
with t h e m o n o l a y e r being c o m p l e t e d (V= Vm) a t
= 0.12 0.04. T h e m o n o l a y e r c a p a c i t y is c o n v e r t e d
to a n u m b e r of molecules b y m u l t i p l i c a t i o n b y
19
3
2.687 x 1 0 (the n u m b e r of molecules in 1 c m of ideal
gas a t S T P ) . M u l t i p l i c a t i o n b y t h e a r e a p e r molecule
t h e n gives t h e specific surface of t h e solid.
T h e B E T e q u a t i o n is based o n a simplified m o d e l of
t h e a d s o r p t i o n process; for a detailed criticism see, for
e x a m p l e , A d a m s o n (1982). A l t e r n a t i v e m o d e l s yield
o t h e r e q u a t i o n s which c a n also be used t o e v a l u a t e t h e
m o n o l a y e r capacity. Since, h o w e v e r , such m o d e l s
often c o n t a i n adjustable p a r a m e t e r s , w h o s e values a r e
c o n v e n t i o n a l l y c h o s e n t o yield a g r e e m e n t with the
B E T Vm, there is little a d v a n t a g e in using t h e m , a n d
they a r e n o t discussed here.

385

Porosity:

Characterization

and

Investigation

Table 1
Some typical adsorbates suitable for specific surface
determination at different temperatures

Adsorbate

Working
temperature
CQ

Saturation vapor
pressure (torr)

Molecular2
area (nm )

Nitrogen
w-Butane
Benzene
Water

- 195.8
0
25
25

760
774.5
95.18
23.756

0.162
0.444
0.430
0.125

A key p a r a m e t e r in d e t e r m i n i n g s from Vm is t h e
a r e a assigned t o a single a d s o r b e d molecule. A selec
tion of c o n v e n t i o n a l l y accepted values is given in
T a b l e 1. T h e s e values h a v e b e e n allocated principally
o n the basis of their ability t o p r o v i d e self-consistency
between values of s d e t e r m i n e d from t h e a d s o r p t i o n
of different v a p o r s . H o w e v e r , there is evidence t h a t
the effective m o l e c u l a r a r e a of a given a d s o r b a t e m a y
d e p e n d o n t h e n a t u r e of t h e solid surface; this, c o m
bined with t h e simplifying a s s u m p t i o n s of t h e B E T
m o d e l , m e a n s t h a t specific surface a r e a s e s t i m a t e d
from gas a d s o r p t i o n h a v e a r a t h e r limited claim t o
a b s o l u t e accuracy.
T h e r e a r e three general m e t h o d s available for
e x p e r i m e n t a l m e a s u r e m e n t of gas a d s o r p t i o n iso
t h e r m s . T h e basic r e q u i r e m e n t is t o m e a s u r e t h e
q u a n t i t y a d s o r b e d p e r g r a m of solid, a t s o m e fixed
t e m p e r a t u r e , as a function of relative v a p o r p r e s s u r e .
T h e t e m p e r a t u r e c h o s e n is usually below t h e critical
t e m p e r a t u r e of t h e gas c o n c e r n e d a n d s h o u l d be o n e
at which the v a p o r pressures a r e conveniently m e a s u r
able; the t e m p e r a t u r e s given in T a b l e 1 a r e often used.
Before t h e m e a s u r e m e n t , t h e s a m p l e m u s t b e freed of
foreign a d s o r b e d m a t e r i a l ( " o u t g a s s e d " ) , usually b y
e x p o s u r e t o high v a c u u m a t elevated t e m p e r a t u r e .
T h e choice of o u t g a s s i n g t e m p e r a t u r e m a y be difficult
for t h e r m a l l y sensitive m a t e r i a l s .
Gravimetric methods depend on estimating the
q u a n t i t y a d s o r b e d from t h e c h a n g e in m a s s of t h e
s a m p l e as it is e x p o s e d t o successively higher relative
v a p o r pressures. B u o y a n c y c o r r e c t i o n s a r e significant
with m a t e r i a l s of low specific surface. C o m m e r c i a l l y
available v a c u u m m i c r o b a l a n c e s h a v e sensitivities of
6
1
1 0 " g g~ o r better, which is a d e q u a t e for such w o r k .
2
( F o r e x a m p l e , a m o n o l a y e r of w a t e r o n 1 m of
surface h a s a m a s s of 0.277 m g . )
V o l u m e t r i c m e t h o d s e m p l o y a gas b u r e t t e t o esti
m a t e t h e n u m b e r of m o l e s of a gas from m e a s u r e
m e n t s of p r e s s u r e , v o l u m e a n d t e m p e r a t u r e . Similar
m e a s u r e m e n t s after e x p o s u r e t o t h e s a m p l e give a
r e d u c e d n u m b e r of m o l e s , t h e difference being t h e
a m o u n t a d s o r b e d . T h e effective v o l u m e of t h e s a m p l e
c h a m b e r is r e d u c e d by t h e v o l u m e o c c u p i e d b y t h e
s a m p l e ; m a k i n g a c c u r a t e a l l o w a n c e for this ( " d e a d s p a c e " c o r r e c t i o n ) b e c o m e s increasingly i m p o r t a n t

386

with s a m p l e s of lower a r e a . Several c o m m e r c i a l v o l u

m e t r i c i n s t r u m e n t s a r e available, s o m e with m i c r o
processor control and data reduction.
F l o w m e t h o d s e m p l o y a t e c h n i q u e similar t o t h a t of
gas c h r o m a t o g r a p h y . A s t r e a m of a gas t h a t is n o t
a d s o r b e d , such as h e l i u m , c o n t a i n i n g a k n o w n partial
p r e s s u r e of t h e a d s o r b a t e is p a s s e d t h r o u g h a p a c k e d
b e d of t h e s a m p l e a n d t h e q u a n t i t y a d s o r b e d is
d e t e r m i n e d b y s o m e k i n d of i n t e g r a t i n g d e t e c t o r
w h i c h m o n i t o r s t h e difference in a d s o r b a t e c o n c e n t r a
tion b e t w e e n i n c o m i n g a n d o u t g o i n g s t r e a m s . T h e
m e t h o d lacks sensitivity with l o w - a r e a solids, b u t it
h a s t h e a d v a n t a g e s t h a t a d s o r p t i o n e q u i l i b r i u m is
r e a c h e d r a p i d l y a n d t h a t o u t g a s s i n g is carried o u t
in t h e h e l i u m s t r e a m ( t h u s o b v i a t i n g t h e need for
high v a c u u m ) . A g a i n , c o m m e r c i a l i n s t r u m e n t s a r e
available.
Several b o o k s give excellent a c c o u n t s of t h e t h e o r y
a n d t e c h n i q u e of surface-area d e t e r m i n a t i o n b y
a d s o r p t i o n m e t h o d s , including Y o u n g a n d Crowell
(1962) a n d G r e g g a n d Sing (1982). S o u r c e s of experi
m e n t a l e r r o r in gas a d s o r p t i o n m e a s u r e m e n t s a r e
discussed b y E v e r e t t et al. (1974).
3.4 Adsorption

from

Solution

A d s o r p t i o n forces also o p e r a t e a t t h e s o l i d - l i q u i d
interface a n d m a y c a u s e local c h a n g e s in t h e c o m p o s i
tion of a s o l u t i o n close t o a solid surface. A c c u m u l a
tion of solute a t t h e surface will c a u s e a c o r r e s p o n d i n g
d e p l e t i o n in t h e b u l k s o l u t i o n , from w h i c h t h e q u a n
tity a d s o r b e d m a y t h e n b e e s t i m a t e d . F o r e x a m p l e ,
t h e d y e m e t h y l e n e b l u e is s t r o n g l y a d s o r b e d from
dilute a q u e o u s s o l u t i o n b y m a n y solids a n d t h e q u a n
tity a d s o r b e d c a n b e d e d u c e d from c o l o r i m e t r i c a n a l y
sis of t h e s o l u t i o n before a n d after a d s o r p t i o n .
A d s o r p t i o n of this k i n d m a y s o m e t i m e s follow t h e
Langmuir equation
n/nm = bc/(l+bc)

(14)

w h e r e is t h e n u m b e r of m o l e s of a d s o r b e d m a t e r i a l
p e r g r a m of solid, in e q u i l i b r i u m w i t h a s o l u t i o n
of m o l a r c o n c e n t r a t i o n c, a n d b is a t e m p e r a t u r e d e p e n d e n t c o n s t a n t loosely related t o t h e s t r e n g t h of
a d s o r p t i o n . T h e m o n o l a y e r c a p a c i t y nm (in similar
u n i t s t o t h o s e of n) c a n b e d e t e r m i n e d from experi
m e n t a l d a t a p l o t t e d in t h e linearized form:
c/n = c/nm+l/nmb

(14a)

T h e specific surface c a n t h e n b e d e t e r m i n e d from a

k n o w l e d g e of t h e a r e a o c c u p i e d b y a single molecule
in t h e m o n o l a y e r .
I n practice, a l t h o u g h such m e a s u r e m e n t s m a y
s o m e t i m e s b e very simple t o m a k e , their i n t e r p r e
t a t i o n is usually extremely u n c e r t a i n . C o m p e t i t i o n
b e t w e e n solute a n d solvent a d s o r p t i o n , p H d e p e n
d e n c e a n d electrical d o u b l e - l a y e r effects in a q u e o u s
systems, a n d wide variability of a p p a r e n t m o l e c u l a r
a r e a s a r e c o m p l i c a t i o n s a b s e n t from gas a d s o r p t i o n

Porosity:

Characterization

and

Table 2
Hydrostatic pressure difference and relative vapor pressure
p/p0 as a function of meniscus radius of curvature r0 for
mercury and water at 25 C

Vapor

Mercury
Solid

r0 ()

Figure 3
Definition of the contact angle

m e t h o d s , w h i c h a r e therefore strongly preferred in

m o s t instances.
3.5 Capillary

Equilibrium

T h e capillary b e h a v i o r of liquids in fine p o r e s is o f

m u c h i m p o r t a n c e in m a n y of t h e practical a p p l i c a
tions of p o r o u s m a t e r i a l s . It also underlies several
indirect m e t h o d s of s t r u c t u r a l e x a m i n a t i o n . T h e inter
action b e t w e e n a given liquid a n d solid is described
q u a n t i t a t i v e l y b y t h e c o n t a c t angle f o r m e d b e t w e e n
the liquid a n d its v a p o r o n a p l a n e , n o n p o r o u s surface
of t h e solid ( F i g . 3). T h e t e r m s w e t t i n g a n d n o n w e t ting refer t o c o n t a c t angles below a n d a b o v e 90,
respectively. W h e n t h e c o n t a c t angle is z e r o , t h e liquid
m a y s p r e a d w i t h o u t limit a c r o s s t h e solid surface.
W h e n a liquid f o r m s a m e n i s c u s within a fine
cylindrical capillary of r a d i u s r, t h e m e a n c u r v a t u r e C
of t h e m e n i s c u s is given (see F i g . 4) b y
C=

Investigation

- 2 / r 0 = - ( 2 cos 0)/r

(15)

w h e r e r 0 is t h e r a d i u s o f c u r v a t u r e of t h e (spherical)
meniscus. ( D i s t o r t i o n b y gravity is negligible in p o r e s
small e n o u g h t o b e of p r a c t i c a l interest.) T h e interfa
cial m e a n c u r v a t u r e C c a n b e d e t e r m i n e d e x p e r i m e n
tally in a n u m b e r of w a y s , w h i c h therefore afford
indirect r o u t e s t o t h e p o r e size r.

100
10
1
0.1
0.05
0.01
0.005
0.002

AP

(MPa)

0.0096
0.096
0.96
9.6
19.2
96
192
480

Water
PlPo

1.000
1.001
1.006
1.059
1.121
1.772
3.14
17.5

(MPa)

0.00144
0.0144
0.144
1.44
2.88
14.4
28.8
72.0

PlPo

1.000
1.000
0.999
0.990
0.979
0.901
0.811
0.593

First, t h e m e c h a n i c a l e q u i l i b r i u m c o n d i t i o n for a
c u r v e d fluid interface w i t h surface t e n s i o n is given
by t h e L a p l a c e e q u a t i o n :
AP = aC

(16)

w h e r e AP is a h y d r o s t a t i c p r e s s u r e difference across
t h e interface. F r o m E q n . (15), C is negative for a
w e t t i n g liquid a n d t h e p r e s s u r e in t h e liquid is less
t h a n t h a t in t h e v a p o r . T h u s , in o r d e r t o w i t h d r a w a
w e t t i n g liquid from a p o r e , a suction m u s t b e applied,
with m a g n i t u d e inversely p r o p o r t i o n a l t o t h e p o r e
size. F o r a n o n w e t t i n g liquid (such a s m e r c u r y against
m o s t solids) C is positive a n d t h e p r e s s u r e in t h e liquid
exceeds t h a t in t h e v a p o r . H e r e , a n excess pressure
m u s t b e a p p l i e d t o force liquid i n t o t h e p o r e , a g a i n
inversely p r o p o r t i o n a l t o p o r e size.
S e c o n d , t h e c o n d i t i o n of diffusional e q u i l i b r i u m
a t t h e s a m e c u r v e d fluid interface is given b y t h e
Kelvin e q u a t i o n (also k n o w n a s t h e G i b b s - T h o m s o n Freundlich equation):
(RT/V^lnp/p^aC

Figure 4
Relationship between radius r of a cylindrical pore and
radius of curvature r0 of the meniscus

- AP

(17)

w h e r e R is t h e gas c o n s t a n t , t h e a b s o l u t e t e m p e r a
t u r e , Vx t h e m o l a r v o l u m e of t h e liquid a n d p/p0 its
relative v a p o r p r e s s u r e ( c o m p a r e E q n . (13)). T h u s ,
w h e n C is negative, a s for a w e t t i n g liquid, < p0 a n d
s u c h a liquid c o n d e n s e d in a p o r e exerts a r e d u c e d
v a p o r p r e s s u r e . T h e relative m a g n i t u d e s of these t w o
effects a r e c o m p a r e d , for w a t e r a n d m e r c u r y , in T a b l e
2. (Kelvin effects for m e r c u r y a r e usually i g n o r e d
b e c a u s e of its low a b s o l u t e v a p o r p r e s s u r e a t r o o m
temperature.)
A t least three indirect m e t h o d s of s t r u c t u r a l e x a m i
n a t i o n a r e b a s e d o n these effects. I n m e r c u r y p o r o s i m e t r y ( v a n B r a k e l 1981), a n e v a c u a t e d weighed
s a m p l e o f a p o r o u s m a t e r i a l is i m m e r s e d in m e r c u r y in
a d i l a t o m e t e r h a v i n g a capillary stem a n d is subjected
t o progressively increasing p r e s s u r e . A s m e r c u r y is
forced i n t o smaller a n d smaller p o r e s , t h e v o l u m e of
p o r e space i n t r u d e d is d e t e r m i n e d from t h e m o v e m e n t
387

Porosity:

Characterization

and

Investigation

of the m e r c u r y m e n i s c u s in the capillary stem. U s i n g

E q n s . (15, 16), t h e applied pressure is c o n v e r t e d t o
a p o r e r a d i u s a n d the integral d i s t r i b u t i o n of p o r e
radii is o b t a i n e d from t h e m e r c u r y i n t r u s i o n curve.
C o m m e r c i a l i n s t r u m e n t s of this type, s o m e fully a u t o
m a t e d , achieve pressures of u p t o 415 M P a , c o r r e s
p o n d i n g t o p o r e s of 1.8 n m r a d i u s . A t pressures a b o v e
a b o u t 30 M P a , c o r r e c t i o n s for t h e compressibility of
m e r c u r y a n d of the d i l a t o m e t e r b e c o m e significant.
C o m p r e s s i o n of the s a m p l e itself will be r e c o r d e d as a
s p u r i o u s c o n t r i b u t i o n t o the p o r e v o l u m e unless a d d i
tional c o r r e c t i o n s a r e m a d e . V a l u e s for t h e surface
tension of m e r c u r y a n d its c o n t a c t angle against t h e
solid m u s t be inserted in E q n s . (15, 16); these a r e
- 1
a n d 141,
c o m m o n l y a s s u m e d t o be 480 m N m
respectively, t h o u g h the justification for this is
slender.
Suction p o r o s i m e t r y is b a s e d o n t h e related p r i n
ciple t h a t , in o r d e r to r e m o v e a w e t t i n g liquid from the
pores, it is necessary either t o a p p l y a r e d u c e d p r e s
sure to the liquid o r t o force it o u t with excess air
pressure. A block of p o r o u s m a t e r i a l is placed o n a
p o r o u s plate, b o t h being initially s a t u r a t e d with t h e
wetting liquid (usually w a t e r ) . S u c t i o n m a y t h e n be
applied t o the u n d e r s i d e of t h e p l a t e , o r excess air
pressure applied a b o v e it. ( T h e p l a t e m u s t be finer
p o r e d t h a n the s a m p l e so t h a t t h e s a m p l e d r a i n s first.)
T h e w a t e r expelled is m e a s u r e d a t successive incre
m e n t s of suction o r pressure a n d the c o r r e s p o n d i n g
p o r e sizes a r e again calculated from E q n s . (15, 16). In
practice, a i r - s a t u r a t e d w a t e r will n o t w i t h s t a n d n e g a
tive pressures (or tensions) exceeding 100-200 k P a ,
c o r r e s p o n d i n g to p o r e radii d o w n t o a b o u t 0.7 .
Smaller p o r e s t h a n this c a n be d r a i n e d only b y
applying excess air pressure.
Evidently m e r c u r y i n t r u s i o n a n d w a t e r d r a i n a g e a r e
physically similar, in t h a t a n o n w e t t i n g p h a s e replaces
a wetting p h a s e within t h e p o r e s in b o t h cases. A basic
difference between t h e m is t h a t m e r c u r y is forced i n t o
the s a m p l e from all directions, w h e r e a s w a t e r is
d r a i n e d t h r o u g h only o n e face.
Capillary c o n d e n s a t i o n relies u p o n t h e a p p l i c a t i o n
of E q n . (17) t o the a d s o r p t i o n of v a p o r s a t high
relative pressures. A s t h e a d s o r p t i o n i s o t h e r m is
extended t o w a r d s s a t u r a t i o n , a n y p o r e s p r e s e n t will
fill progressively by c o n d e n s a t i o n , b e g i n n i n g with t h e
smallest, until atp=p0
all p o r e s will be full. T h e size
of p o r e s filled a t a n y given relative v a p o r p r e s s u r e c a n
be calculated from E q n s . (15, 17) by inserting a p p r o
p r i a t e values of t h e v a r i o u s c o n s t a n t s . T a b l e 2 s h o w s
t h a t conveniently m e a s u r a b l e relative pressures cor
r e s p o n d t o p o r e s in the a p p r o x i m a t e size r a n g e 2 50 n m . T h i s c o r r e s p o n d s t o the size r a n g e defined
earlier as m e s o p o r e s . M a c r o p o r e s a r e t h u s t h o s e p o r e s
in which Kelvin effects a r e negligible; they a r e there
fore m o s t conveniently studied b y i n t r u s i o n o r suction
p o r o s i m e t r y . M i c r o p o r e s lie in a r a n g e w h e r e t h e
validity of t h e Kelvin e q u a t i o n m a y be in d o u b t , a n d
it is likely t h a t they fill by a h o m o g e n e o u s m e c h a n i s m

388

Applied pressure

Suction

Relative vapor
pressure

Figure 5
Hysteresis in capillary equilibria: (a) mercury intrusion;
(b) capillary suction; (c) capillary condensation. In (a) and
(b) the first cycle (single arrow) differs from subsequent
ones

a k i n t o m u l t i l a y e r a d s o r p t i o n , w i t h o u t f o r m a t i o n of a
m e n i s c u s . Special m e t h o d s a r e n e e d e d for the s t u d y of
m i c r o p o r e s ( G r e g g a n d Sing 1982).
A c o m p l i c a t i o n in p o r e size analysis by capillary
c o n d e n s a t i o n arises from t h e fact t h a t while smaller
p o r e s a r e filling by c o n d e n s a t i o n , n o r m a l multilayer
a d s o r p t i o n is p r o c e e d i n g i n d e p e n d e n t l y o n the walls
of larger p o r e s , as yet unfilled. A l t h o u g h m e t h o d s for
s e p a r a t i n g t h e t w o effects h a v e b e e n p r o p o s e d , they
r e m a i n o p e n t o theoretical objection. T h e y also i n t r o
d u c e s o m e a r i t h m e t i c a l c o m p l e x i t y i n t o t h e analysis of
t h e d a t a , preferably h a n d l e d by c o m p u t e r . A p p a r a t u s
suitable for such m e a s u r e m e n t s is similar t o t h a t
described in Sect. 3.3.
T h e three m e t h o d s discussed in this section all rely
heavily o n t h e cylindrical-pore m o d e l o n which E q n .
(15) is b a s e d . O t h e r simple geometrical m o d e l s h a v e
been p r o p o s e d , such as parallel-sided slot-shaped
p o r e s , b u t it is o b v i o u s t h a t t h e c o m p l e x p o r e s h a p e s
f o u n d in reality c a n n o t be described in a n y t r a c t a b l e
w a y . T h e q u e s t i o n of m o d e l d e p e n d e n c e is referred t o
a g a i n in Sect. 4.
A n o t h e r p r o b l e m arises from t h e hysteresis which is
a l m o s t i n v a r i a b l y associated with all three m e t h o d s : a
m e r c u r y i n t r u s i o n c u r v e is n o t r e t r a c e d w h e n t h e
applied p r e s s u r e is slowly r e d u c e d (Fig. 5a), n o r is a
w a t e r d r a i n a g e c u r v e w h e n t h e suction is relaxed (Fig.
5b), a n d t h e d e s o r p t i o n c u r v e is always displaced t o
lower relative pressures t h a n t h e a d s o r p t i o n curve in
the capillary c o n d e n s a t i o n region (Fig. 5c). T h e p r i n
cipal r e a s o n for this is t h e t h e r m o d y n a m i c a l l y irrever
sible m a n n e r in which l i q u i d - v a p o r menisci m o v e
t h r o u g h the p o r e space: dissipative processes o c c u r
b o t h a t t h e m i c r o s c o p i c level within single p o r e s a n d
o n a scale involving c o o p e r a t i v e effects in m u c h larger
g r o u p s of p o r e s . T h e s e s p o n t a n e o u s m e n i s c u s m o v e
m e n t s (which a r e k n o w n as " H a i n e s j u m p s " after the
British physicist w h o first o b s e r v e d t h e m in 1924)
p r e s e n t yet a n o t h e r obstacle t o t h e i n t e r p r e t a t i o n of
p o r e size d i s t r i b u t i o n s o b t a i n e d b y these m e t h o d s .

Porosity:

T h e specific surface m a y also b e c a l c u l a t e d from t h e

m e a s u r e m e n t s discussed in this section. M o s t simply,
this c o u l d b e d o n e b y s u m m i n g t h e a r e a s c o n t r i b u t e d
by p o r e s in e a c h size r a n g e , b u t o n c e a g a i n t h e result
d e p e n d s heavily o n t h e g e o m e t r i c a l p o r e m o d e l
c h o s e n a n d inevitably is a n u n d e r e s t i m a t e of t h e t r u e
p o r e a r e a ( a s s u m i n g , of c o u r s e , t h a t t h e p o r e " s i z e s "
are correct). A n a l t e r n a t i v e m e t h o d e q u a t e s t h e PV
w o r k d o n e o n t h e system b y i n t r u d i n g m e r c u r y i n t o
the p o r e s ( o r d r a i n i n g t h e m b y suction o r r e m o v i n g
capillary c o n d e n s a t e b y e v a p o r a t i o n ) t o t h e surface
w o r k d o n e o n t h e p o r e walls in replacing s o l i d v a c u u m b y s o l i d - m e r c u r y interfaces ( o r in c o r r e s
p o n d i n g c h a n g e s in t h e o t h e r t w o cases). T h i s e q u a
tion is valid, h o w e v e r , o n l y if all t h e w o r k is d o n e
reversibly. T h e n e a r l y universal presence of hysteresis
s h o w s t h a t this c o n d i t i o n is a l m o s t a l w a y s violated.
3.6 Capillary

Imbibition

W h e n a p o r o u s solid is placed in c o n t a c t w i t h a
wetting liquid, t h e liquid is d r a w n i n t o t h e p o r e s b y
capillary a c t i o n . T h i s familiar p h e n o m e n o n is of g r e a t
practical i m p o r t a n c e in m a n y a p p l i c a t i o n s of p o r o u s
m a t e r i a l s . Since t h e i m b i b i t i o n r a t e is related t o t h e
p o r e size, it affords a n o t h e r indirect m e t h o d of s t r u c
tural characterization.
C o n s i d e r a t i o n h e r e is limited t o o n e - d i m e n s i o n a l
flow. T h e driving force for i m b i b i t i o n is given b y E q n .
(16) a n d is inversely p r o p o r t i o n a l t o p o r e size. Viscous
resistance t o flow is given b y t h e Poiseuille e q u a t i o n
a n d increases as t h e flowing liquid p e n e t r a t e s further
a l o n g t h e p o r e s . C o m b i n i n g these t w o e q u a t i o n s
yields t h e W a s h b u r n e q u a t i o n giving t h e d i s t a n c e
p e n e t r a t e d JC as a function of t i m e t:
x = k wt

0 5

(18)

T h e W a s h b u r n c o n s t a n t fcw is given b y
fcw = ( < 7 r / 2 / / )

05

(18a)

w h e r e r is t h e p o r e r a d i u s a n d a n d a r e , respect
ively, t h e surface tension a n d viscosity of t h e i m b i b i n g
liquid. I n this simple t r e a t m e n t , t h e p o r e s a r e t r e a t e d
as u n i f o r m cylinders a n d t h e c o n t a c t angle is a s s u m e d
t o b e zero. It is also a s s u m e d t h a t t h e w e t t i n g front is
s h a r p , o r a t least t h a t it d o e s n o t b e c o m e m o r e diffuse
as i m b i b i t i o n p r o c e e d s .
T h u s , b y m e a s u r i n g as a function of t i m e in a
linear i m b i b i t i o n e x p e r i m e n t , & w c a n b e e v a l u a t e d ,
a n d t h e n c e t h e p o r e size r. Since t h e p o r e s a r e unlikely
t o resemble u n i f o r m cylinders, t h e value o b t a i n e d will
be t h e r a d i u s of a n " e q u i v a l e n t cylindrical p o r e . "

4. Interpretation

of Indirect

Measurements

In all indirect m e t h o d s of p o r e s t r u c t u r a l c h a r a c t e r i
z a t i o n , simplifying a s s u m p t i o n s a r e m a d e . V a r i o u s
m o d e l s a r e i n t r o d u c e d , b o t h of physical processes

Characterization

and

Investigation

such a s a d s o r p t i o n a n d fluid flow a n d of t h e p o r e

s t r u c t u r e itself. I n p a r t i c u l a r , t h e cylindrical-pore
m o d e l , w h i c h is so widely u s e d , grossly oversimplifies
t h e c o m p l e x g e o m e t r y w h i c h is c h a r a c t e r i s t i c of real
p o r o u s m a t e r i a l s . N o t o n l y a r e p o r e s usually highly
i r r e g u l a r in s h a p e , b u t they a r e i n t e r c o n n e c t e d in a
r a n d o m fashion. T h i s last fact affects, in p a r t i c u l a r ,
t h e i n t e r p r e t a t i o n of results o b t a i n e d b y m e r c u r y
p o r o s i m e t r y ( a n d related m e t h o d s ) , in w h i c h it is
a s s u m e d t h a t m e r c u r y p e n e t r a t e s t h e p o r e s in strict
o r d e r of d e c r e a s i n g size, w h e r e a s in fact t h e n e t w o r k is
p e n e t r a t e d in a s e q u e n c e w h i c h d e p e n d s o n its degree
of i n t e r c o n n e c t i v i t y . W h e n large p o r e s a r e accessible
only t h r o u g h smaller o n e s their p e n e t r a t i o n is
d e l a y e d , giving rise t o a s p u r i o u s c o n t r i b u t i o n t o t h e
v o l u m e of small p o r e s a n d a c o r r e s p o n d i n g overesti
m a t e of t h e specific surface. T h i s m a y p a r t l y offset t h e
t e n d e n c y t o u n d e r e s t i m a t i o n arising from t h e simpli
fied p o r e s h a p e t h a t is a s s u m e d .
A t t e m p t s t o e l a b o r a t e t h e m o d e l s used (as in t h e
K o z e n y - C a r m a n e q u a t i o n , for i n s t a n c e ) a r e usually
of little v a l u e , since they c a n n o t a p p r o a c h t h e degree
of c o m p l e x i t y w h i c h really exists, yet they i n t r o d u c e
a r b i t r a r y p a r a m e t e r s , s u c h as s h a p e factors, w h i c h
cannot be independently evaluated.
A further p r o b l e m arises w h e n m e t h o d s differ in
their resolving p o w e r . F o r e x a m p l e , w h e n specific
surface is m e a s u r e d b y gas a d s o r p t i o n , all surface
accessible t o t h e g a s is detected, w i t h a r e s o l u t i o n of
t h e o r d e r of t h e a r e a o c c u p i e d b y o n e a d s o r b e d
m o l e c u l e . Stereological analysis c a n n o t a p p r o a c h this
r e s o l u t i o n . E v e n grosser discrepancies m a y b e f o u n d
if B E T results a r e c o m p a r e d w i t h t h o s e from p e r m e a
bility m e a s u r e m e n t s , in w h i c h t h e irregularity of p o r e
s h a p e is i n a d e q u a t e l y allowed for a n d in w h i c h t h e
m e a s u r e d p e r m e a b i l i t y is largely unaffected b y p o r e s
lying p e r p e n d i c u l a r t o t h e flow d i r e c t i o n .
T h e s e facts suggest t h a t m e a s u r e d p o r e s t r u c t u r a l
p a r a m e t e r s m a y b e a r little r e l a t i o n t o reality a n d m a y
s h o w m a j o r i n t e r n a l inconsistencies. B o t h expec
t a t i o n s a r e fulfilled: for e x a m p l e , a s a m p l e of Berea
s a n d s t o n e w a s f o u n d t o h a v e a specific surface of
2
_1
0.033 m g
from
permeability
measurements,
2
_1
0.37m g
as c a l c u l a t e d f r o m t h e m e r c u r y i n t r u s i o n
2
_1
p o r e size d i s t r i b u t i o n a n d 0 . 9 2 m g
by the B E T
m e t h o d . T h e r e is, of c o u r s e , n o w a y of k n o w i n g w h a t
its " t r u e " specific surface m a y h a v e been. H o w e v e r ,
this d o e s n o t m e a n t h a t s u c h m e a s u r e m e n t s a r e of n o
p r a c t i c a l v a l u e . I n p r a c t i c e , it is often sufficient t o
m a k e relative m e a s u r e m e n t s , as w h e n c o m p a r i n g o n e
material with another or when monitoring progres
sive c h a n g e s in a single m a t e r i a l . C o n s i s t e n t results
c a n t h e n b e o b t a i n e d u s i n g a single m e t h o d of
m e a s u r e m e n t , even t h o u g h their a b s o l u t e m e a n i n g is
u n c e r t a i n . M o r e o v e r , in m a n y a p p l i c a t i o n s it is n o t
necessary t o k n o w t h e s t r u c t u r a l p a r a m e t e r s t h e m
selves, b u t only t h e p r o p e r t i e s w h i c h they influence.
A n illustration m a y h e l p t o m a k e this p o i n t clear.
In t h e p r i n t i n g p r o c e s s , fluid i n k is a b s o r b e d i n t o t h e

389

Porosity:

Characterization

and

Investigation

p o r e s t r u c t u r e of p a p e r b y capillary action; t h e c o n
trolling factors a r e t h e p o r o s i t y a n d p o r e size of t h e
p a p e r . (In practice, t h e process is c o m p l i c a t e d b y
v a r i a t i o n s in p o r e s t r u c t u r e a c r o s s t h e thickness of
clay-coated p a p e r a n d by t h e n o n - N e w t o n i a n viscos
ity of inks a t high s h e a r rates.) T h e p o r e size of a
p a p e r m i g h t be m e a s u r e d directly by m i c r o s c o p i c
e x a m i n a t i o n o r indirectly by a variety of m e t h o d s
such as m e r c u r y i n t r u s i o n o r p e r m e a m e t r y , o r via t h e
W a s h b u r n c o n s t a n t . Very p r o b a b l y , all these m e t h o d s
will give different results a n d only the m i c r o s c o p i c
d a t a will be in a n y w a y related t o the real physical
p o r e structure. It w o u l d be impossible, h o w e v e r , t o
use the m i c r o s c o p i c d a t a t o calculate the capillary
effects o p e r a t i n g in p o r e s of such irregular s h a p e . By
c o n t r a s t , the single " p o r e size" o b t a i n e d from t h e
W a s h b u r n c o n s t a n t , even t h o u g h totally fictitious,
m a y completely describe t h e effect of p o r e s t r u c t u r e
o n the p a p e r ' s p e r f o r m a n c e in t h e p r i n t i n g process.
T h e w i d e s p r e a d practical uses of p o r o u s m a t e r i a l s
ensure t h a t efforts will be c o n t i n u e d t o d e v e l o p a n d
i m p r o v e m e t h o d s of c h a r a c t e r i z i n g their s t r u c t u r e a n d
to u n d e r s t a n d t h e influence of t h a t s t r u c t u r e o n their
p e r f o r m a n c e . In p a r t i c u l a r , there is a need for n o n d e s
tructive test m e t h o d s t h a t c a n be applied in situ.
H o w e v e r , k n o w l e d g e of p o r e s t r u c t u r a l p a r a m e t e r s is
likely t o r e m a i n m o r e empirical t h a n a b s o l u t e .

Bibliography
Adamson A W 1982 Physical Chemistry of Surfaces, 4th
edn. Wiley, New York
Boucher A 1976 Porous materials: structure, properties
and capillary phenomena. J. Mater. Sci. 11: 1734-50
Dullien F A L 1979 Porous Media: Fluid Transport and Pore
Structure. Academic Press, New York
Everett D (ed.) 1972 Manual of symbols and terminology
for physicochemical quantities and units. Appendix II:
definitions, terminology and symbols in colloid and sur
face chemistry. Part I. Pure Appl. Chem. 31: 577-638
Everett D H, Haynes J 1973 Capillary and porous
materials: equilibrium properties. In: Everett D (ed.)
1973 Colloid Science, Chemical Society Specialist Periodi
cal Reports, Vol. 1. The Chemical Society, London.
Chap. 4, pp. 123-72
Everett D H, Ottewill R (eds.) 1970 Proc. Int. Symp.
Surface Area Determination. Butterworth, London
Everett D H, Parfitt G D, Sing S W, Wilson R 1974 The
SCI/IUPAC/NPL project on surface area standards. / .
Appl. Chem. Biotechnol. 24: 199-219
Everett D H, Stone F S (eds.) 1958 Proc. 10th Colston
Research Society Symposium Structure and Properties of
Porous Materials. Butterworth, London
Gregg S J, Sing S W 1982 Adsorption, Surface Area and
Porosity, 2nd edn. Academic Press, London
Gregg S J, Sing S W, Stoeckli F (eds.) 1979 Proc. Int.
Symp. Characterization of Porous Solids. Society of
Chemical Industry, London
Haynes J M, Rossi-Doria (eds.) 1985 Proc. Int. Symp.
RILEM/CNR: Principles and Applications of Pore Struc
tural Characterization. Arrowsmith, Bristol, UK

390

Haynes J M, van Keulen J, Darr G M, Ludwig U, Fagerlund G, Muresan M, Niesel 1973 Determination of
pore properties of constructional and other materials: a
collection of 12 papers. Mater. Constr. (Paris) 6: 169-250
Modry S, Svata (eds.) 1973-4 Proc. Int. Symp. RILEMj
IUPAC: Pore Structure and Properties of Materials. Academia, Prague
Scheidegger A 1974 The Physics of Flow Through Porous
Media, 3rd edn. University of Toronto Press, Toronto,
Canada
Underwood 1970 Quantitative Stereology. AddisonWesley, Reading, MA
van Brakel J (ed.) 1981 Issue devoted to mercury porosimetry. Powder Technol. 29: 1-208
Young D M, Crowell A D 1962 Physical Adsorption of
Gases. Butterworth, London
J. M . H a y n e s
[University of Bristol, Bristol, U K ]

Positron Annihilation Spectroscopy of

Defects in Metals
T h e p o s i t r o n , t h e a n t i p a r t i c l e of the electron, w h e n
i n t r o d u c e d i n t o a m e t a l from a r a d i o a c t i v e source,
c a n t a k e u p a variety of states from which it subse
q u e n t l y a n n i h i l a t e s with a n electron. T h e p o s i t r o n
a n n i h i l a t i o n s p e c t r o s c o p y ( P A S ) techniques of a n g u
lar c o r r e l a t i o n , D o p p l e r b r o a d e n i n g a n d lifetime de
t e r m i n a t i o n a r e b a s e d u p o n o b s e r v a t i o n s of ~ 10
p o s i t r o n - e l e c t r o n p a i r a n n i h i l a t i o n events, each of
w h i c h yields t w o rays. O w i n g t o t h e c o n s e r v a t i o n of
b o t h energy a n d m o m e n t u m in t h e a n n i h i l a t i o n p r o
cess, t h e resulting r a y s a r e e m i t t e d in o p p o s i t e
directions, p l u s o r m i n u s a n a n g u l a r d e v i a t i o n 0, with
energies e q u a l t o t h e rest-mass energy of a n electron
2
o r p o s i t r o n (mc = 5 1 1 keV), plus o r m i n u s a n energy
i n c r e m e n t AE. T h e d i s t r i b u t i o n s of t h e deviations
a n d AE, w h i c h a r e m e a s u r e d in a n g u l a r c o r r e l a t i o n
a n d D o p p l e r b r o a d e n i n g e x p e r i m e n t s , respectively,
c a n yield detailed i n f o r m a t i o n r e g a r d i n g t h e electron
m o m e n t u m states, a n d a c c o r d i n g l y the defect n a t u r e ,
in t h e region in w h i c h t h e p o s i t r o n s a n n i h i l a t e . T h e
p r o b a b i l i t y p e r u n i t time for t h e a n n i h i l a t i o n of a
p o s i t r o n d e p e n d s u p o n t h e electron density exper
ienced b y t h e p o s i t r o n . H e n c e , t h e p o s i t r o n lifetime,
which is d e d u c e d experimentally from a m e a s u r e d
d i s t r i b u t i o n of t h e time i n c r e m e n t s St b e t w e e n the
injection of a p o s i t r o n i n t o t h e m e t a l a n d its subse
q u e n t a n n i h i l a t i o n , yields i n f o r m a t i o n r e g a r d i n g t h e
electron density in t h e region o r regions in w h i c h the
p o s i t r o n s a n n i h i l a t e . M o r e t h a n o n e p o s i t r o n lifetime
c a n be e x t r a c t e d from a St d i s t r i b u t i o n if t h e d o m i n
a n t p o s i t r o n states in t h e m e t a l a r e sufficiently dis
tinct, as w o u l d b e t h e case for p o s i t r o n s a n n i h i l a t i n g
from b o t h free a n d defect-trapped states.

Positron

T h e p o s i t r o n c a n exist in a free, delocalized Blochlike state, similar t o the l o w - m o m e n t u m b a n d states

of electrons in m e t a l s , o r it c a n b e t r a p p e d in loca
lized, b o u n d states in a variety of vacancylike defects.
In m o s t m e t a l s , t h e p o s i t r o n is very sensitive t o defect
regions of significantly l o w e r - t h a n - a v e r a g e electron
density, such as vacancies, small v a c a n c y clusters, a n d
voids, a t which it c a n f o r m r a t h e r deeply b o u n d states.
It is also sensitive t o d i s l o c a t i o n s , g r a i n b o u n d a r i e s
a n d interfaces, which in general represent s o m e w h a t
smaller negative p e r t u r b a t i o n s t o t h e a v e r a g e electron
density in a m e t a l t h a n t h e v a c a n c y - t y p e defects, b u t
which m a y c o n t a i n defects themselves (e.g., j o g s o n a
dislocation line) t h a t c a n t r a p p o s i t r o n s m o r e deeply.
P o s i t r o n s a n n i h i l a t i n g from b o u n d states in these
defect regions of l o w e r - t h a n - a v e r a g e electron density
have longer lifetimes t h a n in defect-free m e t a l s , w h e r e
p o s i t r o n lifetimes r a n g e from a b o u t 100 ps t o 250 p s .
T h e localization of positrons in defects also gives rise
to narrower, more peaked angular correlation and
D o p p l e r - b r o a d e n e d spectra, o w i n g t o t h e lower elec
t r o n m o m e n t a experienced b y t h e p o s i t r o n s in their
defect-trapped state. Since t h e p o s i t r o n is generally
repelled from regions of h i g h e r - t h a n - a v e r a g e electron
density in the m e t a l (e.g., a n interstitial a t o m o r small
interstitial cluster), P A S is able t o distinguish b e t w e e n
the defect clustering processes t h a t involve vacancies
o r interstitials in i r r a d i a t e d m e t a l s .
I n general, a p o s i t r o n a n n i h i l a t i o n p a r a m e t e r , such
as the p o s i t r o n lifetime o r t h e degree of p e a k e d n e s s
(e.g., n o r m a l i z e d p e a k height) of a n a n g u l a r correla
tion o r D o p p l e r - b r o a d e n e d s p e c t r u m , r e s p o n d s t o
p o s i t r o n t r a p p i n g in different defect types b y t e n d i n g
to increase its value m o n o t o n i c a l l y with increasing
p o s i t r o n - d e f e c t b i n d i n g energy. S u c h a p a r a m e t e r
r e s p o n d s in a similar fashion t o a n increasing c o n c e n
t r a t i o n of a given single defect type, as l o n g as this
c o n c e n t r a t i o n c h a n g e increases t h e p r o b a b i l i t y of
p o s i t r o n t r a p p i n g a t t h e defect p r i o r t o a n n i h i l a t i o n .
This sensitivity t o c h a n g i n g defect c o n c e n t r a t i o n
applies, for e x a m p l e , in t h e case of vacancies in t h e
_ 6
4
- 4
r a n g e of ~ 1 0 - 1 0 ~ a t o m fraction. B e y o n d ~ 1 0 ,
the p r o b a b i l i t y of p o s i t r o n t r a p p i n g a p p r o a c h e s
unity. H e n c e , P A S is c a p a b l e of directly following
changes in b o t h t h e n a t u r e a n d t h e c o n c e n t r a t i o n of
vacancylike defect e n s e m b l e s in m e t a l s . By virtue of
its r e s p o n s e t o t h e local e n v i r o n m e n t in t h e defect in
which it is t r a p p e d , t h e a n n i h i l a t i n g p o s i t r o n c a n yield
detailed defect-specific i n f o r m a t i o n . A s a c o m p l e m e n t
to o t h e r e x p e r i m e n t a l m e t h o d s , such as electrical
resistometry, w h i c h c a n n o t d i s c r i m i n a t e b e t w e e n
defects of v a c a n c y o r interstitial c h a r a c t e r , P A S c a n
be used indirectly t o yield i n f o r m a t i o n r e g a r d i n g
interstitial-type defects as well.
T h e c o n t r i b u t i o n s of P A S t o t h e c h a r a c t e r i z a t i o n of
defects in m e t a l s h a v e b e e n p r i m a r i l y in t w o a r e a s : (a)
the d e t e r m i n a t i o n of a t o m i c defect p r o p e r t i e s , p r i m a r
ily t h o s e of m o n o v a c a n c i e s , a n d (b) t h e m o n i t o r i n g
a n d c h a r a c t e r i z a t i o n of m i c r o s t r u c t u r e d e v e l o p m e n t ,

Annihilation

Spectroscopy

of Defects

in

Metals

as o c c u r s d u r i n g p o s t i r r a d i a t i o n a n n e a l i n g . V a c a n c y
f o r m a t i o n , u n d e r c o n d i t i o n s of t h e r m o d y n a m i c equi
librium, h a s been widely a n d successfully studied in
m e t a l s u s i n g P A S m e a s u r e m e n t s as a function of
t e m p e r a t u r e . T h e s e m e a s u r e m e n t s h a v e yielded either
t h e m o s t precise o r t h e o n l y values for t h e m o n o
v a c a n c y f o r m a t i o n e n t h a l p y H u in a large n u m b e r
of m e t a l s . T h e s e values, w h e n s u b t r a c t e d from the
respective l o w - t e m p e r a t u r e a c t i v a t i o n e n t h a l p i e s for
self-diffusion in m e t a l s , Qx = H\y + / / f j , h a v e in a d d i
tion yielded values for t h e a c t i v a t i o n e n t h a l p y for
monovacancy migration, / / f j . Vacancy migration
during postirradiation and postquenching annealing
e x p e r i m e n t s h a s also been investigated by P A S . F r o m
these high- a n d l o w - t e m p e r a t u r e (equilibrium a n d
n o n e q u i l i b r i u m ) m e a s u r e m e n t s of v a c a n c y mobility, a
generally consistent p i c t u r e h a s e m e r g e d . V a c a n c y
f o r m a t i o n in dilute a n d c o n c e n t r a t e d alloys h a s been
studied with P A S , b u t often w i t h s o m e w h a t less
q u a n t i t a t i v e success t h a n in p u r e m e t a l s , o w i n g t o a
p r e s e n t lack of detailed u n d e r s t a n d i n g of t h e w a y in
w h i c h t h e p o s i t r o n interacts w i t h t h e alloy system.
A t o m i c - d e f e c t recovery in m e t a l s after energeticparticle i r r a d i a t i o n , q u e n c h i n g a n d d e f o r m a t i o n h a s
b e e n extensively studied b y P A S . T h e s e studies h a v e
clearly elucidated the temperature range during post
i r r a d i a t i o n a n n e a l i n g (usually d e s i g n a t e d as stage III)
in w h i c h vacancies a r e m o b i l e a n d cluster in a variety
of m e t a l s . Defect-recovery investigations in dilute
alloys h a v e yielded q u a l i t a t i v e i n f o r m a t i o n r e g a r d i n g
t h e i n t e r a c t i o n of v a c a n c y defects with solute a t o m s ,
p a r t i c u l a r l y t h o s e n o r m a l l y in interstitial s o l u t i o n .
E x p e r i m e n t s o n d e f o r m e d m e t a l s h a v e generally suf
fered from a lack of u n d e r s t a n d i n g of the relative
i m p o r t a n c e of t h e variety of d e f e c t - t r a p p e d p o s i t r o n
states t h a t result from d e f o r m a t i o n . T h e clustering of
vacancies t o f o r m voids in electron- a n d n e u t r o n i r r a d i a t e d m e t a l s h a s b e e n studied by P A S , a n d
a t t e m p t s h a v e been m a d e t o c o r r e l a t e t h e o b s e r v e d
p o s i t r o n lifetimes in these clusters with t h e n u m b e r of
vacancies s t o r e d therein. T h e ability of t h e p o s i t r o n t o
detect c o n t a m i n a t i o n of s u c h v o i d s b y g a s e o u s i m p u r
ities h a s also been d e m o n s t r a t e d . T h e s e a p p l i c a t i o n s
of P A S t o m o r e c o m p l e x defect-related p h e n o m e n a
a r e e x p a n d i n g rapidly, as a r e a t t e m p t s a t using t h e full
electron m o m e n t u m i n f o r m a t i o n available from P A S
t o s t u d y t h e detailed a t o m i c a n d electronic s t r u c t u r e s
of defects in m e t a l s .
G e n e r a l reviews of p o s i t r o n a n n i h i l a t i o n in solids
a r e given b y H a u t o j a r v i (1979) a n d , in a m o r e c o n
d e n s e d f o r m for m e t a l s , b y Siegel (1980). T h e applica
tion of P A S t o t h e s t u d y a n d c h a r a c t e r i z a t i o n of
defects in m e t a l s h a s b e e n reviewed b y Siegel (1982).
A variety of a p p l i c a t i o n s of t h e P A S t e c h n i q u e s t o
defects a n d o t h e r p r o b l e m s in m a t e r i a l s science a r e
briefly reviewed a n d described in t h e v o l u m e s edited
b y H a s i g u t i a n d F u j i w a r a (1979) a n d C o l e m a n et al.
(1982).

391

Positron

Annihilation

Spectroscopy

of Defects

in

Metals

cknowledgement

T h e a u t h o r a c k n o w l e d g e s financial s u p p o r t from t h e
U S D e p a r t m e n t of E n e r g y u n d e r C o n t r a c t N o . W - 3 1 109-ENG-38.
See also: Electron Microscope Analysis of Defect Clusters,
Voids and Bubbles; Field-Ion Microscopy: Observation of
Radiation Effects

Bibliography
Coleman G, Sharma S C, Diana L (eds.) 1982 Proc. 6th
Int. Conf. Positron Annihilation. North-Holland, Amster
dam
Hasiguti R R, Fujiwara (eds.) 1979 Positron Annihilation.
Japan Institute of Metals, Sendai, Japan
Hautojarvi (ed.) 1979 Positrons in Solids. Springer, Berlin
Siegel R W 1980 Positron annihilation spectroscopy. Annu.
Rev. Mater. Sci. 10: 393^25
Siegel R W 1982 The characterization of defects in metals by
positron annihilation spectroscopy. In: Wiffen F W,
Spitznagel J A (eds.) 1982 Advanced Techniques for Char
acterizing Microstructures. The Metallurgical Society
(AIME), Warrendale, PA, pp. 4 1 3 ^ 2
R. W . Siegel
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]

Powder Characterization
T h o r o u g h c h a r a c t e r i z a t i o n of a p o w d e r requires suffi
cient analyses o n representative s a m p l e s t o d e t e r m i n e
the d i s t r i b u t i o n of particle sizes, a n e s t i m a t e of typical
particle s h a p e s , the surface a r e a of t h e particles p e r
unit m a s s o r v o l u m e , particle m i c r o s t r u c t u r e a n d
chemical c o m p o s i t i o n (bulk a n d particle surface). T o
a great extent, these characteristics d e t e r m i n e t h e b u l k
p r o p e r t i e s of t h e p o w d e r such as its m a s s p e r u n i t
v o l u m e ( a p p a r e n t density), its ability t o flow freely
(flowability), its r e s p o n s e t o c o m p a c t i o n forces ( c o m
pressibility) a n d the p r o p e r t i e s of c o m p a c t e d a n d
sintered bodies which m a y be c o n s o l i d a t e d from t h e
powder.

a n d D a l l a v a l l e 1959, I r a n i a n d Callis 1963, Allen

1968). Lenel (1980) p r o v i d e s a concise s u m m a r y of
particle-size analysis m e t h o d s with p a r t i c u l a r e m
p h a s i s o n m e t a l p o w d e r s . S o m e of the m o r e widely
used t e c h n i q u e s a r e i n t r o d u c e d in this section.
T h e use of sieves t o s e p a r a t e b u l k p a r t i c u l a t e m a t e r
ial i n t o v a r i o u s size-range fractions is q u i t e simple a n d
h a s b e e n a p o p u l a r m e t h o d for e s t i m a t i n g particle-size
d i s t r i b u t i o n s for m a n y years. T h e t e c h n i q u e is m o s t
often a p p l i e d t o p o w d e r s w h i c h c o n t a i n a significant
fraction of particles larger t h a n a b o u t 45 , al
t h o u g h it m a y b e used t o s e p a r a t e smaller particles
( d o w n t o a b o u t 10 ). Typically, several s t a n d a r d
wire-cloth screens a r e nested from c o a r s e s t ( t o p ) t o
finest ( b o t t o m ) , with a collecting p a n b e n e a t h t h e
finest sieve. T h e p o w d e r s a m p l e is p l a c e d o n t h e t o p
screen a n d t h e stack is secured in a m e c h a n i c a l s h a k e r
a n d s h a k e n for several m i n u t e s t o insure satisfactory
s e p a r a t i o n of particle sizes. Results a r e r e p o r t e d in
t e r m s of t h e weight p e r c e n t a g e of the initial p o w d e r
s a m p l e r e t a i n e d o n e a c h screen in t h e stack a n d in t h e
collecting p a n . T h e sieves c h o s e n for inclusion in the
stack h a v e s t a n d a r d m e s h sizes w h i c h a r e b a s e d o n
t h e n u m b e r of wires p e r u n i t screen d i m e n s i o n ; for
e x a m p l e , a 150 m e s h screen h a s 150 wires p e r r u n n i n g
inch (59 wires p e r c e n t i m e t e r ) . E a c h s t a n d a r d sieve
h a s a c o r r e s p o n d i n g s q u a r e o p e n i n g w h o s e size is
d e p e n d e n t u p o n b o t h t h e n u m b e r of wires p e r u n i t
length in t h e weave a n d t h e size of t h e wire ( s t a n d a r d
for e a c h m e s h d e s i g n a t i o n ) .
Particle-size analysis b y optical o r electron m i c r o s
c o p y m e t h o d s affords t h e a d v a n t a g e of direct
m e a s u r e m e n t c o u p l e d with t h e s i m u l t a n e o u s a c q u i
sition of i n f o r m a t i o n o n t h e physical s h a p e s of t h e
particles a n d t h e extent t o w h i c h they m a y be agglo
m e r a t e d . H o w e v e r , unless sizing a n d c o u n t i n g p r o c e d
ures a r e a u t o m a t e d , it is extremely t e d i o u s t o o b t a i n
statistically significant particle-size d i s t r i b u t i o n d a t a
by direct m i c r o s c o p i c o b s e r v a t i o n .
M a n y specific m e t h o d s of particle-size analysis uti
lize s e d i m e n t a t i o n o r e l u t r i a t i o n p r o c e d u r e s . S u c h
m e t h o d s rely o n t h e a p p l i c a t i o n of t h e S t o k e s e q u a
tion for their utility a n d , d u e t o physical limitations of
e q u i p m e n t a n d t e c h n i q u e , a r e m o s t useful for m e a s u r
ing particle sizes in t h e r a n g e from
about
1
2
1 0 " 10 . T h e S t o k e s e q u a t i o n m a y be w r i t t e n as
1 2

r = [2g(p-p*)/9vtf '

1. Particle

Size and Size

Distribution

In only a relatively few types of p o w d e r is t h e particle

s h a p e sufficiently regular t o p r o v i d e a single definitive
d i m e n s i o n for t h e " s i z e " of a particle. T h e a p p a r e n t
sizes of irregularly s h a p e d particles will be d e p e n d e n t
u p o n the specific m e a s u r e m e n t t e c h n i q u e e m p l o y e d .
N u m e r o u s m e t h o d s h a v e been devised for o b t a i n
ing i n f o r m a t i o n o n t h e a v e r a g e particle size a n d
d i s t r i b u t i o n of particle sizes in a p o w d e r m a s s ( O r r

392

(1)

w h e r e r is t h e r a d i u s a n d is the density of t h e
particle, g is t h e g r a v i t a t i o n a l acceleration, a n d is t h e
t e r m i n a l settling velocity of t h e particle in a fluid of
density p* a n d viscosity . T h e e q u a t i o n a s s u m e s t h a t
viscous d r a g is t h e only r e s t r a i n i n g force o n t h e
particles. W h e n particle s h a p e s o t h e r t h a n spheres a r e
tested a n d e v a l u a t e d o n t h e basis of t h e S t o k e s
e q u a t i o n , t h e particle-size d i s t r i b u t i o n is calculated in
t e r m s of e q u i v a l e n t radii a n d m a y be significantly
different from t h e a p p a r e n t d i s t r i b u t i o n d e t e r m i n e d
by o t h e r m e t h o d s . S e d i m e n t a t i o n t e c h n i q u e s m a y be

Powder

generally divided i n t o t w o categories, t h o s e w h i c h

measure cumulative sedimentation through some tra
vel distance as a function of time a n d t h o s e w h i c h
d e t e r m i n e , also as a function of t i m e , t h e c o n c e n t r a
tion of particles r e m a i n i n g s u s p e n d e d a t a c e r t a i n level
in t h e fluid. E l u t r i a t i o n m e t h o d s r e m o v e particles
finer t h a n a given size from a p o w d e r s a m p l e b y t h e
action of a fluid s t r e a m (usually a gas) t h r o u g h o r o v e r
the p o w d e r . T h e S t o k e s e q u a t i o n is used t o calculate
the equivalent spherical particle size w h o s e t e r m i n a l
settling velocity is t h e s a m e as the fluid velocity. By
using successively g r e a t e r fluid velocities, t h e s a m p l e
c a n be s e p a r a t e d i n t o relatively n a r r o w size r a n g e s .
T h e particle-size d i s t r i b u t i o n s of refractory m e t a l
p o w d e r s a n d s o m e of their c o m p o u n d p o w d e r s , such
as t u n g s t e n c a r b i d e , a r e frequently d e t e r m i n e d b y a
special s e d i m e n t a t i o n t e c h n i q u e called t u r b i d i m e t r y .
In this m e t h o d , a light b e a m p e n e t r a t e s a glass cell
c o n t a i n i n g a dispersion of t h e p o w d e r in a liquid
(often w a t e r ) . A s t h e p o w d e r settles, t h e intensity of
the light b e a m exiting t h e cell increases in a c c o r d a n c e
with the L a m b e r t - B e e r e q u a t i o n a n d is m e a s u r e d b y
the c u r r e n t t h a t it generates in a p h o t o v o l t a i c cell:
7 0 / / = e x p KACx

(2)

This e q u a t i o n describes t h e o b s c u r a t i o n of light b y a

p a r t i c u l a t e s u s p e n s i o n in t e r m s of t h e r a t i o of t h e
t r a n s m i t t e d intensities of a light b e a m in t h e a b s e n c e
of particles / 0 a n d with the s u s p e n s i o n p r e s e n t /. is
a n extinction coefficient, A is t h e projected a r e a p e r
unit m a s s of particles, C is t h e m a s s c o n c e n t r a t i o n of
particles a n d is t h e length of t h e light p a t h t h r o u g h
the suspension. By m o n i t o r i n g t h e c h a n g e in this
intensity r a t i o with settling time, t h e S t o k e s a n d
L a m b e r t - B e e r e q u a t i o n s c a n b e used t o ascertain t h e
relative weights of particles w i t h i n n a r r o w size r a n g e s
in the original dispersion.
M o n o c h r o m a t i c light from a laser s o u r c e c a n b e
used to d e t e r m i n e particle sizes using a n entirely
different principle from t h o s e previously discussed.
Small particles scatter a m o n o c h r o m a t i c b e a m a n d
the scattering angle is a function of t h e particle sizes
(Weiss a n d F r o c k 1976).
D e t e r m i n a t i o n of particle-size d i s t r i b u t i o n s of
p o w d e r s c a n also be a c c o m p l i s h e d by m o n i t o r i n g
c h a n g e s in t h e resistance of a liquid electrolyte c o n
taining t h e dispersed p o w d e r s a m p l e as t h e i n d i v i d u a l
particles p a s s t h r o u g h a n a p e r t u r e c o n t a i n i n g a set of
i m m e r s e d electrodes. Since a particle p a s s i n g b e t w e e n
the electrodes h a s displaced its v o l u m e of electrolyte,
the resistance a c r o s s t h e circuit will be altered a c c o r d
ingly. I n the C o u l t e r c o u n t e r , a s t a n d a r d device t h a t
e m p l o y s this principle t o a n a l y z e particle-size distri
b u t i o n s , there is a n electronic system t h a t c o u n t s
a n d amplifies t h e voltage pulses associated with t h e
passage of individual particles. A l t h o u g h t h e pulse
m a g n i t u d e is c o n t r o l l e d b y t h e particle v o l u m e , t h e
resulting d a t a a r e typically i n t e r p r e t e d in t e r m s of
the equivalent d i a m e t e r s of spheres.

Characterization

T h e a v e r a g e particle size of a p a c k e d b e d of fine

p o w d e r c a n be inferred from t h e resistance w h i c h t h e
b e d p r o v i d e s t o l a m i n a r flow of a fluid. Such a m e t h o d
is often called p e r m e a m e t r y o r p e r m e a b i l i t y , a n d is
b a s e d u p o n t h e c o n c e p t s of K o z e n y a n d C a r m a n t h a t
t h e r e exists a definite r e l a t i o n s h i p b e t w e e n t h e per
meability of a p a c k e d p o w d e r , t h e fractional p o r o
sity of t h e p o w d e r b e d a n d t h e specific surface a r e a
.S w of t h e p o w d e r :
5

ir^L_n
2

2
( 3 )

/> L ( l - < p ) 5 a J
w h e r e is t h e p o w d e r m a t e r i a l density expressed in
3
2
_1
a n d in
g e m " . Sw is typically expressed in c m g
2
c m . T h e p e r m e a b i l i t y t o l a m i n a r flow is d e t e r m i n e d
from t h e v o l u m e t r i c flow r a t e of t h e fluid p e r u n i t b e d
cross section Q, t h e p r e s s u r e g r a d i e n t a n d t h e fluid
viscosity u s i n g t h e D a r c y e q u a t i o n :
= ////>

(4)

T h e n , for a given relative b e d density, t h e p e r m e a b i

lity will be inversely related t o t h e s q u a r e of the
specific surface a r e a of t h e p o w d e r c o m p r i s i n g the
bed. If s o m e specific particle g e o m e t r y is a s s u m e d
(e.g., spheres), t h e specific surface a r e a c a n be t r a n s
lated i n t o a n effective a v e r a g e particle size. F o r a
s p h e r e of d i a m e t e r d, t h e surface a r e a p e r u n i t v o l u m e
is simply 6/d. T h e r e f o r e ,
Sw

61pd

(5)

T h e m a g n i t u d e of Sw o b t a i n e d from t h e p e r m e a b i l i t y
is c h a r a c t e r i s t i c only of t h e surface a r e a within the
p o w d e r b e d o v e r w h i c h t h e fluid flows (i.e., t h e
friction surface). Since a particle a r r a y m a y c o n t a i n
surfaces such as i n t r a p a r t i c l e p o r e s a n d d e a d - e n d
c h a n n e l s (which a r e n o t involved in t h e d y n a m i c s of
t h e fluid flow), Sw will t e n d t o b e u n d e r e s t i m a t e d
c o m p a r e d t o t h e v a l u e o b t a i n e d from a t e c h n i q u e
such as gas a d s o r p t i o n w h i c h senses virtually all of t h e
i n t e r c o n n e c t e d surface of t h e bed.
T h e g a s - a d s o r p t i o n m e t h o d for d e t e r m i n i n g t h e
specific surface a r e a of a p o w d e r relies u p o n a
m e a s u r e m e n t of t h e a m o u n t of a specific gas a d s o r b e d
o n t h e particle surfaces a s s u m i n g a n a d s o r b e d layer of
m o n o m o l e c u l a r thickness a n d s o m e effective areal
c o v e r a g e p e r gas molecule. T h e t e c h n i q u e w a s p i o
neered b y B r u n a u e r , E m m e t t a n d Teller (1938) a n d
b e a r s t h e a c r o n y m i c n a m e B E T (Lowell a n d Shields
1984). G a s a d s o r p t i o n by t h e p o w d e r m a y be either
physical (van d e r W a a l s forces) o r chemical in n a t u r e .
T h e a d s o r p t i o n m e t h o d , in principle, detects all of the
i n t e r c o n n e c t e d surface a r e a in t h e p o w d e r s a m p l e . A s
such, t h e t e c h n i q u e typically results in specific surface
a r e a m e a s u r e m e n t s w h i c h a r e s o m e w h a t larger t h a n
t h o s e o b t a i n e d from p e r m e a b i l i t y m e a s u r e m e n t s . T h i s
difference m a y b e q u i t e significant, d e p e n d i n g p r i m a r
ily u p o n t h e i n t e r n a l s t r u c t u r e a n d surface t o p o g
r a p h y of t h e particles.

393

Powder

Characterization

Table 1
Particle size and specific surface area measurement methods
Approximate
particle size
range ()

Method

Typical equipment

Sieving

US standard 8 in (20-32 cm) sieves with Ro-Tap shaker

3 in (7.62 cm) micromesh sieves with ultrasonic vibration
optical microscope with TV spot scan
electron microscope
roller air analyzer
gaseous medium; micromerograph
liquid medium
optical; turbidimeter
x-ray; sedigraph
Coulter counter
Fisher subsieve sizer
BET
microtrac particle analyzer

Microscopy
Elutriation
Sedimentation
Turbidimetry
Electrolyte resistance
Permeametry
Gas adsorption
Laser scattering

>45
10-50
0.5-100
0.001-5
2-50
2-100
>0.1
0.5-100
0.1-100
>0.5
0.5^0
0.01-25
2-200

ASTM/ANSI
standard
Ell, B214

B293
B430
B330

Source: Hirschhorn (1969) and Lenel (1980)

T h e r e a r e obviously n u m e r o u s m e a n s available for

o b t a i n i n g i n f o r m a t i o n o n the particle sizes of
p o w d e r s . T a b l e 1 p r o v i d e s a s u m m a r y of s o m e of t h e
m o r e useful m e t h o d s , including n o t a t i o n of t h e appli
cable A m e r i c a n Society for T e s t i n g a n d M a t e r i a l s
(ASTM)/American National Standards
Institute
( A N S I ) s t a n d a r d s for particle-size analysis of m e t a l
powders.

2. Particle

Shape

T h e s h a p e s of the individual particles within a p o w d e r

significantly influence its b u l k p r o p e r t i e s , for e x a m p l e ,
p a c k i n g ( a p p a r e n t density), flowability a n d c o m p r e s
sibility. T h e qualitative p a r t i c l e - s h a p e classifications,
defined by t h e I n t e r n a t i o n a l O r g a n i z a t i o n for S t a n
d a r d i z a t i o n in I S O S t a n d a r d 3252, a r e as follows:
(a)

acicularneedle s h a p e d ,

(b)

a n g u l a r r o u g h l y p o l y h e d r a l s h a p e with s h a r p
edges,

(c)

d e n d r i t i c o f b r a n c h e d crystalline s h a p e ,

(d)
(e)

fibrousregularly

o r irregularly t h r e a d l i k e ,

flakyplatelike,

(f)

granularirregular but approximately

mensional,

equidi-

(g)

irregularlacking any symmetry,

(h)

n o d u l a r o f r o u n d e d irregular s h a p e , a n d

(i)

s p h e r o i d a l n o m i n a l l y spherical.

T h e s e general particle m o r p h o l o g i e s a r e s h o w n in F i g .
1. Particle s h a p e s will be d i c t a t e d p r i m a r i l y b y t h e
c o m p o s i t i o n of t h e p a r t i c u l a t e m a t e r i a l a n d t h e m a n u
facturing p r o c e s s used t o p r o d u c e t h e p o w d e r .

394

T h e q u a n t i t a t i v e c h a r a c t e r i z a t i o n of real particle
s h a p e s c a n b e very c o m p l e x a n d often involves t h e
d e t e r m i n a t i o n of o n e o r m o r e s h a p e factors from
analyses of magnified projected particle images. Bedd o w a n d M e l o y (1980) c o n t a i n s several t h o r o u g h
discussions of s h a p e c h a r a c t e r i z a t i o n t e c h n i q u e s a n d
analysis.
P a r t i c l e - s h a p e factors c o m m o n l y p r o v i d e s o m e
m e a s u r e of t h e d e v i a t i o n from a n idealized g e o m e t r y
such as a s p h e r e o r c u b e . F o r e x a m p l e , w h e n three
m u t u a l l y p e r p e n d i c u l a r particle d i m e n s i o n s c a n b e
ascertained, it is possible t o e s t i m a t e b o t h a particle
flatness o r flakiness, a n d t h e m a x i m u m axial aspect
r a t i o . A l t h o u g h nonspecific with respect t o particle
surface t o p o g r a p h y , these p a r a m e t e r s afford a q u a n t i
tative i n d i c a t i o n of t h e d e v i a t i o n of t h e particle from
a n e q u i a x e d m o r p h o l o g y . T w o s h a p e factors w h i c h
c a n b e e v a l u a t e d from projected particle images a r e
illustrated in Fig. 2.
Stereological m e t h o d s c a n be useful in particle
s h a p e c h a r a c t e r i z a t i o n . C o n c e r n e d largely with t h e
a p p l i c a t i o n of g e o m e t r i c a l p r o b a b i l i t i e s t o infer threed i m e n s i o n a l m a t e r i a l s t r u c t u r e s from t h e s t u d y of
p l a n a r sections, stereology c a n p r o v i d e specific q u a n
tities w h i c h m a y be q u i t e useful in particle-shape
c h a r a c t e r i z a t i o n . S u c h p a r a m e t e r s as m e a n surface
c u r v a t u r e , particle p e r i m e t e r a n d m e a n particle
a r e a c a n be d e t e r m i n e d b y established stereological
m e t h o d s using either m a n u a l o r a u t o m a t e d i m a g i n g
equipment.

3. Bulk Powder

Properties

A l t h o u g h t h e characteristics of t h e individual p a r t i
cles c o m p r i s i n g a p o w d e r a r e t h e principal d e t e r m i
n a n t s of t h e b u l k b e h a v i o r of t h a t p o w d e r , it is often

Powder

Characterization

Figure 1
Particle morphologies of powders: (a) acicular, (b) angular, (c) dendritic, (d) fibrous, (e) flaky, (f) granular, (g) irregular,
(h) nodular and (i) spheroidal

impossible t o establish a c c e p t a b l e q u a n t i t a t i v e c a u s e and-effect relationships. Several p r o c e d u r e s h a v e b e e n

developed for c h a r a c t e r i z i n g t h e b e h a v i o r o f b u l k
p o w d e r s , p a r t i c u l a r l y with respect t o p r o p e r t i e s of
i m p o r t a n c e t o s u b s e q u e n t c o n s o l i d a t i o n processing o r
e n d use as a p a r t i c u l a t e m a t e r i a l . Often, s o m e
m e a s u r e of t h e p a c k i n g efficiency of the p o w d e r , its
ability t o flow freely u n d e r t h e a c t i o n of gravity, a n d
its response t o c o m p a c t i o n forces a r e i m p o r t a n t c h a r
acteristics for t h e design of c o n s o l i d a t i o n sequences

for m a n y m e t a l , c e r a m i c a n d m i n e r a l p o w d e r s , includ
ing p h a r m a c e u t i c a l s .
T h e m a s s p e r u n i t v o l u m e of a loose p o w d e r , as
m e a s u r e d u n d e r specific test c o n d i t i o n s , is called its
a p p a r e n t density. F o r free-flowing m e t a l p o w d e r s , the
test involves filling a 25 c m 3 c u p with the p o w d e r
falling t h r o u g h t h e 0.25 c m d i a m e t e r orifice of a
funnel (called t h e H a l l funnel) from a fixed height.
T h e a p p a r a t u s is illustrated in Fig. 3. T h e filled,
levelled c u p is weighed a n d t h e a p p a r e n t density of the

395

Powder

Characterization

Table 2
Tests for bulk properties of metal powders
Property

Figure 2
Particle shape factors derived from projected particle
image dimensions. Both
the elongation E( = a/b) and the
2
surface area 5 ( = C /12.6 A) are unity for a sphere

Apparent density
free-flowing
powders
non-free-flowing
powders
refractory-metal
powders
Flowability (flow
time)
Compressibility

Green strength

p o w d e r d e t e r m i n e d in g e m . T h e a p p a r e n t density
of a non-free-flowing p o w d e r is d e t e r m i n e d in a
similar m a n n e r except t h a t a 0.51 c m funnel orifice
( C a r n e y funnel) is e m p l o y e d .
T h e flowability of a m e t a l p o w d e r is d e t e r m i n e d
using t h e H a l l flow m e t e r a p p a r a t u s described p r e
viously. T h e t i m e r e q u i r e d for 50 g of t h e p o w d e r t o
flow t h r o u g h t h e orifice of t h e H a l l funnel, suitably
corrected for n o n s t a n d a r d test c o n d i t i o n s , is r e p o r t e d
as t h e flowability of t h e p o w d e r .
It is o b v i o u s t h a t b o t h t h e flowability a n d a p p a r e n t
density of a p o w d e r will b e influenced significantly b y
t h e theoretical density of its p a r t i c u l a t e m a t e r i a l . F o r
a given b a s e m a t e r i a l , these b u l k p r o p e r t i e s will b e
d e p e n d e n t u p o n particle-size d i s t r i b u t i o n , particle
s h a p e a n d i n t e r n a l particle s t r u c t u r e (e.g., p r e s e n c e of
voids). I n general, s p h e r o i d a l p o w d e r s , such as t h o s e
p r o d u c e d by inert gas a t o m i z a t i o n , will exhibit t h e

Hall
funnel

Test apparatus

ASTM/ANSI
standard

Hall flowmeter

B212

Carney funnel

B417

Scott volumeter

B329

Hall flowmeter

B213

225 kN (min) compression

machine/press plus steel
or cemented carbide die
set
same as for compressibility
plus three-point bend
test fixture

B331

B312

highest values of relative a p p a r e n t density a n d flowa

bility ( s h o r t e s t flow times). F i n e irregularly s h a p e d
particles, b e c a u s e of t h e h i g h frequency of i n t e r p a r t i cle c o n t a c t s a n d c o n s e q u e n t p o o r settling b e h a v i o r ,
t e n d t o h a v e limited flowability a n d low a p p a r e n t
density.
T h e p r o p e r t i e s r e l a t e d m o s t directly t o t h e b e h a v i o r
of a m e t a l p o w d e r subjected t o c o m p a c t i o n forces a r e
compressibility (compactibility) a n d green s t r e n g t h .
C o m p r e s s i b i l i t y is simply a m e a s u r e of t h e densificat i o n achieved in c o m p a c t i o n a t a specified p r e s s u r e .
G r e e n s t r e n g t h is t h e m a x i m u m o u t e r fiber tensile
stress w h i c h t h e p o w d e r c o m p a c t c a n resist w i t h o u t
fracture in a t h r e e - p o i n t b e n d test.
A s u m m a r y of s o m e b u l k m e t a l p o w d e r c h a r a c t e r i
zation procedures, including applicable A S T M / A N S I
s t a n d a r d s , is given in T a b l e 2.
See also: Powder Mechanics

Bibliography

Figure 3
Hall flowmeter apparatus

396

Allen 1968 Particle Size Measurement: Size, Surface and

Pore Volume. Chapman and Hall, London
American Society for Testing and Materials 1981 Annual
Book of ASTM Standards, Pt. 9. American Society for
Testing and Materials, Philadelphia, PA
Beddow J K, Meloy (eds.) 1980 Testing and Characteri
zation of Powders and Fine Particles. Heyden, London
Brunauer S, Emmett , Teller 1938 Adsorption of
gases in multimolecular layers. J. Am. Chem. Soc. 60:
309-19
Hausner 1973 Handbook of Powder Metallurgy. Chem
ical Publishing, New York
Hirschhorn J S 1969 Introduction to Powder Metallurgy.
American Powder Metallurgy Institute, Princeton, NJ

Powder
Irani R R, Callis C F 1963 Particle Size: Measurement
Interpretation and Application. Wiley, New York
Lenel F V 1980 Powder Metallurgy: Principles and Applica
tions. Metal Powder Industries Federation, Princeton, NJ
Lowell S, Shields J 1984 Powder Surface Area and Porosity.
Chapman and Hall, London
Orr C, Dallavalle J 1959 Fine Particle Measurement.
Macmillan, New York
Poster A R (ed.) 1966 Handbook of Metal Powders. Reinhold, New York
Weiss L, Frock 1976 Rapid analysis of particle size
distributions by laser light scattering. Powder Technol. 14:
287-93

Cubic

Mechanics

Orthorhombic

D . W. Smith
[ M i c h i g a n T e c h n o l o g i c a l University,
Houghton, Michigan, USA]

T e t r a g o n a l - sphenoidal

Powder Mechanics
T h e b e h a v i o r of p o w d e r s c a n n o t be fully described b y
t h e o r y a t present, yet it is of g r e a t i m p o r t a n c e in t h e
practical use of soils, s a n d s , c e m e n t s , ceramics,
p o w d e r m e t a l s , p i g m e n t s , catalysts, p h a r m a c e u t i c a l s
a n d m a n y o t h e r g r a n u l a r solids. A l m o s t all e v e r y d a y
objects g o t h r o u g h a p o w d e r stage a t s o m e p o i n t in
their m a n u f a c t u r e a n d m o r e k n o w l e d g e is needed t o
optimize p o w d e r processing.
M u c h of t h e difficulty in describing p o w d e r m e c h a
nics stems from the r a n g e of s t r u c t u r e s t h a t c a n exist
in a g r a n u l a r m e d i u m (Deresiewicz 1958). F o r ex
a m p l e , a highly c o m p a c t e d pellet m a d e b y pressing
p o w d e r i n t o a m o l d b e h a v e s as a H o o k e a n solid; it is
largely elastic, exhibits a linear stress-strain c u r v e ,
t r a n s m i t s v i b r a t i o n s , displays brittle fracture in ten
sion a n d d e f o r m s plastically w h e n i n d e n t e d . A p h a r
maceutical tablet is a n e x a m p l e of this type. By
contrast, a composition m a d e by mixing powder into
a liquid c a n b e h a v e as a solid gel if t h e particles
c o n n e c t t o form a c o n t i n u o u s s t r u c t u r e with t h e liquid
in t h e interstices, o r c a n b e h a v e as a liquid, flowing
like water, if the particles r e m a i n s e p a r a t e . E m u l s i o n
p a i n t , designed t o c h a n g e from a solid t o a liquid
o n stirring t o b r e a k d o w n t h e particle s t r u c t u r e , is a
g o o d illustration of this. W h e n dispersed in a gas, a
fine p o w d e r c a n b e h a v e as a gas itself, d i s p l a y i n g
B r o w n i a n m o t i o n , diffusion a n d flow. Alternatively, a
bed of p o w d e r fluidized b y p a s s i n g a gas t h r o u g h it
m a y b e h a v e like a boiling liquid, f o r m i n g b u b b l e s of
gas which mix t h e b e d a n d efficiently transfer h e a t .
T h e objective of p o w d e r m e c h a n i c s is t o describe
these p h e n o m e n a theoretically. O n e m a y resolve this
description i n t o three p a r t s :
(a)

the geometrical need t o define the s t r u c t u r e of

the powder mass:

(b)

the physical p r o b l e m of a d h e s i o n a l a n d frictional

i n t e r a c t i o n b e t w e e n t h e grains; a n d

Rhombohedra I

Figure 1
The four dense regular packings of equal rigid spheres

(c)

t h e q u e s t i o n of i n t e r a c t i o n of t h e g r a n u l a r m a t e r
ial with t h e s u r r o u n d i n g s , w i t h stress fields, with
v i b r a t i o n , o r with flowing fluids, for e x a m p l e .

T h i s article investigates these three issues in m o r e

detail.

7. Structure

of Powder

Masses

T h e simplest m o d e l of a p o w d e r is a h e a p of rigid
s m o o t h spheres all t h e s a m e size. Since sphere m o d e l s
h a v e b e e n used t o explain t h e s t r u c t u r e of crystals
( B a r l o w 1883) a n d h a v e also been e m p l o y e d t o simu
late t h e s t r u c t u r e of liquids (Bernal 1964) it is h a r d l y
surprising t h a t p o w d e r s exhibit s o m e solid a n d s o m e
liquid c h a r a c t e r . E x p e r i m e n t s using dispersions of
p o l y m e r spheres in a liquid of t h e s a m e refractive
index h a v e s h o w n t h a t t h e s p h e r e s a r e in a d i s o r d e r e d
liquidlike state a t low c o n c e n t r a t i o n s , b u t form
o r d e r e d a r r a y s a t ~ 5 0 % solids, b e c o m i n g d i s o r d e r e d
a n d glasslike a t c o n c e n t r a t i o n s n e a r 6 0 % (Pusey a n d
v a n M e g e n 1986).
Solid p o w d e r s t r u c t u r e s m a y b e m o d e l l e d by the
four r e g u l a r d e n s e p a c k i n g s of spheres s h o w n in Fig.
1. T h e s e give p a c k i n g v o l u m e fractions ( v o l u m e of
s p h e r e s / v o l u m e of assembly), porosities a n d c o o r d i
n a t i o n n u m b e r s ( p o i n t s of c o n t a c t p e r sphere) as
s h o w n in T a b l e 1. T h e t o p layer of particles is
i n d i c a t e d in F i g . 1 b y t h e full line a n d t h e second layer
by b r o k e n lines. E x c e p t for (simple) cubic stacking,
t h e layering c a n b e varied t o give further complexity,
as e x p l a i n e d b y C u m b e r l a n d a n d C r a w f o r d (1987).
T h e m o s t stable p a c k i n g is t h e densest, t h a t is, the
r h o m b o h e d r a l s t r u c t u r e with a p a c k i n g v o l u m e frac
tion of 0.7405. S u c h p a c k i n g s h a v e been achieved b y
individually placing balls in a regular a r r a y . Slow

397

Powder

Mechanics

Table 1
Properties of the four dense regular packings of equal rigid
spheres

Packing
Porosity
Coordination

Cubic

Orthorhombic

0.5236
0.4764
6

0.6046
0.3954
8

Tetragonalsphenoidal Rhombohedral
0.6981
0.3019
10

0.7405
0.2595
12

s e d i m e n t a t i o n of stable dispersions of m o n o s i z e poly

meric o r c e r a m i c particles h a s also p r o d u c e d r h o m b o
h e d r a l p a c k i n g over small regions, s e p a r a t e d from
o t h e r well-packed a r e a s by d i s o r d e r e d " g r a i n b o u n
d a r i e s " o r by c r a c k s . N o o n e h a s yet been able t o
p r o d u c e these d e n s e close p a c k i n g s over large
v o l u m e s of p o w d e r .
M o s t e x p e r i m e n t s o n p a c k i n g of regular particles
h a v e involved ball bearings p o u r e d i n t o a c o n t a i n e r
a n d then v i b r a t e d t o settle t h e assembly d o w n t o
" d e n s e r a n d o m p a c k i n g , " which c o r r e s p o n d s t o a
p a c k i n g fraction of 0.6366 0.0004 ( F i n n e y 1970,
1983). By r o t a t i n g t h e c o n t a i n e r , o r by merely p o u r i n g
the spheres i n t o t h e c o n t a i n e r , " l o o s e r a n d o m p a c k
i n g " with p a c k i n g fractions between 0.55 a n d 0.58 is
achieved. In this s i t u a t i o n , the c o o r d i n a t i o n of the
spheres is r a n d o m a n d the g e o m e t r y resembles t h a t of
a liquid.
E x p e r i m e n t s s h o w t h a t lead s h o t a n d s a n d give
dense r a n d o m p a c k i n g s which d o n o t v a r y s u b s t a n
tially with particle size, in a c c o r d a n c e with t h e o r y .
H o w e v e r , the a d d i t i o n of several p e r c e n t of w a t e r t o
s a n d decreases the p a c k i n g , t h e decrease b e c o m i n g
m o r e p r o n o u n c e d for finer g r a i n s . T h i s is d u e t o a
capillary layer of w a t e r o n the particles c a u s i n g a d h e
sion between grains. A similar effect o c c u r s for spheri
cal particles less t h a n a b o u t 50 in d i a m e t e r . Such
particles t e n d t o stick t o g e t h e r a n d form less-dense
packings. T h e smaller the spheres, t h e m o r e fluffy a n d
p o r o u s is t h e p o w d e r m a s s , r e a c h i n g p a c k i n g s of
a r o u n d 0.05 for 0.03 d i a m e t e r silica m a d e by a
s m o k e process. M i c r o s c o p y reveals t h a t t h e spheres
are aggregated i n t o c h a i n s by the a d h e s i o n forces in
this case.
A n u m b e r of plausible s t r u c t u r e s for such loose
assemblies h a s been p r o p o s e d by S u t h e r l a n d a n d
H u t c h i n s o n (1965).
P a c k i n g fraction of p o w d e r s c a n be c o n t r o l l e d in
v a r i o u s ways. T o increase p a c k i n g , large spheres a n d
small spheres c a n be mixed so t h a t t h e small grains fill
the g a p s b e t w e e n the large particles (Fig. 2). If the
small spheres a r e very tiny, t h e n they will fill t h e g a p s
with 0.63 of solid m a t e r i a l . T h u s , the t o t a l p a c k i n g is
0.63 + 0 . 6 3 ( 1 - 0 . 6 3 ) = 0.86 a n d t h e v o l u m e r a t i o of
coarse t o fine spheres is 0.63/0.23 = 2.74. T h e s e results
h a v e been confirmed experimentally by filling a c o n
tainer with steel s h o t , v i b r a t i n g it t o achieve dense

398

0.2

0.4

Fine

0.6

0.8

fraction

Figure 2
Increase in packing density achieved by filling the gaps
between large spheres with smaller spheres, for
comparison with experimental results

r a n d o m p a c k i n g , t h e n p o u r i n g fine s h o t t h r o u g h the
interstices a n d v i b r a t i n g again. A r a t i o of d i a m e t e r s of
20/1 is r e q u i r e d t o a p p r o a c h t h e theoretical level. If
t h e s a m e p o w d e r s a r e mixed in a fluid, t h e p a c k i n g
rarely rises a b o v e 0.8 because the fine particles i n t r u d e
b e t w e e n t h e c o a r s e spheres a n d e x p a n d t h e assembly.
A decrease in p a c k i n g is generally o b s e r v e d w h e n
the particles a r e m a d e n o n s p h e r i c a l . F i b r o u s o r p l a t e
like particles c a n form gel s t r u c t u r e s a t v o l u m e frac
tions as low as 0.05. T o explain these effects is
impossible by o r d i n a r y g e o m e t r y . R e c e n t a d v a n c e s in
p a c k i n g t h e o r y h a v e e m e r g e d from c o m p u t e r simula
tion. Particles of a r b i t r a r y s h a p e a r e d e p o s i t e d
a c c o r d i n g t o m a t h e m a t i c a l rules, allowing p a c k i n g
density t o be e v a l u a t e d (Cargill 1984).

2. Problem

of

Contact

O n c e the n u m b e r of interparticle c o n t a c t s h a s been

d e t e r m i n e d from t h e s t r u c t u r e , t h e p r o p e r t i e s of
p o w d e r assemblies m a y be calculated k n o w i n g t h e
size a n d n a t u r e of particle c o n t a c t s .
Particle c o n t a c t s a r e f o r m e d as t h e grains a r e
b r o u g h t t o g e t h e r by gravity o r by mixing in a fluid.
E a c h grain t h e n experiences a v a n d e r W a a l s a t t r a c -

Powder

Mechanics

first calculated t h e c o n t a c t - s p o t d i a m e t e r d using

elasticity t h e o r y t o give
Elastic

=[ -^f]"

deformation

3<l

H e also c o m p u t e d t h e relative d i s p l a c e m e n t o f t h e
s p h e r e centers a s t h e particles were p u s h e d together:
Figure 3
Two elastic spheres, pushed into contact by a force F, and
attracted by a work of adhesion , deform elastically to
give a contact circle of diameter d

tion t o w a r d s n e i g h b o r i n g g r a i n s . If this a t t r a c t i o n is
repulsed b y electrical d o u b l e - l a y e r forces o r b y thick
a d s o r b e d p o l y m e r layers, t h e n t h e particles c a n n o t
achieve full c o n t a c t , b u t r e m a i n s e p a r a t e , c a u s i n g t h e
m i x t u r e t o b e h a v e a s a liquid. S u c h colloidally stable
suspensions c a n b e p o u r a b l e a t high v o l u m e l o a d i n g s
of solids, g r e a t e r t h a n 0.5. O n t h e o t h e r h a n d , w h e n
there is n o l o n g - r a n g e r e p u l s i o n b e t w e e n t h e particles,
the grains c o m e i n t o m o l e c u l a r c o n t a c t a n d c a n form
a s t r u c t u r e t h a t b e h a v e s a s a solid, even t h o u g h t h e
solid p a c k i n g m a y b e a s l o w a s 0.05. T h e force
i m p o s e d o n t h e particles a t t h e c o n t a c t regions m a y b e
considerable, c a u s i n g elastic a n d even plastic defor
m a t i o n w h e n t h e particles a r e sufficiently small.
T h e solution t o t h e p r o b l e m o f elastic c o n t a c t for
t w o e q u a l s m o o t h spheres o f d i a m e t e r Z>, Y o u n g ' s
modulus a n d Poisson's ratio pushed together by
a n external force F a n d pulled i n t o c o n t a c t b y surface
a t t r a c t i o n s defined b y w o r k of a d h e s i o n (the energy
required t o s e p a r a t e u n i t a r e a of interface) w a s given
by J o h n s o n et al. (1971). T h e d i a m e t e r d of t h e c o n t a c t
circle (Fig. 3) is defined b y t h e e q u a t i o n
3

</ = 3(l -

9 ( 1

v 2 ) 2

13 /

^J

( 4 )

T h e n o n l i n e a r i t y of these e q u a t i o n s leads t o t h e n o n H o o k e a n elastic b e h a v i o u r o f n o n c o h e s i v e p o w d e r s

u n d e r c o m p r e s s i v e stress.
W h e n a s h e a r force is a p p l i e d t o t h e c o n t a c t s p o t
b e t w e e n t w o spheres, slip o c c u r s a t t h e edges o f t h e
c o n t a c t , even a t small values o f T, causing energy
dissipation t h r o u g h friction. A s t h e shear force is
raised, this slipped region s p r e a d s t h r o u g h t h e c o n t a c t
s p o t , until gross sliding o c c u r s . T h i s frictional slip
p a g e a c c o u n t s f o r t h e hysteresis o b s e r v e d w h e n
powders are sheared.
C o h e s i v e p o w d e r s , for e x a m p l e c e m e n t o r t i t a n i u m
dioxide p i g m e n t , a r e q u i t e different b e c a u s e they h o l d
t o g e t h e r b y v a n d e r W a a l s a t t r a c t i o n s w h e n all exter
n a l forces h a v e been r e m o v e d . S u c h p o w d e r s d o n o t
b e h a v e a s s e p a r a t e grains, b u t c l u m p i n t o a g g l o m e r
ates, w h i c h d o n o t flow readily b u t c a k e o n t o surfaces.
T h e s e p o w d e r s c a n b e f o r m e d b y p r e s s u r e i n t o tablets
with a c o n s i d e r a b l e tensile s t r e n g t h .
T h e r e a s o n for this b e h a v i o r is t h e soft o r s m o o t h
n a t u r e o f t h e g r a i n s w h i c h allows m o l e c u l a r c o n t a c t
b e t w e e n t h e surfaces. All particles seem t o exhibit this
c o h e s i o n a t sizes b e l o w 1 . A t zero external l o a d
the c o n t a c t - s p o t d i a m e t e r is o b t a i n e d from E q n . (1) a s

'-d^-)]"'

v )^{F+inTD
2 l/2

+ [lnrDF+(irD) ] }

(1)

T h e force n e e d e d t o pull t h e spheres a p a r t w a s f o u n d

to be

W h e n a small n o r m a l l o a d F is applied t o such

c o n t a c t i n g spheres, t h e deflection is given b y
F/

F=\nYD

(2)

L o o k i n g a t these e q u a t i o n s , w e see t h a t there a r e t w o

b r o a d l y different types of p o w d e r : o n e of high w o r k of
a d h e s i o n , t h e so-called cohesive p o w d e r w h i c h
h o l d s t o g e t h e r in t h e a b s e n c e of a n external c o m p a c
tion F; t h e o t h e r of negligible w o r k of a d h e s i o n , t h a t
is, low , t h e n o n c o h e s i v e p o w d e r w h i c h falls a p a r t
once t h e applied l o a d F is r e m o v e d .
N o n c o h e s i v e p o w d e r s a r e exemplified b y 100
s a n d grains o r 1 m m d i a m e t e r ball b e a r i n g s . S u c h
particles h a v e surfaces w h i c h a r e r o u g h c o m p a r e d t o
the r a n g e o f v a n d e r W a a l s forces a n d c o n s e q u e n t l y
give little a d h e s i o n . A s a result, t h e p o w d e r b e h a v e s a s
a collection o f individual g r a i n s , flowing freely a n d
resisting s h e a r only b y t h e a c t i o n o f friction. H e r t z

,= r J ^ l T
2

3
( 6 )

Ll6(l - v ) J
w h i c h s h o w s t h a t cohesive p o w d e r s a r e H o o k e a n a t
low stresses.
C o h e s i v e p o w d e r s m a y b e m a d e less so b y reducing
t h e w o r k of a d h e s i o n b e t w e e n t h e particles. T h i s is
i m p o r t a n t in p h a r m a c e u t i c a l , m e t a l a n d c e r a m i c p r o
cessing w h e r e g o o d flow o f fine p o w d e r s is beneficial.
Surface active a g e n t s such a s stearates, polyethyleneoxide o r silanes m a y b e a d d e d . D i s p e r s i o n in
fluids c a n also r e d u c e if t h e wetting angle is low.
S u r f a c t a n t o r p o l y m e r solutions also p r o m o t e flow
by p r e v e n t i n g m o l e c u l a r c o n t a c t b e t w e e n particle
surfaces.
S o m e t i m e s it is necessary t o m a k e n o n c o h e s i v e
p o w d e r s m o r e cohesive, for e x a m p l e , w h e n stabilizing
399

Powder

Mechanics

l o a d a n d a n increasing m o d u l u s a t higher l o a d s . F o r a
cubic s t a c k i n g of u n i f o r m spheres t h e elastic m o d u l u s
is calculated from E q n s . (3) a n d (4) t o be
3

E* = ^ = [

volume

fraction,

Figure 4
Calculated elastic moduli for regular particle assemblies
plotted against the packing
volume fraction to show the
4,
near dependence on
soils. T h i s m a y be achieved by c e m e n t i n g t h e grains a t
the c o n t a c t p o i n t s using b i n d e r s . Alternatively, t h e
p o w d e r s m a y be c o a t e d with t a c k y b i n d e r s o r r u b b e r y
layers which increase substantially.

3. Interaction

with

Surroundings

T h e m a i n p u r p o s e of p o w d e r m e c h a n i c s is t o p r e d i c t
the response of p o w d e r masses t o external fields such
as stress fields, electrical fields, v i b r a t i o n s o r fluid
flow.
C o n s i d e r first t h e r e s p o n s e t o m e c h a n i c a l stress.
Cohesive p o w d e r s b e h a v e in the simplest w a y b e c a u s e
they give linear, H o o k e a n s t r e s s - s t r a i n curves as
indicated in E q n . (6). F o r a cubic p a c k i n g of spheres
2
the m e a n stress o n e a c h particle is F/D a n d t h e strain
is /D. T h e r e f o r e , Y o u n g ' s m o d u l u s c a n be defined
for this assembly as
.

stress Z=
=

strain

DS

/3

L\6D(\ - v ) J

A similar calculation m a y be carried o u t for o t h e r

regular p a c k i n g s , giving values of Y o u n g ' s m o d u l u s
which lie o n a s m o o t h c u r v e w h e n p l o t t e d a g a i n s t
p a c k i n g fraction (Fig. 4):
2

E*=\7A

/ E T\
<P {^)
4

1/3

/ 3

(9)
K)

T h e d e p e n d e n c e of elastic p r o p e r t i e s o n t h e applied
l o a d F for n o n c o h e s i v e p o w d e r s is relevant t o t h e
p a s s a g e of s o u n d waves t h r o u g h the m a s s . W h e r e a s
cohesive p o w d e r s give n o c h a n g e in w a v e speed as t h e
1 6
l o a d is increased n o n c o h e s i v e assemblies s h o w a n F '
d e p e n d e n c e of c o m p r e s s i o n a l w a v e velocity, b e c a u s e
1/2
w a v e velocity d e p e n d s o n m o d u l u s . T h i s relation
ship h a s been verified experimentally for s a n d .
F u r t h e r extensions of this t h e o r y h a v e been useful for
m e a s u r i n g the fluid c o n t e n t of oil-bearing o r w a t e r
bearing sands.
Deresiewicz (1958) also c o n s i d e r e d t h e stress
r e q u i r e d t o s h e a r a cubic a r r a y of n o n a d h e s i v e spheres
h a v i n g a friction coefficient . T h e cubic stack w a s
originally c o m p r e s s e d isotropically u n d e r a stress 0,
t h e n a n e x t r a stress w a s applied parallel t o o n e of the
c u b e face d i a g o n a l s .
Deresiewicz f o u n d t h a t the angle of failure w a s
given by
t a n 2 = \/

(10)

a n d t h e m i n i m u m failure stress w a s
= 20(

+ (\-

1 2

(11)

T h e r e f o r e , for zero-friction particles, there is n o resis

t a n c e t o s h e a r of a n o n c o h e s i v e p o w d e r . H o w e v e r ,
w h e n there is sensible friction, it is evident t h a t t h e
resistance t o d e f o r m a t i o n is m o r e t h a n a simple
frictional t e r m , d e p e n d i n g also o n t h e s t r u c t u r e .
T h e original i m p e t u s for u n d e r s t a n d i n g the s h e a r
b e h a v i o r of g r a n u l a r m a t e r i a l s c a m e from soil m e c h
anics, t h e science devised by C o u l o m b t o design
e a r t h - r e t a i n i n g walls. C o u l o m b h a d originally sug
gested t h a t w h e n a p o w d e r w a s s h e a r e d in a s h e a r b o x
test, t h e s h e a r stress n e e d e d for failure w a s ( K e e d well 1984)

(8)
T

max = c +

T h e form of this e q u a t i o n h a s been verified experi

mentally ( K e n d a l l et al. 1987) by m a k i n g assemblies
of titania, a l u m i n a , silica a n d zirconia p o w d e r s of
v a r i o u s v o l u m e fractions, t h e n m e a s u r i n g t h e elastic
m o d u l u s . It a p p e a r s t h a t irregular p a c k i n g as well as
o r d e r e d a r r a y s fit this curve. A g r e e m e n t w a s g o o d
for particles u p t o 1 d i a m e t e r . A b o v e this size,
the m o d u l u s d r o p p e d as the p o w d e r s b e c a m e less
cohesive.
N o n c o h e s i v e p o w d e r s b e h a v e entirely differently
because their d e f o r m a t i o n is n o n l i n e a r . T h e y a r e n o t
H o o k e a n m a t e r i a l s , h a v i n g a zero m o d u l u s at z e r o

400

L z) (i-v ) J

Dds

Packing

fE

(12)

w h e r e c is the c o h e s i o n stress which is usually set a t

zero for n o n c o h e s i v e soils, is t h e n o r m a l stress
h o l d i n g t h e p o w d e r in place a n d is identified with
t h e friction coefficient.
F o r very-low-friction m a t e r i a l s (i.e., = 0), E q n .
(12) represents a perfectly plastic m a t e r i a l with c o n
s t a n t yield stress c. S u c h m a t e r i a l s c a n be described b y
t h e well-established t h e o r y of m e t a l plasticity (Hill
1950). T h i s c o n d i t i o n applies a l m o s t perfectly to s o m e
dispersions of p o w d e r in liquid, for i n s t a n c e , m o d e l
ling clay o r p o w d e r m i x e d with p o l y m e r solutions.

Powder

H o w e v e r , for m o s t d r y a n d wet p o w d e r s , t h e fric

tion c a n n o t b e neglected, with b e t w e e n 0.3 a n d 0.6,
so t h a t E q n . (12) represents m o r e c o m p l e x b e h a v i o r ,
with yield stress rising a s t h e n o r m a l stress is
increased.
A l t h o u g h C o u l o m b ' s t h e o r y h a s p r o v e d useful for
m u c h soil engineering, it p r e s u m e s t h a t p o w d e r s b e
have as plastic c o n t i n u a o f c o n s t a n t v o l u m e . In p r a c
tice this is n o t t r u e . W e l l - p a c k e d p o w d e r s e x p a n d as
shear occurs, a p h e n o m e n o n called d i l a t a n c y b y R e y
n o l d s (1885), w h e r e a s imperfectly p a c k e d p o w d e r s a r e
c o n s o l i d a t e d b y s h e a r i n g . It follows, therefore, t h a t
E q n . (12) is n o t strictly correct a n d t h a t t h e friction
coefficient defined b y C o u l o m b is higher t h a n t h e t r u e
value because of t h e e x t r a w o r k involved in dilating
the s t r u c t u r e , as indicated in E q n . (11).
Cohesive p o w d e r s i n t r o d u c e further p r o b l e m s
because friction is t h e n influenced b y a d h e s i o n
between particles ( K e n d a l l 1986). T h e friction coeffi
cient of wet silica w a s s h o w n t o increase from 0.3 t o
0.6 as t h e particles were r e d u c e d in size from 1 m m t o
0.01 m m in d i a m e t e r .
P o w d e r s of such small d i a m e t e r s also display a
tensile strength, w h i c h m a y b e m e a s u r e d b y f o r m i n g
the m a t e r i a l i n t o c o m p a c t s followed b y b e n d testing.
All p o w d e r m a s s e s seem t o b e brittle a n d fail b y a
cracking m e c h a n i s m . C o n s e q u e n t l y , they a r e sensitive
to defects. T h i s w a s tested b y c u t t i n g n o t c h e s i n t o
strips of c o m p a c t e d particles a n d m e a s u r i n g t h e fail
ure stress *, w h i c h w a s f o u n d t o b e described b y
*=

15.6/r/(Dc)

1 /2

(13)

where is t h e p a c k i n g v o l u m e fraction, is t h e w o r k
of a d h e s i o n , D is t h e particle d i a m e t e r a n d c is t h e
n o t c h length. It is clear from this e q u a t i o n t h a t
p o w d e r c o m p a c t s c a n a t t a i n high s t r e n g t h s if t h e
grains a r e small a n d t h e r e a r e n o flaws bigger t h a n t h e
particles themselves. F o r e x a m p l e , a t i t a n i u m dioxide
p o w d e r c o m p a c t c o u l d give a s t r e n g t h of 168 P a a t
0.2 d i a m e t e r . I n reality, all t h e c o m p a c t s e x a m i n e d
c o n t a i n e d flaws m u c h larger t h a n t h e grain size. T h e s e
flaws were often a g g l o m e r a t e s in t h e original p o w d e r ,
too strong to be broken down by the compaction

Mechanics

forces. S t r e n g t h s were generally in t h e M P a r a n g e as a

result of such flaws.
See also: Powder Characterization

Bibliography
Barlow W 1883 Probable nature of the internal symmetry of
crystals. Nature (London) 29: 186-8, 205-7
Bernal J D 1964 The structure of liquids. Proc. R. Soc.
London, Ser. A 280: 299-322
Cargill G S 1984 Radial distribution functions and microgeometry of dense random packings of hard spheres. In:
Johnson D L, Sen (eds.) 1984 Physics and Chemistry
of Porous Media, Conference Proceedings Vol. 107. Am
erican Institute of Physics, New York, pp. 20-36
Cumberland D J, Crawford R J 1987 The Packing of
Particles. Elsevier, Amsterdam
Deresiewicz 1958 Mechanics of granular matter. Adv.
Appl. Mech. 5: 233-306
Finney J L 1970 Random packings and the structure of
simple liquids. I. The geometry of random close packing.
Proc. R. Soc. London, Ser. 319: 479-93
Finney J L 1983 Modelling the atomic structure. In:
Luborsky F (ed.) 1983 Amorphous Metallic Alloys.
Butterworth, London, pp. 42-57
Hill R 1950 The Mathematical Theory of Plasticity. Claren
don, Oxford
Johnson L, Kendall K, Roberts A D 1971 Surface energy
and the contact of elastic solids. Proc. R. Soc. London,
Ser. A 324: 301-13
Keedwell J 1984 Rheology and Soil Mechanics. Elsevier
Applied Science, London
Kendall 1986 Inadequacy of Coulomb's friction law for
particle assemblies. Nature (London) 319: 203-5
Kendall K, Alford McN, Birchall J D 1987 Elasticity of
particle assemblies as a measure of the surface energy of
solids. Proc. R. Soc. London, Ser. A 412: 269-83
Pusey , van Megen W 1986 Phase behaviour of concen
trated suspensions of nearly hard colloidal spheres.
Nature (London) 320: 340-2
Reynolds 1885 On the dilatancy of media composed of
rigid particles in contact. Philos. Mag. Ser. 5 20: 469-81
Sutherland D N, Hutchinson 1965 An open-structured
random solid. Nature (London) 206: 1036-7
K. Kendall
[ICI, R u n c o r n , U K ]

401

R
Raman Spectroscopy
R a m a n s p e c t r o s c o p y is a n analytical t e c h n i q u e t h a t
yields i n f o r m a t i o n a b o u t t h e m o l e c u l a r s t r u c t u r e of
s a m p l e m a t e r i a l s b a s e d o n o b s e r v a t i o n of scattered
light spectra. T h e t e c h n i q u e , as well as t h e p h e n o m e
n o n o n which it is b a s e d , is n a m e d after t h e I n d i a n
physicist, C . V. R a m a n , w h o s e w o r k w a s inspired by
curiosity a b o u t t h e distinct b l u e c o l o r of t h e M e d i t e r
r a n e a n Sea. In 1928, after m o r e t h a n seven years of
studying t h e effects of scattered light, R a m a n r e p o r t e d
his discovery of frequency-shifted lines in t h e scat
tered light spectra of t r a n s p a r e n t s u b s t a n c e s . T h e
shifted lines, R a m a n a n n o u n c e d , were i n d e p e n d e n t of
the exciting r a d i a t i o n a n d characteristic of t h e s a m p l e
itself. F u r t h e r research efforts established t h e univer
sality of t h e p h e n o m e n o n a n d t h e r e l a t i o n s h i p of t h e
R a m a n s p e c t r u m of a m o l e c u l e t o its v i b r a t i o n a l a n d
r o t a t i o n a l frequencies. A l t h o u g h t h e i m p o r t a n c e of
the R a m a n scattering m e t h o d for t h e s t u d y of m o l e c u
lar s t r u c t u r e w a s recognized by t h e scientific c o m
m u n i t y , a lack of suitable i n s t r u m e n t a t i o n i m p e d e d its
early d e v e l o p m e n t as a n analytical t e c h n i q u e . H o w
ever, t h e c o n t r i b u t i o n of R a m a n s p e c t r o s c o p y t o a
wide r a n g e of m o d e r n a p p l i c a t i o n s , including m a t e r
ials science, h a s been e n s u r e d by t h e d e v e l o p m e n t
of t h e laser, which p r o v i d e s a c o n v e n i e n t s o u r c e
of intense m o n o c h r o m a t i c light, a n d of p h o t o e l e c
tric r e c o r d i n g devices, w h i c h offer sensitive signal
detection.

1.

Theory

Light, which is a f o r m of e l e c t r o m a g n e t i c r a d i a t i o n ,
c a n interact with m a t t e r in a n u m b e r of different
ways, s o m e of w h i c h involve t h e transfer of energy
between p h o t o n s a n d molecules. Since differences in
e l e c t r o m a g n e t i c energy c a n b e o b s e r v e d as differences
in wavelength, t h e result of a n energy transfer c a n be
m e a s u r e d with spectroscopic m e t h o d s .
T h e i n t e r a c t i o n of light of a given w a v e l e n g t h with
a p a r t i c u l a r object d e p e n d s o n t h e m o l e c u l a r s t r u c t u r e
of t h e object. I n c i d e n t light m a y be t r a n s m i t t e d ,
reflected, a b s o r b e d o r scattered b y t h e molecules.
Reflection o r t r a n s m i s s i o n o c c u r s with little o r n o
c h a n g e in t h e r a d i a n t energy, so light is reflected o r
t r a n s m i t t e d a t t h e s a m e w a v e l e n g t h as t h e incident
r a d i a t i o n . Light is a b s o r b e d a t w a v e l e n g t h s c o r r e s
p o n d i n g t o energy differences b e t w e e n t w o electron
states of t h e molecule.
M o s t light scattering o c c u r s w i t h o u t gain o r loss of
energy a n d is referred t o as Rayleigh scattering.
H o w e v e r , as R a m a n discovered, a small fraction of

t h e light scattered b y a molecule exhibits a c o n s t a n t

frequency shift from t h e incident light, indicating
energy transferred t o o r from t h e molecule. T h i s
frequency shift, which represents t h e difference in
energy b e t w e e n a n incident a n d a scattered p h o t o n , is
e q u i v a l e n t t o t h e difference b e t w e e n t w o v i b r a t i o n a l
energy states of t h e molecule. It is this energy dif
ference w h i c h is m e a s u r e d in R a m a n spectroscopy.
R a m a n shifts c a n be positive o r negative, d e p e n d
ing o n w h e t h e r energy is lost o r gained in t h e interac
tion w i t h t h e molecule. Lines in t h e R a m a n s p e c t r u m
t h a t a r e shifted t o longer w a v e l e n g t h s , representing a n
energy loss, a r e called S t o k e s lines; a n t i - S t o k e s lines
a r e t h o s e shifted t o s h o r t e r w a v e l e n g t h s , indicating a n
energy gain. Because they result from t h e m o r e fre
q u e n t l y o c c u r r i n g m o l e c u l a r t r a n s i t i o n from g r o u n d
t o excited state, S t o k e s lines a r e of g r e a t e r intensity,
a n d a r e m o r e often studied, t h a n a r e a n t i - S t o k e s lines.
T h e energy differences r e p r e s e n t e d by R a m a n shifts
a r e related t o t h e frequency of t h e v i b r a t i o n a l state by
the e q u a t i o n
AE=h(v0-

vnm)

w h e r e h is P l a n c k ' s c o n s t a n t , v 0 t h e frequency of t h e
incident r a d i a t i o n a n d vnm t h e frequency of t h e R a m a n
b a n d (i.e., t h e frequency of t h e v i b r a t i o n t h a t results
from t h e t r a n s i t i o n b e t w e e n energy levels a n d m).
F o r a n a n t i - S t o k e s s p e c t r u m , t h e frequency t e r m is
T h e intensity of a given v i b r a t i o n is p r o p o r t i o n a l t o
t h e f o u r t h p o w e r of t h e a b s o l u t e frequency of t h e
v i b r a t i o n ; t h a t is, t h e intensity of t h e signal increases
geometrically with t h e difference b e t w e e n incident
a n d v i b r a t i o n a l frequencies. Intensity is also directly
related t o t h e polarizability o r i n d u c e d dipole of t h e
molecule. F o r e x a m p l e , highly p o l a r i z a b l e molecules
like b e n z e n e o r c a r b o n disulfide p r o d u c e s t r o n g e r
signals t h a n w a t e r .

2. Information

Obtained

R a m a n s p e c t r o s c o p y c a n p r o v i d e qualitative, q u a n t i
tative a n d s t r u c t u r a l i n f o r m a t i o n a b o u t a variety of
m a t e r i a l s . M o s t significantly, t h e R a m a n s p e c t r u m
yields i n f o r m a t i o n a b o u t t h e m o l e c u l a r , r a t h e r t h a n
elemental, s t r u c t u r e of t h e s a m p l e .
Because t h e presence of p a r t i c u l a r a t o m i c g r o u p s
a n d chemical b o n d s is indicated by characteristic
frequencies in t h e R a m a n s p e c t r u m , t h e chemical
functional g r o u p s in a c o m p o u n d c a n be identified by
these g r o u p frequencies. T h e further a p p l i c a t i o n of
chemical i n t u i t i o n often leads t o t h e identity of t h e
c o m p o u n d itself.

403

Raman

Spectroscopy

T h e intensities of the b a n d s in a R a m a n s p e c t r u m
c a n be used t o d e t e r m i n e t h e c o n c e n t r a t i o n of a
c o m p o u n d of interest even in t h e presence of o t h e r
c o m p o u n d s . C o n c e n t r a t i o n s t o a few w t % a r e easily
achieved with a n y of several c a l i b r a t i o n t e c h n i q u e s ,
including c o m p a r i s o n with a n e x t e r n a l c a l i b r a t i o n
curve, a p p l i c a t i o n of the s t a n d a r d a d d i t i o n m e t h o d , in
which a k n o w n c o n c e n t r a t i o n of t h e c o m p o u n d is
a d d e d t o the m i x t u r e , o r use of a b a n d c o m m o n t o all
c o m p o n e n t s of t h e m i x t u r e as a n i n t e r n a l s t a n d a r d .
A w e a l t h of s t r u c t u r a l i n f o r m a t i o n a b o u t a c o m
p o u n d c a n be supplied b y R a m a n s p e c t r o s c o p y . F o r
e x a m p l e , it c a n be used t o differentiate a m o n g v a r i o u s
geometric forms of a c o m p o u n d , define t h e c o n f o r m a
tion a n d s y m m e t r y of a p o l y m e r o r d e t e r m i n e t h e
degree of crystallinity of a s u b s t a n c e .
T h e n u m b e r of R a m a n v i b r a t i o n s expected for a
given g e o m e t r y c a n be predicted by g r o u p theoretical
m e t h o d s . By c o m p a r i n g the o b s e r v e d R a m a n spec
t r u m with theoretical values, it is possible t o differen
tiate between g e o m e t r i c forms such as t e t r a h e d r a l a n d
s q u a r e p l a n a r c o o r d i n a t i o n . In several cases R a m a n
spectroscopy h a s p r o v i d e d t h e first evidence t h a t a n
i n o r g a n i c c o m p o u n d exists in o n e g e o m e t r y r a t h e r
than another.
T h e s h a r p n e s s a n d p o s i t i o n of t h e R a m a n b a n d s
are related t o t h e degree of crystallinity of t h e scatter
ing m e d i u m : the m o r e crystalline a m a t e r i a l , t h e
s h a r p e r the R a m a n b a n d s . E l e m e n t a l silicon, used
widely in the s e m i c o n d u c t o r i n d u s t r y , h a s a s t r o n g ,
1
s h a r p b a n d b e t w e e n 520 a n d 525 A c m " in t h e crystal
line state. In the a m o r p h o u s form this b a n d m o v e s t o
- 1
a lower R a m a n shift, as low as 480 A c m , a n d
becomes m u c h b r o a d e r a n d w e a k e r .
T h e R a m a n s p e c t r u m of a p o l y m e r reveals detailed
i n f o r m a t i o n a b o u t its s t r u c t u r e . It is possible t o define
the c o n f o r m a t i o n o r s e c o n d a r y s t r u c t u r e of p o l y m e r s
from the frequency p o s i t i o n s of certain sensitive
b a n d s in the R a m a n s p e c t r u m . I n b i o p o l y m e r s , for
e x a m p l e , t h e a m i d e b e n d i n g m o d e s in t h e 1 2 0 0 1
1700 A c m " region a r e used as m a r k e r s to c h a r a c t e r
ize w h e t h e r the molecule is in a helical, r a n d o m o r
folded-sheet s t r u c t u r e .
T h e degree of s t r u c t u r a l s y m m e t r y of a s u b s t a n c e is
indicated by t h e a m o u n t of v a r i a t i o n in t h e p o l a r i z a
tion characteristics of the R a m a n b a n d s . In a highly
o r d e r e d p o l y m e r , there is a m i x t u r e of b o t h p o l a r i z e d
a n d depolarized b a n d s , while in a d i s o r d e r e d p o l y m e r ,
all the R a m a n active b a n d s a r e polarized. T h e distinc
tion b e t w e e n t h e t w o is evidenced b y t h e intensity of
the b a n d s as viewed t h r o u g h a n a n a l y z e r o r i e n t e d
n o r m a l t o the p o l a r i z a t i o n of the scattered r a d i a t i o n :
the intensity of the p o l a r i z e d b a n d s a p p r o a c h e s z e r o ,
while t h a t of the d e p o l a r i z e d b a n d s is n o n z e r o .
T h e m o l e c u l a r c h a i n length of p o l y m e r s is indicated
by a
special class of low-frequency
bands
- 1
( < 100 A c m ) in t h e R a m a n s p e c t r u m . F o r these
b a n d s , k n o w n as l o n g i t u d i n a l a c o u s t i c m o d e s
( L A M s ) , p o s i t i o n is inversely related t o c h a i n length;

404

t h a t is, the closer t h e b a n d is t o t h e excitation fre

q u e n c y , t h e longer t h e c h a i n length. R a m a n spectros
c o p y c a n also b e used t o follow c h a n g e s in p h a s e as a
function of t e m p e r a t u r e a n d t o m o n i t o r t h e a m o u n t
of h y d r o g e n b o n d i n g in a p o l y m e r system.

5.

Instrumentation

T h e basic i n s t r u m e n t a l r e q u i r e m e n t s for R a m a n spec

t r o s c o p y a r e a s o u r c e of i l l u m i n a t i o n a n d a device for
r e c o r d i n g t h e s p e c t r u m . I n R a m a n ' s original experi
m e n t s , filtered sunlight w a s used as t h e exciting r a d i a
tion a n d t h e scattered b e a m , also filtered, w a s
o b s e r v e d with t h e n a k e d eye. I n s u b s e q u e n t experi
m e n t s , R a m a n a n d his associates e m p l o y e d a m e r c u r y
l a m p as t h e r a d i a t i o n s o u r c e a n d dispersed t h e scat
tered light w i t h a simple s p e c t r o g r a p h . M o d e r n
i n s t r u m e n t a t i o n typically includes a laser as t h e
source of i l l u m i n a t i o n a n d a d o u b l e s p e c t r o m e t e r ,
p o s i t i o n e d a t 90 t o t h e excitation b e a m , for analysis
of t h e scattered light s p e c t r u m . A n optical d i a g r a m of
a typical c o m m e r c i a l R a m a n system is s h o w n in Fig.
1, illustrating b o t h m a c r o - a n d m i c r o i l l u m i n a t o r s . I n
t h e m i c r o s y s t e m t h e objective focuses t h e laser b e a m
a n d collects t h e scattered r a d i a t i o n , which is p a s s e d
o n t o t h e s p e c t r o m e t e r e n t r a n c e slit.
A laser p r o v i d e s a very intense, m o n o c h r o m a t i c
source of i l l u m i n a t i o n t h a t is ideal for R a m a n spec
t r o s c o p y . L a s e r s a r e c h a r a c t e r i z e d as c o n t i n u o u s w a v e ( C W ) o r pulsed s o u r c e a n d in t e r m s of their
principal linesthe w a v e l e n g t h s a t which they p r o
vide m a x i m u m p o w e r . Selection of a laser is deter
m i n e d p r i m a r i l y b y t h e r e q u i r e m e n t s of t h e p a r t i c u l a r
a p p l i c a t i o n , such as t h e need for a C W o r pulsed
s o u r c e a n d t h e o p t i m u m excitation w a v e l e n g t h . T h e
m o r e c o m m o n l y used C W lasers include a r g o n ion
(with principal lines a t 514.5 a n d 488.0 n m ) , k r y p t o n
ion
(647.1
and
530.2 n m )
and
helium-neon
(632.8 n m ) . Pulsed lasers include n e o d y m i u m - d o p e d
y t t r i u m - a l u m i n u m g a r n e t (1060, 530, 355 a n d
265 n m ) , excimer (350, 308, 248, 222 a n d 193 n m ) a n d
n i t r o g e n (337 n m ) . M o s t of these a r e available in
c o m b i n a t i o n with dye lasers, which offer t u n a b l e
excitation frequencies. F o r d y e lasers, a set of inter
c h a n g e a b l e dyes collectively p r o v i d e s a c o n t i n u o u s
selection of excitation w a v e l e n g t h s from the ultra
violet t h r o u g h t h e n e a r infrared.
Because the intensity of t h e R a m a n scatter is very
w e a k with respect t o t h e m o r e p r o m i n e n t Rayleigh
scatter, high dispersion a n d sensitive d e t e c t i o n of t h e
scattered s p e c t r u m a r e essential in R a m a n spectros
c o p y . A d o u b l e s p e c t r o m e t e r is generally e m p l o y e d t o
isolate t h e R a m a n signal in the presence of r a d i a t i o n
6
t h a t is m o r e intense b y a factor of 10 . T w o h o l o g r a phically ruled g r a t i n g s a n d t w o sets of e n t r a n c e a n d
exit slits serve t o m i n i m i z e t h e a m o u n t of u n w a n t e d
r a d i a t i o n . T h e resulting signal is detected b y a redsensitive p h o t o m u l t i p l i e r t u b e ( P M T ) , such as a

Raman

multialkali o r gallium a r s e n i d e P M T , t h a t h a s a high

q u a n t u m efficiency a n d a thermoelectrically c o o l e d
h o u s i n g t o r e d u c e b a c k g r o u n d noise.
T h e signal from t h e d e t e c t o r is usually fed i n t o a
m i c r o c o m p u t e r for s t o r a g e a n d analysis. I n c o m m e r
cially available systems, t h e m i c r o c o m p u t e r c o m b i n e s
the functions of s p e c t r o m e t e r c o n t r o l , d e t e c t i o n elec
tronics a n d d a t a m a n i p u l a t i o n . W i t h such a system,
once t h e s a m p l e is in place a n d t h e resolution h a s been
selected, d a t a c a n b e a c q u i r e d w i t h o u t o p e r a t o r inter
vention. Repetitive s c a n n i n g for signal a v e r a g i n g a n d
frequently used software r o u t i n e s , such a s s m o o t h i n g
a n d calculation of p e a k a r e a s , a r e s t a n d a r d features.
A relatively recent i n n o v a t i o n in R a m a n i n s t r u
m e n t a t i o n is t h e i n c o r p o r a t i o n of a modified researchg r a d e m i c r o s c o p e as t h e s a m p l e i l l u m i n a t o r a n d
collection optics. T h i s a d d i t i o n , which p e r m i t s investi
g a t i o n of m i c r o s c o p i c s a m p l e s with a spatial resolu
tion of 1 , h a s been a great asset t o t h e fields of
geochemistry, s e m i c o n d u c t o r s a n d c o r r o s i o n analysis.
It allows investigators t o o b t a i n m o l e c u l a r a n d s t r u c
tural i n f o r m a t i o n n o n d e s t r u c t i v e l y in situ.

4. Comparison
with Infrared
Other
Techniques

Spectroscopy

and

R a m a n s p e c t r o s c o p y a n d infrared a b s o r p t i o n spec
t r o s c o p y a r e c o m p l e m e n t a r y analytical t e c h n i q u e s .
Both provide vibrational information about the mol
ecule, b u t different d a t a a r e c o n v e y e d in t h e scattering
a n d a b s o r p t i o n s p e c t r a a n a l y z e d , respectively, b y
R a m a n a n d infrared s p e c t r o s c o p y (see Infrared Spec
troscopy). B o t h R a m a n a n d infrared d a t a a r e r e q u i r e d
to characterize fully t h e v i b r a t i o n a l s p e c t r u m of a n

Spectroscopy

u n k n o w n c o m p o u n d , p a r t i c u l a r l y o n e with highly
symmetric geometry.
T h e c o m p l e m e n t a r y n a t u r e of t h e techniques is
exemplified b y their selection rules: a v i b r a t i o n is
R a m a n - a c t i v e if there is a c h a n g e in t h e i n d u c e d
dipole o r polarizability of t h e molecule; it is infraredactive if there is a c h a n g e in t h e p e r m a n e n t dipole.
I o n i c species, such as s o d i u m c h l o r i d e , a r e a m o n g t h e
few types of c o m p o u n d which d o n o t h a v e a R a m a n
s p e c t r u m . A h o m o n u c l e a r d i a t o m i c molecule like
n i t r o g e n d o e s n o t h a v e a n infrared s p e c t r u m , b u t
sodium chloride does.
A p a r t i c u l a r m o l e c u l a r v i b r a t i o n m a y b e observ
able in b o t h spectra, b u t different in intensity. T h e
lower t h e s y m m e t r y of a molecule, t h e greater t h e
o v e r l a p of its R a m a n - a c t i v e a n d infrared-active vibra
tions. I n m o s t real-world s a m p l e s , a high degree of
o v e r l a p p e r m i t s selection of R a m a n o r infrared spec
t r o s c o p y as t h e preferred analytical t e c h n i q u e . In
general, n o n p o l a r c o m p o u n d s a n d s y m m e t r i c vibra
tions a r e m o r e readily o b s e r v e d in R a m a n spectros
c o p y , w h e r e a s infrared s p e c t r o s c o p y favors p o l a r
compounds and asymmetric vibrations.
T a b l e s 1-3 illustrate differences in s a m p l e h a n d l i n g ,
i n s t r u m e n t a t i o n a n d t y p e of i n f o r m a t i o n o b t a i n e d for
the R a m a n a n d infrared t e c h n i q u e s . A s indicated in
the tables, R a m a n s p e c t r o s c o p y offers a n u m b e r of
a d v a n t a g e s over infrared s p e c t r o s c o p y . A p r i m a r y
a d v a n t a g e of R a m a n is t h a t it c a n b e p e r f o r m e d in t h e
visible region of t h e s p e c t r u m , w h e r e sources a r e m o r e
intense a n d d e t e c t o r s a r e m u c h m o r e sensitive t h a n in
t h e infrared. A n o t h e r a d v a n t a g e is t h e spectral r a n g e
of R a m a n i n s t r u m e n t a t i o n . T h e entire s p e c t r u m , from
1
10 t o 4000 c m , c a n be r e c o r d e d in a single scan with
t h e s a m e R a m a n i n s t r u m e n t . I n infrared spectros
c o p y , t h e scan r a n g e is m o r e limited: a different

Spectrograph stage

Focal plane
7 5 mm

outside housing

Turret with
3 kinematic

^-

!--_-0

Slot

(EK-V
Slit

gratings

Filter stage

- -
Subtractive
dispersion

Entrance I
slit

Figure 1
Optical schematic of a typical Raman system

405

Raman

Spectroscopy

Table 1
Comparison of sampling handling in Raman and infrared
3
spectroscopy
Raman
General applicability 95
(%)
Unsuitable materials fluorescent and
colored samples
Sample preparation
liquids
powders
single crystals
polymers
single fibers
gases and vapors
Cells
Micro work
mass ^g)
size ()
Trace work
High and low
temperature
Limits of detection

very simple
very simple
very simple
very simple
very simple (but see
unsuitable
materials)
moderately simple
with microscope
moderately simple
very simple (glass)
good
<1
1
sometimes
moderately simple
good

Infrared
99
single crystals,
metals,
aqueous
solutions
variable
very simple
more difficult
very difficult
more difficult

moderate
laser

Detector
1

Resolution ( c m )
Principal limitation
Wave number
range
1
(Acm )

Purge requirement
Photometry

simple
more complex
(alkali halide)
good
<1
20
sometimes
moderately
simple
very good

406

Infrared

slightly greater
blackbody or
diode laser
photomultiplier tube thermal,
pyroelectric,
bolometers
-0.15
-0.05
energy
energy
10-4000
18(M000 (one
instrument)
10-400
(second
instrument or
alternative
beam splitter,
source and
detector)
no
yes
scattering single
absorption
beam
double beam

a Adapted from Sloane (1971)

Infrared

excellent
symmetric
excellent
excellent
excellent
fair

excellent
asymmetric
very good
excellent
very difficult
good

excellent

difficult

fair

excellent

difficult

Table 2
Comparison 8of instrumentation for Raman and infrared
spectroscopy

Complexity
Source

Fingerprinting
Best vibrations
Structural
Group frequencies
Aqueous solutions
Quantitative
analysis
Low-frequency
modes
Libraries

Raman

a Adapted from Sloane (1971)

a Adapted from Sloane (1971)

Raman

Table 3
Comparison of quality of 8information provided by Raman
and infrared spectroscopy

i n s t r u m e n t , o r at least a c h a n g e of b e a m splitter a n d
1
d e t e c t o r , is r e q u i r e d below 180 c m .
R a m a n also offers a n a d v a n t a g e in s a m p l e p r e p a r a
tion. Typically, there is little o r n o s a m p l e p r e p a r a t i o n
required for R a m a n t e c h n i q u e s , while ir s p e c t r o s c o p y
requires t h e s a m p l e t o be pressed i n t o a pellet with a
K B r m a t r i x o r g r o u n d i n t o a m u l l with m i n e r a l oil.
A q u e o u s s o l u t i o n s , which p o s e serious difficulties for
infrared s p e c t r o s c o p y , p r e s e n t n o p r o b l e m s for
R a m a n , p r i m a r i l y b e c a u s e w a t e r is a p o o r R a m a n
scatterer b u t a s t r o n g ir a b s o r b e r . T h e s a m p l e cells
also c o n t r i b u t e t o t h e difference: glass, which is used
in R a m a n cells, is easy t o h a n d l e , b u t ir cells, typically
m a d e of a n alkali halide o r s o m e o t h e r highly h y g r o
scopic salt, a r e m u c h m o r e delicate.
A n analytical a d v a n t a g e of infrared over R a m a n
s p e c t r o s c o p y is t h e g r e a t e r availability of d o c u m e n t e d
spectra. Extensive spectral libraries facilitate t h e iden
tification of u n k n o w n c o m p o u n d s .
T h e m o l e c u l a r n a t u r e of t h e i n f o r m a t i o n o b t a i n e d
with R a m a n s p e c t r o s c o p y gives it a distinct a d v a n t a g e
over electron t e c h n i q u e s such as electron spectros
c o p y for chemical analysis ( E S C A ) , A u g e r spectros
c o p y a n d electron m i c r o p r o b e s , which yield only
elemental i n f o r m a t i o n . F o r e x a m p l e , R a m a n c a n dis
tinguish b e t w e e n styrene a n d 1,4-butadiene in a s a m
ple, w h e r e a s E S C A c a n d e t e r m i n e only t h a t there is
c a r b o n p r e s e n t (see Electron Spectroscopy for Chem
ical Analysis). T h e R a m a n capability for in situ a n a l y
sis is also a n a d v a n t a g e for m a n y a p p l i c a t i o n s .
F l u o r e s c e n c e interference is a m a j o r d i s a d v a n t a g e
in R a m a n s p e c t r o s c o p y . Because fluorescence is a
m u c h s t r o n g e r effect, it c a n completely o v e r w h e l m t h e
R a m a n s p e c t r u m . W h e n impurities a r e t h e s o u r c e of
t h e fluorescence, t h e p r o b l e m m a y be c o r r e c t e d b y
purifying t h e s a m p l e , for e x a m p l e by recrystallization
o r simply by filtering it t h r o u g h activated c h a r c o a l o r
a l u m i n a . O t h e r a p p r o a c h e s include selecting a n exci
t a t i o n frequency a w a y from t h e fluorescence excita
tion o r q u e n c h i n g t h e fluorescence. A p e r i o d of laser

Raman

Monitor

TV

camera

Rotating

Spectroscopy

Photomultiplier
tube

prism

Optional
viewing port
S p a t i a l filter
,

Collimated

light

Beam
'splitters

HHH)

Reflection
illuminator

- g

>

U*

Objective

~ T s t a g e
Transmission
illuminator

Figure 2
Optical schematic of a triple spectrograph designed for multichannel detectors

i r r a d i a t i o n before d a t a a c q u i s i t i o n c a n be used for

q u e n c h i n g or, in s o l u t i o n w o r k , q u e n c h e r s such a s
m e t h y l iodide, t h a l l i u m n i t r a t e o r a c r y l a m i d e c a n b e
a d d e d t o t h e s a m p l e . T i m e d i s c r i m i n a t i o n is a n effec
tive b u t m o r e expensive s o l u t i o n . Since t h e t i m e scale
1 2
15
for R a m a n scattering, 1 0 s, is s h o r t e r t h a n
t h a t for fluorescence b y several o r d e r s of m a g n i t u d e ,
it is possible t o d i s c r i m i n a t e a g a i n s t fluorescence b y
using p i c o s e c o n d - p u l s e d lasers a n d g a t e d d e t e c t i o n .
C o l o r e d s a m p l e s a r e a n o t h e r p o t e n t i a l p r o b l e m for
R a m a n s p e c t r o s c o p y . If t h e s a m p l e is highly c o l o r e d
a n d a b s o r b s t h e laser excitation, t h e s a m p l e m a y b e
destroyed. T h i s is easily a v o i d e d , h o w e v e r , b y spin
ning t h e s a m p l e a t a few h u n d r e d r p m so t h a t a n e w
p o r t i o n of t h e s a m p l e is c o n s t a n t l y being e x p o s e d .
Alternatively, a cylindrical lens m a y b e used t o focus
the laser t o a line r a t h e r t h a n t o a p o i n t o n t h e s a m p l e ,
t h u s s p r e a d i n g t h e r a d i a t i o n o v e r a larger a r e a a n d
lessening t h e c h a n c e s of d a m a g e .

5. Important

Developments

in

Raman

Spectroscopy
T h e m u l t i c h a n n e l optical d e t e c t o r , o r a r r a y d e t e c t o r ,
h a s b e c o m e increasingly i m p o r t a n t in R a m a n spec
t r o s c o p y . T h i s device e m p l o y s 512 o r 1024 s e p a r a t e

d e t e c t o r elements for s i m u l t a n e o u s o b s e r v a t i o n of a
large s e g m e n t of a s p e c t r u m . Because a m u l t i c h a n n e l
d e t e c t o r eliminates t h e need for p o i n t - b y - p o i n t inte
g r a t i o n of t h e s p e c t r u m , it p e r m i t s m u c h faster d a t a
acquisition. S h o r t e r a c q u i s i t i o n times a r e critical in
t h e investigation of p h a s e c h a n g e s , excited states o r
t r a n s i e n t species such as r e a c t i o n i n t e r m e d i a t e s . T h e
resulting decrease in i r r a d i a t i o n t i m e is also i m p o r t a n t
for u n s t a b l e s a m p l e s .
A d a p t a t i o n s of t h e R a m a n system s p e c t r o m e t e r a r e
necessary t o m a k e it c o m p a t i b l e with a m u l t i c h a n n e l
d e t e c t o r . H i g h dispersion is a p r o b l e m , because it
limits t h e spectral c o v e r a g e , b u t it is still necessary t o
reject t h e n o n - R a m a n scatter. O n e s o l u t i o n is t h e use
of a triple s p e c t r o g r a p h such as t h a t s h o w n in Fig. 2.
A s i n d i c a t e d in t h e d i a g r a m , a short-focal-length,
z e r o - d i s p e r s i o n d o u b l e m o n o c h r o m a t o r acts as a
n o t c h filter t o isolate t h e R a m a n scatter from the
u n w a n t e d r a d i a t i o n . A s p e c t r o g r a p h t h e n disperses it
with a n u n v i g n e t t e d , flat focus across t h e d e t e c t o r
face. T h e triple s p e c t r o g r a p h c a n b e used with either
macrosample or microsample modules.
A t e c h n i q u e w h i c h h a s p r o v e d very effective for
thin films is t h e c o u p l i n g of i n t e g r a t e d optics with the
n o r m a l R a m a n collection optics. T h i s p e r m i t s the
laser t o b e m u l t i p a s s e d t h r o u g h the film several

407

Raman

Spectroscopy

h u n d r e d times, t h e r e b y increasing t h e o b s e r v e d inten

sity of the R a m a n scatter. W i t h this t e c h n i q u e ,
R a m a n spectra h a v e been o b s e r v e d for p o l y m e r films
< 1 thick. I n t e g r a t e d optics m a k e it possible t o
study p o l y m e r - p o l y m e r , s o l i d - g a s o r s o l i d - l i q u i d
interfaces.
In c o n v e n t i o n a l R a m a n e x p e r i m e n t s , t h e excitation
frequency is far r e m o v e d from a n y electronic a b s o r p
tions of t h e molecule. If t h e excitation frequency is
within a n a b s o r p t i o n b a n d , h o w e v e r , t h o s e v i b r a t i o n s
associated with the c h r o m o p h o r i c g r o u p are selecti
6
vely e n h a n c e d by a factor as m u c h as 10 . T h e a m o u n t
of e n h a n c e m e n t in a p a r t i c u l a r instance is r o u g h l y
p r o p o r t i o n a l to t h e intensity of t h e electronic a b s o r p
tion at the excitation frequency. R e s o n a n c e R a m a n
spectroscopy, the t e c h n i q u e b a s e d o n this e n h a n c e
m e n t effect, yields i n f o r m a t i o n t h a t c o u l d n o t be
o b t a i n e d b y c o n v e n t i o n a l R a m a n m e t h o d s . F o r ex
a m p l e , it h a s been used t o investigate e l e c t r o n - p h o n o n i n t e r a c t i o n in s e m i c o n d u c t o r s such as g e r m a n i u m
a n d G a A s . F o r large m a c r o m o l e c u l e s , r e s o n a n c e
R a m a n also p r o v i d e s a d d e d selectivity. Since only t h e
c h r o m o p h o r i c g r o u p v i b r a t i o n s a r e e n h a n c e d , the
n u m b e r of observed v i b r a t i o n s is greatly r e d u c e d a n d
the analysis is simplified.
A n o t h e r t e c h n i q u e for e n h a n c i n g the R a m a n signal
is called surface-enhanced R a m a n
spectroscopy
( S E R S ) . In S E R S , e n h a n c e m e n t by a factor of u p t o
6
10 is d u e t o a d s o r p t i o n of the s a m p l e o n a m e t a l
surface, n o r m a l l y silver b u t s o m e t i m e s gold o r c o p
per. T h e m e t a l surface m a y be a n electrode in a n
electrochemical cell, a thin film d e p o s i t e d u n d e r high
v a c u u m o r a colloidal suspension. F o r m a x i m u m en
h a n c e m e n t , t h e surface of t h e m e t a l m u s t be r o u g h
ened at the m i c r o s c o p i c level. A l t h o u g h m a n y of t h e
e x p e r i m e n t s in this a r e a h a v e b e e n designed t o help
elucidate the m e c h a n i s m of the effect, analytical appli
cations are also being developed. F o r e x a m p l e , S E R S
h a s been used t o s t u d y t h e species p r e s e n t in t h e
d o u b l e layer a r o u n d a n electrode in a n electrochemi
cal cell, including a d s o r b e d a n i o n s , c a t i o n s , solvent
a n d n e u t r a l a b s o r b a t e s . T h e e x p e r i m e n t s a r e d o n e in
situ a n d t h e i n f o r m a t i o n o b t a i n e d is m o r e c o m p r e h e n
sive t h a n t h a t from electrochemical m e t h o d s a l o n e .
Best results h a v e been o b t a i n e d with c o m p o u n d s
c o n t a i n i n g n i t r o g e n a t o m s , such as pyridine a n d
cyanides.

6.

Applications

T h e diverse a p p l i c a t i o n s of R a m a n s p e c t r o s c o p y in
clude m a t e r i a l s analysis of s e m i c o n d u c t o r s , p o l y m e r s ,
p i g m e n t s a n d catalysts, a n d investigations in t h e fields
of physics, g e o c h e m i s t r y a n d b i o c h e m i s t r y . F o r ex
a m p l e , R a m a n s p e c t r o s c o p y h a s been used t o m o n i t o r
impurities d u r i n g the processing of silicon crystals
a n d t o detect toxic m o n o m e r s in c o n t a c t lenses.
H i g h - p u r i t y crystalline silicon is used extensively in

408

Raman

shift

(cm )

Figure 3
Raman spectra of silicon wafers containing interstitial
oxygen (upper trace) and oxygen-free (lower trace).
(Micro-Raman spectrometer with 514.5 nm 0.02 W argon
ion laser source)

t h e m a n u f a c t u r e of s e m i c o n d u c t o r s a n d solar cells.
T h e m o s t c o m m o n m e t h o d for g r o w i n g silicon, the
C z o c h r a l s k i m e t h o d , i n t r o d u c e s interstitial oxygen
a n d s u b s t i t u e n t c a r b o n impurities i n t o t h e silicon
crystal. A l t h o u g h a t low levels these impurities serve
beneficial roles, excluding o t h e r impurities a n d
t h e r e b y p r e v e n t i n g l e a k a g e c u r r e n t s in t h e e n d device,
at higher c o n c e n t r a t i o n s they c a u s e w a r p i n g of t h e
silicon wafer. M o r e o v e r , h e a t m a y c a u s e p r e c i p i t a t i o n
of t h e interstitial oxygen t o f o r m S i 0 2 . R a m a n spec
t r o s c o p y offers a n o n d e s t r u c t i v e t e c h n i q u e for m o n i
t o r i n g i m p u r i t y levels, w h i c h m a y b e altered d u r i n g
t h e m a n u f a c t u r i n g process.
F i g u r e 3 s h o w s m i c r o - R a m a n spectra for t w o sili
c o n wafers, o n e m a n u f a c t u r e d b y t h e C z o c h r a l s k i
m e t h o d ( u p p e r trace), t h e o t h e r g r o w n b y a n a l t e r n a t
ive p r o c e s s t h a t d o e s n o t i n t r o d u c e interstitial oxygen.
B o t h spectra exhibit a p h o n o n b a n d of crystalline
1
silicon a t 525 A c m " . T h e w e a k , b r o a d feature a t
-1
~1000 Acm
is a n o v e r t o n e s p e c t r u m of t h e
-1
525 A c m
p e a k . T h e s p e c t r u m for t h e C z o c h r a l s k i
- 1
wafer clearly s h o w s a b a n d a t 510 Acm , which is d u e
to t h e interstitial oxygen, while t h e lower s p e c t r u m
s h o w s only t h e crystalline silicon b a n d s .
P o l y ( m e t h y l m e t h a c r y l a t e ) ( P M M A ) is a p o l y m e r
used for b o t h c o n t a c t lenses a n d i m p l a n t lenses. T h e
p r o d u c t i o n of P M M A involves b r e a k i n g the d o u b l e
b o n d b e t w e e n c a r b o n a t o m s in t h e m o n o m e r m e t h y l
m e t h a c r y l a t e . A l t h o u g h P M M A c a n be safely i n t r o
d u c e d i n t o t h e b o d y e n v i r o n m e n t , r e p o r t s indicate
t h a t t h e m o n o m e r from w h i c h it is f o r m e d m a y be
toxic. R a m a n s p e c t r o s c o p y c a n b e used t o d e t e r m i n e
t h e residual q u a n t i t y of m o n o m e r in t h e P M M A lens
material.
F i g u r e 4 s h o w s a R a m a n s p e c t r u m for a P M M A
s a m p l e w i t h ~ 1 % m o n o m e r . T h e d e t e r m i n a t i o n is

Reflection

Electron

Microscopy

I I 0

Grasselli J G, Snavely , Bulkin J 1981 Chemical

Applications of Raman Spectroscopy. Wiley, New York
Long D A 1977 Raman Spectroscopy. McGraw-Hill, New
York
Siesler W, Holland-Moritz 1980 Infrared and Raman
Spectroscopy of Polymers. Dekker, New York
Sloane J 1971 The technique of Raman spectroscopy: a
state-of-the-art comparison to infrared. Appl. Spectrosc.
25: 430-9

F . Purcell
[Spex I n d u s t r i e s , E d i s o n ,
N e w Jersey, U S A ]
I
0

1550

2000

Raman shift

(cm)

Figure 4
Raman spectrum of poly(methyl methacrylate) with ~ 1 %
residual monomer. (Raman spectrometer with 488.0 nm
0.125 W argon ion laser source)

m a d e from the intensity of t h e C = C stretching fre

_ 1
q u e n c y a t 1 6 4 0 A c m , w h i c h is p r e s e n t o n l y in t h e
m o n o m e r . T h e intensity of t h e ester c a r b o n y l b a n d a t
-1
serves as a n i n t e r n a l s t a n d a r d , a n d a
1730 A c m
c a l i b r a t i o n c u r v e is established with a few s a m p l e s of
k n o w n m o n o m e r c o n t e n t . C o n c e n t r a t i o n s of a few
h u n d r e d t h s of 1 % m o n o m e r in P M M A c a n b e d e t e r
m i n e d by this m e t h o d .

7. Future

Prospects

Interest in R a m a n s p e c t r o s c o p y , which h a s g r o w n
steadily since t h e 1960s, is likely t o receive further
i m p e t u s from c o n t i n u e d d e v e l o p m e n t s in b o t h tech
niques a n d i n s t r u m e n t a t i o n . A d v a n c e s in c o n t i n u o u s wave ultraviolet lasers will e x t e n d t h e applicability of
r e s o n a n c e R a m a n s p e c t r o s c o p y . I m p r o v e m e n t s in
m u l t i c h a n n e l d e t e c t o r s will increase t h e speed a n d
convenience of R a m a n investigations. D e v e l o p m e n t
of surface-enhanced R a m a n s p e c t r o s c o p y will lead t o
new analytical m e t h o d s for s t u d y i n g surface p h e n o
m e n a . W i d e r availability of c o m p u t e r i z e d systems
will e n a b l e m o r e sophisticated e x p e r i m e n t s a n d d a t a
h a n d l i n g . Extensive spectral libraries a n d c o m p u t e r
ized searches will a d d c o n v e n i e n c e a n d efficiency t o
R a m a n analyses. T h e future of R a m a n s p e c t r o s c o p y
a p p e a r s bright, with p r o m i s e s of faster acquisition
times, better a n d m o r e flexible sources a n d completely
a u t o m a t e d systems.
See also: Infrared Spectroscopy; Polymers: Raman Spec
troscopy

Bibliography
Clark R J H, Hester R (eds.) 1976-84 Advances in Infrared
and Raman Spectroscopy, Vols. 1-11. Wiley, New York

Reflection Electron Microscopy

T h e physical a n d chemical p r o p e r t i e s of surfaces a r e
of f u n d a m e n t a l i m p o r t a n c e in m a n y aspects of m a t e r
ials science, from c o r r o s i o n t o the g r o w t h of novel
s e m i c o n d u c t o r devices, a n d they h a v e been e x a m i n e d
by a wide variety of t e c h n i q u e s over m a n y years. M o s t
of these t e c h n i q u e s give a v e r a g e d results from large
a r e a s of t h e s a m p l e a n d t h e effects of i n h o m o g e n e i t i e s
a r e either i g n o r e d or, a t best, implied indirectly from
t h e d a t a . H o w e v e r , it is often such defects in the form
of dislocations a n d m o n a t o m i c steps t h a t h a v e a
crucial influence o n t h e chemical a n d physical c h a n g e s
t h a t o c c u r a t surfaces. I n o r d e r t o e x a m i n e directly the
role p l a y e d by defects, t e c h n i q u e s with high spatial
r e s o l u t i o n a n d surface sensitivity a r e r e q u i r e d .
In recent years v a r i o u s types of m i c r o s c o p y h a v e
b e e n d e v e l o p e d t h a t c a n i m a g e surfaces with the
r e q u i r e d spatial r e s o l u t i o n a n d o n e of t h e m o s t flex
ible of these is reflection electron m i c r o s c o p y ( R E M ) .
A l t h o u g h R E M w a s a t t e m p t e d s o o n after t h e inven
tion of t h e electron m i c r o s c o p e it w a s only after Y a g i
a n d his c o - w o r k e r s (Yagi 1987) succeeded in m a k i n g
clean flat crystalline silicon surfaces in a n electron
m i c r o s c o p e t h a t m o n a t o m i c steps, dislocations a n d
d y n a m i c surface processes were o b s e r v e d . T h e ability
t o o b s e r v e n u c l e a t i o n a n d g r o w t h processes a n d t o
d e t e r m i n e t h e effect t h a t m o n a t o m i c steps h a v e o n
these c h a n g e s d e m o n s t r a t e d t o surface scientists the
value of real-space i m a g i n g .

7. Imaging

and Image

Interpretation

F o r R E M i m a g i n g in a c o n v e n t i o n a l t r a n s m i s s i o n
electron m i c r o s c o p e , t h e s a m p l e m u s t be flat a n d
crystalline. T o achieve surface sensitivity the electrons
s h o u l d n o t p e n e t r a t e far b e l o w t h e surface a n d this is
achieved b y h a v i n g t h e incident parallel b e a m of
electrons i m p i n g i n g o n t h e surface at a glancing angle.
W i t h this g e o m e t r y t h e electrons reflected from the
surface give rise t o a reflection high-energy electron
diffraction ( R H E E D ) p a t t e r n (see Fig. 1) in the b a c k
focal p l a n e of t h e objective lens. I n o r d e r t o p r o d u c e a

409

Reflection

Electron

Microscopy

Sample

Figure 1
REM image formation

s t r o n g signal the incident b e a m is tilted t o m a k e a

Bragg angle with t h e surface p l a n e s a n d t h e specular
spot is allowed t h r o u g h t h e objective a p e r t u r e a n d
used for i m a g i n g w h e r e a s all t h e o t h e r diffraction
spots are c u t o u t . T h e intensity of t h e i m a g e c a n b e
further e n h a n c e d b y a z i m u t h a l r o t a t i o n of t h e speci
m e n t o a p o s i t i o n w h e r e a surface r e s o n a n c e is excited
(this c a n be considered as a diffraction c o n d i t i o n
w h e r e o n e b e a m travels parallel t o , a n d j u s t b e l o w , t h e
surface). T h e specimen a n d incident b e a m a r e tilted so
t h a t the specular b e a m travels d o w n t h e c e n t e r of t h e
i m a g i n g lens t o r e d u c e spherical a b e r r a t i o n . It c a n b e
seen from Fig. 1 t h a t R E M is a n a l o g o u s t o d a r k field
i m a g i n g in t r a n s m i s s i o n electron m i c r o s c o p y .
T h e g e o m e t r y e m p l o y e d in R E M h a s t w o i n h e r e n t
p r o b l e m s . First, t h e r e is c o n s i d e r a b l e f o r e s h o r t e n i n g
of the i m a g e (by a factor of 1 /sin ^ 2 0 - 5 0 ) r e d u c i n g
the resolution in t h e direction parallel t o t h e b e a m b u t
o n g o o d , flat surfaces this is n o t usually a p r o b l e m
since the defects of interest a r e often well s e p a r a t e d .
Second, only a thin strip of t h e i m a g e is in focus b u t ,
again, this is often n o t a m a j o r p r o b l e m for n e a r
perfect surfaces w h e r e the R H E E D p a t t e r n is c o m
p o s e d of s h a r p s p o t s . T h e d e p t h of field is d e p e n d e n t
o n the a n g u l a r s p r e a d of the electrons being i m a g e d .
If t h e diffraction s p o t is very s h a r p t h e n large a r e a s of
t h e surface c a n b e i m a g e d . F o r r o u g h o r a m o r p h o u s
surfaces t h e s p r e a d of electrons is defined b y t h e
objective a p e r t u r e a n d usually very little i n f o r m a t i o n
c a n be gained a b o u t t h e s a m p l e .
Defects o n a surface a r e m a d e visible because of t h e
presence of diffraction a n d p h a s e c o n t r a s t (see Fig. 2).
410

C h a n g e s of t h e diffraction c o n d i t i o n across t h e s a m
ple will result in c h a n g e s of intensity across t h e i m a g e .
F o r a specimen o r i e n t e d t o t h e B r a g g c o n d i t i o n t h e
d i s t o r t i o n of a t o m i c p l a n e s a r o u n d a defect will
a p p e a r d a r k in t h e i m a g e . T h i s d i s t o r t i o n is d u e t o t h e
strain field a r o u n d t h e e m e r g e n c e of a screw disloca
tion o r a l o n g a step. T h e c o n t r a s t from a screw
dislocation in a s a m p l e t h a t is n o t exactly a t t h e B r a g g
c o n d i t i o n c a n be w o r k e d o u t in a similar w a y , with
o n e of t h e wings a r o u n d t h e d i s l o c a t i o n being closer
t o t h e B r a g g c o n d i t i o n a n d therefore b r i g h t e r a n d the
o t h e r being further from t h e B r a g g c o n d i t i o n a n d
consequently darker. These arguments are based on
t h e c o l u m n a p p r o x i m a t i o n , w h e r e t h e intensity of a n y
region is c o n s i d e r e d t o be e q u a l t o t h a t from a perfect
surface w h o s e o r i e n t a t i o n is t h e s a m e as t h e region
u n d e r c o n s i d e r a t i o n . T h i s intensity i n f o r m a t i o n c a n
b e o b t a i n e d from a r o c k i n g c u r v e calculated for a
perfect crystal a n d , in general, t h e full w i d t h s a t half
m a x i m u m of t h e B r a g g p e a k s a r e in t h e r a n g e 1 0 ~ 3 1 0 " 4 r a d so t h a t surface d i s t o r t i o n s as small as
1 0 " 4 r a d c a n b e detected. Diffraction c o n t r a s t c a n also
s h o w d o m a i n s of surface r e c o n s t r u c t i o n o r a d s o r p
tion in cases w h e r e t h e different d o m a i n s c o n t r i b u t e
different intensities t o certain diffraction s p o t s .
M o s t of a n R E M i m a g e is o u t of focus a n d so
electrons, h a v i n g different optical p a t h lengths d u e t o
d i s t o r t i o n s a r o u n d defects, c a n interfere c o n s t r u c
tively o r destructively giving rise t o d a r k - b r i g h t
fringes a r o u n d steps a n d screw dislocations a n d this
p h a s e c o n t r a s t is often d o m i n a n t in R E M i m a g e s . If
t w o diffraction s p o t s t h a t a r e parallel t o t h e edge of
t h e s a m p l e a r e allowed t h r o u g h t h e objective a p e r t u r e
they c a n interfere t o give lattice fringes t h a t a r e useful

Figure 2
Monatomic steps terminate at the points where screw
dislocations emerge at the surface. At A the dislocation is
in focus and at the Bragg condition, at the dislocation is
slightly off the Bragg condition and at C the black-white
fringe is due to phase contrast from an out-of-focus
dislocation

Reflection

for detecting defects such a s o u t - o f - p h a s e b o u n d a r i e s

o n r e c o n s t r u c t e d surfaces.
A l t h o u g h t h e e x p l a n a t i o n s of c o n t r a s t m e n t i o n e d
a b o v e a r e very useful a n d easy t o u n d e r s t a n d they d o
n o t fully t a k e i n t o a c c o u n t t h e i n t e r a c t i o n of t h e
electrons with t h e s a m p l e . I n reality t h e electrons c a n
travel c o n s i d e r a b l e distances in t h e crystal a n d , for a
c o m p l e t e description of t h e c o n t r a s t , d y n a m i c a l dif
fraction c a l c u l a t i o n s need t o b e e m p l o y e d . T h e elec
t r o n s c a n lose energy b y t h e c r e a t i o n of p l a s m o n s ,
p h o n o n s a n d inner shell excitations so inelastic scat
tering m u s t also b e c o n s i d e r e d .

2.

Observations

O n e of t h e first uses of R E M w a s t o s t u d y t h e p h a s e
c h a n g e o n a silicon (111) surface from 1 1 t o 7 x 7.
H e r e it w a s noticed t h a t n u c l e a t i o n o c c u r s preferen
tially o n t h e t o p side of t h e steps. W h e n gold is
deposited o n t h e silicon (111) 7 x 7 s t r u c t u r e t h e
nucleation of t h e a d s o r b a t e s t r u c t u r e occurs o n t h e
t o p of t h e steps b u t w h e n gold is d e p o s i t e d o n a
p l a t i n u m (111) m o n o l a y e r islands of gold nucleate a t
t h e b o t t o m o f t h e steps. I n t h e l a t t e r case t h e g r o w t h
r a t e d e p e n d s o n t h e w i d t h of t h e lower terraces
indicating t h a t t h e a d a t o m s d o n o t "fall d o w n " t h e
steps. Results like these o b t a i n e d b y R E M s h o w
clearly t h a t w h e n t h e t e r r a c e w i d t h is n a r r o w e r t h a n
the diffusion distance t h e surface d y n a m i c processes
are c o n t r o l l e d b y t h e steps. T h e s e facts s h o u l d b e
b o r n e in m i n d b y all surface scientists since even a
sample c u t t o within | of a low-index p l a n e will h a v e
steps a p p r o x i m a t e l y every 25 n m a n d this is w i t h o u t
allowing for small u n d u l a t i o n s t h a t o c c u r d u r i n g
preparation!
T h e c o n t r o l l e d o x i d a t i o n of surfaces is a n o t h e r a r e a
of research t h a t c a n b e e x a m i n e d b y R E M very
effectively. W h e n a silicon (111) 7 x 7 surface is
oxidized a t 920 it is n o t e d t h a t t h e steps m o v e b a c k
a n d between t h e steps small h o l l o w s a p p e a r . T h e s e
topographic changes are caused by the formation a n d
diffusion of vacancies. T h e vacancies a r e c r e a t e d b y
the s u b l i m a t i o n of SiO. (Similar l o o k i n g h o l l o w s h a v e
also been o b s e r v e d o n n o b l e m e t a l surfaces t h a t h a v e
been p r e p a r e d b y h i g h - t e m p e r a t u r e a n n e a l i n g . )
T h e n u c l e a t i o n a n d g r o w t h of t h r e e - d i m e n s i o n a l
islands o f C u 2 0 o n c o p p e r is also affected b y t h e
presence of steps a n d , conversely, t h e presence of
these islands c a n affect t h e m o v e m e n t of t h e steps.

3. Scanning

REM and Surface

Analyses

R E M c a n also b e p e r f o r m e d using a s c a n n i n g t r a n s
mission electron m i c r o s c o p e ( S T E M ) a n d d u e t o t h e
reciprocity t h e o r e m similar surface i m a g e s a r e
o b t a i n e d (see Electron Microscopy,
Analytical).
The
d i s a d v a n t a g e o f S T E M is t h e l o w e r signal s o t h a t
larger a p e r t u r e s a r e r e q u i r e d . L a r g e r a p e r t u r e s t e n d t o

Electron

Microscopy

decrease t h e d e p t h of field b u t it is possible t o c o m

p e n s a t e for this b y adjusting t h e focus electronically
d u r i n g e a c h scan. T h i s d y n a m i c focusing is especially
useful for i m a g i n g r o u g h o r a m o r p h o u s surfaces since
t h e criterion t h a t s h a r p diffraction s p o t s a r e required
to give a useful d e p t h of focus is n o w unnecessary.
T h e s c a n n i n g f o r m of i m a g i n g also allows t h e fore
s h o r t e n i n g t o b e r e d u c e d b y adjusting t h e s h a p e of t h e
raster o n t h e specimen. It is also possible t o s t o p t h e
p r o b e o n a n y feature of interest o n t h e surface a n d use
t h e v a r i o u s analytical facilities of t h e S T E M t o invest
igate small i n h o m o g e n e i t i e s . T h e s e facilities include
microdiffraction, A u g e r electron s p e c t r o s c o p y (see
Auger Electron Spectroscopy)
a n d electron energy-loss
s p e c t r o s c o p y (see Electron Microscopy,
Analytical).
F o r e x a m p l e , small particles d e p o s i t e d o n surfaces
c a n be c h a r a c t e r i z e d b y their c r y s t a l l o g r a p h y , c h e m
ical c o m p o s i t i o n a n d electronic p r o p e r t i e s .

4. Future

Developments

R E M h a s d e m o n s t r a t e d its p o t e n t i a l a s a tool for

elucidating surface s t r u c t u r e a n d t h e m e c h a n i s m s of
surface r e a c t i o n s . A l t h o u g h it d o e s n o t possess t h e
spatial r e s o l u t i o n of s c a n n i n g tunnelling m i c r o s c o p y
(see Scanning Tunnelling Microscopy
and Spectros
copy) it is in m a n y w a y s a m o r e flexible w a y of
o b s e r v i n g surface c h a n g e s a n d in several l a b o r a t o r i e s
t h e r e a r e p l a n s for b u i l d i n g a tunnelling m i c r o s c o p e
inside a n electron m i c r o s c o p e so t h a t features of
interest o b s e r v e d b y R E M c a n b e e x a m i n e d in m o r e
detail with t h e S T M . M a n y R E M studies h a v e used
s a m p l e s t h a t a r e easily p r e p a r e d (e.g., faceted gold
a n d p l a t i n u m crystals o r cleaved s e m i c o n d u c t o r s ) b u t
in future s a m p l e s of g r e a t e r c o m m e r c i a l a n d a c a d e m i c
interest s h o u l d b e e x a m i n e d . T h i s requires d e d i c a t e d
u l t r a h i g h v a c u u m m i c r o s c o p e s with better cleaning
facilities t h a t will allow t h e p r e p a r a t i o n of m o r e
reactive m a t e r i a l s . T h e ability t o p e r f o r m in situ
r e a c t i o n s will, in general, require a r e a c t i o n cell t o b e
built a r o u n d t h e specimen p o s i t i o n . W i t h these d e
v e l o p m e n t s it will be possible t o p i n p o i n t t h e effects
t h a t surface i n h o m o g e n e i t i e s h a v e o n m a n y i m p o r t a n t
surface r e a c t i o n s .
A l t h o u g h t h e m a i n i m a g e features c a n n o w b e
i n t e r p r e t e d , further w o r k is still r e q u i r e d t o give a
c o m p l e t e theoretical d e s c r i p t i o n of t h e m o r e subtle
i m a g e details. D u e t o t h e c o m p l e x e l e c t r o n - s p e c i m e n
i n t e r a c t i o n this is n o t a trivial p r o b l e m b u t g o o d
p r o g r e s s h a s been m a d e .
See also: Scanning Tunnelling Microscopy and Spectros
copy

Bibliography
Cowley J 1986 Electron microscopy of surface structure.
Prog. Surf. Sci. 21: 209-50

411

Reflection

Electron

Microscopy

Dobson J, Larsen (eds.) 1988 Reflection High Energy

Electron Diffraction and Reflection Electron Imaging of
Surfaces. Plenum, New York
Halliday J S 1965 Reflection electron microscopy. In: Kay D
(ed.) 1965 Techniques for Electron Microscopy, 2nd
edn. Blackwell, Oxford
Smith D J 1986 High resolution electron microscopy in
surface science. In: Vanselow R, Howe R (eds.) 1986
Chemistry and Physics of Solid Surfaces VI. Springer,
Berlin, pp. 413-34
Yagi 1987 Reflection electron microscopy. J. Appl. Crys
tallogr. 20: 147-60
R. H . M i l n e
[University of S t r a t h c l y d e ,
Glasgow, U K ]

Monochromator

Figure 1
The principles of strain measurement, showing the
definition of gauge volume sampled and the direction of
strain measured

Residual Stresses: Measurement Using

Neutron Diffraction
T h e detailed m e a s u r e m e n t of residual stress fields
within c o m p o n e n t s a n d w e l d m e n t s , which are f o r m e d
by i n h o m o g e n e o u s plastic d e f o r m a t i o n or h e a t treat
m e n t such as welding, h a s been a challenge set b y
engineers for m a n y years (see Residual Stresses: Non
destructive Evaluation). M a c r o s t r e s s o r type I stress,
which varies over distances which a r e relatively large
c o m p a r e d with the grain size, is of p r i m e c o n c e r n t o
the engineer. H o w e v e r , microstress o r type II stress,
which varies o n a spatial scale of t h e o r d e r of t h e grain
size, c a n also give i n f o r m a t i o n relevant t o t h e m e c h a
nical b e h a v i o r of m a n y m a t e r i a l s .
T h e n e u t r o n diffraction m e t h o d of stress m e a s u r e
m e n t ( H u t c h i n g s a n d K r a w i t z 1992) closely parallels
a n d c o m p l e m e n t s the x-ray diffraction
method
( N o y a n a n d C o h e n 1987). H o w e v e r , it enables ind e p t h m e a s u r e m e n t s t o be m a d e o n a c c o u n t of the
2
4
m u c h deeper p e n e t r a t i o n , by a factor of 1 0 - 1 0 , of
the n e u t r o n i n t o m o s t m a t e r i a l s . I n c o n t r a s t , the x-ray
m e t h o d examines near-surface stress fields t o a m a x i
m u m d e p t h of ~ 100 . A b s o l u t e m a c r o s t r e s s ten
sors, m a c r o s t r e s s g r a d i e n t s , stresses d u e t o applied
l o a d i n g a n d microstress c a n be m e a s u r e d i n - d e p t h
uniquely, using n e u t r o n diffraction. T h e t e c h n i q u e
was first developed in 1980, parallel w o r k being
carried o u t in the U K (Allen et al. 1981), in G e r m a n y
(Pintschovius et al. 1982) a n d in the U S A ( K r a w i t z et
al. 1982). It is n o w used with confidence w o r l d w i d e as
a n o n d e s t r u c t i v e t e c h n i q u e , p r o v i d i n g new i n f o r m a
tion for the engineer in a n increasing n u m b e r of
a p p l i c a t i o n s . T h e m a j o r d r a w b a c k of the n e u t r o n
diffraction m e t h o d is its need for intense n e u t r o n
b e a m s , available only a t a m e d i u m - o r high-flux
r e a c t o r o r at a n a c c e l e r a t o r - b a s e d , usually timepulsed, n e u t r o n source. T h i s limits its use t o relatively
small p o r t a b l e c o m p o n e n t s , with typical m a x i m u m
d i m e n s i o n of a r o u n d 5 0 - 1 0 0 c m . H o w e v e r , it c a n also

412

be used to test c o m p u t e r c o d e s using m o d e l s a m p l e s ,

t o test a s s u m p t i o n s m a d e in t h e use of p o r t a b l e , b u t
usually m u c h m o r e limited, t e c h n i q u e s a n d t o cali
b r a t e these t e c h n i q u e s for use in t h e factory o r field.
T h e e x p l o r a t i o n of the finer p o i n t s of the n e u t r o n
diffraction t e c h n i q u e is p r o v i d i n g m a t e r i a l s scientists
with n e w insights i n t o t h e f u n d a m e n t a l b e h a v i o r of
m a t e r i a l s u n d e r stress.

1.

Principles

T h e basic principle of the n e u t r o n diffraction m e t h o d

lies in the use of t h e lattice p l a n e spacing of grains t o
act as a n internal strain g a u g e t h r o u g h o u t the c o m
p o n e n t . Full details a r e given b y Allen et al. (1985).
T h e m e t h o d is illustrated in Fig. 1 a n d is first dis
cussed here in t e r m s of a r e a c t o r - b a s e d i n s t r u m e n t ,
w h e r e modified s t a n d a r d h i g h - r e s o l u t i o n p o w d e r n e u
t r o n diffractometers a r e often q u i t e suitable.
T h e w h i t e n e u t r o n b e a m from t h e r e a c t o r is first
m o n o c h r o m a t e d to a chosen wavelength by Bragg
reflection from a large single-crystal m o n o c h r o m a t o r .
T h i s m o n o c h r o m a t e d b e a m is defined in direction b y
a soller slit c o l l i m a t o r , o r b y a p e r t u r e s , t o p a s s over
the "sample axis" a b o u t which the detector rotates.
T h e d e t e c t o r c o u n t s n e u t r o n s scattered t h r o u g h a n
angle , with t h e scattered b e a m a g a i n defined in
direction by a soller slit assembly. B o t h t h e b e a m
incident o n t h e s a m p l e a n d t h e b e a m entering t h e
d e t e c t o r are defined in a r e a by h o r i z o n t a l a n d vertical
a p e r t u r e s in a n e u t r o n a b s o r b i n g m a s k , m a d e of
c a d m i u m for e x a m p l e . T h e " g a u g e v o l u m e " o r
" v o l u m e s a m p l e d " by t h e diffractometer is defined b y
t h e intersection of t h e incident a n d scattered b e a m s ,
as s h o w n in Fig. 1. A s a m p l e placed wholly within this
v o l u m e will h a v e its a v e r a g e p r o p e r t y m e a s u r e d ,

Residual

w h e r e a s a large s a m p l e m a y b e m o v e d t h r o u g h t h e
gauge v o l u m e in o r d e r t o o b t a i n a profile o f a
p r o p e r t y such a s strain.
Polycrystalline m a t e r i a l s give rise t o c o n e s of dif
fracted n e u t r o n s a t angles q>hkl = 26hkl a b o u t t h e inci
d e n t b e a m o n t h e s a m p l e . T h e s e angles a r e given b y
Bragg's law:
2 ^ / S i n ^

(1)

w h e r e dm is t h e lattice s p a c i n g of p l a n e s w i t h Miller
indices hkl. T h e c o n e of scattering arises from t h e
subset of crystallites o r g r a i n s in t h e s a m p l e w h i c h
satisfy B r a g g ' s l a w a n d w h i c h a r e o r i e n t e d s o t h a t t h e
planes a r e a t a n angle t o t h e incident b e a m . I t is
usual t o define a scattering v e c t o r Q = k{ - k(, w h e r e
k{ a n d k{ a r e t h e incident a n d scattered n e u t r o n w a v e
vector of m a g n i t u d e \k\ = 2/, a s s h o w n in F i g . 1.
F o r B r a g g reflection, Q is n o r m a l t o t h e p l a n e s giving
the diffracted b e a m a n d of m a g n i t u d e e q u a l t o t h a t of
the reciprocal lattice vector r of t h e p l a n e s : \Q\ = \rhkl\
(Kittel 1986).
T h e d e t e c t o r is s c a n n e d t h r o u g h <phkl t o d e t e r m i n e
the p e a k - c o u n t angle w h i c h , in t h e case of a large
sample, c o r r e s p o n d s t o t h e a v e r a g e dm of t h e g r a i n s in
the g a u g e v o l u m e s a m p l e d . U s u a l l y a fitting r o u t i n e
using least-squares m i n i m i z a t i o n is used t o d e t e r m i n e
the angle a n d a n g u l a r w i d t h of t h e p e a k . T h e a v e r a g e
lattice m a c r o s t r a i n in t h e v o l u m e s a m p l e d is t h e n
given b y
e

hki

(dhkl

dohjcl)/dohkl

= - (cot eohkl)(q>hkl_

(p0hkl)/2

(2)

w h e r e d0hkl is t h e lattice s p a c i n g of a "stress-free"

sample of t h e s a m e m a t e r i a l c o m p o s i t i o n a n d
(pQhkl = 260hkl is t h e c o r r e s p o n d i n g diffraction angle.
T h e direction in w h i c h t h e strain e m is m e a s u r e d is
t h a t of t h e scattering v e c t o r Q. T h e m e a n lattice
m i c r o s t r a i n in t h e v o l u m e s a m p l e d is related t o t h e
angular peak width, although there m a y be other
contributions.
A s t h e lattice s p a c i n g c a n only c h a n g e elastically, it
is a n elastic strain w h i c h is always m e a s u r e d , b u t this
m a y b e a result of i n t e r g r a n u l a r strains arising from a
plastic d e f o r m a t i o n o r t h e r m a l t r e a t m e n t of t h e s a m
ple. If a n a c c u r a t e value of d0, o r 09 c a n b e m e a s u r e d ,
the strain d e t e r m i n e d is a b s o l u t e . H o w e v e r , o b t a i n i n g
a true 0 m a y p r o v e difficult in practice. A small
a n n e a l e d s a m p l e with m e a s u r e m e n t s m a d e in several
orientations a n d averaged, or a n extreme part of a
c o m p o n e n t , m a y b e t a k e n t o b e in z e r o strain. Alter
natively, a s u m rule o r b o u n d a r y c o n d i t i o n s , after
conversion t o e q u i v a l e n t stress, m a y b e used.
In o r d e r t o d e t e r m i n e t h e strain in different direc
tions in t h e s a m p l e , t h e s a m p l e m u s t b e r o t a t e d
accurately a b o u t t h e c e n t r e of t h e g a u g e v o l u m e s o
t h a t each direction lies a l o n g Q. T h i s is often q u i t e
difficult t o d o in practice a n d requires very careful
a l i g n m e n t a n d centering of t h e s a m p l e . L a r g e s a m p l e s

Stresses:

Measurement

Using Neutron

Diffraction

m a y hit t h e s p e c t r o m e t e r h a r d w a r e , o r p a t h lengths of
t h e b e a m in t h e s a m p l e m a y b e c o m e excessive, p r e
venting some orientations. It should be noted that the
v o l u m e s a m p l e d is i n d e p e n d e n t of t h e vertical height
of t h e a p e r t u r e in t h e scattered b e a m , so in o r d e r t o
increase intensity this c a n b e m a d e a s large a s possible
consistent w i t h t h e r e q u i r e d definition in t h e direction
of e. A vertical d e t e c t o r c a n b e used with a d v a n t a g e .
A t = 90 t h e c o n e b e c o m e s a p l a n e of scattering a n d
this is also t h e o p t i m u m scattering angle for definition
of t h e g a u g e v o l u m e . A l t h o u g h t h e r e s o l u t i o n in strain
increases with a n d is best a t ~ 180, using <p~90
scattering a t b o t h m o n o c h r o m a t o r a n d s a m p l e is
often a g o o d c o m p r o m i s e . H o w e v e r , a n angle of
90 m a y h a v e t h e a d v a n t a g e t h a t it c a n p r o v i d e
m o r e r e a d y access t o t h e p o i n t in t h e s a m p l e a t which
t h e strain is t o b e m e a s u r e d . T h e g a u g e v o l u m e s h a p e
a n d size m u s t b e c h o s e n w i t h d u e c o n s i d e r a t i o n t o
t h e direction a n d m a g n i t u d e o f t h e strain g r a d i e n t ,
t h e intensity of scattering a n d c o n s e q u e n t m e a s u r e
m e n t time, a n d t h e size o f t h e grains in t h e s a m p l e .
3
Typically, g a u g e v o l u m e s a r e b e t w e e n 1 m m a n d
3
27 m m .
T h e u s e o f a h o r i z o n t a l position-sensitive d e t e c t o r
( P S D ) c a n speed u p d a t a collection b y effectively
p e r f o r m i n g t h e scan of a t o n e setting. H o w e v e r , t h e
definition of t h e g a u g e v o l u m e b e c o m e s difficult a s
m a s k s m u s t b e placed very close t o t h e s a m p l e a n d
these m a y p r e v e n t r o t a t i o n o f t h e s a m p l e t o give
s t r a i n s in different d i r e c t i o n s . I t s h o u l d b e n o t e d t h a t ,
in c o n t r a s t with n o r m a l p o w d e r diffraction, higher
w a v e l e n g t h o r d e r s (A/2, A/3, etc.) from t h e m o n o c h r o
m a t o r c a n often b e u s e d w i t h a d v a n t a g e in strain
m e a s u r e m e n t . I n o r d e r t o o b t a i n diffraction angles of
0
0?~9O , n e u t r o n w a v e l e n g t h s in t h e region A = 0 . 1 5 0.25 n m m u s t usually b e used.
A n a l t e r n a t i v e t o a s t e a d y r e a c t o r s o u r c e of n e u
t r o n s is t h e p u l s e d w h i t e b e a m o f n e u t r o n s given b y a
s p a l l a t i o n s o u r c e . I n this case polycrystalline diffrac
tion is o b s e r v e d a t a fixed . O n m o s t s t a n d a r d
p o w d e r diffraction i n s t r u m e n t s is usually a r o u n d
150 t o 180 t o give very g o o d r e s o l u t i o n a n d t i m e
of flight t is used t o scan t h e different lattice p l a n e s .
T h e strain is n o w given b y e = At/t = /, w h e r e t =
L/v = (hrn\K)L is time t a k e n for a n e u t r o n with m a s s m
a n d velocity t o travel a p a t h length L , a n d h is
P l a n c k ' s c o n s t a n t . T h e a d v a n t a g e of this m e t h o d is
t h a t strains m a y b e m e a s u r e d from m a n y lattice
p l a n e s {hkl} a t o n c e . H o w e v e r , Q is nearly a l o n g k{ in
t h e b a c k - s c a t t e r i n g a r r a n g e m e n t . A s for t h e r e a c t o r
i n s t r u m e n t , c o u n t e r s a t 90 m u s t b e used t o give
m e a s u r e m e n t of t h e full strain t e n s o r a n d such instru
m e n t s a r e u n d e r d e v e l o p m e n t . T h e p o s i t i o n i n g of t h e
s a m p l e is even m o r e critical h e r e a s it m a y affect L a n d
h e n c e t.
I n m o s t cases, t h e strain a n d stress a r e triaxial a n d
c a n b e r e p r e s e n t e d b y a strain t e n s o r a n d a stress
t e n s o r . If o n e defines axes Oxyz within t h e s a m p l e
a n d a t a p o i n t with respect t o these axes, t h e n t h e

413

Residual

Stresses:

Measurement

Using Neutron

Diffraction

strain m e a s u r e d in a direction specified by direction

cosines (I'm') relative t o Oxyz is given by
e(l'm'n')

= l'\x

+ m'hyy

+ 2m'n'eyz

+ n'\

2\'m'exy

+ 2'

(3)

A t least six m e a s u r e m e n t s of e(l'm'n') a r e therefore

necessary t o d e t e r m i n e t h e six t e r m s in , b u t clearly
the accuracy c a n be i m p r o v e d if m o r e a r e m a d e . T h e
simplest directions are t h o s e a l o n g a n d a t 45 t o the
axes Oxyz. H a v i n g d e t e r m i n e d , the principal strain

axes OXYZ a n d t h e principal strains a l o n g t h e m

m a y be f o u n d b y d i a g o n a l i z a t i o n . T h e principal inter
nal stresses a l o n g these axes a r e t h e n related, a s s u m
ing a n elastically i s o t r o p i c m o d e l with m a c r o s c o p i c
Y o u n g ' s m o d u l u s a n d P o i s s o n ' s r a t i o v, b y
<f> = [E/(\

+ v ) ] # + {vE/[(\

+ * ? r + zz)>

- 2v)(l + v)]}(er

i = *,Y,Z

(4)

P l a n e strain o r p l a n e stress a r e special cases of these

general expressions. Typically, for steel a shift in
from t h a t of a stress-free s a m p l e of 0.0 a t 90
indicates a strain of a p p r o x i m a t e l y 100 o r a stress
a b o u t 20 M P a . A c c u r a c y in m e a s u r e m e n t of 0.005 is
usually easily o b t a i n e d by p e a k profile fitting using a
c o m p u t e r . Practical p a t h lengths, t h a t is lengths of t h e
total incident p l u s diffracted b e a m s , in steel a n d in
a l u m i n u m a r e typically 50 m m a n d 100 m m , respect
3
ively, for v o l u m e s s a m p l e d of 27 m m . T h i s m e a n s
t h a t it is possible t o m e a s u r e t o a d e p t h of a r o u n d
2.5 c m i n t o steel from a flat surface. L o n g e r p a t h s in
the m a t e r i a l , for d e e p e r p e n e t r a t i o n , c a n be realized
by s a m p l i n g larger v o l u m e s . H o w e v e r , these m a y
b e c o m e unevenly illuminated by t h e n e u t r o n b e a m
because of scattering a n d a b s o r p t i o n . I n principle, all
crystalline m a t e r i a l s c a n be e x a m i n e d , b u t s o m e
materials, such as nickel, scatter n e u t r o n s incoher
ently a n d o t h e r s , such as t i t a n i u m alloy, h a v e small
B r a g g intensities m a k i n g m e a s u r e m e n t s a t d e p t h cor
respondingly m o r e difficult.
In m o s t m a t e r i a l s , t h e values of a n d in E q n . (4)
are d e p e n d e n t o n t h e lattice p l a n e s (hkl) used as t h e
" s t r a i n g a u g e , " since t h e elastic r e s p o n s e of e a c h g r a i n
to a n applied stress is a n i s o t r o p i c . I n d e e d , it is neces
sary to d e t e r m i n e t h e " n e u t r o n elastic c o n s t a n t s " b y
c a l i b r a t i o n using, for e x a m p l e , a c o m p a c t stress rig
which c a n be a c c o m m o d a t e d o n a n e u t r o n diffracto m e t e r (Allen et al. 1989). S u c h a rig allows a k n o w n
uniaxial stress t o be applied in tension o r c o m p r e s s i o n
t o a s a m p l e of m a t e r i a l a n d allows t h e strain t o b e
m e a s u r e d either a l o n g the direction of stress o r per
p e n d i c u l a r t o it. T h e intensity of t h e reflection, related
to its multiplicity a n d t h e effects of a n y t e x t u r e
present, h a s also t o be c o n s i d e r e d w h e n m a k i n g a
choice of hkl.
F o r a single crystal the effective elastic m o d u l u s c a n
readily be calculated a n d , for e x a m p l e , is f o u n d t o
vary by over a factor of t w o b e t w e e n reflections in
ferritic steel (see Residual Stresses:
Nondestructive
414

Evaluation), s h o w i n g t h a t t h e inclusion of t h e effects

of elastic a n i s o t r o p y is of p a r a m o u n t i m p o r t a n c e in
i n t e r p r e t i n g n e u t r o n diffraction stress d a t a . T h e cal
c u l a t i o n of t h e r e s p o n s e of polycrystalline m a t e r i a l t o
a n a p p l i e d uniaxial stress is n o t s t r a i g h t f o r w a r d a n d
a s s u m p t i o n s as t o c o n t i n u i t y a t grain b o u n d a r i e s
m u s t be m a d e t o simplify t h e p r o c e d u r e . T h e t w o
simplest a p p r o x i m a t i o n s give e x t r e m e b o u n d s to the
a c t u a l r e s p o n s e . T h e s e a r e t h e Voigt a n d R e u s s
m o d e l s , in w h i c h strain a n d stress a r e , respectively,
a s s u m e d c o n t i n u o u s across grain b o u n d a r i e s . A m o r e
realistic m o d e l is given by K r o n e r (Sayers 1984, Allen
et al. 1985), which a p p r o x i m a t e s t o t h e m e a n of t h e
Voigt a n d R e u s s b o u n d s (Allen et al. 1989). If stresses
b e y o n d t h e yield p o i n t a r e applied, slip will t e n d t o
o c c u r in t h e grains b u t will be c o n s t r a i n e d by their
s u r r o u n d i n g s . T h e t h e o r y for such effects is n o t yet
fully d e v e l o p e d (Leffers 1981). Results o b t a i n e d from
m e a s u r e m e n t s using stress rigs s h o u l d p r o v i d e key
d a t a for a b e t t e r u n d e r s t a n d i n g of plastic strain a t the
grain i n t e r a c t i o n level. M e a s u r e m e n t s s h o w t h a t t h e
use of the 211 B r a g g reflection is a g o o d practical
choice for steels.
2. Examples

of Strain

and Stress

Field

Measurement
A selection of examples of measurements is briefly given
to illustrate the range of application of the technique.
Full details can be found in the references given.
2.1 Stress in

Weldments

O n e of t h e key uses of t h e n e u t r o n diffraction m e t h o d

of stress m e a s u r e m e n t h a s been t o investigate i n - d e p t h
stresses in a n d a r o u n d t h e weld in a variety of
w e l d m e n t s . T h e s e m e a s u r e m e n t s c a n actually test t h e
a s s u m p t i o n s a n d theories w h i c h h a d h i t h e r t o been
used t o e s t i m a t e t h e stress levels. A n e x a m p l e is t h e
m e a s u r e m e n t of t h e effectiveness of p o s t w e l d h e a t
t r e a t m e n t o n a T - b u t t w e l d m e n t , s h o w n in t h e inset in
Fig. 2, m a d e from 5 0 D steel used in " o f f s h o r e "
a p p l i c a t i o n s (Allen et al. 1988). T h e strain w a s
m e a s u r e d a t a n d below t h e t o e of t h e weld in t h e
center p o s i t i o n before a n d after a p o s t w e l d h e a t
t r e a t m e n t typical of t h a t given t o offshore s t r u c t u r e s .
T h e results a r e s h o w n in F i g . 2, w h e r e it is seen t h a t
t h e strain is essentially r e d u c e d t o zero level by t h e
t r e a t m e n t . T h i s e x a m p l e illustrates t h e use of this
nondestructive technique to examine the same sample
before a n d after processing.
2.2 Residual

Stress in Railroad

Rails

R a i l r o a d rails c o n t a i n residual stresses d u e t o fabrica

tion processes w h i c h a r e modified in use b y the
p a s s a g e of t r a i n s . Such stresses c a n c o n t r i b u t e t o , o r
inhibit, failure in service. A n extensive s t u d y of the
stresses in n e w a n d used rails h a s been m a d e b y
W e b s t e r et al. (1990). T h e y investigated 10 m m thick
sections c u t transverse a n d longitudinally, a n d used a

Residual

Stresses:

Measurement

Using Neutron

Diffraction

after PWHT

-5

-10

-15

-20

Depth f r o m t o e , z ( m m )

Figure 2
Variation of strain ex through the plate beneath the toe of
the weld in a T-butt weldment (inset) before and after
postweld heat treatment (PWHT). The direction of strain
measured is perpendicular to the weld line (after Allen et
al. 1988) (the arrow indicates zero-strain angle)
P S D for r a p i d d a t a collection. A n e x a m p l e of t h e
detailed p a t t e r n of t h e t r a n s v e r s e c o m p o n e n t of resi
d u a l stress f o u n d a c r o s s t h e h e a d of a used rail is
s h o w n in Fig. 3. T h e a s s y m e t r y in t h e p a t t e r n arises
from the fact t h a t t h e r u n n i n g line of wheel c o n t a c t is
offset by + 6 m m from t h e rail c e n t r e .
2.3 Stress During Fatigue Cycling of a Compact
Tension Specimen
T h e m a x i m u m triaxial stress levels a l o n g t h e line of
c r a c k i n g of a small (31.5 m m 49.6 m m 13.1 m m )
c o m p a c t tension specimen of BS 4360 steel h a v e b e e n
m e a s u r e d b y b o l t i n g t h e specimen a t t h e p e a k stress
level ( H u t c h i n g s et al. 1990). T h e specimen h a d b e e n
subjected t o 20 000 cycles of fatigue l o a d i n g , w i t h
a stress intensity level v a r y i n g b e t w e e n a m i n i m u m
of
= 3 M P a ram"2 a n d
a
maximum
of
K= 34 M P a m m 1 / 2, in o r d e r t o p r o d u c e a small c r a c k
of 3.6 m m in length. T h e d a t a w e r e t a k e n with a g a u g e
v o l u m e of 1 m m 3 a n d a r e s h o w n in Fig. 4. T h e stress
field w a s f o u n d t o be n e i t h e r p l a n e strain n o r p l a n e

Figure 3
Transverse residual stress contour levels found from a
series of scans of the gauge volume across the head of a
section of used railroad rail (after Webster et al. 1990)

15

20

25

Distance f r o m s a m p l e c e n t e r ,

(mm)

Figure 4
Triaxial stress variation with position JC (y = = 0) in a
cracked fatigue test specimen bolted in the maximum
crack-tip stress configuration. The arrow denotes the
position of the crack tip on the specimen center line and
the shaded line the outer edge of the specimen (after
Hutchings et al. 1990)
stress, states often a s s u m e d in theoretical calculations,
a n d t h e p e a k stress levels were spatially b r o a d e r a n d
smaller in m a g n i t u d e t h a n expected from t h e o r y
a s s u m i n g p l a n e strain. I n s t r u m e n t a l g a u g e v o l u m e
r e s o l u t i o n c o u l d h a v e c o n t r i b u t e d t o this r e d u c t i o n .
O n r e m o v a l of t h e b o l t t o give the m i n i m u m l o a d
s i t u a t i o n , it w a s f o u n d t h a t t h e p e a k level m o v e d a w a y
from t h e c r a c k tip, with c o n s e q u e n c e s for h y d r o g e n o r
sulfur e m b r i t t l e m e n t .
2.4 Residual
Autofrettaged

Stress Distribution
Tubing

in

Cracked

Steel t u b i n g used for a variety of critical high-pressure

a p p l i c a t i o n s is often a u t o f r e t t a g e d t o inhibit c r a c k
initiation a n d fatigue p r o p a g a t i o n from t h e b o r e . T h e
a u t o f r e t t a g e p r o c e s s i n t r o d u c e s c o m p r e s s i v e residual
stresses a t t h e b o r e , b a l a n c e d b y tensile stresses a t
larger radii. T h e residual stress d i s t r i b u t i o n in a ring
s a m p l e of a n a u t o f r e t t a g e d h i g h - s t r e n g t h , low-alloy
steel t u b e of 60 m m b o r e d i a m e t e r a n d 32 m m wall
thickness h a s been m e a s u r e d b y B o u r k e et al. (1992)
u s i n g a g a u g e v o l u m e of 2 m m 2 m m 2 m m . T h e
t u b e h a d b e e n fatigue c r a c k e d t h r o u g h half t h e wall
thickness i n t o a region w h i c h originally c o n t a i n e d
tensile residual stress. A c o m p a r i s o n of t h e residual
h o o p stresses a l o n g t h e c r a c k with t h o s e a l o n g a
r a d i u s in t h e u n c r a c k e d , little affected side of the ring
is s h o w n in Fig. 5. T h e c r a c k is seen t o cause a
r e d i s t r i b u t i o n of stress, with a s u b s t a n t i a l increase in
residual h o o p tension relative t o t h a t m e a s u r e d in the
u n c r a c k e d side, o b s e r v e d a h e a d of the crack.
2.5 Near-Surface
Residual Stresses Caused by
Shot-Peening
S h o t - p e e n i n g is a c o l d - w o r k i n g process in which t h e
415

Residual

Stresses:

Measurement

uncracked

cracked

Using Neutron

Diffraction

Q_
oSiC
alumina

<024>

alumina

<006>

(C)

Radial position ( m m )

Figure 5
Comparison of residual hoop stress along a radius in the
cracked and uncracked sides of an autofrettaged, fatigued
ring. The crack tip is estimated to be at R ^ 15 mm (after
Bourke et al. 1992)
surface is plastically d e f o r m e d by b o m b a r d m e n t with
fine shot. It is used t o p r o d u c e compressive stress a t
the surface layer of c o m p o n e n t s in o r d e r t o inhibit t h e
p r o p a g a t i o n of surface c r a c k s . T h e c o m p o n e n t s of
residual stress as a function of d e p t h b e n e a t h t h e
surface of a heavily p e e n e d block of nickel-based
superalloy h a v e been m e a s u r e d b y Ezeilo et al. (1992)
using a g a u g e v o l u m e of a p p r o x i m a t e d i m e n s i o n
0.5 m m p e r p e n d i c u l a r t o t h e surface. T h e results a r e
s h o w n in Fig. 6. T h e compressive surface stress
rapidly diminishes a n d a significant tensile region is
observed between d e p t h s of 0.6 m m a n d 2 m m . T h e
n a t u r e of this tensile region w a s first revealed b y such
n e u t r o n diffraction m e a s u r e m e n t s .
2.6 Residual Stress in Composite
Materials
T h e stress in each c o m p o n e n t of a c o m p o s i t e m a t e r i a l
c a n be m e a s u r e d separately from its distinct B r a g g

Figure 6
Residual stress components as a function of depth from
the surface of a shot-peened nickel superalloy block. The
and axes lie in the surface plane of the block (after
Ezeilo et al. 1992)
416

Figure 7
Measured (symbols) and predicted (solid line) residual
average hydrostatic strain as a function of temperature for
whiskers and matrix of a ceramic composite of SiC
whiskers in A1 20 3 (after Majumdar et al. 1991)
reflections. In m o s t studies t o d a t e it is the m e a n
microstress levels in t h e c o m p o n e n t s w h i c h h a v e been
m e a s u r e d , b u t t h e profile of stress as a function of
p o s i t i o n c a n also b e d e t e r m i n e d as in single-phase
m a t e r i a l s . A n e x a m p l e of t h e p o w e r of the t e c h n i q u e
is t h e m e a s u r e m e n t of t h e h y d r o s t a t i c strain as a
function of t e m p e r a t u r e for b o t h t h e SiC whisker a n d
t h e a l u m i n a m a t r i x of a c e r a m i c m a t r i x c o m p o s i t e of
1 5 w t % SiC in A 1 2 0 3 ( M a j u m d a r et al. 1991). T h e
results a r e s h o w n in F i g . 7. B o t h t h e relatively large
c o m p r e s s i v e stress in t h e whiskers a n d t h e smaller
tensile stress in t h e A 1 2 0 3 m a t r i x a r e relieved as t h e
c o m p o s i t e is h e a t e d t o w a r d s t h e fabrication t e m p e r a
t u r e . T h e e x t r a p o l a t e d z e r o strain p o i n t is 1400 C,
s o m e 300 C b e l o w t h e fabrication t e m p e r a t u r e , sug
gesting t h a t d u r i n g t h e initial t e m p e r a t u r e d r o p from
1700 C t o 1400 C t h e m a t e r i a l is relaxing by creep
a n d is n o t b u i l d i n g u p residual stress.

3. Future

Developments

N e u t r o n diffraction p r o v i d e s a u n i q u e , n o n d e s t r u c
tive, a n d a b s o l u t e m e t h o d of residual stress m e a s u r e
m e n t a t d e p t h s of u p t o a p p r o x i m a t e l y 2.5 c m in steel
a n d a p p r o x i m a t e l y 7 c m in a l u m i n u m . H o w e v e r , a
high-flux n e u t r o n s o u r c e m u s t b e used p r e c l u d i n g its
use for in situ m e a s u r e m e n t s o n p l a n t a n d s t r u c t u r e s .
It c a n b e used for p o r t a b l e s a m p l e s of less t h a n 1 m
typical size a n d for t h e v a l i d a t i o n a n d c a l i b r a t i o n of
o t h e r t e c h n i q u e s w h i c h c a n be used in t h e field b u t
w h i c h a r e usually limited in a p p l i c a t i o n . U n f o r t u n
ately, p o r t a b l e n e u t r o n sources of sufficient intensity
for general use in t h e field a r e unlikely t o b e c o m e
available in t h e foreseeable future.
T h e n e u t r o n m e t h o d is also b e c o m i n g increasingly
v a l u a b l e in t h e f u n d a m e n t a l m a t e r i a l s science field, in
t h e u n d e r s t a n d i n g of t h e stress d i s t r i b u t i o n in n e w
m a t e r i a l s t o be used b y engineers such as m e t a l m a t r i x
c o m p o s i t e s a n d in s h e d d i n g light o n t h e strain re-

Residual

sponse at t h e individual g r a i n level of m e t a l s stressed

into the plastic regime. T h e next few years will p r o
vide increasing confidence in t h e use of this relatively
new t e c h n i q u e a n d lead t o t h e d e v e l o p m e n t of s t a n
d a r d s of practice t o be used by engineers. T h e tech
n i q u e h a s n o w t a k e n its place w o r l d w i d e alongside t h e
o t h e r m o r e t r a d i t i o n a l m e t h o d s of n o n d e s t r u c t i v e
testing.

cknowledgement

This w o r k w a s c o m p l e t e d while t h e a u t h o r w a s
e m p l o y e d by the U n i t e d K i n g d o m A t o m i c E n e r g y
A u t h o r i t y w h o r e t a i n possession of the c o p y r i g h t of
the article. P u b l i s h e d with p e r m i s s i o n .
See also: Residual Stresses: Nondestructive Evaluation;
Stress Distribution: Analysis Using Thermoelastic Effect

Nondestructive

Evaluation

of Polycrystals: Mechanisms and Microstructures. Riso

National Laboratory, Roskilde, Denmark, pp. 55-71
Majumdar S, Singh J P, Kupperman D, Krawitz A D 1991
Application of neutron diffraction to measure residual
strains in various engineering composite materials.
J. Eng. Mater. Technol. 113: 51-9
Noyan I C, Cohen J 1987 Residual StressMeasured by
Diffraction and Interpretation. Springer, New York
Pintschovius L, Jung V, Macherauch E, Schafer R, Vohringer 1982 Determination of residual stress distribution
in the interior of technical parts by means of neutron
diffraction. In: Kula E, Weiss V (eds.) 1982 Residual
Stress and Stress Relaxation. Plenum, New York, pp.
467-82
Sayers C 1984 The strain distribution in anisotropic
polycrystalline aggregates subjected to an external stress
field. Philos. Mag. A 49: 243-62
Webster J, Low S, Mills G, Webster G A 1990 Neutron
measurement of residual stresses in a used railway rail.
Mater. Res. Soc. Symp. Proc. 166: 311-16
. T. Hutchings
[AEA Industrial Technology,
Didcot, U K ]

Bibliography
Allen A J, Andreani C, Hutchings , Windsor C G 1981
Measurement of internal stress within bulk materials
using neutron diffraction. NDT Int. October 249-54.
Allen A J, Bourke M, David W I F, Dawes S, Hutchings
, Krawitz A D, Windsor C G 1989 Effects of elastic
anisotropy on the lattice strains in polycrystalline metals
and composites measured by neutron diffraction. In: Beck
G, Denis S, Simon A (eds) 1989 Int. Conf. Residual Stress
ICRS2. Elsevier, London, pp. 78-83.
Allen A J, Hutchings , Rainey V S 1988 Measurement
of through-thickness residual stress in T-butt weldments
of offshore steel by high resolution neutron diffraction.
In: Farley J M, Nicols R W (eds.) 1988 Non-Destructive
Testing. Pergamon, Oxford, pp. 1808-17
Allen A J, Hutchings , Windsor C G, Andreani C 1985
Neutron diffraction methods for the study of residual
stress fields. Adv. Phys. 34: 445-73
Bourke M A M , MacGillivray J, Webster G A, Webster J
1992 Residual stress distribution in cracked autofrettaged
tubing. In: Hutchings and Krawitz 1992, pp. 481-92
Ezeilo A N, Webster S, Webster G A, Webster J 1992
Development of the neutron diffraction technique for the
determination of near surface residual stress in critical gas
turbine components. In: Hutchings and Krawitz 1992, pp.
535-43
Hutchings , Hipplsey C, Rainey V 1990 Neutron
diffraction measurement of the stress field during fatigue
cycling of a cracked test specimen. Mater. Res. Soc.
Symp. Proc. 166: 317-21
Hutchings , Krawitz A D (eds.) 1992 Measurement of
Residual and Applied Stress Using Neutron Diffraction.
Kluwer, Dordrecht, The Netherlands
Kittel C 1986 Introduction to Solid State Physics, 6th edn.
Wiley, New York
Krawitz A D, Brune J E, Schmank J 1982 Measurement
of stress in the interior of solids with neutrons. In: Kula E,
Weiss V (eds.) 1982 Residual Stress and Stress Relaxation.
Plenum, New York, pp. 139-55
Leffers 1981 Microstructures and mechanisms of polycrystal deformation at low temperatures. In: Hansen N,
Horsewell A, Leffers T, Lilholt (eds.) 1981 Deformation

Stresses:

Residual Stresses: Nondestructive

Evaluation
R e s i d u a l stresses a r e stresses w h i c h persist in a m a t e r
ial o r a c o m p o n e n t u n d e r u n i f o r m t e m p e r a t u r e in the
a b s e n c e of externally a p p l i e d l o a d s . T h e y a r e created
w h e n e v e r a m e m b e r is p e r m a n e n t l y d e f o r m e d o r
d i s t o r t e d in a n o n u n i f o r m m a n n e r . T h e residual
stresses a r e a m a n i f e s t a t i o n of t h e elastic d e f o r m a
tions t h a t t h e infinitesimal e l e m e n t s of a m e m b e r m u s t
experience in o r d e r for t h e m t o r e m a i n c o m p a t i b l e
(i.e., t o stay fitted t o g e t h e r ) . Tensile residual stresses
a r e generally d e t r i m e n t a l , increasing susceptibility of
a m e m b e r t o fatigue d a m a g e , stress c o r r o s i o n a n d
fracture. C o m p r e s s i v e residual stresses a r e usually
beneficial, t e n d i n g t o r e d u c e these susceptibilities. In
o r d e r t o p r o p e r l y c o n t r o l residual stressessay, by
the tailoring of m a n u f a c t u r i n g a n d c o n s t r u c t i o n p r o
c e s s e s a n d t o p r o p e r l y a c c o u n t for their presence, it
is first necessary t o m e a s u r e t h e m .

1. General

Considerations

If a p o r t i o n of a residually stressed b o d y is cut a w a y

a n d t h e resulting d e f o r m a t i o n of t h e b o d y is carefully
m e a s u r e d , t h e residual stresses which existed a t the
freshly e x p o s e d surfaces, before they were t h u s
e x p o s e d , c a n frequently be calculated. T h i s t e c h n i q u e
is useful, b u t it c a n be extremely t e d i o u s a n d p a i n s t a k
ing, a n d often analytically difficult. A m o r e serious
d i s a d v a n t a g e of t h e dissection t e c h n i q u e is t h a t it is
destructive t o t h e p a r t being analyzed. F o r r e a s o n s of
time a n d cost it is clear t h a t only a few s a m p l e s c a n be

417

Residual

Stresses:

Nondestructive

Evaluation

e x a m i n e d in this w a y a n d never t h o s e t h a t a r e actually

p u t i n t o service. N o n d e s t r u c t i v e m e t h o d s of m e a s u r
ing residual stresses, o n the o t h e r h a n d , c a n in p r i n
ciple be applied t o every piece in a p r o d u c t i o n lot,
n o t only d u r i n g m a n u f a c t u r e b u t also in service. I n
a d d i t i o n , s o m e of these m e t h o d s a r e , in c o m p a r i s o n
with the destructive t e c h n i q u e , relatively r a p i d a n d
inexpensive.
T h e principal difficulty with t h e n o n d e s t r u c t i v e
m e t h o d s is t h a t they a r e all indirect. N o n e of t h e m
m e a s u r e residual stress per se; r a t h e r they m e a s u r e
s o m e physical q u a n t i t y which is influenced b y t h e
presence of stress, a n d these m e a s u r e m e n t s a r e t h e n
used t o infer t h e n a t u r e a n d t h e m a g n i t u d e s of t h e
stress d i s t r i b u t i o n . T h i s limitation is, of c o u r s e , n o t
uniquely characteristic of residual stress analysis; it
also applies t o c o n v e n t i o n a l e x p e r i m e n t a l stress
analysis, wherein stresses a r e n o t m e a s u r e d b u t calcu
lated from m e a s u r e m e n t s of strains, d e f o r m a t i o n s
a n d forces. T h e difference is t h a t in t h e c o n v e n t i o n a l
stress-analysis s i t u a t i o n t h e r e l a t i o n s h i p s b e t w e e n the
m e a s u r e d q u a n t i t i e s a n d stress a r e relatively well
u n d e r s t o o d a n d u n a m b i g u o u s . In n o n d e s t r u c t i v e
e v a l u a t i o n of residual stresses, o n t h e o t h e r h a n d ,
m e a s u r e m e n t s are m a d e of q u a n t i t i e s such as crystallographic lattice p a r a m e t e r s o r u l t r a s o n i c velocities.
These q u a n t i t i e s a r e often influenced n o t only b y
stress b u t by m a t e r i a l p a r a m e t e r s which a r e difficult t o
quantify, such as metallurgical texture.
T h e r e is a n o t h e r n o t e w o r t h y difference b e t w e e n
c o n v e n t i o n a l e x p e r i m e n t a l stress analysis a n d t h e
e v a l u a t i o n of residual stresses. I n the c o n v e n t i o n a l
case only c h a n g e s in stress a r e m e a s u r e d , for e x a m p l e ,
from the u n l o a d e d t o t h e l o a d e d state (the applied
stresses are zero b y definition, w h e n t h e m e m b e r is n o t
externally l o a d e d ) . I n residual stress e v a l u a t i o n t h e
goal is a n a b s o l u t e stress d e t e r m i n a t i o n even t h o u g h
a n unstressed reference state is generally u n a v a i l a b l e .

2. X-Ray

Diffraction

M o s t n o n d e s t r u c t i v e m e a s u r e m e n t s of residual stress
are m a d e by x-ray diffraction t e c h n i q u e s (see X-Ray
Powder Diffraction), w h e r e b y x-ray b e a m s a r e used t o
m e a s u r e selected c r y s t a l l o g r a p h i c lattice spacings in
the m a t e r i a l t h r o u g h B r a g g ' s law. It is a s s u m e d t h a t
t h e u n i t c h a n g e in lattice spacing is e q u a l t o t h e elastic
strain in t h e c o n t i n u u m a t t h e p o i n t of m e a s u r e m e n t
a n d in a direction p e r p e n d i c u l a r t o t h e lattice p l a n e s .
T h a t is, if d is t h e spacing between lattice p l a n e s
t h a t a r e o r i e n t e d p e r p e n d i c u l a r t o s o m e direction ,
a n d if t h e u n s t r a i n e d lattice spacing is d0, t h e n the
elastic strain in direction is

Figure 1
Rectangular coordinate system at the surface of a
material. Direction y is perpendicular to the page; plane
xy is coincident with the surface of the material; plane xz
is the diffraction plane; and direction is in the
diffraction plane, inclined to by angle

M o n o c h r o m a t i c r a y s , such as t h o s e used in c o n v e n
t i o n a l x-ray diffraction w o r k , p e n e t r a t e crystalline
m a t e r i a l s t o a d e p t h of only a few m i c r o m e t e r s , so t h e
m e t h o d applies only t o t h e n o n d e s t r u c t i v e m e a s u r e
m e n t of surface stresses. A t a free surface (Fig. 1) t h e
n o r m a l stress a n d t h e s h e a r stresses a n d xyz a r e
z e r o a n d h e n c e , b y H o o k e ' s law, t h e n o r m a l stress in
t h e surface in t h e direction is

YT~v^ ~
x

z)

( 2 )

where and are Y o u n g ' s modulus and Poisson's

r a t i o , respectively.
T h e physical g e o m e t r y of x-ray diffraction e q u i p
m e n t d o e s n o t p e r m i t it t o be o r i e n t e d in such a w a y
t h a t lattice spacings parallel t o t h e surface c a n be
m e a s u r e d . T h e r e f o r e , in o r d e r t o use E q n . (2), m u s t
be d e t e r m i n e d from strain m e a s u r e m e n t s m a d e in t w o
directions inclined t o t h e surface. O n e of these direc
tions is usually t a k e n as (i.e., p e r p e n d i c u l a r t o t h e
surface) a n d t h e second is inclined a t s o m e angle ,
typically 45, as s h o w n in Fig. 1. F r o m t h e e q u a t i o n s
for strain at a p o i n t ,

- c o s
.

sin

a n d s u b s t i t u t i n g i n t o E q n . (2),

l + sin

T h e strains in this r e l a t i o n s h i p c a n b e expressed in

t e r m s of lattice s t r a i n s b y u s i n g E q n . ( I ) , t h u s ,

d dn d dn d d

418

Residual

Since (J,
by

d0)/dz

<

1, this expression c a n be replaced

Stresses:

Nondestructive

Table 1
Lattice planes and radiation sources used for residual stress
measurements
Lattice plane

w i t h o u t significant e r r o r a n d , therefore, E q n .
becomes

1 + sin

(3)

dz

(Using B r a g g ' s law, a n e q u i v a l e n t expression m a y b e

written in t e r m s of diffraction angles instead of d
values.) T h i s e q u a t i o n p e r m i t s t h e surface stress t o be
evaluated w i t h o u t m e a s u r i n g either t h e surface strain
o r the u n s t r a i n e d lattice p a r a m e t e r d0.
T h e stress , of c o u r s e , is n o t a principal stress
unless the diffraction p l a n e (in this case the xz p l a n e )
h a s been aligned with a principal stress direction.
In m a n y practical s i t u a t i o n s the principal stress
directions can be estimated quite accurately from con
ditions of s y m m e t r y (e.g., in rolled o r extruded m e m
bers) or from p r i o r experience. W h e n this is n o t the
case, the surface stresses m u s t be evaluated in at least
three directions. T h e m a g n i t u d e s a n d the directions of
the principal stresses in the surface, , a n d can then
be calculated from the m a g n i t u d e s a n d directions of
the m e a s u r e d stresses by the theory of elasticity.
T o m a k e residual stress m e a s u r e m e n t s it is neces
sary t o select a set of lattice p l a n e s a n d a r a d i a t i o n
wavelength w h i c h will p r o v i d e m e a s u r a b l e B r a g g dif
fraction. F o r a n y given m a t e r i a l there a r e a variety of
lattice p l a n e a n d r a d i a t i o n c o m b i n a t i o n s which c a n be
used. F o r g o o d m e a s u r e m e n t sensitivity, it is desirable
to select a c o m b i n a t i o n w h i c h gives a large c h a n g e in
diffraction angle for a given c h a n g e in lattice spacing;
this is achieved w h e n t h e diffraction angle is large. It
is generally c o n s i d e r e d g o o d practice if 2 exceeds
125 or, preferably, 140. S o m e lattice-plane a n d
r a d i a t i o n c o m b i n a t i o n s w h i c h a r e used for residual
stress m e a s u r e m e n t s a r e given in T a b l e 1.
A variety of diffraction e q u i p m e n t is c o m m e r c i a l l y
available for residual stress m e a s u r e m e n t , r a n g i n g
from high-precision l a b o r a t o r y i n s t r u m e n t s t o p o r t
able units t h a t c a n be used in the field. W i t h c a r e
ful a l i g n m e n t , diffraction angles c a n be m e a s u r e d
with a n a c c u r a c y of a p p r o x i m a t e l y 0 . 0 , which
allows d values t o be d e t e r m i n e d t o a p p r o x i m a t e l y
0 . 0 1 p m , a n d lattice-strain values t o a p p r o x i
l
mately 200 m ~ . T h e c o r r e s p o n d i n g u n c e r t a i n t y
in stress values d e p e n d s u p o n t h e elastic c o n s t a n t s ;
1
for a l u m i n u m a n u n c e r t a i n t y of 200 m
in
strain is equivalent t o a n u n c e r t a i n t y of a p p r o x i m
ately 1 4 M P a in stress. F o r steel, w h i c h is r o u g h l y
three times stiffer t h a n a l u m i n u m , the c o r r e s p o n d i n g
u n c e r t a i n t y in stress is 41 M P a . In practical s i t u a t i o n s
it is n o t unrealistic to expect e r r o r s t h a t a r e twice as
large, o r even larger.

Evaluation

Material
Ferritic iron
Austenitic steel
Aluminum
Copper
Magnesium
Nickel

(hkl)

spacings

211
310
651,732
220
420
222
420
511,333
400
420
105
313
420

117.0
90.6
36.4
127.3
80.5
116.9
90.6
77.9
90.4
80.8
97.6
80.8
78.8

X-ray source
3

target

filter

Cr
Co
Mo
Cr
Cu
Cr
Co
Cu
Co
Cu
Fe
Cu
Cu

C
Fe
Zr
V
Ni
V
Fe
Ni
Fe
Ni
Mn
Ni
Ni

a Nominal value in picometers; actual values depend on the alloy and the
strain level b To eliminate K e radiation

T h e e v a l u a t i o n of residual stresses b y the direct

a p p l i c a t i o n of E q n . (4), w h i c h requires t h e m e a s u r e
m e n t of a lattice s p a c i n g in t w o different o r i e n t a t i o n s ,
is c o m m o n l y referred t o as t h e t w o - a n g l e o r the t w o tilt m e t h o d . S o m e w h a t b e t t e r a c c u r a c y m a y be
o b t a i n e d by m e a s u r i n g t h e lattice spacing for a
n u m b e r of angles a n d u s i n g a suitable curve-fitting
2
t e c h n i q u e t o c o m p u t e t h e stress. T h i s is the sin
method.
It is clear, from E q n . (4), t h a t the r a t i o (d dz)/
2
sin s h o u l d be a c o n s t a n t , within e x p e r i m e n t a l
2
e r r o r , b u t s o m e t i m e s , w h e n using t h e sin m e t h o d , it
is f o u n d t h a t t h e r a t i o is n o t . T h i s generally m e a n s
t h a t t h e basic a s s u m p t i o n , r e p r e s e n t e d b y E q n . (1),
d o e s n o t h o l d . I n o t h e r w o r d s , it is n o t always true
t h a t lattice strain, in a p a r t i c u l a r lattice direction, is
a n a c c u r a t e i n d i c a t o r of t h e p r e v a l e n t elastic strain in
t h e c o n t i n u u m a t t h e p o i n t of m e a s u r e m e n t . It a p
p e a r s t h a t u n d e r certain c o n d i t i o n s s o m e lattice direc
tions experience m o r e strain ( a n d s o m e less) t h a n
o t h e r s , even w h e n all a r e o r i e n t e d in t h e s a m e m a c r o
scopic direction. T h e r e is evidence w h i c h suggests t h a t
this c o n d i t i o n is only e n c o u n t e r e d in m a t e r i a l s t h a t
h a v e b e e n subjected t o severe plastic d e f o r m a t i o n in
o n e p r e d o m i n a n t direction (e.g., rolling, d r a w i n g a n d
tension testing) a n d n o t s u b s e q u e n t l y h e a t treated.
O b v i o u s l y , a n a t t e m p t t o e v a l u a t e residual stresses by
the t w o - a n g l e m e t h o d , w h e n this c o n d i t i o n is present,
c a n lead t o r a t h e r serious e r r o r s .
T w o m e t h o d s a r e available for e v a l u a t i n g residual
stresses w h e n this c o n d i t i o n of i n h o m o g e n e o u s plastic
d e f o r m a t i o n is present. O n e is b a s e d o n a n empirical
curve-fitting p r o c e d u r e ( J a m e s a n d C o h e n 1980); the
o t h e r restricts t h e m e a s u r e m e n t process t o selected
lattice p l a n e s which a p p e a r t o o b e y E q n . (1) even
w h e n the c o n d i t i o n exists ( V a n d e Walle 1981 p . 213).

419

Residual

Stresses:

Nondestructive

Evaluation

Table 2
Young's moduli: comparison of lattice and bulk values
Material

Direction

Ferritic iron

<ioo>
<111>

Carbon steel

<211>
<220>
<310>

bulk

bulk

Aluminum

<100>
<111>
<420>

Copper

<400>

Nickel

<313>
<420>

bulk

bulk

bulk

Young's
3
modulus (GPa)

132
284
210
205
232
177
210
63
75
67
70
106
120
230
199
200

a Values shown for bulk material are nominal; actual values may vary
somewhat with alloy

A n o t h e r source of e r r o r , w h i c h is s o m e t i m e s signi
ficant, arises from u n c e r t a i n t i e s in t h e elastic c o n
stants. T h e values of a n d w h i c h s h o u l d b e used
with E q n . (4) a r e n o t t h e c o n v e n t i o n a l values for b u l k
polycrystalline m a t e r i a l s . R a t h e r , they s h o u l d be t h e
values t h a t c o r r e s p o n d t o t h e p a r t i c u l a r lattice direc
tion which is m e a s u r e d . (Crystals a r e elastically a n i s o
tropic a n d the b u l k values of t h e elastic c o n s t a n t s only
represent s o m e a v e r a g e of t h e elastic c o n s t a n t s for t h e
v a r i o u s crystalline o r i e n t a t i o n s . ) M e t h o d s for calcu
lating lattice elastic c o n s t a n t s h a v e been p r o p o s e d b u t
the m o s t reliable values a r e t h o s e d e v e l o p e d in calib
r a t i o n e x p e r i m e n t s in which c h a n g e s in lattice strain
are m e a s u r e d as a function of applied stress (Prevey
1977). F o r a l u m i n u m , t h e elastic c o n s t a n t s a r e n o t
particularly sensitive t o lattice direction, while for
steel t h e b u l k elastic c o n s t a n t s c a n b e used for the
<211> direction w i t h o u t excessive e r r o r . F o r o t h e r
directions a n d o t h e r m a t e r i a l s , significant differences
m a y exist b e t w e e n t h e lattice elastic c o n s t a n t s a n d t h e
bulk values ( T a b l e 2).

3.

^ r = \ + B a

(5)

w h e r e V is t h e u l t r a s o n i c w a v e speed in t h e m a t e r i a l ,
V0 is t h e speed in t h e unstressed state, is t h e stress
a n d is t h e c o n s t a n t of p r o p o r t i o n a l i t y , k n o w n as t h e
a c o u s t o e l a s t i c c o n s t a n t . is a function of V0 a n d t h e
second- a n d t h i r d - o r d e r elastic c o n s t a n t s of the
m a t e r i a l . Reliable values of acoustoelastic a n d thirdo r d e r elastic c o n s t a n t s a r e n o t generally available.
E q u a t i o n (5) is overly simplistic because it d o e s n o t
a c c o u n t for t h e fact t h a t V0 a n d b o t h d e p e n d u p o n
t h e m o d e of t h e u l t r a s o n i c w a v e a n d , f u r t h e r m o r e ,
d e p e n d s u p o n t h e relative directions of t h e u l t r a s o n i c
w a v e a n d t h e stresses. F o r a m o r e precise c h a r a c t e r i
z a t i o n , c o n s i d e r a n elastic b o d y w i t h principal stress
directions i, j a n d k. T h e n , for a l o n g i t u d i n a l w a v e
p r o p a g a t i n g in t h e / direction,
^ l + B f a

+ Bfa+Bfa

(6)
l

w h e r e , a n d ak a r e t h e principal stresses a n d B n
represents t h e effect of p r i n c i p a l stress o n Vr
F o r a s h e a r w a v e p r o p a g a t i n g in direction / a n d
p o l a r i z e d such t h a t particle m o t i o n is in direction j ,
^L=\

(7)

+ Bfaj+B*ak

(8)

+ B !ai+B jaj+B lak

a n d similarly,

l!L=l+B?ai
v

ik0

C o n s i d e r , n o w , a p l a t e u n d e r p l a n e stress c o n
d i t i o n s , such t h a t / is the thickness direction. T h e n , is
zero. If t h e p l a t e m a t e r i a l c a n be a s s u m e d t o b e
acoustoelastically isotropic, t h e n

Ultrasonics

A l t h o u g h t h e x-ray diffraction m e t h o d of m e a s u r i n g
residual stresses is extremely useful, it h a s t w o s h o r t
c o m i n g s : it c a n n o t be used for noncrystalline m a t e r
ials, such as plastics, a n d it c a n n o t m e a s u r e i n t e r n a l
residual stresses nondestructively. Several o t h e r
a p p r o a c h e s t o t h e n o n d e s t r u c t i v e e v a l u a t i o n of resi
d u a l stresses a r e u n d e r d e v e l o p m e n t a l t h o u g h n o n e of
t h e m c a n claim a level of reliability similar t o t h a t
which characterizes careful x-ray diffraction m e a s u r e
m e n t s . U l t r a s o n i c m e t h o d s for t h e m e a s u r e m e n t of

420

residual stresses a r e c o n s i d e r e d h e r e in s o m e w h a t
m o r e detail t h a n o t h e r a p p r o a c h e s because they a p
p e a r t o h a v e p o t e n t i a l for t r e m e n d o u s capability,
versatility a n d usefulness in t h e future.
T h e u l t r a s o n i c a p p r o a c h is b a s e d o n t h e e x p e r i m e n
tally confirmed o b s e r v a t i o n t h a t t h e speed of s o u n d in
a b o d y varies linearly w i t h stress. T h u s , in c o n c e p t u a l
terms,

B'j=B'k,

B<f=B%,

B'l=

Bf

and

Where
is t h e s h e a r w a v e velocity in t h e unstressed
state. ( T h e c o n d i t i o n s u n d e r w h i c h this a s s u m p t i o n is
justified a r e n o t fully u n d e r s t o o d . It is n o t o b v i o u s
t h a t elastic i s o t r o p y (i.e., a n d isotropic) c o n n o t e s
acoustoelastic isotropy.) U n d e r these c o n d i t i o n s ,
E q n s . ( 6 - 8 ) r e d u c e t o , respectively,

Residual
Table 3
3
Acoustoelastic constants for several materials
Material

Steels
AISI 1018
ASTM A516
0.0001
ASTM A533B
0.00007
17-4 PH (cond. A)
304 SS
Rail steel
0.00015
Aluminum alloys
2024-T351
0.00083
2024-T4
6061-T6
6061-T651
0.00056
7075-T651
0.0013
Copper
-0.003

B*{

-0.00083

0.0000

-0.00087
-0.00074
-0.00075

0.00002

-0.0029
-0.0029
-0.0023

0.00097
0.00091

+ ak)

ij

(9)

(10)

-JL=\+Bfa
j+B jak
y

(11)

s0

S o m e values of t h e a c o u s t o e l a s t i c c o n s t a n t s a r e
t a b u l a t e d in T a b l e 3. N o t e t h a t t h e values for a l u m i
n u m alloys a r e substantially larger t h a n t h o s e for
steels, which enables stresses in a l u m i n u m alloys t o be
d e t e r m i n e d with g r e a t e r precision t h a n stresses in
steels. N o t e , also, t h a t t h e n u m e r i c a l values a r e all
quite small, t h a t is, t h e c h a n g e s in u l t r a s o n i c velocity
d u e t o stress a r e q u i t e small. Specialized electronic
e q u i p m e n t is n e e d e d t o m e a s u r e these velocities a c c u r
ately. It is usually m o r e p r a c t i c a l t o m e a s u r e t h e
transit time of a n u l t r a s o n i c w a v e t h r o u g h a m a t e r i a l
t h a n m e a s u r e its velocity. T h u s , if t h e thickness of t h e
plate is h0 in t h e unstressed state a n d h in t h e
unstressed state,

-{i i)(j J
+Bi

IliZljlL=X-^LKiB i-B j){arak)

i0

j^-l+Bfa+Bfa

Nondestructive

Evaluation

h o w e v e r , since unstressed m a t e r i a l is n o t usually

available for t h e e v a l u a t i o n of .
T h e s e difficulties c a n often be a v o i d e d b y using
s h e a r waves r a t h e r t h a n l o n g i t u d i n a l waves a n d t a k
ing a d v a n t a g e of t h e s h e a r - w a v e birefringence ( H s u
1974). T h u s , if Ttj a n d Tik a r e t h e t r a n s i t times for
u l t r a s o n i c s h e a r waves p o l a r i z e d in t h e j a n d k direc
tions, respectively,

a Compiled and adapted from various sources. Most of these data have
not been independently verified and are presented here only to illustrate
comparative magnitudes. All values are in percent per MPa

-L=\+B'j{aj
v

Stresses:

(12)

where Tt a n d Ti0 a r e t h e t r a n s i t times in the stressed

a n d t h e unstressed states, respectively. T h e p r a c t i c a l
i m p l e m e n t a t i o n of this e q u a t i o n p o s e s difficulties,

(13)

ik

Clearly, this a p p r o a c h t o t h e e v a l u a t i o n of residual

stresses, as well as t h a t r e p r e s e n t e d b y E q n . (12), is
m o s t useful w h e n ai o r ak is k n o w n t o be zero o r
nearly z e r o .
T h e r e a r e o t h e r i m p l e m e n t a t i o n s of t h e a c o u s t o
elastic effect which m i g h t b e used t o m e a s u r e residual
stresses. F o r e x a m p l e , u l t r a s o n i c Rayleigh waves c a n
be e m p l o y e d t o e v a l u a t e t h e stress o n t h e surface of a
b o d y ( H u s s o n et al. 1985). In this a p p l i c a t i o n t w o
surf ace-wave t r a n s d u c e r s a r e u s e d o n e t o l a u n c h the
w a v e a n d t h e second t o receive i t a n d the transit
time is m e a s u r e d . T h e d e p t h of p e n e t r a t i o n of a
Rayleigh w a v e d e p e n d s u p o n its frequency a n d so, b y
using several frequencies, s o m e idea of t h e residual
stress g r a d i e n t n o r m a l t o t h e surface c a n be inferred.
In all of these m e t h o d s w h i c h a r e b a s e d o n the
e v a l u a t i o n of t r a n s i t time (or time of flight) n o infor
m a t i o n is o b t a i n e d r e g a r d i n g t h e stress g r a d i e n t in
t h e direction of w a v e p r o p a g a t i o n . R a t h e r , the result
is a n a v e r a g e stress over the p a t h traversed by the
ultrasonic wave. Techniques based on ultrasonic
t o m o g r a p h y offer p r o m i s e , h o w e v e r , for t h e c h a r a c
terization of entire residual d i s t r i b u t i o n s across
selected i n t e r n a l p l a n e s in a solid b o d y ( H i l d e b r a n d
a n d H a r r i n g t o n 1981).
Still a n o t h e r a p p r o a c h , which h a s been used suc
cessfully for e v a l u a t i n g t h e prestress in t o r q u e d bolts,
is b a s e d u p o n m e a s u r e m e n t s of t h e c h a n g e in the
u l t r a s o n i c r e s o n a n c e frequency d u e t o e l o n g a t i o n of
t h e m e m b e r a n d t h e a c o u s t o e l a s t i c effect ( H e y m a n
1977).

4. Barkhausen

Noise

Analysis

A n u m b e r of m a g n e t i c p r o p e r t i e s a r e sensitive t o
stress a n d c a n , in principle a t least, b e used t o p r o v i d e
n o n d e s t r u c t i v e e v a l u a t i o n s of residual stresses in fer
r o m a g n e t i c m a t e r i a l s . D e s p i t e a lack of a d e q u a t e
u n d e r s t a n d i n g of t h e u n d e r l y i n g p h e n o m e n a , B a r k
h a u s e n noise analysis h a s b e e n used t o estimate
residual stresses in several engineering a p p l i c a t i o n s .
If a n e l e c t r o m a g n e t is used t o excite a n a l t e r n a t i n g
m a g n e t i c field in a f e r r o m a g n e t i c m e m b e r , e a c h rever
sal of t h e field generates a b u r s t of B a r k h a u s e n noise.
T h e p e a k a m p l i t u d e of t h e b u r s t , as m e a s u r e d , for
e x a m p l e , with a n inductive coil n e a r t h e surface of t h e
m e m b e r , varies with t h e level of stress at t h e surface.

421

Residual

Stresses:

Nondestructive

Evaluation

T h e r e l a t i o n s h i p between t h e noise a m p l i t u d e a n d t h e
stress is n o n e l i n e a r , however, a n d a p p e a r s t o b e m o s t
useful for the e s t i m a t i o n of stress levels well below t h e
yield strength of t h e m a t e r i a l . A l s o , B a r k h a u s e n noise
is influenced by a variety of m a t e r i a l p a r a m e t e r s o t h e r
t h a n stress, such as c o m p o s i t i o n , t e x t u r e a n d w o r k
h a r d e n i n g . H e n c e , it is i m p e r a t i v e in e a c h a p p l i c a t i o n
t o use calibrated reference s a m p l e s with t h e s a m e
c o m p o s i t i o n a n d processing history as t h e m e m b e r
being analyzed.
T h e limitation of t h e m e t h o d t o t h e m e a s u r e m e n t of
near-surface stresses results from t h e fact t h a t t h e
i n d u c t i o n field from a B a r k h a u s e n j u m p is d a m p e d b y
e d d y c u r r e n t s . T h e r e is evidence t h a t stresses a t s o m e
w h a t greater d e p t h s c a n be p r o b e d if t h e B a r k h a u s e n
j u m p s a r e sensed acoustically r a t h e r t h a n inductively
( B u r k h a r d t et al. 1982).
T h e chief a d v a n t a g e s of t h e B a r k h a u s e n noise
a p p r o a c h to residual stress m e a s u r e m e n t a r e t h a t it is
rapid a n d the e q u i p m e n t n e e d e d t o m a k e t h e m e a s u r e
m e n t c a n be conveniently p o r t a b l e .

5. Other

Methods

M a n y physical p h e n o m e n a a r e sensitive t o stress a n d ,

in principle, c a n be used to e v a l u a t e t h e stress levels in
solid bodies. E x a m p l e s include t h e M o s s b a u e r effect,
positron annihilation and piezospectroscopy.
Photoelasticity also deserves m e n t i o n . T h i s m e t h o d
of e x p e r i m e n t a l stress analysis is well established, b u t
as a m e a n s for e v a l u a t i n g residual stresses it is clearly
useful only for m e m b e r s fabricated from glass o r
t r a n s p a r e n t plastics t h a t h a p p e n t o be optically birefringent.
R e c e n t research h a s a t t e m p t e d t o e x t e n d t h e c o n
ventional x-ray diffraction a p p r o a c h t h r o u g h t h e use
of highly p e n e t r a t i n g r a d i a t i o n . T h e a i m is t o m e a s u r e
residual stresses in t h e interior of solid bodies. T w o
forms of p e n e t r a t i n g r a d i a t i o n a r e being e x p l o r e d ,
t h e r m a l n e u t r o n s a n d high-energy rays, b o t h of
which p r o v i d e significantly m o r e d e p t h of p e n e t r a t i o n
in m o s t s t r u c t u r a l m e t a l s t h a n t h e m o n o c h r o m a t i c xr a y b e a m s which a r e c o n v e n t i o n a l l y used. I n e a c h
case, careful c o l l i m a t i o n of t h e i n c o m i n g a n d t h e
diffracted b e a m s is e m p l o y e d t o focus o n a small,
preselected interior v o l u m e . N e u t r o n diffraction h a s
been used in this w a y t o m e a s u r e t h e lateral strain in
the interior of r o d s subjected t o axial tension, a n d t h e
results agree with analytical p r e d i c t i o n s ( P r a s k a n d
C h o i 1984). T h i s t e c h n i q u e offers p r o m i s e for c h a r a c
terizing the entire residual stress d i s t r i b u t i o n s in refer
ence samples which c o u l d t h e n b e used for c a l i b r a t i n g
or verifying o t h e r m e a s u r e m e n t m e t h o d s .
O n e limitation of t h e n e u t r o n diffraction t e c h n i q u e
is t h a t it generally requires a n u c l e a r r e a c t o r as a
source, which p r e c l u d e s its a p p l i c a t i o n t o residual
stress m e a s u r e m e n t s in m o s t industrial a p p l i c a t i o n s .
H i g h - e n e r g y r a y s , o n t h e o t h e r h a n d , offer p r o m i s e

422

of d e v e l o p m e n t i n t o a field m e t h o d . T h i s m e t h o d
e m p l o y s a s o u r c e of w h i t e r a d i a t i o n , such as is used in
radiographic applications. In contrast to conven
tional x-ray diffraction w h e r e i n t h e wavelength is
preselected a n d t h e diffraction angle is m e a s u r e d , t h e
high-energy x-ray t e c h n i q u e e m p l o y s energy disper
sive s p e c t r o s c o p y t o m e a s u r e t h e w a v e l e n g t h s which
diffract a t preselected diffraction angles (Bechtoldt et
al. 1982).
See also: Residual Stresses: Measurement Using Neutron
Diffraction; Stress Distribution: Analysis Using Thermoelastic Effect

Bibliography
Bechtoldt C J, Placious R C, Boettinger W J, Kuriyama
1982 X-ray residual stress mapping in industrial materials
by energy dispersive diffractometry. Adv. X-Ray Anal. 25:
329-38
Blessing G V, Hsu , Proctor 1984 Ultrasonic-shearwave measurement of known residual stress in aluminum.
Exp. Mech. 24: 218-22
Burkhardt G L, Beissner R E, Matzkanin G A, King J D
1982 Acoustic methods for obtaining Barkhausen noise
stress measurements. Mater. Eval. 40: 669-75
Heyman J S 1977 A CW ultrasonic bolt-strain monitor.
Exp. Mech. 17: 183-7
Hildebrand , Harrington 1981 Mapping of materials
stress with ultrasonic tomography. Mater. Eval. 39: 38390
Hilley , Larson J A, Jatczak C F, Ricklefs R (eds.)
1971 Residual Stress Measurement by X-Ray Diffraction,
2nd edn. Society of Automotive Engineers, New York
Hsu 1974 Acoustical birefringence and the use of
ultrasonic waves for experimental stress analysis. Exp.
Mech. 14: 169-76
Husson D, Bennett S D, Kino G S 1985 Measurement of
stress with surface waves. Mater. Eval. 43: 92-100
James R, Buck 1980 Quantitative nondestructive
measurements of residual stresses. CRC Crit. Rev. Solid
State Mater. Sci. 9: 61-105
James R, Cohen J 1980 The measurement of residual
stresses by x-ray diffraction techniques. In: Herman
(ed.) 1980 Experimental Methods, Treatise on Materials
Science and Technology, Vol. 19, pt. A. Academic Press,
New York, pp. 1-62
Kino G S, Barnett D M, Grayeli N, Herrmann G, Hunter J
B, Ilic D B, Johnson G C, King R B, Scott , Shyne J
C, Steele C R 1980 Acoustic measurements of stress fields
and microstructure. / . Nondestr. Eval. 1: 67-77
Prask J, Choi C S 1984 N D E of residual stress in uranium
by means of neutron diffraction. J. Nucl. Mater. 126: 124
31
Prevey S 1977 A method of determining the elastic
properties of alloys in selected crystallographic directions
for x-ray diffraction residual stress measurement. Adv. XRay Anal. 20: 345-54
Vande Walle L J (ed.) 1981 Residual Stress for Designers and
Metallurgists. ASM, Materials Park, OH
L. M o r d f i n
[ N a t i o n a l B u r e a u of S t a n d a r d s ,
Washington, D C , USA]

s
Scanning Electron Microscopy

T h e signals from the specimen include:

T h e basic principle of the s c a n n i n g electron m i c r o

scope ( S E M ) is t o scan a specimen with a finely
focused electron b e a m of kilovolt energy. A n i m a g e is
formed by s c a n n i n g a c a t h o d e - r a y t u b e in s y n c h r o
nism with the b e a m (Fig. 1) a n d by m o d u l a t i n g the
brightness of this t u b e with beam-excited signals. I n
this way, a n i m a g e is built u p p o i n t - b y - p o i n t w h i c h
shows the v a r i a t i o n s in the g e n e r a t i o n a n d collection
efficiency of the c h o s e n signal at different p o i n t s o n
the specimen.
U n l i k e the t r a n s m i s s i o n electron m i c r o s c o p e , t h e r e
is n o need t o refocus t h e signal-carrying particles
generated in the specimen. T h i s m a k e s it possible t o
e x a m i n e r o u g h , solid specimens with a m i n i m u m of
specimen p r e p a r a t i o n . By using different c o n d i t i o n s
a n d specimens, it is possible t o o b t a i n images s h o w i n g
the surface t o p o g r a p h y , a v e r a g e a t o m i c n u m b e r ,
surface-potential d i s t r i b u t i o n , m a g n e t i c d o m a i n s ,
crystal o r i e n t a t i o n a n d crystal defects in a solid speci
men.

I. Electron-Specimen

(a)

S e c o n d a r y electrons ( S E ) t h e s e leave the speci

m e n with a n energy of typically 1-10 eV, with
50 eV being specified as the u p p e r energy limit.
In fact, m a n y h u n d r e d s of s e c o n d a r y electrons
c a n be excited within the specimen by a single
p r i m a r y electron, b u t only t h o s e which are
excited within ~ 10 n m of the surface c a n escape
i n t o the v a c u u m a n d be detected. T h u s , second
a r y electrons c a n be subdivided i n t o those t h a t
escape from the specimen at the p o i n t w h e r e the
p r i m a r y electron enters the specimen a n d those
t h a t are excited at the p o i n t w h e r e it leaves. In
m o s t cases, the primary-excited s e c o n d a r y elec
t r o n s a r e c a p a b l e of higher resolution t h a n the
others.

(b)

B a c k s c a t t e r e d electrons ( B S E ) t h e s e leave the

specimen with a n a p p r e c i a b l e fraction of the
p r i m a r y - b e a m energy. ( F o r the p u r p o s e of a
definition, a b a c k s c a t t e r e d electron h a s a n
energy g r e a t e r t h a n 50 eV.) I n o r d e r to be b a c k scattered from a thin film o r from a solid target,
a p r i m a r y particle m u s t experience o n e o r m o r e
close e n c o u n t e r s with the nuclei of the target
a t o m s ( R u t h e r f o r d scattering events). T h e t e r m s
rediffused electrons a n d reflected electrons are
s y n o n y m o u s w i t h b a c k s c a t t e r e d electrons.

(c)

Elastically scattered e l e c t r o n s t h e s e h a v e a n
energy loss, from a solid target, of typically less
t h a n ~ 1 eV. In s o m e cases, electrons with c h a r
acteristic energy losses c a n also be detected.
Low-loss electrons ( L L E ) t h e s e a r e b a c k s c a t
tered electrons t h a t h a v e lost less t h a n ~ 1 % of
the p r i m a r y energy in t h e specimen. T h e y c a n
either be selected by a n energy filter, o r be
collected t o g e t h e r with the o t h e r b a c k s c a t t e r e d
electrons by a solid-state o r scintillator BSE
detector. Low-loss-electron images are o b t a i n e d
from a thin surface layer a n d c a n s h o w s t r o n g
t o p o g r a p h i c a n d electron c h a n n e l l i n g c o n t r a s t s .
Low-loss-electron i m a g e s a r e similar in s o m e
respects t o t h o s e o b t a i n e d in the t r a n s m i s s i o n
electron m i c r o s c o p e w h e n o p e r a t e d with a solid
specimen in reflection.
C h a r a c t e r i s t i c rays a n d the c o n t i n u u m x-ray
s p e c t r u m (or b r e m s s t r a h l u n g ) t h e s e c a n also be
p r o d u c e d ; they are described elsewhere (see Elec
tron Microprobe
Analysis).
A u g e r e l e c t r o n s t h e s e leave the specimen with
a n energy d i s t r i b u t i o n t h a t is similar ( b u t n o t
identical) t o t h a t of the characteristic rays.
M a t e r i a l s analysis using A u g e r electrons requires
a n u l t r a h i g h v a c u u m a n d is carried o u t via the

Interactions
1 2

T h e b e a m c u r r e n t / in the S E M is typically 1 0 " 7

1 0 " A with a n energy E0 of 5-50 keV. T h e electron
p e n e t r a t i o n d e p t h is t h e n typically of the o r d e r of a
m i c r o m e t e r a n d t h e b e a m d i a m e t e r 10-100 n m .
In s o m e cases, the r e s o l u t i o n a t t a i n a b l e is limited
directly by the electron p e n e t r a t i o n d e p t h , w h e r e a s in
o t h e r cases a m o r e favorable r e s o l u t i o n c a n b e
obtained.

(d)

(Camera)

Scanning
generator

Tl
Display / \Display i
tube / \ tube
I /
\ 2

Magnification X and Y\
control

Video
amplifier

(e)

Z7777

Specimen

Figure 1

Schematic diagram of a scanning electron microscope

(f)

423

Scanning

Electron

Microscopy

(a)

(b)

Figure 2
TmSe and other phases of the TmxSr,_JSe system: (a) secondary-electron image showing topographic contrast;
(b) backscattered-electron image also showing compositional contrast (normal incidence; E0 = 20 keV; 1=2*
10" )
(Holtzberg F, Schad R G, unpublished)

s c a n n i n g A u g e r m i c r o p r o b e (see Auger
Spectroscopy).
(g)

Electron

C a t h o d o l u m i n e s c e n c e b e a m - i n d u c e d light sig
nals c a n also give a n i m a g e .

(b)

S o u n d w a v e s t h e s e c a n be excited by a pulsed
electron b e a m b e c a u s e of t h e r m a l e x p a n s i o n a n d
c o n t r a c t i o n of t h e i r r a d i a t e d z o n e . T h e y c a n be
detected with a m i c r o p h o n e .

E x c i t a t i o n s within the specimen include:

(a)

424

E l e c t r o n - h o l e p a i r s t h e s e c a n be excited in
either s e m i c o n d u c t i n g o r insulating specimens
t h r o u g h o u t t h e v o l u m e t h a t is i r r a d i a t e d b y the
incident electron b e a m . ( W i t h silicon it requires
3.64 eV p r i m a r y energy for e a c h i n d u c e d elec
t r o n - h o l e pair.) F o r a s e m i c o n d u c t o r , these c a n
be collected by m e a n s of a p-n j u n c t i o n o r a
S c h o t t k y - b a r r i e r j u n c t i o n , o r in a biased region
of m a t e r i a l . I n d u c e d c o n d u c t i v i t y c a n also be
o b t a i n e d t h r o u g h insulating t h i n films. T h e t e r m
i n d u c e d signal implies t h e collection of e l e c t r o n hole p a i r s , a n d this c a n therefore be m a n y times
larger t h a n t h e i n c i d e n t - b e a m c u r r e n t . ( T h e spe
cimen c u r r e n t is o b t a i n e d b y c o n n e c t i n g only a
single wire t o t h e s a m p l e a n d d o e s n o t involve
t h e c r e a t i o n of e l e c t r o n - h o l e p a i r s in t h e s a m
ple.) T h e i n d u c e d signal c a n be displayed t o give
an electron-beam-induced conductivity (EBIC)
i m a g e , which c a n s h o w t h e p o s i t i o n s of p-n
j u n c t i o n s (even w h e n covered with a thin m e t a l
layer) a n d crystal defects in a solid specimen.

2. Image

Contrasts

2.1 Topographic

Contrast

T h e ability of t h e s e c o n d a r y - e l e c t r o n i m a g e t o s h o w
the surface t o p o g r a p h y of a r o u g h specimen is, of
c o u r s e , o n e of t h e m o s t striking features of t h e
m e t h o d (Figs. 2, 3, 4). T o p o g r a p h i c c o n t r a s t t h e n
arises from v a r i a t i o n s in t h e angle of p r i m a r y - e l e c t r o n
incidence, from p o i n t - t o - p o i n t v a r i a t i o n s in t h e ef
ficiency with w h i c h s e c o n d a r y electrons a r e collected
a n d from p e n e t r a t i o n effects a t s h a r p edges.
F o r a s a m p l e t h a t h a s a nearly flat surface, it m a y
be possible t o see t o p o g r a p h i c c o n t r a s t s m o r e clearly
in t h e b a c k s c a t t e r e d - e l e c t r o n i m a g e . I n this i m a g e ,
t o p o g r a p h i c c o n t r a s t c a n be e n h a n c e d by p o s i t i o n i n g
t h e d e t e c t o r with a low takeoff angle relative t o the
surface p l a n e . If t w o solid-state ( s e m i c o n d u c t o r
d i o d e ) b a c k s c a t t e r e d - e l e c t r o n d e t e c t o r s a r e used
a b o v e t h e specimen a n d o n t h e o p p o s i t e sides of the
b e a m , t h e n c o n t r a s t c a n be o b t a i n e d by displaying
t h e s u m signal, while t o p o g r a p h i c c o n t r a s t c a n be
o b t a i n e d b y displaying t h e difference. T o p o g r a p h i c

Scanning

Electron

Microscopy

(a)

Figure 3
Application of SEM to silicon integrated-circuit
manufacture: the shell of S i 0 2 that remains when the
underlying polycrystalline silicon conducting line is
dissolved (Hawks S W, unpublished)

(b)

c o n t r a s t from a low-density s a m p l e c a n be i m p r o v e d
by c o a t i n g it with a t h i n layer of a h e a v y m e t a l .
2.2 Contrast
c o n t r a s t ( c o m p o s i t i o n a l c o n t r a s t ) w a s first utilized
o n a w i d e s p r e a d basis as a n extension t o t h e electron
m i c r o p r o b e t e c h n i q u e (see Electron
Microprobe
Analysis). H e r e , t h e s a m p l e is polished a n d m o u n t e d
p e r p e n d i c u l a r t o t h e b e a m so as t o facilitate t h e
calculation of t h e x-ray a b s o r p t i o n a n d s e c o n d a r y xray
fluorescence
corrections. The backscatteredelectron c u r r e n t is t h e n a m o n o t o n i c a l l y increasing
function of t h e a v e r a g e a t o m i c n u m b e r ( Z ) of t h e
s a m p l e , so t h a t t h e t e r m c o n t r a s t is a p p r o p r i a t e .
T h e d e p t h from w h i c h b a c k s c a t t e r e d electrons escape
into a d e t e c t o r with a high takeoff angle is a b o u t half
of t h e electron p e n e t r a t i o n d e p t h . C h e m i c a l analysis is
possible if t h e specimen is a k n o w n b i n a r y system
such as a diffusion c o u p l e .
If the specimen is tilted a t a n angle, t h e n c o n t r a s t
c a n still be o b t a i n e d in t h e b a c k s c a t t e r e d - e l e c t r o n
i m a g e if t h e collector is in a suitable p o s i t i o n relative
to t h e s a m p l e surface. T h e m o n o t o n i c d e p e n d e n c e of
t h e detected b a c k s c a t t e r e d - e l e c t r o n signal o n t h e
average of t h e specimen m a y t h e n n o longer h o l d ,
a n d t h e d e t e c t o r a n d s a m p l e p o s i t i o n s m a y need t o be
adjusted t o give a g o o d i m a g e .
2.3 Electron-Channelling-Pattern
Contrast
E l e c t r o n - c h a n n e l l i n g - p a t t e r n ( E C P ) c o n t r a s t arises if
the s a m p l e is a single crystal either over a large region
using t h e u s u a l b e a m - s c a n n i n g m o d e (large a r e a E C P )
o r over a smaller region b y r o c k i n g t h e b e a m a b o u t a
p o i n t (selected a r e a E C P ) . Briefly, t h e p r o b a b i l i t y of a
b a c k s c a t t e r i n g event will d e p e n d o n t h e angle b e t w e e n

(c)
Figure 4
Thermal cycling of aluminum film (thickness 1.3 ) on
an oxidized silicon substrate: (a) 250 C, (b) 400 C.
(c) after cooling to 250 C (after Lahiri and Wells 1969
Appl. Phys. Lett. 15: 234-5. American Institute of
Physics, New York. Reproduced with permission)

t h e incident electrons a n d t h e crystal lattice planes.

T h i s c a n give rise t o lines a n d b a n d s of c o n t r a s t in
either t h e s e c o n d a r y - e l e c t r o n o r the b a c k s c a t t e r e d electron i m a g e .
E C P c o n t r a s t c a n be used t o d e t e r m i n e t h e local
c r y s t a l l o g r a p h i c o r i e n t a t i o n , t o s h o w v a r i a t i o n s in
crystal s t r u c t u r e (caused b y ion b o m b a r d m e n t , for
e x a m p l e ) o r t o give i m a g e s of t h e crystal defects in a
solid specimen by m e a n s of t h e low-loss-electron
image.
2.4 Voltage
Contrast
If a p o t e n t i a l difference of a few volts exists between
t w o n e a r b y regions o n t h e surface of the specimen,
t h e n t h e m o r e negative region will a p p e a r b r i g h t e r in
t h e s e c o n d a r y - e l e c t r o n i m a g e . T h i s voltage c o n t r a s t
c a n b e used t o s h o w a reverse-biased p-n j u n c t i o n , a

425

Scanning

Electron

Microscopy

(a)

(b)

Figure 5
Thin-film magnetic recording head: (a) BSE image showing the surface topography (normal incidence; EQ = 45 keV);
(b) lock-in processed BSE image showing the magnetic domain walls (20 kHz excitation frequency)

suitably biased d i s c o n t i n u i t y in a metallic c o n d u c t o r

o r t h e voltage d i s t r i b u t i o n o n t h e surface of a n
oscillating q u a r t z crystal. V o l t a g e c o n t r a s t c a n c a u s e
i m a g e artifacts if t h e specimen is n o n c o n d u c t i n g a n d
charges u n d e r t h e b e a m .
Q u a l i t a t i v e v o l t a g e c o n t r a s t c a n b e o b t a i n e d in t h e
secondary-electron i m a g e w i t h o u t t h e need t o modify
the S E M . Usually, t h e specimen m u s t be tilted t o
w a r d s the detector. T h e r e m u s t be n o o b s t r u c t i o n s
between t h e specimen a n d t h e collector a n d n o insula
t o r s within several centimeters of t h e specimen. S o m e
times it m a y be necessary t o v a r y t h e p o t e n t i a l
between t h e specimen a n d g r o u n d in a d d i t i o n t o
a p p l y i n g a p o t e n t i a l b e t w e e n t h e different p a r t s of t h e
specimen surface.
F o r q u a n t i t a t i v e voltage c o n t r a s t , it m a y be neces
sary t o m e a s u r e the energy d i s t r i b u t i o n of t h e second
a r y electrons with a n energy a n a l y z e r o r energy filter.
S t r o b o s c o p i c voltage c o n t r a s t h a s been o b t a i n e d by
pulsing t h e incident electron b e a m in s y n c h r o n i s m
with t h e voltage cycles of t h e device. V o l t a g e c o n t r a s t
c a n be isolated from t o p o g r a p h i c c o n t r a s t by display
ing t h e difference b e t w e e n t h e i m a g e s t h a t a r e
o b t a i n e d w h e n t h e voltage either is, o r is n o t , applied
t o the s a m p l e .
2.5 Magnetic
Specimens
M a g n e t i c specimens c a n be studied in the S E M in t w o
m a i n w a y s . F o r s a m p l e s such as c o b a l t , y t t r i u m
orthoferrite a n d m a g n e t o p l u m b i t e , t h e fringing field
will m o d u l a t e t h e trajectories of t h e s e c o n d a r y elec
t r o n s b e t w e e n t h e specimen a n d t h e collector. T h i s
shows u p as wide, diffuse b a n d s s u p e r i m p o s e d o n t h e

426

d o m a i n b o u n d a r i e s a n d is d e s i g n a t e d type-1 m a g n e t i c
contrast.
T y p e - 2 m a g n e t i c c o n t r a s t s h o w s u p in t h e b a c k scattered electron i m a g e of m a t e r i a l s such as s i l i c o n i r o n a n d nickel, w h i c h h a v e cubic s y m m e t r y a n d a
sufficiently s t r o n g i n t e r n a l field. D e p e n d i n g o n t h e
e x p e r i m e n t a l a r r a n g e m e n t , this c a n s h o w u p either as
d o m a i n c o n t r a s t (in w h i c h t h e a l t e r n a t i n g d o m a i n s
a p p e a r b r i g h t a n d d a r k ) , o r as wall c o n t r a s t (in which
t h e d o m a i n s a p p e a r t o b e equally b r i g h t b u t t h e
d o m a i n walls a p p e a r as b r i g h t o r d a r k n a r r o w b a n d s ) .
T y p e - 2 m a g n e t i c c o n t r a s t s e l d o m exceeds 1 % of t h e
collected c u r r e n t a n d in m a n y cases m a y be c o n s i d e r a
bly smaller even t h a n this. T h e r e f o r e , it is generally
necessary t o p r e p a r e t h e s a m p l e with a flat, s m o o t h
surface a n d t o orient this in the S E M so as t o
minimize competing image contrasts.
W i t h a r o u g h s a m p l e , it m a y b e a d v a n t a g e o u s t o
s t u d y m a g n e t i c c o n t r a s t b y t h e lock-in e n h a n c e m e n t
t e c h n i q u e . I n general, with t h e lock-in m e t h o d , t h e
idea is t o i n t r o d u c e a m o d u l a t i n g signal i n t o t h e
i m a g e - f o r m i n g p r o c e s s in s o m e w a y a n d t h e n t o detect
t h e resulting v a r i a t i o n s in t h e collected c u r r e n t with a
phase-sensitive d e t e c t o r . T h i s m e t h o d h a s also been
used extensively for r e c o r d i n g A u g e r electron spectra,
by a p p l y i n g t h e reference signal t o t h e energy-filtering
d e t e c t o r . It h a s also been applied t o t h e r m a l - w a v e
m i c r o s c o p y . T o a p p l y this m e t h o d t o m a g n e t i c c o n
trast, t h e excitation signal is applied t o m o v e t h e
d o m a i n walls in t h e specimen, either by a p p l y i n g a n
external field t o a thin-film s a m p l e o r by a p p l y i n g the
c u r r e n t t o t h e driving coil o f a thin-film m a g n e t i c
r e c o r d i n g h e a d (Fig. 5).

Scanning

Tunnelling

Microscopy

and

Spectroscopy

See also: Ceramic Materials: Cathodoluminescence Analy

sis; Electron Microscope Analysis of Defect Clusters, Voids
and Bubbles; Electron Microscopy, Analytical; Field-Ion
Microscopy: Atom-Probe Microanalysis
Bibliography
Goldstein J I, Yakowitz (eds.) 1975 Practical Scanning
Electron Microscopy: Electron and Ion Microprobe Analy
sis. Plenum, New York
Oatley C W 1972 The Scanning Electron Microscope, Part 1,
The Instrument. Cambridge University Press, Cambridge
Oatley C W 1982 The early history of the scanning electron
microscope. J. Appl. Phys. 53(2): R l - 1 3
Thornton R 1968 Scanning Electron Microscopy: Applica
tions to Materials and Device Science. Chapman and Hall,
London
Wells C, Boyde A, Lifshin E, Rezanowich A 1974
Scanning Electron Microscopy. McGraw-Hill, New York
Zworykin V K, Morton G A, Ramberg G, Hillier J, Vance
A W 1945 Electron Optics and the Electron Microscope.
Wiley, New York
O . C . Wells
[IBM, Y o r k t o w n Heights,
New York, USA]

Scanning Tunnelling Microscopy and

Spectroscopy
S c a n n i n g tunnelling m i c r o s c o p y ( S T M ) is a t e c h n i q u e
t h a t uses tunnelling electrons t o p r o d u c e threed i m e n s i o n a l real-space images of t h e surfaces of
materials. T h e t e c h n i q u e is as simple in c o n c e p t a s
stylus profilometry, yet it p r o v i d e s capabilities n o t
available with a n y o t h e r m e a s u r e m e n t m e t h o d . I n less
t h a n five years, S T M developed from a difficult
m e a s u r e m e n t p e r f o r m e d in a h a n d f u l of l a b o r a t o r i e s
a r o u n d t h e w o r l d i n t o a widely accepted m e t h o d of
surface c h a r a c t e r i z a t i o n . T h e excitement over this
surface-analysis m e t h o d , a n d its c o n s e q u e n t r a p i d
d e v e l o p m e n t , stem from t h e fact t h a t i n f o r m a t i o n is
o b t a i n e d a b o u t a t o m i c s t r u c t u r e a n d b o n d i n g in
solids a t u n p r e c e d e n t e d levels of spatial resolution.
T h r e e - d i m e n s i o n a l a t o m i c images c a n b e p r o d u c e d of
s e m i c o n d u c t o r s , semimetals a n d m e t a l s . I m a g i n g a n d
spectroscopic t e c h n i q u e s h a v e been used t o investig
ate surface r e c o n s t r u c t i o n s , a d s o r b a t e r e a c t i o n s a n d
c h a r g e density w a v e f o r m a t i o n , m a k i n g a n i m m e d i a t e
a n d d r a m a t i c i m p a c t in m a n y of t h e t r a d i t i o n a l a r e a s
of surface science. A s t h e t e c h n i q u e b e c o m e s m o r e
accessible, it is being applied t o issues of i m p o r t a n c e
in m a t e r i a l s science, such a s diffusion, n u c l e a t i o n
processes, fracture, fatigue, g r a i n - b o u n d a r y s t r u c t u r e
a n d so o n . I n parallel d e v e l o p m e n t s , a n u m b e r of
techniques b a s e d o n t h e s c a n n i n g t e c h n o l o g y o f S T M
(often referred t o as n e a r field o r s c a n n i n g p r o b e
microscopies) c a n n o w m e a s u r e a t o m i c forces, m a g
netic forces, t h e r m a l g r a d i e n t s a n d p h o t o n emission
with spatial resolution similar t o S T M .

oooo
. oooo
ooboooooo
ooooooooo
s

Sample

Figure 1
Schematic of tunnelling between the tip and sample in the
STM configuration: in constant current imaging the
sample-tip separation is held constant as the tip is
scanned over the sample surface; a series of scans
produces a real space image of constant charge density

/.

Fundamental

Principles

of

Imaging

S T M is t h e m o s t recent of a l o n g list of devices based

o n electron tunnelling t h a t includes: t h e field-ion
microscope, Esaki diodes, Zener diodes, Josephson
j u n c t i o n s a n d inelastic electron tunnelling spectros
c o p y . It w a s t h e earlier d e v e l o p m e n t of these t u n n e l
ling devices t h a t p r o v i d e d a theoretical f r a m e w o r k
t h a t c o u l d b e a l m o s t directly applied t o t h e S T M a t its
i n v e n t i o n . T o s u m m a r i z e this t h e o r y , consider elec
t r o n tunnelling in t h e general case.
A n infinite p o t e n t i a l energy b a r r i e r exists between
t w o p l a n a r surfaces s e p a r a t e d b y a large distance;
h o w e v e r , t h e b a r r i e r b e c o m e s finite w h e n t h e t w o
surfaces a r e in close p r o x i m i t y . W h e n a bias is applied
b e t w e e n t w o surfaces within s o m e n a n o m e t e r s of each
o t h e r , a statistically significant n u m b e r of electrons
with energies lower t h a n t h a t of t h e b a r r i e r will
n e g o t i a t e t h e energy barrier, p r o d u c i n g a " t u n n e l l i n g
c u r r e n t . " A l t h o u g h classically f o r b i d d e n , electron
tunnelling c a n b e explained within t h e w a v e - p a r t i c l e
d u a l i s m c o n c e p t of q u a n t u m m e c h a n i c s . T h e e q u a t i o n
for c u r r e n t resulting from electrons tunnelling
b e t w e e n t w o p l a n a r electrodes in t h e limit of low
t e m p e r a t u r e a n d low applied bias is:
/ = /(*.)

+ eV)]\Ms,\ d{E,

- Et) (1)

w h e r e M s t is t h e tunnelling m a t r i x , f(E) t h e F e r m i
function, e t h e c h a r g e of a n electron, h = h/2n w h e r e h
is P l a n c k ' s c o n s t a n t , a n d t h e subscripts s a n d t refer t o
the electrodes (later specified a s s a m p l e a n d tip,

427

Scanning

Tunnelling

Microscopy

and

Spectroscopy

respectively). T u n n e l l i n g , as it o c c u r s in the S T M
configuration, is described in Fig. 1. O n e electrode is a
metallic p o i n t p r o b e (the tip), the o t h e r a p l a n a r
s e m i c o n d u c t o r o r m e t a l (the sample). Tersoff a n d
H a m a n n (1985) h a v e t a k e n the g e o m e t r y of the S T M
a n d the electronic s t r u c t u r e of t h e tip i n t o c o n s i d e r a
tion a n d e v a l u a t e d the tunnelling m a t r i x in E q n . (1) t o
p r o d u c e a c u r r e n t e q u a t i o n specific t o the S T M .
A s s u m i n g a spherical w a v e function for the tip struc
t u r e a n d using r e a s o n a b l e values for the m a t e r i a l s
p a r a m e t e r s p e r t a i n i n g t o the tip, they o b t a i n for a
c o n s t a n t applied bias:

L ^ y ^ D ^ ^ l ^ d i E . - E )

(2)

in the limit of low t e m p e r a t u r e a n d applied bias,

(V), w h e r e Dt is the density of states of the tip; ,
the tunnelling barrier, is o n first a p p r o x i m a t i o n
R is the r a d i u s of c u r v a t u r e of the tip; is
(^s +
ll
the surface w a v e function; k = Qm(pf \h is the inverse
decay
length
of
the
wave
function.
Since
2
1/2
jV ocexp( - 2A;Z0? ), the tunnelling c u r r e n t at c o n
stant applied bias c a n be expressed in t e r m s of s a m
p l e - t i p s e p a r a t i o n as:

7 = C Z ) s e x p ( - 1.025 > )

(3)

where C is a c o n s t a n t specific t o tip m a t e r i a l a n d

g e o m e t r y a n d Ds is the s a m p l e density of states.
E q u a t i o n (1) e m p h a s i z e s t h a t the c o n t r a s t in the
image is a c o n v o l u t i o n of the electronic s t r u c t u r e of
the s a m p l e , the electronic s t r u c t u r e of the tip a n d the
tunnelling b a r r i e r function (related t o the surface
w o r k function). It is only w h e n the latter t w o c o n t r i
b u t i o n s are c o n s t a n t t h a t the v a r i a t i o n of c o n t r a s t in
the i m a g e c a n be a t t r i b u t e d t o electronic p r o p e r t i e s of
the sample. F o r t u n a t e l y , these c o n d i t i o n s c a n be
easily m e t o n m a n y materials; therefore, E q n . (2), in
which these a s s u m p t i o n s a r e implicit, is a r e a s o n a b l e
approximation.
T o p r o d u c e images, t h e S T M c a n be o p e r a t e d in
t w o m o d e s . I n " c o n s t a n t c u r r e n t " imaging, a feed
b a c k m e c h a n i s m is e n a b l e d w h i c h m a i n t a i n s a c o n
stant c u r r e n t while a c o n s t a n t bias is applied between
the sample a n d tip. A s seen in E q n s . (2) a n d (3), these
c o n d i t i o n s require a c o n s t a n t s a m p l e - t i p s e p a r a t i o n .
A s the tip is scanned over the s a m p l e , the vertical
position of the tip is altered to m a i n t a i n t h a t c o n s t a n t
s e p a r a t i o n . T h e signal required t o alter the vertical tip
position c o n s t r u c t s the i m a g e , w h i c h represents a
c o n s t a n t c h a r g e density c o n t o u r . Altering the level of
the c u r r e n t o r the applied bias p r o d u c e s c o n t o u r s of
different c h a r g e densities. A n alternative i m a g i n g
m o d e is " c o n s t a n t h e i g h t " o p e r a t i o n , in which c o n
s t a n t height a n d c o n s t a n t applied bias are s i m u l t a n
eously m a i n t a i n e d . T h e v a r i a t i o n in c u r r e n t is t h e n
m o n i t o r e d t o p r o d u c e t h e i m a g e as the tip scans the
428

s a m p l e surface. T h e r e are a d v a n t a g e s i n h e r e n t in b o t h
m o d e s of o p e r a t i o n ; the former p r o d u c e s c o n t r a s t
directly related t o electron c h a r g e density profiles,
while the latter p r o v i d e s for faster scan rates n o t being
limited by t h e r e s p o n s e time of the vertical driver.
I m a g e d a t a will be displayed differently, d e p e n d i n g o n
the i n f o r m a t i o n required. A s a n e x a m p l e , Fig. 2
illustrates the line scan, p l a n view a n d threed i m e n s i o n a l r e n d e r i n g of a n a t o m i c resolution c o n
s t a n t c u r r e n t i m a g e of the basal p l a n e of highly
o r i e n t e d pyrolytic g r a p h i t e . A t o m i c r e s o l u t i o n images
are possible only u n d e r o p t i m i z e d s a m p l e a n d tip
conditions. Larger sample-tip separations and blunt
tips h a v e t h e effect of s m e a r i n g the localized s t r u c t u r e
a n d p r o d u c e t o p o g r a p h i c images w i t h s o m e w h a t
lower resolution.

2. Tunnelling

Spectroscopy

T u n n e l l i n g s p e c t r o s c o p y (TS) p e r f o r m e d in the S T M
p r o v i d e s i n f o r m a t i o n a b o u t t h e electronic s t r u c t u r e of
the s a m p l e by p r o b i n g the s a m p l e density of states as
a function of energy. T h e c o n c e p t is similar t o t r a d i
tional s a n d w i c h j u n c t i o n spectroscopy (inelastic elec
t r o n tunnelling spectroscopy, H a n s m a (1982)), the
p r i m a r y differences being t h a t a v a c u u m g a p exists
b e t w e e n the t w o electrodes r a t h e r t h a n a n i n s u l a t o r
a n d only elastic processes h a v e been m o n i t o r e d t o
d a t e . T h e r e a r e also t w o m e t h o d s of p e r f o r m i n g T S .
T h e first, referred t o as p o i n t spectroscopy, involves
m o v i n g the tip t o a feature of interest, disengaging the
feedback m e c h a n i s m , m o d u l a t i n g the tip bias a n d
r e c o r d i n g the resulting v a r i a t i o n in c u r r e n t . T h e idea
lized b a n d s t r u c t u r e in Fig. 3 schematically illustrates
c u r r e n t flow in this situation. W h e n a bias is applied
b e t w e e n the s a m p l e a n d tip, the F e r m i levels of the
t w o m a t e r i a l s a r e displaced with respect t o each o t h e r
allowing electrons within the energy w i n d o w t o tra
verse the v a c u u m g a p . A s the bias is r a m p e d , either
positively o r negatively, the c u r r e n t varies in response
t o the c h a n g i n g electron density in the energy win
d o w . R a m p i n g in b o t h directions p r o b e s b o t h the
occupied a n d u n o c c u p i e d energy states, with the
m a g n i t u d e of the c u r r e n t at a specific voltage directly
related t o the density of states of the sample a t t h a t
energy. Since the c o n s t a n t C in E q n . (3) is a linear
function of voltage, s p e c t r o s c o p y d a t a c a n be related
t o the s a m p l e electronic s t r u c t u r e Ds in the f o r m of
conductance:
I/V=

/2

C*DS e x p ( - 1.025 )

(4)

a n d voltage derivatives thereof. T h e second m e t h o d

of o b t a i n i n g spectroscopic i n f o r m a t i o n involves sim
u l t a n e o u s l y collecting images at v a r i o u s biases. T h i s
c a n be a c c o m p l i s h e d b y m o d u l a t i n g the bias at a high
frequency (with respect t o the time c o n s t a n t of the
feedback controller) a n d r e c o r d i n g t h e c u r r e n t a t

Scanning

Tunnelling

Microscopy

- T i p vacuum

and

Spectroscopy

sample
Surface

BuLk

(a)

+ Tip vacuum

sample
Surface

Bulk

(b)

Figure 3
Idealized representation of the electronic structure of the
sample and tip: Et is the Fermi energy, Ey the valence
band edge, and Ec the conduction band edge; the tip is
modelled as a metal left, the sample as a semiconductor
right; states on the sample surface may be due to surface
reactions or extensions of midgap bulk states; a bias AV
between the sample and tip displaces the Fermi levels with
respect to each other, allowing electrons within the energy
window to traverse the vacuum gap

Figure 2
Comparison of image display modes showing (a) a line
scan, (b) plan view and (c) a three-dimensional rendering
of a constant current image of highly oriented pyrolytic
graphite acquired in air

several discrete values of a p p l i e d bias d u r i n g a scan o r

b y u s i n g t h e s a m e s a m p l e a n d h o l d m e t h o d of p o i n t
s p e c t r o s c o p y a t every i m a g e p o i n t . T h e s i m u l t a n e o u s
collection of m u l t i p l e i m a g e s is s o m e t i m e s referred t o
as c u r r e n t i m a g i n g tunnelling s p e c t r o s c o p y , C I T S . A
c o m p a r i s o n of t h e p e r i o d i c c o n t r a s t in such images
with a t o m i c c h a r g e s u p e r p o s i t i o n a n d t o t a l energy
c a l c u l a t i o n s identifies t h e spatial p o s i t i o n of energy
states (i.e., b o n d s ) with respect t o t h e lattice.
S T M h a s been used extensively in t h e c h a r a c t e r i z a
tion of t h e silicon (111) surface, t o t h e p o i n t t h a t the
(7 x 7) r e c o n s t r u c t i o n of this surface is n o w univer
sally associated with t h e t e c h n i q u e . T h i s familiar
s t r u c t u r e c a n be used t o illustrate b o t h p o i n t spectros
c o p y a n d C I T S of s e m i c o n d u c t o r s . A n e x a m p l e of
p o i n t s p e c t r o s c o p y is given in F i g . 4 w h i c h is t a k e n
from a s t u d y of a l u m i n u m a d s o r p t i o n o n silicon (111)
b y H a m e r s a n d D e m u t h (1988). T h e electronic struc
t u r e of t h e silicon (111) 7 x 7 surface d e t e r m i n e d by
T S is c o m p a r e d w i t h t h a t d e t e r m i n e d by ultraviolet
p h o t o e m i s s i o n a n d inverse p h o t o e m i s s i o n . O c c u p i e d
states a t - 1.6 eV, - 0.85 eV a n d - 0.1 eV, a n d u n o c 429

Scanning

Tunnelling

Microscopy

and

Spectroscopy

3. Microscope

Design

Considerations

T h e h e a r t of a s c a n n i n g tunnelling m i c r o s c o p e c o n
sists of a s c a n n e r a n d a s a m p l e - t i p a p p r o a c h m e c h a n
ism. S c a n n i n g tunnelling m i c r o s c o p e s a r e divided i n t o
t w o classes b a s e d o n t h e configuration of t h e m e c h a n
ism t h a t c o n t r o l s t h e tip. T h e s c a n n e r s a r e m a d e of
piezoelectric elements w h i c h e x p a n d o n a p p l i c a t i o n of
a n electric field, h e n c e the tip c a n be s c a n n e d by
r a m p i n g t h e voltage applied t o t h e different piezoelec
tric elements. F i g u r e 6 schematically illustrates a
s c a n n e r m a d e of three o r t h o g o n a l b a r s a n d o n e m a d e
of a cylinder. E a c h t y p e of s c a n n e r h a s a d v a n t a g e s .
T h e o r t h o g o n a l a r r a n g e m e n t is m o r e linear by virtue
of g e o m e t r y a n d , c o n s e q u e n t l y , requires n o c o m p e n
s a t i o n t o e n s u r e a s q u a r e scan a r e a . T h e cylindrical
s c a n n e r s a r e m o r e stable with respect t o m e c h a n i c a l
v i b r a t i o n s , as indicated b y t h e m e c h a n i c a l r e s o n a n c e

Energy

(eV)

Figure 4
Comparison of density of states by TS point spectroscopy
with photoemission and inverse photoemission spectra;
agreement between various methods verifies the accuracy
of TS data (redrawn after Tromp et al. 1985)

cupied states at + 0.5 eV a n d + 1.6 eV, a r e c h a r a c t e r

istic of the stacking fault a d a t o m s t r u c t u r e of t h e
7 x 7 r e c o n s t r u c t i o n . T h e s e states a r e evident in T S
a n d in p h o t o e m i s s i o n results. T h e excellent a g r e e m e n t
between the energies of the states identified in the T S
s p e c t r u m a n d t h o s e d e t e r m i n e d from p h o t o e m i s s i o n
results illustrates t h e a c c u r a c y w i t h w h i c h tunnelling
spectra characterize surface electronic s t r u c t u r e s . T h e
m e a s u r e m e n t s average over a n a r e a larger t h a n a u n i t
cell a n d each state c o r r e s p o n d s t o t h e energy of a
p a r t i c u l a r b o n d . F o r e x a m p l e , the state a t 0.8 eV
arises from the d a n g l i n g b o n d , w h e r e a s t h e state
a t 1.6 eV c o r r e s p o n d s t o t h e silicon b a c k b o n d .
N a t u r a l l y , the b o n d s a r e localized a t different posi
tions with respect t o t h e a t o m i c lattice; therefore,
images of these states h a v e different geometries b u t
should h a v e the s a m e t r a n s l a t i o n as t h e u n i t cell.
F i g u r e 5 is a schematic r e p r e s e n t a t i o n of c u r r e n t
images t h a t w o u l d b e p r o d u c e d b y C I T S a t + 0.7 eV
a n d - 1.8 eV. N o t e t h a t the features in t h e i m a g e s
a p p e a r quite different b u t d o h a v e the lateral transla
tion of the u n i t cell. I m a g e s i m u l a t i o n s b a s e d o n
theoretical c a l c u l a t i o n s a r e necessary t o i n t e r p r e t
a t o m i c r e s o l u t i o n images; t h a t is, t o relate the features
in the i m a g e t o b o n d types a n d a t o m p o s i t i o n s .

430

Figure 5
Schematic representation of CITS images that would be
obtained at (a) + 0.5 V and (b) - 1.6 V applied bias on
the silicon ( 1 1 1 ) 7 x 7 surface: the unit cell of the
reconstruction is outlined in white (note that the bonding
states occupied by electrons (a) and those not occupied
(b) are in different positions within the unit cell)

Scanning

Tunnelling

Microscopy

and

Spectroscopy

v i b r a t i o n . T u n n e l l i n g c u r r e n t s a r e of t h e o r d e r of 0 . 1 10 A a n d t h e s a m p l e - t i p j u n c t i o n acts like a n
a n t e n n a t o a m b i e n t electric fields; therefore, t h e
m i c r o s c o p e m u s t be effectively shielded a n d electri
cally isolated from external circuits. A t o m i c resolu
tion requires stability of 0.01 n m with respect t o
m e c h a n i c a l v i b r a t i o n s . M e c h a n i c a l noise a t t e n u a t i o n
is achieved b y c o m b i n i n g a series of d a m p i n g stra
tegies. A t a b l e floating o n p n e u m a t i c (air) legs o r
s u s p e n d e d b y l o n g springs will d a m p low-frequency
v i b r a t i o n s ( 0 . 1 - 1 0 0 H z ) . A l t e r n a t i n g stacks of m e t a l
a n d r u b b e r , o r a n y t w o m a t e r i a l s w i t h widely differing
elastic c o n s t a n t s , d a m p m i d r a n g e frequencies ( 5 0 300 H z ) . H i g h e r - f r e q u e n c y v i b r a t i o n s c a n b e elimi
n a t e d b y electrical filtering.

Figure 6
Schematic illustration of orthogonal and cylindrical
arrangements for the piezoelectric elements which move
the STM tip: x, y and refer to the direction of motion
when the controlling voltage is applied as shown

of 12-20 H z c o m p a r e d w i t h 2 - 7 H z for t h e o r t h o g o
nal scanner, b u t a r e intrinsically n o n l i n e a r a n d re
q u i r e h a r d w a r e o r software c o m p e n s a t i o n d u r i n g
scanning. S c a n n e r s a r e c o n t r o l l e d t h r o u g h simple
voltage amplifiers a n d a s t a n d a r d feedback circuit b y
a P C size c o m p u t e r . T h e s e c o n d i m p o r t a n t aspect of
the m i c r o s c o p e design is t h e m e c h a n i s m for b r i n g i n g
t h e s a m p l e a n d tip t o g e t h e r . A s t u n n e l l i n g o c c u r s only
in close p r o x i m i t y t o t h e surface (within 3 n m ) t h e
a p p r o a c h system m u s t b e c a p a b l e of precise r e p r o d u c
ible i n c r e m e n t a l steps of less t h a n 3 n m in o r d e r t o
avoid t i p - t o - s a m p l e c o n t a c t . O n e m e t h o d of s a m p l e tip a p p r o a c h is b a s e d o n differential springs o r levers,
w h e r e t h e sensitivity (i.e., t h e smallest step) is deter
m i n e d b y t h e r a t i o of s p r i n g c o n s t a n t s , o r lengths of
levers, respectively. Electrostrictive w a l k e r s , referred
to as " l o u s e s , " a r e also used. Recently, s t e p p e r m o t o r s
h a v e been d e v e l o p e d with e n o u g h precision t o p r o v i d e
c o n t r o l l e d s a m p l e - t i p a p p r o a c h ; h o w e v e r , these
usually h a v e t h e d i s a d v a n t a g e of n o t being c o m
patible with u l t r a h i g h - v a c u u m ( U H V ) systems. A
general design c o n s i d e r a t i o n is w h e t h e r t h e m i c r o
scope will be c o m p a t i b l e with U H V systems. S u c h
systems p r o v i d e a n e n v i r o n m e n t in w h i c h t o c a r r y o u t
c o n t r o l l e d c h e m i s t r y o n a t o m i c a l l y clean s a m p l e s .
U n d e r these c i r c u m s t a n c e s , i m a g e s a n d T S c a n often
be directly i n t e r p r e t e d . C o m p a t i b i l i t y with U H V im
poses restrictions o n m a t e r i a l choices for s o m e of t h e
components. Commercial microscopes are currently
available for use in a m b i e n t a n d in U H V .
The primary obstacle to attaining atomic resolution
is t h a t i m p o s e d b y electrical noise a n d m e c h a n i c a l

4. Sample

and Tip

Preparation

N o special p r e p a r a t i o n is r e q u i r e d for S T M analysis

in air; h o w e v e r , u n d e r these c o n d i t i o n s o p t i m u m
r e s o l u t i o n is usually n o t a t t a i n e d . T h e exception is
cleaved surfaces of highly o r i e n t e d pyrolitic g r a p h i t e ,
w h i c h a r e often successfully i m a g e d a t a t o m i c resolu
tion in air, as w a s illustrated in F i g . 6. O n m a t e r i a l s
n o t c o n d u c i v e t o a t o m i c i m a g i n g in air, i m a g i n g a t
levels s o m e w h a t lower t h a n a t o m i c r e s o l u t i o n p r o v e s ,
nevertheless, t o b e useful for a large n u m b e r of
a p p l i c a t i o n s . A t o m i c r e s o l u t i o n of s e m i c o n d u c t o r s
such as silicon, gallium a r s e n i d e a n d g e r m a n i u m
requires t h a t clean surfaces b e p r o d u c e d in U H V
c o n d i t i o n s . T h i s is achieved b y in situ cleaving t o
e x p o s e t h e desired surface, o r b y a series of h e a t i n g
a n d i o n - e t c h i n g steps. T h e specific c o n d i t i o n s for the
s a m p l e d e p e n d o n t h e s t r u c t u r e expected o n t h a t
p a r t i c u l a r surface. Similarly, m e t a l s a m p l e surfaces
c a n b e cleaned in situ b y h e a t i n g a n d ion milling.
It h a s been b o t h theoretically a n d experimentally
d e m o n s t r a t e d t h a t t h e g e o m e t r y a n d c h e m i s t r y of t h e
a t o m s a t t h e e n d of the S T M tip affect the i m a g e . A
clean s h a r p tip is critical t o a t t a i n i n g o p t i m u m resolu
tion and unambiguous image interpretation. S T M
tips c a n b e m a d e of a variety of m e t a l s , t h e choice
d e p e n d i n g o n t h e a p p l i c a t i o n . T u n g s t e n tips a r e
favored for i m a g i n g b e c a u s e of their stiffness. T h e y
a r e f o r m e d b y m e c h a n i c a l s h a r p e n i n g with a s t a n d a r d
g r i n d i n g m e d i u m such as 600 grit SiC p a p e r , o r by
electrochemically etching, using N a O H o r K O H in a
d c o r a c electric field. I n o r d e r t o p e r f o r m T S , further
in situ cleaning is necessary t o r e m o v e t h e native oxide
o n t h e t u n g s t e n , o t h e r w i s e t h e spectra will include a
c o n t r i b u t i o n from t h e o x i d e - m e t a l interface o n t h e tip
t h a t will interfere w i t h d e t e r m i n a t i o n of t h e electronic
s t r u c t u r e of t h e s a m p l e . O t h e r refractory m e t a l s a r e
often used t o a v o i d this p r o b l e m , even t h o u g h they
a r e n o t a s stiff as t u n g s t e n , t h e m o s t c o m m o n being
gold, p l a t i n u m a n d p l a t i n u m alloys. T h e s e tips a r e
f o r m e d simply b y c u t t i n g with precision wire cutters.
431

Scanning

Tunnelling

Microscopy

and

Spectroscopy

F o r use in U H V a n d t o o p t i m i z e r e s o l u t i o n , a t m o s
pheric c o n t a m i n a t e s a r e r e m o v e d from the tip by:
(a)

b a c k i n g the tip o u t of tunnelling r a n g e , a p p l y i n g

a high voltage ( 2 0 - 3 0 0 V) t o i n d u c e a n emission
c u r r e n t for a p e r i o d of a few s e c o n d s to several
minutes;

(b)

in situ electron o r ion b o m b a r d m e n t ; o r

(c)

in situ h e a t i n g t o relatively high t e m p e r a t u r e s .

5. Applications

in Materials

Science

S T M h a s been used extensively in t h e s t u d y of silicon,

g e r m a n i u m , gallium arsenide, gold, p a l l a d i u m a n d
g r a p h i t e ( F e e n s t r a 1988). It h a s been useful, n o t only
in d e t e r m i n i n g the g e o m e t r i c a n d electronic s t r u c t u r e s
of v a r i o u s surfaces of these m a t e r i a l s , b u t also in
monitoring structure and bonding during adsorbate
reactions. A l t h o u g h it is for t h e analysis of these
surfaces t h a t S T M is widely k n o w n , it h a s been
applied t o a m u c h wider r a n g e of m a t e r i a l s . Five
studies t h a t illustrate the v a r i o u s m e a s u r e m e n t s p o s
sible in S T M a n d their relevance t o m a t e r i a l s in
vestigations a r e s u m m a r i z e d in this section. T h e s e
examples e m p h a s i z e several i m p o r t a n t p o i n t s in t h e
a p p l i c a t i o n of S T M . W h i l e there is n o d o u b t t h a t t h e
t e c h n i q u e is powerful w h e n o p e r a t e d a t a t o m i c resolu
tion, v a l u a b l e i n f o r m a t i o n is often gained a t resolu
tions of 0.4-0.5 n m , which is o r d e r s of m a g n i t u d e
higher t h a n t h e spatial r e s o l u t i o n achieved b y o t h e r
surface c h a r a c t e r i z a t i o n m e t h o d s b u t n o t q u i t e a t o
mic S T M i m a g i n g . T u n n e l l i n g s p e c t r o s c o p y is as
powerful as S T M i m a g i n g , p e r h a p s even m o r e so, a n d
barrier height m e a s u r e m e n t s a n d local c a p a c i t a n c e
m e a s u r e m e n t s m a y h a v e a similar i m p a c t o n future
investigations. T h e digital n a t u r e of t o p o g r a p h i c im
ages allows c o m p l e x m a t h e m a t i c a l analysis of surface
s t r u c t u r e with relative ease. A s the descriptions of
these studies a r e necessarily brief, the r e a d e r is
referred t o t h e original p a p e r s for c o m p l e t e discus
sions of e x p e r i m e n t a l details.
5.1 Structure of Defects on Silicon
A large fraction of a t o m i c level S T M analysis t o d a t e
h a s involved c o n v e n t i o n a l s e m i c o n d u c t o r m a t e r i a l s ,
particularly silicon. T h e directional b o n d i n g in these
m a t e r i a l s strongly affects the s t r u c t u r e of surfaces. A n
ideally t e r m i n a t e d surface w o u l d c o n t a i n unsatisfied
b o n d s in a system t h a t favors t e t r a h e d r a l c o o r d i n a
tion. This is such a high-energy s i t u a t i o n t h a t these
d a n g l i n g b o n d s interact with e a c h o t h e r t o reduce t h e
surface energy a n d c a n , t h e r e b y , p r o d u c e a surface
a t o m i c s t r u c t u r e with a periodicity larger t h a n t h a t of
the bulk. W h e n the relaxation results in a p e r i o d i c
s t r u c t u r e , t h e surfaces a r e said t o be " r e c o n s t r u c t e d "
(Zangwill 1988). A l t h o u g h large a r e a s a r e r o u t i n e l y
p r o d u c e d with h o m o g e n e o u s l y r e c o n s t r u c t e d sur432

Figure 7
Constant current image of reconstructed silicon (001)
surface with several defects and spatially resolved I-V
spectra showing the variation in the surface bandgap with
lateral position (courtesy of Hamers 1989)

faces, v a c a n c y defects a n d d o m a i n b o u n d a r i e s a r e
invariably o b s e r v e d . T h e use of a t o m i c r e s o l u t i o n T S
t o p r o b e t h e electronic s t r u c t u r e of these defects
directly is illustrated in Fig. 7 ( H a m e r s 1989). I-V
curves a c q u i r e d a t different lateral p o s i t i o n s n e a r a
v a c a n c y type defect a r e s h o w n with the c o n s t a n t
c u r r e n t i m a g e of t h e surface (acquired a t - 1.5 eV).
A w a y from t h e defect (Fig. 7) t h e I-V curves indicate
t h e presence of a surface b a n d g a p b y t h e s h a r p
turn-on
of
tunnelling
current
n e a r - 0.45 eV
a n d + 0.25 eV. N e a r t h e defect t h e s h a r p edges d i s a p
p e a r a n d directly over the defect (Fig. 7) t h e t u n n e l
ling c u r v e exhibits a n e x p o n e n t i a l increase in c u r r e n t
b o t h a b o v e a n d below t h e F e r m i level. T h i s b e h a v i o r
d e m o n s t r a t e s t h a t t h e defect causes a v a r i a t i o n in t h e
local density of states; t h a t is, a h i g h density of states
exists a t t h e F e r m i level d u e t o the presence of a
v a c a n c y . T h e spatially d e p e n d e n t m e a s u r e m e n t s also
p r o v i d e a direct m e a s u r e of t h e lateral extent of t h e
w a v e f u n c t i o n s associated with defects a n d impurities,
d e m o n s t r a t i n g t h a t t h e influence of t h e defect e x t e n d s
over 1.5 n m from its c o r e . T h i s local electronic struc
t u r e is directly related t o chemical reactivity. T h e s e
v a c a n c y sites a r e , therefore, expected t o b e m o r e
c o n d u c t i v e , o r less c o n d u c i v e , t o i n t e r a c t i o n w i t h
a t o m s in t h e vicinity of t h e surface t h a n t h e defect-free
surface. Several studies a l o n g this line h a v e investi
g a t e d site-specific c h e m i s t r y o n s e m i c o n d u c t o r sur
faces.

5.2 Growth Facets on Silicon Carbide Single

Crystals
A simple m e t h o d of p r o d u c i n g silicon c a r b i d e (SiC)
t h a t involves h e a t i n g silica a n d c o k e t o high t e m p e r a -

Scanning

Figure 8
Constant current image of 25 nm square area of SiC
observed in moderate vacuum (10" 7 torr): facets resulting
from the crystal growth mechanism are identified

tures is referred t o as t h e A c h e s o n m e t h o d after its

i n v e n t o r . D u r i n g t h e p r o c e s s single crystals n u c l e a t e
o n seed particles a n d g r o w , usually in t h e presence of
n u m e r o u s i m p u r i t i e s , p r o d u c i n g highly d o p e d m i x e d modification crystals. T h e m o s t c o m m o n i m p u r i t i e s
a r e a l u m i n u m a n d n i t r o g e n w h i c h i n d u c e n- a n d ptype c o n d u c t i v i t y , respectively, a n d c a n be c o m p e n
sating w h e n p r e s e n t s i m u l t a n e o u s l y . T h e s e crystals
provide an opportunity to study growth mechanisms.
T h e S T M i m a g e in F i g . 8 c h a r a c t e r i z e s the surface of
a n o m i n a l l y 6 H modification crystal parallel to t h e
basal p l a n e . G r o w t h facets a r e o b s e r v e d with t h e
vertical d i m e n s i o n of o n e u n i t cell a n d a lateral
d i m e n s i o n of 2 - 3 u n i t cells. T S d a t a a r e also s h o w n as
they a r e a c q u i r e d in t h e f o r m of I-V curves, as
c o n d u c t a n c e w h i c h is t h e first derivative, a n d as
n o r m a l i z e d c o n d u c t a n c e w h i c h is t h e l o g a r i t h m i c der
ivative of these curves (Fig. 9). T h r e e m i d g a p states
are o b s e r v e d in t h e t u n n e l l i n g n o r m a l i z e d c o n d u c
t a n c e s p e c t r u m : a t + 0.3 eV, - 0.45 eV a n d - 0.80 eV.
A l t h o u g h t h e p e a k intensities v a r y , t h e energies of t h e
p e a k s a r e r e p r o d u c i b l e . T h e s e energies c o r r e s p o n d t o
o n e occupied a n d t w o u n o c c u p i e d states, a n d a r e
consistent with t h o s e expected from a l u m i n u m a n d
nitrogen doping.
5.3 Adsorbate Effects on the Electronic Structure of
Zinc Oxide
Zinc oxide ( Z n O ) , t h e m o s t ionic of t h e w u r t z i t e
s e m i c o n d u c t o r s , finds m a j o r a p p l i c a t i o n s in catalysis

Tunnelling

Microscopy

and

Spectroscopy

a n d as v a r i a b l e resistors. It is a m e t a l excess defect

s t r u c t u r e exhibiting -type c o n d u c t i v i t y with a b a n d g a p of 3.34 eV. T h e s t r u c t u r e of internal interfaces in
polycrystalline Z n O a n d t h e surface reactivity (i.e.,
effectiveness in catalyzing reactions) d e p e n d strongly
o n t h e a t o m i c a n d electronic s t r u c t u r e of t h e original
surfaces. T h e a d s o r p t i o n of m o l e c u l a r species in the
a t m o s p h e r e o n t o Z n O surfaces is k n o w n t o affect its
electronic s t r u c t u r e a n d t h u s surface reactivity ( G o p e l
1985). A l t h o u g h S T M c a n c h a r a c t e r i z e j u s t such
r e a c t i o n s , its a p p l i c a t i o n t o oxides w a s only recently
d e m o n s t r a t e d (Bonnell a n d C l a r k e 1988). I m a g i n g ,
s p e c t r o s c o p y a n d t u n n e l b a r r i e r height m e a s u r e m e n t s
were used t o m o n i t o r these surface r e a c t i o n s at a t o m i c
levels of spatial r e s o l u t i o n in a n S T M . It w a s f o u n d
t h a t stable i m a g i n g in air resulted only w h e n t u n n e l
ling o u t of t h e Z n O (i.e., s a m p l e biased negatively
with respect t o the tip) w h e n i m a g e d in air. T h e facets
o n this surface, s h o w n in Fig. 10, r a n g e from 1-7 n m .
Rectification evident in t h e t u n n e l l i n g s p e c t r u m is
typical of S c h o t t k y b a r r i e r f o r m a t i o n in -type semi
c o n d u c t o r s . I n c r e a s e d c o n d u c t a n c e a t lower energies
is evidence of t h e valence b a n d edge, b u t the c o n
d u c t i o n b a n d edge is n o t o b s e r v e d . T h e s e results de
m o n s t r a t e t h a t , w h e n a j u d i c i o u s choice of i m a g i n g
c o n d i t i o n s is m a d e , i m a g i n g of oxides even in the
presence of a S c h o t t k y b a r r i e r a t the s a m p l e - t i p
j u n c t i o n is possible. I n c o n t r a s t t o t h e results in air,
t h e surface is in flat b a n d c o n d i t i o n w h e n e x a m i n e d in
a v a c u u m of 1 0 " 9 t o r r , as i n d i c a t e d by t h e tunnelling
s p e c t r u m , w h e r e b o t h t h e valence a n d c o n d u c t i o n
b a n d edges a r e detected. U n d e r these c o n d i t i o n s
a t o m i c r e s o l u t i o n is possible, as s h o w n by the i m a g e
of a Z n O (lOTO) n o n p o l a r surface in Fig. 10. T h i s
d r a m a t i c difference in surface electronic s t r u c t u r e of
Z n O from t h a t w h i c h o c c u r s in air is a direct result of
c h a n g e s in surface c h e m i s t r y . By m e a s u r i n g t h e
c h a n g e in t u n n e l l i n g c u r r e n t t h a t results from a varia
t i o n in s a m p l e - t i p s e p a r a t i o n ( / vs in E q n . (3)), a n
" a p p a r e n t " t u n n e l b a r r i e r height c a n be d e t e r m i n e d .
T h i s b a r r i e r height is, in principle, related t o the
s a m p l e surface w o r k function. T h e m a g n i t u d e of the
c h a n g e in local surface w o r k function of Z n O deter
m i n e d in t h e S T M ( n o t s h o w n here) is consistent with
m a c r o s c o p i c m e a s u r e m e n t s m a d e in d e s o r p t i o n stud
ies a n d A u g e r analysis of t h e s a m e surfaces verifies t h e
c h a n g e in surface c h e m i s t r y (Fig. 11). T h i s e x a m p l e
illustrates t h e variety of m e a s u r e m e n t s possible in
S T M w h i c h c a n be exploited t o s t u d y local surface
chemistry.

5.4 Conductive

Polymers

D u r i n g t h e 1980s, a n e w class of p o l y m e r i c m a t e r i a l s
h a s been d e v e l o p e d h a v i n g electrical conductivities
c o m p a r a b l e t o t h a t of c o p p e r . In the polyaniline
family of p o l y m e r s , t h e d o p i n g m e c h a n i s m is such
t h a t b o t h t h e n u m b e r of p r o t o n s a n d t h e electrons c a n
be varied i n d e p e n d e n t l y b y c o n t r o l l e d chemical reac-

433

Scanning

Tunnelling

Microscopy

and

Spectroscopy

Tunnelling b i a s tl /
-1.4

1.4 -I . 4

-1.4

1.4 - 1 . 4

Energy

(V)
1.4 -I . 4

1.4

1.4 - 1 . 4

1.4

(eV)

Figure 9
Tunnelling spectra from the SiC surface shown in Fig. 8: (a)-(c) show the current-voltage data as they are acquired;
spectra are often displayed as conductance (d)-(f) or normalized conductance (g)(i); spectra were acquired at three
sample-tip separations (increasing from left to right) and the positions of the peaks marked by the arrows are consistent
at all separations

tion. I n t h e " e m e r a l d i n e " o x i d a t i o n state of p o l y a n i line, t h e n u m b e r of p r o t o n s is systematically altered

while t h e n u m b e r of electrons r e m a i n s c o n s t a n t o n
d o p i n g (by r e a c t i o n with a p r o t o n i c acid). T h e m o d e l s
i n v o k e d t o describe t r a n s p o r t p r o p e r t i e s in c o n d u c t i v e
p o l y m e r s rely o n t h e presence of localized m i d g a p
states d u e t o v a r i a t i o n s in b o n d o r d e r . A necessary
feature of t h e p r o p o s e d c o n d u c t i o n m o d e l s for this
m a t e r i a l is t h a t t h e electronic s t r u c t u r e of partially
r e a c t e d e m e r a l d i n e varies spatially, w i t h t h e scale of
v a r i a t i o n e s t i m a t e d a t tens of n a n o m e t e r s . W h i l e
m e a s u r e m e n t s of electrical b e h a v i o r p r o v i d e indirect
evidence for this spatial v a r i a t i o n of electronic struc
t u r e , T S is t h e only m e t h o d for direct m e a s u r e m e n t .
F i g u r e 12 illustrates t h e t o p o g r a p h i c s t r u c t u r e of spinc o a t e d e m e r a l d i n e h y d r o c h l o r i d e films (Bonnell a n d

434

A n g e l o p o u l o s 1989). T h e t o p o g r a p h i c s t r u c t u r e is
related t o p r o c e s s i n g c o n d i t i o n s a n d , d u e t o its scale,
c o u l d n o t be detected in extensive s c a n n i n g electron
m i c r o s c o p y ( S E M ) analysis. T h e m a t e r i a l is a m o r
p h o u s ; therefore, i n f o r m a t i o n a b o u t a t o m i c b o n d i n g
is n o t expected from t h e S T M i m a g e s . T h e different
types of electronic s t r u c t u r e f o u n d in fully a n d p a r
tially d o p e d e m e r a l d i n e h y d r o c h l o r i d e a r e also c o m
p a r e d in F i g . 13. T h e first t y p e of b e h a v i o r a p p e a r s
s e m i c o n d u c t i n g ; t h e p o s i t i o n of t h e valence (v) a n d
c o n d u c t i o n (c) b a n d edges is indicated b y a decrease
in c o n d u c t a n c e n e a r - 2.1 eV a n d a n increase in c o n
d u c t a n c e n e a r 2.2 eV, respectively. T h e b a n d g a p
d e t e r m i n e d b y T S (4.3 eV) agrees r e a s o n a b l y with t h a t
d e t e r m i n e d b y optical m e t h o d s (4.1 eV). I n t h e s e c o n d
t y p e of region, t h e b a n d edges c a n n o t be identified

Scanning

Tunnelling

Microscopy

and

Spectroscopy

140.0

4.0

-4.0

-3.0

-2.0

-1.0

1.0

2.0

3.0

4.0

T u n n e l l i n g bias (V)
(a)

Figure 10
A comparison of the resolution of topographic imaging of ZnO in (a) air and (b) UHV with the electronic structure
determined by tunnelling spectroscopy; Schottky barrier formation occurs in air as indicated by the variation in the
position of the valence band edge at three different sample-tip separations and the rectified I-V characteristics shown in
the inset; flat band conditions result in UHV, indicated by the observation of both the valence and conduction band edges

a n d t h e electronic s t r u c t u r e a p p e a r s metallic (conti

n u o u s l y increasing c o n d u c t a n c e over 3 eV w i t h n o
m e a s u r a b l e b a n d g a p ) . T h e t h i r d type of region also
h a s a b a n d g a p of a b o u t 4.3 eV a n d a significant state
o c c u p a t i o n a p p e a r s t o be c o n t i n u o u s from t h e t o p of
the valence b a n d t o a b o u t 1.0 eV a n d a n a d d i t i o n a l
u n o c c u p i e d state is clearly resolved a b o u t 1.0 eV
below t h e c o n d u c t i o n b a n d ( b o t h m a r k e d d ) . T h e s e
results p r o v i d e t h e first direct m e a s u r e m e n t of spatial
v a r i a t i o n of electronic s t r u c t u r e in a c o n d u c t i n g
p o l y m e r in s u p p o r t of electron t r a n s p o r t m o d e l s for
these systems.
5.5 Commercial
Applications
In a d d i t i o n t o m a k i n g a n i m p a c t as a research t o o l ,
S T M is b e g i n n i n g t o be exploited in c o m m e r c i a l
a p p l i c a t i o n s such as process c o n t r o l a n d c a l i b r a t i o n .

N o n d e s t r u c t i v e e v a l u a t i o n of t h e smallest structures
c u r r e n t l y m a n u f a c t u r e d is n o t possible with o t h e r
t e c h n i q u e s . A n e x a m p l e is illustrated in the S T M
i m a g e s of Fig. 14 w h i c h s h o w a diffraction g r a t i n g a n d
a n i n t e g r a t e d circuit. T h e diffraction g r a t i n g acts as a
p r i s m t o disperse light a n d is a n i n t e r n a l c o m p o n e n t
of infrared s p e c t r o m e t e r s . S E M lacks t h e vertical
r e s o l u t i o n a n d i n t e r f e r o m e t r y lacks t h e lateral resolu
tion t o c h a r a c t e r i z e t h e t o p o g r a p h y of the diffraction
g r a t i n g ; h o w e v e r , F i g . 14a illustrates h o w easily the
surface s t r u c t u r e of the t o p a n d sides of this 1
g r a t i n g is c h a r a c t e r i z e d with S T M . A second e x a m p l e
of S T M use in d e v e l o p i n g m a n u f a c t u r i n g processes is
given in t h e i m a g e of a n i n t e g r a t e d circuit (Fig. 14b).
S T M c a n be used t o c h a r a c t e r i z e p a t t e r n s p r o d u c e d
b y s t a n d a r d l i t h o g r a p h y processes which a r e used in
the p r o d u c t i o n of electronic devices such as c o m -

435

Scanning

Tunnelling

60

Microscopy

Spectroscopy

7^
0

and

20

oxygen

40

60

E l a p s e d t i m e in v a c u u m

80

100

(h)

>
<

Figure 11
Change in surface chemistry due to desorption of
atmospheric adsorbates when ZnO is introduced into an
UHV environment: the change in "apparent" surface
work function, as determined by the changing slope of the
I/z measurement performed in the STM, and the Auger
analysis are consistent with the desorption of oxygen and
carbon dioxide from the ZnO

p u t e r s . T h e s e m a t e r i a l s a r e n o t necessarily c o n d u c
tive; c o n s e q u e n t l y , d e p o s i t i o n of a thin film of m e t a l is
necessary t o p r o v i d e a c o n d u c t i v e surface for i m a g i n g .
T h e t h r e e - d i m e n s i o n a l i n f o r m a t i o n o b t a i n e d in the
S T M analysis of i n t e g r a t e d circuits c a n n o t b e
o b t a i n e d with o t h e r m e t h o d s of process e v a l u a t i o n
Tunnelling bias

(V)

Figure 13
Three types of electronic structure detected in emeraldine
hydrochloride films: (a) a semiconductor-like structure
with no midgap defect states, (b) a metallic-like structure;
and (c) a structure consisting of midgap states between the
valence and conduction bands

c u r r e n t l y in use. I m p o r t a n t t o t h e p o t e n t i a l of S T M in
c o m m e r c i a l a p p l i c a t i o n s is t h a t these images were
a c q u i r e d in air, t h u s a v o i d i n g t h e c o m p l i c a t i o n s , a n d
e x t r a analysis time, associated with v a c u u m systems.

6. Related

Figure 12
Topographic image of partially protonated emeraldine
hydrochloride, indicating the surface structure that results
from the melt spinning process of film deposition

436

Techniques

T h e s c a n n i n g t e c h n o l o g y of S T M is n o w being
exploited t o m e a s u r e q u a n t i t i e s o t h e r t h a n tunnelling
c u r r e n t a n d local densities of states. T h e m o s t d e
veloped of these n e w " n e a r field" o r " s c a n n i n g p r o b e "
t e c h n i q u e s is a t o m i c force m i c r o s c o p y ( A F M ) , w h i c h
r e c o r d s i n t e r a t o m i c forces b e t w e e n t h e s a m p l e a n d
tip. T h e tip is a t t a c h e d t o a cantilever w i t h a spring
c o n s t a n t of a b o u t 1 N m " 1 a n d r e s o n a n t frequency of
1 - 1 0 k H z . A s t h e tip is s c a n n e d over t h e s a m p l e ,

Scanning

Tunnelling

Microscopy

and

Spectroscopy

Figure 14
Constant current images: (a) a 5 scan of a 1 diffraction grating and (b) a 50 scan of an integrated circuit coated
with a thin layer of goldimages were acquired on a Nanoscope in air (courtesy of Digital Instruments)

437

Scanning

Tunnelling

Microscopy

and

Spectroscopy

deflection of t h e cantilever d u e t o t h e forces b e t w e e n

a t o m s o n t h e surface with t h o s e o n t h e t i p is m o n i
tored to produce a topographic image corresponding
t o a c o n s t a n t force profile. F o r c e s detected r a n g e from
6
9
1 0 " N t o 1 0 ~ N . T h i s i m a g e is a n a l o g o u s t o t h e
c o n s t a n t c u r r e n t i m a g e in S T M . Sensitive d e t e c t i o n of
t h e cantilever deflection is r e q u i r e d t o o p t i m i z e t h e
spatial r e s o l u t i o n of A F M . Several m e t h o d s of force
detection h a v e b e e n e m p l o y e d including: electron
tunnelling, c a p a c i t a n c e , interferometry, a n d deflec
tion of a laser b e a m reflected off t h e cantilever a n d
fiber optic interferometry. T h e last m e t h o d is p r e
ferred for its simplicity a n d v a c u u m c o m p a t i b i l i t y .
Atomic-resolution imaging has been demonstrated o n
i n o r g a n i c i n s u l a t o r s such as b o r o n nitride a n d o r g a n i c
n o n c o n d u c t o r s such a s a m i n o acids, as well a s gra
p h i t e a n d m o l y b d e n u m disilicide. O n e of t h e a d v a n
tages of A F M is t h a t it e x t e n d s t o p o g r a p h i c i m a g i n g
to i n s u l a t o r s a n d biological m a t e r i a l s .
Other techniques based on the new scanning probe
technology of S T M include m a g n e t i c force i m a g i n g ,
t h e r m a l g r a d i e n t i m a g i n g , surface modification such
as n a n o l i t h o g r a p h y , n e a r field optical i m a g i n g , p h o n o n detection, ballistic electron emission m i c r o s c o p y
a n d c a p a c i t a n c e m i c r o s c o p y . It r e m a i n s t o b e seen
which of these n e w m e a s u r e m e n t s will b e c o m e stan
dard characterization techniques.
See also: Atomic Force Microscopy; Mechanical Properties
Microprobe

Bibliography
Bardeen J 1961 Tunneling from a many particle point of
view. Phys. Rev. Lett. 6: 57-9
Bell L D, Kaiser W J 1988 Observation of interface band
structure by ballistic-electron-emission microscopy. Phys.
Rev. Lett. 61: 2368-71
Binnig G, Quate C F, Gerber Ch 1986 Atomic force
microscopy. Phys. Rev. Lett. 56: 930-3
Binnig G, Rohrer 1982 Scanning tunnelling microscope.
Helv. Phys. Acta 55: 726
Binnig G, Rohrer 1987 Scanning tunnelling microscopy
from birth to adolescence. Rev. Mod. Phys. 59: 615-25
Binnig G, Rohrer H, Gerber Ch, Weibel 1982 Surface
studies by scanning tunneling microscopy. Phys. Rev.
Lett. 49: 57-61
Binnig G, Rohrer H, Gerber Ch, Weibel 1983 7 x 7
reconstruction on Si resolved in real space. Phys. Rev.
Lett. 50: 120
Bonnell D A 1988 Characterization of carbides by STM.
J. Mater. Sci. Eng. A 105/106: 55-63
Bonnell D A (ed.) 1990 Scanning Tunneling Microscopy:
Theory and Practice. VCH, New York
Bonnell D A, Angelopoulos 1989 Spatially localized
electronic structure in polyaniline by STM. IBM Re
search Report
Bonnell D A, Clarke D R 1988 Scanning tunneling micros

438

copy and spectroscopy of ceramics: SiC and ZnO. J. Am.

Cer. Soc. 71: 629-37
Feenstra R (ed.) 1988 Proceedings of the Second Inter
national Conference on Scanning Tunneling Microscopy.
/. Vac. Sci. Technol. A 6: 259-556
Garcia (ed.) 1987 Proceedings of the First International
Conference on Scanning Tunneling Microscopy. Surf.
Sci. 181: 1^112
Gopel W 1985 Chemisorption and charge transfer at ionic
semiconductor surfaces: implications in designing gas
sensors. Prog. Surf. Sci. 20: 9-102
Hamers R J 1989 Atomic resolution surface spectroscopy
with the scanning tunneling microscope. Ann. Rev. Phys.
Chem. 40: 531-59
Hamers R J, Demuth J 1988 Atomic structure of Si (111)
(3 x 3) Al. / . Vac. Sci. Technol. A 6: 512-16
Hansma (ed.) 1982 Tunneling SpectroscopyCapabilit
ies, Applications and New Techniques. Plenum, New York
Hansma , Elings V , Marti , Bracker C 1988
Scanning tunneling microscopy and force microscopy:
application to biology and technology. Science 242: 20942
Hansma , Tersoff J 1987 Scanning tunneling micros
copy. J. Appl. Phys. 61: R l - 2 3
Himpsel F, Fauster Th 1984 Probing valence states with
photoemission and inverse photoemission. J. Vac. Sci.
Technol A. 1: 111
Lang 1986 Theory of single atom imaging in the STM.
Phys. Rev. Lett. 56: 1164-8
Lang 1987 Apparent size of an atom in the scanning
tunneling microscope. Phys. Rev. Lett. 58: 45-8
Martin Y, Williams C C, Wickramasinghe 1988 The
techniques for microcharacterization of materials. Scan
ning Microsc. 2: 3-8
Quate C F 1986 Vacuum tunneling: a new technique for
microscopy. Phys. Today 39(8): 26-33
Smith D, Binnig G, Quate C 1986 Detection of phonons
with a STM. Appl. Phys. Lett. 49: 1641-3
Tersoff J, Hamann D R 1985 Theory of scanning tunneling
microscopy. Phys. Rev. 2? 31: 80513
Tromp R M, Hamers R J, Demuth J 1985 Si (001) dimer
structure observed with STM. Phys. Rev. Lett. 55: 1303-7
Wickramasinghe 1989 Scanned-probe microscopes.
Sci. Am. 261: 74-81
Williams C C, Wickramasinghe 1986 Scanning thermal
profiler. Appl. Phys. Lett. 49: 1587-9
Wolfe L 1986 Electron Tunnelling Spectroscopy. Oxford
University Press, Oxford
Zangwill A 1988 Physics at Surfaces. Cambridge University
Press, Cambridge
D . A . Bonnell
[University of P e n n s y l v a n i a , P h i l a d e l p h i a ,
Pennsylvania, U S A ]

Secondary-Ion Mass Spectrometry

M a n y of t h e c o m p l e x n e w m a t e r i a l s d e v e l o p e d t o d a y
derive their u n i q u e p r o p e r t i e s from t h e presence of
multiple p h a s e s o r from local v a r i a t i o n s in elemental
c o n c e n t r a t i o n . Since simply p e r f o r m i n g a b u l k a n a l y -

Secondary-Ion

sis is i n a d e q u a t e in fully c h a r a c t e r i z i n g such m a t e r i a l s ,

a n u m b e r of t e c h n i q u e s for o v e r c o m i n g this l i m i t a t i o n
are often used, including electron m i c r o p r o b e a n a l y
sis, analytical electron m i c r o s c o p y a n d s c a n n i n g
A u g e r analysis. E a c h m e t h o d offers special a d v a n
tages relative t o t h e o t h e r s with r e g a r d t o sensitivity,
quantification of results o r spatial r e s o l u t i o n . A n
a d d i t i o n a l t e c h n i q u e is s e c o n d a r y - i o n m a s s s p e c t r o m
etry ( S I M S ) . It is extremely sensitive with excellent
d e p t h r e s o l u t i o n , m a k i n g it ideally suited t o t h e
e x a m i n a t i o n of d o p a n t profiles in s e m i c o n d u c t o r s ,
b u t it also finds m a n y a p p l i c a t i o n s in m e t a l l u r g y ,
ceramics, m i n e r a l o g y a n d t h e life sciences. T h e basis
of t h e m e t h o d is t h e use of a focused ion b e a m t o
sputter a t o m s from a selected region of interest. Since
a fraction of these s p u t t e r e d a t o m s a r e ionized they
c a n be a n a l y z e d w i t h a m a s s s p e c t r o m e t e r . E l e m e n t a l
d e p t h profiles a r e o b t a i n e d as a direct c o n s e q u e n c e of
the fact t h a t t h e s a m p l e is slowly e r o d e d b y t h e
s p u t t e r i n g p r o c e s s itself. L a t e r a l r e s o l u t i o n is achieved
either b y focusing t h e p r i m a r y - i o n b e a m o n a detail t o
be analyzed (ion m i c r o p r o b e analysis) o r flooding a
s o m e w h a t larger a r e a a n d f o r m i n g a n i m a g e b a s e d o n
the d i s t r i b u t i o n of a specific ion (ion m i c r o s c o p y ) .

1. Ion-Solid

Interaction:

Sputtering

and

Ionization

S p u t t e r e d species, p r o d u c e d b y 1-30 k e V i o n b o m
b a r d m e n t , u n d e r g o a c h a r g e - e x c h a n g e w i t h their local
e n v i r o n m e n t ( s a m p l e surface) resulting in their c o n
version t o positive a n d negative i o n s . T h e s e a n a l y t i
cally i m p o r t a n t s e c o n d a r y ions o r i g i n a t e from a n a r e a
defined laterally b y t h e p r i m a r y - b e a m p e r i p h e r y , typi
cally 1 - s e v e r a l m m , a n d t h e s a m p l e i n t e r a c t i o n
d e p t h , 5 - 5 0 A. T h e m a s s - s p e c t r o m e t r i c analysis of
these s e c o n d a r y i o n s results in a t e c h n i q u e c a p a b l e of
elemental specificity from h y d r o g e n t o u r a n i u m w i t h
detectabilities in t h e p p m ( a t o m i c ) r a n g e .
T h e a c t u a l p h e n o m e n o n of s p u t t e r i n g w a s first
r e p o r t e d in t h e 1850s in gas-discharge e x p e r i m e n t s .
Since these early b e g i n n i n g s , t h e e r o s i o n of solids
by energetic b e a m s h a s received c o n s i d e r a b l e a t t e n
tion a n d m a n y m e c h a n i s m s h a v e b e e n f o r m u l a t e d t o
rationalize t h e s p u t t e r i n g p r o c e s s . C u r r e n t l y , t h e r e
exists n o single m o d e l w h i c h c a n a c c o u n t for all t h e
e x p e r i m e n t a l results.
T h e general t o p i c of s p u t t e r i n g m a y be divided i n t o
t w o categories: (a) physical a n d (b) c h e m i c a l s p u t t e r
ing. Physical s p u t t e r i n g involves t h e transfer of e n e r g y
from t h e incident ion t o t h e t a r g e t a t o m ( s ) resulting in
its (their) ejection. T h i s p r o c e s s is c o n t r a s t e d t o c h e m
ical s p u t t e r i n g w h e r e t h e incident particle results in
the f o r m a t i o n of a m e t a s t a b l e c o m p o u n d a t t h e t a r g e t
surface. B o t h types of s p u t t e r i n g r e q u i r e t h a t t h e
ejected species h a v e significant energy t o o v e r c o m e
the surface p o t e n t i a l b a r r i e r . S p u t t e r i n g c a n o c c u r

Mass

Spectrometry

over a relatively wide r a n g e of incident-ion energies,

from t h e lower eV r a n g e for chemical s p u t t e r i n g t o the
u p p e r k e V region for physical ejection. It s h o u l d be
n o t e d t h a t s p u t t e r i n g is n o t t h e only process b y which
a t a r g e t a t o m m a y b e r e m o v e d with sufficient energy
t o escape t h e s a m p l e surface; o t h e r m e c h a n i s m s in
clude s a m p l e h e a t i n g a n d s u b s e q u e n t e v a p o r a t i o n a n d
b e a m - i n d u c e d d e s o r p t i o n p h e n o m e n a caused by elec
t r o n o r ion i r r a d i a t i o n .
W h e n discussing t h e physical s p u t t e r i n g of a m a t e r
ial, t h e event m a y b e classified b y t h e n u m b e r of target
a t o m s involved. T h e s e classifications a r e typically
categorized i n t o three regimes: (a) t h e k n o c k - o n
regime, (b) the linear-cascade regime a n d (c) t h e spike
regime. T h e first, k n o c k - o n , involves t h e fewest
n u m b e r of t a r g e t a t o m s . H e r e , t h e incident ion
transfers energy t o t h e t a r g e t species after h a v i n g
u n d e r g o n e only a few (or even o n e ) collisions. T h e
s a m p l e a t o m s struck by t h e incident particle receive
significant energy t o escape t h e s a m p l e surface. C o m
paratively, in linear-cascade s p u t t e r i n g t a r g e t a t o m s
receive e n o u g h energy t o c a u s e recoil cascades. T h e s e
recoiled a t o m s , in t u r n , strike o t h e r s a m p l e a t o m s
w h i c h a r e t h e n s p u t t e r e d . Similar t o linear-cascade
s p u t t e r i n g , t h e spike regime involves s p u t t e r i n g via
recoiled s a m p l e a t o m s . T h e spike regime is dis
tinguished by a n even larger density of a t o m s in
m o t i o n within a certain v o l u m e of m a t e r i a l .
T h e s u b s e q u e n t positive a n d negative i o n i z a t i o n of
t h e s p u t t e r e d species is also of interest in S I M S . A s
with t h e s p u t t e r i n g event, t h e i o n i z a t i o n process m a y
be categorized i n t o t w o b r o a d classes: (a) ionization
i n t e r n a l t o t h e target a n d (b) e x t e r n a l processes.
T h e i n t e r n a l i o n i z a t i o n of a t o m s is a n extension of
t h e c h e m i c a l - s p u t t e r i n g event discussed a b o v e . T h i s
a p p r o a c h p u r p o r t s t h e b r e a k i n g of b o n d s by the
incident ion a n d t h e s u b s e q u e n t emission of c h a r g e d
species. M o s t o t h e r m e c h a n i s m s fall i n t o t h e second
c a t e g o r y of i o n i z a t i o n of a s p u t t e r e d species resulting
from r e s o n a n t o r A u g e r i n t e r a c t i o n s between the
d e p a r t i n g a t o m a n d t h e s a m p l e surface.
O f direct interest t o m a t e r i a l s c h a r a c t e r i z a t i o n is
t h e effect o n t h e i o n yield of using either a n electro
negative o r electropositive e l e m e n t as t h e b o m b a r d i n g
species. F o r e x a m p l e , a d s o r p t i o n of a n electronega
tive element, such as oxygen, o n t o a m e t a l surface
increases t h e surface w o r k function. A s the w o r k
function increases, it b e c o m e s energetically m o r e dif
ficult for a n electron t o b e excited over t h e surface
p o t e n t i a l b a r r i e r . T h e result is increased positive-ion
yields d u e t o r e d u c e d n e u t r a l i z a t i o n . Conversely, the
o p p o s i t e s i t u a t i o n o c c u r s with a n electropositive spe
cies. U n d e r cesium b o m b a r d m e n t t h e w o r k function
is lowered, allowing m o r e electrons t o be available for
t h e f o r m a t i o n of negative i o n s . F o r this reason, in
o r d e r t o o p t i m i z e t h e sensitivity of S I M S , oxygen
is typically used in t h o s e analytical situations requir439

Secondary-Ion

Mass

Spectrometry

Figure 1
Schematic illustration of the Cameca IMS-3f ion microscope (courtesy of Cameca Instruments)

ing high sensitivity for the electropositive species,

w h e r e a s a cesium b e a m is used to p r o v i d e t h e
e n h a n c e d s e c o n d a r y yields for
electronegative
elements.
2.

Instrumentation

S I M S i n s t r u m e n t a t i o n c a n r a n g e from
simple
discharge-ion g u n / q u a d r u p o l e m a s s analyzers t o
sophisticated ion m i c r o p r o b e s a n d ion m i c r o s c o p e s .
T h e a c t u a l p r i m a r y - i o n s o u r c e a n d optics, s a m p l e h a n d l i n g capabilities a n d s p e c t r o m e t e r d e t e r m i n e t h e
i n s t r u m e n t ' s analytical p o t e n t i a l a n d price. F o r this
discussion, S I M S i n s t r u m e n t s m a y b e categorized i n t o
three general classes: (a) ion m i c r o p r o b e s t h a t use a
highly focused p r i m a r y b e a m ( 2 - 2 0 d i a m e t e r )
allowing lateral m i c r o a n a l y s i s ; (b) ion m i c r o s c o p e s
t h a t i n c o r p o r a t e a relatively large b e a m ( 5 - 5 0 0 p m
d i a m e t e r ) a n d a stigmatic m a s s s p e c t r o m e t e r t o p r o
vide lateral r e s o l u t i o n s of a p p r o x i m a t e l y 1 p m ; a n d (c)
b i g - b e a m i n s t r u m e n t s (100s p m d i a m e t e r ) t h a t a r e

440

c a p a b l e of surface a n d i n - d e p t h analysis with m i n i m a l

lateral r e s o l u t i o n .
I n t h e p r e v i o u s discussion of s p u t t e r e d - i o n emission
it w a s n o t e d t h a t t h e p r i m a r y - i o n s o u r c e is of u t m o s t
i m p o r t a n c e in d e t e r m i n i n g t h e analytical capabilities
of a given i n s t r u m e n t . O n e of t h e m o s t p o p u l a r types
of i o n s o u r c e is t h e d u o p l a s m a t r o n . T h i s s o u r c e uses a
p l a s m a with b o t h electrostatic a n d m a g n e t i c constric
tion t o p r o d u c e a h i g h - b r i g h t n e s s b e a m . A l t h o u g h , as
previously m e n t i o n e d , m o s t analytical s i t u a t i o n s uti
lize a n oxygen b e a m ( 1 60 ~ o r 3 02 2 +) , t h e d u o p l a s m a t r o m is c a p a b l e of u s i n g a n y inert o r reactive gas. T h e
ions f o r m e d a r e e x t r a c t e d b y a n a p p r o p r i a t e field a n d
accelerated typically from 5 k e V t o 30 keV.
A n o t h e r p o p u l a r ion g u n utilizes a cesium source.
I n this design, a reservoir is l o a d e d with a 1-5 g c h a r g e
of cesium. A t u n g s t e n frit, l o c a t e d a b o v e t h e reservoir,
is t h e n h e a t e d t o a b o u t 1 1 0 0 C . A t this t e m p e r a t u r e ,
t h e reservoir is c o n d u c t i v e l y h e a t e d a n d t h e cesium
v a p o r backfed t o t h e t u n g s t e n frit, with 99 % of t h e
v a p o r being ionized. T h e frit is m a i n t a i n e d c o n c e n t r i c

Secondary-Ion

Depth

(/im)

Figure 2
9
+
SIMS in-depth profile of a 50 kV/lel4 Be implant in
GaAs

with the axis of t h e s o u r c e h o u s i n g by a b e a m - f o r m i n g

electrode. T h e s o u r c e typically delivers 6 0 - 7 0 n A i n t o
2
a 2 0 b e a m d i a m e t e r ( ~ 2 0 m A c m ~ ) . A p a r t from
the p r i m a r y - i o n s o u r c e a n d optics, t h e o t h e r m a j o r
i n s t r u m e n t a l c o m p o n e n t s a r e t h e s a m p l e stage, t h e
m a s s s p e c t r o m e t e r , t h e ion d e t e c t o r a n d t h e d a t a h a n d l i n g system.
Sample-handling requirements are dictated by the
analytical r e q u i r e m e n t s of e a c h i n s t r u m e n t . Since i o n
m i c r o p r o b e s r e q u i r e t h e m o s t stringent s a m p l e c o n
trol they use a m i c r o m a n i p u l a t o r . E x a c t i o n - b e a m
p o s i t i o n i n g is less critical for t h e ion m i c r o s c o p e ,
which is also used for m i c r o a n a l y s i s , b e c a u s e it f o r m s
a n ion i m a g e of t h e regions t o be a n a l y z e d b y t h e use
of selected-area a p e r t u r e s . T h e l a r g e - b e a m S I M S
i n s t r u m e n t h a s t h e least stringent s a m p l e m a n i p u l a
tion r e q u i r e m e n t s b e c a u s e t h e s p a t i a l - r e s o l u t i o n re
q u i r e m e n t is n o t as critical. M a n y i n s t r u m e n t s use
sample holders containing multiple samples which
c a n be l o a d e d o n e a t a time t h r o u g h a direct v a c u u m
lock t o m i n i m i z e p u m p - d o w n time.
T h e m a s s s p e c t r o m e t e r s a r e of t w o basic types,
m a g n e t i c deflection a n d q u a d r u p o l e m a s s filter. D u e
to the initial large s p r e a d of kinetic energies of t h e
s e c o n d a r y i o n s , m o s t i n s t r u m e n t s use s o m e t y p e of
filter for a n energy analysis of t h e s e c o n d a r y ions.
Such a design is f o u n d in all ion m i c r o p r o b e s . T h e y all
use a n electrostatic filter for energy analysis of t h e
s e c o n d a r y ions, followed by m a s s analysis using a

Mass

Spectrometry

m a g n e t i c analyzer. I n s t r u m e n t s using filters for b o t h

energy a n d m a s s analysis a r e called d o u b l e focusing.
T h e i o n - m i c r o s c o p e i n s t r u m e n t uses a different
g e o m e t r y . O n e such i n s t r u m e n t , s h o w n in Fig. 1, is
t h e C a m e c a I M S 3-f. It uses a u n i q u e ion-optics
system t h a t p r o v i d e s d o u b l e - f o c u s i n g m a s s s p e c t r o
m e t r y a n d a c h r o m a t i c ion i m a g i n g . T h e s e c o n d a r y
ions a r e e x t r a c t e d b y a n electrostatic i m m e r s i o n lens.
T h e keys t o this i n s t r u m e n t a r e t h e transfer optics
w h i c h m a t c h t h e exit p a r a m e t e r s of the collection
optics t o the e n t r a n c e p a r a m e t e r s of t h e m a s s spec
t r o m e t e r . T h i s a r r a n g e m e n t allows t h e o p t i m i z i n g , for
a given m a s s r e s o l u t i o n , of the a n a l y z e d a r e a a n d the
s e c o n d a r y - i o n collection angle. T h u s , for a c o n s t a n t
m a s s r e s o l u t i o n , w h e n t h e a r e a a n a l y z e d is r e d u c e d
t h e useful yield is increased, or, alternatively, a n
increase in m a s s r e s o l u t i o n c a n be achieved w i t h o u t
c h a n g i n g the useful yield. T h i s ion optical system
e x t r a c t s , t r a n s p o r t s a n d m a s s analyzes s e c o n d a r y ions
while m a i n t a i n i n g their spatial r e l a t i o n s h i p . A direct
ion i m a g e of a m a s s is p r o d u c e d s i m u l t a n e o u s l y from
t h e entire b o m b a r d e d a r e a . T h i s design p e r m i t s a
m a s s r e s o l u t i o n (/) of a p p r o x i m a t e l y 10 000.
The big-beam instruments employ a quadrupole
m a s s filter with s o m e type of energy analysis. T h e s e
energy analyzers r a n g e from cylindrical electrostatic
a n a l y z e r s t o simple lenses a n d a n a p e r t u r e used t o
p a s s i o n s of a certain energy. T h e q u a d r u p o l e m a s s
filter is used to p r o v i d e S I M S capabilities a t relatively
low c o s t c o m p a r e d t o t h e d o u b l e - f o c u s i n g i o n m i c r o
p r o b e s a n d m i c r o s c o p e s . A l t h o u g h these b i g - b e a m
i n s t r u m e n t s p r o v i d e S I M S capabilities, their analyti
cal p o t e n t i a l is limited. T h e sensitivity of m a n y q u a d
r u p o l e S I M S i n s t r u m e n t s is a b o u t 0.01 a t . % , n o t
m u c h b e t t e r t h a n t h e sensitivities achieved with A u g e r
e l e c t r o n s p e c t r o s c o p y ( A E S ) (see Auger
Electron
Spectroscopy).
F u r t h e r , t h e t r a n s m i s s i o n of a q u a d
r u p o l e S I M S is a p p r o x i m a t e l y p r o p o r t i o n a l t o the
inverse of t h e m a s s of t h e s e c o n d a r y i o n s . T h e s e
i n s t r u m e n t s suffer from b o t h t r a n s m i s s i o n a n d m a s s d i s c r i m i n a t i o n difficulties.
After m a s s analysis, t h e s e c o n d a r y ions a r e
generally detected by electrical m e a n s . Electrical d e
tectors include discrete- a n d c o n t i n u o u s - d y n o d e elec
t r o n multipliers a n d t h e D a l y - t y p e d e t e c t o r . M o s t
often, m a s s spectral d a t a a r e r e c o r d e d using digital
pulse-counting techniques.
R e a d o u t m o d e s v a r y with t h e t y p e of analysis a n d
i n s t r u m e n t . M a s s s p e c t r a m a y be p l o t t e d o n either a n
X-Y r e c o r d e r o r a t h e r m a l p r i n t e r . In ion m i c r o
p r o b e s , i o n images a r e generally displayed o n a n
oscilloscope from which a p e r m a n e n t p h o t o g r a p h
c a n b e t a k e n . T h e C a m e c a i n s t r u m e n t uses a m i c r o channel-plate/fluorescent-screen d e t e c t o r to display
ion i m a g e s a n d m a s s spectral lines w h i c h c a n be
i m a g e d directly o r p h o t o g r a p h e d . Since t h e s p u t t e r i n g
p r o c e s s is c o n t i n u a l l y e r o d i n g a w a y t h e s a m p l e , it is
also possible t o o b t a i n d e p t h profiles. In this m o d e ,
t h e intensity of o n e o r m o r e selected ions is m o n i t o r e d

441

Secondary-Ion

IxlO

IXIO

Mass

Spectrometry

7
E

I 10

I
0

0.39

0.72

1.08

I
1.44

1.80

Total depth ()
Figure 3
SIMS in-depth profile of a GaAs/AlGaAs superlattice showing all 62 layers of the structure resolved

as a function of time. A d e p t h scale c a n t h e n b e

d e t e r m i n e d b y m e a s u r i n g t h e d e p t h of t h e c r a t e r
caused b y t h e s p u t t e r i n g process. T h i s c a n b e d o n e
with a surface profilometer after t h e analysis is c o m
plete.
A l m o s t all i n s t r u m e n t s h a v e s o m e sort of c o m p u t e r
a u t o m a t i o n . W h i l e t h e extent of a u t o m a t i o n varies
from o n e i n s t r u m e n t m a n u f a c t u r e r t o a n o t h e r , a s a
m i n i m u m , m o s t c u r r e n t S I M S systems h a v e a c o m
p u t e r system for d a t a h a n d l i n g . A d e d i c a t e d m i n i c o m
p u t e r also e n a b l e s m a n y c o m p o n e n t s of t h e o p e r a t i n g
electronics t o b e a u t o m a t i c a l l y m o n i t o r e d a n d c o n
trolled. N o t only d o e s t h e c o m p u t e r further simplify
d a t a acquisition a n d r e d u c t i o n , it also h a s t h e a d v a n
tage of m a k i n g t h e overall system m o r e e r r o r free.
A l t h o u g h n o t strictly a n i n s t r u m e n t a l design c o n
sideration, a r e q u i r e m e n t of t h e S I M S t e c h n i q u e is t h e
need for high v a c u u m . H i g h v a c u u m reduces colli
sions between s e c o n d a r y ions a n d g a s molecules a s
well a s m i n i m i z i n g residual g a s c o n t a m i n a n t s t h a t
could interfere with a n analysis. A s with c o m p u t e r
systems, p u m p i n g schemes also v a r y from o n e m a n u
facturer t o a n o t h e r . H o w e v e r , with p r e s e n t v a c u u m

442

capabilities, a S I M S i n s t r u m e n t s h o u l d o p e r a t e in a
8
v a c u u m of a t least 1 0 ~ t o r r . A l s o , m a n y S I M S
i n s t r u m e n t s a r e b a k a b l e t o t e m p e r a t u r e s of 150
180C, a i d i n g in t h e r e m o v a l of c o n t a m i n a n t s from
t h e walls of t h e system. R e c e n t designs in q u a d r u p o l e
m a s s filters h a v e e n a b l e d m a n y i n s t r u m e n t s t o b e
e q u i p p e d w i t h t h e smaller q u a d r u p o l e filters. T h e
relatively inexpensive q u a d r u p o l e systems m a y b e
m o u n t e d in t h e s a m p l e region t o p r o v i d e a n analysis
of a n y residual c o n t a m i n a n t s . Q u a d r u p o l e analyzers
h a v e also e n a b l e d t h e e x p a n s i o n of analytical c a p a b i l
ities b y " a d d i n g o n " t o existing systems. S u c h a d d - o n ,
h y b r i d systems allow c o m p l e m e n t a r y i n f o r m a t i o n t o
be t a k e n o n a given s a m p l e w i t h o u t it h a v i n g t o b e
r e m o v e d from t h e h i g h - v a c u u m e n v i r o n m e n t .
3. Analytical

Applications

of

SIMS

S I M S h a s been a p p l i e d t o m a n y different p r o b l e m s in
a variety of disciplines. T h e m e t h o d h a s p r o v i d e d
i n f o r m a t i o n o n a m y r i a d o f s a m p l e s r a n g i n g from
m i n e r a l s a n d l u n a r particles t o o r g a n i c molecules a n d
biological tissues.

Secondary-Ion

Mass

Spectrometry

directly affect t h e p e r f o r m a n c e characteristics of the

device.
A c o m m o n m e t h o d of i n t r o d u c i n g these d o p a n t s is
i o n i m p l a n t a t i o n . H e r e , a n energetic ion b e a m of the
d o p a n t strikes t h e s e m i c o n d u c t o r t o b e i m p l a n t e d ,
resulting in the i n c o r p o r a t i o n of t h e d o p a n t species.
T h e exact c o n c e n t r a t i o n a n d l o c a t i o n of the d o p a n t
i n - d e p t h m a y be calculated from t h e i o n - b e a m c u r r e n t
density, accelerating p o t e n t i a l , a n d masses of the
d o p a n t a n d i m p l a n t e d s u b s t r a t e . Because of the rela
tively c o n t r o l l e d n a t u r e of ion i m p l a n t a t i o n , its use as
a d o p i n g m e t h o d is q u i t e a t t r a c t i v e . F u r t h e r , since the
a c t u a l p e a k c o n c e n t r a t i o n of a n y d o p a n t - s u b s t r a t e
c o m b i n a t i o n m a y be readily calculated, ion i m p l a n t s
a r e excellent s t a n d a r d s for S I M S . F i g u r e 2 s h o w s
results o b t a i n e d from a 5 0 k e V / l e l 4 9 B e + i m p l a n t in
G a A s . T h e d a t a were t a k e n using 10.5 keV 3 02 ^
p r i m a r y ions a n d by m o n i t o r i n g t h e positive second
a r y i o n s emitted. T h e d e p t h profile of 9B e + is s h o w n
p l o t t e d as beryllium c o n c e n t r a t i o n versus d e p t h . N o t e
t h e u n s u b t r a c t e d limit of d e t e c t i o n for beryllium in
G a A s of a p p r o x i m a t e l y 1 0 14 a t o m s c m - 3.

Figure 4
SIMS ion-imaging analysis showing two different
hydrogen distributions in (a) a nickel-base alloy and
(b) 304 stainless steel

D e p t h profiling is o n e of t h e m o s t c o m m o n a n a l y t i
cal m o d e s of S I M S . I n practice, it is d o n e b y r a s t e r i n g ,
o r s c a n n i n g , t h e p r i m a r y b e a m a c r o s s a s a m p l e sur
face. R a s t e r i n g is necessary b e c a u s e of t h e G a u s s i a n
s h a p e of t h e b e a m . Typically, t h e b e a m is r a s t e r e d
over a large a r e a ( 1 0 0 - 5 0 0 ) with s e c o n d a r y i o n s
selected from a central p o r t i o n of t h e c r a t e r u s i n g
either m e c h a n i c a l o r electronic a p e r t u r i n g . T h i s helps
to eliminate c r a t e r - e d g e effects c a u s e d b y t h e b e a m ' s
G a u s s i a n s h a p e w h i c h c o u l d decrease d e p t h resolu
tion d u e t o s e c o n d a r y - i o n emission from sloping
crater walls.
O n e c o m m o n a p p l i c a t i o n o f d e p t h profiling is t h e
investigation of t h e d i s t r i b u t i o n of electrically active
species, d o p a n t s , in s e m i c o n d u c t o r s . T r a c e a m o u n t s
of these d o p a n t s i n t r o d u c e available states i n t o t h e
region of t h e f o r b i d d e n g a p . T h u s , t h e exact c o n c e n
t r a t i o n a n d i n - d e p t h d i s t r i b u t i o n of these species c a n

A n o t h e r c u r r e n t m e t h o d for t h e f o r m a t i o n of novel
device s t r u c t u r e s is m o l e c u l a r - b e a m epitaxy ( M B E ) .
H e r e , m o d u l a t e d s t r u c t u r e s of s e m i c o n d u c t i n g m a t e r
ials a r e d e p o s i t e d o n a n a p p r o p r i a t e s u b s t r a t e with
a c c u r a t e c o n t r o l s o n d o p i n g c o n c e n t r a t i o n a n d film
thickness. T h e interfacial s h a r p n e s s a n d film thickness
of such systems a r e t w o i m p o r t a n t p a r a m e t e r s . A g a i n ,
a S I M S i n - d e p t h profile p r o v i d e s analytical results
p e r t a i n i n g t o t h e s t r u c t u r e of t h e device. F i g u r e 3
s h o w s a S I M S profile of a G a A s - A l G a A s superlattice p r e p a r e d by M B E . T h e s t r u c t u r e from the
surface c o n t a i n s a 40 A G a A s layer, t h e n 60 alter
n a t i n g layers of G a A s a n d A l G a A s - S i , a n d a second
40 A GaAs layer d e p o s i t e d o n a G a A s s u b s t r a t e . T h e
S I M S d a t a were r e c o r d e d using 8.0 k e V 1 3 C
3 s + prim
a r y i o n s a n d negative s p e c t r o m e t r y . T h e profiles of
2 7 Al", 2 S
8 i~ and 6 G
9 a"
a r e s h o w n p l o t t e d as relative
intensity versus t o t a l d e p t h . D u e t o t h e c h a n g e s in
s p u t t e r i n g r a t e from o n e layer t o a n o t h e r , only t h e
t o t a l d e p t h from t h e surface t o t h e e n d of the S I M S
profile is a c c u r a t e . T h e profiles s h o w all 62 layers well
resolved. Typical d e p t h r e s o l u t i o n in a d e p t h profile
is of t h e o r d e r of 50 A a l t h o u g h this c a n be i m p r o v e d
u p o n by a p p r o x i m a t e l y a factor of t w o with o p t i m i z a
tion of i n s t r u m e n t a l p a r a m e t e r s .
A n o t h e r powerful analytical m o d e of S I M S is the
ability t o p e r f o r m ion i m a g i n g , t h a t is, t o d e t e r m i n e
t h e lateral d i s t r i b u t i o n of a n y element in a s a m p l e .
S u c h a n analysis is of u t m o s t i m p o r t a n c e w h e n loca
lized p h e n o m e n a a r e of c o n c e r n , for e x a m p l e , grainb o u n d a r y chemistry, segregation a n d precipitation.
I n t h e field of m e t a l l u r g y , t h e localization of a
variety of elements in a n u m b e r of alloys systems is of
i m p o r t a n c e d u e t o t h e effects of these elements o n
m a t e r i a l s p r o p e r t i e s such as brittleness, tensile
s t r e n g t h a n d t h e o c c u r r e n c e of subcritical crack
g r o w t h . A l t h o u g h m a n y of these elements c a n be

443

Secondary-Ion

Mass

Spectrometry

I0

'Ca

CaH

C aFOe H

Ca
-

I0

Ca

CaO
CaH

Fe
V
TiH

Ca

Cr
VH
Cr

40

42

44

46

48
50
52
Mass/charge (amu)

g
Al2

54

Fe
NiH
FeH

KO
FeH
CrH

56

58

NN

60

Figure 5
SIMS mass spectrum of a coal-ash sample with both elemental and molecular clusters seen

detected b y a variety of t e c h n i q u e s , such as s c a n n i n g

A u g e r m i c r o s c o p y , S I M S is u n i q u e in t h a t it c a n b e
used t o s t u d y t h e deleterious effects of h y d r o g e n in
alloys a n d steels. F i g u r e 4 s h o w s t w o h y d r o g e n i o n
images in nickel-base alloys. T h e t o p m i c r o g r a p h
shows a h y d r o g e n ion i m a g e ( d a r k p a t c h e s t o right of
center) overlayed o n the nickel i m a g e from t h e s a m e
area of a nickel-base alloy. T h e images were t a k e n
1 3 3
+
C s b o m b a r d m e n t a n d negative-ion
using 8.0 k e V
s p e c t r o m e t r y . T h e field of view is 400 . N o t e t h a t
the h y d r o g e n is relatively u n i f o r m l y d i s t r i b u t e d
t h r o u g h o u t t h e field of view. T h i s h y d r o g e n distribu
tion is c o n t r a s t e d to a similar analysis s h o w n in t h e
b o t t o m m i c r o g r a p h in a stainless steel s a m p l e . T h e
h y d r o g e n (light) a n d nickel ( d a r k ) images a r e a g a i n
snowed overlayed from t h e s a m e area. T h e field of
view in this case is 150 . F r o m this m i c r o g r a p h
there is clear evidence of h y d r o g e n segregation t o t h e
martensite laths.
F r o m t h e S I M S i m a g i n g analysis, it w a s d e m o n
strated t h a t h y d r o g e n segregates differently in t h e
low-alloy a n d t h e stainless steel. T h i s a c c o u n t s for the
different fracture m o d e s of t h e t w o m a t e r i a l s . L o w alloy steels fracture b y b o t h i n t e r g r a n u l a r a n d t r a n s g r a n u l a r m e c h a n i s m s , w h e r e a s stainless steels fracture
at the m a r t e n s i t e laths.
O n e final analytical m o d e is t h e ability of S I M S t o
r e c o r d a m a s s s p e c t r u m . T h i s i n f o r m a t i o n is of use for
b u l k , q u a l i t a t i v e analysis, a n d i s o t o p i c - r a t i o m e a s u r e
m e n t s of interest in geological w o r k . F i g u r e 5 s h o w s a
m a s s s p e c t r u m from 4 0 - 6 0 a m u t a k e n o n coal ash.
3 2
+
T h e d a t a were t a k e n using 10.5 keV 0 2 p r i m a r y i o n s

444

a n d positive-ion s p e c t r o m e t r y . T h e d a t a a r e s h o w n as
relative intensity versus t h e m a s s / c h a r g e r a t i o . T h e
+
+
+
+
s p e c t r u m indicates t h e presence of C a , T i , V , C r ,
+
+
N i a n d F e . A l s o , n o t e t h e presence of m o l e c u l a r
+
+
clusters of t h e elements (e.g., C a H , C a O ) . T h e
f o r m a t i o n of such clusters results from t h e s p u t t e r i n g
process a n d t e n d s t o c o m p l i c a t e even t h e simplest of
S I M S m a s s spectra.
T h e e x a m p l e s of systems t o which S I M S is appli
cable, a n d often u n i q u e , a r e by n o m e a n s e x h a u s t e d in
this discussion. T h e v a r i o u s o p e r a t i n g m o d e s of S I M S
offer t r e m e n d o u s analytical p o t e n t i a l a n d scope.
See also: Laser Microprobe Mass Spectrometry; Laser Sam
pling Inductively Coupled Plasma Mass Spectrometry; Or
ganic Mass Spectrometry

Bibliography
Behrisch R (ed.) 1981 Sputtering by Particle Bombardment
1: Physical Sputtering of Single-Element Solids, Topics in
Applied Physics, Vol. 47. Springer, New York
Benninghoven A, Giber J, Laszlo J, Reidel M, Werner W
(eds.) 1982 Secondary Ion Mass Spectrometry: SIMS III,
Chemical Physics Vol. 19. Springer', New York
Evans C A Jr 1975 Surface and thin film compositional
analysis: description and comparison of techniques. Anal.
Chem. 47: 818A-29A
Evans C A Jr 1975 Surface and thin film analysis. Anal.
Chem. 47: 855A-86A
Heinrich F J (ed.) 1982 Secondary ion mass spectrometry.
In: Geiss R (ed.) 1981 Microbeam Analysis. San Francisco
Press, San Francisco, CA, pp. 202-32

Semiconducting

Katz W 1981 Applied surface analysis. In: Geiss R (ed.)

1981 Microbeam Analysis. San Francisco Press, San
Francisco, CA, pp. 287-95
W. Katz
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]

Semiconducting Materials:
Characterization by Etching
S t r u c t u r a l a n d c h e m i c a l i n h o m o g e n e i t i e s a r e t w o of
t h e m a i n r e a s o n s for l o w yields a n d s h o r t lifetimes of
electronic devices m a d e f r o m s e m i c o n d u c t o r s . I n
c o m p o u n d s e m i c o n d u c t o r s t h e n u m b e r of p o s s i b l e
defects is l a r g e r t h a n in t h e case of e l e m e n t a l s e m i
c o n d u c t o r s , d u e t o t h e w i d e r v a r i e t y of n a t i v e defects
which can occur. Both crystallographic a n d chemical
defects a r e i n t r o d u c e d i n t o b u l k m a t e r i a l d u r i n g
g r o w t h a n d l a t e r a t a n y s t a g e of device p r o c e s s i n g .
F o r this r e a s o n , q u i c k a n d reliable c h a r a c t e r i z a t i o n
t e c h n i q u e s a r e essential for r e v e a l i n g defects a n d
assessing t h e r e a s o n s for t h e i r f o r m a t i o n , especially
w h e n s u c h i n f o r m a t i o n is r e q u i r e d b e f o r e f u r t h e r
p r o c e s s i n g t a k e s p l a c e . Selective e t c h i n g m e e t s t h e s e
r e q u i r e m e n t s a n d , in c o m b i n a t i o n w i t h reflection
m i c r o s c o p y , is widely u s e d in s t u d y i n g defects in
semiconductors. Conventional etching techniques
h a v e a l r e a d y b e c o m e a r o u t i n e m e t h o d of e v a l u a t i n g
t h e d e n s i t y a n d d i s t r i b u t i o n of defects s u c h as d i s l o
c a t i o n s (the s t a n d a r d specification of all c o m m e r
cially a v a i l a b l e s e m i c o n d u c t o r s u b s t r a t e s c o v e r s t h e
etch pit d e n s i t y ( E P D ) ) . I m p o r t a n t f e a t u r e s of this
e t c h i n g m e t h o d a r e simplicity, r a p i d d a t a a c q u i s i t i o n
a n d relatively l o w - c o s t e q u i p m e n t . T h e m e t h o d is,
h o w e v e r , a n i n d i r e c t o n e (i.e., t h e e t c h p i t s a r e
f o r m e d d u e t o t h e p r e s e n c e of defects b u t t h e defects
themselves a r e c o n t i n u o u s l y r e m o v e d a s t h e e t c h i n g
proceeds). As a consequence, to avoid misinterpreta
t i o n , c a l i b r a t i o n w i t h d i r e c t m e t h o d s is often
r e q u i r e d ; a l s o , t h e size of t h e p i t s c a n b e easily
controlled by the time a n d / o r temperature of etch
ing, b e i n g u s u a l l y o r d e r s of m a g n i t u d e l a r g e r t h a n
t h e real size of t h e defects. T h i s last p r o p e r t y is very
useful w h e n a u t o m a t i c c o u n t i n g of t h e E P D is
employed.
T h e rules of f o r m a t i o n of d i s l o c a t i o n - r e l a t e d e t c h
pits a r e relatively well r e c o g n i z e d a n d u n d e r s t o o d for
different types of solids, a m o n g t h e m s e m i c o n d u c
t o r s . H o w e v e r , t h e i n c r e a s i n g d e m a n d for h i g h c o m
p o s i t i o n a l a n d s t r u c t u r a l p e r f e c t i o n in c o m p o u n d
semiconductors has brought about new etching
systems w h i c h p o s s e s s a f u n d a m e n t a l l y
differ
e n t m e c h a n i s m of r e v e a l i n g defects. I n s t e a d of
d i s l o c a t i o n - r e l a t e d e t c h p i t s , hillocks o r c o m p l e x
etch features a r e f o r m e d . I n a d d i t i o n , very h i g h

Materials:

Characterization

by

Etching

defect selectivity is o b t a i n e d o n b o t h c r y s t a l l o g r a p h i c a n d c h e m i c a l i n h o m o g e n e i t i e s w h e n illumi

n a t i o n is u s e d d u r i n g e t c h i n g . T h i s fact h a s b r o u g h t
a b o u t n e w exciting possibilities in c h a r a c t e r i z a t i o n
of c o m p o u n d s e m i c o n d u c t o r s a n d is a m a t t e r of
n u m e r o u s c u r r e n t s t u d i e s . C o n s e q u e n t l y , t h e r e is as
yet n o well-established t h e o r y d e s c r i b i n g t h e f o r m a
t i o n of defect-related e t c h h i l l o c k s , a l t h o u g h s o m e
p r i n c i p l e s a r e a l r e a d y b e c o m i n g clear.

/. General
Solutions

Characteristics

of Chemical

Etching

in

W e t c h e m i c a l e t c h i n g of s e m i c o n d u c t o r s c a n b e
divided i n t o t w o m a i n categories with respect t o t h e
rate-limiting step of surface r e a c t i o n s . T o t h e first
c a t e g o r y b e l o n g processes w h e r e t h e diffusion of
r e a c t a n t s a n d r e a c t i o n p r o d u c t s t o w a r d s o r from t h e
surface is r a t e limiting. T h e o v e r a l l e t c h r a t e (i.e.,
t h e n u m b e r of molecules r e m o v e d p e r u n i t time from
t h e surface) is in this case d e t e r m i n e d b y F i c k ' s first
law of diffusion:

dt

(1)

w h e r e D is t h e diffusion coefficient of r e a c t a n t s in t h e
liquid, Ax is t h e projected surface a r e a a s s u m i n g small
surface irregularities c o m p a r e d with t h e thickness d of
t h e b o u n d a r y liquid layer depleted of r e a c t a n t s a n d c
is t h e c o n c e n t r a t i o n of r e a c t a n t s . A n ideal diffusionlimited e t c h i n g s o l u t i o n p r o d u c e s flat a n d m i r r o r l i k e
surfaces; n o c o m p o s i t i o n a l o r c r y s t a l l o g r a p h i c defects
a r e revealed (polishing etching).
T h e s e c o n d c a t e g o r y covers selective etching (or
defect revealing) w h e r e selectivity refers t o t h e local
differences in t h e etch r a t e o n s t r u c t u r a l o r chemical
i n h o m o g e n e i t i e s in t h e s a m e m a t e r i a l . ( T h e t e r m
" s e l e c t i v e " is also used t o describe chemical polishing
w i t h different e t c h r a t e s o n c o m p o s i t i o n a l differences,
as in h e t e r o s t r u c t u r e s o r a l o n g different crystal
l o g r a p h i c directions. T h i s last chemical t r e a t m e n t is
called selective, a n i s o t r o p i c , preferential o r profile
etching.) I n this case t h e c h e m i c a l activity of t h e
surface, w h i c h for s e m i c o n d u c t o r s d e p e n d s o n crystal
l o g r a p h i c , electronic a n d p a s s i v a t i o n effects, is t h e
rate-limiting step. T h e r a t e of such a n activationc o n t r o l l e d (kinetically c o n t r o l l e d ) p r o c e s s c a n be d e
scribed b y
^ = kAc
dt

(2)

w h e r e k is chemical r a t e c o n s t a n t a n d A is t h e real
surface a r e a . T h e a c t i o n of a n ideal defect selective
etch d o e s n o t d e p e n d o n mixing b e c a u s e diffusion in
t h e liquid is h i g h e r t h a n t h e r a t e of etching. H o w e v e r ,

445

Semiconducting

Materials:

Lateral distance
(a)

(mm)

Characterization

Lateral distance

by

Etching

(mm)

(b)

Figure 1
Surface profiles for (a) diffusion-limited and (b) defectselective etching of compound semiconductors
(D denotes surface irregularities related to defects)

t h e electrostatic effect t h a t arises a t t h e s e m i c o n d u c

t o r - s o l u t i o n interface m i g h t result in c a p t u r e of s o m e
reaction p r o d u c t s (gas b u b b l e s , c o m p l e x e s , precipi
tates) a t the etched surface t o p r o d u c e artifacts n o t
related t o the real defects. T h e r e f o r e , a g i t a t i o n d u r i n g
selective etching in s o m e e t c h a n t s is r e c o m m e n d e d .
T h e t e m p e r a t u r e d e p e n d e n c e of t h e etch r a t e for a
given s e m i c o n d u c t o r - s o l u t i o n system is also i m p o r t
a n t . F o r m a n y systems, w h e n t h e t e m p e r a t u r e is
raised t h e r e a c t i o n r a t e exceeds t h e diffusion r a t e a n d
selective a c t i o n is c h a n g e d i n t o polishing. S u c h a
t r a n s i t i o n is easily recognized o n t h e p l o t of log(etch
rate) vs inverse t e m p e r a t u r e , b e c a u s e selective etching
h a s a higher a c t i v a t i o n energy t h a n polishing. Similar
effects c a n be achieved b y r e d u c i n g the a m o u n t of o n e
c o m p o n e n t of t h e etching m i x t u r e t o such a value t h a t
its diffusion b e c o m e s a rate-limiting factor. O n the
c o n t r a r y , w h e n v i g o r o u s a g i t a t i o n is e m p l o y e d d u r i n g
polishing t h e b o u n d a r y layer thickness s h r i n k s t o z e r o
a n d etching b e c o m e s limited by t h e r e a c t i o n r a t e . T h e
simplest w a y t o a p p r a i s e t h e type of rate-limiting step
of a given s o l u t i o n is t o r e c o r d the r a t e a c r o s s t h e
partially m a s k e d s e m i c o n d u c t o r surface: diffusionlimited etches s h o w increased etch r a t e a t t h e m a s k
edge (the t r e n c h i n g o r " n e g a t i v e c r o w n " effect) as
illustrated in F i g . l a while, for kinetically c o n t r o l l e d
etches, f l a t - b o t t o m e d profiles a r e f o r m e d with local
v a r i a t i o n s of t h e etch r a t e o n defect sites (see Fig. l b ) .
M o r e detailed discussion of these p h e n o m e n a is given
by Miller a n d R o z g o n y i (1980) a n d M u k h e r j e e a n d
W o o d a r d (1985).
It is well established t h a t etching processes for
s e m i c o n d u c t o r s a r e of a n electrochemical n a t u r e .
W h e n a s e m i c o n d u c t o r is i n t r o d u c e d i n t o t h e solution
c o n t a i n i n g oxidizing a n d r e d u c i n g a g e n t s (a r e d o x
system), t w o s e p a r a t e electrochemical r e a c t i o n s o c c u r
s i m u l t a n e o u s l y o n t h e surface. T h e first is o x i d a t i o n
involving p a s s i v a t i n g oxide layer f o r m a t i o n , while t h e
second involves r e d u c t i o n of t h e a d s o r b e d oxide c o m
plexes. D e s p i t e t h e fact t h a t only etching w i t h o u t a n y
external p o t e n t i a l (electroless etching u n d e r o p e n circuit c o n d i t i o n s ) is c o n s i d e r e d here, a mixed p o t e n
tial Vmix is established a t t h e s e m i c o n d u c t o r surface a t
which t h e r e d u c t i o n a n d o x i d a t i o n r e a c t i o n s o c c u r

446

Figure 2
Rapid local etching of -type GaAs due to illumination of
the semiconductor surface using a parallel light beam of
diameter = 50 (scanning electron microscope image,
specimen tilt 45)

with t h e s a m e r a t e (i.e., t h e p a r t i a l a n o d i c a n d c a t h o dic c u r r e n t densities, / + a n d i~ a r e e q u a l ) . F o l l o w i n g

t h e general rules of electrochemical kinetics (Vetter
1967), t h e etch r a t e Ve is t h e n p r o p o r t i o n a l t o the
p a r t i a l c u r r e n t s (Ve oc i+, / " ) . T h i s relation d o e s n o t
h o l d for t h e w h o l e etched surface w h e n a n i n h o m o g e n e o u s s e m i c o n d u c t o r is etched in a kinetically c o n
trolled s o l u t i o n a n d t h e c a t h o d i c p r o t e c t i o n effect
a c c o u n t s for g o o d defect-selective etching (see Sect.
3).
R e c e n t electrochemical studies h a v e p r o v e d t h a t for
dissolution of c o m p o u n d s e m i c o n d u c t o r s in different
r e d o x systems, carriers (particularly holes) a r e
r e q u i r e d . T h e s e holes a r e available from the semicon
d u c t o r itself a n d a r e injected from t h e etching solution
b y a n oxidizing agent. C o n s e q u e n t l y , t h e overall etch
r a t e c a n be strongly influenced b y t h e a d d i t i o n a l
supply of carriers; also, a n y local fluctuation of the
n u m b e r of holes a t the s e m i c o n d u c t o r surface will
i m m e d i a t e l y influence the etch r a t e . T h e first p o s
sibility f o r m s t h e basis of t h e p h o t o e t c h i n g m e t h o d .
F i g u r e 2 illustrates t h e effect of local i l l u m i n a t i o n of
-type G a A s o n t h e etch r a t e in a solution of H F a n d
C r 0 3 . T h e overall etch r a t e is very low, b u t the a r e a
illuminated b y a high-intensity h e l i u m - n e o n laser
b e a m is etched very quickly d u e t o the c r e a t i o n of
p h o t o g e n e r a t e d carriers.
T h e availability of holes a t t h e s e m i c o n d u c t o r sur
face d e p e n d s strongly o n t h e electronic s t r u c t u r e of
t h e m a t e r i a l . In -type c o m p o u n d s e m i c o n d u c t o r s ,
the b a n d s b e n d u p w a r d s d u r i n g electroless etching
a n d a space-charge layer is established, being depleted
of majority carriers (electrons) a n d c o n t a i n i n g s o m e

Semiconducting

i m m o b i l e holes. T h e u s e of light d u r i n g e t c h i n g of ntype m a t e r i a l is therefore effective n o t only t o speed

u p t h e overall r e a c t i o n r a t e b u t also t o reveal t h e
defects: c r y s t a l l o g r a p h i c defects a r e effective sites for
the r e c o m b i n a t i o n of p h o t o g e n e r a t e d carriers while
chemical i n h o m o g e n e i t i e s c a u s e v a r i a t i o n o f t h e
space-charge layer w i d t h . E x a m p l e s of t h e effects of
these m e c h a n i s m s a r e s h o w n in Sects. 2.3 a n d 3. \nptype m a t e r i a l , t h e b a n d s a r e nearly flat d u r i n g electroless etching a n d t h e c o n c e n t r a t i o n of m a j o r i t y carriers
(holes) is high a t t h e surface. T h e p h o t o g e n e r a t e d
carriers r e c o m b i n e r a p i d l y w i t h o u t a n y r e m a r k a b l e
influence o n t h e overall e t c h i n g r a t e , n o r o n defect
selectivity.

2. Dislocation-Related
2.1 Etch

Etch

Figures

Pits

D e p e n d i n g o n t h e m e c h a n i s m of t h e r e a c t i o n t h a t
takes place o n t h e surface of a c o m p o u n d s e m i c o n
d u c t o r , t w o g r o u p s of etch features f o r m e d o n dislo
c a t i o n s c a n b e discerned, n a m e l y etch pits a n d etch
hillocks. T h e first g r o u p , s h o w n schematically in Figs.
3 a - c , covers preferential a n d n o n p r e f e r e n t i a l pits. T h e
s h a p e of t h e etch pits d e p e n d s o n t h e c r y s t a l l o g r a p h i c
o r i e n t a t i o n o f t h e e t c h e d surface a n d o n t h e inclina
tion of t h e d i s l o c a t i o n line. T h e s h a p e of t h e etch
hillocks d e p e n d s only o n t h e inclination o f t h e linear
defect. E t c h pits o n dislocations p e r p e n d i c u l a r t o t h e
surface a r e c e n t r o s y m m e t r i c a l . D i s l o c a t i o n s with dif
ferent inclinations w i t h respect t o t h e etched surfaces
c a n be recognized in Figs. 4 a , 5 a n d 7a. O n t h e basis o f
the shift of t h e b o t t o m p o i n t o f t h e c r y s t a l l o g r a p h i c
pit vs t h e g e o m e t r i c a l c e n t e r of t h e p i t c o n t o u r a t t h e
surface a n d t h e p i t d e p t h d (see F i g . 3 a ) , t h e inclina
tion angle of t h e s t r a i g h t d i s l o c a t i o n line c a n b e
d e t e r m i n e d from t h e simple r e l a t i o n s h i p : tgcn = d/x.
K n o w i n g this angle a n d t h e c o o r d i n a t i o n system from
the external s h a p e of t h e p i t , t h e c r y s t a l l o g r a p h i c
direction of t h e d i s l o c a t i o n line c a n b e calculated.
T h e r e a r e t w o c o n d i t i o n s for t h e f o r m a t i o n of etch
pits. T h e first is related t o t h e t h e r m o d y n a m i c s o f t h e
c r y s t a l - e t c h a n t system. T h e r e m u s t b e a sufficient
p o t e n t i a l ( G i b b s free energy) difference b e t w e e n t h e
defect site a n d t h e perfect lattice in o r d e r t o c r e a t e a
stable nucleus of t h e p i t . D i s l o c a t i o n - r e l a t e d strain
fields a n d / o r t h e associated C o t t r e l l a t m o s p h e r e s a r e
the r e a s o n s for a local increase o f chemical p o t e n t i a l
which is t h e driving force for t h e n u c l e a t i o n o f a p i t .
O n c e t h e stable n u c l e u s is f o r m e d it g r o w s b y t h e
h o r i z o n t a l m o v e m e n t of steps. D e p e n d i n g o n t h e
a t o m i c perfection of t h e steps (i.e., f o r m a t i o n a n d
kinetics of k i n k m o v e m e n t ) , either c r y s t a l l o g r a p h i c
(preferential) o r n o n p r e f e r e n t i a l pits d e v e l o p (Figs.
3b, c). T h e second necessary c o n d i t i o n for t h e f o r m a
tion of p i t o n a d i s l o c a t i o n d e p e n d s o n t h e kinetics
of dissolution of t h e perfect surface a n d t h e defect

Materials:

Characterization

(d)_i

by

Etching

1-

Figure 3
Schematic representation of (a)-(c) etch pits and
(d) hillocks formed on dislocations intersecting the etched
surface: (a) and (d) are cross sections; (b) and (c) are
surface views of preferential and nonpreferential pits,
respectively

a r e a . Well-developed pits a r e f o r m e d w h e n VD$>Vp

a n d K S / F D < 1 0 , w h e r e VD, Vp a n d Vs a r e rates of
d i s s o l u t i o n a t t h e dislocation, h o r i z o n t a l step m o v e
m e n t a n d o n defect-free surface, respectively, a s
s h o w n in F i g . 3a. ( M o r e precise definition of t h e
observability of pits is m e a n i n g l e s s , unless t h e vertical
r e s o l u t i o n o f t h e t e c h n i q u e e m p l o y e d for surface
e x a m i n a t i o n is also t a k e n i n t o a c c o u n t . ) A clear
d e m o n s t r a t i o n of t h e kinetics-related rules of pit
f o r m a t i o n is o b t a i n e d b y s i m u l t a n e o u s etching of
{111}A a n d {111}B surfaces of I I I - V s e m i c o n d u c t o r s .
It is well established t h a t {111}B p l a n e s a r e very
reactive chemically since ( g r o u p V a t o m s ) a r e only
triply b o n d e d t o t h e lattice while their n o r m a l valence
is five. { I l l } A surfaces a r e m u c h less reactive since A
( g r o u p I I I a t o m s ) , a l t h o u g h also triply b o n d e d , a r e
n o r m a l l y trivalent. F i g u r e 4 a s h o w s well-developed
dislocation-related etch pits o n a {11 l } G a surface of a
G a A s wafer after etching in H N 0 3 - H 2 0 solution
(Schell etch). T h e overall etch r a t e Vp is very low b u t
VD is high leading t o t h e f o r m a t i o n of d e e p terraced
pits. O n t h e o p p o s i t e {11 l}As surface t h e overall etch
r a t e Vp is high a n d a l m o s t e q u a l t o VO. T h e pits
c a n n o t therefore d e v e l o p , being only w e a k l y m a r k e d
(Fig. 4 b ) . F o r a detailed description o f t h e k i n e m a t i c
a n d t h e r m o d y n a m i c theories of etch pit f o r m a t i o n ,
see H e i m a n n (1982) a n d S a n g w a l (1987).
T h e s h a p e of t h e preferential etch pits indicates t h e
c r y s t a l l o g r a p h i c o r i e n t a t i o n of t h e etched surfaces.
T h i s is p a r t i c u l a r l y i m p o r t a n t for t h e n o n p o l a r faces
of I I I - V c o m p o u n d s , for e x a m p l e {001}, which still
s h o w p o l a r i t y in t h e p l a n e itself in <TlO> a n d <110>
directions. T h e s e t w o n o n e q u i v a l e n t directions c a n be
distinguished, for i n s t a n c e in G a A s , b y etching in
m o l t e n K O H : pits o n t h e (001) surface a r e e l o n g a t e d
in t h e [110] direction (see F i g . 5a). H o w e v e r , t h e s h a p e
of t h e pits, in this p a r t i c u l a r case t h e extent of

447

Semiconducting

Materials:

Characterization

by

Etching
etching t h a t revealed t h e characteristic
r a d i a l d i s t r i b u t i o n of t h e E P D .

Figure 4
Result of simultaneous etching of two opposite surfaces of
a GaAs wafer in a preferential solution: (a) {11 l}Ga and
(b) { l l l } A s (differential interference contrast (DIC) image)
e l o n g a t i o n of t h e h e x a g o n a l pits, m i g h t be strongly
influenced by the d o p i n g of t h e etched m a t e r i a l .
F i g u r e 5b also s h o w s perfectly h e x a g o n a l pits
o b t a i n e d o n a (001) surface of i n d i u m - a l l o y e d G a A s
after etching in t h e s a m e c o n d i t i o n s as for t h e s a m p l e
in Fig. 5a. I n this case, i n d i u m a t o m s a r e responsible
for t h e c h a n g e in t h e kinetics of step m o v e m e n t o n
different low-index p l a n e s f o r m i n g t h e side walls of
the pits. T h e s a m e effect c a n b e o b t a i n e d using
different etching systems, inhibitors o r by changing the
t e m p e r a t u r e d u r i n g etching. F i g u r e 6 illustrates t h e
effect of variable c o m p o s i t i o n of similar etching sys
tems o n the s h a p e of preferential pits in I n P : H 3 P 0 4 H B r etch is k n o w n to p r o d u c e squarelike pits, t h a t is
with fourfold s y m m e t r y (Fig. 6a), while H N 0 3 H B r etch yields pits elongated a l o n g o n e of the <110>
directions, t h a t is with twofold symmetry (Fig. 6b).
D i s l o c a t i o n s c o n s t i t u t e a c o n t i n u o u s s o u r c e of n u cleation of atomic-size steps. A s a result, t h e size of
t h e pits d e p e n d s o n t h e time a n d / o r t e m p e r a t u r e of
etching. A n y d i s c o n t i n u i t y a l o n g t h e dislocation line
influences the regular n u c l e a t i o n of steps a n d , there
fore, the m o r p h o l o g y of the pits. F i g u r e 7a s h o w s etch
pits f o r m e d o n dislocations heavily d e c o r a t e d b y
precipitates t h a t give rise t o t h e n u c l e a t i o n of m a c r o steps. In t h e e x t r e m e case, dislocation m a y t e r m i n a t e
(or be nucleated) a t a localized microdefect. A s a
c o n s e q u e n c e , t h e c o n t i n u o u s s o u r c e of steps is
r e m o v e d from t h e m a t e r i a l a n d , instead of crystallog r a p h i c pits, shallow (S) pits a r e f o r m e d , as d o c u
m e n t e d in Fig. 7b.
T h e m o s t w i d e s p r e a d use of e t c h i n g p r o c e d u r e s t o
p r o d u c e pits is t o e s t i m a t e t h e density of dislocations
( E P D ) . T h e w h o l e etched wafers (or q u a r t e r s of t h e
(001) o r i e n t e d samples) a r e t h e n subjected t o a u t o m a
tic E P D c o u n t i n g using a m o t o r i z e d m i c r o s c o p e stage
c o u p l e d with a c o m p u t e r i z e d i m a g e analysis system.
F i g u r e 8 s h o w s a (001) G a A s wafer after preferential

448

W-shaped

2.2 Etch Hillocks

I n s o m e r e d o x etching systems used in t h e o p e n circuit c o n d i t i o n s , t h e d o m i n a t i n g role for defectselective a c t i o n o n c o m p o u n d s e m i c o n d u c t o r s is
p l a y e d b y a p a s s i v a t i n g layer. T h e thickness of this
layer increases locally a t t h e defects d e p e n d i n g o n the
degree of c r y s t a l l o g r a p h i c d e f o r m a t i o n of the lattice.
O n t h e d i s l o c a t i o n sites t h e strain field h a s t h e prevail
ing influence o n t h e value of , a l t h o u g h t h e related
Cottrell a t m o s p h e r e of impurities m i g h t also c o n t r i
b u t e indirectly. S u c h increased thickness of t h e passi
v a t i n g layer results in a local decrease of t h e etch r a t e ,
leading t o t h e f o r m a t i o n of hillocks (Fig. 3d). T h e t r u e
characteristic s h a p e of t h e dislocation-related etch
hillock f o r m e d in G a A s d u r i n g etching in r e d o x
s o l u t i o n is s h o w n in Fig. 9. T h e extent of the Cottrell
a t m o s p h e r e c a n be recognized o n t h e optical interfer
ence c o n t r a s t i m a g e (Fig. 9a), b u t is invisible o n t h e
c o r r e s p o n d i n g S E M i m a g e (Fig. 9b) because of the
p o o r e r t o p o g r a p h i c a l c o n t r a s t available in S E M . O n
t h e c o n t r a r y , t h e s u b m i c r o m e t e r - s i z e p r o t r u s i o n (P)
m a r k i n g the p o s i t i o n of t h e o u t c r o p of the dislocation
a t t h e surface, which is visible in t h e S E M i m a g e ,
c a n n o t be recognized o n t h e optical p i c t u r e .
O n e of t h e m a i n virtues of this type of defectselective etching is t h a t t h e defects a r e preserved in the
etched m a t e r i a l . C o n s e q u e n t l y , c a l i b r a t i o n of etching
with o t h e r s t r u c t u r a l o r physical m e t h o d s is possible,
with t h e defects still p r e s e n t in t h e m a t e r i a l . Such a
p r o c e d u r e is usually used w h e n t h e reliability of a n e w
e t c h a n t h a s t o b e tested. D e t a i l e d discussion of etch
ing c o n d i t i o n s a n d n u m e r o u s e x a m p l e s of defect-

Figure 5
Change in the morphology of preferential etch pits on the
(001) surface of GaAs due to differing composition of the
samples: (a) silicon-doped and (b) indium-alloyed
materials (DIC image)

Semiconducting

Materials:

Characterization

by

Etching

Figure 6
Change in the morphology of etch pits on the (001) surfaces of InP due to the different compositions of the etchants: (a)
H 3P0 4-HBr solution and (b) H N 0 3 - H B r solution (DIC image)

related etch pits a n d hillocks in G a A s a r e given by

Stirland a n d S t r a u g h a n (1976).

2.3 Influence of Light

W h e n c o n t r o l l e d i l l u m i n a t i o n is used d u r i n g e t c h i n g
of c o m p o u n d s e m i c o n d u c t o r s , t h e d o m i n a n t role for
the etch r a t e a t t h e defect sites is t a k e n over b y
r e c o m b i n a t i o n processes of p h o t o g e n e r a t e d carriers,
d u e t o b o t h t h e d e f o r m a t i o n field of d i s l o c a t i o n s a n d
the related C o t t r e l l a t m o s p h e r e s . T h i s m e c h a n i s m is
effective o n w-type a n d semi-insulating s e m i c o n d u c
t o r s , excluding /?-type m a t e r i a l for t h e r e a s o n given in
Sect. 1. D u r i n g p h o t o e t c h i n g t h e o u t c r o p s of disloca
tions always c a u s e t h e f o r m a t i o n of well-defined
hillocks similar t o t h a t of F i g . 9 b ; h o w e v e r , t h e
submicrometer protrusions are n o w attributed to the
core r e c o m b i n a t i o n a n d related n e i g h b o r i n g a r e a d e
pleted of p h o t o c a r r i e r s . C o t t r e l l a t m o s p h e r e s a r e

Figure 7
(a) Effect of decoration of dislocations by precipitates on
the morphology of preferential pitsformation of
macrosteps; and (b) transition from crystallographic to S
pits due to termination of dislocations at microdefects
(DIC images)

revealed as either hillocks o r d e p r e s s i o n s d e p e n d i n g

o n their electronic n a t u r e . F i g u r e 10 illustrates these
t w o possibilities o b s e r v e d after p h o t o e t c h i n g of nt y p e G a A s in a r e d o x s o l u t i o n . W h e n the Cottrell
atmosphere contains As-dominating recombinative
defects, there is a local decrease of carriers (holes) for
surface r e a c t i o n a n d w e l l - p r o n o u n c e d hillocks a r e
f o r m e d as s h o w n in Figs. 10a a n d b . W h e n , d u e to
s o m e c o m p o s i t i o n a l modification d u r i n g crystalliza
t i o n , t h e C o t t r e l l a t m o s p h e r e s a r o u n d dislocations are
d o m i n a t e d b y a c c e p t o r - t y p e defects, t h e a m o u n t of
holes increases locally a n d t h e a t m o s p h e r e s a r e etched
at a higher r a t e t h a n t h e m a t r i x (Figs. 10c, d ) . N o t e ,
h o w e v e r , t h a t in b o t h m a t e r i a l s t h e r e c o m b i n a t i o n a t
t h e dislocations themselves leads t o t h e f o r m a t i o n of
identical p r o t r u s i o n s . It is also i m p o r t a n t t o n o t e a
r e m a r k a b l e difference b e t w e e n defect sensitivity
o b t a i n e d using t h e s a m e etching system ( s e m i c o n d u c t o r - e t c h a n t ) with a n d w i t h o u t i l l u m i n a t i o n (cf. Figs.
9a a n d 10c). T h e etch d e p t h r e q u i r e d t o reveal defects
with i l l u m i n a t i o n is s u b m i c r o m e t e r (i.e., it is usually
a n o r d e r of m a g n i t u d e smaller t h a n t h e d e p t h
r e q u i r e d t o reveal dislocations b y etching w i t h o u t
illumination).

Figure 8
Characteristic W-shaped distribution of the EPD on the
(001) oriented 2" GaAs wafer after preferential etching

449

Semiconducting

Materials:

Characterization

by

Etching
0.5

(C) 0.4

0.31-1
0.1
-20-10 0

10 2 0 3 0 4 0
(/urn)

Figure 9
Etch hillock formed on a dislocation in /z-type GaAs during etching in a selective solution without illumination: (a) DIC
image; (b) SEM image, tilt 85; and (c) surface profile along x-x'

3. Revealing

Chemical

Inhomogeneities

T w o types of chemical inhomogeneities are inherent t o

c o m p o u n d semiconductors, namely g r o w t h striations
d u e t o segregation in t h e melt a n d s e c o n d - p h a s e
particles (precipitates) f o r m e d d u r i n g p o s t g r o w t h
cooling a s t h e result of d i m i n i s h i n g solubility in t h e
solid solution. E t c h i n g is o n e of t h e m e t h o d s m o s t
frequently used t o reveal these defects d u e t o its high
sensitivity a n d g o o d spatial r e s o l u t i o n ( w h e n optical
m i c r o s c o p y o r surface profiling a r e used t o r e c o r d t h e
results of etching). F o r g r o w t h striations, etching
b e c o m e s a s e m i q u a n t i t a t i v e t o o l t o e v a l u a t e t h e level
of fluctuation of d o p a n t s . T h e m e c h a n i s m s u n d e r
lying t h e differentiation of t h e etch r a t e o n a r e a s w i t h
different d o p a n t o r i m p u r i t y c o n t e n t a r e basically

diversified d e p e n d i n g o n t h e electronic s t r u c t u r e of
t h e etched m a t e r i a l . I n />-type s e m i c o n d u c t o r s , the
v a r i a b l e etch r a t e o n a r e a s w i t h lower a n d higher p+
carrier c o n c e n t r a t i o n s c a n be explained in t e r m s of
c a t h o d i c p r o t e c t i o n of regions by p+ regions as
illustrated in F i g . 11. T h e open-circuit p o t e n t i a l in this
m i x e d p / p + system a s s u m e s a n i n t e r m e d i a t e value K m ix
b e t w e e n t h e rest p o t e n t i a l s which w o u l d h a v e been
o b t a i n e d in t h e t w o s e p a r a t e a n d p+ samples. A s a
result, t w o different p a r t i a l c u r r e n t s a n d c o r r e s p o n d
ing etch rates a r e established, being higher for the p+
region.
F o r n/n+ systems, a n o t h e r factor b e c o m e s decisive,
n a m e l y t h e w i d t h w of t h e space c h a r g e layer which is
related t o t h e d o p a n t c o n c e n t r a t i o n N. A s increased
d o p a n t c o n c e n t r a t i o n c o r r e s p o n d s t o a d i m i n i s h e d w,
fewer holes a r e available for surface r e a c t i o n in n+
a r e a s c o m p a r e d w i t h a r e a s . T h e s a m e relation h o l d s
for e t c h i n g in t h e d a r k a n d u n d e r i l l u m i n a t i o n b u t t h e

P+

-40

-20

20

40

60

(d)
()

(a)
()

Figure 10
Influence of the electronic properties of the Cottrell
atmospheres on the morphology of etch features formed
during photoetching: (a) and (b) etch hillocks in -type
GaAs grown from arsenic-rich melt; (c) and (d) complex
etch features in -type GaAs grown from gallium-rich
melt; (a) and (c) DIC images; (b) and (d) surface profiles
on the defect-related etch features
450

(b)

Figure 11
(a) Anodic current density ia vs surface polarization V for
/?-type GaAs material with a variable carrier concentration
p/p+ and (b) the corresponding schematic representation
of an etched sample with growth striations due to
segregation of p-type dopant: vp and vp+ are etching
velocities proportional to the partial anodic currents (after
Weyher and van de Ven 1986 J. Crystal Growth 78:
191-217. Reproduced with permission)

Semiconducting

Figure 12
Remarkable alteration of the etch rate during
photoetching of an n/n+ area in GaAs: (a) DIC image of
the surface, (b) surface profile (i.e., relative etch depth)
plotted along x-x' line and (c) well-resolved growth
striations related to the fluctuation of deep recombinative
centers, revealed by photoetching on the (110) longitudinal
section of an undoped GaAs crystal (DIC image)

overall etch r a t e a n d sensitivity is increased w h e n

carriers a r e g e n e r a t e d b y t h e light. A n e x a m p l e of t h e
different etch r a t e in n/n+ system is s h o w n in F i g . 12a
w h e r e n+ facet (coring) w a s revealed in silicon-doped
G a A s by p h o t o e t c h i n g . T h e g r a p h in Fig. 12b r e p r e
sents t h e surface profile (i.e., t h e relative etch d e p t h
p l o t a l o n g the line x-x'). T h e electrochemical p r i n
ciples of etching of such m i x e d systems in I I I - V

Materials:

Characterization

by

Etching

s e m i c o n d u c t o r s a r e discussed in detail by N o t t e n et al.

(1991).
I n semi-insulating c o m p o u n d s the v a r i a t i o n of the
etch r a t e , especially w h e n light is used, is a t t r i b u t e d t o
t h e i n h o m o g e n e o u s d i s t r i b u t i o n of t h e r e c o m b i n a t i v e
impurities (native defects). T h e increased c o n c e n t r a
tion of such defects decreases t h e n u m b e r of carriers
for surface r e a c t i o n a n d , c o n s e q u e n t l y , the etch r a t e
decreases locally. P h o t o e t c h i n g of t h e l o n g i t u d i n a l
sections of u n d o p e d c o m p o u n d crystals is a quick w a y
t o reveal a n d s t u d y t h e s o l i d - l i q u i d interface t h r o u g h
revealing g r o w t h s t r i a t i o n s a n d is c o m m o n l y used for
I I I - V c o m p o u n d crystals. A n e x a m p l e of s h a r p l y
m a r k e d s t r i a t i o n s in high-resistivity u n d o p e d G a A s is
s h o w n in Fig. 12c.
N u m e r o u s recently p u b l i s h e d results h a v e p r o v e d
t h e ability of etching t o visualize t h e presence of
n a n o m e t e r - s i z e precipitates. In this case, precipitates
c o n s t i t u t e n u c l e a t i o n sites for f o r m a t i o n of pits d u e t o
their different chemical c o m p o s i t i o n c o m p a r e d with
t h e h o s t crystal. Since precipitates a r e limited in size,
t h e pits r e m a i n shallow (so-called S pits), g r o w i n g
only h o r i z o n t a l l y as e t c h i n g p r o c e e d s . T h e r e f o r e , the
size of t h e r e s u l t a n t pits d e p e n d s o n the d u r a t i o n of
etching, usually being several o r d e r s of m a g n i t u d e
larger t h a n t h e size of precipitates. F i g u r e 13 illus
t r a t e s characteristic S pits f o r m e d o n arsenic precipi
tates (usually lOOnm in d i a m e t e r as established by
t r a n s m i s s i o n electron m i c r o s c o p y ) d u r i n g selective
sequential etching of G a A s . A s t h e precipitates are
d e c o r a t i n g a dislocation D a l m o s t parallel t o the
surface (Fig. 13a), the r e p e a t e d etching p r o c e d u r e
(Fig. 13b) reveals m o r e of t h e m a n d clearly d e m o n
strates lateral g r o w t h of S pits. D e p e n d i n g o n the
chemical n a t u r e of the precipitates a n d t h e etching
system e m p l o y e d , they m a y also be m o r e resistant
t h a n t h e s u r r o u n d i n g m a t r i x leading t o t h e f o r m a t i o n
of small hillocks.
S t r u c t u r a l e t c h i n g h a s a well-established p o s i t i o n in
t h e fabrication of b u l k c o m p o u n d s e m i c o n d u c t o r
crystals a n d d u r i n g s u b s e q u e n t device fabrication;
E P D measurements are but one example. However,
recently i n t r o d u c e d n e w r e d o x etching systems,
t o g e t h e r with the use of light h a s o p e n e d new possibil
ities in a n a l y z i n g s t r u c t u r a l features o n a m i c r o s c o p i c
scale, such as electronic p r o p e r t i e s of C o t t r e l l a t m o s
p h e r e s o r subtle s t r u c t u r a l t r a n s f o r m a t i o n s d u r i n g
a n n e a l i n g of I I I - V m a t e r i a l s . T h e n e w c o n c e p t s of
revealing defects b a s e d o n t h e electrochemical studies
of e t c h i n g h a v e been described b y N o t t e n et al. (1991),
c o n s t i t u t i n g a basis for t h e i n t e r p r e t a t i o n of c o m p l e x
etch features f o r m e d o n i n h o m o g e n e o u s s e m i c o n d u c
t o r s in r e d o x etching systems.

Figure 13
Shallow pits formed on arsenic precipitates in GaAs
grown from an arsenic-rich melt: (a) etch depth 1 ; and
(b) the same sample, etch depth 3 (DIC images)

Bibliography
Heimann R 1982 Principles of chemical etching. In:
Grabmaier J (ed.) 1982 Crystals Growth, Properties and
Applications, Vol. 8. Springer, Berlin, pp. 173-224

451

Semiconducting

Materials:

Characterization

by

Etching

Miller D C, Rozgonyi G A 1980 Defect characterization by

etching, optical microscopy and x-ray topography. In:
Keller S (ed.) 1980 Handbook on Semiconductors, Vol.
3. North-Holland, Amsterdam, pp. 218-46
Mukherjee S D, Woodard D W 1985 Etching and surface
preparation of GaAs for device fabrication. In: Howes
J, Morgan D V (eds.) 1985 Gallium Arsenide. Wiley, New
York, pp. 119-60
Notten L, van den Meerakker J A M, Kelly J J 1991
Etching of III-V Semiconductors. Elsevier, Oxford
Sangwal 1987 Etching of Crystals. North-Holland,
Amsterdam
Stirland D J, Straughan W 1976 A review of etching and
defect characterization of gallium arsenide substrate
material. Thin Solid Films 31: 139-70
Vetter J 1967 Electrochemical Kinetics. Academic Press,
London
J. L. W e y h e r
[ M A S P E C , P a r m a , Italy]

Semiconducting Materials: Electron

Microscopy
T h a t defects affect t h e p e r f o r m a n c e a n d reliability of
m i n o r i t y carrier devices is well recognized. T o en
h a n c e device p e r f o r m a n c e , t h e m e c h a n i s m s g o v e r n i n g
the i n t r o d u c t i o n of defects i n t o s e m i c o n d u c t i n g
m a t e r i a l s d u r i n g g r o w t h a n d processing m u s t be
u n d e r s t o o d . T o achieve this g o a l , the m i c r o s t r u c t u r e s
of a s - g r o w n a n d processed m a t e r i a l s m u s t be c h a r a c
terized.
Several t e c h n i q u e s , such as defect etching, x-ray
t o p o g r a p h y a n d t r a n s m i s s i o n electron m i c r o s c o p y
( T E M ) , a r e available for s t r u c t u r a l c h a r a c t e r i z a t i o n ,
b u t T E M is u n i q u e in t h a t it h a s a very high spatial
resolution a n d c a n p r o v i d e detailed c r y s t a l l o g r a p h i c
i n f o r m a t i o n . W i t h the c o n t i n u e d d e v e l o p m e n t s in
analytical electron m i c r o s c o p y a n d h i g h - r e s o l u t i o n
T E M ( H R T E M ) , it is n o w possible t o c o u p l e c h e m
ical i n f o r m a t i o n o b t a i n e d a t a n a n o c r y s t a l l i n e level
with s t r u c t u r a l analysis.
U s i n g d i m e n s i o n a l i t y as a criterion, defects c a n b e
classified i n t o four different categories:
(a)

zero d i m e n s i o n a l t y p i c a l e x a m p l e s a r e v a c a n
cies, interstitials, v a c a n c y - i n t e r s t i t i a l p a i r s , a n d
so o n ;

(b)

one dimensionaldislocations
category;

(c)

two dimensionaltypical examples are stacking

faults, twins, g r a i n b o u n d a r i e s , a n d so o n ; a n d

(d)

three d i m e n s i o n a l p r e c i p i t a t e s a n d
b e l o n g t o this c a t e g o r y .

belong to

this

inclusions

Unless the p o i n t defects h a v e clustered t o f o r m dislo

c a t i o n l o o p s , they c a n n o t b e investigated directly
using T E M because of their extremely small size.

452

A l t e r n a t i v e t e c h n i q u e s , such as field-ion m i c r o s c o p y ,
h a v e s h o w n s o m e p r o m i s e for observing t h e m in
different m a t e r i a l s . O n t h e o t h e r h a n d , since its d e
v e l o p m e n t in t h e mid-1950s, T E M h a s played a very
crucial role in u n d e r s t a n d i n g t h e i n t r o d u c t i o n of one-,
t w o - a n d t h r e e - d i m e n s i o n a l defects in s e m i c o n d u c
tors; t h e r e a d e r is referred t o review articles b y
M a h a j a n (1989) a n d Cullis (1990) t o d e v e l o p a n
a p p r e c i a t i o n of this role.
T w o types of specimen a r e used in T E M studies:
p l a n view a n d cross sectional. T h e plan-view speci
m e n s a r e suitable for e x a m i n i n g a s - g r o w n b u l k crys
tals a n d epitaxial layers. H o w e v e r , for e v a l u a t i n g
m u l t i l a y e r s t r u c t u r e s , w h i c h f o r m t h e b a c k b o n e of
state-of-the-art solid-state electronics t e c h n o l o g y ,
cross sections a r e essential. N o t only d o they p r o v i d e
i n f o r m a t i o n o n interfaces b e t w e e n different m a t e r i a l s
c o n s t i t u t i n g a multilayer, b u t also they shed light o n
t h e g e n e r a t i o n a n d p r o p a g a t i o n of defects d u r i n g
g r o w t h a n d processing.
T h e p r e p a r a t i o n of b o t h plan-view a n d crosssectional s a m p l e s t h i n e n o u g h t o p r o v i d e electron
t r a n s p a r e n c y m a y involve either chemical t h i n n i n g o r
ion milling. T h e latter c o n v e n t i o n a l l y e m p l o y s low+
voltage A r ions b u t C h e w a n d Cullis (1987) h a v e
s h o w n t h a t the milling of m a t e r i a l s , such as I n P , C d T e
+
a n d Z n S e , using A r i o n s p r o d u c e s u n w a n t e d surface
artefacts, even a t 77 K . T h e s e c a n , h o w e v e r , b e elim
+
i n a t e d b y t h e a p p l i c a t i o n of reactive I ion milling.
Cross-sectional s a m p l e s c a n be p r e p a r e d using the
p r o c e d u r e p h o t o g r a p h i c a l l y described in Fig. 1. First,
pieces a r o u n d 10 m m x 1 m m a r e cleaved from
polished wafer s a m p l e s . U s i n g a d d i t i o n a l b a c k i n g
b l o c k s of a r o u n d 10 m m x 3 m m x 1 m m (Fig. l a ) of
b u l k silicon, t h e cleaved s a m p l e s a r e b o n d e d face t o
face using s t a n d a r d quick-setting e p o x y resin as
s h o w n in Fig. l b . C a r e is t a k e n d u r i n g t h e b o n d i n g
process t o e n s u r e all b o n d e d surfaces a r e clean a n d
free from p a r t i c u l a t e m a t t e r . C l a m p s with accurately
parallel j a w s a r e used t o h o l d t h e samples t o g e t h e r
u n d e r m o d e r a t e p r e s s u r e d u r i n g setting of the e p o x y
resin. B o n d e d s a m p l e s a r e t h e n polished o n b o t h
e x p o s e d sides (Fig. l c t h e p o s i t i o n of t h e center j o i n
is indicated) a n d specimen disks a r e c u t using a n
u l t r a s o n i c c u t t e r e m p l o y i n g a 600 grit silicon c a r b i d e
abrasive slurry in w a t e r . F o r a d d i t i o n a l s t r e n g t h a n d
ease of h a n d l i n g , thin m e t a l rings a r e b o n d e d t o the
specimen disks w i t h quick-setting e p o x y resin (rings
indicated b y R in Fig. l e ) . T h e disks a r e ultimately
r e m o v e d from t h e s u p p o r t i n g glass slides a n d a r e ion
milled.
T h e following e x a m p l e s h a v e b e e n c h o s e n t o illus
t r a t e t h e roles of T E M a n d H R T E M in s t r u c t u r a l
c h a r a c t e r i z a t i o n of s e m i c o n d u c t o r s :
(a)

replication of dislocations d u r i n g h o m o e p i t a x y ,

(b)

c o p p e r a n d i r o n suicide p r e c i p i t a t i o n o n stacking
faults in silicon as a result of device processing,

(c)

arsenic precipitates in b u l k G a A s crystals, a n d

Semiconducting

Materials:

Electron

Microscopy

p r o t r u s i o n a n d a d e p r e s s i o n a t t h e e m e r g e n c e p o i n t of
t h e d i s l o c a t i o n a t t h e surface in F i g . 2 facilitates t h e
replication p r o c e s s .
F i g u r e 3, r e p r o d u c e d f r o m t h e s t u d y of Cullis a n d
K a t z (1974), s h o w s a silicon device s t r u c t u r e with a n
electrically active r o d defect lying a l o n g t h e p l a n e of
a n inclined s t a c k i n g fault w i t h subsidiary precipitate
a r r a y s . T h i s m i c r o g r a p h w a s o b t a i n e d from a n -type
silicon wafer t h a t h a d u n d e r g o n e a processing se
q u e n c e involving o x i d a t i o n , b o r o n drive in a n d reoxid a t i o n . Cullis a n d K a t z (1974) h a v e s h o w n t h a t such
faults (often m u l t i p l e o v e r l a p p i n g s e e Fig. 3a) a r e
extrinsic in n a t u r e , a r e b o u n d e d b y <111>/3 F r a n k
p a r t i a l s a n d t h a t t h e r o d defects result from i m p u r i t y
i r o n p r e c i p i t a t i o n as F e S i 2 . F u r t h e r m o r e , t h e s u b
sidiary precipitates h a v e b e e n identified as c o p p e r
suicides. H a v i n g fully a n a l y z e d these m i c r o s t r u c t u r a l
features in processed silicon wafers, Cullis a n d K a t z
(1974) devised a processing p r o c e d u r e w h i c h elimi
n a t e d metallic suicide f o r m a t i o n . T h e y were t h u s able
t o e n h a n c e t h e yield of devices fabricated from t h e
p r o c e s s e d wafers.
R e t u r n i n g t o t h e t o p i c of I I I - V c o m p o u n d s , Fig. 4
s h o w s a N o m a r s k i interference c o n t r a s t m i c r o g r a p h

Figure 1
(a)-(f) sequence depicting the different stages of
cross-sectional sample preparation (after Chew and Cullis
1987)

(d)

interfaces in I n P - I n G a A s superlattices a n d c o m
p o s i t i o n profiles a c r o s s t h e I n P - I n G a A s a n d
I n G a A s - I n P interfaces.

F i g u r e 2 s h o w s a t r a n s m i s s i o n electron m i c r o g r a p h
o b t a i n e d from a [110] cross section of a n I n P h o m o epitaxial layer g r o w n b y liquid p h a s e epitaxy o n a
(001) s u b s t r a t e . D i s l o c a t i o n s p r e s e n t in t h e s u b s t r a t e
a r e replicated i n t o t h e epitaxial layer a n d a r e o r i e n t e d
close t o t h e [001] direction. It h a s b e e n a s c e r t a i n e d b y
T E M diffraction c o n t r a s t e x p e r i m e n t s t h a t t h e
Burgers vectors of t h e d i s l o c a t i o n s a r e a[\ 10]/2, w h e r e
a is t h e lattice p a r a m e t e r . T h u s , t h e o b s e r v e d disloca
tions a r e close t o b e i n g perfect edge type, w i t h B u r g e r s
vectors lying in t h e g r o w t h surface.
A n interesting q u e s t i o n is t o a s k h o w , if t h e B u r g e r s
vector of a d i s l o c a t i o n in t h e s u b s t r a t e is parallel t o
the surface, is it replicated i n t o t h e o v e r g r o w t h
because it d o e s n o t p r o d u c e a step o n t h e surface.
B e a m et al. (1990) h a v e a d d r e s s e d this issue a n d h a v e
a r g u e d , b a s e d o n B e a m (1989), t h a t t h e presence of a

Figure 2
Examples of dislocations propagating in the [001]
direction: (a) the interactions with other dislocations
denoted by arrows should be noted and (b) the
dislocations which do not rotate to the [001] direction
should be noted. The plane of the images is (110) (after
Beam et al. 1990)

453

Semiconducting

Materials:

Electron

Microscopy

Figure 3
Rod defect lying along the plane of an inclined stacking
fault with subsidiary precipitate structures; compare
(a) and (b) showing outside-inside contrast given by
Frank partial dislocations. Transmission electron
micrographs recorded using Bragg reflections with
opposing g vectors: bright field, strong beam, s>0 (after
Cullis and Katz 1974)

of a n etched wafer of z i n c - d o p e d , b u l k G a A s . D i s l o
c a t i o n s a p p e a r as linear features in F i g . 4 a n d detailed
e x a m i n a t i o n h a s s h o w n t h a t these features a r e ridges,
resulting from differential e t c h a n t a t t a c k a t disloca
tions a n d t h e m a t r i x . T h e circular b e a d l i k e m a r k i n g s
lying o n t h e ridges a r e pits, a n d delineate precipitate
particles w h i c h h a v e b e e n preferentially a t t a c k e d b y
t h e etch. T o discern t h e n a t u r e of these precipitates,
Cullis et al. (1980) h a v e e x a m i n e d t h e a b o v e crystals
b y T E M a n d a n e x a m p l e t a k e n from their w o r k is
r e p r o d u c e d a s F i g . 5. T h e y h a v e s h o w n using d a r k field i m a g i n g (Fig. 5b) a n d selected a r e a electron
diffraction (Fig. 5c) t h a t t h e precipitates consist of
elemental arsenic w i t h its s t a n d a r d h e x a g o n a l struc
ture. T h e presence of arsenic precipitates in b u l k
G a A s crystals is u n w a n t e d b u t u n d e r s t a n d a b l e .
Generally, a G a A s crystal is g r o w n from a n arsenicrich melt, a n d t h e presence of a n excess arsenic in t h e
crystal ( p r o b a b l y as lattice interstitials) a t t h e g r o w t h
t e m p e r a t u r e c o u l d lead t o t h e f o r m a t i o n of arsenic
precipitates d u r i n g cooling.
W i t h t h e a d v e n t of o r g a n o m e t a l l i c v a p o r p h a s e
epitaxy a n d m o l e c u l a r b e a m epitaxy, it is possible t o
g r o w superlattices a n d q u a n t u m well s t r u c t u r e s w h i c h
find extensive a p p l i c a t i o n s in state-of-the-art devices.
T h e s e a p p l i c a t i o n s require s h a r p a n d chemically
a b r u p t interfaces. I n o r d e r t o p r o d u c e such s t r u c t u r e s ,
strong interaction between the growth and structural
c h a r a c t e r i z a t i o n p e r s o n n e l is desirable. T h i s issue is
e m p h a s i z e d in t h e e x a m p l e s w h i c h follow.
454

Figure 4
Optical Nomarski interference micrograph of an etched,
zinc-doped, /?-type GaAs wafer (after Cullis et al. 1980)

F i g u r e 6a s h o w s a cross section of a q u a n t u m well

layer s t r u c t u r e g r o w n o n (001) I n P by a t m o s p h e r i c
p r e s s u r e o r g a n o m e t a l l i c v a p o r p h a s e epitaxy (Cullis
1990): t h e d a r k a n d light regions a r e I n G a A s a n d I n P
layers, respectively. It is clear t h a t t h e I n G a A s - t o - I n P
g r o w t h interfaces exhibit m a r k e d
undulations.
I n v e s t i g a t i o n s h a v e s h o w n t h a t this a s y m m e t r i c a l
g r o w t h s t r u c t u r e m a y arise from a t least t w o causes.
T h e initial g r o w t h of I n G a A s a n d I n P a p p e a r s t o b e

Semiconducting

Figure 5
Transmission electron micrographs and diffraction pattern
from a region in chromium-doped, semi-insulating GaAs
containing a precipitate at a dislocation: (a) bright field,
strong beam, 220 GaAs reflection operating; (b) dark
field, 114 precipitate reflection operating; and
(c) diffraction pattern showing precipitate reflection
(circled) used to obtain the image in (b) (after Cullis et al.
1980)

n o t always u n i f o r m l y t w o d i m e n s i o n a l , such t h a t
shallow t h r e e - d i m e n s i o n a l islands c a n b e f o r m e d b y
layer n u c l e a t i o n processes. T h i s c a n greatly d i s r u p t
the g r o w t h of very t h i n I n G a A s wells, as c a n b e seen
in Fig. 6 b , w h e r e a flat-topped island is p r e s e n t
b e t w e e n t h e a r r o w e d l o c a t i o n s w i t h i n a well n o m i n
ally 2.5 n m thick. Clearly, in this case t h e I n G a A s
layer is laterally d i s c o n t i n u o u s . F o r t h i c k e r I n G a A s
wells, careful studies using n a r r o w m a r k e r layers
( N o r m a n et al. 1989) h a v e d e m o n s t r a t e d t h a t u n d u l a
tions c a n also arise d u r i n g r e a c t a n t g a s switching a t
t h e e n d of well g r o w t h . H o w e v e r , e a c h of these
deleterious g r o w t h processes c a n b e c o n t r o l l e d b y

Materials:

Electron

Microscopy

Figure 6
Cross-sectional TEM images of InGaAs quantum wells
(dark) in InP (light), dark field (g = 002): (a) continuous
wells with asymmetrical nonplanarity and (b) narrowest
well shows island growth in arrowed region (after Cullis
1990)

suitable choice of gas flow c o n d i t i o n s in the r e a c t o r

a n d b y i m p l e m e n t a t i o n of layer g r o w t h p a u s e s . U n d e r
o p t i m u m c o n d i t i o n s , excellent q u a n t u m well u n i f o r m
ity is o b t a i n e d , as illustrated in Fig. 7. Wells of 2.5 n m
thickness a r e , in this case, c o n t i n u o u s t h r o u g h o u t the
s a m p l e , as is e m p h a s i z e d b y t h e h i g h - r e s o l u t i o n lattice
i m a g e of F i g . 7 b w h e r e only interfacial steps of a t o m i c
d i m e n s i o n s a r e p r e s e n t a t well b o u n d a r i e s .
E v e n if I n G a A s - I n P interfaces exhibit excellent
p l a n a r i t y they m a y n o t b e c o m p o s i t i o n a l l y s h a r p .

455

Semiconducting

Materials:

Electron

Microscopy

^--interfaces.

typical,
error

p\

25

35

11I

InP

InP

0.2
^
As/

direction of
growth

InGaAs
-10

-5

10

15

Distance ( n m )

Figure 8
Variation of composition, expressed in terms of atomic
fractions, across a lOnm-thick InGaAs well measured by
x-ray microanalysis. Note the asymmetry of elemental
distributions (after Cullis 1990)

s t r a t e d . B o t h plan-view a n d cross-section s a m p l e s a r e
i m p o r t a n t for such studies a l t h o u g h cross sectioning,
in p a r t i c u l a r , is essential for investigation of t h e
s h a r p n e s s of interfaces in superlattices a n d q u a n t u m
well s t r u c t u r e s .
See also: Electron Microscopy, Analytical; Electron Micros
copy, High-Resolution
Figure 7
Cross-sectional TEM images of InGaAs quantum wells in
InP showing improved planarity of well boundaries:
(a) dark-field (g = 002) showing wells of three different
thicknesses and (b) [110] high-resolution lattice image of
narrowest well (after Cullis 1990)

This situation c a n o c c u r if t h e flows of p r e c u r s o r gases

a r e n o t switched quickly. Interface s h a r p n e s s o n a
n a n o s c a l e c a n be m e a s u r e d b y exploiting x-ray
microanalysis in a s c a n n i n g t r a n s m i s s i o n electron
m i c r o s c o p e e q u i p p e d w i t h a field-emission g u n . A
c o m b i n a t i o n of the small electron p r o b e , t o g e t h e r
with t h e use of suitably thin ( ~ 40 n m ) cross-sectional
specimens allows t h e local c o m p o s i t i o n a l analysis of
q u a n t u m well s t r u c t u r e s t o be carried o u t . T h i s is
d e m o n s t r a t e d in F i g . 8 w h i c h s h o w s t h a t , for t h e
s a m p l e studied, while t h e I n P - t o - I n G a A s interface is
s h a r p , t h e I n G a A s - t o - I n P interface displays p r i n c i p
ally arsenic ( b u t also gallium) c a r r y over i n t o t h e I n P
barrier. T h e m a r k e d c o m p o s i t i o n a l a s y m m e t r y is
u n d e s i r a b l e for devices a n d c a n be greatly r e d u c e d b y
o p t i m i z a t i o n of gas switching m e t h o d s a n d flow p a t
t e r n s within t h e r e a c t o r .
I n s u m m a r y , t h e role of T E M in t h e s t r u c t u r a l
c h a r a c t e r i z a t i o n of s e m i c o n d u c t o r s h a s been d e m o n -

456

Bibliography
Beam A 1989 Dislocation replication and annihilation in
InP homoepitaxial layers grown by liquid phase epitaxy.
Ph.D. dissertation, Carnegie Mellon University
Beam A, Mahajan S, Bonner W A 1990 Dislocation
replication and annihilation in InP homoepitaxial layers
grown by liquid phase epitaxy. Mater. Sci. Eng. 7: 8 3 101
Chew G, Cullis A G 1987 The preparation of transmis
sion electron microscopy specimens from compound
semiconductors by ion milling. Ultramicroscopy 23: 17598
Cullis A G 1990 The structural characterisation of advanced
compound semiconductor heteroeptaxial systems by
transmission electron microscopy. In: Sumino (ed.)
1990 Defect Control in Semiconductors. Elsevier, Amster
dam, pp. 1097-105
Cullis A G, Augustus D, Stirland D J 1980 Arsenic
precipitation at dislocations in GaAs substrate material.
J. Appl. Phys. 51: 2556-60
Cullis A G, Katz L 1974 Electron microscope study of
electrically active impurity precipitate defects in silicon.
Philos. Mag. 30: 1419-43
Mahajan S 1989 Growth- and processing-induced defects in
semiconductors. Prog. Mater. Sci. 33: 1-82
Norman A G, Butler R, Booker G R, Thrush J 1989
TEM studies using marker layers within GalnAs/InP
quantum well structures to determine the origin of inter
face undulations. In: Cullis A G, Hutchison J L (eds.)

Single-Crystal

1989 Microscopy of Semiconducting Materials 1989. IOP

Publishing, Bristol, U K , pp. 299-304
A . G . Cullis
[Defence R e s e a r c h A g e n c y ,
Malvern, U K ]
S. M a h a j a n
[Carnegie M e l l o n U n i v e r s i t y , P i t t s b u r g h ,
Pennsylvania, USA]

Single-Crystal X-Ray Diffraction

Single-crystal x-ray diffraction, c o m m o n l y referred t o
as x-ray c r y s t a l l o g r a p h y , is a n analytical t e c h n i q u e in
which x-ray m e t h o d s a r e e m p l o y e d t o d e t e r m i n e w i t h
certainty t h e a c t u a l a r r a n g e m e n t of a t o m s w i t h i n a
crystalline specimen. T h e science of x-ray crystallog
r a p h y o r i g i n a t e d in 1912 w i t h t h e discovery b y L a u e
t h a t crystals diffract r a y s . Since t h a t t i m e , singlecrystal x-ray diffraction h a s d e v e l o p e d i n t o t h e m o s t
powerful m e t h o d k n o w n for o b t a i n i n g t h e a t o m i c
a r r a n g e m e n t in t h e solid s t a t e . T h e r a p i d g r o w t h in
t h e use of single-crystal x-ray diffraction a s a r o u t i n e
s t r u c t u r a l c h a r a c t e r i z a t i o n m e t h o d w i t h i n t h e last few
years m a y t o a large e x t e n t b e a t t r i b u t e d t o t h e
d e v e l o p m e n t of c o m p u t e r h a r d w a r e a n d software
c a p a b l e of h a n d l i n g t h e x-ray d a t a easily a n d effi
ciently. C o m p l e t e x-ray c r y s t a l l o g r a p h i c systems a r e
n o w available f r o m several m a n u f a c t u r e r s . S u c h
i n s t r u m e n t s generally include d e d i c a t e d m i n i c o m
p u t e r s w i t h associated h a r d w a r e a n d software for
i n s t r u m e n t c o n t r o l , d a t a r e d u c t i o n , s o l u t i o n a n d refi
n e m e n t of s t r u c t u r e s , a n d display a n d p l o t t i n g of final
results.
A l t h o u g h single-crystal x-ray diffraction h a s i m
p o r t a n t a p p l i c a t i o n s in m a n y diverse fields i n c l u d i n g
m i n e r a l o g y , physics, m e d i c i n e , b i o c h e m i s t r y , m e t a l
lurgy a n d m a t e r i a l s science, t h e m e t h o d is m o s t
widely used b y c h e m i s t s . T h e precise k n o w l e d g e of t h e
m o l e c u l a r g e o m e t r y of c h e m i c a l s u b s t a n c e s is b e c o m
ing increasingly i m p o r t a n t in n e a r l y all fields of c h e m
ical research. C h e m i s t s r o u t i n e l y use such t e c h n i q u e s
as n u c l e a r m a g n e t i c r e s o n a n c e , infrared a n d u l t r a
violet s p e c t r o s c o p y , m a s s s p e c t r o s c o p y a n d e l e m e n t a l
analysis for t h e identification a n d c h a r a c t e r i z a t i o n of
c o m p o u n d s p r e p a r e d a n d isolated in their l a b o r a t o r
ies. T h e e x p e r i m e n t a l d a t a o b t a i n e d f r o m these tech
niques m a y , after suitable analysis a n d i n t e r p r e t a t i o n ,
yield i m p o r t a n t i n f o r m a t i o n c o n c e r n i n g t h e c o m p o s i
tion a n d s t r u c t u r e o f t h e c o m p o u n d . H o w e v e r , s u c h
i n f o r m a t i o n is often i n c o m p l e t e , f r a g m e n t a r y a n d
a m b i g u o u s . T h e r e a r e m a n y classes of c o m p o u n d s
such a s n a t u r a l p r o d u c t s , o r g a n o m e t a l l i c c o m p l e x e s ,
i n o r g a n i c salts, m e t a l cluster systems, a n d o r g a n i c a n d
i n o r g a n i c r e a c t i o n p r o d u c t s for w h i c h t h e s t r u c t u r e
c a n n o t be d e d u c e d even w i t h all of t h e o t h e r m e t h o d s
c o m b i n e d . Single-crystal x-ray diffraction is u n i q u e l y

X-Ray

Diffraction

c a p a b l e of u n a m b i g u o u s l y d e t e r m i n i n g t h e c o m p l e t e
t h r e e - d i m e n s i o n a l m o l e c u l a r s t r u c t u r e s of chemical
s u b s t a n c e s . A l t h o u g h x-ray s t r u c t u r e d e t e r m i n a t i o n
w a s o n c e r e g a r d e d as a difficult a n d t i m e - c o n s u m i n g
p r o c e s s w h i c h c o u l d o n l y b e c a r r i e d o u t b y highly
t r a i n e d c r y s t a l l o g r a p h e r s , recent a d v a n c e s in instru
m e n t a t i o n a n d software h a v e m a d e t h e t e c h n i q u e
available t o chemists as a r o u t i n e analytical t o o l .
C o m p l e t e crystal s t r u c t u r e analyses m a y n o w b e car
ried o u t in less t h a n o n e d a y for simple o r g a n i c
molecules a n d in less t h a n o n e week for c o m p o u n d s
c o n t a i n i n g u p t o 200 n o n h y d r o g e n a t o m s p e r
molecule.
Besides confirming t h e connectivity a n d stereo
c h e m i s t r y of t h e m o l e c u l e , x-ray c r y s t a l l o g r a p h y is
u n i q u e l y c a p a b l e of p r o v i d i n g precise i n f o r m a t i o n
c o n c e r n i n g b o n d lengths, b o n d angles a n d m o l e c u l a r
d i m e n s i o n s . T h i s t y p e of i n f o r m a t i o n is p a r t i c u l a r l y
i m p o r t a n t for t h e analysis of electronic s t r u c t u r e a n d
i n t e r m o l e c u l a r i n t e r a c t i o n s . I n a d d i t i o n , t h e diffrac
tion e x p e r i m e n t s often yield o t h e r i n f o r m a t i o n of
physical significance s u c h a s a m p l i t u d e s of t h e r m a l
m o t i o n of a t o m s o r g r o u p s of a t o m s . Single-crystal xr a y diffraction t e c h n i q u e s h a v e b e e n utilized t o u n
ravel very c o m p l i c a t e d m a c r o m o l e c u l a r s t r u c t u r e s
c o n t a i n i n g m a n y t h o u s a n d s of a t o m s in t h e i n d e p e n
d e n t s t r u c t u r a l unit. Special a t t a c h m e n t s h a v e been
d e v e l o p e d t o allow c o m p o u n d s t o b e studied over
wide r a n g e s of t e m p e r a t u r e s a n d pressures. E x p e r i
m e n t a l x-ray a n d n e u t r o n diffraction studies o n
single crystals h a v e b e e n c o m b i n e d with theoretical
m o l e c u l a r - o r b i t a l c a l c u l a t i o n s in o r d e r t o a n a l y z e t h e
d i s t r i b u t i o n of valence-electron densities.

1.

Fundamentals

A crystal is a solid t h a t h a s a regularly r e p e a t i n g

internal structure, as opposed to a m o r p h o u s mater
ials w h i c h d o n o t . T h e basic b u i l d i n g b l o c k in a crystal
is t h e u n i t cell. A crystal is m a d e u p of millions of
identical u n i t cells a r r a n g e d in a t h r e e - d i m e n s i o n a l
crystal lattice. E a c h crystalline s u b s t a n c e h a s a u n i q u e
set of lattice c o n s t a n t s (a, b, c, , /?, ) w h i c h define t h e
size a n d s h a p e of t h e u n i t cell (see F i g . 1). Based o n
t h e lattice c o n s t a n t s a n d t h e s y m m e t r y w h i c h t h e u n i t
cell possesses, t h e s u b s t a n c e m a y be classified i n t o o n e
of seven crystal systems (i.e., triclinic, m o n o c l i n i c ,
orthorhombic, tetragonal, cubic, trigonal or hexago
n a l ) . Finally, e a c h s u b s t a n c e m a y b e further classified
as b e l o n g i n g t o o n e of 230 t h r e e - d i m e n s i o n a l space
g r o u p s . T h e lattice c o n s t a n t s , crystal system a n d
s p a c e g r o u p a r e i m p o r t a n t physical c o n s t a n t s for
crystalline s u b s t a n c e s a n d m a y b e u s e d in c o n j u n c t i o n
w i t h o t h e r physical m e a s u r e m e n t s (e.g., density, c o n
ductivity, h a r d n e s s ) t o explain t h e p r o p e r t i e s of solidstate m a t e r i a l s .
W h e n a b e a m of parallel m o n o c h r o m a t i c rays of
a p p r o x i m a t e l y 0.1 n m w a v e l e n g t h strikes a single

457

Single-Crystal

X-Ray

Diffraction

dihkl)

Figure 1
Unit-cell nomenclature: the reference axes JC, y9 are
right-handed, the length of the unit-cell edge parallel to
each reference axis is a, b, c, respectively, and the
interaxial angles are , , y, respectively

crystal, t h e crystal acts as a t h r e e - d i m e n s i o n a l dif

fraction g r a t i n g a n d p r o d u c e s a n x-ray diffraction
p a t t e r n ( F i g . 2). T h i s diffraction consists of a t h r e e d i m e n s i o n a l a r r a y of reflections w h i c h satisfy t h e
c o n d i t i o n s of B r a g g ' s law:

nk = 2dsine

(1)

w h e r e is a small integer giving t h e o r d e r of diffrac

tion, is t h e w a v e l e n g t h of t h e incident r a y s , d is t h e
distance b e t w e e n a set of parallel lattice p l a n e s , a n d
is t h e angle b e t w e e n t h e incident x-ray b e a m a n d t h e
a t o m i c lattice p l a n e in t h e crystal (see F i g . 3). T h e

Figure 2
An example of an x-ray diffraction pattern produced by a
randomly oriented single crystal

458

Figure 3
Diagrammatic representation of Bragg's law showing the
diffraction angle and the interplanar spacing d(hkl).
Two rays reflected from the same plane do not suffer any
relative phase change or path difference (AB = CD)

diffraction p a t t e r n for a typical o r g a n i c c o m p o u n d

with 20 n o n h y d r o g e n a t o m s c o n t a i n s a p p r o x i m a t e l y
2000 u n i q u e reflections. T h e spatial a r r a n g e m e n t o f
t h e reflections in a n x-ray diffraction p a t t e r n b e a r s a
reciprocal r e l a t i o n s h i p t o t h e d i m e n s i o n s of t h e u n i t
cell in t h e crystal. E a c h reflection m a y b e assigned a
set o f indices (hkl) w h i c h indicate its l o c a t i o n in t h e
diffraction p a t t e r n o r in reciprocal space. T h e diffrac
tion p a t t e r n in reciprocal space h a s a F o u r i e r t r a n s
f o r m r e l a t i o n s h i p t o t h e electron density in t h e u n i t
cell in real space.
E x p e r i m e n t a l l y , t h e unit-cell p a r a m e t e r s for a crys
talline specimen m a y b e d e t e r m i n e d from a n analysis
of t h e spatial a r r a n g e m e n t of t h e reflections in its xr a y diffraction p a t t e r n . T h e precise m e a s u r e m e n t of
t h e p o s i t i o n s of reflections in reciprocal space is
t e r m e d g e o m e t r i c d a t a collection a n d is c o m m o n l y
carried o u t b y either p h o t o g r a p h i c m e t h o d s using
W e i s s e n b e r g o r precession c a m e r a s o r b y scintillationc o u n t e r m e t h o d s o n a c o m p u t e r - c o n t r o l l e d x-ray
diffractometer. G e o m e t r i c d a t a collection yields a c
c u r a t e c h a r a c t e r i z a t i o n d a t a (i.e., lattice c o n s t a n t s ,
crystal system a n d space g r o u p ) for t h e u n i t cell of
e a c h crystalline specimen. T h e crystal d a t a for k n o w n
substances m a y then be deposited into databases a n d
used t o identify u n k n o w n s a m p l e s b y c o m p a r i s o n in a
m a n n e r a n a l o g o u s t o t h a t u s e d in x-ray p o w d e r
diffraction (see X-Ray Powder Diffraction). G e o m e t r i c
d a t a collection p r o v i d e s direct i n f o r m a t i o n c o n c e r n
ing t h e size a n d s h a p e of t h e cell a n d , in c o m b i n a t i o n
with density a n d elemental analysis m e a s u r e m e n t s , it
m a y also yield i n f o r m a t i o n c o n c e r n i n g t h e cell c o n
t e n t s ; h o w e v e r , it d o e s n o t reveal t h e a c t u a l l o c a t i o n s
of t h e a t o m s within t h e u n i t cell.
T h e d e t e r m i n a t i o n of t h e a r r a n g e m e n t of a t o m s
in t h e u n i t cell requires a very detailed analysis of
t h e relative intensities o f all u n i q u e reflections in t h e
diffraction p a t t e r n . T h e precise m e a s u r e m e n t of t h e
relative intensities of t h e reflections is t e r m e d intensity
d a t a collection. T h e collection o f a c c u r a t e intensity
d a t a r e q u i r e s a c c u r a t e g e o m e t r i c d a t a collection a s a
prerequisite, c o u p l e d w i t h a highly stable x-ray s o u r c e

Single-Crystal

X-Ray

Diffraction

[i^Afc/)! m a y b e calculated directly from t h e m e a s u r e d

intensity I(hkl) for a reflection, since

I(hkl) = k\F(hkl)\

Akhkl)

Figure 4
Structure factor F(hkl) plotted on an Argand diagram.
<x(hkl) is the phase angle and the amplitude is represented
by OF

a n d a very efficient c o u n t i n g system. A n intensity d a t a

set consists of several t h o u s a n d reflections indexed b y
h, k a n d / for w h i c h a n i n t e g r a t e d intensity I(hkl) h a s
been accurately m e a s u r e d .
T h e x-ray diffraction p a t t e r n consists of t h e super
p o s i t i o n of scattered w a v e s o f v a r y i n g a m p l i t u d e a n d
p h a s e . E a c h diffraction m a x i m u m o r reflection h a s
associated with it a s t r u c t u r e factor F(hkt) m e a s u r e d
relative t o t h e scattering b y a single electron. T h e
s t r u c t u r e factor m a y b e r e p r e s e n t e d as a c o m p l e x
vector:

F(hkl) = A(hkl) + iB(hkl)

(2)

w h e r e A(hkl) a n d B(hkl) a r e t h e real a n d i m a g i n a r y

c o m p o n e n t s of F(hkl) (see F i g . 4). T h e m a g n i t u d e o r
length of t h e vector |F(/iA:/)| m a y t h e n b e r e p r e s e n t e d
as

p(xyz)=V- Zll\F(hkl)\
l

2 l/2

+ B(hkl) ]

F(hkl) = l/j

(3)

(4)

w h e r e ^(:/)| is t h e a m p l i t u d e of t h e scattered w a v e
a n d <x(nkl) is its p h a s e angle. F r o m F i g . 4 it m a y b e
seen t h a t
A(hkl) = | F ( A W ) | c o s OL(hkl)

(9)

exp[27ri(Ax,. +

+ lZj)]

(10)

Alternatively, F(hkl) m a y b e expressed a s a n e x p o n e n

tial q u a n t i t y :
FQikl) = I F(hkl) | e x p [ i a ( M / ) ]

If b o t h t h e a m p l i t u d e \F(hkl)\ a n d t h e p h a s e <x(hkl) of
e a c h reflection a r e k n o w n , t h e electron density within
t h e u n i t cell o f t h e crystal c a n b e calculated directly.
O n t h e o t h e r h a n d , if t h e p o s i t i o n s of t h e a t o m s in t h e
u n i t cell a r e k n o w n , b o t h t h e s t r u c t u r e factor a n d
t h e p h a s e for e a c h reflection m a y b e calculated from
t h e s t r u c t u r e factor e q u a t i o n :

12

x cos[2n(hx + ky + Iz) - a(hkl)]

[A(hkl)-\B(hkl)]Y

= [A(hkl)

(8)

w h e r e A: is a c o n s t a n t . H o w e v e r , t h e p h a s e angle <x(hkl)
c a n n o t b e m e a s u r e d e x p e r i m e n t a l l y a n d m u s t there
fore b e o b t a i n e d indirectly t h r o u g h a variety of n u
merical t e c h n i q u e s .
T h e c e n t r a l p r o b l e m in t h e s o l u t i o n of a crystal
s t r u c t u r e is t h e a s s i g n m e n t of p h a s e angles t o e a c h
reflection in t h e d a t a set. T h e s o l u t i o n of t h e p h a s e
p r o b l e m is c o n s i d e r a b l y simplified for crystals which
possess c r y s t a l l o g r a p h i c centers o f s y m m e t r y , since, t o
a first a p p r o x i m a t i o n , t h e i m a g i n a r y c o m p o n e n t s
B(hkt) a r e z e r o for c e n t r o s y m m e t r i c space g r o u p s a n d
t h e p h a s e angles a r e therefore restricted t o values of 0
o r 180. A s t r u c t u r e is c o n s i d e r e d solved w h e n a set of
p h a s e angles h a s b e e n f o u n d w h i c h allows t h e a t o m s
t o b e located a n d t h e e x p e r i m e n t a l diffraction p a t t e r n
t o b e m a t c h e d t o t h e calculated diffraction p a t t e r n .
Since t h e electron density in a crystal varies c o n t i
n u o u s l y a n d periodically in t h r e e - d i m e n s i o n a l space,
t h e electron density p(xyz) a t a p o i n t w i t h fractional
c o o r d i n a t e s x, y, in a u n i t cell of v o l u m e V m a y b e
expressed a s a t h r e e - d i m e n s i o n a l F o u r i e r series:

\F(hkl)\ = {[A(hkl) + iB(hkl)]

(5)

and

B(hkl) = IF(hkl)| sin <x(hkl)

(6)

tan (x(hkl) = B(hkl)/A(hkl)

(7)

and that

w h e r e f} is t h e a t o m i c scattering factor for t h e a t o m

j a n d xJ9 yp Zj a r e its fractional c o o r d i n a t e s . I n a n
a c t u a l s t r u c t u r e d e t e r m i n a t i o n b o t h f o r m s of t h e
F o u r i e r t r a n s f o r m e q u a t i o n s a r e utilized t o arrive a t a
m o d e l s t r u c t u r e from w h i c h t h e o b s e r v e d diffraction
pattern can be reproduced.

2.

Instrumentation

T h e basic h a r d w a r e c o m p o n e n t s of a n a u t o m a t e d
single-crystal x-ray diffractometer system include: (a)
a n x-ray s o u r c e consisting of a high-stability x-ray
g e n e r a t o r , a c o p p e r o r m o l y b d e n u m t a r g e t x-ray t u b e ,
a t u b e shield w i t h associated s h u t t e r s , a t t e n u t o r s a n d
safety i n t e r l o c k s , a m o n o c h r o m a t o r o r ^-filter system,

459

Single-Crystal

X rays

X-Ray

Diffraction

Sample

^Reflections
^ S c i n t i l l a t i o n - c o u n t e r detector

Incident
x-ray beam

X - ray generator
Detector

Figure 5
Block diagram of a typical instrument configuration used
for single-crystal x-ray diffraction analysis

a n d a n i n c i d e n t - b e a m c o l l i m a t o r ; (b) a four-circle
g o n i o m e t e r system w h i c h allows t h e specimen t o b e
precisely o r i e n t e d in a n y p o s i t i o n while r e m a i n i n g in
t h e x-ray b e a m ; (c) a scintillation c o u n t e r d e t e c t o r
system with associated c o l l i m a t o r a n d slits; a n d (d) a n
electronic c o n t r o l console c o n t a i n i n g a m i n i c o m p u t e r
o r m i c r o p r o c e s s o r , a m a g n e t i c t a p e drive a n d / o r
m a s s - s t o r a g e device, a c o m p u t e r t e r m i n a l , a n d inter
faces t o t h e g o n i o m e t e r a n d d e t e c t o r systems. M o d e r n
i n s t r u m e n t s n o r m a l l y include diffractometer c o n t r o l
software w r i t t e n in either B A S I C o r F O R T R A N t o
run on a minicomputer or microprocessor. Structure
d e t e r m i n a t i o n c a l c u l a t i o n s m a y b e carried o u t o n t h e
p r o c e s s o r used for d a t a collection o r they m a y b e
p e r f o r m e d o n a second m i n i c o m p u t e r linked t o t h e
diffractometer c o n t r o l m o d u l e . A large variety of
h a r d w a r e configurations is available commercially,
d e p e n d i n g u p o n t h e r e q u i r e m e n t s of t h e individual
l a b o r a t o r y . A typical i n s t r u m e n t configuration is
illustrated in F i g . 5.
T h e m o s t critical m e c h a n i c a l c o m p o n e n t in a n xr a y diffractometer system is t h e g o n i o m e t e r assembly,
which m u s t b e c a p a b l e of k e e p i n g t h e specimen cen
tered in the incident x-ray b e a m while a t t h e s a m e time
c h a n g i n g its o r i e n t a t i o n in o r d e r t o collect e a c h reflec
tion in reciprocal space. T h e m o s t c o m m o n l y used
t y p e of g o n i o m e t e r is illustrated in Figs. 6 a n d 7. A s
illustrated in F i g . 6, t h e d e t e c t o r m o v e s in a p l a n e
parallel t o t h e i n s t r u m e n t b a s e , referred t o as t h e
e q u a t o r i a l p l a n e , w h i c h c o n t a i n s t h e crystal a n d t h e
incident a n d diffracted x-ray b e a m s for t h e reflection
being m e a s u r e d . T h e value of t h e 20 angle c o r r e s
p o n d s t o twice t h e value of t h e diffraction angle. A
p a r t i c u l a r set of parallel lattice p l a n e s within t h e
crystal m a y b e p o s i t i o n e d in diffracting p o s i t i o n
t h r o u g h t h e a p p r o p r i a t e choice of t h e , a n d
angles. Since only t w o of these three angles a r e
i n d e p e n d e n t , o n e of t h e m m a y be c h o s e n arbitrarily,
t h e r e b y p e r m i t t i n g e a c h reflection t o be m e a s u r e d
from several e q u i v a l e n t o r i e n t a t i o n s . Typically, is

460

Figure 6
Diagram of axes in a four-circle diffractometer

set a t a value e q u a l t o 0 a n d intensity d a t a a r e

collected in t h e 0/20 m o d e , with m o v i n g a t half t h e
speed of 2 as e a c h reflection is s c a n n e d .

3. Experimental

Procedure

T h e first a n d often t h e m o s t difficult step in a crystal

s t r u c t u r e analysis is c o n c e r n e d with t h e selection a n d

Figure 7
A full-circle goniometer used in a commercial x-ray
diffractometer (courtesy of Nicolet X R D Corporation)

Single-Crystal

Figure 8
Thermal ellipsoid plot of the final structure of an organic
compound ( C 1 8H , 8 0 9 )

m o u n t i n g of a suitable specimen. A crystal w h o s e

s t r u c t u r e is t o be d e t e r m i n e d m u s t b e a single crystal
of 0.1-0.5 m m size, n o t c r a c k e d a n d n o t t w i n n e d . T h e
techniques r e q u i r e d t o o b t a i n such crystals v a r y consi
d e r a b l y d e p e n d i n g o n t h e types of c o m p o u n d s t o be
analyzed. Suitable crystals of typical o r g a n i c , o r g a n o metallic o r c o o r d i n a t i o n c o m p l e x e s c a n usually be
g r o w n by slow recrystallization from c o m m o n sol
vents. O t h e r types of c o m p o u n d s m a y r e q u i r e t h e use
of s u b l i m a t i o n , z o n e refinement, solvent diffusion,
low-temperature and/or inert-atmosphere techniques
in o r d e r t o isolate suitable specimens.
O n c e a suitable specimen h a s been selected for
analysis, it is glued o r o t h e r w i s e securely a t t a c h e d t o a
g o n i o m e t e r h e a d in a n a r b i t r a r y o r i e n t a t i o n . T h e
g o n i o m e t e r h e a d is t h e n p l a c e d o n t h e b a s e of t h e
g o n i o m e t e r a s s e m b l y a n d t h e crystal is optically
aligned in t h e c e n t e r of t h e incident x-ray b e a m u s i n g
a m i c r o s c o p e a n d t h e o r t h o g o n a l x, y a n d t r a n s l a t i o nal a d j u s t m e n t s o n t h e g o n i o m e t e r h e a d . T h e a p p r o x
i m a t e a n g u l a r c o o r d i n a t e s for 1 0 - 2 5 reflections a r e
d e t e r m i n e d from either a p r e l i m i n a r y P o l a r o i d p h o t o
g r a p h t a k e n o n t h e i n s t r u m e n t o r from a n a u t o m a t i c
search r o u t i n e . T h e angle settings for these reflections
are t h e n o p t i m i z e d t h r o u g h a n iterative p r o c e s s . A n
a u t o i n d e x i n g r o u t i n e t h e n selects t h e a p p r o p r i a t e u n i t
cell a n d calculates t h e o r i e n t a t i o n m a t r i x a n d lattice
c o n s t a n t s . T h e crystal system is verified p h o t o g r a p h i
cally.
After t h e a b o v e g e o m e t r i c d a t a collection steps
h a v e been c o m p l e t e d a n d a n a c c u r a t e o r i e n t a t i o n
m a t r i x h a s b e e n calculated, intensity d a t a collection
m a y be initiated. T h e r e is a large variety of d a t a collection o p t i o n s available t o suit a n y e x p e r i m e n t a l

X-Ray

Diffraction

r e q u i r e m e n t s . Typically, intensity d a t a a r e collected

sequentially t h r o u g h o u t t h e u n i q u e p o r t i o n of reci
p r o c a l space with systematically a b s e n t reflections
often o m i t t e d . E a c h reflection is m e a s u r e d with a /2
scan t e c h n i q u e , v a r i a b l e scan rates a n d s t a t i o n a r y
b a c k g r o u n d m e a s u r e m e n t s a t e a c h e n d of t h e 2.0
degrees scan. T h e 2 r a n g e is n o r m a l l y 2 0 < 6 O for
m o l y b d e n u m r a d i a t i o n a n d 2 0 ^ 1 2 0 for c o p p e r
r a d i a t i o n . E a c h reflection is r e c o r d e d a s a 96-step
profile for s u b s e q u e n t analysis b y c u r v e fitting tech
n i q u e s . A c o m p l e t e d a t a set m a y r e q u i r e a n y
w h e r e from a few h o u r s t o a few w e e k s d e p e n d i n g o n
t h e c o m p l e x i t y of t h e s t r u c t u r e a n d t h e size of the
specimen.
O n c e t h e intensity d a t a h a v e been collected for a
given specimen, t h e entire d a t a set m u s t b e corrected
for i n s t r u m e n t a l factors, p o l a r i z a t i o n effects, x-ray
a b s o r p t i o n a n d possibly crystal d e c o m p o s i t i o n , a n d
t h e i n t e g r a t e d intensities c o n v e r t e d t o s t r u c t u r e factor
amplitudes through a data reduction process. Once
the structure amplitudes are known, the phase p r o b
lem m u s t b e solved t o find a self-consistent set of
p h a s e s w h i c h c a n b e c o m b i n e d with t h e s t r u c t u r e
factor a m p l i t u d e s t o o b t a i n t h e electron density a n d
t h e r e b y d e t e r m i n e t h e s t r u c t u r e of t h e crystal. A
n u m b e r of c r y s t a l l o g r a p h i c t e c h n i q u e s exist for
o b t a i n i n g t h e p h a s e s of diffracted w a v e s , t h e m o s t
widely utilized a p p r o a c h e s t o t h e s o l u t i o n of t h e p h a s e
p r o b l e m involve t h e use of either vector m e t h o d s
2
b a s e d o n \F(hkl)\ o r direct o r statistical m e t h o d s .
Typically, t h e s o l u t i o n t o t h e s t r u c t u r e yields only
a partial or approximate model which must be
i m p r o v e d b y successive a p p l i c a t i o n s of F o u r i e r t r a n s f o r m m e t h o d s before t h e c o m p l e t e s t r u c t u r e h a s
b e e n d e t e r m i n e d . After t h e entire m o l e c u l a r s t r u c t u r e
h a s b e e n d e t e r m i n e d , t h e a p p r o x i m a t e p o s i t i o n s of t h e
a t o m s a r e refined b y n o n l i n e a r least-squares tech
n i q u e s t o give t h e best fit b e t w e e n t h e calculated a n d
o b s e r v e d intensity d a t a for t h e specimen. T h e refine
m e n t p r o c e s s yields very a c c u r a t e values for a t o m i c

Figure 9
Unit-cell diagram showing the arrangement of molecules
within the cell

461

Single-Crystal

X-Ray

Diffraction

positions from w h i c h b o n d lengths, b o n d angles a n d

o t h e r s t r u c t u r a l p a r a m e t e r s m a y b e calculated.
Finally, o n c o m p l e t i o n of t h e x-ray diffraction a n a l y
sis t h e s t r u c t u r e of the molecule o r crystal lattice m u s t
b e displayed o r p l o t t e d (Figs. 8 a n d 9).

See also: X-Ray Powder Diffraction

1. Theoretical

Outline

I n a n y scattering e x p e r i m e n t , t h e m e a s u r e d intensity
is c o n t r o l l e d b y t h e (total) s t r u c t u r e function St(Q)
(the scattering is a s s u m e d t o be elastic, i.e., n o energy
is e x c h a n g e d b e t w e e n s a m p l e a n d incident r a d i a t i o n )
given b y
St(Q)

= \F(Q)\

(1)

w i t h t h e scattering vector
Bibliography
Glusker J P, Trueblood 1972 Crystal Structure Analy
sis: A Primer. Oxford University Press, New York
International Tables for X-Ray Crystallography
1969
Kynoch Press, Birmingham, UK
Ladd M F C , Palmer R A 1977 Structure Determination by
X-Ray Crystallography. Plenum, New York
Luger 1980 Modern X-Ray Analysis on Single-Crystals.
DeGruyter, New York
Sands D 1969 Introduction to Crystallography. Benjamin,
New York
Stout G H, Jensen L 1968 X-Ray Structure Determi
nation: A Practical Guide. Macmillan, New York
C. F . C a m p a n a
[Nicolet C o r p o r a t i o n , C u p e r t i n o ,
California, U S A ]

Small-Angle Neutron Scattering in

Metallurgy
Small-angle scattering p r o b e s i n h o m o g e n e i t i e s of a
size exceeding t h e w a v e l e n g t h of t h e incident r a d i a
tion. T h e r m a l a n d cold n e u t r o n s a r e t h u s suited t o
reveal a n y density v a r i a t i o n o n a scale r a n g i n g from a
few i n t e r a t o m i c distances t o a b o u t 1 , c a u s e d , for
instance, b y p o s i t i o n a l o r c o m p o s i t i o n a l d i s o r d e r ,
clusters a n d a g g l o m e r a t e s of solute a t o m s a n d p o i n t
defects, finely dispersed p h a s e s ,
fluctuations
and
m o d u l a t i o n s in density a n d / o r c o n c e n t r a t i o n , a n d
local v a r i a t i o n s of m a g n e t i z a t i o n . I n c o n t r a s t t o
rays, n e u t r o n s a r e only w e a k l y a b s o r b e d b y m o s t
m a t e r i a l s . W i t h w a v e l e n g t h s of 0.1 n m t o a b o u t 1 n m ,
s a m p l e s of a thickness of typically a few millimeters t o
a few centimeters m a y b e a n a l y z e d b y small-angle
n e u t r o n scattering ( S A N S ) in t r a n s m i s s i o n , with a
o n e - o r t w o - d i m e n s i o n a l position-sensitive d e t e c t o r t o
m o n i t o r t h e scattering a r o u n d t h e incident b e a m . T h i s
scattering p a t t e r n is c o n t r o l l e d b y t h e real-space cor
relation function of t h e i n h o m o g e n e i t i e s c a u s i n g t h e
scattering " c o n t r a s t . " T h e o r e t i c a l a n d n u m e r i c a l
m o d e l scattering functions m a y b e fitted directly t o
t h e e x p e r i m e n t a l p a t t e r n . I n dilute p a r t i c u l a t e sys
tems, t h e a v e r a g e size of t h e scattering objects ( p a r t i
cles) m a y be o b t a i n e d a l m o s t directly. M o r e involved
e v a l u a t i o n m a y , d e p e n d i n g o n t h e system, yield infor
m a t i o n o n such characteristics as particle s h a p e , p a r t i
cle size d i s t r i b u t i o n , i n t e r n a l c o m p o s i t i o n of particles,
their t o t a l v o l u m e fraction a n d m u t u a l a r r a n g e m e n t .

462

Q = k-k

(2)

w h e r e k0 a n d k a r e t h e w a v e vectors of t h e incident
a n d t h e scattered r a d i a t i o n . F o r elastic scattering,
\k\ = \k0\ a n d Q = \Q\ is simply

w h e r e is t h e w a v e l e n g t h of t h e incident r a d i a t i o n
a n d 2 is t h e scattering angle. " S m a l l " angles m e a n s
limiting Q t o values smaller t h a n a b o u t n/da w h e r e da
is t h e i n t e r a t o m i c d i s t a n c e . T h u s , t h e discrete posi
tions of t h e individual scattering centers will n o t b e
resolved a n d a c o n t i n u o u s function p(r) describing t h e
d i s t r i b u t i o n of scattering length, locally a v e r a g e d over
a n infinitesimal v o l u m e e l e m e n t dr a r o u n d t h e posi
t i o n vector r, m a y be used, leading t o
F(Q)=lp(r)cxp(-iQ.r)dr

(4)

for t h e scattering a m p l i t u d e F(Q) w h e r e V is t h e

sample volume. F o r samples with macroscopic
d i m e n s i o n s , St(Q) vanishes for a n y # 0 if p(r) is
constant t h r o u g h o u t the samples and any measured
small-angle scattering signal is d u e t o local d e v i a t i o n s
of p(r) from t h e m a c r o s c o p i c a v e r a g e p. T h e r e f o r e ,
p(r) - m a y b e used i n s t e a d of p(r) in E q n . ( 4 ) .
F o r r a y s , is given b y t h e locally a v e r a g e d density
of electrons multiplied b y t h e classical electron r a d i u s
( a n d , if relevant, b y t h e f o r m factor). F o r n e u t r o n s ,
t h e scattering length is a n u c l e a r p r o p e r t y which, in
t h e r a n g e o f t h e r m a l a n d s u b t h e r m a l n e u t r o n ener
gies, varies n o n m o n o t o n i c a l l y w i t h a t o m i c m a s s (see
Fig. 1), in c o n t r a s t t o r a y s . T h u s , close n e i g h b o r s in
t h e p e r i o d i c t a b l e m a y b e distinguished a n d t h e use of
stable i s o t o p e s m a y e n h a n c e t h e scattering c o n t r a s t .
S t a r t i n g f r o m E q n . (4), s t r u c t u r e functions m a y b e
calculated for m o d e l d i s t r i b u t i o n s . T h e inverse a p
p r o a c h , t h a t is e v a l u a t i n g p(r) from t h e m e a s u r e d
scattering, is n o t possible in general. F o r statistically
i s o t o p i c systems, r a d i a l d i s t r i b u t i o n functions a n a l o
g o u s t o t h o s e described in t h e article X-Ray
and
Neutron Diffraction Studies of Amorphous Solids m a y
be o b t a i n e d if m e a s u r e m e n t s e x t e n d over a n a p p r o p r i
a t e r a n g e of Q values.
Simplified expressions a r e o b t a i n e d for t h e t w o p h a s e m o d e l , w h e r e small s e c o n d - p h a s e particles of a

Small-Angle

Neutron

Scattering

in

Metallurgy

h o l d s for h < a (disks), if Qh < 1 < Qa.

I n all cases, t h e b e h a v i o r a t very small Q is very
similar: t h e G u i n i e r a p p r o x i m a t i o n is b a s e d o n a n
e x p a n s i o n of t h e e x p o n e n t i a l in E q n . (5) which, for a n
i n t e g r a t i o n a l o n g a c e r t a i n direction of Q, after rein
t e r p r e t i n g t h e q u a d r a t i c t e r m o b t a i n e d for S(Q) as
resulting from a n e x p o n e n t i a l function, leads t o
2

S(Q)>. <.exp(-Q R d)

(10)

where the dimension

2

()

R d=V^lr dq{rd)drd

Figure 1
Neutron scattering lengths of the lighter elements and of
some isotopes (a compilation is given by Kostorz (1979))

h o m o g e n e o u s scattering length density pp a r e e m b e d

d e d in a h o m o g e n e o u s m a t r i x c h a r a c t e r i z e d b y pm
(pp = 0 includes voids a n d cavities, pm = 0 includes
small particles in vacuo). W i t h t h e single-particle
scattering a m p l i t u d e Fp(Q) given b y

F (Q) = (p ~p )i
P

e x p ( - iQ.r) dr

(5)

w h e r e r is t a k e n from t h e g e o m e t r i c a l center of t h e
particle of v o l u m e Vp, a r e d u c e d single-particle scat
tering function
S(Q)=

(6)

(P -PJ%

m a y b e i n t r o d u c e d [5(0) = 1]. S(Q) c a n be calculated

for v a r i o u s particle s h a p e s (see G u i n i e r a n d F o u r n e t
1955). T h e simplest case of a spherical particle yields
sin(QRs)-QRs
c o s ( g / ? s) (Rs = r a d i u s of t h e sphere)
(7)
' s( G * s ) = 9
which decreases t o z e r o a t QRS = 4.493 a n d reaches a
- 3
second m a x i m u m a t QRS = 5.765 ( 5 S = 7.43 1 0 ) ;
further zeroes a n d m a x i m a m a y be o b s e r v e d in a l m o s t
m o n o d i s p e r s e systems. Several a n i s o m e t r i c particles
lead t o a p p r o x i m a t e expressions, for e x a m p l e , for
cylinders of d i a m e t e r 2a a n d length 2h (isotropic
average)

(8)
for Qh>

\>Qa

(rods), while
(9)

m a y d e p e n d o n t h e direction of , as rd is m e a s u r e d
from t h e particle center in t h e direction d p e r p e n d i c u
lar t o k0 within t h e p l a n e defined b y Q a n d k0, with
q(rd) ( = cross-sectional a r e a ) p e r p e n d i c u l a r t o d. T h e
a v e r a g e " i n e r t i a l d i s t a n c e " Rd relative t o t h e p l a n e
c o n t a i n i n g k0 a n d t h e center of m a s s of t h e particle is
a n i n d i c a t i o n of its size a l o n g d.
T h e r a n d o m o r i e n t a t i o n a l a v e r a g e of E q n . (10)
yields

(12)

w h e r e t h e r a d i u s of g y r a t i o n is given by
R2 _

\r dr

(13)
2

F o r u n i f o r m spheres of r a d i u s Rs, R G = 3R /5 a n d t h e
G u i n i e r a p p r o x i m a t i o n h o l d s for QRG
1.2. F o r
o t h e r particle s h a p e s , t h e Q r a n g e m a y be smaller.
A n o t h e r useful a p p r o x i m a t i o n for h o m o g e n e o u s
particles with s h a r p b o u n d a r i e s ( b u t n o s h a r p edges o r
c o r n e r s ) h o l d s for larger Q (larger t h a n t h e reciprocal
value of t h e s h o r t e s t linear d i m e n s i o n of t h e particle):
t h e P o r o d a p p r o x i m a t i o n c o m b i n e s particle v o l u m e
a n d particle surface a r e a Ap a c c o r d i n g t o (orienta
t i o n a l average)
SP(Q)^

vlQ

(14)

T h e e x p e r i m e n t a l l y accessible t o t a l s t r u c t u r e func
tion St(Q) for a system c o n t a i n i n g
particles is a
simple s u p e r p o s i t i o n of TV single-particle scattering
functions only for identical a n d widely s e p a r a t e d
particles. T h e general case of a dense system of
particles, w i t h spatial a n d o r i e n t a t i o n a l c o r r e l a t i o n s
a n d a d i s t r i b u t i o n of sizes, c a n n o t b e solved analyti
cally. Size d i s t r i b u t i o n s m a y b e o b t a i n e d with s o m e
confidence if t h e particles a r e n o t t o o a n i s o m e t r i c a n d
n o interparticle interference intervenes (dilute, i.e.,
v o l u m e fractions of a few p e r c e n t ) . M o d e l calcula
tions o r n u m e r i c a l s i m u l a t i o n m e t h o d s a r e helpful in
m o r e c o m p l e x cases.

463

Small-Angle

Neutron

Scattering

in

Metallurgy

If St(Q) c a n b e m e a s u r e d over^a sufficiently large Q

r a n g e , t h e i n t e g r a t e d intensity m a y b e d e t e r m i n e d
with r e a s o n a b l e accuracy:
1

7 = V ~ J S t ( dQ = (InYW)

6 4 cm

(15)

6 4 cm

In the two-phase model,

3

1-20 m
2

I=(2n) Cp(l-CpXPp-pm)

(16)

w h e r e C p = NVJV
is t h e v o l u m e fraction of t h e
2
particles. F o r i s o t r o p i c systems, Toe$S t(Q)Q dQ is t h e
second m o m e n t of t h e scattering d i s t r i b u t i o n .
W i t h its m a g n e t i c m o m e n t , t h e n e u t r o n also p r o b e s
the local m a g n e t i z a t i o n d i s t r i b u t i o n . A s a result of
1
the
this m a g n e t i c dipole i n t e r a c t i o n , only M (Q),
c o m p o n e n t of t h e F o u r i e r t r a n s f o r m M(Q) of t h e
locally a v e r a g e d m a g n e t i z a t i o n density M(r) w h i c h is
p e r p e n d i c u l a r t o Q, c o n t r i b u t e s t o m a g n e t i c smallangle n e u t r o n scattering. U s i n g p o l a r i z e d n e u t r o n s
a n d n e u t r o n spin analysis, quite detailed i n f o r m a t i o n
o n t h e spatial a n d o r i e n t a t i o n a l d i s t r i b u t i o n of m a g
netization m a y b e o b t a i n e d . A l t h o u g h t h e theoretical
b a c k g r o u n d is well d e v e l o p e d (see references given b y
K o s t o r z (1991)), a p p l i c a t i o n s a r e still very scarce
owing t o e x p e r i m e n t a l limitations.

2. Experimental

Considerations

T h e basic idea of a S A N S e x p e r i m e n t is simple (see

Fig. 2). A b e a m typically a b o u t 1 c m in d i a m e t e r
passes t h r o u g h t h e s a m p l e w h o s e thickness is c h o s e n
to optimize S A N S intensity. T h e direct b e a m is
s t o p p e d b y a n e u t r o n - a b s o r b i n g b e a m s t o p (e.g.,
c a d m i u m o r g a d o l i n i u m ) while a t w o - d i m e n s i o n a l
3
position-sensitive d e t e c t o r (e.g., a B F 3 o r H e g a s
detector) with c o r r e s p o n d i n g electronics is used t o
record the S A N S pattern which m a y be "anisotropic"
in t h e d e t e c t o r p l a n e . ( N o t e t h a t with a fixed s a m p l e
position, t h e s t r u c t u r e function is m e a s u r e d o n t h e
E w a l d sphere with r a d i u s kQ9 n o t o n a p l a n e in
reciprocal space!)
T h e s t r u c t u r e function St(Q) h a s t o b e e x t r a c t e d
from a signal c o n t a i n i n g o t h e r scattering c o n t r i b u
tions a n d e x p e r i m e n t a l b a c k g r o u n d . If a s a m p l e of
thickness D is illuminated b y a n e u t r o n b e a m w h o s e
flux is 0 , t h e c o u n t r a t e in a solid a n g l e a r o u n d
Q is (single-scattering events)
( ) = 0 , [ 5 ( ) + 1]

(17)

w h e r e Ts = exp( >) is t h e t r a n s m i s s i o n of t h e
s a m p l e c o n t r o l l e d b y t h e t o t a l r e m o v a l cross section
(linear a b s o r p t i o n coefficient) c o n t a i n i n g t r u e a b s o r p
tion, i n c o h e r e n t a n d inelastic scattering, B r a g g scat
tering a n d s o o n ; Cl is a c o n s t a n t b a c k g r o u n d d u e t o
i n c o h e r e n t scattering; a n d is t h e d e t e c t o r efficiency.
T h e t e r m s 0 , a n d c a n b e eliminated b y a
c a l i b r a t i o n m e a s u r e m e n t with a s a m p l e of k n o w n
scattering p o w e r (e.g., i n c o h e r e n t scattering from

464

3 0 mm

Sample
2 0 mm

Figure 2
Schematic of a small-angle neutron scattering experiment
with typical dimensions. Lines of equal intensity on the
two-dimensional position-sensitive detector are shown on
the right; they were obtained from a rolled aluminum
alloy sheet. Some texture-related azimuthal variation of
scattering intensity is visible

v a n a d i u m o r w a t e r ) . T h e o p t i m u m s a m p l e thickness is
o b t a i n e d from
= 1 a n d , for m o s t m a t e r i a l s ,
a m o u n t s t o a few millimeters t o several centimeters
for n e u t r o n w a v e l e n g t h s b e t w e e n 0.2 n m a n d 0.6 n m .
W i t h r a y s only very t h i n foils c a n b e investigated in
t r a n s m i s s i o n b e c a u s e of high a b s o r p t i o n a n d w a v e
lengths a b o v e t h e B r a g g cutoff c a n n o r m a l l y n o t b e
used a t all. D o u b l e B r a g g scattering m a y often cause
a d d i t i o n a l scattering a t small angles w h i c h m a y b e
a v o i d e d b y u s i n g " c o l d " n e u t r o n s . T h e available
intensities a n d w a v e l e n g t h s ( u p t o a b o u t 2 n m ) limit
t h e size of scattering objects t o b e analyzed with
such a n a r r a n g e m e n t t o a b o u t 1 . L a r g e r i n h o m o
geneities m a y b e studied with special double-crystal
diffractometers.

3.

Applications

M e t a l l u r g i c a l a p p l i c a t i o n s of S A N S m a y r a n g e from a
simple check of s a m p l e h o m o g e n e i t y t o very detailed
studies of p r e c i p i t a t i o n o r defect a g g l o m e r a t i o n . A
few e x a m p l e s a r e given in t h e following; m o r e m a y b e
f o u n d in recent reviews ( K o s t o r z 1988, 1989, 1991).
T h e e v o l u t i o n of t h e m i c r o s t r u c t u r e of a d e c o m p o s
ing alloy m a y b e studied b y c o m p a r i n g a n u m b e r of
s a m p l e s after v a r i o u s h e a t t r e a t m e n t s .
SANS
measurements must then be performed at tempera
tures w h e r e m i c r o s t r u c t u r a l c h a n g e s a r e suppressed.
T h i s a p p r o a c h is viable for relatively slow processes.
I n - b e a m S A N S m o n i t o r i n g of t h e d e c o m p o s i t i o n o r
reversion of a n alloy is possible a t t e m p e r a t u r e s w h e r e
t h e time c o n s t a n t s a r e a p p r o p r i a t e . W i t h p r e s e n t large
d e t e c t i o n systems, a sufficient n u m b e r of S A N S events
c a n b e detected a t t i m e intervals of less t h a n 0.1 s,
close t o t h e time n e e d e d t o establish a h o m o g e n e o u s
t e m p e r a t u r e a c r o s s a n y s a m p l e . (Cyclic c h a n g e s , such

Small-Angle

Neutron

Scattering

in

Metallurgy

Figure 3
Scaled structure function s(x,t) according to Eqn. (18), = QL(t) = Q/Qm, for (a) Al-6.8 at.%Zn aged at 313
and
3
6
(b) Al-10at.%Zn aged at 291 for the indicated (total) aging times; the continuous line is the function 3x /(2 + x ) (after
Komura et al. 1984, 1985. Reproduced with permission)

as t h o s e i n d u c e d b y elastic, m a g n e t i c o r electric fields,

m a y be resolved a t m u c h smaller intervals if t h e d a t a
are s t o r e d for successive t i m e slices of t h e cycle.)
R e c e n t studies of p h a s e s e p a r a t i o n h a v e b e e n sti
m u l a t e d b y theoretical d e v e l o p m e n t s p r e d i c t i n g s t r u c
t u r e functions a n d kinetic g r o w t h laws for statistically
isotropic systems. P a r t i c u l a r excitement w a s c a u s e d
by a n occasionally a p p a r e n t self-similarity of St(Q9t)
a t c o n s t a n t t e m p e r a t u r e , w h e r e t is t h e a g i n g t i m e ,
resulting from a scaling analysis of S A N S results. If a
u n i q u e characteristic length L(t) c o n t r o l s t h e evolu
tion of a d e c o m p o s i n g system, St(Q,t) c a n be scaled
according to
SXQ,t)
J^Ll

,
= L\t)s[QL(tlt]

(18)

with s(x) i n d e p e n d e n t of t (x = QL{t)) if scaling h o l d s .

F o r L(t), different p a r a m e t e r s a r e used; RG from a
2
p l o t of In St(Q) versus Q a c c o r d i n g t o E q n . (12), o r
l
the inverse of t h e first m o m e n t , \QSX(Q) dQ, o r Q~
w h e r e Qm is t h e Q value ( 0) for a n intensity m a x i
m u m ( S A N S p e a k ) . I n several m o d e l s , Qm(t)
and
Stm(t) = St(Qm,t)
follow p o w e r laws
Qm(t)

= At~\

Slm(t)

= Bt

(19)

with c o n s t a n t s A a n d B, c o n s t a n t e x p o n e n t s a a n d b,
a n d b = 3a if scaling h o l d s . Scaling is expected in t h e
O s t w a l d ripening regime w i t h / = c o n s t a n t ( v o l u m e
fraction a n d c o m p o s i t i o n of particles r e m a i n i n g c o n
s t a n t ) a n d 3a = b = 1. M a n y m o r e c o m p l e x s i t u a t i o n s
a r e n o w often p r e s e n t e d in scaled form. F o r p o l y c r y s talline s a m p l e s , t e x t u r e a n d g r a i n - b o u n d a r y effects

m u s t b e negligible. F o r single crystals, St(Q) m u s t be

p r o p e r l y a v e r a g e d . C o h e r e n c y strains a n d crystalline
a n i s o t r o p y a r e n o t yet fully i n c o r p o r a t e d in a n y
t h e o r y . T h e m o s t suitable systems for a scaling a n a l y
sis will b e t h o s e with small strain i n t e r a c t i o n s . F i g u r e
3 illustrates t h e p r o c e d u r e for S A N S d a t a o b t a i n e d o n
t w o a l u m i n u m - z i n c alloys (polycrystalline). T h e
universal scaling function s h o w n w a s suggested for
t h e off-critical cluster regime of d y n a m i c a l scaling (see
F u r u k a w a 1988). T h o u g h this function seems t o fit
t h e results, it implies t h a t t h e r a t i o of cluster sepa
r a t i o n t o cluster size s h o u l d r e m a i n c o n s t a n t , which is
difficult t o i m a g i n e for later a g i n g stages. I n fact,
o t h e r functions h a v e also been r e p o r t e d for similar
alloys (see references given b y K o s t o r z (1991)). F i g u r e
4 s h o w s t w o S A N S p a t t e r n s for a n A l - 6 . 8 a t . % Z n
single crystal illustrating t h a t m a n y details a r e aver
aged o u t if polycrystals a r e used. O n t h e basis of a
m o d e l c a l c u l a t i o n i n c l u d i n g a size d i s t r i b u t i o n , the
a v e r a g e r a d i u s of t h e G u i n i e r - P r e s t o n z o n e s f o r m i n g
in this alloy is a b o u t 1.6 n m in F i g . 4a. T h e scattering
a t larger Q values indicates spherical particles, b u t t h e
" i s o t r o p i c " interparticle interference ring f o u n d for
polycrystals n o w s h o w s a m a r k e d a z i m u t h a l v a r i a t i o n
of p e a k intensity, w h i c h is related t o a preferred
a l i g n m e n t of z o n e s a l o n g <100>. I n Fig. 4 b t h e p e a k
h a s m o v e d t o smaller Q values (indicating larger z o n e
s e p a r a t i o n s ) . T h e a v e r a g e z o n e r a d i u s is n o w a b o u t
2.2 n m , a n d t h e m o r e r e c t a n g u l a r s h a p e of the isointensity lines a t larger Q relates t o the w e l l - k n o w n fact
t h a t z o n e s exceeding a certain r a d i u s ( 1 - 2 n m d e p e n d
ing o n t h e e x p e r i m e n t a l details) t r a n s f o r m from

465

Small-Angle

Neutron

Scattering

in

Metallurgy

A p a r t from these investigations c o n c e r n i n g p r i m a r

ily t h e m e c h a n i s m s of p h a s e s e p a r a t i o n , c h a n g e s of
precipitate size a n d v o l u m e fraction (including
v a c a n c y o r interstitial clusters) d u r i n g i r r a d i a t i o n o r
plastic d e f o r m a t i o n m a y be studied q u i t e sensitively,
as t h e i n d i v i d u a l p o i n t defects d o n o t c o n t r i b u t e t o t h e
S A N S signal, a n d dislocations h a v e a c o n s i d e r a b l y
smaller scattering p o w e r t h a n m o s t precipitates. M i c
r o s t r u c t u r a l c h a n g e s m a y even b e revealed n o n d e s tructively a s h a s b e e n d e m o n s t r a t e d , for i n s t a n c e , for
turbine blades and superconducting material embed
d e d in a c o p p e r m a t r i x . T h e scattering of dislocations,
t h o u g h w e a k , m a y also be e v a l u a t e d u n d e r f a v o r a b l e
circumstances. In ferromagnetic materials, the magnetoelastic c o u p l i n g m a y e n h a n c e t h e scattering from
strain fields.

Figure 4
Small-angle scattering pattern for an Al-6.8 at.%Zn single
crystal with {110} faces perpendicular to the incident
beam. The other crystallographic orientations are
indicated. After quenching, the crystal was aged in situ at
room temperature for (a) 2 h and (b) 7.5 h. The azimuthal
dependence of the maximum intensity is visible (after
Kostorz 1991)
spherical t o o b l a t e ellipsoidal s h a p e . T h i s t r a n s i t i o n as
well as t h e l o n g - r a n g e c o r r e l a t i o n s a l o n g <100> a r e
primarily d u e t o t h e elastic misfit of c o h e r e n t precipi
tates. I n nickel-rich n i c k e l - a l u m i n u m w h e r e c o h e r e n t ,
o r d e r e d N i 3 A l precipitates form, t h e elastic misfit is
larger. A single crystal of N i - 1 2 a t . % A l aged a t 833
s h o w s a similarly a n i s o t r o p i c S A N S p a t t e r n (Fig. 5a)
with interference m a x i m a a n d l a r g e - b e h a v i o r
related t o a c u b o i d a l s h a p e . If t h e m i s m a t c h b e t w e e n
precipitates a n d m a t r i x is essentially eliminated by a n
a d d i t i o n of m o l y b d e n u m , t h e precipitates r e m a i n
spherical, a n d n o preferred a l i g n m e n t is visible (Fig.
5b). In situ a g i n g e x p e r i m e n t s o n these alloys also
s h o w a m a r k e d c h a n g e in t h e g r o w t h r a t e of precipi
tates, as illustrated in Fig. 6.

466

Figure 5
Isointensity plots (counts in 20 min) of SANS data for
single crystals of (a) Ni-12 at. %A1 aged for 35 min at
833 K, (b) Ni-6.1 at.%Al-9.4 at.%Mo aged for 3.9 h at
883 K. The incident beam ( = 0.66 nm 10%) was
parallel to [110] (after Calderon and Kostorz 1990)

Small-Angle

50

40

30 L-

20

10

,cP

10

/ (h)

Figure 6
Cube of the radius of gyration i? G as a function of aging
time t for / formation in N i - A l - M o single crystals of
variable mismatch m = Aa/ay: A , Ni-12 at.%Al,
m = 1.2%; , Ni-10.3 at.%Al-5.5 at.%Mo, m = 0.6%;
, Ni-6.5 at.%Al-9.6 at.%Mo, m a 0;
O, Ni-6.1 at.%Al-9.4at.%Mo, m 0. The aging
temperature was 833 except for the open circles where it
was 883 (after Calderon and Kostorz 1990)

Neutron

Scattering

in

Metallurgy

V e r y often in S A N S studies of s t r u c t u r a l m a t e r i a l s ,
h o w e v e r , t h e s i m u l t a n e o u s presence of several inh o m o g e n e i t i e s , such a s d e c o m p o s i t i o n p r o d u c t s ,
c a r b i d e s , inclusions a n d p o r e s , c o m p l i c a t e s t h e inter
p r e t a t i o n o f (possibly small) c h a n g e s . If t h e c h a n g e s
o c c u r in t h e tail region o f t h e S A N S curve, t h a t is, if
t h e n e w scattering objects a r e small, such m e a s u r e
m e n t s m a y nevertheless yield useful i n f o r m a t i o n . A d
d i t i o n a l evidence m a y c o m e from m a g n e t i c scattering
t e r m s a s s h o w n , for e x a m p l e , in F i g . 7. H e r e , t h e e x t r a
S A N S intensity, using u n p o l a r i z e d n e u t r o n s , is s h o w n
for a r e a c t o r p r e s s u r e vessel steel i r r a d i a t e d w i t h fast
19
2
n e u t r o n s (3 10 c m " , E> 1 M e V ) a t 563 a n d
s u b s e q u e n t l y a n n e a l e d (24 h a t 693 K ) , w i t h Q either
parallel o r p e r p e n d i c u l a r t o t h e m a g n e t i c field H. T h e
scattering parallel t o / / i s extremely small. A s t h e r a t i o

/ r e m a i n s essentially i n d e p e n d e n t of Q, there is
s t r o n g evidence for only o n e t y p e of defect cluster
( r a d i u s less t h a n 1 n m , v o l u m e fractions less t h a n
3
2 x 10" ). T h e a u t h o r s suggest t h a t v a c a n c y - c o p p e r
or copper-manganese-vacancy aggregates form dur
ing i r r a d i a t i o n w h i c h a r e modified o n a n n e a l i n g a n d
reirradiation.
See also: Polymers: Neutron Scattering; Polymers: X-Ray
Scattering; X-Ray and Neutron Diffraction Studies of
Amorphous Solids

Bibliography

0.5

1.0
2.0
1
0 (nm" )

4.0

Figure 7
SANS intensities (logarithmic scale) due to the defects in a
reactor pressure vessel steel after irradiation with fast
neutrons and a subsequent anneal (see text). The
scattering from an unirradiated reference sample has been
subtracted. Measurements were performed in magnetic
saturation, parallel ( O ) and perpendicular ( ) to the
magnetic field. The solid lines are calculated for spherical
particles of an average radius R = 0.83 nm; AR/R = 0.246
(after Solt et al. 1989. Reproduced with permission)

Binder 1991 Spinodal decomposition. In: Haasen (ed.)

1991 Phase Transformation in Materials, Materials Sci
ence and Technology, Vol. 5. VCH, Weinheim, Germany,
pp. 405-71
Calderon H, Kostorz G 1990 In: Shapiro S M, Jorgensen J
D, Moss S C (eds.) 1990 Neutron Scattering for Materials
Science. Materials Research Society, Pittsburgh, PA, pp.
255-60
Furukawa 1988 Dynamical scalings for phase separations
in liquid and solid systems. / . Appl. Cryst. 21: 805-10
Guinier A, Fournet G 1955 Small-Angle Scattering of XRays. Wiley, New York
Gurevich I, Tarasov L V 1968 Low Energy Neutron Physics.
North-Holland, Amsterdam
Komura S, Osamura K, Fujii H, Takeda 1984 Dynamical
scaling of the structure function in quenched Al-Zn and
Al-Zn-Mg alloys. Phys. Rev. 30: 2944-7
Komura S, Osamura K, Fujii H, Takeda 1985 Time
evolution of the structure function of quenched Al-Zn
and Al-Zn-Mg alloys. Phys. Rev. 31: 1278-301
Kostorz G 1979 Small-angle scattering and its applications
in materials science. In: Kostorz G (ed.) 1979 Neutron
Scattering, A Treatise on Materials Science and Tech
nology, Vol. 15. Academic Press, New York, pp. 227-89
Kostorz G 1988 Small-angle neutron scatteringmetallur
gical applications. Mater. Sci. Forum 27-8: 325-44
Kostorz G 1989 Metallurgical applications of small-angle
scattering. Hyperfine Interact. 45: 91-103
Kostorz G 1991 Small-angle scattering studies of phase
separation and defects in inorganic materials. J. Appl.
Cryst. 24: 444-56
Moon R M, Riste T, Koehler W C 1969 Polarization

467

Small-Angle

Neutron

Scattering

in

Metallurgy

analysis of thermal neutron scattering. Phys. Rev.

920-31
Solt G, Frisius F, Waeber W 1989 In: Steele L (ed.)
Radiation Embrittlement of Nuclear Reactor Pressure
sel Steels, Vol. 8. American Society for Testing
Materials, Philadelphia, PA, pp. 229-42

181:
1989
Ves
and

G. Kostorz
[ Z u r i c h , Z u r i c h , Switzerland]

Solid-State Nuclear Track Detectors:

Applications
In m o s t dielectric solids, energetic c h a r g e d n u c l e a r
particles c a n p r o d u c e c o n t i n u o u s trails of displaced
a t o m s t h a t m a y be simply displayed b y preferential
chemical a t t a c k , in m u c h t h e s a m e m a n n e r t h a t dislo
c a t i o n s a r e etched in m a n y solids. T h e etched t r a c k s
are holes t h a t c o n s t i t u t e p e r m a n e n t r e c o r d s of trajec
tories a n d i n t e r a c t i o n s of n u c l e a r particles. Solids t h a t
record t r a c k s f o r m a f o u r t h t y p e of n u c l e a r particle
detector with u n i q u e , useful differences from c l o u d
chambers, bubble chambers and nuclear p h o t o
graphic emulsions. They are rugged, permanent and
passive, a n d they possess a n a s s o r t m e n t of d e t e c t i o n
t h r e s h o l d s w h i c h aid identification of h e a v y n u c l e a r
particles. T h e y also h a v e a n i m m e n s e variety of b o t h
scientific a n d technological a p p l i c a t i o n s (Fleischer et
al. 1965a, 1972, 1975), a selection of w h i c h will b e
described here.
1. Basics

of Track

Production

and

Revelation

T r a c k s a r e f o r m e d in t h e three m a j o r classes of
insulating solids: crystals, glasses a n d p o l y m e r s

= sin" (vcyvj)
Figure 1
Track geometry for constant general dissolution rate v G
and two different track attack rates vT: the track with the
lower v T is smaller, shorter and blunter (Fleischer 1981)
( Y o u n g 1958, Fleischer a n d Price 1963a, b ) . F i g u r e 1
illustrates h o w chemical e t c h i n g reveals t r a c k s a s
holes t h a t a r e conical in i s o t r o p i c m a t e r i a l s such as
glasses. T h e c o n e angle is s h a r p e r t h e g r e a t e r t h e
value of v T / v G (the r a t i o of t h e preferential r a t e of
d i s s o l u t i o n a l o n g t h e t r a c k t o t h e general a t t a c k r a t e ) .
F i g u r e 2 gives e x a m p l e s of t r a c k s in a plastic, a glass
a n d a crystal. I t illustrates t h e w i d e v a r i a t i o n in t h e
o b s e r v e d value of a n d of t h e size t o w h i c h t r a c k s
m a y b e etched. Small values a r e frequent in crystals
a n d high p o l y m e r s , a n d a r e seen in certain glass

Figure 2
Photographs of etched tracks of different sizes in different classes of solids: (a) 2 3 U
5
fission tracks in muscovite mica;
(b) fission tracks in ordinary glass; (c) 700 long track of a heavy cosmic ray nucleus in the plastic of an Apollo helmet
468

Solid-State

c o m p o s i t i o n s . T h e value of d o e s v a r y w i t h d a m a g e
intensity, as is illustrated b y F i g . 2c.

1.1 Sensitivity of Registration

W h e t h e r a particle registers a t r a c k o r n o t c a n b e
u n d e r s t o o d from a d i a g r a m of i o n i z a t i o n a g a i n s t
energy such as F i g . 3, w h i c h includes e x p e r i m e n t a l
d a t a for t h e p o l y c a r b o n a t e p o l y m e r L e x a n . A s i o n s
slow d o w n , t h e y b e c o m e m o r e efficient a t i o n i z i n g
a t o m s a l o n g t h e i r p a t h a n d , a t s o m e v a l u e of i o n i z a
tion per unit p a t h length, begin to form tracks. T h e
o p e n a n d closed circles in F i g . 3 i n d i c a t e , respectively,
ions t h a t d o n o t o r d o f o r m t r a c k s ; they define t h e
t h r e s h o l d i n d i c a t e d for L e x a n . O t h e r t h r e s h o l d s a r e
given in F i g . 3, a n d a larger c o m p i l a t i o n in T a b l e s 1
a n d 2 s h o w s g r o u p i n g s of m a t e r i a l s b y relative sensiti
vity, s u b d i v i d e d i n t o i n o r g a n i c m a t e r i a l s ( T a b l e 1)
a n d o r g a n i c o n e s ( T a b l e 2). Plastics a r e usually m o r e
sensitive.

1.2 Mechanism of Track Production

F i g u r e 4 describes o u r best u n d e r s t a n d i n g of h o w
t r a c k s a r e f o r m e d (Fleischer et al. 1965b, Fleischer
1981) b y a b u r s t of i o n i z a t i o n c a u s e d b y t h e m o v i n g
c h a r g e d particle. T h e c h a r g e d particle ejects e l e c t r o n s
a l o n g its p a t h , leaving a densely p o p u l a t e d trail of
positive i o n s . T h e s u b s e q u e n t electrostatic r e p u l s i o n
leads t o a t o m i c d i s o r d e r consisting of interstitial
a t o m s , v a c a n t a t o m i c sites, a n d ( p r e s u m a b l y ) b e n t
a n d b r o k e n b o n d s . T h e a t o m i c d i s o r d e r is p e r m a n e n t
for low s t o r a g e t e m p e r a t u r e s a n d it allows l a t e n t
t r a c k s t o b e e t c h e d a n d s t u d i e d l o n g after they w e r e
produced.

1.3 Particle

Energy per nucleon (MeV)

Track

Detectors:

2.

Uses of Etched

Particle

Tracks

T h e a p p l i c a t i o n of particle t r a c k s include b o t h scien

tific uses (Fleischer et al. 1975 C h a p s . 4 - 9 ) a n d
t e c h n o l o g i c a l o n e s (Fleischer et al. 1972, 1975 C h a p .
10).

Table 1
Relative sensitivities of various inorganic detectors"

Detector

Atomic composition

Hypersthene Mg 1 5Fe 0 5Si 2O 6

Olivine

Figure 3
Ionization against velocity for different charged particles
travelling through Lexan polycarbonate (thresholds for
other detectors are also indicated) (Fleischer 1981)

Least-ionizing
ion seen
100 MeV *Fe

MgFeSi64

Labradorite Na 2Ca 3Al 8Si 1 2O 40

Zircon
ZrSi0 4
Bronzite
Enstatite

Mg, 7Fe 0. 3Si 2O 6

Diopside
Augite

CaMg(Si0 3) 2
CaMg 3Fe 3Al 2Si 40 19

170 MeV*Fe
56
170 MeV Fe

Oligoclase
Bytownite
Orthoclase
Quartz

Na 4CaAl 6Si 1 4O 40
NaCa^Si,^
KAlSi 3O g
Si0 2

4MeV 2 8Si
4MeV Si
100 MeV <Ar
100 MeV <Ar

Phlogopite
mica
Muscovite
mica

KMg 2Al 2Si 3O 1 0(OH) 2

MgSi03

Soda lime
glass
Phosphate
glass

28

20

2MeV Ne

KAl 3Si 3O 1 0(OH) 2

Silica glass Si0 2

Flint glass
18Si02:4PbO: 1.5Na 20:K 20
Tektite glass 22Si0 2:2Al 20 3:FeO
(obsidian
similar)

Velocity v/c

Applications

function of i o n i z a t i o n r a t e allows i n d i v i d u a l n u c l e a r
particles t o b e identified b y m e a s u r i n g v T o r a l o n g a
t r a c k (Price et al. 1968. Fleischer et al. 1970). F i g u r e 5
s h o w s h o w t h e t a p e r of a t r a c k s u c h a s is s h o w n in
F i g . 2c is derived geometrically. U s i n g curves such as
t h o s e in F i g . 3 a n d c a l i b r a t i o n d a t a from o t h e r ions,
t h a t p a r t i c u l a r t r a c k is inferred t o b e from a fastm o v i n g zinc ion t h a t c a m e t o rest in t h e d e t e c t o r .

Identification

T h e fact t h a t t h e e t c h i n g r a t e v T a l o n g a t r a c k is a

Nuclear

20

2-4MeV Ne

23Si0 2:5Na 20:5CaO:Al 20 3

20 MeV N e

10P 2O 5:1.6BaO:Ag 20:2K 20:2Al 20 3

a Solid lines represent relatively clear separations; broken lines represent

unclear but likely separations. Some materials have different sensitivities
depending on the etchant used

469

Solid-State

Nuclear

Track

Detectors:

Applications

Table 2
Relative sensitivities of various organic detectors*

Detector
Amber

Atomic
composition
C 2H 30 2

Phenoplaste
Polyethylene

C 7H 60
CH 2

Polystyrene

CH

Polyvinylacetochloride
C 6H 90 2C1
PolyvinylchlorideC2H3C1 + C2H2C12
polyvinyledene chloride
copolymer

Least-ionizing
ion seen

Full-energy
fission
fragments

Fission
fragments

32

42 MeV 3 2S
42 MeV S

( b)

Polyethylene
terephthalate (Cronar,
Melinex)
Polyimide
Ionomeric polyethylene
(Surlyn)

C 5H 40 2

Bisphenol
A-polycarbonate
(Lexan, Makrofol)

C, 6H l 40 3

Polyoxymethylene
(Delrin)

CH 20

Polypropylene

CH 2

lMeV He

Polyvinylchloride
Polymethylmethacralate
(Plexiglas)

C2H3C1
C 5H 80 2

3MeV He

CH 40 4N 2

(a)

36 MeV'O
, 6
36 MeV 0

0.3MeV He

Ionization

Electrostatic
displacement

Figure 4
The ion explosion spike mechanism for track formation in
inorganic solids: the original ionization left by passage of
a charged particle (a) is unstable and ejects ions from their
sites, creating vacancies and interstitials (b); later the
stressed region relaxes elastically, straining the undamaged
matrix (Fleischer et al. 1965b)

28 MeV "B

Etched surface

[-Original
surface

Cellulose acetate butyrate C, 2H 1 80 7

Cellulose triacetate
(Cellit, Triafol-T,
Kodacel TA-401
unplasticized)

C 3H 40 2
Incoming
particle

Cellulose nitrate (Daicell) C 6H 80 9N 2

Allyl diglycol carbonite
(CR-39)

C, 2H 1 80 7

Cellulose nitrate (CN-88

fully nitrated)

C 6H 80 9N 2

0.55 MeV
1.5 MeV

5 MeV

a Solid lines represent relatively clear separations. Many materials have

different sensitivities depending on their exposure to oxygen, ultraviolet
light, etc., and on the etchant used

470

Figure 5
Diagram illustrating how a measure of a diameter D as a
function of distance X on a residual range R from the end
of the track determines the cone angle at positions along
an etched track, allowing particles to be identified
(Feischer et al. 1970)

Solid-State

2.1 Scientific

Figure 6
Radiograph showing the location of plutonium in the
lumbar vertebra of a dog which had been given 2.7 of
2 3 9P ukg- and killed 28 days later (courtesy of W. S. S.
Jee): labelled are three trabeculae with surface deposits of
2 3 9P u (S), osteoclasts with 2 3 Pu
9
aggregates on bone
surfaces (O), macrophages with star-producing aggregates
in bone marrow (M) and bone image (B)

Nuclear

Track

Uses of

Tracks

Detectors:

Applications

T h e first t r a c k s seen w e r e from fission f r a g m e n t s

p r o d u c e d b y e x p o s i n g u r a n i u m t o n e u t r o n s . Since t h e
n u m b e r of t r a c k s p r o d u c e d d e p e n d s o n t h e n e u t r o n
fluence , t h e c o n c e n t r a t i o n of u r a n i u m c ( U ) a n d t h e
cross-section for i n d u c i n g fission, it is possible t o use
t r a c k s for n e u t r o n d o s i m e t r y , u r a n i u m analysis a n d
n u c l e a r cross-section m e a s u r e m e n t s . E a c h of these
a r e a s h a s b e e n b r o a d e n e d over t h e y e a r s . D o s i m e t r y is
possible for energetic nuclei of all t h e e l e m e n t s , n o t
j u s t n e u t r o n s , a n d i n d u c e d r e a c t i o n s allow elements
o t h e r t h a n u r a n i u m t o b e m e a s u r e d ; lithium, b o r o n ,
n i t r o g e n , lead a n d b i s m u t h a r e e x a m p l e s . S p o n t a
n e o u s e m i s s i o n s allow a l p h a e m i t t e r s like 2 2 R
2 n
and
2 2 0R n ,
a n d s p o n t a n e o u s l y fissioning nuclides t o b e
m e a s u r e d . C r o s s sections h a v e b e e n d e t e r m i n e d for a
variety of r e a c t i o n s , i n c l u d i n g t e r n a r y fission. F i g u r e 6
s h o w s a n e x a m p l e of a case w h e r e n o t o n l y is chemical
analysis p e r f o r m e d , b u t sensitive m a p p i n g of t h e
e l e m e n t d i s t r i b u t i o n is also evident. I n F i g . 6, a L e x a n
p o l y c a r b o n a t e d e t e c t o r w a s pressed a g a i n s t a section

mica
sphene"

1000oooooo

whitlockite
</

^7f

apatite^ mica
apa^ite^homblende
allanite

z i r c o n ^ a p a t i t e , sphene
> mica, apatite
. a ippaattiittee
#'tektites
t e k t i t e s F /CM I 2C < ,
s h a r d s , * ^i P
m a tc
lass

,apatite,epidote,sphene-

<3

o b s i d i a n . ' e b s i nd i a
shards^Pumice
obsidians
tektites
zircon

000000

1000

synthetic
glass

v.

uranium - mica

pair

1000000

1000000000

Fission track a g e (years)

Figure 7
Graph comparing fission track ages, measured by counting natural tracks formed by spontaneous fission of 2 3 U
8 , with ages
known by other means, either documented ages for man-made samples or ages measured by other radioactive decay
techniques for the geological samples (Fleischer et al. 1975)

471

Solid-State

Nuclear

Track Detectors:

Applications

2.2 Technological Uses of Tracks

M a n y technological uses a r e merely the a p p l i c a t i o n t o
m o r e a p p l i e d uses of w h a t is described in Sect. 2.1 as
scientific t e c h n i q u e s . O n e e x a m p l e is the m a p p i n g of
u r a n i u m s h o w n in Fig. 6, w h i c h w a s p a r t of a n
a t t e m p t t o quantify d o s e d i s t r i b u t i o n s from internal
r a d i o n u c l i d e s in h u m a n s .

from the l u m b a r v e r t e b r a of a d o g d o s e d with 2 3P9 u ,

n e u t r o n i r r a d i a t e d , a n d t h e n etched t o p r o d u c e a n
image, w h i c h s h o w s the p l u t o n i u m c o n c e n t r a t e d o n
b o n e surfaces a n d in s t a r - p r o d u c i n g aggregates within
the m a r r o w . Typical t r a c k s a r e ~ 10 in length.
M a n y m i n u t e a l p h a t r a c k s from b o r o n p r o d u c e t h e
d a r k i m a g e of the b o n e .
N a t u r a l t r a c k s t h a t a r e s t o r e d in m i n e r a l s a n d
n a t u r a l glasses give us a varied a n d detailed history of
b o t h the e a r t h a n d extraterrestrial b o d i e s . T h e r e c o r d
in the m o o n , meteorites a n d c o s m i c d u s t is m u c h t o o
c o m p l e x t o describe here (see Fleischer et al. 1975
C h a p . 6) b u t for terrestrial r o c k s t h e story is simple.
Except in p a t h o l o g i c a l locales, s p o n t a n e o u s fission of
2 3 8U forms essentially all of the n a t u r a l
fission t r a c k s
found in m i n e r a l s o n e a r t h (Price a n d W a l k e r 1963).
F o r minerals w h e r e such t r a c k s a r e p e r m a n e n t a t
a m b i e n t t e m p e r a t u r e s their a b u n d a n c e a n d a m e a s u r e
of the u r a n i u m c o n c e n t r a t i o n allows geological ages
t o be m e a s u r e d , as Fig. 7 d e m o n s t r a t e s . M a n y m i n e r
als m a y b e d a t e d a n d a vast time s p a n covered
(5 x 1 0 " 1 t o 4.4 10 9 years). T h e sensitivity of t r a c k s
t o h e a t i n g allows d a t i n g of t h e r m a l events in the p a s t
a n d times of i g n e o u s i n t r u s i o n , tectonic uplift a n d
o c e a n b o t t o m s p r e a d i n g t o b e m e a s u r e d . T h e lack of
significantly high fission t r a c k ages relative t o
8
spontaneous
" k n o w n " ages in Fig. 7 implies t h a t 2 3 U
fission is the sole c o n t r i b u t o r of fossil t r a c k s .

H o l e engineering, h o w e v e r , is a wholly distinct

a p p l i c a t i o n . E t c h e d t r a c k s a r e holes; w h e n oriented t o
cross t h i n plastic sheets they c a n be used t o p r o d u c e
filters (Fleischer et al. 1964). I n the c o m m e r c i a l form
of N u c l e p o r e filters they serve a wide r a n g e of func
tions in cleaning particles from gases o r liquids, as
s u b s t r a t e s for viewing such particles (Fig. 8), a n d as
critical elements in c o u n t e r s of viruses o r biological
cells (DeBlois a n d B e a n 1970). H o l e sizes t h a t r a n g e
from 0.010 t o 12 a r e available commercially,
with a variability of 2 % a b o u t the m e a n d i a m e t e r s for
1 holes.
T h e o t h e r m a j o r a r e a of c o m m e r c i a l use of t r a c k
etching is in m e a s u r i n g the c o n c e n t r a t i o n in air of the

Figure 8
Airborne salt particles from marine air near Hawaii,
caught by a Nucleopore filter: the uniform, slightly mat
surface of the filter provides good contrast with
particulates, as shown on this scanning electron
micrograph (photograph taken by E. R. Ackerman of the
US National Center for Atmospheric Research)

Figure 9
Detector cup used for track etching measurements of
indoor 2 2 Rn.
2
A high-permeation membrane cover admits
only the longest-lived radon isotope. A desiccant package
in the cup restricts the condensation of moisture. The
track detector is the rectangular piece of plastic at the
bottom of the cup

472

Solid State:
2 2 2

noble, r a d i o a c t i v e gas
R n (Fleischer et al. 1980),
which in h o m e s is a h a z a r d a n d in t h e g r o u n d is a
tracer for u r a n i u m (Fleischer et al. 1972, G i n g r i c h
1975), oil a n d g a s ( F l e i s c h e r a n d T u r n e r 1984)
and impending e a r t h q u a k e s (Fleischer a n d M o g r o C a m p e r o 1985). T h e s i m p l e , p a s s i v e device t h a t is
used t o p r o d u c e l o n g - t i m e a v e r a g e s of r a d o n c o n c e n
t r a t i o n (Alter a n d Price 1972, F l e i s c h e r a n d M o g r o C a m p e r o 1978) is s h o w n in F i g . 9. T h e t r a c k - d e t e c t
ing plastic a t t h e e n d of t h e c u p r e c o r d s a l p h a
2 2 2
particles e m i t t e d b y
R n w h i c h diffuses i n t o t h e
c h a m b e r . B e c a u s e of t h e s h o r t r a n g e of a l p h a p a r t i
cles f r o m n a t u r a l r a d i o n u c l i d e s , t h e c u p walls a n d
m e m b r a n e shield o u t all e x t r a n e o u s a l p h a p a r t i c l e s ;
t h e m e m b r a n e b y its c h o s e n p e r m e a b i l i t y a d m i t s
2 2 2
only
R n , t h e i s o t o p e of i n t e r e s t . F o r use in t h e
ground the desiccant takes u p moisture that other
wise m i g h t c o n d e n s e o n t h e d e t e c t o r a n d shield it
from r a d o n a l p h a p a r t i c l e s .

Study

Using Muon

Beams

Fleischer R L, Price , Walker R 1975 Nuclear Tracks

in Solids. University of California Press, Berkeley, CA
Fleischer R L, Turner L G 1984 Correlations of radon and
carbon isotopic measurements with petroleum and natu
ral gas at Cement, Oklahoma. Geophys. 49: 810-17
Gingrich J 1975 Results from a new uranium exploration
method. Trans. Am. Inst. Min., Metall. Pet. Eng. 258: 6 1 4
Price , Fleischer R L, Peterson D D, O'Ceallaigh C,
O'Sullivan D, Thompson A 1968 High-resolution study
of low-energy heavy cosmic rays with Lexan track detec
tors. Phys. Rev. Lett. 21: 630-3
Price , Walker R 1963 Fossil tracks of charged
particles in mica and the age of minerals. J. Geophys. Res.
68: 4847-62
Young D A 1958 Etching of radiation damage in lithium
fluoride. Nature (London) 182: 375-7
R. L. Fleischer
[Rensselaer P o l y t e c h n i c I n s t i t u t e , T r o y ,
New York, USA]

See also: Thermoluminescence

Bibliography
Alter W, Price 1972 Radon detection using track
registration material. US Patent No. 3,665,194
DeBlois R W, Bean C 1970 Counting and sizing of
submicron particles by the resistive pulse technique. Rev.
Sci. Instrum. 41: 909-16
Fleischer R L 1981 Nuclear track production in solids.
Prog. Mater. Sci. Chalmers Anniversary Volume: 9 7 123
Fleischer R L, Alter W, Furman S C, Price , Walker
R 1972 Particle track etching. Science 178: 255-63
Fleischer R L, Giard W R, Mogro-Campero A, Turner L
G, Alter W, Gingrich J 1980 Dosimetry of environ
mental radon: methods and theory for low-dose inte
grated measurements. Health Phys. 39: 957-62
Fleischer R L, Hart R Jr, Giard W R 1970 Particle track
identification: application of a new technique to Apollo
helmets. Science 170: 1189-91
Fleischer R L, Mogro-Campero A 1978 Mapping of inte
grated radon emanation for detection of long-distance
migration of gases within the earth: techniques and prin
ciples. J. Geophys. Res. 83: 3539-49
Fleischer R L, Mogro-Campero A 1985 Association of
subsurface radon changes in Alaska and the Northeastern
United States with earthquakes. Geochim Cosmochim.
Acta 49: 1061-71
Fleischer R L, Price 1963a Charged particle tracks in
glass. J. Appl. Phys. 34: 2903-4
Fleischer R L, Price 1963b Tracks of charged particles
in high polymers. Science 140: 121-2
Fleischer R L, Price , Symes 1964 Novel filter for
biological studies. Science 143: 249-50
Fleischer R L, Price , Walker R 1965a Tracks of
charged particles in solids. Science 149: 383-93
Fleischer R L, Price , Walker R 1965b Ion explosion
spike mechanism for formation of charged-particle tracks
in solids. J. Appl. Phys. 36: 3645-52

Solid State: Study Using Muon Beams

T h e positive m u o n p r o v i d e s a r e m a r k a b l e s p e c t r o
scopic p r o b e of t h e solid state. I m p l a n t e d in virtually
a n y m a t e r i a l , its spin p o l a r i z a t i o n m a y be m o n i t o r e d
t o define t h e sites it occupies in lattices o r molecules
a n d t o r e p o r t o n local s t r u c t u r e a n d d y n a m i c s . W i d e
r a n g i n g a p p l i c a t i o n s in solid-state science a r e illus
t r a t e d in this article b y e x a m p l e s in m a g n e t i c s ,
c h e m i s t r y a n d q u a n t u m diffusion.
P r i m a r i l y , t h e m u o n is a sensitive m i c r o s c o p i c m a g
n e t o m e t e r : this e l e m e n t a r y particle h a s spin a n d a
m a g n e t i c m o m e n t a b o u t t h r e e times t h a t of t h e p r o
t o n . T h e frequencies of its r e s o n a n c e o r precession
signals p r o v i d e a direct a n d a c c u r a t e m e a s u r e m e n t of
local m a g n e t i c o r hyperfine fields. Its r e l a x a t i o n func
tions c h a r a c t e r i z e t h e d i s t r i b u t i o n in space o r the
fluctuation in time of these fields.
T h e m u o n is rarely a passive p r o b e , h o w e v e r , since
it r e p r e s e n t s a defect c a r r y i n g u n i t positive c h a r g e .
I n fact its i n t e r a c t i o n s w i t h t h e local e n v i r o n m e n t
a r e c o m m o n l y t h e m a i n focus of interest; studies of
this m o s t f u n d a m e n t a l of defects h a v e eliminated
c o m p l a c e n c y in several a r e a s . T h e i n t e r a c t i o n s ,
chemical a n d elastic, a r e essentially identical with
t h o s e of t h e p r o t o n , so t h a t their s t u d y is i n v a l u a b l e
in s i t u a t i o n s w h e r e h y d r o g e n c a n n o t b e detected
by c o n v e n t i o n a l spectroscopies. Alternatively, w h e n
m u o n a n d p r o t o n b e h a v i o r m a y b e c o m p a r e d , the
c o m p a r i s o n reveals a variety of kinetic a n d d y n a m i c
i s o t o p e effects: t h e m u o n h a s a b o u t o n e - n i n t h t h e
p r o t o n m a s s . T h i s o r d e r of m a g n i t u d e r a t i o greatly
facilitates identification of specifically q u a n t u m
effects (i.e., t h o s e involving z e r o p o i n t energy o r
tunnelling).

473

Solid State:

Study

Using Muon

1. Muon

Production

Methods

in Solid-State

Beams

and Detection:

Nuclear

T h e e x p e r i m e n t a l techniques for p r o d u c i n g a n d
detecting m u o n s h a v e c o m e t o be k n o w n collectively
as //SR, s t a n d i n g for m u o n spin r o t a t i o n , r e l a x a t i o n
a n d r e s o n a n c e (Brewer et al. 1975). T h e y are practised
at t h o s e accelerator l a b o r a t o r i e s o r m e s o n factories
w h e r e low-energy m u o n b e a m s a r e available. T h e
m u o n s derive from t h e decay of p i o n s , themselves
p r o d u c e d w h e n a target of g r a p h i t e o r o t h e r light
element is e x p o s e d t o a sufficiently energetic p r i m a r y
p r o t o n b e a m . T h e success of / / S R s p e c t r o s c o p y relies
o n t w o c i r c u m s t a n c e s . T h e first is t h e intrinsically
high degree of spin p o l a r i z a t i o n of t h e m u o n b e a m s
( u p t o 1 0 0 % for t h o s e collected from the d e c a y of
p i o n s a t rest), a n d t h e fact t h a t this initial p o l a r i z a t i o n
is largely preserved w h e n t h e m u o n s a r e s t o p p e d o r
thermalized in t h e s a m p l e of interest. T h e second is
the m a n n e r in which the s u b s e q u e n t e v o l u t i o n of
p o l a r i z a t i o n within t h e s a m p l e m a y t h e n be displayed.
T h e m u o n is itself a n u n s t a b l e particle, a n d decays
with a lifetime of 2.2 . A s e a c h m u o n decays, it emits
a p o s i t r o n in a direction which is closely c o r r e l a t e d
with its i n s t a n t a n e o u s spin o r i e n t a t i o n . T h i s is t h e
classic e x a m p l e of p a r i t y violation in r a d i o a c t i v e
decay, a n d its discovery by G a r w i n et al. (1957)
represented the s t a r t i n g p o i n t for the d e v e l o p m e n t of
this novel spectroscopy; these a u t h o r s were well
a w a r e of the p o t e n t i a l , a n d c o n c l u d e d their article
with the perceptive s t a t e m e n t " . . . it seems possible
t h a t polarized positive a n d negative m u o n s will
b e c o m e a powerful t o o l for e x p l o r i n g m a g n e t i c fields
in nuclei, a t o m s a n d i n t e r a t o m i c r e g i o n s . "
T h e decay p o s i t r o n s ( emission) m a y be c o u n t e d in
o n e or m o r e directions using scintillation d e t e c t o r s .
This use of " n u c l e a r m e t h o d s " of single particle
c o u n t i n g c o n t r i b u t e s hugely t o t h e r e m a r k a b l e sensiti
vity of / / S R spectroscopy. It p r o v i d e s a form of trigger
detection for m a g n e t i c r e s o n a n c e in which t r a n s i t i o n s
of the m u o n spin (typically in a frequency r a n g e
between kilohertz a n d gigahertz) a r e detected a t t h e
energy of the r a d i o a c t i v e decay. C u r i o u s as it s o u n d s
to use such a short-lived e l e m e n t a r y particle for a
solid-state p r o b e , t h e m u o n lifetime in fact defines a n
invaluable timescale for certain d y n a m i c a l studies,
w h e t h e r of h o p rates in diffusive m o t i o n , o r of fluc
t u a t i n g fields in m a g n e t i c m a t e r i a l s . V a r i o u s reviews
of the techniques a n d a p p l i c a t i o n s a r e available
(e.g., S t o n e h a m 1979, 1983, Schenck 1985, C o x 1987);
the following is a selection of highlights a n d recent
developments.

2. Semiconductors
Defect
Centers

and Insulators:

Hydrogenlike

F o r a fully p o l a r i z e d m u o n b e a m , a n d c o u n t i n g
p o s i t r o n s of all energies, t h e emission is a b o u t twice

474

<

10 > / /

Science

Figure 1
Level crossing resonance spectrum for a muonium defect
center in CuCl (after Schneider 1990: the spectrum
represents resonant polarization transfer from the muon
to the neighboring nuclei, defining the defect site and
determining local superhyperfine interactions)

as intense in t h e " f o r w a r d " direction (parallel t o the

m u o n p o l a r i z a t i o n ) as in the " b a c k w a r d " ( a n t i p a r a l lel) direction. A n y decrease in f o r w a r d - b a c k w a r d
a s y m m e t r y conveniently indicates d e p o l a r i z a t i o n o r
r e l a x a t i o n of t h e m u o n spin. F i g u r e 1 s h o w s a n
e x a m p l e of level crossing r e s o n a n c e in which a n
external m a g n e t i c field, applied parallel t o t h e initial
m u o n p o l a r i z a t i o n , is t u n e d so t h a t the c o m b i n e d
Z e e m a n a n d hyperfine energies of t h e m u o n p r o b e
exactly m a t c h t h a t of t h e s u r r o u n d i n g nuclei. T h e
s p e c t r u m also illustrates t h e f o r m a t i o n in certain
m a t e r i a l s of m u o n i u m , which m a y b e considered t o b e
t h e light i s o t o p e of h y d r o g e n : j u s t as a p r o t o n m a y
pick u p a n electron t o form a h y d r o g e n a t o m so m a y a
m u o n pick u p a n electron t o f o r m a m u o n i u m a t o m ,
+
M u = / z e " (for a discussion, a n d a n i n t r o d u c t i o n t o
m u o n i u m chemistry, see Brewer et al. 1975 a n d
W a l k e r 1983). I n t h e e x a m p l e of Fig. 1, m u o n i u m is
f o r m e d following m u o n i m p l a n t a t i o n in o n e of t h e
c u p r o u s halides a n d t h e s p e c t r u m indicates t h a t t h e
h y d r o g e n l i k e a t o m is t r a p p e d a n d i m m o b i l e a t t h e
t e t r a h e d r a l interstitial site defined by four nearest
+
neighbor C u ions.
T h e r e s o n a n c e e x p e r i m e n t of F i g . 1 m e a s u r e s a
time-averaged a s y m m e t r y a n d c a n benefit from t h e
high intensities n o w available from certain c o n t i n u o u s
m u o n sources. If a p u l s e d m u o n s o u r c e is used, o r if
the d a t a r a t e from a c o n t i n u o u s source is limited so
t h a t individual p o s i t r o n s m a y be c o r r e l a t e d with their

Solid State:

Temperature

(K)

Study

Temperature

(a)

Using Muon

Beams

(K)

(b)

Figure 2
Temperature dependence of muon spin-lattice relaxation rate in KC1, for three values of external field, and the extracted
rates for interstitial hopping (after Kadono 1990)

p a r e n t m u o n s , it is equally possible t o display t h e

e v o l u t i o n o r r e l a x a t i o n of t h e m u o n p o l a r i z a t i o n , a s a
function of t i m e following i m p l a n t a t i o n . M e a s u r e
m e n t s of r e l a x a t i o n r a t e (again in l o n g i t u d i n a l field)
for a n alkali h a l i d e , s h o w n in F i g . 2, r e p r e s e n t spinlattice r e l a x a t i o n of interstitial m u o n i u m d u e t o its
diffusive m o t i o n t h r o u g h this lattice. T h e t w o p e a k s in
r e l a x a t i o n r a t e (or, in m a g n e t i c r e s o n a n c e p a r l a n c e ,
Tx m i n i m a ) s h o w t h a t m u o n i u m m o b i l i t y is lowest in
t h e vicinity of 100 K , a n d increases b o t h a t h i g h e r a n d
lower t e m p e r a t u r e s . T h e l o w - t e m p e r a t u r e b e h a v i o r
represents q u a n t u m m o t i o n of t h e interstitial defect
a n d is m o r e readily o b s e r v e d for m u o n i u m t h a n for
h y d r o g e n b y virtue of its l o w e r m a s s .
F o r m a t e r i a l s in w h i c h h y d r o g e n itself is difficult o r
impossible t o detect, m u o n i u m p r o v e s t o b e a n invalu
able s u b s t i t u t e . T h i s is t h e case, for i n s t a n c e , in t h e
elemental ( g r o u p IV) s e m i c o n d u c t o r s a n d in a n u m b e r
of c o m p o u n d ( I I I - V ) s e m i c o n d u c t o r s ( P a t t e r s o n
1988). F i g u r e 3 illustrates a s t u d y p e r f o r m e d w i t h t h e
m a g n e t i c field a p p l i e d p e r p e n d i c u l a r t o t h e initial
m u o n p o l a r i z a t i o n , so t h a t t h e / / S R signal displays
oscillations c o r r e s p o n d i n g t o precession of t h e p o l a r i
zation. (This is m u o n spin r o t a t i o n , t h e m e t h o d m o s t
c o m m o n l y e m p l o y e d until recently.) F i g u r e 3 is t h e
F o u r i e r t r a n s f o r m of such a signal for gallium a r s e n
ide. T h e r e m a r k a b l e finding, originally m a d e in
silicon b y Brewer et al. (1973), is t h a t t h e r e a r e t w o
distinct m u o n i u m states. O n e of these ( k n o w n as
" n o r m a l " m u o n i u m ) h a s a hyperfine c o u p l i n g w h i c h
is isotropic, a l t h o u g h c o n s i d e r a b l y r e d u c e d f r o m t h e
v a c u u m state a t o m i c value; it c o r r e s p o n d s as expected
t o t h e a t o m t r a p p e d w i t h i n t h e t e t r a h e d r a l interstitial
cage. T h e o t h e r (the so-called " a n o m a l o u s " m u o n i u m
state) h a s a m u c h smaller a n d highly a n i s o t r o p i c
c o u p l i n g , w i t h axial s y m m e t r y a l o n g t h e <III> direc

t i o n s . Its s t r u c t u r e r e m a i n e d a puzzle for m a n y years

b u t is n o w u n d e r s t o o d t o be t h e m o r e stable of t h e
two a n d to represent m u o n i u m located at a bondc e n t e r e d site ( C o x a n d S y m o n s 1986). T h e c o n s e n s u s
of o p i n i o n from q u a n t u m electronic s i m u l a t i o n s is
n o w t h a t this s t r u c t u r e , w h i c h involves a c o n s i d e r a b l e
r e l a x a t i o n of t h e s u r r o u n d i n g lattice, is also t h e m o s t
stable for isolated h y d r o g e n defect centers, b o t h in
their n e u t r a l a n d positively c h a r g e d states.

3. Molecular
Chemistry

Materials:

Muon

and

Muonium

I n m o l e c u l a r m a t e r i a l s , m u o n i u m reacts like a t o m i c
h y d r o g e n t o b e c o m e i n c o r p o r a t e d in a w i d e variety of
m o l e c u l a r species, b o t h d i a m a g n e t i c (closed shell) a n d
p a r a m a g n e t i c ( o p e n shell). T h a n k s t o t h e u n p r e c e
d e n t e d m a s s r a t i o , i s o t o p e effects in t h e r e a c t i o n
kinetics as well as in t h e one-electron m o l e c u l a r
p r o p e r t i e s of t h e p r o d u c t s a r e c o n s i d e r a b l y g r e a t e r
t h a n t h o s e o b s e r v e d w i t h , for e x a m p l e , d e u t e r i u m .
M o s t a t t e n t i o n h a s b e e n p a i d t o t h e hyperfine i s o t o p e
effect in m u o n i u m - s u b s t i t u t e d o r g a n i c radicals, w h i c h
m a y b e t r a c e d t o t h e large z e r o p o i n t energy of
m u o n i u m b o u n d in c o v a l e n t c a r b o n - m u o n i u m o r
o x y g e n - m u o n i u m b o n d s ( R o d u n e r 1988, C l a x t o n et
al. 1990). A similar q u a d r u p o l e i s o t o p e effect h a s
recently b e e n o b s e r v e d in a closed shell species,
n a m e l y t h e m u o n i u m - s u b s t i t u t e d w a t e r molecule
H M u O ( C o x et al. 1990).
T h e labelling of large molecules b y m u o n i u m
a d d i t i o n is a p o t e n t i a l l y i m p o r t a n t t o o l . I n transpolyacetylene, for i n s t a n c e , t h e u n p a i r e d electron
i n t r o d u c e d b y this p r o c e s s is free t o m i g r a t e a l o n g t h e
c h a i n as a b o n d - a l t e r n a t i o n defect o r soliton. T h e
soliton m o t i o n in this a n d o t h e r c o n d u c t i n g p o l y m e r s

475

Solid State:

Study

Using Muon

Beams

Mu*

Mu

15 r

> LULU
0

l
500

1000
Frequency (MHz)

L_
1500

(a)

(b)

Figure 3
(a) The //SR spectrum of GaAs showing frequencies corresponding to the normal (Mu) and anomalous (Mu*) muonium
defect centers (after Kiefl et al. 1985) and (b) the "bond-center"
model for Mu* in which the muon lies close to the node
3
of the singly occupied molecular orbital, constructed from sp hybrids on the host atoms (after Cox and Symons, 1986)

maybe studied via distinctive forms of the muon spin

relaxation (Nagamine et al. 1984, Fischer et al. 1991).
Most recently, formation of the MuC^ radical in
Fullerene C^ (Ansaldo et al. 1991, Kiefl et al. 1992)
promises to provide a valuable probe of reorientational dynamics in this fascinating new phase of carbon.
4. Magnetism:

Spin Structure

and

Dynamics

In the presence of atomic moments on the host lattice,

//SR proves able to probe both the order parameter
and the dynamics. Long-range order gives rise to

spontaneous static internal fields, and, therefore, to

characteristic frequencies in the muon spin rotation
spectra. An example is shown in Fig. 4a. Fluctuations
of the internal fields give rise to muon spin relaxation,
both in the ordered and paramagnetic phases, whose
study nicely complements conventional magnetic
resonance and neutron scattering studies (De Renzi et
al. 1984, Lovesey et al. 1990). Particularly dramatic
are the divergence of relaxation rate corresponding to
the critical slowing down of the fluctuations and the
anisotropy of the correlations. An example of this
behavior is shown in Fig. 4b.

L
I

o o o cPoo

_ 100
Time

()

Temperature

()

(b)

Figure 4
(a) The muon spin rotation signal recorded for L a 2 C u 0 4 in zero external field displays the presence of (antiferro) magnetic
order (after Budnik et al. 1987) and (b) the muon spin relaxation rates recorded for single-crystal erbium with muon spin
parallel (squares) and perpendicular (circles) to the c axis reveal a striking anisotropy in the critical spin fluctuations (after
Hartmann et al. 1990)

476

Solid State:

Study

Using Muon

Beams

2.0
2222

=1.

123
2212

1.0

b
22mT ( R A D
3 5 0 mT ( P S I )

214

_L
1

-40

(a)

()

(b)

Figure 5
(a) Correlation of //SR linewidth with transition temperature Tc for various superconductor families (after Uemura et al.
1990) and (b) its variation with orientation for single-crystal Y B a 2 C u 3 0 7 _ 6 (after Forgan et al. 1990). Linewidth is
proportional to the variance of the internal field and to the inverse square of the London penetration depth

Since the m u o n invariably a d o p t s a n interstitial

position, it is p a r t i c u l a r l y sensitive t o c h a n g e s in t h e
spin s t r u c t u r e , via t h e a l t e r a t i o n in d i p o l a r s u m ; pSR
will, in fact, detect t h e slightest softening of a spin
structure before o t h e r t e c h n i q u e s a n d h a s t h e u n i q u e
ability t o distinguish a c h a n g e in static s t r u c t u r e from
the onset of slow fluctuations. D i r e c t m e a s u r e m e n t s
of m u o n r e l a x a t i o n time cover a d y n a m i c r a n g e of
four decades (centered r o u g h l y o n the m u o n lifetime);
the spin c o r r e l a t i o n times w h i c h m a y b e e x t r a c t e d
d e p e n d o n the a m p l i t u d e of t h e field m o d u l a t i o n
_ 4
involved b u t r a n g e from 1 0 s in w e a k m o m e n t
12
systems t o 1 0 " s in the h a r d m a g n e t s , in m a n y
instances o p e n i n g a time w i n d o w previously inaccess
ible (Kalvius et al. 1986).
T h e r e is n o need for a p o l a r i z i n g field, o r field
cycling sequence, w i t h pSR detection, so m e a s u r e
m e n t s m a y be m a d e directly in zero e x t e r n a l field. T h i s
m a k e s the m u o n a n i n v a l u a b l e p r o b e of " f r a g i l e "

wyvw

w\^vv

(a)

(b)

wvyw
(c)

Figure 6
Interstitial localization of the positive muon as a small
polaron defect in metals (a) and the elemental diffusive
step via phonon-assisted tunnelling (b, c): thermal
fluctuations provide a favorable intermediate
configuration for tunnelling between initial and final sites

systems, such as spin glasses, o r certain h e a v y fermion

systems, w h e r e t h e o r d e r c a n b e d i s t u r b e d o r s u p
pressed even in low external fields.
A topical e x a m p l e involving r a t h e r w e a k m o m e n t
systems is t h e identification of t h e a n t i f e r r o m a g n e t i c
p h a s e s w h i c h a r e t h e p a r e n t c o m p o u n d s t o the v a r i o u s
families of h i g h - t e m p e r a t u r e s u p e r c o n d u c t o r s . T h e
first such is illustrated in Fig. 4a. F o r t h e m u o n ,
" l o n g - r a n g e " m a g n e t i c o r d e r need only m e a n a c o r r e
l a t i o n length l o n g e r t h a n t h e c o n v e r g e n c e r a d i u s for
t h e d i p o l a r s u m , so t h a t m u c h less perfect o r d e r is
m o r e readily d e t e c t a b l e b y this local p r o b e t h a n is
possible by diffraction t e c h n i q u e s . pSR h a s succeeded
in identifying m a g n e t i c p a r e n t c o m p o u n d s for all the
v a r i o u s families of c u p r a t e s u p e r c o n d u c t o r s , b o t h
electron d o p e d a n d h o l e d o p e d ( L u k e et al. 1989, D e
R e n z i et al. 1990).
5. Superconductors:

Mapping

Internal

Fields

It is p e r h a p s t h e s t u d y of t h e s u p e r c o n d u c t i n g p h a s e s
themselves w h i c h h a s recently b r o u g h t pSR m e a s u r e
m e n t s t o t h e a t t e n t i o n of a wide a u d i e n c e . T h e elimi
n a t i o n of a n y o n m o d e l s of h i g h - r c s u p e r c o n d u c t i v i t y
(Kiefl et al. 1990) is a striking illustration of the
sensitivity of t h e m u o n m a g n e t o m e t e r . F o r t h e mixed
state of all t y p e II s u p e r c o n d u c t o r s , c o n v e n t i o n a l a n d
high-7^, the pSR frequency s p e c t r u m serves t o m a p
the d i s t r i b u t i o n of i n t e r n a l flux within the vortex
system ( H e r l a c h et al. 1990); t h e linewidth is directly
p r o p o r t i o n a l t o the field c o n t r a s t ( r a t h e r t h a n the
s q u a r e of this q u a n t i t y , a s for diffraction m e t h o d s )
a n d u n d o u b t e d l y p r o v i d e s t h e m o s t reliable m e a s u r e
m e n t of L o n d o n p e n e t r a t i o n d e p t h . T h i s q u a n t i t y is
i n t i m a t e l y related t o t h e p a i r i n g m e c h a n i s m of the
s u p e r c o n d u c t i n g carriers, via their c o n c e n t r a t i o n a n d
effective m a s s . Its m e a s u r e m e n t for such a wide var-

477

Solid State:

Study

Using Muon

Beams

10
Time

15
(/zs)

(a)

0.1

10

Temperature

100
(K)

(b)

Figure 7
(a) The zero-field relaxation function for muons in copper metal (this ISIS test spectrum is remarkable for displaying
evolution of the polarization beyond eight muon lifetimes, after Karlsson 1989). pSR provided the first demonstration of
this distinctive function, in which the polarization Pz(t) recovers at long elapsed time to ^ of its initial value, as predicted
by Kubo and Toyabe (1987). Relaxation of the J tail proves sensitive to extremely slow diffusion, (b) Collected results for
muon hop rates reveal quantum mobility at low temperatures as well as thermally activated motion (after Kadono et al.
1986)

iety of m a t e r i a l s a s t h e c u p r a t e high-!T c s u p e r c o n d u c
tors, heavy fermion systems, chevrel p h a s e s a n d even
o r g a n i c s u p e r c o n d u c t o r s , a n d t h e discovery o f a sys
tematic v a r i a t i o n with t r a n s i t i o n t e m p e r a t u r e w h i c h
e m b r a c e s all of these ( F i g . 5a) w o u l d b e u n t h i n k a b l e
w i t h o u t / / S R . Single-crystal m e a s u r e m e n t s also b e a r
o u t t h e p r e d i c t e d t e n s o r p r o p e r t i e s (Barford a n d
G u n n 1988) relating t o t h e a l m o s t t w o - d i m e n s i o n a l
c o n d u c t i o n in t h e layered c u p r a t e systems ( F i g . 5b).

6. Muons

in Metals:

Quantum

Dynamics

In m e t a l s , t h e u s e of m u o n s t o m i m i c p r o t o n b e h a v i o r
h a s been exploited t o t h e full, a n d every v a r i a n t of t h e
/zSR techniques b r o u g h t t o b e a r o n q u e s t i o n s relevant
t o h y d r o g e n in m e t a l s . I n p a r t i c u l a r , m u o n s in m e t a l s
h a v e been used t o clarify issues of q u a n t u m mobility:
they serve a s a testing g r o u n d for t h e f u n d a m e n t a l
p r o b l e m o f a q u a n t u m m e c h a n i c a l system (here a n
interstitial defect light e n o u g h t o t u n n e l ) c o u p l e d t o a
classical system (the electron a n d p h o n o n b a t h s ) . T h e
c o u p l i n g is large, so t h a t t h e initial m u o n state (which
m u s t be e x t e n d e d o n e n t r y a t e p i t h e r m a l energy)
collapses t o a localized state, " s e l f - t r a p p e d " w i t h i n a
single interstitial well. I n s e m i c o n d u c t o r s , t h e p h o n o n
c o u p l i n g is responsible for t h e localization; in m e t a l s
t h e electron c o u p l i n g is d o m i n a n t . Screening o f t h e
m u o n p o t e n t i a l b y a local a c c u m u l a t i o n o f electron
density is such a s t o p r e c l u d e t h e f o r m a t i o n of m u o n i u m (i.e., n o p a r a m a g n e t i c m o m e n t is c e n t e r e d o n
t h e m u o n ) a n d t h e local electronic s t r u c t u r e is d i a m a g n e t i c , a s it is for interstitial p r o t o n s . P h o n o n

478

c o u p l i n g is also evident from a slight local r e l a x a t i o n

of t h e lattice, so t h a t t h e overall defect h a s " s m a l l
p o l a r o n " c h a r a c t e r (see F i g . 6 a ) .
O f interest is h o w this entity, t h e interstitial m u o n
t o g e t h e r with its screening c h a r g e a n d lattice distor
tion, c a n m o v e from o n e site t o t h e next in a n
elemental diffusive step. T h e o n s e t of t h e slowest
m o t i o n is a p p a r e n t in t h e zero-field a n d l o w
longitudinal-field m u o n spin-lattice r e l a x a t i o n func
tion. T h e zero-field s p e c t r u m of F i g . 7a is for c o p p e r ,
w h i c h is a g o o d e x a m p l e of a m e t a l in w h i c h h y d r o g e n
is t o o insoluble t o b e s t u d i e d b y c o n v e n t i o n a l spec
troscopies. F a s t e r diffusion b e c o m e s a p p a r e n t in t h e
transverse-field m u o n spin r o t a t i o n spectra, a s a
m o t i o n a l n a r r o w i n g of t h e linewidth a n a l o g o u s t o
t h a t familiar in c o n v e n t i o n a l N M R . T h e h o p rates
d e d u c e d from these v a r i o u s m e a s u r e m e n t s reveal a
b r o a d m i n i m u m in m o b i l i t y a r o u n d 4 0 a n d a n
increase b o t h t o h i g h e r a n d l o w e r t e m p e r a t u r e s ( F i g .
7b). T h e b e h a v i o r is characteristic o f small p o l a r o n
states t h e (cf. t h e case of m u o n i u m in i n s u l a t o r s
s h o w n in F i g . 2). Level crossing r e s o n a n c e confirms
t h a t e q u i v a l e n t interstitial sites a r e involved a t all
t e m p e r a t u r e s ( L u k e et al. 1991). T h e t h e r m a l l y acti
v a t e d h o p p i n g reveals a n a c t i v a t i o n energy w h i c h is
m u c h less t h a n t h e classical b a r r i e r height b e t w e e n
n e i g h b o r i n g interstitial sites, a n d is well described b y
p h o n o n - a s s i s t e d tunnelling, of t h e sort p r o p o u n d e d
by F l y n n a n d S t o n e h a m a n d illustrated in F i g . 6. T h e
low t e m p e r a t u r e increase in m o b i l i t y is m u c h w e a k e r
t h a n for t h e n e u t r a l small p o l a r o n defect in i n s u l a t o r s ,
a n d finds its e x p l a n a t i o n in a d e p a r t u r e from a d i a b a tic b e h a v i o r , n a m e l y a surprising reluctance o n t h e

Solid State:
p a r t of t h e electronic screening c h a n g e t o follow t h e
m u o n m o t i o n ( K o n d o 1985).

7.

Perspectives

T h e s e e x a m p l e s give a glimpse of t h e b r o a d r a n g e of
a p p l i c a t i o n of i m p l a n t e d m u o n studies. Classed w i t h
t h e n u c l e a r - p r o b e spectroscopies, / / S R p r o v i d e s infor
m a t i o n o n local s t r u c t u r e w h i c h ideally c o m p l e m e n t s
t h e fc-space i n f o r m a t i o n o b t a i n e d from diffraction
techniques, a n d c o n t r i b u t e s t o a detailed m i c r o s c o p i c
picture of m a t t e r .
By virtue of t h e m a s s a n d lifetime of t h e m u o n
p r o b e , / / S R studies significantly e x t e n d t h e r a n g e of
d y n a m i c a l p h e n o m e n a accessible t o c o n v e n t i o n a l
magnetic resonance.
T h e p r e s e n t s t a t u s of this relatively novel s p e c t r o s
c o p y is best c o m p a r e d w i t h t h a t of m a g n e t i c r e s o
n a n c e s o m e d e c a d e s a g o . R e s u l t s o n m o d e l systems
validate t h e t e c h n i q u e , b u t h a v e also p r o d u c e d s o m e
surprises ( n o t a b l y a s r e g a r d s h y d r o g e n defects in
s e m i c o n d u c t o r s a n d light interstitial diffusion in
metals) w h i c h h a v e c a u s e d established views t o b e
revised. N e w a n d m o r e c o m p l e x systems m a y n o w b e
tackled w i t h confidence. I n a m o r p h o u s a n d m e s o scopic s t r u c t u r e s , for i n s t a n c e b o t h metallic a n d semi
c o n d u c t i n g ) , issues of site o c c u p a n c y , site c o m p e t i t i o n
with h y d r o g e n a n d diffusion d y n a m i c s a r e well suited
t o m u o n study; such e x p e r i m e n t s a r e in their infancy,
but have considerable potential.
See also: Magnetic Materials: Measurements; Supercon
ducting Materials: Measurements; X-Ray Diffraction,
Time-Resolved

Bibliography
Ansaldo F J, Niedermeyer Ch, Stronach C 1991 Muonium
in Fullerite. Nature 353: 129
Barford W, Gunn J F 1988 The theory of the measure
ment of the London penetration depth in uniaxial type II
superconductors by muon spin rotation. Physica C 156:
515-22
Brewer J H, Crowe , Gygax F N, Schenck A 1975
Positive muons and muonium in matter. In: Hughes V W,
Wu C S (eds.) 1975 Muon Physics. Academic Press, New
York
Brewer J H, Crowe , Johnson R F, Patterson
D,
+
Fleming D G, Schenck A 1973 Anomalous precession
in silicon. Phys. Rev. Lett. 31: 143-6
Budnick J I, Golnick A, Niedermeyer Ch, Recknagel E,
Rossmanith M, Weidinger A, Chamberland B, Filipkowski M, Yang D 1987 Observation of magnetic
ordering in La 2Cu0 4 by muon spin rotation spectroscopy.
Phys. Lett. A 124: 103-6
Claxton A, Graham A M, Cox S F J, Marie D M, Meier
F, Vogel S 1990 Vibrationally averaged spin densities on
muons and protons in the hydroxyl and ethyl radicals.
Hyperfine Interact. 65: 913-26
Cox S F J 1987 Implanted muon studies in condensed matter
science. J. Phys. C 20: 3187-319

Study

Using Muon

Beams

Cox S F J, Smith J A S, Symons C R 1990 Measurements

1 7
of 0 quadrupole interactions and identification of the
diamagnetic fraction in ice by muon level crossing reso
nance. Hyperfine Interact. 65: 993-1004
Cox S F J, Symons C R 1986 Molecular radical models
for the muonium centers in solids. Chem. Phys. Lett. 126:
516-25
De Renzi R, Guidi G, Bucci C, Tedeschi R, Calestani G
1990 The magnetic phase in 2-2-1-2 superconducting
material. Hyperfine Interact. 63: 295-304
De Renzi R, Guidi G, Podini P, Tedeschi R, Bucci C, Cox S
F J 1984 Magnetic properties of MnF 2 and CoF 2 deter
mined by implanted positive muons, II. Sublattice magne
tisation and phase transition. Phys. Rev. 30: 197-204
Fisher A J, Hayes W, Pratt F L 1991 Theory of positive
muons in polyacetylene. / . Phys. Cond. Matter 3: 9823-9
Flynn C P, Stoneham A 1970 Quantum theory of
diffusion with application to light interstitials in metals.
Phys. Rev. 1: 3966-78
Forgan , Lee S L, Sutton S, Abell J S, Cox S F J, Scott C
A, Keller H, Pumpin B, Schneider J W, Simmler H,
Zimmerman P, Savic I 1990 Angle dependence of the
muon relaxation rate in the mixed state for single crystals
of YBa 2Cu 30 7_ < 5. Hyperfine Interact. 63: 71-2
Garwin R L, Lederman L M, Weinrich 1957 Observation
of the failure of conservation of parity and charge conju
gation in meson decays: magnetic moment of the free
muon. Phys. Rev. 105: 1415-17
Hartmann O, Harris S W, Wappling R, Kalvius G M, Asch
L, Dalmas de Reotier P, Yaouanc A 1990 Asymmetric
spin fluctuations in erbium. Hyperfine Interact. 64: 381-2
Herlach D, Mager G, Rosenkranz J, Schmolz M, Schwarz
W, Seeger A, Tempi W, Brandt , Essmann U,
Furderer K, Gladisch 1990 Magnetic flux distribution
in the bulk of pure type-II superconductor niobium
measured with positive muons. Hyperfine Interact. 63:418
Kadono R 1990 Quantum diffusion of muonium in insula
tors. Hyperfine Interact. 64: 615-34
Kadono R, Imazato J, Nishiyama K, Nagamine K, Yamazaki T, Richter D, Welter J-M 1985 Precise measurement
of low temperature diffusion of positive muons in Cu:
evidence for the effect of muon-electron interactions in
metals. Phys. Lett. A 109: 61-4
Kalvius G M, Litterst F J, Asch L, Chappert J 1986 Electron
structure and spin dynamical properties of crystalline and
amorphous rare-earth intermetallics from Mossbauer and
//SR experiments. Hyperfine Interact. 25: 709-36
Karlsson 1989 Nuclear solid state physics. Uppsala
University Research Report. Uppsala University, Upp
sala, Sweden
Kiefl R F, Brewer J H, Affleck I, Cardon J F, Dosanjh P,
Hardy W N, Hsu T, Kadono R, Kempton J R, Kreitsman
S R, Li Q, O'Reilly A H, Riseman , Schleger ,
Stamp C , Zhon , Le L P, Luke G M, Sternlieb B,
Uemura Y J, Hart R, Lay W 1990 Search for
magnetic fields due to anyons in high-!Tc superconductors.
Hyperfine Interact. 63: 139-44
Kiefl R F, Schneider J W, Keller H, Kundig W, Odermatt
W, Patterson D, Blazey W, Estle L, Rudaz S L
1985 Muonium centers in GaAs and GaP. Phys. Rev.
32: 530-2
Kiefl R F, Schneider J W, MacFarlane A, Chow K, Duty
L, Estle L, Hitti B, Lichti R L, Ansaldo J, Schwab C,

479

Solid State:

Study

Using Muon

Beams

Percival W, Wei G, Wlodek S, Kojima K, Romanow W

J, McCauley J Jr, Coustel N, Fischer J E, Smith A
1992 Molecular dynamics of MuC^ in solid C M. Phys.
Rev. Lett. 68: 1347-50
Kondo J 1985 Diffusion of light interstitials in metals.
Physica 135: 279-85
Kubo R, Toyabe 1967 A stochastic model for low field
resonance and relaxation. In: Blinc R (ed.) 1967 Magnetic
Resonance and Relaxation. North-Holland, Amsterdam,
pp. 810-23
Lovesey S W, Cuccoli A, Tognetti V 1990 Theory of
paramagentic and critical spin fluctuations in simple
magnets. Hyperfine Interact. 64: 321-30
Luke G M, Brewer J H, Kreitzmann S R, Noakes D R,
Celio M, Kadono R, Ansaldo J 1991 Muon diffusion
and spin dynamics in copper. Phys. Rev. 43: 3284-97
Luke G M, Sternlieb J, Uemura Y J, Brewer J H, Kadono
R, Kiefl R F, Kreitzman S R, Riseman , Gopalakrishnan J, Sleight A W, Subramanian A, Uchida S,
Takagi H, Tokura Y 1989 Studies of static magnetic order
in electron superconductors and their parent compounds.
Nature 338: 49-51
Nagamine K, Ishida K, Matsuzaki T, Nishiyama K, Kuno
Y, Yamazaki T, Shirikawa 1984 Solitons in polyacetylene produced and probed by positive muons. Phys. Rev.
Lett. 53: 1763-6
Patterson D 1988 Muonium states in semiconductors.
Rev. Mod. Phys. 60: 69-159
Roduner 1988 The positive muon as a probe in free radical
chemistry. Springer Verlag Lecture Notes in Chemistry,
Vol. 49. Springer, Berlin
Schenck A 1985 Muon Spin Rotation Spectroscopy. Hilger,
Bristol, UK
Schneider J W 1990 Thesis Zurich University
Schneider J W, Keller H, Odermatt W, Pumpin B, Savic
I M, Simmler H, Dodds S A, Estle L, DuVarney R C,
Chan K, Kadono R, Kiefl R F, Li Q, Risemann ,
Zhan , Lichti R L, Schwab C 1990 Resolved nuclear
hyperfine structure of muonium in CuCl by means of
muon level crossing resonance. Hyperfine Interact. 64:
543-50
Stoneham A 1979 Muons and muon trapping by solid
state imperfections. Comments Solid State Phys. 9: 77-83
Stoneham A 1983 Muons and muonium in solids. Helv.
Phys. Acta 56: 449-59
Uemura Y J, Le L P, Luke G M, Sternlieb J, Brewer J H,
Carolan J, Hardy W, Kadono R, Kiefl R F, Kreitzman S
R, Riseman , Searman C L, Neumeier J J, Maple
, Saito G, Yamachi H, Takagi H, Uchida S, Gopalakrishnan J, Subramanian A, Sleight A W, Xiao G 1990
Correlations between Tc and njm (carrier density/effec
tive mass) in high-r c and organic superconductors.
Hyperfine Interact. 63: 131-8
Walker D C 1983 Muon and Muonium Chemistry. Cam
bridge University Press, Cambridge
S. F . J. C o x
[Rutherford Appleton Laboratory,
Didcot, U K ]
A. M . Stoneham
[AEA Industrial Technology,
Didcot, U K ]
480

Spark-Source Mass Spectrography

S p a r k - s o u r c e m a s s s p e c t r o g r a p h y ( S S M S ) is a n i n o r
ganic trace-element survey t e c h n i q u e w h i c h is actually
closer in its a p p l i c a t i o n s t o emission s p e c t r o g r a p h y o r
x-ray fluorescence t h a n t o o t h e r m a s s s p e c t r o m e t r i c
m e t h o d s . S S M S differs from o t h e r m a s s s p e c t r o m e t r i c
m e t h o d s in its a p p r o a c h t o ionizing t h e s a m p l e .
Its a i m is t o ionize all the elements in a s a m p l e
regardless of t h e m a t r i x o r elemental associations. T o
a c c o m p l i s h this, s p a r k - s o u r c e i n s t r u m e n t s use r a d i o frequency (rf) voltages of u p t o 100 k V in t h e ioniza
tion process. T h e s e extremely high voltages p r o d u c e
u n i q u e m a s s spectra b u t also i m p o s e restrictions o n
the design of t h e i n s t r u m e n t .

/.

Design

Considerations

I o n s are p r o d u c e d by a n rf s p a r k in w h i c h a n a l t e r n a t
ing c u r r e n t p o t e n t i a l of 10100 k V is g e n e r a t e d in
m i c r o s e c o n d pulses. T h e s p a r k o c c u r s between t w o
s a m p l e electrodes a n d i o n i z a t i o n m a y o c c u r as t h e
result of electron b o m b a r d m e n t of n e u t r a l v a p o r
p r o d u c e d in t h e s p a r k . T h e length of the s p a r k pulse
a n d t h e repetition r a t e a r e c o n t r o l l a b l e .
Since t h e i o n i z a t i o n energy available is m u c h
greater t h a n the i o n i z a t i o n p o t e n t i a l of the v a r i o u s
elements, essentially u n i f o r m i o n i z a t i o n efficiency is
o b t a i n e d . I n t h e o r y this allows a direct d e t e r m i n a t i o n
of elemental c o n c e n t r a t i o n by m e a s u r e m e n t of p h o toplate darkening.
O n e result of t h e e n o r m o u s a m o u n t of energy
involved in t h e i o n p r o d u c t i o n process by rf s p a r k is
a n i o n b e a m w i t h a large energy s p r e a d . E l e c t r o n
i m p a c t a n d t h e r m a l ion sources, for e x a m p l e , use
m u c h less energy in the i o n i z a t i o n process a n d as a
c o n s e q u e n c e energy s p r e a d s of less t h a n 1 eV are t o b e
f o u n d in ion b e a m s from these sources. T h e r e are t w o
3
far-reaching effects of t h e large ( 1 0 eV) energy s p r e a d
in rf s p a r k i o n b e a m s . T h e first dictates the use of a
double-focusing analyzer (Fig. 1) a n d t h e second
requires t h e use of a p h o t o g r a p h i c detector.
F i g u r e 1 illustrates t h e s p a r k - s o u r c e i n s t r u m e n t
s h o w i n g t h e source region w h e r e ions a r e formed, a n d
t h e double-focusing analyzer w h e r e t h e ions are first
energy filtered, t h e n m a s s analyzed a n d
finally
detected by the p h o t o g r a p h i c e m u l s i o n . T h e d o u b l e focusing analyzer used in all S S M S i n s t r u m e n t s is the
M a t t a u c h - H e r z o g analyzer. T h e resolution a t t a i n a b l e
d e p e n d s u p o n t h e energy s p r e a d in t h e ion b e a m , a n d
resolutions in the r a n g e 1000-5000 a r e n o r m a l for
s p a r k i n s t r u m e n t s . T h e p h o t o g r a p h i c emulsion is t h e
best d e t e c t o r for S S M S because its i n t e g r a t i n g p r o p e r
ties n e g a t e t h e wide v a r i a t i o n s in i o n - b e a m intensity
p r o d u c e d by the rf s p a r k source. I n a d d i t i o n , a n entire
m a s s s p e c t r u m from lithium t o u r a n i u m c a n b e s h o w n
o n the p h o t o p l a t e d u e t o t h e focusing p r o p e r t i e s of
t h e M a t t a u c h - H e r z o g analyzer. T h i s ability t o see t h e

Spark-Source

Mass

Spectrograph);

High-voltage
leads for spark
a n d ion

Figure 1
Spark-source instrument showing the source region and double-focusing analyzer

entire c o m p o s i t i o n of a s a m p l e is a g r e a t aid in
analytical s i t u a t i o n s . T h e universally used p h o t o
g r a p h i c e m u l s i o n is t h e llford Q - p l a t e .

2. Sample

Requirements

Since t h e i o n i z a t i o n p r o c e s s d e p e n d s o n b r e a k d o w n of
t h e g a p b e t w e e n t w o electrodes, a p a i r of solid c o n
d u c t i n g electrodes is o b v i o u s l y r e q u i r e d . S a m p l e s a r e
best c o n s i d e r e d a s o n e of t h e following types: solid
c o n d u c t o r s , p o w d e r e d c o n d u c t o r s , solid i n s u l a t o r s ,
p o w d e r e d i n s u l a t o r s , small s a m p l e s a n d liquids.
Solid c o n d u c t o r s n e e d o n l y b e c u t t o a c o n v e n i e n t
size. P o w d e r s , either c o n d u c t o r s o r i n s u l a t o r s , c a n b e
pressed i n t o solid s h a p e s w i t h c o m m e r c i a l s a m p l e
p r e p a r a t i o n dies a n d presses. S o m e m e t a l p o w d e r s
(e.g., silver) m a y b e pressed i n t o electrodes directly,
b u t m o s t m e t a l s a n d all i n s u l a t o r s will need t o b e
mixed w i t h a c o n d u c t o r before b e i n g pressed i n t o
electrodes. By far t h e m o s t useful c o n d u c t o r for these
s a m p l e s is h i g h - p u r i t y g r a p h i t e p o w d e r . U s u a l l y a
50:50 m i x t u r e of s a m p l e a n d g r a p h i t e is t h o r o u g h l y
mixed a n d pressed i n t o h o m o g e n e o u s , d u r a b l e
electrodes.
Solid i n s u l a t o r s a m p l e s p r e s e n t a challenge. If they
are true insulators then n o spark a n d consequently n o
ions c a n b e o b t a i n e d . If a t t e m p t s a r e m a d e t o g r i n d
t h e solid t o a p o w d e r , it will b e c o n t a m i n a t e d t o t h e
p o i n t w h e r e it b e a r s n o r e s e m b l a n c e t o t h e original
s a m p l e . T h e best c o u r s e h e r e is t o try t o r u n solid
i n s u l a t o r s directly. U p t o 100 k V of s p a r k v o l t a g e is
available o n c o m m e r c i a l i n s t r u m e n t s a n d 7 0 - 1 0 0 % of

these voltages will p r o d u c e i o n s from m a n y , s u p

posedly pure, insulators.
M o s t liquid s a m p l e s a r e h a n d l e d q u i t e easily, a n d
due to the opportunity to concentrate the sample,
sensitivities b e l o w 1 p p b c a n b e a t t a i n e d routinely.
T h e p r o c e d u r e involves p i p e t t i n g a k n o w n v o l u m e
o n t o 1 g of h i g h - p u r i t y g r a p h i t e p o w d e r . T h e m i x t u r e
is h e a t e d gently t o distill a w a y t h e liquid. T h e residue
is t h e n m i x e d a n d pressed i n t o electrodes for analysis.

3. Spark-Source

Mass

Spectra

S p a r k - s o u r c e m a s s s p e c t r a a r e u n i q u e in their p r o d u c
t i o n of m u l t i p l y c h a r g e d species. M o s t m a s s s p e c t r o m e t r i c sources p r o d u c e singly c h a r g e d species since
t h e high energy r e q u i r e d for t h e s e c o n d i o n i z a t i o n
p o t e n t i a l is n o t available. W i t h t h e excess energy
available in rf s p a r k sources m a n y stages of multiple
i o n i z a t i o n a s well a s t h e p r o d u c t i o n of m o l e c u l a r
species a r e seen. T h e m o s t intense lines a r e t h o s e d u e
t o singly c h a r g e d i o n s . M u l t i p l e stages of i o n i z a t i o n
a r e visible a s ions w i t h c h a r g e s of + 8 o r m o r e . T h e s e
fall a t
i, i, . . I
of t h e a t o m i c m a s s .
I n a d d i t i o n , certain e l e m e n t s such as c a r b o n a n d
+
silicon will f o r m p o l y a t o m i c clusters (e.g., Si 2 ). T a b l e
1 s h o w s t h e v a r i o u s i o n s p r o d u c e d from a silicon
s a m p l e . O b v i o u s l y , i m p u r i t i e s of interest in t h e 5 6 - 6 0
m/e ( m a s s / c h a r g e ) region will be seriously i m p a i r e d by
interferences from S i ^ . A t h i r d a n d less intense g r o u p
of i o n s arises from i o n i z a t i o n s of m o l e c u l a r species,
+
+
such as S i C in silicon c a r b i d e s a m p l e s o r G a A s
f r o m gallium a r s e n i d e . L a s t of t h e spectral types a r e

481

Spark-Source

Mass

Spectrograph};

Table 1
Ions produced from silicon in an rf spark source
Ion type

detectable o n a 1 n C e x p o s u r e is e q u i v a l e n t t o a n
a t o m i c c o n c e n t r a t i o n of 1 p p m .
m/e

Multiply charged
+
Sii,+ Si2 9,2 +SiJ
Sil 8 +, Si2 9 , Si3V
Si*8 , Si*,*, SiV
Molecular
+
Si2+ (28, 28)
Si2+ (28, 29)
Si2+ (29, 29)
Si2+ (29, 30)
Si2 (30, 30)
Complex
+
SiC + (28, 12)
SiC + (29, 12) (28, 13)
SiC + (30, 12) (29, 13)
SiC (30, 13)

28, 29, 30
14, 14.5, 15
7, 7.25, 7.5
56
57
58
59
60
40
41
42
43

the c o m p l e x ions such as oxides, nitrides a n d h y d r i d e s

of t h e elements being analyzed. T h e o c c u r r e n c e of
these c o m p l e x o r m o l e c u l a r ions c a n b e a m a j o r
p r o b l e m in certain m a t r i c e s . F o r e x a m p l e , t h e analysis
of r a r e - e a r t h oxides p r o d u c e s m a n y R O M y p e i o n s .
D u e t o t h e c o m p l e x isotopic c h a r a c t e r of a l t e r n a t e
r a r e e a r t h s , these oxide ions a r e d e t r i m e n t a l t o highsensitivity r a r e - e a r t h analyses.
A n artifact, called c h a r g e - e x c h a n g e lines, a p p e a r s
in these spectra a n d is t h e result of collisions b e t w e e n
ions a n d residual gas molecules. T h e s e collisions
usually o c c u r between t h e electrostatic a n d m a g n e t i c
analyzers. I n a p r o p e r l y p u m p e d i n s t r u m e n t w i t h
g o o d v a c u u m , c h a r g e - e x c h a n g e lines a r e s e l d o m seen
a n d a r e never a n analytical p r o b l e m .

4. Interpretation

and

Quantitation

Except for t h e special case w h e r e i s o t o p e d i l u t i o n is

used, S S M S c a n only b e c o n s i d e r e d a s e m i q u a n t i t a
tive t e c h n i q u e . A g r e a t deal o f t h o u g h t f u l w o r k h a s
gone into attempts t o calibrate the photographic
emulsion a n d p r o d u c e q u a n t i t a t i v e d a t a , b u t these
h a v e m e t with limited success.
T h e p r o c e d u r e for r u n n i n g samples using p h o t o
g r a p h i c detection involves p r o p e r s a m p l e cleaning
a n d p r e p a r a t i o n , a l i g n m e n t in t h e source, p u m p d o w n
a n d finally s p a r k i n g . A p r e s p a r k p e r i o d is often
advisable since it r e m o v e s c o n t a m i n a n t s i n t r o d u c e d
d u r i n g s a m p l e p r e p a r a t i o n . If surface impurities a r e
of interest, special c a r e m u s t b e t a k e n d u r i n g s a m p l e
handling a n d loading.
T h e r e is r o o m o n t h e 5 c m wide p h o t o p l a t e s for 1 5 30 spectra. A series of g r a d e d e x p o s u r e s a r e m a d e
r a n g i n g from 0.0001 n C t o 1000 n C d e p e n d i n g o n t h e
desired sensitivity. I n general t e r m s , a spectral line j u s t

482

4.1

Interpretation

O n c e t h e p l a t e h a s b e e n e x p o s e d a n d d e v e l o p e d it is
t h e n r e a d y for i n t e r p r e t a t i o n . T h i s step, w h i c h
involves c h o o s i n g a n analytical line o r lines for t h e
q u a n t i t a t i o n of e a c h element, is p r o b a b l y t h e source
of t h e largest e r r o r s in q u a n t i t a t i n g S S M S .
Since S S M S spectra c a n b e q u i t e c o m p l e x t h e task
of c h o o s i n g a n d identifying t h e analytical line is often
difficult. W h e n e v e r possible, t h e identity o f t h e line
c h o s e n s h o u l d b e confirmed b y t h e presence of its
d o u b l y ionized c o u n t e r p a r t a t a p p r o x i m a t e l y t h e cor
rect intensity. F o r e x a m p l e , if t h e line a t m/e 75 is t o
be used t o e s t i m a t e t h e arsenic c o n t e n t of a s a m p l e ,
t h e n t h e a n a l y s t m u s t b e a s s u r e d t h a t there is a line a t
2 +
m/e 37.5 c o r r e s p o n d i n g t o A s , t h a t it is a b o u t o n e t e n t h t h e intensity of t h e line a t m/e 75 a n d t h a t n o
interfering species exist w h i c h c o u l d c o n t r i b u t e t o t h e
lines being used. T h e a n a l y s t m u s t c o n s t a n t l y b e
a w a r e o f t h e m a t r i x u n d e r analysis a n d of all possible
line misidentifications a n d interferences.
T r u e spectral interferences a r e relatively r a r e in t h e
i n t e r p r e t a t i o n of s p a r k s o u r c e spectra a n d m o s t of
these involve m o n o i s o t o p i c elements. I t is difficult, for
e x a m p l e , t o a n a l y z e for trace p h o s p h o r u s (mass 31) in
3+
a n i o b i u m m a t r i x (mass 93) b e c a u s e t h e N b
line a t
m/e 31 is of high intensity a n d completely o b s c u r e s t h e
low-level p h o s p h o r u s line also a t m/e 3 1 .

4.2

Quantitation

O n c e t h e a n a l y s t is certain t h a t t h e lines c h o s e n a r e
valid h e m a y u s e either of t w o m e t h o d s for q u a n t i
tationvisual estimation or microphotometry. T h e
t w o m e t h o d s p r o d u c e essentially t h e s a m e degree of
q u a n t i t a t i o n . T h e visual m e t h o d involves e s t i m a t i o n
of t h e e x p o s u r e necessary t o p r o d u c e a j u s t - d e t e c t a b l e
line of t h e e l e m e n t o f interest. T h i s is related t o a n
i n t e r n a l s t a n d a r d ( m o s t often a small i s o t o p e o f t h e
m a t r i x ) b y t h e following f o r m u l a :
6

C=(EJEi)(X/\00)(IJIi)^l0

(1)

w h e r e C is t h e c o n c e n t r a t i o n of t h e e l e m e n t s o u g h t in
a t o m i c p p m , t h e subscripts s a n d i refer t o t h e
s t a n d a r d a n d i m p u r i t y , is t h e e x p o s u r e necessary t o
p r o d u c e t h e j u s t - d e t e c t a b l e line, X is t h e c o n c e n t r a
t i o n of t h e i n t e r n a l s t a n d a r d a n d / is t h e a b u n d a n c e
( % ) of t h e i s o t o p e used.
T h e m i c r o p h o t o m e t e r m e t h o d involves m e a s u r e
m e n t of t h e b l a c k e n i n g ( o r actually t r a n s m i s s i o n ) o f
t h e spectral lines. A c a l i b r a t i o n curve for e a c h e m u l
sion b a t c h m u s t b e p r e p a r e d b y p l o t t i n g e x p o s u r e
versus b l a c k e n i n g for a n u m b e r of isotopes o f a
s t a n d a r d . T i n is a n excellent element for this p u r p o s e
since it h a s a large n u m b e r o f i s o t o p e s of widely
v a r y i n g a b u n d a n c e . T h i s c a l i b r a t i o n c u r v e is t h e n
used t o o b t a i n a c c u r a t e values of E{ a n d Es from E q n .
(1).

Stress

T h e r e a r e t w o cases w h e r e a c c u r a t e analytical d e
t e r m i n a t i o n s m a y be p e r f o r m e d w i t h S S M S . T h e s e a r e
instances w h e r e electrical d e t e c t i o n is used i n s t e a d of
p h o t o p l a t e detection a n d w h e r e i s o t o p e d i l u t i o n is
used. Electrical d e t e c t i o n involves t h e use of a n elec
t r o n multiplier replacing t h e p h o t o p l a t e in t h e focal
p l a n e . Accuracies of 5 % h a v e b e e n a t t a i n e d r o u
tinely w h e r e s t a n d a r d s a r e available. I s o t o p e d i l u t i o n
is useful in c o m b i n a t i o n w i t h S S M S since all e l e m e n t s
are ionized. T h e N a t i o n a l B u r e a u of S t a n d a r d s r o u
tinely uses S S M S in c o n j u n c t i o n w i t h i s o t o p e d i l u t i o n
for the certification of s t a n d a r d reference m a t e r i a l s .

5.

Applications

Metallurgical a p p l i c a t i o n s cover t h e r a n g e from p a r t

p e r billion level analyses of h i g h - p u r i t y m e t a l s t o
c o m p a r a t i v e analyses of a c c e p t a b l e a n d failed alloys.
S e m i c o n d u c t o r m a t e r i a l s a r e p r i m e c a n d i d a t e s for
S S M S b e c a u s e of their u n u s u a l l y low t o l e r a n c e for
certain impurities. Biological a p p l i c a t i o n s include
e v a l u a t i o n of trace-element c o m p o s i t i o n s in b o d y
fluids o r tissues. E n v i r o n m e n t a l h a z a r d s m a y b e
e v a l u a t e d b y m e a n s of S S M S . T h e s e analyses r a n g e
from t h e d e t e r m i n a t i o n of t r a c e elements in w a t e r , t o
the e v a l u a t i o n of chemical c o m p o s i t i o n of p a r t i c u
lates e m i t t e d from a s b e s t o s facilities, f o u n d r i e s ,
smelters, p a c k i n g p l a n t s a n d p o w e r p l a n t s .
S S M S c o n t i n u e s t o b e a u n i q u e t o o l for trace-level
i m p u r i t y analyses in a wide variety of m a t e r i a l s . T h e r e
is n o o t h e r analytical t e c h n i q u e w h i c h c o m b i n e s t h e
excellent sensitivity a n d c o m p l e t e e l e m e n t c o v e r a g e of
SSMS.
See also: Laser Microprobe Mass Spectrometry; Organic
Mass Spectrometry; Secondary-Ion Mass Spectrometry; XRay Fluorescence Spectrometry
Bibliography
Morrison G 1965 Trace Analysis: Physical Methods.
Interscience, New York
Roboz J 1968 Introduction to Mass Spectrometry: Instru
mentation and Techniques. Interscience, New York
F . D . Leipziger
[Northern Analytical Laboratory, Amherst,
New Hampshire, USA]

Stress Distribution: Analysis Using

Thermoelastic Effect
It is generally k n o w n t h a t a g a s u n d e r g o i n g c o m p r e s
sion h e a t s u p or, conversely, a n e x p a n d i n g gas cools
d o w n . Less well k n o w n is t h a t a similar p h e n o m e n o n ,
referred t o as t h e t h e r m o e l a s t i c effect, o c c u r s w h e n a
solid m a t e r i a l u n d e r g o e s m e c h a n i c a l d e f o r m a t i o n in
t h e elastic regime. O n e r e a s o n for this c o u l d p e r h a p s
be t h e fact t h a t t e m p e r a t u r e c h a n g e s c o r r e s p o n d i n g t o

Distribution:

Analysis

Using

Thermoelastic

Effect

c h a n g e s in stress a r e extremely small for solids. F o r

e x a m p l e , r a p i d l o a d i n g of a mild steel u p t o its yield
p o i n t w o u l d p r o d u c e a t e m p e r a t u r e c h a n g e of only
a b o u t 0.2 C a n d , a s a result, such a c o u p l i n g b e t w e e n
m e c h a n i c a l a n d t h e r m a l excitation is usually neg
lected in m o s t a p p l i c a t i o n s . H o w e v e r , m o d e r n
infrared (ir) d e t e c t i o n a n d signal processing tech
n i q u e s , t o g e t h e r with a well established law relating
t h e c h a n g e s in t e m p e r a t u r e t o c h a n g e s in stress of a
solid b o d y , h a v e e n a b l e d this p h e n o m e n o n t o be
exploited a s a m e a n s of e x p e r i m e n t a l stress analysis.

1.

The Thermoelastic

Effect

The coupling between mechanical deformation and

t h e t h e r m a l energy of a n elastic b o d y w a s n o t e d as
early as t h e t u r n of t h e n i n e t e e n t h c e n t u r y a n d the first
theoretical t r e a t m e n t is a t t r i b u t e d t o L o r d Kelvin in
1853. F o r a g o o d historical review o n this subject, t h e
r e a d e r is referred t o H a r w o o d et al. (1991). Basically,
t h e expression describing c o u p l e d linear t h e r m o e l a s t i city is simply a s t a t e m e n t of t h e laws of c o n s e r v a t i o n
of energy a n d m o m e n t u m w h e r e for a linear isotropic
m a t e r i a l it m a y b e s h o w n (e.g., Boley a n d W e i n e r
1960) t h a t

*v e = c . | ? +
2

r f
0

(1)

in w h i c h is t h e t e m p e r a t u r e difference a b o v e a
reference t e m p e r a t u r e T0; k, p, Ct a n d a r e the
m a t e r i a l coefficients of t h e r m a l c o n d u c t i v i t y , density,
specific h e a t u n d e r c o n s t a n t strain a n d coefficient of
linear t h e r m a l e x p a n s i o n , respectively; S is t h e s u m
of t h e p r i n c i p a l stresses (bulk stress), a n d / d e n o t e s
time.
A further simplification c a n be m a d e w h e n a d i a b a tic c o n d i t i o n s a p p l y , t h a t is w h e n t h e r m a l c o n d u c t i o n
c a n b e c o n s i d e r e d insignificant; t h e left-hand side of
E q n . (1) m a y b e neglected a n d i n t e g r a t i n g with respect
t o / leads t o K e l v i n ' s law:
^ = - K A S

(2)

w h e r e a n d AS a r e t h e c h a n g e s in t e m p e r a t u r e a n d
b u l k stress, respectively, a n d = oil(pCe) is k n o w n as
the thermoelastic constant.
K e l v i n ' s law p r o v i d e s a simple a n d direct link
b e t w e e n t h e d y n a m i c t e m p e r a t u r e a n d b u l k stress a n d
so f o r m s t h e basis for e x p e r i m e n t a l stress analysis b y
t h e m e a s u r e m e n t of t e m p e r a t u r e .

2. Thermometric

Stress

Analysis

A l t h o u g h t h e t h e r m o e l a s t i c effect h a s b e e n well
u n d e r s t o o d since t h e f o u n d i n g w o r k of Kelvin, its
potential practical application was not demonstrated

483

Stress

Distribution:

Analysis

Using Thermoelastic

until Belgen (1967) s h o w e d t h e feasibility of u s i n g ir

r a d i o m e t r y t o h a r n e s s this p h e n o m e n o n as a m e a n s
for stress analysis. W h i l e Belgen's w o r k w a s per
f o r m e d with a single-point r a d i o m e t e r , a c o m m e r c i a l
u n i t b a s e d o n a s c a n n i n g t h e r m o g r a p h i c system
( n a m e d S P A T E , for stress p a t t e r n analysis b y
m e a s u r e m e n t of t h e r m a l emission) b e c a m e avail
able in 1982. A l t h o u g h t h e use of t h e r m o g r a p h i c
techniques t o assess m a t e r i a l a n d / o r s t r u c t u r a l c h a r
acteristics qualitatively w a s k n o w n earlier (see
Vibrothermography),
S P A T E , t h r o u g h E q n . (2),
allows t h e q u a n t i t a t i v e analysis of stress d i s t r i b u t i o n s
in a s t r u c t u r e .
F o r E q n . (2) t o be applicable, n e a r - a d i a b a t i c c o n
ditions m u s t be a t t a i n e d . T h i s requires t h e r a t e of
l o a d i n g t o be significantly higher t h a n t h e r a t e of
t h e r m a l diffusion, a n d in m o s t a p p l i c a t i o n s o n m e t a l s
a cyclic l o a d a t a b o v e 10 H z is usually sufficient. T h e
cyclic n a t u r e of t h e stressing, a n d t h u s t h e t h e r m a l
emission, also allows t h e use of c r o s s c o r r e l a t i o n tech
niques t o b e used in e x t r a c t i n g t h e very small t e m p e r a
t u r e a m p l i t u d e signals.
3.

SPATE

T h e S P A T E system consists of t h r e e p r i n c i p a l c o m
ponents.
(a)

T h e d e t e c t o r h e a d c o n t a i n s a liquid-nitrogencooled c a d m i u m - m e r c u r y - t e l l u r i d e ir d e t e c t o r
which is sensitive in t h e 8 - 1 2 spectral r a n g e .
A small p o i n t l i k e a r e a o n a cyclically l o a d e d
s t r u c t u r e is focused o n t o t h e d e t e c t o r b y a ger
m a n i u m lens a n d either a line o r a n a r e a r a s t e r
scan m a y be p e r f o r m e d via a built-in s c a n n i n g
m i r r o r system.

(b)

A lock-in amplifier (also k n o w n as a c o r r e l a t o r )

is used t o e x t r a c t t h e cyclic c o m p o n e n t of t h e ir
signal c o r r e s p o n d i n g t o t h e a p p l i e d cyclic l o a d .
Typically, this c o m p o n e n t is small c o m p a r e d
with the a b s o l u t e ir being e m i t t e d a n d / o r re
flected b y t h e specimen, a n d t h e c o r r e l a t o r acts
as a v e r y - n a r r o w - b a n d p a s s filter o p e r a t i n g a t t h e
frequency of a reference signal (e.g., from l o a d
cell) t o reject all u n w a n t e d signals.

(c)

T h e c o m p u t e r system p r o v i d e s t h e overall c o n
trol of t h e s c a n n i n g a n d d a t a acquisition u n i t s , as
well as being c a p a b l e of p e r f o r m i n g v a r i o u s
p o s t p r o c e s s i n g , display a n d s t o r a g e functions.

This system c a n achieve a

0.5 m m from a stand-off
t e m p e r a t u r e r e s o l u t i o n of
0.4 M P a for a l u m i n u m o r
4.

linear spatial r e s o l u t i o n of
d i s t a n c e of 0.25 m a n d a
0.001 C ( c o r r e s p o n d i n g t o
1 M P a for mild steel).

Applications

T h e e m e r g e n c e of the S P A T E system h a s m a d e therm o m e t r i c or, m o r e specifically, t h e r m o g r a p h i c stress

484

Effect

analysis ( T S A ) a practical reality. Because of its ability

t o m a k e n o n c o n t a c t full-field m e a s u r e m e n t s from m o s t
materials a n d because its o u t p u t is directly related t o
stress (as distinct t o m a n y o t h e r full-field techniques
which are sensitive only t o displacement, thereby re
quiring a d o u b l e differentiation t o yield stress), T S A
h a s quickly established itself as a powerful m e a n s of
experimental stress analysis. Since 1982, T S A applica
tions h a v e steadily g r o w n b o t h in n u m b e r a n d in scope.
It h a s been used in the analysis of c o m p o n e n t s ranging
from large cast-steel offshore p l a t f o r m j o i n t s t o fresh
b o n e s (e.g., H a r w o o d et al. 1991).
T h e a p p l i c a t i o n of T S A t o fracture p r o b l e m s h a s
also b e e n successful. M u c h of t h e T S A research
carried o u t in linear elastic fracture m e c h a n i c s o n
m e t a l s h a s b e e n carried o u t b y Stanley a n d his c o
w o r k e r s (Stanley 1991). It h a s b e e n s h o w n t h a t frac
t u r e p a r a m e t e r s such as t h e stress intensity factors Kx
a n d Kn c a n be e x t r a c t e d from t h e t h e r m o e l a s t i c d a t a
n e a r t h e c r a c k tip b y a p p r o p r i a t e regression tech
n i q u e s . F u r t h e r , t h e analysis c a n highlight t h e extent
of t h e c r a c k - t i p plasticity z o n e a n d s h o w w h e r e the
single-term r e p r e s e n t a t i o n of t h e analytic solution
b e c o m e s invalid.
I n c o m p o s i t e w o r k , J o n e s et al. (1989) h a v e s h o w n
t h a t T S A c a n b e a p p l i e d t o assess t h e extent of
d e l a m i n a t i o n s c a u s e d b y i m p a c t a n d t h a t a welldefined p a r a m e t e r m a y b e derived t o c h a r a c t e r i z e the
d a m a g e . O n e a d v a n t a g e of T S A over o t h e r n o n d e s
tructive inspection t e c h n i q u e s is t h a t t h e significance
of t h e d a m a g e in t e r m s of altering t h e l o a d p a t h is
directly evident as t h e o u t p u t signal is related t o
m a t e r i a l stresses.
Because of t h e r e q u i r e m e n t for cyclic l o a d i n g , T S A
lends itself n a t u r a l l y t o s t r u c t u r a l d y n a m i c s p r o b l e m s .
E v e n t h e m o s t delicate s t r u c t u r e c a n b e tested as,
b e i n g a n o n c o n t a c t m e t h o d , there is n o a d d e d t r a n s
d u c e r m a s s w h i c h c a n alter t h e d y n a m i c b e h a v i o r of
t h e subject. A g a i n , b e c a u s e t h e o u t p u t is directly
related t o stress, this m e t h o d is p a r t i c u l a r l y suited t o
t h e s t u d y of stress d i s t r i b u t i o n s a t t h e r e s o n a n t fre
quencies (stress m o d e shapes) a n d w o u l d c o m p l e m e n t
o t h e r full-field n o n c o n t a c t t e c h n i q u e s , such as h o l o
g r a p h i c i n t e r f e r o m e t r y , w h i c h a r e m o r e suitable for
analyzing displacement m o d e shapes.
O n e a p p l i c a t i o n w h i c h is well recognized as a n a r e a
w h e r e T S A c a n m a k e a n i m p o r t a n t c o n t r i b u t i o n is its
use in t h e v a l i d a t i o n of n u m e r i c a l m o d e l s . F i n i t e element m e t h o d s ( F E M s ) h a v e l o n g been used t o
analyze components a n d structures under load.
F E M s a r e p a r t i c u l a r l y useful in t h e design stage w h e r e
t h e effect of c o m p o n e n t g e o m e t r y c a n b e studied with
ease, t h u s m a k i n g t h e search for a n o p t i m u m s h a p e
relatively simple. N o e x p e r i m e n t a l m e t h o d offers such
flexibility w i t h o u t i m p o s i n g costs. H o w e v e r , m o d e l
ling is a c c e p t a b l e only w h e n it reflects reality, a n d
m a n y factors in practice c a n lead t o a failure in
m e e t i n g this r e q u i r e m e n t . Oversimplification, i n a d e
q u a t e m e s h o r unrealistic b o u n d a r y c o n d i t i o n s a r e

Stress

Distribution:

Analysis

Using

Thermoelastic

- 5 0

Effect

50

(MPa)
Figure 1

TSA scan of spanner and bolt

j u s t a few of t h e p r o b l e m s t h a t c a n p l a g u e a n F E
analysis. T o g u a r d a g a i n s t m i s r e p r e s e n t a t i o n b y
modelling, T S A p r o v i d e s a c o n v e n i e n t m e a n s for
checking t h e c o m p u t a t i o n . A s t h e t h e r m o e l a s t i c signal
is essentially p r o p o r t i o n a l t o t h e first stress i n v a r i a n t
(S = + 22 + 3 3) , c o m p a r i s o n of surface c o n t o u r s
of S from a n F E analysis w i t h t h o s e o b t a i n e d b y T S A
c a n quickly confirm (or otherwise) t h e validity of t h e
model.
O f c o u r s e , t h e r e a r e still m a n y real-life s i t u a t i o n s
w h e r e F E m o d e l l i n g w o u l d a t best b e a r o u g h a p p r o x
i m a t i o n . F e a t u r e s such as welds, fasteners a n d c o n
tacting b e a r i n g surfaces a r e extremely difficult t o
m o d e l in detail a n d this is w h e r e e x p e r i m e n t a l tech
niques such a s T S A c a n shed m u c h light o n their l o a d
transfer characteristics. F i g u r e 1 s h o w s a T S A scan of
a 19 m m o p e n - e n d e d s p a n n e r a p p l y i n g a clockwise

t o r q u e t o a h e x a g o n a l - h e a d e d bolt. T h e s h a n k section
s h o w s t h e classical b e n d i n g b e h a v i o r w h e r e t h e t o p
side experiences c o m p r e s s i o n while t h e lower side
u n d e r g o e s tension. I n this case, h o w e v e r , t h e n a t u r e of
the contact reactions between the spanner jaws and
t h e b o l t w o u l d b e extremely difficult t o k n o w in
a d v a n c e , a n d t h u s a n a c c u r a t e n u m e r i c a l m o d e l of
this region w o u l d n o t be easy t o achieve.
5. Current

and Future

Developments

A s a relatively n e w t e c h n i q u e , T S A h a s been u n d e r g o
ing a g r e a t deal of d e v e l o p m e n t a n d e v o l u t i o n . M a n y
h a r d w a r e i m p r o v e m e n t s h a v e a l r e a d y been developed
for t h e S P A T E system. Refinements such as a m a c r o lens a t t a c h m e n t , m o t i o n c o m p e n s a t o r a n d a m o r e
powerful c o m p u t e r system h a v e a l r e a d y b e c o m e

485

Stress

Distribution:

Analysis

Using Thermoelastic

available. R e s e a r c h o n a c o u s t i c noise isolation, vari

able a m p l i t u d e l o a d a p p l i c a t i o n s , t h e effects of surface
c o a t i n g thickness a n d t h e influence of i n t e r l a m i n a r
t h e r m a l diffusion in c o m p o s i t e s h a s also b e e n fruitful.
H o w e v e r , o n e of t h e m o s t significant d e v e l o p m e n t s
h a s been t h e discovery of t h e m e a n - s t r e s s effect w h i c h
later led t o t h e r e s h a p i n g of t h e t h e r m o e l a s t i c t h e o r y .
I n a p p l y i n g T S A t o s o m e simple uniaxial speci
m e n s , M a c h i n et al. (1987) f o u n d t h a t t h e t h e r m o e l a s
tic c o n s t a n t a p p e a r e d t o b e d e p e n d e n t o n t h e m e a n
stress (or static stress) applied. S u b s e q u e n t l y , W o n g et
al. (1987) p r e s e n t e d a revised t h e r m o e l a s t i c t h e o r y
t h a t c o u l d a c c o u n t for this o b s e r v e d a n o m a l y . By
treating t h e m a t e r i a l elastic m o d u l i as general func
tions of t e m p e r a t u r e r a t h e r t h a n being c o n s t a n t s ,
h i g h e r - o r d e r t e r m s relating t o t h e static stress a p p e a r
in the d e r i v a t i o n which, effectively, s h o w s t h a t t h e
t h e r m o e l a s t i c r e s p o n s e is slightly n o n l i n e a r . T h i s n o n linearity leads n o t only t o a n effective t h e r m o e l a s t i c
c o n s t a n t t h a t is m e a n - s t r e s s d e p e n d e n t , it also implies
t h a t there s h o u l d b e a higher h a r m o n i c t h e r m a l
r e s p o n s e w h e n a p u r e sinusoidal l o a d is applied. L a t e r
e x p e r i m e n t s h a v e s h o w n t h a t this is in fact t h e case
( W o n g 1991).
W h i l e this h i g h e r - o r d e r ( o r n o n l i n e a r ) effect m a y
in m a n y cases b e neglected, it d o e s raise t h e n e w
possibility of e x p l o i t i n g this p h e n o m e n o n for t h e
m e a s u r e m e n t of r e s i d u a l stresses. I n d e e d , this p o t e n
tial w a s first realized b y W o n g et al. (1988) w h e r e t h e
revised t h e o r y w a s a p p l i e d t o d e t e r m i n e t h e r e s i d u a l
stress d i s t r i b u t i o n in a n a l u m i n u m p l a t e w h i c h h a d
u n d e r g o n e p r i o r plastic d e f o r m a t i o n u n d e r a fourpoint-bend loading configuration. Figure 2 shows
t h e r e s i d u a l stress profile o b t a i n e d u s i n g t h e t h e r m o
elastic a p p r o a c h c o m p a r e d w i t h t h a t d e r i v e d u s i n g
s t r a i n g a u g e d a t a . H o w e v e r , while t h e g o o d a g r e e
m e n t s h o w n in this e x p e r i m e n t is e n c o u r a g i n g , t h e
illustrative case c o n s i d e r e d w a s essentially o n e
d i m e n s i o n a l a n d w o r k t o w a r d s solving t h e m u l t i
d i m e n s i o n a l p r o b l e m is still u n d e r w a y .
P a r t of t h e r e a s o n for t h e difficulties in t h e m u l t i
d i m e n s i o n a l p r o b l e m is t h a t while stress is a t e n s o r ,
t e m p e r a t u r e ( T S A o u t p u t ) is a scalar. T h i s m e a n s t h a t
s o m e i n f o r m a t i o n , such as t h e p r i n c i p a l stress direc
tions, is essentially lost f r o m t h e r m a l m e a s u r e m e n t s
a l o n e , a n d research t o w a r d s u n r a v e l l i n g t h e t h e r m o
elastic signal t o p r o d u c e individual stress c o m p o n e n t s
h a s t h u s b e e n active. I n d e p e n d e n t efforts from Ryall
a n d W o n g (1988) a n d H u a n g et al. (1988) h a v e s h o w n
t h a t b y i m p o s i n g t h e stress e q u i l i b r i u m c o n d i t i o n s
a n d s o m e k n o w n b o u n d a r y c o n s t r a i n t s , stress c o m
p o n e n t s c a n b e successfully s e p a r a t e d from t h e
t h e r m o e l a s t i c d a t a . T h e m o s t recent w o r k of Ryall
et al. (1991) h a s s h o w n t h a t b y u s i n g t h e h i g h e r - o r d e r
t h e r m o e l a s t i c effect in c o n j u n c t i o n w i t h e q u i l i b r i u m ,
stress s e p a r a t i o n c a n in principle be achieved w i t h o u t
t h e need for b o u n d a r y c o n d i t i o n s .
T h e possibilities unveiled b y t h e h i g h e r - o r d e r effect
seem t o h o l d g r e a t p r o m i s e in e x t e n d i n g t h e p o w e r of

486

Effect

200

Q_
5

-200

Figure 2
Residual stress profile of a four-point straightened
specimen; the vertical bars represent the standard error of
the TSA results and the continuous line is the predication
based on the strain gauge data (after Wong et al. 1988.
Reprinted by permission from Nature 332: 613-15.
Copyright 1988 Macmillan Magazines Ltd.)

T S A . H o w e v e r , this h i g h e r - o r d e r effect is extremely

small (typically t w o o r d e r s of m a g n i t u d e less t h a n t h e
a l r e a d y m i n u t e basic t h e r m o e l a s t i c effect) a n d , in
practice, o b t a i n i n g full-field m e a s u r e m e n t o n this
c o m p o n e n t using t h e c u r r e n t system is prohibitively
time c o n s u m i n g . T h e key therefore lies in future
a d v a n c e s in ir d e t e c t i o n a n d signal processing m e t h
o d s , a n d t h e r e a r e a l r e a d y efforts being directed
t o w a r d s t h e e m p l o y m e n t of multiple d e t e c t o r s (e.g.,
focal p l a n e a r r a y s of u p t o 512 512) a n d i m p r o v e d
digital d a t a processing t e c h n i q u e s .
See also: Residual Stresses: Measurement Using Neutron
Diffraction; Residual Stresses: Nondestructive Evaluation;
Vibrothermography
Bibliography
Belgen 1967 Infrared radiometric stress instrumen
tation application range study. ISA Trans. 6: 49-53
Boley A, Weiner J 1960 Theory of Thermal Stresses.
Wiley, New York
Harwood N, Cummings W (eds.) 1991 Thermoelastic
Stress Analysis. Hilger, Bristol, UK
Harwood N, Cummings W M, MacKenzie A 1991 An
introduction to thermoelastic stress. In: Harwood and
Cummings 1991, pp. 1-34
Huang M, Abdel Mohsen , Rowlands R 1988
Determination of individual stresses thermoelastically.
Exp. Mech. 30: 88-94
Jones R, Heller M, Lombardo D, Dunn S, Paul J, Saunders
D 1989 Thermoelastic assessment of damage growth in
composites. Compos. Struct. 12: 315-17
Machin A S, Sparrow J G, Stimson G 1987 Mean stress
dependence of the thermoelastic constant. Strain 23: 27-30

Superconducting

Ryall G, Heller M, Jones R 1992 Determination of stress

components from thermoelastic data without boundary
conditions. J. Appl. Mech. (In press)
Ryall G, Wong A 1988 Determining stress components
from thermoelastic dataa theoretical study. Mech.
Mater. 7: 205-14
Stanley 1991 The application of SPATE in fracture
mechanics. In: Harwood and Cummings 1991, pp. 105-34
Wong A 1991 The thermoelastic effecta higher-order
consideration. In: Harwood and Cummings 1991, pp.
167-82
Wong A K, Dunn S A, Sparrow J G 1988 Residual stress
measurement by means of the thermoelastic effect. Nature
332: 613-15
Wong A K, Jones R, Sparrow J G 1987 Thermoelastic
constant or thermoelastic parameter? J. Phys. Chem.
Solids. 48: 749-53
A. K. W o n g
[Aeronautical Research Laboratory,
F i s h e r m e n s B e n d , Victoria,
Australia]

Superconducting Materials:
Measurements
M a t e r i a l s m a y b e in t h e f o r m of single crystals,
polycrystalline pellets o r cast s a m p l e s , t h i n films o r
c o m m e r c i a l wires. T h e c h a r a c t e r i z a t i o n of t h e super
c o n d u c t i n g p r o p e r t i e s of a m a t e r i a l involves a n u m b e r
of different m e a s u r e m e n t s ; t h e types of m e a s u r e m e n t
a p p r o p r i a t e for a p a r t i c u l a r m a t e r i a l d e p e n d o n t h e
size, s h a p e a n d h o m o g e n e i t y of t h e s a m p l e available.
M o s t m a t e r i a l s exhibit s o m e i n h o m o g e n e i t y a n d
s o m e , for i n s t a n c e g r a n u l a r m a t e r i a l s o r m a t e r i a l s
with high critical c u r r e n t densities, h a v e intrinsic
i n h o m o g e n e i t y . T h e c h a r a c t e r i z a t i o n of i n h o m o g e n
e o u s m a t e r i a l s is c o m p l e x ; even t h e simplest of
m e a s u r e m e n t s r e q u i r e careful i n t e r p r e t a t i o n .
E m p h a s i s is p l a c e d o n t e c h n i q u e s for t h e c h a r a c t e r
ization of e x t r e m e t y p e II s u p e r c o n d u c t i n g m a t e r i a l s .
T w o types of m e a s u r e m e n t c a n b e used t o derive a
n u m b e r of different p a r a m e t e r s . T h e first is a resistive
m e a s u r e m e n t in w h i c h a c u r r e n t is p a s s e d t h r o u g h a
s a m p l e a n d t h e v o l t a g e m e a s u r e d . T h e s e c o n d is a n
inductive m e a s u r e m e n t w h i c h gives i n f o r m a t i o n o n
the m a g n e t i c m o m e n t of t h e s a m p l e . T h i s article
begins b y describing these t w o t e c h n i q u e s a n d t h e
p r e c a u t i o n s t o b e t a k e n if reliable results a r e t o b e
o b t a i n e d . T h e m e a s u r e m e n t of individual m a t e r i a l
p a r a m e t e r s is t h e n described.
1. Resistive

Measurements

I n a resistive m e a s u r e m e n t a c u r r e n t is p a s s e d t h r o u g h
the s a m p l e a n d t h e v o l t a g e b e t w e e n t w o p o i n t s in t h e
current path measured. There are two separate
regimes. I n t h e first regime, very low c u r r e n t s a r e u s e d
t o m e a s u r e t h e critical t e m p e r a t u r e Tc. F o r this p u r
p o s e , t h e g e o m e t r y is n o t very i m p o r t a n t a n d t h e m a i n

Materials:

Measurements

e r r o r s arise from t h e r m o e l e c t r i c effects a n d p o o r

c o n t a c t s . T h e r m o e l e c t r i c effects c a n be eliminated by
c h o p p i n g o r reversing t h e i n p u t c u r r e n t t o check the
v o l t a g e z e r o . M o r e sensitive m e a s u r e m e n t s c a n be
m a d e b y using a n ac drive c u r r e n t a n d a lock-in
amplifier. I n d u c t i v e p i c k u p c a n be recognized because
it h a s a different p h a s e a n d frequency d e p e n d e n c e
from t h e resistive c o m p o n e n t a n d it c a n t h e n be
b a l a n c e d o u t if necessary. In t h e early d a y s of high- Tc
oxide m a t e r i a l s , m a n y a n o m a l o u s a n d i r r e p r o d u c i b l e
results were a n n o u n c e d . T h e s e h a v e been a t t r i b u t e d ,
n o t entirely convincingly, t o c r a c k i n g o r m i c r o s c o p i c
voltaic cells. A n u n a m b i g u o u s value for t h e resistivity
in these c i r c u m s t a n c e s c a n best b e o b t a i n e d b y m e a
suring all p e r m u t a t i o n s of v o l t a g e a n d c u r r e n t leads.
T h e details a r e described b y v a n d e r P a u w (1961) a n d
M o n t g o m e r y (1971). T h e t e c h n i q u e is l a b o r i o u s a n d
c a n n o t be used for t r a n s i e n t effects. W h e n a m a t e r i a l
is i n h o m o g e n e o u s , t h e resistive t r a n s i t i o n is a m e a s u r e
of t h e first percolative s u p e r c o n d u c t i n g p a t h , t h e
fraction of s u p e r c o n d u c t i n g m a t e r i a l a t t h e t r a n s i t i o n
d e p e n d s o n t h e d i m e n s i o n a l i t y of t h e s a m p l e a n d a
c o m p a r i s o n of t h e resistive a n d i n d u c t i v e t r a n s i t i o n s
c a n give q u a n t i t a t i v e i n f o r m a t i o n o n t h e n a t u r e of the
s a m p l e i n h o m o g e n e i t y (Evetts 1983).
T h e s e c o n d regime is t h e h i g h - c u r r e n t regime used
for m e a s u r i n g critical c u r r e n t densities. Since low
voltages a r e involved, t h e r m o e l e c t r i c effects a r e also
i m p o r t a n t , b u t t h e m a i n difficulty is t h e h e a t i n g of t h e
s a m p l e b y t h e t r a n s p o r t c u r r e n t a n d t h e t e n d e n c y of
flux flow t o s t a r t at t h e c u r r e n t c o n t a c t s a n d s p r e a d t o
t h e rest of t h e s a m p l e . Because of t h e self-field of the
c u r r e n t , t h e m o s t m e a n i n g f u l m e a s u r e m e n t s a r e car
ried o u t in a n external field, a p p l i e d p e r p e n d i c u l a r t o
t h e c u r r e n t , w h i c h is m u c h larger t h a n t h e self-field of
t h e c u r r e n t . M e a s u r e m e n t s in parallel fields a r e of
c o n s i d e r a b l e interest b u t m o s t a p p l i c a t i o n s involve
p e r p e n d i c u l a r fields. T o e n s u r e t h a t flux flow s t a r t s
well a w a y from t h e c o n t a c t s t h e center section s h o u l d
b e n a r r o w e d ; alternatively, t h e center section is s o m e
times h e a t e d , b u t this m a k e s t h e t e m p e r a t u r e of t h e
m e a s u r e m e n t u n c e r t a i n . F o r m e a s u r e m e n t s in a solen
oid, wire s a m p l e s a r e usually b e n t i n t o a U s h a p e so
t h a t t h e c o n t a c t s c a n be o u t of t h e high-field region
a n d flux flow s t a r t s a t t h e c e n t r a l section of t h e wire
w h e r e t h e field is t r a n s v e r s e t o t h e s a m p l e .
2. Inductive

Measurements

2.1 DC
Magnetization
T h e m a g n e t i z a t i o n c u r v e gives a g r e a t deal of infor
m a t i o n a b o u t a s u p e r c o n d u c t i n g m a t e r i a l . M o s t stan
d a r d m e t h o d s c a n be used b u t s o m e a r e m o r e suitable
t h a n o t h e r s (see Magnetic Materials:
Measurements).
I n e x t r e m e t y p e II m a t e r i a l s t h e large value of the
G i n z b u r g - L a n d a u parameter poses particular prob
lems. A t low a p p l i e d fields, t h e m a g n e t i z a t i o n curve
c o n t a i n s detail u p t o a few millitesla with a relatively
high susceptibility, while t h e high-field e n d of t h e

487

Superconducting

Materials:

Measurements

curve c a n involve very small m a g n e t i z a t i o n s a t exter

nal fields of u p t o 100 T . N o m e a s u r e m e n t system is
ideal for b o t h .
T h e principle is nearly always t o c h a n g e the flux in
a search coil d u e t o the s a m p l e m a g n e t i z a t i o n ; for
three geometries the signal c a n b e directly related t o
the m a g n e t i z a t i o n w h a t e v e r t h e c u r r e n t d i s t r i b u t i o n
in the sample. If the s a m p l e is in a l o n g solenoidal coil
o r if it is small c o m p a r e d w i t h t h e distance t o t h e
search coil w i n d i n g s , the signal is directly p r o p o r
tional t o the m o m e n t of t h e s a m p l e , w h a t e v e r its
s h a p e . I n a d d i t i o n , if t h e s a m p l e is a l o n g cylinder of
a r b i t r a r y cross section placed inside t w o o p p o s i n g
coils, the signal w h e n it is m o v e d is p r o p o r t i o n a l t o
the m a g n e t i z a t i o n p e r u n i t length. T h e s e geometries
involve loose inductive c o u p l i n g b e t w e e n s a m p l e a n d
search coil, w h i c h t e n d s t o increase s p u r i o u s signals
a n d noise, a n d they a r e n o t t h o s e of o p t i m u m sensiti
vity, for w h i c h the coils s h o u l d closely follow the
specimen outline.
F o r a close-coupled g e o m e t r y , m u t u a l i n d u c t a n c e
tables c a n b e used o r t h e system c a n be c a l i b r a t e d with
a b u l k type I s u p e r c o n d u c t o r . A l t h o u g h t h e c o u p l i n g
factor c h a n g e s s o m e w h a t as c u r r e n t s p e n e t r a t e a type
II s u p e r c o n d u c t o r , this is n o t a very large c o r r e c t i o n
a n d a d i a m a g n e t i c c a l i b r a t i o n s a m p l e is generally
a d e q u a t e . F o r b u l k samples of simple g e o m e t r y , t h e
system is self-calibrating since below the lower critical
field Hcl the s a m p l e c a n b e a s s u m e d t o be perfectly
d i a m a g n e t i c , a l t h o u g h the a c t u a l initial slope of t h e
m a g n e t i z a t i o n curve will d e p e n d o n the d e m a g n e t i z
ing factor for the s a m p l e .
A n u m b e r of m e t h o d s a r e used t o p r o d u c e a n
inductive signal. T h e c o m m o n e s t is p r o b a b l y t o m o v e
the s a m p l e o u t of the search coils o r b e t w e e n t w o
coils. T h e d i s p l a c e m e n t s h o u l d b e k e p t t o a m i n i m u m
since, if the m a g n e t i z a t i o n curve is hysteretic, small
v a r i a t i o n s in t h e external field c a n t a k e a s a m p l e from
o n e b r a n c h of the hysteresis curve t o the o t h e r .
M o v e m e n t i n t o a region of different field will t r a p the
new field a n d b r i n g flux b a c k i n t o t h e coils. A c h a n g e
of a few millitesla is sufficient t o give s p u r i o u s results
if hysteresis is low, so t h a t a small s a m p l e displace
m e n t a t a higher frequency is preferred, as in a
v i b r a t i n g s a m p l e m a g n e t o m e t e r ( V S M ) . S Q U I D sys
tems, a l t h o u g h sensitive, use large d i s p l a c e m e n t s a n d
extreme field h o m o g e n e i t y is needed if the s a m p l e is
hysteretic.
It is possible t o k e e p the s a m p l e s t a t i o n a r y a n d
integrate the signal as t h e applied m a g n e t field is
swept. T h i s is n o t very sensitive over a large field
r a n g e since it is necessary t o b a l a n c e o u t of t h e large
signal d u e t o the applied field. T h e field d i s t r i b u t i o n
from a s u p e r c o n d u c t i n g solenoid d e p e n d s o n b o t h the
field a n d h i s t o r y so t h a t t h e b a l a n c e is n o t c o n s t a n t .
D e m a g n e t i z i n g t h e s a m p l e by h e a t i n g it a b o v e Tc is
effective, b u t time c o n s u m i n g , p a r t i c u l a r l y for h i g h - r c
m a t e r i a l s , a n d it is i m p o r t a n t t h a t t h e h e a t i n g d o e s
n o t m o v e the search coils in the m a g n e t field. T h e

488

m e a s u r e m e n t of c h a n g e s in m a g n e t i z a t i o n c a u s e d b y
flux creep p r e s e n t fewer p r o b l e m s since the c h a n g e
c a n be p i c k e d u p directly as a voltage in the search
coils. T h e signal is m e a s u r e d b y a n i n t e g r a t o r w h i c h
t e n d s t o drift, b u t use of a S Q U I D d e t e c t o r will a v o i d
this p r o b l e m . H o w e v e r , m o s t flux creep e x p e r i m e n t s
m u s t b e m a d e in a fairly large external field so t h a t
flux c r e e p in t h e m a g n e t is t h e d o m i n a n t e r r o r .
Commercial instruments have p o o r coupling between
s a m p l e a n d search coils a n d m a g n e t creep is a m a j o r
limitation.
T e c h n i q u e s w h i c h m e a s u r e the force, o r t o r q u e , o n
a s a m p l e h a v e n o t been u s e d m u c h b u t are sensitive
a n d direct, a l t h o u g h delicate. T h e y h a v e been of
c o n s i d e r a b l e value in m e a s u r e m e n t s o n high-!T c
m a t e r i a l s ( H a g e n a n d Griessen 1989, H a m z i c et al.
1990). T h e F a r a d a y b a l a n c e as n o r m a l l y supplied is
n o t suitable as it p u t s a large a n d variable field
g r a d i e n t a c r o s s t h e s a m p l e . H o w e v e r , by p u t t i n g the
s a m p l e in a u n i f o r m m a i n field a n d a d d i n g a small
g r a d i e n t field w i t h external coils w h i c h c a n b e
c h o p p e d a n d detected w i t h a lock-in amplifier, a
sensitive m a g n e t o m e t e r c a n b e m a d e w h i c h d o e s n o t
m o v e t h e s a m p l e significantly. T h e g r a d i e n t coils
s h o u l d n o t m o v e the flux vortices in t h e s a m p l e b y
m o r e t h a n t h e p i n n i n g i n t e r a c t i o n distance for linear
d i s p l a c e m e n t , a s will be discussed later.
T o r q u e m e a s u r e m e n t s h a v e t h e s a m e a d v a n t a g e s as
a F a r a d a y b a l a n c e in t h a t it is n o t necessary t o m o v e
the s a m p l e p o s i t i o n in t h e m a g n e t field. T o r q u e m a g
n e t o m e t e r s c a n n o t m e a s u r e the reversible c o m p o n e n t
of t h e m a g n e t i z a t i o n , b u t they c a n m e a s u r e a n i s o
t r o p y a n d flux v o r t e x p i n n i n g forces, a l t h o u g h the
g e o m e t r y c a n m a k e q u a n t i t a t i v e i n t e r p r e t a t i o n diffi
cult, p a r t i c u l a r l y if b o t h a r e present.
2.2 AC Techniques
T h e r e s p o n s e of a s u p e r c o n d u c t o r t o a n a l t e r n a t i n g
field allows a n u m b e r of p a r a m e t e r s t o b e m e a s u r e d .
M a n y of t h e s a m e c o n s i d e r a t i o n s a p p l y as t o d c
m e a s u r e m e n t s b u t a c t e c h n i q u e s , particularly w i t h the
a d d i t i o n of a lock-in amplifier, c a n be extremely
c o n v e n i e n t a n d sensitive. T h e simplest configuration
is t o m e a s u r e t h e c h a n g e in i m p e d a n c e of a coil
c o n t a i n i n g the s a m p l e . T h i s m a y b e small a n d greater
sensitivity c a n b e o b t a i n e d by l o o k i n g for the t h i r d
h a r m o n i c , since a s u p e r c o n d u c t o r c a n b e dis
tinguished from o t h e r m a g n e t i c m a t e r i a l s b y the
g e n e r a t i o n of a s t r o n g t h i r d - h a r m o n i c signal.
H o w e v e r , m o s t m e t h o d s use a m u t u a l i n d u c t a n c e
so t h a t the p i c k u p coil voltage is i n d e p e n d e n t of the
m u c h larger drive coil voltage. F o r q u a n t i t a t i v e
m e a s u r e m e n t s the drive coil s h o u l d p r o v i d e a u n i f o r m
field over t h e s a m p l e a n d t h e p i c k u p coils s h o u l d b e
such t h a t the voltage is easily related t o t h e m a g n e t i
z a t i o n , as for d c m a g n e t i c m e a s u r e m e n t s . It is
generally necessary t o use a b a l a n c i n g n e t w o r k t o
cancel o u t u n w a n t e d signals d u e t o m u t u a l i n d u c t a n c e
in t h e leads, capacitive effects a n d g r o u n d l o o p s . T h e

Superconducting

system c a n b e b a l a n c e d either w h e n t h e s a m p l e is
n o r m a l o r w h e n it is s u p e r c o n d u c t i n g , a c c o r d i n g t o
the m e a s u r e m e n t . If it is b a l a n c e d w h e n n o r m a l , t h e
b a l a n c e need only b e set o n c e since it is i n d e p e n d e n t
of s a m p l e size. H o w e v e r , if it is desired t o o b s e r v e
small p e n e t r a t i o n s of flux in a m a i n l y s u p e r c o n d u c t
ing s a m p l e , it is necessary t o b a l a n c e in t h e fully
superconducting state.
T h e a p p a r a t u s is generally a c o m p r o m i s e b e t w e e n
conflicting r e q u i r e m e n t s . M a k i n g t h e system small
reduces t e m p e r a t u r e differences, b u t also r e d u c e s
sensitivity. A n y m e t a l s used t o r e d u c e t e m p e r a t u r e
gradients carry eddy currents which produce spurious
signals. T h e s e o u t - o f - b a l a n c e signals t e n d t o b e t h e
m a i n limitation r a t h e r t h a n noise o r sensitivity. T h e y
arise from d i m e n s i o n a l c h a n g e s in t h e p r o b e , f r o m
c o n v e n t i o n a l soldered j o i n t s , from t h e r m o m e t e r c a n s
t o o close t o t h e coils a n d from e d d y c u r r e n t s in c a n s
r o u n d t h e system a n d t h e s u p e r c o n d u c t i n g m a g n e t .
T h i s last factor is very n o n l i n e a r a t high drive a m p l i
tudes a n d t h e r e is also a d a n g e r o f q u e n c h i n g t h e
m a g n e t if it is close t o its m a x i m u m field. T o m i n i m i z e
external e d d y c u r r e n t s t h e drive coil c a n b e w o u n d a s
t w o coils of t h e s a m e n u m b e r o f a r e a t u r n s excited in
o p p o s i t i o n , a l t h o u g h this reduces t h e available a m p l i
t u d e . A t e c h n i q u e t o limit t h e effects o f t h e r m a l
e x p a n s i o n is t o w i n d drive coils o n q u a r t z t u b e s a n d
p u t t h e search coils o u t s i d e t h e m . T h e signal is t h e n
i n d e p e n d e n t o f c h a n g e s t o t h e search coil d i m e n s i o n s
a n d t h e drive coils c a n b e w o u n d t o b e m o r e n e a r l y
identical since they a r e of t h i c k e r wire ( C o o p e r et al.
1990).
T h e signal f r o m t h e search coils c a n b e t r e a t e d in a
n u m b e r of w a y s d e p e n d i n g o n t h e p a r a m e t e r being
investigated. T h e s e a r e discussed in Sect. 3 .

3. Individual

Parameters

T h e p a r a m e t e r s described in this section m a y n o t h a v e

a single value in a m a t e r i a l b e c a u s e o f m a t e r i a l
a n i s o t r o p y o r b e c a u s e of i n h o m o g e n e i t y . T h u s , h i g h re sintered c e r a m i c m a t e r i a l s c a n b e t r e a t e d a s c o m p o
sites of t w o q u i t e different s u p e r c o n d u c t o r s w i t h t w o
s e p a r a t e sets o f p a r a m e t e r s characteristic o f t h e g r a i n s
a n d g r a i n b o u n d a r i e s . I n o t h e r m a t e r i a l s , different
p a r a m e t e r s c a n v a r y c o n t i n u o u s l y a s , for i n s t a n c e , in
a proximity-coupled composite structure.

3.1 Critical

Temperature

T h i s section describes m e a s u r e m e n t s of Tc in z e r o
m a g n e t i c field.
(a) Resistive measurements. I n a h o m o g e n e o u s s u p e r
c o n d u c t o r t h e resistance goes t o z e r o o v e r a few
millikelvin a n d p r o v i d e s a n a c c u r a t e m e a s u r e m e n t o f
Tc. T h e c o n v e n t i o n a l definition is t h e t e m p e r a t u r e t o
reach half t h e n o r m a l state resistivity. W h a t is
actually m e a s u r e d is t h e t e m p e r a t u r e a t w h i c h t h e

Materials:

Measurements

critical c u r r e n t is e q u a l t o t h e m e a s u r i n g c u r r e n t , so a
check s h o u l d b e m a d e t h a t t h e c u r v e is i n d e p e n d e n t of
t h e m e a s u r i n g c u r r e n t . T h i s is n o r m a l l y t h e case for
c u r r e n t s of a few m i l l i a m p e r e s . A b r o a d t r a n s i t i o n o r
a finite resistance a t l o w t e m p e r a t u r e s is indicative
of i n h o m o g e n e i t y , a l t h o u g h c u r v a t u r e a t t h e hight e m p e r a t u r e e n d of t h e t r a n s i t i o n m a y b e d u e t o
fluctuations. If t h e p r o p o r t i o n of s u p e r c o n d u c t o r is
less t h a n t h e p e r c o l a t i o n t h r e s h o l d , t h e relative r e d u c
t i o n in resistance gives a n i n d i c a t i o n of t h e p r o p o r t i o n
of s u p e r c o n d u c t o r p r e s e n t . A l t h o u g h , in principle, a
n e t w o r k o f fine s u p e r c o n d u c t i n g t h r e a d s c o u l d give
z e r o resistance, this seems t o o c c u r r a t h e r rarely; grain
b o u n d a r y p h a s e s a r e usually less s u p e r c o n d u c t i n g
t h a n t h e b u l k , a l t h o u g h a n o t a b l e e x c e p t i o n is seen in
dilute s o l u t i o n s of i r o n in t i t a n i u m .
(b) Inductive measurements.
A s t h e s a m p l e goes
t h r o u g h Tc it b e c o m e s d i a m a g n e t i c a n d t h e size of t h e
signal a t a n y t e m p e r a t u r e d e p e n d s o n t h e r a t i o of t h e
magnetic penetration depth at that temperature to
t h e d i a m e t e r of t h e s a m p l e . T h e half-way p o i n t of t h e
t r a n s i t i o n is w h e n is a p p r o x i m a t e l y e q u a l t o t h e
r a d i u s of t h e s a m p l e . T h i s p o i n t will b e close t o
t h e p e a k in t h e i m a g i n a r y p a r t of t h e susceptibility o r
in t h e t h i r d h a r m o n i c if t h e a m p l i t u d e is large e n o u g h .
Small s a m p l e s will therefore h a v e wide t r a n s i t i o n s
even if they a r e h o m o g e n e o u s . T h e a m p l i t u d e d e p e n
d e n c e m u s t b e c h e c k e d since small a p p l i e d fields c a n
i n d u c e c u r r e n t densities g r e a t e r t h a n t h e critical cur
r e n t density.
T h e i n d u c e d signal is p r o p o r t i o n a l t o t h e p r o d u c t of
t h e a m p l i t u d e a n d t h e frequency a n d g r e a t e r sensiti
vity c a n b e o b t a i n e d a t high frequencies; u p t o several
m e g a h e r t z is used for oxide s u p e r c o n d u c t o r s . H o w
ever, it is i m p o r t a n t t h a t t h e n o r m a l state resistivity is
such t h a t t h e skin d e p t h is m u c h g r e a t e r t h a n t h e
s a m p l e size; this limits t h e frequency t o less t h a n 1
k H z for b u l k metallic s a m p l e s . T h e d c m a g n e t i z a t i o n
m e a s u r e d b y first c o o l i n g in z e r o field a n d t h e n raising
t h e t e m p e r a t u r e in a small a p p l i e d field gives t h e s a m e
m e a s u r e m e n t a s t h e inductive t e c h n i q u e s e x t r a p o l a t e d
t o z e r o frequency.
(c) Specific heat anomaly. T h i s is a very reliable
m e t h o d o f m e a s u r i n g Tc since it is i n d e p e n d e n t of t h e
s h a p e of a n y i n h o m o g e n e o u s regions a n d m e a s u r e s a
b u l k p r o p e r t y . H o w e v e r , it is time c o n s u m i n g a n d
n e e d s large s a m p l e s a n d s o is n o t very suitable for
s t a n d a r d testing.
(d) The effect of magnetic fields. T h i s is considered in
m o r e detail in Sect. 3.7. I n general, t h e t r a n s i t i o n is
broadened. This m a y be d u e to a greater inhomoge
neity in t h e u p p e r critical field Hc2 t h a n in Tc. H o w
ever, t h e r e a r e o t h e r r e a s o n s for b r o a d e n i n g even in
h o m o g e n e o u s s a m p l e s . F o r a type I I s u p e r c o n d u c t o r
in t h e m i x e d state, z e r o resistance is only achieved b y
t h e p i n n i n g of vortices. If t h e p i n n i n g energy is less
t h a n kBT, t h e r m a l l y a c t i v a t e d flux flow gives a linear
resistivity a n d t h e a c susceptibility will b e slightly

489

Superconducting

Materials:

Measurements

p a r a m a g n e t i c with a value 1 /2K: . T h e inductive t r a n s i

tion only a p p e a r s a t t h e irreversibility line w h e r e
t h e r m a l a c t i v a t i o n s t o p s (see Sect. 3.14). I n c o n v e n
t i o n a l s u p e r c o n d u c t o r s this m a y be very close t o Tc
b u t in oxide s u p e r c o n d u c t o r s t h e t w o t e m p e r a t u r e s
m a y be s e p a r a t e d by tens of degrees. E v e n if t h e
t r a n s i t i o n is close t o Tc t h e i n d u c t i v e signal in t h e
mixed state is d e t e r m i n e d b y t h e p i n n i n g p e n e t r a t i o n
d e p t h A p i n, a n effective p e n e t r a t i o n d e p t h d e t e r m i n e d
b y t h e p i n n i n g centers (see Sect. 3.10). I n reversible
m a t e r i a l s this c a n b e m o r e t h a n 100 ; even q u i t e
massive specimens m a y be of a size c o m p a r a b l e t o A p in
with a c o r r e s p o n d i n g l y b r o a d t r a n s i t i o n t o less t h a n
perfect d i a m a g n e t i s m . T h e detailed i n t e r p r e t a t i o n of
t h e inductive t r a n s i t i o n in a n a p p l i e d field is still t h e
source of s o m e c o n t r o v e r s y .
3.2 Superconducting

Fraction

T h e t e r m s u p e r c o n d u c t i n g fraction is generally t a k e n
t o m e a n t h e p r o p o r t i o n of a fully d i a m a g n e t i c signal
m e a s u r e d either in a n i n d u c t i v e t r a n s i t i o n o r in a
s a m p l e w a r m e d in a small field (i.e., less t h a n Hcl a t
low t e m p e r a t u r e s ) . It will give t h e p r o p o r t i o n of
s u p e r c o n d u c t o r p r e s e n t o n l y in t h e following r a t h e r
unusual circumstances. The superconducting phase
m u s t consist o f particles t h a t a r e large c o m p a r e d w i t h
the m a g n e t i c p e n e t r a t i o n d e p t h w h i c h d o n o t f o r m a n
interconnected structure. Large samples with a con
nected n e t w o r k of s u p e r c o n d u c t o r will give perfect
d i a m a g n e t i s m even with very large v o l u m e fractions
of n o r m a l m a t e r i a l . C o n v e r s e l y , h o m o g e n e o u s s u p e r
c o n d u c t o r s c a n give a very small d i a m a g n e t i s m if t h e
particle size is smaller t h a n t h e m a g n e t i c p e n e t r a t i o n
d e p t h a n d t h e g r a i n s a r e d e c o u p l e d . Since newly
p r e p a r e d m a t e r i a l s a r e often well a w a y from t h e
o p t i m u m c o m p o s i t i o n with a c o r r e s p o n d i n g l y large
p e n e t r a t i o n d e p t h , it is easy t o a s s u m e i n h o m o g e n e i t y
w h e r e n o n e exists. I n t e r p r e t a t i o n of t h e inductive
signal s h o u l d be m a d e in c o n j u n c t i o n with resistive
m e a s u r e m e n t s t o m a k e sure they a r e consistent. A
large d i a m a g n e t i c signal is a l m o s t certainly indicative
of t h e presence of a s u p e r c o n d u c t o r , a l t h o u g h c a r e
m u s t be t a k e n in m e a s u r e m e n t s u s i n g b r i d g e systems
t o m a k e sure t h a t it is n o t a decrease in p a r a m a g n e
tism w h i c h is b e i n g o b s e r v e d . A discussion is p r e
sented by C a m p b e l l et al. (1991).
3.3 Meissner

Fraction

T h e M e i s s n e r effect is t h e e x p u l s i o n of flux w h i c h
o c c u r s w h e n a s u p e r c o n d u c t o r is c o o l e d in a field.
A l t h o u g h s o m e t i m e s q u o t e d as t h e best test of a
s u p e r c o n d u c t o r , it is in fact a c o m p l e x p r o c e s s a n d
m a n y good superconductors have almost no Meissner
effect. I n a t y p e II s u p e r c o n d u c t o r , significant flux
begins t o m o v e t o w a r d s t h e n e a r e s t surface w h e n t h e
t e m p e r a t u r e is low e n o u g h for t h e e x t e r n a l field t o b e
below Hcl. T h e e x t e n t t o w h i c h it c a n get o u t is
d e t e r m i n e d b y flux p i n n i n g , o r the critical c u r r e n t
density Jc, a t this t e m p e r a t u r e . T h e M e i s s n e r fraction

490

is t h e m a g n e t i c m o m e n t expressed as a fraction of t h e
full d i a m a g n e t i c m o m e n t ; it is a c o m p l e x c o m b i n a t i o n
of t h e a p p l i e d field, t h e s a m p l e size a n d t h e s t r e n g t h of
t h e p i n n i n g a n d its v a r i a t i o n w i t h t e m p e r a t u r e . Little
useful i n f o r m a t i o n c a n be o b t a i n e d from it ( C a m p b e l l
et al. 1991).
3.4 Magnetic

Penetration

Depth

Different t e c h n i q u e s h a v e b e e n u s e d t o m e a s u r e the
magnetic penetration depth according to the nature
of t h e s a m p l e s available. If t h e m a t e r i a l is available a s
small particles w h i c h c a n be sized, t h e susceptibility a s
a function of particle size c a n b e used t o give .
Alternatively, t h e size d i s t r i b u t i o n of a r a n d o m sized
s a m p l e c a n be m e a s u r e d a n d t h e susceptibility a s a
function of t e m p e r a t u r e c a n b e fitted t o give t h e best
v a l u e of ( C o o p e r et al. 1989). A similar t e c h n i q u e is
t h e m e a s u r e m e n t of t h e i m a g i n a r y p a r t of t h e m i c r o
w a v e i m p e d a n c e . T h e i m p e d a n c e of a thin-film strip
line of t h e m a t e r i a l h a s also b e e n u s e d ( F i o r y et al.
1988, D r a b e c k et al. 1989). T h e p r o p e r t i e s of t h e
v o r t e x s t a t e n e a r Hcl a n d t h e v a l u e of Hcl a r e directly
related t o . If hysteresis is small, t h e s h a p e of t h e
reversible m a g n e t i z a t i o n c u r v e a t fairly low fields c a n
b e expressed in t e r m s of , a l t h o u g h p a r a m a g n e t i c
c o n t r i b u t i o n s m a k e this difficult in s o m e oxide m a t e r
ials ( M i t r a et al. 1989). T h e r m s field fluctuations of
t h e vortices c a n b e directly r e l a t e d t o a n d values
o b t a i n e d f r o m p o s i t r o n spin r e l a x a t i o n h a v e b e e n
widely q u o t e d ( H a r s h m a n et al. 1989). T h e r e a r e ,
h o w e v e r , o t h e r c o m p o n e n t s t o t h e r m s field fluctua
t i o n s c a u s e d b y p i n n i n g effects w h i c h affect t h e v a l u e
of derived. Finally, a v a l u e for c a n be calculated
f r o m a k n o w l e d g e o f Hcl a n d u s i n g t h e G i n z b u r g L a n d a u theory.
P r o b l e m s arise in all m e t h o d s t h a t use t h e t h e o r y of
flux vortices if t h e particle size is c o m p a r a b l e w i t h t h e
p e n e t r a t i o n d e p t h since, in these c i r c u m s t a n c e s , t h e
a p p a r e n t v a l u e s of Hcl a n d t h e m a g n e t i z a t i o n c u r v e
a r e affected b y t h e p r o x i m i t y of t h e s a m p l e surface.
C o n v e n t i o n a l s u p e r c o n d u c t o r s h a v e small p e n e t r a
t i o n d e p t h s a n d c a n usually be t r e a t e d as large s a m
ples. H o w e v e r , t h e o x i d e s u p e r c o n d u c t o r s c a n h a v e
large p e n e t r a t i o n d e p t h s , p a r t i c u l a r l y w h e n off stoic h i o m e t r y , a n d a r e often only available as small
i n d e p e n d e n t g r a i n s , so t h a t t h e s i t u a t i o n w h e n is
c o m p a r a b l e w i t h t h e p a r t i c l e size frequently o c c u r s .
3.5

Thermodynamic

Critical

Field

T h e t h e r m o d y n a m i c critical field Hc is t h e field a t

w h i c h t h e m a g n e t i c energy e q u a l s t h e c o n d e n s a t i o n
energy; it is therefore i s o t r o p i c . I n a type I s u p e r c o n
d u c t o r Hc c a n b e f o u n d directly from t h e m a g n e t i z a
t i o n c u r v e b u t in a t y p e II s u p e r c o n d u c t o r t h e o n l y
direct m e a s u r e m e n t is f r o m t h e specific h e a t . A review
of specific h e a t m e a s u r e m e n t s c a n b e f o u n d in J u n o d
(1989). T h e t h e r m o d y n a m i c critical field c a n a l s o b e
f o u n d indirectly from m e a s u r e m e n t s of HGl a n d Hc2
using the G i n z b u r g - L a n d a u theory.

Superconducting

3.6 Lower Critical Field

T h e lower critical field Hcl is t h e field a t w h i c h flux
vortices first p e n e t r a t e a l o n g s u p e r c o n d u c t i n g
cylinder. It is difficult t o m e a s u r e b e c a u s e p i n n i n g
effects p r e v e n t flux e n t r y until c o n s i d e r a b l y larger
fields. P i n n i n g c a n o c c u r b o t h d u e t o b u l k effects a n d
surface effects. T h e latter p o s e a p a r t i c u l a r p r o b l e m
since there is n o significant p e n e t r a t i o n until t h e
surface b a r r i e r is o v e r c o m e . Bulk p e n e t r a t i o n leads t o
a detectable c u r v a t u r e of t h e m a g n e t i z a t i o n c u r v e
a b o v e Hcl a n d , if Jc is p r o p o r t i o n a l t o 1/2?, e x t r a p o l a
112
tion of (H- M)
t o z e r o s h o u l d give Hcl. A m o r e
sensitive t e c h n i q u e is t o use t h e a c susceptibility either
as a function of signal a m p l i t u d e o r e x t e r n a l field.
B o t h real a n d i m a g i n a r y p a r t s increase r a p i d l y w h e n
flux first p e n e t r a t e s . A l t h o u g h b u l k p e n e t r a t i o n m a y
be a t fields c o n s i d e r a b l y h i g h e r t h a n Hcl d u e t o
surface p i n n i n g effects, losses a n d p e n e t r a t i o n c a n b e
detected below Hcl b e c a u s e of field c o n c e n t r a t i o n s a t
asperities. I n general, t h e p o i n t of first p e n e t r a t i o n of
flux is m u c h less well defined t h a n is c o m m o n l y
suggested.
Surface b a r r i e r s c a n be r e m o v e d b y diffusing a n
element i n t o t h e surface w h i c h progressively depresses
Tc as the c o n c e n t r a t i o n increases, so t h a t t h e surface is
s p r e a d o u t over several A. T h i s h a s only b e e n effective
in p u r e n i o b i u m using oxygen a n d in P b T l u s i n g
t h a l l i u m (Evetts 1970). W i t h o u t this t r e a t m e n t flux
first p e n e t r a t e s t h e surface a t a b o u t 1.5 times Hcl in
long cylinders. T h e p e n e t r a t i o n of o t h e r s h a p e s
d e p e n d s o n d e m a g n e t i z i n g effects a n d h a s n o t b e e n
investigated very t h o r o u g h l y .
A n e s t i m a t e of t h e effect of p i n n i n g c a n b e o b t a i n e d
from t h e low-field m a g n e t i c hysteresis c u r v e . If t h e
b a r r i e r is s y m m e t r i c for t h e e n t r y a n d exit of flux, Hcl
will b e half w a y b e t w e e n t h e p e a k of t h e increasing
curve a n d t h e p e a k of t h e decreasing c u r v e . A b e t t e r
m e a s u r e m e n t c a n be m a d e b y fitting t h e s h a p e of t h e
curve as calculated b y A b r i k o s o v in fields a b o v e Hcl
w h e r e it is r e a s o n a b l y reversible a n d e x t r a p o l a t i n g
b a c k t o t h e irreversible region. Bulk p i n n i n g effects
a r e r e d u c e d if t h e s a m p l e size is r e d u c e d , so t h a t fitting
curves is easier for small s a m p l e s . H o w e v e r , they m u s t
n o t be t o o small, since for particles smaller t h a n t h e
p e n e t r a t i o n d e p t h t h e field a t w h i c h t h e first v o r t e x
enters is d e t e r m i n e d b y t h e particle size r a t h e r t h a n
#cl-

3.7 Upper Critical Field and

Ginzburg-Landau
Coherence
Length
T h e u p p e r critical field Hc2 is t h e field a t w h i c h t h e
vortex cores o v e r l a p a n d b u l k s u p e r c o n d u c t i v i t y dis
a p p e a r s . It is therefore directly related t o t h e G i n z
b u r g - L a n d a u c o h e r e n c e length . T w o p r o b l e m s
arise: first, t h e fields involved c a n b e very large a n d ,
second, t h e t r a n s i t i o n is s e c o n d o r d e r so t h a t if is
large t h e c h a n g e in p r o p e r t i e s is very small. I n high-7^
oxides fluctuations s m o o t h o u t t h e d i s c o n t i n u i t y m a k
ing it difficult t o define Hc2 precisely. T h e reversible

Materials:

Measurements

m a g n e t i z a t i o n is linear n e a r Hc2 so e x t r a p o l a t i o n of
t h e m a g n e t i z a t i o n c u r v e t o zero m a g n e t i z a t i o n is a
g o o d w a y of d e t e r m i n i n g Hc2. Since t h e slope is 1/
2
(2 - 1), t h e c h a n g e in slope m a y be difficult t o
detect, especially if t h e r e is a p a r a m a g n e t i c m o m e n t .
A clearer t r a n s i t i o n for large is generally seen if t h e
field is k e p t c o n s t a n t a n d t h e t e m p e r a t u r e varied.
E x t r a p o l a t i o n of t h e linear section t o m e e t t h e n o r m a l
state susceptibility gives t h e best value for Hc2 ( W e l p
et al. 1989).
Resistive m e a s u r e m e n t s m a y b e t h e only possible
t e c h n i q u e a t very high fields w h i c h a r e invariably
pulsed so t h a t t h e m e a s u r e m e n t t i m e is limited b u t , as
p o i n t e d o u t previously, this m e a s u r e s t h e irreversibi
lity line r a t h e r t h a n Hc2. A n o t h e r c o m p l i c a t i o n with
resistive m e a s u r e m e n t s is t h a t resistanceless surface
c u r r e n t s c a n b e carried u p t o Hc3, t h e critical field for
t h e n u c l e a t i o n of surface s u p e r c o n d u c t i v i t y . T h e cur
r e n t s a r e n o t large o n r o u g h surfaces a n d c a n b e
e l i m i n a t e d b y p l a t i n g with a n o r m a l m e t a l . H o w e v e r ,
this d o e s m e a n t h a t a resistive t r a n s i t i o n m a y b e
rather uncertain and current dependent.
3.8 Surface Nucleation

Field

The boundary condition on the order parameter at a

v a c u u m o r i n s u l a t i n g surface allows surface s u p e r c o n
ductivity t o exist in fields parallel t o t h e surface u p t o
\JHc2. E x c e p t in t h e case of very-low-/c m a t e r i a l , t h e
m a g n e t i z a t i o n is n o t d e t e c t a b l e b u t t h e resistive t r a n
sition in a field parallel t o a s m o o t h surface c a n be
used t o m e a s u r e HcV T h e possibility of t h e r m a l activa
tion of t h e p o i n t vortices involved leading t o a n
irreversibility line b e t w e e n Hc2 a n d Hc3 h a s n o t been
investigated.
3.9 Resistive Transition and Flux Flow
Resistivity
T h e m o v e m e n t of a flux v o r t e x is lossy, even w i t h o u t
p i n n i n g , a n d it experiences a viscous d r a g , j u s t like
flux in a n o r m a l m e t a l . T h e resulting linear resistivity
is called t h e flux flow resistivity p{ a n d , a c c o r d i n g t o
t h e t h e o r y of B a r d e e n a n d S t e p h e n , decreases a p p r o x
imately linearly from t h e n o r m a l s t a t e value a t Hc2 t o
z e r o a t z e r o field. T h e r e is n o satisfactory t h e o r y for
t h e v o l t a g e - c u r r e n t (VI) characteristics of m a t e r i a l s
w i t h p i n n i n g b u t t h e c o m m o n e s t a s s u m p t i o n is t h a t
= p{(J - Jc) (i.e., t h e flux flow resistivity is given b y
t h e slope of t h e VI c h a r a c t e r i s t i c well a b o v e / J .
A s e c o n d t e c h n i q u e is t o use l o w - a m p l i t u d e oscilla
t i o n s w h i c h d o n o t u n p i n t h e flux lines a n d m e a s u r e
t h e frequency r e s p o n s e . I n principle, this s h o u l d b e a
better technique but experimental measurements are
few a n d it is n o t clear t o w h a t e x t e n t these a c
m e a s u r e m e n t s agree w i t h d c m e a s u r e m e n t s . T h e r e a r e
t w o possible regimes, s e p a r a t e d b y t h e p i n n i n g fre
q u e n c y a b o v e w h i c h viscous forces d o m i n a t e p i n n i n g
forces (Gilchrist a n d M o n c e a u 1968). T h i s requires
t h e skin d e p t h t o b e smaller t h a n t h e p i n n i n g p e n e t r a
tion d e p t h A p in a n d losses d u e t o n o r m a l electrons m u s t
b e c o n s i d e r e d . A t l o w e r frequencies a m o d e l using a

491

Superconducting

Materials:

Measurements

linear r e s t o r i n g force from t h e p i n n i n g wells p l u s a

viscous force d u e t o t h e flux flow resistivity c a n b e
used ( G i t t l e m a n a n d R o s e n b l u m 1966). M e a s u r e
m e n t s of t h e real a n d i m a g i n a r y p a r t s of t h e suscepti
bility give values for t h e t w o p a r a m e t e r s .

3.10 Pinning Penetration Depth

I n t h e mixed state t h e flux line is p i n n e d i n a p i n n i n g
well w h i c h gives a linear r e s t o r i n g force f o r small
d i s p l a c e m e n t s . T h e result is t h a t a n a c signal decays
exponentially from t h e surface a n d p e n e t r a t e s a dis
t a n c e ( C a m p b e l l a n d E v e t t s 1972). T h i s d e p t h is
c o n s i d e r a b l y larger t h a n t h e u s u a l m a g n e t i c p e n e t r a
tion d e p t h o r L o n d o n p e n e t r a t i o n d e p t h a n d c a n b e
m e a s u r e d b y m e a s u r i n g t h e a c susceptibility a s a
function o f external d c field. ( I n a b r i d g e b a l a n c e d
below Tc in zero field t h e signal is p r o p o r t i o n a l t o
?-.)
F o r i n d e p e n d e n t p i n n i n g centers this w o u l d
give t h e c u r v a t u r e o f t h e foot o f t h e p i n n i n g well b u t
collective effects m a k e t h e i n t e r p r e t a t i o n in t e r m s o f
t h e m i c r o s t r u c t u r e c o m p l e x . T h e signal r e m a i n s linear
until t h e v o r t e x d i s p l a c e m e n t is sufficient t o u n p i n flux
lines a t t h e p i n n i n g i n t e r a c t i o n d i s t a n c e (see Sect.
3.11). T h e critical state m o d e l c a n n o t b e a p p l i e d i n
samples t h a t h a v e a d i m e n s i o n c o m p a r a b l e t o A p in i n
t h e direction of p e n e t r a t i o n o f t h e critical state front.

3.11 Pinning Interaction

Distance

T h e p i n n i n g i n t e r a c t i o n d i s t a n c e dpin is t h e d i s t a n c e
flux lines c a n m o v e before they b e c o m e u n p i n n e d . I t is
typically a b o u t a t e n t h o f t h e v o r t e x spacing ( C a m p
bell 1971, C a m p b e l l a n d E v e t t s 1972). T h e v o r t e x
m o v e m e n t a t t h e surface c a n b e derived directly from
t h e susceptibility since t h e voltage in t h e search coils is
p r o p o r t i o n a l t o t h e flux c h a n g e in t h e s a m p l e . If t h e
vortices a t t h e s a m p l e surface m o v e a distance y w h e n
t h e applied flux density is B, t h e flux c h a n g e is By p e r
u n i t length o f surface. N o t e t h a t t h e r e is a n u p p e r
limit t o t h e m o v e m e n t o f t h e m a g n e t i c lines o f force
which applies even in t h e n o r m a l state. F o r a cylindri
cal s a m p l e o f r a d i u s a a n d a n oscillating field o f
a m p l i t u d e Z>, t h e a m p l i t u d e o f t h e flux v o r t e x m o v e
m e n t a t t h e s a m p l e surface is ab/2B. If this is less t h a n
a b o u t a t e n t h o f t h e v o r t e x spacing, t h e r e s p o n s e o f
t h e system will always b e linear a n d t h e critical state
model does n o t apply.
A n alternative t e c h n i q u e f o r investigating t h e dis
p l a c e m e n t o f t h e flux lattice for a n applied force less
t h a n t h e critical d e p i n n i n g force d e p e n d s o n m e a s u r
ing t h e voltage i n a resistive m e a s u r e m e n t f o r a n a c
c u r r e n t with p e a k a m p l i t u d e below t h e critical cur
rent. T h e f o r c e - d i s p l a c e m e n t r e s p o n s e f o r p i n n e d
vortices h a s b e e n m e a s u r e d u s i n g this t e c h n i q u e b y
M c L e a n a n d results a r e given b y Evetts (1983). T h e
initial slope o f t h e f o r c e - d i s p l a c e m e n t r e s p o n s e is
related t o dpin a n d ? b y t h e relations

492

3.12 Critical Current Density

Values of critical density Jc c a n b e m e a s u r e d either b y
direct t r a n s p o r t c u r r e n t s o r inductively. Zero-field
critical c u r r e n t s c a n only b e a r o u g h guide t o t h e
q u a l i t y o f a m a t e r i a l since they a r e affected b y t h e
field g e n e r a t e d b y t h e t r a n s p o r t c u r r e n t ; Jc is said t o b e
self-field limited.
(a) Direct measurements. T h e s e u s e t h e s a m e fourt e r m i n a l t e c h n i q u e a s resistive t r a n s i t i o n s b u t with
m u c h higher currents. Heating a t the current contacts
is a m a j o r p r o b l e m a n d s p u r i o u s results a r e c o m m o n
unless c a r e is t a k e n over t h e design of c u r r e n t c o n t a c t s
a n d t h e l o c a t i o n o f t h e v o l t a g e c o n t a c t s . If a n o r m a l
c o n d u c t i n g s h e a t h is p r e s e n t , c u r r e n t transfer t o t h e
s u p e r c o n d u c t o r m a y t a k e place over a length l o n g
e n o u g h t o o v e r l a p t h e voltage c o n t a c t s , giving a finite
v o l t a g e b e l o w Jc. I n sintered m a t e r i a l s it is i m p o r t a n t
t o k n o w w h e t h e r t h e v o l t a g e c o n t a c t s s p a n grain
b o u n d a r i e s o r a r e so close t h a t they only m e a s u r e t h e
single-grain critical c u r r e n t . F o r practical m a t e r i a l s it
is usually necessary t o c a r r y o u t t h e e x p e r i m e n t s in a
liquid c r y o g e n , since g a s e o u s s u r r o u n d i n g s d o n o t
r e m o v e h e a t fast e n o u g h . H e a t i n g p r o b l e m s s h o u l d b e
suspected if t h e critical c u r r e n t densities b e c o m e inde
p e n d e n t o f m a g n e t i c field o r s h o w hysteresis i n t h e
current applied although variations in internal
t r a p p e d flux c a n c a u s e hysteresis i n Jc i n g r a n u l a r
superconductors. O n e w a y of overcoming heating
p r o b l e m s is t o pulse t h e a p p l i e d c u r r e n t . H o w e v e r ,
there is a limit t o h o w s h o r t t h e pulse c a n b e which is
set b y t h e n e e d f o r flux t o p e n e t r a t e t o t h e center o f
t h e wire before a t r u e resistive voltage c a n b e seen.
T h i s only o c c u r s w h e n t h e skin d e p t h calculated f o r
t h e pulse d u r a t i o n is g r e a t e r t h a n t h e s a m p l e size. T h e
c o n d u c t i v i t y used t o calculate t h e skin d e p t h s h o u l d
b e t h e a v e r a g e f o r t h e m o v i n g flux a n d c a n b e
a m p l i t u d e a n d frequency d e p e n d e n t .
I n h o m o g e n e o u s b u l k s a m p l e s well below t h e irre
versibility line t h e critical c u r r e n t density is n o t very
d e p e n d e n t o n t h e criterion used. F o r i n s t r u m e n t a l
c o n v e n i e n c e 1 is t h e m o s t u s u a l criterion. I n
typical s a m p l e s this c o r r e s p o n d s t o a field o f a b o u t
- 1
. H o w e v e r , t h e limitations o f p a t t e r n i n g
thin films m e a n t h a t t h e s a m e v o l t a g e criterion i n
m e a s u r e m e n t s o n thin-film s a m p l e s often implies elec
tric fields t w o o r t h r e e o r d e r s o f m a g n i t u d e higher.
F o r m a g n e t a p p l i c a t i o n s w h e r e wires m a y b e kilo
m e t e r s i n length a resistivity criterion m a y b e m o r e
a p p r o p r i a t e . I n i n h o m o g e n e o u s m a t e r i a l such a s sin
tered oxides a n d multi-filamentary s u p e r c o n d u c t o r s ,
t h e choice o f a lower electric field criterion c a n lower
t h e critical c u r r e n t density b y a very large factor. I n
these m a t e r i a l s t h e VI characteristic c a n b e a p p r o x i
m a t e d b y a p o w e r l a w o v e r several d e c a d e s of voltage;
such m a t e r i a l s a r e often specified i n t e r m s o f a n
value, w h e r e is a n empirical p o w e r derived b y t h e
best fit o f t h e VI characteristic t o t h e expression

Superconducting

VocI". F o r m a g n e t a p p l i c a t i o n s w h i c h r e q u i r e ex
tremely low electric fields in c o m p o s i t e c o n d u c t o r s t h e
value of is very i m p o r t a n t for design p u r p o s e s ; in
such c o n d u c t o r s the value m a y b e related directly t o
the spatial i n h o m o g e n e i t y in Jc ( P l u m m e r a n d E v e t t s
1987).
(b) Inductive techniques. A n u m b e r of t e c h n i q u e s d e
rive Jc by analysis of t h e signal from a search coil of
the s a m e type as is used t o m e a s u r e inductive transi
tions. T o o b t a i n valid results t h e v o r t e x m o v e m e n t
m u s t b e sufficient t o build u p a critical state (i.e.,
i2
b>(Q)0By /a
w h e r e a is t h e r a d i u s of t h e s a m p l e a n d
0 is the flux q u a n t u m ) . T h e n o n l i n e a r i t y c a u s e d by
flux p i n n i n g c a n b e u s e d in a n u m b e r of w a y s t o
d e t e r m i n e t h e critical c u r r e n t density.
If t h e critical c u r r e n t density is a s s u m e d c o n s t a n t ,
the B e a n critical state m o d e l c a n b e used t o p r e d i c t the
w a v e f o r m , a n d h e n c e t h e t h i r d h a r m o n i c , o r t h e real
a n d i m a g i n a r y p a r t s of t h e susceptibility in t e r m s of
Jc. T h e value c a n t h e n b e c h o s e n t o give t h e best fit t o
the results ( B e a n 1964). T h i s t e c h n i q u e c a n b e
e x t e n d e d by a s s u m i n g a v a r i a t i o n of Jc w i t h such a s
Jcccl/B
a n d fitting t h e p a r a m e t e r s t o the signal a t
v a r i o u s a m p l i t u d e s . If viscous forces a r e t o b e
ignored, t h e frequency m u s t b e such t h a t t h e skin
d e p t h o b t a i n e d from t h e flux flow resistivity is m u c h
greater t h a n t h e s a m p l e size. F r e q u e n c i e s b e t w e e n
100 H z a n d 1000 H z a r e c o m m o n l y used. P a r a m e t e r s
t o describe t h e difference b e t w e e n i n t e r g r a i n a n d
i n t r a g r a i n c u r r e n t s in oxide s u p e r c o n d u c t o r s c a n also
be fitted ( M u l l e r a n d P a u z a 1989, T a k a c s a n d
G o m o r y 1989).
A n o t h e r g r o u p of m e a s u r e m e n t s m e a s u r e s t h e flux
in the s a m p l e directly ( C a m p b e l l 1969, Rollins et al.
1974). T h i s c a n b e d o n e either by i n t e g r a t i n g the
signal in a c o m p u t e r o r from t h e signal from a lock-in
amplifier w h i c h gives t h e flux directly. T h i s requires a
b r o a d e r b a n d d e t e c t o r t h a n the h a r m o n i c analysis, so
increasing t h e noise, b u t it h a s t h e m a j o r a d v a n t a g e
t h a t the t o t a l flux in the s a m p l e is m u c h easier t o
interpret a n d it is n o t necessary t o fit a n u m b e r of
p a r a m e t e r s in c o m p l e x expressions w h i c h m a y b e
based o n invalid a s s u m p t i o n s . A c o m p a r i s o n of the
techniques h a s b e e n m a d e b y K r o e g e r et al. (1975).
F o r a n external field c o n s i d e r a b l y g r e a t e r t h a n
the a m p l i t u d e of t h e a c drive field it c a n generally
be a s s u m e d t h a t Jc is a c o n s t a n t . Differentiation of
the signal from t h e p i c k u p coils with respect t o the
a m p l i t u d e t h e n gives t h e profile of Jc a c r o s s the
sample. T h i s is p a r t i c u l a r l y useful in distinguishing
surface p i n n i n g from b u l k p i n n i n g . I n zero a p p l i e d
field a similar analysis yields t h e critical c u r r e n t
density as a function of for m u c h lower values of
t h a n c a n be achieved in t r a n s p o r t m e a s u r e m e n t s
because of the self-field of t h e c u r r e n t . T h e t e c h n i q u e
c a n b e e x t e n d e d t o give the c o m p l e t e force-displace
m e n t curve for the p i n n e d lattice ( C a m p b e l l 1971,
C a m p b e l l a n d Evetts 1972).

Materials:

Measurements

A p r o b l e m w i t h h i g h - T c m a t e r i a l s is t h a t it is
difficult t o find o u t the effective size of t h e region in
w h i c h c u r r e n t s a r e flowing. T h e m o s t convincing w a y
is t o b r e a k t h e s a m p l e i n t o smaller sizes t o see if the
m a g n e t i z a t i o n c h a n g e s , b u t this is destructive a n d
m a y c h a n g e t h e p r o p e r t i e s . It h a s recently been
p o i n t e d o u t t h a t if the d e m a g n e t i z i n g factor is large,
the slope of the differential susceptibility c a n b e used
t o give t h e size of the c u r r e n t l o o p s a n d this a p p e a r s t o
be a useful t e c h n i q u e ( A n g a d i et al. 1991). H i g h - r c
m a t e r i a l s a r e also a n i s o t r o p i c a n d it m u s t b e a p p r e
ciated t h a t inductive t e c h n i q u e s will always involve
c u r r e n t s flowing in m o r e t h a n o n e direction; if Jc
varies with the direction of c u r r e n t flow a q u a n t i t a t i v e
analysis is difficult.
(c) DC hysteresis. T h e critical c u r r e n t density c a n be
calculated from the hysteresis in the d c m a g n e t i z a t i o n
using t h e critical state m o d e l . T h e m e t h o d is less
sensitive t h a n t e c h n i q u e s b a s e d o n m e a s u r e m e n t of
t h e a c susceptibility b u t since t h e d c m a g n e t i z a t i o n
s h o u l d always be m e a s u r e d it is c o n v e n i e n t t o derive
Jc from such m e a s u r e m e n t s . T h e s a m e p r o b l e m s arise
in deciding o n t h e effective size of the s a m p l e in t h e
case of g r a n u l a r h i g h - T c m a t e r i a l s ; a n u n a m b i g u o u s
c o n c l u s i o n c a n only b e o b t a i n e d from a series of
m e a s u r e m e n t s w h e r e t h e s a m p l e is progressively
r e d u c e d in size.
3.13 Flux Creep
F l u x creep is generally accepted t o b e a result of the
t h e r m a l a c t i v a t i o n of flux lines p a s t p i n n i n g centers. It
leads t o a l o g a r i t h m i c decay of the m a g n e t i z a t i o n if
the a c t i v a t i o n energy U is m u c h g r e a t e r t h a n kBT and
t o c o m p l e t e reversibility a n d zero critical c u r r e n t if U
is c o m p a r a b l e with o r less t h a n kBT. T h e first
m e a s u r e m e n t s were m a d e by m e a s u r i n g t h e decay of a
field t r a p p e d in a h o l l o w cylinder by m e a s u r i n g the
v o l t a g e of a coil inside it ( K i m et al. 1962, Beasley et
al. 1969). Alternatively, t h e coil c a n b e w o u n d r o u n d
t h e o u t s i d e of a solid specimen. T o o b t a i n meaningful
values it is i m p o r t a n t t h a t t h e critical state h a s penet
r a t e d t o t h e center of t h e s a m p l e . A n y t e c h n i q u e
w h i c h m e a s u r e s m a g n e t i z a t i o n c a n b e used t o
m e a s u r e flux creep by m e a s u r i n g t h e m a g n e t i z a t i o n as
a function of time, a l t h o u g h t h e m o s t sensitive tech
n i q u e s m e a s u r e j u s t t h e c h a n g e in m a g n e t i z a t i o n .
M e a s u r e m e n t s a r e easiest in zero applied field b u t it
is i m p o r t a n t t o k n o w h o w a c t i v a t i o n energies v a r y
with field. Since t h e m a g n e t m a y creep a t a similar r a t e
t o t h e specimen, it is n o t easy t o distinguish between
the t w o . I n a d d i t i o n , small c h a n g e s in m a g n e t field,
c a u s e d either by m a g n e t o v e r s h o o t d u r i n g r a m p i n g t o
the m e a s u r e m e n t field o r i n h o m o g e n e i t y over the
region w h e r e t h e s a m p l e is m o v e d , affect the flux creep
r a t e at t h e s a m p l e surface. T o r q u e m a g n e t o m e t r y h a s
p r o v e d a successful t e c h n i q u e , largely eliminating
p r o b l e m s of m a g n e t o v e r s h o o t a n d i n h o m o g e n e i t y .
Simple t h e o r y predicts t h a t AM/M =
(kBT/U)\n(t),

493

Superconducting

Materials:

Measurements

w h e r e is t h e m a g n e t i z a t i o n a n d t is time, so t h a t
w h a t is derived is a n effective a c t i v a t i o n energy.
Statistical effects m a k e this difficult t o i n t e r p r e t in a n y
simple w a y b u t it gives a g o o d g u i d e as t o t h e creep
r a t e in m a g n e t a p p l i c a t i o n s .
3.14 The Irreversibility
Line
T h e t e r m irreversibility line Bixx(T) is a n e w p a r a m e t e r
i n t r o d u c e d for t h e oxide s u p e r c o n d u c t o r s . W h e n t h e
activation energy for flux creep is c o m p a r a b l e t o kBT,
p i n n i n g is ineffective a n d t h e m a g n e t i z a t i o n of t h e
s a m p l e b e c o m e s completely reversible. T h e resistivity
is linear for small c u r r e n t s a n d a l t h o u g h it is less t h a n
t h e flux flow resistivity t h e m a t e r i a l is useless for
practical p u r p o s e s . N o d i a m a g n e t i s m is o b s e r v e d ,
a p a r t from a skin effect a t high frequencies, a n d t h e
low-frequency a c susceptibility is slightly p a r a m a g n e
tic. T h e irreversibility line is n o t precisely defined a n d
c a n be t a k e n as the p o i n t w h e r e t h e m a g n e t i z a t i o n
curve b e c o m e s reversible, t h e p o i n t of z e r o resistance,
t h e start of t h e d i a m a g n e t i c t r a n s i t i o n o r t h e p e a k in
t h e lossy c o m p o n e n t of t h e susceptibility. All these
occur a t similar p o i n t s b u t research is c o n t i n u i n g i n t o
their r e l a t i o n s h i p . O f these t e c h n i q u e s , t h e least reli
able is t h e closing of t h e d c hysteresis c u r v e since this
is ill defined a n d c a n be o b s c u r e d b y i n h o m o g e n e i t y in
t h e m a g n e t . H o w e v e r , l o o k i n g for d i s t o r t i o n in t h e
r e s p o n s e function of a S Q U I D m a g n e t o m e t e r c a n
give g o o d results. It c a n b e seen t h a t m o s t m e t h o d s of
detecting t h e s u p e r c o n d u c t i n g t r a n s i t i o n in a m a g
netic field detect t h e irreversibility line a n d n o t Hc2.
T h e existence of such a line s h o u l d n o t h a v e b e e n
u n e x p e c t e d since t h e energy wells w h i c h p i n flux lines
m u s t r e a c h a d e p t h c o m p a r a b l e with kBT before they
g o t o z e r o a t Hc2. H o w e v e r , t h e d e e p wells a n d low Tc
values e n c o u n t e r e d in c o n v e n t i o n a l s u p e r c o n d u c t o r s
m e a n t t h a t this o c c u r r e d very close t o Hc2 a n d t h e
p h e n o m e n o n w a s n o t o b s e r v e d o r l o o k e d for. I n highTc m a t e r i a l s t h e energy wells a r e smaller relative t o
kBT; t h e irreversibility line is easily distinguished from
Hc2 a n d c a n b e a m a j o r p r o b l e m in practical applica
tions. I n sintered h i g h - T c m a t e r i a l s t h e r e a r e t w o such
lines, o n e for t h e i n t e r g r a i n c u r r e n t s a n d o n e for t h e
intragrain currents.
5.75 AC Losses
M e a s u r e m e n t s of a c losses a r e of t w o types: calori
metric and electromagnetic.
(a) Calorimetric methods. I n o n e t e c h n i q u e t h e h e a t
g e n e r a t e d by losses in t h e s u p e r c o n d u c t o r is m e a s u r e d
by t h e increase in boil-off of t h e cryogenic c o o l a n t .
T h i s gives a n u n a m b i g u o u s loss m e a s u r e m e n t b u t for
a c c u r a t e results it is necessary for t h e loss t o b e
c o n s i d e r a b l y g r e a t e r t h a n t h e b a c k g r o u n d boil-off.
Even with a c a l o r i m e t e r r o u n d t h e s a m p l e t o collect
the gas this m a y b e difficult t o achieve because of t h e
boil-off d u e t o c o n d u c t i o n , p a r t i c u l a r l y if electrical
leads a r e a t t a c h e d t o t h e s a m p l e . T h e b a c k g r o u n d
boil-off is usually d e p e n d e n t o n t h e level of c r y o g e n

494

p r e s e n t a n d t h e c o o l i n g d u e t o increased boil-off c a n
c h a n g e t h e c o n d i t i o n s m a r k e d l y . T h e m o s t reliable
t e c h n i q u e is t o use a null m e t h o d in w h i c h t h e p o w e r
t o a resistor adjacent t o t h e s a m p l e is r e d u c e d in such
a w a y as t o k e e p t h e boil-off c o n s t a n t . T h e r e d u c t i o n
in p o w e r t o t h e resistor is t h e n e q u a l t o t h e dissipation
in t h e s u p e r c o n d u c t o r .
T h i s t e c h n i q u e is used for large v o l u m e s of m a t e r i a l
a n d p a r t i c u l a r l y for m a g n e t coils, w h e r e t h e large
inductive voltage m a k e s electrical m e a s u r e m e n t s inac
c u r a t e . It is generally limited t o t e m p e r a t u r e s for
w h i c h a liquid c r y o g e n c a n b e used, a l t h o u g h in
principle t h e rise in t e m p e r a t u r e of a g a s e o u s c o o l a n t
m i g h t b e used. T h e u l t i m a t e sensitivity is a b o u t 1 m W .
A n o t h e r t e c h n i q u e is t o t h e r m a l l y isolate t h e s a m
ple a n d m e a s u r e t h e r a t e of t e m p e r a t u r e rise. T h i s h a s
n o t b e e n used m u c h as t e m p e r a t u r e g r a d i e n t s a n d t h e
c o n t i n u o u s l y c h a n g i n g t e m p e r a t u r e m a k e t h e results
difficult t o analyze. H o w e v e r , a modification of this
m e t h o d in w h i c h t h e s a m p l e is c o n n e c t e d t o t h e
h e l i u m b a t h b y a t h e r m a l resistance a n d t h e t e m p e r a t
u r e rise is m e a s u r e d in t h e steady state c a n give g o o d
results. S c h m i d t a n d Specht (1990) h a v e used t h e
t e c h n i q u e t o m e a s u r e losses w i t h a r e s o l u t i o n of
10 n W . T h i s m e t h o d is n o t suitable if losses in t h e
presence of a t r a n s p o r t c u r r e n t a r e r e q u i r e d because
of t h e h e a t leak d o w n t h e c u r r e n t leads.
(b) Electrical methods. T h e s e a r e c o n v e n i e n t a n d sen
sitive p r o v i d e d t h e r e is only o n e s o u r c e of p o w e r ,
either a c u r r e n t in a wire o r a m a g n e t i z a t i o n loss. If
t h e p o w e r is c o m i n g from t w o sources such a s a
solenoid a n d a t r a n s p o r t c u r r e n t supply, it is neces
sary t o m e a s u r e b o t h m a g n e t i z a t i o n a n d l o n g i t u d i n a l
voltage. T h i s is t r u e even if o n e of t h e m is n o t
oscillating since a wire c a r r y i n g a n a c c u r r e n t in a n
oscillating m a g n e t i c field will h a v e a voltage i n d u c e d
a l o n g its length w i t h a c o n s e q u e n t p o w e r loss from t h e
supply, leading t o a d y n a m i c resistance. T h e r e c a n b e
c o n s i d e r a b l e p r o b l e m s in b a l a n c i n g o u t inductive
signals from t h e t w o sources a n d a criterion for
b a l a n c e b a s e d o n t h e expected s h a p e of t h e w a v e f o r m
m a y h a v e t o be used. C a l o r i m e t r i c m e t h o d s a r e
p r o b a b l y m o r e reliable in this s i t u a t i o n .
If t h e losses a r e p u r e l y m a g n e t i c , t h e s a m p l e is
placed in a n oscillating field a n d t h e m a g n e t i c res
p o n s e is m e a s u r e d b y o n e of t h e t e c h n i q u e s described
previously. It is t h e n possible t o m e a s u r e t h e a r e a of a
hysteresis l o o p o n t h e M-H curve. H o w e v e r , a m o r e
sensitive m e t h o d is t o m e a s u r e t h e i m a g i n a r y p a r t of
t h e susceptibility. F o r this t e c h n i q u e , it is only t h e
o u t - o f - p h a s e c o m p o n e n t of t h e f u n d a m e n t a l w h i c h
gives t h e loss, so a t u n e d filter is n e e d e d t o eliminate
h a r m o n i c s . T h e m a i n p r o b l e m is in b a l a n c i n g o u t
signals w h i c h a r e n o t d u e t o t h e s a m p l e . It is i m p o r t
a n t t o d o t h e b a l a n c i n g in such a w a y t h a t there is n o t
a large i n - p h a s e c o m p o n e n t since, if this is p r e s e n t , a
very small e r r o r in setting t h e p h a s e leads t o a large
e r r o r in t h e loss. T h e r e f o r e , if t h e p e n e t r a t i o n of t h e

Superconducting

signal is small, the b r i d g e s h o u l d be b a l a n c e d in t h e

s u p e r c o n d u c t i n g state a n d t h e p h a s e set in t h e n o r m a l
state. If the p e n e t r a t i o n is large, t h e b r i d g e s h o u l d b e
b a l a n c e d in t h e n o r m a l s t a t e a n d t h e p h a s e set from
the signal in t h e s u p e r c o n d u c t i n g state. T h i s w o r k s for
losses in a field w h e n t h e losses in zero field c a n b e
a s s u m e d negligible a n d this s t a t e is used for cali
b r a t i o n a n d p h a s e setting. F o r zero-field losses it is
helpful t o be able t o m o v e t h e s a m p l e o u t of t h e coils
t o set t h e p h a s e . A sign t h a t t h e b a l a n c e is c o r r e c t if
the loss is hysteretic is t h e a b s e n c e of a linear signal a t
low a m p l i t u d e s . T h e lossy c o m p o n e n t of t h e suscept
ibility d u e t o hysteresis is a l w a y s p r o p o r t i o n a l t o a t
least t h e s q u a r e of t h e drive signal since t h e s a m p l e
m u s t be driven r o u n d a Rayleigh l o o p .
F o r s a m p l e s c a r r y i n g a c u r r e n t in zero a p p l i e d field
the voltage in p h a s e w i t h t h e c u r r e n t a g a i n gives a n
u n a m b i g u o u s m e a s u r e of t h e loss. A l t h o u g h v o l t a g e s
are smaller t h a n for susceptibility m e a s u r e m e n t s ,
careful design c a n lead t o very small inductive signals
for straight s a m p l e s a n d t h e m e t h o d is very sensitive.
H o w e v e r , for solenoids, t h e large inductive signal will
require a very a c c u r a t e setting of t h e p h a s e for reliable
results.
See also: Magnetic Materials: Measurements

Bibliography
Angadi A, Caplin A D, Laverty J R, Shen X 1991
Nondestructive determination of the current-carrying
length scale in superconducting crystals and thin films.
Physica C 179: 479-87
Bean C 1964 Magnetisation of high field superconductors.
Rev. Mod. Phys. 36: 31-9
Beasley R, Labusch R, Webb W W 1969 Flux creep in
type II superconductors. Phys. Rev. 181: 682-700
Campbell A 1969 The response of pinned flux vortices to
low frequency fields. / . Phys. C 2: 1492-1501
Campbell A M 1971 The interaction distance between flux
lines and pinning centres. J. Phys C 4: 3186-98
Campbell A M, Blunt F J, Johnson J D, Freeman A 1991
Quantitative determination of percentage superconductor
in a new compound. Cryogenics 31: 732-7
Campbell A Evetts J 1972 Flux vortices and transport
currents in type II superconductors. Adv. Phys. 21: 199
428
Cooper J R, Chu C T, Zhou L W, Dunn B, Griiner G 1989
Determination of the magnetic field penetration depth in
superconducting YBaCuO: deviations from the Bardeen
Cooper Schrieffer laws. Phys. Rev. 37: 638-41
2
Cooper J R, Forro L, Collin G, Henry J Y 1990 T
behaviour in the low temperature penetration depth of
oxygen depleted YBaCuO crystals. Solid State Commun.
75: 737-41
Drabeck L, Carini J P, Griiner G, Hylton J, Char K, Beasley
R 1989 Power law temperature dependence of the
electrodynamic properties in oriented YBa 2Cu 30 7_ (5 and
Y ^ C U g O , ^ , films. Phys. Rev. 39: 785-8
Evetts J 1970 Flux pinning by phase boundaries in type II
superconductors. Phys. Rev. 2: 95-6

Materials:

Measurements

Evetts J 1983 The characterization of superconducting

materials: conflicts and correlations. IEEE Trans. Magn.
19: 1109-19
Fiory A T, Hebard A R, Mankiewich , Howard R
1988 Renormalisation of the mean-field superconducting
penetration depth in epitaxial YBaCuO films. Phys. Rev.
Lett. 61: 1419-22
Gilchrist J le G, Monceau 1968 The pinning frequency of
type II superconductors. Philos. Mag. 18: 237-50
Gittleman J I, Rosenblum 1966 Radio frequency measure
ments for subcritical currents. Phys. Rev. Lett. 16: 734-7
Hagen C W, Griessen R 1989 Distribution of activation
energies for thermally activated flux motion in high Tc
superconductors: an inversion scheme. Phys. Rev. Lett.
62: 2857-60
Hamzic A, Fruchter L, Campbell I A 1990 Non-activated
magnetic relaxation in a high Tc superconductor. Nature
345: 515-16
Harshman D R, Schneemeyer L F, Waszczak J V, Aeppli G,
Cava R J, Batlogg B, Rupp L W, Ansaldo J, Williams
D L 1989 Magnetic penetration depth in single-crystal
YBa 2Cu 30 7_ ( 5. Phys. Rev. 39: 851-4
Junod A 1989 Specific heat of high-temperature supercon
ductors: a review. In: Ginsberg D (ed.) 1989 Physical
Properties of High Temperature Superconductors, Vol. 2.
World Scientific, Singapore, pp. 13-120
Kim B, Hempstead C E, Strnad A R 1962 Critical
persistent currents in hard superconductors. Phys. Rev.
Lett. 9: 306-9
Kroeger D M, Koch C C, Charlesworth J 1975 A
comparison of methods for measuring flux gradients in
type II superconductors. / . Low Temp. Phys. 19: 493-512
Mitra S, Chu J H, Lee W C, Johnston D C, Kogan V G 1989
Magnetic field penetration depth of polycrystalline
(Y,Cd)Ba 2Cu 30 7, grain aligned YBaCuO and single crys
tal Bi 2Sr 2CaCu 2O g. Phys. Rev. 40: 2674^7
Montgomery C 1971 Methods for measuring electrical
resistivity of anisotropic materials. / . Appl. Phys. 42:
2971-5
Muller , Pauza A J 1989 Susceptibility of high tempera
ture superconductors in a critical state model. Physica C
159: 717-26
Plummer C J G, Evetts J 1987 Dependence of the shape of
the resistive transition on composite inhomogeneity in
multifilamentary wires. IEEE Trans. Magn. 23: 117982
Rollins R W, Kupfer H, Gey W 1974 Magnetic field profiles
in type II superconductors with pinning using a new ac
technique. / . Appl. Phys. 45: 5392-8
Schmidt C, Specht 1990 AC loss measurements on super
conductors in the microwatt range. Rev. Sci. Instrum. 61:
988-92
Takacs S, Gomory F 1989 Study of flux flow in high Tc
superconductors. Physica C 162: 681-2
van der Pauw L J 1961 Determination of resistivity tensor
and Hall tensor of anisotropic conductors. Philips Res.
Rep. 16: 187-95
Welp U, Kwok W K, Crabtree G W, Vandervoort G, Liu
J 1989 Magnetic measurements of the upper critical
field of YBaCuO single crystals. Phys. Rev. Lett. 62:
1908-11
A. M . Campbell
[University of C a m b r i d g e , C a m b r i d g e , U K ]

495


Texture: Nondestructive
Characterization
T e x t u r e is t h e t e r m a p p l i e d t o t h e presence of a
preferred c r y s t a l l o g r a p h i c o r i e n t a t i o n of t h e crystal
lites (grains) in a polycrystalline m a t e r i a l . F i b e r s
b e c o m e t e x t u r e d d u r i n g g r o w t h o r processing.
M e c h a n i c a l o p e r a t i o n s such as d r a w i n g , rolling o r
swaging i n d u c e t e x t u r e . All such t e x t u r i n g i n t r o d u c e s
a n i s o t r o p y in t h e m e c h a n i c a l p r o p e r t i e s of t h e a g
gregate w h i c h affects t h e r e s p o n s e of t h e m a t e r i a l
d u r i n g further f o r m i n g , f a b r i c a t i o n o r in-service
operations.

/.

General

T h e c o m p l e t e c h a r a c t e r i z a t i o n of t e x t u r e in a s a m p l e
entails t h e d e t e r m i n a t i o n of t h e o r i e n t a t i o n d i s t r i b u
tion function ( O D F ) . T h i s is t h e v o l u m e fraction of
crystallites h a v i n g a specific c r y s t a l l o g r a p h i c orien
t a t i o n relative t o a c o o r d i n a t e system fixed in t h e
s a m p l e . D e t e r m i n a t i o n of t h e O D F requires diffrac
tion d a t a a n d r a t h e r s o p h i s t i c a t e d series-expansion
analysis. O w i n g t o t h e i n t e r a c t i o n s of g r a i n s w i t h their
neighbors, to anisotropically distributed second
p h a s e s o r v o i d s a n d t o o t h e r factors, a k n o w l e d g e of
the O D F is n o t , in general, sufficient t o p r e d i c t all t h e
a n i s o t r o p i c p r o p e r t i e s of a polycrystalline a g g r e g a t e .
Nevertheless, from a k n o w l e d g e of t h e O D F a n d
a p p r o p r i a t e single-crystal p r o p e r t i e s such q u a n t i t i e s
as the a n g u l a r v a r i a t i o n of Y o u n g ' s m o d u l u s a n d t h e
yield locus in t h e rolling p l a n e of steel sheet, a n d t h e
quantitative correlation between texture and the ani
s o t r o p y of m a g n e t o c r y s t a l l i n e energy in F e - S i steel
sheet h a v e b e e n d e t e r m i n e d .
I n the c o n t e x t of n o n d e s t r u c t i v e e v a l u a t i o n ( N D E ) ,
m e a s u r e d a n i s o t r o p y c a n b e a n i n d i c a t o r of degree of
texture. I n h e x a g o n a l , t r i g o n a l o r t e t r a g o n a l crystals
texture gives rise t o a n i s o t r o p y in electrical a n d t h e r
m a l resistance, coefficients of t h e r m a l e x p a n s i o n , ther
moelectric force a n d m a g n e t i c susceptibility. I n cubic
crystals such p r o p e r t i e s as elastic m o d u l u s a n d m a g
n e t i z a t i o n p o w e r losses a r e t e x t u r e d e p e n d e n t . S o m e
of these p r o p e r t i e s h a v e b e e n explicitly e m p l o y e d as
n o n d e s t r u c t i v e p r o b e s of t e x t u r e in m e t a l s .
T e x t u r e in p o l y m e r s is a n i m p o r t a n t special case
because of t h e g r e a t difference in s t r e n g t h b e t w e e n t h e
covalent b o n d s f o r m i n g t h e c h a i n o r b a c k b o n e a n d
the i n t e r c h a i n forces. O r i e n t a t i o n is easily p r o d u c e d in
polymers by deformation, shearing molten material,
film e x t r u s i o n o r b y g r o w t h processes in n a t u r a l
p o l y m e r s . Studies of t e x t u r e in p o l y m e r s h a v e b e e n
reviewed b y W e c k e r a n d M o r r i s (1978).

2. Diffraction

Techniques

W i t h diffraction m e t h o d s all even m o m e n t s of t h e

O D F c a n b e d e t e r m i n e d , w h e r e a s o t h e r techniques
can determine no more than the fourth moment. Xr a y diffraction h a s b e e n t h e p r i n c i p a l t e c h n i q u e for
l a b o r a t o r y t e x t u r e studies for d e c a d e s ; h o w e v e r , t h e
limited d e p t h of p e n e t r a t i o n , ;$ 0.0 l c m , limits the
t e c h n i q u e t o surface N D E . N e u t r o n diffraction,
w h i c h is c o m p l e t e l y a n a l o g o u s t o x-ray diffraction,
h a s seen increasing use b e c a u s e of relatively great
p e n e t r a t i o n (of t h e o r d e r of centimeters) a n d different
scattering selectivity from t h a t of r a y s for different
elements.
I n F i g . 1 a r e s h o w n t h e overall scattering g e o m e t r y
a n d t h e role of m a s k i n g in a n N D E t e x t u r e vs d e p t h
m e a s u r e m e n t w i t h fixed-wavelength n e u t r o n s ( C h o i et

Scattering plane

(b)
Figure 1
(a) A schematic illustration of scattering geometry for a
diffraction experiment. The arrows in the scattering plane
show incoming and diffracted radiation, (b) Details of
symmetric reflection-geometry measurement. The upper
portion shows masking effects (shaded); is the Bragg
angle

497

Texture:

Nondestructive

Characterization

One plate
Cu (400)

Lower

several p l a n e s in a series of spherical h a r m o n i c s , it is

possible t o d e t e r m i n e t h e O D F for t h e s a m p l e .
F o r N D E , t h e following is of interest. F o r a slab
g e o m e t r y , as s h o w n in Fig. l b , t h e d e p t h of s a m p l i n g
c a n be varied b y c h a n g i n g t. T h i s c a n b e a c c o m p l i s h e d
b y c h a n g i n g w a v e l e n g t h o r b y e x a m i n i n g different
o r d e r s of t h e s a m e reflection (e.g., 111 a n d 222). Since
t h e g e o m e t r i c factors c a n b e m e a s u r e d , a p p r o x i m a t e
t e x t u r e as a function of d e p t h c a n b e d e t e r m i n e d
n o n d e s t r u c t i v e l y b y t a k i n g a p p r o p r i a t e l y weighted
differences of t h e p o l e figures for different e x p o s u r e
v o l u m e s . T h i s t y p e of a p p r o a c h m a y b e p a r t i c u
larly useful in c o n j u n c t i o n w i t h time-of-flight n e u t r o n
diffraction ( a n a l o g o u s t o energy-dispersive x-ray dif
fraction) w h e r e i n different (hkl) p l a n e s diffract t h e
a p p r o p r i a t e w a v e l e n g t h of a " w h i t e " n e u t r o n b e a m a t
a fixed scattering angle. I n this case t h e e x p o s u r e
v o l u m e is t h e s a m e for e a c h (hkl) p l a n e for a given
sample orientation.
A l t h o u g h t h e n e u t r o n diffraction a p p r o a c h c a n b e
p u r s u e d only a t a research r e a c t o r o r accelerator
facility, its truly n o n d e s t r u c t i v e c h a r a c t e r h a s been
utilized t o establish t e x t u r e - p e r f o r m a n c e c o r r e l a t i o n s
in certain military a p p l i c a t i o n s a n d for ball b e a r i n g s .
I n t h e future, t h e scope of N D E for t e x t u r e c h a r a c
terization m a y be e n h a n c e d b y utilizing diffraction
t e c h n i q u e s as p r i m a r y s t a n d a r d s a n d , for e x a m p l e ,
u l t r a s o n i c s o r m a g n e t i c m e t h o d s for a c t u a l inspec
tion.
See also: Microtextural Analysis; Pole Figures and Orien
tation Distribution Functions

Cu (200)
two plates

Upper
two plates

Figure 2
Pole figures for texture versus depth measurement for two
stacked copper plates, each 0.08 cm thick misoriented by
45. In each figure, the center represents = 90, the
periphery = 30. ranges from 0 to 360,
circumferentially. The contour lines are drawn in multiples
of random intensity (i.e., intensity for a completely
random-orientation sample). The left-hand column shows
the measured (200) and (400) pole densities for the
two-plate sample, and the (200) pole density for the lower
plate measured alone. The right-hand column shows the
(200) pole density for each plate extracted from the
two-plate data by the difference technique

al. 1979). T h e scattering angle is c h o s e n t o fulfill t h e

Bragg c o n d i t i o n for t h e (hkl) p l a n e of interest, a n d t h e
s a m p l e is r o t a t e d a b o u t t h e t w o m u t u a l l y p e r p e n d i c u
lar axes ( a n d in Fig. 1) t o o b t a i n relative intensit
ies for all possible s a m p l e o r i e n t a t i o n s . T h e m a p of
intensity as a function of s a m p l e o r i e n t a t i o n for a
specific (hkl) p l a n e is usually p l o t t e d as a " p o l e figure"
as s h o w n in Fig. 2. By e x p a n d i n g t h e p o l e figures for

498

Bibliography
Bunge J 1969 Mathematische Methoden der Texturanalyse. Akademie-Verlag, Berlin
Choi C S, Prask J, Trevino S F 1979 Nondestructive
investigation of texture by neutron diffraction. J. Appl.
Crystallogr. 12: 327-31
Klug , Alexander L 1974 X-ray Diffraction Procedures
for Polycrystalline and Amorphous Materials, 2nd edn.
Wiley, New York, Chap. 10, pp. 709-54
Szpunar J 1976 Texture and neutron diffraction. At. Energy
Rev. 14: 199-261
Wecker S M, Morris R 1978 Modern methods of texture
analysis. / . Appl. Crystallogr. 11: 211-20
H . J. P r a s k a n d C . S. C h o i
[ N a t i o n a l B u r e a u of S t a n d a r d s ,
Washington, D C , USA]

Thermal Analysis: An Overview

T h e r m a l analysis refers t o a n y t e c h n i q u e for t h e s t u d y
of m a t e r i a l s w h i c h involves t h e r m a l c o n t r o l . M e a s u r e
m e n t s a r e usually m a d e w i t h increasing t e m p e r a t u r e ,
but isothermal measurements or measurements made
with decreasing t e m p e r a t u r e s a r e also possible. T a b l e

Thermal

Analysis:

An

Overview

Table 1
Thermal analysis techniques

Technique"
Thermometry
Differential thermal analysis
Calorimetry
Dilatometry
Thermomechanical analysis
Thermogravimetry
Dynamic mechanical analysis
Electrate thermal analysis
Electrical conductivity analysis
Emanation thermal analysis
Evolved-gas analysis
Thermal conductivity analysis
Thermal diffusivity analysis
Thermoacoustimetry
Thermofractography
Thermoluminescence analysis
Thermomagnetic analysis
Thermooptical analysis
Thermosonimetry

Measurement
(in addition to
temperature)
time
temperature difference
heat
length or volume
stress, strain
mass
stress, strain, time
electrical discharge current
electrical resistance
release of radioactive
material
pyrolysis with gas analysis
thermal conductivity
thermal diffusivity
sound effects
thermal fractionation
coupled with thin-layer
chromatography
light emission
magnetic susceptibility
microscopy
sound effect

a In addition, any other investigative technique, such as x-ray

diffraction, NMR or spectroscopy, can be coupled with temperature
control and become a thermal analysis technique

1 s h o w s a selection of t h e r m a l analysis t e c h n i q u e s ,
illustrating t h e b r e a d t h of t h e field. I n fact, a n y
measuring technique can be m a d e into a thermal
analysis t e c h n i q u e b y a d d i n g t h e r m a l c o n t r o l . Simul
t a n e o u s use of m u l t i p l e t e c h n i q u e s increases t h e
p o w e r of t h e r m a l analysis, a n d m o d e r n i n s t r u m e n
t a t i o n h a s p e r m i t t e d extensive g r o w t h of a p p l i c a t i o n .
T h e basic theories of t h e r m a l analysis ( e q u i l i b r i u m
t h e r m o d y n a m i c s , irreversible t h e r m o d y n a m i c s a n d
kinetics) a r e well d e v e l o p e d , b u t h a v e t o d a t e n o t b e e n
applied t o a c t u a l e x p e r i m e n t s t o t h e fullest e x t e n t
possible.

1.

Thermometry

T h e r m o m e t r y is b y far t h e oldest a n d simplest t h e r m a l

analysis t e c h n i q u e . It a l w a y s involves t h e m e a s u r e
m e n t of t e m p e r a t u r e a n d usually t h e m e a s u r e m e n t of
time. H e a t i n g a n d c o o l i n g curves h a v e b e e n u s e d for
m a n y years t o establish p h a s e d i a g r a m s (Fig. 1). A n y
type of t h e r m o m e t e r c a n b e used for m e a s u r e m e n t .
T h e m o s t c o m m o n for m a n u a l r e c o r d i n g a r e m e r c u r y in-glass t h e r m o m e t e r s ; a u t o m a t i c r e c o r d i n g a n d d a t a
t r e a t m e n t b e c o m e s possible w i t h resistance ther
mometers and thermocouples.

Time

( c o n s t a n t heat

input)

Concentration

(a)

(b)

Figure 1
(a) A simple eutectic phase diagram and (b) the
corresponding heating curve, with constant heat input
leading to an almost linear temperature rise

C o u p l i n g of t h e r m o m e t r y w i t h o t h e r t e c h n i q u e s
such as m i c r o s c o p y , x-ray diffraction a n d spectros
c o p y is frequent. M e l t i n g t e m p e r a t u r e s a r e readily
seen a n d easily verified b y m i c r o s c o p i c o b s e r v a t i o n .
G l a s s t r a n s i t i o n s , w h i c h c a u s e only a c h a n g e in slope
in t h e t i m e - t e m p e r a t u r e r e c o r d i n g , r e q u i r e higher
precision a n d a r e m o r e s h a r p l y defined b y o b s e r v a t i o n
of t h e d i s a p p e a r a n c e of strain b y p o l a r i z i n g m i c r o s
c o p y . C o n s t a n t t r a n s i t i o n t e m p e r a t u r e r e c o r d i n g is
frequent in t h e f o r m of freezing-point d e t e r m i n a t i o n
(cryoscopy) o r b o i l i n g - p o i n t d e t e r m i n a t i o n (ebulliometry). T h r o u g h two-phase equilibrium thermo
d y n a m i c s t h e c h a n g e s in t r a n s i t i o n t e m p e r a t u r e s a r e
coupled to concentration (mass and molecular mass)
a n d h e a t s of t r a n s i t i o n ( e n t r o p i e s of t r a n s i t i o n ) . H i g h
est a c c u r a c y is r e a c h e d in t h e analysis of linear
macromolecules (polymers). Transition temperature
5
c h a n g e s of as little as 1 0 " a r e m e a s u r e d for t h e
5
d e t e r m i n a t i o n of m o l e c u l a r m a s s e s of t h e o r d e r of 10 .

2. Differential

Thermal

Analysis

I n principle, differential t h e r m a l analysis ( D T A ) is a

t e c h n i q u e w h i c h c o m b i n e s t h e ease of m e a s u r e m e n t of
h e a t i n g o r c o o l i n g curves w i t h t h e q u a n t i t a t i v e
features of c a l o r i m e t r y (see Sect. 3). T e m p e r a t u r e is
m e a s u r e d c o n t i n u o u s l y as for h e a t i n g o r c o o l i n g curve
d e t e r m i n a t i o n s , a n d t h e differential t e m p e r a t u r e
m e a s u r e m e n t p e r m i t s t h e c a l c u l a t i o n of t h e h e a t flow
difference b e t w e e n reference a n d s a m p l e , w h i c h a r e
k e p t in a l m o s t identical e n v i r o n m e n t s ( D T A furnace).
F i g u r e 2 schematically s h o w s a D T A a p p a r a t u s using
t h e r m o c o u p l e s for m e a s u r e m e n t . T h e p r o g r a m m e r
supplies a linear h e a t i n g r a t e . If d u r i n g m e a s u r e m e n t
the temperature gradient within the sample can be
k e p t small, it is possible t o e l i m i n a t e t h e effect of
sample heat conductivity on the sample temperature
itself, a n d h e a t flows c a n b e calculated from t e m -

499

Thermal

Analysis:

An

Overview

AT

Recorder

amplifier
7"

Ice

bath

Programmer
f u r n a c e - control
thermocouple

reference
DTA

sample

P o w e r to heater

furnace

dQT/dt

K(Tb-Tr)

0)

dQJdt

K(Tb-Ts)

(2)

w h e r e t h e t h e r m a l c o n d u c t i v y is d e p e n d e n t o n t h e
g e o m e t r y a n d m a t e r i a l of t h e cell, b u t is i n d e p e n d e n t
of t h e s a m p l e . F o r simplicity, t h e cell a r r a n g e m e n t is
a s s u m e d t o b e s u c h t h a t s a m p l e a n d reference h a v e
t h e s a m e K. Th is t h e D T A furnace o r h e a t i n g b l o c k
t e m p e r a t u r e a n d , a n d Ts a r e t h e reference a n d
s a m p l e t e m p e r a t u r e s , respectively. E q u a t i o n s (1) a n d
(2) a r e simple r e p r e s e n t a t i o n s of N e w t o n ' s law of
c o o l i n g . T h e h e a t flow e q u a t i o n c a n be derived f r o m
E q n s . (1) a n d (2) b y m a k i n g Tb increase linearly w i t h
t h e h e a t i n g r a t e q (i.e., Th= T0 + qt) a n d . a s s u m i n g
t h a t all s a m p l e h e a t flow is u s e d t o increase t h e s a m p l e
T0)),with C pr e p r e s e n t i n g
t e m p e r a t u r e ( i . e . , Q s = Cp(Tsthe (constant) sample heat capacity:
dQJdt

Figure 2
Schematic diagram of a DTA apparatus

500

(3)

T h e s o l u t i o n s of t h e h e a t flow e q u a t i o n in t e r m s of
t o t a l h e a t flow u p t o time t o r t e m p e r a t u r e a r e
(initial c o n d i t i o n s t = 0, Th = Ts = T0 = 0, Q = 0):
Qs = qCpt-

p e r a t u r e m e a s u r e m e n t s . U n d e r such c o n d i t i o n s t h e
t e c h n i q u e is frequently called differential s c a n n i n g
calorimetry (DSC).
D T A o r i g i n a t e d a t t h e t u r n of t h e c e n t u r y w h e n
s i m u l t a n e o u s p h o t o g r a p h i c r e c o r d i n g of t w o t h e r m o
c o u p l e o u t p u t s b e c a m e possible. T h e first m a j o r a p p l i
c a t i o n s were in t h e s t u d y of p h a s e d i a g r a m s a n d
t r a n s i t i o n t e m p e r a t u r e s , a n d q u a l i t a t i v e a n a l y s e s of
m e t a l s , oxides, salts, c e r a m i c s , glasses, m i n e r a l s a n d
soils. By 1952, 1000 r e s e a r c h r e p o r t s o n D T A w e r e
published; by 1972, t h e a n n u a l r a t e of p u b l i c a t i o n s
exceeded 1000. T h i s increase w a s b r o u g h t a b o u t b y
the use of electronics t o increase m e a s u r i n g a c c u r a c y
a n d t o a u t o m a t e d a t a collection a n d t r e a t m e n t . A t
present, D T A is used in a l m o s t all fields of scientific
investigation a n d is especially useful for t h e analysis
of m e t a s t a b l e systems. A m o d e r n design for use w i t h
t e m p e r a t u r e s from 100 t o 1000 is s h o w n in F i g . 3.
1
Typical sensitivies of 10-100 s " h a v e been c l a i m e d
for such i n s t r u m e n t s for 1-10 m g s a m p l e size. H e a t i n g
1
rates m a y r a n g e from 0.5 t o 50 m i n . H e a t c a p a
city m e a s u r e m e n t s as a c c u r a t e as 0 . 5 % h a v e b e e n
r e p o r t e d in f a v o r a b l e cases. T r a n s i t i o n t e m p e r a t u r e s
m a y be d e t e r m i n e d t o 0 . 1 K . E x t r e m e c o n d i t i o n
D T A m a y s p a n h e a t i n g r a t e s from 0.01 t o 10 000
1
m i n " , t e m p e r a t u r e s of m e a s u r e m e n t m a y r e a c h
a b o v e 3000 a n d m e a s u r e m e n t s u p t o p r e s s u r e s of
500 M P a h a v e b e e n achieved.
D T A without a temperature gradient within the
s a m p l e ( < 1.0 K ) , w h i c h c a n easily b e i n t e r p r e t e d
q u a n t i t a t i v e l y , is limited for 1 g s a m p l e s t o a b o u t a
1
1 m i n " h e a t i n g r a t e a n d for 1 m g s a m p l e s t o a b o u t
1
100 m i n " . T h e h e a t flow i n t o t h e reference
(dQJdt)
a n d s a m p l e (dQJdt)
c a n be given b y

= K[qt-(QJCp)]

Ts = qt~

(qC\lK)[\
(qCv/K)[\

- e x p ( - Kt/Cp)]

(4)

- e x p ( - Kt/Cp)]

(5)

U n d e r s t e a d y - s t a t e c o n d i t i o n s (Kt > C p ) the t e m

p e r a t u r e difference b e t w e e n s a m p l e (Ts) a n d b l o c k
(Th = qt) is t h u s directly p r o p o r t i o n a l t o t h e h e a t
c a p a c i t y a n d p e r m i t s c a l c u l a t i o n of e n t h a l p y c h a n g e s
(DSC). T h e exponential term represents the a p p r o a c h
t o s t e a d y s t a t e . F i g u r e 4 illustrates t h e a p p r o a c h t o
s t e a d y s t a t e s t a r t i n g from AT= qt - Ts = 0. F i g u r e 4
also s h o w s t h e c h a n g e in d u r i n g a s h a r p t r a n s i t i o n
in t h e s a m p l e s u c h as is f o u n d , for e x a m p l e , in
melting. D u r i n g t h e t r a n s i t i o n (from tx t o t{) t h e

Silver ring

Thermoelectric
(constanton)
disk

Dummy
Alumel wire
Heating block

Alumel
wire

Chromel wire

Figure 3
A typical DTA (DSC) measuring cell (courtesy of Du
Pont, Analytical Instruments Division)

Thermal

Analysis:

An

Overview

(a)

Time

Figure 4
A typical DTA trace showing first the approach to steady
state ATj, then melting (between times /; and i f), and
finally the renewed approach to steady state

s a m p l e t e m p e r a t u r e r e m a i n s c o n s t a n t , so t h a t AT
increases w i t h a slope e q u a l t o t h e h e a t i n g r a t e q.
W h e n m e l t i n g is c o m p l e t e , a r e n e w e d a p p r o a c h t o
steady state, described b y E q n . (5), o c c u r s . T h e verti
cally a n d h o r i z o n t a l l y s h a d e d a r e a s a r e p r o p o r t i o n a l
t o t h e t o t a l h e a t of fusion. T h e c r o s s h a t c h e d a r e a A is
expressed b y
0

t{yexv[-K(t-tr)/Cp]dt

(6)

T h i s is easily i n t e g r a t e d t o
A =

q(tf-ti)CJK

(7)

which in t u r n is seen t o b e e q u a l t o t h e vertically

s h a d e d a r e a . T h i s simple c a l c u l a t i o n leads t o t h e
c o m m o n l y a p p l i e d " b a s e l i n e m e t h o d " for t h e evalu
a t i o n of t h e h e a t s of t r a n s i t i o n s o r r e a c t i o n s . T h e a r e a
a b o v e t h e baseline is p r o p o r t i o n a l t o t h e h e a t of
transition; t h e baseline is p r o p o r t i o n a l t o t h e h e a t
capacity, b u t d o e s n o t h a v e t o b e e v a l u a t e d . I n cases
w h e r e t h e baseline ( h e a t c a p a c i t y ) is n o t t h e s a m e
before a n d after t h e t r a n s i t i o n , a small c o r r e c t i o n m a y
be necessary.
F i g u r e 5 gives s o m e e x a m p l e s of typical D T A traces
for the indentification of m a t e r i a l s (fingerprinting).
T h e traces c a n also b e used for q u a n t i t a t i v e evalu
a t i o n of t e m p e r a t u r e s a n d h e a t s of t r a n s i t i o n as well
as kinetic p a r a m e t e r s . A typical e x a m p l e of a n a n a l y
sis of a m o r e c o m p l i c a t e d p h a s e d i a g r a m is s h o w n in
Fig. 6. T h e b o t t o m half of F i g . 6 r e p r e s e n t s t h e p h a s e
d i a g r a m for t w o eutectic systems, w i t h s o m e limited
solubility in t h e crystalline state, c o m p o u n d f o r m a
tion a n d a peritectic p o i n t . T h e t o p half of F i g . 6
shows t h e D T A traces c o r r e s p o n d i n g t o t h e c o n c e n
t r a t i o n s a t o f. A n analysis of m e t a s t a b l e crystals of
p o l y o x y m e t h y l e n e is illustrated b y F i g . 7. O n u s i n g
_ 1
low h e a t i n g r a t e s (e.g., 5 C m i n ) , t h e m e t a s t a b l e

300

600
Temperature

900
(C)

Figure 5
Qualitative analysis by DTA. Four D T A curves of pure
substances, (a) Amyl alcohol (2 sample in air
at
- 1
atmospheric pressure, heating rate l O K m i n .
Transitions: 1, some crystallization at - 119C; 2, melting
at - 79 C; 3, boiling at 139 C). (b) Polyethylene
terephthalate) (10 mg sample in_ nitrogen
at atmospheric
1
pressure, heating rate 2 0 K m i n . Transitions: 1, glass
transition at about 75 C, characteristic of noncrystalline
e
materials; 2, crystallization at 145 C; 3, melting at 253 C ;
4, exothermic decomposition above 360 C). (c) Iron
( ~ 30 mg sample in helium
at atmospheric pressure,
_ I
heating rate 2 0 K m i n . Transitions: 1, a- to -
transition at 757 C; 2, - to y-iron transition at 910 C; 3,
y- to <5-iron transition at 1389 C; 4, melting at 1533 C).
(d) Barium chloride ( ~ 10 mg sample
in air at atmospheric
_ l
pressure, heating rate 2 0 K m i n . Transitions: 1 and 2,
loss of water in two stages at 130 and 187 C, respectively;
3, orthorhombic-to-cubic transition at 923 C; 4, melting
at 950 C)

crystals m e l t (first e n d o t h e r m ) , recrystallize (exot h e r m ) , m e l t a g a i n (second e n d o t h e r m ) , recrystallize

a g a i n p a r t i a l l y a n d h a v e a final m e l t i n g e n d o t h e r m .
All m e l t i n g crystals a r e of t h e s a m e crystal s t r u c t u r e
a n d differ o n l y in crystal size a n d perfection. A t faster
h e a t i n g r a t e s t h e recrystallization is increasingly s u p
pressed a n d t h e o n l y m e t a s t a b l e crystal p r e s e n t in t h e
original crystal is revealed.

501

Thermal

Analysis:

Exotherm

An

Overview

Endotherm

Ld

k.
<

/ V 2= I . O

Concentration

/V, =1.0

Figure 6
Hypothetical phase diagram of reasonable complication
(eutectic points, compound formation, partial solid-state
solubility and a peritectic point). The curves a-f drawn
above the phase diagram illustrate typical heating curves
that could be obtained with a differential scanning
calorimeter

3.

temperature

(C)

Figure 7
Typical set of melting curves of polyoxymethylene taken
at the indicated heating rates, for sample masses between
10 and 1 mg. The samples represent solution-grown stacks
of thin, lamellar crystals

Calorimetry

C a l o r i m e t r y w a s first d e v e l o p e d in t h e e i g h t e e n t h
c e n t u r y . Since t h e r e is n o direct h e a t m e t e r , m e a s u r e
m e n t s of h e a t m u s t rely o n s e c o n d a r y effects such a s
t e m p e r a t u r e rises, c h a n g e s of s t a t e , o r c h e m i c a l , elec
trical o r m e c h a n i c a l h e a t - e n e r g y c o n v e r s i o n s . T h e
m a j o r difficulty of c a l o r i m e t r y is t h e fact t h a t t h e r e is
n o perfect i n s u l a t o r for h e a t . T h e r e f o r e , loss calcula
t i o n s t o c o r r e c t for imperfect c o n t a i n m e n t of t h e h e a t
t o b e m e a s u r e d a r e basic t o all c a l o r i m e t r y . I s o t h e r
m a l o r nearly i s o t h e r m a l c a l o r i m e t e r s p e r m i t t h e best
h a n d l i n g of t h e h e a t loss p r o b l e m . A typical e x a m p l e
of a n i s o t h e r m a l c a l o r i m e t e r is s h o w n in F i g . 8. T h e
i s o t h e r m a l e n v i r o n m e n t is c r e a t e d b y a w a t e r - i c e
m i x t u r e . T h e s a m p l e t o b e investigated is d r o p p e d
from a c o n s t a n t - t e m p e r a t u r e reservoir, o r a r e a c t i o n
o r o t h e r c h a n g e of s t a t e is i n d u c e d after t h e e q u i
l i b r i u m t e m p e r a t u r e is achieved. A c h a n g e in t h e h e a t
c o n t e n t of t h e s a m p l e is d e t e c t e d b y t h e v o l u m e
c h a n g e d u e t o t h e m e l t i n g o r crystallization of t h e ice
in t h e i n n e r c a l o r i m e t e r c o n t a i n e r . T h e v o l u m e c h a n g e

502

Sample

Dewar vessel
Figure 8
Bunsen ice calorimeter

Thermal
Adiaoatic d e v i a t i o n :

Temperature:

Analysis:

An

Overview

m e t e r s , w h i c h c a n o p e r a t e o n the a d i a b a t i c o r the
differential c a l o r i m e t e r principle. D S C h a s seen t h e
largest d e v e l o p m e n t recently b e c a u s e of ease of h a n d
ling a n d c o m p u t e r c o u p l i n g . H e a t c a p a c i t y accuracies
h a v e r e a c h e d 0.1 % for s a m p l e m a s s e s as small as
10 m g . T e m p e r a t u r e r a n g e s from 100 t o 1000 a n d
1
h e a t i n g rates b e t w e e n 1 a n d 20 m i n " a r e c o m m o n .
T h e goal of m o s t c a l o r i m e t r y is t h e e s t a b l i s h m e n t of
t h e t h e r m o d y n a m i c functions of systems of interest.
H e a t s of t r a n s i t i o n a n d h e a t capacities lead t o
enthalpy data at various temperatures. Using the
t h e r m o d y n a m i c r e l a t i o n s h i p s for e q u i l i b r i u m ,
H-

H0 +

CpdT

(8)

[\cp/T)dt

(9)

J
S=S0+

jacket

4m

heating and

flow

main top mid bottom U

mm\mi

cooling

Heat:
watthour

meter

pump

pressure
/C^N

+ ++ * L ~ ~

ingoing outgoing
Figure 9
Example of a typical adiabatic calorimeter

is m e a s u r e d by d e t e c t i o n of t h e c h a n g e in m e r c u r y
m a s s inside t h e c a l o r i m e t e r .
Closely related t o i s o t h e r m a l c a l o r i m e t e r s a r e a n e r
oid a n d liquid c a l o r i m e t e r s , in w h i c h a small t e m p e r a
t u r e rise in a solid (metal b l o c k ) o r liquid (water)
reservoir is m e a s u r e d precisely ( 0.001 K ) t o deter
m i n e the c h a n g e in h e a t c o n t e n t of t h e u n k n o w n .
B o m b c a l o r i m e t e r s a r e well k n o w n , being c o m m o n l y
used t o m e a s u r e h e a t s of c o m b u s t i o n t o a precision of
up to 0 . 0 1 % .
A n o t h e r type of c a l o r i m e t e r is t h e a d i a b a t i c calori
meter, in which a n a t t e m p t is m a d e t o m i n i m i z e t h e
h e a t loss by raising o r lowering t h e t e m p e r a t u r e of t h e
s u r r o u n d i n g s t o m a t c h t h e s a m p l e t e m p e r a t u r e (Fig.
9). A d i a b a t i c c a l o r i m e t e r s a r e c o m m o n l y built for
o p e r a t i o n from 10 t o a b o u t 700 K , a n d m a y r e a c h a
precision of 0 . 0 1 % in h e a t c a p a c i t y d e t e r m i n a t i o n s
for large s a m p l e m a s s e s ( 1 0 0 - 5 0 0 g). Special i n s t r u
m e n t a t i o n is available for very low t e m p e r a t u r e s .
In c o m p e n s a t i n g c a l o r i m e t e r s , t h e effect of a c h e m
ical reaction is c o m p e n s a t e d b y h e a t i n g o r cooling.
The best-known compensating calorimeters are those
t h a t m a k e use of t h e Peltier effect ( T i a n - C a l v e t calori
meters) a n d stirred-liquid c a l o r i m e t e r s ; their c o n
struction is usually a d a p t e d t o t h e specific a p p l i c a t i o n .
A b r i d g e t o D T A is achieved with s c a n n i n g calori-

G =

H-TS

(10)

Tt =

AHJASt

()

allows c o m p l e t e t h e r m a l analysis w h e n e v e r h e a t
capacities C p a n d t r a n s i t i o n e n t h a l p i e s AHt a n d
t e m p e r a t u r e s Tt a r e given. S t a n d a r d functions a r e
widely t a b u l a t e d a n d t h e t h e o r y of h e a t capacities is
well d e v e l o p e d .

4. Dilatometry

and Thermomechanical

Analysis

D i l a t o m e t r y deals with t h e d e t e r m i n a t i o n of length o r

v o l u m e as a function of t e m p e r a t u r e . T h e r m o m e c h a
nical analysis ( T M A ) is t h e t e r m applied t o d i l a t o
m e t r y carried o u t u n d e r tension o r l o a d . Historically,
dilatometry and T M A date back to ancient metrol
ogy. O b v i o u s length m e a s u r e m e n t s a r e m a d e t h r o u g h
side-by-side c o m p a r i s o n with a s t a n d a r d ; o b v i o u s
v o l u m e m e a s u r e m e n t is t h r o u g h c o m p a r i s o n with t h e
c o n t e n t of a s t a n d a r d vessel. T h e highest precision in
length m e a s u r e m e n t is achieved b y interferometry,
w h i c h allows, for e x a m p l e , t h e m a i n t e n a n c e of the
8
s t a n d a r d m e t e r t o a precision w i t h i n 1 p a r t in 10 .
V o l u m e d e t e r m i n a t i o n with p y c n o m e t e r s , v o l u m e t r i c
flasks, cylinders, b u r e t t e s a n d pipettes is difficult t o
push beyond 0.01%.
A s c h e m a t i c d r a w i n g of a typical T M A a p p a r a t u s is
s h o w n in Fig. 10. T h e length m e a s u r e m e n t is per
f o r m e d via a linear-variable differential t r a n s f o r m e r
( L V D T ) . A c h a n g e in t h e p o s i t i o n of t h e c o r e , which
floats frictionlessly w i t h i n t h e t r a n s f o r m e r coil, results
in a linear c h a n g e in o u t p u t voltage. A force is applied
t o t h e s a m p l e b y b a l a n c i n g flotation a n d weight.
M e a s u r e m e n t is possible in t h e c o m p r e s s i o n , tension
a n d b e n d i n g m o d e s . T y p i c a l h e a t i n g rates r a n g e from

503

Thermal

Analysis:

An

Overview

-tU^-*

W e i g h t tray

Float
I suspension

Linear - variable
transformer

di f f e r e n t i a l
X

Gas

purge -x

(LVDT)

LVDT c o r e
Probe coupling

\Sample tube

t h e only partially crystallized molecules. T h i s t r e n d is

reversed a s s o m e l o w - t e m p e r a t u r e crystallization sta
bilizes t h e fiber. Close t o t h e m e l t i n g t e m p e r a t u r e Tm
t h e fiber e x p a n d s limitlessly o w i n g t o flow. D e t a i l s o f
m a n u f a c t u r i n g a n d p e r f o r m a n c e variables c a n t h u s b e
quickly e v a l u a t e d b y T M A . Expansivities, s h r i n k a g e ,
glass a n d m e l t i n g t r a n s i t i o n s a r e m o s t easily m e a s u r
able b y T M A .
T w o extensions of T M A a r e p r e s s u r e - v o l u m e temperature determinations a n d dynamic mechanical
analysis. T h e f o r m e r lead t o t h e e q u i l i b r i u m functions
of state a n d a r e available for m a n y s u b s t a n c e s u p t o
t h e gigapascal r a n g e , revealing m a n y h i g h - p r e s s u r e
a n d h i g h - t e m p e r a t u r e crystal forms. T h e latter
involves t i m e - d e p e n d e n t s t r e s s - s t r a i n d e t e r m i n a t i o n
a t v a r i o u s t e m p e r a t u r e s a n d is basic t o t h e analysis of
m e c h a n i c a l p r o p e r t i e s (elasticity a n d viscoelasticity).

5.

Thermogravimetry

T h e r m o g r a v i m e t r y w a s d e v e l o p e d a r o u n d 1900 a n d
basically involves t h e m a s s d e t e r m i n a t i o n of a s a m p l e
u n d e r c o n t r o l l e d i s o t h e r m a l o r linearly v a r y i n g t e m
p e r a t u r e in a given a t m o s p h e r e . A p l o t of m a s s a s a
function of time o r t e m p e r a t u r e is t h e result of a
Figure 10
TMA apparatus (courtesy of Mettler Instrument
Company)
Furnace control
Temperature
program

0.1 t o 40 m i n " . T e m p e r a t u r e r a n g e s from 100 t o

1000 a r e c o m m o n , b u t h i g h - t e m p e r a t u r e T M A t o
2500 is available. S a m p l e sizes a r e usually of t h e
gram a n d centimeter magnitudes.
A typical T M A o f a d r a w n fiber, s u c h a s a polyester
(poly(ethylene t e r e p h t h a l a t e ) ) , is s h o w n schematically
in F i g . 11. Below t h e glass-transition t e m p e r a t u r e Tg
t h e T M A c u r v e s h o w s n o r m a l , a l m o s t linear e x p a n
sion. A t 8 , t h e fiber s h r i n k s o w i n g t o r e l a x a t i o n of

S a m p l e temperature

T-i

DTA

Weight i n d i c a t i o n

DTG

V a c u u m ind.ication

I Other measurements iDiffusion

pump

Diffusion
pump

Thermostat

Power supply

Temperature

Figure 11
TMA of a drawn polyester fiber

504

Figure 12
Schematic diagram of a thermogravimetry apparatus with
differential thermogravimetry (DTG) facility (courtesy of
Mettler Instrument Company)

Thermal

Figure 13
Thermogravimetric analysis of calcium oxalate with the
corresponding DTA curve

t h e r m o g r a v i m e t r i c e x p e r i m e n t . A b l o c k d i a g r a m of a
typical t h e r m o g r a v i m e t r i c a p p a r a t u s is s h o w n in F i g .
12. C o n t i n u o u s m a s s r e c o r d i n g a n d c o m p e n s a t i o n is
possible b y e l e c t r o m a g n e t i c weight c o m p e n s a t i o n .
Sensitivities a r e usually several m i c r o g r a m s . T o t a l
sample m a s s e s m a y r a n g e from milligrams t o g r a m s .
T e m p e r a t u r e r a n g e s a r e usually from r o o m t e m p e r a
ture t o a s high a s 2700 K .
M a j o r a p p l i c a t i o n s of t h e r m o g r a v i m e t r y involve
stability analysis of m a t e r i a l s in different a t m o s p h e r e s
or v a c u u m . A typical e x a m p l e is s h o w n in F i g . 13. T h e
analyzed C a C 2 0 4 . H 2 0 is seen t o d e c o m p o s e in t h r e e
stages:
C a C 20 4. H 2 0 - C a C 20 4 + H 2 0

(12)

C a C 20 4 - C a C 0 3 + CO

(13)

C a C 0 3- C a O + C0

(14)

F i g u r e 13 also s h o w s a D T A c u r v e w h i c h reveals t h a t
the first a n d t h i r d r e a c t i o n s a r e e n d o t h e r m i c , w h e r e a s
the second r e a c t i o n is c o m p l e x , involving a t least o n e
e x o t h e r m i c a n d o n e e n d o t h e r m i c stage.
T h e q u a n t i t a t i v e d a t a analysis of t h e n o n i s o t h e r m a l
reactions is usually a t t e m p t e d using s t a n d a r d r e a c t i o n
kinetics:
d[A]/dt

= k[A]

(15)

w h e r e [A] is t h e r e a c t a n t c o n c e n t r a t i o n , k is t h e
specific r a t e c o n s t a n t a n d is t h e o r d e r of t h e r e a c
tion. T h e t e m p e r a t u r e d e p e n d e n c e o f k is i n c o r p o r
ated in E q n . (15) using t h e A r r h e n i u s e q u a t i o n :
dk/dT=

A e x p ( - EJRT)

(16)

w h e r e E& is t h e a c t i v a t i o n energy. F r e q u e n t l y , h o w
ever, E q n . (15) is a n oversimplification; m o r e c o m p l i
cated a n d m u l t i p l e r e a c t i o n p a t h s often m a k e a simple

Analysis:

An

Overview

analysis impossible. O t h e r difficulties involve t h e p r e

cise s a m p l e - t e m p e r a t u r e m e a s u r e m e n t , w h i c h m u s t
usually b e d o n e b y p o s i t i o n i n g a t h e r m o c o u p l e close
t o , b u t o u t s i d e of, t h e weighing p a n . Since m o s t o f t h e
r e a c t i o n s t o b e studied involve g a s e v o l u t i o n , t h e r a t e
of diffusion of these o u t of t h e s a m p l e m a y influence
t h e p o s i t i o n of t h e e q u i l i b r i u m , so t h a t p a c k i n g d e n
sity a n d s a m p l e size b e c o m e of i m p o r t a n c e . A n inter
esting a p p l i c a t i o n of t h e r m o g r a v i m e t r y is t h e lifetime
p r e d i c t i o n of m a t e r i a l s such a s p o l y m e r s . T h e stability
of t h e m a t e r i a l s is d e t e r m i n e d in a s h o r t - t i m e experi
m e n t a t elevated t e m p e r a t u r e a n d t h e results a r e
e x t r a p o l a t e d u s i n g E q n s . (15) a n d (16) t o use
temperatures.
See also: Polymers: Thermal Analysis; Thermal Analysis:
Recent Developments

Bibliography
Benedict R 1977 Fundamentals of Temperature, Pressure
and Flow Measurements, 2nd edn. Wiley, New York
Buzas I (ed.) 1975 Thermal Analysis, Proc. 4th Int. Conf.
Thermal Analysis. Heyden, London
Chihara (ed.) 1977 Thermal Analysis, Proc. 5th Int. Conf.
Thermal Analysis. Heyden, London
Duval C 1963 Inorganic Thermogravimetric Analysis, 2nd
edn. Elsevier, Amsterdam
MacKenzie R C (ed.) 1970,1972 Differential Thermal Analy
sis. Interscience, New York
Madorsky S L 1964 Thermal Degradation of Organic
Polymers. Interscience, New York
Miller (ed.) 1982 Thermal Analysis, Proc. 7th Int. Conf.
Thermal Analysis. Wiley, New York
Redfern J (ed.) 1965 Thermal Analysis, Proc. 1st Int. Conf.
Thermal Analysis. Macmillan, London
Rossini F D, Sumner S (eds.) 1979 Experimental Thermo
chemistry, Vol. 3. Pergamon, New York
Schwenker R F Jr, Gam D (eds.) 1969 Thermal Analysis,
Proc. 2nd Int. Conf. Thermal Analysis. Academic Press,
New York
Touloukian Y S, Ho C Y (eds.) 1970-79 Thermophysical
Properties of Matter; The TPRC Data Series. A Compre
hensive Compilation of Data. IFI/Plenum, New York
Turi 1981 (ed.) Thermal Analysis of Polymeric Materials.
Academic Press, New York
Weissberger A, Rossiter W (eds.) 1971 Physical Methods
of Organic Chemistry, Physical Methods of Chemistry,
Vol. 1, Pt. V: Determination of Thermodynamic and
Surface Properties. Wiley, New York
Wendlandt W W 1974 Thermal Methods of Analysis, 2nd
edn. Wiley, New York
Wiedemann G (ed.) 1972 Thermal Analysis, Proc. 3rd Int.
Conf Thermal Analysis. Birkhauser, Basel
Wiedemann G (ed.) 1980 Thermal Analysis, Proc. 6th Int.
Conf. Thermal Analysis. Birkhauser, Basel
Wunderlich 1981 Thermal Analysis, Audio Course and
Text. Rensselaer Polytechnic Institute, Troy, N Y
B. W u n d e r l i c h
[Rensselaer P o l y t e c h n i c I n s t i t u t e ,
Troy, New York, USA]

505

Thermal

Analysis:

Recent

Developments

Thermal Analysis: Recent Developments

B o t h t h e i n s t r u m e n t a t i o n a n d t h e a p p l i c a t i o n of ther
m a l analysis a r e e x p a n d i n g rapidly. I n o r d e r t o
c o m p l e m e n t the excellent description of t h e general
m e t h o d s (see Thermal Analysis: An Overview) a n d t h e
c o m p a n i o n article o n a p p l i c a t i o n s t o p o l y m e r s (see
Polymers: Thermal Analysis), stress will be placed o n
the m o s t i m p o r t a n t of t h e t e c h n i q u e s a n d aspects n o t
previously described in detail a n d o n a p p l i c a t i o n s t o
i n o r g a n i c m a t e r i a l s c e r a m i c s , m e t a l s a n d so o n . I n
a d d i t i o n , the g r o w i n g a r e a of interest in t h e applica
tion of feedback t o c o n t r o l t h e t e m p e r a t u r e p r o g r a m
d u r i n g t h e r m o a n a l y t i c a l m e a s u r e m e n t s is c o n s i d e r e d
very briefly. It is h o p e d t h a t these few e x a m p l e s will
convince t h e r e a d e r of the p o w e r a n d versatility of
thermoanalytical methods. They are conceptually
very simple b u t extremely useful in i m a g i n a t i v e h a n d s .

/.

Thermogravimetry

and

Thermomagnetometry

1.1 General and Instrumental

Considerations
T h e r m o g r a v i m e t r y ( T G ) is essentially t h e r m o m a g n e
t o m e t r y ( T M ) while t h e s a m p l e is subjected t o a
magnetic-field g r a d i e n t . C o n s e q u e n t l y t h e t w o tech
niques a r e discussed in t h e s a m e section. T h e i m p o s i
tion of t h e field g r a d i e n t allows d e t e r m i n a t i o n of
m a g n e t i c susceptibility as a function of t e m p e r a t u r e ,
as with a F a r a d a y b a l a n c e . M o r e imaginatively h o w
ever, it c a n be used t o detect t h e f o r m a t i o n o r
d i s a p p e a r a n c e of m a g n e t i c p h a s e s a n d t h e C u r i e t e m
p e r a t u r e Tc or Neel t e m p e r a t u r e of m a t e r i a l s .
W a r n e a n d G a l l a g h e r (1987) h a v e recently reviewed
TM.
In m a n y a p p l i c a t i o n s of these t e c h n i q u e s it is
i m p o r t a n t t o c o n t r o l the a t m o s p h e r e over the s a m p l e
d u r i n g h e a t i n g . C o n s i d e r a b l e efforts h a v e also b e e n
made to operate at other than atmospheric pressure.
A g a r w a l et al. (1987) describe t h e a p p l i c a t i o n of T G
at high pressure. F a r m o r e c o m m o n , h o w e v e r , is T G
a t r e d u c e d pressures. Occasionally, c o r r o s i v e a t m o s
pheres a r e of interest a n d special c a r e m u s t b e t a k e n
t o preserve t h e integrity of t h e b a l a n c e . T h i s is
generally a c c o m p l i s h e d by flowing a n inert a t m o s
phere through the balance chamber and subsequently
blending in t h e corrosive c o m p o n e n t (e.g., h a l o g e n ,
S 0 2 , H 2 0 , etc.) p r i o r t o passing over the s a m p l e . A n
e x t r e m e case of b a l a n c e p r o t e c t i o n a n d isolation is
p r o v i d e d by t h e clever m a g n e t i c - c o u p l i n g device d e
scribed by S c h u b a r t a n d K n o t h e (1972).
1.2 Applications

of TG and

TM

T h e early a p p l i c a t i o n s used T G t o establish t h e region

of c o n s t a n t weight for t h e c o n v e r s i o n of precipitates
to k n o w n weighable species for gravimetric analysis.
This w a s e x t e n d e d t o s t u d y t h e r m a l d e c o m p o s i t i o n s in
general. R e l a t e d t o this is t h e q u e s t i o n of oxidative
stability of p o l y m e r s o r t h e o x i d a t i o n of alloys. It h a s

506

also f o u n d use in such a r e a s as a d s o r p t i o n , lowt e m p e r a t u r e n i t r o g e n a d s o r p t i o n for B E T surface

a r e a a n d p o r o s i t y m e a s u r e m e n t o r elevated t e m p e r a
t u r e a d s o r p t i o n t o identify v a r i o u s catalytically active
sites o n solids.
T h e i m p o r t a n c e of t h e oxygen c o n t e n t in h i g h - T c
oxide s u p e r c o n d u c t o r s h a s a c c e n t u a t e d t h e a l r e a d y
i m p o r t a n t a r e a of d e t e r m i n a t i o n of d e v i a t i o n from
oxygen s t o i c h i o m e t r y , p a r t i c u l a r l y in electronic cera
mics. F o r m a n y oxides t h e electrical c o n d u c t i o n ,
dielectric p r o p e r t i e s a n d m a g n e t i c b e h a v i o r d e p e n d
m a r k e d l y o n small v a r i a t i o n s in oxygen c o n t e n t . T o
5
follow these differences (as little as o n e p a r t in 10 ) a t
elevated t e m p e r a t u r e , requires careful w o r k t o ac
c o u n t for b u o y a n c y , a e r o d y n a m i c forces a n d the
volatility of s a m p l e a n d c o n t a i n e r c o m p o n e n t s .
F i g u r e s 1 a n d 2 from B r a c c o n i a n d G a l l a g h e r (1972)
indicate t h e d a t a themselves (Fig. 1) a n d t h e t h e r m o
d y n a m i c i n t e r p r e t a t i o n in t h e f o r m of a v a n ' t Hoff
D i a g r a m (Fig. 2) for a nickel zinc ferrite. T h e r a t e of
a t t a i n i n g c o n s t a n t weight is a frequent i n d i c a t o r of
metastability. Systems t h a t involve the p r e c i p i t a t i o n
o r dissolution of a second p h a s e a r e particularly
susceptible t o such effects. I n F i g . 1, t h e c h a n g e in
slope of t h e w e i g h t - v s - t e m p e r a t u r e curves is evident a t
t h e t r a n s i t i o n b e t w e e n t h e single-phase a n d t w o - p h a s e
regions; h o w e v e r , t h e time t o r e a c h e q u i l i b r i u m
d e p e n d s m a r k e d l y o n t h e direction of crossing t h e
p h a s e b o u n d a r y . T h e p r e c i p i t a t i o n of t h e second
p h a s e requires n u c l e a t i o n a n d c o n s e q u e n t l y consider
ably m o r e t i m e t o r e a c h e q u i l i b r i u m t h a n the simpler
process of dissolution.
T h e ability to s u p e r c o n d u c t a t t e m p e r a t u r e s a b o v e
77 h a s led t o a n explosion of interest in certain
complex copper-based oxide systems. M o s t of these
materials exhibit a n e n o r m o u s r a n g e of oxygen c o n t e n t
while preserving the s a m e basic structure, which a d d s
to their scientific fascination. Figure 3 contrasts
the oxygen-exchange behavior of three systems:
B a 2 Y C u 3 0 7 , (Gallagher et al. 1987a); B i 2 S r 1 5C a , 5C u 2 0 8
( G r a d e r et al. 1988); a n d P b 2 S r 2 Y C u 3 0 8 (Gallagher et
al. 1989). T h e b a r i u m material reversibly loses 0 2
a b o v e 350 C, forming B a 2 Y C u 3 0 6 4 by the time
1000 C is reached in p u r e oxygen. T h e structure
transforms from o r t h o r h o m b i c to tetragonal symmetry
d u r i n g the loss of oxygen. T h e superconducting
properties i m p r o v e as the oxygen c o n t e n t a p p r o a c h e s
7.00. In contrast, the lead c o m p o u n d reversibly gains
substantial oxygen, reaching a m a x i m u m c o n t e n t at
a r o u n d 500 C. T h e weight gain a b o v e 650 C repre
sents oxidative d e c o m p o s i t i o n to new phases. Also, in
c o n t r a s t t o the b a r i u m c o m p o u n d , the superconduct
ing properties of the lead c o m p o u n d deteriorate with
increasing oxygen content. T h e b i s m u t h c o m p o u n d , o n
the o t h e r h a n d , is relatively stable in oxygen c o n t e n t
a n d only begins t o lose significant oxygen as it
a p p r o a c h e s its incongruent melting p o i n t n e a r 900 C.
I n o r d e r t o c o n v e r t these weight losses t o a b s o l u t e
values of oxygen c o n t e n t , it is necessary t o k n o w t h e

Thermal

- maximum

Analysis:

Recent

Developments

oxidation

0.02

9.96

-stoichiometric composition -

I IOC
Temperature

I
80C

1000

I
700

(C)

Figure 1
Excess oxygen coefficient and corresponding weight of Nio^Zno 1 7 F
7 e2 1 30
8 4 vs temperature and oxygen content of the gas
phase

Temperature
1400

1300

1200

1100

(C)
1000

precise c o m p o s i t i o n a t s o m e reference p o i n t . T h e r e
a r e a variety of analytical m e t h o d s available: r e d u c
t i o n in h y d r o g e n o n a t h e r m o b a l a n c e t o yield t h e
alkaline e a r t h a n d r a r e - e a r t h oxides p l u s c o p p e r a n d /
o r lead m e t a l s is o n e of t h e m o s t c o m m o n l y u s e d
m e t h o d s . It d o e s n o t w o r k for t h e b i s m u t h o r t h a l l i u m
c o m p o u n d s , b e c a u s e of t h e volatility of t h e m e t a l s .
O t h e r w a y s T G is used effectively in s t u d y i n g these
104.0
B a 2Y C u 30 7

103.5

B i 2S r C a 2C u 20 8

103.0

P b 2S r 2Y C u 30 8

102.5
^

102.0

101.5

101.0

100.5

100.0
99.5
99.0

\/T

I0

(K )

Figure 2
Isocompositional phase diagram for ^ 1 7 7F3 e 2 , 3 80 4
constructed with interpolated values from Fig. 1: the
oxygen excess coefficient is indicated on each
isocompositional line

98.5
9

08

100.0

200.0

300.0 400.0

500.0 600.0

Temperature

700.0 800.0

900.0

(C)

Figure 3
-1
TG curves for several oxides heated at 1 C m i n in
oxygen

507

Thermal

Analysis:

Recent

Developments

temperature
to I05C
magnet out

nitrogen

ash only remains

oxygen

ash from
Fig. I

Time

Time

(a)

(b)

Figure 4
Proximate analysis scheme for coal analysis based on T G and T M

systems is t o follow t h e d e c o m p o s i t i o n of p r e c u r s o r
c o m p o u n d s s u c h a s t h e m i x e d o x a l a t e s ( O z a w a 1988)
o r for assaying t h e initial s t a r t i n g c o m p o u n d s . T h e
alkaline a n d r a r e - e a r t h oxides a r e n o t o r i o u s for
a b s o r b i n g large q u a n t i t i e s of H 2 0 a n d C 0 2 , d u r i n g
s t o r a g e a n d m a n y of t h e soluble salts, s u c h as n i t r a t e s
a n d acetates, frequently used for synthesis h a v e
u n c e r t a i n w a t e r c o n t e n t s . D e g r a d a t i o n of t h e
B a 2Y C u 30 7 material on exposure to C 0 2 and H 2 0 has
also been investigated b y T G ( G a l l a g h e r et al. 1988a).
Studies involving p e r m a n e n t gases o r m a t e r i a l s of
high volatility a t relatively low t e m p e r a t u r e (e.g.,
H 2 0 ) a r e easy t o set u p a n d c o n t r o l . It is m o r e difficult
t o p e r f o r m e x p e r i m e n t s t h a t involve t h e v a p o r t r a n s
p o r t of Z n O , P b O , L i 2 0 a n d so o n . T h e t e c h n i q u e
utilized b y H o l m a n (1974) is useful if suitably inert
furnace t u b e s , s a m p l e c o n t a i n e r s a n d s u s p e n s i o n
m a t e r i a l s a r e available. A s a n e x a m p l e , lead-deficient
lead t i t a n a t e ( P b T i 0 3 ) is s u s p e n d e d from a b a l a n c e
a n d s u r r o u n d e d b y t h e t w o - p h a s e m i x t u r e a t either
p h a s e b o u n d a r y . A s t h e t e m p e r a t u r e is raised t o a
p o i n t for a r e a s o n a b l e r e a c t i o n r a t e , t h e lead v a p o r
pressure is m a i n t a i n e d c o n s t a n t a t t h e v a l u e e s t a b
lished b y t h e t w o - p h a s e buffer m a t e r i a l a t t h a t t e m
p e r a t u r e . T h e c h a n g e of t h e s a m p l e c a n b e followed
until it reaches its e q u i l i b r i u m value a t t h a t t e m p e r a
t u r e a n d t h e p a r t i a l p r e s s u r e of t h e lead. If t h e
c o m p o s i t i o n a t t h e p h a s e b o u n d a r y is k n o w n a c c u r
ately, t h e n t h e original lead deficiency c a n be deter
m i n e d . If n o t t h e n only relative values for different
c o n d i t i o n s c a n b e established.
T h e use of c o m b i n e d T G a n d T M for t h e p r o x i m a t e
analysis of coal is s h o w n in F i g . 4 ( A y l m e r a n d R o w e
1982). Clearly resolved weight losses o c c u r for m o i s
t u r e a n d volatiles in n i t r o g e n . Switching t o a n oxi
dizing a t m o s p h e r e allows c o m b u s t i o n of t h e fixed
c a r b o n . After c o o l i n g t o r o o m t e m p e r a t u r e t h e origi-

508

n a l pyrite c o n t e n t is d e t e r m i n e d b y a T M r e d u c t i o n of
t h e i r o n oxide in t h e a s h t o i r o n m e t a l b y h y d r o g e n .
A s i r o n m e t a l f o r m s , t h e a p p a r e n t weight increases
b e c a u s e of t h e s t r o n g m a g n e t i c a t t r a c t i o n of i r o n . T h e
relatively r a p i d a n d simple analysis of these five
c o m p o n e n t s of c o a l agrees very well w i t h results
obtained using the previous m o r e cumbersome
methods.
C h a r l e s (1982) p r o v i d e s a n excellent e x a m p l e of t h e
use of T M t o s t u d y c o r r o s i o n . A T M a p p a r a t u s is
s h o w n in F i g . 5a a n d s o m e results for t h e r a t e of
c o r r o s i o n of steel b y a n a q u e o u s a m m o n i a c a l E D T A
s o l u t i o n a r e p r e s e n t e d in F i g . 5b. T h e o x i d a t i o n of
thin c o b a l t films o r their r e a c t i o n with a silicon
s u b s t r a t e w a s also studied b y T M ( G a l l a g h e r et al.
1987b). O t h e r metallurgical e x a m p l e s of T M a r e given
b y H a g l u n d (1982). T h e use of T M t o establish t h e
presence of m a g n e t i t e a s a n i n t e r m e d i a t e d u r i n g t h e
d e c o m p o s i t i o n of siderite ( F e C 0 3 ) in air o r oxygen
h a s also b e e n described. M a g n e t i t e did n o t f o r m in air
o r oxygen a n d t h e m a g n e t i t e t h a t did f o r m u n d e r inert
c o n d i t i o n s i n c o r p o r a t e d m o s t of t h e divalent i m p u r i
ties (e.g., m a g n e s i u m , c a l c i u m o r m a n g a n e s e ) . U s e of
w e l l - k n o w n values of Tc for p u r e m e t a l s a n d alloys is
a c o m m o n m e t h o d t o c a l i b r a t e t h e t e m p e r a t u r e scale
d u r i n g T G . G a l l a g h e r a n d G y o r g y (1986) described
s o m e of t h e factors t h a t affect t h e a c c u r a c y a n d
c o m p a r e d this m e t h o d w i t h t h e use of m e l t i n g p o i n t s
for t e m p e r a t u r e c a l i b r a t i o n .

2. Differential
Thermal
Scanning
Calorimetry

Analysis

and

Differential

2.1 General and Instrumental

Considerations
T h e scope of t h e t e r m s differential t h e r m a l analysis
( D T A ) a n d differential s c a n n i n g c a l o r i m e t r y ( D S C )

Thermal

,Cahn m o d e l RH
recording balance

nm

^Counter weights

Sealed glass or t i t a n i u m
"reaction tube
Corroding solution

F o i l or powdered
specimen
- Electromagnet

Thermocouple probe
(a)

9 0 C

I20C

I30C

I40C*V^
0

40

80

120

160

200

Recent

Developments

m e a s u r e m e n t of energy u n d e r these c o n d i t i o n . T o the

user, h o w e v e r , t h e practical c o n s i d e r a t i o n is w h e t h e r
o r n o t t h e energy associated w i t h t h e event of interest
c a n o r c a n n o t b e accurately d e t e r m i n e d .

Furnace

150

Analysis:

240

Time (min)
(b)

Figure 5
A TM study of the aqueous corrosion of steel: (a) TMA
apparatus as used for aqueous corrosion work; and
(b) corrosion of 2 mil type 285 carbon steel in 5%
ammoniated EDTA solutions

h a s been t h e subject of d e b a t e w h i c h is succinctly

treated b y M a c k e n z i e (1980). T h e r e are t w o u n c o n t r o versial e n d m e m b e r s : first, D T A , in w h i c h the D T
signal is m e a s u r e d b y t h e r m o c o u p l e s inserted i n t o t h e
sample a n d reference m a t e r i a l s o r in c o n t a c t w i t h
their respective c o n t a i n e r s while t h e s a m p l e a n d refer
ence a r e t h e r m a l l y isolated; a n d s e c o n d , D S C , in
which the t e m p e r a t u r e of the s a m p l e a n d reference
m a t e r i a l a r e k e p t e q u a l a n d t h e difference in t h e
p o w e r supplied o r t h e h e a t flux t o e a c h is m e a s u r e d .
In D S C the difference in energy is directly d e t e r m i n e d .
T h e c o n t r o v e r s i a l m i d d l e g r o u n d arises w h e n a c o n
trolled h e a t leak o r c o n n e c t i o n is m a d e b e t w e e n the
sample a n d reference m a t e r i a l s in D T A . B o e r s m a
(1955) p r o v i d e d a t h e o r y t h a t allows q u a n t i t a t i v e

2.2 Applications of DTA and DSC

T h e general t e n d e n c y is t o t h i n k of these techniques in
t e r m s of solid-state t r a n s i t i o n s , r e a c t i o n s o r d e c o m p o
sitions. H o w e v e r , they a r e equally v a l u a b l e for p r o
cess studies such a s catalysis. C o n s i d e r the o x i d a t i o n
of C O b y oxygen, a highly e x o t h e r m i c reaction,
releasing this h e a t a t t h e surface of t h e catalyst. F i g u r e
6 s h o w s h o w readily D T A o r D S C c a n b e used t o
r a p i d l y a n d conveniently screen relative catalytic a c
tivity a n d t o d e t e r m i n e w h i c h gases m a y p o i s o n this
activity ( G a l l a g h e r et al. 1976). Clearly in Fig. 6a
c o p p e r c h r o m i t e is a s u p e r i o r catalyst t o t h e p a r
tially s u b s t i t u t e d l a n t h a n u m m a n g a n a t e s , while the
s t r o n t i u m - s u b s t i t u t e d m a t e r i a l is t h e best of the latter
g r o u p . T h e ability of 150 p p m of S 0 2 t o p o i s o n the
catalytic activity is o b v i o u s in Fig. 6 b . H i g h - p r e s s u r e
D S C cells a r e c o m m e r c i a l l y available a n d used t o
e v a l u a t e h y d r o g e n a t i o n catalysts ( K o s a k 1976).
T h e use of D S C t o m e a s u r e depression of the
m e l t i n g p o i n t h a s f o u n d w i d e s p r e a d use for p u r i t y
analysis, p a r t i c u l a r l y for p h a r m a c e u t i c a l s ( M o r r o s
a n d S t e w a r t 1976). A n interesting i s o t h e r m a l applica
tion is t o m e a s u r e the i n d u c t i o n time for t h e oxidative
d e g r a d a t i o n of p o l y m e r s a n d t o e v a l u a t e the effective
ness of v a r i o u s a n t i o x i d a n t s ( H o w a r d 1973).
A m a j o r use of D T A a n d D S C is in the a r e a of
p h a s e equilibria a n d crystal g r o w t h . T h e w e a k
s e c o n d - o r d e r ferroelectric p h a s e t r a n s i t i o n ( 1 1 0 0 1200 C) in L i N b 0 3 is a s t r o n g function of t h e lithium
deficiency in t h e m a t e r i a l . Since t h e c o m p o u n d melts
i n c o n g r u e n t l y , it is necessary t o k n o w t h e c o m p o s i
t i o n a t this m e l t i n g p o i n t precisely in o r d e r t o g r o w
h o m o g e n e o u s crystals for use in electrooptic devices.
D e t e c t i n g t h e small c h a n g e in t h e h e a t c a p a c i t y by
D T A a s a function of c o m p o s i t i o n w a s used t o
establish t h e c o n g r u e n t c o m p o s i t i o n a n d t o follow the
defect (cation v a c a n c y ) equilibria in t h e system a s it is
d o p e d with T i 0 2 for device fabrication ( G a l l a g h e r et
al. 1988b).
T h e crystal g r o w t h a n d sintering of the h i g h - r c
s u p e r c o n d u c t i n g m a t e r i a l s is d e p e n d e n t o n the melt
ing t e m p e r a t u r e . I n Sect. 1.2 it w a s s h o w n h o w the
oxygen c o n t e n t of these m a t e r i a l s at a n y t e m p e r a t u r e
varies w i t h the p a r t i a l p r e s s u r e of oxygen. D T A h a s
been used t o s h o w (Fig. 7) h o w t h e melting t e m p e r a t
ures decrease w i t h decreasing p a r t i a l pressure of oxy
gen ( G a l l a g h e r 1987).

3. Evolved

Gas

Analysis

3.1 General Considerations and

Instrumentation
I n t h e previously m e n t i o n e d t e c h n i q u e s , events are
described in t e r m s of their c h a n g e in weight o r h e a t

509

Thermal

Analysis:

Recent

Developments

<

900
100

200
Temperature

300

400

500

(C)

Temperature

(C)

Figure 6
(a) DTA curves for oxidation of CO using catalysts with
a
-1
wide variety of activities (the heating rate is 2 C m i n in
a gas stream
of 2% CO, 2% 0 2 and 96% N 2 at
3
-1
2
100 cm m i n ) : (i) copper chromite,
16.0 mg, 18.0 m g~
2
(ii) Lao 5Sr 0 5Mn0 3, 16.0mg, 31.5 2m g ' ; (iii)
La 0 7 5Ko 2 5Mn0 3, 15.3 mg, 18.7 m g ' ; 2 (iv) La 0 7Pb 0 3MnO 3,
crystals, 3000 ppm Pt, 16.4 mg, 3.1 m g " a n d (vj 2 1
La 0 7Pb 0 3MnO 3, crystals, 1600 ppm Pt, 16.3 mg, 2.0 m g .
(b) DTA curves for the catalytic2 oxidation
of CO using
-1
Lae0 5Sr 0 5MnO
(the heating rate is
3, 15.7 mg, 28.6 m g
1
10 C min" in3 a gas1 stream of 2% CO, 2% 0 2 and 96%
N 2 at 500 cm m i n ) : (i) first cycle, no S 0 2 ; (ii) second
cycle, 150 ppm S 0 2 in gas stream; and (iii) third cycle,
150 ppm S 0 2 in gas stream

c o n t e n t , a n d t h e chemical c o n s e q u e n c e s inferred.
Evolved gas detection is a n a l o g o u s in t h a t t h e p r e s
ence of volatile species is detected b u t n o t their
specific n a t u r e . T h e r e a r e m a n y such q u a l i t a t i v e detec
t o r s t h a t c a n b e used t o sense t h e e v o l u t i o n of volatile
p r o d u c t s (e.g., t h e r m a l c o n d u c t i v i t y , g a s density,
flame i o n i z a t i o n , b r o a d - b a n d optical a t t e n u a t i o n ,
etc.). Evolved gas analysis ( E G A ) , h o w e v e r , utilizes
techniques t h a t a r e c a p a b l e of specifically a n a l y z i n g
the evolved gas (e.g., F o u r i e r t r a n s f o r m infrared
s p e c t r o s c o p y ( F T I R ) , gas c h r o m a t o g r a p h y ( G C ) ,
m a s s s p e c t r o m e t r y ( M S ) , etc.). D e t e c t o r s sensitive t o

510

1000

T e m p e r a t u r e (C)

Figure 7
-1
D T A curves of Ba 2YCu 30 7 at 10 C m i n in various
atmospheres

only a single species (e.g., d e w - p o i n t o r oxygen a n a

lyzers) a r e also used.
E m a n a t i o n t h e r m a l analysis ( E T A ) is a subclass of
E G A . A r a d i o a c t i v e gas is i n c o r p o r a t e d i n t o t h e
sample during preparation or by subsequent implan
t a t i o n . T h e radioactivity of t h e gas s t r e a m p a s s i n g
o v e r t h e s a m p l e is m o n i t o r e d a s t h e t e m p e r a t u r e is
raised. If t h e s a m p l e u n d e r g o e s a p h a s e t r a n s f o r m a
t i o n there is a s u d d e n release of g a s a n d a p e a k in t h e
radioactivity. A s t h e surface a r e a a n d p o r o s i t y of t h e
s a m p l e c h a n g e s , so d o e s t h e r a t e of e v o l u t i o n . T h i s
t e c h n i q u e is reviewed b y Balek (1987).
M o s t often E G A is c o m b i n e d with T G o r D T A /
D S C . T h e r e is also e q u i p m e n t designed solely for
E G A , such a s pyrolysis a t t a c h m e n t s for G C o r G C M S . I n these t e c h n i q u e s , t h e gas is usually a t a t m o s
p h e r i c p r e s s u r e . M S , h o w e v e r , requires t h a t t h e p r e s
4
sure be 1 0 " t o r r o r less, so t h a t a leak system is
required between the sample and the M S . Alternati
vely, w h e n less volatile species a r e of interest the
s a m p l e m a y b e d e c o m p o s e d in a v a c u u m t h r o u g h
h e a t i n g b y a laser b e a m ( L u m 1977) o r a small furnace
( G a l l a g h e r 1978).
3.2 Application

of EGA

T h e r e d u c t i o n of oxides b y h y d r o g e n offers a n o p p o r
t u n i t y t o use a specific g a s d e t e c t o r for H 2 0 ( R o w e et
al. 1983). T h e small r e a c t o r p a c k a g e used in this
research w a s c o n v e n i e n t t o o p e r a t e b e t w e e n t h e poles
of a n e l e c t r o m a g n e t in o r d e r t o d e t e r m i n e t h e effect of
a n e x t e r n a l m a g n e t i c field o n t h e r a t e of r e a c t i o n . T h e
m i n e r a l c o m p o n e n t s in a s b e s t o s v a r y c o n s i d e r a b l y
from o n e t o a n o t h e r . A T G m e t h o d h a d been p r o
p o s e d for analysis; h o w e v e r , E G A analysis b y M S
revealed t h e p r o b l e m s associated with s o m e of the
u n d e r l y i n g a s s u m p t i o n s ( K h o r a m i et al. 1984).
T h e laser h e a t i n g s c h e m e m e n t i o n e d in Sect. 3.1
w a s used b y L u m a n d Feinstein (1981) t o s t u d y the
d e c o m p o s i t i o n of a N o v o l a c e p o x y used t o e n c a p s u
late s e m i c o n d u c t o r s . A n isometric p l o t of t h e t o t a l ion
c u r r e n t a n d m a s s i o n profiles o v e r t h e r a n g e of a t o m i c

Thermal

Analysis:

Recent

Developments

e v o l u t i o n c a n also be o b s e r v e d in F i g . 9, w h e r e t h e
p e a k s n e a r 300 C c o r r e s p o n d w i t h t h e a m o r p h o u s - t o crystalline p h a s e t r a n s i t i o n revealed b y D S C .

4. Dynamic Mechanical
Thermodilatometry

Analysis

4.1 General and Instrumental

Temperature (C)

Figure 8
Isometric plot of mass profiles of evolved gases vs
temperature for Novolac epoxy

masses from 12 t o 122 a s a function of t e m p e r a t u r e

a p p e a r s in F i g . 8. S o m e of t h e m a s s n u m b e r s d u e t o
the e v o l u t i o n of N O a n d p h e n o l a r e identified, while
speculation r e g a r d i n g o t h e r m a s s f r a g m e n t s a n d t h e
m e c h a n i s m of t h e pyrolysis w a s m a d e .
T h e high sensitivity of M S c a n b e effectively u s e d t o
s t u d y t h e very initial stages of a d e c o m p o s i t i o n , s u c h
as for I n P b y G a l l a g h e r a n d C h u (1982). Similarly, t h e
sensitivity is i m p o r t a n t for t h e s t u d y of t h i n films
w h e r e large a m o u n t s of inert s u b s t r a t e m a t e r i a l a r e
involved. K i n s b r o n et al. (1979) s h o w e d h o w t h i n gold
electrodes reacted with t h e u n d e r l y i n g ( G a A l ) A s t o
release arsenic while f o r m i n g a g a l l i u m - g o l d eutectic.
D u n c a n et al. (1988) c o m b i n e d E G A b y M S w i t h
nuclear magnetic resonance ( N M R ) to characterize
a m o r p h o u s h y d r o g e n a t e d b o r o n nitride films. F i g u r e
9 s h o w s M S - E G A results f r o m s p u t t e r e d t h i n films of
T a S i 2 (Levy a n d G a l l a g h e r 1985). I n p r o d u c t i o n , these
devices w e r e e n c a p s u l a t e d w i t h a silica-based glass
w h i c h w a s h e a t e d t o a b o u t 1000 C t o flow evenly.
D u r i n g this p r o c e s s , blisters o c c u r r e d w h i c h w e r e
t r a c e d b y E G A t o t h e release of o c c l u d e d a r g o n
t r a p p e d d u r i n g s p u t t e r i n g . P r e p a r a t i o n w a s modified
t o r e d u c e t h e h i g h - t e m p e r a t u r e a r g o n p e a k a n d solve
t h e p r o b l e m . T h e effect of a p h a s e t r a n s i t i o n o n gas

and

Considerations

A typical d y n a m i c m e c h a n i c a l analysis ( D M A )
a p p a r a t u s is s h o w n schematically in F i g . 10 ( W e n d l a n d t a n d G a l l a g h e r 1981). T h e a m o u n t of energy
necessary t o m a i n t a i n t h e s a m p l e in r e s o n a n t oscilla
t i o n a t c o n s t a n t a m p l i t u d e is p r o p o r t i o n a l t o t h e
e n e r g y lost d u e t o i n t e r n a l friction. T h e driven s a m p l e
a r m is displaced several t e n t h s of a millimeter a n d
released t o s t a r t t h e oscillation. A feedback m e c h a n
ism from t h e linear t r a n s f o r m e r t o t h e driver m a i n
tains t h e a m p l i t u d e of oscillation. D M A is p r i m a r i l y
used in p o l y m e r science t o s t u d y relationships
b e t w e e n s t r u c t u r e a n d p r o p e r t i e s . T h e difference
b e t w e e n a n e l a s t o m e r a n d a stiff plastic c a n b e readily
seen in a p l o t of t h e m o d u l u s vs t e m p e r a t u r e . T h e
v a r i o u s p e a k s in t h e loss ( t a n ) c o r r e l a t e with t o u g h
ness a n d d a m p i n g , w h i c h a r e of g r e a t i m p o r t a n c e in
e l a s t o m e r s . D e t e r m i n i n g t h e frequency a n d t e m p e r a
t u r e d e p e n d e n c e for i n t e r n a l m o t i o n s within p o l y m e r s
is v a l u a b l e in d e t e r m i n i n g t h e n a t u r e of c h a i n seg
m e n t s , crystallinity, plasticizers, a n i s o t r o p i c p r o p e r
ties a n d so o n .
T h e r m a l e x p a n s i o n is a p r o p e r t y of g r e a t t e c h n o l o
gical i m p o r t a n c e . It d e t e r m i n e s w h e t h e r p a r t s will
m a i n t a i n their a l i g n m e n t , c o n t i n u e t o a d h e r e , o r
possibly b i n d as t h e t e m p e r a t u r e shifts. A s t h e t e m
p e r a t u r e varies, c h a n g e s in length o c c u r discontin u o u s l y a t a first-order p h a s e t r a n s i t i o n o r as a
c h a n g e in t h e slope for h i g h e r - o r d e r t r a n s f o r m a t i o n s
such as t h e glass t r a n s i t i o n . T h e s h r i n k a g e of a
m a t e r i a l is o n e of t h e m o s t c o m m o n m e t h o d s for
following t h e sintering p r o c e s s .
4.2 Applications of DMA and
Thermodilatometry
C o m p o s i t e s a r e c u r r e n t l y a fertile field of study. T h e
i n t e r r e l a t i o n of time a n d t e m p e r a t u r e is evident in t h e
D M A results for t h e c u r e p r o c e s s of a g r a p h i t e
e p o x y " p r e p r e g " for m a k i n g a fiber-reinforced c o m
posite, p r e s e n t e d in F i g . 11. T h e m o d u l u s a n d reso
n a n t frequency initially decrease a s t h e t e m p e r a t u r e is
raised. T h e n , u n d e r i s o t h e r m a l c o n d i t i o n s , t h e m o d u
lus c o n t i n u e s t o rise as t h e c u r e r e a c t i o n p r o c e e d s .
T h e r m a l e x p a n s i o n h a s b e e n successful in s t u d y i n g
several aspects of L i N b 0 3 . Since t h e m a t e r i a l is used
for e l e c t r o o p t i c switching, t h e p r e s e r v a t i o n of optical
a l i g n m e n t w i t h i n t h e device p a c k a g e is crucial. Be
sides p r o v i d i n g critical e x p a n s i o n d a t a for v a r i o u s
device c o m p o n e n t s , t h e r m a l e x p a n s i o n w a s used t o
detect subtle t r a n s i t i o n s n e a r a m b i e n t t e m p e r a t u r e .
T h e Tc for a l m o s t s t o i c h i o m e t r i c m a t e r i a l , t h a t is, only
511

Thermal

Analysis:

Recent

Developments

10.0
9.0

()

8.0
7.0
6.0
5.0

<

<

600

800

1000

1000

1200

1200

T e m p e r a t u r e (C)

T e m p e r a t u r e (C)

<

200

400

600

800

1000

1200

T e m p e r a t u r e (C)

4.8

(e)

4.4
4.0
3.6
3.2
2.8
2.4

2.0|

<

<

1.6

l.2|
0.8

0.4|

400

T e m p e r a t u r e (C)

"

600

800

1000

1200

T e m p e r a t u r e (C)

Figure 9
EGA of trapped gases in thin films of sputtered TaSi2: (a) hydrogen, (b) nitrogen, (c) oxygen, (d) water vapor and
(e) argon

slightly lithium deficient, is w h e r e t h e o n s e t of m e l t i n g

obscures t h e t r a n s i t i o n in D T A . It w a s , h o w e v e r ,
successfully m e a s u r e d b y t h e r m o d i l a t o m e t r y ( T D )
( G a l l a g h e r et al. 1988b).
T h e t e n d e n c y of s o m e h i g h - T c s u p e r c o n d u c t o r s t o
t a k e u p large a m o u n t s of oxygen w a s described in
512

Sect. 1.2. T h i s e x c h a n g e of o x y g e n leads t o large

c h a n g e s in e x p a n s i o n u n d e r i s o t h e r m a l c o n d i t i o n s a s
t h e p a r t i a l p r e s s u r e of oxygen is c h a n g e d o v e r t h e
s a m p l e . It is p a r t i c u l a r l y interesting t o n o t e t h a t , while
t h e u p t a k e of o x y g e n in t h e B a 2 Y C u 3 0 7 system
( O ' B r y a n a n d G a l l a g h e r 1987) leads t o a c o n t r a c -

Thermal

Electromechanical
transducer

Analysis:

Recent

Developments

Counter
weight
S a m p l e ~|

Thermocouple

J W

JL

Flexure pivots
.c

IOH

Furnace

Driver

Frequency
display

1000

Damping
display

Programmer

Recorder

t h
Figure 70
Schematic of the Du Pont Model 981 D M A module

40

41

81

121

1400

1600

Figure 12
Sintering behavior of Ti0 2-coated A1 20 3 spheres at
50Cmin~' in air

5. The Use of Feedback

tion, t h e o p p o s i t e effect is t r u e for t h e P b 2 S r 2 Y C u 3 0 8
system.
M o d e r n m e t h o d s of c e r a m i c synthesis frequently
start from a q u e o u s s o l u t i o n a n d p r o c e e d via a p r e c u r
sor c o m p o s i t i o n t o t h e desired p r o d u c t . O k a m u r a et
al. (1986) utilized a hydrolysis p r o c e s s t o p r e p a r e
m i c r o s p h e r e s of A 1 2 0 3 c o a t e d with T i 0 2 . T h e s e
spheres p a c k e d well in t h e p r e s i n t e r i n g c o m p a c t . T h e
sintering stage w a s studied b y d i l a t o m e t r y a n d t h e
s h r i n k a g e as a function of t e m p e r a t u r e is s h o w n in
Fig. 12. T h e relatively r a p i d densification is o b v i o u s
a n d t h e a p p a r e n t excessive e x p a n s i o n a r o u n d 1400 C
is d u e t o t h e i n c o m p l e t e r e a c t i o n a t t h a t stage. T h e
c o m b i n e d densities of a l u m i n a a n d rutile a r e g r e a t e r
t h a n t h a t of t h e final a l u m i n u m t i t a n a t e a n d t h e
m a t e r i a l e x p a n d s s o m e w h a t a s t h e r a t e of r e a c t i o n
exceeds t h e r a t e of sintering n e a r t h e e n d .

1200

T e m p e r a t u r e (C)

161

201

Time

241

281

321

361

401

441

(min)

Figure 11
DMA results for a graphite-epoxy prepreg (courtesy of
Dupont Instruments)

in Thermal

Analysis

C o n t r o l l i n g t h e r a t e of h e a t i n g by feedback from t h e
p r o c e s s v a r i a b l e of interest p r o d u c e results closer t o
e q u i l i b r i u m (i.e., less influenced b y m a s s o r t h e r m a l
t r a n s p o r t ) . A n e x a m p l e from t h e review b y P a u l i k a n d
P a u l i k (1986) is p r e s e n t e d in F i g . 13. P o t a s s i u m
h y d r o g e n c a r b o n a t e is d e c o m p o s e d a t a h e a t i n g r a t e
_1
of 3 C m i n d u r i n g t e m p e r a t u r e r a n g e s w h e r e there
is insignificant weight loss a n d a t t h e r a t e yielding
7
_1
during the decomposition
about 3 * 1 0 ~ k g m i n
stages. C u r v e s (i) a n d (ii) s h o w t h e t e m p e r a t u r e a n d
weight, respectively, as a function of time, while curve
(iii) s h o w s t h e resulting weight vs t e m p e r a t u r e p l o t in
c o m p a r i s o n with t h e c o n v e n t i o n a l T G , c u r v e (iv).
T h e r e is greatly e n h a n c e d r e s o l u t i o n evident in t h e
" q u a s i i s o t h e r m a l " p l o t . R o u q u e r o l (1964) h a s
d e m o n s t r a t e d t h a t similar benefits c a n b e derived
b y u s i n g feedback from a p r e s s u r e sensor t o c o n t r o l
t h e r a t e of h e a t i n g . T h i s is t h e a n a l o g o u s s i t u a t i o n
based on E G A . These m e t h o d s provide a better
u n d e r s t a n d i n g of t h e t r u e processes t a k i n g place d u r
ing d e c o m p o s i t i o n .
T h i s s a m e a p p r o a c h c a n b e utilized in t e c h n o l o g y t o
p r o v i d e a b e t t e r p r o d u c t a t t h e expense of less energy.
H u c k a b e e a n d P a l m o u r (1972) d e m o n s t r a t e d " r a t e c o n t r o l l e d s i n t e r i n g " w h i c h n o t only allowed for a
d e n s e r finer-grained sintered p r o d u c t b u t also saved
energy by reducing the time-temperature needed to
obtain that superior microstructure. This was
achieved b y p r e d e t e r m i n i n g t h e o p t i m u m r a t e of
s h r i n k a g e t h a t w o u l d m a i n t a i n a n o p e n p o r o s i t y so
t h a t a m i n i m u m of t r a p p e d p o r e s w o u l d o c c u r d u r i n g
t h e early stage of sintering. T h e s e t r a p p e d p o r e s a r e
p a r t i c u l a r l y difficult t o e l i m i n a t e in t h e latter stages of
sintering. T h e t e m p e r a t u r e vs t i m e c u r v e (similar t o
c u r v e 1 in F i g . 13) t h a t p r o v i d e d this c o n t r o l l e d
s h r i n k a g e w a s r e c o r d e d in t h e p r e l i m i n a r y e x p e r i m e n t
a n d u s e d for s u b s e q u e n t p r o d u c t i o n .

513

Thermal

Analysis:

Recent

Developments

200

100

Time (min)

KHC03

0
\
3
Q-TG

20

\ t g
\
\
k
f>

2 c o 3

150

200

Temperature (C)

Figure 13
Dehydration of K H C 0 3 measured by TG under
quasi-isothermal (Q) conditions

Bibliography
Agarwal , N o h J S, Schwartz J A, Davini 1987 Effect
of surface acidity of activated carbon on hydrogen stor
age. Carbon 25: 219-26
Aylmer D, Rowe W 1982 Thermo-magneto-gravimetric
analysis of pyrite in coal and lignite. In: Miller (ed.)
1982 Proc. 7th Int. Conf. Thermal Imaging, Vol. 2. Wiley,
Chichester, UK, pp. 1270-5
Balek V 1987 Emanation thermal analysis: a status report.
Thermochim Acta 110: 222-35
Boersma S L 1955 Theory of differential analysismeasure
ment and interpretation. / . Am. Ceram. Soc. 38: 281-7
Bracconi P, Gallagher 1972 Phase diagram of a nickelzinc ferrite of composition: N i 0 6 8 Z
5 n 0 1 7F
7 e 2 1 3O
8 4 +r J. Am.
Ceram. Soc. 62: 171-6
Charles R G 1982 Thermomagnetic analysis as a means for
following corrosion reactions in sealed systems. In: Miller
(ed.) 1982 Proc. 7th Int. Conf. Thermal Imaging, Vol. 1.
Wiley, Chichester, UK, pp. 264-71

514

Duncan , Levy R A, Gallagher , Walsh 1988

Structural characterization of boron nitride films. J. Appl.
Phys. 64: 299(M
Gallagher 1978 An evolved gas analysis system. Ther
mochim. Acta 26: 175-83
Gallagher 1987 Characterization of Ba 2YCu 30 Jt as a
function of oxygen partial pressure. Part I: Thermoanalytical measurements. Adv. Ceram. Mater. 2: 632-9
Gallagher , Chu S G 1982 Kinetics of the dissociation
on InP under vacuum. J. Phys. Chem. 86: 3246-50
Gallagher , Grader G S, O'Bryan 1988a Some
effects of C 0 2 , CO, and H 2 0 upon the properties of
Ba 2YCu 30 7. Mater. Res. Bull. 23: 1491-9
Gallagher , Gyorgy 1986 Curie temperature
standards for thermogravity. The effect of magnetic field
strength and comparison with melting point standards
using Ni and Pb. Thermochim. Acta 109: 19-206
Gallagher , Gyorgy , Schrey F, Hellman F 1987b
Use of thermomagnetometry to follow reactions of thin
films. Thermochim. Acta 121: 231-40
Gallagher , Johnson D W, Vogel 1976 Examples of
the use of DTA for the study of catalytic activity and
related phenomena. In: Rylander . Greenfield (eds.)
1976 Catalysis in Organic Synthesis. Academic Press, New
York
Gallagher , O'Bryan , Brandle C D 1988b Applica
tion of thermal analysis to study the crystal growth.
Thermochim. Acta 133: 1-10
Gallagher , O'Bryan , Cava R J, James A C W P,
Murphy D W, Rhodes W W, Krajewski J J, Peck
W F, Waszczak J V 1989 Oxidation-reduction of
2 8 2 , _ 3 _ ^ 0 8 Chem. Mater. 1: 277
Gallagher , O'Bryan , Sunshine S A, Murphy D W
1987a Oxygen stoichiometry in Ba 2YCu 3O x. Mater. Res.
Bull. 22: 995-1006
Gallagher , Warne S S 1981 Thermomagnetometry and
the thermal decomposition of siderite. Thermochim. Acta
43: 253-67
Grader G S, Gyorgy , Gallagher , O'Bryan ,
Johnson D W, Sunshine S A, Zahurak S M, Jin S,
Sherwood R C 1988 Crystallographic, thermodynamic
and transport properties of B i 2S r 3_ xC a xC u 20 8 +i supercon
ductor. Phys. Rev. 38: 757-60
Haglund 1982 Curie temperature of alloys, its measure
ment and technical importance. J. Therm. Anal. 25: 21-43
Holman R L 1974 Novel uses of the thermomicrobalance in
the determination of nonstoichiometry in complex oxide
systems. J. Vac. Sci. Technol. 11: 43-9
Howard J 1973 DTA for control of stability in polyolefin
wire and cable compounds. Polym. Eng. Sci. 13: 429-34
Huckabee L, Palmour 1972 Rate controlled sintering
of fine grained A1 20 3. Am. Ceram. Soc. Bull. 51: 574-6
Khorami J, Choquette D, Kimmerle F M, Gallagher
1984 Interpretation of EGA and DTG analysis of crysotile asbestos. Thermochim. Acta 76: 87-96
Kinsbron E, Gallagher , English A 1979 Dissociation
of (GaAl) As during alloying of gold contact films. SolidState Electron. 22: 517-24
Kosak J 1976 Catalyst activity via thermal analysis. In:
Rylander , Greenfield (eds.) 1976 Catalysis in
Organic Synthesis. Academic Press, New York, pp. 13748
Levy R A, Gallagher 1985 Argon entrapment and
evolution in sputtered TaSi 2 films. J. Electrochem. Soc.
132: 1986-91

Thermal
Lum R 1977 Direct analysis of polymer pyrolysis using
laser microprobe techniques. Thermochim. Acta 18: 73-94
Lum R M, Feinstein L G 1981 Investigation of the molecu
lar processes controlling corrosion failure mechanisms in
plastic encapsulated semiconductor devices. Microelectron. Reliab. 21: 15-31
Mackenzie R C 1980 Differential thermal analysis and
differential scanning calorimetry. Similarities and dif
ferences. Anal. Proc. (London) 17: 217-20
Morros S A, Stewart D 1976 Automated and computerized
system for purity determination by differential scanning
calorimetry. Thermochim. Acta 14: 13-24
O'Bryan , Gallagher 1987 Characterization of
Ba 2YCu 30 Jt as a function of oxygen partial pressure. Part
II: Dependence of the O-T transition on oxygen content.
Adv. Ceram. Mater. 2: 642-8
Okamura H, Barringer A, Bowen 1986 Preparation
and sintering of monosized A1 20 3Ti0 2 composite
powder. J. Am. Ceram. Soc. 69: C22-24
Ozawa 1988 Application of thermal analysis to kinetic
study of superconducting oxide formation. Thermochim.
Acta 133: 11-16
Paulik F, Paulik J 1986 Thermoanalytical examination
under quasi-isothermal-quasi-isobaric conditions. Ther
mochim. Acta 100: 23-59
Rouquerol J 1964 Thermal analysis under low pressure and
constant rate of decomposition. Bull. Soc. Chim. Fr. 1964:
31-2
Rowe R, Gallagher , Gyorgy 1983 Establishing
the absence of any influence by an external analysis field
upon the intrinsic rate of reduction of magnetite by
hydrogen. / . Chem. Phys. 79: 353-6
Schubart B, Knothe 1972 A new thermogravimetric
instrument for chemical analysis with weighing com
partment hermetically separated. In: Gast (ed.) 1972
Progress in Vacuum Microbalance Techniques, Vol. 1.
Heyden, Norwich, UK, pp. 207-15
Warne S S, Gallagher 1987 Thermomagnetometry.
Thermochim. Acta 110: 269-79
Wendlandt W W, Gallagher 1981 Instrumentation. In:
Turi A (ed.) 1981 Thermal Characterization of Poly
meric Materials. Academic Press, New York, Chap. 1
P. K. Gallagher
[Ohio S t a t e University, C o l u m b u s ,
Ohio, USA]

Thermal Wave Imaging

T h e r m a l wave imaging ( T W I ) refers t o a family of
m e t h o d s which use changes in t e m p e r a t u r e p r o d u c e d
by a temporarily o r positionally m o d u l a t e d h e a t source
to determine spatial variations in the c o m p o s i t i o n ,
s t r u c t u r e a n d p r o p e r t i e s of a solid m a t e r i a l . A n i m
p o r t a n t aspect of T W I is its ability t o i m a g e n o t o n l y
t h e surface of a m a t e r i a l b u t , in s o m e i m p o r t a n t cases,
subsurface features as well. I n a d d i t i o n , t h e i m a g e
c o n t r a s t processes p r e s e n t in T W I differ in i m p o r t a n t
respects from o t h e r i m a g i n g m e t h o d s u s e d for m a t e r
ials c h a r a c t e r i z a t i o n a n d h e n c e c a n p r o v i d e q u a l i t a t i
vely different i n f o r m a t i o n a b o u t t h e specimen. T W I
h a s also b e e n used t o c h a r a c t e r i z e c o m b i n a t i o n s of

Wave

Imaging

m a t e r i a l s used in engineering a p p l i c a t i o n s including

multilayered materials and composites.
I m a g e c o n t r a s t in T W I is c o n t r o l l e d b o t h b y local
h e a t insertion from t h e s o u r c e a n d by h e a t flow in t h e
specimen. T h e s e factors a r e related t o t e m p e r a t u r e
t h r o u g h t h e t h e r m a l diffusion e q u a t i o n . T h i s e q u a t i o n
associates a c h a n g e in t h e v o l u m e i n t e r n a l energy of a
s a m p l e m e a s u r e d b y t e m p e r a t u r e w i t h t h e net
energy flux i n t o t h a t v o l u m e element. A s a result, the
factors w h i c h lead t o i m a g e f o r m a t i o n in T W I are: a
s o u r c e w h i c h delivers energy t o a s a m p l e ; t h e conver
sion of s o m e o r all of t h e d e p o s i t e d energy t o heat;
t h e r m a l a n d possibly m a s s diffusion w h i c h modify t h e
initial t e m p e r a t u r e field c r e a t e d b y t h e source; a n d
m e a s u r e m e n t of a t e m p e r a t u r e - d e p e n d e n t p r o p e r t y of
t h e s a m p l e o r its i m m e d i a t e e n v i r o n m e n t b y a n a p p r o
p r i a t e d e t e c t i o n system ( M u r p h y et al. 1986). A s this
classification suggests, m e m b e r s of t h e T W I family
a r e distinguished b y a specific c o m b i n a t i o n of h e a t i n g
s o u r c e a n d d e t e c t i o n m e t h o d . T h e principal sources
include optical a n d o t h e r e l e c t r o m a g n e t i c sources a n d
particle b e a m sources such as electron a n d ion b e a m s .
T h e spatial d i s t r i b u t i o n of energy w i t h i n a specimen
a n d t h e physical i n t e r a c t i o n s w h i c h describe energy
conversion to heat vary with the source a n d m a y vary
locally in t h e s a m p l e . T h e s e factors modify t h e tem
p e r a t u r e d i s t r i b u t i o n a n d t h r o u g h it t h e i n f o r m a t i o n
c o n t e n t of a n i m a g e . O n t h e d e t e c t i o n side, a variety
of m e t h o d s h a v e b e e n used, b a s e d o n a selected
physical p r o p e r t y of t h e specimen o r its i m m e d i a t e
e n v i r o n m e n t a n d o n t h e d e t e c t i o n t e c h n i q u e itself.
T h e choice of detection m e t h o d c a n also modify the
i n f o r m a t i o n c o n t e n t of a n i m a g e . A s a result, T W I
m e t h o d s , b r o a d l y defined, c a n b e u s e d t o d e t e r m i n e
b o t h t h e r m a l a n d n o n t h e r m a l characteristics of a
m a t e r i a l with a T W I m e t h o d selected for a specific
application.

7. The Temperature

Field in a Uniform

Layered

Solid
T o illustrate t h e general characteristics of t h e r m a l
wave imaging, consider the temperature distribution
p r o d u c e d b y a spatially u n i f o r m optical s o u r c e of
intensity I0 () w h i c h is a m p l i t u d e m o d u l a t e d a t a n
a n g u l a r frequency cwm. T h e r a t e of h e a t d e p o s i t i o n in a
layered solid w i t h a n u p p e r layer of thickness is
(,)

= - ( \ - R)I0 exp[j(o> -

c o m) i ] F e x p ( - z )

w h e r e is t h e d e p t h in t h e s a m p l e , R t h e reflectivity,
t h e a b s o r p t i o n coefficient a n d F t h e fraction of t h e
a b s o r b e d energy t h a t is c o n v e r t e d t o h e a t . G i v e n these
c o n d i t i o n s , t h e specimen t e m p e r a t u r e a t d e p t h c a n
b e d e t e r m i n e d using t h e o n e - d i m e n s i o n a l t h e r m a l
diffusion e q u a t i o n
2

d T,
.ldT/
H(z,t)

x
(z,r)-a
' _ ( * , , ) = - - ^

515

Thermal

Wave

Imaging

w h e r e is t h e t h e r m a l diffusivity, t h e t h e r m a l
c o n d u c t i v i t y a n d C t h e specific h e a t . T h e surface
t e m p e r a t u r e is ( M u r p h y et al. 1992):
,) =

0 ( 1 " R)FI0(a>)

{
2

\- \

2 e x p ( - L/(5 0)cosh(z/<5 0)
1 - T e x p ( - 2 L / ( 5 0)

r e x p ( - L / J 0)

\1+/Si0

= (/ Mn) '
a

0 5

1 - M

)]|

0)

w h e r e 0
is t h e t h e r m a l diffusion l e n g t h
a n d is a n interlayer t h e r m a l m i s m a t c h factor.
Several i m p o r t a n t p r o p e r t i e s of t h e r m a l w a v e
m e t h o d s a r e c o n t a i n e d in E q n . (1).
1.1 Thermal Depth

Profiling

T(Q,co,com) is a p h a s o r possessing m a g n i t u d e a n d
p h a s e a t t r i b u t e s . If L / < 5 0> 1 , t h e n | ( 0 , , ) | a n d
[,,^],
t h e p h a s e of , , ^ , b e c o m e insen
sitive t o t h e presence of t h e lower layer while if
L/S0< 1, b o t h reflect t h e p r e s e n c e of t h e l o w e r layer.
T h i s c o n d i t i o n allows t h e r m a l d e p t h profiling of b u r
ied s t r u c t u r e s t h r o u g h t h e d e p e n d e n c e of | ( 0 , , ) |
a n d | T ( 0 , c o , G ) m) ] o n co m a n d h e n c e o n 0.
[T(0,co,com)] offers s o m e s u b s t a n t i a l a d v a n t a g e s in
T W I since it is insensitive t o c h a n g e s in s a m p l e
reflectivity. S u b s u r f a c e s t r u c t u r e s w h i c h m o d i f y t h e
flow of h e a t in t h e s p e c i m e n c a n b e i m a g e d a n d t h e i r
d e p t h d e t e r m i n e d t h r o u g h t h e d e p e n d e n c e of t h e r m a l
images o n com. A p p l i c a t i o n s i n c l u d e i m a g i n g of v o i d s ,
interfaces a n d regions w h e r e i n t e r l a m i n a r d i s b o n d i n g
o c c u r s in c o m p o s i t e m a t e r i a l s .
1.2 Thermal

Spectroscopy

(0,) also d e p e n d s o n (). By inversion of E q n . (1),

the a b s o r p t i o n s p e c t r u m () c a n b e d e t e r m i n e d even
for o p a q u e specimens p r o v i d e d 0 < 1. F o r highly
a b s o r b i n g m a t e r i a l s (>\)
this d e m a n d s t h a t
S0<\
(large ) . W h e n 0 > 1, (0,) is i n d e p e n d e n t of
a n d v a r i a t i o n s in t h e t h e r m a l p r o p e r t i e s of a specimen
c a n be d e t e r m i n e d w i t h o u t a d m i x t u r e of a spectral
component.
1.3 Extension to Other Electromagnetic
Sources
T h e s e results a r e a p p l i c a b l e t o a n y e l e c t r o m a g n e t i c
s o u r c e for w h i c h e n e r g y d e p o s i t i o n is d e t e r m i n e d b y
t h e e x p o n e n t i a l a b s o r p t i o n profile a s s u m e d in E q n .
(1). H o w e v e r , t h e a b s o r p t i o n m e c h a n i s m s v a r y a c r o s s
the electromagnetic spectrum a n d the interpreta
tion of t h e i m a g e s c h a n g e s w i t h . F o r e x a m p l e , in
t h e x-ray region a b s o r p t i o n involves t r a n s i t i o n s of
i n n e r shell e l e c t r o n s a n d for several m e t a l s t h e s a m p l e

516

t e m p e r a t u r e as a function of x-ray w a v e l e n g t h exhi

bits E X A F S - l i k e s t r u c t u r e n e a r t h e edge. T W I
i m a g e s o b t a i n e d u s i n g m o n o c h r o m a t i c r a y s c a n also
distinguish t h e c o m p o s i t i o n of b u r i e d regions of dif
ferent m e t a l l i z a t i o n in a m i c r o c i r c u i t o n t h e basis of
this p r o p e r t y . A s a s e c o n d e x a m p l e , infrared s o u r c e s
excite v i b r a t i o n a l t r a n s i t i o n s in a specimen. T h i s
p e r m i t s i m a g i n g of selected m o l e c u l a r species in
f a v o u r a b l e cases. T h e general principle t o b e d r a w n
f r o m these e x a m p l e s is t h a t s o u r c e - s p e c i m e n i n t e r a c
t i o n s a r e a basis for i m a g e c o n t r a s t in a d d i t i o n t o t h e
t h e r m a l c o n t r a s t d e s c r i b e d previously.

2.

Imaging

A d e s c r i p t i o n of t h e T W I of m a t e r i a l s requires t h a t
E q n . (1) b e modified t o i n c l u d e spatially d i s t r i b u t e d
s o u r c e s a n d t h r e e - d i m e n s i o n a l h e a t flow in t h e speci
m e n . H o w e v e r , t h e r m a l d e p t h profiling, s p e c t r o s c o p y
a n d s o u r c e - d e p e n d e n t i m a g e c o n t r a s t a r e still p r e s e n t .
T w o g e n e r a l i m a g i n g f o r m a t s exist: spatially localized
h e a t i n g a n d spatially localized d e t e c t i o n . O f c o u r s e ,
b o t h m a y b e p r e s e n t s i m u l t a n e o u s l y (Tarn 1986).
2.1 Localized

Source

Imaging

A localized s o u r c e c r e a t e s a r e g i o n of excess t e m p e r a t
u r e w h o s e size is d e t e r m i n e d b y t h e spatial e x t e n t of
t h e s o u r c e a n d b y t h e r m a l diffusion. I m a g e s a r e
formed by scanning the source over the sample and
r e c o n s t r u c t i n g t h e t e m p e r a t u r e field from s t o r e d d a t a .
B o t h localized d e t e c t i o n , w h i c h m o n i t o r s (0,,) in a
small r e g i o n n e a r t h e s o u r c e , a n d n o n l o c a l i z e d detec
t i o n , w h i c h m o n i t o r s 3 ( 0 , ) a v e r a g e d o v e r t h e s a m
ple, c a n b e u s e d . H o w e v e r , in t h e first case b o t h
t e m p e r a t u r e a n d h e a t flow c a n b e d e t e r m i n e d b y
varying the separation distance between source a n d
d e t e c t o r . T h e lateral spatial r e s o l u t i o n for t h e i m a g i n g
of a b u r i e d feature is d e t e r m i n e d b y t h e r a t i o s SJRQ
a n d SJL w h e r e
is t h e size of t h e s o u r c e ( a s s u m e d
G a u s s i a n ) a n d L is t h e d i s t a n c e b e t w e e n d e t e c t o r a n d
s a m p l e feature. F o r i m a g i n g w h i c h m o n i t o r s t h e
surface t e m p e r a t u r e of t h e s p e c i m e n , L is t h e d e p t h of
t h e feature in t h e s a m p l e . F o r small L t h e r e s o l u t i o n is
a p p r o x i m a t e l y e q u a l t o RQ while for larger L t h e
r e s o l u t i o n is d e t e r m i n e d b y t h e g r e a t e r of S0 a n d RQ,
p r o v i d e d SJL > 1. A r e s o l u t i o n of t h e o r d e r of m i c
r o m e t e r s c a n b e achieved for n e a r - s u r f a c e features
w h e n a focused laser o r particle b e a m s o u r c e is used.
2.2 Generalized

Source

Imaging

A n o n u n i f o r m d i s t r i b u t i o n of h e a t c a n b e p r o d u c e d
b y u n i f o r m i l l u m i n a t i o n in a h e t e r o g e n e o u s s a m p l e
via spatially v a r y i n g a b s o r p t i o n o r s u b s e q u e n t ther
m a l diffusion. I m a g e f o r m a t i o n r e q u i r e s t h a t t h e
t e m p e r a t u r e b e m e a s u r e d u s i n g a localized d e t e c t o r o r
a d e t e c t o r a r r a y . F r o m t h e v i e w p o i n t of t h e t e m p e r a t
u r e field, t h e spatial r e s o l u t i o n w h i c h c a n b e achieved
is d e s c r i b e d b y t h e analysis in Sect. 2.1 a n d d e p e n d s

Thermal
o n ratios of t h e r m a l a n d physical lengths. T h e i m a g e
resolution, h o w e v e r , also d e p e n d s o n t h e d e t e c t i o n
m e t h o d selected as described in Sect. 3.

3. Detection

Methods

All m e t h o d s o f detecting t e m p e r a t u r e m o n i t o r a
physical p r o p e r t y of t h e s a m p l e o r its e n v i r o n m e n t .
T h e m o s t i m p o r t a n t p r o p e r t i e s in use for T W I a r e
infrared (ir) e m i t t a n c e , reflectivity, surface o r v o l u m e
strain, index o f refraction of t h e specimen o r a fluid in
t h e r m a l c o n t a c t w i t h t h e specimen a n d h e a t transfer
to a thin pyroelectric film sensor a t t a c h e d t o t h e
sample. T h e distinctive a s p e c t s o f several m e t h o d s a r e
s u m m a r i z e d in Sects. 3.1-3.2. T h e choice of m e t h o d is
i n t e n d e d t o illustrate h o w i m a g e c o n t r a s t a n d its
i n f o r m a t i o n c o n t e n t c a n c h a n g e with d e t e c t i o n
method.
3.1 Photothermal Radiometric
Methods
R a d i o m e t r i c T W I m o n i t o r s c h a n g e s in m o d u l a t e d ir
emission c a u s e d by t e m p e r a t u r e increases in local
regions of a n externally h e a t e d s a m p l e . T h e S t e f a n B o l t z m a n n law describes t h e t o t a l r a d i a n t e m i t t a n c e
4
Woi a b o d y a t t e m p e r a t u r e as W= w h e r e is
12
- 2
the S t e f a n - B o l t z m a n n c o n s t a n t (5.67 1 0 " W c m
4
K " ) a n d is t h e emissivity. A c h a n g e in s a m p l e
t e m p e r a t u r e p r o d u c e s a c h a n g e in r a d i a n t emit
3
tance \=4
ST w h e r e is t h e a m b i e n t t e m
p e r a t u r e of t h e specimen a n d W h a s been i n t e g r a t e d
3
over ir wavelength. T h e presence of t h e t e r m
implies t h a t this m e t h o d is potentially i m p o r t a n t for
h i g h - t e m p e r a t u r e i m a g i n g . Since d e t e c t i o n is typically
based o n H g C d T e , I n S b a n d o t h e r n a r r o w b a n d g a p
s e m i c o n d u c t o r s , o n l y a restricted b a n d of t h e e m i t t e d
wavelengths is actually detected. It is i m p o r t a n t t h a t
the emission d e p t h of t h e ir r a d i a t i o n in this d e t e c t i o n
b a n d be k n o w n for q u a n t i t a t i v e studies. A significant
a d v a n t a g e of this m e t h o d is t h e availability o f
infrared d e t e c t o r a r r a y s o r s c a n n e d d e t e c t i o n systems
which facilitate t h e i m a g i n g of large a r e a s . H o w e v e r ,
the spatial r e s o l u t i o n w h i c h c a n b e realized b y this
m e t h o d is limited by t h e d e t e c t i o n m e t h o d itself. F o r
ir imaging, t w o lateral spatial features s e p a r a t e d b y a
length d c a n be resolved only w h e n /d < 1 w h e r e is
the ir wavelength. Spatially v a r y i n g s a m p l e emissivity
c a n present a n o t h e r p r o b l e m for i m a g i n g since it c a n
a p p e a r as a noise b a c k g r o u n d . I n T W I t h e effect of
this v a r i a t i o n in s a m p l e emissivity c a n b e m i n i m i z e d
by t a k i n g r a t i o s of i m a g e s o b t a i n e d a t t w o t e m p e r a t
ures o r a t t w o closely spaced w a v e l e n g t h s p r o v i d e d
t h a t t h e emissivity is i n d e p e n d e n t of t e m p e r a t u r e over
the r a n g e o f t e m p e r a t u r e s used a n d t h a t n o localized
absorption bands are near the detection wavelengths.
3.2 Laser Detection Methods: Reflection and
Refraction
Laser detection m e t h o d s c a n m o n i t o r t e m p e r a t u r e -

Wave

Imaging

d e p e n d e n t c h a n g e s in s a m p l e reflectivity, index of
refraction a n d surface d e f o r m a t i o n , as well as index
c h a n g e s in a fluid in t h e r m a l c o n t a c t with t h e s a m p l e .
In laser thermoreflectance, t h e reflected intensity of a
p r o b e laser b e a m from a s a m p l e region h e a t e d by a
source is m e a s u r e d as a function of a n d r, the
distance b e t w e e n t h e s o u r c e a n d p r o b e b e a m centers,
h e r e a s s u m e d G a u s s i a n . T h i s intensity is modified b y
t e m p e r a t u r e - i n d u c e d c h a n g e s in t h e reflectivity a n d ,
in t h e case of s e m i c o n d u c t o r s , b y reflectivity c h a n g e s
induced by a photogenerated electron-hole plasma.
I m a g e f o r m a t i o n a n d i m a g e resolution a r e influenced
b y t h e t e m p e r a t u r e field, a s described previously, a n d
by carrier t r a n s p o r t a n d diffusion. A c o m p e t i t i o n
b e t w e e n t h e r m a l a n d p l a s m a effects m a y exist in s o m e
f r e q u e n c y - t i m e regimes ( F o u r n i e r et al. 1986). T o
analyze these effects, a n electron diffusion length
05
= [ y / J / c o J , w h e r e D is t h e diffusion coefficient,
m u s t b e i n t r o d u c e d . Special cases classified by the
r a t i o of t o a physical length in t h e s a m p l e a r e found.
A similar classification w a s described in Sect. 2 . 1 . T h e
resulting images c a n be selected t o exhibit principally
t e m p e r a t u r e d i s t r i b u t i o n effects, t h e e l e c t r o n - h o l e
p l a s m a d i s t r i b u t i o n effects o r effects associated with
the t e m p e r a t u r e d i s t r i b u t i o n derived from e l e c t r o n hole r e c o m b i n a t i o n . T h e spatial resolution for detec
tion using these laser m e t h o d s is d e t e r m i n e d by the
d i a m e t e r s of t h e s o u r c e a n d p r o b e b e a m s a n d surface
features s e p a r a t e d b y d > 1 p m c a n b e resolved.
W h e n t h e index of refraction is used for detection,
the index g r a d i e n t field p r o d u c e d by t h e source devi
ates a p r o b e b e a m . F o r o p a q u e s a m p l e s this field is in
the air a b o v e t h e s a m p l e a n d q u a n t i t a t i v e m e a s u r e
m e n t s of t h e s a m p l e t e m p e r a t u r e c h a n g e s c a n be m a d e
since t h e v a r i a t i o n of t h e index of refraction with
t e m p e r a t u r e is k n o w n . T h e t h e r m a l diffusivity c a n b e
d e t e r m i n e d in a local m e a s u r e m e n t ( K u o et al. 1989).
F o r t r a n s p a r e n t s a m p l e s , t h e index g r a d i e n t field of
t h e s a m p l e c a n be used as t h e deflecting agency a n d
t h e internal t e m p e r a t u r e d i s t r i b u t i o n a n d h e a t flow
measured. Thermal, plasma and other nonthermal
factors c a n c o n t r i b u t e t o t h e i m a g e s o b t a i n e d .
Surface strain as a p a r a m e t e r for t h e r m a l w a v e
d e t e c t i o n i n t r o d u c e s a d d i t i o n a l elements t o image
f o r m a t i o n a n d c o n t r a s t . First, surface strain c a n b e
monitored near the heating location or at a remote
l o c a t i o n via t h e elastic r e s p o n s e of t h e specimen. N e a r
the h e a t i n g l o c a t i o n , t h e r m a l e x p a n s i o n associated
with h e a t i n g n o r m a l l y causes a local bulge in the
surface of a p l a n a r s a m p l e w h i c h c a n b e detected by
interferometry o r b y d e v i a t i o n of a p r o b e b e a m .
D e t e c t i o n a t a r e m o t e l o c a t i o n o c c u r s t h r o u g h ultra
sonic w a v e p r o p a g a t i o n a t high co m o r t h r o u g h
q u a s i s t a t i c d e f o r m a t i o n a t low co m. D e t e c t i o n is b y a
piezoelectric t r a n s d u c e r c o n n e c t e d t o t h e specimen o r
by optical i n t e r f e r o m e t r y o r related techniques. In this
case, t h e elastic p r o p e r t i e s of t h e specimen c o n t r i b u t e
to the image contrast. As an example, granular mater
ials, including m e t a l s , s h o w e n h a n c e d g r a i n - b o u n d a r y

517

Thermal

Wave

Imaging

20

60

100

20

60

160

180

40

80

160

200

()

(/xm)

100

!20

140

180

x {))

20

60

100

140

180

()

Figure 1
Thermal wave images of closed vertical cracks in a single region of an aluminum sample: (a) magnitude and (b) phase
images obtained using transverse beam deflection; (c) magnitude image from normal beam deflection; and (d) magnitude
image from piezoelectric detection. The same focused, scanned laser source was used to obtain all four images. The
sample contained inclusions which appear as closed level contours in the images and a tightly closed vertical crack. The
inclusions labelled A allow different images to be correlated. The crack is evident in (a) and (b) but absent in (c) and (d).
Piezoelectric images obtained at higher modulation frequencies also show the crack. This set demonstrates how the
information content of a thermal wave image depends on the specific method used
c o n t r a s t w h e n t h e r m o e l a s t i c d e t e c t i o n is used, w h i c h
is n o t seen in t h e p u r e l y t h e r m a l case.
F i g u r e 1 s h o w s images of a c r a c k e d a l u m i n u m
s a m p l e o b t a i n w i t h different d e t e c t i o n m e t h o d s a n d
demonstrates how information content depends on
the detection method.
4. Particle

Sources

Particle b e a m sources exhibit a c o m p l e x d e p o s i t i o n of

energy with d e p t h in t h e specimen a n d with b e a m

518

p a r a m e t e r s . T h e y also exhibit n o n t h e r m a l i m a g e c o n
t r a s t effects w h e n u s i n g a n y of t h e T W I m e t h o d s
described previously. E l e c t r o n b e a m s were o n e of t h e
earliest of t h e T W I sources d e v e l o p e d a n d w h e n used
with elastic w a v e d e t e c t i o n , in a m e t h o d t e r m e d
s c a n n i n g electron a c o u s t i c m i c r o s c o p y ( S E A M ) , give
h i g h - r e s o l u t i o n i m a g e s of t h e p r o p e r t i e s of m a t e r i a l s .
A p p l i c a t i o n s include visualization of t h e grain struc
t u r e in t h e heat-affected z o n e of welds a n d i m a g i n g of
t h e d i s t r i b u t i o n of d o p a n t ions in s e m i c o n d u c t o r s .
H o w e v e r , a satisfactory q u a n t i t a t i v e t h e o r y of i m a g e

Thermal

Wave

Imaging

Figure 2
Electron source TWI of subsurface structure: (a) SEM and (b) SEAM at beam voltages of 5 kV showing the surface of an
integrated circuit; (c) SEM at 30 kV continues to image the surface features whereas (d) SEAM at 30 kV images structures
located below the specimen surface
f o r m a t i o n u s i n g elastic w a v e d e t e c t i o n h a s n o t yet
been d e v e l o p e d a n d t h e m e t h o d is limited t o q u a l i t a
tive investigations of m a t e r i a l s p r o p e r t i e s . R e c e n t l y ,
b o t h r a d i o m e t r i c a n d laser deflection m e t h o d s h a v e
been a p p l i e d t o t h e s t u d y of electron b e a m - m a t e r i a l s
interactions. These thermal m e t h o d s can provide
q u a n t i t a t i v e i n f o r m a t i o n a b o u t a specimen.
4.1 Electron Injection and
Thermalization
Time-resolved m e a s u r e m e n t s of electron injection,
internal i o n i z a t i o n a n d t h e r m a l i z a t i o n h a v e b e e n

o b t a i n e d for s e m i c o n d u c t o r s , u s i n g r a p i d l y m o d u
lated b e a m s of e l e c t r o n s . T h e specimen r e s p o n s e is
m o n i t o r e d b y t h e deflection of a p r o b e laser b e a m
w h o s e p o s i t i o n is s c a n n e d t h r o u g h t h e i n t e r n a l index
g r a d i e n t field f o r m e d b y b o t h electron density a n d
t h e r m a l g r a d i e n t s . T h e results a r e i n t e r p r e t e d using a
modified version of E q n . (1) t o d e t e r m i n e t h e electron
d i s t r i b u t i o n inside t h e specimen, t h e t h e r m a l distribu
t i o n function H(r, i) a n d t h e r e l a x a t i o n times. D y n a
m i c i m a g e s h a v e been m a d e .
F i g u r e 2 c o m p a r e s surface a n d subsurface i m a g e s

519

Thermal

Wave

Imaging

of a microcircuit using s c a n n i n g electron m i c r o s c o p y

(SEM) and SEAM.

5.

Summary

T W I offers a m e n u of o p p o r t u n i t i e s for m a t e r i a l s
c h a r a c t e r i z a t i o n . T h e c o n t r a s t m e c h a n i s m s available
for i m a g e f o r m a t i o n include: (a) a specific i n t e r a c t i o n
between s o u r c e a n d specimen w h i c h p e r m i t s c o n t r a s t
o n the basis of c o m p o s i t i o n o r t h e energy d e p o s i t i o n
with d e p t h in t h e s a m p l e ; (b) t h e r m a l c o n t r a s t , w h i c h
is b a s e d o n t h e t h e r m a l diffusion length o r time w h i c h
d e p e n d s o n the t h e r m a l p a r a m e t e r s of t h e specimen
and on the separation distance between thermal
source a n d object; a n d (c) d e t e c t o r c o n t r a s t , w h i c h
d e p e n d s o n t h e physical p a r a m e t e r selected t o be a
m e a s u r e of specimen t e m p e r a t u r e . E x a m p l e s of detec
t o r c o n t r a s t factors include the t h e r m a l l y driven local
elastic r e s p o n s e of a specimen w h i c h is p r e s e n t w h e n
surface d e f o r m a t i o n of t h e s a m p l e is m o n i t o r e d , t h e
infrared a b s o r p t i o n s p e c t r u m of t h e s a m p l e in t h e
spectral region used for d e t e c t i o n w h e n ir e m i t t a n c e is
t h e p r o p e r t y m o n i t o r e d a n d t h e electron d i s t r i b u t i o n
w h e n several of the laser d e t e c t i o n m e t h o d s a r e used.
In conclusion, w h e n e v e r T W I is used for c h a r a c t e r i z a
tion, selection of a family m e m b e r a p p r o p r i a t e t o t h e
i n t e n d e d a p p l i c a t i o n is essential.
See also: Stress Distribution: Analysis Using Thermoelastic
Effect

Bibliography
Fournier D, Boccara C, Skumanich A, Amer 1986
Photothermal investigation of transport in semiconduc
torstheory and experiment. / . Appl. Phys. 59: 787-95
Kuo , Favro L D, Thomas R L 1989 Mirage detection of
thermal waves In: Sell J A (ed.) 1989 Photothermal
Investigations of Solids and Liquids. Academic Press, New
York, pp. 191-212
Murphy J C, Spicer J W M, Aamodt L C 1986 Image
contrast processes in thermal and thermoacoustic imag
ing. IEEE Trans. Ultrason. Ferroelec. Frequency Control
33: 529-41
Murphy J C, Spicer J W M, Aamodt L C 1992 Principles of
photothermal detection in solids. In: Mandelis A (ed.)
1992 Photothermal and Photoacoustic Science and Tech
nology, Vol. 1. Elsevier, Amsterdam, pp. 41-94
Sawada T, Kasai 1987 Nondestructive inspection of
stacking faults and dislocations of semiconductor wafers
by photoacoustic microscopy (PAM) and photothermal
beam deflection. In: Mandelis A (ed.) 1987 Photoacoustic
and Thermal Wave Phenomena in Semiconductors. NorthHolland, Amsterdam, pp. 5-26
Tarn A C 1986 Applications of photoacoustic sensing tech
niques. Rev. Mod. Phys. 58: 384-131
J. C. M u r p h y
[ J o h n s H o p k i n s University, L a u r e l ,
Maryland, USA]

520

Thermodynamic Activity: Measurement

T h e activity at of a c o m p o n e n t / in a s o l u t i o n o r
c o m p o u n d , relative t o t h a t of p u r e / a t t h e s a m e
t e m p e r a t u r e , is defined as t h e r a t i o of t h e fugacities of
i in t h e t w o states. I n systems of metallurgical interest,
in w h i c h the e q u i l i b r i u m v a p o r pressures exerted b y
c o n d e n s e d p h a s e s a r e low e n o u g h t h a t ideal b e h a v i o r
of t h e v a p o r p h a s e c a n be a s s u m e d , fugacity c a n be
e q u a t e d w i t h p a r t i a l p r e s s u r e . H e n c e , b y definition,
*,=/>///>?

(1)

w h e r e p{ is t h e p a r t i a l p r e s s u r e of i exerted by t h e
s o l u t i o n o r c o m p o u n d a n d p? is t h e s a t u r a t e d v a p o r
p r e s s u r e of p u r e / a t t h e s a m e t e m p e r a t u r e .
A l t h o u g h activities a r e t h e r m o d y n a m i c functions
of state, their m a g n i t u d e s a n d v a r i a t i o n s a r e deter
mined by the interactions a m o n g the constituent
particles of t h e system, w h i c h , in t u r n , d e t e r m i n e
b o n d energies a n d influence t h e spatial configurations
a s s u m e d by t h e particles. T h u s , m e a s u r e m e n t of a c
tivities within a class of similar simple systems c a n be
expected t o p r o v i d e , a t best, s o m e f u n d a m e n t a l
u n d e r s t a n d i n g of t h e n a t u r e s of these i n t e r a c t i o n s , or,
at least, a basis for c o r r e l a t i o n of t h e b e h a v i o r , which
c a n t h e n be used for e x t r a p o l a t i o n of the b e h a v i o r of
m o r e c o m p l e x systems.
T h e m o l a r free energy of f o r m a t i o n of a s o l u t i o n o r
c o m p o u n d from its p u r e c o m p o n e n t s is o b t a i n e d from
M
t h e activities of t h e c o m p o n e n t s as AG = RT Nt In
at, w h e r e TV, is t h e m o l e fraction of t h e c o m p o n e n t /.
A s t h e v a r i o u s p h a s e equilibria o c c u r r i n g in a m a t e r
ials system a r e d e t e r m i n e d by t h e v a r i a t i o n s , with
c o m p o s i t i o n , t e m p e r a t u r e a n d p r e s s u r e , of t h e relative
free energies of t h e v a r i o u s p h a s e s , such equilibria c a n
be m o s t precisely d e t e r m i n e d by a c c u r a t e m e a s u r e
m e n t of activity. A l s o , t h e activity of a c o m p o n e n t in
a s o l u t i o n is a m e a s u r e of t h e m i n i m u m free energy
r e q u i r e d t o c o n v e r t t h e c o m p o n e n t from its state in
s o l u t i o n t o t h e p u r e state in a n y p r o p o s e d e x t r a c t i o n
o r refining p r o c e s s .
I n a d d i t i o n t o t h e d e t e r m i n a t i o n of activities b y
a p p l i c a t i o n of E q n . (1) t o t h e m e a s u r e m e n t of v a p o r
p r e s s u r e , activities h a v e been d e t e r m i n e d from t h e
e s t a b l i s h m e n t of e q u i l i b r i u m in chemical r e a c t i o n
systems a n d b y m e a s u r e m e n t of t h e e l e c t r o m o t i v e
forces of reversible galvanic cells.
I n t h e m a j o r i t y of t h e e x p e r i m e n t a l m e t h o d s t h e
activity of only o n e c o m p o n e n t is m e a s u r e d . In such
cases t h e activities of t h e o t h e r c o m p o n e n t s c a n be
o b t a i n e d by i n t e g r a t i o n of t h e G i b b s - D u h e m e q u a
tion. F o r c o n s t a n t t e m p e r a t u r e a n d t o t a l p r e s s u r e this
expression is TV, d(\n a) = 0 or, in a m o r e c o n v e n i e n t
form, Ni d(\n ) = 0, w h e r e y, = aJNt is t h e activity
coefficient of /. A p p l i e d t o t h e b i n a r y system A - B in
which t h e v a r i a t i o n of is k n o w n a c r o s s t h e entire
r a n g e of c o m p o s i t i o n ,
In y B( a U V B) = -

'

(NA /NB)

d(\n y A )

(2)

Thermodynamic

1. Activity
Measurement

Determination
of Vapor

by

Experimental

Pressure

T h e choice of e x p e r i m e n t a l t e c h n i q u e for t h e
m e a s u r e m e n t of v a p o r p r e s s u r e is d e t e r m i n e d b y t h e
m a g n i t u d e of the p r e s s u r e t o be m e a s u r e d . T h e
various techniques that have been developed can be
classified as a b s o l u t e m e t h o d s (direct a n d indirect
static m e t h o d s ) a n d indirect m e t h o d s (effusion a n d
t r a n s p i r a t i o n m e t h o d s ) . T h e earlier activity m e a s u r e
m e n t s were m a d e o n b i n a r y alloys of m e r c u r y w i t h
zinc, gold, silver a n d t h a l l i u m a t t e m p e r a t u r e s n e a r
the boiling p o i n t of m e r c u r y . T h e p a r t i a l p r e s s u r e of
m e r c u r y exerted b y a n a m a l g a m is so m u c h g r e a t e r
t h a n the p a r t i a l p r e s s u r e of t h e o t h e r c o m p o n e n t t h a t
the former c a n be e q u a t e d w i t h t h e t o t a l v a p o r
pressure of t h e a m a l g a m . In t h e first investigations t h e
alloy w a s used as t h e sealing liquid in a U - t u b e nullp o i n t m a n o m e t e r . T h e v a p o r in e q u i l i b r i u m w i t h t h e
alloy is c o n t a i n e d in t h e closed a r m of t h e m a n o m e t e r ,
a n d h y d r o g e n , the p r e s s u r e of w h i c h is m e a s u r e d a t a
second m a n o m e t e r , is i n t r o d u c e d i n t o t h e o t h e r a r m
until t h e meniscuses in b o t h a r m s a r e a t t h e s a m e
level. T h e v a p o r p r e s s u r e s of a m a l g a m s a t lower
t e m p e r a t u r e s h a v e been m e a s u r e d using v a r i o u s d e
vices such as m e m b r a n e m a n o m e t e r s , q u a r t z spiral
manometers and ionization gauges.
T h e p a r t i a l p r e s s u r e s of zinc a n d c a d m i u m o v e r aA g - Z n - C d alloys a n d zinc over -brasses h a v e b e e n
m e a s u r e d by r e s o n a n c e a b s o r p t i o n s p e c t r o s c o p y . I n
s t u d y i n g t h e zinc alloys, light p r o d u c e d b y a s p a r k
between zinc electrodes is p a s s e d t h r o u g h a s a m p l e of
v a p o r in e q u i l i b r i u m w i t h t h e alloy a n d t h e a b s o r p
tion of the 307.6 n m r e s o n a n c e line is m e a s u r e d . A s
the 303.5 n m r e s o n a n c e line is n o t a b s o r b e d , it is
used as a n i n t e r n a l s t a n d a r d , a n d t h e v a p o r p r e s s u r e
of zinc o b t a i n e d from Beer's law a s l n ( / 3 07 J
Im5)
= Kapd/T, w h e r e / is t h e intensity of t h e t r a n s
m i t t e d light, Ka is t h e a b s o r p t i o n coefficient, is t h e
a b s o l u t e t e m p e r a t u r e a n d d is t h e d i s t a n c e travelled b y
the light t h r o u g h t h e s a m p l e of v a p o r .
T h e d e w - p o i n t m e t h o d is well suited t o systems
c o n t a i n i n g a distinctly volatile c o m p o n e n t , a n d h a s
been applied t o m e a s u r e m e n t of t h e activity of zinc in
b i n a r y alloys c o n t a i n i n g c o p p e r , a l u m i n u m , silver,
gold, z i r c o n i u m , t h o r i u m , u r a n i u m a n d y t t r i u m a n d
of t h e activity of c a d m i u m in s i l v e r - c a d m i u m alloys.
E x p e r i m e n t a l l y , t h e alloy is placed a t o n e e n d of a
long, initially e v a c u a t e d t u b e w h i c h is h e a t e d t o t h e
desired t e m p e r a t u r e Tx. T h e t e m p e r a t u r e of t h e o t h e r
e n d of t h e t u b e is l o w e r e d until c o n d e n s a t i o n of t h e
volatile c o m p o n e n t is o b s e r v e d a t t h e t e m p e r a t u r e T2.
A s t h e p r e s s u r e within t h e t u b e is u n i f o r m , t h e p a r t i a l
pressure of t h e volatile c o m p o n e n t exerted b y t h e
alloy a t Tx e q u a l s t h e s a t u r a t e d v a p o r p r e s s u r e of t h e
p u r e volatile c o m p o n e n t a t T2. T h e use of fused silica
t u b e s , w h i c h p e r m i t s visual o b s e r v a t i o n of c o n d e n s a
tion at the c oole r e n d , h a s limited t h e t e m p e r a t u r e t o
less t h a n 1 1 0 0 C a n d , generally, m e a s u r e m e n t s h a v e

Activity:

Measurement

b e e n m a d e in t h e r a n g e 4 0 0 - 9 0 0 C. In a similar
isopiestic t e c h n i q u e , t h e p u r e volatile c o m p o n e n t is
p l a c e d in t h e cool e n d of a n initially e v a c u a t e d t u b e
m a i n t a i n e d in a k n o w n t e m p e r a t u r e g r a d i e n t a n d
weighed q u a n t i t i e s of t h e p u r e s e c o n d c o m p o n e n t a r e
t h e n p l a c e d a t intervals a l o n g t h e t e m p e r a t u r e g r a d i
ent. T h e volatile c o m p o n e n t is transferred from the
v a p o r p h a s e t o t h e specimens of n o n v o l a t i l e c o m
p o n e n t until t h e alloys in e q u i l i b r i u m w i t h t h e prevail
ing p r e s s u r e of t h e volatile c o m p o n e n t a r e f o r m e d . In
this t e c h n i q u e , w h i c h h a s been a p p l i e d t o m e a s u r e
m e n t of t h e activities of a l u m i n u m in solid A l - F e a n d
A l - N i alloys, t h e c o m p o s i t i o n s of t h e e q u i l i b r i u m
alloys a r e d e t e r m i n e d gravimetrically. A p p l i c a t i o n of
t h e d e w - p o i n t a n d isopiestic t e c h n i q u e s t o the
m e a s u r e m e n t of activity r e q u i r e s k n o w l e d g e of the
t e m p e r a t u r e d e p e n d e n c e of t h e s a t u r a t e d v a p o r pres
sure of t h e volatile c o m p o n e n t .
I n t h e t r a n s p i r a t i o n t e c h n i q u e a n inert carrier gas is
p a s s e d o v e r a s a m p l e a t a flow r a t e t h a t p e r m i t s
e v a p o r a t i o n of t h e alloy t o o c c u r t o t h e extent neces
sary t o s a t u r a t e t h e car r i er gas. T h i s t e c h n i q u e h a s
b e e n used t o m e a s u r e t h e activities in liquid F e - C u
a n d F e - N i alloys. T h e m a t e r i a l e v a p o r a t e d from the
s a m p l e is c o n d e n s e d d o w n s t r e a m a n d is chemically
a n a l y z e d . T h e t o t a l a m o u n t of e v a p o r a t i o n i n t o u n i t
v o l u m e of t h e car r i er gas a t t h e t o t a l p r e s s u r e is
d e t e r m i n e d b y m e a s u r i n g t h e weight loss of the s a m
ple o r b y q u a n t i t a t i v e analysis of t h e a m o u n t of
c o n d e n s a t e r eco v er ed from a k n o w n v o l u m e of gas. If
Fe, nCu a n d nHe a r e t h e n u m b e r s of m o l e s of i r o n ,
c o p p e r a n d h e l i u m carrier g a s in t h e s a m p l e d v o l u m e ,
respectively, t h e n t h e p a r t i a l p r e s s u r e of i r o n is cal
c u l a t e d from t h e ideal-gas law as pFe = PnFJ(nFe
+
nCu + nHe). A n a d v a n t a g e of this t e c h n i q u e is t h a t the
activities of b o t h c o m p o n e n t s a r e m e a s u r e d a n d hence
i n t e r n a l consistency of t h e results c a n b e checked
u s i n g t h e G i b b s - D u h e m e q u a t i o n . H o w e v e r , in o r d e r
t h a t surface d e p l e t i o n of t h e m o r e volatile c o m p o n e n t
be a v o i d e d , t h e r a t e s of diffusion in t h e alloy m u s t be
faster t h a n t h e r a t e s of e v a p o r a t i o n .
I n t h e effusion t e c h n i q u e t h e alloy t o be studied is
p l a c e d in a K n u d s e n cell (a sealed crucible c o n t a i n i n g
a small orifice in its lid) a n d t h e crucible is h e a t e d in
v a c u u m t o t h e desired t e m p e r a t u r e . P h a s e e q u i l i b r i u m
is established b e t w e e n t h e v a p o r p h a s e a n d t h e c o n
d e n s e d p h a s e in t h e cell a n d , if t h e d i m e n s i o n s of t h e
orifice a r e small in c o m p a r i s o n w i t h t h e m e a n free
p a t h of t h e v a p o r species, t h e p a s s a g e of v a p o r species
t h r o u g h t h e orifice is n o t d i s t u r b e d b y collisions.
T h u s , t h e rates of effusion of t h e v a p o r species are
p r o p o r t i o n a l t o their v a p o r p r e s s u r e s within the cell.
F r o m t h e kinetic t h e o r y of gases, t h e n u m b e r of
particles in a v a p o r p h a s e striking u n i t a r e a of the
c o n t a i n i n g wall in u n i t t i m e is 0.25 nc, w h e r e is the
112
is
density of t h e v a p o r species a n d c = (SRT/)
t h e a v e r a g e speed of t h e particles (M is m o l a r m a s s ) .
T h u s , t h e weight loss W d u e t o effusion t h r o u g h a n
l/2
orifice of a r e a A in time / is W = pAt/(2nMRT)
and

521

Thermodynamic

Activity:

Measurement

hence t h e p r e s s u r e of the species in t h e cell is

1 2
If a r a d i o a c t i v e t r a c e r is
p = (W/At)
(2nRT/M) ' .
a d d e d t o t h e alloy, very small a m o u n t s of effusing
s u b s t a n c e c a n be detected. F o r e x a m p l e , y-ray spec
t r o m e t r y of n e u t r o n - i r r a d i a t e d A u - C u alloys h a s
m a d e possible t h e m e a s u r e m e n t of q u a n t i t i e s as small
1 0
as 1 0 " g . T h e t r a n s p i r a t i o n a n d effusion t e c h n i q u e s
require t h a t t h e m o l e c u l a r weights of t h e v a p o r spe
cies b e k n o w n a n d hence they c a n only b e used t o
study systems in w h i c h n o c o m p l e x v a p o r molecules
are formed.
T h e p r o b l e m s c a u s e d by c o m p l e x molecule f o r m a
tion c a n be eliminated by m a s s - s p e c t r o m e t r i c analysis
of t h e v a p o r effusing from t h e K n u d s e n cell. I n t h e
K n u d s e n cell/time-of-flight m a s s s p e c t r o m e t e r c o m
b i n a t i o n t h e b e a m of particles effusing from t h e cell is
i n t r o d u c e d i n t o t h e i o n i z a t i o n c h a m b e r of t h e m a s s
s p e c t r o m e t e r t h r o u g h a slit. I o n i z a t i o n is p r o d u c e d b y
a pulsing electron b e a m ; after e a c h pulse of e l e c t r o n s
the ionization c h a m b e r is cleared of ions b y a pulse of
small negative p o t e n t i a l . T h e ions a r e t h e n subjected
to a c o n t i n u o u s l y m a i n t a i n e d high negative p o t e n t i a l
which accelerates t h e m i n t o a field-free drift t u b e ; t h e
time required for a given singly c h a r g e d ion of m a s s m
t o traverse t h e drift t u b e a n d b e detected is p r o p o r
112
tional t o (m/e) . T h e ion c u r r e n t /+ m e a s u r e d for t h e
species i is related t o t h e v a p o r p r e s s u r e of / b y
Pi = Kil+T

(3)

w h e r e t h e c o n s t a n t K{ is d e t e r m i n e d b y t h e i o n i z a t i o n
cross section of t h e ion, t h e d e t e c t o r sensitivity a n d
t h e g e o m e t r y of the K n u d s e n - c e l l ion s o u r c e . T h e
a p p l i c a t i o n of the t e c h n i q u e t o m e a s u r e m e n t of activi
ties in b i n a r y systems w a s greatly facilitated b y a
m a n i p u l a t i o n of t h e G i b b s - D u h e m e q u a t i o n w h i c h
allows the v a r i a t i o n s with c o m p o s i t i o n of t h e activity
coefficients of the individual c o m p o n e n t s t o b e
o b t a i n e d from the c o r r e s p o n d i n g m e a s u r e d r a t i o of
the activity coefficients:
= - j " V

In y B ( a t NB)

d[\n(yA/yB)]

(4)

F r o m E q n . (3),
'A

/B

Pa
OC

pb

_?*
OC

77-

y* *

s u b s t i t u t i o n of w h i c h i n t o E q n . (4) gives
In )> B(at7V B) = - J %

v a n a d i u m , c h r o m i u m , iron, c o b a l t , nickel, c o p p e r ,
silver, gold, a l u m i n u m , t h a l l i u m , lead, tin, b i s m u t h ,
antimony and indium.

2. Activity Determination
by
Heterogeneous
Equilibrium

Establishing

Heterogeneous equilibrium at constant temperature

a n d p r e s s u r e requires t h a t t h e p a r t i a l m o l a r free
energy, a n d h e n c e activity, of e a c h c o m p o n e n t of t h e
system be t h e s a m e in e a c h of t h e p h a s e s present; t h a t
is, cii (in p h a s e I) = a( (in p h a s e II) = a, (in p h a s e
III) = . . . T h u s , if t h e activity of a c o m p o n e n t c a n b e
fixed a t a k n o w n value in a n y o n e of t h e p h a s e s , its
value in every o t h e r p h a s e is k n o w n .
O n e of t h e simpler h e t e r o g e n e o u s equilibria
involves a b i n a r y liquid s a t u r a t e d w i t h o n e of its
c o m p o n e n t s . I n a simple b i n a r y eutectic system exhi
biting virtually c o m p l e t e m u t u a l immiscibility in t h e
solid state, t h e s a t u r a t e d liquids o n the liquidus lines
a r e in e q u i l i b r i u m w i t h virtually p u r e solids. T h u s , in
t h e m e l t of a n -rich c o m p o s i t i o n a t t h e liquidus
t e m p e r a t u r e , t h e activity of A relative t o p u r e liquid
A as t h e s t a n d a r d state e q u a l s t h e activity of p u r e
solid A relative t o liquid A as t h e s t a n d a r d state, b o t h
w h e r e AGmA
being given b y aA = exp( - AGmJRT)9
is t h e m o l a r free energy of m e l t i n g of A a t t h e
t e m p e r a t u r e T. Activities h a v e been calculated in this
m a n n e r a l o n g liquidus lines in systems such as A g - S i
and Ag-Pb.
I r o n a n d silver a r e virtually immiscible in t h e liquid
state, a n d w h e n silicon is a d d e d as a solute t o coexist
ing liquid i r o n a n d silver it is d i s t r i b u t e d between t h e
t w o liquids in such a w a y t h a t its activity is t h e s a m e in
b o t h p h a s e s . T h e activities of silicon in liquid i r o n a n d
liquid F e - C alloys h a v e been d e t e r m i n e d b y chemical
analysis of e q u i l i b r a t e d i r o n a n d silver liquids c o n
t a i n i n g silicon, a n d k n o w l e d g e of t h e activity of
silicon in A g - S i alloys. I n a similar m a n n e r , t h e
activity of silver in A l - A g alloys h a s been d e t e r m i n e d
from m e a s u r e m e n t of t h e e q u i l i b r i u m p a r t i t i o n i n g of
silver b e t w e e n t h e virtually immiscible liquids a l u m i
n u m a n d lead, a n d t h e activity of a l u m i n u m in A l - C o
alloys h a s b e e n d e t e r m i n e d b y p a r t i t i o n i n g a l u m i n u m
b e t w e e n t h e virtually immiscible liquids silver a n d
cobalt.
T h e respective e q u i l i b r i u m c o n s t a n t s for t h e reac
tions C 0 2 + C ( g r a p h i ^t e) 2 C O a n d C O + | 0 2 ^ C 0 2 a r e

d[\n(lX //+ )

K =

5 PcolPco2 c

()

and
-\n(NA/NB)]
U s e of a m a s s s p e c t r o m e t e r requires t h a t a p r e s s u r e of
8
less t h a n 1 0 ~ a t m be m a i n t a i n e d in t h e a r e a s of t h e
ion s o u r c e , a n a l y z e r a n d d e t e c t o r . T h i s t e c h n i q u e h a s
been applied t o m e a s u r e m e n t of activities in a large
n u m b e r of b i n a r y a n d t e r n a r y systems c o n t a i n i n g

522

6=Pco2/PcoPo2

(6)

T h u s , a t a fixed t e m p e r a t u r e , w h i c h d e t e r m i n e s t h e
values of K5 a n d K6, a C O - C 0 2 , gas m i x t u r e of k n o w n
Pco a n d PCQ2 h a s a n activity of c a r b o n given b y E q n .
(5) a n d a p a r t i a l p r e s s u r e of o x y g e n given b y E q n . (6).
Similarly,
by
virtue
of
the
equilibrium

Thermodynamic

H 2 + ^ 0 2 ^ H 2 0 , a n H 2 - H 2 0 m i x t u r e of k n o w n pH2
a n d pH20 exerts a u n i q u e p a r t i a l p r e s s u r e of o x y g e n a t
a n y t e m p e r a t u r e . By virtue of t h e e q u i l i b r i u m
H 2 + ^ S 2 ^ H 2 S , a n H 2 - H 2 S m i x t u r e of k n o w n pH2 a n d
pHlS exerts a u n i q u e p a r t i a l p r e s s u r e of sulfur a t a n y
t e m p e r a t u r e , a n d , b y virtue of t h e e q u i l i b r i u m C ( g r a p. h
and
i t e) + 2 H 2 ^ C H 4 , a C H 4 - H 2 m i x t u r e of k n o w n pCH2
pH2 h a s a u n i q u e activity of c a r b o n a t a n y t e m p e r a
ture. C o n s e q u e n t l y , C O - C 0 2 a n d C H 4 - H 2 m i x t u r e s
c a n be used as gas p h a s e s of fixed activity of c a r b o n
for use in t h e e s t a b l i s h m e n t of h e t e r o g e n e o u s equili
bria b e t w e e n a gas p h a s e a n d a c o n d e n s e d p h a s e .
Similarly, C O - C 0 2 a n d H 2 - H 2 0 m i x t u r e s c a n b e used
as gas p h a s e s of fixed oxygen p r e s s u r e a n d H 2 - H 2 S
m i x t u r e s c a n be used as gas p h a s e s of fixed sulfur
pressure.
T h e activities of c a r b o n in liquid a n d solid i r o n
h a v e been d e t e r m i n e d b y e q u i l i b r a t i n g i r o n with C O C 0 2 and C H 4 - H 2 mixtures a n d measuring the equi
librium c a r b o n c o n t e n t of t h e m e t a l p h a s e , a n d t h e
activities of oxygen a n d sulfur in liquid i r o n h a v e b e e n
d e t e r m i n e d b y e q u i l i b r a t i n g i r o n with H 2 0 - H 2 a n d
H 2 S - H 2 m i x t u r e s , respectively. I n simpler g a s - m e t a l
equilibria, t h e activities of h y d r o g e n a n d n i t r o g e n in
iron h a v e been d e t e r m i n e d b y m e a s u r i n g t h e solubili
ties of the gases a s functions of gas p r e s s u r e . Activities
in t h e system F e - F e 2 0 3 h a v e b e e n d e t e r m i n e d b y
e x p e r i m e n t a l o b s e r v a t i o n of t h e v a r i a t i o n of t h e c o m
p o s i t i o n of small s a m p l e s of c o n d e n s e d p h a s e s w i t h
temperature and oxygen pressure imposed by an
equilibrating gas p h a s e . T h e v a r i a t i o n , with c o m p o s i
tion, of the activity of i r o n in t h e system is d e t e r m i n e d
by G i b b s - D u h e m i n t e g r a t i o n of t h e c o r r e s p o n d i n g
m e a s u r e d v a r i a t i o n of t h e e q u i l i b r i u m p a r t i a l p r e s s u r e
of oxygen. T h e oxygen c o n t e n t of liquid i r o n in
e q u i l i b r i u m with p u r e liquid F e O a t 1600 C is
0.23 w t % . If t h e oxide of a less n o b l e m e t a l t h a n i r o n
is dissolved in t h e liquid F e O , t h e activity of F e O , a n d
hence t h e e q u i l i b r i u m oxygen c o n t e n t of t h e liquid
iron, is decreased. If t h e latter is JC w t % , t h e activity of
F e O , relative t o p u r e i r o n - s a t u r a t e d F e O as t h e s t a n
d a r d state, in t h e oxide s o l u t i o n is x / 0 . 2 3 . T h i s tech
n i q u e h a s been used t o d e t e r m i n e t h e activity of F e O
in C a O - F e O a n d C a O - F e O - S i 0 2 melts s a t u r a t e d
with liquid i r o n .
O n e step m o r e c o m p l e x is t h e e s t a b l i s h m e n t of
e q u i l i b r i u m b e t w e e n a gas p h a s e a n d t w o c o n
densed p h a s e s . T h e e q u i l i b r i u m b e t w e e n m a n g a n e s e ,
M n O a n d a C O - C 0 2 m i x t u r e , expressed
as
M n + C 0 2 ^ M n O + C O , requires t h a t
K

PCO UnO IPCOI Mn

()

T h u s , a t a given t e m p e r a t u r e , t h e e q u i l i b r i u m b e t w e e n
p u r e m a n g a n e s e (at u n i t activity) a n d m a n g a n e s e s a t u r a t e d p u r e M n O (at u n i t activity) o c c u r s a t a
y en
u n i q u e value of t h e r a t i o pCo/Pco2 g i
b y E q n . (7). If
a m e t a l m o r e n o b l e t h a n m a n g a n e s e is e m b e d d e d in
a n excess of M n O a n d subjected t o a lower
pco/Pco2
r a t i o , m a n g a n e s e is transferred from t h e M n O t o t h e

Activity:

Measurement

m e t a l p h a s e until t h e activity of m a n g a n e s e r e q u i r e d
s
b y E q n . (7) a n d b y t h e i m p o s e d pColPco2
* estab
lished. T h e m a n g a n e s e c o n t e n t of t h e alloy c o r r e s
p o n d i n g t o t h e i m p o s e d activity is d e t e r m i n e d b y
chemical analysis. T h e o t h e r c o m p o n e n t of t h e alloy
m u s t be sufficiently m o r e n o b l e t h a n m a n g a n e s e t h a t
f o r m a t i o n a n d s o l u t i o n of its o x i d e in t h e M n O p h a s e
is negligible. T h e activity of m a n g a n e s e in M n - P t
alloys h a s been d e t e r m i n e d in this m a n n e r . T h e a c
tivity of M n O in o x i d e m e l t s c o n t a i n i n g oxides m o r e
stable t h a n M n O c a n s u b s e q u e n t l y b e f o u n d b y
e q u i l i b r a t i n g a small s a m p l e of p l a t i n u m with a n
excess of o x i d e m e l t a n d a C O - C 0 2 g a s m i x t u r e .
A g a i n , as m a n g a n e s e is d i s t r i b u t e d b e t w e e n t h e P t M n alloy a n d t h e oxide m e l t in a c c o r d a n c e w i t h E q n .
(7) a n d t h e i m p o s e d PcolPco? c h e m i c a l analysis of t h e
e q u i l i b r a t e d P t - M n alloy yields aMn a n d h e n c e , from
E q n . (7), t h e value of aMnQ in t h e o x i d e melt. I n this
a p p l i c a t i o n , t h e o t h e r oxide c o m p o n e n t m u s t be of a
m e t a l w h i c h is sufficiently less n o b l e t h a n m a n g a n e s e
t h a t t h e e x t e n t of its s o l u t i o n in t h e P t - M n p h a s e is
negligible. T h i s t e c h n i q u e h a s b e e n used t o d e t e r m i n e
t h e activity of M n O in systems s u c h as M n O - S i 0 2 ,
M n O - T i 0 2, M n O - A l 20 3, M n O - B 20 3 and M n O C a O - S i 0 2.
O t h e r e x a m p l e s of d e t e r m i n a t i o n of activities b y
establishing e q u i l i b r i u m b e t w e e n a b i n a r y alloy, a
n o n m e t a l l i c p h a s e of k n o w n c o m p o s i t i o n a n d a gas
p h a s e include:
Fe(in F e - N i alloys) + H 2 0 ; = F e O + H 2
2Cr(in C r - N i alloys) + 3 H 2 0 ^ C r 2 0 3 + 3 H 2
3 M n ( i n M n - C u alloys) + C H 4 ^ M n 3 C + 2 H 2
2 C u ( i n C u - A u alloys) + H 2 S ^ C u 2 S + H 2
3Si(in S i - A g alloys) + N 2 ( i n N 2 - H 2 m i x t u r e s )
^ S i 3N 4

(8)

A g a i n , in this a p p l i c a t i o n , t h e " i n e r t " m e t a l m u s t b e

sufficiently m o r e n o b l e t h a n t h e p r i m a r y c o m p o n e n t
m e t a l t h a t its o c c u r r e n c e in t h e e q u i l i b r i u m n o n m e t a l
lic p h a s e is negligible. C o r r e c t i o n s a r e r e q u i r e d in
systems w h e r e t h e n o n m e t a l l i c p h a s e is n o t a line
c o m p o u n d (i.e., o n e with a negligible r a n g e of n o n s t o i c h i o m e t r y ) . T h u s , for e x a m p l e , in E q n . (8) t h e
activity of F e O is t h a t in t h e w u s t i t e e q u i l i b r a t e d with
t h e i m p o s e d p a r t i a l p r e s s u r e of oxygen relative t o
i r o n - s a t u r a t e d w u s t i t e as t h e s t a n d a r d state. E q n . (8)
h a s also b e e n u s e d t o d e t e r m i n e t h e activity of F e O in
F e O - S i 0 2 m e l t s b y establishing t h e e q u i l i b r i u m
F e + H 2 0 ^ F e O (in F e O - S i 0 2 melts) + H 2 .
If t h e difference b e t w e e n t h e reactivities of t h e
m e t a l s is small e n o u g h t h a t a n oxide s o l u t i o n is
p r o d u c e d in e q u i l i b r i u m w i t h t h e b i n a r y alloy p h a s e , a
different a p p r o a c h is t a k e n . F o r e x a m p l e , if a small
specimen of a n F e - M n alloy is e q u i l i b r a t e d with a n
excess of a n F e O - M n O solid s o l u t i o n , t h e e x c h a n g e
e q u i l i b r i u m F e + M n O ; = M n + F e O is established,

523

Thermodynamic

Activity:

Measurement

wherein =
flMnflFe0/aFeaMn0.
F r o m chemical analysis
of t h e e q u i l i b r a t e d F e - M n alloy a n d k n o w l e d g e of t h e
activities in t h e system F e - M n , t h e r a t i o yFe0/yMn0
in
the e q u i l i b r a t i n g oxide s o l u t i o n is o b t a i n e d as
OVeo/yMno) = ^ F e

^MnO l Mn

FcO

a n d G i b b s - D u h e m i n t e g r a t i o n of t h e v a r i a t i o n of this
r a t i o with c o m p o s i t i o n in the o x i d e s o l u t i o n a c c o r d
ing t o E q n . (4) yields t h e i n d i v i d u a l activity coeffi
cients, a n d hence activities, of t h e c o m p o n e n t s of t h e
oxide s o l u t i o n . T h i s t e c h n i q u e h a s b e e n used t o deter
m i n e activities in t h e systems F e 2 S i 0 4 - C o 2 S i 0 4 a n d
F e 2S i 0 4- M n 2S i 0 4.
Activities h a v e been d e t e r m i n e d b y establishing
e q u i l i b r i u m a m o n g three c o n d e n s e d p h a s e s a n d a g a s
p h a s e . A s a n e x a m p l e , t h e activity of S i 0 2 in C a O M g 0 - A l 2 0 3 - S i 0 2 melts has been determined by
establishing t h e e q u i l i b r i u m
S i 0 2 + 2C;=Si + 2 C O

(9)

in systems c o m p r i s i n g a silicate melt, solid g r a p h i t e ,

liquid i r o n a n d C O gas a t 1 a t m p r e s s u r e , a n d b y
establishing the e q u i l i b r i u m
S i 0 2 + 2SiC^3Si 4- 2 C O

(10)

in systems c o m p r i s i n g a silicate melt, solid SiC, liquid

iron a n d C O gas a t 1 a t m p r e s s u r e . T h e activity of
S i 0 2 is o b t a i n e d from chemical analysis of t h e equili
b r a t e d liquid p h a s e s , k n o w l e d g e of t h e e q u i l i b r i u m
c o n s t a n t s for t h e r e a c t i o n s given b y E q n s . (9) a n d (10)
a n d k n o w l e d g e of the activity of silicon in F e - S i - C
melts. G i b b s - D u h e m i n t e g r a t i o n of t h e results h a s
yielded activities in the systems C a O - S i 0 2 , C a O A 1 20 3, M g O - S i 0 2 , C a O - A l 2 0 3 - S i 0 2 , M g O - C a O S i 0 2 and M g O - A l 20 3- S i 0 2.

3. Electrochemical

Measurement

of

ionic c o n d u c t o r c o n t a i n i n g
ions of metal A of valence z A

alloy A - B

the cell r e a c t i o n is A ( p u r e ) - A ( i n t h e A - B alloy), for

which AG = RT In aA (in t h e A - B alloy). T h u s , t h e
activity of A in t h e alloy is o b t a i n e d as l n a A .
= -zAFE/RT.
T h e d e t e r m i n a t i o n of activity b y
m e a s u r e m e n t of t h e e m f of a n electrochemical cell
requires t h a t t h e electrolyte b e a p u r e l y ionic c o n d u c
t o r a n d t h a t t h e valency z A b e defined. A further
r e q u i r e m e n t is t h a t t h e e x t e n t of t h e e x c h a n g e r e a c t i o n
at t h e c a t h o d e - e l e c t r o l y t e interface b e t w e e n in t h e
alloy a n d A in the electrolyte be negligible. If this
c o n d i t i o n is n o t m e t t h e m e a s u r e d e m f c o n t a i n s a
c o n t r i b u t i o n of u n k n o w n m a g n i t u d e arising from t h e

524

Al(l)| A l

3 +

(in K C l - N a C l ) | A l - A g ( l )

Similarly, t h e activities of c a d m i u m in C d - P b , C d - B i ,
C d - S b a n d C d - S n alloys a n d t h e activities of c o p p e r
in C u - A u m e l t s a n d silver in A g - A u m e l t s h a v e b e e n
d e t e r m i n e d from c o n c e n t r a t i o n cells w i t h liquid chlor
ide electrolytes.
T h e cell
M g ( l ) | M g C l 2( l ) | C l 2( g , l a t m )
is a f o r m a t i o n cell in w h i c h t h e cell r e a c t i o n is
M g + Cl 2;=MgCl 2. W i t h p u r e liquid m a g n e s i u m p u r e
liquid M g C l 2 a n d C l 2 a t 1 a t m p r e s s u r e , t h e freeenergy c h a n g e is t h e s t a n d a r d free-energy c h a n g e
0
A G a n d t h e e m f is t h e s t a n d a r d e m f E= - AG2F.
Alloying t h e a n o d e w i t h a m o r e n o b l e m e t a l s u c h as
a l u m i n u m alters t h e free-energy c h a n g e for t h e cell
0
r e a c t i o n t o AG = A G - RT In aMg (in t h e alloy) a n d
h e n c e t h e cell e m f t o
= E + (RT/2F)\n

aMg(m

t h e alloy)

(11)

E q n . (11) h a s b e e n u s e d t o d e t e r m i n e t h e activities of
m a g n e s i u m in M g - A l m e l t s from e m f m e a s u r e m e n t s
in t h e r a n g e 7 0 0 - 8 8 0 C.
Similarly, t h e f o r m a t i o n cell
P b ( l ) | P b O ( l ) | 0 2( g , l a t m )

Activity

T h e emf of a reversible galvanic cell is related t o t h e

free-energy c h a n g e AG for the cell r e a c t i o n b y
AG = zFE, w h e r e F is F a r a d a y ' s c o n s t a n t a n d is
the n u m b e r of F a r a d a y s r e q u i r e d for t h e cell r e a c t i o n .
T h u s , in a c o n c e n t r a t i o n cell of the t y p e
pure
metal A

transfer of electrolyte b e t w e e n r e g i o n s of different

c o m p o s i t i o n . I n p r a c t i c e , t h e e x t e n t of t h e e x c h a n g e
r e a c t i o n is r e n d e r e d negligible b y e n s u r i n g t h a t is
significantly m o r e n o b l e t h a n A . M o l t e n c h l o r i d e s a r e
p u r e l y ionic c o n d u c t o r s a n d h e n c e these m e l t s a r e
p o p u l a r as liquid electrolytes. T h e c o n c e n t r a t i o n s of
low-valent c a t i o n s in t h e electrolyte a r e m i n i m i z e d
b y dissolving t h e c h l o r i d e s in m i x t u r e s of alkali
chlorides.
T h e activity of a l u m i n u m in A l - A g melts in the
r a n g e 7 0 0 - 8 0 0 C h a s b e e n o b t a i n e d f r o m m e a s u r e
m e n t of t h e emfs of cells of t h e t y p e

h a s a s t a n d a r d e m f = - AG/2F. A l l o y i n g t h e P b O
electrolyte w i t h t h e o x i d e of a less n o b l e m e t a l , such as
S i 0 2 , c h a n g e s t h e cell e m f t o
E=E-

(RT/2F)\n

aPbo(m

P b O - S i 0 2)

a n d this h a s b e e n used as t h e basis for electrochemical

d e t e r m i n a t i o n of t h e activities in t h e system P b O - S i 0 2
in t h e r a n g e 8 5 0 - 1 0 5 0 C.
W i t h i n w i d e r a n g e s of t e m p e r a t u r e a n d oxygen
p r e s s u r e , Z r 0 2 a n d T h 0 2 , in t h e fluorite s t r u c t u r e
stabilized, respectively, b y solid s o l u t i o n with C a O
a n d Y 2 0 3 , exhibit u n u s u a l l y h i g h conductivities a n d
2 t r a n s p o r t n u m b e r s for O
of essentially u n i t y . C o n
sequently, C a O - Z r 0 2 and Y 2 0 3 - T h 0 2 have been used
as solid electrolytes in o x y g e n c o n c e n t r a t i o n cells of
the type
P t , 0 2( g , a t
p r e s s u r e Px)

CaO-Zr02

0 2( g , a t
p r e s s u r e P 2) , P t

in w h i c h t h e cell r e a c t i o n is 0 2 ( g , a t p r e s s u r e

Px)

Thermoluminescence

0 2 ( g , a t p r e s s u r e P2) a n d t h e cell e m f is = - AG/

4F= - (RT/4F) l n ( P 2 / P , ) . T h e o x y g e n p r e s s u r e a t t h e
electrodes c a n b e fixed b y u s i n g e q u i l i b r a t e d m e t a l m e t a l - o x i d e c o u p l e s ; for e x a m p l e , with F e - F e O a n d
N i - N i O t h e cell b e c o m e s
Fe, F e O | C a O - Z r 0 2| N i , N i O
with a cell r e a c t i o n of N i O + F e ^ F e O + N i . W i t h
the electrodes F e - F e O a n d ( F e - N i ) - F e O , t h e cell
reaction is F e ( p u r e ) -* Fe(in t h e F e - N i alloy) a n d t h e
cell emf is
= (RT/2F)\n

a F e( i n t h e alloy)

Gaskell D R 1981 Introduction to Metallurgical Thermo

dynamics, 2nd edn. McGraw-Hill, New York
Hultgren R R, Desai D, Hawkins D T, Gleiser M, Kelley
1973 Selected Values of the Thermodynamic Proper
ties of Binary Alloys. ASM, Materials Park, OH
Kubaschewski O, Alcock C 1979 Metallurgical Thermo
chemistry, 5th edn. Pergamon, New York
Steiner A, Komarek L 1964 Thermodynamic activities in
solid Ni-Al alloys. Trans. Metall. Soc. AIME 230: 786-90
Wagner C 1952 Thermodynamics of Alloys. AddisonWesley, Reading, MA
D . R. Gaskell
[ P u r d u e University, W e s t Lafayette,
Indiana, USA]

(12)

T h i s m e t h o d is similar t o t h a t discussed in c o n n e c t i o n
with E q n . (8). In t h e chemical e q u i l i b r a t i o n t e c h n i q u e
the oxygen p r e s s u r e is i m p o s e d a n d t h e F e - N i alloy in
e q u i l i b r i u m w i t h F e O a n d t h e i m p o s e d oxygen p r e s
sure is p r o d u c e d in t h e e x p e r i m e n t a l a p p a r a t u s . I n t h e
emf t e c h n i q u e t h e o x y g e n p r e s s u r e in e q u i l i b r i u m with
a given F e - N i alloy a n d F e O is m e a s u r e d . E q n . (12)
h a s been used as t h e basis for electrochemical deter
m i n a t i o n of t h e activities in a large n u m b e r of solid
a n d liquid b i n a r y alloy systems, t h e m a j o r i t y of w h i c h
h a v e c o n t a i n e d i r o n , c o b a l t , nickel o r c o p p e r as t h e
less n o b l e m e t a l . T h e activity of silicon in F e - S i alloys
at 1 5 5 0 C a n d 1600 C h a s been d e t e r m i n e d with
electrodes of c h r o m i u m , C r 2 0 3 a n d S i 0 2 , F e - S i , a n d
activities in t h e systems T a - W a n d T a - M o h a v e b e e n
d e t e r m i n e d with a Y 2 0 3 - T h 0 2 electrolyte a n d t a n t a
l u m , T a 2 0 5 a n d T a - X , T a 2 O s electrodes. T h e activities
of S n O in S n O - S i 0 2 melts a n d P b O in P b O - S i 0 2
melts h a v e b e e n d e t e r m i n e d from cells of t h e t y p e M ,
M O | C a O - Z r 0 2l M , M O - S i 0 2.
O t h e r solid electrolytes w h i c h h a v e been used in
clude b e t a - a l u m i n a a n d soft s o d a glass for m e a s u r e
m e n t of the activity of s o d i u m in alloys, a n d glasses
+
+
a n d A g for s t u d y , respectively, of
containing K
p o t a s s i u m a n d silver alloys. It c a n b e expected t h a t , as
new solid-state electrolytes a r e d e v e l o p e d for possible
use in fuel cells, they will be a p p l i e d t o t h e d e t e r m i
n a t i o n of activities b y e m f m e a s u r e m e n t s .
See also: Phase Diagrams and Phase Stability: Calculations
Bibliography
Belton G R, Fruehan R J 1971 The determination of
activities by mass-spectrometry: some additional
methods. Metall. Trans. 2: 291-6
Chandrasekharaiah S, Sreedharan , Chattopadhyay
G 1980 Thermodynamic studies of alloys and intermetallic compounds. In: Subbarao C (ed.) 1980 Solid Electro
lytes and their Applications. Plenum, New York, pp. 9 9 126
Elliott J F 1981 Physical chemistry of liquid metal solutions.
In: Tien J K, Elliott J F (eds.) 1981 Metallurgical Trea
tises. The Metallurgical Society (AIME), Warrendale,
PA, pp. 41-58
Elliott J F, Gleiser M, Ramakrishna V 1963 Thermo
chemistry for Steelmaking. Addison-Wesley, Reading,
MA

Thermoluminescence
T h e r m o l u m i n e s c e n c e ( T L ) is a p r o c e s s in w h i c h a
m a t e r i a l , previously subjected t o ionizing r a d i a t i o n , is
h e a t e d so t h a t s o m e of t h e s t o r e d energy is released in
t h e f o r m of light. M a n y i n s u l a t o r a n d s e m i c o n d u c t o r
m a t e r i a l s exhibit this p r o p e r t y . A few i n s u l a t o r m a t e r
ials with t h e m o s t f a v o r a b l e t h e r m o l u m i n e s c e n t
p r o p e r t i e s a r e used for r a d i a t i o n d o s i m e t r y ; t h e light
o u t p u t allows a m e a s u r e of t h e received d o s e . Simi
larly, t h e r m o l u m i n e s c e n c e is used in a r c h e o l o g y for
t h e d a t i n g of c e r a m i c objects w h i c h h a v e been irra
d i a t e d b y n a t u r a l r a d i a t i o n d u r i n g their lifetime. T h e
s a m e m e t h o d c a n be used for t h e d a t i n g of geological
formations.
T h e r m o l u m i n e s c e n c e is of interest as a physical
p r o c e s s n o w recognized a s b e i n g p a r t of a larger
g r o u p of processes k n o w n as t h e r m a l l y s t i m u l a t e d
r e l a x a t i o n s in solids ( B r a u n l i c h 1979). It h a s b e c o m e
a n i m p o r t a n t t e c h n i q u e for s t u d y i n g t h e t r a p p i n g
of electrons a n d holes a t p o i n t a n d line defects in
crystals.

1.

Apparatus

A p p a r a t u s used for m e a s u r i n g t h e r m o l u m i n e s c e n c e
usually consists of: (a) a h e a t i n g e l e m e n t which h e a t s
t h e specimen, usually a t a linear h e a t i n g r a t e g o v e r n e d
by a t e m p e r a t u r e c o n t r o l l e r a n d p r o g r a m m e r ; (b) a
photomultiplier tube and power supply to measure
t h e intensity of t h e e m i t t e d light; (c) a system t o
m e a s u r e t h e p h o t o m u l t i p l i e r signal; a n d (d) a n x-y
p l o t t e r t o display t h e t h e r m o l u m i n e s c e n t intensity as a
c u r r e n t versus t e m p e r a t u r e p l o t , called a glow curve
(Fig. 1). A n optical filter c a n be e m p l o y e d t o r e d u c e
t h e infrared r a d i a t i o n from t h e h e a t e r e n t e r i n g t h e
p h o t o m u l t i p l i e r t u b e w h i c h typically b e c o m e s signi
ficant a b o v e 400 C. T h e light d e t e c t i o n system is
completely enclosed a n d a n a t m o s p h e r e of n i t r o g e n
m a y be used w i t h p o w d e r s a m p l e s t o minimize a
s p u r i o u s b a c k g r o u n d emission k n o w n as t r i b o l u m i nescence. R a p i d r e a d o u t rates a r e s o m e t i m e s favored

525

Thermoluminescence
h e a t e d , t h e electron m a y b e t h e r m a l l y released from
its t r a p b y a t t a i n i n g t h e a c t i v a t i o n energy t o j u m p
into the conduction band, and then migrate to a
t r a p p e d h o l e a n d r e c o m b i n e w i t h t h e emission of light
(Fig. 2b). If t h e electrons a t t e m p t t o leave t h e t r a p a t a
frequency 5 , t h e n t h e p r o b a b i l i t y of escape P, a s s u m
ing a B o l t z m a n n d i s t r i b u t i o n of energies, is

dc
ammeter

High - v o l t a g e
dc s u p p l y

Photomultiplier

tube
100

150

Temperature

Infrared

Thermocouple

filter

I Programmer

L i g h t - t i g h t seal

Thermoluminescent
sample

Temperature
controller

Resistance
heater

= S e x p ( - E/kT)

200

C O

Power

(1)

T h e simplest m o d e l for t h e r m o l u m i n e s c e n c e is t h e
first-order-kinetics m o d e l in w h i c h it is a s s u m e d t h a t
t h e intensity of light e m i t t e d , 7, is p r o p o r t i o n a l t o t h e
r a t e of release of electrons from their t r a p s , w h i c h is in
t u r n p r o p o r t i o n a l t o t h e n u m b e r of t r a p p e d electrons.
T h e b a c k r e a c t i o n , t h e r e t r a p p i n g of electrons, is
a s s u m e d t o b e negligible. If t h e r e a r e t r a p p e d
electrons ( a n d t r a p p e d holes) t h e r a t e of release of
electrons is
- dn/dt = nP

(2)

Figure 1
Apparatus for the measurement of thermoluminescence

w h e r e is t h e p r o b a b i l i t y of a n electron being
released f r o m its t r a p p e r u n i t t i m e . T h e t h e r m o l u m i
nescent intensity c a n t h e n b e expressed as

for low-intensity glow p e a k s b e c a u s e they increase t h e

p e a k - t o - b a c k g r o u n d r a t i o a n d t h e r e b y increase t h e
sensitivity. C o m m e r c i a l r e a d o u t systems a r e n o w
widely available b u t systems a r e still c o n s t r u c t e d b y
m a n y researchers.
A s o m e w h a t different a p p r o a c h , w h i c h yields m o r e
detailed i n f o r m a t i o n for f u n d a m e n t a l research, is t o
m e a s u r e t h e intensity of t h e light as a function of
wavelength d u r i n g h e a t i n g . T h i s is a c c o m p l i s h e d b y
rapidly s c a n n i n g t h e e m i t t e d light w i t h a s p e c t r o m e t e r
before t h e light enters t h e p h o t o m u l t i p l i e r t u b e . F a i r child et al. (1978) h a v e d e v e l o p e d a system w h i c h ,
with t h e aid of a c o m p u t e r , d r a w s a perspective
of a t h r e e - d i m e n s i o n a l p l o t of t h e w a v e l e n g t h a n d
intensity of t h e e m i t t e d light as a function of t h e
temperature.

w h e r e c is a c o n s t a n t . It is possible t o i n t e g r a t e this
e q u a t i o n for t h e case of a linear h e a t i n g r a t e
b e t w e e n t e m p e r a t u r e 0 , w h e n n0 electrons a r e
t r a p p e d , for e x a m p l e , after i r r a d i a t i o n , a n d T, t o
d e t e r m i n e t h e intensity / as a function of t e m p e r a t u r e .

1=

- cdn/dt = cnS exp( -

^Conduction
e J

E/kT)

band

Electron
trap

h
\
^

(3)

Hole
trap

Valence band

(a)
2. Atomic

Processes

in

Thermoluminescence

W h e n ionizing r a d i a t i o n falls o n a n i n s u l a t i n g solid,

t h a t is, o n e with a valence b a n d s e p a r a t e d b y a large
energy g a p from t h e c o n d u c t i o n b a n d (which m a y b e
crystalline, a m o r p h o u s o r p o l y m e r i c ) , it c a n c a u s e t h e
ejection of electrons from a n a t o m , leaving b e h i n d a
hole. T h e excited electrons m o v e in t h e c o n d u c t i o n
b a n d a n d t h e holes in t h e valence b a n d t h r o u g h o u t
the crystal. M o s t of these r e c o m b i n e , b u t a small
p e r c e n t a g e a r e t r a p p e d , usually a t p o i n t defects in t h e
crystal lattice. Similarly, i o n s c a n b e displaced t o f o r m
interstitials a n d vacancies w h i c h c a n also r e c o m b i n e
o r b e c o m e t r a p p e d . F i g u r e 2a r e p r e s e n t s t h e g e n e r a
tion of electrons a n d holes a n d their s u b s e q u e n t
t r a p p i n g in a m e t a s t a b l e state. If t h e m a t e r i a l is n o w

526

Conduction

band
e

Light
emitted

Valence

band
( b )

Figure 2
Band model for (a) the formation of electrons and holes
by ionizing radiation, and their trapping, and (b) the
release of electrons from their traps, the recombination
with holes and the emission of light, as a result of heating
the sample

Thermoluminescence

T h e solution is:
I=cn0S
x f

5.
exp( -

E/kT)exp
exp(-E/kT)dT

(-s/)
(4)

F i g u r e 3a r e p r e s e n t s t h e v a r i a t i o n of t h e n u m b e r of
t r a p p e d electrons with t e m p e r a t u r e for a c o n s t a n t
h e a t i n g r a t e . F i g u r e 3b s h o w s t h e associated light
o u t p u t as a function of t e m p e r a t u r e (i.e., t h e glow
p e a k ) a n d is described b y E q n . (4). V a r i o u s m e t h o d s
h a v e been devised t o a n a l y z e e x p e r i m e n t a l glow p e a k s
to o b t a i n t h e a c t i v a t i o n energies a n d t h e p r e e x p o nential factors S ( C h e n a n d K i r s c h 1981). In p r a c t i c e ,
m o r e t h a n o n e glow p e a k is generally f o u n d a n d
frequently these p e a k s o v e r l a p , w h i c h m a y m a k e t h e m
difficult t o analyze. S o m e t i m e s t h e p e a k s c a n b e
s e p a r a t e d b y r e a d i n g t h e m o u t successively, t h a t is,
partially r e a d i n g o u t a p e a k , d r o p p i n g t h e t e m p e r a
t u r e a n d t h e n r e r e a d i n g t h e p e a k . T h e single p e a k m a y
t h e n be a n a l y z e d t o give a n d S values. T h i s is called
p e a k cleaning. Alternatively, c o m p u t e r m e t h o d s of
curve fitting m a y be used t o a n a l y z e t h e individual
p e a k s m a k i n g u p a glow curve. A d j u s t a b l e p a r a m e t e r s
in these fitting p r o c e d u r e s a r e t h e a c t i v a t i o n energy E,
t h e p r e e x p o n e n t i a l S a n d t h e o r d e r of t h e kinetics.
A n alternative m o d e l for alkali halide crystals h a s
been p r o p o s e d ( A u s i n a n d A l v a r e z - R i v a s 1972) in
which t h e activated p r o c e s s for d e t r a p p i n g is associ
a t e d with t h e liberation of interstitial a t o m s , r a t h e r
t h a n electrons a n d holes.

Temperature

Figure 3
A plot of (a) the variation in the number of trapped
electrons in a previously irradiated sample with
temperature increasing with time, and (b) the resultant
glow peak arising from the release of electrons and their
recombination with holes

Dosimetry

T h e fact t h a t i r r a d i a t e d m a t e r i a l s c a n emit light w h e n

h e a t e d m a k e s t h e m p o t e n t i a l l y useful as d o s i m e t e r s .
In p r a c t i c e , r a d i a t i o n d o s i m e t e r s a r e used for t w o
p u r p o s e s : first, t o m o n i t o r received d o s e s for safety
p u r p o s e s , for e x a m p l e , of p e r s o n n e l in n u c l e a r p o w e r
s t a t i o n s ; a n d second, t o m e a s u r e a n d c o n t r o l the
d o s e s of r a d i a t i o n being applied, for e x a m p l e , in
r a d i a t i o n t r e a t m e n t of p a t i e n t s a n d with d i a g n o s t i c
rays. T h e m o s t i m p o r t a n t m a t e r i a l used for p e r s o n a l
d o s i m e t r y is L i F d o p e d w i t h m a g n e s i u m a n d tita
n i u m . T h i s m a t e r i a l exhibits several T L p e a k s , b u t if it
is c o o l e d m o d e r a t e l y quickly from 400 C t o r o o m
t e m p e r a t u r e a n d t h e n aged for 24 h a t 80 C, only the
m a j o r p e a k a t a b o u t 200 C r e m a i n s ; this p e a k is used
for d o s i m e t r y , t h a t is, t h e a r e a of t h e p e a k o r t h e p e a k
height gives a m e a s u r e of t h e r a d i a t i o n d o s e . Because
this is n o t a n a b s o l u t e m e t h o d , it is necessary t o first
establish a c a l i b r a t i o n p l o t of k n o w n d o s e vs
m e a s u r e d T L intensity. D o s i m e t e r s w h i c h h a v e been
e x p o s e d a n d r e a d o u t t o give a p a r t i c u l a r intensity c a n
t h e n be c o m p a r e d with t h e c a l i b r a t i o n p l o t t o deter
mine the dose.
L i F h a s t h e a d v a n t a g e t h a t , unlike film b a d g e s
(which h a v e t r a d i t i o n a l l y been used for d o s i m e t r y ) , it
h a s a linear r e l a t i o n s h i p b e t w e e n d o s e received a n d
T L emission a t all d o s e s b e l o w a b o u t 10 G y . A b o v e
this level, superlinearity (a d e p e n d e n c e steeper t h a n
linear) is o b s e r v e d .
L i F also h a s t h e p r o p e r t y of b e i n g tissue equivalent,
t h a t is, its a b s o r p t i o n of r a d i a t i o n is very similar t o
t h a t of b o d y tissue so t h a t t h e m e a s u r e d d o s e c o r r e s
p o n d s closely t o t h e b o d y d o s e . T h e t h i r d favorable
factor is t h a t t h e t h e r m o l u m i n e s c e n t r e s p o n s e t o
ionizing r a d i a t i o n is i n d e p e n d e n t of t h e energy of t h e
2
r a d i a t i o n , except for energies below 1 0 k e V . L i F c a n
be used t o detect r a y s , r a y s , electrons a n d p r o t o n s ;
6
m o r e o v e r , it is possible w i t h L i - e n r i c h e d L i F t o
detect t h e r m a l n e u t r o n s .
Very m a n y studies h a v e b e e n m a d e of L i F t o
u n d e r s t a n d t h e m e c h a n i s m of t h e r m o l u m i n e s c e n c e ,
b u t this is still a subject of c o n t r o v e r s y . M a g n e s i u m
a n d t i t a n i u m ions a r e essential d o p a n t s , a n d a s t a n
d a r d i z e d h e a t t r e a t m e n t is r e q u i r e d for o p t i m u m
performance.
T o d a y there a r e several practical d o s i m e t e r m a t e r
ials t o c h o o s e from d e p e n d i n g o n t h e a p p l i c a t i o n , for
e x a m p l e , lithium b o r a t e glass a n d C a F 2 , which is
extremely sensitive. T h e p r i m a r y r e q u i r e m e n t is t h a t a
d o s i m e t e r s h o u l d h a v e a glow p e a k a t a c o n v e n i e n t
t e m p e r a t u r e such as 200 C so t h a t t h e electrons,
t r a p p e d d u r i n g i r r a d i a t i o n , a r e completely "frozen
i n " a t r o o m t e m p e r a t u r e . T h e d o s i m e t e r is t h e n able
t o a c c u m u l a t e a d o s e over a p e r i o d of u p t o a year, o r
m o r e , w h i c h is faithfully m e a s u r e d b y t h e t h e r m o l u
5
minescence. D o s e s as low a s 1 0 " G y c a n b e
m e a s u r e d . R a d i a t i o n from t h e s u r r o u n d i n g s typically
3
gives a d o s e of a b o u t 1 0 " G y a year.

527

Thermoluminescence

4.

Dating

T h e r m o l u m i n e s c e n c e h a s been a p r i m a r y t e c h n i q u e
for d a t i n g in a r c h e o l o g y . It d e p e n d s o n t h e fact t h a t in
the p a s t s o m e c e r a m i c objects were fired d u r i n g their
m a n u f a c t u r e , t o t e m p e r a t u r e s a b o v e 500 C. T h i s
firing t r e a t m e n t e m p t i e d the t h e r m o l u m i n e s c e n t t r a p s
in the materials, for e x a m p l e , in q u a r t z particles, so
t h a t only t h e r a d i a t i o n t h a t w a s received s u b s e q u e n t l y
from n a t u r a l r a d i a t i o n c o n t r i b u t e d t o their t h e r m o l u
minescence. T h i s being so, a k n o w l e d g e of the d o s e
rate received by t h e object e n a b l e s t h e d a t e of its
m a n u f a c t u r e t o be calculated:
_ d o s e a c q u i r e d since firing
annual dose rate
_ t h e r m o l u m i n e s c e n c e x r a d s p e r unit of T L
r a d s per year
T h e t e r m " r a d s p e r unit of T L " m u s t be d e t e r m i n e d
from a l a b o r a t o r y c a l i b r a t i o n p l o t m a d e with the
same m a t e r i a l . S o m e difficulties m a y arise from
the fact t h a t h e a t i n g u p the s a m p l e t o r e a d o u t the
t h e r m o l u m i n e s c e n c e m a y t h e n affect its sensitivity t o
a calibrating d o s e . O t h e r c o m p l i c a t i o n s arise from the
fact t h a t different forms of r a d i a t i o n h a v e different
p e n e t r a t i o n d e p t h s . F o r e x a m p l e , particles p e n e t r a t e
d e p t h s of m i c r o m e t e r s , electrons millimeters a n d y
rays centimeters. Particles of q u a r t z will c o n s e q u e n t l y
receive different a n n u a l doses, d e p e n d e n t o n their
size, from their s u r r o u n d i n g s . Sophisticated p r o c e d
ures h a v e been developed t o c i r c u m v e n t these p r o b
lems (Aitken 1974). T h e n a t u r a l d o s e r a t e arising from
radioactive u r a n i u m , t h o r i u m , p o t a s s i u m a n d cosmic
rays c a n be d e t e r m i n e d from a c o m b i n a t i o n of c h e m
ical analysis, c o u n t i n g a n d t h e r m o l u m i n e s c e n c e
dosimetry. Since t h e half-lives of r a d i o a c t i v e u r a n i u m ,
t h o r i u m a n d p o t a s s i u m a r e very m u c h longer t h a n the
5
age of a n y m a n - m a d e ceramics (less t h a n 10 years),
the dose received is n o r m a l l y r e g a r d e d as being c o n
s t a n t with time.
It s h o u l d be m a d e clear t h a t only fractions of a
g r a m of material are necessary for t h e r m o l u m i n e s
cence a n d this c a n be r e m o v e d u n o b t r u s i v e l y from
ancient objects. T h e t e c h n i q u e w h e n carefully applied
c a n give a n a c c u r a c y of d a t i n g t o 1 0 % . In recent
years it h a s b e c o m e a powerful tool in t h e detection of
a r t forgeries ( F l e m i n g 1975).
T h e s a m e principles a p p l y t o t h e d a t i n g of geolo
gical rocks. Q u a r t z in the e a r t h ' s crust h a s received so
m u c h ionizing r a d a t i o n t h a t the t r a p s h a v e b e c o m e
s a t u r a t e d . H o w e v e r , w h e r e t h e r o c k s h a v e been
h e a t e d sufficiently, for e x a m p l e , by t h e flow of lava
from v o l c a n o s , t h e p r e v i o u s r a d i a t i o n effects a r e
erased. It t h e n b e c o m e s possible by m e a n s of t h e r m o
luminescence, t o establish the d a t e at which they were
last h e a t e d intensively. T h e r e is a n u p p e r limit of
528

a b o u t 10 years for t h e d a t i n g of r o c k s b y t h e r m o
luminescence, because over longer p e r i o d s t h e n a t u r a l
r a d i a t i o n s a t u r a t e s t h e t r a p s t h a t give rise t o t h e glow
p e a k s used in d a t i n g . T h e lower limit of d a t i n g
d e p e n d s o n t h e t h e r m o l u m i n e s c e n t sensitivity of a
m a t e r i a l b u t is typically a few years.

5. Material

Identification

T h e high sensitivity a n d simplicity of t h e r m o l u m i n e s

cence as a t e c h n i q u e allows it t o be used for identifica
tion. F o r e x a m p l e , a p a r t i c u l a r t y p e of m a t e r i a l m a y
be distinguished by its glow curve. O n e such applica
tion is in t h e identification of silicate d u s t s c a u s i n g
silicosis (Kriegseis a n d S c h a r m a n 1980). It h a s also
been discovered t h a t very intense s h o c k waves c a n
h a v e the effect of r e d u c i n g t h e t h e r m o l u m i n e s c e n c e
r e s p o n s e so t h a t , for e x a m p l e , t h e collision of a
m e t e o r i t e w t h t h e e a r t h ' s crust c a n be identified
( D o u g l a s et al. 1970).
See also: Art Forgeries: Scientific Detection

Bibliography
Aitken J 1974 Physics and Archaeology. Clarendon,
Oxford
Ausin V, Alvarez-Rivas J L 1972 Thermoluminescence and
annealing of F centers in KC1 y-radiated at toom temper
ature. J. Phys. C 5: 82-96
Becker 1973 Solid State Dosimetry. CRC, Cleveland, OH
Braunlich (ed.) 1979 Thermally stimulated relaxations in
solids. Top. Appl. Phys. 37: Springer, Berlin
Cameron J R, Suntharalingam N, Kenny G 1968 Thermo
luminescent Dosimetry. University of Wisconsin Press,
Madison, WI
Chen R, Kirsch Y 1981 Analysis of Thermally Stimulated
Processes. Pergamon, Oxford
Douglas G, Morency M, McDougall D J 1970 Detection of
strain in rocks using an intrinsic "semini-insulator" char
acteristic of some materials. Mod. Geol. 1: 211-17
Fairchild R G, Mattern L, Lengweiler K, Levey W 1978
Thermoluminescence of LiF TLD 100: emission-spectra
measurements. J. Appl. Phys. 49: 4512-22
Fleming S J 1975 Authenticity in Art: The Scientific Detec
tion of Forgery. Institute of Physics, London, pp. 73-97
Fleming S J 1979 Thermoluminescence Techniques in Archae
ology. Oxford University Press, New York
Kriegseis W, Scharman A 1980 Toxicity determination of
quartz and coal mine dust by thermoluminescence. Nucl.
Instr. Meth. 175: 239-40
McKeever S W S 1984 Thermoluminescence. Cambridge
University Press, Cambridge
McKinlay A F 1981 Thermoluminescence Dosimetry. Hilger,
London
Taylor G C, Lilley 1978 The analysis of thermolumines
cent glow peaks in LiF (TLD-100). J. Phys. D 11: 567-81
E. Lilley
[Norton, Northboro, Massachusetts, USA]

Thermophysical

Thermophysical Measurements,
Subsecond
U s i n g s u b s e c o n d pulse h e a t i n g t e c h n i q u e s it is p o s
sible t o reach t e m p e r a t u r e regions t h a t a r e n o t access
ible t o s t e a d y - s t a t e e x p e r i m e n t s , w h i c h a r e limited t o
t e m p e r a t u r e s below a b o u t 2000 K . T h i s article p r e
sents a description a n d general survey of s u b s e c o n d
t h e r m o p h y s i c s research including b o t h r a p i d resistive
h e a t i n g (volume) a n d pulse laser h e a t i n g (surface)
techniques. T h e e m p h a s i s will b e o n m e a s u r e m e n t s a t
very high t e m p e r a t u r e s . Pulse h e a t i n g t e c h n i q u e s a r e
used for t h e d e t e r m i n a t i o n of t h e t h e r m o p h y s i c a l
p r o p e r t i e s of m a t t e r for t e m p e r a t u r e s from a b o u t
1500 u p t o a b o u t 10 000 K . T h e time regime
12
covered is 1 - 1 0 " s. T h e s e investigations e n a b l e t h e
s t u d y of t h e b e h a v i o r of m a t t e r u n d e r c o n d i t i o n s b o t h
n e a r t o a n d far from t h e r m o d y n a m i c e q u i l i b r i u m .

1. Advantages

of Pulse Heating

Techniques

T r a d i t i o n a l static s t e a d y - s t a t e t e c h n i q u e s for t h e
m e a s u r e m e n t of t h e r m o p h y s i c a l p r o p e r t i e s a r e
generally limited t o t e m p e r a t u r e s below a b o u t
2000 K . T h i s limitation is a result of t h e chemical
i n t e r a c t i o n of t h e specimens with t h e c o n t a i n e r s , t h e
loss of m e c h a n i c a l s t r e n g t h , a n d p r o b l e m s with h e a t
transfer, e v a p o r a t i o n a n d electrical i n s u l a t i o n while
the s a m p l e a n d its e n v i r o n m e n t a r e k e p t for p e r i o d s of
u p t o h o u r s a t high t e m p e r a t u r e s . F a s t d y n a m i c
m e t h o d s h a v e been d e v e l o p e d t o a v o i d these difficult
ies a n d t o p e r m i t t h e e x t e n s i o n of t h e m e a s u r e m e n t s
to higher t e m p e r a t u r e s . T h e p r o p e r t i e s of m a t t e r a t
high t e m p e r a t u r e s a r e useful for h i g h - t e m p e r a t u r e
technologies s u c h a s a e r o s p a c e , n u c l e a r energy a n d
the e s t a b l i s h m e n t of t e m p e r a t u r e reference p o i n t s ,
including a p p l i c a t i o n s which a r e subjected t o hight e m p e r a t u r e / h i g h - p r e s s u r e c o n d i t i o n s , as well as for
m o d e l l i n g a n d basic t h e o r y .
Such pulse h e a t i n g e x p e r i m e n t s p e r f o r m t h e entire
m e a s u r e m e n t in less t h a n 1 s. T h e h e a t i n g rates used
4
_1
1 0
_1
and 1 0 K s
a n d require
vary b e t w e e n 1 0 K s
r e c o r d i n g e q u i p m e n t with s h o r t r e s p o n s e times. T h e
scope of this article is restricted t o resistive selfh e a t i n g m e t h o d s a n d t o laser h e a t i n g t e c h n i q u e s .
O t h e r t e c h n i q u e s for p r o p e r t y m e a s u r e m e n t s u p t o
5 0 0 0 - 1 0 000 K , such as chemical flames, s h o c k waves,
solar h e a t i n g , fission/fusion a n d high-energy electron
o r n e u t r o n h e a t i n g , will n o t b e t a k e n i n t o c o n s i d e r a
tion here.

2. Resistive

Pulse

Heating

2.1
Experimental
R a p i d v o l u m e h e a t i n g m e t h o d s a r e limited t o electri
cally c o n d u c t i n g m a t e r i a l s a n d involve resistive selfh e a t i n g of t h e specimen b y passing a n electrical
c u r r e n t pulse t h r o u g h it. S t a r t i n g a t r o o m t e m p e r a

Measurements,

Subsecond

t u r e , t h e m e a s u r e m e n t s c a n b e p e r f o r m e d far i n t o t h e
liquid p h a s e of t h e investigated m a t e r i a l . D e p e n d i n g
o n t h e h e a t i n g r a t e r e q u i r e d , t h e energy is s t o r e d in a
b a t t e r y b a n k (slow) o r in a c a p a c i t o r b a n k (fast). T h e
m e t a l s a m p l e s u s u a l l y wires, foils o r t u b e s a r e
c o n t a i n e d in a c o n t r o l l e d e n v i r o n m e n t c h a m b e r .
M e a s u r e m e n t s c a n be p e r f o r m e d in v a c u u m o r u n d e r
a m b i e n t pressures u p t o 5 k b a r u n d e r nearly isobaric
c o n d i t i o n s , t h e pressurized m e d i u m n o r m a l l y being
argon or water.
A functional d i a g r a m of a typical resistive pulse
h e a t i n g system is given in F i g . 1; t h e details of t h e
c o m p o n e n t s vary with t h e time scale of t h e m e a s u r e
m e n t . T h e discharge circuit typically consists of the
energy s t o r a g e , t h e m a i n switch (e.g., high-voltage
m e r c u r y v a p o r ignition t u b e ) a n d t h e specimen
c h a m b e r with w i n d o w s for optical diagnostics,
t o g e t h e r with t h e pressure c o n t r o l . A d d i t i o n a l re
q u i r e m e n t s a r e a c r o w b a r switch t o s t o p t h e experi
m e n t a t a n y desired m o m e n t a n d t h e c h a r g i n g unit.
The measured quantities are the current through
t h e s a m p l e , t h e voltage a c r o s s t h e s a m p l e , t h e t e m p e r
a t u r e of t h e s a m p l e , which is d e t e r m i n e d using optical
p y r o m e t e r s , a n d o t h e r optical m e a s u r e m e n t s (e.g.,
s a m p l e v o l u m e , velocity of s o u n d , see T a b l e 1), as well
as t h e a m b i e n t p r e s s u r e . T h e r e c o r d i n g e q u i p m e n t is
n o r m a l l y placed in a shielded r o o m : t h e faster t h e rise
time of a n e x p e r i m e n t , t h e b e t t e r t h e shielding h a s t o
be. T h e r e c o r d e d d a t a a r e e v a l u a t e d after t h e experi
m e n t with t h e aid of a c o m p u t e r .
D u r i n g t h e c o u r s e of o n e fast pulse e x p e r i m e n t , it is
possible t o o b t a i n d a t a for, for e x a m p l e , e n t h a l p y ,
t e m p e r a t u r e , specific electric resistivity, specific
v o l u m e as a function of time (while t h e specimen
rapidly passes t h r o u g h a wide r a n g e of states) a n d
s o u n d velocity a t a desired t e m p e r a t u r e (as well as
o t h e r q u a n t i t i e s , as cited in T a b l e 1) reaching far i n t o
the liquid p h a s e of t h e investigated m a t e r i a l . F r o m
these q u a n t i t i e s it is possible t o calculate, for liquid
m e t a l s , t h e specific h e a t a t c o n s t a n t p r e s s u r e , the
t h e r m a l e x p a n s i o n coefficient, G r u n e i s e n ' s y, a d i a b a tic a n d i s o t h e r m a l b u l k m o d u l i i a n d compressibilities,
specific h e a t a t c o n s t a n t p r e s s u r e a n d specific h e a t a t
constant volume.
F o r t h e solid m a t e r i a l , d a t a for t h e r m o p h y s i c a l
p r o p e r t i e s , such a s solid-solid t r a n s i t i o n t e m p e r a t u r e s
a n d energies, n o r m a l spectral e m i t t a n c e , h e m i s p h e r i
cal t o t a l e m i t t a n c e a n d t h e r m a l c o n d u c t i v i t y (see
T a b l e 1), c a n be o b t a i n e d by slower pulse experi
m e n t s . E x a c t f o r m u l a e for t h e calculation of these
t h e r m o p h y s i c a l p r o p e r t i e s s h o u l d be t a k e n from t h e
review articles of G a t h e r s (1986) a n d of Cezairliyan
(1988).
T h e pulse h e a t i n g t e c h n i q u e s described here a r e
usually classified u n d e r three categories, d e p e n d i n g o n
t h e r e q u i r e d time resolution of t h e m e a s u r i n g e q u i p
m e n t : millisecond resolution systems, m i c r o s e c o n d
r e s o l u t i o n systems a n d s u b m i c r o s e c o n d resolution
systems.

529

Thermophysical

Measurements,

Subsecond

Circuit
inductivity

Circuit
resistivity

Shielded

Pressure(
control

diiCharging

Crowbar

unit

switch

Temperature

<

measurement
.

Other optical measurements

room

<

hi

Voltage
measurement
Current
Current

probe

measurement

Start
Main
switch

Figure 1
A typical resistive pulse heating system

2.2 Experiments with Millisecond Time

Resolution
T h e t e m p e r a t u r e r a n g e covered in millisecond t i m e
resolution e x p e r i m e n t s is from a b o u t 1000 u p t o t h e
melting t e m p e r a t u r e of t h e specimen. T h e loss of
stability of t h e s a m p l e a t m e l t i n g a n d t h e collapse d u e
t o gravity n o r m a l l y d e t e r m i n e t h e u p p e r t e m p e r a t u r e
limit in this time regime. T h e a m b i e n t pressures a r e
from v a c u u m u p t o 1 b a r . I n t h e 1 s t o 1 m s r a n g e t h e
techniques a r e generally well d e v e l o p e d a n d allow
accurate measurements. The uncertainties
are
between 1 % a n d 3 % . T h e c u r r e n t t h r o u g h t h e s a m p l e
is d e t e r m i n e d from t h e m e a s u r e m e n t of t h e voltage
across a s t a n d a r d resistance placed in series with t h e
specimen. T h e voltage a c r o s s t h e m i d d l e p a r t of t h e
s a m p l e is m e a s u r e d b y knife-edge p r o b e s . A small
r e c t a n g u l a r hole in t h e wall of t h e specimen a p r o x i m a t e s b l a c k b o d y c o n d i t i o n s for optical t e m p e r a t u r e
m e a s u r e m e n t s . T h e p y r o m e t e r s n o w used h a v e silicon
p h o t o d i o d e s with interference filters a s d e t e c t o r s ,
because the use of p h o t o m u l t i p l i e r t u b e s is m o r e
u n c e r t a i n o w i n g t o drift p r o b l e m s d u r i n g t h e
experiments.
T h e e x p e r i m e n t a l q u a n t i t i e s a r e r e c o r d e d every
0.4 m s with a digital d a t a acquisition system. T h e
t h e r m o p h y s i c a l p r o p e r t i e s t h a t m a y be o b t a i n e d with
millisecond time r e s o l u t i o n a r e listed in T a b l e 1.
T h e only possibility of o b t a i n i n g d a t a for t h e liquid
p h a s e with millisecond time r e s o l u t i o n is t o p e r f o r m
this type of e x p e r i m e n t in a m i c r o g r a v i t y e n v i r o n
m e n t . T h e a b s e n c e of gravity e n a b l e s investigation in
t h e first 50 of the liquid p h a s e of t h e s a m p l e .
M i c r o g r a v i t y s i m u l a t i o n e x p e r i m e n t s with N A S A ' s

530

K C - 1 3 5 aircraft h a v e been p e r f o r m e d successfully b y

Cezairliyan et al. (1990).
Millisecond time r e s o l u t i o n investigations, exactly
as described here, a r e carried o u t a t a very precise
level a t t h e N a t i o n a l I n s t i t u t e of S t a n d a r d s a n d T e c h
n o l o g y , G a i t h e r s b u r g , M a r y l a n d , U S A , b y A . Cezair
liyan a n d c o - w o r k e r s a n d a t t h e I s t i t u t o di M e t r o l o g i a
" G . C o l o n e t t i , " T o r i n o , Italy, b y F . Righini a n d
co-workers.
A t t h e I n s t i t u t e for T h e r m a l E n g i n e e r i n g a n d
E n e r g y R e s e a r c h , Boris K i d r i c h I n s t i t u t e of N u c l e a r
Sciences, Belgrade, K . M a g l i c a n d c o - w o r k e r s use
t h e r m o c o u p l e s directly welded t o t h e s a m p l e s t o per
form temperature measurements. As the current
t h r o u g h t h e s a m p l e influences these m e a s u r e m e n t s , a
special c o m p e n s a t i o n t o e v a l u a t e t r u e t e m p e r a t u r e s
h a s t o b e used. T h e h e a t i n g of t h e specimen typically
lasts 1 s a n d t h e s a m p l i n g r a t e is 1 k H z .
T h e slow pulse h e a t i n g system o p e r a t e d by I.
P e t r o v a a n d c o - w o r k e r s a t t h e I n s t i t u t e of H i g h
T e m p e r a t u r e s , I V T A N , M o s c o w , with a h e a t i n g time
of a b o u t 1 s, a g a i n uses a n optical p y r o m e t e r for
t e m p e r a t u r e m e a s u r e m e n t s , w i t h s a m p l i n g rates of
a b o u t 40 . O n e of their m a i n interests is t h e invest
igation of alloys such as t u n g s t e n - c o p p e r .
2.3 Experiments with Microsecond
Time Resolution
T h e t e m p e r a t u r e r a n g e c o v e r e d in m i c r o s e c o n d time
r e s o l u t i o n e x p e r i m e n t s is from a b o u t 2000 u p t o
a b o u t 6000 K , d e p e n d i n g o n t h e m a t e r i a l investi
gated. T h u s t h e e x p e r i m e n t s lead far i n t o t h e liquid
p h a s e of t h e m e t a l . T h e stability limit for this k i n d of

Thermophysical

Measurements,

Subsecond

Table 1
Thermophysical properties that may be measured by dynamic (subsecond) heating methods
Heating method

Time
resolution

Resistive heating

ms

Laser heating

Solids

Liquids

heat capacity
thermal expansion
electrical resistivity
hemispherical total emittance
normal spectral emittance
phase transitions
solid-solid transformation temperature
solid-solid transformation energy
melting temperature
apparent temperature at melting point
deduced from radiance
thermal conductivity
mechanical properties"
8
velocity of sound

surface tension8
heat of fusion8
heat capacity
8
electrical resistivity
8
hemispherical total emittance
phase transitions

heat of fusion
heat capacity
electrical resistivity
thermal expansion
velocity of sound
melting temperature
phase transitions
apparent temperature at melting point
deduced from radiance
8
thermal conductivity
8
normal spectral emittance

heat of fusion
heat capacity
cv
electrical resistivity
thermal expansion
velocity of sound
melting temperature
phase transitions
apparent temperature at melting point
deduced from radiance
Gruneisen
adiabatic bulk modulus
isothermal bulk modulus
adiabatic compressibility
isothermal compressibility
8
thermal conductivity
8
normal spectral
emittance
8
heat of fission 8
surface tension

heat of fusion
heat capacity
thermal expansion
normal spectral emittance
melting temperature
vapor pressure
partial pressures
reflectivity
phase transitions
hemispherical total emittance
transmission
thermal conductivity

heat of fusion
heat capacity
thermal expansion
normal spectral emittance
melting temperature
vapor pressure
partial pressures
reflectivity
phase transitions
8
surface tension
8
viscosity

ns

phase transitions
reflectivity
transmission
thermal conductivity

phase transitions
reflectivity

ps

phase transitions
reflectivity
transmission
velocity of sound

phase transitions
reflectivity

a in development stage

531

Thermophysical

Measurements,

Subsecond

e x p e r i m e n t s is set by the o n s e t of c o m p l e x g e o m e t r y .
7
T h e h e a t i n g rates a r e typically in t h e r a n g e 1 0 8
_ 1
1 0 K s . M o r e o v e r , t o achieve high t e m p e r a t u r e s ,
high pressures h a v e t o be applied, r a n g i n g u p t o
5 kbar.
M i c r o s e c o n d t e c h n i q u e s h a v e r e a c h e d a high level
of d e v e l o p m e n t a n d achieve a c c u r a t e m e a s u r e m e n t s
o n liquid m e t a l s . T h e uncertainties a r e b e t w e e n 2 %
a n d 7 % . T h e c u r r e n t t h r o u g h t h e s a m p l e is m e a s u r e d
using a high-precision c u r r e n t p r o b e a n d the voltage
a l o n g the s a m p l e is m e a s u r e d by knife-edge p r o b e s o r
with o h m i c voltage dividers.
T h e surface r a d i a n c e of t h e h o t surface is detected
b y fast p y r o m e t e r s w i t h silicon p h o t o d i o d e s c o m b i n e d
with interference niters. T h e c o n s t a n t r a d i a t i o n of t h e
melting s a m p l e is used as a fixed p o i n t of t h e t e m p e r
a t u r e calculations, using the K i r c h h o f f - P l a n c k law.
T e m p e r a t u r e s a r e calculated from m e a s u r e d intensit
ies by f o r m i n g ratios of t h e intensity a t a r b i t r a r y
p o i n t s to t h e intensity a t melt. T h i s is carried o u t
u n d e r the a s s u m p t i o n t h a t , b e c a u s e of t h e lack of
emissivity d a t a for this region, t h e emissivity a t t h e
melting p o i n t e(X9Tm) is e q u a l t o the emissivity in t h e
liquid p h a s e (,).
V o l u m e s a r e m e a s u r e d with s h a d o w g r a p h systems
by backlighting t h e s a m p l e , t h e s a m e m e a s u r e m e n t s
p r o v i n g t h e stability of t h e specimen. S o m e systems
a r e also able t o m e a s u r e s o u n d velocities in t h e pulse
h e a t e d samples a t different t e m p e r a t u r e s .
T h e e x p e r i m e n t a l q u a n t i t i e s a r e r e c o r d e d every
100 ns with digital d a t a acquisition systems. T h e
t h e r m o p h y s i c a l p r o p e r t i e s o b t a i n e d with m i c r o s e c o n d
time resolution a r e listed in T a b l e 1.
T h e well-equipped a p p a r a t u s described previously
is t h a t of R . S. H i x s o n a n d c o - w o r k e r s a t t h e L o s
A l a m o s N a t i o n a l L a b o r a t o r y , N e w M e x i c o , U S A . By
m e a s u r i n g t h e speed of s o u n d in liquid m e t a l s they a r e
able t o calculate all the t h e r m o p h y s i c a l p r o p e r t i e s
cited for fast pulse h e a t i n g systems in Sect. 2 . 1 . O t h e r
o p e r a t i o n a l systems will n o w be discussed.
A t the N a t i o n a l Institute of S t a n d a r d s a n d T e c h
nology in G a i t h e r s b u r g , M a r y l a n d , U S A , a m i c r o
second r e s o l u t i o n system w a s recently established b y
J. L. M c C l u r e a n d c o - w o r k e r s . T h e w h o l e e x p e r i m e n
tal s e t u p is h o u s e d in a shielded r o o m , with all the
recording equipment outside.
In E u r o p e , at t h e C o m m i s s a r i a t a l'Energie A t o m i q u e in Paris, A . B e r t h a u l t a n d c o - w o r k e r s h a v e e s t a b
lished nearly the s a m e system as t h a t in L o s A l a m o s .
T h i s i n s t r u m e n t a t i o n is n o w being o p e r a t e d by T .
T h e v e n i n . T h e i r results, m a i n l y o n t r a n s u r a n i u m ele
m e n t s , a r e confidential.
E. K a s c h n i t z a n d G . P o t t l a c h e r a t t h e Institut fur
Experimentalphysik der Technischen
Universitat
G r a z , A u s t r i a , h a v e also b e g u n t o establish a m i c r o
second resolution system similar t o t h e o n e in L o s
A l a m o s . T h i s system is still u n d e r c o n s t r u c t i o n , b u t
they h a v e a l r e a d y been able t o r e p o r t s o m e i m p r o v e
m e n t s , such as a fast p y r o m e t e r sensitive d o w n t o t h e

532

m e l t i n g t e m p e r a t u r e of c o p p e r , m e a s u r e m e n t s of
s o u n d velocity in solid m e t a l s a n d the first results o n
t h e emissivity of liquid m e t a l s .
M . A . Scheindlin a n d c o - w o r k e r s a t t h e Institute of
H i g h T e m p e r a t u r e s , I V T A N , M o s c o w , o p e r a t e a sys
7
l
t e m with h e a t i n g rates of 10 s ~ . T h e onset of their
p y r o m e t e r is a t 2500 K . T h i s g r o u p also p e r f o r m s
e x p e r i m e n t s with laser pulse h e a t i n g a n d c o n n e c t s t h e
results o b t a i n e d b y b o t h m e t h o d s .
A n o t h e r pulse h e a t i n g system is o p e r a t e d by M .
M a r t y n y u k a n d c o - w o r k e r s at t h e Patrice L u m u m b a
P e o p l e ' s F r i e n d s h i p University, M o s c o w . T h e m a i n
interest of this g r o u p is in t h e investigation of p h a s e
transitions.
2.4 Experiments
Resolution

with Submicrosecond

Time

T h e t e m p e r a t u r e r a n g e covered in s u b m i c r o s e c o n d
time r e s o l u t i o n e x p e r i m e n t s is from a b o u t 2000 u p
t o m o r e t h a n 10 000 K , a g a i n d e p e n d i n g o n t h e m a t e r
ial investigated. I n this k i n d of e x p e r i m e n t , the reach
ing of t h e s p i n o d a l line in t h e V p l a n e of t h e classical
v a n d e r W a a l s e q u a t i o n of state is t h e stability limit.
F u r t h e r h e a t i n g will p r o d u c e r a p i d v o l u m e e x p a n s i o n ;
t h e so-called " w i r e e x p l o s i o n " will t a k e place a n d
i n t e r r u p t electrical c o n d u c t i v i t y . T h e h e a t i n g rates
9
_ 1
applied a r e m o r e t h a n 1 0 K s . T h e s e high h e a t i n g
rates also allow investigations a t 1 b a r , b u t m o r e
a c c u r a t e results a r e o b t a i n e d a t a m b i e n t pressures u p
to 5 kbar.
S u b m i c r o s e c o n d t e c h n i q u e s allow t h e investigation
of liquid m e t a l s u p t o t h e e n d of their liquid p h a s e .
Because of t h e time regime ( s a m p l i n g r a t e e a c h 10 ns
o r less) a n d t h e wide t e m p e r a t u r e r a n g e , the uncer
tainties will increase from 5 % t o 1 5 % . G e n e r a l l y , the
o b t a i n e d results a r e in g o o d a g r e e m e n t with the
results from m i c r o s e c o n d t e c h n i q u e s .
T h e a c h i e v e m e n t of h e a t i n g rates g r e a t e r t h a n
9
_1
requires a very low inductivity for t h e dis
10 Ks
c h a r g e circuit a n d a very g o o d shielding of the
m e a s u r e d signals. T h i s calls for a coaxially m o u n t e d
discharge system with d o u b l e coaxially shielded m e a
suring lines leading t o a screened r o o m which includes
the recording equipment.
E x p e r i m e n t s with s u b m i c r o s e c o n d time resolution
a r e p e r f o r m e d a t t h e I n s t i t u t fur E x p e r i m e n t a l p h y s i k
d e r T e c h n i s c h e n U n i v e r s i t a t G r a z , A u s t r i a . T h e only
difference from t h e m i c r o s e c o n d m e a s u r e m e n t s is the
m e a s u r e m e n t of c u r r e n t , w h i c h is carried o u t with t h e
aid of a n i n d u c t i o n coil a n d s u b s e q u e n t electrical RC
i n t e g r a t i o n of t h e i n d u c e d signal. Besides the d e t e r m i
n a t i o n of t h e r m o p h y s i c a l p r o p e r t i e s u p t o very high
t e m p e r a t u r e s , e x p e r i m e n t s h a v e also b e e n m a d e o n
o b t a i n i n g critical p o i n t d a t a for m e t a l s by investiga
tions a t elevated pressures. T h e first results o n lead
h a v e been r e p o r t e d b y P o t t l a c h e r a n d J a g e r (1990).
A t t h e I n s t i t u t e of H i g h T e m p e r a t u r e s , I V T A N ,
M o s c o w , Savvatimskii a n d c o - w o r k e r s a r e interested
in e x p l o d i n g wires p h e n o m e n a a n d they a r e also

Thermophysical

determining
metals.

3. Laser

thermophysical

Pulse

properties

of

liquid

Heating

3.1
Experimental
T h e m a i n a d v a n t a g e of laser pulse h e a t i n g is t h a t it
c a n be used for t h e investigation of all k i n d s of
m a t e r i a l s in a d d i t i o n t o m e t a l s such as c e r a m i c s , fuel
m a t e r i a l s a n d n o n m e t a l s . T h e energy is delivered t o
the s a m p l e in a localized w a y so t h a t efficient h e a t i n g
results a n d small specimens c a n be used. T h e use of
u l t r a s h o r t laser pulses results in very fast h e a t i n g ;
t h u s , extremely high t e m p e r a t u r e s m a y be achieved.
By using this t e c h n i q u e t h e a m o u n t of m a t t e r being
h e a t e d is c o n s i d e r a b l y smaller, b u t t h e m a i n d i s a d v a n
tage is, in m o s t cases, t h a t t h e laser energy d e p o s i t i o n
r a t e c a n n o t be assessed precisely.
I n this k i n d of e x p e r i m e n t , a s h o r t pulse of laser
r a d i a t i o n h e a t s small p a r t s of t h e surface of a plain
s a m p l e or, w i t h o u t c o n t a i n m e n t , t h e full v o l u m e of a
small levitating s p h e r e ( 5 0 0 - 1 0 0 0 p m d i a m e t e r ) from
r o o m t e m p e r a t u r e u p t o t h e liquid p h a s e . A g a i n , t h e
samples a r e inside a c o n t r o l l e d e n v i r o n m e n t c h a m b e r
a n d the m e a s u r e m e n t s c a n b e p e r f o r m e d in v a c u u m
(laser h e a t i n g , v a c u u m ( L H V ) ) o r u n d e r a m b i e n t
pressures u p t o 2 k b a r (laser h e a t i n g , p r e s s u r e ( L H P ) ) .
T h e pressurized m e d i u m is inert gas.
A s c h e m a t i c display of t h e e x p e r i m e n t a l t e c h n i q u e
a n d s o m e m a i n items of i n s t r u m e n t a t i o n of a laser
pulse h e a t i n g system a r e s h o w n in F i g . 2. T h e details
of the c o m p o n e n t s v a r y for different m e a s u r e m e n t s
a n d for different t e c h n i q u e s .
T h e e x p e r i m e n t a l s e t u p for p e r f o r m i n g laser h e a t
ing m e a s u r e m e n t s is c e n t e r e d o n a pulsed laser s o u r c e ,

Time control, data

Mass
spectrometer

Figure 2
A laser pulse heating system

aquisition

Measurements,

Subsecond

usually a n N d : Y A G m o d e - l o c k e d laser. T h e o u t p u t
r a d i a t i o n ( r e c t a n g u l a r laser pulse, = 1.06 p m , 90 fs
t o 1 m s pulse d u r a t i o n , G a u s s i a n spatial p o w e r
7
2
profile, p o w e r densities u p t o 1 0 W c m ) m a y be
frequency c o n v e r t e d b y h a r m o n i c g e n e r a t i o n in n o n
linear crystals, r e a c h i n g visible a n d ultraviolet w a v e
lengths. T h e laser pulse is focused o n t h e polished
surface of t h e s a m p l e a n d p r o v i d e s t h e excitation u p
t o t e m p e r a t u r e s of 5 0 0 0 - 1 0 000 K. T h e h e a t e d a r e a of
the t a r g e t r a n g e s from 1 m m t o 3 m m in d i a m e t e r . T h e
s a m p l e itself is inside a c o n t r o l l e d e n v i r o n m e n t
c h a m b e r ( n o t indicated in Fig. 2).
T h e light e m i t t e d from t h e centre of the target is
detected optically by a high-speed p y r o m e t e r ; the
c a l c u l a t i o n of t h e t e m p e r a t u r e of t h e target surface
b e c o m e s possible o n certain a s s u m p t i o n s ; the s a m e is
t r u e for the d e t e r m i n a t i o n of spectral a n d t o t a l emit
t a n c e a n d for ultrafast p h a s e t r a n s i t i o n s . M e a s u r e
m e n t s of v o l u m e p r o p e r t i e s o n acoustically levitating
spheres such as density, t h e r m a l e x p a n s i o n , e n t h a l p y
a n d h e a t c a p a c i t y rely o n t h e a c h i e v e m e n t of t e m p e r
a t u r e u n i f o r m i t y o r t h e a c c u r a t e k n o w l e d g e of t h e
t e m p e r a t u r e profile t h r o u g h o u t t h e s a m p l e . A s in
m o s t cases t h e laser energy d e p o s i t i o n r a t e c a n n o t be
assessed precisely, t h e c o o l i n g tail of the levitation
e x p e r i m e n t s is used preferentially (e.g., for t h e deter
m i n a t i o n of Cp(X), from t h e g r a p h of t e m p e r a t u r e vs
time).
A m a s s s p e c t r o m e t e r is used t o d e t e r m i n e the
p a r t i a l pressures of t h e v a r i o u s n e u t r a l a n d ionized
g a s e o u s species of t h e v a p o r jet. S p e c t r o s c o p i c t e m
p e r a t u r e m e a s u r e m e n t s a n d high-speed p h o t o g r a p h y
of t h e e v a p o r a t i n g j e t a r e r e q u i r e d as i n p u t d a t a t o
investigate t h e gas d y n a m i c e x p a n s i o n m e c h a n i s m a t
e x t r e m e rates of e v a p o r a t i o n a n d t o estimate b a c k scattering effects.
A p r o b i n g laser b e a m c a n be focused o n t h e center
of the h e a t e d a r e a of t h e s a m p l e a n d t h e reflected a n d /
o r t r a n s m i t t e d b e a m energies a r e m e a s u r e d by light
d e t e c t o r s . T h e s e signals, o n c e n o r m a l i z e d , p r o v i d e
reflectivity a n d / o r t r a n s m i s s i o n d a t a for t h e p r o b e d
w a v e l e n g t h a t a certain p o i n t in time. F r o m the
i n s t a n t a n e o u s values of reflectivity a n d t r a n s m i s s i o n ,
it is possible to d e d u c e the c o m p l e x index of refraction
of t h e m a t e r i a l d u r i n g t h e i n t e r a c t i o n .
O t h e r investigation m e t h o d s a r e also used, b u t a r e
n o t i n d i c a t e d in Fig. 2, such as x-ray investigations of
t h e s a m p l e s (levitated spheres) t o o b t a i n v o l u m e d a t a
as well as density.
After r e c o r d i n g t h e m e a s u r e m e n t s with fast digital
e q u i p m e n t , this difficult t e c h n i q u e needs a lot of
theoretical b a c k g r o u n d i n f o r m a t i o n a b o u t optical
p y r o m e t r y , t h e energy b a l a n c e of the s a m p l e , Fresnel
f o r m u l a e a n d so o n in o r d e r t o calculate from the
m e a s u r e d d a t a p r o p e r t i e s such as t e m p e r a t u r e , emissi
vity, C p , t h e c o m p l e x index of refraction a n d so o n .
O w i n g t o t h e c o m p l e x c a l i b r a t i o n a n d analytical
p r o c e d u r e s , the u n c e r t a i n t y of the o b t a i n e d t h e r m o
physical p r o p e r t i e s increases strongly a n d their inter-

533

Thermophysical

Measurements,

Subsecond

p r e t a t i o n s a r e n o t resolved satisfactorily as yet. F o r

C p values, for e x a m p l e , o b t a i n e d from laser pulse
h e a t i n g e x p e r i m e n t s o n levitating spheres, a n u n c e r
t a i n t y of a t least 3 0 % h a s t o be a s s u m e d .
The thermophysical properties obtained with the
aid of laser pulse h e a t i n g a r e listed in T a b l e 1. F o r
m o r e e x p e r i m e n t a l a n d theoretical b a c k g r o u n d infor
m a t i o n o n L H V a n d L H P e x p e r i m e n t s , see t h e review
articles by O h s e (1990a, b ) . T h e laser pulse h e a t i n g of
very small s a m p l e s in d i a m o n d anvil cells will n o t b e
considered here.
3.2 Pulse Duration of Laser Heating
Experiments
(a) Millisecond
heating pulses. I n t h e millisecond
r a n g e , laser h e a t i n g is used for m e a s u r i n g t h e t h e r m a l
diffusivity a n d s o m e t i m e s also t h e h e a t c a p a c i t y of
m a t e r i a l s in t h e solid as well as in t h e liquid p h a s e
near the melting point. In the microsecond range,
pulsed laser h e a t i n g is used t o o b t a i n t h e r m o p h y s i c a l
p r o p e r t i e s of h i g h - m e l t i n g - p o i n t m a t e r i a l s , as it is
used in n u c l e a r r e a c t o r t e c h n o l o g y a t high t e m p e r a
tures.
A t t h e E u r o p e a n I n s t i t u t e for T r a n s u r a n i u m Ele
m e n t s , K a r l s r u h e , G e r m a n y , C. R o n c h i a n d J. P.
H i e r n a u t h a v e h e a t e d acoustically levitated, spherical
samples of fuel m a t e r i a l s in a p r e s s u r e vessel (pres
sures from v a c u u m u p t o 4000 b a r ) b y m e a n s of four
symetrically a r r a n g e d laser b e a m s (100 m s pulse
d u r a t i o n ) . T h e y use a very sophisticated investigation
system a n d p e r f o r m time-resolved electrical, optical
a n d x-ray m e a s u r e m e n t t e c h n i q u e s from w h i c h t h e
t e m p e r a t u r e , spectral a n d t o t a l e m i t t a n c e , density,
t h e r m a l e x p a n s i o n , e n t h a l p y a n d h e a t c a p a c i t y of t h e
s a m p l e c a n be o b t a i n e d u p t o t e m p e r a t u r e s a b o v e
5000 K .
A t t h e Institute of H i g h T e m p e r a t u r e s , I V T A N ,
M o s c o w , M . A . Scheindlin a n d c o - w o r k e r s h a v e t w o
different facilities ( 1 m s o r 20 ns pulse d u r a t i o n ,
1.06 ) for investigations u n d e r a m b i e n t pressures
from v a c u u m u p t o 1000 b a r . T h e y investigate p h a s e
t r a n s i t i o n s , such as melting, v a p o r i z a t i o n a n d s u b
limation, optical p r o p e r t i e s , such as t h e a n g u l a r distri
b u t i o n of reflected light, a n d they also use t h e c o o l i n g
tail of t h e e x p e r i m e n t for t h e d e t e r m i n a t i o n of Cp(X)
from t h e t e m p e r a t u r e vs time g r a p h . T h i s g r o u p is t h e
only o n e which c a n c o m b i n e its o w n results o b t a i n e d
by resistive pulse h e a t i n g with t h o s e o b t a i n e d b y laser
pulse h e a t i n g .
(b) Nanosecond heating pulses. T h e r e is s o m e a d v a n
tage in the use of laser pulses in t h e n a n o s e c o n d r a n g e
in t e r m s of efficiency in h e a t i n g a n d stability of t h e
h e a t e d a r e a after melting. D u r i n g h e a t i n g a n d r a p i d
cooling, time-resolved ellipsometry a n d t r a n s i e n t re
flectivity m e a s u r e m e n t s a r e used t o d e t e r m i n e t h e
electronic s t r u c t u r e of m o l t e n m a t e r i a l s . T h e s e tech
niques a r e limited t o excitations n o t involving excess
ive m a t e r i a l e v a p o r a t i o n , w h i c h m i g h t affect optical
a n d electrical m e a s u r e m e n t s .

534

N a n o s e c o n d laser-induced p h a s e t r a n s i t i o n s a n d
m e t a s t a b l e p h a s e s q u e n c h i n g a r e being investigated a t
t h e D i p a r t i m e n t o di Fisica of t h e University of C a t a
nia, Italy, b y P . Baeri. T h e m e a s u r e m e n t s allow t h e
d e t e r m i n a t i o n of m e l t i n g p o i n t s a n d t h e e v a l u a t i o n of
heat capacity and thermal conductivity.
A t t h e Physics D e p a r t m e n t of t h e G e n e r a l M o t o r s
Research Laboratories, Warren, Michigan, USA, G.
Eesley h a s used a n optical t r a n s i e n t reflectance tech
n i q u e with p i c o s e c o n d laser pulses t o c h a r a c t e r i z e
b o t h t h e t h e r m a l a n d a c o u s t i c t r a n s p o r t d y n a m i c s of
thin m e t a l films. T h e t r a n s i e n t thermoreflectance a n d
piezoreflectance m e a s u r e m e n t s c a n be e x t e n d e d i n t o
t h e f e m t o s e c o n d time d o m a i n t o investigate t h e d y n a
mics of energy t r a n s p o r t u n d e r n o n e q u i l i b r i u m elec
t r o n lattice t e m p e r a t u r e differences.
M . Malvezzi a t t h e D i p a r t i m e n t o di E l e t t r o n i c a of
t h e U n i v e r s i t y of P a v i a , Italy, h a s built u p a very
m a t u r e system for p i c o s e c o n d laser pulses (30 p s ,
1.06 ) t o m e a s u r e time-resolved reflectivity a n d / o r
t r a n s m i s s i o n values, p h a s e t r a n s i t i o n s a n d timeresolved ellipsometry. I n f o r m a t i o n o n t h e optical
dielectric function of t h e m a t e r i a l u n d e r t h e c o n
d i t i o n s of t h e e x p e r i m e n t c a n be o b t a i n e d .
(c) Femtosecond heating pulses. T h e u l t i m a t e regime
in t h e surface h e a t i n g of solids o c c u r s with femto
s e c o n d pulses. H e r e , t h e laser pulse d u r a t i o n s r e a c h
t h e characteristic times for energy r e l a x a t i o n of t h e
p h o t o e x c i t e d electron gas t o t h e lattice. T h e h e a t is
d e p o s i t e d in s u c h a s h o r t t i m e t h a t the h e a t c o n d u c
tion o u t of t h e l i g h t - a b s o r b i n g v o l u m e d o e s n o t o c c u r
within t h e laser pulse d u r a t i o n . E x t r e m e l y high t e m
p e r a t u r e s a r e g e n e r a t e d in a shallow layer w h i c h is still
in a quiescent s t a t e a n d c a n b e o b s e r v e d before m a t t e r
escapes t h e i r r a d i a t e d a r e a b y e v a p o r a t i o n o r a b l a
tion. T h e field of t h e r m o p h y s i c s is still in its infancy
h e r e , a l t h o u g h these c i r c u m s t a n c e s a r e extremely at
tractive in t h e s t u d y of h i g h - t e m p e r a t u r e regimes of
c o n d e n s e d m a t t e r a n d they o p e n n e w possibilities in
t h e field of t h e r m o p h y s i c a l m e a s u r e m e n t s .
Time-resolved optical reflectivity m e a s u r e m e n t s
a n d t h e d e t e c t i o n of ultrafast p h a s e t r a n s i t i o n s with
t h e aid of f e m t o s e c o n d laser pulses (90 fs, 0.62 )
h a v e b e e n p e r f o r m e d a t t h e University of T e x a s a t
Austin, U S A , by M . D o w n e r and co-workers.
A t t h e I n s t i t u t fur L a s e r u n d P l a s m a p h y s i k ,
U n i v e r s i t a t Essen, G e r m a n y , D . v o n d e r L i n d e h a s
1 4
_1
o b t a i n e d h e a t i n g rates of 1 0 K s w i t h laser pulses
of 20 p s d u r a t i o n . T h i s results in d y n a m i c a l super
h e a t i n g of t h e solid p h a s e a n d allows t h e s t u d y of melt
front velocities in s u p e r h e a t e d s a m p l e s .
F e m t o s e c o n d e x p e r i m e n t s h a v e also been per
f o r m e d a t t h e N a t i o n a l C o u n c i l of C a n a d a , O t t a w a ,
C a n a d a , b y P . C o r k u m . H i s research is also c o n c e n
t r a t e d o n t h e physics t h a t is implied b y t h e fast t i m e
scales a n d t h e high intensities available.
A t t h e U n i v e r s i t y of C h i c a g o , U S A , N . Scherer h a s
used u l t r a s h o r t laser pulses t o s t u d y a n d investigate

Thermophysical

the ultrafast s p e c t r o s c o p y of c o n d e n s e d p h a s e d y n a
mics a n d f e m t o s e c o n d chemistry.

4. Future

Developments

Pulse h e a t i n g t e c h n i q u e s a r e , as s h o w n in this article,

a g o o d tool for o b t a i n i n g i n f o r m a t i o n a b o u t t h e
t h e r m o p h y s i c a l p r o p e r t i e s of m a t t e r , especially in t h e
liquid p h a s e . F u t u r e p r o g r e s s in h i g h - t e m p e r a t u r e
technologies d e p e n d s strongly o n t h e availability of
reliable t h e r m o p h y s i c a l , t h e r m o c h e m i c a l a n d t h e r m o
d y n a m i c h i g h - t e m p e r a t u r e d a t a . T h i s is of e x t r e m e
i m p o r t a n c e a t very high t e m p e r a t u r e s , w h e r e d a t a c a n
differ d r a m a t i c a l l y from p r e d i c t i o n s b a s e d o n t h e
e x t r a p o l a t i o n of l o w - t e m p e r a t u r e d a t a . T h e r e f o r e ,
future research o n s u b s e c o n d t h e r m o p h y s i c s m u s t
c o n t i n u e t h e d e v e l o p m e n t of n e w a n d m o r e a c c u r a t e
dynamic measurement techniques. F o r example, the
melting p o i n t of c a r b o n is still u n c e r t a i n w i t h i n a
r a n g e of 500 a n d very little is k n o w n a b o u t t h e
emissivity of liquid m e t a l s .
M e a s u r e m e n t s a t higher t e m p e r a t u r e s a n d p r e s
sures s h o u l d lead t o critical p o i n t d a t a for m e t a l s
which, except for t h e alkali m e t a l s a n d s o m e m e t a l s
such as m e r c u r y , lead a n d i n d i u m c a n only b e
estimated.
T h e g e n e r a t i o n of n e w m a t e r i a l s with higher melt
ing p o i n t s t h a n t h e p u r e elements s h o u l d also b e
possible with these t e c h n i q u e s . F o r e x a m p l e , h a f n i u m
nitride reaches a m e l t i n g t e m p e r a t u r e of 4600 (for
c o m p a r i s o n , t h e m e l t i n g t e m p e r a t u r e of p u r e h a f n i u m
is 2500 K ) . F o r z i r c o n i u m with x e n o n a n d k r y p t o n
c o m p o u n d s , a m e l t i n g t e m p e r a t u r e of a b o u t 8000 is
predicted by a g r o u p of R u s s i a n theorists!
In future, t h e c o m p a r i s o n of e q u i l i b r i u m a n d t r a n
sient t e c h n i q u e s will clarify t h e limits of validity of
ultrafast h e a t i n g t e c h n i q u e s . A c c o m p a n y i n g t h e o r
etical w o r k will significantly c o n t r i b u t e t o a n u n d e r
s t a n d i n g of m a t t e r u n d e r e x t r e m e c o n d i t i o n s of
t e m p e r a t u r e a n d p r e s s u r e a n d u n d e r c o n d i t i o n s far
r e m o v e d from t h e r m o d y n a m i c e q u i l i b r i u m .
See also: X-Ray Diffraction, Time-Resolved

Bibliography
Baeri 1990 Nanosecond laser-induced phase transitions
and metastable phases quenching. Philos. Mag. B. 61:
587-600
Berthault A, Aries L, Matricon J 1986 High-pressure hightemperature thermophysical measurements on tantalum
and tungsten. Int. J. Thermophys. 7: 167-79
Cezairliyan A 1988 Pulse calorimetry. In: Ho C Y (ed.) 1988
Specific Heat of Solids, CINDAS Data Series on Material
Properties, Vols. 1, 2. Hemisphere Publishing, New York,
pp. 323-53.
Cezairliyan A, Gathers G R, Malvezzi A M, Miiller A P,
Righini F, Shaner J W 1990 Issues and future directions in
subsecond thermophysics research. Int. J. Thermophys.
11: 819-33

Measurements,

Subsecond

Cezairliyan A, Miiller A 1990 A dynamic technique for

thermophysical measurements at high temperatures in a
microgravity environment. Int. J. Thermophys. 11: 653-62
Dobrosavljevic A S, Maglic D 1989 Evaluation of a direct
pulse heating method for measurement of specific heat
and electric resistivity in the range 300-1900 K. High
Temp. High Pressures 21: 411-21
Eesley G L 1990 Picosecond dynamics of thermal and
acoustic transport in metal films. Int. J. Thermophys. 11:
811-17
Gathers G R 1986 Dynamic methods for investigating
thermophysical properties of matter at very high temper
atures and pressures (a review). Rep. Prog. Phys. 49: 34196
Hiernaut J P, Ronchi C 1989 Calorimetric measurements
with acoustic levitation in high-temperature heating ex
periments with pulsed laser beams. High. Temp. High
Pressures. 21: 119-30
Hixson R S, Winkler A 1990 Sound speed and thermo
physical properties of liquid iron and nickel. Phys. Rev.
42: 6485-91
Kaschnitz E, Pottlacher G, Jager 1992 A new microse
cond pulse heating system to investigate thermophysical
properties of solid and liquid metals. Int. J. Thermophys.
13: 699-710.
Kirillin A V, Kovalenko D, Romanenko S V, Kheifets L
M, Sheindlin A 1986 Apparatus and methods for
examining the properties of refractory substances at high
temperatures and pressures by stationary laser heating.
Teplofiz. Vysokikh Temperatur. 24: 364-9
Korobienko V H, Sawatimskii A 1 1990 Electrical resistivity
and enthalpy of nickel for the solid and the liquid state.
Teplofiz. Vysokikh Temperatur. 28: 914-24
McClure J L, Cezairliyan A 1990 Microsecond-resolution
electrical measurements in high-current discharges. Int. J.
Thermophys. 11: 739-51
Malvezzi A 1990 Picosecond laser heating and melting of
graphite. Int. J. Thermophys. 11: 797-809
Martynyuk 1989 Critical point parameter of metals, a
review. Doctrine of the Peoples Friendship University,
Moscow
Miiller A P, Cezairliyan A 1990 Thermal expansion of
tungsten in the range 1500-3600 by a transient interferometric technique. Int. J. Thermophys. 11: 619-28
Ohse R W 1990a Extension of thermophysical and thermo
dynamic property measurements by laser pulse heating up
to 10,000 , I: under pressure (a review). Int. J. Thermo
phys. 11: 753-69
Ohse R W 1990b Extension of thermophysical and thermo
dynamic property measurements by laser pulse heating up
to 10,000 , II: under vacuum (a review). Int. J. Thermo
phys. 11: 11'1-87
Petrova I I, Chekhovskii V Ya 1988 Measurement of the
heat capacity of pyrolytic graphite by an impulsive
method. High Temp. 26: 198-202
Pottlacher G, Jager 1990 Measurement of thermophysical
properties of lead by a subsecond pulse-heating method in
the range 2000-5000 K. Int. J. Thermophys. 11: 719-29
Pottlacher G, Kaschnitz E, Jager 1991 High-pressure
high-temperature thermophysical measurements on
molybdenum. J. Phys. Condens. Matter 3: 1-10
Reitze D H, Wang X, Ahn H, Downer C 1989 Femto
second laser melting of graphite. Phys. Rev. B. 40:
11986-9
Righini F, Bussolino G C, Rosso A, Roberts R 1990

535

Thermophysical

Measurements,

Subsecond

Thermal conductivity by a pulse heating method: theory

and experimental apparatus. Int. J. Thermophys. 11: 62941
Sheindlin A, Senchenko V 1987 Apparatus for com
plex study of the thermodynamic properties of electrically
conducting materials under conditions of impulsive heat
ing with a high-density current. High Temp. 25: 281-6
G. Pottlacher
[Technische U n i v e r s i t a t G r a z ,
G r a z , Austria]

Thin Films: Characterization by X Rays

In recent years thin films h a v e b e c o m e of m a j o r
i m p o r t a n c e in several a r e a s of science a n d tech
nology. Optical c o m p o n e n t m a n u f a c t u r e r s e m p l o y
surface c o a t i n g s t o modify optical characteristics.
T h e m a t e r i a l s i n d u s t r y uses thin-film c o a t i n g s a n d
surface modification for i m p r o v e d c o r r o s i o n a n d
w e a r resistance. T h e r e is a s t r o n g interest in the
m a g n e t i c p r o p e r t i e s of thin films in o r d e r t o increase
the density of r e c o r d e d i n f o r m a t i o n t h r o u g h the use
of c o n t i n u o u s m a g n e t i c m e d i a . T h e m o d e r n electro
nics i n d u s t r y could n o t exist w i t h o u t its extremely
a d v a n c e d thin-film t e c h n o l o g y which is a central
r e q u i r e m e n t for the m a n u f a c t u r e of i n t r e g r a t e d cir
cuits. T h e s e e x a m p l e s certainly d o n o t c o n s t i t u t e a n
exhaustive list of the a p p l i c a t i o n s of thin films in the
m o d e r n w o r l d , b u t they d o serve t o illustrate the
variety of a r e a s in which they a r e f o u n d .
It is h a r d l y surprising t o discover t h a t as thin films
a n d surfaces h a v e increased in technological i m p o r t
ance so surface-specific analysis t e c h n i q u e s h a v e d e
veloped accordingly. M a n y of these are b a s e d o n the
interaction of electron o r ion b e a m s with the surface.
F o r d e p t h profiling, destructive m e t h o d s are often the
only solution. X - r a y diffraction h a s for a l o n g time
been the definitive m e t h o d for crystal s t r u c t u r e deter
m i n a t i o n . T h e p e n e t r a t i o n d e p t h of rays in solids is,
however, m a n y m i c r o m e t e r s a n d c o n v e n t i o n a l dif
fraction techniques are often of limited use in study
ing t h i n n e r structures a n d surfaces.

I n these e q u a t i o n s is the x-ray wavelength, e a n d m

are the c h a r g e a n d m a s s of the electron, c is the
velocity of light, Nt is the n u m b e r of a t o m s of type / in
the unit cell, Zi t h e c o r r e s p o n d i n g a t o m i c n u m b e r ,
a n d f \ a n d f" a r e t h e real a n d i m a g i n a r y r e s o n a n t (or
a n o m a l o u s ) a t o m i c scattering factors.
F o r solids a n d liquids a n d are of the o r d e r of
5
1 0 " o r less, a n d h e n c e is slightly less t h a n unity. T h e
index of refraction of air a t x-ray wavelengths is
effectively u n i t y a n d , therefore, as w a s p o i n t e d o u t by
C o m p t o n (1923), rays m a y u n d e r g o total external
reflection from s m o o t h surfaces for incident angles
/2
below a certain critical angle q>c defined by 0 ~
(2) .
<pc is typically a few t e n t h s of a degree. P a r r a t t (1954)
developed the necessary t h e o r y t o describe the reflec
tion of rays from a s m o o t h h o m o g e n e o u s surface.
T h e reflectivity R of the surface as a function of
incident angle is given by the r a t i o of reflected inten
sity IT t o incident intensity I0 a n d c a n be written as
R(<p) = t(<p)

Reflection

of X

Rays

T h e index of refraction of m a t t e r at x-ray w a v e

lengths c a n be expressed as

=1--

(1)

where
2 2

o = (X e /2nmc )ZNi(Zi+fi)

(2)

and
2

/? = / 2 ^ ) 7 / 7 )

536

(3)

+,

(4)

where
2A

+ 4 / ? ] ' + ( - \)

+ 4 >

= [( - ])

1 2

(5)

(6)

and
2

IB

= [( - ,)

+ ( - \)

O n e of the m o s t i m p o r t a n t p o i n t s t o n o t e is t h a t the
p e n e t r a t i o n of the rays i n t o the surface for < (pc
d o e s n o t d r o p t o zero. A n evanescent w a v e effectively
p r o b e s a few n a n o m e t e r s i n t o the s a m p l e surface. T h e
p e n e t r a t i o n d e p t h z 1 / e, defined as t h e d e p t h at which
the electric field h a s d r o p p e d t o 1 /e of its value at the
s a m p l e surface, is d e p e n d e n t o n a n d for small , is
given by

(7)

' *~4
Finally, it is interesting t o calculate the evanescent
w a v e intensity at t h e surface. T h i s is given by the
p r o d u c t of the electric field a n d its c o m p l e x conju
gate, a n d its d e p e n d e n c e o n is described by
EE*(<p) ^

1. Specular

= (Z +,

41<p
( + Af

(8)

w h e r e I is t h e incident b e a m intensity.
C u r v e s of ( ^ ) , zlle(<p) a n d \) are s h o w n in Fig.
1. It is i m m e d i a t e l y a p p a r e n t t h a t by v a r y i n g t h e
incident angle of a b e a m of rays o n a s m o o t h surface
the d e p t h of p e n e t r a t i o n c a n be controlled in a r a n g e
from a few n a n o m e t e r s t o m a n y m i c r o m e t e r s . T h i s is
the basis for t h e v a r i o u s thin-film analysis m e t h o d s
discussed in the following sections.
I n t h e o r y , a perfectly s m o o t h flat surface for which
t h e a b s o r p t i o n coefficient for r a y s is zero will h a v e a
reflection coefficient R(q>) of unity for all values of
from zero t o the critical angle 0, a b o v e which R(<p)

Thin Films:

0
Incident

2
angle

Figure 1
Typical curves of reflectivity (R), penetration depth ( z l / e)
and evanescent wave intensity (EE*) as a function of
incident angle () for rays incident on a smooth flat
surface

w o u l d d r o p s h a r p l y a n d tail off t o z e r o for large . I n

practice this is never t h e case a n d t h e s h a p e of t h e
reflectivity curve, t o g e t h e r with t h e m e a s u r e d value of
0, c o n t a i n s i n f o r m a t i o n o n the surface density,
r o u g h n e s s a n d refractive index. T h e effects of r o u g h
ness c a n be t a k e n i n t o a c c o u n t in theoretical m o d e l s .
F o r surfaces o n w h i c h a t h i n film h a s been d e p o s
ited a n a d d i t i o n a l effect often manifests itself. A b o v e
= tpc, p e a k s a n d t r o u g h s a p p e a r in t h e reflectivity
curve. T h e s e were first r e p o r t e d b y Kiessig (1931a, b)
w h o derived a f o r m u l a for t h e p o s i t i o n of the m a x i m a
as a function of :

where is t h e a n g u l a r p o s i t i o n of t h e m t h m a x i m u m
a n d d is t h e film thickness. T h e s e " K i e s s i g fringes"
c a n be u n d e r s t o o d as a n effect arising from t h e
interference b e t w e e n t h e b e a m reflected from t h e
surface of the film a n d from t h e film-substrate inter
face. A s c a n be seen from E q n . (9), analysis of Kiessig
fringes c a n yield i n f o r m a t i o n o n t h e film thickness
a n d electronic density. Surface a n d interface r o u g h
ness m a y also b e c o n s i d e r e d in theoretical m o d e l s a n d
experimentally a p p e a r s as a r e d u c t i o n in fringe c o n
trast from the theoretical c a l c u l a t i o n for perfectly
s m o o t h interfaces. M o d e r n c o m p u t e r s a n d c o m p u t a
tional m e t h o d s m a y be used t o a n a l y z e t h e reflectivity
curves of surfaces with several d e p o s i t e d layers. A n
elegant illustration of this g r a z i n g x-ray reflectometry
( G X R R ) t e c h n i q u e is described by Le Boite et al.
(1988) w h o c o m p a r e it with R u t h e r f o r d b a c k s c a t t e r
ing as a n analysis t e c h n i q u e for thin-film mixing b y
ion b e a m s . H o w e v e r , the t e c h n i q u e is certainly n o t
w i t h o u t its limitations: systems giving p o o r fringe
c o n t r a s t d u e t o different densities b e t w e e n layers a r e

Characterization

by X

Rays

u n s u i t a b l e for G X R R , a n d t h e s a m p l e m u s t be fairly
large (for a c c u r a t e a l i g n m e n t ) , very s m o o t h a n d flat.
O n e further t e c h n i q u e for thin-film c h a r a c t e r i z a
tion m a y be m e n t i o n e d a t this p o i n t : total-reflection
x-ray fluorescence ( T X R F ) . T h i s is a simple modifica
tion of t h e s t a n d a r d t e c h n i q u e for c o m p o s i t i o n a l
analysis, w h e r e b y t h e surface is illuminated w i t h a n xr a y b e a m a n d t h e resulting x-ray fluorescence spec
t r u m yields i n f o r m a t i o n o n t h e a t o m i c species present.
In t h e glancing angle g e o m e t r y , a fine slit is used t o
collimate t h e b e a m , e n a b l i n g a c c u r a t e c o n t r o l of t h e
incident angle. D e p t h profiling of c o m p o s i t i o n is t h u s ,
in principle, feasible t h o u g h t h e t e c h n i q u e is n o r m a l l y
o n l y used for identifying a n d q u a n t i f y i n g surface
species. T X R F w a s originally d e v e l o p e d for c o m
p o s i t i o n a l analysis of trace elements d e p o s i t e d (e.g.,
from s o l u t i o n ) o n t o a n optically flat x-ray reflecting
surface, b u t its a p p l i c a t i o n t o thin-film a n d surface
analysis is o b v i o u s . Identification of interfacial a t o m i c
species is also possible.

2. Glancing

Angle

X-Ray

Diffraction

C o n v e n t i o n a l x-ray diffractometers a r e often used

t o investigate thin-film s t r u c t u r e s . T h e w e l l - k n o w n
B r a g g - B r e n t a n o (or -2) focusing g e o m e t r y suffers a
m a j o r d i s a d v a n t a g e in m a n y instances since x-ray
scattering from t h e s u b s t r a t e m a y o v e r w h e l m t h a t
from t h e thin film. T h i s p r o b l e m is partially o v e r c o m e
by using t h e S e e m a n - B o h l i n focusing g e o m e t r y ,
w h e r e t h e incident angle is k e p t c o n s t a n t a n d the
d e t e c t o r is s c a n n e d a r o u n d t h e focusing circle. U n f o r
t u n a t e l y , t h e m i n i m u m practical incident angle is
a b o u t 5 a n d t h e diverging incident b e a m p r e v e n t s
a c c u r a t e c o n t r o l of t h e p e n e t r a t i o n d e p t h . T h i s type
of a r r a n g e m e n t is, h o w e v e r , often extremely useful
in thin-film s t r u c t u r e analysis a n d is available
commercially.
I n o r d e r t o further r e d u c e t h e angle of incidence it is
necessary t o a b a n d o n focusing a r r a n g e m e n t s a n d use
a parallel b e a m g e o m e t r y . I n o r d e r t o m a i n t a i n a n g u
lar r e s o l u t i o n , Soller slits a r e e m p l o y e d . T h e r e s u l t a n t
loss of intensity t h a t this entails is q u i t e serious. I n
a d d i t i o n , m o v i n g t o incident angles n e a r t h e critical
angle for t o t a l external reflection (q>c) greatly reduces
t h e x-ray intensity o n t h e s a m p l e surface.
Finally, below (pc t h e d e p t h of p e n e t r a t i o n of t h e
incident b e a m m a y d r o p b y several o r d e r s of m a g n i
t u d e , with a c o r r e s p o n d i n g decrease in t h e intensity
diffracted b y t h e s a m p l e . It is n o t surprising, there
fore, t o find t h a t m o s t studies of very thin films a n d
surfaces e m p l o y s y n c h r o t r o n s t o r a g e rings as the
x-ray s o u r c e , as t h e intensity is high e n o u g h t o
s t u d y surface c o a t i n g s of a fraction of a m o n o l a y e r .
P a r a l l e l - b e a m glancing angle diffractometer facilities
a r e f o u n d a t m o s t s y n c h r o t r o n r a d i a t i o n facilities. It
s h o u l d be stressed, h o w e v e r , t h a t c o n v e n t i o n a l x-ray
sources m a y very often b e e m p l o y e d for effective thin-

537

Thin Films:

Characterization

by X

Rays

film glancing angle diffraction studies using incident

angles j u s t a b o v e 0 in o r d e r t o e n h a n c e t h e surface
sensitivity as m u c h as possible while m a i n t a i n i n g a
r e a s o n a b l e diffracted intensity. R o t a t i n g a n o d e
sources m a y even be powerful e n o u g h in certain cases
for very thin film a n d for surface studies for < 0.
T w o specific techniques h a v e been developed for
glancing angle diffraction. T h e first, described by L i m
et al. (1987), is a modification of t h e S e e m a n - B o h l i n
focusing g e o m e t r y (see Fig. 2). I n s t e a d of a diverging
incident b e a m , a slit h a s been a d d e d t o allow a c c u r a t e
c o n t r o l of the angle of incidence o n the s a m p l e .
Diffraction from t h e entire illuminated section of t h e
s a m p l e surface is collected via a Soller slit for a n g u l a r
resolution. I n t h e case of s y n c h r o t r o n r a d i a t i o n facili
ties the incident b e a m will a l r e a d y h a v e passed
t h r o u g h a m o n o c h r o m a t o r before the e n t r a n c e slit.
F o r c o n v e n t i o n a l sources t h e m o n o c h r o m a t o r is
usually placed after the exit Soller slit. Alternatively, a
solid-state s e m i c o n d u c t o r d e t e c t o r m a y be e m p l o y e d
(these h a v e a typical energy resolution of a b o u t 2 % )
t o discriminate in favor of t h e characteristic Ka lines
of the source. T h i s a r r a n g e m e n t is, for o b v i o u s rea
sons, k n o w n as the glancing incidence a s y m m e t r i c
Bragg ( G I A B ) g e o m e t r y a n d is well suited t o t h e s t u d y
of polycrystalline o r a m o r p h o u s thin films since lat
tice i n f o r m a t i o n is o b t a i n e d at v a r y i n g angles with
respect to the surface as the d e t e c t o r (20) angle
changes.
T h e second glancing angle diffraction t e c h n i q u e
w a s first described by M a r r a et al. (1979) a n d h a s been
t e r m e d glancing incidence x-ray scattering ( G I X S ) . I n
this g e o m e t r y b o t h t h e incident b e a m a n d the detected
r a d i a t i o n a r e at a glancing angle with respect t o the
surface (see Fig. 3). T h e d e t e c t o r is r o t a t e d r o u n d the
n o r m a l t o t h e s a m p l e surface so t h a t only lattice
planes very nearly p e r p e n d i c u l a r t o the s a m p l e surface
c o n t r i b u t e to the diffracted signal. In o r d e r t o m a i n
tain a r e a s o n a b l e a n g u l a r resolution, Soller slits m u s t
be included in the incident b e a m as well as in t h e
detector section. T h i s , t o g e t h e r with the fact t h a t
the scattered r a d i a t i o n suffers m o r e a b s o r p t i o n in the

Detector

SLit

Sample

Figure 2
GIAB surface diffraction geometry

538

Detector

Figure 3
GIXS surface diffraction geometry

s a m p l e t h a n in the case of G I A B , m a k e s the t e c h n i q u e

r a t h e r u n s u i t a b l e for polycrystalline o r a m o r p h o u s
thin films. It m a y , h o w e v e r , be used as a c o m p l e m e n
t a r y t e c h n i q u e t o G I A B in such cases as t h e analysis
of crystallite o r i e n t a t i o n a n d / o r strain. W h e r e G I X S
really c o m e s i n t o its o w n as a thin-film analysis
t e c h n i q u e is in t h e s t u d y of epitaxial layers o n single
crystal s u b s t r a t e s . In this case the c o m p l e t e surface
m a y c o n t r i b u t e t o t h e diffracted intensity, t h e r e b y
m a k i n g the t e c h n i q u e feasible with powerful c o n v e n
tional sources, even a t incident angles less t h a n <pc.
S a m p l e d e t e c t o r (20) scans in t h e G I X S g e o m e t r y ,
t o g e t h e r with so-called " s c a n s " (where only the
s a m p l e is r o t a t e d ) a t v a r y i n g angles of incidence,
p r o v i d e i n f o r m a t i o n a b o u t epitaxial relationship,
crystallite size ( a n d o r i e n t a t i o n a l s p r e a d ) a n d lattice
strain for epitaxial thin films.

3. Surface

X-Ray

Absorption

Spectroscopy

X - r a y a b s o r p t i o n s p e c t r o s c o p y ( X A S ) is a wellk n o w n t e c h n i q u e for s t r u c t u r a l c h a r a c t e r i z a t i o n t h a t
h a s d e v e l o p e d rapidly d u e t o t h e increased availability
of high-intensity s y n c h r o t r o n x-ray sources. X A S is
generally divided i n t o t w o regimes: x-ray a b s o r p t i o n
n e a r edge s t r u c t u r e ( X A N E S ) a n d e x t e n d e d x-ray
a b s o r p t i o n fine s t r u c t u r e ( E X A F S ) . X A N E S deals
with the s t r u c t u r e in the a b s o r p t i o n coefficient close t o
a n inner shell a b s o r p t i o n edge of t h e p a r t i c u l a r a t o m i c
species u n d e r investigation in the s a m p l e , while
E X A F S is c o n c e r n e d with t h e oscillations observed in
the a b s o r p t i o n coefficient u p t o several h u n d r e d elec
t r o n volts a b o v e t h e a b s o r p t i o n edge. B o t h furnish
i n f o r m a t i o n a b o u t t h e local s t r u c t u r e a r o u n d the
a b s o r b i n g a t o m i c species a n d a r e t h u s p a r t i c u l a r l y
useful in t h e s t u d y of a m o r p h o u s solids o r dilute
species in h o s t e n v i r o n m e n t s , w h e r e x-ray diffraction
is of limited use, X A N E S also gives the valence state
of the a b s o r b i n g species.
T h e subject of interest is h o w t o a p p l y X A S t o the
s t u d y of thin films o r surfaces. T h e first surfacesensitive X A S t e c h n i q u e , k n o w n as surface E X A F S

Thin Films:

(or S E X A F S ) , w a s p r o p o s e d a n d d e v e l o p e d in t h e late
1970s. T h e basis o f this m e t h o d is t h a t t h e surface
p h o t o e l e c t r o n yield is closely related t o t h e surface xr a y a b s o r p t i o n coefficient. T h e small escape d e p t h of
t h e p h o t o e l e c t r o n s (a few n a n o m e t e r s ) e n s u r e s surface
sensitivity, so t h a t S E X A F S is only of use in s t u d y i n g
surfaces (e.g., a b s o r b e d a t o m s o r m o n o l a y e r s ) o r very
thin films.
By e m p l o y i n g t h e glancing angle g e o m e t r y d e
scribed previously a n o t h e r r a n g e of surface a n d inter
face t e c h n i q u e s b e c o m e s possible. Reflection E X A F S ,
o r R e f l E X A F S , w a s first r e p o r t e d b y B a r c h e w i t z et al.
(1978). T h i s m e t h o d (see F i g . 4) consists of reflecting
a n x-ray b e a m off t h e s a m p l e surface a n d m e a s u r i n g
t h e r a t i o of reflected t o incident intensity ( / r / / 0) a s a
function of t h e x-ray energy ( ) . T h e surface a b s o r p
tion s p e c t r u m m a y t h u s b e f o u n d , w i t h a n effective
p e n e t r a t i o n d e p t h of a few n a n o m e t e r s . T h e possibili
ties of this t e c h n i q u e d o n o t , h o w e v e r , s t o p h e r e . F o r
surfaces with thin d e p o s i t e d films it is often possible
t o reflect t h e incident b e a m off t h e
film-substrate
interface. R e f l E X A F S in this case will b e sensitive t o
t h e c o m p l e t e d e p t h of t h e film, p l u s a few n a n o m e t e r s
of t h e s u b s t r a t e . Since X A S is " a t o m specific," t h e
possibilities for s t u d y i n g t h e interfacial region a r e
immediately a p p a r e n t . T h e signal-to-noise r a t i o of
such a surface-sensitive X A S t e c h n i q u e m a y often b e
c o n s i d e r a b l y e n h a n c e d b y m o n i t o r i n g t h e x-ray fluor
escence from t h e s a m p l e surface ( / F d e t e c t o r ) i n s t e a d
of t h e reflected b e a m intensity (see F i g . 4). Solidstate d e t e c t o r s m a y b e u s e d h e r e w i t h c o n s i d e r a b l e
effect t o further r e d u c e u n w a n t e d b a c k g r o u n d signal.
Fluorescence-detected E X A F S ( o r F L E X A F S ) a t
glancing angle is p a r t i c u l a r l y suitable w h e n s t u d y i n g
the e n v i r o n m e n t s of a t o m s with low c o n c e n t r a t i o n
a n d in c o n t r a s t w i t h R e f l E X A F S m a y b e e m p l o y e d a t
incident angles a b o v e ^ c , m a k i n g it m o r e versatile.

4. Current

Situation

C h a r a c t e r i z a t i o n t e c h n i q u e s for t h i n films a n d sur

faces using r a y s h a v e d e v e l o p e d r a p i d l y in recent

Detector

slit

"Knife edge"

Figure 4
Experimental arrangement for ReflEXAFS and glancing
angle FLEXAFS

Characterization

by X

Rays

years. It s h o u l d b e n o t e d , h o w e v e r , t h a t these tech

n i q u e s a r e still in their infancy a n d a r e certainly n o t
w i t h o u t their d r a w b a c k s . All t e c h n i q u e s t h a t e m p l o y
t h e glancing angle g e o m e t r y p u t severe r e q u i r e m e n t s
o n t h e s a m p l e surface q u a l i t y in t e r m s of s m o o t h n e s s
a n d flatness, a n d o n s a m p l e sizefor glancing angle
w o r k surface d i m e n s i o n s n e e d t o b e large e n o u g h
2
(usually several c m ) for a c c u r a t e a l i g n m e n t . F o r
a c c u r a t e lattice p a r a m e t e r m e a s u r e m e n t s , G I A B dif
fraction d a t a need t o b e c o r r e c t e d for refractive index
effects w h i c h b e c o m e i m p o r t a n t a t s u c h l o w i n c i d e n t
angles. L i m et al. (1987) h a v e discussed this a n d
p r o p o s e d a n e x p e r i m e n t a l p r o c e d u r e for d e t e r m i n i n g
t h e c o r r e c t i o n factors w h i c h a r e difficult t o d e d u c e
theoretically for n o n p e r f e c t surfaces. I t w a s s h o w n b y
M a r t e n s a n d R a b e (1981) t h a t glancing angle X A S is
n o t a l w a y s a s s t r a i g h t f o r w a r d as it m a y a p p e a r , with
angle of incidence effects p r o d u c i n g c h a n g e s b o t h in
t h e a m p l i t u d e a n d p h a s e o f t h e E X A F S oscillations.
F o r t u n a t e l y , these c a n usually b e a c c o u n t e d for.
M u c h further d e v e l o p m e n t c a n certainly b e
expected in t h e v a r i o u s t e c h n i q u e s described in this
article, t o g e t h e r with a c o n t i n u e d increase in their use
as m o r e researchers b e c o m e a w a r e o f their p o t e n t i a l
for n o n d e s t r u c t i v e c h a r a c t e r i z a t i o n o f surfaces, inter
faces a n d thin films.
See also: Ion Backscattering Analysis; X-Ray Absorption
Spectroscopy: EXAFS and XANES Techniques; X-Ray
Fluorescence Spectrometry; X-Ray Powder Diffraction

Bibliography
Aiginger H, Wobrauschek 1985 Total reflectance x-ray
spectrometry. In: Barrett C S, Predecki , Leyden D
(eds.) 1985 Advances in X-Ray Analysis, Vol. 28. Plenum,
New York, pp. 1-10
Barchewitz R, Cremonese-Visicato M, Onori G 1978 X-ray
photoabsorption of solids by specular reflection. J. Phys.
C 11: 4439^15
Born M, Wolf 1980 Principles of Optics. Pergamon,
Oxford
Compton A 1923 The total reflection of x-rays. Philos.
Mag. 45: 1121-31
Doerner F, Brennan S 1988 Strain distribution in thin
aluminum films using x-ray depth profiling. J. Appl. Phys.
63(1): 126-31
Eisenberger P, Citrin P, Hewitt R, Kincaid 1981
SEXAFS: new horizons in surface structure determi
nation. CRC Crit. Rev. Solid State Mater. Sci. 10(2): 191207
Fox R, Gurman S J 1980 EXAFS and surface EXAFS from
measurements of x-ray reflectivity. J. Phys. C 13: L249-53
Heald S M, Keller E, Stern A 1984 Fluorescence detection
of surface EXAFS. Phys. Lett. A 103(3): 155-8
Huang C, Toney F, Brennan S, Rek 1987 Analysis of
cobalt-doped iron oxide thin films by synchrotron radia
tion. Thin Solid Films 154: 439-45
Kiessig 1931a Interference of Rontgen rays on thin layers.
Ann. Physik 10: 769-88
Kiessig 1931b Investigation of the total reflection of
Rontgen rays. Ann. Physik 10: 715-68

539

Thin Films: Characterization

by X

Rays

Le Boite G, Traverse A, Nevot L, Pardo B, Corno J 1988

Grazing x-ray reflectometry and Rutherford backscattering 2. Complementary techniques for the study of
thin-film mixing. Nucl. Instrum. Methods 29: 653-60
Lee A, Citrin , Eisenberger , Kincaid 1981
Extended x-ray absorption of fine structureits strengths
and limitations as a structural tool. Rev. Mod. Phys. 53:
769-806
Lim G, Parrish W, Ortiz C, Bellotto M, Hart 1987
Grazing incidence synchrotron x-ray diffraction method
for analyzing thin films. J. Mater. Res. 2: 471-7
Marra W C, Eisenberger P, Cho A Y 1979 X-ray totalexternal-reflection-Bragg diffraction: a structural study of
the GaAs-Al interface. J. Appl. Phys. 50: 6927-33
Martens G, Rabe 1981 The extended x-ray absorption fine
structure in the reflectivity at the edge of Cu. / . Phys. C
14: 1523-34
Parratt L G 1954 Surface studies of solids by total reflection
of x-rays. Phys. Rev. 95: 359-69
Segmiiller A 1987 Characterization of epitaxial films by
grazing-incidence x-ray diffraction. Thin Solid Films 154:
33-42
Vineyard G 1982 Grazing-incidence diffraction and the
distorted-wave approximation for the study of surfaces.
Phys. Rev. 26: 4146-59
Wong J 1986 Extended x-ray absorption fine structure: a
modern structural tool in materials science. Mater. Sci
Eng. 80: 107-28
P. N . Gibson
[Joint R e s e a r c h C e n t r e C E C ,
I s p r a , Italy]

Transmission Electron Microscopy:

Convergent-Beam and Microdiffraction
Techniques
F o r the s t u d y of crystalline m a t e r i a l s , t h e t r a n s m i s
sion electron m i c r o s c o p e is especially powerful
because it c a n form b o t h images a n d diffraction
p a t t e r n s from the s a m e a r e a . T h e i m a g e s reveal s a m
ple m o r p h o l o g y a n d t h e diffraction p a t t e r n s give
crystallographic i n f o r m a t i o n ; t o g e t h e r they p e r m i t
the c h a r a c t e r i z a t i o n of s t r u c t u r a l defects. Recently,
the p o w e r of electron diffraction t o deliver crystallo
g r a p h i c i n f o r m a t i o n h a s been greatly e n h a n c e d by the
d e v e l o p m e n t of a family of t e c h n i q u e s t h a t m a k e
" m i c r o d i f f r a c t i o n " possible. O l d e r t e c h n i q u e s were
limited, p a r t i c u l a r l y in t h a t r a t h e r large a r e a s (greater
t h a n 1 in d i a m e t e r ) of t h e specimen c o n t r i b u t e d t o
the p a t t e r n . Microdiffraction t e c h n i q u e s a r e t h o s e in
which t h e p a t t e r n is o b t a i n e d from s u b m i c r o m e t e r
a r e a s d o w n t o a few n a n o m e t e r s in s o m e cases.
T h e s e techniques a r e i m p o r t a n t n o t only because they
p e r m i t t h e s t u d y of the specimen o n a finer scale b u t
because (as indicated below) the diffraction p a t t e r n s
themselves a r e richer. T h e y c a n be used t o d e t e r m i n e
s a m p l e thickness, crystal s y m m e t r y , t h e identity of
p h a s e s , v a r i a t i o n of lattice p a r a m e t e r , a t o m i c p o t e n
tials a n d crystal s t r u c t u r e s .

540

O f t h e v a r i o u s microdiffraction t e c h n i q u e s , o n e
c o n v e r g e n t - b e a m diffractionhas
become
more
widely used t h a n the o t h e r s , a n d this article will
c o n c e n t r a t e o n it.

/.

Basic

Ideas

In x-ray a n d n e u t r o n diffraction from crystals it is

n o r m a l t o assert t h a t diffraction occurs only w h e n
B r a g g ' s law is satisfied. T h i s is r e a s o n a b l e because t h e
i n t e r a c t i o n b e t w e e n solids a n d rays o r n e u t r o n s is
w e a k a n d a m o r e careful t h e o r y (or e x p e r i m e n t )
s h o w s t h a t significant diffraction occurs only if the
5
crystal is within 1 0 " r a d (i.e., s e c o n d s of arc) of the
exact B r a g g angle. In c o n t r a s t , t h e i n t e r a c t i o n of
electrons w i t h solids is s t r o n g a n d , as a result, the
r a n g e of angles a b o u t t h e B r a g g angle over which
2
diffraction o c c u r s c a n be a b o u t 1 0 " r a d (i.e., of the
o r d e r of a degree) for low-index reflections, which is
c o m p a r a b l e with t h e B r a g g angle itself.
T h e result of this is t h a t , w h e r e a s a single crystal in
a n x-ray b e a m typically d o e s n o t diffract a n d h a s t o be
t u r n e d t o a special o r i e n t a t i o n t o p r o d u c e even a
single diffracted b e a m , in electron diffraction m a n y
b e a m s a r e excited a t all crystal o r i e n t a t i o n s . M o r e
over, m a n y of these b e a m s c a n h a v e intensities as
great as t h e intensity in t h e direct b e a m . H i g h - e n e r g y
electron diffraction carried o u t in a t r a n s m i s s i o n
electron m i c r o s c o p e is therefore a c o m p l e x d y n a m i c a l
process in which electrons a r e scattered b a c k a n d
forth a m o n g m a n y b e a m s . A s a result, the intensities
in t h e diffracted b e a m s a r e a sensitive function of t h e
angle b e t w e e n t h e incident electron b e a m a n d the
crystal s t r u c t u r e . T h e analytical p o w e r of c o n v e r g e n t b e a m diffraction arises because c o n v e r g e n t - b e a m p a t
t e r n s display this v a r i a t i o n of intensity with angle.

2. Experimental

Details

In earlier diffraction t e c h n i q u e s , p a r t i c u l a r l y selecteda r e a diffraction, t h e s a m p l e w a s illuminated with a

parallel b e a m of electrons a n d a r a t h e r large a r e a of
specimen c o n t r i b u t e d t o t h e p a t t e r n . A l t h o u g h this
k i n d of p a t t e r n m i g h t a p p e a r t o give i n f o r m a t i o n
a b o u t diffraction intensities for a p a r t i c u l a r orien
t a t i o n , it did n o t , b e c a u s e it w a s always t h e result of
a n a v e r a g i n g over t h e r a n g e of o r i e n t a t i o n a n d thick
ness within t h e field of view a n d this w o u l d a l m o s t
always d e g r a d e t h e i n f o r m a t i o n in t h e p a t t e r n . I n
c o n v e r g e n t - b e a m diffraction, b y c o n t r a s t , t h e incident
electron b e a m is focused o n t o t h e specimen (Fig. 1),
so t h a t only t h e small a r e a of t h e s a m p l e t h a t is
illuminated c o n t r i b u t e s t o t h e resulting diffraction
p a t t e r n . E l e c t r o n s a r e incident o n t h e specimen a t a
r a n g e of angles s i m u l t a n e o u s l y . F i g u r e 1 s h o w s h o w
t h e c o n e of incident electrons p r o d u c e s disks in the
diffraction p a t t e r n : o n e c o r r e s p o n d i n g t o t h e direct

Transmission

Electron

Microscopy:

Convergent-Beam

and

Microdiffraction

t h e best m e a n s of m a k i n g this m e a s u r e m e n t . If the

s a m p l e is set a t a " t w o - b e a m o r i e n t a t i o n , " t h a t is,
satisfying the B r a g g c o n d i t i o n for o n e reflection a n d
r e d u c i n g t o a m i n i m u m t h e effect of all o t h e r reflec
tions, t h e diffracted (or " d a r k - f i e l d " ) disk s h o w s a set
of parallel fringes. T h e s p a c i n g of t h e m i n i m a in these
fringes leads, via a simple g r a p h i c a l m e t h o d , to a
value of t h e thickness of t h e crystal.
T h i s a p p l i c a t i o n of t h e c o n v e r g e n t - b e a m t e c h n i q u e
is u n u s u a l in t h a t m o s t o t h e r a p p l i c a t i o n s of the
m e t h o d , including all t h e o t h e r s discussed here, re
q u i r e t h e crystal t o be set a t a zone-axis o r i e n t a t i o n
(i.e., with t h e axis of t h e b e a m parallel t o a low-index
h i g h - s y m m e t r y axis of t h e crystal), r a t h e r t h a n the
two-beam orientation.

Figure 1
Schematic diagram to show the formation of
convergent-beam electron diffraction patterns

b e a m a n d o n e for e a c h B r a g g reflected b e a m . F i g u r e 2
s h o w s a n e x a m p l e of a c o n v e r g e n t - b e a m p a t t e r n . T h e
v a r i a t i o n of intensity w i t h i n e a c h disk is a m a p of t h e
w a y intensity varies a s a function of t h e angle b e t w e e n
the incident b e a m a n d t h e crystal s t r u c t u r e . E a c h
p o i n t in t h e disk relates t o electrons incident a t a
distinct o r i e n t a t i o n . It is this intensity v a r i a t i o n w i t h i n
t h e disks o f t h e c o n v e r g e n t - b e a m p a t t e r n t h a t m a k e s
such p a t t e r n s so m u c h m o r e i n f o r m a t i v e t h a n o t h e r
diffraction t e c h n i q u e s .
I n m o s t m o d e r n t r a n s m i s s i o n electron m i c r o s c o p e s ,
it is easy t o o b t a i n such p a t t e r n s ; t h e only r e q u i r e m e n t
is t o be able t o tilt t h e s a m p l e t o line u p t h e c h o s e n
o r i e n t a t i o n of t h e crystal with t h e axis of i l l u m i n a t i o n .
Earlier m i c r o s c o p e s c o u l d n o t p r o d u c e such p a t t e r n s
because they lacked t h e electron optical s t r u c t u r e t o
form the focused p r o b e a n d b e c a u s e c o n t a m i n a t i o n
levels were t o o high.
F u r t h e r details of t h e m i c r o s c o p e o p e r a t i o n t o f o r m
c o n v e r g e n t - b e a m p a t t e r n s c a n be f o u n d in t h e Biblio
graphy.

3.

Applications

3.1 Film-Thickness
Determination
T h e r e a r e m a n y a p p l i c a t i o n s for w h i c h it is necessary
t o k n o w t h e local thickness of t h e a r e a u n d e r o b s e r v a
tion in a n electron m i c r o s c o p e . I n t h e case of crystal
line s a m p l e s , c o n v e r g e n t - b e a m diffraction p r o v i d e s

3.2 Phase Identification or "'Fingerprinting"

In t h e p e r i o d since c o n v e r g e n t - b e a m diffraction
became a practical a n d convenient technique, patterns
h a v e been o b t a i n e d from m a n y z o n e axes in m a n y
p h a s e s . F r o m this a c c u m u l a t e d experience it is p o s
sible t o assert t h a t t h e p a t t e r n o b t a i n e d a t each
different z o n e axis from e a c h different p h a s e is dis
tinct. It is t r u e t h a t t h e p a t t e r n s c h a n g e with specimen
thickness a n d with t h e o p e r a t i n g voltage of t h e m i c r o
scope. H o w e v e r , it is usually possible t o recognize a
p a r t i c u l a r p a t t e r n even if t h e voltage o r thickness d o e s
n o t c o r r e s p o n d t o t h a t of the p a t t e r n used for c o m
p a r i s o n . It is also t r u e t h a t there m a y be similarities
b e t w e e n t h e p a t t e r n s o b t a i n e d from different p h a s e s
b u t only w h e n t h e projected crystal s t r u c t u r e s of the
t w o p h a s e s a r e very similar.
T h e s e c a v e a t s i m p l y t h e need for s o m e c a u t i o n
in t h e use of t h e t e c h n i q u e ; nonetheless, t h e use
of c o n v e r g e n t - b e a m p a t t e r n s a t zone-axis orient
a t i o n s (zone-axis p a t t e r n s o r " z a p s " ) c a n p r o v i d e a
very direct a n d positive w a y of identifying crys
talline p h a s e s . T h e first t i m e a p h a s e is studied by
c o n v e r g e n t - b e a m diffraction its identification m a y be
m o r e o r less difficult; it will involve c o n v e n t i o n a l
diffraction analysis, s y m m e t r y d e t e r m i n a t i o n (see
Sect. 3.3) a n d energy-dispersive x-ray s p e c t r o s c o p y
( E D X ) p e r h a p s with electron-energy-loss spectros
c o p y ( E E L S ) if available. T h e c o m b i n a t i o n of unitcell, s p a c e - g r o u p a n d chemical i n f o r m a t i o n p r o v i d e d
by these t e c h n i q u e s will n o r m a l l y be e n o u g h t o p r o
vide a u n i q u e identification of t h e p h a s e from stan
d a r d t a b u l a t i o n s of k n o w n p h a s e s . If a c o m p r e h e n s i v e
set of z a p s is o b t a i n e d for t h e principal z o n e axes of
this s a m p l e , t h e n t h e next time t h e s a m e p h a s e is
e n c o u n t e r e d it c a n be identified a l m o s t immediately
by c o m p a r i n g a z a p with t h o s e previously o b t a i n e d as
a s t a n d a r d . T h i s identification c a n s o m e t i m e s be m a d e
w i t h o u t even t a k i n g a p i c t u r e , by recognizing the
p a t t e r n o n t h e screen of t h e m i c r o s c o p e ( a l t h o u g h
t a k i n g a p i c t u r e is r e c o m m e n d e d for c o n f i r m a t i o n ) .
Z a p s from imperfect crystals a r e d i s t o r t e d a n d this
c a n inhibit p h a s e identification by p a t t e r n recogni
tion. T h e k i n d of features w h i c h c a n give rise t o

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Figure 2
An example of a convergent-beam electron diffraction pattern at a zone-axis orientation: the pattern is from V 3Si at the
[110] zone axis taken at an electron-beam energy of 80 kV (courtesy of D. Konitzer)

Figure 3
Convergent-beam pattern from V 3Si at the [111] zone axis at 80 kV taken at a short camera length to show both the
zero-layer reflections and the outer ring that form the first-order Laue zone: note that the zero-layer reflections, near the
center of the pattern, have sixfold symmetry while the first-order ring shows only threefold (courtesy of D. Konitzer)

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p a t t e r n d i s t o r t i o n s a r e d i s l o c a t i o n s , p l a n a r faults a n d
large v a r i a t i o n s in thickness within t h e electron p r o b e .
Since it frequently h a p p e n s t h a t p h a s e identification is
s o u g h t for small particles of a w k w a r d s h a p e (e.g.,
precipitates in g r a i n b o u n d a r i e s o r grains in a finely
dispersed s t r u c t u r e ) , it m a y n o t b e possible t o o b t a i n
g o o d c o n v e r g e n t - b e a m p a t t e r n s from t h e specimen.
In this case, t h e a p p r o p r i a t e a p p r o a c h is t o p r e p a r e
special s a m p l e s , with large g r a i n s of g o o d crystal, of
those p h a s e s w h o s e presence is suspected. T h e s e
special s a m p l e s c a n b e used t o o b t a i n " s t a n d a r d s e t s "
of z a p s . It is t h e n often possible t o o b t a i n t h e identifi
c a t i o n of t h e p h a s e s b y c o m p a r i n g t h e d i s t o r t e d
p a t t e r n s from t h e specimen with t h e ( u n d i s t o r t e d )
s t a n d a r d sets.
T h i s m e t h o d of identifying p h a s e s is a n i m p o r t a n t
a d d i t i o n t o t h e m o r e u s u a l m e t h o d s of identification
by unit-cell analysis o r by E D X s p e c t r o s c o p y . B o t h of
these latter m e t h o d s a r e subject t o e r r o r a n d a m
biguity. T h e r e a r e m a n y p h a s e s t h a t h a v e similar
lattice p a r a m e t e r s o r lattice p a r a m e t e r s t h a t v a r y w i t h
c o m p o s i t i o n . E D X analysis c a n also be misleading,
especially w h e n t h e particle is e m b e d d e d in a m a t r i x ;
b o t h t h e m a t r i x a n d local c o m p o s i t i o n v a r i a t i o n a t t h e
surface of t h e specimen c a n c o n t r i b u t e t o results t h a t
lead t o e r r o r . F o r these r e a s o n s , t h e initial identifica
tion of a p h a s e , n o t previously seen, s h o u l d b e m a d e
with g r e a t care, using, w h e n e v e r possible, a large
perfect g r a i n o r a g r a i n o n a n e x t r a c t i o n replica r a t h e r
t h a n o n e e m b e d d e d in a m a t r i x . H o w e v e r , o n c e t h e
identification is m a d e , these p r o b l e m s b e c o m e irrele
vant; the c o n v e r g e n t - b e a m p a t t e r n will m a k e a direct
identification.
3.3 Symmetry
Determination
T h e value of k n o w i n g t h e s y m m e t r y of a crystal is n o t
limited t o t h e w a y in w h i c h limiting a search t o o n e
o u t of 230 space g r o u p s aids t h e identification of a
crystal p h a s e . M a n y physical p h e n o m e n a a n d p r o
cesses a r e subject t o c o n s t r a i n t s related t o s y m m e t r y .
T h e n u m b e r of t w i n n i n g m o d e s , t h e n u m b e r of over
g r o w t h v a r i a n t s , t h e m o d e s of p h a s e t r a n s f o r m a t i o n
a n d t h e presence o r a b s e n c e of piezoelectric a n d
pyroelectric effects, for e x a m p l e , all d e p e n d o n t h e
s y m m e t r y of t h e crystal.
Historically, crystal s y m m e t r y h a s been d e t e r m i n e d
by x-ray diffraction b u t this m e t h o d suffers from t w o
limitations: e r r o n e o u s results c a n b e o b t a i n e d if t h e
crystal in q u e s t i o n is f o u n d with a high density of
faults o r twins; a n d n o result a t all c a n be o b t a i n e d if
only a small s a m p l e is available. E l e c t r o n diffraction
o v e r c o m e s these p r o b l e m s . A n electron diffraction
p a t t e r n c a n be o b t a i n e d from a single g r a i n d o w n t o a
few u n i t cells in size a n d , if a crystal h a s faults o r
twins, t h e i m a g e of t h e s a m p l e f o r m e d in t h e i m a g e
m o d e of t h e m i c r o s c o p e allows a defect-free region t o
be c h o s e n t o f o r m t h e diffraction p a t t e r n .
T h e s y m m e t r y of a c o n v e r g e n t - b e a m p a t t e r n a t a
z o n e axis reflects t h e s y m m e t r y of t h e specimen.

Microscopy:

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and

Microdiffraction

H o w e v e r , t h e a i m is, usually, n o t t o d e t e r m i n e the

s y m m e t r y of t h e s a m p l e b u t t o d e t e r m i n e the sym
m e t r y of t h e s a m p l e ' s crystal s t r u c t u r e . Careful s t u d
ies h a v e s h o w n t h a t p r o v i d e d t h e s a m p l e , within t h e
region of t h e electron p r o b e , is (a) a p p r o x i m a t e l y
u n i f o r m in thickness a n d n o t t o o thin, (b) n o t b u c k
led, (c) n o t tilted t o a very steep angle a n d (d) free
from defects a n d strain, a n d p r o v i d e d t h e electron
p r o b e itself is large e n o u g h t o cover several unit cells,
t h e n t h e s y m m e t r y in t h e z a p s a c c u r a t e l y reflect the
s y m m e t r y of t h e crystal s t r u c t u r e .
T h e use of c o n v e r g e n t - b e a m p a t t e r n s t o d e t e r m i n e
crystal s y m m e t r y n o r m a l l y p r o c e e d s in t w o stages.
T h e s y m m e t r i e s of t h e p a t t e r n s a r e used t o d e t e r m i n e
t h e crystal p o i n t g r o u p a n d t h e n i n f o r m a t i o n o n screw
axes a n d glide p l a n e s d e t e r m i n e d from " f o r b i d d e n "
reflections is used t o d e t e r m i n e t h e space g r o u p .
T h e s y m m e t r y of t h e diffraction a t a z o n e axis is
described b y t h e "diffraction g r o u p . " H o w e v e r , in
general, n o t all t h e s y m m e t r y elements of the diffrac
tion g r o u p a r e reflected in s y m m e t r i e s of a single o n axis c o n v e r g e n t - b e a m p a t t e r n (since t h e r e a r e 31
diffraction g r o u p s b u t only 10 t w o - d i m e n s i o n a l crys
t a l l o g r a p h i c p o i n t g r o u p s ) . H o w e v e r , different p a r t s
of a z a p m a y s h o w different s y m m e t r i e s . F o r e x a m p l e ,
in F i g . 3 t h e o u t e r ring of reflections (the H O L Z ring;
see Sect. 3.4) d o e s n o t h a v e t h e s a m e s y m m e t r y as the
reflections n e a r t h e center (the z e r o layer). T h i s extra
i n f o r m a t i o n m a y be used t o r e d u c e t h e n u m b e r of
possible diffraction g r o u p s . I n s o m e cases, in o r d e r t o
c o m p l e t e t h e d e t e r m i n a t i o n of t h e diffraction g r o u p ,
a n a d d i t i o n a l c o n v e r g e n t - b e a m p a t t e r n tilted slightly
off t h e z o n e axis m a y b e r e q u i r e d . H o w e v e r , in m o s t
cases, s y m m e t r y i n f o r m a t i o n a t m o r e t h a n o n e z o n e
axis is n e e d e d t o c o m p l e t e t h e d e t e r m i n a t i o n of the
crystal p o i n t g r o u p . A s a result, r a t h e r t h a n m a k i n g
t h e small a d j u s t m e n t of tilt a t t h e first z o n e axis, it is
usually m o r e efficient t o tilt t h r o u g h a large angle t o a
n e w z o n e axis. T h e i n c o m p l e t e i n f o r m a t i o n a t each
axis will usually p e r m i t a n u n a m b i g u o u s d e t e r m i
n a t i o n of t h e p o i n t g r o u p . T h e key p o i n t is t h a t , b y
o b s e r v i n g t h e s y m m e t r i e s in z a p s a t a small n u m b e r of
o r i e n t a t i o n s , t h e p o i n t g r o u p of t h e crystal is u n i q u e l y
determined.
T h e identification of t r a n s l a t i o n a l s y m m e t r y ele
m e n t s (screw axes a n d glide p l a n e s ) is also m o r e
powerful in electron diffraction t h a n b y o t h e r tech
n i q u e s . G l i d e p l a n e s a n d two-fold screw axes give rise
t o " k i n e m a t i c a l l y f o r b i d d e n reflections," reflections
w i t h s t r u c t u r e factor z e r o . I n electron diffraction these
reflections c a n a n d d o o c c u r with c o n s i d e r a b l e inten
sity, b y d o u b l e diffraction. H o w e v e r , a t p a r t i c u l a r
o r i e n t a t i o n s ( a l o n g r a d i a l s y m m e t r y directions a n d a t
t h e exact B r a g g angle), t h e double-diffraction r o u t e s
c a n be p a i r e d in a n t i p h a s e a n d t h e intensity is a g a i n
z e r o . I n t h e c o n v e r g e n t - b e a m disks, these " d y n a m i c a l
e x t i n c t i o n s " a r e manifested by d a r k b a r s t h r o u g h the
c o r r e s p o n d i n g disks. If t h e presence of t h e d a r k b a r is
used in c o n j u n c t i o n with t h e s y m m e t r y of t h e p a t t e r n ,

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it is possible t o say w h e t h e r a screw axis o r a glide

p l a n e o r b o t h a r e present in t h e s t r u c t u r e . T h i s
i n f o r m a t i o n leads t o the d e t e r m i n a t i o n of t h e space
g r o u p . In only a very few cases d o ambiguities r e m a i n
a n d m o s t of these c a n be distinguished by the identifi
c a t i o n of forbidden reflections (as for rays) even
t h o u g h d y n a m i c a l extinctions a r e n o t present. O n l y
the e n a n t i o m o r p h i c p a i r s (space g r o u p s distinguished
by being right- a n d left-handed) c a n n o t be identified
by these techniques; they c a n be distinguished b y
electron diffraction if t h e s t r u c t u r e is k n o w n a n d a full
c o m p u t e r s i m u l a t i o n of t h e diffraction p a t t e r n is
m a d e (this identification is also very difficult by a n y
o t h e r technique).
3.4 Lattice Parameter and Strain
A t s o m e z o n e axes, the central disk of t h e z a p is criss
crossed by a set of fine lines (see Electron
Diffraction).
These lines, which a r e associated with diffraction t o
a n o u t e r ring of reflections, m o v e as a very sensitive
function of b o t h t h e voltage of t h e m i c r o s c o p e a n d of
the spacing of the c o r r e s p o n d i n g set of a t o m i c p l a n e s .
Small c h a n g e s in t h e positions of the lines c a n ,
therefore, be used t o m o n i t o r v a r i a t i o n in lattice
p a r a m e t e r . T h i s d e t e r m i n a t i o n requires a m o d e r a t e l y
thick s a m p l e (say, lOOnm) which in t u r n implies a
limit of a few tens of n a n o m e t e r s in t h e lateral
d i m e n s i o n s of the region of crystal t h a t c o n t r i b u t e s t o
the lattice p a r a m e t e r m e a s u r e m e n t . T h e precision of
3
the m e a s u r e m e n t is typically 1 in 10 a n d c a n a p
4
p r o a c h 1 in 10 if the specimen is cooled.
T h e r e a s o n for t h e relatively high precision (con
ventional electron diffraction m e t h o d s h a v e a preci
sion of p e r h a p s only 1%), w i t h o u t the need for
calibration, involves t w o ideas: (a) t h e lines a r e fine,
hence their position c a n be m e a s u r e d accurately; a n d
(b) the positions of the lines a r e m e a s u r e d relative t o
each o t h e r a t the center of t h e p a t t e r n .
T h e lines a r e fine because e a c h d a r k line in t h e
central disk is associated with a b r i g h t line in a n o u t e r
ring of reflections (like t h e o u t e r ring in Fig. 3, say).
T h e o u t e r rings of reflections a r e k n o w n as highero r d e r L a u e zones ( H O L Z ) a n d , as a result, the corres
p o n d i n g lines in t h e central disk are k n o w n as H O L Z
lines. Since the B r a g g reflection i n t o a h i g h e r - o r d e r
L a u e z o n e is associated with a high-index p o i n t in t h e
reciprocal lattice a n d a c o r r e s p o n d i n g l y w e a k F o u r i e r
c o m p o n e n t of the p o t e n t i a l , t h e scattering is w e a k .
Diffraction occurs only close t o t h e B r a g g angle (in
c o n t r a s t with low-index reflections) a n d the H O L Z
lines a r e n a r r o w .
If the p o s i t i o n s of the lines in t h e o u t e r ring of
reflections (i.e., the H O L Z itself) were m e a s u r e d , t h e
precision w o u l d be low (even with careful c a l i b r a t i o n )
because the m e a s u r e m e n t w o u l d be trying t o reveal
small c h a n g e s in a long distance (the r a d i u s of the
H O L Z ) o n a scale t h a t is n o n l i n e a r because of t h e
a b e r r a t i o n s of the electron lenses. H o w e v e r , by l o o k
ing a t small relative shifts in t h e H O L Z lines in t h e

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central disk, it is possible t o m a k e precise m e a s u r e

m e n t s , as indicated a b o v e . T h e nonlinearities of t h e
i n s t r u m e n t a r e essentially eliminated a n d n o cali
b r a t i o n is n e e d e d because t h e low-index reflections
p r o v i d e a scale.
T h i s t e c h n i q u e h a s been used, for e x a m p l e , t o p l o t
the lattice p a r a m e t e r profile of s e m i c o n d u c t o r h e t e r o j u n c t i o n s , t o m e a s u r e t h e difference in lattice p a r a m
eter b e t w e e n p h a s e s , t o m o n i t o r t h e u n i f o r m i t y of
c o m p o s i t i o n (where lattice p a r a m e t e r is a function of
c o m p o s i t i o n ) a n d t o d e t e r m i n e t h e strain a r o u n d
c u b o i d / precipitates in nickel-base superalloys.
3.5 Other Areas of Application
T h e four a r e a s discussed a b o v e a r e , a n d will p r o b a b l y
c o n t i n u e t o be, the m a i n a r e a s of a p p l i c a t i o n of
c o n v e r g e n t - b e a m t e c h n i q u e s . T h e y a r e the best d e
veloped a n d they d o n o t require a n y significant
a m o u n t of c o m p u t i n g o r t h e o r y . H o w e v e r , there a r e
o t h e r a r e a s in which c o n v e r g e n t - b e a m diffraction c a n
give v a l u a b l e i n f o r m a t i o n ; s o m e of these a r e indicated
in the following.
In t h e p r e c e d i n g a p p l i c a t i o n s , use w a s m a d e of
t h o s e aspects of t h e p a t t e r n s which c a n be i n t e r p r e t e d
directly b y eye: the p a t t e r n , its s y m m e t r y a n d the
p o s i t i o n of the lines. H o w e v e r , in o r d e r t o calculate
t h e detailed intensity d i s t r i b u t i o n in t h e p a t t e r n s it is
necessary t o c a r r y o u t a full d y n a m i c a l diffraction
calculation. T h e i n p u t s t o this calculation a r e the
crystal s t r u c t u r e including the a t o m i c p o s i t i o n s , the
a t o m i c p o t e n t i a l s including t h e D e b y e - W a l l e r factors
a n d a b s o r p t i o n coefficients. I n v e r t i n g this calculation
t o o b t a i n a t o m i c p o t e n t i a l s o r a t o m p o s i t i o n s in the
unit cell is, in general, n o t possible a t present. H o w
ever, p r o g r e s s is being m a d e t o w a r d s t h a t e n d a n d , in
specific cases, it h a s been possible t o i m p r o v e a t o m i c p o t e n t i a l d a t a a n d t o solve crystal structures.
I n a d d i t i o n t o its p o w e r t o c h a r a c t e r i z e perfect
crystals, studies h a v e been m a d e o n t h e w a y in which
defects a n d d i s o r d e r affect z a p s .
A n o t h e r a r e a of interest is the use of very small
electron p r o b e s . If a m i c r o s c o p e is fitted with a fieldemission g u n , a p r o b e as small as 0.5 n m c a n still c a r r y
e n o u g h c u r r e n t t o form a n experimentally useful
diffraction p a t t e r n . T h i s o p e n s t h e possibility of
o b t a i n i n g diffraction p a t t e r n s from regions smaller
t h a n t h e u n i t cell a n d o b t a i n i n g i n f o r m a t i o n o n , for
e x a m p l e , local c o o r d i n a t i o n . P r o b e s o n this scale m a y
also yield v a l u a b l e i n f o r m a t i o n o n local s t r u c t u r e in
a m o r p h o u s m a t e r i a l s , especially if used in conjunc
tion with a d v a n c e d , c o m p u t e r - b a s e d i m a g e analysis
techniques.
C o n v e r g e n t - b e a m diffraction h a s b r o u g h t a b o u t ,
indirectly, a n i m p r o v e m e n t in t h e use of electron
diffraction for unit-cell d e t e r m i n a t i o n . C o n v e r g e n t b e a m p a t t e r n s often h a v e useful i n f o r m a t i o n a t large
diffraction angles (Fig. 3) which require t h e use of
s h o r t c a m e r a lengths. A s a result, it h a s been realized
t h a t small c a m e r a length p a t t e r n s p r o v i d e a simple

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m e a n s for d e t e r m i n i n g t h e u n i t cell of t h e s t r u c t u r e
from a single p a t t e r n .
A l t h o u g h specimens for t r a n s m i s s i o n electron
m i c r o s c o p y a r e never m o r e t h a n a few h u n d r e d n a n o
m e t e r s thick a n d h e n c e all t r a n s m i s s i o n electron
m i c r o s c o p y uses s a m p l e s in which surface c h a r a c t e r i s
tics are i m p o r t a n t , m o s t studies a r e c o n c e r n e d with
characterizing the " b u l k " material. Convergent-beam
techniques, in p a r t i c u l a r , a r e c o n c e r n e d with t h e
crystal s t r u c t u r e ( a n d its defects) of the infinite crystal
from which t h e s a m p l e is cut.
O n the o t h e r h a n d , as t h e q u a l i t y of t h e v a c u u m in
the i n s t r u m e n t h a s i m p r o v e d , electron m i c r o s c o p y h a s
b e c o m e m o r e a n d m o r e involved in surface studies.
Specimens t h a t h a v e a t o m i c a l l y s m o o t h surfaces c a n
s h o w a n o m a l o u s diffraction effects if their thickness
d o e s n o t c o r r e s p o n d t o a n integer n u m b e r of u n i t cells
(or the w r o n g integer n u m b e r of cells in s o m e cases).
T h e s e effects c a n be used t o i m a g e surface steps, for
example.
N e w h i g h - r e s o l u t i o n electron m i c r o s c o p e s h a v e
m a d e d r a m a t i c c o n t r i b u t i o n s t o surface studies b y
direct i m a g i n g of surfaces seen edge o n . N e w (or
newly revived) reflection surface i m a g i n g t e c h n i q u e s
h a v e s h o w n s p e c t a c u l a r i m a g e s of surface steps,
surface-reconstruction p h a s e t r a n s f o r m a t i o n s a n d
surface defects.
C o n v e r g e n t - b e a m diffraction, t o o , c a n be carried
o u t in a reflection m o d e from surfaces t h a t a r e a t o m i
cally s m o o t h (or nearly so). R e c e n t results suggest
t h a t , as in t r a n s m i s s i o n , surface c o n v e r g e n t - b e a m
p a t t e r n s will p r o v e a powerful tool t h a t is c o m p l e m e n
t a r y t o t h e o t h e r m e t h o d s of surface c h a r a c t e r i z a t i o n
in the electron m i c r o s c o p e .

4.

Conclusion

C o n v e r g e n t - b e a m diffraction is a t e c h n i q u e t h a t h a s
m a n y virtues. It is e x p e r i m e n t a l l y r a t h e r simple a n d
c a n be u n d e r t a k e n o n m o s t m o d e r n m i c r o s c o p e s
w i t h o u t i n s t r u m e n t a l modification. T h e i n f o r m a t i o n
is o b t a i n e d from very small regions of the specimen.
T h e p a t t e r n s a r e very rich in i n f o r m a t i o n . T h e princi
pal a p p l i c a t i o n s (fingerprinting, s y m m e t r y d e t e r m i
n a t i o n , m e a s u r e m e n t of lattice p a r a m e t e r v a r i a t i o n ,
thickness d e t e r m i n a t i o n ) require m i n i m a l , if a n y ,
c o m p u t i n g . Finally, the p a t t e r n s a r e a g r e e a b l e t o
w o r k with b e c a u s e they a r e visually interesting a n d
often beautiful.

cknowledgement

This w o r k w a s s u p p o r t e d by t h e U S D e p a r t m e n t of
Energy. T h i s e n t r y is a revision of a n article in Applied
Surface Science t o w h o m a c k n o w l e d g e m e n t is m a d e .
See also: Electron
Analytical

Diffraction;

Electron

Microscopy,

Microscopy:

Convergent-Beam

and

Microdiffraction

Bibliography
Chemelle P, Ribes A, Portier R, Thomas J 1983 Introduc
tion to some applications of convergent beam electron
diffraction (in French). J. Microsc. Spectrose. Electron. 8:
401-18
Convergent Beam Electron Diffraction of Alloy Phases 1984
by the Bristol Group, compiled by John Mansfield.
Hilger, Bristol, UK
Fraser L 1983 Applications of convergent-beam electron
diffraction to nickel-base superalloys. J. Microsc. Spectrosc. Electron. 8: 431-41
Fung , McKernan S, Steeds J W, Wilson J A 1981
Broken hexagonal symmetry in the locked-in state of
2Ha-TeSe 2, and the discommensurate microstructure of
its incommensurate CDW states. / . Phys. C 14: 5417-32
Goodman P, Olsen A, Whitfield J 1985 Mirror-symmetric
and non-mirror-symmetric glide planes in CuAs-Se, _xSx,l:
a convergent beam electron diffraction study. Ultramic
roscopy 16: 227-32
Jones , Rackham G M, Steeds J W 1977 Higher order
Laue zone effects in electron diffraction and their use in
lattice parameter determination. Proc. R. Soc. London,
Ser. A 354: 197-222
Kaufman J, Fraser L 1984 Characterization of meta
stable crystalline phases in the Al-Ge alloy system. Acta
Metall. 33: 191-203
Kelly , Jostsons A, Blake R G, Napier J G 1975 The
determination of foil thickness by scanning transmission
electron microscopy. Phys. Status Solidi A 31: 771-80
Porter A J, Ecob R C, Ricks R A 1983 Coherency strain
fields: magnitude and symmetry. J. Microsc. 129: 327-36
Spence J C H, Carpenter R W 1986 Electron microdiffrac
tion. In: Joy D C, Romig A D Jr, Goldstein J (eds.)
1986 Principles of Analytical Electron
Microscopy.
Plenum, New York
Steeds J W 1979 Convergent beam electron diffraction. In:
Hren J J, Goldstein J I, Joy D C (eds.) 1979 Introduction
to Analytical Electron Microscopy. Plenum, New York,
pp. 387-422
Steeds J W 1984 Electron crystallography. In: Chapman J
N, Craven A J (eds.) 1984 Quantitative Electron Micros
copy, Scottish Universities Summer School in Physics,
Edinburgh, pp. 49-96
Tanaka M, Saito R, Watanabe D 1980 Symmetry determi
nation of the room-temperature form of L n N b 0 4
(Ln = La, Nd) by convergent-beam electron diffraction.
Acta Crystallogr., Sect. A 36: 350-2
Tanaka M, Sekii H, Nagasawa 1983 Space-groups deter
mination by dynamic extinction in convergent-beam elec
tron diffraction. Acta Crystallogr., Sect. A 39: 825-37
Tanaka M, Terauchi 1985 Convergent-Beam Electron
Diffraction. JEOL, Tokyo
Thomas J, Portier R, Gandais 1983 Introduction to the
theory and practice of convergent beam electron diffrac
tion (in French). J. Microsc. Spectrosc. Electron. 8: 34399
Vincent R, Bird D M, Steeds J W 1984 Structure of AuGeAs
determined by convergent-beam electron diffraction: I,
derivation of basic structure; II, refinement of structural
parameters. Philos. Mag. A 50: 745-86
J. A . E a d e s
[University of Illinois, U r b a n a ,
Illinois, U S A ]

545


Vibrothermography
V i b r o t h e r m o g r a p h y is a n o n d e s t r u c t i v e e v a l u a t i o n
( N D E ) t e c h n i q u e t h a t c a n be used t o locate a n d
identify regions of discontinuities in a variety of
m a t e r i a l s . T h e m e t h o d uses real-time video t h e r m o g
r a p h y t o detect t h e r m a l g r a d i e n t s resulting from t h e
t r a n s f o r m a t i o n of m e c h a n i c a l v i b r a t i o n a l energy i n t o
h e a t . T h e r m o g r a p h y refers t o t h e d e t e c t i o n a n d m a p
p i n g of i s o t h e r m a l c o n t o u r lines o n t h e surface of a
b o d y . R e a l - t i m e video t h e r m o g r a p h y refers t o t h e
detection of infrared r a d i a t i o n from t h e surface, t h e
electronic c o n d i t i o n i n g of t h e received e l e c t r o m a g n e
tic signals a n d t h e display of these as i s o t h e r m a l
c o n t o u r lines o n a c a t h o d e r a y t u b e . V i b r o t h e r m o
g r a p h y is especially useful for t h e d e t e c t i o n of d e l a m i n a t i o n s o r d e l a m i n a t i o n - l i k e d a m a g e in a d v a n c e d
c o m p o s i t e m a t e r i a l s (see Composite Materials:
Non
destructive Evaluation). It h a s , h o w e v e r , s h o w n itself
to be a d a p t a b l e t o h o m o g e n e o u s m a t e r i a l s as well.
T h e m e c h a n i c a l v i b r a t i o n a l energy w h i c h is a p p l i e d
to the material to develop the thermal gradient pat
terns is a m a j o r a t t r i b u t e of t h e t e c h n i q u e . T h e r e a r e
o t h e r w a y s of using t h e r m o g r a p h y t o detect local
thermal conductivity inhomogeneities. F o r example,
the b o d y c a n be h e a t e d externally. T h e r m o g r a p h y will
t h e n detect h o t a n d cold regions c a u s e d b y t h e local
v a r i a t i o n s in t h e r m a l conductivities. H o w e v e r , these
t h e r m a l c o n d u c t i v i t y v a r i a t i o n s m a y b e c a u s e d by a
n u m b e r of effects, such as p h a s e segregation, w h i c h
m a y n o t be related t o d a m a g e d e v e l o p e d b y in-service
l o a d s . T h e benefit of a p p l y i n g m e c h a n i c a l v i b r a t i o n a l
energy t o t h e specimen is t h a t this energy will i n t e r a c t
with localized regions of d a m a g e , c a u s i n g preferential
t r a n s f o r m a t i o n of h e a t w h i c h is d e t e c t a b l e by t h e r m o
g r a p h y . Since t h e m e c h a n i c a l s t r e n g t h , stiffness a n d
life of a n y s t r u c t u r a l c o m p o n e n t a r e ultimately affec
ted by t h e stress state existing inside t h e b o d y , a n
N D E m e t h o d w h i c h c a n directly o r indirectly react t o
the internal stress s t a t e will be m o r e responsive t o t h e
m e c h a n i c a l state of t h e m a t e r i a l . I n o t h e r w o r d s ,
v i b r o t h e r m o g r a p h y is a n N D E m e t h o d w h i c h is dir
ectly responsive t o t h e stress state in t h e m a t e r i a l
while o t h e r t e c h n i q u e s for establishing t h e r m a l g r a d i
ents a r e n o t .

1. Description

of

Technique

V i b r o t h e r m o g r a p h y is a n active N D E m e t h o d . T h a t
is, s o m e external s o u r c e of energy m u s t be a p p l i e d t o
t h e b o d y in o r d e r for t h e N D E t e c h n i q u e t o be able t o
detect the d a m a g e d o r flawed regions existing in t h e
m a t e r i a l . S u c h t e c h n i q u e s a r e distinguished from p a s

sive N D E m e t h o d s , such as a c o u s t i c emission, which

r e s p o n d t o internally self-generated energy. I n the
case of v i b r o t h e r m o g r a p h y , as its n a m e implies, t h e
e n e r g y i n p u t is in t h e f o r m o f v i b r a t i o n a l m e c h a n i c a l
energy. I n general, t h e v i b r a t i o n a l energy m a y be
described by several different p a r a m e t e r s , such as
a m p l i t u d e , frequency a n d w a v e f o r m . A p p l i c a t i o n s of
t h e t e c h n i q u e h a v e e m p h a s i z e d t w o distinct forms of
v i b r a t i o n a l energy: (a) h i g h - a m p l i t u d e , low-frequency
a n d (b) l o w - a m p l i t u d e , high-frequency sinusoidal
w a v e f o r m s . It is likely t h a t t h e energy dissipative
m e c h a n i s m s in these t w o cases t h a t give rise t o t h e
t h e r m a l g r a d i e n t s a r e different, a n d t h u s e a c h case
s h o u l d b e discussed separately.
F o r h i g h - a m p l i t u d e , low-frequency m e c h a n i c a l
v i b r a t i o n s , t h e energy is typically a p p l i e d t o the
s p e c i m e n b y a fatigue testing m a c h i n e . T h e specimen
t o be studied is placed in t h e l o a d frame a n d l o a d e d
with a m p l i t u d e s p e r h a p s 2 0 - 9 0 % of t h e u l t i m a t e
s t r e n g t h of t h e m a t e r i a l a n d a t frequencies in the
r a n g e of 5 - 5 0 H z . I n this s i t u a t i o n , t h e energy dissipa
tive m e c h a n i s m s a r e a l m o s t certainly viscoelastic o r
anelastic in n a t u r e . T h e level of l o a d i n g is severe
e n o u g h t h a t local regions of fatigue d a m a g e initiate
a n d p r o g r e s s d u r i n g t h e test. Because of this, this
p a r t i c u l a r a p p l i c a t i o n of v i b r o t h e r m o g r a p h y is n o t
n o n d e s t r u c t i v e . H o w e v e r , if t h e specimen is t o be
fatigue tested a n y w a y , infrared r a d i a t i o n will n a t u r
ally be e m i t t e d a n d this t e c h n i q u e c a n be used t o
follow t h e d e v e l o p m e n t of fatigue d a m a g e . I n d e e d ,
t h e v i b r o t h e r m o g r a p h i c m e t h o d h a s p r o v e d in such
cases t o be a n a c c u r a t e i n d i c a t o r of early fatigue
d a m a g e d e v e l o p m e n t (Reifsnider a n d S t i n c h c o m b
1975), early in t h e sense t h a t t h e d a m a g e is n o t yet
detectable by other, usual N D E methods.
F o r l o w - a m p l i t u d e , high-frequency m e c h a n i c a l
v i b r a t i o n s , t h e p r a c t i c e is t o a t t a c h o n e e n d o r side
of t h e specimen t o a m e c h a n i c a l s h a k e r , t h e r e b y
a p p l y i n g only inertial l o a d s t o t h e b o d y . Typical
frequencies used in this a p p l i c a t i o n r a n g e from
15 k H z t o 50 k H z , b u t m a y b e increased t o t h e
h u n d r e d s of k i l o h e r t z if suitable s h a k e r s a r e available.
T h e s t r a i n s a n d stresses d e v e l o p e d in t h e m a t e r i a l
u n d e r this inertial l o a d i n g a r e relatively small. I n
p a r t i c u l a r , they a r e small e n o u g h so as n o t t o c a u s e
a n y a d d i t i o n a l d a m a g e in t h e specimen themselves. It
is n o t clear a t t h e p r e s e n t time exactly w h a t physical
m e c h a n i s m s a r e r e s p o n s i b l e for t h e t r a n s f o r m a t i o n of
m e c h a n i c a l t o h e a t energy in this instance. H o w e v e r ,
o b s e r v a t i o n s seem t o indicate t h a t t h e h e a t i n g is
c a u s e d b y t h e local frictional r u b b i n g o r s l a p p i n g of
i n t e r n a l surfaces.
O n e m i g h t also a p p l y intense, high-frequency ultra
s o u n d t o a b o d y , for i n s t a n c e , with a n u l t r a s o n i c
547

Vibrothermography

h o r n . T h i s h a s been tried, with g o o d results in h o m o

geneous m a t e r i a l s ( M i g n o g n a a n d G r e e n 1980). T h i s
a p p l i c a t i o n is also likely, h o w e v e r , t o itself c a u s e
d a m a g e t o t h e b o d y being studied.
W h a t e v e r m e a n s is used to i n t r o d u c e m e c h a n i c a l
v i b r a t i o n a l energy i n t o t h e specimen, t h e s e c o n d p a r t
of t h e p r o c e d u r e is identical. It is simply necessary t o
observe the v i b r a t e d b o d y with a c a m e r a w h i c h is
sensitive to infrared r a d i a t i o n . Infrared r a d i a t i o n is
t h a t p a r t of t h e e l e c t r o m a g n e t i c s p e c t r u m with w a v e
lengths longer t h a n t h o s e of visible red light a n d
smaller t h a n t h o s e associated with m i c r o w a v e s . T h e r e
are several commercially available infrared c a m e r a s .
Generally, these c a m e r a s a r e associated with a n elec
tronic c o n d i t i o n i n g system which displays t h e
received signals o n either a b l a c k - a n d - w h i t e o r a c o l o r
c a t h o d e ray t u b e . T h e c a m e r a m e c h a n i c a l l y scans,
t h r o u g h a system of revolving m i r r o r s , t h e a r e a being
investigated so t h a t a real-time video i m a g e of t h e
surface is p r e s e n t e d o n t h e m o n i t o r . S h a d i n g s of g r a y
o n the b l a c k - a n d - w h i t e m o n i t o r o r distinctive c o l o r
b a n d s o n t h e color m o n i t o r a r e used t o distinguish t h e
thermal gradient patterns. One can measure absolute
t e m p e r a t u r e with such a device only if the emissivity
of t h e r a d i a t i n g surface is k n o w n a n d if a p p r o p r i a t e
c a l i b r a t i o n is p e r f o r m e d . T h i s is n o t r e q u i r e d , h o w
ever, for a p p l i c a t i o n of t h e v i b r o t h e r m o g r a p h y tech
n i q u e since only t h e r m a l g r a d i e n t s a r e r e q u i r e d t o
locate regions c o n t a i n i n g stress raisers.
A n i m p o r t a n t need for further d e v e l o p m e n t of
v i b r o t h e r m o g r a p h y as a n N D E m e t h o d is t h e m a t h e
matical m o d e l l i n g of the physical p h e n o m e n a r e s p o n
sible for the t r a n s f o r m a t i o n of m e c h a n i c a l t o h e a t
energy a r o u n d the regions of d a m a g e in t h e m a t e r i a l .
Classically, very large n u m b e r s of b o t h linear a n d
n o n l i n e a r dissipative m e c h a n i s m s h a v e b e e n identified
in m a t e r i a l s a n d m a t e r i a l systems. T h e s e include such
p h e n o m e n a as anelastic effects (such as a t o m i c diffu
sion, o r d e r - d i s o r d e r processes a n d t h e r m a l diffusion),
viscoelastic effects, t h e r m o e l a s t i c effects a n d stressw a v e losses. Analysis of these m e c h a n i s m s (Reifsnider
et al. 1980) h a s indicated t h a t only a few of these
a p p e a r t o be c a p a b l e of p r o d u c i n g t h e h e a t p a t t e r n s
which h a v e been o b s e r v e d a n d w h i c h a r e discussed in
the next section. T h e excitations w h i c h h a v e b e e n
used t o p r o d u c e t h e o b s e r v e d results h a v e b e e n in
the frequency r a n g e of a b o u t 1 H z t o 100 k H z . I n
this frequency r a n g e , m a n y of t h e classical dissi
pative m e c h a n i s m s c a n n o t p r o d u c e t h e degree of
h e a t i n g t h a t h a s actually been o b s e r v e d . T h e few
m e c h a n i s m s t h a t m i g h t a c c o u n t for t h e h e a t p r o
d u c e d include viscoelastic dissipation, s t a n d i n g w a v e
r e s o n a n t dissipation, plastic slip a n d t h e r u b b i n g
or c l a p p i n g t o g e t h e r of adjacent surfaces (which
p r o d u c e s h e a t i n g b y s o m e frictional surface effects).
O f these, t h e last effect a p p e a r s t o be t h e m o s t
i m p o r t a n t in t e r m s of t h e ease w i t h w h i c h d e l a m i n a tion-like flaws c a n be o b s e r v e d , as described in t h e
following.

548

2.

Applications

V i b r o t h e r m o g r a p h y h a s been applied t o t h e d e t e c t i o n
of d a m a g e in b o t h h o m o g e n e o u s a n d c o m p o s i t e
m a t e r i a l s . T h i s is a u n i q u e t h e r m o g r a p h i c t e c h n i q u e
in t h a t t h e h e a t o b s e r v e d is p r o d u c e d b y the specimen
r a t h e r t h a n b y a n o u t s i d e source. T h e h e a t so p r o
d u c e d is p r o p o r t i o n a l t o t h e m e c h a n i c a l energy dissi
p a t e d b y t h e m a t e r i a l a t e a c h p o i n t . T h e energy
dissipated, in t u r n , is p r o p o r t i o n a l t o t h e level of
stress a t t h a t p o i n t . I n a d d i t i o n , it s h o u l d b e n o t e d
t h a t t h e h e a t d e v e l o p m e n t will d e p e n d o n t h e inte
g r a t e d , o r c o m p l e t e , state of d a m a g e in t h e m a t e r i a l .
H e n c e , it s h o u l d b e possible t o o b s e r v e t h e severity
a n d d i s t r i b u t i o n of d a m a g e in a b o d y b y observing t h e
severity a n d d i s t r i b u t i o n of stress indicated by t h e
heat pattern.
A s a n illustration of this, o n e m i g h t n o t e t h a t m a n y
real m a t e r i a l s h a v e n o b o u n d a r i e s of m a t e r i a l p h a s e s
w h i c h exist o n a scale large e n o u g h t o influence
significantly engineering b e h a v i o r . H e n c e it is r e a s o n
able t o call these m a t e r i a l s h o m o g e n e o u s o n t h e
m a c r o s c o p i c level. A l t h o u g h these m a t e r i a l s m a y h a v e
p h a s e b o u n d a r i e s a t t h e m i c r o level, u n d e r v i b r a t o r y
excitation, t h e m a c r o s c o p i c h e a t p a t t e r n p r o d u c e d in
a n unflawed, h o m o g e n e o u s plate is u n i f o r m a n d cor
r e s p o n d s t o w h a t is called a h o m o g e n e o u s state of
stress. W h e n a d i s c o n t i n u i t y such a s a hole, n o t c h o r
c r a c k is p r e s e n t , t h e stress field also b e c o m e s n o n u n i
f o r m a n d t h e o b s e r v e d h e a t p a t t e r n indicates t h e s a m e
t y p e of c h a n g e . F i g u r e 1 s h o w s t h e d i s t r i b u t i o n of
h y d r o s t a t i c stress a r o u n d a circular h o l e in a finite
p l a t e ; F i g . 2 is t h e c o r r e s p o n d i n g d i a g r a m for inp l a n e s h e a r stress. A v i b r o t h e r m o g r a p h i c p i c t u r e w a s
o b t a i n e d for a m e t h y l m e t h a c r y l a t e p l a t e , 25 m m wide
by 175 m m l o n g b y 6.25 m m thick with a 6.25 m m
center h o l e . T h i s p l a t e w a s l o a d e d in a s e r v o h y d r a u l i c
testing frame a t a m a x i m u m of 5 0 % of the u l t i m a t e
l o a d a n d a t a frequency of 30 H z . T h e i s o t h e r m
p a t t e r n t r a c e d from t h e t h e r m o g r a p h i c p i c t u r e is
s h o w n in Fig. 3. A c o m p a r i s o n of Figs. 1 a n d 2 with 3
strongly suggests t h a t t h e h e a t p a t t e r n is r e p r e s e n t a
tive of t h e stress d i s t r i b u t i o n in t h e plate. T h e very
close similarity b e t w e e n Figs. 2 a n d 3 especially
suggests t h a t t h e s h e a r stress in this case is m o r e
i m p o r t a n t in g e n e r a t i n g t h e h e a t energy t h a n is the
hydrostatic component.
V i b r o t h e r m o g r a p h y h a s b e e n applied t o c o m p o s i t e
m a t e r i a l s with excellent results. T h e m e t h o d h a s
p r o v e d itself t o be m o s t useful in detecting the early
f o r m a t i o n of d a m a g e d u r i n g t h e fatigue testing of
c o m p o s i t e s a n d in detecting
delamination-like
d a m a g e in c o m p o s i t e s w h e n t h e l o w - a m p l i t u d e , highfrequency excitation m e t h o d is e m p l o y e d . T h e basic
m e c h a n i s m s of fatigue d a m a g e in a d v a n c e d c o m p o
site m a t e r i a l s a r e q u i t e different from t h a t in h o m o
g e n e o u s m a t e r i a l s . I n s t e a d of t h e initiation of a
fatigue c r a c k a n d its p r o p a g a t i o n in a self-similar
fashion, as o c c u r s in h o m o g e n e o u s m a t e r i a l s , fatigue

Vibrothermography

Figure 3
Isothermal contours traced from thermographic picture of
methyl methacrylate plate fatigue loaded at 30 Hz

Figure 1
Distribution of hydrostatic stress component around a
hole in a finite-sized plate

Figure 2
Distribution of in-plane shear stress component around a
hole in a finite-sized plate (after Talug et al. 1979)

d a m a g e in c o m p o s i t e s consists of v a r i o u s c o m
b i n a t i o n s of m a t r i x c r a c k i n g , fiber m a t r i x d e b o n d i n g ,
d e l a m i n a t i o n , void g r o w t h a n d local fiber b r e a k a g e . A
t e c h n i q u e t o detect a n d m o n i t o r nondestructively
d a m a g e d e v e l o p m e n t in c o m p o s i t e s m u s t be c a p a b l e
of assessing t h e c o m b i n e d effect of t h e n u m e r o u s
d a m a g e m o d e s w h i c h f o r m t h e d a m a g e state. T h e
v i b r o t h e r m o g r a p h i c t e c h n i q u e h a s p r o v e d itself t o be
directly a p p l i c a b l e t o detecting d a m a g e initiation a n d
t o m o n i t o r i n g d a m a g e g r o w t h in c o m p o s i t e s since a
large p e r c e n t a g e of t h e energy released d u r i n g the
d a m a g e processes is c o n v e r t e d t o h e a t . In b o r o n
e p o x y c o m p o s i t e m a t e r i a l , for e x a m p l e , v i b r o
t h e r m o g r a p h y detected, q u i t e early in t h e fatigue test,
local h o t s p o t s in t h e b o d y ( M a r c u s a n d S t i n c h c o m b
1975). W h e n t h e test w a s m o m e n t a r i l y h a l t e d , n o
evidence of d a m a g e c o u l d b e f o u n d by o t h e r m e a n s .
O n r e s t a r t i n g t h e fatigue test, t h e h o t s p o t s r e a p
p e a r e d a n d after m a n y m o r e a d d i t i o n a l l o a d cycles,
o n e w a s finally able t o detect d e v e l o p i n g d a m a g e in
t h e s a m e l o c a t i o n s as t h e h o t regions. O t h e r w o r k , in
graphite epoxy material, has shown that vibrothermo
g r a p h y c a n be used t o m e a s u r e d a m a g e g r o w t h rates
in real t i m e ( H e n n e k e et al. 1979). In this instance, t h e
local h o t s p o t s d e v e l o p e d a r o u n d a n o t c h t h a t w a s
m a c h i n e d in t h e specimen initially, a n d m o v e d with
t h e d a m a g e a s it p r o g r e s s e d a n d grew a w a y from the
notch.
F o r t h e d e t e c t i o n of d a m a g e t h a t a l r e a d y exists in a
specimen d u e t o m a n u f a c t u r i n g defects o r p r e v i o u s
l o a d i n g h i s t o r y , t h e l o w - a m p l i t u d e , high-frequency
m o d e of excitation h a s p r o v e d t o b e very g o o d in
locating delaminations or delamination-like damage
in c o m p o s i t e s . T h i s m o d e of excitation, as n o t e d
earlier, d o e s n o t a d d t o t h e m e c h a n i c a l d a m a g e
a l r e a d y existing in t h e b o d y . A n interesting effect of

549

Vibrothermography

t h e t h r e e w h i t e s p o t s a c r o s s t h e w i d t h of t h e specimen
j u s t b e l o w t h e h o r i z o n t a l center line of the p i c t u r e .
T h e h o l e itself is barely visible as t h e gray region j u s t
b e l o w t h e line of t h e t h r e e w h i t e s p o t s . T h e interesting
t h i n g a b o u t this t h e r m o g r a p h is t h e large h o t region,
i n d i c a t e d b y t h e large w h i t e a r e a o n t h e u p p e r righth a n d side of t h e specimen. T h i s region d e l a m i n a t e d
internally as a result of t h e l o a d i n g applied t o the
specimen. W h i l e t h e m a t c h s t i c k fracture w a s visible t o
t h e eye, this d e l a m i n a t e d region w a s n o t , a n d if it were
n o t for t h e v i b r o t h e r m o g r a p h y t e c h n i q u e , this w o u l d
have gone unnoticed.
T h e v i b r o t h e r m o g r a p h y t e c h n i q u e is also appli
cable t o m o r e c o m p l e x specimen geometries t h a n the
plates previously discussed. T h e t e c h n i q u e h a s been
applied t o full-size helicopter r o t o r blades m a d e from
c o m p o s i t e m a t e r i a l s , m u l t i b l a d e d r o t o r s used in air
c o m p r e s s o r s , a n d a u t o m o b i l e d o o r s . I n e a c h case,
t h e r m a l g r a d i e n t s d e v e l o p e d in regions w h e r e stress
c o n c e n t r a t i o n s existed d u e t o i n t e r n a l defects, d a m a g e
o r o t h e r stress raisers. H e n c e , it a p p e a r s t h a t t h e
v i b r o t h e r m o g r a p h y t e c h n i q u e will lend itself t o field
use as well as t o l a b o r a t o r y investigations.
See also: Stress Distribution: Analysis Using Thermoelastic
Effect

Bibliography
Figure 4
Thermograph of boron epoxy composite plate

this m o d e of excitation is t h a t t h e resulting h e a t

p a t t e r n s a r e very sensitive t o t h e frequency of m e c h a
nical excitation. A s o n e varies t h e frequency, the local
t h e r m a l g r a d i e n t s will d i s a p p e a r a n d r e a p p e a r . T h i s
frequency d e p e n d e n c e h a s been s h o w n t o b e related t o
the size a n d g e o m e t r y of t h e d a m a g e d region (Russell
a n d H e n n e k e 1984). If o n e h a s previously f o u n d a
suitable frequency, w h e n t h e s h a k e r is first t u r n e d o n ,
the t h e r m a l g r a d i e n t s will establish themselves within
3 - 5 s. T h e s e g r a d i e n t s will m o r e o r less r e m a i n c o n
s t a n t while t h e a b s o l u t e t e m p e r a t u r e s will c o n t i n u e t o
rise until a steady state is r e a c h e d . I n s o m e instances,
the h o t t e s t regions in glass e p o x y specimens
h a v e a t t a i n e d values a b o u t 2 0 - 3 0 C a b o v e r o o m
temperature.
A n e x a m p l e of a t h e r m o g r a p h i c p i c t u r e t a k e n dir
ectly from t h e c a t h o d e r a y t u b e m o n i t o r is s h o w n in
Fig. 4. T h i s specimen w a s a b o r o n e p o x y l a m i n a t e d
plate 25.4 m m wide b y 152.4 m m l o n g b y 1.3 m m
thick with a 6.35 m m circular hole in t h e center of t h e
specimen. T h e specimen w a s l o a d e d in t h r e e - p o i n t
b e n d i n g until a m a t c h s t i c k fracture o c c u r r e d a c r o s s
t h e p l a t e a t t h e p o s i t i o n of t h e hole. I n t h e t h e r m o
g r a p h , Fig. 4, this m a t c h s t i c k fracture is evidenced b y

550

Henneke G II, Reifsnider L, Stinchcomb W W 1979

Thermographyan NDI method for damage detection.
J. Met. 31: 11-15
Marcus L A, Stinchcomb W W 1975 Measurement of
fatigue damage in composite materials. Exper. Mech. 15:
55-60
Mignogna R B, Green R Jr 1980 Nondestructive evalu
ation of the effects of dynamic stress produced by highpower ultra sound in materials. In: Stinchcomb W W (ed.)
1980 Mechanics of Nondestructive Testing. Plenum, New
York, pp. 231-48
Reifsnider L, Henneke G, Stinchcomb W W 1980 The
mechanics of vibrothermography. In: Stinchcomb W W
(ed.) 1980 Mechanics of Nondestructive Testing. Plenum,
New York, pp. 249-76
Reifsnider L, Stinchcomb W W 1975 Investigation of
dynamic heat emission patterns in mechanical and chem
ical systems. In: Warren C (ed.) 1975 Proc. 2nd Biennial
Infrared Information Exchange 1974. AGA Corporation,
St. Louis, MO, pp. 45-58
Russell S S, Henneke G II 1984 Dynamic effects during
vibrothermographic N D E of composites. NDT Int. 17:
19-25
Talug A, Reifsnider L, Stinchcomb W W 1979 Thermo
graphic monitoring of damage growth. In: Miller R A
(ed.) 1979 Proc. 4th Biennial Infrared Information Ex
change, 1978. AGA Corporation, St. Louis, MO
E. G . H e n n e k e II
[Virginia P o l y t e c h n i c I n s t i t u t e a n d
State University, B l a c k s b u r g ,
Virginia, U S A ]

w
Wood: Acoustic Emission and
Acousto-UItrasonic Characteristics
A c o u s t i c emission ( A E ) a n d a c o u s t o - u l t r a s o n i c s ( A U )
a r e useful t e c h n i q u e s for d e t e r m i n i n g t h e integrity of
w o o d a n d w o o d - b a s e d m a t e r i a l s . A c o u s t i c emission
arises from m a t e r i a l u n d e r stress a n d c a n b e sensed
with piezoelectric t r a n s d u c e r s , usually c o u p l e d t o t h e
surface of t h e m a t e r i a l . M a t e r i a l s c o n t a i n i n g flaws o r
w e a k a r e a s g e n e r a t e A E a t lower stress levels t h a n
t h o s e of g r e a t e r integrity. A U c o m b i n e s t h e sensitivity
of A E t r a n s d u c e r s w i t h u l t r a s o n i c t r a n s m i t t e r s t o
e v a l u a t e t h e c h a n g e in energy c o n t e n t of a signal a s it
passes t h r o u g h t h e m a t e r i a l . I n general, a decrease in
energy c o n t e n t signifies less m a t e r i a l integrity. A E h a s
been used w i t h w o o d - b a s e d m a t e r i a l s since t h e 1960s;
A U , w h i c h h a s b e e n in f o r m a l existence since t h e late
1970s, h a s only recently b e e n used. T h e a p p l i c a t i o n of
A E and A U to wood-based materials has been sub
stantially a i d e d b y d e v e l o p m e n t s in assessing t h e
integrity of fiber-reinforced plastics ( F R P s ) , w h i c h
h a v e m a n y characteristics similar t o t h o s e of w o o d .
F R P s , like w o o d , r e q u i r e special t e c h n i q u e s t o detect
i n t e r n a l flaws, in c o n t r a s t t o m e t a l s w h e r e x-ray
t e c h n i q u e s a r e usually sufficient.
W o o d - b a s e d m a t e r i a l s h a v e A E characteristics
similar t o t h o s e of fiber-reinforced c o m p o s i t e s . S o m e
indications of w e a k e r ( o r w e a k e n e d ) m a t e r i a l o r s t r u c
t u r e a r e emissions a t low stress levels, a n d increased
n u m b e r s a n d / o r r a t e s of events. A n o t h e r i n d i c a t o r of
w e a k e n e d m a t e r i a l is a low Felicity r a t i o , w h i c h is
d e t e r m i n e d f r o m a s e q u e n c e of l o a d / u n l o a d cycles
d u r i n g w h i c h A E is m o n i t o r e d . I n s o m e m a t e r i a l s , n o
A E o c c u r s d u r i n g r e l o a d i n g until t h e p r e v i o u s stress is
r e a c h e d , giving a l o a d r a t i o (Felicity r a t i o ) of u n i t y
(this is referred t o as t h e K a i s e r effect). H o w e v e r ,
m a n y m a t e r i a l s , such a s c o m p o s i t e s , h a v e a Felicity
r a t i o of less t h a n u n i t y , n o t o b e y i n g t h e K a i s e r effect.
A c o u s t o - u l t r a s o n i c s differs f r o m A E in t h a t a n
active pulser is used t o inject stress w a v e s t h a t a r e
received b y c o n v e n t i o n a l A E sensors, a n d t h e result
ing w a v e f o r m is a n a l y z e d t o d e t e r m i n e t h e c h a n g e
in signal c o n t e n t from p u l s e r t o sensor. A U differs
from c o n v e n t i o n a l u l t r a s o n i c t e c h n i q u e s in t h a t m o r e
subtle flaws, such as p o o r - q u a l i t y b o n d i n g , c a n b e
detected. I n m o s t a p p l i c a t i o n s , t h e p u l s i n g e l e m e n t is
also a c o n v e n t i o n a l A E sensor t h a t is energized w i t h a
n a r r o w , h i g h - v o l t a g e pulse, b u t o t h e r m e a n s of sur
face s t i m u l a t i o n c a n b e used, i n c l u d i n g m e c h a n i c a l
i m p a c t , laser b u r s t s a n d electrical discharges.

1. Acoustic
Properties
1
Typical u l t r a s o n i c velocities a r e 1 k r n s " a c r o s s t h e

_1

grain and 5 k m s
a l o n g t h e g r a i n for l u m b e r a n d
veneer. R e c o n s t i t u t e d m a t e r i a l s s u c h a s c o m p o s i t e
p a n e l s h a v e velocities similar t o solid w o o d a c r o s s t h e
g r a i n . W o o d - b a s e d m a t e r i a l s a r e a b o u t a n o r d e r of
m a g n i t u d e g r e a t e r in a t t e n u a t i o n t h a n geological
m a t e r i a l s a n d t w o o r d e r s of m a g n i t u d e g r e a t e r t h a n
m e t a l s . A t t e n u a t i o n in w o o d is m u c h g r e a t e r across
t h a n a l o n g t h e g r a i n . Because of these differences, A E
s e n s o r p o s i t i o n i n g is critical, p a r t i c u l a r l y for solid
w o o d w h e r e t h e g r a i n direction is well defined.
Since a t t e n u a t i o n increases e x p o n e n t i a l l y w i t h fre
q u e n c y , t h e u s a b l e u p p e r frequency level for sensors
o n w o o d - b a s e d m a t e r i a l s is a b o u t 100-200 k H z . I n
this frequency r a n g e , a t t e n u a t i o n a l o n g a n d a c r o s s t h e
_1
1
a n d 200 d B m , respect
g r a i n is a b o u t 3 0 d B m
ively. T h e effects of w o o d density a n d m o i s t u r e c o n
t e n t o n a t t e n u a t i o n h a v e n o t b e e n clearly d e t e r m i n e d ,
b u t a p p e a r t o b e of lower o r d e r as c o m p a r e d with
g r a i n angle. O b v i o u s l y , t h e m o r e a t t e n u a t i n g t h e
m a t e r i a l , t h e g r e a t e r t h e limit o n sensitivity. H o w e v e r ,
t h e m o r e a t t e n u a t i n g m a t e r i a l s h a v e a n a d v a n t a g e in
d a m p i n g o u t e x t e r n a l u n w a n t e d signals, p e r m i t t i n g
t h e use of higher gains t o o b t a i n t h e n e e d e d sensiti
vity. A t t e n u a t i o n also results f r o m g e o m e t r i c s p r e a d
ing of t h e signal as it travels t h r o u g h t h e m a t e r i a l ; for
p l a n a r m a t e r i a l s , a t t e n u a t i o n is p r o p o r t i o n a l t o the
d i s t a n c e f r o m t h e s o u r c e , a n d for b u l k m a t e r i a l s , t o
t h e s q u a r e of t h e d i s t a n c e . F o r w o o d - b a s e d m a t e r i a l s ,
t h e g e o m e t r i c s p r e a d i n g m a y b e a n i s o t r o p i c because
of t h e g r a i n direction effect.

2. Coupling

of Transducers

to

Wood-Based

Materials
A c o u s t i c i m p e d a n c e (the p r o d u c t of velocity a n d
d e n s i t y ) is t h e d e t e r m i n i n g p a r a m e t e r for acoustic
c o u p l i n g of o n e m a t e r i a l t o a n o t h e r . F o r w o o d a l o n g
t h e g r a i n , a c o u s t i c i m p e d a n c e is similar t o t h a t of
m e t a l s ; a c r o s s t h e g r a i n it is c o m p a r a b l e t o plastics
a n d w a t e r . C o u p l i n g p r e s e n t s t h e greatest source of
variability a n d t h e m a j o r i m p e d i m e n t t o on-line
i m p l e m e n t a t i o n of A E o r A U in processing w o o d b a s e d m a t e r i a l s . F o r A E l a b o r a t o r y studies, c o u p l i n g
is generally effected u s i n g either a c o u p l a n t (grease
type) o r b y b o n d i n g t h e sensor t o t h e m a t e r i a l . Special
p r o b l e m s in c o u p l i n g t o w o o d - b a s e d m a t e r i a l s include
p o r o s i t y a n d r o u g h n e s s of t h e surface. Because of this,
grease-type c o u p l a n t s a r e very difficult t o use w i t h o u t
t h e m b e i n g forced i n t o t h e m a t e r i a l ; this c h a n g e s t h e
p r e s s u r e a t t h e face of t h e sensor. B o n d e d c o u p l i n g
w i t h c o n t a c t o r h o t m e l t adhesives c a n b e used t o
o v e r c o m e such p r o b l e m s . B o n d e d c o u p l i n g will
usually give a b o u t a 3 d B increase in efficiency over

551

Wood:

Acoustic

Emission

and Acousto-Ultrasonic

c o u p l a n t s because of transfer of t h e s h e a r - w a v e c o m
p o n e n t . B o n d i n g m u s t be used c a u t i o u s l y since differ
ential e x p a n s i o n of t h e b o n d e d interfaces c a n c a u s e
failure within t h e b o n d o r g e n e r a t e stresses t h a t m i g h t
cause e x t r a n e o u s A E . F o r m a n y A U a p p l i c a t i o n s , t h e
surface m u s t b e s c a n n e d , w h i c h c a n be d o n e t h r o u g h
d r y c o u p l i n g using rigid o r e l a s t o m e r i c m a t e r i a l s ,
w h e r e c o u p l i n g p r e s s u r e m u s t be high e n o u g h t o
" s q u e e z e " o u t air g a p s a n d m a i n t a i n consistent local
pressure o n t h e m a t e r i a l . F o r b o t h A E a n d A U , m o s t
on-line uses involve m a t e r i a l s t h a t a r e m o v i n g ,
generally r e q u i r i n g a d r y c o u p l i n g system a n d a d d i n g
considerable c o m p l e x i t y in s e n s o r / c o u p l i n g design.
D r y c o u p l i n g i n t r o d u c e s a loss of a b o u t 2 0 - 3 0 d B (at
7 0 k P a ) , which c a n be r e d u c e d t o a b o u t 10 d B with
increased pressure (300 k P a ) . Alternatively, b u t with
s o m e risk with h y g r o s c o p i c m a t e r i a l s , c o u p l i n g c a n b e
achieved b y using a w a t e r mist a t t h e c o n t a c t a r e a .

3. Defect

Location

L o c a t i o n of t h e origin of A E emissions c a n be a c c o m
plished by using m u l t i p l e sensors a n d m e a s u r i n g time
of arrival of the s a m e event. W i t h t w o sensors, t h e
definition of l o c a t i o n is limited t o a p l a n e p e r p e n d i c u
lar t o t h e line b e t w e e n t h e sensors. T h e a d d i t i o n of
m o r e sensors p e r m i t s m o r e precise definition of t h e
origin, a s s u m i n g t h a t t h e m a t e r i a l is r e a s o n a b l y
h o m o g e n e o u s a n d t h e event r a t e is n o t t o o high t o
distinguish b e t w e e n events. F o r solid w o o d , t h e rela
t i o n s h i p of velocity t o g r a i n o r i e n t a t i o n a n d t h e high,
a n i s o t r o p i c a t t e n u a t i o n r e q u i r e special p r e c a u t i o n s in
sensor l o c a t i o n a n d i n t e r p r e t a t i o n of time intervals.
S o m e of t h e m o r e nearly i s o t r o p i c w o o d - b a s e d c o m
posites, such as certain types of fiberboard a n d p a r t i c
l e b o a r d , p e r m i t g o o d l o c a t i o n r e s o l u t i o n . In c o n t r a s t ,
p l y w o o d presents special p r o b l e m s from b o t h t h e
grain o r i e n t a t i o n of t h e plies a n d b o u n d a r i e s b e t w e e n
plies. O r i e n t e d s t r a n d b o a r d s h o u l d b e h a v e i n t e r m e
diately b e t w e e n p a r t i c l e b o a r d a n d p l y w o o d .

4.

Applications

A l t h o u g h there a r e a limited n u m b e r of e x a m p l e s of
direct a p p l i c a t i o n of A E a n d A U in q u a l i t y assess
ment (QA) and quality control (QC), a substantial
research effort is u n d e r w a y t h a t will p r o v i d e t h e
b a c k g r o u n d for d e v e l o p m e n t of further industrial
systems for n o n d e s t r u c t i v e e v a l u a t i o n a n d testing.
T h e r e p o r t e d research in A E a n d A U for w o o d - b a s e d
m a t e r i a l s c a n be placed in four m a j o r categories:
fracture/fracture m e c h a n i c s , d r y i n g (as m o n i t o r e d b y
f o r m a t i o n of checks), decay a n d m a c h i n i n g . O n l y t h e
first c a t e g o r y lacks c u r r e n t Q C / Q A efforts. A l t h o u g h
a b o u t 5 0 % of the r e p o r t e d research h a s been in
fracture/fracture m e c h a n i c s , a m a j o r a r e a of e m p h a s i s
since 1980 h a s been in w o o d drying. T h e m o s t recent

552

Characteristics

research h a s been in l a b o r a t o r y assessment of w o o d

d e c a y using b o t h A E a n d A U .
4.1 Fracture and Fracture
Mechanics
T h e first w o r k o n w o o d in w h i c h piezoelectric sensors
were used w a s in t h e mid-1960s for general A E
b e h a v i o r in s t a n d a r d m e c h a n i c a l tests a n d c r a c k p r o
p a g a t i o n . L o c a l failures from slow extension of intrin
sic flaws p r o d u c e d emissions a t levels as low a s 5 - 1 0 %
of u l t i m a t e s t r e n g t h , with irregular " r u n - a n d - s t o p "
flaw g r o w t h . S u b s e q u e n t l y , it w a s f o u n d t h a t longitu
dinal tension w a s c h a r a c t e r i z e d b y early flaw g r o w t h
a t 5 - 2 0 % of u l t i m a t e stress, with a linear increase in
events t o n e a r failure. I n c o n t r a s t , A E from transverse
tension s h o w e d a l o g - l o g r e s p o n s e vs d e f o r m a t i o n ,
b u t for b o t h types of tensile l o a d i n g , t o t a l events t o
failure a v e r a g e d a b o u t 300 events p e r cubic centimeter
of specimen. L o n g i t u d i n a l c o m p r e s s i o n p r o d u c e d
only a b o u t 0 . 1 % of t h e " A E d e n s i t y " (events/volume)
of tensile tests. I n flexure, c u m u l a t i v e events increased
linearly with deflection t o t h e p r o p o r t i o n a l limit,
c o n t i n u i n g b e y o n d it in a linear m a n n e r b u t a t a m u c h
lower slope t o n e a r failure. In creep u n d e r flexural
l o a d i n g a t 8 0 % u l t i m a t e stress, A E a c c u m u l a t e d step
wise from a p p a r e n t r e d i s t r i b u t i o n of stress c o n c e n t r a
tions d u r i n g irregular flaw g r o w t h . M o d e I cleavage
tests p r o d u c e d a u n i f o r m d i s t r i b u t i o n of A E over the
1
c r a c k length, with a b o u t 8 a n d 24 events m m " for
s o a k e d a n d d r y specimens, respectively.
I n specimens t h a t c o n t a i n defects, t h e r a t e of emis
sions increases n e a r the p r o p o r t i o n a l limit. H i g h e r
emission levels of these specimens o c c u r w i t h o u t
c o r r e s p o n d i n g c h a n g e s in m o d u l u s of r u p t u r e . T h e
critical l o a d in fracture t o u g h n e s s correlates highly
with c u m u l a t i v e A E c o u n t s . T h e initiation of m i c r o
scopic c o m p r e s s i o n lines h a s been p o s t u l a t e d as t h e
cause of early events a t 4 0 - 5 0 % u l t i m a t e l o a d in static
b e n d i n g . E a r l y A E h a s b e e n used as a screening test t o
eliminate flawed specimens from studies.
Solid w o o d u n d e r tensile stress parallel t o t h e grain
p r o d u c e s A E in sequential slow-rate a n d r a p i d - r a t e
p e r i o d s . T h e slow r a t e is a t t r i b u t e d t o extension of
preexisting m i c r o s c o p i c flaws in t h e cell walls, which
h a s been confirmed microscopically. T h e cause of the
r a p i d A E r a t e a p p e a r s t o be brittle failure of t r a c h e i d s
since this r a t e is p r o p o r t i o n a l t o c r a c k velocity. A E
o u t p u t varies with w o o d species, b u t h a s n o t been
related t o gross physical o r a n a t o m i c a l p r o p e r t i e s .
A l s o , w h e n t h e A E r a t e is high, t h e o b s e r v e d shearing
failure, w h i c h reduces c r a c k velocity, is low. A E h a s
been used in static b e n d i n g t o distinguish t h e effect of
c o m p r e s s i o n failures in t y p h o o n - d a m a g e d w o o d t h a t
c a u s e a lower m o d u l u s of r u p t u r e ( M O R ) b u t
u n c h a n g e d m o d u l u s of elasticity ( M O E ) , from t h e
effect of k n o t s in w h i c h b o t h M O E a n d M O R a r e
lowered. A s s u m i n g a linear r e l a t i o n s h i p of t o t a l
2
c o u n t s t o (load-at-failure) , t h e slopes a r e q u i t e dif
ferent b e t w e e n clear w o o d a n d w o o d c o n t a i n i n g either
k n o t s o r c o m p r e s s i o n failures, p r o v i d i n g a m u c h

Wood:

Acoustic

clearer s e p a r a t i o n of t h e c o n t r i b u t i n g s o u r c e t h a n if
considering only M O R . T e n s i o n fatigue h a s b e e n
observed t o c a u s e a n e x p o n e n t i a l increase of A E w i t h
cycles; the c o n t r i b u t i o n of A E from l o a d i n g a n d
u n l o a d i n g , h o w e v e r , w a s n o t eliminated.
C l e a r specimens stressed in flexure g e n e r a t e c o m
p a r a b l y little A E until n e a r t h e u l t i m a t e stress, in
c o n t r a s t t o high activity in m a t e r i a l c o n t a i n i n g d e
fects. T h e initiation a n d p r o p a g a t i o n of failures c a n
be detected by u s i n g l o c a t i o n t e c h n i q u e s w i t h t w o o r
m o r e sensors. T h e initiation of flaws in b o t h l a b o r a
t o r y a n d full-size specimens c a n b e c o r r e l a t e d with t h e
location of n a t u r a l o r artificial defects.
4.2
Composites
W o o d - b a s e d c o m p o s i t e m a t e r i a l s emit A E a t s u b s t a n
tially lower stress levels t h a n o c c u r s with solid w o o d .
F o r e x a m p l e , in static b e n d i n g tests, c o m p o s i t e m a t e r
ials begin emissions a t a b o u t 1 0 - 2 0 % of t h e u l t i m a t e
stress, w h e r e a s clear solid w o o d begins a t a b o u t 4 0 5 0 % . T h e smaller t h e c o n s t i t u e n t particle in t h e
b o a r d , the higher t h e stress level of initial emissions.
In A E m o n i t o r i n g d u r i n g i n t e r n a l b o n d (IB) tests o n
c o m p o s i t e s , a clear r e l a t i o n s h i p w a s f o u n d b e t w e e n
one-half of t h e t o t a l events a n d u l t i m a t e stress. I n
p a r t i c l e b o a r d with c o n t r o l l e d resin levels, t o t a l events
t o failure c o r r e l a t e d w i t h resin level. A l s o , A E d a t a
correlated m u c h b e t t e r w i t h I B values t h a n d i d speci
m e n density. S o m e limited d a t a indicate a high c o r r e
lation of A E w i t h A U m e a s u r e d b y t r a n s m i s s i o n . T h e
Felicity r a t i o of p a r t i c l e b o a r d a p p e a r s t o b e r e a s o n
ably c o n s t a n t (at a b o u t 0.9) u p t o failure.
A E h a s b e e n m e a s u r e d from i n t e r n a l microfailures
d u r i n g t h e thickness swelling of p a r t i c l e b o a r d a t high
relative h u m i d i t y . T h e active p e r i o d of A E coincides
with irreversible swelling ( s p r i n g b a c k ) . W o o d - f i b e r
h a r d b o a r d with c o n t r o l l e d p r e t r e a t m e n t s tested in
c o m p r e s s i o n n o r m a l t o t h e face p r o d u c e d c u m u l a t i v e
A E t h a t c o r r e l a t e d well w i t h thickness swelling from
boil-swell tests, i n d i c a t i n g t h a t c u m u l a t i v e A E m a y b e
a g o o d n o n d e s t r u c t i v e p r e d i c t o r of d i m e n s i o n a l stabi
lity. W h e n t h e s a m e t y p e of m a t e r i a l s were subjected
t o cyclic w a t e r - s o a k e x p o s u r e , stress-wave factor
( S W F ) values decreased with increasing n u m b e r s of
cycles, c o r r e s p o n d i n g t o increasing d a m a g e . H o w
ever, u n d a m a g e d b o a r d s w i t h h i g h e r S W F h a d lower
thickness swelling, suggesting t h a t S W F c o u l d p r e d i c t
the degree of d i m e n s i o n a l stability.
4.3
Machining
A E characteristics h a v e been d e t e r m i n e d for c u t t i n g
o p e r a t i o n s t h a t a p p r o x i m a t e veneer peeling. T h e
p r i m a r y s o u r c e of A E w a s f o u n d t o b e c h a n g e s in
plastic d e f o r m a t i o n in t h e s h e a r z o n e a t t h e tip of t h e
c u t t i n g t o o l . T h e A E c o u n t r a t e , while n o t well
correlated with c u t t i n g forces, w a s m o r e sensitive t o
the c u t t i n g p r o c e s s t h a n t h e r m s signal. T h e A E
output was considered potentially m o r e important to
m o n i t o r tool w e a r t h a n c u t t i n g forces. T h i s w o r k h a s

Emission

and Acousto-Ultrasonic

Characteristics

been e x t e n d e d t o p r e l i m i n a r y tests o n m o n i t o r i n g A E
from circular saw c u t t i n g , using several types of
coupling attachments to the blade.
4.4 Drying and Drying

Control

O n e of t h e m o r e p r o m i s i n g a p p l i c a t i o n s of A E is for
m o n i t o r i n g a n d c o n t r o l l i n g t h e d r y i n g process of
l u m b e r . A E h a s b e e n used t o sense t h e d e v e l o p m e n t of
surface checks in b o t h h a r d w o o d s a n d softwoods.
T h e a c t u a l fracture of t h e surface h a s been directly
o b s e r v e d s i m u l t a n e o u s l y w i t h A E emissions. By c o n
trolling t h e e n v i r o n m e n t a l c o n d i t i o n s t o p r e v e n t high
r a t e s of emissions, it is possible t o d r y faster with less
d e g r a d a t i o n . Several investigators h a v e d e m o n s t r a t e d
t h e feasibility of c o n t r o l l i n g c h e c k i n g d u r i n g h a r d
w o o d d r y i n g b y using a fixed level of A E t o c o n t r o l
d r y i n g c o n d i t i o n s . H a r d w o o d s generally check m u c h
m o r e readily t h a n s o f t w o o d s a n d c o n s e q u e n t l y h a v e
A E r a t e s a b o u t a n o r d e r of m a g n i t u d e greater. H o w
ever, a m o n g h a r d w o o d s , t h e r e d o e s n o t a p p e a r t o be a
g o o d c o r r e l a t i o n b e t w e e n p r o p e n s i t y t o check a n d A E
r a t e . A E h a s been s h o w n t o r e s p o n d r a p i d l y t o
c h a n g i n g surface R H c o n d i t i o n s , i n d e p e n d e n t of
w h e t h e r e n d grain o r side g r a i n is e x p o s e d . G e o m e t r y
c a n h a v e a large effect o n A E g e n e r a t i o n , d e p e n d i n g
o n t h e direction of m o i s t u r e m o v e m e n t a n d t h e degree
of stress d e v e l o p m e n t . T h e r e is s o m e evidence t h a t A E
d u r i n g d r y i n g also originates from fracture of w a t e r
capillaries, a n a l o g o u s t o A E from w a t e r stress in
plants.
4.5 Biological

Degradation

Several m e c h a n i c a l tests, including static b e n d i n g a n d

t r a n s v e r s e c o m p r e s s i o n , h a v e s h o w n t h a t A E activity
increases substantially in d e c a y e d w o o d . T h i s effect
also o c c u r s within t h e incipient d e c a y r a n g e , which is
very difficult t o detect w i t h a n y o t h e r analytical
t e c h n i q u e . A s u b s t a n t i a l n u m b e r of variables (includ
ing w o o d a n d fungus species) a n d testing configu
r a t i o n s m u s t be u n d e r s t o o d if t h e t e c h n i q u e is t o m o v e
from l a b o r a t o r y t o field testing. P r e l i m i n a r y tests
using a c o u s t o - u l t r a s o n i c s s h o w s o m e p r o m i s e of
N D T d e t e c t i o n of d e c a y e d w o o d . M a r i n e - b o r e r
d a m a g e h a s been s i m u l a t e d b y drilled holes in w o o d e n
piling a n d u n d e r l o a d i n g g e n e r a t e d A E in p r o p o r t i o n
t o t h e degree of d a m a g e . C o u p l i n g t h r o u g h w a t e r in
w h i c h t h e piling w a s i m m e r s e d w a s f o u n d t o be m o r e
efficient t h a n direct surface c o n t a c t t o t h e piling.
4.6
Adhesives
T h e characteristics of A E for adhesively b o n d e d a r e a s
h a v e n o t b e e n well defined. T h e r e is s o m e d a t a t h a t
indicates lower A E levels for brittle t h a n for flexible
adhesives, even for failure a t t h e s a m e u l t i m a t e stress.
In p l y w o o d I B testing, it w a s f o u n d t h a t w o o d failure
c o u l d b e differentiated from adhesive failure by the
s h a p e of t h e A E vs strain curves, which were linear
for adhesive a n d curvilinear for w o o d failure, respect
ively. S o m e p r e l i m i n a r y p l y w o o d w o r k h a s been d o n e

553

Wood: Acoustic

Emission

and Acousto-Ultrasonic

in static b e n d i n g t o u n d e r s t a n d t h e effect of voids o r

p o o r l y b o n d e d a r e a s o n A E with t h e objective of
assessing full-size-panel integrity.
Several l a b o r a t o r y studies h a v e been m a d e o n t h e
c h a r a c t e r of A E from fingerjointed s t r u c t u r a l l u m b e r
in static b e n d i n g . A l t h o u g h t h e s t r e n g t h of clear w o o d
h a v i n g fully c u r e d b o n d s c o u l d be p r e d i c t e d with
r e a s o n a b l e e r r o r a t 5 0 % a n d 8 0 % of u l t i m a t e l o a d ,
the presence of defects in t h e w o o d a n d / o r
fingerjoints
increased the e r r o r in p r e d i c t i o n . H o w e v e r , l o c a t i o n
techniques h a v e s h o w n t h a t even in fingerjointed clear
w o o d , t h e emissions o c c u r p r e d o m i n a n t l y from t h e
a r e a of t h e j o i n t . I n c o n t r a s t , clear w o o d w i t h o u t
fingerjoints h a s a fairly u n i f o r m d i s t r i b u t i o n of emis
sions a l o n g t h e length. A E h a s also b e e n used in a n
analysis of failure m o d e s o f different furniture-joint
c o m b i n a t i o n s . T h e c u r i n g of adhesives with w o o d
substrates h a s been m o n i t o r e d using a c o u s t o - u l t r a sonics. C u r e time h a s been quantified for several types
of adhesives b y calculating t h e half-time b e t w e e n
initial a n d final t r a n s m i s s i o n values.
See also: Acoustic Emission

Bibliography
Ansell 1982 Acoustic emission from softwoods in
tension. Wood Sci. Technol. 16: 35-58
Beall F C 1985 Relationship of acoustic emission to internal
bond strength of wood-based composite panel materials.
J. Acoust. Emission 4(1): 19-29
Beall F C 1986 Effect of moisture conditioning on acoustic
emission from particleboard. J. Acoust. Emission 5(2): 7

Beall F C 1987 Acousto-ultrasonic monitoring of glueline

curing. Wood Fiber Sci. 19(2): 204-14

554

Characteristics

Beall F C, Wilcox W W 1987 Relationship of acoustic

emission during radial compression to mass loss from
decay. For. Prod. J. 37(4): 3 8 ^ 2
Beattie A G 1983 Acoustic emission, principles and instru
mentation. / . Acoust. Emission 2(1/2): 95-128
Becker F 1982 Acoustic emissions during wood drying.
Holz Roh- Werkst. 40: 345-50
DeBaise G R, Porter A W, Pentoney R 1966 Morphology
and mechanics of wood fracture. Mater. Res. Stand.
6(10): 493-9
Dedhia D D, Wood W 1980 Acoustic emission analysis of
Douglas-fir fingerjoints. Mater. Eval. (11): 28-32
dos Reis L M, McFarland D 1986 On the acoustoultrasonic characterization of wood fiber hardboard. / .
Acoust. Emission 5(2): 67-70
Hamstad A 1986 A review: acoustic emission, a tool for
composite-materials studies. Exp. Mech. 26(1): 7-13
Lemaster R L, Klamecki , Dornfeld D A 1982 Analysis
of acoustic emission in slow speed wood cutting. Wood
Sci. 15(2): 150-60
Niemz P, Wagner M, Theis 1983 State and possible
applications of acoustic emission analysis in wood re
search. Holztechnologie 24(2): 91-5
Noguchi M, Kitayama S, Satoyoshi K, Umetsu J 1987
Feedback control for drying Zelkova serrata using inprocess acoustic emission monitoring. For. Prod. J. 37(1):
28-34
Sato K, Kamei N, Fushitani M, Noguchi 1984 Discus
sion of tensile fracture of wood using acoustic emissions.
A statistical analysis of the relationships between the
characteristics of AE and fracture stress. / . Jpn. Wood
Res. Soc. 30(8): 653-9
Vary A, Lark R F 1979 Correlation of fiber composite
tensile strength with, the ultrasonic stress wave factor. / .
Test. Eval. 7(4): 185-91
F . C . Beall
[University of California, Berkeley,
California, U S A ]


X-Ray Absorption Spectroscopy:
EXAFS and XANES Techniques
X - r a y spectroscopies, in v a r i o u s forms, h a v e l o n g
been exploited for s t u d y i n g t h e electronic a n d crystallographic s t r u c t u r e of solids. M o s t extensively uti
lized, of c o u r s e , a r e diffraction t e c h n i q u e s e m p l o y e d
for the p u r p o s e of e x t r a c t i n g c r y s t a l l o g r a p h i c infor
m a t i o n . H o w e v e r , x-ray a b s o r p t i o n studies a r e cur
rently experiencing a s t r o n g surge of scientific interest
resulting from recent i m p o r t a n t a d v a n c e s , b o t h in
theoretical u n d e r s t a n d i n g a n d in e x p e r i m e n t a l c a p a
bility. E x p e r i m e n t a l l y , t h e E X A F S (extended x-ray
a b s o r p t i o n fine structure) a n d X A N E S (x-ray a b s o r p
tion near-edge fine s t r u c t u r e ) techniques a r e dis
tinguished simply b y their spectral r a n g e s ( m e a s u r e d
relative t o a n x-ray a b s o r p t i o n edge). T h e distinction
is m a d e since x-ray-induced electronic excitations in
the vicinity of t h e edge involve c o n s i d e r a t i o n s t h a t a r e
s o m e w h a t different from t h e m o r e energetic p r o
cesses. Oscillatory s t r u c t u r e in t h e x-ray a b s o r p t i o n
coefficient t h a t m a y b e o b s e r v e d in t h e higher spectral
r a n g e (40 eV ^ hv ^ 1000 eV a b o v e t h e edge) is called
E X A F S , while X A N E S refers t o t h e s t r u c t u r e in t h e
i m m e d i a t e vicinity of t h e edge (i.e., for hv ^ 50 eV
a b o v e t h e edge). T h e s e x-ray a b s o r p t i o n t e c h n i q u e s
h a v e u n i q u e capabilities a n d a r e being used t o s t u d y a
wide variety of c o m p l e x m a t e r i a l s . Studies of a m o r
p h o u s m a t e r i a l s , catalysts, biological m a t e r i a l s a n d
solutions h a v e been r e p o r t e d .
I n this article, t h e u n d e r l y i n g theoretical c o n c e p t s
of E X A F S a n d X A N E S a r e outlined a n d recent
experimental a d v a n c e s a r e discussed. A d v a n t a g e s a n d
limitations of t h e x-ray a b s o r p t i o n spectroscopies,
a n d types of p r o b l e m s m o s t suited for these tech
niques, will b e discussed. M o r e detailed discussions
are available in literature reviews, a n d t h e extensive
review b y Lee et al. (1981) is particularly r e c o m
m e n d e d t o t h e interested reader.

1. Theory

and Comparison

with

()\(/\}\ ()

*(*) = Z^jH)f(k)sm[2krj

)]

j
2

x exp( - 2k ) )exp( - 2/)

(2)

1.6,-

Experiment

W i t h i n t h e electric dipole a p p r o x i m a t i o n , t h a t p a r t of
the a b s o r p t i o n coefficient resulting from p h o t o e m i s sion from a core state is given b y
2

a n a m b i t i o u s theoretical effort is being m a d e t o

u n d e r s t a n d t h e X A N E S region. I n c o n t r a s t , t h e
E X A F S region a p p e a r s t o b e r a t h e r well u n d e r s t o o d .
T h u s w e will p r o c e e d t o discuss E X A F S a n d follow
with a discussion of t h e n e a r - e d g e region.
I n t h e E X A F S regions, p h o t o e j e c t e d electrons a r e
excited t o final states far a b o v e t h e F e r m i level. A t
these energies, t h e t o t a l final density of states varies
s m o o t h l y (with hv), a n d oscillatory b e h a v i o r in ()
results only from v a r i a t i o n s in t h e m a t r i x element. I n
this case, a single-scattering (i.e., w e a k scattering)
a p p r o x i m a t i o n c a n b e used t o calculate t h e final-state
w a v e function. T h i s w a v e function c a n b e viewed a s
an outgoing wave superimposed on a wave backscattered from t h e s u r r o u n d i n g a t o m s . T h i s b a c k s c a t t e r e d
w a v e interferes, either destructively o r constructively
( d e p e n d i n g o n hv), with t h e o u t g o i n g w a v e , t h u s
p r o d u c i n g oscillations in (). T h i s oscillatory b e
h a v i o r is illustrated in t h e E X A F S spectra of nickel
(Fig. 1). T h e oscillatory p a r t of () m a y t h e n b e
isolated with t h e relation x(k) = ( 0)/0,
where
0 is a s m o o t h l y v a r y i n g b a c k g r o u n d a n d k
l/2
2n/h[2m(E - E0)] .
H e r e , m is t h e electron m a s s ,
h is P l a n c k ' s c o n s t a n t a n d E0 is t h e zero of energy of
the o u t g o i n g electron. A p l o t of kx(k) for t h e d a t a of
Fig. 1 is s h o w n in F i g . 2a.
Sayers et al. (1971) s h o w e d t h a t x(k) is related t o
a t o m i c p a r a m e t e r s b y t h e expression

0.7h

0)

w h e r e is t h e p h o t o n energy, p(E) is t h e density of

final states a n d < / | r | / > is t h e electric-dipole m a t r i x
element. I n t h e n e a r - e d g e region ( X A N E S ) , t h e calcu
lation of () is difficult because b o t h t h e m a t r i x
element a n d t h e density of final states d e p e n d , in
c o m p l i c a t e d w a y s , o n t h e p h o t o n energy. A t present,

8500

9000
Energy

(eV)

Figure 1
The absorption coefficient (multiplied by the thickness
JC) of nickel as a function of energy at 38
555

X-Ray

Absorption

Spectroscopy:

EXAFS

and XANES

Ac

(b)

Figure 2
(a) The EXAFS spectrum, kx{k) vs k, and (b) the radial
distribution function, ^(r) vs r, for nickel at 38 K. The
numbers in parentheses are the number of atoms per shell,
indicated at the known shell distances

w h e r e r} is t h e d i s t a n c e from t h e c e n t r a l ( a b s o r b e r )
a t o m t o t h e yth shell of a t o m s , Nj is t h e n u m b e r of
a t o m s in the shell, is a D e b y e - W a l l e r - l i k e factor
which m e a s u r e s t h e a i s o r d e r of t h e a t o m s in t h e yth
shell relative t o t h e central a t o m a n d is a m e a n free
p a t h , e s t i m a t e d t o be 3.5-5 A. T h e a m p l i t u d e function
ffi) a n d t h e p h a s e function ) c a n be calculated
theoretically o r d e t e r m i n e d empirically from c o m
p o u n d s of k n o w n s t r u c t u r e . I n principle, therefore,
the p a r a m e t e r s Np rp cr, a n d c a n b e d e t e r m i n e d
for the first few n e a r - n e i g h b o r shells. I n practice,
however, there a r e limits o n t h e n u m b e r of p a r a m e t e r s
t h a t c a n be i n d e p e n d e n t l y d e t e r m i n e d a n d also o n t h e
a c c u r a c y of t h e d e t e r m i n a t i o n s . In m a n y cases, dis
tances between the central a t o m a n d t h e first shell of
s u r r o u n d i n g n e i g h b o r s in a n u n k n o w n m a t e r i a l c a n
be d e t e r m i n e d t o 0 . 0 1 A, a n d t h e n u m b e r of first
n e a r n e i g h b o r s c a n be m e a s u r e d t o b e t t e r t h a n 2 0 %
accuracy.
Analysis of E X A F S spectra is c o n s i d e r a b l y a i d e d
by calculating t h e F o u r i e r t r a n s f o r m of kx(k).
Because of the special form of E q n . (2), t h e F o u r i e r
t r a n s f o r m of kx(k) is a p a r t i c u l a r l y useful inter
p r e t a t i o n . T h e t r a n s f o r m #?(r) is a r a d i a l - d e p e n d e n t
function t h a t a p p r o x i m a t e l y m e a s u r e s the spatial dis
t r i b u t i o n of b a c k s c a t t e r i n g a t o m s relative t o t h e cen
556

Techniques

tral a t o m . <p(r) is called t h e E X A F S r a d i a l d i s t r i b u t i o n

function ( R D F ) . T h i s function is unlike r a d i a l distri
b u t i o n functions d e t e r m i n e d b y diffraction t e c h n i q u e s
in t h a t , with E X A F S , t h e R D F is m e a s u r e d relative t o
a n identifiable c e n t r a l a t o m . T h e F o u r i e r t r a n s f o r m
q>(r) of t h e nickel E X A F S s p e c t r a s h o w n in Fig. 2a is
p r e s e n t e d in Fig. 2 b . T h e p e a k s ( a p p r o x i m a t e l y ) spe
cify t h e r a d i a l p o s i t i o n s of t h e n e a r shells of a t o m s
t h a t s u r r o u n d t h e nickel a b s o r b e r : t h e o b s e r v e d p e a k s
c o r r e s p o n d t o t h e first four n e a r - n e i g h b o r shells. A l s o
indicated a r e t h e k n o w n shell distances a n d t h e
n u m b e r of a t o m s p e r shell. T h e shifts b e t w e e n t h e
p e a k p o s i t i o n s a n d t h e k n o w n shell distances result
from t h e t e r m q>(k) (in E q n . (2)), w h i c h w a s n o t
included in t h e t r a n s f o r m of F i g . 2 b . A l s o , t h e a m p l i
2
t u d e s a r e d a m p e d b y t h e 1/r a n d exp( -/)
terms.
Inclusion of t h e <pfk) t e r m in E q n . (2) allows a n
a c c u r a t e d e t e r m i n a t i o n of t h e atomic-shell radii.
O f c o u r s e , t h e s t r u c t u r a l p a r a m e t e r s for nickel were
previously k n o w n from diffraction studies. T h e nickel
E X A F S results w e r e p r e s e n t e d t o illustrate s t a n d a r d
d a t a - a n a l y s i s t e c h n i q u e s a n d t h e t y p e of i n f o r m a t i o n
t h a t c o u l d be d e t e r m i n e d from a n u n k n o w n m a t e r i a l .
A s e c o n d e x a m p l e p r e s e n t s results from a n E X A F S
s t u d y of u r a n i u m in dilute a q u e o u s s o l u t i o n . A radial
d i s t r i b u t i o n function, o b t a i n e d from analysis of u r a
n i u m L-edge d a t a , is s h o w n in Fig. 3. T h e a q u e o u s
s a m p l e c o n t a i n e d u r a n i u m in 0.02 m o l a r c o n c e n t r a
tion (360 p p m ) . T w o p r o m i n e n t p e a k s a r e seen in Fig.
3. T h e n e a r p e a k c o r r e s p o n d i n g t o a U - O s e p a r a t i o n
of ~ 1 . 7 A, results from t w o tightly b o u n d oxygen
a t o m s t h a t b i n d t o u r a n i u m in t h e linear-chain " u r a n y l " configuration. Five o r six m o r e oxygen a t o m s ,
l o c a t e d a t ~ 2 . 4 A, p r o d u c e t h e s e c o n d p e a k . D e b y e W a l l e r factors o b t a i n e d for t h e t w o shells indicate
t h a t t h e s e c o n d oxygen shell is m u c h less tightly
b o u n d t o t h e u r a n i u m a t o m . T h e m o r e d i s t a n t oxygen
a t o m s p r o b a b l y c o r r e s p o n d t o w a t e r molecules t h a t

(A)

Figure 3
The uranium L-edge radial-distribution function, <p(R) vs
R, for a 0.02 molar uranium aqueous solution

X-Ray

Absorption

form a h y d r a t i o n shell. T h e s e results for a dilute

a q u e o u s s a m p l e were easily a c q u i r e d a n d p r o v i d e d
i n f o r m a t i o n t h a t w o u l d b e o t h e r w i s e difficult t o
obtain.
E X A F S spectra c a n b e described with a simple
formalism. O n t h e o t h e r h a n d , x-ray spectra in t h e
n e a r vicinity of a n a b s o r p t i o n edge c a n n o t be so
simply related t o m a t e r i a l s p a r a m e t e r s . X A N E S dir
ectly p r o b e s u n o c c u p i e d electron states of t h e p h o t o ionized ion. T h e s e states a r e sensitive t o chemical
b o n d i n g a n d h e n c e t o c r y s t a l l o g r a p h i c o r d e r a n d ion
electronegativity. C o n s e q u e n t l y , X A N E S spectra a r e
influenced b y t h e types of a t o m s involved a n d b y t h e
c o o r d i n a t i o n s y m m e t r y of t h o s e a t o m s in p r o x i m i t y
t o t h e a b s o r b e r . T h e spectra a r e , of c o u r s e , influenced
by t h e q u a n t u m n u m b e r s of t h e initial (core electron)
state since t h e excitations a r e p r e d o m i n a n t l y electric
dipole interactions. T h u s , the a n g u l a r m o m e n t u m of t h e
(initial-state) core electron d e t e r m i n e s t h o s e a n g u l a r m o m e n t u m c o m p o n e n t s of t h e u n o c c u p i e d states t h a t
a r e t o be p r o b e d . F o r K - e d g e X A N E S spectra ( I s c o r e
state), the dipole selection rule allows t r a n s i t i o n s only
t o e m p t y states w h i c h h a v e s y m m e t r y . T h e s e e m p t y
states consist of h y b r i d i z e d orbitals which, by n a t u r e ,
a r e c o m p l e x a n d r e q u i r e extensive c o m p u t a t i o n t o
describe in detail. N o n e t h e l e s s , certain c o m m o n
physical characteristics a p p a r e n t l y c a n p r o d u c e c o m
m o n features in X A N E S s p e c t r a w i t h t h e result t h a t
X A N E S c a n be extremely useful as a fingerprinting
t e c h n i q u e , for e x a m i n i n g u n k n o w n m a t e r i a l s (see, for
e x a m p l e , M a y l o t t e et al. 1981). I n m a n y cases,
valence, s y m m e t r y of t h e c e n t r a l a t o m site a n d even
crystal s t r u c t u r e c a n b e d e t e r m i n e d b y c o m p a r i n g t h e
u n k n o w n sample to characterized standards.
T o illustrate, K - e d g e X A N E S spectra a r e s h o w n in
Fig. 4 for a n u m b e r of t r a n s i t i o n m e t a l oxides t h a t
occur in several different p h a s e s . All spectra c o r r e s
p o n d t o x-ray a b s o r p t i o n n e a r t h e metallic e l e m e n t
edge a n d a r e displayed with t h o s e edges aligned.
T h e K - e d g e excitation energy varies from a p p r o x i
m a t e l y 4040 eV in c a l c i u m t o a b o u t 8330 eV in nickel.
N o t e t h a t within e a c h p h a s e t h e spectra a r e q u i t e
similar in a p p e a r a n c e ( s h o w i n g relative i n d e p e n d e n c e
from the choice of t r a n s i t i o n element) b u t s p e c t r a for
different crystal p h a s e s a r e distinctly different.

2. Experimental

Considerations

Since E X A F S oscillation a m p l i t u d e s a r e usually a

small fraction of t h e a b s o r p t i o n - e d g e step height,
E X A F S m e a s u r e m e n t s r e q u i r e a very high precision
d e t e r m i n a t i o n of t h e x-ray a b s o r p t i o n coefficient,
a l t h o u g h a b s o l u t e m e a s u r e m e n t s of () a r e n o t
required. I n general, noise levels s h o u l d b e less t h a n
- 0 . 1 % of t h e signal a m p l i t u d e . (Generally, X A N E S
spectra c a n be a c q u i r e d m o r e quickly a n d for m o r e
dilute s a m p l e s t h a n is possible using t h e E X A F S
technique.) C h a r a c t e r i s t i c w a v e l e n g t h s of E X A F S

Spectroscopy:

EXAFS

and XANES

CaO

: V / \ ^ L o T i 0 3_

V.

;
/ / ^ \

Techniques

MnO

f.

Fe0 M
5 q Q 05

LaMn03

w / /
L

/ : ^ \

'

J*

(b)

A^CeVO^

N d/ 0 > M
5 o

At

^ l

T5 i 0

r\

_ 0

C O A I 2O 4

\ ^

Pi

NiO

.*

(a)

CoO

1 1 1 1 1 1 1 1 1

'
1

Ve

1 1 1 1 1 1

IA\

Energy

Figure 4
K-edge XANES spectra for (a) perovskites,
(b) monoxides, (c) zircon-type oxides and (d) spinels

oscillations a r e such t h a t t h e e x p e r i m e n t a l resolution

s h o u l d a l w a y s b e as g o o d as 1 5 e V a n d preferably
b e t t e r t h a n 10 eV. T h e high-precision a n d highr e s o l u t i o n r e q u i r e m e n t s a r e best served by very high
intensity sources. T h e m o s t intense x-ray sources ( n o w
available in several l o c a t i o n s a r o u n d t h e w o r l d ) a r e
high-energy electron s t o r a g e rings which g e n e r a t e
extremely intense fluxes of s y n c h r o t r o n r a d i a t i o n .
Utilizing d o u b l e - c r y s t a l m o n o c h r o m a t o r s , these faci
lities often p r o d u c e x-ray b e a m s w i t h 1-2 eV resolu
8
12
1
tion a n d fluxes of 10 10 p h o t o n s s " . W i t h x-ray
b e a m s of such high intensity a n d r e s o l u t i o n , highq u a l i t y spectra c a n often b e a c q u i r e d very quickly (in
m i n u t e s of r u n time). T h e s e extremely high intensities
also m a k e possible t h e s t u d y of dilute c o n c e n t r a t i o n s
( p p m levels) of a b s o r b e r dispersed in a h o s t m a t r i x .
W i t h a p p r o p r i a t e d e t e c t i o n t e c h n i q u e s , surface a t o m s
m a y also be selectively studied. A l s o , with s y n c h r o
tron radiation, both X A N E S and E X A F S measure
m e n t s c a n be c o n v e n i e n t l y m a d e in o n e e x p e r i m e n t a l
r u n . D i s a d v a n t a g e s in t h e use of s y n c h r o t r o n r a d i a
tion a r e t h e restricted access t o t h e x-ray b e a m a n d
c o m p l i c a t i o n s associated with c o n d u c t i n g experi
ments at distant locations.

557

X-Ray

Absorption

Spectroscopy:

EXAFS

and XANES

A n e x p e r i m e n t a l alternative is also available with

m o d e r n l a b o r a t o r y x-ray sources. ( B o t h l a b o r a t o r y
a n d s y n c h r o t r o n sources a r e discussed in Stern
(1980).) W i t h a 10-12 eV b a n d w i d t h , a flux of
7
1
is achievable. T h e high-intensity
10 p h o t o n s s "
l a b o r a t o r y systems d e p e n d u p o n a curved-crystal
m o n o c h r o m a t o r t o focus diverging r a d i a t i o n , p r o
d u c e d b y c o n v e n t i o n a l x-ray g e n e r a t o r s , o n t o t h e
sample. F o r concentrated materials, high-quality
E X A F S spectra (e.g., t h e d a t a of F i g . 1) a r e typically
r e c o r d e d in r u n times of 10-30 m i n . F o r X A N E S ,
w h e r e t h e higher resolution ( b u t smaller energy
range) is n e e d e d , r u n times a r e c o m p a r a b l e . M a t e r i a l s
c o n t a i n i n g dilute c o n c e n t r a t i o n s of a b s o r b e r in a lowa t o m i c - n u m b e r m a t r i x c a n also b e studied with preci
sion. F o r e x a m p l e , spectra for a catalyst c o n t a i n i n g
0.1 w t % of t r a n s i t i o n m e t a l dispersed in a silica o r
a l u m i n a h o s t h a v e been o b s e r v e d in the l a b o r a t o r y .
K - e d g e E X A F S m e a s u r e m e n t s a r e readily o b t a i n
able for m a t e r i a l s c o n t a i n i n g elements of a t o m i c
n u m b e r between 19 ( p o t a s s i u m ) a n d 47 (silver). F o r
Z < 19, the available E X A F S spectral r a n g e is sever
ely limited. A l s o , high a b s o r p t i o n rates for t h e low xray energies (required a t low Z ) a d d e x p e r i m e n t a l
c o m p l i c a t i o n s . F o r > 50, t h e level lifetime b r o a d
ening b e c o m e s large (intrinsically limiting achievable
resolution). E l e m e n t s with values b e t w e e n 56 (bar
i u m ) a n d 94 ( p l u t o n i u m ) c a n b e studied using L-edge
E X A F S . L-edge m e a s u r e m e n t s h a v e limited value for
< 56 because the L edge is n o t sufficiently s e p a r a t e d
from o t h e r a b s o r p t i o n edges.

3. Strengths

and Weaknesses

of EXAFS

and

XANES
E X A F S is a t e c h n i q u e t h a t is p r i m a r i l y useful for
measuring crystallographic structure parameters. The
m e a s u r e m e n t is a t o m specific, p r o v i d i n g a local r a d i a l
d i s t r i b u t i o n function for t h o s e a t o m s d i s t r i b u t e d
a b o u t the central ( a b s o r b e r ) a t o m .
F o r simple systems with l o n g - r a n g e o r d e r , a c c u r a
cies in t h e s t r u c t u r a l p a r a m e t e r s achievable w i t h
E X A F S a r e inferior t o t h o s e achievable using diffrac
tion t e c h n i q u e s p r o v i d i n g t h a t t h e m a t e r i a l s a r e n o n dilute. E X A F S plays t h e m o r e i m p o r t a n t role in
o b t a i n i n g s t r u c t u r a l i n f o r m a t i o n for a m o r p h o u s
m a t e r i a l s , solutions a n d dilute systems of v a r i o u s
k i n d s (such as h e t e r o g e n e o u s catalysts, biological
m a t e r i a l s a n d i m p u r i t y a t o m s in crystalline solids).
X A N E S is a spectroscopic t o o l useful for p r o b i n g
the u n o c c u p i e d electron states within 50 eV of t h e
F e r m i level. By m o n i t o r i n g a b s o r p t i o n edges associ
a t e d with different c o r e levels, electric dipole selection
rules c a n be used t o a d v a n t a g e in identifying e m p t y
states of specific a n g u l a r m o m e n t u m c h a r a c t e r . A s a
tool for p r o b i n g these e m p t y electron states, X A N E S
c o m p l e m e n t s a n u m b e r of o t h e r spectroscopies (such
as b r e m s s t r a h l u n g i s o c h r o m a t s p e c t r o s c o p y , u l t r a

558

Techniques

violet
photoemission
and
optical
reflectivity).
X A N E S c a n b e used a s a m a t e r i a l s c h a r a c t e r i z a t i o n
t o o l . N o v a c u u m is r e q u i r e d for these m e a s u r e m e n t s
(a significant e x p e r i m e n t a l convenience) a n d , often,
m a t e r i a l s with very low c o n c e n t r a t i o n of a b s o r b e r c a n
be studied w i t h ease.
E X A F S a n d X A N E S a r e , in a certain sense, redis
covered spectroscopies. T h e p h e n o m e n a h a v e b e e n
k n o w n for d e c a d e s , b u t only recently h a v e a d v a n c e s
in theoretical u n d e r s t a n d i n g a n d i n s t r u m e n t d e v e l o p
m e n t b e e n a d e q u a t e t o d e m o n s t r a t e t h e p r o m i s e of
t h e spectroscopies for m a t e r i a l s studies.
See also: X-Ray and Neutron Diffraction Studies of Amor
phous Solids; X-Ray Powder Diffraction

Bibliography
Lee A, Citrin , Eisenberger , Kincaid 1981
Extended x-ray absorption fine structure: its strengths
and limitations as a structural tool. Rev. Mod. Phys. 53:
769-806
Maylotte D H, Wong J, St Peters R L, Lytle L W, Greegor
R 1981 X-ray absorption spectroscopic investigation of
trace vanadium sites in coal. Science 214: 554-6
Sayers D E, Stern A, Lytle F W 1971 New technique for
investigating noncrystalline structures: Fourier analysis
of the extended x-ray absorption fine structure. Phys. Rev.
Lett. 27: 1204-7
Stern A (ed.) 1980 Workshop on Laboratory EXAFS
Facilities and Their Relation to Synchroton Radiation
Sources, AIP Conference Proceedings No. 64. American
Institute of Physics, New York
G . S. K n a p p a n d B. W . Veal
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]

X-Ray and Neutron Diffraction Studies

of Amorphous Solids
X - r a y a n d n e u t r o n diffraction t e c h n i q u e s p l a y a n
i m p o r t a n t role in t h e science of a m o r p h o g r a p h y
w h i c h is c o n c e r n e d w i t h t h e s t r u c t u r e s of a m o r p h o u s
solids a n d their systematic classification. A s with
crystalline solids, a k n o w l e d g e of s t r u c t u r e is a n
i m p o r t a n t prerequisite for u n d e r s t a n d i n g t h e p r o p e r
ties of a n a m o r p h o u s m a t e r i a l a n d t h u s utilizing it
a p p r o p r i a t e l y . T h e r e is, h o w e v e r , a n i m p o r t a n t dif
ference b e t w e e n diffraction studies of crystalline
solids a n d t h e c o r r e s p o n d i n g investigation of a m o r
p h o u s m a t e r i a l s . G i v e n g o o d diffraction d a t a over a
r e a s o n a b l e region of reciprocal space, it is in practice
possible t o d e t e r m i n e t h e s t r u c t u r e of simple crystal
line solids absolutely. T h i s is n o t t r u e for a m o r p h o u s
m a t e r i a l s ; t h e fact t h a t they a r e n o r m a l l y i s o t r o p i c o n
a m a c r o s c o p i c scale m e a n s t h e m a x i m u m t h a t c a n be
o b t a i n e d from a diffraction e x p e r i m e n t is a o n e d i m e n s i o n a l c o r r e l a t i o n function, from which t h e

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r e g e n e r a t i o n of t h e u n d e r l y i n g t h r e e - d i m e n s i o n a l
s t r u c t u r e c a n never be u n i q u e . T h u s , diffraction s t u d
ies of a m o r p h o u s solid s t r u c t u r e s fall n a t u r a l l y i n t o
t w o stages: t h e a c t u a l e x p e r i m e n t c u l m i n a t i n g in t h e
d e r i v a t i o n of a real-space c o r r e l a t i o n function, a n d
the i n t e r p r e t a t i o n of this c o r r e l a t i o n function in t e r m s
of a t h r e e - d i m e n s i o n a l s t r u c t u r e .

/.

The Real-Space

Correlation

Function

T h e s t r u c t u r e s of simple c o v a l e n t crystalline a n d
a m o r p h o u s solids a r e c o m p a r e d schematically in t w o
d i m e n s i o n s in Fig. 1. F o r t h e crystal, t h e s t r u c t u r e
m a y b e specified in t e r m s of a u n i t cell a n d t r a n s l a tional s y m m e t r y , t h e latter leading t o t h e s h a r p B r a g g
p e a k s which a r e characteristic of t h e diffraction p a t
tern of crystalline solids. T h e s t r u c t u r e of a n a m o r
p h o u s solid, o n t h e o t h e r h a n d , is c h a r a c t e r i z e d b y a
lack of s y m m e t r y , periodicity a n d l o n g - r a n g e o r d e r ,
resulting in a diffraction p a t t e r n which is a c o n t i n u o u s
function of t h e scattering vector Q. T h u s , in o r d e r t o
completely specify t h e s t r u c t u r e of a n a m o r p h o u s
solid it w o u l d b e necessary t o specify t h e c o o r d i n a t e s
of all the a t o m s p r e s e n t , which is clearly impossible
for a n y real m a t e r i a l .
T h e i s o t r o p i c n a t u r e of a n a m o r p h o u s m a t e r i a l
leads t o a s t r u c t u r a l d e s c r i p t i o n in t e r m s of a o n e d i m e n s i o n a l real-space c o r r e l a t i o n function, w h i c h is
essentially a o n e - d i m e n s i o n a l a n a l o g u e of t h e P a t e r son function used for single crystals. F o r a m o n a t o
mic m a t e r i a l , t h e r a d i a l density p(r) describes t h e
n u m b e r density a t a d i s t a n c e r from a n a r b i t r a r i l y
chosen origin a t o m (see Fig. 2), a n d is a gross a v e r a g e
over all the a t o m s in t h e s a m p l e t a k e n as center. p is
the a v e r a g e n u m b e r density for the w h o l e s a m p l e . T h e
n u m b e r of n e i g h b o r s b e t w e e n r a n d r 4- dr is given by
2

g(r)dr = 4nr p(r)

dr

in which g(r) is k n o w n as t h e r a d i a l
function. T h e c o r r e l a t i o n function,
t(r) = 4nrp(r)

(1)

(2)

s h o u l d be used in t h e analysis of diffraction d a t a since

it is in this function t h a t e x p e r i m e n t a l b r o a d e n i n g is
b o t h s y m m e t r i c a n d i n d e p e n d e n t of r. T h e differential
c o r r e l a t i o n function d(r) is o b t a i n e d o n s u b t r a c t i n g
the a v e r a g e density c o n t r i b u t i o n 4nrp from t(r):
d(r) = 4nr[p(r)-p]

(3)

F o r a s a m p l e c o n t a i n i n g elements t h e s t r u c t u r e m a y
be described in t e r m s of n(n 4- l ) / 2 i n d e p e n d e n t c o m
p o n e n t c o r r e l a t i o n functions of t h e f o r m
tjk(r)

= 4nrpjk{r)

(b)

distribution

(4)

which describe t h e d i s t r i b u t i o n of element k a t o m s

a b o u t t h e yth a t o m in t h e s a m p l e c o m p o s i t i o n unit.

Figure 1
Structures of simple covalent (a) crystalline and
(b) amorphous solids

2. Experimental

Techniques

A n x-ray o r n e u t r o n diffraction e x p e r i m e n t involves a

m e a s u r e m e n t of t h e scattered intensity as a function
of t h e elastic scattering vector, the m a g n i t u d e of
w h i c h is given by
Q = (47rM)sin

(5)

w h e r e is t h e incident w a v e l e n g t h a n d 20 is the
scattering angle. A l t h o u g h for a n a m o r p h o u s solid
t h e s t r u c t u r a l i n f o r m a t i o n is essentially c o n t a i n e d
within t h e elastic scattering, it is c o n v e n t i o n a l t o
p e r f o r m a t o t a l diffraction e x p e r i m e n t in which the

559

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(a)

t (r)

-- 4

Studies

of Amorphous

(b)

(r)

(d )

Figure 2
Real-space correlation functions: (a) radial density;
(b) radial-distribution function; (c) total correlation
function; (d) differential correlation function

detector r e c o r d s b o t h the elastic scattering a n d inelas

tic ( p h o n o n ) scattering. In o r d e r to achieve the neces
sary v a r i a t i o n in Q it is possible t o scan 2 a t a fixed
incident w a v e l e n g t h ( c o n v e n t i o n a l technique) o r
to m a k e m e a s u r e m e n t s as a function of a t c o n
stant scattering angle (dispersion o r time-of-flight
technique).
T h e t w o techniques for n e u t r o n s a r e c o m p a r e d in
Figs. 3 a n d 4. In the c o n v e n t i o n a l s t e a d y - s t a t e - r e a c t o r
twin-axis experiment (Fig. 3), t h e flux () of t h e r m a l
n e u t r o n s extracted from the m o d e r a t o r / r e f l e c t o r of a
steady-state reactor h a s a M a x w e l l i a n d i s t r i b u t i o n of
velocities a n d is time i n d e p e n d e n t . A b e a m of w a v e
length A, selected by the m o n o c h r o m a t o r crystal, is
incident o n the s a m p l e a n d scattered i n t o t h e d e t e c t o r
t h r o u g h a variable angle 20. T h e variable-wavelength
time-of-flight t e c h n i q u e (Fig. 4) is usually e m p l o y e d
with a pulsed accelerator source. E l e c t r o n s o r p r o t o n s
strike a heavy-metal target, p r o d u c i n g pulses of fast
n e u t r o n s which are partially m o d e r a t e d before being
incident o n t h e s a m p l e a n d scattered i n t o d e t e c t o r s
situated at fixed angles 20. E a c h d e t e c t o r r e c o r d s the
scattered intensity as a function of time-of-flight for
the distance from t h e m o d e r a t o r via the s a m p l e t o the
detector. F o r a n y n e u t r o n , the time-of-flight is simply
related to t h r o u g h t h e velocity a n d de Broglie's
relationship, a n d t h e diffraction p a t t e r n I(Q) m a y be
extracted by dividing t h e m e a s u r e d intensity by the
i n c i d e n t - n e u t r o n s p e c t r u m s h a p e . T h e great a d v a n
tage of a pulsed-accelerator source over a steady-state
r e a c t o r is t h a t the former is u n d e r m o d e r a t e d , giving
560

Solids

rise t o a s t r o n g e p i t h e r m a l c o m p o n e n t in (). T h e s e
s h o r t - w a v e l e n g t h n e u t r o n s allow d a t a to be o b t a i n e d
to m u c h higher values of Q, resulting in a c o r r e s p o n d
ing increase in real-space resolution.
A c c u r a t e q u a n t i t a t i v e x-ray diffraction m e a s u r e
m e n t s o n a m o r p h o u s solids usually e m p l o y a m o d i
fied p o w d e r - c o u n t e r diffractometer
(see
X-Ray
Powder Diffraction). T h e situation for x-rays is c o m
plicated by t h e presence of i n c o h e r e n t C o m p t o n scat
tering which a t high values of Q c a n completely
s w a m p the r e q u i r e d c o h e r e n t c o n t r i b u t i o n . Since
neither the w a v e l e n g t h d i s t r i b u t i o n n o r the i n t e g r a t e d
intensity of the C o m p t o n scattering from a given
s a m p l e c a n b e satisfactorily calculated, it is necessary
t o r e m o v e this c o n t r i b u t i o n by m e a n s of a diffractedb e a m m o n o c h r o m a t o r . M a n y researchers h a v e used a
single m o n o c h r o m a t o r in t h e diffracted b e a m b u t t h e
difficulty with this a r r a n g e m e n t is t h a t white b a c k
g r o u n d r a d i a t i o n from the x-ray t u b e c a n be C o m p
t o n scattered i n t o the m o n o c h r o m a t o r envelope. A
m u c h better a r r a n g e m e n t , s h o w n in Fig. 5, e m p l o y s a
m o n o c h r o m a t o r in b o t h t h e incident a n d diffracted
b e a m s ( W a r r e n a n d M a v e l 1965). A c o n v e n t i o n a l
curved-crystal m o n o c h r o m a t o r is used in t h e incident
b e a m (silver ^ = 0.05594 n m ) b u t t h a t in the
diffracted b e a m c o m p r i s e s a foil with a n a b s o r p t i o n
edge at a w a v e l e n g t h slightly longer t h a n the c h a r a c
teristic line of the x-ray t u b e ( r u t h e n i u m edge:
= 0.05605 n m ) such t h a t t h e c o h e r e n t intensity will
excite fluorescence w h e r e a s t h e C o m p t o n scattering
will n o t . T h e fluorescent r a d i a t i o n is t h e n r e c o r d e d by
the detector.
T h e dispersion t e c h n i q u e is also possible with rays
using a s e m i c o n d u c t o r detector. T h e a d v a n t a g e of this
m e t h o d is t h a t for c o m p l e x s a m p l e e n v i r o n m e n t s
(such as c r y o s t a t s , furnaces a n d high-pressure cells)
only t w o o r three small w i n d o w s a r e needed, a fixed
angle a p a r t . Similarly, all values of Q a r e e x a m i n e d
simultaneously, m a k i n g the t e c h n i q u e ideally suited
t o following p h a s e c h a n g e s o r s t u d y i n g kinetic effects.
O u t s i d e such special a p p l i c a t i o n s , however, x-ray
variable-wavelength experiments are unlikely t o p r o v e
i m p o r t a n t for w o r k o n a m o r p h o u s m a t e r i a l s o w i n g t o
the difficulty of accurately d e t e r m i n i n g t h e incident
s p e c t r u m a n d m a k i n g c o r r e c t i o n s for a b s o r p t i o n a n d
C o m p t o n scattering.
A n y m e a s u r e m e n t requires a certain n u m b e r of
c o r r e c t i o n s t o t h e basic d a t a b u t in a g o o d e x p e r i m e n t
these c o r r e c t i o n s a r e minimized o r p u t i n t o a form in
which they a r e easily h a n d l e d . N o r m a l l y , corrections
a r e included for:
(a)

c o u n t e r paralysis t i m e t h i s c o r r e c t i o n is b e c o m
ing increasingly i m p o r t a n t with m o d e r n highintensity x-ray a n d n e u t r o n sources;

(b)

i n s t r u m e n t a l b a c k g r o u n d a n d scattering
a n y s a m p l e c o n t a i n e r used;

(c)

a b s o r p t i o n , self-shielding a n d multiple scatter

ingthese c o r r e c t i o n s a r e closely c o u p l e d a n d

from

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Solids

Figure 3
Conventional neutron diffractometer

c a n only be t r e a t e d i n d e p e n d e n t l y if o n e o r o t h e r
of t h e m is small;
(d)

(e)

x-ray effects including p o l a r i z a t i o n a n d re

sidual C o m p t o n scattering n o t r e m o v e d by t h e
diffracted-beam m o n o c h r o m a t o r ; a n d
n e u t r o n s t a t i c - a p p r o x i m a t i o n d i s t o r t i o n s (Placzek corrections).

F o l l o w i n g c o r r e c t i o n it is necessary t o n o r m a l i z e t h e
d a t a t o a b s o l u t e units. T h i s m a y be achieved either b y
the use of self-consistent i n t e g r a t i o n t e c h n i q u e s or, for
n e u t r o n s , by m e a s u r i n g t h e ( i n c o h e r e n t ) s c a t t e r i n g
from a s t a n d a r d v a n a d i u m s a m p l e .

3. Outline

Theory

T h e corrected x-ray o r n e u t r o n diffraction

takes the general form
/(G) = / e( Q ) +

i(0

pattern

ma

for n e u t r o n s , a n d by a similar expression for rays

except t h a t t h e a t o m i c n u m b e r replaces the n e u t r o n
scattering length b. T h e j s u m m a t i o n is t a k e n over the
a t o m s in o n e unit of c o m p o s i t i o n . T h e F o u r i e r t r a n s
form in E q n . (7) is n o r m a l l y p e r f o r m e d numerically
using a high-speed digital c o m p u t e r .
T h e fact t h a t d a t a c a n only be o b t a i n e d for Q ^
Qmax m e a n s t h a t the r e l a t i o n s h i p between T(r) a n d
the c o m p o n e n t c o r r e l a t i o n functions tjk(r) is o n e of
convolution:

T{r) =

j*g/(0M(0sin rQ dQ (7)

(8)

T(r) = 4nrp^bj)2

(6)

in which P(Q) is t h e self-scattering ( i n d e p e n d e n t

scattering) a n d i(Q) is t h e distinct scattering (interfer
ence scattering). T h e r e q u i r e d s t r u c t u r a l i n f o r m a t i o n
c o n t a i n e d within i(Q) m a y be e x t r a c t e d by m e a n s of a
F o u r i e r t r a n s f o r m a t i o n of the interference function
Qi(Q) as outlined for n e u t r o n s in Fig. 6:

T(r) = T\r) +

w h e r e M(Q) is a modification function t o allow for

t h e fact t h a t d a t a c a n only be o b t a i n e d for Q less t h a n
o r e q u a l to s o m e m a x i m u m value Q m a x, a n d is zero for
2>e x- T(r) is given by

TLt)k{r)
J k
/OO

tjk(u)[P'jk(r

- u)

Jo

-P'jk(r

+ u)]du

(9)

T h e k s u m m a t i o n is t a k e n over a t o m types (elements),

u is a d u m m y c o n v o l u t i o n variable a n d the p r i m e
indicates o r for n e u t r o n s o r rays, respectively.
T h e c o r r e s p o n d i n g p e a k functions
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Target

Pulsed
electron

Cadmium + indium decoupler

BEAM

'olyethylene moderator
Concrete shielding wall

Evacuated flight tube

Solids

fl(Q) before F o u r i e r t r a n s f o r m a t i o n t o yield the socalled a t o m i c c o r r e l a t i o n function. T h e fact t h a t the Q

d e p e n d e n c e of / (Q) is different for each element
m e a n s t h a t t h e s h a p e of Pfk(r) c h a n g e s for each
independent component.
4. Methods

Borax in resin

92

U fjssion chamber
Focusing angle

B4C in resin
Variable Second
f|ight-pbth

BAC in rubber

Figure 4
Time-of-flight neutron diffractometer

P%(r)

= ( ^ )

M ( 0 C O S rQ dQ

(10)
define t h e e x p e r i m e n t a l resolution in real space.
fj(Q) a n d fk(Q)
being a t o m i c scattering factors
a n d / e(0 the a v e r a g e form factor p e r electron for the
s a m p l e j n q u e s t i o n . F o r n e u t r o n s , t h e scattering
lengths b a r e i n d e p e n d e n t of Q a n d the factor bjbk is a
simple scaling factor, w h e r e a s for rays it is c o n v e n
tional t o divide Qi(Q) b y t h e " s h a r p e n i n g " function

562

of

Interpretation

A s a l r e a d y n o t e d , b o t h Qi (Q) a n d T(r) are o n e d i m e n s i o n a l r e p r e s e n t a t i o n s of a t h r e e - d i m e n s i o n a l

s t r u c t u r e a n d a r e a gross a v e r a g e over t h e w h o l e
i r r a d i a t e d v o l u m e . I n a d d i t i o n , a s s h o w n by E q n . (9),
the e x p e r i m e n t a l c o r r e l a t i o n function is b r o a d e n e d by
P(r) a n d a single diffraction e x p e r i m e n t o n a m u l t i
element s a m p l e yields only a weighted s u m of the
individual c o m p o n e n t s tjk(r). V a r i o u s m e t h o d s exist
for experimentally d e t e r m i n i n g the individual c o m p o
n e n t s of Qi(Q) a n d T(r) for a p o l y a t o m i c system, all
of w h i c h involve a v a r i a t i o n of / ( ) o r b for o n e o r
m o r e of t h e c o n s t i t u e n t elements. F o r b o t h rays a n d
n e u t r o n s , it is possible t o utilize the p h e n o m e n o n of
a n o m a l o u s dispersion (the w a v e l e n g t h d e p e n d e n c e of
/ ( ) o r b n e a r a n a b s o r p t i o n edge o r resonance,
respectively), a n d for n e u t r o n s there are also the
t e c h n i q u e s of isotopic s u b s t i t u t i o n (b varies for dif
ferent isotopes of t h e s a m e element) a n d m a g n e t i c
diffraction. T h e successful use of each of these tech
n i q u e s is, h o w e v e r , limited t o relatively few favorable
s a m p l e s a n d , in m o s t cases, the m a x i m u m t h a t c a n b e
achieved is a c o m b i n a t i o n of x-ray a n d n e u t r o n
diffraction t e c h n i q u e s for w h i c h the c o m p o n e n t
weighting functions are different.
T h e d a t a o b t a i n e d from a n e x p e r i m e n t a l investiga
tion of a n a m o r p h o u s solid m a y t h u s r a n g e from a
single t o t a l c o r r e l a t i o n function T(r) t o a c o m p l e t e
d e t e r m i n a t i o n of all the individual c o m p o n e n t s t'jk(r).
T h e object in e a c h case is t o extract the m a x i m u m
i n f o r m a t i o n o n t h e s t r u c t u r e of the m a t e r i a l in q u e s
tion. M o s t a m o r p h o u s solids c o n t a i n a well-defined
s t r u c t u r a l u n i t w h i c h gives rise t o o n e o r m o r e rela
tively s h a r p p e a k s in the c o r r e l a t i o n function a t low r
from w h i c h it is possible t o e x t r a c t i n f o r m a t i o n o n
b o n d distances a n d angles by m e a n s of peak-fitting
techniques. T h e w a y in w h i c h t h e individual s t r u c t u r a l
units p a c k t o g e t h e r , the i n t e r m e d i a t e - r a n g e o r d e r , is
t h e n usually investigated t h r o u g h m o d e l calculations.
4.1 Peak Fitting
If it is a s s u m e d t h a t the d i s t r i b u t i o n of distances
a b o u t a m e a n value
is G a u s s i a n in tjk(f) with a r o o t 112
m e a n - s q u a r e d e v i a t i o n (ujk) ,
t h e n the resulting
c o n t r i b u t i o n t o Qi(Q) is of the form
s

Qijk(Q)

-r , ^
njkfj(Q)fk(Q)

in

ikQ

e x p i - i g ^ ) (11)

w h e r e nJk is t h e n u m b e r of /c-type a t o m s a r o u n d a t o m
j at this distance, a n d f{Q) represents either f(Q) o r b
for rays o r n e u t r o n s , respectively. T h e c o r r e s p o n d
ing real-space c o r r e l a t i o n function, including the c o n -

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of Amorphous

Solids

Scaler

Figure 5
Fluorescent-foil x-ray diffraction technique

t r i b u t i o n from P(r), c a n b e o b t a i n e d b y F o u r i e r
t r a n s f o r m a t i o n of E q n . (11) w i t h t h e s a m e value of
g m ax a n d modification function a s used e x p e r i m e n
tally. It is t h u s possible t o o b t a i n t h e p a r a m e t e r s njk,rjk
1 /2
a n d (w#) b y p e r f o r m i n g a least-squares fit t o t h e
e x p e r i m e n t a l d a t a in real space o r t o t h e e x p e r i m e n t a l
interference function a t h i g h Q, w h e r e only t h e s h a r p
est real-space p e a k s c o n t r i b u t e .

7(0)=/ (0)*/(0)
self

()=

{)+

J Q/lQ)M[Q)

distinct

sin rO

dO

Figure 6
Steps in the calculation of the real-space correlation
function T(r) from the corrected intensity / ( g )

4.2 Model
Calculations
T h e limited n a t u r e of t h e m e a s u r e d c o r r e l a t i o n func
tion m e a n s t h a t in o r d e r t o e x t r a c t m o r e t h a n j u s t
average interatomic distances a n d coordination
n u m b e r s it is necessary t o r e s o r t t o s o m e f o r m of
m o d e l a n d t o ascertain h o w well this agrees with
e x p e r i m e n t . Qi(Q) a n d T(r) e m p h a s i z e different a s
pects of t h e s t r u c t u r e a n d it is therefore m o s t i m p o r t
a n t t o m a k e such c o m p a r i s o n s in b o t h real a n d
intensity space, a n d in t h e f o r m e r t o correctly incor
p o r a t e t h e p e a k function P(r). Similarly, n o m a t t e r
h o w g o o d t h e a g r e e m e n t o b t a i n e d is, t h e m o d e l in
q u e s t i o n is only o n e possible fit t o t h e d a t a a n d hence
it is essential t o c o n s i d e r , a n d if possible eliminate, all
a l t e r n a t i v e m o d e l s . A variety of s t r u c t u r a l m o d e l s a n d
m o d e l l i n g t e c h n i q u e s h a s b e e n e m p l o y e d in t h e s t u d y
of a m o r p h o u s solids a n d s o m e of t h e m o r e i m p o r t a n t
of these a r e s u m m a r i z e d b e l o w .
(a)

C r y s t a l - b a s e d m o d e l s . A g r e a t deal of i n f o r m a
tion o n t h e s t r u c t u r e of a m o r p h o u s solids c a n be
o b t a i n e d from a simple c o m p a r i s o n with t h e
c o r r e s p o n d i n g crystalline p o l y m o r p h s . M o r e
f o r m a l crystal-based m o d e l s , such as t h e q u a s i crystalline m o d e l , s t a r t w i t h a n a p p r o p r i a t e crys
tal s t r u c t u r e a n d restrict t h e l o n g e r - r a n g e o r d e r
t o i n t e r a t o m i c spacings less t h a n s o m e c h a r a c t e r
istic c o r r e l a t i o n length.

(b)

Random-network models. The random-network

t h e o r y h a s b e e n t h e m o s t successful in describing
t h e s t r u c t u r e of t r a d i t i o n a l oxide glasses a n d
amorphous semiconductors. Random-network

563

X-Ray

and Neutron

Diffraction

Studies

of Amorphous

m o d e l s m a y be built either by h a n d o r using a

computer.
(c)

C h a i n a n d ring m o d e l s . T h e s e m o d e l s a r e a p p r o
p r i a t e for m a t e r i a l s c o n t a i n i n g only divalent
a t o m s (e.g., selenium) o r larger t w o - c o n n e c t e d
g r o u p i n g s of a t o m s such as t h o s e f o u n d in or
ganic p o l y m e r s ( e . g . , C H 2 ) .

(d)

Random-sphere-packing
models.
Random
sphere p a c k i n g s p r o v i d e a useful s t a r t i n g p o i n t
for m o d e l s of a m o r p h o u s metallic alloys a n d
m a t e r i a l s w h o s e s t r u c t u r e s a r e g o v e r n e d by p r e
d o m i n a n t l y ionic forces such as vitreous Z n C l 2 .

(e)

Molecular models. Models based on a r a n d o m

p a c k i n g of a p p r o x i m a t e l y spherical molecules
h a v e been used t o describe t h e s t r u c t u r e of s o m e
v a p o r - d e p o s i t e d thin films (e.g. C C 1 4 , A s - S a n d
A s 2 0 3 ) . T h e formalism e m p l o y e d closely follows
t h a t for m o l e c u l a r liquids.

(f)

A m o r p h o u s - c l u s t e r m o d e l s . A m o r p h o u s clusters
a r e c o m p o s e d of a t o m s in a regular b u t n o n c r y s t a l l o g r a p h i c configuration frequently b a s e d o n
p e n t a g o n a l d o d e c a h e d r a o r fivefold s y m m e t r y .
Cluster size is limited d u e t o a slight m i s m a t c h
between adjacent s t r u c t u r a l u n i t s , w h i c h leads t o
increasing d i s t o r t i o n as t h e cluster g r o w s .

(g)

M o n t e C a r l o a n d m o l e c u l a r d y n a m i c s simula
tions. T h e s t r u c t u r e s of a r a n g e of simple inor
ganic glasses h a v e been s i m u l a t e d using p u r e l y
ionic p o t e n t i a l s . A g a i n t h e m e t h o d s e m p l o y e d
closely follow t h o s e for related liquids.

5. Neutron

Magnetic

Diffraction

A s with crystalline m a t e r i a l s , t h e fact t h a t t h e n e u t r o n

h a s a m a g n e t i c m o m e n t m e a n s t h a t it is possible t o
use n e u t r o n diffraction t o p r o b e the m a g n e t i c struc
t u r e of a m o r p h o u s solids. M a g n e t i c o r d e r i n g in a n
a m o r p h o u s solid m a y o c c u r either s p o n t a n e o u s l y
below s o m e m a g n e t i c - o r d e r i n g t r a n s i t i o n t e m p e r a t u r e
or else be i n d u c e d b y t h e a p p l i c a t i o n of a s t r o n g
m a g n e t i c field. A full description of t h e f o r m a l i s m of
n e u t r o n m a g n e t i c scattering a n d t h e results o b t a i n e d
is given in W r i g h t (1980).

6. Accuracy

and

Limitations

A discussion of the a c c u r a c y a n d limitations of t h e

t e c h n i q u e c a n b e divided i n t o t w o p a r t s : t h e a c c u r a c y
of t h e e x p e r i m e n t a l d a t a a n d t h a t of t h e resulting
t r a n s f o r m , a n d t h e extent of t h e a m b i g u i t y of a n y
i n t e r p r e t a t i o n of these d a t a . T h e a c c u r a c y of t h e
e x p e r i m e n t a l d a t a c a n m o s t easily be g a u g e d b y t h e
b e h a v i o r of the t r a n s f o r m a t low r, below the first t r u e
p e a k . If t h e t r a n s f o r m is well b e h a v e d in this region,
t h e n t h e d a t a a r e of r e a s o n a b l e quality. G r e a t c a r e is
needed in m a k i n g this assessment, h o w e v e r , as s o m e

564

Solids

a u t h o r s either p l o t t h e r a d i a l d i s t r i b u t i o n function
r 7 \ r ) , w h i c h h a s t h e effect of r e d u c i n g t h e a m p l i t u d e
of e r r o r ripples a t low r, o r use these false oscillations
as a criterion for tidying their d a t a before p u b l i c a t i o n
a n d d o n o t include the original u n t r e a t e d t r a n s f o r m .
In t h e a b s e n c e of o t h e r i n f o r m a t i o n such d a t a m u s t be
r e g a r d e d with t h e u t m o s t suspicion.
Similar t e c h n i q u e s a r e s o m e t i m e s used t o r e m o v e
t h e effects of t e r m i n a t i n g t h e d a t a a t finite Q m a x.
I n f o r m a t i o n t h e o r y , h o w e v e r , indicates t h a t it is im
possible t o replace t h e u n m e a s u r e d d a t a w i t h o u t
making some assumption a b o u t the material under
investigation so t h a t t h e resulting c o r r e l a t i o n function
merely b e c o m e s o n e possible m o d e l which fits the
results r a t h e r t h a n a n u n b i a s e d F o u r i e r t r a n s f o r m . It
s h o u l d also be n o t e d t h a t in principle b o t h Qi(Q) a n d
T(r) c o n t a i n t h e s a m e i n f o r m a t i o n expressed in a
different f o r m , a l t h o u g h in practice t h e i n f o r m a t i o n
c o n t e n t of T(r) is slightly r e d u c e d by t h e use of a
modification function. T h e finite u p p e r limit in Q
m e a n s t h a t in T(r) e a c h c o m p o n e n t tjk{r) is c o n v o
luted with t h e a p p r o p r i a t e p e a k f u n c t i o n p ( r ) , b u t the
i n f o r m a t i o n for a p a r t i c u l a r d i s t a n c e is still c o n c e n
t r a t e d a r o u n d t h a t d i s t a n c e (whereas it is s p r e a d
t h r o u g h o u t reciprocal space).
T h e u n i q u e n e s s of a n y s t r u c t u r a l i n f o r m a t i o n
e x t r a c t e d from t h e d a t a is m u c h m o r e difficult t o
j u d g e . A s a l r e a d y stressed, t h e o n e - d i m e n s i o n a l
n a t u r e of t h e c o r r e l a t i o n function m e a n s t h a t it is
impossible t o u n a m b i g u o u s l y d e t e r m i n e t h e s t r u c t u r e
of a n a m o r p h o u s solid. T h e reliability of a n y i n t e r p r e
t a t i o n , therefore, d e p e n d s n o t only o n t h e q u a l i t y of
the fit t o the e x p e r i m e n t a l d a t a in b o t h real a n d
reciprocal space, b u t also o n the n u m b e r of o t h e r
possible m o d e l s w h i c h h a v e been tried a n d satisfactor
ily rejected. T h e fact t h a t diffraction d a t a a r e a n
a v e r a g e for t h e w h o l e i r r a d i a t e d v o l u m e , a n d include
a t m o s t only p a r t of a n y small-angle scattering which
m a y be p r e s e n t , m e a n s t h a t t h e d a t a a r e relatively
insensitive t o p h a s e s e p a r a t i o n . In m o s t cases, it is
n o t possible t o d e t e r m i n e t h e individual c o m p o n e n t
a n d in this situation
c o r r e l a t i o n functions tjk(r),
e x t e n d e d x-ray a b s o r p t i o n fine-structure t e c h n i q u e s
can provide important complementary information.
Finally, it m u s t n o t be f o r g o t t e n t h a t a great deal of
o t h e r s t r u c t u r a l i n f o r m a t i o n c a n be o b t a i n e d from the
results of indirect p r o b e s such as optical s p e c t r o s c o p y
a n d m a g n e t i c r e s o n a n c e s p e c t r o s c o p y . All of these
d a t a m u s t also be consistent with a n y c h o s e n struc
tural model.
See also: Single-Crystal X-Ray Diffraction; X-Ray Absorp
tion Spectroscopy: EXAFS and XANES Techniques;
X-Ray Powder Diffraction

Bibliography
Elliott S R 1984 Physics of Amorphous Materials. Longman,
London

X-Ray

and Neutron

Gaskell 1991 Models for the structure of amorphous

solids. In: Zarzycki J (ed.) 1991 Glasses and Amorphous
Solids. VCH, Weinheim, Germany, pp. 175-278
Wagner C J 1978 Direct methods for the determination of
atomic-scale structure of amorphous solids (x-ray, elec
tron and neutron scattering). J. Non-Cryst. Solids 3 1 : 1 40
Wagner C J 1980 Diffraction analysis of metallic, semi
conducting and inorganic glasses. J. Non-Cryst. Solids 42:
3-21
Warren 1969 X-Ray Diffraction. Addison-Wesley,
Reading, MA
Warren , Mavel G 1965 Elimination of the Compton
component in amorphous scattering. Rev. Sci. Instrum.
36: 196-7
Wong J, Angell C A 1976 Glass: Structure by Spectroscopy.
Dekker, New York, Chap. 2
Wright A C 1974 The structure of amorphous solids by xray and neutron diffraction. Adv. Struct. Res. Diffr.
Methods 5: 1-84
Wright A C 1980 Neutron magnetic scattering studies of
amorphous solids. / . Non-Cryst. Solids 40: 325-46
Wright A C 1984 Basic amorphography. In: Fleury A,
Golding (eds.) 1984 Coherence and Energy Transfer in
Glasses. Plenum, New York, pp. 1-38
Wright A C, Leadbetter A J 1976 Diffraction studies of glass
structure. Phys. Chem. Glasses 17: 122-45
Zallen R 1983 The Physics of Amorphous Solids. Wiley, New
York
A. C. Wright
[J. J. T h o m p s o n Physical L a b o r a t o r y ,
Reading, U K ]

X-Ray and Neutron Diffuse Scattering

of Radiation-Induced Defects
In the p a s t several years m a n y f u n d a m e n t a l q u e s t i o n s
involving r a d i a t i o n - i n d u c e d defects in m e t a l s h a v e
been a n s w e r e d using diffuse x-ray a n d n e u t r o n scat
tering t e c h n i q u e s . T h e s e t e c h n i q u e s c a n be e m p l o y e d
to investigate b o t h p o i n t defects, t h a t is, vacancies
a n d interstitial a t o m s , a n d p o i n t defect a g g l o m e r a t e s
u p t o sizes t h a t c a n be i m a g e d in a n electron m i c r o
scope. A s m i c r o s c o p i c p r o b e s of defect p r o p e r t i e s a n d
i n t e r a c t i o n s , t h e t e c h n i q u e s c a n p r o v i d e u n i q u e infor
m a t i o n which is difficult t o o b t a i n by o t h e r m e t h o d s .

I. Diffuse

X-Ray

Scattering

T h e u n d e r l y i n g principles of diffuse x-ray scattering

a r e r a t h e r s t r a i g h t f o r w a r d . In a perfect crystal, t h e xray scattering intensity is z e r o e v e r y w h e r e except a t
the B r a g g p e a k , t h a t is, w h e n t h e scattering vector k
coincides with a reciprocal lattice v e c t o r h. W h e n a
defect is i n t r o d u c e d i n t o t h e lattice, t h e perfect cancel
lation of scattered w a v e s a w a y from t h e B r a g g p e a k is
d e s t r o y e d a n d a diffuse scattering intensity results.
F o r a low c o n c e n t r a t i o n of r a n d o m l y d i s t r i b u t e d

Diffuse

Scattering

of Radiation-Induced

Defects

defects, t h e diffuse intensity c a n be o b t a i n e d from the

relation ( D e d e r i c h s 1973)
2

(1)

S=c\F(k)\

w h e r e c is the c o n c e n t r a t i o n of defects a n d F(k) is the

"defect s t r u c t u r e f a c t o r . " T h i s s t r u c t u r e factor c a n be
expressed in the form
i

^)=/?+/te '-"(e *-'"-l)

(2)

w h e r e a n d fk a r e the a t o m i c scattering factors of the

defect a n d h o s t a t o m s respectively, a n d t" is the
d i s p l a c e m e n t vector of a t o m n, a w a y from its n o r m a l
n
lattice site a t r . E q u a t i o n (2) s h o w s t h a t the scattering
intensity arises from b o t h the defect itself ( L a u e
scattering), a n d from t h e d i s p l a c e m e n t s of the lattice
a t o m s c a u s e d by t h e defect. T o d e t e r m i n e t h e t y p e a n d
c o n f i g u r a t i o n of t h e defects in a n i r r a d i a t e d specimen,
scattering intensities a r e m e a s u r e d at different p o i n t s
in reciprocal space a n d c o m p a r e d with intensities
calculated for likely defect configurations. A m a j o r
p a r t of the p r o b l e m of c o u r s e is t o calculate the
d i s p l a c e m e n t field of t h e defect. F i g u r e 1 illustrates
h o w this p r o c e d u r e w a s e m p l o y e d t o d e t e r m i n e the
configuration of self-interstitial a t o m s in electroni r r a d i a t e d a l u m i n u m . T h e <100> split configuration is
t h e o n l y r e a s o n a b l e choice.
T h e difficulty in a c q u i r i n g d a t a like t h o s e in Fig. 1 is
t h a t for p o i n t s far from t h e B r a g g p e a k s the defect
scattering intensity is small a n d t h e b a c k g r o u n d aris
ing from C o m p t o n a n d t h e r m a l diffuse scattering is
high. F o r t h e d a t a s h o w n in Fig. 1, a 100 k W source
a n d a 100-detector system w a s r e q u i r e d ( H a u b o l d
1975). C l o s e t o t h e B r a g g p e a k t h e scattering intensity
from defects increases r a p i d l y , a n d this scattering
( H u a n g scattering) c a n m o r e easily b e m e a s u r e d .
C a l c u l a t i o n s s h o w t h a t the scattering in this region
arises p r i m a r i l y from t h e d i s p l a c e m e n t s of a t o m s far
from t h e defect center. Such d i s p l a c e m e n t s c a n be
calculated using elastic c o n t i n u u m t h e o r y a n d this
greatly simplifies t h e theoretical p r o b l e m . T h e m a g n i
t u d e of t h e H u a n g scattering d e t e r m i n e s t h e relax
a t i o n v o l u m e of the defect, a n d t h e a n i s o t r o p y of the
scattering reflects the s y m m e t r y . O w i n g t o the less
d e m a n d i n g r e q u i r e m e n t s of the H u a n g m e a s u r e
m e n t s , they h a v e been used extensively t o d e t e r m i n e
r e l a x a t i o n v o l u m e s a n d c o n f i g u r a t i o n s of interstitial
a t o m s in m e t a l s of fee, bec a n d h e p s t r u c t u r e s .
H u a n g scattering also p r o v i d e s a very sensitive
m e t h o d for m o n i t o r i n g defect clustering. T h i s is p o s
sible b e c a u s e t h e H u a n g scattering is p r o p o r t i o n a l t o
t h e s q u a r e of t h e r e l a x a t i o n v o l u m e of t h e defect. F o r
t h e e x a m p l e of a c o n c e n t r a t i o n of c single defects,
e a c h of r e l a x a t i o n v o l u m e V, a n d forming agglomer
ates of size d u r i n g a n a n n e a l i n g t r e a t m e n t , the
H u a n g scattering intensities before a n d after a n n e a l
ing a r e given by
5b

occ(AF)

(3)

e f o r e

S a [ l eor c ( c / ) ( A F )

(4)

565

X-Ray

and Neutron

022

Diffuse

Scattering

of Radiation-Induced

Defects

222
? _

Scattering angle

()

Figure 1
Comparison of the measured diffuse scattering intensity from electron-irradiated aluminum with intensities calculated
assuming different self-interstitial atom configurations (after Haubold 1975)

respectively, so t h a t their r a t i o yields

^after /^before

2. Neutron
(5)

T h u s the average n u m b e r of defects in a cluster c a n be

determined.
Scattering intensities for dislocation l o o p s h a v e
also been studied ( E h r h a r t et al. 1982). F i g u r e 2 s h o w s
the calculated scattering intensity for a n interstitial
4
a t o m F r a n k l o o p in nickel p l o t t e d as Sq vs qR for q
parallel t o h (q = k - h), w h e r e R is the r a d i u s of the
4
l o o p . T h e l o o p r a d i u s c a n b e o b t a i n e d by p l o t t i n g Sq
against q t o locate the p e a k p o s i t i o n qQ9 a n d setting the
p r o d u c t q0R e q u a l t o the p e a k p o s i t i o n s h o w n in Fig.
2. T h e height of the p e a k yields the l o o p c o n c e n t r a
tion.

Diffuse

Elastic

Scattering

In Sect. 1 a t t e n t i o n w a s focused m o s t l y o n x-ray

scattering very n e a r t h e B r a g g p e a k s . F o r m u l t i c o m
p o n e n t systems, t h a t is, alloys a n d c o m p o u n d s , a
w e a l t h of i n f o r m a t i o n is available from the diffuse
scattering b e t w e e n t h e B r a g g p e a k s . Let us follow the
t r e a t m e n t first c o n s i d e r e d by Borie a n d S p a r k s (1971)
for a c o n c e n t r a t e d cubic b i n a r y s u b s t i t u t i o n a l alloy,
where both composition and positional disorder pre
vail. If we define real space i n t e r a t o m i c vectors pt =
Im In = /(a, 2) + m(a2 2) + ( a 3 2), a n d reciprocal
lattice c o o r d i n a t e s Q = hlbl + h2b2 + 33 such t h a t /,
m, a r e integers a n d A h2, h3 a r e c o n t i n u o u s vari
ables, t h e n t h e differential scattering cross section,
n o r m a l i z e d in L a u e m o n o t o n i c u n i t s , is expressed as
dajdO.
CACB(fA-b'B)

+ ( , ) + , ( . )
2

+ ? ( 1 , 2 , 3 ) + 2 ( 2 , 3 )
+ ^ ^ , , ) + A,

h2Sxy(hh2,h3)

+ MjS^Mj,*,) + , 5 ^ (

, 2)

(6)

with
^SRO

lmn
a

os

sc

2 COS

7TNAJ

(7)

c o s 2 cos 3

(8)

l,m,n

Figure 2
Scattering intensities close to (400) reflections in a [100] q
direction calculated for dislocation loops with radius
20 A in nickel (after Ehrhart et al. 1982)
566

Qx

l,m,n

yimn '

lh\

X-Ray

Rx

= 6 lmn sin nlhx c o s nmh2 c o s nnh3

(9)

l,m,n

*mn

sm

ms

wnh-! sin nnh3

(10)

l,m,n

C, a r e c o n c e n t r a t i o n s of species a n d b\ a r e n e u t r o n
scattering lengths weighted b y a p p r o p r i a t e D e b y e Waller factors. A detailed discussion c a n b e f o u n d in
S c h m a t z (1973) a n d B a u r (1979). T h e t e r m s in Rx
c o n t a i n i n f o r m a t i o n a b o u t static d i s p l a c e m e n t effects
described in Sect. 1; 7 S RO p r o v i d e s details o f s h o r t r a n g e o r d e r a n d clustering a m o n g defects. T h e u s e o f
s y m m e t r y a r g u m e n t s in a detailed discussion o f these
e q u a t i o n s c a n b e f o u n d in S c h w a r t z a n d C o h e n
(1977). T h e p o i n t h e r e is t h a t t h e F o u r i e r coefficients
in E q n s . ( 8 - 1 0 ) , for r a y s , c o n t a i n a t o m i c scattering
factors f(Q) a n d t h u s a r e n o t strictly periodic. F o r
n e u t r o n s , n u c l e a r scattering lengths a r e a p p r o p r i a t e
a n d hence t h e a p p l i c a t i o n o f n e u t r o n s offers signific
a n t a d v a n t a g e over r a y s .
Diffuse elastic n e u t r o n scattering ( D E N S ) tech
niques allow u s t o r e m o v e t h e c o m p l i c a t i o n s o f
t i m e - d e p e n d e n t p h e n o m e n a such a s p h o n o n inelastic
scattering, a n d a r e m u c h less sensitive t o surface
effects since n e u t r o n a b s o r p t i o n cross sections a r e
m u c h smaller t h a n x-ray c o u n t e r p a r t s . T h e largest
sources of b a c k g r o u n d in x-ray m e a s u r e m e n t s a r e
C o m p t o n a n d t h e r m a l diffuse scattering; these a r e
eliminated using D E N S t e c h n i q u e s . H o w e v e r , c a r e
m u s t b e t a k e n in t h e n e u t r o n case t o a v o i d n u c l e a r
spin a n d i s o t r o p i c d i s o r d e r scattering. T h e m a i n dis
a d v a n t a g e s o f D E N S stem from limited n e u t r o n
fluxes available a t steady state sources; h o w e v e r , n e w
i n s t r u m e n t a t i o n a n d t h e a d v e n t of pulsed n e u t r o n
sources m a y allow u s t o m i n i m i z e this limitation (see
C o h e n et al. (1975)).

Acknowledgement
T h e w o r k o f t h e a u t h o r s is s u p p o r t e d b y t h e U S
Government under contract N o . W-31-109-ENG-38.
See also: Electron Microscope Analysis of Defect Clusters,
Voids and Bubbles; X-Ray Powder Diffraction

Bibliography
Baur G S 1979 Diffuse elastic neutron scattering from non
magnetic materials. In: Herman (ed.) 1979 A Treatise
on Materials Science and Technology, Vol. 15. Academic
Press, New York, pp. 291
Borie B, Sparks C J Jr 1971 The interpretation of intensity
distributions from distorted binary alloys. Acta Crystallogr. Sect. A 27: 198-201
Cohen J B, Faber J, Batterman W, Baur G S, King S S,
Larson C, Summerfeld G C 1975 Advanced Uses of
Pulsed Neutron Sources, ANL-76-10, Vol. 2. Argonne
National Laboratory, Argonne, IL, p. 88

Diffraction,

Time-Resolved

Dederichs 1973 The theory of diffuse x-ray scattering

and its application to the study of point defects and their
clusters. J. Phys. F3: 471-96
Ehrhart 1978 The configuration of atomic defects as
determined from scattering studies. / . Nucl. Mater. 69/70:
200-14
Ehrhart P, Trinkaus H, Larson C 1982 Diffuse scattering
from dislocation loops. Phys. Rev. 25: 834-48
Haubold H-G 1975 In: Robinson , Young F W Jr (eds.)
1975 Fundamental Aspects of Radiation Damage in
Metals.
National Technical Information Service,
Springfield, VA, p. 268
Schmatz W 1973 X-ray and neutron scattering studies on
disordered crystals. In: Herman (ed.) 1973 A Treatise in
Materials Science and Technology, Vol. 2. Academic
Press, New York, pp. 105-229
Schwartz L H, Cohen J 1977 Diffraction From Materials.
Academic Press, New York, pp. 403-24
J. F a b e r J r a n d R . S. A v e r b a c k
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]

X-Ray Diffraction, Time-Resolved

X - r a y diffraction h a s p l a y e d a k e y role in t h e develop
ment of o u r understanding of the structure of mater
ials. Since its i n c e p t i o n , efforts h a v e been m a d e t o
m e a s u r e t h e s t r u c t u r a l c h a n g e s which o c c u r d u r i n g
m a t e r i a l s processing t r e a t m e n t s . T o a n s w e r such
q u e s t i o n s , which inherently involve t h e time e v o l u t i o n
of s t r u c t u r e s , t h e time r e s o l u t i o n o f t h e diffraction
measurement must be considered. With conventional
x-ray sources, a s f o u n d in m o s t l a b o r a t o r i e s , t h e time
r e q u i r e d t o m e a s u r e a diffraction p a t t e r n r a n g e s from
minutes t o days. With the advent of new synchrotron
x-ray sources, this t i m e c a n b e r e d u c e d t o milli
seconds.
Diffraction m e a s u r e m e n t s s t u d y i n g time e v o l u t i o n
c a n b e categorized i n t o three types: p r e t r e a t m e n t a n d
p o s t - t r e a t m e n t m e a s u r e m e n t s , in situ s t r o b o s c o p i c
m e a s u r e m e n t s a n d direct in situ
time-resolved
m e a s u r e m e n t s . P r e t r e a t m e n t a n d p o s t - t r e a t m e n t tech
n i q u e s involve x-ray m e a s u r e m e n t s w h i c h a r e m a d e
before a n d after processing. Often, s o m e a t t e m p t is
m a d e d u r i n g processing t o a r r e s t t h e s t r u c t u r a l evolu
tion in m i d p r o c e s s . Classic e x a m p l e s of such m e a s u r e
m e n t s a r e diffraction m e a s u r e m e n t s m a d e after h e a t
t r e a t m e n t s in w h i c h t h e s a m p l e s a r e a n n e a l e d a t high
t e m p e r a t u r e s for v a r y i n g a m o u n t s o f time. F o r fast
processes, p r e t r e a t m e n t a n d p o s t - t r e a t m e n t m e a s u r e
m e n t s a r e often n o t possible o r a r e fraught with
systematic e r r o r s in w h i c h t h e s t r u c t u r e evolves in
u n e x p e c t e d w a y s d u r i n g t h e processing used t o arrest
t h e time e v o l u t i o n . I n spite o f these limitations, time
resolutions shorter than the required measurement
time of a diffraction p a t t e r n a r e possible.
S t r o b o s c o p i c t e c h n i q u e s a r e b a s e d o n a n ability t o
cycle a s a m p l e r e p e a t e d l y t h r o u g h a process. T h i s
567

X-Ray

Diffraction,

Time-Resolved

allows m e a s u r e m e n t s t o a v e r a g e over m a n y cycles a n d

build u p a diffraction p a t t e r n slowly over time b u t
with high time resolution. T h i s t e c h n i q u e is n o t
always applicable, since n o t all processing c a n b e
cycled o r cycled r e p r o d u c i b l y e n o u g h . T h i s t e c h n i q u e
is very powerful a n d h a s been used t o o b t a i n m i c r o
second a n d even n a n o s e c o n d time resolution.
T h e final m e t h o d , w h i c h h a s t h e m o s t stringent
r e q u i r e m e n t s , is r e p e a t e d real-time m e a s u r e m e n t s .
This m e t h o d h a s t h e a d v a n t a g e t h a t t h e analysis of
the d a t a is m o r e s t r a i g h t f o r w a r d a n d systematic
e r r o r s a r e greatly reduced. T h e time resolution of this
t e c h n i q u e directly d e p e n d s o n t h e time t o a c q u i r e a
diffraction p a t t e r n which, in o p t i m u m c o n d i t i o n s , c a n
be a few milliseconds o r even s h o r t e r .
D e s c r i p t i o n s of h o w diffraction m e a s u r e m e n t s a r e
m a d e a n d t h e i n f o r m a t i o n o b t a i n e d a r e given in t h e
articles Single-Crystal
X-Ray Diffraction, X-Ray and
Neutron Diffraction Studies of Amorphous Solids a n d
X-Ray Powder Diffraction. I n p a r t i c u l a r , t h e article o n
x-ray p o w d e r diffraction p r e s e n t s a list of the principle
uses of t h e m e t h o d . Time-resolved x-ray diffraction
allows t h e m e a s u r e m e n t of t h e time e v o l u t i o n of
this i n f o r m a t i o n . P r e t r e a t m e n t a n d p o s t - t r e a t m e n t
m e a s u r e m e n t t e c h n i q u e s use c o n v e n t i o n a l x-ray dif
fraction m e a s u r e m e n t s a n d t h u s will n o t b e discussed
here. T h i s article e m p h a s i z e s t h e use of in situ tech
niques a n d m o s t of t h e e m p h a s i s will b e o n direct
m e t h o d s . O f c o u r s e , a n y direct m e t h o d which reduces
the time needed t o m e a s u r e a diffraction p a t t e r n c a n
be used b y all t h e t e c h n i q u e s .

/.

Direct

Measurements

R e c e n t a d v a n c e s in x-ray sources a n d diffraction

g e o m e t r y h a v e led t o t e c h n i q u e s with e n o u g h x-ray
diffraction intensity so t h a t a diffraction p a t t e r n c a n
be a c q u i r e d in 1 m s . F o r this it is desirable t o h a v e 100
to 1000 c o u n t s in t h e m a x i m u m of a diffraction
p a t t e r n in o r d e r t o o b t a i n a high e n o u g h signal-tonoise r a t i o for analysis. M e a s u r e m e n t s of 1 m s t i m e
5
6
resolution t h e n require c o u n t rates exceeding 10 10
c o u n t s p e r second in t h e diffracted b e a m . It is quickly
realized t h a t c o n v e n t i o n a l x-ray d e t e c t o r s a r e n o t fast
e n o u g h for this type of m e a s u r e m e n t .
T h e m i n i m u m time t o o b t a i n a diffraction p a t t e r n is
t h u s usually d e t e r m i n e d either b y a l o w diffraction
intensity w h i c h limits t h e q u a l i t y of t h e diffraction
p a t t e r n o r b y t h e d e t e c t o r which limits t h e c o u n t i n g
speed.
A n x-ray diffraction e x p e r i m e n t consists of a n
incident b e a m of rays, usually m o n o c h r o m a t i c ,
which strike a s a m p l e a n d scatter i n t o a d e t e c t o r
system. T o decrease t h e time r e q u i r e d for m e a s u r i n g a
diffraction p a t t e r n , it is necessary t o increase t h e
n u m b e r of x-ray p h o t o n s which strike t h e s a m p l e a n d /
o r increase t h e d e t e c t i o n efficiency. T h e m o s t intense
x-ray sources a r e s y n c h r o t r o n s . T h e s e sources a r e

568

m o r e t h a n six o r d e r s of m a g n i t u d e b r i g h t e r t h a n
c o n v e n t i o n a l r o t a t i n g a n o d e x-ray sources a n d synch
r o t r o n facilities scheduled t o b e c o m p l e t e d in t h e m i d 1990s will b e yet a n o t h e r t h o u s a n d times brighter.
H a v i n g selected a s o u r c e , three w a y s exist t o increase
the t o t a l flux in t h e incident b e a m : use m o r e w a v e
lengths of t h e s o u r c e , use m o r e angles of t h e s o u r c e o r
use s o m e c o m b i n a t i o n of b o t h . Often, t h e resulting
increase in flux is a t t h e expense of lowering t h e
diffraction r e s o l u t i o n of t h e e x p e r i m e n t .
Before p r o c e e d i n g , it is w o r t h w h i l e m e n t i o n i n g a n
essential difference b e t w e e n t w o types of m e a s u r e
m e n t s , p o w d e r diffraction a n d single-crystal dif
fraction. B r a g g ' s law requires t w o c o n d i t i o n s t o b e
satisfied for diffraction. O n e results b e c a u s e t h e angle
of incidence of t h e r a y s o n t h e diffracting p l a n e s
m u s t b e correct a n d t h e s e c o n d b e c a u s e rays will
diffract only in certain directions. T h e incident angle
r e q u i r e m e n t m e a n s t h a t for time-resolved diffraction
o n single crystals it is also necessary, except in special
cases, t o c h a n g e t h e o r i e n t a t i o n of t h e crystal. F o r
p o w d e r s , crystallites exist a t all o r i e n t a t i o n s a n d so
t h e first r e q u i r e m e n t is always satisfied a n d only t h e
p l a c e m e n t of t h e x-ray d e t e c t o r a t t h e correct scatter
ing angles is needed. A n o t h e r i m p o r t a n t difference
b e t w e e n a single crystal a n d a p o w d e r s a m p l e of t h e
s a m e m a t e r i a l is t h e relative intensity of a typical
B r a g g p e a k . F o r a single crystal t h e intensity of a
B r a g g p e a k is localized i n t o a n intense small solid
angle of scattering. I n c o n t r a s t , t h e m a n y o r i e n t a t i o n s
of crystallites in a polycrystalline s a m p l e result in a
c o n e of scattering of w h i c h diffractometers only
m e a s u r e a small fraction.
T h e m o s t o b v i o u s w a y t o i m p r o v e t h e detection
efficiency in a c o n v e n t i o n a l p o w d e r diffraction experi
m e n t is t o use m a n y d e t e c t o r s a n d therefore collect
m a n y scattering angles s i m u l t a n e o u s l y . T h i s is c o n
veniently d o n e using o n e - d i m e n s i o n a l a n d t w o d i m e n s i o n a l d e t e c t o r a r r a y s , w h i c h a r e often referred
to a s position-sensitive d e t e c t o r s . T h e diffraction reso
lution of these d e t e c t o r s is partially d e t e r m i n e d b y t h e
physical size o f e a c h d e t e c t o r element a n d t h e time
r e s o l u t i o n is d e t e r m i n e d b y t h e electronics, which
limits t h e m a x i m u m m e a s u r a b l e c o u n t r a t e . T h e
oldest position-sensitive d e t e c t o r is a p r o p o r t i o n a l
wire d e t e c t o r . T h e y c o n v e n t i o n a l l y give 100 spa
tial r e s o l u t i o n a n d c a n s p a n a region of 510 c m in
either a straight line o r a l o n g a circular a r c . T h e s e
d e t e c t o r s h a v e a very l o w intrinsic b a c k g r o u n d . T h e i r
p r i m a r y deficiency is t h a t they h a v e a relatively low
m a x i m u m c o u n t r a t e of a r o u n d 50 000 rays p e r
second i n t e g r a t e d over t h e w h o l e detector. Since
50 000 c o u n t s s p r e a d over a diffraction p a t t e r n is
a b o u t t h e m i n i m u m n u m b e r of c o u n t s r e q u i r e d t o
define a diffraction p a t t e r n , this limits t h e m i n i m u m
time p e r diffraction p a t t e r n t o a r o u n d 1 s. M o r e
recently, p h o t o d i o d e a r r a y s ( S t e p h e n s o n 1988) a n d
c h a r g e - c o u p l e d device ( C C D ) a r r a y s ( R o d r i c k s et al.
1989) h a v e b e c o m e available for x-ray detection. T h e y

X-Ray

h a v e m u c h higher m a x i m u m c o u n t rates a n d faster

r e a d o u t times. T h e i r p r i n c i p a l deficiency is their
s h o r t e r length a n d higher intrinsic b a c k g r o u n d . F o r
p h o t o d i o d e a r r a y s , r e a d o u t times of several millise
c o n d s are possible a n d a r r a y s w i t h t o t a l lengths of 2 5 c m a r e available. E a c h d i o d e is typically 25 in
length. T h e m a x i m u m c o u n t r a t e of e a c h d i o d e c a n b e
6
greater t h a n rays p e r second. C C D a r r a y s a r e
available with r e a d o u t times of several m i c r o s e c o n d s ,
w h e n used as o n e - d i m e n s i o n a l a r r a y s (streak c a m e r a
m o d e ) . T h e i r t o t a l d i m e n s i o n s a r e typically less t h a n
1 c m with e a c h d e t e c t o r d i m e n s i o n being a p p r o x i m
ately 25 . E x a m p l e s of t h e use of these d e t e c t o r s
for time-resolved m e a s u r e m e n t s a r e given in t h e
following.
T h e r a n g e of angles s i m u l t a n e o u s l y incident o n a
s a m p l e c a n be increased by using a c u r v e d focusing
m o n o c h r o m a t o r . I n c r e a s i n g t h e r a n g e of incident
angles is p a r t i c u l a r l y a d v a n t a g e o u s for single-crystal
e x p e r i m e n t s since this relaxes t h e need for c h a n g i n g
the o r i e n t a t i o n of t h e s a m p l e . O n e e x a m p l e of a n
e x p e r i m e n t t a k i n g a d v a n t a g e of this is given b y
C l a r k e et al. (1991). U s i n g a b e n t g e r m a n i u m
m o n o c h r o m a t o r crystal, a n incident a n g u l a r r a n g e of
0.07 w a s o b t a i n e d with a diffraction r e s o l u t i o n of 3
3
p a r t s in 10 . T h e y used a C C D d e t e c t o r as a o n e d i m e n s i o n a l position-sensitive d e t e c t o r t o collect a
r a n g e of scattered angles. T h i s d e t e c t o r allows diffrac
tion profiles t o be t a k e n as r a p i d l y as o n e every 25 .
In their e x p e r i m e n t , C l a r k e et al. m e a s u r e d t h e (004)
Bragg p e a k of thin films of G a 0 9 5I n 0 0 5A s epitaxially
grown on G a A s . They present data acquired during
r a p i d t h e r m a l a n n e a l i n g with a time r e s o l u t i o n of
100 m s per p a t t e r n .
A n o t h e r w a y t o increase t h e incident b e a m intensity
is t o increase t h e m o n o c h r o m a t o r b a n d p a s s , t h e
resulting increase in time r e s o l u t i o n being m o r e desir
able t h a n t h e loss in diffraction r e s o l u t i o n . X - r a y
m o n o c h r o m a t o r s for diffraction e x p e r i m e n t s typically
w o r k by using d y n a m i c a l diffraction from perfect
single crystals, t h e choice of m o n o c h r o m a t o r crystals
then d e t e r m i n i n g t h e w a v e l e n g t h b a n d p a s s . T h e avail
ability of large h i g h - q u a l i t y single crystals of silicon
a n d g e r m a n i u m m e a n s t h a t they a r e m o s t c o m m o n l y
used. T h e b a n d p a s s for t h e (111) B r a g g p e a k of silicon
is 0.01 % a n d for G e ( l 11) is 0 . 0 2 % . T h e s e values result
in a r e a s o n a b l y high diffraction r e s o l u t i o n a n d h i g h e r
resolution c a n b e o b t a i n e d b y using h i g h e r o r d e r
Bragg reflections. A b a n d p a s s of 1 % is usually m o r e
t h a n e n o u g h diffraction r e s o l u t i o n a n d c a n lead t o a
large increase in intensity relative t o S i ( l l l ) o r
G e ( l 11). T h e difficulty in o b t a i n i n g large h i g h - q u a l i t y
single crystals of t h e a p p r o p r i a t e m a t e r i a l c a n
be sidestepped by using artificially m o d u l a t e d m a t e r
ials. O n e such e x a m p l e uses t u n g s t e n - s i l i c o n m u l t i
layers with a p e r i o d of 2.3 n m ( S t e p h e n s o n 1988). U s e
of these multilayer m o n o c h r o m a t o r s a n d a p h o t o d i o d e a r r a y linear d e t e c t o r h a s resulted in a system
c a p a b l e of a c q u i r i n g diffraction p a t t e r n s with a t i m e

Diffraction,

Time-Resolved

r e s o l u t i o n of a few milliseconds from small polycrys

talline m e t a l r i b b o n s . T h i s s e t u p h a s been used t o
m e a s u r e t h e crystallization of metallic glasses ( S u t t o n
et al. 1988) a n d t h e o r d e r i n g in C u 3 A u ( L u d w i g et al.
1988).
I n energy-dispersive x-ray diffraction, a wellcollimated b e a m containing m a n y
wavelengths
(energies) strikes a s a m p l e a n d scatters i n t o a n energysensitive d e t e c t o r a t s o m e fixed scattering angle.
B r a g g ' s law m e a n s t h a t only c e r t a i n w a v e l e n g t h s will
scatter i n t o t h a t angle a n d diffraction profiles similar
t o c o n v e n t i o n a l p o w d e r x-ray diffraction
are
o b t a i n e d . T h i s t e c h n i q u e h a s t h e a t t r a c t i v e feature
t h a t only o n e incident angle a n d o n e diffraction angle
need b e a c c o m m o d a t e d in t h e s a m p l e c h a m b e r . It is
often u s e d in h i g h - p r e s s u r e diffraction m e a s u r e m e n t s
u s i n g d i a m o n d anvil cells. S o far this t e c h n i q u e h a s
n o t b e e n widely used for time-resolved m e a s u r e m e n t s
b u t for t h e p r e s s u r e e x p e r i m e n t s , diffraction profiles
a r e c o n v e n t i o n a l l y a c q u i r e d w i t h timescales of several
m i n u t e s . T h e diffraction r e s o l u t i o n of these experi
m e n t s is a g a i n of o r d e r 1 % . X - r a y s a r e m e a s u r e d b y
a n intrinsic g e r m a n i u m solid-state d e t e c t o r which
h a v e a m a x i m u m c o u n t r a t e of a r o u n d 5000 rays p e r
s e c o n d . T h e r e f o r e , until faster d e t e c t o r s b e c o m e avail
able, t h e best time r e s o l u t i o n will r e m a i n several
s e c o n d s p e r p a t t e r n . A n e x a m p l e of this type of
m e a s u r e m e n t is r e p o r t e d b y B a u b l i t z et al. (1981).
C o n c o m i t a n t with t h e s h o r t e n i n g time p e r diffrac
t i o n p a t t e r n , direct m e t h o d s r e q u i r e the d e v e l o p m e n t
of s a m p l e c h a m b e r s w h i c h allow t h e c h a n g i n g of t h e
s a m p l e e n v i r o n m e n t o n c o m p a r a b l e timescales. Ste
p h e n s o n et al. (1989) a n d B r a u e r et al.(1990) describe
t e c h n i q u e s d e v e l o p e d for fast in situ t e m p e r a t u r e
c h a n g e s . T h e i r t e c h n i q u e s a r e b a s e d o n using small
metallic ribbons w h i c h a r e h e a t e d b y J o u l e selfh e a t i n g a n d t h e t e m p e r a t u r e is m e a s u r e d b y a fast
6
- 1
infrared p y r o m e t e r . H e a t i n g rates of 1 0 K s
and
1
c o o l i n g rates of 1500 s " w i t h o u t o v e r s h o o t i n g a r e
demonstrated.
2. Stroboscopic

Measurements

T h e diffraction geometries for s t r o b o s c o p i c m e a s u r e

m e n t s a r e t h e s a m e as for t h e direct m e t h o d s a l r e a d y
described. S t r o b o s c o p i c m e t h o d s c a n be used w h e n
t h e time r e s o l u t i o n is limited b y low c o u n t i n g rates
a n d n o t by t h e m a x i m u m c o u n t r a t e of the d e t e c t o r
system. T h e y c a n also b e used t o e x t e n d the r a n g e of
diffraction angles.
T w o e x a m p l e s serve t o d e m o n s t r a t e t h e p o w e r of
t h e s t r o b o s c o p i c t e c h n i q u e . T h e first e x a m p l e is a n
e x p e r i m e n t t o m e a s u r e t h e m e l t i n g a n d recrystallizat i o n of a silicon surface d u r i n g a h i g h - p o w e r laser
pulse ( L a r s o n et al. 1986). By t a k i n g a d v a n t a g e of t h e
p u l s e d n a t u r e of a s y n c h r o t r o n source a n d by synch
r o n i z i n g t h e laser pulses a n d m e a s u r e m e n t s t o the
x-ray pulses, a t i m e r e s o l u t i o n of less t h a n 1 ns w a s
achieved.

569

X-Ray

Diffraction,

Time-Resolved

T h e second e x a m p l e uses n e w diffraction tech

niques developed t o s t u d y t h e surfaces of crystals.
W a n g a n d O c k o (1992) studied t h e (111) surface of
single crystals of gold in situ in a n electrochemical cell.
W i t h diffraction m e a s u r e m e n t s s y n c h r o n i z e d t o vol
tage pulses applied t o t h e cell, they were able t o s t u d y
the time r e s p o n s e of a surface r e c o n s t r u c t i o n i n d u c e d
o n the surface of t h e gold single-crystal electrode with
a time resolution of a few seconds.

5. Future

Possibilities

This article h a s focused o n the t e c h n i q u e s of in situ

real-time diffraction m e a s u r e m e n t s a n d diffraction
geometries r a t h e r t h a n o n results. Time-resolved xr a y diffraction is a rapidly evolving field a n d the
choice of t h e best t e c h n i q u e t o use often d e p e n d s o n
t h e system u n d e r study.
T h e resulting increase in intensity from the use of
s y n c h r o t r o n s as x-ray sources h a s m e a n t a n e n o r m o u s
increase in possibilities, n o t only for time-resolved
m e a s u r e m e n t s , b u t for all x-ray diffraction. T h e rela
tively recent a d v e n t of s y n c h r o t r o n s d e d i c a t e d for xr a y sources h a s also led t o accessibility for a wide
r a n g e of users. N e w diffraction t e c h n i q u e s , new x-ray
detector d e v e l o p m e n t s a n d t h e m o r e intense s y n c h r o
t r o n sources c u r r e n t l y u n d e r c o n s t r u c t i o n m e a n t h a t
time-resolved x-ray diffraction will c o n t i n u e its r a p i d
evolution for m a n y years to c o m e .
I n conclusion, a n e x a m p l e of o n e such new tech
n i q u e will be given. It h a s been s h o w n b y S u t t o n et al.
(1991) t h a t a spatially c o h e r e n t b e a m of 0.155 n m
rays c a n be o b t a i n e d with sufficient intensity t o per
form a diffraction e x p e r i m e n t . T h i s m e a n s t h a t a
technique called d y n a m i c light scattering o r intensity
fluctuation s p e c t r o s c o p y c a n be e x t e n d e d i n t o t h e
h a r d x-ray region. W i t h light, this t e c h n i q u e is c o m
m o n l y used t o m e a s u r e t h e kinetics of t r a n s i t i o n s in
t r a n s p a r e n t m a t e r i a l s o n length scales of t h e o r d e r of
the wavelength of light o r longer. W i t h rays, t h e
t e c h n i q u e c a n be used for o p a q u e m a t e r i a l s a n d for
m u c h s h o r t e r length scales. It is also o n e of t h e few
techniques which c a n directly m e a s u r e kinetic p a r a m
eters in equilibrium systems.
See also: Thermophysical
X-Ray Powder Diffraction

Measurements,

Subsecond;

Bibliography
Baublitz A Jr, Arnold V, Ruoff A L 1981 Energy
dispersive x-ray diffraction from high pressure polycrystalline specimens using synchrotron radiation. Rev. Sci.
Instrum. 52: 1616-24
Brauer S, Ryan D H, Strom-Olsen J O, Sutton M, Stephen
son G 1990 Pyrometric temperature controller for
million degree per second heating. Rev. Sci. Instrum. 61:
2214-19

570

Clarke R, Dos Passos W, Lowe W, Rodricks G, Brizard C

1991 Real-time x-ray studies of strain kinetics in
hijGa^jjAs quantum well structures. Phys. Rev. Lett. 66:
317-20
Larson C, Tischler J Z, Mills D 1986 Nanosecond
resolution time-resolved x-ray study of silicon during
pulsed-laser irradiation. / . Mater. Res. 1: 144-54
Ludwig F Jr, Stephenson G B, Jordan-Sweet J L, Mainville J, Yang Y S, Sutton 1988 Nucleated and continu
ous ordering in Cu 3Au. Phys. Rev. Lett. 61: 1859-62
Rodricks B, Clarke R, Smither R, Fontaine A 1989 A
virtual phase CCD detector for synchrotron radiation
applications. Rev. Sci. Instrum. 60: 2586-91
Stephenson G 1988 Time resolved x-ray scattering using a
high intensity multilayer monochromator. Nucl. Methods
Instrum. A 266: 447-51
Stephenson G B, Ludwig F Jr, Jordan-Sweet J L, Mainville J, Yang Y S, Sutton 1989 Instrumentation for
millisecond-resolution scattering studies. Rev. Sci.
Instrum. 60: 1537-40
Sutton M, Mochrie S G, Greytak T, Nagler S E, Bermann L
Held G, Stephenson G 1991 Observation of speckle
by diffraction with coherent x-rays. Nature. 352: 608-10
Sutton M, Yang Y S, Mainville J, Strom-Olsen J O,
Altounian Z, Stephenson G B, Ludwig F Jr 1988
Crystallization of amorphous NiZr 2. Mater. Sci. Eng. 97:
307-11
Wang J, Ocko 1992 In situ x-ray diffraction and
reflectivity studies of the Au(III)/electrolyte interface:
reconstruction and anion adsorption. Phys. Rev. (in
press)
M. Sutton
[McGill University, M o n t r e a l , C a n a d a ]

X-Ray Fluorescence Spectrometry

I n s t r u m e n t a l element-analysis m e t h o d s b a s e d o n xr a y spectra m a y be classified by m e a n s of spectral
excitation a n d dispersion. X - r a y fluorescence s p e c t r o
m e t r y ( X R F S ) uses x-ray excitation a n d either
w a v e l e n g t h o r energy dispersion. A m o n g elemental
analysis m e t h o d s , x-ray fluorescence s p e c t r o m e t r y is
u n s u r p a s s e d in its c o m b i n a t i o n of convenience, speed,
a n d precision a n d a c c u r a c y , a n d in its versatility a n d
latitude of applicable elements a n d c o n c e n t r a t i o n
r a n g e s , i n s t r u m e n t c o m p o n e n t s a n d accessories, oper
a t i o n a l m o d e s a n d c o n d i t i o n s , analytical techniques
a n d specimen forms. T h i s article outlines the
principles, i n s t r u m e n t a t i o n , a n d t e c h n i q u e s of w a v e
length-dispersive x-ray
fluorescence
spectrometric
analysis.

1. Definition,

Scope,

Advantages,

Limitations

X - r a y fluorescence s p e c t r o m e t r y is a n o n d e s t r u c t i v e
i n s t r u m e n t a l m e t h o d of qualitative a n d q u a n t i t a t i v e
analysis for chemical elements b a s e d o n the w a v e
lengths a n d intensities of their x-ray-excited spectral

X-Ray

lines. " P r i m a r y " rays, usually from a n x-ray t u b e ,

excite each specimen element t o emit its x-ray spectral
lines, which h a v e w a v e l e n g t h s characteristic of t h a t
element (qualitative analysis) a n d intensities related t o
its c o n c e n t r a t i o n ( q u a n t i t a t i v e analysis).
I n favorable cases, c o m m e r c i a l flat-crystal spec
t r o m e t e r s a r e applicable t o all elements d o w n t o
a t o m i c n u m b e r 9 (fluorine), c o n c e n t r a t i o n s from 100
1
to 0.0001 w t % in solids a n d d o w n t o ~ 0 . 1 g m in
liquids, isolated m a s s e s d o w n t o ~ 1 n g , a n d films a s
" t h i n " as ~ 0 . 0 1 m o n o l a y e r . Special accessories per
mit analysis for beryllium, b o r o n , c a r b o n , n i t r o g e n
a n d oxygen. Sensitivity decreases m a r k e d l y for ele
m e n t s below a t o m i c n u m b e r 13 ( a l u m i n u m ) .
Specimens c a n h a v e practically a n y form (see Sect.
11).
Typical
maximum
specimen
size
is
2
20 c m x 2.5 c m thick, b u t special accessories appli
cable t o s o m e i n s t r u m e n t s p e r m i t analysis o n very
large a n d very small specimens a n d small selected
areas. T h e effective specimen a r e a is defined b y a
2
w i n d o w e d m a s k a n d is typically 1-5 c m . T h e effective
specimen thickness is d e t e r m i n e d n o t b y t h e d e p t h t o
which t h e p r i m a r y rays p e n e t r a t e , b u t b y t h e d e p t h
from which t h e m e a s u r e d rays c a n e m e r g e . I n
general, this layer is 0 . 1 - 1 m m , a n d is d e e p e r t h e
s h o r t e r t h e m e a s u r e d w a v e l e n g t h a n d t h e lower t h e
specimen a b s o r p t i o n for t h a t wavelength. F o r q u a n t i
tative analysis, all specimens m u s t b e "infinitely
t h i c k " for all m e a s u r e d w a v e l e n g t h s o r else h a v e t h e
s a m e thickness. X - r a y fluorescence s p e c t r o m e t r y c a n
be used t o m e a s u r e t h e thickness of layers less t h a n
infinitely thick b u t o f t h e s a m e c o m p o s i t i o n .
Analytical precision m a y b e 0.1 % relative for
m a j o r a n d m i n o r c o n s t i t u e n t s , b u t is m u c h p o o r e r for
traces. Analytical a c c u r a c y is d e t e r m i n e d b y t h e a c
c u r a c y of t h e s t a n d a r d s , t h e physical a n d chemical
similarity of s t a n d a r d s a n d samples, a n d t h e efficacy
of t h e m a t r i x c o r r e c t i o n m e t h o d (see Sect. 10). T h e
m e t h o d is substantially n o n d e s t r u c t i v e , b u t s o m e
m a t e r i a l s u n d e r g o radiolysis a n d / o r r a d i a t i o n d a m a g e
in t h e intense p r i m a r y r a d i a t i o n , o r o x i d a t i o n in t h e
o z o n e it p r o d u c e s . W h e n as-received s a m p l e s c a n b e
analyzed with m i n i m a l p r e p a r a t i o n , t h e m e t h o d is
extremely r a p i d a n d c o n v e n i e n t .
M a n u a l a n d a u t o m a t i c sequential x-ray s p e c t r o m
eters (see Sect. 8) cost a b o u t 75 000 a n d 150 000 U S
dollars, respectively. T h e m a n u a l i n s t r u m e n t c a n b e
c o n v e r t e d t o t h e sequential. A n a u t o m a t i c s i m u l t a n
e o u s s p e c t r o m e t e r (see Sect. 8) costs a b o u t 225 000 U S
dollars for 10 c h a n n e l s a n d u p t o 350 000 U S d o l l a r s
for 30. X - r a y t u b e s cost a b o u t 5000 U S d o l l a r s a n d
last a few t h o u s a n d h o u r s .

2. X Rays and X-Ray

Spectra

X rays m a y b e defined a s e l e c t r o m a g n e t i c r a d i a t i o n in
5
the wavelength region ~ 1 0 ~ - 1 0 n m p r o d u c e d b y
deceleration of high-energy electrons a n d / o r b y elec-

Fluorescence

Spectrometry

Wavelength

Figure 1
Section of an atom of an element of high atomic number,
showing the electron transitions that produce the principal
characteristic x-ray spectral lines and the x-ray spectrum
from an x-ray tube having a target of high atomic number
and operated at high potential (from Introduction to
X-Ray Spectrometric Analysis, courtesy of Plenum Press)

t r o n t r a n s i t i o n s t o t h e inner orbits of a t o m s . I n
analytical x-ray fluorescence s p e c t r o m e t r y , t h e appli
cable spectral region is ~ 0 . 0 1 - 2 n m a n d with special
accessories t o ~ 1 0 n m . X rays a r e characterized b y
w a v e l e n g t h ( n m ) p h o t o n energy (eV), a n d inten
sity / ( p h o t o n s , o r " c o u n t s , " p e r second). T h e w a v e
length a n d p h o t o n energy a r e related reciprocally:
E= 124 000/A. T h e c o n s t a n t in this e q u a t i o n is (he/
11
e) x 1 0 n m m~ \ w h e r e h is P l a n c k ' s c o n s t a n t , c is t h e
velocity of light a n d e is t h e electron c h a r g e . T h e r e a r e
t w o types of x-ray emission spectra: c o n t i n u o u s a n d
characteristic-line (see F i g . 1).
The continuous spectrum, continuum or "brehmss t r a h l u n g " o c c u r s in significant intensity only with
electron excitation a n d arises from d e c r e m e n t a l decel
e r a t i o n of electrons. It is c h a r a c t e r i z e d by a c o n t i n u
o u s b a n d of wavelengths, s t a r t i n g a t a m i n i m u m
w a v e l e n g t h d e t e r m i n e d b y t h e electron acceleration
p o t e n t i a l V (A m in = 124 000/) rising t o m a x i m u m
intensity a t 1.5 A m i n, a n d decreasing in intensity a t
increasing wavelength (Fig. 1).
C h a r a c t e r i s t i c x-ray line spectra arise w h e n v a c a n
cies o c c u r in t h e K , L a n d shells of a t o m s a n d
electrons from shells further o u t fall i n t o these v a c a n
cies, t h e r e b y losing energy, which a p p e a r s as x-ray
photons. Fig. 1 shows the transitions that produce the
principal lines a n d t h e s y m b o l s a n d relative intensities

571

X-Ray

Fluorescence

Spectrometry

M i l l

of these lines. E l e m e n t s of low, i n t e r m e d i a t e a n d high

a t o m i c n u m b e r h a v e K , K - L a n d K - L - M spectra,
respectively. F o r a specified line, say K a ^ w a v e l e n g t h
decreases ( p h o t o n energy increases) m o n o t o n i c a l l y as
a t o m i c n u m b e r increases, regardless of physical a n d
chemical state.

3. Excitation

of Characteristic

X-Ray

Spectra

Excitation of x-ray line spectra consists in expulsion

of K-, L- a n d / o r M-shell electrons in large n u m b e r s .
Excitation m a y b e effected by high-energy particles
(electrons, p r o t o n s , d e u t e r o n s , a l p h a s a n d heavier
ions) o r high-energy p h o t o n s (x a n d rays). E a c h h a s
a d v a n t a g e s a n d limitations, a n d s p e c t r o m e t e r s a p p l y
ing each are in use. Interest here is limited t o t h e
electron excitation t h a t p r o d u c e s t h e p r i m a r y b e a m in
the x-ray t u b e a n d the x-ray excitation t h a t o c c u r s
w h e n this b e a m irradiates the specimen.
Excitation requires energy. T h e m i n i m u m energy
t h a t a n electron m u s t h a v e t o expel a specified elec
t r o n from a specified orbital in a n a t o m of a specified
element is the excitation p o t e n t i a l . T h e m i n i m u m
p h o t o n energy o r t h e m a x i m u m w a v e l e n g t h t h a t a
p h o t o n m u s t h a v e t o expel t h a t electron is the critical
a b s o r p t i o n energy o r a b s o r p t i o n edge. E a c h element
h a s o n e K , three L a n d five excitation p o t e n t i a l s ,
critical energies a n d a b s o r p t i o n edges c o r r e s p o n d i n g
to the orbitals in Fig. 1, insofar as the element h a s
those orbitals.
F o r a specified element, t h e closer a n electron
orbital lies t o t h e positive a t o m nucleus, t h e m o r e
tightly it is b o u n d a n d t h e higher t h e excitation
energy, t h a t is, t h e higher the excitation p o t e n t i a l o r
critical energy a n d the s h o r t e r the a b s o r p t i o n edge.
Similarly, for a specified orbital, say L I I I , t h e higher
the a t o m i c n u m b e r , the m o r e tightly t h e electrons a r e
b o u n d a n d t h e higher t h e excitation energy.
In x-ray
fluorescence
s p e c t r o m e t e r s , t h e x-ray
source used to excite the specimen is usually a n x-ray
t u b e , b u t a r a d i o i s o t o p e is s o m e t i m e s used. In t h e xray t u b e (see Sect. 5), electrons p r o d u c e c o n t i n u u m
r a d i a t i o n by stepwise deceleration a n d the target line
s p e c t r u m b y the c r e a t i o n of electron-orbital v a c a n
cies. T h e p r i m a r y b e a m c o m p r i s e s t h e t a r g e t line
spectrum superimposed on the continuum. The char
acteristic s p e c t r u m of each specimen element is
excited only by p r i m a r y c o n t i n u u m a n d target lines of
wavelength s h o r t e r t h a n the a b s o r p t i o n edges of its K ,
L a n d / o r orbitals.
T h e p r i m a r y b e a m excites n o c o n t i n u u m in the
specimen b u t the specimen scatters p r i m a r y rays.
T h u s , the rays leaving the specimen c o m p r i s e the
emitted characteristic spectra of t h e specimen ele
m e n t s a n d the scattered p r i m a r y c o n t i n u u m a n d tar
get lines. Scattered c o n t i n u u m largely c o n s t i t u t e s t h e
b a c k g r o u n d of t h e specimen s p e c t r u m .

572

Figure 2
Distinction between wavelength dispersion (right of
specimen), in which the rays are dispersed spacially by
wavelength prior to detection, and energy dispersion (left
of specimen), in which all rays are detected
simultaneously and detector output pulses are separated
by amplitude electronically (from Introduction to X-Ray
Spectrometric Analysis, courtesy of Plenum Press)

4.

Dispersion

A n y analytical m e t h o d involving x-ray spectral lines

m u s t p r o v i d e a m e a n s t o p e r m i t a line of e a c h
specimen element t o be m e a s u r e d individually. T w o
such m e a n s a r e in c o m m o n use. I n energy dispersion,
t h e d e t e c t o r receives e m i t t e d a n d scattered rays
directly from t h e specimen a n d for e a c h a b s o r b e d
p h o t o n p r o d u c e s a n electric pulse of a m p l i t u d e p r o
p o r t i o n a l t o the p h o t o n energy (see Sect. 7). T h e
amplified d e t e c t o r o u t p u t u n d e r g o e s electronic pulseheight analysis t o s e p a r a t e t h e pulses for e a c h spectral
line. I n w a v e l e n g t h dispersion (see Sect. 6), t h e rays
a r e s e p a r a t e d spacially by w a v e l e n g t h b y crystal dif
fraction p r i o r t o detection, so t h a t usually t h e d e t e c t o r
receives only o n e w a v e l e n g t h a t a time. F i g u r e 2
illustrates the t w o m o d e s in a highly simplified form
for three of t h e m a n y w a v e l e n g t h s e m i t t e d o r scat
tered by t h e s a m p l e .

5. InstrumentationX-Ray

Generator

T h e wavelength-dispersive x-ray fluorescence spec

t r o m e t e r c o m p r i s e s a n x-ray g e n e r a t o r (x-ray t u b e
a n d p o w e r supply), specimen c h a m b e r , s p e c t r o goniometer,
and
electronic
detection
and
r e a d o u t system.
T h e x-ray t u b e c o m p r i s e s a m e t a l target a n d t u n g
sten filament in a n x - r a y - p r o o f m e t a l h e a d h a v i n g a
thin beryllium w i n d o w a n d sealed t o a r e e n t r a n t glass
t u b e . T h e t u b e a n d h e a d c o n s t i t u t e a sealed highv a c u u m enclosure. In o p e r a t i o n , t h e filament is h e a t e d
t o incandescence b y electric c u r r e n t a n d emits elec
t r o n s , which a r e accelerated to t h e target w h e r e they

X-Ray

Fluorescence

Spectrometry

5 0 kV

Figure 3
X-ray generator: the solid and dashed waveforms at the top correspond to the high (solid arrow) and low (dashed arrow)
settings of the autotransformer. The resistor and capacitor constitute the constant-potential filter. The switch represents
various automatic safety devices

excite x-ray emission, w h i c h emerges t h r o u g h t h e

beryllium w i n d o w . T h e t a r g e t m u s t b e w a t e r c o o l e d
because o p e r a t i o n at, say, 5 0 k V - 5 0 m A dissipates
2500 W , of w h i c h only 1-2% p r o d u c e s r a y s , t h e
r e m a i n d e r h e a t . T u n g s t e n is t h e m o s t c o m m o n
g e n e r a l - p u r p o s e t a r g e t , b u t c h r o m i u m is preferable
for excitation of s p e c t r a of elements 9 - 2 3 ( f l u o r i n e vanadium).
T h e x - r a y - t u b e p o w e r s u p p l y c o m p r i s e s a lowp o w e r a c supply for t h e x-ray t u b e filament, highp o t e n t i a l d c s u p p l y for t h e target, stabilization circuits
a n d safety devices. F i g u r e 3 s h o w s the m a i n c o m p o
n e n t s a n d the sequence of a c a n d d c w a v e f o r m s . T h e
filament supply c o m p r i s e s a r h e o s t a t a n d s t e p - d o w n
t r a n s f o r m e r , delivers u p t o ~ 1 0 V - 5 A a c , a n d per
mits v a r i a t i o n of t h e filament p o w e r a n d t h e r e b y of
t e m p e r a t u r e , electron emission a n d t u b e c u r r e n t . T h e
target supply c o m p r i s e s a v a r i a b l e a u t o t r a n s f o r m e r ,
step-up t r a n s f o r m e r , rectifier a n d o p t i o n a l c o n s t a n t p o t e n t i a l filter, a n d delivers u p t o 50, 75 o r 100 k V a t
u p t o 75 m A full-wave p u l s a t i n g o r c o n s t a n t - p o t e n t i a l
dc. T h e t a r g e t p o t e n t i a l a n d c u r r e n t m a y b e varied
from zero t o m a x i m u m values with their respective
c o n t r o l s a n d a r e indicated o n their respective m e t e r s .
Provision is m a d e for stabilization o f t h e a c line,
target p o t e n t i a l (kV) a n d t u b e c u r r e n t ( m A ) . Safety
devices a u t o m a t i c a l l y s h u t off t h e s u p p l y w h e n t h e
electric c u r r e n t a n d c o o l i n g - w a t e r p r e s s u r e exceed
preset limits a n d / o r t h e c a b i n e t d o o r s a r e o p e n e d .
T h e flat-crystal wavelength-dispersive s p e c t r o m e t e r
(see Sect. 6) is extremely wasteful of e m i t t e d specimen
spectral r a d i a t i o n , so h i g h - p o w e r ( ^ 2500 W ) g e n e r a
t o r s a r e r e q u i r e d . E n e r g y dispersion uses n o g o n i
o m e t e r , so t h e d e t e c t o r is n e a r t h e specimen a n d
intercepts a large solid angle of r a d i a t i o n , p e r m i t t i n g

excitation b y l o w - p o w e r ( ^ 100 W ) x-ray o r r a d i o i s o

t o p e sources.

6. InstrumentationSpecimen
Spectrogoniometer

Chamber

and

S o m e s p e c t r o g o n i o m e t e r s a r e s e p a r a t e self-contained
table-top instruments having the x-ray-tube window
directed d o w n w a r d i n t o a c h a m b e r h a v i n g a r e m o v
able d r a w e r for specimens ~ 2 . 5 c m in d i a m e t e r a n d
thickness. T h e s e i n s t r u m e n t s c a n be r e a r r a n g e d with
t h e x-ray w i n d o w u p w a r d ("inverted o p t i c s " ) for very
large specimens, such as i n g o t s , engine p a r t s a n d a r t
objects. I n m o s t s p e c t r o m e t e r s , t h e g o n i o m e t e r h a s
inverted optics b u t is enclosed o n all sides, limiting
m a x i m u m specimen size t o ~ 5 c m d i a m e t e r by
~ 2 . 5 c m thick. T h e specimen c h a m b e r m a y h o l d a
single specimen o r p r o v i d e for a u t o m a t i c sequential
i n d e x i n g of u p t o 30.
T h e s p e c t r o g o n i o m e t e r (Fig. 4) c o m p r i s e s t w o colli
m a t o r s , a n a n a l y z e r crystal a n d a d e t e c t o r a r r a n g e d
o n a m a n u a l o r m o t o r - d r i v e n precision r o t a t i n g
m e c h a n i s m . T h e c o l l i m a t o r s consist of spaced parallel
m e t a l foils rigidly held in rectilinear m e t a l tunnels.
T h e single-crystal b a r serves as a n x-ray diffraction
g r a t i n g . T h e d e t e c t o r is described in Section 7. O n e
c o l l i m a t o r is fixed a t t h e o u t p u t e n d of t h e specimen
c h a m b e r . T h e crystal is bisected b y a n d r o t a t e s a b o u t
t h e g o n i o m e t e r axis a t angle 0 p e r u n i t time as the
o t h e r c o l l i m a t o r a n d d e t e c t o r r o t a t e t o g e t h e r a t angle
20 p e r u n i t time. A t w a v e l e n g t h s s h o r t e r t h a n
~ 0 . 2 5 n m the specimen-crystal-detector radiation
p a t h m a y be air, b u t a t longer w a v e l e n g t h s x-ray
573

X-Ray

Fluorescence

Spectrometry

Figure 4
X-ray spectrogoniometer and electronic detection and readout components. The pulse diagrams show pulse height versus
time. The pulse-height selector passes pulses having amplitude between two discriminator settings, baseline BL and
window width W

a b s o r p t i o n in air is p r o h i b i t i v e a n d t h e g o n i o m e t e r is
enclosed in a flexible helium-flushed h o o d o r a rigid
vacuum hood.
T h e c o n s t i t u e n t elements in t h e specimen emit their
characteristic x-ray spectra in all directions, b u t only a
b u n d l e of rays parallel t o the foils of t h e first collima
t o r reaches t h e crystal. A t each a n g u l a r p o s i t i o n , t h e
crystal diffracts only t h e w a v e l e n g t h t h a t satisfies
the B r a g g law: = 2d sin 0, w h e r e d is the i n t e r p l a n a r
spacing of the crystal planes parallel t o the surface
a n d is a n integer defining the diffraction o r d e r . N o t e
t h a t a t a specified m o r e t h a n o n e w a v e l e n g t h c a n be
diffracted: in first o r d e r (n = 1), /2 in second o r d e r
(n 2 ) , . . . , / in t h o r d e r . T h u s , as t h e crystal
r o t a t e s over its r a n g e , it diffracts in sequence all
incident x-ray w a v e l e n g t h s u p t o a m a x i m u m of
2d n m . Several crystals h a v i n g different d spacings a r e
required t o cover t h e entire w a v e l e n g t h region, for
e x a m p l e , lithium fluoride (2d 0.403 n m ) , p e n t a e r y t h r i tol ( P E T , 2 ^ 0 . 8 7 4 n m ) a n d p o t a s s i u m h y d r o g e n
p h t h a l a t e ( K H P , 2</2.66 n m ) .

7. InstrumentationElectronic
Readout
Components

Detection

and

T h e d e t e c t o r r o t a t e s with t h e crystal, is always in

position t o receive a n y diffracted rays, a n d for e a c h
a b s o r b e d x-ray p h o t o n p r o d u c e s a n electric pulse of
a m p l i t u d e p r o p o r t i o n a l t o t h e p h o t o n energy. T h r e e
types of d e t e c t o r a r e c o m m o n l y used in analytical xr a y s p e c t r o m e t e r s : t h e gas-filled p r o p o r t i o n a l c o u n t e r

574

(Fig. 4) c o m p r i s e s a cylindrical m e t a l - t u b e c a t h o d e
h a v i n g a n axial wire a n o d e a n d insulating e n d s , a n d
filled with a gas, usually a r g o n o r x e n o n . T w o d i a m e t
rically o p p o s i t e x-ray w i n d o w s a r e p r o v i d e d . F o r
wavelengths shorter than ~ 0 . 2 5 n m the windows m a y
be p e r m a n e n t l y sealed beryllium o r mica. F o r longer
w a v e l e n g t h s , the w i n d o w s m u s t be of thin plastic,
usually 6- o r 3- M y l a r , t o reduce x-ray a b s o r p t i o n .
Such w i n d o w s a r e n o t gas-tight, so t h e gas, usually a
9 0 - 1 0 v o l . % m i x t u r e of a r g o n a n d m e t h a n e , is passed
c o n t i n u o u s l y t h r o u g h these "flow c o u n t e r s . " T h e
scintillation c o u n t e r c o m p r i s e s a disk of t h a l l i u m activated s o d i u m iodide, N a l ( T l ) , affixed o u t s i d e t h e
p h o t o c a t h o d e e n d of a multiplier p h o t o t u b e . T h e
lithium-drifted silicon, Si(Li), d e t e c t o r is a disk of
specially t r e a t e d single-crystal silicon.
E a c h x-ray p h o t o n a b s o r b e d in a gas-filled, scintil
lation o r silicon d e t e c t o r ejects a n electron from, say,
the o u t e r m o s t orbital of a gas, iodine o r silicon a t o m ,
respectively, a n d i m p a r t s substantially all of its p h o
t o n energy t o kinetic energy of this p h o t o e l e c t r o n . I n
t h e gas-filled detector, this p h o t o e l e c t r o n e x p e n d s its
energy in p r o d u c i n g m o r e gas-ion/electron p a i r s .
E a c h of these s e c o n d a r y electrons initiates a n " a v a
l a n c h e " of still m o r e i o n - e l e c t r o n p a i r s so t h a t for
4
e a c h electron p r o d u c e d b y the p h o t o e l e c t r o n ~ 1 0 6
10 electrons r e a c h t h e a n o d e wire t o c o n s t i t u t e a n
o u t p u t pulse. I n t h e scintillation detector, t h e p h o t o
electron e x p e n d s its energy in f o r m i n g a b u r s t of
blue-light p h o t o n s , ~ 1 0 % of w h i c h strike t h e p h o t o c a t h o d e of t h e multiplier p h o t o t u b e a n d result in a
p h o t o e l e c t r o n arriving a t t h e electron multiplier. E a c h

X-Ray

such electron results in a n o u t p u t pulse of ~ 1 0

electrons a t t h e multiplier o u t p u t . I n t h e Si(Li) detec
tor, t h e p h o t o e l e c t r o n e x p e n d s its energy in elevating
electrons from t h e filled energy b a n d s t o t h e c o n d u c
tion b a n d . T h e s e c o n d u c t i o n - b a n d electrons a l o n e
c o n s t i t u t e t h e o u t p u t pulse; t h e r e is n o m u l t i p l i c a t i o n
c o r r e s p o n d i n g with t h e a v a l a n c h i n g a n d electron m u l
tiplication of t h e gas a n d scintillation d e t e c t o r s . Evi
dently, t h e higher t h e incident x-ray p h o t o n energy,
t h e m o r e energetic is t h e initial p h o t o e l e c t r o n a n d t h e
m o r e i o n - e l e c t r o n p a i r s , light p h o t o n s a n d e l e c t r o n hole p a i r s a r e p r o d u c e d in t h e respective d e t e c t o r s .
T h i s is t h e basis of t h e p r o p o r t i o n a l i t y of t h e o u t p u t pulse a m p l i t u d e a n d x - r a y - p h o t o n energy.
D e t e c t o r sensitivity varies widely with x-ray w a v e
length, so it is c o m m o n p r a c t i c e t o use a t w o - w i n d o w
flow c o u n t e r for t h e l o n g - w a v e l e n g t h region b a c k e d
by a scintillation c o u n t e r for s h o r t e r w a v e l e n g t h s , as
s h o w n in Fig. 4.
T h e d e t e c t o r o u t p u t is a series of electric pulses of
m e a n a m p l i t u d e p r o p o r t i o n a l t o x - r a y - p h o t o n energy,
o n e for e a c h a b s o r b e d p h o t o n . If t h e crystal s i m u l t a n
eously diffracts m o r e t h a n o n e w a v e l e n g t h (,
/2,...,
/), t h e d e t e c t o r o u t p u t c o n t a i n s pulses of m o r e t h a n
o n e a m p l i t u d e . I n F i g . 4, three such a m p l i t u d e s a r e
s h o w n h i g h , m e d i u m a n d low, r e p r e s e n t i n g r a y s of
/2, a n d d e t e c t o r noise, respectively. T h e p r e a m p l i
fier a n d amplifier amplify all pulses w i t h o u t c h a n g e in
relative a m p l i t u d e . T h e pulse-height selector passes
only pulses h a v i n g a m p l i t u d e in t h e " w i n d o w "
between t w o preset levels, t h e " b a s e l i n e " a n d
" w i n d o w w i d t h . " I n t h e figure, t h e noise a n d higha m p l i t u d e pulses a r e rejected, t h e m e d i u m pulses
passed. T h e r a t e m e t e r integrates t h e selector o u t p u t
over a certain t i m e interval a n d displays t h e pulse r a t e
o r frequency o n a m e t e r o r c h a r t r e c o r d e r . T h e scaler
actually c o u n t s t h e pulses a n d displays t h e n u m b e r
digitally. T h e t i m e r is a digital clock a n d displays
c o u n t i n g time. T h e o p t i o n a l c o m p u t e r calculates c o m
p o s i t i o n from s t o r e d intensity d a t a a n d m a y o p e r a t e
an automatic spectrometer. The printer prints out
intensity a n d / o r c o m p o s i t i o n d a t a .

8. InstrumentationAutomated
Special-Purpose
Spectrometers

and

T h e i n s t r u m e n t described in Sect. 6 is a single-channel

manual or semiautomatic spectrometer. C o m p o n e n t s
(collimators, crystal, d e t e c t o r ) a n d o p e r a t i n g c o n
ditions (x-ray t u b e k V - m A , d e t e c t o r p o t e n t i a l , a m p l i
fier gain, pulse-selector settings) a r e c h a n g e d
m a n u a l l y o r by m a n u a l l y o p e r a t e d selectors. T w o
types of fully a u t o m a t i c s p e c t r o m e t e r s a r e in c o m m o n
use, sequential o r s i m u l t a n e o u s .
T h e sequential s p e c t r o m e t e r is a single-channel u n i t
p r o g r a m m e d t o index sequentially t o t h e 2 angle of
each spectral line, select a p p r o p r i a t e c o m p o n e n t s a n d
c o n d i t i o n s a n d m e a s u r e intensity, t h e n index t h e n e x t

Fluorescence

Spectrometry

specimen i n t o p o s i t i o n a n d r e p e a t t h e process c o n
tinually, all a u t o m a t i c a l l y a n d u n a t t e n d e d .
The simultaneous multichannel spectrometer has
a r r a y e d a b o u t t h e specimen, like s p o k e s a b o u t a wheel
h u b , u p t o 15 m e t a l p l a t e s , e a c h h o u s i n g o n e o r t w o
s p e c t r o m e t e r s c o m p r i s i n g c o l l i m a t o r s , crystal a n d d e
tector, a n d e a c h h a v i n g a r e a d o u t c h a i n . T h u s , the
i n s t r u m e n t c o m p r i s e s u p t o 30 c h a n n e l s . M o s t of
these a r e preset t o a specific x-ray line. T h e o t h e r s a r e
m o t o r - d r i v e n " s c a n n i n g " s p e c t r o m e t e r s of t h e type
described in Section 6. T h e s e a r e used for qualitative
analysis a n d for elements d e t e r m i n e d t o o infrequently
t o w a r r a n t preset c h a n n e l s . T h e s e i n s t r u m e n t s c a n
a c c u m u l a t e intensity d a t a for u p t o 30 elements in 1-2
m i n , w h e r e u p o n t h e next specimen is indexed i n t o
p o s i t i o n a n d m e a s u r e d , a n d so o n , all a u t o m a t i c a l l y
and unattended.
I n b o t h sequential a n d s i m u l t a n e o u s i n s t r u m e n t s ,
t h e intensity d a t a for s a m p l e s a n d s t a n d a r d s is i n p u t
t o a (usually) d e d i c a t e d c o m p u t e r for direct calcu
l a t i o n a n d p r i n t o u t of c o m p o s i t i o n . Such fully
a u t o m a t e d i n s t r u m e n t s a r e of inestimable value for
i n d u s t r i a l l a b o r a t o r i e s r e q u i r e d t o a n a l y z e daily very
large n u m b e r s of specific alloys, c e m e n t s , ceramics,
glasses, a n d so o n , a t m i n i m a l cost.
S p e c t r o m e t e r s for t h e u l t r a l o n g - w a v e l e n g t h region
( ^ 2 n m ) use x-ray g e n e r a t o r s c o m p r i s i n g special wind o wless x-ray t u b e s o p e r a t e d a t u p t o ~ 10 k V a n d t o
~ 500 m A , special p s e u d o c r y s t a l s h a v i n g 2d spacings
of 1 0 - 1 5 n m a n d w i n d o w l e s s d e t e c t o r s , all o p e r a t i n g
in high, clean v a c u u m .
T h e r e a r e relatively lightweight p o r t a b l e w a v e
length-dispersive s p e c t r o m e t e r s t h a t o p e r a t e from
b a t t e r i e s o r g e n e r a t o r s for field a n d e n v i r o n m e n t a l
use, b u t m o s t such a p p l i c a t i o n s use energy-dispersive
spectrometers.
Dynamic process-control spectrometers monitor
a n d c o n t r o l industrial processes, such as plating, ore
p r o c e s s i n g a n d reclaiming of p r e c i o u s m e t a l s . A n xray spectrometer at some point along the production
line m o n i t o r s , say, t i n - p l a t e thickness o n c o n t i n u o u s l y
m o v i n g sheet steel. W h e n t h e m o n i t o r e d x-ray inten
sity falls o u t s i d e previously established limits, the
i n s t r u m e n t either signals a n o p e r a t o r o r adjusts the
p l a t i n g c o n d i t i o n s t o c o r r e c t t h e fault.

9.

Operation

Q u a l i t a t i v e analysis is p e r f o r m e d by setting t h e crystal

a n d c o l l i m a t o r - d e t e c t o r a r m a t 0, t h e n m o t o r - d r i v
ing t h e m a t 0 a n d 2 p e r u n i t time, respectively,
t h r o u g h t h e a n g u l a r r a n g e of t h e g o n i o m e t e r as the
r a t e m e t e r r e c o r d s i n s t a n t a n e o u s x-ray intensity. T h e
result is a c h a r t of x-ray intensity as a function of 2,
s h o w i n g p e a k s , e a c h r e p r e s e n t i n g a different x-ray
line. T h e p e a k p o s i t i o n s (20) indicate t h e wavelengths
a n d t h e r e b y t h e x-ray lines a n d elements present. T h e
intensities give i n f o r m a t i o n a b o u t c o n c e n t r a t i o n s .

575

X-Ray

Fluorescence

Spectrometry

Q u a n t i t a t i v e analysis is p e r f o r m e d by setting t h e
g o n i o m e t e r at t h e 20 angle of a specified x-ray line,
say c o p p e r . T h e s e a l e r - t i m e r c o u n t s c o p p e r
pulses for a " p r e s e t t i m e " o r times the a c c u m u l a t i o n
of a " p r e s e t c o u n t . " M e a s u r e m e n t s a r e m a d e o n e a c h
s a m p l e a n d o n s t a n d a r d s similar t o t h e s a m p l e s b u t
h a v i n g k n o w n c o m p o s i t i o n . T h e s t a n d a r d d a t a is used
to establish a m a t h e m a t i c a l r e l a t i o n s h i p o r c a l i b r a t i o n
curve of c o p p e r intensity against c o p p e r c o n c e n
t r a t i o n , t o which the s a m p l e intensity d a t a is applied.
Alternatively, t h e intensity d a t a m a y be e n t e r e d in t h e
c o m p u t e r for calculation of c o m p o s i t i o n . T h e s a m e
p r o c e d u r e is followed for the o t h e r s a m p l e elements.

10. Matrix

Effects

It m i g h t be expected t h a t spectral-line intensity of

analyte element A from s a m p l e X , 7 A X, a n d from p u r e
A , 7 A A, w o u l d be related by IAX = C A X/ A A, w h e r e C A X is
the m a s s fraction of A in X . T h i s relation s e l d o m
applies d u e t o m a t r i x effects, the effects of the overall
specimen o n t h e x-ray line intensity of t h e a n a l y t e .
M a t r i x effects m a y b e physical (e.g., surface texture,
p o r o s i t y , particle size a n d c o m p o s i t i o n a l h e t e r o g e
neity) o r chemical ( a b s o r p t i o n - e n h a n c e m e n t effects of
o t h e r elements in the s p e c i m e n m a t r i x e l e m e n t s o n
analyte-line intensity). / A X from several specimens of
identical c o m p o s i t i o n m a y vary if t h e specimens differ
in the physical features cited, especially for longwavelength lines. / A X from several specimens of identi
cal physical n a t u r e a n d A c o n c e n t r a t i o n m a y vary
with t h e c o n c e n t r a t i o n of o n e o r m o r e m a t r i x ele
m e n t s . T h e s e m a t r i x elements m a y r e d u c e 7 A X b y
preferentially a b s o r b i n g t h e a n a l y t e line a n d / o r t h e
p r i m a r y rays m o s t efficient in exciting it. C o n v e r
sely, the m a t r i x elements m a y e n h a n c e 7 A X if their o w n
x-ray lines h a v e wavelengths s h o r t e r t h a n t h e a n a l y t e line a b s o r p t i o n edge a n d excite analyte-line emission
in a d d i t i o n t o t h a t excited by the p r i m a r y rays.
Physical effects a r e dealt with by t h e specimen
p r e p a r a t i o n t e c h n i q u e (see Sect. 11), a b s o r p t i o n e n h a n c e m e n t effects by choice of analytical m e t h o d
(see Sect. 12).

11. Specimen

Forms and

Preparation

F o r qualitative analysis, it is sufficient t h a t the s a m p l e

fit in the specimen h o l d e r . H o w e v e r , for q u a n t i t a t i v e
analysis all samples a n d s t a n d a r d s in t h e analytical set
m u s t h a v e t h e s a m e form a n d t h e s a m e suitable
h o m o g e n e i t y , finish, particle-size d i s t r i b u t i o n , p o r o s
ity a n d so o n . W h e n samples c a n be analyzed a s received with m i n i m a l p r e p a r a t i o n , x-ray
fluorescence
s p e c t r o m e t r y c a n analyze large n u m b e r s of samples
rapidly a n d conveniently. H o w e v e r , s u b s t a n t i a l p r e
p a r a t i o n , possibly involving c h a n g e in form, is
required w h e n : (a) samples a r e u n s t a b l e o r h a v e severe

576

physical m a t r i x effects; (b) a n a d d i t i o n o r dilution

m e t h o d (Sect. 12) is required; a n d / o r (c) s t a n d a r d s are
u n a v a i l a b l e in t h e as-received form, o r t h e s a m e
m a t e r i a l m u s t be analyzed in several forms, such as
ingot, b a r , s h o t a n d p o w d e r . S u c h p r e p a r a t i o n d e
creases t h e speed a n d convenience. T h e principal
specimen f o r m s a r e described in the following
sections.
11.1 Solids
Solids include b u l k m e t a l , m i n e r a l , slag, ceramic,
glass, plastic, w o o d a n d r u b b e r . F i n i s h e d stock (e.g.,
b a r a n d sheet) m a y require n o p r e p a r a t i o n o t h e r t h a n
c u t t i n g t o size. Pieces sawed from ingot, r o d , rock,
r a w stock a n d so o n , usually require polishing. Prefer
ential r e m o v a l of p h a s e s , s m e a r i n g of soft p h a s e s , a n d
c o n t a m i n a t i o n b y polishing abrasive m u s t be avoided.
11.2
Powders
P o w d e r s m a y be used: (a) loose in d i s p o s a b l e M y l a r covered plastic c u p s ; (b) as b r i q u e t s , with o r w i t h o u t
b i n d e r , usually with a protective b a c k o r ring o r in a
shallow m e t a l dish; o r (c) s p r e a d in a thin layer
b e t w e e n M y l a r films stretched over a plastic c u p .
All s a m p l e s a n d s t a n d a r d s in a solid, p o w d e r o r
b r i q u e t set m u s t h a v e t h e s a m e surface finish o r
particle size. T h e longer t h e wavelength t o be
m e a s u r e d , t h e finer the finish o r particles m u s t be;
~ 20 is sufficient for lines d o w n to a t o m i c
n u m b e r 11 ( s o d i u m ) .
11.3 Glass or other Fused Disks
G l a s s o r o t h e r fused disks a r e used w h e n severe
physical m a t r i x effects p r e c l u d e use of t h e original
solid o r p o w d e r . T h e s a m p l e is fused with a lowmelting flux (such as p o t a s s i u m pyrosulfate) o r a
high-melting glass-forming flux (such as s o d i u m tetra
b o r a t e ) . T h e n o w h o m o g e n e o u s melt c a n be cast as a
disk o r pulverized a n d used as a p o w d e r .
11.4 Liquids and Slurries
L i q u i d s a n d slurries a r e held in d i s p o s a b l e M y l a r covered plastic c u p s . All samples a n d s t a n d a r d s in a
set m u s t h a v e the s a m e m a t r i x , for e x a m p l e , t h e s a m e
acid in the s a m e c o n c e n t r a t i o n . L i q u i d s a r e p r o n e t o
b u b b l e f o r m a t i o n a n d p r e c i p i t a t i o n in t h e intense
p r i m a r y x-ray b e a m .
11.5 Supported
Specimens
S u p p o r t e d specimens c o m p r i s e : (a) m i c r o s a m p l e s
d e p o s i t e d o n filter p a p e r , Millipore filters, thin M y l a r
film, o r such like, by e v a p o r a t i o n of liquid d r o p s o r b y
filtration
of liquids a n d gases; (b) m i c r o samples
a d s o r b e d by i o n - e x c h a n g e resin, m e m b r a n e o r p a p e r ;
(c) thin films, including platings, c o a t i n g s , e v a p o r a t e d
films, c o r r o s i o n layers a n d residues; (d) b u l k m a t e r i a l s
r e d u c e d t o t h i n layers; a n d (e) p a p e r , textile, a n d such
like for analysis of filler, sizing, ink, d y e a n d so o n .
S u p p o r t e d specimens a r e less t h a n infinitely thick.

X-Ray

11.6 Fabricated Forms and Parts

F a b r i c a t e d forms a n d p a r t s of small size c a n be placed
in m o s t s p e c t r o m e t e r s . Very large specimens, such as
ingots, engine p a r t s a n d a r t objects, c a n be a c c o m m o
dated on some instruments.
T h e p o w d e r , b r i q u e t , fusion a n d liquid f o r m s h a v e
the a d v a n t a g e t h a t s t a n d a r d s c a n be synthesized.

12. Analytical

Methods

M o s t analytical x-ray fluorescence s p e c t r o m e t r i c

m e t h o d s m a y be classified in seven categories b a s e d
o n their a p p r o a c h t o c o m p e n s a t i n g a b s o r p t i o n e n h a n c e m e n t effects.
12.1 Calibration
Standardization
X - r a y line intensities from s a m p l e s a r e c o m p a r e d with
those from s t a n d a r d s as similar t o t h e s a m p l e s as
possible in form a n d c o m p o s i t i o n , as described in
Section 9. W h e n m i n o r o r trace c o n s t i t u e n t s within
n a r r o w specification limits a r e t o be d e t e r m i n e d , a
single s t a n d a r d h a v i n g c o m p o s i t i o n n e a r m i d r a n g e
m a y suffice: C x / C s = Ix/Is w h e r e C, /, S a n d X a r e
c o n c e n t r a t i o n , intensity, s t a n d a r d a n d s a m p l e , re
spectively. In d e t e r m i n i n g nickel in stainless steel,
nickel intensity d e p e n d s o n b o t h nickel a n d c h r o
m i u m c o n c e n t r a t i o n . I n such cases, a set of curves
c a n be established, here, nickel intensity versus
c o n c e n t r a t i o n , e a c h c u r v e for a different c h r o m i u m
c o n c e n t r a t i o n . Actually, all analytical x-ray s p e c t r o
metric m e t h o d s r e q u i r e c a l i b r a t i o n s t a n d a r d s , except
s t a n d a r d a d d i t i o n a n d dilution (see below), b u t
these m e t h o d s h a v e features t h a t w a r r a n t s e p a r a t e
classification.
12.2 Internal

Standardization

T h e c a l i b r a t i o n - s t a n d a r d m e t h o d is i m p r o v e d b y
q u a n t i t a t i v e a d d i t i o n t o all s a m p l e s a n d s t a n d a r d s of
a n element h a v i n g excitation, a b s o r p t i o n a n d en
h a n c e m e n t p r o p e r t i e s similar t o t h o s e of t h e a n a l y t e
in t h e p a r t i c u l a r m a t r i x . T h e c a l i b r a t i o n function is
the a n a l y t e / i n t e r n a l - s t a n d a r d intensity r a t i o versus
analyte concentration.
12.3 Standardization
with Scattered X Rays
T h e intensity of a selected w a v e l e n g t h from t h e p r i m
ary rays scattered by t h e specimen is used t o c o r r e c t
a b s o r p t i o n - e n h a n c e m e n t ( a n d o t h e r ) effects. T h e
wavelength m a y be from t h e c o n t i n u u m o r a t a r g e t
line. T h e c a l i b r a t i o n function is a n a l y t e / s c a t t e r e d
intensity r a t i o versus c o n c e n t r a t i o n .
12.4 Matrix-Dilution
Methods
All samples a n d s t a n d a r d s a r e t r e a t e d with a
" d i l u e n t , " which c o n s t i t u t e s a n e w c o n s t a n t m a t r i x .
T h e diluent m a y be a high c o n c e n t r a t i o n of lowa t o m i c - n u m b e r m a t e r i a l , such as a p o w d e r , solvent o r

Microanalysis,

Quantitative

fusion flux, o r a low c o n c e n t r a t i o n of h i g h - a t o m i c n u m b e r m a t e r i a l , such as l a n t h a n u m oxide.

12.5 Thin-Film
Methods
T h e specimens a r e so thin t h a t
absorptione n h a n c e m e n t effects substantially d i s a p p e a r . S o m e
s a m p l e s a r e inherently thin films, o t h e r s c a n be p r e
p a r e d in thin-film form (Sect. 11).
12.6 Standard Addition and Dilution
A n a l y t e c o n c e n t r a t i o n is altered q u a n t i t a t i v e l y in a
p o r t i o n of s a m p l e . Intensities from t r e a t e d a n d
u n t r e a t e d p o r t i o n s a r e applied t o e q u a t i o n s . T h e
m e t h o d requires n o s t a n d a r d s a n d is useful for " o n e o f - a - k i n d " s a m p l e s a n d s a m p l e s for which s t a n d a r d s
are unavailable.
12.7 Mathematical
Methods
Intensities from s a m p l e s a n d s t a n d a r d s a r e applied to
sets of c o m p l e x m a t h e m a t i c a l e q u a t i o n s established
for e a c h m a t r i x system. C o m p u t e r calculation is
required.
See also: Electron Microprobe Analysis; X-Ray Absorption
Spectroscopy: EXAFS and XANES Techniques; X-Ray
Microanalysis, Quantitative

Bibliography
Bertin 1975 Principles and Practice of X-Ray Spectro
metric Analysis, 2nd edn. Plenum, New York
Bertin 1978 Introduction to X-Ray Spectrometric Analy
sis. Plenum, New York
Herglotz , Birks L S (eds.) 1978 X-Ray Spectrometry.
Dekker, New York
Jenkins R 1974 An Introduction to X-Ray Spectrometry.
Heyden, London
Jenkins R, De Vries J L 1969 Practical X-Ray Spectrometry,
2nd edn. Springer, New York
E. P. Bertin
[RCA Laboratories, Princeton,
N e w Jersey, U S A ]

X-Ray Microanalysis, Quantitative

Electron-excited x-ray analysis, as described in the
articles Electron Microprobe Analysis, Electron Mic
roscopy, Analytical
a n d Scanning Electron
Micros
copy, p r o d u c e s d a t a o n relative elemental intensities
from w h i c h c o n c e n t r a t i o n s c a n be calculated. Q u a l i
tative analysis consists of identifying t h e elements
p r e s e n t from t h e energies (or wavelengths) of the
p e a k s p r e s e n t in the x-ray s p e c t r u m . T h i s process
m a y b e q u i t e difficult, b e c a u s e with the wavelengthdispersive ( W D ) s p e c t r o m e t e r only a p o r t i o n of the
s p e c t r u m m a y h a v e been analyzed, a n d with the
energy-dispersive ( E D ) s p e c t r o m e t e r the greater p e a k
w i d t h s ( p o o r e r r e s o l u t i o n ) m a y p r o d u c e overlaps t h a t
577

X-Ray

Microanalysis,

Quantitative

o b s c u r e s o m e p e a k s o r hide small p e a k s in statistical

fluctuations.
Whether accomplished using the opera
t o r ' s experience a n d k n o w l e d g e of t h e s a m p l e , o r
using c o m p u t e r i z e d aids t o find a n d label p e a k s , t h e
qualitative result simply identifies w h i c h elements a r e
p r e s e n t in d e t e c t a b l e a m o u n t s a n d d o e s n o t p r o v i d e
c o m p o s i t i o n i n f o r m a t i o n o n t h e s a m p l e (or t h e local
region selected for analysis).
T h e first, essential step t o w a r d s q u a n t i t a t i v e results
is o b t a i n i n g net intensities for t h e v a r i o u s elements.
T h e s p e c t r u m b a c k g r o u n d in W D analysis c a n usually
b e m e a s u r e d next t o t h e p e a k b y adjusting t h e crystal
angle. T h i s is less easy t o a c c o m p l i s h with t h e E D
system b e c a u s e the p e a k s a r e b r o a d a n d often inter
fere, a n d t h e b a c k g r o u n d m a y be q u i t e n o n l i n e a r . T h e
c o n t i n u u m b a c k g r o u n d consists of b r e m s s t r a h l u n g
r a y s p r o d u c e d b y t h e deceleration of t h e m o v i n g
electrons by t h e electrostatic field n e a r a t o m i c nuclei.
It c a n be m o d e l l e d for the entire s p e c t r u m as p a r t of
the iterative q u a n t i t a t i v e c o r r e c t i o n process (as it
d e p e n d s o n t h e s a m p l e c o m p o s i t i o n ) for ideal flat,
h o m o g e n e o u s b u l k specimens. L o c a l fitting of
semiempirical curves is also used, especially w h e n t h e
samples a r e n o t ideal o r t h e m e a s u r e d s p e c t r u m
b a c k g r o u n d includes o t h e r sources of r a y s , for
instance d u e t o scattering from t h e s a m p l e h o l d e r in
t h e analytical electron m i c r o s c o p e ( A E M ) .
O n e of t h e m o s t c o m m o n m e t h o d s used t o o b t a i n
net elemental p e a k s is t o a p p l y a derivative filter t o t h e
s p e c t r u m w h i c h suppresses t h e m o r e g r a d u a l l y vary
ing b a c k g r o u n d c o m p a r e d t o t h e p e a k s , followed b y
least-squares fitting of p e a k s h a p e s either m e a s u r e d
from s t a n d a r d s a n d s t o r e d , o r g e n e r a t e d in t h e c o m
p u t e r . I n principle, this s h o u l d c a u s e p r o b l e m s d u e t o
a b s o r p t i o n edges in t h e s p e c t r u m (which d e p e n d u p o n
c o m p o s i t i o n ) o r p o o r fitting if t h e p e a k s h a p e o r
a l i g n m e n t varies w i t h i n s t r u m e n t a l factors. I n p r a c
tice, t h e m e t h o d w o r k s well m o s t of t h e time a n d is
widely used. D e b a t e s b e t w e e n m a n u f a c t u r e r s c o n
tinue over t h e relative m e r i t s of using m e a s u r e d a n d
g e n e r a t e d s t a n d a r d spectra, using n o n l i n e a r fitting
m e t h o d s t h a t c a n a c c o m m o d a t e p e a k shifts, a n d s o
on.

/.

ZAF

Corrections

O f t h e v a r i o u s m e t h o d s used t o calculate c o n c e n t r a
tions from net elemental intensities, t h e c o n v e n t i o n a l
Z A F m e t h o d is b y far t h e m o s t widely used for b u l k
specimens. Z A F refers t o t h e s e p a r a t e a t o m i c n u m b e r
Z , a b s o r p t i o n A a n d fluorescence F c o r r e c t i o n s w h i c h
a r e calculated as a function of a n ( a s s u m e d ) c o m p o s i
tion a n d multiplied b y t h e m e a s u r e d intensity r a t i o
( m e a s u r e d intensity divided b y p u r e element intensity
m e a s u r e d u n d e r identical circumstances):
Concentration = (
Intensity \
V P u r e intensity /

578

/
1_
\ ZAF )

T h e c o r r e c t i o n describes t h e relative ability of

different e l e m e n t s t o scatter electrons a n d be ionized
b y t h e m , t h e A t e r m c o r r e c t s for t h e fraction of r a y s
w h i c h a r e a b s o r b e d in t h e specimen o n their w a y o u t
(a function of t h e d e p t h a t w h i c h they a r e g e n e r a t e d )
a n d t h e F c o r r e c t i o n a c c o u n t s for a d d i t i o n a l x-ray
intensity p r o d u c e d b y i o n i z a t i o n s c a u s e d b y t h e
a b s o r p t i o n of o t h e r r a y s , r a t h e r t h a n directly b y t h e
electron b e a m . T h e c a l c u l a t i o n p r o c e s s is iterative, as
progressively b e t t e r estimates of c o m p o s i t i o n a r e
made.
P r o g r a m s t h a t r o u t i n e l y a p p l y this c o r r e c t i o n p r o
cedure can be run on most desk-top or personal
c o m p u t e r s . T h e e q u a t i o n s used t o m o d e l t h e v a r i o u s
t e r m s a r e well refined a n d q u i t e a c c u r a t e ( a few
p e r c e n t ) for t h e general r u n of analytical p r o b l e m s ,
b u t t h e a p p r o x i m a t i o n s e m p l o y e d d o n o t p r o d u c e as
g o o d results for elements with very low o r high a t o m i c
n u m b e r s , e x t r e m e analysis c o n d i t i o n s (especially
accelerating v o l t a g e o r specimen surface inclination),
o r n o n i d e a l s a m p l e geometries (in principle, t h e
m e t h o d applies o n l y t o b u l k h o m o g e n e o u s specimens
with flat, polished surfaces).
Z A F p r o g r a m s h a v e been e x t e n d e d in v a r i o u s
w a y s . F o r m i n e r a l specimens in which a large n u m b e r
of e l e m e n t s a r e p r e s e n t b u t w h i c h v a r y o n l y slightly
from s t a n d a r d t o u n k n o w n , t h e t e r m s c a n b e precalc u l a t e d a n d fitted t o linear s i m u l t a n e o u s e q u a t i o n s
t h a t p r o v i d e a m u c h faster s o l u t i o n for t h e elemental
c o n c e n t r a t i o n s . F o r c o m b i n a t i o n s of light a n d h e a v y
elements, a c o r r e c t i o n for fluorescence of c h a r a c t e r i s
tic r a y s b y t h e c o n t i n u u m c a n b e included. P u r e
e l e m e n t a l intensities c a n be calculated from c o m
p o u n d s t a n d a r d s , from o t h e r n e a r b y elements in t h e
p e r i o d i c t a b l e , o r from semiempirical e q u a t i o n s
r e q u i r i n g n o m e a s u r e m e n t s a t all.
T h e last t w o possibilities for eliminating t r a d i t i o n a l
s t a n d a r d s m e a s u r e m e n t s a r e often described a s " s t a n d a r d l e s s " m e t h o d s a n d a r e n o w r o u t i n e l y accepted for
use w i t h E D s p e c t r o m e t e r s , in w h i c h t h e s p e c t r o m e t e r
r e s p o n s e a s a function of energy is well k n o w n a n d
q u i t e c o n s t a n t . F o r elements in t h e r a n g e 11 < <
45 (i.e., e l e m e n t s a n a l y z e d b y their K-shell electrons)
t h e results from s t a n d a r d l e s s analysis a r e c o m p a r a b l e
t o c o n v e n t i o n a l m e t h o d s , a n d m a y b e s u p e r i o r if t h e
i n s t r u m e n t stability d o s n o t p e r m i t s t a n d a r d s t o b e
m e a s u r e d u n d e r exactly identical c o n d i t i o n s a s t h e
u n k n o w n s . F o r h i g h e r (aii4 lpwer) a t o m i c n u m b e r
elements, or when mixed
L- a n d M-shell r a y s a r e
used, t h e results a r e jpoprer 'for t h e s t a n d a r d l e s s
m e t h o d s , a n d indeed for the, Z A F a p p r o a c h in
general.
F o r light e l e m e n t s in p a r t i c u l a r , t h e large a b s o r p
tion c o r r e c t i o n n e e d e d , p o o r l y k n o w n f u n d a m e n t a l
c o n s t a n t s , difficulty in d e t e r m i n i n g precise intensities
d u e t o significant p e a k o v e r l a p s o r v a r i a t i o n in p e a k
s h a p e s o r spectral b a c k g r o u n d , a n d s t r o n g influence
of t h e specimen surface c o m b i n e t o p r o d u c e r a t h e r
large e r r o r s . Often, b e t t e r results c a n b e o b t a i n e d b y

X-Ray

using k n o w n elemental stoichiometrics for t h e light

elements, o r d e t e r m i n i n g t h e m b y difference from
1 0 0 % as c o m p a r e d t o m e a s u r e m e n t a n d c a l c u l a t i o n .
W h e n light element analysis m u s t be p e r f o r m e d , it is
possible t o use a () (where is density a n d is
d e p t h ) in which t h e d e p t h profile of the g e n e r a t e d
x-ray intensity is c o m p u t e d using semiempirical
e q u a t i o n s b a s e d o n m e a s u r e m e n t s , a n d a b s o r p t i o n is
directly s u m m e d o v e r d e p t h with m u c h g r e a t e r a c c u r
acy t h a n t h e Z A F m e t h o d .

2. Other Specimen

Microanalysis,

Quantitative

Figure 1
Example of a Monte Carlo simulation of a few trajectories
for 20 keV electrons in nickel

Geometries

F o r thin specimens, as e n c o u n t e r e d in t h e A E M ,
a b s o r p t i o n is negligible a n d fluorescence d i s a p p e a r s ,
so t h e c o r r e c t i o n p r o c e d u r e is further simplified. O n l y
the relative efficiency with w h i c h different e l e m e n t s
c a n be excited a n d emit characteristic rays a n d t h e
sensitivity of t h e s p e c t r o m e t e r a t different energies
r e m a i n . T h i s c a n be calculated either from f u n d a m e n
tal p a r a m e t e r s o r m e a s u r e d from a s t a n d a r d specimen
( b o t h m e t h o d s h a v e their a d h e r e n t s ) , t o p r o d u c e a
factor relating t h e m e a s u r e d intensity r a t i o s from
different elements t o their c o n c e n t r a t i o n s :
Concentration!
Concentration

Intensity!
2 1

Intensity2

F o r n o r m a l specimens, this is usually s u p p l e m e n t e d

by t h e a s s u m p t i o n t h a t XC, = 1. F o r s a m p l e s t h a t a r e
n o t ideally thin, a c o r r e c t i o n for x-ray a b s o r p t i o n c a n
be applied b u t results in t h e c a l c u l a t i o n b e c o m i n g
iterative since t h e a b s o r p t i o n d e p e n d s u p o n c o n c e n
tration.
T h e r e h a s been m u c h recent interest in a d a p t i n g
quantitative correction calculations to m o r e complex
specimen geometries, such as p a r t i c u l a t e s , t h i n films
o n s u b s t r a t e s a n d n o n p l a n a r surfaces. O n e a p p r o a c h
uses t h e fact t h a t t h e r a t i o of p e a k (characteristic)
intensity t o b a c k g r o u n d ( c o n t i n u u m ) intensity is rela
tively insensitive t o s a m p l e g e o m e t r y . T h i s is b e c a u s e
in m a n y c i r c u m s t a n c e s t h e a b s o r p t i o n c o r r e c t i o n is
t h e m o s t i m p o r t a n t , a n d since t h e c o n t i n u u m is gener
a t e d with a d e p t h profile r o u g h l y similar t o t h e
characteristic r a y s it is subjected t o a similar
a m o u n t of a b s o r p t i o n . Z A F m o d e l s adjusted t o use
p e a k - t o - b a c k g r o u n d r a t i o s h a v e s h o w n p r o m i s e for
particulates a n d r o u g h surfaces b u t t h e b a c k g r o u n d g e n e r a t i o n m o d e l s a r e n o t yet c a p a b l e of p r o d u c i n g
consistent results w i t h b e t t e r t h a n 5 - 1 0 % a c c u r a c y .
A n o t h e r a p p r o a c h t o p a r t i c u l a t e analysis uses
semiempirical c a l i b r a t i o n curves t o modify q u a n t i t a
tive results calculated as for a b u l k s a m p l e , as a
function of t h e o b s e r v e d s h a p e o r size of particles.
Particularly in t h e s c a n n i n g electron m i c r o s c o p e
( S E M ) , few specimens h a v e ideally flat surfaces. C o n
ventional Z A F m o d e l s c a n often b e a p p l i e d if t h e
local surface is p l a n a r (e.g., m a n y fracture surfaces)
p r o v i d e d its o r i e n t a t i o n c a n b e d e t e r m i n e d b y stereos-

c o p y . Alternatively, s p e c t r a c a n b e o b t a i n e d a t t w o
different accelerating voltages a n d c a l c u l a t i o n used t o
d e t e r m i n e t h e o r i e n t a t i o n angle t h a t gives t h e s a m e
c o m p o s i t i o n a n s w e r for b o t h analyses.
T h e accelerating v o l t a g e is a l w a y s a p a r a m e t e r of
p r i m e i m p o r t a n c e for q u a n t i t a t i v e analysis. W i t h a n
E D s p e c t r o m e t e r , it is best d e t e r m i n e d b y t h e cutoff
p o i n t of t h e c o n t i n u u m b a c k g r o u n d . T h i s is generally
more accurate than any meter on the microscope, and
also t a k e s i n t o a c c o u n t a n y deceleration of t h e elec
tron beam that m a y occur due to sample charging.

3. Monte

Carlo

Modelling

T h e m e t h o d w h i c h is in principle c a p a b l e of dealing
with a n y k i n d of specimen g e o m e t r y is M o n t e C a r l o
m o d e l l i n g . R a t h e r g o o d m o d e l s a r e n o w available for
e a c h of t h e individual processes b y w h i c h m o v i n g
electrons lose energy a n d slow d o w n , a n d excite
characteristic o r c o n t i n u u m rays from a t o m s . By
using c o m p u t e r r a n d o m - n u m b e r g e n e r a t o r s t o s a m p l e
these p r o b a b i l i t y d i s t r i b u t i o n s it is possible t o follow
t h e p a t h s of a statistically useful n u m b e r (typically a t
least several t h o u s a n d , a n d m a n y m o r e in s o m e cases)
of electrons as they scatter from a t o m s in t h e speci
men, encounter various geometric boundaries and
generate rays which can be summed. (Figure 1
s h o w s a n e x a m p l e of a M o n t e C a r l o p l o t of electron
trajectories.) T h i s m e a n s t h a t a n y b o u n d a r y c o n
d i t i o n s , surface o r subsurface irregularities, c o m p o s i
t i o n h e t e r o g e n e i t y o r o t h e r s a m p l e peculiarities c a n be
set u p a n d t h e x-ray yield calculated.
I n practice, this is n o t a g o o d q u a n t i t a t i v e c o r r e c
tion t o o l , for several r e a s o n s . First, t h e calculation
p r o c e e d s from t h e full d e s c r i p t i o n of t h e s a m p l e ,
w h i c h is u n k n o w n , t o t h e x-ray intensities, which c a n
be m e a s u r e d . E x c e p t in simple cases, for instance, the
thickness of a c o a t i n g layer, it is difficult t o iterate the
u n k n o w n p a r a m e t e r s t o achieve a g r e e m e n t . Second,
t h e c o m p u t e r t i m e n e e d e d t o t r a c k e n o u g h electrons
t o o b t a i n g o o d results is n o t trivial. S o m e very useful
simplifications of t h e full M o n t e C a r l o a p p r o a c h h a v e

579

X-Ray

Microanalysis,

Quantitative

been p r o d u c e d t h a t allow t h e m o d e l s t o r u n quickly in

d e s k - t o p a n d p e r s o n a l c o m p u t e r s , b u t these a r e n o t
able t o m o d e l s o m e of t h e m o r e subtle effects o r t o be
used in a real-time c o r r e c t i o n scheme. T h e m o s t
n o t a b l e simplification is the " m u l t i p l e s c a t t e r i n g "
m o d e l in w h i c h t h e individual e l e c t r o n - a t o m i n t e r a c
tions are l u m p e d t o g e t h e r i n t o a c o n t i n u o u s slowingd o w n m o d e l t h a t zigzags in only a few d o z e n steps
t h r o u g h the s a m p l e .
It h a s p r o v e d practical t o p r e c o m p u t e c a l i b r a t i o n
curves of x-ray intensity against t h e thickness a n d
c o m p o s i t i o n of p l a n a r multilayer c o a t i n g s o n s u b
strates, which c a n t h e n be used in real-time analysis.
T h e greatest use of M o n t e C a r l o m e t h o d s h a s been t o
test a n d verify o t h e r c o r r e c t i o n m e t h o d s a n d t o evalu
ate f u n d a m e n t a l p a r a m e t e r s for electron a n d x-ray
interactions. T h e p r o g r a m s h a v e b e e n especially use
ful in u n d e r s t a n d i n g a n d m o d e l l i n g t h e g e n e r a t i o n of
s e c o n d a r y a n d b a c k s c a t t e r e d electrons, for instance t o
develop o p t i m u m d e t e c t o r geometries o r t o establish
m e a s u r e m e n t m e t h o d s for electronic devices a n d
o t h e r small s t r u c t u r e s e x a m i n e d in t h e s c a n n i n g elec
tron microscope (SEM).

4. Dimensions

of

Analysis

F o r h e t e r o g e n e o u s samples o r n o n i d e a l surfaces it is
i m p o r t a n t t o k n o w the d i m e n s i o n s of t h e region in
which the electrons scatter a n d rays a r e g e n e r a t e d .
In thin sections ( A E M ) this is basically a t r u n c a t e d
c o n e , s p r e a d i n g from t h e incident electron b e a m ,
w h o s e angle d e p e n d s u p o n electron voltage a n d t h e
s a m p l e ' s a t o m i c n u m b e r a n d density. W h i l e t h e m e a n
d i a m e t e r of the a n a l y z e d v o l u m e c a n be very small
(less t h a n 50 n m ) for thin specimens, this is often still
i n a d e q u a t e t o analyze selectively individual precipi
tates a n d inclusions. T h e m a t r i x is included in t h e
excited region a n d m a k e s q u a n t i t a t i v e analysis diffi
cult if n o t impossible. Physical s e p a r a t i o n of t h e
features of interest from t h e m a t r i x , for e x a m p l e , with
a n e x t r a c t i o n replica, is s o m e t i m e s a practical solu
tion. In analyzing small features in thin specimens, the
use of extremely small electron b e a m s (to achieve t h e
best possible spatial resolution) p r o d u c e s very low
c o u n t rates, w h i c h m a k e s a n y e x t r a n e o u s b a c k g r o u n d
d u e t o electron scattering in t h e m i c r o s c o p e , for
instance, m o r e i m p o r t a n t , a n d also restricts a c c u r a c y
because of limited c o u n t i n g statistics.
In b u l k samples, subsurface s t r u c t u r e s m a y be
invisible in t h e S E M i m a g e b u t still c o n t r i b u t e t o t h e
analysis. T h e excited region is generally described as a
t e a r d r o p o r sphere. T h e p r o b a b i l i t y of electron scat
tering d e p e n d s o n a t o m i c n u m b e r (the c h a r g e o n t h e
nucleus) so t h a t the s h a p e of t h e excited v o l u m e
b e c o m e s m o r e flattened ( b r o a d c o m p a r e d t o its d e p t h )
for h i g h - Z specimens, a n d conversely b e c o m e s d e e p e r
c o m p a r e d t o its b r e a d t h for l o w - Z specimens. T h e
electron r a n g e d e p e n d s p r i m a r i l y o n t h e electron

580

Figure 2
Schematic diagram of the variation in size and shape of
the electron excited region with specimen atomic number
and electron accelerating voltage

energy, so t h e size of t h e excited region is c o n t r o l l e d

p r i m a r i l y b y t h e choice of accelerating voltage. T h i s is
i n d i c a t e d in F i g . 2.
It m a y also b e i m p o r t a n t t o r e m e m b e r t h a t different
elements h a v e different i o n i z a t i o n p o t e n t i a l s , so t h a t
electrons m a y b e c a p a b l e of exciting o n e element
d e e p e r in t h e s a m p l e t h a n a n o t h e r . I n general, t h e size
of t h e excited region is different for each element in
t h e specimen a n d m a y v a r y from as little as 0.2 p m t o
tens of m i c r o m e t e r s . S e c o n d a r y effects such as fluor
escence of detected r a y s b y o t h e r rays c a n e x t e n d
t o a m u c h larger v o l u m e .
If heterogeneity is suspected because of the size of
t h e excited region, it is wise t o analyze several loca
tions, o r t o p e r f o r m analysis o n t h e p o i n t of interest a t
several accelerating voltages (different d e p t h s of exci
t a t i o n ) , a n d c o m p a r e t h e m for uniformity. It s h o u l d
be n o t e d t h a t it is definitely n o t g o o d practice t o
collect a s p e c t r u m while s c a n n i n g t h e b e a m in a raster
over a large h e t e r o g e n e o u s region (either in t e r m s of
c o m p o s i t i o n o r surface o r i e n t a t i o n ) a n d t h e n p e r f o r m
a q u a n t i t a t i v e c o r r e c t i o n of t h e s p e c t r u m t o o b t a i n a n
" a v e r a g e " result. T h e v a r i o u s x-ray g e n e r a t i o n ,
a b s o r p t i o n a n d emission effects a r e definitely n o n l i
n e a r , a n d c a n n o t be a v e r a g e d in this w a y . T h e n o t i o n
t h a t this k i n d of " a v e r a g e " analysis is b e t t e r t h a n
n o t h i n g is d a n g e r o u s , a n d a l t h o u g h widely practised
s h o u l d definitely b e a v o i d e d . If a n " a v e r a g e " analysis
is r e q u i r e d , it c a n b e o b t a i n e d b y a n a l y z i n g a repre
sentative n u m b e r of s e p a r a t e ( r a n d o m ) p o i n t s , per
f o r m i n g a q u a n t i t a t i v e c o r r e c t i o n for e a c h ( p e r h a p s
t a k i n g i n t o a c c o u n t different surface o r i e n t a t i o n s ) ,
a n d t h e n a v e r a g i n g t h e resulting c o m p o s i t i o n a l d a t a .
See also: Electron Microprobe Analysis; Electron Micros
copy, Analytical; Scanning Electron Microscopy; X-Ray
Fluorescence Spectrometry

X-Ray

Bibliography
Heinrich F J 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Heinrich F J, Newbury D E, Yokowitz (eds.) 1976 Use
of Monte-Carlo Calculations in Electron Probe Microana
lysis and Scanning Electron Microscopy, National Bureau
of Standards Special Publication 460. US Department of
Commerce, Washington, DC
Russ J C 1984 Fundamentals of Dispersive X-Ray Analysis.
Butterworth, London
Scott V D, Love G 1983 Quantitative Electron Probe Mic
roanalysis. Ellis Horwood, Chichester, UK
Vollath D 1986 Some fundamental considerations to pre
cede image analysis. Bull. Mater. Sci. (India) 8: 169-82
J. C. R u s s
[ N o r t h C a r o l i n a State University,
Raleigh, N o r t h C a r o l i n a , U S A ]

Diffraction

m e t h o d . H o w e v e r , as in all analytical m e t h o d s it is
advisable w h e n e v e r possible t o s u p p l e m e n t x-ray in
f o r m a t i o n with d a t a from related m e t h o d s such a s
electron m i c r o s c o p y , x-ray fluorescence s p e c t r o s c o p y
a n d electron m i c r o p r o b e analysis.
T h e principal uses of t h e x-ray p o w d e r m e t h o d a r e :
(a)

identification of crystalline p h a s e s including q u a

litative a n d q u a n t i t a t i v e analysis of m i x t u r e s of
phases;

(b)

distinguishing b e t w e e n m i x t u r e s , v a r i o u s types
of solid s o l u t i o n s a n d p o l y m o r p h s ;

(c)

distinguishing b e t w e e n t h e a m o r p h o u s a n d crys
talline states;

(d)

precision m e a s u r e m e n t o f lattice p a r a m e t e r s a n d
thermal expansion;

(e)

d e t e r m i n a t i o n of t h e degree of preferred orien

t a t i o n a n d crystalline texture;

(f)

m e a s u r e m e n t of certain physical characteristics,

such as small crystallite sizes, strain, perfection,
lattice d i s o r d e r a n d d a m a g e ;

(g)

d e t e r m i n a t i o n of p h a s e s a n d p r o p e r t i e s as a
function of specimen e n v i r o n m e n t either in situ
o r after t r e a t m e n t a t t e m p e r a t u r e s from liquid
helium t o a b o u t 2000 C, a n d pressures u p t o
several h u n d r e d k b a r , in air, v a c u u m o r selected
gas.

X-Ray Powder Diffraction

X - r a y p o w d e r ( o r polycrystalline) diffraction h a s
played a very i m p o r t a n t role in t h e d e v e l o p m e n t of
science a n d t e c h n o l o g y . Since its i n t r o d u c t i o n in 1917,
by Hull in the U S A a n d i n d e p e n d e n t l y by D e b y e a n d
Scherrer in Switzerland, it h a s b e c o m e t h e i n d i s p e n s
able principal m e t h o d for identifying crystalline
p h a s e s of i n o r g a n i c , m e t a l a n d alloy, o r g a n i c , a n d
p o l y m e r m a t e r i a l s . T h e r e a r e n o w over 10 000 x-ray
p o w d e r diffraction i n s t r u m e n t s t h r o u g h o u t t h e w o r l d
used in m a n y a p p l i c a t i o n s for t h e n o n d e s t r u c t i v e
analysis a n d c h a r a c t e r i z a t i o n of chemicals, m i n e r a l s ,
ceramics, m e t a l s a n d o t h e r m a t e r i a l s . O n l y small
specimens a r e r e q u i r e d for analysis, a n d they m a y b e
in the form o f p o w d e r s , solid sections, thin films o n
s u b s t r a t e s , precipitates, d u s t s o r residues. C o m p l e t e xray systems a r e available from a n u m b e r of m a n u f a c
turers a n d m o d e r n i n s t r u m e n t s usually include a
m i n i c o m p u t e r for a u t o m a t e d c o n t r o l , d a t a r e d u c t i o n
a n d analysis.
A k n o w l e d g e of t h e crystal s t r u c t u r e of m a t e r i a l s is
essential in u n d e r s t a n d i n g t h e p r o p e r t i e s a n d h o w t o
identify t h e m , their b e h a v i o r u n d e r v a r i o u s c o n
ditions, a n d for t h e c h a r a c t e r i z a t i o n of t h e m a t e r i a l a t
all stages of its p r e p a r a t i o n . T h e r e p r o d u c t i o n of
m a t e r i a l s with tightly c o n t r o l l e d p r o p e r t i e s often re
quires x-ray analysis. A l t h o u g h single crystals a r e
preferred for d e t e r m i n i n g crystal s t r u c t u r e s o f n e w
m a t e r i a l s , s o m e m a t e r i a l s a r e available only as small
polycrystals. I n recent years t h e r e h a v e b e e n i m p o r t
a n t a d v a n c e s in using p o w d e r s for crystal s t r u c t u r e
d e t e r m i n a t i o n a n d refinement. M a n y s t r u c t u r e s a r e
already k n o w n a n d this i n f o r m a t i o n is used w i t h t h e
p o w d e r m e t h o d in m a n y types of studies t h a t a r e
essential for c h a r a c t e r i z i n g a n d a n a l y z i n g m a t e r i a l s .
T h e i m p o r t a n c e of these t e c h n i q u e s t o m a t e r i a l s
science will be a p p r e c i a t e d from t h e following list, all
of which c a n be best p e r f o r m e d b y t h e x-ray p o w d e r

Powder

1. Basis of

Method

B r a g g ' s law defines t h e c o n d i t i o n s for o b t a i n i n g x-ray

diffraction from a crystalline m a t e r i a l :
n = 2dsm

(1)

w h e r e is a small integer giving t h e o r d e r of diffrac

tion a n a l o g o u s t o a ruled g r a t i n g ; is t h e w a v e l e n g t h
of t h e characteristic line r a y s from t h e x-ray t u b e
a n d is usually t h e C u K a d o u b l e t with C u K a a j
= 0.1540562 n m ; d is t h e d i s t a n c e ( n m ) between a set
of parallel lattice planes; a n d is t h e angle between
t h e incident collimated x-ray b e a m a n d a n a t o m i c
lattice p l a n e in t h e crystal. T h e t e r m reflection
generally refers t o t h e individual diffractions a n d
s h o u l d n o t be confused with t h e t o t a l reflection of
r a y s a t very small angles from highly polished
surfaces.
T h e reflection angle for a p a r t i c u l a r set of lattice
p l a n e s (hkl) is:
1

2 0 = 2 s i n - [ A / 2 ^ / )]

(2)

w h e r e (hkl) a r e t h e Miller indices defining t h e orien

t a t i o n of t h e p l a n e w i t h respect t o t h e crystallographic
axes. Reflection o c c u r s only a t t h o s e angles w h e r e
scattering from successive lattice p l a n e s is in p h a s e ,
a n d this requires t h e p a t h difference t o b e a n integral
m u l t i p l e of t h e w a v e l e n g t h . F o r e x a m p l e , the
(hkl) = (\\\)
p l a n e of a silicon specimen reflects

581

X-Ray

Powder

Diffraction

CuKa,
rays a t 28.44 (20), from
which
d{lu) = 0.31357 n m . T h e second o r d e r d o e s n o t o c c u r
because of t h e lattice s y m m e t r y of the silicon a n d the
= 0.10453 n m . In
third o r d e r = 3 is a t 94.95
333)
is used instead of
crystallographic w o r k (hkl) =
= 3.
T h e relative intensities of the reflections a r e given
by

I,(hkl)

,|2
=

'

( 1+

cos-

K s i n 2 0 s i n

2 0 '\
2
)

(in:

Si ( 2 2 0 )

Si (311) --

D(220)

Si (422)
Si ( 4 0 0 ) | ? i (331)
0 (311J
(

(b)

|"">

(220)
(311)
(200)

(40
l ?2 2) )2

0)(33)
(422)
I
|(420) '

(I00).j
(C )

002)
(101)

(110)

(103) J
(112)
(102)
(300)

30

40

50

60

70

80

90

29
Figure 1
X-ray powder diffraction patterns of substances with
similar atomic arrangements: (a) silicon and diamond,
(b) sphalerite (face-centered-cubic ZnS), and (c) wurtzite
(hexagonal ZnS). The dashed lines connect the common
fundamental reflections

(4)

( T h e l o w e r - s y m m e t r y crystal systems require a d d i

tional terms.) F o r e x a m p l e , d i a m o n d a n d silicon h a v e
the s a m e d i a m o n d cubic s t r u c t u r e , with e a c h a t o m
linked by t e t r a h e d r a l b o n d i n g t o four c o n t a c t i n g
n e i g h b o r s . T h e a t o m i c d i a m e t e r of c a r b o n is smaller
t h a n t h a t of silicon a n d a0 of d i a m o n d is 0.35667 n m
a n d silicon 0.54301 n m . B o t h h a v e t h e s a m e p a t t e r n s
except for t h e larger d{hkl) values of silicon w h i c h o c c u r
at smaller reflection angles as s h o w n in Fig. 1. S p h a
lerite (-ZnS) h a s a similar s t r u c t u r e , b u t t h e a l t e r n a
tion of Z n - S - Z n a t o m s f o r m s a face-centered-cubic
lattice which gives t h e s a m e p a t t e r n plus a few a d d i
tional reflections. T h e p o l y m o r p h w u r t z i t e ( a - Z n S )
also h a s a similar f r a m e w o r k , b u t is h e x a g o n a l . T h e
lower s y m m e t r y a d d s m o r e reflections b u t t h e funda
m e n t a l reflections a r e identical with t h e o t h e r p a t
terns. T h e lattice type is d e t e r m i n e d by t h e reflections
that are present and absent.

582

(III)

...

w h e r e Fis the s t r u c t u r e factor of t h e hkl reflection a n d

is d e t e r m i n e d b y t h e p o s i t i o n s of t h e a t o m s , their
scattering factors a n d p h a s e s ; m is t h e multiplicity
factor which is a n integer o b t a i n e d b y c o m b i n i n g all
the + a n d - p e r m u t a t i o n s of h, k a n d / (in t h e case of
a c u b e , hOO, m = 6); a n d the t r i g o n o m e t r i c t e r m is t h e
L o r e n t z p o l a r i z a t i o n factor for p o w d e r diffractometry. In p o w d e r diffraction t h e specimen m u s t c o n t a i n
a large n u m b e r of small r a n d o m l y o r i e n t e d crystallites
to o b t a i n t h e correct values of t h e relative intensities
of all the possible lattice p l a n e s .
T h e p o w d e r p a t t e r n is a set of reflections in which
the lattice spacings a n d t h e relative intensities a r e
u n i q u e for each crystalline s u b s t a n c e . It is this p r o p
erty t h a t m a k e s it possible t o identify a s u b s t a n c e by
c o m p a r i n g its p a t t e r n with t h a t of a k n o w n s u b s t a n c e .
P a t t e r n s of m i x t u r e s a r e s u p e r i m p o s e d individual
p a t t e r n s . T h e n u m b e r of reflections r a n g e s from three
to a b o u t o n e h u n d r e d in t h e 2 r a n g e u p t o 90 with
C u K a r a d i a t i o n . T h e n u m b e r increases with unit-cell
d i m e n s i o n s a n d with decreasing s y m m e t r y of the
crystal s t r u c t u r e , a n d is generally i n d e p e n d e n t of the
chemical c o m p o s i t i o n .
Similar crystal s t r u c t u r e s give similar x-ray p a t t e r n s
in which the p e a k p o s i t i o n s will be shifted if t h e
m a t e r i a l s h a v e different lattice p a r a m e t e r s . T h e lattice
spacing d is related t o the lattice p a r a m e t e r a0 in cubic
crystals by
2\l/2

Si

(a)

2. Instrument

and Experimental

Methods

T h e m a j o r i n s t r u m e n t for x-ray p o w d e r diffraction

t h a t is used t o a n a l y z e virtually all types of m a t e r i a l , is
t h e focusing x-ray diffractometer with scintillation- o r
p r o p o r t i o n a l - c o u n t e r d e t e c t o r ( P a r r i s h 1965). T h e
basic a r r a n g e m e n t of t h e i n s t r u m e n t is s h o w n in F i g .
2. T h e c u r v e d m o n o c h r o m a t o r is usually highly
o r i e n t e d pyrolytic g r a p h i t e w h i c h reflects a b o u t 5 0 %
C u K a . It is set t o reflect only t h e K a d o u b l e t a n d
eliminates all o t h e r w a v e l e n g t h s from t h e x-ray t u b e
a n d specimen
fluorescence.
The detector rotates
a r o u n d t h e p o i n t a t twice t h e a n g u l a r speed of t h e
specimen so t h a t t h e specimen surface is always a t
a n d t h e receiving slit a t 2.
T h e diffractometer is driven b y a s y n c h r o n o u s
1
m o t o r , usually a t m i n , a n d t h e intensities
r e c o r d e d with a r a t e m e t e r a n d strip c h a r t . T h e
intensities a n d 2 values a r e r e a d from t h e c h a r t a n d

X-Ray

the lattice spacings calculated from t h e B r a g g e q u a

tion. M i n i c o m p u t e r s h a v e been i n t r o d u c e d t o a u t o
m a t e t h e p r o c e s s a n d collect t h e d a t a in digital f o r m
for c o m p u t e r d a t a r e d u c t i o n . A s t e p p i n g m o t o r re
places the s y n c h r o n o u s m o t o r a n d t h e p a t t e r n is
s c a n n e d stepwise w i t h selected a n g u l a r i n c r e m e n t s
2 = 0.01-0.05 a n d c o u n t time 0 . 1 s o r l o n g e r
d e p e n d i n g o n t h e n a t u r e of t h e p a t t e r n a n d t h e
required statistical a c c u r a c y . T h e d a t a a r e t h e n a u t o
matically r e d u c e d t o a set of d values a n d p e a k
intensities with a p e a k - s e a r c h o r profile-fitting p r o
gram. Algorithms have been developed which de
crease t h e t i m e for d a t a collection a n d r e d u c t i o n b y
m o r e t h a n o n e o r d e r of m a g n i t u d e c o m p a r e d w i t h
m a n u a l m e t h o d s a n d t h u s significantly increase t h e
precision. H i g h - s p e e d d a t a collection a t a r a t e of 30
1
(20) m i n using a c o n v e n t i o n a l sealed-off x-ray t u b e
a n d p e a k - s e a r c h d a t a r e d u c t i o n in less t h a n a m i n u t e
are n o w possible.
A different diffraction m e t h o d i n t r o d u c e d b y G i e s sen a n d G o r d o n in 1968 uses a solid-state d e t e c t o r
a n d m u l t i c h a n n e l pulse-height analyzer. T h e reflec
tions arise from t h e c o n t i n u o u s x-ray s p e c t r u m a n d
the B r a g g law in this case is

3. Phase

12.398

2nne.E,hkl)

w h e r e 0 is n o w t h e selected angle of incidence for all

reflections with d e t e c t o r a t 20, a n d is t h e energy in
keV for t h e reflection (hkl). By d e c r e a s i n g 20 t h e
p e a k s b e c o m e m o r e s e p a r a t e d o n a n energy scale, b u t
also b r o a d e r . T h e energies of t h e pulses a r e p r o p o r
tional t o t h e x-ray energies a n d a r e electronically

Diffraction

s o r t e d i n t o n a r r o w energy c h a n n e l s b y t h e pulse
height analyzer. T h e Si(Li) crystal d e t e c t o r m u s t be
k e p t a t l i q u i d - n i t r o g e n t e m p e r a t u r e a t all times.
T h e r e is n o need for s c a n n i n g b e c a u s e all the
reflections a r e r e c o r d e d s i m u l t a n e o u s l y . T h e m e t h o d
h a s t h e a d v a n t a g e t h a t a recognizable p a t t e r n (with
low statistical a c c u r a c y ) c a n be o b t a i n e d in less t h a n a
m i n u t e with a c o n v e n t i o n a l x-ray t u b e , o r in a few
s e c o n d s with a s y n c h r o t o n x-ray b e a m ; f u r t h e r m o r e ,
since there a r e n o m o v i n g p a r t s , specimen devices for
h e a t i n g a n d c o o l i n g a r e relatively easy t o m a k e .
H o w e v e r , t h e r e s o l u t i o n , w h i c h is d e t e r m i n e d by t h e
d e t e c t o r , is m o r e t h a n o n e o r d e r of m a g n i t u d e lower
t h a n t h a t of a s c a n n i n g diffractometer, a n d t h e p e a k t o - b a c k g r o u n d r a t i o m u c h lower, m a k i n g it useful
only for t h e simple p a t t e r n s .
C o n s i d e r a b l e c a r e is r e q u i r e d t o p r e p a r e speci
m e n s for x-ray diffraction. O n l y t h e surface layer of
thickness d e t e r m i n e d b y t h e a b s o r p t i o n c o n t r i b u t e s t o
t h e diffraction, a n d therefore h o m o g e n e i t y , flatness,
p a c k i n g a n d similar factors a r e i m p o r t a n t in s a m p l e
p r e p a r a t i o n . T h e specimen s h o u l d b e a b o u t 1-2 c m in
d i a m e t e r , a l t h o u g h smaller specimens c a n b e used.
T h e crystallites s h o u l d b e small, preferably less t h a n
a b o u t 20 , a n d t h e specimen r o t a t e d a b o u t 70 r p m
a r o u n d a n axis n o r m a l t o t h e surface t o o b t a i n g o o d
values of t h e relative intensities. T h e p o w d e r m a y be
c e m e n t e d with a 5 % s o l u t i o n of a m y l a c e t a t e in
c o l l o d i o n , o r with vaseline t o a glass slide, a shallow
cylindrical h o l d e r o r single-crystal p l a t e c u t in a
direction t h a t d o e s n o t p r o d u c e a reflection in t h e
a n g u l a r r a n g e r e c o r d e d [e.g., silicon (510)]. F i l m s a s
thin as 3 0 - 4 0 n m c a n be a n a l y z e d if they a r e well
crystallized.

Figure 2
Geometry of the x-ray powder diffractometer in the
focusing plane: F, line focus of x-ray tube; PS, parallel foil
assembly to limit divergence in plane of drawing; DS,
divergence slit; Sp, specimen; O, diffractometer axis of
rotation; , Bragg angle; RS, receiving slit; AS, antiscatter
slits; M, curved crystal monochromator; D, scintillation or
proportional counter; SpFC, specimen focusing circle
(radius varies with 0); DC, diffractometer circle with 20
scale; MFC, monochromator focusing circle

Powder

( 5

Identification

T h e identification of crystalline p h a s e s requires a file

of k n o w n s t a n d a r d d a t a for c o m p a r i s o n . T h e P o w d e r
Diffraction File p u b l i s h e d b y t h e I n t e r n a t i o n a l C e n t e r
for P o w d e r Diffraction ( S w a r t h m o r e , P e n n s y l v a n i a )
is t h e m o s t c o m p r e h e n s i v e d a t a set available a n d is
widely used for this p u r p o s e . It n o w c o n t a i n s d a t a for
a b o u t 38 000 s u b s t a n c e s in t h e f o r m of c a r d s , b o o k s
a n d m a n u a l s for h a n d searching, a n d o n m a g n e t i c
t a p e o r diskettes for r a p i d c o m p u t e r searching.
T h e time a n d success in m a k i n g identifications a r e
d e p e n d e n t o n t h e q u a l i t y of t h e e x p e r i m e n t a l d a t a a n d
t h e d a t a in t h e reference file. H a n d search usually
begins with t h e H a n a w a l t S e a r c h M a n u a l in w h i c h the
d a t a a r e a r r a n g e d in g r o u p s a n d s u b g r o u p s b a s e d o n
t h e t w o highest-intensity d values. T h e h a n d m e t h o d
h a s been used for m a n y years b u t requires consider
able time a n d experience a n d b e c o m e s m o r e difficult
when there are mixtures.
M i n i c o m p u t e r s e a r c h - m a t c h p r o g r a m s h a v e been
d e v e l o p e d t o m a k e r a p i d c o m p r e h e n s i v e searches of
t h e s t o r e d digital files ( P a r r i s h et al. 1982). T h e

583

X-Ray

Powder

Diffraction

p r o g r a m s use selectable t e r r o r w i n d o w s , a u t o m a t i c
d a t a c o r r e c t i o n with internal s t a n d a r d s , chemicald a t a prescreening a n d o t h e r o p t i o n s t o facilitate the
identification, a n d c o m p u t e a figure of merit w h i c h
gives the " g o o d n e s s of fit" of the u n k n o w n c o m p a r e d
with each of the selected p o t e n t i a l s t a n d a r d s . T h e
c o m p u t e r also displays the p a t t e r n s of the u n k n o w n
with each of the selected s t a n d a r d s for direct visual
c o m p a r i s o n . (All the p o w d e r p a t t e r n s in this article
are c o m p u t e r - g e n e r a t e d . ) It is n o w possible t o collect
the d a t a , reduce it t o a set of d a n d / values a n d
identify the c o n s t i t u e n t s of a n a v e r a g e m a t e r i a l in 1 0 20 m i n . If a user file is m a d e with a g r o u p of m a t e r i a l s
likely t o be f o u n d in a p a r t i c u l a r type of a p p l i c a t i o n ,
identification time is greatly reduced because the size
of the s t a n d a r d file is m u c h smaller a n d its q u a l i t y c a n
be controlled.
T h e r e are a large n u m b e r of a p p l i c a t i o n s of the
p o w d e r m e t h o d based o n p h a s e identification. A
typical l a b o r a t o r y use is t o follow the c o u r s e of a
solid-state chemical r e a c t i o n which c a n n o t be per
formed by chemical analysis b e c a u s e the b a t c h
c o m p o s i t i o n r e m a i n s the s a m e . F o r e x a m p l e , large
single-crystal b o u l e s of G d 3 G a 5 0 1 2, g a r n e t are used as
substrates for m a g n e t i c b u b b l e devices. T h e i r g r o w t h
requires a starting g a r n e t p o w d e r p r e p a r e d by sinter
ing a blend of G d 2 0 3 a n d G a 2 0 3 in p r o p e r p r o p o r t i o n s
to the correct t e m p e r a t u r e .
T h e p a t t e r n s required for this analysis were m a d e
with a m i n i c o m p u t e r - a u t o m a t e d diffractometer (see
Fig. 3). T h e u p p e r p a t t e r n is the s t a r t i n g oxide mix
ture blend a n d the tick m a r k s a r e the p e a k p o s i t i o n s .
T h e following t w o p a t t e r n s are the s t a n d a r d s identi
fied by c o m p u t e r s e a r c h - m a t c h : the cubic form of aG d 2 0 3 a n d the m o n o c l i n i c / ? - G a 2 0 3 . T h e intensities in
b o t h s t a n d a r d s h a v e been scaled by the c o m p u t e r t o
a p p r o x i m a t e t h o s e in the blend. T h o s e p e a k s m a t c h
ing the blend a r e identified by the lower set of tick
m a r k s . T h e e x p a n d e d p a t t e r n (Fig. 3b) s h o w s the
partially c o m p l e t e d c o n v e r s i o n t o g a r n e t a n d the
small a m o u n t of residual / ? - G a 2 0 3 indicates the cor
rect sintering c o n d i t i o n s h a v e a l m o s t been r e a c h e d .
T h e m a x i m u m n u m b e r of p h a s e s t h a t c a n be identi
fied in a specimen d e p e n d s o n the complexity of the
p a t t e r n s a n d the degree of o v e r l a p p i n g . Profile fitting
c a n be used t o s e p a r a t e the o v e r l a p p i n g reflections
a n d t o d e t e r m i n e the individual intensities (Parrish
a n d H u a n g 1979). M i x t u r e s of six p h a s e s c a n b e
p e r f o r m e d routinely with c o m p u t e r m e t h o d s .
T h e m i n i m u m a m o u n t of a p h a s e t h a t is detectable
in a m i x t u r e is d e p e n d e n t o n the a b s o r p t i o n , crystalli
nity a n d p e a k - t o - b a c k g r o u n d r a t i o s . T h e lower limits
r a n g e from a b o u t 0 . 1 - 5 w t % . Very small a m o u n t s of
a sample (in the m i c r o g r a m r a n g e ) c a n be detected,
b u t even smaller samples require special t e c h n i q u e s
using high-brilliance r o t a t i n g - a n o d e x-ray t u b e s .
Q u a n t i t a t i v e d e t e r m i n a t i o n of t h e c o n c e n t r a t i o n of
each p h a s e in a m i x t u r e requires careful specimen
p r e p a r a t i o n a n d m e a s u r e m e n t s of a few of the higher-

584

Oxide

mixture

ci-

Ll

J-

.A,

G d 20 3

, A,

> . A ,..-

/ 3 - G a 20 3
...

30

, 6 A A

. A

40

50

<

I
26

32

G A
38

20

Figure 3
Patterns of (a) mixed blend of two oxides and the phases
identified by computer search-match, and (b) after
sintering showing conversion to garnet Gd 3Ga 50 12 (G) and
residual -Ga 20 3(A) and a-Gd 2Q 3(D)

intensity reflections of e a c h c o n s t i t u e n t . It is also

necessary t o m a k e a second set of m e a s u r e m e n t s after
a d d i n g a k n o w n weight of a s t a n d a r d o r o n e of the
c o n s t i t u e n t s t o correct for differences in reflecting
p o w e r a n d a b s o r p t i o n a m o n g the p h a s e s . Q u a n t i t a
tive analyses of u p t o six c o n s t i t u e n t s h a v e been
r e p o r t e d in such c o m p l e x m a t e r i a l s a s c e m e n t s a n d
r o c k s , with accuracies of a few p e r c e n t a b s o l u t e .
T h e x-ray m e t h o d is essential for w o r k i n g o u t p h a s e
d i a g r a m s a n d is often used in c o n j u n c t i o n with differ
ential t h e r m a l analysis a n d m i c r o s c o p e studies. T h e
m a t e r i a l s a r e either q u e n c h e d a n d m e a s u r e d at r o o m
t e m p e r a t u r e , o r x-ray m e a s u r e m e n t s m a d e at c o n
trolled high t e m p e r a t u r e s . T h e p h a s e b o u n d a r i e s c a n
be d e t e r m i n e d from t h e x-ray p a t t e r n w h i c h gives the
structures of the p h a s e s , their p r o p o r t i o n s a n d lattice
parameters.
I n a s u b s t i t u t i o n a l solid s o l u t i o n the c o m p o s i t i o n
varies b u t the s t r u c t u r e r e m a i n s the s a m e , except for

X-Ray

4. Lattice-Parameter

Powder

Diffraction

Determination

T h e lattice p a r a m e t e r a0 is frequently r e q u i r e d in
m a t e r i a l s c h a r a c t e r i z a t i o n . A n u m b e r of reflections
s h o u l d be m e a s u r e d a n d their relation t o a0 is given by
E q n . (4). Careful e x p e r i m e n t a l t e c h n i q u e s m u s t be
used t o o b t a i n a c c u r a t e values. S y s t e m a t i c e r r o r s are
t h e p r i n c i p a l c a u s e of low a c c u r a c y a n d they c a n be
m i n i m i z e d by using h i g h e r - a n g l e reflections. T h e r e a r e
t w o basic r e a s o n s for this: (a) i n s t r u m e n t a l a b e r r a
t i o n s a n d specimen d i s p l a c e m e n t e r r o r s increase
r a p i d l y with decreasing reflection angle, a n d (b) the
h i g h e r t h e reflection angle t h e g r e a t e r t h e a c c u r a c y , as
s h o w n b y t h e differential f o r m of t h e B r a g g e q u a t i o n :
Figure 4
X-ray diffractometer pattern of a small quantity of
crystalline quartz (two peaks) on a glass substrate

c h a n g e s in t h e lattice p a r a m e t e r a0 if t h e s u b s t i t u t i n g
a t o m s h a v e different sizes. T h e r e is a very r o u g h linear
relation b e t w e e n c o m p o s i t i o n a n d a0 a n d t h e c o m p o
sition m a y b e d e t e r m i n e d from t h e shifts in p e a k
positions. The substituting atoms are randomly
a r r a n g e d o n t h e lattice sites, b u t in s o m e cases p r o p e r
annealing may produce a long-range order which can
be detected b y t h e a p p e a r a n c e of a d d i t i o n a l p e a k s
called s u p e r s t r u c t u r e reflections. T h e y a r e generally
m u c h w e a k e r t h a n t h e f u n d a m e n t a l reflections a n d
d e p a r t u r e s from perfect l o n g - r a n g e o r d e r further
w e a k e n s t h e m . Interstitial a n d defect types of solid
solutions m a y b e detected b y c o m p a r i n g t h e m e a s u r e d
density with t h e density c a l c u l a t e d from t h e unit-cell
volume.
T h e crystalline a n d a m o r p h o u s states c a n be readily
distinguished. A n a m o r p h o u s solid h a s only local
short-range order without the repeating long-range
lattice o r d e r characteristic of t h e crystalline state. T h e
diffraction from a n a m o r p h o u s s u b s t a n c e is a b r o a d
h u m p e x t e n d i n g o v e r a w i d e a n g u l a r r a n g e as s h o w n
b y t h e p a t t e r n of a m i c r o s c o p e slide ( F i g . 4). If t h e
m a t e r i a l c o n t a i n s a crystalline p o r t i o n o r begins t o
devitrify, t h e crystalline p a t t e r n is s u p e r i m p o s e d as
illustrated b y t h e a d d i t i o n of a few m i c r o g r a m s of
q u a r t z p o w d e r o n t o t h e slide. T h e crystalline p e a k
intensities a r e m u c h higher a n d t h e (101) reflection of
the s a m e m a s s of q u a r t z w o u l d b e a b o u t 260 times
higher t h a n t h e t o p of t h e a m o r p h o u s b a n d . M o s t
a m o r p h o u s p a t t e r n s a r e similar a n d c a n n o t b e used t o
identify m a t e r i a l s . R a d i a l d i s t r i b u t i o n functions c a n
be derived t o d e t e r m i n e local a t o m i c a r r a n g e m e n t s
( W a r r e n 1969). C r y s t a l l i n e - t o - a m o r p h o u s weight
ratios m a y be a p p r o x i m a t e l y d e t e r m i n e d f r o m t h e
relative intensities of all t h e crystalline reflections a n d
the a m o r p h o u s p a r t . T h i s usually requires s t a n d a r d s
of k n o w n r a t i o s . H o w e v e r , if p o o r l y crystallized
m a t e r i a l is p r e s e n t t h e d e t e r m i n a t i o n b e c o m e s m u c h
m o r e difficult o r impossible.

Ad/d=

-A0cos 0

(6)

T h e e x p e r i m e n t a l e r r o r 0 (in r a d i a n s ) is rarely less

t h a n 0.0 (20), w h i c h c o r r e s p o n d s t o Ad/d= 0 . 0 4 %
a t 25 (20) a n d 0 . 0 0 1 5 % a t 160.
A n i n t e r n a l s t a n d a r d such as silicon, w h o s e lattice
p a r a m e t e r is k n o w n t o high a c c u r a c y , m a y be a d d e d
t o t h e specimen t o d e t e r m i n e t h e c o r r e c t i o n s for
systematic e r r o r s . T h e reflection angle c a n be
m e a s u r e d by a p e a k - s e a r c h o r b y a profile-fitting
p r o c e d u r e , a n d t h e lattice p a r a m e t e r d e t e r m i n e d from
a least-squares fit, preferably w e i g h t i n g t h e higherangle reflections. T h e lattice p a r a m e t e r c a n be deter
m i n e d with a precision of 0.10.01 % a n d o n e o r d e r of
m a g n i t u d e higher w i t h very careful t e c h n i q u e s . T h e r
m a l e x p a n s i o n a n d its v a r i a t i o n s with crystal direction
in n o n c u b i c crystals c a n b e d e t e r m i n e d from m e a s u r e
m e n t s of a0 a t different t e m p e r a t u r e s .
T h e l a t t i c e - p a r a m e t e r d e t e r m i n a t i o n is usually car
ried o u t w i t h polycrystalline specimens b u t t h e r e a r e
i m p o r t a n t a p p l i c a t i o n s for single crystals. F o r ex
a m p l e , t h e g r o w t h of single-crystal g a r n e t b o u l e s
requires a n a c c u r a t e l a t t i c e - p a r a m e t e r m e a s u r e m e n t
t o o b t a i n t h e correct G d : G a r a t i o . T h e lattice p a r a
m e t e r varies w i t h t h e r a t i o a n d t h e c o m p o s i t i o n c a n be
d e t e r m i n e d w i t h far g r e a t e r precision from a m e a s u r e
m e n t of a0 t h a n is possible w i t h fluorescence o r
electron m i c r o p r o b e e l e m e n t a l analysis. T h e m e t h o d
requires a fine c o l l i m a t e d x-ray b e a m (Fig. 5) a n d t w o
m e a s u r e m e n t s of t h e s a m e reflection o n e a c h side of
t h e direct b e a m as i n d i c a t e d b y t h e t w o p o s i t i o n s of
crystal C I . T h e p r o c e d u r e is simplified b y t h e use
of t w o d e t e c t o r s t o m e a s u r e t h e angle 36O-40 from
w h i c h a0 c a n be calculated.
A similar t e c h n i q u e c a n b e used t o m e a s u r e the
difference in lattice p a r a m e t e r s of a n epitaxial
film a( a n d t h e single-crystal s u b s t r a t e as. T h e lat
tice m i s m a t c h Aa/a = (asaf)/tfs
d e t e r m i n e s the
stress-induced a n i s o t r o p y , o n e of t h e t w o sources of
m a g n e t i c uniaxial a n i s o t r o p y in g a r n e t films. T h e
difference in reflection angles of t h e film a n d s u b s t r a t e
4
d e t e r m i n e s Ad/d = Aa/a 10~ . A double-crystal
t e c h n i q u e is desirable t o o b t a i n sufficient resolution t o
s e p a r a t e t h e closely spaced reflections. T h e m e t h o d

585

X-Ray

Powder

Diffraction

5. Preferred

Orientation

N o n r a n d o m d i s t r i b u t i o n of crystallites in a m a t e r i a l is
called preferred o r i e n t a t i o n o r t e x t u r e . It m a y result
from t h e m e t h o d of p r e p a r a t i o n a n d c a n m a r k e d l y
affect t h e p r o p e r t i e s . F o r e x a m p l e , t h e crystallites in a
c o l d - d r a w n wire orient w i t h t h e s a m e c r y s t a l l o g r a p h i c
direction parallel t o t h e wire axis, a n d in rolled m e t a l
sheets certain p l a n e s orient parallel t o t h e surface a n d
t h e rolling direction w h e n t h e grains r o t a t e a n d align
d u r i n g t h e plastic d e f o r m a t i o n . Preferred o r i e n t a t i o n
also o c c u r s in castings, electrochemical d e p o s i t i o n
a n d t h i n films. T h e degree of preferred o r i e n t a t i o n c a n
be d e t e r m i n e d with a pole-figure device a t t a c h e d t o
t h e diffractometer t o m e a s u r e intensities for different
specimen o r i e n t a t i o n s . T h e intensities c a n b e p l o t t e d
o n a s t e r e o g r a p h i c projection a n d c o n t o u r e d t o s h o w
t h e a n g u l a r d i s t r i b u t i o n of t h e n o r m a l s t o selected
lattice p l a n e s in v a r i o u s c r y s t a l l o g r a p h i c directions.
Such p l o t s a r e used t o follow s t r u c t u r a l c h a n g e s in
metallurgical m a t e r i a l s subjected t o m e c h a n i c a l a n d
t h e r m a l processes.

(b)

Figure 5
(a) Method for precision lattice-parameter measurement of
single-crystal plate and mismatch of epitaxial film on
substrate by parallel double-crystal method, and
(b) profiles of pair of films F and C on substrate S

uses a n o n d i v e r g e n t m o n o c h r o m a t i c b e a m from a
high-quality g a r n e t wafer C 2 m o u n t e d a p p r o x i m a t e l y
parallel t o C I , d e t e c t o r D l is m o v e d t o , a n d t h e
specimen C I r o t a t e d t o pick u p t h e reflections s h o w n
in the lower p a r t of Fig. 5. (In p r a c t i c e C I a n d C 2 c a n
be i n t e r c h a n g e d . ) T h e e x a m p l e s h o w n is a p a i r of
films F a n d C of different c o m p o s i t i o n s g r o w n o n t h e
s u b s t r a t e S with lattice p a r a m e t e r s of F > S > C . T h e
p e a k s e p a r a t i o n of C a n d S is 112" ( c o r r e s p o n d i n g t o
4
Aa/a = 2.1 x 10~ ) a n d b e t w e e n F a n d S is
4
76" = 2.2 x 1 0 " from which t h e m e a n strain in e a c h
film c a n be calculated. T h e large difference in a0
between film F d e p o s i t e d o n film C c a u s e d a s y m m e t
ric b r o a d e n i n g of t h e F profile i n d i c a t i n g n o n u n i f o r m
strain. T h i s is a n e x a m p l e of t h e u n i q u e analytical
capabilities of x-ray diffraction in which t h e indi
vidual p r o p e r t i e s of physically s u p e r i m p o s e d m a t e r
ials c a n be d e t e r m i n e d .

586

I n m a t e r i a l s science it is often necessary t o p r e p a r e

thin films in w h i c h t h e crystallites h a v e specific orien
t a t i o n s w i t h respect t o t h e surface in o r d e r t o achieve
t h e desired physical o r m a g n e t i c p r o p e r t i e s . T h e d e
gree of preferred o r i e n t a t i o n t h a t c a n b e achieved
d e p e n d s o n t h e s t r u c t u r e of t h e s u b s t r a t e , m e t h o d of
p r e p a r a t i o n , m o r p h o l o g y a n d related factors. It c a n
be d e t e r m i n e d from t h e relative intensities of e a c h of
t h e reflections c o m p a r e d with t h o s e of a r a n d o m l y
oriented p o w d e r [e.g., 7(220) powder/film]. If a
p o w d e r is n o t available t h e r a n d o m p a t t e r n c a n b e
calculated from t h e crystal s t r u c t u r e . T h e m e a s u r e
m e n t s a r e m a d e with a diffractometer b e c a u s e only
t h o s e crystallites w h o s e lattice p l a n e s a r e within a b o u t
of parallelism with t h e surface c a n reflect.
I n e x t r e m e cases of preferred o r i e n t a t i o n only a
single reflection o c c u r s , s h o w i n g t h a t t h e entire film
h a s t h a t lattice p l a n e parallel t o t h e surface. T h e
a b s o l u t e intensity m a y also b e m u c h higher t h a n the
p o w d e r . If t h e s a m e specimen is m e a s u r e d in t r a n s
mission using a modification of t h e i n s t r u m e n t geo
m e t r y in F i g . 1, only t h e p l a n e s n o r m a l t o t h e surface
will be able t o reflect. C o m p a r i s o n of t h e relative
intensities of t h e reflection a n d t r a n s m i s s i o n p a t t e r n s
gives a g o o d m e a s u r e of t h e preferred o r i e n t a t i o n . I n p l a n e o r i e n t a t i o n c a n be d e t e r m i n e d b y setting t h e
diffractometer o n a p e a k a n d m e a s u r i n g t h e intensity
as t h e film is slowly r o t a t e d a r o u n d a n axis n o r m a l t o
t h e surface. If there is r a n d o m i n - p l a n e o r i e n t a t i o n t h e
intensity will be u n i f o r m a n d preferred o r i e n t a t i o n
causes b r o a d p e a k s a n d valleys in such a scan.
6.

Imperfections

R e a l crystals rarely h a v e t h e ideal s t r u c t u r e of a

perfectly r e p e a t i n g lattice. V a r i o u s types of imperfec
tions a r e p r e s e n t a n d m a n y of t h e m modify t h e
physical p r o p e r t i e s of t h e m a t e r i a l . S o m e imperfec-

X-Ray

84

85

86

87

88

1
89

20

Figure 6
X-ray diffractometer reflection profiles of Pd(222) thin
film broadened by strain and standard well-crystallized
powder W(220); peak intensities normalized

tions c a u s e easily o b s e r v a b l e c h a n g e s in t h e x-ray

pattern. F o r example, crushing a n d grinding m a y
cause large s t r a i n s w h i c h p r o d u c e b r o a d e n e d reflec
tions w i t h d i m i n i s h e d p e a k h e i g h t s . S t r a i n release b y
a n n e a l i n g c a n b e followed b y t h e s h a r p e n i n g o f t h e
reflections. F i g u r e 6 s h o w s t h e b r o a d (222) reflection
of a highly s t r a i n e d t h i n film o f p a l l a d i u m a n d t h e
m u c h n a r r o w e r (220) reflection o f well-crystallized
t u n g s t e n p o w d e r free o f strain; t h e latter results o n l y
from t h e i n s t r u m e n t function i n h e r e n t in t h e experi
mental method.
In analyses b a s e d o n profile m e a s u r e m e n t s , it is first
necessary t o s u b t r a c t t h e effect o f t h e i n s t r u m e n t
function t o derive t h e p u r e diffraction effects f r o m t h e
specimen. T h e i n s t r u m e n t g e o m e t r y , a b e r r a t i o n s a n d
x-ray spectral line s h a p e s c o n v o l v e t o p r o d u c e profile
s h a p e s w h i c h v a r y w i t h 20. T h e s e basic line s h a p e s c a n
be m e a s u r e d w i t h well-crystallized specimens free o f
line b r o a d e n i n g ( F i g . 6). C o m p u t e r p r o g r a m s a r e
desirable t o m a k e t h e c a l c u l a t i o n s .
T h e x-ray s t u d y o f i m p e r f e c t i o n s in polycrystalline
m a t e r i a l s r e q u i r e s t h a t a c o n s i d e r a b l e fraction o f t h e
a t o m s a r e involved t o m a k e t h e effect d e t e c t a b l e , a n d
the results a r e t h u s statistical r a t h e r t h a n o n t h e basis
of a few u n i t cells. Small-scale i m p e r f e c t i o n s a r e b e t t e r
d e t e r m i n e d b y special x-ray single-crystal a n d e l e c t r o n
m i c r o s c o p e studies. T h e r e h a v e b e e n v a r i o u s types o f
imperfections e l u c i d a t e d b y x-ray diffraction such a s
o r d e r - d i s o r d e r in solid s o l u t i o n s , plastic a n d elastic
deformation, homogeneous a n d inhomogeneous
strains, e r r o r s in layer s t a c k i n g , twin faulting a n d
small crystallite size. T h e s e c a u s e subtle c h a n g e s in
t h e x-ray p a t t e r n b y s y m m e t r i c a n d a s y m m e t r i c
b r o a d e n i n g o f t h e profiles a n d small shifts in t h e p e a k
p o s i t i o n s . T h e analyses r e q u i r e a c c u r a t e m e a s u r e m e n t
of t h e profile s h a p e s , profile-fitting m e t h o d s a n d
Fourier-series analysis o f t h e profiles u s i n g t h e coeffi
cients t o r e p r e s e n t t h e b r o a d e n i n g .

Powder

Diffraction

X - r a y m e t h o d s a r e used a s a n o n d e s t r u c t i v e
m e t h o d t o d e t e r m i n e residual elastic strains. A l
t h o u g h t h e elastic c o n s t a n t s v a r y c o n s i d e r a b l y with
c r y s t a l l o g r a p h i c d i r e c t i o n they a r e r o u g h l y i s o t r o p i c
in r a n d o m polycrystalline m a t e r i a l s . U s i n g small xr a y b e a m s , s t r a i n s c a n b e m e a s u r e d in small a r e a s a n d
steep s t r a i n g r a d i e n t s c a n b e d e t e r m i n e d . T h e m e t h o d
is b a s e d o n t h e fact t h a t t h e lattice s p a c i n g d{hkl,
c h a n g e s w i t h a p p l i e d stress a n d acts a s a n i n t e r n a l
s t r a i n g a u g e . U n i f o r m l o n g - r a n g e tensile strain in
creases t h e d values a n d shifts t h e p e a k s t o smaller
angles w i t h o u t b r o a d e n i n g . N o n u n i f o r m s t r a i n s c a u s e
b r o a d e n i n g w i t h o u t shifts. B o t h elastic a n d plastic
d e f o r m a t i o n strains c a u s e shifts a n d b r o a d e n i n g .
W h e n t h e d i m e n s i o n s of crystallites a r e less t h a n
a b o u t 1 t h e profiles begin t o b r o a d e n a n d t h e
b r o a d e n i n g increases w i t h d e c r e a s i n g size. B o t h size
a n d strain b r o a d e n i n g c a n b e m e a s u r e d w h e n they
coexist b y u s i n g t h e F o u r i e r m e t h o d a n d several
o r d e r s o f a reflection; t h e size factor is i n d e p e n d e n t of,
a n d t h e d i s t o r t i o n d e p e n d e n t o n , t h e o r d e r of t h e
reflection.
A simplified m e t h o d frequently used t o d e t e r m i n e
small crystallite sizes a s s u m e s t h e r e a r e n o strains o r
o t h e r sources of line b r o a d e n i n g . It uses t h e Scherrer
equation:
=

cos 0 ^ B( 2 0 )

w h e r e t{hkl) is t h e a v e r a g e d i m e n s i o n o f t h e crystallites
n o r m a l t o t h e (hkl) diffracting p l a n e , k is a c o n s t a n t
usually t a k e n a s 0.9, is t h e w a v e l e n g t h ( n m ) 0
t h e B r a g g angle a n d PB (2) t h e particle size line
b r o a d e n i n g in r a d i a n s m e a s u r e d a s t h e full-width
h a l f - m a x i m u m ( F W H M ) . (2) is o b t a i n e d from
>

>

/ B(2^) = [ / O ^ ) - ^ S T ( 2 ^ ) ]

1 /2

(8)

w h e r e P0 (20) is t h e w i d t h o f t h e m e a s u r e d profile a n d
PST(29) t h e w i d t h of t h e i n s t r u m e n t function profile.
F o r a given t t h e b r o a d e n i n g increases a s l / c o s 0 ,
b u t t h e intensities decrease w i t h increasing 2 a n d
d e c r e a s i n g r, m a k i n g it m o r e difficult t o m a k e accur
a t e m e a s u r e m e n t s . I n p r a c t i c e t h e useful r a n g e of t h e
m e t h o d is a b o u t 5 - 3 0 0 n m . A l t h o u g h t c a n b e deter
m i n e d for several d i r e c t i o n s b y u s i n g different (hkl)
p l a n e s , it is desirable t o u s e s c a n n i n g electron m i c r o s
c o p y t o d e t e r m i n e t h e m o r p h o l o g y b e c a u s e if t h e
particles a r e needles o r p l a t e s t h e results c o u l d b e in
e r r o r . T h e t w o m e t h o d s a r e c o m p l e m e n t a r y since t h e
x-ray m e t h o d gives t h e a v e r a g e crystallite size a n d t h e
m i c r o s c o p e t h e particle size, w h i c h m a y b e clusters of
crystallites.
Diffuse s c a t t e r i n g within a few degrees o f t h e direct
b e a m (small-angle diffraction) is a m e t h o d used for
particle size d e t e r m i n a t i o n typically from a few n a n o
m e t e r s t o tens o f n a n o m e t e r s . It is a p p l i c a b l e t o
a m o r p h o u s a s well a s crystalline m a t e r i a l s , a n d is used
for a n a l y z i n g s u s p e n s i o n s , single-chain d i m e n s i o n s of

587

X-Ray

Powder

Diffraction

p o l y m e r solutions, lamellar s e p a r a t i o n distances in

semicrystalline p o l y m e r s a n d p h a s e - b o u n d a r y thick
nesses in t w o - p h a s e systems. T h e m e t h o d requires
special i n s t r u m e n t a t i o n a n d c o l l i m a t o r s d u e t o t h e
necessity of m e a s u r i n g so close t o t h e p r i m a r y b e a m .
See also: Single-Crystal X-Ray Diffraction; X-Ray and
Neutron Diffraction Studies of Amorphous Solids

Bibliography
Azaroff L V, Buerger J 1958 The Powder Method in XRay Crystallography. McGraw-Hill, New York
Barrett C S, Massalski 1966 Structure of Metals:
Crystallographic Methods, Principles and Data, 3rd edn.
McGraw-Hill, New York
Guinier A 1956 Theorie et Technique de la Radiocristallographie. Dunod, Paris
International Tables for X-Ray Crystallography
1969.
Kynoch, Birmingham, UK
Klug , Alexander L 1974 X-Ray Diffraction Proced
ures for Poly crystalline and Amorphous Materials, 2nd

588

edn. Wiley, New York

Lipson S, Steeple 1970 Interpretation of X-Ray Powder
Diffraction Patterns. Macmillan, London
Parrish W 1965 X-Ray Analysis Papers. Philips (Centrex).
Eindhoven, The Netherlands
Parrish W, Ayers G L, Huang C 1982 A versatile
minicomputer x-ray search/match system. Advances in XRay Analysis, Vol. 25. Plenum, New York, pp. 221-9
Parrish W, Huang C 1979 Accuracy of the profile fitting
method for x-ray polycrystalline diffractometry. In: Block
S, Hubbard C R (eds.) 1979 Accuracy in Powder Diffrac
tion, NBS Special Publication No. 567. National Bureau
of Standards, Washington, DC, pp. 95-110
Peiser S, Rooksby , Wilson A J C (eds.) 1955 X-Ray
Diffraction by Polycrystalline Materials. Institute of Phys
ics, London
Schwartz L H, Cohen J 1977 Diffraction from Materials.
Academic Press, New York
Warren 1969 X-Ray Diffraction. Addison-Wesley,
Reading, MA
W. P a r r i s h
[IBM, S a n J o s e , California, U S A ]


X-Ray Absorption Spectroscopy:
EXAFS and XANES Techniques
X - r a y spectroscopies, in v a r i o u s forms, h a v e l o n g
been exploited for s t u d y i n g t h e electronic a n d crystallographic s t r u c t u r e of solids. M o s t extensively uti
lized, of c o u r s e , a r e diffraction t e c h n i q u e s e m p l o y e d
for the p u r p o s e of e x t r a c t i n g c r y s t a l l o g r a p h i c infor
m a t i o n . H o w e v e r , x-ray a b s o r p t i o n studies a r e cur
rently experiencing a s t r o n g surge of scientific interest
resulting from recent i m p o r t a n t a d v a n c e s , b o t h in
theoretical u n d e r s t a n d i n g a n d in e x p e r i m e n t a l c a p a
bility. E x p e r i m e n t a l l y , t h e E X A F S (extended x-ray
a b s o r p t i o n fine structure) a n d X A N E S (x-ray a b s o r p
tion near-edge fine s t r u c t u r e ) techniques a r e dis
tinguished simply b y their spectral r a n g e s ( m e a s u r e d
relative t o a n x-ray a b s o r p t i o n edge). T h e distinction
is m a d e since x-ray-induced electronic excitations in
the vicinity of t h e edge involve c o n s i d e r a t i o n s t h a t a r e
s o m e w h a t different from t h e m o r e energetic p r o
cesses. Oscillatory s t r u c t u r e in t h e x-ray a b s o r p t i o n
coefficient t h a t m a y b e o b s e r v e d in t h e higher spectral
r a n g e (40 eV ^ hv ^ 1000 eV a b o v e t h e edge) is called
E X A F S , while X A N E S refers t o t h e s t r u c t u r e in t h e
i m m e d i a t e vicinity of t h e edge (i.e., for hv ^ 50 eV
a b o v e t h e edge). T h e s e x-ray a b s o r p t i o n t e c h n i q u e s
h a v e u n i q u e capabilities a n d a r e being used t o s t u d y a
wide variety of c o m p l e x m a t e r i a l s . Studies of a m o r
p h o u s m a t e r i a l s , catalysts, biological m a t e r i a l s a n d
solutions h a v e been r e p o r t e d .
I n this article, t h e u n d e r l y i n g theoretical c o n c e p t s
of E X A F S a n d X A N E S a r e outlined a n d recent
experimental a d v a n c e s a r e discussed. A d v a n t a g e s a n d
limitations of t h e x-ray a b s o r p t i o n spectroscopies,
a n d types of p r o b l e m s m o s t suited for these tech
niques, will b e discussed. M o r e detailed discussions
are available in literature reviews, a n d t h e extensive
review b y Lee et al. (1981) is particularly r e c o m
m e n d e d t o t h e interested reader.

1. Theory

and Comparison

with

()\(/\}\ ()

*(*) = Z^jH)f(k)sm[2krj

)]

j
2

x exp( - 2k ) )exp( - 2/)

(2)

1.6,-

Experiment

W i t h i n t h e electric dipole a p p r o x i m a t i o n , t h a t p a r t of
the a b s o r p t i o n coefficient resulting from p h o t o e m i s sion from a core state is given b y
2

a n a m b i t i o u s theoretical effort is being m a d e t o

u n d e r s t a n d t h e X A N E S region. I n c o n t r a s t , t h e
E X A F S region a p p e a r s t o b e r a t h e r well u n d e r s t o o d .
T h u s w e will p r o c e e d t o discuss E X A F S a n d follow
with a discussion of t h e n e a r - e d g e region.
I n t h e E X A F S regions, p h o t o e j e c t e d electrons a r e
excited t o final states far a b o v e t h e F e r m i level. A t
these energies, t h e t o t a l final density of states varies
s m o o t h l y (with hv), a n d oscillatory b e h a v i o r in ()
results only from v a r i a t i o n s in t h e m a t r i x element. I n
this case, a single-scattering (i.e., w e a k scattering)
a p p r o x i m a t i o n c a n b e used t o calculate t h e final-state
w a v e function. T h i s w a v e function c a n b e viewed a s
an outgoing wave superimposed on a wave backscattered from t h e s u r r o u n d i n g a t o m s . T h i s b a c k s c a t t e r e d
w a v e interferes, either destructively o r constructively
( d e p e n d i n g o n hv), with t h e o u t g o i n g w a v e , t h u s
p r o d u c i n g oscillations in (). T h i s oscillatory b e
h a v i o r is illustrated in t h e E X A F S spectra of nickel
(Fig. 1). T h e oscillatory p a r t of () m a y t h e n b e
isolated with t h e relation x(k) = ( 0)/0,
where
0 is a s m o o t h l y v a r y i n g b a c k g r o u n d a n d k
l/2
2n/h[2m(E - E0)] .
H e r e , m is t h e electron m a s s ,
h is P l a n c k ' s c o n s t a n t a n d E0 is t h e zero of energy of
the o u t g o i n g electron. A p l o t of kx(k) for t h e d a t a of
Fig. 1 is s h o w n in F i g . 2a.
Sayers et al. (1971) s h o w e d t h a t x(k) is related t o
a t o m i c p a r a m e t e r s b y t h e expression

0.7h

0)

w h e r e is t h e p h o t o n energy, p(E) is t h e density of

final states a n d < / | r | / > is t h e electric-dipole m a t r i x
element. I n t h e n e a r - e d g e region ( X A N E S ) , t h e calcu
lation of () is difficult because b o t h t h e m a t r i x
element a n d t h e density of final states d e p e n d , in
c o m p l i c a t e d w a y s , o n t h e p h o t o n energy. A t present,

8500

9000
Energy

(eV)

Figure 1
The absorption coefficient (multiplied by the thickness
JC) of nickel as a function of energy at 38
555

X-Ray

Absorption

Spectroscopy:

EXAFS

and XANES

Ac

(b)

Figure 2
(a) The EXAFS spectrum, kx{k) vs k, and (b) the radial
distribution function, ^(r) vs r, for nickel at 38 K. The
numbers in parentheses are the number of atoms per shell,
indicated at the known shell distances

w h e r e r} is t h e d i s t a n c e from t h e c e n t r a l ( a b s o r b e r )
a t o m t o t h e yth shell of a t o m s , Nj is t h e n u m b e r of
a t o m s in the shell, is a D e b y e - W a l l e r - l i k e factor
which m e a s u r e s t h e a i s o r d e r of t h e a t o m s in t h e yth
shell relative t o t h e central a t o m a n d is a m e a n free
p a t h , e s t i m a t e d t o be 3.5-5 A. T h e a m p l i t u d e function
ffi) a n d t h e p h a s e function ) c a n be calculated
theoretically o r d e t e r m i n e d empirically from c o m
p o u n d s of k n o w n s t r u c t u r e . I n principle, therefore,
the p a r a m e t e r s Np rp cr, a n d c a n b e d e t e r m i n e d
for the first few n e a r - n e i g h b o r shells. I n practice,
however, there a r e limits o n t h e n u m b e r of p a r a m e t e r s
t h a t c a n be i n d e p e n d e n t l y d e t e r m i n e d a n d also o n t h e
a c c u r a c y of t h e d e t e r m i n a t i o n s . In m a n y cases, dis
tances between the central a t o m a n d t h e first shell of
s u r r o u n d i n g n e i g h b o r s in a n u n k n o w n m a t e r i a l c a n
be d e t e r m i n e d t o 0 . 0 1 A, a n d t h e n u m b e r of first
n e a r n e i g h b o r s c a n be m e a s u r e d t o b e t t e r t h a n 2 0 %
accuracy.
Analysis of E X A F S spectra is c o n s i d e r a b l y a i d e d
by calculating t h e F o u r i e r t r a n s f o r m of kx(k).
Because of the special form of E q n . (2), t h e F o u r i e r
t r a n s f o r m of kx(k) is a p a r t i c u l a r l y useful inter
p r e t a t i o n . T h e t r a n s f o r m #?(r) is a r a d i a l - d e p e n d e n t
function t h a t a p p r o x i m a t e l y m e a s u r e s the spatial dis
t r i b u t i o n of b a c k s c a t t e r i n g a t o m s relative t o t h e cen
556

Techniques

tral a t o m . <p(r) is called t h e E X A F S r a d i a l d i s t r i b u t i o n

function ( R D F ) . T h i s function is unlike r a d i a l distri
b u t i o n functions d e t e r m i n e d b y diffraction t e c h n i q u e s
in t h a t , with E X A F S , t h e R D F is m e a s u r e d relative t o
a n identifiable c e n t r a l a t o m . T h e F o u r i e r t r a n s f o r m
q>(r) of t h e nickel E X A F S s p e c t r a s h o w n in Fig. 2a is
p r e s e n t e d in Fig. 2 b . T h e p e a k s ( a p p r o x i m a t e l y ) spe
cify t h e r a d i a l p o s i t i o n s of t h e n e a r shells of a t o m s
t h a t s u r r o u n d t h e nickel a b s o r b e r : t h e o b s e r v e d p e a k s
c o r r e s p o n d t o t h e first four n e a r - n e i g h b o r shells. A l s o
indicated a r e t h e k n o w n shell distances a n d t h e
n u m b e r of a t o m s p e r shell. T h e shifts b e t w e e n t h e
p e a k p o s i t i o n s a n d t h e k n o w n shell distances result
from t h e t e r m q>(k) (in E q n . (2)), w h i c h w a s n o t
included in t h e t r a n s f o r m of F i g . 2 b . A l s o , t h e a m p l i
2
t u d e s a r e d a m p e d b y t h e 1/r a n d exp( -/)
terms.
Inclusion of t h e <pfk) t e r m in E q n . (2) allows a n
a c c u r a t e d e t e r m i n a t i o n of t h e atomic-shell radii.
O f c o u r s e , t h e s t r u c t u r a l p a r a m e t e r s for nickel were
previously k n o w n from diffraction studies. T h e nickel
E X A F S results w e r e p r e s e n t e d t o illustrate s t a n d a r d
d a t a - a n a l y s i s t e c h n i q u e s a n d t h e t y p e of i n f o r m a t i o n
t h a t c o u l d be d e t e r m i n e d from a n u n k n o w n m a t e r i a l .
A s e c o n d e x a m p l e p r e s e n t s results from a n E X A F S
s t u d y of u r a n i u m in dilute a q u e o u s s o l u t i o n . A radial
d i s t r i b u t i o n function, o b t a i n e d from analysis of u r a
n i u m L-edge d a t a , is s h o w n in Fig. 3. T h e a q u e o u s
s a m p l e c o n t a i n e d u r a n i u m in 0.02 m o l a r c o n c e n t r a
tion (360 p p m ) . T w o p r o m i n e n t p e a k s a r e seen in Fig.
3. T h e n e a r p e a k c o r r e s p o n d i n g t o a U - O s e p a r a t i o n
of ~ 1 . 7 A, results from t w o tightly b o u n d oxygen
a t o m s t h a t b i n d t o u r a n i u m in t h e linear-chain " u r a n y l " configuration. Five o r six m o r e oxygen a t o m s ,
l o c a t e d a t ~ 2 . 4 A, p r o d u c e t h e s e c o n d p e a k . D e b y e W a l l e r factors o b t a i n e d for t h e t w o shells indicate
t h a t t h e s e c o n d oxygen shell is m u c h less tightly
b o u n d t o t h e u r a n i u m a t o m . T h e m o r e d i s t a n t oxygen
a t o m s p r o b a b l y c o r r e s p o n d t o w a t e r molecules t h a t

(A)

Figure 3
The uranium L-edge radial-distribution function, <p(R) vs
R, for a 0.02 molar uranium aqueous solution

X-Ray

Absorption

form a h y d r a t i o n shell. T h e s e results for a dilute

a q u e o u s s a m p l e were easily a c q u i r e d a n d p r o v i d e d
i n f o r m a t i o n t h a t w o u l d b e o t h e r w i s e difficult t o
obtain.
E X A F S spectra c a n b e described with a simple
formalism. O n t h e o t h e r h a n d , x-ray spectra in t h e
n e a r vicinity of a n a b s o r p t i o n edge c a n n o t be so
simply related t o m a t e r i a l s p a r a m e t e r s . X A N E S dir
ectly p r o b e s u n o c c u p i e d electron states of t h e p h o t o ionized ion. T h e s e states a r e sensitive t o chemical
b o n d i n g a n d h e n c e t o c r y s t a l l o g r a p h i c o r d e r a n d ion
electronegativity. C o n s e q u e n t l y , X A N E S spectra a r e
influenced b y t h e types of a t o m s involved a n d b y t h e
c o o r d i n a t i o n s y m m e t r y of t h o s e a t o m s in p r o x i m i t y
t o t h e a b s o r b e r . T h e spectra a r e , of c o u r s e , influenced
by t h e q u a n t u m n u m b e r s of t h e initial (core electron)
state since t h e excitations a r e p r e d o m i n a n t l y electric
dipole interactions. T h u s , the a n g u l a r m o m e n t u m of t h e
(initial-state) core electron d e t e r m i n e s t h o s e a n g u l a r m o m e n t u m c o m p o n e n t s of t h e u n o c c u p i e d states t h a t
a r e t o be p r o b e d . F o r K - e d g e X A N E S spectra ( I s c o r e
state), the dipole selection rule allows t r a n s i t i o n s only
t o e m p t y states w h i c h h a v e s y m m e t r y . T h e s e e m p t y
states consist of h y b r i d i z e d orbitals which, by n a t u r e ,
a r e c o m p l e x a n d r e q u i r e extensive c o m p u t a t i o n t o
describe in detail. N o n e t h e l e s s , certain c o m m o n
physical characteristics a p p a r e n t l y c a n p r o d u c e c o m
m o n features in X A N E S s p e c t r a w i t h t h e result t h a t
X A N E S c a n be extremely useful as a fingerprinting
t e c h n i q u e , for e x a m i n i n g u n k n o w n m a t e r i a l s (see, for
e x a m p l e , M a y l o t t e et al. 1981). I n m a n y cases,
valence, s y m m e t r y of t h e c e n t r a l a t o m site a n d even
crystal s t r u c t u r e c a n b e d e t e r m i n e d b y c o m p a r i n g t h e
u n k n o w n sample to characterized standards.
T o illustrate, K - e d g e X A N E S spectra a r e s h o w n in
Fig. 4 for a n u m b e r of t r a n s i t i o n m e t a l oxides t h a t
occur in several different p h a s e s . All spectra c o r r e s
p o n d t o x-ray a b s o r p t i o n n e a r t h e metallic e l e m e n t
edge a n d a r e displayed with t h o s e edges aligned.
T h e K - e d g e excitation energy varies from a p p r o x i
m a t e l y 4040 eV in c a l c i u m t o a b o u t 8330 eV in nickel.
N o t e t h a t within e a c h p h a s e t h e spectra a r e q u i t e
similar in a p p e a r a n c e ( s h o w i n g relative i n d e p e n d e n c e
from the choice of t r a n s i t i o n element) b u t s p e c t r a for
different crystal p h a s e s a r e distinctly different.

2. Experimental

Considerations

Since E X A F S oscillation a m p l i t u d e s a r e usually a

small fraction of t h e a b s o r p t i o n - e d g e step height,
E X A F S m e a s u r e m e n t s r e q u i r e a very high precision
d e t e r m i n a t i o n of t h e x-ray a b s o r p t i o n coefficient,
a l t h o u g h a b s o l u t e m e a s u r e m e n t s of () a r e n o t
required. I n general, noise levels s h o u l d b e less t h a n
- 0 . 1 % of t h e signal a m p l i t u d e . (Generally, X A N E S
spectra c a n be a c q u i r e d m o r e quickly a n d for m o r e
dilute s a m p l e s t h a n is possible using t h e E X A F S
technique.) C h a r a c t e r i s t i c w a v e l e n g t h s of E X A F S

Spectroscopy:

EXAFS

and XANES

CaO

: V / \ ^ L o T i 0 3_

V.

;
/ / ^ \

Techniques

MnO

f.

Fe0 M
5 q Q 05

LaMn03

w / /
L

/ : ^ \

'

J*

(b)

A^CeVO^

N d/ 0 > M
5 o

At

^ l

T5 i 0

r\

_ 0

C O A I 2O 4

\ ^

Pi

NiO

.*

(a)

CoO

1 1 1 1 1 1 1 1 1

'
1

Ve

1 1 1 1 1 1

IA\

Energy

Figure 4
K-edge XANES spectra for (a) perovskites,
(b) monoxides, (c) zircon-type oxides and (d) spinels

oscillations a r e such t h a t t h e e x p e r i m e n t a l resolution

s h o u l d a l w a y s b e as g o o d as 1 5 e V a n d preferably
b e t t e r t h a n 10 eV. T h e high-precision a n d highr e s o l u t i o n r e q u i r e m e n t s a r e best served by very high
intensity sources. T h e m o s t intense x-ray sources ( n o w
available in several l o c a t i o n s a r o u n d t h e w o r l d ) a r e
high-energy electron s t o r a g e rings which g e n e r a t e
extremely intense fluxes of s y n c h r o t r o n r a d i a t i o n .
Utilizing d o u b l e - c r y s t a l m o n o c h r o m a t o r s , these faci
lities often p r o d u c e x-ray b e a m s w i t h 1-2 eV resolu
8
12
1
tion a n d fluxes of 10 10 p h o t o n s s " . W i t h x-ray
b e a m s of such high intensity a n d r e s o l u t i o n , highq u a l i t y spectra c a n often b e a c q u i r e d very quickly (in
m i n u t e s of r u n time). T h e s e extremely high intensities
also m a k e possible t h e s t u d y of dilute c o n c e n t r a t i o n s
( p p m levels) of a b s o r b e r dispersed in a h o s t m a t r i x .
W i t h a p p r o p r i a t e d e t e c t i o n t e c h n i q u e s , surface a t o m s
m a y also be selectively studied. A l s o , with s y n c h r o
tron radiation, both X A N E S and E X A F S measure
m e n t s c a n be c o n v e n i e n t l y m a d e in o n e e x p e r i m e n t a l
r u n . D i s a d v a n t a g e s in t h e use of s y n c h r o t r o n r a d i a
tion a r e t h e restricted access t o t h e x-ray b e a m a n d
c o m p l i c a t i o n s associated with c o n d u c t i n g experi
ments at distant locations.

557

X-Ray

Absorption

Spectroscopy:

EXAFS

and XANES

A n e x p e r i m e n t a l alternative is also available with

m o d e r n l a b o r a t o r y x-ray sources. ( B o t h l a b o r a t o r y
a n d s y n c h r o t r o n sources a r e discussed in Stern
(1980).) W i t h a 10-12 eV b a n d w i d t h , a flux of
7
1
is achievable. T h e high-intensity
10 p h o t o n s s "
l a b o r a t o r y systems d e p e n d u p o n a curved-crystal
m o n o c h r o m a t o r t o focus diverging r a d i a t i o n , p r o
d u c e d b y c o n v e n t i o n a l x-ray g e n e r a t o r s , o n t o t h e
sample. F o r concentrated materials, high-quality
E X A F S spectra (e.g., t h e d a t a of F i g . 1) a r e typically
r e c o r d e d in r u n times of 10-30 m i n . F o r X A N E S ,
w h e r e t h e higher resolution ( b u t smaller energy
range) is n e e d e d , r u n times a r e c o m p a r a b l e . M a t e r i a l s
c o n t a i n i n g dilute c o n c e n t r a t i o n s of a b s o r b e r in a lowa t o m i c - n u m b e r m a t r i x c a n also b e studied with preci
sion. F o r e x a m p l e , spectra for a catalyst c o n t a i n i n g
0.1 w t % of t r a n s i t i o n m e t a l dispersed in a silica o r
a l u m i n a h o s t h a v e been o b s e r v e d in the l a b o r a t o r y .
K - e d g e E X A F S m e a s u r e m e n t s a r e readily o b t a i n
able for m a t e r i a l s c o n t a i n i n g elements of a t o m i c
n u m b e r between 19 ( p o t a s s i u m ) a n d 47 (silver). F o r
Z < 19, the available E X A F S spectral r a n g e is sever
ely limited. A l s o , high a b s o r p t i o n rates for t h e low xray energies (required a t low Z ) a d d e x p e r i m e n t a l
c o m p l i c a t i o n s . F o r > 50, t h e level lifetime b r o a d
ening b e c o m e s large (intrinsically limiting achievable
resolution). E l e m e n t s with values b e t w e e n 56 (bar
i u m ) a n d 94 ( p l u t o n i u m ) c a n b e studied using L-edge
E X A F S . L-edge m e a s u r e m e n t s h a v e limited value for
< 56 because the L edge is n o t sufficiently s e p a r a t e d
from o t h e r a b s o r p t i o n edges.

3. Strengths

and Weaknesses

of EXAFS

and

XANES
E X A F S is a t e c h n i q u e t h a t is p r i m a r i l y useful for
measuring crystallographic structure parameters. The
m e a s u r e m e n t is a t o m specific, p r o v i d i n g a local r a d i a l
d i s t r i b u t i o n function for t h o s e a t o m s d i s t r i b u t e d
a b o u t the central ( a b s o r b e r ) a t o m .
F o r simple systems with l o n g - r a n g e o r d e r , a c c u r a
cies in t h e s t r u c t u r a l p a r a m e t e r s achievable w i t h
E X A F S a r e inferior t o t h o s e achievable using diffrac
tion t e c h n i q u e s p r o v i d i n g t h a t t h e m a t e r i a l s a r e n o n dilute. E X A F S plays t h e m o r e i m p o r t a n t role in
o b t a i n i n g s t r u c t u r a l i n f o r m a t i o n for a m o r p h o u s
m a t e r i a l s , solutions a n d dilute systems of v a r i o u s
k i n d s (such as h e t e r o g e n e o u s catalysts, biological
m a t e r i a l s a n d i m p u r i t y a t o m s in crystalline solids).
X A N E S is a spectroscopic t o o l useful for p r o b i n g
the u n o c c u p i e d electron states within 50 eV of t h e
F e r m i level. By m o n i t o r i n g a b s o r p t i o n edges associ
a t e d with different c o r e levels, electric dipole selection
rules c a n be used t o a d v a n t a g e in identifying e m p t y
states of specific a n g u l a r m o m e n t u m c h a r a c t e r . A s a
tool for p r o b i n g these e m p t y electron states, X A N E S
c o m p l e m e n t s a n u m b e r of o t h e r spectroscopies (such
as b r e m s s t r a h l u n g i s o c h r o m a t s p e c t r o s c o p y , u l t r a

558

Techniques

violet
photoemission
and
optical
reflectivity).
X A N E S c a n b e used a s a m a t e r i a l s c h a r a c t e r i z a t i o n
t o o l . N o v a c u u m is r e q u i r e d for these m e a s u r e m e n t s
(a significant e x p e r i m e n t a l convenience) a n d , often,
m a t e r i a l s with very low c o n c e n t r a t i o n of a b s o r b e r c a n
be studied w i t h ease.
E X A F S a n d X A N E S a r e , in a certain sense, redis
covered spectroscopies. T h e p h e n o m e n a h a v e b e e n
k n o w n for d e c a d e s , b u t only recently h a v e a d v a n c e s
in theoretical u n d e r s t a n d i n g a n d i n s t r u m e n t d e v e l o p
m e n t b e e n a d e q u a t e t o d e m o n s t r a t e t h e p r o m i s e of
t h e spectroscopies for m a t e r i a l s studies.
See also: X-Ray and Neutron Diffraction Studies of Amor
phous Solids; X-Ray Powder Diffraction

Bibliography
Lee A, Citrin , Eisenberger , Kincaid 1981
Extended x-ray absorption fine structure: its strengths
and limitations as a structural tool. Rev. Mod. Phys. 53:
769-806
Maylotte D H, Wong J, St Peters R L, Lytle L W, Greegor
R 1981 X-ray absorption spectroscopic investigation of
trace vanadium sites in coal. Science 214: 554-6
Sayers D E, Stern A, Lytle F W 1971 New technique for
investigating noncrystalline structures: Fourier analysis
of the extended x-ray absorption fine structure. Phys. Rev.
Lett. 27: 1204-7
Stern A (ed.) 1980 Workshop on Laboratory EXAFS
Facilities and Their Relation to Synchroton Radiation
Sources, AIP Conference Proceedings No. 64. American
Institute of Physics, New York
G . S. K n a p p a n d B. W . Veal
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]

X-Ray and Neutron Diffraction Studies

of Amorphous Solids
X - r a y a n d n e u t r o n diffraction t e c h n i q u e s p l a y a n
i m p o r t a n t role in t h e science of a m o r p h o g r a p h y
w h i c h is c o n c e r n e d w i t h t h e s t r u c t u r e s of a m o r p h o u s
solids a n d their systematic classification. A s with
crystalline solids, a k n o w l e d g e of s t r u c t u r e is a n
i m p o r t a n t prerequisite for u n d e r s t a n d i n g t h e p r o p e r
ties of a n a m o r p h o u s m a t e r i a l a n d t h u s utilizing it
a p p r o p r i a t e l y . T h e r e is, h o w e v e r , a n i m p o r t a n t dif
ference b e t w e e n diffraction studies of crystalline
solids a n d t h e c o r r e s p o n d i n g investigation of a m o r
p h o u s m a t e r i a l s . G i v e n g o o d diffraction d a t a over a
r e a s o n a b l e region of reciprocal space, it is in practice
possible t o d e t e r m i n e t h e s t r u c t u r e of simple crystal
line solids absolutely. T h i s is n o t t r u e for a m o r p h o u s
m a t e r i a l s ; t h e fact t h a t they a r e n o r m a l l y i s o t r o p i c o n
a m a c r o s c o p i c scale m e a n s t h e m a x i m u m t h a t c a n be
o b t a i n e d from a diffraction e x p e r i m e n t is a o n e d i m e n s i o n a l c o r r e l a t i o n function, from which t h e

X-Ray

and Neutron

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Studies

of Amorphous

Solids

r e g e n e r a t i o n of t h e u n d e r l y i n g t h r e e - d i m e n s i o n a l
s t r u c t u r e c a n never be u n i q u e . T h u s , diffraction s t u d
ies of a m o r p h o u s solid s t r u c t u r e s fall n a t u r a l l y i n t o
t w o stages: t h e a c t u a l e x p e r i m e n t c u l m i n a t i n g in t h e
d e r i v a t i o n of a real-space c o r r e l a t i o n function, a n d
the i n t e r p r e t a t i o n of this c o r r e l a t i o n function in t e r m s
of a t h r e e - d i m e n s i o n a l s t r u c t u r e .

/.

The Real-Space

Correlation

Function

T h e s t r u c t u r e s of simple c o v a l e n t crystalline a n d
a m o r p h o u s solids a r e c o m p a r e d schematically in t w o
d i m e n s i o n s in Fig. 1. F o r t h e crystal, t h e s t r u c t u r e
m a y b e specified in t e r m s of a u n i t cell a n d t r a n s l a tional s y m m e t r y , t h e latter leading t o t h e s h a r p B r a g g
p e a k s which a r e characteristic of t h e diffraction p a t
tern of crystalline solids. T h e s t r u c t u r e of a n a m o r
p h o u s solid, o n t h e o t h e r h a n d , is c h a r a c t e r i z e d b y a
lack of s y m m e t r y , periodicity a n d l o n g - r a n g e o r d e r ,
resulting in a diffraction p a t t e r n which is a c o n t i n u o u s
function of t h e scattering vector Q. T h u s , in o r d e r t o
completely specify t h e s t r u c t u r e of a n a m o r p h o u s
solid it w o u l d b e necessary t o specify t h e c o o r d i n a t e s
of all the a t o m s p r e s e n t , which is clearly impossible
for a n y real m a t e r i a l .
T h e i s o t r o p i c n a t u r e of a n a m o r p h o u s m a t e r i a l
leads t o a s t r u c t u r a l d e s c r i p t i o n in t e r m s of a o n e d i m e n s i o n a l real-space c o r r e l a t i o n function, w h i c h is
essentially a o n e - d i m e n s i o n a l a n a l o g u e of t h e P a t e r son function used for single crystals. F o r a m o n a t o
mic m a t e r i a l , t h e r a d i a l density p(r) describes t h e
n u m b e r density a t a d i s t a n c e r from a n a r b i t r a r i l y
chosen origin a t o m (see Fig. 2), a n d is a gross a v e r a g e
over all the a t o m s in t h e s a m p l e t a k e n as center. p is
the a v e r a g e n u m b e r density for the w h o l e s a m p l e . T h e
n u m b e r of n e i g h b o r s b e t w e e n r a n d r 4- dr is given by
2

g(r)dr = 4nr p(r)

dr

in which g(r) is k n o w n as t h e r a d i a l
function. T h e c o r r e l a t i o n function,
t(r) = 4nrp(r)

(1)

(2)

s h o u l d be used in t h e analysis of diffraction d a t a since

it is in this function t h a t e x p e r i m e n t a l b r o a d e n i n g is
b o t h s y m m e t r i c a n d i n d e p e n d e n t of r. T h e differential
c o r r e l a t i o n function d(r) is o b t a i n e d o n s u b t r a c t i n g
the a v e r a g e density c o n t r i b u t i o n 4nrp from t(r):
d(r) = 4nr[p(r)-p]

(3)

F o r a s a m p l e c o n t a i n i n g elements t h e s t r u c t u r e m a y
be described in t e r m s of n(n 4- l ) / 2 i n d e p e n d e n t c o m
p o n e n t c o r r e l a t i o n functions of t h e f o r m
tjk(r)

= 4nrpjk{r)

(b)

distribution

(4)

which describe t h e d i s t r i b u t i o n of element k a t o m s

a b o u t t h e yth a t o m in t h e s a m p l e c o m p o s i t i o n unit.

Figure 1
Structures of simple covalent (a) crystalline and
(b) amorphous solids

2. Experimental

Techniques

A n x-ray o r n e u t r o n diffraction e x p e r i m e n t involves a

m e a s u r e m e n t of t h e scattered intensity as a function
of t h e elastic scattering vector, the m a g n i t u d e of
w h i c h is given by
Q = (47rM)sin

(5)

w h e r e is t h e incident w a v e l e n g t h a n d 20 is the
scattering angle. A l t h o u g h for a n a m o r p h o u s solid
t h e s t r u c t u r a l i n f o r m a t i o n is essentially c o n t a i n e d
within t h e elastic scattering, it is c o n v e n t i o n a l t o
p e r f o r m a t o t a l diffraction e x p e r i m e n t in which the

559

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(a)

t (r)

-- 4

Studies

of Amorphous

(b)

(r)

(d )

Figure 2
Real-space correlation functions: (a) radial density;
(b) radial-distribution function; (c) total correlation
function; (d) differential correlation function

detector r e c o r d s b o t h the elastic scattering a n d inelas

tic ( p h o n o n ) scattering. In o r d e r to achieve the neces
sary v a r i a t i o n in Q it is possible t o scan 2 a t a fixed
incident w a v e l e n g t h ( c o n v e n t i o n a l technique) o r
to m a k e m e a s u r e m e n t s as a function of a t c o n
stant scattering angle (dispersion o r time-of-flight
technique).
T h e t w o techniques for n e u t r o n s a r e c o m p a r e d in
Figs. 3 a n d 4. In the c o n v e n t i o n a l s t e a d y - s t a t e - r e a c t o r
twin-axis experiment (Fig. 3), t h e flux () of t h e r m a l
n e u t r o n s extracted from the m o d e r a t o r / r e f l e c t o r of a
steady-state reactor h a s a M a x w e l l i a n d i s t r i b u t i o n of
velocities a n d is time i n d e p e n d e n t . A b e a m of w a v e
length A, selected by the m o n o c h r o m a t o r crystal, is
incident o n the s a m p l e a n d scattered i n t o t h e d e t e c t o r
t h r o u g h a variable angle 20. T h e variable-wavelength
time-of-flight t e c h n i q u e (Fig. 4) is usually e m p l o y e d
with a pulsed accelerator source. E l e c t r o n s o r p r o t o n s
strike a heavy-metal target, p r o d u c i n g pulses of fast
n e u t r o n s which are partially m o d e r a t e d before being
incident o n t h e s a m p l e a n d scattered i n t o d e t e c t o r s
situated at fixed angles 20. E a c h d e t e c t o r r e c o r d s the
scattered intensity as a function of time-of-flight for
the distance from t h e m o d e r a t o r via the s a m p l e t o the
detector. F o r a n y n e u t r o n , the time-of-flight is simply
related to t h r o u g h t h e velocity a n d de Broglie's
relationship, a n d t h e diffraction p a t t e r n I(Q) m a y be
extracted by dividing t h e m e a s u r e d intensity by the
i n c i d e n t - n e u t r o n s p e c t r u m s h a p e . T h e great a d v a n
tage of a pulsed-accelerator source over a steady-state
r e a c t o r is t h a t the former is u n d e r m o d e r a t e d , giving
560

Solids

rise t o a s t r o n g e p i t h e r m a l c o m p o n e n t in (). T h e s e
s h o r t - w a v e l e n g t h n e u t r o n s allow d a t a to be o b t a i n e d
to m u c h higher values of Q, resulting in a c o r r e s p o n d
ing increase in real-space resolution.
A c c u r a t e q u a n t i t a t i v e x-ray diffraction m e a s u r e
m e n t s o n a m o r p h o u s solids usually e m p l o y a m o d i
fied p o w d e r - c o u n t e r diffractometer
(see
X-Ray
Powder Diffraction). T h e situation for x-rays is c o m
plicated by t h e presence of i n c o h e r e n t C o m p t o n scat
tering which a t high values of Q c a n completely
s w a m p the r e q u i r e d c o h e r e n t c o n t r i b u t i o n . Since
neither the w a v e l e n g t h d i s t r i b u t i o n n o r the i n t e g r a t e d
intensity of the C o m p t o n scattering from a given
s a m p l e c a n b e satisfactorily calculated, it is necessary
t o r e m o v e this c o n t r i b u t i o n by m e a n s of a diffractedb e a m m o n o c h r o m a t o r . M a n y researchers h a v e used a
single m o n o c h r o m a t o r in t h e diffracted b e a m b u t t h e
difficulty with this a r r a n g e m e n t is t h a t white b a c k
g r o u n d r a d i a t i o n from the x-ray t u b e c a n be C o m p
t o n scattered i n t o the m o n o c h r o m a t o r envelope. A
m u c h better a r r a n g e m e n t , s h o w n in Fig. 5, e m p l o y s a
m o n o c h r o m a t o r in b o t h t h e incident a n d diffracted
b e a m s ( W a r r e n a n d M a v e l 1965). A c o n v e n t i o n a l
curved-crystal m o n o c h r o m a t o r is used in t h e incident
b e a m (silver ^ = 0.05594 n m ) b u t t h a t in the
diffracted b e a m c o m p r i s e s a foil with a n a b s o r p t i o n
edge at a w a v e l e n g t h slightly longer t h a n the c h a r a c
teristic line of the x-ray t u b e ( r u t h e n i u m edge:
= 0.05605 n m ) such t h a t t h e c o h e r e n t intensity will
excite fluorescence w h e r e a s t h e C o m p t o n scattering
will n o t . T h e fluorescent r a d i a t i o n is t h e n r e c o r d e d by
the detector.
T h e dispersion t e c h n i q u e is also possible with rays
using a s e m i c o n d u c t o r detector. T h e a d v a n t a g e of this
m e t h o d is t h a t for c o m p l e x s a m p l e e n v i r o n m e n t s
(such as c r y o s t a t s , furnaces a n d high-pressure cells)
only t w o o r three small w i n d o w s a r e needed, a fixed
angle a p a r t . Similarly, all values of Q a r e e x a m i n e d
simultaneously, m a k i n g the t e c h n i q u e ideally suited
t o following p h a s e c h a n g e s o r s t u d y i n g kinetic effects.
O u t s i d e such special a p p l i c a t i o n s , however, x-ray
variable-wavelength experiments are unlikely t o p r o v e
i m p o r t a n t for w o r k o n a m o r p h o u s m a t e r i a l s o w i n g t o
the difficulty of accurately d e t e r m i n i n g t h e incident
s p e c t r u m a n d m a k i n g c o r r e c t i o n s for a b s o r p t i o n a n d
C o m p t o n scattering.
A n y m e a s u r e m e n t requires a certain n u m b e r of
c o r r e c t i o n s t o t h e basic d a t a b u t in a g o o d e x p e r i m e n t
these c o r r e c t i o n s a r e minimized o r p u t i n t o a form in
which they a r e easily h a n d l e d . N o r m a l l y , corrections
a r e included for:
(a)

c o u n t e r paralysis t i m e t h i s c o r r e c t i o n is b e c o m
ing increasingly i m p o r t a n t with m o d e r n highintensity x-ray a n d n e u t r o n sources;

(b)

i n s t r u m e n t a l b a c k g r o u n d a n d scattering
a n y s a m p l e c o n t a i n e r used;

(c)

a b s o r p t i o n , self-shielding a n d multiple scatter

ingthese c o r r e c t i o n s a r e closely c o u p l e d a n d

from

X-Ray

and Neutron

Diffraction

Studies

of Amorphous

Solids

Figure 3
Conventional neutron diffractometer

c a n only be t r e a t e d i n d e p e n d e n t l y if o n e o r o t h e r
of t h e m is small;
(d)

(e)

x-ray effects including p o l a r i z a t i o n a n d re

sidual C o m p t o n scattering n o t r e m o v e d by t h e
diffracted-beam m o n o c h r o m a t o r ; a n d
n e u t r o n s t a t i c - a p p r o x i m a t i o n d i s t o r t i o n s (Placzek corrections).

F o l l o w i n g c o r r e c t i o n it is necessary t o n o r m a l i z e t h e
d a t a t o a b s o l u t e units. T h i s m a y be achieved either b y
the use of self-consistent i n t e g r a t i o n t e c h n i q u e s or, for
n e u t r o n s , by m e a s u r i n g t h e ( i n c o h e r e n t ) s c a t t e r i n g
from a s t a n d a r d v a n a d i u m s a m p l e .

3. Outline

Theory

T h e corrected x-ray o r n e u t r o n diffraction

takes the general form
/(G) = / e( Q ) +

i(0

pattern

ma

for n e u t r o n s , a n d by a similar expression for rays

except t h a t t h e a t o m i c n u m b e r replaces the n e u t r o n
scattering length b. T h e j s u m m a t i o n is t a k e n over the
a t o m s in o n e unit of c o m p o s i t i o n . T h e F o u r i e r t r a n s
form in E q n . (7) is n o r m a l l y p e r f o r m e d numerically
using a high-speed digital c o m p u t e r .
T h e fact t h a t d a t a c a n only be o b t a i n e d for Q ^
Qmax m e a n s t h a t the r e l a t i o n s h i p between T(r) a n d
the c o m p o n e n t c o r r e l a t i o n functions tjk(r) is o n e of
convolution:

T{r) =

j*g/(0M(0sin rQ dQ (7)

(8)

T(r) = 4nrp^bj)2

(6)

in which P(Q) is t h e self-scattering ( i n d e p e n d e n t

scattering) a n d i(Q) is t h e distinct scattering (interfer
ence scattering). T h e r e q u i r e d s t r u c t u r a l i n f o r m a t i o n
c o n t a i n e d within i(Q) m a y be e x t r a c t e d by m e a n s of a
F o u r i e r t r a n s f o r m a t i o n of the interference function
Qi(Q) as outlined for n e u t r o n s in Fig. 6:

T(r) = T\r) +

w h e r e M(Q) is a modification function t o allow for

t h e fact t h a t d a t a c a n only be o b t a i n e d for Q less t h a n
o r e q u a l to s o m e m a x i m u m value Q m a x, a n d is zero for
2>e x- T(r) is given by

TLt)k{r)
J k
/OO

tjk(u)[P'jk(r

- u)

Jo

-P'jk(r

+ u)]du

(9)

T h e k s u m m a t i o n is t a k e n over a t o m types (elements),

u is a d u m m y c o n v o l u t i o n variable a n d the p r i m e
indicates o r for n e u t r o n s o r rays, respectively.
T h e c o r r e s p o n d i n g p e a k functions
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Target

Pulsed
electron

Cadmium + indium decoupler

BEAM

'olyethylene moderator
Concrete shielding wall

Evacuated flight tube

Solids

fl(Q) before F o u r i e r t r a n s f o r m a t i o n t o yield the socalled a t o m i c c o r r e l a t i o n function. T h e fact t h a t the Q

d e p e n d e n c e of / (Q) is different for each element
m e a n s t h a t t h e s h a p e of Pfk(r) c h a n g e s for each
independent component.
4. Methods

Borax in resin

92

U fjssion chamber
Focusing angle

B4C in resin
Variable Second
f|ight-pbth

BAC in rubber

Figure 4
Time-of-flight neutron diffractometer

P%(r)

= ( ^ )

M ( 0 C O S rQ dQ

(10)
define t h e e x p e r i m e n t a l resolution in real space.
fj(Q) a n d fk(Q)
being a t o m i c scattering factors
a n d / e(0 the a v e r a g e form factor p e r electron for the
s a m p l e j n q u e s t i o n . F o r n e u t r o n s , t h e scattering
lengths b a r e i n d e p e n d e n t of Q a n d the factor bjbk is a
simple scaling factor, w h e r e a s for rays it is c o n v e n
tional t o divide Qi(Q) b y t h e " s h a r p e n i n g " function

562

of

Interpretation

A s a l r e a d y n o t e d , b o t h Qi (Q) a n d T(r) are o n e d i m e n s i o n a l r e p r e s e n t a t i o n s of a t h r e e - d i m e n s i o n a l

s t r u c t u r e a n d a r e a gross a v e r a g e over t h e w h o l e
i r r a d i a t e d v o l u m e . I n a d d i t i o n , a s s h o w n by E q n . (9),
the e x p e r i m e n t a l c o r r e l a t i o n function is b r o a d e n e d by
P(r) a n d a single diffraction e x p e r i m e n t o n a m u l t i
element s a m p l e yields only a weighted s u m of the
individual c o m p o n e n t s tjk(r). V a r i o u s m e t h o d s exist
for experimentally d e t e r m i n i n g the individual c o m p o
n e n t s of Qi(Q) a n d T(r) for a p o l y a t o m i c system, all
of w h i c h involve a v a r i a t i o n of / ( ) o r b for o n e o r
m o r e of t h e c o n s t i t u e n t elements. F o r b o t h rays a n d
n e u t r o n s , it is possible t o utilize the p h e n o m e n o n of
a n o m a l o u s dispersion (the w a v e l e n g t h d e p e n d e n c e of
/ ( ) o r b n e a r a n a b s o r p t i o n edge o r resonance,
respectively), a n d for n e u t r o n s there are also the
t e c h n i q u e s of isotopic s u b s t i t u t i o n (b varies for dif
ferent isotopes of t h e s a m e element) a n d m a g n e t i c
diffraction. T h e successful use of each of these tech
n i q u e s is, h o w e v e r , limited t o relatively few favorable
s a m p l e s a n d , in m o s t cases, the m a x i m u m t h a t c a n b e
achieved is a c o m b i n a t i o n of x-ray a n d n e u t r o n
diffraction t e c h n i q u e s for w h i c h the c o m p o n e n t
weighting functions are different.
T h e d a t a o b t a i n e d from a n e x p e r i m e n t a l investiga
tion of a n a m o r p h o u s solid m a y t h u s r a n g e from a
single t o t a l c o r r e l a t i o n function T(r) t o a c o m p l e t e
d e t e r m i n a t i o n of all the individual c o m p o n e n t s t'jk(r).
T h e object in e a c h case is t o extract the m a x i m u m
i n f o r m a t i o n o n t h e s t r u c t u r e of the m a t e r i a l in q u e s
tion. M o s t a m o r p h o u s solids c o n t a i n a well-defined
s t r u c t u r a l u n i t w h i c h gives rise t o o n e o r m o r e rela
tively s h a r p p e a k s in the c o r r e l a t i o n function a t low r
from w h i c h it is possible t o e x t r a c t i n f o r m a t i o n o n
b o n d distances a n d angles by m e a n s of peak-fitting
techniques. T h e w a y in w h i c h t h e individual s t r u c t u r a l
units p a c k t o g e t h e r , the i n t e r m e d i a t e - r a n g e o r d e r , is
t h e n usually investigated t h r o u g h m o d e l calculations.
4.1 Peak Fitting
If it is a s s u m e d t h a t the d i s t r i b u t i o n of distances
a b o u t a m e a n value
is G a u s s i a n in tjk(f) with a r o o t 112
m e a n - s q u a r e d e v i a t i o n (ujk) ,
t h e n the resulting
c o n t r i b u t i o n t o Qi(Q) is of the form
s

Qijk(Q)

-r , ^
njkfj(Q)fk(Q)

in

ikQ

e x p i - i g ^ ) (11)

w h e r e nJk is t h e n u m b e r of /c-type a t o m s a r o u n d a t o m
j at this distance, a n d f{Q) represents either f(Q) o r b
for rays o r n e u t r o n s , respectively. T h e c o r r e s p o n d
ing real-space c o r r e l a t i o n function, including the c o n -

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Scaler

Figure 5
Fluorescent-foil x-ray diffraction technique

t r i b u t i o n from P(r), c a n b e o b t a i n e d b y F o u r i e r
t r a n s f o r m a t i o n of E q n . (11) w i t h t h e s a m e value of
g m ax a n d modification function a s used e x p e r i m e n
tally. It is t h u s possible t o o b t a i n t h e p a r a m e t e r s njk,rjk
1 /2
a n d (w#) b y p e r f o r m i n g a least-squares fit t o t h e
e x p e r i m e n t a l d a t a in real space o r t o t h e e x p e r i m e n t a l
interference function a t h i g h Q, w h e r e only t h e s h a r p
est real-space p e a k s c o n t r i b u t e .

7(0)=/ (0)*/(0)
self

()=

{)+

J Q/lQ)M[Q)

distinct

sin rO

dO

Figure 6
Steps in the calculation of the real-space correlation
function T(r) from the corrected intensity / ( g )

4.2 Model
Calculations
T h e limited n a t u r e of t h e m e a s u r e d c o r r e l a t i o n func
tion m e a n s t h a t in o r d e r t o e x t r a c t m o r e t h a n j u s t
average interatomic distances a n d coordination
n u m b e r s it is necessary t o r e s o r t t o s o m e f o r m of
m o d e l a n d t o ascertain h o w well this agrees with
e x p e r i m e n t . Qi(Q) a n d T(r) e m p h a s i z e different a s
pects of t h e s t r u c t u r e a n d it is therefore m o s t i m p o r t
a n t t o m a k e such c o m p a r i s o n s in b o t h real a n d
intensity space, a n d in t h e f o r m e r t o correctly incor
p o r a t e t h e p e a k function P(r). Similarly, n o m a t t e r
h o w g o o d t h e a g r e e m e n t o b t a i n e d is, t h e m o d e l in
q u e s t i o n is only o n e possible fit t o t h e d a t a a n d hence
it is essential t o c o n s i d e r , a n d if possible eliminate, all
a l t e r n a t i v e m o d e l s . A variety of s t r u c t u r a l m o d e l s a n d
m o d e l l i n g t e c h n i q u e s h a s b e e n e m p l o y e d in t h e s t u d y
of a m o r p h o u s solids a n d s o m e of t h e m o r e i m p o r t a n t
of these a r e s u m m a r i z e d b e l o w .
(a)

C r y s t a l - b a s e d m o d e l s . A g r e a t deal of i n f o r m a
tion o n t h e s t r u c t u r e of a m o r p h o u s solids c a n be
o b t a i n e d from a simple c o m p a r i s o n with t h e
c o r r e s p o n d i n g crystalline p o l y m o r p h s . M o r e
f o r m a l crystal-based m o d e l s , such as t h e q u a s i crystalline m o d e l , s t a r t w i t h a n a p p r o p r i a t e crys
tal s t r u c t u r e a n d restrict t h e l o n g e r - r a n g e o r d e r
t o i n t e r a t o m i c spacings less t h a n s o m e c h a r a c t e r
istic c o r r e l a t i o n length.

(b)

Random-network models. The random-network

t h e o r y h a s b e e n t h e m o s t successful in describing
t h e s t r u c t u r e of t r a d i t i o n a l oxide glasses a n d
amorphous semiconductors. Random-network

563

X-Ray

and Neutron

Diffraction

Studies

of Amorphous

m o d e l s m a y be built either by h a n d o r using a

computer.
(c)

C h a i n a n d ring m o d e l s . T h e s e m o d e l s a r e a p p r o
p r i a t e for m a t e r i a l s c o n t a i n i n g only divalent
a t o m s (e.g., selenium) o r larger t w o - c o n n e c t e d
g r o u p i n g s of a t o m s such as t h o s e f o u n d in or
ganic p o l y m e r s ( e . g . , C H 2 ) .

(d)

Random-sphere-packing
models.
Random
sphere p a c k i n g s p r o v i d e a useful s t a r t i n g p o i n t
for m o d e l s of a m o r p h o u s metallic alloys a n d
m a t e r i a l s w h o s e s t r u c t u r e s a r e g o v e r n e d by p r e
d o m i n a n t l y ionic forces such as vitreous Z n C l 2 .

(e)

Molecular models. Models based on a r a n d o m

p a c k i n g of a p p r o x i m a t e l y spherical molecules
h a v e been used t o describe t h e s t r u c t u r e of s o m e
v a p o r - d e p o s i t e d thin films (e.g. C C 1 4 , A s - S a n d
A s 2 0 3 ) . T h e formalism e m p l o y e d closely follows
t h a t for m o l e c u l a r liquids.

(f)

A m o r p h o u s - c l u s t e r m o d e l s . A m o r p h o u s clusters
a r e c o m p o s e d of a t o m s in a regular b u t n o n c r y s t a l l o g r a p h i c configuration frequently b a s e d o n
p e n t a g o n a l d o d e c a h e d r a o r fivefold s y m m e t r y .
Cluster size is limited d u e t o a slight m i s m a t c h
between adjacent s t r u c t u r a l u n i t s , w h i c h leads t o
increasing d i s t o r t i o n as t h e cluster g r o w s .

(g)

M o n t e C a r l o a n d m o l e c u l a r d y n a m i c s simula
tions. T h e s t r u c t u r e s of a r a n g e of simple inor
ganic glasses h a v e been s i m u l a t e d using p u r e l y
ionic p o t e n t i a l s . A g a i n t h e m e t h o d s e m p l o y e d
closely follow t h o s e for related liquids.

5. Neutron

Magnetic

Diffraction

A s with crystalline m a t e r i a l s , t h e fact t h a t t h e n e u t r o n

h a s a m a g n e t i c m o m e n t m e a n s t h a t it is possible t o
use n e u t r o n diffraction t o p r o b e the m a g n e t i c struc
t u r e of a m o r p h o u s solids. M a g n e t i c o r d e r i n g in a n
a m o r p h o u s solid m a y o c c u r either s p o n t a n e o u s l y
below s o m e m a g n e t i c - o r d e r i n g t r a n s i t i o n t e m p e r a t u r e
or else be i n d u c e d b y t h e a p p l i c a t i o n of a s t r o n g
m a g n e t i c field. A full description of t h e f o r m a l i s m of
n e u t r o n m a g n e t i c scattering a n d t h e results o b t a i n e d
is given in W r i g h t (1980).

6. Accuracy

and

Limitations

A discussion of the a c c u r a c y a n d limitations of t h e

t e c h n i q u e c a n b e divided i n t o t w o p a r t s : t h e a c c u r a c y
of t h e e x p e r i m e n t a l d a t a a n d t h a t of t h e resulting
t r a n s f o r m , a n d t h e extent of t h e a m b i g u i t y of a n y
i n t e r p r e t a t i o n of these d a t a . T h e a c c u r a c y of t h e
e x p e r i m e n t a l d a t a c a n m o s t easily be g a u g e d b y t h e
b e h a v i o r of the t r a n s f o r m a t low r, below the first t r u e
p e a k . If t h e t r a n s f o r m is well b e h a v e d in this region,
t h e n t h e d a t a a r e of r e a s o n a b l e quality. G r e a t c a r e is
needed in m a k i n g this assessment, h o w e v e r , as s o m e

564

Solids

a u t h o r s either p l o t t h e r a d i a l d i s t r i b u t i o n function
r 7 \ r ) , w h i c h h a s t h e effect of r e d u c i n g t h e a m p l i t u d e
of e r r o r ripples a t low r, o r use these false oscillations
as a criterion for tidying their d a t a before p u b l i c a t i o n
a n d d o n o t include the original u n t r e a t e d t r a n s f o r m .
In t h e a b s e n c e of o t h e r i n f o r m a t i o n such d a t a m u s t be
r e g a r d e d with t h e u t m o s t suspicion.
Similar t e c h n i q u e s a r e s o m e t i m e s used t o r e m o v e
t h e effects of t e r m i n a t i n g t h e d a t a a t finite Q m a x.
I n f o r m a t i o n t h e o r y , h o w e v e r , indicates t h a t it is im
possible t o replace t h e u n m e a s u r e d d a t a w i t h o u t
making some assumption a b o u t the material under
investigation so t h a t t h e resulting c o r r e l a t i o n function
merely b e c o m e s o n e possible m o d e l which fits the
results r a t h e r t h a n a n u n b i a s e d F o u r i e r t r a n s f o r m . It
s h o u l d also be n o t e d t h a t in principle b o t h Qi(Q) a n d
T(r) c o n t a i n t h e s a m e i n f o r m a t i o n expressed in a
different f o r m , a l t h o u g h in practice t h e i n f o r m a t i o n
c o n t e n t of T(r) is slightly r e d u c e d by t h e use of a
modification function. T h e finite u p p e r limit in Q
m e a n s t h a t in T(r) e a c h c o m p o n e n t tjk{r) is c o n v o
luted with t h e a p p r o p r i a t e p e a k f u n c t i o n p ( r ) , b u t the
i n f o r m a t i o n for a p a r t i c u l a r d i s t a n c e is still c o n c e n
t r a t e d a r o u n d t h a t d i s t a n c e (whereas it is s p r e a d
t h r o u g h o u t reciprocal space).
T h e u n i q u e n e s s of a n y s t r u c t u r a l i n f o r m a t i o n
e x t r a c t e d from t h e d a t a is m u c h m o r e difficult t o
j u d g e . A s a l r e a d y stressed, t h e o n e - d i m e n s i o n a l
n a t u r e of t h e c o r r e l a t i o n function m e a n s t h a t it is
impossible t o u n a m b i g u o u s l y d e t e r m i n e t h e s t r u c t u r e
of a n a m o r p h o u s solid. T h e reliability of a n y i n t e r p r e
t a t i o n , therefore, d e p e n d s n o t only o n t h e q u a l i t y of
the fit t o the e x p e r i m e n t a l d a t a in b o t h real a n d
reciprocal space, b u t also o n the n u m b e r of o t h e r
possible m o d e l s w h i c h h a v e been tried a n d satisfactor
ily rejected. T h e fact t h a t diffraction d a t a a r e a n
a v e r a g e for t h e w h o l e i r r a d i a t e d v o l u m e , a n d include
a t m o s t only p a r t of a n y small-angle scattering which
m a y be p r e s e n t , m e a n s t h a t t h e d a t a a r e relatively
insensitive t o p h a s e s e p a r a t i o n . In m o s t cases, it is
n o t possible t o d e t e r m i n e t h e individual c o m p o n e n t
a n d in this situation
c o r r e l a t i o n functions tjk(r),
e x t e n d e d x-ray a b s o r p t i o n fine-structure t e c h n i q u e s
can provide important complementary information.
Finally, it m u s t n o t be f o r g o t t e n t h a t a great deal of
o t h e r s t r u c t u r a l i n f o r m a t i o n c a n be o b t a i n e d from the
results of indirect p r o b e s such as optical s p e c t r o s c o p y
a n d m a g n e t i c r e s o n a n c e s p e c t r o s c o p y . All of these
d a t a m u s t also be consistent with a n y c h o s e n struc
tural model.
See also: Single-Crystal X-Ray Diffraction; X-Ray Absorp
tion Spectroscopy: EXAFS and XANES Techniques;
X-Ray Powder Diffraction

Bibliography
Elliott S R 1984 Physics of Amorphous Materials. Longman,
London

X-Ray

and Neutron

Gaskell 1991 Models for the structure of amorphous

solids. In: Zarzycki J (ed.) 1991 Glasses and Amorphous
Solids. VCH, Weinheim, Germany, pp. 175-278
Wagner C J 1978 Direct methods for the determination of
atomic-scale structure of amorphous solids (x-ray, elec
tron and neutron scattering). J. Non-Cryst. Solids 3 1 : 1 40
Wagner C J 1980 Diffraction analysis of metallic, semi
conducting and inorganic glasses. J. Non-Cryst. Solids 42:
3-21
Warren 1969 X-Ray Diffraction. Addison-Wesley,
Reading, MA
Warren , Mavel G 1965 Elimination of the Compton
component in amorphous scattering. Rev. Sci. Instrum.
36: 196-7
Wong J, Angell C A 1976 Glass: Structure by Spectroscopy.
Dekker, New York, Chap. 2
Wright A C 1974 The structure of amorphous solids by xray and neutron diffraction. Adv. Struct. Res. Diffr.
Methods 5: 1-84
Wright A C 1980 Neutron magnetic scattering studies of
amorphous solids. / . Non-Cryst. Solids 40: 325-46
Wright A C 1984 Basic amorphography. In: Fleury A,
Golding (eds.) 1984 Coherence and Energy Transfer in
Glasses. Plenum, New York, pp. 1-38
Wright A C, Leadbetter A J 1976 Diffraction studies of glass
structure. Phys. Chem. Glasses 17: 122-45
Zallen R 1983 The Physics of Amorphous Solids. Wiley, New
York
A. C. Wright
[J. J. T h o m p s o n Physical L a b o r a t o r y ,
Reading, U K ]

X-Ray and Neutron Diffuse Scattering

of Radiation-Induced Defects
In the p a s t several years m a n y f u n d a m e n t a l q u e s t i o n s
involving r a d i a t i o n - i n d u c e d defects in m e t a l s h a v e
been a n s w e r e d using diffuse x-ray a n d n e u t r o n scat
tering t e c h n i q u e s . T h e s e t e c h n i q u e s c a n be e m p l o y e d
to investigate b o t h p o i n t defects, t h a t is, vacancies
a n d interstitial a t o m s , a n d p o i n t defect a g g l o m e r a t e s
u p t o sizes t h a t c a n be i m a g e d in a n electron m i c r o
scope. A s m i c r o s c o p i c p r o b e s of defect p r o p e r t i e s a n d
i n t e r a c t i o n s , t h e t e c h n i q u e s c a n p r o v i d e u n i q u e infor
m a t i o n which is difficult t o o b t a i n by o t h e r m e t h o d s .

I. Diffuse

X-Ray

Scattering

T h e u n d e r l y i n g principles of diffuse x-ray scattering

a r e r a t h e r s t r a i g h t f o r w a r d . In a perfect crystal, t h e xray scattering intensity is z e r o e v e r y w h e r e except a t
the B r a g g p e a k , t h a t is, w h e n t h e scattering vector k
coincides with a reciprocal lattice v e c t o r h. W h e n a
defect is i n t r o d u c e d i n t o t h e lattice, t h e perfect cancel
lation of scattered w a v e s a w a y from t h e B r a g g p e a k is
d e s t r o y e d a n d a diffuse scattering intensity results.
F o r a low c o n c e n t r a t i o n of r a n d o m l y d i s t r i b u t e d

Diffuse

Scattering

of Radiation-Induced

Defects

defects, t h e diffuse intensity c a n be o b t a i n e d from the

relation ( D e d e r i c h s 1973)
2

(1)

S=c\F(k)\

w h e r e c is the c o n c e n t r a t i o n of defects a n d F(k) is the

"defect s t r u c t u r e f a c t o r . " T h i s s t r u c t u r e factor c a n be
expressed in the form
i

^)=/?+/te '-"(e *-'"-l)

(2)

w h e r e a n d fk a r e the a t o m i c scattering factors of the

defect a n d h o s t a t o m s respectively, a n d t" is the
d i s p l a c e m e n t vector of a t o m n, a w a y from its n o r m a l
n
lattice site a t r . E q u a t i o n (2) s h o w s t h a t the scattering
intensity arises from b o t h the defect itself ( L a u e
scattering), a n d from t h e d i s p l a c e m e n t s of the lattice
a t o m s c a u s e d by t h e defect. T o d e t e r m i n e t h e t y p e a n d
c o n f i g u r a t i o n of t h e defects in a n i r r a d i a t e d specimen,
scattering intensities a r e m e a s u r e d at different p o i n t s
in reciprocal space a n d c o m p a r e d with intensities
calculated for likely defect configurations. A m a j o r
p a r t of the p r o b l e m of c o u r s e is t o calculate the
d i s p l a c e m e n t field of t h e defect. F i g u r e 1 illustrates
h o w this p r o c e d u r e w a s e m p l o y e d t o d e t e r m i n e the
configuration of self-interstitial a t o m s in electroni r r a d i a t e d a l u m i n u m . T h e <100> split configuration is
t h e o n l y r e a s o n a b l e choice.
T h e difficulty in a c q u i r i n g d a t a like t h o s e in Fig. 1 is
t h a t for p o i n t s far from t h e B r a g g p e a k s the defect
scattering intensity is small a n d t h e b a c k g r o u n d aris
ing from C o m p t o n a n d t h e r m a l diffuse scattering is
high. F o r t h e d a t a s h o w n in Fig. 1, a 100 k W source
a n d a 100-detector system w a s r e q u i r e d ( H a u b o l d
1975). C l o s e t o t h e B r a g g p e a k t h e scattering intensity
from defects increases r a p i d l y , a n d this scattering
( H u a n g scattering) c a n m o r e easily b e m e a s u r e d .
C a l c u l a t i o n s s h o w t h a t the scattering in this region
arises p r i m a r i l y from t h e d i s p l a c e m e n t s of a t o m s far
from t h e defect center. Such d i s p l a c e m e n t s c a n be
calculated using elastic c o n t i n u u m t h e o r y a n d this
greatly simplifies t h e theoretical p r o b l e m . T h e m a g n i
t u d e of t h e H u a n g scattering d e t e r m i n e s t h e relax
a t i o n v o l u m e of the defect, a n d t h e a n i s o t r o p y of the
scattering reflects the s y m m e t r y . O w i n g t o the less
d e m a n d i n g r e q u i r e m e n t s of the H u a n g m e a s u r e
m e n t s , they h a v e been used extensively t o d e t e r m i n e
r e l a x a t i o n v o l u m e s a n d c o n f i g u r a t i o n s of interstitial
a t o m s in m e t a l s of fee, bec a n d h e p s t r u c t u r e s .
H u a n g scattering also p r o v i d e s a very sensitive
m e t h o d for m o n i t o r i n g defect clustering. T h i s is p o s
sible b e c a u s e t h e H u a n g scattering is p r o p o r t i o n a l t o
t h e s q u a r e of t h e r e l a x a t i o n v o l u m e of t h e defect. F o r
t h e e x a m p l e of a c o n c e n t r a t i o n of c single defects,
e a c h of r e l a x a t i o n v o l u m e V, a n d forming agglomer
ates of size d u r i n g a n a n n e a l i n g t r e a t m e n t , the
H u a n g scattering intensities before a n d after a n n e a l
ing a r e given by
5b

occ(AF)

(3)

e f o r e

S a [ l eor c ( c / ) ( A F )

(4)

565

X-Ray

and Neutron

022

Diffuse

Scattering

of Radiation-Induced

Defects

222
? _

Scattering angle

()

Figure 1
Comparison of the measured diffuse scattering intensity from electron-irradiated aluminum with intensities calculated
assuming different self-interstitial atom configurations (after Haubold 1975)

respectively, so t h a t their r a t i o yields

^after /^before

2. Neutron
(5)

T h u s the average n u m b e r of defects in a cluster c a n be

determined.
Scattering intensities for dislocation l o o p s h a v e
also been studied ( E h r h a r t et al. 1982). F i g u r e 2 s h o w s
the calculated scattering intensity for a n interstitial
4
a t o m F r a n k l o o p in nickel p l o t t e d as Sq vs qR for q
parallel t o h (q = k - h), w h e r e R is the r a d i u s of the
4
l o o p . T h e l o o p r a d i u s c a n b e o b t a i n e d by p l o t t i n g Sq
against q t o locate the p e a k p o s i t i o n qQ9 a n d setting the
p r o d u c t q0R e q u a l t o the p e a k p o s i t i o n s h o w n in Fig.
2. T h e height of the p e a k yields the l o o p c o n c e n t r a
tion.

Diffuse

Elastic

Scattering

In Sect. 1 a t t e n t i o n w a s focused m o s t l y o n x-ray

scattering very n e a r t h e B r a g g p e a k s . F o r m u l t i c o m
p o n e n t systems, t h a t is, alloys a n d c o m p o u n d s , a
w e a l t h of i n f o r m a t i o n is available from the diffuse
scattering b e t w e e n t h e B r a g g p e a k s . Let us follow the
t r e a t m e n t first c o n s i d e r e d by Borie a n d S p a r k s (1971)
for a c o n c e n t r a t e d cubic b i n a r y s u b s t i t u t i o n a l alloy,
where both composition and positional disorder pre
vail. If we define real space i n t e r a t o m i c vectors pt =
Im In = /(a, 2) + m(a2 2) + ( a 3 2), a n d reciprocal
lattice c o o r d i n a t e s Q = hlbl + h2b2 + 33 such t h a t /,
m, a r e integers a n d A h2, h3 a r e c o n t i n u o u s vari
ables, t h e n t h e differential scattering cross section,
n o r m a l i z e d in L a u e m o n o t o n i c u n i t s , is expressed as
dajdO.
CACB(fA-b'B)

+ ( , ) + , ( . )
2

+ ? ( 1 , 2 , 3 ) + 2 ( 2 , 3 )
+ ^ ^ , , ) + A,

h2Sxy(hh2,h3)

+ MjS^Mj,*,) + , 5 ^ (

, 2)

(6)

with
^SRO

lmn
a

os

sc

2 COS

7TNAJ

(7)

c o s 2 cos 3

(8)

l,m,n

Figure 2
Scattering intensities close to (400) reflections in a [100] q
direction calculated for dislocation loops with radius
20 A in nickel (after Ehrhart et al. 1982)
566

Qx

l,m,n

yimn '

lh\

X-Ray

Rx

= 6 lmn sin nlhx c o s nmh2 c o s nnh3

(9)

l,m,n

*mn

sm

ms

wnh-! sin nnh3

(10)

l,m,n

C, a r e c o n c e n t r a t i o n s of species a n d b\ a r e n e u t r o n
scattering lengths weighted b y a p p r o p r i a t e D e b y e Waller factors. A detailed discussion c a n b e f o u n d in
S c h m a t z (1973) a n d B a u r (1979). T h e t e r m s in Rx
c o n t a i n i n f o r m a t i o n a b o u t static d i s p l a c e m e n t effects
described in Sect. 1; 7 S RO p r o v i d e s details o f s h o r t r a n g e o r d e r a n d clustering a m o n g defects. T h e u s e o f
s y m m e t r y a r g u m e n t s in a detailed discussion o f these
e q u a t i o n s c a n b e f o u n d in S c h w a r t z a n d C o h e n
(1977). T h e p o i n t h e r e is t h a t t h e F o u r i e r coefficients
in E q n s . ( 8 - 1 0 ) , for r a y s , c o n t a i n a t o m i c scattering
factors f(Q) a n d t h u s a r e n o t strictly periodic. F o r
n e u t r o n s , n u c l e a r scattering lengths a r e a p p r o p r i a t e
a n d hence t h e a p p l i c a t i o n o f n e u t r o n s offers signific
a n t a d v a n t a g e over r a y s .
Diffuse elastic n e u t r o n scattering ( D E N S ) tech
niques allow u s t o r e m o v e t h e c o m p l i c a t i o n s o f
t i m e - d e p e n d e n t p h e n o m e n a such a s p h o n o n inelastic
scattering, a n d a r e m u c h less sensitive t o surface
effects since n e u t r o n a b s o r p t i o n cross sections a r e
m u c h smaller t h a n x-ray c o u n t e r p a r t s . T h e largest
sources of b a c k g r o u n d in x-ray m e a s u r e m e n t s a r e
C o m p t o n a n d t h e r m a l diffuse scattering; these a r e
eliminated using D E N S t e c h n i q u e s . H o w e v e r , c a r e
m u s t b e t a k e n in t h e n e u t r o n case t o a v o i d n u c l e a r
spin a n d i s o t r o p i c d i s o r d e r scattering. T h e m a i n dis
a d v a n t a g e s o f D E N S stem from limited n e u t r o n
fluxes available a t steady state sources; h o w e v e r , n e w
i n s t r u m e n t a t i o n a n d t h e a d v e n t of pulsed n e u t r o n
sources m a y allow u s t o m i n i m i z e this limitation (see
C o h e n et al. (1975)).

Acknowledgement
T h e w o r k o f t h e a u t h o r s is s u p p o r t e d b y t h e U S
Government under contract N o . W-31-109-ENG-38.
See also: Electron Microscope Analysis of Defect Clusters,
Voids and Bubbles; X-Ray Powder Diffraction

Bibliography
Baur G S 1979 Diffuse elastic neutron scattering from non
magnetic materials. In: Herman (ed.) 1979 A Treatise
on Materials Science and Technology, Vol. 15. Academic
Press, New York, pp. 291
Borie B, Sparks C J Jr 1971 The interpretation of intensity
distributions from distorted binary alloys. Acta Crystallogr. Sect. A 27: 198-201
Cohen J B, Faber J, Batterman W, Baur G S, King S S,
Larson C, Summerfeld G C 1975 Advanced Uses of
Pulsed Neutron Sources, ANL-76-10, Vol. 2. Argonne
National Laboratory, Argonne, IL, p. 88

Diffraction,

Time-Resolved

Dederichs 1973 The theory of diffuse x-ray scattering

and its application to the study of point defects and their
clusters. J. Phys. F3: 471-96
Ehrhart 1978 The configuration of atomic defects as
determined from scattering studies. / . Nucl. Mater. 69/70:
200-14
Ehrhart P, Trinkaus H, Larson C 1982 Diffuse scattering
from dislocation loops. Phys. Rev. 25: 834-48
Haubold H-G 1975 In: Robinson , Young F W Jr (eds.)
1975 Fundamental Aspects of Radiation Damage in
Metals.
National Technical Information Service,
Springfield, VA, p. 268
Schmatz W 1973 X-ray and neutron scattering studies on
disordered crystals. In: Herman (ed.) 1973 A Treatise in
Materials Science and Technology, Vol. 2. Academic
Press, New York, pp. 105-229
Schwartz L H, Cohen J 1977 Diffraction From Materials.
Academic Press, New York, pp. 403-24
J. F a b e r J r a n d R . S. A v e r b a c k
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]

X-Ray Diffraction, Time-Resolved

X - r a y diffraction h a s p l a y e d a k e y role in t h e develop
ment of o u r understanding of the structure of mater
ials. Since its i n c e p t i o n , efforts h a v e been m a d e t o
m e a s u r e t h e s t r u c t u r a l c h a n g e s which o c c u r d u r i n g
m a t e r i a l s processing t r e a t m e n t s . T o a n s w e r such
q u e s t i o n s , which inherently involve t h e time e v o l u t i o n
of s t r u c t u r e s , t h e time r e s o l u t i o n o f t h e diffraction
measurement must be considered. With conventional
x-ray sources, a s f o u n d in m o s t l a b o r a t o r i e s , t h e time
r e q u i r e d t o m e a s u r e a diffraction p a t t e r n r a n g e s from
minutes t o days. With the advent of new synchrotron
x-ray sources, this t i m e c a n b e r e d u c e d t o milli
seconds.
Diffraction m e a s u r e m e n t s s t u d y i n g time e v o l u t i o n
c a n b e categorized i n t o three types: p r e t r e a t m e n t a n d
p o s t - t r e a t m e n t m e a s u r e m e n t s , in situ s t r o b o s c o p i c
m e a s u r e m e n t s a n d direct in situ
time-resolved
m e a s u r e m e n t s . P r e t r e a t m e n t a n d p o s t - t r e a t m e n t tech
n i q u e s involve x-ray m e a s u r e m e n t s w h i c h a r e m a d e
before a n d after processing. Often, s o m e a t t e m p t is
m a d e d u r i n g processing t o a r r e s t t h e s t r u c t u r a l evolu
tion in m i d p r o c e s s . Classic e x a m p l e s of such m e a s u r e
m e n t s a r e diffraction m e a s u r e m e n t s m a d e after h e a t
t r e a t m e n t s in w h i c h t h e s a m p l e s a r e a n n e a l e d a t high
t e m p e r a t u r e s for v a r y i n g a m o u n t s o f time. F o r fast
processes, p r e t r e a t m e n t a n d p o s t - t r e a t m e n t m e a s u r e
m e n t s a r e often n o t possible o r a r e fraught with
systematic e r r o r s in w h i c h t h e s t r u c t u r e evolves in
u n e x p e c t e d w a y s d u r i n g t h e processing used t o arrest
t h e time e v o l u t i o n . I n spite o f these limitations, time
resolutions shorter than the required measurement
time of a diffraction p a t t e r n a r e possible.
S t r o b o s c o p i c t e c h n i q u e s a r e b a s e d o n a n ability t o
cycle a s a m p l e r e p e a t e d l y t h r o u g h a process. T h i s
567

X-Ray

Diffraction,

Time-Resolved

allows m e a s u r e m e n t s t o a v e r a g e over m a n y cycles a n d

build u p a diffraction p a t t e r n slowly over time b u t
with high time resolution. T h i s t e c h n i q u e is n o t
always applicable, since n o t all processing c a n b e
cycled o r cycled r e p r o d u c i b l y e n o u g h . T h i s t e c h n i q u e
is very powerful a n d h a s been used t o o b t a i n m i c r o
second a n d even n a n o s e c o n d time resolution.
T h e final m e t h o d , w h i c h h a s t h e m o s t stringent
r e q u i r e m e n t s , is r e p e a t e d real-time m e a s u r e m e n t s .
This m e t h o d h a s t h e a d v a n t a g e t h a t t h e analysis of
the d a t a is m o r e s t r a i g h t f o r w a r d a n d systematic
e r r o r s a r e greatly reduced. T h e time resolution of this
t e c h n i q u e directly d e p e n d s o n t h e time t o a c q u i r e a
diffraction p a t t e r n which, in o p t i m u m c o n d i t i o n s , c a n
be a few milliseconds o r even s h o r t e r .
D e s c r i p t i o n s of h o w diffraction m e a s u r e m e n t s a r e
m a d e a n d t h e i n f o r m a t i o n o b t a i n e d a r e given in t h e
articles Single-Crystal
X-Ray Diffraction, X-Ray and
Neutron Diffraction Studies of Amorphous Solids a n d
X-Ray Powder Diffraction. I n p a r t i c u l a r , t h e article o n
x-ray p o w d e r diffraction p r e s e n t s a list of the principle
uses of t h e m e t h o d . Time-resolved x-ray diffraction
allows t h e m e a s u r e m e n t of t h e time e v o l u t i o n of
this i n f o r m a t i o n . P r e t r e a t m e n t a n d p o s t - t r e a t m e n t
m e a s u r e m e n t t e c h n i q u e s use c o n v e n t i o n a l x-ray dif
fraction m e a s u r e m e n t s a n d t h u s will n o t b e discussed
here. T h i s article e m p h a s i z e s t h e use of in situ tech
niques a n d m o s t of t h e e m p h a s i s will b e o n direct
m e t h o d s . O f c o u r s e , a n y direct m e t h o d which reduces
the time needed t o m e a s u r e a diffraction p a t t e r n c a n
be used b y all t h e t e c h n i q u e s .

/.

Direct

Measurements

R e c e n t a d v a n c e s in x-ray sources a n d diffraction

g e o m e t r y h a v e led t o t e c h n i q u e s with e n o u g h x-ray
diffraction intensity so t h a t a diffraction p a t t e r n c a n
be a c q u i r e d in 1 m s . F o r this it is desirable t o h a v e 100
to 1000 c o u n t s in t h e m a x i m u m of a diffraction
p a t t e r n in o r d e r t o o b t a i n a high e n o u g h signal-tonoise r a t i o for analysis. M e a s u r e m e n t s of 1 m s t i m e
5
6
resolution t h e n require c o u n t rates exceeding 10 10
c o u n t s p e r second in t h e diffracted b e a m . It is quickly
realized t h a t c o n v e n t i o n a l x-ray d e t e c t o r s a r e n o t fast
e n o u g h for this type of m e a s u r e m e n t .
T h e m i n i m u m time t o o b t a i n a diffraction p a t t e r n is
t h u s usually d e t e r m i n e d either b y a l o w diffraction
intensity w h i c h limits t h e q u a l i t y of t h e diffraction
p a t t e r n o r b y t h e d e t e c t o r which limits t h e c o u n t i n g
speed.
A n x-ray diffraction e x p e r i m e n t consists of a n
incident b e a m of rays, usually m o n o c h r o m a t i c ,
which strike a s a m p l e a n d scatter i n t o a d e t e c t o r
system. T o decrease t h e time r e q u i r e d for m e a s u r i n g a
diffraction p a t t e r n , it is necessary t o increase t h e
n u m b e r of x-ray p h o t o n s which strike t h e s a m p l e a n d /
o r increase t h e d e t e c t i o n efficiency. T h e m o s t intense
x-ray sources a r e s y n c h r o t r o n s . T h e s e sources a r e

568

m o r e t h a n six o r d e r s of m a g n i t u d e b r i g h t e r t h a n
c o n v e n t i o n a l r o t a t i n g a n o d e x-ray sources a n d synch
r o t r o n facilities scheduled t o b e c o m p l e t e d in t h e m i d 1990s will b e yet a n o t h e r t h o u s a n d times brighter.
H a v i n g selected a s o u r c e , three w a y s exist t o increase
the t o t a l flux in t h e incident b e a m : use m o r e w a v e
lengths of t h e s o u r c e , use m o r e angles of t h e s o u r c e o r
use s o m e c o m b i n a t i o n of b o t h . Often, t h e resulting
increase in flux is a t t h e expense of lowering t h e
diffraction r e s o l u t i o n of t h e e x p e r i m e n t .
Before p r o c e e d i n g , it is w o r t h w h i l e m e n t i o n i n g a n
essential difference b e t w e e n t w o types of m e a s u r e
m e n t s , p o w d e r diffraction a n d single-crystal dif
fraction. B r a g g ' s law requires t w o c o n d i t i o n s t o b e
satisfied for diffraction. O n e results b e c a u s e t h e angle
of incidence of t h e r a y s o n t h e diffracting p l a n e s
m u s t b e correct a n d t h e s e c o n d b e c a u s e rays will
diffract only in certain directions. T h e incident angle
r e q u i r e m e n t m e a n s t h a t for time-resolved diffraction
o n single crystals it is also necessary, except in special
cases, t o c h a n g e t h e o r i e n t a t i o n of t h e crystal. F o r
p o w d e r s , crystallites exist a t all o r i e n t a t i o n s a n d so
t h e first r e q u i r e m e n t is always satisfied a n d only t h e
p l a c e m e n t of t h e x-ray d e t e c t o r a t t h e correct scatter
ing angles is needed. A n o t h e r i m p o r t a n t difference
b e t w e e n a single crystal a n d a p o w d e r s a m p l e of t h e
s a m e m a t e r i a l is t h e relative intensity of a typical
B r a g g p e a k . F o r a single crystal t h e intensity of a
B r a g g p e a k is localized i n t o a n intense small solid
angle of scattering. I n c o n t r a s t , t h e m a n y o r i e n t a t i o n s
of crystallites in a polycrystalline s a m p l e result in a
c o n e of scattering of w h i c h diffractometers only
m e a s u r e a small fraction.
T h e m o s t o b v i o u s w a y t o i m p r o v e t h e detection
efficiency in a c o n v e n t i o n a l p o w d e r diffraction experi
m e n t is t o use m a n y d e t e c t o r s a n d therefore collect
m a n y scattering angles s i m u l t a n e o u s l y . T h i s is c o n
veniently d o n e using o n e - d i m e n s i o n a l a n d t w o d i m e n s i o n a l d e t e c t o r a r r a y s , w h i c h a r e often referred
to a s position-sensitive d e t e c t o r s . T h e diffraction reso
lution of these d e t e c t o r s is partially d e t e r m i n e d b y t h e
physical size o f e a c h d e t e c t o r element a n d t h e time
r e s o l u t i o n is d e t e r m i n e d b y t h e electronics, which
limits t h e m a x i m u m m e a s u r a b l e c o u n t r a t e . T h e
oldest position-sensitive d e t e c t o r is a p r o p o r t i o n a l
wire d e t e c t o r . T h e y c o n v e n t i o n a l l y give 100 spa
tial r e s o l u t i o n a n d c a n s p a n a region of 510 c m in
either a straight line o r a l o n g a circular a r c . T h e s e
d e t e c t o r s h a v e a very l o w intrinsic b a c k g r o u n d . T h e i r
p r i m a r y deficiency is t h a t they h a v e a relatively low
m a x i m u m c o u n t r a t e of a r o u n d 50 000 rays p e r
second i n t e g r a t e d over t h e w h o l e detector. Since
50 000 c o u n t s s p r e a d over a diffraction p a t t e r n is
a b o u t t h e m i n i m u m n u m b e r of c o u n t s r e q u i r e d t o
define a diffraction p a t t e r n , this limits t h e m i n i m u m
time p e r diffraction p a t t e r n t o a r o u n d 1 s. M o r e
recently, p h o t o d i o d e a r r a y s ( S t e p h e n s o n 1988) a n d
c h a r g e - c o u p l e d device ( C C D ) a r r a y s ( R o d r i c k s et al.
1989) h a v e b e c o m e available for x-ray detection. T h e y

X-Ray

h a v e m u c h higher m a x i m u m c o u n t rates a n d faster

r e a d o u t times. T h e i r p r i n c i p a l deficiency is their
s h o r t e r length a n d higher intrinsic b a c k g r o u n d . F o r
p h o t o d i o d e a r r a y s , r e a d o u t times of several millise
c o n d s are possible a n d a r r a y s w i t h t o t a l lengths of 2 5 c m a r e available. E a c h d i o d e is typically 25 in
length. T h e m a x i m u m c o u n t r a t e of e a c h d i o d e c a n b e
6
greater t h a n rays p e r second. C C D a r r a y s a r e
available with r e a d o u t times of several m i c r o s e c o n d s ,
w h e n used as o n e - d i m e n s i o n a l a r r a y s (streak c a m e r a
m o d e ) . T h e i r t o t a l d i m e n s i o n s a r e typically less t h a n
1 c m with e a c h d e t e c t o r d i m e n s i o n being a p p r o x i m
ately 25 . E x a m p l e s of t h e use of these d e t e c t o r s
for time-resolved m e a s u r e m e n t s a r e given in t h e
following.
T h e r a n g e of angles s i m u l t a n e o u s l y incident o n a
s a m p l e c a n be increased by using a c u r v e d focusing
m o n o c h r o m a t o r . I n c r e a s i n g t h e r a n g e of incident
angles is p a r t i c u l a r l y a d v a n t a g e o u s for single-crystal
e x p e r i m e n t s since this relaxes t h e need for c h a n g i n g
the o r i e n t a t i o n of t h e s a m p l e . O n e e x a m p l e of a n
e x p e r i m e n t t a k i n g a d v a n t a g e of this is given b y
C l a r k e et al. (1991). U s i n g a b e n t g e r m a n i u m
m o n o c h r o m a t o r crystal, a n incident a n g u l a r r a n g e of
0.07 w a s o b t a i n e d with a diffraction r e s o l u t i o n of 3
3
p a r t s in 10 . T h e y used a C C D d e t e c t o r as a o n e d i m e n s i o n a l position-sensitive d e t e c t o r t o collect a
r a n g e of scattered angles. T h i s d e t e c t o r allows diffrac
tion profiles t o be t a k e n as r a p i d l y as o n e every 25 .
In their e x p e r i m e n t , C l a r k e et al. m e a s u r e d t h e (004)
Bragg p e a k of thin films of G a 0 9 5I n 0 0 5A s epitaxially
grown on G a A s . They present data acquired during
r a p i d t h e r m a l a n n e a l i n g with a time r e s o l u t i o n of
100 m s per p a t t e r n .
A n o t h e r w a y t o increase t h e incident b e a m intensity
is t o increase t h e m o n o c h r o m a t o r b a n d p a s s , t h e
resulting increase in time r e s o l u t i o n being m o r e desir
able t h a n t h e loss in diffraction r e s o l u t i o n . X - r a y
m o n o c h r o m a t o r s for diffraction e x p e r i m e n t s typically
w o r k by using d y n a m i c a l diffraction from perfect
single crystals, t h e choice of m o n o c h r o m a t o r crystals
then d e t e r m i n i n g t h e w a v e l e n g t h b a n d p a s s . T h e avail
ability of large h i g h - q u a l i t y single crystals of silicon
a n d g e r m a n i u m m e a n s t h a t they a r e m o s t c o m m o n l y
used. T h e b a n d p a s s for t h e (111) B r a g g p e a k of silicon
is 0.01 % a n d for G e ( l 11) is 0 . 0 2 % . T h e s e values result
in a r e a s o n a b l y high diffraction r e s o l u t i o n a n d h i g h e r
resolution c a n b e o b t a i n e d b y using h i g h e r o r d e r
Bragg reflections. A b a n d p a s s of 1 % is usually m o r e
t h a n e n o u g h diffraction r e s o l u t i o n a n d c a n lead t o a
large increase in intensity relative t o S i ( l l l ) o r
G e ( l 11). T h e difficulty in o b t a i n i n g large h i g h - q u a l i t y
single crystals of t h e a p p r o p r i a t e m a t e r i a l c a n
be sidestepped by using artificially m o d u l a t e d m a t e r
ials. O n e such e x a m p l e uses t u n g s t e n - s i l i c o n m u l t i
layers with a p e r i o d of 2.3 n m ( S t e p h e n s o n 1988). U s e
of these multilayer m o n o c h r o m a t o r s a n d a p h o t o d i o d e a r r a y linear d e t e c t o r h a s resulted in a system
c a p a b l e of a c q u i r i n g diffraction p a t t e r n s with a t i m e

Diffraction,

Time-Resolved

r e s o l u t i o n of a few milliseconds from small polycrys

talline m e t a l r i b b o n s . T h i s s e t u p h a s been used t o
m e a s u r e t h e crystallization of metallic glasses ( S u t t o n
et al. 1988) a n d t h e o r d e r i n g in C u 3 A u ( L u d w i g et al.
1988).
I n energy-dispersive x-ray diffraction, a wellcollimated b e a m containing m a n y
wavelengths
(energies) strikes a s a m p l e a n d scatters i n t o a n energysensitive d e t e c t o r a t s o m e fixed scattering angle.
B r a g g ' s law m e a n s t h a t only c e r t a i n w a v e l e n g t h s will
scatter i n t o t h a t angle a n d diffraction profiles similar
t o c o n v e n t i o n a l p o w d e r x-ray diffraction
are
o b t a i n e d . T h i s t e c h n i q u e h a s t h e a t t r a c t i v e feature
t h a t only o n e incident angle a n d o n e diffraction angle
need b e a c c o m m o d a t e d in t h e s a m p l e c h a m b e r . It is
often u s e d in h i g h - p r e s s u r e diffraction m e a s u r e m e n t s
u s i n g d i a m o n d anvil cells. S o far this t e c h n i q u e h a s
n o t b e e n widely used for time-resolved m e a s u r e m e n t s
b u t for t h e p r e s s u r e e x p e r i m e n t s , diffraction profiles
a r e c o n v e n t i o n a l l y a c q u i r e d w i t h timescales of several
m i n u t e s . T h e diffraction r e s o l u t i o n of these experi
m e n t s is a g a i n of o r d e r 1 % . X - r a y s a r e m e a s u r e d b y
a n intrinsic g e r m a n i u m solid-state d e t e c t o r which
h a v e a m a x i m u m c o u n t r a t e of a r o u n d 5000 rays p e r
s e c o n d . T h e r e f o r e , until faster d e t e c t o r s b e c o m e avail
able, t h e best time r e s o l u t i o n will r e m a i n several
s e c o n d s p e r p a t t e r n . A n e x a m p l e of this type of
m e a s u r e m e n t is r e p o r t e d b y B a u b l i t z et al. (1981).
C o n c o m i t a n t with t h e s h o r t e n i n g time p e r diffrac
t i o n p a t t e r n , direct m e t h o d s r e q u i r e the d e v e l o p m e n t
of s a m p l e c h a m b e r s w h i c h allow t h e c h a n g i n g of t h e
s a m p l e e n v i r o n m e n t o n c o m p a r a b l e timescales. Ste
p h e n s o n et al. (1989) a n d B r a u e r et al.(1990) describe
t e c h n i q u e s d e v e l o p e d for fast in situ t e m p e r a t u r e
c h a n g e s . T h e i r t e c h n i q u e s a r e b a s e d o n using small
metallic ribbons w h i c h a r e h e a t e d b y J o u l e selfh e a t i n g a n d t h e t e m p e r a t u r e is m e a s u r e d b y a fast
6
- 1
infrared p y r o m e t e r . H e a t i n g rates of 1 0 K s
and
1
c o o l i n g rates of 1500 s " w i t h o u t o v e r s h o o t i n g a r e
demonstrated.
2. Stroboscopic

Measurements

T h e diffraction geometries for s t r o b o s c o p i c m e a s u r e

m e n t s a r e t h e s a m e as for t h e direct m e t h o d s a l r e a d y
described. S t r o b o s c o p i c m e t h o d s c a n be used w h e n
t h e time r e s o l u t i o n is limited b y low c o u n t i n g rates
a n d n o t by t h e m a x i m u m c o u n t r a t e of the d e t e c t o r
system. T h e y c a n also b e used t o e x t e n d the r a n g e of
diffraction angles.
T w o e x a m p l e s serve t o d e m o n s t r a t e t h e p o w e r of
t h e s t r o b o s c o p i c t e c h n i q u e . T h e first e x a m p l e is a n
e x p e r i m e n t t o m e a s u r e t h e m e l t i n g a n d recrystallizat i o n of a silicon surface d u r i n g a h i g h - p o w e r laser
pulse ( L a r s o n et al. 1986). By t a k i n g a d v a n t a g e of t h e
p u l s e d n a t u r e of a s y n c h r o t r o n source a n d by synch
r o n i z i n g t h e laser pulses a n d m e a s u r e m e n t s t o the
x-ray pulses, a t i m e r e s o l u t i o n of less t h a n 1 ns w a s
achieved.

569

X-Ray

Diffraction,

Time-Resolved

T h e second e x a m p l e uses n e w diffraction tech

niques developed t o s t u d y t h e surfaces of crystals.
W a n g a n d O c k o (1992) studied t h e (111) surface of
single crystals of gold in situ in a n electrochemical cell.
W i t h diffraction m e a s u r e m e n t s s y n c h r o n i z e d t o vol
tage pulses applied t o t h e cell, they were able t o s t u d y
the time r e s p o n s e of a surface r e c o n s t r u c t i o n i n d u c e d
o n the surface of t h e gold single-crystal electrode with
a time resolution of a few seconds.

5. Future

Possibilities

This article h a s focused o n the t e c h n i q u e s of in situ

real-time diffraction m e a s u r e m e n t s a n d diffraction
geometries r a t h e r t h a n o n results. Time-resolved xr a y diffraction is a rapidly evolving field a n d the
choice of t h e best t e c h n i q u e t o use often d e p e n d s o n
t h e system u n d e r study.
T h e resulting increase in intensity from the use of
s y n c h r o t r o n s as x-ray sources h a s m e a n t a n e n o r m o u s
increase in possibilities, n o t only for time-resolved
m e a s u r e m e n t s , b u t for all x-ray diffraction. T h e rela
tively recent a d v e n t of s y n c h r o t r o n s d e d i c a t e d for xr a y sources h a s also led t o accessibility for a wide
r a n g e of users. N e w diffraction t e c h n i q u e s , new x-ray
detector d e v e l o p m e n t s a n d t h e m o r e intense s y n c h r o
t r o n sources c u r r e n t l y u n d e r c o n s t r u c t i o n m e a n t h a t
time-resolved x-ray diffraction will c o n t i n u e its r a p i d
evolution for m a n y years to c o m e .
I n conclusion, a n e x a m p l e of o n e such new tech
n i q u e will be given. It h a s been s h o w n b y S u t t o n et al.
(1991) t h a t a spatially c o h e r e n t b e a m of 0.155 n m
rays c a n be o b t a i n e d with sufficient intensity t o per
form a diffraction e x p e r i m e n t . T h i s m e a n s t h a t a
technique called d y n a m i c light scattering o r intensity
fluctuation s p e c t r o s c o p y c a n be e x t e n d e d i n t o t h e
h a r d x-ray region. W i t h light, this t e c h n i q u e is c o m
m o n l y used t o m e a s u r e t h e kinetics of t r a n s i t i o n s in
t r a n s p a r e n t m a t e r i a l s o n length scales of t h e o r d e r of
the wavelength of light o r longer. W i t h rays, t h e
t e c h n i q u e c a n be used for o p a q u e m a t e r i a l s a n d for
m u c h s h o r t e r length scales. It is also o n e of t h e few
techniques which c a n directly m e a s u r e kinetic p a r a m
eters in equilibrium systems.
See also: Thermophysical
X-Ray Powder Diffraction

Measurements,

Subsecond;

Bibliography
Baublitz A Jr, Arnold V, Ruoff A L 1981 Energy
dispersive x-ray diffraction from high pressure polycrystalline specimens using synchrotron radiation. Rev. Sci.
Instrum. 52: 1616-24
Brauer S, Ryan D H, Strom-Olsen J O, Sutton M, Stephen
son G 1990 Pyrometric temperature controller for
million degree per second heating. Rev. Sci. Instrum. 61:
2214-19

570

Clarke R, Dos Passos W, Lowe W, Rodricks G, Brizard C

1991 Real-time x-ray studies of strain kinetics in
hijGa^jjAs quantum well structures. Phys. Rev. Lett. 66:
317-20
Larson C, Tischler J Z, Mills D 1986 Nanosecond
resolution time-resolved x-ray study of silicon during
pulsed-laser irradiation. / . Mater. Res. 1: 144-54
Ludwig F Jr, Stephenson G B, Jordan-Sweet J L, Mainville J, Yang Y S, Sutton 1988 Nucleated and continu
ous ordering in Cu 3Au. Phys. Rev. Lett. 61: 1859-62
Rodricks B, Clarke R, Smither R, Fontaine A 1989 A
virtual phase CCD detector for synchrotron radiation
applications. Rev. Sci. Instrum. 60: 2586-91
Stephenson G 1988 Time resolved x-ray scattering using a
high intensity multilayer monochromator. Nucl. Methods
Instrum. A 266: 447-51
Stephenson G B, Ludwig F Jr, Jordan-Sweet J L, Mainville J, Yang Y S, Sutton 1989 Instrumentation for
millisecond-resolution scattering studies. Rev. Sci.
Instrum. 60: 1537-40
Sutton M, Mochrie S G, Greytak T, Nagler S E, Bermann L
Held G, Stephenson G 1991 Observation of speckle
by diffraction with coherent x-rays. Nature. 352: 608-10
Sutton M, Yang Y S, Mainville J, Strom-Olsen J O,
Altounian Z, Stephenson G B, Ludwig F Jr 1988
Crystallization of amorphous NiZr 2. Mater. Sci. Eng. 97:
307-11
Wang J, Ocko 1992 In situ x-ray diffraction and
reflectivity studies of the Au(III)/electrolyte interface:
reconstruction and anion adsorption. Phys. Rev. (in
press)
M. Sutton
[McGill University, M o n t r e a l , C a n a d a ]

X-Ray Fluorescence Spectrometry

I n s t r u m e n t a l element-analysis m e t h o d s b a s e d o n xr a y spectra m a y be classified by m e a n s of spectral
excitation a n d dispersion. X - r a y fluorescence s p e c t r o
m e t r y ( X R F S ) uses x-ray excitation a n d either
w a v e l e n g t h o r energy dispersion. A m o n g elemental
analysis m e t h o d s , x-ray fluorescence s p e c t r o m e t r y is
u n s u r p a s s e d in its c o m b i n a t i o n of convenience, speed,
a n d precision a n d a c c u r a c y , a n d in its versatility a n d
latitude of applicable elements a n d c o n c e n t r a t i o n
r a n g e s , i n s t r u m e n t c o m p o n e n t s a n d accessories, oper
a t i o n a l m o d e s a n d c o n d i t i o n s , analytical techniques
a n d specimen forms. T h i s article outlines the
principles, i n s t r u m e n t a t i o n , a n d t e c h n i q u e s of w a v e
length-dispersive x-ray
fluorescence
spectrometric
analysis.

1. Definition,

Scope,

Advantages,

Limitations

X - r a y fluorescence s p e c t r o m e t r y is a n o n d e s t r u c t i v e
i n s t r u m e n t a l m e t h o d of qualitative a n d q u a n t i t a t i v e
analysis for chemical elements b a s e d o n the w a v e
lengths a n d intensities of their x-ray-excited spectral

X-Ray

lines. " P r i m a r y " rays, usually from a n x-ray t u b e ,

excite each specimen element t o emit its x-ray spectral
lines, which h a v e w a v e l e n g t h s characteristic of t h a t
element (qualitative analysis) a n d intensities related t o
its c o n c e n t r a t i o n ( q u a n t i t a t i v e analysis).
I n favorable cases, c o m m e r c i a l flat-crystal spec
t r o m e t e r s a r e applicable t o all elements d o w n t o
a t o m i c n u m b e r 9 (fluorine), c o n c e n t r a t i o n s from 100
1
to 0.0001 w t % in solids a n d d o w n t o ~ 0 . 1 g m in
liquids, isolated m a s s e s d o w n t o ~ 1 n g , a n d films a s
" t h i n " as ~ 0 . 0 1 m o n o l a y e r . Special accessories per
mit analysis for beryllium, b o r o n , c a r b o n , n i t r o g e n
a n d oxygen. Sensitivity decreases m a r k e d l y for ele
m e n t s below a t o m i c n u m b e r 13 ( a l u m i n u m ) .
Specimens c a n h a v e practically a n y form (see Sect.
11).
Typical
maximum
specimen
size
is
2
20 c m x 2.5 c m thick, b u t special accessories appli
cable t o s o m e i n s t r u m e n t s p e r m i t analysis o n very
large a n d very small specimens a n d small selected
areas. T h e effective specimen a r e a is defined b y a
2
w i n d o w e d m a s k a n d is typically 1-5 c m . T h e effective
specimen thickness is d e t e r m i n e d n o t b y t h e d e p t h t o
which t h e p r i m a r y rays p e n e t r a t e , b u t b y t h e d e p t h
from which t h e m e a s u r e d rays c a n e m e r g e . I n
general, this layer is 0 . 1 - 1 m m , a n d is d e e p e r t h e
s h o r t e r t h e m e a s u r e d w a v e l e n g t h a n d t h e lower t h e
specimen a b s o r p t i o n for t h a t wavelength. F o r q u a n t i
tative analysis, all specimens m u s t b e "infinitely
t h i c k " for all m e a s u r e d w a v e l e n g t h s o r else h a v e t h e
s a m e thickness. X - r a y fluorescence s p e c t r o m e t r y c a n
be used t o m e a s u r e t h e thickness of layers less t h a n
infinitely thick b u t o f t h e s a m e c o m p o s i t i o n .
Analytical precision m a y b e 0.1 % relative for
m a j o r a n d m i n o r c o n s t i t u e n t s , b u t is m u c h p o o r e r for
traces. Analytical a c c u r a c y is d e t e r m i n e d b y t h e a c
c u r a c y of t h e s t a n d a r d s , t h e physical a n d chemical
similarity of s t a n d a r d s a n d samples, a n d t h e efficacy
of t h e m a t r i x c o r r e c t i o n m e t h o d (see Sect. 10). T h e
m e t h o d is substantially n o n d e s t r u c t i v e , b u t s o m e
m a t e r i a l s u n d e r g o radiolysis a n d / o r r a d i a t i o n d a m a g e
in t h e intense p r i m a r y r a d i a t i o n , o r o x i d a t i o n in t h e
o z o n e it p r o d u c e s . W h e n as-received s a m p l e s c a n b e
analyzed with m i n i m a l p r e p a r a t i o n , t h e m e t h o d is
extremely r a p i d a n d c o n v e n i e n t .
M a n u a l a n d a u t o m a t i c sequential x-ray s p e c t r o m
eters (see Sect. 8) cost a b o u t 75 000 a n d 150 000 U S
dollars, respectively. T h e m a n u a l i n s t r u m e n t c a n b e
c o n v e r t e d t o t h e sequential. A n a u t o m a t i c s i m u l t a n
e o u s s p e c t r o m e t e r (see Sect. 8) costs a b o u t 225 000 U S
dollars for 10 c h a n n e l s a n d u p t o 350 000 U S d o l l a r s
for 30. X - r a y t u b e s cost a b o u t 5000 U S d o l l a r s a n d
last a few t h o u s a n d h o u r s .

2. X Rays and X-Ray

Spectra

X rays m a y b e defined a s e l e c t r o m a g n e t i c r a d i a t i o n in
5
the wavelength region ~ 1 0 ~ - 1 0 n m p r o d u c e d b y
deceleration of high-energy electrons a n d / o r b y elec-

Fluorescence

Spectrometry

Wavelength

Figure 1
Section of an atom of an element of high atomic number,
showing the electron transitions that produce the principal
characteristic x-ray spectral lines and the x-ray spectrum
from an x-ray tube having a target of high atomic number
and operated at high potential (from Introduction to
X-Ray Spectrometric Analysis, courtesy of Plenum Press)

t r o n t r a n s i t i o n s t o t h e inner orbits of a t o m s . I n
analytical x-ray fluorescence s p e c t r o m e t r y , t h e appli
cable spectral region is ~ 0 . 0 1 - 2 n m a n d with special
accessories t o ~ 1 0 n m . X rays a r e characterized b y
w a v e l e n g t h ( n m ) p h o t o n energy (eV), a n d inten
sity / ( p h o t o n s , o r " c o u n t s , " p e r second). T h e w a v e
length a n d p h o t o n energy a r e related reciprocally:
E= 124 000/A. T h e c o n s t a n t in this e q u a t i o n is (he/
11
e) x 1 0 n m m~ \ w h e r e h is P l a n c k ' s c o n s t a n t , c is t h e
velocity of light a n d e is t h e electron c h a r g e . T h e r e a r e
t w o types of x-ray emission spectra: c o n t i n u o u s a n d
characteristic-line (see F i g . 1).
The continuous spectrum, continuum or "brehmss t r a h l u n g " o c c u r s in significant intensity only with
electron excitation a n d arises from d e c r e m e n t a l decel
e r a t i o n of electrons. It is c h a r a c t e r i z e d by a c o n t i n u
o u s b a n d of wavelengths, s t a r t i n g a t a m i n i m u m
w a v e l e n g t h d e t e r m i n e d b y t h e electron acceleration
p o t e n t i a l V (A m in = 124 000/) rising t o m a x i m u m
intensity a t 1.5 A m i n, a n d decreasing in intensity a t
increasing wavelength (Fig. 1).
C h a r a c t e r i s t i c x-ray line spectra arise w h e n v a c a n
cies o c c u r in t h e K , L a n d shells of a t o m s a n d
electrons from shells further o u t fall i n t o these v a c a n
cies, t h e r e b y losing energy, which a p p e a r s as x-ray
photons. Fig. 1 shows the transitions that produce the
principal lines a n d t h e s y m b o l s a n d relative intensities

571

X-Ray

Fluorescence

Spectrometry

M i l l

of these lines. E l e m e n t s of low, i n t e r m e d i a t e a n d high

a t o m i c n u m b e r h a v e K , K - L a n d K - L - M spectra,
respectively. F o r a specified line, say K a ^ w a v e l e n g t h
decreases ( p h o t o n energy increases) m o n o t o n i c a l l y as
a t o m i c n u m b e r increases, regardless of physical a n d
chemical state.

3. Excitation

of Characteristic

X-Ray

Spectra

Excitation of x-ray line spectra consists in expulsion

of K-, L- a n d / o r M-shell electrons in large n u m b e r s .
Excitation m a y b e effected by high-energy particles
(electrons, p r o t o n s , d e u t e r o n s , a l p h a s a n d heavier
ions) o r high-energy p h o t o n s (x a n d rays). E a c h h a s
a d v a n t a g e s a n d limitations, a n d s p e c t r o m e t e r s a p p l y
ing each are in use. Interest here is limited t o t h e
electron excitation t h a t p r o d u c e s t h e p r i m a r y b e a m in
the x-ray t u b e a n d the x-ray excitation t h a t o c c u r s
w h e n this b e a m irradiates the specimen.
Excitation requires energy. T h e m i n i m u m energy
t h a t a n electron m u s t h a v e t o expel a specified elec
t r o n from a specified orbital in a n a t o m of a specified
element is the excitation p o t e n t i a l . T h e m i n i m u m
p h o t o n energy o r t h e m a x i m u m w a v e l e n g t h t h a t a
p h o t o n m u s t h a v e t o expel t h a t electron is the critical
a b s o r p t i o n energy o r a b s o r p t i o n edge. E a c h element
h a s o n e K , three L a n d five excitation p o t e n t i a l s ,
critical energies a n d a b s o r p t i o n edges c o r r e s p o n d i n g
to the orbitals in Fig. 1, insofar as the element h a s
those orbitals.
F o r a specified element, t h e closer a n electron
orbital lies t o t h e positive a t o m nucleus, t h e m o r e
tightly it is b o u n d a n d t h e higher t h e excitation
energy, t h a t is, t h e higher the excitation p o t e n t i a l o r
critical energy a n d the s h o r t e r the a b s o r p t i o n edge.
Similarly, for a specified orbital, say L I I I , t h e higher
the a t o m i c n u m b e r , the m o r e tightly t h e electrons a r e
b o u n d a n d t h e higher t h e excitation energy.
In x-ray
fluorescence
s p e c t r o m e t e r s , t h e x-ray
source used to excite the specimen is usually a n x-ray
t u b e , b u t a r a d i o i s o t o p e is s o m e t i m e s used. In t h e xray t u b e (see Sect. 5), electrons p r o d u c e c o n t i n u u m
r a d i a t i o n by stepwise deceleration a n d the target line
s p e c t r u m b y the c r e a t i o n of electron-orbital v a c a n
cies. T h e p r i m a r y b e a m c o m p r i s e s t h e t a r g e t line
spectrum superimposed on the continuum. The char
acteristic s p e c t r u m of each specimen element is
excited only by p r i m a r y c o n t i n u u m a n d target lines of
wavelength s h o r t e r t h a n the a b s o r p t i o n edges of its K ,
L a n d / o r orbitals.
T h e p r i m a r y b e a m excites n o c o n t i n u u m in the
specimen b u t the specimen scatters p r i m a r y rays.
T h u s , the rays leaving the specimen c o m p r i s e the
emitted characteristic spectra of t h e specimen ele
m e n t s a n d the scattered p r i m a r y c o n t i n u u m a n d tar
get lines. Scattered c o n t i n u u m largely c o n s t i t u t e s t h e
b a c k g r o u n d of t h e specimen s p e c t r u m .

572

Figure 2
Distinction between wavelength dispersion (right of
specimen), in which the rays are dispersed spacially by
wavelength prior to detection, and energy dispersion (left
of specimen), in which all rays are detected
simultaneously and detector output pulses are separated
by amplitude electronically (from Introduction to X-Ray
Spectrometric Analysis, courtesy of Plenum Press)

4.

Dispersion

A n y analytical m e t h o d involving x-ray spectral lines

m u s t p r o v i d e a m e a n s t o p e r m i t a line of e a c h
specimen element t o be m e a s u r e d individually. T w o
such m e a n s a r e in c o m m o n use. I n energy dispersion,
t h e d e t e c t o r receives e m i t t e d a n d scattered rays
directly from t h e specimen a n d for e a c h a b s o r b e d
p h o t o n p r o d u c e s a n electric pulse of a m p l i t u d e p r o
p o r t i o n a l t o the p h o t o n energy (see Sect. 7). T h e
amplified d e t e c t o r o u t p u t u n d e r g o e s electronic pulseheight analysis t o s e p a r a t e t h e pulses for e a c h spectral
line. I n w a v e l e n g t h dispersion (see Sect. 6), t h e rays
a r e s e p a r a t e d spacially by w a v e l e n g t h b y crystal dif
fraction p r i o r t o detection, so t h a t usually t h e d e t e c t o r
receives only o n e w a v e l e n g t h a t a time. F i g u r e 2
illustrates the t w o m o d e s in a highly simplified form
for three of t h e m a n y w a v e l e n g t h s e m i t t e d o r scat
tered by t h e s a m p l e .

5. InstrumentationX-Ray

Generator

T h e wavelength-dispersive x-ray fluorescence spec

t r o m e t e r c o m p r i s e s a n x-ray g e n e r a t o r (x-ray t u b e
a n d p o w e r supply), specimen c h a m b e r , s p e c t r o goniometer,
and
electronic
detection
and
r e a d o u t system.
T h e x-ray t u b e c o m p r i s e s a m e t a l target a n d t u n g
sten filament in a n x - r a y - p r o o f m e t a l h e a d h a v i n g a
thin beryllium w i n d o w a n d sealed t o a r e e n t r a n t glass
t u b e . T h e t u b e a n d h e a d c o n s t i t u t e a sealed highv a c u u m enclosure. In o p e r a t i o n , t h e filament is h e a t e d
t o incandescence b y electric c u r r e n t a n d emits elec
t r o n s , which a r e accelerated to t h e target w h e r e they

X-Ray

Fluorescence

Spectrometry

5 0 kV

Figure 3
X-ray generator: the solid and dashed waveforms at the top correspond to the high (solid arrow) and low (dashed arrow)
settings of the autotransformer. The resistor and capacitor constitute the constant-potential filter. The switch represents
various automatic safety devices

excite x-ray emission, w h i c h emerges t h r o u g h t h e

beryllium w i n d o w . T h e t a r g e t m u s t b e w a t e r c o o l e d
because o p e r a t i o n at, say, 5 0 k V - 5 0 m A dissipates
2500 W , of w h i c h only 1-2% p r o d u c e s r a y s , t h e
r e m a i n d e r h e a t . T u n g s t e n is t h e m o s t c o m m o n
g e n e r a l - p u r p o s e t a r g e t , b u t c h r o m i u m is preferable
for excitation of s p e c t r a of elements 9 - 2 3 ( f l u o r i n e vanadium).
T h e x - r a y - t u b e p o w e r s u p p l y c o m p r i s e s a lowp o w e r a c supply for t h e x-ray t u b e filament, highp o t e n t i a l d c s u p p l y for t h e target, stabilization circuits
a n d safety devices. F i g u r e 3 s h o w s the m a i n c o m p o
n e n t s a n d the sequence of a c a n d d c w a v e f o r m s . T h e
filament supply c o m p r i s e s a r h e o s t a t a n d s t e p - d o w n
t r a n s f o r m e r , delivers u p t o ~ 1 0 V - 5 A a c , a n d per
mits v a r i a t i o n of t h e filament p o w e r a n d t h e r e b y of
t e m p e r a t u r e , electron emission a n d t u b e c u r r e n t . T h e
target supply c o m p r i s e s a v a r i a b l e a u t o t r a n s f o r m e r ,
step-up t r a n s f o r m e r , rectifier a n d o p t i o n a l c o n s t a n t p o t e n t i a l filter, a n d delivers u p t o 50, 75 o r 100 k V a t
u p t o 75 m A full-wave p u l s a t i n g o r c o n s t a n t - p o t e n t i a l
dc. T h e t a r g e t p o t e n t i a l a n d c u r r e n t m a y b e varied
from zero t o m a x i m u m values with their respective
c o n t r o l s a n d a r e indicated o n their respective m e t e r s .
Provision is m a d e for stabilization o f t h e a c line,
target p o t e n t i a l (kV) a n d t u b e c u r r e n t ( m A ) . Safety
devices a u t o m a t i c a l l y s h u t off t h e s u p p l y w h e n t h e
electric c u r r e n t a n d c o o l i n g - w a t e r p r e s s u r e exceed
preset limits a n d / o r t h e c a b i n e t d o o r s a r e o p e n e d .
T h e flat-crystal wavelength-dispersive s p e c t r o m e t e r
(see Sect. 6) is extremely wasteful of e m i t t e d specimen
spectral r a d i a t i o n , so h i g h - p o w e r ( ^ 2500 W ) g e n e r a
t o r s a r e r e q u i r e d . E n e r g y dispersion uses n o g o n i
o m e t e r , so t h e d e t e c t o r is n e a r t h e specimen a n d
intercepts a large solid angle of r a d i a t i o n , p e r m i t t i n g

excitation b y l o w - p o w e r ( ^ 100 W ) x-ray o r r a d i o i s o

t o p e sources.

6. InstrumentationSpecimen
Spectrogoniometer

Chamber

and

S o m e s p e c t r o g o n i o m e t e r s a r e s e p a r a t e self-contained
table-top instruments having the x-ray-tube window
directed d o w n w a r d i n t o a c h a m b e r h a v i n g a r e m o v
able d r a w e r for specimens ~ 2 . 5 c m in d i a m e t e r a n d
thickness. T h e s e i n s t r u m e n t s c a n be r e a r r a n g e d with
t h e x-ray w i n d o w u p w a r d ("inverted o p t i c s " ) for very
large specimens, such as i n g o t s , engine p a r t s a n d a r t
objects. I n m o s t s p e c t r o m e t e r s , t h e g o n i o m e t e r h a s
inverted optics b u t is enclosed o n all sides, limiting
m a x i m u m specimen size t o ~ 5 c m d i a m e t e r by
~ 2 . 5 c m thick. T h e specimen c h a m b e r m a y h o l d a
single specimen o r p r o v i d e for a u t o m a t i c sequential
i n d e x i n g of u p t o 30.
T h e s p e c t r o g o n i o m e t e r (Fig. 4) c o m p r i s e s t w o colli
m a t o r s , a n a n a l y z e r crystal a n d a d e t e c t o r a r r a n g e d
o n a m a n u a l o r m o t o r - d r i v e n precision r o t a t i n g
m e c h a n i s m . T h e c o l l i m a t o r s consist of spaced parallel
m e t a l foils rigidly held in rectilinear m e t a l tunnels.
T h e single-crystal b a r serves as a n x-ray diffraction
g r a t i n g . T h e d e t e c t o r is described in Section 7. O n e
c o l l i m a t o r is fixed a t t h e o u t p u t e n d of t h e specimen
c h a m b e r . T h e crystal is bisected b y a n d r o t a t e s a b o u t
t h e g o n i o m e t e r axis a t angle 0 p e r u n i t time as the
o t h e r c o l l i m a t o r a n d d e t e c t o r r o t a t e t o g e t h e r a t angle
20 p e r u n i t time. A t w a v e l e n g t h s s h o r t e r t h a n
~ 0 . 2 5 n m the specimen-crystal-detector radiation
p a t h m a y be air, b u t a t longer w a v e l e n g t h s x-ray
573

X-Ray

Fluorescence

Spectrometry

Figure 4
X-ray spectrogoniometer and electronic detection and readout components. The pulse diagrams show pulse height versus
time. The pulse-height selector passes pulses having amplitude between two discriminator settings, baseline BL and
window width W

a b s o r p t i o n in air is p r o h i b i t i v e a n d t h e g o n i o m e t e r is
enclosed in a flexible helium-flushed h o o d o r a rigid
vacuum hood.
T h e c o n s t i t u e n t elements in t h e specimen emit their
characteristic x-ray spectra in all directions, b u t only a
b u n d l e of rays parallel t o the foils of t h e first collima
t o r reaches t h e crystal. A t each a n g u l a r p o s i t i o n , t h e
crystal diffracts only t h e w a v e l e n g t h t h a t satisfies
the B r a g g law: = 2d sin 0, w h e r e d is the i n t e r p l a n a r
spacing of the crystal planes parallel t o the surface
a n d is a n integer defining the diffraction o r d e r . N o t e
t h a t a t a specified m o r e t h a n o n e w a v e l e n g t h c a n be
diffracted: in first o r d e r (n = 1), /2 in second o r d e r
(n 2 ) , . . . , / in t h o r d e r . T h u s , as t h e crystal
r o t a t e s over its r a n g e , it diffracts in sequence all
incident x-ray w a v e l e n g t h s u p t o a m a x i m u m of
2d n m . Several crystals h a v i n g different d spacings a r e
required t o cover t h e entire w a v e l e n g t h region, for
e x a m p l e , lithium fluoride (2d 0.403 n m ) , p e n t a e r y t h r i tol ( P E T , 2 ^ 0 . 8 7 4 n m ) a n d p o t a s s i u m h y d r o g e n
p h t h a l a t e ( K H P , 2</2.66 n m ) .

7. InstrumentationElectronic
Readout
Components

Detection

and

T h e d e t e c t o r r o t a t e s with t h e crystal, is always in

position t o receive a n y diffracted rays, a n d for e a c h
a b s o r b e d x-ray p h o t o n p r o d u c e s a n electric pulse of
a m p l i t u d e p r o p o r t i o n a l t o t h e p h o t o n energy. T h r e e
types of d e t e c t o r a r e c o m m o n l y used in analytical xr a y s p e c t r o m e t e r s : t h e gas-filled p r o p o r t i o n a l c o u n t e r

574

(Fig. 4) c o m p r i s e s a cylindrical m e t a l - t u b e c a t h o d e
h a v i n g a n axial wire a n o d e a n d insulating e n d s , a n d
filled with a gas, usually a r g o n o r x e n o n . T w o d i a m e t
rically o p p o s i t e x-ray w i n d o w s a r e p r o v i d e d . F o r
wavelengths shorter than ~ 0 . 2 5 n m the windows m a y
be p e r m a n e n t l y sealed beryllium o r mica. F o r longer
w a v e l e n g t h s , the w i n d o w s m u s t be of thin plastic,
usually 6- o r 3- M y l a r , t o reduce x-ray a b s o r p t i o n .
Such w i n d o w s a r e n o t gas-tight, so t h e gas, usually a
9 0 - 1 0 v o l . % m i x t u r e of a r g o n a n d m e t h a n e , is passed
c o n t i n u o u s l y t h r o u g h these "flow c o u n t e r s . " T h e
scintillation c o u n t e r c o m p r i s e s a disk of t h a l l i u m activated s o d i u m iodide, N a l ( T l ) , affixed o u t s i d e t h e
p h o t o c a t h o d e e n d of a multiplier p h o t o t u b e . T h e
lithium-drifted silicon, Si(Li), d e t e c t o r is a disk of
specially t r e a t e d single-crystal silicon.
E a c h x-ray p h o t o n a b s o r b e d in a gas-filled, scintil
lation o r silicon d e t e c t o r ejects a n electron from, say,
the o u t e r m o s t orbital of a gas, iodine o r silicon a t o m ,
respectively, a n d i m p a r t s substantially all of its p h o
t o n energy t o kinetic energy of this p h o t o e l e c t r o n . I n
t h e gas-filled detector, this p h o t o e l e c t r o n e x p e n d s its
energy in p r o d u c i n g m o r e gas-ion/electron p a i r s .
E a c h of these s e c o n d a r y electrons initiates a n " a v a
l a n c h e " of still m o r e i o n - e l e c t r o n p a i r s so t h a t for
4
e a c h electron p r o d u c e d b y the p h o t o e l e c t r o n ~ 1 0 6
10 electrons r e a c h t h e a n o d e wire t o c o n s t i t u t e a n
o u t p u t pulse. I n t h e scintillation detector, t h e p h o t o
electron e x p e n d s its energy in f o r m i n g a b u r s t of
blue-light p h o t o n s , ~ 1 0 % of w h i c h strike t h e p h o t o c a t h o d e of t h e multiplier p h o t o t u b e a n d result in a
p h o t o e l e c t r o n arriving a t t h e electron multiplier. E a c h

X-Ray

such electron results in a n o u t p u t pulse of ~ 1 0

electrons a t t h e multiplier o u t p u t . I n t h e Si(Li) detec
tor, t h e p h o t o e l e c t r o n e x p e n d s its energy in elevating
electrons from t h e filled energy b a n d s t o t h e c o n d u c
tion b a n d . T h e s e c o n d u c t i o n - b a n d electrons a l o n e
c o n s t i t u t e t h e o u t p u t pulse; t h e r e is n o m u l t i p l i c a t i o n
c o r r e s p o n d i n g with t h e a v a l a n c h i n g a n d electron m u l
tiplication of t h e gas a n d scintillation d e t e c t o r s . Evi
dently, t h e higher t h e incident x-ray p h o t o n energy,
t h e m o r e energetic is t h e initial p h o t o e l e c t r o n a n d t h e
m o r e i o n - e l e c t r o n p a i r s , light p h o t o n s a n d e l e c t r o n hole p a i r s a r e p r o d u c e d in t h e respective d e t e c t o r s .
T h i s is t h e basis of t h e p r o p o r t i o n a l i t y of t h e o u t p u t pulse a m p l i t u d e a n d x - r a y - p h o t o n energy.
D e t e c t o r sensitivity varies widely with x-ray w a v e
length, so it is c o m m o n p r a c t i c e t o use a t w o - w i n d o w
flow c o u n t e r for t h e l o n g - w a v e l e n g t h region b a c k e d
by a scintillation c o u n t e r for s h o r t e r w a v e l e n g t h s , as
s h o w n in Fig. 4.
T h e d e t e c t o r o u t p u t is a series of electric pulses of
m e a n a m p l i t u d e p r o p o r t i o n a l t o x - r a y - p h o t o n energy,
o n e for e a c h a b s o r b e d p h o t o n . If t h e crystal s i m u l t a n
eously diffracts m o r e t h a n o n e w a v e l e n g t h (,
/2,...,
/), t h e d e t e c t o r o u t p u t c o n t a i n s pulses of m o r e t h a n
o n e a m p l i t u d e . I n F i g . 4, three such a m p l i t u d e s a r e
s h o w n h i g h , m e d i u m a n d low, r e p r e s e n t i n g r a y s of
/2, a n d d e t e c t o r noise, respectively. T h e p r e a m p l i
fier a n d amplifier amplify all pulses w i t h o u t c h a n g e in
relative a m p l i t u d e . T h e pulse-height selector passes
only pulses h a v i n g a m p l i t u d e in t h e " w i n d o w "
between t w o preset levels, t h e " b a s e l i n e " a n d
" w i n d o w w i d t h . " I n t h e figure, t h e noise a n d higha m p l i t u d e pulses a r e rejected, t h e m e d i u m pulses
passed. T h e r a t e m e t e r integrates t h e selector o u t p u t
over a certain t i m e interval a n d displays t h e pulse r a t e
o r frequency o n a m e t e r o r c h a r t r e c o r d e r . T h e scaler
actually c o u n t s t h e pulses a n d displays t h e n u m b e r
digitally. T h e t i m e r is a digital clock a n d displays
c o u n t i n g time. T h e o p t i o n a l c o m p u t e r calculates c o m
p o s i t i o n from s t o r e d intensity d a t a a n d m a y o p e r a t e
an automatic spectrometer. The printer prints out
intensity a n d / o r c o m p o s i t i o n d a t a .

8. InstrumentationAutomated
Special-Purpose
Spectrometers

and

T h e i n s t r u m e n t described in Sect. 6 is a single-channel

manual or semiautomatic spectrometer. C o m p o n e n t s
(collimators, crystal, d e t e c t o r ) a n d o p e r a t i n g c o n
ditions (x-ray t u b e k V - m A , d e t e c t o r p o t e n t i a l , a m p l i
fier gain, pulse-selector settings) a r e c h a n g e d
m a n u a l l y o r by m a n u a l l y o p e r a t e d selectors. T w o
types of fully a u t o m a t i c s p e c t r o m e t e r s a r e in c o m m o n
use, sequential o r s i m u l t a n e o u s .
T h e sequential s p e c t r o m e t e r is a single-channel u n i t
p r o g r a m m e d t o index sequentially t o t h e 2 angle of
each spectral line, select a p p r o p r i a t e c o m p o n e n t s a n d
c o n d i t i o n s a n d m e a s u r e intensity, t h e n index t h e n e x t

Fluorescence

Spectrometry

specimen i n t o p o s i t i o n a n d r e p e a t t h e process c o n
tinually, all a u t o m a t i c a l l y a n d u n a t t e n d e d .
The simultaneous multichannel spectrometer has
a r r a y e d a b o u t t h e specimen, like s p o k e s a b o u t a wheel
h u b , u p t o 15 m e t a l p l a t e s , e a c h h o u s i n g o n e o r t w o
s p e c t r o m e t e r s c o m p r i s i n g c o l l i m a t o r s , crystal a n d d e
tector, a n d e a c h h a v i n g a r e a d o u t c h a i n . T h u s , the
i n s t r u m e n t c o m p r i s e s u p t o 30 c h a n n e l s . M o s t of
these a r e preset t o a specific x-ray line. T h e o t h e r s a r e
m o t o r - d r i v e n " s c a n n i n g " s p e c t r o m e t e r s of t h e type
described in Section 6. T h e s e a r e used for qualitative
analysis a n d for elements d e t e r m i n e d t o o infrequently
t o w a r r a n t preset c h a n n e l s . T h e s e i n s t r u m e n t s c a n
a c c u m u l a t e intensity d a t a for u p t o 30 elements in 1-2
m i n , w h e r e u p o n t h e next specimen is indexed i n t o
p o s i t i o n a n d m e a s u r e d , a n d so o n , all a u t o m a t i c a l l y
and unattended.
I n b o t h sequential a n d s i m u l t a n e o u s i n s t r u m e n t s ,
t h e intensity d a t a for s a m p l e s a n d s t a n d a r d s is i n p u t
t o a (usually) d e d i c a t e d c o m p u t e r for direct calcu
l a t i o n a n d p r i n t o u t of c o m p o s i t i o n . Such fully
a u t o m a t e d i n s t r u m e n t s a r e of inestimable value for
i n d u s t r i a l l a b o r a t o r i e s r e q u i r e d t o a n a l y z e daily very
large n u m b e r s of specific alloys, c e m e n t s , ceramics,
glasses, a n d so o n , a t m i n i m a l cost.
S p e c t r o m e t e r s for t h e u l t r a l o n g - w a v e l e n g t h region
( ^ 2 n m ) use x-ray g e n e r a t o r s c o m p r i s i n g special wind o wless x-ray t u b e s o p e r a t e d a t u p t o ~ 10 k V a n d t o
~ 500 m A , special p s e u d o c r y s t a l s h a v i n g 2d spacings
of 1 0 - 1 5 n m a n d w i n d o w l e s s d e t e c t o r s , all o p e r a t i n g
in high, clean v a c u u m .
T h e r e a r e relatively lightweight p o r t a b l e w a v e
length-dispersive s p e c t r o m e t e r s t h a t o p e r a t e from
b a t t e r i e s o r g e n e r a t o r s for field a n d e n v i r o n m e n t a l
use, b u t m o s t such a p p l i c a t i o n s use energy-dispersive
spectrometers.
Dynamic process-control spectrometers monitor
a n d c o n t r o l industrial processes, such as plating, ore
p r o c e s s i n g a n d reclaiming of p r e c i o u s m e t a l s . A n xray spectrometer at some point along the production
line m o n i t o r s , say, t i n - p l a t e thickness o n c o n t i n u o u s l y
m o v i n g sheet steel. W h e n t h e m o n i t o r e d x-ray inten
sity falls o u t s i d e previously established limits, the
i n s t r u m e n t either signals a n o p e r a t o r o r adjusts the
p l a t i n g c o n d i t i o n s t o c o r r e c t t h e fault.

9.

Operation

Q u a l i t a t i v e analysis is p e r f o r m e d by setting t h e crystal

a n d c o l l i m a t o r - d e t e c t o r a r m a t 0, t h e n m o t o r - d r i v
ing t h e m a t 0 a n d 2 p e r u n i t time, respectively,
t h r o u g h t h e a n g u l a r r a n g e of t h e g o n i o m e t e r as the
r a t e m e t e r r e c o r d s i n s t a n t a n e o u s x-ray intensity. T h e
result is a c h a r t of x-ray intensity as a function of 2,
s h o w i n g p e a k s , e a c h r e p r e s e n t i n g a different x-ray
line. T h e p e a k p o s i t i o n s (20) indicate t h e wavelengths
a n d t h e r e b y t h e x-ray lines a n d elements present. T h e
intensities give i n f o r m a t i o n a b o u t c o n c e n t r a t i o n s .

575

X-Ray

Fluorescence

Spectrometry

Q u a n t i t a t i v e analysis is p e r f o r m e d by setting t h e
g o n i o m e t e r at t h e 20 angle of a specified x-ray line,
say c o p p e r . T h e s e a l e r - t i m e r c o u n t s c o p p e r
pulses for a " p r e s e t t i m e " o r times the a c c u m u l a t i o n
of a " p r e s e t c o u n t . " M e a s u r e m e n t s a r e m a d e o n e a c h
s a m p l e a n d o n s t a n d a r d s similar t o t h e s a m p l e s b u t
h a v i n g k n o w n c o m p o s i t i o n . T h e s t a n d a r d d a t a is used
to establish a m a t h e m a t i c a l r e l a t i o n s h i p o r c a l i b r a t i o n
curve of c o p p e r intensity against c o p p e r c o n c e n
t r a t i o n , t o which the s a m p l e intensity d a t a is applied.
Alternatively, t h e intensity d a t a m a y be e n t e r e d in t h e
c o m p u t e r for calculation of c o m p o s i t i o n . T h e s a m e
p r o c e d u r e is followed for the o t h e r s a m p l e elements.

10. Matrix

Effects

It m i g h t be expected t h a t spectral-line intensity of

analyte element A from s a m p l e X , 7 A X, a n d from p u r e
A , 7 A A, w o u l d be related by IAX = C A X/ A A, w h e r e C A X is
the m a s s fraction of A in X . T h i s relation s e l d o m
applies d u e t o m a t r i x effects, the effects of the overall
specimen o n t h e x-ray line intensity of t h e a n a l y t e .
M a t r i x effects m a y b e physical (e.g., surface texture,
p o r o s i t y , particle size a n d c o m p o s i t i o n a l h e t e r o g e
neity) o r chemical ( a b s o r p t i o n - e n h a n c e m e n t effects of
o t h e r elements in the s p e c i m e n m a t r i x e l e m e n t s o n
analyte-line intensity). / A X from several specimens of
identical c o m p o s i t i o n m a y vary if t h e specimens differ
in the physical features cited, especially for longwavelength lines. / A X from several specimens of identi
cal physical n a t u r e a n d A c o n c e n t r a t i o n m a y vary
with t h e c o n c e n t r a t i o n of o n e o r m o r e m a t r i x ele
m e n t s . T h e s e m a t r i x elements m a y r e d u c e 7 A X b y
preferentially a b s o r b i n g t h e a n a l y t e line a n d / o r t h e
p r i m a r y rays m o s t efficient in exciting it. C o n v e r
sely, the m a t r i x elements m a y e n h a n c e 7 A X if their o w n
x-ray lines h a v e wavelengths s h o r t e r t h a n t h e a n a l y t e line a b s o r p t i o n edge a n d excite analyte-line emission
in a d d i t i o n t o t h a t excited by the p r i m a r y rays.
Physical effects a r e dealt with by t h e specimen
p r e p a r a t i o n t e c h n i q u e (see Sect. 11), a b s o r p t i o n e n h a n c e m e n t effects by choice of analytical m e t h o d
(see Sect. 12).

11. Specimen

Forms and

Preparation

F o r qualitative analysis, it is sufficient t h a t the s a m p l e

fit in the specimen h o l d e r . H o w e v e r , for q u a n t i t a t i v e
analysis all samples a n d s t a n d a r d s in t h e analytical set
m u s t h a v e t h e s a m e form a n d t h e s a m e suitable
h o m o g e n e i t y , finish, particle-size d i s t r i b u t i o n , p o r o s
ity a n d so o n . W h e n samples c a n be analyzed a s received with m i n i m a l p r e p a r a t i o n , x-ray
fluorescence
s p e c t r o m e t r y c a n analyze large n u m b e r s of samples
rapidly a n d conveniently. H o w e v e r , s u b s t a n t i a l p r e
p a r a t i o n , possibly involving c h a n g e in form, is
required w h e n : (a) samples a r e u n s t a b l e o r h a v e severe

576

physical m a t r i x effects; (b) a n a d d i t i o n o r dilution

m e t h o d (Sect. 12) is required; a n d / o r (c) s t a n d a r d s are
u n a v a i l a b l e in t h e as-received form, o r t h e s a m e
m a t e r i a l m u s t be analyzed in several forms, such as
ingot, b a r , s h o t a n d p o w d e r . S u c h p r e p a r a t i o n d e
creases t h e speed a n d convenience. T h e principal
specimen f o r m s a r e described in the following
sections.
11.1 Solids
Solids include b u l k m e t a l , m i n e r a l , slag, ceramic,
glass, plastic, w o o d a n d r u b b e r . F i n i s h e d stock (e.g.,
b a r a n d sheet) m a y require n o p r e p a r a t i o n o t h e r t h a n
c u t t i n g t o size. Pieces sawed from ingot, r o d , rock,
r a w stock a n d so o n , usually require polishing. Prefer
ential r e m o v a l of p h a s e s , s m e a r i n g of soft p h a s e s , a n d
c o n t a m i n a t i o n b y polishing abrasive m u s t be avoided.
11.2
Powders
P o w d e r s m a y be used: (a) loose in d i s p o s a b l e M y l a r covered plastic c u p s ; (b) as b r i q u e t s , with o r w i t h o u t
b i n d e r , usually with a protective b a c k o r ring o r in a
shallow m e t a l dish; o r (c) s p r e a d in a thin layer
b e t w e e n M y l a r films stretched over a plastic c u p .
All s a m p l e s a n d s t a n d a r d s in a solid, p o w d e r o r
b r i q u e t set m u s t h a v e t h e s a m e surface finish o r
particle size. T h e longer t h e wavelength t o be
m e a s u r e d , t h e finer the finish o r particles m u s t be;
~ 20 is sufficient for lines d o w n to a t o m i c
n u m b e r 11 ( s o d i u m ) .
11.3 Glass or other Fused Disks
G l a s s o r o t h e r fused disks a r e used w h e n severe
physical m a t r i x effects p r e c l u d e use of t h e original
solid o r p o w d e r . T h e s a m p l e is fused with a lowmelting flux (such as p o t a s s i u m pyrosulfate) o r a
high-melting glass-forming flux (such as s o d i u m tetra
b o r a t e ) . T h e n o w h o m o g e n e o u s melt c a n be cast as a
disk o r pulverized a n d used as a p o w d e r .
11.4 Liquids and Slurries
L i q u i d s a n d slurries a r e held in d i s p o s a b l e M y l a r covered plastic c u p s . All samples a n d s t a n d a r d s in a
set m u s t h a v e the s a m e m a t r i x , for e x a m p l e , t h e s a m e
acid in the s a m e c o n c e n t r a t i o n . L i q u i d s a r e p r o n e t o
b u b b l e f o r m a t i o n a n d p r e c i p i t a t i o n in t h e intense
p r i m a r y x-ray b e a m .
11.5 Supported
Specimens
S u p p o r t e d specimens c o m p r i s e : (a) m i c r o s a m p l e s
d e p o s i t e d o n filter p a p e r , Millipore filters, thin M y l a r
film, o r such like, by e v a p o r a t i o n of liquid d r o p s o r b y
filtration
of liquids a n d gases; (b) m i c r o samples
a d s o r b e d by i o n - e x c h a n g e resin, m e m b r a n e o r p a p e r ;
(c) thin films, including platings, c o a t i n g s , e v a p o r a t e d
films, c o r r o s i o n layers a n d residues; (d) b u l k m a t e r i a l s
r e d u c e d t o t h i n layers; a n d (e) p a p e r , textile, a n d such
like for analysis of filler, sizing, ink, d y e a n d so o n .
S u p p o r t e d specimens a r e less t h a n infinitely thick.

X-Ray

11.6 Fabricated Forms and Parts

F a b r i c a t e d forms a n d p a r t s of small size c a n be placed
in m o s t s p e c t r o m e t e r s . Very large specimens, such as
ingots, engine p a r t s a n d a r t objects, c a n be a c c o m m o
dated on some instruments.
T h e p o w d e r , b r i q u e t , fusion a n d liquid f o r m s h a v e
the a d v a n t a g e t h a t s t a n d a r d s c a n be synthesized.

12. Analytical

Methods

M o s t analytical x-ray fluorescence s p e c t r o m e t r i c

m e t h o d s m a y be classified in seven categories b a s e d
o n their a p p r o a c h t o c o m p e n s a t i n g a b s o r p t i o n e n h a n c e m e n t effects.
12.1 Calibration
Standardization
X - r a y line intensities from s a m p l e s a r e c o m p a r e d with
those from s t a n d a r d s as similar t o t h e s a m p l e s as
possible in form a n d c o m p o s i t i o n , as described in
Section 9. W h e n m i n o r o r trace c o n s t i t u e n t s within
n a r r o w specification limits a r e t o be d e t e r m i n e d , a
single s t a n d a r d h a v i n g c o m p o s i t i o n n e a r m i d r a n g e
m a y suffice: C x / C s = Ix/Is w h e r e C, /, S a n d X a r e
c o n c e n t r a t i o n , intensity, s t a n d a r d a n d s a m p l e , re
spectively. In d e t e r m i n i n g nickel in stainless steel,
nickel intensity d e p e n d s o n b o t h nickel a n d c h r o
m i u m c o n c e n t r a t i o n . I n such cases, a set of curves
c a n be established, here, nickel intensity versus
c o n c e n t r a t i o n , e a c h c u r v e for a different c h r o m i u m
c o n c e n t r a t i o n . Actually, all analytical x-ray s p e c t r o
metric m e t h o d s r e q u i r e c a l i b r a t i o n s t a n d a r d s , except
s t a n d a r d a d d i t i o n a n d dilution (see below), b u t
these m e t h o d s h a v e features t h a t w a r r a n t s e p a r a t e
classification.
12.2 Internal

Standardization

T h e c a l i b r a t i o n - s t a n d a r d m e t h o d is i m p r o v e d b y
q u a n t i t a t i v e a d d i t i o n t o all s a m p l e s a n d s t a n d a r d s of
a n element h a v i n g excitation, a b s o r p t i o n a n d en
h a n c e m e n t p r o p e r t i e s similar t o t h o s e of t h e a n a l y t e
in t h e p a r t i c u l a r m a t r i x . T h e c a l i b r a t i o n function is
the a n a l y t e / i n t e r n a l - s t a n d a r d intensity r a t i o versus
analyte concentration.
12.3 Standardization
with Scattered X Rays
T h e intensity of a selected w a v e l e n g t h from t h e p r i m
ary rays scattered by t h e specimen is used t o c o r r e c t
a b s o r p t i o n - e n h a n c e m e n t ( a n d o t h e r ) effects. T h e
wavelength m a y be from t h e c o n t i n u u m o r a t a r g e t
line. T h e c a l i b r a t i o n function is a n a l y t e / s c a t t e r e d
intensity r a t i o versus c o n c e n t r a t i o n .
12.4 Matrix-Dilution
Methods
All samples a n d s t a n d a r d s a r e t r e a t e d with a
" d i l u e n t , " which c o n s t i t u t e s a n e w c o n s t a n t m a t r i x .
T h e diluent m a y be a high c o n c e n t r a t i o n of lowa t o m i c - n u m b e r m a t e r i a l , such as a p o w d e r , solvent o r

Microanalysis,

Quantitative

fusion flux, o r a low c o n c e n t r a t i o n of h i g h - a t o m i c n u m b e r m a t e r i a l , such as l a n t h a n u m oxide.

12.5 Thin-Film
Methods
T h e specimens a r e so thin t h a t
absorptione n h a n c e m e n t effects substantially d i s a p p e a r . S o m e
s a m p l e s a r e inherently thin films, o t h e r s c a n be p r e
p a r e d in thin-film form (Sect. 11).
12.6 Standard Addition and Dilution
A n a l y t e c o n c e n t r a t i o n is altered q u a n t i t a t i v e l y in a
p o r t i o n of s a m p l e . Intensities from t r e a t e d a n d
u n t r e a t e d p o r t i o n s a r e applied t o e q u a t i o n s . T h e
m e t h o d requires n o s t a n d a r d s a n d is useful for " o n e o f - a - k i n d " s a m p l e s a n d s a m p l e s for which s t a n d a r d s
are unavailable.
12.7 Mathematical
Methods
Intensities from s a m p l e s a n d s t a n d a r d s a r e applied to
sets of c o m p l e x m a t h e m a t i c a l e q u a t i o n s established
for e a c h m a t r i x system. C o m p u t e r calculation is
required.
See also: Electron Microprobe Analysis; X-Ray Absorption
Spectroscopy: EXAFS and XANES Techniques; X-Ray
Microanalysis, Quantitative

Bibliography
Bertin 1975 Principles and Practice of X-Ray Spectro
metric Analysis, 2nd edn. Plenum, New York
Bertin 1978 Introduction to X-Ray Spectrometric Analy
sis. Plenum, New York
Herglotz , Birks L S (eds.) 1978 X-Ray Spectrometry.
Dekker, New York
Jenkins R 1974 An Introduction to X-Ray Spectrometry.
Heyden, London
Jenkins R, De Vries J L 1969 Practical X-Ray Spectrometry,
2nd edn. Springer, New York
E. P. Bertin
[RCA Laboratories, Princeton,
N e w Jersey, U S A ]

X-Ray Microanalysis, Quantitative

Electron-excited x-ray analysis, as described in the
articles Electron Microprobe Analysis, Electron Mic
roscopy, Analytical
a n d Scanning Electron
Micros
copy, p r o d u c e s d a t a o n relative elemental intensities
from w h i c h c o n c e n t r a t i o n s c a n be calculated. Q u a l i
tative analysis consists of identifying t h e elements
p r e s e n t from t h e energies (or wavelengths) of the
p e a k s p r e s e n t in the x-ray s p e c t r u m . T h i s process
m a y b e q u i t e difficult, b e c a u s e with the wavelengthdispersive ( W D ) s p e c t r o m e t e r only a p o r t i o n of the
s p e c t r u m m a y h a v e been analyzed, a n d with the
energy-dispersive ( E D ) s p e c t r o m e t e r the greater p e a k
w i d t h s ( p o o r e r r e s o l u t i o n ) m a y p r o d u c e overlaps t h a t
577

X-Ray

Microanalysis,

Quantitative

o b s c u r e s o m e p e a k s o r hide small p e a k s in statistical

fluctuations.
Whether accomplished using the opera
t o r ' s experience a n d k n o w l e d g e of t h e s a m p l e , o r
using c o m p u t e r i z e d aids t o find a n d label p e a k s , t h e
qualitative result simply identifies w h i c h elements a r e
p r e s e n t in d e t e c t a b l e a m o u n t s a n d d o e s n o t p r o v i d e
c o m p o s i t i o n i n f o r m a t i o n o n t h e s a m p l e (or t h e local
region selected for analysis).
T h e first, essential step t o w a r d s q u a n t i t a t i v e results
is o b t a i n i n g net intensities for t h e v a r i o u s elements.
T h e s p e c t r u m b a c k g r o u n d in W D analysis c a n usually
b e m e a s u r e d next t o t h e p e a k b y adjusting t h e crystal
angle. T h i s is less easy t o a c c o m p l i s h with t h e E D
system b e c a u s e the p e a k s a r e b r o a d a n d often inter
fere, a n d t h e b a c k g r o u n d m a y be q u i t e n o n l i n e a r . T h e
c o n t i n u u m b a c k g r o u n d consists of b r e m s s t r a h l u n g
r a y s p r o d u c e d b y t h e deceleration of t h e m o v i n g
electrons by t h e electrostatic field n e a r a t o m i c nuclei.
It c a n be m o d e l l e d for the entire s p e c t r u m as p a r t of
the iterative q u a n t i t a t i v e c o r r e c t i o n process (as it
d e p e n d s o n t h e s a m p l e c o m p o s i t i o n ) for ideal flat,
h o m o g e n e o u s b u l k specimens. L o c a l fitting of
semiempirical curves is also used, especially w h e n t h e
samples a r e n o t ideal o r t h e m e a s u r e d s p e c t r u m
b a c k g r o u n d includes o t h e r sources of r a y s , for
instance d u e t o scattering from t h e s a m p l e h o l d e r in
t h e analytical electron m i c r o s c o p e ( A E M ) .
O n e of t h e m o s t c o m m o n m e t h o d s used t o o b t a i n
net elemental p e a k s is t o a p p l y a derivative filter t o t h e
s p e c t r u m w h i c h suppresses t h e m o r e g r a d u a l l y vary
ing b a c k g r o u n d c o m p a r e d t o t h e p e a k s , followed b y
least-squares fitting of p e a k s h a p e s either m e a s u r e d
from s t a n d a r d s a n d s t o r e d , o r g e n e r a t e d in t h e c o m
p u t e r . I n principle, this s h o u l d c a u s e p r o b l e m s d u e t o
a b s o r p t i o n edges in t h e s p e c t r u m (which d e p e n d u p o n
c o m p o s i t i o n ) o r p o o r fitting if t h e p e a k s h a p e o r
a l i g n m e n t varies w i t h i n s t r u m e n t a l factors. I n p r a c
tice, t h e m e t h o d w o r k s well m o s t of t h e time a n d is
widely used. D e b a t e s b e t w e e n m a n u f a c t u r e r s c o n
tinue over t h e relative m e r i t s of using m e a s u r e d a n d
g e n e r a t e d s t a n d a r d spectra, using n o n l i n e a r fitting
m e t h o d s t h a t c a n a c c o m m o d a t e p e a k shifts, a n d s o
on.

/.

ZAF

Corrections

O f t h e v a r i o u s m e t h o d s used t o calculate c o n c e n t r a
tions from net elemental intensities, t h e c o n v e n t i o n a l
Z A F m e t h o d is b y far t h e m o s t widely used for b u l k
specimens. Z A F refers t o t h e s e p a r a t e a t o m i c n u m b e r
Z , a b s o r p t i o n A a n d fluorescence F c o r r e c t i o n s w h i c h
a r e calculated as a function of a n ( a s s u m e d ) c o m p o s i
tion a n d multiplied b y t h e m e a s u r e d intensity r a t i o
( m e a s u r e d intensity divided b y p u r e element intensity
m e a s u r e d u n d e r identical circumstances):
Concentration = (
Intensity \
V P u r e intensity /

578

/
1_
\ ZAF )

T h e c o r r e c t i o n describes t h e relative ability of

different e l e m e n t s t o scatter electrons a n d be ionized
b y t h e m , t h e A t e r m c o r r e c t s for t h e fraction of r a y s
w h i c h a r e a b s o r b e d in t h e specimen o n their w a y o u t
(a function of t h e d e p t h a t w h i c h they a r e g e n e r a t e d )
a n d t h e F c o r r e c t i o n a c c o u n t s for a d d i t i o n a l x-ray
intensity p r o d u c e d b y i o n i z a t i o n s c a u s e d b y t h e
a b s o r p t i o n of o t h e r r a y s , r a t h e r t h a n directly b y t h e
electron b e a m . T h e c a l c u l a t i o n p r o c e s s is iterative, as
progressively b e t t e r estimates of c o m p o s i t i o n a r e
made.
P r o g r a m s t h a t r o u t i n e l y a p p l y this c o r r e c t i o n p r o
cedure can be run on most desk-top or personal
c o m p u t e r s . T h e e q u a t i o n s used t o m o d e l t h e v a r i o u s
t e r m s a r e well refined a n d q u i t e a c c u r a t e ( a few
p e r c e n t ) for t h e general r u n of analytical p r o b l e m s ,
b u t t h e a p p r o x i m a t i o n s e m p l o y e d d o n o t p r o d u c e as
g o o d results for elements with very low o r high a t o m i c
n u m b e r s , e x t r e m e analysis c o n d i t i o n s (especially
accelerating v o l t a g e o r specimen surface inclination),
o r n o n i d e a l s a m p l e geometries (in principle, t h e
m e t h o d applies o n l y t o b u l k h o m o g e n e o u s specimens
with flat, polished surfaces).
Z A F p r o g r a m s h a v e been e x t e n d e d in v a r i o u s
w a y s . F o r m i n e r a l specimens in which a large n u m b e r
of e l e m e n t s a r e p r e s e n t b u t w h i c h v a r y o n l y slightly
from s t a n d a r d t o u n k n o w n , t h e t e r m s c a n b e precalc u l a t e d a n d fitted t o linear s i m u l t a n e o u s e q u a t i o n s
t h a t p r o v i d e a m u c h faster s o l u t i o n for t h e elemental
c o n c e n t r a t i o n s . F o r c o m b i n a t i o n s of light a n d h e a v y
elements, a c o r r e c t i o n for fluorescence of c h a r a c t e r i s
tic r a y s b y t h e c o n t i n u u m c a n b e included. P u r e
e l e m e n t a l intensities c a n be calculated from c o m
p o u n d s t a n d a r d s , from o t h e r n e a r b y elements in t h e
p e r i o d i c t a b l e , o r from semiempirical e q u a t i o n s
r e q u i r i n g n o m e a s u r e m e n t s a t all.
T h e last t w o possibilities for eliminating t r a d i t i o n a l
s t a n d a r d s m e a s u r e m e n t s a r e often described a s " s t a n d a r d l e s s " m e t h o d s a n d a r e n o w r o u t i n e l y accepted for
use w i t h E D s p e c t r o m e t e r s , in w h i c h t h e s p e c t r o m e t e r
r e s p o n s e a s a function of energy is well k n o w n a n d
q u i t e c o n s t a n t . F o r elements in t h e r a n g e 11 < <
45 (i.e., e l e m e n t s a n a l y z e d b y their K-shell electrons)
t h e results from s t a n d a r d l e s s analysis a r e c o m p a r a b l e
t o c o n v e n t i o n a l m e t h o d s , a n d m a y b e s u p e r i o r if t h e
i n s t r u m e n t stability d o s n o t p e r m i t s t a n d a r d s t o b e
m e a s u r e d u n d e r exactly identical c o n d i t i o n s a s t h e
u n k n o w n s . F o r h i g h e r (aii4 lpwer) a t o m i c n u m b e r
elements, or when mixed
L- a n d M-shell r a y s a r e
used, t h e results a r e jpoprer 'for t h e s t a n d a r d l e s s
m e t h o d s , a n d indeed for the, Z A F a p p r o a c h in
general.
F o r light e l e m e n t s in p a r t i c u l a r , t h e large a b s o r p
tion c o r r e c t i o n n e e d e d , p o o r l y k n o w n f u n d a m e n t a l
c o n s t a n t s , difficulty in d e t e r m i n i n g precise intensities
d u e t o significant p e a k o v e r l a p s o r v a r i a t i o n in p e a k
s h a p e s o r spectral b a c k g r o u n d , a n d s t r o n g influence
of t h e specimen surface c o m b i n e t o p r o d u c e r a t h e r
large e r r o r s . Often, b e t t e r results c a n b e o b t a i n e d b y

X-Ray

using k n o w n elemental stoichiometrics for t h e light

elements, o r d e t e r m i n i n g t h e m b y difference from
1 0 0 % as c o m p a r e d t o m e a s u r e m e n t a n d c a l c u l a t i o n .
W h e n light element analysis m u s t be p e r f o r m e d , it is
possible t o use a () (where is density a n d is
d e p t h ) in which t h e d e p t h profile of the g e n e r a t e d
x-ray intensity is c o m p u t e d using semiempirical
e q u a t i o n s b a s e d o n m e a s u r e m e n t s , a n d a b s o r p t i o n is
directly s u m m e d o v e r d e p t h with m u c h g r e a t e r a c c u r
acy t h a n t h e Z A F m e t h o d .

2. Other Specimen

Microanalysis,

Quantitative

Figure 1
Example of a Monte Carlo simulation of a few trajectories
for 20 keV electrons in nickel

Geometries

F o r thin specimens, as e n c o u n t e r e d in t h e A E M ,
a b s o r p t i o n is negligible a n d fluorescence d i s a p p e a r s ,
so t h e c o r r e c t i o n p r o c e d u r e is further simplified. O n l y
the relative efficiency with w h i c h different e l e m e n t s
c a n be excited a n d emit characteristic rays a n d t h e
sensitivity of t h e s p e c t r o m e t e r a t different energies
r e m a i n . T h i s c a n be calculated either from f u n d a m e n
tal p a r a m e t e r s o r m e a s u r e d from a s t a n d a r d specimen
( b o t h m e t h o d s h a v e their a d h e r e n t s ) , t o p r o d u c e a
factor relating t h e m e a s u r e d intensity r a t i o s from
different elements t o their c o n c e n t r a t i o n s :
Concentration!
Concentration

Intensity!
2 1

Intensity2

F o r n o r m a l specimens, this is usually s u p p l e m e n t e d

by t h e a s s u m p t i o n t h a t XC, = 1. F o r s a m p l e s t h a t a r e
n o t ideally thin, a c o r r e c t i o n for x-ray a b s o r p t i o n c a n
be applied b u t results in t h e c a l c u l a t i o n b e c o m i n g
iterative since t h e a b s o r p t i o n d e p e n d s u p o n c o n c e n
tration.
T h e r e h a s been m u c h recent interest in a d a p t i n g
quantitative correction calculations to m o r e complex
specimen geometries, such as p a r t i c u l a t e s , t h i n films
o n s u b s t r a t e s a n d n o n p l a n a r surfaces. O n e a p p r o a c h
uses t h e fact t h a t t h e r a t i o of p e a k (characteristic)
intensity t o b a c k g r o u n d ( c o n t i n u u m ) intensity is rela
tively insensitive t o s a m p l e g e o m e t r y . T h i s is b e c a u s e
in m a n y c i r c u m s t a n c e s t h e a b s o r p t i o n c o r r e c t i o n is
t h e m o s t i m p o r t a n t , a n d since t h e c o n t i n u u m is gener
a t e d with a d e p t h profile r o u g h l y similar t o t h e
characteristic r a y s it is subjected t o a similar
a m o u n t of a b s o r p t i o n . Z A F m o d e l s adjusted t o use
p e a k - t o - b a c k g r o u n d r a t i o s h a v e s h o w n p r o m i s e for
particulates a n d r o u g h surfaces b u t t h e b a c k g r o u n d g e n e r a t i o n m o d e l s a r e n o t yet c a p a b l e of p r o d u c i n g
consistent results w i t h b e t t e r t h a n 5 - 1 0 % a c c u r a c y .
A n o t h e r a p p r o a c h t o p a r t i c u l a t e analysis uses
semiempirical c a l i b r a t i o n curves t o modify q u a n t i t a
tive results calculated as for a b u l k s a m p l e , as a
function of t h e o b s e r v e d s h a p e o r size of particles.
Particularly in t h e s c a n n i n g electron m i c r o s c o p e
( S E M ) , few specimens h a v e ideally flat surfaces. C o n
ventional Z A F m o d e l s c a n often b e a p p l i e d if t h e
local surface is p l a n a r (e.g., m a n y fracture surfaces)
p r o v i d e d its o r i e n t a t i o n c a n b e d e t e r m i n e d b y stereos-

c o p y . Alternatively, s p e c t r a c a n b e o b t a i n e d a t t w o
different accelerating voltages a n d c a l c u l a t i o n used t o
d e t e r m i n e t h e o r i e n t a t i o n angle t h a t gives t h e s a m e
c o m p o s i t i o n a n s w e r for b o t h analyses.
T h e accelerating v o l t a g e is a l w a y s a p a r a m e t e r of
p r i m e i m p o r t a n c e for q u a n t i t a t i v e analysis. W i t h a n
E D s p e c t r o m e t e r , it is best d e t e r m i n e d b y t h e cutoff
p o i n t of t h e c o n t i n u u m b a c k g r o u n d . T h i s is generally
more accurate than any meter on the microscope, and
also t a k e s i n t o a c c o u n t a n y deceleration of t h e elec
tron beam that m a y occur due to sample charging.

3. Monte

Carlo

Modelling

T h e m e t h o d w h i c h is in principle c a p a b l e of dealing
with a n y k i n d of specimen g e o m e t r y is M o n t e C a r l o
m o d e l l i n g . R a t h e r g o o d m o d e l s a r e n o w available for
e a c h of t h e individual processes b y w h i c h m o v i n g
electrons lose energy a n d slow d o w n , a n d excite
characteristic o r c o n t i n u u m rays from a t o m s . By
using c o m p u t e r r a n d o m - n u m b e r g e n e r a t o r s t o s a m p l e
these p r o b a b i l i t y d i s t r i b u t i o n s it is possible t o follow
t h e p a t h s of a statistically useful n u m b e r (typically a t
least several t h o u s a n d , a n d m a n y m o r e in s o m e cases)
of electrons as they scatter from a t o m s in t h e speci
men, encounter various geometric boundaries and
generate rays which can be summed. (Figure 1
s h o w s a n e x a m p l e of a M o n t e C a r l o p l o t of electron
trajectories.) T h i s m e a n s t h a t a n y b o u n d a r y c o n
d i t i o n s , surface o r subsurface irregularities, c o m p o s i
t i o n h e t e r o g e n e i t y o r o t h e r s a m p l e peculiarities c a n be
set u p a n d t h e x-ray yield calculated.
I n practice, this is n o t a g o o d q u a n t i t a t i v e c o r r e c
tion t o o l , for several r e a s o n s . First, t h e calculation
p r o c e e d s from t h e full d e s c r i p t i o n of t h e s a m p l e ,
w h i c h is u n k n o w n , t o t h e x-ray intensities, which c a n
be m e a s u r e d . E x c e p t in simple cases, for instance, the
thickness of a c o a t i n g layer, it is difficult t o iterate the
u n k n o w n p a r a m e t e r s t o achieve a g r e e m e n t . Second,
t h e c o m p u t e r t i m e n e e d e d t o t r a c k e n o u g h electrons
t o o b t a i n g o o d results is n o t trivial. S o m e very useful
simplifications of t h e full M o n t e C a r l o a p p r o a c h h a v e

579

X-Ray

Microanalysis,

Quantitative

been p r o d u c e d t h a t allow t h e m o d e l s t o r u n quickly in

d e s k - t o p a n d p e r s o n a l c o m p u t e r s , b u t these a r e n o t
able t o m o d e l s o m e of t h e m o r e subtle effects o r t o be
used in a real-time c o r r e c t i o n scheme. T h e m o s t
n o t a b l e simplification is the " m u l t i p l e s c a t t e r i n g "
m o d e l in w h i c h t h e individual e l e c t r o n - a t o m i n t e r a c
tions are l u m p e d t o g e t h e r i n t o a c o n t i n u o u s slowingd o w n m o d e l t h a t zigzags in only a few d o z e n steps
t h r o u g h the s a m p l e .
It h a s p r o v e d practical t o p r e c o m p u t e c a l i b r a t i o n
curves of x-ray intensity against t h e thickness a n d
c o m p o s i t i o n of p l a n a r multilayer c o a t i n g s o n s u b
strates, which c a n t h e n be used in real-time analysis.
T h e greatest use of M o n t e C a r l o m e t h o d s h a s been t o
test a n d verify o t h e r c o r r e c t i o n m e t h o d s a n d t o evalu
ate f u n d a m e n t a l p a r a m e t e r s for electron a n d x-ray
interactions. T h e p r o g r a m s h a v e b e e n especially use
ful in u n d e r s t a n d i n g a n d m o d e l l i n g t h e g e n e r a t i o n of
s e c o n d a r y a n d b a c k s c a t t e r e d electrons, for instance t o
develop o p t i m u m d e t e c t o r geometries o r t o establish
m e a s u r e m e n t m e t h o d s for electronic devices a n d
o t h e r small s t r u c t u r e s e x a m i n e d in t h e s c a n n i n g elec
tron microscope (SEM).

4. Dimensions

of

Analysis

F o r h e t e r o g e n e o u s samples o r n o n i d e a l surfaces it is
i m p o r t a n t t o k n o w the d i m e n s i o n s of t h e region in
which the electrons scatter a n d rays a r e g e n e r a t e d .
In thin sections ( A E M ) this is basically a t r u n c a t e d
c o n e , s p r e a d i n g from t h e incident electron b e a m ,
w h o s e angle d e p e n d s u p o n electron voltage a n d t h e
s a m p l e ' s a t o m i c n u m b e r a n d density. W h i l e t h e m e a n
d i a m e t e r of the a n a l y z e d v o l u m e c a n be very small
(less t h a n 50 n m ) for thin specimens, this is often still
i n a d e q u a t e t o analyze selectively individual precipi
tates a n d inclusions. T h e m a t r i x is included in t h e
excited region a n d m a k e s q u a n t i t a t i v e analysis diffi
cult if n o t impossible. Physical s e p a r a t i o n of t h e
features of interest from t h e m a t r i x , for e x a m p l e , with
a n e x t r a c t i o n replica, is s o m e t i m e s a practical solu
tion. In analyzing small features in thin specimens, the
use of extremely small electron b e a m s (to achieve t h e
best possible spatial resolution) p r o d u c e s very low
c o u n t rates, w h i c h m a k e s a n y e x t r a n e o u s b a c k g r o u n d
d u e t o electron scattering in t h e m i c r o s c o p e , for
instance, m o r e i m p o r t a n t , a n d also restricts a c c u r a c y
because of limited c o u n t i n g statistics.
In b u l k samples, subsurface s t r u c t u r e s m a y be
invisible in t h e S E M i m a g e b u t still c o n t r i b u t e t o t h e
analysis. T h e excited region is generally described as a
t e a r d r o p o r sphere. T h e p r o b a b i l i t y of electron scat
tering d e p e n d s o n a t o m i c n u m b e r (the c h a r g e o n t h e
nucleus) so t h a t the s h a p e of t h e excited v o l u m e
b e c o m e s m o r e flattened ( b r o a d c o m p a r e d t o its d e p t h )
for h i g h - Z specimens, a n d conversely b e c o m e s d e e p e r
c o m p a r e d t o its b r e a d t h for l o w - Z specimens. T h e
electron r a n g e d e p e n d s p r i m a r i l y o n t h e electron

580

Figure 2
Schematic diagram of the variation in size and shape of
the electron excited region with specimen atomic number
and electron accelerating voltage

energy, so t h e size of t h e excited region is c o n t r o l l e d

p r i m a r i l y b y t h e choice of accelerating voltage. T h i s is
i n d i c a t e d in F i g . 2.
It m a y also b e i m p o r t a n t t o r e m e m b e r t h a t different
elements h a v e different i o n i z a t i o n p o t e n t i a l s , so t h a t
electrons m a y b e c a p a b l e of exciting o n e element
d e e p e r in t h e s a m p l e t h a n a n o t h e r . I n general, t h e size
of t h e excited region is different for each element in
t h e specimen a n d m a y v a r y from as little as 0.2 p m t o
tens of m i c r o m e t e r s . S e c o n d a r y effects such as fluor
escence of detected r a y s b y o t h e r rays c a n e x t e n d
t o a m u c h larger v o l u m e .
If heterogeneity is suspected because of the size of
t h e excited region, it is wise t o analyze several loca
tions, o r t o p e r f o r m analysis o n t h e p o i n t of interest a t
several accelerating voltages (different d e p t h s of exci
t a t i o n ) , a n d c o m p a r e t h e m for uniformity. It s h o u l d
be n o t e d t h a t it is definitely n o t g o o d practice t o
collect a s p e c t r u m while s c a n n i n g t h e b e a m in a raster
over a large h e t e r o g e n e o u s region (either in t e r m s of
c o m p o s i t i o n o r surface o r i e n t a t i o n ) a n d t h e n p e r f o r m
a q u a n t i t a t i v e c o r r e c t i o n of t h e s p e c t r u m t o o b t a i n a n
" a v e r a g e " result. T h e v a r i o u s x-ray g e n e r a t i o n ,
a b s o r p t i o n a n d emission effects a r e definitely n o n l i
n e a r , a n d c a n n o t be a v e r a g e d in this w a y . T h e n o t i o n
t h a t this k i n d of " a v e r a g e " analysis is b e t t e r t h a n
n o t h i n g is d a n g e r o u s , a n d a l t h o u g h widely practised
s h o u l d definitely b e a v o i d e d . If a n " a v e r a g e " analysis
is r e q u i r e d , it c a n b e o b t a i n e d b y a n a l y z i n g a repre
sentative n u m b e r of s e p a r a t e ( r a n d o m ) p o i n t s , per
f o r m i n g a q u a n t i t a t i v e c o r r e c t i o n for e a c h ( p e r h a p s
t a k i n g i n t o a c c o u n t different surface o r i e n t a t i o n s ) ,
a n d t h e n a v e r a g i n g t h e resulting c o m p o s i t i o n a l d a t a .
See also: Electron Microprobe Analysis; Electron Micros
copy, Analytical; Scanning Electron Microscopy; X-Ray
Fluorescence Spectrometry

X-Ray

Bibliography
Heinrich F J 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Heinrich F J, Newbury D E, Yokowitz (eds.) 1976 Use
of Monte-Carlo Calculations in Electron Probe Microana
lysis and Scanning Electron Microscopy, National Bureau
of Standards Special Publication 460. US Department of
Commerce, Washington, DC
Russ J C 1984 Fundamentals of Dispersive X-Ray Analysis.
Butterworth, London
Scott V D, Love G 1983 Quantitative Electron Probe Mic
roanalysis. Ellis Horwood, Chichester, UK
Vollath D 1986 Some fundamental considerations to pre
cede image analysis. Bull. Mater. Sci. (India) 8: 169-82
J. C. R u s s
[ N o r t h C a r o l i n a State University,
Raleigh, N o r t h C a r o l i n a , U S A ]

Diffraction

m e t h o d . H o w e v e r , as in all analytical m e t h o d s it is
advisable w h e n e v e r possible t o s u p p l e m e n t x-ray in
f o r m a t i o n with d a t a from related m e t h o d s such a s
electron m i c r o s c o p y , x-ray fluorescence s p e c t r o s c o p y
a n d electron m i c r o p r o b e analysis.
T h e principal uses of t h e x-ray p o w d e r m e t h o d a r e :
(a)

identification of crystalline p h a s e s including q u a

litative a n d q u a n t i t a t i v e analysis of m i x t u r e s of
phases;

(b)

distinguishing b e t w e e n m i x t u r e s , v a r i o u s types
of solid s o l u t i o n s a n d p o l y m o r p h s ;

(c)

distinguishing b e t w e e n t h e a m o r p h o u s a n d crys
talline states;

(d)

precision m e a s u r e m e n t o f lattice p a r a m e t e r s a n d
thermal expansion;

(e)

d e t e r m i n a t i o n of t h e degree of preferred orien

t a t i o n a n d crystalline texture;

(f)

m e a s u r e m e n t of certain physical characteristics,

such as small crystallite sizes, strain, perfection,
lattice d i s o r d e r a n d d a m a g e ;

(g)

d e t e r m i n a t i o n of p h a s e s a n d p r o p e r t i e s as a
function of specimen e n v i r o n m e n t either in situ
o r after t r e a t m e n t a t t e m p e r a t u r e s from liquid
helium t o a b o u t 2000 C, a n d pressures u p t o
several h u n d r e d k b a r , in air, v a c u u m o r selected
gas.

X-Ray Powder Diffraction

X - r a y p o w d e r ( o r polycrystalline) diffraction h a s
played a very i m p o r t a n t role in t h e d e v e l o p m e n t of
science a n d t e c h n o l o g y . Since its i n t r o d u c t i o n in 1917,
by Hull in the U S A a n d i n d e p e n d e n t l y by D e b y e a n d
Scherrer in Switzerland, it h a s b e c o m e t h e i n d i s p e n s
able principal m e t h o d for identifying crystalline
p h a s e s of i n o r g a n i c , m e t a l a n d alloy, o r g a n i c , a n d
p o l y m e r m a t e r i a l s . T h e r e a r e n o w over 10 000 x-ray
p o w d e r diffraction i n s t r u m e n t s t h r o u g h o u t t h e w o r l d
used in m a n y a p p l i c a t i o n s for t h e n o n d e s t r u c t i v e
analysis a n d c h a r a c t e r i z a t i o n of chemicals, m i n e r a l s ,
ceramics, m e t a l s a n d o t h e r m a t e r i a l s . O n l y small
specimens a r e r e q u i r e d for analysis, a n d they m a y b e
in the form o f p o w d e r s , solid sections, thin films o n
s u b s t r a t e s , precipitates, d u s t s o r residues. C o m p l e t e xray systems a r e available from a n u m b e r of m a n u f a c
turers a n d m o d e r n i n s t r u m e n t s usually include a
m i n i c o m p u t e r for a u t o m a t e d c o n t r o l , d a t a r e d u c t i o n
a n d analysis.
A k n o w l e d g e of t h e crystal s t r u c t u r e of m a t e r i a l s is
essential in u n d e r s t a n d i n g t h e p r o p e r t i e s a n d h o w t o
identify t h e m , their b e h a v i o r u n d e r v a r i o u s c o n
ditions, a n d for t h e c h a r a c t e r i z a t i o n of t h e m a t e r i a l a t
all stages of its p r e p a r a t i o n . T h e r e p r o d u c t i o n of
m a t e r i a l s with tightly c o n t r o l l e d p r o p e r t i e s often re
quires x-ray analysis. A l t h o u g h single crystals a r e
preferred for d e t e r m i n i n g crystal s t r u c t u r e s o f n e w
m a t e r i a l s , s o m e m a t e r i a l s a r e available only as small
polycrystals. I n recent years t h e r e h a v e b e e n i m p o r t
a n t a d v a n c e s in using p o w d e r s for crystal s t r u c t u r e
d e t e r m i n a t i o n a n d refinement. M a n y s t r u c t u r e s a r e
already k n o w n a n d this i n f o r m a t i o n is used w i t h t h e
p o w d e r m e t h o d in m a n y types of studies t h a t a r e
essential for c h a r a c t e r i z i n g a n d a n a l y z i n g m a t e r i a l s .
T h e i m p o r t a n c e of these t e c h n i q u e s t o m a t e r i a l s
science will be a p p r e c i a t e d from t h e following list, all
of which c a n be best p e r f o r m e d b y t h e x-ray p o w d e r

Powder

1. Basis of

Method

B r a g g ' s law defines t h e c o n d i t i o n s for o b t a i n i n g x-ray

diffraction from a crystalline m a t e r i a l :
n = 2dsm

(1)

w h e r e is a small integer giving t h e o r d e r of diffrac

tion a n a l o g o u s t o a ruled g r a t i n g ; is t h e w a v e l e n g t h
of t h e characteristic line r a y s from t h e x-ray t u b e
a n d is usually t h e C u K a d o u b l e t with C u K a a j
= 0.1540562 n m ; d is t h e d i s t a n c e ( n m ) between a set
of parallel lattice planes; a n d is t h e angle between
t h e incident collimated x-ray b e a m a n d a n a t o m i c
lattice p l a n e in t h e crystal. T h e t e r m reflection
generally refers t o t h e individual diffractions a n d
s h o u l d n o t be confused with t h e t o t a l reflection of
r a y s a t very small angles from highly polished
surfaces.
T h e reflection angle for a p a r t i c u l a r set of lattice
p l a n e s (hkl) is:
1

2 0 = 2 s i n - [ A / 2 ^ / )]

(2)

w h e r e (hkl) a r e t h e Miller indices defining t h e orien

t a t i o n of t h e p l a n e w i t h respect t o t h e crystallographic
axes. Reflection o c c u r s only a t t h o s e angles w h e r e
scattering from successive lattice p l a n e s is in p h a s e ,
a n d this requires t h e p a t h difference t o b e a n integral
m u l t i p l e of t h e w a v e l e n g t h . F o r e x a m p l e , the
(hkl) = (\\\)
p l a n e of a silicon specimen reflects

581

X-Ray

Powder

Diffraction

CuKa,
rays a t 28.44 (20), from
which
d{lu) = 0.31357 n m . T h e second o r d e r d o e s n o t o c c u r
because of t h e lattice s y m m e t r y of the silicon a n d the
= 0.10453 n m . In
third o r d e r = 3 is a t 94.95
333)
is used instead of
crystallographic w o r k (hkl) =
= 3.
T h e relative intensities of the reflections a r e given
by

I,(hkl)

,|2
=

'

( 1+

cos-

K s i n 2 0 s i n

2 0 '\
2
)

(in:

Si ( 2 2 0 )

Si (311) --

D(220)

Si (422)
Si ( 4 0 0 ) | ? i (331)
0 (311J
(

(b)

|"">

(220)
(311)
(200)

(40
l ?2 2) )2

0)(33)
(422)
I
|(420) '

(I00).j
(C )

002)
(101)

(110)

(103) J
(112)
(102)
(300)

30

40

50

60

70

80

90

29
Figure 1
X-ray powder diffraction patterns of substances with
similar atomic arrangements: (a) silicon and diamond,
(b) sphalerite (face-centered-cubic ZnS), and (c) wurtzite
(hexagonal ZnS). The dashed lines connect the common
fundamental reflections

(4)

( T h e l o w e r - s y m m e t r y crystal systems require a d d i

tional terms.) F o r e x a m p l e , d i a m o n d a n d silicon h a v e
the s a m e d i a m o n d cubic s t r u c t u r e , with e a c h a t o m
linked by t e t r a h e d r a l b o n d i n g t o four c o n t a c t i n g
n e i g h b o r s . T h e a t o m i c d i a m e t e r of c a r b o n is smaller
t h a n t h a t of silicon a n d a0 of d i a m o n d is 0.35667 n m
a n d silicon 0.54301 n m . B o t h h a v e t h e s a m e p a t t e r n s
except for t h e larger d{hkl) values of silicon w h i c h o c c u r
at smaller reflection angles as s h o w n in Fig. 1. S p h a
lerite (-ZnS) h a s a similar s t r u c t u r e , b u t t h e a l t e r n a
tion of Z n - S - Z n a t o m s f o r m s a face-centered-cubic
lattice which gives t h e s a m e p a t t e r n plus a few a d d i
tional reflections. T h e p o l y m o r p h w u r t z i t e ( a - Z n S )
also h a s a similar f r a m e w o r k , b u t is h e x a g o n a l . T h e
lower s y m m e t r y a d d s m o r e reflections b u t t h e funda
m e n t a l reflections a r e identical with t h e o t h e r p a t
terns. T h e lattice type is d e t e r m i n e d by t h e reflections
that are present and absent.

582

(III)

...

w h e r e Fis the s t r u c t u r e factor of t h e hkl reflection a n d

is d e t e r m i n e d b y t h e p o s i t i o n s of t h e a t o m s , their
scattering factors a n d p h a s e s ; m is t h e multiplicity
factor which is a n integer o b t a i n e d b y c o m b i n i n g all
the + a n d - p e r m u t a t i o n s of h, k a n d / (in t h e case of
a c u b e , hOO, m = 6); a n d the t r i g o n o m e t r i c t e r m is t h e
L o r e n t z p o l a r i z a t i o n factor for p o w d e r diffractometry. In p o w d e r diffraction t h e specimen m u s t c o n t a i n
a large n u m b e r of small r a n d o m l y o r i e n t e d crystallites
to o b t a i n t h e correct values of t h e relative intensities
of all the possible lattice p l a n e s .
T h e p o w d e r p a t t e r n is a set of reflections in which
the lattice spacings a n d t h e relative intensities a r e
u n i q u e for each crystalline s u b s t a n c e . It is this p r o p
erty t h a t m a k e s it possible t o identify a s u b s t a n c e by
c o m p a r i n g its p a t t e r n with t h a t of a k n o w n s u b s t a n c e .
P a t t e r n s of m i x t u r e s a r e s u p e r i m p o s e d individual
p a t t e r n s . T h e n u m b e r of reflections r a n g e s from three
to a b o u t o n e h u n d r e d in t h e 2 r a n g e u p t o 90 with
C u K a r a d i a t i o n . T h e n u m b e r increases with unit-cell
d i m e n s i o n s a n d with decreasing s y m m e t r y of the
crystal s t r u c t u r e , a n d is generally i n d e p e n d e n t of the
chemical c o m p o s i t i o n .
Similar crystal s t r u c t u r e s give similar x-ray p a t t e r n s
in which the p e a k p o s i t i o n s will be shifted if t h e
m a t e r i a l s h a v e different lattice p a r a m e t e r s . T h e lattice
spacing d is related t o the lattice p a r a m e t e r a0 in cubic
crystals by
2\l/2

Si

(a)

2. Instrument

and Experimental

Methods

T h e m a j o r i n s t r u m e n t for x-ray p o w d e r diffraction

t h a t is used t o a n a l y z e virtually all types of m a t e r i a l , is
t h e focusing x-ray diffractometer with scintillation- o r
p r o p o r t i o n a l - c o u n t e r d e t e c t o r ( P a r r i s h 1965). T h e
basic a r r a n g e m e n t of t h e i n s t r u m e n t is s h o w n in F i g .
2. T h e c u r v e d m o n o c h r o m a t o r is usually highly
o r i e n t e d pyrolytic g r a p h i t e w h i c h reflects a b o u t 5 0 %
C u K a . It is set t o reflect only t h e K a d o u b l e t a n d
eliminates all o t h e r w a v e l e n g t h s from t h e x-ray t u b e
a n d specimen
fluorescence.
The detector rotates
a r o u n d t h e p o i n t a t twice t h e a n g u l a r speed of t h e
specimen so t h a t t h e specimen surface is always a t
a n d t h e receiving slit a t 2.
T h e diffractometer is driven b y a s y n c h r o n o u s
1
m o t o r , usually a t m i n , a n d t h e intensities
r e c o r d e d with a r a t e m e t e r a n d strip c h a r t . T h e
intensities a n d 2 values a r e r e a d from t h e c h a r t a n d

X-Ray

the lattice spacings calculated from t h e B r a g g e q u a

tion. M i n i c o m p u t e r s h a v e been i n t r o d u c e d t o a u t o
m a t e t h e p r o c e s s a n d collect t h e d a t a in digital f o r m
for c o m p u t e r d a t a r e d u c t i o n . A s t e p p i n g m o t o r re
places the s y n c h r o n o u s m o t o r a n d t h e p a t t e r n is
s c a n n e d stepwise w i t h selected a n g u l a r i n c r e m e n t s
2 = 0.01-0.05 a n d c o u n t time 0 . 1 s o r l o n g e r
d e p e n d i n g o n t h e n a t u r e of t h e p a t t e r n a n d t h e
required statistical a c c u r a c y . T h e d a t a a r e t h e n a u t o
matically r e d u c e d t o a set of d values a n d p e a k
intensities with a p e a k - s e a r c h o r profile-fitting p r o
gram. Algorithms have been developed which de
crease t h e t i m e for d a t a collection a n d r e d u c t i o n b y
m o r e t h a n o n e o r d e r of m a g n i t u d e c o m p a r e d w i t h
m a n u a l m e t h o d s a n d t h u s significantly increase t h e
precision. H i g h - s p e e d d a t a collection a t a r a t e of 30
1
(20) m i n using a c o n v e n t i o n a l sealed-off x-ray t u b e
a n d p e a k - s e a r c h d a t a r e d u c t i o n in less t h a n a m i n u t e
are n o w possible.
A different diffraction m e t h o d i n t r o d u c e d b y G i e s sen a n d G o r d o n in 1968 uses a solid-state d e t e c t o r
a n d m u l t i c h a n n e l pulse-height analyzer. T h e reflec
tions arise from t h e c o n t i n u o u s x-ray s p e c t r u m a n d
the B r a g g law in this case is

3. Phase

12.398

2nne.E,hkl)

w h e r e 0 is n o w t h e selected angle of incidence for all

reflections with d e t e c t o r a t 20, a n d is t h e energy in
keV for t h e reflection (hkl). By d e c r e a s i n g 20 t h e
p e a k s b e c o m e m o r e s e p a r a t e d o n a n energy scale, b u t
also b r o a d e r . T h e energies of t h e pulses a r e p r o p o r
tional t o t h e x-ray energies a n d a r e electronically

Diffraction

s o r t e d i n t o n a r r o w energy c h a n n e l s b y t h e pulse
height analyzer. T h e Si(Li) crystal d e t e c t o r m u s t be
k e p t a t l i q u i d - n i t r o g e n t e m p e r a t u r e a t all times.
T h e r e is n o need for s c a n n i n g b e c a u s e all the
reflections a r e r e c o r d e d s i m u l t a n e o u s l y . T h e m e t h o d
h a s t h e a d v a n t a g e t h a t a recognizable p a t t e r n (with
low statistical a c c u r a c y ) c a n be o b t a i n e d in less t h a n a
m i n u t e with a c o n v e n t i o n a l x-ray t u b e , o r in a few
s e c o n d s with a s y n c h r o t o n x-ray b e a m ; f u r t h e r m o r e ,
since there a r e n o m o v i n g p a r t s , specimen devices for
h e a t i n g a n d c o o l i n g a r e relatively easy t o m a k e .
H o w e v e r , t h e r e s o l u t i o n , w h i c h is d e t e r m i n e d by t h e
d e t e c t o r , is m o r e t h a n o n e o r d e r of m a g n i t u d e lower
t h a n t h a t of a s c a n n i n g diffractometer, a n d t h e p e a k t o - b a c k g r o u n d r a t i o m u c h lower, m a k i n g it useful
only for t h e simple p a t t e r n s .
C o n s i d e r a b l e c a r e is r e q u i r e d t o p r e p a r e speci
m e n s for x-ray diffraction. O n l y t h e surface layer of
thickness d e t e r m i n e d b y t h e a b s o r p t i o n c o n t r i b u t e s t o
t h e diffraction, a n d therefore h o m o g e n e i t y , flatness,
p a c k i n g a n d similar factors a r e i m p o r t a n t in s a m p l e
p r e p a r a t i o n . T h e specimen s h o u l d b e a b o u t 1-2 c m in
d i a m e t e r , a l t h o u g h smaller specimens c a n b e used.
T h e crystallites s h o u l d b e small, preferably less t h a n
a b o u t 20 , a n d t h e specimen r o t a t e d a b o u t 70 r p m
a r o u n d a n axis n o r m a l t o t h e surface t o o b t a i n g o o d
values of t h e relative intensities. T h e p o w d e r m a y be
c e m e n t e d with a 5 % s o l u t i o n of a m y l a c e t a t e in
c o l l o d i o n , o r with vaseline t o a glass slide, a shallow
cylindrical h o l d e r o r single-crystal p l a t e c u t in a
direction t h a t d o e s n o t p r o d u c e a reflection in t h e
a n g u l a r r a n g e r e c o r d e d [e.g., silicon (510)]. F i l m s a s
thin as 3 0 - 4 0 n m c a n be a n a l y z e d if they a r e well
crystallized.

Figure 2
Geometry of the x-ray powder diffractometer in the
focusing plane: F, line focus of x-ray tube; PS, parallel foil
assembly to limit divergence in plane of drawing; DS,
divergence slit; Sp, specimen; O, diffractometer axis of
rotation; , Bragg angle; RS, receiving slit; AS, antiscatter
slits; M, curved crystal monochromator; D, scintillation or
proportional counter; SpFC, specimen focusing circle
(radius varies with 0); DC, diffractometer circle with 20
scale; MFC, monochromator focusing circle

Powder

( 5

Identification

T h e identification of crystalline p h a s e s requires a file

of k n o w n s t a n d a r d d a t a for c o m p a r i s o n . T h e P o w d e r
Diffraction File p u b l i s h e d b y t h e I n t e r n a t i o n a l C e n t e r
for P o w d e r Diffraction ( S w a r t h m o r e , P e n n s y l v a n i a )
is t h e m o s t c o m p r e h e n s i v e d a t a set available a n d is
widely used for this p u r p o s e . It n o w c o n t a i n s d a t a for
a b o u t 38 000 s u b s t a n c e s in t h e f o r m of c a r d s , b o o k s
a n d m a n u a l s for h a n d searching, a n d o n m a g n e t i c
t a p e o r diskettes for r a p i d c o m p u t e r searching.
T h e time a n d success in m a k i n g identifications a r e
d e p e n d e n t o n t h e q u a l i t y of t h e e x p e r i m e n t a l d a t a a n d
t h e d a t a in t h e reference file. H a n d search usually
begins with t h e H a n a w a l t S e a r c h M a n u a l in w h i c h the
d a t a a r e a r r a n g e d in g r o u p s a n d s u b g r o u p s b a s e d o n
t h e t w o highest-intensity d values. T h e h a n d m e t h o d
h a s been used for m a n y years b u t requires consider
able time a n d experience a n d b e c o m e s m o r e difficult
when there are mixtures.
M i n i c o m p u t e r s e a r c h - m a t c h p r o g r a m s h a v e been
d e v e l o p e d t o m a k e r a p i d c o m p r e h e n s i v e searches of
t h e s t o r e d digital files ( P a r r i s h et al. 1982). T h e

583

X-Ray

Powder

Diffraction

p r o g r a m s use selectable t e r r o r w i n d o w s , a u t o m a t i c
d a t a c o r r e c t i o n with internal s t a n d a r d s , chemicald a t a prescreening a n d o t h e r o p t i o n s t o facilitate the
identification, a n d c o m p u t e a figure of merit w h i c h
gives the " g o o d n e s s of fit" of the u n k n o w n c o m p a r e d
with each of the selected p o t e n t i a l s t a n d a r d s . T h e
c o m p u t e r also displays the p a t t e r n s of the u n k n o w n
with each of the selected s t a n d a r d s for direct visual
c o m p a r i s o n . (All the p o w d e r p a t t e r n s in this article
are c o m p u t e r - g e n e r a t e d . ) It is n o w possible t o collect
the d a t a , reduce it t o a set of d a n d / values a n d
identify the c o n s t i t u e n t s of a n a v e r a g e m a t e r i a l in 1 0 20 m i n . If a user file is m a d e with a g r o u p of m a t e r i a l s
likely t o be f o u n d in a p a r t i c u l a r type of a p p l i c a t i o n ,
identification time is greatly reduced because the size
of the s t a n d a r d file is m u c h smaller a n d its q u a l i t y c a n
be controlled.
T h e r e are a large n u m b e r of a p p l i c a t i o n s of the
p o w d e r m e t h o d based o n p h a s e identification. A
typical l a b o r a t o r y use is t o follow the c o u r s e of a
solid-state chemical r e a c t i o n which c a n n o t be per
formed by chemical analysis b e c a u s e the b a t c h
c o m p o s i t i o n r e m a i n s the s a m e . F o r e x a m p l e , large
single-crystal b o u l e s of G d 3 G a 5 0 1 2, g a r n e t are used as
substrates for m a g n e t i c b u b b l e devices. T h e i r g r o w t h
requires a starting g a r n e t p o w d e r p r e p a r e d by sinter
ing a blend of G d 2 0 3 a n d G a 2 0 3 in p r o p e r p r o p o r t i o n s
to the correct t e m p e r a t u r e .
T h e p a t t e r n s required for this analysis were m a d e
with a m i n i c o m p u t e r - a u t o m a t e d diffractometer (see
Fig. 3). T h e u p p e r p a t t e r n is the s t a r t i n g oxide mix
ture blend a n d the tick m a r k s a r e the p e a k p o s i t i o n s .
T h e following t w o p a t t e r n s are the s t a n d a r d s identi
fied by c o m p u t e r s e a r c h - m a t c h : the cubic form of aG d 2 0 3 a n d the m o n o c l i n i c / ? - G a 2 0 3 . T h e intensities in
b o t h s t a n d a r d s h a v e been scaled by the c o m p u t e r t o
a p p r o x i m a t e t h o s e in the blend. T h o s e p e a k s m a t c h
ing the blend a r e identified by the lower set of tick
m a r k s . T h e e x p a n d e d p a t t e r n (Fig. 3b) s h o w s the
partially c o m p l e t e d c o n v e r s i o n t o g a r n e t a n d the
small a m o u n t of residual / ? - G a 2 0 3 indicates the cor
rect sintering c o n d i t i o n s h a v e a l m o s t been r e a c h e d .
T h e m a x i m u m n u m b e r of p h a s e s t h a t c a n be identi
fied in a specimen d e p e n d s o n the complexity of the
p a t t e r n s a n d the degree of o v e r l a p p i n g . Profile fitting
c a n be used t o s e p a r a t e the o v e r l a p p i n g reflections
a n d t o d e t e r m i n e the individual intensities (Parrish
a n d H u a n g 1979). M i x t u r e s of six p h a s e s c a n b e
p e r f o r m e d routinely with c o m p u t e r m e t h o d s .
T h e m i n i m u m a m o u n t of a p h a s e t h a t is detectable
in a m i x t u r e is d e p e n d e n t o n the a b s o r p t i o n , crystalli
nity a n d p e a k - t o - b a c k g r o u n d r a t i o s . T h e lower limits
r a n g e from a b o u t 0 . 1 - 5 w t % . Very small a m o u n t s of
a sample (in the m i c r o g r a m r a n g e ) c a n be detected,
b u t even smaller samples require special t e c h n i q u e s
using high-brilliance r o t a t i n g - a n o d e x-ray t u b e s .
Q u a n t i t a t i v e d e t e r m i n a t i o n of t h e c o n c e n t r a t i o n of
each p h a s e in a m i x t u r e requires careful specimen
p r e p a r a t i o n a n d m e a s u r e m e n t s of a few of the higher-

584

Oxide

mixture

ci-

Ll

J-

.A,

G d 20 3

, A,

> . A ,..-

/ 3 - G a 20 3
...

30

, 6 A A

. A

40

50

<

I
26

32

G A
38

20

Figure 3
Patterns of (a) mixed blend of two oxides and the phases
identified by computer search-match, and (b) after
sintering showing conversion to garnet Gd 3Ga 50 12 (G) and
residual -Ga 20 3(A) and a-Gd 2Q 3(D)

intensity reflections of e a c h c o n s t i t u e n t . It is also

necessary t o m a k e a second set of m e a s u r e m e n t s after
a d d i n g a k n o w n weight of a s t a n d a r d o r o n e of the
c o n s t i t u e n t s t o correct for differences in reflecting
p o w e r a n d a b s o r p t i o n a m o n g the p h a s e s . Q u a n t i t a
tive analyses of u p t o six c o n s t i t u e n t s h a v e been
r e p o r t e d in such c o m p l e x m a t e r i a l s a s c e m e n t s a n d
r o c k s , with accuracies of a few p e r c e n t a b s o l u t e .
T h e x-ray m e t h o d is essential for w o r k i n g o u t p h a s e
d i a g r a m s a n d is often used in c o n j u n c t i o n with differ
ential t h e r m a l analysis a n d m i c r o s c o p e studies. T h e
m a t e r i a l s a r e either q u e n c h e d a n d m e a s u r e d at r o o m
t e m p e r a t u r e , o r x-ray m e a s u r e m e n t s m a d e at c o n
trolled high t e m p e r a t u r e s . T h e p h a s e b o u n d a r i e s c a n
be d e t e r m i n e d from t h e x-ray p a t t e r n w h i c h gives the
structures of the p h a s e s , their p r o p o r t i o n s a n d lattice
parameters.
I n a s u b s t i t u t i o n a l solid s o l u t i o n the c o m p o s i t i o n
varies b u t the s t r u c t u r e r e m a i n s the s a m e , except for

X-Ray

4. Lattice-Parameter

Powder

Diffraction

Determination

T h e lattice p a r a m e t e r a0 is frequently r e q u i r e d in
m a t e r i a l s c h a r a c t e r i z a t i o n . A n u m b e r of reflections
s h o u l d be m e a s u r e d a n d their relation t o a0 is given by
E q n . (4). Careful e x p e r i m e n t a l t e c h n i q u e s m u s t be
used t o o b t a i n a c c u r a t e values. S y s t e m a t i c e r r o r s are
t h e p r i n c i p a l c a u s e of low a c c u r a c y a n d they c a n be
m i n i m i z e d by using h i g h e r - a n g l e reflections. T h e r e a r e
t w o basic r e a s o n s for this: (a) i n s t r u m e n t a l a b e r r a
t i o n s a n d specimen d i s p l a c e m e n t e r r o r s increase
r a p i d l y with decreasing reflection angle, a n d (b) the
h i g h e r t h e reflection angle t h e g r e a t e r t h e a c c u r a c y , as
s h o w n b y t h e differential f o r m of t h e B r a g g e q u a t i o n :
Figure 4
X-ray diffractometer pattern of a small quantity of
crystalline quartz (two peaks) on a glass substrate

c h a n g e s in t h e lattice p a r a m e t e r a0 if t h e s u b s t i t u t i n g
a t o m s h a v e different sizes. T h e r e is a very r o u g h linear
relation b e t w e e n c o m p o s i t i o n a n d a0 a n d t h e c o m p o
sition m a y b e d e t e r m i n e d from t h e shifts in p e a k
positions. The substituting atoms are randomly
a r r a n g e d o n t h e lattice sites, b u t in s o m e cases p r o p e r
annealing may produce a long-range order which can
be detected b y t h e a p p e a r a n c e of a d d i t i o n a l p e a k s
called s u p e r s t r u c t u r e reflections. T h e y a r e generally
m u c h w e a k e r t h a n t h e f u n d a m e n t a l reflections a n d
d e p a r t u r e s from perfect l o n g - r a n g e o r d e r further
w e a k e n s t h e m . Interstitial a n d defect types of solid
solutions m a y b e detected b y c o m p a r i n g t h e m e a s u r e d
density with t h e density c a l c u l a t e d from t h e unit-cell
volume.
T h e crystalline a n d a m o r p h o u s states c a n be readily
distinguished. A n a m o r p h o u s solid h a s only local
short-range order without the repeating long-range
lattice o r d e r characteristic of t h e crystalline state. T h e
diffraction from a n a m o r p h o u s s u b s t a n c e is a b r o a d
h u m p e x t e n d i n g o v e r a w i d e a n g u l a r r a n g e as s h o w n
b y t h e p a t t e r n of a m i c r o s c o p e slide ( F i g . 4). If t h e
m a t e r i a l c o n t a i n s a crystalline p o r t i o n o r begins t o
devitrify, t h e crystalline p a t t e r n is s u p e r i m p o s e d as
illustrated b y t h e a d d i t i o n of a few m i c r o g r a m s of
q u a r t z p o w d e r o n t o t h e slide. T h e crystalline p e a k
intensities a r e m u c h higher a n d t h e (101) reflection of
the s a m e m a s s of q u a r t z w o u l d b e a b o u t 260 times
higher t h a n t h e t o p of t h e a m o r p h o u s b a n d . M o s t
a m o r p h o u s p a t t e r n s a r e similar a n d c a n n o t b e used t o
identify m a t e r i a l s . R a d i a l d i s t r i b u t i o n functions c a n
be derived t o d e t e r m i n e local a t o m i c a r r a n g e m e n t s
( W a r r e n 1969). C r y s t a l l i n e - t o - a m o r p h o u s weight
ratios m a y be a p p r o x i m a t e l y d e t e r m i n e d f r o m t h e
relative intensities of all t h e crystalline reflections a n d
the a m o r p h o u s p a r t . T h i s usually requires s t a n d a r d s
of k n o w n r a t i o s . H o w e v e r , if p o o r l y crystallized
m a t e r i a l is p r e s e n t t h e d e t e r m i n a t i o n b e c o m e s m u c h
m o r e difficult o r impossible.

Ad/d=

-A0cos 0

(6)

T h e e x p e r i m e n t a l e r r o r 0 (in r a d i a n s ) is rarely less

t h a n 0.0 (20), w h i c h c o r r e s p o n d s t o Ad/d= 0 . 0 4 %
a t 25 (20) a n d 0 . 0 0 1 5 % a t 160.
A n i n t e r n a l s t a n d a r d such as silicon, w h o s e lattice
p a r a m e t e r is k n o w n t o high a c c u r a c y , m a y be a d d e d
t o t h e specimen t o d e t e r m i n e t h e c o r r e c t i o n s for
systematic e r r o r s . T h e reflection angle c a n be
m e a s u r e d by a p e a k - s e a r c h o r b y a profile-fitting
p r o c e d u r e , a n d t h e lattice p a r a m e t e r d e t e r m i n e d from
a least-squares fit, preferably w e i g h t i n g t h e higherangle reflections. T h e lattice p a r a m e t e r c a n be deter
m i n e d with a precision of 0.10.01 % a n d o n e o r d e r of
m a g n i t u d e higher w i t h very careful t e c h n i q u e s . T h e r
m a l e x p a n s i o n a n d its v a r i a t i o n s with crystal direction
in n o n c u b i c crystals c a n b e d e t e r m i n e d from m e a s u r e
m e n t s of a0 a t different t e m p e r a t u r e s .
T h e l a t t i c e - p a r a m e t e r d e t e r m i n a t i o n is usually car
ried o u t w i t h polycrystalline specimens b u t t h e r e a r e
i m p o r t a n t a p p l i c a t i o n s for single crystals. F o r ex
a m p l e , t h e g r o w t h of single-crystal g a r n e t b o u l e s
requires a n a c c u r a t e l a t t i c e - p a r a m e t e r m e a s u r e m e n t
t o o b t a i n t h e correct G d : G a r a t i o . T h e lattice p a r a
m e t e r varies w i t h t h e r a t i o a n d t h e c o m p o s i t i o n c a n be
d e t e r m i n e d w i t h far g r e a t e r precision from a m e a s u r e
m e n t of a0 t h a n is possible w i t h fluorescence o r
electron m i c r o p r o b e e l e m e n t a l analysis. T h e m e t h o d
requires a fine c o l l i m a t e d x-ray b e a m (Fig. 5) a n d t w o
m e a s u r e m e n t s of t h e s a m e reflection o n e a c h side of
t h e direct b e a m as i n d i c a t e d b y t h e t w o p o s i t i o n s of
crystal C I . T h e p r o c e d u r e is simplified b y t h e use
of t w o d e t e c t o r s t o m e a s u r e t h e angle 36O-40 from
w h i c h a0 c a n be calculated.
A similar t e c h n i q u e c a n b e used t o m e a s u r e the
difference in lattice p a r a m e t e r s of a n epitaxial
film a( a n d t h e single-crystal s u b s t r a t e as. T h e lat
tice m i s m a t c h Aa/a = (asaf)/tfs
d e t e r m i n e s the
stress-induced a n i s o t r o p y , o n e of t h e t w o sources of
m a g n e t i c uniaxial a n i s o t r o p y in g a r n e t films. T h e
difference in reflection angles of t h e film a n d s u b s t r a t e
4
d e t e r m i n e s Ad/d = Aa/a 10~ . A double-crystal
t e c h n i q u e is desirable t o o b t a i n sufficient resolution t o
s e p a r a t e t h e closely spaced reflections. T h e m e t h o d

585

X-Ray

Powder

Diffraction

5. Preferred

Orientation

N o n r a n d o m d i s t r i b u t i o n of crystallites in a m a t e r i a l is
called preferred o r i e n t a t i o n o r t e x t u r e . It m a y result
from t h e m e t h o d of p r e p a r a t i o n a n d c a n m a r k e d l y
affect t h e p r o p e r t i e s . F o r e x a m p l e , t h e crystallites in a
c o l d - d r a w n wire orient w i t h t h e s a m e c r y s t a l l o g r a p h i c
direction parallel t o t h e wire axis, a n d in rolled m e t a l
sheets certain p l a n e s orient parallel t o t h e surface a n d
t h e rolling direction w h e n t h e grains r o t a t e a n d align
d u r i n g t h e plastic d e f o r m a t i o n . Preferred o r i e n t a t i o n
also o c c u r s in castings, electrochemical d e p o s i t i o n
a n d t h i n films. T h e degree of preferred o r i e n t a t i o n c a n
be d e t e r m i n e d with a pole-figure device a t t a c h e d t o
t h e diffractometer t o m e a s u r e intensities for different
specimen o r i e n t a t i o n s . T h e intensities c a n b e p l o t t e d
o n a s t e r e o g r a p h i c projection a n d c o n t o u r e d t o s h o w
t h e a n g u l a r d i s t r i b u t i o n of t h e n o r m a l s t o selected
lattice p l a n e s in v a r i o u s c r y s t a l l o g r a p h i c directions.
Such p l o t s a r e used t o follow s t r u c t u r a l c h a n g e s in
metallurgical m a t e r i a l s subjected t o m e c h a n i c a l a n d
t h e r m a l processes.

(b)

Figure 5
(a) Method for precision lattice-parameter measurement of
single-crystal plate and mismatch of epitaxial film on
substrate by parallel double-crystal method, and
(b) profiles of pair of films F and C on substrate S

uses a n o n d i v e r g e n t m o n o c h r o m a t i c b e a m from a
high-quality g a r n e t wafer C 2 m o u n t e d a p p r o x i m a t e l y
parallel t o C I , d e t e c t o r D l is m o v e d t o , a n d t h e
specimen C I r o t a t e d t o pick u p t h e reflections s h o w n
in the lower p a r t of Fig. 5. (In p r a c t i c e C I a n d C 2 c a n
be i n t e r c h a n g e d . ) T h e e x a m p l e s h o w n is a p a i r of
films F a n d C of different c o m p o s i t i o n s g r o w n o n t h e
s u b s t r a t e S with lattice p a r a m e t e r s of F > S > C . T h e
p e a k s e p a r a t i o n of C a n d S is 112" ( c o r r e s p o n d i n g t o
4
Aa/a = 2.1 x 10~ ) a n d b e t w e e n F a n d S is
4
76" = 2.2 x 1 0 " from which t h e m e a n strain in e a c h
film c a n be calculated. T h e large difference in a0
between film F d e p o s i t e d o n film C c a u s e d a s y m m e t
ric b r o a d e n i n g of t h e F profile i n d i c a t i n g n o n u n i f o r m
strain. T h i s is a n e x a m p l e of t h e u n i q u e analytical
capabilities of x-ray diffraction in which t h e indi
vidual p r o p e r t i e s of physically s u p e r i m p o s e d m a t e r
ials c a n be d e t e r m i n e d .

586

I n m a t e r i a l s science it is often necessary t o p r e p a r e

thin films in w h i c h t h e crystallites h a v e specific orien
t a t i o n s w i t h respect t o t h e surface in o r d e r t o achieve
t h e desired physical o r m a g n e t i c p r o p e r t i e s . T h e d e
gree of preferred o r i e n t a t i o n t h a t c a n b e achieved
d e p e n d s o n t h e s t r u c t u r e of t h e s u b s t r a t e , m e t h o d of
p r e p a r a t i o n , m o r p h o l o g y a n d related factors. It c a n
be d e t e r m i n e d from t h e relative intensities of e a c h of
t h e reflections c o m p a r e d with t h o s e of a r a n d o m l y
oriented p o w d e r [e.g., 7(220) powder/film]. If a
p o w d e r is n o t available t h e r a n d o m p a t t e r n c a n b e
calculated from t h e crystal s t r u c t u r e . T h e m e a s u r e
m e n t s a r e m a d e with a diffractometer b e c a u s e only
t h o s e crystallites w h o s e lattice p l a n e s a r e within a b o u t
of parallelism with t h e surface c a n reflect.
I n e x t r e m e cases of preferred o r i e n t a t i o n only a
single reflection o c c u r s , s h o w i n g t h a t t h e entire film
h a s t h a t lattice p l a n e parallel t o t h e surface. T h e
a b s o l u t e intensity m a y also b e m u c h higher t h a n the
p o w d e r . If t h e s a m e specimen is m e a s u r e d in t r a n s
mission using a modification of t h e i n s t r u m e n t geo
m e t r y in F i g . 1, only t h e p l a n e s n o r m a l t o t h e surface
will be able t o reflect. C o m p a r i s o n of t h e relative
intensities of t h e reflection a n d t r a n s m i s s i o n p a t t e r n s
gives a g o o d m e a s u r e of t h e preferred o r i e n t a t i o n . I n p l a n e o r i e n t a t i o n c a n be d e t e r m i n e d b y setting t h e
diffractometer o n a p e a k a n d m e a s u r i n g t h e intensity
as t h e film is slowly r o t a t e d a r o u n d a n axis n o r m a l t o
t h e surface. If there is r a n d o m i n - p l a n e o r i e n t a t i o n t h e
intensity will be u n i f o r m a n d preferred o r i e n t a t i o n
causes b r o a d p e a k s a n d valleys in such a scan.
6.

Imperfections

R e a l crystals rarely h a v e t h e ideal s t r u c t u r e of a

perfectly r e p e a t i n g lattice. V a r i o u s types of imperfec
tions a r e p r e s e n t a n d m a n y of t h e m modify t h e
physical p r o p e r t i e s of t h e m a t e r i a l . S o m e imperfec-

X-Ray

84

85

86

87

88

1
89

20

Figure 6
X-ray diffractometer reflection profiles of Pd(222) thin
film broadened by strain and standard well-crystallized
powder W(220); peak intensities normalized

tions c a u s e easily o b s e r v a b l e c h a n g e s in t h e x-ray

pattern. F o r example, crushing a n d grinding m a y
cause large s t r a i n s w h i c h p r o d u c e b r o a d e n e d reflec
tions w i t h d i m i n i s h e d p e a k h e i g h t s . S t r a i n release b y
a n n e a l i n g c a n b e followed b y t h e s h a r p e n i n g o f t h e
reflections. F i g u r e 6 s h o w s t h e b r o a d (222) reflection
of a highly s t r a i n e d t h i n film o f p a l l a d i u m a n d t h e
m u c h n a r r o w e r (220) reflection o f well-crystallized
t u n g s t e n p o w d e r free o f strain; t h e latter results o n l y
from t h e i n s t r u m e n t function i n h e r e n t in t h e experi
mental method.
In analyses b a s e d o n profile m e a s u r e m e n t s , it is first
necessary t o s u b t r a c t t h e effect o f t h e i n s t r u m e n t
function t o derive t h e p u r e diffraction effects f r o m t h e
specimen. T h e i n s t r u m e n t g e o m e t r y , a b e r r a t i o n s a n d
x-ray spectral line s h a p e s c o n v o l v e t o p r o d u c e profile
s h a p e s w h i c h v a r y w i t h 20. T h e s e basic line s h a p e s c a n
be m e a s u r e d w i t h well-crystallized specimens free o f
line b r o a d e n i n g ( F i g . 6). C o m p u t e r p r o g r a m s a r e
desirable t o m a k e t h e c a l c u l a t i o n s .
T h e x-ray s t u d y o f i m p e r f e c t i o n s in polycrystalline
m a t e r i a l s r e q u i r e s t h a t a c o n s i d e r a b l e fraction o f t h e
a t o m s a r e involved t o m a k e t h e effect d e t e c t a b l e , a n d
the results a r e t h u s statistical r a t h e r t h a n o n t h e basis
of a few u n i t cells. Small-scale i m p e r f e c t i o n s a r e b e t t e r
d e t e r m i n e d b y special x-ray single-crystal a n d e l e c t r o n
m i c r o s c o p e studies. T h e r e h a v e b e e n v a r i o u s types o f
imperfections e l u c i d a t e d b y x-ray diffraction such a s
o r d e r - d i s o r d e r in solid s o l u t i o n s , plastic a n d elastic
deformation, homogeneous a n d inhomogeneous
strains, e r r o r s in layer s t a c k i n g , twin faulting a n d
small crystallite size. T h e s e c a u s e subtle c h a n g e s in
t h e x-ray p a t t e r n b y s y m m e t r i c a n d a s y m m e t r i c
b r o a d e n i n g o f t h e profiles a n d small shifts in t h e p e a k
p o s i t i o n s . T h e analyses r e q u i r e a c c u r a t e m e a s u r e m e n t
of t h e profile s h a p e s , profile-fitting m e t h o d s a n d
Fourier-series analysis o f t h e profiles u s i n g t h e coeffi
cients t o r e p r e s e n t t h e b r o a d e n i n g .

Powder

Diffraction

X - r a y m e t h o d s a r e used a s a n o n d e s t r u c t i v e
m e t h o d t o d e t e r m i n e residual elastic strains. A l
t h o u g h t h e elastic c o n s t a n t s v a r y c o n s i d e r a b l y with
c r y s t a l l o g r a p h i c d i r e c t i o n they a r e r o u g h l y i s o t r o p i c
in r a n d o m polycrystalline m a t e r i a l s . U s i n g small xr a y b e a m s , s t r a i n s c a n b e m e a s u r e d in small a r e a s a n d
steep s t r a i n g r a d i e n t s c a n b e d e t e r m i n e d . T h e m e t h o d
is b a s e d o n t h e fact t h a t t h e lattice s p a c i n g d{hkl,
c h a n g e s w i t h a p p l i e d stress a n d acts a s a n i n t e r n a l
s t r a i n g a u g e . U n i f o r m l o n g - r a n g e tensile strain in
creases t h e d values a n d shifts t h e p e a k s t o smaller
angles w i t h o u t b r o a d e n i n g . N o n u n i f o r m s t r a i n s c a u s e
b r o a d e n i n g w i t h o u t shifts. B o t h elastic a n d plastic
d e f o r m a t i o n strains c a u s e shifts a n d b r o a d e n i n g .
W h e n t h e d i m e n s i o n s of crystallites a r e less t h a n
a b o u t 1 t h e profiles begin t o b r o a d e n a n d t h e
b r o a d e n i n g increases w i t h d e c r e a s i n g size. B o t h size
a n d strain b r o a d e n i n g c a n b e m e a s u r e d w h e n they
coexist b y u s i n g t h e F o u r i e r m e t h o d a n d several
o r d e r s o f a reflection; t h e size factor is i n d e p e n d e n t of,
a n d t h e d i s t o r t i o n d e p e n d e n t o n , t h e o r d e r of t h e
reflection.
A simplified m e t h o d frequently used t o d e t e r m i n e
small crystallite sizes a s s u m e s t h e r e a r e n o strains o r
o t h e r sources of line b r o a d e n i n g . It uses t h e Scherrer
equation:
=

cos 0 ^ B( 2 0 )

w h e r e t{hkl) is t h e a v e r a g e d i m e n s i o n o f t h e crystallites
n o r m a l t o t h e (hkl) diffracting p l a n e , k is a c o n s t a n t
usually t a k e n a s 0.9, is t h e w a v e l e n g t h ( n m ) 0
t h e B r a g g angle a n d PB (2) t h e particle size line
b r o a d e n i n g in r a d i a n s m e a s u r e d a s t h e full-width
h a l f - m a x i m u m ( F W H M ) . (2) is o b t a i n e d from
>

>

/ B(2^) = [ / O ^ ) - ^ S T ( 2 ^ ) ]

1 /2

(8)

w h e r e P0 (20) is t h e w i d t h o f t h e m e a s u r e d profile a n d
PST(29) t h e w i d t h of t h e i n s t r u m e n t function profile.
F o r a given t t h e b r o a d e n i n g increases a s l / c o s 0 ,
b u t t h e intensities decrease w i t h increasing 2 a n d
d e c r e a s i n g r, m a k i n g it m o r e difficult t o m a k e accur
a t e m e a s u r e m e n t s . I n p r a c t i c e t h e useful r a n g e of t h e
m e t h o d is a b o u t 5 - 3 0 0 n m . A l t h o u g h t c a n b e deter
m i n e d for several d i r e c t i o n s b y u s i n g different (hkl)
p l a n e s , it is desirable t o u s e s c a n n i n g electron m i c r o s
c o p y t o d e t e r m i n e t h e m o r p h o l o g y b e c a u s e if t h e
particles a r e needles o r p l a t e s t h e results c o u l d b e in
e r r o r . T h e t w o m e t h o d s a r e c o m p l e m e n t a r y since t h e
x-ray m e t h o d gives t h e a v e r a g e crystallite size a n d t h e
m i c r o s c o p e t h e particle size, w h i c h m a y b e clusters of
crystallites.
Diffuse s c a t t e r i n g within a few degrees o f t h e direct
b e a m (small-angle diffraction) is a m e t h o d used for
particle size d e t e r m i n a t i o n typically from a few n a n o
m e t e r s t o tens o f n a n o m e t e r s . It is a p p l i c a b l e t o
a m o r p h o u s a s well a s crystalline m a t e r i a l s , a n d is used
for a n a l y z i n g s u s p e n s i o n s , single-chain d i m e n s i o n s of

587

X-Ray

Powder

Diffraction

p o l y m e r solutions, lamellar s e p a r a t i o n distances in

semicrystalline p o l y m e r s a n d p h a s e - b o u n d a r y thick
nesses in t w o - p h a s e systems. T h e m e t h o d requires
special i n s t r u m e n t a t i o n a n d c o l l i m a t o r s d u e t o t h e
necessity of m e a s u r i n g so close t o t h e p r i m a r y b e a m .
See also: Single-Crystal X-Ray Diffraction; X-Ray and
Neutron Diffraction Studies of Amorphous Solids

Bibliography
Azaroff L V, Buerger J 1958 The Powder Method in XRay Crystallography. McGraw-Hill, New York
Barrett C S, Massalski 1966 Structure of Metals:
Crystallographic Methods, Principles and Data, 3rd edn.
McGraw-Hill, New York
Guinier A 1956 Theorie et Technique de la Radiocristallographie. Dunod, Paris
International Tables for X-Ray Crystallography
1969.
Kynoch, Birmingham, UK
Klug , Alexander L 1974 X-Ray Diffraction Proced
ures for Poly crystalline and Amorphous Materials, 2nd

588

edn. Wiley, New York

Lipson S, Steeple 1970 Interpretation of X-Ray Powder
Diffraction Patterns. Macmillan, London
Parrish W 1965 X-Ray Analysis Papers. Philips (Centrex).
Eindhoven, The Netherlands
Parrish W, Ayers G L, Huang C 1982 A versatile
minicomputer x-ray search/match system. Advances in XRay Analysis, Vol. 25. Plenum, New York, pp. 221-9
Parrish W, Huang C 1979 Accuracy of the profile fitting
method for x-ray polycrystalline diffractometry. In: Block
S, Hubbard C R (eds.) 1979 Accuracy in Powder Diffrac
tion, NBS Special Publication No. 567. National Bureau
of Standards, Washington, DC, pp. 95-110
Peiser S, Rooksby , Wilson A J C (eds.) 1955 X-Ray
Diffraction by Polycrystalline Materials. Institute of Phys
ics, London
Schwartz L H, Cohen J 1977 Diffraction from Materials.
Academic Press, New York
Warren 1969 X-Ray Diffraction. Addison-Wesley,
Reading, MA
W. P a r r i s h
[IBM, S a n J o s e , California, U S A ]

LIST OF CONTRIBUTORS

Contributors are listed in alphabetical order together with their addresses. Titles of articles that they have authored follow
in alphabetical order. W h e r e articles are coauthored, this has been indicated by an asterisk preceding the title.

Aubertin, F .
Universitat des Saarlandes
Fachbereich 12.1
Werkstoffwissenschaften
D-6600 Saarbriicken
Germany
*Mossbauer

France
^Ceramic Materials: Cathodoluminescence

Spectroscopy

Averback, R. S.
Materials Science and Technology Division
Building 212
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
USA
*X-Ray and Neutron Diffuse Scattering of RadiationInduced Defects

Bair, . E.
AT&T Bell Laboratories
600 Mountain Avenue
Murray Hill, NJ 07974
USA
Polymers: Tests for Thermal
Polymers: Thermal Analysis

Properties

Bakhru, H.
Physics Department
State University of New York
1400 Washington Avenue
Albany, NY 12222
USA
Ion Backscattering

Analysis

Banerjee, D.
Defence Metallurgical Research Laboratory
Ministry of Defence
Government of India
Kanchanbagh P. O.
Hyderabad 500 258
India
Channelling-Enhanced
Microanalysis
Barrett, R.
CNRS
Laboratoire de Crystallographie
BP 166
F-38042 Grenoble C6dex 09

Analysis

Beall, F . C.
Forest Products Laboratory
University of California
1301 South 46th Street
Berkeley, CA 94720
USA
Wood: Acoustic Emission and
Acousto-Ultrasonic
Characteristics
Benton, J. L.
Room 1E-336
AT&T Bell Laboratories
600 Mountain Avenue
Murray Hill, NJ 07974-2070
USA
Junction Transient
Spectroscopy
Berry, G. C.
Department of Chemistry
Carnegie Mellon University
Pittsburgh, PA 15213
USA
Polymers: Molecular Weight and its

Distribution

Berlin, E. P.
RCA Laboratories
Princeton, NJ 08540
USA
X-Ray Fluorescence

Spectrometry

Blamire, M . G.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Anodization

Spectroscopy

Bleichert, H.
Institut fur Festkorperforschung, Kernforschungsanlage
Julich GmbH
KFA Julich
Postfach 1915
D-5170 Julich
Germany
*Gamma-Ray
Diffractometry
589

List of

Bonnell

Contributors

Bonnell, D. A.
Department of Materials Science and Engineering
University of Pennsylvania
3231 Walnut Street
Philadelphia, PA 19104-6272
USA

Castle, J. E.
Department of Metallurgy and Materials Technology
University of Surrey
Guildford
GU2 5XH
UK

Scanning Tunnelling Microscopy

Corrosion and Oxidation Study Techniques

and

Spectroscopy

Bremer, F. J.

Choi, C. S.

Institut fur Festkorperforschung, Kernforschungsanlage

Julich GmbH
KFA Julich
Postfach 1915
D-5170 Julich
Germany

National Bureau of Standards

Washington, DC 20234
USA
*Texture: Nondestructive
Characterization
Clarke, B.
MS6 Division
Royal Aerospace Establishment
Farnborough
Hampshire
GU14 6TD
UK
^Composite Materials: Nondestructive
Evaluation

*Gamma-Ray

Dijfractometry

Brimhall, J. L.
Battelle-Pacific Northwest Laboratories
PO Box 999
Richland, WA 99352
USA
Electron Microscope Analysis of Defect Clusters,
and Bubbles

Voids

Cahn, R. W.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Microtextural Analysis
Campana, C. F.
Nicolet Corporation
1006 Bubb Road
Cupertino, CA 95014
USA
Single-Crystal X-Ray Diffraction
Campbell, A. M.
Department of Engineering
University of Cambridge
Trumpington Street
Cambridge
CB2 1PZ
UK
Superconducting

Materials:

Conant, F. S.
143 Gunarh Drive
Akron, OH 44139
USA
Elastomers: Tests for Mechanical

Properties

Cooper, M. J.
Department of Physics
University of Warwick
Coventry
CV4 7AL
UK
Compton

Scattering

Cox, S. F. J.

Measurements

Carnahan, C. Jr
Chemical and Structural Analysis Branch
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Gas and Liquid Chromatography
590

Clarke, . T.
Technical Operations Inc.
One Beacon Street
Boston, MA 21108
USA
Gamma Radiography

ISIS Pulsed Muon Facility

Rutherford Appleton Laboratory
Chilton
Didcot
Oxfordshire
OX11 0QX
UK
*Solid State: Study Using Muon Beams
Crist, B.
Department of Materials Science and Engineering
Northwestern University
Evanston, IL 60208

List of
USA
Polymers: X-Ray
Cullis, A. G.
Defence Research Agency
Electronics Division
Royal Signals and Radar Establishment
St Andrews Road
Malvern
Worcestershire
WR14 3PS
UK
* Semiconducting Materials: Electron Microscopy
Davies, G. J.
Department of Metallurgy
University of Sheffield
Mappen Street
Sheffield
SI 3JD
UK
Functions

D e a n , S . W . Jr
Air Products and Chemicals Inc.
PO Box 538
Allentown, PA 18105
USA
Corrosion: Test Methods
Denoyer, E. R.
The Perkin-Elmer Corporation
761 Main Avenue
Norwalk, CT 06859-0215
USA
Laser Sampling Inductively Coupled Plasma
Spectrometry

Elliott, . E.
MST Division
Los Alamos National Laboratory
Mail Stop 549
Los Alamos, NM 87545
USA
*Microengineering of Materials:

Characterization

F a b e r , J. Jr
Materials Science and Technology Division
Building 212
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
USA
*X-Ray and Neutron Diffuse Scattering of RadiationInduced Defects
Fleischer, R. L.
Earth and Environmental Sciences Department
Rensselaer Polytechnic Institute
Troy, NY 12180-3590
USA
Solid-State Nuclear Track Detectors:

Mass

Donahue, P. E.
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
*Nuclear Magnetic Resonance
Spectroscopy

Eades, J. A.
Center for Microanalysis of Materials
University of Illinois at Urbana-Champaign
104 Goodwin Avenue
Urbana, IL 61801
USA
Transmission Electron Microscopy:
Convergent-Beam
and Microdiffraction
Techniques
Early, T. A.
Materials Characterization Laboratory

Frank

General Electric Corporate Research and Development

PO Box 8
Schenectady, NY 12301
USA
Nuclear Magnetic Resonance Spectroscopy of Solids

Scattering

Pole Figures and Orientation Distribution

Contributors

Applications

Fleming, S. J.
MASCA, University Museum
University of Pennsylvania
33rd and Spruce Streets
Philadelphia, PA 19104
USA
Art Forgeries: Scientific

Detection

Flower, . M.
Department of Metallurgy and Materials Science
Imperial College of Science, Technology and Medicine
London
SW7 2AZ
UK
Electron Microscopy,
High-Voltage
Foreman, L. R.
MST Division
Los Alamos National Laboratory
Mail Stop 549
Los Alamos, NM 87545
USA
*Microengineering of Materials:
Characterization
Frank, D. G.
The Surface Center
Department of Chemistry

591

Frank

List of

University of Cincinnati
Cincinnati, OH 45221-0172
USA
*Auger Microscopy,

Angular

Distribution

Fray, D. J.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Gas Sensors, Solid-State
Gallagher, P. K.
Department of Chemistry
The Ohio State University
120 West 18th Avenue
Columbus, OH 43210-1173
USA
Thermal Analysis: Recent Developments

Radiography

Gaskell, D. R.
School of Materials Engineering
Chemical/Metallurgical Engineering Building
Purdue University
West Lafayette, IN 47907
USA
Thermodynamic Activity: Measurement
Gibson, P. N.
Physics Division
Joint Research CentreCEC
Ispra Establishment
1-21020 Ispra (Varese)
Italy
Thin Films: Characterization

by X Rays

Gilmore, R.
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Acoustic

Microscopy

Gonser, U.
Universitat des Saarlandes
Fachbereich 12.1
Werkstoffwissenschaften
D-6600 Saarbriicken
Germany
*Mossbauer
Spectroscopy
592

Graham, C. D. Jr
Department of Materials Science and Engineering
University of Pennsylvania
3231 Walnut Street
Philadelphia, PA 19104-6272
USA
Magnetic Materials:
Measurements

Harrington, J. A.
Hughes Research Laboratories
3011 S Malibu Canyon Road
Malibu, CA 90265
USA
Optical Calorimetry
Hawkins, W. L.
26 High Street
Montclair, NJ 07042
USA
Polymers: Tests for Degradation

and

Stabilization

Haynes, J. M.
School of Chemistry
University of Bristol
Cantocks Close
Bristol
BS8ITS
UK

Garrett, D. A.
National Bureau of Standards
Washington, DC 20234
USA
Neutron

Contributors

Porosity: Characterization

and

Investigation

Hemsley, D. A.
Institute of Polymer Technology
Loughborough University of Technology
Loughborough
Leicestershire
LE11 3TU
UK
Polymers: Light

Microscopy

Henneke, E. G. II
Department of Engineering Science and Mechanics
Virginia Polytechnic Institute and State University
Blacksburg, VA 24061
USA
Vibrothermography
Hofmann, S.
Max-Planck-Institut fur Metallforschung
Institut fur Werkstoffwissenschaft
Seestrasse 92
D-7000 Stuttgart 1
Germany
Depth Profiling
Holik, A. S.
Chemical and Structural Analysis Branch
General Electric Corporate Research and Development

List of

Contributors

Knapp

PO Box 8
Schenectady, NY 12301
USA
Optical Microscopy

Murray Hill, NJ 07974

USA
Polymer Dielectric Properties:

Houston, J. E.
Sandia National Laboratories
Albuquerque, NM 37115
USA

Kallmes, O. J.
M/K Systems Inc.
12 Garden Street
Danvers, MA 01923
USA

*Chemical Analysis of Solid

Suifaces

Hsu, S. L.
Department of Polymer Science and Engineering
University of Massachusetts
Amherst, MA 01003
USA
Polymers: Raman Spectroscopy
Hubbard, A. T.
The Surface Center
Department of Chemistry
University of Cincinnati
Cincinnati, OH 45221-0172
USA
*Auger Microscopy,

Angular

Distribution

Hutchings, . T.
The National Nondestructive Testing Centre
AEA Industrial Technology
Harwell Laboratory
Didcot
Oxfordshire
OX11 OR A
UK
Residual Stresses: Measurement Using Neutron
Diffraction
Jannink, G.
Service de Physique du Solide et de Resonance
Magnetique
Centre d'Etudes Nucleaires Saclay
F-91191 Gif Sur Yvette Cedex
France
Polymers: Neutron Scattering
Johansson, S. A. E .
Department of Nuclear Physics
Lund Institute of Technology
Solvegatan 14
S-223 62 Lund
Sweden
Particle-Induced X-Ray Emission
Johnson, G. E .
Room 7D214
AT&T Bell Laboratories
600 Mountain Avenue

Paper and Paperboard:

Test Methods

Destructive

Mechanical

Testing

Katz, W .
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Secondary-Ion Mass Spectrometry
Kaufman, S.
AT&T Bell Laboratories
2000 Northeast Expressway
Norcross, GA 30071
USA
Polymers: Tests for

Flammability

Kelly, M . A.
Surface Science Laboratories Inc.
1206 Charleston Road
Mountain View, CA 94043
USA
Electron Spectroscopy for Chemical
Kendall, K.
ICI
PO Box 8
Runcorn
Cheshire
WA7 4QE
UK
Powder

Analysis

Mechanics

Kirchheim, R.
Max-Planck-Institut fur Metallforschung
Seestrasse 92
D-7000 Stuttgart 1
Germany
Hydrogen as a Metallurgical

Probe

Klinman, R.
Bethlehem Steel Corporation
Bethlehem, PA 18016
USA
Grain
Size:
Nondestructive
Evaluation
Knapp,
G. S.
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
593

List of

Knapp

USA
*X-Ray Absorption Spectroscopy:
Techniques

EXAFS and XANES

Knowles, . M.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Electron Microscopy,

Contributors
PO Box 8
Schenectady, NY 12301
USA
Liquid Chromatography Mass

Spectroscopy

Lilley, E.
Norton Company
Goddard Road
Northboro, MA 01532-1545
USA
Thermoluminescence

High-Resolution
Lind, . V.

Koenig, J. L.
Macromolecular Science Department
Case Western Reserve University
University Circle
Cleveland, OH 44106
USA
*Elastomers: Spectroscopic

Characterization

Kostorz, G.
Institut fur Angewandte Physik
Zurich
CH-8093 Zurich
Switzerland
Small-Angle Neutron Scattering in Metallurgy
Leake, J. A.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
*Laser Microprobe Mass Spectrometry
Leipziger, F. D.
Northern Analytical Laboratory
3 Northern Boulevard
Amherst, NH 03031
USA
Spark-Source Mass

Spectrography

Lifshin, E.
Chemical and Structural Analysis Branch
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
An Introduction to Investigation and Characterization of
Materials
Electron Microprobe Analysis
Ligon, W. V.
Room 2A40
Building K-l
General Electric Corporate Research and Development
594

Container Corporation of America

PO Box 1648
Wilmington, DE 19899
USA
Polymers: Tests for Mechanical
Properties
Mahajan, S.
Department of Metallurgical Engineering and Materials
Science
Carnegie Institute of Technology
Carnegie Mellon University
Pittsburgh, PA 15213
USA
*Semiconducting

Materials: Electron

Microscopy

Marcus, H. L.
Mechanical Engineering Department
University of Texas
Mail Drop TAY167
Austin, TX 78712
USA
Auger Electron

Spectroscopy

Milne, R. H.
Department of Physics and Applied Physics
University of Strathclyde
Colville Building
North Portland Street
Glasgow
G l 1XN
UK
Reflection Electron

Microscopy

Miodownik, A. P.
Department of Materials Science and Engineering
University of Surrey
Guildford
GU2 5XH
UK
Phase Diagrams and Phase Stability:
Calculations
Mordfin, L.
Office of NDE
National Bureau of Standards
Washington, DC 20234

List of
USA
Residual Stresses: Nondestructive

Evaluation

Morris, W . G.
Building K-l
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Atomic Force

Microscopy

Murch, G. E .
Department of Chemical and Materials Engineering
University of Newcastle
Newcastle
NSW 2308
Australia
Diffusion: Novel Measurement Methods
Murphy, J. C.
Applied Physics Laboratory
The Johns Hopkins University
Johns Hopkins Road
Laurel, M D 20723-6099
USA
Thermal Wave Imaging

Pendry, J. B.
Department of Physics
The Blackett Laboratory
Imperial College of Science, Technology and Medicine
Prince Consort Road
London
SW7 2B2
UK
Electron Diffraction,
Low-Energy
Pethica, J. B.
Department of Materials
University of Oxford
Parks Road
Oxford
3PH
UK
Electron Tunnelling Spectroscopy

Nondestructive

Evaluation

Pottlacher, G.

Page, T. F .
Materials Division
Department of Mechanical, Materials and Manufacturing
Engineering
Herschel Building
University of Newcastle upon Tyne
Newcastle upon Tyne
NE1 7RU
UK

Parrish, W .
[deceased; late of IBM, USA]
X-Ray Powder Diffraction

Patterson, D. J.
Macromolecular Science Department
Case Western Reserve University
University Circle
Cleveland, OH 44106
USA
* Elastomers: Spectroscopic
Characterization

Paper and Paperboard:

Characterization

*Ceramic Materials: Cathodoluminescence

Renton

Pfeifer, R. J.
AccuRay Corporation
650 Ackerman Road
Columbus, OH 43202
USA

Oliver, W . C.
Metals and Ceramics Division
Oak Ridge National Laboratory
PO Box 2008
Oak Ridge, TN 37831
USA
Mechanical Properties
Microprobe
Onoda, G. Y.
157A Metallurgy Building
University of Florida
Gainesville, FL 32611
USA
Ceramic Powders: Packing

Contributors

Analysis

Institut fur Experimentalphysik

Technische Universitat Graz
Petersgasse 16
A-8010 Graz
Austria
Thermophysical Measurements,
Subsecond
Prask, H. J.
NBS Research Reactor
National Bureau of Standards
Washington, DC 20234
USA
*Texture: Nondestructive
Characterization
Purcell, F .
Spex Industries Inc.
3880 Park Avenue
Edison, NJ 08820
USA
Raman Spectroscopy

Renton, W . J.
Advanced Composites Division
595

List of

Renton

USA

Vought Corporation
PO Box 225907
Dallas, TX 75265
USA

Powder

Properties

Russ, J. C.
Analytical Instrumentation Facility
Department of Materials Science and Engineering
North Carolina State University
Box 7916
Raleigh, NC 27695
USA
Fractals
Quantitative

Rye, R. R.
Sandia National Laboratories
Albuquerque, NM 37115
USA
*Chemical Analysis of Solid Surfaces
Seidman, D. N.
Graduate School of Applied Science and Technology
Materials Science Division
Bergamann Building
Givat Ram Campus
Hebrew University of Jerusalem
91904 Jerusalem
Israel
Field-Ion Microscopy: Atom-Probe
Microanalysis
Field-Ion Microscopy: Observation of Radiation Effects
Shrader, S. R.
Shrader Analytical and Consulting Laboratories
3450 Lovett Avenue
Detroit, MI 48210
USA
Organic Mass

Characterization

Sobel, H. R.

Adhesives: Tests for Mechanical

X-Ray Microanalysis,

Contributors

Spectrometry

Applied Research Laboratories

9545 Wentworth Street
Sunland, CA 91040
USA
Optical Emission

Spectroscopy

Srolovitz, D. J.
Department of Materials Science and Engineering
University of Michigan
Ann Arbor, MI 48109-2136
USA
Microstructural Evolution: Computer Simulation
Stone, D. E. W.
MS6 Division
Royal Aerospace Establishment
Farnborough
Hampshire
GU14 6TD
UK
^Composite Materials: Nondestructive
Evaluation
Stoneham, A. M.
AEA Industrial Technology
Harwell Laboratory
Didcot
Oxfordshire
OX11 0RA
UK
*Solid State: Study Using Muon Beams
Stupin, D. M.
MST Division
Los Alamos National Laboratory
Mail Stop 549
Los Alamos, NM 87545
USA
*Microengineering

of Materials:

Characterization

Siegel, R. W.
Materials Science and Technology Division
Argonne National Laboratory
9700 South Cass Avenue
Argonne, IL 60439
USA
Positron Annihilation Spectroscopy of Defects in Metals
Smith, A. L.
Dow Corning
Midland, MI 48640
USA

Sutton, M.
Centre for the Physics of Materials and Department of
Physics
3600 University Street
McGill University
Montreal
Qu6bec
H3A 2T8
Canada

Infrared

X-Ray Diffraction,

Spectroscopy

Smith, D. W.
Department of Metallurgical Engineering
Michigan Technological University
Houghton, MI 49931
596

Time-Resolved

Szarowski, D. H.
Wadsworth Center for Laboratories and Research
New York State Department of Health
PO Box 509
Albany, NY 12201-0509

List of
USA
*Confocal Optical

Contributors

Wunderlich

UK
*Laser Microprobe

Microscopy

Mass

Spectrometry

Wells, O. C.
IBM
Thomas J Watson Research Center
PO Box 218
Yorktown Heights, NY 10598
USA
Scanning Electron Microscopy

Tate, D. R.
11415 Farmland Drive
Rockville, M D 20852
USA
Hardness
Characterization
Tatro, C. A.
L-342
Lawrence Livermore National Laboratory
PO Box 808
Livermore, CA 94550
USA

Weyher, J. L.
MASPEC
Consiglio Nazionale delle Ricerche
ViaChiavari 18/A16/D
1-43100 Parma
Italy

Acoustic

Semiconducting

Emission

Tulin, V. A.
Institute of Solid State Physics
Chernogclovka
Moscowskaya Oblasit
142432
Russia
Electron Spin Resonance
Turner, J. N.
Wadsworth Center for Laboratories and Research
New York State Department of Health
PO Box 509
Albany, NY 12201-0509
USA
*Confocal Optical Microscopy
Veal, B. W.
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
USA
*X-Ray Absorption Spectroscopy:
Techniques

EXAFS and XANES

Vesely, D.
Department of Materials Technology
Brunei University
Uxbridge
UB8 3PH
UK
Polymers: Electron Microscopy

Wallach, E. R.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ

Materials: Characterization

by Etching

Williams, D. B.
Department of Materials Science and Engineering
Whitaker Laboratory
Lehigh University
Bethlehem, PA 18015-3195
USA
Electron Diffraction
Electron Energy-Loss
Spectrometry
Electron Microscopy,
Analytical
Williams, E. A.
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
*Nuclear Magnetic Resonance

Spectroscopy

Wong, A. K.
Aircraft Structures Division
Aeronautical Research Laboratory
506 Lorimer Street
Fishermens Bend
Victoria 3207
Australia
Stress Distribution:

Analysis Using Thermoelastic

Effect

Wright, A. C.
J J Thomson Physical Laboratory
Whiteknights
Reading
RG6 2AF
UK
X-Ray and Neutron Diffraction Studies of Amorphous
Solids
Wunderlich, B.
Department of Chemistry
Rensselaer Polytechnic Institute
Troy, NY 12181
USA
Thermal Analysis: An Overview
597

SUBJECT INDEX

The Subject Index has been compiled to assist the reader in locating all references to a particular topic in the
Encyclopedia. Entries m a y have up to three levels of heading. W h e r e there is a substantive discussion of the topic, the
page numbers appear in bold italic type. As a further aid to the reader, cross-references have also been given to terms
of related interest. These can be found at the bottom of the entry for the first-level term to which they apply. Every effort
has been m a d e to m a k e the index as comprehensive as possible and to standardize the terms used.

ABS (acrylonitrile-butadiene-styrene)
copolymers 332
specific heat 376
transmission electron microscopy 332
Absorption coefficients
bulk absorption 279
optical calorimetry 279
surface absorption 279
thin films 280
AC losses
superconducting materials
calorimetric methods 494
electrical methods 494
Accelerated tests
corrosion 80
polymer stability 357
Acheson method 433
Acoustic emission 1
analog instrumentation 2
composites 64
vibroacoustic emission 64
digital instrumentation 2
fatigue tests 2
fiber-reinforced plastics 551
inspection 3
piezoelectric transducers 2
response characteristics 1
root-mean-square meters 2
scanning electron microscopy 424
signal processing 2
stresses 1
welds 3
wood 551
adhesives 553
applications 552
biological degradation 553
composites 553
cutting 553
defects 552
drying 553
fracture 552
mechanical testing 552
piezoelectric transducers 551
quality control 552
Acoustic microscopy 4
biological materials 4
chemical bonding 4
elastic properties 4
electron acoustic microscopy 7
history 4
photoacoustic microscopy 6
piezoelectric transducers 7

quality assurance 9
scanning acoustic microscopy 4
scanning laser acoustic microscopy 8
surface deformation 4
Acoustic properties
wood 551
Acoustoelastic constants 421
Acoustooptical devices
confocal optical microscopy 69
Acoustoultrasonics
wood 551
applications 552
Activity see Thermodynamic activity
Additives
fluorescence microscopy 342
Adhesive bonding 9
bond lines 64
bond strength 10
peel tests 13
composites 64
creep-compliance curves 10
fatigue 10
hygroscopic expansion 10
mechanical properties 9
nondestructive evaluation 64
powders 399
test methodology 13
test specimens 10
butt joint 12
double lap joint 13
evaluation criteria 10
Iosipescu specimen 13
napkin-ring specimen 13
scarf joint 12
single lap joint 10
thick-adherend symmetric lap joint 11
thermal expansion 10
viscoelastic response 10
Adhesives 9
acoustic emission 553
deformation 14
mechanical properties 9
viscoelastic response 10
wood 553
Adiabatic calorimetry 371
adiabatic thermocouple calorimetry 279
calorimeters 503
Adsorption
gases
particle size distribution 393
porosity 385
porosity 385
599

Adsorption
Brunauer-Emmett-Teller equation 385
flow methods 386
gravimetric methods 386
Langmuir equation 386
vapors 385
volumetric methods 386
scanning tunnelling microscopy 433
solutions 386
vapors 385
ZnO 433
Air pollution
particle-induced x-ray emission 313
Alloys
binary equilibrium 523
defects
amorphous materials 190
crystalline materials 190
see also Metallurgy, specific alloys
- phase transformations 189
Alpha-particle effects 122
Alternating-gradient magnetometers 226
Alumina
optical microscopy 291
packing characterization 48, 49
Aluminum
defects 518, 566
diffuse x-ray scattering 566
electron energy-loss spectroscopy 113
scanning electron microscopy 425
thermal wave imaging 517
Aluminum alloys
Al-Ag alloys 125
Al-Cu alloys 131, 138
Al-Cu-Mg-Ag alloys 133
Al-Li alloys 316
Al-Li-Be alloys 235, 236
Al-Li-Cu-Mg alloys 106
Al-Si alloys 136
Al-Zn alloys 465
high-voltage electron microscopy 139
hydrogen embrittlement 139
optical microscopy 291
phase diagrams 316
small-angle neutron scattering 465
Aluminum carbide
Auger electron spectroscopy 32
Amorphous materials
alloys
hydrogen probes 190
Ni-Ti alloys 190
Ni-Zr alloys 190
Pd-Si alloys 190
electron diffraction 108
metals 263
Mossbauer spectroscopy 263
neutron diffraction 558
interpretation 562
model calculations 562, 563
neutron magnetic diffraction 564
peak fitting 562
real-space correlation functions 559
scattering vector 559
polymers
glass-transition temperature 380
small-angle neutron scattering 351

600

Subject

Index
small-angle x-ray scattering 379, 380
structure 379
x-ray diffraction 558
Compton scattering 560
dispersion technique 560
fluorescent-foil x-ray diffraction 560, 563
interpretation 562
model calculations 562, 563
peak fitting 562
quantitative analysis 560
real-space correlation functions 559
scattering vector 559
x-ray powder diffraction 581, 585
Amyl alcohol
differential thermal analysis 501
Analog instrumentation
acoustic emission 2
Analytical electron microscopy 123
Al-Ag alloys 125
electron energy-loss spectroscopy 125
quantification 126
electron scattering 123, 125
instrumentation 123
scanning transmission electron microscopes 123
Ni-Cr-Fe alloys 125
on-line data manipulation 126
stainless steel 127
transmission electron microscopy 123
x-ray emission 124
x-ray microanalysis 124, 578
Aneroid calorimeters 503
bomb calorimeters 503
Angular correlation
positron annihilation spectroscopy 390
Angular distribution Auger microscopy 34
angular distribution measurement 35
applications 37
Auger electron emission 35
bulk crystals 38
depth profiling 36
iodine 37, 40
monolayers 34
iodine 40
silver 37
multielemental samples 36
multiple Auger transitions 35
platinum 38, 40
real-space imaging 36
single crystals 38
platinum 38
specimen requirements 36
surfaces 34
thin films 34
see also Auger electron spectroscopy
Anisotropy see Magnetic properties
Anodization spectroscopy 14
applications 15
buried layers 16
chemical composition 14
depth profiling 14
GaAs 15
layer uniformity 16
microstructure 14
multilayers 15
Nb-Ta 15

Subject
sample preparation 15
IIIV semiconductors 15
structure 15
theory 14
ionic hopping conduction 14
thin films 14
Antiferromagnetic phases
muon probes 477
Archaeology
particle-induced x-ray emission 313
thermoluminescence dating 528
Art forgeries 16
bronze statuary 21
metallography 22
ceramics 17
Etruscan art 17
history 17
paintings 19
particle-induced x-ray emission 313
radiography 19
particle-induced x-ray emission 313
silver coinage 20
corrosion potential polarography 21
stamps 313
thermoluminescence dating 18
radiography 19
Ash
nondestructive evaluation 303
ASTM tests
flammability 361
ozone resistance 359
polymers 361
weatherability 360
Atmospheric tests
corrosion 80
Atom-probe microanalysis 151
imaging atom-probe mass spectroscopy 153
mass-to-charge ratio 151
microstructure 152
pulsed-laser atom-probe field-ion microscope 153
radiation effects 154
advantages 154
time-of-flight field-ion microscope 152
Atomic force microscopy 23, 436
applications 23, 27
ball bearings 27
brittle materials 27
compact disk 25
computer processing 25
growth processes 28
image display 25
limitations 26
microstructure 27
Ni-based superalloys 27
piezoelectric transducers 23, 24
polymers 28
qualitative analysis 25
quantitative analysis 26
calibration 26
scanning 23, 24
surface defects 26
surface forces 23
thin films 28
Atomic number
mass attenuation coefficients 267

Index

Austenitic

stainless

steel

scanning electron microscopy 423

x-ray microanalysis 578
Atomic structure
angular distribution Auger microscopy 34
atomic force microscopy 24
channelling-enhanced microanalysis 51
electron diffraction 104
electron energy-loss spectroscopy 112
high-resolution electron microscopy 127
infrared spectroscopy 193
low-energy electron diffraction 110
mass-to-charge ratio 151
scanning tunnelling microscopy 427
x-ray absorption spectroscopy
extended x-ray absorption fine structure 555
x-ray absorption near-edge fine structure 555
x-ray crystallography 457
see also Structure
Auger electron spectroscopy 28
A14C 32
angular distribution 34
applications 33
Auger electron energy 29
measurement 31
Auger signals 30
backscattering factors 31
CO 57
catalytic properties 33
ceramics
MgO 34
chemical effects 21
Co(CO)3NO 57
corrosion 76
decay processes 29
depth profiling 32, 83
Fe-Cr-Ni stainless steel 89, 90
Ni-Cr-Fe alloys 90
Ni-In alloys 89, 90
Poisson distribution 89
Ta-Si multilayers 86, 87
TiN-Si multilayers 87
escape depths 29
fracture 33
graphite 32
inert-ion sputtering 32
interfaces 33
ionization cross sections 31
molecular structure 406
Mo(CO) 57
near-surface region 32
NO 57
peak widths 31
quantitative analysis 32
scanning electron microscopy 423
semiconducting materials 33
silver 31
solid surfaces 54, 57
surfaces 29
vacuum requirements 33
valence levels 57
ZnO 433, 436
see also Angular distribution Auger microscopy
Austenitic stainless steel
microstructure 236

601

Austenitic

stainless

steel

Subject

microtextural analysis 256

weld embrittlement 235, 237
see also Stainless steel
Autofluorescence
polymers 342
Autofrettage
neutron diffraction 415
Backscattering
electron backscattering patterns 257
ion backscattering analysis 199
Rutherford backscattering 200
scanning electron microscopy 241, 423
ultrasonic techniques 180
Balances
Faraday balance 488, 506
magnetic balances 225
microbalances 75
quartz piezobalances 75
thermobalances 75, 507
Ball bearings
atomic force microscopy 27
Band structure
cathodoluminescence 43
Barium chloride
differential thermal analysis 501
Barkhausen effect
grain size evaluation 181
residual stresses 421
Basis weight
paper and paperboard 302
Becke line test
polarized-light microscopy 339
Beer's law 521
Beta emission
muon probes 474
Beta sensors
nondestructive evaluation 303
Binding energy
electron spectroscopy for chemical analysis 140
Biological materials
acoustic emission 4
atomic force microscopy 438
confocal optical microscopy 69
electron spin resonance 147
electrospray liquid chromatography mass spectrometry 223
human transferrin 224
particle-induced x-ray emission 312, 313
peptides 223
Raman spectroscopy 404
solid-state nuclear track detection 471
spark-source mass spectrography 483
tissue 461
x-ray crystallography 461
Birefringence
polarized-light microscopy 338
polymers 338
polypropylene 339
Bisphenol A polycarbonate resin
carbon-13 nuclear magnetic resonance spectroscopy 275
Bitter magnets 230
Boltzmann factor 145
Bomb calorimeters 503
Bonding (chemical)
acoustic emission 4

602

Index
electron spectroscopy for chemical analysis 140
Mylar 141
organic compounds 294
scanning tunnelling microscopy 427
Borides
laser microprobe mass spectrometry 211
Boron nitride
electron energy-loss spectroscopy 115
electron microprobe analysis 119
Bragg's law
convergent-beam transmission electron microscopy 540
electron diffraction 105
gamma-ray diffractometry 166
neutron diffraction 413
texture 498
single-crystal x-ray diffraction 568
x-ray crystallography 116, 458
x-ray diffraction 418
x-ray powder diffraction 568, 581
Bridges
dielectric measurements 327
General Radio Company capacitance bridge 327
Harris low-frequency bridge 327
Brinell hardness test 183
Brittle materials
atomic force microscopy 27
Bromobutane
mass spectrometry 294
Bronze statuary
art forgeries 21
metallography 22
Brunauer-Emmett-Teller equation 385
Bubbles
helium 122
molybdenum 122
neutron effects 122
transmission electron microscopy 122
Building materials
flammability tests 363
Bunsen ice calorimeter 502
Bursting strength
destructive mechanical testing 301
2-Butanone
mass spectrometry 295
Calcium oxalate
thermogravimetry 505
Calibration
atomic force microscopy 26
infrared spectrometers 195, 196, 199
ion sputtering 84
laser sampling inductively coupled plasma mass
spectrometry 218
nondestructive evaluation 308
scanning tunnelling microscopy 435
x-ray fluorescence spectrometry 577
x-ray microanalysis 580
Caliper
nondestructive evaluation 307
Calorimeters
adiabatic calorimeters 503
aneroid calorimeters 503
compensating calorimeters 503
isothermal calorimeters 502
laser calorimeters 279

Subject
Ohio State University calorimeter 364
scanning calorimeters 503
Calorimetry 502
adiabatic calorimetry 371
thermocouple calorimetry 279
differential scanning calorimetry 508
applications 509
measuring cell 500
polymers 371, 375
qualitative analysis 375
thermal degradation 359
thermosetting resins 376
dynamic calorimetry 371
flammability of polymers 364
optical calorimetry 279
Peltier effect 503
specific heat 371
superconducting materials 494
thermodynamic properties 503
see also Thermal analysis
Capillarity
capillary condensation 388
contact angle 387
imbibition rate 389
Kelvin equation 387
Laplace equation 387
mercury porosimetry 387
pore size 387
porosity 387
specific surface 389
suction porosimetry 388
Washburn equation 389
wetting 387
Carbon
carbon-13 nuclear magnetic resonance spectroscopy 101,
270
Carbon-fiber-reinforced composites
impact damage 60, 62
nondestructive evaluation 58
Carbon monoxide
Auger electron spectroscopy 57
chemical analysis 54
differential thermal analysis 509
ultraviolet photoelectron spectroscopy 56
Carbon steel
low-carbon steel 323
texture 323
Castings
gamma radiography 163
Catalysts
Auger electron spectroscopy 33
differential thermal analysis 509
gas detectors 178
Cathodoluminescence
band structure mapping 43
ceramics 43
defect densities 43, 45
diamond 46
dislocation array 45
electron-hole recombination 43, 45
imaging mode 44
impurity levels 43
instrumentation 44
MgO 45
microstructure 43

Index

Chemical

analysis

A1 20 - Z r 0 2 45
Zr0 2 45
phase distributions 45
photon emission mechanisms 43
sample preparation 44
scanning electron microscopy 424
semiconducting materials 43
SiC fiber 46
spatial resolution 44
spectroscopy 44
Ceramics
Al 20 3-water mixtures 48
A l 2 0 3 - Z r 0 2 45
art forgeries 17
Auger electron spectroscopy 34
cathodoluminescence 43
dating
thermoluminescence 528
defect densities 43, 45
diamond 46
dynamic mechanical analysis 513
gas sensors 175
impurities 43
MgO 45
microstructure 43, 45
particle-induced x-ray emission 313
phase distributions 45
powders
density 47, 48
mixtures 48
packing characterization 47
particulate system 47
porosity 48, 49
specific volume 47, 48
voids 48
volume 47
volume fraction 48
SiC fiber 46
solid electrolyte gas sensors 175
terracotta 17
Ti0 2-coated A1 20 3 513
Zr0 2 45
see also specific compounds
Channelling
ion backscattering
analysis 203
+
Si-BF 2 203
selected-area channelling patterns 257
see also Electron channelling
Channelling-enhanced microanalysis 50
applications 50
atomic structure 51
axial channelling 51
beam convergence 53
electron energy-loss spectroscopy 51
electron scattering 50
planar channelling 50
probe size 53
sensitivity 53
Charpy impact test 369
Chemical analysis
CO chemisorption 54
electron energy-loss spectroscopy 125
electron microprobe analysis 115
electron microscopy 123
electron spectroscopy 139

603

Chemical

analysis

Subject

ion backscattering analysis 199

laser microprobe mass spectrometry 209
organic materials 211, 213
Raman spectroscopy 403
concentration 404
solid-state nuclear track detectors 471
solid surfaces 53
x-ray microanalysis 577
thin films 536
see also Elemental analysis
Chemical bonds see Bonding (chemical)
Chemical composition
anodization spectroscopy 14
depth profiling 83
infrared spectroscopy 193
liquid chromatography mass spectrometry 220
mixtures 220
Chemical inhomogeneities
etching 445, 450
dopant concentration 45
growth striations 450
second-phase particles 450
semiconducting materials 445
GaAs 450
Chemical sensors 775
Chemical shift
nuclear magnetic resonance spectroscopy 270, 273
carbon-13 nuclear magnetic resonance spectroscopy 272
chemical shift anisotropy 273
Chemiluminescence
polymers 359
Chemisorption
CO 54
Chromatography
polymers
molecular weight distribution 350
see also Gas chromatography, Liquid chromatography,
Size-exclusion chromatography
Chromium alloys
Cr-Fe-Si alloys 317
Cr-W alloys 321
Clay
x-ray spectroscopy 304
Cliff-Lorimer equations 125
Coal
secondary-ion mass spectrometry 444
thermogravimetry-thermomagnetometry 508
Coatings
inertial-confinement fusion
electron beam characterization 241
x-ray inspection 243
optical calorimetry 280
Coercive force 232
Colorimetry
filter colorimeters 304
Colors
nondestructive evaluation 304
pigment analysis
particle-induced x-ray emission 313
radiography 19
Compaction
396
Compensating calorimeters 503
Composites
acoustic emission 551, 553
Al-SiC 114

604

Index
boron epoxy 549
carbon-fiber-reinforced materials 58
defects 59
delamination 59, 61, 547, 548
dynamic mechanical analysis 511
electron energy-loss spectroscopy 114
fiber-reinforced plastics 551
graphite-epoxy prepreg 511
nondestructive evaluation 58
adhesive-bonded joints 64
defects 59
delamination 59, 61, 547, 548
fabrication processes 59
laminates 59
porosity 59
residual stresses
neutron diffraction 416
SiC-Al 20 3 416
SPATE 484
thermal wave imaging 515
vibrothermography 547
wood-based composites 553
Compressive strength
polymers 368
Compton scattering 65
amorphous solids 560
concrete 66
densitometry 67
electronic properties 67
gamma-ray scattering 65
line shape analysis 66, 67
synchrotron sources 66, 67
theory 65
Compton profiles 66
Klein-Nishina cross sections 65
voids 67
x-ray diffraction 560
x-ray scattering 65
Computer-aided tomography
composites 62
voids 63
Computer applications
confocal optical microscopy 68, 72
dielectric measurements
transient methods 326
differential scanning calorimetry 371
inertial-confinement fusion
electron beam characterization 243
x-ray inspection 244
mechanical testing 370
nondestructive evaluation 302
Raman spectroscopy 355
secondary-ion mass spectrometry 442
SPATE 484
x-ray crystallography 457
x-ray powder diffraction 582
phase identification 583
Computer simulation
microstructural evolution 246
continuum models 246
equation-of-motion methods 252
Monte Carlo methods 247
Concentration
Raman spectroscopy 404
Concrete

Subject
mass attenuation 66
Conductive polymers
scanning tunnelling microscopy 433
Confocal optical microscopy 68
beam scanning instruments 69
acoustooptical devices 69
specimen scanning systems 69
computer systems 68, 72
graphics workstations 68, 72
confocal imaging 68
fluorescence microscopy 69
plexiglass 71
polarization 69
three-dimensional visualization 69
fibers 71
inside transparent materials 71
integrated circuits 72
photoresists 72
surfaces 70
see also Optical microscopy
Contact area
mechanical properties microprobe 233
Convergent-beam electron diffraction 107
copper 108
garnet 107
microscopy 537
Convergent-beam transmission electron microscopy 537
applications 538
Bragg's law 537
crystal symmetry 539
electron probes 541
film thickness 538
higher-order Laue zones 539, 541
lattice parameters 539
phase analysis 538
strain 539
unit cells 541
V 3Si 541
zone-axis patterns 538
Conversion electron Mossbauer spectroscopy 263
Copolymers
ABS copolymers
transmission electron microscopy 332
small-angle neutron scattering 352
Copper
convergent-beam electron diffraction 108
crystal growth 167
gamma-ray diffractometry 167
hardness 237
ion implantation 237
texture 498
direct pole figures 323
Copper alloys
Cu-Fe alloys 261
Cu-Ni alloys 118
Corrosion 75
aqueous corrosion 74, 77
Auger electron microscopy 76
chemistry 76, 78
Ellingham diagrams 76
classification 74
electrochemical methods 77, 79, 80
polarography 77
potentiometry 77
ellipsometry 76

Index

Crystal

growth

film thickness 76
gaseous corrosion 74
gravimetry 75
kinetics 74, 77
microtextural analysis 258
morphology 76, 78
resistance 258
Rutherford backscattering 77
steel 508
stress-corrosion cracking 78
structure 76
test methods 78
accelerated tests 80
corrosion resistance 79
corrosivity 79
electrical resistance 79
field tests 79
immersion tests 80
laboratory tests 79
objectives 79
quality assurance 79
service tests 79
simulated atmospheric tests 80
standards 79, 80
thermomagnetometry 508
volumetric methods 75
weight gain 75
x-ray electron probe microanalyzer 76
x-ray excited photoelectron spectroscopy 76
Young's modulus 77
see also Oxidation
Corrosion potential polarography 21
Cottrell atmospheres 448
Counterfeiting see Art forgeries
Cracking
aluminum 518
autofrettaged tubing 415
neutron diffraction 415
polymers
polyethylene 330
small-angle x-ray scattering 380
scanning electron microscopy 330
thermal wave imaging 517
Creep
polymers 368
Creep-compliance curves 10
Critical current density 487
dc hysteresis 493
direct measurements 492
inductive techniques 493
Critical field 490
resistive measurements 491
Critical temperature 487, 489
inductive measurements 489
resistive measurements 489
Cryogenics
inertial-confinement fusion 239
Crystal-diffraction spectrometers
electron microprobe analysis 116
flow proportional counters 117
Crystal growth
gamma-ray diffractometry 166
copper 167
scanning tunnelling microscopy 432
SiC 432

605

Crystal

orientation

Subject

Crystal orientation
scanning electron microscopy 423
Crystal structure
convergent-beam transmission electron microscopy 537
symmetry 539
gamma-ray diffractometry 165
imperfections 586
lattice constants 457
muon probes 473
phase angle 459
semiconducting materials 452
space groups 457
structure factors 459
symmetry 539
transmission electron microscopy 452
unit cells 457
x-ray absorption spectroscopy
extended x-ray absorption fine structure 555
x-ray absorption near-edge fine structure 555
x-ray crystallography 457
x-ray powder diffraction 581
see also Structure
Crystalline materials
alloys
Nb-V alloys 190
hydrogen probes 190
angular distribution Auger microscopy 38
electron spin resonance 147
polymers
small-angle neutron scattering 352
solid-state nuclear track detection 468
Crystallinity
Raman spectroscopy 404
Crystallites
orientation distribution functions
texture 322, 325
Euler angles 325
size
x-ray powder diffraction 581, 587
Crystallization

*VA. 263

Fe 7 8Mo 263
metals 263
polymers 380
Cuprous chloride
defects 474
Curie method 225
Curie temperature 229
Curing
thermosetting resins 376
Current imaging tunnelling spectroscopy 429
silicon 429, 430
Cutting
wood
acoustic emission 553
Damage
vibrothermography 547
Darcy's law 384
Dating
solid-state nuclear track detectors 471
Debye-Waller factors
low-energy electron diffraction 110
Mossbauer spectroscopy 259
Deep-level transient spectroscopy 205

606

Index
applications 207
GaAs 207
hydrogen passivation 207
InP 207
semiconductor devices 207
silicon 205, 206
theory 206
Defects
aluminum
diffuse x-ray scattering 566
electron-irradiated 566
alloys
amorphous materials 190
crystalline materials 190
Nb-V alloys 190
Ni-Ti alloys 190
Ni-Zr alloys 190
Pd-Si alloys 190
atomic force microscopy 26
ceramics
cathodoluminescence 43, 45
composites
nondestructive evaluation 59
convergent-beam transmission electron microscopy 537
CuCl 474
deep-level transient spectroscopy 205
electron diffraction 107
high-voltage electron microscopy 137
inertial-confinement fusion 238
electron beam characterization 241
x-ray inspection 244
junction transient spectroscopy 205
metals
diffuse x-ray scattering 565
dislocation density 188
electronic states 390
field-ion microscopy 154
grain boundaries 188
hydrogen probes 187
interstitials 187
neutron diffuse elastic scattering 566
positron annihilation spectroscopy 390
vacancies 188
muon probes 474
radiation-induced defects
diffuse x-ray scattering 565
diffuse elastic scattering 566
reflection electron microscopy 410
scanning electron microscopy 423
scanning tunnelling microscopy 432
semiconducting materials
etching 445
GaAs 207
InP 207
silicon 205
transmission electron microscopy 120, 452
wood
acoustic emission 552
x-ray powder diffraction 581, 586
see also Disorder
Deformation
polymers 380
Degradation
polymers 357
autofluorescence 342

Subject
thermal degradation 357
Delamination
nondestructive evaluation 59
ultrasonic inspection 61
vibrothermography 547, 548
Dendritic growth
equations-of-motion simulation 252
Densitometry 67
Density
packing characterization 47, 48
porosity 384
powders 395
ceramics 47, 48
Depth profiling 83
anodization spectroscopy 14
Auger electron spectroscopy 32, 83
angular distribution Auger microscopy 36
GaAs-AlGaAs superlattices 442, 443
GaAs:Be441,443
ion backscattering analysis 200
ion sputtering 83
laser microprobe mass spectrometry 213
laser sampling inductively coupled plasma mass
spectrometry 217
Rutherford backscattering 96
secondary-ion mass spectrometry 83
GaAs-AlGaAs superlattices 442, 443
GaAs:Be441,443
secondary-ion mass spectroscopy 95
thermal wave imaging 516
x-ray photoelectron spectrometry 83
Destructive mechanical testing
paper and paperboard 299
bond failure 301
bursting strength 301
fiber pullout 301
load-elongation characteristics 299
sheet failure 301
shrinkage 299
tearing strength 301
tensile strength 301
see also Mechanical testing, Nondestructive evaluation
Dew point 521
Diamond
cathodoluminescence 46
x-ray powder diffraction 582
Dielectric constant see Permittivity
Dielectric loss tangent
polymers 326
Dielectric measurements
bridges 327
electrode systems 328
microwave techniques 328
polymers 325
resonant methods 327
capacitance variation method 327
re-entrant cavity 327
solid-state nuclear track detection 468
transient methods 326
computer processing 326
permittivity 326
transmission lines 326, 328
Dielectric properties
polymers 325
theory 325

Index

Dilatometry

admittance 326
dielectric loss tangent 326
permittivity 326
Differential interference-contrast microscopy
polymers 341
epoxy resins 341
fracture 341
polypropylene 342
quantitative analysis 341
spherulitic morphology 342
surface roughness 341
Differential scanning calorimetry 508
applications 509
measuring cell 500
polymers 371, 375
polymer blends 375
thermal degradation 359
thermosetting resins 376
quantitative analysis 375
see also Differential thermal analysis
Differential thermal analysis 499, 508
amyl alcohol 501
applications 509
BaCl 501
heat flow 499
iron 501
metastable systems 500
polyoxymethylene 501
oxidation of CO 509
phase diagrams 500
polymers
poly (ethylene terephthalate) 501
thermal degradation 359
quantitative analysis 499
see also Differential scanning calorimetry
Differential interference-contrast microscopy 290
Diffuse x-ray scattering
electron-irradiated aluminum 566
metals
aluminum 566
nickel 566
radiation-induced defects 565
Diffusion
diffusion coefficients 92
Fick's laws 445
hydrogen
in palladium 189
metallurgical probe 187, 189
Mossbauer spectroscopy 94, 264
nuclear magnetic resonance 93
nuclear reaction analysis 95
polymers
molecular weight distribution 350
thermogravimetric analysis 377
quasielastic neutron scattering 92
coherent scattering function 93
incoherent scattering function 92
radiotracer techniques 92
Rutherford backscattering analysis 96
secondary-ion mass spectroscopy 95
self-diffusion coefficients
lithium 94
Digital instrumentation
acoustic emission 2
Dilatometry 503

607

Dilatometry
thermodilatometry 511
Discharges
optical emission spectroscopy 285
Discontinuities
acoustic emission /
Dislocations
dislocation loops
nickel 121
diffuse x-ray scattering 566
etching
dislocation density 448
etch hillocks 447, 448
etch pits 447, 449
GaAs 447
InP 448, 449
semiconducting materials 445
junction transient spectroscopy 205
metals
hydrogen probes 188
MgO 45
reflection electron microscopy 410
screw dislocations 410
semiconducting materials 445
GaAs 447, 454
InP 448, 449, 453
substructure
equations of motion simulation 253
transmission electron microscopy 453
Disorder
low-energy electron diffraction 109
see also Defects
Dispersive spectrophotometers 304
Dopants
etching 450
junction transient spectroscopy 205
semiconducting materials
ion implantation 443
molecular-beam epitaxy 443
secondary-ion mass spectrometry 443
Doppler broadening
positron annihilation spectroscopy 390
Dosimetry
archeological ceramics 528
geological 528
solid-state nuclear track detectors 471
thermoluminescence 527
Drying
wood
acoustic emission 553
Ductility
microtextural analysis 258
Dyes
rhodamine-B 213
Dynamic calorimetry 371
Dynamic mechanical analysis 511
applications 511
ceramics 513
composites 511
graphite-epoxy prepreg 511
instrumentation 513
thermal expansion 511
see also Thermodilatometry
Eddy current inspection 64
Effusion

608

Subject

Index
vapor pressure
gamma-ray spectrometry 522
mass spectrometry 522
thermodynamic activity 521
Elastic properties
acoustic emission 4
elastic deformation 418
nondestructive evaluation 308
paper and paperboard 308
polymers 368
powders 399
x-ray powder diffraction 418, 587
Elastic scattering
concrete 67
Elastomers
applications 103
carbon-13 nuclear magnetic resonance 101
fabrication 102
infrared spectroscopy 99, 101
mechanical properties 101
microstructure 99
molecular structure 99
plasticity 102
polybutadiene 99
polyisoprene 101
proton nuclear magnetic resonance 100, 101
quality control 102
specifications 103
spectroscopy 99
viscoelasticity 102
Electric admittance
polymers 326
Electric quadrupole interactions
Mossbauer spectroscopy 261
Electrical conductivity
solid-state gas sensors 177
humidity 177
superconducting materials 487
Electrical resistance 79
Electrochemistry
corrosion 77, 79, 80
etching 446
gas sensors 175
hydrogen 176
Nernst equation 175
oxygen 176
sulfur-containing gases 176
liquid chromatography 173
particle size distribution 393
thermodynamic activity 524
Electrode systems
dielectric measurements 328
three-terminal electrode systems 328
Electron acoustic microscopy 7
Electron backscattering patterns
microtextural analysis 257
Electron beam characterization
inertial-confinement fusion 240
thermal wave imaging 518
Electron beam damage
transmission electron microscopy
energy-loss analysis 333
polymer thin films 332
x-ray analysis 333
Electron channelling

Subject
scanning electron microscopy 425
see also Channelling
Electron diffraction 104
Al-Li-Cu-Mg alloys 106
amorphous materials 108
atomic structure 104
convergent-beam electron diffraction 107
defects 107
diffraction patterns 104
indexing 105
Kikuchi lines 108
low-energy electron diffraction 108
reflection high-energy electron diffraction 409
second-phase particles 107
theory 104
Bragg's law 105
Ewald spheres 105
Laue equations 104
Electron energy-loss spectroscopy 112
aluminum 113
Al-SiC composites 114
analytical electron microscopy 125
BN 115
channelling-enhanced microanalysis 51
detection limits 113
energy-loss spectrum 112
deconvolution 113
plasmon peak shifts 113
quantification 113
fine-structure effects 114, 126
imaging 114
instrumentation 112
limitations 114
lithium 112
low-energy-electron loss spectroscopy 54, 55
phase analysis 538
signal-to-noise ratio 127
spatial resolution 113
stainless steel 127
Electron energy states
electron microprobe analysis 116
emeraldine hydrochloride 434
scanning tunnelling microscopy 428, 434
silicon 429, 430
ZnO 433, 435
see also Vibrational states
Electron-hole recombination
cathodoluminescence 43, 45
scanning electron microscopy 424
Electron irradiation
aluminum
diffuse x-ray scattering 566
Electron microprobe analysis 115
BN 119
Cu-Ni alloys 118
electron energy level transitions 116
electron microprobe analyzers 115
applications 118
crystal-diffraction spectrometers 116
energy-dispersive spectrometers 117
operating principles 115
quantitative analysis 118
microstructure 119
molecular structure 406
Moseley's law 115

Index

Electron

spin

resonance

x-ray emission 115

x-ray maps 119
see also Electron microscopy, Microprobe analysis
Electron microscopy
chemical analysis 123
high-resolution electron microscopy 127
high-resolution high-voltage electron microscopy 136
high-voltage electron microscopy 134
microstructure 120
particle size distribution 392
polymers 329
replica techniques 330
specimen preparation 329
semiconducting materials 452
see also Electron microprobe analysis, Reflection electron
microscopy, Scanning electron microscopy, Scanning
transmission electron microscopy, Transmission
electron microscopy
Electron-nuclear double resonance 148
Electron optics
high-resolution electron microscopy 128
high-voltage electron microscopy 135
scanning transmission electron microscopy 124
Electron probes
convergent-beam transmission electron microscopy 541
Electron scattering
analytical electron microscopy 123, 125
high-resolution electron microscopy 128
inelastic electron scattering 125
low-energy electron diffraction 110
Electron spectroscopy for chemical analysis 139
applications 144
characteristics 139
chemical bonding 140
chemical shifts 140
history 140
instrumentation 143
detector systems 144
electron spectrometers 143
hemispherical analyzers 143
x-ray sources 143
molecular structure 406
Mylar 141
polymers 142
quantitative analysis 142
quartz 143
spectrometers 143
theory 140
binding energy 140
see also X-ray photoelectron spectroscopy
Electron spin resonance 144
applications 148
biological materials 147
Boltzmann factor 145
dipole-dipole interactions 146
electron-nuclear double resonance 148
electron spin resonance spectrometers 145
Fermi contact interactions 146
free radicals
crystalline materials 147
organic materials 146
hyperfine field interactions 146
molecules 147
quantum mechanics 144
spin-lattice relaxation 145

609

Electron

spin

resonance

spin-orbit interactions 147

spin-spin relaxation 146
transition metal ions 147
triplet spin state 147
Zeeman effect 144, 146
Electron tunnelling spectroscopy 149
applications 150
Fermi levels 149
inelastic tunnelling spectroscopy 149
metal-oxide-metal structures 149
molecules 149
semiconductors 149
superconductors 149
Josephson effect 150
vacuum tunnelling 150
see also Scanning tunnelling microscopy, Tunnelling
spectroscopy
Electronegativity
Mossbauer spectroscopy 261
Electronic devices
deep-level transient spectroscopy 207
see also Integrated circuits
Electronic properties
Compton scattering 67
electron energy-loss spectroscopy 112
electron spin resonance 144
Fermi contact interactions 146
triplet spin state 147
Zeeman effect 144, 146
electron tunnelling spectroscopy 149
Fermi levels 149
positron annihilation spectroscopy 390
x-ray absorption spectroscopy
extended x-ray absorption fine structure 555
x-ray absorption near-edge fine structure 555
Electrospray method 223
Elemental analysis
electron microprobe analysis 115
electron spectroscopy for chemical analysis 139
imaging atom-probe mass spectroscopy 153
inertial-confinement fusion 242
laser sampling inductively coupled plasma mass
spectrometry 215
optical emission spectroscopy 281
particle-induced x-ray emission 309
spatial distribution 311
secondary-ion mass spectrometry 438
lateral distribution 443
solid-state nuclear track detectors 471
spark-source mass spectrography 480
x-ray fluorescence spectrometry 570
x-ray microanalysis 577
ZAF method 242
see also Chemical analysis
Ellingham diagrams 76
Ellipsometry 76
Elongation
polymers 366
Elutriation
particle size distribution 392
Emanation thermal analysis 510
Emeraldine hydrochloride 434, 436
Empirical relationships
phase diagram calculations 317
Energy-dispersive spectrometers 538

610

Subject

Index
analytical electron microscopy 124
electron microprobe analysis 117
signal-to-noise ratio 127
x-ray diffraction 569
Energy-loss analysis
electron beam damage 333
Enthalpy
polymers 373
Entropy
phase diagram calculations
first-principle calculations 321
semiempirical relationships 319
Epitaxial films
x-ray powder diffraction 585
Epoxy resins
differential interference-contrast microscopy 341
Epstein test 231
Equation of motion methods
microstructural evolution 252
dendritic growth 252
dislocation substructure 253
front tracking 252
grain growth 253, 254
particle methods 253
Etching
chemical inhomogeneities 445, 450
defects 445
dislocations
dissolution kinetics 447
etch hillocks 447, 448
etch pits 447, 449
GaAs 447
InP 448, 449
thermodynamics 447
electrochemical reactions 446
etch rate 445
photoetching 446, 449, 451
selective etching 445
semiconducting materials 445
GaAs 447
InP 448, 449
solid-state nuclear track detection 468
wet chemical etching 445
Ethyl chloride
mass spectrometry 293
Ethylbenzene
carbon-13 nuclear magnetic resonance spectroscopy 272
proton nuclear magnetic resonance spectroscopy 270
Euler angles 325
Evolved gas analysis 509
applications 510
emanation thermal analysis 510
Novolac epoxies 510
TaSi2 thin films 511
Ewald spheres 105
Extended energy-loss fine-structure spectroscopy 114, 126
Extended x-ray absorption fine structure 535, 555
advantages 558
fluorescence detection 536
Fourier transforms 556
instrumentation 557
limitations 558
nickel 555
radial distribution functions 556
reflections 535

Subject
theory 555
uranium 556
x-ray sources 557
Fabrication see Processing
Faraday balance 488, 506
Faraday method 225
Faraday-Mossbauer effect 264
Fast atom bombardment
liquid chromatography mass spectrometry 224
Fatigue
acoustic emission 2
adhesive bonds 10
composites 548
neutron diffraction 415
vibrothermography 548
Feedback
thermal analysis 513
Femtosecond time resolution
thermophysical measurements 531
Fermi levels
electron spin resonance 146
electron tunnelling spectroscopy 149
hydrogen 187
metallurgical probes 187
Ferrites
nickel zinc ferrite 506
Ferromagnetic resonance frequency 230
Fiber-reinforced plastics
acoustic emission 551
Fibers
confocal optical microscopy 71
paper and paperboard
destructive mechanical testing 299
fiber pullout 301
polyesters 503
polyethylene 71
SiC 46
Fick's laws 445
Field-ion microscopy
atom-probe microanalysis 151
microstructure 152
defects
metals 154
field evaporation 151
ionic model 152
pulse-field evaporation 152
field-ion microscopes 151
resolution 152
time-of-flight atom-probe field-ion microscopes 152
field ionization 151
gold 151
radiation effects 154
advantages 154
applications 155
contrast effects 154
displacement cascades 154
monovacancies 154
voids 155
Films see Foils, Thin films
Filter colorimeters 304
Finite-element analysis
SPATE 484
Fire see Flammability
First-principle calculations

Index

Foner

magnetometer

phase diagrams 320

entropy of mixing 321
interaction energies 320
lattice stabilities 320
magnetic parameters 321
Flame ionization
gas chromatography 171
Flame spectroscopy 283
burners 283
Flammability
fire development regimes 361
developing regime tests 361, 363
fully developed regime tests 361
incipient regime tests 361
polymers 361
ASTM test methods 361
building materials 363
calorimetry 364
fire endurance 365
flame spread classification 364
flash-ignition temperature 361
heat release 364
horizontal tests 363
oxygen index test 362
polyisocyanurate 364
polyurethane foam 364
relative flammability 362
self-ignition temperature 262
smoke value 363, 365
Steiner tunnel furnace 363
vertical tests 363
Flexural strength
polymers 368
Flory-Schulz distribution functions 344
Flow
Hall flowmeter 395
porous media 386
powders 396
Fluorescence
extended x-ray absorption fine structure 536
Raman spectroscopy 406
x-ray microanalysis 578
see also X-ray fluorescence spectrometry
Fluorescence microscopy
confocal optical microscopy 69
biological materials 69
polymers 342
additives 342
autofluorescence 342
poly(vinylidene chloride) 342
Fluorescent-foil x-ray diffraction 560, 563
Flux creep 493
Flux flow 491
Flux pinning 492
Fluxgate magnetometers 228
Fluxmeters 226
Foams
flammability 364
polyisocyanurate 364
polyurethane 364
Focusing x-ray diffractometers 582
Foils
Al-Si alloys 136
high-voltage electron microscopy 134, 136
Foner magnetometer 227

611

Forgeries
Forgeries see Art forgeries
Fourier transform spectroscopy
extended x-ray absorption fine structure 556
infrared spectroscopy 195
nuclear magnetic resonance spectroscopy 271
free-induction decay 271
Fractals 156
fractal dimension
Brunauer-Emmett-Teller measurement 159
Feret's diameter 158
Koch islands 156
linear least-squares fit 158
measurement 157
raster-scanned images 159
Richardson plots 156
self-similarity 157
shape analysis 156
applications 160
fracture 160
liquid droplets 160
mammalian brains 160
particle aggregation 160
river systems 160
surfaces 156, 159
Fracture
acoustic emission 552
Auger electron spectroscopy 33
confocal optical microscopy 70
fractals 160
microtextural analysis 258
polymers
differential interference-contrast microscopy 341
polyethylene 330
scanning electron microscopy 330
SPATE 484
steels 33
wood 552
Free energy
phase diagram calculations 315
Free radicals
electron spin resonance
crystalline materials 147
organic materials 146
Friction 399, 401
Fugacity 520
Fusion
laser sampling inductively coupled plasma mass
spectrometry 217
see also Inertial-confinement fusion
Gallium arsenide
anodization spectroscopy 15
defects
deep-level transient spectroscopy 207
muon probes 475
dislocations
etch hillocks 448, 450
etch pits 447
transmission electron microscopy 454
etching
chemical inhomogeneities 450
photoetching 446, 451
GaAs-AlGaAs superlattices 442, 443
precipitates 451
transmission electron microscopy 454

612

Subject

Index
secondary-ion mass spectrometry
depth profiling 441, 443
GaAs-AlGaAs superlattices 442, 443
transmission electron microscopy 454
see also III-V Semiconductors
Gamma radiography 163
exposure techniques 164
inspection 163
radioactive sources 163
steel 163
Gamma-ray diffractometry 165
applications 166
crystal growth 166
copper 167
crystal structure 165
gamma-ray diffractometers 165
multilayers
Ta-Si multilayers 168
phase transformations 165
Ni 3Al 167
order-disorder transformations 167
rocking curves 166
stress
TaSi2 thin films 168
theory
Bragg's law 166
Darwin's mosaic model 166
Gamma-ray emission
particle-induced gamma-ray emission 310
positron annihilation spectroscopy 390
Gamma-ray scattering 65
Gamma-ray spectroscopy
effusion 522
Mossbauer spectroscopy 259
Garnets
convergent-beam electron diffraction 107
Gd 3Ga 5O u
x-ray powder diffraction 584
Gas analysis
evolved gas analysis 509
Gas chromatography 169
detectors 171
flame photometric detectors 171
flame-ionization detectors 171
Hall electrolytic-conductivity detectors 172
infrared detectors 172
mass spectrometers 172
thermal-conductivity detectors 171
gas chromatograms 170
gas chromatographs 169
gas-liquid chromatography 170
gas-solid chromatography 170
infrared spectroscopy 197
mass spectrometry 172, 296
poly chlorinated biphenyl mixture 172
sample introduction 172
separating columns 170
capillary columns 171
packing materials 170
volatile materials 169
see also Chromatography
Gas sensors
catalytic gas detectors 178
electrical conductivity changes 177
electrochemical sensors 175

Subject

gas-sensitive resistors 177

humidity 177
hydrogen 176
oxygen 176, 177
semiconductor junction devices 178
solid-state sensors 175
sulfur-containing gases 176
surface acoustic wave sensors 177
see also Sensors
Gases
thermodynamic activity 522
Gaussmeters 228
Gels
liquid chromatography 174
General Radio Company capacitance bridge 327
Geology
secondary-ion mass spectrometry 444
solid-state nuclear track detectors 471
Gibbs-Duhem equation 520
Gibbs-Thomson-Freundlich equation 387
Ginzburg-Landau theory 487
coherence length 491
Glancing angle x-ray diffraction
glancing incidence asymmetric Bragg geometry 534, 536
lattice parameters 536
Seeman-Bohlin focusing geometry 534
thin films 534
Glancing incidence x-ray scattering 534
Glass
laser sampling inductively coupled plasma mass
spectrometry 218
solid-state nuclear track detection 468
x-ray fluorescence spectrometry 576
Glass-transition temperature
polymers 373
amorphous polymers 380
small-angle x-ray scattering 380
Gold
field-ion microscopy 151
gold-197
Mossbauer spectroscopy 261
ion backscattering analysis 204
photoacoustic microscopy 6
Goniometers
x-ray crystallography 460
x-ray fluorescence spectrometry 573
Grain boundaries
grain-boundary design 257
metals
hydrogen probes 188
palladium 189
segregation 188
microstructural evolution 247
microtextural analysis 257
see also Microstructure
Grain growth
equation-of-motion simulation 253, 254
Monte Carlo simulation 247
Grain orientation
direct pole figures 323
microtextural analysis 255
see also Texture
Grain size
MgO 247
Monte Carlo simulation 249

Index

High-resolution

electron

microscopy

nondestructive evaluation 179

magnetic methods 180
ultrasonic techniques 179
polycrystalline materials 179
tin 247
see also Microstructure
Grain structure
microstructural evolution 246
neutron diffraction 412
scanning acoustic microscopy 5
see also Microstructure
Graphics workstations
confocal optical microscopy 68, 72
Graphite
Auger electron spectroscopy 32
graphite-epoxy prepreg
dynamic mechanical analysis 511
Gravimetry
corrosion 75
porosity 386
Grazing x-ray reflectometry 534
Guinier approximation
small-angle neutron scattering 463
Hall effect 228
Hall flowmeters 395
Hardness 183
Brinell test 183
conversion tables 186
copper 237
Knoop test 185
mechanical properties microprobe 235
microhardness tests 185
portable testers 186
Rockwell test 184
sapphire 235, 236
Scleroscope test 185
Vickers test 184, 185
Harris low-frequency bridges 327
Heat flow
differential thermal analysis 499
thermography 547
Heat of formation 319
Heisenberg's uncertainty principle 259
Hemispherical analyzers 143
Heterogeneous equilibrium 522
binary alloys 523
eutectic systems 522
equilibrium partitioning 522
gas-metal equilibrium 523
gas mixture 522
gas-three condensed phases equilibrium 524
gas-two condensed phases equilibrium 523
thermodynamic activity 522
2-Hexamone
mass spectrometry 295
High-resolution electron microscopy 127
Al-Cu alloys 131
Al-Cu-Mg-Ag alloys 133
applications 131
axial illumination 130
Cu-NiPd multilayers 132, 133
electron scattering 128
high-voltage electron microscopy 136
image formation 128

613

High-resolution

electron

microscopy

instrumentation 128
electron optics 128
microscope resolution 130
silicon 131
transmission electron microscopy 452
zeolites 128, 131
High-resolution mass spectrometry 296
High-resolution optical microscopy
laser microprobe mass spectrometry 209
High-temperature measurements
thermophysical properties 525
High-voltage electron microscopy 127
Al-Cu alloys 138
Al-Si alloys 136
diffraction patterns 135
foils 126
high-resolution high-voltage electron microscopy 136
image formation 135
in situ experiments 138
electron-beam-enhanced reactivity 139
gas-solid reactions 138
hydrogen embrittlement 139
oxidation 138
phase transformations 138
reduction 138
instrumentation 135
electron optics 135
magnetite 138
microstructure 136
Ni ?Al 137
point-defect clusters 137
radiation damage 135, 136, 139
Holographic interferometry
inertial-confinement fusion 240
Homoepitaxial growth
InP 453
Hooke's law 418
Hopkinson effect 229
Huang scattering
diffuse x-ray scattering 565
Humidity
solid-state gas sensors 177
Hydrogen
diffusion in palladium 189
embrittlement 187, 188
aluminum alloys 139
gas sensors 176
metallurgical probes 187
chemical potential 187
density of sites 187
diffusivity 187, 189
Fermi level 187
hydrogen distribution 187
statistical mechanics 187
trap concentration 189
passivation 207
segregation 443, 444
Hygroscopic expansion
adhesive bonds 10
Hyperfine field interactions
electron spin resonance 146
Mossbauer spectroscopy 260
texture 264
Hysteresis
porosimetry 388

614

Subject

Index
see also Magnetic properties
Imaging see specific techniques
Imaging atom-probe mass spectroscopy 153
Immersion testing
composites 60
corrosion 80
Impact strength
carbon-fiber-reinforced composites 60, 62
polymers 369
Impurities
ceramics 43
junction transient spectroscopy 205
In situ techniques
time-resolved x-ray diffraction 567
x-ray powder diffraction 581
Inclusions
polymer films
laser microprobe mass spectrometry 212
poly (vinyl chloride) 212
Inconel
scanning acoustic microscopy 5
Indene
infrared spectroscopy 195
Indentation
mechanical properties microprobe 233
Indium phosphide
deep-level transient spectroscopy 207
defects 207
dislocations
etch pits 448, 449
homoepitaxial growth 453
transmission electron microscopy 453
see also IIIV Semiconductors
Inductively coupled plasma
laser sampling inductively coupled plasma mass
spectrometry 215
optical emission spectroscopy 283
Inelastic tunnelling spectroscopy 149
Inert-ion sputtering 32
Inertial-confinement fusion 238
defects 238
electron beam characterization 240
computer analysis 243
defects 241
microradiography 242
quantitative analysis 242
scanning electron microscopy 240
surface roughness 242
thickness 241
optical methods 239
interferometry 239
optical microscopy 239
transparent materials 239
targets 238
cryogenic materials 239
thickness 238
x-ray inspection 243
computer analysis 244
defects 244
gas fill pressures 244
microfocus digital radiography 244
microradiography 243
microtomography 244
thickness 243

Subject
see also Fusion
Infrared detection
thermal wave imaging 517
vibrothermography 548
see also Infrared sensors
Infrared radiometry
SPATE 484
thermometric stress analysis 483
Infrared sensors
nondestructive evaluation
limitations 306
paper and paperboard 305
see also Infrared detection
Infrared sources
thermal wave imaging 516
Infrared spectroscopy 193, 405
applications 198, 199
atoms 193
attenuated total reflectance 197
chemical composition 193
Fe 2(CO) 9 54
gas chromatography 197
indene 195
infrared spectrometers 193
calibration 195, 196, 199
dispersive spectrometers 193
Fourier-transform spectrometers 195
interferometer spectrometers 196
optical-null grating spectrometers 194
ratio-recording spectrometers 195
standardization 195
tunable laser spectrometers 195
window materials 193
liquid chromatography 197
mixtures 193, 199
molecules 193
nuclear magnetic resonance 198
polybutadiene 99
polyisoprene 101
polystyrene 196
qualitative analysis 197, 198
sampling
attenuated total reflectance 197
grindable solids 197
liquid films 196
microsamples 197
powdered solids 197
pyrolysis 197
solutions 196, 198
thin layers 195
solid surfaces 54
specimen preparation 405
structure 193
theory 193
vibrational frequencies 193, 194, 405
Inks
particle-induced x-ray emission 313
Inorganic materials
solid-state nuclear track detectors 469
Inspection
acoustic emission 3
composites 58
gamma radiography 163
laser-beam devices 305
neutron radiography 267

Index

Ion backscattering

analysis

paper and paperboard 305

ultrasonic inspection 59
x-ray inspection
inertial confinement fusion 243
Instrumentation see specific techniques
Insulating materials
atomic force microscopy 438
muon probes 474
Integrated circuits
confocal optical microscopy 72
ion backscattering analysis 202
metallization 202
microindentation tests 234
scanning electron microscopy 520
scanning electron acoustic microscopy 520
scanning tunnelling microscopy 435, 437
silicon 425
see also Electronic devices
Integrated optics
Raman spectroscopy 407
Interaction energies
phase diagram calculations 315
first-principle calculations 320
Interatomic forces
atomic force microscopy 436
Interfaces
Auger electron spectroscopy 33
depth profiling 83
high-resolution electron microscopy 128
semiconducting materials
InGaAs-InP 454
transmission electron microscopy 454
Interference microscopy
interference-contrast microscopy 291
differential interference-contrast microscopy 291
interference-fringe microscopy 289
multiple-beam interferometry 290
polymers 340
differential interference-contrast microscopy 341
quantitative analysis 341
Interferometry
inertial-confinement fusion 239
4 manipulator 240
holographic interferometry 240
laser interferometry 239
phase modulation 240
white-light interferometry 239
optical calorimetry 280
Interstitials
junction transient spectroscopy 205
metals 187
Raman spectroscopy 408
silicon 408
transmission electron microscopy 121
Inverse photoemission 429
Iodine
angular distribution Auger microscopy 37, 40
Ion backscattering analysis 199
applications 200, 202
chemical analysis 199
depth profiling 200
quality control 200
Rutherford backscattering 200
applications 202
channelling 203

615

Ion backscattering

analysis

differential scattering cross sections 201

energy loss 200
film thickness measurement 202
gold 204
limitations 202
mass analysis 200
microprobe analysis 203
NbSi 2 202
Pt-Si multilayers 202
quantitative analysis 201
S i - B F / 202
Ion beam effects 122
Ion detection
laser microprobe mass spectrometry 209, 210
laser sampling inductively coupled plasma mass
spectrometry 217
Ion exchange
liquid chromatography 174
Ion implantation
copper 237
sapphire 235, 236
semiconducting materials 443
Ion microprobes 95, 441
Ion microscopes 441
Ion sources
secondary-ion mass spectrometry 440
Ion sputtering
Auger electron spectroscopy 32
depth profiling 83
calibration 84
distortional effects 84
Ni-Cr multilayers 87, 88
optimized conditions 85
quantitative evaluation 87
Ta 0 5 - T a 85, 87
see also Sputtering
Ionic conductivity
hopping conduction
anodization spectroscopy 14
solid electrolyte gas sensors 175
Ionization
mass spectrometry 292
secondary-ion mass spectrometry 439
silicon 481
solid-state nuclear track detectors 469
spark-source mass spectrography 480, 481
Iron
differential thermal analysis 501
iron-57 Mossbauer spectroscopy 259
Iron alloys
F e

40

N i

40 20

32

Fe 7 8Mo 2B 20 263
Mossbauer spectroscopy 263
ISO standards
particle-shape classifications 394
Isomer shift
Mossbauer spectroscopy 260
Isothermal calorimeters 502
Bunsen ice calorimeter 502
Isotopes
gold-197 261
iron-57 259
laser sampling inductively coupled plasma mass
spectrometry 215
Mossbauer spectroscopy 259

616

Subject

Index
nuclear magnetic resonance spectroscopy 273, 277
carbon-13 nuclear magnetic resonance spectroscopy 270,
271, 275
radon-222 473
solid-state nuclear track detection 471
Jamin-Lebevedev interferometer 239
Joining see Adhesive bonding
Josephson effect 150
Junction transient spectroscopy 205
defects 205
semiconductor materials 205, 206
Kelvin equation 387
Kelvin's law 483
Kiessig fringes 534
Kikuchi lines 108
Kinetic rate theory 247
Klein-Nishina cross section 65
Knoop hardness test 185
Koch islands 156
Kohler illumination
optical microscopes 288
Kossel method 257
Kozeny equations 385
Kramers-Kronig analysis 113
Laminates
nondestructive evaluation 59
Langmuir equation 386
Laplace equation 387
Larmor frequency 269
Laser interferometry
inertial-confinement fusion 239
Laser microprobe mass spectrometry 209
applications 211
borides in Ni-based superalloys 211
depth resolution 213
inclusions 211
instrumentation 209
ion detection 209, 210
laser ablation 210
mass resolution 211
mass-to-charge ratio 209
microstructure 211
Nd-YAG laser 210
Ni-based superalloys 211
optical microscopy system 209
organic materials 211, 213
polymer films 212
quantification 214
rhodamine-B dye 213
spatial resolution 210
surfaces 209
see also Lasers, Mass spectroscopy
Laser sampling inductively coupled plasma mass spectrometry
275
calibration 218
depth profiling 217
glass 218
instrumentation 215
ionization 216
isotopes 215
laser-solid interaction 217
fusion 217

Subject
laser ablation 217
vaporization 217
Nd-YAG lasers 216
pulsed lasers 217
quantitative analysis 218
sensitivity 217
spatial resolution 217
standardization 218
trace element analysis 215
see also Lasers, Mass spectroscopy
Lasers
ablation 210
confocal optical microscopy 69
infrared spectrometers 195
interferometry 239
microprobe mass spectrometry 209
Nd-YAG lasers 210, 216, 529
nondestructive evaluation 305
optical calorimetry 279
particle size distribution 393
photoacoustic microscopy 6
pulsed lasers 217
atom-probe field-ion microscope 153
subsecond thermophysical measurements 529
Raman spectrometers 355
Raman spectroscopy 404
scanning laser acoustic microscopy 8
semiconductor diode lasers 195
subsecond thermophysical measurements 529
thermal wave imaging 517
thermoreflectance 517
see also Laser microprobe mass spectrometry, Laser
sampling inductively coupled plasma mass
spectrometry
Lattice dynamics
Mossbauer spectroscopy 259
Lattice parameters
convergent-beam transmission electron microscopy 539
glancing angle x-ray diffraction 536
x-ray crystallography 457
x-ray powder diffraction 581
Lattice stabilities
phase diagram calculations 315
first-principle calculations 320
Laue equations 104
Laue method
microtextural analysis 257
Layered structures see Multilayers
Lenses
optical microscopes 286
Light microscopy see Optical microscopy
Light scattering
polymers
molecular weight distribution 346
photon correlation light scattering 349
Rayleigh scattering 346
small-angle light scattering 338
Raman spectroscopy 403
Linear variable differential transformers 230, 503
Liquid chromatography 169, 173
detectors 173
derivitization detectors 173
differential-refractive-index detectors 173
electrochemical detectors 173
infrared detectors 173

Index

Machining

ultraviolet-absorbance detectors 173

gel-permeation chromatography 174
polystyrene 174
infrared spectroscopy 197
ion-exchange chromatography 174
liquid chromatographs 173
liquid-liquid chromatography 173
liquid-solid chromatography 173
separating columns 173
packing materials 173
see also Chromatography, Liquid chromatography mass
spectrometry
Liquid chromatography mass spectrometry 220
biological materials
human transferrin 224
peptides 223
interfacing 220
direct liquid injection 220
electrospray method 223
gas atom bombardment 224
moving belt interface 221
particle beam interface 222
thermospray method 222
ionization techniques 220
mixtures 220
nebulizers 222
separating columns 220
micro-liquid columns 220
see also Liquid chromatography, Mass spectroscopy
Liquid crystals
polarized-light microscopy 339
Liquid films
infrared spectroscopy 196
Liquids
structure
nuclear magnetic resonance spectroscopy 269, 273
x-ray fluorescence spectrometry 576
Lithium
electron energy-loss spectroscopy 112
self-diffusion coefficients
nuclear magnetic resonance 94
Lithium niobate
surface acoustic wave gas sensors 177
thermal expansion 511
thermodilatometry 511
Load-elongation characteristics
paper and paperboard 299
Low-energy electron diffraction 108
applications 111
atomic structure 110
Debye-Waller behavior 110
diffraction patterns 109
diffracted intensities 109
disorder 109
electron scattering 110
scattering potential 110
tf-factor 111
Schrodinger equation 109
Low-energy-electron loss spectroscopy
Ni-CO 55
solid surfaces 54, 55
Luminescence see Chemiluminescence
Machining
wood

617

Machining
acoustic emission 553
Magic-angle spinning
nuclear magnetic resonance spectroscopy 275
Magnesium oxide
Auger electron spectroscopy 34
cathodoluminescence 45
dislocation arrays 45
grain size 249
Monte Carlo simulation 249
Magnetic domains
scanning electron microscopy 423
Magnetic prism spectrometers
analytical electron microscopy 126
electron energy-loss spectroscopy 112, 126
Magnetic properties 225
antiferromagnetic phases 477
Curie temperature 229
Hopkinson effect 229
ferromagnetic resonance frequency 230
flux density 226
grain size evaluation 180
Barkhausen effect 181
image effect 229
magnetic fields 228
Hall effect 228
nuclear magnetic resonance 228
magnetic losses
Epstein test 231
magnetic moments 225
magnetic susceptibility 226
thermomagnetometry 506
magnetization 225
coercive force 232
Curie method 225
demagnetizing fields 228
Faraday method 225
force methods 225
induction methods 226
magnetic anisotropy 229
magnetic hysteresis 228
remanent induction 232
sample field measurement 226
saturation magnetization 225
small-angle neutron scattering 464, 467
superconducting materials 487
superconducting quantum interference device
measurements 227
magnetostriction 230
maximum energy product 232
Neel temperature 229
neutron magnetic diffraction 564
phase diagram calculations 318
first-principle calculations 321
permanent magnetic materials 231
scanning electron microscopy 426
soft magnetic materials 231
superconductors 226, 231
thermomagnetometry 506
see also Hysteresis
Magnetic recording heads
scanning electron microscopy 426
Magnetic techniques 225
alternating-gradient magnetometers 226
electronic fluxmeters 226
fluxgate magnetometers 228

618

Subject

Index
Foner magnetometer 227
gaussmeters 228
rotating-coil gaussmeters 228
linear variable differential transformers 230
magnetic balances 225
muon probes 475
antiferromagnetic phases 477
SQUID magnetometers 227, 488, 494
torque magnetometers 229
vibrating-sample magnetometers 227, 488
Magnetite
high-voltage electron microscopy 138
reduction 138
Magnetometers see Magnetic techniques
Magnets
Bitter magnets 230
superconducting magnets 230
see also Permanent magnet materials
Mass attenuation
concrete 66
neutron radiography 267
Mass spectroscopy
atom-probe microanalysis 151
bromobutane 294
2-butanone 295
effusion 522
ethyl chloride 293
gas chromatography 172, 296
2-hexamone 295
high-resolution mass spectrometry 296
imaging atom-probe mass spectroscopy 153
ionization 293
bond energy 294
exact mass 293
fragmentation 293
mass spectra 29
mass spectrometers 292
organic materials 292
phenetole 295
pyrolysis 297
quantitative analysis 297
subsecond thermophysical measurements 530
time-of-flight spectrometers 209
see also Laser microprobe mass spectrometry, Laser
sampling inductively coupled plasma mass
spectrometry, Liquid chromatography mass
spectrometry, Secondary-ion mass spectroscopy,
Spark-source mass spectrography
Mass-to-charge ratio
atom-probe microanalysis 151
laser microprobe mass spectrometry 209
Mathematical analysis
fractals 156
Mattauch-Herzog analyzer 480
Mechanical impedance
nondestructive evaluation 63
Mechanical properties
adhesives 9
Al-Li-Be alloys 235, 236
copper 237
elastomers 101
fractals 160
hardness 183
microindentation tests 233
integrated circuits 234

Subject
nickel 234, 236
microprobes 232
microtextural analysis 257
nickel 234, 236
paper and paperboard 308
polymers 366
amorphous polymers 367
flexural properties 368
impact properties 369
tensile properties 366
time-dependent properties 368
rapidly solidified materials
Al-Li-Be alloys 235, 236
rubber 367
sapphire 235, 236
texturing 497
Mechanical properties microprobe 232
applications 232, 235
descriptive models 236
hardness 235, 236
microhardness 233
microindentation tests 233
contact area 233
nanoindenters 233
microstructure 236
rapidly solidified materials 235
wear 235
weld embrittlement 235
Young's modulus 235
Mechanical testing
elastomers 101
dynamic tests 102
quality control 102
reproducibility 103
standards 104
static tests 102
hardness 183
Brinell test 183
conversion tables 186
indentation tests 183, 185
Knoop test 185
microhardness tests 185
portable testers 186
rebound tests 185
Rockwell test 184
Scleroscope test 185
standardization 183, 186
Vickers test 184, 185
paper and paperboard
destructive testing 299
nondestructive evaluation 302
polymers 366
Charpy impact test 369
computer processing 370
tensile testing 301
wood 552
see also Destructive mechanical testing, Nondestructive
evaluation
Medicine
particle-induced x-ray emission 312, 313
Meissner fraction 490
Melting
polymers 372
polyethylene 372
small-angle x-ray scattering 380

Index

Microindentation

Mercury porosimetry 387

Metal-oxide-metal structures
electron tunnelling spectroscopy 149
Metallization
ion backscattering analysis 202
Metallurgy
art forgeries 22
bronze statuary 22
decomposing alloys 464
hydrogen probes 187
amorphous materials 190
crystalline materials 190
dislocation density 188
grain boundary segregation 188
interstitials 187
nanocrystalline materials 189
oxidation 189
statistical mechanics 187
vacancies 188
secondary-ion mass spectrometry 443
small-angle neutron scattering 462
decomposing alloys 464
spark-source mass spectrography 483
see also Alloys, Metals, specific materials
Metals
amorphous metals
Mossbauer spectroscopy 263
defects
diffuse x-ray scattering 565
dislocation density 188
field-ion microscopy 154
grain boundaries 188
hydrogen probes 187
interstitials 187
nanocrystalline materials 189
neutron diffuse elastic scattering 566
positron annihilation spectroscopy 390
vacancies 188, 391
microstructure
positron annihilation spectroscopy 391
microtextural analysis 255
muon probes 478
polaron defects 477, 478
tunnelling 478
subsecond thermophysical measurements 526
see also Metallurgy, specific metals
Metastable systems
differential thermal analysis 500
polyoxymethylene 501
Methyl methacrylate
vibrothermography 549
Microcircuits see Integrated circuits
Microdiffraction techniques
convergent-beam transmission electron microscopy 537
scanning transmission electron microscopy 334
Microengineering 238
Microfocus digital radiography
inertial-confinement fusion 244
Microgravity
subsecond thermophysical measurements 528
Microhardness 185
mechanical properties microprobe 233
Microindentation
integrated circuits 234
mechanical properties microprobe 233

619

Microindentation
nickel 234, 236
Microprobe analysis
ion backscattering analysis 203
gold 204
microelectronics 203
laser microprobe mass spectrometry 209
mechanical properties 232
see also Electron microprobe analysis
Microradiography
inertial-confinement fusion
electron beam characterization 242
x-ray inspection 243
see also Radiography
Microscopy see specific techniques
Microsecond time resolution
thermophysical measurements 528
Microstructural evolution
computer simulation 246
equation-of-motion methods 252
Monte Carlo methods 247
dislocation substructure 253
grain boundaries 247
grain growth 153, 154, 247
dendritic growth 252
grain size 249
grain structure 246
Ostwald ripening 250, 253
primary recrystallization 249
processing conditions 246
second-phase particles 250, 253
secondary recrystallization 249
sintering 250
vacancy diffusion 247
see also Microstructure
Microstructure
Al-Si alloys 136
A l 2 O r Z r 0 2 45
anodization spectroscopy 14
atom-probe microanalysis 152
atomic force microscopy 27
Ni-based superalloys 27
austenitic stainless steel 235
cathodoluminescence 43, 45
elastomers 99
electron energy-loss spectroscopy 112
electron microprobe analysis 119
high-voltage electron microscopy 136
laser microprobe mass spectrometry 21
mechanical properties microprobe 235
metals
positron annihilation spectroscopy 391
Ni-based superalloys 27, 211
polymers
light microscopy 336
polarized-light microscopy 337, 338
polyethylene 337
polypropylene 338, 342
small-angle light-scattering 338
semiconducting materials
transmission electron microscopy 452
small-angle neutron scattering 462
decomposing alloys 464
spherulitic morphology, 331, 337
polyethylene 334
polypropylene 338, 342

620

Subject

Index
transmission electron microscopy 120
ZK) 2 45
see also Grain boundaries, Grain size, Grain structure,
Microstructural evolution, Surface morphology
Microtextural analysis 255
austenitic stainless steel 256
electron backscattering patterns 257
Kossel method 257
Laue method 257
mechanical properties 257
grain-boundary design 257
representation 256
Rodrigues-Frank method 256
scanning electron microscopy 257
selected-area channelling patterns 257
silicon steels 257
Microtomography
inertial-confinement fusion 244
Microwave heating
plexiglass 71
Microwave spectroscopy
electron spin resonance 145
Microwave techniques
dielectric measurements 328
nondestructive evaluation 306
Miedema's method 319
Milling tests
polymers 357
Millisecond time resolution
thermophysical measurements 528, 539
Miscibility gap
Cr-W alloys 321
Mixtures
alumina-water 48
ceramic powders 48
infrared spectroscopy 193, 199
liquid chromatography mass spectrometry 220
x-ray powder diffraction 581
Moisture
nondestructive evaluation 305, 306
Molecular-beam epitaxy
semiconducting materials
GaAs-AlGaAs superlattices 443
secondary-ion mass spectrometry 443
Molecular configurations
polymers
amorphous polymers 351
polymer dynamics 353
Raman spectroscopy 356
small-angle scattering 351
tacticity 356
Molecular structure
elastomers
carbon-13 nuclear magnetic resonance 101
infrared spectroscopy 99
polybutadiene 99
polyisoprene 101
proton nuclear magnetic resonance 100, 101
liquid chromatography mass spectrometry 220
muon probes 473
Raman spectroscopy 403
x-ray crystallography 457
see also Structure
Molecular weight distribution 349
distribution functions 344, 346, 348

Subject

applications 345
intrinsic viscosity, 348
light scattering 346
osmotic pressure 346
photon correlation light scattering 349
physical properties 345
size-exclusion chromatography 348, 350
liquid chromatography mass spectrometry 220
measurement
chromatography 350
diffusion methods 350
discrete methods 350
one-parameter functions 344
exponential functions 345
Flory-Schulz distribution 344
Poisson distribution 345
polymers 343
chromatography 350
coefficient of skewness 344
diffusion 350
measurement 349
polydispersity index 343
sedimentation 349
size-exclusion chromatography 348, 350
three-parameter functions 345
two-parameter functions 345
logarithmic normal distribution 345
normal functions 345
Schulz-Zimm distribution 345
Molecules
electron spin resonance 147
electron tunnelling spectroscopy 149
infrared spectroscopy 193
Molybdenum
alpha-particle bombardment 122
helium bubbles 122
transmission electron microscopy 122
Monolayers
angular distribution Auger microscopy 34
corrosion 76
corrugated 41
iodine 40
silver 37
Monovacancies
positron annihilation spectroscopy 391
Monte Carlo methods
inertial-confinement fusion 243
microstructural evolution 247
grain boundaries 247
grain growth 247
grain size 247
Ostwald ripening 250, 253
primary recrystallization 249
second-phase particles 250, 253
secondary recrystallization 249
sintering 250
two-phase structure 250
vacancy diffusion 247
x-ray microanalysis 579
Morphology see Surface morphology
Moseley's law 115
Mossbauer spectroscopy 259
amorphous metals 263
applications 261
conversion electron Mossbauer spectroscopy 263

Index

Muon

crystallization 263

* 2 263
F

2 0

32

probes

Cu-Fe alloys 261

Debye-Waller factor 259
diffusion 94, 264
dimers 261
electronegativity 261
Faraday-Mossbauer effect 264
gamma-ray emission 259
gold-197 261
Heisenberg's uncertainty principle 259
hyperfine field interactions 260
electric quadrupole interactions 261
isomer shift 260
nuclear Zeeman effect 260
instrumentation 260
iron-57 259
isotopes 264
lattice dynamics 259
monomers 261
Mossbauer effect 94
phase analysis 262
Ti-Fe alloys 262
phase transformations 264
X210Crl2 steel 263
polarimetry 264
quantum mechanics 259
structure
Fe^Ni 263
surfaces 263
texture 264
Multichannel optical detectors 407
Multilayers
anodization spectroscopy 15
layer uniformity 16
Cu-NiPd multilayers 132, 133
depth profiling 86
gamma-ray diffractometry 168
high-resolution electron microscopy 128, 132
Nb-Ta multilayers 15
Ni-Cr multilayers
depth profiling 87, 88
semiconducting materials 452
Ta-Si multilayers
gamma-ray diffractometry 168
depth profiling 86, 87
thermal wave imaging 515
Multiple-beam interferometry 290
Muon probes 473
beta emission 474
antiferromagnetic phases 477
CuCl 474
defects 474
insulating materials 474
KC1475
magnetic structure 475
metals 478
quantum mechanics 478
tunnelling 478
muonium formation 474
muonium labelling 475
polaron defects 477, 478
semiconducting materials 474
GaAs 475

621

Muon

probes

spin-lattice relaxation 475

spin polarization 474
spin rotation spectra 474
spin structure 477
superconducting materials
internal field mapping 477
YBa,Ok0 7 ,477
Mylar
electron spectroscopy for chemical analysis 142
Nanocrystalline materials
hydrogen probe 189
metals 189
palladium 189
Nanoindenters 233
Nanosecond time resolution
thermophysical measurements 531
National Bureau of Standards smoke chamber 365
Nebulizers
liquid chromatography mass spectrometry 222
Neel temperature 229
Nernst equation 175
Neutron diffraction
amorphous solids 558
accuracy 564
corrections 560
instrumentation 559
interpretation 562
limitations 564
model calculations 563
neutron magnetic diffraction 564
peak fitting 562
real-space correlation functions 559
scattering vector 559
steady-state reactor 560
theory 561
time-of-flight technique 560, 562
limitations 412
position-sensitive detectors 413
residual stresses 412
applications 414
composites 416
cracking 415
fatigue 415
grain structure 312
Ni-based superalloys 416
railroad rails 414
shot-peening 415
SiC-Al 20 3416
weldments 414
spallation source 413
texture 497
Bragg's law 498
theory 412
Neutron diffuse elastic scattering 566
Neutron effects
bubble formation 123
nickel 121
Neutron magnetic diffraction 564
Neutron radiography 267
applications 268
composites 62
instrumentation 267
mass attenuation coefficients 267
neutron imaging 268

622

Subject

Index
neutron-nucleus scattering 267
neutron sources 267
Neutron scattering
neutron diffuse elastic scattering 566
polymers 351
amorphous polymers 351
copolymers 352
crystalline polymers 352
networks 352
neutron spin echo spectrometers 353
phonons 351
polyelectrolytes 352
polymer dynamics 353
small-angle scattering 351
thermal-neutron scattering 351
vibrational states 351
quasielastic neutron scattering 92
see also Small-angle neutron scattering
Neutron spin echo spectrometers 353
Nickel
dislocation loops 121
diffuse x-ray scattering 566
extended x-ray absorption fine structure 555
microindentation tests 234, 236
neutron irradiation 121
transmission electron microscopy 121
voids 121
Nickel alloys
atomic force microscopy 27
laser microprobe mass spectrometry 211
hydrogen segregation 443, 444
neutron diffraction 416
Ni-Al alloys 465, 466
Ni Al 137, 167
Ni-Cr-Fe alloys 90, 125
Ni-In alloys 89, 90
Ni-Ti alloys 190
Ni-Zr alloys 190
secondary-ion mass spectrometry 443, 444
small-angle neutron scattering 465
superalloys 416
atomic force microscopy 27
neutron diffraction 416
Nickel zinc ferrite
thermogravimetry 506
van't Hoff diagram 506
Niobium
ion irradiation 122
transmission electron microscopy 122
voids 122
Niobium alloys
Nb-Ta alloys 15
Nb-V alloys 190
Niobium suicide 202
Nondestructive evaluation
acoustic emission / , 64
composites 58
acoustic emission 64
adhesive-bonded joints 64
defects 59
delamination 59, 61
eddy current inspection 64
mechanical impedance 63
optical methods 63
porosity 59

Subject
qualitative analysis 59
quality assurance 59
quantitative analysis 59
radiography 61
thermography 63
ultrasonic inspection 59
vibration techniques 63
visual inspection 59
grain size 179
magnetic methods 180
ultrasonic techniques 179
hardness testing 183
portable testers 186
paper and paperboard 302
ash measurement 303
basis weight 302
caliper 307
color 304
computer processing 302
correlation techniques 308
energy-coupling subsystem
head-positioning subsystem 307
infrared sensors 305
mechanical properties 308
microwave sensors 305
moisture 305, 306
opacity 304
optical techniques 304
piezoelectric transducers 308
quality control 308
radio-frequency sensors 306
sensors 302
signal processing 302
ultrasonic techniques 308
verification 308
x-ray sensors 303
particle-induced x-ray emission 312
polymers 497
residual stresses 417
Barkhausen noise analysis 421
limitations 418
neutron diffraction 412
ultrasonic techniques 419
x-ray diffraction 418
scanning tunnelling microscopy 435
SPATE 484
texture 497
neutron diffraction 497
polymers 497
x-ray diffraction 497
thin films 532
vibrothermography 547
wood 551
x-ray fluorescence spectrometry 570
x-ray powder diffraction 581
see also Destructive mechanical testing, Mechanical
testing, specific techniques
Novolac epoxies
evolved gas analysis 510
Nuclear magnetic resonance
classical mechanics 269
diffusion 93
lithium 94
spin-lattice relaxation 93
spin-spin relaxation 93

Index

Optical

emission

spectroscopy

electron-nuclear double resonance 148

Larmor frequency 269
magnetic field 228
proton nuclear magnetic resonance 100, 101
quantum mechanics 269
spin-lattice relaxation 269
spin-spin coupling 269, 270, 273
Nuclear magnetic resonance spectroscopy 269
carbon-13 nuclear magnetic resonance spectroscopy 101,
272
bisphenol A polycarbonate resin 275
chemical shifts 272
liquids 270, 271
off-resonance decoupling 272
polybutadiene 101
solids 275
chemical shift 270, 273
ethylbenzene 272
Fourier transform nuclear magnetic resonance spectroscopy
271
free-induction decay 271
infrared spectroscopy
liquid structure 269, 273
organic materials 269
proton nuclear magnetic resonance spectroscopy 270
solids 273
applications 276
chemical processes 276
chemical shift anisotropy 273
cross-polarization 274
dipole-dipole interactions 273, 276
homonuclear decoupling 274, 276
instrumentation 275
limitations 277
magic-angle spinning 275
polymers 277
quantitative analysis 276
sample requirements 276
solutions 269, 273
Nuclear reaction analysis
diffusion 96
nonresonant nuclear reactions 96
resonant nuclear reactions 96
Nuclear track detectors 468
Nuclear Zeeman effect
Mossbauer spectroscopy 260
Nuclepore filters 472
Opacity
inertial-confinement fusion 240
nondestructive evaluation 304
paper and paperboard 304
Optical calorimetry 279
absorption coefficients 279
adiabatic thermocouple calorimetry 279
interferometry 280
laser calorimeters 279
optical path length 280
temperature rise 279
thin-film absorption 280
Optical emission spectroscopy 281
emission sources 281, 283
arcs 284
electric sparks 284
electrical flames 283

623

Optical

emission

spectroscopy

flames 283
gas discharges 285
glow-discharge lamps 285
hot hollow-cathode lamps 285
inductively coupled plasma 283
line spectra 281
quantitative analysis 281
spectrometers 281
Czerny-Turner mounting 282
multichannel spectrometers 282
Paschen-Runge mounting 282
photodiode array detectors 282
photomultiplier tube detectors 282
reflection gratings 281
sequential spectrometers 282
Optical materials
infrared windows 193
reflection loss 194
transmission range 194
Optical microscopy 286
aluminum alloys 291
aluminum oxide 291
applications 289
bright-field illumination 289
dark-field illumination 289
inertial-confinement fusion 239
interference microscopy 289
interference-contrast microscopy 291, 340
interference-fringe microscopy 289
laser microprobe mass spectrometry 209
optical microscopes 286
aberrations 287
aperture diaphragm 288
depth of field 288
field diaphragm 288
Kohler illumination 288
magnification 287
numerical aperture 286
objective lenses 286
resolution 286
particle size distribution 392
polarized-light illumination 289, 337
polymers 336
specimen preparation 336
reflected-light methods
differential interference-contrast microscopy 341
fluorescence microscopy 342
resolution 341
transmitted light methods 337
interference-contrast microscopy 340
phase-contrast microscopy 340
polarized-light microscopy 337
see also Confocal optical microscopy
Optical path length
optical calorimetry 280
Optical properties
composites 63
nondestructive evaluation 63
paper and paperboard 304
Order-disorder transformations
gamma-ray diffractometry 167
Ni3Al 167
phase diagram calculations 318
Organic materials
bond energy 294

624

Subject

Index
electron spin resonance 146
gas chromatography 169
laser microprobe mass spectrometry 211, 213
mass spectrometry 292
nuclear magnetic resonance spectroscopy 269
particle-induced x-ray emission 313
solid-state nuclear track detectors 470
x-ray crystallography 461
Orientation distribution functions
texture 497
neutron diffraction 497
x-ray diffraction 497
Oscilloscopes 60
Osmotic pressure 346
Ostwald ripening 250, 253
Oven aging tests 357
Oxidation 74
CO 509
differential thermal analysis 509
ion backscattering analysis 202
NbSi 2 202
palladium alloys 189
polymers 357
reflection electron microscopy 411
thermal degradation
differential scanning calorimetry 359
differential thermal analysis 359
polymers 357
thermogravimetric analysis 359
see also Corrosion
Oxygen
gas sensors 176, 177
Oxygen coefficients 506
Oxygen index test
flammability 362
Ozone resistance
polymers 359
ASTM test methods 359
Packing density
ceramic powders 47
Paintings
art forgeries 19
particle-induced x-ray emission 313
pigment analysis 19
radiography 19
Pair-potential theory 319
Palladium
nanocrystalline
- phase transformations 189
grain boundary segregation 189
hydrogen diffusion 189
oxidation 189
strain
x-ray powder diffraction 587
Palladium alloys
oxidation 189
Pd-Si alloys 190
Paper and paperboard
destructive mechanical testing 299
bond failure 301
bursting strength 301
fiber pullout 301
load-elongation characteristics 299
sheet failure 301

Subject
shrinkage 299
tearing strength 301
tensile strength 301
nondestructive evaluation 302
ash measurement 303
basis weight 302
caliper 307
color 304
computer processing 302
correlation techniques 308
infrared sensors 305
mechanical properties 308
microwave sensors 306
moisture 305, 306
opacity 304
optical techniques 304
particle-induced x-ray emission 313
piezoelectric transducers 308
quality control 308
radio-frequency sensors 306
ultrasonic techniques 308
verification 308
x-ray attenuation 303
Paramagnetic resonance 144
Particle-induced gamma-ray emission 310
Particle-induced x-ray emission 309
advantages 312
air pollution
aerosols 313
applications 313
art forgeries
paintings 313
stamps 313
biological materials 312, 313
tissue 312
ceramics 313
detection limits 311
elemental analysis 309
external beam techniques 310
instrumentation 309
light elements 310
medical applications 312, 313
microbeam techniques 311
detection limits 312
spatial resolution 311, 312
nondestructive evaluation 312
paper 313
printing inks 313
proton elastic scattering analysis 310
quantitative analysis 309
sampling 310
sensitivity 312
water 314
wood 314
Particles
fractals 160
shape 394
morphology 394
stereological analysis 394
size 392
x-ray powder diffraction 587
small-angle neutron scattering 462
sources
thermal wave imaging 518
see also Powders

Index

Phase

stability

Passivation
deep-level transient spectroscopy 207
Peel tests 13
Peltier effect 503
Penetrant enhanced radiography
composites 62
Peptides
electrospray liquid chromatography mass spectrometry 223
Permanent magnet materials 231
coercive force 232
maximum energy product 232
remanent induction 232
see also Magnets
Permeability
particle size distribution 393
porosity 384
Darcy's law 384
Kozeny equations 385
Permittivity
electron energy-loss spectroscopy 113
Kramers-Kronig analysis 113
polymers 326, 328
microwave techniques 328
transient methods 326
Phase analysis
cathodoluminescence 45
ceramics 45
convergent-beam transmission electron microscopy 538
Mossbauer spectroscopy 262
Ti-Fe alloys 262
x-ray powder diffraction 581, 583
Phase angles
x-ray crystallography 459
Phase-contrast microscopy 340
Phase diagrams
Al-Li alloys 316
calculations 315
Miedema's method 319
empirical relationships 317
first-principle calculations 320
magnetic terms 318, 321
modelling 317
pair-potential theory 319
semiempirical relationships 319
differential thermal analysis 500
entropy 319, 321
heat of formation 319
interaction energies 315, 320
Cr-W alloys 321
lattice stabilities 315
metastable phases 316
Al-Li alloys 316
multicomponent systems 316
Cr-Fe-Si alloys 317
ordering 318
thermodynamics 315
free energy 315
thermometry 499
x-ray powder diffraction 584
Phase separation
small-angle neutron scattering 465
Phase stability
calculations 315
Miedema's method 319
empirical relationships 317

625

Phase

stability

first-principle calculations 320

magnetic terms 318, 321
modelling 317
pair-potential theory 319
semiempirical relationships 319
entropy 319, 321
heat of formation 319
interaction energies 315, 320
Cr-W alloys 321
lattice stabilities 315
metastable phases 316
multicomponent systems 316
ordering 318
thermodynamics 315
free energy 315
Phase transformations
- phase transformation 189
Al-Cu alloys 138
gamma-ray diffractometry 165
high-voltage electron microscopy 138
Mossbauer spectroscopy 264
Ni 3Al 167
order-disorder transformations 167
palladium 189
polymers 380
small-angle x-ray scattering 380
steel 264
Phenetole 295
Phonons
neutron scattering 351
Photoacoustic microscopy 6
gold foil 6
Photoelectric absorption 67
Photoelectron spectroscopy
solid surfaces 55
ultraviolet photoelectron spectroscopy 54
valence levels 56
x-ray photoelectron spectroscopy 54, 139
Photoemission
detector systems 143
electron spectroscopy for chemical analysis 139
Photoetching
semiconducting materials 446, 449
GaAs 446
Photography 530
Photon correlation light scattering 349
Photoresists
confocal optical microscopy 72
Photothermal radiometry 517
Physical properties
polymers 345
Piezoelectric transducers
acoustic emission 2, 7, 551
atomic force microscopy 23, 24
coupling to wood 551
nondestructive evaluation 308
Piezoelectricity
surface acoustic wave gas sensors 177
Pigments
paintings
particle-induced x-ray emission 313
stamps
radiography 19
Plasma
laser sampling inductively coupled plasma mass

626

Subject

Index
spectrometry 215
Plastic deformation
elastomers 102
polymers 380
residual stresses 419
small-angle x-ray scattering 380
x-ray diffraction 419
Plastics
flammability 361
Platinum
angular distribution Auger microscopy 38, 40
Platinum alloys
Pt-Si alloys 202
Plexiglass
confocal optical microscopy 71
Point defects
high-voltage electron microscopy 137
junction transient spectroscopy 205
Point spectroscopy
scanning tunnelling microscopy 428
Poisson's ratio
Auger electron spectrometry 90
neutron diffraction 414
x-ray diffraction 418
Polarimetry
Mossbauer spectroscopy 264
Polarized confocal optical microscopy 69
Polarized-light microscopy
Becke line test 339
birefringence 338
identification 338
liquid crystals 339
microhotstage 338
polymers 337
polyethylene 337
quantitative analysis 339
refractive index 339
small-angle light scattering 338
spherulite morphology 337
thermal effects 338
Polaron defects
muon probes 477, 478
Pole figures
copper 498
direct pole figures 323
interpretation 325
inverse pole figures 324
normalization factors 324
texture 322
x-ray goniometry 323
Polyamides
thermal degradation 359
Polybutadiene
carbon-13 nuclear magnetic resonance 101
infrared spectroscopy 99
molecular structure 99
proton nuclear magnetic resonance 100
Polychlorinated biphenyl mixture
gas chromatography 172
Polycrystalline materials
grain size 179
microtextural analysis 255
neutron diffraction 413
texture 322
Polydispersity index 343

Subject
Polyelectrolytes
small-angle neutron scattering 352
Polyesters
thermomechanical analysis 503
Polyethylene
confocal optical microscopy 71
crack propagation 330
fracture 330
melting 372
microstructure 337
polarized-light microscopy 337
scanning electron microscopy 330, 331
scanning transmission electron microscopy 334, 335
thermal degradation 359
thermodynamic properties 372
transmission electron microscopy 332
Poly(ethylene terephthalate)
differential thermal analysis 501
Polyisocyanurate
flammability 364
Polyisoprene
infrared spectroscopy 101
proton nuclear magnetic resonance 101
Polymer blends
compatibility 375
differential scanning calorimetry 375
polyethylene-polycarbonate 330
scanning electron microscopy 330
Polymer films
inclusions 212
laser microprobe mass spectrometry 212
poly(vinyl chloride) 212
transmission electron microscopy 331
Polymers
additives
fluorescence microscopy 342
amorphous polymers
glass-transition temperature 380
mechanical properties 367
small-angle neutron scattering 351
small-angle x-ray scattering 379, 380
structure 379
atomic force microscopy 28
birefringence 338
compressive strength 368
conductive polymers 433
copolymers 352
crazes 380
creep 368
crystalline polymers
small-angle neutron scattering 352
small-angle x-ray scattering 380
deformation 380
degradation 357
autofluorescence 342
thermal degradation 357
dielectric properties 325
differential interference-contrast microscopy 341
diffusion
molecular weight distribution 350
thermogravimetric analysis 377
elasticity 368
electron microscopy 329
replica techniques 330
scanning electron microscopy 329

Index

Polymers

scanning transmission electron microscopy 333

specimen preparation 329
surface morphology 329
transmission electron microscopy 331
electron spectroscopy for chemical analysis 142
elongation 366
emeraldine hydrochloride 434, 436
enthalpy 373
flammability 361
fracture 341
fluorescence microscopy 342
glass-transition temperature 373
identification 338
intrinsic viscosity 348
light microscopy 336
interference-contrast microscopy 340
phase-contrast microscopy 340
polarized-light microscopy 337
light scattering 346
mechanical properties 366
flexural properties 368
impact properties 369
stress-strain diagrams 366
tensile properties 366
time-dependent properties 368
melting 372
small-angle neutron scattering 351
small-angle x-ray scattering 380
microstructure
light microscopy 336
spherulite morphology 331
molecular configurations
Raman spectroscopy 356
small-angle neutron scattering 351
tacticity 356
molecular weight distribution 343
chromatography 350
determination 349
intrinsic viscosity 348
light scattering 346
osmotic pressure 346
photon correlation light scattering 349
physical properties 345
sedimentation 349
size-exclusion chromatography 348, 350
networks 352
neutron scattering 351
phonons 351
polymer dynamics 353
small-angle neutron scattering 351
vibrational states 351
nondestructive evaluation 497
nuclear magnetic resonance spectroscopy 277
osmotic pressure 346
oxidation 357
ozone resistance 359
phase transformations 380
photon correlation light scattering 349
physical properties 345
polyelectrolytes 352
polymer dynamics 353
Raman spectroscopy 354, 404
refractive index 339
scanning tunnelling microscopy 434
sedimentation 349

627

Polymers
semicrystalline polymers
small-angle x-ray scattering 379
structure 379
size-exclusion chromatography 348, 350
small-angle neutron scattering 351
small-angle x-ray scattering 378
solid-state nuclear track detection 468
specific heat 371
stabilization 357
stress relaxation 368
structure
degree of regularity 356
Raman spectroscopy 354
secondary structure 356
small-angle x-ray scattering 378
surface roughness 341
texture 497
thermal analysis 358, 371, 375
thermal properties 371
thermodynamic properties 372
thermogravimetric analysis 377
thermosetting resins 376
voids 380
water absorption 377
weatherability 360
x-ray scattering 378
small-angle x-ray scattering 378
yield strength 366
Young's modulus 367
see also specific materials
Poly(methyl methacrylate)
Raman spectroscopy 408
Polyoxymethylene
differential thermal analysis 501
Polypropylene
differential interference-contrast microscopy 342
polarized-light microscopy 338, 339
Polystyrene
gel-permeation chromatography 174
infrared spectroscopy, standard 195
interference-contrast microscopy 340
phase-contrast microscopy 340
specific heat 374
Polyurethane
flammability 364
Polyvinyl chloride)
laser microprobe mass spectrometry 212
thermal degradation 359
Poly(vinylidene chloride)
fluorescence microscopy 342
Porod approximation
small-angle neutron scattering 463
Porosity 381
ceramic powders
packing characterization 48, 49
composites
nondestructive evaluation 59
pore size 381
pore structure 381
adsorption 385
capillarity 387
density 384
direct methods 382
indirect methods 384, 389
permeability to fluids 384

628

Subject

Index
stereological analysis 383
porosimetry
capillary condensation 388
hysteresis 388
mercury porosimetry 387
suction porosimetry 388
specific surface 381
Position-sensitive detectors 413
Positron annihilation spectroscopy 390
defect states 390
microstructure 391
positron lifetime 390
vacancies 391
Potassium chloride
spin-lattice relaxation 475
Potassium hydrogen carbonate
thermogravimetry 513
Powders 392
bulk properties 394
apparent density 395
compaction 396
flowability 396
ceramics
density 47, 48
packing characterization 47
particulate system 47
porosity 48, 49
voids 48
volume 47
specific volume 47, 48
volume fraction 48
infrared spectroscopy 197
packing 47, 397
particle shape 394
particle size distribution 392
adsorption of gases 393
electrolyte resistance 393
elutriation 392
laser scattering 393
microscopy 392
permeametry 393
sedimentation 392
sieving 392
turbidimetry 393
powder mechanics 397
adhesion 399
cohesive powders 399, 400
contact 398
elastic properties 399
friction 399, 401
noncohesive powders 399, 400
packing 397
soil 400
stress effects 400
van der Waals attraction 398
Young's modulus 400
specific surface 393
x-ray diffraction 581
Bragg's law 568
x-ray fluorescence spectrometry 576
see also Particles
Precipitates
etching 450
GaAs 454
Ni-Al alloys 466

Subject
silicon device structure 453
small-angle neutron scattering 466
transmission electron microscopy 453
thermogravimetry 506
thermomagnetometry 506
see also Second-phase particles
Preferred orientation see Texture
Printing inks
particle-induced x-ray emission 313
Processing
composites 59
destructive mechanical testing 299
elastomers 102
microstructural evolution 246
nondestructive evaluation 59
nuclear magnetic resonance spectroscopy 276
paper and paperboard 299
scanning tunnelling microscopy 435
solid-state gas sensors 175
time-resolved x-ray diffraction 567
x-ray fluorescence spectrometry 575
Proton elastic scattering analysis 310
Proton nuclear magnetic resonance
ethylbenzene 270
polybutadiene 100
polyisoprene 101
tetramethylsilane 270
Pulse heating
subsecond thermophysical measurements 525
Pulse-height analyzers 583
Pulsed-laser atom-probe field-ion microscopes 153
Pyrolysis
infrared spectroscopy 197
mass spectrometry 297
Pyrometry
subsecond thermophysical measurements 528
Quadrupole interactions
Mossbauer spectroscopy 261
Quadrupole mass filters 441
Qualitative analysis see specific techniques
Quality control
acoustic emission 9
wood 552
corrosion tests 79
elastomers 102
ion backscattering analysis 200
nondestructive evaluation 59
paper and paperboard 308
Quantitative analysis
atomic force microscopy 26
Auger electron spectroscopy 32
differential interference-contrast microscopy 341
differential scanning calorimetry 508
differential thermal analysis 499
electron probe analysis 118
electron spectroscopy for chemical analysis 142
inductive measurements 488
inertial-confinement fusion 242
interference-fringe microscopy 341
ion backscattering analysis 201
laser sampling inductively coupled plasma mass
spectrometry 218
mass spectrometry 297
nondestructive evaluation 59

Index

Raman

spectroscopy

nuclear magnetic resonance spectroscopy 276

optical emission spectroscopy 281
particle-induced x-ray emission 309
polarized light microscopy 339
Rutherford backscattering 201
scanning electron microscopy 425
spark-source mass spectrography 482
SPATE 484
thermogravimetry 505
x-ray diffraction 560
x-ray fluorescence spectrometry 575
x-ray microanalysis 125, 482, 577
x-ray powder diffraction 584
Quantum mechanics
electron spin resonance 144
Mossbauer spectroscopy 259
muon probes 478
nuclear magnetic resonance 269
Raman spectroscopy 354
Quantum wells
transmission electron microscopy 454
Quartz
electron spectroscopy for chemical analysis 143
x-ray powder diffraction 585
Quasielastic neutron scattering 92
Radiation damage
alpha-particle effects 122
field-ion microscopy 154
metals 154
monovacancies 154
voids 155
high-voltage electron microscopy 135, 136, 139
Ni 3Al 137
Rutherford collision process 137
transmission electron microscopy 120
ion beam effects 122
neutron effects
bubble formation 123
nickel 121
Radio-frequency techniques 306
Radioactivity
decay 163
emanation thermal analysis 510
gamma radiography 163
Radiography
composites 61
computer-aided tomography 62
microfocus digital radiography 244
neutron radiography 62
see also Inertial-confinement fusion, X radiography
Radiometry
diffusion 92
photothermal radiometry 517
Radon
radon-222 solid-state nuclear track detection 473
Railroad rails
neutron diffraction 414
Raman spectroscopy 403
applications 356, 408
chemical analysis 403
crystallinity 404
fluorescence interference 406
instrumentation 355, 404, 497
computer processing 355

629

Raman

spectroscopy

integrated optics 407

laser sources 404
multichannel optical detectors 407
Raman spectrometers 355
low-frequency vibrations 356
molecular structure 356, 403
polymers 354, 404
applications 356
degree of regularity 356
molecular configurations 356
poly(methyl methacrylate) 408
secondary structure 356
structure 354
vibrational states 354, 356
Raman effect 354, 403
classical theory 354
quantum mechanics 354
resonance Raman spectroscopy 408
silicon 408
specimen preparation 405
Stokes lines 403
surface-enhanced Raman spectroscopy 408
vibrational states 405
Rayleigh scattering
polymers 346
Rayleigh waves
ultrasonics 421
Real-time measurements
scanning laser acoustic microscopy 8
time-resolved x-ray diffraction 568
video thermography 547
Recording see Magnetic recording heads
Reduction (chemical)
high-voltage electron microscopy 138
Re-entrant cavities
dielectric measurement 327
Reflection electron microscopy 409
defects 410
imaging 409
oxidation 411
phase contrast 410
reflection high-energy electron diffraction 409
scanning reflection electron microscopy 411
screw dislocations 410
silicon 411
specimen preparation 411
vacancies 411
see also Electron microscopy
Reflection extended x-ray absorption fine structure 535
Reflection high-energy electron diffraction 409
Refractive index
infrared window materials 194
liquid chromatography 173
polarized-light microscopy 339
polymers 339
subsecond thermophysical measurements 530
thermal wave imaging 517
Remanent induction 232
Residual stresses
acoustic emission 4
composites 416
SiC-Al 20 3 416
cracking 415
autofrettaged tubing 415
elastic deformation 418

630

Subject

Index
fatigue cycling 415
Hooke's law 418
nondestructive evaluation 417
Barkhausen noise analysis 421
neutron diffraction 412
ultrasonic techniques 420
x-ray diffraction 418
plastic deformation 419
Poisson's ratio 414, 418
railroad rails 414
shot-peening 415
superalloys 416
thermoelastic effect 486
weldments 414
Young's modulus 414, 418
see also Stresses
Resistivity see Electrical conductivity
Resistors
solid-state gas sensors 177
Resonance absorption spectroscopy 521
Resonance Raman spectroscopy 408
Rhodamine-B
laser microprobe mass spectrometry 213
Richardson plots 156
Rocking curves 166
Rockwell hardness test 184
Rodrigues-Frank method 256
Root-mean-square meters
acoustic emission 2
Rotating-coil gaussmeters 228
Rubbers
mechanical properties 367
Rutherford backscattering
corrosion 77
diffusion 96
depth profiling 96
high-voltage electron microscopy 137
ion backscattering analysis 200
applications 202
channelling 203
differential scattering cross sections 201
energy loss 200
film thickness measurement 202
gold 204
kinematic factor 200
limitations 202
mass analysis 200
microprobe analysis 203
NbSi 2 202
Pt-Si alloys 202
quantitative analysis 201
S i - B F / 202
4

Sampling
inertial-confinement fusion 238
infrared spectroscopy 195
laser sampling inductively coupled plasma mass
spectrometry 275
nuclear magnetic resonance spectroscopy 276
particle-induced x-ray emission 310
see also Specimen preparation
Sapphire
hardness 235
ion implantation 235, 236
wear 235

Subject
Young's modulus 235, 236
Scanning acoustic microscopy 4
grain structure 5
Inconel 5
US penny 6
Scanning calorimeters 503
Scanning electron acoustic microscopy 518
applications 518
integrated circuits 520
Scanning electron microscopy 423
acoustic emission 424
aluminum films 425
Auger electron spectroscopy 423
backscattered electrons 423
cathodoluminescence 424
electron-hole pairs 424
electron-specimen interactions 423
image contrasts 424
electron-channelling-pattern contrast 425
magnetic contrast 426
topographic contrast 424
voltage contrast 425
contrast 425
inertial-confinement fusion 240
absorbed current electrons 241
backscattered electrons 241
secondary electrons 241
signal detection 240
x-ray emission 242
integrated circuits 425, 520
microtextural analysis 257
polymers 329
polyethylene 330, 331
polyethylene-polycarbonate blend 330
resolution range 341
quantitative analysis 425
secondary electron emission 423
silicon 425
TmSr, Se424
x

1 -x

x-ray emission 423

x-ray microanalysis
quantitative analysis 579
see also Electron microscopy, Scanning transmission
electron microscopy
Scanning force microscopy see Atomic force microscopy
Scanning laser acoustic microscopy 8
metallized ribbon 8
real-time imaging 8
Scanning reflection electron microscopy 411
Scanning thermography
SPATE 484
Scanning transmission electron microscopy
analytical electron microscopy 123
electron optics 124
polyethylene 334, 335
spherulite morphology 334
polymers 333
microdiffraction technique 334
reflection electron microscopy 411
see also Electron microscopy, Scanning electron
microscopy, Transmission electron microscopy
Scanning tunnelling microscopy 427
applications 432
calibration 435
conductive polymers 433

Index

Sedimentation

electron energy states 433, 435

electron tunnelling 427
imaging 427
line scan 428
plan view 428
three-dimensional rendering 428
integrated circuits 435, 437
microscopes 430
nondestructive evaluation 435
process control 435
Schottky barrier formation 433, 435
silicon 429, 430
defects 432
SiC 432
specimen preparation 431
tip preparation 431
ZnO 433, 435
see also Electron tunnelling spectroscopy, Tunnelling
spectroscopy
Schottky barriers
scanning tunnelling microscopy 433, 435
Schrodinger equations 109
Schulz-Zimm distribution functions 345
Scleroscope hardness test 185
Screw dislocations
reflection electron microscopy 410
Second-phase particles
etching 450
GaAs 451
microstructural evolution 250, 253
Ni-based superalloys 211
small-angle neutron scattering 462
see also Precipitates
Secondary electron emission
scanning electron microscopy 241, 423
Secondary-ion mass spectroscopy 438
applications 442
geology 444
metallurgy 443
coal ash 444
depth profiling 83, 95, 443
GaAs:Be441,443
GaAs-Si multilayers 88, 89, 90
GaAs-AlGaAs superlattices 442, 443
semiconducting materials 443
diffusion 95
hydrogen segregation 443, 444
instrumentation 440
computer processing 442
ion microprobes 95, 441
ion microscopes 441
ion sources 440
mass spectrometers 441
quadrupole mass filters 441
ion-solid interactions 439
ionization 439
sputtering 439
mass spectra 444
nickel alloys 443, 444
stainless steel 443, 444
see also Mass spectroscopy
Sedimentation
particle size distribution 392
Stokes equation 392
turbidimetry 393

631

Sedimentation

Subject

polymers
molecular weight distribution 349
Seeman-Bohlin focusing geometry 534
Segregation
hydrogen
metals 188
secondary-ion mass spectrometry 443, 444
Semiconducting materials
Auger electron spectroscopy 33
cathodoluminescence 43
crystal structure 452
defects 452
depth profiling 443
dislocations
etch hillocks 447, 448
etch pits 447, 449
doping 443
electron tunnelling spectroscopy 149
etching 445
dislocations 445
electrochemical reactions 446
GaAs 446
photoetching 446, 449, 451
interfaces
InGaAs-InP 454
transmission electron microscopy 454
x-ray microanalysis 456
junction transient spectroscopy 205, 206
microstructure 452
multilayers 452
muon probes 474
scanning tunnelling microscopy 427
secondary-ion mass spectroscopy 443
thermal wave imaging 519
transmission electron microscopy 452
see also III-V Semiconductors, specific compounds and
elements
Semiconductor devices
diode lasers 195
gas sensors 175
III-V Semiconductors
anodization spectroscopy 15
see also Semiconducting materials, specific compounds
Semiempirical relationships
phase diagram calculations 319
Sensors
beta sensors 302
gas sensors 175
infrared sensors 305
microwave sensors 305
nondestructive evaluation 302
paper and paperboard 302
optical properties 304
radio-frequency sensors 306
x-ray sensors 303
Shape analysis
fractals 156
Shear strength
adhesive bonds 10
Shear waves
ultrasonics 421
Shore Durometer
portable hardness tester 186
Shot-peening
residual stresses 415

632

Index
Shrinkage
destructive mechanical testing 299
Sieving
particle size distribution 392
Signal processing
acoustic emission 2
nondestructive evaluation
paper and paperboard 302
Silicon
defects
deep-level transient spectroscopy 205, 206
scanning tunnelling microscopy 432
device structure 453
high-resolution electron microscopy 131
interstitials 481
ionization 481
Raman spectroscopy 408
reflection electron microscopy 411
scanning electron microscopy 425
spark-source mass spectrography 481
structure 131
surfaces
inverse photoemission 429
scanning tunnelling microscopy 429, 431
ultraviolet photoemission 429
transmission electron microscopy 453
x-ray powder diffraction 582
see also Semiconducting materials
Silicon carbide
Acheson method 433
cathodoluminescence 46
fibers 46
growth facets 432
scanning tunnelling microscopy 433
tunnelling spectroscopy 434
Silicon steels
microtextural analysis 257
Silver
angular distribution Auger microscopy 37
Auger electron spectroscopy 31
coinage
art forgeries 20
corrosion potential polarography 21
Single crystals
angular distribution Auger microscopy 38
platinum 38
x-ray diffraction 457
Bragg's law 568
Sintering
dynamic mechanical analysis 513
microstructural evolution 250
Monte Carlo simulation 250
Ti0 2-coated A1 20 3 513
Size-exclusion chromatography
polymers 348
molecular weight distribution 350
see also Chromatography
Slurries
x-ray fluorescence spectrometry 576
Small-angle light scattering 338
Small-angle neutron scattering
Al-Zn alloys 465
amorphous polymers 351
molecular configurations 351
applications 464

Subject
copolymers 352
crystalline polymers 352
metallurgy 462
second-phase particles 462
microstructure
decomposing alloys 464
neutron scattering 462
Guinier approximation 463
magnetization distribution 464, 467
Porod approximation 463
Ni-Al alloys 466
phase separation 465
scaling analysis 465
polyelectrolytes 352
polymer networks 352
precipitates 466
procedure 464
see also Neutron scattering
Small-angle x-ray scattering 378
instrumentation 378
polymers
amorphous polymers 379
crazes 380
deformations 380
glass-transition temperature 380
phase transformations 380
semicrystalline polymers 279
voids 380
see also X-ray scattering
Smoke
flammability of polymers 363
National Bureau of Standards smoke chamber 365
Soft magnetic materials
power loss 231
Soil mechanics 400
Solid solutions
x-ray powder diffraction 581, 584
Solid-state gas sensors 175
Solid-state nuclear track detectors
applications 468
dosimetry 471
etching 468
geological samples 471
hole engineering 472
inorganic 469
ionization 469
Nuclepore filters 472
organic 470
particle identification 469
radon-222 mapping 473
sensitivity 469
track production 468
uranium mapping 471
Solidification
mechanical properties microprobes 235
Solids
infrared spectroscopy 196, 199
muon probes 473
nuclear magnetic resonance spectroscopy 273
x-ray fluorescence spectrometry 576
Solutions
infrared spectroscopy 196, 198
nuclear magnetic resonance spectroscopy 269, 273
Space groups 457
Spark-source mass spectrography 480

Index

Specimen

preparation

applications 483
instrumentation 480
interpretation 482
ion production 480
mass spectra 481
quantitative analysis 482
silicon 481
specimen preparation 481
see also Mass spectroscopy
SPATE 484
applications 484
composites 484
computer processing 484
fracture 484
instrumentation 484
numerical model validation 484
quantitative analysis 484
spanner and bolt 485
structural dynamics 484
see also Stresses
Specific heat
ABS resin 376
polymers 371
calorimetry 371
polystyrene 374
superconducting materials 489, 490
Specific surface
porosity 381
adsorption from solution 386
adsorption of gases and vapors 385, 393
capillarity 387
stereological analysis 383
powders
adsorption of gases 393
Specific volume
ceramic powders
mixtures 48
packing characterization 47
Specifications
elastomers 103
Specimen preparation
infrared spectroscopy 405
polymers
cutting 331
electron microscopy 329
light microscopy 336
solvent casting 332
transmission electron microscopy 331
Raman spectroscopy 405
reflection electron microscopy 411
scanning tunnelling microscopy 431
semiconducting materials 452
spark-source mass spectrography 481
transmission electron microscopy
polymer thin films 331
semiconducting materials 452
x-ray crystallography 461
x-ray fluorescence spectrometry 571, 576
fabricated parts 577
glass 576
liquids 576
powders 576
slurries 576
solids 576
supported specimens 576

633

Specimen

preparation

x-ray powder diffraction 583

see also Sampling
Spectrogoniometers 573
Spectrometers see specific techniques
Spectrophotometers
dispersive spectrophotometers 304
Spectroscopy see specific techniques
Sphalerite
x-ray powder diffraction 582
Spherulitic morphology see Microstructure
Spin-lattice relaxation
diffusion 93
rotating reference frame 94
electron spin resonance 145
KC1 475
muon probes 475
nuclear magnetic resonance 269
Spin-orbit interactions
electron spin resonance
effective spin Hamiltonian 148
transition metal ions 147
Spin-spin coupling
nuclear magnetic resonance 269, 270, 273
Spin-spin relaxation
diffusion 93
electron spin resonance 146
Sputtering
secondary-ion mass spectrometry 439
see also Ion sputtering
SQUIDs
magnetometers 227, 488, 494
Stability
polymers 357
accelerated tests 357
stabilizers 358
thermal stability 357
Stainless steel
Auger electron spectroscopy 89, 90
electron energy-loss spectroscopy 127
hydrogen segregation
secondary-ion mass spectrometry 443, 444
transmission electron microscopy 127
see also Austenitic stainless steel, Steel
Stamps
particle-induced x-ray emission 313
Standardization
ASTM test methods
flammability of polymers 361
ozone resistance 359
weatherability 360
corrosion tests 79, 80
hardness testing 183
conversion tables 186
infrared spectroscopy 195
ISO standards
particle shape 394
laser sampling inductively coupled plasma mass
spectrometry 218
mechanical test methods 104
x-ray fluorescence spectrometry 577
Statistical mechanics
hydrogen probes 187
Steel
Auger electron spectroscopy 33
carbon steel 323

634

Subject

Index
corrosion 508
fracture 33
gamma radiography 163
silicon steels 257
stainless steel 127
texture 324
thermomagnetometry 508
X210Crl2 steel 264
see also Stainless steel
Steiner tunnel furnace 363
Stereological analysis
particle shape 394
porosity 383
Stokes equation 392
Stokes lines
Raman spectroscopy 403
Strain
convergent-beam transmission electron microscopy 539
neutron diffraction 412
palladium 587
tungsten 587
x-ray powder diffraction 581, 587
Stress analysis
thermoelastic effects 483
higher-order thermoelastic effects 486
infrared radiometry 484
Kelvin's law 483
mean-stress effects 486
residual stresses 486
SPATE 484
thermometric stress analysis 483
vibrothermography 548
Stress-corrosion cracking 78
Stress pattern analysis by measurement of thermal emission
see SPATE
Stress relaxation
polymers 368
Stress-strain relationships
polymers 366
powders 400
Stresses
acoustic emission 1
gamma-ray diffractometry 168
TaSi2 thin films 168
see also Residual stresses, SPATE
Stroboscopic techniques 567, 569
Structural dynamics
SPATE 484
Structure
amorphous solids
neutron diffraction 558
scattering vector 559
x-ray diffraction 558
angular distribution Auger microscopy 34
anodization spectroscopy 15
channelling-enhanced microanalysis 51
corrosion 76
N i

F4o 4o 2o

263

glancing angle x-ray diffraction 534

infrared spectroscopy 193
liquid chromatography mass spectrometry 220
liquids 269, 273
Mossbauer spectroscopy 263
nuclear magnetic resonance spectroscopy 269, 273
polymers

Subject
degree of regularity 356
Raman spectroscopy 354
secondary structure 356
small-angle x-ray scattering 378
silicon 131
surfaces
atomic force microscopy 23
low-energy electron diffraction 111
thin films 534
time-resolved x-ray diffraction 567
see also Atomic structure, Crystal structure, Molecular
structure
Subsecond thermophysical measurements 525
laser pulse heating 527, 529
femtosecond time resolution 531
high-speed photography 530
mass spectrometry 530
millisecond time resolution 530
nanosecond time resolution 531
refractive index 530
spectroscopic temperature measurements 530
metals 526
microgravity experiments 528
pulse heating 525
pyrometry 528
resistive pulse heating 526
microsecond time resolution 528
millisecond time resolution 528
submicrosecond time resolution 529
Sulfur
gas sensors 176
Superalloys
Ni-based alloys 416
Superconducting materials 487
ac losses 494
critical current density 487, 492
critical temperature 487
electron tunnelling spectroscopy 149
Josephson effect 150
flux creep 493
flux flow resistivity 491
Ginzburg-Landau theory 487
coherence length
inductive measurements 487
ac techniques 488
critical current density 493
critical temperature 489
dc magnetization 487, 493
quantitative analysis 488
irreversibility line 494
La 2Cu0 4 476
lower critical field 491
magnetic properties 226, 231
field effects 489, 491
magnetization 487
magnets 230
penetration depth 490
Meissner fraction 490
muon probes 476
internal field mapping 477
nickel zinc ferrite 506
oxygen content 506
pinning interaction distance 492
pinning penetration depth 492
resistive measurements 487

Index

Surfaces

critical temperature 489

pinning interaction distance 492
upper critical field 491
specific heat 490
heat anomaly 489
superconducting fraction 490
surface nucleation field 491
thermodynamic critical field 490
thermogravimetry 506
upper critical field 491
YBa 2Cu 30 7 4 7 7
Superconducting quantum interference devices see SQUIDs
Superlattices
GaAs-AlGaAs 442, 443
secondary-ion mass spectrometry 442, 443
transmission electron microscopy 454
Surface acoustic wave sensors 177
Surface deformation
acoustic emission 4
Surface-enhanced Raman spectroscopy 408
Surface force microscopy see Atomic force microscopy
Surface morphology
convergent-beam transmission electron microscopy 537
particle shape 394
polymers
electron microscopy 329
spherulite morphology 331
see also Microstructure
Surface roughness see Surface topography
Surface strain
thermal wave imaging detection 517
Surface topography
atomic force microscopy 23, 436
differential interference-contrast microscopy 341
electron beam characterization 242
emeraldine hydrochloride 434, 436
fractals 159
inertial-confinement fusion 242
polymers 341
scanning electron microscopy 423
topographic contrast 424
Surface x-ray absorption spectroscopy 535
Surfaces
angular distribution Auger microscopy 34
atomic force microscopy 436
Auger electron spectroscopy 29
chemical analysis 53
confocal optical microscopy 70
convergent-beam transmission electron microscopy 542
depth profiling 83
electron diffraction 104
electron microscopy 329
electron spectroscopy for chemical analysis 139
field-ion microscopy 151
fractals 156
fracture 70
high-resolution electron microscopy 128
laser microprobe mass spectrometry 209
low-energy electron diffraction 108
Mossbauer spectroscopy 263
near-surface region 32, 34, 38
polymers 329
reflection electron microscopy 409
scanning electron microscopy 423
scanning reflection electron microscopy 411

635

Surfaces
scanning tunnelling microscopy 427
silicon 411, 429
structure 111
vibrational spectroscopy 54
Auger electron spectroscopy 54, 57
infrared spectroscopy 54
low-energy-electron loss spectroscopy 54, 55
photoelectron spectroscopy 55
ultraviolet photoelectron spectroscopy 54, 55
x-ray photoelectron spectroscopy 54, 55
x-ray characterization 533
Synchrotron radiation
Compton scattering 66, 67
time-resolved x-ray diffraction 568
x-ray absorption spectroscopy 557
x-ray powder diffraction 583
Tacticity
Raman spectroscopy 356
Tantalum oxide
depth profiling 85, 87
Tantalum silicide
evolved gas analysis 511
gamma-ray diffractometry 168
Tearing strength
destructive mechanical testing 301
Temperature see Thermal analysis
Tensile strength
adhesive bonds 10
destructive mechanical testing 301
paper and paperboard 301
polymers 366
Terracotta
art forgeries 17
Testing see specific methods
Tetramethylsilane
proton nuclear magnetic resonance spectroscopy 270
Texture
crystallite orientation distribution functions 322, 497
copper 498
killed steel 324
low-carbon steel 323
microtextural analysis 255
Mossbauer spectroscopy 264
neutron diffraction 497
nondestructive evaluation 497
pole figures, 322
copper 498
direct pole figures 323
inverse pole figures 324
x-ray goniometry 323
polymers 497
x-ray diffraction 497
x-ray powder diffraction 581, 586
see also Grain orientation
Thermal analysis
calorimetry 502
optical calorimetry 279
differential scanning calorimetry 359, 499, 508
differential thermal analysis 359, 508
dilatometry 503
thermodilatometry 511
dynamic mechanical analysis 511
evolved gas analysis 509
emanation thermal analysis 510

636

Subject

Index
feedback 513
overview 498
polymers 358, 371, 375
recent developments 506
thermogravimetry 358, 504, 506
thermomagnetometry 506
thermomechanical analysis 503
thermometry 499
see also Calorimetry
Thermal conductivity
composites 63
gas chromatography 171
thermography 63
vibrothermography 547
Thermal degradation
chemiluminescence 359
differential scanning calorimetry 359
differential thermal analysis 359
milling tests 357
oven aging tests 358
oxidation 357
oxygen uptake 358
ozone resistance 359
polymers 357
polyamides 359
polyethylene 359
polyvinyl chloride) 359
thermal analysis 358
thermogravimetric analysis 358
weatherability 360
Thermal diffusion
thermal wave imaging 515
Thermal emission see SPATE
Thermal expansion
adhesive bonds 10
dynamic mechanical analysis 511
LiNb0 3511
thermodilatometry 511
x-ray powder diffraction 581
Thermal gradients
vibrothermography 547
Thermal properties
polymers 371
extrapolation techniques 372
Thermal wave imaging 575
detection methods 517
imaging 516
generalized source imaging 516
localized source imaging 516
infrared sources 516
particle sources 518
electron injection 519
thermalization 519
photothermal radiometry 517
scanning electron acoustic microscopy 518
semiconducting materials 519
temperature distribution 515
thermal depth profiling 516
thermal diffusion 515
thermal spectroscopy 516
x-ray sources 516
Thermal-neutron scattering
polymers 351
Thermobalances 377
thermogravimetry 507

Subject
Thermodilatometry 511
applications 511
LiNb0 3511
see also Dynamic mechanical analysis
Thermodynamic activity 520
electrochemical measurements 524
fugacity 520
heterogeneous equilibrium 522
binary alloys 523
binary eutectic system 522
partitioning 522
gas-metal equilibrium 523
gas mixture 522
gas-three condensed phases equilibrium 524
gas-two condensed phases equilibrium 523
vapor pressure 520
dew point 521
effusion 521
resonance absorption spectroscopy 521
transpiration 521
Thermodynamic critical field 490
Thermodynamic properties
activity 520
calorimetry 503
polymers 372
polyethylene 372
Thermodynamics
etch pit formation 447
Gibbs-Duhem equation 520
phase diagram calculations 315
Thermoelasticity
stress analysis 483
higher-order thermoelastic effects 486
infrared radiometry 484
Kelvin's law 483
mean-stress effects 486
residual stresses 486
SPATE 484
Thermography
composites 63
thermal conductivity 63
real-time video thermography 547
vibrothermography 547
Thermogravimetry 504, 506
applications 506
calcium oxalate 505
coal 508
KHC0 3513
polymers 377
polyamides 359
polyethylene 359
polyvinyl chloride) 359
thermal degradation 358
thermal oxidation 359
precipitates 506
quantitative analysis 505
superconducting materials 506
nickel zinc ferrite 506
thermobalances 377, 507
thermomagnetometry 506
Thermoluminescence 525
art forgeries 18
atomic processes 526
dating
archeological ceramics 528

Index

Time

resolution

dosimetry 527
Thermomagnetometry 506
applications 506
coal 508
corrosion 508
magnetic susceptibility 506
precipitates 506
steel 508
Thermomechanical analysis 503
drawn polyester fibers 504
Thermometric stress analysis 483
infrared radiometry 483
SPATE 484
Thermometry 499
Thermophysical properties
subsecond measurements 525
Thermoreflectance 517
Thermosetting resins 376
Thermospray method
liquid chromatography mass spectrometry 222
Thick films see Foils
Thin films
angular distribution Auger microscopy 34
anodization spectroscopy 14
atomic force microscopy 28
buried layers 16
depth profiling 83
electron diffraction 104
epitaxial films
x-ray powder diffraction 585
NbSi 2
ion backscattering analysis 202
oxidation 202
optical calorimetry 280
polymers 331
Pt-Si 202
TaSi2
evolved gas analysis 511
gamma-ray diffractometry 168
thickness 76
convergent-beam transmission electron microscopy 538
corrosion product films 76
inertial-confinement fusion 238
infrared spectroscopy 195
ion backscattering analysis 202
transmission electron microscopy 331
x-ray characterization 537
extended x-ray absorption fine structure 535
glancing angle x-ray diffraction 534
glancing incidence x-ray scattering 534
grazing x-ray reflectometry 534
surface x-ray absorption spectroscopy 535
total-reflection x-ray fluorescence 534
x-ray fluorescence spectrometry 577
x-ray microanalysis 579
x-ray powder diffraction 585
Thomson-Gibbs equation 372
Tian-Calvet calorimeters 503
Time-of-flight techniques
atom-probe field-ion microscopes 152
laser microprobe mass spectrometry 209
neutron diffraction 560, 562
Time resolution
subsecond thermophysical measurements 528
x-ray diffraction 567

637

Time-resolved

x-ray

diffraction

Subject

Time-resolved x-ray diffraction 567

direct measurements 568
energy-dispersive x-ray diffraction 569
in situ techniques 567
monochromators 569
position-sensitive detectors 568
real-time measurements 568
stroboscopic techniques 568, 569
synchrotron radiation 568
Tin
grain size 249
Titanium alloys
Ti-Fe alloys 262
Titanium oxide
ash content 304
Topography
fractals 159
see also Surface topography
Torque magnetometers 229
Total-reflection x-ray fluorescence 534
Trace elements
laser sampling inductively coupled plasma mass
spectrometry 215
Transducers see Piezoelectric transducers
Transient methods
dielectric measurements 326
Transition metal oxides 557
Transition metals 147
Transmission electron microscopy
ABS copolymer 332
analytical electron microscopy 123
convergent-beam transmission electron microscopy 537
dislocations
GaAs 454
InP 453
electron optics 124
high-resolution electron microscopy 127
high-resolution transmission electron microscopy 452
high-voltage electron microscopy 134
microdiffraction techniques 537
microstructure 120
bubbles 122
defect clusters 120
interstitials 121
vacancies 121
voids 121
molybdenum 122
nickel 121
niobium 122
polymers
polyethylene 332
spherulite morphology 331
thin films 331
precipitates
GaAs 454
silicon device structure 453
quantum wells 454
radiation damage 120
semiconducting materials 452
GaAs 454
InGaAs-InP 454
InP 453
interfaces 454
multilayers 452
silicon 453

638

Index
specimen preparation 452
stainless steel 127
superlattices 454
see also Electron microscopy, Scanning transmission
electron microscopy
Transmission lines
dielectric measurements 326, 328
Transparent materials
confocal optical microscopy 71
inertial-confinement fusion 239
Transpiration 521
Tungsten
x-ray powder diffraction 587
Tunnelling spectroscopy 428
current imaging tunnelling spectroscopy 429
electron energy states 428
point spectroscopy 428
SiC 434
ZnO 435
see also Electron tunnelling spectroscopy, Scanning
tunnelling microscopy
Turbidimetry
particle size distribution 393
Ultrasonic properties
wood 551
Ultrasonic techniques
acoustoultrasonics 551
grain size evaluation 179
backscatter technique 180
single-frequency technique 180
two-frequency technique 180
inspection
A-scan 60
B-scan 60
C-scan 60
composites 59
delamination 61
imaging systems 61
immersion testing 60
impact damage 60, 62
jet probes 61
roller probes 61
nondestructive evaluation 308
residual stresses 419
acoustoelastic constants 421
Rayleigh waves 421
shear waves 421
vibrothermography 547
wave propagation 179
Ultraviolet photoelectron spectroscopy
CO 56
Pd-CO 56
Rh^(CO)]6 56
solid surfaces 54, 55
Ultraviolet photoemission
silicon 429
Unit cells
convergent-beam transmission electron microscopy 541
electron diffraction 105
phase analysis 538
x-ray crystallography 457
Uranium
extended x-ray absorption fine structure 556
solid-state nuclear track detection 471

Subject
Vacancies
field-ion microscopy
displacement cascades 154
monovacancies 154
junction transient spectroscopy 205
metals
hydrogen probes 188
monovacancies 391
positron annihilation spectroscopy 391
microstructural evolution 247
reflection electron microscopy 411
transmission electron microscopy 121
Vacuum tunnelling 150
Valence levels
Auger electron spectroscopy 57
photoelectron spectroscopy 56
van der Waals attraction
powders 398
van't Hoff diagrams
nickel zinc ferrite 506
Vanadium suicide
convergent-beam transmission electron microscopy 541
Vapor pressure
Beer's law 521
thermodynamic activity 520
dew point 521
effusion 521
resonance absorption spectroscopy 521
transpiration 521
Vaporization
laser sampling inductively coupled plasma mass
spectrometry 217
Vibrating-sample magnetometers 227
Vibrational states
infrared spectroscopy 405
polymers
neutron scattering 351
Raman spectroscopy 354
Raman spectroscopy 354, 405
solid surfaces 54
see also Electron energy states
Vibroacoustic emission
composites 64
Vibrothermography 547
applications 548
composites
boron epoxy 549
delamination 547, 548
fatigue testing 548
high-amplitude low-frequency mechanical vibrations 547
high-frequency ultrasound 547
infrared detection 547, 548
low-amplitude high-frequency mechanical vibrations 547
methyl methacrylate 549
real-time video thermography 547
stress distribution 548
thermal conductivity 547
Vickers hardness test 184, 185
Video techniques
real-time video thermography 547
Viscoelasticity
adhesives 10
elastomers 102
Viscosity
polymers 348

Index

X-ray

absorption

spectroscopy

Visual inspection
composites 59
Voids
ceramic powders 48
composites 63
Compton scattering 67
computer-aided tomography 63
field-ion microscopy 155
nickel 121
niobium 122
polymers 380
small-angle x-ray scattering 380
transmission electron microscopy 121
Volatile materials
gas chromatography 169
Volumetric methods
ceramic powders 47
corrosion 75
Washburn equation 389
Water
absorption in polymers 377
particle-induced x-ray emission 314
Waveguides see Transmission lines
Wavelength-dispersive x-ray fluorescence spectrometry 570
Wear
mechanical properties microprobe 235
sapphire 235
Weatherability
ASTM test methods 360
laboratory tests 360
outdoor exposure 360
polymers 360
weatherometers 360
Welds
acoustic emission 3
austenitic stainless steel 235, 237
gamma radiography 163
neutron diffraction 414
Wetting 387
Wood
acoustic emission 551
adhesives 553
biological degradation 553
composites 553
cutting 553
defects 552
drying 553
fracture 552
particle-induced x-ray emission 314
quality control 552
X radiography
art forgeries 19
composites 61
penetrant enhanced radiography 62
X-ray absorption spectroscopy
extended x-ray absorption fine structure 535, 555
advantages 558
Fourier transforms 556
instrumentation 557
limitations 558
nickel 555
radial distribution function 556

639

X-ray absorption

spectroscopy

theory 555
uranium 556
x-ray sources 557
surfaces 535
x-ray absorption near edge fine structure 535, 5 5 5
advantages 558
instrumentation 557
limitations 558
theory 555
transition metal oxides 557
x-ray sources 557
X-ray analysis
electron-beam damage 333
index of refraction 533
thin films 531
x-ray fluorescence spectrometry 577
x-ray microanalysis 5 7 7
x-ray reflection 533
Kiessig fringes 534
see also X-ray microanalysis, specific techniques
X-ray crystallography 457
Bragg's law 458
computer processing 457
instrumentation 459
goniometers 460
lattice constants 457
organic materials 461
phase angle 459
procedure 460
space groups 457
specimen preparation 461
structure factor 459
unit cells 457
X-ray diffraction 458
amorphous solids 558
accuracy 564
Compton scattering 560
corrections 560
dispersion technique 560
fluorescent-foil x-ray diffraction 560, 563
instrumentation 559
interpretation 562
limitations 564
model calculations 563
peak fitting 562
quantitative analysis 560
real-space correlation function 559
scattering vector 559
theory 561
crystal symmetry 539
glancing angle x-ray diffraction 534
residual stresses 418
elastic deformation 418
plastic deformation 419
x-ray sources 419
single crystals 457
Bragg's law 568
texture 497
time-resolved x-ray diffraction 567
see also X-ray powder diffraction
X-ray electron microanalyzers 76
X-ray emission
analytical electron microscopy 124
crystal-diffraction spectrometers 116
electron microprobe analysis 115

640

Subject

Index
Bragg's law 116
x-ray maps 119
energy-dispersive spectrometers 117, 124
flow proportional counter 117
particle-induced x-ray emission 309
scanning electron microscopy 242, 423
X-ray fluorescence spectrometry 570
absorption-enhancement effects 577
analytical methods 577
calibration 577
mathematical methods 577
matrix-dilution methods 577
standard addition and dilution 577
standardization 577
thin films 577
x-ray scattering 577
dispersion 572
instrumentation 572
automation 571, 575
electronic detection 574
readout components 574
spectrogoniometers 573
x-ray generators 572
matrix effects 576
nondestructive evaluation 303
paper and paperboard 303
quantitative analysis 576
specimen preparation 571, 576
spectral excitation 572
total-reflection 534
x-ray sources 572
see also Fluorescence
X-ray inspection
inertial-confinement fusion 243
X-ray microanalysis
Al-Ag alloys 125
analytical electron microscopy 124
InGaAs-InP 456
Ni-Cr-Fe alloys 125
quantitative analysis 125, 5 7 7
calibration 580
Cliff-Lorimer equation 125
dimensions of analysis 580
energy-dispersive 577
Monte Carlo modelling 579
specimen geometry 579
wavelength-dispersive 577
ZAF corrections 578
see also X-ray analysis
X-ray photoelectron spectroscopy 139
corrosion 76
depth profiling 83
Ni-Cr alloys 88
solid surfaces 54, 55
see also Electron spectroscopy for chemical analysis
X-ray powder diffraction 581
amorphous materials 581, 585
applications 584
Bragg's law 568, 581
computer processing 583
crystal imperfections 581, 586
crystallite size 581, 587
diamond 582
epitaxial films 585
Gd 3Ga 50 12 garnet 584

Subject
in situ measurements 581
instrumentation 582
focusing x-ray diffractometers 582
pulse-height analyzer 583
lattice parameters 581, 585
mixtures 581
particle size 587
phase diagrams 584
phase identification 581, 583
computer matching 583
quantitative analysis 584
quartz 585
reflections 581
silicon 582
solid solutions 581, 584
specimen preparation 583
synchrotron radiation 583
texture 581, 586
thermal expansion 581
ZnS 582
see also X-ray diffraction
X-ray reflectometry 533
grazing x-ray reflectometry 534
Kiessig fringes 534
X-ray scattering
Compton scattering 65
diffuse x-ray scattering 565
Huang scattering 565
glancing incidence x-ray scattering 534
polymers 378
x-ray fluorescence spectrometry 577
see also Small-angle x-ray scattering
X-ray sensors
nondestructive evaluation 303
x-ray fluorescence spectrometry 574
X-ray sources
electron spectroscopy for chemical analysis 143
synchrotron radiation
time-resolved x-ray diffraction 568
x-ray absorption spectroscopy 557
x-ray powder diffraction 583
thermal wave imaging 516

Index

Zone-axis

patterns

x-ray absorption spectroscopy 557

x-ray fluorescence spectrometry 572
X-ray spectroscopy
ash 303
clay 304
T i 0 2 304
X-ray texture goniometry 323
Yield strength
polymers 366
Young's modulus 420
corrosion 77
mechanical properties microprobe 235
polymers 367
powders 400
residual stresses
neutron diffraction 414
x-ray diffraction 418
sapphire 235, 236
ZAF method
elemental analysis 242
plasma mass spectrometry 242
x-ray microanalysis 578
Zeeman effect
electron spin resonance 144, 146
nuclear Zeeman effect 260
Zeolites
high-resolution electron microscopy 128, 131
Zero gravity experiments
subsecond thermophysical measurements 528
Zinc oxide
Auger electron spectroscopy 433, 436
scanning tunnelling microscopy 433
tunnelling spectroscopy 435
Zinc sulfide
x-ray powder diffraction 582
Zirconium oxide
cathodoluminescence 45
oxygen sensors 176
Zone-axis patterns
convergent-beam transmission electron microscopy 538

641