Zirconolite (CaZrTi₂O₇) has been identified as a candidate ceramic wasteform for the immobilisation and disposal of Pu inventories, for which there is no foreseen future use. Here, we provide an overview of relevant zirconolite solid solution chemistry with respect to Ce, U and Pu incorporation, alongside a summary of the available literature on zirconolite aqueous durability. The zirconolite phase may accommodate a wide variety of tri- and tetravalent actinide and rare-earth dopants through isovalent and heterovalent solid solution, e.g. CaZr_1–xPu_xTi₂O₇ or Ca_1–xPu_xZrTi_2–2xFe_2xO₇. The progressive incorporation of actinides within the zirconolite-2M parent structure is accommodated through the formation of zirconolite polytypoids, such as zirconolite-4M or 3T, depending on the choice of substitution regime and processing route. A variety of standardised durability tests have demonstrated that the zirconolite phase exhibits exceptional chemical durability, with release rates of constituent elements typically <10⁻⁵ gm⁻²·d⁻¹. Further work is required to understand the extent to which polytype formation and surrogate choice influence the dissolution behaviour of zirconolite wasteforms.

Zirconolite is considered to be a suitable wasteform material for the immobilization of Pu and other minor actinide species produced through advanced nuclear separations. Here, we present a comprehensive investigation of Dy³⁺ incorporation within the self-charge balancing zirconolite Ca_1–xZr_1–xDy_2xTi₂O₇ solid solution, with the view to simulate trivalent minor actinide immobilization. Compositions in the substitution range 0.10 ≤ x ≤ 1.00 (Δx = 0.10) were fabricated by a conventional mixed oxide synthesis, with a two-step sintering regime at 1400 °C in air for 48 h. Three distinct coexisting phase fields were identified, with single-phase zirconolite-2M identified only for x = 0.10. A structural transformation from zirconolite-2M to zirconolite-4M occurred in the range 0.20 ≤ x ≤ 0.30, while a mixed-phase assemblage of zirconolite-4M and cubic pyrochlore was evident at Dy concentrations 0.40 ≤ x ≤ 0.50. Compositions for which x ≥ 0.60 were consistent with single-phase pyrochlore. The formation of zirconolite-4M and pyrochlore polytype phases, with increasing Dy content, was confirmed by high-resolution transmission electron microscopy, coupled with selected area electron diffraction. Analysis of the Dy L₃-edge XANES region confirmed that Dy was present uniformly as Dy³⁺, remaining analogous to Am³⁺. Fitting of the EXAFS region was consistent with Dy³⁺ cations distributed across both Ca²⁺ and Zr⁴⁺ sites in both zirconolite-2M and 4M, in agreement with the targeted self-compensating substitution scheme, whereas Dy³⁺ was 8-fold coordinated in the pyrochlore structure. The observed phase fields were contextualized within the existing literature, demonstrating that phase transitions in CaZrTi₂O₇–REE³⁺Ti₂O₇ binary solid solutions are fundamentally controlled by the ratio of ionic radius of REE³⁺ cations.

The structural and chemical properties of zirconolite (ideally CaZrTi₂O₇) as a host phase for separated REE–actinide-rich wastes are considered. Detailed analysis of both natural and synthetic zirconolite-structured phases confirms that a selection of zirconolite polytype structures may be obtained, determined by the provenance, crystal chemistry, and/or synthesis route. The production of zirconolite ceramic and glass–ceramic composites at an industrial scale appears most feasible by cold pressing and sintering (CPS), pressure-assisted sintering techniques such as hot isostatic pressing (HIP), or a melt crystallization route. Moreover, we discuss the synthesis of zirconolite glass ceramics by the crystallization of B–Si–Ca–Zr–Ti glasses containing actinides in conditions of increased temperatures relevant to deep borehole disposal (DBD).