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.

"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)

• Preface page xiAcknowledgements xiiiList of Abbreviations xv1. Introduction 11.1 Categories of Waste and Waste Generation in the Modern World 11.1.1 Radioactive Wastes from Nuclear Power and Defence Operations 21.1.2 Toxic and Hazardous Wastes 71.1.3 Other Sources of Waste Material 91.2 General Disposal Options 111.3 Radiation Issues 191.4 Waste Disposal and the Oklo Natural Nuclear Reactors 211.5 Nuclear Accidents and the Lessons Learnt 25References 312. Materials Toxicity and Biological Effects 372.1 Metals 382.1.1 Beryllium, Barium and Radium 382.1.2 Vanadium 392.1.3 Chromium, Molybdenum and Tungsten 402.1.4 Manganese, Technetium and Rhenium 402.1.5 Platinum-Group Metals 412.1.6 Nickel 422.1.7 Copper, Silver and Gold 422.1.8 Zinc, Cadmium and Mercury 432.1.9 Aluminium and Thallium 452.1.10 Tin and Lead 462.1.11 Arsenic, Antimony and Bismuth 482.1.12 Selenium, Tellurium and Polonium 492.1.13 Thorium, Uranium, Neptunium, Plutonium and Americium 502.2 Compounds 512.3 Asbestos 51References 553. Glass and Ceramic Based Systems and General Processing Methods 573.1 Glass Formation 583.1.1 Glass-Forming Ability 583.1.2 Thermal Stability 613.2 Types of Glass 613.2.1 Silicate and Borosilicate Glasses 613.2.2 Phosphate Glasses 613.2.3 Rare Earth Oxide Glasses 623.2.4 Alternative Glasses 623.3 Ceramics 623.4 Glass-Ceramics 633.5 Glass and Ceramic Based Composite Systems 683.6 Processing of Glass and Ceramic Materials 683.6.1 Melting and Vitrifi cation 693.6.2 Powder Processing and Sintering 693.6.3 Hot Pressing 693.6.4 Sol-Gel Processing 703.6.5 Self-Propagating High Temperature Synthesis 703.6.6 Microwave Processing 70References 714. Materials Characterization 754.1 Chemical Analysis 754.2 Thermal Analysis 764.3 Structural Analysis 784.3.1 Optical and Electron Microscopy 784.3.2 Energy Dispersive Spectroscopy 794.3.3 X-ray and Neutron Diffraction 794.3.4 Infra-Red and Raman Spectroscopy 804.3.5 Mössbauer Spectroscopy 804.3.6 Nuclear Magnetic Resonance 804.4 Mechanical Properties 814.4.1 Fracture Mechanics 814.4.2 Flexural Strength of Materials 834.4.3 Lifetime Behaviour 834.5 Chemical Durability and Standardized Tests 874.6 Radiation Stability 924.7 Other Properties Relevant to Wasteforms 944.8 Use of Nonradioactive Surrogates 94References 965. Radioactive Wastes 1015.1 Sources and Waste Stream Compositions 1015.1.1 Nuclear Reactor Spent Fuel Wastes 1025.1.2 Defence Wastes 1075.1.3 Surplus Materials 1085.1.4 Special or Unusual Categories of Radioactive Waste 1095.2 General Immobilization Options 111References 1156. Immobilization by Vitrification 1216.1 Vitrification History and the Advancement of Melter Design 1216.1.1 Pot Processes 1226.1.2 Continuous Melting by Induction Furnace 1246.1.3 Joule-Heated Ceramic Melters 1286.1.4 Cold Crucible Induction Melters 1316.1.5 Plasma Arc/Torch Melters 1356.1.6 Microwave Processing 1386.1.7 In situ Melting 1386.1.8 Bulk Vitrification 1386.1.9 Alternative Melting Techniques 1386.1.10 Vitrification Incidents and the Lessons that have been Learnt 1406.2 Difficult Waste Constituents 1446.2.1 Molybdenum and Caesium 1446.2.2 Platinum Group Metals 1476.2.3 Technetium 1496.2.4 Chromium, Nickel and Iron 1506.2.5 Halides 1506.2.6 Sulphates 1506.2.7 Phosphates 1516.3 Effect of Specific Batch Additives on Melting Performance 1516.4 Types of Glass and Candidate Glass Requirements 1516.4.1 Silicate and Borosilicate Glass 1516.4.2 Phosphate Glasses 1636.4.3 Rare Earth Oxide Glasses 1656.4.4 Alternative Glasses 1666.5 Glass-Forming Ability 1686.6 Alternative Methods for Producing Glassy Wasteforms 1696.6.1 Sintered and Porous Glass 1696.6.2 Hot-Pressed Glass 1716.6.3 Microwave Sintering 1756.6.4 Self-Sustaining Vitrification 1766.6.5 Plasma Torch Incineration and Vitrification 177References 1777. Immobilization of Radioactive Materials as a Ceramic Wasteform 1857.1 Titanate and Zirconate Ceramics 1857.2 Phosphate Ceramics 2037.3 Aluminosilicate Ceramics 2077.4 Alternative Ceramics 2097.5 Cement Based Systems 211References 2128. Immobilization of Radioactive Materials as a Glass-Ceramic Wasteform 2218.1 Barium Aluminosilicate Glass-Ceramics 2228.2 Barium Titanium Silicate Glass-Ceramics 2228.3 Calcium Magnesium Silicate Glass-Ceramics 2228.4 Calcium Titanium Silicate Glass-Ceramics 2278.5 Basaltic Glass-Ceramics 2288.6 Zirconolite Based Glass-Ceramics 2308.7 Alternative Silicate Based Glass-Ceramics 2348.8 Phosphate Based Glass-Ceramics 234References 2379. Novel Hosts for the Immobilization of Special or Unusual Categories of Radioactive Wastes 2419.1 Silicate Glasses 2419.2 Phosphate Glasses 2469.3 Alternative Vitrification Routes 2499.4 Ceramic-Based Hosts 2519.5 Glass-Encapsulated Composite and Hybrid Systems 2539.6 Oxynitride Glasses 2599.7 Plutonium Disposition 260References 26610. Properties of Radioactive Wasteforms 27510.1 Thermal Stability 27510.2 Chemical Durability 27610.2.1 General Principles of Glass Durability 27710.2.2 Durability of Silicate Based Glasses in Water 28210.2.3 Durability of Silicate Based Glasses in Groundwaters and Repository Environments 29110.2.4 Durability of Phosphate Based Glasses 29610.2.5 Lessons to be Learnt from Archaeological Glasses 29710.2.6 Ceramic Durability 30110.2.7 Glass-Ceramic Durability 30810.2.8 Durability of Glass-Encapsulated Ceramic Hybrid Wasteforms 30910.2.9 Influence of Colloids 31010.3 Radiation Stability 31110.3.1 Glass Stability 31110.3.2 Ceramic Stability 31610.3.3 Glass-Encapsulated Ceramic Hybrid Stability 32310.4 Natural Analogues 32410.5 Mechanical Properties 32810.6 Alternative Properties 333References 33411. Structural and Modelling Studies 34311.1 Structural Studies 34311.1.1 Vitreous Wasteforms 34311.1.2 Ceramic Wasteforms 34911.2 Modelling Studies 35011.2.1 Modelling Techniques 35011.2.2 Vitreous Wasteforms 35011.2.3 Ceramic Wasteforms 356References 35712. Sources and Compositions of Nonradioactive Toxic and Hazardous Wastes, and Common Disposal Routes 36112.1 Incinerator Wastes 36512.2 Sewage and Dredging Sludges 36812.3 Zinc Hydrometallurgical and Red Mud Wastes 37012.4 Blast Furnace Slags and Electric Arc Furnace Dusts 37012.5 Alternative Metallurgical Wastes and Slags 37012.6 Metal Finishing and Plating Wastes 37112.7 Coal Ash and Fly Ash from Thermal Power Stations 37412.8 Cement Dust and Clay-Refining Wastes 37912.9 Tannery Industry Wastes 37912.10 Asbestos 38012.11 Medical Wastes 38012.12 Electrical and Electronic Wastes 38312.13 Alternative Wastes 384References 38513. Vitrification of Nonradioactive Toxic and Hazardous Wastes 38913.1 Incinerator Wastes 39213.2 Sewage and Dredging Sludges 39713.3 Zinc Hydrometallurgical and Red Mud Wastes 39813.4 Blast Furnace Slags and Electric Arc Furnace Dusts 39913.5 Alternative Metallurgical Wastes and Slags 40113.6 Metal Finishing and Plating Wastes 40313.7 Coal Ash and Fly Ash from Thermal Power Stations 40413.8 Cement Dust, Clay-Refining and Tannery Industry Wastes 40613.9 Asbestos 40613.10 Medical Waste 40713.11 Electrical and Electronic Wastes 40813.12 Alternative Wastes 40813.13 Mixed Nonradioactive Hazardous Wastes 40913.14 Glass-Ceramics for Nonradioactive Waste Immobilization 41013.15 Commercial Hazardous Waste Vitrification Facilities 418References 42014. Alternative Treatment Processes, and Characterization, Properties and Applications of Nonradioactive Wasteforms 42914.1 Alternatives to Vitrification 42914.2 Use of Alternative Waste Sources to Prepare New Materials 43514.3 Use of Waste Glass to Prepare New Materials 43514.4 Characterization, Properties and Applications of Nonradioactive Wasteforms 43614.4.1 Mechanical Properties 43614.4.2 Chemical Durability 44014.4.3 Structural and Modelling Studies 44114.4.4 Use of Less Hazardous or Nontoxic Surrogates 44214.5 Applications 444References 44515. Influence of Organic, Micro-Organism and Microbial Activity on Wasteform Integrity 45115.1 Micro-Organism Activity and Transport Mechanisms 45215.2 Repository Environments 45415.3 Repository Analogues 45715.4 Wasteforms 458References 46216. Concluding Remarks, Comparisons between Radioactive and Nonradioactive Waste Immobilization, and Outlook for the Future 46516.1 Mixed Radioactive and Nonradioactive Wastes 46516.2 System and Wasteform Comparisons 46716.2.1 Treatment Facilities 46716.2.2 Wasteforms 46916.3 Immediate and Short-Term Future Outlook 47316.4 Medium and Longer Term Future Outlook 47416.4.1 Generation IV Nuclear Energy Systems 47416.4.2 Element Partitioning and Transmutation 47816.5 Choosing a Wasteform 47916.5.1 Wasteforms Studied in the Past and Short-Term Future Direction 47916.5.2 Alternative Wasteforms and Longer Term Future Direction 48416.6 Wasteform Characterization 48616.7 Standards, Regulatory Requirements, and Performance Assessments 48716.8 Overall Conclusions 489References 490Index 493

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.

"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)

• Preface page xiAcknowledgements xiiiList of Abbreviations xv1. Introduction 11.1 Categories of Waste and Waste Generation in the Modern World 11.1.1 Radioactive Wastes from Nuclear Power and Defence Operations 21.1.2 Toxic and Hazardous Wastes 71.1.3 Other Sources of Waste Material 91.2 General Disposal Options 111.3 Radiation Issues 191.4 Waste Disposal and the Oklo Natural Nuclear Reactors 211.5 Nuclear Accidents and the Lessons Learnt 25References 312. Materials Toxicity and Biological Effects 372.1 Metals 382.1.1 Beryllium, Barium and Radium 382.1.2 Vanadium 392.1.3 Chromium, Molybdenum and Tungsten 402.1.4 Manganese, Technetium and Rhenium 402.1.5 Platinum-Group Metals 412.1.6 Nickel 422.1.7 Copper, Silver and Gold 422.1.8 Zinc, Cadmium and Mercury 432.1.9 Aluminium and Thallium 452.1.10 Tin and Lead 462.1.11 Arsenic, Antimony and Bismuth 482.1.12 Selenium, Tellurium and Polonium 492.1.13 Thorium, Uranium, Neptunium, Plutonium and Americium 502.2 Compounds 512.3 Asbestos 51References 553. Glass and Ceramic Based Systems and General Processing Methods 573.1 Glass Formation 583.1.1 Glass-Forming Ability 583.1.2 Thermal Stability 613.2 Types of Glass 613.2.1 Silicate and Borosilicate Glasses 613.2.2 Phosphate Glasses 613.2.3 Rare Earth Oxide Glasses 623.2.4 Alternative Glasses 623.3 Ceramics 623.4 Glass-Ceramics 633.5 Glass and Ceramic Based Composite Systems 683.6 Processing of Glass and Ceramic Materials 683.6.1 Melting and Vitrifi cation 693.6.2 Powder Processing and Sintering 693.6.3 Hot Pressing 693.6.4 Sol-Gel Processing 703.6.5 Self-Propagating High Temperature Synthesis 703.6.6 Microwave Processing 70References 714. Materials Characterization 754.1 Chemical Analysis 754.2 Thermal Analysis 764.3 Structural Analysis 784.3.1 Optical and Electron Microscopy 784.3.2 Energy Dispersive Spectroscopy 794.3.3 X-ray and Neutron Diffraction 794.3.4 Infra-Red and Raman Spectroscopy 804.3.5 Mössbauer Spectroscopy 804.3.6 Nuclear Magnetic Resonance 804.4 Mechanical Properties 814.4.1 Fracture Mechanics 814.4.2 Flexural Strength of Materials 834.4.3 Lifetime Behaviour 834.5 Chemical Durability and Standardized Tests 874.6 Radiation Stability 924.7 Other Properties Relevant to Wasteforms 944.8 Use of Nonradioactive Surrogates 94References 965. Radioactive Wastes 1015.1 Sources and Waste Stream Compositions 1015.1.1 Nuclear Reactor Spent Fuel Wastes 1025.1.2 Defence Wastes 1075.1.3 Surplus Materials 1085.1.4 Special or Unusual Categories of Radioactive Waste 1095.2 General Immobilization Options 111References 1156. Immobilization by Vitrification 1216.1 Vitrification History and the Advancement of Melter Design 1216.1.1 Pot Processes 1226.1.2 Continuous Melting by Induction Furnace 1246.1.3 Joule-Heated Ceramic Melters 1286.1.4 Cold Crucible Induction Melters 1316.1.5 Plasma Arc/Torch Melters 1356.1.6 Microwave Processing 1386.1.7 In situ Melting 1386.1.8 Bulk Vitrification 1386.1.9 Alternative Melting Techniques 1386.1.10 Vitrification Incidents and the Lessons that have been Learnt 1406.2 Difficult Waste Constituents 1446.2.1 Molybdenum and Caesium 1446.2.2 Platinum Group Metals 1476.2.3 Technetium 1496.2.4 Chromium, Nickel and Iron 1506.2.5 Halides 1506.2.6 Sulphates 1506.2.7 Phosphates 1516.3 Effect of Specific Batch Additives on Melting Performance 1516.4 Types of Glass and Candidate Glass Requirements 1516.4.1 Silicate and Borosilicate Glass 1516.4.2 Phosphate Glasses 1636.4.3 Rare Earth Oxide Glasses 1656.4.4 Alternative Glasses 1666.5 Glass-Forming Ability 1686.6 Alternative Methods for Producing Glassy Wasteforms 1696.6.1 Sintered and Porous Glass 1696.6.2 Hot-Pressed Glass 1716.6.3 Microwave Sintering 1756.6.4 Self-Sustaining Vitrification 1766.6.5 Plasma Torch Incineration and Vitrification 177References 1777. Immobilization of Radioactive Materials as a Ceramic Wasteform 1857.1 Titanate and Zirconate Ceramics 1857.2 Phosphate Ceramics 2037.3 Aluminosilicate Ceramics 2077.4 Alternative Ceramics 2097.5 Cement Based Systems 211References 2128. Immobilization of Radioactive Materials as a Glass-Ceramic Wasteform 2218.1 Barium Aluminosilicate Glass-Ceramics 2228.2 Barium Titanium Silicate Glass-Ceramics 2228.3 Calcium Magnesium Silicate Glass-Ceramics 2228.4 Calcium Titanium Silicate Glass-Ceramics 2278.5 Basaltic Glass-Ceramics 2288.6 Zirconolite Based Glass-Ceramics 2308.7 Alternative Silicate Based Glass-Ceramics 2348.8 Phosphate Based Glass-Ceramics 234References 2379. Novel Hosts for the Immobilization of Special or Unusual Categories of Radioactive Wastes 2419.1 Silicate Glasses 2419.2 Phosphate Glasses 2469.3 Alternative Vitrification Routes 2499.4 Ceramic-Based Hosts 2519.5 Glass-Encapsulated Composite and Hybrid Systems 2539.6 Oxynitride Glasses 2599.7 Plutonium Disposition 260References 26610. Properties of Radioactive Wasteforms 27510.1 Thermal Stability 27510.2 Chemical Durability 27610.2.1 General Principles of Glass Durability 27710.2.2 Durability of Silicate Based Glasses in Water 28210.2.3 Durability of Silicate Based Glasses in Groundwaters and Repository Environments 29110.2.4 Durability of Phosphate Based Glasses 29610.2.5 Lessons to be Learnt from Archaeological Glasses 29710.2.6 Ceramic Durability 30110.2.7 Glass-Ceramic Durability 30810.2.8 Durability of Glass-Encapsulated Ceramic Hybrid Wasteforms 30910.2.9 Influence of Colloids 31010.3 Radiation Stability 31110.3.1 Glass Stability 31110.3.2 Ceramic Stability 31610.3.3 Glass-Encapsulated Ceramic Hybrid Stability 32310.4 Natural Analogues 32410.5 Mechanical Properties 32810.6 Alternative Properties 333References 33411. Structural and Modelling Studies 34311.1 Structural Studies 34311.1.1 Vitreous Wasteforms 34311.1.2 Ceramic Wasteforms 34911.2 Modelling Studies 35011.2.1 Modelling Techniques 35011.2.2 Vitreous Wasteforms 35011.2.3 Ceramic Wasteforms 356References 35712. Sources and Compositions of Nonradioactive Toxic and Hazardous Wastes, and Common Disposal Routes 36112.1 Incinerator Wastes 36512.2 Sewage and Dredging Sludges 36812.3 Zinc Hydrometallurgical and Red Mud Wastes 37012.4 Blast Furnace Slags and Electric Arc Furnace Dusts 37012.5 Alternative Metallurgical Wastes and Slags 37012.6 Metal Finishing and Plating Wastes 37112.7 Coal Ash and Fly Ash from Thermal Power Stations 37412.8 Cement Dust and Clay-Refining Wastes 37912.9 Tannery Industry Wastes 37912.10 Asbestos 38012.11 Medical Wastes 38012.12 Electrical and Electronic Wastes 38312.13 Alternative Wastes 384References 38513. Vitrification of Nonradioactive Toxic and Hazardous Wastes 38913.1 Incinerator Wastes 39213.2 Sewage and Dredging Sludges 39713.3 Zinc Hydrometallurgical and Red Mud Wastes 39813.4 Blast Furnace Slags and Electric Arc Furnace Dusts 39913.5 Alternative Metallurgical Wastes and Slags 40113.6 Metal Finishing and Plating Wastes 40313.7 Coal Ash and Fly Ash from Thermal Power Stations 40413.8 Cement Dust, Clay-Refining and Tannery Industry Wastes 40613.9 Asbestos 40613.10 Medical Waste 40713.11 Electrical and Electronic Wastes 40813.12 Alternative Wastes 40813.13 Mixed Nonradioactive Hazardous Wastes 40913.14 Glass-Ceramics for Nonradioactive Waste Immobilization 41013.15 Commercial Hazardous Waste Vitrification Facilities 418References 42014. Alternative Treatment Processes, and Characterization, Properties and Applications of Nonradioactive Wasteforms 42914.1 Alternatives to Vitrification 42914.2 Use of Alternative Waste Sources to Prepare New Materials 43514.3 Use of Waste Glass to Prepare New Materials 43514.4 Characterization, Properties and Applications of Nonradioactive Wasteforms 43614.4.1 Mechanical Properties 43614.4.2 Chemical Durability 44014.4.3 Structural and Modelling Studies 44114.4.4 Use of Less Hazardous or Nontoxic Surrogates 44214.5 Applications 444References 44515. Influence of Organic, Micro-Organism and Microbial Activity on Wasteform Integrity 45115.1 Micro-Organism Activity and Transport Mechanisms 45215.2 Repository Environments 45415.3 Repository Analogues 45715.4 Wasteforms 458References 46216. Concluding Remarks, Comparisons between Radioactive and Nonradioactive Waste Immobilization, and Outlook for the Future 46516.1 Mixed Radioactive and Nonradioactive Wastes 46516.2 System and Wasteform Comparisons 46716.2.1 Treatment Facilities 46716.2.2 Wasteforms 46916.3 Immediate and Short-Term Future Outlook 47316.4 Medium and Longer Term Future Outlook 47416.4.1 Generation IV Nuclear Energy Systems 47416.4.2 Element Partitioning and Transmutation 47816.5 Choosing a Wasteform 47916.5.1 Wasteforms Studied in the Past and Short-Term Future Direction 47916.5.2 Alternative Wasteforms and Longer Term Future Direction 48416.6 Wasteform Characterization 48616.7 Standards, Regulatory Requirements, and Performance Assessments 48716.8 Overall Conclusions 489References 490Index 493

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.

"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)

• Preface page xiAcknowledgements xiiiList of Abbreviations xv1. Introduction 11.1 Categories of Waste and Waste Generation in the Modern World 11.1.1 Radioactive Wastes from Nuclear Power and Defence Operations 21.1.2 Toxic and Hazardous Wastes 71.1.3 Other Sources of Waste Material 91.2 General Disposal Options 111.3 Radiation Issues 191.4 Waste Disposal and the Oklo Natural Nuclear Reactors 211.5 Nuclear Accidents and the Lessons Learnt 25References 312. Materials Toxicity and Biological Effects 372.1 Metals 382.1.1 Beryllium, Barium and Radium 382.1.2 Vanadium 392.1.3 Chromium, Molybdenum and Tungsten 402.1.4 Manganese, Technetium and Rhenium 402.1.5 Platinum-Group Metals 412.1.6 Nickel 422.1.7 Copper, Silver and Gold 422.1.8 Zinc, Cadmium and Mercury 432.1.9 Aluminium and Thallium 452.1.10 Tin and Lead 462.1.11 Arsenic, Antimony and Bismuth 482.1.12 Selenium, Tellurium and Polonium 492.1.13 Thorium, Uranium, Neptunium, Plutonium and Americium 502.2 Compounds 512.3 Asbestos 51References 553. Glass and Ceramic Based Systems and General Processing Methods 573.1 Glass Formation 583.1.1 Glass-Forming Ability 583.1.2 Thermal Stability 613.2 Types of Glass 613.2.1 Silicate and Borosilicate Glasses 613.2.2 Phosphate Glasses 613.2.3 Rare Earth Oxide Glasses 623.2.4 Alternative Glasses 623.3 Ceramics 623.4 Glass-Ceramics 633.5 Glass and Ceramic Based Composite Systems 683.6 Processing of Glass and Ceramic Materials 683.6.1 Melting and Vitrifi cation 693.6.2 Powder Processing and Sintering 693.6.3 Hot Pressing 693.6.4 Sol-Gel Processing 703.6.5 Self-Propagating High Temperature Synthesis 703.6.6 Microwave Processing 70References 714. Materials Characterization 754.1 Chemical Analysis 754.2 Thermal Analysis 764.3 Structural Analysis 784.3.1 Optical and Electron Microscopy 784.3.2 Energy Dispersive Spectroscopy 794.3.3 X-ray and Neutron Diffraction 794.3.4 Infra-Red and Raman Spectroscopy 804.3.5 Mössbauer Spectroscopy 804.3.6 Nuclear Magnetic Resonance 804.4 Mechanical Properties 814.4.1 Fracture Mechanics 814.4.2 Flexural Strength of Materials 834.4.3 Lifetime Behaviour 834.5 Chemical Durability and Standardized Tests 874.6 Radiation Stability 924.7 Other Properties Relevant to Wasteforms 944.8 Use of Nonradioactive Surrogates 94References 965. Radioactive Wastes 1015.1 Sources and Waste Stream Compositions 1015.1.1 Nuclear Reactor Spent Fuel Wastes 1025.1.2 Defence Wastes 1075.1.3 Surplus Materials 1085.1.4 Special or Unusual Categories of Radioactive Waste 1095.2 General Immobilization Options 111References 1156. Immobilization by Vitrification 1216.1 Vitrification History and the Advancement of Melter Design 1216.1.1 Pot Processes 1226.1.2 Continuous Melting by Induction Furnace 1246.1.3 Joule-Heated Ceramic Melters 1286.1.4 Cold Crucible Induction Melters 1316.1.5 Plasma Arc/Torch Melters 1356.1.6 Microwave Processing 1386.1.7 In situ Melting 1386.1.8 Bulk Vitrification 1386.1.9 Alternative Melting Techniques 1386.1.10 Vitrification Incidents and the Lessons that have been Learnt 1406.2 Difficult Waste Constituents 1446.2.1 Molybdenum and Caesium 1446.2.2 Platinum Group Metals 1476.2.3 Technetium 1496.2.4 Chromium, Nickel and Iron 1506.2.5 Halides 1506.2.6 Sulphates 1506.2.7 Phosphates 1516.3 Effect of Specific Batch Additives on Melting Performance 1516.4 Types of Glass and Candidate Glass Requirements 1516.4.1 Silicate and Borosilicate Glass 1516.4.2 Phosphate Glasses 1636.4.3 Rare Earth Oxide Glasses 1656.4.4 Alternative Glasses 1666.5 Glass-Forming Ability 1686.6 Alternative Methods for Producing Glassy Wasteforms 1696.6.1 Sintered and Porous Glass 1696.6.2 Hot-Pressed Glass 1716.6.3 Microwave Sintering 1756.6.4 Self-Sustaining Vitrification 1766.6.5 Plasma Torch Incineration and Vitrification 177References 1777. Immobilization of Radioactive Materials as a Ceramic Wasteform 1857.1 Titanate and Zirconate Ceramics 1857.2 Phosphate Ceramics 2037.3 Aluminosilicate Ceramics 2077.4 Alternative Ceramics 2097.5 Cement Based Systems 211References 2128. Immobilization of Radioactive Materials as a Glass-Ceramic Wasteform 2218.1 Barium Aluminosilicate Glass-Ceramics 2228.2 Barium Titanium Silicate Glass-Ceramics 2228.3 Calcium Magnesium Silicate Glass-Ceramics 2228.4 Calcium Titanium Silicate Glass-Ceramics 2278.5 Basaltic Glass-Ceramics 2288.6 Zirconolite Based Glass-Ceramics 2308.7 Alternative Silicate Based Glass-Ceramics 2348.8 Phosphate Based Glass-Ceramics 234References 2379. Novel Hosts for the Immobilization of Special or Unusual Categories of Radioactive Wastes 2419.1 Silicate Glasses 2419.2 Phosphate Glasses 2469.3 Alternative Vitrification Routes 2499.4 Ceramic-Based Hosts 2519.5 Glass-Encapsulated Composite and Hybrid Systems 2539.6 Oxynitride Glasses 2599.7 Plutonium Disposition 260References 26610. Properties of Radioactive Wasteforms 27510.1 Thermal Stability 27510.2 Chemical Durability 27610.2.1 General Principles of Glass Durability 27710.2.2 Durability of Silicate Based Glasses in Water 28210.2.3 Durability of Silicate Based Glasses in Groundwaters and Repository Environments 29110.2.4 Durability of Phosphate Based Glasses 29610.2.5 Lessons to be Learnt from Archaeological Glasses 29710.2.6 Ceramic Durability 30110.2.7 Glass-Ceramic Durability 30810.2.8 Durability of Glass-Encapsulated Ceramic Hybrid Wasteforms 30910.2.9 Influence of Colloids 31010.3 Radiation Stability 31110.3.1 Glass Stability 31110.3.2 Ceramic Stability 31610.3.3 Glass-Encapsulated Ceramic Hybrid Stability 32310.4 Natural Analogues 32410.5 Mechanical Properties 32810.6 Alternative Properties 333References 33411. Structural and Modelling Studies 34311.1 Structural Studies 34311.1.1 Vitreous Wasteforms 34311.1.2 Ceramic Wasteforms 34911.2 Modelling Studies 35011.2.1 Modelling Techniques 35011.2.2 Vitreous Wasteforms 35011.2.3 Ceramic Wasteforms 356References 35712. Sources and Compositions of Nonradioactive Toxic and Hazardous Wastes, and Common Disposal Routes 36112.1 Incinerator Wastes 36512.2 Sewage and Dredging Sludges 36812.3 Zinc Hydrometallurgical and Red Mud Wastes 37012.4 Blast Furnace Slags and Electric Arc Furnace Dusts 37012.5 Alternative Metallurgical Wastes and Slags 37012.6 Metal Finishing and Plating Wastes 37112.7 Coal Ash and Fly Ash from Thermal Power Stations 37412.8 Cement Dust and Clay-Refining Wastes 37912.9 Tannery Industry Wastes 37912.10 Asbestos 38012.11 Medical Wastes 38012.12 Electrical and Electronic Wastes 38312.13 Alternative Wastes 384References 38513. Vitrification of Nonradioactive Toxic and Hazardous Wastes 38913.1 Incinerator Wastes 39213.2 Sewage and Dredging Sludges 39713.3 Zinc Hydrometallurgical and Red Mud Wastes 39813.4 Blast Furnace Slags and Electric Arc Furnace Dusts 39913.5 Alternative Metallurgical Wastes and Slags 40113.6 Metal Finishing and Plating Wastes 40313.7 Coal Ash and Fly Ash from Thermal Power Stations 40413.8 Cement Dust, Clay-Refining and Tannery Industry Wastes 40613.9 Asbestos 40613.10 Medical Waste 40713.11 Electrical and Electronic Wastes 40813.12 Alternative Wastes 40813.13 Mixed Nonradioactive Hazardous Wastes 40913.14 Glass-Ceramics for Nonradioactive Waste Immobilization 41013.15 Commercial Hazardous Waste Vitrification Facilities 418References 42014. Alternative Treatment Processes, and Characterization, Properties and Applications of Nonradioactive Wasteforms 42914.1 Alternatives to Vitrification 42914.2 Use of Alternative Waste Sources to Prepare New Materials 43514.3 Use of Waste Glass to Prepare New Materials 43514.4 Characterization, Properties and Applications of Nonradioactive Wasteforms 43614.4.1 Mechanical Properties 43614.4.2 Chemical Durability 44014.4.3 Structural and Modelling Studies 44114.4.4 Use of Less Hazardous or Nontoxic Surrogates 44214.5 Applications 444References 44515. Influence of Organic, Micro-Organism and Microbial Activity on Wasteform Integrity 45115.1 Micro-Organism Activity and Transport Mechanisms 45215.2 Repository Environments 45415.3 Repository Analogues 45715.4 Wasteforms 458References 46216. Concluding Remarks, Comparisons between Radioactive and Nonradioactive Waste Immobilization, and Outlook for the Future 46516.1 Mixed Radioactive and Nonradioactive Wastes 46516.2 System and Wasteform Comparisons 46716.2.1 Treatment Facilities 46716.2.2 Wasteforms 46916.3 Immediate and Short-Term Future Outlook 47316.4 Medium and Longer Term Future Outlook 47416.4.1 Generation IV Nuclear Energy Systems 47416.4.2 Element Partitioning and Transmutation 47816.5 Choosing a Wasteform 47916.5.1 Wasteforms Studied in the Past and Short-Term Future Direction 47916.5.2 Alternative Wasteforms and Longer Term Future Direction 48416.6 Wasteform Characterization 48616.7 Standards, Regulatory Requirements, and Performance Assessments 48716.8 Overall Conclusions 489References 490Index 493