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PRINCIPLES OF
INORGANIC MATERIALS
DESIGN

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PRINCIPLES OF
INORGANIC MATERIALS
DESIGN
SECOND EDITION

John N. Lalena

The Evergreen State College

David A. Cleary
Gonzaga University

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Copyright # 2010 by John Wiley & Sons, Inc. All rights reserved
Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data:
Lalena, John N.
Principles of inorganic materials design/John. N. Lalena, David. A. Cleary. – 2nd ed., rev.,
updated, and expanded.
p. cm.
Includes index.
ISBN 978-0-470-40403-4 (cloth)
1. Chemistry, Inorganic–Materials. 2. Chemistry, Technical–Materials. I. Cleary, David A. II.
Title.

QD151.3.L35 2010
546–dc22
2009025906
Printed in the United States of America
10 9

8 7 6

5 4

3 2

1

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CONTENTS
FOREWORD TO SECOND EDITION

xiii

FOREWORD TO FIRST EDITION

xv

PREFACE TO SECOND EDITION

xix


PREFACE TO FIRST EDITION

xxi

ACRONYMS

1

xxiii

CRYSTALLOGRAPHIC CONSIDERATIONS

1

1.1

2
2
3
5
5
8
9
9

1.2
1.3
1.4
1.5


Degrees of Crystallinity
1.1.1 Monocrystalline Solids
1.1.2 Quasicrystalline Solids
1.1.3 Polycrystalline Solids
1.1.4 Semicrystalline Solids
1.1.5 Amorphous Solids
Basic Crystallography
1.2.1 Space Lattice Geometry
Single Crystal Morphology and its Relationship
to Lattice Symmetry
Twinned Crystals
Crystallographic Orientation Relationships in Bicrystals

31
36
38

1.5.1
1.5.2

38
43

The Coincidence Site Lattice
Equivalent Axis-Angle Pairs

1.6 Amorphous Solids and Glasses
Practice Problems
References


45
50
52
v

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CONTENTS

2

3

MICROSTRUCTURAL CONSIDERATIONS

55

2.1

Materials Length Scales
2.1.1 Experimental Resolution of Material Features
2.2 Grain Boundaries in Polycrystalline Materials
2.2.1 Grain-Boundary Orientations
2.2.2 Dislocation Model of Low Angle Grain Boundaries
2.2.3 Grain-Boundary Energy
2.2.4 Special Types of Low-Energy Grain Boundaries
2.2.5 Grain-Boundary Dynamics

2.2.6 Representing Orientation Distributions in Polycrystalline
Aggregates
2.3 Materials Processing and Microstructure
2.3.1 Conventional Solidification
2.3.2 Deformation Processing
2.3.3 Consolidation Processing
2.3.4 Thin-Film Formation
2.4 Microstructure and Materials Properties
2.4.1 Mechanical Properties
2.4.2 Transport Properties
2.4.3 Magnetic and Dielectric Properties
2.4.4 Chemical Properties
2.5 Microstructure Control and Design
Practice Problems
References

56
59
61
61
63
65
66
67

CRYSTAL STRUCTURES AND BINDING FORCES

97

3.1


3.2

Structure Description Methods
3.1.1 Close Packing
3.1.2 Polyhedra
3.1.3 The Unit Cell
3.1.4 Pearson Symbols
Cohesive Forces in Solids
3.2.1 Ionic Bonding
3.2.2 Covalent Bonding
3.2.3 Metallic Bonding
3.2.4 Atoms and Bonds as Electron Charge Density

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70
70
78
78
79
82
83
84
88
90
90
93
94


97
98
101
103
103
103
103
106
109
110


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CONTENTS

3.3

4

Structural Energetics
3.3.1 Lattice Energy
3.3.2 The Born – Haber Cycle
3.3.3 Goldschmidt’s Rules and Pauling’s Rules
3.3.4 Total Energy
3.3.5 Electronic Origin of Coordination Polyhedra in
Covalent Crystals
3.4 Common Structure Types
3.4.1 Iono-Covalent Solids

3.4.2 Intermetallic Compounds
3.5 Structural Disturbances
3.5.1 Intrinsic Point Defects
3.5.2 Extrinsic Point Defects
3.5.3 Structural Distortions
3.5.4 Bond Valence Sum Calculations
3.6 Structure Control and Synthetic Strategies
Practice Problems
References

111
112
117
118
120

THE ELECTRONIC LEVEL I: AN OVERVIEW OF BAND THEORY

175

The Many-Body Schroădinger Equation
Bloch’s Theorem
Reciprocal Space
A Choice of Basis Sets
4.4.1 Plane-Wave Expansion – The Free-Electron Models
4.4.2 The Fermi Surface and Phase Stability
4.4.3 Bloch Sum Basis Set – The LCAO Method
4.5 Understanding Band-Structure Diagrams
4.6 Breakdown of the Independent Electron Approximation
4.7 Density Functional Theory – The Successor to the Hartree – Fock

Approach
Practice Problems
References

176
179
184
187
188
189
192
193
197

4.1
4.2
4.3
4.4

5

122
127
127
144
153
154
156
157
160

163
167
169

198
199
201

THE ELECTRONIC LEVEL II: THE TIGHT-BINDING
ELECTRONIC STRUCTURE APPROXIMATION

203

5.1
5.2

204
210

The General LCAO Method
Extension of the LCAO Treatment to Crystalline Solids

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CONTENTS

5.3


6

7

Orbital Interactions in Monatomic Solids
5.3.1 s-Bonding Interactions
5.3.2 p-Bonding Interactions
5.4 Tight-Binding Assumptions
5.5 Qualitative LCAO Band Structures
5.5.1 Illustration 1: Transition Metal Oxides with Vertex-Sharing
Octahedra
5.5.2 Illustration 2: Reduced Dimensional Systems
5.5.3 Illustration 3: Transition Metal Monoxides with Edge-Sharing
Octahedra
5.5.4 Corollary
5.6 Total Energy Tight-Binding Calculations
Practice Problems
References

213
213
217
221
223

TRANSPORT PROPERTIES

241


6.1
6.2

An Introduction to Tensors
Thermal Conductivity
6.2.1 The Free Electron Contribution
6.2.2 The Phonon Contribution
6.3 Electrical Conductivity
6.3.1 Band Structure Considerations
6.3.2 Thermoelectric, Photovoltaic, and Magnetotransport
Properties
6.4 Mass Transport
6.4.1 Atomic Diffusion
6.4.2 Ionic Conduction
Practice Problems
References

241
248
249
251
254
258

METAL – NONMETAL TRANSITIONS

285

7.1


287
289
293
293
295
299

7.2
7.3

Correlated Systems
7.1.1 The Mott – Hubbard Insulating State
7.1.2 Charge-Transfer Insulators
7.1.3 Marginal Metals
Anderson Localization
Experimentally Distinguishing Disorder from Electron Correlation

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231
233
237
238
239
240

263
272
273

280
281
282


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CONTENTS

8

7.4 Tuning the M – NM Transition
7.5 Other Types of Electronic Transitions
Practice Problems
References

302
305
307
308

MAGNETIC AND DIELECTRIC PROPERTIES

311

8.1

313
316
317

319
325

Phenomenological Description of Magnetic Behavior
8.1.1 Magnetization Curves
8.1.2 Susceptibility Curves
8.2 Atomic States and Term Symbols of Free Ions
8.3 Atomic Origin of Paramagnetism
8.3.1 Orbital Angular Momentum Contribution – The Free
Ion Case
8.3.2 Spin Angular Momentum Contribution – The Free
Ion Case
8.3.3 Total Magnetic Moment – The Free Ion Case
8.3.4 Spin – Orbit Coupling – The Free Ion Case
8.3.5 Single Ions in Crystals
8.3.6 Solids
8.4 Diamagnetism
8.5 Spontaneous Magnetic Ordering
8.5.1 Exchange Interactions
8.5.2 Itinerant Ferromagnetism
8.5.3 Noncolinear Spin Configurations and
Magnetocrystalline Anisotropy
8.6 Magnetotransport Properties
8.6.1 The Double Exchange Mechanism
8.6.2 The Half-Metallic Ferromagnet Model
8.7 Magnetostriction
8.8 Dielectric Properties
8.8.1 The Microscopic Equations
8.8.2 Piezoelectricity
8.8.3 Pyroelectricity

8.8.4 Ferroelectricity
Practice Problems
References

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326
327
328
329
330
336
339
339
341
350
353
359
361
361
363
364
365
367
370
371
372
373



x

CONTENTS

9

10

OPTICAL PROPERTIES OF MATERIALS

377

9.1 Maxwell’s Equations
9.2 Refractive Index
9.3 Absorption
9.4 Nonlinear Effects
9.5 Summary
Practice Problems
References

377
381
390
395
400
400
401

MECHANICAL PROPERTIES


403

10.1
10.2

404
407
408
413

Stress and Strain
Elasticity
10.2.1 The Elasticity Tensor
10.2.2 Elastically Isotropic Solids
10.2.3 The Relation Between Elasticity and the
Cohesive Forces in a Solid
10.2.4 Superelasticity, Pseudoelasticity, and the
Shape Memory Effect
10.3 Plasticity
10.3.1 The Dislocation-Based Mechanism to Plastic Deformation
10.3.2 Polycrystalline Metals
10.3.3 Brittle and Semibrittle Solids
10.3.4 The Correlation Between the Electronic Structure
and the Plasticity of Materials
10.4 Fracture
Practice Problems
References

11


PHASE EQUILIBRIA, PHASE DIAGRAMS, AND
PHASE MODELING
11.1

Thermodynamic Systems and Equilibrium
11.1.1 Equilibrium Thermodynamics
11.2 Thermodynamic Potentials and the Laws
11.3 Understanding Phase Diagrams
11.3.1 Unary Systems
11.3.2 Binary Metallurgical Systems
11.3.3 Binary Nonmetallic Systems

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430
433
439
447
448
450
451
454
456

461
462
465
469
472

472
472
477


xi

CONTENTS

11.3.4 Ternary Condensed Systems
11.3.5 Metastable Equilibria
11.4 Experimental Phase-Diagram Determinations
11.5 Phase-Diagram Modeling
11.5.1 Gibbs Energy Expressions for Mixtures and
Solid Solutions
11.5.2 Gibbs Energy Expressions for Phases with
Long-Range Order
11.5.3 Other Contributions to the Gibbs Energy
11.5.4 Phase Diagram Extrapolations – the
CALPHAD Method
Practice Problems
References

12

13

478
483
484

485
485
488
493
494
498
499

SYNTHETIC STRATEGIES

501

12.1

Synthetic Strategies
12.1.1 Direct Combination
12.1.2 Low Temperature
12.1.3 Defects
12.1.4 Combinatorial Synthesis
12.1.5 Spinodal Decomposition
12.1.6 Thin Films
12.1.7 Photonic Materials
12.1.8 Nanosynthesis
12.2 Summary
Practice Problems
References

502
503
504

512
514
514
517
519
521
526
526
528

AN INTRODUCTION TO NANOMATERIALS

531

13.1
13.2

532
534
535
536
537
538
538
539

History of Nanotechnology
Nanomaterials Properties
13.2.1 Electrical Properties
13.2.2 Magnetic Properties

13.2.3 Optical Properties
13.2.4 Thermal Properties
13.2.5 Mechanical Properties
13.2.6 Chemical Reactivity

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CONTENTS

13.3

More on Nanomaterials Preparative Techniques
13.3.1 Top-Down Methods for the Fabrication of
Nanocrystalline Materials
13.3.2 Bottom-Up Methods for the Synthesis of
Nanostructured Solids
References

541
542
544
556

APPENDIX 1

559


APPENDIX 2

565

APPENDIX 3

569

INDEX

575

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FOREWORD TO SECOND EDITION
Materials science is one of the broadest of the applied science and engineering fields since
it uses concepts from so many different subject areas. Chemistry is one of the key fields of
study, and in many materials science programs students must take general chemistry as a
prerequisite for all but the most basic of survey courses. However, that is typically the last
true chemistry course that they take. The remainder of their chemistry training is accomplished in their materials classes. This has served the field well for many years, but over
the past couple of decades new materials development has become more heavily dependent upon synthetic chemistry. This second edition of Principles of Inorganic Materials
Design serves as a fine text to introduce the materials student to the fundamentals of
designing materials through synthetic chemistry and the chemist to some of the issues
involved in materials design.
When I obtained my BS in Ceramic Engineering in 1981, the primary fields of
materials science – ceramics, metals, polymers, and semiconductors – were generally
taught in separate departments, although there was frequently some overlap. This was particularly true at the undergraduate level, although graduate programs frequently had more
subject overlap. During the 1980s, many of these departments merged to form materials
science and engineering departments that began to take a more integrated approach to the

field, although chemical and electrical engineering programs tended to cover polymers
and semiconductors in more depth. This trend continued in the 1990s and included
the writing of texts such as The Production of Inorganic Materials by Evans and De
Jonghe (Prentice Hall College Division, 1991), which focused on traditional production
methods. Synthetic chemical approaches became more important as the decade progressed and academia began to address this in the classroom, particularly at the graduate
level. The first edition of Principles of Inorganic Materials Design strove to make this
material available to the upper division undergraduate student.
The second edition of Principles of Inorganic Materials Design corrects several gaps
in the first edition to convert it from a very good compilation of the field into a text that is
very usable in the undergraduate classroom. Perhaps the biggest of these is the addition of
practice problems at the end of every chapter since the second best way to learn a subject
is to apply it to problems (the best is to teach it) and this removes the burden of creating
the problems from the instructor. Chapter 1, Crystallographic Considerations, is new and
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FOREWORD TO SECOND EDITION

both reviews the basic information in most introductory materials courses and clearly
presents the more advanced concepts such as the mathematical description of crystal
symmetry that are typically covered in courses on crystallography of physical chemistry.
Chapter 10, Mechanical Properties, has also been expanded significantly to provide both
the basic concepts needed by those approaching the topic for the first time and the solid
mathematical treatment needed to relate the mechanical properties to atomic bonding,
crystallography, and other material properties treated in previous chapters. This is particularly important as devices use smaller active volumes of material, since this seldom
results in the materials being in a stress free state.

In summary, the second edition of Principles of Inorganic Materials Design is a very
good text for several applications: a first materials course for chemistry and physics students; a consolidated materials chemistry course for materials science students; and a
second materials course for other engineering and applied science students. It is also
serves as the background material to pursue the chemical routes to make these new
materials described in texts such as Inorganic Materials Synthesis and Fabrication by
Lalena and Cleary (John Wiley & Sons, 2008). Such courses are critical to insure that
students from different disciplines can communicate as they move into industry and
face the need to design new materials or reduce costs through synthetic chemical routes.
MARTIN W. WEISER

Martin earned his BS in Ceramic Engineering from Ohio State University and MS and
PhD in Materials Science and Mineral Engineering from the University of California,
Berkeley. At Berkeley he conducted fundamental research on sintering of powder compacts and ceramic matrix composites. After graduation he joined the University of New
Mexico (UNM) where he was a Visiting Assistant Professor in Chemical Engineering and
then Assistant Professor in Mechanical Engineering. At UNM he taught introductory and
advanced Materials Science classes to students from all branches of Engineering. He continued his research in ceramic fabrication as part of the Center for Micro-Engineered
Ceramics and also branched out into solder metallurgy and biomechanics in collaboration
with colleagues from Sandia National Laboratory and the UNM School of Medicine,
respectively.
Martin joined Johnson Matthey Electronics in a technical service role supporting the
Discrete Power Products Group (DPPG). In this role he also initiated JME’s efforts to
develop Pb-free solders for power die attach that came to fruition in collaboration with
J. N. Lalena several years later after JME was acquired by Honeywell. Martin spent
several years as the Product Manager for the DPPG and then joined the Six Sigma
Plus Organization after earning his Six Sigma Black Belt working on polymer/metal
composite thermal interface materials (TIMs). He spent the last several years in the
R&D group as both a Group Manager and Principle Scientist where he lead development
of improved Pb-free solders and new TIMs.

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FOREWORD TO FIRST EDITION
Whereas solid-state physics is concerned with the mathematical description of the varied
physical phenomena that solids exhibit and the solid-state chemist is interested in probing
the relationships between structural chemistry and physical phenomena, the materials
scientist has the task of using these descriptions and relationships to design materials
that will perform specified engineering functions. However, the physicist and the chemist
are often called upon to act as material designers, and the practice of materials design
commonly requires the exploration of novel chemistry that may lead to the discovery
of physical phenomena of fundamental importance for the body of solid state physics.
I cite three illustrations where an engineering need has led to new physics and chemistry
in the course of materials design.
In 1952, I joined a group at the M. I. T. Lincoln Laboratory that had been charged
with the task of developing a square B– H hysteresis loop in a ceramic ferrospinel that
could have its magnetization reversed in less than 1 ms by an applied magnetic field
strength less than twice the coercive field strength. At that time, the phenomenon of a
square B– H loop had been obtained in a few iron alloys by rolling them into tapes so
as to align the grains, and hence the easy magnetization directions, along the axis of
the tape. The observation of a square B – H loop led Jay Forrester, an electrical engineer,
to invent the coincident-current, random-access magnetic memory for the digital computer since, at that time, the only memory available was a 16 Â 16 byte electrostatic storage
tube. Unfortunately, the alloy tapes gave too slow a switching speed. As an electrical
engineer, Jay Forrester assumed the problem was eddy-current losses in the tapes, so
he had turned to the ferrimagnetic ferrospinels that were known to be magnetic insulators.
However, the polycrystalline ferrospinels are ceramics that cannot be rolled!
Nevertheless, the Air Force had financed the M. I. T. Lincoln Laboratory to develop
an Air Defense System of which the digital computer was to be a key component.
Therefore, Jay Forrester was able to put together an interdisciplinary team of electrical
engineers, ceramists, and physicists to realize his random-access magnetic memory
with ceramic ferrospinels.

The magnetic memory was achieved by a combination of systematic empiricism,
careful materials characterization, theoretical analysis, and the emergence of an unanticipated phenomenon that proved to be a stroke of good fortune. A systematic mapping of
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the structural, magnetic, and switching properties of the Mg– Mn– Fe ferrospinels as a
function of their heat treatments revealed that the spinels, in one part of the phase diagram, were tetragonal rather than cubic and that compositions, just on the cubic side of
the cubic-tetragonal phase boundary, yield sufficiently square B– H loops if given a
carefully controlled heat treatment. This observation led me to propose that the tetragonal
distortion was due to a cooperative orbital ordering on the Mn3ỵ ions that would lift the
cubic-field orbital degeneracy; cooperativity of the site distortions minimizes the cost in
elastic energy and leads to a distortion of the entire structure. This phenomenon is now
known as a cooperative Jahn – Teller distortion since Jahn and Teller had earlier pointed
out that a molecule or molecular complex, having an orbital degeneracy, would lower its
energy by deforming its configuration to a lower symmetry that removed the degeneracy.
Armed with this concept, I was able almost immediately to apply it to interpret the structure and the anisotropic magnetic interactions that had been found in the manganese –
oxide perovskites since the orbital order revealed the basis for specifying the rules for
the sign of a magnetic interaction in terms of the occupancies of the overlapping orbitals
responsible for the interatomic interactions. These rules are now known as the
Goodenough– Kanamori rules for the sign of a superexchange interaction. Thus an engineering problem prompted the discovery and description of two fundamental phenomena
in solids that ever since have been used by chemists and physicists to interpret structural
and magnetic phenomena in transition-metal compounds and to design new magnetic
materials. Moreover, the discovery of cooperative orbital ordering fed back to an
understanding of our empirical solution to the engineering problem. By annealing at

the optimum temperature for a specified time, the Mn3ỵ ions of a cubic spinel would
migrate to form Mn-rich regions where their energy is lowered through cooperative,
dynamic orbital ordering. The resulting chemical inhomogeneities acted as nucleating
centers for domains of reverse magnetization that, once nucleated, grew away from the
nucleating center. We also showed that eddy currents were not responsible for the slow
switching of the tapes, but a small coercive field strength and an intrinsic damping
factor for spin rotation.
In the early 1970s, an oil shortage focused worldwide attention on the need to
develop alternative energy sources; and it soon became apparent that these sources
would benefit from energy storage. Moreover, replacing the internal combustion
engine with electric-powered vehicles, or at least the introduction of hybrid vehicles,
would improve the air quality, particularly in big cities. Therefore, a proposal by the
Ford Motor Company to develop a sodium – sulfur battery operating at 3008C with
molten electrodes and a ceramic Naỵ-ion electrolyte stimulated interest in the design
of fast alkali-ion conductors. More significant was interest in a battery in which Liỵ
rather than Hỵ is the working ion, since the energy density that can be achieved
with an aqueous electrolyte is lower than what, in principle, can be obtained with a nonaqueous Liỵ-ion electrolyte. However, realization of a Liỵ-ion rechargeable battery
would require identication of a cathode material into/from which Liỵ ions can be
inserted/extracted reversibly. Brian Steele of Imperial College, London, first suggested
use of TiS2, which contains TiS2 layers held together only by Vander Waals S22 – S22
bonding; lithium can be inserted reversibly between the TiS2 layers. M. Stanley
Whittingham’s demonstration was the first to reduce this suggestion to practice while

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he was at the EXXON Corporation. Whittingham’s demonstration of a rechargeable
Li – TiS2 battery was commercially nonviable because the lithium anode proved
unsafe. Nevertheless, his demonstration focused attention on the work of the chemists
Jean Rouxel of Nantes and R. Schoăllhorn of Berlin on insertion compounds that provide
a convenient means of continuously changing the mixed valency of a fixed transitionmetal array across a redox couple. Although work at EXXON was halted, their demonstration had shown that if an insertion compound, such as graphite, was used as the anode,
a viable lithium battery could be achieved; but use of a less electropositive anode would
require an alternative insertion-compound cathode material that provided a higher voltage
versus a lithium anode than TiS2. I was able to deduce that no sulfide would give a significantly higher voltage than that obtained with TiS2 and therefore that it would be
necessary to go to a transition-metal oxide. Although oxides other than V2O5 and
MoO3, which contain vandyl or molybdyl ions, do not form layered structures analogous
to TiS2, I knew that LiMO2 compounds exist that have a layered structure similar to that of
LiTiS2. It was only necessary to choose the correct M3ỵ cation and to determine how much
Li could be extracted before the structure collapsed. That was how the Li12xCoO2 cathode
material was developed, which now powers the cell telephones and laptop computers.
The choice of M ẳ Co, Ni, or Ni0.5ỵdMn0.52d was dictated by the position of the redox
energies and an octahedral site-preference energy strong enough to inhibit migration of
the M atom to the Li layers on removal of Li. Electrochemical studies of these cathode
materials, and particularly of Li12xNi0.5ỵdMn0.52dO2, have provided a demonstration
of the pinning of a redox couple at the top of the valence band. This being a concept of
singular importance for interpretation of metallic oxides having only M – O– M interactions, of the reason for oxygen evolution at critical Co(IV)/Co(III) or Ni(IV)/Ni(III)
ratios in Li12xMO2 studies, and of why Cu(III) in an oxide has a low-spin configuration.
Moreover, exploration of other oxide structures that can act as hosts for insertion of Li as a
guest species have provided a means of quantitatively determining the influence of a
counter cation on the energy of a transition-metal redox couple. This determination
allows tuning of the energy of a redox couple, which may prove important for the
design of heterogenous catalysts.
As a third example, I turn to the discovery of high-temperature superconductivity in
the copper oxides, first announced by Bednorz and Muăller of IBM Zuărich in the summer
of 1986. Karl A. Muăller, the physicist of the pair, had been thinking that a dynamic Jahn –
Teller ordering might provide an enhanced electron– phonon coupling that would raise

the superconductive critical temperature TC. He turned to his chemist colleague
Bednorz to make a mixed-valent Cu3ỵ/Cu2ỵ compound since Cu2ỵ has an orbital degeneracy in an octahedral site. This speculation led to the discovery of the family of high-TC
copper oxides; however, the enhanced electron– phonon coupling is not due to a conventional dynamic Jahn –Teller orbital ordering, but rather to the first-order character of the
transition from localized to itinerant electronic behavior of s-bonding Cu : 3d electrons of
(x 2 2 y 2) symmetry in CuO2 planes. In this case, the search for an improved engineering
material has led to a demonstration that the celebrated Mott – Hubbard transition is
generally not as smooth as originally assumed, and it has introduced an unanticipated
new physics associated with bond-length fluctuations and vibronic electronic properties.
It has challenged the theorist to develop new theories of the crossover regime that can

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describe the mechanism of superconductive pair formation in the copper oxides, quantum
critical-point behavior at low temperatures, and an anomalous temperature dependence of
the resistivity at higher temperatures as a result of strong electron – phonon interactions.
These examples show how the challenge of materials design from the engineer may
lead to new physics as well as to new chemistry. Sorting out of the physical and chemical
origins of the new phenomena feed back to the range of concepts available to the designer
of new engineering materials. In recognition of the critical role in materials design of
interdisciplinary cooperation between physicists, chemists, ceramists, metallergists,
and engineers that is practiced in industry and government research laboratories, John
N. Lalena and David A. Cleary have initiated, with their book, what should prove to
be a growing trend toward greater interdisciplinarity in the education of those who will
be engaged in the design and characterization of tomorrow’s engineering materials.
JOHN B. GOODENOUGH


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PREFACE TO SECOND EDITION
In our first attempt at writing a textbook on the highly interdisciplinary subject of
inorganic materials design, we recognized the requirement that the book needed to
appeal to a very broad-based audience. Indeed, practicioneers of materials science and
engineering come from many different educational backgrounds, each emphasizing
different aspects. These include: solid-state chemistry, condensed-matter physics, metallurgy, ceramics, mechanical engineering, and materials science and engineering (MS&E).
Unfortunately, we did not adequately anticipate the level of difficulty that would be
associated with successfully implementing the task of attracting readers from so many
disciplines that, though distinct, possess the common threads of elucidating and utilizing
structure/property correlation in the design of new materials.
As a result, the first edition had a number of shortfalls. First and foremost, owing
to a variety of circumstances, there were many errors that, regrettably, made it into the
printed book. Great care has been taken to correct each of these. In addition to simply
revising the first edition, however, the content has been updated and expanded as well.
As was true with the first edition, this book is concerned, by and large, with theoretical
structure/property correlation as it applies to materials design. Nevertheless, a small
amount of space is dedicated to the empirical practice of synthesis and fabrication.
Much more discussion is devoted to these specialized topics concerned with the
preparation of materials, as opposed to their design, in numerous other books, one of
which is our companion textbook, Inorganic Materials Synthesis and Fabrication.
Some features added to this second edition include an expanded number of worked
examples and an appendix containing solutions to selected end-of-chapter problems. The
overall goal of our second edition is, quite simply, to rectify the problems we encountered
earlier, thereby producing a work that is much better suited as a tool to the working
professionals, educators, and students of this fascinating field.
J. N. LALENA, D. A. CLEARY


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PREFACE TO FIRST EDITION
Inorganic solid-state chemistry has matured into its own distinct subdiscipline. The reader
may wonder why we have decided to add another textbook to the plethora of books
already published. Our response is that we see a need for a single source presentation
that recognizes the interdisciplinary nature of the field. Solid-state chemists typically
receive a small amount of training in condensed matter physics, and none in materials
science or engineering, and yet all of these traditional fields are inextricably part of
inorganic solid-state chemistry.
Materials scientists and engineers have traditionally been primarily concerned
with the fabrication and utilization of materials already synthesized by the chemist and
identified by the physicist as having the appropriate intrinsic properties for a particular
engineering function. Although the demarcation between the three disciplines remains
in an academic sense, the separate job distinctions for those working in the field is
fading. This is especially obvious in the private sector, where one must ensure that
materials used in real commercial devices not only perform their primary function, but
also meet a variety of secondary requirements.
Individuals involved with these multidisciplinary and multitask projects must be prepared to work independently or to collaborate with other specialists in facing design challenges. In the latter case, communication is enhanced if each individual is able to speak
the “language” of the other. Therefore, in this book we introduce a number of concepts
that are not usually covered in standard solid-state chemistry textbooks. When this occurs,
we try to follow the introduction of the concept with an appropriate worked example to
demonstrate its use. Two areas that have lacked thorough coverage in most solid-state

chemistry texts in the past, namely microstructure and mechanical properties, are treated
extensively in this book.
We have kept the mathematics to a minimum – but adequate – level, suitable for a
descriptive treatment. Appropriate citations are included for those needing the quantitative details. It is assumed that the reader has sufficient knowledge of calculus and elementary linear algebra, particularly matrix manipulations, and some prior exposure to
thermodynamics, quantum theory, and group theory. The book should be satisfactory
for senior level undergraduate or beginning graduate students in chemistry. One will
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PREFACE TO FIRST EDITION

recognize from the Table of Contents that entire textbooks have been devoted to each of
the chapters in this book, and this limits the depth of coverage out of necessity. Along
with their chemistry colleagues, physics and engineering students should also find the
book to be informative and useful.
Every attempt has been made to extensively cite all the original and pertinent
research in a fashion similar to that found in a review article. Students are encouraged
to seek out this work. We have also included biographies of several individuals who
have made significant fundamental contributions to inorganic materials science in the
twentieth century. Limiting these to the small number we have room for was, of
course, difficult. The reader should be warned that some topics have been left out. In
this book, we only cover nonmolecular inorganic materials. Polymers and macromolecules are not discussed. Nor are the other extreme, for example, molecular electronics.
Also omitted are coverages of surface science, self assembly, and composite materials.
We are grateful to Professor John B. Wiley, Dr. Nancy F. Dean, Dr. Martin
W. Weiser, Professor Everett E. Carpenter, and Dr. Thomas K. Kodenkandath for reviewing various chapters in this book. We are grateful to Professor John F. Nye, Professor
John B. Goodenough, Dr. Frans Spaepen, Dr. Larry Kaufman, and Dr. Bert

Chamberland for providing biographical information. We would also like to thank
Professor Philip Anderson, Professor Mats H. Hillert, Professor Nye, Dr. Kaufman,
Dr. Terrell Vanderah, Dr. Barbara Sewall, and Mrs Jennifer Moss for allowing us to
use photographs from their personal collections. Finally, we acknowledge the inevitable
neglect our families must have felt during the period taken to write this book. We are
grateful for their understanding and tolerance.
J. N. LALENA, D. A. CLEARY

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ACRONYMS
AC
AFMs
AOT
APW
BCC
BM
BMGs
BO
BVS
BZ
CALPHAD
CB
CCP
CCSL
CDW
CFSE
CI
CMR

CO
CsCl
CSL
CTAB
CTE
CVD
CVM
DE
DFT
DMFT
DOS
DR1

alternating current
antiferromagnets
aerosol OT (sodium dioctylsulfosuccinate)
augmented plane wave
body-centered cubic
Bohr magneton
bulk metallic glasses
Block orbitals – then cited as being referred to as Block sums
through text
bond-valence sums
Brillouin zone
CALculation of PHAse Diagrams
carbazole-9-carbonyl chloride
cubic-closed package
constrained coincidence site lattice
charge density wave
crystal field stabilization energy

configuration interaction
colossal magnetoresistance
crystal orbital
cesium chloride
coincidence site lattice
cetyltrimethylammonium bromide
coefficient of thermal expansion
chemical vapor deposition
cluster variation method
double exchange
density-functional theory
dynamical mean field theory
density-of-states
Disperse Red 1
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