Insights into the UO2+x/U4O9 phase characterization in oxidized UO2 pellets as a function of hyper-stoichiometry

Abstract

We present new insights into the study of the UO2+x/U4O9 equilibrium in UO2 as a function of the hyper-stoichiometry (x) by coupling HERFD-XANES at the uranium M4-edge with micro-Raman spectroscopy mapping. XANES allowed the measurement of uranium speciation in the samples, while Raman spectroscopy was used to individually characterize the composition and localization of the different oxide phases. UO2 pellets were oxidized under dry conditions at temperatures above the UO2+x/U4O9 phase transition to reach hyper-stoichiometries in the range of 0.01 ≤ x ≤ 0.1. Combining both techniques, we could determine the proportions of U4O9 and UO2+x. We show that at a low O/U ratio, U4O9 is present as small clusters inside UO2 grains. As the O/U increases, we found evidence of the formation of a network of U4O9 crystallized inside the UO2+x grains. The variation of the UO2+x phase hyper-stoichiometry (x) was evaluated as a function of the sample oxidation.