Glasses and the Glass Transition

Glasses and the Glass Transition......Page 1
Foreword......Page 7
Contents......Page 11
Preface......Page 19
Contributors......Page 21
1 Introduction......Page 23
2.1 Glasses: First Attempts at a Classification......Page 31
2.2.1 The Fundamental Laws of Classical Thermodynamics and Consequences......Page 36
2.2.2 Thermodynamic Evolution Criteria, Stability Conditionsand the Thermodynamic Description of Nonequilibrium States......Page 44
2.2.3 Phases and Phase Transitions:Gibbs's Phase Rule, Ehrenfest's Classification, and the Landau Theory......Page 48
2.3 Crystallization, Glass Transition and Devitrification of Glass-Forming Melts: an Overview of Experimental Results......Page 58
2.4.1 Temperature Dependence of the Viscosity......Page 68
2.4.2 Significance of Viscosity in the Glass Transition......Page 76
2.4.3 Molecular Properties Connected with the Viscosity......Page 79
2.5.1 Heat Capacity......Page 81
2.5.2 Temperature Dependence of the Thermodynamic Functions: Simon's Approximation......Page 87
2.5.3 Further Methods of Determination of Caloric Properties of Glass-Forming Melts and Glasses......Page 96
2.5.4 Change of Mechanical, Optical and Electrical Properties in the Glass Transition Range......Page 98
2.6 Thermodynamic Nature of the Glassy State......Page 104
2.7 Concluding Remarks......Page 110
3.1 Introduction......Page 113
3.2.1 Basic Assumptions......Page 117
3.2.2 General Thermodynamic Dependencies......Page 118
3.2.3 Application to Vitrification and Devitrification Processes......Page 122
3.3.1 Kinetics of Relaxation......Page 125
3.3.2 Thermodynamic Properties: Generalized Equation of State......Page 127
3.4.1 Description of the Cyclic Processes under Consideration......Page 129
3.4.2 Temperature Dependence of the Structural Order Parameter in Cyclic Cooling and Heating Processes......Page 130
3.4.3 Definition of the Glass Transition Temperature via the Structural Order Parameter: the Bartenev--Ritland Equation......Page 132
3.4.4 Structural Order Parameter and Entropy Production......Page 135
3.4.5 Temperature Dependence of Thermodynamic Potentials at Vitrification......Page 137
3.4.6 Cyclic Heating-Cooling Processes: General Results......Page 145
3.5.1 Introduction......Page 147
3.5.2 Derivation......Page 149
3.5.3 Comparison with Experimental Data......Page 159
3.5.4 Discussion......Page 164
3.6.1 Brief Overview......Page 165
3.6.2 Model-Independent Definition of Fictive (Internal) Pressure and Fictive Temperature......Page 168
3.7 On the Behavior of the Viscosity and Relaxation Time at Glass Transition......Page 171
3.8.1 Introduction......Page 174
3.8.2 Glasses as Systems with Frozen-in Thermodynamic Fluctuations: Mueller and Porai-Koshits......Page 175
3.9 Results and Discussion......Page 180
4.1 Introduction......Page 187
4.2.1 Application of Free Volume Concepts......Page 188
4.2.2 A First Exception: Water......Page 191
4.2.3 Structural Changes of Liquids and Their Effect on the Pressure Dependence of the Viscosity......Page 193
4.2.4 Discussion......Page 195
4.3.1 Basic Equations: Aim of the Analysis......Page 196
4.3.2 Analysis......Page 197
4.3.3 Discussion......Page 199
5.1 Introduction......Page 201
5.2 Experimental Evidence on Specific Heats and Change of Caloric Properties in Glasses and in Disordered Solids: Simon's Approximations......Page 204
5.3 Consequences of Simon's Classical Approximation: the G(T) Course......Page 216
5.4 Change of Kinetic Properties at Tg and the Course of the Vitrification Kinetics......Page 217
5.5 The Frenkel--Kobeko Postulate in Terms of the Generic Phenomenological Approach and the Derivation of Kinetic and Thermodynamic Invariants......Page 220
5.6 Glass Transitions in Liquid Crystals and Frozen-in Orientational Modes in Crystals......Page 230
5.7 Spectroscopic Determination of Zero-Point Entropies in Molecular Disordered Crystals......Page 234
5.8 Entropy of Mixing in Disordered Crystals, in Spin Glasses and in Simple Oxide Glasses......Page 235
5.9 Generalized Experimental Evidence on the Caloric Properties of Typical Glass-Forming Systems......Page 237
5.10 General Conclusions......Page 241
6.1 Introduction......Page 245
6.2.1 Main Principles of Data Collection......Page 247
6.2.2 Reasons to Use the Stated Principles of Data Collection......Page 250
6.2.3 Problems in Collecting the Largest Possible Amounts of Glass Property Data......Page 252
6.2.4 Main Principles of Data Presentation......Page 253
6.3.1 About the Reliability of Experimental Data......Page 254
6.3.2 Analysis of Data on Properties of Binary Systems......Page 255
6.4.1 The Moral Aspect of the Problem......Page 268
6.4.2 An Example of Systematically Unreliable Experimental Data......Page 269
6.4.3 Concluding Remarks......Page 273
6.5 General Conclusion......Page 275
7.1 Introduction: 120 Years in Search of a Silver Bullet......Page 277
7.2.1 Simple Additive Formulae......Page 279
7.2.2 Additivity and Linearity......Page 280
7.2.3 Deviations from Linearity......Page 281
7.3.2 Gehlhoff and Thomas: Simulation of Small Effects......Page 282
7.3.3 Gilard and Dubrul: Polynomial Models......Page 284
7.4.1 Nonlinear Effects and Glass Structure......Page 286
7.4.2 Specifics of the Structural Approach to Glass Property Prediction......Page 288
7.4.4 Evaluation of the Contribution of Boron Oxide to Glass Properties......Page 289
7.4.5 Use of Other Structural Characteristics in Appen's and Demkina's Models......Page 293
7.4.6 Recalculation of the Chemical Compositions of Glasses......Page 294
7.4.7 Use of Atomic Characteristics in Glass and Melt Property Prediction Models......Page 300
7.4.8 Ab Initio and Other Direct Methods of Simulation of Glass Structure and Properties......Page 301
7.5.1 Simulation of Viscosity as a Function of Chemical Composition and Temperature......Page 302
7.5.2 Approaches to Simulation of Concentration Dependencies of Viscosity Characteristics......Page 304
7.5.3 Conclusion......Page 307
7.6.2 Linear and Polynomial Models......Page 308
7.6.3 Calculation of Liquidus Temperature: Neural Network Simulation......Page 311
7.6.4 Approach of the Author......Page 313
7.6.5 Fluegel: a Global Model as a Combination of Local Models......Page 318
7.6.6 Integrated Approach: Evaluation of the Most Probable Property Values and Their Errors by Using all Available Models and Large Arrays of Data......Page 319
7.7 Simulation of Concentration Dependencies of Glass Properties in Nonoxide Systems......Page 321
7.8 Summary: Which Models Were Successful in the Past?......Page 323
7.9 Instead of a Conclusion: How to Catch a Bluebird......Page 328
8.1 Introduction......Page 333
8.2 Ways to Describe the Glass Transition, the Properties of Glasses and of Defect Crystals: a Recapitulation......Page 335
8.3 Simon's Approximation, the Thermodynamic Structural Factor, the Kinetic Fragility of Liquids and the Thermodynamic Properties of Defect Crystals......Page 340
8.4.1 Enthalpy Accumulated at the Glass Transitions......Page 346
8.4.2 Free Energy Accumulated at the Glass Transition and in Defect Crystals......Page 349
8.5 Three Direct Ways to Liberate the Energy, Frozen-in in Glasses: Crystallization, Dissolution and Chemical Reactions......Page 353
8.5.1 Solubility of Glasses and Its Significance in Crystal Synthesis and in the Thermodynamics of Vitreous States......Page 354
8.5.2 The Increased Reactivity of Glasses and the Kinetics of Chemical Reactions Involving Vitreous Solids......Page 361
8.6 The Fourth Possibility to Release the Energy of Glass: the Glass/Crystal Galvanic Cell......Page 362
8.7 Thermoelectric Driving Force at Metallic Glass/Crystal Contacts: the Seebeck and the Peltier Effects......Page 366
8.8.1 Introductory Remarks......Page 370
8.8.2 Agriglasses, Glasses as Nuclear Waste Forms and Possible Medical Applications of Dissolving Organic Glasses......Page 372
8.8.3 Glasses as Amorphous Battery Electrodes, as Battery Electrolytes and as Battery Membranes......Page 374
8.8.4 Photoeffects in Amorphous Solids and the Conductivity of Glasses......Page 375
8.9 Some Conclusions and a Discussion of Results and Possibilities......Page 376
9.1 Introduction......Page 379
9.2 A Brief Historical Recollection......Page 382
9.3 The Classical Thermodynamic Approach......Page 385
9.4 Nonequilibrium States and Classical Thermodynamic Treatment......Page 388
9.5 Zero-Point Entropy of Glasses and Defect Crystals: Calculations and Structural Dependence......Page 390
9.6 Thermodynamic and Kinetic Invariants of the Glass Transition......Page 391
9.7 Experimental Verification of the Existence of Frozen-in Entropies......Page 393
9.8 Principle of Thermodynamic Correspondence and Zero-Point Entropy Calculations......Page 398
9.9 A Recapitulation: the Third Principle of Thermodynamics in Nonequilibrium States......Page 399
10.1 Introductory Remarks......Page 401
10.2 “Sirsu”, “Shvistras”, “Hyalos”,“Vitrum”, “Glaes”, “Staklo”, “Cam”......Page 402
10.3 “Vitreous”, “Glassy” and “Glasartig”, “Vitro-crystalline”......Page 404
10.4 Glasses in Byzantium, in Western Europe, in Venice, in the Balkans and Several Other Issues......Page 406
10.5 Concluding Remarks......Page 407
References......Page 409
Index......Page 429