Assessment of solid/liquid equilibria in the (U, Zr)O_2+y system

Abstract

Solid/liquid equilibria in the system UO₂–ZrO₂ are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the only study available in the literature on the whole pseudo-binary system. In addition, a minimum melting point is identified here for compositions near (U_0.6Z_r0.4)O_2+y, around 2800 K. The solidus line is rather flat on a broad range of compositions around the minimum. It increases for compositions closer to the pure end members, up to the melting point of pure UO₂ (3130 K) on one side and pure ZrO₂ (2970 K) on the other. Solid state phase transitions (cubic-tetragonal-monoclinic) have also been observed in the ZrO₂-rich compositions X-ray diffraction. Investigations under 0.3 MPa air (0.063 MPa O₂) revealed a significant decrease in the melting points down to 2500 K–2600 K for increasing uranium content (x(UO₂)> 0.2). This was found to be related to further oxidation of uranium dioxide, confirmed by X-ray absorption spectroscopy. For example, a typical oxidised corium composition U_0.6Zr_0.4O_2.13 was observed to solidify at a temperature as low as 2493 K. The current results are important for assessing the thermal stability of the system fuel – cladding in an oxide based nuclear reactor, and for simulating the system behaviour during a hypothetical severe accident.