Stephane Gin

As borosilicate glasses are used in many countries to immobilize fission products and minor actinides after spent fuel reprocessing before storage in a deep geological repository, assessing that their chemical durability is of paramount importance. Here, pristine and preirradiated (952 MeV, 136Xe) SiO 2 –B 2 O 3 –Al 2 O 3 –Na 2 O glasses with the same molar ratios as in the French SON68 and ISG glasses have been subjected to aqueous corrosion in deionized water and in silica‐saturated solution to measure the initial and longer term alteration rates. Pristine and preirradiated glasses corrode following the same mechanisms, but the preirradiation has a strong impact on the initial dissolution rate (increase by a factor of 5.6), and on the alteration layer depth in silica‐saturated conditions (by two‐ to threefolds). The later result is related to the formation of a more porous, less passivating gel on the preirradiated glass specimen. Using both experimental spectroscopies (NMR, IR, and SFG) and classical molecular dynamics, the radiation effects on the glass structure and water diffusion have been assessed. After preirradiation, the density and the polymerization degree of the glass decrease, whereas the topological disorder increases. In consequence, water diffusion accelerates. These observations allow to correlate the radiation impact on the alteration behavior to the structural changes.

We study reactivity and leaching at the calcium sodium borosilicate (CNBS)–water interface by means of a Car–Parrinello ab initio molecular dynamics simulation over a simulation time of 100 ps. With an emphasis on the comparison between the behaviors of Ca2+ and Na+ cations at the CNBS glass–water interface, different mechanism events during the trajectory are revealed, discussed, and correlated with other density functional theory calculations. We show that Na+ ions can be released in solution, while Ca2+ cannot leave the surface of CNBS glass. This release is correlated with the vacancy energy of Ca2+ and Na+ cations. Here, we found that the CNBS structure with the Na+ cation vacancy is energetically more favorable than the structure with the Ca2+ cation vacancy. The calcium adsorption site has been shown to have a greater affinity for water than can be found in the case of the sodium site, demonstrating that affinity may not be considered a major factor controlling the release of cations from the glass to the solution.