Inorganic Chemistry, Vol.57, No.23, 14890-14894, 2018
Peculiar Thermal Behavior of UO2 Local Stucture
Most materials expand with temperature because of the anharmonicity of lattice vibration, and only a few shrink with increasing temperature. UO2, whose thermal properties are of significant importance for the safe use of nuclear energy, was considered for a long time to belong to the first group. This view was challenged by recent in situ synchrotron X-ray diffraction measurements, showing an unusual thermal decrease of the U-O distances. This thermal shrinkage was interpreted as a consequence of the splitting of the U-O distances due to a change in the U local order from Fm (3) over barm to Pa (3) over bar. In contrast to these previous investigations and using an element-specific synchrotron-based spectroscopic method, we show here that the U sublattice remains locally of the fluorite type from 50 to 1265 K, and that the decrease of the first U-O bond lengths is associated with an increase of the disorder.