Principles of Inorganic Materials Design

PRINCIPLES OF INORGANIC MATERIALS DESIGN......Page 5
CONTENTS......Page 7
FOREWORD TO SECOND EDITION......Page 15
FOREWORD TO FIRST EDITION......Page 17
PREFACE TO SECOND EDITION......Page 21
PREFACE TO FIRST EDITION......Page 23
ACRONYMS......Page 25
1 CRYSTALLOGRAPHIC CONSIDERATIONS......Page 29
1.1.1 Monocrystalline Solids......Page 30
1.1.2 Quasicrystalline Solids......Page 31
1.1.4 Semicrystalline Solids......Page 33
1.1.5 Amorphous Solids......Page 36
1.2.1 Space Lattice Geometry......Page 37
1.3 Single Crystal Morphology and its Relationship to Lattice Symmetry......Page 59
1.4 Twinned Crystals......Page 64
1.5.1 The Coincidence Site Lattice......Page 66
1.5.2 Equivalent Axis-Angle Pairs......Page 71
1.6 Amorphous Solids and Glasses......Page 73
Practice Problems......Page 78
References......Page 80
2 MICROSTRUCTURAL CONSIDERATIONS......Page 83
2.1 Materials Length Scales......Page 84
2.1.1 Experimental Resolution of Material Features......Page 87
2.2.1 Grain-Boundary Orientations......Page 89
2.2.2 Dislocation Model of Low Angle Grain Boundaries......Page 91
2.2.3 Grain-Boundary Energy......Page 93
2.2.4 Special Types of Low-Energy Grain Boundaries......Page 94
2.2.6 Representing Orientation Distributions in Polycrystalline Aggregates......Page 95
2.3.1 Conventional Solidification......Page 98
2.3.3 Consolidation Processing......Page 106
2.3.4 Thin-Film Formation......Page 107
2.4 Microstructure and Materials Properties......Page 110
2.4.1 Mechanical Properties......Page 111
2.4.2 Transport Properties......Page 112
2.4.3 Magnetic and Dielectric Properties......Page 116
2.5 Microstructure Control and Design......Page 118
Practice Problems......Page 121
References......Page 122
3.1 Structure Description Methods......Page 125
3.1.1 Close Packing......Page 126
3.1.2 Polyhedra......Page 129
3.2.1 Ionic Bonding......Page 131
3.2.2 Covalent Bonding......Page 134
3.2.3 Metallic Bonding......Page 137
3.2.4 Atoms and Bonds as Electron Charge Density......Page 138
3.3 Structural Energetics......Page 139
3.3.1 Lattice Energy......Page 140
3.3.2 The Born–Haber Cycle......Page 145
3.3.3 Goldschmidt’s Rules and Pauling’s Rules......Page 146
3.3.4 Total Energy......Page 148
3.3.5 Electronic Origin of Coordination Polyhedra in Covalent Crystals......Page 150
3.4.1 Iono-Covalent Solids......Page 155
3.4.2 Intermetallic Compounds......Page 172
3.5 Structural Disturbances......Page 181
3.5.1 Intrinsic Point Defects......Page 182
3.5.2 Extrinsic Point Defects......Page 184
3.5.3 Structural Distortions......Page 185
3.5.4 Bond Valence Sum Calculations......Page 188
3.6 Structure Control and Synthetic Strategies......Page 191
Practice Problems......Page 195
References......Page 197
4 THE ELECTRONIC LEVEL I: AN OVERVIEW OF BAND THEORY......Page 203
4.1 The Many-Body Schrödinger Equation......Page 204
4.2 Bloch’s Theorem......Page 207
4.3 Reciprocal Space......Page 212
4.4 A Choice of Basis Sets......Page 215
4.4.1 Plane-Wave Expansion – The Free-Electron Models......Page 216
4.4.2 The Fermi Surface and Phase Stability......Page 217
4.4.3 Bloch Sum Basis Set – The LCAO Method......Page 220
4.5 Understanding Band-Structure Diagrams......Page 221
4.6 Breakdown of the Independent Electron Approximation......Page 225
4.7 Density Functional Theory – The Successor to the Hartree–Fock Approach......Page 226
Practice Problems......Page 227
References......Page 229
5 THE ELECTRONIC LEVEL II: THE TIGHT-BINDING ELECTRONIC STRUCTURE APPROXIMATION......Page 231
5.1 The General LCAO Method......Page 232
5.2 Extension of the LCAO Treatment to Crystalline Solids......Page 238
5.3.1 σ-Bonding Interactions......Page 241
5.3.2 π-Bonding Interactions......Page 245
5.4 Tight-Binding Assumptions......Page 249
5.5 Qualitative LCAO Band Structures......Page 251
5.5.1 Illustration 1: Transition Metal Oxides with Vertex-Sharing Octahedra......Page 256
5.5.2 Illustration 2: Reduced Dimensional Systems......Page 259
5.5.3 Illustration 3: Transition Metal Monoxides with Edge-Sharing Octahedra......Page 261
5.5.4 Corollary......Page 265
5.6 Total Energy Tight-Binding Calculations......Page 266
Practice Problems......Page 267
References......Page 268
6.1 An Introduction to Tensors......Page 269
6.2 Thermal Conductivity......Page 276
6.2.1 The Free Electron Contribution......Page 277
6.2.2 The Phonon Contribution......Page 279
6.3 Electrical Conductivity......Page 282
6.3.1 Band Structure Considerations......Page 286
6.3.2 Thermoelectric, Photovoltaic, and Magnetotransport Properties......Page 291
6.4 Mass Transport......Page 300
6.4.1 Atomic Diffusion......Page 301
6.4.2 Ionic Conduction......Page 308
Practice Problems......Page 309
References......Page 310
7 METAL–NONMETAL TRANSITIONS......Page 313
7.1 Correlated Systems......Page 315
7.1.1 The Mott–Hubbard Insulating State......Page 317
7.1.3 Marginal Metals......Page 321
7.2 Anderson Localization......Page 323
7.3 Experimentally Distinguishing Disorder from Electron Correlation......Page 327
7.4 Tuning the M–NM Transition......Page 330
7.5 Other Types of Electronic Transitions......Page 333
Practice Problems......Page 335
References......Page 336
8 MAGNETIC AND DIELECTRIC PROPERTIES......Page 339
8.1 Phenomenological Description of Magnetic Behavior......Page 341
8.1.1 Magnetization Curves......Page 344
8.1.2 Susceptibility Curves......Page 345
8.2 Atomic States and Term Symbols of Free Ions......Page 347
8.3 Atomic Origin of Paramagnetism......Page 353
8.3.1 Orbital Angular Momentum Contribution – The Free Ion Case......Page 354
8.3.2 Spin Angular Momentum Contribution – The Free Ion Case......Page 355
8.3.3 Total Magnetic Moment – The Free Ion Case......Page 356
8.3.4 Spin–Orbit Coupling – The Free Ion Case......Page 357
8.3.5 Single Ions in Crystals......Page 358
8.3.6 Solids......Page 364
8.5 Spontaneous Magnetic Ordering......Page 367
8.5.1 Exchange Interactions......Page 369
8.5.2 Itinerant Ferromagnetism......Page 378
8.5.3 Noncolinear Spin Configurations and Magnetocrystalline Anisotropy......Page 381
8.6 Magnetotransport Properties......Page 387
8.6.2 The Half-Metallic Ferromagnet Model......Page 389
8.7 Magnetostriction......Page 391
8.8 Dielectric Properties......Page 392
8.8.1 The Microscopic Equations......Page 393
8.8.2 Piezoelectricity......Page 395
8.8.3 Pyroelectricity......Page 398
8.8.4 Ferroelectricity......Page 399
Practice Problems......Page 400
References......Page 401
9.1 Maxwell’s Equations......Page 405
9.2 Refractive Index......Page 409
9.3 Absorption......Page 418
9.4 Nonlinear Effects......Page 423
Practice Problems......Page 428
References......Page 429
10 MECHANICAL PROPERTIES......Page 431
10.1 Stress and Strain......Page 432
10.2 Elasticity......Page 435
10.2.1 The Elasticity Tensor......Page 436
10.2.2 Elastically Isotropic Solids......Page 441
10.2.3 The Relation Between Elasticity and the Cohesive Forces in a Solid......Page 449
10.2.4 Superelasticity, Pseudoelasticity, and the Shape Memory Effect......Page 458
10.3 Plasticity......Page 461
10.3.1 The Dislocation-Based Mechanism to Plastic Deformation......Page 467
10.3.2 Polycrystalline Metals......Page 475
10.3.3 Brittle and Semibrittle Solids......Page 476
10.3.4 The Correlation Between the Electronic Structure and the Plasticity of Materials......Page 478
10.4 Fracture......Page 479
Practice Problems......Page 482
References......Page 484
11 PHASE EQUILIBRIA, PHASE DIAGRAMS, AND PHASE MODELING......Page 489
11.1 Thermodynamic Systems and Equilibrium......Page 490
11.1.1 Equilibrium Thermodynamics......Page 493
11.2 Thermodynamic Potentials and the Laws......Page 497
11.3.2 Binary Metallurgical Systems......Page 500
11.3.3 Binary Nonmetallic Systems......Page 505
11.3.4 Ternary Condensed Systems......Page 506
11.3.5 Metastable Equilibria......Page 511
11.4 Experimental Phase-Diagram Determinations......Page 512
11.5.1 Gibbs Energy Expressions for Mixtures and Solid Solutions......Page 513
11.5.2 Gibbs Energy Expressions for Phases with Long-Range Order......Page 516
11.5.3 Other Contributions to the Gibbs Energy......Page 521
11.5.4 Phase Diagram Extrapolations – the CALPHAD Method......Page 522
Practice Problems......Page 526
References......Page 527
12 SYNTHETIC STRATEGIES......Page 529
12.1 Synthetic Strategies......Page 530
12.1.1 Direct Combination......Page 531
12.1.2 Low Temperature......Page 532
12.1.3 Defects......Page 540
12.1.5 Spinodal Decomposition......Page 542
12.1.6 Thin Films......Page 545
12.1.7 Photonic Materials......Page 547
12.1.8 Nanosynthesis......Page 549
Practice Problems......Page 554
References......Page 556
13 AN INTRODUCTION TO NANOMATERIALS......Page 559
13.1 History of Nanotechnology......Page 560
13.2 Nanomaterials Properties......Page 562
13.2.1 Electrical Properties......Page 563
13.2.2 Magnetic Properties......Page 564
13.2.3 Optical Properties......Page 565
13.2.5 Mechanical Properties......Page 566
13.2.6 Chemical Reactivity......Page 567
13.3 More on Nanomaterials Preparative Techniques......Page 569
13.3.1 Top-Down Methods for the Fabrication of Nanocrystalline Materials......Page 570
13.3.2 Bottom-Up Methods for the Synthesis of Nanostructured Solids......Page 572
References......Page 584
APPENDIX 1......Page 587
APPENDIX 2......Page 593
APPENDIX 3......Page 597
INDEX......Page 603