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 ............................. 1
1.1. Degrees of Crystallinity .............................. 2
1.1.1. Monocrystalline Solids ........................ 2
1.1.2. Quasicrystalline Solids ....................... 3
1.1.3. Poly crystalline 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 Relationship to
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
2. MICROSTRUCTURAL CONSIDERATIONS ............................. 55
2.1. 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
Polycrystalline Aggregates ................... 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
Practice Problems .......................................... 93
References ................................................. 94
3. CRYSTAL STRUCTURES AND BINDING FORCES ...................... 97
3.1. 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
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 in Covalent 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
Practice Problems ......................................... 167
References ................................................ 169
4. THE ELECTRONIC LEVEL I: AN OVERVIEW OF BAND THEORY ........ 175
4.1. The Many-Body Schrodinger 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-Fock Approach ........................... 198
Practice Problems ......................................... 199
References ................................................ 201
5. THE ELECTRONIC LEVEL II: THE TIGHT-BINDING ELECTRONIC
STRUCTURE APPROXIMATION ................................... 203
5.1. The General LCAO Method ............................. 204
5.2. Extension of the LCAO Treatment to Crystalline
Solids .............................................. 210
5.3. Orbital Interactions in Monatomic Solids ............ 213
5.3.1. σ-Bonding Interactions ...................... 213
5.3.2. π-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-Sharing Octahedra ............... 228
5.5.2. Illustration 2: Reduced Dimensional
Systems ..................................... 231
5.5.3. Illustration 3: Transition Metal Monoxides
with Edge-Sharing Octahedra ................. 233
5.5.4. Corollary ................................... 237
5.6. Total Energy Tight-Binding Calculations ............. 238
Practice Problems ......................................... 239
References ................................................ 240
6. TRANSPORT PROPERTIES ...................................... 241
6.1. 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 Magneto
transport Properties ........................ 263
6.4. Mass Transport ...................................... 272
6.4.1. Atomic Diffusion ............................ 273
6.4.2. Ionic Conduction ............................ 280
Practice Problems ......................................... 281
References ................................................ 282
7. METAL-NONMETALTRANSITIONS ................................. 285
7.1. 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
7.4. Tuning the M-NM Transition .......................... 302
7.5. Other Types of Electronic Transitions ............... 305
Practice Problems ......................................... 307
References ................................................ 308
8. MAGNETIC AND DIELECTRIC PROPERTIES ........................ 311
8.1. 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 Free Ion Case ........................... 326
8.3.2. Spin Angular Momentum Contribution -
The Free Ion 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 and
Magnetocrystalline 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
Practice Problems ......................................... 372
References ................................................ 373
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