Heat capacity anomaly in UO2 in the vicinity of 1300 K:: an improved description based on high resolution X-ray and neutron powder diffraction studies

X-ray and neutron powder diffraction studies of UO2 were performed under controlled oxygen partial pressure between room temperature and 1673 K. More than 40 neutron diffraction patterns were recorded. The thermal expansion coefficient of UO2 and the temperature dependence of Debye-Waller factors for oxygen and uranium atoms were determined. The dependence of Debye-Waller factors as a function of temperature is linear and the thermal expansion coefficient follows the classical Debye regime within the temperature range 300-1000 K. Above 1200 K, a departure from this quasi-harmonic behavior is clearly observed. Both an abnormal increase of the thermal expansion and of the oxygen sublattice disorder are evidenced. The departure of the lattice parameter from a linear thermal variation is found to be thermally activated with an effective activation energy close to 1 eV, very similar to the activation energy already found for the electrical conductivity. This new result suggests that polarons may affect the mean lattice parameter. A new thermodynamic model is then proposed to explain the heat capacity thermal variation by only three contributions: harmonic phonons, thermal expansion and polarons. (c) 2004 Elsevier Ltd. All rights reserved.