Gmelin Handbook of lnorganic Chemistry
8th Edition
Gmelin Handbock Volumes on Radium and Actinides
Ac Actinium* - 1942 Actinium Suppl. Vol. 1 - 1981
Np,Pu ... PartA1, I (New Suppl. Series Vol. Nr. 7 a) } - 1973 Part A 1, II" (New Suppl. Series Vol. Nr. 7 b) (Elements) - 1974 Part A2o (New Suppl. Series Vol. Nr. 8) - 1973
Part B 1 o (New Suppl. Series Vol. Nr. 31) (Metals) - 1976
Part B2* (New Suppl. Series Vol. Nr. 38) } (AIIoys)
- 1976 Part B3* (New Suppl. Series Vol. Nr. 39) - 1977
Part Co (New Suppl. Series Vol. Nr. 4) (Compounds) - 1972
Part D 1 o (New Suppl. Series Vol. Nr. 20) } (Chemistry in Solution)
- 1975 Part D2o (New Suppl. Series Vol. Nr. 21) - 1975
Index- 1979
Pa Protactinium Main Volume* - 1942 Protactinium Suppl. Vol. 1 o (Element) - 1977
Ra
Th
u
Protactinium Suppl. Vol. 2° (Metal. Alloys. Compounds. Chemistry in Solution) - 1977
Radium Main Volume* Radium Suppl. Vol. 1 *
Radium Suppl. Vol. 2
Thorium Main Volume* Thorium Suppl. Vol. C1 *
Thorium Suppl. Vol. C2 *
Uranium Main Valurne * Uranium Suppl. Vol. A 1 * Uranium Suppl. Vol. A2o Uranium Suppl. Vol. A3 * Uranium Suppl. Vol. A4 Uranium Suppl. Vol. C1 *
Uranium Suppl. Vol. C2 *
Uranium Suppl. Vol. C3 * Uranium Suppl. Vol. er Uranium Suppl. Vol. C8* Uranium Suppl. Vol. C9 Uranium Suppl. Vol. C11
Uranium Suppl. Vol. C14 Uranium Suppl. Vol. D2 Uranium Suppl. Vol. E1 Uranium Suppl. Vol. E2o
Completely or o in part in German
- 1928 (History. Cosmochemistry. Geochemistry) - 1977 (Element. Compounds) - 1977
- 1955 (Compounds with Rare Gases, Hydrogen, Oxygen) - 1978 (Ternary and Polynary Oxides) - 1976
- 1936 (Uranium Deposits) - 1979 (Isotopes) - 1980 (Technology. Uses) - 1981 (lrradiated Fuel. Reprocessing) -1982(present volume) (Compounds with Rare Gases and Hydrogen. Uranium-Oxygen System) - 1977 (U 3 0 8 and U0 3 Oxides. Hydroxides and Oxide Hydrates. Peroxides) - 1978 (Ternary and Polynary Oxides) - 1975 (Compounds with Nitrogen) - 1981 (Compounds with Fluorine) - 1980 (Compounds with Chlorine, Bromine,lodine) -1979 (Compounds with Selenium, Tellurium, and Baron)- 1981 (Compounds with P, As, Sb, Bi, Ge) - 1981 (Solvent Extraction) - 1982 (Coordination Compounds) - 1979 (Coordination Compounds) - 1980
Grnelin Handbuch der Anorganischen Chemie
BEGRÜNDET VON
ACHTE AUFLAGE BEGONNEN
FORTGEFÜHRT VON
HERAUSGEGEBEN VOM
Achte völlig neu bearbeitete Auflage
Leopold Gmelin
im Auftrag der Deutschen Chemischen Gesellschaft von R. J. Meyer
E. H. E. Pietsch und A. Kotowski Margot Becke-Goehring
Gmelin-lnstitut für Anorganische Chemie der Max-Pianck-Gesellschaft zur Förderung der Wissenschaften Direktor: Ekkehard Fluck
Springer-Verlag Berlin Heidelberg GmbH 1982
Gmelin-lnstitut für Anorganische Chemie der Max-Pianck-Gesellschaft zur Förderung der Wissenschaften
KURATORIUM (ADVISORY BOARD)
Dr. J. Schaafhausen, Vorsitzender (Hoechst AG, Frankfurt/Main-Höchst), Dr. G. Breil (RuhrchemieAG, Oberhausen-Holten), Dr. G. Broja (Bayer AG, Leverkusen), Prof. Dr. G. Fritz (Universität Karlsruhe), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. R. Hoppe (Universität Gießen), Prof. Dr. R. Lüst ( Präsidentder Max-Pianck-Gesellschaft, München), Dr. H. Moell (BASF-Aktiengesellschaft, Ludwigshafen), Prof. Dr. E. L. Muetterties (University of California,Berkeley,California), Prof. Dr. H. Nöth (Universität München), Prof. Dr.A. Rabenau (Max-Pianck-lnstitut für Festkörperforschung, Stuttgart), Prof. Dr. Dr. h.c. mult. G. Wilke (Max-Pianck-lnstitut für Kohlenforschung, Mülheim/Ruhr)
DIREKTOR (DIRECTOR)
Prof. Dr. Dr. h.c. Ekkehard Fluck
HAUPTREDAKTEURE (CHIEF EDITORS)
STELLVERTRETENDER DIREKTOR (DEPUTY DIRECTOR)
Dr. W. Lippert
Dr. K.-C. Buschbeck, Ständiger Hauptredakteur Dr. H. Bergmann, Dr. H. Bitterer, Dr. H. Katscher, Dr. R. Keim, Dipl.-lng. G. Kirschstein, Dipi.Phys. D. Koschel, Dr. U. Krüerke, Dr. H. K. Kugler, Dr. E. Schleitzer- Rust, Dr. A. Slawisch, Dr. K. Swars, Dr. B. v. Tschirschnitz-Geibler, Dr. R. Warncke
MITARBEITER (STAFF)
Z. Amerl, D. Barthel, Dr. N. Baumann, I. Baumhauer, Dr. K. Beeker, Dr. W. Behrendt, Dr. L. Berg, Dipi.-Chem. E. Best, M. Brandes, E. Brettschneider, E. Cloos, Dipi.-Phys. G. Czack, I. Deim, Dipi.-Chem. H. Demmer, R. Dombrowsky, R. Dowideit, Dipi.-Chem.A. Drechsler, Dipi:-Chem. M. Drößmar, M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust, I. Fischer, Dr. R. Froböse, J. Füssel, Dipl.-lng. N. Gagel, Dipi.-Chem. H. Gedschold, E. Gerhardt, Dr. U. W. Gerwarth, M.-L. Gerwien, Dipi.-Phys. D. Gras, Dr. V. Haase, H. Hartwig, B. Heibel, Dipi.-Min. H. Hein, G. Heinrich-Sterze!, H.-P. Hente, H. W. Herold, U. Hettwer, U. Hilberger, Dr. I. Hinz, Dr. W. Hoffmann, Dipi.-Chem. K. Holzapfel, Dipi.-Chem. W. Karl, H.-G. Karrenberg, Dipi.-Phys. H. Keller-Rudek, I. Knauss, Dipi.-Phys. E. Koch, Dr. E. Koch, Dipi.-Chem. K. Koeber, Dipi.-Chem. H. Köttelwesch, R. Kalb, E. Kranz, Dipi.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr. P. Kuhn, M. Langer, M.-L. Lenz, Dr. A. Leonard, Dipi.-Chem. H. List, H.Mathis, E. Meinhard, Dr. P. Merlet, K. Meyer, M. Michel, K. Nöring, C. Pielenz, E. Preißer, I. Rangnow, Dipi.-Phys. H.-J. RichterDitten, Dipi.-Chem. H. Rieger, E. Rieth, Dr. J. F. Rounsaville, E. Rudolph, G. Rudolph, Dipi.Chem. S. Ruprecht, D. Schädle, V. Schlicht, Dipi.-Chem. D. Schneider, Dr. F. Schröder, Dipi.Min. P. Schubert, A. Schwärze!, Dipl.-lng. H. M. Somer, E. Sommer, Dr. P. Stieß, M. Teichmann, Dr. W. Töpper, U. Trautwein, Dipl.-lng. H. Vanecek, Dipi.-Chem. P. Velic, Dipl.lng. U. Vetter, Dipi.-Phys. J. Wagner, R. Wagner, Dipi.-Chem. S. Waschk, Dr. G. Weinberger, Dr. H. Wendt, Dr. B. Wöbke, K. Wolff, Dr. A. Zelle, U. Ziegler
FREIE MITARBEITER (CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF)
Dr. I. Kubach, Prof. Dr. P. F. Linde, Prof. Dr. Y. Marcus, Dr. K. Rumpf, Dr. R. C. Sangster, Dr. R. P. Taylor, Dr. U. Trobisch
EM. WISSENSCHAFTLICHES MITGLIED
(EMERITUS MEMBER OF THE INSTITUTE)
AUSWÄRTIGE WISSENSCHAFTLICHE MITGLIEDER
(CORRESPONDENT MEMBERS OF THE INSTITUTE)
Prof. Dr. Dr. E. h. Margot Becke
Prof. Dr. Hans Bock Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)
Grnelin Handbook of lnorganic Chemistry
AUTHORS
CHIEF EDITORS
8th Edition
u Uranium Supplement Valurne A4
Behavior of Uranium Fuels in Nuclear Reactors. Reprocessing of Spent Nuclear Fuels
With 173 illustrations
Helmut Aßmann, Kraftwerk Union AG, Erlangen
Erich Merz, Kernforschungsanlage, Jülich
Aristides Naoumidis, Kernforschungsanlage, Jülich
Hubertus Nickel, Kernforschungsanlage, Jülich
Heinz Stehle, Kraftwerk Union AG, Erlangen
Gilbert N. Walton, Department of Chemical Engineering and Chemical Technology, Imperial College, London University, London, U.K.
Kari-Christian Buschbeck, Gmelin-lnstitut, Frankfurt am Main
Cornelius Keller, Supervising scientific coordinator for the Uranium Supplement Volumes, Schule für Kerntechnik, Kernforschungszentrum Karlsruhe
System Number 55
Springer-Verlag Berlin Heidelberg GmbH 1982
LITERATURE CLOSING DATE: END OF 1979
IN MANY GASES MORE REGENT DATA HAVE BEEN CONSIDERED
Library of Congress Catalog Card Number: Agr 25-1383
ISBN 978-3-662-06016-2 ISBN 978-3-662-06014-8 (eBook) DOI 10.1007/978-3-662-06014-8
This work is subject to copyright. All rights are reserved whether the whole or part of the material is concerned specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under §54 of the German Copyright Law where copies are made for other then for private use, a Iee is payable to "Verwertungsgesellschaft Wort", Munich.
© by Springer- Verlag Berlin Heidelberg 1981
Originally published by Springer-Verlag, Berlin · Heidelberg · New York 1981 Softcoverreprint of the hardcover8th edition 1981
The use of generat descriptive names, trade marks, etc. in the Gmelin Handbook, even if the !armer arenot especially identified, is not tobe taken as a sign !hat such names, as understood by the Trade Marksand Merchandise Marks Act, may according be used freely by anyone.
Preface
The present volume A4 of the "Uranium" series of the Gmelin Handbook deals with two very important technological aspects of the nuclear fuel cycle:
- the behavior of fuel elements during burnup in a nuclear reactor, and - the reprocessing of spent fuel to recover the non-fissioned uranium and newly created materials.
The usefullifetime of a fuel element in a nuclear reactor depends strongly on the change of its chemical and physical properties during irradiation. Properties like thermal conductivity, swelling, creep, and oxygen-to-metal ratio are strongly affected by the intense neutron field and the energetic fission products. Furthermore, the high temperature gradient in a fuel element also produces alterations of the initial fuel. such as densification or U: Pu segregation. All of these effects are thoroughly discussed for the different kinds of fuels to be used in modern nuclear reactors today or in the future. The vast amount of very often Contradietory results in sometimes difficultly obtainable Iiterature has been summarized to create a compendium in this field with the two sections, on oxide and on carbide and nitride fuels, respectively.
The chapters on reprocessing of spent fuels deal only with fuel elements of the uraniumthorium fuel cycle and with those containing fuel highly enriched in 235U. The treatment of U02
and (U,Pu)02 has already been given in the transuranic element series.
Due to the vast amount of Iiterature published within the topics of this book, only selected and important papers have been mentioned here. For other references see the "General References" etc. in this book. The Iiterature is evaluated for the period up to the end of 1979, in many cases more recent Iiterature has been considered.
I thank the authors from industry and the nuclear research centers for their excellent collaboration. I thank also the Gmelin Institute, with Prof. Dr. Y. Marcus, who translated the originally German text into English, Dr. K. C. Buschbeck as the supervising editor and Prof. Dr. Dr. h.c. E. Fluck as director, for its support and encouragement.
Frankfurt am Main December 1981 Cornelius Keller
Table of Contents
1 The Behavior of Uranium Fuels in Nuclear Reactors.
1.1 Oxide Fuels . .
lntroduction and Survey
1.1.1 Effects of the Fission Fragments in the Crystal Lattice
Properties of the Fission Fragment Spike . . lncreased Seit-Diffusion . . . . . . . . . . Formation and Annealing of Lattice Defects .
1.1 .2 Mechanical Behavior . . . . . . . . .
Elastic Behavior. . . . . . . . . . . . . . Plastic Behavior and Behavior upon Fracture Creep Behavior . . . .
Theoretical Models . . . . . Experimental Results . . . . Primary and Transient Creep .
1.1.3 Thermal Behavior. . . . .
Thermal Conductivity and Conductivity Integral of U02 .
Experimental Results . . . . . . . . . . . . . . . Thermal Expansion and Specific Heat Capacity. . . . .
1.1 .4 Behavior of the Fission Products and Release of Fission Gases
Concentration of the Fission Products. Solid and Volatile Fission Products . . . . .
Fission Products in the Fuel . . . . . . . The Behavior of Volatile Fission Products .
Behavior of the Fission Gases in the Fuel The Formation and Growth of Bubbles Bubble Migration .....
The Release of Fission Gases .. Experimental . . . . . . . . Models for Low Tamperatures Models for Intermediate Tamperatures Model for High Tamperatures .... The Diffusion Coefficient of Fission Gases
Page
1
3
5
5 8 8
11
11 12 14 17 19 26
29
29 30 35
39
40 40 41 44 45 46 48 50 50 50 51 63 64
1.1.5 Changes in Dimensions lnduced by Irradiation (Densification and Swelling) . 70
lrradiation-lnduced Densification . . . . . . . . . . . . . . . . . . . . . . . 71 Theoretical Models for Thermally Activated and lrradiation-lnduced Densification 71 Experimental Studies . . . 77
Swelling by Fission Products. . . . 80 Experimental Results . . . . . . 80 Mechanistic and Empirical Models 84
The Superposition of Swelling, Densification, and Other Deformative Phenomena . 86
II
1.1 .6 Restructuring. . . . . . . . . . . . . . . . .
Phenomenological Description of the Structural Zones Crack Patterns and Relocation Grain Growth. . . . .
Theoretical Models . . . . Experimental Results . . .
Pore Migration, Columnar Grain Growth, Central Void
1.1.7 Changes in the Stoichiometry, Redistribution of Oxygen and Uranium/
Page 92
92 95 98 98 99
102
Plutonium . . . . . . . 106
Thermodynamic Data Base. . Changes in the Stoichiometry
Fuel in Steel Cladding. . Fuel in Zircaloy Cladding .
Redistribution of Oxygen . . Redistribution of Uranium and Plutonium in a Mixed Oxide.
1.1.8 Interaction with the Cladding ..
107 110 110 112 112 118
123
lnterior Corrosion in Zircaloy Cladding 124 lnterior Corrosion in Steel Cladding. . 124 Cooperative Mechanical and Chemical lnteractions. 126
Mechanical Interaction between Fuel and Cladding 126 Stress Corrosion Cracking (SCC) Arising from Pellet/Ciad Interaction (PCI) 127
1.1.9 Behavior of Oxidic Nuclear Fuels in Defective Fuel Rods.
Water Cooled Fuel Elements . Sodium Cooled Fuel Elements . . . . . .
1.2 Carbide and Nitride Nuclear Fuels.
1.2.1 lntroduction . . . . . . . . . . . .
1.2.2 Properties in the Non-lrradiated State
Mechanical Properties . Creep Behavior . . . . . .
Carbides ....... . Nitrides, Carbide Nitrides
Elastic Properties Strength . . . . Hardness ....
Thermal Properties Coefficient of Thermal Expansion.
Carbides ....... . Nitrides, Carbide Nitrides
Thermal Conductivity Carbides. Nitrides .... .
Diffusion ...... . Seit-Diffusion in Uranium Carbides.
Effect of the Composition on the Diffusion of Uranium.
135
135 137
139
139
142
143 143 143 146 148 150 151 153 153 153 154 156 156 160 164 164 165
III
Page Effect of lmpurities on the Diffusion of Uranium. 166 Effect of Nitrogen on the Diffusion of Uranium 167 Diffusion of Other Actinides in Carbides . . . 167 The Contribution of Grain-Boundary Diffusion 168
Diffusion of Carbon in Carbides . . . . . . . . 169 The Effect of Nitrogen on the Mobility of the Carbon 170
Self-Diffusion of Metal Atoms in Nitrides. . . . . 170 Diffusion of Nitrogen in Nitrides . . . . . . . . . 171 Diffusion of Fission Gases in Carbides and Nitrides 171
Electrical Resistivity . 175 Carbides . . . . . . . . . . . . 175 Nitrides . . . . . . . . . . . . 177
Compatibility with Metallic Materials 180 Compatibility of Carbidic Fuels and Breeding Materials with Austenitic Steels 180 Compatibility of UC with Other Metallic Materials . . . . 184 Compatibility of (U,Pu)C with Various Cladding Materials 185 Compatibility of Nitride Fuels with the Cladding. 187 Compatibility of Uranium Carbide Nitrides. . . . . . . . 188
1 .2.3 Irradiation Behavior. . . . . . . . . . 191
Changes in the Physical Properties . . . . . 191 lrradiation-lnduced Creep Processes in UC and UN 191 Irradiation Effects on Diffusional Processes 192 Change of the Hardness on Irradiation 193 Changes ofThermal Conductivity . 194 Changes of the Electrical Resistivity 195
In-Pile Compatibility. . . . . . . . . 196 Carbide Fuels. . . . . . . . . . . 196
Results of Irradiation of UC with Cr-Ni Steels. 197 UC with Tungsten . . . . . 198 UCwithNb-1%Zr..... 198 (U,Pu)C with Stainless Steel 198 (U,Pu)C with Nb-1% Zr 201
Nitride Fuels . . . . . . . 201 lrradiation-lnduced Swelling . 204
Uranium Carbide . . . . . 204 lrradiation-lnduced Swelling of (U,Pu)C Mixed Carbides. 209 Nitride and Nitrogen-Containing Carbide Fuels: UN, U(C,N). (U,Pu)N, and (U,Pu)(C,N) . . . . . . . . . . . . . . . . . . . . . 214 Mechanism of the Swelling of Carbide and Nitride Fuels . 218
The Release of Gaseous Fission Products . 227 Mechanisms of the Fission Gas Release. . . . . . . . . 227 Fission Gas Release from UC . . . . . . . . . . . . . 228
The Temperature Dependence of the Fission Gas Release from UC 228 Effect of the Stoichiometry on the Fission Gas Release from UC 230 Effect of the Porosity and the Microstructure . 231 Effect of the Burnup and of the Power Density 233
Fission Gas Release from (U,Pu)C . . 234 Fission Gas Release from Nitride Fuels . . . . . 241
IV
The Behavior of Solid Fission Products and of Plutonium in Carbide and Nitride Fuels during Irradiation . . . . . . . . . . . . . . . . . . . . .
Solid Fission Products in the Fuel . . . . . . . . . . . . . . . The Distribution of Plutonium in Carbide and Nitride Fuels . . . . Interaction of the Fuel and the Fission Products with the Cladding
2 Reprocessing of Spent Nuclear Fuels
2.1 lntroduction . . . . . . . . . . . .
2.2 Reprocessing of Spent Fuel of the U-Pu Nuclear Fuel Cycles
2.3 The Reprocessing of Enriched 235 U Fuels
2.3.1 I ntroduction . . . . . .
2.3.2 Storage of lrradiated Fuel
2.3.3 Disassembly of Fuel . .
Mechanical Operations . . . Chemical Methods of Decladding and Dissolution
Aluminium Based Fuel Uranium Metal . . . . . . Zirconium Based Fuel . . . Stainless Steel Canned Fuel Other Types of Fuel.
2.3.4 Dissolvers . . . .
2.3.5 Solvent Extraction
2.3.6 Pyrometallurgical Processing.
lntroduction . . . Fluoride Volatility . Melt Processing. .
2.4 Reprocessing of Spent 232Th- 233 U Fuels . . . . . .
2.4.1 Application of the Thorium Cycle for Energy Production
Nuclear Reactions and the Buildup of Actinides in the Thorium Cycle The Use of Thorium in Various Reactor Systems . Types of Fuel Elements . . . . . . . . . .
2.4.2 Classification of Reprocessing Methods.
Page
250 251 254 256
258
258
258
259
259
262
262
262 263 263 264 264 265 265
266
268
272
272 273 273
276
276
276 277 278
283
Listing of the Processes . . . . . . . . . . 284 The History of the Development of 232Th- 233 U Reprocessing 286 Composition of the lrradiated Fuel Elements . . . . . . . . 289
2.4.3 Head-End Processing of lrradiated Thorium-Containing Fuel Elements. 293
Removal of the Metallic Cladding of the Fuel . . . . . . . . . . . . . . 294 Removal of the Pyrolytic Carbon Coating and of the Graphite Matrix of HTR Fuel Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
Dissolution of Thorium-Containing Fuels and Fertile Materials. Treatment of the Off-Gases . . . . . . . . . . . . . . Adjustment of the Feed Solution . . . . . . . . . . . .
2.4.4 Chemical Separation by Means of Solvent Extraction
Chemistry of the Aqueous Process Solution . . Choice of the Extraction System . . . . . . . Characteristics of the Processes and the Plants. Extraction with Ketones Extraction with Ethers . . . . . . . . . . . Extraction as Chelates . . . . . . . . . . . Extraction with Alkylphosphorus Compounds Extraction with Amines . . . . . . . . . .
2.4.5 Extractive Reprocessing of Thorium-Containing Nuclear Fuels and Breeding
V
Page 298 300 302
310
310 310 310 311 312 312 312 313
Materials with the HN0 3 -TBP-Kerosene System 317
General Aspects. . . . . . . . . . . . . . . . . . . . . The Chemistry of the Separation . . . . . . . . . . . . . Chemical and Radiation-Chemical Stability of the Extractant The THOREX Process . . . . . . . . . . . . . . . . . .
2.4.6 Chemical Separation by Means of Sorption and Ion Exchange
317 317 319 320
326
Primary Separation by Ion Exchange . . . . . . . . . . . . . . 327 Purification of the Uranium Product by Sorption and Ion Exchange 328 Extraction Chromatography . . . . . . . . . . . . . . . . 329
2.4.7 Reprocessing by Means of Halide Volatilization Processes 332
Fluorination of Solids . . . 333 Fluorination of Malten Salts 334 Purification of UF6 • • • • 335 Chlorination of Solids . . . 336
2.4.8 Reprocessing by Application of Pyrochemical Processes 341
Fractional Crystallization and Distillation. . . . . . . 342 Distribution between lmmiscible Metal and Salt Melts 343 Oxidation-Reduction Reactions, Slag Formation . . 344 Electrochemical Separation Processes . . . . . . . 345
2.4.9 Refabrication of New Nuclear Fuels from 233U 349
Radiation Safety Provisions in the Handling of 233U 349 Processes for the Refabrication of 233 U Fuels . . . 350 Production of Fuel Particles for the Recycling of 233 U in Advanced Reactor Systems 351
Table of Gonversion Factors . . . . . . . . . . . . . . . . . . . . . . . . 358