Table Of ContentGmelin 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) - 1976
} (AIIoys)
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) - 1975
} (Chemistry in Solution)
Part D2o (New Suppl. Series Vol. Nr. 21) - 1975
Index- 1979
Pa Protactinium Main Volume* - 1942
Protactinium Suppl. Vol. 1 o (Element) - 1977
Protactinium Suppl. Vol. 2° (Metal. Alloys. Compounds. Chemistry in
Solution) - 1977
Ra Radium Main Volume* - 1928
Radium Suppl. Vol. 1 * (History. Cosmochemistry.
Geochemistry) - 1977
Radium Suppl. Vol. 2 (Element. Compounds) - 1977
Th Thorium Main Volume* - 1955
Thorium Suppl. Vol. C1 * (Compounds with Rare Gases, Hydrogen,
Oxygen) - 1978
Thorium Suppl. Vol. C2 * (Ternary and Polynary Oxides) - 1976
u
Uranium Main Valurne * - 1936
Uranium Suppl. Vol. A 1 * (Uranium Deposits) - 1979
Uranium Suppl. Vol. A2o (Isotopes) - 1980
Uranium Suppl. Vol. A3 * (Technology. Uses) - 1981
Uranium Suppl. Vol. A4 (lrradiated Fuel. Reprocessing) -1982(present volume)
Uranium Suppl. Vol. C1 * (Compounds with Rare Gases and Hydrogen.
Uranium-Oxygen System) - 1977
Uranium Suppl. Vol. C2 * (U 0 and U0 Oxides. Hydroxides and Oxide
3 8 3
Hydrates. Peroxides) - 1978
Uranium Suppl. Vol. C3 * (Ternary and Polynary Oxides) - 1975
er
Uranium Suppl. Vol. (Compounds with Nitrogen) - 1981
Uranium Suppl. Vol. C8* (Compounds with Fluorine) - 1980
Uranium Suppl. Vol. C9 (Compounds with Chlorine, Bromine,lodine) -1979
Uranium Suppl. Vol. C11 (Compounds with Selenium, Tellurium,
and Baron)- 1981
Uranium Suppl. Vol. C14 (Compounds with P, As, Sb, Bi, Ge) - 1981
Uranium Suppl. Vol. D2 (Solvent Extraction) - 1982
Uranium Suppl. Vol. E1 (Coordination Compounds) - 1979
Uranium Suppl. Vol. E2o (Coordination Compounds) - 1980
Completely or o in part in German
Grnelin Handbuch
der Anorganischen Chemie
Achte völlig neu bearbeitete Auflage
BEGRÜNDET VON Leopold Gmelin
ACHTE AUFLAGE BEGONNEN im Auftrag der Deutschen Chemischen Gesellschaft
von R. J. Meyer
FORTGEFÜHRT VON E. H. E. Pietsch und A. Kotowski
Margot Becke-Goehring
HERAUSGEGEBEN VOM Gmelin-lnstitut für Anorganische Chemie
der Max-Pianck-Gesellschaft zur Förderung der Wissen
schaften
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) STELLVERTRETENDER DIREKTOR (DEPUTY DIRECTOR)
Prof. Dr. Dr. h.c. Ekkehard Fluck Dr. W. Lippert
HAUPTREDAKTEURE (CHIEF EDITORS)
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. Richter
Ditten, 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 Prof. Dr. Dr. E. h. Margot Becke
(EMERITUS MEMBER OF THE INSTITUTE)
AUSWÄRTIGE WISSENSCHAFTLICHE MITGLIEDER Prof. Dr. Hans Bock
(CORRESPONDENT MEMBERS OF THE INSTITUTE) Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)
Grnelin Handbook
of lnorganic Chemistry
8th Edition
u
Uranium
Supplement Valurne A4
Behavior of Uranium Fuels in Nuclear Reactors. Reprocessing
of Spent Nuclear Fuels
With 173 illustrations
AUTHORS 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.
CHIEF EDITORS 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 uranium
thorium fuel cycle and with those containing fuel highly enriched in 235U. The treatment of U02
and (U,Pu)0 has already been given in the transuranic element series.
2
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
Page
1 The Behavior of Uranium Fuels in Nuclear Reactors.
1.1 Oxide Fuels . . 1
lntroduction and Survey 3
1.1.1 Effects of the Fission Fragments in the Crystal Lattice 5
Properties of the Fission Fragment Spike . . 5
lncreased Seit-Diffusion . . . . . . . . . . 8
Formation and Annealing of Lattice Defects . 8
1.1 .2 Mechanical Behavior . . . . . . . . . 11
Elastic Behavior. . . . . . . . . . . . . . 11
Plastic Behavior and Behavior upon Fracture 12
Creep Behavior . . . . 14
Theoretical Models . . . . . 17
Experimental Results . . . . 19
Primary and Transient Creep . 26
1.1.3 Thermal Behavior. . . . . 29
Thermal Conductivity and Conductivity Integral of U02. 29
Experimental Results . . . . . . . . . . . . . . . 30
Thermal Expansion and Specific Heat Capacity. . . . . 35
1.1 .4 Behavior of the Fission Products and Release of Fission Gases 39
Concentration of the Fission Products. 40
Solid and Volatile Fission Products . . . . . 40
Fission Products in the Fuel . . . . . . . 41
The Behavior of Volatile Fission Products . 44
Behavior of the Fission Gases in the Fuel 45
The Formation and Growth of Bubbles 46
Bubble Migration ..... 48
The Release of Fission Gases .. 50
Experimental . . . . . . . . 50
Models for Low Tamperatures 50
Models for Intermediate Tamperatures 51
Model for High Tamperatures .... 63
The Diffusion Coefficient of Fission Gases 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
Page
1.1 .6 Restructuring. . . . . . . . . . . . . . . . . 92
Phenomenological Description of the Structural Zones 92
Crack Patterns and Relocation 95
Grain Growth. . . . . 98
Theoretical Models . . . . 98
Experimental Results . . . 99
Pore Migration, Columnar Grain Growth, Central Void 102
1.1.7 Changes in the Stoichiometry, Redistribution of Oxygen and Uranium/
Plutonium . . . . . . . 106
Thermodynamic Data Base. . 107
Changes in the Stoichiometry 110
Fuel in Steel Cladding. . 110
Fuel in Zircaloy Cladding . 112
Redistribution of Oxygen . . 112
Redistribution of Uranium and Plutonium in a Mixed Oxide. 118
1.1.8 Interaction with the Cladding .. 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. 135
Water Cooled Fuel Elements . 135
Sodium Cooled Fuel Elements . . . . . . 137
1.2 Carbide and Nitride Nuclear Fuels. 139
1.2.1 lntroduction . . . . . . . . . . . . 139
1.2.2 Properties in the Non-lrradiated State 142
Mechanical Properties . 143
Creep Behavior . . . . . . 143
Carbides ....... . 143
Nitrides, Carbide Nitrides 146
Elastic Properties 148
Strength . . . . 150
Hardness .... 151
Thermal Properties 153
Coefficient of Thermal Expansion. 153
Carbides ....... . 153
Nitrides, Carbide Nitrides 154
Thermal Conductivity 156
Carbides. 156
Nitrides .... . 160
Diffusion ...... . 164
Seit-Diffusion in Uranium Carbides. 164
Effect of the Composition on the Diffusion of Uranium. 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
