The immobilization of chloride-containing actinide waste in a calcium phosphate ceramic host: Ageing studies
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The immobilization of chloride-containing actinide waste in a calcium phosphate ceramic host: ageing studies B. L. Metcalfe, I. W. Donald, R. D. Scheele* and D. M. Strachan* Atomic Weapons Establishment, Aldermaston, Berkshire, UK *Pacific Northwest National Laboratory, Richland, WA, USA ABSTRACT Immobilization of radioactive wastes arising from the pyrochemical reprocessing of Pu metal with calcium phosphate as the host material has been investigated. Initial studies in which non-active elements are substituted for the actinide elements present in the wastes demonstrated that effective immobilization of both the cations and chloride ions was achieved within the chlorapatite Ca5(PO4)3Cl, and spodiosite, Ca2(PO4)Cl, mineral phases produced during the solid state reaction between host and waste. Followup studies with radioactive simulated waste composed of CaCl2, PuCl3 and AmCl3 have confirmed the viability of the process and the durability of the product in aqueous solution. More recently a study of the long-term radiological stability and chemical durability of the ceramic product has commenced in which accelerated ageing of the ceramic phases is being achieved through the replacement of the 239Pu (half life 24,360y) that is contained in the actual waste by the short lived isotope 238Pu (half life 86.4y). The preparation of non-active and active samples and the crystal phases formed in each system as determined with XRD are herein reported. Data are presented which show that there is no detectable change in the XRD pattern of the samples containing 238Pu after 532 days of ageing, corresponding to around 400 years of real time ageing employing 239 Pu. The detailed effects of ageing on the crystal structure and on the chemical durability of samples in aqueous solution are reported. INTRODUCTION Work to identify potential host materials for the immobilization of actinide bearing wastes arising from the pyrochemical reprocessing of plutonium has demonstrated that calcium phosphate appears to fulfil the necessary criteria [1-5]. Using samarium as the non-active surrogate for the actinide constituents we observed that the solid state reaction between calcium phosphate and simulated Type I waste, essentially a chloride rich waste containing actinides, led to the formation of chlorapatite and spodiosite. Apatite is highly non-stoichiometric with a general formula A5(BO4)3(OH, F, Cl), where A can be a variety of mono-, di- and tri-valent cations including Ca, Ba, Na, Pb, Sr, La, Ce and B is commonly P. This shows it has the ability to incorporate a wide range of ions into the structure, including the potentially problematic chloride anions present in the waste. Similarly spodiosite, A2(PO4)Cl, can incorporate a range of cations and theoretically up to 16.9 wt % of chlorine when A is Ca. It was found that the mixed chlorapatite/ spodiosite powder could not be converted into a dense monolithic form by sintering and so other methods to achieve this were investigated. Bonding using a glass was considered the best option
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