Functionally Graded Materials Design Pro

FUNCTIONALLY GRADED
MATERIALS
Design, Processing and Applications
MATERIALS TECHNOLOGY SERIES
Series editor: Renee G. Ford
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FUNCTIONALLY GRADED
MATERIALS
Design, Processing and Applications
edited by
Y. Miyamoto
Professor, Joining and Welding Research Institute
Osaka University
W. A. Kaysser
Director, Institute for Materials Research
German Aerospace Center
B.H. Rabin
President, GA Powders, Inc.
A. Kawasaki
Professor, Faculty of Engineering
Tohoku University
Renee G. Ford
President, Renford Communications, Ltd.
SPRINGER SCIENCE+ BUSINESS MEDIA. llC

Library of Congress Cataloging-in-Publication Data
Functionally graded materials : design, processing, and applications I

edited by Y. Miyamoto.
p. em. --(Materials technology series)
ISBN 978-0-412-60760-8 ISBN 978-1-4615-5301-4 ( eBook)
DOI 10.1007/978-1-4615-5301-4
I. Functionally gradient materials. I. Miyamoto, Yoshinari.
II. Series: Materials technology series (Springer Science+Business Media, LLC)
TA418.9.F85F86 1999
620.1'1--dc21 99-40751
CIP
Copyright ® 1999 by Springer Science+Business Media New York

Originally published by Kluwer Academic Publishers in 1999
Softcover reprint of the hardcover 1st edition1999
All rights reserved. No part of this publication may be reproduced, stored in a

retrieval system or transmitted in any form or by any means, mechanical, photo-
copying, recording, or otherwise, without the prior written permission of the
publisher, Springer Science+Business Media, LLC
Printed on acid-free paper.

ABOUT THE SCULPTURE SHOWN ON THE COVER
The cover image of "Winged Torso", a sculpture which is composed of a cast polyester
resin substrate that has been flame-sprayed fIrst with zinc and then with bronze. After
polishing, the patina of the fmal piece is similar to foundry bronze and the high fIdelity
of the substrate's features is maintained. Throughout history, sculpture has been the
focus of interaction between mankind's need for creative expression and the available
materials technology. The Fusion Bronze™ process used to create this sculpture by
Boston sculptor Barbara Rubin-Katz l unites flame sprayed functionally graded metals
with the sculptor's art.
FUSION BRONZE™
The Fusion Bronze™ process utilizes molten metal spray technology in which an electric
current melts a bronze wire. The molten bronze (at about 1OOO°C) is entrained in a flow
of compressed air in a confmed space. This creates a jet of very small liquid bronze
particles that can coat a sculptural substrate (plaster, resin, Fiberglas™, or even paper,
wax, or wood) with a bronze overlayer. If the sculptural substrate is a material which
might be deformed or destroyed by contact with molten bronze, a layer of zinc, which
melts at about 400°C, is applied fIrst and then the bronze is deposited. The zinc acts as
a thermal plane dissipating the heat as the bronze is applied. Thus the fusion bronze
overlayer is truly a Functionally Graded Material (FGM).
0.10 inch
Surface
/ Oxide
o
Substrate - Cast
Zinc Layer or
Polyester Resin
Sulfide
Patina
Schematic of the Microstructure of a FGM, Fusion Bronze sculpture.
IBaroara Rubin-Katz trained at the Philadelphia College of Art and the Pennsylvania Academy of Fine Arts,
and also studied classical figurative sculpture with Evangelos Frudakis in Philadelphia. On moving to Boston
she continued her studies under the guidance of the late Peter Abate, a noted New England sculptor and
teacher. She started showing her work publicly in the late 1980's and from the outset received recognition
and awards. Since the early 1990's her work has been seen in many exhibitions at the Copley Society of
Boston, the Federal Reserve Bank of Boston, Fanueil Hall, Hellenic College, Montserrat College of Art,
Bradford College, Worcester Polytechnic Institute and many regional galleries. In 1992 the Copley Society
of Boston awarded Barbara Rubin-Katz the highly esteemed designation of "Copley Artist".
Contents
Contributors IX
Preface Xlll
Acknowledgements xv
INTRODUCTION 1
LESSONS FROM NATURE 7
GRADED MICROSTRUCTURES 29
MODELING AND DESIGN 63
THE CHARACTERIZATION OF PROPERTIES 89
PROCESSING AND FABRICATION 161
APPLICATIONS 247
SUMMARY AND OUTLOOK 315
Index 319
Contributors
Prof. N. Arakt(5.3.2, 5.3.4)*

Department of Energy and Mechanical Engineering, Shizuoka
University, Hamamatsu 432-8011, Japan
Dr. L. Chen (1)
Institute for Materials Research, Tohoku University, Katahira 2-1-1,
Aoba-ku, Sendai 980-0812, Japan
Dr. N. Cherradi_(5.3.3)
38 Avenue de Montoie CH-I007 Lausanne, Switzerland
Prof. M. J. Cima_( 6.7.1)
Massachusetts Institute of Technology, 77 Mass. Ave., Room 12-011,
Cambridge, MA 02139, U.S.A.
Prof. F. Erdogan (5.4.3a, 5.4.3b)
Department of Mechanical Engineering and Mechanics, Lehigh
University, Bethlehem PA, 18015, U.S.A.
Dr. R. G. Ford (Ch.1 - 8)
Editor-in-chief, Materials Technology, P.O. Box 72, Harrison, NY
10582-0072, U.S.A.
Prof. M. Gasik (7.5)
Laboratory of Materials Processing and Powder Metallurgy, Helsinki
University of Technology, Vuorimiehentie 2A, FIN-02150 Espoo, Finland
Prof. A. M. Glaeser_(6.6.2)
Department of Materials Science and Mineral Engineering, Hearst
Mining Building, University of Cali fomi a Berkley, CA 94720 U.S.A.
Prof. T. Hirai (6.3.5, 7.2.1b)
Institute for Materials Research, Tohoku University, Katahira 2-1-1,
Aoba-ku, Sendai 980-0812, Japan
x Contributors
Dr. K. Hirano (5.4.3c)

Department of Materials Science and Bioengineering, Mechanical
Engineering Laboratory, AIST, MIT!, Namiki, 1-2, Tsukuba, 305-0044,
Japan
Mr. T. Hirano (4.3.2, 7.3.2c)
Electronic Engineering Laboratory, Daikin Industries, Ltd., Aza-Ohtani,
Okamoto, Kusatsu-City, 525-0044, Japan
Prof. B. I1schner (6.2.1, 6.2.3a)
Swiss Federal Institute of Technology, MX-D, EPFL Ecublens, CH-1015
Lausanne, Switzerland
Dr. H. Imai (7.3.3)
Research Association for Nuclear Facility Decommissioning, 821-100,
Funaishikawa, Tokai, Ibaraki, 319-1111, Japan
Dr. Y. Itoh (7.3.3)
Power and Industrial Systems Research and Development Center,
Toshiba Corporation, Ukijima 2-1, Kawasaki, Kawsaki-City, 210-0862,
Japan
Dr. C. Kawai (5.5.4)
Itami Research Laboratories, Sumitomo Electric Industries, Ltd., 1-1-1,
Koya-Kita, Itami, Hyogo, 664-0016, Japan
Prof. A. Kawasaki (Ch.5, 5.1,5.3.1,5.3.5,5.4.1,5.4.2,5.4.4,5.4.5,5.5)
Department of Materials Processing, Faculty of Engineering, Tohoku
University, Sendai 980-8579, Japan
Prof. Dr. W. A. Kaysser (Ch.6 and 7, 6.1, 6.2, 6.3.1, 6.3.2, 6. 3. 3a,
6.3.4, 6.3.6, 6.3.7a, 6.4, 6.5, 6.6.1, 6.6.3, 6. 7.2, 7.1, 7.2.1c, 7.3.1, 7.3.2a,
7.3.2b, 7.3.4, 7.4)
Director, Institute of Materials Research, German Aerospace Center
51140 Cologne, Germany
Prof. Y. Koike (7.7)
Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi,
Kohoku-ku, Yokohama, 223-0061, Japan
Prof. M. KoizumU 1)
REC, Ryukoku University, Otsu, 520-2123, Japan
Mr. K. Kurihara (6.3.5)
Fujitsu Laboratories Ltd., 10-1, Wakamiya Morinosato, Atsugi-shi,
Kanagawa, 243-0122, Japan
Prof. J. J. LannuttU6.2.1a)
Department of Materials Science and Engineering, Ohio State University,
477 Watts Hall, 2041 College Road, Columbus, OH 43210-1179 U.S.A.
Prof. M. I. MendelsonJ6.3.3b, 7.2.1b, 7.2.2, 7.2.3)
College of Science and Engineering, Loyola-Marymount University,
Loyola Blvd. at 80th West St., Los Angeles, CA 90045-2699 U.S.A.
Contributors Xl
Prof. Y. Miyamoto (Ch.l- 8, 1, 5.2, 6.2.3f, 6.7.1, 7.7, 7.8.2, 8)

Joining and Welding Research Institute, Osaka University, Ibaraki,
Osaka 567-0047, Japan
Dr. T. Nagano (6.7.3)
Japan Science and Technology Corporation, Ceramic Superplasticity
Project, Fine Ceramic Center, Atsuta, Rokuno 2-4-1, Nagoya 456-8587,
Japan
Dr. M. Niino (1)
Kakuda Research Center, National Aerospace Laboratory, STA Kakuda,
Miyagi 981-1525, Japan
Prof. I. Nishida (7.3.2c)
National Research Institute for Metals, 1-2-1, Sengen, Tsukuba-shi,
Ibaraki, 305-0047, Japan
Prof. F. Nogata (2)
Department of Mechanical System Engineering, Faculty of Engineering,
Gifu University, Yanagido 1-1, Gifu, 501-1193, Japan
Dr. H. Ohnishi (7.8.1)
Department of Orthopaedic Surgery, Artificial Joint Section and
Biomaterial Research Laboratory, Osaka Minami National Hospital, 677-2,
Kido-Cho, Wachinagano-Shi, Osaka, 586-0001, Japan
Dr. B. H. Rabin (Ch. 3 and 4, 3, 4)
President, GAPowders Inc., 2300 N. Yellowstone Idaho Falls, ID 83404,
U.S.A.
Mr. K. S. Ramesh (4.3.4)
Battelle Pacific Northwest Laboratory, Richland, WA 99352-9668,
U.S.A.
Dr. P. Sarkar (6.3. 7b)
Advanced Industrial Materials and Processes Group, Alberta Research
Council, 250 Karl Clark Road, Edmonton, Alberta, Canada, T6N 1E4
Prof. M. Sasaki (6.3.5, 7.2.1b)
Department of Materials Science, Faculty of Engineering, Muroran
Industrial University, Muzumoto, 27-1, Muroran, 050-0071, Japan
Mr. N. Shimoda (6.3.3b)
Steel Research Laboratories, Nippon Steel Corporation, 20-1, Shintomi
Futtsu, Chiba, 293-8511, Japan
Prof. I. Shiota_(7.4.1)
Department of Chemical Engineering, Kogakuin University, 2665-1,
Nakano, Hachioji, Tokyo, 192-0015, Japan
Dr. Y. Tada_(7.2.1a, 7.2.1b)
Foundation for Promotion of Japanese Aerospace Technology, 1-16-6
Izumi-Chuo, Izumi-ku, Sendai, Miyagi, 981-3133, Japan
Prof. M. Tamura_(6.2.2)
xu Contributors
Department of Materials Science and Engineering, National Defense

Academy, 1-10-20 Hashirimizu Yokosuka-City, 239-8686, Japan
Dr. T. Tateishi (7.8.3)
Bio-Group, National Institute for Advanced Interdisciplinary Research,
AIST, MITI, Higashi 1-1-4, Tsukuba 305-0046, Japan
Dr. R. L. Williamson (3, 4)
Idaho National Engineering and Environmental Laboratory, P.O. Box
1625, Idaho Falls, ID 83404, U.S.A.
Dr. J. Yoo (6. 7.1)
Massachusetts Institute of Technology, 77 Mass. Ave., Room 12-011
Cambridge, MA 02139, U.S.A.
Prof. J. Yoshino (7.6)
Department of Physics, Tokyo Institute of Technology, Ohokayama,
Meguro, Tokyo 152-0033, Japan
* The numbers in parentheses are the contributed sections and edited

chapters.
Preface
Seven years have elapsed since Dr. Renee Ford, editor-in-chief of

Materials Technology, first suggested to me to publish a book on
Functionally Graded Materials (FGMs). She said that the FGM concept, then
largely unknown outside of Japan and a relatively few laboratories
elsewhere, would be of great interest to everyone working in the materials
field because of its potentially universal applicability. There was no book
about FGMs in English at that time, although the number of research papers,
review articles, and FGM conference proceedings had been increasing
yearly. We discussed what the book should cover, and decided it should
present a comprehensive description from basic theory to the most recent
applications of FGMs. This would make it useful both as an introduction to
FGMs for those simply curious about what this new materials field was all
about, and also as a textbook for researchers, engineers, and graduate
students in various material fields. The FGM Forum in Japan generously
offered to support this publication program.
Because it is very difficult for an individual author to write a book that
covers such a wide range of various aspects of many different materials, I
invited more than 30 eminent materials scientists throughout the world, who
were associated with FGM research, to contribute selected topics. I also
asked several leading researchers in this field to edit selected chapters: Dr.
Barry H. Rabin, then at the U.S. Department of Energy's Idaho National
Engineering and Environmental Laboratory and now President of GA
Powders, Inc.; Dr. Wolfgang A. Kaysser, Director of the Institute for
Materials Research at the German Aerospace Center in Cologne; and Dr.
Akira Kawasaki, Professor of Materials Science at Tohoku University in
Japan. Dr. Ford reviewed each edited chapter and rewrote the book in a
XIV Preface
uniform style. This approach proved to be very time consuming, and is the
major reason for the time it has taken to complete this book for publication.
However, it has been constantly updated to reflect the latest developments.
A unique feature of this book is that its writing and production has been
accomplished completely electronically. Nothing was printed on paper until
the book's actual pUblication. Internet communication has developed rapidly
worldwide since we started the actual writing and editing in 1994. We
decided to use e-mail for communicating and for transmitting the files to
each other. However, at the beginning we encountered some confusion and
incompatibility when exchanging files. Part of the problem was due initially
to inexperience with using the Internet and part due to our different
computer systems - some of us are Macintosh users and others use pes.
However, we soon overcame our hardware and software incompatibilities,
developed a system for file identification so we could keep track of the most
recent versions of each chapter, and became quite adept at electronic editing.
Older manuscripts were updated quickly and the latest research results were
added easily using e-mail. Many of the figures and tables were reformed or
newly prepared using computer graphics by my colleagues, Dr. J. S. Lin and
Miss K. Agu assisted by some of my students. Finally, Dr. Rabin formatted
the entire manuscript for submission to the publisher electronically. We are
proud that this is the first book written and edited completely electronically
spanning three continents.
The sculpture on the book's cover is by the contemporary artist, Barbara
Rubin-Katz. Throughout human history, sculpture has been the focus of
interaction between the need for artistic expression and the materials
technology available. The fusion bronze process used in creating this
sculpture, which unites flame sprayed functionally graded metals with the
sculptor's art, exemplifies this tradition. This abstract sculpture of a torso
symbolizes that optimized FGMs can be used to create beauty as well as
function.
Dr. Yoshinari Miyamoto, Editor
Professor ofMaterials Science, Joining and Welding Research Institute,

Osaka University. Japan
Acknowledgements
The authors would like to gratefully acknowledge the sponsorship of

FGM FORUM, The Society for Non-Traditional Technology, Kotohira
Kaikan Bldg. 1-2-8, Toranomon, Minato-ku, Tokyo 105-0001, Japan. We
also appreciate the tremendous patience and support shown by all the
contributors.
Chapter 1
INTRODUCTION
Keywords: Element, material ingredient
1. DEFINITIONS AND HISTORICAL PERSPECTIVE
In a Functionally Graded Material (FGM) both the composition and the

structure gradually change over the volume, resulting in corresponding
changes in the properties of the material. The structural unit of an FGM is
referred to as an element [1] or a material ingredient [2, 3]. It is a conceptual
unit for constructing an FGM that includes various aspects of its chemical
composition, physical state, and geometrical configuration. The term,
material ingredient, probably expresses the overall concept best. Typical
examples are listed in Table 1.1. Material ingredients can resemble
biological units such as cells and tissues. For example, bamboo, shell, tooth,
and bone all have graded structures consisting of biological material
ingredients. Graded structures and functions in nature are discussed in
Chapter 2 on Lessons from Nature.
T,ahIll
e , , FGM scan be Compose d 0 fV' anous M.ateria11ngred'lents,
Chemical inorganic, organic, ceramic, metal, polymer
Physical electronic state, ionic state
crystalline state, dipole moment, magnetic moment
band gap, potential well, barrier
Geometrical granule, rod, needle, fiber, platelet, sheet
pore, texture, orientation
Biological complex macromolecule, organelle, cell, tissue
2 Chapter 1
In the simplest FGMs, two different material ingredients change

gradually from one to the other as illustrated in Figure 1.1 (a). The material
ingredients can also change in a discontinuous way such as the stepwise
gradation illustrated in Figure 1.1 (b). This type of structure can also be
considered an FGM. The most familiar FGM is compositionally graded from
a refractory ceramic to a metal. It can incorporate incompatible functions
such as the heat, wear, and oxidation resistance of ceramics with the high
toughness, high strength, machinability, and bonding capability of metals
without severe internal thermal stress.
(a) (b)
Figure 1.1 . (a) Continuous and (b) stepwise graded structures.
Pores also are important material ingredients of FGMs. A gradual

increase in the pore distribution from the interior to the surface can impart
many properties such as mechanical shock resistance, thermal insulation,
catalytic efficiency, and the relaxation of thermal stress. Even if the
gradation of the material ingredients is limited to a specific location in the
material such as the interface, a joint, or a surface as shown in Figure 1.2, the
material can be considered to be an FGM because it incorporates the FGM
concept. Although this concept can be extended to materials with functions
that are designed to change gradually over time or with environmental
conditions, such as a drug delivery system, these time dependent functions
are actually produced by tailoring the spatial gradation of the material
ingredients. The creation of multiple or new functions with graded
structures, rather than the graded material itself, is the basis for the FGM
concept as reflected in this book.
The general idea of structural gradients first was advanced for composites
and polymeric materials in 1972 [4, 5]. Various models were suggested for
gradients in composition, in filament concentration, and in polymerization
along with possible applications for the resulting graded structures.
However, there was no actual investigation about how to design, fabricate,
and evaluate graded structures until the 1980s.
Introduction 3
Figure 1.2. Local gradients at the joint (a) and surface (b).
In 1985, the use of continuous texture control was proposed in order to

increase the adhesion strength and minimize the thermal stress in the ceramic
coatings and joints being developed for the reusable rocket engine [6]. The
developers realized that this continuous control of a property could be
extended to a more general concept that could be applied to impart new
properties and functions to any material by gradually changing its texture or
composition. At this time, the concept of the material ingredient was
introduced for designing such materials [1].
In 1986, these types of materials were termed functionally gradient
materials, which soon became abbreviated to the now familiar, FGM. In
1995, as a consequence of a discussion at the Third International Symposium
on FGMs held in Lausanne in 1994, it was decided to change the full name
to functionally graded materials because it is more accurate both
descriptively and grammatically.
Since FGMs are not homogeneous materials, it was recognized that in
order to create them, comprehensive studies would need to be done in design
methodology and theoretical modeling as well as in processing and
evaluation. Therefore, in 1987 a 5-year research program, "Fundamental
Studies on the Relaxation of Thermal Stress by Tailoring Graded
Structures," was initiated in Japan [7]. The program's focus was to develop
FGMs for high temperature use with the objective of using them for the
hypersonic space plane. Since 1989, the results of these research and
development programs have been disseminated worldwide via papers,
articles, international meetings, and exchange programs. An international
symposium on FGMs has been held every 2 years starting with the first one
in 1990 in Sendai followed by San Francisco, Lausanne, Tsukuba, and
4 Chapter 1
Dresden. Today, the FGM concept extends over a variety of materials fields
worldwide.
2. OVERVIEW OF APPLICATIONS
The FGM concept is applicable to many fields, as illustrated in Figure

1.3. In the engineering applications to cutting tools, machine parts, and
engine components, incompatible functions such as heat, wear, and
corrosion resistance plus toughness, and machinability are incorporated into
a single part. For example, throwaway chips for cutting tools made of graded
tungsten carbide/cobalt (WC/Co) and titanium carbonitride (TiCN)-WC/Co
have been developed and commercialized that incorporate the desirable
properties of high machining speed, high feed rates, and long life [8].
Various combinations of these ordinarily incompatible functions can be
applied to create new materials for aerospace, chemical plants, and nuclear
energy reactors.
ENGINEERING
NUCLEAR ENERGY
Nudear reactor ~enls
Figure 1.3. Potentially applicable fields for FGMs.

Introduction 5
The FGM concept is also applicable to functional materials. A graded

potential for electrons or ions can be tailored by using techniques such as
molecular beam epitaxy (MBE), metal-organic chemical vapor deposition
(MOCVD), and scanning probe microscopy (SPM) to create graded
structures on the atomic scale. This can produce unique quantum effects that
could result in new applications for semiconductor and sensor materials.
Graded band theory and its application to semiconductor materials are
discussed in Chapter 7.
The application of FGMs to biomaterials is growing in importance. Over
2500 surgical operations to incorporate graded hip prostheses have been
successfully performed in Japan over the past twelve years. These graded hip
implants enable a strong bond to develop between the titanium implant, bone
cement, hydroxyapatite (HAp), and bone. The bone tissue penetrates HAp
granules inserted between the implant and the bone forming a graded
structure. The application of the FGM concept to hip implants is also
discussed in Chapter 7.
There are many potentially useful applications of the FGM concept. For
example, structural walls that combine the two functions of thermal and
sound insulation with good specific strength could be made by the gradation
of both the porosity and the composition. Also, it might be possible to design
attractive interference colors for automobiles by dispersing graded coated
particles such as titanium dioxide/mica (Ti02/mica) in the body coating.
Graded combinations of flexibility or elasticity and rigidity could enhance
sports equipment such as golf clubs, tennis rackets, and skis. The sculpture
on the book's cover shows the use of gradation in the creation of a work of
art.
By exploiting the myriad possibilities inherent in the FGM concept, it is
anticipated that the properties of materials will be optimized and new
functions for them created. A comprehensive discussion of design,
modeling, processing, and evaluation of FGMs as well as their applications
is covered in this book.
REFERENCES
1. Hirai, T. (1996) Functional gradient material, in Processing o/Ceramics, Part 2, (ed. R.J.
Brook), Materials Science and Technology, 17B, 293-341, VCH Publishers, Weinheim.
2. Mortensen, A. and Suresh, S. (1995) Functionally graded metals and metal-ceramic
composites: Part I "Processing", International Materials Reviews, 40(6), 239-265.
3. Mortensen, A. and Suresh, S. (1998) Fundamentals o/Functionally Graded Materials,
10M Communications Ltd., London.
4. Bever, M.B. and Duwez, P.E. (1972) Gradients in composite materials, Mater. Sci. Eng.,
10, 1-8.
6 Chapter 1
5. Shen, M. and Bever, M.B. (1972) Gradients in polymeric materials, J. Mater. Sci., 7, 741-
746.
6. Niino, M. et. al. (1984) Fabrication of a high pressure thrust chamber by the eIP forming
method, AIAA Paper No. 84-1227.
7. Koizumi, M. and Niino, M. (1995) Overview ofFGM research in Japan, in Functionally
Gradient Materials, (eds. B.H. Rabin and I. Shiota), MRS Bull. XX, 19-21.
8. Miyamoto, Y. (1997) Applications ofFGM in Japan, in Functionally Graded Materials:
Manufacture, Properties, and Applications, (eds. A. Ghosh et al.) Ceramic Transactions,
Am. Ceram. Soc. 76, 171-189.
Chapter 2
LESSONS FROM NATURE
Keywords: Biological structure, composite material, multifunctionality, optimum design,

mechanosensor, intelligent material system, adaptability, self-optimization,
self-adaptive modeling, structural efficiency, weight-cost, fiber reinforcement,
microstructure, cellular structure, bamboo, mollusk shell, palm tree, bone
1. INTRODUCTION
In examining biological load carriers such as the stems of plants and the
trunks of trees, animal bones, mollusk shells, and other biological hard
tissues, it can be seen that their geometry changes to accommodate to their
physical environment. This implies that they are highly adapted to all
boundary and loading conditions defined by their environment. Only the
most economical construction is able to survive the intense competition for
energy as well as the external physical conditions with the minimal amount
of materials available to them in their limited living space. For example, the
interior structure (architecture) of a bone has an optimized shape with
respect to the direction of principal stress and the magnitude of the shear
stress [1]. This has been explained to be due to an optimized mechanical
design that is characterized by uniform stress distribution with no localized
stress peaks [2]. This suggests that both bone and other biological tissues are
managed by a self-optimizing system with sensing mechanisms that can
detect external mechanical stimuli in order to control the modeling and
remodeling of the skeletal system [3]. It can be inferred, therefore, that the
shape and ingenious construction of biological hard tissues are the result of a
continuous process of intelligent optimization.
8 Chapter 2
The basic characteristics of biological hard tissue, such as microstructure,

function, and modeling systems both fascinate and inspire the designers of
engineering structure. The basic difference between biological and artificial
structures is that the former has living organisms that can be characterized
by multi functionality, hierarchical organization, and adaptability [4, 5].
Consequently, biological structures are complicated and nonuniform. This
suggests that an intelligent and functional combination of elements,
materials, and components with different strengths in the same structure can
result in hybrid systems whose properties are designated for specific
purposes.
This chapter describes the ingenious construction, strength, and natural
process of optimization by a cell-based mechanosensing system in certain
biological tissues. Bamboo, is used as an example for the development of
new material and structural concepts, such as composites of multiphased and
functionally graded materials.
2. GENERAL MORPHOLOGICAL
CHARACTERISTICS OF BIOLOGICAL TISSUE
A structure can be defined as any assemblage of materials intended for

sustaining loads [6]. Although it is difficult to distinguish between structures
and materials in biological structural systems, from a macroscopic viewpoint
there are three ways to sustain external loads as shown in Figures 2.1, 2.2,
and 2.3.
1. By changing the microstructure (that is by moderating the thickness
and/or the shape), e.g., bamboo, mollusk shell.
2. By changing the size and/or shape of a body, e.g., the trunk of a tree and
the stem of a plant, the shaft of a leaf or a feather.
3. By combining the first two types, e.g., human and animal bone, the
spicule of a sea urchin, a rat tooth.
Graded structures of the first type (1) are more common in nature than
the other two types.
Lesson from Nature 9
lamellar
foliated
bamboo
nacre
• fibe r plaooment
• volume densuty mol usc shell
Purplish Washington clarY

(Saxidomus purpuratus)
Figure 2.1. A way to accommodate or sustain external loads by changing the microstructure
(1) in biological systems.
sunnyG) ® ® 0 ®
side shaft
4A ~~
4, I
100 -..I 500
.I
900
13)0
1700
L:2700 nm
The shape of a ClOSS section of the leaf

CD ® ® (3) ®
~~~~~ tree trurk
Figure 2.2. A way to accommodate or sustain external loads by changing the size and/or
shape of a body (2) in biological systems.
10 Chapter 2
Femur head
• shape and size

• para sity
animal bone tooth
Figure 2.3. Away to accommodate or sustain external loads by combining types (1) and (2) in
biological systems.
3. A NATURAL PROCESS OF OPTIMIZATION:

ADAPTIVE MODELING WITH A CELL-BASED
MECHANOSENSOR
3.1 Bamboo
Bamboo belongs to the genus Bambuseae in the grass family,

Gramineae. Like other grasses, bamboo grows in thick clumps, but like trees
it often attains great heights. In some species in Asian monsoon forests, the
woody, hollow aerial stems of bamboo often grow to heights of about 30 m
and to diameters of about 25 cm.
When the transverse section of a bamboo stem is cut, many beautiful
brown spots can be seen (Figure 2.4 (a». These small spots on the outside
and the inside of the cross section vary widely in shape. Figure 2.4 (b) is an
enlarged photograph of one of these spots located near the inside of the cross
section. It is shaped like a flower. In the center, there are two large holes
(these are vessels in the xylem -- the supporting and water conducting tissue
of vascular plants), and a few small holes (these are sieve tubes in the
phloem -- the food conducting tissue of vascular plants). If both of these
holes are replaced by one big hole, the significance of the flower shape can
be understood by comparing it with the stress distribution around a single
hole in an infinite plate (see Figure 2.5 (a)) and around three holes in an
actual plate, when both are subjected to uniaxial tension (see Figure 2.5 (b) -
- a photo of elastic stress patterns). The optimum way to reinforce these
holes is to insert fiber bundles in accordance with the stress distribution.
Therefore, the shape of the fiber bundles (the black areas in Figure 2.4 (b)
that consist of four or five hundred fine fibers per bundle) suggests the
presence of stress around the vascular structures in the xylem and phloem.
L....-_ _ _.....I' Smm L..--...J O.1mm
(a) Transverse section through (b) Enlargement of

the stem of Moso bamboo a vascular bundle
Figure 2.4. A transverse section showing the placement of fiber bundles. (a) Transverse
section through the stem of Moso bamboo. (b) Enlargement of a vascular bundle.
The contours of biological structures such as tree stems, red deer antlers,
human tibia, and tiger claws have been shown to be highly optimized with
respect to their mechanical strength and minimum weight [2, 6]. This implies
that biological structures may possess mechanical sensing capability.
Voltage signal curves obtained from a bamboo stem SUbjected to an external
bending moment, measured using an electrocardiograph, are shown in
Figures 2.6 and 2.7 (the box shows a typical biological electric signal) [7].
The curves indicate the presence of a spike on loading and unloading. The
higher voltage signal was recorded on the compression side rather than the
tension side of the bamboo stem. This implies that the sensitivity of a
bamboo cell is greater for detecting compression (stress/strain) than tension.
These signals could be used to trigger adaptive growth related to the
direction of the stress. Data, obtained from other plants (see Figure 2.8),
show that the characteristic features of the signals depend on the kinds of
12 Chapter 2
plants. In addition, no voltage signals were induced from a specimen boiled

in hot water for 1 hour or from a dried specimen that lost 50% of its weight.
Because boiling or drying specimens kills the plant cells, the voltage signals
recorded must have been produced by live cells in the stressed materials [8].
This indicates that live bamboo cells have the ability to sense at least some
of the information induced by external mechanical stimuli.
cr
L...J 1 mm
cr
(a) Stress distribution around (b) Photoelastic stress pattern

a hole in an infinite plate around three holes
Figure 2.5. Stress distribution around holes in the structure of bamboo. (a) Stress distribution
around a hole in an infinite plate. (b) Photoelastic stress pattern around three holes.
Moso bamboo
(Phyllostachys pubescens Mazel)
voltmeter
@ CD @
~r
:';'"
W=19.6 N
Figure 2.6. Experimental set up to measure the voltage signals of bamboo.

stress duration ® bipolar lead system

gj
~I--...L.....-"""'T'"----r-
Tension
en
CD-
Compression
@-
>
E
o~IC==========~~
stress duration
20min .
@=CD-(g)
Typical bone signal
[Williams,et aI. ~9751
@- t--J,...J"',,----_ _----1-.L~
~I'--l--===========----I
stress duration
G)® : unipolar lead system
Figure 2.7. A typical example of the voltage signals induced by the bending moment of a
bamboo stem. The induced signals were recorded using unipolar and bipolar lead systems that
make possible recording both tension and compression points.
Piezoelectric properties have been found in bone subjected to stress [9].

Several experimental observations have been reported that bone
demonstrates a piezoelectric effect [10, 11, 12, 13]. This is used to explain
the concept of stress- or strain-induced bone remodeling referred to as Wolfs
law [4]. It appears that bone converts mechanical stress to an electrical
potential that influences the activity of osteoclasts (large cells in growing
bone) and osteoblasts (bone-forming cells) [14]. As described above, the
interior structure of bone (trabecular architecture) is arranged in compressive
and tensile systems corresponding to the direction of the principal stress [1].
The properties of the voltage signals induced in bamboo may be similar
to the piezoelectric effect in bone. Therefore, the electrical properties of both
bone and bamboo probably play an important role in the modeling and
remodeling of the skeletal system in biological hard tissue. As evidence,
bamboo that was grown on steep ground has an enlarged vascular bundle [8].
The deformed contours of the bamboo stem and the asymmetric shape of the
fiber bundles (deformed petal shape) reflect the biased loading conditions of
their environment. The recorded electric signals and the location of the fiber
14 Chapter 2
1
recorded signals
i 1.1. bipolar lead system
v-t curve stress dll"a tion

, i
restingpo1ential ~
II ~[~ rubber plant

(Firus elastica Roxb)
'-----'
"1"1 ~[E9
20 min.
palm tree
(Butia ya tay)
fig tree
(Firus carica Unn)
~~[~ bamboo
(Mosobamboo)
Figure 2.B. Typical examples of the voltage signals induced by the bending moment of
certain plants including bamboo.
bundles suggest that bamboo has a stress/strain-induced adaptive modeling

system.
The data suggest that bamboo cells may possess a mechanosensor that
determines the shapes in which they grow, such as the thickness of the stem
and the volume density of the fiber, thereby compensating for the applied
external load in order to obtain a homogeneous distribution of the stress.
Bamboo could be regarded as an "intelligent material system" that has a
mechanosensor. The volume density of the fiber and its distribution in the
bamboo provide important information about its mechanical properties.
In bone remodeling, it is known that a bone that is bent by a mechanical
load adapts by depositing new bone on the concave (compression) side, and
by resorbing the bone on the convex (tension) side [4]. In this way the bone
becomes adapted to an imposed mechanical stress. A similar adaptation
(growing) mechanism can be seen with plants. Specifically, the compression
side of a softwood tree grows faster than the tension side (called
compression wood), and the tension side of a hardwood tree grows faster
than the compression side (called tension wood).
Figure 2.9 shows the transverse section of two tree stems: a Japanese
cedar (softwood) and an ash (hardwood). Figure 2.10 shows the voltage
signals induced in them by the bending moment of these two types of plants.
The sensitivity of the electrical signals induced from the tension and
compression sides is consistent with the growth direction of the tree trunks.
Thus the growing mechanism of plants is governed by the ability of the cells
to detect stresses. The evidence indicates that electrical signals control the
growth of plants subjected to a load. Figure 2.11 is a scanning electron
micrograph of the fractured fibers that form the backbone of bamboo. The
distribution of fiber density at two different transverse sections (the lower
position is specimen A and the upper is specimen B) in a bamboo stem is
shown in Figure 2.12. This graph indicates that in a bamboo stem, the fiber
density gradually increases from the inside to the outside surface as well as
from the lower part to the upper part. These graded structures produce a
uniform internal stress distribution in both the radial and axial directions. To
examine the mechanical properties of bamboo, tension tests were performed
on very small specimens with cross-sectional areas of about 0.25 mm 2• The
specimens were taken from nine areas arranged as shown in Figure 2.4.
Softwood HaJdwood
A tree growng on
steep ground
Figure 2.9. The growing sections of two types of trees: Japanese cedar and ash.
Figure 2.13 shows the tensile strength and Young's modulus for
specimens A and B along the transverse section of a bamboo stem. It can be
seen that the strength of the bamboo stem gradually increases from the inside
to the outside, and also that specimen B is stronger than specimen A. This is
the same variation in the volume density of the fibers that was previously
noted in Figure 2.12. The strength of an inner specimen (No.9 in Figure 2.4
16 Chapter 2
stressed duration stressed duration

~===========::::!.----1 tension side
CD
(j) y \'
r (
~ >
E
~ n-r--~-----'y coI11l ression
o
[
side <2.>
<D@: unipolar lead system """1Driin. '----'
10mn.
Typical examples ofthe voltage sign als in duced for two types of trees:
softwood and haltlwood
Figure 2. JO. The voltage signals of a Japanese cedar and an ash tree induced by stress,
tension, and compression. Note the portion grown to sustain extemalloads and the
sensitivity of the tree cells.
(a)) made of pure ground tissue was found to be about 25 MPa. Using the
rule of mixtures, the strength of a pure fiber was estimated to be about 810
MPa, which is equivalent to steel (600-1000 MPa). Furthermore, the Young's
modulus of a pure fiber was found to be 55 GPa, which is about 25% that of
steel (200 GPa). These data show that bamboo has high strength and
flexibility with low rigidity.
Figure 2. J J. A scanning electron micrograph of fractured fibers in a vascular bundle.
The model selected to examine graded structures and strength in terms of

the stress analysis of the transverse section of a composite beam, is a
cantilevered beam carrying a uniformly distributed load between points I and
100~--------~Q~~------------~
kt
Epidermis
r
-ffffi-III-&-i-+-+- t:7. 9mm
0=106.3
i=84.5 t:10.9mm
O(inside) 0.5 1.0

Distance from inner surface, rlt
Figure 2.12. The distribution of fiber density along the transverse section of a bamboo
stem.
II (see Figure 2.12). This could be regarded as corresponding to pressure

exerted by the wind on branches and leaves. The results show that the ratio
of the measured strength (au) to the calculated strength (aj), au/aj, has almost
the same value, about 25-30, for all test points on the composite beam, in
both specimens A and B. This is believed to be one of the safety factors in
this plant. It implies that a bamboo structure is designed to have uniform
strength everywhere, both in the radial direction on the transverse section
and in the axial (lengthwise) direction. Therefore it has been concluded that
bamboo has a self-optimizing graded structure constructed with a system for
sensing external mechanical stimuli. This could be considered a model of an
intelligent adaptive system.
3.2 The leaf shaft of a palm tree
The conventional image of a palm tree is a tall tree with a single trunk
and large feather- or fan-shaped leaves. Furthermore, palms, which are both
tropical and subtropical trees, can withstand very strong winds that might
blow from almost any direction. Figure 2.2 shows the change in shape of the
cross section of a palm tree perpendicular to the leaf shaft. Figure 2.14 plots
18 Chapter 2
100% fiber-tensile slren~h estimated

by the rule of mixtures
Ii
Q.
~
::l 0
tl 600
s:
.... 500
C)
...5i
1ii 400
~
1/1
...5i
1ij'
Q.
~
W
60
50
-e-.
0
0
.•
100% fiber- Young's modJlus estimated
by the rule of mixture
0
\.
0
e
0
e
55 GPa
0
•o_
Ii
::l 40
:a
0
30
o CBt=10.9mm
• @t=7.9 ~ Modulus of elasticity of a rTiniature ,
E sp3cirnen. @
1/1
-C) 20
I:
~
> 10
o O~ ~O
(inside) (outside)
Distance from inner surface, r/t
Figure 2. J3. The distribution of tensile strength and Young's modulus along the transverse
section of a bamboo stem.
the torsional rigidity (Glp, where G is the shear modulus and Ip is the polar
moment of inertia of an area) along the shaft. The data indicate that this plant
is protected from strong winds because it has low torsional rigidity (X/L=
more than 0.7) with minimal resistance, which allows the leaves to move
freely.
Figure 2.15 shows the experimental set up to measure voltage signals
induced by tension and compression stresses on the leaf shaft of a palm tree
(a different specimen than the one in Figure 2.14). The data show the
detection capability of the cell as seen in Figure 2.16. It also appears that the
-
( \J
E 10
•
-
(.)
Z
'<t
0
or-
X
0-
CJ
>.
:!::! 5
:2
0>
·c
ctS
c:
0
·00
~
0
I-
0
0 0.5 1
XlL
XlL=0.44
I---~x
L=2700mm
Figure 2. J4. The torsional rigidity of the leaf shaft of the palm tree, Butia yatay.
electrical signal controls the growth activity of the leaf shaft to conform to
the physical environment. This exemplifies a typical design for a biological
structural system of type (2).
20 Chapter 2
Butia
yatay
(J)(2): unipolar lead system

® bipolar lead system
Figure 2. J5. The experimental set up to measure the voltage signals of the palm tree, Butia
yatay. Half-size diagnostic EKG electrodes are pasted on the top and bottom sides of the
leaf s shaft.
stressed duration
tension side
-tt)
>
E
0
a) stressed duration 10min
>
E
0
-G)
b) stressed duration 10min
Figure 2. J6. Typical voltage signals induced by the bending moment of the palm tree, Butia
yatay. Upper graph: voltage signals oftension(<D) and compression(~) points. Lower graph:
voltage signal of the difference (@) between the tension and the compression stress.
3.3 Bone
Bone consists of a protein, collagen, and an inorganic mineral phase,

hydroxyapatite [Cas(P04)J(OH)]. Figure 2.17 shows the tensile strength and
Young's modulus along the transverse section of the humerus bone (a section
of compact bone) of a young rhinoceros [16]. It indicates high strength at the

outside that gradually become lower toward the inside. Because there are
many miniature blood vessels inside the compact bone, a variation in
porosity is observed along the transverse section of this compact bone [17].
It is known that the degree and distribution of porosity affect the tensile
strength and the Young's modulus [18]. Therefore, bone has a graded
structure created by altering the porosity of the bone.
Rhinoceros humerus
(8.5 kN, weight)
m ~
~ 200 ~40 ~-- 1 mm
<Ii b)
.2
::J
~20
'"
§
>-
a) ~______~5~2~m~m~__~~
Figure 2.17. The mechanical properties of the humerus bone of a rhinoceros [11].
Bone also exhibits a piezoelectric effect, which would lead one to believe
that this effect is used both for detecting an external stress and to remodel
bone structures so that no peak stress occurs at any point [8]. Therefore,
bone structure and strength (tensile strength and Young's modulus) can be
shown to result from a continuous process of self-optimization by an
intelligent, adaptive modeling system.
22 Chapter 2
3.4 Mollusk shells
Mollusk shells consist of one or more ceramic phases embedded in a

proteinaceous matrix. The mineral in these ceramic phases is mainly calcium
carbonate (CaC0 3), which is unsuitable as a structural material because of its
brittleness. Nevertheless, shells are by nature remarkably strong and tough
structures. In order to examine their mechanical properties, a relatively large
shell, the Purplish Washington clam was chosen. Figure 2.18 shows a clam
shell of the Purplish Washington clam and its structure. Figure 2.19 shows
the tensile strength and Young's modulus in the crosswise (BB') direction of
this shell. As can be seen, the strength gradually increases toward the inside
from the outside. This is also true for the microhardness.
How do shells construct a structure with extremely high strength by using
the same material in three different phases? Figures 2.19 and 2.20 show that
the microstructure of a shell is different in each of its three phases. The
outside section, a lamellar structure, consists of 40 x 5 x 0.5 J..lm crystal
plates; the midsection, a foliated structure, consists of 0.1 x 10 J..lm
needlelike crystals; and the inside section, a nacreous structure, consists of 5
x 5 x 0.2 J..lm crystal plates.
It is known that the mechanical properties of shells depend on the
combination of different structural types, and that a nacreous structure is
considerably stronger than other types. There are several structural features
of nacre that contribute to its strength: the thickness of the sheets (~ 0.5 J..lm);
the uniform thickness of the plates; and the staggered arrangement of the
blocks [19]. In addition, a softer area is located at the phase boundaries
(Figure 2.18) that toughens the structure by allowing flexible deformation
rather than rigid phase boundaries. These examples of ingenious
construction show that shell structures have limited strength to protect them
from external stresses such as point loading and hydraulic pressure. The
stress analysis along the thickness (YY') direction indicates that the structure
of the shell also has uniform strength ((Ju/(Jj is about 4.5). Therefore, one can
conclude that mollusk shells form graded structures by combining different
microstructures to achieve uniform strength.
The structural efficiency in terms of weight-cost for some performance
indices based on loading-bearing modes for selected materials is summarized
in Table 2.1 [6,20,21,22]. Some of the data plotted in Figure 2.21 show the
relationship between the specific modulus, E/p, and the specific strength,
(J/p. It can be seen that pure bamboo fiber, the shaft of a feather, and wood
all have excellent specific strengths comparable to engineering alloys and
ceramics, and that bone and antler have almost the same strength as
engineering alloys. Also, in terms of -.J Ej p, which governs the weight-cost
of overall deformability, bamboo fiber is superior to steel.
78mm
Figure 2.18. A clam shell of the Purplish Washington clam and its structure.
-
Microhardness Hv (300g)
~~4~__~~~~~1~__~N
~-
N
T
",E T
..:.s.
Ul
Ul
Q)
)~
-
c:i~
co
.x: ;<-,-t- I<>i
<D .U r-
o~
C:;:G)
-
IO.
0
--'
50 40 30 20
St rength (fu
10
Young's modulus E(GPa)
(M Pa)
o
lJ
Distribution of tensile strength,
Young's modulus and microhardness
Purplish Washington clam J.Q..mm
(Saxdomus purpura/us)
Figure 2.19. The mechanical properties of a clam shell.

24 Chapter 2
Table 2.1. The structural efficiency in terms of weight-cost for selected materials and the
performance index for a mode of loading.
Materials E(GPa)*l (E/p)*('<'E/p)* a u (MPa)*2 (aulp)* (a/3/p) * p*3
Ref.
_~Qd_s!e.:l___ ~O_O _____(~5..:6) __ (1.:.82 __ 4..02-.?~0___ J~I.:~42 ___ iI!;9.:~·~t __ 7·~ _____ _
Carbon 200 (25.6) (1.8) 450-700 (58-90) (7.5-10) 7.8
steel
_~r~.? !t.:~ __ .?~o _____(~5..:6) __ (1.:.82 __ 8_02-1~.o.9 ___(!~2:1.?±t _ il}:ljj2.. __ 7.~ _____ _
_~I_a~<ry~ ___ 73______(~6) ___ (3.:.02 __ 1_42-.?~0____(~0.:~9.?2.. __ i9J~.-~3.:.6] __ ~.~ _____ _
Ceramics:
_ ~i~______ ~~O _____(~I] ___ (.5.:.02 __4..°2 ______(!2)2 ____ i~6J2 ____ 2'~ _____ _
_ ~~2 _ _ _ _ _ !7_0 _____(!4..61 __ (3.:.52 __ 1_62 ______(~3) _____ 17..: 9) _____ 2·7 _____ _
Ah03 390 (100) (5.0) 500 (128) (63.0) 3.9
Bamboo:
_~'!!~ _____ ~I______(!7..:8] __ (3J2 __ 2}7 ______(~3_42 ____ i 3_6.:0. 2___ _1·1 ~ __ ~ __
_ !!1~t~~ ____ ~ ______(!.~7) __ (1.:.02 __ 2) _______(!8..:4) ____ 6..:3) ____ _ 1'2~i __ ~ __
_ ~l!.f~ f!b_e~ __ ~5_____ J~2)) __ Q.:.02 __ 8}2 ______(~7_02 ____ i 8}}2 ___ _ l·Q~ __ ~ __
Wood II (27.5) (8.3) 100 (250) (53.8) 0.4 20
(pine)
Mollusc shell:
Purplish Wa.
clam 32.4 (11.8) (2.0) 44.1 (16) (4.5) 2.75 8
~nacre2
Bone:
rhino 13 (6.5) (1.7) 15O (75) (14.0) 2.01 16
J~l!~e!"!t _________________________________________________ _
antler 14 (7.3) (1.92 200 (105) (18.02 1.9 20
Leaf shaft:
palm tree 2 (1.8) (1.2) 4 (3.6) (2.3) 1.1 8
(Butia
yatay)
Feather
shaft:
Stanley 7.2 (10.7) (4.0) 310 (462) (68.3) 0.67 8
____________________________________________________ _
duck 12 (16.2) (4.6) 245 (331) (52.9) 0.74 8
*1: E=Young's modulus, *2: au: Tensile strength, *3: p: Density (Mg, megagram)
*Performance index for a mode ofloading[21,22]:
E/p=GPaI(Mg/m\ a u/p=MPaI(Mg/m 3 ) for tension.
('<'E/p)=" GPaI(Mg/m3), (au 2131p)=MPa2l3 /(Mg/m3) for bending.
4. WHAT CAN BE LEARNED
The ultimate goals of this work are to understand the principles of design
and the processes found in biological materials, and to apply these findings
to develop new and superior structural concepts for materials. For example,
al{t.5
Direction of
G) Lamellar 5
@ Foiated
II
G) Nacre
5~·2Ilm
5
Size of one
crystal
Figure 2.20. The microstructure of a clam shell.
---.
cf) 10
3
.g
0>
~ 102
~
a..
~
10
-...a. crane
W
(If
::;,
'5
"0
0 Engineering
E polymers
t.l
~Q.
10- 1
(j)
10-2
10- 1 10
Specific strength, 0u/p (MPaI(Mg/m 3 ))
Figure 2.21. The specific modulus, E/p, as a function of the specific strength, alp, for some
selected biological hard tissues.
26 Chapter 2
composites of multi phased and functionally graded materials could be

created by using or modifying models found in living organisms. Thus rather
than developing new materials with high stiffness (see Figure 2.22), it might
be more advantageous to create structures using the optimal placement of
fibers, various microstructures, or porous or cellular structures. In addition,
the self-optimizing, cell-based sensing system for analyzing external
physical stimuli adapted by plants could serve as a useful model for
constructing new, intelligent, multiphased materials systems.
REFERENCES
I. Koch, I.C. (1917) The laws of bone architecture, Am. J Anat., 21, 177-198.
2. Mattheck, C. and Burkhardt, S. (1990) A new method of structural shape optimization
based on biological growth, Internat/. J Fat., 12 (3), 185-190.
3. Mattheck, C. (1990) Engineering components grow like trees, MaterialwissenschaJt und
WerkstofJtechnik, 21, 143-168.
4. Wolff, I. (1870) XXII: Uber die innere Architecture der Knochen und ihre Bedeutung fUr
die Frage von Knochenwachsthum (Concerning the internal architecture of bone and its
implication for the study of bone growth), Archiv for Pathologisch Anatomie, 50 (3), 389-
450.
5. Srinivasan, A.V., Haritos, G.K., and Hedberg, F.L. (1991) Biomimetics: Advancing man-
made materials through guidance from nature, App. Mech. Rev., 44 (11), 463-481.
6. Gordon, I.E. (1978) Structures or Why Things Don't Fall Down, Penguin Books, London,
17.
7. Williams, W.S. and Breger, L. (1975) Piezoelectricity in tendon and bone, J Biomech., 8,
407-413.
8. Nogata, F. and Takahashi, H. (1995) Intelligent functionally graded material: bamboo, J
Compos. Eng., 5 (7), 743-751.
9. Fukada, E. and Yasuda, I. (1957) On the piezoelectric effect of bone, J Phys. Soc. Jap. 12
(10), 1158-1162.
10. Martin, R.B. (1972) The effects of geometric feedback in the development of
osteoporosis, J Biomech., 5, 447-455.
11. Gjelsvik, A. (1973) Bone remodeling and piezoelectricity-I, ibid., 6,69-77.
12. Cowin, S.c. and Hegedus, D.H. (1976) Bone remodeling I: Theory of adaptive
elasticity, J Elastic. 6 , 313-326.
13. Cowin, S.c. and Van Buskirk, W.C. (1978) Internal bone remodeling induced by a
medullary pin, J Biomech., 11,269-275.
14. Hayes, W.C. et al. (1982) Stress-morphology relationships in trabecular bone of the
patella, in Finite Elements in Biomechanics, (eds. R.H. Gallagher, et al.), John Wiley &
Sons, New York, 223-268.
15. Japan Society of Wood (1991) World of Beautiful Wood (in Japanese), Ohtsu, Japan,
Kaiseisha, 25.
16. Currey, I.D. and Nogata, F. (1991) unpublished data, investigation performed at
University of York, U.K.
17. NHK Project team (1989) Human Body (in Japanese), NHK publications, Tokyo, 50.
18. Alexander, R.M. (1984) Animal Mechanics (second edition), Blackwell Scientific
Publications, London, 123.
19. Currey, J.D. (1980) Mechanical properties of mollusk shell in The Mechanical Properties
0/Biological Materials, 34th Symposium of the Society for Experimental Biology, (eds.
J.F.V. Vincent and J.D. Currey), Cambridge University Press, London, 75-97.
20. Gordon, J.E. (1988) The Science o/Structures and Materials, Scientific American
Library, New York, 25 and 176.
21. Ashby, M.F. (1992) Materials Selection in Mechanical Design, Pergamon Press, Oxford,
35.
22. Ashby, M.F. et al. (1995) The mechanical properties of natural materials I, Material
property charts in Proceedings o/the Royal Society London, Series A, Mathematical and
Physical Sciences, 450, 123-140.
Chapter 3
GRADED MICROSTRUCTURES
Keywords: Structure, microstructure, microstructure characterization, microstructural

analysis, nonuniform materials, characteristic dimensions, spatial variation,
volume fraction, connectivity, field parameter.
1. INTRODUCTION
It is well known that microstructure plays a predominant role in

determining material behavior. Materials engineers therefore seek to control
microstructure through processing. Processing studies have traditionally
focused on optimizing microstructural characteristics with the intent of
producing a uniform microstructure throughout the material. Increasing
microstructural uniformity has long been considered a fruitful means of
improving properties. In contrast, FGMs are produced containing deliberate
spatial nonuniformities in their microstructures. By treating microstructure
as a variable that is dependent on position, different material characteristics
can be incorporated in a single component. Such a component can be
considered a materials system integrated at the microstructural level to
achieve optimum performance in a specific application. This is what
distinguishes FGMs from other materials.
Quantitative microstructural analysis methods aid in understanding the
fundamental relationships between structure and properties needed for
effective utilization of this new class of materials. For example, certain
aspects of the microstructure must be specified as a function of position so
that local material properties can be estimated for modeling purposes.
Alternatively, an FGM designed using modeling techniques must be
30 Chapter 3
described in terms of the spatial distribution of its key microstructural

features that define goals for synthesis and processing.
The most widely studied implementation of the FGM concept involves
the joining of dissimilar materials (e.g. ceramic-to-metal bonding), where
residual stresses develop during cooling as a result of the property mismatch
across the bonded interface. These FGMs typically consist of an interiayer
between the ceramic and metal that exhibits a gradual transition in the
relative amounts (volume fractions) of the ceramic- and metal-rich phases.
The spatial variation in volume fraction is optimized to minimize the thermal
stresses that can cause thejoint to fail during fabrication or while in service.
Although this is one of the most important applications for FGMs, the FGM
concept can extend far beyond this. It has been suggested that, in principle, a
spatial variation in any microstructural feature can be produced through
appropriate manipulation of material and processing variables [1]. Countless
material combinations and microstructural arrangements are therefore
possible. It is reasonable to expect that all types of microstructures known
from the study of spatially uniform materials are relevant to the field of
FGMs.
FGMs can be produced by numerous processing methods that are
described in detail in Chapter 6 [1, 2]. Undoubtedly, FGMs produced by
different processing methods will exhibit vastly different microstructures. To
illustrate the wide range of possibilities, Figure 3.1 shows several examples
of graded materials. Differences occur due to other factors besides
processing, since within a given graded material, different microstructural
types exist at different locations. This level of complexity presents
significant challenges for quantitative analysis. For this reason it is important
to establish a common framework to describe and analyze FGM
microstructures.
The goals of this chapter are to present a brief overview of the relevant
principles of microstructural analysis, and to discuss spatially nonuniform
microstructures with particular attention to differences between these
materials and conventional (spatially uniform) materials.
Graded Microstructures 31
2. RELEVANT PRINCIPLES OF
MICROSTRUCTURE CHARACTERIZATION
2.1 Background
The goal of microstructural analysis is to develop a quantitative

description of microstructure that can be used to establish its relationship to
properties and processing. The level of effort required to fully characterize a
given material, as well as the choice of appropriate analysis methods, will
depend to a large extent on the kind of information desired and the accuracy
needed. Excellent reviews of microstructural analysis principles and
applications can be found in the literature [3-5], therefore only a brief
introduction is presented here.
Figure 3.1. Examples of different graded microstructures produced by various processing

methods (a) powder processed alumina-nickel (AI 20 3-Ni), (b) thermal sprayed AhOrNi, (c)
chemical vapor deposited silicon carbide-carbon (CVD SiC-C), (d) vapor deposited
aluminum-silicon (AI-Si)
32 Chapter 3
In general, microstructures consist of three different types of elements --

phases, interfaces, and defects, all of which are relevant to the study of
FGMs. Within this framework, numerous features can be identified. To
arrive at a useful description of microstructure, certain characteristics of the
microstructural features of interest must be quantified. Table 3.1 lists the
basic elements that compose all microstructures, along with some common
features of interest and examples of characteristics used to describe them.
Characterization typically involves specifying a combination of
crystallographic parameters (e.g., crystal structure and chemical
composition) and geometrical parameters (e.g., volume fraction, size, shape,
orientation, and spatial arrangement) for the various microstructural
elements. The primary focus of most analyses is on specifying the chemical
composition and geometrical parameters for the phases present. However,
other information is often important, depending on the material and the
application. For example, point defect concentrations influence the electrical
properties in semiconductors, and dislocation density affects the strength of
cold-worked metals.
Table 3..
1 The Basic Elements of Microstructure
Typical Features
Elements of Interest Example Characteristics
phases grains, particles, fibers, voids state of matter, chemical composition,
volume fraction, crystallinity, size,
shape, orientation
interfaces surfaces, grain boundaries, specific boundary area, contiguity,
interphase boundaries degree of order (coherency), impurity
segregation
defects vacancies, impurities, number density, arrangements, size
dislocations, cracks
Real microstructures are three-dimensional, yet most analyses are

performed on two-dimensional metallographic cross sections. There are
various options available for conducting two-dimensional analyses. In the
simplest case, two-dimensional parameters are used to describe the
microstructure directly. The fraction of an area and the mean length of an
intercept are examples. More complex two-dimensional parameters, such as
shape factors, can be defined and used to describe phase morphology. Three-
dimensional descriptions using stereological parameters such as volume
fraction or specific surface area can often be derived from two-dimensional
measurements. However, for certain parameters (e.g., size distributions)
simplifying assumptions must be made regarding the shape and arrangement
of the features. Direct evaluation of three-dimensional geometry can only be
made by laborious serial sectioning methods.
Analysis of two-dimensional cross sections involves numerous steps.

Foremost, careful specimen preparation is required to obtain an image that is
representative of the material and suitable for quantitative analysis. This can
be a challenge with FGMs because of the vastly different material
characteristics that can be encountered within a single specimen. In addition,
the instrument used to generate the image must have adequate resolution to
distinguish the features of interest. Furthermore, the image itself must have
enough contrast to allow the features of interest to be identified.
Once an image is obtained, it can be analyzed using point counting, linear
analysis or areal analysis methods. Point counting and linear analyses can
provide highly accurate results and are simple to perform. Recently, fully
automated image analysis systems and powerful software packages have
become commercially available. These instruments make it relatively easy to
obtain large amounts of data rapidly. However, problems related to the
acquisition and interpretation of digital images are common. In automated
instruments, the measurements performed by the computer involve
manipulating and analyzing the characteristics of a very finely spaced grid of
points (pixels) that compose the digitized image.
Typically, average values are sought for the geometrical parameters. But
individual microstructural constituents rarely need to be described. This
forms the basis for the statistical nature of most microstructural
measurements. Quantities measured on individual microstructural
constituents are called feature parameters, whereas those that are
representative of many features are called field parameters. Field parameters
are usually obtained and reported assuming that the microstructure is
uniform (i.e. only random errors are present) within the area of
measurement. This assumption can have significant implications with
respect to the analysis of graded microstructures, as will be discussed in this
chapter.
Many different parameters can be used to characterize microstructures.
Their selection depends on the nature of the material being examined and the
kind of information being sought. Several key parameters in the
characterization ofFGM microstructures are discussed below.
2.2 Crystal Parameters
2.2.1 Composition
Phase composition must be specified for any multicomponent system.

Composition is typically expressed in either weight or atomic (mole)
percent. In the case of single-phase materials (i.e. solid solutions), the
34 Chapter 3
volume average or bulk composition of the material is specified. In the case

of multi phase materials the composition of each phase must be specified in
addition to the bulk composition. Under equilibrium conditions, phase
diagrams can provide useful information about the composition of the phases
present. However, quantitative chemical analysis must be employed to
accurately measure actual compositions. Such analyses can be performed
using a wide variety of techniques, each having certain advantages and
disadvantages. The choice of method depends on the material and the
degree of accuracy required. Common techniques include x-ray diffraction,
x-ray fluorescence, energy dispersive x-ray analysis, and wet chemical
analysis, among others. Only a few methods are capable of determining
composition locally at the microscopic scale, a particularly useful piece of
information in the study ofFGMs.
2.2.2 Crystal structure
The structure of an atomic or molecular condensed phase can be

described by the degree of short-range or long-range order present.
Amorphous phases exhibit only short-range order, whereas completely
crystalline phases exhibit long-range order. For each crystalline phase
present in a material, the crystal structure must be specified. Under
equilibrium conditions, phase diagrams can also provide useful information
about the crystallographic structure of the phases present. Experimentally,
conventional x-ray diffraction or electron diffraction techniques provide
most of the desired crystallographic information. In certain cases, more
sophisticated techniques are needed to obtain information about phase defect
structures, the extent of ordering, and the like.
2.3 Geometrical Parameters
2.3.1 Nomenclature
In the analysis of microstructures it is necessary to use a common

nomenclature to avoid confusion. Following conventional notation, in the
following discussion volumes are denoted V, surfaces are denoted S, areas
are denoted A, lines are denoted L, points are denoted P, and numbers are
denoted N. Subscripts are used to refer to the test region, bars are used to
represent mean values, and Greek letters are used to represent individual
phases.
2.3.2 Volume fraction
Volume fraction is perhaps the single most important microstructural

parameter of interest in multiphase materials. The volume fraction of phase
b, expressed as VyCf)), is given by:
V~
VyCf)) = Vo
C3.1)
where V ~ is the volume of the b phase within the test region and Vo is
the volume of the test region. Volume fraction can be determined from
linear, areal, or point counting analysis since, within the limits of statistical
errors, these yield equivalent results. Thus,
(3.2)
where AACf)), LLCf)), and PpCf)) represent the area, length, and number
of points of the b phase per unit test area, per unit test length, and per
number of test points, respectively. For a material containing n distinct
phases the following relationship holds:
VyCI) + Vy(2) + ... VyCn) = 1 (3.3)
Thus, in a two-phase material it is sufficient to analyze the volume

fraction of only one of the phases. Care must be taken when using this
formula, since in some cases phases may be present that are either not
anticipated or not readily observed. An example would be the presence of
residual porosity in a powder processed two-phase material, where for the
purposes of Equation 3.3 porosity should be treated as a third phase.
2.3.3 Boundary area density and specific boundary area
The surface or interfacial area of a phase per unit volume is known as the
boundary (or interface) area density. The boundary area density of the b
phase determined relative to the total volume of the test region, expressed as
SyCf)), is given by:
(3.4)
36 Chapter 3
where S(~) is the surface area of the b phase, PL(~) is the number of
intersection points with the b phase boundary per unit length of a test line,
and LA(~) is the length of the b phase boundary per unit test area. Note that
in applying Equation 3.4, grain boundary intersections must be counted
twice because the boundary is shared by two surfaces.
The surface or interfacial area of a phase can also be related to the
volume of the phase itself. In this case, the specific boundary ( or interface)
area is obtained, expressed as:
Sv(~') = S(~) = Sv(~) = 2PL(~) = 4. LA(~)

V(~) Vv(~) Pp(~) 1t AA(~) (3.5)
It has been pointed out that, other than volume fraction, the boundary
area density and specific boundary area are probably the most important
microstructural parameters [5]. This is because they relate directly to many
microstructural phenomena and material properties, they are three-
dimensional quantities obtained from two-dimensional analyses without
assumptions regarding phase shape or arrangement, and they are extremely
useful for defining other microstructural parameters.
2.3.4 Size
The most commonly used method for expressing the size of grains or
second phases involves the mean intercept length, L, expressed as:
- Lo 1
L=-=-
N NL (3.6)
where N is the number of grain boundaries intersected along a test line of

length Lo. NL is simply the number of grains (or grain boundaries counted
once) per unit length of test line. This method of specifying dimensions is
also the most general, since no assumptions about grain shape are required.
This measure can also be applied to determine the mean linear size of
particles or agglomerates of a second phase embedded in a matrix, using the
formula:
[(~) = Lo· Vv(~) = Vv(~)

N(~) NL(~) (3.7)
where N(~) is the number of b particles intersected along a test line of

length Lo. Similarly, the mean linear spacing between particles can be
expressed as:
L(~-~) = Lo'( 1- Vv(~)) = 1 - Vv(~)

N(~) NL(~) (3.8)
A distribution of grain or particle sizes generally exists and is often of

interest. A complete discussion of size distribution analysis is beyond the
scope of this review. In general, data on the size of microstructural features
is obtained in the form of intercept (linear chord length) distributions
obtained from cross sections, and analyzed in the form of frequency plots
(histograms) or cumulative frequency plots. The most commonly used
distributions are the Gaussian and log-normal functions. Distributions are
described by parameters such as the mean, mode, median, and standard
deviation.
2.3.5 Shape
The most common descriptions of phase shape are those based on simple
geometrical objects, such as spheres and cubes (or other regular polyhedra)
for which straightforward relations exist between the characteristic
dimensions and such measurable quantities as surface area and volume.
Other (irregular) shapes can be described using qualitative descriptors such
as flakes, ligaments, ellipsoids, and whiskers. Quantitative descriptions for
these features can be quite simple or complex, depending on the information
required. The shape of individual features is most easily described based on
planar shape parameters obtained from cross sections or projections. For
example, the aspect ratio is defined as the maximum particle dimension
divided by the minimum particle dimension, and is equal to 1 for a sphere, 3
- 10 for an ellipsoid or ligament, and as high as 200 for needles or whiskers.
Another commonly used shape parameter compares the length of the
perimeter of a planar object with the circumference of a circle having the
same area. In three dimensions, there is considerable difficulty in capturing
all aspects of shape characterization of spatially distributed features using a
single parameter. Typically, shape parameters defined for three-dimensional
objects attempt to describe the deviation from spherical shape by combining
both volume and surface area measurements into a dimensionless factor.
However, the presence of a distribution in the size of features often
complicates the interpretation of these results.
38 Chapter 3
2.3.6 Connectivity
As the content of the second phase of a two-phase material is increased,

there is a critical volume fraction at which the transition from a dispersed
phase to an interconnected microstructure takes place. A phase is said to be
connected in three dimensions when a continuous path can be found through
the material within that phase without intersecting the other phase. A
quantitative measure of connectivity is the mean number of contacts that a
particle or grain makes with particles or grains of the same phase.
Unfortunately, the number of contacts per particle measured in two
dimensions cannot be directly related to the three-dimensional connectivity.
More frequently, the critical volume fraction (percolation threshold) at
which the transition from a dispersed phase to an interconnected
microstructure takes place is specified. While this value is difficult to
measure metallographically, applicable methods have been described [3].
More typically, transport-based methods, such as electrical or thermal
conductivity, are used to determine the percolation threshold, particularly
when the two phases have markedly different transport properties. Whether
or not a phase is connected strongly influences the properties of a two-phase
material. This microstructural transition is of particular importance in FGMs.
2.3.7 Contiguity
Contiguity is a measure of the relative amount of a phase in contact with

itself within a two-phase mixture. This parameter has also been shown to
correlate with many properties of two-phase mixtures. Contiguity can be
defined from the specific boundary areas as [6]:
Sv(~~)
C=------
Sv(~~) + Sv(a~) (3.9)
where Sv(~~) represents the specific interface area for contact between
b grains, Sv(a~) represents the specific interface area for contact between a
and b grains, and NL(~~) and NL(a~) represent the number of
intersections with b-b and a-b boundaries per unit length of the test line,
respectively. The contiguity characterizes the skeletal nature of the
microstructure, but does not specify whether or not the phase is connected in
three dimensions.
2.3.8 Other features
A number of other characteristics of microstructural features can be

quantified if they are useful for establishing relationships with processing or
properties. Examples of topics that may be of interest include among others:
the degree and direction of preferred orientation (texture); issues related to
arrangement or packing of microstructural features (e.g., coordination
number, particle density, nearest neighbor spacing); surface curvature; and
angles between interfaces (e.g., contact angle, dihedral angle) [1,2].
2.4 Useful Mathematical Relationships
There are many mathematical relationships between the microstructural

parameters that are useful. For example, in a single-phase material the grain
boundary surface area is inversely proportional to the mean linear grain size:
- 4
L=-
Sy (3.10)
In a two-phase material, the mean linear particle size of the second phase
L(I3) is related to the contiguity C, volume fraction Vy (l3) and the mean
distance between particles LCI3-I3) by the relation '
[(13) =[(13-13 ). (I-C). VyCI3)

1- VyCI3) (3.11 )
Therefore, only three independent parameters must be determined from

the experimental data in order to calculate the value for the other
microstructural parameter in Equation 3.11.
In actual microstructures, the distribution of the shape, spatial
arrangement, and size features is complicated. The stereological parameters
described above are useful for characterizing these microstructures, but are
often unsuitable for use in modeling the behavior of the material. Therefore,
simplified geometrical models for which well-defined mathematical
relationships exist are often employed. For example, the specific surface area
of spheres of radius r is given by:
4nr2 3
Sy=---
4/3.nr3 r
(3.12)
40 Chapter 3
and from the relationship between the mean linear particle size and the
surface area:
3L
r=-
4 (3.13)
This expression can be used to calculate the radius of equally sized

spheres of a second phase from the mean linear particle size measured on the
cross section. Other commonly used geometrical models involve the
assumption of equally sized cubes or spheres arranged in space according to
a periodic lattice. Using such models, along with the relationships for the
surface areas and volumes of these objects, many useful relationships can be
readily derived that are extremely useful for comparing experimental
measurements with theoretical predictions, such as the distance between
particle centers or the spacing between particle surfaces.
3. UNIQUE ASPECTS OF SPATIALLY

NONUNIFORM MATERIALS
3.1 General Comments
In the broadest sense, a graded material can be defined as any material in

which the microstructure exhibits a spatial variation in at least one
dimension. FGMs refer to a special class of graded materials in which the
microstructural variation (and associated variation in properties or functions)
has been designed and intentionally introduced into the material to optimize
its performance in a particular application, or under a specific set of
functional requirements.
Many materials contain gradients in composition; some of these (e.g.,
carburized steel) are produced by transport-based processes that have been
utilized for many years. Although the composition gradient often also gives
rise to gradients in other microstructural features, these spatial distributions
are constrained by the processes used to produce them (e.g., solid state
diffusion). With the emergence of the FGM concept, the idea of spatial
variations in microstructure has been broadened beyond composition to
include essentially all microstructural parameters. Now, for example, in
addition to composition (or volume fraction), it is reasonable to discuss
gradients in the size, shape, and arrangement of phases.
In addition, many new fabrication routes have been developed that allow
controlled spatial distributions of these microstructural features to be
introduced into a material. Thus, in principle, microstructural gradients can
be designed a priori, and spatial distributions within the material can be
established that are very different from those previously accessible via
transport-based processes. This is an important distinction between the
FGMs being produced today and the graded materials of the past. It is also
the reason that microstructural characterization issues are so important in
this field.
Some materials are referred to as "compositionally graded" to reflect that
chemical composition is their primary variable of interest. However, it
should be recognized that chemical gradients are not necessary for a material
to have a graded microstructure. Neither does this term imply that
composition is the only microstructural parameter varied in such a material.
For example, a material's resistance to fatigue crack initiation might be
improved simply by altering the grain size as a function of position near the
material's surface. This type of material could be considered an FGM even
in the absence of any compositional gradient. Similarly, in order to improve
the corrosion resistance of a single-phase solid solution, the composition of
an alloying element could be varied as a function of distance near the
material's surface. Such a material could be considered an FGM, even
though no changes in the geometrical features of the microstructure are
evident.
These examples illustrate that a variation in any of the microstructural
features described in the previous section can be considered within the
context of FGMs. Furthermore, within a single graded material, a spatial
variation often exists in more than one microstructural feature. A material
described as being "compositionally graded" may therefore also contain
gradients in the amount, size, shape, or arrangement of a second phase. The
different microstructural gradients present within a material can be related to
one another through conservation laws or fundamental geometrical
relationships. Alternatively, it is possible that the different gradients have
been introduced completely independently of each other in order to impart
multiple functions to the material. This is often the case with FGMs.
The level of complexity possible in microstructures containing multiple
graded features is illustrated in Figure 3.2 using a hypothetical graded
material as an example. Without noting how or why this material might
have been formed, the following qualitative observations can be made. First,
the volume fraction of b increases with increasing distance from left to right.
The size of the b particles also increases in the same direction. In addition,
the b particles become more angular, and there is more contact between
them as the volume fraction of b increases. At the far left, the microstructure
42 Chapter 3
consists of isolated b particles distributed uniformly throughout a matrix of

a, whereas at the far right the b phase forms an interconnected network with
islands of a existing along grain boundaries of b. The porosity present within
this structure is located only within certain localized regions in the structure.
For those parts of the material that contain nearly equal amounts of a and b,
the porosity is located entirely within the a phase. At high contents of b, the
size of the porosity is smaller and located entirely within the b phase.
The purpose of this example is solely to illustrate the kinds of variations
that may be present within a given graded material. It should be emphasized
that some features within the material may not have been introduced
intentionally, i.e. they may simply be present as a result of processing. Such
features mayor may not be of interest to the FGM designer, depending on
their degree of influence on the material's performance. Obviously, in cases
where the features are not relevant, less effort needs to be spent for their
characterization. However, features that are critical for achieving the desired
performance generally warrant a greater characterization effort. Close
collaboration between the design, materials processing, and microstructural
characterization efforts therefore is required.
In most cases, microstructural gradients discussed in the literature have
been one-dimensional (I-D). This kind of graded material is the easiest to
visualize, fabricate, and model. However, two-dimensional (2-D) and three-
dimensional (3-D) gradients are not only possible, but may be desirable and
necessary for effectively implementing the gradient materials concept in
practical applications. For example, consider the simple application of
minimizing the thermal mismatch stresses that occur between two joined
dissimilar materials. If edge effects are ignored while designing the
Figure 3.2. Diagram ofa hypothetical graded structure that has gradients in several
different microstructural features.
microstructure of the component, then the stress distribution will be found to

be purely a function of axial distance along the length of the specimen.
Under such circumstances, a i-D microstructural gradient will be sufficient
for reducing the peak thermal stress. However, in actual parts, edges and
comers invariably result in 2-D and 3-D stress distributions that are highly
geometry dependent. In these cases, 2-D and 3-D microstructural gradients
may be necessary to minimize residual stresses. A diagram of differences
between i-D, 2-D, and 3-D graded materials is shown in Figure 3.3. Little
work has been conducted to date on the fabrication of materials containing
2-D and 3-D microstructural gradients. This is an important area for future
research.
1-0
2-D
3-D
Figure 3.3. Diagram illustrating the difference between materials graded in 1-,2-, and 3-
dimensions.
Because any of the common microstructural features can be considered

as variables within a graded material, characterization of a graded structure
typically involves many of the same analysis methods used for
44 Chapter 3
characterizing spatially homogeneous materials. However, since the graded

material is spatially nonuniform, there are special considerations with
respect to quantitative analysis of the spatial distribution of the
characteristics of features.
3.2 Characteristic Dimensions
Just as microstructural features can have sizes from the atomic to the
macroscopic, gradients can also exist on any size scale. Examples of the
common size scales are listed in Table 3.2, along with the associated ranges
of dimensions for the size of the relevant microstructural features plus
examples of graded structures for each of the size scales.
Table 3.2. Characteristic Microstructural Length Scales

Typical Feature
Size Scale Dimensions Examples of Graded Structures
atomic < lOOrun epitaxial films, optical thin films
microscopic lOO run - lOO Ilm diffusion bonding, interfaces in composites
meso scopic lOO !lm - 1.0 mm surface hardening, thermal barrier coatings
macroscopic > 1.0mm graded ceramic-metal joints
In order to apply the description and analysis of graded materials across

the wide range of size scales covered by this field, it is important to
understand the relationships between the different dimensions involved in
their analysis. At least three fundamental characteristic length scales can be
identified, as shown schematically in Figure 3.4. The first, designated D 1,
involves the dimensions of the particular microstructural feature of interest;
the second, designated D2, involves the dimensions over which the
microstructure can be considered to be "locally homogeneous," and the
third, D3, involves the dimensions over which the various locally
homogeneous regions are combined to produce the spatial variation in
microstructure.
The first characteristic dimension is relatively straightforward, and in the
case of grains or second phase particles, can be represented by the mean
intercept length, as defined above. In graded multi phase materials,
compositional variations often are discussed in terms of the volume fraction
of the phases, for which the mean intercept length provides the appropriate
characteristic dimension. However, these materials are also sometimes
referred to as being "compositionally graded." Since volume fraction can be
correlated with chemical composition, use of this term is valid. Confusion
can result, however, because composition gradients can also exist within
single-phase materials. In such cases the more appropriate characteristic

length scale is on the order of atomic dimensions.
To avoid ambiguity about the appropriate length scale, the term
"compositionally graded" probably should be restricted to single-phase
materials where composition is the primary microstructural variable of
interest. Multiphase materials should be referred to more appropriately as
being "phase graded" or "volume fraction graded". The dimension DJ can
change at different locations, and in a multi phase material each phase can
have its own characteristic dimension.
To understand the second characteristic length scale, D2, it is necessary to
introduce the concept of a "locally uniform" microstructure, which is of
particular importance in the field of FGMs. The first reason, discussed in
Chapter 4, is the need to estimate local thermomechanical properties in order
to model, design, and predict FGM behavior. The second reason relates to
the statistical nature of the field parameter measurements performed during
microstructural analysis.
Within the field of composite materials, mechanical and physical
properties can be modeled at either the macroscopic or microscopic levels.
In general, macroscopic models predict the average or global response of a
composite using only the volume fraction and the properties of the individual
phases. Since all composites are heterogeneous at the microscopic scale,
,•
these models are simplistic in that microstructural details such as
a •
Figure 3.4. Diagram illustrating the relationship between the three characteristic
dimensions within a graded material.
46 Chapter 3
reinforcement size, shape, arrangement, and orientation are often ignored.

Whether empirically based or derived from continuum assumptions, these
models usually give rise to the well known rule-of-mixtures formulations.
By accounting in various ways for the interaction between the phases, the
rule-of-mixtures estimates can be modified to include some microstructural
details (e.g., arrangement of the phases or degree of contact between the
phases). In all cases, however, the validity of rule-of-mixtures approaches
relies on the implicit assumption that the material is homogeneous (spatially
uniform in terms of properties) on a macroscopic scale, i.e. the dimensions
of the discrete microstructural constituents are small compared to the size
scale of the material at which properties are measured. When the dimensions
of the material are comparable to the dimensions of the constituents, this
assumption is violated and local stress and strain fields must be accounted
for.
The application of macroscopic models for estimating material behavior
in FGMs therefore implicitly involves the "locally uniform" assumption. The
dimensions of the "locally uniform" region within the FGM must remain
sufficiently large compared with the dimensions of the microstructural
constituents to justify use of these models. Thus, for the purposes of this
discussion, D2 » D\.
Microscopic models typically employ mean-field theories to estimate the
overall deformation response of a composite by considering the behavior of
the constituent phases [1, 7-10]. The most common method involves
computing the average stress and strain fields for discrete particles isolated
within a matrix phase using various forms of Eshelby's equivalent inclusion
method [11]. In these models, microstructural details such as the amount,
size, shape, and orientation of the reinforcement can be taken into
consideration. However, only the microstructures of dispersed particles (and
by implication limited volume fractions) can be treated. The finite element
method (FEM) has also been used extensively to investigate the effects of
microstructural details on deformation response. In this way, localized
nonuniformities in the deformation fields can be studied.
Using either micromechanics or FEM approaches more realistic, yet still
relatively simple, microstructures can be modeled using various unit cell
arrangements. In general, however, because these models do not account for
large-scale nonuniformities in microstructure, their application in estimating
material behavior in FGMs involves treating the spatial distribution of the
microstructure as a series of discrete, "locally uniform" layers, each having a
different microstructure.
The deformation response of a graded material also has been modeled
without recourse to the "locally uniform" assumption, by using random unit
cell arrangements that take microstructure nonuniformities into account
explicitly [12]. The point of this discussion is to emphasize that in almost all
FGM modeling studies the concept of a "locally uniform" material is
employed. From a microstructural analysis standpoint, it is necessary to
recognize its importance.
The third characteristic dimension, 0 3 , relates to the overall dimensions
of the graded region of the material, regardless of the microstructural details
or their spatial distribution. This dimension has a significant effect on the
macroscopic behavior of the structure, and is important in the modeling and
design of graded materials (discussed in Chapter 4). A key point is that the
length scale, 0 3 , must be larger than O2 to be effective in significantly
altering the local material properties as a function of position.
With respect to microstructural analysis, the determination of an
appropriate size for the test region must be based on knowledge of all three
length scales. Recall that the measurement of field parameters representing
specific microstructural features is performed assuming that the material is
spatially homogeneous within the region of measurement. Typically, a
number of features are measured within a given test region. Several test
regions are then analyzed, and an estimate (mean) and standard deviation
(error) for the measurement are subsequently determined. Errors arising
from random scatter within a particular test field can be reduced by making
the test region large compared with the feature size (i.e. by ensuring a
sufficiently large number of features are counted within the field). Thus, the
characteristic dimension of the particular microstructural feature, 0], is
useful for determining an appropriate (minimum) size for the test region.
Within practical limits, larger test regions are more desirable for
minimizing errors. In contrast, errors arising from the random scatter
between different fields measured on the same specimen are minimized by
examining many fields. Random spatial inhomogeneities in the
microstructure contribute to an increased error in the field-to-field
measurement. However, if a systematic spatial variation in microstructure
exists, and information about the spatial distribution is sought (as is true in
the analysis of graded materials), the field-to-field variations cannot be
treated as errors.
Alternatively, a series of systematically arranged test regions are needed
and within each test region the material must be assumed to be
homogeneous. The appropriate (maximum) size of the test region is then
limited by the characteristic dimension of the microstructural variation, 0 3,
and smaller test regions are more desirable for minimizing position-to-
position errors. Ideally, the dimensions of the test region should be
comparable to or less than the dimension O2, since at each analysis location
along the graded direction, several representative test regions must be
analyzed.
48 Chapter 3
It can be seen from this discussion that serious measurement errors can
occur when the test region is on the same size scale as any of the
characteristic dimensions. Tradeoffs will therefore be likely to exist with
respect to the accuracy with which either the microstructural feature itself or
its spatial variation can be determined from a single set of measurements. To
illustrate, consider the hypothetical graded material shown in Figure 3.4. The
results of performing image analyses to determine volume fraction, using
test regions of different sizes, are shown in Figure 3.5. In Figure 3.5 (a), the
analysis region was chosen smaller than the characteristic dimensions of the
b particles (i.e. < DJ)' Unreliable results are obtained near the left side of
Figure 3.4 where these particles are widely spaced. In comparison, because
the analysis region is larger than the smallest characteristic dimension of the
a phase, it could detect the locally high concentration of b that occurs about
two-thirds of the way across the structure. In Figure 3.5 (b), the analysis
region is approximately the same size as the characteristic dimension D 2, and
all the trends in volume fraction are correctly observed. In Figure 3.5 (c) the
analysis region is large compared with D3 • This analysis was unsuccessful at
detecting the local variations in volume fraction.
These problems can be further exacerbated in the more general case
when spatial variations exist for several different microsrtuctural features,
and when the different features each have different characteristic
dimensions, as in Figure 3.2. Similar to the case shown in Figure 3.4, both
DJ and D2 can vary as a function of position within the material thereby
causing further complications for analysis. In order to characterize such
variations, several measurements along the length of the material may be
required using different analysis techniques and test regions of different
sIzes.
3.3 Diffusion and Phase Diagram Considerations
The evolution of microstructure is controlled by the thermodynamic and

kinetic characteristics of the materials system, its thermal history, synthesis
method, and thermomechanical processing. Diffusion and phase equilibria
considerations are therefore expected to play a significant role in
establishing and altering microstructural gradients. Although a complete
understanding of these topics is lacking, several important points can be
emphasized.
It is an important law of nature that gradients are unstable and provide a
driving force for mechanisms for their elimination. Therefore, all materials
containing microstructural gradients are in a nonequilibrium state. As such
they are subject to processes such as diffusion or viscous flow that can
significantly alter the original microstructure. In the case of a
compositionally graded material, when there is solubility for one component

in the other, diffusion fluxes can become significant at elevated
temperatures, thereby allowing chemical homogenization to occur. Both
solubilities and diffusion coefficients are strongly temperature dependent.
Therefore, temperature plays a significant role in the stability of
compositional gradients.
Size of Test Region: Image Analysis Results

1.0
0.8
c
0 0.6
'""
A- ~
'~"
0.2 0.4 0.6 0.8 1.0

normalizectiistance
1.0
0.8
B 0.6
'""
B • ~ ~
'"~ 0.4
0.2
O.
.0 0.2 0.4 0.6 0.8 1.0
normalizedistance
1.0
0.8
B 0.6
C .. ~
~
'"
~ 0.4
0.4 0.6 0.8 1.0

norma/ized:lstance
Figure 3.5. Results of image analysis using different sized test regions to determine the
volume fraction distribution in the hypothetical microstructure shown in Figure 3.4.
50 Chapter 3
Equilibrium is achieved when chemical potential gradients have been

eliminated, which usually, although not always, corresponds to a
compositionally homogeneous state. Even after chemical homogenization is
attained, diffusion processes can continue to cause significant
microstructural changes by reducing the free energy of the system. Most
significant among these are microstructural coarsening phenomena, such as
grain growth and Ostwald ripening, which involve a reduction in the free
energy through the elimination of interfacial surface area. A major effort has
been undertaken to understand and model coarsening in spatially
homogeneous materials, but little work has been done to examine these
phenomena within materials that initially contain microstructural gradients.
This remains an important area for future research.
The importance of diffusion and phase equilibria considerations is
illustrated in the simple case of a compositionally graded material produced
by interdiffusion between two solids, as shown in Figure 3.6. In this case,
composition is the primary variable of interest. Chemical composition is
determined as a function of position, temperature, and time by the governing
differential equations describing mass transport. Using appropriate initial
and boundary conditions, the composition profile within the material at any
point in time (shown schematically in Figure 3.6) can be predicted provided
the diffusion coefficients are known. Both analytical and numerical
techniques are widely used to solve the diffusion equations for many
technologically important problems. Once fabricated, the composition
profile of an FGM represents the initial conditions needed for obtaining
solutions to subsequent diffusion problem formulations.
The extent to which diffusion influences a graded microstructure can be
qualitatively predicted based on phase diagram features such as solubilities,
the presence of intermediate phases, and phase transformations. For
example, possessing information about the variation of composition with
position, and employing the assumption of local equilibrium at phase
boundaries, important microstructural information can be predicted for any
given temperature. Figure 3.6 illustrates schematically the relationship
between the phase variations in the composition, the phase diagram, and the
expected equilibrium microstructure for hypothetical composition gradients
created between two pure materials A and B. Three different cases involving
very simple binary phase diagrams are shown.
This example illustrates in a simple way the important role on
microstructure that can be played by diffusion and phase relationships. More
complicated phase diagrams are often encountered in real systems.
Consequently, interdiffusion can also cause the formation of new phases,
dissolution, gas evolution, and similar effects that can be detrimental to the
material's performance. Many graded materials and FGMs are intended for
pure 8
Q)
u
C
«l
.~
"0
pure A
~
:::l
1§
~ a
~ T---------------- --- ---
A 8
%8
I!!
:::l
~ ,~--~~----~
~ T -'- - - -- - -- -- - -- -- - --
E a (3
2 a+(3
A 8
%8
,
---: -~-:.~: :::~
A 8
%8
Figure 3.6. Diagram showing the relationship between a hypothetical composition profile,
phase diagram, and the expected equilibrium microstructure at temperature T for graded
materials in some simple binary systems.
52 Chapter 3
use in elevated temperature applications, therefore the influence of diffusion

on microstructure must be considered. As is the case for composite
materials, suitable combinations of materials with good chemical
compatibility can be selected in order to minimize changes in the
microstructure due to diffusion. In such cases, by designing and fabricating
arbitrary compositions and complex graded microstructures reasonable
stability of the original microstructure can be expected. Knowledge of phase
stability, interdiffusion rates, and mutual solubilities is therefore of critical
importance for producing materials with adequate stability. This is
particularly important in systems where extensive chemical reactions can
have deleterious effects on the mechanical integrity of the material. Because
there is a considerable lack of data for many systems of interest, more
fundamental research is needed.
Even with availability of the relevant thermodynamic and kinetic data,
details of the microstructure are difficult to predict since processing often
results in highly nonequilibrium structures. It should also be emphasized that
the phase diagram only specifies the composition of the phases present and
their relative amounts but does not provide any information on
microstructural geometry. Modeling the details of the evolution of
microstructural geometry in two-phase materials is an important area of
study in the field of materials science. Significant progress is being made
using a variety of modeling techniques to predict the size, shape, and
arrangement of second phases for special cases involving spatially uniform
materials. Technologically important examples include grain growth,
coarsening of second phase particles, and the evolution of pore structures
during sintering. Much more work is needed in order to apply these
modeling techniques to the complicated, nonuniform microstructures found
in FGMs.
3.4 Dispersed versus Connected Microstructures
Much of the work on FGMs relates to materials consisting of two-phase

mixtures. Figure 3.7 shows a schematic representation of the common
microstructural changes that occur in a material as the second phase content
is increased [13]. At low volume fractions of the second phase it exists as
isolated particles dispersed within a matrix phase. The dispersed particles
can be either single crystal or polycrystalline. The particles can be randomly
distributed within the matrix, or they can exist preferentially at sites such as
grain boundaries or grain junctions. The volume fraction, size, and spacing
of dispersed particles can be interrelated through the use of simple
geometrical models similar to those described in the previous section. Such
models have been used extensively, for example, to predict the yield stress
of dispersion strengthened alloys or to model coarsening of second phase

particles.
o
••
•
o
• •
Figure 3. 7. Schematic of microstructural changes that occur in a two-phase material as the
volume fraction of the second phase increases.
As the content of the second phase of a two-phase material increases, the

particles begin to interact through the formation of particle-particle contacts.
This leads to the formation of an agglomerated microstructure in which the
second phase remains dispersed, but often consists of polycrystalline
aggregates containing many particles or grains. The contiguity parameter
discussed above is extremely useful for characterizing the degree of particle
contact in these materials [6].
A B A B
c: c:
-
.Q
( /)
o
o
~
(/)
o
a. a.
E E
o o
u u
distance distance
Figure 3.8. Diagram showing the difference between a layered microstructure and a
continuously graded microstructure.
As the volume fraction is increased further, a critical microstructural

transition takes place in which the second phase is no longer dispersed but
54 Chapter 3
rather becomes interconnected over long distances. The transition from a

dispersed to an interconnected second phase structure can have a profound
effect on the behavior of the material [14]. Transport based properties such
as electrical or thermal conductivity, or gas permeability in porous solids, are
particularly sensitive methods for determining when an interconnected
structure is formed. In addition, certain mechanical properties, such as elastic
modulus and fracture toughness, are also strongly affected by long-range
connectivity of the second phase.
Connectivity in microstructures has been studied extensively using
percolation models [13-15]. These models treat the microstructure as a
network of nodes and interconnections in which composition is measured by
the number of completed connections or occupied nodes (lattice sites for
orderly packed structures). At a critical composition, the network becomes
connected over long-range distances. Typically, there is a sharp transition in
properties over a very narrow range of composition near the transition point.
In actual microstructures, the critical composition for the development of
an interconnected second phase often must be measured indirectly, since
metallographic methods underestimate the degree of particle or grain contact
that exists in three dimensions. Transport-based methods, such as electrical
or thermal conductivity, are extremely useful, particularly when the two
phases have markedly different transport properties. Many studies on
connectivity and percolation have been carried out, generally on mixtures of
conducting and nonconducting phases. The critical composition for second
phase connectivity has been found to depend on several factors, including
the packing arrangement (coordination number) and shape of the second
phase particles, and the relative sizes of the constituents (e.g., particle or
grain size ratio) [16].
In three-dimensional structures, both phases typically will be connected
at intermediate compositions, as shown in Figure 3.7. For example, in a fully
dense, two-phase mixture composed of equal sized grains, both phases will
be connected between approximately 18 and 82 volume % [17]. Maximum
interconnectivity will always occur between 40 and 60 volume %. FGMs
involving two-phase mixtures that vary from 100% of phase a to 100% of
phase b will always contain both kinds of dispersed phase microstructures
(i.e. a particles within a b matrix, and b particles within an a matrix), as well
as a wide compositional range in which the microstructures are characterized
by two interconnected phases.
3.5 Smoothly Varying versus Discretely Layered

Structures
Graded microstructures can be characterized by the nature of the spatial

variation in the microstructure. There are two general types of spatial
distributions, as shown schematically in Figure 3.8. In the first type, the
change in composition (or any other microstructural feature) occurs
continuously with position. In the second type, the microstructural feature
changes in a stepwise fashion, giving rise to a multilayered structure with
interfaces existing between discrete layers. Whether a material's
microstructure has continuous or stepwise spatial variation, it can be
represented using a continuous mathematical function.
The difference between these two fundamental types of microstructures
is important and can have implications with respect to the processing,
modeling, and behavior of FGMs. For example, certain processing methods
are only capable of producing one type of structure or the other [2]. As
already mentioned, a multilayered structure can conveniently be represented
for modeling purposes using a continuous mathematical function. Although
modeling may yield misleading results if the interfaces significantly affect
the behavior of the material. Certain material properties are known to be
influenced by the presence of internal interfaces, depending on the extent of
the discontinuity that exists. Therefore it is important to distinguish between
what actually exists at the microscopic level, what is represented
mathematically, and what is measured experimentally.
A multilayered structure can be made to approach a continuously varying
structure if the layer thickness is made smaller and smaller. But as
previously noted, for all practical purposes the thickness of an individual
layer need only be reduced below the characteristic size scale of the
microstructural features before the effects of the stepwise structure become
ambiguous. Many recently developed fabrication methods involving discrete
layer formation can be adapted to produce continuously graded structures.
Whether the effort and expense needed to accomplish this are practical or
even desirable must be evaluated on a case-by-case basis.
The representation of a multilayered structure by a continuous
mathematical function is usually accomplished by specifying the average
layer composition at some position within the individual layers. The most
obvious location to choose is the midpoint of the layers. However the
starting or ending interface can also be used.
56 Chapter 3
3.6 Mathematical Descriptions of Gradients
Mathematical functions are frequently used to represent the spatial

variation in microstructure within graded materials. A number of
mathematical functions can be used, depending on the nature of the material,
the particular microstructural feature being described, and the goals of
mathematical modeling.
Linear gradients, which are common in steady state transport problems,
represent the simplest mathematical form. Perhaps the earliest and most
widely known nonlinear mathematical functions used for describing
gradients involve the error function, erf(x). This function appears frequently
in solutions to the differential equation describing unsteady-state transport
(Fick's second law) which, in the case of solid state diffusion, can be written
generally as:
(3.14)
where C is concentration, t is time, and D is the interdiffusion coefficient.

In the one-dimensional case, this equation takes the familiar form:
dC =~5dC)
dt dx\ dx (3.15)
Depending on the initial and boundary conditions, the solution to this

equation can vary considerably. However, solutions for many practical
problems of interest are readily available [18]. As an example, Figure 3.9
shows schematically a problem involving one-dimensional diffusion
between two semi-infinite solids having compositions C 1 and C2 . For the
special case in which D is independent of composition, the solution to this
diffusion problem for all x>O takes the form:
,
CC-Co
-C -_ I2 12fu exp(-x2)dx -_erf (X)
r;::::
2 0 'V 1t 0 2"1 Dt (3.16)
where Co is the average concentration of C 1 and C2• Since erf(x) = -erf(-

x) the composition profile is symmetrical about x=O. The general form of
this function is shown in Figure 3.9.
original interface
/
C C1
Y
o
~
en / i n i l i a l di stribution
o
c..
E
o X=O~,
u
I
distance, x
1.0
0.8
C-C 2 0.6
C1-C2
0.4
0.2
0
-2 -1 0 1 2
X/(4Dt)1/2
Figure 3.9. Diagram showing the composition profile (top) of a diffusion couple, and the
profile at a later time t (bottom) for a system that exhibits complete solid solubility. The
solution to the diffusion equation is the error function, as shown in the bottom diagram.
In contrast to diffusion problems in which composition is of interest,

most research on FGMs has involved analysis of the distribution of second
phases as the primary microstructural variable of concern. However, at least
for simple systems the volume fraction of the second phase can be predicted
from compositional information using phase diagrams. Therefore, for FGMs
fabricated by transport-based methods, the diffusion equations are extremely
useful.
A number of non-transport-based methods (also called constructive
methods) can be used to fabricate FGMs [2]. In these materials, the initial
distribution of second phases (or more generally any microstructural
parameter) can be created without the constraints imposed by Equation 3.16.
There is thus a need for other, more general mathematical functions, for
58 Chapter 3
describing microstructural gradients. The most common of these, initially

suggested by Japanese researchers, involves a power law function, that when
written in terms of the volume fraction of the b phase takes the form:
vv(J3) =(X)P (3.17)
where X is the dimensionless distance across the graded material, shown

in Figure 3.10 and defined as:
(3.18)
where x 1 and x2 define the end positions of the graded material, x is the
distance into the graded layer from the x 1 interface, and p is the variable that
determines the shape of the curve representing the spatial distribution of the
volume fraction. The advantages of this function are that it is simple, and by
selecting values of p either greater or less than one, a wide variety of
distribution shapes can be represented, as shown in Figure 3.10. When
p=1.0, a linear spatial distribution is obtained.
The disadvantage of this function is that it does not allow for the
possibility of including inflection points or local maxima and minima in the
spatial distribution, as would be required for representing the material shown
in Figure 3.4. Although little or no work to date has focused on producing
materials containing nonmonatonic microstructural variations, they certainly
could be desirable in certain circumstances. To allow for the possibility of
describing arbitrary spatial distributions, other functions would be more
appropriate. The simplest of these would be the polynomial function:
(3.19)
Other functional possibilities would be equally valid, although the need

for more elaborate functions has not been justified yet.
~~
1
1
1
1
X
• I
- I
1 1
2
1
..
1
1
1
....
X=x, X=~ distance
1.0r---~--r---~--r---~--r---~--~--~~
0.8
c
0
-
~
....
c
~
c
0.6
8 0.4
~
~
....
Q)
0.2
0.0 ~""";:;;;;"'_======~---''------'-_"'"----1.._....o.----I
0.0 0.2 0.4 0.6 0.8 1.0
relative distance, X
Figure 3.10. Diagram showing various profiles for phase distribution obtained by varying the
exponent in the power law equation.
60 Chapter 3
4. EXAMPLES
In most of the literature about FGMs, the characterization of the

microstructure has been limited to describing the distribution of the volume
fractions within FGM specimens, and its relation to various properties. There
have been relatively few studies focusing on microstructural
characterization.
In one study on powder processed, partially stabilized zirconia/stainless
steel (PSZ/SS) FGMs, the transition from a dispersed to an interconnected
microstructure was investigated from 2-D cross sections using fractal
geometry concepts [19]. An interconnected phase was assumed to
correspond to a percolation cluster for which a mass fractal dimension was
determined, and a surface fractal dimension was assumed to characterize a
dispersed phase microstructure. It was shown that at the critical volume
fraction corresponding to the transition from a dispersed to an interconnected
microstructure, the mass and surface fractal dimensions were equal. Beyond
the critical volume fraction, the analysis based on the assumed
microstructural type broke down. In this way, it was shown that the critical
volume fraction could be determined by analyzing metallographic cross
sections. The critical volume fraction determined using fractal analysis was
in agreement with the value determined using conductivity measurements. In
a similar study on nickel/magnesium oxide (NilMgO) FGMs, density
scaling functions were used to obtain the mass fractal dimension and to
identify the ranges over which percolation clusters and interpenetrating
phases exist [20].
In another detailed study on PSZ/SS composites used in the fabrication of
FGMs, phase connectivity and percolation were investigated using
metallographic examination, serial sectioning, and idealized packing
simulations [21]. Two dimensional measurements of the Betti number were
made to quantify the range of volume fractions for both dispersed and
interconnected microstructures. For the particle size ratio used to produce
these materials, the phases were interconnected between about 15 and 45
volume % PSZ. Outside of this range, the materials exhibited dispersed
phase microstructures. At a volume fraction of 32 volume % PSZ, the mean
curvature of the metallceramic interface was shown to be zero, presumably
corresponding to the situation where the matrix and dispersed phases are
indistinguishable.
The percolation probability for the stainless steel phase determined by
serial sectioning was shown to be in reasonable agreement with that
calculated using a simple packing model. The metal phase appears to
undergo a percolation transition over the volume fraction range from 30 to
80 volume % PSZ. From 60 to 80 volume % PSZ the metal phase was
presumed to exist as tree-like clusters extending over relatively long

distances but with very few interconnecting branches. The conclusion is that
sufficient metal connectivity is required to obtain good electrical
conductivity and fracture toughness in these composites, and that the 2-D
measurements appear to provide a convenient means of determining the
degree of metal connectivity.
REFERENCES
1. Hirai, T. (1996) Functional gradient materials in Materials Science and Technology,
Vol.17B, Processing o/Ceramics, Part 2, (ed. RJ. Brook), VCH Verlagsgesellschaft mbH,
Weinheim, Germany, 293-341.
2. Mortensen, A. and Suresh, S. (1995) Functionally graded metals and metal-ceramic
composites, Part 1 Processing, Int. Mater. Reviews, 40 (6), 239-265.
3. DeHoff, R.T. and Rhines, F.N. (ed.) (1968) Quantitative Microscopy, McGraw-Hill, New
York.
4. Underwood, E.E. (1970) Quantitative Stereo logy, Addison-Wesley, Reading, MA.
5. Exner, H.E. and Hougardy, H.P. (1988) Quantitative Image Analysis o/Microstructures,
DGM Informationsgesellschaft mbH., Oberursel, Germany.
6. Gurland, J. (1966) An estimate of contact and continuity of dispersions in opaque samples,
Trans. AIME, 236, 642-646.
7. Hirano, T. et al. (1990) On the design offunctionally gradient materials, in Proc. First Int.
Symp. on FGM'90, (eds. M. Yamanouchi et al..), The Society of Non-Traditional
Technology, 5-10.
8. Wakashima, K. and Tsukamoto, H. (1990) Micromechanical approach to the
thermomechanics of ceramic-metal gradient materials, ibid., 19-26.
9. Markworth, A.J. et al. (1995) Modeling Studies Applied to Functionally Graded Materials,
J Mater. Sci., 30, 2183-2193.
10. Suresh, S. and Mortensen, A. (1997) Functionally graded metals and metal-ceramic
composites, Part II, Thermomechanical properties, International Materials Reviews, 45,
85-116.
11. Eshelby, J.D. (1957) The Determination of the elastic field of an ellipsoidal inclusion,
and related problems, Proc. Royal Society, Series A, A241, 376-396.
12. Weissenbek, E. et al. (1997) Elasto-plastic deformation of compositionally graded metal-
ceramic composites, Acta Materialia, 45 (8), 3401-3417.
13. Nan, c.-W. (1993) Physics of inhomogeneous inorganic materials, Progress in Materials
Science, 37,1-116.
14. Deutscher, G. et al. (ed.) (1983) Percolation Structures and Processes, Adam Hilger,
Briston, UK.
15. Stauffer, D. (1985) Introduction to Percolation Theory, Taylor and Francis, London.
16. German, R.M. (1989) Particle Packing Characteristics, Metal Powder Industries
Federation, Princeton, NI, 253-274.
17. Cahn, I.W. (1966) A model for connectivity in multiphase structures, Acta Metall, 14,
477-480.
18. Geiger, G.H. and Poirier, D.R. (1973) Transport Phenomena in Metallurgy, Addison-
Wesley, Reading, MA, 473-513.
62 Chapter 3
19. Muramatsu, K. et al. (1990) Fractal analysis of the microstructural transition in PIM
functionally graded materials, inProc. First Int. Symp. on FGM'90, (eds. M. Yamanouchi
et a/.), The Society of Non-Traditional Technology, 53-58.
20. Nan, c.-W. et al. (1993) The physics of metaIIceramic functionally graded materials in
Ceramic Trans., 34, Proc. Second Int'/. Symp. on FGM'92, (eds. J.B. Holt et al.), The
American Ceramic Society, Westerville, OH, 75-82.
2l. Watanabe, R. et at. (1995) Microstructural characterization ofmetaVceramic functionally
gradient materials, in Proc. a/The Third Int '/. Symp. on Structural and Functional
Gradient Materials, (eds. B. Ilschner and N. Cherradi), Presses Polytechniques et
Universitaires Romandes, Lausanne, Switzerland, 3-8.
Chapter 4
MODELING AND DESIGN
Keywords: Modeling, finite element method, residual thermal stress, rule of mixtures,
elastic modulus, shear modulus, bulk modulus, micromechanical approach,
representative volume element, Poisson's ratio, Young's modulus, isostrain,
isostress, flow stress, strain hardening, fuzzy logic technique, yttria-stabilized
zirconia, partially stabilized zirconia, elastic-plastic deformation, creep,
power-law creep
1. INTRODUCTION
With the advent of powerful computers and robust software,

computational modeling has emerged as a very informative and cost
effective tool for materials design and analysis. Modeling often can both
eliminate costly experiments and provide more information than can be
obtained experimentally. Computational modeling has clearly played an
important role in FGM research to date, and because of the considerable
complexity involved, is expected to play an even greater role in future
developments. This chapter introduces some of the common approaches
used in modeling FGMs, identifies the major difficulties involved, and, it is
hoped, provides useful guidance for future simulation efforts. It focuses
mainly on continuum models of the bulk response of FGMs due to thermal
or mechanical loading.
Since the term "modeling" is quite general, the discussion first centers on
a more specific definition of modeling as used in this chapter. A hypothetical
FGM application is introduced and a variety of models are discussed, each
designed to address a particular issue or concern. Typical modeling
approaches are then described, leading to the conclusion that the most
significant difficulty in FGM modeling is the accurate determination of the
64 Chapter 4
material properties of the interlayers. The main body of the chapter then
provides a detailed discussion on the estimation of FGM properties,
including numerous comparisons with experimental data. Where possible,
specific recommendations are made.
2. BACKGROUND
Models are commonly used by scientists. However, modeling is a general

term that has a variety of meanings. Essentially, models are some
representation of reality, either actual physical objects such as a model
airplane or simply mathematical entities. Mathematical models are
developed in a variety of length scales, ranging from the atomic level (e.g.,
molecular models) to fully integrated systems. As used in this chapter,
modeling refers to the use of either analytical or numerical mathematical
solutions of the basic laws of physics to simulate the response of real
materials. More specifically, these solutions are designed to predict the bulk
thermomechanical response (e.g., temperature, displacement, stress, and
strain fields) of FGMs subjected to varying thermal or mechanical loading
conditions. The ability to accurately predict the temperature, stress, and
strain fields is important, since such parameters can strongly affect the
performance and structural integrity of FGM components.
2.1 A Hypothetical Example
A hypothetical FGM application illustrates some of the types of

mathematical models that can be used with these materials, and how such
models can assist in improving a component's design, lifetime, and
performance. Consider an exhaust valve for an internal combustion diesel
engine, shown schematically in Figure 4.1, which controls the flow of
exhaust gases from the combustion chamber. Under normal operating
conditions, the valve is subjected to high temperatures (combustion gases),
thermal cycling (engine start-up and shut-down), and mechanical loading
(forces from rapid opening and closing). To permit higher operating
temperatures and improve engine efficiency, an FGM has been proposed as a
protective layer (i.e., a thermal barrier coating) on the valve face [1]. A
consideration of the fabrication and application of the valve illustrates
various ways in which mathematical modeling can be advantageous.
65
face FGM layer
seat
stem
Figure 4.1. Schematic of an exhaust valve for an internal combustion diesel engine shown as
a hypothetical FGM application.
Thermal barrier coatings are typically applied via spray deposition or

other deposition processes at high temperatures. On cooling, thermal residual
stresses develop due to differences in the properties of the materials,
particularly thermal expansion coefficients. Such stresses exist even if the
cooling process is sufficiently slow for the temperatures to remain spatially
uniform, and can be large enough to cause the component to fail. A
numerical solution of the basic equations of mechanics (Le., a finite element
model) can provide estimates of the residual thermal stress and strain levels
in both the valve body and the FGM coating.
During operation, the valve face is exposed to high temperature
combustion gases, yet the valve seat remains relatively cool due to
intermittent contact (while closed) with the engine head. Thus a large
thermal gradient exists across the valve. The temperature field can be
approximated by solving the energy equation either analytically or
numerically. Unfortunately, large thermal gradients can lead to large thermal
stresses. The thermal gradients can be the result of normal operating
conditions, as described above, or can be cyclic, such as occur during start-
up or shut-down.
By combining a thermal analysis (solution of the energy equation) with a
mechanics analysis, the effect of the temperature field on component stresses
and thus component integrity can be predicted. Almost always, these
66 Chapter 4
analyses can be decoupled since the mechanical analysis has little effect on
the temperature field. During operation, the valve also undergoes mechanical
loading/unloading cycles as it rapidly opens and closes. Further analyses can
be used to determine the resulting stress and strain fields from this applied
loading. For all the models described, parametric studies, in which changes
in geometry, material properties, or loading are considered, can provide
added insight and lead to optimized designs.
2.2 Modeling Approaches
For each type of model discussed in the above example, the basic partial
differential equations from continuum mechanics are applicable and are
well-established and understood [2]. Since the basic conservation equations
are generally applicable to any continuum, they are not affected by the
addition of an FGM layer. For simple geometries and reasonably simple
material properties (e.g., elastic behavior) analytical solutions are often
available. For more complex geometries or constitutive behavior, robust
numerical solution techniques (e.g., finite element methods) can be used to
provide accurate approximate solutions. A wide variety of software is
commercially available [3].
With respect to numerical solutions that employ finite size computational
cells, an FGM layer typically is approximated as a series of perfectly bonded
interlayers, with each layer having slightly different material properties than
its neighbors. Material properties are thus assumed to change continuously in
the direction of the gradient. Numerical studies using continuum models
have been designed recently to investigate localized microstructural effects
[4, 5]. Essentially, these studies use very fine computational meshing to
simulate individual grains of ceramics or metals (in either periodic or
random arrangements), and also to simulate the evolution of local stress and
strain fields. Results from these models reveal detailed information about
microstructural behavior at the grain size level. It is anticipated they will
provide insight for FGM optimization.
For the macrolevel continuum models, clearly the most significant
difficulty encountered is the accurate determination of material properties for
each interlayer. This complication is the main factor that sets FGM models
apart from standard analyses. Because of its importance to accurate
simulations, the estimation of material properties is the crux of this chapter.
67
3. ESTIMATION OF MATERIAL PROPERTIES
3.1 General Comments
Realistic predictions of the thermomechanical behavior of FGMs require

appropriate constitutive relations containing accurate thermophysical
property data. Since a tailored spatial variation in microstructure is
intentionally introduced in an FGM, a variety of different microstructures
can exist within a graded region. Thermophysical properties, which are
dependent both on individual phase properties and on microstructural details,
such as volume fraction; size, shape, orientation, and spatial distribution of
the phases; and phase connectivity, similarly can vary strongly with position.
Property estimates are further complicated because often both the production
processes and the intended applications for FGMs involve significant
temperature variations. Because of the vast number of measurements
required, experimental data are limited, often including information only for
the individual phases. Clearly, the ability to provide reasonable estimates of
material properties based on complex microstructures and limited
experimental data is a challenging but important component of the modeling
process.
An FGM is a heterogeneous material that consists of regions of different
materials or even of the same material in different states. In developing
estimates of thermophysical properties, a basic assumption is that the
microscopic length scale for the material is much larger than molecular
dimensions, but much smaller than the characteristic length of the
macroscopic sample. A heterogeneous material can then be regarded as a
continuum on the microscopic scale, and thus macroscopic or "effective"
properties can be used.
It is important to recognize that FGMs are basically composite materials.
Efforts to determine analytically the effective thermophysical properties of
composites were initiated more than a century ago by such famous scientists
as J. C. Maxwell, Lord Rayleigh, and Albert Einstein [6]. Because of
increased interest recently in composites for industrial applications, the
subject of composite properties has been thoroughly developed, and a large
literature base exists. Several extensive review articles are available, that
provide both good overviews of the subject and insight into the significant
complexities involved [6-8]. This chapter examines some of the more
practical techniques that have been applied to FGMs, and provides
background information and typical examples for commonly encountered
thermomechanical properties. The overall goal is to provide sufficient
information to guide the selection of appropriate techniques for estimating
material properties.
68 Chapter 4
This section begins by identifying and briefly describing some of the

common techniques used to estimate thermophysical properties in FGMs,
starting with the simplest and progressing to the more complex. Specific
thermal and mechanical material properties are considered next, including
comparisons of the various estimation techniques and, where available,
comparisons with measured data. It should be noted that the experimental
data selected for comparison was restricted to the FGM literature, principally
the first five international symposia (1990, 1992, 1994, 1996, and 1998 ).
This was done both to keep the comparisons focused on FGM materials and
to demonstrate the limited set of property data that exists for these materials.
3.2 Approaches
3.2.1 Rules of mixtures
A common approach for estimating the material properties of FGMs is to

apply a rule of mixtures. Although actually not physical or mathematical
rules, these relationships can be used to approximate thermal or mechanical
properties of a composite material in terms of the individual properties and
relative amounts of the constituents.
The simplest is the classical linear rule of mixtures (Voight estimate) for
two constituent materials [9]:
(4.1)
where P is a typical property, V is the volume fraction, and the subscripts

a and Bare used to distinguish the two constituents. The Voight estimate is
simply a volume based arithmetic mean. Another well-known mixture rule is
the harmonic mean (Reuss estimate) [10]:
(4.2)
In their most basic form, the above rules of mixtures are employed using
bulk constituent properties, assuming no interactions between phases.
Because of their simplicity, they are often used for FGMs, since a single
relationship can be used for all volume fractions and microstructures.
However, also because of their simplicity, their validity is limited.
In an effort to include interaction effects between constituent materials,
the rules of mixtures also are described and used in a modified form, either
by utilizing in-situ constituent properties [11] or by including empirical data.
69
Complex stress-strain data have been approximated using this empirical

approach.
Recently, a generalized rule of mixtures has been described for
application to FGMs that includes the effects of grain shape and phase
distribution [12]. Since this approach is derived solely from continuum
mechanics, it is free of empirical considerations. Excellent agreement is
claimed between the generalized rule of mixtures and experimental results
drawn from the literature.
3.2.2 Variational approach
This approach involves the application of variational principles of

thermomechanics (e.g., elasticity theory for elastic moduli, diffusion theory
for thermal conductivity) to derive bounds for effective thermophysical
properties. Assuming homogeneous, isotropic materials, and applying
variational methods to linear elasticity theory, relations have been obtained
(Hashin and Shtrikman or HS) for the upper (U) and lower (L) bounds on the
effective bulk modulus (K) and shear modulus (G) [13]:
v~
KL =Ka + - - - - - ' - - - - - (4.3)
1 + 3Va
K~ - Ka 3Ka + 4G a
Ku = K~ + ____V.;...la.:io..-~-- (4.4)
1 + 3V~
Ka - K~ 3K~+ 4G~
(4.5)
(4.6)
70 Chapter 4
Because of the isotropic assumption, all other elastic properties can be

calculated directly from the bulk and shear moduli.
A similar approach has been applied to electromagnetic theory to obtain
bounds on the effective magnetic permeability [14]. By direct analogy, these
results can be used to compute effective bounds on thermal conductivity (k):
(4.7)
(4.8)
For both the elastic and thermal properties, the above relations are the
best possible bounds that can be derived based only on the constituent
properties and volume fractions. To improve on these bounds, additional
information, such as the spatial distribution of the phases (i.e. the
microstructure) is needed [13, 14].
3.2.3 Micromechanical approaches
3.2.3.1 Standard Methods

In contrast to the variational techniques, micromechanical approaches
attempt to include information about the spatial distribution of the
constituents in the material. The standard micromechanical approach is
based on the concept of a unit cell or representative volume element (RVE)
to represent the microstructure of the composite. A large variety of
thermophysical property relationships can be formulated based on various
unit volume geometries, bonding assumptions, loading conditions, and
boundary conditions.
One of the earliest and simplest micromechanical approaches (Kerner)
assumes a spherical reinforcement particle in a uniform isotropic medium,
with perfect bonding between the phases [15]. Considering both elastic [15]
and thermal [16] problems for two phases, relations are obtained for the
effective bulk (K) and shear moduli (G), the thermal conductivity (k), and
the coefficient of thermal expansion (a):
71
V K V K [3Ka + 4Ga]
K = a a + [3 [3 3K[3 + 4Ga
(4.9)
V + V [ 3Ka + 4G a ]
a [3 3K[3 + 4G a
(4.1 0)
(4.11 )
(4.12)
where v is Poisson's ratio.

A more recent effort (Wakashima and Tsukamoto) employed a "mean-
field" approach characterized by a random dispersion of misfitting
ellipsoidal inhomogeneities, induding an interaction effect to account for the
typically large number of ellipsoids that interact [17]. This approach was
based on earlier work involving a single ellipsoid in a uniform elastic
domain [18]. The interaction is accounted for as an approximation using the
"average stress in matrix" concept [19]. Relations were derived for the
effective bulk (K) and shear moduli (G), thermal conductivity (k),
volumetric specific heat (C), and coefficient ofthermal expansion (a):
(4.13)
72 Chapter 4
(4.14)
(4.15)
(4.16)
u= (4.17)
For both the Kerner [15] and the Wakashima and Tsukamoto [17]
approaches, the assumption of which phase is the matrix and which the
reinforcement provides two unique functions analogous to the HS bounds.
Even more recently, microstructural effects have been incorporated using
a periodic arrangement of perfectly bonded cubic inclusions uniformly
distributed in a continuous matrix (Ravichandran) [20]. Upper and lower
bounds for the elastic properties of a unit cell are then derived by
considering both parallel and series arrangements of the two phases
respectively, loaded in isostrain and isostress configurations. Relations are
provided in terms of the Young's modulus (E).
(4.18)
(4.19)
73
(4.20)
In developing Equations 4.18-4.20, it was assumed that the Poisson's

ratios of the constituent materials are equivalent, and it was also noted that a
similar development provides identical relations for the shear moduli. Since
the composite materials are assumed isotropic, the Young's modulus can be
related easily to the bulk modulus provided by the approaches discussed
above. Although the rules of mixtures (Equations 4.1-4.2) are usually
considered simple averages, for the elastic moduli they can also be formally
derived using this micromechanical approach.
3.2.3.2 Higher Order Methods

In applying micromechanical approaches to FGMs, a need for higher
order methods has been identified. Cases have been considered in which the
size of the inclusion phase is large relative to the overall dimension of the
composite, and approaches have been developed that apparently eliminate
the difficult and still largely unresolved issue of what constitutes a
representative volume element or unit cell in an FGM [21]. The theory
explicitly couples local and global effects. This higher order approach has
been implemented in a computer program, MAC (Micromechanics Analysis
Code) that apparently can predict the responses of both continuous and
discontinuous multiphased composites with arbitrary internal
microstructures and reinforcement shapes [22]. Similarly, conventional
micromechanical theory has been generalized to allow linear variations in
local and applied stress and strain fields [23]. This method makes it possible
to estimate the significance of the reinforcement gradients on the effective
properties of an FGM.
3.2.3.3 Numerical Solutions

There is now a considerable effort to combine conventional
micromechanical approaches with numerical solution techniques in order to
estimate the effective properties of composite materials. Since analytical
solutions are only available for simple cell geometries (typically spheres and
bricks) and patterns, numerical techniques permit a look at more complex
representative volume elements, boundary and loading conditions, and
interface properties. To date, efforts have included the effects of localized
damage (plasticity, cracking) that potentially could have a significant impact
on effective properties. A recent review provides an excellent summary of
the large body of literature being developed in this area [24].
74 Chapter 4
3.2.4 Empirical approaches
In the absence of complete experimental data, it is possible to combine

theoretical approaches (e.g., rule of mixtures) with limited empirical data to
predict material properties. One example is the modified rule of mixtures
that has been used to predict the non-linear, stress-strain behavior of FGMs
illustrated schematically in Figure 4.2 [25]. Stress-strain curves for the
composite material are constructed by dividing both the stress and the strain
between the constituents using the linear rule of mixtures, as follows:
(4.21)
(4.22)
where O'n , O'~ and En, E~ are the true stress and strain of the ceramic and
metal, respectively, and O'c and Ec are the composite flow stress and strain.
Since these equations do not specify the absolute amount of stress and strain
transfer, an additional equation,
(4.23)
that defines the ratio of stress to strain transfer is required. As illustrated

in Figure 4.2, q is the slope of a correspondence line on the stress-strain
curve, with large slopes approaching the isostrain condition (En = E~ = cc) and
small slopes the isostress condition (O'n = O'~ = O'c). Values for q are obtained
empirically and, in general, depend on many factors, including composition,
flow stress ratio and strain hardening of the constituent phases, their
microstructural arrangement, and the applied strain. A constant q value
obtained from experiments with systems involving coarse two-phase
microstructures comprised of hard and soft constituents has been assumed as
a first approximation, [25, 26].
3.2.5 Fuzzy logic techniques
In each of the micromechanical techniques described above [15, 17, 20],

the analytical relations provide two unique functions based on the
assumption of which phase is the matrix and which the reinforcement. In an
FGM, the deliberate variation in its microstructure can result in separate
75
regions where a given material acts as either the matrix or the reinforcement,
or something intermediate. Thus one function might adequately describe one
microstructure within the FGM and the second another microstructure, with
a connecting region that is not well described by either function.
To address this issue, Kerner's micromechanical method has been
combined with fuzzy logic techniques to provide a smooth transition
between bounding curves [27]. In effect, this approach provides an
averaging equation that uses one of the two bounding functions at extreme
volume fractions, whereas at intermediate volume fractions the effective
properties are taken as some weighted average of the bounds. Additional
information, which is usually obtained empirically, is required to define the
interpolation functions and the volume fractions over which averaging
occurs.
(l -ceramic phase
(l ~ metal phase
-
c - composite
V - volume fraction
q - tie line slope
-
15'
£c
Strain (£)
Figure 4.2. Illustration of the modified rule of mixtures used to approximate stress-strain
curves for FGMs.
3.3 Thermophysical Properties
3.3.1 Thermal expansion coefficient
With respect to temperature changes in FGMs (either during their

processing or their application), probably the most important thermal
property is the thermal expansion coefficient. For a given temperature
76 Chapter 4
change, thermal stresses are directly related to the thermal expansion

difference between the two constituent materials.
Figure 4.3 shows the effective thermal expansion coefficient (normalized
between zero and one) as a function of volume fraction as predicted by the
simple rule of mixtures (Equations 4.1-4.2) and the Kerner (Equation 4.12)
and Wakashima (Equation 4.17) micromechanical theories. Experimental
data for six metal/ceramic and two ceramic/ceramic FGMs are included for
comparison. Since the micromechanical relations are functions of the
mechanical properties (e.g., the bulk and shear moduli) they are shown for
an actual metal/ceramic composite. The Ni-Ah03 system was chosen for this
comparison since it has the largest thermal expansion difference of all the
material systems considered, and thus maximizes the spread between the
upper and lower bounds.
2.50
- - Voight ROM
2.25
- - - Reuss ROM
2.00 ••••••••• Kerner. Wakashima
o Ni/MgO [4.281
1 .75
o 304SS/PSZ [4.281
1 .50 Ni 3 AI/TiC [4.281
... 6
tS
I
v Ni/TiN [4.29]
1 .25
tr ~ Ni/ AI20 3 [4.301
...
"-
tS 1 .00 ~ Ni/Zr02 [4.311
I
tS X TiN/Si 3 N. [4.291
0.75
~ TiC/SiC (4.321
0.50
0.25
0.00
-0.25
0.0 0.2 0.4 0.6 0.8 1. 0
V,
Figure 4.3. The effective thennal expansion coefficient as a function of volume fraction as
predicted by the rule of mixtures and the Kerner and Wakashima micromechanical theories.
Experimental data for six metal/ceramic and two ceramic/ceramic FGMs are included for
comparison. The subscripts (1 and 2) in the labels of the axes correspond to the first and
second materials listed in the legend.
77
The Kerner and Wakashima theories provide identical functions, well

within the bounds provided by the rule of mixtures. The spread between the
two is quite small, even for the large thermal expansion difference between
Ni and Ah03. Clearly there is significant scatter in the available
experimental thermal expansion data for FGMs. Based on a general
comparison of the predictions and experimental data, there appears to be no
justification for using other than a simple linear rule of mixtures for
estimating the effective thermal expansion coefficients of FGM materials.
With respect to the effects of porosity, experiments with porous materials
have concluded that there is no influence of porosity on the effective
coefficient of thermal expansion [28, 31].
3.3.2 Thermal conductivity
Figure 4.4 compares the effective thermal conductivity (normalized

between zero and one) as a function of volume fraction for a two-constituent
composite, as predicted by the rule of mixtures (Equations 4.1-4.2), the HS
variational technique (Equations 4.7-4.8), and the Kerner (Equation 4.11)
and Wakashima (Equation 4.15) micromechanical approaches. Three
separate plots are provided corresponding to conductivity ratios (kl/k2) of
32, 12.5, and 3.5. Experimental data for three metal/ceramic FGMs with
corresponding conductivity ratios are included for comparison.
The variational technique and the two micromechanical theories produce
identical results for thermal conductivity, providing upper and lower curves
that lie well within the rule of mixtures approximations. These bounding
functions are quite close for moderate thermal conductivity ratios (e.g., k 1/k2
= 3.5 in Figure 4.3(c)) but diverge considerably as this ratio increases. The
comparison between theoretical predictions and experimental data provides
interesting and valuable insight for the estimation of thermal conductivity in
FGMs. Compared with the thermal expansion coefficient, the linear rule of
mixtures is clearly inadequate, which indicates the need for the kind of
additional information included in the micromechanical theories.
A clear example is shown in Figure 4.4(a), where experimental data for
the same material system (Ni/Zr02) from two different sources are plotted.
The data sets are widely apart, with the Takemura [33] data nicely fit by the
lower micromechanical theory (appropriate for metal particles in a ceramic
matrix) and the Matsumura [34] by the upper relation (appropriate for
ceramic particles in a metal matrix). The Takemura material was produced
using layered powders and sintering, resulting in a ceramic matrix, and the
Matsumura material by an electroplating technique, resulting in a metal
matrix. The comparison with micromechanical theory is thus very good.
78 Chapter 4
At a reduced conductivity ratio (k]ik2=12.5, Figure 4A(b», the data for

hot pressed 304SSIYSZ (304 stainless steeVyttria-stabilized zirconia) are
reasonably well represented by an average of the upper and lower HS or
micromechanical bounds. Data for the thermal sprayed material are not well
characterized by any of the relations, which may be due to porosity. A three-
material theory (e.g., metal/ceramic/void) is probably needed for materials
with considerable porosity. At the lowest conductivity ratio considered
(k]/k2=3.5, Figure 4.4(c)), the upper and lower HS and micromechanical
relations are quite close and the data are reasonably well represented by
either function.
1.1
1. a - - Voight ROM
- - - Reuss ROM
0.9
••••••.•• HS, Kerner, and Wakashimo .......
0.8 o Ni/Zr02 [4.33]
IiI d ' [I
C Ni/Zr02 [4.34]
0.7
..0.... : I
~ 0.6 !I
...
1-
!
: I
......
';;
I
0.5
0.4
P
I
I
... I
0.3 0.""
.' I
I
0.2 ...~.......... ",/'
0.1 '"
0.0
-0.1
0.0 0.2 0.4 0.6 0.8 1.0
VI
(a)
Figure 4.4. The effective thennal conductivity as a function of volume fraction as predicted
by the rule of mixtures, the HS variational technique, and the Kerner and Wakashima
micromechanical theories. Experimental data for three metal/ceramic FGMs with conductivity
ratios (k/k2) of32 (Figure 4.4(a», 12.5 (Figure 4.4(b», and 3.5 (Figure 4.4(c» are show for
79
1.2
1.1 - - Voight ROil
- - - Reuss ROil
1.0
...•.•..• HS, Kerner, and Wakashima
0.9 o 304SS/YSZ - hot pre .. (4.351
0.8 o 304SS/YSZ - spray [4.351
...N
0.7
...'- 0.6
......,
';:; 0.5
0.4
0.3
0.2
0.1
0.0
-0.1
0.0 0.2 0.4 0.6 0.8 1.0
V,
(b)
1.1
1.0 - - Voight ROW

- - - Reuss ROil
0.9 ......... HS, Kerner, and Wakashima ....:.:.•)
o
0.8
0.7
IN100/ZrOz (4.361
......::::. .::···~II
~ 0.6
}
......,
';:; 0.5
0.4
0.3
0.2
0.1
0.0
-0.1
0.0 0.2 0.4 0.6 0.8 1.0
V,
(c)
Figure 4.4. The effective thennal conductivity as a function of volume fraction as predicted
by the rule of mixtures, the HS variational technique, and the Kerner and Wakashima
micromechanical theories. Experimental data for three metal/ceramic FGMs with conductivity
ratios (k 1ik2) of32 (Figure 4.4(a)), 12.5 (Figure 4.4(b)), and 3.5 (Figure 4.4(c)) are show for
80 Chapter 4
3.3.3 Heat capacity
Of the approaches reviewed above, only the Wakashima

micromechanical theory and the simple rules of mixtures can be used to
estimate the effective volumetric heat capacity. Experimental data for this
property are very limited in the FGM literature, probably because it is less
important than the thermal expansion coefficient or conductivity (heat
capacity is only needed for transient analyses and has no effect on the steady
state). The available data are insufficient to either support or refute the linear
or nonlinear rule of mixtures. Because the micromechanical approach
(Equation 4.16) results in a simple linear relation that is the same as the
linear rule of mixtures (Equation 4.1), a linear approximation is
recommended.
3.4 Mechanical Properties
3.4.1 Elastic modulus
For an isotropic material (which is assumed here), all elasticity properties

can be expressed in terms of just two independent constants. As shown
above, the HS, Kerner, and Wakashima relations are all derived in terms of
the bulk and shear moduli, whereas Ravichandran's approach assumes that
the constituents have equivalent Poisson's ratios and provides a relationship
for the Young's modulus. Since the Young's modulus can be computed
easily from the bulk and shear moduli, it can be used to make comparisons
between the various approaches.
Figure 4.5 compares the effective Young's modulus (normalized between
zero and one) as a function of the volume fraction for a two component
composite as predicted by the rule of mixtures (Equations 4.1-4.2), the HS
variational method (Equations 4.3-4.6), and the Kerner (Equations 4.9-4.10),
Wakashima (Equations 4.13-4.14), and Ravichandran (Equations 4.18- 4.20)
micromechanical approaches. Three separate plots are shown corresponding
to modulus ratios (E l fE 2) of 3.7, 1.9, and 1.2. Experimental data for three
FGMs with corresponding modulus ratios are included for comparison.
During the process of generating data for the plots it was discovered that the
seemingly very different analytical relations for the HS and Kerner
approximations produced identical numerical results. Therefore, they were
combined into a single set of curves in each of the Figures.
Figures 4.5(b) and 4.5(c) indicate that for moderate mismatch ratios the
HS, Wakashima, and Ravichandran bounds yield almost identical results.
Furthermore, the upper and lower bounds are quite close, and probably
within the experimental error for single-phase properties. As the mismatch
81
ratio increases, shown in Figure 4.S(a), the upper and lower bounds
increasingly separate. Of the various methods considered here, the
Ravichandran approach produces the closest upper and lower bounds,
followed by the Wakashima bounds, then the HS bounds, and finally the rule
of mixtures. The Ravichandran bounds are reasonably close, even for
relatively large mismatch ratios. Again, the comparison of theory with the
experimental data provides interesting and important insights into the
prediction of properties.
For the metal/metal (W/Cu) FGM shown in Figure 4.S(a), in general the
experimental data appear to fall between the linear rule of mixtures relation
and any of the upper bounds from the variational or micromechanical
approaches, since they are all similar. Taking into consideration
experimental accuracy, it is expected that either the linear or anyone of the
non-linear upper relations should provide a reasonable prediction of the
effective modulus. However, because data were available for only one
metal-metal FGM, the generalizability of this suggestion is uncertain.
1.1
1.0 - - Voight/Reuss ROW

- - HS, Kerner
0.9
----- Wakashima
0.8 ......... Rovichandran
0.7
o W/Cu [4.37J
~ 0.6
'-
~ 0.5
,
<oj
<oj 0.4
0.3
0.2
0.1
0.0
-0.1
0.0 0.2 0.4 0.6 0.8 1.0
(a)
Figure 4.5. The effective Young's modulus as a function of volume fraction as predicted by
the rule of mixtures, the HS variational technique, and the Kerner, Wakashima, and
Ravichandran micro mechanical theories. Experimental data for three FGMs with modulus
ratios (E/E 2) of3.7 (Figure 4.5(a», 1.9 (Figure 4.5(b», and 1.2 (Figure 4.5(c» are shown for
comparison. The subscripts (I and 2) in the labels of the axes correspond to the first and
82 Chapter 4
, .6
- - Voight/Reuss ROW
, .4
- - H5, Kerner
----- Walca.hima
, .2
......... Rovichandron
, .0 o AI Z0 3/Ni - part. reinforced [4.381

o AI 2 0 3/Ni - interpenetrating [4.381
...L
N
... 0.8
......
";:;
I 0.6
0.4 0
0.2 C
0.0 0
0
-0.2
0.0 0.2 0.4 0.6 0.8 f .0
V,
(b)
, .2
,. , - - Voight/Reuss ROW
, .a - - H5. K,rner
----- Wakashima
0.9 ......... Ravlchandran
0.8 o PSZ/304SS [4.281
0.7
~
...L 0.6
......
";:;
I
0.5
o
0.4
0.3
0.2 o o
O. ,
0.0
-0. ,
0.0 0.2 0.4 0.6 O.B , .a
V,
(c)
Figure 4.5. The effective Young's modulus as a function of volume fraction as predicted by
the rule of mixtures, the HS variational technique, and the Kerner, Wakashima, and
Ravichandran micromechanical theories. Experimental data for three FGMs with modulus
ratios (E/E 2 ) of3.7 (Figure 4.5(a», 1.9 (Figure 4.5(b», and 1.2 (Figure 4.5(c» are shown for
comparison. The subscripts (I and 2) in the labels of the axes correspond to the first and
83
For the interpenetrating phase ceramic/metal (AhOiNi) FGM shown in

Figure 4.5(b), the comparison of experimental data with any of the
variational or micromechanical theories is excellent for ceramic/metal
volume fractions of 0.2 and 0.4, but very poor at 0.6. For the particle-
reinforced material, the 0.2 volume fraction is in reasonable agreement, but
at larger volume fractions, none of the predictions fits the experimental data
well. This discrepancy is attributed to damage effects from debonding
between phases, poor sinter bonding between contiguous ceramic particles,
or particle fracture. These possible damage effects are not included in the
theories. The fit has been improved by including damage effects in the
Ravichandran micromechanical approach [38]. Even when the moduli of the
two phases are very similar, such as for the 304SS/PSZ FGM shown in
Figure 4.4 c, the comparison is not good for ceramic/metal volume fractions
above about 0.2. Again, this is believed to be due to damage effects.
3.4.2 Plasticity
Although clearly important for many FGM applications, few simulations

to date have included plasticity effects. In most cases, elastic behavior has
been assumed, sometimes resulting in significant errors. The major reason
plasticity effects are neglected is because of the difficulty and uncertainty
involved in predicting effective properties. Examples of stress-strain curves
for FGMs exemplify this point.
Figure 4.6(a) shows experimentally obtained stress-strain curves for a
PSZINi (partially stabilized zirconia/nickel) FGM produced by hot-pressing
[39]. Although not shown in this Figure, pure nickel exhibits classic elastic-
plastic behavior, while pure PSZ is linear-elastic to failure. With only 20
volume % PSZ, the composite displays typical elastic-plastic deformation
similar to pure nickel, while at 40 and 80 volume % PSZ, the response is
linear elastic. At 60 volume % PSZ, however, the response becomes
nonlinear again. It is suggested that this nonlinear behavior is due to a
microstructure transition at this composition, resulting in loose connectivity
ofthe two phases [39].
Figure 4.6(b) shows experimentally obtained stress-strain curves for a
YSZ/SS304 FGM produced by sintering [35]. The pure stainless steel shows
typical stress-strain behavior for a metallic material, with a failure strain of
approximately 11 %. Each of the composite compositions displays slightly
nonlinear behavior, with failure strains of approximately 0.5% or less.
Interestingly, the 40 volume % YSZ material appears to be more nonlinear
than the 20 volume % YSZ.
The two sets of data described above vary considerably, even in basic
trends. Although not shown, additional data are available for an Ah03INi
84 Chapter 4
FGM [38] and indicate even different behavior. The data clearly show the
difficulty of accurately describing this complex behavior with simple
theories such as the modified rule of mixtures (Equations4.21-23). Such
relationships can provide rough approximations of stress-strain behavior, but
are apparently too simplistic for most ceramic/metal FGMs because of
microstructural complexities and local damage.
3.4.3 Creep
As with plasticity, creep behavior in FGMs has not been well

researched, and little is known about the estimation of effective properties.
The use of simple interpolation schemes like the linear (Equation 4.1) or
modified rule of mixtures (Equations 4.21- 23) is questionable because of
the extreme nonlinearity in typical creep constitutive relations (e.g., power-
law creep with powers on the order of 5 or more). In very recent work, the
fracture behavior in a creeping FGM has been modeled [40]. However, the
creep properties of the single FGM layer considered in this study are simply
assumed.
4. COMMENTS ABOUT FGM DESIGN
The modeling of material properties and component behavior, the focus

of this chapter, is a very useful tool for the design engineer. In general, the
design of an FGM is expressed in terms of its constituent materials, its
geometry, and the spatial distribution of its composition, microstructural
features, and properties. These specifications can then be used during
processing to create the desired FGM microstructure, or they can be used to
predict the behavior of a larger system containing an FGM component.
During any design study, the materials modeler and the design engineer
must communicate effectively about the geometry, loading conditions,
performance requirements, and failure criteria for the FGM component
under consideration. The modeler needs to know specifically what kind of
information (e.g., stresses, temperatures) is desired, what level of accuracy is
required, and what kind of property data are available for input into the
model. The designer needs to know specifically what materials properties
(e.g., mechanical, thermal) are most important for obtaining accurate
modeling results, and also should be made aware of what boundary
conditions and other assumptions are used in the model, and how these can
affect the modeling results. Only when all of these issues have been
adequately addressed can a modeling study be conducted that will be useful
for design purposes.
85
600
550 I
I
500 I
I
450 I
I
400 I
...
'0' 350 I
I
..
~ I
300
I
,
J: 250 ,,
'" ,,
200 .... ,1
:,
: ,
150 /,' -- 20PSZ/BONi
.~' - - - 40PSZ/60NI
100 .y
.>
50 ~
,~. -----
......•..
60PSZ/40Ni
BOPSZ/20Ni
0
0.0 0.2 0.4 0.6 O. B 1.0
Slrain (%)
450
400
350
300
...
'0'
~
250
:
J:
200
'" 150
-- OYSZ/l00SS
- - 20YSZ/BOSS
100
- - - 40YSZ/60SS
50 ----- 60YSZ/40SS
.......•. BOYSZ/20SS
0.6 O.B 1.0

Slrain (I)
Figure 4.6. Experimental stress-strain data for (a) a partially stabilized zirconia/nickel FGM
[39] and (b) an yttria-stabilized zirconia/stainless stee1304 FGM [35].
Previous modeling studies concerned with residual stresses in ceramic-

metal structures bonded with an FGM interlayer can be used to illustrate
some of the difficulties associated with modeling and design issues. For
example, consider the simple calculation of residual stresses induced during
the cooling of a thin disk versus a long, bar-shaped specimen, where the
same materials properties are used in the calculations. In a long bar that has
86 Chapter 4
an FGM sandwiched between a ceramic at one end and a metal at the other,
the modeling results show there is a large tensile stress acting on the ceramic
near the interface at the edge of the specimen. Therefore, cracks would be
expected to initiate in this region and propagate parallel to the interface.
By comparison, it has been shown that a thin disk composed of an
FGM sandwiched between a ceramic surface and a metal surface undergoes
significant bending. This results in large tensile stresses on the surface of the
ceramic, which act parallel to the interface. Therefore cracks would be
expected to be initiated on the ceramic surface and propagate perpendicular
to the interface. Consequently, two different stress components and resulting
failure modes are associated with these different geometries. Each would
require a different FGM design solution.
All FGM design problems rely heavily on modeling, and highly
accurate modeling results are dependent on the availability of reliable
material property data and detailed constitutive models. Examples of the
ways in which modeling studies of FGMs can be applied for design purposes
are given in Chapters 5 and 7.
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Symposium on Functionally Graded Materials, Fall Meeting of the Materials Research
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2. Malvern, L.E. (1969) Introduction to the mechanics ofa continuous medium, Prentice Hall,
Inc., Englewood Cliffs, N.J.
3. ABAQUS Computer Program (1997) Hibbitt, Karlsson & Sorenson Inc., Pawtucket, RI.
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8. Nan, C.W. (1993) Progress in Materials SCience, 37, 1.
9. Voight, W. (1889) Wied. Ann., 38,573.
10. Reuss, A. (1929) ZAMM, 9,49.
II. Cho, K. and Gurland, 1. (1988) Met. Trans. A, 19A, 2027.
12. Fan, Z., Tsakiropoulos, P., and Miodownik, A.P. (1994) J. Mater. Sci., 29, 141.
13. Hashin, Z. and Shtrikman, S. (1963) 1 Mech. Phys. Solids, 11, 127.
14. Hashin, Z. and Shtrikman, S. (1962)1 Appl. Phys., 33, 3125.
15. Kerner, E.H. (1956) Proc. Phys. Soc., B69, 808.
16. Taki, M. et al. (1990) A fundamental study on the application ofFGM to high-
temperature rotating members, in Proc. of The First In! 'I. Symp. on FGM'90, (eds. M.
Yamanouchi et al.), Functionally Gradient Materials Forum, Toranomom, Minato-ku,
Tokyo, Japan, 353-358.
17. Wakashima, K. and Tsukamoto, H. (1992) ISIJ International, 32, 883.
18. Eshelby, J.D. (1957) Proc. Royal Soc. London, 241, 376.
19. Mori, T. and Tanaka, K. (1973) Acta Metall., 21, 571.
87
20. Ravichandran, K. (1994) JAm. Ceram. Soc., 77[5], 1178.

21. Aboudi, J., Pindera, M., and Arnold, S. (1996) Int. J Solids Structures, 33[7],931.
22. Wilt, T.E. and Arnold, S.M. (October 1994) Micromechanics Analysis Code, NASA
Technical Memorandum I 06706.
23. Zuiker, J. and Dvorak, G. (1994) Composites Engineering, 4, 19.
24. Suresh, S. and Mortensen, A. (1998) Fundamentals o/Functionally Graded Materials,
10M
Communications Ltd., London.
25. Williamson, R.L., Rabin, B.H., and Drake, 1.T. (l993) J Appl. Phys., 74, 1310.
26. Fischmeister, H. and Karlsson, B. (1977) Z. Metallkde, 69,311.
27. Hirano, T., Teraki, J., and Yamada, T. (1990) On the design of functionally gradient
materials, in Proc. o/The First Int'l. Symp. on FGM'90, (eds. M. Yamanouchi et al.),
Functionally Gradient Materials Forum, Toranomom, Minato-ku, Tokyo, Japan, 5-10.
28. Zhai, P.C., Jiang, C.R., and Zhang, Q.J. (1993) Application of three-phase micro-
mechanical theories to ceramic/metal functionally gradient materials, in Ceramic
Transactions 34, Proc. Second Int 'I. Symp. on FGM '92, (eds. J.B. Holt et al.), The
American Ceramics Society, Westerville, OH, 449-456.
29. Larker, R. and Beckman, T. (1995) Compositional gradation between silicon nitride and
superalloys using ShN 4/TiN CMC and TiNlNi MMC layers, in Proc. Third Int 'I. Symp. on
Structural and Functional Gradient Materials, (eds. B. Ilschner and N. Cherradi), Presses
polytechniques et universitaires romandes, Lausanne, Switzerland, 495-501.
30. Bruck, H.A. and Rabin, B.H. (1999) An Evaluation of Rule-of-Mixtures Predictions of
Thermal Expansion in Powder Processed Ni-A1203 Composites, J Amer. Ceramic Soc., in
press.
31. Takemuma, M. et al. (1990) Proceedings, The First International Symposium on FGM,
(eds. M. Yamanouchi et al.), Functionally Gradient Materials Forum, Toranomom,
Minato-ku, Tokyo, Japan, 97-100.
32. Kawai, C. et al. (1990) Oxidation resistant coating with TiC-SiC gradient composition on
carbon fiber reinforced composites by CVD, in Proc. o/The First Int 'I. Symp. on FGM'90,
(eds. M. Yamanouchi et at.), Functionally Gradient Materials Forum, Toranomom,
Minato-ku, Tokyo, Japan, 77- 82.
33. Takemuma, M. et al .. (1993) Evaluation of thermal and mechanical properties of
functionally gradient material of ZrOz-Ni system, in Ceramic Transactions 34, Proc.
Second Int 'I Symp. on FGM'92, (eds. 1.B. Holt et at.), The American Ceramics Society,
Westerville, OH, 271-278.
34. Matsumura, S. et at. (1993) A technology to form FGMs by composite electroforming,
ibid., 331-338.
35. Igari, T. et al. (1990) Mechanical properties offunctionally gradient material for fast
breeder reactor, in Proc. o/The First Int'l. Symp. on FGM'90, (eds. M. Yamanouchi et
al.), Functionally Gradient Materials Forum, Toranomom, Minato-ku, Tokyo, Japan, 209-
213.
36. Akama, S. (1997) Mechanical and thermal properties ofPSZlNi-base superalloy
composite, in Proc. o/The Fourth Int 'I. Symp. on FGM '96 , (eds. I. Shiota and Y.
Miyamoto), Elsevier Science B.V., Amsterdam, The Netherlands, 451- 456.
37. Jedamzik, R. and Neubrand, A. (l997) Ceramics Group, TU-Darmstadt, Germany, private
communication.
38. Bruck, H.A. and Rabin, B.H. (1998) Evaluating Microstructural and Damage Effects in
Rule-of-Mixtures Predictions of the Mechanical Properties ofNi-AIz03 Composites for
Use in Modeling Functionally Graded Materials, J Mater. Sci., 33, I-II.
88 Chapter 4
39. Zhu, J.C. e! a/. (1997) Mechanical performance of Zr02-Ni functionally graded material
by powder metallurgy, in Proc. Fourth In! 'I. Symp. on FGM'96, (eds. I. Shiota and Y.
Miyamoto), Elsevier Science B.V., Amsterdam, The Netherlands, 203-208.
40. Biner, S.B. (1997) Engineering Fracture Mechanics, 56, 657.
Chapter 5
THE CHARACTERIZATION OF PROPERTIES
Keywords: Electrical conductivity, Betti number, percolation, fractal, quasi-electric field,

graded band semiconductor, dielectric permittivity, dielectric constant,
capacitance, ceramic actuator, piezoelectricity, thermal conductivity, thermal
diffusivity, thermal expansion, thermal stress, effective thermal conductivity,
apparent thermal diffusivity, Fourier number, PSZlNiCrAIY, ~-TiffiC,
VN 2 C, Young's modulus, AIIAhNi, Poisson's ratio, acoustic microscope,
PSZ/SS, NiAIIAI, residual stress, TiBlTi, CulNi/Cu, strain hardening, fracture
mechanics, fracture toughness, stress intensity factor, fatigue, creep,
toughening ratio, TiC-Ni, Cr3C21Ni/Cr3C2, thermal stress, finite element
method, partially stabilized zirconia/stainless steel, acoustic emission, PSZlNi,
TiB2/Cu, TiClNi, thermal fatigue, SiCITiCICC.
1. INTRODUCTION
The technology of Functionally Graded Materials (FGMs) enables the

realization of innovative and multiple functions that cannot be achieved with
conventional homogeneous materials. Predetermined chemical composition
profiles (the spatial distribution of their components) as well as
predetermined transitions in their microstructure, are intentionally
introduced to perform desired functions. Therefore, in order to use FGMs in
practical applications, it is important to characterize their properties.
The characterization of properties includes evaluating the local
microstructure and properties of the FGM to determine the potential
performance of the designed structure and the distribution of its properties. It
also includes the evaluation of the overall performance of the material's
properties. In the microstructural evaluation, it is necessary to quantitatively
determine the size, configuration, orientation, and contiguity of phases. This
can be accomplished using ordinary image analysis. In some cases,
90 Chapter 5
conventional techniques can be used such as microscale chemical analysis

and microhardness tests. But in others, some modifications in the techniques
are necessary because the continuous change in the properties in a local
region make measurement difficult. However, in evaluating the overall
performance of properties such as electrical, magnetic, thermal, and
mechanical, if conventional methods are not applicable, it may be necessary
to modifY them or even to develop new techniques.
Furthermore, fracture behavior in a ceramic/metal FGM can change from
brittle to ductile fracture due to the gradual change in the contiguity of the
ductile, metal phase. Consequently, the overall mechanical behavior of an
FGM has to be evaluated not only on the macroscopic scale but also on the
microscopic scale, such as for damage growth, microcrack initiation at
interfaces, and crack propagation. The evaluation of thermal stress is also
important, because thermal stresses are generated during an FGM's
fabrication and heat treatment as well as by differences in the coefficients of
thermal expansion (CTE) of its components.
In many applications, an FGM is exposed to regular or alternating
thermal loading with a high temperature gradient between its two ends.
Therefore, its thermal stability must be evaluated, because microstructural
changes may have occurred due to Ostwald ripening (the reorganization of
many small particles into fewer larger particles), and also because the
compositional distribution may be unstable due to the diffusion of
component elements. In addition, if the FGM will be subjected to rapid
heating and cooling at elevated temperatures, its thermal shock resistance,
thermal fatigue characteristics, temperature profile, and the overall heat flow
must be evaluated.
Some of the methods now used for evaluating the performance of FGMs
are described in this chapter. However, many of these still need to be
standardized, and new techniques need to be developed.
2. ELECTRICAL PROPERTIES
2.1 Electrical Conductivity in Graded Materials
In homogeneous materials electrical conductivity (or resistivity) is

assumed to be constant. In the case of FGMs, however, it changes spatially
corresponding to the graded composition and structure. The electrical
conductivity of an FGM should be expressed as a function of position. For
example, c(x) expresses the conductivity profile of an FGM with a one-
dimensional gradation as illustrated in Figure 5.1. In an ideal case, the curve
is completely continuous, which indicates the absence of a sharp interface.
91
The conductance between positions Xl and X2 in an FGM with a cross

sectional area, S, is expressed by integrating the conductivity profile as
follows:
(5.1 )
Position x
Figure 5.1. Conductivity profiles of an FGM.
The electrical current flowing through an FGM with a length .e. is written
as:
]= sv (5.2)
J:dx/O"(x)
where V is the applied voltage.

The profile of the voltage drop between positions Xl and x 2 is given by:
92 Chapter 5
Vf2 dx/a(x)
v( x) = _--,~I=------ (5.3)
fodx/a(x)
The Joule heat (e) between Xl and x 2 ' and the total heat (E) generated by
a current through an FGM are derived as follows:
SV2 f;2 dx/a(x)

e(x, - x,) ~ U:dx/O"(X)r (5.4)
SV2
E= --,---- (5.5)
foldx1a(x)
When the electrical conductivity is measured along the direction

perpendicular to the gradation as indicated in Figure 5.2, the conductance
along the length, (Y2 - Yl)' and the width, (Xl - x 2), of the gradation can be
described as follows:
s = f hf~ a(x)dxdy = (Y2 - Yl) f~ a(x)dx (5.6)

~ ~ ~
The relation between electrical conductivity and a graded structure has

been studied for an FGM of stainless steellzirconia (SS/Zr02) [1, 2]. Figure
5.2 shows the dependence of the electrical conductivity on the composition
of homogeneous composites of stainless steel and Zr02. Each polycrystalline
composite (A and B) was made by vacuum sintering mixtures of two
different size powders of stainless steel and zr0 2. (A: 70 J..lm SS /2-lO J..lm
Zr02 and B: 180 J..lm SS/3 J..lm Zr02). The large change in conductivity
between 20 and 60 volume % Zr02 reflects the change in connectivity of the
matrix phase. The region of high conductivity below 20 volume % Zr02
contains dispersed nonconducting Zr02 in the stainless steel matrix. In the
zone of high to low conductivity from 20 to 60 volume % Zr02, the
composite has a skeletal structure of both phases. In the insulating zone, the
matrix changes to the Zr02 phase and the stainless steel phase is isolated.
The phase connectivity in a two-phase mixture is characterized by the
Betti number, which is a topological parameter for the connectivity of a
network [3]. Figure 5.3 shows the Betti number derived by analyzing the
93
connectivity of the stainless steel phase as a function of the volume fraction

of Zr02. The similarity of the change in both the Betti number and the
electrical conductivity as a function of the volume fraction of Zr02 suggests
a direct relation between the electrical resistivity and the connectivity of the
phases.
1.2 ~--""T"""-- ......---.....---.....,....-----.

----.t*H;- (A)
1.0 -------:----------------.-:------"(B)"----
---- ---- ~--- ----- ... -- _.- --_ .. ~- .. -------- -_. _.

0.8
!! ;
0.6 ............ :. . . . . . . . ~m~mlmmm • •

0.4
, "
0.2 .......... " ........... 1................. .........•.......

1
0.0
:, : , J :, ,
L . . . - - - " " " - - - -........--......;10;..;;;::........"""""'iI---..
0.0 0.2 0.4 0.6 0.8 1.0

Volume fraction of Zr02
Figure 5.2. The electrical conductivity as a function of the volume fraction of zr0 2 for the
stainless steel/ Zr02 composites. Curves (A) and (B) represent the data for composites
sintered by combining two different particle sizes: A: 70 /lm SS/2-IO /l 2and B: 180 /lm
SSt 3 /lm zr0 2.
The change in conductivity in a two-phase mixture of an insulator and a

conductor can be regarded as a percolation problem [4]. Such a complex
structure can be analyzed using fractal theory [5]. Figure 5.4 shows the
relation of the fractal dimension, D, as a function of the volume fraction of
Zr02 in SS/Zr02 composites. From percolation theory, the D value is known
to be equal to 1.896 when clusters are connected infinitely in two
dimensions. If the fractal dimension for the stainless steel phase is above this
critical value, a continuous path is formed resulting in metallic conductivity.
94 Chapter 5
400~----~----~------~----~----~
-----Jlk-- (A)
Q)
(/) --it--- (6)
co
-a 3001-····················:\
Q)
Q)
til
(/)
(/)
J!2
c:
.(ij 200 1-.................. .,. .. \
til
100 /-...................;...... \ ............;..... \ ...............;...... .
oL---~----~--~~~~~----~
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5.3. The Betti number as a function of the volume fraction of ZrOz for the stainless
steel phase in the stainless steel/ZrOz composites. Curves (A) and (B) refer to Figure 5.2.
In designing and analyzing the electrical properties of FGMs, it is important

to know the relation of the conductivity profile to the change in structure.
2.2 Quasi-Electric Fields in Graded Semiconductors
Graded band engineering of semiconductors was initiated in the 1980s

with the development of molecular beam epitaxy (MBE). This technique
enables the preparation of compositional gradation as well as superlattices
on an atomic scale. Figure 5.5 shows energy band diagrams for
compositionally graded semiconductors [6]. In the case of an intrinsic
semiconductor (a), the graded conduction and valence band edges, Ec (z)
dEc dE v
F =-- F. = + -
and Ev (z), produce" quasi-electric" fields, e dz and h dz ,
that can accelerate the velocity of carriers. For extrinsic semiconductors, the
band diagrams change somewhat as shown in Figure 5.5 (b) and (c).
95
2.1
2.0
0 1.9
c
0
'(ij
cQ) - --- --. --;--. ------- ---- ------;-' .- ------------ _.. _. ~.------ .. _. .... _.
1.8 _
-...
'6 :, :,
Cii 1.7 ----------1--·------------·····-r·--·-------------
u
ctS
u.
1.6 ... -~--- ---- "----- .. ----.. ~
1.5
1.4 L...-_ _....I-_ _......._ _ _...I..-_ _- ' -_ _- - '
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5.4, The fractal dimension as a function of the volume fraction of zr0 2 in the stainless
steellZr0 2 composites.
e~
~EC(Z)
~EV(Z)
--------------- Ef
@~
Fh
(a) (b) (c)
Figure 5.5. Energy band diagrams of graded bandgap semiconductors: (a) intrinsic, (b) p-
type, (c) n-type. Fe is the quasi-electric field for electrons, Fh is the quasi-electric field for
holes, EJz) is the conduction band edge, Elz) is the valence band edge, and n f is the Fermi
level.
96 Chapter 5
In a p-type graded-gap material, there is no effective field acting on holes

dE
while the effective field for electrons is F = - - - g . This is because of
e dz
cancellation between the quasi-electric field, ~, due to the drifting and
accumulation of holes and the resultant space charge field. This effective
field can be significantly greater than in the intrinsic case. For an n-type
material the effective field can act on holes.
The concept of a graded band material is expected to modify the carrier
transport and optical properties of semiconductors and to be applicable to
various devices such as high speed transistors, efficient photodiodes, lasers.
2.3 Dielectric Properties in Graded Materials
Dielectric materials are widely used for capacitors, piezoelectric devices,

surface acoustic devices, electronic memories, and the like. The dielectric
property is represented by the dielectric permittivity, E, which depends on
the frequency of the applied electromagnetic wave. If E changes spatially in
a graded material along its width like the conductivity profile, a(x), the
electrical capacitance through the cross sectional area S and the width f is
expressed as follows:
S
fdx
C== - - - (5.7)
oE(X)
where e(X) is the profile of the dielectric permittivity for an FGM.

Ceramic capacitors are produced presently by introducing various
additives into barium titanate (BaTi0 3) in order to lower the temperature
coefficient of the dielectric constant. If the Curie point of a capacitor (the
transition temperature between the ferroelectric and paraelectric phases) can
be changed as a function of position by grading its composition, the
transition from the ferroelectric to the paraelectric phase would be
broadened with respect to the temperature. Consequently, the temperature
coefficient of the dielectric constant could be lowered. Figure 5.6 shows the
temperature dependence of the capacitance for a Bal _xSrx Ti03 FGM
compared with that of BaTi03 [7]. In the FGM, five different layers with
compositions (x == 1.00,0.70,0.54,0.47,0) are stacked together. This type of
graded capacitor is expected to have lower temperature coefficient and
higher dielectric permittivity for a wide range of temperatures.
In ceramic actuators a piezoelectric plate is sandwiched between two
metal electrodes. Usually these plates are bonded with an adhesive, which
97
-
(J)
Co)
c
res
'ures
1.00
c.. 0.75 r0-

~
~
~
1kHz
..:\
... ... /•• /':,
res
Co) ~
-0 Ba 1 ' XSrJi03 FGM ~ /':, •
(J)
0.50 ~ /':, /':, 0
.~
(ij l'> \ /':, /':,
...0
E
0.25 ~
/':, /':,t::,/':,/':,/':,/':,
BaTi03
Z
• I I I I I I I • I •
0.00
0 40 80 120 160
Temperature CC)
Figure 5.6. A comparison of the temperature dependence of the capacitance for a Bal.
xSr, Ti0 3 FGM and BaTi0 3 .
can result in several problems (peeling off, softening at high temperatures,

cracking at low temperatures). By fabricating an actuator with a sandwiched
structure consisting of a piezoelectric layer, an intermediate compositionally
graded layer, and a ceramic layer with a high dielectric constant, as
illustrated in Figure 5.7, the adhesive problems can be eliminated.
Piezoelectric maerial
Electrode
Intermediate
} layer
High dielectric constant maerial
Figure 5.7. The structure of an FGM piezoelectric actuator.
The FGM with a periodic structure composed of a piezoelectric material

and a high dielectric constant material can be used for an ultrasonic motor
that is driven by a sinusoidal progressive wave [8, 9]. Figure 5.8 is a diagram
98 Chapter 5
of such a graded piezoelectric actuator. The composition of the piezoelectric

material, A, and the high dielectric constant material, B, are
Pb(Ni1/3Nb2l3)o.5(Tio.7ZroJ)o. 5 0 3 and Pb(Ni1/3Nb2l3)o7(Tio.7Zro.3)o303,
respectively. The symmetric structure of the FGM elements can prevent
warping during fabrication.
-
Figure 5.8. A schematic of an ultrasonic motor with graded piezoelectric actuator showing the
progressive motion it produces.
An optical fiber with a graded index is another example of a graded

dielectric material. If a material is not magnetic, the following relation exists
between the dielectric constant and the refractive index:
(5.8)
where n is the refractive index and Eo is the dielectric constant of

vacuum. The spatial change of the dielectric permittivity produces a similar
spatial change in the refractive index. An optical fiber with a graded index is
a material tailored to have a higher index in its core than in its outer layer in
order to transmit light with total refraction.
3. THERMAL PROPERTIES
Some general methods for analyzing the thermophysicaJ properties of

FGMs, mainly thermal conductivity and thermal diffusivity, are described in
this section, and thermophysical properties under both steady state and
transient heating conditions are evaluated. The analysis of transient
characteristics such as temperature response is important for optimizing
99
graded structures that can withstand thermal cycling conditions at high

temperatures.
3.1 Thermal Expansion
The thermal expansion of FGMs is an important characteristic that affects

their mechanical behavior in severe thermal environments such as for engine
components and space structures. The thermal expansion coefficient (CTE)
of a material, defined as the linear expansion of the strain per unit of
temperature change, is measured with a dilatometer [10]. The thermal
expansion of metal-ceramic composites with different compositions has been
studied extensively in order to optimize their graded compositions through
the relaxation of thermal stress. However, no model exists that is valid for
the full range of compositions. To precisely measure geometric change of an
FGM, or the distribution of local thermal expansion, two- or three-
dimensional measurement techniques must be used, such as the moire
interferometry [11], laser interferometry [12], or digital image correlation
[13, 14].
3.2 Thermal Conductivity
For homogeneous materials, the heat shielding ability is fairly well

understood, and the heat transport is described by the thermal conductivity
and the thermal diffusivity. These properties can be readily measured.
However, most conventional methods cannot predict the distribution of
thermophysical properties in FGMs directly. The measurable temperature is
limited to the surface of a material under heat flux. For the total heat
resistance of an FGM, the steady state method can be used to determine
thermal conductivity.
If the thermal conductivity of a component in an FGM is Ai, the effective
thermal conductivity Ae can be expressed as a total property by the
following equation:
(5.9)
where L is the total thickness of the FGM, Ii is the thickness of the FG M

component with a thermal conductivity of Ai, a is the thermal diffusivity, c
is the heat capacity, p is the density, and n ---t 00 denotes that the material is
composed of components with continuous properties. The effective thermal
conductivity is obtained from the thermal resistance LIA", which is
100 Chapter 5
determined by dividing the mean temperature gradient between the front and
back surfaces by the rate of heat flow through the FGM.
Therefore, a set of thermal conductivities for the components of an FGM
can give its total heat resistance. However, this set of thermal conductivities
does not correspond to the thermal conductivity ofthe FGM.
Thermal conductivity is calculated using the following formula:
A=acp (5.10)
This formula must be modified for heterogeneous materials such as

FGMs, or the results will be inaccurate.
There are steady state and transient methods for measuring the thermal
conductivity of materials. Thermal diffusivity is measured directly by the
laser flash method, which can measure temperatures as high as 700·C. When
the front surface of an FGM is heated by a laser pulse and the temperature
response at the back surface is measured, the effective thermal diffusivity,
ae , is obtained from the half-time to reach the maximum temperature.
Combining Equation 5.10 with the mean values for the specific heat
capacity, cm, and the density, Pm, gives an apparent value for the thermal
conductivity, Aa , of an FGM. However, as shown below, it cannot describe
the thermal conduction process. In general, the thermal conduction equation
for a material is expressed as follows [15]: (See also Appendix 5.3 A for the
derivation of the equation for the heat conduction of a material with no heat
source and sink.)
ar a ar
pC-=-(A-) (5.11)
at (}z (}z
For an FGM, this equation can be replaced by:
(5.12)
where
Pm =- Jp(z'}dz,
1
Lo
L
Cm = -J
1
Pm L
L
0
p(z)c(z)dz (5.13)
For a two-layered composite in which each layer has different

thermophysical properties, the apparent thermal diffusivity, aa, is obtained
101
from the temperature response at the composite's back surface using the
relation expressed in Equation 5.12. The apparent thermal conductivity, Aa,
can then be calculated by combining the mean specific heat capacity, em, and
the density, r m, using Equation 5.10. The result of this calculation is shown
by the dashed line in Figure 5.9 [16, 17]. The solid line shows the effective
thermal conductivity, Ae, calculated from the following relation:
103
a/a;F5.36
p/r2=7.64xlO 3
...... 102 c,/c2=0.377
I
::.:: )'./1;F1.55xlO 4
......
I
E
~
'-' 10'
~
til
c....:
100
10"
.4=t,+e,=3mm
o 2 3
it (mm)
Figure 5.9. A comparison of the thennal conductivities for an FGM. The apparent thermal
conductivity Aa and the effective thennal conductivity Ae were obtained from equation
(5.3.4) and (5.3.6), respectively.
(5.14)
In this calculation, the thickness of the composite is assumed to be

L ={£ 1+ £2) = 3 mm. The thermal conductivity is plotted as a function of
the thickness of the first layer. There is a large difference between the
102 Chapter 5
apparent thermal conductivity, Aa , and the effective thermal conductivity,

Ae , in this simple two-layered model. This is discussed further below.
3.3 Temperature Distribution under Steady State

Heating
Under steady state conditions, heat flow is independent of time.

Therefore, Equation 5.11 becomes:
V(AVT) = 0 (5.15)
It is assumed that the sample is thermally insulated and that the heat
flows along the z axis as shown in Figure 5.10. For the sample of length L (z
= 0 to z = L), the boundary conditions can then be written as T(O) = T sand
T(L) = Tb.
tttt t
Material B
z
Figure 5.10. Schematic of a graded sample under steady state heating.
The equation for unidirectional heat flow for a plate-shaped sample is:
103
~(A(Z) dT) = 0 (5.16)

dz dz
and its solution is:
Z dz
T(z)=AJ-+B (5.17)
o Il(z)
Applying the boundary conditions, the constants A and B can be defined.

The temperature distribution is then expressed as:
T(z)=T - 1', -~ f~ (5.18)

s J~ oll(z)
o Il(z)
This equation does not take into consideration the temperature

dependence of the material's properties. The variation of thermal
conductivity with temperature can be neglected when the temperature range
is not too large [18].
For example, a finite element modeling program based on Equation 5.18
can be used to estimate the temperature distribution in a tungsten carbide
cobalt (WC/Co) FGM. The analytical model is based on a rectangular body
with a thickness L in the z-direction, in which the composition gradually
changes from one side to the other according to the following relation [19]:
(5.19)
Where z is the distance from the top surface of the FGM, L is the
thickness, and p is an exponent that controls the distribution function.
The graded region is treated as a series of bonded composite interlayers
with compositions ranging from 5 to 25 weight % cobalt. The thermal
conductivity for different compositions is computed by the linear
interpolation of data compiled from the literature [20, 21].
Figure 5.11 shows the estimated temperature distribution for various
compositions of a 25 x 14 x 2 mm plate shaped WC/Co FGM prepared by
centrifugal powder metallurgy and attached to a substrate [22]. The
computation used a heat flux of 1 MW/m2 (top surface temperature of
727°C) with fixed boundary conditions (a set temperature and a perfect
contact). The analysis shows that the temperature difference through the
thickness of the graded sample is relatively small, and can only be varied
within about 20·C by controlling the composition.
104 Chapter 5
Figure 5.12 shows the actual temperature distribution for two

homogeneous WC/Co composites and a graded sample that were welded to
an iron block and heated on their top surface with a burner rig [23]. The
surface temperature was measured with an infrared pyrometer and a welded
thermocouple. The average heat flux was determined from the axial
temperature distribution in the iron block, which was measured using five
thermocouples installed along the axis of the block at 5 mm intervals starting
from its top surface.
(95 wt.%WC) (75 wt.%WC

1000
Q'
-- 990
@
~
L...
Q)
0.
E 0.2
~ 0.4
980 0.6
P=1
2
4
6
970 L.......J.--L-L.---L.---'---L.---'---L.---'----J
0.0 0.2 0.4 0.6 0.8 1.0

Normalized distance (z/d)
Figure 5.11. Estimated temperature distributions for tungsten carbide/cobalt (WC/Co) FGMs
with various compositions.
Because of tungsten carbide's good thermal conductivity, the temperature

throughout the sample decreases with increasing WC content. In the graded
sample, the heat flux behavior is average between 5 and 15 weight % Co.
The temperature at the interface between the sample and the iron block was
estimated by linear extrapolation of the measured values. This temperature is
in agreement with that obtained from the finite element analysis, and the
comparisons between the numerical simulation and the values deduced from
experiments also are in good agreement.
105
3.4 Temperature Response under Transient Heating
The development of an analytical solution for the transient temperature

response in FGMs is needed both for practical applications such as thermal
analysis of the space shuttle during re-entry and for evaluation of thermal
conductivity by a transient method. It is a complicated problem because a set
of nonlinear partial differential equations has to be solved. There are two
approaches to solving the transient temperature response. The first considers
a multilayered model with each layer having constant thermophysical
properties as shown in Figure 5.13. The second considers a simplified
situation where the nonlinear equation can be made linear by regulating the
distribution of thermophysical properties. Although there are a number of
transient heating methods, such as pulsewise, stepwise, and periodic, the
pulsewise heat flux corresponding to the laser flash method is shown here as
a practical example [24, 25].
..•
1200
WC/Co85/15
WC/Co95/5
1000
--
.-
~ 800
-....Q::J)
....coQ)
c..
600
E
Q)
~
400
200
o
o 5 10 15 20 25
Thickness (mm)
Figure 5.12. Measured temperature distributions for homogeneous and graded tungsten
carbide/cobalt (WC/Co) composites.
106 Chapter 5
3.4.1 An approximate solution for the temperature response using a

multilayered material model
As shown in Figure 5.13, the heat conduction in a multilayered material

with n-Iayers can be described by a set of one-dimensional heat conduction
equations. Under the boundary condition of pulsewise heat flux, the
analytical solution for the transient temperature response can be obtained by
using a Laplace transformation [24]. If the infinitesimal thickness of each
layer is considered, the solution for multilayered materials can be extended
to FGMs, which are continuous with respect to composition and
thermophysical properties. Using the perturbation method, the solution for
the approximate temperature response is derived as follows [25]:
Heat flux
, , , , , ,
'. " " "
11
layer 1 al PI cl
Layer 2 a2 P2 c2 12
Layer 3 a3 P3 c3 'J
,,
,,
,,
,,
,,
,,
layer n-1 a n-l P n-l c n-l In-1
Layer n an Pn cn In
n
o
z
Temperature detector
Figure 5.13. A model of a multilayered material in which the thermophysical properties of

.en
each layer are constant (lin = thermal diffusivity, rn = density, Cn = heat capacity, and = the
thickness of the nth layer).
107
e p
= 1+ 2 f (_I)k cos(knr)e
~
-(kn)2 Fo (1 + lP
~
) (5.20)
k=l
with
r=-f-Z,
1 d 0
~ 17L -ya(z)
r:r:\)
z
f0 dz
'h = _L~a(z)
(5.21)
(5.22)
where 8 p is the temperature response normalized with respect to the

maximum temperature rise; 1h is the square root of the total thermal
diffusion time, that is the duration for thermal diffusion through the total
11L, which is actually a normalized diffusion time; ,=

thickness; , is the ratio of the square root of the thermal diffusion time to
1 signifies the front
surface and' =0 the back surface; lPp,k is the correction term (when the
properties of two neighboring layers are fairly close, lP p,k can be ignored, i.e.
lPp,k = 0); Fa is the Fourier number, a nondimensional time, which is
expressed as at I L2 for a homogeneous material [24].
When the correction term is ignored, the form of the approximate
temperature response solution (Equation 5.20) is the same as that for a
homogeneous material under pulsewise heating, except for the meaning of ,
and Fa. Therefore, an FGM can be treated as a homogeneous material in
which the apparent thermal diffusivity, a;,
is expressed as follows:
(5.23)
The dimensionless temperature response at the back surface (' = 0) will

correspond to that of a single-layered material when the Fourier number is
expressed as:
(5.24)
where a(z) in Equation 5.23 describes the distribution of the thermal

diffusivity along the z direction. Therefore, a;
can be referred to as the
108 Chapter 5
1.5 ,-,----.,...----.,-----..,.-----,
,
" ...
........... , .......
1.0
' ..... '-
------------_ _------
....
::>
0.5
0.0 .........
O""::"_---'~_ __ _ L _ _ _- - - ' -_ _ __ _ '
0.0 0.1 0.2 0.3 0.4

Fo
Figure 5.14. The normalized temperature response in an FGM as a function of the Fourier
number with position. The solid curves are obtained from the exact analytical solution, the
dashed curves from the approximate solution without correction terms, and the longlshort-
dashed curves from the approximate solution with correction terms.
effective thermal diffusivity. However, as the value of the correction term,

f/Jp,k' increases, the "effective" component of is diminished. a;
3.4.2 Comparison of the approximate solution with the analytical
solution
For certain situations, there are exact but complex analytical solutions for
the temperature response under transient heating conditions [26]. These can
be used to evaluate the validity of the approximate solutions. In Figure 5.14,
the solid curves represent the analytical solutions, the dashed curves - the
approximate solutions without correction terms (Equation 5.20, when
f/J p,k =U), and the long/short-dashed curves - the approximate solutions with
the correction terms. When' = 0 and 0.25, the approximate solutions and the
analytical solutions agree reasonably well. Furthermore, the approximate
solutions without the correction terms are closer to the analytical solutions
than with the correction terms. However, when 0.5 or greater, the
approximate solutions do not correctly describe the temperature response in
,=
anFGM.
It can be concluded that Equation 5.20 without the correction term:
109
(5.25)
can be used to evaluate the temperature response of an FGM's back

surface in most actual situations such as when using the laser flash method.
Therefore, from an engineering standpoint, it is significant that the apparent
thermal diffusivity, a;, as expressed in Equation 5.23, can be considered an
effective parameter for describing thermal diffusion in an FGM.
While this evaluation method does not deal with thermal conductivity
directly but rather with thermal diffusivity, it avoids the error of deriving the
thermal conductivity from the relation Aa = a;cmPm (Equation 5.10).
However, if the distribution of the heat capacity and density (c, p) is known
and that of the thermal diffusivity is measured, the thermal conductivity can
be estimated. The effective thermal conductivity also can be obtained from
Equation 5.9.
3.5 Thermal Stability
Because a graded composition and structure are not usually in a state of

thermodynamic equilibrium, they may not be stable at high temperatures.
Thermally activated atoms diffuse along the temperature and composition
gradients and disrupt the graded structures. Therefore it is essential to
evaluate the thermal stability of FGMs as a function of service temperature
and time, particularly for applications at high temperatures.
In the case of plasma spray coatings of FGMs of partially stabilized
zirconia/nickel, chromium, aluminum, yttrium (PSZINiCrAIY), the PSZ is
re-sintered when heated at 1200°C, and vertical cracks appears due to
inhomogeneous shrinkage. However, no change occurs in the graded
structure between 600°C-1200°C [27].
The thermal stability of linearly graded ~-titanium/titanium carbide (~
TilTiC) and vanadium/vanadium carbide (VN 2C) FGMs has been evaluated
numerically [28]. In general, carbon atoms in metals diffuse much faster than
metal atoms in metals or carbon atoms in carbides. Therefore, changes in the
graded composition of these FGMs can be predicted by analyzing the carbon
diffusion with temperature.
When these FGMs are exposed to a temperature gradient of 1427°C on
the carbide side and 927°C on the metal side, the carbide tends to be
condensed at the high temperature side for the ~- Ti/TiC system and at the
low temperature side for the VN 2C system, as shown in Figures 5.15 and
5.16, respectively. Carbon diffusion in metals is governed by the heat of
110 Chapter 5
transportI, Q*, and the partial molar enthalpy of solution, l1Hs, with respect
to the carbon atom solute.
40 r---------------....,
TiC
30
ii
:e ~Ti + TiC
c
0
~
....
C
Q) 20
u
c
0
u
c
0
.0
....
<1l
0
10
~Ti
o~~~~~~~==~===c
o 0.1 0.2 0.3 0.4 0.5
Distance (mm)
Figure 5.15. The change in the graded structure of a ~ titanium/titanium carbide (~- Ti/TiC)
FGM with time when exposed to a temperature range of927°C"-1427°C.
For the ~-Ti/TiC system, the estimated value ofQ* + l1Hs is negative (-
4.2 kJ/mol ), so the carbon atoms diffuse toward the high temperature side
and TiCx is formed. While for the VIV 2C system, the estimated value of Q*
+ l1Hs is positive ( 44.5 kJ/mol), and a V2C rich phase is formed at the low
temperature side. The increase of the carbide layers of TiCx and V2C and the
I It is defined as the heat transported by the diffusion of solute atoms. When a part of an
homogeneous alloy is heated, the thermal diffusion occurs along the temperature gradient
produced and the solute atoms diffuse. If the heat of transport is negative, its direction is
opposite to that of atom diffusion. In this case, solute atoms diffuse toward the higher
temperature side. While it is positive, the directions both of heat and of atom transport
coincide.
111
metal layers of Ti and V respectively on both sides gradually results in

disrupting the graded structures. Therefore, before using an FGM in a high
temperature application, the temperature range and time duration it can
safely sustain must be investigated. However, in order to extend the service
temperature and lifetime of FGMs, materials that inhibit the diffusion of
atoms sometimes need to be applied.
Temperature (K)
1700 1500 1400 1300 1200
40~--~~--~~--~----~-----'
c
o
...
'iij
E
~
c
8
c
.8
Qj
o
Distance (mm)
Figure 5.16. The change in the graded structure of a vanadium/vanadium carbide (V N 2C)
FGM with time when exposed to a temperature range from 927°C-1427 DC.
112 Chapter 5
4. MECHANICAL PROPERTIES
An FGM is a material in which elastic properties such as the Young's

modulus, Poisson's ratio, the thermal expansion coefficient and thus the
internal stress, as well as the microstructure, change spatially. Therefore, an
FGM's toughness and strength cannot be evaluated simply by applying
conventional fracture mechanics. This section addresses the analysis and
measurement of spatially changing elastic properties; the influence of
internal or residual stress on strength; fracture mechanics as applied to
FGMs; and the evaluation of fracture toughness, creep, and fatigue.
4.1 Elastic Properties
The modulus of elasticity, E, also known as the Young's modulus, is the

slope of a straight line when a material's stress is plotted as a function of its
elastic strain. It relates to stiffness. The higher the value of E, the stiffer the
material. In general, the Young's modulus is constant for a given material at
a given temperature. In the case ofFGMs, however, it changes spatially.
For determining the overall Young's modulus of an FGM, the stress-
strain curve can be measured by attaching a strain gauge to the sample's
surface during a conventional four-point-bending test. The dependence of
the Young's modulus on an FGM's composition can be estimated by
measuring the flexural resonant frequencies of a rectangular bar specimen
using a forced-resonance technique [29]. The Young's modulus of an
aluminum/nickel aluminide (AIIAI3Ni) FGM estimated by this method varies
from 80 to 102 GPa between the Al and the AhNi surfaces compared with
187 GPa for AhNi [30).
The distribution of the Young's modulus and Poisson's ratio (the ratio of
the transverse or lateral strain to the axial strain) can be measured
simultaneously by using a line-focus-beam (LFB) acoustic microscope,
shown schematically in Figure 5.17 [31, 32, 33, 34, 35]. The relative
intensity of the received surface-reflected wave is measured as a function of
the distance between the acoustic lens and the specimen. The measurement
frequency of 215 MHz, which is the frequency at the center of the LFB
acoustic lens, is used for the analysis, and distilled water is used as an
acoustic coupler. Velocity measurements of two types of surface wave
modes: leaky surface acoustic waves (LSA W) and leaky surface-skimming
compressive waves (LSSCW) are derived from the Young's modulus, E, and
Poisson's ratio, Y, according to a modification of elasticity theory [36]:
113
O.87+1.12v ~
CLSAW = 1+ v ~2ci+ v)p (5.26)
E(l- v)
CLSSCW = (1 + v)(l- 2v)p
(5.27)
These equations are valid if two assumptions are made: (1) CLSAW and
CLSSCW are nearly equal to the velocity of the Rayleigh wave and the
longitudinal wave, respectively [33, 34]; and (2) the samples are isotropic
and acoustically homogeneous. This depends on the relation between the
microstructural size and the ultrasonic wavelength. That is, the measurement
with the acoustic microscope of the velocity at the higher frequency (shorter
wave length) has higher resolution for the localized velocity measurement.
However, if the estimated elastic constant is too localized, it could deviate
somewhat from the macroscopic elastic constant in Equations 5.26 and 5.27.
Pulse mode Digital wave

measurement memorizer
system
Computer system
controller r---
analyzer
Acoustic lens
(LFB 0 r PFB)
Transducer
Digital
voltmeter
Couplant
(wate r)
~Thermocouple
\/
1'-..'-..'-..'-..'-..'-..'-..'-... . . . . . . . . . . Specimen
Mechanical stage Stepping

motor
system
Figure 5.17. Schematic of an acoustic microscope.

114 Chapter 5
The estimated elastic constants as a function of composition for an FGM

of partially stabilized zirconia/stainless steel (PSZ/SS) along with acoustic
data for its homogeneous components are shown in Figure 5.18. The elastic
constant distribution is in good agreement with the data for the components.
The marked change in the elastic constants in the region of the 60 volume %
PSZ layer could be attributed to debonding at the metal/ceramic interfaces.
250
co
Q..
~
I/) 200
::::J
'5
"C
0
E
I/)
-0) 150
c: --0-- FGM
::::J
0
>- --e- Homogeneous compo site
100
0 20 40 60 80 100
0.5
0.4
0
...
~
I/)
0.3
-c:
0
I/)
I/) 0.2
·0
Q..
-<>- FGM
0.1 --e- Homogeneous composite
0.0
0 20 40 60 80 100
Volume fraction of PSZ (%)
Figure 5.18. The estimated Young's modulus and Poisson's ratio for PSZ/SS FGMs.
4.2 Deformation and Strength
Both the strength and the deformation behavior of materials are generally
evaluated by tensile tests and three- or four-point bending tests. The bending
strength of an AIlNiAl FGM is 3-4 times greater than NiAl itself [37]. At
115
temperatures up to 727°C, the fracture is not catastrophic because the

propagation of a crack that is initiated in the aluminum side is retarded in the
NiAI phase.
The residual stress strongly influences the tensile behavior of FGMs by
shifting the stress state to tension or compression, and by strain hardening
when the elastic limit is exceeded. The strain to failure in FGMs is
determined by that of the lowest ductile component. The relation between
the true stress and the applied load can be deduced using laminate theory.
In a titanium/titanium boride (TilTiB) laminate (three layers: 80 mol %
TiB, 40 mol % TiB, and Ti, prepared by pulsed electric current sintering),
the residual tensile stress below 300 MPa appears in the 80 mol % TiB layer.
Almost the same amount of stress was reduced in the bending strength of the
TiITiB FGM as in the 80 mol % TiB monolayer (400 MPa). The variation in
the bending strength of this TiB layer with relative thickness agrees
qualitatively with the calculation of the residual stress generated during
cooling from the processing temperature [38].
Figure 5.19 shows the measured and calculated residual stresses in
CulNi/Cu FGMs prepared by cold compaction followed by annealing at
800°C [39]. The regions between the pure copper and pure nickel layers
consist of Cu-Ni alloys with different compositions. These alloys are known
to have a solid solution strengthening effect. For example, Cu-20 weight %
Ni and Cu-80 weight % Ni have higher yield stresses and ultimate strengths
than pure copper and nickel, respectively. Therefore, the behavior of these
FGMs cannot be predicted by applying a simple rule of mixtures to the
properties of their components, pure copper and pure nickel.
The residual stress was measured by etching off one side
electrochemically and monitoring the deflection of the graded alloy part
[40]. Numerical data were obtained by calculating the stress produced during
cooling from the stress free temperature, using a finite element code
(ABAQUS) [41]. In the annealed FGMs, the calculated residual stresses
were as high as 100 MPa. However, they were negligible in the cold
compacted ones.
The calculated residual stress can be used to determine the stress-strain
behavior of an annealed FGM. For example, at x/d values of 0.1 for Cu-20Ni
and 0.9 for Cu-80Ni, where x is the distance from one end of a graded layer
with thickness d, after processing, these layers are under a tensile stress of 80
MPa. Therefore they yield at a lower strain than samples with the same
composition of layers in a stress free state. On the other hand, a layer that is
initially under compression will be unloaded elastically first before starting
to be loaded in tension.
Numerical analysis has shown that some parts of an FGM are subject to
plastic yielding during cooling after processing [41]. This plastic
116 Chapter 5
defonnation is accompanied by strain hardening. The highest plastic strain

encountered in a CulNi/Cu FGM is about 0.1 % for both the pure copper and
the pure nickel layers. A correction can be introduced for the strain
hardening of individual layers by horizontally shifting their stress-strain
curves, if the following assumptions are made: (1) plastic deformations in
tension and compression have the same strain hardening effect, (2) plastic
deformations created at any temperature between room temperature and
400°C produce a similar strengthening effect, and (3) the strain hardened
layers of an FGM are deformed elastically under the applied tensile load up
to the plastic strain already encountered during cooling.
150
Tension
100
'@"
CL 50
~
I/)
I/)
....
Q)
iii
0 \ , ... ... ,
iii
:l
"
"0 -50
'iii
Q)
a:
-100
Compression
-150
0.0 1.0
Thickness (mm)
Figure 5.19. Residual stresses in CulNilCu FGMs after cold compaction and annealing at
800·C. The solid curves with and without closed squares are the results obtained from the
finite element analysis and the experiment for annealed samples. The dashed curve is the
experimental result for cold pressed samples.
In Figure 5.20, the stress-strain curves for a CulNi/Cu FGM and a virtual
FGM, which is composed of data for six layers of homogeneous material,
are compared with a curve that takes into account the effects of both residual
stresses and plastic strain hardening. The good agreement between this curve
and the stress-strain behavior of an actual FGM confirms the validity of the
analysis and the assumptions.
117
150r-----~------~------~----_,
C? 100
a..
~
(/)
...
(/)
CJ.)
en 50
0.1 0.2 0.3 0.4

Strain (%)
Figure 5.20. Stress-strain data for the CulNi/Cu FGMs corrected for residual stresses as well
as for strain hardening. The curve with open circles was determined experimentally for
annealed samples; the curve with open rhombuses was determined numerically for virtual
CulNi/Cu FGMs composed of six homogeneous layers; and the curve with crosses is the
curve for the virtual FGMs corrected for residual stresses and plastic hardening.
4.3 Toughness
4.3.1 Fracture mechanics
In developing FGMs, research on the mechanics, particularly on the

fracture mechanics of these new classes of inhomogeneous materials is
needed mainly to provide technical support to materials scientists, and
design and manufacturing engineers. Fracture mechanics has been used quite
successfully both as a screening tool during material processing and as a
design and maintenance tool for assessing service life. In a broad sense
fracture is the creation of new surfaces in solids. Fracture mechanics deals
with studying the effects of the applied load, the geometry of the component
or the flaw, and the environmental conditions on the failure of engineering
materials and structures. The macroscopic theories of fracture are based on
the principles of continuum solid mechanics and classical thermodynamics.
(See Appendix 5.4A for the derivation of the fundamental criteria for
fracture initiation and propagation.)
118 Chapter 5
4.3.2 Stress singularities in FGMs
In applying fracture mechanics to FGMs the basic principles and

techniques with respect to fracture instability, the nonlinear fracture and the
subcritical crack growth remain unchanged. However, because of the
inhomogeneity in thermophysical and strength related properties, difficulties
arise in characterizing the material and in solving the actual crack problems.
From the standpoint of the asymptotic behavior of the stress state near a
crack tip in FGMs, the significant problem appears to be the investigation of
the influence of the parameters related to the material's inhomogeneity on
the power of stress singularity and on the angular distribution of stresses.
The stress singularity is the magnitude of the exponent in the equation
that describes the asymptotic stress field at the crack tip. This exponent
determines how rapidly the stress increases as the crack tip is approached.
The problem has been considered for FGMs with smoothly varying elastic
properties [43, 44] and for inhomogeneous materials having a kink in the
distribution of elastic parameters [45, 47]. For the plane strain problem of a
crack in an inhomogeneous material the leading terms in the asymptotic
expansion of stresses near the crack tip are shown to be [43]:
~ hij (8)] exp[rg(8)] , (i,j = r, 8)

Ot/2r
(5.28)
where f1ij and f2ij are identical to that given in Equation 5.4.A2
(Appendix 5.4A) for homogeneous materials [42], and gee) is a known
bounded function representing the inhomogeneity of the material. A similar
expression is found for the antiplane shear problem [45]. From Equation
5.28 and from similar results in the literature [45, 46, 47], as r~O, the
inhomogeneity of the material seems to have no effect on the asymptotic
behavior of the stress state. The expressions in Equation 5.4.A2 remain valid
provided that the elasticity parameters E and v are continuous at and near the
crack tip, but are not necessarily differentiable functions of the space
coordinates.
If E and v are discontinuous, that is, if the medium consists of bonded
(homogeneous or inhomogeneous) dissimilar materials, the stress state
around the tip of an interface crack or a crack intersecting the interface is
known to have certain anomalous behavior [48, 49]. The stresses and crack
opening displacements very near the crack tip have the asymptotic form:
119
K K
uy + iu x == -* .Jr exp{jw logr), a», + ia xy == l2rexp{jwlogr)
f.11 "'i £r
(5.29)
for an interface crack, and have the form:
k1
a »' = a'
- O<a<1 (5.30)
r
for a crack perpendicular to the interface, where K is a complex and k1

is a real constant representing the stress intensity factors, and f.11, f.12, and
(0 are known bimaterial constants 2 [48, 49]. The stress and displacement
oscillations given by Equation 5.29 are physically unacceptable, whereas the

main shortcoming of the nonsquare root singularity in Equation 5.30 is that
the standard fracture criterion based on the energy balance concept and the
self-similarity of crack tip stress and displacement behavior is no longer
directly applicable. In the case of FGMs, with or without a kink or slope
discontinuity in the material property distribution, (0 is zero, a is 1/2, and the
asymptotic analysis shows that not only the .Jr
singularity but also the
angular distribution of stresses and displacements around the crack tip turn
out to be identical to those found for cracks in homogeneous materials [45,
46]. The significance of this result is that in applying computational fracture
mechanics to FGMs, such as the method of finite element analysis, the
techniques developed for the treatment of crack tip singularities in
homogeneous materials can be used without any modification.
The above assertions about the asymptotic behavior of stresses are
restricted to the leading terms only. The inhomogeneity of the material
would indeed influence the higher order terms as shown in Equation 5.28. In
general, the size of the so-called K-controlled region around the crack tip in
FGMs would be expected to be smaller than that in homogeneous materials.
For example, in a recent asymptotic study of a mode I problem for a crack
perpendicular to the kink line 3 of the property distribution, as r~O the crack
surface displacement was shown to be [50]:
(5.31 )
2 The two constants (known also as Dundurs parameters) that are certain functions of the
shear moduli and Poisson's ratios of two bonded elastic solids.
3 the line of slope discontinuity in the thermomechanical parameters of FGMs.
120 Chapter 5
where A1, A2, and A3 are constants, and A1 is a measure of the mode I
stress intensity factor. The constant A3 becomes zero for homogeneous
materials.
The plane strain crack problem for an infinite inhomogeneous medium is
first considered in which the elastic properties vary in the x' direction only,
the crack is located along the x axis, and 8 is the angle between the x and
x' axes (0 < 8 < nI2). It is assumed that Poisson's ratio is constant (v = 0.3),
and the inhomogeneity of the material is represented by a dimensionless
parameter al3 through E(x' ) = Eo exp(,Bx'), where a is the half-crack
length. The solution of the mixed mode problem plus extensive results can
be found in reference [43].
Some typical results for constant strain loading,
C~(X',+oo) = Co' perpendicular to x' are given in Table 5.1 The term
8=0 corresponds to a mode I problem for which k2 is zero and k1 is the
maximum. However, for 8 = nl2 the loading is parallel to the crack and all
stress intensity factors are zero. The stress intensity factors at the crack tip x
= a, on the stiffer side of the medium, are always greater than at x = - a.
Table 5.2 shows some limited results comparing the plane strain [43] and
the penny-shaped crack [44] solutions for FGMs under uniform tension, ao
perpendicular to the plane of the crack, where E (x,y) = Eo exp (13 y) and E
(r, z) = Eo exp (13 z), v = 0,3 and 13 = 0 corresponds to a homogeneous
medium. In both cases the stress intensity factors in FGMs are greater than
that in homogeneous materials, and the influence of the inhomogeneity of
the material on k) and k2 is more pronounced for a plane strain crack than for
a penny-shaped crack.
Table 5.3 shows some results for the stress intensity factor in an FGM
plane under remote bending through fixed grips, namely,
c ~ (Xl ,+00) = c1 XI . Figure 5.21 shows the normalized stress intensity
factors for the basic surface crack problem in an FGM plate. The geometry
of the medium is shown in Figure 5.21 a. It is assumed that Poisson's ratio, v
= 0.3, E(x) = E) exp(l3x), and I3h = log (E21E), where E)= E(O) and E2 = E(h).
Figure 5.21 shows the results for various values of the material
inhomogeneity parameter E21E), and for three primary loading conditions:
loading by a fixed grip, C.w (x ,+00) = co; membrane or pin loading4 N
along the x = hl2 axis; and bending, M. The stresses used to normalize the
results are defined by:
4 the in-plane (as opposed to bending or transverse shear) component of the extemalloads
applied to the boundaries of plates, shells, or layered materials.
121
Table 5.1. The Effect of a~ and 8 on the Stress Intensity Factors; v = 0.3; Loading: Uniform
Strain, co, Away from the Crack Region, ko = Eo £0 -Ja.
a~ 8ht kl{a}/ko kl{-a}1ko kzia}/ko kz{-a}1ko
0 1.196 0.825 0 0
0.1 1.081 0.750 -0.321 -0.254
0.2 0.781 0.548 -0.514 -0.422
0.25 0.3 0.414 0.290 -0.504 -0.437
0.4 0.121 0.075 -0.304 -0.282
0.5 0 0 0 0
0 1.424 0.674 0 0
0.1 1.285 0.617 -0.344 -0.213
0.2 0.925 0.460 -0.548 -0.365
0.5 0.3 0.490 0.247 -0.532 -0.397
0.4 0.146 0.059 -0.314 -0.269
0.5 0 0 0 0
0 6.317 0.115 0 0
0.1 5.376 0.117 -0.867 -0.037
0.2 3.315 0.115 -1.l55 -0.090
2.5 0.3 1.441 0.082 -0.900 -0.158
0.4 0.369 0.004 -0.429 -0.179
0.5 0 0 0 0
(5.32)
The stress intensity factors, k1' such as those given by Figure 5.21 are
needed for the subcritical crack growth characterization of FGMs. The
influence of Poisson's ratio, v, on the stress intensity factors is relatively
insignificant [43, 44]. Therefore in problems associated with cracks,
assuming a constant v would not be a serious limitation. (For further studies
on the fracture mechanics ofFGMs see [51, 52, 53, 54, 55].)
Table 5.2. Stress Intensity Factors for a Plane Strain or a Penny-Shaped Crack in an FGM
Under Uniform Tension, 0 o, Perpendicular to the Plane of the Crack; v = 0.3.
a~ 0 0.1 0.25 0.5 1.0 2.5 5.0
Plane Strain Crack
k1/oo.J(i 1.008 0.036 1.l01 1.258 1.808 2.869
kzloo..{a 0 0.026 0.065 0.129 0.263 0.697 1.567

Penn~-ShapedCrack
2a o.J(i In)
k1/( 1.002 1.012 1.038 1.118 1.442 2.083
k2/(2aO.J(i In) 0 0.017 0.041 0.083 0.168 0.440 0.960

122 Chapter 5
y
5 r--~--""'T'"-~n
E21 E J = 10.
5.
1.
0.2
0.1
o b h x
O'----'----'---~
o 0.2 0.4 0.6
blh
(a) (b)
5...---...---...------. 4...--"T"'""-....,.----r---.~
E IE =0.1
2 J 0.2
4 1.
5. 3
10.
O~--L---L--~ o L..-_"--_-'--_....L-_....
o 0.2 0.4 0.6 o 0.2 0.4 0.6 0.8
blh blh
(c) (d)
Figure 5.21. The nonnalized mode I stress intensity factor in an FGM plate with a surface
crack: (a) the part-crack geometry, (b) loading by a constant strain eo or fixed grips, (c)
membrane loading N, (d) bending moment M.
123
Table 5.3. Normalized Stress Intensity Factors in an FGM Plate Under Bending Away From
the Crack Region; v=O.3, kb= C 1Eo ..ra .
a@ Sin kJ(a)~ kJ(-I)/kb k2(a)~
o 0.809 -0.304 0 o
0.1 0.683 -0.268 -0.214 0.087
0.5 0.2 0.397 -0.178 -0.278 0.128
0.3 0.139 -0.076 -0.184 0.105
0.4 0.018 -0.013 -0.053 0.039
0.5 o o o o
4.3.3 Crack tip blunting toughening model for ceramic/metal

composites and FGMs
This section discusses the effect of a ductile metallic phase on the

fracture toughness of ceramic/metal composites and FGMs. Figure 5.22
illustrates the ductile phase toughening mechanism in ceramics. The
presence of a ductile metallic phase plastically blunts the tip of an initial
sharp crack as the load is increased. As a result, the crack opens up, thereby
increasing the fracture toughness. The toughening ratio of a composite
material consisting of a matrix and toughening phases, can be formulated
applying the rule of mixtures to the HRR5 field analysis at a crack tip [56,
57, 58]. The yield stress (j y and the effective fracture strain Cf can then be
expressed as follows:
(5.33)
(5.34)
where V_ and V_ are the volume fractions of the matrix phase, (a) and
toughening phase, {I
Using HRR field theory, the toughening ratio of the composite to the
matrix can be derived as follows:
(n+l)/2n
1 Kc [I+V,B (L-I )]<n-l)/2n x [ I+V,B ( A-I )]<n+l)/2n [ _Ec ]
/\,=-=
Km Em
(5.35)
5 Hutchinson-Rice-Rosengreen analysis of small deformation plasticity around a crack tip.

124 Chapter 5
where Kc and Km are the stress intensity factors, Ee and Em are the
Young's modulus of the composite and matrix, and a; a;
are the yield
stress, cj and cj are the fracture strain of the matrix and toughening
phases, and n is the reciprocal of the strain hardening exponent N. The
matrix and composite materials are assumed to have equal Poisson's ratios.
The toughening ratio, A, can eventually be expressed as a function of the
volume fraction of the toughening phase.
Ceramic phase
Blunted crack tip Cleavage fracture
Figure 5.22. Schematic illustration of the ductile-metallic-phase toughening mechanism.
Figure 5.23 shows the toughening ratio, A, of the composites titanium

carbide-nickel (TiC-Ni) and chromium carbide nickel (Cr3C2-Ni) as a
function of the Ni content, prepared by self-propagating high temperature
synthesis plus hot isostatic pressing (SHSIHIP) [59]. At a Ni fraction of 50
weight %, the fracture toughness is increased by a factor of 4 or 5. The small
difference between the Cr3C2-Ni and TiC-Ni composites could reflect the
inherent differences in the mechanical properties of Cr3C2 and TiC ceramics.
125
8 r-----------------------------,
"'" 6
o
-..:::;
~
0>4
C
'2
Q)
..c TiC/Ni NonFGMs
0> - Calculated
::J 2 o Experimental
~ CI'3C2INi NonFGMs
- Calculated
o Ex erimental
o
o 20 40 60
Ni content wr'/o
Figure 5.23. A comparison of the calculated and the experimentally determined A for TiC-Ni
and Cr3C2-Ni composites.
Figure 5.24 shows the profiles of local fracture toughness and hardness in
the symmetrically graded FGM, Cr3C2/Ni/Cr3C2, [60]. The numbers in the
center of the figure indicate the weight fraction of Ni in the green body for a
laminate configuration with a stepped gradient composition. The solid and
open circles show whether cracking occurred during the hardness test (solid
circle = cracked). The hardness curve shows the presence of a smooth
gradient rather than a stepped one. X-ray microanalysis indicates the
occurrence ofNi migration during the SHSfHIP process.
The fracture toughness estimated using the relation between K1C and the
Ni fractions in homogeneous composites of Cr3CrNi is shown as a solid line
in Figure 5.24. This agrees with the fracture toughness, 12.7 MPa.m 112,
measured in the thickness direction at the center of the Cr3C2/Ni/Cr3C2 FGM
by a four-point bend test for chevron-notched specimens [61]. However, the
estimated toughness is larger than the actual one. This may be due to the
residual stress effect.
126 Chapter 5
16 30
C13 Cr3C2fNi FGMs
~
l
Cl.
CJ
-....
14
20 cQ):
> c:
:c 12 0
()
10 Z
10
• Experimental
- Estimated from Final Comp.Ratio.
20
10 - - - - -
01....-----'-----'------''------1
o 2.65 5.3
Specimen width mm
Figure 5.24. Profiles of the hardness and fracture toughness of a CrJCzINi FGM.
4.4 Creep and Fatigue
The evaluation of the creep and fatigue properties of FGMs is necessary

to ensure the durability and integrity of structural components. A great deal
of effort has been devoted to studying crack initiation, the rate of crack
propagation, and overall life prediction for conventional homogeneous
materials. However, relatively little has been published on these subjects for
FGMs.
127
Because of the difference in the thermal expansion coefficient of

materials composing an FGM, the residual stress field that is generated
during cooling from the processing temperature plays an important role in
crack propagation behavior. In addition, the variation of composition within
the plastic zone around the crack tip, and the long range elastic fields, can
change the mechanical response compared with homogeneous materials.
Alloying can cause a change in the lattice constants, which produces a
bending moment in a beam with a monotonic gradient. In a beam with a
symmetrical gradient, it produces a central zone under tensile stress and two
outer layers under compressive stress. These effects are magnified in an
FGM that is exposed to temperature changes, because the coefficient of
thermal expansion depends on the localized composition.
The elastic modulus is also a function of the composition and its related
elastic residual stresses. Recently, it has been reported that creep in an FGM
layer can reduce the residual stresses during both fabrication and actual
thermal loading [62, 63]. It is important to be aware that the reduction in
thermal residual stresses during thermal loading can transform a stress state
into its opposite state, for example from compression to tension. In an FGM
this can result in cracking [58].
The stress amplitude required to maintain a constant rate of fatigue crack
propagation has been demonstrated for sintered binary Cu-Ni alloys with
graded compositions [64, 65]. Fatigue crack propagation tests were carried
out on bending test specimens with both homogeneous and graded
compositions using frequencies of about 100 kHz. The cracks were
propagated parallel and/or perpendicular to the gradient.
For homogeneous test specimens, the rate of fatigue crack propagation
follows the nth power of the stress intensity factor, which is called Paris' law.
It is not clear whether the linear regime of the Paris' plot is valid over the
entire concentration range. In the test mode used, the crack propagation rate
was constant. When the crack propagation direction was parallel to the
gradient, the range of the stress intensity factor, ~K, increased with
increasing nickel content, maintaining a constant crack propagation rate
(da/dN), as shown in Figure 5.25.
In a specimen with a symmetric gradient and pure copper in the center,
the crack path was determined by the pattern of the concentration. There is
no clear explanation for the wavy shape of the crack propagation, shown in
Figure 5.26. As can be seen in Figure 5.27, in a CU/Cu50Ni sample with a
symmetric gradient, the crack deviates into the copper rich side. This
deviation is thought to be due to the specific material properties
characteristic of this composition, and also to the long range elastic field, the
residual stress distribution, and the compositional changes within the plastic
zone around the crack tip. The distribution of the residual stress in graded
128 Chapter 5
copper-nickel alloys is a consequence of the difference between the thermal

expansion coefficients of copper and nickel. This leads to tension in the
copper rich part and compression in the nickel rich part, which can increase
as well as decrease the rate of crack propagation. The creep and fatigue
properties of an FGM would be improved if the distribution of the internal
stress could be tailored by controlling its compositional gradients.
Fraction of Ni [wt .%]

25 50 75 100
6 ~----~----~----~----~----~
<I
4
o 2
Crad< length a [mm]
Figure 5.25. Crack propagation in a graded CulNi FGM (daldN = a constant). The crack
propagation direction is parallel to the gradient.
4.5 Nondestructive Evaluation
For FGMs to gain acceptability in industrial applications, quality control

using nondestructive evaluation (NDE) is required for each processing and
assembly step. Although numerous NDE methods have been developed for
testing a variety of engineering materials, their application to FGMs is still
limited.
Plasma sprayed coatings of a Zr02INiCrAIY FGM on stainless steel
substrates, which were damaged due to the thermal shock from irradiation
with a CO2 laser, were inspected using a water-immersion ultrasonic method
[66]. Because of the roughness of the plasma sprayed coating's surface,
detecting surface cracks from the echo of ultrasonic waves injected at the
surface proved to be difficult. However, the transmission echo from an
ultrasonic pulse injected from the back surface and focused through the
129
coating layer at both the surface and the coating interface, contained a great
deal of information about the thermal shock damage. A scanning acoustic
microscope used to characterize the same coatings could detect the
difference between the velocity of the surface waves from damaged and
undamaged regions at the polished surface of metal-ceramic composites with
various mixing ratios [67].
3 8
7
Q)
u 6
>.
()
2 5
.....
E
oS 4
z
-c 3
III
-c 2
2
Crad< length a [mm]
Figure 5.26. Crack propagation in a graded Ni/CulNi FGM (da/dN = a constant). The crack
propagation direction is perpendicular to the gradient.
~Cu.- 50Ni' .
, "7
gradient
500 j,.IlTI • Cu .
Figure 5.27. Micrograph of a crack in a graded CulCu50Ni FGM perpendicular to the
gradient.
130 Chapter 5
Invisible microcracks can be detected with an optical microscope. As

previously noted, a line-focus beam acoustic microscope has been used
successfully to determine the elastic properties and their distribution in
PSZ/SS FGMs [68]. Acoustic emission, which can analyze the onset of a
crack, its propagation, and fracture modes can be used to determine the
microscopic fracture mechanism for metal - ceramic composites [69]. For
the successful application of FGMs, their design, processing, and
nondestructive evaluation must be closely linked [70].
5. COMPLEX BEHAVIOR
FGMs are expected to be used for applications such as engine

components, the airframes of reusable rockets, and space transportation
vehicles, which encounter extremely high cyclic heat loads in severe
oxidation and corrosive environments. Under actual heat loading conditions,
both microscopic and macroscopic stresses are generated by large drops in
temperature during the transition from startup to shutdown, and also by
differences between the thermal expansion of the ceramic-rich and the
metal-rich layers. Therefore, it is important to analyze the internal thermal
stresses in FGMs and to evaluate their resistance at high temperatures to
thermal shock, thermal fatigue, oxidation, and corrosion.
5.1 Thermal Stress
Thermal stress is generated because of constraints in the deformation of

components that are subjected to certain thermomechanical boundary
conditions such as inhomogeneous temperature distribution in a
homogeneous component; uniform heating of an inhomogeneous
component, for example in a metal/ceramic joint [71, 72]; and the rapid
heating and cooling of a component's surface [73, 74]. In FGMs, some or all
of the following conditions are accompanied by thermal stress: cooling from
the processing temperature, a steady state temperature gradient field, and
transient temperature distribution due to thermal shock and cyclic thermal
loading during operation [75, 76]. Therefore, as the first step in developing
an FGM, one must know the thermal stress present in each of these
conditions. The relation between the estimated thermal stress and the
observed fracture mode can be used in defining the design criteria.
Two problems that must be addressed when designing FGMs for
fabrication by powder metallurgy are: minimizing the thermal stress
generated during cooling from the sintering temperature in order to prevent
bending or cracking [77, 78], and minimizing the thermal stress generated by
131
a temperature gradient [79]. The first problem can be analyzed using

experimentally determined thermal expansion coefficients and elastic
constants. The second problem involves taking into consideration the
properties of materials that are temperature dependent in designing the
optimum composition for an FGM exposed to a temperature gradient. For
thermal barrier applications, no self-consistent design scheme for
minimizing the thermal stress in a temperature gradient has been developed
that can be used to optimize the composition for both process and service
conditions. However it has been found that the optimum composition for
process conditions is also relatively effective for service conditions.
Estimating the optimum composition for an object with a given shape
and size under a particular thermal loading condition, requires knowing the
dependence on the composition of properties such as thermal expansion and
thermal conductivity, and the elastic and plastic constants. As a first
approximation, a linear law can be assumed for the dependence of these
properties on a material's composition [80]. However, because a material's
properties depend strongly on its microstructure, the relationship between
properties and microstructure has been also investigated over a wide range of
compositions [81, 82, 83].
5.1.1 A thermal stress analysis case study
For the thermal stress analysis of a partially stabilized zirconia (Zr02)

Istainless steel (PSZ/SS) FGM two types of models are used: a cylinder and
a disk sintered at 1450°C and cooled to room temperature. For the stress
calculation, the stepwise variation of composition in the interlayer is
assumed. Since the model is symmetrical, only half of the cross section is
considered. The finite element mesh, which is divided into 900 rectangular
elements, is shown in Figure 5.28. The elastic constants and thermal
expansion coefficients of PSZ and SS are given in Table 5.4. The properties
of the interlayer material are estimated assuming their linear dependencies
on composition.
Table 5..
4 Thennal and Mechanical Properties of the Model Materials
Material E (MPa) G(MPa) u .aLK"ll
PSZ 1.75 x 105 0.673 X 105 0.3 10.0 x 10<;
ShN4 3.0 1.18 0.27 3.6
W 4.0 1.539 0.3 6.0
SS 1.96 0.784 0.26 14.0
As shown in Figure 5.29, the composition of the interlayer is represented

by the following power law equation:
132 Chapter 5
C = (xld)P (5.36)
where C is the volume fraction of the partially stabilized zirconia (PSZ)

phase, d is the thickness of the interlayer, x is the distance from the stainless
steel phase, and p is a numerical constant related to the phase distribution or
compositional gradient. The plastic deformation and the temperature
dependence of the physical constants are neglected. However, since the
plastic deformation can reduce the stress concentration, this calculation may
overestimate the thermal stress.
"0
I
Part A
.- ~~§§§
08
-NODAL POINTS : 1010
-ELEMENTS : 900
(mm)
030
FGM sample
)- -
eu sample holder
1 __
Figure 5.28. Mesh division for the finite element analysis of cylindrical and disk-shaped
FGMs. Number of cylinder elements, 1125 and nodal points, 1216. Number of disk elements,
900 and nodal points, 10 10
133
C=~x/d}P
1.0
N
en
a..
'0
c
:u....ca
0
u. 0.5
Q)
E
:J
0
>
U
0.0
0.0 0.5 1.0
88304 x/d P8Z
Figure 5.29. Compositional gradients in the interlayer as a function of the normalized

distance. x is the distance from the metal end and d is the thickness of the interlayer.
5.1.2 Thermal stress during fabrication
As shown in Figure 5.30, the maximum tensile stress is near the surface
of the ceramic side of a PSZ/SS FGM. The effect of the composition of the
interlayer on the axial component of the thermal stress is shown in Figure
5.31. As the constant p decreases, the position of the maximum stress shifts
toward the metal side, thereby reducing the stress in the ceramic side. From
the variation of the stress distribution curve, there seems to be an optimum
composition for the reduction of the maximum stress.
Figure 5.32 shows the effect of the thickness of the PSZ layer on the
maximum tensile stress. As the thickness decreases from 5 mm to 1 mm, the
maximum axial stress is reduced sharply by about 75 %. However, as Figure
5.33 indicates there is no evident effect of the sample's diameter on the
maximum tensile stress.
134 Chapter 5
Center line Center line
PSZ
2
4
6
8
10
-2
-2
0 0
2
40%
-10 2
-8
-6
-4
SS304
(Unit: 1 11 OOMPa) 10mm

~
(a) {b)p=1
Figure 5.30. Contour maps of axial thermal stress: (a) directly bonded PSZ/SS and (b)
compositionally graded PSZ/SS.
When joining a large area with a thin interlayer, the circumferential stress
should be taken into account. As shown in Figure 5.34, there is an inverse
relation between the circumferential stress on the outer periphery of the PSZ
and the axial stress.
Figure 5.35 shows the distribution of axial, circumferential, and shear
stresses in a disk-shaped sample of PSZ/SS cooled from 1450°C. The axial
stress is highest at the surface on the side of the ceramic rich region, while
the circumferential stress is highest at the center of the top surface. The
maximum values for the axial and circumferential stresses are about the
same, and the distribution of the radial stress and the circumferential stress is
similar. Because the shear stress is small compared with the axial and
circumferential stresses it can be ignored in this case. The maximum values
for the axial, radial, and circumferential stresses, which are all dependent on
135
1000 .!
(11
a.. ';;
:E
..... ...is
rn ~
! 0 .~
10
'ii Q.
S
~ -1000 o
CJ
88
~ ~ 4 ~ 0 2 468
Distance I mm
Figure 5.31. The distribution of the axial stress for different compositional profiles (p): A =
0.23, B = 0.7, C = 1.0, D = 3.0.
-
C/)
C/)
~
C/)
(ij
.~
E
:J
E
.~
E
~
~ 0.5
Q)
c:
8
(Linear composition-control)
o~----~--~~--~~--~~--~
o 2 3 4 5
Thickness of the P8Z layer (mm)
Figure 5.32. The dependence of the maximum axial stress on the thickness of the interlayer.
136 Chapter 5
2.0 ..... ---...,..----"1""""----,
In
In
~
ti
"iii
.~
E
::J
E 1.0
.~
E
~ PSZ
~ ~~~.--l4
Qi
a:
(Linear composition-control)
o~------~--------~------~
o 10 20 30
Diameter of the PSZ layer (mm)
Figure 5.33. The dependence of the maximum axial stress on the diameter of the graded
PSZ/SS.
Diameter of the PSZ (mm)

10 20 30
t
¢
i3
300 I" -I
Cij"
0...
~ (t=5mm)
In
In
~ 200
J
ti
~
E
~
Q)
E
::J
~ 100
6 (¢=8mm)
o~--~--~----~--~--~--~
o 2 3 4 5
Thickness of the PSZ layer (mm)
Figure 5.34. The dependence of the circumferential stress at the top periphery ofPSZ on the
diameter and the thickness of the PSZ.
137
(a )
6
4
0
0 0
(Unit 1/100 MPa )
( b )6
2
-2
-6
-4
--
~
4
·2 0
~
·2 0
·2
.......
6
4 :..--
2
0
(Unit 1/100 MPa)

0
(c )
o
o
o
r-------~------------~~~2
o o o
(Unit 1/100 MPa)
Figure 5.35. Stress distribution in a disk shaped PSZ/SS FGM. (a) axial stress, (b)
circumferential stress, (c) shear stress
the thickness of the sample, are shown in Figure 5.36. The axial stress
predominates at the surface on the side of a disk-shaped sample, when its
thickness is 2 mm or larger.
Cracks often form in samples that do not have optimized compositional
gradients. The optimum compositional gradient for reducing axial stress in
the PSZ/SS specimens that are about 8 mm in diameter and 4 mm thick with
138 Chapter 5
sintered joints, is shown in Figure 5.37. In the sample with the optimum
composition in which the axial stress is at a minimum, the exponent pis 0.7.
No cracks are formed in this specimen and the bending strength is about 250
MPa. But in the samples that do not have optimized compositions, for
example, if p equals 1, cracks occur in the PSZ near the interlayer; and if p
equals 0.3, cracks occur in the 70 volume % PSZ phase.
1500
• ~ axial stress
t:Jc
_ _ _ radial
- -0 - - circumferential
--fr-- shear
ca
a.. I 10
6
D+~D
Ul 1000
Ul
~
Cij
(ij
E
Qi
---------0
:5
E
::J
E
·x 500
III
::E
o~----~----~----~----~----------~
0.0 1.0 2.0 3.0 4.0 5.0
Thickness of SS and PSZ layers (mm)
Figure 5.36. The relation between the maximum thermal stresses and the thickness of the PSZ
and stainless steel layers.
5.1.3 The thermal stress state under actual thermal loading
In thermal shock tests, numerous cracks are produced in the center of an

FGM part where the combustion flame impinges. These vertical cracks are
initiated at the surface as shown in Figure 5.38. Some are deflected parallel
to the surface, but there is no delamination. Figure 5.39, a fracture mode map
for PSZ/SS FGMs, indicates the presence of a damaged region and a crack-
free region [78]. The critical surface temperature, which is defined as the
139
temperature at which the first crack is formed (about l027°C for a PSZ/SS
FGM), is almost constant, and is independent of the sample's size and phase
UJ
-
UJ
Q)
10lnterlayers
'-
UJ
"0, PSZ
1
.!!!
)(
(CJ
• SS C=(x/d)P
1.0
E
:::l
E
)(
(CJ 0.5
E
-
Q)
.~
(CJ 0.0
1) 0.0 0.5 1.0
a: x/d
0
0.1 0.5 1.0 5.0 10
Exponentp
Figure 5.37. The maximum axial stress in an FGM nonnalized with respect to the stress in
direct bonding, as a function of the exponent p (x is the distance from the PSZ phase). The
minimum in each curve indicates the optimum phase distribution for effective thennal stress
relaxation in the compositionally graded model.
Smm
Figure 5.38. Typical damage on the surface of the PSZ after a burner heating test.
140 Chapter 5
distribution. Crack generation can be monitored by acoustic emission (AE).

During heating there are no AE signals. However, many are detected after
the onset of cooling, indicating the formation of cracks.
Surface crack formation and its extended behavior are closely associated
with the thermal stress fields created in FGMs during heating and cooling.
Figure 5.40 shows the stress distribution in the radial and circumferential
directions, on the surface of a disk-shaped sample during steady state heating
at the maximum thermal output. Both the radial and the circumferential
stresses in the central region are compressive (about 1.3 GPa), and the stress
decreases towards the edge inversely with the radial distance.
2000
L::,. PSZlSS FGM
0 PSZ spray
coating
1600 0 (non-FGM)
p Vertical crack
(\) L::,.
~
(J
C1l
't:
:J 1200
II)
0
0.
.8
(\)
£
0
'0
....
(\) 800
:J Crack free
iii
....
(\)
0.
E
(\)
I-
400
o~~~~~~--~~~~~~~
o 200 400 600 800 1000 1200

Temperature of the bottom surface ( ·C )
Figure 5.39. A fracture mode map for PSZ/stainless steel samples that includes regions with
vertical cracks and regions without cracks.
The distribution of radial and axial stresses along the center axis are
shown in Figure 5.41. The compressive stress, which is at a maximum on the
top surface, decreases towards the bottom surface along the center axis. The
141
radial stress changes to a tensile stress within the stainless steel layer, and
the axial stress, which is associated with delamination, is relatively small.
Therefore, during heating the stresses at the center of the top surface are in
biaxial compression that decreases inversely with the radial distance from
the periphery.
0
~
a..
C
~ -0.5
b
"0
ta... -1.0
b
1/1
1/1
(l)
"-
iii -1.5
iii
E
"-
(l)
F -2.0
0 5 10 15
Radius r (mm)
Figure 5.40. The distribution of the thermal stresses a r and as at the heated surface of a disk-
shaped PSZ/SS FGM with linear composition control.
2.0
""'
m ......
a.. SS / PSZ FGM Stainless steel Ni
C
N 1.0
0
"0
c:
m...
0
0
l:!
~.rJ'
(l)
~ -1.0 (Jr
8 ...,
iii
E L1S __
"-
(l)
.s::
f- -2.0
0 2 3 4 5
Depthd (mm)
Figure 5.41. The distribution of the thermal stresses, a r and a z along the center axis of a disk-
shaped PSZ/SS FGM from the top surface to the bottom surface.
142 Chapter 5
Figure 5.42 shows typical distributions for the transient thennal stress in
the radial direction at the top surface of an FGM during heating and
subsequent cooling, taking into account non-linear deformation of the
components and temperature dependent material properties. As can be seen,
heating generates a large compressive stress at 0.1 s, but after 300 s the
stress is relaxed at the center. This is because the surface temperature
reaches the brittle-to-ductile transition temperature thereby allowing the non-
linear defonnation of PSZ to occur. During cooling, however, the resulting
inelastic strain rapidly converts the stress into tensile stress. From the
residual radial stress after cooling, it has been determined that the high
tensile stress is limited to the layer close to the surface. This is because the
temperature decreases abruptly toward the inside, and non-linear
defonnation is limited to a shallow depth from the surface.
center periphery center hery

or-------------~~ ~.~------------~~.
_2500'----.L..-.....--'--~--' .2500 L.-~_.L..-....._-'----'_-'

o 5 10 15 o 5 10 15
Radial distance (mm) Radial distance (mm)
(a) heating (b) cooling
Figure 5.42. The transient thermal stress in the radial direction at the top surface of an FGM
during heating and subsequent cooling.
Based on this thermal stress analysis, a mechanism for the fonnation of

vertical cracks has been proposed. During heating as shown in Figure 5.43,
the top surface of the FGM is in a high biaxial compressive stress state. The
stresses induce non-linear deformation when the top surface is heated above
the transition temperature. During the cooling cycle, the stress converts into
a tensile stress that is high enough to exceed the fracture strength of PSZ,
thus causing vertical cracking. Figure 5.44 shows the dependence on the
phase distribution of the maximum compressive stress at the top surface.
compositional gradient.
143
Vertical crack
initiation ,
" ,
~,' Fracture stress
Compressive stress . strain
Figure 5.43. A conceptual model for the formation of vertical cracks during a burner heating
test on a ceramic/metal FGM.
Iii'
2.0 I
a..
~
(/)
(/)
~
1.5 r0- O 0 -
iii 0
-
Q)
>
'(jj 1.0 r- 0
(/)
~
c. 0
E
0
U
0.5 r- -
.!I<:
ctl
Q)
a.. I
0.0
0.1 10
Gradient exponent, p
Figure 5.44. The peak compressive stress at the top surface of an FGM as a function of its
compositional gradient.
5.2 Thermal Shock
Figure 5.45 shows tests for evaluating the development of FGMs as

thermal barrier coatings [84]. The first step includes several fundamental
tests for determining basic thermomechanical properties of the homogeneous
components. Various heating methods such as laser, plasma-arc, burner, and
144 Chapter 5
electron beam are used for testing thermal shock and thermal fatigue. For
example, the thermal shock resistance of a plasma sprayed FGM coating of
PSZlNiCrAIY on stainless steel (SS) was evaluated by using a CO2 laser to
irradiate the coating's surface, as shown in Figure 5.46 [84]. NiCrAIY or
NiCoCrAlY is used as a bond coat to improve the adhesion of the ceramic
coating to the metal components. The thermal shock resistance is
characterized by determining the critical power density, Pc (the critical laser
power divided by the area of the spot), when the first vertical crack appears.
The effectiveness of the graded coating is evidenced by a threefold increase
in its thermal shock resistance compared with a homogeneous composite
coating.
Tests Sample size
Service performance
Test of actual device

Large scale thermal loading test
Simulated service test
100 ....... 300 mm
Small scale thermal loading test
Component test in a simulated environment 50 ....... 100 mm
Thermal shock / fatigue test

Single parameter test Thermal barrier performance test
(Special) Erosion / corrosion test
30mm
Single parameter test Fracture strength test

(Standard) Fracture toughness test
Thermal property measurement
Figure 5.45. Evaluative tests for developing FGMs with thermal barrier properties.
Specimen
Chopper
Tranalatlon Stage
Figure 5.46. Schematic of the laser beam thermal shock test. (AE = acoustic emission)
145
Heating with a plasma arc has been used to evaluate the oxidation and
thermal shock resistance of the PSZINiCrAIY FGM coating on SS [85]. To
induce a temperature gradient, the top surface was exposed to an argon CAr)
plasma containing a controlled amount of oxygen, while the bottom surface
was cooled by flowing Ar. The oxidation rate of the coating, which is
independent of its graded composition, follows the parabolic law. The
oxidation behavior is largely controlled by the formation of an alumina film
(Al z0 3 ) on the NiCrAlY.
]~
8 ..- , . /
,./,./
-
6
..- ..-
./
'l'·
1
control unit )
3 8
liz Oz
12
Cu holder
Figure 5.47. Schematic of the test system for the burner heating test, and the configuration for
holding the sample. (I) test sample, (2) torch, (3) cooling chamber, (4) shutter, (5) protective
plate, (6) acoustic emission (AE) sensor, (7) pyrometer, (8) thermocouples, (9) AE apparatus,
(10) monitor, (11) regulatory valve, (12) cooling water supply.
A burner heating test, shown schematically in Figure 5.47, was used to

evaluate the thermal shock and fatigue resistance of FGM coatings for
applications such as the thrust chamber of a rocket engine [86, 87] and the
leading edge in advanced gas turbine blades [88]. The test samples were
prepared by powder metallurgy and plasma spray coating. The temperature
at which the first crack forms was used as a measure of the coating's
performance as a thermal barrier. This temperature was almost constant for
146 Chapter 5
various samples and heating conditions, indicating the dependence of the

thermal barrier property on the material. The fracture mechanism map,
shown in Figure 5.48, for correlating the temperatu~e with coating damage,
indicates the higher spalling resistance of the FGM coating compared with a
conventional Zr02 single-layer coating.
2000..------1 o No crack
0 No crack 20Ou IB Vertical crack
IB Vertical crack
• Delamination • Delamination
1600 1600
•• •
.
HI HI
P 1200 DO IB QTarget
....... 0 o 0 IB
co , co ,4
o .. .' I- 8O() 00 , {j
I- 800 q, 0
o 0 ' .. " . ' 0
, , ,0
,,
0
o "If
0 00 ,
o ,fY' 0 o0' "
400 , 400 ,,
, ,,
"",,/ ,,
,,
0
o~0~2~00:--:4:1:-00=-=6l::00=-=80:-::0:--1:-:000 o 200 400 600 800 1000
Tb ("C) Tb (OC)
(a) Homogeneous component (b) FGM
Figure 5.48. A fracture mechanism map for (a) a homogeneous component and (b) an FGM.
(T. = the temperature of the top surface. Tb = the temperature of the bottom surface.)
5.3 Thermal Fatigue
Thermal fatigue has been tested for a number of FGMs: titanium

diboride/copper (TiB2/Cu) [89], titanium carbide/nickel (TiCINi) [90],
partially stabilized zirconia/nickel (PSZlNi) [91], and silicon carbide/carbon-
carbon (SiCICC) [92] prepared by self-propagating high temperature
synthesis (SHS), self-propagating high temperature synthesis plus hot
isostatic pressing (SHS/HIP), low pressure plasma spray (LPPS), and
chemical vapor deposition and chemical vapor infiltration (CVD/CVI),
respectively. The test involved estimating the variation of the effective
thermal conductivity with thermal cycling.
A diagram of the test apparatus is shown in Figure 5.49 [93]. The sample
is exposed to large temperature differences by heating the top surface with
the beam of a 30 kW xenon (Xe) arc lamp, and cooling the bottom surface
147
with liquid nitrogen. The heating and cooling cycles are effected by opening
and closing a shutter between two reflectors.
Ifthe effective thermal conductivity (Ie) of a material is defined as:
(5.37)
where q is the heat flux loaded on the sample, Ts is the average

temperature of the top surface, Tb is the temperature of the bottom surface,
and L is the thickness of the sample.
Video Radiation
pyrometer
Vacuum
vessel
To stack
DC power supply
Figure 5.49. Diagram of the test apparatus for cyclic heating using a Xe arc lamp.
Then, the normalized effective thermal conductivity, ite ' is expressed as:
(5.38)
where I (n)e is the effective thermal conductivity after n heating cycles

and I (l)e is the effective thermal conductivity at initial heating under steady
state conditions.
148 Chapter 5
Results of thermal fatigue tests for TiB 2/Cu FGMs are shown in Figure
5.50. The temperature difference between the top surface (~ 427°C) and the
bottom surface of each sample is - 300°C. The normalized effective thermal
conductivity of the 8 layer sample (GT -48) is almost constant up to 30
cycles, but decreases significantly at 40 cycles. While with the 13 layer
sample (GT-51) it decreases somewhat with increasing thermal cycling. The
large vertical cracks generated during thermal cycling decrease the effective
thermal conductivity due to the thermal resistance of cracks and pores. The
larger number of cracks in the 8 layer sample than in the 13 layer one is
attributed to higher thermal stress.
1.5
--0-- GT-48 (8 layers)

~
.> - -6- - GT-51 (13 layers)
U:::J
"0
c:
0
0
Iii
...E
Q)
-=
Q)
.~
t5
Q)
:t: 0.5
Q)
"0
Q)
.!:::!
Iii
E
0
z
0
0 10 20 30 40 50
Number of cycles
Figure 5.50. Effect of cyclic thermal exposure on the degradation of the normalized effective
thermal conductivity of the TiB2/Cu FGM samples: GT-48 and GT-51.
The results of thermal fatigue tests for TiClNi FGMs are shown in Figure
5.51. The temperature difference in each of the samples is 350°C-650°C
between the top surface (727°C-1127°C) and the bottom surface. In the OM-
62 sample, which was tailored so that the phase distribution parameter for a
mole fraction of Ni was p=0.3, spalling occurred during the 9th heating
cycle. In the OM-63 (p=1.0), a large vertical crack appeared on the surface at
the start of the 20th heating cycle. This crack probably occurred during the
previous cooling step. The normalized effective thermal conductivity of
149
samples OM-61 and OM-64 decreased with an increase in thermal cycling.

These results lead to the conclusion that for reducing thermal stress and
extending a TiClNi FGM's life, the optimum exponent of the phase
distribution function should be 0.5 - 0.7.
---*- OM-62 (n=0.3)

--0-- OM-61 (n=0.5)
--fr-- OM-64 (n=0.7)
- { } - OM-63 (n=1.0)
o o~----~------~----~------~
10 20 30 40
Number of cycles
Figure 5.51. The effect of cyclic thennal exposure on the degradation of the nonnalized
effective thennal conductivity of the TiClNi FGM samples: OM-61, 62, 63, and 64.
Figure 5.52 shows test results for a PSZINi FGM. The temperature of the
bottom surface was maintained at 700°C during thermal exposure. During
initial heating the maximum temperature of the top surface was 827°C,
reaching 1227°C after 45 cycles. The normalized effective thermal
conductivity decreases to a minimum at 25 cycles and remains at 60 % of the
initial value. There are large vertical macro cracks and small delaminations.
However, macrocracks (a large decrease in effective thermal conductivity)
do not occur when the temperature of the bottom surface is maintained at -
127°C [93]. The vertical cracks are apparently generated in earlier cycles due
to the higher temperature of the bottom surface. This can cause inelastic
deformation of the metal phases, which can act to relax the thermal stresses.
150 Chapter 5
1.5 r----r---,---.,.---r--.....,
---f:r- NS-55
10 20 30 40 50
Number of cycles
Figure 5.52. The effect of cyclic thermal exposure on the degradation of the normalized
effective thermal conductivity of the PSZINi FGM sample: NS-55.
The variation in the normalized effective thermal conductivity of SiCICC

FGMs is shown in Figure 5.53. The maximum temperature of the top
surface, 1627°C-I727°C, is during the initial cycle, and the temperature of
the bottom surface is 727°C-I027°C. The normalized effective thermal
conductivity of each sample decreases with an increase in the number of
cycles. When a heat flux of - 0.5 MW/m2 is loaded on SiCICC FGM
samples (JS-57 and JS-58) and a non-FGM sample coated with a single layer
of SiC (JS-59), the normalized effective thermal conductivity of the non-
FGM (JS-59) degrades the fastest, and spalling at its surface occurs at the
20th thermal cycle. In addition, the degradation of the normalized effective
thermal conductivity of the FGM sample (JS-57) is half that of the non-FGM
US-59). This indicates that a SiCICC graded layer can improve thermal
fatigue resistance and prevent spalling. When a higher heat flux of 1.1
MW/m2 is loaded on the FGM (JS-58), the decrease of the normalized
effective thermal conductivity is larger than that of the FGM(JS-57). This
implies that the higher thermal stress associated with a higher heat flux
would accelerate the propagation of flaws in some FGMs.
These experimental results indicate that the exposure of FGMs to thermal
cycling generates flaws such as cracks and spalling, which results in a
decrease in normalized effective thermal conductivity. The change in the
normalized effective thermal conductivity can be used to investigate thermal
fatigue.
151
--0- JS-57 SiC/CC FGM

.?:-
.s: ~JS-58
1.0
n:::J
--0-- JS-59 SiC/CC non-FGM
'0
C
aC)
0.8
'iii
E
a;
-:= 0.6
Q)
>
UQ)
==Q) 0.4
'0
Q)
.!::!
Spalling
'iii (heating phase)
E 0.2
0
z
0
0 10 20 30
Number of cycles
Figure 5.53. The effect of cyclic thennal exposure on the degradation of the nonnalized
effective thennal conductivity of the SiC/CC FGM samples: JS-57 and JS-58 compared with
the non-FGM sample, JS-59.
5.4 Oxidation and Corrosion
Graded SiC coatings adhere well to graphite components and prevent

their oxidation. SiC/C FGM coatings made by chemical vapor deposition
(CVD) have good oxidation resistance up to 800°C in air [94], and those
made by a thermal reaction between graphite and silicon powders up to
1400°C [95]. FGMs composed of a graded layer of 30 /lm thick SiC/C in
chemical vapor infiltrated (CVI) woven carbon fiber are tough and oxidation
resistant [96]. When subsequently coated by CVD with a 100 /lm thick layer
of SiC, they are highly oxidation resistant to cyclic heating between 350°C-
1525°C.
Although FGMs can be protectively coated against oxidation and
corrosion, surface cracks are sometimes produced as a result of the tensile
stress created during heating and cooling. These cracks then can act as
conduits for oxidation. An increase in the volume of one or more of an
FGM's components due to oxidation can open the cracks further, or produce
152 Chapter 5
new cracks, ultimately causing spalling. Introducing a compressive stress in

the surface layer can inhibit cracking.
A silicon carbide/titanium carbide/carbon-carbon FGM (SiC/TiC/CC)
coating deposited by CVD on a CC composite induces a strong compressive
residual stress (500 MPa to 1000 MPa) in the surface SiC layer because of
the higher thermal expansion rate of TiC. It has good oxidation resistance at
1300°C with few surface cracks [97]. However, as the TiC layer becomes
oxidized through the cracks, the increased volume of the titanium dioxide
(Ti0 2) seals the cracks, as shown in Figure 5.54. It is expected that this self-
healing effect will be incorporated in the design ofFGMs.
Figure 5.54. Crack sealing with Ti0 2 formed along the thermal crack in the coated layer of
SiCffiC on the C/C composite, after heating in air at IIOO'C for Ih.
A graded SiC/TiC layer has been deposited by CVD on stainless steel

(SS304) as a potential material for a system to produce hydrogen by the
thermochemical dissolution of water [98]. A material for this system must be
resistant up to 727°C to corrosion by the highly corrosive bromine-oxygen-
hydrogen bromide (Br2-02-HBr) gases produced in this process. The graded
coating showed superior corrosion resistance in both isothermal and cyclic
tests compared with stainless steel coated with a monolayer of TiC or SiC.
This indicates that the high temperature corrosion resistance of FGMs could
be further improved by optimizing their graded composition and
microstructure.
An understanding about the properties of FGMs as well as their
characterization is fundamental both to their successful processing, discussed
in Chapter 6, and to their applications, described in Chapter 7.
IS3
APPENDIX 5.3 A
The derivation of the heat conduction equation for a material when

there is no heat source and sink.
Consider a small region R in a body and its boundary surface S. Then the
amount of heat escaping from R per unit time is:
ffQ·ndA (S.3A.l)
where Q. n is the component of Q in the direction of the external unit

normal vector n of S. From the divergence theorem, one obtains:
ff Q·ndA = -fffV(XVT)dxdydz (S.3A.2)

R
The total amount of the heat Q contained in R is:
Q = f f f cpTdxdydz (S.3A.3)
R
where c is the specific heat of the material and p is the density.

The rate ofthe decrease ofQ is:
-JQ ar
- = - If Jcp-dxdydz (5.3A.4)
at R at
which must equal the quantity of heat escaping from R.

Thus:
ar
f f f cp-:;:dxdydz = f f fV(}'VT)dxdydz (S.3A.S)
R at R
Since this holds for any region R in the body, one can obtain:
(S.3A.6)
154 Chapter 5
APPENDIX 5.4 A
Derivation of the fundamental criteria for fracture initiation and

propagation
The fundamental criteria for fracture initiation and propagation can be
derived by using the concept of energy balance at the crack front, which for
an equilibrium crack can be expressed as [42]:
d
-(U - V) = G ::::; Gc (5.4A.l)
dA
where U is the work done by the external loads, V is the strain energy,
and A is the crack surface area. G (the left hand side of Equation 5.4A.l) is
the energy available, and G c is the energy required to create a unit area of
new fracture surface. These terms are referred to as the crack driving force
and the fracture toughness, respectively.
By using the mechanism of crack closure, it can be shown that the crack
driving force can be evaluated from the asymptotic stresses and
displacements near the crack tip. In homogeneous materials the asymptotic
stresses, in turn, are obtained from the elasticity solution as follows [42]:
k1 k3
(lij (r,O) = $/1(0)
2r IJ
+ 5k22r 121~ (0) , (liz (r, 0) = $ hi (0) ,
(i,j = r,O) (5.4A.2)
where f 1ij , f2ij , f3i are known functions,

Iwe(O) = 12re(O) = 13e(O) = 1, and the constants kl , k2 and k3 represent
the magnitude of the applied loads and severity of the part/flaw geometry
and are known respectively, as the mode I, II, and III stress intensity factors.
Thus, by evaluating the local energy release, it can be shown that:
(5.4A.3)
where E, v, and !-l are respectively, the Young's modulus, Poisson's ratio,
and the shear modulus, and K] = Jiik l , Ku =.J1ik2' KDJ =..fiik3. For
155
the important case of a mode I condition, for example, the fracture criterion
Equation 5.4A.l) becomes:
(5.4A.4)
The criterion, as expressed by (5.4A.l) or (5.4A.4), is very useful to

study the question of fracture stability. However, many of the fracture
failures such as fatigue and creep crack growth and stress corrosion cracking
involve a period of subcritical crack propagation. In modeling these failure
processes, the stress intensity factor, kj , or the strain energy release rate, G j ,
(I = 1,2,3), are known to be very effective.
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FGM'90, Sendai, (eds. M. Yamanouchi, M. Koizumi, T. Hirai, and I. Shiota), FGM
Forum, Tokyo, Society for Non-traditional Technology, 53-58.
2. Kawasaki, A. and Watanabe, R. (1997) Concept and PIM fabrication of functionally
gradient materials, Ceramics International, 23, 73-83.
3. DeHoff, R.T. (1968) Curvature and the topological properties of interconnected phases, in
Quantitative Microscopy, (eds. R. T.DeHoff and F.N .Rhines), McGraw-Hill, New York,
291-325.
4. Stauffer, D. (1985) Introduction to Percolation Theory, Taylor & Francis, London.
5. Mandelbrot, B.B. (1982) Fractal Geometry o/Nature, W.H. Freeman, San Francisco.
6. Capasso, F. (1987) Bad-gap engineering and interface engineering, from graded-gap
structures to tunable band discontinuities, in Heterojunction Band Discontinuities, (eds. F.
Capasso and G. Margaritondo), Elsevier, Amsterdam, 400-450.
7. Sarker, A. et al. (1997) Electrophoretic forming of functionally-graded barium/strontium
titanate ceramics, in Proc. o/The Fourth Int'/. Symp. on FGM'96, Tsukuba, (eds. I. Shiota
and Y. Miyamoto), Elsevier, Amsterdam, 221-26.
8. Kawai, T. and Miyazaki, S. (1990) Development of a piezo-ceramic actuator with
functionally gradient material, J Ceram. Soc. Jpn. Int. Ed. 98, 168-172.
9. Miyazaki, S., Kawai, T., and Aragaki, M. (1991) A piezoelectric pump driven by a flexural
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37. Lannutti, J. 1. (1994) Functionally graded materials, properties, potential and design
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41. Delfosse, D. (1990) Structural part with a concentration gradient produced by powder
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Institute of Technology, Lausanne.
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elastic plane, Engineering Fracture Mechanics, 47,533-545.
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nonhomogeneous medium. ASME J Appl. Mech., 60, 406-413.
45. Erdogan, F. (1985) The crack problem for bonded nonhomogeneous materials under
antiplane shear loading, ASME J Appl. Mech., 52, 823-828.
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49. Cook, T. S. and Erdogan, F. (1972) Stresses in bonded materials with a crack
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Engineering Mathematics, 26, 467-480.
51. Erdogan, F. and Wu, B.H. (1996); Crack problems in FGM layers under thermal stresses,
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52. Erdogan, F. (1995) Fracture mechanics of functionally graded materials, J Composites
Engineering, 5, 753-770.
53. Erdogan, F. and Ozturk, M. (1995) Periodic cracking of functionally graded coatings, Int.
J Engng. Sci., 33, 2179-2195.
54. Ozturk, M. and Erdogan, F. (1996) Axisymmetric crack problem in bonded materials with
a graded interfacial region. Int. J Solids Structures, 33, 193-217.
55. Chen, Y.F. and Erdogan, F. (1996) The interface crack problem for a nonhomogeneous
coating bonded to a homogeneous substrate, J Mech. Phys. Solids, 44, 771-787.
56. Hirano, K. and Suzuki, T. (1990) Fracture mechanics of functionally gradient materials at
an ultra-high temperature, in Proc. of The First Int 'I. Symp. on FGM'90, (eds. M.
Yamanouchi, M. Koizumi, T. Hirai, and I. Shiota), Sendai, Japan, FGM Forum, Society
for Non-traditional Technology, Tokyo, 313-319.
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57. Hirano, K. (1994) Toughening mechanism for ceramics by a ductile metallic phase, J
Materials Science Letters, 13, 1219-1221.
58. Chan, K. S. (1992) Influence of microstructure on intrinsic and extrinsic toughening in an
alpha-two titanium aluminide alloy, Metal, Trans., 23A, 183-199.
59. Miyamoto, Y. et at. (1992) HIP in SHS technology, Int. J Self-Propagating High-
Temperature Synthesis 1,147-154.
60. Tanihata, K. et at. (1993) Fabrication ofCr3C2INi functionally gradient materials by gas-
pressure combustion sintering, Ceramic Transactions, 34, in Proc.ofThe Second Int 'I.
Symp. on FGM'92, (eds. 1. B. Holt, M. Koizumi, T Hirai, and Z. A. Munir), American
Ceramic Society, Westerville, 361-368.
61. Munz. D. G., Shanon, 1. L., Jr., and Budsey, R. T. (1980) Fracture toughness calculation
from maximum load in four point bend tests of chevron notch specimens, Int. J Fract., 16,
R137-RI41.
62. Williamson, L. R., Rabin, H. B., and Byerly, G. (1993) Residual stress in joint ceramic-
metal structures: FGM studies of interlayer and creep effects, ibid., 3 I 5-322.
63. Kokini, K. and Takeuchi, R. Y. (1994) Initiation of surface cracks in multilayer ceramic
thermal barrier coatings under thermal loads, Material Science and Engineering, A189,
301-309.
64. Blumm, M., Dollmeier, K., and Ilschner, B. (1995) Experimental investigation of fatigue
crack propagation in room temperature bending tests with Cu-Ni graded alloys, in Proc.
The Third Int 'I. Symp. on Structural and Functional Gradient Materials, (eds. B. Ilschner
and N. Cherradi), Presses Polytechniques et Universitaires Romandes, Lausanne, 315-320.
65. Delfosse, D. and Ilschner, B. (1992) Pulvermetallurgische herstellung von
gradientenwerkstoffen, Mat. Wiss und Werkstofflech., 23, 235-240.
66. Shimada, M., Yoshii, T. and Akiyama, S. (1991) Ultrasonic Testing ofThermal Shock
Damage on Plasma Sprayed FGM Coating, in Proc. of4th Domestic Symposium on
FGMs, FGM Forum Japan, 31-35.
67. Nishimori, H., Hayakawa, Y., and Nonaka, T (1991) Nondestructive evaluation of
functionally gradient materials using ultrasound (2), ibid., 53-60.
68. Makino, A., Araki, N., and Ishiguro, T. (1993) Transient temperature response in FGM for
step-or pulsewise heating, Ceramic Transactions, 34, in Proc.ofThe Second Int 'I. Symp.
on FGM'92, (eds. J.B. Holt, M. Koizumi, T Hirai, and Z.A. Munir), American Ceramic
Society, Westerville, 305-312.
69. Saito, M. et at. (1990) Acoustic emission study on stress-induced transformation and
micro fracture in zirconia and metal fiber/zirconia composites, in Proc. of The 10th
International Acoustic Emission Symposium, Sendai, 97-104.
70. Takahashi, H. and Hashida, T. (1990) Development of an evaluation method of
functionally gradient materials, Japan Soc. Mech. Eng., Intern. J, Series I, 33, 281-287.
71. Kawasaki, A. and Watanabe, R. (1988) Powder metallurgical fabrication of the thermal
stress relief-type of functionally gradient materials, in Proc. of Int. Con! on Sintering '87
Tokyo, (eds. S. Somiya et al.. ), Elsevier, London, 2, 1197-1202.
72. Nicholas, G.M. and Crispin, M.R. (1982) Diffusion bonding stainless steel to alumina
using alminium interface, J Mat. Sci., 17,3347-3360.
73. Faber, TK. Huang, D.M., and Evans, G.A. (1981) Quantitative studies of thermal shock
in ceramics based on a novel test technique. JAm. Ceram. Soc., 64, 296-301.
74. Schneider, A.G. and Petzow, G. (1991) Thermal shock testing of ceramics- a new testing
method, JAm. Ceram. Soc., 74, 98-102.
159
75. Watanabe, R. and Kawasaki, A. (1991) Recent development offunctionally gradient

materials for special application to space plane, in Proc. ofSymp. on Composite Materials
ofICAM91, Strasbourg, France, 197-208.
76. Niino, M., Hirai, T., and Watanabe, R. (1987) Functionally gradient material- high
temperature use for space rocket, J Japan Society ofComposite Materials, 13 (6) 257-264.
77. Kawasaki, A. and Watanabe, R. (1987) Finite element analysis of thermal stress of the
metaVceramic multi-layer composites with controlled composition gradients, J Japan Inst.
Metals, 51, 525-529.
78. Kawasaki, A. and Watanabe, R. (1993) Fabrication of disk-shaped functionally gradient
materials by hot pressing and their thermomechanical performance, in Ceramic
Transactions, 34, Proc. of The Second Int'l. Symp. on FGM'92, (eds. lB. Holt, M.
Koizumi, T. Hirai, and Z.A. Munir), Westerville, Am. Ceram. Soc., 157-164.
79. Kawasaki, A. and Watanabe, R. (1992) Thermal shock fracture mechanism of
metaVceramic functionally gradient materials, in Proc. Intern. Workshop on Thermal
Shock and Thermal Fatigue Behavior ofAdvanced Ceramic, Schloss Ringberg, (eds. G.
Petzow and G.A. Schneider), Kluwer Academic Publishers, Netherlands, (1993), 509-520.
80. Watanabe, R., Kawasaki, A., and Takahashi, H. (1991) Mechanics and mechanisms of
damage in composites and multi-materials, ESISII (ed. D. Baptiste), Mechanical
Engineering Publications, London, 285-289.
81. Kawasaki, A. and Watanabe, R. (1990) Microstructural designing and fabrication of disk
shaped functionally gradient material by powder metallurgy, J Japan Soc. Powder and
Powder Metallurgy, 37, 253-256.
82. Watanabe, R. and Kawasaki, A. (1989) The relation between microstructural transition
and material properties in sintered functionally gradient material, in Proc. 3rd Domestic
Symposium on FGMs, Tokyo, Sept., FGM Forum Japan, 35-48.
83. Kawasaki, A. and Watanabe, R. (1997) Concept and PIM fabrication offunctionally
gradient materials, Ceramic International, 23, 73-83.
84. Takahashi, H. and Hashida, T. (1990) Development of an evaluation method for
functionally gradient materials. Japan Soc. Mech. Eng., Intern. J., Series J, 33, 281-287.
85. Takahashi, H. et al. (1994) Oxidation/thermal shock fracture evaluation procedure by
plasma-arc heating for functionally gradient materials, in Proc. 3rd IUMRS Intern.
Conference on Advanced Materials, Tokyo, Japan, Aug. 31-Sept. 4, 16B, 1291-1294.
86. Cherradi, N., Dollmeier, K., and Ilschner, B. (1993) PSZ-chrome nickel graded materials.
Powder Technology-Thermal Properties, 229-236.
87. Kawasaki, A. and Watanabe, R. (1992) Thermal shock fracture mechanism of
metal/ceramic functionally gradient materials, in Proc. Intern. Workshop on Thermal
Shock and Thermal Fatigue Behavior ofAdvanced Ceramic, Schloss Ringberg, (eds. G.
Petzow and G.A. Schneider), Kluwer Academic Publishers, Netherlands, (1993), 509-520.
88. Hashida, T. et at.. (1994) Burner heating method for determining thermal shock resistance
of ceramic coatings for gas turbine rotor blades, in Proc. of 3rd IUMRS Intern. Conference
on Advanced Materials, Tokyo, Japan, Aug. 31-Sept. 4, 16B, 1291-1294.
89. Yanagisawa, N., Sata, N., and Sanada, N. (1990) Fabrication of TiBz-Cu functionally
gradient material by SHS process, ibid., 179-184.
90. Miyamoto, Y. et al. (1990) Gas-pressure combustion sintering of TiC-Ni FGM, ibid., 257-
262.
91. Shimoda, N. et al. (1990) Production of functionally gradient materials by applying low
pressure plasma spray, ibid., 151-156.
92. Uemura, S., Sohda, Y., and Kude, Y. (1990) SiC/C functionally gradient material
prepared by chemical vapor deposition, ibid., 237-242.
160 Chapter 5
93. Kumakawa, A. et al. (1990) Experimental study on thermo-mechanical properties of

FGMs at high heat fluxes, ibid., 291-295.
94. Fujii, K. et al. (1992) Functionally graded material of silicon carbide and carbon as
advanced oxidation-resistance graphite, J Nucl. Mater., 187,204-208.
95. Yamamoto, O. et al. (1993) Preparation of carbon materials with SiC-concentration
gradient by silicon impreg durations and its oxidation behavior, J Eur. Ceram. Soc., 12,
435-440.
96. Kude, Y. (1993) Carbon/carbon composites using high performance carbon fibers, in
Proc. of 4th Symp. on High-Performance Materialsfor Severe Environments, 1-12.
97. Kawai, C., et al. (1990) Oxidation resistant coating with TiC-SiC gradient composition on
carbon fiber reinforced composites by CVD, in Proc. of The First Int 'I. Symp. on FGM'90,
(eds. M. Yamanouchi, M. Koizumi, T. Hirai, and I. Shiota), FGM Forum, Tokyo, Society
for Non-traditional Technology, 77-82.
98. Sasaki, M., Hiratani, T., and Hirai, T. (1993) Corrosion resistance ofan SiClTiC FGM-
coated stainless steel in a Br2-02-Ar atmosphere, in Ceramic Transactions, 34, Proc.
Second Int'l. Symp. on FGM'92, (eds. J.B. Holt, M. Koizumi, T. Hirai, and Z.A. Munir)
American Ceramic Society, Westerville, 369-376.
Chapter 6
PROCESSING AND FABRICATION
Keywords: FGM processing, constructive based processing, transport based processing,

powder metallurgy, powder stacking, sedimentation, fiber stacking, slip
casting, consolidation, sintering, hot pressing, infiltration, solid state sintering,
differential sintering, percolation, pulsed electric current sintering, spark
plasma sintering, plasma activated sintering, liquid phase sintering, hot
isostatic pressing, microwave sintering, reaction sintering, self-propagating
high temperature synthesis, combustion synthesis, underwater-shock
explosion, melt infiltration, laser beam cladding, repair, spray deposition,
spray forming, thermal spraying, electron beam physical vapor deposition,
magnetron sputtering, chemical vapor deposition, reaction layers, transient
liquid phase sintering, electrophoresis, electrodeposition, preform, solid state
diffusion, thermal field, electrical field, PMA(THF) /PVC, SiC/C, PZT,
settling, centrifugal casting, verneuil process, microgravity, solid state joining,
transient liquid phase joining, solid freeform fabrication, CAD, laminated
object manufacturing, stereolithography, selective laser sintering, 3-
dimensional printing, fused deposition modeling, zirconia toughened alumina,
drug delivery device, extrusion freeform fabrication, diffusion bonding, sol-gel
infiltration, superplastic forming.
1. INTRODUCTION
Since the mid-1980s the processing of FGM materials and structures has
become of increasing academic interest. This is reflected in the considerable
number of papers that have been published on specific processing routes.
During the first Japanese FGM program (1987 to 1991) processing methods
were developed for FGM parts to be used as high temperature components
of a hypersonic space plane [1, 2, 3]. These early methods included powder
metallurgy, physical and chemical vapor deposition, plasma spraying, self-
162 Chapter 6
propagating high temperature synthesis (SHS), and galvanoforming (see

Figure 6.1). Since 1991, many variations of the initially used methods as
wel1 as a considerable number of new processing routes have been
developed. Today, the spectrum of processing options ranges from methods
already established before FGMs became a well-defined subject, such as
processing similar to the case-hardening of steel, to more recently developed
methods, such as solid freeform fabrication.
CAD System: Fractal & Percolation Theories:

Inverse design model Quantitative analysis of gradation
Selection of composition &
microstructure
Optimization of gradation Micromechanical Modeling:
Fuzzy function Correlation of graded
microstructures & properties
( Stress Analysis by FEM )
FGM Samples:
Process Developments: Disk: SiC/C, PSZlSUS, PSZlNi,
CVD, PVD, PM, Plasma Spray AIN/SiC,TiC/Ni, Cr3C2/Ni,
SHS, Galvano Forming, TiB2/Ni

CVD/CVI, PM/CVD, SHS/HIP, Nose cone: SiC/CC
PS/GF Rod: PSZJNi, TiB2/Cu
[]
Figure 6.1. Major results of the 1987-1991 FGM research program on the "Fundamental
Study on Relaxation of Thermal Stress for High Temperature Materials by the Tailoring of
Graded Structures" [2].
Published comprehensive reviews on the processing of FGMs approach

the systematic ordering of processing methods in different ways [4, 5, 6]. In
one of these reviews the processing methods are classified into those based
on constructive processing and those based on mass transport [4]. In
constructive processing the FGM is constructed layer-by-Iayer starting with
163
an appropriate distribution of the FGM's constituents, often in a precursor of

the component. These techniques are called constructive processes because
gradients are literally constructed in space. Constructive processes are
distinguished from a second class of FGM processes that depend on natural
transport phenomena such as the flow of a fluid, the diffusion of atomic
species, or the conduction of heat to create gradients within a component [4].
In this book the fabrication of FGMs is categorized into bulk, layer,
preform, and melt processing, as shown in Figure 6.2. The major distinction
made is the object into which the gradient is introduced. Processing to
achieve this objective can include one or more constructive or mass transport
mechanisms, or a combination of these, as well as solid, liquid, or gaseous
aggregation states. Bulk processing utilizes those methods that initially
create a bulk material that has graded porosity, composition, or phase
configuration. This is accomplished largely by forming stacks of powder,
fibers, or even sheets by means of normal gravity, centrifugal forces, or
pressure induced flow. The stacks are then consolidated either by pore
elimination which results in their shrinkage, or infiltration, essentially
without any concomitant shrinkage.
Stacking Stack consolidation

- powder - pore elimination
- fibers - infiltration
- sheets
Molecular Mechanical
c::> deposition
- vapor
deposition
- lamination
- electro - spraying
Diffusion Graded fields
c::> - solid
-liquid
- vapor
- thermal
- electrical
- others
Settling Solidification
Figure 6.2. Processing methods for creating FGMs and their classification in this book.
164 Chapter 6
Layer processing can be achieved by mechanical deposition, which

includes lamination and thermal spraying. It also can be achieved by the
deposition of molecules or atoms as with physical and chemical vapor
deposition, or with mechanisms based on electrotransport or chemical
reaction. Most of the layer deposition methods also can be used to produce
bulk FGMs if adequate time is allocated, or if other specific processing
parameters are applied. In addition, layer processing involves interlayers
that, for example, can be formed by the transient liquid phase bonding of
bulk or sheet components. Preforms can be porous or dense, homogeneous
or inhomogeneous, and mayor may not contain gradients introduced
intentionally.
Preform processing is applied to initiate or to modify existing gradients
in a preform. The conventional processing methods are solid state, liquid
phase, or vapor phase diffusion. Graded fields can be used to introduce the
gradients into the FGM.
Melt processing comprises elements both of constructive processing and
of processing associated with mass transfer. Gradual phase separation under
normal or enhanced gravity can be treated similarly to sedimentation in
particulate processing. Specific solidification methods, such as the Verneuil
(or flame-fusion)6 technique for growing graded single crystals, can be
treated similarly to thermal spraying, and the formation of gradients during
the solidification of melt pools can be regarded as a mechanism dominated
by mass transport.
In Section 7, several advanced manufacturing techniques that include
constructive and transport based processing steps are discussed in detail.
2. BULK PROCESSING
Bulk materials with graded properties, such as porosity, composition,

mechanical response, or chemical reactivity, can be fabricated initially by
bulk processes that include the stacking of powder, fibers, or even sheets
under normal gravity or other enhancing forces. In addition to dry stacking,
sedimentation in aqueous or organic fluids and spray and slurry deposition
can be used. Slurry deposition can be treated as powder stacking if an
arrangement of slurry layers is formed, or as stacking of individual sheets
6 In the Verneuil technique for growing crystals, also known as flame fusion, the powdered
materials are passed through the high temperature flame of an oxyhydrogen torch, where they
are melted, followed by their deposition on the tip of a rod, thereby promoting crystallization.
165
that are initially fabricated by a slurry method (or other processing route).
Powder stacking by pouring, slurry, or spray deposition can be used to
produce thin graded surface layers on graded or ungraded substrates. The
spraying of suspensions is described in this section; thermal spraying is
described in the section on layer processing; and slurry techniques are
described in both of these sections.
Graded stacks are consolidated into components or partially finished
material by methods that produce the desired functional properties. Starting
with a particulate stack, processes such as sintering, hot pressing, or hot
isostatic pressing are used to modify the contact areas between the individual
particles or to modify the pores in bulk materials with residual porosity.
These processes can reduce the porosity, which results in macroscopic
shrinkage of the stacks. The infiltration of porous stacks decreases their
porosity with little attendant shrinkage.
2.1 Powder Stacking
The bulk processing of FGMs by powder stacking, shown in Figure 6.3,

involves the following sequential steps with a selected combination of
metals and ceramics: determination of the optimum distribution of the
composition for effective functioning of the FGM; stepwise or continuous
stacking of premixed powder according to a predesigned spatial distribution
of the composition (the composition profile); and consolidation of the
powder stack [7].
FGM components with a compositional gradient can be readily produced
from powder that consists of at least two powder species with different
chemical compositions. All of the chemical compositions in-between the
chemical compositions of the different unblended powders are considered to
be equivalent to mixtures of the powders with defined volume ratios. To
obtain compositional gradients, two different powders are distributed in the
FGM component in volume ratios with equivalent gradients. The control of
the minimum size of the spatial distribution of the composition depends on
the particle size of the starting powders and on the method of powder
stacking. Layer-by-Iayer stacking enables controlling its size to 0.2 mm [8].
While the spray deposition method enables controlling it to a minimum size
of 0.01 mm [9].
To obtain FGM components with density gradients, a single powder can
be stacked so that the packing density is gradually changed. Alternatively,
mixtures of two or more powders that fill the space differently can be packed
together.
166 Chapter 6
Select powders
V
Add sintering aids for ceramic
Mix intermediate compositions
___ ------L----r----~-
o
o o 0..
o o
o o <+
0. .
o o o
o
Sinter Hot press HIP
Figure 6.3. Flow chart of the processing steps involved in the fabrication of FGMs by
particulate technology [7].
2.1.1 Powder stacking under normal gravity
Materials with unidirectional compositional gradients have been

produced using a wide variety of experimental powder layering techniques.
Scaling up any of these processes for commercialization depends on their
potential for automation. One of the simplest methods, with respect to ease
of reproducibility and minimizing the necessary process control, involves
multilayer powder configurations with a discrete composition in each layer
and stepwise changes in composition from one layer to the next. With
advanced techniques such as thin sheet lamination, shown in Figure 6.4,
layers can be formed from powder slurries 100 to 1500 Ilm thick [10]. A
preform is obtained by removing the organic binders from the layers [11].
In one automated technique for powder stacking under normal gravity, a
suspension is sprayed onto a heated substrate. During the spraying process
the composition of the suspension is continuously changed, and variation in
167
the composition and the spray deposition site are continuously controlled by
a simple computer program. Another computer-controlled method, shown in
Figure 6.5, enables the formation of sheets with a wide variety of
compositional gradients. A powder sieve is positioned above a moving
conveyor belt that transports the substrate. Vibrating the sieve causes a
continuous shower of powder to fall onto the passing conveyor belt. The
thickness of the forming powder stack ranges from zero before the conveyer
belt reaches the vibrating sieve to a maximum when it leaves the area under
the sieve. The compositional gradient of the powder composition in the
plane of the sieve results in gradients in the composition of the sheet
perpendicular to the substrate [12]. This method has been investigated for
fabricating metal strips with a composition at the upper and lower surfaces
of Cu-15Ni-8Sn (in weight %) and a compositional gradient into the interior
of the strip, which consists of pure Cu metal.
1
Ceramics
powder
B'nder Metal
'~:~~~:~~~
Mixing Defoaming Doctor blade
Figure 6.4. Stack formation by a multiple layer technique.
synchronized powder distributor
~A~Y .)\~A'
YL
vibrating ", •.,.v.,.._
C
~~
Wl©lll. lID
----------
graded powder strip
~
powder rolling
+
sintering
Figure 6.5. Schematic of the automated powder stacking apparatus developed for strip
production [II].
168 Chapter 6
In sedimentation processes, a powder or fiber stack is formed after

removal of the liquid. The conventional sedimentation method is based
simply on the force of gravity causing particles with different sizes, shapes,
and densities to settle at different speeds. It is possible to control the
sedimentation rates of different phases almost independently of their relative
particle size or density. Therefore, if the sensitivity to the addition of
agglomerating additives in the solvent is different for particles of different
phases, it should be possible to control agglomeration by the specific
addition of those additives. When the sedimentation process was tested with
a nickel aluminidelalumina (NiAllAh03) powder mixture in a hydrophilic
methanol solution, there was a marked enhancement in the settling speed of
the NiAI due to the presence of aqueous capillary bridges [13].
A variation of this process reduces drying stresses in FGMs [14]. To
prepare a NiAll Ah03 FGM as a sequence of discrete layers with different
compositions, premixed powders for each layer of the composition were
mixed with dry hexane, then ultrasonicated, diluted by water, ultrasonicated
again, and finally allowed to settle in a predetermined sequence using a
perforated plate device mounted on the die of a hot press, shown in Figure
6.6. The die of the hot press was used to avoid any problems with handling
the delicate, layered stack before consolidation by hot pressing. After all the
layers had settled, solvent removal was slowly initiated to allow relaxation
and complete drying. The powder stacks were then hot pressed [15].
2.1.2 Powder stacking under centrifugal forces
Powder stacking under centrifugal forces enables the formation of

structures with continuous or stepwise gradients. It was initially developed
for fabricating experimental samples [16] that were used for processing
highly porous sintered parts with pore size gradients [17]. Either type of
gradient can be obtained by stacking mixtures of powders of different sizes
or shapes or of both. Figure 6.7 shows the setup for centrifugal powder
forming with a unit for proportionally dispensing two different microsized
powders, the filler, and the solid components of the binder. An additional
reservoir contains the liquid component of the binder system, which is
sprayed into a rotating centrifugal cylinder to fix the vertical arrangement of
the stack by reacting with the solid components of the binder.
Stainless steel rings with graded porosity have been made from stainless
steel powder by stacking controlled ratios of two different fractions: a coarse
(40-63 f..l.m) spherical powder and a finer (15 f..l.m) irregular powder. The
powder stacks were debinded and then consolidated by sintering in hydrogen
[17]. The resulting rings had a gradient in their pore size due to the
169
difference in the average size of the powder fractions, and a gradient in their
total porosity due to the difference in the shape of the powders.
;- r-
Stainle ss
[ 0 000000[ D~steeipi ate
Teflon
c olumn~
!tl
,»:
"Ill
,»:
~
')1 ~:
Mo
)(foil
,);
~
~ ~ I
"iJ~ BN
coating
Graphite
foil
Figure 6.6. Settling of powders in the die of a hot press [13].
Vibration supported mixing

and powder transport
Components binder
liQuid
~ CJ:) 83 EB
Proportioning
steps
0 = = Centrifugal
CD CD CD CD
Mixing
Supply
Centrifugal
forming
Cl Metal powder
.. Solid binder
Figure 6.7. Centrifugal powder fonning equipment [15].

170 Chapter 6
Centrifugal powder stacking also can be used to produce graded

tungsten-copper (W-Cu) components [18]. A mixture of Wand Cu powder
with a continuously changing mixing ratio is deposited using a semi-
automated computer controlled feeding system. Because of their relatively
low density, the centrifugally stacked powder cylinders are consolidated by
hot isostatic pressing (HIP). Graded W -Cu components also can be made by
Cu-infiltration ofpresintered W powder stacks with graded porosity.
Centrifugal casting at high rotation speeds can greatly increase the
sedimentation force. After centrifuging cylindrical containers filled with
suspensions of powders of different sizes, shapes, and compositions for
several hours, the supernatant is poured off, and the stacked cylindrical green
bodies are dried and sintered. The settling behavior of the particulates is
controlled by adjusting the pH and by the addition of various stabilizers and
deflocculants. To make it easier to handle the green bodies (unsintered
parts), binders such as polyvinyl acetate (PVA) are added, which also may
prevent cracking during drying. Models have been developed for the
stacking characteristics of complex suspensions [19].
Flat membranes of commercial alumina (Ah03) powders with a graded
pore-size distribution from 40 to 250 nm across a membrane thickness of
about 5 mm can be fabricated by centrifugal casting [20]. A narrower pore-
size distribution with pores no larger than 200 nm can be obtained using
flocculated suspensions, and a graded pore structure is clearly seen in
samples prepared from stabilized suspensions with a solids content of 10
volume %.
2.1.3 Powder stacking under pressure induced flow
Slip casting, a technique used for shaping ceramics, is a typical method

for powder stacking under pressure induced flow. A cavity in a plaster of
Paris mold is filled with a slurry containing particles of a ceramic material.
The slurry liquid is absorbed by the mold through capillary forces and the
ceramic particles, which are generally larger than the capillary channels, are
left behind on the walls of the mold cavity. When a desired wall thickness
has been reached, the excess slip is drained from the mold and the green
body is removed for drying. Repeated slip casting of slurries with different
compositions can be used to produce laminated FGMs.
A schematic of graded casting in which a slip flows continuously through
the mold during the casting step is shown in Figure 6.8 [21]. Other
configurations also have been proposed [22]. The common element is the
presence of several reservoirs containing suspensions of the materials to be
cast. The composition of the slip fed into the mold is controlled to
correspond to the desired composition of the stacks being deposited. The slip
171
is continuously circulated through the mold, and suspensions from the

reservoirs are added by flow pumps at computer-controlled flow rates. The
mixing of the suspensions is enhanced by the use of in-line stationary, spiral-
shaped plastic mixers to create turbulence during the flow through the feed
tubes.
Reservoirs Stirrer
A~ ~~~~LL~
Cast layer
Figure 6.8. Schematic of the process for producing graded materials by slip casting [21].
If appropriate models and data are used for predicting the casting kinetics
for the slip being used, the process can be controlled to produce a specified
compositional gradient [23]. Equations have been developed to predict the
composition of the slip in the recirculating reservoir at any point in time.
This can be done by knowing the initial slip composition in the reservoirs
and how the various parameters such as the flow rate from the reservoirs, the
volume absorption rate of the mold, and the total free volume of the mold,
change as a function of time. These equations can be incorporated into the
process control model.
When designing a mold to produce a part by graded casting, the path that
the slip will follow when traveling through the mold must be taken into
consideration to avoid any zones where the slip is stagnant. To prevent the
formation of lateral compositional gradients, the slip can be injected at
various points along the length of the mold. The slip casting approach can be
used with any material that can be suspended in a suitable liquid. Slips
typically consist of a material in powder form dispersed in a carrier such as
water or an organic liquid. Slip casting has been used conventionally to
manufacture ceramic parts. However, it has been modified recently to a slip
172 Chapter 6
casting-sedimentation process for fabricating graded metal-ceramic

composites [24].
Examples of linear and parabolic changes of compositions produced in
alumina zirconia (Ah03-Zr02) tubes are shown in Figure 6.9. When these
tubes are cooled from the sintering temperature, the alumina-rich surface
area is subjected to compressive stress because of the higher thermal
expansion coefficient of the zirconia-rich inner area. Using the same design
strategy, this process also can be used to produce other ceramic-ceramic
composites such as mullite-zirconia (mullite is an alumina-silica mineral)
[25].
0.9
0 '"
-<'<
<{
c:
0
0.8
U
co
~
Q)
E 0.7
:::I
(5
>
0.6
0.5
0 2 3
Distance from outer surface (mm)
Figure 6.9. Examples of linear and parabolic compositional changes produced in alumina
zirconia composite tubes.
This approach can also be used to produce parts in which the degree of
porosity is graded. For example, bubbles can be introduced by adding
foaming agents to one of the reservoirs. Similarly to other stacking methods,
microstructural gradients can be obtained by the time-controlled addition of
particles or dopants as a second phase. This has been demonstrated with the
addition of zirconia or mullite to alumina. Both retard grain growth in
alumina [26, 27].
In the formation of graded ceramic gears by centrifugal ceramic casting,
a ceramic slurry is poured into a rotating plaster of Paris mold with the
negative shape of the gear [28]. By changing the composition of the slurry, a
173
gear-shaped green (presintered) ceramic body with compositionally graded

layers can be formed. Tough zirconia gears have been fabricated that
incorporate both compositional and morphological gradients from alumina
platelets in the surface layer to fine alumina particles toward the interior.
2.2 Fiber and Sheet Stacking
The most important properties of carbon/carbon (CIC) composites after

their mechanical properties, are their thermal conduction and thermal
expansion. The potential relationships between tailored, graded CIC
composite fiber configurations and their resulting thermophysical properties
have been investigated [29]. Carbon fibers have highly anisotropic
thermophysical properties. The room temperature thermal conductivity of
carbon fibers made by chemical vapor deposition (CVD) can be as high as
2000 W/m·K parallel to the basal plane of the hexagonal graphitic structure
(which is also parallel to the fiber axis), but only 10 W/m·K perpendicular to
the basal plane. The fiber strength is high and the thermal expansion along
the fiber axis is close to zero or even negative, whereas it is positive
perpendicular to the fiber axis. Quasi-isotropic fiber configurations can be
constructed with zero expansion between 20°C and 500°C by means of this
anisotropic thermal expansion effect.
Unidirectional CIC composites made from pitch-based fibers in pitch-
derived carbon matrices maintain an anisotropic thermal conductivity of 700
W/m·K parallel to the fiber bundles. It has been shown that the considerable
contribution of anisotropic thermal conductivity in CIC composites is due to
the anisotropic behavior of the matrix. The matrix crystals tend to grow
epitaxially to the carbon fibers, thereby enhancing the crystallographic
anisotropy within and between fiber bundles. In a three-dimensional CIC
composite fabricated with a total fiber fraction of 55 volume %, 75% of the
fibers are oriented in one direction. This results in up to a fivefold difference
in thermal conductivity between this direction and the other two directions.
FGMs can be produced by laminating or stacking thin sheets with
different compositions, as shown in Figure 6.10 [30]. Mixtures with different
compositions of the starting powders, Zr02 and Ni, are processed into
aqueous slurries containing binder, deflocculant, and plasticizer additives.
Air and excess water are removed in an evaporation step before film casting.
Next the individual sheets are stacked by pressing them together, followed
by drying the stack with slow heating, and then sintering it. The green sheets
are flexible and can be easily formed into various geometries.
174 Chapter 6
<' »
~~W~~I~]~~
Laminating Oebinding
?
Sintering
Figure 6.10. The production of compositionally layered bulk materials by sheet lamination.
2.3 Stack Consolidation by Pore Elimination
2.3.1 Solid state sintering
Besides the usual advantages and disadvantages of consolidating powder

stacks by solid state sintering, there are several challenges to be met for the
successful fabrication of FGMs. In general, with stacked powders that have
different mixing ratios according to a predesigned composition, and with the
desired sample size and shape, the compacting and sintering behavior
normally varies from one layer to the other. If no special measures are taken,
different sintering behavior will cause various localized sintering faults such
as warping, necking, splitting, and crack formation [31]. The sintering
behavior of the different mixing ratios or compositions is characterized by
three parameters of the shrinkage curve: the onset temperature of shrinkage,
the slope of the shrinkage curve as a function of the temperature, and the
integral net shrinkage. In order to control shrinkage, these three parameters
must be taken into consideration [32].
Figure 6.11 a shows an example of the different sintering behavior of
various mixing ratios of stainless steel (SS304) and partially stabilized
zirconia powder. The purpose of controlling sintering is to obtain similar
shrinkage in all areas of the FGM part independent of the green density and
composition of the compact. Among the methods used to control sintering
are varying the particle sizes and introducing temperature gradients. Figure
6.11 b shows an example of sintering control by varying the powder particle
size for the same material systems shown in Figure 6.11a [32]. A similar
approach has been used for powder blends of Mo-AIN (molybdenum-
aluminum nitride) [33], for partially stabilized Zr02-Ni FGMs [34, 35] and
175
for ZrOrNi composites [36]. In the last study, shrinkage was equalized by
using bimodal powders for the Zr02 phase.
PSZlSUS=0.18 ~m/0.09 ~m
25r-r---r---r---r-~~
6. 20 vol% PSZ 6. 20 vol% PSZ
.40 vol% PSZ .40vol% PSZ
20 20
.50 vol% PSZ o 60vol% PSZ
o 60vol% PSZ .80 vol% PSZ
@
Q) Q)
g> 10 g>10
~ ~
c .§
'':::
.t: .t:
(j) 5 (j) 5
Temperature CC)
(b)
Figure 6.11. a and b: Adjustment of sintering shrinkage by controlling the powder particle
size in a mixture of stainless steel 202 and zirconia powder [31].
The addition of small amounts of sintering aids raises the densification

rate during sintering of the ceramic phase in MgOlNi (magnesium
oxide/nickel) and TiClNbAI (titanium carbide/nickel aluminide) FGMs. The
addition of Fe203 (iron oxide) to MgO reduces its sintering temperature close
to that of nickel [37], and the sintering rate of titanium carbide (TiC)
approaches that of NbAI with the addition of chromium carbide (Cr3C2)
[38]. Another way to equalize local sintering rates throughout an FGM is to
densify the powder compact within an appropriate temperature gradient.
This has been successfully accomplished using laser beam surface heating
[39], microwave sintering [40], and pulsed current heating with a stepped or
tapered die [41, 42, 43, 44].
In general, predicting the densification kinetics of an FGM structure
requires an in-depth understanding of the densification behavior of all the
compositions present. Various theories have been proposed to address the
question of control by volume and size ratios. The distribution of the phases
is determined by the volume fraction, the size of the phase, and the wetting
behavior, for example the interface energy values of the boundaries between
176 Chapter 6
phase 1/phase 2, phase 1/phase 1, phase 2/phase 2, and between the solid
phases and the gas phase.
When the interface energies between all the solid phases are
approximately equal, low volume fractions of phase 2 in phase 1 lead to
densification of the composite, which is controlled by the percolating matrix
(phase 1) as long as the size of the microstructures of both phases is similar.
At higher volume fractions, when significant percolation of phase 2 occurs,
densification can change drastically. Above a certain volume fraction, if the
presence of phase 2 dominates, the shrinkage of the composite is accelerated
if phase 2 sinters faster than phase 1. However, if phase 2 sinters much more
slowly than phase I, the percolating phase 2 strongly hinders the
densification of the composite. This relation can be seen in practice when the
size of the particles and the diffusion coefficients of phase 2 result in a zero
sintering rate for this phase. A typical example is a metal-ceramic composite
with a ceramic phase that does not sinter at the normal sintering temperature
of the metal.
The exact volume fraction beyond which percolation of the inclusions
essentially prevents the overall shrinkage of the composite powder compact,
largely depends on the ratio between the size of the matrix powder and the
size of the ceramic inclusions [32]. If the size of the matrix powder is fine,
and the particle size of the ceramic inclusions is coarse, a high volume
fraction of the inclusions is required for direct percolation between the
inclusions. If the particle size of the inclusions is small compared with the
particle size of the matrix powder, a volume fraction of the inclusions as low
as 10% is sufficient to prevent effective sintering of the matrix.
Figure 6.12 shows the volume fraction of equal sized spherical inclusions
of phase 2 above which there is sufficient percolation of this phase to
prevent sintering of the matrix. These values for as-packed green powder
compacts have been combined from both experimental data and calculated
values for various FGMs [45]. These theoretical calculations assume that
the lower limit that prevents densification of the composite is a percolation
in which each inclusion has an average of three contacts with the other
inclusions.
When there is good wetting of the inclusions by the matrix phase, the
interface energy between phase I/phase 2 is much lower than the interface
energies between phase 2/vapor phase and phase 2/phase 2. In this case,
during sintering the matrix (phase 1) spreads in between all the phase 2
inclusions, which results in densification during sintering by rearrangement
[49]. If the size of the inclusions is extremely small, even the presence of a
small volume can suppress the sintering of the percolating phase. Fine
inclusions at the grain boundaries of contacting matrix grains decrease the
ability of the grain boundaries to act as vacancy sources or sinks.
177
0.6 r - - , - - - . . , - - , - - - , 1 .0 r---,......---,----"T----,
c:: • computer simulation
c:: o • experimental data
o
U UJw 0.5
:;::: w 0.8
OUJ •
co ~co
~CO -..c:
-..c:
wOo ~~0.6
~~
::J:=
0.4 15g
OUJ
>- ~Cii 0.4
c::CO
00 00
'(i)::
.~:: 0.3 .20
_0
o
oc:: 0.2
c::
0.21....--..I...---...I...--....l.----1 O.OI....--.l....-_..L.-_..1.-_...J
o 1 2 3 4 0.01 0.1 10 100
Matrix particle radius/ Matrix particle radius!
inclusion radius inclusion radius
(a) (b)
Figure 6.12. (a) Volume fraction of an equisized spherical inclusion phase above which there
is sufficient percolation of this phase to prevent the sintering of the matrix in an as packed
green powder compact ([6.1 [9] after data from [45]). (b) Experimental data for the volume
fraction of the second phase at the onset of percolation, measured in densified FGM
composites produced by powder metallurgy, superimposed on the theoretical curve for (a)
([6.1 [9] after data from [45, 46, 47]).
Pulsed electric current sintering (also called spark plasma sintering or

plasma activated sintering), shown schematically in Figure 6.13, is one of
the more advanced sintering methods. For example, to form graded
structures, cemented carbide powders with different cobalt contents are
stacked into multiple layers on steel in a hot pressing die. This is followed by
the application of pressure via two pistons plus extremely short simultaneous
electric pulses via two electrodes on the upper side of the sample. Thick,
dense cemented carbide layers are formed that are bonded to the steel
without cracking or flaking off [50,51]. The FGM's residual stress properties
can be controlled by supplementing the electric pulses with a temperature
gradient produced by a graphite die with a specifically designed external
shape. The supplementary temperature gradient for homogeneously sintering
an FGM of Zr02ITiAI (zirconia/titanium aluminide) has been experimentally
determined [50]. By appropriate modification of the temperature gradient,
this FGM can be processed to contain residual stresses that are sufficiently
compressive to suppress fracture in its zr0 2 rich regions [51].
178 Chapter 6
Upper
pu nChele~e
+ P
if///'
I"-
Sintering press J
...OJ
.0
E ,.....'-
III
Upper ...0 roo--
...
~
o
f:7777J. v ...
"powt
C) punch iii ~
.5
"8o
OJ
c: ...
(5
OJ 'E
"- }Slntenng die
C)
OJ
0
()
~~ (/)
""5
o<:S
Co
() T
I Positioning I
E ~ 0
::J Lower '-,.....
::J
punch
~
> Operating environment
(Vacuum& argon gas)
v
/ I Water cooling I
Lower
pu nch electrode
31t-- I Thermometer
I
Figure 6.13. The system configuration for pulsed electric current sintering [42].
2.3.2 Liquid phase sintering
During liquid phase sintering, a powder compact is heated to a

temperature at which it is partially melted and a stationary or transient liquid
phase is present. A molten volume fraction is selected that is low enough to
retain the geometry of the compact. In compacts of fine powder « 10 /lm)
the solid particles are rearranged by capillary forces so that the local density
of their packing is higher. In addition, at optimal wetting conditions capillary
forces exert a negative pressure on the liquid phase. If solution
reprecipitation occurs it can cause the adjacent solid particles to conform to
the compact's shape.
Generally, shape conformation causes shrinkage by increasing the
volume fraction of the solid phase per unit volume [52, 53, 54]. Shape
conformation at low volume fractions of the liquid phase refers to the
development of polyhedral shaped grains with rounded corners or edges
from spherical or irregularly shaped particles. It is associated with the
dissolution of the solid phase in the melt, and its reprecipitation at sites with
lower chemical potential. Since grain growth during liquid phase sintering is
179
based on the same principles, shape conformation and grain coarsening are
closely related. In general, the composition of the reprecipitated solid phase
is close to the equilibrium composition. Thus both grain growth and shape
conformation lead to rapid chemical homogenization [55]. Furthermore, the
relaxation of local stresses inhibits the buildup of long range stresses, which
frequently hinders densification during solid state sintering. Liquid phase
sintering is an established processing method for densifying and
homogenizing materials such as the cemented carbide, tungsten carbide-
cobalt (WC-Co), a hard metal; tungsten-nickel-iron (W-Ni-Fe), a heavy
metal; and SIALON ceramics (Si6-zAlzOzNs-z), at moderate temperatures and
small volume fractions of the melt phase.
It is not always easy to retain the functional gradients of graded powder
stacks during liquid phase sintering. In the porous areas, the melt tends to
flow from the areas with larger pores toward those with smaller ones. These
are usually areas with smaller particles or where the density of the compact
is higher [56, 57]. At the same porosity and pore size, the melt is distributed
evenly throughout the compact. This implies that the initial gradients of the
melt forming phase become equalized during sintering. Nevertheless, the
fabrication of graded cemented carbides, particularly WC-Co, by liquid
phase sintering is an established process [58].
2.3.3 Transient liquid phase sintering
By using transient viscous flow sintering mechanisms in ceramic FGM

systems, it is possible to realize the benefits of liquid phase sintering by
avoiding the disadvantages of residual glassy phases. The transient liquid
phase is added intentionally into the system as a chemically deposited thin
coating on each particle of the different starting powders. The presence of
the same amorphous coating surrounding the particles of various
components in a discontinuously graded FGM leads to its simultaneous local
densification at same rates and temperature similar to a non-graded material.
The presence of a viscous phase (i.e. Si02) on the powders prevents solid
state sintering before densification due to the considerable reduction in
densification temperature. Because of the absence of solid state sintering, the
formation of extended rigid regions characterized by solid state bridges
between the particles can be avoided. Further heating following the
densification in the presence of a viscous phase causes extensive phase
reactions between the core particles and the surrounding viscous matrix. By
initially selecting stoichiometric compositions, all the components will fully
crystallize and sinter to dense materials at lower temperatures « 1500°C)
[59].
180 Chapter 6
For example, a mullite/SbN4 (silicon nitride) discontinuously graded

composite was processed with a- Ah03 and a - S bN4 powders that were
initially coated with a Si02 (silica) layer by a sol-gel process [60]. In this
coating process, particles of a-Ah03 and a-SbN4 are dispersed in ethanol
containing a dispersant and surfactants (triethanolamine and polyethylene
glycol) and mixed with tetraethylorthosilane (TEOS) solution. The TEOS,
which is hydrolyzed by addition of a basic aqueous solution (pH> 10),
condenses on each particle as a very thin layer « 50 J,tm). After the
composite is densified, the mullite and the X-phase (Si12Alls039Ns) are
crystallized by a solution and reprecipitation process. The resulting FGM
consists of graded layers of mullite and the X-phase, but not of Ah03 and
Si02, or of Ah03, SbN4, and Si02 as in the starting composition.
2.3.4 Hot pressing and hot isostatic pressing
The undesirable effect of nonuniformity in sintering can be mitigated to a

large extent by using hot pressing or hot isostatic pressing (HIP). External
pressures up to 40 MPa during hot pressing and up to 200 MPa in hot
isostatic pressing produce stress states in particle contact areas that are
almost equivalent to the stresses created by sintering particles that are 50 or
10 nm in size. When the particles are larger, these stresses cause local plastic
flow in the neck areas and, most importantly, lead to the activation of
dislocation-based creep as the major densification mechanism [61, 62].
Densification by this power law creep is essentially independent of the
particle size as long as the dislocation density is not influenced strongly by
the size of the grains or the particles. One of the major benefits of both hot
pressing and hot isostatic pressing is the partial destruction of the long range
stresses, which can be a precondition for the achievement of the crucial
complete densification of FGMs that have local variations in their green
density.
Intermetallic nickel aluminide (NiAI) compounds containing a graded
addition of Cr have been prepared by uniaxially hot pressing a large number
of layers [63]. After blending in a planetary mill, NiAI powder « 44 J,tm in
diameter) containing 2.5, 5, 7.5, 10, and 20 weight % Cr powder « 44 J,tm in
diameter) was stacked in 1.5 mm thick layers, then uniaxially hot pressed.
The final thickness of the consolidated pellets was 4 mm with a few percent
residual porosity. Subsequent homogenization was partially achieved by heat
treatment. In this as well as in other work, the pressure limitations « 60
MPa) in the preparation of hot pressed FGMs often result in residual
porosity [63]. During cooling from the hot pressing temperature, fine crack
patterns can develop in disc shaped samples that have gradients in their
coefficients of thermal expansion. Densification during hot pressing often
181
can be enhanced by small amounts of sintering additives [55]. For example,

adequate densification of the titanium carbide (TiC) rich areas of II-layer
TiClNbAI FGM discs that are 30 mm in diameter and 6 mm thick can be
achieved by the addition of 3 volume % chromium carbide (Cr 3C2 ). After hot
pressing the resulting discs are dense and flaw-free [64].
Hot isostatic pressing (HIP) is of additional value if near-net shaping can
be obtained at the same time. It has been used to fabricate a turbine blade
with a microstructural gradient in the transition region from the base to the
foil by stacking titanium aluminide (TiAI) powder, containing varying
amounts of alloying elements such as Cr, in a HIP can for a turbine blade. In
the base of the can, the powder stack was Cr-free; in the transition region
from the base to the airfoil the Cr content of the powder stack was increased
sharply; and in the airfoil itself the Cr content was uniform. The gradient in
the Cr content produced a predesigned microstructural and mechanical
gradient in the turbine blade [65].
The first step in the fabrication of an FGM turbine blade by HIP is to
form a near net shape steel can by die pressing followed by welding low
carbon steel sheets. The HIP can is filled initially with TiAI powder that
contains an increasing Cr content as described above, then degassed, sealed,
and HIPed. To avoid reaction between the TiAI powder and the steel can, the
HIP temperature is kept below 1 I 50°C. After consolidation, the steel can is
removed by chemical pickling in sulfuric acid, and the near-net-shaped FGM
TiAI blade is machined to final dimensions.
Hot isostatic pressing also has been used to produce tungsten (W)
preforms with graded porosity for further infiltration with another metal such
as molten copper (Cu) [66]. First, a layer of W powder is unidirectionally
cold compacted at high pressure. This is followed by pouring a second layer
of W powder on the compacted first layer, and then compacting the two
layer stack at a lower pressure than the first layer alone. This procedure is
repeated with decreasing pressure to obtain ultimately a compacted six-layer
stack of W powder with graded density. During subsequent sintering the
variations in density are partially retained.
Similar density gradients in sintered stacks of W powder have been
obtained by using stacks of different W powder sizes. When the W layer
with the highest density is sintered to a residual porosity below 8 volume %
all the pores are isolated. This makes it possible to completely eliminate the
pores by containerless HIP (also known as sinter-HIP). The open porosity
that dominates the other layers is unchanged during the containerless HIP
procedure. Using this method, Cu-infiltrated W components have been
produced for the first wall of a fusion reactor in which a pore-free and Cu-
free W surface faces toward the plasma [66].
182 Chapter 6
2.3.5 Microwave sintering
Microwave heating with 2.45 GHz is a pressureless heating method that

provides a "self regulating" heating pattern (thermal gradient) to a heated
bulk material. The thermal gradient is governed by the material's
compositional gradient [67]. Microwave radiation is dissipated as heat
within the volume of a material according to several different mechanisms
[68]. The basic electric and dielectric properties of the material govern both
the penetration depth of the radiation and the conversion efficiency of the
low frequency microwaves.
The heating behavior of a particular material is determined both by the
amount of power dissipated and by the heat loss of the sample due to
radiation or convection. In general, the energy dissipated by dielectric losses
increases markedly with increasing temperature. When the surface of a
material loses heat by convective or radiant heat transfer to the environment,
self-enhancing temperature gradients can develop due to a reduction in the
dissipation of microwave energy at the cooler surface areas. Self-
enhancement is particularly pronounced for materials that have low thermal
conductivity. This thermal gradient could be used intentionally, but then
might lead to a catastrophic "thermal runaway" in the interior of the heated
part.
Graded layered stacks of cubic magnesium-iron-doped nanocrystalline
Zr02, Zr02-Ni, Ni-NiO, and steel can be produced by sequential slip casting
onto porous steel substrates with different porosities. Porosity variations in
the ceramic regions are obtained by the addition of different amounts of
commercial Zr02 powder. After drying and calcining in a vacuum, the
layered stacks are microwave sintered as shown in Figure 6.14, in a single
mode resonant cavity or in a multi-mode cavity, using carbon as the
susceptor material. As shown in Figure 6.15, after pressureless sintering, the
graded layered stacks are crack-free. Efficient heating within the ceramic-
metal mixture at the beginning of the microwave sintering process is
particularly important. Coupling of the microwaves with the surface skins of
the metal particles supplies sufficient local heating to facilitate dielectric
dissipation in the ceramic phase. Compacts of Zr02 or Ah03 powder that do
not contain metallic inclusions cannot be sintered without initial separate
preheating.
In microwave sintering experiments that start with a homogeneous
mixture of Ah03 powder plus 5 weight % Zr02 powder, selective transport
and enrichment of the melt of the eutectic composition containing > 40%
Zr02 results in a substantial enrichment of Zr02 in the interior of the sample.
Microwave sintering of Ah03 powder compacts after preheating produces a
measurable gradient in the grain size from the interior to the periphery [69].
183
/r---- Pyrometer - - - - - . ,
,....----,1 L..I- ______...J L-_~I 1
....__.....
FGM/SGM
VCeramic = VMetal / VCeramic« VMetal

Thermal
Insulation
Figure 6.14. Casketing of samples for microwave sintering experiments: (left) with an
additional metallic heat sink to support a vertical thermal gradient; (right) with a susceptor
composed of porous, laminated carbon-felt or SiC to improve the heating of a small amount
of ceramic phase on top of a metal matrix [69).
c-ZrO:! Ni-Addition Ni+NiO Addition bulk steel
Figure 6.15. An FGM of cubic zirconia-nickel-nickel oxide-steel (c-Zr0 2-Ni-NiO-steel)

microwave sintered.
2.3.6 Reactive powder processing (Combustion processing)
In combustion processes in which two or more phases of a powder stack

or preform react exothermically, the reaction is sustained with the heat that is
released. A combustion wave at high temperatures (up to 4000°C) and speed
(up to 20 cm/s) expands the reaction area [70, 71]. There are three initial
ways that an FGM can be produced by combustion processes [72]. Figure
6.l6 illustrates a general method to fabricate dense FGMs by synthesis from
a graded powder stack. This method has been developed largely by Japanese
researchers [73, 74]. A graded material also can be synthesized from a two-
layered powder stack by controlled impregnation during reactive processing
[75]. In addition, it can be produced from a compositionally homogeneous
184 Chapter 6
powder stack because the high-temperature, multi-component melt allows

the phase separation to be controlled.
D I..---------.,;~
V
Ignition
/" .......
Dense FGM
Compositionally
graded reactant-
powder mixtures
Figure 6.16. A schematic of the combustion process to fabricate dense FGMs.
Combustion synthesis has been used particularly for producing hard

materials such as TiC-Ni, TiB2-Al, and TiB 2-eu; the intermetallics NiAl,
TiNi, and TiAl; and also ceramic composites. Powder compacts can be
heated homogeneously to temperatures at which the synthesis reaction is
initiated. This results in uncontrolled and often multiple self-ignition at
different sites in the compact. This process is referred to as self-ignition or
thermal explosion reactive sintering.
During self propagating high temperature synthesis (also known as SHS)
a powder compact is heated to a temperature below the self-ignition
temperature, and ignition is initiated at one location on the compact. The
self-sustaining reaction then spreads completely through all the unreacted
regions. In most cases, the reaction results in the formation of a liquid, which
densities the compact rapidly. However, in some cases, the combustion is
controlled by reaction with a gas phase that is present, which can affect
densitication. In general, the duration of the reaction is short compared with
sintering. Therefore, the initial concentration gradient in the powder compact
is largely retained. Sharp discontinuities in the concentration gradients in the
initial powder stacks usually are leveled out during reactive sintering.
185
Materials produced by combustion synthesis often are highly porous due

to the evolution of gases, the formation of phases with lower density, or
incomplete densification during transient liquid phase sintering. The
formation of porosity can be suppressed by combining combustion synthesis
with hot pressing in closed dies, with hot isostatic pressing, or with other
methods that exert uniaxial or hydrostatic pressure on the sample during the
reaction.
Despite the success of combustion processing for producing composite
powders, a number of problems are encountered when scaling up this
process to produce FGMs. The control of the combustion temperature must
kept within a range that ensures both achieving the desired densification and
reaction state throughout the FGM part and preventing the unintentional
vaporization of the material. The maximum temperature can be controlled by
the addition of prereacted components that act as diluents for the reactants.
This effect has been demonstrated by the addition of titanium diboride
(TiB2) to the reactants Ti-Ni and Ti-Ni-B [76], and the addition of titanium
carbide (TiC) to the reactant Ti-Ni-C [77]. These diluents also can act as
"passive steric hindrance" for the densification of the compact. Optimization
of the amount of diluents is therefore important to fabricate dense FGMs.
The FGM material combinations that have been prepared by combustion
processing are listed in Table 6.1.
Table 6.1. Various FGMs Produced by Combustion Processes.

FGMs Density-Increase Methods References
TiClNi Hydrostatic pressing 71,72
TiCINi 3AI Hot pressing 73
Cr3CzINi Hydrostatic pressing 74
TiBzINi Hydrostatic pressing 70
TiB2/CU Hydrostatic pressing 68,69,75
Spring-pressurization 76
(MoSiz-SiC)/TiAI Hydrostatic pressing 77
AIz0 3/Cu Centrifugal pressing 78
DiamondlTiB 2-Si Dynamic pressing 79,80
2.3.7 Other stack consolidation processes
Underwater shock explosion has been used to produce stacks of silicon

nitride (SbN4) [87], and also to consolidate a variety of FGMs such as
CulSS304 (stainless steel 304 's composition is 0.08%C, 2%Mn, 1%Si, 18-
20%Cr, 8-10.5%Ni, 0.045%P, 0.03%S, the rest Fe), Ti/TiAI, and
SbN4/SS304 [88]. The experimental apparatus consists of an explosive
charge, a container for the water, and a container for the powder stacks. The
energy of the shock wave increases because of its compression when
186 Chapter 6
traveling from the larger cross-section of the water containment area to the
much smaller cross section of the explosion site and the powder stack
container. Pressures as high as 11 GPa are created for several milliseconds.
3. LAYER PROCESSING
Coating a substrate is a conventional method for protecting it against

oxidation and wear or to decrease the heat flux into the substrate. A coating
layer can also be used to add a functional capability produced by the coating
itself or by the combined effect of both the coating and the substrate.
Additional functions can be obtained with coatings that have electric or
magnetic properties different from those of the substrate. Coatings can also
be designed to have multiple functions. For example, a wear resistant hard
coating can both protect a cutting tool and act as a hard cutting edge. A
metallic bond coating in a thermal barrier system, which produces a
chemical bond between a turbine blade and a zirconia thermal barrier layer,
also can act to protect the superalloy airfoil from oxidation.
Thin layers in the nanometer range are usually deposited by atomistic
transport processes via diffusion in the solid state, the liquid phase, or the
vapor phase; or by convective transport often supported by electric or
magnetic fields. Chemical surface reaction methods such as conventional
surface hardening by carbonization or nitridation result in surface
modification by atomic solid state diffusion transport.
Much higher deposition rates and thus lower costs for producing thicker
coatings are achieved by mechanical deposition processes that include
microlamination, cladding, and spray deposition (e.g., spray forming or
thermal spraying). Layer processing also includes the fabrication of
interlayers for the transient liquid phase bonding of bulk and sheet
components. Thin solid or liquid reaction layers also can form due to
interdiffusion when two bulk materials with different compositions are
brought into contact. The gradients can be broad or narrow depending on the
system and the processing parameters. Short processing times produce
transition layers. Prolonged processing times can result in the formation of
graded bulk materials.
In the subsequent sections, the fabrication of thick coatings by cladding,
spray forming, and thermal spraying is discussed. Deposition processes
based on atomistic transport are categorized into those based on vapor
transport, such as physical and chemical vapor deposition; on diffusion in
the solid or liquid states; and on electromigration processes.
187
3.1 Cladding
In surface engineering, laser beams are used as a high intensity heat

source for hardening, alloying, and cladding. The characteristic features of
laser processes are high localized heating and cooling rates, short interaction
times between the heated materials and their surroundings, and a very low
integral heat input [89]. Laser cladding has been applied largely to steel
substrates using high power CO2 lasers and conventional hardfacing
materials, such as NiCrBSi; the Co-based superalloy, Stellite® (Co-28Cr-
4W-3Ni-lC); and WC-Co. More recently, a wider range of materials has
been clad successfully, for example, oxide ceramics on steel and aluminum
substrates, and composite claddings containing diamonds and other hard
particles that can be damaged by heat. The composites have been obtained
by using solid state Nd:Y AG lasers that make it possible to improve the
control of the cladding process at low intensities. In laser cladding processes
the powder can be predeposited, or more commonly it is fed continuously
into a melt pool on the surface of the substrate. The melt pool is generated
and maintained through interaction with the laser beam. It forms a cladding
track after solidification as the substrate is scanned relative to the beam, as
shown in Figure 6.17.
Laser beam
stream
Relative movement
~
Figure 6.17. A schematic of the laser beam cladding process [89].
Solid freeform processes that use a laser require precision powder fed
cladding. For example, Nd:Y AG lasers that allow the laser energy to be
delivered by an optical fiber have a much simpler but more highly flexible
188 Chapter 6
laser beam guiding system. The use of this system produces good results
both with graded coatings and with 3-dimensional contouring using a robot.
With this process, thin, graded multilayer claddings are obtained using
predeposited powder, thereby suppressing melt pool convection through
buoyancy forces [90].
Figure 6.18 shows the variations of the microstructure, the concentration
of the elements, and the hardness throughout the four layers (each about 200
J!m thick) of a NiCrBSi alloy cladding with increasing Cr3C2 content (0, 10,
30, and 50 volume %), deposited on a steel substrate using the powder feed
process. The carbide distribution within each layer is relatively
homogeneous. The final 0.8 mm thick coating, which contains only a small
amount of residual porosity, has a surface roughness of RZ,ISO = 30 to 35 J!m
and a maximum Vickers hardness of 800 HV [89].
3.2 Spray Deposition
3.2.1 Spray forming
Spray forming, shown schematically in Figure. 6.19, combines several

techniques from other fabrication methods such as powder metallurgy and
rapid quenching. Initially, a metallic melt is atomized into a spray of fine
droplets, typically between 10 and 150 J!m. When these droplets solidify in
free flight or remain individual particles after impinging on the spray
chamber walls, the resulting powder is used as starting material for
subsequent powder metallurgical processing. When the spray of fine droplets
is directed toward a mandrel or a substrate, and if the droplets are still in a
partially liquid state at the moment of impingement, the process is referred to
as spray forming [91]. The gaseous atomizing medium, e.g., Ar or N 2,
usually is unreactive with the metal being atomized. Thick plates or bars can
be formed on the substrate by continued spray deposition [92].
Spray forming can be used to produce both monolithic and composite
materials. For composites, fine reinforcement particles, such as SiC or
A1 20 3, are added either to the initial metal or to the spray. By changing the
deposition parameters, the amount of dendrites that form before the droplets
impinge, the grain size, and other microstructural features can be tailored to
produce an FGM. Similarly, continuously varying the quantity, and
ultimately the quality, of the reinforcing particles added to the spray can
produce well-designed FGM structures. Because spray forming is still a
developmental method and experiments are costly to perform, little work in
producing FGMs has been done to date. With respect to their relative rates of
production, spray forming is considerably faster than either plasma or flame
189
spraying. Materials that can be spray formed successfully are limited to

those that are relatively unreactive, can be melted, and cannot be dissociated.
(a)
~ 100~-----,------~----~----~r---------,
:l
.!:!.
c: 80
o
~
C 80
8
§ 40
()
CQ)
E
Q)
ill O~--~~-===~~~~~--~~--~--~
(b)
900r------,------~----_r----,_----------,
o~ 800
>
J:
700
';;;'600
III
Q) 500
c:
'E 400
IU
J: 300
~
Q) 200
5""" 100
O~----~----~--~~--~----~----~
o 200 400 600 800 1000 1200
Distance from Surface [lJm]
(c)
Figure 6.18. a) Microstructural section of a four-layer cladding ofNiCrBSi graded by varying

the Cr3C2 content. b) Concentration profile ofNi, Cr, and Fe. c) Gradient in the Vickers
hardness [89].
190 Chapter 6
3.2.2 Thermal spraying
In thermal spraying, feedstock (in the form of powder, rods, or wire) is

introduced into a combustion plasma or other heat sources, such as arcs or
laser beams. Arc spray methods use electrically conductive wire as
feedstock, while combustion methods use powder or wire. Powders are used
for plasma or laser beam spraying. The particles melt in transit and impinge
the substrate where they flatten, undergo rapid solidification, and form a
deposit through successive impingement. Thermal spraying is used largely to
produce metal, ceramic, or polymer protective coatings, but it is also used to
form bulk ceramics [93]. The relatively high porosity of FGMs should be
taken into consideration when fabricating them by thermal spraying [94].
1.METAL . -Overpressure
DELIVERY
, Induction power
2.ATOMIZATION
~ iii,..------
r.. pr_ure
3.TRANSFER
OF DROPLETS
State of the top surface
4.CONSOLIDATION
- - Spray height
5.PREFORM
_ _ _ Substrate motion
Figure 6.19. A schematic of spray forming [92].
The majority of plasma spray torches are gas stabilized. The plasma
originates within a gas that acts to form and sustain a flame. These torches
generally operate for extended periods of time at 30 to 40 kW, and have a
material throughput of 2 to 5 kg/h. Low pressure plasma spraying, shown in
Figure 6.20, is usually conducted in a low pressure inert gas filled chamber
191
[95]. It has extended the capabilities of the deposition process to reactive

metals and intermetallics. The higher particle velocities of low pressure
plasma spraying compared with air pressure plasma spraying, deposit oxide
free metallic coatings with low porosity for applications such as oxidation
resistant protective coatings on turbine airfoils and other high pressure
turbine parts [96].
Plasma control
_. _.. _.. _. - _. _.. _. _.. _. _.. _ ....
console
t--~--r----r--r
®®®®
,
............. --- .. --.
' - - - -
Ii Ii Ii Ii
r - - - -, - - - - - - - -:- I
:.-
, I t9 Torc,h
Torch motion
'~-1\ ~(\
: I
.-----+--, controller
Arc/Powder gas
UUU
.------i8 Normal
power
EB supply
tC;>. Reversing
transfer Arc
I(]:I
...--_ _ _ _+-_ _ _ _ _ _--; tfi:>. power
'6' supply
Mandrel - C:=::::;:~=~==1
I Deposit motion controller
Rotation/Transiation
"-----------
/
Envi ronmental
Heat
exchanger
Filter
chamber
Figure 6.20. A schematic oflow pressure plasma spray forming [95].
Plasma spraying is a favorable processing method for functionally graded

materials because highly refractory phases can be melted simultaneously
with a metal, blending the two in ratios that can be predetermined by
controlling the relative feed rates of the two powdered materials. Since the
192 Chapter 6
deposit is formed through the sequential buildup of layers, several

approaches can be used to produce a graded deposit. These can be broadly
classified as single torch multiple feeders for blended or composite powders;
mUltiple torch independent feeding systems for each component; and
combinations of wire/powder feed systems.
A basic requirement for fabricating FGMs is that dissimilar materials
(e.g., a metal and a ceramic with large differences in their densities and
melting points) are homogeneously mixed in the desired proportions in the
planes non!lal to the thickness direction. In addition, the desired
compositional pattern should be achieved with good reproducibility in the
direction of the heat flow.
Considerable experimental work has been done on fabricating FGMs by
plasma spraying. In the early stage of the development of graded spray
coatings, FGMs of YSZlNiCrAIY (yttria partially stabilized zirconialnickel-
chromium-aluminum-yttrium) were produced on steel by air plasma
spraying [97, 98]. An example of an FGM produced by low pressure plasma
spraying is the fabrication of YSZlNiCr with a four-port plasma torch
operating in a chamber in which ceramic and metal powders are
simultaneously introduced into the plasma flame, shown in Figure 6.21 [99].
Identical types of powders are delivered through diametrically opposed ports
so that the dissimilar particle mixture is uniformly distributed in the flame
while maintaining the necessary axial symmetry with respect to the axis of
the torch. High density coatings are produced at high deposition rates when
the average particle size is 57 ~m. When this system is programmed for a
PSZlNiCr powder feed ratio, and automatically sprayed according to the
program, the FGM composition can be controlled with sufficient accuracy to
meet the requirements for the coating. Figure 6.22 shows a cross sectional
view of a graded PSZlNiCr coating on a stainless steel substrate [100].
The characteristic solidification patterns of these FGM coatings, with
columnar microstructures in the single-phase regions normal to the substrate
of both the NiCr and the PSZ, can be seen in transmission electron
micrographs. This is a typical feature of plasma sprayed microstructures
formed by the deposition of droplets with a high ratio of melt to solid [100].
The microstructure is transformed into more equiaxed grains if the NiCr
droplets coalesce at a slower cooling rate. This can occur if the local heat
source is shielded by the presence of a high volume fraction of the Zr02
phase, which has a low thermal conductivity of about 2 W/m·K.
Depending on processing parameters such as particle size, environmental
pressure, and the distance between the torch and the substrate, the porosity
of plasma sprayed layers can range from as little as a few percent to 20
percent. This makes it possible to introduce porosity gradients into plasma
sprayed layers [101].
193
Current
I
Plasma gas
I
Ceramic
(through 2
ports)
-to ~_M.ml
[] (through 2
ports)
j
~
, Coating
Substrate
Figure 6.21. A low pressure plasma torch with multiple feeding ports for metal and ceramic
powders [99].
NiCr
O-O-~.
. ..
. ::. 4," . 0' , .. .... 100 !1Il1
Figure 6.22. Cross sectional transition electron micrograph of a low pressure plasma sprayed
PSZI NiCr FGM coating [99].
194 Chapter 6
A laser beam is another heat source for thermal spraying. When powder
mixtures of Al with 10, 30, and 50 weight % SiC are directed into a 2kW
continuous wave CO 2 laser beam focused on an Inconel 625 (Fe-Ni base
superalloy) substrate, a graded multilayer structure is formed [90].
3.3 Physical Vapor Deposition
3.3.1 Electron beam - physical vapor deposition
Electron beam-physical vapor deposition (EB-PVD) is a promlsmg

technology for the production of thermal barrier coatings. Among the
advantageous features of EB-PVD are that the coatings produced have
smooth surfaces without requiring additional polishing; they have good
erosion resistance in service; and there is no closure of cooling holes.
However, the most important advantage is their outstanding thermal shock
resistance, thus considerably longer life, which is related to their columnar
microstructure. The state-of-the-art-material for thermal barrier coatings is
Zr02 stabilized with 6-8 weight % Y203 (YSZ), which is composed of the
non-transformable tetragonal t'-phase [102]. The equipment used for
depositing thermal barrier coatings via EB-PVD, shown in Figure 6.23,
consists of several containers for loading, preheating, and deposition plus a
device for rotating and manipulating the samples. In order to ensure
continuous deposition, ingots of the metallic or ceramic coating material are
fed into crucibles below a deposition vessel. Evaporation of the coating
materials is achieved by the application of high-energy electron beams (150
kW and higher). Vaporization during EB-PVD depends on the vapor
pressure of each compound. This makes it difficult to evaporate materials
simultaneously that have large differences in their vapor pressures (e.g.,
Zr02 and Ce02).
Using a single source coater only certain chemical gradients have been
produced successfully, such as density graded YSZ and chemically graded
bond coats [102, 103]. Another approach to obtain a graded structure is to
use a mixture of aluminum, alumina, and zirconia as the starting composition
in the form of pressed tablets on top of YSZ ingots [104]. Chemically
controlled graded coatings can be fabricated readily by vaporizing from
multiple sources using one or more electron guns. By adjusting the electron
beam parameters, different deposition rates can be obtained for each source
by independently adjusting the temperature of the melt pool. If the
evaporation rates of two components, for example alumina and zirconia, are
changed continuously, a defined gradient of the composition over the coating
thickness is obtained
195
Because of the different deposition conditions that are required to

maintain adequate evaporation of the alumina, the zirconia, and their various
mixtures, the substrate temperature increases with increasing zirconia
content in the vapor cloud. Initially, a thin, pure layer of alumina is
deposited on top of a NiCoCrAlY bond coat, followed by compositionally
graded aluminalYSZ layers, and topped with pure YSZ. The formation of a
continuous chemical gradient can be seen in Figure 6.24 [105]. (For clarity,
the graded layer is shown as a fractured cross section.) Although there is still
a discontinuity in the gray scale of the scanning electron micrograph in
Figure 6.24, the spatial distribution of the concentration shows only a
slightly steeper change in the concentration in this area.
Electron gun
Jumping electron beam
--
Alumina
vapor cloud
~ ~ Zirconia
vapor cloud
Crucible
PYSZ-ingot
Figure 6.23. A schematic of an electron beam - physical vapor deposition coater with two
evaporation sources heated by a single jumping beam [105].
Experiments indicate that dual-source EB-PVD can produce a discrete

graded layer even though only one electron-beam gun is used. The
application of jumping beam technology for ceramics requires a fast beam
deflection system capable of beam scanning frequencies up to 1 kHz. The
key to reproducible evaporation behavior is to adjust the beam pattern and
the beam focus for the different ceramics. This can be difficult to accomplish
196 Chapter 6
because zirconia requires two to three times more energy for evaporation
than alumina, but the beam power cannot be changed quickly during the
jumping procedure.
70 lr
60
~ 50
~
c
;
.2 40
QI 30
!!
8 20
10
1 2 3 4 5
distance
Figure 6.24. Distribution of the elements (above) and fractograph (below) of a graded
alumina-yttria stabilized zirconia (Ah03- YSZ) coating. [105].
3.3.2 Sputtering
Sputtering is commonly used for depositing thin films for applications in

microelectronics, optics, energy generation, and mechanical and chemical
engineering. The almost unlimited selection of substrates and coating
materials includes plastics, metals, and ceramics for the substrates, and
metals and ceramics for the coatings.
197
The principle of the sputtering process is illustrated in Figure 6.25. The

deposition process is generally carried out in a vacuum chamber that is
evacuated and refilled with an inert gas, usually argon, at from 10 to 10- 1 Pa.
For coating deposition, a high voltage is applied to both electrodes. (The
target material is on the cathode.) The high voltage ionizes part of the inert
gas producing a plasma. Because of the specific polarization, the inert gas
ions are accelerated toward the target material and bombard its surface.
When the energy of the impinging ions exceeds the binding energy of the
target atoms, the target surface is sputtered. As shown on Figure 6.25, the
ejected target atoms deposit on the substrate to form the coating. In many
industrial applications, an additional magnet system is used to obtain higher
deposition rates. In reactive sputtering, an element from the process gas is
also incorporated into the coating. For example, titanium nitride (TiN)
coatings for the wear protection of tools are produced by sputtering a pure Ti
target in an Ar-N2 atmosphere.
l
....------<0 Power suppl y
Magnet-
system ~~~l1~arg~et~(c~
......
~.kArgon ion
a ~Q
Q
4 - Target atom
S Q ~ ~. V Electron
s-
~ ~ Q
o 0 0 De-coaling
&Jbs trate
Figure 6.25. A schematic of magnetron sputtering [109].
The various sputtering processes for the deposition of single- and

multilayered coating systems by using single andlor multi-source equipment
is versatile state-of-the-art technology that is widely used in industrial
applications. However, there are only a few applications for graded coatings.
Surgical implants made of the titanium alloy Ti-6AI-4V are coated with
compositionally graded TiN films by reactive DC (direct current) sputtering
to improve the implant's biocompatibility and to relax the stresses
concentrated at the interface between the alloy and the coating [106]. For
this application, the nitrogen partial pressure of the Ar-N 2 gas mixture is
continuously increased during deposition in order to vary the composition
198 Chapter 6
from metallic titanium at the interface of the alloy and the coating to
stoichiometric TiN at the coating's outer surface.
Another application of graded sputtered coatings is for protecting high
temperature materials against oxidation. Molybdenum can be protected with
a functionally graded coating of MoSh + SiC (molybdenum disilicide +
silicon carbide), which is deposited by RF (radio frequency) magnetron
sputtering from a composite target. The compositional gradient in the
coating is achieved by varying two of the deposition parameters: the applied
power and the argon pressure [107]. For obtaining large compositional
changes in the coating, co-sputtering is more effective than varying the
deposition parameters.
Intermetallic titanium aluminide (TiAI) coatings for the oxidation
protection of titanium alloys can be produced by co-sputtering Ti and Al
from different sputtering sources [108]. By modifying the applied power for
each source, the composition of the coating theoretically can be varied from
o to 100% of either Ti or Al or both. For this application, the composition is
continuously varied from 25% Al at the substrate coating interface to 75%
Al at the outermost surface, as shown in Figure 6.26. This compositionally
graded coating, which was designed both to minimize interdiffusion and
stresses between the substrate and the coating and to provide maximum
oxidation protection, has excellent oxidation resistance under cyclic and
isothermal conditions [109]. Graded TiAI coatings also have high
mechanical performance under cyclic loading [110].
100
<ll
0~ '§
::i. 80 (jj
.c
c: ~
.g (f)
'w
0
60
a.
E
0
u 40
cuu
'E 20
<ll
.I::.
()
0
25
Distance [11m]
Figure 6.26. Graded Ti-AI coatings for the oxidation protection of titanium alloys: a)
schematic and b) EDX profile of the graded coating [110].
199
3.4 Chemical Vapor Deposition
In chemical vapor deposition (CVD), shown schematically in Figure

6.27, a deposit is formed on a substrate by subjecting source gases (e.g.,
hydrides, bromides, or chlorides) that fill the reaction chamber, to various
types of energy such as heat, light, and plasma [111]. FGMs can be
synthesized at slow to moderate deposition rates by changing the ratio of the
source gas mixture, or by controlling the deposition temperature, the gas
pressure, or the gas flow rate. Because of its slow deposition rate, CVD is
largely used for infiltrating stacks or preforms, or for the fabrication of thin
layers.
Ribbon heater Pressure regulator
\
----
- -
-, Water-<:ooled
reaction
-I I
I I chamber
II
II
II
. II Wort<. coil
Constant reservor I I ~
I 0
temperature bath L - I 0
- I
Mass flowmeter I I 0
~ I 0 o
I I Pressure
I I gauge
II
II
: ~ _______ j Pump
I.!; - - - - - - - - -I Pressure regulatcr
Figure 6.27. A schematic of the setup for the preparation ofa SiC/C FGM by chemical vapor
deposition [111].
A typical example of an FGM application of CVD is the formation of a

graded SiC coating on graphite in which there is a continuous transition from
SiC to C. Compositionally controlled source gas mixtures of
tetrachlorosilane-methane-hydrogen (SiCI4 -CRt-H2) are used at deposition
temperatures between 1400°C and 1500°C and pressures between 1.3 and 6.5
kPa. The computer controlled variation of the SiCI 4 /CH4 gas ratio controls
the change in the SiC/C deposition ratio with time. Graphite substrates with
FGM coatings of SiC/C between 200 and 800 /lm thick are shown in Figure
6.28 [112].
Similarly, graded coatings of zirconium carbide/carbon (ZrC/C) on a C/C
composite can be deposited from gaseous mixtures of zirconium chloride-
methane-hydrogen (ZrCI 4 -CH4-H2) at temperatures between 1400°C and
200 Chapter 6
1600°C [113]. Other FGM protective coatings that have been deposited by
CVD on C/C composites are boron nitride/silicon nitride (BN/SbN 4) and
carbon/boron carbide/silicon carbide (C/B 4c/SiC) [114]. In addition, FGM
films of 1 mm thick titanium carbide/carbon (TiC/C) have been deposited to
protect materials facing the plasma in fusion reactors.
Diamond is a useful material both for electrical components and machine
tools because of its extreme hardness, thermal conductivity, and chemical
and thermal stability. In a novel CVD process developed specifically to
fabricate a diamond/WC FGM, plasma spraying is combined with the
simultaneous synthesis of a diamond film by DC plasma jet CVD using a
single torch apparatus, shown in Figure 6.29 [115]. Graded intermediate
layers are formed by controlled feeding of powdered WC using hydrogen as
the plasma gas. The intermediate layers improve the normally poor adhesion
of diamond films due to their low thermal expansion coefficient, high
deposition temperature, and high elastic modulus. These properties of
diamond films cause high thermal stresses to develop at the interface
between the diamond film and the substrate.
SiC/C graded zone
, 0.1 mm ,
Figure 6.28. Cross-sectional view of the microstructure of a SiC/C FGM prepared by

chemical vapor deposition at 1500°C and 1.3 kPa [Ill].
201
H2 + CH4
He + Powi,er -0 . - - - - -1
Substrate
holder
Substrate
III \\
/1 \
Figure 6.29. A schematic of the single torch apparatus specifically developed for the
deposition of a diamond/metal FGM [113].
As shown in Figure 6.30, the intermediate layers, which are composed of

a mixture of diamond and metal or ceramic, produce a composition gradient
from the plasma sprayed layer to the diamond film. The composition
gradient causes a continuous change in the thermal expansion coefficient of
the intermediate layers thereby effectively relaxing thermal stresses and
improving the adhesion strength tenfold.
Diamond is synthesized by feeding a mixture of hydrogen and methane
between the two electrodes of a plasma gas initiated by a DC arc discharge.
A composite with a diamond matrix and WC particles is produced by
feeding WC powders to the plasma torch at the same time as the He carrier
gas. The graded diamond film is formed by first depositing a plasma sprayed
layer using only hydrogen as the plasma gas. Methane is then added to the
plasma gas, and the feed rate of the WC powders is gradually reduced. In the
last step, only diamond is deposited without feeding any powder.
3.5 Chemical Reaction
An FGM can be produced by a chemical reaction on the surface of a

material. For example, a C/SiC FGM can be formed on the surface of a
carbon material by heating it in Si powder at 1450°C for 3 hours [116]. Also
joining similar or dissimilar materials with thin sheets of a different material
202 Chapter 6
inserted between them frequently results in the creation of new phases in the
joining area [117, 118].
Figure 6. 30. Scanning electron micrograph and the compositional distribution of an FGM
diamond film [114].
3.6 Constructive Deposition by Electrotransport
3.6.1 Electrodeposition
An electrodeposition method can be used to form a Cu-Ni FGM with a

controlled concentration gradient in which up to 30 volume % of fine (lJ.lm)
Ab03 powder is incorporated in the deposited Cu-Ni [119]. The volume
fraction of AhO 3 particles incorporated in the Ni- Cu-Ah03 structure is
controlled by the particle content in the liquid electrolyte [120].
Electrolyte jet streams directed onto the substrate have proven to be
beneficial for enhancing the deposition of compositionally graded layers.
They enable the deposition at high rates of metallic materials such as nickel-
phosphorus (Ni-P) alloys because of an increase in the limiting current
density [121]. When SiC or Ah03 particles are added to the jet, their volume
203
fraction in the deposit changes with the jet velocity, while at the same time
the P content is controlled by jet polishing.
As the velocity of the jets increases between 0.5 and 16 mis, the volume
fraction of electrodeposited SiC particles decreases from 30 to 0 volume %.
The mechanism of codeposition via jet electroplating is explained in the
following way. Nickel hydration ions in the form of anion clusters are
present on the surface of the SiC particles in the electrolyte. The SiC
particles enveloped by the nickel hydration anions are transferred
energetically to the surface of the cathode by the electrolyte jet. Following
their dehydration and reduction, the nickel hydration ions adsorbed on the
SiC particles become nickel atoms immediately adjacent to the cathode
surface. The particles now behave differently in that they directly contact the
cathode surface and are simultaneously covered with crystallizing nickel.
Figure 6.31 shows the microhardness and X-ray intensity of an
electrodeposited Ni FGM with a compositional gradient of SiC particles.
~~--~----~--~----~~950
u;-
900 N
0
ci
?;:
::I:
~ ui
'ecn 850
(fJ
Q)
c
C
Q)
...
"0
ctj
..c
...0
I:)
800 ~
~~~~--~----~---L~750
o 10 20 30 40
Distance from interface, ds/).lm
Figure 6.31. The microhardness and X-ray intensity of an electrodeposited Ni FGM with a
compositional gradient of SiC-particles [121].
204 Chapter 6
3.6.2 Electrophoresis
Electrophoretic deposition is a colloidal process in which on the

application of a DC electric field particles are deposited from a stable
suspension onto a shaped electrode that has an opposite charge, shown
schematically in Figure 6.32. Recently, electrophoretic deposition has been
applied to fabricating composites and micro laminar ceramics [122 -124],
nonplanar laminates [125], fiber composites [126], and FGMs [123, 127,
128]. The deposition rate is controlled by the deposition current density and
the concentration of the particles in the suspension .
• ~
•• •
4 •
---e· •
• •
Figure 6.32. A schematic of an electrophoretic deposition cell showing the process [128).
The mechanism for electrophoretic deposition is still in question. One

that has been proposed recently is the distortion of the spatial symmetry of
the double layer (diffuse-double-layer or lyosphere) that forms around
particles when submerged in a liquid. Oxide surfaces, for example, can be
considered to undergo the following reactions to produce either H+ or OH-:
205
(at low pH)
and
(M-OHtsurface + OR === (M-Orsurface + H20 (at high pH)
Such a system could be an oxide particle with a first layer that is

positively charged and a second, more extended, deformable layer of
negatively charged ions. The overall double layer can still be positive. An
electric field makes the particle with its double layer system move toward
the negative electrode (cathode) where it is deposited after discharging.
(Coagulation can have a marked effect on the process.) Due to the migration,
the double layer becomes polarized. This implies that the thinning of the
negatively charged second layer occurs in the migration direction of the
system. All the oxide particles show this polarization, and the particles with
bipolar double layers coagulate throughout the suspension. The coagUlation
reverses when the electric field is removed. However, it can become
irreversible if there is sufficient asymmetric thinning of the double layers for
van der Waals interaction between the particles
FGMs with a continuous or stepwise transition from Ah03 to YSZ,
AhOiMoSi 2, Ab03INi, and YSZINi all have been prepared by
electrophoretic deposition. The gradient is obtained by a stepwise or
continuous change in the concentration of Ab03, YSZ, MoSb, or Ni
particles in the suspension during deposition. Laminated and graded
Ah03/Zr02 ceramics have been fabricated from ethanol suspensions at a pH
of 3.5. Both suspensions are stable and positively charged at this highly
acidic pH. After drying the deposits were sintered.
Figure 6.33 is a micrograph of an FGM about 4 mm thick composed of
six layers in 20 volume % steps. The Ab03 (dark phase) and YSZ (light
phase) phases are homogeneously distributed throughout the microstructure.
The end composed of pure Ah03 has an average grain size of 6 11m that
reduces to 2 11m in the 80 volume % layer. The sharp interface between the
layers, which has an irregularity roughly corresponding to the scale of the
grain sizes, is clearly visible in the microstructure.
The experimental set-up for the electrophoretic deposition of FGMs with
continuously graded compositions is shown in Figure 6.34. The deposition
starts when a Zr02 suspension and an Ab03 suspension are slowly injected
using a syringe pump into the bottom of the electrophoretic bath where they
become mixed (the mixing area is shielded from the deposit). The spatial
distribution of the composition (composition profile) of the Ah03 can be
precisely controlled via the deposition current density, the rate of pumping
of the Ah03 suspension, and the concentration ofthe suspension.
206 Chapter 6
Figure 6.33. The scanning electron micrograph microstructures of a step-graded Al 2 0 3IYSZ

FGM. The dark phase is Al 2 0 3 and the light phase is YSZ [\28].
207
Figure 6.34. The experimental set up for the synthesis of ceramic/ceramic and ceramic/metal
FGMs with continuously graded compositions [128].
4. PREFORM PROCESSING
Stacks or other preforms that do not contain gradients initially can be

graded using preform processing. In addition, preform processing can be
used to enhance or reduce the gradients of graded preforms. The preforms
can be porous or dense, or may even consist of an arrangement of bulk
materials or layers that is itself homogeneous thus would not be considered
anFGM.
Most of the methods of preform processing are based on the traditional
transport mechanisms used to create gradients in materials. Heat and mass
diffusion, for example, have been used for centuries to create functional,
microstructural and/or compositional gradients in steel. A second group of
methods is based on the application of external, largely stationary, fields. For
example, thermal gradients can be applied to sinter porous preforms to
different local densities, and electrical fields can produce a graded porosity
when a porous preform is electrolytically dissolved.
208 Chapter 6
4.1 Solid State and Liquid Phase Diffusion
When diffusion couples with different compositions are heated,

interdiffusion can create gradients. These gradients are obvious in solid
solutions, but are also present to a widely varying degree in intermetallic
compounds formed as reaction products during interdiffusion. Solid state
diffusion methods have been used frequently to fabricate FGMs.
During annealing at about 2000°C, solid solution gradients are formed
between a rhenium (Re) layer and a molybdenum (Mo) layer that have been
deposited by chemical vapor deposition (CVD). Inserting a thin tungsten
(W) layer between the Re and Mo layers reduces the interdiffusion between
the Re and Mo [129]. When diffusion couples of Cu-lO weight % Sn (tin)
and AI-0.5 weight % Sn are heated at 500°C, four intermetallic compounds
develop based on Cu-AI.
In alumina (Ah03) uniformly doped with Ti, a dopant gradient is
developed during sintering in a carefully controlled atmosphere [130]. When
compacts of high-purity Ah03 powder that either are not doped, or are
doped with 500 ppm Ti 4+ and 2000 ppm Ti 4+ , are sintered at 1500°C in a
vacuum, the Ti 4 + is reduced to Ti 3+ in their peripheral regions. This is
indicated by their pink color, which is characteristic of Te+-doped alumina.
The centers of the compacts remain white, however, indicating that the Ti 4 +
oxidation state of the dopant is unchanged. The gradient in the oxidation
state of the dopant has a pronounced effect on both the microstructural
development and the rate of grain boundary migration. The peripheral
regions contain equiaxed grains whereas the central regions show the onset
of grain elongation and evidence of faceting.
When a polymethylacrylate (PMA) solution is poured on a
polyviny1chloride (PVC) substrate, the PVC starts to dissolve in the PMA
and diffuses in the solution to the side facing the air (see Figure 6.35) [131].
Diffusion continues as long as the solvent tetrahydrofuran (THF) is present
in the PMAIPVC solution. When the solvent has completely evaporated, the
local PMA/PVC composition ratio is frozen in. Different initial ratios of
PMA and the solvent THF lead to different times required for complete
evaporation of the THF, and thus to different concentration profiles resulting
from the diffusion of the PVC into the PMA. Small volume ratios of
THF/PMA produce steep gradients close to the initial interface between the
solid PVC substrate and the PMA solution, with the PVC and PMA phases
still present. Higher THF/PMA ratios produce extended zones between the
PVC and PMA phase, with smooth compositional gradients. Still higher
THF/PMA ratios provide sufficient time for the complete consumption of
the initial PMA and PVC phases by interdiffusion. This results in the
formation of a solid solution with a narrow composition gradient.
209
~
Evaporation
PMA solution
DiSsohtion and
Diffusion
Figure 6.35. Schematic of the PMA(THF)IPVC system to fabricate FGMs [131].
4.2 Liquid and Gaseous Flow
When zirconium phosphide (ZrP) powder is uniaxially pressed at 75 MPa

then isostatically pressed at 100 MPa, bars are formed with a
homogeneously distributed porosity of about 38 %. After the powder
compacts are evacuated and pressure infiltrated with epoxy resin for varying
lengths of time, a concentration distribution of the epoxy resin is observed
even following prolonged infiltration. The kinetics of the infiltration process
are diffusion controlled, and the infiltration depth varies as the square root of
the ratio of the pores to the viscosity [132]. An identical pore filling process
has been demonstrated when pressed bars of the superconductors yttrium-
barium-copper-oxide (YBCO) and barium-strontium-copper-oxide are
infiltrated with epoxy resin [133, 134].
To produce FGMs of WC-Co cemented carbides, presintered compacts of
WC-l weight % Co are rapidly immersed in a melt of WC-20 weight % Co,
which only partially eliminates their high porosity. The resulting material
has a gradient structure in which the residual porosity increases with
increasing distance from the surface of the compact that was in contact with
the melt. The hardness (Vickers) ranges from 1200 HV close to the contact
areas, to between 1020 and 1080 HV furthest away, corresponding to Co
concentrations of6 and 12 weight %, respectively [135].
A compositionally graded silicon carbide-silicon carbide/graphite (SiC-
SiC/C) material composed of a SiC surface coating, an intermediate SiC/C
layer, and a graphite matrix can be made by reacting gaseous SiO (silicon
monoxide) with graphite followed by CVD coating with a homogeneous SiC
210 Chapter 6
layer. The SiO is vaporized in a high purity helium carrier gas stream at
1300°C that transports the SiO through isotropic, fine-grained graphite at
1350°C. The reaction between the SiO and the graphite results in the
formation of SiC within the graphite, with the development of a narrow
gradient in SiC content between the surface and the interior of the graphite.
The maximum Si content within the graphite can be varied between 0.17 and
5.1 weight % by controlling the reaction rates [136].
4.3 Processing in Thermal Fields
With the exception of the self-propagating high temperature synthesis

(SHS) process, when producing a metal-ceramic FGM by powder
metallurgical methods, the ceramic is usually heated without the application
of a thermal gradient [137]. However, a density gradient can be created by
applying temperature gradients during sintering. For example, a cylindrical
lead zirconate titanate (PZT) powder compact was sintered by heating one
side externally with an infrared lamp [138]. During sintering (1 hour), a
stationary temperature gradient of 150°C was maintained between the heated
surface and the inside of the cylinder, at a distance of 5 mm from the heated
surface. After sintering, the density in the surface area was considerably
higher than in the corresponding interior of the cylinder, and this difference
was paralleled in the piezoelectric properties of the PZT material.
Microwave heating is a pressureless heating process that provides a self-
regulating heating pattern governed by the compositional gradient. Radiation
at a frequency of 2.45 GHz has been identified as a general heating method
with a self-regulating potential for compositional gradients [139]. The
creation of compositional and grain size gradients in homogeneous ceramic
materials as a consequence of certain characteristic mechanisms of
microwave heating also has been investigated [140].
4.4 Processing with Electrical Fields
In a novel method based on the infiltration of refractory porous preforms

with a molten metal or polymer, a gradient in the electrochemical potential is
set up inside a porous preform. This produces a gradient in the rate of
electrochemical dissolution or deposition of the preform material, and
consequently creates a graded porosity. A macroscopic electrokinetic model
of the gradation process has been developed, and the influence of
experimental parameters such as current density, electrode and electrolyte
resistivity, and geometrical factors on the spatial distribution of the gradation
has been compared with experimental observation. An FGM of
211
tungsten/copper (W/Cu) was produced, and some of its properties have been
determined as a function of position [141].
4.5 Processing with Other Fields
Gradients in plastic strain can be used to produce FGMs with graded

magnetic properties [142]. The paramagnetic phase in austenitic stainless
steels, such as Fe-18Cr-8Ni, is transformed into the ferromagnetic alpha
prime (a ') phase by plastic deformation at low temperatures. Since the
amount of the deformation induced martensite increases with the local strain,
the saturation magnetization of the deformed austenitic stainless steel should
also increase with increasing strain. As indicated in Figure 6.36, this could
make it possible to produce large FGM parts with gradients in their magnetic
saturation.
0.5 0.5
• Specimen (B)
ra
"iii
0.4
• Specimen (C) .2l
...... 0.4
c:
0
c: ~
.~ N 0.3
iii ~
c:
Q) 0)
ra
E 0.2
::J
,=:
c:
0
0.1 ~::J 0.1
iii
en
0
10 20 30 40 50 60 0 10 20 30 40 50 60
Distance / mm Distance / mm
(a) (b)
Figure 6.36. a) Distribution of the plastic strain (a) and saturation magnetization (b) in two
austenitic stainless steel specimens with different geometries (B and C) [142].
212 Chapter 6
5. MELT PROCESSING
The use of melt processing to form FGMs has been very limited. Two
reasons may be the difficulty in fine-tuning and controlling the formation of
extended compositional gradients in melts and the incompatibility of many
phases in the molten state.
5.1 Settling under Gravity
Mixtures of phases with considerable differences in their densities may

separate under normal gravity when kinetic and steric conditions allow the
heavier phases to settle [143]. In some respects, settling under gravity
resembles powder s·ettling and stacking from aqueous and non-aqueous
particle dispersions. In aqueous dispersions, the liquid phase is drained off
after settling, producing a powder stack that is then dried. However, settling
under gravity during melt treatment ends with the solidification of the melt.
In other words, in melt processing the liquid phase is an integral part of the
final solidified product.
A number of model experiments have been performed with W-Fe-Ni
heavy metal alloys where the almost pure tungsten grains (density
approximately 1900 kg/m3) are dispersed in a W-Fe-Ni melt (density
approximately 1000 kg/m\ The volume fraction of the W-particles
decreases from the bottom to the top of a cast column due to density
gradients resulting from initial settling and subsequent enhancement of the
differences in the density by shape accommodation of the W-based grains to
allow a more optimal packing of the solid material [144].
5.2 Settling under Centrifugal Forces
Centrifugal force enables the creation of a gradient compositional

distribution in a ceramic powder mixed with a metal because of the
difference between the densities of the molten metal and the ceramic
material. In the centrifugal casting of thick-walled rings of SiC/AI FGMs,
molten Al containing 10 volume % SiC is poured into a rotating 90 mm long
thick-walled tube with an outer wall diameter of 90 mm and a wall thickness
of 10 mm [145]. The mold's rotational speed produces forces on the melt
equivalent to 23 to 143 times the gravitational force. The molten material
solidifies during the rotation after a certain rotation time has elapsed. Figure
6.37 shows a schematic of an FGM fabrication set-up that uses centrifugal
force during solidification [146].
In Al-Ni melts, when AI-Ni alloys containing less than 30 mass % Ni are
used, the intermetallic compound AhNi (containing more than 5.7 mass %
213
Ni) is initially nucleated during cooling [147]. Because of the difference in

density between AhNi (= 4000 kg/m3) and molten AI-20 mass % Ni alloy
(3930 kg/m 3), a graded radial distribution of the AbNi phase within the cross
section is obtained (see Figure 6.38). These model materials have been
examined via a series of experiments that included an evaluation of their
graded Young's modulus and the measurement of their residual stresses after
cooling to room temperature.
Figure 6.37. Schematic ofan FGM fabrication set-up that uses centrifugal force during
solidification [145].
5.3 Solidification
The potential of the Verneuil process (also called the flame fusion
process) to fabricate FGMs has been demonstrated with various aluminum
oxide based materials [148]. The main component of a conventional
Verneuil system is a vertical, inverted oxyhydrogen burner composed of
several concentric tubes. Hydrogen is transported through the outer tube to
feed the flame that burns in a ceramic muffle, and oxygen and the crystalline
powder are fed through the inner tube. A seed crystal is positioned in such a
manner that only a thin film of the liquid phase is present at the top surface
of the crystal. The crystal grows at constant conditions if the rate that the
molten droplets are fed to the melt film and the rate that the melt film
solidifies on the crystal (i.e. the crystal growth rate) are in proper balance
[149]. The standard material used for the Verneuil process is Ah03
(aluminum oxide). Because of the small volume of the liquid phase, this
process is well-suited for growing graded chromium doped alumina (ruby-
214 Chapter 6
sapphire) crystals with sharp transitions between the Cr-rich (40 %) and the
Cr-poor (15 %) regions, as well as for growing crystals with transition
regions of several centimeters. The recent development of a low-temperature
flame fusion technique makes it possible for the Vemeuil process to work in
the temperature range between 800°C and 2500°C.
60 120
0
50 110
>- III
a..
40 100 {!J
ZM -...
<i: (/l
:J
'0 30 90 "S
"C
0~ 0
Q) E
E 20 - : Estimated V, curve 80 (/l
:J -0)
"0 X : Experimental V, for G=23 t:
> o : Experimental V, for G=147
:J
0
10 70 >-
- - - : Young's modulus
0 60
0.0 0.2 0.4 0.6 0.8 1.0
Specific thickness
Figure 6.38. Distribution profile of the Al3Ni phase in the aluminum based phase and the
corresponding graded distribution of the Young's modulus. (G represents the centrifugal
acceleration of the mold) [147].
Under gravity conditions, buoyancy convection and gravitational

segregation caused by density differences often produce compositional
gradients in melts. When gravity conditions are rapidly changed into
microgravity conditions, these compositional gradients can be stabilized for
a brief time. Research using this method to produce FGMs has been carried
out by synthesizing indium antimonide (lnSb) with various compositions
[150].
6. JOINING
Joining dissimilar materials is complicated by unanticipated chemical

reactions and by stresses produced during the joining process or in service.
215
From an end-use perspective, applications at elevated temperatures (e.g., for

gas turbines or heat exchangers) require the use of interfacial layers with
high temperature properties sufficient to exploit the potential of joints of
ceramic or other high temperature materials. To keep production costs low
and to limit thermal stresses and reactions, a rapid mass production method
is desirable that could be applied at low joining temperatures.
6.1 Solid State Joining
Combining different nickel-base superalloys is desirable when a variety

of high temperature properties are required for turbine engine components.
The joining of various components via solid state bonding has been studied
in the laboratory. A bladed disk can be manufactured by joining a fine-
grained powder metallurgy material such as Astroloy® (Cr 15.0 weight %,
Co 17.0 weight %, Mo 5.0 weight %, Ti 3.5 weight %, Al 4.0 weight % and
balance Ni) to blades made from directionally solidified or single crystal
materials by either hot isostatic or hot uniaxial pressing. Coextrusion has
been used to join two disc materials with different microstructures, one for
the hub that has high strength and good low cycle fatigue, and one for the
rim with good creep resistance. The gradation in the grain size and the
secondary strengthening phase (gamma prime precipitation) in the
microstructure occurs over distances that are controlled by diffusion, and
that also can be manipulated by the insertion of nickel-base (Ni-20Cr) foils
as intermediate layers between the fine-grained and the coarse-grained
components. During the joining process, the microstructural development is
characterized by the elimination of pores, the formation of submicrometer
oxides or carbides at the joint, and by gamma prime phase precipitation and
diffusion phenomena in the vicinity of the interface. The mechanical tests of
uniaxial tension, creep, and fatigue show reproducible values exceeding
those of the weakest material used as a component [151].
Graded silicon nitride/titanium nitride (ShN4ITiN) ceramic matrix
composites (CMCs) and TiNlNi metal matrix composites (MMCs) have
been prepared by hot isostatic pressing (HIP) to demonstrate a joining
concept aimed at reducing the residual stress in joints between SbN4 and
Incoloy 909 (a Fe-Ni base superalloy). Due to the abnormal grain growth in
the superalloy at higher temperatures, the hot isostatic pressing temperature
for simultaneously joining and densifying the TiNlNi MMC was limited to
980°C. To obtain layer regions with low Ni matrix content and high strength,
Ni-coated coarse TiN powders with fine TiN and Ni additions were used
[152].
A new welding technology for joining dissimilar materials has been
tested with two different stainless steels. A short, bar-shaped transitional
216 Chapter 6
joint with a graded composition that varies along its length, made by
blending the two parent powders then hot isostatic pressing, was placed
between the two different steels before joining them. Because of
thermodynamic interactions between the hot isostatically pressed powder
particles of the parent materials, the transition zone contains phase
constituents different from those in the parent materials. Using fundamental
thermodynamic and kinetic principles, the microstructure of the transition
zone was predicted correctly. Investigation of the creep properties show
values above those of the weaker of the two parent materials with decreasing
stress level and increasing test duration [153].
6.2 Transient Liquid Phase Joining
Transient liquid phase (TLP) joining was originally developed for joining
Ni-based superalloys with appropriately designed interlayers at low
temperatures and low bonding pressures. It produces joints that can be used
subsequently at elevated temperatures [154, 155].
FGM structures need to be designed with gradients in the interlayers for
joining that are temporary and serve largely to facilitate processing [156].
The interlayers generally consist of a thick core layer of a high melting point
metal combined with a thin cladding layer of a low melting point material, as
illustrated in Figure 6.39. The former affects the physical and thermal
properties, while the latter makes it possible to reduce the processing
temperature. The components are selected using phase diagrams, so that they
interact to form a refractory alloy or compound. Isothermal solidification of
the liquid layer occurs due to the diffusion of the low melting point
component of the core layer [157]. To minimize the processing time and to
maximize the diffusion rate of the low melting component in the core layer,
or in the compound layer formed by the reaction, the thickness of the liquid
film should be minimized. Good wetting is another essential requirement for
superior bonds [158]. Whereas the wetting of metals by metal melts is
adequate for many systems, the wetting of ceramics by liquid metals often
requires facilitation by the addition of certain elements.
Inserting a graded CulNb/Cu foil between two Ab03 plates has been
found to facilitate their bonding by means of a transient liquid phase [159].
During hot pressing in a vacuum at 1150°C, the molten Cu-rich regions of
the foil react with the Nb to form a solid phase. The temporary presence of
the Cu-rich melt is sufficient to produce good bonding between the two
alumina plates, and the presence of the Nb core layer provides a close
thermal expansion mismatch between the metal interlayer and the ceramic
plates. Although the CulNb/Cu system does not become completely
homogenized due to the low solubility and slow diffusion of Cu into Nb, the
217
joining of the plates is successful. Comparable wetting experiments indicate

that the presence of Nb in the graded Cu foil reduces the contact angle of the
Cu on the Ab03 plates.
t =0
I Ceramic
I Cladding
a) Cae
Cladding
I Ceramic
I
t>O
b)
t = 00
I Ceramic
I
c) Interlayer
I Ceramic
I
Figure 6.39. An illustration of multilayer interiayer design and evolution. (a) Initially, a sharp
discontinuity exists between the thicker core layer and the thinner cladding layers. (b) After
some annealing and interdiffusion, the interiayer becomes homogenized, which increases the
remelting temperature. (c) After prolonged annealing or use at elevated temperatures, a
uniform interlayer is formed [155].
As shown in Figure 6.40, joining Ab03 ceramics with Cu/80Ni-20Cr/Cu

interlayers [158] is relatively successful compared with CulNi/Cu interlayers
218 Chapter 6
[160] with respect to the average strength and strength distribution. The
latter joining system shows high strength but the values are scattered. The
scatter appears to be associated with two factors: incomplete wetting and the
formation of a nickel spinel (NiAIz04) reaction product along the
ceramic/metal interface. In the Cu/80Ni-20Cr/Cu joining system, wetting is
improved by tailoring the chemistry of the transient liquid phase and no
reaction product is formed. Among the graded systems for the transient
liquid phase joining of SbN4 that have been investigated, Au/80Ni-20Cr/Au
interlayers have been found to produce bonds with failure strengths
approaching those of the SbN4 [161].
100
90
80
70
60
50
-
'#
>-
:!::
40
30
:sCIS
e
Jl
Q.
20
...
G)
.2
'ji
LL
10
0
x
40 60 80 100 150 200 300

Failure strength (MPa)
Figure 6.40. The failure probability vs. the failure strength for unbonded reference Ah03 (X);
for a CulNi/Cu interlayer bonded alumina (D); for a Cr-precoated CulNilCu interlayer
bonded alumina ( ...); and for a Cu/80-Ni20Cr/Cu interlayer bonded AhOl.) [155].
Partial transient liquid phase bonding has been developed for joining SiC
ceramics via nonmetallic multilayer interlayers. It is characterized by a
composition gradient in the low melting phase that limits the amount of melt
formed. (By comparison, the low melting interlayers in transient liquid phase
joining melt completely.) A Ge interlayer is used as a transient liquid phase
former in conjunction with core layers of Si or reaction bonded SiC [162]. In
219
joining bulk SiC using Ge interlayers and liquid Si, functionally graded
interlayers have been shown to prevent interfacial reactions and to level out
the shear stresses from potentially weak sharp interfaces to thicker interfacial
layers [163].
When used as an insert material, an alloy of Al with O.S weight % Sn to
prevent the formation of an undesirable oxide film on the surface of the
aluminum, relaxes the thermomechanical stress between ceramics that are
diffusion bonded with metals. Good bonds are obtained with the AI-Sn alloy
(ceramic/AI-Sn alloy/metal) for many pairs of ceramics with metals when
the bonding is carried out at temperatures (SOO°C - 600°C) below the melting
temperature of Al [164].
6.3 Liquid Phase Joining
Eutectic bonding utilizes the presence of a liquid phase throughout the

joining procedure. Typically, a metal and an intermetallic compound are
combined using a eutectic reaction between both materials to create an
amount of melt sufficient for joining. For example, in the production of
FGMs of TilTbSn and TiITi5Si3 by this method, solidification during cooling
results in bonding of the intermetallic to the metal part, and also to the
formation of a compositional gradient perpendicular to the initial eutectic
melt layer. At controlled slow solidification rates of the eutectic, the ratio of
metal to intermetallic compound changes almost linearly between the two
adjacent plates. Rapid cooling produces a less defined compositional
gradient. The difference between the thermal expansion coefficients of Ti
and the intermetallic compounds is much smaller than between metals and
ceramics. Therefore only moderate stresses are created in the solidified
transition layer [16S].
7. ADVANCED MANUFACTURING TECHNIQUES
This section describes three state-of-the-art techniques to manufacture

FGMs: solid freeform fabrication or layered manufacturing, a rapid
prototyping technique; sol-gel processing and fiber stacking, a chemical
technique; and diffusion bonding utilizing superplasticity.
7.1 Solid Freeform Fabrication
Solid freeform fabrication (SFF) is a developing technology of potential

commercial importance because of its capability for rapid prototyping. Parts
220 Chapter 6
made of engineering plastics, ceramics, metals, and composites, with

complex geometries, can be produced in days rather than the weeks or even
months required using conventional processing technologies. The ability to
do cost-effective and iterative design with these techniques enables ceramic
components to be created from the start using ceramic design guidelines,
rather than fitting ceramic parts into component geometries designed for
metals [166]. Solid freeform fabrication is a computer controlled, layer-by-
layer, additive process in which a standard CAD (computer aided design)
file of a part is first converted to a rapid prototyping format (an STL file) and
sliced into a series of horizontal planes. The method for transferring this
layered CAD design information into a physical reconstruction of the actual
part depends on the SFF technology used.
There are many ways to categorize the increasing number of SFF
processes [167-170]. Some typical SFF systems are shown schematically in
Figure 6.41. Laminated object manufacturing (LOM) builds three-
dimensional objects with complex geometries from flat sheets of material
that are laid down one at a time and laminated to the previous layer (Figure
6.41a) [171]. The perimeter of each layer is cut by a CO2 laser directed over
its surface. Information from a CAD file is used to determine the laser's path
and speed. The laser also cuts the excess material into cubes, which act as a
support during the process but can be removed easily manually to reveal the
completed part.
Laminated object manufacturing was originally designed to produce
paper models of parts from adhesive paper. These are then used to test form
and fit in the same way as foam or cardboard prototypes. Ceramic or metal
parts (e.g., alumina, aluminum nitride, silicon nitride, hydroxyapatite, and
stainless steel) have been made in a similar way by replacing the paper with
tape-cast, flat sheets consisting of fine ceramic or metal particles dispersed
in a polymer matrix. The thin sheets or tapes are easily cut by the laser
because the polymer decomposes at high temperatures. The resulting part is
then fired to burn off the polymer and sinter the ceramic or metal powder to
form a dense object [172]. Parts with complex geometries can be built. The
LOM process can be adapted readily to create compositionally graded
structures by using tape cast sheets composed of varying proportions of two
different materials. However, compositional gradients in LOM-built
components are limited to the region of the part along the build axis.
In the SFF process, stereolithography, lasers are used to selectively cure
resins layer-by-Iayer to build complex shapes (Figure 6.41 b) [173]. Thin
layers of liquid photopolymer are spread and a laser beam is tracked over the
surface of the reservoir. The polymer's curing is initiated by the laser, and
only the regions exposed to the beam undergo polymerization. Then a new
layer of liquid polymer is spread above the cured component, which is
221
lowered incrementally. The speed of the laser scan and the intensity of the
beam determine the depth of polymerization. When the laser scanning is
completed, the uncured material is drained off revealing the finished part.
The presence of excess uncured polymer facilitates removing the part. When
building complex shapes with features such as overhangs or undercuts,
temporary structures are added to support them.
x-v scanning x-v scanning mirror on

Galvanometer drives
Laser beam z
Elevator
UV curable liquid
Supply roll
x-v positioning system

II
galvanometer I P d flIlfl: I
drives ower t'of"' . .
be spread. Ink'Jet pnnt head
ROllerl1 : . .
Formed object spreader :~ Binder Jet
I x , : Formed object
.......-'T'"''---<-....---.;_ - • •
o
Powder Powder
-Piston
t..J
Figure 6.41. Schematics of various SFF techniques. (a) Laminated object manufacturing
(LOM) builds components by laminating and cutting sheets of paper or thin tapes of plastics
filled with ceramic or metal powders. (b) Stereo lithography uses a laser to initiate curing
locally in a reservoir of the molten polymer. (c) Selective laser sintering (SLS) builds parts
from fusible powder by locally heating the surface of a powder bed with a laser. (d) Three
dimensional printing (3DP) builds parts by ink-jet printing binder onto a powder bed followed
by conventional powder processing of the green part built. (e) A heated extrusion head is used
to shape three-dimensional objects in the fused deposition modeling (FDM) process. (t)
Extrusion freeform fabrication (EFF) with dual extrusion cylinders and a mixing head can be
used to build FGMs.
222 Chapter 6
Many of the commercially available stereolithography machines are used

to produce acrylic or epoxy components for prototyping applications. Some
of these components are used as patterns for casting processes, and have
proven to reduce the lead time for new products effectively. Although most
of the work in stereo lithography has been with polymeric parts, ceramic-
filled polymer parts have also been produced [174]. Composite structures
made of ceramic particles in a polymer matrix are fired to decompose the
polymer and densify the ceramic. Parts with varying compositions could be
fabricated by filling the liquid polymers with two or more different
materials, and structures with a one-dimensional compositional gradient
could be built as with LOM.
A laser is also used for the SFF process, selective laser sintering (SLS),
shown in Figure 6.41 (c). In this case, laser energy is directed toward the
surface of the layer to initiate localized bonding [175, 176]. The bonding
mechanism for SLS, unlike stereo lithography, involves partial melting and
fusing of a thermoplastic powder. The powder is spread in thin layers and
the laser beam is traced over its surface. This causes the thermoplastic
powder to melt in the regions of the powder bed exposed to the laser beam.
Subsequent resolidification results in local bonding within each layer as well
as bonding to the layer immediately below. The powder spreading and laser
scanning steps are repeated until the part is completed. The part is retrieved
simply by brushing away the loose particles, since the area not exposed to
the laser remains unsolidified. Unlike the stereolithography process, support
structures are not required since the packed powder particles are rigid
enough to prevent the solidified portions from moving. Compositionally
graded structures can be created by SLS in the same way as by LOM and
stereolithography. Green (unsintered) parts containing compositional
gradients can be built by spreading powder mixtures that have varying
compositions.
In three-dimensional printing (3DP), the SLS technology has been
adapted to form objects by selectively binding the powder particles (Figure
6.41 d) [177, 178]. First, a thin layer of a powdered material is spread in a
container. The printhead assembly then scans over the powder bed,
depositing binder droplets in selected regions. 3DP employs ink-jet printing
technology to generate and place the binder droplets. When a layer has been
printed, the floor of the powder container lowers to allow another layer of
the powder to be spread. Information about the new layer is relayed from a
computer and the next layer is printed. These steps are repeated until the
final layer is printed. The binder bonds the powder locally within the layer
and also to the layer below. Loose powder is removed, and the 3-
dimensional green part is now ready for strengthening and densifying
processing.
223
The 3DP process has been used to produce complex components in a

wide range of materials including ceramics [179], glass [180], metals [181],
and engineering plastics [182]. The support provided by the powder bed
makes it possible to exploit the versatility of the process for creating
complex parts with overhangs, undercuts, and internal volumes without
requiring temporary support structures. In addition, different materials can
be dispensed through separate nozzles, which is a concept analogous to color
ink jet printing. The materials can be deposited as particulates suspended in a
liquid, or dissolved in a liquid carrier, or in the molten state. The proper
placement of binder droplets can be used to control the local composition
and to fabricate components with true three-dimensional compositional
gradients. Compositional control is a unique feature of SFF processes that
use the deposition of material to build parts.
In the SFF process fused deposition modeling (FDM), the thermoplastic
starting material is in the form of filaments that are fed to a heated extruder
(Figure 6.41e) [183]. Fine beads (0.026 - 0.125 cm in diameter) of the
molten plastic are extruded from the extruder head, which moves in the x- Y
direction, onto a fixtureless platform that moves in the Z-direction. Three-
dimensional objects are made by computer control of the movement of both
the extruder head and the platform. Material is extruded and deposited layer-
by-layer only in those areas defined by the CAD program. Control of both
the extrusion head's translational velocity and the extrusion rate are required
to ensure accuracy in the component's dimensions. The rheology of the
molten thermoplastic needs to be tightly controlled, since the final quality of
the part is closely related to the absence of knit lines between adjacent beads
and also the ability to make sharp cuts in the extruded beads. FDM has
recently been adapted for fabricating ceramic parts by using filaments made
of a thermoplastic filled with ceramic particles [184]. Parts with
compositional gradients can be built by loading the thermoplastic filaments
with different materials.
The fused deposition of ceramics and metals (FDC and FDMet) have
been demonstrated successfully with silicon nitride, lead zirconate titanate,
alumina, silica, and hydroxyapatite ceramics, as well as stainless steel and
tool steel. Parts made by FDM have microstructures and properties identical
to those made by conventional powder processes. Four different materials
can be deposited at a time with a recently designed machine that has four
extrusion heads [185].
In Extrusion Freeform Fabrication (EFF) which is similar to FDM, layers
of self-supporting viscous suspensions of highly loaded (20 volume % to 60
volume %) thermoplastics are sequentially deposited using a computer-
controlled extrusion head that builds a 3-D body (Figure 6.41f) [186]. For
fabricating FGMs, the EFF system has been modified by using two extruders
224 Chapter 6
that dispense different materials into a small mixing head. The composition
of the two-component extrudate is controlled by proportioning the feed rate
of the raw materials from the extruders, thereby creating a continuous
compositional gradient in the final component. Examples of ceramic to metal
graded compositions successfully made with EFF include alumina (Ah03) to
nickel aluminide (NiAI), zirconia (Zr02) to NiAI, Ab03 to 305 stainless
steel, Ah03 to the nickel-base superalloy, Inconel 625, and tungsten carbide
(WC) to NiAI [187].
In an investigation to fabricate FGMs by EFF, eight polymerizable
slurries were loaded with ceramics or metals including Ah03, Zr02, NiAI,
TiB2, TiC, WC, 304 stainless steel, and Inconel 625 [188]. The slurries were
processed by ball milling the raw powders in two different acrylate monomer
vehicles with solids loadings of 44 to 58 volume %. Their rheological
properties showed thixotropic behavior (thinning when under shear stress but
thickening on standing). This is advantageous for the EFF process since it
enables low pressure extrusion and accurate deposition of the freeformed
material with minimal spreading of the layers once the slurry is deposited.
Initiators such as peroxycarbonate are added to the slurries just prior to
extrusion to enable rapid curing or gelation after their extrusion.
In order to produce FGMs, an EFF machine has been configured with
dual extrusion cylinders having separate slurry reservoirs for the individual
ceramic and metal slurries (Figure 6.41 f). The flow of the individual slurries
is passed through a Y-block into a small mixing head containing an in-line
static mixer and out through a deposition needle. The extrusion head then
sweeps out the designed path while depositing the liquid slurries to build up
a 3-dimensional FGM body. Figure 6.42 shows the microstructure of an
Ah03-304 stainless steel FGM made by EFF [189].
"
!.
.
'-1' mm
!
- - - - - - - - - -- .I u~:.'i
Figure 6.42. Scanning electron micrograph of a section of an Ah03·304 stainless steel (SS)
FGM produced by extrusion freeform fabrication (EFF) [168].
225
After hot pressing, the FGM billets have a slightly bowed appearance --
concave on the metal side and convex on the ceramic side. This would be
expected given the differences in the thermal contraction coefficients of the
two different materials. The density of the pure metal end is close to 100%
of theoretical, while the pure ceramic end is relatively dense (84-94%)
despite the fairly low hot pressing temperature (1175°C -1350°C).
Other systems for the localized deposition of material that use precision
heads for laser surface cladding also are being used to make rapidly
prototyped metal and ceramic parts [89]. The fabrication of three-
dimensional objects without the use of tooling has rapidly progressed from
simple models to complex functional prototypes. Parts can be produced in a
wide variety of materials including wax, thermoplastics, thermosets,
photopolymers, paper, metals, ceramics, and glass fiber reinforced
composites. It is now possible to create one, two, and three dimensional
FGMs by several SFF techniques.
t-ZTA
Compositionally
Graded Layer
~1~~+-+-~I~I~-4-+~1
o 1.5 3
mol% Y20 3
Figure 6.43. Schematic of a 3D-printed zirconia toughened alumina (ZrA) multilayer plate.
In the alumina-zirconia (Ah03-Zr02) ceramic system, zirconia-

toughened alumina (ZTA), the continuous phase is alumina (70-95%) and
the second phase is zirconia particulates (5-30%). The transformation of the
monoclinic to the tetragonal phase (transformation toughening) and the
stabilization of the tetragonal phase in the zirconia by addition of a suitable
dopant results in the strengthening and toughening of this ceramic system
[190]. Three-dimensional printing can be used to build a ZTA component
226 Chapter 6
with a compositional gradient. First a mixture of spray dried particles of

alumina and undoped zirconia is spread, and next a polymeric binder is
selectively deposited onto the powder layer to define the macroscopic shape
of the component. A second nozzle then prints an aqueous solution of the
yttrium nitrate (YN03k6H20 dopant onto selected areas of the part. The
proportion of the tetragonal Zr02 in the final component is controlled locally
by appropriate selection of the process parameters. Figure 6.43 shows a
schematic of a 3D-printed ZTA plate with a compositional gradient. Once
the 3DP build process is completed, post processing including isostatic
pressing, binder burnout, and pressureless sintering is carried out to fully
densify the component.
Figure 6.44 shows the relative volume fraction of the two different
crystalline forms of Zr02 (monoclinic and tetragonal) as a function of
position, based on x-ray diffraction analysis (XRD). The linear variation of
the monoclinic Zr02 along the thickness illustrates successful fabrication of
the compositionally graded multilayered ZTA by 3DP. Deviation from
linearity near the monoclinic ZT A surface can be explained by the presence
of very fine Zr02 particles that are not large enough to transform.
100
C\I • •
0....
NI
80 •
E
'0
c
60 •
0
:;:=
- •
40
-
0
~
( ])
•
E
::J
20 •
0
>
0%
0 250 500 750 1000
Position (/lm)
Figure 6.44. The calculated relative volume fraction of monoclinic zirconia content through
the thickness of ZTA multilayer plates.
The evolution of residual stress and curvature within ZTA multilayers

with a compositional gradient has been studied [191]. The mismatch in both
the coefficients of thermal expansion and the zirconia transformation strain
227
were used to derive the analytical solutions for the residual stress and the
curvature. The experimentally measured curvature from a 3D-printed ZTA
multilayer was 6.4 m- I while the predicted values ranged from 3.9 to 5.7 m-\
shown in Figure 6.45 as the shaded area. Such analytical tools can be used to
design compositional gradients within components to optimize the
mechanical properties of 3D-printed ZT A parts.
0.5
E Measured Curvature (S.4m')
.s 0.3
c
0
fj
0.1 \.
~
Qj -0.1 \
0 Predicted curvature based on 3-5% Zr02 expansion (3.9 - 5.7m")
-0.3
-15 -10 -5 o 5 10 15
Distance from the center of the plate (mm)
Figure 6.45. The calculated and the measured curvature in 3D-printed ZTA multilayer plates.
Another example of an SFF-derived component with localized

compositional variation is a 3D-printed drug delivery device (DDD). This is
an example of a nonstructural application for a compositionally graded
material. It is used for controlling the release rates of different drugs. The
macroscopic configuration of a model device 3D-printed with a plastic
matrix that undergoes hydrolytic degradation is shown in Figure 6.46. A
number of compartments are built into this device and various drugs are
inserted appropriately. When a DDD is inside a patient, either by
implantation or ingested orally, resorption of the plastic matrix results in
release of the drugs from the micro-reservoirs. The lag time required to
release drugs from each of the compartments can be designed to meet the
specific prescriptions of individual patients. The composition and
microstructure of the matrix as well as the thickness of the compartment
walls strongly affect both the rate and the mechanism of resorption. In a
preliminary investigation, the controlled release of various dyes from 3D-
printed model devices was tested with promising results [189, 193].
7.2 Graded Ceramic Matrix Composites Made via a sol-

gel technique
Graded ceramic matrix composites can be fabricated by a number of

methods [193]. One innovative process, illustrated in Figure 6.47, fabricates
228 Chapter 6
functionally graded ceramic composites reinforced with woven fibers that

can be oriented in different directions in the same composite. Sol-gel
techniques are used to combine several different fiber and matrix materials
that have various desired properties [194, 195]. First, the fibers in a two-
dimensional woven fabric are impregnated with a fiber-matrix interface
precursor (a liquid alkoxide mixture) that reacts with the fibers to form an
interface between the fibers and the matrix to minimize reaction between
them. It also acts as a diffusion barrier to protect the fibers from chemical
attack. Depending on both the matrix material and the fiber, several different
interface precursors can be used either alone or in various combinations, as
indicated in Table 6.2 [196, 197, 198]. The liquid alkoxide interface
precursor mixture slowly hydrolyzes and polycondenses, forming a gel by
reacting with atmospheric moisture.
(a)
(b)
P !=J Q
Q
J Q 12.
[\-- !=J Q (c)
P. !=J Q
Figure 6.46. (a) Schematic of a 3D-printed model drug delivery device (DOD). The top lid is
open to show the internal shape. (b) A DOD with strategic placement of two different drugs.
The differently shaded circles represent different drugs placed in the compartments. (c) A
DOD with compositional variation to control the drug release rate. The thick lines represent
the walls with a substantially lower rate of desorption than the walls represented by thin lines.
Tributyl Borate.In the next processing step, a fine, porous amorphous

matrix precursor powder suspended in chi oro benzene is deposited on the
229
layers of woven fiber fabric. This powder is prepared by rapid hydrolysis of

the appropriate mixture of alkoxides in propanol. The resulting gel is dried
(750°C) to drive off most of the water in the polymeric oxide network. In the
final processing step, the doubly impregnated layers of woven fabric are
stacked in a graphite mold and hot pressed (1000°C - 1400°C) [199]. A
liquid sintering aid (B 20 3 or Ge03) is also used, which is eliminated either
by incorporation into the matrix or by volatilizing. Therefore it does not
contribute to the formation of second phases at the grain boundaries.
Special additives fj\ Woven fabrics preparation

whiskers,powder I..:J ~
A ®~ Impregnation with the interface precursor

Matri~ precursor Infiltration +
(ultraflne powder) Interface in situ gelation
.. (~r~g~i~~~) ~hYdrOIYSiS-POIYCOndensatiOn)
DisperSion - - - ---,
(+ SOlventS\ n cycles
®
eventually
L~
--- ..
J
Deposit of the
matrix precursor
~Stacking-sticking
~ Hot-pressing
@ _ ..... ~ ..... IComposite I 4 0
0. . . . . . ®
. . . . . . ~
Drying
Figure 6.47. Flow diagram of the sol-gel process for fabricating functionally graded ceramic
matrix composites incorporating different fibers and matrices in the same composite [198].
Porosity in the ceramic matrix is minimized « 5%) by the use of a very

reactive matrix precursor plus an interface precursor. This results in the
formation of a liquid phase that acts both to densify the matrix (via liquid
phase sintering) and to maximize the contact between the grains of the
matrix precursor during the hot pressing step.
In order to improve the linear elastic limit of the composite, the matrix is
further reinforced via submicrometer and nanometer size precipitates [196].
Since in the sol-gel process the homogeneity of the liquid alkoxide mixture
that forms the gel is maintained up to the nucleation stage, which occurs at a
relatively low temperature, the precipitates formed are in the submicrometer
range. Because of the presence of these reinforcing submicrometer
particulates, cracks are arrested immediately after their initiation. The net
effect of this sol-gel process is to produce what could be regarded as a
multi scale reinforced composite, which is reinforced at the millimeter scale
230 Chapter 6
by the woven fiber network, at the micrometer scale by the fiber-matrix

interface, and at the nanometer scale by the precipitate/matrix interface.
Table 6.2. Examples of Fiber Reinforced Ceramic Matrix Composites with Functionally
Tailored Layers.
Composite (M/F) Matrix (M) Interface Fiber (F)
Mullite'
NASICON b No No
Components
No No Nicalon NLM 202 c
NexteI 440 d
Mullite/SiC Mullite ALOSi"+TBBf Nicalon NLM 202 c
Mullite/SiC Mullite/Zr02 ALOSI+TBB/ZPg Nicalon NLM 202 c
TEOGe h
MullitelMullite Mullite ALOSI+TB NexteI 440
MullitelMullite Mullite ZP Nextel440
NASICON/SiC NASICON ZP+ TBPi+ TBB Nicalon NLM 202 c
+TEOSi
NASICONlMullite Nextel440
Celsiank/SiC Celsian ALOSI+TBB Nicalon NLM 202 c
CeisianJ/SiC Celsian ZP+TBP+TBB Nicalon NLM 202 c
+TEOS
Zr02/SiC Zirconia (Zr02) TEOS+TBB+ Nicalon NLM 202
CaSm/ZP+CaS
3Ah03·2Si02·0.1B203.
b Na29Zr2Si1.9P1.1012'
c Two-dimensional fabrics woven along the four directions within the plane.
d Satin weave fabric.
e Aluminum silicon ester
f [(OBuh-Al-O-Si (OEthM
g Zirconium propoxide.
h Germanium ethoxide.
i Tributyl phosphate.
i Tetraethylorthosilicate.
k BaAhShOs.
J Al 20 doped CeIsian.
mCalcium at 750·C in air
Figure 6.48 illustrates graphically the relative shrinkage of stacked layers

of doubly impregnated woven fibers during the hot pressing cycle in the
formation of a SiC reinforced mullite composite. At the beginning of the
cycle, a low pressure of 2-5 MPa is applied to maintain optimum contact
between the impregnated woven fiber layers. Above 500°C, when the
polymerized interface precursor has been dehydrated, the pressure is
increased to 25 MPa, which is just below the densification temperature (Td)
of the matrix and the melting point of the sintering aid. By selecting the
appropriate interface precursors, the dwell temperature required to achieve
231
maximum densification (T d = 200°C - 300°C) can be raised or lowered about

lOO°C. This makes it possible to combine several different kinds of
impregnated fiber/matrix layers in the same composite (for example using A
and B materials as the matrix, the following associations are possible: AB,
AABB, ABAB, CABBAC, etc.) thereby tailoring the physical and lor
chemical properties for a particular application.
dwell
, - _.
, .-
,,
OJ
Cl
Jlc:1 ,
,,
~
Ul
OJ
>
~
Qj
a:
2 3 h time
Figure 6.48. Shrinkage plots during the hot pressing cycle for two stacks of fabric layers
(mullite matrix reinforced with SiC fibers) impregnated with different interface precursor
mixtures. The arrows indicate the pressure increases. The dwell temperatures are l350 DC and
l300 DC [198].
1_mm
::;;a::sr
Figure 6.49. Scanning electron micrographsofpolished sections of two different fiber

reinforced ceramic composites. a) Four woven Nexte1440™ layers (a mullite-like
aluminosilicate with low permittivity) with two layers ofNicalon NLM 202™ fibers (silicon
carbide with semiconducting properties) and a NASICON matrix (Na29Zr2SiI9PU012, a
superionic conductor). The Nextellayers lower the permittivity of the outer surface of the
composite thereby favoring the transmission of electromagnetic energy, whereas the Nicalon
layers create high dielectric losses and increase the composite's mechanical strength. b) In
this composite, a mullite matrix (gray) plus a zirconia matrix (white) both reinforced with
silicon carbide fibers combine mullite's good chemical stability with zirconia's hardness
[198].
232 Chapter 6
Figure 6.49 shows examples of fabricated composites that combine

various kinds of woven fibers (e.g., SiC, mullite) with various kinds of
matrix materials (e.g., NASICON, celsian, zirconia, mullite). For example,
radar absorbent composites can be made by combining materials that have
different electromagnetic properties. While composites for durable aircraft
components can be made by combining materials that have high hardness,
such as zirconia, with those that have good corrosion resistance, such as
mullite and celsian [200].
7.3 Superplastic Forming Combined with Diffusion

Bonding
In superplastic forming certain fine-grained materials, ceramics as well as

metals, can undergo exceptionally high tensile elongation at high
temperatures, which makes it possible to produce near-net-shape large and
complex-shaped components. Superplastic forming methods (e.g., blow
molding, vacuum forming, thermoforming) are characterized by low strain
rates, and can be particularly advantageous for materials that are difficult or
costly to machine, such as metal matrix composites, intermetallic
compounds, ceramics, and FGMs. Combining superplastic forming with
simultaneous diffusion bonding further extends the fabrication range for
large and complex-shaped components [201,202].
In conventional solid state diffusion bonding, the surfaces of components
from similar or dissimilar materials are pressed together at elevated
temperatures. During the initial bonding stage the original contact areas are
increased by elastic and plastic deformation and grain and/or phase
boundaries develop in the contact areas. The residual pores at the interfacial
region are eliminated by grain boundary and volume diffusion. The rate of
elimination depends on the applied pressure and the surface curvature of the
pores as well as their size and shape. The size of the pores is reduced if the
initially contacting surfaces of the components fit smoothly and if the
flattening of the initial points of contact by plastic deformation occurs at low
pressures. Thus materials with high yield strength and rough surfaces usually
require high pressure and high temperatures (close to the sintering
temperature) for complete diffusion bonding.
By using a superplastic metal or ceramic as the basic material for a
component, or as an insert in the joining area, the temperature and pressure
for plastic yield are substantially reduced. Therefore superplastic diffusion
bonding makes it possible to achieve optimal bonding at moderate
conditions without requiring mirror polishing of the bonding surface. At
present, superplastic forming combined with diffusion bonding is used
primarily for manufacturing aircraft parts from titanium alloys. The high cost
233
of this process can be justified by the increased flexibility of design, the

reduced number of mechanical joints, and a significant reduction of the
number of parts therefore reduced assembly costs.
Figure 6.50. The interfaces of a stack of six thin sheets each about 180 I-lm thick with Alz0 3
mole fractions ofO, 20, 40, 60, 80 and 100 % respectively, formed by diffusion bonding
during superplastic deformation of the stack (the initial surface roughness of the thin sheets is
3 I-lm, the deformation rate is 0.01 mm/min , and the total strain is 17%) [201].
234 Chapter 6
It has been shown that a graded sheet 1 mm thick can be produced in the
Zr02 (Y 203)-Ah03 composite system, by diffusion bonding a stack of six
very thin sheets (each about 180 /lm thick) containing increasing mole
fractions of Ah03 of 0, 20, 40, 60, 80 and 100 % respectively [203]. During
diffusion bonding the total strain of the superplastic stack is 17 %. The
internal interfaces of the graded sheet can be seen in Figure 6.50.
As innovative techniques for processing FGMs have been developed,
these have led to many interesting new applications, as can be seen in the
next chapter. However, the reverse is also true, creative ways to use FGMs
have motivated the development of many of the innovative processes
described in this chapter.
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155. Glaeser, A.M. (1997) The use of transient FGM interlayers for joining advanced
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156. Shalz, M.L. et al. (1993) Ceramic joining I, partial transient liquid phase bonding of
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157. Tuah-Poku, I., Dollar, M., and Massalski, T.B. (1988) A study of the transient liquid
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158. Shalz, M.L. et al. (1994) Ceramic joining II, partial transient liquid phase bonding of
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159. Glaeser, A.M. et al. (1993) A transient FGM interlayer based approach to joining
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160. Locatelli, M.R. et al. (1994) Transient liquid phase bonding of alumina ceramics via
microdesigned Ni-based interlayers, International Ceramic Monographs, 1, [151], 203-
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161. Ceccone, G. et al. (1996) An evaluation of the partial transient liquid phase bonding of
ShN4 using Au-coated Ni-22Cr foils, Acta Materialia, 44, 657.
162. Kagegawa, K. and Glaeser, A.M. (1997) Transient FGM joining of silicon carbide
ceramic, a feasibility study, Composites, 28B, 85-91.
163. Rabin, B.H. (1990) Modified tape casting method for ceramic joining, application to
joining of silicon carbide, 1. ofAm. Ceram. Soc., 73, 2757-2759.
164. Itoh, I. et al. (1994) Insert metal of Al-Sn alloy for diffusion bonding in the atmosphere,
in Proc. of The Third Int 'I. Symp. on FGM'94, (eds. B. Ilschner and N. Cherradi), Presses
165. Kirihara, S., Tsujimoto, T., and Tomota, Y. (1997) Development ofmetal/intermetallic
compound functionally graded material produced by eutectic bonding method, in Proc. of
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166. Agarwala, M.K. et al. (1996) FDC, Rapid fabrication of structural components, Am.
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176. Vail, N.K., Barlow, lW., and Marcus, H.L. (1993) SiC preforms for metal infiltration by
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directly from a CAD model, 1. Eng. Ind., 114,481-488.
178. Sachs, E. et al. (1992) CAD-casting, The direct fabrication of ceramic shells and cores
by three dimensional printing, Man. Rev., 5[167], 117-126.
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Chapter 7
APPLICATIONS
Keywords: Apollo, space plane, SiC/C FGM, HOPE, CVI, rocket combustor, TBC,
Nicalon® SiC fibers, Nextel® mullite fibers, Nasicon, EB-PVD, diesel engine,
titanium aluminides, TiAI, thermal barrier coatings, superalloy, turbine blade,
creep, ductility, solar receiver, thermionic converter, C/C cavity,
thermoelectric converter, figure of merit, magnetic fusion reactor, W/Cu, fuel
cell, SOFC, cutting tool, cemented carbide, WC-Co, throwaway chip,
diamond/SiC, razor blade, Si 3N 4 -Cu FGM, graded porosity, gas-reinforced
materials, GASARs, graded bandgap, graded semiconductor, heterojunction,
heterostructure, quasi-electric field, bipolar transistor, graded-index, GRIN,
refractive index, step index, optical glass fiber, multimedia, optical polymer
fiber, CVD, VAD, hip joint, Ti-6AI-4V, bone material interface, implant,
porous metal, bone cement, hydroxyapatite, orthopedics, bioactive ceramics,
biocompatibility
1. INTRODUCTION
The FGM concept is applicable to almost all material fields. Examples of

a variety of real and potential applications in transport systems, energy
conversion systems, cutting tools, machine parts, semiconductors, optics,
and biosystems are described in this chapter. Potential applications include
those structural and engineering uses that require combinations of
incompatible functions such as refractoriness or hardness with toughness, or
chemical inertness with toughness. In aerospace and nuclear energy
applications, reliability rather than cost is the key issue. But in applications
such as cutting tools, high temperature rollers, and engine components,
which require wear, heat, mechanical shock, and corrosion resistance; the
key issues are the cost/performance ratio and reliability.
248 Chapter 7
Two applications now commercialized are high performance cutting tools

of tungsten carbide/cobalt (WC/Co) based FGMs and razor blades of an iron
aluminide/stainless steel FGM (FeAlISS). A more reliable hip prosthesis in
which a biocompatible graded interface forms between the bone and the
implant has been demonstrated successfully clinically. The successful FGM
applications for cutting tools and biomaterials have in common that their
graded structures are formed in situ, and their relatively small size makes it
feasible to process them cost effectively.
To protect the environment and conserve nonrenewable energy resources,
energy conversion systems that do not produce atmospheric pollutants such
as thermionic and thermoelectric converters, fuel cells, and solar batteries
are under active development. The incorporation of the concept into their
total FGM design can improve their conversion efficiency by optimizing
their electronic potential, thermal stress resistance, and chemical durability.
Although the practical applications of FGMs have not yet been fully
realized and exploited, it is the belief of the contributors to this book that the
impact of the FGM concept itself, which can potentially impact almost all
materials research and development, will begin to emerge in the 21 st
century.
2. TRANSPORT SYSTEMS
2.1 Space Vehicle Components
2.1.1 Vehicle protection during reentry
Space vehicles flying at hypersonic speeds experience extremely high

temperatures from aerodynamic heating due to friction between the vehicle
surface and the atmosphere. Two types exist or are on the drawing board:
vehicles like the U.S. space shuttle and the capsules formerly used for the
Apollo missions that are launched vertically into space by a rocket
propulsion system; and fully reusable spacecraft planned during the late
1980s such as the U.S. National Aerospace Plane (NASP), the Japanese
Single Stage to Orbit (SSTO), and the German Sanger program. These latter
are all based on a horizontal takeoff either from a ground-based runway or
from a horizontally flying carrier.
In the first type, after sufficient acceleration the rocket system completely
separates from the space vehicle. During reentry at velocities greater than 11
km/s, rapid heating of the leading edge, where the heat protection shield is
249
located, occurs at altitudes between 120 and 50 km, and maximum

temperatures (the radiant equilibrium temperature) above 2500·C develop.
Because the relatively flat heat protection shield is exposed to the extreme
heat of reentry for just a few minutes and is used only one time, it can be
fabricated from ablative materials.
The reentry velocity of the U.S. space shuttle at an altitude of 120 km is
below 8 km/s, and the maximum temperature experienced is about 1500°C
for a few minutes. Structural components that experience the maximum
exposure to heat such as the nose cone, the leading edges, the rudder, and the
flapperons need to be made of non-metallic carbon/carbon composites (C/C)
with adequate oxidation protection coatings. Nickel and titanium alloys can
be used in other areas of the spacecraft that are exposed to less extreme heat.
However, this may result in weight penalties. For temperatures up to 1200°C,
ceramic tiles can be used, and for temperatures from 300°C to 550°C,
alternative thermal barrier protection systems based on multi wall Ti sheets
can be used.
Horizontally launched space planes that are accelerated by air-breathing
engines (e.g., jet engines) fly in the atmosphere at hypersonic speeds for a
longer time than vehicles launched vertically by rockets. Therefore, the
space plane experiences its maximum exposure to heat during its launch into
space. Initially, one of the main objectives of investigating FGMs deposited
by chemical vapor deposition (CVD-FGMs) was to develop thermal barrier
coatings for a space plane. In a comparison test, models of the components
of a nose cone (hemispherical C/C composites 50 mm in diameter) were
coated with an ungraded 100 ).lm thick protective layer of SiC (silicon
carbide). Similar C/C composite models were coated first with a graded
SiC/C FGM by penetrative CVD followed by deposition of the 100 ).lm thick
SiC protective layer. All the coated nose cone models were subjected for 1
minute at 1900°C to a supersonic gas flow (at Mach 3) containing an amount
of oxygen approximately equal to a standard atmosphere. The nose cones
with the SiC/C FGM intermediate layer showed no discernible change in
structure even after 10 cycles. In contrast, those without the intermediate
SiC/C layer between the C/C substrate and the ungraded SiC coating
deteriorated after the first cycle [1]. Sheets of SiC/C FGMs produced by
CVD provide excellent thermal stability and thermal insulation at 1227°C, as
well as excellent thermal fatigue properties and resistance to thermal shock
[2].
2.1.2 Rocket and scramjet engines
A C/C combustion chamber with a SiC/C FGM protective layer has been
developed for the reaction control system engine for HOPE, a Japanese
250 Chapter 7
space shuttle under development. The simplified design shown,

schematically in Figure 7.1, has high heat resistance at thermal conditions
simulated by a hot gas flow test [3]. The 30 Jlm thick graded layer of SiCIC
was made by chemical vapor infiltration (CVI) and subsequently coated with
a 100 Jlm thick SiC layer by CVD. Repeated hot gas flow tests indicated that
the FGM coated material was very resistant to delamination and cracking
[4]. However, after stationary or pulsed combustion for 500 seconds, some
partial delamination and corrosion occurred at the SiC layer. This was
attributed to the cyclic thermal stress along the inner wall of the thrust
chamber [5]. Figure 7.2 shows the SiCIC FGM coated engine during a test
[3].
SiC layer (100l-lm) CVD/CVI CIC combu stion

FGM layer (40l-lm) ~ chamber
Inj~-:.I.. ~
NTO c;> ~=--'
MMHC;>r:-I~~~L;~
~--------248~--------~
Figure 7.1. Schematic of the carbon/carbon (C/C) composite combustion chamber for the
engine of the reaction control system of the Japanese space shuttle, HOPE, with an FGM
protective layer of silicon carbide/carbon (SiC/C) [3]. The propellants are NTO (nitrogen
tetroxide: N 20 4 ) and MMH (monomethylhydrazine: N 2H3 CH 3).
Other CVD-SiCIC FGMs produced for rocket combustors have

undergone critical tests with nitrogen tetroxide and monomethyl hydrazine
propellants at firing cycles of 55 seconds with subsequent quenching by
liquid nitrogen. The maximum outer wall temperature of these model
combustors was 1376°C to 1527°C, while the inner wall temperature reached
1677°C to 2027°C. No damage to the combustors was observed after two test
cycles [I].
Most rocket engines use TBC (thermal barrier coating) materials that
have been previously developed for turbine engine applications. The heat
flux in the path of the hot gases is much greater in rocket engines than in
turbine engines. Here the TBCs are exposed to a hostile environment, that is
higher temperatures and more severe thermal transients, but for shorter
mission cycles. Hence, the TBCs are mainly deposited as thin structures «
251
0.2 mm thick) to reduce the probability of coating failure. In large

combustion chambers, the heat flux is so high that high conductivity copper
alloys are used to diffuse the heat away from the inner surface. In this
application, TBes are not ordinarily used because the heat cannot be
dissipated fast enough to avoid local hot spots and coating failures [6].
Figure 7.2. The engine shown in Figure 7.1 during a test carried out in both stationaJ)' and
pulsed modes using the mixed propellants NTO and MMH). (Photo courtesy of National
Aerospace Laboratory, Japan.) [3].
In large liquid propellant rocket engines, TBes are mainly used in the
high pressure hydrogen and oxidizer turbopumps shown in Figure 7.3 [6]. In
the production of both hydrogen and oxidizer turbopumps, TBes have been
used as liners for the spark igniters and pre burners, for turbo housing liners,
for turbine blade shanks (located between the blade platform and root), and
for vane shrouds. Experimental coatings have been used on the turbine blade
platforms and vane airfoils. In addition, TBes have potential applications in
the upper part of the main combustion chamber as coatings on the inter-
propellant plate, spark igniter, and injector baffle tips.
Graded TBes have been considered also for other rocket engines such as
small regeneratively cooled thrust chambers in orbital maneuvering systems
[7]. These zirconia/nickel (Zr02INi) FGM chambers are prepared by a
combination of galvanoforming and plasma spraying. The graded layer is
first deposited (up to 25% Zr02 on a Ni metal chamber) by galvanoforming
and subsequently coated to 100% Zr02 by plasma spraying. No delamination
252 Chapter 7
of zr02 was observed after 550 seconds of combustion. In order to assure the
reliability of the Zr02/Ni FGM, it was necessary to engineer the
microstructure to form strong layers as well as to further optimize the graded
structures, and also to control the reaction with a propellant [8]. As noted
above, graded TBCs are potentially applicable for engine and airframe
structures in reusable hypersonic vehicles [9].
MAIN COMBUSTION HIGH PRESSURE

CHAMBER OXIDIZER TURBOPOMP
HIGH PRESSURE
HYDROGEN
TURBOPUMP
Figure 7.3. Cross sectional schematic of a rocket engine showing the potential location of
thermal barrier coatings (TBCs) in the high pressure hydrogen turbopurnp (left), main
combustion chamber (center), and high pressure oxidizer turbopurnp (right) [6].
2.1.3 Stealth missiles
Stealthiness is now a required specification for modern weapons. Parts

made of specific materials can be used to absorb the emitted electromagnetic
energy to minimize waves reflected in the direction of the enemy radar
receiver. In some applications, e.g. high velocity missiles, the materials can
be subjected to high thermomechanical stress. For these applications, the
most promising new materials are ceramic matrix composites reinforced
253
with ceramic woven fabrics. The use of long, continuous ceramic fibers
embedded in a refractory ceramic matrix creates a composite material with
much greater toughness than monolithic ceramics, which have an intrinsic
inability to tolerate mechanical damage without brittle rupture.
The conducting properties of these ceramic composites depend on the
fibers, the matrix, the interfaces, and other parameters such as the topology
of the arrangement of the various phases. Nicalon® SiC fibers, which have
semiconducting properties, and Nextel® mullite (3Ah03_2Si02_ 0.1 B20 3)
fibers, which are completely dielectric, are used in the preparation of oxide
matrix ceramic composites. Nasicon matrix composites reinforced with long
semiconducting and/or dielectric fibers can have mechanical and electrical
properties, ranging from dc to microwave frequencies [10]. The Nasicon
solid solution, structural formula Na\+xZr2SixP3-x012 (0 ::s; x ::s; 3), which has
an electrical conductivity that varies by four orders of magnitude as a
function of x, is a useful system for investigating the preparation and
properties of ceramic matrix composites with tailored microwave properties.
2.2 Aeroengines
Thermal barrier coatings are used for military and commercial

aeroengines as well as for gas turbine engines for automobiles, helicopters,
marine vehicles, and electric power generators [6, 11]. The TBCs are mainly
used where hot-gas pathways are located in order to increase the temperature
of the turbine inlet. Compared with coatings for diesel engines, the coatings
for turbine engines operate under higher heat fluxes, higher temperatures,
and greater thermal transients [12]. In addition, turbine engine coatings are
subject to hot corrosion and particulate erosion. Coatings for the hot-gas
pathways are usually thin « 0.4 mm) to reduce spalling. For other
applications, e.g. seals that are not in the path of the hot gas, the coatings can
be thicker.
Figure 7.4 shows a schematic cross section of a military turbine aircraft
engine with a wide variety of TBC applications. Although the commercial
turbine engines have similar applications for TBCs, they do not have
augmentor (afterburner) or nozzle sections. TBCs in commercial aircraft are
deposited on the inside liners (i.e., panels and walls) of combustors where
the fuel ignites with air [13], and on the platforms of turbine vanes and
blades where the hot gases expand into the turbine section [14]. Coatings on
the airfoils of blades and vanes where the temperatures, thermal fatigue, and
corrosion are critical are largely produced by electron beam-physical vapor
deposition (EB-PVD ). For the other applications, plasma spraying is
generally used. Thick (2.5 mm) plasma sprayed TBCs are used for
abradable blade outer air seals where the rotating blades cut a gas-path seal
254 Chapter 7
in the porous coatings [15]. In military aircraft turbines, TBCs also are used
on augmentor components, e.g. tail cones, flame holders, heat shields, and
duct liners, and in the nozzle section they are being used experimentally on
the verging/diverging flaps and on seals where the hot gases exit the engine
[6].
Combustor Liners
Turbine V
Blade Outer Air Seals
Figure 7.4. Cross sectional schematic of the turbine engine ofa military aircraft showing the
general location ofTBCs on components (redrawn by [6] from a chart supplied courtesy of
United Technologies).
Turbine blades are one of the most highly stressed rotating parts in gas
turbines. In order to increase the efficiency and performance of
turboengines, gas inlet temperatures in the high pressure turbines must be
increased, and component cooling must be decreased. Here, ceramic TBCs
with a low thermal conductivity applied on turbine components playa key
role. EB-PVD is a promising technology for the production of TBCs with
some advantageous properties. TBCs deposited via EB-PVD have smooth
surfaces without requiring additional polishing, good erosion resistance in
service, and no closure of the cooling holes. But the most important
advantage is their outstanding thermal shock resistance, which is related to
their columnar microstructure. This results in their having considerably
extended lifetimes. The state-of-the-art-material for TBCs is zirconia (zr02)
stabilized with 6-8 weight % yttria (Y 203) that consists of a tetragonal t/-
phase (nontransformable to the monoclinic phase) [16]. Ceramic TBCs are
connected to components by thin metallic bond coats, which also protect the
components from hot corrosion and oxidation. Conventional bond coats are
single layers of MCrAIY (where M = Ni or NiCo) or Pt-AI based materials.
To increase the lifetime of the MCrAIY layers the dissolution of the y-
phase in the superalloy by interdiffusion of Al and Cr must be minimized or
255
if possible, prevented. Therefore, interdiffusion between the superalloy and

the bond coat must be low. This is achieved by increasing diffusion barrier
elements such as platinum or palladium and reducing the Al and Cr contents
at this interface. In contrast, at the interface between the bond coat and the
ceramic TBC, the concentration of oxide forming elements, such as Al and
Cr, in the bond coat should be as high as possible to build up a dense, stable,
and thus protective, alumina (Ab03) scale. The optimal concentration
distribution could be met by grading the composition across the coating
thickness [17, 18].
The interface between the bond coat and the ceramic top coat is the most
critical region with respect to the lifetime of EB-PVD processed TBCs. One
of the major failure mechanisms is the formation of thermally grown oxides
(TGO), particularly alumina, that are generated during processing and grow
by diffusion of oxygen through the protective zirconia layer, and subsequent
reaction with Al at the interface of the zirconia and the bond coat. The
formation of these oxides produces stresses that ultimately cause spallation
of the TBC.
Graded TBC systems are potentially advantageous compared with TBC
systems that have ungraded layers. Gradients can be introduced that combine
the thermal insulation of zirconia with the low oxygen diffusivity of
alumina. Laterally graded alumina/zirconia coatings have been produced by
EB-PVD in order to investigate the morphology, the phases, and the
chemical compositions of the different Ab03-Zr02-mixtures that correspond
to the different regions of a graded TBC [19]. The use of FGMs to join high
temperature materials is being actively investigated.
2.3 Thermal Protection in Diesel Engines
TBCs are utilized in diesel engines for trucks, buses, locomotive, marine
vehicles, tanks, military transport engines, and farm vehicles [20]. Their
advantages in this application are increased power density, reduced heat loss,
and reduced fuel consumption [21, 22]. In addition, TBCs have been shown
to reduce exhaust emissions [23]. Figure 7.5 shows the commercial
application of TBCs at various locations on a diesel engine. Thick (2.5 mm)
TBCs are used on piston crowns, and thinner (0.5 mm) ones are used on
valve faces and cylinder heads. Experimental TBCs have been tested on
cylinder liners, exhaust valve systems and valve seats [12]. It has been
shown that a 5% reduction in fuel consumption is obtained by insulating the
combustion chamber with 2 mm thick functionally graded TBCs [24]. This
performance gain could be increased to an overall 54% thermal efficiency
for certain advanced diesel engine concepts. It has been shown that graded
TBCs have a much longer lifetime [24-26].
256 Chapter 7
Valve Face;:;..~~II'"
Figure 7. 5. Cross sectional schematic of a diesel engine showing the location of rBCs on
various components [6].
3. ENERGY CONVERSION SYSTEMS
3.1 Components for Conventional Fuel Burning Systems
The majority of today's power stations still burn conventional fuels. By

optimizing combustion techniques and combining stationary gas turbines
with steam turbines, efficiencies close to 60 % have been achieved. The
incorporation of advanced material concepts such as FGMs could further
improve the efficiency of these systems [27].
Of particular interest is the replacement of the heavy superalloys by
lighter materials particularly for large fast rotating components. Basic
requirements for widespread application of a replacement material are higher
specific creep strength than superalloys and ductility levels of at least 1 % -
2 % [28]. The low specific weight of 3.9 kg/m 3 makes y-titanium aluminides
(TiAI) candidate materials for turbomachinery applications at intermediate
temperatures (600°C to 800°C) with potential to replace cast superalloys
[29]. Unfortunately, y-titanium aluminides are either strong or adequately
ductile depending on the microstructure, but do not fulfill both requirements
257
at the same time. Heat treatment in the a.-phase field results in fully lamellar
microstructures with excellent creep strength but poor ductility. Heat
treatment in the a. + ~ two-phase field results in duplex microstructures with
acceptable creep strength and ductility that while low is also acceptable.
In gas turbine blades, the ductility has to be maximized in the root block
where temperatures are low due to cooling via the turbine disc. Creep
performance is of minor concern in the root area. In contrast, the airfoils
have to exhibit maximum high temperature strength and creep resistivity.
Ductility is of secondary importance at the blade area. A gradient from a
fully lamellar microstructure at the foil to a duplex microstructure at the root
would provide the desired mechanical properties at both sites.
The underlying principle to obtain the desired gradient of properties is to
create a gradient in the equilibrium volume ratio of the a.+~ phase during
isothermal annealing. This is achieved by introducing a gradient of ternary
alloying elements such as Cr thereby shifting the volume ratio. At a
homogeneous annealing temperature of 1375°C a duplex microstructure
forms in Ti-48AI, and a near to fully lamellar microstructure develops if
sufficient Cr is present. Table 7.1 quantifies the continuous gradient with
respect to the volume fraction of lamellar grains obtained with a
concentration gradient of the ternary alloying elements. Turbine blades of
titanium aluminide with gradients in Cr content have been produced by hot
isostatic pressing. Measurement of the mechanical properties of machined
pieces cut from tested Ti4sAhCr2Nbrri46AbCrsNb2Ta turbine blades that
were evaluated after heat treatment at 1350°C for 2 hours, confirms the
presence of the expected microstructural and mechanical gradients [29].
Table 7.1. The Microstructure of TiAl Alloys as a Function of the Heat Treatment
Temperature and the Alloying Additions [29].
Ti48Al duplex duplex duplex

Ti47AhCr duplex near lamellar fully lamellar
Ti48AhCr2Nb2Ta duplex near lamellar fully lamellar
Ti47AhCr3N~ Ta fully lamellar fully lamellar fully lamellar
In the hot turbine sections of stationary gas turbines combustion gases at

about 1400°C enter the turbine section. However, an internal air cooling
system with a highly advanced design reduces the surface temperature of the
turbine blades to 1050°C or lower. Unfortunately, both the superalloy
material used for the airfoils and the cooling technology are developed to a
performance limit that is unlikely to allow a sizable increase in the inlet
temperature in the near future, unless it becomes possible to develop ceramic
TBCs with a guaranteed service life of at least 25,000 hours and several
thousand restarts.
258 Chapter 7
Premixing the fuel and air before combustion is a method that has a high
potential of achieving an optimized fuel efficiency at low emission levels of
soot, hydrocarbon, and nitrogen oxide (NOx) gases. The critical step for this
combustion concept is the reliable decoupling of the evaporation of the
liquid fuel from the burn zone. This is accomplished by spraying the liquid
fuel on the porous outer surface of an evaporator tube. The vaporized fuel is
transported by the flowing air to the inner side of the tube where combustion
takes place. Therefore, the inner side of the tube must be hermetically sealed,
and there needs to be a porosity gradient from the outer side to the inner side
of the tube.
Porous silicon carbide ceramics are proving to be the most promising
materials for liquid fuel evaporator tubes in gas turbine combustors with
premix burners. During the operation of these tubes, temperature gradients
that are 1500·C at the inner and 550·C at the outer tube wall, are produced
perpendicular to the tube walls. A comparison of finite element modeling
calculations for various systems with both stepped and continuous graded
functions indicates that the use of a specifically designed porosity can
reduce the probability of failure significantly [30, 31].
3.2 Components for Integrated

ThermioniclThermoelectric Systems
The goal of the second Japanese FGM program [32] was to develop high-
efficiency (-40%) hybrid energy conversion system (HYDECS) using
different types of converters adopted for different temperature ranges [33].
Specifically these were a thermionic element at 2000 K, thermoelectric
elements at a lower temperature of 11 OOK, and a heat radiator at an about
300 K [34]. Figure 7.6 shows a schematic of a hybrid direct energy
conversion system proposed in the second Japanese FGM program [35]. In
order to develop an efficient and durable device, an optimized system with
low heat loss and minimal degradation had to be developed. A number of
interface problems needed to be solved with respect to heat and carrier
transportation, materials joining, thermal stress, electrical contact, and
insulation under severe thermal conditions. In the proposed design, the solar
heat receiver is an FGM cavity made of a carbon/carbon (C/C) composite
[34].
259
Graded CIC heat reservoi"
TIC emitte
Graded SiGe ---~
Graded PbTe
Graded AI NNoI radiator
Figure 7.6. Schematic of a hybrid direct energy conversion system consisting of thermionic
and thermoelectric converters.
3.2.1 Solar receiver system
The heat flow through C/C composites via conduction can be controlled
by the design of the fiber architecture. Figure 7.7 a and b shows a C/C
composite cavity for a sunshine heat receiver produced with a graded
arrangement of the fibers [36]. Optimal thermal management in the receiver
requires a high heat flux from the top surface, where the concentrated sun
beams are absorbed, to the bottom surface that transmits the heat to the
transformers. The loss of heat due to heat flux perpendicular to the path from
the top surface to the bottom surface must be minimized. The C/C cavity is
shielded by multiply folded molybdenum cylinders.
A properly designed cylindrical C/C receiver should provide high
thermal conductivity from the flat top surface to the bottom surface, and low
thermal conductivity to the outer cylinder walls. The graded C/C composite
cavity has a gradient both in fiber volume fraction, which increases toward
the central axis of the cavity, and fiber orientation, which in the central areas
is essentially parallel to the axis of the cylindrical cavity. Toward the outer
260 Chapter 7
regions of the cavity more and more fibers are directed circumferentially to
the cylinder [36]. The temperature at the transmitting bottom planar surface
of the receiver is increased by 100 to 1S0°C due to the FGM design of the
cavity as indicated in Figure 7.8.
Solar Rays
,~t ~~
~'--""-'--.""
,u"""
Figure 7.7. A C/C composite cavity for a solar heat receiver fabricated using an FGM
alignment of the fibers. (a) Schematic showing the fiber alignment. (b) A C/C composite
cavity indicating typical temperatures at the inner and outer walls [29].
2000
1900
g 1800
~
::l
iii 1700
....
Q)
c. 1600
E
Q)
f- 1500
1400
0 10 20 30
Distance from center of back wall (mm)
Figure 7.B. Comparison of the temperatures at the bottom transmitting plane of an FGM and a
non-FGM C/C solar heat receiver [29].
261
3.2.2 Thermionic converter system
Thermionic conversion is based on the principle that electrons discharged

from a hot emitter will move to a low temperature collector located on the
opposite side [34]. By applying the FGM concept, the performance of the
thermionic converter can be optimized by decreasing the energy loss
between the emitter and the converter (the barrier index). For this objective
the work function of the emitter needs to be optimized, while the work
function ofthe collector needs to be decreased as much as possible.
The radiated heat from the bottom of the C/C cavity is received by a
titanium carbide (TiC) plate. Titanium carbide has a high melting point and a
high emissivity ("" 0.9), which allows an efficient absorption of heat from a
wide range of the solar spectrum at high temperatures [37, 38]. The heat is
conducted to a rhenium (Re) plate that operates as a thermionic converter
emitter. The transition layers between the heat receiving TiC plate and the
Re emitter should have excellent heat conductivity, should relax the thermal
stresses, and should act as a diffusion barrier between the Re and TiC. This
transition was achieved by a combination of graded layers of TiC/Mo -
MoW - WRe [35]. The collector electrode was made of sputtered niobium
oxide with a very low work function (1.38 eV) on a molybdenum (Mo)
electrode [39]. Using this arrangement, a thermionic conversion system was
constructed with a maximum output of 80 K W1m2 at emitter-collector
temperatures of 1600°C -760°C and a cesium reservoir temperature of 330°C
[38] .
The conventional emitter electrode consists of a tungsten (W) plate. The
dual work function emitter, which is composed of high work function metal-
ceramic composite layers on a low work function W plate, has good electron
emission characteristics. The work function of the collector is decreased by
coating conventional W or Mo electrodes with their metallic oxides. These
two measures combined are expected to result in a major improvement in the
power output. Fabrication of this composite emitter electrode is difficult
because of the high thermal stresses and the interfaces between the ceramic
layers and the metal plates. It is anticipated that by applying the FGM
concept the thermal stresses in these components will be reduced.
3.2.3 Thermoelectric converter system
The efficiency of a thermoelectric power converter is proportional to the

temperature difference between its hot and cold sides. In the case of a
homogeneous material, the thermoelectric figure of merit, Z, shows a distinct
temperature dependence with a peak value that depends on the nature of the
carriers and their concentration. At each temperature a composition exists
262 Chapter 7
that has the highest possible Z value. The pronounced temperature difference
between the hot and cold sides of the converter may require different
material systems to attain the highest figures of merit as indicated in Figure
7.9. Thus from 1300 K to 900 K, the silicon germanium compound, Si. 8Ge.2,
could be used, while lead telluride (PbTe) and bismuth telluride (Bb Te3)
would be advantageous from 900 K to 500 K and 500 K to 300 K,
respectively (see Figure 7.8) [40, 41, 42].
3.5
SZ
""-
..-
'-"
3.0
C')
0
..- 2.5
><
N
......
;::
2.0
-
Q)
E
1.5
0
....
Q) ,
1.0
:::J
Cl
u: ,\'"
PbTe
0.5
0
200 400 600 800 1000 1200
Temperature T (K)
Figure 7.9. Estimation of the figure of merit for an FGM composed of three compounds
(straight line) with partly adapted compositions ofBi2 Te3, PbTe and SiGe in limited
temperature ranges (dashed line).
Figure 7.10 compares the maximum output power of graded PbTe having
different carrier concentrations (a-layer: 3.51 x 10 25 /m 3, b-layer: 2.6 x
1025 /m 3 , c-layer: 2.26 x 10251m3 ) with the maximum output power when each
layer has homogeneous carrier concentrations. The PbTe containing a graded
concentration of the dopant lead iodide (PbI 2) was prepared by laminating
together powders consisting of three different concentrations of the dopant,
followed by hot pressing. The output power was measured at the temperature
of the cold side (500 K). It was shown that PbTe with a graded carrier
concentration has a maximum power of 253 W1m for a temperature
263
differential of 486 K, which is 11 % higher than the highest power for

homogeneous PbTe with the a-layer carrier concentration composition.
- 300
~
E
•
~a-Iayer
FGM
(jj ~b-Iayer
3: 200
0 - 0 - - c-Iayer
a.
E
:::J
E
'xItS
E 100
Q)
>
UQ)
:t:
W
0
0 100 200 300 400 500 600
Temperature difference (6 K)
Figure 7.10. Variation of the figure of merit in an n-type lead telluride (PhTe) conversion unit
with the carrier concentration and temperature, plus an estimation of the figure of merit in the
case of an optimized gradient in the carrier concentration.
The presence of both hot and cold sides requires attaching durable
electrodes to the thermoelectric components that are both compatible with
the thermal expansion mismatch and are sufficiently electrically conductive.
As noted above, SiGe is one of the materials under consideration for use in
thermoelectric conversion at high temperatures. Dense graded SiGe units
with electrodes have been fabricated by a one-step sintering process using
hot isostatic pressing (HIP) with glass encapsulation, shown in Figure 7.11
[43]. Materials with low electrical resistivity, tungsten, molybdenum
disilicide, and titanium diboride (W, MoSi 2, and TiB 2) were selected for the
electrodes. They were blended with silicon nitride (ShN 4 ) in order to reduce
the thermal expansion mismatch in the joints between the electrodes and the
thermoelectric conversion unit.
Two types of units have been designed: WlMoSh/SiGe for phosphorus
doped n-type SiGe and W/TiB 2 /SiGe for boron doped p-type SiGe. The
graded design of the electrodes provides a smooth profile for the electrical
resistivity that decreases continuously from the SiGe to the electrodes, and
ensures the stability of the thermoelectric properties at least up to 1100 K. A
conversion unit made of an n-type SiGe FGM with gradation in the
264 Chapter 7
concentration of the phosphorus dopant shows a marked improvement in

output power characteristics.
W+40 vol.% Si,Ns
MoSi 2+55 vol.% Si3N4

SiGe (0.5 at.% P)
111111\111111111\111111111\1111 \ I
1 2 3 4
Figure 7.11 . A dense, graded n-type silicon germanide (SiGe) conversion unit produced by
single-step hot isostatic pressing with sintering. (ShN4 : silicon nitride, MoSh: molybdenum
disilicide).
A system with an optimized FGM configuration is predicted to provide a

conversion efficiency of 20.6% compared with approximately 18.7% for a
conventional ungraded system. Optimization includes determination of the
most advantageous length for each stage of the configuration and also of the
most advantageous number of devices that are connected in series and
parallel. In addition, radiation heat loss is taken into consideration because of
the elevated operation temperature of the SiGe stage. A 2- dimensional finite
difference method was developed requiring the upper and lower end
temperatures, the temperature dependent values of thermal (K) and electrical
(0") conductivity, and the Thomson coefficienC 't ('t = T dex./dT, ex. = the
Seebeck coefficient8) [44]. Other computational design procedures use
electron and phonon transport coefficients calculated by band theory
combined with an elastic thermal stress analysis by 2-dimensional finite
element modeling [45]. Transport properties also have been calculated that
7 The Thomson coefficient is defined as the ratio of the voltage between two points on a
homogeneous conductor to the difference in temperature of those points when an electric
current flows between them.
8 The Seebeck coefficient is defined as the ratio of the open-circuit voltage to the temperature
difference between the hot and cold junctions of dissimilar conductors in the same circuit.
265
include in part the influence of microstructural features such as grain

boundaries [46, 47, 48, 49].
3.3 Components for the Fusion and Nuclear Reactor

Field
The fabrication of the components that are directly exposed to the plasma
in steady-state magnetic fusion reactors, such as the diverter plate and the
first wall, is the key technology for the successful development of these
reactors in the near future. These components are subjected to extremely
high heat fluxes and incident particle fluxes that cause thermal shock,
thermal fatigue, and erosion. Materials for components exposed to plasma
have been investigated worldwide with particular emphasis on materials for
armor, on bonding techniques, and on heat flux tests [50, 51]. FGMs have
been proposed as possible solutions for reducing the deleterious effects of
thermal stresses [52].
A diverter plate of a graded tungsten/copper material has been produced
by sintering a tungsten skeleton with graded porosity to a mechanical
stability that allows its subsequent melt infiltration with copper [53]. The
tungsten side of the FGM can withstand the highest temperature hot spots in
the plasma, while the opposite copper-rich side has sufficient thermal
conductivity for adequate cooling with water. This graded composite has
proven to be effective up to heat fluxes of 15 MW/m 2 (see Figure 7.12),
which is the required qualification for diverter plates exposed to the plasma
in the International Thermonuclear Experimental Reactor (ITER).
The graded tungsten/copper target of the beam attained a steady state
after 10 seconds of irradiation. The maximum surface temperature of the
tungsten did not reach 830°C, and no surface fissures, cracks, or spalling
were observed after up to 40 seconds of irradiation [54]. Using the same
electron beam irradiation system and a particle beam engineering facility,
chemical vapor deposited FGM coatings of titanium carbide/carbon 1 mm
thick were evaluated at a surface heat flux of up to 70 MW/m2 for several
seconds. The FGM film sustained temperature differences as high as 1500°C
without cracking or melting [55].
3.4 Components for Fuel Cells
Fuel cells are electrochemical devices that convert chemical energy

directly into electrical energy. Electricity and heat are generated by the
electrochemical combination of a fuel with an oxidant. They offer several
advantages including a relatively high conversion efficiency, low emission
266 Chapter 7
of pollutants, a potential for cogeneration of electricity and heat, fuel and

product flexibility, and minimal siting restrictions compared with other
1 :~~ m
power plants.
i
25 l
1500 12
4 • ....t.rIail !II, I
"" CU
~1~~·_~
__~__~__~_S_wH-.~.-__~__~~T-41
~ n
..
~
1ii
n
~ 5OOj--t~~~~~~-r--~~
~
initial t8l'l1Ml'atll'e of coollnl water (298K)
o 5 10 15
Electron beam power density (MWIniI-)
(a)
TI
i n
! ...,. In..
~I ~\.
TC
.5
;'
"
. ...i~
~ 0
o.~
I'"
0.. ...
f- -
(b)
Figure 7.12. The results of electron beam irradiation tests. (a) The temperature distribution
during heating to a stationary heat flux of 15 MW/m 2. (b) The effect of the electron beam
power density on measured temperatures.
Fuel cell systems are categorized based on their electrolyte materials.

One type is the solid oxide fuel cell (SOFC) system. This consists of a
cathode on the air side and an anode on the fuel side, with both sides
267
separated by an oxide electrolyte with a high ionic conductivity. Oxygen

from the air is reduced at the cathode side to 0 2- by gaining two electrons,
and diffuses through the electrolyte to the anode. Fuels such as H 2, C~ or
natural gas, are oxidized at the anode side to H 20 or CO thereby releasing
electrons to the external circuit at the cathode. Solid oxide fuel cells require
a number of functional electrochemical components and contact materials as
shown in Figure 7.13 [56]. The electrodes are connected to the electrolyte by
electrode/electrolyte interfaces with low interfacial polarization and
chemical compatibility. This transition region can have a large triple-phase
boundary length (electrode/electrolyte/gas) or can be a mixed conductor.
Interface electrode/interconnect
good mechanicaVelectrical contact
Cu nent collector
chemical compatibility
Electrode main strucbJre
Electrode: 1I333333333333333333333:IB=-r-_ low in· plain resistivity, porosity for gas diffusion
... Interface electrode/electrolyte
Electrolyte bw nterfacial polarization
more electrode/electrolyte/gas
il terfaces or mixed conductor
chemical compatibility
Figure 7.13. Electrochemical components and materials required for the electrode/electrolyte
layers of solid oxide fuel cells [56].
The main electrode requires a low in-plane resistivity and sufficient

porosity for gas diffusion. The current collector is connected to the electrode
by an interface region that must maintain good mechanical and electrical
contact between the electrode and the current collector and also adequate
chemical compatibility. The operating conditions require lifetimes of several
ten thousands of hours at temperatures between 800°C and 1000°C in an
oxidizing atmosphere. Most of the components are made of ceramic
materials or metals with high-temperature oxidation resistance. For example,
yttria stabilized zirconia or YSZ (Y 203-Zr02) has been used for the
electrolyte, lanthanum strontium manganite (Lal_xSrxMn03) for the cathode
(air electrode), nickel-zirconia (Ni-Zr02) for the anode (fuel electrode), and
lanthanum strontium chromite (Lal_xSrxCr03), or high temperature alloys for
the interconnects (current collectors).
For solid oxide fuel cells that can operate at lower temperatures to be
technically feasible, the electrolyte resistance needs to be lowered. This can
be achieved by reducing the thickness of the YSZ-electrolyte and by
minimizing the electrolyte/electrode interfacial losses by using more
efficient electrodes. In addition, the fabrication conditions and the operation
268 Chapter 7
of all of the components must be compatible. Gradient configurations should

improve the operation of this fuel cell [56].
For current SOFC systems a large part of the voltage losses arise on the
cathode side (air side). Therefore, it would be desirable to optimize the
cathode layers, the cathode/electrolyte, and the cathode/interconnect
interfaces. From a material selection standpoint the cathode material should
fulfill the following requirements: high electronic conductivity, high ionic
conductivity, high catalytic activity for oxygen reduction, chemical
compatibility with the electrolyte and interconnects, compatibility of the
thermal expansion coefficient with the other components in the fuel cell,
stability in air at high temperatures, absence of destructive phase
transformations, and the ability to be formed into films. The use of a gradient
material in this application is most likely to satisfy the many seemingly
contradictory requirements [56].
One approach is to use a graded multilayer configuration of strontium
doped lanthanum chromite (La\.xSrxCr03) because the thermal expansion
coefficient of this material and the electrolyte are similar, and also because it
is chemically compatible with zirconia (zr0 2), the fuel cell's main material.
In order to increase the electrical conductivity of the homogeneous La\.
xSrxCr03, the Sr content is increased toward the electrode side in two graded
steps. Replacing the fuel cell's original interconnect made of the
homogeneous material with the graded three-layer interconnect increases its
power output by 40% [56].
Strontium doped lanthanum manganite (LSM) is a material of choice for
the cathode of solid oxide fuel cells because of its chemical stability, good
electrical conductivity, and relatively low overpotential for oxygen
reduction. It has been shown experimentally that addition of the electrolyte,
yttria stabilized zirconia (YSZ), improves the cathode's performance. During
actual operation the LSM and YSZ content as well as the porosity and pore
size need to be continuously varied in order to optimize the triple phase
boundary length and the current collection. When vacuum plasma sprayed
cathodes with different gradations in their LSM-YSZ content were tested in
planar substrate-type solid oxide fuel cells, both the cathode performance
and the cell's lifetime were affected by the different concentration profiles
[57].
The use of the more active lanthanum cobaltite (LaCo0 3) in cathodes
creates compatibility problems with the YSZ electrolyte. Ceria-based
materials (Ce02), however, show no interaction in contact with LaCo0 3.
Therefore the incorporation of a cerium-gadolinium-oxide (CGO) protective
layer between the electrolyte and the cathode was considered a possible
solution. A low temperature densified ceria material and interdiffusion
phenomena between YSZ and CGO were investigated to determine the
269
feasibility of cofiring the double layered ceria-zirconia electrolyte. The best

results were produced by a graded composition of the solid solution phase of
YSZ-CGO [58].
By using materials with eutectic microstructures (regular arrays of
lamellae or rods) for the anodes of solid oxide fuel cells (SOFCs), both their
electrochemical activity and their thermal stability can be increased. To
produce a eutectic of NiO-YSZ, a microwave melting process was developed
that allows crystallization to occur within a wide temperature gradient. The
microstructure resulting from melting the electrodes directly onto the top of
the YSZ electrolyte substrate is composed of partly aligned lamellae
perpendicular to its surface. The thickness of the alternating NiO-YSZ
lamellae is graded over the thickness of the electrode; it increases with
increasing distance from the substrate. In terms of functionality, this means
that there is an inverse gradient between the electrochemically active triple
phase boundaries (gas - Ni - YSZ) after the NiO is reduced to Ni. During the
reduction process, the microstructural gradient of the thickness of the
lamellae (or the inverse gradient of their density) is converted into a
functional gradient of electrochemically active sites. This is because the
graded density of YSZ lamellae coated with Ni particles represents an
increasing number of triple phase boundaries per unit area. This model
elucidates how this type of eutectic microstructure could also lower the
overpotential of SOFCs [59].
Natural gas, which consists mainly of methane, is the most promising
fuel for stationary applications of SOFCs. The endothermic steam reforming
of this fuel within the anode chamber of the SOFC stack (internal reforming)
is applied advantageously to reduce the cost and increase efficiency. The
reforming reaction, which is catalyzed by the NilYSZ anode, is rapid, and
depends to a great extent on the temperature distribution within the SOFC
stack. However, within the stack's fuel inlet area, a considerable degree of
cooling can occur resulting in large temperature gradients. To prevent this
local cooling, the catalytic activity for reforming of the NilYSZ anode must
be decreased at the top layer of the anode material, which is in contact with
the initial fuel gas mixture, without decreasing the activity in the interior of
the anode. Therefore, for optimal performance, the anode should be designed
as an FGM. To reduce the NilYSZ anode's catalytic activity, a sol-gel
method has been used to coat and infiltrate it with YSZ while retaining its
gas permeability and electrical conductivity [60].
In an SOFC with a planar design, a metallic bipolar plate is used to
separate the ceramic single cells. These ceramic single cells consist of a YSZ
electrolyte, cathodes of strontium doped lanthanum manganite, and anodes
of a Ni-cermet. During their operation (at 950°C) an electrical contact
between the metallic plate and the screen printed electrodes has to be
270 Chapter 7
maintained. This problem can be solved using intermediate layers between

the metallic plate and the single cells. However, these layers must be ductile,
at least before the initial heating of the stack. Porous layers fulfill this
requirement. In addition, however, because the used metal forms a Cr03
scale that volatilizes as CrO at 950°C in an oxygen atmosphere, a protective
layer is needed to prevent Cr03 evaporation from the metallic bipolar plate.
This is because the Cr03 condenses in the cathode and leads to a decrease in
the long term stability of the SOFC. In contrast to the contact layer this
protective layer must be dense.
In the initial attempts to develop a gradient material as a solution for this
problem, different compositions of the system (La, Sr) (Mn, Co) 0 3 were
investigated for the contact layers, and both doped LaCr03 and doped YCr03
were investigated for the protective layers [61].
4. CUTTING TOOLS
4.1 Wear Resistant Bulk Materials
The Japanese sword exemplifies a classic application of the FGM

concept. It is composed of steel with a gradient in carbon content from the
surface (-0.6% carbon) to the interior (-0.25%) [62]. The graded carbon
composition results in a tough sword with a sharp edge that remains sharp
during prolonged use due to its increased wear resistance. This sophisticated
technology, which was established about 1000 years ago, gave these classic
swords and knives superior hardness and toughness.
More recently, in order to extend machining efficiency, the cutting
speeds and feed rates have been substantially increased. Therefore, modern
cutting tools need to withstand considerable thermomechanical stresses and
require substantial thermochemical resistance against reaction with the parts
being machined. Various techniques to fabricate compositionally graded
tools and graded multilayer coatings have been developed to cope with the
increasingly harsh conditions at the cutting tool tip and in the bulk of the
parts being machined [63].
Construction parts and tools generally are subjected to a range of loads
that cannot be satisfied by a single material or composition. For example,
cemented carbide (tungsten carbide-cobalt; WC-Co) tools often require
extreme hardness at the surface regions of the cutting edges but a stronger
and tougher base material. If the size and configuration of the carbide
particles remain the same, the hardness of the WC-Co system depends
almost linearly on the binder (Co) content, with Vickers hardness of HVI 0 =
271
2100 at 5 volume % binder and 1100 at 30 volume % binder. At the same

binder content, the hardness increases with decreasing grain size.
Unfortunately, the transverse rupture strength and the fracture toughness
(K1c) decrease with increasing hardness almost independent of compositional
and microstructural details. These relationships between microstructure and
properties are the basis for FGM cutting tools.
Cylindrical or bar-shaped compacts (formed at 150 to 300 MPa pressure)
with a three-layered configuration have been fabricated [64]. The
composition and/or grain size of the two peripheral layers are different from
that of the central layer. The cobalt (Co) content varies between 5.5 and 11
weight %, the tungsten carbide (WC) grain size in the sintered alloys is
between 0.4 J.lm and 4 J.lm. During liquid phase sintering (1400°C- 1450°C)
the melt flow is controlled by the phase distribution and the grain size of the
carbide phase. As expected, if the layers contain carbides of equal size, the
cobalt content tends to equalize throughout the compacts during sintering
almost independent of the initial Co distribution. If the size of the WC
particles in the layers differs, melt enrichment in those areas with smaller
sized carbide particles is observed. Figure 7.14 (a) and (b) shows the Co
distribution in a three-layered bar before (a) and after (b) liquid phase
sintering.
Functionally-graded cutting tools for high speed cutting or for machining
at high feed rates have been developed by Sumitomo Electric Industries Ltd.
One is a graded WC/Co throwaway chip [65, 66]. It is designed with a
decreasing Co concentration from the surface to the interior, which causes
the hardness at the cutting tool's surface to be higher than its interior.
Graded and ungraded cutting tools are compared in Figure 7.15. This
gradient in hardness results in both considerably higher damage resistance
and higher wear resistance than a cutting tool with a homogeneous
composition. The graded composition in WC/Co is produced during
sintering by controlling the atmosphere and the rates of heating and cooling.
In addition, the WC/Co FGM is coated with a layer of titanium nitride
(TiN), a layer of alumina (AI 20 3), and a layer of titanium carbonitride
(TiCN) by chemical vapor deposition. These graded and multiply coated
WC/Co FGM cutting tool chips are very resistant to flank wear.
Furthermore, they have the advantage of high machining speed combined
with a high feed rate. Their graded composition can also control the internal
stress arising from the thermal expansion mismatch. A simple, asymmetric
gradient in composition such as in a ceramic/metal FGM can relax thermal
stress, while a symmetric or radial gradient can induce a sizable compressive
stress at the outer ceramic layer, resulting in stress reinforcement similar to
tempered glass or prestressed concrete [67, 68].
272 Chapter 7
20 -0-- before sintering

wC-Co wC-Co
18
• after sintering
;g
0.
16
"0 14
~
12
C
Q) 10
C
0
()
8
....
Q) 6
"0
C 4
CD
2
0
0 2 3 4 5 6
Distance (mm)
(a)
2200
wC-Co WC-CO
2000
S 1800
>
~
wc-TiC-TaC-Co
en 1600
en
Q)
c
....
"0 1400
CIS -0-- before sintering
I
1200 • after sintering
1000
0,0 1,0 2,0 3,0 4,0 5,0 6,0
Distance (mm)
(b)
Figure 7.14. Flow in a 3-layer bar caused by compositional differences in the carbide phase
before and after sintering: (a) binder (Co) composition, (b) microhardness. (After [64]).
Tough FGM cutting tools based on this model were commercialized in

1996. To fabricate them, green (unsintered) compacts of a mixture of
powdered TiCN, 40 weight % WC, 10 weight % Co, and 5 weight % Ni are
sintered at 1400°C in a vacuum for 1 hour under controlled nitrogen
pressure. The WC in the outer layer dissolves in the Co-Ni melt and
273
reprecipitates as a solid solution of (TiW)(CN) at the surface. The molten

metal continues to flow onto the surface when the atmosphere and other key
parameters such as the cooling rate are controlled. This process results in a
gradation in cobalt content as seen in Figure 7.16, thus hardness from high at
the surface to low in the interior after the surface layer of metal is removed
because the hardness decreases with increasing Co metal content [69]. The
thin surface layer of the cutting tool is composed almost completely of
ceramic without any metal binder. This results in a high hardness of 22 GPa,
and the compositional gradient in the Co metal phase produces a high
surface compressive stress of 0.8 GPa, as shown in Figure 7.17. The high
surface hardness and compressive stress plus the toughness of the interior
almost doubles the wear resistance, and increases the tool life as much as
fivefold compared with conventional cermet tools.
«i' 1 8 r - - - - - - - - - - - - - - - - .
&
-rn
rn
Q)
16
IAC151
c
"0
14
.....
ctl
.!: Conventional coated chip
rn 12
.....
Q)
..lo::
()
10
:>
6
.....
.~ 8
:: o 50 100 150 200 250
Distance from the surface (J.I. m)
Figure 7.15. Comparison between the hardness at the surface of a cemented carbide (wc/co)
FGM (ACl5) cutting tool and a conventional tool [65).
The in-situ formation of a graded structure from a homogeneous green

body by controlling the atmosphere and processing parameters such as the
cooling rate, is a promising approach for a cost effective process. Other
process controls such as the heating rate and the nonuniformity of heating or
cooling could also be useful for the in situ formation of graded structures.
Graded cutting tools have also been made for interrupted cutting from
cermets of TiC-NiMo in which the percentage of TiC in the graded layer
ranged from 95 weight % at the top surface to 86 weight % at the transition
274 Chapter 7
site to plain steel [70]. A gradient structure was obtained by brazing together
segments having different compositions. Successful cutting results
demonstrate that enhanced performance can be obtained using the gradient
concept to prevent damaging tensile loads. The fabrication method for these
graded cutting tools was based on previous work to produce gradient armor
[71 ].
-
(J)
c...
50
~
40
-
0
()
0 30
>-
:=:
-
C/l
c: 20
Q)
c:
>- 10
...,
en
x 0
0 20 40 60 80 100 120
Distance from the surface ( f.!m)
Figure 7.16. The cobalt concentration (X-ray intensity) as a function of the distance from the
surface ofa TiCN/WC/Co-Ni FGM measured by electron probe microanalysis [69].
275
-«S
Q. 24 1.0 (ij"
Q.
~ 22
(/)
(/)
0.8 ~
(/)
-
CD
20
c
...
(/)
...«S
'0 0.6 CD
(/)
.r::. 18
~ 0.4 .~
16 (/)
~
...0.CD
(/)
(,)
0.2
:> 14
E
...
I
0 0
(,) 0 ()
~ 20 40 60 80 100 120
Distance from the surface (~m)
Figure 7. J 7. The hardness and the compressive residual stress as a function of the distance
from the surface of a TiCNIWC/Co-Ni FGM, indicating the high hardness and compressive
strength at the surface [69].
Diamond cutting tools are increasingly used for high precision machining
of soft components, such as plastic contact lenses, polygonal mirrors for
laser printers, and hard disk substrates made of aluminum alloys.
Conventional diamond cutting tools are manufactured by joining a diamond
crystal onto a metallic alloy shank with a silver solder containing active
metals. However, the machining accuracy is relatively poor due to the silver
solder's lack of stiffness, which causes vibrations during machining. This
problem was solved in 1992 with the development of extremely stiff FGM
diamond tools with a graded layer of diamond/SiC between the diamond
chip and the SiC shank [72].
These FGM diamond tools are produced by a reaction sintering process
shown schematically in Figure 7.1S. The shank is formed from a green
compact made of several graded layers of SiC powder mixed with from 0 -
SO volume % diamond powder and a polymer binder. The compact is heated
to carbonize the binders and subsequently infiltrated with molten silicon.
The silicon and carbon react to form new SiC grains that bond the existing
SiC grains with the diamond particles. As shown in Figure 7.19, a thin layer
of the diamond chip at the interface with the graded diamond/SiC layer
reacts with silicon and converts to SiC, resulting in the formation of a
strongly integrated body without metal interfaces. Finite element analysis
indicates that the formation of the graded layer can reduce the thermal stress
at the joint of the diamond chip and the SiC shank from 400 MPa to 150
MPa. An almost sixfold improvement in machining precision has been
reported for these tools, with as much as a 30% extension in tool life.
276 Chapter 7
However, despite their performance advantages, FGM cutting tools are still
too expensive to manufacture to be commercially cost competitive.
....,
,
Diamond particle SiC particle Polymer
...
~
~
...
........ I
........
I ...·t·,.·
1":_
~OMiXing
~...-~ ~
Pre-compaction
of non-FGM
t=:J
~ Shaping of the tool's shank
with a FGM joining layer
Carbonization of polymer Diamond

chip
_-----_
~R eactlon
. .. h
slntenng toget er
with a diamond chip
Diamond tool
FGM layer
Figure 7.18. Schematic of the process for fabricating diamond/SiC FGM cutting tools [72].
Nevertheless, it is easier to apply the FGM concept to cutting tools than

to larger and more complex FGM components, since their effectiveness can
be assessed quite quickly with relatively simple tests. For this reason, it is
anticipated that the practical applications of functionally-graded cutting tools
will continue to grow, and the transfer of the resulting advances in the
technology to other applications for FGMs will soon follow.
4.2 Wear Resistant Coatings
Several types of graded coatings for the cutting edges of tools have been
developed recently. These are coatings in which the carbide/nitride content is
277
varied from the substrate interface to the surface, and also coatings in which
nitrides of different metals are alloyed so that their final compositions are
graded. For specialized applications such as drilling and milling, bifunctional
coatings are used that are built with anti galling hard coatings like titanium
nitride and self-lubricating moderately hard coatings like WC/C, in which a
diamond like carbon matrix is strengthened by incorporation of WC crystals
[73].
Graded cemented carbide coatiQgs on steel substrates relieve the thermal
stress associated with homogeneous WC/Co coatings. These graded coatings
are made by stacking on the steel substrate, multiple layers of cemented
carbide powders in which the Co content is compositionally graded. This is
followed by sintering via pulsed electric current sintering. Because of the
low sintering temperature and the short sintering time the desired graded
composition of the cemented carbide is maintained, and a crack-free WC/Co
coating is obtained on the steel substrate [74].
In 1995 Matsushita Electric Industries introduced an advanced electric
shaver with thin FGM blades of stainless steel that have a hard intermetallic
compound of an iron aluminide (Fe-AI) precipitated on their surface. The
graded composition results in a hard but flexible surface aimed at producing
a smooth and comfortable shave [75].
Figure 7.19. Schematic of the bonding between a diamond chip and a diamond/SiC FGM
[72).(CD - diamond chip, ~ -bonding phase, @ - diamond particles, @ - reaction sintered SiC).
5. MACHINE PARTS
There is little published information about the applications of graded

materials as engineering components other than for coatings and wear
resistant materials [76]. Therefore, it is difficult to classify the application of
an FGM that exhibits several functions concurrently, for example, a silicon
carbide reinforced carbon-carbon composite (SiC/C-C) that acts as a
278 Chapter 7
structural part of the heat collector for an energy conversion system and also
provides thermal stress relaxation, heat conduction, and oxidation protection.
The major application of FGMs for machine parts is for joints, largely
metal-ceramic joints for gas and steam turbines [77, 78, 79]. The advantage
of using an FGM joint is chiefly for thermal stress relaxation and improving
the strength and toughness of the joints. Figure 7.20 shows a schematic of an
alumina-nickel superalloy specimen joint for mechanical testing made by
plasma spraying and diffusion bonding [77, 78, 79]. Because the rupture
strength of graded joints is 3-8 times higher than for directly bonded joints,
they are expected to provide longer service life at elevated temperatures.
100
-
~
'0
80
~
CD 60
III
1\1
.r.
Q. 40
~ 20
~
0
234 5
Thickness of the graded layer (mm)
Figure 7.20. Schematic of an alumina - nickel (AIz03-Ni) alloy graded joint for high-
temperature applications. The graded layer is composed of AIzOiNiCrAIY plasma sprayed
layers with different contents of the metal phase [78].
279
Another FGM application that involves thermal stress relaxation and a

low coefficient of friction is in the welding apparatus used, for example, for
the automated electric arc welding of the large aluminum sheets used in
building huge ships such as liquid natural gas (LNG) tankers. This welding
device uses sliding water-cooled copper "shoes" that move along the seam
and support the molten aluminum bath. Figure 7.21 indicates the location of
the FGM component. The electric arc between the melt and the electrode
wire oscillates between the shoes on the sheets being welded together. The
inserts, -which prevent both reaction between the molten aluminum and the
copper and the shoes from sticking to the hot aluminum surface, are usually
made of silicon nitride to obtain a low friction coefficient and a good seam.
However, their life is limited under the thermal cycling conditions during
normal operation. This problem is alleviated with a SbN4-Cu FGM
fabricated by a process, shown in Figure 7.21, that combines powder
metallurgy and infiltration. The FGM design improves the stability of the
inserts, reduces their thermal stress, and retains their low coefficient of
friction [80].
Engine components are also being designed using ceramic-based FGMs
to improve their thermal fatigue life by making them more heat-insulating.
For example, in a hybrid design for the pistons of a diesel engine for
passenger cars, the ceramic content is gradually reduced with increasing
distance from the piston head [76, 81].
Materials with graded porosity produced by conventional powder
metallurgical methods are used for filters and membranes [76, 82, 83]. A
new technique, gas-metal eutectic transformation in metal-hydrogen
systems, discovered in Russia, can be used to produce graded near net-shape
components of strong, permeable, porous materials called GASARs (the
Russian word for gas-reinforced), shown in Figure 7.22 (a) [84, 85]. The
transformation involves the decomposition of a molten metal that does not
form a stable hydride (e.g., copper, aluminum, iron, or brass) but reacts with
hydrogen at high pressures to produce both a solid and a gas phase via a
eutectic. The solidification processing involves the charging or saturation of
the liquid metal melt with gaseous hydrogen until the eutectic composition is
reached, followed by directional melt solidification. The hydrogen level in
the melt, the gas pressure over the melt during solidification, the direction
and rate of heat removal, and the chemical composition of the alloy, all
influence the amount of porosity, and the shape, size, and orientation of the
pores. Pore sizes can range from 5 J.!m to 10 mm and pore volume from 5%
to 75%.
280 Chapter 7
Welded sheets
Oscillation of the guide

~
Electrode wie
Sliding oopper shoe

(water-cooled)
Movement direction
Figure 7.21 . The process for arc welding two large aluminum sheets, and the microstructure
of the Si)N4 -Cu FGM insert plate [77].
An FGM rectangular bronze GASAR with grading in the diameters of the

pores, is shown in Figure 7.22 (b) [78]. FGM GASARs can be made both by
controlling the gas-eutectic in the phase diagram and by appropriately
designing the cooling system [86]. GASARs are claimed to be the strongest
281
permeable porous materials, thus usable for structural load-bearing

components. Other suggested applications include as filters, catalysts,
mufflers, heat exchangers, self-lubricating bearings, silencers, vibration
dampers, and shock absorbers [84]. The potential for grading their porosity
plus varying the shape of the pores and their distribution in radial and axial
directions can give these materials additional useful properties such as
anisotropic heat conductivity, liquid/gas permeability through the thickness,
and nonlinear thermal elastic-plastic behavior [85] .
./ --' "
6,'
/ . /,;,~
(~\I
, /'
\~S.~:
.... _ .. '"
~~lf/t1/
~9 •• '
/'--/'9--~
••....• ........
/'
• •••
/'/'
.
••
.
/'?
'l
6
'"II
.. ...•.
••• • ••• ••••• ~'1
• • • • • •••• . d~' ~
• ~ •••. ! ••.•• ; It" I
e ..•• ~ .•....•...
~ •• ' /'
•.........
'., : /'
Porosity gradient
(b) •
Figure 7.22. Various geometrical structural types ofGASARs (gas-reinforced materials),
produced under different processing conditions of gas-eutectic reactions; (a) ungraded
GASARs, and (b) a graded GASAR[80].
Structural components have also been made of nickel- and iron-based

superalloy FGMs containing a Ti(C,N) graded metal phase [87]. In copper-
graphite FGMs made by controlled mechanical alloying, that is by arresting
the process at predetermined intervals, then arranging the various fractions
sequentially and hot pressing them, both the graphite concentration and the
particle size distribution are graded. Casting molds with high thermal
conductivity and wear resistance, and a relatively low coefficient of friction
282 Chapter 7
have been made by joining this FGM to a graphite part by vacuum brazing
with a copper-based solder [78].
6. GRADED BANDGAP SEMICONDUCTORS
The concept of graded bandgap structures in semiconductor research was

introduced in 1957 with the theoretical investigation of their potential
application to transistors [88]. This section describes the unique and
desirable functions and applications of graded band-gap structures in
semiconductors.
6.1 Semiconductor Heterojunctions
Semiconductor heterojunctions can be regarded as an extension of

multiple heterostructures. In considering the band diagrams of abrupt
heterojunctions (where the composition changes from that of one to that of
the other within one atomic layer) without interface defects, two
semiconductors are assumed with different energy bandgaps, Egl and E g2 ,
electron affinities, Xl and X2, and Fermi energies, EFI and E F2 , as shown in
Figure 7.23 (a). Electron affinity is defined as the energy to transfer an
electron from the edge of the conduction band to the vacuum level. Unlike
the work function, which is defined as the energy to take an electron from
the Fermi energy level to the vacuum level, electron affinity is a
characteristic quantity for each semiconductor because it depends on the
concentrations of impurities.
vaCUUJn level
X2 ¢lz
XI ¢II CB
CB
!~E('
- - - - - - - EFl Egz
-----~·v
Egi
VB ~
- --- - - -
c
semiconduclor I semiconductor 2
(a) (b)
Figure 7.23. (a) The essential band parameters for semiconductors, and (b) the energy band
diagram of the heterostructures composed of the semiconductors shown in (a).
283
When these two semiconductors are brought into contact, the energy
differences of the conduction band, Ec=Ec\-Ec2' and the valence band,
Ev'=Evt-EV2, are conserved, because it can be assumed, as a first order
approximation, that the bulk properties of the semiconductors are conserved
even in the vicinity of the interface. At the same time, electrons close to the
junction in semiconductor 1 move toward semiconductor 2, resulting in band
bending as shown in Figure 7.23 (b).
The significant features of heterojunctions are the presence of energy
steps at the junction owing to band discontinuities. Therefore, staircase-
shaped energy band profiles can be prepared by stacking different
semiconductors one after another. A smooth energy band profile, rather than
a staircase-shaped profile, should then be achieved readily by reducing the
distance between the interfaces and gradually changing their compositions.
The precise values of energy band discontinuities for various
semiconductor pairs have been studied both theoretically and experimentally
for a long time, since they are among the most important parameters for
designing heterostructures. However, experimentally determined band
discontinuities are somewhat different from estimated values that are based
on the simple assumption discussed above. This is because crystalline
periodicity is not present at surfaces and interfaces.
Figure 7.24 indicates the relative energy levels of the bandgaps for
typical semiconductors when heterostructures are prepared that are based on
a theoretical model [89]. Band lineups of heterojunctions composed of any
two semiconductors shown in Figure 7.24 are possible. However, given the
variety of possible combinations, heterojunctions of practical importance are
quite limited, since lattice mismatch causes dislocations and dangling bonds
that generally act as effective scattering and recombination centers for
carriers. As an approximation, the lattice mismatch of heterojunctions should
be reduced to less than 0.3 %.
6.2 The Functions of Graded Bandgap Structures
The functions of graded structures in semiconductors can be classified as:

crystallographic, electronic, and optical. The crystallographic function is the
simplest. Heterostructures are usually prepared using epitaxial growth
techniques on suitable substrate crystals. However, epitaxial substrates are
limited to elemental or binary semiconductors such as silicon (Si), gaIIium
arsenide (GaAs), and indium phosphide (InP), because it is difficult to
produce crystals of alloys with uniform and accurately designed lattice
constants. When substrates with matching lattices cannot be obtained, a thick
buffer layer, in which the lattice constant is changed from that of the
substrate to that of the material to be grown, is deposited on the substrate
284 Chapter 7
prior to the growth of the desired layer. Misfit dislocations are introduced
gradually during the growth of a buffer layer so that substantial reduction of
dislocation density in the required layers can be obtained. Although this
function is very primitive, such a buffer layer has been utilized even in
commercially available devices, such as orange-colored, light-emitting
diodes.
r'--''''
II
, I
1 !
I i
! I 1:"...."--,
, I
~ ! I i !'".''''~'
II I I
!'··_·-t
~ i
i~ Ii I r'''-1
-Un , ·8- '-"f1-D-~Gg ~

SI G.
GaP InP
GaA. InA. AISb
CdT.
AlAs
AlP
ZnS.
Figure 7.24. The band discontinuities ofheterojunctions are shown as relative positions of
bandgaps based on a theoretical model [88]. The dashed line indicates the midgap energy,
which is the energy to be aligned when the heterojunction is formed.
Electronic functions are of particular importance and specific to graded

bandgap structures. In graded semiconductor structures, the conduction band
edge energy, Ec (r), and the valence band edge energy, Ev (r ), which are
functions of the coordinates, Ec (r ) and Ev (r ), are the lowest energies for
electrons and holes, respectively. In addition, the energies of carriers with
higher energies can be represented as the sum of the kinetic energy, K, and
the band edge energies. Therefore, Ec (r ) and Ev (r ) can be regarded as
potential energies for electrons and holes, respectively.
When the potential energy of a body, U (r ) has a gradient, the body
receives a force of F = - grad U (r ). The forces on electrons and holes
exerted by external electric fields are equal in magnitude but opposite in
direction, as shown in Figure 7.25 (a). Similarly, electrons and holes in
graded structures receive forces due to their position that depend on the band
edge energies as if they were in an electric field. However, gradients in the
conduction band edge energies and the valence band edge energies should no
longer be equal in graded structures, as shown in Figures 7.25 (b) and (c).
285
Forces on electrons and holes can be controlled by designing graded

structures. This type of quasi-field effect for graded structures has been
previously proposed [88] . Therefore, based on this effect, it should be
possible to use the potential profile to control the behavior of carriers.
~
"""~.
(a) (b) (c)
Figure 7.25. The forces on the carriers (electrons and holes) in a uniform semiconductor in (a)
an external electric field, and (b) and (c) in graded bandgap structures.
E
E
rI---~,'
~:
[, /
p ---+--.p
-----II 1,---
(a) (b)
Figure 7.26. Examples of energy levels and densities of state in micro-heterostructures. (a) A
square well and (b) a harmonic potential well.
Energy spikes formed at abrupt heterojunctions act as potential barriers

for carriers and substantially reduce the current flow normal to the
heterojunction. However, such energy barriers can be removed by gradually
changing the composition of the alloy. Moreover, even the scale of the
286 Chapter 7
potential profile can be reduced to about 10 nm where quantum size effects

dominate and the concept of the potential profile is still operative. A variety
of wave functions and densities of state can be obtained by designing graded
band gap structures. Examples of quantized levels and the density of state p,
with graded potentials are shown in Figure 7.26. Several practical devices
based on quantum effects, such as high electron mobility transistors
(HEMTs) and quantum well lasers, have already been developed.
In general, the dielectric constants of semiconductors are inversely
proportional to their bandgap energies. Photonic devices such as
semiconductor laser diodes include waveguide structures that consist of
semiconductor heterojunctions.
6.3 Applications of Graded Bandgap Structures
Bipolar transistors were the first application of graded bandgap structures

investigated [88]. Figure 7.27 indicates the energy band profile of a bipolar
transistor. The power gain of a bipolar transistor depends on the injection
efficiency of the emitter current, which is defined as the ratio of the current
injected from the emitter to the base region and the total emitter current.
Since the injection efficiency of a homojunction bipolar transistor is
proportional to the ratio of the concentration of the impurity dopant between
the base and the emitter regions, the concentration of the base dopant must
be reduced in order to obtain high injection efficiency. However, this results
in high base resistance and inferior frequency response.
electron
inject~~ Base
Emitter h~e
injection
Collector
Figure 7.27. Schematic of the energy band profile ofa bipolar transistor under operating
conditions.
287
The injection efficiency of heterojunction bipolar transistors (HBTs) that

have wide bandgap emitters can be improved without reducing the
concentration of the base impurity due to the presence of the energy steps in
a heterojunction. A band profile of this type of HBT with abrupt
heterojunctions is shown in Figure 7.28 (a). However, as discussed above,
the energy spikes at a heterojunction reduce the injection current. This has
led to the development of the graded emitter HBT structures shown in Figure
7.28 (b). The graded base HBTs, shown in Figure 7.28 (c) are another type
of structure. Their frequency response is improved by the acceleration of the
injection of minority carriers into the base layers by a built-in field.
However, the base layers in the most recent HBT structures are so thin that
the acceleration effect is no longer significant. The current structure of
standard HBTs is intermediate between those shown in Figures 7.28 (a) and
(b).
Graded bandgap structures are also being considered for heterojunction
solar cell structures in which wide bandgap materials are used to reduce the
ineffective photo-absorption at the exterior of p-n junctions. A graded
bandgap structure rather than a abrupt heterojunction is expected also to
further improve solar cells, since the built-in field can lower the
recombination rate of photogenerated carriers and improve their collection
efficiency at the electrodes [90].
~
~ ! Collector
Emitter
(a) (c)
Figure 7.28. Ihe three major heterojullctioll bipolar transistor (RBI) structures are: (a) an
abruptjullctioll RBI, (b) a graded bandgap emitter RBI, and (c) a graded bandgap base RBI.
A semiconductor laser contains a waveguide structure, a so-called double

heterostructure (DH), in which a narrow bandgap layer is sandwiched
between wide bandgap materials. The threshold current for the operation of
this laser is sharply reduced by the inclusion of DH structures, due to the
simultaneous confinement of photons and carriers within a narrow bandgap
layer. Separate confinement heterostructures (SCH), in which carriers and
288 Chapter 7
photons are confined by different DH structures, are of particular importance

for quantum well lasers. Graded index (GRIN) SCH lasers, shown in Figure
7.29 (b), have superior characteristics compared with conventional SCH
lasers, shown in Figure 7.29 (a), because photoabsorption in the cladding
layers can be reduced, and the carrier capture into a well layer is enhanced
by the built-in field in the cladding layers [91].
(a) (b)
Figure 7.29. The energy band profiles of single quantum well lasers. (a) A conventional
separate confinement heterostructure (SCH) laser, and (b) a graded index (GRIN) SCH laser.
7. GRADED INDEX MATERIALS
The terms gradient index and graded index, abbreviated GRIN, are used
to indicate an inhomogeneous medium in which the refractive index varies
continuously. Such GRIN materials possess unique and useful optical
properties that cannot be achieved with conventional optical materials,
which have a constant refractive index. The most common application is for
optical glass or polymer fibers in which the refractive index is changed
stepwise or gradually along the radial direction. A light wave can propagate
reflecting or curving with the change of refractive index through a fiber.
Many applications for GRIN materials have been reported for optical fiber
communications and microoptics. In this section, graded index optics and
some applications are described [92].
7.1 Graded Index (GRIN) Optics
In a conventional optical system, the refractive index within each optical

component is considered to be homogeneous. Therefore, in the design of
such systems, focusing and imaging properties are determined by varying the
curvature of each lens component. However, if the refractive index varies
289
continuously within a lens material, a light beam is gradually curved

according to the index distribution inside the lens. This results in changing
focusing properties.
The ray trajectory through such GRIN media, where the refractive index
varies as a function of position, satisfies the ray equation [93]:
-d [ n(r)-
dr] =Vn(r) (7.7.1)
ds ds
where r = xi + yj + zk is the position vector of a point on the ray, n is the

refractive index distribution, and ds is a differential element of each path
length along the ray. There are three types of gradient index lenses, as shown
in Figure 7.30; axial, radial, and spherical. When the refractive index linearly
decreases along the z axis in the axial GRIN lens, all parallel light rays focus
into one point without any spherical aberration. However, a conventional
homogeneous lens with the same dimension causes a large spherical
aberration.
A radial or cylindrical GRIN rod consists of a cylinder with the refractive
index distribution indicated in Equation 7.7.2 :
(7.7.2)
where no and nCr) are the refractive indices at the central axis and at a
distance r from the central axis respectively, and A is a positive distribution
constant.
Axial-GRIN Radial-GRIN Spherical-GRIN
z ---{}-----t-_m)--z t)
Figure 7.30. The three types of graded index (GRIN) lenses.
Since the refractive index is symmetrical on its axis, in a paraxial

condition Equation 7.7.1 is reduced to:
1 dn(r)
(7.7.3)
nCr) dr
290 Chapter 7
Substituting Equation 7.7.2 into Equation 7.7.3 and assuming n(r) = no

gives:
(7.7.4)
Solving Equation 7.7.4 gives:
r = ro cos( -fAz) + ~ (dr) sin( -fAz) (7.7.5)

-v A dz z=o
In such a GRIN rod, rays injected at r = ro follow approximately

sinusoidal paths according to Equation 7.7.5, as shown in Figure 7.31. The
symbol L denotes the period of the sinusoidal ray paths and is related to the
distribution constant A.
L= 2n (7.7.6)
-fA
Since all rays in Figure 7.31 pass through one point at Ll2 and L, for an
object at one end of a GRIN rod, the rod will form an inverted image with
unit magnification at a distance Ll2 and an upright image after a distance L.
Such GRIN rod lenses have been used as connectors and couplers for optical
fibers, and as imaging lens arrays in photocopiers.
oL-----~~----~------~------~------~z
Figure 7.31. The paths of light rays through a radial GRIN rod.
291
7.2 GRIN Glass Fibers
There are three types of optical glass fibers as illustrated in Figure 7.32.
Step-index type fibers (a and c) are composed of a core glass with a high
refractive index and a cladding glass with a low refractive index. The light
passes through the fiber and is reflected at the interface of the core and the
cladding glass. A graded-index type fiber (b) is fabricated so that the
refractive index continuously changes along the radial direction. The light is
curved in this fiber according to the graded index and is propagated without
leaking. Fibers (a) and (b) have several paths for the light wave to travel,
while fiber (c) is limited to a single path. Only single-mode, step-index
fibers, indicated by (c), are used for optical communication because of their
superior data-carrying performance.
Amp
R~frdeacUve ~ '~~~~~~~~j~
1\ In x
••
....+--I40-100llm
•• : .::::~:::]
._. '•
.....
Clad
Core
Clad
p a) Multimode step-index fiber
A1\m R~fr~t~e~ ~~~~~~::::j~Clad

~
••
Index
40-100llm - -Core
t
--: ~:~~:~~:~:J C~d
t
b) Multimode graded-index fiber
,-,A<-mp_~Re_:;tl:~~;~:.~E: ~
t t
c) Singlemode step-index fiber
Figure 7.32. Schematic showing how the pulse spreads through step-index type and graded-
index type optical fibers.
In the multimode step-index fiber (a), light spreads an impulse over a

time interval that is equal to the difference of the arrival times of the slowest
and fastest modes. In the multimode graded-index fiber (b), if the index
profile is optimum, all modes propagate at the same velocity without
292 Chapter 7
spreading an impulse. This results in a significant increase in the bandwidth

of the carrier wave, or its data-carrying capacity, compared with the
multimode step-index fiber (a).
Glass fibers can be made of silica glass, borosilicate glass, soda-lime
glass, or other multicomponent glasses. A silica glass fiber is produced by
chemical vapor deposition (CVD) [94] or vapor axial deposition (VAD)
[95]. In the CVD process, gaseous silicon tetrachloride (SiCI 4) plus gaseous
germanium tetrachloride (GeCI 4) or phosphorus oxychloride (POCI 3) as
dopants, flowing through a silica (Si0 2) tube with oxygen as the carrier gas,
are heated to above 1300'C. The resulting combustion products, fine
particles of silicon dioxide (Si02) and germanium Ge02 or phosphorus
pentoxide (P 20 5), are deposited on the walls of the silica tube. The presence
of the Ge02 or P20 5 increases the refractive index of the silica glass. The
glass preform is fabricated by heat treatment above 1700'C followed by hot
drawing to a fiber about 100 /lm in diameter.
In the VAD process, a porous rod is produced by the deposition of fine
particles of Ge02 or P20 5 using an oxygen-hydrogen flame. In order to
fabricate fibers with a graded refractive index, the amount of Ge02 or P20 5
deposited is controlled to increase at the center of the preform and decrease
toward its periphery. The V AD process produces high performance optical
fibers in which there is a low attenuation of light below 0.5 dB/km.l
Eliminating impurities that absorb light, such as hydroxyl ions (OK),
transition metals, and rare earth ions as well as minimizing the presence of
structural imperfections that can scatter the light are key factors in
decreasing attenuation of the propagated light.
Figure 7.33 is a schematic of a process for producing graded index fibers
of borosilicate glass using a double crucible [96]. The inner crucible is
charged with a thallium monoxide-boric oxide-silicon dioxide (ThO-B 20 3-
Si0 2) glass, which has the higher index, and the outer crucible is charged
with a sodium monoxide-boric acid-silicon dioxide (Na20-B 20 3-Si02) glass,
which has the lower index. During hot drawing of a glass fiber from the
bottom of the molten glasses, the two glasses come into contact and TI+ ions
diffuse out to the cladding glass, while Na+ ions diffuse into the core glass,
resulting in the formation of a graded refractive index.
The diameter of the core is between 40 - 100 /lm for multimode wave
fibers and between 5 - 15 /lm for single mode wave fibers. Because the
attenuation of silica fibers is at a minimum between 1.3 - 1.55 /lm, this
wavelength band has been adopted for optical communication system by
using Inl_xGaxAsyPl_y semiconductor lasers.
293
11 glass (Core glass)
Double cnx:ible
Figure 7.33. Schematic for fabricating graded-index glass fibers by an ion exchange method.
7.3 GRIN Polymers
The advantage of GRIN polymers is the ease of obtaining GRIN

materials with a short reaction time and a large GRIN region compared with
GRIN glasses. In general, GRIN polymers are produced by the
copolymerization of two or more kinds of monomers (M!, M2, •.. ), which
results in a material with two or more different refractive indices. If the
copolymer composition is controlled in the axial, radial, or spherical
direction, the corresponding GRIN material is produced.
In the copolymerization of monomers M\ and M2, the refractive index n
of the copolymer is related to the copolymer composition by the Lorentz-
Lorenz equation:
n Z -1 nr -1 n~ -1
-Z- = - - v +--v (7.7.7)
n + 2 nr + 2 \ n~ + 2 Z
where n\ and nz are the refractive indices of the monomers M\ and M2 ,

and VI and V2 are the volume fractions of each monomer unit, respectively.
A number of fabrication techniques have been proposed for GRIN polymers.
294 Chapter 7
The basic mechanism for forming the graded index can be classified into two
types: a diffusion process and a process that utilizes the difference in the
reactivities of the monomers [92].
7.3.1 The diffusiou process
Figure 7.34 shows the distribution of the refractive index obtained by the
vapor phase diffusion of the monomer, 2,2,2-trifluoroethyl methacrylate,
into a diethylene glycol bis (allyl carbonate) gel substrate at 70°C, followed
by heat treatment to complete polymerization [92]. Since the refractive index
of the diethylene glycol gel (nD= 1.50) is higher than the 2,2,2-trifluoroethyl
methacrylate (nD = 1.42), the refractive index, n, of the polymer gradually
increases with the distance x. The label of the ordinate, np , is the refractive
index of the substrate's surface. The curves with broken lines are theoretical.
They were derived from the diffusion equation by converting the
concentration at a distance x to the refractive index using equation 7.7.7.
c-c.
o
.s 0.00
x
Cll
'C
.£:
Cll
.~
t5
....
Cll
'O....:i
15
Cll
(J
c:
....
Cll
Cll
;:
15
a 3 6 9
Distance x (mm)
Figure 7.34. The distribution of the refractive index obtained by the diffusion of 2,2,2-
trifluoroethyl methacrylate vapor into a diethylene glycol bis(allyl carbonate) gel substrate for
lhour (squares) and 2 hours (circles). The broken lines were calculated from diffusion theory.
7.3.2 The monomer reactivity process
In the copolymerization reaction between monomers Mi and M j , the

monomer reactivity ratio rij is defined as:
295
i =1,2, .....
kii [ •
,nJ
'ij = - ] = 1,2, .... ,n (7.7.8)
k.'1 ••
l:t]
where kiiand kij are the propagation rate constants in the following
copolymerization reactions:
kij >M.M..
I ,
kij >M.M.·
I 1
(7.7.9)
In the photocopolymerization process to produce a radial GRIN rod in

which the refractive index monotonically decreases from the central axis to
the periphery of the rod, a glass tube including the monomer mixture is
rotated on its axis and irradiated by UV light from the side, as illustrated in
Figure 7.35 [97]. The copolymer gradually forms from the inner wall of the
tube, and solidifies upward through the tube's central axis. In the case of a
binary monomer system (M\ and Mz), the monomer pairs should satisfy the
condition:
where n\ and nz are the refractive indices of the homopolymers M\ and

Mz respectively. In the case where monomer MJ is more reactive than
monomer Mz, the polymer formed at the initial stage of polymerization at the
periphery has a lower refractive index. But the polymer formed during the
final stage of polymerization, in the center region of the tube, has a higher
refractive index. Consequently, the refractive index of the resulting radial
GRIN rod is at a maximum at the central axis and gradually decreases
toward the periphery.
7.4 Low loss, High Bandwidth GRIN Polymer Optical

Fibers
Recently, there has been considerable interest in the development of a

polymer optical fiber (POF) for short-distance communication applications
such as local area networks (LANs), data links, and multimodal bus
networks, because their ease of processing and large diameters enable high
efficiencies of fiber coupling and beam insertion [98]. A GRIN POF (GI
POF ) has a much higher bandwidth (> 500 MHz·km) than a multimodal
step-index (SI) POF (2-5 MHz·km). For short-distance communications,
which require many junctions and connections of optical fibers, a flexible
296 Chapter 7
POF with a large diameter would be most desirable. However, the SI POFs
will not be able to cover the entire bandwidth (about several hundred
megahertz) that will be required in the near future for LANs and for fast data
link applications. Therefore, GI POFs have been explored to provide light
wave media with large data-carrying capacity.
·
~
Glass Tube
··,,
; Shading
Monomer
Mixture ,
...
........................... "' .................... "'//1'//.'
,,
A ,
······· . ·...... r...... ·· ............
...
8
Liquid Phase
..... UV
C
Gel,0.;, •• ,.. ............... _-
<10$'& ,
,
......................... i .........................
..
,,, '//////,
,,
, ,
Figure 7.35. A schematic of the photocopolymerization process for fabricating radial GRIN
polymer rods.
8. FUNCTIONALLY GRADED BIOMATERIALS

FOR ARTIFICIAL JOINTS
Several of the organs of animals such as skin, blood vessels, and bones
are composed of multilayers that have different properties. These layers bind
together creating, in effect, a functionally graded material. Therefore,
incompatibility and separation at the interface never occur under normal
physiological conditions. Consequently, the ideal technique would be to
297
mimic such natural bonding in order to obtain a fixation of a prosthesis to

bone that will be stable for many years. In this section, examples of
orthopedic and dental implants are described as well as the development of
hip joint materials of nitrided Ti and the alloy, Ti-6AI-4V, with graded
structures and functions.
8.1 A Graded Interface for Bone in Orthopedic Implants
Conventional methods of fixing an artificial bone and joint prosthesis to

bone include: (l) total close contact of the prosthesis to the bone as shown
in Figure 7.36, (2) direct mechanical fixation with screws or spikes, and (3)
filling the space between the prosthesis and bone with
polymethylmethacrylate (PMMA) bone cement (see sections 8.1.2 and
8.1.3). In addition, prostheses coated with a porous metal have been used
recently for fixation. In this case, the prosthesis is expected to become
mechanically fixed to the bone due to bone ingrowth into the pores of the
porous metal coating. However, there are still many problems to overcome
with these methods because of the mechanical nature of the bonding.
Recently, several calcium phosphate ceramics that can bond to a bone
physicochemically, such as the bioactive ceramic, hydroxyapatite (HAp),
have been studied extensively, and their clinical application has been rapidly
adopted [99-108]. Furthermore, although binding bone to bioactive ceramics
is an excellent method in itself, since these bioactive ceramics lack sufficient
strength, many investigators have developed methods of coating bioactive
ceramics on the surface of metals or on the ceramic alumina (aluminum
oxide: Ah03) to create a composite material.
8.1.1 Cementless fixation
8.1.1.1 A smooth surface and a HAp coating on a smooth surface

In this method, the prosthesis is fixed to the bone without bone cement
(see Figure 7.36). During surgery, a prosthetic component with a smooth
surface on the area that contacts the bone is tightly inserted into a bone
cavity. To maximize the contact area, the bone cavity is reamed into the
same shape as the component. In this case, a connective tissue membrane
(living soft tissue) is intermediate between the component and the bone. This
may cause pain during weight bearing while walking due to micromotion of
the prosthesis in the bone, and subsequently the prosthesis may even loosen
in the bone. To prevent these potential problems, the surface of the
component is coated with a 50-100 /lm layer of hydroxyapatite (HAp) by a
plasma spraying method commonly used for coating HAp. The HAp-coated
298 Chapter 7
component bonds chemically to the bone by means of the HAp. However,

this also may result in failure if the component is moved before the onset of
chemical bonding, normally 2-3 weeks after surgery when a connective
tissue membrane has formed.
Bone
Conneclive Tissue HAp Coaling
Artificial Joinl _ _ _-'
Componenl
ICementless Fixation I ISmooth Surface I I HAp Coating I

(a) (b) (c)
Figure 7.36. Diagram of the interface between the prosthesis and the bone in a cementless
fixation. Figures (b) and (c) are based on microscopic observation. Figure (b) indicates that
when a prosthesis with a smooth surface is implanted into the bone, connective soft tissues
will interpose following the surgeI)'. Figure (c) indicates that when a prosthesis with a smooth
surface on which HAp is coated is implanted into the bone, the HAp coating will form a bond
with the bone.
There is a further potential problem, several years after total hip

replacement the HAp coating may separate from the base metal of the
component, or the HAp coating may break off in the body after continued
weight bearing during walking, because of the repetitive strong shear stress
on the stem in the femur. The breaking off of HAp from the component
might be prevented if the coating is graded. However, because the HAp
coating on the outermost layer (closest to the bone) is pure, the possibility of
its breaking at the interface between the bone and the HAp still exists.
In animal experiments using the tibia of beagles, (see Figure 7.37) the
adhesive strength (shear strength) to bone of test samples coated with HAp
were 3-5 MPa, 6-12 MPa, 8-11 MPa, and 12-14 MPa at 2, 4, 6, and 12
weeks respectively after implantation. During push-out tests, breaking
299
frequently occurred at the area coated with HAp. In clinical cases as well,
breaking at the HAp coating and also HAp peeling-off from the base metal
has been reported frequently.
Figure 7.37. Histological section of an animal bone at 6 wecks after implantation of the
prosthesis coated with HAp. (B: bone, H: hydroxyapatite coating, Ti: titanium).
8.1.1.2 Porous metal and HAp coating on porous metal

A more effective method for adhering a prosthesis to bone is to coat it
with a porous metal because new bone ingrowth into the pores occurs after
implantation (shown in Figure 7.38). The rate of adhesion is fastest and the
strength is highest when the pore sizes are 300 to 600 ~m. A porous surface
can be created by spraying with metal, or coating with beads or a fiber mesh.
Plasma spraying a HAp coating on the porous metal further increases the
adhesion strength and rate of binding to the bone. To create the porous metal
surface, beads, 750 ~m in diameter, of a titanium alloy (Ti-6AI-4V) are
coated in two layers. Changes after the implantation of specimens in the
bones of mature rabbits and goats under unloaded conditions are measured at
regular intervals. In the HAp-coated specimens, after 7-10 days the ingrowth
of bone tissue into every specimen is comparable to that seen in non-HAp-
coated specimens after about 3 weeks. Ultimately, almost all of the HAp
coated on the beads become bound to the bone by growing into the pores.
Consequently, there is a large amount of bone ingrowth into the pores
between the titanium alloy beads.
After push-out tests, the adhesion of the HAp-coated specimens to the
bone at 2, 4 , and 6 weeks after implantation is 4 times (2 MPa on average),
3 times (5 MPa on average), and 2 times (15 MPa on average) respectively,
greater than the adhesion of non-HAp-coated specimens. It becomes almost
equivalent after 12 weeks (26 MPa on average). During the push-out tests,
breakage occurs at the area of the bone around the implants. From these
300 Chapter 7
results, the interface between the bone and the coated specimen appears to be
adequately fixed. When a cross section of this interface is examined, three
graded zones are seen: a zone of titanium alloy, a zone of titanium alloy with
bone ingrowth, and a zone of bone, as shown in Figure 7.39.
Bone
Bone Ingrowth Bone Ingrowth
Rough Surface
Metal Base
Late Postoperative
Period (Over 12 weeks)
Early Postoperative
Period (1 • 2 weeks later)
(a) (b) (e) (d)
Figure 7.38. Diagram of the interface between porous metal and bone. (b) From microscopic
examination it is seen that immediately after surgery there is no bone ingrowth. (c) At 1-2
weeks bone ingrowth begins in some areas. (d) At over 12 weeks after surgery bone ingrowth
into the pores is accomplished.
When beads of the titanium alloy are coated with HAp, a larger amount
of bone ingrowth occurs earlier and bonds to the beads physicochemically,
thereby providing stronger adhesion. In animal experiments using beagles,
when an uncoated prosthesis is implanted, bonding to the bone frequently
fails during weight bearing. However, the probability of successful fixation
via bone ingrowth increases greatly when a prosthesis coated with HAp is
implanted. Therefore, porous metal with a HAp coating appears to remedy
the biggest drawbacks of cementless prostheses. It promises to prevent pain
while walking caused by micromotion or loosening of a prosthesis fixed
without bone cement, and also allows weight bearing earlier after
implantation.
301
1000J,lm
Figure 7.39. Histological examination at 6 months after the implantation of HAp coated
granules on a prosthesis under loaded condition (back scattered electron image). (B: A layer
of bone, P: A layer of porous beads with bone ingrowth, M: A layer of metal.)
Therefore it can be concluded that when a smooth surface is coated with

HAp the coating may separate from the metal. Even when a HAp layer is
applied as an FGM, the outermost layer can be destroyed. When porous
metal is not coated with HAp, even if there is bone ingrowth into the porous
beads, pain may occur due to micromotion because of spaces between the
bone tissue and the beads. But when the beads are coated with HAp, no
micromotion can occur because a large amount of bone grows into the pores
earlier and bonds to the HAp physicochemically. In addition, the layer
between the material and the bone is also graded.
8.1.2 Polymethylmethacrylate bone cement fixation
In this conventional technique, shown in Figure 7.40,

polymethylmethacrylate (PMMA) bone cement is used to fix the prosthesis
to the bone. The bone cement is prepared during surgery by mixing and
kneading the polymeric powder with the liquid monomer. The mixture, in
the form of a slurry, is poured into the bone cavity, and the prosthesis is then
inserted into the bone cavity and fixed in place. The cement hardens
(polymerizes) in about 10-15 minutes after kneading. This is a conventional
302 Chapter 7
bone cement fixation technique. A prosthesis can be completely fixed in the

bone immediately after surgery. However, a connective tissue membrane
(living soft tissue membrane) can become interposed between the bone and
the bone cement several weeks after implantation (see Figure 7.40 (b».
Occasionally, this may cause the prosthesis to loosen at the interface
between the bone cement and the bone. Figure 7.40 (c) illustrates the use of
interface bioactive bone cement fixation to overcome this difficulty.
Connective Tissue
Bone Cement
Artificial Joint Bone Cement
Component
Interface Bioactive Bone

Fixation with Bone Cement
(PMMA) I Bone Cement Fixation I Cement Fixation
(a) (c)
Figure 7.40. Diagrams of the interface between polymethylmethacrylate (PMMA) bone

cement and bone, and also of the interface in IBBC (interface bioactive bone cement) fixation.
Figures (b) and (c) are based on microscopic observation. (b) When the prosthesis is fixed to
the bone with PMMA bone cement, connective soft tissues will often subsequently become
interposed between the bone cement and the bone. (c) When 1-3 layers of HAp granules, 100-
300 mm in diameter, are interposed between the bone cement and the bone at the time of
cementing, the bone cement, HAp, and bone will become bonded in a functionally graded
condition after several weeks.
8.1.3 Interface bioactive bone cement fixation
Interface bioactive bone cementation (IBBC) is a technique developed to

overcome the problems that can occur at the interface between PMMA bone
cement and the bone. Specifically, one to three layers of fine HAp granules
(100-300 /lm in diameter) are placed between the bone and bone cement.
303
Therefore only the interface becomes a bioactive bone cement. The bone
cement mechanically adheres to the HAp granules and the HAp granules
chemically bond to the bone (see Figure 7.41). In an animal experiment in
which interface bioactive bone cementation was performed in the femoral
condyles of mature rabbits, ingrowth was observed in almost all spaces
between the HAp granules after 2 weeks, and fixation was completely
accomplished after 6 weeks. After a push-out test, the bonding strength to
the bone at 2, 6, 12, and 24 weeks was on average 3.8, 5.0, 5.5, and 9.0 MPa,
respectively.
Interface Bioactive Bone Cementation
Bone Cement HAp Granules Bone Bone Ingrowth

(PMMA)
.....--------.
Immediately After Late Postoperative
Surgery Appearance
(1.1) (b)
Figure 7.41. The fonnation of a porous surface on the surface of the bone by coating it with
granules of HAp.
Histologically, at 6 weeks there were four different graded zones at the

interface between the bone, the HAp granules, and the bone cement: a zone
of bone, a zone of HAp granules with bone ingrowth, a zone of HAp
granules with bone cement, and a zone of bone cement (see Figure 7.42).
After push-out tests at 6 weeks, breakage occurred at the zone of the bone or
304 Chapter 7
the zone of the HAp granules with bone ingrowth. This can be explained by
the presence of an FGM layer at the interface.
100,um
(e)
Figure 7.42. Back scattered electron image of the histological examination of the interface
between the bone and the bone cement at 7 months after surgery using the IBBC fixation
technique. (B: bone, H.B.: a layer of HAp granules with bone ingrowth, C.H.: a layer of bone
cement with HAp granules, C: a layer of bone cement, B.C.: bone cement)
In the case of the HAp coating on a smooth surface, after the push-out
test breakage occurred at the outermost layer of the HAp coating. From
these results, it can be concluded that the IBBC technique combines the
advantageous properties of cement fixation with those of a cementless
fixation of a HAp coating on a smooth surfaced prosthesis. Specifically, a
good bond can be obtained immediately after surgery, and adequate fixation
can be obtained indefinitely.
A HAp coating on porous metal is disadvantageous compared with the
IBBC technique because the prosthesis is covered with the HAp coated
porous metal only at the proximal part of the femor so that the entire surface
of the prosthesis cannot be covered with bone. Therefore, the proximal part
of the prosthesis will bind to the bone too strongly. This will cause the bone
surrounding the prosthesis to atrophy and weaken because the weight of the
body is not transmitted to the bone but to the prosthesis. In the IBBC
technique the entire surface of the prosthesis can be covered completely with
bone. Therefore, when the prosthesis binds to the bone with sufficient
305
strength, the load of the body's weight is largely transmitted to the bone, and
thus the bone will not become atrophied or weakened.
The IBBC technique has been used clinically in Japan since 1985 at
Osaka-Minami National Hospital for more than 2500 cases involving total
hip and total knee replacement. The absence of radiolucent lines at the bone
interface in X-rays post surgery indicates that no spaces are present between
the bone cement, the HAp granules, and the bone. Because the morphology
of the living body resembles that of an FGM, it is advantageous for a
prosthesis, such as an artificial bone and joint, to possess a similarly graded
form in order to achieve an organic linkage between the prosthesis and the
bone.
8.2 Dental Implants
Functionally graded dental implants composed of titanium plus HAp

have good biocompatibility and mechanical toughness [109]. A schematic
of the structure of such an FGM dental implant is shown in Figure 7.43. The
TilHAp FGM is produced by sintering (at 1300·C in argon, using radio
frequency) a graded green body consisting of various compositions of Ti, 5
weight % Pd, and 20 to 30 weight % HAp. The bending strength (150 MPa)
of the resulting material is similar to human bone. Animal implant tests show
that newly formed bone is in contact with most of the TilHAp FGMs, but
only partially in contact with an implant of Ti metal. After 8 weeks, no
inflammation was observed in either the Ti or Ti/HAp animal implants
[110].
8.3 A Nitrided Titanium Alloy Stem
Titanium and its alloy, Ti-6AI-4V, have high biocompatibility relative to

other metallic alloys that are currently used in orthopedics. However, since
serious cell toxicity caused by vanadium has been reported, there is concern
about the potential for local and systemic effects due to vanadium ions
released from the Ti-6AI-4 V alloy. Despite its desirable properties of
stiffness and fatigue strength, this alloy has a higher coefficient of friction
and lower wear resistance than ceramics such as alumina (Ah03) and
zirconia (Zr02). Therefore, it is unsuitable for the frictional component of an
artificial joint.
The combination of Ti-6AI-4V and ultrahigh molecular weight
polyethylene (UHMWPE) for prosthetic joints generates an unacceptable
quantity of Ti-6AI-4V and UHMWPE wear particles due to the relatively
poor frictional properties of this alloy. These wear particles have been
implicated as a contributing factor in the development of aseptic loosening
306 Chapter 7
of the prosthesis [111, 112]. Moreover, once the protective oxide film on the
alloy's surface is worn off by an electrolytic solution such as the body fluid,
the alloy becomes corroded rapidly [113]. The titanium, aluminum, and
vanadium ions released have been reported to inhibit the formation of
hydroxyapatite [114, 115]. This could affect normal osteoid mineralization
and remodeling, which could result in loosening of the implant. Vanadium
metal is also very toxic to cells, although a trace amount of vanadium is an
essential element nutritionally [116, 117].
.s::.
..... ,Q
C') .....
c: ctI
....
Q) c..
..... E
(j) o
C,)
o
III
•
A ""'''---- ---....;>~B
o
Figure 7.43. Schematic of the structure of an FGM dental implant.
A number of surface modification methods have been developed to

prevent the release of harmful ions or to harden the surface of metals. In the
case of Ti and Ti-6AI-4V, titanium nitride or oxide is synthesized on the
surface. Because Ti has an affinity for nitrogen as well as for oxygen, the
nitridation is successfully accomplished by heating the Ti or Ti-6AI-4V to
about 800'C in a gaseous nitrogen atmosphere. Compared with other
techniques including ion implantation and sputter coating, nitridation has the
advantage of low operating costs and minimal limitation on the sample's
shape. The biocompatibility of the nitrided Ti-6AI-4V is promising both in
vitro and in vivo [118].
Figure 7.44 shows the Vickers hardness of surface-nitrided Ti and Ti-
6AI-4V at various depths from the surface, measured by a 25 g indenter. It is
maximum at the surface: 1168 for the surface-nitrided Ti and 925 for the
surface-nitrided Ti-6AI-4V. The hardness gradually decreases toward the
interior to 116 at a depth of 60 !lm for the surface-nitrided Ti, and to 210 at a
depth of 50 !lm for the surface-nitrided Ti-6AI-4V. Because the Vickers
307
hardness of 116 and 210 correspond to that of Ti and Ti-6AI-4 V

respectively, the thickness of the nitrided layer is estimated to be 50-60 11m
for both materials. Nitrogen diffusion forms a compositionally graded layer
that results in a tough, nitrided surface. The frictional properties of surface
nitrided Ti-6AI-4V are superior to alumina for the frictional component of an
artificial joint plus it has high corrosion resistance.
1200 ~
•-0 Surface-nitrided Ti-6AI-4 V
~
1000 Surface-nitrided Ti
en
en
Q)
c 800
....
'0
<11
600
~\
1\
L:
en
....
Q)
~
() 400
:>
200
~\ ~
0
o 20 40 60 80
100
Depth from the surface (11m)
Figure 7.44. Vickers hardness of surface-nitrided Ti and Ti-6AI-4V at various depths from the
surface.
Within only ten years the thinking about ways to use FGMs has grown
from the initial limited one of relieving stress when combining two
dissimilar materials like a metal and a ceramic to the many and varied
applications described in this chapter. It is anticipated that these represent
only the beginning for potential applications of this useful concept.
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Chapter 8
SUMMARY AND OUTLOOK
Since the first international symposium on FGMs, held in Sendai, Japan

in 1990, research and development incorporating this concept has expanded
to many different fields worldwide. From the 70 papers at the Sendai
Symposium the number has grown to 240 at the 5th symposium held in
Dresden, Germany in 1998. The topics covered at this meeting included
computer-aided design and modeling; measurement; characterization;
fabrication by bulk, layer, melt, preform and other processes; joining;
thermal barrier coatings; various applications to cutting tools; heat resistant
materials; energy conversion; functional components with graded
ferroelectric, magnetic, and optical properties; and biomedical systems. In
addition, a number of papers have been published in scientific journals and
presented at numerous meetings with FGM sessions.
This book was written to provide a comprehensive description of the
design, processing, and applications of FGMs developed during the past ten
years. In the second chapter entitled, Lessons from Nature, the architecture
of graded structures in living bodies is shown to embody the essence and
image of the FGM concept. Indeed, it is surprising to see how living
organisms form and optimize graded structures in order to become
accommodated to complex environments and sustain life. The graded
distribution of fibrous tissue and porosity or graded texture can increase the
specific strength and protect against breakdown. Biomedical implants with
graded structures in the bone/apatite/metal system or in a ceramic are
gaining acceptance as both safe and effective prostheses. Also it has been
observed that the combination of graded structures with piezoelectric stress
sensing can control the growth or healing of living tissue. The incorporation
of sensing functions in graded structures will enable the production of a
316 Chapter 8
variety of materials that are sensitive and responsive to external and internal
environmental stimuli including damage, fatigue, and degradation.
The investigation of the mechanical and thermomechanical behavior of
FGMs has created a new field of study in materials engineering. For
example, analyzing crack propagation or delamination in a non-
homogeneous material that has a gradually changing composition and
structure presents a challenging problem. Local structures and properties and
the external load and temperature are correlated with an FGM's geometry.
The profile of stress or strain is determined by this type of correlation, which
strongly affects an FGM's mechanical and thermomechanical stability. The
role of stress is essential for both the structural and the functional
applications of FGMs.
The metamorphosis of FGMs due to atomic diffusion and/or chemical
reaction in their graded composition and structure not only can cause
degradation but also can provide active functions such as for the drug
delivery device described in Chapter 6. Dynamical modeling of the
mechanical, thermal, and chemical behavior of FGMs is needed to develop
the design methodology for fabricating active FGMs that are stable.
A wide variety of processing techniques to fabricate FGMs have been
proposed. However, only those that are cost effective probably will become
feasible for commercial application. The development of relatively simple
and productive fabrication processes by means of powder stacking,
laminating, or coating graded layers, as well as the fabrication of small size
FGMs such as machine tools, machine parts, small engine components, and
hip joints are all expected to encourage commercialization in the near-term.
In the future, FGMs with complex properties and shapes including three-
dimensional gradients will be produced by computer-aided design and
manufacturing techniques. Various combinations of freeform fabrication and
compositional gradation techniques are under development. These advanced
processes should soon make it possible to eliminate the present relatively
laborious and time-consuming methods for processing and optimizing
graded structures and functions.
Various examples of the design and fabrication of FGMs to use for
transportation, energy conversion, mechanical systems, semiconducting
applications, and optical and biological systems are introduced in this book.
Other applications to electromagnetic, medical, and agricultural systems are
being actively investigated [1].
A completely or partially graded structure can be formed in any material
and component. Therefore, the application of the FGM concept is virtually
unlimited. Materials science as developed in the 20th century is based on
homogeneous material systems. It is likely that the 21 st century will see the
development of a new materials science and technology for non-
317
homogeneous materials and systems that have optimized structures like

FGMs.
REFERENCES
I. Hirai, T. and Chen, L. (1999) Recent and prospective development of functionally graded
materials in Japan, in Functionally Graded Materials 1998, ed.W.A.Kaysser, Materials
Science Forum, vols. 308-311, Trans Tech Publications Ltd., ZUrich, 717-722.
Index
Acoustic emission, 89, 140, 144, 145 Bone, 1,5,7,8,13,14,20,21,22,

Acoustic microscope, 89, 112, 113, 26,248,297,298,299,300,301,
129, 130, 156 302,303,304,305,312,315
Actuator, 96, 97, 98 bone cement, 247, 297, 300, 301,
Alumina zirconia, 172 302,303,304,305
Arc spray methods, 190 bone material interface, 247
AuJ80Ni-2OCr/Au, 218 Boron nitride/silicon nitride, 200
Ba l _.Sr.Ti0 3, 96, 97 Boundary area density, 35
Bamboo, 1,7,8, 10, 11, 12, 13, 14, Boundary conditions, 50, 56, 70, 84,
15,17, 18,22,26 102, 103, 130
BaTi03, 96, 97 Boundary surface, 153
Bending test, 112, 114, 127 Brittle-to-ductile transition
Betti number, 60, 89, 92, 94 temperature, 142
BizTe3 ,262 Bulk modulus, 63, 69, 70, 73
Biaxial compression, 141 Bulk processing, 163
Bioactive ceramics, 247,297 Buoyancy convection, 214
Biocompatibility, 197,247,305,306, Burner heating test, 139, 143, 145
313 ClB 4C/SiC, 200
Biocompatible graded interface, 248 C/C, 152, 173, 199,240,247,249,
Biological structure, 7 250,258,259,260,261
Bipolar transistor, 247, 286, 287 C/C cavity, 247, 259, 261
Bismuth telluride, 262 C/C composites, 173, 200, 240, 249,
Blow molding, 232 259
BN/Si 3N4 , 200 C/SiC FGM, 201
Bond coat, 144, 195,255 CaC03,22
CAD, 161,220,223,243
320 Index
Capacitance, 89, 96, 97 Combustion synthesis, 161, 184, 185,

Capacitor, 96 238,241
Capillary forces, 170, 178 Composites, 7, 68,74, 123,253,297
Carbon, 31, 87, 109, 110, 146, 151, Composition profile, 50, 51, 56, 57,
152,160,173,181,182,183,201, 165,205
235,240,250,258,265,270,275, Compositionally graded layer, 307
277,307,309 Compositionally graded
Carbon fibers, 160, 173 semiconductors, 94
Carbonlboron carbide/silicon carbide, Compositionally graded silicon
200 carbide-silicon carbide/graphite,
Carbon/carbon composites, 173,249, 209
307 Compositionally graded TiN films,
Cellular structure, 7 197
Celsian, 232 Compositionally graded tools, 270
Cemented carbide, 177, 179,237, Conductivity profile, 90, 94, 96
270,273,277,311 Connectivity, 29, 38, 54, 60, 61, 67,
Centrifugal casting, 161, 170, 212, 83,92
235,312 Consolidation, 161, 165, 168, 181,
Centrifugal forces, 168 185,236,239,312
Centrifugal powder stacking, 170 Constitutive relations, 67, 84
Ceramic actuator, 89, 155 Constructive processes, 163
Ceramic-ceramic composites, 172, Constructive processing, 161, 162,
245 164
Characteristic dimensions, 29, 37,45, Contact angle, 39, 217
48 Containerless HIP, 181
Characteristic length scales, 44 Contiguity, 32, 38, 39, 53, 89, 90
Chemical reaction, 164,201,316 Continuous multi phased composites,
Chemical surface reaction methods, 73
186 Continuum mechanics, 66, 69
Chemical vapor deposition, 5,31,87, Continuum models, 63, 66
146, 151, 152, 159, 160, 161, 164, Continuum solid mechanics, 117
173,186,199,200,208,209,240, Controlled spatial distributions, 41
247,249,250,271,292 Convective transport, 186
Chemical vapor infiltration, 146,250 Coordination number, 39, 54
Cladding, 186, 187, 188, 189,216, Copper-graphite FGMs, 281
217,225,239,244,288,291,292 Corrosion, 4, 41,130,151,152,232,
Coefficient of thermal expansion, 70, 247,250,253,254,307,313
71, 77, 127 Corrosion resistance, 152
Coextrusion, 215 Co-sputtering, 198
Cold compaction, 115, 116 Cr3CjNilCr3C2 , 89, 125
Combustion plasma, 190 Crack driving force, 154
Combustion processing, 183 Crack opening displacement, 118
Index 321
Crack propagation, 90, 126, 127, 128, 228,232,233,234,241,242,243,

129,158,316 245,255,261,267,278,294,307,
Creep, 63, 84, 89, 112, 126, 127, 128, 311,316
155,158,180,215,216,256,257 Diffusion bonding, 161,219,232,
Critical power density, 144 234
Critical surface temperature, 138 Diffusion equations, 50, 57
Critical volume fraction, 38, 60 Digital image correlation, 99, 155
Crystal structure, 32, 34 Dihedral angle, 39
Cu/80Ni-2OCr/Cu,217 Dilatometer,99
CulNb/Cu, 216 Discontinuous multi phased
CulNi/Cu, 89, 117,218 composites, 73
Cu/SS304, 185 Discontinuously graded FGM, 179
Cu-Ni FGM, 202 Dispersed phase microstructures, 54,
Curie point, 96 60
Cutting tools, 4, 186,247,248,270, Dispersion strengthened alloys, 53
271,272,273,275,276,311,315 Divergence theorem, 153
Cyclic heat loads, 130 Drug delivery device, 161, 227, 228,
Cyclic thermal loading, 130 316
Defects, 32, 282 Drug delivery system, 2
Deformation, 22, 46, 61, 63, 83, 114, Effective field, 96
123,130,132,142,211,232,233 Elastic constant, 113, 114
Densification, 175, 176, 179, 180, Elastic limit, 115, 229
181,184,185,230 Elastic modulus, 54, 63, 69, 73
Dental implants, 297 127,200
Deposition current density, 204 Elasticity theory, 69, 112
Design, 2, 3, 5, 19,24,42,45,47,61, Electric shaver, 277
63,64,84,85,86,87,130,131, Electrical conductivity, 61, 89, 90,
152,157,172,217,220,227,233, 92,93,253,268,269
235,240,248,250,257,258,259, Electrical resistivity, 93, 263
260,263,264,269,279,288,308, Electrodeposition, 161,202
310,315,316 Electromigration, 186
Diamond, 200,201, 202, 238,240, Electron beam-physical vapor
275,276,277,311 deposition, 161, 194, 195,239,
Diamond/SiC, 247, 275, 277 240,247,253,254,255,308
DiamondlWC FGM, 200 Electrophoresis, 161
Dielectric constant, 89,96,97,98 Electrophoretic deposition, 204, 241
Dielectric permittivity, 89,96,98 Electrotransport, 164
Diesel engine, 64, 65, 247, 255, 256, Energy conversion systems, 247, 248,
279,308 256
Diffusion, 40, 44, 48, 50, 56, 57, 69, Enthalpy of solution, 110
90,109,110,111,158,163,176, Epitaxial growth, 283
186,207,208,209,215,216,219, Error function, 56, 57
322 Index
Eshelby's equivalent inclusion Functionally graded dental implants,

method,46 305
Eutectic bonding, 219 Fused deposition modeling, 161
Extrusion freeform fabrication, 161, Fusion reactor, 181
224,244 Fuzzy logic, 63, 75
Fabrication, 60, 163, 166, 174,316 Gallium arsenide, 283
Failure criteria, 84 GASARs, 247, 279, 280, 281
Fatigue, 41,89,90, 112, 126, 127, Geometrical models, 39, 40, 52
128, 130, 145, 148, 150, 155, 158, Geometrical parameters, 32, 33
215,240,249,253,265,279,305, Glass fibers, 292
316 Graded Alp/Zr02 ceramics, 205
Fatigue crack propagation, 127, 158 Graded band engineering, 94
FGM processing, 161,234 Graded band semiconductor, 89
Fiber bundles, 11, 13, 173 Graded bandgap, 95, 247, 282, 284,
Fiber composites, 204 285,286,287
Fiber reinforcement, 7 Graded bulk materials, 186
Fiber stacking, 161, 173,219 Graded C/C composite, 173
Fick's second law, 56 Graded C/C composite cavity, 259
Field parameter, 29, 45 Graded casting, 170, 171
Figure of merit, 247, 261, 262, 263, Graded cemented carbides, 179, 237
310 Graded ceramic gears, 172
Film casting, 173 Graded ceramic matrix composites,
Finite element method (FEM), 46, 227
63, 119, 131,309 Graded chromium doped alumina,
Flame fusion, 164,213,242 213
Foaming agents, 172 Graded CulNb/Cu, 216
Forced-resonance technique, 112 Graded fields, 164
Fourier number, 89, 107, 108 Gradedindex,98,247,288,289,291,
Fractal dimension, 60, 93, 95 292,293,312,294
Fracture, 54, 61, 83, 84, 89, 90, 112, Graded index polymer optical fiber,
115,117,119, 121, 123, 124, 125, 295
126, 130, 138, 140, 142, 146, 154, Graded magnetic properties, 211
155,159,177,241,271 Graded metal-ceramic composites,
fracture initiation, 117, 154 61,172
fracture mechanics, 89, 112, 117, Graded multilayer coatings, 270
118, 119, 121, 157 Graded porosity, 279
fracture mechanism map, 146 Graded properties, 164
fracture toughness, 54, 61, 89, 112, Graded PSZlNiCr coating, 192
123,124,125,126,154,271 Graded radial distribution, 213
Fuelcell,247,266,268, 310 Graded semiconductor, 247, 284
Functionally graded biomaterials, 96 Graded sheet, 234
nitrided titanium alloy stem, 305 Graded SiC coating, 199
Index 323
Graded silicon nitride/titanium GRIN, 247, 288, 289, 290, 291, 293,
nitride, 215 295,296
Graded single crystals, 164 GRIN polymers, 293
Graded structures, 2 HAp, 5, 297, 298, 299, 300, 301, 302,
Graded thermal barrier coatings 303,304,305
(TBCs),251 Hardwood, 15
Graded tungsten/copper, 265 Hashin and Shtrikman, 69, 72, 77, 78,
Graded tungsten-copper, 170 79,80,81,82
Graded Young's modulus, 213 Heat capacity, 80,99, 106, 109
Gradients Heat flow, 90,100,102,192,259
arrangement of phases gradient, 40 Heat flux, 99, 103, 104, 105, 106,
asymmetric gradient, 271 147,150,186,236,250,259,265,
composition gradient, 40 266,308,310
compositional gradient, 41, 132, Heat of transport, 110
137,142,143,165,167,171,182, Heat resistance, 99, 100,250
198,203,210,219,222,224,226, Heterogeneous materials, 100
240,273 Heterojunction, 247, 284, 285, 287
compositional gradients, 49, 128, Heterostructure, 247, 287, 288
137,165,166,167,171,207,208, HIP, 124, 125, 146, 158, 170, 180,
210,212,214,220,222,223,227, 181,215,263,311. See hot
244 isostatic pressing
continuous gradients, 168 Hip implants, 5
density gradients, 165, 181,212 Hip joint, 247, 297
grain size gradients, 210 Hip prosthesis, 248
magnetic saturation gradients, 211 Hot isostatic pressing (HIP), 124,
mechanical gradient, 181 146,161,165,170,180,185,215,
microstructural gradient, 181 216,235,257,263,264
one-dimensional gradient, 42 Hot pressing, 159, 161, 165, 168,
self-enhancing temperature 177,180,185,216,225,229,230,
gradients, 182 231,262,281
shape gradient, 40 Hutchinson-Rice-Rosengreen theory,
size gradient, 40 123
stepwise gradients, 168 Hybrid energy conversion system
temperature gradient, 90, 100, 109, (HYDECS), 258
110,130, 131, 145, 175, 177,210, Hydroxyapatite (HAp), 5, 20, 220,
236,241,269 223,247,297,299,306,312,313
thermal gradients, 65, 207 Hypersonic space plane, 3
three-dimensional gradient, 42 Implant, 5,197,247,248,306,313
two-dimensional gradient, 42 Inclusions, 72, 176, 182,234
volume fraction gradient, 40 Indium antimonide, 214
Gravitational segregation, 214 Indium phosphide, 283
Inelastic deformation, 149
324 Index
Infiltration, 161, 163, 165, 170, 181, Laplace transformation, 106

209,210,235,241,243,265,279 Laser beam cladding, 161, 187
Intelligent adaptive system, 17 Laser beam surface heating, 175
Intelligent material system, 7, 14 Laser cladding, 187, 225
Interconnected microstructures, 60 Laser flash method, 100, 105, 109
Interconnected second phase, 54 Laser interferometry, 99
Interdiffusion, 50, 56, 186, 198,208, Laser processes, 187
217,254,268,310 Layer processing, 163, 186
Interdiffusion rates, 52 Layer-by-Iayer stacking, 165
Interface bioactive bone cementation, Layered manufacturing, 219
302 Lead telluride, 262, 263
Interface energy, 175, 176 Lead zirconate titanate, 210, 223
Interfaces, 32, 39,44,55,90, 114, Linear elasticity, 69
219,233,234,253,261,267,268, Liquid phase diffusion, 164
275,283 Liquid phase joining, 219
Interlayers, 64, 66,103,131,164, Magnetic fusion reactor, 247
186,216,217,218,240,242,243 Magnetron sputtering, 161, 197, 198
Intermetallic compounds 208, 219, Material ingredient, 1, 3
232 Mean intercept length, 36, 44
AIIAI3Ni, 89, 112 Mean linear spacing, 37
iron aluminide/stainless steel Mean-field, 46, 71
FGM,248 Mechanical design, 7
NiAI,89, 114, 168, 180, 184,224, Mechanosensor,7, 14
234,235,237 Melt infiltration, 161
nickel aluminide, 112, 168, 175, Melt processing, 163,212
180,224 Metal matrix composites, 232
titanium aluminide, 158, 181, 198, Metal-ceramic composite, 176,261
257,309 Metal-ceramic joints, 278
Isothermal solidification, 216 MgOlNi,175
Japanese sword, 270 Microcrack, 90
Jet electroplating, 203 Microgravity, 161,214,242
Joining, 30,134,201,214,215,216, Microhardness, 22, 90, 203, 272
217,218,219,232,240,242,243, Microlaminar ceramics, 204
258,275,282,315 Microlamination, 186
Joining dissimilar materials, 214 Micromechanical approach, 63, 70,
Kerner's model, 70, 72, 75, 76, 77, 73,80,81,83
78,79,80,81,82,86 Microscopic length scale, 67
La l .,Sr,Cr03, 268 Microstructure, 7
Laminate theory, 115 microstructural analysis, 29, 30,
Laminated object manufacturing, 161 31,45,47
Lamination, 164, 174,235,236 microstructure characterization, 29
Lanthanum cobaltite, 268
Index 325
microstructural features, 30, 32, Optical communication system, 292

37,39,40,41,42,43,44,47,55, Optical fibers, 98, 187,247,288,
84,188,265 290,291,292,295,312
microstructural transition, 38, 53, Optical microscope, 130
62, 155, 159 Optical polymer fiber, 247
microstructural variation, 40, 47 Orthopedic implants, 297
Modified rule of mixtures, 74 Osteoblasts, 13
Modulus of elasticity. See Young's Osteoclasts, 13
modulus Ostwald ripening, 50, 90
Moire interferometry, 99 Oxidation resistance, 2, 151, 152,
Mollusk shell, 7, 8, 27 198,267
Mullite, 232 Oxidation resistant protective
MullitelSi3N4, 180 coatings, 191
Mullite-zirconia, 172 Palm tree, 7,17,18,19,20,24
Multifunctionality, 7, 8 Paris' law, 127
Multilayered material, 106 Partially stabilized zirconia, 60, 63,
Multilayered structure, 55 83,85, 109, 114, 131, 132, 146,
Multimedia, 247 174,192
Multiple graded features, 41 PbTe,262
Nap-Bp3-Si02,292 Percolation, 38,54,60,89,93, 161,
NASICON, 232, 245, 247, 253, 308 176,177,236
Near-net shape, 181 percolation clusters, 60
Nextel, 230, 231, 247, 253 percolation models, 54
Ni/MgO,60 percolation threshold, 38
NiAI, 89, 114, 168, 180, 184,224, Perturbation method, 106
234,235,237 Phase distribution, 59, 69, 132, 139,
NiAl/AI,89 142,148,271
Ni-AIP3' 76,87,234 Phase equilibria, 48, 50
Nicalon, 230, 231, 247, 253 Phase shape, 36, 37
Nickel aluminide, 112, 168, 175, 180, Phase stability, 52, 308
224 Piezoelectric, 13,21,26,96,97,98,
Nickel/magnesium oxide, 60 155,210,241,315
Nickel-base superalloys, 215 Piezoelectric effect, 13,21,26
Nickel-phosphorus, 202 Piezoelectricity, 26, 89
Ni-NiO, 182 Pixels, 33
NiO-YSZ, 269 Plasma spraying, 109, 145, 146, 159,
Nitrided titanium alloy stem, 305 161,190,191,192,200,239,251,
Nondestructive evaluation, 128, 130 253,278,297,310
Non-linear deformation, 142 air plasma spraying, 192
Nonplanar laminates, 204 low pressure plasma spraying, 192
Numerical solution techniques, 66, Plaster of Paris mold, 170
73 Plastic deformation, 116, 132, 232
326 Index
Plasticity, 73, 83, 84, 123 Reactive powder processing, 183

Poisson's ratio, 63, 71, 89, 112, 114, Reactive sputtering, 197
120,121, 154 Refractive index, 98, 247, 288, 289,
Polyhedral shaped grains, 178 291,292,293,294,295
Polymer optical fiber, 295, 296 Refractory porous preforms, 210
polymethylmethacrylate (PMMA) Representative volume element, 63
bone cement, 301 Reuss estimate, 68
Porous metal, 247, 297, 299, 300, Rocket combustor, 247
301,304,312 Rule of mixtures, 16,46,63,68,69,
Powder stacking, 161, 164, 165, 166, 73,74,75,76,77,78,79,80,81,
167,170,316 82,84,115,123
Power-law, 63, 84 Saturation magnetization, 211
Preform, 161, 164, 166, 183,207, Sedimentation, 161, 164, 168, 170,
210,292,315 172
Preform processing, 163, 164,207 Seebeck coefficient, 264
Pressure induced flow, 170 Self-adaptive modeling, 7
PSZ, 60,83,87, 109, 114, 130, 131, Self-healing effect, 152
132, 133, 134, 136, 137, 138, 139, Self-optimization, 7, 21
140,141,142,144,145,146,149, Self-propagating high temperature
150,156,159,192,193,236,239 synthesis (SHS), 124, 125, 146,
PSZlNi,89 158,159,161,162,184,210,238,
PSZlNiCrAlY, 89 311
PSZJSS,60,89, 114, 130, 131, 133, Semiconductor heterojunctions, 282
134, 136, 137, 138, 141 Separate confinement
Pyrometer, 104, 145 heterostructures, 287
PZT, 161,210,241 Settling, 161, 168, 170,212
Quantum well, 286, 288 settling under centrifugal forces,
Quasi-electric field, 89,95,96,247 212
Radar absorbent composites, 232 settling under gravity, 212
Rapid prototyping, 219 Shape conformation, 178
extrusion freeform fabrication, Shape parameters, 37
161,224,244 Shear modulus, 18,63,69,70, 71,
fused deposition modeling, 161 73,76,80,119,154
laminated object manufacturing, Sheet stacking, 173
161 Shrinkage curve, 174
stereolithography, 161,220,222 Si.sGe.2, 262
three-dimensional printing, 161 Si)NjfiN, 215
Rapid quenching, 188 Si)N4-Cu FGM, 247, 279, 280
Ravichandran model, 72, 80, 81, 82, Si().zAl,OzNs-z' 179
83,87 SIALON,179
Rayleigh wave, 113 SiC/C, 151, 159, 161, 199,200,240,
Reaction layers, 161, 186 241,247,249,250,277,307
Index 327
SiCffiC/CC, 89, 152 Solid state joining, 161

SiC-SiC/C, 209 Solution reprecipitation, 178
Silicon, 283 Space plane, 159, 161,247,249
Silicon germanium, 262 Spalling, 146, 148, 150, 152, 253,
Sintering, 52 265
differential sintering, 161 Spalling resistance, 146
liquid phase sintering, 161, 179, Spark plasma sintering, 161, 177
271 Spatial gradation, 2
liquid sintering aid, 229 Spatial variation, 29, 30, 40, 41, 44,
microwave sintering, 161, 175, 47,48,55,56,67
182 Specific boundary area, 32, 35, 36
plasma activated sintering, 161, Specific heat, 71, 100, 101, 153
177 Specific surface area, 32, 39
pulsed electric current sintering, Spray deposition, 65, 161, 165, 167,
115,161,177,178,277 186,188,239
reaction sintering, 161 Spray forming, 161, 186, 188, 190,
selective laser sintering, 161 234
sintering faults, 174 Sputtering, 196
sinter-HIP, 181 Step index, 247
solid state sjntering, 161, 174, 179 Stereolithography, 161,220,222
thermal explosion reactive STL file, 220
sintering, 184 Strain
transient liquid phase sintering, inelastic strain, 142
161, 179 isostrain, 63, 72, 74
transient viscous flow sintering, plane strain, 118, 120
179 strain energy release rate, 155
Slip casting, 161, 170, 171, 182,235 strain hardening, 63, 74, 89, 115,
Slip casting-sedimentation process, 116, 117, 124
172 strain to failure, 115
Slurry deposition, 164 stress-strain, 74, 83, 116
Softwood, 14, 15 stress-strain behavior, 74, 84, 115
Solar receiver, 247 stress-strain curve, 112, 116
Sol-gel infiltration, 161 Strength,2
Sol-gel process, 180,219,229 bending strength, 114, 115
Sol-gel techniques, 228 tensile strength, 15, 18,20,21,22
Solid freeform fabrication, 161, 162, Stress 2
219 axial stress, 133, 134, 137, 138,
Solid freeform processes, 187 141
Solid oxide fuel cell, 247, 266, 268, asymptotic stresses, 154
269,270,310 circumferential stress, 134, 137
Solid state diffusion, 161, 164, 186 compressive stress, 127, 140, 142,
Solid state diffusion bonding, 232 152,271,273
flow stress, 63, 74
328 Index
isostress, 63, 72, 74 Surface curvature, 39, 232

maximum tensile stress, 133 Surgical implants, 197
principal stress, 7, 13 Tensile test, 114
residual stress, 89, 112, 115, 127, Thermal runaway, 182
142,152,226,227 Thermal analysis, 65, 105
residual stresses, 30, 43, 85, 115, Thermal barrier coatings (TBCs), 44,
116,117,127,157,177,213 64,86,143,158,194,239,247,
residual thermal stress, 63 249,250,252,308,309,315
shear stress, 7, 134, 137,224,298 Thermal conductivity, 38, 54,69,70,
stress corrosion cracking, 155 71,77,78,79,89,98,99,100,
stress distribution, 7, 10, 15,43, 101, 103, 104, 105, 109, 131, 146,
127, 133, 140 147,148,149,150,151,173,182,
stress intensity factor, 89, 120, 192,200,254,259,265,281
121, 122, 127, 154, 155 Thermal cycling, 64, 99, 146, 148,
stress singularity, 118 149,150,279
stress state, 115, 118, 142 Thermal diffusion, 107, 110
stress-strain, 74, 83, 116 Thermal diffusivity, 89, 98, 99, 100,
stress-strain behavior, 74, 84, 115 106, 107, 109, 156
stress-strain curve, 112, 116 Thermal expansion, 65, 75, 76, 77,
tensile stress, 151 80,89,90,99,112,127,128,130,
thermal residual stresses, 65, 127 131,152,156,172,173,180,200,
thermal stress, 43,89, 130, 131, 201,216,219,226,263,268,271
132, 133, 138, 139, 148, 149,271, Thermal expansion coefficient
279 (TCE), 65, 75, 76, 77,80,99, 112,
thermal stresses, 30, 65, 76, 90, 127,128,131,156,172,200,201,
130,138,141,149,157,200,201, 219,268
215,261,265 Thermal fatigue, 89, 144, 146, 150
thermal stress relaxation, 278 Thermal shock, 90, 128, 130, 138,
transient thermal stress, 142 144,145,158,159,194,249,254,
yield stress, 123, 124 265
Strontium doped lanthanum Thermal spraying, 161, 164, 165,
chromite, 268 186, 190, 194
Strontium doped lanthanum Thermal stability, 90,109,200,241,
manganite, 268 249,269,309
Subcritical crack propagation, 155 Thermionic conversion, 261
Superalloy, 87,186,187,194,215, Thermionic converter, 247, 261, 309
224,247,254,257,278,281,311 Thermocouple, 104
Superiattice, 94 Thermoelectric converter, 247, 261
Superplastic diffusion bonding, 232 Thermoforming, 232
Superplastic forming, 161,232 Thermomechanical behavior, 67, 316
Superplasticity, 219 Thermomechanical response, 64
Surface crack formation, 140
Index 329
Thermophysical properties, 67, 68, Tungsten carbide-cobalt, 179,270

69,98,99,100,105,106,173 Tungsten/copper, 211
Thin sheet lamination, 166 Turbine airfoils, 191
Thomson coefficient, 264 Turbine blade, 181, 186,247,251
Three-dimensional FGMs, 223 Two-phase material, 35, 38, 39, 53
Three-dimensional printing, 161 Two-phase mixtures, 38, 52, 54
Ti(C,N) graded metal, 281 Ultrasonic motor, 97
TilHAp FGMs, 305 Underwater shock explosion, 161,
Tiffi 3Sn FGM, 219 185
TiffisSi3,219 VN2C, 89, 109, 110, 111
Ti-6AI-4V, 197,240,247,297,299, Vacuum forming, 232
305,306,307,313 VAD, 247, 292
TiAI, 181, 184, 185, 198,237,238, Van der Waals interaction, 205
247,256,257,309 Vanadium/vanadium carbide, 109,
TiBffi,89 111
TiBjCu, 89, 146, 148, 185 Vapor phase diffusion, 164
TiB 2-AI, 184 Variational approach, 69
TiB2-Cu, 184 Variational principles, 69
TiC/C,2oo Verneuil process, 161, 213
TiCINi, 89, 149 Viscous phase, 179
TiCINi3AI, 175, 181, 185,236,237 Voight estimate, 68
TiC-Ni,89, 124, 184 W/Cu, 81,211,247
TiNINi,215 Wakashima model, 61, 71, 72, 76,
TiNi,184 77,78,79,80,81,82,86,156
Titanium aluminide, 158, 181, 198, Water-immersion ultrasonic method,
257,309 128
Titanium carbide/carbon, 200 Waveguide, 286,287, 312
TlP-BP3-Si02,292 WC/Co,4, 103, 104, 105,248,271,
Torsional rigidity, 18, 19 273,274,275,277
Toughening ratio, 89, 123, 124 WC-Co, 179, 187,209,236,241,
Transient heating, 98, 105, 108 247,270
Transient liquid phase bonding, 164, Wear resistance, 270, 271, 273, 281,
186,218,242,243 305
Transient liquid phase joining, 161, Wear resistant coatings, 276
218 Weight-cost, 7, 22, 24
Transient temperature response, 105, Welding technology, 215
106 W-Ni-Fe, 179
Transition zone, 216 Wolfs law, 13
Transport based processing, 161, 164 Young's modulus, 18,24,63,72,73,
Transport properties, 38, 54 80,81,82,89,112,114,154,156
Transport-based methods, 38, 57 YSZJNiCrAIY, 192
Tungsten carbidelcobalt, 248 YSZlSS304, 83
330 Index
Yttria-stabilized zirconia, 63, 78, 85

Zirconia, 232
Zirconia toughened alumina, 161,
225
Zirconia/titanium aluminide, 177
Zirconium carbide/carbon, 199
Zirconium phosphide, 209
ZrC/C, 199
Zr02 (yp3)-AIP3,234
ZrO/fiAI, 177
Zr02-Ni, 174, 182
ZTA, 225, 226, 227

Functionally Graded Materials Design Pro

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FUNCTIONALLY GRADED

Series editor: Renee G. Ford

The Materials Technology series is dedicated to state-of-the-art areas of

Ceramic Injection Molding

Cryochemical Technology of Advanced Materials

Modelling of Materials Processing

SPRINGER SCIENCE+ BUSINESS MEDIA. llC

Functionally graded materials : design, processing, and applications I

Copyright ® 1999 by Springer Science+Business Media New York

All rights reserved. No part of this publication may be reproduced, stored in a

Printed on acid-free paper.

Schematic of the Microstructure of a FGM, Fusion Bronze sculpture.

LESSONS FROM NATURE 7

MODELING AND DESIGN 63

THE CHARACTERIZATION OF PROPERTIES 89

PROCESSING AND FABRICATION 161

SUMMARY AND OUTLOOK 315

Prof. N. Arakt(5.3.2, 5.3.4)*

Dr. K. Hirano (5.4.3c)

Prof. Y. Miyamoto (Ch.l- 8, 1, 5.2, 6.2.3f, 6.7.1, 7.7, 7.8.2, 8)

Department of Materials Science and Engineering, National Defense

* The numbers in parentheses are the contributed sections and edited

Seven years have elapsed since Dr. Renee Ford, editor-in-chief of

Dr. Yoshinari Miyamoto, Editor

Professor ofMaterials Science, Joining and Welding Research Institute,

The authors would like to gratefully acknowledge the sponsorship of

Keywords: Element, material ingredient

1. DEFINITIONS AND HISTORICAL PERSPECTIVE

In a Functionally Graded Material (FGM) both the composition and the

In the simplest FGMs, two different material ingredients change

Figure 1.1 . (a) Continuous and (b) stepwise graded structures.

Pores also are important material ingredients of FGMs. A gradual

In 1985, the use of continuous texture control was proposed in order to

The FGM concept is applicable to many fields, as illustrated in Figure

Figure 1.3. Potentially applicable fields for FGMs.

The FGM concept is also applicable to functional materials. A graded

LESSONS FROM NATURE

Keywords: Biological structure, composite material, multifunctionality, optimum design,

The basic characteristics of biological hard tissue, such as microstructure,

A structure can be defined as any assemblage of materials intended for

Purplish Washington clarY

The shape of a ClOSS section of the leaf

• shape and size

animal bone tooth

3. A NATURAL PROCESS OF OPTIMIZATION:

Bamboo belongs to the genus Bambuseae in the grass family,

L....-_ _ _.....I' Smm L..--...J O.1mm

(a) Transverse section through (b) Enlargement of

plants. In addition, no voltage signals were induced from a specimen boiled

(a) Stress distribution around (b) Photoelastic stress pattern

Figure 2.6. Experimental set up to measure the voltage signals of bamboo.

stress duration ® bipolar lead system

G)® : unipolar lead system

Piezoelectric properties have been found in bone subjected to stress [9].

i 1.1. bipolar lead system

v-t curve stress dll"a tion

II ~[~ rubber plant

bundles suggest that bamboo has a stress/strain-induced adaptive modeling

stressed duration stressed duration

Figure 2. J J. A scanning electron micrograph of fractured fibers in a vascular bundle.

The model selected to examine graded structures and strength in terms of

O(inside) 0.5 1.0

II (see Figure 2.12). This could be regarded as corresponding to pressure

3.2 The leaf shaft of a palm tree