Molecular Dynamics study of the effects of non-stoichiometry and oxygen Frenkel pairs on the thermal conductivity of uranium dioxide

In the present work, calculations of the thermal conductivity of UO2 were carried out applying classical Molecular Dynamics for the isothermal-isobaric (NPT) statistical ensemble, using the Green–Kubo approach. The thermal conductivity calculated for perfect stoichiometric UO2 is in good agreement with the literature data over the temperature range corresponding to heat transfer by phonons (up to 1700 K). The effect of non-stoichiometry on the thermal conductivity was calculated taking into account the presence of polarons. It was found that for the same value of the stoichiometry deviation, the effect of oxygen vacancies (hypo-stoichiometry) is more pronounced than the effect of oxygen interstitials (hyper-stoichiometry). Then the influence of the oxygen Frenkel pairs on the thermal conductivity was calculated. The simultaneous impact of non-stoichiometry and OFP on the thermal conductivity was investigated and it was shown that the two effects can be combined using the interpretation obtained with the classical phonons scattering theory. Finally, simplified correlations were deduced for the calculation of the thermal conductivity of UO2 taking into account the effect of non-stoichiometry and of Frenkel pairs, these two effects being present during irradiation.