β-Irradiation Effects on the Formation and Stability of CaMoO4 in a Soda Lime Borosilicate Glass Ceramic for Nuclear Waste Storage

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• 作者：Karishma B. PatelBruno Boizot ; Sébastien P. Facq ; Giulio I. Lampronti ; Sylvain Peuget ; Sophie Schuller ; Ian Farnan
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：February 6, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：1558-1573
• 全文大小：781K
• ISSN：1520-510X

文摘

Molybdenum solubility is a limiting factor to actinide loading in nuclear waste glasses, as it initiates the formation of water-soluble crystalline phases such as alkali molybdates. To increase waste loading efficiency, alternative glass ceramic structures are sought that prove resistant to internal radiation resulting from radioisotope decay. In this study, selective formation of water-durable CaMoOb>4b> in a soda lime borosilicate is achieved by introducing up to 10 mol % MoOb>3b> in a 1:1 ratio to CaO using a sintering process. The resulting homogeneously dispersed spherical CaMoOb>4b> nanocrystallites were analyzed using electron microscopy, X-ray diffraction (XRD), Raman and electron paramagnetic resonance (EPR) spectroscopies prior to and post irradiation, which replicated internal β-irradiation damage on an accelerated scale. Following 0.77 to 1.34 GGy of 2.5 MeV electron radiation CaMoOb>4b> does not exhibit amorphization or significant transformation. Nor does irradiation induce glass-in-glass phase separation in the surrounding amorphous matrix, or the precipitation of other molybdates, thus proving that excess molybdenum can be successfully incorporated into a structure that it is resistant to β-irradiation proportional to 1000 years of storage without water-soluble byproducts. The CaMoOb>4b> crystallites do however exhibit a nonlinear Scherrer crystallite size pattern with dose, as determined by a Rietveld refinement of XRD patterns and an alteration in crystal quality as deduced by anisotropic peak changes in both XRD and Raman spectroscopy. Radiation-induced modifications in the CaMoOb>4b> tetragonal unit cell occurred primarily along the c-axis indicating relaxation of stacked calcium polyhedra. Concurrently, a strong reduction of Mo⁶⁺ to Mo⁵⁺ during irradiation is observed by EPR, which is believed to enhance Ca mobility. These combined results are used to hypothesize a crystallite size alteration model based on a combination of relaxation and diffusion-based processes initiated by added energy from β-impingement and second-order structural modifications induced by defect accumulation.