Structural changes of Nd- and Ce-doped ammonium diuranate microspheres during the conversion to U$_{1-y}Ln_y$O$_{2\pm x}$

The structural changes of ammonium diuranate (ADU) microspheres, prepared by the sol-gel route via internal gelation, were investigated during thermal treatments in oxidative and reducing conditions. In particular, in-situ simultaneous thermogravimetric analyses and in-situ high-temperature scanning electron microscopy investigations were carried out on un-doped ADU microspheres, and ADU microspheres doped with 10 mol% neodymium or 10 mol% cerium. Calcination in air caused the surface of the particles to crack, but with increasing temperature up to 900 °C some healing, and additionally, shrinkage occurred. The extent of the fractures and the amount of shrinkage was, however, significantly more pronounced in a particle prepared with a tetravalent Ce precursor, as compared to particles prepared with a trivalent Nd or Ce precursor. The macroscopic behaviour could be related to the release of volatile decomposition products and the calcined compositions were identified as (Ln-doped) α-U3O8 by X-ray powder diffraction. During thermal treatment in reducing conditions a transition from a (Ln-doped) α-U3O8 phase to a (Ln-doped) UO2±x phase was observed. After exposure to a hydrogen containing gas mixture, this transition occurred rapidly in un-doped particles, and in particles prepared with trivalent Nd or Ce dopant precursors at 700 °C. Despite the fast reduction reaction, severe fractures appeared in the particles above temperatures of 850 °C, indicating that such behaviour is mainly attributed to sintering effects and less to the phase transition. In contrast, a more delayed reduction reaction was observed in particles prepared with a tetravalent dopant precursor and the described effects appeared less severe.