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

Synthesis and characterisation of high ceramic fraction brannerite (UTi2O6) glass-ceramic composites

Brannerite, UTi2O6, glass-ceramic composites have been prepared, using UO2 and TiO2 as the ceramic phase precursors. A range of cold-press and sinter samples with varying glass:ceramic ratios have been prepared under argon at 1200 °C to investigate the effect of glass content on formation of brannerite. Ceramic brannerite formed well in all compositions, even at low (10% by weight) glass fractions, with UO2 as a minor product. Three further brannerite glass-ceramics have been prepared by hot isostatic pressing to investigate the compatibility of this system to HIPing. The samples HIPed at 1200 °C form brannerite, with UO2 as a minor phase with slightly higher abundance than in the cold-press and sinter samples

The formation of stoichiometric uranium brannerite (UTi2O6) glass-ceramic composites from the component oxides in a one-pot synthesis

Brannerite glass-ceramic composites have been suggested as suitable wasteform materials for high-actinide content wastes, but the formation of glass-ceramic composites containing stoichiometric uranium brannerite (UTi2O6) has not been well-studied. Uranium brannerite glass-ceramic composites were synthesised at by a one-pot cold-press and sinter route from the component oxides. As a comparison, two further samples were produced using an alkoxide-nitrate route. A range of compositions with varying molar ratios of uranium and titanium oxides (from 1:2 to 1:3.20) were synthesised, with a range of different heat treatments (1200 °C for 12–48 h, and 1250 °C for 12 h). All compositions were analysed by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray near-edge spectroscopy, and found to contain UTi2O6 as the majority crystalline phase forming within a glass matrix of nominal stoichiometry Na2AlBSi6O16. In compositions with UO2:TiO2 ratios of 1:2 and 1:2.28, particles of UO2 were observed in the glass matrix, likely due to dissolution of TiO2 in the glass phase; this was prevented by the addition of excess TiO2. This work demonstrates the suitability of this system to produce highly durable wasteforms with excellent actinide waste loading, even with a simple one-pot process. Some grains of brannerite consist of a UO2 particle encapsulated in a shell of UTi2O6, suggesting that brannerite crystallises around particles of UO2 until either the UO2 is fully depleted, or the kinetic barrier becomes too large for further diffusion to occur. We propose that the formation of brannerite within glass-ceramic composites at lower temperatures than that for pure ceramic brannerite is caused by an increase in the rate of diffusion of the reactants within the glass

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

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

Laboratory based X-ray absorption spectroscopy of iron phosphate glasses for radioactive waste immobilisation: a preliminary investigation.

We report the application of laboratory based X-ray absorption spectroscopy to the speciation of Fe in iron phosphate glasses prepared by conventional and microwave melting. Analysis of the weak pre-edge features in Fe K-edge XANES data demonstrated glasses produced by microwave melting to have a higher fraction of reduced Fe2+ species, since microwave melts do not have sufficient time to equilibrate with the prevailing oxygen partial pressure, compared to counterparts produced by conventional melting. Furthermore, our laboratory XANES data are consistent with the formation of octahedral Fe2+ at the expense of tetrahedral Fe3+ species, with increasing Fe2+ content. These findings are consistent with the previous findings of our 57Fe Mossbauer study, synchrotron XANES data, and current understanding of the structure of iron phosphate glasses, and demonstrate the utility of laboratory based XANES for routine speciation of Fe in these and other materials

On the existence of AgM9(VO4)(6)I (M = Ba, Pb)

The syntheses of the reported compounds AgM9(VO4)6I (M ¼ Ba, Pb) were reinvestigated. Stoichiometric amounts of AgI with either M3(VO4)2 (M ¼ Ba, Pb) or PbO and V2O5 were reacted in the solid-state at elevated temperatures in air or in flame-sealed quartz vessels. The resulting products were characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, and thermal analyses. Results show that, for all reaction conditions, the target AgM9(VO4)6I (M ¼ Ba, Pb) phases could not be isolated. Instead, heterogeneous phase distributions of primarily M3(VO4)2 (M ¼ Ba, Pb) and AgI were obtained. These findings demonstrate that AgI incorporation into single phase, iodine-deficient apatite derivatives for the immobilization of iodine-129 are not feasible under such conditions. This conclusion is important for the conditioning of iodine-129 in advanced reprocessing flowsheets, where iodine is typically sequestered as AgI

Solid solubility in the CeTi2O6–CeTiNbO6 system: a multi-element X-ray spectroscopic study

In order to investigate the limits of solid solubility between Ce-brannerite (CeTi2O6) and Ce-aeschynite (CeTiNbO6), materials in the system CeTi2–xNbxO6 have been produced by a solid state route and characterised by XRD and XANES at the Ce L3-, Ti K- and Nb K-edges, including Rietveld method refinements and linear combination fitting. Significant solid solubility was observed at the brannerite end, with near-single-phase brannerite observed for x = 0.2, 0.4, and only minor aeschynite observed where x = 0.6 which was identified as exceeding the limit of solubility of Nb. All Nb was present as Nb5+, with the substitution of Nb5+ into the brannerite structure permitted by the reduction of the same fraction of Ce4+ to Ce3+. This work expands the crystal chemistry of the titanate brannerites, with Ce-site oxidation states of less than 4+ being possible where sufficient charge-balancing species are available on the Ti-site

The effect of pre-treatment parameters on the quality of glass-ceramic wasteforms for plutonium immobilisation, consolidated by hot isostatic pressing

Glass-ceramics with high glass fractions (70 wt%) were fabricated in stainless steel canisters by hot isostatic pressing (HIP), at laboratory scale. High (600 C) and low (300 C) temperature pre-treatments were investigated to reduce the canister evacuation time and to understand the effect on the phase assemblage and microstructure of the hot isostatically pressed product. Characterisation of the HIPed materials was performed using scanning electron microscopy (SEM), coupled with energy dispersive Xray analysis (EDX) and powder X-ray diffraction (XRD). This analysis showed the microstructure and phase assemblage was independent of the variation in pre-treatment parameters. It was demonstrated that a high temperature pre-treatment of batch reagents, prior to the HIP cycle, is beneficial when using oxide precursors, in order to remove volatiles and achieve high quality dense materials. Sample throughput can be increased significantly by utilising a high temperature ex-situ calcination prior to the HIP cycle. Investigation of glass-ceramic wasteform processing utilising a glass frit precursor, produced a phase assemblage and microstructure comparable to that obtained using oxide precursors. The use of a glass frit precursor should allow optimised throughput of waste packages in a production facility, avoiding the need for a calcination pre-treatment required to remove volatiles from oxide precursors

Advanced gas-cooled reactor SIMFuel fabricated by Hot Isostatic Pressing: a feasibility investigation

The manufacture of a simulant UK Advanced Gas Cooled Reactor (AGR) spent nuclear fuel (SIMFuel) was achieved by Hot Isostatic Pressing (HIP). Characterisation of HIP AGR SIMFuels, tailored to burn ups of 25 GWd/t U and 43 GWd/t U (after 100 years cooling) demonstrated fission product partitioning, phase assemblage, microstructure and porosity in good agreement with spent nuclear fuels and SIMFuels, and AGR fuels in particular. A pivotal advantage of the application of the HIP manufacturing method is the retention of volatile fission products within the resultant SIMFuel as the result of using a hermetically-sealed container. This new approach to SIMFuel manufacture should enable the production of more accurate spent nuclear fuel surrogates to support research on spent fuel management, recycle, and disposal, and the thermal treatment of fuel residues and debris