Preface to the Second Edition xvii
Preface to the First Edition xix
PART 1 STRUCTURES AND MICROSTRUCTURES 1
1 The electron structure of atoms 3
1.1 The hydrogen atom 3
1.1.1 The quantum mechanical description 3
1.1.2 The energy of the electron 4
1.1.3 Electron orbitals 5
1.1.4 Orbital shapes 5
1.2 Many-electron atoms 7
1.2.1 The orbital approximation 7
1.2.2 Electron spin and electron configuration 7
1.2.3 The periodic table 9
1.3 Atomic energy levels 11
1.3.1 Spectra and energy levels 11
1.3.2 Terms and term symbols 11
1.3.3 Levels 13
1.3.4 Electronic energy level calculations 14
Further reading 15
Problems and exercises 16
2 Chemical bonding 19
2.1 Ionic bonding 19
2.1.1 Ions 19
2.1.2 Ionic size and shape 20
2.1.3 Lattice energies 21
2.1.4 Atomistic simulation 23
2.2 Covalent bonding 24
2.2.1 Valence bond theory 24
2.2.2 Molecular orbital theory 30
2.3 Metallic bonding and energy bands 35
2.3.1 Molecular orbitals and energy bands 36
2.3.2 The free electron gas 37
2.3.3 Energy bands 40
2.3.4 Properties of metals 41
2.3.5 Bands in ionic and covalent solids 43
2.3.6 Computation of properties 44
Further reading 45
Problems and exercises 46
3 States of aggregation 49
3.1 Weak chemical bonds 49
3.2 Macrostructures, microstructures and nanostructures 52
3.2.1 Structures and scale 52
3.2.2 Crystalline solids 52
3.2.3 Quasicrystals 53
3.2.4 Non-crystalline solids 54
3.2.5 Partly crystalline solids 55
3.2.6 Nanoparticles and nanostructures 55
3.3 The development of microstructures 57
3.3.1 Solidification 58
3.3.2 Processing 58
3.4 Point defects 60
3.4.1 Point defects in crystals of elements 60
3.4.2 Solid solutions 61
3.4.3 Schottky defects 62
3.4.4 Frenkel defects 63
3.4.5 Non-stoichiometric compounds 64
3.4.6 Point defect notation 66
3.5 Linear, planar and volume defects 68
3.5.1 Edge dislocations 68
3.5.2 Screw dislocations 69
3.5.3 Partial and mixed dislocations 69
3.5.4 Planar defects 69
3.5.5 Volume defects: precipitates 70
Further reading 73
Problems and exercises 73
4 Phase diagrams 77
4.1 Phases and phase diagrams 77
4.1.1 One-component (unary) systems 77
4.1.2 The phase rule for one-component (unary) systems 79
4.2 Binary phase diagrams 80
4.2.1 Two-component (binary) systems 80
4.2.2 The phase rule for two-component (binary) systems 81
4.2.3 Simple binary diagrams: nickel-copper as an example 81
4.2.4 Binary systems containing a eutectic point: tin-lead as an example 83
4.2.5 Intermediate phases and melting 87
4.3 The iron-carbon system near to iron 88
4.3.1 The iron-carbon phase diagram 88
4.3.2 Steels and cast irons 89
4.3.3 Invariant points 89
4.4 Ternary systems 90
4.5 Calculation of phase diagrams: CALPHAD 93
Further reading 94
Problems and exercises 94
5 Crystallography and crystal structures 101
5.1 Crystallography 101
5.1.1 Crystal lattices 101
5.1.2 Crystal systems and crystal structures 102
5.1.3 Symmetry and crystal classes 104
5.1.4 Crystal planes and Miller indices 106
5.1.5 Hexagonal crystals and Miller-Bravais indices 109
5.1.6 Directions 110
5.1.7 Crystal geometry and the reciprocal lattice 112
5.2 The determination of crystal structures 114
5.2.1 Single crystal X-ray diffraction 114
5.2.2 Powder X-ray diffraction and crystal identification 115
5.2.3 Neutron diffraction 118
5.2.4 Electron diffraction 118
5.3 Crystal structures 118
5.3.1 Unit cells, atomic coordinates and nomenclature 118
5.3.2 The density of a crystal 119
5.3.3 The cubic close-packed (A1) structure 121
5.3.4 The body-centred cubic (A2) structure 121
5.3.5 The hexagonal (A3) structure 122
5.3.6 The diamond (A4) structure 122
5.3.7 The graphite (A9) structure 123
5.3.8 The halite (rock salt, sodium chloride, B1) structure 123
5.3.9 The spinel (H11) structure 125
5.4 Structural relationships 126
5.4.1 Sphere packing 126
5.4.2 Ionic structures in terms of anion packing 128
5.4.3 Polyhedral representations 129
Further reading 131
Problems and exercises 131
PART 2 CLASSES OF MATERIALS 137
6 Metals, ceramics, polymers and composites 139
6.1 Metals 139
6.1.1 The crystal structures of pure metals 140
6.1.2 Metallic radii 141
6.1.3 Alloy solid solutions 142
6.1.4 Metallic glasses 145
6.1.5 The principal properties of metals 146
6.2 Ceramics 147
6.2.1 Bonding and structure of silicate ceramics 147
6.2.2 Some non-silicate ceramics 149
6.2.3 The preparation and processing of ceramics 152
6.2.4 The principal properties of ceramics 154
6.3 Silicate glasses 154
6.3.1 Bonding and structure of silicate glasses 155
6.3.2 Glass deformation 157
6.3.3 Strengthened glass 159
6.3.4 Glass-ceramics 160
6.4 Polymers 161
6.4.1 Polymer formation 162
6.4.2 Microstructures of polymers 165
6.4.3 Production of polymers 170
6.4.4 Elastomers 173
6.4.5 The principal properties of polymers 175
6.5 Composite materials 177
6.5.1 Fibre-reinforced plastics 177
6.5.2 Metal-matrix composites 177
6.5.3 Ceramic-matrix composites 178
6.5.4 Cement and concrete 178
Further reading 181
Problems and exercises 182
PART 3 REACTIONS AND TRANSFORMATIONS 189
7 Diffusion and ionic conductivity 191
7.1 Self-diffusion, tracer diffusion and tracer impurity diffusion 191
7.2 Non-steady-state diffusion 194
7.3 Steady-state diffusion 195
7.4 Temperature variation of diffusion coefficient 195
7.5 The effect of impurities 196
7.6 Random walk diffusion 197
7.7 Diffusion in solids 198
7.8 Self-diffusion in one dimension 199
7.9 Self-diffusion in crystals 201
7.10 The Arrhenius equation and point defects 202
7.11 Correlation factors for self-diffusion 204
7.12 Ionic conductivity 205
7.12.1 Ionic conductivity in solids 205
7.12.2 The relationship between ionic conductivity and diffusion coefficient 208
Further reading 209
Problems and exercises 209
8 Phase transformations and reactions 213
8.1 Sintering 213
8.1.1 Sintering and reaction 213
8.1.2 The driving force for sintering 215
8.1.3 The kinetics of neck growth 216
8.2 First-order and second-order phase transitions 216
8.2.1 First-order phase transitions 217
8.2.2 Second-order transitions 217
8.3 Displacive and reconstructive transitions 218
8.3.1 Displacive transitions 218
8.3.2 Reconstructive transitions 219
8.4 Order-disorder transitions 221
8.4.1 Positional ordering 221
8.4.2 Orientational ordering 222
8.5 Martensitic transformations 223
8.5.1 The austenite-martensite transition 223
8.5.2 Martensitic transformations in zirconia 226
8.5.3 Martensitic transitions in Ni-Ti alloys 227
8.5.4 Shape-memory alloys 228
8.6 Phase diagrams and microstructures 230
8.6.1 Equilibrium solidification of simple binary alloys 230
8.6.2 Non-equilibrium solidification and coring 230
8.6.3 Solidification in systems containing a eutectic point 231
8.6.4 Equilibrium heat treatment of steel in the Fe-C phase diagram 233
8.7 High-temperature oxidation of metals 236
8.7.1 Direct corrosion 236
8.7.2 The rate of oxidation 236
8.7.3 Oxide film microstructure 237
8.7.4 Film growth via diffusion 238
8.7.5 Alloys 239
8.8 Solid-state reactions 240
8.8.1 Spinel formation 240
8.8.2 The kinetics of spinel formation 241
Further reading 242
Problems and exercises 242
9 Oxidation and reduction 247
9.1 Galvanic cells 247
9.1.1 Cell basics 247
9.1.2 Standard electrode potentials 249
9.1.3 Cell potential and Gibbs energy 250
9.1.4 Concentration dependence 251
9.2 Chemical analysis using galvanic cells 251
9.2.1 pH meters 251
9.2.2 Ion selective electrodes 253
9.2.3 Oxygen sensors 254
9.3 Batteries 255
9.3.1 'Dry' and alkaline primary batteries 255
9.3.2 Lithium-ion primary batteries 256
9.3.3 The lead-acid secondary battery 257
9.3.4 Lithium-ion secondary batteries 257
9.3.5 Lithium-air batteries 259
9.3.6 Fuel cells 260
9.4 Corrosion 262
9.4.1 The reaction of metals with water and aqueous acids 262
9.4.2 Dissimilar metal corrosion 264
9.4.3 Single metal electrochemical corrosion 265
9.5 Electrolysis 266
9.5.1 Electrolytic cells 267
9.5.2 Electroplating 267
9.5.3 The amount of product produced during electrolysis 268
9.5.4 The electrolytic preparation of titanium by the FFC Cambridge Process 269
9.6 Pourbaix diagrams 270
9.6.1 Passivation, corrosion and leaching 270
9.6.2 The stability field of water 270
9.6.3 Pourbaix diagram for a metal showing two valence states, M2th and M3th 271
9.6.4 Pourbaix diagram displaying tendency for corrosion 273
Further reading 274
Problems and exercises 275
PART 4 PHYSICAL PROPERTIES 279
10 Mechanical properties of solids 281
10.1 Strength and hardness 281
10.1.1 Strength 281
10.1.2 Stress and strain 282
10.1.3 Stress-strain curves 283
10.1.4 Toughness and stiffness 286
10.1.5 Superelasticity 286
10.1.6 Hardness 287
10.2 Elastic moduli 289
10.2.1 Young's modulus (the modulus of elasticity) (E or Y) 289
10.2.2 Poisson's ratio (n) 291
10.2.3 The longitudinal or axial modulus (L or M) 292
10.2.4 The shear modulus or modulus of rigidity (G or m) 292
10.2.5 The bulk modulus, K or B 293
10.2.6 The Lame modulus (l) 293
10.2.7 Relationships between the elastic moduli 293
10.2.8 Ultrasonic waves in elastic solids 293
10.3 Deformation and fracture 295
10.3.1 Brittle fracture 295
10.3.2 Plastic deformation of metals 298
10.3.3 Dislocation movement and plastic deformation 298
10.3.4 Brittle and ductile materials 301
10.3.5 Plastic deformation of polymers 302
10.3.6 Fracture following plastic deformation 302
10.3.7 Strengthening 304
10.3.8 Computation of deformation and fracture 306
10.4 Time-dependent properties 307
10.4.1 Fatigue 307
10.4.2 Creep 308
10.5 Nanoscale properties 312
10.5.1 Solid lubricants 312
10.5.2 Auxetic materials 313
10.5.3 Thin films and nanowires 315
10.6 Composite materials 317
10.6.1 Young's modulus of large particle composites 317
10.6.2 Young's modulus of fibre-reinforced composites 318
10.6.3 Young's modulus of a two-phase system 319
Further reading 320
Problems and exercises 321
11 Insulating solids 327
11.1 Dielectrics 327
11.1.1 Relative permittivity and polarisation 327
11.1.2 Polarisability 329
11.1.3 Polarisability and relative permittivity 330
11.1.4 The frequency dependence of polarisability and relative permittivity 331
11.1.5 The relative permittivity of crystals 332
11.2 Piezoelectrics, pyroelectrics and ferroelectrics 333
11.2.1 The piezoelectric and pyroelectric effects 333
11.2.2 Crystal symmetry and the piezoelectric and pyroelectric effects 335
11.2.3 Piezoelectric mechanisms 336
11.2.4 Quartz oscillators 337
11.2.5 Piezoelectric polymers 338
11.3 Ferroelectrics 340
11.3.1 Ferroelectric crystals 340
11.3.2 Hysteresis and domain growth in ferroelectric crystals 341
11.3.3 Antiferroelectrics 344
11.3.4 The temperature dependence of ferroelectricity and antiferroelectricity 344
11.3.5 Ferroelectricity due to hydrogen bonds 345
11.3.6 Ferroelectricity due to polar groups 347
11.3.7 Ferroelectricity due to medium-sized transition-metal cations 348
11.3.8 Poling and polycrystalline ferroelectric solids 349
11.3.9 Doping and modification of properties 349
11.3.10 Relaxor ferroelectrics 351
11.3.11 Ferroelectric nanoparticles, thin films and superlattices 352
11.3.12 Flexoelectricity in ferroelectrics 353
Further reading 354
Problems and exercises 355
12 Magnetic solids 361
12.1 Magnetic materials 361
12.1.1 Characterisation of magnetic materials 361
12.1.2 Magnetic dipoles and magnetic flux 362
12.1.3 Atomic magnetism 363
12.1.4 Overview of magnetic materials 365
12.2 Paramagnetic materials 368
12.2.1 The magnetic moment of paramagnetic atoms and ions 368
12.2.2 High and low spin: crystal field effects 369
12.2.3 Temperature dependence of paramagnetic susceptibility 371
12.2.4 Pauli paramagnetism 373
12.3 Ferromagnetic materials 374
12.3.1 Ferromagnetism 374
12.3.2 Exchange energy 376
12.3.3 Domains 378
12.3.4 Hysteresis 380
12.3.5 Hard and soft magnetic materials 380
12.4 Antiferromagnetic materials and superexchange 381
12.5 Ferrimagnetic materials 382
12.5.1 Cubic spinel ferrites 382
12.5.2 Garnet structure ferrites 383
12.5.3 Hexagonal ferrites 383
12.5.4 Double exchange 384
12.6 Nanostructures 385
12.6.1 Small particles and data recording 385
12.6.2 Superparamagnetism and thin films 386
12.6.3 Superlattices 386
12.6.4 Photoinduced magnetism 387
12.7 Magnetic defects 389
12.7.1 Magnetic defects in semiconductors 389
12.7.2 Charge and spin states in cobaltites and manganites 390
Further reading 393
Problems and exercises 393
13 Electronic conductivity in solids 399
13.1 Metals 399
13.1.1 Metals, semiconductors and insulators 399
13.1.2 Electron drift in an electric field 401
13.1.3 Electronic conductivity 402
13.1.4 Resistivity 404
13.2 Semiconductors 405
13.2.1 Intrinsic semiconductors 405
13.2.2 Band gap measurement 407
13.2.3 Extrinsic semiconductors 408
13.2.4 Carrier concentrations in extrinsic semiconductors 409
13.2.5 Characterisation 411
13.2.6 The p-n junction diode 413
13.3 Metal-insulator transitions 416
13.3.1 Metals and insulators 416
13.3.2 Electron-electron repulsion 417
13.3.3 Modification of insulators 418
13.3.4 Transparent conducting oxides 419
13.4 Conducting polymers 420
13.5 Nanostructures and quantum confinement of electrons 423
13.5.1 Quantum wells 424
13.5.2 Quantum wires and quantum dots 425
13.6 Superconductivity 426
13.6.1 Superconductors 426
13.6.2 The effect of magnetic fields 427
13.6.3 The effect of current 428
13.6.4 The nature of superconductivity 428
13.6.5 Josephson junctions 430
13.6.6 Cuprate high-temperature superconductors 430
Further reading 438
Problems and exercises 438
14 Optical aspects of solids 445
14.1 Light 445
14.1.1 Light waves 445
14.1.2 Photons 447
14.2 Sources of light 449
14.2.1 Incandescence 449
14.2.2 Luminescence and phosphors 450
14.2.3 Light-emitting diodes (LEDs) 453
14.2.4 Solid-state lasers 454
14.3 Colour and appearance 460
14.3.1 Luminous solids 460
14.3.2 Non-luminous solids 460
14.3.3 Attenuation 461
14.4 Refraction and dispersion 462
14.4.1 Refraction 462
14.4.2 Refractive index and structure 464
14.4.3 The refractive index of metals and semiconductors 465
14.4.4 Dispersion 465
14.5 Reflection 466
14.5.1 Reflection from a surface 466
14.5.2 Reflection from a single thin film 467
14.5.3 The reflectivity of a single thin film in air 469
14.5.4 The colour of a single thin film in air 469
14.5.5 The colour of a single thin film on a substrate 470
14.5.6 Low-reflectivity (antireflection) and high-reflectivity coatings 471
14.5.7 Multiple thin films and dielectric mirrors 471
14.6 Scattering 472
14.6.1 Rayleigh scattering 472
14.6.2 Mie scattering 475
14.7 Diffraction 475
14.7.1 Diffraction by an aperture 475
14.7.2 Diffraction gratings 476
14.7.3 Diffraction from crystal-like structures 477
14.7.4 Photonic crystals 478
14.8 Fibre optics 479
14.8.1 Optical communications 479
14.8.2 Attenuation in glass fibres 479
14.8.3 Dispersion and optical fibre design 480
14.8.4 Optical amplification 482
14.9 Energy conversion 483
14.9.1 Photoconductivity and photovoltaic solar cells 483
14.9.2 Dye sensitized solar cells 485
14.10 Nanostructures 486
14.10.1 The optical properties of quantum wells 486
14.10.2 The optical properties of nanoparticles 487
Further reading 489
Problems and exercises 489
15 Thermal properties 495
15.1 Heat capacity 495
15.1.1 The heat capacity of a solid 495
15.1.2 Classical theory of heat capacity 496
15.1.3 Quantum theory of heat capacity 496
15.1.4 Heat capacity at phase transitions 497
15.2 Thermal conductivity 498
15.2.1 Heat transfer 498
15.2.2 Thermal conductivity of solids 498
15.2.3 Thermal conductivity and microstructure 500
15.3 Expansion and contraction 501
15.3.1 Thermal expansion 501
15.3.2 Thermal expansion and interatomic potentials 502
15.3.3 Thermal contraction 503
15.3.4 Zero thermal contraction materials 505
15.4 Thermoelectric effects 506
15.4.1 Thermoelectric coefficients 506
15.4.2 Thermoelectric effects and charge carriers 508
15.4.3 The Seebeck coefficient of solids containing point defect populations 509
15.4.4 Thermocouples, power generation and refrigeration 509
15.5 The magnetocaloric effect 512
15.5.1 The magnetocaloric effect and adiabatic cooling 512
15.5.2 The giant magnetocaloric effect 513
Further reading 514
Problems and exercises 514
PART 5 NUCLEAR PROPERTIES OF SOLIDS 517
16 Radioactivity and nuclear reactions 519
16.1 Radioactivity 519
16.1.1 Naturally occurring radioactive elements 519
16.1.2 Isotopes and nuclides 520
16.1.3 Nuclear equations 520
16.1.4 Radioactive series 521
16.1.5 Nuclear stability 523
16.2 Artificial radioactive atoms 524
16.2.1 Transuranic elements 524
16.2.2 Artificial radioactivity in light elements 527
16.3 Nuclear decay 527
16.3.1 The rate of nuclear decay 527
16.3.2 Radioactive dating 529
16.4 Nuclear energy 531
16.4.1 The binding energy of nuclides 531
16.4.2 Nuclear fission 532
16.4.3 Thermal reactors for power generation 533
16.4.4 Fuel for space exploration 535
16.4.5 Fast breeder reactors 535
16.4.6 Fusion 535
16.4.7 Solar cycles 536
16.5 Nuclear waste 536
16.5.1 Nuclear accidents 537
16.5.2 The storage of nuclear waste 537
Further reading 538
Problems and exercises 539
Subject Index 543
