Solid State Chemistry and its Applications (eBook)

Anthony R. West (Autor)

eBook Download: EPUB

2022 | 2. Auflage
1908 Seiten
John Wiley & Sons (Verlag)
978-1-118-69557-9 (ISBN)

Infos

SOLID STATE CHEMISTRY AND ITS APPLICATIONS

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.

ANTHONY R. WEST

Department of Materials Science and Engineering, University of Sheffield, UK

Inhalt

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

2 Crystal Defects, Non-stoichiometry and Solid Solutions 119

3 Bonding in Solids 161

4 Synthesis, Processing and Fabrication Methods 221

5 Crystallography and Diffraction Techniques 265

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

7 Phase Diagrams and Their Interpretation 381

8 Electrical Properties 469

9 Magnetic Properties 563

10 Optical Properties: Luminescence, Lasers and Transparent Conductors 589

11 Heterogeneous Materials, Electroceramics and Impedance Spectroscopy 619

12 Thermal and Thermoelectric Properties 647

13 Functional Materials: Some Important Examples 663

14 Glass 697

15 Structural Materials: Cement, Refractories and Structural Ceramics 743

16 Oxides of the Elements, Their Properties and Uses 771

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

Textauszug

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, α‐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 β‐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, γ‐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...

Produkt-Details

• Erscheint lt. Verlag: 6.4.2022
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Technik ► Maschinenbau
• Schlagworte: Amorphous solids • ch1700 • ch2404 • ch2406 • ch2410 • Chemie • Chemistry • defect equilibria • Electroceramics • Festkörperchemie • glass chemistry • inorganic chemistry applications • inorganic chemistry textbook • Materialeigenschaften • Materials Science • Materialwissenschaften • ph1900 • Point groups • properties of materials • solid state chemistry • solid state chemistry applications • solid thermodynamics
• ISBN-10: 1-118-69557-7 / 1118695577
• ISBN-13: 978-1-118-69557-9 / 9781118695579