Glasses and the glass transition

Select an Action

Place Hold(s)
Add to My Lists
Email
Print

Title:

Personal Author:

Schmelzer, J. (Jürn)

Publication Information:

Weinheim : Wiley-VCH Verlag, c2011

Physical Description:

xx, 408 p. : ill. ; 25 cm.

ISBN:

9783527409686

Abstract:

"Written by the best researchers in the field, this up-to-date treatise fills the gap for a high-level work discussing current materials and processes. It covers all the steps involved, from vitrification, relaxation and viscosity, right up to the prediction of glass properties, paving the way for improved methods and applications. For solid state physicists and chemists, materials scientists, and those working in the ceramics industry."--Publisher description.

Subject Term:

Glass

Added Author:

Gutzow, I. (Iwan)

Mazurin, Oleg Vsevolodovich

Available:*

Library	Item Barcode	Call Number	Material Type	Item Category 1	Status
Searching... PSZ JB	30000010278975	TA450 S34 2011	Open Access Book	Book	Searching... Unknown

On Order

Summary

Written by renowned researchers in the field, this up-to-date treatise fills the gap for a high-level work discussing current materials and processes. It covers all the steps involved, from vitrification, relaxation and viscosity, right up to the prediction of glass properties, paving the way for improved methods and applications.
For solid state physicists and chemists, materials scientists, and those working in the ceramics industry.

With a preface by L. David Pye and a foreword by Edgar D. Zanotto

Author Notes

Jrn W. P. Schmelzer studied theoretical physics at the Universities of Odessa (Ukraine) and Rostock (Germany). He taught this discipline for many years at the Universities of Rostock and Addis Ababa (Ethiopia). Since 1995, he has been working simultaneously at the Joint Institute for Nuclear Research in Dubna near Moscow, organizing there since 1997 international research workshops on the theory of phase transitions and possible applications, in particular to materials science. In 2009, Dr. Schmelzer was awarded the Marin Drinov Medal of the Bulgarian Academy of Sciences for his longstanding cooperation with Bulgarian scientists, the present book being one of the results ofthisfruitful work.
Ivan S. Cutzow has been working at the Institute of Physical Chemistry of the Bulgarian Academy of Sciences (BAS), Sofia, since his graduation. In 1998, he founded there and headed till 2004 the Department of Amorphous Materials. He has been a Full Member of BAS since 2003. Simultaneously, he worked as a lecturer at universities in Bulgaria, Germany, the USA, and Brazil. Professor Gutzow's scientific interests focus on structure, thermodynamics and crystallization of glass-forming systems. He described nucleation in glasses as a non-stationary process, developed methods of nucleation catalysis and synthesis of glass-ceramics, and formulated glass transition models; based on thermodynamics of irreversible processes.
In 2002, Professor Gutzow was awarded the Alexander von Humboldt Research Prize (Germany).

Jürn W. P. Schmelzer and Ivan S. GutzowIvan S. Gutzow and Jürn W. P. SchmelzerJürn W. P. Schmelzer and Ivan S. GutzowJürn W. P. SchmelzerIvan S. Gutzow and Boris P. Petroff and Snejana V. Todorova and Jürn W. P. SchmelzerOleg V. MazurinAlexander I. PrivenIvan S. Gutzow and Snejana V. TodorovaIvan S. Gutzow and Jurn W. P. SchmelzerIvan S. Gutzow

Foreword	p. V
Preface	p. XVII
Contributors	p. XIX
1 Introduction	p. 1
2 Basic Properties and the Nature of Glasses: an Overview	p. 9
2.1 Glasses: First Attempts at a Classification	p. 9
2.2 Basic Thermodynamics	p. 14
2.2.1 The Fundamental Laws of Classical Thermodynamics and Consequences	p. 14
2.2.2 Thermodynamic Evolution Criteria, Stability Conditions and the Thermodynamic Description of NonequiUbrium States	p. 22
2.2.3 Phases and Phase Transitions: Gibbs's Phase Rule, Ehrenfest's Classification, and the Landau Theory	p. 26
2.3 Crystallization, Glass Transition and Devitrification of Glass-Forming Melts: an Overview of Experimental Results	p. 36
2.4 The Viscosity of Glass-Jorming Melts	p. 46
2.4.1 Temperature Dependence of the Viscosity	p. 46
2.4.2 Significance of Viscosity in the Glass Transition	p. 54
2.4.3 Molecular Properties Connected with the Viscosity	p. 57
2.5 Thermodynamic Properties of Glass-Forming Melts and Glasses: Overview on Experimental Results	p. 59
2.5.1 Heat Capacity	p. 59
2.5.2 Temperature Dependence of the Thermodynamic Functions: Simon's Approximation	p. 65
2.5.3 Further Methods of Determination of Caloric Properties of Glass-Forming Melts and Glasses	p. 74
2.5.4 Change of Mechanical, Optical and Electrical Properties in the Glass Transition Range	p. 76
2.6 Thermodynamic Nature of the Glassy State	p. 82
2.7 Concluding Remarks	p. 88
3 Generic Theory of Vitrification of Glass-Forming Melts	p. 91
3.1 Introduction	p. 91
3.2 Basic Ideas and Equations of the Thermodynamics of Irreversible Processes and Application to Vitrification and Devitrification Processes	p. 95
3.2.1 Basic Assumptions	p. 95
3.2.2 General Thermodynamic Dependencies	p. 96
3.2.3 Application to Vitrification and Devitrification Processes	p. 100
3.3 Properties of Glass-Forming Melts: Basic Model Assumptions	p. 103
3.3.1 Kinetics of Relaxation	p. 103
3.3.2 Thermodynamic Properties: Generalized Equation of State	p. 105
3.4 Kinetics of Nonisothermal Relaxation as a Model of the Glass Transition: Change of the Thermodynamic Functions in Cyclic Cooling-Heating Processes	p. 207
3.4.1 Description of the Cyclic Processes under Consideration	p. 107
3.4.2 Temperature Dependence of the Structural Order Parameter in Cyclic Cooling and Heating Processes	p. 108
3.4.3 Definition of the Glass Transition Temperature via the Structural Order Parameter: the Bartenev-Ritland Equation	p. 110
3.4.4 Structural Order Parameter and Entropy Production	p. 113
3.4.5 Temperature Dependence of Thermodynamic Potentials at Vitrification	p. 115
3.4.5.1 Configurational Contributions to Thermodynamic Functions	p. 115
3.4.5.2 Some Comments on the Value of the Configurational Entropy at Low Temperatures and on the Kauzmann Paradox	p. 112
3.4.6 Cyclic Heating-Cooling Processes: General Results	p. 113
3.5 The Prigogine-Defay Ratio	p. 115
3.5.1 Introduction	p. 115
3.5.2 Derivation	p. 117
3.5.2.1 General Results	p. 117
3.5.2.2 Quantitative Estimates	p. 133
3.5.2.3 An Alternative Approach: Jumps of the Thermodynamic Coefficients in Vitrification	p. 135
3.5.3 Comparison with Experimental Data	p. 137
3.5.3.1 The Prigogine-Defay Ratio	p. 137
3.5.3.2 Change of Young's Modulus in Vitrification	p. 140
3.5.4 Discussion	p. 142
3.6 Fictive (Internal) Pressure and Fictive Temperature as Structural Order Parameters	p. 143
3.6.1 Brief Overview	p. 143
3.6.2 Model-Independent Definition of Fictive (Internal) Pressure and Fictive Temperature	p. 146
3.7 On the Behavior of the Viscosity and Relaxation Time at Glass Transition	p. 149
3.8 On the Intensity of Thermal Fluctuations in Cooling and Heating of Glass-Forming Systems	p. 152
3.8.1 Introduction	p. 152
3.8.2 Glasses as Systems with Frozen-in Thermodynamic Fluctuations: Mueller and Porai-Koshits	p. 153
3.8.3 Final Remarks	p. 158
3.9 Results and Discussion	p. 158
4 Generic Approach to the Viscosity and the Relaxation Behavior of Glass-Forming Melts	p. 165
4.1 Introduction	p. 165
4.2 Pressure Dependence of the Viscosity	p. 166
4.2.1 Application of Free Volume Concepts	p. 166
4.2.2 A First Exception: Water	p. 169
4.2.3 Structural Changes of liquids and Their Effect on the Pressure Dependence of the Viscosity	p. 172
4.2.4 Discussion	p. 173
4.3 Relaxation Laws and Structural Order Parameter Approach	p. 174
4.3.1 Basic Equations: Aim of the Analysis	p. 174
4.3.2 Analysis	p. 175
4.3.3 Discussion	p. 177
5 Thermodynamics of Amorphous Solids, Glasses, and Disordered Crystals	p. 179
5.1 Introduction	p. 179
5.2 Experimental Evidence on Specific Heats and Change of Caloric Properties in Glasses and in Disordered Solids: Simon's Approximations	p. 182
5.3 Consequences of Simon's Classical Approximation: the ¿ G(T) Course	p. 194
5.4 Change of Kinetic Properties at T g and the Course of the Vitrification Kinetics	p. 195
5.5 The Frenkel-Kobeko Postulate in Terms of the Generic Phenomenological Approach and the Derivation of Kinetic and Thermodynamic Invariants	p. 198
5.6 Glass Transitions in Liquid Crystals and Frozen-in Orientational Modes in Crystals	p. 208
5.7 Spectroscopic Determination of Zero-Point Entropies in Molecular Disordered Crystals	p. 212
5.8 Entropy of Mixing in Disordered Crystals, in Spin Glasses and in Simple Oxide Glasses	p. 213
5.9 Generalized Experimental Evidence on the Caloric Properties of Typical Glass-Forming Systems	p. 215
5.10 General Conclusions	p. 219
6 Principles and Methods of Collection of Glass Property Data and Analysis of Data Reliability	p. 223
6.1 Introduction	p. 223
6.2 Principles of Data Collection and Presentation	p. 225
6.2.1 Main Principles of Data Collection	p. 225
6.2.2 Reasons to Use the Stated Principles of Data Collection	p. 228
6.2.3 Problems in Collecting the Largest Possible Amounts of Glass Property Data	p. 230
6.2.4 Main Principles of Data Presentation	p. 231
6.3 Analysis of Existing Data	p. 232
6.3.1 About the Reliability of Experimental Data	p. 232
6.3.2 Analysis of Data on Properties of Binary Systems	p. 233
6.3.2.1 General Features of the Analysis	p. 233
6.3.2.2 Some Factors Leading to Gross Errors	p. 237
6.3.2.3 Some Specific Examples of the Statistical Analysis of Experimental Data	p. 239
6.3.2.4 What is to Do if the Number of Sources Is Too Small?	p. 243
6.4 About the Reliability of the Authors of Publications	p. 246
6.4.1 The Moral Aspect of the Problem	p. 246
6.4.2 An Example of Systematically Unreliable Experimental Data	p. 247
6.4.3 Concluding Remarks	p. 251
6.5 General Conclusion	p. 253
7 Methods of Prediction of Glass Properties from Chemical Compositions	p. 255
7.1 Introduction: 120 Years in Search of a Silver Bullet	p. 255
7.2 Principle of Additivity of Glass Properties	p. 257
7.2.1 Simple Additive Formulae	p. 257
7.2.2 Additivity and Linearity	p. 258
7.2.3 Deviations from Linearity	p. 259
7.3 First Attempts of Simulation of Nonlinear Effects	p. 260
7.3.1 Winkelmann and Schott: Different Partial Coefficients for Different Composition Areas	p. 260
7.3.2 Gehlhoff and Thomas: Simulation of Small Effects	p. 260
7.3.3 Gilard and Dubrul: Polynomial Models	p. 262
7.4 Structural and Chemical Approaches	p. 264
7.4.1 Nonlinear Effects and Glass Structure	p. 264
7.4.2 Specifics of the Structural Approach to Glass Property Prediction	p. 266
7.4.3 First Trials of Application of Structural and Chemical Ideas to the Analysis of Glass Property Data	p. 267
7.4.4 Evaluation of the Contribution of Boron Oxide to Glass Properties	p. 267
7.4.4.1 Model by Huggins and Sun	p. 268
7.4.4.2 Models by Appen and Demkina	p. 268
7.4.5 Use of Other Structural Characteristics in Appen's and DemMha's Models	p. 271
7.4.6 Recalculation of the Chemical Compositions of Glasses	p. 272
7.4.7 Use of Atomic Characteristics in Glass and Melt Property Prediction Models	p. 278
7.4.8 Ab Initio and Other Direct Methods of Simulation of Glass Structure and Properties	p. 279
7.4.9 Conclusion	p. 280
7.5 Simulation of Viscosity of Oxide Glass-Forming Melts in the Twentieth Century	p. 280
7.5.1 Simulation of Viscosity as a Function of Chemical Composition and Temperature	p. 280
7.5.2 Approaches to Simulation of Concentration Dependencies of Viscosity Characteristics	p. 282
7.5.2.1 Linear Approach	p. 282
7.5.2.2 Approach of Mazurin: Summarizing of Effects	p. 283
7.5.2.3 Approach of Lakatos: Redefinition of Variables	p. 284
7.5.2.4 Polynomial Models	p. 284
7.5.3 Conclusion	p. 285
7.6 Simulation of Concentration Dependencies of Glass and Melt Propertie at the Beginning of the Twenty-First Century	p. 286
7.6.1 Global Glass Property Databases as a Catalyst for Development of Glass Property Models	p. 286
7.6.2 Linear and Polynomial Models	p. 286
7.6.3 Calculation of Liquidus Temperature: Neural Network Simulation	p. 28!
7.6.4 Approach of the Author	p. 291
7.6.4.1 Background	p. 291
7.6.4.2 Model	p. 292
7.6.4.3 Comparison with Previous Models	p. 294
7.6.4.4 Conclusion	p. 296
7.6.5 Fluegel: a Global Model as a Combination of Local Models	p. 296
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	p. 297
7.7 Simulation of Concentration Dependencies of Glass Properties in Nonoxide Systems	p. 299
7.8 Summary: Which Models Were Successful in the Past?	p. 301
7.9 Instead of a Conclusion: How to Catch a Bluebird	p. 306
8 Glasses as Accumulators of Free Energy and Other Unusual Applications of Glasses	p. 311
8.1 Introduction	p. 311
8.2 Ways to Describe the Glass Transition, the Properties of Glasses and of Defect Crystals: a Recapitulation	p. 313
8.3 Simon's Approximation, the Thermodynamic Structural Factor, the Kinetic Fragility of liquids and the Thermodynamic Properties of Defect Crystals	p. 318
8.4 The Energy, Accumulated in Glasses and Defect Crystals: Simple Geometric Estimates of Frozen-in Entropy and Enthalpy	p. 324
8.4.1 Enthalpy Accumulated at the Glass Transitions	p. 324
8.4.2 Free Energy Accumulated at the Glass Transition and in Defect Crystals	p. 327
8.5 Three Direct Ways to liberate the Energy, Frozen-in in Glasses: Crystallization, Dissolution and Chemical Reactions	p. 332
8.5.1 Solubility of Glasses and Its Significance in Crystal Synthesis and in the Thermodynamics of Vitreous States	p. 332
8.5.2 The Increased Reactivity of Glasses and the Kinetics of Chemical Reactions Involving Vitreous Solids	p. 339
8.6 The Fourth Possibility to Release the Energy of Glass: the Glass/Crystal Galvanic Cell	p. 340
8.7 Thermoelectric Driving Force at Metallic Glass/Crystal Contacts: the Seebeck and the Peltier Effects	p. 344
8.8 Unusual Methods of Formation of Glasses in Nature and Their Technical Significance
8.8.1 Introductory Remarks	p. 348
8.8.2 Agriglasses, Glasses as Nuclear Waste Forms and Possible Medical Applications of Dissolving Organic Glasses	p. 350
8.8.3 Glasses as Amorphous Battery Electrodes, as Battery Electrolytes and as Battery Membranes	p. 352
8.8.4 Photoeffects in Amorphous Solids and the Conductivity of Glasses	p. 353
8.9 Some Conclusions and a Discussion of Results and Possibilities	p. 354
9 Glasses and the Third Law of Thermodynamics	p. 357
9.1 Introduction	p. 357
9.2 A Brief Historical Recollection	p. 360
9.3 The Classical Thermodynamic Approach	p. 363
9.4 Nonequilibrium States and Classical Thermodynamic Treatment	p. 366
9.5 Zero-Point Entropy of Glasses and Defect Crystals: Calculations and Structural Dependence	p. 368
9.6 Thermodynamic and Kinetic Invariants of the Glass Transition	p. 369
9.7 Experimental Verification of the Existence of Frozen-in Entropies	p. 371
9.8 Principle of Thermodynamic Correspondence and Zero-Point Entropy Calculations	p. 376
9.9 A Recapitulation: the Third Principle of Thermodynamics in Nonequilibrium States	p. 377
10 On the Etymology of the Word "Glass" in European Languages and Some Final Remarks	p. 379
10.1 Introductory Remarks	p. 379
10.2 "Sirsu", "Shvistras", "Hyalos","Vitrum", "Glaes", "Staklo", "Cam"	p. 380
10.3 "Vitreous", "Glassy" and "Glasartig", "Vitro-crystalline"	p. 382
10.4 Glasses in Byzantium, in Western Europe, in Venice, in the Balkans and Several Other Issues	p. 384
10.5 Concluding Remarks	p. 385
References	p. 387
Index	p. 407

Available:*

On Order

Summary

Summary

Author Notes

Table of Contents