Deconvoluting Cr states in Cr-doped UO₂ nuclear fuels via bulk and single crystal spectroscopic studies

Cr-doped UO₂ is a leading accident tolerant nuclear fuel where the complexity of Cr chemical states in the bulk material has prevented acquisition of an unequivocal understanding of the redox chemistry and mechanism for incorporation of Cr in the UO₂ matrix. To resolve this, we have used electron paramagnetic resonance, high energy resolution fluorescence detection X-ray absorption near energy structure and extended X-ray absorption fine structure spectroscopic measurements to examine Cr-doped UO₂ single crystal grains and bulk material. Ambient condition measurements of the single crystal grains, which have been mechanically extracted from bulk material, indicated Cr is incorporated substitutionally for U⁺⁴ in the fluorite lattice as Cr⁺³ with formation of additional oxygen vacancies. Bulk material measurements reveal the complexity of Cr states, where metallic Cr (Cr⁰) and oxide related Cr⁺² and Cr⁺³₂O₃ were identified and attributed to grain boundary species and precipitates, with concurrent (Cr⁺³_xU⁺⁴_1-x)O_2-0.5x lattice matrix incorporation. The deconvolution of chemical states via crystal vs. powder measurements enables the understanding of discrepancies in literature whilst providing valuable direction for safe continued use of Cr-doped UO₂ fuels for nuclear energy generation.