The detrimental effects of the fission gas Xe on the performance of oxide nuclear fuels are well known. However, less well known are the mechanisms that govern fission gas evolution. Here, in order to better understand bulk Xe behavior (diffusion mechanisms) in UO2±x we calculate the relevant activation energies using density functional theory (DFT) techniques. By analyzing a combination of Xe solution thermodynamics, migration barriers and the interaction of dissolved Xe atoms with U, we demonstrate that Xe diffusion predominantly occurs via a vacancy-mediated mechanism. Since Xe transport is closely related to diffusion of U vacancies, we have also studied the activation energy for this process. In order to best reproduce experimental data for the Xe and U activation energies, it is critical to consider the active charge-compensation mechanism for intrinsic defects in UO2±x. Due to the high thermodynamic cost of reducing U 4+ ions, any defect formation occurring at a fixed composition, i.e. no change in UO2±x stoichiometry, always avoids such reactions, which, for example, implies that the ground-state configuration of an O Frenkel pair in UO2 does not involve any explicit local reduction (oxidation) of U ions at the O vacancy (interstitial).

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The distribution and atomic structure of grain boundaries has been investigated in UO2. Our scanning electron microscopic/electron backscatter diffraction experiments on a depleted UO2 sample showed real nuclear fuels contain a combination of special coincident site lattice (CSL) and general boundaries. The experimental data indicated that ∼16% of the boundaries were CSL boundaries and the CSL distribution was dominated by low Σ boundaries; namely Σ9, Σ3, and Σ5 Based on our experimental observations, the structures of select low Σ (Σ5 tilt, Σ5 twist, Σ3 tilt) and a random boundary were analyzed in greater detail using empirical potential atomic‐scale calculations. Our calculations indicate that the boundaries have very different structures and each CSL boundary had multiple minima on the γ‐surface. The presence of a significant fraction of CSL boundaries and the differences in their structures are expected to have important consequences on fuel properties.

The stabilities of selected fission products-Xe, Cs, and Sr-are investigated as a function of non-stoichiometry x in UO(2 ± x). In particular, density functional theory (DFT) is used to calculate the incorporation and solution energies of these fission products at the anion and cation vacancy sites, at the divacancy, and at the bound Schottky defect. In order to reproduce the correct insulating state of UO(2), the DFT calculations are performed using spin polarization and with the Hubbard U term. In general, higher charge defects are more soluble in the fuel matrix and the solubility of fission products increases as the hyperstoichiometry increases. The solubility of fission product oxides is also explored. Cs(2)O is observed as a second stable phase and SrO is found to be soluble in the UO(2) matrix for all stoichiometries. These observations mirror experimentally observed phenomena.