Glass Chemistry

1 Historical Development of Glass Chemistry.- 1.1 The Beginnings of Glass Research.- 1.2 History of the Chemistry of Optical Glass.- 1.2.1 Ernst Abbe and Otto Schott.- 1.2.2 Carl Zeiss and the Zeiss Foundation.- 1.2.3 The Development of New Optical Glasses after 1939.- 1.3 History of Technical Glass.- 2 Freezing of a Melt to a Vitreous Solid.- 2.1 Fusion and Crystallization. General.- 2.2 Significant Differences Between Crystalline and Non-crystalline (Glassy) Solids.- 2.3 Standard Viscosity Temperatures for Solidification of Glasses.- 2.4 Annealing of Optical Glass.- 3 Structural Elements of Silicates.- 3.1 The SiO4 Tetrahedron as the Basic Building Block of Silicates.- 3.2 Building Units of Natural Crystalline Silicates.- 4 Classical Theories of Glass Structure.- 4.1 Glass Structure According to Tammann (since 1903).- 4.2 Glass Formation According to Goldschmidt.- 4.3 The Zachariasen-Warren Network Theory.- 4.4 Extension of the Network Theory by Dietzel.- 4.5 Additional Concepts Supplementing the Network Theory.- 4.6 Lebedev's Crystallite Theory.- 4.7 Further Development of the Crystallite Theory.- 4.8 Kinetic Theory.- 5 Methodology in Glass Research.- 5.1 Structure of Liquids and Melts.- 5.2 The Nuclear Magnetic Resonance Method as Applied to Glass Research.- 5.2.1 Introduction.- 5.2.2 Basic NMR Theory.- 5.2.3 Dipolar Interaction.- 5.2.4 Chemical Shift.- 5.2.5 Quadrupole Interaction.- 5.3 Electron Microscopy.- 5.3.1 Introduction.- 5.3.2 Relations Between Light and Electron Microscopy.- 5.3.3 Imaging and Preparation of Samples.- 5.3.3.1 Direct Penetration of the Sample by Electrons.- 5.3.3.2 Carbon Replica Method after Bradley.- 5.3.3.3 Further Development of the Experimental Technique of Bradley's Carbon Replica.- 5.3.3.4 Treatment of Glass Surfaces Prior to Replication.- 5.3.4 The Scanning Electron Microscope and Electron Microprobe.- 6 Microphase Separation.- 6.1 Early History.- 6.2 Electron Microscopy Evidence for Immiscibility Phenomena in Glasses.- 6.3 Theoretical Treatment.- 6.3.1 Thermodynamics of Phase Separation. General (Kortüm).- 6.3.1.1 Conditions of Equilibrium and Stability.- 6.3.1.2 Derivation of Stability Conditions for a Binary Mixed Phase.- 6.3.1.3 Characterization of the Regions of Immiscibility in Binary and Ternary Systems.- 6.3.2 Thermodynamics of Immiscibility in Glasses.- 6.3.3 Kinetics of Immiscibility in Glasses.- 6.4 Experimental Evidence.- 6.4.1 Functional Change of Microphases.- 6.4.2 Multiple Phase Separation.- 6.4.3 Shells around Microphases.- 6.4.4 Droplet Agglomeration after Secondary Phase Separation.- 6.4.5 Composition of Microphases and Distribution of Heavy Metal Ions.- 6.4.6 General Conclusions on Immiscibility Behavior and Microstructure.- 6.4.7 Control of Phase Separation.- 7 Structure and Properties of Colorless Glasses.- 7.1 Silica Glass.- 7.2 Alkali Silicate Glasses.- 7.2.1 The Mixed-Alkali Effect.- 7.3 Alkaline Earth and Alkali-Alkaline Earth Silicate Glasses.- 7.4 Borate and Borosilicate Glasses.- 7.4.1 Binary Alkali Borate Glasses. The "Boron Anomaly".- 7.4.1.1 Temperature Dependence of the Boric Acid Anomaly.- 7.4.1.2 Tendency Toward Immiscibility.- 7.4.1.3 Present State of Interpretations of the "Boron Anomaly".- 7.4.2 Borosilicate Glasses.- 7.4.2.1 The Ternary System Na2O-B2O3-SiO2.- 7.4.2.2 Vycor-Type Glasses.- 7.4.2.3 Pyrex-Type Glasses.- 7.5 Glasses of High Lead Content.- 7.5.1 Glass Formation in Lead-Containing Systems.- 7.5.2 Phase Separation in Glasses Containing Lead.- 7.5.3 Structurally Conditioned Coloration of High-Lead Silicate Glasses.- 7.6 Phosphate Glasses.- 7.6.1 Structure of Phosphate Glasses.- 7.6.2 Phase Separation in Pure Phosphate Glasses.- 7.7 Tellurite Glasses.- 7.7.1 Glass-Formation Range and Optical Properties of Tellurite Glasses.- 7.7.2 Structure of Tellurite Glasses.- 7.8 Beryllium Fluoride Glasses - "Model Glasses".- 7.8.1 Theoretical Discussion of "Model Glasses".- 7.8.2 Ranges of Glass Formation in BeF2 Model Systems. Properties of These Glasses.- 7.8.2.1 Density Plots.- 7.8.2.2 Refractive Index Plots.- 7.8.3 Phase Separation in Pure BeF2 Glasses.- 7.8.4 Fluoride Glasses Free of Beryllium.- 7.8.5 Fluorophosphate Glasses.- 7.9 Zirconium Fluoride Glasses.- 7.9.1 Glass Formation, Structure and Properties.- 7.10 Germanate Glasses.- 7.10.1 Glass Formation from GeO2 and Germanate Melts.- 7.10.2 Structure and Properties.- 7.11 Glasses Containing Arsenic Oxide.- 7.11.1 Glass Formation.- 7.11.2 Structure and Properties of Glasses of High Arsenic Oxide Content.- 7.12 Glasses Containing Antimony Oxide.- 7.12.1 Glass Formation and Some Important Properties.- 7.12.2 Structure.- 7.13 Glasses Containing Bismuth Oxide.- 7.14 Limited Glass Formation in Systems of Exclusively Scientific Interest.- 7.14.1 Titanate Glasses.- 7.14.2 Vanadate Glasses.- 7.14.3 Nitrate Glasses.- 7.14.4 Carbonate Glasses and Glasses Based on ZnCl2.- 7.14.5 Oxyhalide Glasses.- 7.14.6 Oxynitride Glasses.- 7.14.7 Oxycarbonate Glasses.- 7.14.8 High-H2O Glasses.- 7.15 Metal Glasses.- 7.16 Vitreous Carbon.- 7.17 The Sol-Gel Method for Production of Glasses and Glass Ceramics.- 7.17.1 Introduction.- 7.17.2 The Alkoxide Sol-Gel Method.- 7.17.3 The Silica Hydrosol Process.- 7.17.4 The Ormocer Method.- 7.17.5 The Importance and Application of Gel Glasses.- 8 New Optical High-Performance Glasses.- 8.1 Fundamental Principles of the Dispersion Behaviour of Glasses.- 8.2 Change of the Dispersion with the Introduction of Additional Absorption Centers.- 8.3 Optical Glasses with Unusual Partial Dispersions.- 8.4 Athermal Optical Glasses.- 8.5 Non-linear Refraction.- 8.6 Prerequisites on the Raw Material for the Production of Optical Glasses.- 9 Structure and Properties of Colored Glasses.- 9.1 General.- 9.2 Absorption of Colorless Base Glasses.- 9.3 Glasses Colored by Ions.- 9.3.1 Dependence of Absorption on Network-Former.- 9.3.2 Dependence of Absorption on Modifiers.- 9.3.3 Dependence of Absorption on the Valency of the Chromophore.- 9.3.4 Dependence of Absorption on the Coordination Number of the Chromophore.- 9.3.4.1 Coordination Change Due to Change in Chromophore Concentration.- 9.3.4.2 Coordination Change of Chromophore Due to Concentration Change of Network-Modifier.- 9.3.4.3 Coordination Change of Chromophore Due to Changed Network-Former.- 9.3.5 Problems of Interpretation.- 9.3.6 Technologically Important Chromophores and Selected Transmission Curves.- 9.4 Striking Glasses.- 9.4.1 Composition, Preparation, and Absorption Behavior.- 9.4.2 Base Glass Structure and Coloring Mechanism in "Striking" Glasses.- 9.4.3 Coloring Mechanism in Striking Glasses.- 9.4.4 Related Glasses with Other Chromophores.- 9.5 Glasses Colored by Metal Colloids (Ruby Glasses).- 9.5.1 Composition, Fabrication, and Absorption Behavior.- 9.5.2 Structure and Coloring Mechanism in True Ruby Glasses.- 9.5.3 Silver Stain.- 9.6 IR-Absorbing Glasses (Heat-Absorbing Glasses).- 9.6.1 Application of Heat-Absorbing Glasses and Absorption Behavior of Glasses Containing Fe2+ and Fe3+ Ions.- 9.6.2 Development, Production, and Properties of Heat-Absorbing Glasses.- 9.7 IR-Transmitting Glasses.- 9.7.1 IR-Transmission of Solids.- 9.7.2 IR-Transmission of Germanate, Tellurite, and Aluminate Glasses.- 9.7.3 IR-Transmitting Chalcogenide Glasses.- 9.7.3.1 Arsenic Sulfide Glasses.- 9.7.3.1 Other Chalcogenide Systems.- 9.8 Opacified Glasses.- 9.8.1 Mechanisms of Opacification.- 9.8.2 History and Classification of Opacified Glasses.- 9.8.3 Phosphate Opal Glasses.- 9.8.4 Fluorine Opal Glasses.- 9.8.5 Opal Glasses Based on SnO2, TiO2, ZrO2, CeO2, ZnO, and Other Compounds.- 9.8.6 Light Scattering and Color of Microdisperse Two-Phase Glasses.- 10 Crystallization of Glasses.- 10.1 General.- 10.2 Theoretical Considerations.- 10.2.1 Homogeneous Nucleation.- 10.2.2 Heterogeneous Nucleation.- 10.2.3 Crystal Growth.- 10.3 Crystallization as a Defect in Glass.- 10.4 Controlled Crystallization.- 10.4.1 Principles of Controlled Crystallization.- 10.4.2 Pioneering Developments at Corning Glass Works.- 10.4.2.1 Glass Ceramics with Minimal Coefficients of Thermal Expansion.- 10.4.2.1.1 Composition, Production, and Application.- 10.4.2.1.2 Structure and Properties.- 10.4.2.2 Machinable Glass Ceramics.- 10.4.2.2.1 General, Composition, Production.- 10.4.2.3 New Mica-Containing Glass Ceramics.- 10.4.2.4 Chain Silicate Glass Ceramics.- 10.4.2.5 Strengthening of a Special Glass by the Chemcor Process.- 10.4.3 Fundamental Investigations in the Development of Glass-Ceramics at the Otto Schott Institute of the Friedrich Schiller University in Jena.- 10.4.3.1 Nucleation and Crystallization Kinetics of a Base Glass from the Mg0-Al203-Si02 System.- 10.4.3.2 Doping of the Base Glass with 11.2 mol% Fluorine Ions.- 10.4.3.3 High-Strength Glass Ceramics Containing Spinel.- 10.4.3.4 Single Doping of the Base Glass with 2-10 mol% TiO2 (Ti2O3) also Leads to High Strength Glass Ceramics.- 10.4.3.5 Double Doping of the Base Glass with 11.2 mol % F and 5.2 mol % Na2O Yields Machinable Glass Ceramics.- 10.4.3.6 Ferrimagnetic Glass Ceramics.- 10.4.4 Development of Bioglass Ceramics for Medicine.- 10.4.4.1 Introduction.- 10.4.4.2 Development of Bioglass Ceramics, Present State, Requirements and Targets.- 10.4.4.3 Development of Biocompatible and Machinable Glass Ceramics.- 10.4.4.4 Development of Bioactive Glass Ceramics.- 10.5 Bioactive, Piezoelectric, Phosphate Glass Ceramics Free of Silica.- 10.5.1 Development Trends of Phosphate Glass Ceramics.- 10.5.2 Structure and Crystallization Behavior of Phosphate Glasses.- 10.5.3 Development of Pure Biophosphate Glass Ceramics.- 10.5.4 Animal Experiments at the Academy of Medicine of Dresden on the Intergrowth Between Phosphate Glass-Ceramic Implants and Bones.- 10.5.5 Clinical Tests of the New Bioglass Ceramics on Humans.- 10.5.6 Summary and Outlook.- 10.6 Sintered and Special Glass Ceramics.- 10.6.1 Sintered Glass Ceramics.- 10.6.2 Special Glass Ceramics.- 11 The Strength of Glass.- 11.1 Theoretical Strength.- 11.2 Effective Strength: Attempts at Theoretical and Practical Explanations.- 11.2.1 Theoretical Concepts Regarding the Strength of Glass.- 11.2.2 Experimental Investigations.- 11.2.2.1 A Demonstration of Griffith Flaws.- 11.2.2.2 Strength After Elimination of Crude Surface Defects.- 11.2.2.3 Fatigue.- 11.2.2.4 Aging.- 11.2.3 The Strength of Glass Fibers.- 11.3 Strengthening Methods in Practice.- 11.3.1 Tempering.- 11.3.2 Compound Glass.- 11.3.3 Silicon-Organic Coatings.- 11.3.4 Dealkalizing.- 11.3.5 Ion Exchange: "Chemical Strengthening".- 11.3.6 Multiple Layer Glass.- 12 Interaction Between High Energy Radiation and Glass.- 12.1 General Considerations.- 12.2 Photosensitive Glasses Based on the Formation of Metal Colloids.- 12.3 Photosensitive Glasses Based on Partial Crystallization in Lithium and Barium Silicate Systems.- 12.3.1 Composition and Preparation.- 12.3.2 Structure, Properties, and Microprocesses.- 12.3.3 Special Properties and Applications, Photoform, Photoceram.- 12.3.3.1 Photoform.- 12.3.3.2 Photoceram.- 12.4 Dosimeter Glasses.- 12.5 Photochromic Systems and Glasses.- 12.5.1 Requirements of Photochromic Systems.- 12.5.2 Combination of Photochromic Organic Compounds and Glass.- 12.5.3 Inorganic Photochromic Glasses.- 12.5.3.1 Development and Application.- 12.5.3.2 Photochromic Glasses Activated by Rare Earths.- 12.5.3.3 Borosilicate Glasses Doped with Silver Halides.- 12.5.3.4 Borosilicate Glasses Doped with Silver Molybdate and Tungstate.- 12.5.3.5 Borosilicate Glasses Doped with Copper or Cadmium Halides.- 12.5.3.6 Thermally Darkening Photochromic Glasses ("TDPC").- 12.6 Laser Glasses.- 12.6.1 Introduction.- 12.6.2 Light Absorption and Light Emission in Solids.- 12.6.3 The Solid Laser.- 12.6.3.1 Laser Principle - Oscillator - Optical Pumps.- 12.6.3.2 Mode of Operation of Lasers.- 12.6.3.3 Properties of a Solid Laser Material.- 12.6.4 Efficiency Increase by Sensitization.- 12.6.5 Applications of Lasers.- 12.7 Radiation Protection and Radiation-Resistant ("Protected") Glasses.- 12.8 Transmission Changes of Colored Glasses under ? Irradiation.- 12.9 Solarization.- 13 Survey of the Physical Basis of Some Glass Properties.- 13.1 Introduction.- 13.2 Refraction of Light, Dispersion and Abbe's Value.- 13.3 Density.- 13.4 Molar Refraction.- 13.5 Thermal Expansion.- 13.6 Viscosity.- 13.7 Strain.- 13.8 Surface Tension.- 13.9 Heat Conductivity, Specific Heat.- 13.10 Electrical Conductivity.- References.