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Apatites are often seen as good potential candidates for the immobilization of halide-rich wastes. In particular, phosphate apatites have received much attention in recent years, however, their synthesis often produces complicated multi-phase systems, with a number of secondary phases forming [1.2]. Calcium vanadinite (Ca5(VO4)3Cl) demonstrates a much simpler phase system, with only a single Ca2V2O7 secondary phase which can easily be retarded by the addition of excess CaCl2. However, when doping with SmCl3 (as an inactive analogue for AnCl3) the Sm forms a wakefieldite (SmVO4) phase rather than being immobilized within the vanadinite, a result of having to form an energetically unfavourable Ca vacancy in order for the lattice to remain neutral overall. It has been postulated that charge-balancing the lattice via co-substitution of a monovalent cation will be less disfavoured and therefore help stabilise formation of a (Ca5-2xSmxAx)(VO4)3Cl solid solution (A = monovalent cation). This has been investigated using a combined modelling and experimental approach. Static lattice calculations performed using Li+, Na+ and K+ as charge-balancing species have shown the energy cost to be less than half that of charge-balancing via formation of a Ca vacancy. As a result, solid state synthesis of (Ca5-2xSmxLix)(VO4)3Cl, (Ca5−2xSmxNax)(VO4)3Cl and (Ca5-2xSmxKx)(VO4)3Cl solid solutions have been trialled, and analysis of the resulting products has shown a significant reduction in both the SmVO4 and Ca2V2O7 secondary phases across all dopant levels.

Sodalite (Na8[AlSiO4]6Cl2), a naturally occurring Cl-containing mineral, has long been regarded as a potential immobilization matrix for the chloride salt wastes arising from pyrochemical reprocessing operations, as it allows for the conditioning of the waste salt as a whole without the need for any pre-treatment. Here the consolidation and densification of Sm-doped sodalite (as an analogue for AnCl3) has been investigated with the aim of producing fully dense (i.e. > 95 % t.d.) ceramic monoliths via conventional cold-press-and-sinter techniques at temperatures of < 1000 °C. Microstructural analysis of pressed and sintered sodalite powders under these conditions is shown to produce poorly sintered, porous, inhomogeneous pellets. However, by the addition of a sodium aluminophosphate glass sintering aid, fully dense Sm-sodalite ceramic monoliths can successfully be produced by sintering at temperatures as low as 800 °C.

Calcium chlorosilicate (Ca3(SiO4)Cl2) is seen as a potential host phase for the immobilization of Cl-rich wastes arising from pyrochemical reprocessing, a waste stream often containing a mix of both di- and trivalent cations. Substitution of trivalent cations into the lattice requires some form of charge compensation to ensure the lattice remains charge neutral overall. Whilst previous work has only examined this through the formation of Ca vacancies, this study investigates the feasibility of charge-balancing via the substitution of a monovalent cation onto the Ca sites of the lattice. To that end, a series of static lattice calculations were performed to determine the site selectivity of monovalent cations of differing size when substituted onto the Ca sites of the calcium chlorosilicate lattice and the solution energies for the overall substitution processes compared with those for charge compensation via vacancy formation. In all cases the monovalent charge-balancing species shows a clear preference for substitution onto the Ca1 site in the calcium chlorosilicate lattice. The solution energy of the substitution process increases with the increasing ionic radii of both the mono- and trivalent species as the steric stresses associated with substitution of larger cations than the Ca2+ host increase. As such, only charge-balancing using Li+, Na+ or K+ is more favourable than via formation of a Ca vacancy.

Zirconolite (CaZrTi2O7), a durable and compositionally flexible titanate ceramic for the immobilization of separated actinides, is currently the UK’s preferred candidate phase for the immobilization of plutonium dioxide arising from aqueous reprocessing. Here, its suitability as a waste-form for actinide chlorides arising from pyrochemical reprocessing is investigated through synthesis via a molten salt mediated reaction using a number of different salt eutectics (MgCl2:NaCl, CaCl2:NaCl and KCl:NaCl). It is found that the effectiveness of the molten salt synthesis of zirconolite is governed by the solubility of ZrO2 in the salt medium used; the synthesis proceeding via the formation of a perovskite (CaTiO3) intermediate which then reacts with ZrO2 to form zirconolite via a solution-diffusion mechanism. Most notably, in the KCl:NaCl eutectic different zirconolite polytypes are formed at different synthesis temperatures, with zirconolite-3T forming at 900 °C, giving way to zirconolite-2M at 1200 °C.

Apatites are often seen as good potential candidates for the immobilization of halide-rich wastes and, in particular, chlorapatite (Ca5(PO4)3Cl) has received much attention in recent years. However, synthesis of chlorapatite waste-forms can produce a complicated multi-phase system, with a number of secondary phases forming, including β-TCP (Ca3(PO4)2), spodiosite (Ca2(PO4)Cl) and pyrophosphate (Ca2P2O7), many of which require elevated temperatures and extended calcinations times to reduce. Calcium vanadinite (Ca5(VO4)3Cl) demonstrates a much simpler phase system, with calcination at 750 °C yielding Ca5(VO4)3Cl together a small quantity of a Ca2V2O7secondary phase, the formation of which can be retarded by the addition of excess CaCl2. Characterization of compositions doped with SmCl3as an inactive analogue for AnCl3show the Cl to be immobilized in the vanadinite whilst the Sm forms a wakefieldite (SmVO4) phase.

Single-phase calcium chlorosilicate and sodalite, two potential ceramic waste-forms for the immobilisation of CaCl2-based pyroprocessing wastes, have been fabricated at temperatures below the volatilisation point of CaCl2. Solid solutions doped with Sm3+ as an inactive analogue for trivalent actinides have been fabricated and characterised. XRD analysis shows both phases will successfully accommodate Sm3+, with the sodalite in particular remaining single-phase. Fabrication of Sm-doped calcium chlorosilicate in air results in the formation of SmOCl and Ca(Si2O5) secondary phases, however, calcination in an inert atmosphere is shown to successfully retard the formation of SmOCl allowing for higher levels of doping.