principles of inorganic materials design...principles of inorganic materials design second edition...

PRINCIPLES OFINORGANIC MATERIALS

DESIGN

SECOND EDITION

John N. LalenaThe Evergreen State College

David A. ClearyGonzaga University

InnodataFile Attachment9780470567531.jpg


DESIGN


DESIGN

SECOND EDITION

John N. LalenaThe Evergreen State College

David A. ClearyGonzaga University

Copyright # 2010 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New JerseyPublished 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 2010546–dc22

2009025906

Printed in the United States of America

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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 xxiii

1 CRYSTALLOGRAPHIC CONSIDERATIONS 11.1 Degrees of Crystallinity 2

1.1.1 Monocrystalline Solids 2

1.1.2 Quasicrystalline Solids 3

1.1.3 Polycrystalline Solids 5

1.1.4 Semicrystalline Solids 5

1.1.5 Amorphous Solids 8

1.2 Basic Crystallography 9

1.2.1 Space Lattice Geometry 9

1.3 Single Crystal Morphology and its Relationshipto Lattice Symmetry 31

1.4 Twinned Crystals 36

1.5 Crystallographic Orientation Relationships in Bicrystals 38

1.5.1 The Coincidence Site Lattice 38

1.5.2 Equivalent Axis-Angle Pairs 43

1.6 Amorphous Solids and Glasses 45

Practice Problems 50

References 52

v

2 MICROSTRUCTURAL CONSIDERATIONS 552.1 Materials Length Scales 56

2.1.1 Experimental Resolution of Material Features 59

2.2 Grain Boundaries in Polycrystalline Materials 61

2.2.1 Grain-Boundary Orientations 61

2.2.2 Dislocation Model of Low Angle Grain Boundaries 63

2.2.3 Grain-Boundary Energy 65

2.2.4 Special Types of Low-Energy Grain Boundaries 66

2.2.5 Grain-Boundary Dynamics 67

2.2.6 Representing Orientation Distributions in PolycrystallineAggregates 67

2.3 Materials Processing and Microstructure 70

2.3.1 Conventional Solidification 70

2.3.2 Deformation Processing 78

2.3.3 Consolidation Processing 78

2.3.4 Thin-Film Formation 79

2.4 Microstructure and Materials Properties 82

2.4.1 Mechanical Properties 83

2.4.2 Transport Properties 84

2.4.3 Magnetic and Dielectric Properties 88

2.4.4 Chemical Properties 90

2.5 Microstructure Control and Design 90


References 94

3 CRYSTAL STRUCTURES AND BINDING FORCES 973.1 Structure Description Methods 97

3.1.1 Close Packing 98

3.1.2 Polyhedra 101

3.1.3 The Unit Cell 103

3.1.4 Pearson Symbols 103

3.2 Cohesive Forces in Solids 103

3.2.1 Ionic Bonding 103

3.2.2 Covalent Bonding 106

3.2.3 Metallic Bonding 109

3.2.4 Atoms and Bonds as Electron Charge Density 110

CONTENTSvi

3.3 Structural Energetics 111

3.3.1 Lattice Energy 112

3.3.2 The Born–Haber Cycle 117

3.3.3 Goldschmidt’s Rules and Pauling’s Rules 118

3.3.4 Total Energy 120

3.3.5 Electronic Origin of Coordination Polyhedra inCovalent Crystals 122

3.4 Common Structure Types 127

3.4.1 Iono-Covalent Solids 127

3.4.2 Intermetallic Compounds 144

3.5 Structural Disturbances 153

3.5.1 Intrinsic Point Defects 154

3.5.2 Extrinsic Point Defects 156

3.5.3 Structural Distortions 157

3.5.4 Bond Valence Sum Calculations 160

3.6 Structure Control and Synthetic Strategies 163


References 169

4 THE ELECTRONIC LEVEL I: AN OVERVIEW OF BAND THEORY 1754.1 The Many-Body Schrödinger Equation 176

4.2 Bloch’s Theorem 179

4.3 Reciprocal Space 184

4.4 A Choice of Basis Sets 187

4.4.1 Plane-Wave Expansion – The Free-Electron Models 188

4.4.2 The Fermi Surface and Phase Stability 189

4.4.3 Bloch Sum Basis Set – The LCAO Method 192

4.5 Understanding Band-Structure Diagrams 193

4.6 Breakdown of the Independent Electron Approximation 197

4.7 Density Functional Theory – The Successor to the Hartree–FockApproach 198


References 201

5 THE ELECTRONIC LEVEL II: THE TIGHT-BINDINGELECTRONIC STRUCTURE APPROXIMATION 203

5.1 The General LCAO Method 204

5.2 Extension of the LCAO Treatment to Crystalline Solids 210

CONTENTS vii

5.3 Orbital Interactions in Monatomic Solids 213

5.3.1 s-Bonding Interactions 213

5.3.2 p-Bonding Interactions 217

5.4 Tight-Binding Assumptions 221

5.5 Qualitative LCAO Band Structures 223

5.5.1 Illustration 1: Transition Metal Oxides with Vertex-SharingOctahedra 228

5.5.2 Illustration 2: Reduced Dimensional Systems 231

5.5.3 Illustration 3: Transition Metal Monoxides with Edge-SharingOctahedra 233

5.5.4 Corollary 237

5.6 Total Energy Tight-Binding Calculations 238


References 240

6 TRANSPORT PROPERTIES 2416.1 An Introduction to Tensors 241

6.2 Thermal Conductivity 248

6.2.1 The Free Electron Contribution 249

6.2.2 The Phonon Contribution 251

6.3 Electrical Conductivity 254

6.3.1 Band Structure Considerations 258

6.3.2 Thermoelectric, Photovoltaic, and MagnetotransportProperties 263

6.4 Mass Transport 272

6.4.1 Atomic Diffusion 273

6.4.2 Ionic Conduction 280


References 282

7 METAL–NONMETAL TRANSITIONS 2857.1 Correlated Systems 287

7.1.1 The Mott–Hubbard Insulating State 289

7.1.2 Charge-Transfer Insulators 293

7.1.3 Marginal Metals 293

7.2 Anderson Localization 295

7.3 Experimentally Distinguishing Disorder from Electron Correlation 299

CONTENTSviii

7.4 Tuning the M–NM Transition 302

7.5 Other Types of Electronic Transitions 305


References 308

8 MAGNETIC AND DIELECTRIC PROPERTIES 3118.1 Phenomenological Description of Magnetic Behavior 313

8.1.1 Magnetization Curves 316

8.1.2 Susceptibility Curves 317

8.2 Atomic States and Term Symbols of Free Ions 319

8.3 Atomic Origin of Paramagnetism 325

8.3.1 Orbital Angular Momentum Contribution – The FreeIon Case 326

8.3.2 Spin Angular Momentum Contribution – The FreeIon Case 327

8.3.3 Total Magnetic Moment – The Free Ion Case 328

8.3.4 Spin–Orbit Coupling – The Free Ion Case 329

8.3.5 Single Ions in Crystals 330

8.3.6 Solids 336

8.4 Diamagnetism 339

8.5 Spontaneous Magnetic Ordering 339

8.5.1 Exchange Interactions 341

8.5.2 Itinerant Ferromagnetism 350

8.5.3 Noncolinear Spin Configurations andMagnetocrystalline Anisotropy 353

8.6 Magnetotransport Properties 359

8.6.1 The Double Exchange Mechanism 361

8.6.2 The Half-Metallic Ferromagnet Model 361

8.7 Magnetostriction 363

8.8 Dielectric Properties 364

8.8.1 The Microscopic Equations 365

8.8.2 Piezoelectricity 367

8.8.3 Pyroelectricity 370

8.8.4 Ferroelectricity 371


References 373

CONTENTS ix

9 OPTICAL PROPERTIES OF MATERIALS 3779.1 Maxwell’s Equations 377

9.2 Refractive Index 381

9.3 Absorption 390

9.4 Nonlinear Effects 395

9.5 Summary 400


References 401

10 MECHANICAL PROPERTIES 40310.1 Stress and Strain 404

10.2 Elasticity 407

10.2.1 The Elasticity Tensor 408

10.2.2 Elastically Isotropic Solids 413

10.2.3 The Relation Between Elasticity and theCohesive Forces in a Solid 421

10.2.4 Superelasticity, Pseudoelasticity, and theShape Memory Effect 430

10.3 Plasticity 433

10.3.1 The Dislocation-Based Mechanism to Plastic Deformation 439

10.3.2 Polycrystalline Metals 447

10.3.3 Brittle and Semibrittle Solids 448

10.3.4 The Correlation Between the Electronic Structureand the Plasticity of Materials 450

10.4 Fracture 451


References 456

11 PHASE EQUILIBRIA, PHASE DIAGRAMS, ANDPHASE MODELING 461

11.1 Thermodynamic Systems and Equilibrium 462

11.1.1 Equilibrium Thermodynamics 465

11.2 Thermodynamic Potentials and the Laws 469

11.3 Understanding Phase Diagrams 472

11.3.1 Unary Systems 472

11.3.2 Binary Metallurgical Systems 472

11.3.3 Binary Nonmetallic Systems 477

CONTENTSx

11.3.4 Ternary Condensed Systems 478

11.3.5 Metastable Equilibria 483

11.4 Experimental Phase-Diagram Determinations 484

11.5 Phase-Diagram Modeling 485

11.5.1 Gibbs Energy Expressions for Mixtures andSolid Solutions 485

11.5.2 Gibbs Energy Expressions for Phases withLong-Range Order 488

11.5.3 Other Contributions to the Gibbs Energy 493

11.5.4 Phase Diagram Extrapolations – theCALPHAD Method 494


References 499

12 SYNTHETIC STRATEGIES 50112.1 Synthetic Strategies 502

12.1.1 Direct Combination 503

12.1.2 Low Temperature 504

12.1.3 Defects 512

12.1.4 Combinatorial Synthesis 514

12.1.5 Spinodal Decomposition 514

12.1.6 Thin Films 517

12.1.7 Photonic Materials 519

12.1.8 Nanosynthesis 521

12.2 Summary 526


References 528

13 AN INTRODUCTION TO NANOMATERIALS 53113.1 History of Nanotechnology 532

13.2 Nanomaterials Properties 534

13.2.1 Electrical Properties 535

13.2.2 Magnetic Properties 536

13.2.3 Optical Properties 537

13.2.4 Thermal Properties 538

13.2.5 Mechanical Properties 538

13.2.6 Chemical Reactivity 539

CONTENTS xi

13.3 More on Nanomaterials Preparative Techniques 541

13.3.1 Top-Down Methods for the Fabrication ofNanocrystalline Materials 542

13.3.2 Bottom-Up Methods for the Synthesis ofNanostructured Solids 544

References 556

APPENDIX 1 559

APPENDIX 2 565

APPENDIX 3 569

INDEX 575

CONTENTSxii

FOREWORDTOSECONDEDITION

Materials science is one of the broadest of the applied science and engineering fields sinceit uses concepts from so many different subject areas. Chemistry is one of the key fields ofstudy, and in many materials science programs students must take general chemistry as aprerequisite for all but the most basic of survey courses. However, that is typically the lasttrue chemistry course that they take. The remainder of their chemistry training is accom-plished in their materials classes. This has served the field well for many years, but overthe past couple of decades new materials development has become more heavily depen-dent upon synthetic chemistry. This second edition of Principles of Inorganic MaterialsDesign serves as a fine text to introduce the materials student to the fundamentals ofdesigning materials through synthetic chemistry and the chemist to some of the issuesinvolved in materials design.

When I obtained my BS in Ceramic Engineering in 1981, the primary fields ofmaterials science – ceramics, metals, polymers, and semiconductors – were generallytaught in separate departments, although therewas frequently some overlap. This was par-ticularly true at the undergraduate level, although graduate programs frequently had moresubject overlap. During the 1980s, many of these departments merged to form materialsscience and engineering departments that began to take a more integrated approach to thefield, although chemical and electrical engineering programs tended to cover polymersand semiconductors in more depth. This trend continued in the 1990s and includedthe writing of texts such as The Production of Inorganic Materials by Evans and DeJonghe (Prentice Hall College Division, 1991), which focused on traditional productionmethods. Synthetic chemical approaches became more important as the decade pro-gressed and academia began to address this in the classroom, particularly at the graduatelevel. The first edition of Principles of Inorganic Materials Design strove to make thismaterial available to the upper division undergraduate student.

The second edition of Principles of Inorganic Materials Design corrects several gapsin the first edition to convert it from a very good compilation of the field into a text that isvery usable in the undergraduate classroom. Perhaps the biggest of these is the addition ofpractice problems at the end of every chapter since the second best way to learn a subjectis to apply it to problems (the best is to teach it) and this removes the burden of creatingthe problems from the instructor. Chapter 1, Crystallographic Considerations, is new and

xiii

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

In summary, the second edition of Principles of Inorganic Materials Design is a verygood text for several applications: a first materials course for chemistry and physics stu-dents; a consolidated materials chemistry course for materials science students; and asecond materials course for other engineering and applied science students. It is alsoserves as the background material to pursue the chemical routes to make these newmaterials described in texts such as Inorganic Materials Synthesis and Fabrication byLalena and Cleary (John Wiley & Sons, 2008). Such courses are critical to insure thatstudents from different disciplines can communicate as they move into industry andface 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 andPhD in Materials Science and Mineral Engineering from the University of California,Berkeley. At Berkeley he conducted fundamental research on sintering of powder com-pacts and ceramic matrix composites. After graduation he joined the University of NewMexico (UNM)where hewas a Visiting Assistant Professor in Chemical Engineering andthen Assistant Professor in Mechanical Engineering. At UNM he taught introductory andadvancedMaterials Science classes to students from all branches of Engineering. He con-tinued his research in ceramic fabrication as part of the Center for Micro-EngineeredCeramics and also branched out into solder metallurgy and biomechanics in collaborationwith colleagues from Sandia National Laboratory and the UNM School of Medicine,respectively.

Martin joined Johnson Matthey Electronics in a technical service role supporting theDiscrete Power Products Group (DPPG). In this role he also initiated JME’s efforts todevelop Pb-free solders for power die attach that came to fruition in collaboration withJ. N. Lalena several years later after JME was acquired by Honeywell. Martin spentseveral years as the Product Manager for the DPPG and then joined the Six SigmaPlus Organization after earning his Six Sigma Black Belt working on polymer/metalcomposite thermal interface materials (TIMs). He spent the last several years in theR&D group as both a Group Manager and Principle Scientist where he lead developmentof improved Pb-free solders and new TIMs.

FOREWORD TO SECOND EDITIONxiv

FOREWORD TO FIRST EDITION

Whereas solid-state physics is concerned with the mathematical description of the variedphysical phenomena that solids exhibit and the solid-state chemist is interested in probingthe relationships between structural chemistry and physical phenomena, the materialsscientist has the task of using these descriptions and relationships to design materialsthat will perform specified engineering functions. However, the physicist and the chemistare often called upon to act as material designers, and the practice of materials designcommonly requires the exploration of novel chemistry that may lead to the discoveryof 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 chemistryin the course of materials design.

In 1952, I joined a group at the M. I. T. Lincoln Laboratory that had been chargedwith the task of developing a square B–H hysteresis loop in a ceramic ferrospinel thatcould have its magnetization reversed in less than 1 ms by an applied magnetic fieldstrength less than twice the coercive field strength. At that time, the phenomenon of asquare B–H loop had been obtained in a few iron alloys by rolling them into tapes soas to align the grains, and hence the easy magnetization directions, along the axis ofthe 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 compu-ter since, at that time, the only memory available was a 16 � 16 byte electrostatic storagetube. Unfortunately, the alloy tapes gave too slow a switching speed. As an electricalengineer, Jay Forrester assumed the problem was eddy-current losses in the tapes, sohe 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 developan 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 electricalengineers, ceramists, and physicists to realize his random-access magnetic memorywith ceramic ferrospinels.

The magnetic memory was achieved by a combination of systematic empiricism,careful materials characterization, theoretical analysis, and the emergence of an unantici-pated phenomenon that proved to be a stroke of good fortune. A systematic mapping of

xv

the structural, magnetic, and switching properties of the Mg–Mn–Fe ferrospinels as afunction of their heat treatments revealed that the spinels, in one part of the phase dia-gram, were tetragonal rather than cubic and that compositions, just on the cubic side ofthe cubic-tetragonal phase boundary, yield sufficiently square B–H loops if given acarefully controlled heat treatment. This observation led me to propose that the tetragonaldistortion was due to a cooperative orbital ordering on the Mn3þ ions that would lift thecubic-field orbital degeneracy; cooperativity of the site distortions minimizes the cost inelastic energy and leads to a distortion of the entire structure. This phenomenon is nowknown as a cooperative Jahn–Teller distortion since Jahn and Teller had earlier pointedout that a molecule or molecular complex, having an orbital degeneracy, would lower itsenergy 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 struc-ture 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 forthe sign of a magnetic interaction in terms of the occupancies of the overlapping orbitalsresponsible for the interatomic interactions. These rules are now known as theGoodenough–Kanamori rules for the sign of a superexchange interaction. Thus an engin-eering problem prompted the discovery and description of two fundamental phenomenain solids that ever since have been used by chemists and physicists to interpret structuraland magnetic phenomena in transition-metal compounds and to design new magneticmaterials. Moreover, the discovery of cooperative orbital ordering fed back to anunderstanding of our empirical solution to the engineering problem. By annealing atthe optimum temperature for a specified time, the Mn3þ ions of a cubic spinel wouldmigrate to form Mn-rich regions where their energy is lowered through cooperative,dynamic orbital ordering. The resulting chemical inhomogeneities acted as nucleatingcenters for domains of reverse magnetization that, once nucleated, grew away from thenucleating center. We also showed that eddy currents were not responsible for the slowswitching of the tapes, but a small coercive field strength and an intrinsic dampingfactor for spin rotation.

In the early 1970s, an oil shortage focused worldwide attention on the need todevelop alternative energy sources; and it soon became apparent that these sourceswould benefit from energy storage. Moreover, replacing the internal combustionengine 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 theFord Motor Company to develop a sodium–sulfur battery operating at 3008C withmolten electrodes and a ceramic Naþ-ion electrolyte stimulated interest in the designof fast alkali-ion conductors. More significant was interest in a battery in which Liþ

rather than Hþ is the working ion, since the energy density that can be achievedwith an aqueous electrolyte is lower than what, in principle, can be obtained with a non-aqueous Liþ-ion electrolyte. However, realization of a Liþ-ion rechargeable batterywould require identification of a cathode material into/from which Liþ ions can beinserted/extracted reversibly. Brian Steele of Imperial College, London, first suggesteduse of TiS2, which contains TiS2 layers held together only by Vander Waals S

22–S22

bonding; lithium can be inserted reversibly between the TiS2 layers. M. StanleyWhittingham’s demonstration was the first to reduce this suggestion to practice while

FOREWARD TO FIRST EDITIONxvi

he was at the EXXON Corporation. Whittingham’s demonstration of a rechargeableLi–TiS2 battery was commercially nonviable because the lithium anode provedunsafe. Nevertheless, his demonstration focused attention on the work of the chemistsJean Rouxel of Nantes and R. Schöllhorn of Berlin on insertion compounds that providea convenient means of continuously changing the mixed valency of a fixed transition-metal array across a redox couple. Although work at EXXON was halted, their demon-stration 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 wouldrequire an alternative insertion-compound cathode material that provided a higher voltageversus a lithium anode than TiS2. I was able to deduce that no sulfide would give a sig-nificantly higher voltage than that obtained with TiS2 and therefore that it would benecessary to go to a transition-metal oxide. Although oxides other than V2O5 andMoO3, which contain vandyl or molybdyl ions, do not form layered structures analogousto TiS2, I knew that LiMO2 compounds exist that have a layered structure similar to that ofLiTiS2. It was only necessary to choose the correctM

3þ cation and to determine howmuchLi could be extracted before the structure collapsed. That was how the Li12xCoO2 cathodematerial was developed, which now powers the cell telephones and laptop computers.The choice of M ¼ Co, Ni, or Ni0.5þdMn0.52d was dictated by the position of the redoxenergies and an octahedral site-preference energy strong enough to inhibit migration ofthe M atom to the Li layers on removal of Li. Electrochemical studies of these cathodematerials, and particularly of Li12xNi0.5þdMn0.52dO2, have provided a demonstrationof the pinning of a redox couple at the top of the valence band. This being a concept ofsingular importance for interpretation of metallic oxides having only M–O–M inter-actions, 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 aguest species have provided a means of quantitatively determining the influence of acounter cation on the energy of a transition-metal redox couple. This determinationallows tuning of the energy of a redox couple, which may prove important for thedesign of heterogenous catalysts.

As a third example, I turn to the discovery of high-temperature superconductivity inthe copper oxides, first announced by Bednorz and Müller of IBM Zürich in the summerof 1986. Karl A. Müller, the physicist of the pair, had been thinking that a dynamic Jahn–Teller ordering might provide an enhanced electron–phonon coupling that would raisethe superconductive critical temperature TC. He turned to his chemist colleagueBednorz to make a mixed-valent Cu3þ/Cu2þ compound since Cu2þ has an orbital degen-eracy in an octahedral site. This speculation led to the discovery of the family of high-TCcopper oxides; however, the enhanced electron–phonon coupling is not due to a conven-tional dynamic Jahn–Teller orbital ordering, but rather to the first-order character of thetransition from localized to itinerant electronic behavior of s-bonding Cu :3d electrons of(x2 2 y2) symmetry in CuO2 planes. In this case, the search for an improved engineeringmaterial has led to a demonstration that the celebrated Mott–Hubbard transition isgenerally not as smooth as originally assumed, and it has introduced an unanticipatednew 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

FOREWARD TO FIRST EDITION xvii

describe the mechanism of superconductive pair formation in the copper oxides, quantumcritical-point behavior at low temperatures, and an anomalous temperature dependence ofthe resistivity at higher temperatures as a result of strong electron–phonon interactions.

These examples show how the challenge of materials design from the engineer maylead to new physics as well as to new chemistry. Sorting out of the physical and chemicalorigins of the new phenomena feed back to the range of concepts available to the designerof new engineering materials. In recognition of the critical role in materials design ofinterdisciplinary cooperation between physicists, chemists, ceramists, metallergists,and engineers that is practiced in industry and government research laboratories, JohnN. Lalena and David A. Cleary have initiated, with their book, what should prove tobe a growing trend toward greater interdisciplinarity in the education of those who willbe engaged in the design and characterization of tomorrow’s engineering materials.

JOHN B. GOODENOUGH

FOREWARD TO FIRST EDITIONxviii

PREFACE TO SECOND EDITION

In our first attempt at writing a textbook on the highly interdisciplinary subject ofinorganic materials design, we recognized the requirement that the book needed toappeal to a very broad-based audience. Indeed, practicioneers of materials science andengineering come from many different educational backgrounds, each emphasizingdifferent aspects. These include: solid-state chemistry, condensed-matter physics, metal-lurgy, ceramics, mechanical engineering, andmaterials science and engineering (MS&E).Unfortunately, we did not adequately anticipate the level of difficulty that would beassociated with successfully implementing the task of attracting readers from so manydisciplines that, though distinct, possess the common threads of elucidating and utilizingstructure/property correlation in the design of new materials.

As a result, the first edition had a number of shortfalls. First and foremost, owingto a variety of circumstances, there were many errors that, regrettably, made it into theprinted book. Great care has been taken to correct each of these. In addition to simplyrevising 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 theoreticalstructure/property correlation as it applies to materials design. Nevertheless, a smallamount of space is dedicated to the empirical practice of synthesis and fabrication.Much more discussion is devoted to these specialized topics concerned with thepreparation of materials, as opposed to their design, in numerous other books, one ofwhich is our companion textbook, Inorganic Materials Synthesis and Fabrication.

Some features added to this second edition include an expanded number of workedexamples and an appendix containing solutions to selected end-of-chapter problems. Theoverall goal of our second edition is, quite simply, to rectify the problems we encounteredearlier, thereby producing a work that is much better suited as a tool to the workingprofessionals, educators, and students of this fascinating field.

J. N. LALENA, D. A. CLEARY

xix

PREFACE TO FIRST EDITION

Inorganic solid-state chemistry has matured into its own distinct subdiscipline. The readermay wonder why we have decided to add another textbook to the plethora of booksalready published. Our response is that we see a need for a single source presentationthat recognizes the interdisciplinary nature of the field. Solid-state chemists typicallyreceive a small amount of training in condensed matter physics, and none in materialsscience or engineering, and yet all of these traditional fields are inextricably part ofinorganic solid-state chemistry.

Materials scientists and engineers have traditionally been primarily concernedwith the fabrication and utilization of materials already synthesized by the chemist andidentified by the physicist as having the appropriate intrinsic properties for a particularengineering function. Although the demarcation between the three disciplines remainsin an academic sense, the separate job distinctions for those working in the field isfading. This is especially obvious in the private sector, where one must ensure thatmaterials used in real commercial devices not only perform their primary function, butalso meet a variety of secondary requirements.

Individuals involved with these multidisciplinary and multitask projects must be pre-pared to work independently or to collaborate with other specialists in facing design chal-lenges. In the latter case, communication is enhanced if each individual is able to speakthe “language” of the other. Therefore, in this book we introduce a number of conceptsthat 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 todemonstrate its use. Two areas that have lacked thorough coverage in most solid-statechemistry texts in the past, namely microstructure and mechanical properties, are treatedextensively in this book.

We have kept the mathematics to a minimum – but adequate – level, suitable for adescriptive treatment. Appropriate citations are included for those needing the quantitat-ive details. It is assumed that the reader has sufficient knowledge of calculus and elemen-tary linear algebra, particularly matrix manipulations, and some prior exposure tothermodynamics, quantum theory, and group theory. The book should be satisfactoryfor senior level undergraduate or beginning graduate students in chemistry. One will

xxi

recognize from the Table of Contents that entire textbooks have been devoted to each ofthe chapters in this book, and this limits the depth of coverage out of necessity. Alongwith their chemistry colleagues, physics and engineering students should also find thebook to be informative and useful.

Every attempt has been made to extensively cite all the original and pertinentresearch in a fashion similar to that found in a review article. Students are encouragedto seek out this work. We have also included biographies of several individuals whohave made significant fundamental contributions to inorganic materials science in thetwentieth century. Limiting these to the small number we have room for was, ofcourse, difficult. The reader should be warned that some topics have been left out. Inthis book, we only cover nonmolecular inorganic materials. Polymers and macromol-ecules 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. MartinW.Weiser, Professor Everett E. Carpenter, and Dr. Thomas K. Kodenkandath for review-ing various chapters in this book. We are grateful to Professor John F. Nye, ProfessorJohn B. Goodenough, Dr. Frans Spaepen, Dr. Larry Kaufman, and Dr. BertChamberland for providing biographical information. We would also like to thankProfessor Philip Anderson, Professor Mats H. Hillert, Professor Nye, Dr. Kaufman,Dr. Terrell Vanderah, Dr. Barbara Sewall, and Mrs Jennifer Moss for allowing us touse photographs from their personal collections. Finally, we acknowledge the inevitableneglect our families must have felt during the period taken to write this book. We aregrateful for their understanding and tolerance.

J. N. LALENA, D. A. CLEARY

PREFACE TO FIRST EDITIONxxii

ACRONYMS

AC alternating currentAFMs antiferromagnetsAOT aerosol OT (sodium dioctylsulfosuccinate)APW augmented plane waveBCC body-centered cubicBM Bohr magnetonBMGs bulk metallic glassesBO Block orbitals – then cited as being referred to as Block sums

through textBVS bond-valence sumsBZ Brillouin zoneCALPHAD CALculation of PHAse DiagramsCB carbazole-9-carbonyl chlorideCCP cubic-closed packageCCSL constrained coincidence site latticeCDW charge density waveCFSE crystal field stabilization energyCI configuration interactionCMR colossal magnetoresistanceCO crystal orbitalCsCl cesium chlorideCSL coincidence site latticeCTAB cetyltrimethylammonium bromideCTE coefficient of thermal expansionCVD chemical vapor depositionCVM cluster variation methodDE double exchangeDFT density-functional theoryDMFT dynamical mean field theoryDOS density-of-statesDR1 Disperse Red 1

xxiii

DSC (lattice) displacement shift complete (lattice)DSC differential scanning calorimetryDTA differential thermal analysisEAM embedded atom methodEBS electrostatic bond strengthEBSD electron-backscatter diffractionECAE equal-channel angular extrusionECAP equal-channel angular pressingEDTA ethylenediamine tetraacetateEMF electromagnetic fieldEOS equation of stateEPMA electron probe microanalysisFC field cooledFCC face-centered cubicGE General Electric corporationGLAD glancing angle depositionGMR giant magnetoresistanceGMR giant magnetoresistiveGTOs Gaussian-type orbitalsHCP hexagonal close packedHeIM helium ion microscopeHOMO highest occupied molecular orbitalHRTEM high-resolution transmission electron microscopyIC integrated circuitsIR infrared radiationJT Jahn–TellerLCAO linear combination of atomic orbitalsLCOAO linear combination of orthogonalized atomic orbitalsLDA local density approximationLDA–DSF local density approximation–density function theoryLHB lower Hubbard bandLRO long-range [translational] orderLSDA local spin-density approximationLUMO lowest unoccupied molecular orbitalM. I. T. Massachusetts Institute of TechnologyMC Monte CarloMMC metal matrix compositeM–NM metallic–non-metallicMO molecular orbitalMOCVD metalorganic chemical vapor depositionMP Møller–PlessetMPB morphotropic phase boundaryMRO medium-range orderMS&E materials science and engineering

ACRONYMSxxiv

MSD microstructure sensitive designMWNT multi-walled carbon nanotubesNA numerical apertureND normal directionsNFE nearly free electronNMR nuclear magnetic resonanceODF orientation distribution functionPCF (single-mode) photonic crystal fiberPLD pulsed laser depositionPVD physical vapor depositionPVP poly(vinylpyrrolidone)PZT Pb(Zr,Ti)O3RD radial directionsRKKY Rudderman–Kittel–Kasuya–YoshidaRP Ruddlesden–PopperRPA random-phase approximationSALC symmetry-adapted linear combinationSANS small angle Newton scatteringSAXS small angle X-ray scatteringSC simple cubicSCF self-consistent fieldSDS sodium dodecylsulfateSDW spin density waveSEM scanning electron microscopeSHS self-propagating high-temperature synthesisSMA shape memory alloysSP spin-polarizedSPD severe plastic deformationSRO short-range orderSTM scanning tunneling microscopeSTOs Slater-type orbitalsSWNT single-walled carbon nanotubesTB tight bindingTD transverse directionsTE ThermoelectricTEM transmission electron microscopeTEOS tetraethyl orthosilicateTGG templated grain growthTIM thermal interface materialTOPO trioctylphosphine oxideTSSG top-seeded solution growthUFG ultrafine-grainedUHB upper Hubbard bandUTS ultimate tensile strength

ACRONYMS xxv

VEC valence electron concentrationVRH variable range hoppingVSEPR valence shell electron pair repulsionXRD X-ray diffractionZFC zero-field cooled

ACRONYMSxxvi

1

CRYSTALLOGRAPHICCONSIDERATIONS

There are many possible classification schemes for solids that can be envisioned. We cancategorize a material based solely on its chemical composition (inorganic, organic, orhybrid), the primary bonding type (ionic, covalent, metallic), its structure type (catenationpolymer, extended three-dimensional network), or its crystallinity (crystalline or noncrys-talline). It is the latter scheme that is the focus of this chapter. A crystalline materialexhibits a large degree of structural order in the arrangement of its constituent particles,be they atoms, ions, or molecules, over a large length scale whereas a noncrystallinematerial exhibits structural order only over a very short-range length scale correspondingto the first coordination sphere. It is structural order – the existence of a methodicalarrangement among the component particles – that makes the systematic study anddesign of materials with prescribed properties possible.

A crystal may be explicitly defined as a homogeneous solid consisting of a peri-odically repeating three-dimensional pattern of particles. Mathematically, there arethree key structural features to crystals.

1. Regularity, which may be described as equality of parts

2. Symmetry, the repetition of these regularities

Principles of Inorganic Materials Design, Second Edition. By John N. Lalena and David A. ClearyCopyright # 2010 John Wiley & Sons, Inc.

1

3. Long-range [translational] order (LRO), referring to the periodicity, or regularityin the arrangement of the material’s atomic or molecular constituents on a length-scale at least a few times larger than the size of these groups.

It is the presence of this long-range order that allows crystals to scatter incoming waves,of appropriate wavelengths, so as to produce discrete diffraction patterns, which, in turn,ultimately enables ascertainment of the actual atomic positions and, hence, crystallinestructure.

1.1 DEGREES OF CRYSTALLINITY

Crystallinity, like most things, can vary in degree. Even single crystals typicallyhave intrinsic point defects (e.g. lattice site vacancies) and extrinsic point defects (e.g.impurities), as well as extended defects such as dislocations. Defects are critical to thephysical properties of crystals and will be extensively covered in later chapters. Whatwe are referring to here with the degree of crystallinity is not the simple presence ofdefects, but rather the spectrum of crystallinity that encompasses the entire range fromcrystalline to fully disordered amorphous solids. Table 1.1 lists the various classes.Let’s take each of them in the order shown.

1.1.1 Monocrystalline Solids

At the top of the list is the single crystal, or monocrystal, which has the highest degree oforder. Several crystalline materials of enormous technological or commercial importanceare used in monocrystalline form. Figure 1.1a shows a drawing of a highly symmetricalquartz crystal, such as might be grown freely suspended in a fluid. For a crystal, the entiremacroscopic body can be regarded as a monolithic three-dimensional space-filling rep-etition of the fundamental crystallographic unit cell. Typically, the external morphologyof a single crystal is faceted (consisting of faces), as in Figure 1.1a, although this need notbe the case. The word habit is used to describe the overall external shape of a crystalspecimen. Habits, which can be polyhedral or nonpolyhedral, may be described ascubic, octahedral, fibrous, acicular, prismatic, dendritic (tree-like), platy, blocky, orblade-like, among many others. The point symmetry of the crystal’s morphologicalform cannot exceed the point symmetry of the lattice.

TABLE 1.1. Degrees of Crystallinity

Type Defining Features

Monocrystalline LROQuasicrystalline Noncrystallographic rotational symmetry, no LROPolycrystalline Crystallites separated by grain boundariesSemicrystalline Crystalline regions separated by amorphous regionsAmorphous andglassy state

No LRO, no rotational symmetry, does possess short-rangeorder (SRO)

CRYSTALLOGRAPHIC CONSIDERATIONS2

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