The kinetics and mechanisms of simulated British Magnox waste glass dissolution as a function of pH, silicic acid activity and time in low temperature aqueous systems

Abstract

Dissolution of a simulated British Magnox waste glass is governed by two pH-dependent processes. At low pH, dissolution is governed by reactions occurring predominantly at non-Si sites and residual Si-rich gels develop at the glass surface as B, Al and modifier cations are selectively leached. Here, extensive proton promoted hydrolysis of BO and AlO bonds is coupled with hydration and ion exchange processes. Hydrolysis of siloxane bonds governs the rate of dissolution at high pH and the glass dissolves congruently as the silicate network breaks down extensively. Differences in the surface chemistries and morphologies of glass samples reacted in strongly acidic and highly alkaline media reflect the net effects of these processes. The rate of the congruent dissolution process is influenced by the activity of silicic acid. The results are compared with published data for other glass formulations and are discussed in the context of proposed kinetic dissolution models.