Candidate waste forms for immobilisation of waste chloride salt from pyroprocessing of spent nuclear fuel

摘要

Sodalite/glass bodies prepared by hot isostatic pressing (HIPing) at ～850 °C/100 MPa are candidates for immobilising fission product-bearing waste KCl-LiCl pyroprocessing salts. To study the capacity of sodalite to structurally incorporate such pyroprocessing salts, K, Li, Cs, Sr, Ba and La were individually targeted for substitution in a Na site in sodalite (Na vacancies targeted as charge compensators for alkaline and rare earths) and studied by X-ray diffraction and scanning electron microscopy after sintering in the range of 800-1000 °C. K and Li appeared to enter the sodalite, but Cs, Sr and Ba formed aluminosilicate phases and La formed an oxyapatite phase. However these non-sodalite phases have reasonable resistance to water leaching. Pure chlorapatite gives superior leach resistance to sodalite, and alkalis, alkaline and rare earth ions are generally known to enter chlorapatite, but attempts to incorporate simulated waste salt formulations into HIPed chlorapatite-based preparations or to substitute Cs alone into the structure of Ca-based chlorapatite were not successful on the basis of scanning electron microscopy. The materials exhibited severe water leachability, mainly in regard to Cs release. Attempts to substitute Cs into Ba- and Sr-based chlorapatites also did not look encouraging. Consequently the use of apatite alone to retain fission product-bearing waste pyroprocessing salts from electrolytic nuclear fuel reprocessing is problematical, but chlorapatite glass-ceramics may be feasible, albeit with reduced waste loadings. Spodiosite, Ca _2(PO _4)Cl, does not appear to be suitable for incorporation of Cl-bearing waste containing fission products.