I18-Microfocus Spectroscopy
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Clare L.
Thorpe
,
Nick
Aldred
,
Stuart
Creasey-Gray
,
Martin C.
Stennett
,
Eperke A.
Rencz
,
Susan
Nehzati
,
Latham T.
Haigh
,
Garry
Manifold
,
Nishta
Vallo
,
Christoph
Lenting
,
Claire L.
Corkhill
,
Russell J.
Hand
Diamond Proposal Number(s):
[38045]
Open Access
Abstract: Glass ingots of lead silicate composition from the shipwreck of the Albion were studied to ascertain the chemistry and mineralogy of alteration products after exposure to seawater for 220 years. Alteration observed on natural samples was compared to that of the same glasses exposed to short-term, high temperature, laboratory dissolution tests in synthetic seawater and significant differences were observed. Alteration layers on natural samples were more chemically complex having sequestered high concentrations of elements present only at trace quantities in seawater. Electron microprobe analysis and microfocus x-ray absorption spectroscopy shows that P, most likely released by biological activity in the vicinity of the wreck, accumulated in naturally altered samples to form Pb–Ca-phosphate phases whilst Pb-sulphate phases formed in laboratory tests. Meanwhile Fe, present at < 0.3 wt % in the glass and ppb concentrations in seawater, accumulated to form Fe-silicates whilst Mg-silicates predominated in laboratory tests. Biologically induced corrosion of naturally altered samples was also considered. Experiments conducted to test barnacle settlement rates suggest that biotoxic elements within the glass, primarily Pb but potentially also Cu, Co and Ni deterred barnacle settlement. Despite this toxicity, some colonisation of the glass surface by both barnacles and bryozoan did occur and, whilst barnacles appeared to protect against chemical attack, bryozoan colonies caused increased cracking, possibly due stress created at the glass surface. Results highlight the challenges in recreating open, natural systems in laboratory settings and demonstrate that elements present at low concentrations can have a significant impact over long timescales.
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May 2025
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B18-Core EXAFS
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Diamond Proposal Number(s):
[20872]
Open Access
Abstract: The safe and secure management of civil separated plutonium is a UK government and NDA priority. One potential solution to address this considers the manufacture of a modified version of mixed oxide (MOX) fuel, comprising PuO2 dispersed within a UO2 matrix and doped with a suitable neutron absorbing element to maintain criticality control. As an initial step to understand whether an industrially-relevant, proven MOX fuel fabrication process could offer a potential route to the production of a Pu-disposition matrix based on MOX, a series of Gd-doped UO2 pellets were prepared by Orano at the CDA workshop of the MELOX facility in France. Characterisation was performed to quantify the density, morphology (grain size and porosity), Gd distribution and Gd incorporation mechanism. It was found that the materials produced were highly reproducible and similar in density and morphology, irrespective of the variables investigated, and similar to unirradiated UOX and MOX fuel. Gd was distributed in a similar manner to the distribution of PuO2 in unirradiated MIMAS (MIcronisation of a MASter Blend) MOX fuel and evidence for the existence of a solid solution between Gd2O3 and UO2 was ascertained, which could be viewed as favourable from a GDF post-closure criticality control perspective. The source of the powder had the greatest effect on the final characteristics of the Pu-disposition MOX pellets, due to sintering reactivity; however, these differences were minor. These results are a promising step towards the full-scale manufacture of ceramics suitable for the immobilisation and disposition of separated PuO2 in a GDF, should policy dictate.
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Oct 2024
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[28515]
Open Access
Abstract: Mn-doped UO2 is under consideration for use as an accident tolerant nuclear fuel. We detail the synthesis of Mn-doped UO2 prepared via a wet co-precipitation method, which was refined to improve the yield of incorporated Mn. To verify the Mn-doped UO2 defect chemistry, X-ray absorption spectroscopy at the Mn K-edge was performed, in addition to X-ray diffraction, Raman spectroscopy and high-energy resolved fluorescence detection X-ray absorption near edge spectroscopy at the U M4-edge. It was established that Mn2+ directly substitutes for U4+ in the UO2 lattice, accompanied by oxygen vacancy (Ov) charge compensation. In contrast to other divalent-element doped UO2 materials, compelling evidence for U5+ in a charge compensating role was not found. This work furthers understanding of the structure and crystal chemistry of Mn-doped UO2, which could show potential advantages as a novel efficient advanced nuclear fuel.
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Jan 2024
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B18-Core EXAFS
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Diamond Proposal Number(s):
[1724]
Open Access
Abstract: ThTi2O6 derived compounds with the brannerite structure were designed, synthesised, and characterised with the aim of stabilising incorporation of U5+ or U6+, at dilute concentration. Appropriate charge compensation was targeted by co-substitution of Gd3+, Ca2+, Al3+, or Cr3+, on the Th or Ti site. U L3 edge X-ray Absorption Near Edge Spectroscopy (XANES) and High Energy Resolution Fluorescence Detected U M4 edge XANES evidenced U5+ as the major oxidation state in all compounds, with a minor fraction of U6+ (2–13%). The balance of X-ray and Raman spectroscopy data support uranate, rather than uranyl, as the dominant U6+ speciation in the reported brannerites. It is considered that the U6+ concentration was limited by unfavourable electrostatic repulsion arising from substitution in the octahedral Th or Ti sites, which share two or three edges, respectively, with neighbouring polyhedra in the brannerite structure.
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Aug 2023
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B18-Core EXAFS
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Lewis R.
Blackburn
,
Luke T.
Townsend
,
Malin C.
Dixon Wilkins
,
Toshiaki
Ina
,
Merve
Kuman
,
Shi-Kuan
Sun
,
Amber R.
Mason
,
Laura J.
Gardner
,
Martin C.
Stennett
,
Claire L.
Corkhill
,
Neil C.
Hyatt
Diamond Proposal Number(s):
[17243]
Open Access
Abstract: Indium (In) is a neutron absorbing additive that could feasibly be used to mitigate criticality in ceramic wasteforms containing Pu in the immobilised form, for which zirconolite (nominally CaZrTi2O7) is a candidate host phase. Herein, the solid solutions Ca1-xZr1-xIn2xTi2O7 (0.10 ≤ x ≤ 1.00; air synthesis) and Ca1-xUxZrTi2-2xIn2xO7 (x = 0.05, 0.10; air and argon synthesis) were investigated by conventional solid state sintering at a temperature of 1350 °C maintained for 20 h, with a view to characterise In3+ substitution behaviour in the zirconolite phase across the Ca2+, Zr4+ and Ti4+ sites. When targeting Ca1-xZr1-xIn2xTi2O7, single phase zirconolite-2M was formed at In concentrations of 0.10 ≤ x ≤ 0.20; beyond x ≥ 0.20, a number of secondary In-containing phases were stabilised. Zirconolite-2M remained a constituent of the phase assemblage up to a concentration of x = 0.80, albeit at relatively low concentration beyond x ≥ 0.40. It was not possible to synthesise the In2Ti2O7 end member compound using a solid state route. Analysis of the In K-edge XANES spectra in the single phase zirconolite-2M compounds confirmed that the In inventory was speciated as trivalent In3+, consistent with targeted oxidation state. However, fitting of the EXAFS region using the zirconolite-2M structural model was consistent with In3+ cations accommodated within the Ti4+ site, contrary to the targeted substitution scheme. When deploying U as a surrogate for immobilised Pu in the Ca1-xUxZrTi2-2xIn2xO7 solid solution, it was demonstrated that, for both x = 0.05 and 0.10, In3+ was successfully able to stabilise zirconolite-2M when U was distributed predominantly as both U4+ and average U5+, when synthesised under argon and air, respectively, determined by U L3-edge XANES analysis.
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Jun 2023
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B18-Core EXAFS
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Diamond Proposal Number(s):
[17782, 24074]
Open Access
Abstract: Crystal chemical design principles were applied to synthesise novel U4+ dominant and titanium excess betafite phases Ca1.15(5)U0.56(4)Zr0.17(2)Ti2.19(2)O7 and Ca1.10(4)U0.68(4)Zr0.15(3)Ti2.12(2)O7, in high yield (85–95 wt%), and ceramic density reaching 99% of theoretical. Substitution of Ti on the A-site of the pyrochlore structure, in excess of full B-site occupancy, enabled the radius ratio (rA/rB = 1.69) to be tuned into the pyrochlore stability field, approximately 1.48 ≲ rA/rB ≲ 1.78, in contrast to the archetype composition CaUTi2O7 (rA/rB = 1.75). U L3-edge XANES and U 4f7/2 and U 4f5/2 XPS data evidenced U4+ as the dominant speciation, consistent with the determined chemical compositions. The new betafite phases, and further analysis reported herein, point to a wider family of actinide betafite pyrochlores that could be stabilised by application of the underlying crystal chemical principle applied here.
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Jun 2023
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B18-Core EXAFS
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Diamond Proposal Number(s):
[17782]
Open Access
Abstract: Portland cement-based grouts used for radioactive waste immobilisation contain a Ca- and Si-rich binder phase, known as calcium–silicate–hydrate (C–S–H). Depending on the blend of cement used, the Ca/Si ratio can vary considerably. A range of C–S–H minerals with Ca/Si ratios from 0.6 to 1.6 were synthesised and contacted with aqueous U(VI) at 0.5 mM and 10 mM concentrations. Solid-state 29Si MAS-NMR spectroscopy was applied to probe the Si coordination environment in U(VI)-contacted C–S–H minerals and, in conjunction with U LIII-edge X-ray absorption spectroscopy analysis, inferences of the fate of U(VI) in these systems were made. At moderate or high Ca/Si ratios, uranophane-type uranyl silicates or Ca-uranates dominated, while at the lowest Ca/Si ratios, the formation of a Ca-bearing uranyl silicate mineral, similar to haiweeite (Ca[(UO2)2Si5O12(OH)2]·3H2O) or Ca-bearing weeksite (Ca2(UO2)2Si6O15·10H2O) was identified. This study highlights the influence of Ca/Si ratio on uranyl sequestration, of interest in the development of post-closure safety models for U-bearing radioactive waste disposal.
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Feb 2023
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B18-Core EXAFS
I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[20872, 24074, 28515]
Open Access
Abstract: Advanced Cr-doped UO2 fuels are essential for driving safe and efficient generation of nuclear energy. Although widely deployed, little is known about their fundamental chemistry, which is a critical gap for development of new fuel materials and radioactive waste management strategies. Utilising an original approach, we directly evidence the chemistry of Cr(3+)2O3–doped U(4+)O2. Advanced high-flux, high-spectral purity X-ray absorption spectroscopy (XAS), corroborated by diffraction, Raman spectroscopy and high energy resolved fluorescence detection-XAS, is used to establish that Cr2+ directly substitutes for U4+, accompanied by U5+ and oxygen vacancy charge compensation. Extension of the analysis to heat-treated simulant nuclear fuel reveals a mixed Cr2+/3+ oxidation state, with Cr in more than one physical form, explaining the substantial discrepancies that exist in the literature. Successful demonstration of this analytical advance, and the scientific underpinning it provides, opens opportunities for an expansion in the range of dopants utilised in advanced UO2 fuels.
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Dec 2022
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I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[20189]
Open Access
Abstract: A primary target towards the clean-up operation of the Fukushima disaster is the retrieval of Molten Core-Concrete Interaction (MCCI) products, presently residing on the basement of the damaged nuclear reactor Units 1–3. MCCI is a fusion of materials, composed of both nuclear fuel cladding and neighbouring structural components. Determining the currently unknown, physical and mechanical properties of MCCI is essential for successful and timely retrieval. In this paper, we aim to experimentally quantify the mechanical properties of a material fabricated to resemble MCCI. A small-scale representative specimen was mechanically tested using Hertzian indentation stepwise loading. Synchrotron X-ray computed tomography was conducted at several loading stages to reveal the sample microstructure and mechanical degradation. The acquired tomograms were analysed by digital volume correlation to measure full-field displacements and strains developed within the sample volume. Young’s modulus and Poisson ratio were determined via this combined methodology.
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Jul 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[17243]
Open Access
Abstract: Within the context of the UK's radioactive waste vitrification programme, which utilises a lithium-sodium borosilicate glass modified with CaO and ZnO to immobilise high level nuclear waste, an investigation was undertaken to evaluate the effects on the structure and chemical durability of altering the CaO to ZnO ratio. Using a 6-component simplified alkali aluminoborosilicate glass, replacement of CaO by ZnO, even in moderate amounts, had a marked effect on the glass structure. Zn K-edge EXAFS identified that Zn existed within two distinct environments, both containing Zn in tetrahedral coordination. At high CaO content, Zn was coordinated in a “hardystonite-like” (Ca2ZnSi2O7) environment, while higher ZnO content induced destabilization and nano-scale phase separation occurred, forming discrete tri-clusters of Si/Al–O–Zn in a “willemite-like” (Zn2SiO4) environment. The presence of these environments was corroborated by thermal analysis and 29Si MAS NMR data. Despite this phase separation, glasses with higher ZnO content were found to exhibit the lowest normalized dissolution rates under dilute conditions, as determined using the Single-Pass Flow-Through methodology. Chemical structure analysis indicates that such behaviour is a result of enhanced polymerization of the glass network in the presence of Zn, and a reduced propensity for Si–O–Zn bond hydrolysis in water, resolving a long-running literature debate on the role of Zn on the dissolution of glass in the forward rate. Evidence is presented that indicates the phase-separated regions dissolve at somewhat different rates. These results enhance understanding of CaO[thin space (1/6-em)]:[thin space (1/6-em)]ZnO-containing glass behaviour, important to assess the long-term safety of radioactive waste management and disposal strategies.
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Jan 2022
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