Brannerite, UTi2O6: Crystal chemistry, synthesis, properties, and use for actinide waste immobilization

Аннотация

The host materials suggested for immobilization of actinide waste of military or civil origin often contain the secondary (U,Pu)Ti2O6 phase of brannerite structure. For example, the materials for incorporation of excess plutonium, mainly consisting of pyrochlore, contain up to 30% brannerite. This is a usual phase in titanate host materials for isolating spent nuclear fuel (SNF) and products of its reprocessing, including waste from production of ^99mТс for medical purposes and other kinds of waste with high U and Pu content. Despite simple ideal stoichiometry, brannerite can contain large amounts of rare earths. This feature is due to the presence of uranium not only in the 4+ oxidation state, but also in the 5+ and 6+ states, which favors the exchange of rare earth elements (REE), e.g., in accordance with the scheme 2U⁴⁺ ↔ U⁵⁺ + REE³⁺. The REE amount in brannerite reaches 0.5–0.7 atom per formula unit. Therefore, brannerite is of interest as a host material for the rare earth–actinide fraction of high-level waste (HLW). To evaluate the prospects for such use of brannerite, data on the radiation resistance of brannerite and its behavior in aqueous solutions are analyzed. In these properties, brannerite is inferior to pyrochlore and zirconolite. The rate of actinide leaching from brannerite is higher by an order of magnitude than from these phases, but lower by 3–4 orders of magnitude than from glass host materials. Natural brannerite is stable in media with weakly alkaline and reducing waters. Therefore, brannerite seems suitable for immobilization of rare earth–actinide waste. This host material can be synthesized by sintering or cold crucible induction melting followed by crystallization.