Written Evidence: House of Lords Select Committee on Science and Technology Committee Inquiry on Priorities for Nuclear Research and Technologies

Individual submission: to House of Lords Select Committee on Science & Technolog

Synthesis and Characterization of Brannerite Wasteforms for the Immobilization of Mixed Oxide Fuel Residues

A possible method for the reduction of civil Pu stockpiles is the reuse of Pu in mixed oxide fuel (MOX). During MOX fuel production, residues unsuitable for further recycle will be produced. Due to their high actinide content MOX residues require immobilization within a robust host matrix. Although it is possible to immobilize actinides in vitreous wasteforms; ceramic phases, such as brannerite (UTi2O6), are attractive due to their high waste loading capacity and relative insolubility. A range of uranium brannerites, formulated GdxU1-xTi2O6, were prepared using a mixed oxide route. Charge compensation of divalent and trivalent cations was expected to occur via the oxidation of U4+ to higher valence states (U5+ or U6+). Gd3+ was added to act as a neutron absorber in the final Pu bearing wasteform. X-ray powder diffraction of synthesised specimens found that phase distribution was strongly affected by processing atmosphere (air or Ar). In all cases prototypical brannerite was formed accompanied by different secondary phases dependent on processing atmosphere. Microstructural analysis (SEM) of the sintered samples confirmed the results of the X-ray powder diffraction. The preliminary results presented here indicate that brannerite is a promising host matrix for mixed oxide fuel residues

Characterisation of co-mixed HIP wasteforms for Magnox sludge and clinoptilolite wastes

Co-mixed simulant wasteforms consisting of calcined Magnox sludge simulant and clinoptilolite, with additions of a glass forming frit and CeO2 or U3O8 were processed using Hot Isostatic Pressing (HIP). This enabled the production of high waste loaded materials, with the successful incorporation of both simulant and active material. These formed heterogeneous glass-ceramic products, with decomposition of raw materials and some vitreous phase formation. The aqueous durability of these materials was assessed over a 28-day period using a modified PCT test, and favourably compared to the durability of an international glass. Overall this verifies the potential for HIP technology to be used in wasteform production, with potential large reductions in waste volume, especially if co-mixed wastes are considered

Hot isostatic pressing: thermal treatment trials of inactive and radioactive simulant UK intermediate level waste

Hot Isostatic Pressing (HIPing) is a batch process thermal treatment technology where wastes are heated and compressed within a sealed stainless steel canister; typically resulting in durable, high density ceramics or glasses with minimal loss of volatile elements, and accountability of active inventories. The University of Sheffield has a small-scale research HIP with capability to process simulant wasteforms containing radioactive materials, to help underpin larger-scale industrial applications of this technology. It was under this remit that a series of trials were undertaken, to produce small simulant radioactive wasteforms incorporating problematic UK waste streams such as Magnox sludges and clinoptilolite ion-exchange material. Each trial was successfully batched, sealed, and HIPed at 1250 °C, resulting in solidified products entirely contained within the steel HIP canisters. The ability to safely produce active wasteforms within the same facility validates the active furnace isolation chamber (AFIC) system. Overall the success of these trials demonstrate the ability of smaller research HIP facilities to build up the scientific and technical case for further implementation of HIP technology as a viable waste treatment option

Reactive spark plasma synthesis of CaZrTi2O7 zirconolite ceramics for plutonium disposition

Near single phase zirconolite ceramics, prototypically CaZrTi 2 O 7 , were fabricated by reactive spark plasma sintering (RSPS), from commercially available CaTiO 3 , ZrO 2 and TiO 2 reagents, after processing at 1200 °C for only 1 h. Ceramics were of theoretical density and formed with a controlled mean grain size of 1.9 ± 0.6 μm. The reducing conditions of RSPS afforded the presence of paramagnetic Ti 3+ , as demonstrated by EPR spectroscopy. Overall, this study demonstrates the potential for RSPS to be a disruptive technology for disposition of surplus separated plutonium stockpiles in ceramic wasteforms, given its inherent advantage of near net shape products and rapid throughput

MoO3 incorporation in magnesium aluminosilicate glasses

Molybdate has a very low solubility in silicate and borosilicate glass systems and its excess presence in nuclear waste glass can cause the formation of a readily soluble “yellow phase”. In this study, the incorporation of molybdenum oxide (MoO3) in a magnesium aluminosilicate glass system has been investigated. The prepared glasses show a higher than 90% molybdenum retention rate and up to 5.34 mol% (12.28 wt%) MoO3 can be incorporated into these glasses without causing visible phase separation. The incorporation of MoO3 increases glass density, decreases glass transition and crystallisation temperatures and intensifies Raman bands assigned to vibrations of MoO42− units. When excess molybdate is added liquid–liquid phase separation and crystallisation occurs. The separated phase is spherical, 200–400 nm in diameter and randomly dispersed. Based on powder X-ray diffraction, Raman spectroscopy and transmission electron microscopy, the separated phase is identified as MgMoO4

Development, characterization and dissolution behavior of calcium-aluminoborate glass wasteforms to immobilize rare-earth oxides

Calcium-aluminoborate (CAB) glasses were developed to sequester new waste compositions made of several rare-earth oxides generated from the pyrochemical reprocessing of spent nuclear fuel. Several important wasteform properties such as waste loading, processability and chemical durability were evaluated. The maximum waste loading of the CAB compositions was determined to be ~56.8 wt%. Viscosity and the electrical conductivity of the CAB melt at 1300 °C were 7.817 Pa·s and 0.4603 S/cm, respectively, which satisfies the conditions for commercial cold-crucible induction melting (CCIM) process. Addition of rare-earth oxides to CAB glasses resulted in dramatic decreases in the elemental releases of B and Ca in aqueous dissolution experiments. Normalized elemental releases from product consistency standard chemical durability test were <3.62·10-5 g·m-2for Nd, 0.009 g·m-2for Al, 0.067 g·m-2for B and 0.073 g·m-2for Ca (at 90, after 7 days, for SA/V = 2000m-1); all meet European and US regulation limits. After 20 d of dissolution, a hydrated alteration layer of ~ 200-nm-thick, Ca-depleted and Nd-rich, was formed at the surface of CAB glasses with 20 mol% Nd2O3whereas boehmite [AlO(OH)] secondary crystalline phases were formed in pure CAB glass that contained no Nd2O3

Development of phosphate glass and multi-phase titanate ceramic compositions for thermal treatment of irradiated nuclear fuel residues

The highly heterogeneous nature of UK legacy damaged and degraded spent nuclear fuels and so called, 'orphan fuels', prohibits the use of standard conditioning methods. An inventory of UK residual fuels yielded an account for three main fuel types: Magnox, AGR (advanced gas-cooled reactor) and MOx (mixed oxides). A series of glass and ceramic type host systems have been investigated for potential conditioning of these high uranium content spent fuel materials. Electron microscopy and powder X-ray diffraction techniques were used to characterise the prototypical wasteforms. Two sets of low-melt temperature phosphate glass compositions were trialled with additions of CeO2 to simulate the fluorite structure and large ionic radius of U in oxide fuels. Evolution of monazite-type phases at simulant oxide fuel loadings above 15 wt.% highlighted a potential development into a glass-ceramic hybrid assemblage. Investigation into the use of an alkoxide nitrate synthesis route for SYNROC-F type ceramic precursors has allowed for the demonstration of a sintered host pyrochlore phase containing up to ~40 wt.% fuel simulant CeO2. Gas evolution has led to increased porosity at higher temperatures and longer sintering times, this may be mitigated by higher pre-calcination temperatures