We compare typical reductive sintering conditions for U, Pu mixed oxides (4 h at 1700 °C in Ar/6 % H2 + 1200 ppm H2O) with lower temperature and mildly oxidative conditions (2 h at 1200 °C in CO/CO2 = 1/9) and report on the resulting microstructures and homogeneity. We show that lower temperature and mildly oxidative conditions, without cover gas change, can give close-to stoichiometric, crack-free MOX pellets with a relative density of ∼ 95 %, and we propose ways to improve the homogenisations of PuO2 and UO2 and increase the grain size.

We show that a homogeneous single-phase mixed oxide is obtained by blending and sintering commercial UO₂ and nanocrystalline PuO₂ powder; whereas, under the same conditions, conventional PuO₂ powder obtained from oxalate precipitation and composed of platelets, yields two-phase mixed oxide. The use of nanometric PuO₂ results in a larger final grain size.

Phase equilibria in the ThF₄-PuF₃ system were measured by differential scanning calorimetry. Samples were encapsulated to prevent leakage during the measurements and to prevent fluoride contamination of the instrument. Formation of intermediate compounds and solid solutions was investigated by X-ray diffraction. A thermodynamic model based on the CALPHAD approach was developed for the measured system. Good fit between measurements and phase equilibria calculated using the model was achieved.