Читать книгу Solid State Chemistry and its Applications - Anthony R. West - Страница 4

1 Chapter 1Figure 1.1 (a) Section through the NaCl structure, showing (b–e) possible re...Figure 1.2 Cubic unit cell of NaCl, a = b = c. Figure 1.3 (a) The seven crystal systems and their unit cell shapes; (b) fiv...Figure 1.4 (a) Threefold and (b) twofold rotation axes; (c) the impossibilit...Figure 1.5 Two‐dimensional Penrose tiling constructed by packing together tw...Figure 1.6 Hypothetical twinned structure showing fivefold symmetry. Figure 1.7 Symmetry elements: (a) mirror plane; (b) centre of symmetry; (c) ...Figure 1.8 Arrangement of coins with heads (H) and tails (T) illustrating (a...Figure 1.9 (a) Two‐, three‐ and fourfold axes and (b, c) mirror planes of a ...Figure 1.10 (a) Tetragonal unit cell of CaC2: note the cigar‐shaped carbide ...Figure 1.11 Representation of (a) the NaCl structure in two dimensions by (b...Figure 1.12 The unit cells of the 14 Bravais lattices: axes refer to the ab ...Figure 1.13 (a) Lattice planes (in projection); (b) derivation of Miller ind...Figure 1.14 Miller indices for a hexagonal lattice. Figure 1.15 Examples of Miller indices: (a) (101); (b) (100); (c) (200); (d)...Figure 1.16 (a) A cp layer of equal‐sized spheres; (b) a non‐cp layer with c...Figure 1.17 Two cp layers arranged in A and B positions. The B layer occupie...Figure 1.18 Three close packed layers in ccp sequence. Figure 1.19 Coordination number 12 of shaded sphere in (a) hcp and (b) ccp s...Figure 1.20 Face centred cubic, fcc, unit cell of a ccp arrangement of spher...Figure 1.21 (a, b) Hexagonal unit cell of an hcp arrangement of spheres show...Figure 1.22 (a) Unit cell dimensions for a face centred cubic unit cell with...Figure 1.23 Tetrahedral and octahedral sites between two cp anion layers, se...Figure 1.24 Available cation sites, 1–12, in an fcc anion array. Figure 1.25 (a, b) Tetrahedral sites T+, T– and their relation to a cube. (c...Figure 1.26 (a) hcp arrangement of Br atoms in crystalline Al2Br6; (b) Al at...Figure 1.27 (a) The C60 molecule; one pentagon surrounded by five hexagons i...Figure 1.28 Cation–cation separation in octahedra which share (a) corners an...Figure 1.29 Unit cell of (a, d) NaCl, (b, e) ZnS, sphalerite, and (c, f) Na2...Figure 1.30 Alternative view of the antifluorite structure. Figure 1.31 Unit cell of the rock salt structure showing edge‐sharing octahe...Figure 1.32 The rock salt structure as an array of edge‐sharing octahedra....Figure 1.33 The sphalerite (zinc blende) structure showing (a) the unit cell...Figure 1.34 The antifluorite structure of Na2O showing the unit cell in term...Figure 1.35 The wurtzite and nickel arsenide structures: (a–c) the hexagonal...Figure 1.36 The primitive cubic unit cell of CsCl. Figure 1.37 The rutile structure, TiO2: (a) the unit cell; (b) TiO6 octahedr...Figure 1.38 (a) Octahedral sites in an ideal hcp array; (b) edge‐sharing oct...Figure 1.39 The CdI2 structure: (a) the basal plane of the hexagonal unit ce...Figure 1.40 The CdCl2 structure. Figure 1.41 (a–d) The perovskite structure of SrTiO3. (e) A close packed Sr,...Figure 1.42 (a) Crystal structure of CaCu3Ti4O12. (b) The brownmillerite ...Figure 1.43 The structure of (a) ReO3, (b) tungsten bronze NaxWO3, (c, d) br...Figure 1.44 Representative parts of the spinel structure. (a) One octant of ...Figure 1.45 Olivine structure of LiFePO4. Figure 1.46 Crystal structures of (a) corundum, (b) ilmenite and (c, d) LiNb...Figure 1.47 Some cation‐ordered fluorites showing cation positions relative ...Figure 1.48 The pyrochlore structure, which may be regarded as a distorted, ...Figure 1.49 The garnet crystal structure. Figure 1.50 (a) The K2NiF4 structure. (b) The Bi2O2 layers that form part of...Figure 1.51 The crystal structure of MgB2 as (a) an oblique projection showi...Figure 1.52 Silicate anions with (a) bridging and (b) non‐bridging oxygens. ...Figure 1.53 The point groups (a, b) 2, (c, d) 3, and (e–h) m. Figure 1.54 The point groups (a) and (b, c) .Figure 1.55 The three orthorhombic point groups 222, mm2, and mmm. Figure 1.56 Equivalent positions in the point group 222. In step 1, a 2‐fold...Figure 1.57 Trigonal point group 32. Figure 1.58 The symmetry of the methylene dichloride molecule, CH2Cl2, point...Figure 1.59 The symmetry of the methyl chloride molecule, CH3Cl, point group...Figure 1.60 (a) The convention used to label axes and origin of space groups...Figure 1.61 Two tetrahedra in a centrosymmetric arrangement. Figure 1.62 Monoclinic space group C2 (No 5); coordinates of equivalent posi...Figure 1.63 Monoclinic space group C2/m (No 12). Coordinates of general equi...Figure 1.64 Orthorhombic space group P2221 (No 17); Coordinates of equivalen...Figure 1.65 Orthorhombic space group F222 (No 22); coordinates of equivalent...Figure 1.66 Tetragonal space group I41 (No 80); coordinates of equivalent po...Figure 1.67 The symmetry elements in space group P42/mnm.

2 Chapter 2Figure 2.1 Energy changes on introducing defects into a perfect crystal. Figure 2.2 2D representation of a Schottky defect with cation and anion vaca...Figure 2.3 (a) 2D representation of a Frenkel defect in AgCl; (b) interstiti...Figure 2.4 Fraction of Frenkel defects in AgCl as a function of temperature. Figure 2.5 The F‐centre, an electron trapped on an anion vacancy. Figure 2.6 (a) H‐centre and (b) V‐centre in NaCl. Figure 2.7 Split interstitial defect in an fcc metal. Figure 2.8 Split interstitial in a bcc metal, e.g. α‐Fe. Symbols as in Fig. ...Figure 2.9 Koch cluster postulated to exist in wüstite, Fe 1–x O. ...Figure 2.10 Interstitial defect cluster in UO2+x. Uranium positions (not sho...Figure 2.11 Ordered, primitive cubic unit cell of β′‐brass, CuZn....Figure 2.12 Interstitial sites for carbon in (a) α‐Fe and (b) γ‐Fe....Figure 2.13 Solid solution mechanisms involving substitution of aliovalent c...Figure 2.14 Density data for cubic CaO‐stabilised zirconia solid solutions f...Figure 2.15 Density data for solid solutions of YF3 in CaF2. Figure 2.16 Effect of dopants on the ferroelectric Curie temperature of BaTi...Figure 2.17 Formation of CS planes in WO3 and related structures. Each cross...Figure 2.18 Domain texture in a single crystal. Figure 2.19 Antiphase domains and boundaries in an ordered crystal AB: A, op...Figure 2.20 Edge dislocation in projection. Figure 2.21 Migration of an edge dislocation under the action of a shearing ...Figure 2.22 Screw dislocation. Figure 2.23 A quarter dislocation loop. Figure 2.24 Generation and motion of a dislocation loop. Figure 2.25 Locking of an edge dislocation at an impurity atom. Figure 2.26 Burgers vector in (a), (b) cp and (c), (d) non‐cp directions....Figure 2.27 Slip occurs more easily if the slip plane is a cp plane, as in (...Figure 2.28 (a) Tensile stress–strain curve for single‐crystal Mg; (b, c) te...Figure 2.29 Climb of an edge dislocation by vacancy migration. Figure 2.30 (a) An edge dislocation and (b) a partial dislocation in an fcc ...Figure 2.31 Collapse of the structure around a cluster of vacancies, thereby...Figure 2.32 Array of edge dislocations at a low angle grain boundary.

3 Chapter 3Figure 3.1 Electron density contour map of LiF (rock salt structure): a sect...Figure 3.2 Variation of electron density along the line connecting adjacent ...Figure 3.3 Ionic radii as a function of coordination number for cations M+ t...Figure 3.4 Radius ratio calculation for octahedral coordination. Figure 3.5 Lattice energy (dashed line) of ionic crystals as a function of i...Figure 3.6 Variation of Pauling electronegativities with position in the Per...Figure 3.7 Mooser–Pearson plot for AB compounds containing A group cations. ...Figure 3.8 Bond valence–bond length universal correlation curve for bonds be...Figure 3.9 Splitting of d energy levels in (a) an octahedral and (b) a tetra...Figure 3.10 Radii in octahedral coordination of (a) divalent and (b) trivale...Figure 3.11 Lattice energies of transition metal difluorides determined from...Figure 3.12 Energy level diagram for the d levels in a d 9 ion experiencing ...Figure 3.13 Orientation of d orbitals in a tetrahedral field. Figure 3.14 The structure of red PbO, showing the presence of the inert pair...Figure 3.15 Plot of ψ and 4πr2ψ2 for 1s, 2s and 3s orbitals of a hydrogen at...Figure 3.16 The three p and five d orbitals. Note the axes for labelling eac...Figure 3.17 Bonding σ s and antibonding MOs on H2, and their relative ...Figure 3.18 Overlap of 2p orbitals to give (a) σ p bonding orbital, (b) Figure 3.19 Energy level diagram for MOs on (a) the F2 molecule formed from ...Figure 3.20 The mixing of (a) σ p and σ s MOs and (b) and MO...Figure 3.21 Energy level diagram for N2 showing the four hybrid σ MOs, σ1, σ...Figure 3.22 Energy level diagram for the HF molecule. Figure 3.23 Shapes of the (a) NH3 and (b) H2O molecules. Figure 3.24 Valence bond descriptions of some inorganic compounds and struct...Figure 3.25 Band structure of (a) and (b) metals, (c) semimetals, (d) semico...Figure 3.26 Effect of interatomic spacing on atomic energy levels and bands ...Figure 3.27 (a) Free electron theory of a metal; electrons in a potential we...Figure 3.28 Density of states versus energy. Figure 3.29 Potential energy of electrons as a function of distance through ...Figure 3.30 Density of states showing a band gap in semiconductors and insul...Figure 3.31 Positive and negative charge carriers. Figure 3.32 (a) Section through the TiO structure, parallel to a unit cell f...Figure 3.33 (a) Resonating bond model proposed initially to explain the stru...Figure 3.34 (a) Electronic structure of C60 and (b) band filling in K3C60.

4 Chapter 4Figure 4.1 Idealised reaction mixture composed of grains of MgO and Al2O3. I...Figure 4.2 Nucleation of MgAl2O4 spinel on (a) MgO and (b) Al2O3. Letters A,...Figure 4.3 Fishes to birds: Escher drawing. Figure 4.4 Spinel product layer separating MgO and Al2O3 reactant grains. Figure 4.5 (a) Solution chemistry of Al showing amphoteric behaviour and eff...Figure 4.6 Reagents and esterification mechanism in the Pechini process. Figure 4.7 (a) Pressure–temperature relations for water at constant volume. ...Figure 4.8 The Bayer process for the extraction of α‐Al2O3 from bauxite, whi...Figure 4.9 SEM images of various metal oxide nanostructures. Figure 4.10 Structures of (a) graphite, in oblique projection showing the tw...Figure 4.11 Stacking of octahedral layers in LDHs showing (a) two‐layer repe...Figure 4.12 Synthesis of polymer‐intercalated LDH showing (a) in situ polyme...Figure 4.13 (a, b) Simple vapour‐phase transport experiment for the transpor...Figure 4.14 Single‐source precursor molecules for MOCVD. Figure 4.15 (a) A three‐coordinate Si atom in a‐Si; (b) the band structure s...Figure 4.16 (a) Phase diagram for carbon; (b) schematic surface of diamond f...Figure 4.17 (a) Cathode sputtering equipment and (b) vacuum evaporation equi...Figure 4.18 Deposition of TiO2 films by ALD. Figure 4.19 Ultrasonic spray pyrolysis: (a) photograph of an aerosol fountai...Figure 4.20 Fluorescence of CdSe quantum dots controlled by particle size wh...Figure 4.21 Process diagram for preparation of SnO2 gas sensors comparing we...Figure 4.22 Czochralski method for crystal growth. Figure 4.23 (a) Stockbarger method. T m = crystal melting point. (b) Bridg...

5 Chapter 5Figure 5.1 Structural features of inorganic solids across the length scales ...Figure 5.2 The electromagnetic spectrum. Figure 5.3 (a) Generation of Cu Kα X‐rays. A 1s electron is ionised; a 2p el...Figure 5.4 (a) Schematic design of a filament X‐ray tube. (b) Use of Ni to f...Figure 5.5 Schematic diagram of a synchrotron storage ring. Figure 5.6 (a) Lines on an optical grating act as secondary sources of light...Figure 5.7 Diffraction of light by an optical grating. Figure 5.8 Derivation of Bragg’s law. Figure 5.9 The X‐ray diffraction experiment. Figure 5.10 The different X‐ray diffraction techniques. Figure 5.11 The powder method. Figure 5.12 Formation of a cone of diffracted radiation. Figure 5.13 Schematic Debye–Scherrer photograph. Figure 5.14 (a) Theorem of a circle used to focus X‐rays. (b) Arrangement of...Figure 5.15 X‐ray powder diffraction patterns of (a) cristobalite and (b) gl...Figure 5.16 (a) Crystal monochromator M, source S and sample X, in a focusin...Figure 5.17 Section of the powder XRD patterns of BaTiO3 showing the cubic p...Figure 5.18 XRD patterns of some rock salt‐related phases (a) CoO, (b) LiCoO...Figure 5.19 (a) Scattering of X‐rays by electrons in an atom. (b) Form facto...Figure 5.20 (a) bcc α‐Fe; (b) (100) planes; (c) (200) planes. Figure 5.21 (a) (110) and (b) (111) planes in NaCl. Figure 5.22 (a, b) (100) planes for an orthogonal unit cell (α = β = γ = 90°...Figure 5.23 Calculated (red crosses), observed (green curves) and difference...Figure 5.24 Electron density map for NaCl. Figure 5.25 Antiferromagnetic superstructure in MnO, FeO and NiO, showing ps...Figure 5.26 Schematic neutron and powder XRD patterns for MnO for λ = 1.542 ...Figure 5.27 (a) Monoclinic unit cell in projection down b with (001) and (10...Figure 5.28 Construction of the reciprocal lattice; point Z represents the r...Figure 5.29 (a) Schematic section through the reciprocal lattice of a single...Figure 5.30 Reciprocal lattice of a body‐centred orthorhombic unit cell show...Figure 5.31 Reciprocal lattice of a face‐centred orthorhombic unit cell; lat...Figure 5.32 (a) zero layer, hk0, of a primitive hexagonal reciprocal lattice...Figure 5.33 Construction of the Ewald sphere of reflection showing (a) deriv...Figure 5.34 Formation of a schematic SAD pattern by a monochromatic electron...Figure 5.35 X‐ray powder diffraction patterns of (a) cristobalite and (b) Si...Figure 5.36 PDF results for SiO2 glass. Figure 5.37 The low‐r PDF region of the oxygen‐deficient perovskite, La0.5Ba...Figure 5.38 Broadening of X‐ray reflections due to small particle size....Figure 5.39 Part of a diffractometer trace for a mixture of MgO (small parti...

6 Chapter 6Figure 6.1 (a) Simplified ray diagram for an optical microscope. (b) Basic c...Figure 6.2 (a) The transmission of light along an optical fibre and (b) esca...Figure 6.3 Simplified ray diagram for an electron microscope showing diffrac...Figure 6.4 Working ranges of various techniques used for viewing solids. TEM...Figure 6.5 Some of the processes that occur on bombarding a sample with elec...Figure 6.6 Basic components of an electron microscope. Figure 6.7 Reflection and transmission signals in SEM and TEM modes Figure 6.8 Principle of the scanning electron microscope. Figure 6.9 Penetration and escape depths in SEM. Figure 6.10 Processes responsible for Auger electron emission. Figure 6.11 Auger spectra of (Pb0.4Sr0.6)TiO3/SiO2/Si layered structure afte...Figure 6.12 Cathodoluminescence: (a) excitation across the band gap; (b) rad...Figure 6.13 (a) Normalised CL spectra for undoped AlN and AlN doped with 0.2...Figure 6.14 High‐resolution electron micrograph of an intergrowth tungsten b...Figure 6.15 (a) TEM bright field micrograph of an ilmenite (Ilm) sample cont...Figure 6.16 Atomic resolution HAADF‐STEM image of Al72Ni20Co8 along the 10‐f...Figure 6.17 Schematic illustration of atomic resolution imaging and analysis...Figure 6.18 Principal regions of the electromagnetic spectrum and the associ...Figure 6.19 (a) Energy level transitions involved in IR and Raman spectrosco...Figure 6.20 IR spectra of (a) calcite, CaCO3, (b) NaNO3 and (c) gypsum, CaSO...Figure 6.21 Laser Raman spectra of (a) quartz and (b) cristobalite. Figure 6.22 Possible electronic transitions in a solid. These involve electr...Figure 6.23 Schematic of a typical UV/visible absorption spectrum. Figure 6.24 (a) The four mI states for a nucleus with spin I = 3/2 (i) in th...Figure 6.25 29Si NMR spectrum of xonotlite. Also shown schematically is t...Figure 6.26 Schematic 29Si NMR spectra of silicates containing different Q4 ...Figure 6.27 (a) Schematic ESR absorption peak, (b) the first derivative of t...Figure 6.28 (a) Flowsheet showing relations between various diffraction, mic...Figure 6.29 Al Kβ emission spectra of three Al‐containing materials....Figure 6.30 Variation of X‐ray absorption coefficient with wavelength for Cu...Figure 6.31 AEFS spectra of CuCl and CuCl2·2H2O. Figure 6.32 EXAFS spectrum of Cu. Figure 6.33 EXAFS‐derived partial RDFs for an amorphous Cu46Zr54 alloy: (a) ...Figure 6.34 Origins of ESCA and Auger spectra. Figure 6.35 Schematic XPS and AES spectra of Na+ in a sodium‐containing soli...Figure 6.36 Schematic XPS 2p spectra of Na2S2O3 and Na2SO4. Each peak is a d...Figure 6.37 XPS spectrum of Cr 3s, 3p electrons in KCr3O8. Figure 6.38 XPS spectra for tungsten bronzes. Figure 6.39 (a) The Mössbauer effect. The energy of the γ‐rays is modified w...Figure 6.40 Chemical shifts in Fe‐containing compounds and minerals. ...Figure 6.41 Mössbauer spectrum of KFeS2 (a) quadrupole splitting above and (...Figure 6.42 Schematic TG curve for a single‐step decomposition reaction....Figure 6.43 Decomposition of CaCO3 in different atmospheres. Figure 6.44 The DTA method. Graph (b) results from the set‐up shown in (a) a...Figure 6.45 Schematic TG and DTA curves for kaolin minerals. Curves vary dep...Figure 6.46 Some schematic reversible and irreversible changes: (a) dehydrat...Figure 6.47 Schematic DTA curves showing melting of crystals on heating and ...Figure 6.48 Use of DTA for phase diagram determination: (a) a simple binary ...Figure 6.49 Schematic, stepwise decomposition of calcium oxalate hydrate by ...

7 Chapter 7Figure 7.1 Binary join CaO–SiO2 in the ternary system Ca–Si–O. Note the meth...Figure 7.2 Schematic diagram showing stable, unstable and metastable conditi...Figure 7.3 Schematic P versus T phase diagram of a one‐component system....Figure 7.4 The system H2O. Figure 7.5 The system SiO2. Figure 7.6 Simple eutectic binary system. Figure 7.7 Principle of moments. Figure 7.8 Binary systems showing a compound AB melting congruently (a) and ...Figure 7.9 Binary system showing compound AB with (a) an upper limit of stab...Figure 7.10 Binary system with a complete range of solid solutions. Figure 7.11 The plagioclase feldspar system, anorthite–albite. Figure 7.12 Binary solid solution systems with (a) thermal minima and (b) th...Figure 7.13 Simple eutectic system showing partial solid solubility of the e...Figure 7.14 The system Mg2SiO4‐Zn2SiO4. Figure 7.15 Binary system with partial solid solution formation. Figure 7.16 Binary system with incongruently melting compound and partial so...Figure 7.17 Simple eutectic system with solid–solid phase transitions. Figure 7.18 Binary solid solution systems with polymorphic phase transitions...Figure 7.19 Binary eutectic system with polymorphic transitions and partial ...Figure 7.20 Liquid immiscibility domes in phase diagrams. Figure 7.21 MgO–SiO2 phase diagram. Figure 7.22 The Fe–C diagram. Figure 7.23 Partial diagram for lime‐rich compositions in the system CaO–SiO...Figure 7.24 Na–S phase diagram and open‐circuit cell voltage as a function o...Figure 7.25 Na2O–SiO2 phase diagram. N = Na2O, S = SiO2, N2S = Na4SiO4, NS =...Figure 7.26 Li2SiO3–SiO2 phase diagram. LS = Li2SiO3, LS2 = Li2Si2O5. The ex...Figure 7.27 Purification of Si by zone refining: impurities concentrate in t...Figure 7.28 ZrO2–Y2O3 phase diagram. M, T and C refer to the monoclinic, tet...Figure 7.29 Bi2O3–Fe2O3 phase diagram. Figure 7.30 Summary of the changes that can occur in a single‐phase material...Figure 7.31 Triangular grid or composition triangle used to represent the co...Figure 7.32 Two possible arrangements of compatibility triangles in a simple...Figure 7.33 Ternary systems containing ranges of binary solid solutions. Num...Figure 7.34 Possible doping mechanisms with charge compensation and solid so...Figure 7.35 Ternary phase diagrams to represent BaTiO3 which has lost some o...Figure 7.36 Representation of a 4‐component, quaternary phase diagram as a p...Figure 7.37 (a) Simple ternary eutectic system showing univariant curves and...Figure 7.38 Isothermal sections of Fig. 7.37(a) at temperatures T 1 and T 2. Figure 7.39 Possible melting relations in a ternary system that contains a c...Figure 7.40 The joins BC‐A in Fig. 7.39. Figure 7.41 Ternary systems containing (a) an incongruently melting binary p...Figure 7.42 (a) Congruently‐melting phase BC with a lower limit of stability...Figure 7.43 Self‐consistency between melting behaviour and subsolidus compat...Figure 7.44 Solid–liquid compatibility relations in ternary systems with a b...Figure 7.45 (a) Crystallisation pathway in a ternary system with a binary so...Figure 7.46 (a–d) Phase diagram CaO–Al2O3–SiO2 separated into parts highligh...Figure 7.47 Transformation from structure (a) to any of structures (b–d) req...Figure 7.48 Displacive phase transition between (a) rock salt and (b) CsCl s...Figure 7.49 (a) Ordered cation arrangement in tetragonal LiFeO2; a = 4.057, ...Figure 7.50 (a) Ferroelectric KH2PO4 and (b) antiferroelectric NH4H2PO4; • P...Figure 7.51 (a–f) Temperature‐dependence of thermodynamic properties of phas...Figure 7.52 Thermodynamic properties of phases involved in second‐order phas...Figure 7.53 Specific heat of crystalline quartz. Figure 7.54 Schematic free energy–temperature diagrams showing polymorphic t...Figure 7.55 Temperature dependence of the transition rates for a typical fir...Figure 7.56 Difference in free energy between polymorphs I and II at (a) T c...Figure 7.57 Change in free energy of nuclei as a function of radius. Figure 7.58 Critical size of nuclei as a function of temperature. Figure 7.59 Effect of temperature on nucleation rate, R. Figure 7.60 Arrhenius plot for the rate of transition β ↔ γ in Li2ZnSiO4....Figure 7.61 Time – temperature – transformation, TTT diagram for the transit...Figure 7.62 Topotactic mechanism for the transformation between (a) β and (b...Figure 7.63 Formation of a martensite plate within a parent austenite crysta...Figure 7.64 Monoclinic (M)–tetragonal (T) martensitic transformation in zirc...Figure 7.65 Two possible orientations for NH4 + ions in phase II of NH4Cl. ...

8 Chapter 8Figure 8.1 Resistivity of metals, which typically is constant below ~20 K an...Figure 8.2 (a) Polyethylene, (b) polyacetylene, (c) poly‐p‐phenylene and (d)...Figure 8.3 (a) Tetracyanoquinodimethane (TCNQ), (b) chloranil, (c) p‐phenyle...Figure 8.4 Electrical resistance of YBa2Cu3O7 as a function of temperature. ...Figure 8.5 (a) The Meissner effect showing repulsion of a superconductor, S‐...Figure 8.6 Crystal structures of (a) Chevrel phase, (b) ZrCuSiAs and (c) PbF...Figure 8.7 Perovskite‐related cuprate structures showing (a) octahedral, (b)...Figure 8.8 Crystal structure of (a) YBa2Cu3O7 and (b) YBa2Cu3O6. Figure 8.9 (a) Tc versus oxygen contents 7−δ for YBa2Cu3OS showing the impor...Figure 8.10 Conductivity of metals, semiconductors and insulators. Figure 8.11 Relation between electronic properties and magnitude of the band...Figure 8.12 (a) p‐Type semiconductivity in gallium‐doped silicon; (b) n‐type...Figure 8.13 Variation of effective mass, m *, with wave vector, k (d) and it...Figure 8.14 A p‐n junction. (a) Energy levels in p‐type and n‐type semicondu...Figure 8.15 Migration of cation vacancies, i.e. Na + ions, in NaCl. Figure 8.16 Schematic ionic conductivity of doped NaCl crystals. Parallel li...Figure 8.17 (a) Pathway for Na+ migration in NaCl. (b)Triangular interstice ...Figure 8.18 Ionic conductivity of ‘pure’ NaCl as a function of reciprocal te...Figure 8.19 (a) Migration of interstitial Ag+ ions by (1) direct interstitia...Figure 8.20 (a) Effect of Cd2+ on conductivity of AgCl crystals. (b) Effect ...Figure 8.21 Solid electrolytes as intermediate between normal crystalline so...Figure 8.22 Ionic conductivity of some solid electrolytes with concentrated ...Figure 8.23 Oxide layers in β‐alumina showing four‐layer spinel blocks betwe...Figure 8.24 Oxide packing in (a) β″‐ and (b) β‐alumina; structure of the β p...Figure 8.25 Conduction plane in β‐alumina; the base of the hexagonal unit ce...Figure 8.26 Conductivity of some single‐crystal β‐ and β″‐aluminas....Figure 8.27 (a) Crystal structure of NaZr2(PO4)3. (b) Hollandite. Figure 8.28 (a) Crystal structure of α‐Agl showing bcc arrangement of l− ion...Figure 8.29 (a) Conductivity of PbF2 as a function of reciprocal temperature...Figure 8.30 Conductivity data for selected oxygen ion conductors (BICUVOX = ...Figure 8.31 Ionic and electronic conductivity domains as a function of oxyge...Figure 8.32 (a) Conductivity at 100 °C of solid solutions based on Li4SiO4, ...Figure 8.33 Conductivity data for a selection of proton conductors. Figure 8.34 (a) Electrochemical cell containing a solid electrolyte. (b) The...Figure 8.35 (a) Components of a secondary lithium battery; (b) redox potenti...Figure 8.36 A thin‐film electrochromic device based on a tungsten bronze int...Figure 8.37 (a) Oxygen concentration cell with stabilised zirconia solid ele...Figure 8.38 (a) Dielectric material between the plates of a parallel plate c...Figure 8.39 Response of various electroceramic materials to a small applied ...Figure 8.40 (a) The polar water molecule, (b) reorientation of water molecul...Figure 8.41 Dipole orientation (schematic) in (a) a ferroelectric, (b) an an...Figure 8.42 (a) Dielectric constant of barium titanate ceramic. (b) Curie‐We...Figure 8.43 (a) Antiferroelectric‐ferroelectric transition in PbZrO3 as a fu...Figure 8.44 Displacement of phosphorus within a pO2(OH)2 tetrahedron giving ...Figure 8.45 Phase diagram for the PZT system. Figure 8.46 A multilayer ceramic capacitor. Figure 8.47 Positive temperature coefficient resistivity in semiconducting B...

9 Chapter 9Figure 9.1 Schematic magnetic phenomena in a 1D crystal: (a) paramagnetism; ...Figure 9.2 Variation of flux density or number of lines of force in (a) diam...Figure 9.3 Reciprocal of susceptibility versus temperature for substances th...Figure 9.4 Some properties of ferromagnetic materials: (a) saturation magnet...Figure 9.5 Antiferromagnetic coupling of spins of d electrons on Ni2+ ions t...Figure 9.6 Rectangular hysteresis loop showing coercivity, Hc, and remanence...Figure 9.7 Ferromagnetic ordering in bcc α‐Fe, fcc Ni and hcp Co. Figure 9.8 Occupied energy levels (shaded) and density of states N (E) for 3...Figure 9.9 Schematic splitting of 3d band into two sub‐bands: (a) in the abs...Figure 9.10 Magnetic structure of antiferromagnetic and ferrimagnetic spinel...Figure 9.11 Variation of magnetic moment with composition for ferrite solid ...Figure 9.12 Variation of magnetic moment at 0 K of garnets. Curve 1, calcula...Figure 9.13 Spontaneous magnetisation in dysprosium iron garnet. Figure 9.14 Packing arrangement of oxygens and Ba in the magnetoplumbite str...Figure 9.15 Primary and secondary coils wound on a transformer core. Figure 9.16 Read–write magnetic recording head. Figure 9.17 Improvements in magnetic recording densities for floppy disks, r...Figure 9.18 Giant magnetoresistance in FeCr multilayer structures: (a) antif...Figure 9.19 Dramatic decrease in resistivity of Pr0.7Ca0.3MnO3 in response t...

10 Chapter 10Figure 10.1 (a) The electromagnetic spectrum in the region of visible light;...Figure 10.2 (a) Population of energy levels by thermal activation. (b) Energ...Figure 10.3 The interaction of light with a solid. The light can be reflecte...Figure 10.4 Schematic representation of luminescence involving (a) an activa...Figure 10.5 Schematic design of a fluorescent lamp. Figure 10.6 Luminescence spectra of activated ZnS phosphors after UV irradia...Figure 10.7 Ground state potential energy diagram for a luminescent centre i...Figure 10.8 Ground and excited state PE diagrams for a luminescent centre. Figure 10.9 Non‐radiative energy transfer involved in operation of a sensiti...Figure 10.10 (a) Anti‐Stokes and (b) normal luminescence phenomena. Figure 10.11 Energy levels of the Cr3+ ion in ruby crystal and laser emissio...Figure 10.12 A four‐level laser system. Figure 10.13 Design of a ruby laser. Figure 10.14 Energy levels of the Nd 3+ ion in neodymium lasers. Figure 10.15 (a) A p–n junction showing (b) two components of a charged depl...Figure 10.16 Construction and operation of a laser diode. Figure 10.17 Operation of a junction diode in the photoconductive mode. Figure 10.18 Operation of a photomultiplier based on photoemission. Figure 10.19 Snell's law governing the angles of incidence and refraction wh...Figure 10.20 The confinement of a light beam to pass along an optical fibre ...Figure 10.21 Photovoltaic cells involving electrochemical processes that use...Figure 10.22 Crystal structure of In2O3 with the bixbyite, or C‐rare earth s...Figure 10.23 Band structure of (a) insulating, un‐doped In2O3 with no occupi...Figure 10.24 Burstein‐Moss effect showing the band gap, E g, and the optical...Figure 10.25 Variation of optical band gap energy with carrier concentration...Figure 10.26 Transparency window for two SnO2 films with different conductiv...Figure 10.27 The delafossite crystal structure of CuAlO2. It contains linear...Figure 10.28 SEM images of a Si‐infiltrated inverse opal in two orientations...

11 Chapter 11Figure 11.1 (a) A parallel RC element, (b) definitions of resistivity and pe...Figure 11.2 Admittance equations and plots for a parallel RC element. Figure 11.3 Impedance equations and plots for a parallel RC element. Figure 11.4 Equations and plots for a parallel RC element in the M* formali...Figure 11.5 Equations and plots for a parallel RC element in the ε * formali...Figure 11.6 Impedance complex plane plot of a series RC element. Figure 11.7 (a) A series combination of two parallel RC elements, (b, c) cor...Figure 11.8 A parallel RC element in series with a capacitor. Figure 11.9 (a, b) A parallel RC element containing a CPE; logarithmic spect...Figure 11.10 Brickwork model for ceramics containing grains and grain bounda...Figure 11.11 Typical impedance response for a ceramic with conductive grains...Figure 11.12 Charge spill‐over at a non‐ohmic, sample‐electrode contact, ass...Figure 11.13 Schematic, idealised impedance of an oxide ion conducting ceram...Figure 11.14 (a) the Debye circuit for dielectric processes, (b) combination...

12 Chapter 12Figure 12.1 Schematic variation in density of states distribution with tempe...Figure 12.2 (a) Formation of a pn junction and (b) associated band structure...Figure 12.3 A thermocouple measuring circuit. Figure 12.4 Thermocouple emf vs temperature. Figure 12.5 Construction of a thermopile. Figure 12.6 Thermoelectric module for both cooling and power generation. Figure 12.7 Parameters that affect thermoelectric efficiency, zT and their d...Figure 12.8 Schematic temperature dependence of heat capacity; n refers to t...Figure 12.9 Correlation between thermal expansion coefficient and (a) electr...Figure 12.10 Variation of potential energy with interatomic distance between...Figure 12.11 Temperature‐dependence of the cubic unit cell parameter of ScF3...Figure 12.12 Schematic lateral displacement of bridging anions (yellow) lead...

13 Chapter 13Figure 13.1 The phase diagram Ti–TiO2. Figure 13.2 Free energy vs grain size for rutile, anatase and brookite. Figure 13.3 (a) Calculated electronic structures of (i) anatase and (ii) rut...Figure 13.4 XPS spectra and schematic density of states of black and white T...Figure 13.5 UV–vis absorption spectra of (a) pure TiO2, (b–d) Cr implanted T...Figure 13.6 Schematic diagram of a photo‐electrochemical cell for hydrogen g...Figure 13.7 (a) Photocatalytic water splitting: the potentials for the two h...Figure 13.8 (a) Schematic photo‐degradation of organics on TiO2 under UV irr...Figure 13.9 The four fundamental two‐terminal circuit elements: resistor, ca...Figure 13.10 How memristance works, based on the first TiO2‐based device. Th...Figure 13.11 Schematic operation of an Electrochemical Metallisation, or ECM...Figure 13.12 Structure of one of the 12 framework cavities that form the uni...Figure 13.13 (a, b) Optical absorption and (c, d) electrical conductivity of...Figure 13.14 (a) Magnetic susceptibility of two single crystals of C12A7 ele...Figure 13.15 Typical V/I response of a ZnO varistor ceramic showing three re...Figure 13.16 Schematic model of a double Schottky barrier showing (a) trap s...Figure 13.17 Crystal structures of (a) M3AX2 (b) M′2M″AX2 and (c) (M′2/3M″1/...Figure 13.18 Layer structure of hexagonal BN. Figure 13.19 Crystal structure of layered MoS2.

14 Chapter 14Figure 14.1 Glass‐forming oxides of p‐ block elements in the periodic table....Figure 14.2 Volume–temperature characteristics for crystals, liquid, underco...Figure 14.3 Heat capacity and entropy as a function of temperature for cryst...Figure 14.4 Estimation of ideal glass transition temperature, T 0. Figure 14.5 (a) Dependence of rate of crystallisation of an undercooled liqu...Figure 14.6 (a) A schematic 2D representation of sodium silicate glass struc...Figure 14.7 (a) Free energy–composition curves and (b) phase diagram for a s...Figure 14.8 Viscosity of B2O3 above the glass transition temperature; dashed...Figure 14.9 Rapidly‐cooled drops, or Prince Rupert Drops, of molten glass....Figure 14.10 (a) Schematic energy wells and barriers to conduction in a glas...Figure 14.11 (a) Viscosity of molten S as a function of temperature. (b) ...Figure 14.12 2D representation of the structure of (a) crystalline Ge and (b...Figure 14.13 Stages in photocopying. (a) Charging. (b) Exposure. (c) Dischar...Figure 14.14 Metastable liquid immiscibility dome in the system sodium tetra...Figure 14.15 (a) Schematic roller quenching method, (b) the Be‐Zr phase diag...Figure 14.16 Magnetisation curves for Fe75P15C10 (a, b) and Co78P22 (c, d). ...Figure 14.17 (a) single mode fluoride glass fibre; the core diameter is simi...Figure 14.18 Rates of homogeneous nucleation and growth in a viscous liquid. Figure 14.19 Two‐stage heating process used in the production of glass‐ceram...Figure 14.20 Three methods for bioglass production.

15 Chapter 15Figure 15.1 Stages in the manufacture and use of Portland cement. Figure 15.2 Subsolidus equilibria in the system CaO–Al2O3–SiO2. Typical comp...Figure 15.3 Melting relations in the lime‐rich corner of the system CaO–Al2O...Figure 15.4 Subsolidus phase diagram for the system CaO–Al2O3–Fe2O3. Composi...Figure 15.5 Schematic free energy relations for the polymorphism of C2S. Figure 15.6 Crystal structure of (a) Ca3Al2O6. (b) Tobermorite. (c) a...Figure 15.7 Development of compressive strengths on hydration. Figure 15.8 (a) Schematic free energy diagram for the C3S composition; polym...Figure 15.9 Schematic sequence of reactions involved in alkali activation of...Figure 15.10 Phase diagram for the system CaO–Al2O3. Figure 15.11 Progressive stages of sintering, starting from (a) a loosely co...Figure 15.12 The dihedral angle and its effect on the amount of grain‐to‐gra...Figure 15.13 Phase diagrams of the systems: (a) Al2O3–SiO2, (b) Fe3O4–SiO2, ...

16 Appendix BFigure B.1 To show the relation between ccp and the fcc unit cell. Figure B.2 The cp layers in a ccp structure. Figure B.3 Templates for making tetrahedra and octahedra. Figure B.4 Some polyhedral linkages.

17 Appendix CFigure C.1 Relation of a tetrahedron to a cube. Figure C.2 Relation of an octahedron to a cube. Figure C.3 Hexagonal unit cell; c/a = 1.633.

18 Appendix EFigure E.1 The 32 crystallographic point groups.

19 Appendix FFigure F.1 Potential energy barriers to ionic motion in a crystalline solid,...

20 QuestionsFigure Q1 Phase diagram for the MgAl2O4–Al2O 3 system.