The role of surfaces, chemical interfaces, and disorder on plutonium incorporation in pyrochlores
R Perriot and PP Dholabhai and BP Uberuaga, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 18, 22852-22863 (2016).
Pyrochlores, a class of complex oxides with formula A(2)B(2)O(7), are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu3+ and Pu4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound. We also find that pyrochlore/pyrochlore bicrystals A(2)B(2)O(7)/A(2)'B-2'O-7 can be used to immobilize Pu3+ and Pu4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. In particular, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.
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