A sample of zirconolite with nominal composition Ca0.80Ce0.20ZrTi1.60Cr0.40O7 was processed via Hot Isostatic Pressing (HIP), with a dwell temperature and pressure of 1320 °C/100 MPa maintained for 4 h. The produced wasteform was characterised by powder XRD, SEM–EDS, Ce L3 and Cr K-edge XANES. A significant portion of the Ce inventory did not fully partition within the zirconolite phase, instead remaining as CeO2 within the microstructure. Inspection of the stainless steel–ceramic interface detailed the presence of an interaction region dominated by a Cr-rich oxide layer. No significant Cr or Fe migration was observed, although a greater concentration of perovskite was observed at the periphery, relative to the bulk ceramic matrix. The X-ray absorption features of Cr remained analogous with Cr3+ accommodation within TiO6 octahedra in the zirconolite matrix. The absorption edge of Ce was comprised of contributions from zirconolite-2M and unincorporated CeO2, with an average oxidation state of Ce3.9+. As zirconolite-2M accounted for > 92 wt% of the overall phase assemblage, it is clear that the dominant oxidation state of Ce in this phase was Ce4+.
Graphic abstract
Indium (In) is a neutron absorbing additive that could feasibly be used to mitigate criticality in ceramic wasteforms containing Pu in the immobilised form, for which zirconolite (nominally CaZrTi2O7) is a candidate host phase. Herein, the solid solutions Ca1-xZr1-xIn2xTi2O7 (0.10 ≤ x ≤ 1.00; air synthesis) and Ca1-xUxZrTi2-2xIn2xO7 (x = 0.05, 0.10; air and argon synthesis) were investigated by conventional solid state sintering at a temperature of 1350 °C maintained for 20 h, with a view to characterise In3+ substitution behaviour in the zirconolite phase across the Ca2+, Zr4+ and Ti4+ sites. When targeting Ca1-xZr1-xIn2xTi2O7, single phase zirconolite-2M was formed at In concentrations of 0.10 ≤ x ≤ 0.20; beyond x ≥ 0.20, a number of secondary In-containing phases were stabilised. Zirconolite-2M remained a constituent of the phase assemblage up to a concentration of x = 0.80, albeit at relatively low concentration beyond x ≥ 0.40. It was not possible to synthesise the In2Ti2O7 end member compound using a solid state route. Analysis of the In K-edge XANES spectra in the single phase zirconolite-2M compounds confirmed that the In inventory was speciated as trivalent In3+, consistent with targeted oxidation state. However, fitting of the EXAFS region using the zirconolite-2M structural model was consistent with In3+ cations accommodated within the Ti4+ site, contrary to the targeted substitution scheme. When deploying U as a surrogate for immobilised Pu in the Ca1-xUxZrTi2-2xIn2xO7 solid solution, it was demonstrated that, for both x = 0.05 and 0.10, In3+ was successfully able to stabilise zirconolite-2M when U was distributed predominantly as both U4+ and average U5+, when synthesised under argon and air, respectively, determined by U L3-edge XANES analysis.
Zirconolite is a candidate ceramic wasteform under consideration for the immobilisation of the UK civil PuO2 inventory. In the present work, a baseline dual-substituted zirconolite with the target composition (Ca0.783Gd0.017Ce0.2)(Zr0.883Gd0.017Ce0.1)(Ti1.6Al0.4)O7 was fabricated by hot isostatic pressing (HIPing). In order to optimise the microstructure properties and improve the obtained yield of the zirconolite phase, a range of planetary ball milling parameters were investigated prior to consolidation by HIP. This included milling the batched oxide precursors at 400 rpm for up to 120 min, the pre-milling of CeO2 (PuO2 surrogate) to reduce the particle size and using a CeO2 source with finer particle size (<5 µm). The HIPed zirconolite product consisted of both zirconolite-2M and zirconolite-3T polytypes in varying proportions; however, an additional perovskite phase was obtained in varying quantities as a secondary phase. Ce L3-edge X-ray absorption spectroscopy was utilised to determine the Ce oxidation state. In this study, the ideal milling parameter for the fabrication of zirconolite waste forms was defined as 60 min at 400 rpm.
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