Charge compensation mechanisms in Nd-doped UO2 samples for stoichiometric and hypo-stoichiometric conditions: Lack of miscibility gap

The evolution of the crystal lattice of samples made of UO2 doped with different concentrations of Nd in stoichiometric and hypo-stoichiometric conditions has been systematically studied by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The substitution of a trivalent cation for the U4+ initial position is responsible for creating local structural disorder and changes in the oxidation states. In this scenario, the lattice parameter is affected and the concentration of U5+ and formation of oxygen vacancies as well, since these are the mechanisms necessary to maintain the charge neutrality. The systematic oxidation of U4+ as predominant charge compensation mechanism over the formation of vacancies can be reduced by performing a thermal treatment under reducing conditions. This paper presents an experimental characterization of the uranium oxidation state mixture and local structure using XAS techniques in samples with chemical formula (U1-yNdy)O2-x, with y = 0.04, 0.17 and 0.25 (0