Study of Crystallization Mechanisms in the French Nuclear Waste Glass


The development of glass materials for long-term storage of high-level waste implies determining the glass thermal stability and notably assessing the risk of devitrification. Previous studies of the French nuclear waste glass have identified the crystalline phases and the domains in which they form, and have shown that devitrification is minimal. Modeling the long-term crystallization behavior requires an investigation of the thermodynamic and kinetic mechanisms liable to induce crystallization during cooling. The first step in this approach is to determine the nucleation and growth curves for each of the component phases. Crystals including CaMoO4, CeO2 and ZnCr2O4 were identified in glasses heat-treated at temperatures between 630°C and 1110°C, and the time and thermal dependence of the CaMoO4 morphology were evaluated. The nucleation and growth kinetics of these phases were determined by optical microscopy and SEM, and the impact of impurities was addressed by studying two glasses, with and without platinoid elements. The results indicated enhanced nucleation kinetics in glass containing platinoid elements. No induction time was observed before permanent nucleation in either of the glasses, and rapid saturation of nucleation kinetics—synonymous with the depletion of active centers of nucleation— was detected after a few hours. Furthermore, similar growth kinetics were observed in both glasses. The nucleation and growth curves coincided for all the phases. Peak values were much higher for nucleation than for growth kinetics, confirming the need for a thorough investigation of the mechanisms occurring in and below the glass transition range, i.e. in the non-equilibrium state.

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Orlhac, X., Fillet, C. & Phalippou, J. Study of Crystallization Mechanisms in the French Nuclear Waste Glass. MRS Online Proceedings Library 556, 263 (1998).

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