Carbon driven oxygen retention in uranium oxycarbide (UCO) fluorite phase

Abstract

The behavior of oxygen in uranium oxycarbide (UCO) has been investigated using density functional theory. To assess the role of carbon on the stability of oxygen point defects, we first determined the formation energies of oxygen vacancy and interstitial for different carbon configurations. Subsequently, we evaluated the barriers for migration of various oxygen defects in the UCO matrix. Our results show that carbon atoms create strong attraction centers for oxygen atoms, as a consequence the spontaneous formation of oxygen Frenkel pairs in the fluorite structure is promoted. Moreover, the strong affinity of oxygen atoms for sites in the first coordination shell of a carbon center leads to the formation of CO, and thus reducing the mobility of oxygen atoms in the UCO fuel. Upon formation, the CO remains fixed at the carbon site due to significant hybridization with uranium atoms, therefore behaving as trap sites for oxygen atoms. Our findings indicate that the formation of CO molecules increases the retention of oxygen atoms inside the UCO matrix. Consequently, carbon atoms in the UCO matrix contribute to mitigating the deleterious effects that oxygen release from the fuel kernel has on the structural integrity of the silicon carbide layer in tristructural isotropic (TRISO) particles.