Diffusion chimique dans les verres borosilicates d'intérêt nucléaire

Abstract : Chemical diffusion is a key-phenomenon during nuclear glass synthesis. At high temperature, diffusion leads to homogenization of the melt contributing to the transformation of heterogeneous waste and frit precursors to a homogeneous glass after cooling. In contrast, in the supercooled liquid, diffusion is a critical factor affecting phase separation and/or crystallization processes that must be avoided when producing a high quality final product.In this manuscript, the impact of chemical diffusion on crystallization and liquid homogenization is studied for a simplified sodium borosilicate glass between its glass transition temperature and its synthesis temperature. For this kind of system, qualified as multicomponent, the description of diffusive phenomena requires the calculation of a diffusion matrix that takes into account diffusive couplings between species. These couplings can be written in the form of diffusive mechanisms or “diffusive exchanges” that are invariant with temperature. The activation energies associated with these exchanges are close to the activation energy of shear viscosity which suggests that viscous flow and chemical diffusion are driven by a single mechanism related to the frequency of Si-O and B-O bond breaking. It is also highlighted that in the supercooled liquid, the principal diffusive exchange (SiO2-Na2O) and the secondary diffusive exchange (SiO2-B2O3) play a significant role on the kinetics and direction of growth of crystalline phases which are formed in our system. These results are used to rationalise the evolution of compositional gradients in the vicinity and far from crystals. In the last part of this work, a complexification of the glasses was initiated by adding lanthanum to simulate one of the main lanthanides of the R7T7 nuclear glass composition. The data collected reveal diffusive couplings between lanthanum and silicon. These couplings, combined with the other results explain the formation of a lanthanum borosilicate phase (LaBSiO5).
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Hélène Pablo. Diffusion chimique dans les verres borosilicates d'intérêt nucléaire. Matériaux. Museum national d'histoire naturelle - MNHN PARIS, 2017. Français. ⟨NNT : 2017MNHN0014⟩. ⟨tel-02014713⟩

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