Corrosion of iron and low alloyed steel within a water saturated brick of clay under anaerobic deep geological disposal conditions: An integrated experiment

The aim of this study was to determine the corrosion behaviour of iron and low alloyed steels under simulated geological disposal conditions, related to long-term disposal of nuclear wastes in the site of Bure (Meuse-Haute Marne, Champagne, France). The dedicated experiment was a fully integrated set-up: three different bars of material (iron, steel or nickel) have been introduced inside a solid block of clay, which has been saturated with synthetic Bure water and maintained at 90 degrees C during 8 months. Two types of clay have been tested: first, a compacted MX80 (Wyoming, USA) and second, argilite directly taken from the Bure site (Callovo-Oxfordian). In situ electrochemistry has been performed: impedance spectra, chronopotentiometry... The samples have been analysed using a combination of techniques, such as SEM, XRD, EDS, mu XAS, mu Raman, gravimetry after desquamation. In both cases, the steel or the iron seemed to passivate in contact with the clay. Post-processing of the EIS determined the corrosion rates and the changes in the kinetics have been noticed. The post mortem analysis of the corrosion products showed in both cases the presence of an internal layer made of magnetite (Raman, EDX). The external layer was made of partially Ca-substituted siderite (Fe1-xCaxCO3), which could play an extra role in the passivation. Moreover, the samples embedded in the Bure argilite presented an intermediate unique layer containing Fe, O, Na and Si. This study suggests the corrosion products started to react with the silica issued from the dissolution of the Bure clay minerals, resulting in clay minerals neo-formation and in corrosion kinetic changes. (C) 2008 Elsevier B.V. All rights reserved.