Table of Contents

Preface xxi

Companion Website xxiii

Biography xxv

Solid State Chemistry, an Overview of the Discipline: Chemistry – Solid State

Chemistry – Materials Chemistry – Materials Science and Engineering 1

1 Crystal Structures, Crystal Chemistry, Symmetry and Space Groups 7

1.1 Unit Cells and Crystal Systems 7

1.2 Symmetry 9

1.3 Symmetry and Choice of Unit Cell 16

1.4 Lattice, Bravais Lattice 18

1.5 Lattice Planes and Miller Indices 20

1.6 Indices of Directions 22

1.7 d-Spacing Formulae 23

1.8 Crystal Densities and Unit Cell Contents 23

1.9 Description of Crystal Structures 24

1.10 Close Packed Structures – Cubic and Hexagonal Close Packing 25

1.11 Relationship Between Cubic Close Packed and Face Centred Cubic 27

1.12 Hexagonal Unit Cell and Close Packing 27

1.13 Density of Close Packed Structures 28

1.14 Unit Cell Projections and Atomic Coordinates 30

1.15 Materials that can be Described as Close Packed 31

1.16 Structures Built of Space-Filling Polyhedra 39

1.17 Some Important Structure Types 42

1.18 Point Groups and Space Groups 99

2 Crystal Defects, Non-stoichiometry and Solid Solutions 119

2.1 Perfect and Imperfect Crystals 119

2.2 Types of Defect: Point Defects 120

2.3 Solid Solutions of Ionic Materials 131

2.4 Extended Defects 143

2.5 Dislocations and Mechanical Properties of Solids 147

3 Bonding in Solids 161

3.1 Overview: Ionic, Covalent, Metallic, van der Waals and Hydrogen Bonding in Solids 161

3.2 Ionic Bonding 162

3.3 Covalent Bonding 196

3.4 Metallic Bonding and Band Theory 207

3.5 Bands or Bonds: A Final Comment 220

4 Synthesis, Processing and Fabrication Methods 221

4.1 General Observations 221

4.2 Solid State Reaction or Shake ‘n Bake Methods 221

4.3 Low Temperature or Chimie Douce Methods 230

4.4 Gas-Phase Methods 247

4.5 High-Pressure Methods 258

4.6 Crystal Growth 261

5 Crystallography and Diffraction Techniques 265

5.1 General Comments: Molecular and Non-Molecular Solids 265

5.2 Characterisation of Solids 267

5.3 X-Ray Diffraction 268

5.4 Electron Diffraction 301

5.5 Neutron Diffraction 302

5.6 The Reciprocal Lattice 306

5.7 Total scattering and pair distribution function (PDF) analysis 319

5.8 Line broadening of XRD powder patterns, domain (particle) size measurement and strain effects 322

6 Other Characterisation Techniques: Microscopy, Spectroscopy, Thermal Analysis 325

6.1 Diffraction and Microscopic Techniques: What Do They Have in Common? 325

6.2 Optical and Electron Microscopy Techniques 326

6.3 Spectroscopic Techniques 345

6.4 Thermal Analysis (TA) 370

6.5 Strategy to Identify, Analyse and Characterise ‘Unknown’ Solids 376

7 Phase Diagrams and Their Interpretation 381

7.1 The Phase Rule, the Condensed Phase Rule and Some Definitions 381

7.2 One-Component Systems 386

7.3 Two-Component Condensed Systems 389

7.4 Some Tips and Guidelines for Constructing Binary Phase Diagrams 411

7.5 Ternary Systems 413

7.6 Phase Transitions 439

8 Electrical Properties 469

8.1 Survey of Electrical Properties and Electrical Materials 469

8.2 Metallic Conductivity 471

8.3 Superconductivity 476

8.4 Semi conductivity 492

8.5 Ionic Conductivity 502

8.6 Dielectric Materials 547

8.7 Ferroelectrics 553

8.8 Pyroelectrics 558

8.9 Piezoelectric 558

8.10 Applications of Ferro-, Pyro- and Piezoelectric 559

9 Magnetic Properties 563

9.1 Physical Properties 563

9.2 Magnetic Materials, their Structures and Properties 572

9.3 Applications: Structure–Property Relations 582

9.4 Recent Developments 586

10 Optical Properties: Luminescence, Lasers and Transparent Conductors 589

10.1 Visible Light and the Electromagnetic Spectrum 589

10.2 Sources of Light, Thermal Sources, Black Body Radiation and Electronic Transitions 589

10.3 Scattering Processes: Reflection, Diffraction and Interference 592

10.4 Luminescence and Phosphors 592

10.5 Configurational Coordinate Model 594

10.6 Some Phosphor Materials 596

10.7 Anti-Stokes Phosphors 597

10.8 Stimulated Emission, Amplification of Light and Lasers 598

10.9 Photodetectors 604

10.10 Fibre-Optics 606

10.11 Solar Cells and Photovoltaics 607

10.12 Transparent Conducting Oxides, TCOs, Smart Windows and Energy Management of Buildings 610

10.13 Photonic Crystals, Photonic Bandgaps and Opals 616

11 Heterogeneous Materials, Electro ceramics and Impedance Spectroscopy 619

11.1 Homogeneous and Heterogeneous Solids 619

11.2 Resistivities and Permittivities of Materials; The Parallel RC Element 621

11.3 Impedance Formalisms, Alternating Currents and Equivalent Circuits 624

11.4 Applications of Impedance Spectroscopy 634

12 Thermal and Thermoelectric Properties 647

12.1 Thermoelectric Effects 647

12.2 Thermal Properties: Heat Capacity, Thermal Conductivity, Thermal Expansion 656

13 Functional Materials: Some Important Examples 663

13.1 TiO2: Rutile, Anatase and Other Ti–O Phases 663

13.2 Ca12Al14O33, Mayenite: An Oxide Ion Conductor, Component of Cement and a uperconducting Electride 680

13.4 Two-dimensional Structures: MXenes 689

13.5 Low-dimensional Solids: Graphene, BN, Transition Metal Dichalcogenides and Black Phosphorus 692

14 Glass 697

14.1 Factors That Influence Glass Formation 698

14.2 Thermodynamics of Glass Formation; the Behaviour of Liquids on Cooling 700

14.3 Kinetics of Crystallisation and Glass Formation 703

14.4 Structure of Glasses 706

14.5 Liquid Immiscibility and Phase Separation in Glasses 710

14.6 Viscosity of Glasses and Melts 715

14.7 Electrical (Ionic) Conductivity of Glass and the Mixed Alkali Effect 718

14.8 Bonds, Bands and Semiconducting Glasses 721

14.9 Mechanical Properties and Strengthening of Glass 727

14.10 Commercial Silicate and Borate Glasses 728

14.11 Metallic Glasses 730

14.12 Fluoride Glasses 733

14.13 Glass-Ceramics 736

14.14 Bioglasses 740

15 Structural Materials: Cement, Refractories and Structural Ceramics 743

15.1 Cements 743

15.2 Refractories and Structural Ceramics 761

16 Oxides of the Elements, Their Properties and Uses 771

16.1 Oxides of s-Block Elements 771

16.2 Acid-Base Classification of Oxides 773

16.3 Oxides of p-Block Elements 773

16.4 Oxides of d-block (Transition) Elements 774

16.5 Oxides of Lanthanides and Actinides 776

16.6 Oxides of the Elements Overview 776

Appendix A: Interplanar Spacings and Unit Cell Volumes 795

Appendix B: Model Building 797

Appendix C: Geometrical Considerations in Crystal Chemistry 801

Appendix D: The Elements and Some of Their Properties 805

Appendix E: The 32 Crystallographic Point Groups 811

Appendix F: The Arrhenius Equation for Ionic Conductivity 815

Appendix G: A Guide to the Use of Electrode Potentials 819

Further Reading 823

Questions 837

Index 851

About the Author

ANTHONY R. WEST, Department of Materials Science and Engineering, University of Sheffield, UK.