Recent advances in the study of the UO2–PuO2 phase diagram at high temperatures

Abstract

Recently, novel container-less laser heating experimental data have been published on the melting behaviour of pure PuO2 and PuO2-rich compositions in the uranium dioxide–plutonium dioxide system. Such data showed that previous data obtained by more traditional furnace heating techniques were affected by extensive interaction between the sample and its containment. It is therefore paramount to check whether data so far used by nuclear engineers for the uranium-rich side of the pseudo-binary dioxide system can be confirmed or not. In the present work, new data are presented both in the UO2-rich part of the phase diagram, most interesting for the uranium–plutonium dioxide based nuclear fuel safety, and in the PuO2 side. The new results confirm earlier furnace heating data in the uranium-dioxide rich part of the phase diagram, and more recent laser-heating data in the plutonium-dioxide side of the system. As a consequence, it is also confirmed that a minimum melting point must exist in the UO2–PuO2 system, at a composition between x(PuO2)=0.4 and x(PuO2)=0.7 and 2900K⩽T⩽3000K. Taking into account that, especially at high temperature, oxygen chemistry has an effect on the reported phase boundary uncertainties, the current results should be projected in the ternary U–Pu–O system. This aspect has been extensively studied here by X-ray diffraction and X-ray absorption spectroscopy. The current results suggest that uncertainty bands related to oxygen behaviour in the equilibria between condensed phases and gas should not significantly affect the qualitative trend of the current solid–liquid phase boundaries.