Fundamentals of. Inorganic Glasses. Arun K. Varshneya. New York State College of Ceramics Alfred University Alfred, NY

Transcription

1 Fundamentals of Inorganic Glasses Arun K. Varshneya New York State College of Ceramics Alfred University Alfred, NY & Saxon Glass Technologies, Inc. Alfred, NY

2 CONTENTS Preface to the first edition Preface to the second edition v vii CHAPTER1 Introduction Brief History Glass Families of Interest Vitreous Silica Soda-Lime Glass Borosilicate Glass Lead Silicate Glass Aluminosilicate Glass Other Silica-Based Oxide Glasses Other Non-Silica-Based Oxide Glasses Halide Glasses Amorphous Semiconductors Chalcogenide and Chalcohalide Glasses Glassy Metals Glass-Like Carbon Oxyhalide, Oxynitride, and Oxycarbide Glasses A Brief Note on Glasses Found in Nature 12 Summary 14 Exercises 15 References 15 CHAPTER 2 Fundamentals of the Glassy State What is Glass? The V-T Diagram Pair Correlation Function and Radial Distribution Function Anomalies in the V-T Diagram 29 Summary 31 Exercises 32 References 32 ix

3 CHAPTER3 Glass Formation Principles Structural Theories of Glass Formation Zachariasen's Random Network Theory Sun's Single Bond Strength Criterion Phillips' Topological Constraints Hypothesis Russian Workers' Criticism of Zachariasen's Hypothesis The Kinetic Theory of Glass Formation The Nucleation Rate Crystal Growth Rate T-T-T Diagram 63 Summary 69 Exercises 70 References 71 CHAPTER4 Glass Microstructure: Phase Separation and Liquid Immiscibility Thermodynamics of Mixing More Formal Analysis of Phase Separation Electron Microscopy to Observe Phase Separation in Glass Observations of Phase Separation in Glass Observations of Controlled-Crystallization in Glass (Glass-Ceramics) 94 Summary 97 Exercises 98 References 99 CHAPTER5 Glass Compositions and Structures 5.1 Presentation of Glass Formulae 5.2 Silica Glass 5.3 Boric Oxide Glass 5.4 Alkali Silicate Glasses 5.5 Alkali-Alkaline Earth-Silicate Glasses 5.6 Alkali Borate Glasses 5.7 The Boron Anomaly 5.8 Alkali Borosilicate Glasses 5.9 Alkali Aluminosilicate Glasses HO

4 5.10 Lead, Bismuth, Thallium Silicate or Borate Glasses Phosphate Glasses Other Oxide Glasses Amorphous Silicon and Germanium Glassy Metals Chalcogenide and Chalcohalide Glasses Halides and Heavy Metal Fluoride Glasses (HMFG) 155 Summary 159 Exercises 160 References 161 CHAFTER 6 Composition-Structure-Property Relationship Principles General Principles Additivity Relationships 168 Summary 170 References 170 CHAPTER7 Density and Molar Volume Definitions Methods of Measurement Dependence upon Cooling Rate, Temperature and Composition Densification of Glasses by High Pressure or Irradiation Calculation of Density 181 Summary 183 Exercises 183 References 184 CHAPTER8 Elastic Properties and Microhardness of Glass Introduction Elastic Properties of Glass The Terminology of Elasticity Methods of Measuring Elastic Moduli Elastic Moduli Versus Glass Composition Temperature and Pressure Dependence of Elastic Moduli 198 xi

5 8.2.5 The Atomistic Approach to Elastic Behavior Microhardness of Glass Microhardness and Its Measurement Microhardness vs. Glass Composition 208 Summary 209 Exercises 210 References 210 CHAPTER9 The Viscosity and Surface Tension of Glass Introduction Viscosity-Temperature Dependence Viscosity Reference Points Measurement of Viscosity Viscosity vs. Composition and Temperature Data Viscosity of Common Soda-Lime Silicate Glass at Room Temperature (The "Urban Legend") Non-Newtonian Viscosity Volume Viscosity Surface Tension of Glass Methods of Measurement Dependence of Surface Tension on Composition 243 Summary 243 Exercises 245 References 246 CHAPTER10 Thermal Expansion of Glass Introduction Definitions Methods of Thermal Expansion Measurement Thermal Expansion vs. Composition and Temperature Concepts of Glass Expansion Thermal Stresses and the Thermal Shock Resistance 258 Summary 262 Exercises 262 References 264 xii

6 CHAPTER11 Heat Capacity of Glass Introduction Measurement of Heat Capacity Composition Dependence Temperature Dependence 267 Summary 272 Exercises 272 References 272 CHAPTER12 Thermal Conductivity of Glass Introduction Measurement of Thermal Conductivity Composition and Temperature Dependence 276 Summary 279 Exercises 279 References 279 CHAPTER 13 Glass Transition Range Behavior Introduction Viscoelastic Properties of Glass About Relaxation Maxwell Element Voigt-Kelvin Element Delayed elasticity Structural Relaxation due to Temperature Change Viscosity-Free Volume Theories of Glass Transition Thermodynamics of the Glass Transition Thermodynamic Orders of Phase Transition Adam-Gibbs Model of Cooperative Relaxations (Contributed by John C. Mauro) Stillinger Model of Inherent Structures (Contributed by John C. Mauro) Configurational Contributions to Physical Properties at the Glass Transition Kinetics of the Glass Transition 328 xm

7 Summary Exercises References 'Watching' the Relaxation (Concept of the Deborah number) Tool's Fictive Temperature Theory About the DTA and DSC of the Glass Transition Difficulties with Tool's Single T Concept Narayanaswamy's Model of Structural Relaxation Description of the Crossover Experiment in Terms of Narayanaswamy's Model for Relaxation Tiling Model (Contributed by John C. Mauro) Propeties Data in the T g Range Development of Permanent Stresses in Glass by Cooling Through the Transition Range Concepts of Annealing and Tempering CHAPTER14 Permeation, Diffusion and lonic Conduction in Glass Introduction More on the Atomic Theory of Diffusion and Electrical Conduction Mechanisms of Diffusion Correlation Effects Haven Ratio Isotope Effect Temperature Dependence of Diffusion and Electrical Conduction Measurement of Gas Permeability Measurement of Diffusion Coefficients Self-Diffusion Coefficients Measurement of Chemical Diffusion Coefficients Measurement of Electrical Conductivity Data on Permeability and Molecular Diffusion of Gases in Glass Data on lonic Diffusion and Electrical Conduction in Glass Some Aspects of Diffusion and Conduction Phenomena Ion Exchange Multicomponent Diffusion »V

8 Fast Ion Conduction Anionic Conduction 405 Summary 407 Exercises 408 References 409 CHAPTER15 Dielectric Properties Introduction Measurement of Dielectric Properties Data on Dielectric Properties and AC Conduction in Glass 424 Summary 429 References 430 CHAPTER 16 Electronic Conduction Introduction Concepts of Electronic Conduction in Amorphous Solids Defects in Amorphous Solids and Their Management Photoconductivity, Photoluminescence & Xerography Photovoltaics and Solar Cell Switching and Computer Memory Device 458 References 461 CHAPTER 17 Chemical Durability Introduction Mechanisms of Durability and Weatherability Measurement of Chemical Durability Data on Chemical Durability Methods of Improving Chemical Durability 473 Summary 474 Exercises 475 References 475 CHAPTER 18 Strength and Toughness Introduction 477 xv

9 18.2 Theoretical Strength of a flawless Brittle Solid Strength of a Flawed Brittle Solid: Griffith's Analysis Elementary Fracture Mechanics Concepts Glass Fatigue Mechanism of Strength Based upon Slow Crack Growth Elementary Fractographic Analysis Fracture Statistics Life Prediction Experimental Measurement of Glass Strength and Fracture Toughness Data on Strength and Fatigue Parameters Strengthening and Toughening 513 Summary 520 Exercises 521 References 522 CHAPTER 19 Optical Properties Introduction Some Theoretical Concepts Dispersion Scattering Absorption in the Visible Region (Colors in Glass) Absorption in the UV Absorption in the IR Photoelastic Properties Anomalous Birefringence Measurement of Optical Properties Data on Optical Properties Special Applications Photosensitive Glasses Nonlinear Optics Glass as a Laser Host Fiber Optics Coatings on Glass to Improve Optical Quality 577 Summary 579 Exercise 580 References 581 XVI

10 CHAPTER20 Fundamentals of Inorganic Glass Making Laboratory melting of glasses Oxide Glasses Chalcogenide Glasses Heavy Metal Fluoride Glasses (HMFG) Thioborates Continuous Melting of Glass Non-Fusion Based Techniques of Glass Making Glass Making Directly from the Solid State Glass Making Directly from the Gaseous State Glass Making via the Sol-Gel Process Introduction Raw Materials Typical Experimental Procedure The Forming of Glass Products Glass Container Fiat glass Glass Tubes and Rods Glass Fibers 624 Exercise 632 References 632 APPENDIX-I Elements of Linear Elasticity 635 APPENDIX-II SciGlass Database (By O. V. Mazurin and A. I. Priven) 645 Capabilities of SciGlass 646 About the Student version of SciGlass 647 References 648 APPENDIX-III Who wants to earn an A? 649 Answers 665 APPENDIX-IV Units, Conversion and General Data 667 Fundamen tals of Inorganic Glasses xvii

11 Subject Index 671 xviii