Towards a link between the energetic heterogeneities of the edge faces of smectites and their stability in the context of metallic corrosion

In the context of the potential confinement of high-level radioactive wastes (HLW) within the clay engineered barrier system (EBS) in deep geological formations, the evolution of the retention properties of smectite when interacting with Fe(0) needs to be assessed. If some potential natural analogues describing iron-clay reactivity are easily found, metallic iron-clay interactions are poorly described in studies regarding the Earth. Therefore, experimental investigations are needed. Several parameters influence Fe(0)-clay interactions, such as temperature, the interlayer composition of swelling clays, and the presence of octahedral Fe3+, etc. From a geometrical point of view, it is thought that clay destabilization is mainly controlled by phenomena starting at the edge faces of the particles. In the present work, the rates of the smectite-Fe(0) reaction at 80 degrees C were assessed by XRD, Moessbauer, and CEC analyses for three smectites. The investigations show marked differences in the degree of stability, which cannot be explained by the crystal-chemistry rules established in previous studies. Therefore, the Fe(0)-smectite interactions were studied in view of textural and energetic surface quantitative analyses. The studied smectites have equivalent nitrogen BET-specific surface areas, equivalent argon edge surface areas and slightly different basal surface areas. This similarity in particle shape indicates that the edge surface area cannot be accounted for when explaining the observed differences in reactivity. However, a correlation is obtained between smectite reactivity and the energetic heterogeneity of its edge faces. This is interpreted in terms of a multiplication of the number of sites on the edge faces, where the electron transfer between Fe(0) and the smectite structure can occur. (authors)