Solid State Chemistry and its Applications

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

• Preface xxiCompanion Website xxiiiBiography xxvSolid State Chemistry, an Overview of the Discipline: Chemistry – Solid StateChemistry – Materials Chemistry – Materials Science and Engineering 11 Crystal Structures, Crystal Chemistry, Symmetry and Space Groups 71.1 Unit Cells and Crystal Systems 71.2 Symmetry 91.3 Symmetry and Choice of Unit Cell 161.4 Lattice, Bravais Lattice 181.5 Lattice Planes and Miller Indices 201.6 Indices of Directions 221.7 d-Spacing Formulae 231.8 Crystal Densities and Unit Cell Contents 231.9 Description of Crystal Structures 241.10 Close Packed Structures – Cubic and Hexagonal Close Packing 251.11 Relationship Between Cubic Close Packed and Face Centred Cubic 271.12 Hexagonal Unit Cell and Close Packing 271.13 Density of Close Packed Structures 281.14 Unit Cell Projections and Atomic Coordinates 301.15 Materials that can be Described as Close Packed 311.16 Structures Built of Space-Filling Polyhedra 391.17 Some Important Structure Types 421.18 Point Groups and Space Groups 992 Crystal Defects, Non-stoichiometry and Solid Solutions 1192.1 Perfect and Imperfect Crystals 1192.2 Types of Defect: Point Defects 1202.3 Solid Solutions of Ionic Materials 1312.4 Extended Defects 1432.5 Dislocations and Mechanical Properties of Solids 1473 Bonding in Solids 1613.1 Overview: Ionic, Covalent, Metallic, van der Waals and Hydrogen Bonding in Solids 1613.2 Ionic Bonding 1623.3 Covalent Bonding 1963.4 Metallic Bonding and Band Theory 2073.5 Bands or Bonds: A Final Comment 2204 Synthesis, Processing and Fabrication Methods 2214.1 General Observations 2214.2 Solid State Reaction or Shake ‘n Bake Methods 2214.3 Low Temperature or Chimie Douce Methods 2304.4 Gas-Phase Methods 2474.5 High-Pressure Methods 2584.6 Crystal Growth 2615 Crystallography and Diffraction Techniques 2655.1 General Comments: Molecular and Non-Molecular Solids 2655.2 Characterisation of Solids 2675.3 X-Ray Diffraction 2685.4 Electron Diffraction 3015.5 Neutron Diffraction 3025.6 The Reciprocal Lattice 3065.7 Total scattering and pair distribution function (PDF) analysis 3195.8 Line broadening of XRD powder patterns, domain (particle) size measurement and strain effects 3226 Other Characterisation Techniques: Microscopy, Spectroscopy, Thermal Analysis 3256.1 Diffraction and Microscopic Techniques: What Do They Have in Common? 3256.2 Optical and Electron Microscopy Techniques 3266.3 Spectroscopic Techniques 3456.4 Thermal Analysis (TA) 3706.5 Strategy to Identify, Analyse and Characterise ‘Unknown’ Solids 3767 Phase Diagrams and Their Interpretation 3817.1 The Phase Rule, the Condensed Phase Rule and Some Definitions 3817.2 One-Component Systems 3867.3 Two-Component Condensed Systems 3897.4 Some Tips and Guidelines for Constructing Binary Phase Diagrams 4117.5 Ternary Systems 4137.6 Phase Transitions 4398 Electrical Properties 4698.1 Survey of Electrical Properties and Electrical Materials 4698.2 Metallic Conductivity 4718.3 Superconductivity 4768.4 Semi conductivity 4928.5 Ionic Conductivity 5028.6 Dielectric Materials 5478.7 Ferroelectrics 5538.8 Pyroelectrics 5588.9 Piezoelectric 5588.10 Applications of Ferro-, Pyro- and Piezoelectric 5599 Magnetic Properties 5639.1 Physical Properties 5639.2 Magnetic Materials, their Structures and Properties 5729.3 Applications: Structure–Property Relations 5829.4 Recent Developments 58610 Optical Properties: Luminescence, Lasers and Transparent Conductors 58910.1 Visible Light and the Electromagnetic Spectrum 58910.2 Sources of Light, Thermal Sources, Black Body Radiation and Electronic Transitions 58910.3 Scattering Processes: Reflection, Diffraction and Interference 59210.4 Luminescence and Phosphors 59210.5 Configurational Coordinate Model 59410.6 Some Phosphor Materials 59610.7 Anti-Stokes Phosphors 59710.8 Stimulated Emission, Amplification of Light and Lasers 59810.9 Photodetectors 60410.10 Fibre-Optics 60610.11 Solar Cells and Photovoltaics 60710.12 Transparent Conducting Oxides, TCOs, Smart Windows and Energy Management of Buildings 61010.13 Photonic Crystals, Photonic Bandgaps and Opals 61611 Heterogeneous Materials, Electro ceramics and Impedance Spectroscopy 61911.1 Homogeneous and Heterogeneous Solids 61911.2 Resistivities and Permittivities of Materials; The Parallel RC Element 62111.3 Impedance Formalisms, Alternating Currents and Equivalent Circuits 62411.4 Applications of Impedance Spectroscopy 63412 Thermal and Thermoelectric Properties 64712.1 Thermoelectric Effects 64712.2 Thermal Properties: Heat Capacity, Thermal Conductivity, Thermal Expansion 65613 Functional Materials: Some Important Examples 66313.1 TiO2: Rutile, Anatase and Other Ti–O Phases 66313.2 Ca12Al14O33, Mayenite: An Oxide Ion Conductor, Component of Cement and a uperconducting Electride 68013.4 Two-dimensional Structures: MXenes 68913.5 Low-dimensional Solids: Graphene, BN, Transition Metal Dichalcogenides and Black Phosphorus 69214 Glass 69714.1 Factors That Influence Glass Formation 69814.2 Thermodynamics of Glass Formation; the Behaviour of Liquids on Cooling 70014.3 Kinetics of Crystallisation and Glass Formation 70314.4 Structure of Glasses 70614.5 Liquid Immiscibility and Phase Separation in Glasses 71014.6 Viscosity of Glasses and Melts 71514.7 Electrical (Ionic) Conductivity of Glass and the Mixed Alkali Effect 71814.8 Bonds, Bands and Semiconducting Glasses 72114.9 Mechanical Properties and Strengthening of Glass 72714.10 Commercial Silicate and Borate Glasses 72814.11 Metallic Glasses 73014.12 Fluoride Glasses 73314.13 Glass-Ceramics 73614.14 Bioglasses 74015 Structural Materials: Cement, Refractories and Structural Ceramics 74315.1 Cements 74315.2 Refractories and Structural Ceramics 76116 Oxides of the Elements, Their Properties and Uses 77116.1 Oxides of s-Block Elements 77116.2 Acid-Base Classification of Oxides 77316.3 Oxides of p-Block Elements 77316.4 Oxides of d-block (Transition) Elements 77416.5 Oxides of Lanthanides and Actinides 77616.6 Oxides of the Elements Overview 776Appendix A: Interplanar Spacings and Unit Cell Volumes 795Appendix B: Model Building 797Appendix C: Geometrical Considerations in Crystal Chemistry 801Appendix D: The Elements and Some of Their Properties 805Appendix E: The 32 Crystallographic Point Groups 811Appendix F: The Arrhenius Equation for Ionic Conductivity 815Appendix G: A Guide to the Use of Electrode Potentials 819Further Reading 823Questions 837Index 851