Solid State Chemistry and its Applications
Description
A comprehensive treatment of solid state chemistry complete with supplementary material and full colour illustrations from a leading expert in the field.
Solid State Chemistry and its Applications, Second Edition delivers an advanced version of West's classic text in solid state chemistry, expanding on the undergraduate Student Edition to present a comprehensive treatment of solid state chemistry suitable for advanced students and researchers. The book provides the reader with an up-to-date account of essential topics in solid state chemistry and recent developments in this rapidly developing field of inorganic chemistry.
Significant updates and new content in this second edition include:
* A more extensive overview of important families of inorganic solids including spinels, perovskites, pyrochlores, garnets, Ruddlesden-Popper phases and many more
* New methods to synthesise inorganic solids, including sol-gel methods, combustion synthesis, atomic layer deposition, spray pyrolysis and microwave techniques
* Advances in electron microscopy, X-ray and electron spectroscopies
* New developments in electrical properties of materials, including high Tc superconductivity, lithium batteries, solid oxide fuel cells and smart windows
* Recent developments in optical properties, including fibre optics, solar cells and transparent conducting oxides
* Advances in magnetic properties including magnetoresistance and multiferroic materials
* Homogeneous and heterogeneous ceramics, characterization using impedance spectroscopy
* Thermoelectric materials, MXenes, low dimensional structures, memristors and many other functional materials
* Expanded coverage of glass, including metallic and fluoride glasses, cement and concrete, geopolymers, refractories and structural ceramics
* Overview of binary oxides of all the elements, their structures, properties and applications
Featuring full color illustrations throughout, readers will also benefit from online supplementary materials including access to CrystalMaker¯® software and over 100 interactive crystal structure models.
Perfect for advanced students seeking a detailed treatment of solid state chemistry, this new edition of Solid State Chemistry and its Applications will also earn a place as a desk reference in the libraries of experienced researchers in chemistry, crystallography, physics, and materials science.
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ANTHONY R. WEST, Department of Materials Science and Engineering, University of Sheffield, UK.
Content
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
Solid State Chemistry, an Overview of the Discipline: Chemistry - Solid State Chemistry - Materials Chemistry - Materials Science and Engineering
Chemistry is an evolving subject! Traditionally, there have been three branches of chemistry: organic, physical and inorganic, with some arguments in favour of including analytical as a fourth branch. An alternative, fairly new classification (favoured by the author!) divides chemistry into two broad areas: molecular (which includes liquids and gases) and non-molecular (or solid state). The ways in which we think about, make, analyse and use molecular and non-molecular substances are completely different, as shown by a comparison of one 'simple' substance in each category, toluene and aluminium oxide:
Comparison of the chemistries of molecular and non-molecular materials
Characteristic Toluene Aluminium oxide Formula Fixed, C6H5CH3 Usually fixed, Al2O3, but for other oxides may be variable, e.g. Fe1-x O Are defects present? Not allowed: missing or mis-placed atoms give rise to different molecules Unavoidable: small concentration of vacancies, interstitials and dislocations are always present Doping possibilities Not possible without producing a different molecule Doping or solid solution formation allows control and optimisation of properties, e.g. ruby is Cr-doped Al2O3 Structure and its determination Molecular structure can be determined spectroscopically: NMR/Mass Spec/IR. Determine packing arrangement, bond lengths and angles, by single crystal X-ray diffraction. Usually, structural information is then complete. Full characterisation of a solid requires structural and compositional information across the length scales from local, to unit cell, nano and microscales. Many diffraction, spectroscopic and microscopic techniques are needed for full characterisation. Properties and applications Controlled by molecular formula and configuration; cannot be modified by doping. Some properties (e.g. pharmaceutical activity) may depend on molecular packing arrangements in crystals. Properties/applications depend on crystal structure, defects, dopants, surface structure, particle size and whether the material is a powder, single crystal, film, etc. Consider the diverse applications of Al2O3: films and ceramics used as insulators; powders used as abrasive; with Cr3+ dopants, ruby is used for lasers; porous solids used as catalyst supports.Thus, for toluene, once its formula and molecular structure had been determined there were few remaining issues to be resolved other than, perhaps, the detailed packing arrangement of molecules in crystalline toluene at low temperatures or the possible discovery and evaluation, even today, of as-yet unknown chemical, biological or pharmaceutical properties of pure toluene.
Alumina, by contrast, is a highly complex material; its properties, and therefore potential applications, depend on different aspects of its structure (bulk, defect, surface, nano), the methods needed to fabricate it in different forms and shapes, the possibility of doping to modify its properties and the characterisation or determination of its structure (and its composition, whether homogeneous or heterogeneous, if doped) across all length scales. This is solid state chemistry!
The biggest contrast between molecular and non-molecular materials is that the latter can be doped, allowing modification and control of properties such as magnetism, superconductivity and colour/optical band gap. By contrast, attempts to dope molecules are inevitably frustrated since replacing one atom in the molecule by another, or creating defects such as missing atoms, lead to entirely different molecules.
In recent decades, materials chemistry has emerged as a distinct branch of chemistry which covers both non-molecular, solid state materials (oxides, halides, etc.) and many molecular materials (especially, functional polymers and organic solids with potentially useful physical properties). Materials chemistry cuts across the traditional disciplines of chemistry but also includes something extra which is an interest in the physical properties of compounds and materials. In the past, solid state physics and materials science have been the usual 'home' for physical properties; but now, they are an intrinsic part of solid state and materials chemistry.
The distinction between materials chemistry and materials science is often unclear but can be summarised broadly as follows:
Materials chemistry
Synthesis - structure determination - physical properties - new materials.
Materials science
Processing and fabrication - characterisation - optimisation of properties and testing - improved/new materials for engineering applications in products or devices.
Materials science focuses on materials that are already known to be useful or have the potential to be developed for applications, either by compositional control to optimise properties or by fabrication into desired forms, shapes or products. Materials science therefore includes whatever aspects of chemistry, physics and engineering that are necessary to achieve the desired aims.
Materials chemistry is much more than just a subset of materials science, however, since it is freed from the constraint of a focus on specific applications; materials chemists love to synthesise new materials and measure their properties, some of which may turn out to be useful and contribute to the development of new industries, but they do this within an overarching interest in new chemistry, new structures and improved understanding of structure - composition - property relationships.
A curious fact is that, in the early days of chemistry, inorganic chemistry had as its main focus, the elements of the periodic table and their naturally occurring or easy-to-make compounds such as oxides and halides. Inorganic chemistry subsequently diversified to include organometallic chemistry and coordination chemistry but interestingly, many traditional inorganic materials have returned to centre-stage and are now at the heart of solid state materials science. Examples include: Cr-doped Al2O3 for lasers; doped Si semiconductors for microelectronics; doped ZrO2 as the solid electrolyte in solid oxide fuel cells; BaTiO3 as the basis of the capacitor industry with a total annual production worldwide exceeding 1012 units; copper oxide-based materials for superconductor applications; and many, many more. The scope for developing new solid state materials/applications is infinite, judging by the 'simple' example of Al2O3 described above. Most such materials tend not to suffer from problems such as volatilisation, degradation and atmospheric attack, which are often a drawback of molecular materials, and can be used safely in the environment.
It is important to recognise also that physical properties of inorganic solids often depend on structure at different length scales, as shown by the following examples:
Thus, in the case of ruby, which is a natural gemstone and was the first material in which LASER action - light amplification by stimulated emission of radiation - was demonstrated, two structural aspects are important. One is the host crystal structure of corundum, a-Al2O3 and the other is the Cr3+ dopant which substitutes at random for about 1% of the Al3+ ions in the corundum lattice: the Cr-O bond lengths and the octahedral site symmetry are controlled by the host structure; the two together combine to give the red ruby colour by means of d-d transitions within the Cr chromophore and the possibility of accessing the long-lived excited states that are necessary for LASER action.
A remarkable example of the effect of crystal structure details at the unit cell scale on properties is shown by dicalcium silicate, Ca2SiO4 which is readily prepared in two polymorphic forms at room temperature. One, the ß-polymorph, reacts with water to give a semicrystalline calcium silicate hydrate which sets rock-solid and is a main constituent of concrete; the other polymorph, ?-Ca2SiO4, does not react with water. Just think, the entire construction industry rests on the detailed polymorphism of dicalcium silicate! It is not sufficient that one of the key components of cement has the right composition, Ca2SiO4; in addition, the precise manner in which ions are packed together in the solid state is critical to its hydration properties and whether or not it turns into concrete.
At the nanoscale, crystalline particles may contain many hundreds of unit cells but often their properties are different from powders, ceramics or single crystals of the same material with larger-sized grains simply because of the influence of surface energies. In small nanoparticles, surface free energies and structures increasingly dominate the total free energy of a material, as shown by the colour, and associated band gap, of CdS nanoparticles (or colloids in older terminology) which can be fine-tuned by controlling the...
