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Properties of Glass-Forming Melts

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Edition: 1st
Format: Hardcover
Pub. Date: 2005-05-12
Publisher(s): CRC Press
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Summary

This book presents state-of-the-art information concerning properties and processes involved in glass melts. Based upon contributions by renowned authors and scientists working with glass melt systems, Properties of Glass-Forming Melts is an excellent compilation of the current knowledge on property data, mechanisms, measurement techniques, and structure-related properties of glass-forming. The authors provide in-depth analyses of such topics as glass-melt density, thermal expansion, heat conductivity, and chemical activities. Each chapter combines fundamental concepts with a compilation of recent and reliable data that is essential in the modeling of glass melting, fining, conditioning, and forming. The book first discusses the glass-forming melts, thermodynamics, transport properties, and redox effects of glass. This provides a sound basis to the analysis of important properties of glass melts such as viscosity, surface tension, density, and heat capacity as well as more generalized subjects of heat transfer and gas solubility. A chapter on electrical properties provides a solid foundation for understanding glass melting via direct Joule heating of the melt. The examination of the corrosive nature of molten glasses will be of great interest to tank designers and operators. This unique handbook concludes with an overview of nuclear waste vitrification, a growing discipline that relies on current data and encourages research in glass melts. This book is an ideal starting place for future-generation glass scientists and an effective reference for scientists who require data on the behavior of viscous melts and for glass technologists who apply mathematical models simulating the melting and forming processes. Properties of Glass-Forming Melts offers a one-of-a-kind and valuable source of reliable data and insight by those with firsthand knowledge and experiences in this field.

Table of Contents

Chapter 1 Glass-Forming Melts 1(10)
L. David Pye
1.1 Introduction
1(1)
1.2 Purpose of This Chapter
1(1)
1.3 Historical Context
2(1)
1.2 Thermodynamic Description of Phases and Phase Transformation
2(1)
1.3 Conditions for Phase Stability and Phase Transformation
3(1)
1.4 Classification of Phase Transformations
3(1)
1.5 Phase Transformations in Glass-Forming Systems
3(2)
1.6 The Vitreous State
5(1)
1.7 Phase Separation
5(1)
1.8 Nucleation Theory
6(1)
1.9 Theory of Glass Formation
7(1)
1.10 Glass-Forming Melts
7(1)
1.11 The Structure of Glass-Forming Melts
8(1)
1.12 The Properties of Glass-Forming Melts
8(1)
References
8(3)
Chapter 2 Thermodynamic Properties 11(16)
Kaj H. Karlsson and Rainer Backman
2.1 Introduction
11(1)
2.2 Heat Capacity
12(1)
2.3 Liquidus Temperature
13(10)
2.3.1 Experimental Methods
14(1)
2.3.2 Polynomial Modeling
14(3)
2.3.2.1 EURAM Model
16(1)
3.2.2 Extended Babcock Model
17(3)
2.3.3 Thermodynamic Modeling
20(9)
2.3.3.1 Quasichemical Binary System
21(1)
2.3.3.2 Extension to Ternary Systems
22(1)
2.4 Future Development
23(2)
References
25(2)
Chapter 3 Redox Behavior and Electrochemical Behavior of Glass Melts 27(30)
Christian RĂĽssel
3.1 Introduction
27(2)
3.2 Theory
29(4)
3.2.1 Model: Ions in a Dielectric Continuum
29(1)
3.2.2 Thermodynamic
29(3)
3.2.3 Kinetics of Redox Reactions
32(1)
3.2.4 Diffusivity of Polyvalent Elements in Glass Melts
32(1)
3.3 Nomenclature, Definitions, Units
33(1)
3.4 Methods of Measurements
33(5)
3.4.1 Thermodynamic Measurements
33(4)
3.4.2 Measurement of Self Diffusion Coefficients
37(1)
3.4.3 Kinetic Measurements
37(1)
3.5 Known Results
38(14)
3.5.1 Effect of Experimental Parameters on the Redox Ratio
38(1)
3.5.1.1 Effect of the Oxygen Activity
38(1)
3.5.1.2 Effect of Temperature
38(1)
3.5.2 Occurrence of Redox Species and the Electrochemical Series in a Soda-Lime-Silica Glass Melt
38(2)
3.5.3 Effect of the Glass Composition on the Redox Ratio
40(7)
3.5.3.1 Two-Component Systems
42(1)
3.5.3.2 Multicomponent Systems
43(4)
3.5.3.3 Waste Glasses
47(1)
3.5.4 Redox Kinetics
47(5)
References
52(5)
Chapter 4 Transport Phenomena in Molten Glass: A Continuum Approach 57(18)
Rand A. Murnane and Robert R. Thomas
4.1. Introduction
57(1)
4.2 The Nature of Glass Viscosity
58(1)
4.3 Conservation of Mass
59(1)
4.4 Conservation of Momentum
60(1)
4.5 Equation of Mechanical Energy
61(1)
4.6 Energy Transport and Effective Thermal Conductivity
61(2)
4.7 Equation of Energy
63(1)
4.8 Dimensional Analysis
63(1)
4.9 Boundary-Layer Concerns
64(1)
4.10 Mass Transport Equations of Change
65(1)
4.11 Glass Process Applications
65(6)
4.11.1 Melter
65(3)
4.11.2 Refiner and Distributor
68(1)
4.11.3 Forehearth
68(2)
4.11.4 Bowls and Orifices
70(1)
4.12 Future Applications
71(1)
Glossary
71(1)
Operators
72(1)
References
73(2)
Chapter 5 Viscosity of Molten Glasses 75(68)
David Martlew
5.1 Theoretical Considerations and Definitions
75(11)
5.1.1 Introduction
75(1)
5.1.2 Definitions and Nomenclature
76(1)
5.1.3 The Objectives of This Chapter
77(1)
5.1.4 Viscosity and Temperature
78(1)
5.1.5 The Form of the Viscosity vs. Temperature Relation
79(3)
5.1.6 Fitting the VFT Equation to Experimental Data
82(2)
5.1.7 Non-Newtonian Behavior
84(1)
5.1.8 Estimation of Viscosity Characteristics from Composition
84(2)
5.2 Methods of Measurement
86(7)
5.2.1 Introduction
86(1)
5.2.2 Experimental Issues
87(1)
5.2.3 Rotational Viscometers
87(2)
5.2.4 Fiber Elongation Viscometers
89(2)
5.2.5 Bending Beam Viscometers
91(2)
5.3 Tables of Viscosity Data
93(45)
5.3.1 Single-Component Systems
93(3)
5.3.2 Two-Component Melts
96(25)
5.3.3 Three-Component Melts
121(10)
5.5.4 Complex and Commercial Glass Systems
131(2)
5.3.5 Calculation of Viscosity from Composition
133(5)
Acknowledgments
138(1)
References
138(5)
Chapter 6 The Surface Tension of Glass-Forming Melts 143(50)
Douglas A. Weirauch, Jr.
6.1 Introduction
144(10)
6.1.1 The Technological Significance of Glass Melt Surface Tension
144(1)
6.1.2 The Concept of Liquid Surface Tension
144(2)
6.1.3 Bonding and Surface Tension - A Comparison of Liquids
146(2)
6.1.4 The Effect of Temperature on Glass Surface Tension
148(1)
6.1.5 The Effect of Glass Composition on Surface Tension
149(4)
6.1.6 The Effect of Atmosphere on Surface Tension
153(1)
6.2 The Measurement of Surface Tension
154(9)
6.2.1 The Capillary Rise Method
155(1)
6.2.2 The Drop Weight Method
155(2)
6.2.3 The Fiber Elongation Method
157(1)
6.2.4 The Dipping Cylinder Method
157(1)
6.2.5 Maximum Bubble Pressure Technique
158(1)
6.2.6 Drop Shape Methods
159(3)
6.2.6.1 The Sessile Drop Technique
159(2)
6.2.6.2 The Pendant Drop Technique
161(1)
6.2.6.3 Image Analysis for Drop Shape Techniques
162(1)
6.2.7 A Comparison of Surface Tension Measurement Techniques
162(1)
6.3 Data for Selected Systems
163(1)
6.3.1 Data Compilations
163(1)
6.3.2 Outline of Sources of High-Temperature Surface Tension Data for Non-Metallic Liquids
164(1)
Acknowledgments
164(12)
References
176(17)
Chapter 7 Density of Glass Melts 193(34)
Oleg V. Mazurin
7.1 Introduction
193(1)
7.2 Methods of Measurements
194(4)
7.3 About the Information System
198(1)
7.4 Influence of Temperature
198(5)
7.4.1 Introduction
198(1)
7.4.2 Experimental Data
199(4)
7.5 Influence of Composition
203(15)
7.5.1 Introduction
203(1)
7.5.2 Density of Silicate Melts
204(7)
7.5.2.1 Density of Binary Sodium Silicate Melts
204(5)
7.5.2.2 Density of Mixed Alkali Silicate Melts
209(1)
7.5.2.3 Influence of Bivalent Oxides on Density of Alkali Silicate Melts
210(1)
7.5.2.4 Influence of Other Oxides on Density of Alkali Silicate Melts
210(1)
7.5.2.5 Densities of Alkali-Free Silicate Melts
211(1)
7.5.3 Density of Borate Melts
211(7)
7.5.4 Density of Various Types of Melts
218(1)
7.6 Calculation of Melt Densities
218(3)
References
221(6)
Chapter 8 Heat Capacity of Glass Melts 227(22)
Alexander I. Priven and Oleg V. Mazurin
8.1 Introduction
227(1)
8.2 Temperature Dependencies of Heat Capacity of Glass-Forming Substances
228(2)
8.3 General Characteristics of Existing Experimental Data on Heat Capacity of Glass Melts
230(1)
8.4 Composition Dependences of Heat Capacity of Glass Melts
230(4)
8.4.1 The Relativity of the Influence of Chemical Composition on Heat Capacity
230(1)
8.4.2 Prediction of Heat Capacity of Glass Melts from Chemical Composition
231(20)
8.4.2.1 Method by Stebbins et al
231(1)
8.4.2.2 Method by Gudovich and Primenko
231(1)
8.4.2.3 Method by Priven
231(2)
8.4.2.4 Practical Recommendations for Using the Methods
233(1)
8.5 Numerical Data
234(1)
Acknowledgment
234(11)
References
245(4)
Chapter 9 Heat Transfer in Glass-Forming Melts 249(46)
M.K. Choudhary and R.M. Potter
9.1 Introduction
250(1)
9.2 Formulation of Heat Transfer Problem in Glass Melts
251(37)
9.2.1 Differential Thermal Energy Balance
251(1)
9.2.2 Heat Transfer by Conduction
251(2)
9.2.3 Heat Transfer by Convection
253(1)
9.2.4 Heat Transfer by Radiation
254(13)
9.2.4.1 Planck's Law
254(1)
9.2.4.2 Stefan-Boltzmann Law
255(1)
9.2.4.3 Intensity of Radiation
255(2)
9.2.4.4 Surface Radiation
257(1)
9.2.4.5 Radiation in an Absorbing, Emitting Medium
257(10)
9.2.5 Thermal Conductivity of Glass
267(3)
9.2.5.1 Phonon Thermal Conductivity
267(1)
9.2.5.2 Calculation of Room Temperature Phonon Conductivity
268(2)
9.2.6 Photon thermal conductivity
270(36)
9.2.6.1 Introduction
270(1)
9.2.6.2 Calculation of Photon Thermal Conductivity from Spectral Data
271(2)
9.2.6.3 Glass Absorption Coefficients
273(3)
9.2.6.4 First Row Transition Metal Ion Absorption in Silicate Glass
276(6)
9.2.6.5 Hydroxyl Ion Absorption in Silicate Glass
282(1)
9.2.6.6 Calculation of Photon Thermal Conductivity
283(3)
9.2.6.7 Errors Associated with the Calculation
286(2)
9.3 Summary
288(1)
Acknowledgments
289(1)
References
289(6)
Chapter 10 Electrical Conductivity of Glass Melts 295(44)
Oleg V. Mazurin and Oleg A. Prokhorenko
10.1 Introduction
295(2)
10.2 Methods of Measurements
297(4)
10.3 The Influence of Composition of Electrical Resistivity of Glass-Forming Melts
301(5)
10.4 Method of Calculation of Electrical Resistivity of Glass-Forming Melts
306(2)
10.4.1 Calculation of Electrical Resistivity of Commercial Soda-Lime-Silica Melts
306(1)
10.4.2 Glasses of Sodium Borosilicate System
307(1)
10.5 Electrical Resistivity Data
308(27)
Acknowledgments
335(1)
References
335(4)
Chapter 11 How the Properties of Glass Melts Influence the Dissolution of Refractory Materials 339(52)
George A. Pecoraro
11.1 Introduction
340(16)
11.1.1 Thermodynamics of Glass Melt Corrosivity toward Refractories
342(1)
11.1.2 Refractory Dissolution: General Considerations
342(12)
11.1.2.1 Dissolution Kinetics Equations
343(1)
11.1.2.2 Kinetics of Solute Dissolution in Stagnant Liquid
344(1)
11.1.2.3 Temperature Dependency of Dissolution Kinetics
345(1)
11.1.2.4 Refractory Dissolution Kinetics under Natural Convection Conditions
346(2)
11.1.2.5 Kinetics of Refractory Dissolution Driven by Surface Tension Conditions
348(1)
11.1.2.6 Kinetics of Dissolution of Refractories by Upward and Downward Drilling Conditions
349(2)
11.1.2.7 Kinetics of Refractories Dissolution Driven by Forced Convection Conditions
351(1)
11.1.2.8 Kinetics of Dissolution of a Rotating Refractory Disc
352(1)
11.1.2.9 Summary of the Influence of Glass Melt Properties on Their Corrosivity toward Refractories
353(1)
11.1.3 Definition of Symbols
354(1)
11.1.4 Deviations of Commercial Refractory Materials from Idealized Solute Materials
354(2)
11.2 Refractory Dissolution Experimental Procedures
356(3)
11.2.1 Static Finger or Pencil Tests
356(1)
11.2.1 Static "T" Tests
357(1)
11.2.2 Small Refractory Basin Tests
357(1)
11.2.3 Dynamic Rotating Cylinder or Disc Tests
358(1)
11.3 Laboratory Studies of Dissolution of Refractory Materials in Glass Melts
359(29)
11.3.1 Studies of Refractory Dissolution in One-Component Glass Melts
359(5)
11.3.1.1 Quartz Glass Dissolution B2O3
359(2)
11.3.1.2 Tungsten Metal Corrosion in B2O3
361(3)
11.3.1.3 Al2O3 Dissolution in V2O5
364(1)
11.3.2 Studies of Refractory Dissolution in Two-Component Glass Melts
364(10)
11.3.2.1 Crystalline and Glass Quartz Dissolution in Na2O-B2O3
364(1)
11.3.2.2 Quartz Glass Dissolution in Na2O-SiO2
365(2)
11.3.2.3 Quartz Glass Dissolution in Na5O-SiO, and K5O-SiO
367(3)
11.3.2.4 Tungsten Metal Corrosion in Na2O-B2O3
370(4)
11.3.3 Studies of Refractory Dissolution in Three Component Glass Melts
374(8)
11.3.3.1 Sapphire and Alumina and Alumino-Silicate Refractories Dissolution in CaO-Al2O3-SiO2
375(4)
11.3.2.2 Quartz Glass Dissolution in Na2O-CaO-SiO2, K2O-PbO-SiO2 Na2O-B2OgSiO2 and CaO-Al203-SiO2
379(1)
11.3.3.3 Al2O3 and ZrO2 and Fused AZS Dissolution in Alkali-Barium-Silicate
380(2)
11.3.3.4 Upward Drilling of High Al2O3, Corundum, SnO2 and Fusion Cast AZS and ACZS Refractories in Soda-Alumina-Lime-Silica Glass Melts
382(1)
11.3.4 Applications of Dissolution Kinetic Principles to Refractory Systems Design-Refractory Chemistry
382(25)
11.3.4.1 Basin Wall Refractory Considerations
384(2)
11.3.4.2 Throats
386(1)
11.3.4.3 Bottom Paving
386(1)
11.3.4.4 Refractory Metals
387(1)
References
388(3)
Chapter 12 Nuclear Waste Glasses 391(14)
John D. Vienna
12.1 Introduction
391(1)
12.2 Key Nuclear Waste-Glass Properties
392(3)
12.3 Glass Property-Composition Relationships
395(3)
12.4 Summary
398(1)
References
398(7)
Chapter 13 Solubility of Gases in Glass Melts 405(78)
Fritz W. Krämer
13.1 Introduction
406(1)
13.2 Physical Solubility
407(4)
13.2.1 Dependence on Glass Composition
408(1)
13.2.2 Dependence on Temperature
409(1)
13.2.3 Dependence on Pressure
410(1)
13.3 Chemical Solubility
411(2)
13.3.1 Dependence on Glass Composition
411(1)
13.3.2 Dependence on Temperature
412(1)
13.3.3 Dependence on Pressure
412(1)
13.4 Solubilities
413(8)
13.4.1 Hydrogen and Water
413(1)
13.4.2 Carbon Dioxide
414(1)
13.4.3 Sulfur
414(3)
13.4.4 Oxygen
417(3)
13.4.5 Nitrogen
420(1)
13.5 Calculation of Gas Solubility
421(1)
13.6 Measurement of Gas Solubility
421(4)
13.6.1 Saturation of Melts with Gases
421(1)
13.6.2 Gas Detection
422(3)
13.6.2.1 Extraction and Gas Analysis
422(1)
13.6.2.2 Physical Measuring Methods
423(2)
13.7 Application of Gas Solubility
425(4)
13.7.1 Glass Melt Structure
425(1)
13.7.2 Glass Melting Process
426(2)
13.7.2.1 Melting
426(1)
13.7.2.2 Fining and Conditioning
426(1)
13.7.2.3 Foaming and Reboil
427(1)
13.7.3 Bubble Defect Trouble Shooting
428(1)
13.8 Solubility Data
429(46)
References
475(8)
Index 483

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