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EUROPEAN COMMISSION COBECOMA State-Of-The-Art EUROPEAN COMMISSION 5th EURATOM FRAMEWORK PROGRAMME 1998-2002 KEY ACTION : NUCLEAR FISSION COBECOMA State-of-the-art document on the COrrosion BEhaviour of COntainer MAterials CONTRACT N° FIKW-CT-20014-20138 FINAL REPORT B. Kursten1, E. Smailos2, I. Azkarate3, L. Werme4, N.R. Smart5, G. Santarini6 1 SCK•CEN, Mol, Belgium (co-ordinator) 2 FZK.INE, Karlsruhe, Germany 3 INASMET, San Sebastian, Spain 4 SKB, Stockholm, Sweden 5 SERCO ASSURANCE, Abingdon, United Kingdom 6 CEA/SACLAY, Gif Sur Yvette, France Reporting Period: September 1, 2001 to December 31, 2003 Dissemination level : CO: confidential, only for partners of the COBECOMA project MT: Mid-term October 2004 W&SF – COBECOMA TABLE OF CONTENTS TABLE OF CONTENTS....................................................................................................................I PREFACE ........................................................................................................................................1 OBJECTIVES...................................................................................................................................2 EXECUTIVE SUMMARY .................................................................................................................4 KEYWORDS ..................................................................................................................................15 GLOSSARY OF TERMS................................................................................................................16 LIST OF ABBREVIATIONS AND ACRONYMS............................................................................22 PART A A.1 INTRODUCTION ....................................................................................................................26 A.2 HOST ROCK FORMATIONS FOR HLW/SPENT FUEL DISPOSAL....................................34 A.2.1 DISPOSAL IN SALT .............................................................................................................34 A.2.1.1 Characterisation of the host rock formation considered in Germany......................34 A.2.2 DISPOSAL IN CLAY.............................................................................................................35 A.2.2.1 Characterisation of the argillaceous host rock formation and bentonitic backfill material considered in Belgium ...............................................................................35 A.2.2.2 Characterisation of the host rock formation considered in France .........................38 A.2.2.3 Characterisation of the argillaceous host rock formation and bentonitic backfill material considered in Spain...................................................................................39 A.2.2.3.1 Characterisation of the argillaceous host rock formation..................................................40 A.2.2.3.2 Characterisation of the bentonitic backfill material ...........................................................40 A.2.3 DISPOSAL IN GRANITE .......................................................................................................43 A.2.3.1 Characterisation of the host rock formation considered in Sweden/Finland...........43 A.2.3.2 Characterisation of the host rock formation considered in Spain ...........................44 A.2.4 DISPOSAL IN CEMENTITIOUS BACKFILL ...............................................................................46 A.3 SCIENTIFIC BACKGROUND OF CORROSION DURING THE AEROBIC AND ANAEROBIC PERIOD ...........................................................................................................49 A.3.1 CORROSION OF FE-BASED MATERIALS................................................................................49 A.3.1.1 Effects of environmental factors..............................................................................51 A.3.1.1.1 Role of the chemistry of the aqueous environment in contact with the metallic materials .....................................................................................................................................51 A.3.1.1.2 Role of temperature......................................................................................................53 A.3.1.2 Role of pH ...............................................................................................................53 A.3.1.3 Role of radiation ......................................................................................................54 A.3.2 CORROSION OF NI-BASED MATERIALS ................................................................................56 A.3.3 CORROSION OF CU-BASED MATERIALS ...............................................................................59 A.3.3.1 Copper corrosion in the presence of oxygen ..........................................................59 A.3.3.1.1 Influence of chloride in the presence of oxygen ...........................................................60 2- A.3.3.1.2 Influence of other anions (SO4 , ammonia) .................................................................61 A.3.3.1.3 Mechanism for the corrosion of copper in compacted buffer material saturated with saline, O2-containing groundwater...............................................................................61 A.3.3.2 Copper corrosion in the absence of oxygen ...........................................................62 A.3.3.2.1 Influence of chloride .....................................................................................................62 i A.3.3.2.2 Influence of sulphide ....................................................................................................62 A.3.4 CORROSION OF TI-BASED MATERIALS.................................................................................64 A.4 EXPERIMENTAL RESULTS..................................................................................................67 A.4.1 CORROSION STUDIES RELEVANT TO THE GERMAN DISPOSAL CONCEPT IN ROCK SALT ...........67 A.4.1.1 Laboratory-scale corrosion experiments.................................................................69 A.4.1.1.1 Screening experiments.................................................................................................69 A.4.1.1.2 Experiments to evaluate the candidate metallic materials ...........................................70 A.4.1.1.2.1 Background..........................................................................................................70 A.4.1.1.2.2 Corrosion of unalloyed and low-alloyed steels in brines ......................................72 A.4.1.1.2.2.1 General and localised corrosion .................................................................72 A.4.1.1.2.2.1.1 Influence of brine composition and temperature on steel corrosion in brines..................................................................................................72 A.4.1.1.2.2.1.2 Influence of pH on steel corrosion in brines .......................................77 A.4.1.1.2.2.1.3 Influence of chemical species on steel corrosion in brines.................79 A.4.1.1.2.2.1.4 Influence of gamma irradiation on steel corrosion in brines ...............83 A.4.1.1.2.2.1.4.1 Investigations at 90°C (in the MgCl2-rich Q-brine) .....................83 A.4.1.1.2.2.1.4.2 Investigations at 150°C (in the three test brines 1, 2, and 3) .....84 A.4.1.1.2.2.1.5 Influence of welding on steel corrosion in brines................................88 A.4.1.1.2.2.2 Stress corrosion cracking (SCC).................................................................91 A.4.1.1.2.2.2.1 MgCl2-rich ‘Q’-brine ............................................................................91 A.4.1.1.2.2.2.2 NaCl-rich brine ‘3’ ...............................................................................93 A.4.1.1.2.3 Corrosion of Hastelloy C-4 in brines ....................................................................95 A.4.1.1.2.4 Corrosion of Ti 99.8-Pd in brines .........................................................................99 A.4.1.1.3 Experiments on real specimens originating from the POLLUX-disposal container ....102 A.4.1.1.3.1 Background........................................................................................................102 A.4.1.1.3.2 Results and discussion ......................................................................................103 A.4.1.1.3.3 Conclusions .......................................................................................................106 A.4.1.2 In-situ corrosion experiments .............................................................................. 107 A.4.1.2.1 Investigations in rock salt at rock temperature ...........................................................107 A.4.1.2.2 Brine Migration Test (investigations in rock salt / limited amounts of brine at HLW design temperature)...................................................................................................108 A.4.1.2.3 Testing of welded tubes (model containers) in rock salt / brine at HLW design temperature................................................................................................................109 A.4.1.2.4 Long-term testing under normal operating conditions at high temperature ...............110 A.4.1.2.4.1 Results from the DEBORA-Experiment.............................................................111 A.4.1.2.4.2 Results from the BAMBUS II-Experiment..........................................................112 A.4.1.2.5 Conclusions................................................................................................................114
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