Waste Immobilization in Glass and Ceramic Based Hosts: Radioactive, Toxic and Hazardous Wastes

516 Pages·2010·9.734 MB·English

by  Ian W. Donald(auth.)

Waste Immobilization
in Glass and
Ceramic Based Hosts
Waste Immobilization in Glass and Ceramic Based Hosts: Radioactive, Toxic and Hazardous Wastes Ian W. Donald
© British Crown Owned Copyright 2010/MOD. ISBN: 978-1-444-31937-8
Waste Immobilization
in Glass and
Ceramic Based Hosts
Radioactive, Toxic and
Hazardous Wastes
IAN W. DONALD
Materials Science Research Division,
Atomic Weapons Establishment, UK
A John Wiley & Sons, Ltd., Publication
This edition fi rst published 2010
© Crown Copyright 2010/MoD. Published with the permission of the Controller of Her Britannic Majesty’s Stationery
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Library of Congress Cataloging-in-Publication Data
Donald, Ian W.
Waste immobilization in glass and ceramic based hosts : radioactive, toxic, and hazardous wastes / Ian W. Donald.
p. cm.
Includes bibliographical references and index.
ISBN 978-1-4443-1937-8 (cloth)
1. Hazardous wastes–Solidifi cation. 2. Radioactive wastes–Vitrifi cation. I. Title.
TD1063.D66 2010
628.4'2–dc22
2009054396
A catalogue record for this book is available from the British Library.
ISBN HB: 978-1-444-31937-8
Set in 10 on 12 pt Times by Toppan Best-set Premedia Limited
Printed and bound in Great Britain by CPI Antony Rowe, Chippenham, Wiltshire
Contents
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
vi Contents
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
Contents vii
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 Vitrifi cation 121
6.1 Vitrifi cation 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 Vitrifi cation 138
6.1.9 Alternative Melting Techniques 138
6.1.10 Vitrifi cation Incidents and the Lessons that have been Learnt 140
6.2 Diffi cult 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 Specifi c 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 Vitrifi cation 176
6.6.5 Plasma Torch Incineration and Vitrifi cation 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
viii Contents
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 Vitrifi cation 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 Infl uence 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
Contents ix
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-Refi ning 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. Vitrifi cation 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-Refi ning 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
x Contents
13.15 Commercial Hazardous Waste Vitrifi cation Facilities 418
References 420
14. Alternative Treatment Processes, and Characterization, Properties and
Applications of Nonradioactive Wasteforms 429
14.1 Alternatives to Vitrifi cation 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. Infl uence 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
Over the last few years the problem of what to do with waste materials both radioactive
and, more recently, nonradioactive, has become an increasingly important environmental
and political issue.
In the case of radioactive wastes from reprocessed nuclear fuel and certain defence
operations, vitrifi cation has been the vanguard of past and current treatment options. More
recently, the threat of global warming and the need for low carbon energy sources has
brought nuclear issues back to the forefront of scientifi c, technical and public awareness,
with the building of new nuclear power plants, coupled with the longer term likelihood
of a future generation of advanced closed fuel cycle nuclear energy systems, the so - called
Generation IV systems (GenIV). As worldwide demand for uranium increases with these
new requirements, and stocks are depleted, fuel recycling, with the corresponding genera-
tion of various categories of radioactive wastes, will become an ever more important
issue. Of serious concern at this time is the lack of specialists in areas relating to nuclear
power and particularly nuclear waste, and this book provides an up - to - date reference
source at this critical time, with the emphasis on waste immobilization. On the other hand,
it is becoming increasingly essential from an environmental perspective, as regulated
land - fi ll sites become full and/or more expensive, that more be done to address problems
associated with the ever increasing volume of nonradioactive hazardous wastes, until
recently treated with somewhat less respect than their radioactive counterparts. One solu-
tion to this problem is to turn hazardous wastes into vitrifi ed or ceramic products where
the hazardous elements are chemically immobilized and made passively safe, and it is in
this area that certain practical lessons can be learnt from the nuclear industry with its long
history and experience of waste treatment and vitrifi cation technologies. An added advan-
tage and incentive in the case of nonradioactive wastes is that, rather than generating a
product that must be disposed of, treatment may actually turn hazardous wastes into useful
products with practical applications.
T his book brings together all aspects of waste immobilization, draws comparisons
between the different types of wastes and treatments, and outlines where lessons learnt
in the radioactive waste fi eld can be of benefi t in the treatment of nonradioactive wastes.
These are areas very much of topical interest, rarely covered together despite the similari-
ties that can be drawn. A wide range of topics is covered, beginning with introductory
chapters which outline environmental aspects and provide information relating to generic
sources and categories of wastes, potential disposal options, and where lessons can be
learnt from nature and from certain incidents and accidents that have occurred from time
to time. In the following chapters, immobilization of high level waste and special catego-
ries of intermediate level waste are covered in depth. Details of specifi c waste systems