Phase equilibria in the UO2–PuO2 system under a temperature gradient

The phase behaviour of U0.80Pu0.20O1.95 was investigated under a steady-state temperature gradient between the solidus and liquidus by a short-time power-to-melt irradiation experiment. The radial U, Pu, Am and O profiles in the fuel pin after redistribution were measured by X-ray microanalysis. During irradiation, an inner fuel melt forms which is separated from the outer solid only by one concentric liquid–solid-phase boundary. The UO2 concentration increases to 85% and the PuO2 concentration decreases to 15% on the solid side of the interface. Opposite gradients occur on the liquid side of the interface. The concentration discontinuity is a consequence of the necessary equality of the chemical potentials of UO2 and PuO2 on both sides of the phase boundary which corresponds to a 2750°C isotherm. The radial oxygen profile results in an O/(U + Pu) ratio of 2.00 at the fuel surface and 1.92 at the central void of the fuel. The redistribution is caused by the thermal diffusion of oxygen vacancies in the lattice along the temperature gradient. This process is quantified by the heat of transport Q*v which ranges between −10 kJ/mol at the central void and about −230 kJ/mol near the fuel surface.