Synthesis of Garnet/Perovskite-Based Ceramic for the Immobilization of Pu-Residue Wastes

Abstract

AbstractThe use of garnet/perovskite-based ceramic, with formula type (Y, Gd,..) 3(AI, Ga,..) 5O12 12/(Y, Gd,..)(A1, Ga,..)O3, was tested for immobilizing plutonium residue wastes. Pu residue wastes originate from nuclear weapons production and can contain more than 50% of impurities including such elements as Am, Al, Mg, Ga, Fe, K, La, Na, Mo, Nd, Si, Ta, Ce, Ba, B, W, Zn, Zr, C and Cl. While for some of these residues, direct conversion to typical glass or ceramic forms may be difficult, ceramic forms based on durable actinide host-phases are preferred for Pu, Am and other actinides immobilization. Garnet/perovskite crystalline host-phases are chemically and mechanically durable and desirable for the incorporation of Pu and most of the impurity elements in the Pu residue wastes in the lattices of host-phases in the form of solid solutions. Experiments on the synthesis of garnet/perovskite ceramic samples were carried out using melting in air at temperatures from 1300°C (for samples doped with 10 wt.% Pu residue waste simulant) to 2000°C (for samples doped with 10 wt.% Ce or U). Samples were studied by XRD, SEM and cathodoluminescence techniques. It was found that the garnet phase can incorporate upto 6 wt.% Ce and up to 4.0-5.5 wt.% U, which is correlated with the increase of Ga content and decrease of Al content in the melt. In one of the features of the melt, the perovskite phase formation substitutes for the formation of garnet. The capacity of the perovskite lattice to accommodate Ce and U is higher than the capacity of garnet, reaching about 8 and 7 wt.%, respectively. It was shown that cathodoluminescence can be effectively used to determine the valence state of Ce and U, an important step to optimize the starting precursor preparation. Incase of U4+ in the melt, the charge-compensating elements (Sn2+, Ca2+...) are needed to successfully incorporate U in the garnet lattice.