211

Chapter 9

E.S.C.A.

STUDIES OF CLAY MINERALS

Paul CANESSON
U n i v e r s i t i . de P o i t i e r s , L a b o r a t o i r e de Chimie X I , 40 Avenue du Recteur Pineau,
86022 - P o i t i e r s - France.
INTRODUCTION

9.1

Since t h e f i r s t r e v i e w p u b l i s h e d b y K. Siegbahn e t a l . (1967) summing up t h e

main r e s u l t s o b t a i n e d i n Uppsala by X-ray P h o t o e l e c t r o n Spectroscopy (X.P.S.)

l o t o f l a b o r a t o r i e s have been concerned w i t h t h i s t e c h n i q u e . The main f e a t u r e s

of t h i s new t o o l r e s t i n i t s v e r y h i g h s e l e c t i v i t y f o r t h e s u r f a c e o f t h e sample
t o be a n a l y s e d and i n i t s a b i l i t y t o d e t e c t a l l t h e elements except hydrogen.
T h i s l a s t c a p a c i t y has a l l o w e d K. Siegbahn t o c a l l t h i s t e c h n i q u e E l e c t r o n Spect r o s c o p y f o r Chemical A n a l y s i s (ESCA)

I n a d d i t i o n t o t h e v a l e n c e e l e c t r o n s , each atom i n a compound has c o r e e l e c t r o n s t h a t a r e n o t i n v o l v e d i n t h e b o n d i n g ( e x c e p t hydrogen). The e n e r g i e s o f

t h e s e e l e c t r o n s a r e c h a r a c t e r i s t i c o f t h e i n d i v i d u a l atoms; y e t , t h e y a r e a l s o
r e s p o n s i v e t o changes i n t h e e l e c t r o n i c environment and t h e y may be used t o p r o v i d e i n f o r m a t i o n on bonding.
S i n c e so much r e l e v a n t i n f o r m a t i o n seems t o be d i r e c t l y a v a i l a b l e f r o m t h e
e l e c t r o n energy d i s t r i b u t i o n , i t i s n o t s u r p r i s i n g t h a t d i r e c t o b s e r v a t i o n o f
e l e c t r o n energy l e v e l s by e l e c t r o n s p e c t r o s c o p y s h o u l d s t a n d o u t a s t h e most
p o w e r f u l t o o l t o answer t h e q u e s t i o n s "What elements ? " "How many o f them ? "
"What t y p e o f b o n d i n g ?".
N e v e r t h e l e s s , anyone w o r k i n g w i t h an ESCA system must keep i n mind t h a t , i n
most cases, t h e r e s u l t s o b t a i n e d f r o m t h i s t e c h n i q u e can be o f i n t e r e s t o n l y by
comparison w i t h t h o s e o b t a i n e d b y any o t h e r means t h a t we know o f . Moreover, i n
o r d e r t o o b t a i n good r e s u l t s and because o f i t s h i g h s e l e c t i v i t y f o r t h e s u r f a c e ,
i t i s necessary t h a t X.P.S.

(e.g.

induced problems s h o u l d be s a t i s f a c t o r i l y s o l v e d

c h o i c e o f a s u p p o r t , c h a r g i n g e f f e c t and c h o i c e o f a r e f e r e n c e , carbon

c o n t a m i n a t i o n o v e r l a y e r and i t s e f f e c t s . . . ) .
B e a r i n g i n mind t h e p a r t i c u l a r case o f c l a y s and c l a y m i n e r a l s , t h e b a s i c
p r i n c i p l e s o f X.P.S.

(ESCA) and t h e p r e c a u t i o n s t o be t a k e n f o r spectrum i n t e r -

p r e t a t i o n s w i l l be summarized i n t h e f i r s t p a r t o f t h i s s t u d y , b e f o r e r e v i e w i n g
t h e main r e s u l t s t h a t have a l r e a d y been o b t a i n e d i n o u r p a r t i c u l a r t o p i c o f
interest.

212

B A S I C PRINCIPLES OF PHOTOELECTRON SPECTROSCOPY.

9.2
9.2.1

Fundamental r e l a t i o n and consequences.

The fundamental proce'ss o c c u r i n g i n X . P . S .

( o r ESCA) i s a p h o t o e l e c t r i c e f f e c t .

An X-ray o f known energy, hv, impinges on a sample, e j e c t i n g e l e c t r o n s f r o m i t ,

w i t h k i n e t i c e n e r g i e s (EK) g i v e n by t h e fundamental r e l a t i o n :
EK = hv - E l B

where E l B i s t h e energy t o be s u p p l i e d t o a p a r t i c u l a r atom i n o r d e r t o b r i n g

o u t a p a r t i c u l a r e l e c t r o n f r o m i t s fundamental l e v e l i n s i d e t h e sample t o t h e
s t a t e o f a s i n g l e e l e c t r o n w i t h a k i n e t i c energy equal t o z e r o under vacuum. I f
t h e Fermi l e v e l i s t a k e n as r e f e r e n c e f o r t h e b i n d i n g energy s c a l e , E l B i s t h e
sum o f two terms, namely EB, t r u e b i n d i n g energy o f t h e e l e c t r o n o f i n t e r e s t ,
and @ which r e p r e s e n t s t h e work f u n c t i o n o f t h e sample. The k i n e t i c energy o f
t h e e j e c t e d e l e c t r o n can be w r i t t e n :

An a c c u r a t e measurement o f EK i s o b t a i n e d w i t h an e l e c t r o n s p e c t r o m e t e r and
d e t a i l e d r e v i e w s o f i n s t r u m e n t a t i o n may be f o u n d elsewhere (Siegbahn, 1967;
J e n k i n , 1977).
An X.P.S.

spectrum r e p r e s e n t s a number o f p h o t o e j e c t e d e l e c t r o n s f r o m t h e

sample versus t h e i r k i n e t i c energy o r t h e i r b i n d i n g energy. A s h a r p l i n e appears

f o r e v e r y e l e c t r o n i c l e v e l (with, o f course, a b i n d i n g energy l o w e r t h a n h v ) o f
a l l t h e elements p r e s e n t i n t h e a n a l y z e d p r o d u c t . X.P.S.

i s sensitive t o a l l the

elements w i t h an a t o m i c number g r e a t e r t h a n 2 and t h e t a b l e o f b i n d i n g e n e r g i e s

g i v e n by Siegbahn e t a l . (1967) i s always c o n v e n i e n t f o r t h e a t t r i b u t i o n o f t h e
observed peaks i n a spectrum, t h u s X.P.S.
The e x a c t p r o f i l e o f an X.P.S.

appears as an a n a l y t i c a l t o o l .

l i n e i s a complicated convolution product bet-

ween t h e n a t u r a l p r o f i l e o f t h e l e v e l o f i n t e r e s t , t h e r e s o l u t i o n o f t h e a n a l y z i n g energy system and t h e p r o f i l e o f t h e e x c i t i n g r a d i a t i o n . Working w i t h v e r y

narrow X-ray l i n e s as a s o u r c e w i l l enhance r e s o l u t i o n . F o r t h i s reason,
A1 Ka ( h v = 1486.6 eV)

and Mg Ka (1353.6 eV) l i n e s a r e c u r r e n t l y used as X-ray

sources.
This basic p r i n c i p l e reveals t h e f i r s t l i m i t a t i o n o f e l e c t r o n spectroscopy. A
g o o d d e t e r m i n a t i o n o f t h e k i n e t i c e n e r g y o f t h e e j e c t e d e l e c t r o n s c a n o n l y b e achieved

i f t h e i r mean f r e e p a t h i n s i d e t h e s p e c t r o m e t e r i s g r e a t e r t h a n t h e l e n g t h t h e y
have t o t r a v e l between t h e sample and t h e d e t e c t o r ; p r e s e n t l y s p e c t r o m e t e r s a r e
o p e r a t e d under vacuum b e t t e r t h a n 10-8

10-9 t o r r .

Under t h e s e c o n d i t i o n s t h e u s e r must make s u r e t h a t t h e s u r f a c e o f t h e sample

does n o t undergo any t r a n s f o r m a t i o n under u l t r a h i g h vacuum. S i n c e t h e r e i s no

213
t e m p e r a t u r e l i m i t a t i o n , i t i s always p o s s i b l e t o a v o i d a m o d i f i c a t i o n o f t h e
s u r f a c e by c o o l i n g t h e sample a t temperatures as l o w as t h a t o f l i q u i d n i t r o g e n .
Moreover, t h e vapour p r e s s u r e o f t h e sample must be l o w e r t h a n t h e r e s i d u a l p r e s sure i n s i d e t h e spectrometer, p r a c t i c a l l y l i m i t i n g e l e c t r o n spectroscopy t o t h e
study o f s o l i d s .
Working w i t h c l a y s , t h i s l i m i t a t i o n may be a s o u r c e o f d i f f i c u l t i e s s i n c e
t h e s e m i n e r a l s most o f t e n e x i s t w i t h a h i g h w a t e r c o n t e n t and keeping c l a y m i n e r a l s
under vacuum can i n d u c e d e h y d r a t i o n r e a c t i o n s t h a t may change t h e s u r f a c e p r o p e r t i e s . F o r example, when m e s o - t e t r a p h e n y l p o r p h y r i n (TPP) i s adsorbed i n t h e i n t e r l a y e r s p a c e , o f m o n t m o r i l l o n i t e , t h e X.P.S.

spectrum o f t h e N 1 s l e v e l i s s u e d

from t h e adsorbed m o l e c u l e suggests t h a t t h e r e e x i s t s some e x t r a p r o t o n a t i o n of

t h e TPP m o l e c u l e (Canesson e t a l . ,

1978). Vacuum b e t t e r t h a n lo-* t o r r and X-ray

bombardment would i m p l y a d e s o r p t i o n o f adsorbed w a t e r , and i t i s w e l l known

t h a t c l a y s w i t h a v e r y l o w w a t e r c o n t e n t have t h e i r a c i d i t y enhanced ( F r i p i a t
e t al.,

1965; B a i l e y e t a l . ,

1976). T h e r e f o r e i n s i d e t h e s p e c t r o m e t e r t h e c l a y

s u r f a c e a c t s as a super a c i d medium f o r t h e adsorbed TPP.

9.2.2

R e l a x a t i o n process.

I f a vacancy i s c r e a t e d i n an i n n e r e l e c t r o n s h e l l b y X-ray i r r a d i a t i o n , t h e

e x c i t e d atom w i l l r e v e r t t o t h e ground s t a t e by e i t h e r e m i t t i n g c h a r a c t e r i s t i c
X-ray r a d i a t i o n o r by r a d i a t i o n l e s s t r a n s i t i o n s , t h e s o - c a l l e d Auger t r a n s i t i o n s .
I n t h e X-ray case, t h e i n n e r vacancy i s f i l l e d w i t h an e l e c t r o n f r o m an o u t e r
s h e l l and t h e r e l e a s e d energy i s e m i t t e d as e l e c t r o m a g n e t i c r a d i a t i o n i n an X-ray
quantum. I n t h i s case, t h e r e l a x a t i o n process i s t h e s o - c a l l e d X-ray f l u o r e s c e n c e .
I n t h e Auger case, t h e r e l e a s e d energy i s i n s t e a d t r a n s f e r r e d t o a n o t h e r e l e c t r o n i n one o f t h e o u t e r s h e l l s . T h i s e l e c t r o n i s t h e n r e l e a s e d and l e a v e s t h e
atom. The Auger process can be c o n s i d e r e d as t h e sum o f X-ray f l u o r e s c e n c e and
t h e p r i m b y process o f X.P.S..

A c o m p l i c a t i o n i n X.P.S.

spectroscopy i s t h a t

Auger e l e c t r o n s e m i t t e d f r o m t h e sample a r e a l s o a n a l y z e d i n t h e s p e c t r o m e t e r
and appear i n t h e X.P.S.

s p e c t r a . S i n c e t h e Auger process i n v o l v e s t h r e e d i f f e -

r e n t l e v e l s i n s i d e one atom, t h e c o r r e s p o n d i n g Auger peaks a r e r a t h e r broad w i t h

r e s p e c t t o t h e p r i m a r y X.P.S.
s c a l e o f a s o - c a l l e d X.P.S.

e l e c t r o n s . Ift h e p o s i t i o n on t h e k i n e t i c energy
e l e c t r o n depends on t h e n a t u r e o f t h e anode o f t h e

X-rays source, Auger e l e c t r o n s do n o t , because t h e i r k i n e t i c energy i s o n l y

dependent on t h e n a t u r e o f t h e c o n s i d e r e d atom.
9.2.3

X.P.S.

as a s u r f a c e t e c h n i q u e

The e x c i t i n g r a d i a t i o n used i s a b f e t o e j e c t e l e c t r o n s f r o m atoms a t r a t h e r

i m p o r t a n t depths, b u t i t i s w e l l known t h a t e l e c t r o n s w i t h e n e r g i e s o f a few
keV o r l e s s p e n e t r a t e o n l y v e r y t h i n l a y e r s o f s o l i d m a t t e r . P h o t o e l e c t r o n s

2 14
produced by a Mg K a l i n e f o r example emerge f r o m a s u r f a c e l a y e r c o n t a i n i n g some
hundred a t o m i c l a y e r s . The f r a c t i o n t h a t emerges w i t h o u t energy l o s s becomes
e x c e e d i n g l y s m a l l as t h i s l i m i t i s approached. The average d e p t h a t w h i c h t h o s e
e l e c t r o n s observed i n t h e e l e c t r o n l i n e s a r e produced may be o n l y a few t e n s o f
an

i.The

s o - c a l l e d escape d e p t h o f p h o t o e l e c t r o n s depends on s e v e r a l f a c t o r s ,

e.g. t h e n a t u r e , d e n s i t y and c r y s t a l s t r u c t u r e o f t h e sample m a t e r i a l , t h e energy

o f the radiation involved f o r e x c i t a t i o n

... .

I t i s w e l l known t h a t t h e escape

depth i s s u b s t a n t i a l l y g r e a t e r i n s i d e an o x i d e t h a n i n t h e c o r r e s p o n d i n g m e t a l ,
and t h e more e n e r g e t i c t h e X-ray s o u r c e i s , t h e g r e a t e r t h e escape depth. The
v a r i a t i o n s o f t h e mean f r e e p a t h o f e l e c t r o n s versus t h e i r k i n e t i c energy must
be t a k e n i n t o account f o r 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 s o f X.P.S.
9.2.4

spectra.

Choice o f a r e f e r e n c e l i n e

We have seen t h a t X.P.S.

can be used as a q u a l i t a t i v e a n a l y t i c a l t e c h n i q u e .

L e t us now emphasize t h a t t h e e x a c t p o s i t i o n on t h e b i n d i n g energy s c a l e o f a

p a r t i c u l a r l e v e l does n o t depend o n l y upon t h e n a t u r e o f t h i s l e v e l o f t h e c o n s i dered element b u t a l s o on i t s chemical environment. O x i d a t i o n s t a t e , t y p e o f
bonding, n a t u r e o f t h e n e a r e s t neighbour have an i n f l u e n c e on t h e k i n e t i c energy
o f t h e p h o t o e j e c t e d e l e c t r o n s , and i n my o p i n i o n one o f t h e p r i n c i p a l advantages
o f X.P.S.

r e s t s here. One can e a s i l y a d m i t t h a t t h e more p o s i t i v e an element i n

a sample i s , t h e more d i f f i c u l t a f u r t h e r i o n i s a t i o n w i l l be, even i n c o r e l e v e l s .

T h i s f a c t induces chemical s h i f t s i n t h e p o s i t i o n o f t h e observed l e v e l . T h i s
s h i f t i s always l o w (e.g.

5 eV f r o m m e t a l l i c molybdenum t o molybdenum t r i o x i d e

(Cimino and De A n g e l i s , 1975) b u t i t c a r r i e s o u t some fundamental i n f o r m a t i o n .

I t f o l l o w s t h a t t h e e x a c t p o s i t i o n o f a g i v e n l e v e l can be s a i d t o be o n l y depen-

d e n t on t h e n a t u r e o f t h i s l e v e l and t h e r e a l charge o f t h e element o f i n t e r e s t

i n s i d e t h e sample. I n o r d e r t o a v o i d any u n c e r t a i n t y i n t h e i n t e r p r e t a t i o n o f
s p e c t r a , t h e b i n d i n g e n e r g i e s d e t e r m i n a t i o n s must be as a c c u r a t e as p o s s i b l e .
T h i s r a i s e s one o f t h e m a j o r problems w i t h X.P.S.:

any l a c k o f p r e c i s i o n i n

t h e d e t e r m i n a t i o n o f k i n e t i c energy o f p h o t o e j e c t e d e l e c t r o n s w i l l i n d u c e t h e
same i n a c c u r a c y f o r b i n d i n g e n e r g i e s . A c c o r d i n g t o t h e b a s i c p r i n c i p l e o f X.P.S.,
some e l e c t r o n s a r e e j e c t e d f r o m t h e sample, t h e r e s u l t o f w h i c h i s a n e t p o s i t i v e
charge on t h e a n a l y z e d s u r f a c e , even i f t h e sample i s i n good e l e c t r i c c o n t a c t
w i t h t h e s p e c t r o m e t e r ; w o r k i n g w i t h i n s u l a t o r s o r semi-conductors does n o t cancel
t h i s charging e f f e c t .
I n a s t a t i o n a r y s t a t e , a c o n s t a n t p o s i t i v e charge remains on t h e s u r f a c e ,
which i n t u r n c r e a t e s a r e t a r d i n g e l e c t r i c f i e l d f o r t h e e l e c t r o n s l e a v i n g t h e
sample. I t can be e a s i l y understood t h a t i t i s o f p r i m e i m p o r t a n c e t o a c c o u n t
f o r t h i s effect,

and t h e b i n d i n g energy s c a l e must be c a l i b r a t e d f o r e v e r y sample.

Various methods have been proposed i n t h e l i t t e r a t u r e f o r t h e c a l i b r a t i o n o f X.P.S.

s p e c t r a (Ebel, 1974; Hnatowich e t a l . ,

1971; O g i l v i e and Wolberg, 1972).

215
One o f t h e f i r s t methods c o n s i s t s i n u s i n g t h e C 1 s l e v e l o r i g i n a t i n g f r o m
a carbon c o n t a m i n a t i o n o v e r l a y e r . E s p e c i a l l y w i t h t h e f i r s t commercial X.P.S.
systems, t h e vacuum was n o t o f v e r y good q u a l i t y and t h e samples were c o a t e d
w i t h a l a y e r o f carbon c o n t a i n i n g p r o d u c t s ( p r o b a b l y e s s e n t i a l l y hydrocarbons
f r o m pump o i l s ) . T h i s carbon c o n t a m i n a t i o n has been used w i d e l y f o r c a l i b r a t i o n
purpose, t h e b i n d i n g energy o f t h e C 1 s l e v e l b e i n g a r b i t r a r i l y f i x e d between
283.5 eV and 285.5 eV, depending on t h e a u t h o r s . P r e c i s i o n i n b i n d i n g energy
d e t e r m i n a t i o n s has been e s t i m a t e d a t 0.2 eV i n t h i s case (Ebel, 1974; Contour
and Mouvier, 1975). T h i s method

i s o b v i o u s l y t h e e a s i e s t t o use, b u t i t f a i l s

now w i t h new ESCA systems because t h e carbon c o n t a m i n a t i o n o v e r l a y e r i s t o o small,

i f n o t absent. I t does n o t work e i t h e r when t h e r e a r e more t h a n one carbon spe-

c i e s i n t h e spectrum o f t h e C 1 s l i n e ; t h i s i s t h e case f o r s t u d i e s o f adsorbed

carbon c o n t a i n i n g molecules (Defosse and Canesson, 1976).
The second method c o n s i s t s i n e v a p o r a t i n g a g o l d l a y e r as t h i n as p o s s i b l e
o n t o t h e s u r f a c e o f t h e sample, t h e 4 f d o u b l e t o f g o l d b e i n g used as a standard.
T h i s t e c h n i q u e has been much d e s c r i b e d (Urch and Weber, 1974); n e v e r t h e l e s s , i t
can be used p r o v i d e d some p r e c a u t i o n s a r e t a k e n . The g o l d l a y e r i s n o t evenly
spread on t h e s u r f a c e b u t i t shows i s l a n d s (Brunner and Zogg, 1974) and t h e
e l e c t r i c c o n t a c t between t h e sample and t h e s e i s l a n d s may n o t be as good as expected. Gold i s a b l e t o r e a c t w i t h some compounds, e s p e c i a l l y m e t a l l i c species,
l e a d i n g t o t h e f o r m a t i o n o f a l l o y s which, i n t u r n , i n d u c e a s h i f t o f t h e Au 4 f
l e v e l s (Friedman e t a l . ,

1973 a; Friedman e t a l . ,

1973 b ) . Gold e v a p o r a t i o n can

a c t as argon bombardment and a m o d i f i c a t i o n o f t h e s u r f a c e may occur, o r some

s u p e r f i c i a l r e a c t i o n s such as r e d u c t i o n can show up. B e f o r e u s i n g t h i s g o l d
d e c o r a t i o n t e c h n i q u e f o r t h e b i n d i n g energy s c a l e c a l i b r a t i o n , i t i s o f t h e
g r e a t e s t i m p o r t a n c e t o r e c o r d a l l X.P.S.

s p e c t r a f o r q u a n t i t a t i v e purposes b e f o r e

and a f t e r g o l d e v a p o r a t i o n and t h i s p r a c t i c a l l y m u l t i p l i e s a p p r e c i a b l y t h e t i m e
f o r r e c o r d i n g t h e s p e c t r a f o r one sample.
Whenever p o s s i b l e , t h e l a s t method i s t h e b e s t i n my o p i n i o n .

A w e l l defined

l e v e l o f one element p r e s e n t i n t h e sample i s t a k e n as r e f e r e n c e and i t s b i n d i n g

energy v a l u e i s a r b i t r a r i l y f i x e d . T h i s method i m p l i c i t e l y assumes t h a t , when
s t u d y i n g v a r i o u s samples, one element i s p r e s e n t i n a l l o f them and t h e b i n d i n g
energy v a l u e o f i t s c o r e l e v e l s does n o t b r i n g a b o u t any m o d i f i c a t i o n , which
means t h a t t h e chemical environment o f t h i s element i s t h e same f r o m one sample
t o an o t h e r . Working w i t h c l a y s i s an enormous advantage, s i n c e p r a c t i c a l l y a l l
c l a y m i n e r a l s c o n t a i n s i l i c o n i n an oxygen t e t r a h e d r a l environment, and one can
assume t h a t t h e b i n d i n g energy o f t h e S i 2p l e v e l i s p r a c t i c a l l y t h e same f o r
a l l samples. I n t h i s case, p r e c i s i o n i n b i n d i n g energy d e t e r m i n a t i o n s can be
e s t i m a t e d a t 0.1 eV ( O g i l v i e and W o l b e r t , 1972). Moreover, when adsorbed compounds
a r e i n v e s t i g a t e d , i t has been demonstrated t h a t a d s o r p t i o n does n o t b r i n g about
any s h i f t i n t h e b i n d i n g e n e r g i e s o f t h e adsorbant l e v e l s (Brundle, 1974).

216
I n c o n c l u s i o n , i f t h e b i n d i n g energy s c a l e c a l i b r a t i o n remains a problem i n

X.P.S.,

w o r k i n g w i t h c l a y s p e r m i t s t h e use o f an i n t e r n a l s t a n d a r d and t h i s i s

t h e b e s t method f o r t h i s purpose.
9.2.5

P o s s i b i l i t i e s o f quantitative analysis.

B e f o r e c o n s i d e r i n g t h e v a r i o u s f a c t o r s t h a t a r e i n v o l v e d i n t h e i n t e n s i t y of
peak, l e t us f i r s t examine t h e s e n s i t i v i t y of t h i s t e c h n i q u e . To b e g i n

an X.P.S.

w i t h , i t must be p o i n t e d o u t t h a t X.P.S.

i s n o t a b l e t o d e t e c t t r a c e s . The extreme

d e t e c t i o n l i m i t i s about 0 . 1 % o f t h e a n a l y z e d l a y e r , b u t , i n o r d e r t o deduce
some i n f o r m a t i o n from an X.P.S.

spectrum, t,he s i g n a l - t o - n o i s e r a t i o must n o t

be t o o bad and i t i s r a t h e r d i f f i c u l t t o p u t f o r w a r d any c o n c l u s i o n s on t h e

chemical environment o f s p e c i e s w i t h a c o n t e n t l o w e r t h a n 0.3
analyzed l a y e r . N e v e r t h e l e s s when w o r k i n g w i t h X.P.S.,

0.5

i n the

a d i s t i n c t i o n must be

made between t h e b u l k c o m p o s i t i o n and what i s s t u d i e d , namely t h e s u r f a c e compos i t i o n . I f t h e r e i s some s u p e r f i c i a l e n r i c h m e n t i n t h e elements o f i n t e r e s t , t h e

d e t e c t i o n l i m i t can be as l o w as p.p.b.
e t al.,

expressed as b u l k c o n t e n t r a t i o s ( H e r c u l e s

1973).

L e t us now examine what i n f l u e n c e s i n t e n s i t y , expressed as t h e i n t e g r a t e d s u r face a r e a of an X.P.S.

peak. T h i s i n t e n s i t y i s p r o p o r t i o n a l t o :

t h e p h o t o e l e c t r o n i c c r o s s s e c t i o n ux o f t h e c o n s i d e r e d l e v e l
t h e mean f r e e p a t h Ax o f t h e e j e c t e d p h o t o e l e c t r o n s i n s i d e t h e sample
t h e s o - c a l l e d l u m i n o s i t y Lx o f t h e system f o r t h e l i n e o f i n t e r e s t
t h e c o n c e n t r a t i o n Cx o f t h e c o n s i d e r e d element i n s i d e t h e a n a l y z e d l a y e r of

t h e sample.
The i n t e n s i t y Ix
o f a l i n e x can b e w r i t t e n :

Ix
= k ox X, Lx C x

k b e i n g a p r o p o r t i o n a l i t y c o n s t a n t , depending on t h e s p e c t r o m e t e r dhd i t s w o r k i n g
conditions.

I f t h e various

CT

v a l u e s can be c a l c u l a t e d f o r t h e X-ray s o u r c e o f i n t e r e s t

( S c o t f i e l d , 1976), t h e v a l u e s o f k and Lx cannot be e a s i l y determined. I n t e n s i t i e s a r e used as i n t e n s i t y r a t i o s between t h e peak o f i n t e r e s t and a peak o f

reference,

n o t e d r. The r a t i o R,

between t h e s e two v a l u e s i s equal t o :

I n t h i s e q u a t i o n , X i s a f u n c t i o n o f t h e k i n e t i c energy o f t h e c o n s i d e r e d
electrons. I n t h e f i r s t approximation, Ax i s p r o p o r t i o n a l t o

(Carter e t a l .
KX

217
1975), w h i c h means t h a t R x can be w r i t t e n as

L x a l s o depends upon t h e E

KX

value; from t h i s c o r r e l a t i o n , i t i s n o t possible

t o o b t a i n any i n f o r m a t i o n because t h e c o r r e c t r e l a t i o n s h i p i s f u n c t i o n o f t h e
w o r k i n g mode o f t h e c o n s i d e r e d ESCA system. Over t h e r e c e n t y e a r s , some compilat i o n s have been made, which a r e v e r y u s e f u l . Wagner (1972) compared t h e i n t e n s i t y r a t i o s o f t h e l e v e l s issued from various s a l t s , t h e i n t e n s i t y o f the

F 1s

l i n e b e i n g t a k e n a r b i t r a r i l y as u n i t y and he has d e t e r m i n e d t h e r e l a t i v e u n i t a r y
i n t e n s i t i e s o f v a r i o u s l e v e l s o f most c u r r e n t l y s t u d i e d elements. The same k i n d
of work was a l s o done by Nefedov e t a l . ,

(1973, 1975, 1977). These a u t h o r s d i d

use t h e Na 1 s l e v e l s as r e f e r e n c e f o r t h e r e l a t i v e u n i t a r y i n t e n s i t i e s s c a l e .
I n a l l t h e s e r e f e r e n c e s t h e e f f e c t o f t h e carbon c o n t a m i n a t i o n o v e r l a y e r was
n e g l e c t e d . I f t h e a n a l y z e d s u r f a c e i s covered by such a l a y e r o f t h i c k n e s s d,
t h e t r u e Rx r a t i o i s t r a n s f o r m e d i n t o a measured R I x r a t i o , the- r e l a t i o n s h i p
between them b e i n g :
Rlx=Rx

XIr

exp[

and A ' x b e i n g t h e mean f r e e p a t h s o f e l e c t r o n s i n s i d e t h e c o n t a m i n a t i n g

l a y e r . R e s p e c t i v e l y f r o m ( 6 ) , i t i s p o s s i b l e t o d e f i n e c l e a r l y when t h e contam i n a t i o n o v e r l a y e r can be n e g l e c t e d , namely :

when d i s equal t o zero, namely when t h e r e i s no c o n t a m i n a t i o n and,

when 1 / X l r

1 / A I x i s n e a r l y equal t o z e r o , which means t h a t A\

cs

A;(.

L f one

assumes t h a t A ' v a l u e s behave i n t h e same way as r e a l A , t h e l a t t e r c o n d i t i o n

b e i n g o b t a i n e d i f t h e p h o t o e j e c t e d e l e c t r o n s f r o m t h e r e f e r e n c e l i n e and t h e
l i n e o f i n t e r e s t have t h e same k i n e t i c energy. T h i s case i s t h e most f a v o u r a b l e
f o r q u a n t i t a t i v e a n a l y s i s purposes because i n t h i s case Ax # Ar and t h e sampling
d e p t h i s t h e same f o r t h e two l i n e s o f i n t e r e s t . On t h e c o n t r a r y , e.g.
EK,

if

>z E K ~ , t h e sampling d e p t h i s n o t e x a c t l y t h e same f o r t h e r and x l i n e s .

T h i s e f f e c t o f a s u p e r f i c i a l l a y e r was c l e a r l y shown by Defoss& e t a l . (1975).

Working w i t h n i c k e l exchanged z e o l i t e s , t h e c r a c k i n g o f benzene on t h e s u r f a c e
induces a carbon l a y e r w h i c h d i m i n i s h e s b y a f a c t o r o f 5 t h e r a t i o

R N i = ' N i 2p 3 / 2 / I S i

2p

A l l t h e f a c t o r s t h a t may i n f l u e n c e q u a n t t a t i v e d e t e r m i n a t i o n s by X.P.S.

were

s t u d i e d i n d e t a i l by Wagner ( 1 9 7 7 ) .
A f t e r t h e s e g e n e r a l c o n s i d e r a t i o n s a b o u t t h e X.P.S.

t e c h n i q u e , l e t us now

2 18
examine what i n f o r m a t i o n has a l r e a d y been o b t a i n e d w i t h t h i s p o w e r f u l and v e r s a t i l e technique.
9.3

APPLICATIONS OF X.P.S.
Since X.P.S.

TO CLAYS AND CLAY MINERALS.

can be used as an a n a l y t i c a l t o o l f o r q u a n t i t a t i v e s u r f a c e ana-

l y s i s as w e l l as f o r d e t e r m i n a t i o n o f t y p e o f bonding, i t i s d i f f i c u l t t o a r b i t r a r i l y separate t h e r e s u l t s obtained r e s p e c t i v e l y . A l l i n f o r m a t i o n i s contained

i n t h e same spectrum and I have chosen t o examine s e p a r a t e l y s t a n d a r d a n a l y s i s
o f b u l k m i n e r a l s and what i s t y p i c a l l y s u r f a c e a n a l y s i s , namely a d s o r p t i o n s t u d i e s .
9.3.1

Minerals analvsis

A t t e n t i o n must be drawn on t h e f a c t t h a t X.P.S.

does n o t e n a b l e us t o d i s t i n -

g u i s h between two c o o r d i n a t i o n numbers f o r t h e same c a t i o n w i t h t h e same n a t u r e

o f l i g a n d s i n t h e c o o r d i n a t i o n sphere. I n s p i t e o f r e s u l t s p u b l i s h e d i n t h e e a r l y
t i m e s of X.P.S.

(Nicholls e t al.,

1974; L i n d s a y e t a l . ,

1972), s e v e r a l a u t h o r s (Anderson and Swartz,

1973) have shown t h a t t h e r e i s no d i f f e r e n c e i n t h e b i n d i n g

energy v a l u e o f t h e A1 2p l e v e l i n an oxygen environment whatever i t s c o o r d i n a t i o n number : e i t h e r f o u r o r s i x . Keeping i n mind t h a t t h e e x a c t p o s i t i o n on t h e

b i n d i n g energy s c a l e o f a p a r t i c u l a r l e v e l i s o n l y dependent on t h e r e a l charge
o f t h e element o f i n t e r e s t , such r e s u l t i s n o t s u r p r i z i n g . I n c r e a s i n g t h e c o o r d i n a t i o n number o f A13+ f r o m f o u r t o s i x w i l l i n d u c e an i n c r e a s e i n t h e mean
A1-0 bond l e n g t h and so t h e s t a t i s t i c a l e f f e c t o f t h e oxygen environment on t h e
r e a l charge o f t h e c e n t r a l c a t i o n w i l l be t h e same. The r e s u l t s o b t a i n e d by
Nicholls

e t a l . (1972) a r e r a t h e r n i c e l y e x p l a i n e d by L i n d s a y e t a l . (1973).

The d i f f e r e n c e i n b i n d i n g energy o f t h e A1 2p l e v e l ( 1 . 4 eV) between m i c r o l i n e

(aluminum i n f o u r f o l d c o o r d i n a t i o n ) and A1203 (aluminum i n s i x f o l d c o o r d i n a t i o n )
i s a consequence o f t h e presence o f potassium i n m i c r o l i n e ; i t reduces t h e e l e c tron

a t t r a c t i n g a b i l i t y o f t h e oxygen atoms, so t h e r e a l charge o f A13+ i o n s

i s lowered w i t h r e s p e c t t o t h a t i n A1203 and t h e b i n d i n g energy o f t h e A1 2p

l e v e l i s a l s o lowered i n m i c r o l i n e .

I f t h e c o o r d i n a t i o n number has no i n f l u e n c e on t h e b i n d i n g energy, on t h e

c o n t r a r y , Urch and Murphy (1974) have i n t e r p r e t e d t h e d i f f e r e n c e s i n b i n d i n g
e n e r g i e s o f A1 2p and A1 2s c o r e l e v e l s o f a s e r i e s o f a l u m i n o s i l i c a t e s m i n e r a l s
as i n f l u e n c e d by t h e A1-0 bond l e n g t h s . These a u t h o r s concluded t h a t b i n d i n g
energy i n c r e a s e s w i t h t h e A1-0 d i s t a n c e .
When w o r k i n g w i t h ESCA on a l u m i n o s i l i c a t e s m i n e r a l s , one can g e n e r a l l y a d m i t
t h a t t h e b i n d i n g e n e r g i e s o f c o r e l e v e l s o f t h e main c o n s t i t u e n t s , namely S i , A1
and 0 do n o t v a r y t o o much f r o m one sample t o an o t h e r . T h i s assumption was v e r i f i e d many t i m e s i n t h e l i t e r a t u r e b y s e v e r a l a u t h o r s on a l o t o f m i n e r a l s l i k e
k y a n i t e , s i l l i m a n i t e and m u l l i t e (Anderson e t a l . ,

1974), k a o l i n i t e , c h l o r i t e

219
and i l l i t e (Koppelman and D i l l a r d , 1975) and 12 n a t u r a l s i l i c a t e s and a l u m i n o s i l i c a t e s (Carriere e t al.,

1977). T a k i n g t h e S i 2p l i n e as a s t a n d a r d , t h e A1 2s

and 0 1s l i n e s o f m o n t m o r i l l o n i t e do n o t show any m o d i f i c a t i o n i n b i n d i n g energy

and i n t e n s i t y , whatever t h e charge b a l a n c i n g c a t i o n : Na+, Fez+, N i 2 + , Mn2+, Cu2+,
Co2+, Sn4+. These r e s u l t s were o b t a i n e d f r o m a s t u d y o f c a t i o n exchanged montm o r i l l o n i t e s (Canesson e t a l . ,

1978).

About t h e b u l k chemical c o m p o s i t i o n o f s e v e r a l m i n e r a l s , Adams e t a l . ,

have demonstrated t h a t X.P.S.

(1977)

can p r o v i d e b u l k q u a n t i t a t i v e c o m p o s i t i o n o f a i r -

s t a b l e homogeneous s o l i d s w i t h an accuracy o f c.a.

5 %. From t h e i r c o m p i l a t i o n

o f a l o t o f p o l y c r i s t a l l i n e and m o n o c r i s t a l l i n e samples, t h e y concluded t h a t

t h e r e i s no s u p e r f i c i a l s e g r e g a t i o n o f any o f t h e c o n s t i t u e n t s o f k a o l i n i t e ,
t a l c , m o n t m o r i l l o n i t e , l a p o n i t e , l e p i d o l i t e , c r y o l i t e and z e o l i t e . The o n l y dev i a t i o n f r o m b u l k c o m p o s i t i o n i s observed f o r m o n o c r i s t a l l i n e p h l o g o p i t e , which
e x h i b i t s a h i g h e r c o n t e n t i n aluminum i o n s i n t h e analyzed r e g i o n t h a n i n t h e
b u l k , even a f t e r r e p e a t e d c l e a v a g e s . The reason would be t h a t t h i s m i n e r a l cleaves
i n r e g i o n s w i t h a h i g h aluminum c o n t e n t . More s u r p r i s i n g i s t h e l a c k o f d i s c r e pancy f o r Y z e o l i t e s , s i n c e , as i t was shown by s e v e r a l a u t h o r s , a d e p l e t i o n i n
aluminum i o n s i s observed i n t h e f i r s t a t o m i c l a y e r s o f s y n t h e t i c Y z e o l i t e s
(Tempere e t a1 . , 1977; Defosse e t a1

. , 1977).

S i m i l a r r e s u l t s were p u b l i s h e d by Koppelman and D i l l a r d ( 1 9 7 8 ) . These a u t h o r s

found t h a t t h e S i / A l s u r f a c e r a t i o i s t h e same as i n t h e b u l k f o r k a o l i n i t e and
c h l o r i t e . F o r i l l i t e , t h e y n o t e d a d e p l e t i o n i n potassium i n t h e analyzed l a y e r
s i n c e t h e S i / K r a t i o deduced f r o m X.P.S.

i n t e n s i t i e s i s l o w e r t h a n t h a t determined

by more c l a s s i c a l a n a l y t i c a l methods. F o r t h e o t h e r elements (Mg, A1 and Fe),

which a r e c o n s t i t u t i v e o f t h e t e t r a h e d r a l and o c t a h e d r a l l a y e r s , t h e S i / M e t a l
r a t i o s were w i t h i n 6 % o f t h e b u l k chemical c o m p o s i t i o n . I t was suggested t h a t
t h e observed d i s c r e p a n c i e s a r o s e because no c o r r e c t i o n f o r e l e m e n t a l depth i n
t h e sample was made..Potassium i n t h e i n t e r l a y e r space i n i l l i t e i s a t a depth
g r e a t e r t h a n o t h e r exposed c a t i o n s , r e d u c i n g t h e S i / K X.P.S.
The c a t i o n t h a t has focused most X.P.S.

intensity ratio.

workers e f f o r t s i n t h e f i e l d o f n a t u r a l

m i n e r a l s , i s u n d o u b t e d l y i r o n . I t s chemical s t a t e (Fez+ o r Fe3+) was t e n t a t i v e l y

s t u d i e d by Adams e t a l . (1972); t h e y were u n a b l e t o d i s t i n g u i s h between f e r r i c
and f e r r o u s i r o n s p e c i e s i n t h e m i n e r a l s t h e y examined. T h i s i s n o t s u r p r i s i n g
s i n c e t h e Fe 2p 3/2 l e v e l i s r a t h e r b r o a d and t h e i r o n c o n t e n t , e x c e p t i n some
m i n e r a l s o f t h e mica f a m i l y i s r a t h e r l o w i n a l u m i n o s i l i c a t e s . The c o r r e s p o n d i n g
X.P.S.

peaks a r e ill d e f i n e d , w i t h a l o w s i g n a l t o n o i s e r a t i o . Moreover, t h e

observed s h i f t s between Fez+ and Fe3+ i n p u r e i r o n o x i d e s a r e r a t h e r l o w (Mac

I n t y r e and Z e t a r u k , 1977; Asami and Hashimoto, 1977). N e v e r t h e l e s s , Koppelman
and D i l l a r d (1975) were a b l e t o d i s t i n g u i s h between Fez+ and Fe3+ i n i l l i t e . The
comparison of t h e Fe 2p 3/2 l i n e i s s u e d f r o m n o n t r o n i t e (Fez+ s p e c i e s o n l y ) ,

220
c h l o r i t e (Fez+ s p e c i e s o n l y ) and i11 it e , a1 lowed t h e a u t h o r s t o decompose t h e
Fe 2p 3/2 X.P.S.

p r o f i l e o f i l l i t e i n t o two i r o n s p e c i e s , namely Fe2+ and Fe3+.

The r e l a t i v e abundance o f Fe3+ as determined by t h e r e l a t i v e s u r f a c e a r e a o f t h e

c o r r e s p o n d i n g X.P.S.
mineral .

peak i s i n good agreement w i t h Mossbauer d a t a on t h e same

S t u c k i e t a l . ( 1 9 7 6 ) , s t u d y i n g n o n t r o n i t e and b i o t i t e , a l s o observed a s h i f t
between t h e Fe 2p 3 / 2 s p e c t r a o f t h e s e m i n e r a l s . Upon r e d u c t i o n by e i t h e r h y d r a z i n e o r d i t h i o n i t e t h e Fe 2p l e v e l s o f n o n t r o n i t e e x h i b i t a broadening t o g e t h e r
w i t h a s h i f t towards

l o w e r b i n d i n g e n e r g i e s . On t h e c o n t r a r y , o x i d a t i o n o f b i o -

t i t e by bromine induces a s h i f t towards h i g h e r b i n d i n g e n e r g i e s . W i t h such compound, t h e observed s p e c t r a a r e o f r a t h e r p o o r q u a l i t y and any c o n c l u s i o n on t h e

r e l a t i v e q u a n t i t i e s o f t h e v a r i o u s i r o n s p e c i e s would be r a t h e r s p e c u l a t i v e .

Si2

C r u d e kaalinitc

___.x
'I i n c r e a s i n g

:time
I
I

0.8

I
I

deferrating treatment

0.6

0.4
0.2
0.1

0:2

013

014

015'

si2p

F i g . 9.1.
Behaviour o f t h e Fe 2p/Si 2p r a t i o v e r s u s t h e A 1 2p/Si 2p r a t i o f o r
t h e YBi k a o l i n i t e a f t e r v a r i o u s c o n t a c t t i m e s w i t h ammonium o x a l a t e s o l u t i o n .

221
I r o n i n k a o l i n i t e i s a n o t h e r problem many c l a y r e s e a r c h e r s have t a c k l e d (e.g.
see Angel and V i n c e n t (1978); Angel e t a l . (1977); H e r b i l l o n e t a l . (1976) and
r e f e r e n c e s t h e r e i n ) . Working w i t h X.P.S.

on a p a r t i c u l a r t r o p i c a l s o i l k a o l i n i t e ,

namely t h e Y B i sample d e s c r i b e d by H e r b i l l o n e t a l . (1976), i t i s p o s s i b l e t o

s t u d y t h e Fe 2p l e v e l s i n c e t h e i r o n c o n t e n t o f t h i s p a r t i c u l a r c l a y i s h i g h .
Moreover, t h i s k a o l i n i t e can be c l e a n e d t o some e x t e n t by e x t r a c t i n g t h e c o a t i n g
i r o n o x i d e by ammonium o x a l a t e , as a l r e a d y mentioned by H e r b i l l o n e t a l . (1976).
On F i g u r e 9.1 t h e e v o l u t i o n o f t h e Fe 2p/Si 2p r a t i o i s p l o t t e d a g a i n s t t h e
A1 2p/Si 2p r a t i o f o r v a r i o u s c o n t a c t t i m e s between t h e c l a y and t h e s o l u t i o n .
The c u r v e c l e a r l y shows two d i s t i n c t p a r t s . I n t h e i n i t i a l s t a g e s o f t h e a t t a c k ,
i t can be n o t e d t h a t t h e Fe 2p/Si 2p r a t i o decreases, t h e A1 2p/Si 2p r a t i o r e -

m a i n i n g p r a c t i c a l l y c o n s t a n t . F o r l o n g e r c o n t a c t t i m e s , t h e two r a t i o s behave i n
t h e same way. The c r u d e k a o l i n i t e p a r t i c l e s seem c o a t e d w i t h a h i g h i r o n and a
l o w aluminum c o n t e n t g e l . A f t e r t h i s c o a t i n g has been d i s s o l v e d , t h e k a o l i n i t e
c r i s t a l i s a t t a c k e d by t h e complexing s o l u t i o n and i r o n and aluminum i o n s a r e
s i m u l t a n e o u s l y removed. These r e s u l t s c o n f i r m t h e f a c t a l r e a d y p o i n t e d o u t by
E.P.R.,

t h a t a f r a c t i o n o f the t o t a l i r o n content o f kaolinites i s inside the

s t r u c t u r e o f t h e m i n e r a l , p r o b a b l y s u b s t i t u t i n g A13+ i o n s . From t h i s study, i t

was n o t p o s s i b l e t o draw any c o n c l u s i o n a b o u t t h e o x i d a t i o n s t a t e o f i r o n s i n c e
t h e X.P.5.

Fig.9.2.

peaks were t o o broad.

Geometrical c o n s i d e r a t i o n s f o r X-rays p h o t o e l e c t r o n s d i f f r a c t i o n .

222
W i t h p o l y c r i s t a l l i n e samples, as i t has been a l r e a d y p o i n t e d o u t , X.P.S.

i s not

a b l e t o d i s t i n g u i s h between t h e v a r i o u s p o s s i b l e environments o f a g i v e n i o n . Working

w i t h s i n g l e c r y s t a l s , Evans e t a l .

(1979) have developed a method which a l l o w s some

comparisons between t h e v a r i o u s l o c a t i o n s i n s i d e t h e s t r u c t u r e . The s o - c a l l e d X-rays

p h o t o e l e c t r o n s d i f f r a c t i o n i s based on t h e a n g u l a r d e p e n d e n c e o f t h e v a r i o u s i n t e n s i t y r a t i o s o f a w e l l o r i e n t e d sample. By r o t a t i n g t h e s i i l g l e c r y s t a l a l o n g t h e c
a x i s (see f i g u r e 9 . 2 ) ,

the angle

between t h e e x c i t i n g r a d i a t i o n a n d t h e a n a l y z e d

electrons being f i x e d b y t h e geometryof t h e spectrometer, i t i s p o s s i b l e t o vary

the

e a n g l e c o n t i n u o u s l y f r o m 0 t o 90". The o u t g o i n g p h o t o e l e c t r o n s c a n b e d i f f r a c -

t e d by t h e atoms s u r r o u n d i n g t h e e m i t t i n g one and t h e n u m b e r o f c o l l e c t e d p h o t o e l e c t r o n s a t t h e e n t r a n c e s l i t o f t h e s p e c t r o m e t e r depends on t h a t a n g l e . I f two elements

A and B a r e l o c a t e d i n s i d e t h e c r y s t a l l a t t i c e o n t h e same k i n d o f s i t e s , i . e . w i t h

t h e same number o f t h e same s u r r o u n d i n g i o n s , t h e A / B X.P.S.

w i l l n o t v a r y when

peaks i n t e n s i t y r a t i o

changes. I f t h e two s i t e s a r e n o t e q u i v a l e n t , a dependence

oftheintensity ratio with

e w i l l be observed. I f , f o r example, t h e A e l e m e n t i s

d i s t r i b u t e d between two k i n d s o f s i t e s , one b e i n g e q u i v a l e n t t o t h e B environment,

w h i l e t h e o t h e r i s n o t , an i n t e r m e d i a t e s i t u a t i o n w i l l be observed and a c c o r d i n g l y
the i n t e n s i t y r a t i o w i l l bemodified.
T a k i n g t h e i n t e n s i t y o f t h e S i 2p l i n e as r e f e r e n c e , Evans e t a l . (1979) s t u d i e d t h e l o c a t i o n o f t h e v a r i o u s c a t i o n s i n muscovite, l e p i d o l i t e , p h l o g o p i t e and
b o t h n a t u r a l and Pb exchanged v e r m i c u l i t e . R e s u l t s o b t a i n e d by t h e X-rays p h o t o e l e c t r o n d i f f r a c t i o n patterns confirm those p r e d i c t e d by t h e s t r u c t u r a l determination

o f t h e isomorphous s u b s t i t u t i o n s i n m u s c o v i t e and l e p i d o l i t e . They a l s o

c o n f i r m t h e s u r f a c e e n r i c h m e n t i n A13+ i o n s i n t h e r e g i o n s o f f a c i l e cleavage
f o r p h l o g o p i t e and v e r m i c u l i t e , aluminum b e i n g a l m o s t e x c l u s i v e l y i n f o u r f o l d
coordination i n these regions.
A s i m i l a r s t u d y on t i t a n i u m c o n t a i n i n g b i o t i t e and p h l o g o p i t e (Evans and

R a f t e r y , 1980) has shown t h a t t i t a n i u m i s more l i k e l y T i 3 + t h a n T i 4 + i n t h e s e

micas. Moreover, a l l t h e t i t a n i u m i o n s a r e l o c a t e d i n o c t a h e d r a l s i t e s , n o t
e x a c t l y e q u i v a l e n t t o t h o s e o f Mg and Fe i o n s s i n c e t h e a u t h o r s observed a var i a t i o n with the

e a n g l e o f t h e T i 2p/Mg

2s i n t e n s i t y r a t i o .

T h i s a p p l i c a t i o n i s , i n my o p i n i o n , one o f t h e most p o w e r f u l i n X.P.S..

U n f o r t u n a t e l y , i t i s l i m i t e d t o t h e s t u d y o f s i n g l e c r y s t a l s , o r , perhaps, i n
t h e most f a v o u r a b l e cases, t o w e l l o r i e n t e d p o l y c r i s t a l l i n e samples.
9.3.2

AdsorDtion studies

Because i t s h i g h s e l e c t i v i t y f o r t h e s u r f a c e a n a l y s i s , X.P.S.

i s undoubtedly

an i d e a l t o o l f o r t h i s k i n d o f s t u d i e s . Working w i t h t h r e e c l a y m i n e r a l s , namely
k a o l i n i t e , i l l i t e and c h l o r i t e , Koppelman and D i l l a r d have s t u d i e s t h e adsorpt i o n o f Fe3+ and C r 3 + (1975), N i 2 + and Cu2'

(1977),

Cr3+

(1980 a ) , two complexes

o f C r 3 + i o n s (1980 b ) and v a r i o u s c o b a l t i o n s (1978 b ) . The comparison o f b i n d i n g

223
e n e r g i e s between an adsorbed i o n c o r e l e v e l and t h e same i o n c o r e l e v e l i n s i d e t h e
s t r u c t u r e , r e v e a l e d a g e n e r a l l o w e r i n g i n b i n d i n g energy o f t h e photopeak i s s u e d
f r o m adsorbed s p e c i e s , i f a d s o r p t i o n i s performed a t l o w pH v a l u e s .

The r e l a t i v e

l o w e r i n g o f t h e b i n d i n g energy f o r adsorbed i o n s w i t h r e s p e c t t o t h e same l a t t i c e

i o n s i s i n t e r p r e t e d as an i n c r e a s e i n e l e c t r o n d e n s i t y on t h e adsorbed metal due
t o the negative surface p o t e n t i a l o f t h e various clays. For adsorption a t higher
pH values, t h e X.P.S.

photopeaks o f adsorbed s p e c i e s a r e s i m i l a r i n b i n d i n g ener-

g i e s t o t h o s e o f t h e c o r r e s p o n d i n g h y d r o x i d e s . The q u a n t i t y o f adsorbed i o n s was

found t o v a r y always i n t h e f o l l o w i n g o r d e r : c h l o r i t e > i l l i t e > k a o l i n i t e .
The b e h a v i o u r o f Cu2+ i s q u i t e d i f f e r e n t . I n t h e adsorbed s t a t e , Koppelman and
D i l l a r d (1977) n o t e d an i n c r e a s e i n t h e b i n d i n g energy o f t h e Cu 2p 3/2 l e v e l
w i t h r e f e r e n c e t o t h e same l e v e l i n d i o p t a s e . T h i s i n c r e a s e i 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 o f Cu(OH)+ s u p e r f i c i a l s p e c i e s .
R e s u l t s c o n c e r n i n g a d s o r p t i o n o f some m i n e r a l complexes such as [ C O ( H ~ O ) ~ I ~ +
and [ C O ( N H ~ ) ~ ]on
~ +c h l o r i t e (Koppelman and D i l l a r d , 1978 b ) and [Cr(NH3)513+ and
[ C r ( e t h y l e n e diamine) 313'

on c h l o r i t e , i l l i t e and k a o l i n i t e (Koppelman and

D i l l a r d , 1980 b ) l e a d t o t h e same c o n c l u s i o n t h a t t h e adsorbed s p e c i e s behave as

h y d r a t e d c a t i o n s . C o n t a c t i n g c h l o r i t e w i t h s o l u t i o n o f [ C O ( N H ~ ) ~3' ] induces an
i n c r e a s e i n t h e pH o f t h e s o l u t i o n t o g e t h e r w i t h a r e d u c t i o n o f C03'

species i n t o

h y d r a t e d Co2+ s p e c i e s . The l o s s o f n i t r o g e n can be p u t f o r w a r d by a decrease o f t h e

N ls/Co 2p 3 / 2 r a t i o . A d s o r p t i o n o f chromium complexes i s a l s o c h a r a c t e r i z e d by

an i n c r e a s e i n t h e pH o f t h e s o l u t i o n and a c l a y c a t a l y z e d h y d r o l y s i s o f t h e amine
complexes.
S t u d y i n g t h e exchange p r o p e r t i e s o f b e i d e l l i t e , Adams and Evans (1979) deduced
t h e c a t i o n exchange c a p a c i t i e s o f t h a t c l a y f r o m X.P.S.

i n t e n s i t i e s measurements.

The r e s u l t s t h u s o b t a i n e d a r e i n c l o s e r e l a t i o n w i t h t h e C . E . C .
by chemical methods f o r Na+ and Ca2+ c a t i o n s . F o r K',
an a p p a r e n t excess o f t h e C.E.C.

values determined

Pb2+ and Ba2+ t h e y n o t e d

w i t h r e s p e c t t o t h e chemical v a l u e . T h i s excess

i s i n t e r p r e t e d as a consequence o f a s t r o n g a d s o r p t i o n o f t h e s e c a t i o n s on t h e
edges o r on t h e e x t e r n a l s u r f a c e o f t h e c l a y p a r t i c l e s .
Working w i t h l a r g e o r g a n i c molecules such as p o r p h y r i n s , Canesson e t a l . (1978)
were a b l e t o s t u d y t h e r e a c t i v i t y o f t h e s e molecules i n t h e i n t e r l a m e l l a r space
o f m o n t m o r i l l o n i t e . Meso-tetraphenyl p o r p h y r i n (TPP) and m e s o - t e t r a p y r i d y l
p h y r i n (TPyP) can undergo w i t h i n

por-

t h e c l a y s t r u c t u r e e i t h e r p r o t o n a t i o n o r com-

p l e x a t i o n . S i n c e t h e p o s i t i o n on t h e b i n d i n g energy s c a l e o f t h e N Is l e v e l i s s u e d
from adsorbed molecules i s s e n s i t i v e t o t h e s u r f a c e environment (Defosse and
Canesson,

1976), i t i s p o s s i b l e t o d i f f e r e n c i a t e p y r o l i t i c from t h e aza n i t r o g e n

atoms. Moreover, t h e i n t e n s i t y r a t i o between t h e two N 1s l e v e l s p e r m i t s a quant i t a t i v e d e t e r m i n a t i o n o f t h e v a r i o u s s p e c i e s . I t was concluded t h a t TPP undergoes p r o t o n a t i o n and t h a t t h e e x t e n t o f m e t a l l a t i o n i n t h e i n t e r l a m e l l a r space
depends upon t h e n a t u r e o f t h e exchangeable c a t i o n , t h e s t a b i l i t y o r d e r b e i n g

224
Cu2+ > Co2+, Sn4+ > Fez+, Mn2'.

The s i t u a t i o n i s q u i t e d i f f e r e n t w i t h TPyP s i n c e

t h i s molecule can undergo p r o t o n a t i o n on t h e p y r i d y l s u b s t i t u e n t s c o m p a t i b l e w i t h

m e t a l l a t i o n o f t h e p o r p h i n r i n g . T h i s i s observed w i t h Co2' and Cu2+ i n t e r l a y e r
as c a t i o n s . W i t h o t h e r c a t i o n s , c o m p l e x a t i o n i s n o t complete and r e s u l t s o b t a i n e d
by X.P.S.
al.,

c o n f i r m t h o s e o b t a i n e d by U . V .

and v i s i b l e s p e c t r o s c o p y (Van Damme e t

1978).

From t h i s survey o f X.P.S.

concluded t h a t X.P.S.

t e c h n i q u e s a p p l i e d on c l a y

m i n e r a l s , i t can be

emerges as a p r o m i s i n g t o o l .

Since s u r f a c e p r o p e r t i e s o f c l a y s and c l a y m i n e r a l s a r e o f m a j o r i m p o r t a n c e

X.P.S.

cannot f a i l t o occupy a more p r o m i n e n t p l a c e i n t h e f u t u r e f o r a b e t t e r un-

derstanding o f t h e various i n t e r a c t i o n s o f these minerals w i t h t h e external environment. The use o f X.P.S.

i s t h u s e x p e c t e d t o spread more b r o a d l y , n o t o n l y i n

t h e p a r t i c u l a r t o p i c o f c l a y m i n e r a l s , b u t a l s o i n a l l f i e l d s o f s c i e n c e f o r which
surface p r o p e r t i e s a r e o f major i n t e r e s t .

REFERENCES
Adams, I . , Thomas, J.M. and B a n c r o f t , J.M., 1972. An ESCA s t u d y o f s i l i c a t e
m i n e r a l s . E a r t h P l a n e t . S c i . L e t t . , 16: 429-432.
Adams, J.M., Evans, S., Reid, P . I . , Thomas, J.M. and W a l t e r s , M.J., 1977. Q u a n t i t a t i v e a n a l y s i s o f a l u m i n o s i l i c a t e s and o t h e r s o l i d s by X-ray p h o t o e l e c t r o n
spectroscopy. A n a l . Chem., 49: 2001-2008.
Adams, J.M. and Evans, S . , 1979. Exchangeand s e l e c t i v e s u r f a c e u p t a k e o f c a t i o n s
by l a y e r e d s i l i c a t e s u s i n g 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.). Clays,
Clay M i n e r . , 27: 248-252.
Anderson, P.R. and Swartz, W.E., J r . , 1974. 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 of
some a l u m i n o s i l i c a t e s . I n o r g . Chem., 13: 2293-2294.
Angel, B.R., C u t t l e r , A.H., R i c h a r d s , K.S. and V i n c e n t , W.E.J., 1977. S y n t h e t i c
k a o l i n i t e s doped w i t h fez' and Fe3+ i o n s . Clays, Clay Miner., 25: 381-383.
Angel, B.R. and V i n c e n t , W.E.J.,
1978. E l e c t r o n s p i n resonance s t u d i e s o f i r o n
o x i d e s a s s o c i a t e d w i t h t h e s u r f a c e o f k a o l i n s . Clays, C l a y M i n e r . , 26: 263-272.
Asami, K . and Hashimoto, K., 1977. The X-ray p h o t o e l e c t r o n s p e c t r a o f s e v e r a l
o x i d e s o f i r o n and chromium. C o r r o s i o n Science, 17: 559-570.
Brundle, C.R.,
1974. E l e c t r o n s p e c t r o s c o p y s t u d i e s o f a d s o r p t i o n and o x i d a t i o n
processes a t metal s u r f a c e s . J . E l e c t r o n . S p e c t r o s . R e l a t . Phenom., 5: 291-319.
Brunner, J. and Zogg, H., 1974. A n g u l a r dependence o f X-ray p h o t o e l e c t r o n s . J.
E l e c t r o n S p e c t r o s c . R e l a t . Phenom., 5 : 911-920.
Canesson, P., Cruz, M . I . and Van Damme H . , 1978. X.P.S. s t u d y o f t h e i n t e r a c t i o n
o f some p o r p h y r i n s and m e t a l l o p o r p h y r i n s w i t h m o n t m o r i l l o n i t e . Proc. V I t h I n t e r n . C l a y Conf.; M o r t l a n d , M.M. and Farmer, V . C . , e d i t o r s - E l s e v i e r , Amsterdam
pp. 217-225.
C a r r i e r e , B., D e v i l l e , J.P., B r i o n , 0. and Escard, J., 1977. X-ray p h o t o e l e c t r o n
s t u d y o f some s i l i c o n - o x y g e n compounds. J. E l e c t r o n Spectrosc. R e l a t . Phenom.
10: 85-91.
Cimino, A. and De A n g e l i s , B.A.,
1975. The a p p l i c a t i o n o f X-ray p h o t o e l e c t r o n
spectroscopy t o t h e s t u d y o f molybdenum o x i d e s and s u p p o r t e d molybdenum o x i d e c a t a l y s t s . J. C a t a l . , 36: 11-22.
Contour, J.P. and Mouvier, H.,
1975. R e l i a b i l i t y o f t h e carbon 1s l i n e f r o m cont a m i n a t i o n as an i n t e r n a l s t a n d a r d i n p h o t o e l e c t r o n s p e c t r a . J . E l e c t r o n Spect r o s c . R e l a t . Phenom., 7: 85-90.

225
Defosse, C., Friedman, R.M. and F r i p i a t , J., 1975. Etude p r e l i m i n a i r e des c o n d i t i o n s de p r e t r a i t e m e n t , de r e d u c t i o n e t d ' a d s o r p t i o n des z e o l i t h e s Y echangees
au n i c k e l p a r s p e c t r o s c o p i e des p h o t o e l e c t r o s n . B u l l . SOC. Chim. F r . , no 7-8:

1513-1518.

Defosse, C. and Canesson; P., 1976. P o t e n t i a l i t y of p h o t o e l e c t r o n spectroscopy

i n t h e c h a r a c t e r i z a t i o n o f s u r f a c e a c i d i t y : p h o t o e l e c t r o n and i n f r a r e d spect r o s c o p i c c o m p a r a t i v e s t u d y o f p y r i d i n e a d s o r p t i o n on NH - Y z e o l i t e a c t i v a t e d
4
a t v a r i o u s temperatures. J . Chem. SOC. Faraday Frans. I, 72: 2565-2576.
Defosse, C. Delmon, B. and Canesson, P . , 1977. X.P.S. s t u d y o f HY z e o l i t e s :
c h a r a c t e r i z a t i o n o f s u p e r f i c i a l c o m p o s i t i o n and a c i d i t y . Proc. 4th I n t e r n .
Conf. on M o l e c u l a r Sieves, M o l e c u l a r Sieves-11, ACS symposium s e r i e s , 40: 85-95
Ebel, M.F., 1974. Experiments on t h e c h a r g i n g e f f e c t f o r e l e c t r i c a l l y non conduct i v e samples i n t h e 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 . Vak. Tech., 23: 33-39.
Evans, S . , Adam, J.M. and Thomas J.M., 1979. The s u r f a c e s t r u c t u r e and composit i o n o f l a y e r e d s i l i c a t e m i n e r a l s : novel i n s i g h t s f r o m X-ray p h o t o e l e c t r o n
d i f f r a c t i o n , K-emission s p e c t r o s c o p y and cognate t e c h n i q u e s . P h i l . Trans. Roy.
SOC., London, A 292: 563-591.
Evans, S. and R a f t e r y , E., 1980. X-ray p h o t o e l e c t r o n s t u d i e s o f t i t a n i u m i n b i o t i t e a n d p h l o g o p i t e . C l a y M i n e r a l s , 1 5 : 209-218.
Friedman, R.M., Hudis, J., Perlman, M.L. and Watson, R.E.,
1973 a. E l e c t r o n i c
b e h a v i o r i n a l l o y s . G o l d - t i n . Phys. Rev. 6, 8: 2433-2440.
Friedman, R.M., Watson, R.E., Hudis, J . and Perlman, M.L., 1973 b. E l e c t r o n b i n d i n g i n m e t a l s . Grey and w h i t e t i n . Phys. Rev. B, 8: 3569-3575.
F r i p i a t , J.J., J e l l i , A.N.,
P o n c e l e t , G and Andre, J., 1965. Thermodynamic p r o p e r t i e s o f adsorbed w a t e r m o l e c u l e s and e l e c t r i c a l c o n d u c t i o n i n m o n t m o r i l l o n i t e
and s i l i c a s . J . Phys. Chem., 69: 2185.
H e r b i l l o n , A.J., Mestdagh, M.M., V i e l v o y e , L. and Derouane, E.G., 1976. I r o n i n
k a o l i n i t e w i t h s p e c i a l r e f e r e n c e t o k a o l i n i t e f r o m t r o p i c a l s o i l s . Clay M i n e r a l s ,

11: 201-220.

H e r c u l e s , D.M., Cox, L.E., O n i s i c k , S . , Wichols, G.D. and Carver, J.C., 1973.

E l e c t r o n s p e c t r o s c o p y (ESCA) : use f o r t r a c e a n a l y s i s . Anal. Chem., 45: 1973-

1975.

Hnatowich, D.J., Hudis, J., P e r l n a n , M.L. and R a g a i n i , R.C.,

1971. D e t e r m i n a t i o n
of c h a r g i n g e f f e c t i n 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 o f non c o n d u c t i n g s o l i d s .
J. Appl. Phys., 42: 4883-4886.
J e n k i n , J.G., Leckey, R.C.G. and Liesegang, J., 1977. The development o f X-ray
p h o t o e l e c t r o n spectroscopy : 1900-1960. J . E l e c t r o n Spectrosc. R e l a t . Phenom.

12: 35.

K a r i c k h o f f , S.W. and B a i l e y , G.W.,

1976. P r o t o n a t i o n o f o r g a n i c bases i n c l a y w a t e r systems. Clays and C l a y Miner., 24: 170.
Koppelman, M.H. and D i l l a r d , J.G., 1975. An ESCA s t u d y o f sorbed metal i o n s on
c l a y m i n e r a l s . Marine Chemistry i n t h e c o a s t a l environment, ACS symposium
s e r i e s , 18: 186-201.
Koppelman, M.H. and D i l l a r d , J.G., 1977. A s t u d y o f t h e a d s o r p t i o n o f N i ( 1 1 )
and Cu (11) by c l a y m i n e r a l s . Clays and C l a y Miner., 25: 457-462.
Koppelman, M.H. and D i l l a r d , J.G., 1978 a. The a p p l i c a t i o n o f 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. o r E.S.C.A.) t o t h e s t u d y o f m i n e r a l s u r f a c e c h e m i s t r y .
Proc. VIth I n t e r n . C l a y Conf., M o r t l a n d , M.M. and Farmer, V.C., e d i t o r s ,
E l s e v i e r , Amsterdam, pp. 153-166.
Koppelman, M.H. and D i l l a r d , J.G., 1978 b . An 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 i c
(X.P.S.) s t u d y o f c o b a l t adsorbed on t h e c l a y m i n e r a l c h l o r i t e . J. C o l l o i d
and I n t e r f . S c i . , 66: 345-351.
Koppelman, M.H., Emerson, A.B. and D i l l a r d , J.G., 1980 a. Adsorbed C r (111) on
c h l o r i t e , i l l i t e , and k a o l i n i t e : an 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 i c s t u d y .
Clays and Clay Miner., 28: 119-124.
Koppelman, M.H. and D i l l a r d , J.G., 1 9 8 4 b. A d s o r p t i o n o f C r (NH3),j3+ and Cr(en)33t
on c l a y m i n e r a l s and t h e c h a r a c t e r i z a t i o n o f chromium by X-ray p h o t o e l e c t r o n
spectroscopy. Clays and C l a y Miner., 28: 211-216.
Mc I n t y r e , N.S. and Z e t a r u k , D.G., 1977. 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 i c s t u d i e s
o f i r o n o x i d e s . A n a l . Chem., 11: 1521-1529.

226
Sergushin, N.P., Band, I . M . and Trzhaskovskaya, M.B., 1973. RelaNefedov, V . I . ,
t i v e i n t e n s i t i e s i n X-ray p h o t o e l e c t r o n s p e c t r a . J . E l e c t r o n Spectrosc. Relat.
Phenom., 2: 383-403.
Nefedov, V . I . and Sergushin, N.P., Salyn, U.V., Band, I . M . and Trzhaskovskaya, M.
B., 1975. R e l a t i v e i n t e n s i t i e s i n X-ray p h o t o e l e c t r o n spectra; p a r t 11. J.
E l e c t r o n Spectrosc. R e l a t . Phenom., 7: 175-185.
Nefedov, V . I . and Yarzhemsky, V.G.,
1977. R e l a t i v e i n t e n s i t i e s i n X-ray photoelect r o n spectra; p a r t 111. J . E l e c t r o n Spectros. R e l a t . Phenom., 11: 1-11.
O g i l v i e , J.L. and Wolbert, A., 1972. I n t e r n a l standard f o r e l e c t r o n spectroscopy
f o r chemical a n a l y s i s s t u d i e s o f supported c a t a l y s t s . Appl. Spectrosc., 26:
401-403.
S c o f i e l d , J.H., 1976. H a r t r e e - S l a t e r subshell p h o t o i o n i z a t i o n cross - s e c t i o n s
a t 1254 and 1487 eV. J . E l e c t r o n Spectrosc. Relat. Phenom., 8: 129-137.
Siegbahn, K., Nordling, C., Fahlamn, A., Nordberg, R. Hamrin, K., Hedman, J.,
Johansson, G., Bergmark, T., Karlsson, S.E., Lindgren, I. and Lindberg, B.,
1967. ESCA, atomic, molecular and s o l i d s t a t e s t r u c t u r e s t u d i e d by means o f
e l e c t r o n spectroscopy. Nova Acta Regiae S o c i e t a t i s Scientiarum Upsaliensis,
Ser. I V , Vol. 20.
S t u c k i , J.W., Roth, C.B. and B a i t i n g e r , W.E.,
1976. A n a l y s i s o f i r o n - b e a r i n g c l a y
m i n e r a l s by e l e c t r o n spectroscopy f o r chemical a n a l y s i s (ESCA). Clays and c l a y
Miner., 24: 289-292.
Tempere, J . Fr., Delafosse D . and Contour, J.P., 1977. Z e o l i t e s u r f a c e composit i o n by X.P.S..
Proc. 4 t h I n t e r n . Conf. on M o l e c u l a r Sieves, M o l e c u l a r Sieves
11, ACS symposium 'series, 40: 76-85.
Urch, D.S. and Webber, M., 1974. U n s u i t a b i l i t y o f g o l d as standard f o r nonconduct i n g samples i n X-ray p h o t o e l e c t r o n spectroscopy. J. E l e c t r o n Spectrosc. Relat.
Phenom., 5: 791-798.
Urch, D.S. and Murphy, S., 1974. The r e l a t i o n s h i p between bond l e n g t h s and o r b i t a l
i o n i z a t i o n energies f o r a s e r i e s o f a l u m i n o s i l i c a t e s . J . E l e c t r o n Spectrosc.
R e l a t . Phenom., 5: 167-171.
Van Dame, H., Crespin, M., Obrecht, F . , Cruz, M . I . and F r i p i a t , J.J., 1978.
Acid-base and complexation behavior o f p o r p h y r i n s i n t h e i n t r a c r y s t a l space o f
s w e l l i n g c l a y s : meso-tetraphenylporphyrin and meso-tetra ( 4 - p y r i d y l ) p o r p h y r i n
i n r n o n t m o r i l l o n i t e s . J. C o l l o i d I n t e r f . Sci., 66: 43-54.
Wagner, C.D.,
1972. S e n s i t i v i t y o f d e t e c t i o n o f t h e elements by p h o t o e l e c t r o n
spectrometry. Anal. Chem., 44: 1050-1053.
1977. Factors a f f e c t i n g q u a n t i t a t i v e determinations by X-ray photoWagner, C.D.,
e l e c t r o n spectroscopy. Anal. Chem., 49: 1282-1290.