Search

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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Static dissolution experiments were carried out with the reference International Simple Glass under hyperalkaline pH at 70 °C and very high SA/V ratio. Three aspects of glass dissolution behavior were investigated, (1) the rate drop regime and the residual rate (stage II), (2) the formation of secondary phases including thermodynamic aspects, and (3) the microstructure of the interface of altered glass and secondary phases. A very low residual rate of 6 × 10 -6 g/m 2 d was determined based on boron release, which was several orders of magnitude lower than the initial rate established between the start of the experiments and the first sampling on day 59. The presence of a porous layer with a thickness varying between 80 nm and 250 nm and a pore size between 10 nm and 50 nm was observed. CSH phases with a low Ca/Si ratio of 0.3-0.4 and zeolites were also visible at the surface of the altered glass grains, but no glass alteration resumption occurred, probably due to an important pH decrease already at day 59. Thermodynamic calculations assuming congruent glass dissolution and precipitation of the dissolved aqueous species confirmed the precipitation of CSH phases and zeolites.