Synthesis and characterisation of Ce-doped zirconolite Ca0.80Ce0.20ZrTi1.60M0.40O7 (M = Fe, Al) formed by reactive spark plasma sintering (RSPS)

Reactive spark plasma sintering has been utilised as a high-throughput processing route for the synthesis of two simulant zirconolite wasteform materials, targeting Ca0.80Ce0.20ZrTi1.60M0.40O7 (M = Fe3+ and Al3+). Materials were processed under 15 MPa uniaxial pressure, with heating/cooling rates of 100 °C/min to 1320 °C, maintained under vacuum. Despite moderate yield (> 80 wt%) of zirconolite-2M, a considerable Ce-rich perovskite phase was formed in both formulations, attributed to complete reduction of the Ce inventory to Ce3+, as determined by Ce L3-edge XANES analysis. The composition charge balanced with Al3+ was favoured on the basis of lower accompanying perovskite fraction.