Neptunium characterization in uranium dioxide fuel: Combining a XAFS and a thermodynamic approach

The effect of Np incorporation in a UO2 matrix on redox state of U and Np cations has been investigated by X-ray absorption spectroscopy (XAS) on three samples: (U0.9Np0.1)O2, (U0.9Np0.1)O2+x and pure NpO2 as a reference for Np(IV) oxidation state. XANES and EXAFS analysis show that only Uranium is oxidized in higher (V) and (VI) oxidation states in the hyperstoichiometric (U0.9Np0.1)O2+x sample in comparison to the stoichiometric (U0.9Np0.1)O2 where U appears at the (IV) oxidation state. Neptunium cation always remains at the (IV) oxidation state whatever the oxygen stoichiometry. Thermodynamic calculations performed to complete the experimental study, lead to the same conclusion. Separate UO2-NpO2 phases and homogeneous solid solution were considered. The latter case shows that the energy of mixing is insignificant in this system. These combined experimental and theoretical approaches demonstrate that any excess of oxygen in the system is carried by Uranium.