Effects of stoichiometry on the defect clustering in uranium dioxide

This study addresses the on-going topic of point defects and point defect clusters in uranium dioxide. Molecular statics simulation using an extended pair potential model that accounts for disproportionation equilibrium as charge compensation has been applied to assess the effect of disproportionation on structural properties and clustering in non-stoichiometric uranium dioxide. The defective structures are scanned in minute detail using a powerful and versatile analysing tool, called ASTRAM, developed in-house for the purpose. Unlike pair potential models ignoring disproportionation effects, our model reproduces volume changes observed experimentally in non-stoichiometric UO2-x and UO2+x. The oxygen defect energetics computed is in good agreement with data in the literature. The model is used to assess the clustering that occurs in bulk samples of non-stoichiometric uranium dioxide. This study confirms the generation of split-interstitial clusters as the dominant defect type in non-stoichiometric uranium dioxide. A new key mechanism for defect clustering in hyper-stoichiometric uranium dioxide is proposed that is based on the progressive aggregation of primitive blocks identified as 1-vacancy split-interstitial clusters.