Solid-State Chemistry

This book invites you on a tour through the most relevant topics of solid-state chemistry. It provides an up-to-date overview about fascinating structures of inorganic matter and new research developments. The reader will also gain crucial insights into many aspects of material science, from ceramics to superconductors. One chapter is specifically dedicated to the most rapidly evolving field of material science: metal-organic frameworks (MOFs). The book contains a chapter which is often neglected in others due to its complexity, the intermetallic phases. A concise but very didactic introduction to crystallographic specifications ensures that the reader will gain a deeper understanding of the crystal structures presented in the book. The book places special emphasis on the graphical illustrations which were specifically designed to promote real insights into the structural features. Instead of having to decipher hard to distinguish graphics the reader has an eye-opening experience. A further added value is that many references to the original research publications are given which enables easy follow-up for more detailed study. * Crystal structure and symmetry, space groups * Metallic and Intermetallic Compounds, Ceramics Metal-organic frameworks Cover Half Title Also of interest Solid-State Chemistry Copyright Preface Contents 1. Introduction 2. Categorizing and description of crystal structures 2.1 Symmetry 2.2 Sphere (and rod) packings 2.3 Coordination polygons/polyhedra and the five Pauling rules 2.3.1 The five Pauling rules 2.3.2 Effective coordination numbers, linking coordination polyhedra, and Niggli notation 2.4 Prototypical compounds – structure types 2.5 Networks (nets) 3. Symmetry of crystals 3.1 The concept of the unit cell 3.1.1 The metric and the stoichiometry 3.1.2 Lattice points and motifs/bases 3.1.3 The seven crystal systems 3.2 The 14 Bravais lattices – centring of unit cells 3.3 Crystallographic point groups (crystal classes) – the morphology of crystals 3.3.1 Point symmetry elements 3.3.2 The 32 crystal classes 3.4 Further (micro-) translations – glide planes and screw axes 3.4.1 Glide planes 3.4.2 Screw axes 3.5 The 230 space groups 3.5.1 Nomenclature of space groups 3.5.2 Deriving point groups from space groups 3.5.3 International tables for crystallography 4. Densest sphere packings 4.1 The hexagonal closest packing 4.2 The cubic closest packing 4.3 Voids in the hcp and ccp packing 4.4 Locations of interstitial sites along the packing direction 4.5 Stacking variants/polytypes 5. Some important structure types 5.1 Metal structures – sphere packings in action 5.1.1 Cu (ccp or fcc) (Strukturbericht type A1) 5.1.2 Mg (hcp) (Strukturbericht type A3) 5.1.3 Lanthanoids and actinoids – stacking variants 5.1.4 W (bcc) (Strukturbericht type A2) 5.1.5 α-Polonium 5.1.6 Special metal structures 5.2 (Ionic) compounds based on densest sphere packings 5.3 Compounds based on a cubic closest packing 5.3.1 NaCl (Strukturbericht type B1) 5.3.2 CdCl2 (Strukturbericht type C19) 5.3.3 CrCl3, AlCl3, and RhBr3 5.3.4 CaF2 (Strukturbericht type C1) 5.3.5 MgAl2O4 (spinel) (Strukturbericht type H11) 5.3.6 CaTiO3 (perovskite, Strukturbericht type E21) 5.4 Compounds based on a hexagonal closest packing 5.4.1 NiAs (Strukturbericht type B8) 5.4.2 CdI2 (Strukturbericht type C6) 5.4.3 β-V2N (Strukturbericht type L’32) 5.4.4 CaCl2 (Strukturbericht type C35), TiO2 (rutile) (Strukturbericht type C4), and FeS2 (marcasite) (Strukturbericht type C18) 5.4.5 BiI3 (Strukturbericht type D05) 5.4.6 β-TiCl3 and MoBr3/ZrI3/RuBr3 5.4.7 α-Al2O3 (corundum, Strukturbericht type D51) and FeTiO3 (ilmenite, type E22) 5.4.8 ZnS (wurtzite) (Strukturbericht type B4) 5.4.9 Olivine (Mg,Mn,Fe)2SiO4 (Strukturbericht type S12) 5.5 Other important structure types not based on densest packings 5.5.1 CsCl (Strukturbericht type B2) 5.5.2 MoS2 (Strukturbericht type C7) Further reading 6. Defects in solids 6.1 Point defects 6.1.1 Point defects in crystals of elements 6.1.2 Point defects in ionic compounds 6.1.3 Kröger-Vink notation for point defects 6.1.4 Colour centres – a special kind of point defects 6.1.5 Swapping places – order-disorder phenomena and the relation between superstructures and sublattices 6.1.6 Non-stoichiometric compounds and defect clusters 6.1.7 Substitutional and interstitial solid solutions 6.2 Line defects – dislocations 6.2.1 Edge dislocations 6.2.2 Screw dislocations 6.2.3 Movement of dislocations – plastic deformation 6.2.4 Crystallographic shear planes 6.3 Planar defects 6.3.1 Stacking faults, turbostratification, and interstratification 6.3.2 Internal boundaries in single crystals – mosaicity 6.3.3 Grain boundaries 6.3.4 Twin boundaries 6.4 Volume defects Conclusion and further reading 7. Phase diagrams 7.1 One-component systems 7.2 Two-component systems 7.2.1 Complete miscibility – solid solutions 7.2.2 Singly eutectic systems 7.2.3 Systems with compound formation that melt congruently 7.2.4 Systems with compound formation but incongruent melting 7.2.5 Systems with compound formation with an upper or lower limit of stability Further reading 8. Electronic structure of solid-state compounds 8.1 Bloch functions, Bloch’s theorem, the quantum number k, and crystal orbitals 8.2 Bandwidth, density of states, and the Fermi level 8.3 The Peierls distortion 8.4 Band structures in two- and three-dimensional systems 8.5 Examples of real band structures 8.5.1 ReO3 – a d1 compound with metallic properties 8.5.2 MoS2 – a d2 semiconductor with an indirect band gap 8.6 Direct and indirect band gaps Further reading 9. Magnetic properties of solid-state compounds 9.1 Diamagnetism and paramagnetism 9.1.1 Quantifying the magnetic moments of paramagnetic substances 9.1.2 Pauli paramagnetism 9.2 Cooperative magnetic phenomena 9.2.1 Ferromagnetism 9.2.2 Antiferromagnetism and superexchange interactions 9.2.3 Ferrimagnetism and double exchange 9.3 Some magnetic materials 9.3.1 Cubic spinel ferrites 9.3.2 Garnets 9.3.3 Hexagonal ferrites – magnetoplumbites Further reading 10. Phosphors, lamps, lasers, and LEDs 10.1 Phosphors 10.1.1 Fluorescent lamps 10.1.2 Phosphors for CRTs of TVs and computer screens 10.2 (Solid-state) lasers 10.2.1 Operation conditions 10.2.2 The ruby and the He-Ne laser 10.2.3 Classification of lasers 10.3 LEDs Further reading 11. Superconductivity 11.1 From the metallic to the superconducting state 11.1.1 The Meissner-Ochsenfeld effect and type I and type II superconductors 11.1.2 The BCS theory 11.2 Superconducting materials 11.2.1 The elements 11.2.2 Binary compounds, alloys, and intermetallics 11.2.3 Oxo cuprates – the high-temperature superconducting revolution 11.2.4 Further superconducting compounds Further reading 12. Ceramics 12.1 Definition and classification of ceramics and the ceramic method 12.2 (Alumo)silicate ceramics (traditional ceramics) 12.3 Binary oxide ceramics 12.3.1 α-Al2O3 12.3.2 ZrO2 12.3.3 TiO2, MgO, and BeO 12.4 Mixed oxide ceramics 12.4.1 Aluminium titanate 12.4.2 Barium titanate and lead zirconate titanate 12.5 Boride ceramics 12.6 Carbide ceramics 12.6.1 Boron carbide 12.6.2 Silicon carbide 12.7 Silicide ceramics 12.8 Nitride ceramics 12.8.1 Boron nitride 12.8.2 Aluminium nitride 12.8.3 Silicon nitride and SiALONs 12.8.4 Aluminium oxynitride 12.9 Glass-ceramics Further reading 13. Intermetallic phases 13.1 Classification scheme 13.2 Ordered solid solutions – superstructures 13.2.1 Superstructures of the bcc packing 13.2.2 Superstructures derived from densest packings (ccp or hcp) 13.3 Hume-Rothery phases 13.3.1 The γ-brass structure 13.4 Zintl phases 13.5 Packing-dominated phases (Frank-Kasper and Laves phases) 13.5.1 The geometrical principles in FK phases and the FK coordination polyhedra 13.5.2 Laves phases 13.5.3 Variants of Laves phases 13.5.4 σ-, μ-, M, P, and R phases 13.5.5 The Cr3Si structure (Strukturbericht type A15) 14. Porous crystals, reticular chemistry, and the net approach 14.1 Zeolites and zeotypes 14.1.1 Structural chemistry and building units of zeolites 14.1.2 Technically important zeolites 14.2 Metal-organic frameworks 14.2.1 Carbon capture and sequestration 14.2.2 Hydrogen storage 14.2.3 Methane storage 14.2.4 Water harvesting from air 14.2.5 Other (potential) applications 14.3 Networks and topology 14.3.1 Graphs and nets 14.3.2 Turning crystal structures into their underlying nets 14.3.3 Topology and net descriptors 14.3.4 Characterizing and identifying nets Further reading Appendix A: Strukturbericht designations and Pearson symbols References Subject index Formula index