Treatise on Solid State Chemistry

1 Diffusion.- 1. Introduction.- 2. The Phenomenology of Diffusion.- 2.1. Fick’s Laws.- 2.2. Self-Diffusion and Chemical Diffusion. The Kirkendall Effect.- 2.3. Experimental Methods for Measuring Diffusion Coefficients.- 2.4. The Thermodynamic Description of Diffusion.- 3. The Atomic Theory of Diffusion.- 3.1. The Basic Random Walk Expressions.- 3.2. Chemical Diffusion.- 3.3. Self-Diffusion Correlation.- 3.4. The Theory of Atomic Jump Rates.- 3.5. The Temperature and Pressure Dependence of D.- 4. Experimental and Theoretical Results. A Brief Summary.- 4.1. Diffusion in Metals.- 4.2. Diffusion in Ionic Crystals.- References.- 2 Factors Influencing the Reactivity of Solids.- 1. General Outline.- 2. Decomposition and Related Reactions.- 2.1. General.- 2.2. The Effect of Mechanical Strain, Additives, and Pre-irradiation upon the Thermal Decomposition of an Inorganic Compound: Ammonium Perchlorate.- 2.3. The Role of Surface Impurities and of Shear Structures in the Thermal Decomposition of Transition Metal Oxides.- 2.4. The Significance of Localized Energy Levels in the Photolysis of Inorganic Compounds.- 2.5. Topochemical Effects in the Photodimerization of Organic Molecules.- 3. Solid-Gas Reactions.- 3.1. Tarnishing Reactions.- 3.2. Other Reactions; The Role of Hydrogen Pressure and of Vacancies in the Reduction of Additives in an Alkali Halide Matrix.- 4. Solid-Solid Reactions.- 4.1. General.- 4.2. Factors Influencing Solid-Solid Reactivity.- 5. Solid-Liquid Reactions.- 5.1. General.- 5.2. Dissolution of Semiconductors: Influence of Conductivity Type, Illumination, Applied Voltage, Crystal Face, and Inhibitors in Solution.- 5.3. The Role of Dislocations in Etching.- 6. Reactions at the Surface of Solids.- 6.1. Heterogeneous Catalysis.- 6.2. Electrode Reactions.- 7. Conclusions.- References.- 3 High-Temperature Reactivity.- 1. Introduction.- 2. Equilibrium Thermodynamics for High-Temperature Reactivity.- 2.1. Free Energy Equations and Calculations.- 2.2. Enthalpy and Entropy.- 2.3. Thermodynamic Data Compilations.- 3. Phase Diagrams and Chemical Reactions.- 3.1. The Phase Rule.- 3.2. Writing Chemical Equations.- 3.3. High-Temperature Reactions.- 4. General Behavior and Trends in High-Temperature Reactions..- 4.1. High-Temperature versus Room-Temperature Reactions.- 4.2. Trends in Reaction Entropies.- 4.3. Principle of Successive Entropy States.- 4.4. Chemical Behavior of Solid-Gas Systems.- 4.5. Examples of Reaction Types in Solid-Gas Systems.- 5. Summary and Concluding Remarks.- Appendix: Sources of High-Temperature Thermodynamic Data.- Acknowledgments.- References.- 4 Decomposition Reactions.- 1. Introduction.- 2. Dislocations and Enhanced Reactivity.- 3. Kinetics of Solid Decomposition.- 4. Nucleus Formation.- 4.1. Single-Step Nucleation.- 4.2. Multistep Nucleation.- 5. Nucleus Growth.- 6. Kinetic Equations of Nucleus Formation and Growth.- 7. Exponential Acceleratory Period.- 8. Abnormal Initial Growth.- 8.1. Calculation of Normal Growth Constant.- 8.2. The Induction Period.- 9. Reversible Decompositions.- 10. Aging.- 11. General Discussion.- References.- 5 Solid-State Reactions.- 1. Introduction.- 1.1. General Remarks.- 1.2. Brief Summary of Defect Thermodynamics.- 1.3. Some Aspects of the Phenomenological Diffusion Theory Relevant to Solid-Solid Reactions.- 1.4. Descriptive Examples of Solid-State Reactions.- 2. Chemical Reactions in the Solid State.- 2.1. Reactions between Atomic Defects.- 2.2. Reactions between Ionic Crystals.- 2.3. Reactions in and between Metals.- 3. Special Solid-Solid Reactions.- 3.1. Powder Reactions.- 3.2. Topochemical Reactions.- 3.3. Double Reactions.- 3.4. Concluding Remarks.- Acknowledgment.- References.- 6 Solid-State Electrochemistry.- 1. General Aspects of Solid Electrolytes.- 1.1. Disorder Equilibria in Solid Electrolytes and between Solid Electrolytes and the Environment.- 1.2. Transport Phenomena of Ions and Electrons in Solid Electrolytes.- 2. Galvanic Cells with Solid Electrolytes for Thermodynamic Measurement.- 2.1. General Properties of Cells with Solid Electrolytes.- 2.2. Galvanic Cells with Solid Electrolytes for AG Measurements.- 2.3. Galvanic Cells with Solid Electrolytes for Activity Measurements.- 2.4. Coulometric Titration.- 3. Galvanic Cells with Solid Electrolytes for Kinetic Investigations.- 3.1. Electrochemical Measurements of Oxygen Diffusion in Metals at High Temperatures using a Zirconia-Based Electrolyte.- 3.2. The Kinetics of the Formation of Solid Nickel Sulfide on Nickel at 400°C.- 3.3. Electrochemical Studies of the Transfer of Silver, Silver Ions, and Electrons across the Phase Boundary Solid Silver/Solid Silver Sulfide.- 3.4. Electrochemical Investigations of the Evaporation of Iodine from Copper Iodide.- 3.5. Electrochemical Knudsen Cells for Investigating the Thermodynamics of Vapors.- References.- 7 The Photographic Process.- 1. Early Developments.- 2. The Emulsion System.- 3. Sensitometric Properties.- 4. Ionic Disorder in the Silver Halides.- 5. Electron and Hole Mobility.- 6. Photoelectric Effect in Emulsion Grains.- 7. Ultraviolet Response and Band Structure.- 8. Phonon- and Disorder-Assisted Processes.- 9. Luminescence and Induced Absorption.- 10. Mechanism of Latent Image Formation.- Acknowledgments.- References.- 8 Gas-Solid Reactions—Oxidation.- 1. Introduction.- 2. Chemisorption and Nucleation in the Initial Stage of Oxidation.- 3. Defect Structure of Halides, Oxides, and Sulfides.- 3.1. Defect Structure in Silver Halides.- 3.2. Defect Structure in p-Type Oxides and Sulfides.- 3.3. Defect Structure in n-Type Oxides and Sulfides.- 4. General Nature of Transport Processes in Ionic Crystals.- 4.1. Diffusion-Controlled Oxidation—The Parabolic Rate.- Law.- 4.2. Local Cell Action during Metal Oxidation.- 4.3. Grain Boundary and Short-Circuit Diffusion in the Growing Oxide Layer.- 4.4. Metal Oxidation with Simultaneous Diffusion of Oxygen in the Metal.- 5. Phase Boundary Reactions and Evaporation of the Scale—The Linear Rate Law.- 6. Catastrophic Oxidation.- 7. Oxide Layer Formation with Several Phases.- 8. Oxidation of Alloys.- 8.1. The Semiconductor Valence Approach to Alloy Oxidation.- 8.2. Selective Oxidation of Noble Alloys.- 8.3. Formation of Complex Oxide Layers.- 8.4. Internal Oxidation.- 9. Passivity and Inhibition in High-Temperature Metal Oxidation.- 10. Thin Oxide Layer Formation.- 10.1. The Linear Rate Law.- 10.2. A Cubic Rate Law.- 10.3. Space-Charge Effects in Oxide Growth—The Fourth-Power Rate Law.- 10.4. Logarithmic and Reciprocal Logarithmic Rate Laws.- 11. Concluding Remarks.- References.- 9 Metal-Liquid Reactions: Corrosion.- 1. Definitions of Corrosion.- 2. Thermodynamic Considerations.- 3. Kinetic Considerations.- 4. Alloy Corrosion.- 4.1. Dealloying.- 4.2. Other Significant Alloying Effects.- 5. Passivity.- 5.1. Anodic Passivation.- 5.2. Mechanism of Passivation.- 6. Aggravating Factors in Corrosion.- 6.1. Galvanic Corrosion.- 6.2. Crevice Corrosion.- 6.3. Concentration Cell Corrosion.- 6.4. Erosion Corrosion.- 6.5. Corrosion in the Presence of Cyclic Stresses.- 7. Control of Corrosion.- 7.1. Cathodic Protection:.- 7.2. Anodic Protection.- 7.3. Inhibition.- 7.4. Organic Coatings.- 8. Morphology of Corrosion.- 8.1. General Corrosion.- 8.2. Pitting.- 9. Metallurgical Factors.- 9.1. Introduction.- 9.2. Orientation of Grains.- 9.3. Effects of Dislocations and Cold Work.- 9.4. Grain Boundaries.- 9.5. Compositionally Different Phases.- 9.6. Effect of Deformation on Corrosion Processes.- 9.7. Tunneling.- 9.8. Interaction of Corrosion and Deformation Processes.- 9.9. Interaction of Hydrogen with Metals.- 10. Intergranular and Interfacial Corrosion.- 10.1. Introduction.- 10.2. Intergranular Corrosion in Sensitized Stainless Steel.- 10.3. Exfoliation of Aluminum.- 10.4. Intergranular Attach in the Absence of Precipitation.- 10.5. Grain Boundary Fracture Simulated by Hydrogen Entry.- 11. Environmentally Induced Cracking Phenomena.- 11.1. Introduction.- 11.2. Organization of the Data.- 11.3. Fundamental Aspects of Environmental Effects on Crack Propagation.- 11.4. Phenomenological Influences on Stress Corrosion Cracking.- Acknowledgments.- References.- 10 Sintering.- 1. Introduction.- 2. Sintering of Powdered Metals and Ceramics.- 3. Phenomenological Description of Sintering in the Absence of a Liquid Phase.- 3.1. Particle Joining.- 3.2. Sintering Temperature.- 4. The Driving Force for Sintering.- 4.1. The Kelvin Equation.- 4.2. Curvature in Three Dimensions.- 4.3. Application to Particle Joining and Pore Elimination.- 4.4. Importance of Grain Boundary Energy.- 4.5. Powder Activity.- 5. Grain Growth during Sintering.- 5.1. Particle Growth during the Early Stages of Sintering.- 5.2. Grain Boundary Motion in Solids.- 5.3. Interactions between Pores or Other Inclusions and Grain Boundaries.- 5.4. Exaggerated Grain Growth.- 5.5. Pore-Free Products from Sintering.- 6. Other Sintering Modes.- 6.1. Liquid-Phase Sintering.- 6.2. Hot Pressing.- 6.3. Reaction Sintering.- 7. Theory of Sintering.- 7.1. Driving Force and Mechanisms.- 7.2. Common Characteristics of Sintering Models.- 7.3. Development of Microstructure.- 7.4. Sintering Stages.- 7.5. Initial-Stage Sintering Models.- 7.6. Intermediate-Stage Sintering Models.- 7.7. Final-Stage Sintering Models.- 8. Summary.- Acknowledgment.- References.- 11 Reactions of Solid Polymers.- 1. Introduction.- 1.1. The Chain Structure of Addition Polymers.- 1.2. Molecular Weight Distribution.- 1.3. Chain Conformation and Polymer Morphology.- 1.4. Types of Polymer Reactions.- 2. Chain Scission and Cross-Linking; General.- 2.1. Effects of Chain Scission.- 2.2. Effects of Cross-Linking.- 2.3. Simultaneous Scission and Cross-Linking.- 3. Degradation and Oxidation.- 3.1. Thermal Degradation.- 3.2. Oxidative Degradation.- 3.3. Ozone Degradation.- 3.4. Flammability.- 3.5. Chemical Degradation.- 4. Cross-Linking.- 4.1. Cross-Linking and Mechanical Properties.- 4.2. Cross-Linking Reactions.- 5. Effects of Radiation.- 5.1. Ultraviolet Photooxidation.- 5.2. High-Energy Radiation.- 5.3. Photoresists and Electron-Resists.- 6. Reactions under Mechanical Stress.- References.