Dissolution of simulated nuclear waste glass at high surface area to solution volume, high pH and 70 °C: comparison of international simple glass and SON68 glass

Abstract

Long-term static dissolution experiments, lasting up to ∼1500 days, were conducted on International Simple Glass (ISG) and SON68 glass under hyperalkaline pH, at 70 °C, and at a very high glass surface area to solution volume ratio. The study compared (1) glass dissolution kinetics, (2) secondary phase formation, and (3) the microstructure of the altered glass and secondary phase interface. Boron release indicated rapid initial dissolution followed by a slowdown mainly due to a significant pH drop. ISG reached a residual rate regime, while SON68 approached this regime near the experiment's end, with both glasses having similar final dissolution rates. Electron microscopy (SEM, TEM, EDS) of the reacted glass surfaces and the alteration products revealed nontronite formation on SON68, while C(A)SH phases and later rhodesite appeared on ISG, in addition to phillipsite-type zeolite formation observed in both experimental series. TEM observations revealed a porous, foam-like surface altered layer (SAL) near the pristine glass. SON68's SAL nanostructure, more complex than ISG's, had two porous zones, hindering water transfer and glass constituent release, in addition to a pH drop reducing silica network hydrolysis. TEM-EDS showed cation exchange and iron depletion in SON68's SAL, leading to nontronite formation. Secondary phases at the SAL-solution interface did not destabilize the SAL, and no alteration resumption was observed due to the pH drop below the threshold necessary for an alteration resumption due to zeolite formation. In conclusion, the combination of alkaline conditions and very high reaction progress does not lead to the dissolution of the glass by a dissolution-reprecipitation mechanism, as typically observed at much lower SA/V ratios. At the relatively mildly alkaline pH reached within the first year of the experiments, the diffusion of cations through the SAL becomes rate-controlling.