Ian W Donald
Waste Immobilization in Glass and Ceramic Based Hosts
Radioactive, Toxic and Hazardous Wastes
Ian W Donald
Waste Immobilization in Glass and Ceramic Based Hosts
Radioactive, Toxic and Hazardous Wastes
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The problem of what to do with waste materials both radioactive and, more recently, non-radioactive, is an increasingly important environmental and political issue. Radioactive waste management practices vary worldwide but currently the most common method is to turn highly radioactive waste into a vitrified product, in order to render it passively safe before disposal. With mounting pressure on land-fill sites, and increased environmental concern, the issue of toxic and hazardous waste management must also be properly addressed. This book brings together all aspects of waste immobilization,…mehr
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The problem of what to do with waste materials both radioactive and, more recently, non-radioactive, is an increasingly important environmental and political issue. Radioactive waste management practices vary worldwide but currently the most common method is to turn highly radioactive waste into a vitrified product, in order to render it passively safe before disposal. With mounting pressure on land-fill sites, and increased environmental concern, the issue of toxic and hazardous waste management must also be properly addressed. This book brings together all aspects of waste immobilization, draws comparisons between the different types of wastes and treatments, and outlines where lessons learnt by the nuclear industry may be usefully applied in the treatment of non-radioactive wastes. A wide range of topics is covered, including vitrification techniques, ceramic and glass-ceramic wasteforms, novel hosts, toxic and hazardous wastes, influence of microbial activity, and the treatment of new generation wastestreams. Waste Immobilization in Glass and Ceramic Based Hosts provides an up-to-date reference source at this critical time, when the need for low carbon energy sources has brought nuclear power back to the forefront, and non-radioactive toxic and hazardous wastes pose an increasing threat to the environment.
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Produktdetails
- Produktdetails
- Verlag: Wiley
- Seitenzahl: 526
- Erscheinungstermin: 24. Mai 2010
- Englisch
- Abmessung: 249mm x 173mm x 33mm
- Gewicht: 1016g
- ISBN-13: 9781444319378
- ISBN-10: 144431937X
- Artikelnr.: 31691586
- Verlag: Wiley
- Seitenzahl: 526
- Erscheinungstermin: 24. Mai 2010
- Englisch
- Abmessung: 249mm x 173mm x 33mm
- Gewicht: 1016g
- ISBN-13: 9781444319378
- ISBN-10: 144431937X
- Artikelnr.: 31691586
Ian Donald, Atomic Weapons Establishment (AWE), UK. Ian Donald has specialised in various areas of glass technology for over 30 years. After receiving a PhD from the University of Leeds? in 1973 he continued with postdoctoral studies at the University of Warwick. This was followed by research on metallic glasses at the University of Sheffield.?Subsequently, Dr. Donald joined the Atomic Weapons Research Establishment (later to become the Atomic Weapons Establishment,?ARE) in 1981. He was promoted to the grade of Distinguished Scientist in 2002, and was awarded the John Challens Medal for Lifetime Achievement by AWE in 2006. His work at AWE?has included a diverse range of topics and has covered speculative research on a variety of glass, ceramic and glass-ceramic materials, as well as component development programmes including the research and development of chemically strengthened glasses with frangible (command-break) properties, glass-coated microwire, glass- and glass-ceramic-to-metal seal devices and coatings, glass and glass-ceramic matrix composites and, over the last 14 years, glasses and ceramics as hosts for immobilizing radioactive wastes. Over this period, Dr Donald has presented many papers at international conferences on waste-related topics. Dr Donald is an elected member of national and international technical committees on glass including the Basic Science and Technology Committee of the Society of Glass Technology together with the Committee on Nucleation, Crystallization and Glass-Ceramics of the International Commission on Glass, representing the UK. He is also a Fellow of both the Institute of Materials, Minerals and Mining and the Society of Glass Technology, is an Associate Member of the Institute of Physics, has served time as a Visiting Professor at the University of Reading, is author or co-author of over 100 technical publications in the open literature, including a book written at the invitation of the Society of Glass Technology on Glass-to-Metal Seals, and is a member of the EPSRC Peer Review College.
Preface page xi
Acknowledgements xiii
List of Abbreviations xv
1. Introduction 1
1.1 Categories of Waste and Waste Generation in the Modern World 1
1.1.1 Radioactive Wastes from Nuclear Power and Defence Operations 2
1.1.2 Toxic and Hazardous Wastes 7
1.1.3 Other Sources of Waste Material 9
1.2 General Disposal Options 11
1.3 Radiation Issues 19
1.4 Waste Disposal and the Oklo Natural Nuclear Reactors 21
1.5 Nuclear Accidents and the Lessons Learnt 25
References 31
2. Materials Toxicity and Biological Effects 37
2.1 Metals 38
2.1.1 Beryllium, Barium and Radium 38
2.1.2 Vanadium 39
2.1.3 Chromium, Molybdenum and Tungsten 40
2.1.4 Manganese, Technetium and Rhenium 40
2.1.5 Platinum-Group Metals 41
2.1.6 Nickel 42
2.1.7 Copper, Silver and Gold 42
2.1.8 Zinc, Cadmium and Mercury 43
2.1.9 Aluminium and Thallium 45
2.1.10 Tin and Lead 46
2.1.11 Arsenic, Antimony and Bismuth 48
2.1.12 Selenium, Tellurium and Polonium 49
2.1.13 Thorium, Uranium, Neptunium, Plutonium and Americium 50
2.2 Compounds 51
2.3 Asbestos 51
References 55
3. Glass and Ceramic Based Systems and General Processing Methods 57
3.1 Glass Formation 58
3.1.1 Glass-Forming Ability 58
3.1.2 Thermal Stability 61
3.2 Types of Glass 61
3.2.1 Silicate and Borosilicate Glasses 61
3.2.2 Phosphate Glasses 61
3.2.3 Rare Earth Oxide Glasses 62
3.2.4 Alternative Glasses 62
3.3 Ceramics 62
3.4 Glass-Ceramics 63
3.5 Glass and Ceramic Based Composite Systems 68
3.6 Processing of Glass and Ceramic Materials 68
3.6.1 Melting and Vitrifi cation 69
3.6.2 Powder Processing and Sintering 69
3.6.3 Hot Pressing 69
3.6.4 Sol-Gel Processing 70
3.6.5 Self-Propagating High Temperature Synthesis 70
3.6.6 Microwave Processing 70
References 71
4. Materials Characterization 75
4.1 Chemical Analysis 75
4.2 Thermal Analysis 76
4.3 Structural Analysis 78
4.3.1 Optical and Electron Microscopy 78
4.3.2 Energy Dispersive Spectroscopy 79
4.3.3 X-ray and Neutron Diffraction 79
4.3.4 Infra-Red and Raman Spectroscopy 80
4.3.5 Mössbauer Spectroscopy 80
4.3.6 Nuclear Magnetic Resonance 80
4.4 Mechanical Properties 81
4.4.1 Fracture Mechanics 81
4.4.2 Flexural Strength of Materials 83
4.4.3 Lifetime Behaviour 83
4.5 Chemical Durability and Standardized Tests 87
4.6 Radiation Stability 92
4.7 Other Properties Relevant to Wasteforms 94
4.8 Use of Nonradioactive Surrogates 94
References 96
5. Radioactive Wastes 101
5.1 Sources and Waste Stream Compositions 101
5.1.1 Nuclear Reactor Spent Fuel Wastes 102
5.1.2 Defence Wastes 107
5.1.3 Surplus Materials 108
5.1.4 Special or Unusual Categories of Radioactive Waste 109
5.2 General Immobilization Options 111
References 115
6. Immobilization by Vitrification 121
6.1 Vitrification History and the Advancement of Melter Design 121
6.1.1 Pot Processes 122
6.1.2 Continuous Melting by Induction Furnace 124
6.1.3 Joule-Heated Ceramic Melters 128
6.1.4 Cold Crucible Induction Melters 131
6.1.5 Plasma Arc/Torch Melters 135
6.1.6 Microwave Processing 138
6.1.7 In situ Melting 138
6.1.8 Bulk Vitrification 138
6.1.9 Alternative Melting Techniques 138
6.1.10 Vitrification Incidents and the Lessons that have been Learnt 140
6.2 Difficult Waste Constituents 144
6.2.1 Molybdenum and Caesium 144
6.2.2 Platinum Group Metals 147
6.2.3 Technetium 149
6.2.4 Chromium, Nickel and Iron 150
6.2.5 Halides 150
6.2.6 Sulphates 150
6.2.7 Phosphates 151
6.3 Effect of Specific Batch Additives on Melting Performance 151
6.4 Types of Glass and Candidate Glass Requirements 151
6.4.1 Silicate and Borosilicate Glass 151
6.4.2 Phosphate Glasses 163
6.4.3 Rare Earth Oxide Glasses 165
6.4.4 Alternative Glasses 166
6.5 Glass-Forming Ability 168
6.6 Alternative Methods for Producing Glassy Wasteforms 169
6.6.1 Sintered and Porous Glass 169
6.6.2 Hot-Pressed Glass 171
6.6.3 Microwave Sintering 175
6.6.4 Self-Sustaining Vitrification 176
6.6.5 Plasma Torch Incineration and Vitrification 177
References 177
7. Immobilization of Radioactive Materials as a Ceramic Wasteform 185
7.1 Titanate and Zirconate Ceramics 185
7.2 Phosphate Ceramics 203
7.3 Aluminosilicate Ceramics 207
7.4 Alternative Ceramics 209
7.5 Cement Based Systems 211
References 212
8. Immobilization of Radioactive Materials as a Glass-Ceramic Wasteform 221
8.1 Barium Aluminosilicate Glass-Ceramics 222
8.2 Barium Titanium Silicate Glass-Ceramics 222
8.3 Calcium Magnesium Silicate Glass-Ceramics 222
8.4 Calcium Titanium Silicate Glass-Ceramics 227
8.5 Basaltic Glass-Ceramics 228
8.6 Zirconolite Based Glass-Ceramics 230
8.7 Alternative Silicate Based Glass-Ceramics 234
8.8 Phosphate Based Glass-Ceramics 234
References 237
9. Novel Hosts for the Immobilization of Special or Unusual Categories of
Radioactive Wastes 241
9.1 Silicate Glasses 241
9.2 Phosphate Glasses 246
9.3 Alternative Vitrification Routes 249
9.4 Ceramic-Based Hosts 251
9.5 Glass-Encapsulated Composite and Hybrid Systems 253
9.6 Oxynitride Glasses 259
9.7 Plutonium Disposition 260
References 266
10. Properties of Radioactive Wasteforms 275
10.1 Thermal Stability 275
10.2 Chemical Durability 276
10.2.1 General Principles of Glass Durability 277
10.2.2 Durability of Silicate Based Glasses in Water 282
10.2.3 Durability of Silicate Based Glasses in Groundwaters and Repository
Environments 291
10.2.4 Durability of Phosphate Based Glasses 296
10.2.5 Lessons to be Learnt from Archaeological Glasses 297
10.2.6 Ceramic Durability 301
10.2.7 Glass-Ceramic Durability 308
10.2.8 Durability of Glass-Encapsulated Ceramic Hybrid Wasteforms 309
10.2.9 Influence of Colloids 310
10.3 Radiation Stability 311
10.3.1 Glass Stability 311
10.3.2 Ceramic Stability 316
10.3.3 Glass-Encapsulated Ceramic Hybrid Stability 323
10.4 Natural Analogues 324
10.5 Mechanical Properties 328
10.6 Alternative Properties 333
References 334
11. Structural and Modelling Studies 343
11.1 Structural Studies 343
11.1.1 Vitreous Wasteforms 343
11.1.2 Ceramic Wasteforms 349
11.2 Modelling Studies 350
11.2.1 Modelling Techniques 350
11.2.2 Vitreous Wasteforms 350
11.2.3 Ceramic Wasteforms 356
References 357
12. Sources and Compositions of Nonradioactive Toxic and Hazardous Wastes,
and Common Disposal Routes 361
12.1 Incinerator Wastes 365
12.2 Sewage and Dredging Sludges 368
12.3 Zinc Hydrometallurgical and Red Mud Wastes 370
12.4 Blast Furnace Slags and Electric Arc Furnace Dusts 370
12.5 Alternative Metallurgical Wastes and Slags 370
12.6 Metal Finishing and Plating Wastes 371
12.7 Coal Ash and Fly Ash from Thermal Power Stations 374
12.8 Cement Dust and Clay-Refining Wastes 379
12.9 Tannery Industry Wastes 379
12.10 Asbestos 380
12.11 Medical Wastes 380
12.12 Electrical and Electronic Wastes 383
12.13 Alternative Wastes 384
References 385
13. Vitrification of Nonradioactive Toxic and Hazardous Wastes 389
13.1 Incinerator Wastes 392
13.2 Sewage and Dredging Sludges 397
13.3 Zinc Hydrometallurgical and Red Mud Wastes 398
13.4 Blast Furnace Slags and Electric Arc Furnace Dusts 399
13.5 Alternative Metallurgical Wastes and Slags 401
13.6 Metal Finishing and Plating Wastes 403
13.7 Coal Ash and Fly Ash from Thermal Power Stations 404
13.8 Cement Dust, Clay-Refining and Tannery Industry Wastes 406
13.9 Asbestos 406
13.10 Medical Waste 407
13.11 Electrical and Electronic Wastes 408
13.12 Alternative Wastes 408
13.13 Mixed Nonradioactive Hazardous Wastes 409
13.14 Glass-Ceramics for Nonradioactive Waste Immobilization 410
13.15 Commercial Hazardous Waste Vitrification Facilities 418
References 420
14. Alternative Treatment Processes, and Characterization, Properties and
Applications of Nonradioactive Wasteforms 429
14.1 Alternatives to Vitrification 429
14.2 Use of Alternative Waste Sources to Prepare New Materials 435
14.3 Use of Waste Glass to Prepare New Materials 435
14.4 Characterization, Properties and Applications of Nonradioactive
Wasteforms 436
14.4.1 Mechanical Properties 436
14.4.2 Chemical Durability 440
14.4.3 Structural and Modelling Studies 441
14.4.4 Use of Less Hazardous or Nontoxic Surrogates 442
14.5 Applications 444
References 445
15. Influence of Organic, Micro-Organism and Microbial Activity on
Wasteform Integrity 451
15.1 Micro-Organism Activity and Transport Mechanisms 452
15.2 Repository Environments 454
15.3 Repository Analogues 457
15.4 Wasteforms 458
References 462
16. Concluding Remarks, Comparisons between Radioactive and Nonradioactive
Waste Immobilization, and Outlook for the Future 465
16.1 Mixed Radioactive and Nonradioactive Wastes 465
16.2 System and Wasteform Comparisons 467
16.2.1 Treatment Facilities 467
16.2.2 Wasteforms 469
16.3 Immediate and Short-Term Future Outlook 473
16.4 Medium and Longer Term Future Outlook 474
16.4.1 Generation IV Nuclear Energy Systems 474
16.4.2 Element Partitioning and Transmutation 478
16.5 Choosing a Wasteform 479
16.5.1 Wasteforms Studied in the Past and Short-Term Future Direction 479
16.5.2 Alternative Wasteforms and Longer Term Future Direction 484
16.6 Wasteform Characterization 486
16.7 Standards, Regulatory Requirements, and Performance Assessments 487
16.8 Overall Conclusions 489
References 490
Index 493
Acknowledgements xiii
List of Abbreviations xv
1. Introduction 1
1.1 Categories of Waste and Waste Generation in the Modern World 1
1.1.1 Radioactive Wastes from Nuclear Power and Defence Operations 2
1.1.2 Toxic and Hazardous Wastes 7
1.1.3 Other Sources of Waste Material 9
1.2 General Disposal Options 11
1.3 Radiation Issues 19
1.4 Waste Disposal and the Oklo Natural Nuclear Reactors 21
1.5 Nuclear Accidents and the Lessons Learnt 25
References 31
2. Materials Toxicity and Biological Effects 37
2.1 Metals 38
2.1.1 Beryllium, Barium and Radium 38
2.1.2 Vanadium 39
2.1.3 Chromium, Molybdenum and Tungsten 40
2.1.4 Manganese, Technetium and Rhenium 40
2.1.5 Platinum-Group Metals 41
2.1.6 Nickel 42
2.1.7 Copper, Silver and Gold 42
2.1.8 Zinc, Cadmium and Mercury 43
2.1.9 Aluminium and Thallium 45
2.1.10 Tin and Lead 46
2.1.11 Arsenic, Antimony and Bismuth 48
2.1.12 Selenium, Tellurium and Polonium 49
2.1.13 Thorium, Uranium, Neptunium, Plutonium and Americium 50
2.2 Compounds 51
2.3 Asbestos 51
References 55
3. Glass and Ceramic Based Systems and General Processing Methods 57
3.1 Glass Formation 58
3.1.1 Glass-Forming Ability 58
3.1.2 Thermal Stability 61
3.2 Types of Glass 61
3.2.1 Silicate and Borosilicate Glasses 61
3.2.2 Phosphate Glasses 61
3.2.3 Rare Earth Oxide Glasses 62
3.2.4 Alternative Glasses 62
3.3 Ceramics 62
3.4 Glass-Ceramics 63
3.5 Glass and Ceramic Based Composite Systems 68
3.6 Processing of Glass and Ceramic Materials 68
3.6.1 Melting and Vitrifi cation 69
3.6.2 Powder Processing and Sintering 69
3.6.3 Hot Pressing 69
3.6.4 Sol-Gel Processing 70
3.6.5 Self-Propagating High Temperature Synthesis 70
3.6.6 Microwave Processing 70
References 71
4. Materials Characterization 75
4.1 Chemical Analysis 75
4.2 Thermal Analysis 76
4.3 Structural Analysis 78
4.3.1 Optical and Electron Microscopy 78
4.3.2 Energy Dispersive Spectroscopy 79
4.3.3 X-ray and Neutron Diffraction 79
4.3.4 Infra-Red and Raman Spectroscopy 80
4.3.5 Mössbauer Spectroscopy 80
4.3.6 Nuclear Magnetic Resonance 80
4.4 Mechanical Properties 81
4.4.1 Fracture Mechanics 81
4.4.2 Flexural Strength of Materials 83
4.4.3 Lifetime Behaviour 83
4.5 Chemical Durability and Standardized Tests 87
4.6 Radiation Stability 92
4.7 Other Properties Relevant to Wasteforms 94
4.8 Use of Nonradioactive Surrogates 94
References 96
5. Radioactive Wastes 101
5.1 Sources and Waste Stream Compositions 101
5.1.1 Nuclear Reactor Spent Fuel Wastes 102
5.1.2 Defence Wastes 107
5.1.3 Surplus Materials 108
5.1.4 Special or Unusual Categories of Radioactive Waste 109
5.2 General Immobilization Options 111
References 115
6. Immobilization by Vitrification 121
6.1 Vitrification History and the Advancement of Melter Design 121
6.1.1 Pot Processes 122
6.1.2 Continuous Melting by Induction Furnace 124
6.1.3 Joule-Heated Ceramic Melters 128
6.1.4 Cold Crucible Induction Melters 131
6.1.5 Plasma Arc/Torch Melters 135
6.1.6 Microwave Processing 138
6.1.7 In situ Melting 138
6.1.8 Bulk Vitrification 138
6.1.9 Alternative Melting Techniques 138
6.1.10 Vitrification Incidents and the Lessons that have been Learnt 140
6.2 Difficult Waste Constituents 144
6.2.1 Molybdenum and Caesium 144
6.2.2 Platinum Group Metals 147
6.2.3 Technetium 149
6.2.4 Chromium, Nickel and Iron 150
6.2.5 Halides 150
6.2.6 Sulphates 150
6.2.7 Phosphates 151
6.3 Effect of Specific Batch Additives on Melting Performance 151
6.4 Types of Glass and Candidate Glass Requirements 151
6.4.1 Silicate and Borosilicate Glass 151
6.4.2 Phosphate Glasses 163
6.4.3 Rare Earth Oxide Glasses 165
6.4.4 Alternative Glasses 166
6.5 Glass-Forming Ability 168
6.6 Alternative Methods for Producing Glassy Wasteforms 169
6.6.1 Sintered and Porous Glass 169
6.6.2 Hot-Pressed Glass 171
6.6.3 Microwave Sintering 175
6.6.4 Self-Sustaining Vitrification 176
6.6.5 Plasma Torch Incineration and Vitrification 177
References 177
7. Immobilization of Radioactive Materials as a Ceramic Wasteform 185
7.1 Titanate and Zirconate Ceramics 185
7.2 Phosphate Ceramics 203
7.3 Aluminosilicate Ceramics 207
7.4 Alternative Ceramics 209
7.5 Cement Based Systems 211
References 212
8. Immobilization of Radioactive Materials as a Glass-Ceramic Wasteform 221
8.1 Barium Aluminosilicate Glass-Ceramics 222
8.2 Barium Titanium Silicate Glass-Ceramics 222
8.3 Calcium Magnesium Silicate Glass-Ceramics 222
8.4 Calcium Titanium Silicate Glass-Ceramics 227
8.5 Basaltic Glass-Ceramics 228
8.6 Zirconolite Based Glass-Ceramics 230
8.7 Alternative Silicate Based Glass-Ceramics 234
8.8 Phosphate Based Glass-Ceramics 234
References 237
9. Novel Hosts for the Immobilization of Special or Unusual Categories of
Radioactive Wastes 241
9.1 Silicate Glasses 241
9.2 Phosphate Glasses 246
9.3 Alternative Vitrification Routes 249
9.4 Ceramic-Based Hosts 251
9.5 Glass-Encapsulated Composite and Hybrid Systems 253
9.6 Oxynitride Glasses 259
9.7 Plutonium Disposition 260
References 266
10. Properties of Radioactive Wasteforms 275
10.1 Thermal Stability 275
10.2 Chemical Durability 276
10.2.1 General Principles of Glass Durability 277
10.2.2 Durability of Silicate Based Glasses in Water 282
10.2.3 Durability of Silicate Based Glasses in Groundwaters and Repository
Environments 291
10.2.4 Durability of Phosphate Based Glasses 296
10.2.5 Lessons to be Learnt from Archaeological Glasses 297
10.2.6 Ceramic Durability 301
10.2.7 Glass-Ceramic Durability 308
10.2.8 Durability of Glass-Encapsulated Ceramic Hybrid Wasteforms 309
10.2.9 Influence of Colloids 310
10.3 Radiation Stability 311
10.3.1 Glass Stability 311
10.3.2 Ceramic Stability 316
10.3.3 Glass-Encapsulated Ceramic Hybrid Stability 323
10.4 Natural Analogues 324
10.5 Mechanical Properties 328
10.6 Alternative Properties 333
References 334
11. Structural and Modelling Studies 343
11.1 Structural Studies 343
11.1.1 Vitreous Wasteforms 343
11.1.2 Ceramic Wasteforms 349
11.2 Modelling Studies 350
11.2.1 Modelling Techniques 350
11.2.2 Vitreous Wasteforms 350
11.2.3 Ceramic Wasteforms 356
References 357
12. Sources and Compositions of Nonradioactive Toxic and Hazardous Wastes,
and Common Disposal Routes 361
12.1 Incinerator Wastes 365
12.2 Sewage and Dredging Sludges 368
12.3 Zinc Hydrometallurgical and Red Mud Wastes 370
12.4 Blast Furnace Slags and Electric Arc Furnace Dusts 370
12.5 Alternative Metallurgical Wastes and Slags 370
12.6 Metal Finishing and Plating Wastes 371
12.7 Coal Ash and Fly Ash from Thermal Power Stations 374
12.8 Cement Dust and Clay-Refining Wastes 379
12.9 Tannery Industry Wastes 379
12.10 Asbestos 380
12.11 Medical Wastes 380
12.12 Electrical and Electronic Wastes 383
12.13 Alternative Wastes 384
References 385
13. Vitrification of Nonradioactive Toxic and Hazardous Wastes 389
13.1 Incinerator Wastes 392
13.2 Sewage and Dredging Sludges 397
13.3 Zinc Hydrometallurgical and Red Mud Wastes 398
13.4 Blast Furnace Slags and Electric Arc Furnace Dusts 399
13.5 Alternative Metallurgical Wastes and Slags 401
13.6 Metal Finishing and Plating Wastes 403
13.7 Coal Ash and Fly Ash from Thermal Power Stations 404
13.8 Cement Dust, Clay-Refining and Tannery Industry Wastes 406
13.9 Asbestos 406
13.10 Medical Waste 407
13.11 Electrical and Electronic Wastes 408
13.12 Alternative Wastes 408
13.13 Mixed Nonradioactive Hazardous Wastes 409
13.14 Glass-Ceramics for Nonradioactive Waste Immobilization 410
13.15 Commercial Hazardous Waste Vitrification Facilities 418
References 420
14. Alternative Treatment Processes, and Characterization, Properties and
Applications of Nonradioactive Wasteforms 429
14.1 Alternatives to Vitrification 429
14.2 Use of Alternative Waste Sources to Prepare New Materials 435
14.3 Use of Waste Glass to Prepare New Materials 435
14.4 Characterization, Properties and Applications of Nonradioactive
Wasteforms 436
14.4.1 Mechanical Properties 436
14.4.2 Chemical Durability 440
14.4.3 Structural and Modelling Studies 441
14.4.4 Use of Less Hazardous or Nontoxic Surrogates 442
14.5 Applications 444
References 445
15. Influence of Organic, Micro-Organism and Microbial Activity on
Wasteform Integrity 451
15.1 Micro-Organism Activity and Transport Mechanisms 452
15.2 Repository Environments 454
15.3 Repository Analogues 457
15.4 Wasteforms 458
References 462
16. Concluding Remarks, Comparisons between Radioactive and Nonradioactive
Waste Immobilization, and Outlook for the Future 465
16.1 Mixed Radioactive and Nonradioactive Wastes 465
16.2 System and Wasteform Comparisons 467
16.2.1 Treatment Facilities 467
16.2.2 Wasteforms 469
16.3 Immediate and Short-Term Future Outlook 473
16.4 Medium and Longer Term Future Outlook 474
16.4.1 Generation IV Nuclear Energy Systems 474
16.4.2 Element Partitioning and Transmutation 478
16.5 Choosing a Wasteform 479
16.5.1 Wasteforms Studied in the Past and Short-Term Future Direction 479
16.5.2 Alternative Wasteforms and Longer Term Future Direction 484
16.6 Wasteform Characterization 486
16.7 Standards, Regulatory Requirements, and Performance Assessments 487
16.8 Overall Conclusions 489
References 490
Index 493
Preface page xi
Acknowledgements xiii
List of Abbreviations xv
1. Introduction 1
1.1 Categories of Waste and Waste Generation in the Modern World 1
1.1.1 Radioactive Wastes from Nuclear Power and Defence Operations 2
1.1.2 Toxic and Hazardous Wastes 7
1.1.3 Other Sources of Waste Material 9
1.2 General Disposal Options 11
1.3 Radiation Issues 19
1.4 Waste Disposal and the Oklo Natural Nuclear Reactors 21
1.5 Nuclear Accidents and the Lessons Learnt 25
References 31
2. Materials Toxicity and Biological Effects 37
2.1 Metals 38
2.1.1 Beryllium, Barium and Radium 38
2.1.2 Vanadium 39
2.1.3 Chromium, Molybdenum and Tungsten 40
2.1.4 Manganese, Technetium and Rhenium 40
2.1.5 Platinum-Group Metals 41
2.1.6 Nickel 42
2.1.7 Copper, Silver and Gold 42
2.1.8 Zinc, Cadmium and Mercury 43
2.1.9 Aluminium and Thallium 45
2.1.10 Tin and Lead 46
2.1.11 Arsenic, Antimony and Bismuth 48
2.1.12 Selenium, Tellurium and Polonium 49
2.1.13 Thorium, Uranium, Neptunium, Plutonium and Americium 50
2.2 Compounds 51
2.3 Asbestos 51
References 55
3. Glass and Ceramic Based Systems and General Processing Methods 57
3.1 Glass Formation 58
3.1.1 Glass-Forming Ability 58
3.1.2 Thermal Stability 61
3.2 Types of Glass 61
3.2.1 Silicate and Borosilicate Glasses 61
3.2.2 Phosphate Glasses 61
3.2.3 Rare Earth Oxide Glasses 62
3.2.4 Alternative Glasses 62
3.3 Ceramics 62
3.4 Glass-Ceramics 63
3.5 Glass and Ceramic Based Composite Systems 68
3.6 Processing of Glass and Ceramic Materials 68
3.6.1 Melting and Vitrifi cation 69
3.6.2 Powder Processing and Sintering 69
3.6.3 Hot Pressing 69
3.6.4 Sol-Gel Processing 70
3.6.5 Self-Propagating High Temperature Synthesis 70
3.6.6 Microwave Processing 70
References 71
4. Materials Characterization 75
4.1 Chemical Analysis 75
4.2 Thermal Analysis 76
4.3 Structural Analysis 78
4.3.1 Optical and Electron Microscopy 78
4.3.2 Energy Dispersive Spectroscopy 79
4.3.3 X-ray and Neutron Diffraction 79
4.3.4 Infra-Red and Raman Spectroscopy 80
4.3.5 Mössbauer Spectroscopy 80
4.3.6 Nuclear Magnetic Resonance 80
4.4 Mechanical Properties 81
4.4.1 Fracture Mechanics 81
4.4.2 Flexural Strength of Materials 83
4.4.3 Lifetime Behaviour 83
4.5 Chemical Durability and Standardized Tests 87
4.6 Radiation Stability 92
4.7 Other Properties Relevant to Wasteforms 94
4.8 Use of Nonradioactive Surrogates 94
References 96
5. Radioactive Wastes 101
5.1 Sources and Waste Stream Compositions 101
5.1.1 Nuclear Reactor Spent Fuel Wastes 102
5.1.2 Defence Wastes 107
5.1.3 Surplus Materials 108
5.1.4 Special or Unusual Categories of Radioactive Waste 109
5.2 General Immobilization Options 111
References 115
6. Immobilization by Vitrification 121
6.1 Vitrification History and the Advancement of Melter Design 121
6.1.1 Pot Processes 122
6.1.2 Continuous Melting by Induction Furnace 124
6.1.3 Joule-Heated Ceramic Melters 128
6.1.4 Cold Crucible Induction Melters 131
6.1.5 Plasma Arc/Torch Melters 135
6.1.6 Microwave Processing 138
6.1.7 In situ Melting 138
6.1.8 Bulk Vitrification 138
6.1.9 Alternative Melting Techniques 138
6.1.10 Vitrification Incidents and the Lessons that have been Learnt 140
6.2 Difficult Waste Constituents 144
6.2.1 Molybdenum and Caesium 144
6.2.2 Platinum Group Metals 147
6.2.3 Technetium 149
6.2.4 Chromium, Nickel and Iron 150
6.2.5 Halides 150
6.2.6 Sulphates 150
6.2.7 Phosphates 151
6.3 Effect of Specific Batch Additives on Melting Performance 151
6.4 Types of Glass and Candidate Glass Requirements 151
6.4.1 Silicate and Borosilicate Glass 151
6.4.2 Phosphate Glasses 163
6.4.3 Rare Earth Oxide Glasses 165
6.4.4 Alternative Glasses 166
6.5 Glass-Forming Ability 168
6.6 Alternative Methods for Producing Glassy Wasteforms 169
6.6.1 Sintered and Porous Glass 169
6.6.2 Hot-Pressed Glass 171
6.6.3 Microwave Sintering 175
6.6.4 Self-Sustaining Vitrification 176
6.6.5 Plasma Torch Incineration and Vitrification 177
References 177
7. Immobilization of Radioactive Materials as a Ceramic Wasteform 185
7.1 Titanate and Zirconate Ceramics 185
7.2 Phosphate Ceramics 203
7.3 Aluminosilicate Ceramics 207
7.4 Alternative Ceramics 209
7.5 Cement Based Systems 211
References 212
8. Immobilization of Radioactive Materials as a Glass-Ceramic Wasteform 221
8.1 Barium Aluminosilicate Glass-Ceramics 222
8.2 Barium Titanium Silicate Glass-Ceramics 222
8.3 Calcium Magnesium Silicate Glass-Ceramics 222
8.4 Calcium Titanium Silicate Glass-Ceramics 227
8.5 Basaltic Glass-Ceramics 228
8.6 Zirconolite Based Glass-Ceramics 230
8.7 Alternative Silicate Based Glass-Ceramics 234
8.8 Phosphate Based Glass-Ceramics 234
References 237
9. Novel Hosts for the Immobilization of Special or Unusual Categories of
Radioactive Wastes 241
9.1 Silicate Glasses 241
9.2 Phosphate Glasses 246
9.3 Alternative Vitrification Routes 249
9.4 Ceramic-Based Hosts 251
9.5 Glass-Encapsulated Composite and Hybrid Systems 253
9.6 Oxynitride Glasses 259
9.7 Plutonium Disposition 260
References 266
10. Properties of Radioactive Wasteforms 275
10.1 Thermal Stability 275
10.2 Chemical Durability 276
10.2.1 General Principles of Glass Durability 277
10.2.2 Durability of Silicate Based Glasses in Water 282
10.2.3 Durability of Silicate Based Glasses in Groundwaters and Repository
Environments 291
10.2.4 Durability of Phosphate Based Glasses 296
10.2.5 Lessons to be Learnt from Archaeological Glasses 297
10.2.6 Ceramic Durability 301
10.2.7 Glass-Ceramic Durability 308
10.2.8 Durability of Glass-Encapsulated Ceramic Hybrid Wasteforms 309
10.2.9 Influence of Colloids 310
10.3 Radiation Stability 311
10.3.1 Glass Stability 311
10.3.2 Ceramic Stability 316
10.3.3 Glass-Encapsulated Ceramic Hybrid Stability 323
10.4 Natural Analogues 324
10.5 Mechanical Properties 328
10.6 Alternative Properties 333
References 334
11. Structural and Modelling Studies 343
11.1 Structural Studies 343
11.1.1 Vitreous Wasteforms 343
11.1.2 Ceramic Wasteforms 349
11.2 Modelling Studies 350
11.2.1 Modelling Techniques 350
11.2.2 Vitreous Wasteforms 350
11.2.3 Ceramic Wasteforms 356
References 357
12. Sources and Compositions of Nonradioactive Toxic and Hazardous Wastes,
and Common Disposal Routes 361
12.1 Incinerator Wastes 365
12.2 Sewage and Dredging Sludges 368
12.3 Zinc Hydrometallurgical and Red Mud Wastes 370
12.4 Blast Furnace Slags and Electric Arc Furnace Dusts 370
12.5 Alternative Metallurgical Wastes and Slags 370
12.6 Metal Finishing and Plating Wastes 371
12.7 Coal Ash and Fly Ash from Thermal Power Stations 374
12.8 Cement Dust and Clay-Refining Wastes 379
12.9 Tannery Industry Wastes 379
12.10 Asbestos 380
12.11 Medical Wastes 380
12.12 Electrical and Electronic Wastes 383
12.13 Alternative Wastes 384
References 385
13. Vitrification of Nonradioactive Toxic and Hazardous Wastes 389
13.1 Incinerator Wastes 392
13.2 Sewage and Dredging Sludges 397
13.3 Zinc Hydrometallurgical and Red Mud Wastes 398
13.4 Blast Furnace Slags and Electric Arc Furnace Dusts 399
13.5 Alternative Metallurgical Wastes and Slags 401
13.6 Metal Finishing and Plating Wastes 403
13.7 Coal Ash and Fly Ash from Thermal Power Stations 404
13.8 Cement Dust, Clay-Refining and Tannery Industry Wastes 406
13.9 Asbestos 406
13.10 Medical Waste 407
13.11 Electrical and Electronic Wastes 408
13.12 Alternative Wastes 408
13.13 Mixed Nonradioactive Hazardous Wastes 409
13.14 Glass-Ceramics for Nonradioactive Waste Immobilization 410
13.15 Commercial Hazardous Waste Vitrification Facilities 418
References 420
14. Alternative Treatment Processes, and Characterization, Properties and
Applications of Nonradioactive Wasteforms 429
14.1 Alternatives to Vitrification 429
14.2 Use of Alternative Waste Sources to Prepare New Materials 435
14.3 Use of Waste Glass to Prepare New Materials 435
14.4 Characterization, Properties and Applications of Nonradioactive
Wasteforms 436
14.4.1 Mechanical Properties 436
14.4.2 Chemical Durability 440
14.4.3 Structural and Modelling Studies 441
14.4.4 Use of Less Hazardous or Nontoxic Surrogates 442
14.5 Applications 444
References 445
15. Influence of Organic, Micro-Organism and Microbial Activity on
Wasteform Integrity 451
15.1 Micro-Organism Activity and Transport Mechanisms 452
15.2 Repository Environments 454
15.3 Repository Analogues 457
15.4 Wasteforms 458
References 462
16. Concluding Remarks, Comparisons between Radioactive and Nonradioactive
Waste Immobilization, and Outlook for the Future 465
16.1 Mixed Radioactive and Nonradioactive Wastes 465
16.2 System and Wasteform Comparisons 467
16.2.1 Treatment Facilities 467
16.2.2 Wasteforms 469
16.3 Immediate and Short-Term Future Outlook 473
16.4 Medium and Longer Term Future Outlook 474
16.4.1 Generation IV Nuclear Energy Systems 474
16.4.2 Element Partitioning and Transmutation 478
16.5 Choosing a Wasteform 479
16.5.1 Wasteforms Studied in the Past and Short-Term Future Direction 479
16.5.2 Alternative Wasteforms and Longer Term Future Direction 484
16.6 Wasteform Characterization 486
16.7 Standards, Regulatory Requirements, and Performance Assessments 487
16.8 Overall Conclusions 489
References 490
Index 493
Acknowledgements xiii
List of Abbreviations xv
1. Introduction 1
1.1 Categories of Waste and Waste Generation in the Modern World 1
1.1.1 Radioactive Wastes from Nuclear Power and Defence Operations 2
1.1.2 Toxic and Hazardous Wastes 7
1.1.3 Other Sources of Waste Material 9
1.2 General Disposal Options 11
1.3 Radiation Issues 19
1.4 Waste Disposal and the Oklo Natural Nuclear Reactors 21
1.5 Nuclear Accidents and the Lessons Learnt 25
References 31
2. Materials Toxicity and Biological Effects 37
2.1 Metals 38
2.1.1 Beryllium, Barium and Radium 38
2.1.2 Vanadium 39
2.1.3 Chromium, Molybdenum and Tungsten 40
2.1.4 Manganese, Technetium and Rhenium 40
2.1.5 Platinum-Group Metals 41
2.1.6 Nickel 42
2.1.7 Copper, Silver and Gold 42
2.1.8 Zinc, Cadmium and Mercury 43
2.1.9 Aluminium and Thallium 45
2.1.10 Tin and Lead 46
2.1.11 Arsenic, Antimony and Bismuth 48
2.1.12 Selenium, Tellurium and Polonium 49
2.1.13 Thorium, Uranium, Neptunium, Plutonium and Americium 50
2.2 Compounds 51
2.3 Asbestos 51
References 55
3. Glass and Ceramic Based Systems and General Processing Methods 57
3.1 Glass Formation 58
3.1.1 Glass-Forming Ability 58
3.1.2 Thermal Stability 61
3.2 Types of Glass 61
3.2.1 Silicate and Borosilicate Glasses 61
3.2.2 Phosphate Glasses 61
3.2.3 Rare Earth Oxide Glasses 62
3.2.4 Alternative Glasses 62
3.3 Ceramics 62
3.4 Glass-Ceramics 63
3.5 Glass and Ceramic Based Composite Systems 68
3.6 Processing of Glass and Ceramic Materials 68
3.6.1 Melting and Vitrifi cation 69
3.6.2 Powder Processing and Sintering 69
3.6.3 Hot Pressing 69
3.6.4 Sol-Gel Processing 70
3.6.5 Self-Propagating High Temperature Synthesis 70
3.6.6 Microwave Processing 70
References 71
4. Materials Characterization 75
4.1 Chemical Analysis 75
4.2 Thermal Analysis 76
4.3 Structural Analysis 78
4.3.1 Optical and Electron Microscopy 78
4.3.2 Energy Dispersive Spectroscopy 79
4.3.3 X-ray and Neutron Diffraction 79
4.3.4 Infra-Red and Raman Spectroscopy 80
4.3.5 Mössbauer Spectroscopy 80
4.3.6 Nuclear Magnetic Resonance 80
4.4 Mechanical Properties 81
4.4.1 Fracture Mechanics 81
4.4.2 Flexural Strength of Materials 83
4.4.3 Lifetime Behaviour 83
4.5 Chemical Durability and Standardized Tests 87
4.6 Radiation Stability 92
4.7 Other Properties Relevant to Wasteforms 94
4.8 Use of Nonradioactive Surrogates 94
References 96
5. Radioactive Wastes 101
5.1 Sources and Waste Stream Compositions 101
5.1.1 Nuclear Reactor Spent Fuel Wastes 102
5.1.2 Defence Wastes 107
5.1.3 Surplus Materials 108
5.1.4 Special or Unusual Categories of Radioactive Waste 109
5.2 General Immobilization Options 111
References 115
6. Immobilization by Vitrification 121
6.1 Vitrification History and the Advancement of Melter Design 121
6.1.1 Pot Processes 122
6.1.2 Continuous Melting by Induction Furnace 124
6.1.3 Joule-Heated Ceramic Melters 128
6.1.4 Cold Crucible Induction Melters 131
6.1.5 Plasma Arc/Torch Melters 135
6.1.6 Microwave Processing 138
6.1.7 In situ Melting 138
6.1.8 Bulk Vitrification 138
6.1.9 Alternative Melting Techniques 138
6.1.10 Vitrification Incidents and the Lessons that have been Learnt 140
6.2 Difficult Waste Constituents 144
6.2.1 Molybdenum and Caesium 144
6.2.2 Platinum Group Metals 147
6.2.3 Technetium 149
6.2.4 Chromium, Nickel and Iron 150
6.2.5 Halides 150
6.2.6 Sulphates 150
6.2.7 Phosphates 151
6.3 Effect of Specific Batch Additives on Melting Performance 151
6.4 Types of Glass and Candidate Glass Requirements 151
6.4.1 Silicate and Borosilicate Glass 151
6.4.2 Phosphate Glasses 163
6.4.3 Rare Earth Oxide Glasses 165
6.4.4 Alternative Glasses 166
6.5 Glass-Forming Ability 168
6.6 Alternative Methods for Producing Glassy Wasteforms 169
6.6.1 Sintered and Porous Glass 169
6.6.2 Hot-Pressed Glass 171
6.6.3 Microwave Sintering 175
6.6.4 Self-Sustaining Vitrification 176
6.6.5 Plasma Torch Incineration and Vitrification 177
References 177
7. Immobilization of Radioactive Materials as a Ceramic Wasteform 185
7.1 Titanate and Zirconate Ceramics 185
7.2 Phosphate Ceramics 203
7.3 Aluminosilicate Ceramics 207
7.4 Alternative Ceramics 209
7.5 Cement Based Systems 211
References 212
8. Immobilization of Radioactive Materials as a Glass-Ceramic Wasteform 221
8.1 Barium Aluminosilicate Glass-Ceramics 222
8.2 Barium Titanium Silicate Glass-Ceramics 222
8.3 Calcium Magnesium Silicate Glass-Ceramics 222
8.4 Calcium Titanium Silicate Glass-Ceramics 227
8.5 Basaltic Glass-Ceramics 228
8.6 Zirconolite Based Glass-Ceramics 230
8.7 Alternative Silicate Based Glass-Ceramics 234
8.8 Phosphate Based Glass-Ceramics 234
References 237
9. Novel Hosts for the Immobilization of Special or Unusual Categories of
Radioactive Wastes 241
9.1 Silicate Glasses 241
9.2 Phosphate Glasses 246
9.3 Alternative Vitrification Routes 249
9.4 Ceramic-Based Hosts 251
9.5 Glass-Encapsulated Composite and Hybrid Systems 253
9.6 Oxynitride Glasses 259
9.7 Plutonium Disposition 260
References 266
10. Properties of Radioactive Wasteforms 275
10.1 Thermal Stability 275
10.2 Chemical Durability 276
10.2.1 General Principles of Glass Durability 277
10.2.2 Durability of Silicate Based Glasses in Water 282
10.2.3 Durability of Silicate Based Glasses in Groundwaters and Repository
Environments 291
10.2.4 Durability of Phosphate Based Glasses 296
10.2.5 Lessons to be Learnt from Archaeological Glasses 297
10.2.6 Ceramic Durability 301
10.2.7 Glass-Ceramic Durability 308
10.2.8 Durability of Glass-Encapsulated Ceramic Hybrid Wasteforms 309
10.2.9 Influence of Colloids 310
10.3 Radiation Stability 311
10.3.1 Glass Stability 311
10.3.2 Ceramic Stability 316
10.3.3 Glass-Encapsulated Ceramic Hybrid Stability 323
10.4 Natural Analogues 324
10.5 Mechanical Properties 328
10.6 Alternative Properties 333
References 334
11. Structural and Modelling Studies 343
11.1 Structural Studies 343
11.1.1 Vitreous Wasteforms 343
11.1.2 Ceramic Wasteforms 349
11.2 Modelling Studies 350
11.2.1 Modelling Techniques 350
11.2.2 Vitreous Wasteforms 350
11.2.3 Ceramic Wasteforms 356
References 357
12. Sources and Compositions of Nonradioactive Toxic and Hazardous Wastes,
and Common Disposal Routes 361
12.1 Incinerator Wastes 365
12.2 Sewage and Dredging Sludges 368
12.3 Zinc Hydrometallurgical and Red Mud Wastes 370
12.4 Blast Furnace Slags and Electric Arc Furnace Dusts 370
12.5 Alternative Metallurgical Wastes and Slags 370
12.6 Metal Finishing and Plating Wastes 371
12.7 Coal Ash and Fly Ash from Thermal Power Stations 374
12.8 Cement Dust and Clay-Refining Wastes 379
12.9 Tannery Industry Wastes 379
12.10 Asbestos 380
12.11 Medical Wastes 380
12.12 Electrical and Electronic Wastes 383
12.13 Alternative Wastes 384
References 385
13. Vitrification of Nonradioactive Toxic and Hazardous Wastes 389
13.1 Incinerator Wastes 392
13.2 Sewage and Dredging Sludges 397
13.3 Zinc Hydrometallurgical and Red Mud Wastes 398
13.4 Blast Furnace Slags and Electric Arc Furnace Dusts 399
13.5 Alternative Metallurgical Wastes and Slags 401
13.6 Metal Finishing and Plating Wastes 403
13.7 Coal Ash and Fly Ash from Thermal Power Stations 404
13.8 Cement Dust, Clay-Refining and Tannery Industry Wastes 406
13.9 Asbestos 406
13.10 Medical Waste 407
13.11 Electrical and Electronic Wastes 408
13.12 Alternative Wastes 408
13.13 Mixed Nonradioactive Hazardous Wastes 409
13.14 Glass-Ceramics for Nonradioactive Waste Immobilization 410
13.15 Commercial Hazardous Waste Vitrification Facilities 418
References 420
14. Alternative Treatment Processes, and Characterization, Properties and
Applications of Nonradioactive Wasteforms 429
14.1 Alternatives to Vitrification 429
14.2 Use of Alternative Waste Sources to Prepare New Materials 435
14.3 Use of Waste Glass to Prepare New Materials 435
14.4 Characterization, Properties and Applications of Nonradioactive
Wasteforms 436
14.4.1 Mechanical Properties 436
14.4.2 Chemical Durability 440
14.4.3 Structural and Modelling Studies 441
14.4.4 Use of Less Hazardous or Nontoxic Surrogates 442
14.5 Applications 444
References 445
15. Influence of Organic, Micro-Organism and Microbial Activity on
Wasteform Integrity 451
15.1 Micro-Organism Activity and Transport Mechanisms 452
15.2 Repository Environments 454
15.3 Repository Analogues 457
15.4 Wasteforms 458
References 462
16. Concluding Remarks, Comparisons between Radioactive and Nonradioactive
Waste Immobilization, and Outlook for the Future 465
16.1 Mixed Radioactive and Nonradioactive Wastes 465
16.2 System and Wasteform Comparisons 467
16.2.1 Treatment Facilities 467
16.2.2 Wasteforms 469
16.3 Immediate and Short-Term Future Outlook 473
16.4 Medium and Longer Term Future Outlook 474
16.4.1 Generation IV Nuclear Energy Systems 474
16.4.2 Element Partitioning and Transmutation 478
16.5 Choosing a Wasteform 479
16.5.1 Wasteforms Studied in the Past and Short-Term Future Direction 479
16.5.2 Alternative Wasteforms and Longer Term Future Direction 484
16.6 Wasteform Characterization 486
16.7 Standards, Regulatory Requirements, and Performance Assessments 487
16.8 Overall Conclusions 489
References 490
Index 493
"The author's renowned expertise in immobilisation technology for wastes is clearly reflected in this book, which provides an exhaustive review of the subject. It would benefit readers involved in waste management of both nuclear and nonradioactive industries." (Materials World, 1 January 2012)
"I am recommending to everyone interested to read the book of Prof Donald on glass and ceramic hosts: you will find a wealth of factual data on glasses and ceramics as well as bright ideas and hints for your activities." (Materials Views, 27 April 2011)
"I am recommending to everyone interested to read the book of Prof Donald on glass and ceramic hosts: you will find a wealth of factual data on glasses and ceramics as well as bright ideas and hints for your activities." (Materials Views, 27 April 2011)