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New glassy matrices, able to incorporate new highly concentrated radioactive liquid wastes (HLW), are being studied. Investigations were performed on rare earth-rich glasses, known as very durable matrices. The selected basic glass composition was (wt. %): 51.0 SiO2 – 8.5 B2O3–12.2 Na2O – 4.3 Al2O3 – 4.8 CaO – 3.2 ZrO2 – 16.0 Nd2O3. To determine both the environment around the rare earth in this glass and its evolution according to its concentration (1.3 – 30 wt. % Nd2O3), EXAFS (Extended X-Ray Absorption Fine Structure) spectroscopy at the LIII-edge of neodymium and optical absorption spectroscopy were used. By coupling these two characterisation methods, several hypotheses are proposed about the nature of the rare earth neighbouring in the glass.
Models have been developed to calculate the density, molten-state viscosity and initial corrosion rate according to the chemical composition of glass formulations used to vitrify high-level fission product solutions from reprocessed light water reactor fuel. Developed from other published work, these models have been adapted to allow for the effects of platinoid (Ru, Pd, Rh) inclusions on the molten glass rheology.
The French LWR reference glass R7T7 was leached at temperatures between 100°C and 300°C at a pressure of 10 MPa.
An activation energy of 25 kJ/mole was found between 100°C and 250°C which is different from the 60 kJ/mole previously found between 25°C and 70°C. It is suggested that a potential glass hydration mechanism becomes predominant when dissolution is significantly slowed by high concentrations of silica in solution. At 300°C, a complete change in the corrosion mechanisms is found as the glass undergoes a rapid hydrothermal alteration
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