Characterization of the alteration products formed at the surface of LaYSiAlO and CeYSiAlO glasses using ERDA and RBS techniques

Abstract

Leaching tests have been performed on LnYSiAlO glasses (Ln = La or Ce) that are considered as potential matrices for the specific immobilization of minor actinides. Elastic recoil detection analysis (ERDA) performed on leached samples indicated a superficial hydration of LaYSiAlO glass of about 100–150 nm. This hydrated layer is (Al, Y)-enriched according to SEM-EDS analysis, suggesting the formation of hydroxide (or hydroxycarbonates) compounds including these two elements. This process leads to a very efficient passivation of the material due to the low solubility of Al and Y hydroxides (and hydroxycarbonates) species in near neutral media, even when the solution is rapidly replenished is dynamic leaching experiments. Rutherford Backscattering Spectrometry elemental mapping revealed very localized and significantly Y-enriched deposits at the surface of the sample after leaching. This could be the sign of heterogeneities already present on the pristine glass. These may be correlated with the weak solubility of yttrium (and rare earth) elements in silicate matrices (Y + Ln initial content in the glass ≈11 at.%). In the case of CeYSiAlO glass, a thin layer was formed on the solid after leaching. The simulation of the corresponding RBS spectra showed a surface (Y, Ce)-enrichment and (Al, Si)-depletion in both cases. This could be explained by the oxidation of trivalent cerium initially present in the glass structure during leaching. This might be explained by the low solubility of Ce(IV)-compounds (CeO2 and/or Ce(OH)4) in solution leading to an enrichment of this element at the glass/solution interface, to form a mixture of amorphous CeO2 and Y(OH)3, as confirmed by XPS and XRD experiments.