Society of Glass Technology

The second edition of Arun Varshneya’s Fundamentals of Inorganic Glasses has been published by the Society of Glass Technology. The introductory chapter looks at a brief history of glasses and glass making. 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; and oxyhalide, oxynitride, and oxycarbide glasses. The chapter finishes with a brief note on glasses found in nature.
The remaining chapters are on: Fundamentals of the Glassy State; Glass Formation Principles; Glass Microstructure: Phase Separation and Liquid Immiscibility; Glass Compositions and Structures; Composition–Structure–Property Relationship Principles; Density and Molar Volume; Elastic Properties and Microhardness of Glass; The Viscosity and Surface Tension of Glass; Thermal Expansion of Glass; Heat Capacity of Glass; Thermal Conductivity of Glass; Glass Transition Range Behavior; Permeation, Diffusion and Ionic Conduction in Glass; Dielectric Properties; Electronic Conduction; Chemical Durability; Strength and Toughness; Optical Properties; and Fundamentals of Inorganic Glass Making. There are also Appendices on Elements of Linear Elasticity; the SciGlass Database by O. V. Mazurin and A. I. Priven (including a student version on CD); Who wants to earn an A? (More questions and answers in addition to those at the end of each chapter.); Units, Conversion and General Data.

Published September 2006, 234 mm × 156 mm, 704 pages with some colour but mostly black and white illustrations, ISBN 0-900682-51-5 paperback, ISBN 0-900682-53-1 (hardback).
Hardback £60 (£45 SGT members, journal subscribers and students)
Paperback £45 (£35 SGT members, journal subscribers and students)

Contents
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Preface to the first edition			v
Preface to the second edition			vii

CHAPTER 1
Introduction			1
1.1		Brief History	1
1.2		Glass Families of Interest	2
1.2.1		Vitreous Silica	2
1.2.2		Soda–Lime Glass	4
1.2.3		Borosilicate Glass	4
1.2.4		Lead Silicate Glass	4
1.2.5		Aluminosilicate Glass	6
1.2.6		Other Silica-Based Oxide Glasses	6
1.2.7		Other Non-Silica-Based Oxide Glasses	7
1.2.8		Halide Glasses	7
1.2.9		Amorphous Semiconductors	8
1.2.10		Chalcogenide and Chalcohalide Glasses	9
1.2.11		Glassy Metals	10
1.2.12		Glass-Like Carbon	11
1.2.13		Oxyhalide, Oxynitride, and Oxycarbide Glasses	11
1.3		A Brief Note on Glasses Found in Nature	12
Summary			14
Exercises			15
References			15

CHAPTER 2
Fundamentals of the Glassy State			17
2.1		What is Glass?	17
2.2		The V–T Diagram	18
2.3		Pair Correlation Function and Radial Distribution Function	21
2.4		Anomalies in the V–T Diagram	29
Summary			31
Exercises			32
References			32

CHAPTER 3
Glass Formation Principles				35
3.1	Structural Theories of Glass Formation			36
3.1.1	Zachariasen’s Random Network Theory			37
3.1.2	Sun’s Single Bond Strength Criterion			40
3.1.3	Phillips’ Topological Constraints Hypothesis			43
3.2	Russian Workers’ Criticism of Zachariasen’s Hypothesis			48
3.3	The Kinetic Theory of Glass Formation			52
3.3.1	The Nucleation Rate			52
3.3.2	Crystal Growth Rate			58
3.3.3	T–T–T Diagram			63
Summary				69
Exercises				70
References				71

CHAPTER 4
Glass Microstructure: Phase Separation and Liquid Immiscibility				73
4.1		Thermodynamics of Mixing		74
4.2		More Formal Analysis of Phase Separation		82
4.3		Electron Microscopy to Observe Phase Separation in Glass		87
4.4		Observations of Phase Separation in Glass		88
4.5		Observations of Controlled–Crystallization in Glass (Glass-Ceramics)		94
Summary				97
Exercises				98
References				99

CHAPTER 5
Glass Compositions and Structures				101
5.1		Presentation of Glass Formulæ		101
5.2		Silica Glass		102
5.3		Boric Oxide Glass		110
5.4		Alkali Silicate Glasses		113
5.5		Alkali-Alkaline Earth-Silicate Glasses		118
5.6		Alkali Borate Glasses		120
5.7		The Boron Anomaly		121
5.8		Alkali Borosilicate Glasses		125
5.9		Alkali Aluminosilicate Glasses		129
5.10		Lead, Bismuth, Thallium Silicate or Borate Glasses		131
5.11		Phosphate Glasses		132
5.12		Other Oxide Glasses		137
5.13		Amorphous Silicon and Germanium		139
5.14		Glassy Metals		144
5.15		Chalcogenide and Chalcohalide Glasses		148
5.16		Halides and Heavy Metal Fluoride Glasses (HMFG)		155
Summary				159
Exercises				160
References				161

CHAPTER 6
Composition–Structure–Property Relationship Principles				165
6.1 General Principles				165
6.2 Additivity Relationships				168
Summary				170
References				170

CHAPTER 7
Density and Molar Volume				173

7.1	Definitions		173
7.2	Methods of Measurement		174
7.3	Dependence upon Cooling Rate, Temperature and Composition		175
7.4	Densification of Glasses by High Pressure or Irradiation		179
7.5	Calculation of Density		181
Summary			183
Exercises			183
References			184

CHAPTER 8
Elastic Properties and Microhardness of Glass			187
8.1	Introduction		187
8.2	Elastic Properties of Glass		188
8.2.1	The Terminology of Elasticity		188
8.2.2	Methods of Measuring Elastic Moduli		190
8.2.3	Elastic Moduli Versus Glass Composition		194
8.2.4	Temperature and Pressure Dependence of Elastic Moduli		198
8.2.5	The Atomistic Approach to Elastic Behavior		199
8.3	Microhardness of Glass		202
8.3.1	Microhardness and Its Measurement		202
8.3.2	Microhardness vs. Glass Composition		208
Summary			209
Exercises			210
References			210

CHAPTER 9
The Viscosity and Surface Tension of Glass			213
9.1	Introduction		213
9.2	Viscosity–Temperature Dependence		216
9.3	Viscosity Reference Points		220
9.4	Measurement of Viscosity		221
9.5	Viscosity vs. Composition and Temperature Data		226
9.6	Viscosity of Common Soda–Lime Silicate Glass at Room
	Temperature (The “Urban Legend”)		234
9.7	Non-Newtonian Viscosity		236
9.8	Volume Viscosity		240
9.9	Surface Tension of Glass		241
9.9.1	Methods of Measurement		241
9.9.2	Dependence of Surface Tension on Composition		243
Summary			243
Exercises			245
References			246

CHAPTER 10
Thermal Expansion of Glass			249
10.1	Introduction		249
10.2	Definitions		249
10.3	Methods of Thermal Expansion Measurement		250
10.4	Thermal Expansion vs. Composition and Temperature		253
10.5	Concepts of Glass Expansion		257
10.6	Thermal Stresses and the Thermal Shock Resistance		258
Summary			262
Exercises			262
References			264

Chapter 11
Heat Capacity of Glass			265
11.1	Introduction		265
11.2	Measurement of Heat Capacity		266
11.3	Composition Dependence		266
11.4	Temperature Dependence		267
Summary			272
Exercises			272
References			272

CHAPTER 12
Thermal Conductivity of Glass			273
12.1	Introduction		273
12.2	Measurement of Thermal Conductivity	274
12.3	Composition and Temperature Dependence	276
Summary		279
Exercises		279
References		279

CHAPTER 13
Glass Transition Range Behavior		281
13.1	Introduction	281
13.2	Viscoelastic Properties of Glass	283
13.2.1	About Relaxation	284
13.2.2	Maxwell Element	289
13.2.3	Voigt–Kelvin Element	292
13.2.4	Delayed elasticity	293
13.3	Structural Relaxation due to Temperature Change	294
13.4	Viscosity–Free Volume Theories of Glass Transition	296
13.5	Thermodynamics of the Glass Transition	302
13.5.1	Thermodynamic Orders of Phase Transition	310
13.5.2	Adam–Gibbs Model of Cooperative Relaxations
	(Contributed by John C. Mauro)	315
13.5.3	Stillinger Model of Inherent Structures
	(Contributed by John C. Mauro)	318
13.5.4	Configurational Contributions to Physical Properties at the Glass Transition	324
13.6	Kinetics of the Glass Transition	328
13.6.1	‘Watching’ the Relaxation (Concept of the Deborah Number)	328
13.6.2	Tool’s Fictive Temperature Theory	328
13.6.3	About the DTA and DSC of the Glass Transition	332

13.6.4		Difficulties with Tool’s Single Tf Concept	334
13.6.5		Narayanaswamy’s Model of Structural Relaxation	339
13.6.6		Description of the Crossover Experiment in Terms of
		Narayanaswamy’s Model for Relaxation	341
13.6.7		Tiling Model (Contributed by John C. Mauro)	343
13.7		Propeties Data in the Tg Range	346
13.8		Development of Permanent Stresses in Glass by Cooling Through the Transition Range
			352
13.9		Concepts of Annealing and Tempering	357
		Summary	363
Exercises			366
References			367

CHAPTER 14
Permeation, Diffusion and Ionic Conduction in Glass				371
14.1	Introduction			371
14.2	More on the Atomic Theory of Diffusion and Electrical
	Conduction			376
14.2.1	Mechanisms of Diffusion			376
14.2.2	Correlation Effects			378
14.2.3	Haven Ratio			379
14.2.4	Isotope Effect			379
14.2.5	Temperature Dependence of Diffusion and Electrical
	Conduction			380
14.3	Measurement of Gas Permeability			381
14.4	Measurement of Diffusion Coefficients			382
14.4.1	Self-Diffusion Coefficients			382
14.4.2	Measurement of Chemical Diffusion Coefficients			384
14.5	Measurement of Electrical Conductivity			385
14.6	Data on Permeability and Molecular Diffusion of Gases
	in Glass			388
14.7	Data on Ionic Diffusion and Electrical Conduction in Glass			390
14.8	Some Aspects of Diffusion and Conduction Phenomena			397
14.8.1	Ion Exchange			397
14.8.2	Multicomponent Diffusion			402
14.8.3	Fast Ion Conduction			404
14.8.4	Anionic Conduction			405
Summary				407
Exercises				408
References				409

CHAPTER 15
Dielectric Properties				413
15.1	Introduction			413
15.2	Measurement of Dielectric Properties			422
15.3	Data on Dielectric Properties and AC Conduction in Glass			424
Summary				429
References				430

CHAPTER 16
Electronic Conduction				433
16.1	Introduction			433
16.2	Concepts of Electronic Conduction in Amorphous Solids			434
16.3	Defects in Amorphous Solids and Their Management			448
16.4	Photoconductivity, Photoluminescence & Xerography			452
16.5	Photovoltaics and Solar Cell			456
16.6	Switching and Computer Memory Device			458
References				461

CHAPTER 17
Chemical Durability				463
17.1	Introduction			463
17.2	Mechanisms of Durability and Weatherability			464
17.3	Measurement of Chemical Durability			465
17.4	Data on Chemical Durability			466
17.5	Methods of Improving Chemical Durability			473
Summary				474
Exercises				475
References				475

CHAPTER 18
Strength and Toughness				477
18.1	Introduction			477
18.2	Theoretical Strength of a flawless Brittle Solid			478
18.3	Strength of a Flawed Brittle Solid: Griffith’s Analysis			480
18.4	Elementary Fracture Mechanics Concepts			482
18.5	Glass Fatigue			484
18.6	Mechanism of Strength Based upon Slow Crack Growth			492
18.7	Elementary Fractographic Analysis			494
18.8	Fracture Statistics			500
18.9	Life Prediction			504
18.10	Experimental Measurement of Glass Strength and
	Fracture Toughness			506
18.11	Data on Strength and Fatigue Parameters			511
18.12	Strengthening and Toughening			513
Summary				520
Exercises				521
References				522

CHAPTER 19
Optical Properties				525
19.1 Introduction				525
19.2 Some Theoretical Concepts				527
19.2.1	Dispersion			527
19.2.2	Scattering			531
19.2.3	Absorption in the Visible Region (Colors in Glass)			533
19.2.4	Absorption in the UV			545

19.2.5	Absorption in the IR	548
19.2.6	Photoelastic Properties	550
19.2.7	Anomalous Birefringence	555
19.3	Measurement of Optical Properties	556
19.4	Data on Optical Properties	557
19.5	Special Applications	564
19.5.1	Photosensitive Glasses	564
19.5.2	Nonlinear Optics	565
19.5.3	Glass as a Laser Host	569
19.5.4	Fiber Optics	571
19.5.5	Coatings on Glass to Improve Optical Quality	577
Summary		579
Exercise		580
References		581
CHAPTER 20
Fundamentals of Inorganic Glass Making		583
20.1	Laboratory melting of glasses	583
20.1.1	Oxide Glasses	583
20.1.2	Chalcogenide Glasses	588
20.1.3	Heavy Metal Fluoride Glasses (HMFG)	589
20.1.4	Thioborates	589
20.2	Continuous Melting of Glass	590
20.3	Non-Fusion Based Techniques of Glass Making	597
20.3.1	Glass Making Directly from the Solid State	598
20.3.2	Glass Making Directly from the Gaseous State	599
20.3.3	Glass Making via the Sol-Gel Process	600
20.3.3.1	Introduction	600
20.3.3.2	Raw Materials	602
20.3.3.3

The objects of the Society of Glass Technology are to encourage and advance the study of the history, art, science, design, manufacture, after treatment, distribution and end use of glass of any and every kind. These aims are furthered by meetings, publications, the maintenance of a library and the promotion of association with other interested persons and organisations.