Structure, properties and formation of PuCrO3 and PuAlO3 of relevance to doped nuclear fuels

Abstract

We have employed a variety of computational methods to understand the behaviour of Pu, generated by neutron capture reactions in UO₂ fuel, with Cr₂O₃ and Al₂O₃, two common UO₂ fuel dopants. Structure search calculations using density functional theory and empirical potentials show that PuCrO₃ and PuAlO₃ are likely to form in these systems. The lowest energy structure adopted by both compounds is predicted to be the orthorhombic (Pnma) GdFeO₃-type perovskite structure. Relative to UO₂, the thermal conductivity of PuCrO₃ was calculated to be approximately three times smaller over the explored temperature range and therefore the presence of this phase will impact the microstructure, fission product distribution and gas release properties of UO₂-based fuels. In contrast, the PuAlO₃ phase had a similar thermal conductivity to UO₂. Calculated defect energies suggest that defects in both PuCrO₃ and PuAlO₃ will be dominated by antisite defects and that their radiation tolerances are similar to that of UO₂. Calculation of the solution and partition energies of a range of trivalent cations indicate that minor actinides are likely to substitute for Pu in the perovskite structure having an impact on the in-reactor behaviour of Cr-containing fuels and subsequently the waste reprocessing route.