Solid State Chemistry and its Applications. Anthony R. West

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Solid State Chemistry and its Applications - Anthony R. West

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is a Fellow of the Royal Society of Chemistry, the Institute of Physics, the Institute of Materials, Minerals and Mining (IOM3), and the Royal Society of Edinburgh. Over the years he has received several awards, including an Industrial Award in Solid State Chemistry from the RSC (1996), the Griffiths Medal and Prize from the IOM3 (2008), the Epsilon de Oro Award from the Spanish Society of Glass and Ceramics (2007) and the Chemical Record Lectureship from the Chemical Societies of Japan (2007). He has been awarded the 2013 John B. Goodenough Award in Materials Chemistry by the RSC, a lifetime award which recognises exceptional and sustained contributions to the field of materials chemistry.

      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.
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.

      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,

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