Synthesis of zirconolite-2M ceramics for immobilisation of neptunium

Praseodymium-doped zirconolite ceramics targeting nominal composition Ca1-xPrxZrTi2-5x/3Al5x/3O7 (x ≤ 0.20, Δx = 0.05) were fabricated by a mixed oxide solid state reaction, at 1350 °C in air for 20 h. Praseodymium (Pr) was employed as a surrogate for neptunium (Np), with Al3+ co-accommodated to provide charge balance. High-resolution transmission electron microscopy and electron diffraction analyses confirmed that zirconolite crystallised as the 2 M monoclinic polytype throughout the phase evolution, with no evidence of transformation to other polytype structures. Phase assemblage and microstructural data were consistent with zirconolite occupying a high fraction of the phase assemblage (>ca. 93 wt %), alongside a minor secondary perovskite phase at all levels of targeted Pr incorporation. Despite this, it was demonstrated near theoretical density formed through a solid-state fabrication route, and we therefore propose that, through analogy with the corresponding Pr solid solution, zirconolite may be a suitable candidate for the immobilisation of Np-bearing wastes.