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Browsing by Author "Gregg, DJ"

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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.
Ceramic conversion and densification of zirconium phosphonate sorbent materials
(Elsevier, 2018-04-01) Veliscek-Carolan, J; Thorogood, GJ; Gregg, DJ; Tansu, M; Hanley, TL
The simple conversion of zirconium phosphonate sorbent materials, with known affinity for lanthanide elements, to durable ceramic waste forms via thermal treatment has been demonstrated. The use of zirconium phosphonate enables both removal of targeted elements from spent nuclear fuel and immobilisation into leach resistant solid products to be achieved using a single material. Thermal conversion was performed on the zirconium phosphonate both before and after loading with europium, which acted as a surrogate for the chemically similar minor actinides. Without europium loaded, the zirconium phosphonate sorbent formed predominantly KZr2(PO4)3 upon heating, independent of the processing conditions used. A maximum relative density of 87% was achieved with cold isostatic pressing (200 MPa) and sintering at 1200 °C for 12 h. When the zirconium phosphonate sorbent was loaded with europium, the phase composition formed upon thermal treatment was more complex. Specifically, mixtures of ZrP2O7, Eu0.33Zr2(PO4)3, EuPO4 and Zr2O(PO4)2 were formed, with phase compositions depending on the temperatures and pressures used. The simplest phase composition for the europium loaded material was achieved via uniaxial pressing (120 MPa) and sintering at 1300 °C for 1 h, although the ceramic pellet produced under these conditions had a relative density of only 53%. The loaded europium deported primarily to a EuPO4 phase, which is known to be highly stable and leach resistant. As such, these zirconium phosphonate materials have potential utility for treatment of nuclear wastes. © 2019 Elsevier B.V.
Crystal chemistry and structures of uranium-doped gadolinium zirconates
(Elsevier, 2013-07-01) Gregg, DJ; Zhang, YJ; Zhang, ZM; Karatchevtseva, I; Blackford, MG; Triani, G; Lumpkin, GR
A series of uranium-containing gadolinium zirconate samples have been fabricated at 1450 °C in oxidizing, inert and reducing atmospheres. X-ray diffraction, Raman spectroscopy and transmission electron microscopy have been utilized to confirm adoption of pyrochlore or defect fluorite structures. X-ray diffraction allowed determination of the bulk averaged structure while Raman spectroscopy and transmission electron microscopy were used to determine ordering at the microdomain scale. Diffuse reflectance, X-ray absorption near edge structure and X-ray photoelectron spectroscopies indicated a predominantly U6+ oxidation state for all the air-sintered samples, even when Ca2+ or A-site vacancies were incorporated to charge balance for U4+, a mixed U5+/U6+ oxidation state was found for samples sintered in argon, while a mixed U4+/U5+ oxidation state occurred for sintering under N2–3.5%H2. This demonstrates a degree of uranium oxidation state control through sintering conditions, and the potential of using gadolinium zirconates as host materials for uranium in nuclear waste applications.© 2013, Elsevier B.V.
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.
Formation of (Cr,Al)UO4 from doped UO2 and its influence on partition of soluble fission products
(Elsevier, 2013-11-01) Cooper, MWD; Gregg, DJ; Zhang, YJ; Thorogood, GJ; Lumpkin, GR; Grimes, RW; Middleburgh, SC
CrUO4 and (Cr, Al)UO4 have been fabricated by a sol–gel method, studied using diffraction techniques and modelled using empirical pair potentials. Cr2O3 was predicted to preferentially form CrUO4 over entering solution into hyper-stoichiometric UO2+x by atomic scale simulation. Further, it was predicted that the formation of CrUO4 can proceed by removing excess oxygen from the UO2 lattice. Attempts to synthesise AlUO4 failed, instead forming U3O8 and Al2O3. X-ray diffraction confirmed the structure of CrUO4 and identifies the existence of a (Cr, Al)UO4 phase for the first time (with a maximum Al to Cr mole ratio of 1:3). Simulation was subsequently used to predict the partition energies for the removal of fission products or fuel additives from hyper-stoichiometric UO2+x and their incorporation into the secondary phase. The partition energies are consistent only with smaller cations (e.g. Zr4+, Mo4+ and Fe3+) residing in CrUO4, while all divalent cations are predicted to remain in UO2+x. Additions of Al had little effect on partition behaviour. The reduction of UO2+x due to the formation of CrUO4 has important implications for the solution limits of other fission products as many species are less soluble in UO2 than UO2+x. © 2013, Elsevier B.V.
Gd2Zr2O7 and Nd2Zr2O7 pyrochlore prepared by aqueous chemical synthesis
(Elsevier, 2013-12-01) Kong, L; Karatchevtseva, I; Gregg, DJ; Blackford, MG; Holmes, R; Triani, G
Pyrochlore structured Gd2Zr2O7 and Nd2Zr2O7 are produced via complex precipitation processing. A suite of characterization techniques, including FTIR, Raman, X-ray and electron diffraction, TEM, SEM as well as nitrogen sorption are employed to investigate the structural and grain size evolution of the synthesized and calcined powder. Results show that Gd2Zr2O7 with the pyrochlore structure are produced after calcination at 1400 °C for 12 h while Nd2Zr2O7 has already formed the pyrochlore structure at 1200 °C. This method allows the formation of dense materials at relatively low temperature, with bulk densities over 92% of the theoretical values achieved after sintering at 1400 °C for 50 h. This unique aqueous synthetic method provides a simple pathway to produce pyrochlore lanthanide zirconate without using either organic solvent and/or mechanical milling procedures, making the synthesis protocol an attractive potential scale-up production of highly refractory ceramics. © 2013, Elsevier Ltd.
He and Au ion radiation damage in sodalite, Na4Al3Si3O12Cl
(Elsevier, 2014-10) Vance, ER; Gregg, DJ; Davis, J; Ionescu, M
Sodalite, a candidate ceramic for the immobilisation of pyroprocessing nuclear waste, showed no observable lattice dilatation in grazing incidence X-ray diffraction when irradiated with up to 1017 5 MeV He ions/cm2. However micro-Raman scattering showed considerable spectral broadening characteristic of radiation damage near the end of the ∼22 μm He range. Partial amorphism plus nepheline formation was observed in grazing incidence X-ray diffraction when sodalite was irradiated by 1016 12 MeV Au ions/cm2. Nepheline appeared less susceptible to 12 MeV Au ion damage than sodalite, with ∼25% less amorphous fraction at 1016 ions/cm2. © 2014, Elsevier B.V.
Hot isostatic pressing of ceramics, glass and glass-ceramics for immobilisation of intermediate-and high-level nuclear waste
(Australian Institute of Physics, 2018-01-31) Vance, ER; Gregg, DJ; Chavara, DT
Different classes of nuclear wastes are briefly described, together with an idea of the required qualities of the processed waste for geological disposal. The main Synroc project at ANSTO these days is immobilisation of the upcoming ~5000L/yr intermediate-level waste from the production of the 99Mo radiopharmaceutical and this has been demonstrated inactively by hot isostatic pressing (HIP) a glass at full scale, together with showing its resilience to compositional variations of 10% for all main components, minor impurities and HIP temperature and pressure. Other work deals with HIP immobilisation of zirconolite-based glass-ceramics for surplus PuO2 immobilisation, glass-ceramics and ceramics for U-rich legacy ANSTO 99Mo intermediate-level and low-level waste, immobilisation of pyroprocessing fluoride-salt waste, spent power plant fuel, refractory glasses and CuI.
Hot isostatically pressed (HIPed) fluorite glass‐ceramic wasteforms for fluoride molten salt wastes
(John Wiley & Sons, Inc., 2020-06-07) Gregg, DJ; Vance, ER; Dayal, P; Farzana, R; Aly, Z; Holmes, R; Triani, G
Molten pyroprocessing salts can be used to dissolve used nuclear fuel from a reactor allowing recovery of the actinides. Previously, ANSTO have demonstrated hot isostatically pressed (HIPed) sodalite glass‐ceramic wasteforms for eutectic (Li,K)Cl salts containing fission products, but this system cannot be used for the analogous molten alkali fluoride salts (eg, FLiNaK), which have utility in the application of the next generation of nuclear reactors. In this work, a novel glass‐ceramic composite wasteform has been prepared by HIPing, as a candidate for the immobilization of fission product‐bearing FLiNaK salts. The wasteform has been tailored to immobilize the high fluoride content of the waste within fluorite, whereas the waste alkali elements are incorporated in a durable sodium aluminoborosilicate glass, with total waste loadings of ~17‐21 wt% achieved. It was also demonstrated that the speciation of Mo‐ and Sb‐simulated fission products was altered by adding Ti metal due to a controlled redox environment. The resulting candidate wasteform has been studied by X‐ray diffraction and scanning electron microscopy, including the HIP canister‐wasteform interaction zone, and its performance assessed via leaching studies using the PCT and ASTM C1220 leaching protocols. Dr Vance very much enjoyed the challenge of wasteform design for problematic nuclear wastes, for which fission product‐bearing FLiNaK salts are a clear example. His ability to hone in on a wasteform solution with viable waste loadings that meet performance requirements was testament to his nearly 40 years experience in nuclear waste immobilization. The samples discussed in this work represent the last wasteform materials that he prepared. © 1999-2020 John Wiley & Sons, Inc.
Immobilization of iodine via copper iodide
(Elsevier, 2018-07) Vance, ER; Grant, C; Karatchevtseva, I; Aly, Z; Stopic, A; Harrison, JJ; Thorogood, GJ; Wong, HKY; Gregg, DJ
CuI is a candidate wasteform for the immobilization of the fission product 129I. CuI can be made simply by the addition of CuCl to an I− bearing solution such that exchange of Cl− with I− takes place. The CuI material can then be consolidated into a wasteform by sintering at approximately 550 °C in argon or by hot isostatically pressing at 550 °C with 100 MPa of pressure. A waste loading of greater than 60 wt.% is achievable with good water leach resistance, in keeping with the low solubility product of CuI. However, like the well known wasteform candidate AgI, CuI decomposes in water containing metallic Fe. To compensate this deficiency, the sintered CuI wasteform can be further protected by surrounding it by Sn powder and HIPing at the low temperature of 200 °C. © 2018 Elsevier B.V
Incorporation of Ba in Al and Fe pollucite
(Elsevier B.V., 2016-09-01) Vance, ER; Gregg, DJ; Griffiths, GJ; Gaugliardo, PR; Grant, C
Ba, the transmutation product of radioactive Cs, can be incorporated at levels of up to ∼0.07 formula units in Cs(1−2x)BaxAlSi2O6 aluminium pollucite formed by sol-gel methods and sintering at 1400 °C, with more Ba forming BaAl2Si2O8 phases. The effect of Ba substitution in pollucite-structured CsFeSi2O6 was also studied and no evidence of Ba substitution in the pollucite structure via cation vacancies or Fe2+ formation was obtained. The Ba entered a Fe-silicate glass structure. Charge compensation was also attempted with a Cs+ + Fe3+ ↔ Ba2+ + Ni2+ scheme but again the Ba formed a glass and NiO was evident. PCT leaching data showed CsFeSi2O6 to be very leach resistant. © 2016 Elsevier B.V.
The incorporation of neptunium and plutonium in thorutite (ThTi2O6)
(Elsevier, 2013-12-25) Zhang, YJ; Gregg, DJ; Lumpkin, GR; Begg, BD; Jovanovic, M
The incorporation of neptunium (Np) and plutonium (Pu) into the brannerite structured lattice was studied using thorutite (ThTi2O6) as host lattice and sintering in air. The uncompensated Np and Pu doped samples and the low Y-charge compensated Np and Pu doped samples showed main phases as designed together with trace amounts of rutile. Those samples with larger amounts of Y produced yttrium pyrochlores as an additional minor phase. XRD analyses reveal anisotropic changes of the cell parameters; the a-parameter contracts while b- and c-parameters expand with mean cationic radius. This is in reasonable agreement with previous experimental data on ThTi2O6 and Ce0.975Ti2O5.95. Attempts to form Np or Pu valences >4+ by adding Y as a charge compensator were unsuccessful, suggesting that tetravalent Np and Pu ions are favoured in air-fired thorutite. © 2013, Elsevier B.V.
The incorporation of plutonium in lanthanum zirconate pyrochlore
(Elsevier, 2013-11-01) Gregg, DJ; Zhang, YJ; Middleburgh, SC; Conradson, SD; Triani, G; Lumpkin, GR; Vance, ER
The incorporation of plutonium (Pu) within lanthanum zirconate pyrochlore was investigated using air, argon, and N2–3.5%H2 sintering atmospheres together with Ca2+ and Sr2+ incorporation for charge compensation. The samples have been characterised in the first instance by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectroscopy (DRS). The results show Pu can be exchanged for La3+ on the A-site with and without charge compensation and for Zr4+ on the B-site. DRS measurements were made over the wavenumber range of 4000–19,000 cm−1 and the Pu in all air- and argon-sintered samples was found to be present as Pu4+ while that in samples sintered in N2–3.5%H2 was present as Pu3+. The Pu valence was confirmed for three of the samples using X-ray near-edge absorption spectroscopy (XANES). Pu valences >4+ were not observed in any of the samples. © 2013, Elsevier B.V.
Incorporation of uranium in pyrochlore oxides and pressure-induced phase transitions
(Elsevier - ScienceDirect, 2014-11-01) Zhang, FX; Lang, M; Tracy, C; Ewing, RC; Gregg, DJ; Lumpkin, GR
Uranium-doped gadolinium zirconates with pyrochlore structure were studied at ambient and high-pressure conditions up to 40 GPa. The bonding environment of uranium in the structure was determined by x-ray photoelectron and Raman spectroscopies and x-ray diffraction. The uranium valence for samples prepared in air is mainly U6+, but U4+ is present in pyrochlores fabricated in an argon atmosphere. Rietveld refinement of the XRD pattern suggests that uranium ions in pyrochlores are on the 16d site in 6-fold coordination with oxygen. At pressures greater than 22 GPa, the pyrochlore structure transformed to a cotunnite-type phase. The cotunnite high-pressure phase transformed to a defect fluorite structure on the release of pressure. © 2014 Elsevier Inc.
Ion beam irradiation effects in strontium zirconium phosphate with NZP-structure type
(Elsevier Science BV, 2014-03-01) Gregg, DJ; Karatchevtseva, I; Thorogood, GJ; Davis, J; Bell, BDC; Jackson, M; Dayal, P; Ionescu, M; Triani, G; Short, KT; Lumpkin, GR; Vance, ER
Ceramics with the sodium zirconium phosphate or NZP type structure have potential as nuclear waste form and inert matrix materials. For both applications the material will be subjected to self-radiation damage from alpha-decay of the incorporated actinides. In this study, ion-beam irradiation using Au- and He-ions has been used to simulate the consequences of a-decay and the effects of irradiation on the structural and macroscopic properties (density and hardness) have been investigated. Irradiation by Au-ions resulted in a significant volume contraction of similar to 7%, a reduction in hardness of similar to 30% and a loss in long-range order at fluences above 10(14) Au-ions/cm(2). In contrast, little effect on the material properties was noted for samples irradiated with He-ions up to a fluence of 10(17) ions/cm(2). Thermal annealing was investigated for the highest fluence Au-ion irradiated sample and significant decomposition was observed. © 2014, Elsevier Ltd.
Ion beam irradiation of ABO4 compounds with the fergusonite, monazite, scheelite, and zircon structures
(https://doi.org/10.1111/jace.17288, 2020-06-04) de los Reyes, M; Aughterson, RD; Gregg, DJ; Middleburgh, SC; Zaluzec, NJ; Huai, P; Ren, CL; Lumpkin, GR
The effects of irradiation on CaWO4, SrWO4, BaWO4, YVO4, LaVO4, YNbO4, and LaNbO4 were investigated on thin crystals using 1.0 MeV Kr ions at 50‐1000 K. All of the ABO4 compounds can be amorphized with calculated damage cross sections (σa = 1/Fc0) in the range of ~0.30‐1.09 × 10‐14 cm2 ion−1 at zero Kelvin. The analysis of fluence‐temperature data returned critical temperatures for amorphization (Tc) of 311 ± 1, 358 ± 90, 325 ± 19, 415 ± 17, 541 ± 6, 636 ± 26, and 1012 ± 1 K, respectively, for the compounds listed above. Compared with previous in situ irradiation of ABO4 orthophosphate samples using 0.8 MeV Kr ions, the Tc values of LaVO4 and YVO4 are higher than those of LaPO4 and YPO4 by 82 K and 124 K, respectively. The Tc values of the three scheelite structures, CaWO4, SrWO4, and BaWO4, indicate that they are the most radiation tolerant compounds under these conditions. The A‐B cation anti‐site energies, EfAB, determined by DFT range from 2.48 to 10.58 eV and are highly correlated with the A‐B cation ionic radius ratio, rA/rB, but are not correlated with Tc across the different structure types, suggesting that the formation and migration energies of Frenkel defects play a more important role in damage recovery in these compounds. We also discuss the role of cation and anion charge/iconicity as determined by DFT. ABO4 compounds with the zircon structure and B = P or V have a distinct advantage over those with B = Si as the damaged regions do not appear to be significantly affected by polymerization of (PO4)3− or (VO4)3− groups which might stabilize the amorphous fraction and ultimately lead to phase separation as observed in zircon (ZrSiO4). © 1999-2020 John Wiley & Sons, Inc.
Leaching behaviour of and Cs disposition in a UMo powellite glass–ceramic
(Elsevier, 2014-05) Vance, ER; Davis, J; Olufson, KP; Gregg, DJ; Blackford, MG; Griffiths, GJ; Farnan, J; Sullivan, J; Sprouster, D; Campbell, C; Hughes, J
A UMo powellite glass–ceramic designed by French workers to immobilise Mo-rich intermediate-level waste was found to be quite leach resistant in water at 90 °C with the dissolution of Cs, Mo, Na, B and Ca not exceeding 2 g/L in normalised PCT tests. 133Cs solid state nuclear magnetic resonance and scanning electron microscopy (SEM) showed the Cs to inhabit the glass phase. The microstructures were not greatly affected by cooling rates between 1 and 5 °C/min or by introducing 10 times as much Cs and Sr. Protracted leach tests at 90 °C showed surface alteration as evidenced by SEM and particularly transmission electron microscopy; the main alteration phase was a Zn aluminosilicate but several other alteration phases were evident. Voidage in the alteration layers was indicated from enhanced lifetimes in po sitron annihilation lifetime spectroscopy. © 2014, Elsevier B.V.
A novel chemical route to prepare La2Zr2O7 pyrochlore
(John Wiley and Sons, 2012-11-09) Kong, L; Karatchevtseva, I; Gregg, DJ; Blackford, MG; Holmes, R; Triani, G
Lanthanum zirconate has been prepared via a new chemical synthesis method by combining sol–gel processing and complex precipitation. The synthesis was carried out in aqueous solution under ambient conditions. The synthesized powder possessed the pyrochlore superstructure upon calcination above 1200°C. A suite of characterization techniques, including FTIR, Raman, X-ray and electron diffraction, TEM, SEM, and nitrogen sorption were employed to investigate the microstructural evolution and bulk properties. Dense ceramics (>90% relative density) were obtained after sintering at 1400°C, without need for additional processing (i.e., hot or cold isostatic pressing) or any milling steps. A mechanism has been proposed that elucidates molecular assembly of this chemical synthesis method. © 2012, The American Ceramic Society.
Novel chemical synthesis and characterization of CeTi2O6 brannerite
(ACS Publications, 2014-06-13) Kong, L; Gregg, DJ; Karatchevtseva, I; Zhang, ZM; Blackford, MG; Middleburgh, SC; Lumpkin, GR; Triani, G
Cerium titanate CeTi2O6 was prepared by a new soft chemistry route in aqueous solution. A suite of characterization techniques, including X-ray diffraction, thermal analysis, vibrational spectroscopy, and scanning and transmission electron spectroscopy, were employed to investigate the brannerite structure formation and its bulk properties. The synthesized powder formed the brannerite crystal structure upon calcination at temperatures as low as 800 °C. Samples sintered at 1350 °C possess a high level of crystallinity. X-ray absorption near-edge structure results indicate the presence of six-coordinated Ce4+ in the brannerite samples. © 2014, American Chemical Society.
Novel synthesis and thermal property analysis of MgO–Nd2Zr2O7 composite
(Elsevier, 2016-11-15) Kong, L; Zhang, J; Maeda, Y; Blackford, MG; Li, S; Triani, G; Gregg, DJ
MgO-Nd2Zr2O7composites with ratios of 50–70 vol% MgO were produced via a one-pot combustion synthesis. A suite of characterization techniques, including X-ray diffraction, scanning and transmission electron microscopy were employed to investigate the structural properties while dilatometry, simultaneous thermal analysis and laser flash analysis were used to characterize the thermal properties of the composites. Dense pellets were produced after sintering at 1400 °C with grain sizes between 200 and 500 nm for both phases. The thermal properties of the composites are similar to those produced using standard methods. The composite with 70 vol% MgO was found to have the highest thermal conductivity below 1000 °C, while above this temperature the thermal conductivity was found to be similar and independent of MgO content. This novel synthesis route produces materials which show significant improvements in homogeneity with smaller particle sizes when compared to current standard synthesis techniques without significantly reducing thermal conductivity. © 2016 Elsevier Ltd.

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