Browsing by Author "Kimpton, JA"

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    Alkali metal-modified P2 NaxMnO2: crystal structure and application in sodium-ion batteries
    (American Chemical Society, 2020-08-18) Sehrawat, D; Rawal, A; Cheong, S; Avdeev, M; Ling, CD; Kimpton, JA; Sharma, N
    Sodium-ion batteries (NIBs) are an emerging alternative to lithium-ion batteries because of the abundance of sodium resources and their potentially lower cost. Here we report the Na0.7MnO2 solid state synthesized at 1000 °C that shows two distinct phases; one adopts hexagonal P2-type P63/mmc space group symmetry, and the other adopts orthorhombic Pbma space group symmetry. The phase ratio of P2 to the orthorhombic phase is 55.0(5):45.0(4). A single-phase P2 structure is found to form at 1000 °C after modification with alkali metals Rb and Cs, while the K-modified form produces an additional minor impurity. The modification is the addition of the alkali elements during synthesis that do not appear to be doped into the crystal structure. As a cathode for NIBs, parent Na0.7MnO2 shows a second charge/discharge capacity of 143/134 mAh g–1, K-modified Na0.7MnO2 a capacity of 184/178 mAh g–1, Rb-modified Na0.9MnO2 a capacity of 159/150 mAh g–1, and Cs-modified Na0.7MnO2 a capacity of 171/163 mAh g–1 between 1.5 and 4.2 V at a current density of 15 mA g–1. The parent Na0.7MnO2 is compared with alkali metal (K, Rb, and Cs)-modified NaxMnO2 in terms of surface morphology using scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy, scanning electron microscopy, 23Na solid-state nuclear magnetic resonance, and X-ray photoelectron spectroscopy and in terms of electrochemical performance and structural electrochemical evolution using in situ or operando synchrotron X-ray diffraction. © 2020 American Chemical Society
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    Aluminum borohydride complex with ethylenediamine: crystal structure and dehydrogenation mechanism studies
    (American Chemical Society, 2016-04-20) Gu, QF; Wang, ZY; Filinchuk, Y; Kimpton, JA; Brand, HEA; Li, Q; Yu, XB
    We report the structure of an aluminum borohydride ethylenediamine complex, Al(EDA)3·3BH4·EDA. This structure was successfully determined using X-ray powder diffraction and was supported by first-principles calculations. The complex can be described as a mononuclear complex exhibiting three-dimensional supramolecular structure, built from units of Al[C2N2H8]3, BH4, and ethylenediamine (EDA) molecules. Examination of the chemical bonding indicates that this arrangement is stabilized via dihydrogen bonding between the NH2 ligand in EDA and the surrounding BH4. The partial ionic bonding between the Al and N atoms in EDA forms a five-member ring (5MR), an Al[NCCN] unit. The calculated H2 removal energies confirm that it is energetically favorable to remove the loosely bonded EDA and H atoms with N–H···H–B dihydrogen bonds upon heating. Our results suggest that the NH2 terminal ligand in the EDA molecule combines with a H atom in the BH4 group to release H2 at elevated temperature, and our results confirm that the experimental result Al(EDA)3·3BH4·EDA can release 8.4 wt % hydrogen above 149 °C with detectable EDA molecules. This work provides insights into the dehydrogenation behavior of Al(EDA)3·3BH4·EDA and has implications for future development of promising high-performance metal borohydride ethylenediamine complexes. © 2016 American Chemical Society
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    Anomalous thermal expansion in orthorhombic perovskite SrIrO3: Interplay between spin-orbit coupling and the crystal lattice
    (Americal Physical Society, 2014-06-16) Blanchard, PER; Reynolds, EM; Kennedy, BJ; Kimpton, JA; Avdeev, M; Belik, AA
    The structure of the orthorhombic (Pbnm) polytype of SrIrO3 has been investigated between 3 and 1100 K using a combination of synchrotron and neutron diffraction methods. The orthorhombic structure persists to 1100 K, the highest temperature available in this work. This is a consequence of the larger than expected octahedral tilting estimated from the neutron diffraction studies. We postulate that the strong spin-orbit coupling of the Ir4+ cation, which splits the t2g band, introduces additional strain on the lattice. This introduces unusual thermal expansion of the cell. SrIrO3 was characterized by resistivity, magnetization, and specific heat measurements. Metallic conductivity was observed between 2 and 300 K without indication of the previously reported metal-insulator transition. The Sommerfeld constant γ was 3.12(2) mJ mol−1 K−2, and a Fermi-liquid behavior was observed between 2 and 30 K with positive magnetoresistence of up to 2% (at 70 kOe and between 2 and 50 K).© 2014, American Physical Society.
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    Bayesian analysis of in-situ high-resolution X-ray diffraction synchrotron experiments of Ti-6Al-4V specimens undergoing tensile loading
    (The American Society of Mechanical Engineers, 2019-06) Armstrong, N; Lynch, PA; Kada, SR; Cizek, P; Kimpton, JA; Antoniou, RA
    Linking the accumulation of microstructural damage prior to crack initiation to the lifing of aero-engines components would help to better predict the time that a component spends in this crack initiation stage. We present the results and analysis of in-situ high-resolution X-ray diffraction (XRD) experiments of a Ti-6Al-4V specimen that experienced tensile loading using medium energy synchrotron X-rays (≤ 21 keV) carried out at the Australian Synchrotron. The XRD analysis characterised XRD line-broadening due to the build-up of dislocations and the formation of crystallites in α- and β-Ti-6Al-4V specimens. Using Bayesian XRD analysis methods, the density, spatial arrangement of dislocations, and crystallite size information for α- and β-phases of the Ti-6Al-4V was extracted from the XRD line-profiles, as a function of applied load. The XRD analysis was then compared and validated with transmission electron microscopy (TEM) analysis of the specimen before and after the loading. Comparison of the TEM and XRD analysis reveals broad agreement in terms of the microstructural damage of Ti-6Al-4V specimens. © 2019 by ASME and the Government of Australia
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    Br-doped Li4Ti5O12 and composite TiO2 anodes for Li-ion batteries: synchrotron x-ray and in situ neutron diffraction studies
    (John Wiley & Sons, Inc, 2011-09-01) Du, GD; Sharma, N; Peterson, VK; Kimpton, JA; Jia, DZ; Guo, ZP
    Synchrotron X-ray diffraction data were used to determine the phase purity and re-evaluate the crystal-structure of Li4Ti5O12-xBrx electrode materials (where the synthetic chemical inputs are x = 0.05, 0.10 0.20, 0.30). A maximum of x′ = 0.12 Br, where x′ is the Rietveld-refined value, can be substituted into the crystal structure with at least 2% rutile TiO2 forming as a second phase. Higher Br concentrations induced the formation of a third, presumably Br-rich, phase. These materials function as composite anodes that contain mixtures of TiO2, Li4Ti5O12-xBrx, and a Br-rich third, unknown, phase. The minor quantities of the secondary phases in combination with Li4Ti5O12-xBrx where x′ ∼ 0.1 were found to correspond to the optimum in electrochemical properties, while larger quantities of the secondary phases contributed to the degradation of the performance. In situ neutron diffraction of a composite anatase TiO2/Li4Ti5O12 anode within a custom-built battery was used to determine the electrochemical function of the TiO2 component. The Li4Ti5O12 component was found to be electrochemically active at lower voltages (1.5 V) relative to TiO2 (1.7 V). This enabled Li insertion/extraction to be tuned through the choice of voltage range in both components of this composite or in the anatase TiO2 phase only. The use of composite materials may facilitate the development of multi-component electrodes where different active materials can be cycled in order to tune power output. Copyright © 2011 Wiley-VCH Verlag GmbH & Co.
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    Cation antisite disorder in uranium-doped gadolinium zirconate pyrochlores
    (Elsevier, 2014-09-01) Gregg, DJ; Zhang, ZM; Thorogood, GJ; Kennedy, BJ; Kimpton, JA; Griffiths, GJ; Guagliardo, PR; Lumpkin, GR; Vance, ER
    The incorporation of uranium into gadolinium zirconate (Gd2Zr2O7) is investigated by synchrotron X-ray powder diffraction and X-ray absorption near-edge structure (XANES) spectroscopy. The results suggest that the uranium cation is largely located on the pyrochlore B-site instead of the targeted A-site. Cation disorder in Gd2Zr2O7 and U-doped Gd2Zr2O7 is investigated by positron annihilation lifetime spectroscopy (PALS) which demonstrates the absence of cation vacancies in these systems. This work provides direct evidence for cation antisite (A- and B-site mixing) disorder in U-doped and off-stoichiometric Gd2Zr2O7 pyrochlore. © 2014, Elsevier B.V.
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    Crystal structure and phase transitions in the uranium perovskite, Ba2SrUO6
    (Elsevier, 2013-02-01) Reynolds, EM; Kennedy, BJ; Thorogood, GJ; Gregg, DJ; Kimpton, JA
    The structure of one of the oxides proposed to be present in the grey phase of irradiated mixed oxide fuel, the double perovskite Ba2SrUO6 has been investigated from room temperature to 1300 K using synchrotron X-ray powder diffraction methods. The divalent strontium and hexavalent uranium are found to be fully ordered in the double-perovskite arrangement of alternating octahedra sharing corner oxygen atoms. At room temperature Ba2SrUO6 adopts a monoclinic structure in space group P21/n. Heating to above 900 K induces a first order transition to a rhombohedral structure, and further heating to above 1200 K results in a continuous transition to a cubic structure. The sequence of structures is associated with the progressive loss of cooperative tilting of the corner sharing SrO6 and UO6 octahedra. © 2012, Elsevier B.V.
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    Crystal structure of propio­nitrile (CH3CH2CN) determined using synchrotron powder X-ray diffraction
    (International Union of Crystallography, 2020-01) Brand, HEA; Gu, QF; Kimpton, JA; Auchettl, R; Ennis, C
    The structure and thermal expansion of the astronomical molecule propio­nitrile have been determined from 100 to 150 K using synchrotron powder X-ray diffraction. This temperature range correlates with the conditions of Titan's lower stratosphere, and near surface, where propio­nitrile is thought to accumulate and condense into pure and mixed-nitrile phases. Propio­nitrile was determined to crystallize in space group, Pnma (No. 62), with unit cell a = 7.56183 (16) Å, b = 6.59134 (14) Å, c = 7.23629 (14), volume = 360.675 (13) Å3 at 100 K. The thermal expansion was found to be highly anisotropic with an eightfold increase in expansion between the c and b axes. These data will prove crucial in the computational modelling of propio­nitrile–ice systems in outer Solar System environments, allowing us to simulate and assign vibrational peaks in the infrared spectra for future use in planetary astronomy. © 2020 International Union of Crystallography
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    Effect of oxygen partial pressure on the formation mechanisms of complex Ca-rich ferrites
    (The Iron and Steel Institute of Japan Keidanren Kaikan, 2013-01-01) Webster, NAS; Pownceby, MI; Madsen, IC; Kimpton, JA
    The formation mechanisms of the complex Ca-rich ferrite iron ore sinter bonding phases SFCA and SFCA-I, during heating of a synthetic sinter mixture in the range 298-1623 K and at pO(2) = 0.21, 5 x 10(-3) and 1 x 10(-4) atm, were determined using in situ X-ray diffraction. SFCA and, in particular, SFCA-I are desirable bonding phases in iron ore sinter, and improved understanding of the effect of parameters such as pO(2) on their formation may lead to improved ability to maximise their formation. in industrial sintering processes. SFCA-I and SFCA were both observed to form at pO(2) = 0.21 and 5 x 10-3 atm, with the formation of SFCA-I preceding SFCA formation in each case, but via distinctly different mechanisms at each pO(2). No SFCA-I was observed at pO(2) = 1 x 10-4 atm; instead, a Ca-rich phase designated CFAlSi, formed at 1 420 K. By 1 456 K, CFAlsi had decomposed to form melt and a small amount of SFCA. Such a low pO(2) during heating of industrial sinter mixtures is, therefore, undesirable, since it would not result in the formation of an abundance of SFCA and SFCA-I bonding phases. In addition, CFA phase, which was determined by Webster et al. (Metall. Mater. Trans. B, 43(2012), 1344) to be a key precursor phase in the formation of SFCA at pO(2) = 5 x 10(-3) atm, was also observed to form at pO(2) = 0.21 and 1 x 10(-4) atm, with the amount decreasing with increasing pO(2). Copyright © The Iron and Steel Institute of Japan 2013.
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    Effects of 18O isotope substitution in multiferroic RMnO3 (R = Tb, Dy)
    (Australian Institute of Physics, 2016-02-05) Graham, PJ; Narayanan, N; McIntyre, GJ; Hutchison, WD; Ulrich, C; Reynolds, N; Rovillain, P; Hester, JR; Kimpton, JA; Yethiraj, M; Pomjakushina, E; Condor, K; Kenzelmann, M
    Multiferroic materials demonstrate desirable attributes for next-generation multifunctional devices as they exhibit coexisting ferroelectric and magnetic orders. In type-II multiferroics, coupling exists that allows ferroelectricity to be manipulated via magnetic order and vice versa, offering potential in high-density information storage and sensor applications. Despite extensive investigations into the subject, questions of the physics of magnetoelectric coupling in multiferroics remain, and competing theories propose different mechanisms. The aim of this investigation was to study changes in the statics and dynamics of structural, ferroelectric and magnetic orders with oxygen-18 isotope substitution to shine light into the coupling mechanism in multiferroic RMnO3 (R=Tb, Dy) systems. We have performed Raman spectroscopy on 16O and 18O-substituted TbMnO3 single crystals. Oxygen-18 isotope substitution reduces all phonon frequencies significantly. However, specific heat measurements determine no changes in Mn3+ (28 and 41 K) magnetic phase transition temperatures. Pronounced anomalies in peak position and linewidth at the magnetic and ferroelectric phase transitions. While the anomalies at the sinusoidal magnetic phase transition (41 K) are in accordance to the theory of spin-phonon coupling, further deviations develop upon entering the ferroelectric phase (28 K). Furthermore, neutron diffraction measurements on 16O and 18O-substituted DyMnO3 powders show structural deviations at the ferroelectric phase transition (17 K) in the order of 100 fm in the b direction. The Pbnm space group is centrosymmetric and therefore does not allow ferroelectricity via atomic displacements, however our Reitveld analysis for the subgroup P21 shows significant displacements and polarisation along b that is comparable to the experimental value, making it the most promising candidate for ionic displacement induced polarisation in DyMnO3. These combined results demonstrate that structure is an important consideration in the emergence of ferroelectricity in these materials.
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    Effects of 18O isotope substitution in multiferroic RMnO3 (R=Tb, Dy)
    (Australian Institute of Physics, 2015-02-02) Graham, PJ; Narayanan, N; Reynolds, NM; Li, F; Rovillain, P; Bartkowiak, M; Hester, JR; Kimpton, JA; Yethiraj, M; Pomjakushina, E; Conder, K; Kenzelmann, M; McIntyre, GJ; Hutchison, WD; Ulrich, C
    Multiferroic materials demonstrate desirable attributes for next-generation multifunctional devices as they exhibit coexisting ferroelectric and magnetic orders. In type-II multiferroics, coupling exists that allows ferroelectricity to be manipulated via magnetic order and vice versa, offering potential in high-density information storage and sensor applications. Despite extensive investigations into the subject, questions of the physics of magnetoelectric coupling in multiferroics remain, and competing theories propose different mechanisms. The aim of this investigation was to study changes in the statics and dynamics of structural, ferroelectric and magnetic orders with oxygen-18 isotope substitution to shine light into the coupling mechanism in multiferroic RMnO3 (R=Tb, Dy) systems. We have performed Raman spectroscopy on 16O and 18O-substituted TbMnO3 single crystals. Oxygen-18 isotope substitution reduces all phonon frequencies significantly. However, specific heat measurements determine no changes in Mn3+ (28 and 41 K) magnetic phase transition temperatures. Pronounced anomalies in peak position and linewidth at the magnetic and ferroelectric phase transitions are seen. While the anomalies at the sinusoidal magnetic phase transition (41 K) are in accordance to the theory of spin-phonon coupling, further deviations develop upon entering the ferroelectric phase (28 K). Furthermore, neutron diffraction measurements on 16O and 18O-substituted DyMnO3 powders show structural deviations at the ferroelectric phase transition (17 K) in the order of 100 fm. These results indicate that the structure is actively involved in the emergence of ferroelectricity in these materials.
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    Fundamentals of silico-ferrite of calcium and aluminum (SFCA) and SFCA-I iron ore sinter bonding phase formation: effects of CaO:SiO2 ratio
    (Springer Link, 2014-07-22) Webster, NAS; Pownceby, MI; Madsen, IC; Studer, AJ; Manuel, JR; Kimpton, JA
    Effects of basicity, B (CaO:SiO2 ratio) on the thermal range, concentration, and formation mechanisms of silico-ferrite of calcium and aluminum (SFCA) and SFCA-I iron ore sinter bonding phases have been investigated using an in situ synchrotron X-ray diffraction-based methodology with subsequent Rietveld refinement-based quantitative phase analysis. SFCA and SFCA-I phases are the key bonding materials in iron ore sinter, and improved understanding of the effects of processing parameters such as basicity on their formation and decomposition may assist in improving efficiency of industrial iron ore sintering operations. Increasing basicity significantly increased the thermal range of SFCA-I, from 1363 K to 1533 K (1090 °C to 1260 °C) for a mixture with B = 2.48, to ~1339 K to 1535 K (1066 °C to 1262 °C) for a mixture with B = 3.96, and to ~1323 K to 1593 K (1050 °C to 1320 °C) at B = 4.94. Increasing basicity also increased the amount of SFCA-I formed, from 18 wt pct for the mixture with B = 2.48 to 25 wt pct for the B = 4.94 mixture. Higher basicity of the starting sinter mixture will, therefore, increase the amount of SFCA-I, considered to be more desirable of the two phases. Basicity did not appear to significantly influence the formation mechanism of SFCA-I. It did, however, affect the formation mechanism of SFCA, with the decomposition of SFCA-I coinciding with the formation of a significant amount of additional SFCA in the B = 2.48 and 3.96 mixtures but only a minor amount in the highest basicity mixture. In situ neutron diffraction enabled characterization of the behavior of magnetite after melting of SFCA produced a magnetite plus melt phase assemblage. © 2014, The Minerals, Metals & Materials Society and ASM International.
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    High temperature diffraction studies of in-situ crystallization of nanostructured TiO2 photocatalysts
    (The Ameican Ceramic Society, 2012-01-01) Low, IM; Pang, WK; Prida, VDL; Vega, V; Kimpton, JA; Ionescu, M
    The in-situ crystallization of anatase and rutile on chemically-treated Ti-foils in the temperature range 20-900 degrees C has been investigated using synchrotron radiation diffraction and x-ray diffraction. The processing methodology has a profound influence on the morphology, crystallite size and growth rate of nanostructured TiO2. The anatase formed was metastable and transformed to rutile at similar to 800 degrees C. Increasing the temperature from 400 to 900 degrees C caused the sharpening of anatase (101) peaks and resulted in a concomitant coarsening in crystallite size. The surface of annealed samples exhibited TiO2 nanorods, nanowires or nanotubes depending on the processing method. Ion-beam analysis has indicated the existence of composition gradation within the annealed TiO2 samples at the near-surface. © 2012, The American Ceramic Society.
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    Improved micro-CT of SiC/SiC ceramic matrix composite
    (Australian Institute of Physics, 2016-02-02) Thornton, J; Zonneveldt, M; Arhatari, BD; Kimpton, JA; Sesso, M; Kim, SY; Hall, C
    Ceramic matrix composites composed of silicon carbide fibres in a silicon carbide matrix (SiC/SiC) are being introduced into gas turbine engines. Their introduction will increase engine thrust by allowing high operating temperatures and also reduce weight. Unlike monolithic ceramics they are effectively tough with elastic energy being consumed in fibre pull-out during crack propagation. However, much work still needs to be done before these materials are fully understood. The authors have been mapping the crack propagation in SiC/SiC using micro-CT and in-situ mechanical loading. Bright synchrotron X-ray sources were used to provide the intensity to map the crack propagation in practical times. One run was performed using the IMBL using 25 keV X-rays, and a second using the powder diffraction beam line at 15 keV. The first run showed fibre pull-out but failed to resolve the effects of the fibre coatings. The use of 15 keV improved the image quality and enabled fibre coatings to be resolved. The poster will compare the two experimental set-ups and the two sets of images and discuss what factors contributed to the improvement in image quality. Ideas for further improvements will also be presented.
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    In situ XRD investigation of the evolution of surface layers on Pb-alloy anodes
    (Cambridge University Press, 2017-08-22) Clancy, M; Styles, MJ; Beetles, CJ; Birbilis, N; Kimpton, JA; Webster, NAS
    The electrochemical behaviour of a number of Pb-based anode alloys, under simulated electrowinning conditions, in a 1.6 M H2SO4 electrolyte at 45 °C was studied. Namely, the evolution of PbO2 and PbSO4 surface layers was investigated by quantitative in situ synchrotron X-ray diffraction (S-XRD) and subsequent Rietveld-based quantitative phase analysis (QPA). In the context of seeking new anode alloys, this research shows that the industry standard Pb-0.08Ca-1.52Sn (wt%) anode, when exposed to a galvanostatic current and intermittent power interruptions, exhibited poor electrochemical performance relative to select custom Pb-based binary alloys; Pb–0.73Mg, Pb–5.05Ag, Pb–0.07Rh, and Pb–1.4Zn (wt%). The in situ S-XRD measurements and subsequent QPA indicated that this was linked to a lower proportion of β-PbO2, relative to PbSO4, on the Pb-0.08Ca-1.52Sn alloy at all stages of the electrochemical cycling. The best performing alloy, in terms of minimisation of overpotential during normal electrowinning operation and minimising the deleterious effects of repeated power interruptions – both of which are significant factors in energy consumption – was determined to be Pb–0.07Rh. © Cambridge University Press 2022
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    An investigation of goethite-seeded Al(OH)(3) precipitation using in situ x-ray diffraction and rietveld-based quantitative phase analysis
    (Wiley-Blackwell, 2010-06) Webster, NAS; Madsen, IC; Loan, MJ; Knott, RB; Naim, F; Wallwork, KS; Kimpton, JA
    An in situ X-ray diffraction investigation of goethite-seeded Al(OH)3 precipitation from synthetic Bayer liquor at 343 K has been performed. The presence of iron oxides and oxyhydroxides in the Bayer process has implications for alumina reversion, which causes significant process losses through unwanted gibbsite precipitation, and is also relevant for the nucleation and growth of scale on mild steel process equipment. The gibbsite, bayerite and nordstrandite polymorphs of Al(OH)3 precipitated from the liquor; gibbsite appeared to precipitate first, with subsequent formation of bayerite and nordstrandite. A Rietveld-based approach to quantitative phase analysis was implemented for the determination of absolute phase abundances as a function of time, from which kinetic information for the formation of the Al(OH)3 phases was determined. © 2010, Wiley-Blackwell. The definitive version is available at www3.interscience.wiley.com
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    An investigation of the mechanisms of goethite, hematite and magnetite-seeded Al(OH)(3) precipitation from synthetic Bayer liquor
    (Elsevier, 2011-09-01) Webster, NAS; Loan, MJ; Madsen, IC; Knott, RB; Kimpton, JA
    The precipitation of Al(OH)3 from synthetic Bayer liquor at 70 degrees C seeded with goethite, hematite and magnetite particles was investigated in order to gain insight into the nucleation and growth mechanisms in the presence of these materials. A combination of characterisation techniques was employed including conductivity analysis, particle size analysis, electron microscopy and in situ synchrotron X-ray diffraction. The magnetite seed was less active for promoting Al(OH)(3) precipitation than the goethite and hematite, based on a comparison of the induction time before the onset of measurable precipitation. For each seed material, the early stages of precipitation were characterised by relatively slow deposition of gibbsite on the seed particles. Precipitation then proceeded via a two-stage mechanism, where gibbsite and small amounts of bayerite and nordstrandite precipitated concurrently. The outcomes of this investigation have implications for the nucleation and growth of scale on mild steel process equipment, and are also relevant for alumina reversion which causes significant process losses through uncontrolled precipitation. (C) 2011 Elsevier B.V.
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    Ion-transport phenomena and anomalous transformations in strontium uranium oxides.
    (International Union of Crystallography, 2017-12-01) Murphy, GL; Zhang, Z; Avdeev, M; Wang, CH; Beridze, G; Kowalski, PM; Gu, QF; Kimpton, JA; Johannessen, B; Kennedy, BJ
    Structural-chemical elucidation of low dimensional ternary uranium oxide systems is considered an essential aspect of thenuclear fuel cycle since understanding of their physicochemical properties may guide the storage and disposal of spentnuclear fuel [1]. The study of these systems allows for further exploration of the peculiar, exotic and poorly knownproperties of materials containing, or which can access, 5f electrons. SrUO₄ exemplifies this, a potential waste form resultingfrom reaction between spent UO₂+x fuel and the fission daughter Sr-90. We have found, through a combination of in situsynchrotron X-ray powder diffraction and X-ray absorption spectroscopy, that during its first order rhombohedral-orthorhombic transition under oxidising conditions, the rhombohedral form of SrUO₄, α, undergoes a spontaneousreduction of the uranium valence state through oxygen vacancy formation [2]. The process is synergetic, as the triality ofoxygen vacancy formation, subsequent ion diffusion and uranium reduction, seemingly reduces the activation energy barrierfor the transformation to the thermodynamically favoured stoichiometric orthorhombic form, β-SrUO₄. However formation ofthe orthorhombic form is only possible if a source of oxygen is present, without this, the oxygen deficient α-SrUO₄-xremains rhombohedral as shown by in situ neutron powder diffraction measurements. These experimental observations arefurther supported by ab initio DFT+U calculations using the self consistently calculated Hubbard U parameter values andbond valence sums calculations [2-3]. These methods indicate the affinity for α-SrUO₄-x to retain oxygen vacancies asopposed to β-SrUO₄, a consequence of the crystal lattice’s ability to stabilise the coordination environment of the Sr²⁺ cationvia the flexibility of uranium to undergo reduction through vacancy formation. CaUO4, isostructural to α-SrUO₄ , but unlike α-SrUO₄ does not have a stable orthorhombic polymorph as shown by both insitu synchrotron X-ray powder diffraction measurements and ab initio calculations. Introducing Sr ions into the CaUO₄ latticein the form of a solid solution, α-Sr₁-xCaxUO₄ (0 < x < 0.4), provides a means to atomically engineer the lattice to promoteoxygen vacancy formation, and presumably diffusion, at high temperatures. When CaUO₄ or α-SrUO₄ is treated underhighly reducing conditions, both materials undergo unusual reconstructive phase transformations at high temperatures to amonoclinic structure. These phase transformations are reversible, and cooling the sample yields the correspondingrhombohedral structure again. It is remarkable that the ordered monoclinic structure is favoured at high temperatures andthe disordered rhombohedral structure at low temperatures. This investigation in SrUO₄ highlights the rich and remarkablestructural chemistry and crystallography that may be found within poorly understood actinide systems whilst demonstratingthe successful marriage of experimental and theoretical approaches towards elucidating their chemical and physicalphenomena. © International Union of Crystallography
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    Nonstoichiometry in strontium uranium oxide: understanding the rhombohedral–orthorhombic transition in SrUO4
    (American Chemical Society, 2016-08-29) Murphy, GL; Kennedy, BJ; Kimpton, JA; Gu, QF; Johannessen, B; Beridze, G; Kowalski, PM; Bosbach, D; Avdeev, M; Zhang, Z
    In situ neutron and synchrotron X-ray diffraction studies demonstrate that SrUO4 acts as an oxygen transfer agent, forming oxygen vacancies under both oxidizing and reducing conditions. Two polymorphs of SrUO4 are stable at room temperature, and the transformation between these is observed to be associated with thermally regulated diffusion of oxygen ions, with partial reduction of the U6+ playing a role in both the formation of oxygen deficient α-SrUO4−δ and its subsequent transformation to stoichiometric β-SrUO4. This is supported by ab initio calculations using density functional theory calculations. The oxygen vacancies play a critical role in the first order transition that SrUO4 undergoes near 830 °C. The changes in the oxidation states and U geometry associated with the structural phase transition have been characterized using X-ray absorption spectroscopy, synchrotron X-ray diffraction, and neutron diffraction. © 2016 American Chemical Society
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    Observations of temperature stability of γ-zirconium hydride by high-resolution neutron powder diffraction
    (Elsevier, 2016-03-15) Wang, Z; Steuwer, A; Liu, N; Maimaitiyili, T; Avdeev, M; Blomqvist, J; Bjerkén, C; Curfs, C; Kimpton, JA; Daniels, JE
    The phase evolution in a zirconium–50 deuterium (Zr–50D, at.%) alloy system during thermal cycling has been investigated using in situ high-resolution neutron powder diffraction. The results showed that the peritectoid reaction α-Zr + δ-ZrD → γ-ZrD previously suggested to occur at high temperatures does not take place in the system. Slow cooling, from high temperatures (≥520 K) to room temperature at a rate of 5 K min−1, promoted the γ-hydride formation rather than fast cooling as reported earlier. In contrast to the observation that the δ-hydride present in the system remained at temperatures up to 740 K, the produced γ phase transformed to δ-hydride in the temperature range of 370 K–559 K, with the transformation completing at approximately 559 K. It is confirmed that the formation of the γ-hydride was reproducible with slow cooling, and a diffusion-controlled sluggish δ-to γ-hydride transformation is suggested to be responsible for the favorable development of γ-hydride during slow cooling. © 2015 Elsevier B.V.