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

Solubility, speciation and local environment of chlorine in zirconolite glass–ceramics for the immobilisation of plutonium residues

The immobilisation and disposal of fissile materials from civil and defence nuclear programmes requires compatible, passively safe and proliferation resistant wasteforms. In this study, we demonstrate the application of an albite glass–zirconolite ceramic material for immobilisation of chloride contaminated plutonium oxide residues in the United Kingdom. The chlorine solubility limit in the albite glass phase was determined to be 1.0 ± 0.1 wt%, above the maximum envisaged chorine inventory of 0.5 wt%, attainable at a 20 wt% PuO2 incorporation rate within the ceramic. Cl K-edge of X-ray Absorption Near Edge Spectroscopy (XANES) was exploited to confirm partitioning of Cl to the glass phase, speciated as the chloride anion, with exsolution of crystalline NaCl above the chlorine solubility limit. Combinatorial fitting of Cl XANES data, utilising a library of chemically plausible reference spectra, demonstrated the association of Cl with Na and Ca modifier cations, with environments characteristic of the aluminosilicate chloride minerals eudialyte, sodalite, chlorellestadite and afghanite. Adventitious incorporation of Ca, Zr and Ti within the albite glass phase apparently assists chlorine solubility, by templating a local chemical environment characteristic of the mineral reference compounds. The partitioning of Ce, as a Pu analogue, within the glass–ceramic was not adversely impacted by incorporation of Cl. The significance of this research is in demonstrating the compatibility of the glass–ceramic wasteform toward Cl solubility at the expected incorporation rate, below the determined solubility limit. Thus, an upstream heat treatment facility to remove chloride contamination, as specified in the current conceptual flowsheet, would not be required from the perspective of wasteform compatibility, thus providing scope to de-risk the technology roadmap and reduce the projected capital and operational plant costs

A preliminary validation study of PuO2 incorporation into zirconolite glass-ceramics

Zirconolite glass-ceramics are being developed as potential wasteforms for the disposition of Pu wastes in the UK. Previous studies utilised a variety of surrogates whilst this work uses both cold-press and sinter and hot isostatic press methods to validate the wasteform with PuO2. A cold press and sinter sample was fabricated as part of a validation study for plutonium incorporation in hot isostatically pressed (HIPed) wasteforms. The results confirmed the cold-press and sinter, achieved successful waste incorporation and a microstructure and phase assemblage that was in agreement with those expected of a HIPed equivalent. A HIP sample was fabricated of the same composition and characterised by SEM and XRD. Results were in agreement with the sintered sample and achieved complete waste incorporation into the glass-ceramic wasteform. These samples have demonstrated successful incorporation of PuO2 into glass-ceramic HIPed wasteforms proposed for processing Pu-based waste-streams in the UK

Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses

The local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg)2SiO4, pyroxenes (Fe,Mg)SiO3, calcic FeO-CaSiO3, and a calcium aluminosilicate composition, where total iron content is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer. Remarkably, XANES pre-edge peak areas imply mean Fe-O coordination numbers (nFeO) close to 5 in all cases, with only a slight tendency toward higher values in the most iron rich melts, suggesting an intermediate role for both Fe(II) and Fe(III) in terms of network formation. End member coordination numbers for Fe(II)-O and Fe(III)-O are estimated to be similar, having means (and standard deviations) of 5.0(2) and 4.9(1), respectively. As such, the preference for ferric iron to occupy lower coordination sites than ferrous is weak, in contrast to published behavior in some alkali-rich systems, which may explain the larger published viscosity variations with Fe3+/ΣFe in alkali-, compared to alkaline earth-iron silicates. Temperature effects on nFeO are inferred to be small based on the melt data, as well as by comparison to glasses formed on quenching. Positive shifts of the pre-edge peak centroids observed in many cases on quenching are attributed to rapid oxidation enabled by the stirring of the melt droplets by the levitation gas jet. Fe3+/ΣFe values were estimated from XANES pre-edge peaks using published calibrations and compared to semi-empirical thermodynamic model calculations and Mössbauer measurements on quench products. Whilst showing positive correlation, the comparisons highlight the limitations involved in applying XANES calibrations and models for Fe3+/ΣFe derived from measurements on glasses, to high temperature basic melts. Fe3+/ΣFe varies from approximately zero up to about 65% in the high temperature melts and 75% in the glasses