Immobilization of cesium and iodine into Cs3Bi2I9 perovskite-silica composites and core-shell waste forms with high waste loadings and chemical durability

[Display omitted] •Develop pervoskite ceramic waste forms with high I and Cs loading and excellent chemical durability.•Consolidate Cs3Bi2I9-silica composite and core-shell structures into dense pellet by spark plasma sintering.•Understand the surface alteration and passivation mechanisms and their impacts on chemical durability. Cs3Bi2I9, a defect perovskite derivative, is a potential host phase to immobilize iodine and cesium with high waste loadings. In this work, two strategies were explored to form Cs3Bi2I9-silica composites and a core-shell structure in order to improve chemical durability of waste form materials meanwhile maintaining high waste loadings. Cs3Bi2I9 loadings as high as 70 wt.% were incorporated into a silica matrix to form silica-ceramic composites, and 20 wt.% Cs3Bi2I9 was encapsulated into silica to form a core–shell structure by low temperature spark plasma sintering. Chemical durability of the composite and core-shell waste forms was evaluated by semi-dynamic leaching experiments, and Cs and I were incongruently released from waste form matrices. A BiOI alteration layer formed, acting as a passivation layer to reduce the release of radionuclides. The long-term iodine release rate was low (30 mg m−2 day-1) for the 70 wt.% Cs3Bi2I9–silica composite leached in deionized water at 90 °C, which can be further reduced to 5 × 10−3 mg m−2 day−1 for the 20 wt.% core-shell structure. This work highlights a robust way to immobilize the highly mobile radionuclides with high waste loadings through encapsulation into durable matrices and a surface passivating mechanism that can greatly reduce the elemental transport from waste form materials and significantly enhance their chemical durability.