The two-word title of this book can only give an indication about its content and approach to the subject it deals with. In the course of time, the term has gradually become somewhat blurred. The reason is easy to see: similar problems are now more and more frequently studied by different branches of natural science. The term "mixed crystals" has acquired specific connotations in physics, chemistry, biology, and geology. One and the same term can now serve as a name for things which are either not quite the same or sometimes quite different. And this is precisely what happened to the two words in the title of the book. One of them, the term "crystal", for which crystallography had an un­ ambiguous definition, is now employed by biologists to describe the structure of cell membranes and by chemists who use it to denote degrees of polymer crystallinity. "Crystal" has thus become a broad term that can help describe any solid, or just a condensed state of a substance, if the solid has a suf­ ficient degree of order in the arrangement of its components. But the book is called "~lixed Crystals". The other word in its title, the adjective "mixed", has also developed several meanings. It is now thought ap­ plicable to both homogeneous and heterogeneous systems, that is, to crystals composed of different molecules and also to solids that are a mixture of crys­ tals with different structures.

Inhalt

1. Introduction.- 1.1 The Early History.- 1.2 Developments of the Twentieth Century.- 1.3 Outline of the Book.- 2. Phase Diagrams.- 2.1 Fundamentals.- 2.2 Conditions of Stability in Mixed Crystals.- 2.3 Types of Phase Diagrams.- 2.3.1 Crystallization of Two Pure Components from the Liquid Phase.- 2.3.2 Unlimited Solubility.- 2.3.3 Limited Solubility.- 2.3.4 Component Forming a Complex.- 2.3.5 Intermediate Phases.- 2.3.6 Transformations in the Solid State.- 2.3.7 Phase Diagrams of Optical Enantiomers.- 2.4 Determination of Phase Diagrams.- 2.4.1 Differential Thermal Analysis.- 2.4.2 X-Ray Phase Analysis of Polycrystalline Specimens.- 2.4.3 Growth of Mixed Single Crystals.- 2.4.4 Method of Contacting Specimens.- 3. Particle Packing in a Crystal.- 3.1 Elements of the Theory of Space Lattices.- 3.2 Geometric Model.- 3.2.1 Close-Packed Spheres.- 3.2.2 Representation of Atoms by Spheres.- 3.2.3 Representation of Atoms by Truncated Spheres.- 3.2.4 Hexagonal Packing.- 3.2.5 Body-Centered Cubic Structure.- 3.2.6 Ionic Crystals.- 3.2.7 Molecular Crystals.- 3.3 Structure of Single-Phase Mixed Crystals.- 3.3.1 Ordered Crystals.- 3.3.2 Disordered Crystals.- 3.3.3 Degree of Long-Range Order.- 3.3.4 Static Concentration Waves.- 3.3.5 Short-Range Order.- 3.3.6 Size and Shape Factors.- 4. Free Energy of a Solid Solution.- 4.1 General Formula for the Free Energy.- 4.2 Solid Solution Characterized by One Interaction Parameter.- 4.2.1 Free Energy of Mixing.- 4.2.2 The Ordering Model.- 4.3 Limited Solubility.- 4.3.1 Relationship Between the Energy of Mixing and Solubility.- 4.3.2 The Calculation of Solubility by a Given Substitution Scheme.- 4.4 Permutation of Particles in a Rigid Lattice.- 4.5 Lattice Distortions.- 4.6 Thermal Vibrations.- 5. Heterophase Systems.- 5.1 Eutectic Crystallization.- 5.1.1 Mechanism of Uncontrolled Crystallization.- 5.1.2 Unidirectional Crystallization.- 5.2 Decomposition of Solid Solutions.- 6. X-Ray Scattering.- 6.1 X-Ray Scattering by a Single Crystal.- 6.2 Scattering by One- and Two-Dimensional Systems.- 6.3 Thermal Vibrations.- 6.4 X-Ray Diffraction by Solid Solutions.- 6.4.1 Lattice Distortions.- 6.4.2 Structure of the Average Unit Cell.- 6.5 X-Ray Diffuse Scattering by Solid Solutions.- 6.5.1 Short-Range Order.- 6.5.2 Energy of Mixing.- 6.6 X-Ray Structure Analysis.- 7. Intermetallic Compounds.- 7.1 Classification Schemes for Intermetallic Compounds.- 7.2 Geometrical Analysis.- 7.3 AB Compounds.- 7.3.1 AuCu Type.- 7.3.2 CsCl Type.- 7.3.3 NaTl Type.- 7.3.4 Zinc Blende (ZnS) Type.- 7.3.5 NiAs Type.- 7.3.6 NaC1 Type.- 7.4 Compounds AB2.- 7.4.1 MgCu2 Type.- 7.4.2 AlB2 Type.- 7.4.3 CuAl2 Type.- 7.4.4 MgZn2 Type.- 7.5 Compounds AB3.- 7.5.1 SiCr3 Type.- 7.5.2 Type BiF3.- 7.5.3 AuCu3 Type.- 7.6 Number 13.- 7.6.1 Compounds AB13.- 7.6.2 Compounds AmBn with m = 1 and n=12.- 7.6.3 Compounds AmBn with m = 2 and n=11.- 7.6.4 Compounds AmBn with m = 3 and n=10.- 7.6.5 Compounds AmBn with m = 4 and n= 9.- 7.6.6 Compounds AmBn with m = 5 and n= 8.- 7.6.7 Compounds AmBn with m = 7 and n= 6.- 7.7 Close-Packing Principle for Intermetallic Compounds.- 8. Solid Solutions of Metals.- 8.1 Unlimited Solubility.- 8.1.1 Elements with the fcc Lattice.- 8.1.2 Elements with the HCP Lattice.- 8.1.3 Elements with the bcc Lattice.- 8.2 Terminal Solid Solutions.- 8.3 Solid Solutions on the Basis of Intermetallic Compounds.- 8.4 Ordering.- 8.4.1 Investigation of the Order-Disorder Transition by X-Ray Diffuse Scattering.- 8.4.2 Disorder in Cu3Au.- 8.4.3 Fe-Al Phase Diagram.- 8.4.4 Determination of the Degree of Long-Range Order by X-Ray Diffraction.- 8.4.5 Short-Range Order.- 9. Inorganic Solid Solutions.- 9.1 Isomorphous Substitutions in Alkali Halide Salts.- 9.2 Effect of the Difference in Ionic Size on the Solubility Limits in Systems of Inorganic Compounds.- 9.3 Theory of Ionic Substitutional Solid Solutions.- 9.3.1 General Remarks.- 9.3.2 Review of Suggested Theories.- 9.4 Interstitial Solid Solutions.- 10. Conditions of Formation of Substitutional Organic Solid Solutions.- 10.1 Geometrical Analysis of Substitution.- 10.1.1 Major Rule of Solubility.- 10.1.2 Exceptions to the Basic Rule of Solubility.- 10.2 Conditions of Continuous Solubility.- 10.2.1 Crystals of the Components Belonging to the Same Structure Type.- 10.2.2 Continuous Loss of Symmetry.- 10.3 Energy Calculations.- 10.3.1 Approximate Estimation of Mixing Energy.- 10.3.2 Possibility of Calculating Phase Diagrams.- 10.4 Unit-Cell Dimensions of Solid Solutions.- 10.4.1 Lattice Loosening.- 10.4.2 Interblock Solubility.- 11. Ordering in Organic Solid Solutions.- 11.1 One-Component Crystals with Orientational Disorder.- 11.1.1 Disorder with Increase in Crystal Symmetry.- 11.1.2 Disorder with No Increase in Crystal Symmetry.- 11.2 Orientational Disorder in Binary Systems.- 11.2.1 Disorder Due to Admixture Molecules.- 11.2.2 Lattices with Crystallographically Inequivalent Positions.- 12. Structures of Organic Solid Solutions.- 12.1 Diphenyl-2,2?-Dipyridyl [12.2,3].- 12.2 Para-Dibromobenzene - Para-Chloronitrobenzene [12.4].- 12.3 Acenaphthene - ?-Nitronaphthalene [12.8].- 12.4 Naphthalene - Coumarine [12.11].- 12.5 Dicarboxylic Acids [12.21,22].- 12.6 Naphthalene and Its ? Derivatives [10.14,16,11.25].- 12.7 Solid Solutions of Optically Active Substances or Enantiomers.- 12.7.1 Carvoxime.- 12.7.2 Carvoximebenzene [12.34].- 12.8 Durene-Para-Dibromobenzene [12.36].- 12.8.1 X-Ray Diffraction Analysis.- 12.8.2 Substitution Energy Computation.- 12.8.3 Probability Calculations of Different Guest Molecule Orientations.- 12.8.4 Calculation for Oriented Short-Range Order Correlation.- 12.9 Tolane Diphenylmercury [12.391.- 12.9.1 Diphenylmercury Phase.- 12.9.2 Tolane Phase.- 12.9.3 Diffuse X-Ray Scattering Studies.- 13. Complexes.- 13.1 Quasi-Valence Bonds Between Molecules of the Components.- 13.2 Complexes of Aromatic and Nitro Compounds.- 13.3 Packing Complexes.- 13.3.1 Hydroquinone-Based Clathrates.- 13.3.2 Clathrate Hydrates.- 13.3.3 Urea and Thiourea Complexes.- 13.3.4 Inclusion of Molecules into Intramolecular Cavities: Tri-o-Thymotide and Cyclodextrin Complexes.- 13.3.5 Inclusion of Molecules into Intermolecular Voids.- 13.3.6 Non-Inclusion Complexes.- 13.4 Layered Complexes.- 14. Polymers.- 14.1 The Structure of Polymeric Materials.- 14.1.1 A Polymer Molecule.- 14.1.2 Packing of Polymer Molecules.- 14.2 The Structure of Polymer Blends.- 14.2.1 Both Polymers are Amorphous.- 14.2.2 One Component Crystallizes.- 14.2.3 Both Components Crystallize.- 14.2.4 Some Remarks on the Technology of Polymer Blends.- 14.3 Bl…