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Sample records for pyrochlore

  1. Aspects of reduction clorination of pyrochlore concentrates

    International Nuclear Information System (INIS)

    Gameiro, D.H.; Brocchi, E.A.

    1985-01-01

    Reduction chlorination experiments were carried out with two different Brazilian pyrochlore concentrates in order to evaluate the effects of some variables on the extent of niobium pentoxide gaseification as well as to compare the behavior of concentrate under the same chlorination conditions. The pyrochlore concentrates from Araxa (MG) and Catalao (GO), Brazil, were submitted to X ray diffraction and X ray fluorescence analysis for determining their chemical compositions. Kinetic curves were obtained with the main variables being temperature and percentage of reducing agent. Analysis of the condensed material in terms of Nb 2 O 5 indicated that chlorination can be used to produce niobium pentoxide. (Author) [pt

  2. Weyl magnons in breathing pyrochlore antiferromagnets

    Science.gov (United States)

    Li, Fei-Ye; Li, Yao-Dong; Kim, Yong Baek; Balents, Leon; Yu, Yue; Chen, Gang

    2016-01-01

    Frustrated quantum magnets not only provide exotic ground states and unusual magnetic structures, but also support unconventional excitations in many cases. Using a physically relevant spin model for a breathing pyrochlore lattice, we discuss the presence of topological linear band crossings of magnons in antiferromagnets. These are the analogues of Weyl fermions in electronic systems, which we dub Weyl magnons. The bulk Weyl magnon implies the presence of chiral magnon surface states forming arcs at finite energy. We argue that such antiferromagnets present a unique example, in which Weyl points can be manipulated in situ in the laboratory by applied fields. We discuss their appearance specifically in the breathing pyrochlore lattice, and give some general discussion of conditions to find Weyl magnons, and how they may be probed experimentally. Our work may inspire a re-examination of the magnetic excitations in many magnetically ordered systems. PMID:27650053

  3. Strain engineered pyrochlore at high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye; Fuentes, Antonio F.; Park, Changyong; Ewing, Rodney C.; Mao, Wendy L.

    2017-05-22

    Strain engineering is a promising method for next-generation materials processing techniques. Here, we use mechanical milling and annealing followed by compression in diamond anvil cell to tailor the intrinsic and extrinsic strain in pyrochlore, Dy2Ti2O7 and Dy2Zr2O7. Raman spectroscopy, X-ray pair distribution function analysis, and X-ray diffraction were used to characterize atomic order over short-, medium-, and long-range spatial scales, respectively, under ambient conditions. Raman spectroscopy and X-ray diffraction were further employed to interrogate the material in situ at high pressure. High-pressure behavior is found to depend on the species and concentration of defects in the sample at ambient conditions. Overall, we show that defects can be engineered to lower the phase transformation onset pressure by ~50% in the ordered pyrochlore Dy2Zr2O7, and lower the phase transformation completion pressure by ~20% in the disordered pyrochlore Dy2Zr2O7. These improvements are achieved without significantly sacrificing mechanical integrity, as characterized by bulk modulus.

  4. Tunable Magnon Weyl Points in Ferromagnetic Pyrochlores.

    Science.gov (United States)

    Mook, Alexander; Henk, Jürgen; Mertig, Ingrid

    2016-10-07

    The dispersion relations of magnons in ferromagnetic pyrochlores with Dzyaloshinskii-Moriya interaction are shown to possess Weyl points, i. e., pairs of topologically nontrivial crossings of two magnon branches with opposite topological charge. As a consequence of their topological nature, their projections onto a surface are connected by magnon arcs, thereby resembling closely Fermi arcs of electronic Weyl semimetals. On top of this, the positions of the Weyl points in reciprocal space can be tuned widely by an external magnetic field: rotated within the surface plane, the Weyl points and magnon arcs are rotated as well; tilting the magnetic field out of plane shifts the Weyl points toward the center Γ[over ¯] of the surface Brillouin zone. The theory is valid for the class of ferromagnetic pyrochlores, i. e., three-dimensional extensions of topological magnon insulators on kagome lattices. In this Letter, we focus on the (111) surface, identify candidates of established ferromagnetic pyrochlores which apply to the considered spin model, and suggest experiments for the detection of the topological features.

  5. Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

    Science.gov (United States)

    Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

    2012-03-13

    A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

  6. Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

    Energy Technology Data Exchange (ETDEWEB)

    Finkeldei, Sarah Charlotte

    2015-07-01

    Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO{sub 2} based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO{sub 2} based pyrochlores. ZrO{sub 2} - Nd{sub 2}O{sub 3} pellets

  7. Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

    International Nuclear Information System (INIS)

    Finkeldei, Sarah Charlotte

    2015-01-01

    Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO 2 based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO 2 based pyrochlores. ZrO 2 - Nd 2 O 3 pellets with pyrochlore and defect

  8. Analysis of coordination polyhedra symmetry in pyrochlore and zirconolite structures

    International Nuclear Information System (INIS)

    Troole, A.Y.; Stefanovsky, S.V.

    1999-01-01

    Zirconolite and pyrochlore are considered as promising host phases for high level waste (HLW). However, correct information on substitution mechanisms, forms of dopants incorporation in their structures and distortions in coordination polyhedra is presently unavailable. To clarify these points the authors use the electron paramagnetic resonance (EPR). Pyrochlore and three of zirconolite polytypes: zirconolite-2M, zirconolite-3T, and zirconolite-3O are considered. Pyrochlore is the parent structure for zirconolite since any zirconolite variety is produced by means of distortion of the initial pyrochlore structure. Space groups of pyrochlore and basic polymorphous zirconolite varieties found from XRD and TEM data, as well as interatomic distances and angles, were taken from reference data. This allows the determination of the most probable sites for impurities, substitution mechanisms, and local symmetry of coordination polyhedra (initial). Ions chosen for EPR were Gd(III) as an analog of trivalent rare earth and actinide elements which are also occurred in HLW and Fe(III) as a typical corrosion product which occurs in all HLW. For Gd(III) a strong ligand field approximation is suggested, theoretical computation using perturbation theory in this approximation has been carried out. All the non-diagonal members plus magnetic field were chosen as perturbation and formulate for transition frequencies, estimations of fine structure and g-factors parameters in the given approximation have been obtained

  9. Frustration under pressure: Exotic magnetism in new pyrochlore oxides

    Directory of Open Access Journals (Sweden)

    C. R. Wiebe

    2015-04-01

    Full Text Available Pyrochlore structures, of chemical formula A2B2O7 (A and B are typically trivalent and tetravalent ions, respectively, have been the focus of much activity in the condensed matter community due to the ease of substitution of rare earth and transition metal ions upon the two interpenetrating corner-shared tetrahedral lattices. Over the last few decades, superconductivity, spin liquid states, spin ice states, glassy states in the absence of chemical disorder, and metal-insulator transitions have all been discovered in these materials. Geometric frustration plays a role in the relevant physics of all of these phenomena. In the search for new pyrochlore materials, it is the RA/RB cation radius ratio which determines the stability of the lattice over the defect fluorite structure in the lower limit. Under ambient pressure, the pyrochlores are stable for 1.36 ≤ RA/RB ≤ 1.71. However, using high pressure synthesis techniques (1-10 GPa of pressure, metastable pyrochlores exist up to RA/RB = 2.30. Many of these compounds are stable on a timescale of years after synthesis, and provide a means to greatly enhance exchange, and thus test theories of quantum magnetism and search for new phenomena. Within this article, we review new pyrochlore compounds synthesized via high pressure techniques and show how the ground states are extremely sensitive to chemical pressure.

  10. Processing glass-pyrochlore composites for nuclear waste encapsulation

    International Nuclear Information System (INIS)

    Pace, S.; Cannillo, V.; Wu, J.; Boccaccini, D.N.; Seglem, S.; Boccaccini, A.R.

    2005-01-01

    Glass matrix composites have been developed as alternative materials to immobilize nuclear solid waste, in particular actinides. These composites are made of soda borosilicate glass matrix, into which particles of lanthanum zirconate pyrochlore are encapsulated in concentrations of 30 vol.%. The fabrication process involves powder mixing followed by hot-pressing. At the relatively low processing temperature used (620 deg. C), the pyrochlore crystalline structure of the zirconate, which is relevant for containment of radioactive nuclei, remains unaltered. The microstructure of the composites exhibits a homogeneous distribution of isolated pyrochlore particles in the glass matrix and strong bonding at the matrix-particle interfaces. Hot-pressing was found to lead to high densification (95% th.d.) of the composite. The materials are characterized by relatively high elastic modulus, flexural strength, hardness and fracture toughness. A numerical approach using a microstructure-based finite element solver was used in order to investigate the mechanical properties of the composites

  11. Incorporation of uranium in pyrochlore oxides and pressure-induced phase transitions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, F.X., E-mail: zhangfx@umich.edu [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Lang, M.; Tracy, C.; Ewing, R.C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Gregg, D.J.; Lumpkin, G.R. [Institute of Materials Engineering, ANSTO, Locked Bag 2001, Kirrawee DC 2232, NSW (Australia)

    2014-11-15

    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 U{sup 6+}, but U{sup 4+} 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. - Graphical abstract: In U-bearing pyrochlore, U ions mainly occupy the 16d site and replace the smaller Zr{sup 4+}, part of the oxygen will occupy the 8b site, which is empty to most pyrochlores. At pressure of 22 GPa, the pyrochlore lattice is not stable and transforms to a cotunnite-type structure. The high-pressure structure is not stable and transform to a fluorite or back to the pyrochlore structure when pressure is released. - Highlights: • We found that U ions mainly occupy the smaller cation site in U-bearing pyrochlore. • Pyrochlore structure is not stable at pressure of more than 20 GPa. • The quenched sample has a pyrochlore or a disordered fluorite structure.

  12. Thermal annealing of natural, radiation-damaged pyrochlore

    Energy Technology Data Exchange (ETDEWEB)

    Zietlow, Peter; Beirau, Tobias; Mihailova, Boriana; Groat, Lee A.; Chudy, Thomas; Shelyug, Anna; Navrotsky, Alexandra; Ewing, Rodney C.; Schlüter, Jochen; Škoda, Radek; Bismayer, Ulrich

    2017-01-01

    Abstract

    Radiation damage in minerals is caused by the α-decay of incorporated radionuclides, such as U and Th and their decay products. The effect of thermal annealing (400–1000 K) on radiation-damaged pyrochlores has been investigated by Raman scattering, X-ray powder diffraction (XRD), and combined differential scanning calorimetry/thermogravimetry (DSC/TG). The analysis of three natural radiation-damaged pyrochlore samples from Miass/Russia [6.4 wt% Th, 23.1·10

  13. Thermal annealing of natural, radiation-damaged pyrochlore

    Energy Technology Data Exchange (ETDEWEB)

    Zietlow, Peter; Mihailova, Boriana [Hamburg Univ. (Germany). Dept. of Earth Sciences; Beirau, Tobias [Hamburg Univ. (Germany). Dept. of Earth Sciences; Stanford Univ., CA (United States). Dept. of Geological Sciences; and others

    2017-03-01

    Radiation damage in minerals is caused by the α-decay of incorporated radionuclides, such as U and Th and their decay products. The effect of thermal annealing (400-1000 K) on radiation-damaged pyrochlores has been investigated by Raman scattering, X-ray powder diffraction (XRD), and combined differential scanning calorimetry/thermogravimetry (DSC/TG). The analysis of three natural radiation-damaged pyrochlore samples from Miass/Russia [6.4 wt% Th, 23.1.10{sup 18} α-decay events per gram (dpg)], Panda Hill/Tanzania (1.6 wt% Th, 1.6.10{sup 18} dpg), and Blue River/Canada (10.5 wt% U, 115.4.10{sup 18} dpg), are compared with a crystalline reference pyrochlore from Schelingen (Germany). The type of structural recovery depends on the initial degree of radiation damage (Panda Hill 28%, Blue River 85% and Miass 100% according to XRD), as the recrystallization temperature increases with increasing degree of amorphization. Raman spectra indicate reordering on the local scale during annealing-induced recrystallization. As Raman modes around 800 cm{sup -1} are sensitive to radiation damage (M. T. Vandenborre, E. Husson, Comparison of the force field in various pyrochlore families. I. The A{sub 2}B{sub 2}O{sub 7} oxides. J. Solid State Chem. 1983, 50, 362, S. Moll, G. Sattonnay, L. Thome, J. Jagielski, C. Decorse, P. Simon, I. Monnet, W. J. Weber, Irradiation damage in Gd{sub 2}Ti{sub 2}O{sub 7} single crystals: Ballistic versus ionization processes. Phys. Rev. 2011, 84, 64115.), the degree of local order was deduced from the ratio of the integrated intensities of the sum of the Raman bands between 605 and 680 cm{sup -1} divided by the sum of the integrated intensities of the bands between 810 and 860 cm{sup -1}. The most radiation damaged pyrochlore (Miass) shows an abrupt recovery of both, its short- (Raman) and long-range order (X-ray) between 800 and 850 K, while the weakly damaged pyrochlore (Panda Hill) begins to recover at considerably lower temperatures (near 500 K

  14. Evolution of pyrochlore composition in a carbonatite complex of the Eastern European platform

    International Nuclear Information System (INIS)

    Nechelyastnov, G.N.; Pozharitskaya, L.K.

    1986-01-01

    X-ray microanalysis is used to study 29 pyrochlore group mineral samples of the East European platform carbonatite complex. Pyrochlore sequential evolution: frm high in tantalum and uranium, passing uranium poor in tantalum to low in tantalum and uranium and also an increased content of iron, manganese, magnesium and lead, is shown. Calcium, niobium, tantalum non-homogeneous distribution in pyrochlore grains is detected. Peculiarities of pyrochlore group mineral composition reflect the effect of specific geologic-structural position of the East European platform carbonatites high depth of formation and intensive development of deformations) on general evolution for pyrochlore of carbonatite complexes and related to it pyrochlore specific nature, in particular, high uranium and low niobium contents

  15. A spin-frustrated cobalt(II) carbonate pyrochlore network.

    Science.gov (United States)

    Zheng, Yanzhen; Ellern, Arkady; Kögerler, Paul

    2011-11-01

    The crystal structure of the cobalt(II) carbonate-based compound cobalt(II) dicarbonate trisodium chloride, Co(CO(3))(2)Na(3)Cl, grown from a water-ethanol mixture, exhibits a three-dimensional network of corner-sharing {Co(4)(μ(3)-CO(3))(4)} tetrahedral building blocks, in which the Co(II) centres define a pyrochlore lattice and reside in a slightly distorted octahedral Co(O-CO(2))(6) environment. The space outside the hexagonal framework defined by these interlinked groups is occupied by Na(+) and Cl(-) ions. Antiferromagnetic coupling between adjacent Co(II) centres, mediated by carbonate bridges, results in geometric spin frustration which is typical for pyrochlore networks. The Co and Cl atoms reside on the special position 3, one Na atom on position 2 and a carbonate C atom on position 3.

  16. Exchange interactions in two-state systems: rare earth pyrochlores

    Science.gov (United States)

    Curnoe, S. H.

    2018-06-01

    The general form of the nearest neighbour exchange interaction for rare earth pyrochlores is derived based on symmetry. Generally, the rare earth angular momentum degeneracy is lifted by the crystal electric field (CEF) into singlets and doublets. When the CEF ground state is a doublet that is well-separated from the first excited state the CEF ground state doublet can be treated as a pseudo-spin of some kind. The general form of the nearest neighbour exchange interaction for pseudo-spins on the pyrochlore lattice is derived for three different types of pseudo-spins. The methodology presented in this paper can be applied to other two-state spin systems with a high space group symmetry.

  17. Soft modes in the easy plane pyrochlore antiferromagnet

    International Nuclear Information System (INIS)

    Champion, J D M; Holdsworth, P C W

    2004-01-01

    Thermal fluctuations lift the high ground state degeneracy of the classical nearest neighbour pyrochlore antiferromagnet, with easy plane anisotropy, giving a first-order phase transition to a long range ordered state. We show, from spin wave analysis and numerical simulation, that even below this transition a continuous manifold of states, of dimension N 2/3 , exist (N is the number of degrees of freedom). As the temperature goes to zero a further 'order by disorder' selection is made from this manifold. The pyrochlore antiferromagnet Er 2 Ti 2 O 7 is believed to have an easy plane anisotropy and is reported to have the same magnetic structure. This is perhaps surprising, given that the dipole interaction lifts the degeneracy of the classical model in favour of a different structure. We interpret our results in the light of these facts

  18. Theoretical and experimental investigations of frustrated pyrochlore magnets

    International Nuclear Information System (INIS)

    Champion, John Dickon Mathison

    2001-01-01

    This thesis describes the investigation of frustrated magnetic systems based on the pyrochlore lattice of corner-sharing tetrahedra. Monte Carlo simulations and analytical calculations have been performed on a pyrochlore ferromagnet with local (111) easy-axis anisotropy related to the problem of 'spin ice'. The anisotropy-temperature-magnetic field phase diagram was determined. It contained a tricritical point as well as features related to some real ferroelectrics. A pyrochlore antiferromagnet with local (111) easy-plane anisotropy was studied by Monte Carlo simulation. A general expression for its degenerate ground states was discovered and normal- modes out of the ground states were calculated. Both systems are frustrated yet have a long-range ordered state at low temperature. The degeneracy lifting observed is discussed as well as the reasons for its presence. The rare-earth titanate series Ln 2 Ti 2 O 7 (Ln = rare earth), crystallizes in the Fd3-barm space group, with the magnetic ions situated on the 16c sites which constitute the pyrochlore lattice. Crystal-field effects are known to play a significant role in the frustration observed in these compounds. Powder neutron diffraction was performed on gadolinium and erbium titanate. Both systems are frustrated antiferromagnets yet show long-range magnetic order at ∼ 1 K and ∼ 1.2 K respectively. The magnetic structures of both these compounds have been determined by powder neutron diffraction techniques and related to other theoretical results as well as the theoretical results of the author. Further neutron scattering experiments on the 'spin ice' materials Ho 2 Ti 2 O 7 and Dy 2 Ti 2 O 7 are also described. (author)

  19. Yttrium bismuth titanate pyrochlore mixed oxides for photocatalytic hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Merka, Oliver

    2012-10-18

    In this work, the sol-gel synthesis of new non-stoichiometric pyrochlore titanates and their application in photocatalytic hydrogen production is reported. Visible light response is achieved by introducing bismuth on the A site or by doping the B site by transition metal cations featuring partially filled d orbitals. This work clearly focusses on atomic scale structural changes induced by the systematical introduction of non-stoichiometry in pyrochlore mixed oxides and the resulting influence on the activity in photocatalytic hydrogen production. The materials were characterized in detail regarding their optical properties and their atomic structure. The pyrochlore structure tolerates tremendous stoichiometry variations. The non-stoichiometry in A{sub 2}O{sub 3} rich compositions is compensated by distortions in the cationic sub-lattice for the smaller Y{sup 3+} cation and by evolution of a secondary phase for the larger Bi{sup 3+} cation on the A site. For TiO{sub 2} rich compositions, the non-stoichiometry leads to a special vacancy formation in the A and optionally O' sites. It is shown that pyrochlore mixed oxides in the yttrium bismuth titanate system represent very active and promising materials for photocatalytic hydrogen production, if precisely and carefully tuned. Whereas Y{sub 2}Ti{sub 2}O{sub 7} yields stable hydrogen production rates over time, the bismuth richer compounds of YBiTi{sub 2}O{sub 7} and Bi{sub 2}Ti{sub 2}O{sub 7} are found to be not stable under irradiation. This drawback is overcome by applying a special co-catalyst system consisting of a precious metal core and a Cr{sub 2}O{sub 3} shell on the photocatalysts.

  20. Hydrothermal synthesis of electrode materials pyrochlore tungsten trioxide film

    Science.gov (United States)

    Guo, Jingdong; Li, Yingjeng James; Stanley Whittingham, M.

    Hydrothermal synthesis methods have been successfully used to prepare new transition-metal oxides for cathodes in electrochemical devices such as lithium batteries and electrochromic windows. The tungsten oxides were the first studied, but the method has been extended to the oxides of molybdenum, vanadium and manganese. Sodium tungsten oxide films with the pyrochlore structure have been prepared on gold/alumina and indium-doped tin oxide substrates. These films reversibly and rapidly intercalate lithium and hydrogen ions.

  1. Synthesis and characterization of bismuth zinc niobate pyrochlore nanopowders

    Directory of Open Access Journals (Sweden)

    Sonia Maria Zanetti

    2007-09-01

    Full Text Available Bismuth zinc niobate pyrochlores Bi1.5ZnNb1.5O7 (alpha-BZN, and Bi2(Zn1/3Nb2/32O 7 (beta-BZN have been synthesized by chemical method based on the polymeric precursors. The pyrochlore phase was investigated by differential scanning calorimetry, infrared spectroscopy, and X ray diffraction. Powder and sintered pellets morphology was examined by scanning electron microscopy. The study of alpha-BZN phase formation reveals that, at 500 °C, the pyrochlore phase was already present while a single-phased nanopowder was obtained after calcination at 700 °C. The crystallization mechanism of the beta-BZN is quite different, occurring through the crystallization of alpha-BZN and BiNbO4 intermediary phases. Both compositions yielded soft agglomerated powders. alpha-BZN pellets, sintered at 800 °C for 2 hours, presented a relative density of 97.3% while those of beta-BZN, sintered at 900 °C for 2 hours, reached only 91.8%. Dielectric constant and dielectric loss, measured at 1 MHz, were 150 and 4 x/10-4 for a-BZN, and 97 and 8 x 10-4 for beta-BZN.

  2. Properties and recrystallization of radiation damaged pyrochlore and titanite

    Energy Technology Data Exchange (ETDEWEB)

    Zietlow, Peter

    2016-11-02

    Radiation damage in minerals is caused by the alpha-decay of incorporated radionuclides, such as U and Th and their decay products. The effect of thermal annealing (400-1400 K) on radiation-damaged pyrochlores has been investigated by Raman scattering, X-ray powder diffraction (XRD), and combined differential scanning calorimetry/thermogravimetry (DSC/TG) (Zietlow et al., in print). The analysis of three natural radiation-damaged pyrochlore samples from Miass/Russia (6.4 wt% Th, 23.1.10{sup 18} a-decay events per gram (dpg)), Zlatoust/Russia (6.3 wt% Th, 23.1.10{sup 18} dpg), Panda Hill/Tanzania (1.6 wt% Th, 1.6.10{sup 18} dpg), and Blue River/Canada (10.5 wt% U, 115.4.10{sup 18} dpg), are compared with a crystalline reference pyrochlore from Schelingen (Germany). The type of structural recovery depends on the initial degree of radiation damage (Panda Hill 28 %, Blue River 85 %, Zlatoust and Miass 100 % according to XRD), as the recrystallization temperature increases with increasing degree of amorphization. Raman spectra indicate reordering on the local scale during annealing-induced recrystallization. As Raman modes around 800 cm{sup -1} are sensitive to radiation damage (Vandenborre and Husson 1983, Moll et al. 2011), the degree of local order was deduced from the ratio of the integrated intensities of the sum of the Raman bands between 605 and 680 cm{sup -1} devided by the sum of the integrated intensities of the bands between 810 and 860 cm{sup -1}. The most radiation damaged pyrochlores (Miass and Zlatoust) show an abrupt recovery of both, its short- (Raman) and long-range order (X-ray) between 800 and 850 K. The volume decrease upon recrystallization in Zlatoust pyrochlore was large enough to crack the sample repeatedly. In contrast, the weakly damaged pyrochlore (Panda Hill) begins to recover at considerably lower temperatures (near 500 K), extending over a temperature range of ca. 300 K, up to 800 K (Raman). The pyrochlore from Blue River shows in its

  3. Structural response of titanate pyrochlores to swift heavy ion irradiation

    International Nuclear Information System (INIS)

    Shamblin, Jacob; Tracy, Cameron L.; Ewing, Rodney C.; Zhang, Fuxiang; Li, Weixing; Trautmann, Christina; Lang, Maik

    2016-01-01

    The structure, size, and morphology of ion tracks resulting from irradiation of five different pyrochlore compositions (A 2 Ti 2 O 7 , A = Yb, Er, Y, Gd, Sm) with 2.2 GeV 197 Au ions were investigated by means of synchrotron X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Radiation-induced amorphization occurred in all five materials analyzed following an exponential rate as a function of ion fluence. XRD patterns showed a general trend of increasing susceptibility of amorphization with increasing ratio of A- to B-site cation ionic radii (r A /r B ) with the exception of Y 2 Ti 2 O 7 and Sm 2 Ti 2 O 7 . This indicates that the track size does not necessarily increase with r A /r B , in contrast with results from previous swift heavy ion studies on Gd 2 Zr 2-x Ti x O 7 pyrochlore materials. For Y 2 Ti 2 O 7 , this effect is attributed to the significantly lower electron density of this material relative to the lanthanide-bearing pyrochlores, thus lowering the electronic energy loss (dE/dx) of the high-energy ions in this composition. An energy loss normalization procedure was performed which reveals an initial increase of amorphous track size with r A /r B that saturates above a cation radius ratio larger than Gd 2 Ti 2 O 7 . This is in agreement with previous low-energy ion irradiation experiments and first principles calculations of the disordering energy of titanate pyrochlores indicating that the same trends in disordering energy apply to radiation damage induced in both the nuclear and electronic energy loss regimes. HRTEM images indicate that single ion tracks in Yb 2 Ti 2 O 7 and Er 2 Ti 2 O 7 , which have small A-site cations and low r A /r B , exhibit a core-shell structure with a small amorphous core surrounded by a larger disordered shell. In contrast, single tracks in Gd 2 Ti 2 O 7 and Sm 2 Ti 2 O 7 , have a larger amorphous core with minimal disordered shells.

  4. The fluorite-pyrochlore transformation of Ho2-yNdyZr2O7

    International Nuclear Information System (INIS)

    Clements, Richard; Hester, James R.; Kennedy, Brendan J.; Ling, Chris D.; Stampfl, Anton P.J.

    2011-01-01

    Twelve members of the Ho 2-y Nd y Zr 2 O 7 series, prepared using conventional solid state methods, have been characterised by neutron powder diffraction. Ho 2 Zr 2 O 7 has a defect fluorite structure whereas Nd 2 Zr 2 O 7 is found to adopt the ordered pyrochlore structure with the composition induced fluorite-pyrochlore transformation occurring near y=1. Rietveld analysis on the neutron data for all the compositions reveals an increase in lattice parameter as a function of y across the entire series, with a small discontinuity associated with the transformation. The neutron profile results suggest that domains of pyrochlore-type initially begin to form before crystallising into a separate phase, and therefore that anion and cation ordering processes are distinct. There is a strong correlation between the extent of disorder in the anion sublattice and the x-parameter of 48f oxygen. These results point the way to a better understanding of the stability observed in pyrochlore structures. - Graphical abstract: Neutron diffraction profiles for Nd 2-y Ho y Zr 2 O 7 type oxides reveal details of the transformation from the ordered pyrochlore structure (y=0) to the disordered fluorite structure (y=2). Highlights: → Structures of twelve members of the Ho 2-y Nd y Zr 2 O 7 series studied using neutron powder diffraction. → Domains of pyrochlore-type materials form at low doping levels. → Higher doping stabilises the pyrochlore. → Anion and cation ordering processes are distinct.

  5. Large-scale calculation of ferromagnetic spin systems on the pyrochlore lattice

    Energy Technology Data Exchange (ETDEWEB)

    Soldatov, Konstantin, E-mail: soldatov_ks@students.dvfu.ru [School of Natural Sciences, Far Eastern Federal University, Vladivostok (Russian Federation); Nefedev, Konstantin, E-mail: nefedev.kv@dvfu.ru [School of Natural Sciences, Far Eastern Federal University, Vladivostok (Russian Federation); Institute of Applied Mathematics, Far Eastern Branch, Russian Academy of Science, Vladivostok (Russian Federation); Komura, Yukihiro [CIJ-solutions, Chuo-ku, Tokyo 103-0023 (Japan); Okabe, Yutaka, E-mail: okabe@phys.se.tmu.ac.jp [Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397 (Japan)

    2017-02-19

    We perform the high-performance computation of the ferromagnetic Ising model on the pyrochlore lattice. We determine the critical temperature accurately based on the finite-size scaling of the Binder ratio. Comparing with the data on the simple cubic lattice, we argue the universal finite-size scaling. We also calculate the classical XY model and the classical Heisenberg model on the pyrochlore lattice. - Highlights: • Calculations of the ferromagnetic models on the pyrochlore lattice were performed. • Precise critical temperatures were determined using Binder ratio finite-size scaling. • The universal finite-size scaling was argued.

  6. Experimental hydrothermal alteration of crystalline and radiation-damaged pyrochlore

    International Nuclear Information System (INIS)

    Geisler, T.; Seydoux-Guillaume, A.-M.; Poeml, P.; Golla-Schindler, U.; Berndt, J.; Wirth, R.; Pollok, K.; Janssen, A.; Putnis, A.

    2005-01-01

    We have performed hydrothermal experiments with a crystalline microlite and a heavily self-irradiation-damaged (i.e., X-ray amorphous) betafite in a solution containing 1 mol/l HCl and 1 mol/l CaCl 2 at 175 deg. C for 14 days. The well-crystalline microlite grains were partly (∼5-10 μm rim) replaced by a Ca and Na-poorer, defect pyrochlore phase with a larger unit-cell and a sharp chemical gradient at the interface (on a nm scale) to the unreacted core. The amorphous betafite grains (up to ∼2 mm in diameter), on the other hand, were completely transformed into an intergrowth of different crystalline phases (polycrystalline anatase and rutile, a yet unidentified Nb-Ta oxide, and a Y-REE phase), showing complex non-equilibrium structures. Our experimental observations bear a remarkable resemblance to those made on natural samples. They indicate that the processes of the fluid-pyrochlore interaction are influenced by self-irradiation structural damage and that thermodynamic equilibrium models can hardly be applied to adequately describe such systems

  7. Adiabatic cooling processes in frustrated magnetic systems with pyrochlore structure

    Science.gov (United States)

    Jurčišinová, E.; Jurčišin, M.

    2017-11-01

    We investigate in detail the process of adiabatic cooling in the framework of the exactly solvable antiferromagnetic spin-1/2 Ising model in the presence of the external magnetic field on an approximate lattice with pyrochlore structure. The behavior of the entropy of the model is studied and exact values of the residual entropies of all ground states are found. The temperature variation of the system under adiabatic (de)magnetization is investigated and the central role of the macroscopically degenerated ground states in cooling processes is explicitly demonstrated. It is shown that the model parameter space of the studied geometrically frustrated system is divided into five disjunct regions with qualitatively different processes of the adiabatic cooling. The effectiveness of the adiabatic (de)magnetization cooling in the studied model is compared to the corresponding processes in paramagnetic salts. It is shown that the processes of the adiabatic cooling in the antiferromagnetic frustrated systems are much more effective especially in nonzero external magnetic fields. It means that the frustrated magnetic materials with pyrochlore structure can be considered as very promising refrigerants mainly in the situations with nonzero final values of the magnetic field.

  8. New Type of Quantum Criticality in the Pyrochlore Iridates

    Directory of Open Access Journals (Sweden)

    Lucile Savary

    2014-11-01

    Full Text Available Magnetic fluctuations and electrons couple in intriguing ways in the vicinity of zero-temperature phase transitions—quantum critical points—in conducting materials. Quantum criticality is implicated in non-Fermi liquid behavior of diverse materials and in the formation of unconventional superconductors. Here, we uncover an entirely new type of quantum critical point describing the onset of antiferromagnetism in a nodal semimetal engendered by the combination of strong spin-orbit coupling and electron correlations, and which is predicted to occur in the iridium oxide pyrochlores. We formulate and solve a field theory for this quantum critical point by renormalization group techniques and show that electrons and antiferromagnetic fluctuations are strongly coupled and that both these excitations are modified in an essential way. This quantum critical point has many novel features, including strong emergent spatial anisotropy, a vital role for Coulomb interactions, and highly unconventional critical exponents. Our theory motivates and informs experiments on pyrochlore iridates and constitutes a singular realistic example of a nontrivial quantum critical point with gapless fermions in three dimensions.

  9. Atomic disorder in Gd{sub 2}Zr{sub 2}O{sub 7} pyrochlore

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, F. X. [State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, Hebei 066004 (China); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, Michigan 48109 (United States); Lang, M. [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States); Ewing, R. C. [Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305 (United States)

    2015-05-11

    Gd{sub 2}Zr{sub 2}O{sub 7} pyrochlore with different degrees of cation disorder were synthesized by isothermal annealing at various temperatures (1100–1550 °C), and the related changes in the structure were investigated by ambient and high pressure x-ray diffraction (XRD) measurements. Unit cell parameters increase almost linearly with increasing treatment temperature. The degree of cation order in pyrochlore also increases with the increase of temperature, but saturates at ∼60%. The compressibility of the pyrochlore structures decreases when the degree of cation order increases. High pressure XRD measurements also indicate that the phase stability of Gd{sub 2}Zr{sub 2}O{sub 7} is not very sensitive to the degree of atomic disorder in the pyrochlore structure.

  10. Study on the chemical treatment processes of the uranium pyrochlore of Araxa

    International Nuclear Information System (INIS)

    Batista, H.F.; Fernandes, M.D.

    Several processes are presented for the chemical treatment, in laboratory scale, of the uranium pyrochlore concentrates found in Araxa (Minas Gerais, Brazil), aiming to the extraction of uranium, thorium and rare earths, besides the recovery of niobium pentoxide [pt

  11. Steam Reforming of CH4 Using Ni- Substituted Pyrochlore Catalysts

    Science.gov (United States)

    Haynes, Daniel J.

    The steam reforming of methane (SMR) continues to remain an important industrial reaction for large-scale production of H2 as well as synthesis gas mixtures which can be used for the production of useful chemicals (e.g. methanol). Although SMR is a rather mature technology, traditional nickel based catalysts used industrially are subjected to severe temperatures and reaction conditions, which lead to irreversible activity loss through sintering, support collapse, and carbon formation. Pyrochlore-based mixed oxide have been identified as refractory materials that can be modified through the substitution of catalytic metals and other promoting species into the structure to mitigate these issues causing deactivation. For this study, a lanthanum zirconate pyrochlore catalyst was substituted with Ni to determine whether the oxide structure could effectively stabilize the activity of the catalytic metal during the SMR. The effect of different variables including calcination temperature, a comparison of a substituted versus supported Ni pyrochlore catalyst, Ni weight loading, and Sr promotion have been evaluated to determine the location of the Ni in the structure, and their effect on catalytic behavior. It was revealed that the effect of calcination temperature on a 6wt% Ni substituted pyrochlore produced by the Pechini method demonstrated very little Ni was soluble in the pyrochlore lattice. It was further revealed that by XRD, TEM, and atom probe tomography that, despite the metal loading, Ni exsolves from the structure upon crystallization of the pyrochlore at 700°C, and forms NiO at the surface and grain boundaries. An additional separate La2ZrNiO6 perovskite phase also began to form at higher temperatures (>800°C). Increasing calcination temperature was found to lead to slight sintering of the NiO at the surface, which made the NiO more reducible. Meanwhile decreasing the Ni weight loading was found to produce a lower reduction temperature due to the presence of

  12. The XPS study of pyrochlore matrixes for the radioactive waste disposal

    Directory of Open Access Journals (Sweden)

    Teterin Anton Yu.

    2010-01-01

    Full Text Available Two pyrochlore ceramic samples were studied in this work. The X-ray diffraction and the scanning electron microscopy showed that the ceramics with the calculated composition CaThSn2O7 was formed by the dominating pyrochlore phase with the traces of thorianite and hematite, while the CaThZr2O7 ceramics - by the dominating pyrochlore phase with the minor admixtures of thorianite and perovskite. The real compositions of pyrochlore phases determined by the scaning electron microscopy are Ca0.88Th0.92Sn2O6.72 and Ca0.84Th0.80Zr2O6.44. On the basis of the X-ray photoelectron spectral parameters of the outer and core electrons in the binding energy range of 0-1250 eV it was found that tin, zirconium and thorium in pyrochlore are at least 93%-94% tetravalent. Sn-O and Zr-O interatomic distances in BO6-octahedrons in the pyrochlore were found to be 0.210 nm and 0.220 nm, respectively, and these octahedrons are possible to be tetragonaly distorted.

  13. Thermodynamic stability of actinide pyrochlore minerals in deep geologic repository environments

    International Nuclear Information System (INIS)

    Wang, YIFENG; Xu, HUIFANG

    2000-01-01

    Crystalline phases of pyrochlore (e.g., CaPuTi 2 O 7 , CaUTi 2 O 7 ) have been proposed as a durable ceramic waste form for disposal of high level radioactive wastes including surplus weapons-usable plutonium. In this paper, the authors use a linear free energy relationship to predict the Gibbs free energies of formation of pyrochlore phases (CaMTi 2 O 7 ). The Pu-pyrochlore phase is predicted to be stable with respect to PuO 2 , CaTiO 3 , and TiO 2 at room temperatures. Pu-pyrochlore is expected to be stable in a geologic repository where silica and carbonate components are absent or limited. The authors suggest that a repository in a salt formation be an ideal environment for disposal of high level, pyrochlore-based ceramic wastes. In such environment, adding CaO as a backfill will make pyrochlore minerals thermodynamically stable and therefore effectively prevent actinide release from these mineral phases

  14. Weyl magnons in pyrochlore antiferromagnets with an all-in-all-out order

    Science.gov (United States)

    Jian, Shao-Kai; Nie, Wenxing

    2018-03-01

    We investigate topological magnon band crossings of pyrochlore antiferromagnets with all-in-all-out (AIAO) magnetic order. By general symmetry analysis and spin-wave theory, we show that pyrochlore materials with AIAO orders can host Weyl magnons under external magnetic fields or uniaxial strains. Under a small magnetic field, the magnon bands of the pyrochlore with AIAO background can feature two opposite-charged Weyl points, which is the minimal number of Weyl points realizable in quantum materials, and has not been experimentally observed so far. We further show that breathing pyrochlores with AIAO orders can exhibit Weyl magnons upon uniaxial strains. These findings apply to any pyrochlore material supporting AIAO orders, irrespective of the forms of interactions. Specifically, we show that the Weyl magnons are robust against direct (positive) Dzyaloshinskii-Moriya interactions. Because of the ubiquitous AIAO orders in pyrochlore magnets including R2Ir2O7 , and experimentally achievable external strain and magnetic field, our predictions provide a promising arena to witness the Weyl magnons in quantum magnets.

  15. Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln = Nd, Gd, Er) at high pressure.

    Science.gov (United States)

    Turner, Katlyn M; Tracy, Cameron L; Mao, Wendy L; Ewing, Rodney C

    2017-11-09

    Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln=Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare it to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant property that influences their compression response. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the bond in stannate pyrochlore is more covalent than the bonds in titanates, zirconate, and hafnates. In stannates, the pyrochlore cation and anion sublattices begin to disorder at 0.3 GPa. The extent of sublattice disorder vs. pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to a cotunnite-like structure (Pnma) at ~28 GPa; similar transitions have been observed in titanate, zirconate, and hafnate pyrochlore at varying pressures with cation radius ratio. The extent of the phase transition vs. pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multiscale defect-fluorite + weberite structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlore treated to similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B0, of stannates varies linearly and inversely with cation radius ratio. The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates, and suggest that the size of the Ln3+ cation is a primary determining factor of B0. Additionally, when normalized to rA/rB, the bulk moduli of stannates are comparable to those of zirconates and hafnates, which vary from titanates. Our results suggest that the cation radius ratio strongly influences the bulk moduli of stannates as well as

  16. Ion irradiation of rare-earth- and yttrium-titanate-pyrochlores

    International Nuclear Information System (INIS)

    Wang, S.X.; Wang, L.M.; Ewing, R.C.; Govindan Kutty, K.V.

    2000-01-01

    Pyrochlore, A 1-2 B 2 O 6 (O,OH,F) 0-1 , is an actinide-bearing phase in Synroc, a polyphase ceramic proposed for the immobilization of high level nuclear waste. Structural damage due to alpha-decay events can significantly affect the chemical and physical stability of the nuclear waste form. Pyrochlore can effectively incorporate a variety of actinides into its structure. Four titanate pyrochlores were synthesized with compositions of Gd 2 Ti 2 O 7 , Sm 2 Ti 2 O 7 , Eu 2 Ti 2 O 7 and Y 2 Ti 2 O 2 . These samples were irradiated with 1 MeV Kr + in order to simulate alpha-decay damage and were observed by in situ electron microscopy. Irradiations were conducted from 25 K to 1023 K. At room temperature, Gd-, Sm- and Eu-pyrochlores amorphized at a dose of ∼2x10 14 ions/cm 2 (∼0.5 dpa) and Y-pyrochlore amorphized at 4x10 14 ions/cm 2 (∼0.8 dpa). The amorphization dose became higher at elevated temperatures with different rates of increase for each composition. The critical temperatures for amorphization are ∼1100 K for Gd-, Sm-, Eu-pyrochlore and ∼780 K for Y-pyrochlore. The rare-earth-pyrochlores are more susceptible to amorphization and have higher critical temperatures than Y-pyrochlore. The difference in amorphization dose and critical temperature is attributed to the different cascade sizes caused by the different cation masses of the target. Based on a model of cascade quenching, the larger cascade is related to a lower amorphization dose and higher critical temperature. The irradiated materials were studied by electron diffraction and high-resolution electron microscopy. All the pyrochlores transformed to a fluorite substructure prior to the completion of amorphization of the observed regions. This transformation was caused by the disordering between cations and between oxygen and oxygen vacancies. The concurrence of cation disordering with amorphization suggests the partial recrystallization of the displacement cascades. Isolated cascade damage

  17. Many-Body Theory of Pyrochlore Iridates and Related Materials

    Science.gov (United States)

    Wang, Runzhi

    In this thesis we focus on two problems. First we propose a numerical method for generating optimized Wannier functions with desired properties. Second we perform the state of the art density functional plus dynamical mean-field calculations in pyrochlore iridates, to investigate the physics induced by the cooperation of spin-orbit coupling and electron correlation. We begin with the introduction for maximally localized Wannier functions and other related extensions. Then we describe the current research in the field of spin-orbit coupling and its interplay with correlation effects, followed by a brief introduction of the `hot' materials of iridates. Before the end of the introduction, we discuss the numerical methods employed in our work, including the density functional theory; dynamical mean-field theory and its combination with the exact diagonalization impurity solver. Then we propose our approach for constructing an optimized set of Wannier functions, which is a generalization of the functionality of the classic maximal localization method put forward by Marzari and Vanderbilt. Our work is motivated by the requirement of the effective description of the local subspace of the Hamiltonian by the beyond density functional theory methods. In extensions of density functional theory such as dynamical mean-field theory, one may want highly accurate description of particular local orbitals, including correct centers and symmetries; while the basis for the remaining degrees of freedom is unimportant. Therefore, we develop the selectively localized Wannier function approach which allows for a greater localization in the selected subset of Wannier functions and at the same time allows us to fix the centers and ensure the point symmetries. Applications in real materials are presented to demonstrate the power of our approach. Next we move to the investigation of pyrochlore iridates, focussing on the metal-insulator transition and material dependence in these compounds. We

  18. Investigation into the magnetic properties of pyrochlore-type rare-earth hafnates

    Energy Technology Data Exchange (ETDEWEB)

    Chun, Jung Hwan; Kremer, Reinhard K.; Lin, Chengtian [MPI for Solid State Research, Stuttgart (Germany)

    2015-07-01

    Cubic rare-earths transition metal pyrochlores with composition R{sub 2}TM{sub 2}O{sub 7} have attracted broad attention because of their unusual magnetic ground state properties related to geometrical frustration of the pyrochlores lattice. So far, the investigation focused mainly on 3d and 4d transition metal systems. The magnetic properties of rare-earths 5d TM pyrochlores are comparatively less well studied. Here we report on the single-crystal growth and the magnetic properties of some rare-earth hafnates (R =Nd, Gd, Dy; TM = Hf) of composition R{sub 2}Hf{sub 2}O{sub 7}. Nd{sub 2}Hf{sub 2}O{sub 7} and Gd{sub 2}Hf{sub 2}O{sub 7} crystallize with the cubic pyrochlores structure whereas diverging reports on the structure of Dy{sub 2}Hf{sub 2}O{sub 7} are available in literature. Crystals of R{sub 2}Hf{sub 2}O{sub 7} have been grown and their structural and magnetic properties have been investigated. Our investigations confirm Nd{sub 2}Hf{sub 2}O{sub 7} and Gd{sub 2}Hf{sub 2}O{sub 7} to crystallize in the cubic pyrochlores structure. Antiferromagnetic ordering below ∝0.5 K has been observed by magnetic susceptibility and heat capacity measurements for both compounds.

  19. Characterization, Microstructure, and Dielectric properties of cubic pyrochlore structural ceramics

    KAUST Repository

    Li, Yangyang

    2013-05-01

    The (BMN) bulk materials were sintered at 1050°C, 1100°C, 1150°C, 1200°C by the conventional ceramic process, and their microstructure and dielectric properties were investigated by Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Transmission electron microscopy (TEM) (including the X-ray energy dispersive spectrometry EDS and high resolution transmission electron microscopy HRTEM) and dielectric impedance analyzer. We systematically investigated the structure, dielectric properties and voltage tunable property of the ceramics prepared at different sintering temperatures. The XRD patterns demonstrated that the synthesized BMN solid solutions had cubic phase pyrochlore-type structure when sintered at 1050°C or higher, and the lattice parameter (a) of the unit cell in BMN solid solution was calculated to be about 10.56Å. The vibrational peaks observed in the Raman spectra of BMN solid solutions also confirmed the cubic phase pyrochlore-type structure of the synthesized BMN. According to the Scanning Electron Microscope (SEM) images, the grain size increased with increasing sintering temperature. Additionally, it was shown that the densities of the BMN ceramic tablets vary with sintering temperature. The calculated theoretical density for the BMN ceramic tablets sintered at different temperatures is about 6.7521 . The density of the respective measured tablets is usually amounting more than 91% and 5 approaching a maximum value of 96.5% for sintering temperature of 1150°C. The microstructure was investigated by using Scanning Transmission Electron Microscope (STEM), X-ray diffraction (XRD). Combined with the results obtained from the STEM and XRD, the impact of sintering temperature on the macroscopic and microscopic structure was discussed. The relative dielectric constant ( ) and dielectric loss ( ) of the BMN solid solutions were measured to be 161-200 and (at room temperature and 100Hz-1MHz), respectively. The BMN solid

  20. Effect of Ion Irradiation in Cadmium Niobate Pyrochlores

    International Nuclear Information System (INIS)

    Jiang, Weilin; Weber, William J.; Thevuthasan, Suntharampillai; Boatner, Lynn A.

    2003-01-01

    Irradiation experiments have been performed for cadmium niobate pyrochlore (CdNb2O) single crystals at both 150 and 300 K using 1.0 MeV Au ions over fluences ranging from 0.01 to 0.10 ions/nm. In-situ 3.0 MeV He Rutherford backscattering spectrometry along the -axial channeling direction (RBS/C) has been applied to study the damage states ranging from small defect concentrations to a fully amorphous state. Results show that the crystal can be readily amorphized under the irradiation conditions. Room-temperature recovery of the defects produced at 150 K has been observed, while the defects produced at 300 K are thermally stable at room temperature. Results also indicate that the RBS/C analysis used in this study induced negligible damage in the near-surface regime. In addition, irradiation at and below room temperature using He and C3 ions leads to surface exfoliation at the corresponding damage peaks

  1. Emergent Topological Phenomena in Thin Films of Pyrochlore Iridates

    Science.gov (United States)

    Yang, Bohm-Jung; Nagaosa, Naoto

    2014-06-01

    Because of the recent development of thin film and artificial superstructure growth techniques, it is possible to control the dimensionality of the system, smoothly between two and three dimensions. In this Letter we unveil the dimensional crossover of emergent topological phenomena in correlated topological materials. In particular, by focusing on the thin film of pyrochlore iridate antiferromagnets grown along the [111] direction, we demonstrate that the thin film can have a giant anomalous Hall conductance, proportional to the thickness of the film, even though there is no Hall effect in 3D bulk material. Moreover, in the case of ultrathin films, a quantized anomalous Hall conductance can be observed, despite the fact that the system is an antiferromagnet. In addition, we uncover the emergence of a new topological phase, the nontrivial topological properties of which are hidden in the bulk insulator and manifest only in thin films. This shows that the thin film of correlated topological materials is a new platform to search for unexplored novel topological phenomena.

  2. Density Functional Theory Study of Leaching Performance of Different Acids on Pyrochlore (100) Surface

    Science.gov (United States)

    Yang, Xiuli; Fang, Qing; Ouyang, Hui

    2018-06-01

    Pyrochlore leaching using hydrofluoric, sulfuric, and hydrochloric acids has been studied via experimental methods for years, but the interactions between niobium atoms on the pyrochlore surface and different acids have not been investigated. In this work, first-principles calculations based on density functional theory were used to elucidate the leaching performance of these three acids from the viewpoint of geometrical and electronic structures. The calculation results indicate that sulfate, chloride, and fluoride anions influence the geometric structure of pyrochlore (100) to different extents, decreasing in the order: sulfate, fluoride, chloride. Orbitals of O1 and O2 atoms of sulfate hybridized with those of surface niobium atom. Fluorine orbitals hybridized with those of surface niobium atoms. However, no obvious overlap exists between any orbitals of chlorine and surface niobium, revealing that chlorine does not interact chemically with surface niobium atoms.

  3. Dielectric properties and microstructural characterization of cubic pyrochlored bismuth magnesium niobates

    KAUST Repository

    Zhang, Yuan

    2013-08-06

    Cubic bismuth pyrochlores in the Bi2O3 Bi 2O3-MgO-Nb2O5 Nb2O 5 system have been investigated as promising dielectric materials due to their high dielectric constant and low dielectric loss. Here, we report on the dielectric properties and microstructures of cubic pyrochlored Bi 1.5 MgNb 1.5 O 7 Bi1.5MgNb1.5O7 (BMN) ceramic samples synthesized via solid-state reactions. The dielectric constant (measured at 1 MHz) was measured to be ∼ 120 ∼120 at room temperature, and the dielectric loss was as low as 0.001. X-ray diffraction patterns demonstrated that the BMN samples had a cubic pyrochlored structure, which was also confirmed by selected area electron diffraction (SAED) patterns. Raman spectrum revealed more than six vibrational models predicted for the ideal pyrochlore structure, indicating additional atomic displacements of the A and O′ O\\' sites from the ideal atomic positions in the BMN samples. Structural modulations of the pyrochlore structure along the [110] and [121] directions were observed in SAED patterns and high-resolution transmission electron microscopy (HR-TEM) images. In addition, HR-TEM images also revealed that the grain boundaries (GBs) in the BMN samples were much clean, and no segregation or impure phase was observed forming at GBs. The high dielectric constants in the BMN samples were ascribed to the long-range ordered pyrochlore structures since the electric dipoles formed at the superstructural direction could be enhanced. The low dielectric loss was attributed to the existence of noncontaminated GBs in the BMN ceramics. © 2013 Springer-Verlag Berlin Heidelberg.

  4. Crystal chemistry of pyrochlore from the Mesozoic Panda Hill carbonatite deposit, western Tanzania

    Science.gov (United States)

    Boniface, Nelson

    2017-02-01

    The Mesozoic Panda Hill carbonatite deposit in western Tanzania hosts pyrochlore, an ore and source of niobium. This study was conducted to establish the contents of radioactive elements (uranium and thorium) in pyrochlore along with the concentration of niobium in the ore. The pyrochlore is mainly hosted in sövite and is structurally controlled by NW-SE (SW dipping) or NE-SW (NW dipping) magmatic flow bands with dip angles of between 60° and 90°. Higher concentrations of pyrochlore are associated with magnetite, apatite and/or phlogopite rich flow bands. Electron microprobe analyses on single crystals of pyrochlore yield very low UO2 concentrations that range between 0 and 0.09 wt% (equivalent to 0 atoms per formula unit: a.p.f.u.) and ThO2 between 0.55 and 1.05 wt% (equivalent to 0.1 a.p.f.u.). The analyses reveal high concentrations of Nb2O5 (ranging between 57.13 and 65.50 wt%, equivalent to a.p.f.u. ranging between 1.33 and 1.43) and therefore the Panda Hill Nb-oxide is classified as pyrochlore sensu stricto. These data point to a non radioactive pyrochlore and a deposit rich in Nb at Panda Hill. The Panda Hill pyrochlore has low concentrations of REEs as displayed by La2O3 that range between 0.10 and 0.49 wt% (equivalent to a.p.f.u. ranging between 0 and 0.01) and Ce2O3 ranging between 0.86 and 1.80 wt% (equivalent to a.p.f.u. ranging between 0.02 and 0.03), Pr2O3 concentrations range between 0 and 0.23 wt% (equivalent to 0 a.p.f.u.), and Y2O3 is 0 wt% (equivalent to 0 a.p.f.u.). The abundance of the REEs in pyroclore at the Panda Hill Carbonatite deposit is of no economic significance.

  5. Static magnetic susceptibility, crystal field and exchange interactions in rare earth titanate pyrochlores.

    Science.gov (United States)

    Malkin, B Z; Lummen, T T A; van Loosdrecht, P H M; Dhalenne, G; Zakirov, A R

    2010-07-14

    The experimental temperature dependence (T = 2-300 K) of single crystal bulk and site susceptibilities of rare earth titanate pyrochlores R(2)Ti(2)O(7) (R = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) is analyzed in the framework of crystal field theory and a mean field approximation. Analytical expressions for the site and bulk susceptibilities of the pyrochlore lattice are derived taking into account long range dipole-dipole interactions and anisotropic exchange interactions between the nearest neighbor rare earth ions. The sets of crystal field parameters and anisotropic exchange coupling constants have been determined and their variations along the lanthanide series are discussed.

  6. Electrical conductivities and chemical stabilities of mixed conducting pyrochlores for SOFC applications

    DEFF Research Database (Denmark)

    Holtappels, P.; Poulsen, F.W.; Mogensen, Mogens Bjerg

    2000-01-01

    Pyrochlores with praseodymium as the A-site cation and zirconium, tin, cerium and manganese cations on the B-site were prepared in air and their electrical conductivities were investigated as a function of oxygen partial pressure and temperature. Pure Pr2Zr2O7+/-delta as well as samples modified...

  7. Investigation of annealed and metamict pyrochlore minerals by x-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Greegor, R.B.; Lytle, F.W.; Ewing, R.C.; Chakoumakos, B.C.; Lumpkin, G.R.

    1984-01-01

    Materials of the pyrochlore structure type exhibit a variety of interesting properties including phases capable of acting as hosts for actinides in radioactive wastes. Studies of curium doped gadolinium titanate phases (Gd 2 Ti 2 O 7 ) have been made which showed that the radiation damage ingrowth followed an exponential relationship. For the study reported here a series of synthetic pyrochlores were produced having the titanate phase with the general formula (RE) 2 Ti 2 O 7 , RE = Er, Y 2 , Gd 2 , Dy, La. Additionally a set of metamict (radiation damaged) pyrochlores was examined in both a natural and post temperature annealed state. Experiments were conducted on these samples using the Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) techniques. In summary, these studies show that in pyrochlore structure types the Ti-O cage undergoes changes due to radiation damage. The individual Ti-O bonds become more disordered which leads to a loss of short and long range order and, ultimately, to expansion of the bulk material. 2 refs., 2 figs

  8. Experimental Insights into Ground-State Selection of Quantum XY Pyrochlores

    Science.gov (United States)

    Hallas, Alannah M.; Gaudet, Jonathan; Gaulin, Bruce D.

    2018-03-01

    Extensive experimental investigations of the magnetic structures and excitations in the XY pyrochlores have been carried out over the past decade. Three families of XY pyrochlores have emerged: Yb2B2O7, Er2B2O7, and, most recently, [Formula: see text]Co2F7. In each case, the magnetic cation (either Yb, Er, or Co) exhibits XY anisotropy within the local pyrochlore coordinates, a consequence of crystal field effects. Materials in these families display rich phase behavior and are candidates for exotic ground states, such as quantum spin ice, and exotic ground-state selection via order-by-disorder mechanisms. In this review, we present an experimental summary of the ground-state properties of the XY pyrochlores, including evidence that they are strongly influenced by phase competition. We empirically demonstrate the signatures for phase competition in a frustrated magnet: multiple heat capacity anomalies, suppressed TN or TC, sample- and pressure-dependent ground states, and unconventional spin dynamics.

  9. Structural properties of the geometrically frustrated pyrochlore Tb2Ti2O7

    International Nuclear Information System (INIS)

    Han, Sang-Wook; Gardner, Jason S.; Booth, Corwin H.

    2004-01-01

    Although materials that exhibit nearest-neighbor-only antiferromagnetic interactions and geometrical frustration theoretically should not magnetically order in the absence of disorder, few such systems have been observed experimentally. One such system appears to be the pyrochlore Tb 2 Ti 2 O 7 . However, previous structural studies indicated that Tb 2 Ti 2 O 7 is an imperfect pyrochlore. To clarify the situation, we performed neutron powder diffraction (NPD) and x-ray absorption fine structure (XAFS) measurements on samples that were prepared identically to those that show no magnetic order. The NPD measurements show that the long-range structure of Tb 2 Ti 2 O 7 is well ordered with no structural transitions between 4.5 and 600 K. In particular, mean-squared displacements (u 2 's) for each site follow a Debye model with no offsets. No evidence for Tb/Ti site interchange was observed within an upper limit of 2%. Likewise, no excess or deficiency in the oxygen stoichiometry was observed, within an upper limit of 2% of the nominal pyrochlore value. Tb L III and Ti K-edge XAFS measurements from 20-300 K similarly indicate a well-ordered local structure. Other aspects of the structure are considered. We conclude that Tb 2 Ti 2 O 7 has, within experimental error, an ideal, disorder-free pyrochlore lattice, thereby allowing the system to remain in a dynamic, frustrated spin state to the lowest observed temperatures

  10. Static magnetic susceptibility, crystal field and exchange interactions in rare earth titanate pyrochlores

    NARCIS (Netherlands)

    Malkin, B. Z.; Lummen, T. T. A.; van Loosdrecht, P. H. M.; Dhalenne, G.; Zakirov, A. R.

    2010-01-01

    The experimental temperature dependence (T = 2-300 K) of single crystal bulk and site susceptibilities of rare earth titanate pyrochlores R2Ti2O7 (R = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) is analyzed in the framework of crystal field theory and a mean field approximation. Analytical expressions for the

  11. Intricate disorder in defect fluorite/pyrochlore: a concord of chemistry and crystallography

    Czech Academy of Sciences Publication Activity Database

    Simeone, D.; Thorogood, G.J.; Huo, D.; Luneville, L.; Baldinozzi, G.; Petříček, Václav; Porcher, F.; Ribis, J.; Mazerolles, L.; Largeau, L.; Berar, J.F.; Surble, S.

    2017-01-01

    Roč. 7, Jun (2017), 1-7, č. článku 3727. ISSN 2045-2322 Institutional support: RVO:68378271 Keywords : disorder * atomic scale * metallic allys * oxides * fluorite/pyrochlore Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 4.259, year: 2016

  12. Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

    Science.gov (United States)

    Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

    2012-05-14

    The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Combined experimental–theoretical study of the optoelectronic properties of non-stoichiometric pyrochlore bismuth titanate

    KAUST Repository

    Noureldine, Dalal; Lardhi, Sheikha F.; Ziani, Ahmed; Harb, Moussab; Cavallo, Luigi; Takanabe, Kazuhiro

    2015-01-01

    A combination of experimental and computational methods was applied to investigate the crystal structure and optoelectronic properties of the non-stoichiometric pyrochlore Bi2−xTi2O7−1.5x. The detailed experimental protocol for both powder and thin

  14. Transmission electron microscopic study of pyrochlore to defect-fluorite transition in rare-earth pyrohafnates

    Energy Technology Data Exchange (ETDEWEB)

    Karthik, Chinnathambi, E-mail: Karthikchinnathambi@boisestate.edu [Department of Materials Science and Engineering, Boise State University, 1910 University drive, Boise, ID 83725 (United States); Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415 (United States); Anderson, Thomas J. [Department of Materials Science and Engineering, Boise State University, 1910 University drive, Boise, ID 83725 (United States); Gout, Delphine [Oak Ridge National Lab, Neutron Scattering Science Division, Oak Ridge, TN (United States); Ubic, Rick [Department of Materials Science and Engineering, Boise State University, 1910 University drive, Boise, ID 83725 (United States); Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415 (United States)

    2012-10-15

    A structural transition in rare earth pyrohafnates, Ln{sub 2}Hf{sub 2}O{sub 7} (Ln=Y, La, Pr, Nd, Tb, Dy, Yb and Lu), has been identified. Neutron diffraction showed that the structure transforms from well-ordered pyrochloric to fully fluoritic through the lanthanide series from La to Lu with a corresponding increase in the position parameter x of the 48f (Fd3{sup Macron }m) oxygen site from 0.330 to 0.375. As evidenced by the selected area electron diffraction, La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} exhibited a well-ordered pyrocholoric structure with the presence of intense superlattice spots, which became weak and diffuse (in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}) before disappearing completely as the series progressed towards the Lu end. High resolution electron microscopic studies showed the breakdown of the pyrochlore ordering in the form of antiphase domains resulting in diffused smoke-like superlattice spots in the case of Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. - Graphical abstract: Transmission electron microscopic studies showed the ordered pyrochlore to defect fluorite transition in rare-earth pyrohafnates to occur via the formation of anti-phase domains to start with. Highlights: Black-Right-Pointing-Pointer Pyrochlore to fluorite structural transition in rare earth pyrohafnates. Black-Right-Pointing-Pointer La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} showed well ordered pyrochlore structure. Black-Right-Pointing-Pointer Short range ordering in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Break down of pyrochlore ordering due to antiphase boundaries. Black-Right-Pointing-Pointer Rest of the series showed fluoritic structure.

  15. Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, Er) at high pressure

    Science.gov (United States)

    Turner, Katlyn M.; Tracy, Cameron L.; Mao, Wendy L.; Ewing, Rodney C.

    2017-12-01

    Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare their response to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant feature that influences their response on compression. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the 〈Sn-O〉 bond in stannate pyrochlore is more covalent than the 〈B-O〉 bonds in titanates, zirconate, and hafnates. In stannates, based on in situ Raman spectroscopy, pyrochlore cation and anion sublattices begin to disorder with the onset of compression, first measured at 0.3 GPa. The extent of sublattice disorder versus pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to an orthorhombic, cotunnite-like structure at ~28 GPa similar transitions have been observed in titanate, zirconate, and hafnate pyrochlores at varying pressures (18-40 GPa) with cation radius ratio. The extent of the phase transition versus pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multi-scale defect-fluorite  +  weberite-type structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlores under similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B 0, of stannates varies linearly and inversely with cation radius ratio from 1 1 1 GPa (Nd2Sn2O7) to 251 GPa (Er2Sn2O7). The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates and suggest that the size of the Ln3+ cation is the primary determining factor of B 0. Additionally, when normalized to r A

  16. The pressure-induced structural response of rare earth hafnate and stannate pyrochlore from 0.1-50 GPa

    Science.gov (United States)

    Turner, K. M.; Rittman, D.; Heymach, R.; Turner, M.; Tracy, C.; Mao, W. L.; Ewing, R. C.

    2017-12-01

    Complex oxides with the pyrochlore (A2B2O7) and defect-fluorite ((A,B)4O7) structure-types undergo structural transformations under high-pressure. These compounds are under consideration for applications including as a proposed waste-form for actinides generated in the nuclear fuel cycle. High-pressure transformations in rare earth hafnates (A2Hf2O7, A=Sm, Eu, Gd, Dy, Y, Yb) and stannates (A2Sn2O7, A=Nd, Gd, Er) were investigated to 50 GPa by in situ Raman spectroscopy and synchrotron x-ray diffraction (XRD). Rare-earth hafnates form the pyrochlore structure for A=La-Tb and the defect-fluorite structure for A=Dy-Lu. Lanthanide stannates form the pyrochlore structure. Raman spectra revealed that at ambient pressure all compositions have pyrochlore-type short-range order. Stannate compositions show a larger degree of pyrochlore-type short-range ordering relative to hafnates. In situ high-pressure synchrotron XRD showed that rare earth hafnates and stannates underwent a pressure-induced phase transition to a cotunnite-like (Pnma) structure that begins between 18-25 GPa in hafnates and between 30-33 GPa in stannates. The phase transition is not complete at 50 GPa, and upon decompression, XRD indicates that all compositions transform to defect-fluorite with an amorphous component. In situ Raman spectroscopy showed that disordering in stannates and hafnates occurs gradually upon compression. Pyrochlore-structured hafnates retain short-range order to a higher pressure (30 GPa vs. <10 GPa) than defect-fluorite-structured hafnates. Hafnates and stannates decompressed from 50 GPa show Raman spectra consistent with weberite-type structures, also reported in irradiated stannates. The second-order Birch-Murnaghan equation of state fit gives a bulk modulus of 250 GPa for hafnate compositions with the pyrochlore structure, and 400 GPa for hafnate compositions with the defect-fluorite structure. Stannates have a lower bulk modulus relative to hafnates (between 80-150 GPa

  17. Stability of the Weyl-semimetal phase on the pyrochlore lattice

    Science.gov (United States)

    Berke, Christoph; Michetti, Paolo; Timm, Carsten

    2018-04-01

    Motivated by the proposal of a Weyl-semimetal phase in pyrochlore iridates, we consider a Hubbard-type model on the pyrochlore lattice. To shed light on the question as to why such a state has not been observed experimentally, its robustness is analyzed. On the one hand, we study the possible phases when the system is doped. Magnetic frustration favors several phases with magnetic and charge order that do not occur at half filling, including additional Weyl-semimetal states close to quarter filling. On the other hand, we search for density waves that break translational symmetry and destroy the Weyl-semimetal phase close to half filling. The uniform Weyl semimetal is found to be stable, which we attribute to the low density of states close to the Fermi energy.

  18. Preparation and characterization of bismuth ruthenate pyrochlore via solid state reaction and sol-gel methods

    Directory of Open Access Journals (Sweden)

    Mayuree Sansernnivet

    2010-01-01

    Full Text Available Bismuth ruthenate pyrochlores, potential cathode materials for intermediate temperature solid oxide fuel cells(ITSOFCs, were prepared via solid-state and sol-gel method. Effects of the preparation routes and conditions on the phase and microstructures of the materials were investigated in this study using XRD and SEM. The study showed that the preparation method and the adding sequence of the starting meterials have a significant effect on the crystal phase and the particle size obtained. Sol-gel synthesis could yield a material with only pyrochlore structure, i.e. Bi2Ru2O7, while the solid state method yielded powder with a small amount of the secondary RuO2 phase. The sol-gel synthesis resulted in materialswith a finer particle size (~0.3-1.0 μm compared to powder synthesized via the solid state reaction method.

  19. Compositional Evolution of Pyrochlore-Group Minerals in Carbonatites of the Belaya Zima Pluton, Eastern Sayan

    Science.gov (United States)

    Khromova, E. A.; Doroshkevich, A. G.; Sharygin, V. V.; Izbrodin, L. A.

    2017-12-01

    Pyrochlore-group minerals are the main concentrators of niobium in carbonatites of the Belaya Zima alkaline pluton. Fluorcalciopyrochlore, kenopyrochlore and hydropyrochlore were identified in chemical composition. Their main characteristics are given: compositional variation, morphology, and zoning. During evolution from early calcite to late ankerite carbonatites, the UO2, TiO2, REE, and Y contents gradually increased. All carbonatite types are suggested to contain initial fluorcalciopyrochlore. However, in calcite-dolomite and ankerite carbonatites, it is partially or completely hydrated due to hydrothermal processes at the late stage of the pluton. This hydration resulted in the appearance of kenopyrochlore and hydropyrochlore due to removal of Ca, Na and F, and input of Ba, H2O, K, Si, Fe, and probably U and REE. At the last stage of the pluton, this hydrated pyrochlore was replaced by Fe-bearing columbite.

  20. Structural properties of the geometrically frustrated pyrochlore Tb2Ti2O7

    Energy Technology Data Exchange (ETDEWEB)

    Han, Sang-Wook; Gardner, Jason S.; Booth, Corwin H.

    2004-06-14

    Although materials that exhibit nearest-neighbor-only antiferromagnetic interactions and geometrical frustration theoretically should not magnetically order in the absence of disorder, few such systems have been observed experimentally. One such system appears to be the pyrochlore Tb{sub 2}Ti{sub 2}O{sub 7}. However, previous structural studies indicated that Tb{sub 2}Ti{sub 2}O{sub 7} is an imperfect pyrochlore. To clarify the situation, we performed neutron powder diffraction (NPD) and x-ray absorption fine structure (XAFS) measurements on samples that were prepared identically to those that show no magnetic order. The NPD measurements show that the long-range structure of Tb{sub 2}Ti{sub 2}O{sub 7} is well ordered with no structural transitions between 4.5 and 600 K. In particular, mean-squared displacements (u{sup 2}'s) for each site follow a Debye model with no offsets. No evidence for Tb/Ti site interchange was observed within an upper limit of 2%. Likewise, no excess or deficiency in the oxygen stoichiometry was observed, within an upper limit of 2% of the nominal pyrochlore value. Tb L{sub III} and Ti K-edge XAFS measurements from 20-300 K similarly indicate a well-ordered local structure. Other aspects of the structure are considered. We conclude that Tb{sub 2}Ti{sub 2}O{sub 7} has, within experimental error, an ideal, disorder-free pyrochlore lattice, thereby allowing the system to remain in a dynamic, frustrated spin state to the lowest observed temperatures.

  1. High-pressure synthesis and characterizations of the R2Pt2O7 pyrochlores.

    Science.gov (United States)

    Cai, Yunqi; Cui, Qi; Cheng, Jinguang; Dun, Zhiling; Zhou, Haidong; Ma, Jie; Cruz, C. Dela; Yan, Jiaqiang; Li, Xiang; Zhou, Jianshi

    Pyrochlore R2B2O7 where R3 + stands for rear-earth ion and B4 + for a nonmagnetic cation such as Sn4 +or Ti4 +consist of an important family of geometrically frustrated magnets, which have been the focus of extensive investigations over last decades. To further enlarge the R2B2O7, we have chosen to stabilize the Pt-based cubic pyrochlores under HPHT conditions for two reasons: (1) Pt4 + is in a low-spin state which ionic radius is located in between Ti4 + (0.605\\x85) and Sn4 + (0.69\\x85), and (2) Pt4 + has a spatially much more extended 5d orbitals and thus enhanced Pt 5d-O 2p hybridizations that might modify the local anisotropic exchange interactions. Such an effect has never been taken into account in the previous studies. In this work, we will present the detailed characterizations on the pyrochlores R2Pt2O7 obtained under HPHT conditions. This work is supported by the National Science Foundation of China (Grant Nos.11304371, 11574377), part of the work was supported by the CEM, and NSF MRSEC, under Grant DMR-1420451, and Grant No. NSF-DMR-1350002.

  2. High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jaemin [Department; Shih, Pei-Chieh [Department; Tsao, Kai-Chieh [Department; Pan, Yung-Tin [Department; Yin, Xi [Department; Sun, Cheng-Jun [X-ray; Yang, Hong [Department

    2017-08-17

    Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap between Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.

  3. Emergence of magnetic order in ultra-thin pyrochlore iridate films

    Science.gov (United States)

    Cheema, Suraj; Serrao, Claudy; Mundy, Julia; Patankar, Shreyas; Birgeneau, Robert; Orenstein, Joseph; Salahuddin, Sayeef; Ramesh, Ramamoorthy

    We report on thickness-dependent magnetotransport in (111) - oriented Pb2Ir2O7-x (Pb227) epitaxial thin films. For thicknesses greater than 4 nm, the magnetoresistance (MR) of metallic Pb227 is positive, linear and non-saturated up to 14 T. Meanwhile at 4 nm, the conduction turns nonmetallic and the MR becomes negative and asymmetric upon field-cooling; such traits are reminiscent of all-in-all-out (AIAO) magnetic order in the insulating pyrochlore iridates. Hysteretic low-field MR dips and trained-untrained resistivity bifurcations suggest the presence of magnetic conducting domain walls within the chiral AIAO spin structure. Beyond just AIAO order, angular-dependent MR indicates a magnetic phase space hosting 2-in-2-out (2I2O) spin ice order. Such anomalous magnetotransport calls for re-evaluation of the pyrochlore iridate phase diagram, as epitaxially strained Pb227 exhibits traits reminiscent of both the insulating magnetic and metallic spin-liquid members. Furthermore, these results open avenues for realizing topological phase predictions in (111) - oriented pyrochlore slabs of kagome-triangular iridate heterostructures. This work is supported by the Office of Basic Energy Sciences of the US Department of Energy under Contract No. DE-AC02-05CH11231.

  4. Tm-doped TiO2 and Tm2Ti2O7 pyrochlore nanoparticles: enhancing the photocatalytic activity of rutile with a pyrochlore phase.

    Science.gov (United States)

    De Los Santos, Desiré M; Navas, Javier; Aguilar, Teresa; Sánchez-Coronilla, Antonio; Fernández-Lorenzo, Concha; Alcántara, Rodrigo; Piñero, Jose Carlos; Blanco, Ginesa; Martín-Calleja, Joaquín

    2015-01-01

    Tm-doped TiO2 nanoparticles were synthesized using a water-controlled hydrolysis reaction. Analysis was performed in order to determine the influence of the dopant concentration and annealing temperature on the phase, crystallinity, and electronic and optical properties of the resulting material. Various characterization techniques were utilized such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and UV-vis spectroscopy. For the samples annealed at 773 and 973 K, anatase phase TiO2 was obtained, predominantly internally doped with Tm(3+). ICP-AES showed that a doping concentration of up to 5.8 atom % was obtained without reducing the crystallinity of the samples. The presence of Tm(3+) was confirmed by X-ray photoelectron spectroscopy and UV-vis spectroscopy: the incorporation of Tm(3+) was confirmed by the generation of new absorption bands that could be assigned to Tm(3+) transitions. Furthermore, when the samples were annealed at 1173 K, a pyrochlore phase (Tm2Ti2O7) mixed with TiO2 was obtained with a predominant rutile phase. The photodegradation of methylene blue showed that this pyrochlore phase enhanced the photocatalytic activity of the rutile phase.

  5. George E. Valley, Jr. Prize Talk: Quantum Frustrated Magnetism and its Expression in the Ground State Selection of Pyrochlore Magnets

    Science.gov (United States)

    Ross, Kate

    In the search for novel quantum states of matter, such as highly entangled Quantum Spin Liquids, ``geometrically frustrated'' magnetic lattices are essential for suppressing conventional magnetic order. In three dimensions, the pyrochlore lattice is the canonical frustrated geometry. Magnetic materials with pyrochlore structures have the potential to realize unusual phases such as ``quantum spin ice'', which is predicted to host emergent magnetic monopoles, electrons, and photons as its fundamental excitations. Even in pyrochlores that form long range ordered phases, this often occurs through unusual routes such as ``order by disorder'', in which the fluctuation spectrum dictates the preferred ordered state. The rare earth-based pyrochlore series R2Ti2O7 provides a fascinating variety of magnetic ground states. I will introduce the general anisotropic interaction Hamiltonian that has been successfully used to describe several materials in this series. Using inelastic neutron scattering, the relevant anisotropic interaction strengths can be extracted quantitatively. I will discuss this approach, and its application to two rare earth pyrochlore materials, Er2Ti2O7 and Yb2Ti<2O7, whose ground state properties have long been enigmatic. From these studies, ErTi2O7 and Yb2Ti2O7 have been suggested to be realizations of "quantum order by disorder" and "quantum spin ice", respectively. This research was supported by NSERC of Canada and the National Science Foundation.

  6. Ion-Exchange Reaction Of A-Site In A2Ta2O6 Pyrochlore Crystal Structure

    Directory of Open Access Journals (Sweden)

    Matsunami M.

    2015-06-01

    Full Text Available Na+ or K+ ion rechargeable battery is started to garner attention recently in Place of Li+ ion cell. It is important that A+ site ion can move in and out the positive-electrode materials. When K2Ta2O6 powder had a pyrochlore structure was only dipped into NaOH aqueous solution at room temperature, Na2Ta2O6 was obtained. K2Ta2O6 was fabricated from a tantalum sheet by a hydrothermal synthesize with KOH aqueous solution. When Na2Ta2O6 was dipped into KOH aqueous solution, K2Ta2O6 was obtained again. If KTaO3 had a perovskite structure was dipped, Ion-exchange was not observed by XRD. Because a lattice constant of pyrochlore structure of K-Ta-O system is bigger than perovskite, K+ or Na+ ion could shinny through and exchange between Ta5+ and O2− ion site in a pyrochlore structure. K+ or Na+ ion exchange of A2Ta2O6 pyrochlore had reversibility. Therefore, A2Ta2O6 had a pyrochlore structure can be expected such as Na+ ion rechargeable battery element.

  7. Speciation of uranium in La{sub 2}Zr{sub 2}O{sub 7} pyrochlore by TRPLS

    Energy Technology Data Exchange (ETDEWEB)

    Mohapatra, M.; Rajeswari, B.; Hon, N. S.; Kadam, R. M., E-mail: rmkadam@barc.gov.in; Natarajan, V. [Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400085 (India)

    2015-06-24

    We discuss the speciation of uranium in lanthanum zirconate (La{sub 2}Zr{sub 2}O{sub 7} =LZO) pyrochlore ceramic prepared via a gel-combustion route. Uranium concentration in the pyrochlore was optimized to 2 mol%. XRD and SEM experiments were carried out to assess the phase and homogeneity of the prepared samples. Time resolved photoluminescence (TRPLS) investigations were carried out for understanding the species stabilized in the pyrochlore host. It was observed that, uranium exists as uranate ion (UO{sub 6}{sup 6−}) in the zirconate host where it replaces the ‘Zr’ ions at its regular site with surrounding defect centers created for charge compensation.

  8. Ceramic Single Phase High-Level Nuclear Waste Forms: Hollandite, Perovskite, and Pyrochlore

    Science.gov (United States)

    Vetter, M.; Wang, J.

    2017-12-01

    The lack of viable options for the safe, reliable, and long-term storage of nuclear waste is one of the primary roadblocks of nuclear energy's sustainable future. The method being researched is the incorporation and immobilization of harmful radionuclides (Cs, Sr, Actinides, and Lanthanides) into the structure of glasses and ceramics. Borosilicate glasses are the main waste form that is accepted and used by today's nuclear industry, but they aren't the most efficient in terms of waste loading, and durability is still not fully understood. Synroc-phase ceramics (i.e. hollandite, perovskite, pyrochlore, zirconolite) have many attractive qualities that glass waste forms do not: high waste loading, moderate thermal expansion and conductivity, high chemical durability, and high radiation stability. The only downside to ceramics is that they are more complex to process than glass. New compositions can be discovered by using an Artificial Neural Network (ANN) to have more options to optimize the composition, loading for performance by analyzing the non-linear relationships between ionic radii, electronegativity, channel size, and a mineral's ability to incorporate radionuclides into its structure. Cesium can be incorporated into hollandite's A-site, while pyrochlore and perovskite can incorporate actinides and lanthanides into their A-site. The ANN is used to predict new compositions based on hollandite's channel size, as well as the A-O bond distances of pyrochlore and perovskite, and determine which ions can be incorporated. These new compositions will provide more options for more experiments to potentially improve chemical and thermodynamic properties, as well as increased waste loading capabilities.

  9. XPS studies of ceramics with pyrochlore structure for radioactive wastes disposal

    International Nuclear Information System (INIS)

    Teterin, Yu.A.; Vukchevich, L.; Ivanov, K.E.; Utkin, I.O; Teterin, A. Yu.; Maslakov, K.I.; Yudintseva, T.S.; Yudintsev, S.V.; Stefanovsky, S.V.; Lapina, M.I. . E-mail address of corresponding author: vukas@rc.pmf.cg.ac.yu; Vukchevich, L.)

    2005-01-01

    X-ray photoelectron spectroscopy (XPS) study of ceramics CaThSn 2 O 7 and CaThZr 2 O 7 with pyrochlore structure used as matrixes for the disposal of long lived high level radioactive wastes was done. On the basis of the XPS parameters of the core and outer electrons in the binding energy range 0 - 1000 eV the oxidation states of the included metals were determined, quantitative elemental and ionic analysis was carried out and a conclusion on the monophaseness of the studied samples was drawn. The obtained data agree with the X-ray diffraction and scanning electron microscopy results. (author)

  10. Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

    Science.gov (United States)

    Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

    2018-06-01

    Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

  11. Structural, magnetic, and electronic transport properties of pyrochlore iridate Pr2Ir2O7

    Science.gov (United States)

    Kumar, Harish; Chaurasia, Rachna; Kumari, Pratibha; Paramanik, A. K.

    2018-04-01

    We have studied the structural, magnetic, and electronic transport properties of pyrochlore iridate Pr2Ir2O7. Structural investigation has been done using x-ray powder diffraction and Rietveld analysis. Pr2Ir2O7 crystallize in cubic crystallographic phase with Fd-3m space group. Temperature dependent magnetization data does not show magnetic bifurcation down to 2 K. Electrical resistivity data of Pr2Ir2O7 exhibits metallic behavior throughout temperature range. Below 50 K, a small rise in resistivity data of Pr2Ir2O7 is observed down to 12 K.

  12. Spin freezing in the geometrically frustrated pyrochlore antiferromagnet Tb2Mo2O7

    DEFF Research Database (Denmark)

    Gaulin, B.D.; Reimers, J.N.; Mason, T.E.

    1992-01-01

    The magnetic metal ions in the cubic pyrochlore Tb2Mo2O7 form an infinite three-dimensional network of corner-sharing tetrahedra with a very high potential for frustration in the presence of antiferromagnetism. We have performed neutron scattering measurements which show short-range spatial...... correlations that develop continuously with decreasing temperature, while the characteristic time scale for the fluctuating moments decreases dramatically below T(f) is similar to 25 K. Therefore, this pure material, which possesses frustration that is purely geometrical in origin, displays a spin-glass state...

  13. Isomorphic Structural Transition in the β-Pyrochlore Oxide Superconductor KOs2O6

    Science.gov (United States)

    Yamaura, Jun-ichi; Takigawa, Masashi; Yamamuro, Osamu; Hiroi, Zenji

    2010-04-01

    A phase transition observed at Tp = 7.65 K in the β-pyrochlore oxide superconductor KOs2O6 is studied by means of heat capacity, 39K-NMR, and X-ray diffraction measurements using high-quality single crystals. We find evidence of an isomorphic structural transition at Tp without the off-center freezing of the K ion even below Tp. It is possibly related to the rattling motion of the K ion in an oversized atomic cage.

  14. High-pressure resistivity measurements on the β-pyrochlore oxide KOs2O6

    Science.gov (United States)

    Ogusu, Hiroki; Takeshita, Nao; Yamaura, Jun-Ichi; Okamoto, Yoshihiko; Hiroi, Zenji

    2010-12-01

    High-pressure resistivity measurements are performed on a high-quality single crystal of the β-pyrochlore oxide KOs2O6 in the pressure range of 1.0 to 5.0 GPa. The superconducting transition temperature T increases slightly from 9.6 K at ambient pressure to 9.8 K at 1.0 GPa, decreases gradually with increasing pressure, and suddenly drops from 6.5 K to 3.2 K across P=3.6GPa. The drop of T at P is likely to be related to a change in the rattling vibration associated with a symmetry-breaking structural transition.

  15. Low-temperature specific heat of the β-pyrochlore oxide superconductors under high pressure

    Science.gov (United States)

    Isono, T.; Iguchi, D.; Machida, Y.; Izawa, K.; Salce, B.; Flouquet, J.; Ogusu, H.; Yamaura, J.; Hiroi, Z.

    2011-01-01

    We report the results of the low-temperature specific heat measurements of the single crystalline β-pyrochlore oxide superconductors AOs 2O 6 (A=K, Rb, and Cs) under high pressure up to 13 GPa. We find that superconducting transition temperature ( Tc) monotonically increases for CsOs 2O 6 and RbOs 2O 6, while the one for KOs 2O 6 decreases by applying the pressure. With further increasing the pressure, Tc is suddenly suppressed at the same lattice volume for all compounds, concomitant with the first-order structural phase transition.

  16. Rattling motion in β-pyrochlore compounds explored by the millimeter-wave conductivity measurement

    International Nuclear Information System (INIS)

    Maeda, Atsutaka; Oba, Kentaro; Imai, Yoshinori; Yamaura, Jun-ichi; Hiroi, Zenji

    2010-01-01

    Complex conductivity is investigated at 19 GHz and 44 GHz in the normal state in β-pyrochlore materials, AOs 2 O 6 (A = Cs, Rb and K). In Cs material, large enhancement of the quasiparticle (QP) scattering time, τ, is observed at low temperatures, whereas there is no such enhancement in Rb and K materials. This indicates that rattling motion is absent in Cs material, whether in K and Rb materials it plays the role as a scatterer for QPs. In Rb materials, we find charge excitation possibly originated from the rattling motion.

  17. Topological Magnon Bands and Unconventional Superconductivity in Pyrochlore Iridate Thin Films

    Science.gov (United States)

    Laurell, Pontus; Fiete, Gregory A.

    2017-04-01

    We theoretically study the magnetic properties of pyrochlore iridate bilayer and trilayer thin films grown along the [111] direction using a strong coupling approach. We find the ground state magnetic configurations on a mean field level and carry out a spin-wave analysis about them. In the trilayer case the ground state is found to be the all-in-all-out (AIAO) state, whereas the bilayer has a deformed AIAO state. For all parameters of the spin-orbit coupled Hamiltonian we study, the lowest magnon band in the trilayer case has a nonzero Chern number. In the bilayer case we also find a parameter range with nonzero Chern numbers. We calculate the magnon Hall response for both geometries, finding a striking sign change as a function of temperature. Using a slave-boson mean-field theory we study the doping of the trilayer system and discover an unconventional time-reversal symmetry broken d +i d superconducting state. Our study complements prior work in the weak coupling limit and suggests that the [111] grown thin film pyrochlore iridates are a promising candidate for topological properties and unconventional orders.

  18. Quantum phase transitions and anomalous Hall effect in a pyrochlore Kondo lattice

    Science.gov (United States)

    Grefe, Sarah; Ding, Wenxin; Si, Qimiao

    The metallic variant of the pyrochlore iridates Pr2Ir2O7 has shown characteristics of a possible chiral spin liquid state [PRL 96 087204 (2006), PRL 98, 057203 (2007), Nature 463, 210 (2010)] and quantum criticality [Nat. Mater. 13, 356 (2014)]. An important question surrounding the significant anomalous Hall response observed in Pr2Ir2O7 is the nature of the f-electron local moments, including their Kondo coupling with the conduction d-electrons. The heavy effective mass and related thermodynamic characteristics indicate the involvement of the Kondo effect in this system's electronic properties. In this work, we study the effects of Kondo coupling on candidate time-reversal-symmetry-breaking spin liquid states on the pyrochlore lattice. Representing the f-moments as slave fermions Kondo-coupled to conduction electrons, we study the competition between Kondo-singlet formation and chiral spin correlations and determine the zero-temperature phase diagram. We derive an effective chiral interaction between the local moments and the conduction electrons and calculate the anomalous Hall response across the quantum phase transition from the Kondo destroyed phase to the Kondo screened phase. We discuss our results' implications for Pr2Ir2O7 and related frustrated Kondo-lattice systems.

  19. Spin-1/2 Heisenberg antiferromagnet on the pyrochlore lattice: An exact diagonalization study

    Science.gov (United States)

    Chandra, V. Ravi; Sahoo, Jyotisman

    2018-04-01

    We present exact diagonalization calculations for the spin-1/2 nearest-neighbor antiferromagnet on the pyrochlore lattice. We study a section of the lattice in the [111] direction and analyze the Hamiltonian of the breathing pyrochlore system with two coupling constants J1 and J2 for tetrahedra of different orientations and investigate the evolution of the system from the limit of disconnected tetrahedra (J2=0 ) to a correlated state at J1=J2 . We evaluate the low-energy spectrum, two and four spin correlations, and spin chirality correlations for a system size of up to 36 sites. The model shows a fast decay of spin correlations and we confirm the presence of several singlet excitations below the lowest magnetic excitation. We find chirality correlations near J1=J2 to be small at the length scales available at this system size. Evaluation of dimer-dimer correlations and analysis of the nature of the entanglement of the tetrahedral unit shows that the triplet sector of the tetrahedron contributes significantly to the ground-state entanglement at J1=J2 .

  20. Structural disorder and transport in ternary oxides with the pyrochlore structure. Final report; FINAL

    International Nuclear Information System (INIS)

    Tuller, Harry L.

    2001-01-01

    This research program has focused on the structure-electrical property relations in families of pyrochlore compounds which exhibit, on the one hand, controlled levels of structural disorder and on the other, controlled levels of ionic and electronic conductivities. Models have been developed to evaluate the often complex defect chemistry of these systems. Much progress has been made in extracting key thermodynamic and kinetic data. From a technological standpoint, novel solid electrolytes and compatible mixed conducting electrodes have been identified and the concept of the single phase monolithic fuel cell design has been demonstrated and patented. Related work on lanthanum gallate-based perovskites has shown even more promising results for use of such materials in the monolithic fuel cell structures. Recent work on the Bi(sub 3)Zn(sub 2)Sb(sub 3)O(sub 14) Pyrochlore, a phase found at grain boundaries in varistors, was also completed. This material was found to be a mixed ionic-electronic conductor with interesting implications for grain boundary equilibration kinetics in SnO-base varistor materials. Three of the most recent projects are summarized in this paper. The results of work on the perovskites are reported in recent publications

  1. Disorder-induced transition from grain boundary to bulk dominated ionic diffusion in pyrochlores

    International Nuclear Information System (INIS)

    Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

    2017-01-01

    In this paper, we use molecular dynamics simulations to investigate the role of grain boundaries (GBs) on ionic diffusion in pyrochlores, as a function of the GB type, chemistry of the compound, and level of cation disorder. We observe that the presence of GBs promotes oxygen transport in ordered and low-disordered systems, as the GBs are found to have a higher concentration of mobile carriers with higher mobilities than in the bulk. Thus, in ordered samples, the ionic diffusion is 2D, localized along the grain boundary. When cation disorder is introduced, bulk carriers begin to contribute to the overall diffusion, while the GB contribution is only slightly enhanced. In highly disordered samples, the diffusive behavior at the GBs is bulk-like, and the two contributions (bulk vs. GB) can no longer be distinguished. There is thus a transition from 2D/GB dominated oxygen diffusivity to 3D/bulk dominated diffusivity versus disorder in pyrochlores. Finally, these results provide new insights into the possibility of using internal interfaces to enhance ionic conductivity in nanostructured complex oxides.

  2. Direct Measurement of Surface Dissolution Rates in Potential Nuclear Waste Forms: The Example of Pyrochlore.

    Science.gov (United States)

    Fischer, Cornelius; Finkeldei, Sarah; Brandt, Felix; Bosbach, Dirk; Luttge, Andreas

    2015-08-19

    The long-term stability of ceramic materials that are considered as potential nuclear waste forms is governed by heterogeneous surface reactivity. Thus, instead of a mean rate, the identification of one or more dominant contributors to the overall dissolution rate is the key to predict the stability of waste forms quantitatively. Direct surface measurements by vertical scanning interferometry (VSI) and their analysis via material flux maps and resulting dissolution rate spectra provide data about dominant rate contributors and their variability over time. Using pyrochlore (Nd2Zr2O7) pellet dissolution under acidic conditions as an example, we demonstrate the identification and quantification of dissolution rate contributors, based on VSI data and rate spectrum analysis. Heterogeneous surface alteration of pyrochlore varies by a factor of about 5 and additional material loss by chemo-mechanical grain pull-out within the uppermost grain layer. We identified four different rate contributors that are responsible for the observed dissolution rate range of single grains. Our new concept offers the opportunity to increase our mechanistic understanding and to predict quantitatively the alteration of ceramic waste forms.

  3. High-pressure effects on the superconductivity of β-pyrochlore oxides AOs2O6

    International Nuclear Information System (INIS)

    Muramatsu, Takaki; Takeshita, Nao; Terakura, Chikeko; Takagi, Hidenori; Tokura, Yoshinori; Yonezawa, Shigeki; Muraoka, Yuji; Hiroi, Zenji

    2006-01-01

    High-pressure effects on the superconducting transitions of β-pyrochlore oxide superconductors AOs 2 O 6 (A=Cs, Rb, K) are studied by measuring resistivity under high pressures up to 16 GPa. The superconducting transition temperature T c first increases with increasing pressure in all the compounds and then exhibits a broad maximum at 7.6 K (6 GPa), 8.2 K (2 GPa) and 10 K (0.6 GPa) for A=Cs, Rb and K, respectively. Finally, the superconductivity is suppressed completely at a critical pressure near 7 and 6 GPa for A=Rb and K and probably above 10 GPa for A=Cs. Characteristic changes in the temperature dependence of resistivity of RbOs 2 O 6 under high pressure. The residual resistivity largely increases with pressure above 4 GPa and, as a result, resistivity indicates small temperature dependence down to 4.2 K at 7 GPa and application of further pressure up to 10 GPa indicates that temperature dependence of resistivity decrease below 100 K. This characteristic behavior in the β-pyrochlore oxides may originate from the nesting of nearly octahedron shape of Fermi surface

  4. Topological Magnon Bands and Unconventional Superconductivity in Pyrochlore Iridate Thin Films.

    Science.gov (United States)

    Laurell, Pontus; Fiete, Gregory A

    2017-04-28

    We theoretically study the magnetic properties of pyrochlore iridate bilayer and trilayer thin films grown along the [111] direction using a strong coupling approach. We find the ground state magnetic configurations on a mean field level and carry out a spin-wave analysis about them. In the trilayer case the ground state is found to be the all-in-all-out (AIAO) state, whereas the bilayer has a deformed AIAO state. For all parameters of the spin-orbit coupled Hamiltonian we study, the lowest magnon band in the trilayer case has a nonzero Chern number. In the bilayer case we also find a parameter range with nonzero Chern numbers. We calculate the magnon Hall response for both geometries, finding a striking sign change as a function of temperature. Using a slave-boson mean-field theory we study the doping of the trilayer system and discover an unconventional time-reversal symmetry broken d+id superconducting state. Our study complements prior work in the weak coupling limit and suggests that the [111] grown thin film pyrochlore iridates are a promising candidate for topological properties and unconventional orders.

  5. Odd-parity magnetoresistance in pyrochlore iridate thin films with broken time-reversal symmetry

    Science.gov (United States)

    Fujita, T. C.; Kozuka, Y.; Uchida, M.; Tsukazaki, A.; Arima, T.; Kawasaki, M.

    2015-01-01

    A new class of materials termed topological insulators have been intensively investigated due to their unique Dirac surface state carrying dissipationless edge spin currents. Recently, it has been theoretically proposed that the three dimensional analogue of this type of band structure, the Weyl Semimetal phase, is materialized in pyrochlore oxides with strong spin-orbit coupling, accompanied by all-in-all-out spin ordering. Here, we report on the fabrication and magnetotransport of Eu2Ir2O7 single crystalline thin films. We reveal that one of the two degenerate all-in-all-out domain structures, which are connected by time-reversal operation, can be selectively formed by the polarity of the cooling magnetic field. Once formed, the domain is robust against an oppositely polarised magnetic field, as evidenced by an unusual odd field dependent term in the magnetoresistance and an anomalous term in the Hall resistance. Our findings pave the way for exploring the predicted novel quantum transport phenomenon at the surfaces/interfaces or magnetic domain walls of pyrochlore iridates. PMID:25959576

  6. Energetics of stepwise disordering transformation in pyrochlores, RE2Ti2O7 (RE = Y, Gd and Dy)

    International Nuclear Information System (INIS)

    Hayun, Shmuel; Tran, Tien B.; Lian, Jie; Fuentes, Antonio F.; Navrotsky, Alexandra

    2012-01-01

    Graphical abstract: The transformation from disordered to more order state in the pyrochlore system go through multiple energetics steps; the cation sublattice rearrangement is control by the diffusion of the cations while the anion sublattice display an irreversible transformation from a disordered to a higher-ordered state via diffusionless transformation. - Abstract: The capacity to incorporate actinide cations makes pyrochlore titanates first-choice phases in titanate-based waste form ceramics. Despite broad interest in the pyrochlore order–disorder transformation due to the cumulative effects of 238 U, 235 U and 232 Th radioactive decay and their daughter products, only limited thermodynamic data, mainly based on simulations of ion-beam irradiation experiments, have been reported. In this work, for the first time, heavily disordered pyrochlores, RE 2 Ti 2 O 7 (RE = Y, Gd and Dy), from mechanical milling of their constituent oxides, were thermochemically investigated. Two types of thermal events were identified using high-temperature differential scanning calorimetry and correlated to the structural disorder in the cation and anion sublattices. Moreover, the excess formation energy measured by oxide melt solution calorimetry shows that the smaller the ionic radius of the RE, the easier it is to remove damage domains.

  7. X-ray diffraction study of the Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore disordering sequence under irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Soulié, Aurélien, E-mail: aurelien.soulie@cea.fr [CEA, DEN, Service de Recherches de Métallurgie Physique, Université Paris-Saclay, F-91191 Gif sur Yvette (France); CEA, DEN, Service de Recherches de Métallurgie Appliqué, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Menut, Denis [CEA, DEN, Service de Recherches de Métallurgie Appliqué, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Crocombette, Jean-Paul [CEA, DEN, Service de Recherches de Métallurgie Physique, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Chartier, Alain [CEA, DEN, Service de la Corrosion et du Comportement des Matériaux dans leur Environnement, Laboratoire de Modélisation, de Thermodynamique et de Thermochimie, Université Paris-Saclay, F-91191 Gif sur Yvette (France); Sellami, Neila [Univ. Paris Sud, ICMMO-SP2M, Bât. 410, F-91405 Orsay (France); Sattonnay, Gaël [Univ. Paris-Sud, CSNSM, CNRS, IN2P3, Bât. 108, F-91405 Orsay (France); Monnet, Isabelle [CIMAP, CEA, CNRS, Université de Caen, BP 5133, F-14070 Caen Cedex 5 (France); and others

    2016-11-15

    The disordering sequence of Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore, a nano-oxide phase that strengthens ODS steels under irradiation is studied in the experimental and modeling framework. XRD analysis has been performed considering both swift heavy ion and low energy/low mass ion irradiations. The simulation within molecular dynamics of Frenkel pair accumulation proves able to reproduce the variation of the amorphization fluence with temperature. XRD patterns calculated from the simulations reproduce well the patterns observed experimentally in the literature. Both experiments and calculations point to a first transition from pyrochlore to fluorite before an eventual amorphization. For swift heavy ion irradiations with 93 MeV Xe ions, tracks of direct impact amorphization are visible by HRTEM. Advanced refinement shows that one third of the pyrochlore impacted by an ion transforms into fluorite, while two third are directly amorphized. - Highlights: • A comparison between swift heavy ion and low energy/low mass ion irradiation of Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore is performed. • Simulations of the irradiation with Molecular dynamics reproduce the amorphization dose at low energy/mass ion irradiation. • Advanced refinement of X-ray diffraction patterns gives the evolution of phase fractions in pyrochlore under irradiation. • The disordering sequence a transition from pyrochlore to defect fluorite before an eventual amorphization.

  8. Quantum Spin Ice under a [111] Magnetic Field: From Pyrochlore to Kagome.

    Science.gov (United States)

    Bojesen, Troels Arnfred; Onoda, Shigeki

    2017-12-01

    Quantum spin ice, modeled for magnetic rare-earth pyrochlores, has attracted great interest for hosting a U(1) quantum spin liquid, which involves spin-ice monopoles as gapped deconfined spinons, as well as gapless excitations analogous to photons. However, the global phase diagram under a [111] magnetic field remains open. Here we uncover by means of unbiased quantum Monte Carlo simulations that a supersolid of monopoles, showing both a superfluidity and a partial ionization, intervenes the kagome spin ice and a fully ionized monopole insulator, in contrast to classical spin ice where a direct discontinuous phase transition takes place. We also show that on cooling, kagome spin ice evolves towards a valence-bond solid similar to what appears in the associated kagome lattice model [S. V. Isakov et al., Phys. Rev. Lett. 97, 147202 (2006)PRLTAO0031-900710.1103/PhysRevLett.97.147202]. Possible relevance to experiments is discussed.

  9. Phase transition and water incorporation into Eu2Sn2O7 pyrochlore at high pressure

    Science.gov (United States)

    Zhang, F. X.; Lang, M.; Ewing, R. C.

    2016-04-01

    Structural changes of europium stannate pyrochlore, Eu2Sn2O7, have been investigated at high pressures with in situ Raman spectroscopy, photoluminescence (PL), and synchrotron X-ray diffraction (XRD) techniques. The XRD measurements suggest that a pressure-induced phase transition starts at 34.4 GPa. The PL spectrum from Eu3+ cations also suggests a phase transition above 36 GPa. XRD analysis shows that the unit cell of the cubic phase deviates from the equation of state at pressures above 23.8 GPa. This is due to the incorporation of water from the pressure medium in the structure at high pressures, which is confirmed by optical spectroscopy measurements.

  10. A spin-liquid with pinch-line singularities on the pyrochlore lattice.

    Science.gov (United States)

    Benton, Owen; Jaubert, L D C; Yan, Han; Shannon, Nic

    2016-05-26

    The mathematics of gauge theories lies behind many of the most profound advances in physics in the past 200 years, from Maxwell's theory of electromagnetism to Einstein's theory of general relativity. More recently it has become clear that gauge theories also emerge in condensed matter, a prime example being the spin-ice materials which host an emergent electromagnetic gauge field. In spin-ice, the underlying gauge structure is revealed by the presence of pinch-point singularities in neutron-scattering measurements. Here we report the discovery of a spin-liquid where the low-temperature physics is naturally described by the fluctuations of a tensor field with a continuous gauge freedom. This gauge structure underpins an unusual form of spin correlations, giving rise to pinch-line singularities: line-like analogues of the pinch points observed in spin-ice. Remarkably, these features may already have been observed in the pyrochlore material Tb2Ti2O7.

  11. Cluster-Glass Phase in Pyrochlore X Y Antiferromagnets with Quenched Disorder

    Science.gov (United States)

    Andrade, Eric C.; Hoyos, José A.; Rachel, Stephan; Vojta, Matthias

    2018-03-01

    We study the impact of quenched disorder (random exchange couplings or site dilution) on easy-plane pyrochlore antiferromagnets. In the clean system, order by disorder selects a magnetically ordered state from a classically degenerate manifold. In the presence of randomness, however, different orders can be chosen locally depending on details of the disorder configuration. Using a combination of analytical considerations and classical Monte Carlo simulations, we argue that any long-range-ordered magnetic state is destroyed beyond a critical level of randomness where the system breaks into magnetic domains due to random exchange anisotropies, becoming, therefore, a glass of spin clusters, in accordance with the available experimental data. These random anisotropies originate from off-diagonal exchange couplings in the microscopic Hamiltonian, establishing their relevance to other magnets with strong spin-orbit coupling.

  12. Structural order parameter in the pyrochlore superconductor Cd sub 2 Re sub 2 O sub 7

    CERN Document Server

    Sergienko, I A

    2003-01-01

    It is shown that both structural phase transitions in Cd sub 2 Re sub 2 O sub 7 , which occur at T sub s sub 1 = 200 K and T sub s sub 2 = 120 K, are due to an instability of the Re tetrahedral network with respect to the same doubly degenerate long-wavelength phonon mode. The primary structural order parameter transforms according to the irreducible representation E sub u of the point group O sub h. We argue that the transition at T sub s sub 1 may be of the second order, in accordance with experimental data. We obtain the phase diagram in the space of phenomenological parameters and propose a thermodynamic path that Cd sub 2 Re sub 2 O sub 7 follows upon cooling. Coupling of the itinerant electronic system and localized spin states in pyrochlores and spinels to atomic displacements are discussed. (author)

  13. Low temperature spin dynamics and high pressure effects in frustrated pyrochlores

    Science.gov (United States)

    Mirebeau, Isabelle

    2008-03-01

    Frustrated pyrochlores R2M2O7, where R^3+ is a rare earth and M^4+ a transition or sp metal ion, show a large variety of exotic magnetic states due to the geometrical frustration of the pyrochlore lattice, consisting of corner sharing tetrahedra for both R and M ions. Neutron scattering allows one to measure their magnetic ground state as well as the spin fluctuations, in a microscopic way. An applied pressure may change the subtle energy balance between magnetic interactions, inducing new magnetic states. In this talk, I will review recent neutron results on Terbium pyrochlores, investigated by high pressure neutron diffraction and inelastic neutron scattering. Tb2M2O7 pyrochlores show respectively a spin liquid state for M=Ti [1], an ordered spin ice state for M= Sn [2], and a spin glass state with chemical order for M=Mo [3]. In Tb2Ti2O7 spin liquid, where only Tb^3+ ions are magnetic, an applied pressure induces long range antiferromagnetic order due to a small distortion of the lattice and magneto elastic coupling [4]. In Tb2Sn2O7, the substitution of Ti^4+ by the bigger Sn^4+ ion expands the lattice, inducing a long range ordered ferromagnetic state, with the local structure of a spin ice [2] and unconventional spin fluctuations [2,5]. The local ground state and excited crystal field states of the Tb^3+ ion were recently investigated by inelastic neutron scattering in both compounds [6]. Tb2Mo2O7, where Mo^4+ ions are also magnetic, shows an even more rich behaviour, due to the complex interaction between frustrated Tb and Mo lattices, having respectively localized and itinerant magnetism. In Tb2Mo2O7 spin glass, the lattice expansion induced by Tb/La substitution yields an ordered ferromagnetic state, which transforms back to spin glass under applied pressure [7]. New data about the spin fluctuations in these compounds, as measured by inelastic neutron scattering, will be presented. The talk will be dedicated to the memory of Igor Goncharenko, a renowned

  14. Multilayer Thermal Barrier Coating (TBC) Architectures Utilizing Rare Earth Doped YSZ and Rare Earth Pyrochlores

    Science.gov (United States)

    Schmitt, Michael P.; Rai, Amarendra K.; Bhattacharya, Rabi; Zhu, Dongming; Wolfe, Douglas E.

    2014-01-01

    To allow for increased gas turbine efficiencies, new insulating thermal barrier coatings (TBCs) must be developed to protect the underlying metallic components from higher operating temperatures. This work focused on using rare earth doped (Yb and Gd) yttria stabilized zirconia (t' Low-k) and Gd2Zr2O7 pyrochlores (GZO) combined with novel nanolayered and thick layered microstructures to enable operation beyond the 1200 C stability limit of current 7 wt% yttria stabilized zirconia (7YSZ) coatings. It was observed that the layered system can reduce the thermal conductivity by approximately 45 percent with respect to YSZ after 20 hr of testing at 1316 C. The erosion rate of GZO is shown to be an order to magnitude higher than YSZ and t' Low-k, but this can be reduced by almost 57 percent when utilizing a nanolayered structure. Lastly, the thermal instability of the layered system is investigated and thought is given to optimization of layer thickness.

  15. Phonon Dynamics and Multipolar Isomorphic Transition in β-Pyrochlore KOs2O6

    Science.gov (United States)

    Hattori, Kazumasa

    2011-02-01

    We investigate with a microscopic model anharmonic K-cation oscillation observed by neutron experiments in β-pyrochlore superconductor KOs2O6, which also shows a mysterious first-order structural transition at Tp = 7.5 K. We have identified a set of microscopic model parameters that successfully reproduce the observed tem perature dependence and the superconducting transition temperature. Considering changes in the parameters at Tp, we can explain puzzling experimental results about electron--phonon coupling and neutron data. Our analysis demonstrates that the first-order transition is multipolar transition driven by the octupolar component of K-cation oscillations. The octupole moment does not change the symmetry and is characteristic to noncentrosymmetric K-cation potential.

  16. Anisotropic vortex pinning in the β-pyrochlore oxide superconductor KOs 2O 6

    Science.gov (United States)

    Ishii, Y.; Yamaura, J.; Okamoto, Y.; Maeda, A.; Hiroi, Z.

    2011-11-01

    Vortex pinning in the β-pyrochlore oxide superconductor KOs2O6 with Tc = 9.6 K is investigated by measuring magnetic torque. A large anisotropy of magnetic torque is observed in the superconducting state below Tp = 7.6 K, where a first-order structural transition takes place, in spite of the inherent isotropic nature of the structural and electronic properties. Magnetic torque is enhanced at external magnetic fields parallel to the [1 1 1] and [0 0 1] directions. Moreover, a pronounced peak effect is also observed in the magnetic field dependence of the torque in these two directions. We consider that the observed anisotropy is related to a microstructure associated with the structural transition.

  17. Electronic Structure of the Pyrochlore-Type Ru Oxides through the Metal--Insulator Transition

    International Nuclear Information System (INIS)

    Okamoto, J.; Fujimori, S.I.; Okane, T.; Fujimori, A.; Abbate, M.; Yoshii, S.; Sato, M.

    2003-01-01

    The electronic structures of the pyrochlore-type Ru oxides Sm 2-x Ca x Ru 2 O 7 and Sm 2-x Bi x Ru 2 O 7 , which show metal-insulator transition with increasing Ca or Bi concentration, have been studied by ultraviolet photoemission spectroscopy. Spectral changes near the Fermi level are different but reflect the tendency of their transport properties in both systems. The Sm 2-x Ca x Ru 2 O 7 system shows an energy shift, which is expected from the increase of hole in the Ru 4d t 2g band and the Sm 2 - x Bi x Ru 2 O 7 system shows spectral weight transfer within the Ru 4d t 2g band, which is expected to be observed in bandwidth-control Mott-Hubbard system. (author)

  18. Irradiation-induced amorphization of Cd2Nb2O7 pyrochlore

    International Nuclear Information System (INIS)

    Meldrum, A.; White, C. W.; Keppens, V.; Boatner, L. A.; Ewing, R. C.

    2001-01-01

    Several investigations have recently been undertaken in order to achieve a more complete understanding of the radiation-damage mechanisms in A 2 B 2 O 7 pyrochlore-structure compounds. The present work represents the first systematic study of the irradiation-induced amorphization of a pyrochlore with A- and B-site cation valences of +2 and +5, respectively. Relatively large single crystals of Cd 2 Nb 2 O 7 were grown for these experiments. In situ ion-irradiation experiments were carried out in a transmission electron microscope in conjunction with ex situ Rutherford backscattering measurements of ion-irradiated Cd 2 Nb 2 O 7 single crystals. Cd 2 Nb 2 O 7 can be amorphized in situ by Ne or Xe ions at temperatures up to 480 and 620 K, respectively. At room temperature, the amorphization fluence was 36 times higher for 280 keV Ne + than for 1200 keV Xe 2+ , corresponding to a displacement dose that was higher by a factor of 3. Disordering of Cd and Nb over the available cation sites occurs at intermediate ion doses prior to amorphization. The temperature dependence of the amorphization dose is modeled, and the results are compared to those of a previous model. The bulk-sample Rutherford backscattering spectroscopy (RBS) results were generally consistent with the in situ TEM measurements. Effects of crystallographic orientation and ion charge state had relatively little effect on the damage accumulation in bulk crystals. The RBS data are consistent with a defect-accumulation, cascade-overlap model of amorphization of Cd 2 Nb 2 O 7 , as are the in situ TEM observations

  19. Phase Competition in the Palmer-Chalker X Y Pyrochlore Er2Pt2O7

    Science.gov (United States)

    Hallas, A. M.; Gaudet, J.; Butch, N. P.; Xu, Guangyong; Tachibana, M.; Wiebe, C. R.; Luke, G. M.; Gaulin, B. D.

    2017-11-01

    We report neutron scattering measurements on Er2Pt2O7 , a new addition to the X Y family of frustrated pyrochlore magnets. Symmetry analysis of our elastic scattering data shows that Er2Pt2O7 orders into the k =0 , Γ7 magnetic structure (the Palmer-Chalker state), at TN=0.38 K . This contrasts with its sister X Y pyrochlore antiferromagnets Er2Ti2O7 and Er2Ge2O7 , both of which order into Γ5 magnetic structures at much higher temperatures, TN=1.2 and 1.4 K, respectively. In this temperature range, the magnetic heat capacity of Er2Pt2O7 contains a broad anomaly centered at T*=1.5 K . Our inelastic neutron scattering measurements reveal that this broad heat capacity anomaly sets the temperature scale for strong short-range spin fluctuations. Below TN=0.38 K , Er2Pt2O7 displays a gapped spin-wave spectrum with an intense, flat band of excitations at lower energy and a weak, diffusive band of excitations at higher energy. The flat band is well described by classical spin-wave calculations, but these calculations also predict sharp dispersive branches at higher energy, a striking discrepancy with the experimental data. This, in concert with the strong suppression of TN, is attributable to enhanced quantum fluctuations due to phase competition between the Γ7 and Γ5 states that border each other within a classically predicted phase diagram.

  20. Novel rattling of K atoms in aluminium-doped defect pyrochlore tungstate

    International Nuclear Information System (INIS)

    Shoko, Elvis; Kearley, Gordon J; Peterson, Vanessa K; Thorogood, Gordon J; Mutka, Hannu; Koza, Michael M; Yamaura, Jun-ichi; Hiroi, Zenji

    2014-01-01

    Rattling dynamics have been identified as fundamental to superconductivity in defect pyrochlore osmates and aluminium vanadium intermetallics, as well as low thermal conductivity in clathrates and filled skutterudites. Combining inelastic neutron scattering (INS) measurements and ab initio molecular dynamics (MD) simulations, we use a new approach to investigate rattling in the Al-doped defect pyrochlore tungstates: AAl 0.33 W 1.67 O 6 (A = K, Rb, Cs). We find that although all the alkali metals rattle, the rattling of the K atoms is unique, not only among the tungstates but also among the analogous defect osmates, KOs 2 O 6 and RbOs 2 O 6 . Detailed analysis of the MD trajectories reveals that two unique features set the K dynamics apart from the rest, namely, (1) quasi one-dimensional local diffusion within a cage, and (2) vibration at a range of frequencies. The local diffusion is driven by strongly anharmonic local potentials around the K atoms exhibiting a double-well structure in the direction of maximum displacement, which is also the direction of local diffusion. On the other hand, vibration at a range of frequencies is a consequence of the strong anisotropy in the local potentials around the K atoms as revealed by directional magnitude spectra. We present evidence to show that it is the smaller size rather than the smaller mass of the K rattler which leads to the unusual dynamics. Finally, we suggest that the occurrence of local diffusion and vibration at a range of frequencies in the dynamics of a single rattler, as found here for the K atoms, may open new possibilities for phonon engineering in thermoelectric materials. (paper)

  1. Multifunctional Sm2-xDyxZr2O7 pyrochlore system: potential ionic conductors and photocatalysts

    International Nuclear Information System (INIS)

    Grover, V.; Sayed, Farheen N.; Bhattacharyya, K.; Jain, D.; Pillai, C.G.S.; Tyagi, A.K.; Arya, A.

    2010-01-01

    Full text: Pyrochlores have garnered considerable interest over the years because of a range of potentially useful properties such as fast-ion (mainly anion) conductivity, electrical conductivity, catalysis, luminescence etc. In present work a series of Sm 2-x Dy x Zr 2 O 7 compounds (0.0 ≤ x ≤ 2.0) were synthesized by gel combustion and characterized by Powder XRD and Raman spectroscopic studies. XRD studies revealed the system to be single-phasic throughout with the retention of pyrochlore phase till 40 mol% of Dy 3+ beyond which, an order-disorder phase transition occurred resulting in a defect fluorite structure. Surprisingly, Raman studies showed the retention of pyrochlore type ordering till the other end member, i.e. Dy 2 Zr 2 O 7 . This is the first study, which reports the retention of a weak pyrochlore type superstructure in Dy 2 Zr 2 O 7 system. Ionic conductivity measurements were performed on these samples, which showed that the activation Energy (E a ) increases with increase in Dy 3+ mol% owing to the decreased mobility with increasing degree of disorder. The representative nquist Plots are given for Sm 2 Zr 2 O 7 . These materials have a definite band gap absorbing mainly in the UV region which makes them good candidates for photocatalysed dye degradation studies. Potential of some of these compositions as photocatalysts was also explored and they were found to efficiently catalyse the degradation of Xylenol Orange with t 1/2 decreasing from pure Sm 2 Zr 2 O 7 to pure Dy 2 Zr 2 O 7

  2. Radiation damage effects in pyrochlore and zirconolite ceramic matrices for the immobilization of actinide-rich wastes

    International Nuclear Information System (INIS)

    Lumpkin, G.R.; Begg, B.D.; Smith, K.L.

    2000-01-01

    Actinide-doping experiments using short-lived 238 Pu and 244 Cm have demonstrated that pyrochlore and zirconolite become fully amorphous at a dose of 0.2-0.5 x 10 16 α/mg at ambient temperature and exhibit bulk swelling of 5-7%. Detailed studies of natural samples have included determination of the critical amorphization dose, long-term annealing rate, microstructural changes as a function of dose, and the thermal histories of the host rocks. Together, the laboratory based work and studies of natural samples indicate that the critical amorphization dose will increase by about a factor of 2-4 for samples stored at temperatures of 100-200 deg. C for up to 10 million years. These studies of alpha-decay damage have been complemented by heavy ion irradiation studies over the last ten years. Most of the irradiation work has concerned the critical amorphization dose as a function of temperature in thin films; however, some work has been carried out on bulk samples. The irradiation work indicates that most pyrochlore and zirconolite compositions will have similar critical amorphization doses at low temperatures (e.g., below 300-400 deg. C). Pyrochlore with Zr as the major B-site cation transform to a defect fluorite structure with increasing ion irradiation dose, but do not become amorphous. (authors)

  3. Combined experimental–theoretical study of the optoelectronic properties of non-stoichiometric pyrochlore bismuth titanate

    KAUST Repository

    Noureldine, Dalal

    2015-10-27

    A combination of experimental and computational methods was applied to investigate the crystal structure and optoelectronic properties of the non-stoichiometric pyrochlore Bi2−xTi2O7−1.5x. The detailed experimental protocol for both powder and thin-film material synthesis revealed that a non-stoichiometric Bi2−xTi2O7−1.5x structure with an x value of ∼0.25 is the primary product, consistent with the thermodynamic stability of the defect-containing structure computed using density functional theory (DFT). The approach of density functional perturbation theory (DFPT) was used along with the standard GGA PBE functional and the screened Coulomb hybrid HSE06 functional, including spin–orbit coupling, to investigate the electronic structure, the effective electron and hole masses, the dielectric constant, and the absorption coefficient. The calculated values for these properties are in excellent agreement with the measured values, corroborating the overall analysis. This study indicates potential applications of bismuth titanate as a wide-bandgap material, e.g., as a substitute for TiO2 in dye-sensitized solar cells and UV-light-driven photocatalysis.

  4. Potassium Disorder in the Defect Pyrochlore KSbTeO6: A Neutron Diffraction Study

    Directory of Open Access Journals (Sweden)

    José Antonio Alonso

    2017-01-01

    Full Text Available KSbTeO6 defect pyrochlore has been prepared from K2C2O4, Sb2O3, and 15% excess TeO2 by solid-state reaction at 850 °C. Direct methods implemented in the software EXPO2013 allowed establishing the basic structural framework. This was followed by a combined Rietveld refinement from X-ray powder diffraction (XRD and neutron powder diffraction (NPD data, which unveiled additional structural features. KSbTeO6 is cubic, a = 10.1226(7 Å, space group F d 3 ¯ m , Z = 8 and it is made of a mainly covalent framework of corner-sharing (Sb,TeO6 octahedra, with weakly bonded K+ ions located within large cages. The large K-O distances, 3.05(3–3.07(3 Å, and quite large anisotropic atomic displacement parameters account for the easiness of K+ exchange for other cations of technological importance.

  5. Superconductivity mediated by anharmonic phonons: application to β-pyrochlore oxides

    Science.gov (United States)

    Hattori, Kazumasa; Tsunetsugu, Hirokazu

    2010-03-01

    We investigate three dimensional anharmonic phonons under tetrahedral symmetry and superconductivity mediated by these phonons. Three dimensional anharmonic phonon spectra are calculated directly by solving Schr"odinger equation and the superconducting transition temperature is determined by using the theory of strong coupling superconductivity assuming an isotropic gap function. With increasing the third order anharmonicity b of the tetrahedral potential, we find a crossover in the energy spectrum to a quantum tunneling regime. We obtain strongly enhanced transition temperatures around the crossover point. The first order transition observed in KOs2O6 is discussed in terms of the first excited state energy δ, and the coupling constant λ in the strong coupling theory of superconductivity. Our results suggest that the decrease of λ and increase of δ below the first order transition temperature. We point out that the change in the oscillation amplitude and characterizes this isomorphic transition. The chemical trends of the superconducting transition temperature, λ, and δ in the β-pyrochlore compounds are also discussed.

  6. Observation of magnetic polarons in the magnetoresistive pyrochlore Lu2V2O7

    International Nuclear Information System (INIS)

    Storchak, Vyacheslav G; Brewer, Jess H; Eshchenko, Dmitry G; Mengyan, Patrick W; Zhou Haidong; Wiebe, Christopher R

    2013-01-01

    Materials that exhibit colossal magnetoresistance (CMR) have attracted much attention due to their potential technological applications. One particularly interesting model for the magnetoresistance of low-carrier-density ferromagnets involves mediation by magnetic polarons (MP)—electrons localized in nanoscale ferromagnetic ‘droplets’ by their exchange interaction. However, MP have not previously been directly detected and their size has been difficult to determine from macroscopic measurements. In order to provide this crucial information, we have carried out muon spin rotation measurements on the magnetoresistive semiconductor Lu 2 V 2 O 7 in the temperature range from 2 to 300 K and in magnetic fields up to 7 T. Magnetic polarons with characteristic radius R ≈ 0.4 nm are detected below about 100 K, where Lu 2 V 2 O 7 exhibits CMR; at higher temperature, where the magnetoresistance vanishes, these MP also disappear. This observation confirms the MP-mediated model of CMR and reveals the microscopic size of the MP in magnetoresistive pyrochlores. (paper)

  7. First-principles study of strong correlation effects in pyrochlore iridates

    Energy Technology Data Exchange (ETDEWEB)

    Shinaoka, Hiroshi [Department of Physics, Saitama University (Japan); Hoshino, Shintaro [Department of Basic Science, The University of Tokyo (Japan); Troyer, Matthias [Theoretische Physik, ETH Zuerich (Switzerland); Werner, Philipp [Department of Physics, University of Fribourg (Switzerland)

    2016-07-01

    The pyrochlore iridates A{sub 2}Ir{sub 2}O{sub 7} (A=Pr, Nd, Y, etc.) are an ideal system to study fascinating phenomena induced by strong electron correlations and spin-orbit coupling. In this talk, we study strong correlation effects in the prototype compound Y{sub 2}Ir{sub 2}O{sub 7} using the local density approximation and dynamical mean-field theory (LDA+DMFT). We map out the phase diagram in the space of temperature, onsite Coulomb repulsion U, and filling. Consistent with experiments, we find that an all-in/all-out ordered insulating phase is stable for realistic values of U. We reveal the importance of the hybridization between j{sub eff} = 1/2 and j{sub eff} = 3/2 states under the Coulomb interaction and trigonal crystal field. We demonstrate a substantial band narrowing in the paramagnetic metallic phase and non-Fermi liquid behavior in the electron/hole doped system originating from long-lived quasi-spin moments induced by nearly flat bands. We further compare our results with recent experimental results of Eu{sub 2}Ir{sub 2}O{sub 7} under hydrostatic pressure.

  8. Single crystal growth and structure refinements of CsMxTe2-xO6 (M = Al, Ga, Ge, In) pyrochlores

    International Nuclear Information System (INIS)

    Siritanon, Theeranun; Sleight, A.W.; Subramanian, M.A.

    2011-01-01

    Graphical abstract: Single crystals of CsM x Te 2-x O 6 pyrochlores with M = Al, Ga, Ge, and In have been grown and structure refinements indicate deviations from ideal stoichiometry presumably related to mixed valency of tellurium. Highlights: → Single crystals of CsM x Te 2-x O 6 pyrochlores with M = Al, Ga, Ge, and In have been grown. → Structure refinements from single crystal X-ray diffraction data confirm e structure. → Deviations from ideal stoichiometry suggest mixed valency of tellurium and hence conductivity. -- Abstract: Single crystals of CsM x Te 2-x O 6 pyrochlores with M = Al, Ga, Ge, and In have been grown from a TeO 2 flux. Structure refinements from single crystal X-ray diffraction data are reported. These results are used to discuss deviations from ideal stoichiometry that result in electronic conductivity presumably related to mixed valency of tellurium.

  9. Conductivity and hydration trends in disordered fluorite and pyrochlore oxides: A study on lanthanum cerate–zirconate based compounds

    DEFF Research Database (Denmark)

    Besikiotis, Vasileios; Ricote, Sandrine; Jensen, Molly Hjorth

    2012-01-01

    In the present contribution we discuss the influence of order/disorder on the concentration and mobility of ionic charge carriers in undoped and acceptor (calcium) doped fluorite and pyrochlore structured lanthanum cerate–zirconate solid solutions: (La1−yCay)2(Ce1−xZrx)2O7−δ (y=0, 0.02, 0.10; x=0...... enthalpy becomes more exothermic with higher cerium content, i.e. with more disordered materials. The proton conductivity decreases upon acceptor substitution of La3+ with Ca2+ which is attributed to trapping of the charge carriers by the effectively negative acceptor....

  10. Cooper-pair formation by anharmonic rattling modes in the β-pyrochlore superconductor KOs2O6

    Science.gov (United States)

    Chang, Jun; Eremin, Ilya; Thalmeier, Peter

    2009-05-01

    We study the influence of anharmonic rattling phonons in the β-pyrochlore superconductor KOs2O6 using the strong-coupling Eliashberg approach. In particular, by analyzing the specific heat data, we find that the rattling phonon frequency changes discontinuously at the critical temperature of the first-order phase transition. Solving the strong-coupling Eliashberg equations with effective temperature-dependent α2F(ω), we investigate the consequence of this first-order phase transition for the anomalous temperature dependence of the superconducting gap. We discuss our results in the context of the recent experimental data.

  11. Structural vs. intrinsic carriers: contrasting effects of cation chemistry and disorder on ionic conductivity in pyrochlores

    International Nuclear Information System (INIS)

    Perriot, Romain; Uberuaga, Blas P.

    2015-01-01

    We use molecular dynamics simulations to investigate the role of cation disorder on oxygen diffusion in Gd 2 Zr 2 O 7 (GZO) and Gd 2 Ti 2 O 7 (GTO) pyrochlores, a class of complex oxides which contain a structural vacancy relative to the basic fluorite structure. The introduction of disorder has distinct effects depending on the chemistry of the material, increasing the mobility of structural carriers by up to four orders of magnitude in GZO. In contrast, in GTO, there is no mobility at zero or low disorder on the ns timescale, but higher disorder liberates the otherwise immobile carriers, allowing diffusion with rates comparable to GZO for the fully disordered material. Here, we show that the cation disorder enhances the diffusivity by both increasing the concentration of mobile structural carriers and their individual mobility. The disorder also influences the diffusion in materials containing intrinsic carriers, such as additional vacancies VO or oxygen interstitials OI. And while in ordered GZO and GTO the contribution of the intrinsic carriers dominates the overall diffusion of oxygen, OI in GZO contributes along with structural carriers, and the total diffusion rate can be calculated by assuming simple additive contributions from the two sources. Although the disorder in the materials with intrinsic defects usually enhances the diffusivity as in the defect-free case, in low concentrations, cation antisites AB or BA, where A = Gd and B = Zr or Ti, can act as traps for fast intrinsic defects. The trapping results in a lowering of the diffusivity, and causes a non-monotonic behavior of the diffusivity with disorder. Conversely, in the case of slow intrinsic defects, the main effect of the disorder is to liberate the structural carriers, resulting in an increase of the diffusivity regardless of the defect trapping.

  12. Induced quadrupolar singlet ground state of praseodymium in a modulated pyrochlore

    Science.gov (United States)

    van Duijn, J.; Kim, K. H.; Hur, N.; Ruiz-Bustos, R.; Adroja, D. T.; Bridges, F.; Daoud-Aladine, A.; Fernandez-Alonso, F.; Wen, J. J.; Kearney, V.; Huang, Q. Z.; Cheong, S.-W.; Perring, T. G.; Broholm, C.

    2017-09-01

    The complex structure and magnetism of Pr2 -xBixRu2O7 was investigated by neutron scattering and extended x-ray absorption fine structure. Pr has an approximate doublet ground state and the first excited state is a singlet. While the B -site (Ru) is well ordered throughout, this is not the case for the A -site (Pr/Bi). A broadened distribution for the Pr-O2 bond length at low temperature indicates the Pr environment varies from site to site even for x =0 . The environment about the Bi site is highly disordered ostensibly due to the 6 s lone pairs on Bi3 +. Correspondingly, we find that the non-Kramers doublet ground-state degeneracy, otherwise anticipated for Pr in the pyrochlore structure, is lifted so as to produce a quadrupolar singlet ground state with a spatially varying energy gap. For x =0 , below TN, the Ru sublattice orders antiferromagnetically, with propagation vector k =(0 ,0 ,0 ) as for Y2Ru2O7 . No ordering associated with the Pr sublattice is observed down to 100 mK. The low-energy magnetic response of Pr2 -xBixRu2O7 features a broad spectrum of magnetic excitations associated with inhomogeneous splitting of the Pr quasidoublet ground state. For x =0 (x =0.97 ), the spectrum is temperature dependent (independent). It appears disorder associated with Bi alloying enhances the inhomogeneous Pr crystal-field level splitting so that intersite interactions become irrelevant for x =0.97 . The structural complexity for the A -site may be reflected in the hysteretic uniform magnetization of B -site ruthenium in the Néel phase.

  13. Crystal-field study of magnetization and specific heat properties of frustrated pyrochlore Pr2Zr2O7

    International Nuclear Information System (INIS)

    Alam, J.; Jana, Y.M.; Biswas, A. Ali

    2016-01-01

    The experimental results of temperature dependent dc magnetic susceptibility, field dependent isothermal magnetization, magnetic specific heat and entropy of the pyrochlore Pr 2 Zr 2 O 7 are simulated and analyzed using appropriate D 3d crystal-field (CF) and anisotropic molecular field tensors at Pr-sites in the self-consistent mean-field approach involving four magnetically non-equivalent rare-earth spins on the tetrahedral unit of the pyrochlore structure. CF level pattern and wave-functions of the ground 3 H 4 multiplet of the Pr 3+ ions are obtained considering intermediate coupling between different Russell-Saunders terms of the 4f 2 electronic configurations of Pr-ion and J-mixing effects. CF analysis shows that the CF ground-state of the Pr 3+ ion in Pr 2 Zr 2 O 7 is a well-isolated doublet, with significant admixtures of terms coming from |M J =±4〉 and |M J =±1〉, and the Pr-spins are effectively Ising-like along the local <111> axes. Magnetic specific heat in zero-field is simulated by considering a temperature dependence of the exchange splitting of the ground doublet. - Highlights: • Full CF diagonalization using intermediate coupling and J-mixing. • Pr-spins are Ising-like along local [111] axis. • Magnetic specific heat is due to temperature dependence exchange splitting of ground CF doublet.

  14. Structures and solid solution mechanisms of pyrochlore phases in the systems Bi2O3-ZnO-(Nb, Ta)2O5

    International Nuclear Information System (INIS)

    Tan, K.B.; Khaw, C.C.; Lee, C.K.; Zainal, Z.; Miles, G.C.

    2010-01-01

    Research highlights: → Combined XRD and ND Rietveld structural refinement of pyrochlores. → Structures and solid solution mechanisms of Bi-pyrochlores. → Bi and Zn displaced off-centre to different 96g A-site positions. → Summary of composition-structure-property of Bi-pyrochlores. - Abstract: The crystal structures of two pyrochlore phases have been determined by Rietveld refinement of combined X-ray and neutron powder diffraction data. These are stoichiometric, Bi 1.5 ZnTa 1.5 O 7 and non-stoichiometric Bi 1.56 Zn 0.92 Nb 1.44 O 6.86 . In both structures, Zn is distributed over A- and B-sites; Bi and Zn are displaced off-centre, to different 96g A-site positions; of the three sets of oxygen positions, O(1) are full, O(2) contain vacancies and O(3) contain a small number of oxygen, again in both cases. Comparisons between these structures, those of related Sb analogues and literature reports are made.

  15. Two-magnon scattering in the 5d all-in-all-out pyrochlore magnet Cd2Os2O7.

    Science.gov (United States)

    Nguyen, Thi Minh Hien; Sandilands, Luke J; Sohn, C H; Kim, C H; Wysocki, Aleksander L; Yang, In-Sang; Moon, S J; Ko, Jae-Hyeon; Yamaura, J; Hiroi, Z; Noh, Tae Won

    2017-08-15

    5d pyrochlore oxides with all-in-all-out magnetic order are prime candidates for realizing strongly correlated, topological phases of matter. Despite significant effort, a full understanding of all-in-all-out magnetism remains elusive as the associated magnetic excitations have proven difficult to access with conventional techniques. Here we report a Raman spectroscopy study of spin dynamics in the all-in-all-out magnetic state of the 5d pyrochlore Cd 2 Os 2 O 7 . Through a comparison between the two-magnon scattering and spin-wave theory, we confirm the large single ion anisotropy in this material and show that the Dzyaloshinskii-Moriya and exchange interactions play a significant role in the spin-wave dispersions. The Raman data also reveal complex spin-charge-lattice coupling and indicate that the metal-insulator transition in Cd 2 Os 2 O 7 is Lifshitz-type. Our work establishes Raman scattering as a simple and powerful method for exploring the spin dynamics in 5d pyrochlore magnets.Pyrochlore 5d transition metal oxides are expected to have interesting forms of magnetic order but are hard to study with conventional probes. Here the authors show that Raman scattering can be used to measure magnetic excitations in Cd 2 Os 2 O 7 and that it exhibits complex spin-charge-lattice coupling.

  16. Geometrical frustration in the ferromagnetic pyrochlore Ho2Ti2O7

    DEFF Research Database (Denmark)

    Harris, M.J.; Bramwell, S.T.; McMorrow, D.F.

    1997-01-01

    We report a detailed study of the pyrochlore Ho2Ti2O7, in which the magnetic ions (Ho3+) are ferromagnetically coupled with J similar to 1 K. We show that the presence of local Ising anisotropy leads to a geometrically frustrated ground state, preventing long-range magnetic order down to at least 0...

  17. Electrical transport properties of manganese containing pyrochlore type semiconducting oxides using impedance analyses

    International Nuclear Information System (INIS)

    Sumi, S.; Prabhakar Rao, P.; Mahesh, S.K.; Koshy, Peter

    2012-01-01

    Graphical abstract: DC conductivity variation of CaCe 1−x Mn x SnNbO 7−δ (x = 0, 0.2, 0.4 and 0.6) with inverse of temperature. Variation of conductivity with Mn concentration at 600 °C is shown in the inset. Display Omitted Highlights: ► We have observed that the structural ordering as well as grain size increase with Mn substitution. ► Impedance analysis proved that a correlated barrier hopping type conduction mechanism is involved in the materials. ► Activation energy as well as electrical conductivity increases with increase in Mn substitution. ► Localization of electrons associated with Mn 2+ and structural ordering are the key factors for the increased activation energy with Mn substitution. ► All the materials showed good NTC thermistor properties. -- Abstract: A new series of manganese containing pyrochlore type semiconducting oxides CaCe 1−x Mn x SnNbO 7−δ (x = 0, 0.2, 0.4 and 0.6) have been synthesized to study the effect of Mn substitution on the structure, microstructure and electrical properties of these samples. X-ray diffraction and scanning electron microscopy studies revealed an increase of structural ordering and grain size respectively with increase of Mn substitution. Rietveld analysis and Raman spectroscopy were also employed to corroborate the XRD results. The bulk resistance measurements with temperature exhibit negative temperature coefficient behavior. The impedance analysis of the samples revealed a non-Debye type relaxation existed in the materials. The ac conductivity variation with temperature and frequency indicates a correlated barrier hopping type conduction mechanism in these materials. The barrier height and the intersite separation for hopping influence the electrical conductivity of these samples and are found to be a function of localization of electrons associated with the Mn 2+ ions and the unit cell volume respectively. The Mn substitution increases both electrical conductivity and activation energy

  18. Quantum Magnetism Applied to the Iron-Pnictides and Rare Earth Pyrochlores

    Science.gov (United States)

    Applegate, Ryan

    This dissertation presents computational studies of two families of magnetic materials of significant current interest. The iron pnictides are new high temperature superconductors with interesting parent compound antiferromagnetism. The rare earth pyrochlore material Yb2Ti2O7 is a candidate quantum spin ice. The magnetic and structural phases of individual iron pnictides have both many common features and material specific differences. In an attempt to unify these behaviors as instances of a larger theoretical picture, we use Monte Carlo simulations of a two-dimensional Hamiltonian with coupled Heisenberg-spin and Ising-orbital degrees of freedom. We introduce spin-space and single-ion anisotropies and study the finite temperature transitions in our model. We develop a phase diagram and propose that the interplay of spin and orbital physics in the presence of anisotropy could explain how material details affect the transitions of the pnictide materials. Nuclear magnetic resonance (NMR) can study magnetic materials via the hyperfine interaction and the coupling between the nuclear moment and the field produced by the samples local moment environment. Recent measurements suggest that Zn doped BaFe2As2 may have quantum fluctuations about the striped phase that produce a distribution of fields at As nuclear sites. The non-magnetic ion Zn replaces Fe and can be treated as an impurity which can be studied by a zero-temperature Ising Series expansion method. We propose a Heisenberg-like J1a-J 1b-J2 model which has small ferromagnetic exchanges along the b axis and strong antiferromagnetic exchanges along the a axis. In our impurity model we find that the magnetic moments are everywhere reduced by quantum fluctuations, except on the nearest neighbor site in the AFM direction. We suggest that the presented impurity model may provide an explanation for the experimental measurements. Based on a recently proposed quantum spin ice model, we use numerical linked cluster (NLC

  19. Effect of excess Mg and Excess Nb incorporation into the B-site of pyrochlore in the Pb-Mg-Nb-O system

    Directory of Open Access Journals (Sweden)

    Mergen, A.

    2002-12-01

    Full Text Available In the Pb-Mg-Nb-O system, excess Mg and excess Nb incorporation into the B-site of PMN pyrochlore were investigated along the compositons of Pb1.83Mg0.29+xNb1.71-xO6.39-1.5x where x=0.1, 0.2, 0.3, 0.4, 0.522 and Pb1.83Mg0.29-xNb1.71+xO6.39+1.5x where x=0.1, 0.2, 0.29 respectively. Excess Mg incorporation led to the formation of perovskite and excess Nb resulted in formation of Pb2Nb2O7 monoclinic pyrochlore. The densities of the PMN pyrochlore-PMN perovskite mixtures decreased with an increase in Mg concentration. The relative permittivity of the mixtures increased with decreasing pyrochlore content. The effect of pyrochlore on the permittivity follows the Weiner’s mixture rule up to a pyrochlore content of 50 vol%.

    Se investigó la incorporación en lugares B de pirocloro PMN de un exceso de Mg y un exceso de Nb. En el sistema Pb-Mg-Nb-O2 las composiciones analizadas fueron Pb1.83Mg0.29+xNb1.71-xO6.39-1.5x donde x=0.1, 0.2, 0.3, 0.4, 0.522 y en Pb1.83Mg0.29-xNb1.71+xO6.39+1.5x donde x= 0.1, 0.2,0.29. El exceso de Mg condujo a la formación de perovskita y el exceso de Nb resultó en la formación del pirocloro monolínico, Pb2Nb2O7. La densidad de la mezcla de PMN pirocloro-perovskita dismunuye con el aumento de la concentración de Mg. La permitividad dieléctrica de las mezclas aumenta con la disminución del contenido de pirocloro. El efecto del pirocloro sobre la permitividad sigue la regla de mezclas de Weiner hasta conenidos de pirocloro del 50%.

  20. Investigations of the magnetic properties in the pyrochlore Ho{sub 2}Ti{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Schoenemann, Rico; Herrmannsdoerfer, Thomas; Green, Elizabeth Lauren; Wang, Zhaosheng; Wosnitza, Joachim [Dresden High Magnetic Field Laboratory, Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany); Skrotzki, Richard [Dresden High Magnetic Field Laboratory, Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany); Department of Chemistry and Food Chemistry, TU Dresden, Dresden (Germany); Kaneko, Hiroshi; Suzuki, Haruhiko [Faculty of Mathematics and Physics, Kanazawa University, Kanazawa (Japan)

    2013-07-01

    Pyrochlore compounds such as R{sub 2}Ti{sub 2}O{sub 7} (where R is Ho or Dy) have an highly degenerate ground state where the R{sup 3+} moments obey the ''ice rules''. This provides access to study extraordinary physical phenomena, like the formation of magnetic monopoles. Recent publications evidence monopoles which can be probed using high frequency (adiabatic) susceptibility measurements. We performed ac susceptibility measurements on a single-crystal Ho{sub 2}Ti{sub 2}O{sub 7} sample at low temperatures down to 30 mK and magnetic fields up to 14 T. Based on isothermal frequency sweeps we were able to determine spin relaxation rates. Both the real and imaginary parts of the temperature-dependent magnetic susceptibility measurements show the spins freezing below 1 K and provide insight into the magnetic-monopole density.

  1. Sudden Disappearance of the First-Order Transition in β-Pyrochlore KOs2O6 under Low Pressure

    Science.gov (United States)

    Umeo, Kazunori; Kubo, Hirokazu; Yamaura, Jun-ichi; Hiroi, Zenji; Takabatake, Toshiro

    2009-12-01

    We report the first observation of the pressure effect on the first-order transition at Tp = 7.5 K in the β-pyrochlore oxide superconductor KOs2O6 by specific-heat measurement. The peak in the specific heat at Tp disappeared at a low pressure of 0.02 GPa. With increasing pressure up to 0.02 GPa, the coefficient of the T5 dependence of the specific heat increases by 30%. This finding implies that low-energy excitations of phonons are enhanced by the suppression of the first-order transition. However, the specific-heat jump at Tc is unchanged with pressure up to 1 GPa, indicating that the strong coupling superconductivity is rather robust under pressure.

  2. Nuclear resonance scattering study of iridates, iridium and antimony based pyrochlores

    International Nuclear Information System (INIS)

    Alexeev, P.

    2017-04-01

    these compounds. In order to broaden the perspectives of NRS with the 73 keV resonance the first room temperature NRS on iridium metal is carried out. The results demonstrate NRS as a powerful research tool for the studies of iridium physics due to the high energy of the resonant photons and the high natural abundance of the "1"9"3Ir isotope under study, paving the way for studies of magnetism and electronic properties under extreme conditions. The second part of this work is dedicated to vibrational spectroscopy with Nuclear Inelastic Scattering (NIS). A sapphire backscattering monochromator was designed, installed and tested at the beamline. It provides high energy resolution due to the sub-mK temperature control, though the resolution is limited from theoretically proposed sub-meV to meV by the quality of currently available sapphire crystals. With this device the energy resolution of 1.3(1) meV at 23.88 keV and of 3.2(4) meV at 37.13 keV was achieved. Following this development, the vibrational spectra of antimony in defect pyrochlore Ag-Sb-O compounds have been measured by means of NIS at 37.13 keV. Density of phonon states for the Sb(III) and for the Sb(V) site has been unambiguously revealed. The difference in site-specific antimony modes illustrates the importance of lattice dynamics for the engineering of these compounds.

  3. Nuclear resonance scattering study of iridates, iridium and antimony based pyrochlores

    Energy Technology Data Exchange (ETDEWEB)

    Alexeev, P.

    2017-04-15

    on Ir nucleus have been determined for these compounds. In order to broaden the perspectives of NRS with the 73 keV resonance the first room temperature NRS on iridium metal is carried out. The results demonstrate NRS as a powerful research tool for the studies of iridium physics due to the high energy of the resonant photons and the high natural abundance of the {sup 193}Ir isotope under study, paving the way for studies of magnetism and electronic properties under extreme conditions. The second part of this work is dedicated to vibrational spectroscopy with Nuclear Inelastic Scattering (NIS). A sapphire backscattering monochromator was designed, installed and tested at the beamline. It provides high energy resolution due to the sub-mK temperature control, though the resolution is limited from theoretically proposed sub-meV to meV by the quality of currently available sapphire crystals. With this device the energy resolution of 1.3(1) meV at 23.88 keV and of 3.2(4) meV at 37.13 keV was achieved. Following this development, the vibrational spectra of antimony in defect pyrochlore Ag-Sb-O compounds have been measured by means of NIS at 37.13 keV. Density of phonon states for the Sb(III) and for the Sb(V) site has been unambiguously revealed. The difference in site-specific antimony modes illustrates the importance of lattice dynamics for the engineering of these compounds.

  4. Pyrochlore type semiconducting ceramic oxides in Ca-Ce-Ti-M-O system (M = Nb or Ta)-Structure, microstructure and electrical properties

    International Nuclear Information System (INIS)

    Deepa, M.; Prabhakar Rao, P.; Radhakrishnan, A.N.; Sibi, K.S.; Koshy, Peter

    2009-01-01

    A new series of pyrochlore type ceramic semiconducting oxides in Ca-Ce-Ti-M-O (M = Nb or Ta) system has been synthesized by the conventional ceramic route. The electrical conductivity measurements show that these oxides exhibit semiconducting behavior and the conductivity increases with the Ce content in the compound. Activation energy of the current carriers is in the range of 0.5-1.6 eV. The electrical conductivity in these oxides is due to the presence of Ce 3+ , which remains in the reduced state without being oxidized to Ce 4+ by structural stabilization. The photoluminescence and X-ray photoelectron spectroscopy analysis corroborate the presence of Ce in the 3+ state. Impedance spectral analysis is carried out to evaluate the transport properties and indicates that the conduction in these compounds is mainly due to electronic contribution. The X-ray powder diffraction and Raman spectroscopy analysis establishes that these oxides belong to a cubic pyrochlore type structure.

  5. Structural and photoluminescence properties of stannate based displaced pyrochlore-type red phosphors: Ca(3-x)Sn₃Nb₂O₁₄:xEu³⁺.

    Science.gov (United States)

    Sreena, T S; Prabhakar Rao, P; Francis, T Linda; Raj, Athira K V; Babu, Parvathi S

    2015-05-14

    New stannate based displaced pyrochlore-type red phosphors, Ca(3-x)Sn3Nb2O14:xEu(3+), were prepared via a conventional solid state method. The influence of partial occupancy of Sn in both A and B sites of the pyrochlore-type oxides on the photoluminescence properties was studied using powder X-ray diffraction, FT-Raman, transmission electron microscopy, scanning electron microscopy with energy dispersive spectrometry, UV-visible absorption spectroscopy, and photoluminescence excitation and emission spectra with lifetime measurements. The structural analysis establishes that these oxides belong to a cubic displaced pyrochlore type structure with a space group Fd3̄m. These phosphors exhibit strong absorptions at near UV and blue wavelength regions and emit intense multiband emissions due to Eu(3+ 5)D0-(7)F(0, 1, 2) transitions. The absence of characteristic MD transition splitting points out that local cation disorder exists in this type of displaced pyrochlores, reducing the D(3d) inversion symmetry, which is not evidenced by such disorder in the X-ray diffraction analysis. The unusual forbidden intense sharp (5)D0-(7)F0 transition indicates single site occupancy of Eu(3+) with a narrower range of bonding environment, preventing the cluster formation. This is supported by the stable (5)D0 lifetime with Eu(3+) concentration. The Judd-Ofelt intensity parameter assessment corroborates these results. The CIE color coordinates of these phosphors were found to be (0.60, 0.40), which are close to the NTSC standard values (0.67, 0.33) for a potential red phosphor.

  6. Effects of sintering temperature on the pyrochlore phase in PZT nanotubes and their transformation to the perovskite phase by coating with PbO multilayers.

    Science.gov (United States)

    Han, Jin Kyu; Choi, Yong Chan; Jeon, Do Hyen; Lee, Min Ku; Bu, Sang Don

    2014-11-01

    We report the phase evolution of Pb(Zr0.52Ti0.48)O3 nanotubes (PZT-NTs), from the pyrochlore to perovskite phase, with an outer diameter of about 420 nm and a wall thickness of about 10 nm. The PZT-NTs were fabricated in pores of porous anodic alumina membrane (PAM) using a spin coating of PZT sol-gel solution and subsequent annealing at 500-700 degrees C in oxygen gas. The pyrochlore phase was found to be formed at 500 degrees C, and also found not to be transformed into the perovskite phase, even though annealing was performed at higher temperatures to 700 degrees C. Elementary distribution analysis of PZT-NTs embedded in PAM reveal that Pb diffusion from nanotubes into pore walls of PAM is one of the main reasons. By employing firstly an additional PbO coating on the pyrochlore nanotubes and then subsequent annealing at 700 degrees C, we have successfully achieved an almost pure perovskite phase in nanotubes. These results suggest that PbO acts as a Pb-compensation agent in the Pb- deficient PZT-NTs. Moreover, our method can be used in the synthesis of all metal-oxide materials, including volatile elements.

  7. Atomic-scale microstructures, Raman spectra and dielectric properties of cubic pyrochlore-typed Bi1.5MgNb1.5O7 dielectric ceramics

    KAUST Repository

    Li, Yangyang

    2014-07-01

    Single-phase cubic pyrochlore-typed Bi1.5MgNb 1.5O7 (BMN) dielectric ceramics were synthesized at temperatures of 1050-1200 °C by solid-state reaction method. Their atomic-scale microstructures and dielectric properties were investigated. X-ray diffraction patterns revealed that the BMN ceramics had an average cubic pyrochlore structure, whereas the Raman spectra indicated that they had an essentially cubic symmetry with small local deviations at the A and O\\' sites of the cubic pyrochlore structure. This was confirmed by selected electron area diffraction (SAED) patterns, where the reflections of {442} (not allowed in the cubic pyrochlore with Fd3̄m symmetry) were clearly observed. SEM and TEM images revealed that the average grain size was increased with the sintering temperature, and an un-homogeneous grain growth was observed at high temperatures. HRTEM images and SAED patterns revealed the single-crystalline nature of the BMN ceramic grains. Energy dispersive spectroscopy (EDS) elemental mapping studies indicated that the compositional distributions of Bi, Mg, Nb and O elements in the ceramic grains were homogenous, and no elemental precipitation was observed at the grain boundary. Quantitative EDS data on ceramic grains revealed the expected cationic stoichiometry based on the initial composition of Bi1.5MgNb1.5O7. Dielectric constants of all the BMN samples exhibited almost frequency independent characteristic in the frequency range of 102-106 Hz, and the highest value was 195 for the BMN ceramics sintered at sintered at 1150 °C with the highest bulk density. The dielectric losses were stable and less than 0.002 in the frequency range of 102-105 Hz. The high dielectric constants of the present BMN samples can be ascribed to the local atomic deviations at the A and O\\' sites from the ideal atomic positions of the pyrochlore structure, which affect the different polarization mechanisms in the BMN ceramics, and which in turn enhance the dielectric

  8. Atomic-scale microstructures, Raman spectra and dielectric properties of cubic pyrochlore-typed Bi1.5MgNb1.5O7 dielectric ceramics

    KAUST Repository

    Li, Yangyang; Zhu, Xinhua; Al-Kassab, Talaat

    2014-01-01

    Single-phase cubic pyrochlore-typed Bi1.5MgNb 1.5O7 (BMN) dielectric ceramics were synthesized at temperatures of 1050-1200 °C by solid-state reaction method. Their atomic-scale microstructures and dielectric properties were investigated. X-ray diffraction patterns revealed that the BMN ceramics had an average cubic pyrochlore structure, whereas the Raman spectra indicated that they had an essentially cubic symmetry with small local deviations at the A and O' sites of the cubic pyrochlore structure. This was confirmed by selected electron area diffraction (SAED) patterns, where the reflections of {442} (not allowed in the cubic pyrochlore with Fd3̄m symmetry) were clearly observed. SEM and TEM images revealed that the average grain size was increased with the sintering temperature, and an un-homogeneous grain growth was observed at high temperatures. HRTEM images and SAED patterns revealed the single-crystalline nature of the BMN ceramic grains. Energy dispersive spectroscopy (EDS) elemental mapping studies indicated that the compositional distributions of Bi, Mg, Nb and O elements in the ceramic grains were homogenous, and no elemental precipitation was observed at the grain boundary. Quantitative EDS data on ceramic grains revealed the expected cationic stoichiometry based on the initial composition of Bi1.5MgNb1.5O7. Dielectric constants of all the BMN samples exhibited almost frequency independent characteristic in the frequency range of 102-106 Hz, and the highest value was 195 for the BMN ceramics sintered at sintered at 1150 °C with the highest bulk density. The dielectric losses were stable and less than 0.002 in the frequency range of 102-105 Hz. The high dielectric constants of the present BMN samples can be ascribed to the local atomic deviations at the A and O' sites from the ideal atomic positions of the pyrochlore structure, which affect the different polarization mechanisms in the BMN ceramics, and which in turn enhance the dielectric constants of

  9. Atomic scale simulations of pyrochlore oxides with a tight-binding variable-charge model: implications for radiation tolerance

    International Nuclear Information System (INIS)

    Sattonnay, G; Tétot, R

    2014-01-01

    Atomistic simulations with new interatomic potentials derived from a tight-binding variable-charge model were performed in order to investigate the lattice properties and the defect formation energies in Gd 2 Ti 2 O 7 and Gd 2 Zr 2 O 7 pyrochlores. The main objective was to determine the role played by the defect stability on the radiation tolerance of these compounds. Calculations show that the titanate has a more covalent character than the zirconate. Moreover, the properties of oxygen Frenkel pairs, cation antisite defects and cation Frenkel pairs were studied. In Gd 2 Ti 2 O 7 the cation antisite defect and the Ti-Frenkel pair are not stable: they evolve towards more stable defect configurations during the atomic relaxation process. This phenomenon is driven by a decrease of the Ti coordination number down to five which leads to a local atomic reorganization and strong structural distortions around the defects. These kinds of atomic rearrangements are not observed around defects in Gd 2 Zr 2 O 7 . Therefore, the defect stability in A 2 B 2 O 7 depends on the ability of B atoms to accommodate high coordination number (higher than six seems impossible for Ti). The accumulation of structural distortions around Ti-defects due to this phenomenon could drive the Gd 2 Ti 2 O 7 amorphization induced by irradiation. (paper)

  10. Quasiparticle Breakdown and Spin Hamiltonian of the Frustrated Quantum Pyrochlore Yb2 Ti2 O7 in a Magnetic Field

    Science.gov (United States)

    Thompson, J. D.; McClarty, P. A.; Prabhakaran, D.; Cabrera, I.; Guidi, T.; Coldea, R.

    2017-08-01

    The frustrated pyrochlore magnet Yb2 Ti2 O7 has the remarkable property that it orders magnetically but has no propagating magnons over wide regions of the Brillouin zone. Here we use inelastic neutron scattering to follow how the spectrum evolves in cubic-axis magnetic fields. At high fields we observe, in addition to dispersive magnons, a two-magnon continuum, which grows in intensity upon reducing the field and overlaps with the one-magnon states at intermediate fields leading to strong renormalization of the dispersion relations, and magnon decays. Using heat capacity measurements we find that the low- and high-field regions are smoothly connected with no sharp phase transition, with the spin gap increasing monotonically in field. Through fits to an extensive data set of dispersion relations combined with magnetization measurements, we reevaluate the spin Hamiltonian, finding dominant quantum exchange terms, which we propose are responsible for the anomalously strong fluctuations and quasiparticle breakdown effects observed at low fields.

  11. All-in-all-out magnetic domain size in pyrochlore iridate thin films as probed by local magnetotransport

    Energy Technology Data Exchange (ETDEWEB)

    Fujita, T. C.; Uchida, M., E-mail: uchida@ap.t.u-tokyo.ac.jp; Kozuka, Y.; Ogawa, S. [Department of Applied Physics and Quantum-Phase Electronics Center (QPEC), University of Tokyo, Tokyo 113-8656 (Japan); Tsukazaki, A. [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); PRESTO, Japan Science and Technology Agency (JST), Tokyo 102-0075 (Japan); Arima, T. [Department of Advanced Materials Science, University of Tokyo, Kashiwa 277-8561 (Japan); RIKEN Center for Emergent Matter Science (CEMS), Wako 351-0198 (Japan); Kawasaki, M. [Department of Applied Physics and Quantum-Phase Electronics Center (QPEC), University of Tokyo, Tokyo 113-8656 (Japan); RIKEN Center for Emergent Matter Science (CEMS), Wako 351-0198 (Japan)

    2016-01-11

    Pyrochlore iridates have attracted growing attention because of a theoretical prediction of a possible topological semimetal phase originating from all-in-all-out spin ordering. Related to the topological band structure, recent findings of the magnetic domain wall conduction have stimulated investigations of magnetic domain distribution in this system. Here, we investigate the size of magnetic domains in Eu{sub 2}Ir{sub 2}O{sub 7} single crystalline thin films by magnetoresistance (MR) using microscale Hall bars. Two distinct magnetic domains of the all-in-all-out spin structure are known to exhibit linear MR but with opposite signs, which enables us to estimate the ratio of the two domains in the patterned channel. The linear MR for 80 × 60 μm{sup 2} channel is nearly zero after zero-field cooling, suggesting random distribution of domains smaller than the channel size. In contrast, the wide distribution of the value of the linear MR is detected in 2 × 2 μm{sup 2} channel, reflecting the detectable domain size depending on each cooling-cycle. Compared to simulation results, we estimate the average size of a single all-in-all-out magnetic domain as 1–2 μm.

  12. Quasiparticle Breakdown and Spin Hamiltonian of the Frustrated Quantum Pyrochlore Yb_{2}Ti_{2}O_{7} in a Magnetic Field.

    Science.gov (United States)

    Thompson, J D; McClarty, P A; Prabhakaran, D; Cabrera, I; Guidi, T; Coldea, R

    2017-08-04

    The frustrated pyrochlore magnet Yb_{2}Ti_{2}O_{7} has the remarkable property that it orders magnetically but has no propagating magnons over wide regions of the Brillouin zone. Here we use inelastic neutron scattering to follow how the spectrum evolves in cubic-axis magnetic fields. At high fields we observe, in addition to dispersive magnons, a two-magnon continuum, which grows in intensity upon reducing the field and overlaps with the one-magnon states at intermediate fields leading to strong renormalization of the dispersion relations, and magnon decays. Using heat capacity measurements we find that the low- and high-field regions are smoothly connected with no sharp phase transition, with the spin gap increasing monotonically in field. Through fits to an extensive data set of dispersion relations combined with magnetization measurements, we reevaluate the spin Hamiltonian, finding dominant quantum exchange terms, which we propose are responsible for the anomalously strong fluctuations and quasiparticle breakdown effects observed at low fields.

  13. Catalytic Oxidation of Soot on a Novel Active Ca-Co Dually-Doped Lanthanum Tin Pyrochlore Oxide

    Directory of Open Access Journals (Sweden)

    Lijie Ai

    2018-04-01

    Full Text Available A novel active Ca-Co dually-doping pyrochlore oxide La2−xCaxSn2−yCoyO7 catalyst was synthesized by the sol-gel method for catalytic oxidation of soot particulates. The microstructure, atomic valence, reduction, and adsorption performance were investigated by X-ray powder diffraction (XRD, scanning electron microscope (SEM, Fourier-transform infrared spectroscopy (FT-IR, X-ray photoelectron spectroscopy (XPS, H2-TPR (temperature-programmed reduction, and in situ diffuse reflection infrared Fourier transformed (DRIFTS techniques. Temperature programmed oxidation (TPO tests were performed with the mixture of soot-catalyst under tight contact conditions to evaluate the catalytic activity for soot combustion. Synergetic effect between Ca and Co improved the structure and redox properties of the solids, increased the surface oxygen vacancies, and provided a suitable electropositivity for oxide, directly resulting in the decreased ignition temperature for catalyzed soot oxidation as low as 317 °C. The presence of NO in O2 further promoted soot oxidation over the catalysts with the ignition temperature decreased to about 300 °C. The DRIFTS results reveal that decomposition of less stable surface nitrites may account for NO2 formation in the ignition period of soot combustion, which thus participate in the auxiliary combustion process.

  14. Superconducting and Structural Transitions in the β-Pyrochlore Oxide KOs2O6 under High Pressure

    Science.gov (United States)

    Ogusu, Hiroki; Takeshita, Nao; Izawa, Koichi; Yamaura, Jun-ichi; Ohishi, Yasuo; Tsutsui, Satoshi; Okamoto, Yoshihiko; Hiroi, Zenji

    2010-11-01

    Rattling-induced superconductivity in the β-pyrochlore oxide KOs2O6 is investigated under high pressure up to 5 GPa. Resistivity measurements in a high-quality single crystal reveal a gradual decrease in the superconducting transition temperature Tc from 9.7 K at 1.0 GPa to 6.5 K at 3.5 GPa, followed by a sudden drop to 3.3 K at 3.6 GPa. Powder X-ray diffraction experiments show a structural transition from cubic to monoclinic or triclinic at a similar pressure. The sudden drop in Tc is ascribed to this structural transition, by which an enhancement in Tc due to a strong electron-rattler interaction present in the low-pressure cubic phase is abrogated as the rattling of the K ion is completely suppressed or weakened in the high-pressure phase of reduced symmetry. In addition, we find two anomalies in the temperature dependence of resistivity in the low-pressure phase, which may be due to subtle changes in rattling vibration.

  15. Anomalous pressure dependence of the superconducting transition temperature in the β-Pyrochlore KOs2O6

    Science.gov (United States)

    Miyoshi, Kiyotaka; Takaichi, Yuta; Takeuchi, Jun

    2009-03-01

    DC magnetic measurements have been performed for β-pyrochlore superconductor KOs2O6 (Tc = 9.6 K) under pressure for the precise determination of the pressure dependence of Tc, using a miniature diamond anvil cell combined with a commercial SQUID magnetometer. It is found that the critical temperature Tc shows a maximum of ~10 K at P=0.5 GPa. The maximum of Tc is higher than that for CsOs2O6 and RbOs2O6, in both of which Tc is known to increase and saturate at Tcm = 8.8 K by the application of pressure, suggesting the enhanced superconductivity due to the rattling of K ions in an oversized cage of Os-O network. For the further application of pressure, Tc decreases linearly but the decreasing rate appears to be suddenly changed at P~2 GPa and Tc~8 K. The sharp bend of the Tc — P line probably corresponds to the transition concerning to the rattling motion which occurs at Tp=7.5 K at ambient pressure, suggesting the positive pressure dependence of Tp.

  16. Signatures of a gearwheel quantum spin liquid in a spin-1/2 pyrochlore molybdate Heisenberg antiferromagnet

    Science.gov (United States)

    Iqbal, Yasir; Müller, Tobias; Riedl, Kira; Reuther, Johannes; Rachel, Stephan; Valentí, Roser; Gingras, Michel J. P.; Thomale, Ronny; Jeschke, Harald O.

    2017-12-01

    We theoretically investigate the low-temperature phase of the recently synthesized Lu2Mo2O5N2 material, an extraordinarily rare realization of a S =1 /2 three-dimensional pyrochlore Heisenberg antiferromagnet in which Mo5 + are the S =1 /2 magnetic species. Despite a Curie-Weiss temperature (ΘCW) of -121 (1 ) K, experiments have found no signature of magnetic ordering or spin freezing down to T*≈0.5 K. Using density functional theory, we find that the compound is well described by a Heisenberg model with exchange parameters up to third nearest neighbors. The analysis of this model via the pseudofermion functional renormalization group method reveals paramagnetic behavior down to a temperature of at least T =| ΘCW|/100 , in agreement with the experimental findings hinting at a possible three-dimensional quantum spin liquid. The spin susceptibility profile in reciprocal space shows momentum-dependent features forming a "gearwheel" pattern, characterizing what may be viewed as a molten version of a chiral noncoplanar incommensurate spiral order under the action of quantum fluctuations. Our calculated reciprocal space susceptibility maps provide benchmarks for future neutron scattering experiments on single crystals of Lu2Mo2O5N2 .

  17. Use of linear free energy relationship to predict Gibbs free energies of formation of pyrochlore phases (CaMTi2O7)

    International Nuclear Information System (INIS)

    Xu, H.; Wang, Y.

    1999-01-01

    In this letter, a linear free energy relationship is used to predict the Gibbs free energies of formation of crystalline phases of pyrochlore and zirconolite families with stoichiometry of MCaTi 2 O 7 (or, CaMTi 2 O 7 ,) from the known thermodynamic properties of aqueous tetravalent cations (M 4+ ). The linear free energy relationship for tetravalent cations is expressed as ΔG f,M v X 0 =a M v X ΔG n,M 4+ 0 +b M v X +β M v X r M 4+ , where the coefficients a M v X , b M v X , and β M v X characterize a particular structural family of M v X, r M 4+ is the ionic radius of M 4+ cation, ΔG f,M v X 0 is the standard Gibbs free energy of formation of M v X, and ΔG n,M 4+ 0 is the standard non-solvation energy of cation M 4+ . The coefficients for the structural family of zirconolite with the stoichiometry of M 4+ CaTi 2 O 7 are estimated to be: a M v X =0.5717, b M v X =-4284.67 (kJ/mol), and β M v X =27.2 (kJ/mol nm). The coefficients for the structural family of pyrochlore with the stoichiometry of M 4+ CaTi 2 O 7 are estimated to be: a M v X =0.5717, b M v X =-4174.25 (kJ/mol), and β M v X =13.4 (kJ/mol nm). Using the linear free energy relationship, the Gibbs free energies of formation of various zirconolite and pyrochlore phases are calculated. (orig.)

  18. Order-disorder phase transformations in quaternary pyrochlore oxide system: Investigated by X-ray diffraction, transmission electron microscopy and Raman spectroscopic techniques

    International Nuclear Information System (INIS)

    Radhakrishnan, A.N.; Prabhakar Rao, P.; Sibi, K.S.; Deepa, M.; Koshy, Peter

    2009-01-01

    Order-disorder transformations in a quaternary pyrochlore oxide system, Ca-Y-Zr-Ta-O, were studied by powder X-ray diffraction (XRD) method, transmission electron microscope (TEM) and FT-NIR Raman spectroscopic techniques. The solid solutions in different ratios, 4:1, 2:1, 1:1, 1:2, 1:4, 1:6, of CaTaO 3.5 and YZrO 3.5 were prepared by the conventional high temperature ceramic route. The XRD results and Rietveld analysis revealed that the crystal structure changed from an ordered pyrochlore structure to a disordered defect fluorite structure as the ratios of the solid solutions of CaTaO 3.5 and YZrO 3.5 were changed from 4:1 to 1:4. This structural transformation in the present system is attributed to the lowering of the average cation radius ratio, r A /r B as a result of progressive and simultaneous substitution of larger cation Ca 2+ for Y 3+ at A sites and smaller cation Ta 5+ for Zr 4+ at B sites. Raman spectroscopy and TEM analysis corroborated the XRD results. - Graphical abstract: Selected area electron diffraction (SAED) patterns showed highly ordered diffraction maxima with characteristic superlattice weak diffraction spots of the pyrochlore structure for (a) Ca 0.6 7Y 1.33 Zr 1.33 Ta 0.33 O 7 (C2YZT2) and bright diffraction maxima arranged in a ring pattern of the fluorite structure for (b) Ca 0.29 7Y 1.71 Zr 1.71 Ta 0.29 O 7 (CY6Z6T).

  19. C60 and U ion irradiation of Gd2TixZr2-xO7 pyrochlore

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jiaming; Toulemonde, Marcel; Lang, Maik; Costantini, Jean Marc; Della-Negra, Serge; Ewing, Rodney C.

    2015-08-01

    Gd2TixZr2-xO7 (x = 0 to 2) pyrochlore was irradiated by 30 MeV C60 clusters, which provide an extremely high ionizing energy density. Here, high-resolution transmission electron microscopy revealed a complex ion-track structure in Gd2Ti2O7 and Gd2TiZrO7, consisting of an amorphous core and a shell of a disordered, defect-fluorite structure.

  20. High-pressure synthesis and characterization of the effective pseudospin S =1 /2 XY pyrochlores R2P t2O7 (R =Er ,Yb )

    Science.gov (United States)

    Cai, Y. Q.; Cui, Q.; Li, X.; Dun, Z. L.; Ma, J.; dela Cruz, C.; Jiao, Y. Y.; Liao, J.; Sun, P. J.; Li, Y. Q.; Zhou, J. S.; Goodenough, J. B.; Zhou, H. D.; Cheng, J.-G.

    2016-01-01

    We report on the high-pressure syntheses and detailed characterizations of two effective pseudospin S =1 /2 XY pyrochlores E r2P t2O7 and Y b2P t2O7 via x-ray/neutron powder diffraction, dc and ac magnetic susceptibility, and specific-heat measurements down to 70 mK. We found that both compounds undergo long-range magnetic transitions at TN ,C≈0.3 K , which are ascribed to an antiferromagnetic- and ferromagnetic-type order for E r2P t2O7 and Y b2P t2O7 , respectively, based on the field dependence of their transition temperatures as well as the systematic comparisons with other similar pyrochlores R2B2O7 (R =Er ,Yb ;B =Sn ,Ti ,Ge ). The observed TN of E r2P t2O7 is much lower than that expected from the relationship of TN versus the ionic radius of B4 + derived from the series of E r2B2O7 , while the TC of Y b2P t2O7 is the highest among the series of ferromagnetic compounds Y b2B2O7 (B =Sn ,Pt ,Ti ). Given the monotonic variation of the lattice constant as a function of the B -cation size across these two series of R2B2O7 (R =Er ,Yb ), the observed anomalous values of TN ,C in the Pt-based XY pyrochlores imply that another important factor beyond the nearest-neighbor R -R distance is playing a role. In light of the anisotropic exchange interactions Jex={Jz z,J±,J±±,Jz ± } for the S =1 /2 XY pyrochlores, we have rationalized these observations by considering a weakened (enhanced) antiferromagnetic planar J± (ferromagnetic Ising-like Jz z) due to strong Pt 5 d -O 2 p hybridization within the plane perpendicular to the local [111] direction.

  1. The atomic structure of protons and hydrides in Sm1.92Ca0.08Sn2O7-δ pyrochlore from DFT calculations and FTIR spectroscopy

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Eurenius, K. E. J.; Rossmeisl, Jan

    2012-01-01

    A combined density functional theory and Fourier transform infrared spectroscopy study of the structure and specific site preference of protons and hydrides in the pyrochlore Sm1.92Ca0.08Sn2O7-δ is presented. Two protonic sites of particular high stability are identified, both located on O(1......) oxygen atoms closely associated with a Ca dopant. Further, the unexpected presence of Ho hydride defects in undoped, oxygen deficient Sm2Sn2O7 is reported. Finally, the stretching frequencies and relative intensities for these and other sites are calculated. The main features of the Fourier transform...

  2. Synthesis and electrical properties of the pyrochlore-type Gd2-yLayZr2O7 solid solution

    Directory of Open Access Journals (Sweden)

    León, C.

    2008-06-01

    Full Text Available Different compositions in the pyrochlore-type Gd2-yLayZr2O7 solid solution (0 ≤ y ≤ 1 were prepared at room-temperature by mechanically milling stoichiometric mixtures of the corresponding oxides. Irrespective of their lanthanum content, as-prepared powder samples consist of single-phase anion deficient fluorite materials, although long-range ordering of cations and anion vacancies characteristic of pyrochlores was observed in all cases after firing the samples at 1500°C. Interestingly, activation energy for oxygen migration in the series decreases as La-content increases, from 1.13 eV for Gd2Zr2O7 to 0.81 eV for GdLaZr2O7, whereas ionic conductivity was found to be almost La-content independent, at least for y ≤ 0.8 at T = 500°C and y ≤ 0.4 at T = 800°C. These results are explained in terms of weaker ion-ion interactions in better ordered structures (i.e., as La-content increases and highlight the importance of structural ordering/disordering in determining the dynamics of mobile oxygen ions.Partiendo de mezclas estequiométricas de los óxidos correspondientes, se prepararon por molienda mecánica y a temperatura ambiente diferentes composiciones en la solución sólida Gd2-yLayZr2O7 (0 ≤ y ≤ 1 con estructura de tipo pirocloro y conductora de iones oxígeno. Independientemente del contenido de lantano, los polvos extraídos del molino presentaron difractogramas similares al de una fluorita no estequiométrica aunque en todos los casos, el tratamiento térmico a 1500°C indujo la aparición del ordenamiento de largo alcance de cationes y vacancias aniónicas característico de pirocloros. La energía de activación para el proceso de migración de iones oxígeno en la serie disminuye a medida que se incrementa el contenido de lantano, desde 1.13 eV de Gd2Zr2O7 hasta 0.81 eV de GdLaZr2O7, mientras que la conductividad resultó ser prácticamente independiente del mismo hasta y ≤ 0.8 para T = 500°C e y ≤ 0.4 para T = 800

  3. Absence of magnetic long-range order in Y2CrSbO7 : Bond-disorder-induced magnetic frustration in a ferromagnetic pyrochlore

    Science.gov (United States)

    Shen, L.; Greaves, C.; Riyat, R.; Hansen, T. C.; Blackburn, E.

    2017-09-01

    The consequences of random nonmagnetic-ion dilution for the pyrochlore family Y2(M 1 -xN x)2O7 (M = magnetic ion, N = nonmagnetic ion) have been investigated. As a first step, we experimentally examine the magnetic properties of Y2CrSbO7 (x =0.5 ), in which the magnetic sites (Cr3 +) are percolative. Although the effective Cr-Cr spin exchange is ferromagnetic, as evidenced by a positive Curie-Weiss temperature, ΘCW ≃19.5 K , our high-resolution neutron powder diffraction measurements detect no sign of magnetic long-range order down to 2 K. In order to understand our observations, we construct a lattice model to numerically study the bond disorder introduced by the ionic size mismatch between M and N , which reveals that the bond disorder percolates at xb ≃0.23 , explaining the absence of magnetic long-range order. This model could be applied to a series of frustrated magnets with a pyrochlore sublattice, for example, the spinel compound Zn (Cr1 -xGax )2O4 , wherein a Néel to spin glass phase transition occurs between x =0.2 and 0.25 [Lee et al., Phys. Rev. B 77, 014405 (2008), 10.1103/PhysRevB.77.014405]. Our study stresses the non-negligible role of bond disorder on magnetic frustration, even in ferromagnets.

  4. Pyrochlore type semiconducting ceramic oxides in Ca-Ce-Ti-M-O system (M = Nb or Ta)-Structure, microstructure and electrical properties

    Energy Technology Data Exchange (ETDEWEB)

    Deepa, M. [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695019 (India); Prabhakar Rao, P., E-mail: padala_rao@yahoo.com [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695019 (India); Radhakrishnan, A.N.; Sibi, K.S.; Koshy, Peter [Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695019 (India)

    2009-07-01

    A new series of pyrochlore type ceramic semiconducting oxides in Ca-Ce-Ti-M-O (M = Nb or Ta) system has been synthesized by the conventional ceramic route. The electrical conductivity measurements show that these oxides exhibit semiconducting behavior and the conductivity increases with the Ce content in the compound. Activation energy of the current carriers is in the range of 0.5-1.6 eV. The electrical conductivity in these oxides is due to the presence of Ce{sup 3+}, which remains in the reduced state without being oxidized to Ce{sup 4+} by structural stabilization. The photoluminescence and X-ray photoelectron spectroscopy analysis corroborate the presence of Ce in the 3+ state. Impedance spectral analysis is carried out to evaluate the transport properties and indicates that the conduction in these compounds is mainly due to electronic contribution. The X-ray powder diffraction and Raman spectroscopy analysis establishes that these oxides belong to a cubic pyrochlore type structure.

  5. Synthesis, crystal structure, and magnetic properties of pyrochlore-type Eu{sub 2}Ta{sub 2}(O,N){sub 7+δ}

    Energy Technology Data Exchange (ETDEWEB)

    Anke, Bjoern; Hund, Sophie; Lorent, Christian; Lerch, Martin [Institut fuer Chemie, Technische Universitaet Berlin (Germany); Janka, Oliver; Block, Theresa; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany)

    2017-12-13

    Pyrochlore-type Eu{sub 2}Ta{sub 2}(O,N){sub 7+δ} phases were prepared by reaction of ammonia with an amorphous europium tantalum oxide precursor. {sup 151}Eu Moessbauer and EPR spectroscopy as well as magnetic susceptibility measurements point to the presence of exclusively Eu{sup 3+}. For phase-pure samples (X-ray powder diffraction), the nitrogen content varies between 1.0 and 1.8 wt %, leading to compositions in the range Eu{sub 2}Ta{sub 2}O{sub 7.1}N{sub 0.6} - Eu{sub 2}Ta{sub 2}O{sub 6.5}N{sub 1.0}. Pyrochlore-type phases are structurally derived from the fluorite type with 1/8 of the anions missing, resulting in an ideal composition A{sub 2}B{sub 2}X{sub 7}. In Eu{sub 2}Ta{sub 2}(O,N){sub 7+δ} the excess anions partly occupy these vacancies. The prepared phases are colorless with a direct optical bandgap of 4.3 eV and they show the typical Van Vleck paramagnetic behavior known for trivalent Eu atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. An unusual hybrid fluoride featuring a [V7F27]6- chain motif based on a pyrochlore-like building unit

    International Nuclear Information System (INIS)

    Aldous, David W.; Slawin, Alexandra M.Z.; Lightfoot, Philip

    2008-01-01

    A new hybrid vanadium (III) fluoride [C 4 H 12 N 2 ] 3 [V 7 F 27 ] has been synthesised solvothermally. The crystal structure (trigonal, R3-bar c; a=17.367(2) A, c=19.604(2) A) reveals an unusual and novel chain motif consisting of pyrochlore-like heptameric units of corner-sharing octahedra, which are further linked into linear chains of alternating triple and single octahedral groups. The chains are separated by hydrogen-bonded piperazinium moieties. Magnetic susceptibility data show moderate antiferromagnetic interactions but no long-range order above 2 K, consistent with pronounced one-dimensional character, as well as frustration arising within the triangular units of magnetic ions in the chains. - Graphical abstract: A unique chain-structure vanadium(III) fluoride [C 4 H 12 N 2 ] 3 [V 7 F 27 ], based on a pyrochlore-like building unit, has been prepared solvothermally. Despite antiferromagnetic interactions, no long-range magnetic order occurs above 2 K, suggesting possible frustration

  7. Structures and solid solution mechanisms of pyrochlore phases in the systems Bi{sub 2}O{sub 3}-ZnO-(Nb, Ta){sub 2}O{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Tan, K.B., E-mail: tankb@science.upm.edu.m [Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor (Malaysia); Khaw, C.C. [Department of Engineering, Universiti Tunku Abdul Rahman, 53300 Setapak, Kuala Lumpur (Malaysia); Lee, C.K. [Academic Science Malaysia, 902-4 Jalan Tun Ismail, 50480 Kuala Lumpur (Malaysia); Zainal, Z. [Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor (Malaysia); Miles, G.C. [Department of Engineering Materials, The University of Sheffield, Mappin Street, Sheffield, S1 3JD (United Kingdom)

    2010-10-22

    Research highlights: {yields} Combined XRD and ND Rietveld structural refinement of pyrochlores. {yields} Structures and solid solution mechanisms of Bi-pyrochlores. {yields} Bi and Zn displaced off-centre to different 96g A-site positions. {yields} Summary of composition-structure-property of Bi-pyrochlores. - Abstract: The crystal structures of two pyrochlore phases have been determined by Rietveld refinement of combined X-ray and neutron powder diffraction data. These are stoichiometric, Bi{sub 1.5} ZnTa{sub 1.5}O{sub 7} and non-stoichiometric Bi{sub 1.56}Zn{sub 0.92}Nb{sub 1.44}O{sub 6.86}. In both structures, Zn is distributed over A- and B-sites; Bi and Zn are displaced off-centre, to different 96g A-site positions; of the three sets of oxygen positions, O(1) are full, O(2) contain vacancies and O(3) contain a small number of oxygen, again in both cases. Comparisons between these structures, those of related Sb analogues and literature reports are made.

  8. Self-assembled, rare earth tantalate pyrochlore nanoparticles for superior flux pinning in YBa2Cu3O7-δ films

    International Nuclear Information System (INIS)

    Harrington, S A; Durrell, J H; Wimbush, S C; Kursumovic, A; MacManus-Driscoll, J L; Maiorov, B; Wang, H; Lee, J H

    2009-01-01

    Addition of pyrochlore rare earth tantalate phases, RE 3 TaO 7 (RTO, where RE = rare earth, Er, Gd and Yb) to YBa 2 Cu 3 O 7-δ (YBCO) is shown to vastly improve pinning, without being detrimental to the superconducting transition temperature. The closely lattice matched to RTO phase provides a lower interfacial energy with YBCO than BaZrO 3 (BZO) and produces very fine (∼5 nm) particles with high linearity in their self-assembly along c. Critical current densities of 0.86, 0.38 MA cm -2 at 1 and 3 T (for fields) parallel to the c axis were recorded at 77 K in 0.5-1.0 μm thick films and a transition temperature of 92 K was observed even in the highest level doped sample (8 mol%). (rapid communication)

  9. Spin correlations in the pyrochlore slab compounds Ba2Sn2Ga10-7pZnCr7pO22

    International Nuclear Information System (INIS)

    Bonnet, P; Payen, C; Mutka, H; Danot, M; Fabritchnyi, P; Stewart, J R; Mellergaard, A; Ritter, C

    2004-01-01

    The low-temperature properties of a diluted antiferromagnetic pyrochlore slab of S = 3/2 spins are investigated through a study of the frustrated oxides Ba 2 Sn 2 Ga 10-7p ZnCr 7p O 22 (p>0.85). Powder neutron diffraction and 119 Sn Moessbauer absorption show no evidence of long-range magnetic order above 1.5 K. As in SrCr 9q Ga 12-9q O 19 , diffuse magnetic scattering, indicative of short range spin-spin correlations, is observed at low temperature. The dependence of the low-temperature sub-Curie bulk susceptibility to weak site depletion is the inverse of that observed in SrCr 9q Ga 12-9q O 19

  10. Synthesis, crystal structure and luminescent properties of a new pyrochlore type tungstate CsGa0.333W1.667O6

    Science.gov (United States)

    Zhao, Dan; Zhao, Ji; Fan, Yun-Chang; Ma, Zhao; Zhang, Rui-Juan; Liu, Bao-Zhong

    2018-06-01

    High temperature solution reaction leads to a new tungstate compound CsGa0.333W1.667O6, whose structure was determined by single-crystal X-ray diffraction analysis. The results show that it crystallizes in pyrochlore structure with cubic space group Fd-3m and a = 10.2529 (13) Å. In this structure, Ga and W atoms are in a statistical disorder manner. The self-activated luminescent properties CsGa0.333W1.667O6 were studied. Under the excitation of 323 nm, the emission spectrum exhibits a blue emission centered at 466 nm with the chromaticity coordinates (0.1838, 0.1814).

  11. High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

    Energy Technology Data Exchange (ETDEWEB)

    Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye; Fuentes, Antonio F.; Yan, Jinyuan; Ewing, Rodney C.; Mao, Wendy L.

    2017-01-28

    In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A2B2O7 pyrochlore (A=Eu, Dy; B=Ti, Zr) up to ~50GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B=Ti and ~16 GPa B=Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionic radii, i.e., A=Dy, proceeding faster than those with a larger ionic radii, i.e., A=Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B=Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A=Eu than A=Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu2Zr2O7 as compared with the initially defect-fluorite structured Dy2Zr2O7.

  12. Photoluminescence properties of ‘red’ emitting La{sub 2}Zr{sub 2}O{sub 7}:Eu pyrochlore ceramics for potential phosphor application

    Energy Technology Data Exchange (ETDEWEB)

    Mohapatra, M., E-mail: manojm@barc.gov.in; Rajeswari, B.; Hon, N.S.; Kadam, R.M.; Natarajan, V.

    2015-10-15

    Lanthanum zirconate (La{sub 2}Zr{sub 2}O{sub 7}=LZO) pyrochlores doped with varying concentrations of Eu were synthesized using a low temperature gel-combustion synthesis route and characterized using X-ray diffraction, scanning electron microscopic and photoluminescence techniques. The final annealing temperature of the system could be brought down to 700 °C to produce a single phase compound. In addition, the optimum activator ion concentration for maximum luminescence yield was evaluated for the system. The site occupancy for the Eu ions was also investigated which suggested that at 500 °C, the ions were on the surface of the LZO host and later diffused into the lattice and replaced the La{sup 3+} ions on annealing at 700 °C 5 h. However, due to difference in the ionic radii, the doped RE ions were of the inversion center forming a D{sub 2d} symmetry around them. For the first time the radiative properties and the commercial utility of the LZO system have been investigated. These parameters were used to get an idea about the M–L bond covalency in the system. The radiative properties suggested the system can be used as a potential ‘red’ emitting phosphor. - Highlights: • Synthesis of lanthanum zirconate pyrochlores doped with Eu using gel-combustion route. • Optimization of dopant ion concentration and annealing temperature and evaluation of its local site symmetry. • Evaluation of various photo-physical properties for the Eu-LZO system to investigate the M–L bond covalency. • Investigation of the commercial utility of the system by calculating the color coordinates. • Comparison of the emission properties with commercial sample.

  13. Synthesis, magnetic properties and Moessbauer spectroscopy for the pyrochlore family Bi{sub 2}BB Prime O{sub 7} with B=Cr and Fe and B Prime =Nb, Ta and Sb

    Energy Technology Data Exchange (ETDEWEB)

    Blanco, Maria C. [INFIQC (CONICET), Dpto. de Fisicoquimica, Fac. de Ciencias Quimicas, U.N.C., Cordoba (X5000HUA) (Argentina); Franco, Diego G. [INFIQC (CONICET), Dpto. de Fisicoquimica, Fac. de Ciencias Quimicas, U.N.C., Cordoba (X5000HUA) (Argentina); Centro Atomico Bariloche - CNEA, Av. E. Bustillo 9500, S.C. de Bariloche (8500), R.N. (Argentina); Jalit, Yamile; Pannunzio Miner, Elisa V. [INFIQC (CONICET), Dpto. de Fisicoquimica, Fac. de Ciencias Quimicas, U.N.C., Cordoba (X5000HUA) (Argentina); Berndt, Graciele; Paesano, Andrea [Departamento de Fisica, Universidade Estadual de Maringa, Parana (Brazil); Nieva, Gladys [Centro Atomico Bariloche - CNEA, Av. E. Bustillo 9500, S.C. de Bariloche (8500), R.N. (Argentina); Carbonio, Raul E., E-mail: carbonio@mail.fcq.unc.edu.ar [INFIQC (CONICET), Dpto. de Fisicoquimica, Fac. de Ciencias Quimicas, U.N.C., Cordoba (X5000HUA) (Argentina)

    2012-08-15

    The samples Bi{sub 2}BB Prime O{sub 7}, with B=Cr and Fe and B Prime =Nb, Ta and Sb were prepared by solid state method. The crystallographic structure was investigated on the basis of X-ray powder diffraction data. Rietveld refinements show that the crystal structure is cubic, space group Fd-3m. The Bi{sup 3+} cation on the eight-coordinate pyrochlore A-site shows displacive disorder, as a consequence of its lone pair electron configuration. There is also a considerable A-site disorder shown by Rietveld Analysis and confirmed in the case of the iron containing samples with Moessbauer spectroscopy. The magnetic measurements show paramagnetic behavior at all temperatures for the Cr oxides. The Fe pyrochlores show antiferromagnetic order around 10 K.

  14. Re-examination of the crystal structure of the β-pyrochlore oxide superconductor KOs 2O 6 by X-ray and convergent-beam electron diffraction analyses

    Science.gov (United States)

    Yamaura, Jun-Ichi; Hiroi, Zenji; Tsuda, Kenji; Izawa, Koichi; Ohishi, Yasuo; Tsutsui, Satoshi

    2009-01-01

    The crystal structure of the β-pyrochlore oxide superconductor KOs 2O 6 is re-examined. A single-crystal X-ray diffraction (XRD) analysis at room temperature first revealed that the compound crystallizes in a cubic structure with the centrosymmetric space group Fd3¯m, as in conventional pyrochlore oxides. Later, however, Schuck et al. claimed a different non-centrosymmetric F4¯3m structure based on their single-crystal XRD analysis. To unambiguously determine the true crystal structure of KOs 2O 6, we carried out high-resolution synchrotron powder X-ray and convergent-beam electron diffraction measurements at room temperature. The space group was determined with high reliability to be centrosymmetric Fd3¯m, not F4¯3m. This confirms the importance of the K atom location in a high-symmetry site, which causes unusually large rattling of the K atom.

  15. Investigation of structural and electrical properties of vanadium substituted disordered pyrochlore-type Ho{sub 2−x}V{sub x}Zr{sub 2}O{sub 7} nanostructure

    Energy Technology Data Exchange (ETDEWEB)

    Karamat, Nazia, E-mail: naziakaramatgoraya@yahoo.com [Institute of Chemical Sciences, Bahauddin Zakariya University, Multan (Pakistan); Ashiq, Muhammad Naeem, E-mail: naeemashiqqau@yahoo.com [Institute of Chemical Sciences, Bahauddin Zakariya University, Multan (Pakistan); Najam-ul-Haq, Muhammad [Institute of Chemical Sciences, Bahauddin Zakariya University, Multan (Pakistan); Ali, Irshad; Iqbal, M. Asif; Irfan, Muhammad [Department of Physics, Bahauddin Zakariya University, Multan (Pakistan); Abbas, Yasir; Athar, Muhammad [Institute of Chemical Sciences, Bahauddin Zakariya University, Multan (Pakistan)

    2014-04-01

    Graphical abstract: - Highlights: • Normal microemulsion method has been used for the synthesis of zirconates nanomaterials. • Structure shifted towards highly disordered pyrochlore state with substitution. • The electrical resistivity increase with the vanadium content. • The dielectric constant show resonance behavior. • The synthesized materials are suitable for microwave devices. - Abstract: Disordered pyrochlore system with composition Ho{sub 2−x}V{sub x}Zr{sub 2}O{sub 7} (where x = 0, 0.25, 0.50, 0.75 and 1) has been synthesized by the normal microemulsion route to examine the effect of vanadium substitution on structural and electrical properties. The prepared compounds are characterized by several techniques including X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, energy dispersive X-ray fluorescence (ED-XRF), energy dispersive spectra (EDS), scanning electron microscopy (SEM), temperature dependent electrical and frequency dependent dielectric measurements. The XRD analysis confirms the formation of disordered pyrochlore phase with crystallite size 7–30 nm while a second phase is also observed in the highly substituted materials. The increase in resistivity is attributed to the removal of low energy pathway due to cation disordering. The dielectric constant decreases due to lowering of dipole moment with substitution and its resonance behavior shifted toward higher frequencies. The electrical and dielectric measurements suggest that materials are suitable for high frequency electronic devices, such as oscillators, resonators and frequency filters.

  16. Synthesis by two methods and crystal structure determination of a new pyrochlore-related compound Sm{sub 2}FeTaO{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Torres-Martinez, Leticia M., E-mail: lettorresg@yahoo.com [Departamento de Ecomateriales y Energia, Facultad de Ingenieria Civil, Universidad Autonoma de Nuevo Leon, Cd. Universitaria, San Nicolas de los Garza, Nuevo Leon 66450 (Mexico); Ruiz-Gomez, Miguel A. [Departamento de Ecomateriales y Energia, Facultad de Ingenieria Civil, Universidad Autonoma de Nuevo Leon, Cd. Universitaria, San Nicolas de los Garza, Nuevo Leon 66450 (Mexico); Facultad de Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, Av. Manuel Nava 6, San Luis Potosi, S.L.P. 78290 (Mexico); Figueroa-Torres, M.Z.; Juarez-Ramirez, Isaias [Departamento de Ecomateriales y Energia, Facultad de Ingenieria Civil, Universidad Autonoma de Nuevo Leon, Cd. Universitaria, San Nicolas de los Garza, Nuevo Leon 66450 (Mexico); Moctezuma, Edgar [Facultad de Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, Av. Manuel Nava 6, San Luis Potosi, S.L.P. 78290 (Mexico); and others

    2012-04-16

    Graphical abstract: The monoclinic (space group C2/c) structure of a new compound, Sm{sub 2}FeTaO{sub 7} shows an alternating Sm-O and Fe/Ta-O layers. In the Fe/Ta-O layer, Fe/Ta1 and Fe/Ta3 cations are coordinated by six oxygen atoms, forming irregular octahedral interconnected into a hexagonal tungsten bronze (HTB) type network. The HTB layer is a fundamental framework in the pyrohlore-related structure. Highlights: Black-Right-Pointing-Pointer Pyrochlore-related compound Sm{sub 2}FeTaO{sub 7} prepared by solid state reaction and sol-gel. Black-Right-Pointing-Pointer Sm{sub 2}FeTaO{sub 7} crystallizes with a monoclinic crystal structure and space group C2/c. Black-Right-Pointing-Pointer The compound is synthesized by sol-gel at lower temperature and time than solid state. Black-Right-Pointing-Pointer Surface area of sol-gel Sm{sub 2}FeTaO{sub 7} is 10 times higher than that prepared by solid state. - Abstract: This paper reports on the synthesis of a new pyrochlore-related compound Sm{sub 2}FeTaO{sub 7} by both solid state reaction and sol-gel synthesis routes. Structural features were determined by X-ray powder diffraction and Rietveld refinement and were corroborated using Transmission Electron Microscopy (TEM). The results revealed that Sm{sub 2}FeTaO{sub 7} crystallized in the monoclinic system with space group C2/c and the following cell parameters: a = 13.1307(5) Angstrom-Sign , b = 7.5854(3) Angstrom-Sign , c = 11.6425(4) Angstrom-Sign and {beta} = 100.971(2) Degree-Sign . The monoclinic structure of Sm{sub 2}FeTaO{sub 7} showed an arrangement of alternating Sm-O and Fe/Ta-O layers and two types of irregular octahedra of Fe/Ta-O, which are interconnected into a hexagonal tungsten bronze (HTB)-type network. On the other hand, Sm{sub 2}FeTaO{sub 7} prepared by sol-gel was obtained with lower particle sizes than the solid state produced compound. The difference in particle size causes a difference of one order of magnitude in the specific surface area. In

  17. First-principles study on cubic pyrochlore iridates Y2Ir2O7 and Pr2Ir2O7

    International Nuclear Information System (INIS)

    Ishii, Fumiyuki; Mizuta, Yo Pierre; Kato, Takehiro; Ozaki, Taisuke; Weng Hongming; Onoda, Shigeki

    2015-01-01

    Fully relativistic first-principles electronic structure calculations based on a noncollinear local spin density approximation (LSDA) are performed for pyrochlore iridates Y 2 Ir 2 O 7 and Pr 2 Ir 2 O 7 . The all-in, all-out antiferromagnetic (AF) order is stablized by the on-site Coulomb repulsion U > U c in the LSDA+U scheme, with U c ∼ 1.1 eV and 1.3 eV for Y 2 Ir 2 O 7 and Pr 2 Ir 2 O 7 , respectively. AF semimetals with and without Weyl points and then a topologically trivial AF insulator successively appear with further increasing U. For U = 1.3 eV, Y 2 Ir 2 O 7 is a topologically trivial narrow-gap AF insulator having an ordered local magnetic moment ∼0.5μ B /Ir, while Pr 2 Ir 2 O 7 is barely a paramagnetic semimetal with electron and hole concentrations of 0.016/Ir, in overall agreements with experiments. With decreasing oxygen position parameter x describing the trigonal compression of IrO 6 octahedra, Pr 2 Ir 2 O 7 is driven through a non-Fermi-liquid semimetal having only an isolated Fermi point of Γ 8 + , showing a quadratic band touching, to a Z 2 topological insulator. (author)

  18. Pseudo-Goldstone Magnons in the Frustrated S=3/2 Heisenberg Helimagnet ZnCr_{2}Se_{4} with a Pyrochlore Magnetic Sublattice

    Directory of Open Access Journals (Sweden)

    Y. V. Tymoshenko

    2017-11-01

    Full Text Available Low-energy spin excitations in any long-range ordered magnetic system in the absence of magnetocrystalline anisotropy are gapless Goldstone modes emanating from the ordering wave vectors. In helimagnets, these modes hybridize into the so-called helimagnon excitations. Here we employ neutron spectroscopy supported by theoretical calculations to investigate the magnetic excitation spectrum of the isotropic Heisenberg helimagnet ZnCr_{2}Se_{4} with a cubic spinel structure, in which spin-3/2 magnetic Cr^{3+} ions are arranged in a geometrically frustrated pyrochlore sublattice. Apart from the conventional Goldstone mode emanating from the (0 0 q_{h} ordering vector, low-energy magnetic excitations in the single-domain proper-screw spiral phase show soft helimagnon modes with a small energy gap of ∼0.17  meV, emerging from two orthogonal wave vectors (q_{h} 0 0 and (0 q_{h} 0 where no magnetic Bragg peaks are present. We term them pseudo-Goldstone magnons, as they appear gapless within linear spin-wave theory and only acquire a finite gap due to higher-order quantum-fluctuation corrections. Our results are likely universal for a broad class of symmetric helimagnets, opening up a new way of studying weak magnon-magnon interactions with accessible spectroscopic methods.

  19. A novel isomorphic phase transition in β-pyrochlore oxide KOs2O6: a study using high resolution neutron powder diffraction

    Science.gov (United States)

    Sasai, Kenzo; Kofu, Maiko; Ibberson, Richard M.; Hirota, Kazuma; Yamaura, Jun-ichi; Hiroi, Zenji; Yamamuro, Osamu

    2010-01-01

    We have carried out adiabatic calorimetric and neutron powder diffraction experiments on the β-pyrochlore oxide KOs2O6, which has a superconducting transition at Tc = 9.6 K and another novel transition at Tp = 7.6 K. A characteristic feature of this compound is that the K ions exhibit rattling vibrations in the cages formed by O atoms even at very low temperatures. The temperature and entropy of the Tp transition is in good agreement with previous data measured using a heat relaxation method, indicating that the present sample is of high purity and the transition entropy, 0.296 J K-1 mol-1, does not depend on the calorimetric method used. The neutron powder diffraction data show no peak splitting nor extra peaks over the temperature range between 2 and 295 K, suggesting that the Tp transition is a rather unusual isomorphic transition. Rietveld analysis revealed an anomalous expansion of the lattice and a deformation of the O atom cage below 7.6 K. In the low-temperature phase, the distribution of scattering density corresponding to the K ions becomes broader whilst maintaining its maximum at the cage center. Based on these findings, we suggest that the Tp transition is due to the expansion of the cage volume and cooperative condensation of the K ions into the ground state of the rattling motion.

  20. Comparison of the Supercooled Spin Liquid States in the Pyrochlore Magnets Dy2Ti2O7 and Ho2Ti2O7

    Science.gov (United States)

    Eyal, Anna; Eyvazov, Azar B.; Dusad, Ritika; Munsie, Timothy J. S.; Luke, Graeme M.; Davis, J. C. Séamus

    Despite a well-ordered crystal structure and strong magnetic interactions between the Dy or Ho ions, no long-range magnetic order has been detected in the pyrochlore titanates Ho2Ti2O7 and Dy2Ti2O7. The low temperature state in these materials is governed by spin-ice rules. These constrain the Ising like spins in the materials, yet does not result in a global broken symmetry state. To explore the actual magnetic phases, we simultaneously measure the time- and frequency-dependent magnetization dynamics of Dy2Ti2O7 and Ho2Ti2O7 using toroidal, boundary-free magnetization transport techniques. We demonstrate a distinctive behavior of the magnetic susceptibility of both compounds, that is indistinguishable in form from the permittivity of supercooled dipolar liquids. Moreover, we show that the microscopic magnetic relaxation times for both materials increase along a super-Arrhenius trajectory also characteristic of supercooled glass-forming liquids. Both materials therefore exhibit characteristics of a supercooled spin liquid. Strongly-correlated dynamics of loops of spins is suggested as a possible mechanism which could account for these findings. Potential connections to many-body spin localization will also be discussed.

  1. Heat capacity and magnetic properties of fluoride CsFe{sup 2+}Fe{sup 3+}F{sub 6} with defect pyrochlore structure

    Energy Technology Data Exchange (ETDEWEB)

    Gorev, M.V., E-mail: gorev@iph.krasn.ru [Kirensky Institute of Physics, Russian Academy of Sciences, Siberian Branch, 660036 Krasnoyarsk (Russian Federation); Institute of Engineering Physics and Radio Electronics, Siberian State University, 660074 Krasnoyarsk (Russian Federation); Flerov, I.N. [Kirensky Institute of Physics, Russian Academy of Sciences, Siberian Branch, 660036 Krasnoyarsk (Russian Federation); Institute of Engineering Physics and Radio Electronics, Siberian State University, 660074 Krasnoyarsk (Russian Federation); Tressaud, A. [Institut de Chimie de la Matière Condensée, ICMCB-CNRS, Université Bordeaux, 33608 Pessac Cedex (France); Bogdanov, E.V. [Kirensky Institute of Physics, Russian Academy of Sciences, Siberian Branch, 660036 Krasnoyarsk (Russian Federation); Astafijev Krasnoyarsk State Pedagogical University, 660049 Krasnoyarsk (Russian Federation); Kartashev, A.V. [Kirensky Institute of Physics, Russian Academy of Sciences, Siberian Branch, 660036 Krasnoyarsk (Russian Federation); Krasnoyarsk State Agrarian University, 660049 Krasnoyarsk (Russian Federation); Bayukov, O.A. [Kirensky Institute of Physics, Russian Academy of Sciences, Siberian Branch, 660036 Krasnoyarsk (Russian Federation); Eremin, E.V. [Kirensky Institute of Physics, Russian Academy of Sciences, Siberian Branch, 660036 Krasnoyarsk (Russian Federation); Institute of Engineering Physics and Radio Electronics, Siberian State University, 660074 Krasnoyarsk (Russian Federation); Krylov, A.S. [Kirensky Institute of Physics, Russian Academy of Sciences, Siberian Branch, 660036 Krasnoyarsk (Russian Federation)

    2016-05-15

    Heat capacity, Mössbauer and Raman spectra as well as magnetic properties of fluoride CsFe{sub 2}F{sub 6} with defect pyrochlore structure were studied. In addition to recently found above room temperature three successive structural transformations Pnma-Imma-I4{sub 1}amd-Fd-3m, phase transition of antiferromagnetic nature with the 13.7 K Neel temperature and a broad heat capacity anomaly with a maximum at about 30 K were observed. The room temperature symmetry Pnma is unchanged at least down to 7 K. Simple model of indirect bond used to estimate the exchange interactions and to propose a magnetic structure model. - Graphical abstract: The ordered arrangement of Fe{sup 2+} and Fe{sup 3+} ions in high-spin states as well as antiferromagnetic phase transition followed by significant magnetic frustrations were found in pyrocholore-related CsFe{sup 2+}Fe{sup 3+}F{sub 6}. A magnetic structure was proposed using a simple model of indirect bonds. - Highlights: • The Pnma structure in pyrocholore CsFe{sub 2}F{sub 6} is stable down to helium temperature. • Mössbauer spectra confirmed the ordering of Fe{sup 2+} and Fe{sup 3+} ions. • Antiferromagnetic transformation and significant magnetic frustrations are found. • Experimental magnetic entropy agrees with entropy for Fe ions in high-spin state. • Superexchange interactions were calculated and a magnetic structure was proposed.

  2. Nanostructured KTaTeO6 and Ag-doped KTaTeO6 Defect Pyrochlores: Promising Photocatalysts for Dye Degradation and Water Splitting

    Science.gov (United States)

    Venkataswamy, Perala; Sudhakar Reddy, CH.; Gundeboina, Ravi; Sadanandam, Gullapelli; Veldurthi, Naveen Kumar; Vithal, M.

    2018-03-01

    In this study, the nanostructured parent KTaTeO6 (KTTO) and Ag-doped KTaTeO6 (ATTO) catalysts with defect pyrochlore structure were prepared by solid-state and ion-exchange methods, respectively. The synthesized materials were characterized by various techniques to determine their chemical composition, morphology and microstructural features. The XRD studies show that both KTTO and ATTO have cubic structure (space group Fd3m) with high crystallinity. The doping of Ag altered the BET surface area of parent KTTO. The nano nature of the samples was studied by TEM images. A considerable red-shift in the absorption edge is observed for ATTO compared to KTTO. Incorporation of Ag+ in the KTTO lattice is clearly identified from EDX, elemental mapping and XPS results. Degradation of methyl violet and solar water splitting reactions were used to access the photocatalytic activity of KTTO and ATTO. The results obtained suggest that compared to KTTO, the ATTO showed higher photocatalytic activity in both cases. The favourable properties such as high surface area, more surface hydroxyl groups, stronger light absorption in visible region and narrower band gap energy were supposed to be the reasons for the high activity observed in ATTO.

  3. Diffraction and spectroscopic study of pyrochlores Bi{sub 2−x}Fe{sub 1+x}SbO{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Qingdi; Blanchard, Peter E.R. [School of Chemistry, The University of Sydney, Sydney, NSW 2006 (Australia); Kennedy, Brendan J., E-mail: kennedyb@chem.usyd.edu.au [School of Chemistry, The University of Sydney, Sydney, NSW 2006 (Australia); Ling, Chris D.; Liu, Samuel [School of Chemistry, The University of Sydney, Sydney, NSW 2006 (Australia); Avdeev, Max [Australian Nuclear Science and Technology Organisation, Lucas Heights, New South Wales 2234 (Australia); Aitken, Jade B. [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia); Institute of Materials Structure Science, KEK, Tsukuba, Ibaraki 305-0801 (Japan); School of Chemistry, The University of Sydney, Sydney, NSW 2006 (Australia); Tadich, Anton; Brand, Helen E.A. [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

    2014-03-15

    Highlights: • Fe rich pyrochlores of the type Bi{sub 2−x}Fe{sub 1+x}SbO{sub 7} were prepared by solid state methods. • Structures determined using a combination of neutron and synchrotron X-ray diffraction. • Fe partially occupies the 8-coordinate site. • Dispacive disorder of the Bi cations observed as a consequence of the 6s{sup 2} electrons. • Non-Vegard behaviour seen at low Fe contents due to disorder. -- Abstract: The structural and electronic properties of the series Bi{sub 2−x}Fe{sub 1+x}SbO{sub 7} (0 ⩽ x ⩽ 0.6) were investigated using a combination of diffraction and spectroscopy. Synchrotron and neutron diffraction analysis show that Fe{sup 3+} cations substitute for Bi{sup 3+} onto the A site with increasing x, which was further confirmed by analysis of the Fe K/L-edge X-ray absorption near-edge spectra. The diffraction analysis indicated the presence of displacive disorder along the A{sub 2}O chains, likely the result of the Bi{sup 3+} 6s{sup 2} lone pair, as well as non-Vegard-like behaviour of the lattice parameters in the Fe-poor region. Fe K-edge extended X-ray absorption fine-structure analysis of Bi{sub 2}FeSbO{sub 7} confirmed the displacive disorder of the Bi{sup 3+} cations as well as Sb{sup 5+} and Fe{sup 3+} disorder on the B site.

  4. Unusual spin frozen state in a frustrated pyrochlore system NaCaCo{sub 2}F{sub 7} as observed by NMR

    Energy Technology Data Exchange (ETDEWEB)

    Sarkar, R.; Brueckner, F.; Klauss, H.H. [IFP, TU Dresden (Germany); Krizan, J.W.; Cava, R.J. [Department of Chemistry, Princeton University, Princeton, NJ (United States)

    2016-07-01

    We present {sup 23}Na -and {sup 19}F NMR results on the magnetically frustrated pyrochlore NaCaCo{sub 2}F{sub 7} with a frustration index of f = θ{sub CW}/T{sub f} ∝ 56. Recent neutron scattering experiments proposed XY like antiferromagnetic spin clusters at low energies in NaCaCo{sub 2}F{sub 7}. {sup 23}Na NMR -spectra reveal the presence of two magnetically non equivalent Na sites in conjunction with the local Co{sup 2+} spin structure. Below 3.6 K both the {sup 23}Na -and {sup 19}F spectra broaden due to the formation of static spin correlations. A huge reduction of the {sup 19}F -and {sup 23}Na NMR signal intensity hints at a quasi-static field distribution in NaCaCo{sub 2}F{sub 7} in this regime. The {sup 19}F spin-lattice relaxation rate {sup 19}(1/T{sub 1}) exhibits a peak at around 2.9 K, at the same temperature range where ac and dc susceptibility data show a broad maximum. The character of the spin fluctuation appears to be isotropic. The overall temperature dependence of {sup 19}(1/T{sub 1}) can be described by the BPP theory considering a fluctuating hyperfine field with an autocorrelation function. The correlation time of the autocorrelation function exhibits an activation behavior further indicating the spin-frozen state. While the present NMR studies suggest the spin frozen state at low temperatures, μSR investigations however reveal the presence of so called persistent spin dynamics down to 20 mK implying an exotic ground state in NaCaCo{sub 2}F{sub 7}.

  5. Lattice dynamical investigation of the Raman and infrared wave numbers and heat capacity properties of the pyrochlores R2Zr2O7 (R = La, Nd, Sm, Eu)

    Science.gov (United States)

    Nandi, S.; Jana, Y. M.; Gupta, H. C.

    2018-04-01

    A short-range electrostatic forcefield model has been applied for the first time to investigate the Raman and infrared wave numbers in pyrochlore zirconates R2Zr2O7 (R3+ = La, Nd, Sm, Eu). The calculations of phonons involve five stretching and four bending force constants in the Wilson GF matrix method. The calculated phonon wave numbers are in reasonable agreement with the observed spectra in infrared and Raman excitation zones for all of these isomorphous compounds. The contributions of force constants to each mode show a similar trend of variation for all of these compounds. Furthermore, to validate the established forcefield model, we calculated the standard thermodynamic functions, e.g., molar heat capacity, entropy and enthalpy, and compared the results with the previous experimental data for each compound. Using the derived wave numbers for the acoustic and optical modes, the total phonon contribution to the heat capacity was calculated for all these zirconate compounds. The Schottky heat capacity contributions were also calculated for the magnetic compounds, Nd2Zr2O7, Sm2Zr2O7 and Eu2Zr2O7, taking account of crystal-field level schemes of the lanthanide ions. The derived total heat capacity and the integrated values of molar entropy and molar enthalpy showed satisfactory correlations at low temperatures with the experimental results available in the literature for these compounds. At higher temperatures, the discrepancies may be caused by the anharmonic effects of vibrations, phonon dispersion, distribution of phonon density of states, etc.

  6. Order and disorder in the local and long-range structure of the spin-glass pyrochlore, Tb{sub 2}Mo{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Yu; Huq, Ashfia; Booth, Corwin H.; Ehlers, Georg; Greedan, John E.; Gardner, Jason S.

    2011-02-11

    To understand the origin of the spin-glass state in molybdate pyrochlores, the structure of Tb{sub 2}Mo{sub 2}O{sub 7} is investigated using two techniques: the long-range lattice structure was measured using neutron powder diffraction (NPD), and local structure information was obtained from the extended x-ray absorption fine structure (EXAFS) technique. While the long-range structure appears generally well ordered, enhanced mean-squared site displacements on the O(1) site and the lack of temperature dependence of the strongly anisotropic displacement parameters for both the Mo and O(1) sites indicate some disorder exists. Likewise, the local structure measurements indicate some Mo-Mo and Tb-O(1) nearest-neighbor disorder exists, similar to that found in the related spin-glass pyrochlore, Y{sub 2}Mo{sub 2}O{sub 7}. Although the freezing temperature in Tb{sub 2}Mo{sub 2}O{sub 7}, 25 K, is slightly higher than in Y{sub 2}Mo{sub 2}O{sub 7}, 22 K, the degree of local pair distance disorder is actually less in Tb{sub 2}Mo{sub 2}O{sub 7}. This apparent contradiction is considered in light of the interactions involved in the freezing process.

  7. Dielectric and magnetic properties, and electronic structure of multiferroic perovskite PbFe.sub.0.5./sub.Ta.sub.0.5./sub.O.sub.3./sub. and incipient ferroelectric pyrochlore Pb.sub.2./sub.Fe.sub.0.34./sub.Ta.sub.1.84./sub.O.sub.7.11./sub. single crystals and ceramics

    Czech Academy of Sciences Publication Activity Database

    Kania, A.; Miga, S.; Talik, E.; Gruszka, I.; Szubka, M.; Savinov, Maxim; Prokleška, J.; Kamba, Stanislav

    2016-01-01

    Roč. 36, č. 14 (2016), s. 3369-3381 ISSN 0955-2219 R&D Projects: GA ČR GA15-08389S Institutional support: RVO:68378271 Keywords : lead iron tantalate * perovskite multiferroic * pyrochlore * incipient ferroelectric * X-ray photoelectron spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.411, year: 2016

  8. Atomic-scale microstructural characterization and dielectric properties of crystalline cubic pyrochlore Bi1.5MgNb1.5O7 nanoparticles synthesized by sol-gel method

    KAUST Repository

    Zhang, Yuan; Zhu, Xinhua; Zhou, Shunhua; Zhu, Jianmin; Liu, Zhiguo; Al-Kassab, Talaat

    2013-01-01

    Here, we report the atomic-scale microstructural characterization and dielectric properties of crystalline cubic pyrochlore Bi1.5MgNb 1.5O7 (BMN) nanoparticles with mean size of 70 nm, which were synthesized by sol-gel method. The crystallinity, phase formation, morphology, and surface microstructure of the BMN nanoparticles were characterized by X-ray diffraction (XRD), Raman spectra, transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM), respectively. The phase evolution of the BMN nanoparticles investigated by XRD patterns showed that uniform cubic pyrochlore BMN nanoparticles were obtained after calcination at temperature of 800 C, and their structural information was revealed by Raman spectrum. TEM images demonstrated that the BMN nanoparticles had a spherical morphology with an average particle size of 70 nm, and their crystalline nature was revealed by HRTEM images. In addition, HRTEM images also demonstrate a terrace-ledge-kink (TLK) surface structure at the edges of rough BMN nanoparticles, where the terrace was on the (100) plane, and the ledge on the (001) plane. The formation of such a TLK surface structure can be well explained by a theory of periodic bond chains. Due to the surface structural reconstruction in the BMN nanoparticles, the formation of a tetragonal structure in a rough BMN nanoparticle was also revealed by HRTEM image. The BMN nanoparticles exhibited dielectric constants of 50 at 100 kHz and 30 at 1 MHz, and the dielectric loss of 0.19 at 1 MHz. © 2013 Springer Science+Business Media Dordrecht.

  9. Atomic-scale microstructural characterization and dielectric properties of crystalline cubic pyrochlore Bi1.5MgNb1.5O7 nanoparticles synthesized by sol-gel method

    KAUST Repository

    Zhang, Yuan

    2013-12-24

    Here, we report the atomic-scale microstructural characterization and dielectric properties of crystalline cubic pyrochlore Bi1.5MgNb 1.5O7 (BMN) nanoparticles with mean size of 70 nm, which were synthesized by sol-gel method. The crystallinity, phase formation, morphology, and surface microstructure of the BMN nanoparticles were characterized by X-ray diffraction (XRD), Raman spectra, transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM), respectively. The phase evolution of the BMN nanoparticles investigated by XRD patterns showed that uniform cubic pyrochlore BMN nanoparticles were obtained after calcination at temperature of 800 C, and their structural information was revealed by Raman spectrum. TEM images demonstrated that the BMN nanoparticles had a spherical morphology with an average particle size of 70 nm, and their crystalline nature was revealed by HRTEM images. In addition, HRTEM images also demonstrate a terrace-ledge-kink (TLK) surface structure at the edges of rough BMN nanoparticles, where the terrace was on the (100) plane, and the ledge on the (001) plane. The formation of such a TLK surface structure can be well explained by a theory of periodic bond chains. Due to the surface structural reconstruction in the BMN nanoparticles, the formation of a tetragonal structure in a rough BMN nanoparticle was also revealed by HRTEM image. The BMN nanoparticles exhibited dielectric constants of 50 at 100 kHz and 30 at 1 MHz, and the dielectric loss of 0.19 at 1 MHz. © 2013 Springer Science+Business Media Dordrecht.

  10. Characterisation and dissolution studies on the uranium pyrochlore mineral betafite (Ca,U)_2(Nb,Ti,Ta)_2O_7

    International Nuclear Information System (INIS)

    McMaster, S.; Ram, R.; Tardio, J.; Bhargava, S.

    2014-01-01

    The pyrochlore group mineral, betafite (nominally (Ca,U)_2(Nb,Ti,Ta)_2O_7); is a refractory uranium mineral found in many ore deposits, including the currently mined deposit at Rössing, Namibia and the currently unmined deposit at Saima Massif, China. The decreasing abundance of “easy to leach” uranium minerals (i.e. uraninite), has led to interest in the extraction of uranium from refractory uranium minerals such as betafite. In the current study, three naturally occurring betafite mineral samples (obtained from Ambatofotsky and Miarinarivo, Madagascar (BAM and BMM respectively) and Silver Crater Mine, Canada (BSC)) were characterised using ex-situ high temperature X-Ray Diffraction (XRD), multi acid digestion / ICP-MS analysis (composition) and X-Ray Photoelectron Spectroscopy (XPS). Dissolution of the three samples was also investigated under conditions similar to those used in commercial tank based uranium leaching processes. XRD analysis showed that all three samples were highly metamict. Samples BMM and BSC showed no assignable diffraction lines before heat treating, whereas the XRD pattern obtained for sample BAM contained diffraction lines that confirmed the presence of crystalline anatase (TiO_2). Heat treatment studies on the samples showed that the betafite in the samples was converted into a crystalline form at 700°C in all 3 samples. Gangue minerals, rutile, Nb-rutile, UTiNb_2O_1_0, and studitite were also found to be present in the heat treated samples. Multi acid digestion ICP-MS analysis showed the natural samples contained between 16 and 26% w/w uranium as well as all the major elements present typically in betafite. XPS analysis was conducted on the unheated betafite samples. XPS analysis showed that the uranium in the samples was predominately in U"5"+ oxidation state. Some U"6"+ was also identified though this was most likely restricted to the outer surface of the samples. Dissolution studies (batch mode) were conducted under the following

  11. Synthesis and characterization of Bi{sub 1.56}Sb{sub 1.48}Co{sub 0.96}O{sub 7} pyrochlore sun-light-responsive photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Naceur, Benhadria, E-mail: nacer1974@yahoo.fr [Laboratory of Inorganic Materials Chemistry and Application, Department of Materials Engineering, University of Science and Technology of Oran (USTO M.B), BP 1505, El M’naouar, 31000 Oran (Algeria); Abdelkader, Elaziouti, E-mail: elaziouti_a@yahoo.com [Laboratory of Inorganic Materials Chemistry and Application, Department of Materials Engineering, University of Science and Technology of Oran (USTO M.B), BP 1505, El M’naouar, 31000 Oran (Algeria); Dr Moulay Tahar University, Saida (Algeria); Nadjia, Laouedj, E-mail: nlaouedj@yahoo.fr [Laboratory of Inorganic Materials Chemistry and Application, Department of Materials Engineering, University of Science and Technology of Oran (USTO M.B), BP 1505, El M’naouar, 31000 Oran (Algeria); Dr Moulay Tahar University, Saida (Algeria); Sellami, Mayouf, E-mail: Mourad7dz@yahoo.fr [Laboratory of Inorganic Materials Chemistry and Application, Department of Materials Engineering, University of Science and Technology of Oran (USTO M.B), BP 1505, El M’naouar, 31000 Oran (Algeria); Noureddine, Bettahar, E-mail: nbettahar2001@yahoo.fr [Laboratory of Inorganic Materials Chemistry and Application, Department of Materials Engineering, University of Science and Technology of Oran (USTO M.B), BP 1505, El M’naouar, 31000 Oran (Algeria)

    2016-02-15

    Graphical abstract: Heterogeneous photo Fenton process with dye sensitized mechanism of RhB by Bi{sub 1.56}Sb{sub 1.48}Co{sub 0.96}O{sub 7} compound. - Highlights: • Bi{sub 1.56}Sb{sub 1.48}Co{sub 0.96}O{sub 7} (BSCO) catalyst was synthesized by improved solid state reaction method. • BSCO/H{sub 2}O{sub 2}/UVA and BSCO/H{sub 2}O{sub 2}/SL catalyst systems exhibit excellent photocatalytic activities for rhodamine B. • The photocatalytic degradation was preceded via heterogeneous photo Fenton mechanism process. • ·OH radicals are the main reactive species for the degradation of RhB. - Abstract: Novel nanostructure pyrochlore Bi{sub 1.56}Sb{sub 1.48}Co{sub 0.96}O{sub 7} was successfully synthesized via solid state reaction method in air. The as-synthesized photocatalyst was characterized by X-ray diffraction, Scanning electron microscopy and UV–vis diffuse reflectance spectroscopy techniques. The results showed that the BSCO was crystallized with the pyrochlore-type structure, cubic crystal system and space group Fd3m. The average particle size and band gap for BSCO were D = 76.29 nm and E{sub g} = 1.50 eV respectively. Under the optimum conditions for discoloration of the dye: initial concentration of 20 mg L{sup −1} RhB, pH 7, 25 °C, 0.5 mL H{sub 2}O{sub 2} and BSCO/dye mass ration of 1 g L{sup −1}, 97.77 and 90.16% of RhB were removed with BSCO/H{sub 2}O{sub 2} photocatalytic system within 60 min of irradiation time under UVA- and SL irradiations respectively. Pseudo-second-order kinetic model gave the best fit, with highest correlation coefficients (R{sup 2} ≥ 0.99). On the base of these results, the mechanism of the enhancement of the discoloration efficiency was discussed. .

  12. Study of the nearly constant dielectric loss regime in ionic conductors with pyrochlore-like structure; Estudio del regimen de perdidas dielectricas constantes en conductores ionicos con estructura de tipo pirocloro

    Energy Technology Data Exchange (ETDEWEB)

    Diaz-Guillen, M. r.; Fuentes, A. F.; Diaz-Guillen, J. a.; Santamaria, J.; Leon, C.

    2012-07-01

    We report on ac conductivity measurement of oxide ion conductors with composition Gd{sub 2}(ZryTi{sub 1}-y){sub 2}O{sub 7} and a pyrochlore type structure, at temperatures between -20 and 250 degree centigrade and in the frequency range from 1 Hz to 3 MHz by using impedance spectroscopy. Results show that a crossover from a power law dependence to a linear frequency dependence (or nearly constant loss behavior) in the ac conductivity can be clearly observed in a wide temperature range. This crossover is found to be thermally activated, and its activation energy ENCL to be much lower than the activation energy Edc for the dc conductivity. We also found that the values of ENCL are almost independent of composition, and therefore of the concentration of mobile oxygen vacancies, unlike those of Edc. Moreover, for each composition, the values of E{sub N}CL=0.67{+-}0.04 eV are very similar to those estimated for the energy barrier for the ions to leave their cages, E{sub {alpha}}=0.69{+-}0.05 eV. These results support that the nearly constant loss behavior, ubiquitous in ionic conductors, is originated from caged ion dynamics. (Author) 33 refs.

  13. Preparation, structural characterization, and enhanced electrical conductivity of pyrochlore-type (Sm{sub 1-x}Eu{sub x}){sub 2}Zr{sub 2}O{sub 7} ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Xia, X.L. [Institute for Advanced Ceramics, School of Materials Science and Engineering, Harbin Institute of Technology, Harbin (China); Institute of Oceanography Instruments, Shandong Academy of Science, Chinese National Engineering Research Center for Marine Monitoring Equipment, Qingdao (China); Liu, Z.G.; Ouyang, J.H. [Institute for Advanced Ceramics, School of Materials Science and Engineering, Harbin Institute of Technology, Harbin (China); Zheng, Y. [Institute of Oceanography Instruments, Shandong Academy of Science, Chinese National Engineering Research Center for Marine Monitoring Equipment, Qingdao (China)

    2012-08-15

    (Sm{sub 1-x}Eu{sub x}){sub 2}Zr{sub 2}O{sub 7} (0 {<=} x {<=} 1.0) samples are prepared by solid state reaction method using Sm{sub 2}O{sub 3}, Eu{sub 2}O{sub 3}, and ZrO{sub 2} as starting materials. The phase composition and microstructure of (Sm{sub 1-x}Eu{sub x}){sub 2}Zr{sub 2}O{sub 7} ceramics are investigated by X-ray diffraction (XRD), scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM) coupled with selected area electron diffraction and Raman spectroscopy. XRD and TEM show that all the samples exhibit a single pyrochlore-type structure. HRTEM observation indicates that the whole grain interior of Sm{sub 2}Zr{sub 2}O{sub 7} ceramic is a perfect crystal free of any dislocation. Raman spectroscopy reveals that the degree of structural disorder of (Sm{sub 1-x}Eu{sub x}){sub 2}Zr{sub 2}O{sub 7} ceramics increases gradually with increasing Eu content. The electrical conductivity of (Sm{sub 1-x}Eu{sub x}){sub 2}Zr{sub 2}O{sub 7} ceramics is investigated by impedance spectroscopy in the air and hydrogen atmospheres, respectively. The electrical conductivity of (Sm{sub 1-x}Eu{sub x}){sub 2}Zr{sub 2}O{sub 7} ceramics increases with increasing Eu content at identical temperature levels. Both the activation energy E{sub g} and the pre-exponential factor {sigma}{sub 0g} for the grain conductivity gradually increase with increasing Eu content. As the ionic conductivity shows no obvious change in both air and hydrogen atmospheres, the conduction of (Sm{sub 1-x}Eu{sub x}){sub 2}Zr{sub 2}O{sub 7} is purely ionic with negligible electronic conduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Thermo-selective Tm(x)Ti(1-x)O(2-x/2) nanoparticles: from Tm-doped anatase TiO2 to a rutile/pyrochlore Tm2Ti2O7 mixture. An experimental and theoretical study with a photocatalytic application.

    Science.gov (United States)

    Navas, Javier; Sánchez-Coronilla, Antonio; Aguilar, Teresa; De los Santos, Desireé M; Hernández, Norge C; Alcántara, Rodrigo; Fernández-Lorenzo, Concha; Martín-Calleja, Joaquín

    2014-11-07

    This is an experimental and theoretical study of thulium doped TiO2 nanoparticles. From an experimental perspective, a method was used to synthesize thulium-doped TiO2 nanoparticles in which Tm(3+) replaces Ti(4+) in the lattice, which to our knowledge has neither been reported nor studied theoretically so far. Different proportions of anatase and rutile phases were obtained at different annealing temperatures, and XRD and Raman spectroscopy also revealed the presence of a pyrochlore phase (Tm2Ti2O7) at 1173 K. Thus, the structure of the Tm-doped nanoparticles was thermally-controlled. Furthermore, XPS showed the presence of Tm(3+) in the samples synthesized, which produces oxygen vacancies to maintain the local neutrality in the lattice. The presence of Tm(3+) in the samples led to changes in the UV-Vis absorption spectra, so they showed photoluminescence properties and new states in the band gap, which produce a new lower energy electronic transition than the main TiO2 one. Periodic DFT calculations were performed to understand the experimentally produced structures. The production of oxygen vacancies was analysed and the changes generated in the structure were fully detailed. The DOS and PDOS analyses confirmed the experimental results obtained using UV-Vis spectroscopy, and showed that the new electronic states in the band gap are due to interactions of the f state of Tm and the p state of O. Likewise, the charge study and the ELF analysis indicate that when Tm is introduced into the TiO2 structure, the Ti-O bond around the oxygen vacancy is strengthened. Finally, an example of a photocatalytic application was developed to show the high efficiency of the samples due to the heterojunction in the interfaces of the phases in the samples, which improved the charge separation and the good charge carrier mobility due to the presence of the pyrochlore phase, as was also shown theoretically.

  15. Preparation, optical, and photocatalytic studies of defect pyrochlores: KCr{sub 0.33}W{sub 1.67}O{sub 6} and A{sub x}Cr{sub 0.33}W{sub 1.67}O{sub 6}{center_dot}nH{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Ravi, G.; Veldurthi, Naveen Kumar [Osmania University, Department of Chemistry (India); Prasad, Muvva D. [University of Hyderabad, School of Chemistry (India); Muniratnam, N. R. [Centre for Materials Electronics Technology (C-MET) (India); Prasad, G. [Osmania University, Department of Physics (India); Vithal, M., E-mail: mugavithal@gmail.com [Osmania University, Department of Chemistry (India)

    2013-09-15

    Nano sized defect pyrochlores of compositions KCr{sub 0.33}W{sub 1.67}O{sub 6} and A{sub x}Cr{sub 0.33}W{sub 1.67}O{sub 6}{center_dot}nH{sub 2}O (A = Sn, Ag, Bi, Sm, Eu, and Gd) have been synthesized by sol-gel and ion exchange methods, respectively. These oxides were characterized by thermogravimetric analysis, powder X-ray diffraction, energy dispersive spectra, transmission electron microscopy, UV-Vis diffuse reflectance spectra, Raman spectra, and Fourier transform infrared spectra. Spontaneous exchange of K{sup +} with A ion is accompanied by insertion of water also into the lattice. KCr{sub 0.33}W{sub 1.67}O{sub 6} and A{sub x}Cr{sub 0.33}W{sub 1.67}O{sub 6}{center_dot}nH{sub 2}O crystallize in cubic lattice and isomorphous with KSbWO{sub 6}. The optical properties of Cr{sup 3+} were investigated. Substitution of K{sup +} by A ion leads to a shift of absorption onset to longer wavelengths marginally. The Raman spectra of all the samples are characteristic of defect pyrochlore system. The photocatalytic degradation of methylene blue aqueous solution was investigated using these oxides. The results obtained were fitted with the Langmuir-Hinshelwood model to study the degradation kinetics. Both Sn{sup 2+} and Bi{sup 3+}-doped KCr{sub 0.33}W{sub 1.67}O{sub 6} exhibit higher photoactivity in the degradation of methylene blue. The structure/composition of the photocatalyst remains the same even after fourth cycle of photodegradation.

  16. Process for treatment of pyrochlore concentrates

    International Nuclear Information System (INIS)

    Charlot, G.

    1976-01-01

    A continuous process is described for extraction of niobium, rare earths and thorium from niobium ore concentrates which includes digesting the ore with a hot solution containing 13 to 16 moles of sulphuric acid per liter, diluting the solution to a concentration of 10 to 13 moles of sulphuric acid per liter, separating the insolubles from the solution which includes alkaline earth sulphates and the sulphates of thorium and rare earths that are present, reducing titanium in solution to the trivalent state and diluting the solution to a concentration of 5 to 7 moles of sulphuric acid per liter, separating the precipitated niobium oxide and sulphates of thorium and rare earths, and then concentrating the resulting solution to the level desired for recycle to the digestion stage. 10 Claims, No Drawings

  17. Frustrated pyrochlore oxides, Y2Mn2O7, Ho2Mn2O7, and Yb2Mn2O7: Bulk magnetism and magnetic microstructure

    DEFF Research Database (Denmark)

    Greedan, J.E.; Raju, N.P.; Maignan, A.

    1996-01-01

    The bulk magnetic properties, including de and ac susceptibilities and heat capacity, of the pyrochlore oxides Ho2Mn2O7 and Yb2Mn2O7 are reported and compared with those of the previously studied Y2Mn2O7. In the latter case the magnetic Mn4+ ions occupy the 16c sites in Fd3m which define...... for all three materials are reported for the Q range 10(-2) Angstrom(-1) to 2x10(-1) Angstrom(-1) and the temperature range 6-100 K. Data for the full Q range can be fitted for all three materials to a model consisting of a Lorentzian and a Lorentzian-squared term, i.e., I(Q)=A/(Q(2)+1/xi(1)(2))+B/(Q(2......)+1/xi(2)(2))(2), a cross section commonly found in spin-glass-like materials. A surprising result is that the correlation lengths xi(1) and xi(2) are unequal and in general xi(2)>xi(1). xi(1) remains finite reaching maximum values which range from 10 to 20 Angstrom depending on the compound, while xi(2...

  18. Synthesis and characterization of pyrochlore-type yttrium titanate ...

    Indian Academy of Sciences (India)

    2Key Laboratory of Radioactive Geology and Exploration Technology Fundamental Science for National Defense, ... soft-chemistry technique viz. citric acid sol–gel method (CAM). ... waste (in particular, actinides) (Ewing et al 2004; Pace et al.

  19. Ellipsometry investigation of perovskite/pyrochlore PZT thin film stacks

    Czech Academy of Sciences Publication Activity Database

    Deineka, Alexander; Glinchuk, M. D.; Jastrabík, Lubomír; Suchaneck, G.; Gerlach, G.

    2001-01-01

    Roč. 258, - (2001), s. 271-276 ISSN 0015-0193 R&D Projects: GA MŠk LN00A015; GA ČR GA202/00/1425 Institutional research plan: CEZ:AV0Z1010914 Keywords : ferroelectric film * depth profile * interface Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.471, year: 2001

  20. Protonic defects in pure and doped La2Zr2O7 pyrochlore oxide

    DEFF Research Database (Denmark)

    Björketun, Mårten; Knee, Christopher S.; Nyman, B. Joakim

    2008-01-01

    migration pathway that enables long-range transport is proposed. In addition, the interaction energies between protons and divalent Ba, Sr, Ca, and Mg dopants located on the La- and Zr-sites have been calculated. All interactions are found to be attractive; they are strong in the case of Ba and Mg and quite...

  1. Structure, Raman spectra and defect chemistry modelling of conductive pyrochlore oxides

    DEFF Research Database (Denmark)

    Poulsen, F.W.; Glerup, M.; Holtappels, P.

    2000-01-01

    -O(x) and V-O on the O site, interstitial oxygens O-i", and delocalised electrons and electron holes. Four mass action law expressions govern such a model. The defect model can rationalise why home-valent doping, i.e. substitution of Zr(4+) by Ce(4+), can lead to an increase in ionic conductivity...

  2. A new triclinic modification of the pyrochlore-type KOs 2O 6 superconductor

    Science.gov (United States)

    Katrych, S.; Gu, Q. F.; Bukowski, Z.; Zhigadlo, N. D.; Krauss, G.; Karpinski, J.

    2009-03-01

    A new modification of KOs 2O 6, the representative of a new structural type (Pearson symbol a P18, a=5.5668(1) Å, b=6.4519(2) Å, c=7.2356(2) Å, α=65.377(3)°, β=70.572(3)°, γ=75.613(2)° space group P-1, no. 2 was synthesized employing high pressure technique. Its structure was determined by single-crystal X-ray diffraction. The structure can be described as two OsO 6 octahedral chains relating to each other through inversion and forming big voids with K atoms inside. Quantum chemical calculations were performed on the novel compound and structurally related cubic compound. High-pressure X-ray study showed that cubic KOs 2O 6 phase was stable up to 32.5(2) GPa at room temperature.

  3. Ultrasonic measurement of β-type pyrochlore oxide KOs2O6

    Science.gov (United States)

    Kamiya, Ryosuke; Yoshizawa, Masahito; Nakanishi, Yoshiki; Nakamura, Mitsuteru; Yamaura, Jun-ichi; Hiroi, Zenji

    2010-01-01

    We have measured the temperature dependence of the elastic constants of KOs2O6 single crystal. The longitudinal elastic constant 1/3(C11 + 2C12 + 4C44) and the transverse one 1/3(C11 - C12 + C44), which are obtained by the corresponding sound velocities propagating along direction, show a remarkable elastic softening toward low temperatures. No elastic anomaly was observed at the superconducting transition temperature. On the other hand, an anomaly was found at TP = 7.5 K. These results suggests that the irreducible representation of T2 in Td point group play an important role for the phase transition at Tp.

  4. Novel vortex distribution in the β-pyrochlore superconductor KOs2O6

    Science.gov (United States)

    Shibauchi, T.; Konczykowski, M.; van der Beek, C. J.; Okazaki, R.; Matsuda, Y.; Yamaura, J.; Nagao, Y.; Hiroi, Z.

    2009-03-01

    By utilizing the micro-Hall probe array, we study the superconducting and the vortex states in a single crystal of KOS2O6 near the first-order transition at Tp ~ 8 K, which is associated with a change in the rattling motion of K ions. We show that below the first-order transition, the lower critical field exhibits a distinct decrease, suggesting that the electron-phonon coupling is weakened below the transition. At high magnetic fields, the local magnetization shows an unexpectedly large jump at Tp with a sign change near the sample edges. Our results demonstrate a novel redistribution of vortices whose energy is reduced abruptly below the first-order transition at Tp.

  5. A new triclinic modification of the pyrochlore-type KOs2O6 superconductor

    International Nuclear Information System (INIS)

    Katrych, S.; Gu, Q.F.; Bukowski, Z.; Zhigadlo, N.D.; Krauss, G.; Karpinski, J.

    2009-01-01

    A new modification of KOs 2 O 6 , the representative of a new structural type (Pearson symbol aP18, a=5.5668(1) A, b=6.4519(2) A, c=7.2356(2) A, α=65.377(3) o , β=70.572(3) o , γ=75.613(2) o space group P-1, no. 2 was synthesized employing high pressure technique. Its structure was determined by single-crystal X-ray diffraction. The structure can be described as two OsO 6 octahedral chains relating to each other through inversion and forming big voids with K atoms inside. Quantum chemical calculations were performed on the novel compound and structurally related cubic compound. High-pressure X-ray study showed that cubic KOs 2 O 6 phase was stable up to 32.5(2) GPa at room temperature. - Graphical abstract: A new modification of KOs 2 O 6 , the representative of a new structural type (Pearson symbol aP18, a=5.5668(1) A, b=6.4519(2) A, c=7.2356(2) A, α=65.377(3) o , β=70.572(3) o , γ=75.613(2) o space group P-1, no. 2 was synthesized employing high pressure technique. The structure can be described as two OsO 6 octahedral chains relating to each other through inversion and forming big voids with K atoms inside

  6. C60 and U ion irradiation of Gd2TixZr2-xO7 pyrochlore

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jiaming; Toulemonde, Marcel; Lang, Maik; Costantini, Jean Marc; Della-Negra, Serge; Ewing, Rodney C.

    2015-08-01

    Abstract

  7. Fundamental aspects of actinide-zirconium pyrochlore oxides: Systematic comparison of the Pu, Am, Cm, Bk and Cf systems

    International Nuclear Information System (INIS)

    Haire, R.G.; Raison, P.E.

    2000-01-01

    Zirconium- and hafnium-based oxide materials have gained attraction for various nuclear applications. These materials have features in common with one of the early, well-publicized inorganic ceramics for immobilizing nuclear waste. Our interests have addressed the fundamental structural and chemical properties of these oxide systems. We pursued both the crystal chemical constraints of the oxide matrices, as well as the importance of the chemistry of the f-elements. By incorporating five actinide elements in our studies, we were able to compare systematically the materials science of these materials with the fundamental chemistry and electronic configurations of these actinides employed. It is expected that this basic information will be useful technologically in the realm of tailor-made materials for different applications

  8. Magnetic Excitations across the Metal-Insulator Transition in the Pyrochlore Iridate Eu2Ir2O7

    Science.gov (United States)

    Chun, Sae Hwan; Yuan, Bo; Casa, Diego; Kim, Jungho; Kim, Chang-Yong; Tian, Zhaoming; Qiu, Yang; Nakatsuji, Satoru; Kim, Young-June

    2018-04-01

    We report a resonant inelastic x-ray scattering study of the magnetic excitation spectrum in a highly insulating Eu2 Ir2 O7 single crystal that exhibits a metal-insulator transition at TMI=111 (7 ) K . A propagating magnon mode with a 20 meV bandwidth and a 28 meV magnon gap is found in the excitation spectrum at 7 K, which is expected in the all-in-all-out magnetically ordered state. This magnetic excitation exhibits substantial softening as the temperature is raised towards TMI and turns into a highly damped excitation in the paramagnetic phase. Remarkably, the softening occurs throughout the whole Brillouin zone including the zone boundary. This observation is inconsistent with the magnon renormalization expected in a local moment system and indicates that the strength of the electron correlation in Eu2 Ir2 O7 is only moderate, so that electron itinerancy should be taken into account in describing its magnetism.

  9. Thermal expansion and conductivity of RE2Sn2O7 (RE = La, Nd, Sm, Gd, Er and Yb) pyrochlores

    International Nuclear Information System (INIS)

    Feng, J.; Xiao, B.; Zhou, R.; Pan, W.

    2013-01-01

    Graphical abstract: Calculated cohesive energies and formation enthalpies of RE 2 Sn 2 O 7 compounds. The formation enthalpies at 298 K are more close to the experimental values. -- The calculated cohesive energies and formation enthalpies of Rare earth stannate (RE 2 Sn 2 O 7 ) compounds are in good agreement with the corresponding experimental values. The thermal expansion coefficients (TECs) of rare earth stannates are 7–9 × 10 −6 K −1 at high temperature. The results show that local spin density approximation predicts smaller TECs than the real values. The computed thermal conductivity of RE 2 Sn 2 O 7 is 1.8–2.5 W (m · K) −1 at 1273 K using the Slack–Clarke model, indicating that RE 2 Sn 2 O 7 compounds exhibit good thermal insulating properties at high temperature

  10. Superconducting to spin-glass state transformation in β-pyrochlore KxOs2O6

    Science.gov (United States)

    Lee, C. C.; Lee, W. L.; Lin, J.-Y.; Tsuei, C. C.; Lin, J. G.; Chou, F. C.

    2011-03-01

    β-pyrochore KOs2O6, which shows superconductivity below ~9.7 K, has been converted into KxOs2O6 (x≲(2)/(3)-(1)/(2)) electrochemically to show spin-glass-like behavior below ~6.1 K. A room-temperature sample surface potential versus charge transfer scan indicates that there are at least two two-phase regions for x between 1 and 0.5. A rattling model of superconductivity for the title compound has been examined using electrochemical potassium de-intercalation. The significant reduction of superconducting volume fraction due to minor potassium reduction suggests the importance of defect and phase coherence in the rattling model. Magnetic susceptibility, resistivity, and specific heat measurement results have been compared between the superconducting and spin-glass-like samples.

  11. Full-gap superconductivity with strong electron correlations in the β-pyrochlore KOs2O6

    International Nuclear Information System (INIS)

    Kasahara, Y.; Shimono, Y.; Kato, T.; Hashimoto, K.; Shibauchi, T.; Matsuda, Y.; Yonezawa, S.; Muraoka, Y.; Yamaura, J.; Nagao, Y.; Hiroi, Z.

    2008-01-01

    To elucidate the superconducting gap structure and the influence of rattling motion on quasiparticle dynamics in the superconducting state of KOs 2 O 6 , the thermal conductivity and microwave surface impedance were measured at low temperatures. The magnetic field dependence of thermal conductivity and temperature dependence of penetration depth demonstrate full-gap superconductivity in KOs 2 O 6 . The quasiparticle scattering time is strongly enhanced in the superconducting state, indicating a strong electron inelastic scattering in the normal state. These results highlight that KOs 2 O 6 is unique among superconductors with strong electron correlations

  12. Magnetic order, magnetic correlations, and spin dynamics in the pyrochlore antiferromagnet Er2Ti2O7

    Science.gov (United States)

    Dalmas de Réotier, P.; Yaouanc, A.; Chapuis, Y.; Curnoe, S. H.; Grenier, B.; Ressouche, E.; Marin, C.; Lago, J.; Baines, C.; Giblin, S. R.

    2012-09-01

    Er2Ti2O7 is believed to be a realization of an XY antiferromagnet on a frustrated lattice of corner-sharing regular tetrahedra. It is presented as an example of the order-by-disorder mechanism in which fluctuations lift the degeneracy of the ground state, leading to an ordered state. Here we report detailed measurements of the low-temperature magnetic properties of Er2Ti2O7, which displays a second-order phase transition at TN≃1.2 K with coexisting short- and long-range orders. Magnetic susceptibility studies show that there is no spin-glass-like irreversible effect. Heat capacity measurements reveal that the paramagnetic critical exponent is typical of a 3-dimensional XY magnet while the low-temperature specific heat sets an upper limit on the possible spin-gap value and provides an estimate for the spin-wave velocity. Muon spin relaxation measurements show the presence of spin dynamics in the nanosecond time scale down to 21 mK. This time range is intermediate between the shorter time characterizing the spin dynamics in Tb2Sn2O7, which also displays long- and short-range magnetic order, and the time scale typical of conventional magnets. Hence the ground state is characterized by exotic spin dynamics. We determine the parameters of a symmetry-dictated Hamiltonian restricted to the spins in a tetrahedron, by fitting the paramagnetic diffuse neutron scattering intensity for two reciprocal lattice planes. These data are recorded in a temperature region where the assumption that the correlations are limited to nearest neighbors is fair.

  13. Band structure of metallic pyrochlore ruthenates Bi2Ru2O7 and Pb2Ru2O/sub 6.5/

    International Nuclear Information System (INIS)

    Hsu, W.Y.; Kasowski, R.V.; Miller, T.; Chiang, T.

    1988-01-01

    The band structure of Bi 2 Ru 2 O 7 and Pb 2 Ru 2 O/sub 6.5/ has been computed self-consistently from first principles for the first time by the pseudofunction method. We discover that the 6s bands of Bi and Pb are very deep and unlikely to contribute to the metallic behavior as previously believed. The unoccupied 6p bands, however, are only several eV above the Fermi energy and are mixed with the Ru 4d band at the Fermi surface via the framework O atoms, leading to band conduction and delocalized magnetic moments. The predicted location of the 6s bands and the location and width of the O 2p band are confirmed by synchrotron radiation and ultraviolet electron spectroscopy of single crystals

  14. Spin-glass state in the mixed system (Co1-xFex)2(OH)3Cl on deformed pyrochlore lattice

    International Nuclear Information System (INIS)

    Fujihala, M.; Hagihala, M.; Zheng, X.G.; Kawae, T.

    2009-01-01

    Magnetic interactions in a new geometrically frustrated system (Co 1-x Fe x ) 2 (OH) 3 Cl are investigated using magnetic susceptibility and μSR study. While Co 2 (OH) 3 Cl is ferromagnetic and Fe 2 (OH) 3 Cl antiferromagnetic, the partially substituted series (Co 1-x Fe x ) 2 (OH) 3 Cl show spin-glass behaviours, wherein ferromagnetic interactions prevail for low Fe concentration and antiferromagnetic ones prevail for high Fe concentration. In special, analysis of the AC magnetic susceptibility and ZF-μ + SR for the x=0.5 sample suggest that CoFe(OH) 3 Cl has both features of chemically disordered random spin glass and geometrically frustrated spin glass. It is also the first spin-glass system for the newly found geometric frustration series M 2 (OH) 3 X.

  15. Intermediate temperature ionic conductivity of Sm1.92Ca0.08Ti2O7–δ pyrochlore

    DEFF Research Database (Denmark)

    Eurenius, Karinh E. J.; Bentzer, Henrik Karnøe; Bonanos, Nikolaos

    2011-01-01

    (500–300 °C). The impedance measurements revealed the conductivity to be mainly ionic under all conditions, with the highest total conductivity measured being 0.045 S/m under wet oxygen at 500 °C. Both bulk and grain boundary conductivity was predominantly ionic, but electronic conductivity appeared...... to play a slightly larger part in the grain boundaries. EMF data confirmed the conductivity to be mainly ionic, with oxide ions being the major conducting species at 500 °C and protons becoming increasingly important below this temperature....

  16. Synthesis of BZN-(α) and BZN-(β) pyrochloric ceramics by the solid state relation; Sintese das ceramicas pirocloricas BZN-α e BZN-β pela relacao em estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Farias, F.C.; Alves, A.G.; Alves, Y.M.; Pereira, F.M.M.; Barroso, M.B., E-mail: werleyfarias@gmail.com [Universidade Federal do Cariri (UFCA), Juazeiro do Norte, CE (Brazil); Pereira, C.A.; Saraiva, I.R. [Faculdade DeVry Fanor (FANOR), Fortaleza, CE (Brazil); Conde, W.S.; Sombra, A.B. [Laboratorio de Telecomunicacoes e Ciencia e Engenharia de Materiais (LOCEM), CE (Brazil)

    2016-07-01

    The ceramics the base of Bi{sub 2}O{sub 3}-ZnO-Nb{sub 2}O{sub 5} (BZN) have two main phases, Bi{sub 1,5}ZnNb{sub 1,5}O{sub 7} (α) and Bi{sub 2}Zn{sub 2/3}Nb{sub 4/3}O{sub 7} (β) with cubic and monoclinic crystal structures, respectively. This study was aimed to summarize the BZN-α phase and BZN-β chemically homogeneous and observe the phase transformations that occur in the system, using the ceramic method. They were characterized by scanning electron microscopy (SEM), X-Ray Diffraction (XRD), and the Rietveld method in structural refinement and Infrared Spectroscopy. The BZN-α phase is presented in pure sintering temperatures used, although BZN-β phase has brought the remaining stages of its formation process, as Bi{sub 5}Nb{sub 3}O{sub 15} and BiNbO{sub 4}. For BZN-α were observed absorptions at 469 and 328 cm{sup -1}, attributed to the metal-oxygen stretch the BZN-β showed absorption bands at wavelengths of 601, 515, 447 and 328 cm{sup -1}, also being assigned metal-oxygen bond. (author)

  17. Transparent nanoscale floating gate memory using self-assembled bismuth nanocrystals in Bi(2) Mg(2/3) Nb(4/3) O(7) (BMN) pyrochlore thin films grown at room temperature.

    Science.gov (United States)

    Jung, Hyun-June; Yoon, Soon-Gil; Hong, Soon-Ku; Lee, Jeong-Yong

    2012-07-03

    Bismuth nanocrystals for a nanoscale floating gate memory device are self-assembled in Bi(2) Mg(2/3) Nb(4/3) O(7) (BMN) dielectric films grown at room temperature by radio-frequency sputtering. The TEM cross-sectional image shows the "real" structure grown on a Si (001) substrate. The image magnified from the dotted box (red color) in the the cross-sectional image clearly shows bismuth nanoparticles at the interface between the Al(2) O(3) and HfO(2) layer (right image). Nanoparticles approximately 3 nm in size are regularly distributed at the interface. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Quantum paraelectric behavior of pyrochlore Pb.sub.1.83./sub.Mg.sub.0.29./sub.Nb.sub.1.71./sub.O.sub.6.39./sub..

    Czech Academy of Sciences Publication Activity Database

    Kamba, Stanislav; Nuzhnyy, Dmitry; Denisov, Sergey; Veljko, Sergiy; Bovtun, Viktor; Savinov, Maxim; Petzelt, Jan; Kalnberga, M.; Sternberg, A.

    2007-01-01

    Roč. 76, - (2007), 054125/1-054125/6 ISSN 1098-0121 R&D Projects: GA ČR(CZ) GA202/06/0403 Institutional research plan: CEZ:AV0Z10100520 Keywords : quantum paraelectrics * soft mode * infrared spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.172, year: 2007

  19. Deliberate exotic magnetism via frustration and topology

    Science.gov (United States)

    Nisoli, Cristiano; Kapaklis, Vassilios; Schiffer, Peter

    2017-03-01

    Introduced originally to mimic the unusual, frustrated behaviour of spin ice pyrochlores, artificial spin ice can be realized in odd, dedicated geometries that open the door to new manifestations of a higher level of frustration.

  20. Chemical synthesis and characterization of nano-sized rare-earth ...

    Indian Academy of Sciences (India)

    2

    pyrochlore samples indicated a single phase crystalline material with a cubic ... vary with the size and the surface area of the particles.6 Thus, a method to ..... From qualitative band-model consideration of the type discussed by Goodenough.

  1. Effect of cerium additive and secondary phase analysis on Ag0.5Bi0 ...

    Indian Academy of Sciences (India)

    Technical University of Madrid (UPM), Madrid 28012, Spain. MS received 27 ... XRD analysis showed the presence of pyrochlore structure and secondary phase when more .... The present work reports the effect of incorporation of cerium in ...

  2. Advanced Oxide Material Systems for 1650 Deg. C Thermal/Environmental Barrier Coating Applications

    National Research Council Canada - National Science Library

    Zhu, Dongming; Fox, Dennis S; Bansal, Narottam P; Miller, Robert A

    2004-01-01

    ... systems under engine high-heat-flux and severe thermal cycling conditions. In this report, the thermal conductivity and water vapor stability of selected candidate hafnia-, pyrochlore-, and magnetoplumbite-based TEBC materials are evaluated...

  3. High throughput synthesis and characterization of the PbnNb2O5+n (0.5 < n < 4.1) system on a single chip

    International Nuclear Information System (INIS)

    Mirsaneh, Mehdi; Hayden, Brian E.; Miao Shu; Pokorny, Jan; Perini, Steve; Furman, Eugene; Lanagan, Michael T.; Ubic, Rick; Reaney, Ian M.

    2011-01-01

    Most high throughput studies focus on assessing the effect of composition within a single known fundamental structure type, such as perovskite. Here we demonstrate how high throughput synthesis and screening can be used to establish structure-property relations in the PbO-Nb 2 O 5 system, for which eight distinct fundamental structure types are known to exist. PbNb 4 O 11 , PbNb 2 O 6 and pyrochlore could be easily distinguished by X-ray diffraction (XRD). However, XRD was insensitive to distortions of the pyrochlore structure and instead Raman spectroscopy was utilized to determine changes in symmetry from cubic to rhombohedral as the PbO concentration increased. High throughput screening of the capacitance revealed permittivity (ε r ) maxima in the PbNb 4 O 11 (ε r = 700) and cubic pyrochlore phases (ε r = 450). The ε r of PbNb 4 O 11 has not to date been reported but the value for cubic pyrochlore is higher than that reported for bulk ceramics (ε r = 270). Initial high electric field studies also revealed exceptionally high tunability (four times that reported for bismuth zinc niobate-based pyrochlores) of the capacitance in the pyrochlore phase.

  4. Sintering Characteristics of Multilayered Thermal Barrier Coatings Under Thermal Gradient and Isothermal High Temperature Annealing Conditions

    Science.gov (United States)

    Rai, Amarendra K.; Schmitt, Michael P.; Bhattacharya, Rabi; Zhu, Dongming; Wolfe, Douglas E.

    2014-01-01

    Pyrochlore oxides have most of the relevant attributes for use as next generation thermal barrier coatings such as phase stability, low sintering kinetics and low thermal conductivity. One of the issues with the pyrochlore oxides is their lower toughness and therefore higher erosion rate compared to the current state-of-the-art TBC material, yttria (6 to 8 wt%) stabilized zirconia (YSZ). In this work, sintering characteristics were investigated for novel multilayered coating consisted of alternating layers of pyrochlore oxide viz Gd2Zr2O7 and t' low k (rare earth oxide doped YSZ). Thermal gradient and isothermal high temperature (1316 C) annealing conditions were used to investigate sintering and cracking in these coatings. The results are then compared with that of relevant monolayered coatings and a baseline YSZ coating.

  5. The effect of B-site substitution on structural transformation and ionic conductivity in Ho2(ZryTi1−y)2O7

    International Nuclear Information System (INIS)

    Shafique, Muhammad; Kennedy, Brenden J.; Iqbal, Yaseen; Ubic, Rick

    2016-01-01

    Compounds in the pyrochlore system Ho 2 (Zr y Ti 1−y ) 2 O 7 exhibit an order-disorder transition from pyrochlore to a defect-fluorite type structure. Compositions in this system were prepared via mechanical milling, followed by a two-step sintering process. Structural characterization was carried out via Rietveld refinements using neutron powder diffraction data, supported by X-ray diffraction to determine the phase and location of the pyrochlore-fluorite transformation. Unit-cell parameters were determined for the whole series using Rietveld refinements as well as the Nelson–Riley function. The neutron refinement results confirmed that the cation disorder was independent of the anion Frenkel disorder. The relation between the x-parameter in the oxygen 48f position and anion Frenkel disorder was found to be linear for the pyrochlore structure. The ionic conductivity studies were undertaken via AC impedance analysis to determine the electronic behaviour and its relation to the structural change in the temperature range 300°C–700 °C. The trends in ionic conductivity and activation energy were explained structurally via neutron powder diffraction and X-ray diffraction data. The pyrochlore-fluorite boundary composition (at y = 0.5) exhibited the lowest activation energy and highest ionic conductivity. - Highlights: • Ho 2 (Zr y Ti 1-y ) 2 O 7 structure changed from ordered pyrochlore to defect-fluorite at y = 0.6. • Ho 2 (Zr 0.5 Ti 0.5 ) 2 O 7 exhibited high ionic conductivity and low activation energy. • Doping improved stability in ionic conductivity behaviour at lower temperature.

  6. SYNROC C: preparation and radwaste distribution

    International Nuclear Information System (INIS)

    Ryerson, F.J.; Hoenig, C.L.; Smith, G.S.

    1981-01-01

    Results of the synthesis of SYNROC C from both high surface area (16m 2 /g) and low surface area (4m 2 /g) powders at low and high oxygen fugacities indicate variations in radionuclide distribution. These results are most striking for the partitioning of uranium between perovskite and zirconolite. In highly active powders, the formation of a pyrochlore precursor ensures that equilibrium partitioning is approached. In less active powders, no low temperature pyrochlore is formed. As a result, the uranium partitioning is a function of nucleation processes. At high oxygen fugacities, uranium is rejected from perovskite and an additional uranium rich phase is formed precluding the synthesis of SYNROC C in air

  7. Interface formation and defect structures in epitaxial La2Zr2O7 thin films on (111) Si

    International Nuclear Information System (INIS)

    Seo, J.W.; Fompeyrine, J.; Guiller, A.; Norga, G.; Marchiori, C.; Siegwart, H.; Locquet, J.-P.

    2003-01-01

    We have studied the growth of epitaxial La 2 Zr 2 O 7 thin films on (111) Si. Although the interface structure can be strongly affected by the Si oxidation during the deposition process, epitaxial growth of La 2 Zr 2 O 7 was obtained. A detailed study by means of transmission electron microscopy reveals two types of structures (pyrochlore and fluorite) with the same average chemical composition but strong differences in reactivity and interface formation. The structural complexity of the ordered pyrochlore structure seems to prevent excess oxygen diffusion and interfacial SiO 2 formation

  8. Actinides compounds for the transmutation: scientific contributions of american and japanese collaborations; Composes d'actinides pour la transmutation: apports scientifiques de collaborations americaines et japonaises

    Energy Technology Data Exchange (ETDEWEB)

    Raison, Ph.; Albiot, T

    2000-07-01

    This paper deals with the minor actinides transmutation and the scientific contribution of the ORNL and the JAERI. It presents researches on the Am-Zr-Y-O system in the framework of the heterogeneous reprocessing, the curium and pyrochlore structures, with the ORNL contribution and phase diagrams, data of Thermodynamics, actinides nitrides, with the JAERI. (A.L.B.)

  9. Hydroxycalciopyrochlore from a regionally metamorphic marble at Bližná, Southwestern Czech Republic

    Czech Academy of Sciences Publication Activity Database

    Drábek, M.; Frýda, J.; Šarbach, M.; Skála, Roman

    2017-01-01

    Roč. 194, č. 1 (2017), s. 49-59 ISSN 0077-7757 Institutional support: RVO:67985831 Keywords : hydroxycalciopyrochlore * pyrochlore * carbonatite-like marble * marble * Moldanubian Varied Group Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Mineralogy Impact factor: 0.811, year: 2016

  10. Bulletin of Materials Science | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science. N J KARALE. Articles written in Bulletin of Materials Science. Volume 40 Issue 7 December 2017 pp 1335-1345. Chemical synthesis and characterization of nano-sized rare-earth ruthenium pyrochlore compounds Ln 2 Ru 2 O 7 (Ln = rare earth) · R A PAWAR A K NIKUMBH ...

  11. Pramana – Journal of Physics | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Nd2Sn2O7 pyrochlores with the substitution of Zr4+ were prepared by conventional ceramic double sintering technique. The single-phase formation was confirmed by X-ray diffraction and neutron diffraction techniques. Relative intensity calculations for X-ray diffraction analysis were performed for oxygen positional ...

  12. S K Paranjpe

    Indian Academy of Sciences (India)

    Home; Journals; Pramana – Journal of Physics. S K Paranjpe. Articles written in Pramana – Journal of Physics. Volume 63 Issue 2 August 2004 pp 189-197 Contributed Papers : Neutron diffraction. Structural study and electrical properties of Zr-doped Nd2Sn2O7 pyrochlore compounds · Y D Kolekar S B Kulkarni Keka ...

  13. Fundamental aspects of Am and Cm in zirconia-based materials. Investigations using X-ray diffraction and Raman spectroscopy

    International Nuclear Information System (INIS)

    Raison, P.E.; Haire, R.G.; Assefa, Z.

    2002-01-01

    We have investigated incorporation of americium and curium in selected zirconia-based materials. Fundamental aspects were explored via X-ray diffraction and Raman spectroscopy. First explored was the pseudo ternary system, AmO 2 -ZrO 2 -Y 2 O 3 . It was found that stable, cubic solid solutions (Am x Zr 1-x Y y )O 2-2/y can be obtained for selected compositions. The cell parameters of the cubic phases were established as being linear with the AmO 2 content. For the Cm 2 O 3 -ZrO 2 system, it was determined that diphasic materials are produced, except for two compositions: 25 mol% and 50 mol% of CmO 1.5 . For these compositions a single-phase cubic fluorite type solid solution (a=5.21A±0.01) and a pyrochlore oxide Cm 2 Zr 2 O 7 (a=10.63A±0.02) are formed, respectively. The stability of pyrochlore oxides is also being investigated as a function of self-irradiation, using shorter-lived isotopes, one being the californium pyrochlore 249 Cf 2 Zr 2 O 7 . We obtained evidence that after six months of storage the pyrochlore oxide is undergoing structural change. Additional studies are in progress. (author)

  14. A novel high-temperature commensurate superstructure in a natural bariopyrochlore: A structural study by means of a multiphase crystal structure refinement

    Czech Academy of Sciences Publication Activity Database

    Bindi, L.; Petříček, Václav; Withers, R. L.; Zoppi, M.; Bonazzi, P.

    2006-01-01

    Roč. 179, - (2006), s. 716-725 ISSN 0022-4596 R&D Projects: GA ČR(CZ) GA202/03/0430 Institutional research plan: CEZ:AV0Z10100521 Keywords : pyrochlore * superstructure * X-ray data * multiphase structure refinement * TEM study Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.107, year: 2006

  15. Topological honeycomb magnon Hall effect: A calculation of thermal Hall conductivity of magnetic spin excitations

    Energy Technology Data Exchange (ETDEWEB)

    Owerre, S. A., E-mail: solomon@aims.ac.za [African Institute for Mathematical Sciences, 6 Melrose Road, Muizenberg, Cape Town 7945, South Africa and Perimeter Institute for Theoretical Physics, 31 Caroline St. N., Waterloo, Ontario N2L 2Y5 (Canada)

    2016-07-28

    Quite recently, the magnon Hall effect of spin excitations has been observed experimentally on the kagome and pyrochlore lattices. The thermal Hall conductivity κ{sup xy} changes sign as a function of magnetic field or temperature on the kagome lattice, and κ{sup xy} changes sign upon reversing the sign of the magnetic field on the pyrochlore lattice. Motivated by these recent exciting experimental observations, we theoretically propose a simple realization of the magnon Hall effect in a two-band model on the honeycomb lattice. The magnon Hall effect of spin excitations arises in the usual way via the breaking of inversion symmetry of the lattice, however, by a next-nearest-neighbour Dzyaloshinsky-Moriya interaction. We find that κ{sup xy} has a fixed sign for all parameter regimes considered. These results are in contrast to the Lieb, kagome, and pyrochlore lattices. We further show that the low-temperature dependence on the magnon Hall conductivity follows a T{sup 2} law, as opposed to the kagome and pyrochlore lattices. These results suggest an experimental procedure to measure thermal Hall conductivity within a class of 2D honeycomb quantum magnets and ultracold atoms trapped in a honeycomb optical lattice.

  16. Niobium-Thorium-Strontium-Rare Earth Element Mineralogy and Preliminary Sulphur Isotope Geochemistry of the Eaglet Property, East-Central British Columbia (NTS 093A/10W)

    Czech Academy of Sciences Publication Activity Database

    Hora, Z. D.; Langrová, Anna; Pivec, Edvín; Žák, Karel

    2010-01-01

    Roč. 2009, č. 1 (2010), s. 93-96 ISSN 0381-243X Institutional research plan: CEZ:AV0Z30130516 Keywords : fluorite * celestite * pyrochlore * thorite * titanbetafite * bastnaesite * sulphur isotopes * Eaglet deposit * MINFILE 093A46 Subject RIV: DD - Geochemistry http://www.empr.gov.bc.ca/Mining/Geoscience/PublicationsCatalogue/Fieldwork/Documents/2009/08_Hora_2009.pdf

  17. Untitled

    Indian Academy of Sciences (India)

    Materials Science Research Centre, Indian Institute of Technology, Madras 600 036,. India. MS received 10 May 1980. Abstract. Complete series of solid solutions exist in the mixed oxide pyrochlore system, Erº (Vºl. Feºf) vs W:O, with the crystal structure changing from cubic to rhombohedral at x = 0.25. The compounds are ...

  18. Er2Ti2O7: Evidence of quantum order by disorder in a frustrated antiferromagnet

    DEFF Research Database (Denmark)

    Champion, J.D.M.; Harris, M.J.; Holdsworth, P.C.W.

    2003-01-01

    Er(2)Ti(2)O(7) has been suggested to be a realization of the frustrated XY pyrochlore lattice antiferromagnet, for which theory predicts fluctuation-induced symmetry breaking in a highly degenerate ground state manifold. We present a theoretical analysis of the classical model compared...

  19. Actinides compounds for the transmutation: scientific contributions of american and japanese collaborations

    International Nuclear Information System (INIS)

    Raison, Ph.; Albiot, T.

    2000-01-01

    This paper deals with the minor actinides transmutation and the scientific contribution of the ORNL and the JAERI. It presents researches on the Am-Zr-Y-O system in the framework of the heterogeneous reprocessing, the curium and pyrochlore structures, with the ORNL contribution and phase diagrams, data of Thermodynamics, actinides nitrides, with the JAERI. (A.L.B.)

  20. Radiation effects in uranium-niobium titanates

    International Nuclear Information System (INIS)

    Lian, J.; Wang, S.X.; Wang, L.M.; Ewing, R.C.

    2000-01-01

    Pyrochlore is an important actinide host phase proposed for the immobilization of high level nuclear wastes and excess weapon plutonium.[1] Synthetic pyrochlore has a great variety of chemical compositions due to the possibility of extensive substitutions in the pyrochlore structure.[2] During the synthesis of pyrochlore, additional complex titanate phases may form in small quantities. The response of these phases to radiation damage must be evaluated because volume expansion of minor phases may cause micro-fracturing. In this work, two complex uranium-niobium titanates, U 3 NbO 9.8 (U-rich titanate) and Nb 3 UO 10 (Nb-rich titanate) were synthesized by the alkoxide/nitrate route at 1300 deg. C under an argon atmosphere. The phase composition and structure were analyzed by EDS, BSE, XRD, EMPA and TEM techniques. An 800 KeVKr 2+ irradiation was performed using the IVEM-Tandem Facility at Argonne National Laboratory in a temperature range from 30 K to 973 K. The radiation effects were observed by in situ TEM

  1. Colloidal alloys with preassembled clusters and spheres.

    Science.gov (United States)

    Ducrot, Étienne; He, Mingxin; Yi, Gi-Ra; Pine, David J

    2017-06-01

    Self-assembly is a powerful approach for constructing colloidal crystals, where spheres, rods or faceted particles can build up a myriad of structures. Nevertheless, many complex or low-coordination architectures, such as diamond, pyrochlore and other sought-after lattices, have eluded self-assembly. Here we introduce a new design principle based on preassembled components of the desired superstructure and programmed nearest-neighbour DNA-mediated interactions, which allows the formation of otherwise unattainable structures. We demonstrate the approach using preassembled colloidal tetrahedra and spheres, obtaining a class of colloidal superstructures, including cubic and tetragonal colloidal crystals, with no known atomic analogues, as well as percolating low-coordination diamond and pyrochlore sublattices never assembled before.

  2. Lanthanide ions doped Y2Sn2O7 nano-particles: low temperature synthesis and photoluminescence study

    International Nuclear Information System (INIS)

    Nigam, Sandeep; Sudarsan, V.; Vatsa, R.K.

    2008-01-01

    During the past decade, pyrochlore-type oxides (A 2 B 2 O 7 ) have emerged as important host matrices for lanthanide doped luminescent materials due to their higher thermal stability. Up to now, conventional solid-state reaction is the most commonly used synthetic method for preparation, of rare-earth pyrochlore oxides. This synthesis route employs a solid-state reaction of metal-oxide with appropriate rare-earth oxides at high temperature (>1200 deg C) for a long time (several days). However, in present work, Y 2 Sn 2 O 7 nanoparticles co-doped with lanthanide ions Tb 3+ and Ce 3+ were prepared based on the urea hydrolysis of Y 3+ , Sn 4+ , and Ln 3+ in ethylene glycol medium at 150 deg C followed by heating at 500, 700 and 900 deg C

  3. Combined wet-chemical process to synthesize 65PMN-35PT nanosized powders

    International Nuclear Information System (INIS)

    Santos, Luis P.S.; Longo, Elson; Leite, Edson R.; Camargo, Emerson R.

    2004-01-01

    Columbite MgNb 2 O 6 precursors were synthesized by a wet-chemical method by means of the dissolution of Nb 2 O 5 .5H 2 O and magnesium carbonate in a solution of oxalic acid. Pure 65PMN-35PT powders could be obtained by the columbite method with the use of the partial oxalate and oxidant peroxo methods. Powders were characterized by X-ray diffraction and FT-Raman spectroscopy showing that pure 65PMN-35PT are obtained when the powders are calcined up to 800 deg. C, without any trace of Pb-Nb pyrochlore. Cubic Pb 1,86 Mg 0.24 Nb 1.76 O 6.5 pyrochlore phase is formed by lead loss in the powders calcined at 900 deg. C and higher temperatures as undoubtedly characterized by Raman spectroscopy

  4. Synroc for plutonium disposal

    International Nuclear Information System (INIS)

    Johnston, A.; Vance, E.R.

    1999-01-01

    A pyrochlore-rich titanate ceramic has been chosen by the US DOE for excess weapons Pu immobilisation in the USA. The development of this wasteform was based on the Synroc strategy which aims to immobilise radioactive waste in durable multiphase titanate ceramics with phases chosen to he similar to titanate minerals that exist in nature and have immobilised U and Th for billions of years. The evolution of the pyrochlore-rich ceramic for Pu immobilisation from earlier Synroc variants is described and the choice of process steps is discussed. Leaching studies demonstrate that the release rate of Pu from the wasteforms in aqueous media is very low and similar to those of U and the neutron absorbers Gd and Hf that will ensure avoidance of nuclear criticality in repository environments

  5. Theoretical study of disorder in Ti-substituted La2Zr2O7

    International Nuclear Information System (INIS)

    Chartier, Alain; Meis, Constantin; Weber, William J.; Corrales, L. Rene

    2002-01-01

    Pyrochlores have the striking feature that their radiation resistance is highly dependent on their composition. In this work, the propensity of a pyrochlore to transform to a cation-disordered structure and the influence of titanium ions is ascertained from the mechanisms of defect formation. A detailed study of defect formation and migration activation energies in Ti-substituted La 2 Zr 2 O 7 is carried out by modern theoretical computational methods that include the use of a classical interatomic potential with a modified shell model to capture the effects of local charge transfer. The results show that La 2 Zr 2 O 7 has a tendency towards cation disorder, whereas, substitution of Zr with Ti makes this tendency energetically less favorable

  6. PDF analysis on re-crystallized structure from amorphous BiT

    Energy Technology Data Exchange (ETDEWEB)

    Yoneda, Yasuhiro [Japan Atomic Energy Research Institute, Synchrotron Radiation Research Center, Kouto 1-1-1, Mikazuki-cho, Sayo-gun, Hyogo 679-5148 (Japan)]. E-mail: yoneda@spring8.or.jp; Kohara, Shinji [Synchrotron Radiation Research Laboratory, Japan Synchrotron Radiation, Research Institute, Kouto 1-1-1, Mikazuki-cho, Sayo-gun, Hyogo 679-5198 (Japan); Hamazaki, Shin' ichi [Department of Electronics, Iwaki Meisei University, Iino 5-5-1, Chuohdai, Fukushima 970-8551 (Japan); Takashige, Masaaki [Department of Electronics, Iwaki Meisei University, Iino 5-5-1, Chuohdai, Fukushima 970-8551 (Japan); Mizuki, Jun' ichiro [Japan Atomic Energy Research Institute, Synchrotron Radiation Research Center, Kouto 1-1-1, Mikazuki-cho, Sayo-gun, Hyogo 679-5148 (Japan)

    2005-08-15

    A glass sample of composition Bi{sub 4}Ti{sub 3}O{sub 12} was prepared by rapid quenching. The as-quenched sample was confirmed to be amorphous by synchrotron X-ray measurements. The crystallization process of the amorphous sample was also investigated by high-energy X-ray diffraction and by atomic pair distribution function analysis. The perovskite layer in the crystal Bi{sub 4}Ti{sub 3}O{sub 12} is transformed to a pyrochlore structure in the amorphous sample. The amorphous sample first crystallized to a metastable phase by acquiring long-range ordering of the pyrochlore structure at T {sub cryst1}, and then secondary crystallized into a reverted Bi{sub 4}Ti{sub 3}O{sub 12} structure at T {sub cryst2}.

  7. Association of igneous phophate and uranium

    International Nuclear Information System (INIS)

    Loureiro, F.E.V.L.

    1980-10-01

    Data from Catalao permit some brief comments about the association of igneous phosphate and uranium, and on the possible economic importance of this type of mineralization in spite of the low grades of metals observed. Chemical and mineralogical analyses of carbonatites, phosphate ore and different phosphate concentrates, reveal the existence of important low-grade reserves of Th, Nb, Zr, U and La, and possibly of other metals such as V and Cu. Uranium is enriched 1.6 and 1.2 times, respectively, in the residual muds and flotation wastes produced at the processing plant of Goiasfertil operating in the area. The uranium is associated with two types of minerals, the first one comprised primarily of phosphates of the gorceixite group and secondarily of apatite and dahllite. THe second association is with pyrochlore, or rather barium-pyrochlore. Further investigations of similar occurences may define more clearly and specifically the various factors controlling the observed enrichment in heavy elements. (Author) [pt

  8. Direct crystallization of perovskite phase in PMN-PT thin films prepared by polyvinylpyrrolidone modified sol-gel processing and their properties

    International Nuclear Information System (INIS)

    Du, Z.H.; Zhang, T.S.; Zhu, M.M.; Ma, J.

    2009-01-01

    A modified sol-gel processing has been developed by using polyvinylpyrrolidone (PVP) as modifier and lead nitrate as lead source to synthesize (1-x)Pb(Mg 1/3 ,Nb 2/3 )O 3 -xPbTiO 3 (PMN-PT) thin films with x=0.23-0.43. With PVP additions, perovskite phase could directly crystallize from amorphous films at the temperature as low as 430 deg. C via bypassing the metastable phase-pyrochlore and crystallinity was significantly enhanced. The PVP addictives have been optimized with molecular weight 1/3 ,Nb 2/3 )O 3 -PbTiO 3 films via bypassing pyrochlore phase.

  9. Study of dissolution factors of U, Th and Ta

    International Nuclear Information System (INIS)

    Santos, Maristela; Medeiros, Geiza; Zouain, Felipe; Cunha, Kenya Dias da; Pitassi, Gabriel; Lima, Cintia; Leite, Carlos Vieira Barros; Nascimento, Jose Eduardo; Dalia, Kely Cristina

    2009-01-01

    Air pollution can be a problem in industrial processes, but monitoring and controlling the aerosols in the work place is not enough to estimate the occupational risk due to dust particle inhalation. The solubility in lung fluid is considered to estimate this risk. The aim of this study is to determine in vitro specific dissolution parameters for thorium (Th), uranium (U) and tantalum (Ta) associated to crystal lattice of a niobium mineral (pyrochlore). Th, U and Ta dissolution factors in vitro were obtained using the Gamble solution (Simulant Lung Fluid, SLF), PIXE (Particle Induced X ray Emission) and alpha spectrometry as analytical techniques. Ta, Th and U are present in the pyrochlore crystal lattice as oxide; however they have shown different dissolution parameters. The rapid dissolution fraction (fr), rapid dissolution rate (λr); slow dissolution rate (fs) and slow dissolution fraction ((λs) measured for tantalum oxide were equal to 0.1, 0.45 d -1 and 0.00007 d -1 , respectively; for uranium oxide fr was equal to 0.05, (λr equal to 1.1 d -1 ; (λs equal to 0.000068 d -1 ; for thorium oxide fr was 0.025, (λr was 1.5 d -1 and (λs: 0.000065 d -1 . These results show that chemical behavior of these 3 compounds in the SLF could not be represented by the same parameter. The ratio of uranium concentration in urine and feces samples from workers exposed to pyrochlore dust particle was determined. These values agree with the theoretical values of estimated uranium concentration using specific parameters for uranium oxide present in pyrochlore. (author)

  10. Uranium prospecting in alkaline mountain chimneys of Serra Negra and Salitre - Minas Gerais, Brasil

    International Nuclear Information System (INIS)

    Souza Filho, J.G.C.

    1974-01-01

    The occurence of radioactive minerals such as apatite and pyrochlore, in the alkaline chimneys of Serra Negra and Salitre (Minas Gerais, Brazil), is discussed. Also mentioned are other minerals of interest associated with the alkaline magma such as columbite, fluorite, monazite, zircon, baddeleyite, etc, which in favourable conditions may occur in deposits of great economical value, and which may present high contents of rare earths, thorium and uranium

  11. Diversity of Ti–Sn–W–Nb–Ta oxide minerals in the classic granite-related magmatic–hydrothermal Cínovec/Zinnwald Sn–W–Li deposit (Czech Republic)

    Czech Academy of Sciences Publication Activity Database

    Breiter, Karel; Korbelová, Zuzana; Chládek, Š.; Uher, P.; Knésl, I.; Rambousek, P.; Honig, S.; Šešulka, V.

    2017-01-01

    Roč. 29, č. 4 (2017), s. 727-738 ISSN 0935-1221 R&D Projects: GA ČR GA14-13600S Institutional support: RVO:67985831 Keywords : rutile * cassiterite * scheelite * wolframite * columbite-group minerals * pyrochlore-supergroup minerals * granite * greisen * Cínovec * Zinnwald Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Mineralogy Impact factor: 1.362, year: 2016

  12. Structural study and electrical properties of Zr-doped Nd2Sn2O7 ...

    Indian Academy of Sciences (India)

    applications as neutron absorbers and radioactive waste forms for final disposal. [2,3]. The cubic pyrochlore structure, space group Fd3m, has eight molecules of the general formula A2B2O6O in the unit cell. The anion array consists of three independent sites O(1), O(2) and O(3), occupying the locations 48f, 8a and 8b.

  13. Critical behavior of 2 and 3 dimensional ferro- and antiferromagnetic spin ice systems in the framework of the Effective Field Renormalization Group technique

    OpenAIRE

    Garcia-Adeva, A. J.; Huber, D. L.

    2001-01-01

    In this work we generalize and subsequently apply the Effective Field Renormalization Group technique to the problem of ferro- and antiferromagnetically coupled Ising spins with local anisotropy axes in geometrically frustrated geometries (kagome and pyrochlore lattices). In this framework, we calculate the various ground states of these systems and the corresponding critical points. Excellent agreement is found with exact and Monte Carlo results. The effects of frustration are discussed. As ...

  14. Oxygen potentials of transuranium oxides

    International Nuclear Information System (INIS)

    Haruyoshi Otobe; Mituso Akabori; Arai Yasuo; Kazuo Minato

    2008-01-01

    The oxygen potentials of pyrochlore-type Pu 2 Zr 2 O 7+y , fluorite-type (Pu 0.5 Zr 0.5 )O 2-x and AmO 2-x have been measured by the electromotive force (EMF) method with a zirconia solid-electrolyte. The oxygen potentials of these oxides were reviewed. The phase relations, microstructure, equilibrium state of these oxides were discussed, referring to the isothermal curve of the oxygen potentials. (authors)

  15. Phase transition in metastable perovskite Pb(AlNb)0,5O3

    International Nuclear Information System (INIS)

    Zhabko, T.E.; Olekhnovich, N.M.; Shilin, A.D.

    1987-01-01

    Dielectric properties of metastable perovskite Pb(AlNb) 0.5 O 3 and X-ray temperature investigations of both perovskite and pyrochlore modifications of the given compound are studied. Samples with the perovskite structure are prepared from the pyrochlorephase at 4-5 GPa pressure and 1170-1270 K. Ferroelectric phase transition is shown to occur in the metastable perovskite phase Pb(AlNb) 0.5 O 3 at 170 K

  16. Structural determination of new solid solutions [Y2-x Mx ][Sn2-x Mx ]O7-3x/2 (M = Mg or Zn by Rietveld method

    Directory of Open Access Journals (Sweden)

    Mohamed Douma

    2010-12-01

    Full Text Available New [Y2-x Mx][Sn2-x Mx]O7-3x/2 (0 ≤x≤ 0.30 for M = Mg and 0 ≤x≤ 0.36 for M = Zn solid solutions with the pyrochlore structure were synthesized via high-temperature solid-state reaction method. Powder X-ray diffraction (PXRD patterns and Fourier transform infrared (FT-IR spectra showed that these materials are new non-stoichiometric solid solutions with the pyrochlore type structure. The structural parameters for the solids obtained were successfully determined by Rietveld refinement based on the analysis of the PXRD diagrams. Lattice parameter (a of these solid solutions decreases when x increases in both series. All samples obtained have the pyrochlore structure Fd-3m, no. 227 (origin at center -3m with M2+ (M = Mg2+ or Zn2+ cations in Y3+ and Sn4+ sites, thus creating vacancies in the anionic sublattice.

  17. Computer simulations applied in materials

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-07-01

    This workshop takes stock of the simulation methods applied to nuclear materials and discusses the conditions in which these methods can predict physical results when no experimental data are available. The main topic concerns the radiation effects in oxides and includes also the behaviour of fission products in ceramics, the diffusion and segregation phenomena and the thermodynamical properties under irradiation. This document brings together a report of the previous 2002 workshop and the transparencies of 12 presentations among the 15 given at the workshop: accommodation of uranium and plutonium in pyrochlores; radiation effects in La{sub 2}Zr{sub 2}O{sub 7} pyrochlores; first principle calculations of defects formation energies in the Y{sub 2}(Ti,Sn,Zr){sub 2}O{sub 7} pyrochlore system; an approximate approach to predicting radiation tolerant materials; molecular dynamics study of the structural effects of displacement cascades in UO{sub 2}; composition defect maps for A{sup 3+}B{sup 3+}O{sub 3} perovskites; NMR characterization of radiation damaged materials: using simulation to interpret the data; local structure in damaged zircon: a first principle study; simulation studies on SiC; insertion and diffusion of He in 3C-SiC; a review of helium in silica; self-trapped holes in amorphous silicon dioxide: their short-range structure revealed from electron spin resonance and optical measurements and opportunities for inferring intermediate range structure by theoretical modelling. (J.S.)

  18. Synthesis, characterization and luminescence study of Eu3+ doped Y2Sn2O7 nano-particles

    International Nuclear Information System (INIS)

    Nigam, Sandeep; Sudarsan, V.; Vatsa, R.K.

    2011-01-01

    In recent years, advanced materials derived from Pyrochlore-type oxides (A 2 B 2 O 7 ), have been of extensive scientific and technological interest. Chemical substitution of A or B sites of pyrochlore oxide by rare earth ions is a widely used approach to prepare thermally stable, lanthanide ion doped luminescent materials. The present study deals with the synthesis and characterization of Eu 3+ doped Y 2 Sn 2 O 7 : nanoparticles prepared by the hydrolysis of Y 3+ , Sn 4+ , and Eu 3+ in ethylene glycol medium followed by heating at 700 deg C for 4 hours. As prepared samples are amorphous in nature and 700 deg C heated sample showed well crystalline pyrochlore structure in XRD studies. Average particle size is calculated from the width of the X-ray diffraction peaks and found to t be around 5 nm. Luminescence measurements were carried out for as prepared and 700 deg C heated samples. The undoped as prepared sample showed a broad emission peak around 420 nm after excitation at 285 nm. While for 700 deg C undoped heated sample, the peak maxima was shifted to 435 nm. The emission spectrum for doped as prepared samples is characterized by both host emission around 420 nm along with the characteristic Eu 3+ emission peaks in the visible region. However, very poor Eu 3+ emission from heated sample was observed

  19. Liandratite from Karkonosze pegmatites, Sudetes, Southwestern Poland

    Science.gov (United States)

    Matyszczak, Witold

    2018-06-01

    The chemical composition of liandratite, U6+(Nb,Ta)2O8, was determined from material collected in Niobium, Yttrium, Fluorine type (NYF) pegmatites of the Karkonosze intrusion (Sudetes, SW Poland). Liandratite occurs mainly as rims, up to 40 µm thick, and fracture infillings in fergusonite-(Y) and other Nb-Ta-Ti minerals. Its formation was related to the fluid-driven alteration of primary minerals by three potential mechanisms: (i) direct replacement of a primary mineral by liandratite; (ii) breakdown of the primary mineral to liandratite and a product with the composition of minerals of the pyrochlore group; (iii) multistage alteration, which involved: removal of A-site cations (mostly Y + REE with the exception of U4+) and formation of phases with the composition of pyrochlore group minerals; then crystallization of U-, Bi-, Pb-rich pyrochlores and their replacement by liandratite. The chemical compositions of liandratite formed by the breakdown of different primary minerals are also different, mainly in their U, Ti and Nb contents. Excess Ti, relative to the U6+Nb2O8 end-member, is incorporated into the structure together with additional U. The Ti content of liandratite, and partially through this the U content, are dependent on the nature of the precursor mineral.

  20. Nanoscopic characterization of Pr2Zr2O7 at Zr sites

    International Nuclear Information System (INIS)

    Martinez, J.A.; Caracoche, M.C.; Rodriguez, A.M.; Rivas, P.C.; Bondioli, F.; Manfredini, T.; Ferrari, A.M.

    2005-01-01

    By using Perturbed Angular Correlation Spectroscopy, a suitable technique to explore internal fields at nanoscopic scale, the electric field gradients at Zr 4+ sites in the Pr 2 Zr 2 O 7 compound have been determined as a function of temperature. Three nonequivalent nanoconfigurations are present, which have been interpreted with the aid of point charge model calculations. Two of them correspond to pyrochlore - oxygen defective and perfect structures -, and the third one to the pyrochlore-related defect fluorite structure. The most abundant interaction is a disordered and fluctuating electric field gradient, which describes the oxygen defective pyrochlore. As temperature increases, its gradual and reversible transformation towards the perfect form is observed. Below 750 C the oxygen vacancies movement, which exhibits an activation energy of 0.14 eV, is assumed to be due to vacancies jumping among 48f equivalent sites. At higher temperatures the movement is interpreted as the fast diffusion of oxygen vacancies involving 48f and 8b sites, thus giving place to anionic disorder. The activation energy for this movement has been determined to be of 0.85 eV. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  1. Synthesis and structural characterization of Ce-doped bismuth titanate

    International Nuclear Information System (INIS)

    Pavlovic, Nikolina; Srdic, Vladimir V.

    2009-01-01

    Ce-modified bismuth titanate nanopowders Bi 4-x Ce x Ti 3 O 12 (x ≤ 1) have been synthesized using a coprecipitation method. DTA/TG, FTIR, XRD, SEM/EDS and BET methods were used in order to investigate the effect of Ce-substitution on the structure, morphology and sinterability of the obtained powders. The phase structure investigation revealed that after calcinations at 600 deg. C powder without Ce addition exhibited pure bismuth titanate phase; however, powders with Ce (x = 0.25, 0.5 and 0.75) had bismuth titanate pyrochlore phase as the second phase. The strongest effect of Ce addition on the structure was noted for the powder with the highest amount of Ce (x = 1) having a cubic pyrochlore structure. The presence of pure pyrochlore phase was explained by its stabilization due to the incorporation of cerium ions in titanate structure. Ce-modified bismuth titanate ceramic had a density over 95% of theoretical density and the fracture in transgranular manner most probably due to preferable distribution of Ce in boundary region

  2. Forging Fast Ion Conducting Nanochannels with Swift Heavy Ions: The Correlated Role of Local Electronic and Atomic Structure

    Energy Technology Data Exchange (ETDEWEB)

    Sachan, Ritesh [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Material Science and Technology Division; Cooper, Valentino R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Material Science and Technology Division; Liu, Bin [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; Aidhy, Dilpuneet S. [Univ. of Wyoming, Laramie, WY (United States). Dept. of Mechanical Engineering; Voas, Brian K. [Iowa State Univ., Ames, IA (United States). Dept. of Materials Science and Engineering; Lang, Maik [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Nuclear Engineering; Ou, Xin [Chinese Academy of Sciences (CAS), Shanghai (China). State Key Lab. of Functional Material for Informatics; Trautmann, Christina [GSI Helmholtz Centre for Heavy Ion Research, Darmstadt (Germany); Technical Univ. of Darmstadt (Germany). Dept. of Materials Science; Zhang, Yanwen [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Material Science and Technology Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; Chisholm, Matthew F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Material Science and Technology Division; Weber, William J. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Material Science and Technology Division

    2016-12-19

    Atomically disordered oxides have attracted significant attention in recent years due to the possibility of enhanced ionic conductivity. However, the correlation between atomic disorder, corresponding electronic structure, and the resulting oxygen diffusivity is not well understood. The disordered variants of the ordered pyrochlore structure in gadolinium titanate (Gd2Ti2O7) are seen as a particularly interesting prospect due to intrinsic presence of a vacant oxygen site in the unit atomic structure, which could provide a channel for fast oxygen conduction. In this paper, we provide insights into the subangstrom scale on the disordering-induced variations in the local atomic environment and its effect on the electronic structure in high-energy ion irradiation-induced disordered nanochannels, which can be utilized as pathways for fast oxygen ion transport. With the help of an atomic plane-by-plane-resolved analyses, the work shows how the presence of various types of TiOx polyhedral that exist in the amorphous and disordered crystalline phase modify the electronic structures relative to the ordered pyrochlore phase in Gd2Ti2O7. Finally, the correlated molecular dynamics simulations on the disordered structures show a remarkable enhancement in oxygen diffusivity as compared with ordered pyrochlore lattice and make that a suitable candidate for applications requiring fast oxygen conduction.

  3. Growth and alteration of uranium-rich microlite

    International Nuclear Information System (INIS)

    Giere, R.; Swope, R. J.; Buck, E. C.; Guggenheim, R.; Mathys, D.; Reusser, E.

    2000-01-01

    Uranium-rich microlite, a pyrochlore-group mineral, occurs in 440 Ma old lithium pegmatites of the Mozambique Belt in East Africa. Microlite exhibits a pronounced growth zoning, with a U-free core surrounded by a U-rich rim (UO 2 up to 17 wt.%). The core exhibits conjugate sets of straight cracks (cleavage planes) which provided pathways for a late-stage U-enriched pegmatitic fluid which interacted with the U-free microlite to produce a distinct U enrichment along the cracks and led to the formation of the U-rich rim. Following the stage of U incorporation into microlite, a second generation of hydrothermal fluids deposited mica along the cleavage planes. Subsequent to these two hydrothermal stages, the host rock was uplifted and subjected to intense low-temperature alteration during which Na, Ca and F were leached from the microlite crystals. This alteration also led to a hydration of microlite, but there is no evidence of U loss. These low-temperature alteration effects were only observed in the U-rich rim which is characterized by a large number of irregular cracks which are most probably the result of metamictization, as indicated by electron diffraction images and powder X-ray patterns. The pyrochlore-group minerals provide excellent natural analogues for pyrochlore-based nuclear waste forms, because samples of variable age and with high actinide contents are available

  4. UV laser micromachining of piezoelectric ceramic using a pulsed Nd:YAG laser

    International Nuclear Information System (INIS)

    Zeng, D.W.; Xie, C.S.; Li, K.; Chan, H.L.W.; Choy, C.L.; Yung, K.C.

    2004-01-01

    UV laser (λ=355 nm) ablation of piezoelectric lead zirconate titanate (PZT) ceramics in air has been investigated under different laser parameters. It has been found that there is a critical pulse number (N=750). When the pulse number is smaller than the critical value, the ablation rate decreases with increasing pulse number. Beyond the critical value, the ablation rate becomes constant. The ablation rate and concentrations of O, Zr and Ti on the ablated surface increase with the laser fluence, while the Pb concentration decreases due to the selective evaporation of PbO. The loss of the Pb results in the formation of a metastable pyrochlore phase. ZrO 2 was detected by XPS in the ablated zone. Also, the concentrations of the pyrochlore phase and ZrO 2 increase with increasing laser fluence. These results clearly indicate that the chemical composition and phase structure in the ablated zone strongly depend on the laser fluence. The piezoelectric properties of the cut PZT ceramic samples completely disappear due to the loss of the Pb and the existence of the pyrochlore phase. After these samples were annealed at 1150 C for 1 h in a PbO-controlled atmosphere, their phase structure and piezoelectric properties were recovered again. Finally, 1-3 and concentric-ring 2-2 PZT/epoxy composites were fabricated by UV laser micromachining and their thickness modes were measured by impedance spectrum analysis and a d 33 meter. Both composites show high piezoelectric properties. (orig.)

  5. Computer simulations applied in materials

    International Nuclear Information System (INIS)

    2003-01-01

    This workshop takes stock of the simulation methods applied to nuclear materials and discusses the conditions in which these methods can predict physical results when no experimental data are available. The main topic concerns the radiation effects in oxides and includes also the behaviour of fission products in ceramics, the diffusion and segregation phenomena and the thermodynamical properties under irradiation. This document brings together a report of the previous 2002 workshop and the transparencies of 12 presentations among the 15 given at the workshop: accommodation of uranium and plutonium in pyrochlores; radiation effects in La 2 Zr 2 O 7 pyrochlores; first principle calculations of defects formation energies in the Y 2 (Ti,Sn,Zr) 2 O 7 pyrochlore system; an approximate approach to predicting radiation tolerant materials; molecular dynamics study of the structural effects of displacement cascades in UO 2 ; composition defect maps for A 3+ B 3+ O 3 perovskites; NMR characterization of radiation damaged materials: using simulation to interpret the data; local structure in damaged zircon: a first principle study; simulation studies on SiC; insertion and diffusion of He in 3C-SiC; a review of helium in silica; self-trapped holes in amorphous silicon dioxide: their short-range structure revealed from electron spin resonance and optical measurements and opportunities for inferring intermediate range structure by theoretical modelling. (J.S.)

  6. First-principles calculation of structural and energetic properties for A2Ti2O7 (A = Lu, Er, Y, Gd, Sm, Nd, La)

    International Nuclear Information System (INIS)

    Zhang, Z.L.; Xiao, H.Y.; Zu, Xiaotao T.; Gao, Fei; Weber, William J.

    2009-01-01

    A first-principles method has been employed to investigate the structural and energetic properties for A2Ti2O7 (A = Lu, Er, Y, Gd, Sm, Nd, La), including the formation energies of the cation antisite-pair, the anion Frenkel pair that defines anion-disorder, and the coupled cation antisite-pair/anion-Frenkel. It is proposed that the interaction may have more significant influence on the radiation resistance behavior of titanate pyrochlores, although the interactions are relatively much stronger than the interactions. It is found that the defect formation energies are not simple functions of the A-site cation radii. The formation energy of the cation antisite-pair increases continuously as the A-site cation varies from Lu to Gd, and then decreases continuously with the variation of the A-site cation from Gd to La, in excellent agreement with the radiation-resistance trend of the titanate pyrochlores. The band gaps in these pyrochlores were also measured, and the band gap widths changed continuously with cation radius.

  7. A novel high-temperature commensurate superstructure in a natural bariopyrochlore: A structural study by means of a multiphase crystal structure refinement

    International Nuclear Information System (INIS)

    Bindi, L.; Petricek, V.; Withers, R.L.; Zoppi, M.; Bonazzi, P.

    2006-01-01

    Additional X-ray diffraction effects yielding an eightfold commensurate superstructure [a=20.974(5)A] of the ideal pyrochlore structure were observed after annealing at 873K of a thallium-doped bariopyrochlore single crystal. Electron diffraction indicated the coexistence of two cubic phases, the pyrochlore structure and a new F-centred, cubic phase. The superstructure was solved and refined in the space group F4-bar 3m. The two phases were combined together and refined as independently diffracting to R=0.0628. The resulting unit-cell content is (A,-bar ) 20 Nb 16 Ti 2 O 53 (Z=8), with A=Ba, Tl, Ce, Th. For some atomic positions of the superstructure, third- and fourth-order anharmonic ADP's were used to account for the specific density shape having a continuous character as typical for ionic conductors. There are three distinct clusters in the superstructure, leading to a new structure type no longer strictly of pyrochlore-structure type

  8. Structural, hyperfine and Raman properties of RE2FeSbO7 compounds

    International Nuclear Information System (INIS)

    Berndt, G.; Silva, K.L.; Ivashita, F.F.; Paesano, A.; Blanco, M.C.; Miner, E.V.P.; Carbonio, R.E.; Dantas, S.M.; Ayala, A.P.; Isnard, O.

    2015-01-01

    Highlights: • We prepared monophasic RE 2 FeSbO 7 pyrochlores. • RE 2 FeSbO 7 compounds were characterized regarding crystallographic, vibrational and hyperfine properties. • We find out that a site disorder takes place for the RE’s of larger ionic radii. • Lattice parameters, Raman bands and quadrupole splittings were shown to depend correlatedly on the RE ionic radius. - Abstract: Pyrochlores of the RE 2 FeSbO 7 type were synthesized by ball-milling followed by annealing in free atmosphere at high temperatures. The samples prepared were characterized by X-ray diffraction, Raman spectroscopy and 57 Fe Mössbauer spectroscopy, at room temperature. The results showed that RE 2 FeSbO 7 compounds have a cubic structure, i.e., Fd-3m (#227) space group, and that a site disorder takes place for the RE’s of larger ionic radii. Lattice parameters, Raman bands and quadrupole splittings were shown to depend correlatedly on the RE ionic radius. This behavior is discussed in terms of the pyrochlore crystallographic structure

  9. Heavy ion irradiation effects of brannerite-type ceramics

    International Nuclear Information System (INIS)

    Lian, J.; Wang, L.M.; Lumpkin, G.R.; Ewing, R.C.

    2002-01-01

    Brannerite, UTi 2 O 6 , occurs in polyphase Ti-based, crystalline ceramics that are under development for plutonium immobilization. In order to investigate radiation effects caused by α-decay events of Pu, a 1 MeV Kr + irradiation on UTi 2 O 6 , ThTi 2 O 6 , CeTi 2 O 6 and a more complex material, composed of Ca-containing brannerite and pyrochlore, was performed over a temperature range of 25-1020 K. The ion irradiation-induced crystalline-to-amorphous transformation was observed in all brannerite samples. The critical amorphization temperatures of the different brannerite compositions are: 970 K, UTi 2 O 6 ; 990 K, ThTi 2 O 6 ; 1020 K, CeTi 2 O 6 . The systematic increase in radiation resistance from Ce-, Th- to U-brannerite is related to the difference of mean atomic mass of A-site cation in the structure. As compared with the pyrochlore structure-type, brannerite phases are more susceptible to ion irradiation-induced amorphization. The effects of structure and chemical compositions on radiation resistance of brannerite-type and pyrochlore-type ceramics are discussed

  10. Yttria-stabilized zirkonia / gadolinium zirconate double-layer plasma-sprayed thermal barrier coating systems (TBCs)

    Energy Technology Data Exchange (ETDEWEB)

    Bakan, Emine

    2015-07-01

    Thermal barrier coating (TBC) research and development is driven by the desirability of further increasing the maximum inlet temperature in a gas turbine engine. A number of new top coat ceramic materials have been proposed during the last decades due to limited temperature capability (1200 C) of the state-of-the-art yttria-stabilized zirconia (7 wt. % Y{sub 2}O{sub 3}-ZrO{sub 2}, YSZ) at long term operation. Zirconate pyrochlores of the large lanthanides((Gd → La){sub 2}Zr{sub 2}O{sub 7}) have been particularly attractive due to their higher temperature phase stability than that of the YSZ. Nonetheless, the issues related with the implementation of pyrochlores such as low fracture toughness and formation of deleterious interphases with thermally grown oxide (TGO, Al{sub 2}O{sub 3}) were reported. The implication was the requirement of an interlayer between the pyrochlores and TGO, which introduced double-layer systems to the TBC literature. Furthermore, processability issues of pyrochlores associated with the different evaporation rates of lanthanide oxides and zirconia resulting in unfavorable composition variations in the coatings were addressed in different studies. After all, although the material properties are available, there is a paucity of data in the literature concerning the properties of the coatings made of pyrochlores. From the processability point of view the most reported pyrochlore is La{sub 2}Zr{sub 2}O{sub 7}. Hence, the goal of this research was to investigate plasma-sprayed Gd{sub 2}Zr{sub 2}O{sub 7} (GZO) coatings and YSZ/GZO double-layer TBC systems. Three main topics were examined based on processing, performance and properties: (i) the plasma spray processing of the GZO and its impact on the microstructural and compositional properties of the GZO coatings; (ii) the cycling lifetime of the YSZ/GZO double-layer systems under thermal gradient at a surface temperature of 1400 C; (iii) the properties of the GZO and YSZ coatings such as

  11. Yttria-stabilized zirkonia / gadolinium zirconate double-layer plasma-sprayed thermal barrier coating systems (TBCs)

    International Nuclear Information System (INIS)

    Bakan, Emine

    2015-01-01

    Thermal barrier coating (TBC) research and development is driven by the desirability of further increasing the maximum inlet temperature in a gas turbine engine. A number of new top coat ceramic materials have been proposed during the last decades due to limited temperature capability (1200 C) of the state-of-the-art yttria-stabilized zirconia (7 wt. % Y 2 O 3 -ZrO 2 , YSZ) at long term operation. Zirconate pyrochlores of the large lanthanides((Gd → La) 2 Zr 2 O 7 ) have been particularly attractive due to their higher temperature phase stability than that of the YSZ. Nonetheless, the issues related with the implementation of pyrochlores such as low fracture toughness and formation of deleterious interphases with thermally grown oxide (TGO, Al 2 O 3 ) were reported. The implication was the requirement of an interlayer between the pyrochlores and TGO, which introduced double-layer systems to the TBC literature. Furthermore, processability issues of pyrochlores associated with the different evaporation rates of lanthanide oxides and zirconia resulting in unfavorable composition variations in the coatings were addressed in different studies. After all, although the material properties are available, there is a paucity of data in the literature concerning the properties of the coatings made of pyrochlores. From the processability point of view the most reported pyrochlore is La 2 Zr 2 O 7 . Hence, the goal of this research was to investigate plasma-sprayed Gd 2 Zr 2 O 7 (GZO) coatings and YSZ/GZO double-layer TBC systems. Three main topics were examined based on processing, performance and properties: (i) the plasma spray processing of the GZO and its impact on the microstructural and compositional properties of the GZO coatings; (ii) the cycling lifetime of the YSZ/GZO double-layer systems under thermal gradient at a surface temperature of 1400 C; (iii) the properties of the GZO and YSZ coatings such as thermal conductivity, coefficient of thermal expansion as well

  12. Crystal structures of orthorhombic, hexagonal, and cubic compounds of the Sm(x)Yb(2−x)TiO5 series

    International Nuclear Information System (INIS)

    Aughterson, Robert D.; Lumpkin, Gregory R.; Reyes, Massey de los; Sharma, Neeraj; Ling, Christopher D.; Gault, Baptiste; Smith, Katherine L.; Avdeev, Maxim; Cairney, Julie M.

    2014-01-01

    A series of single phase compounds with nominal stoichiometry Sm (x) Yb (2−x) TiO 5 (x=2, 1.4, 1, 0.6, and 0) have been successfully fabricated to generate a range of crystal structures covering the most common polymorphs previously discovered in the Ln 2 TiO 5 series (Ln=lanthanides and yttrium). Four of the five samples have not been previously fabricated in bulk, single phase form so their crystal structures are refined and detailed using powder synchrotron and single crystal x-ray diffraction, neutron diffraction and transmission electron microscopy. Based on the phase information from diffraction data, there are four crystal structure types in this series; orthorhombic Pnma, hexagonal P6 3 /mmc, cubic (pyrochlore-like) Fd-3m and cubic (fluorite-like) Fm-3m. The cubic materials show modulated structures with variation between long and short range ordering and the variety of diffraction techniques were used to describe these complex crystal structure types. - Graphical abstract: A high resolution image of the compound Sm 0.6 Yb 1.4 TiO 5 showing contrast from lattice fringes and the corresponding fast Fourier transform (FFT) of the HREM image with pyrochlore related diffraction spots marked “P” and fluorite marked “F”. The crystal is oriented down the [1 1 0] zone axis based on the Fd-3m structure. The ideal crystal structure (no vacancies) of the cubic, pyrochlore-like (Sm 0.6 Yb 1.4 TiO 5 ). - Highlights: • First fabrication of bulk single-phase material with stoichiometry Sm 2 TiO 5 . • Systematic study of crystal structure types within Ln 2 TiO 5 series (Ln=lanthanides). • A novel technique using IFFT of HREM images to study cubic structures

  13. Novel Functionally Graded Thermal Barrier Coatings in Coal-Fired Power Plant Turbines

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jing [Indiana Univ., Indianapolis, IN (United States)

    2016-11-01

    This project presents a detailed investigation of a novel functionally graded coating material, pyrochlore oxide, for thermal barrier coating (TBC) in gas turbines used in coal-fired power plants. Thermal barrier coatings are refractory materials deposited on gas turbine components, which provide thermal protection for metallic components at operating conditions. The ultimate goal of this research is to develop a manufacturing process to produce the novel low thermal conductivity and high thermal stability pyrochlore oxide based coatings with improved high-temperature durability. The current standard TBC, yttria stabilized zirconia (YSZ), has service temperatures limited to <1200°C, due to sintering and phase transition at higher temperatures. In contrast, pyrochlore oxide, e.g., lanthanum zirconate (La2Zr2O7, LZ), has demonstrated lower thermal conductivity and better thermal stability, which are crucial to high temperature applications, such as gas turbines used in coal-fired power plants. Indiana University – Purdue University Indianapolis (IUPUI) has collaborated with Praxair Surface Technologies (PST), and Changwon National University in South Korea to perform the proposed research. The research findings are critical to the extension of current TBCs to a broader range of high-temperature materials and applications. Several tasks were originally proposed and accomplished, with additional new opportunities identified during the course of the project. In this report, a description of the project tasks, the main findings and conclusions are given. A list of publications and presentations resulted from this research is listed in the Appendix at the end of the report.

  14. Magnetic Order and Crystal Field Excitations in Er2Ru2O7: A Neutron Scattering Study

    International Nuclear Information System (INIS)

    Ehlers, Georg; Gardner, Jason

    2009-01-01

    The magnetic pyrochlore Er 2 Ru 2 O 7 has been studied with neutron scattering and susceptibility measurements down to a base temperature of 270 mK. For the low temperature phase in which the Er sublattice orders, new magnetic Bragg peaks are reported which can be indexed with integer (hkl) for a face centered cubic cell. Inelastic measurements reveal a wealth of crystal field levels of the Er ion and a copious amount of magnetic scattering below 15 meV. The three lowest groups of crystal field levels are at 6.7, 9.1 and 18.5 meV.

  15. Response of Gd 2 Ti 2 O 7 and La 2 Ti 2 O 7 to swift-heavy ion irradiation and annealing

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sulgiye; Lang, Maik; Tracy, Cameron L.; Zhang, Jiaming; Zhang, Fuxiang; Trautmann, Christina; Rodriguez, Matias D.; Kluth, Patrick; Ewing, Rodney C.

    2015-07-01

    Swift heavy ion (2 GeV 181Ta) irradiation-induced amorphization and temperature-induced recrystallization of cubic pyrochlore Gd2Ti2O7 (Fd3¯m) are compared with the response of a compositionally-similar material with a monoclinic-layered perovskite-type structure, La2Ti2O7 (P21). The averaged electronic energy loss, dE/dx, was 37 keV/nm and 35 keV/nm in Gd2Ti2O7 and La2Ti2O7, respectively. Systematic analysis of the structural modifications was completed using transmission electron microscopy, synchrotron X-ray diffraction, Raman spectroscopy, and small-angle X-ray scattering. Increasing ion-induced amorphization with increasing ion fluence was evident in the X-ray diffraction patterns of both compositions by a reduction in the intensity of the diffraction maxima concurrent with the growth in intensity of a broad diffuse scattering halo. Transmission electron microscopy analysis showed complete amorphization within ion tracks (diameter: ~10 nm) for the perovskite-type material; whereas a concentric, core–shell morphology was evident in the ion tracks of the pyrochlore, with an outer shell of disordered yet still crystalline material with the fluorite structure surrounding an amorphous track core (diameter: ~9 nm). The radiation response of both titanate oxides with the same stoichiometry can be understood in terms of differences in their structures and compositions. While the radiation damage susceptibility of pyrochlore A2B2O7 materials decreases as a function of the cation radius ratio rA/rB, the current study correlates this behavior with the stability field of monoclinic structures, where rLa/rTi > rGd/rTi. Isochronal annealing experiments of the irradiated materials showed complete recrystallization of La2Ti2O7 at 775 °C and of Gd2Ti2O7 at 850 °C. The annealing behavior is discussed in terms of enhanced damage recovery in La2Ti2O7, compared to the pyrochlore compounds Gd2Ti2O7. The difference in the recrystallization behavior may be related to structural

  16. Aspects of chlorination and its potential to produce niobium pentoxide

    International Nuclear Information System (INIS)

    Brocchi, E.A.; Jeffes, J.H.E.

    1984-01-01

    Reduction chlorination of niobium pentoxide were carried out under different experimental conditions in order to study the effects of some variables of the process. In order to evaluate the efficiency of the recovery of niobium pentoxide which could be obtained as condensed material a group of experiments were also carried out with pyrochlore concentrate. The results showed that a balance of factors such as temperature, percentage of carbon in the initial charge and porosity cause the progress of the reaction to be controlled by different mechanisms and indicate that chlorination can be used to produce niobium pentoxide-especially if applied on rich starting material. (Author) [pt

  17. Key insights on the structural characterization of textured Er{sub 2}O{sub 3}-ZrO{sub 2} nano-oxides prepared by a surfactant-free solvothermal route

    Energy Technology Data Exchange (ETDEWEB)

    Julian-Lopez, Beatriz, E-mail: julian@qio.uji.es [Departamento de Quimica Inorganica y Organica, Universitat Jaume I, Avda. Vicente Sos Baynat s/n, 12071 Castellon (Spain); Luz, Veronica de la; Gonell, Francisco; Cordoncillo, Eloisa [Departamento de Quimica Inorganica y Organica, Universitat Jaume I, Avda. Vicente Sos Baynat s/n, 12071 Castellon (Spain); Lopez-Haro, Miguel; Calvino, Jose J. [Departamento de Ciencia de los Materiales e Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Campus Rio San Pedro, Puerto Real, 11510 Cadiz (Spain); Escribano, Purificacion [Departamento de Quimica Inorganica y Organica, Universitat Jaume I, Avda. Vicente Sos Baynat s/n, 12071 Castellon (Spain)

    2012-04-05

    Highlights: Black-Right-Pointing-Pointer Structural resolution of fluorite vs. pyrochlore in small nanocrystals. Black-Right-Pointing-Pointer Simple template-free solvothermal synthesis of Er{sub 2}O{sub 3}-ZrO{sub 2} nanooxides. Black-Right-Pointing-Pointer Good control over size, morphology and surface properties (280 m{sup 2} g{sup -1}). - Abstract: Zirconia-mixed oxides can exhibit cubic fluorite and pyrochlore structure. Their discrimination is not easy in nanooxides with a crystal size close to that of a few unit cells. In this work, high resolution transmission electron microscopy (HRTEM) has been employed to provide key insights on the structural characterization of a nanometric and porous mixed Er{sub 2}O{sub 3}-ZrO{sub 2} oxide. The material was prepared by a simple template-free solvothermal route that provided nanocrystalline powders at low temperature (170 Degree-Sign C) with spherical morphology, and high surface area ({approx}280 m{sup 2} g{sup -1}). The porosity was mainly originated from the assembling of organic complexing agents used in the synthesis to limit the crystal growth and to control hydrolysis and condensation reaction rates. The samples were characterized by thermal analysis, X-ray diffraction, scanning electron microscopy and N{sub 2} adsorption measurements. A detailed study by HRTEM was conducted on microtomed samples. It was observed that the material was made of nanocrystals packed into spherical agglomerates. HRTEM simulations indicated that it is not possible to identify the pyrochlore phase in nanoparticles with diameter below 2 nm. In our samples, the analysis of the HRTEM lattice images by means of fast Fourier transform (FFT) techniques revealed well defined spots that can be assigned to different planes of a cubic fluorite-type phase, even in the raw material. Raman spectroscopy was also a powerful technique to elucidate the crystalline phase of the materials with the smallest nanoparticles. HREM and Raman results evidenced

  18. Rare earth silicate (Ce, La, Nd, Ca, Th) SiO4 and cheralite (Th, Ca, Ce, La) (Psi)O4 are the responsible minerals for the anomalies of Morro de Ferro

    International Nuclear Information System (INIS)

    Fujimori, K.

    1982-01-01

    The Rare Earth silicate (La, Ce, Nd, Ca, Th)SiO 4 and cheralite (identified by Prof. Freeborn on a sample prepared from drilling core) were recognized as the most probable radioactive minerals that gave origin to high radioactive anomaly at Morro do Ferro hill together with coffinite, thorite, pyrochlore, apatite, etc., that are found in small quantity. The acids produced by decomposition of pyrite and fluorite have etched these radioactive minerals giving the high radioactive anomaly caracterized by high grade desiquilibrium of 232 Th serie. (Author) [pt

  19. Prospecting and exploration of rare earth bearing mineral resources in India: an overview

    International Nuclear Information System (INIS)

    Mohanty, R.

    2014-01-01

    Rare earth elements (REE) have a wide range of applications including nuclear and the REE bearing minerals occur in varied geological environments.The commercial rare earth bearing minerals are monazite ((Ce,La,Pr,Nd,Th,Y)PO 4 ), xenotime (YPO 4 ), bastnasite ((Ce,La,Y)CO 3 F) and pyrochlore ((Na,Ca) 2 Nb 2 O 6 (OH,F) which occur either as placer concentrations or in tracer quantities in rocks. While Monazite contains dominantly LREE, Xenotime and Bastnasite are richer in HREE. The exploration and evaluation of these two types of occurrences follow different methodologies

  20. Synthesis, Characterization and Thermal Diffusivity of Holmium and Praseodymium Zirconates

    OpenAIRE

    Stopyra M.; Niemiec D.; Moskal G.

    2016-01-01

    A2B2O7 oxides with pyrochlore or defected fluorite structure are among the most promising candidates for insulation layer material in thermal barrier coatings. The present paper presents the procedure of synthesis of holmium zirconate Ho2Zr2O7 and praseodymium zirconate Pr2Zr2O7 via Polymerized-Complex Method (PCM). Thermal analysis of precursor revealed that after calcination at relatively low temperature (700°C) fine-crystalline, single-phase material is obtained. Thermal diffusivity was me...

  1. Direct Flotation of Niobium Oxide Minerals from Carbonatite Niobium Ores

    Science.gov (United States)

    Ni, Xiao

    Currently the recovery of niobium oxide minerals from carbonatite niobium ores relies on the use of non-selective cationic collectors. This leads to complicated process flowsheets involving multiple desliming and multiple reverse flotation stages, and low niobium recovery. In this research, anionic collectors that are capable of strong chemisorption on the niobium minerals were studied with the objective of directly floating the niobium oxide minerals from the carbonatite ores. In the flotation of both high purity minerals and Niobec ores, it was shown that the combination of hydroxamic acid and sodium metaphosphate was an effective reagent scheme for the direct flotation of niobium oxide from its ores. Batch flotation on the Niobec Mill Feed showed that over 95% of niobium oxide was recovered into a rougher concentrate that was less than 47% of the original feed mass. Preliminary cleaning tests showed that the reagent scheme could also be used to upgrade the rougher concentrate, although the depression of iron oxide minerals required further study. X-ray photoelectron spectroscopic (XPS) measurement results confirm that OHA (octyl hydroxamic acid) could chemisorb on pyrochlore surface while only physically adsorb on calcite, judging by the chemical shifts of electron binding energies in the elements in both OHA and the mineral surfaces. When hydroxamic acid was adsorbed on calcite surface, the binding energies of the N 1s electrons, at 400.3 eV, did not shift. However, after adsorption on pyrochlore, the N 1s binding energy peak split into two peaks, one at a binding energy of around 399 eV, representing chemically adsorbed OHA, the other at between 400 and 401 eV. The experimental data suggested a strong chemisorption of the OHA on pyrochlore surface in the form of a vertical head-on orientation of the OHA molecules so that the pyrochlore was strongly hydrophobized even at low OHA concentrations, followed by possibly randomly oriented physisorbed OHA molecules

  2. Synthesis and characterization of organic-inorganic hybrids formed between conducting polymers and crystalline antimonic acid

    Directory of Open Access Journals (Sweden)

    Beleze Fábio A.

    2001-01-01

    Full Text Available In this paper we report the synthesis and characterization of novel organic-inorganic hybrid materials between the crystalline antimonic acid (CAA and two conductive polymers: polypyrrole and polyaniline. The hybrids were obtained by in situ oxidative polymerization of monomers by the Sb(V present in the pyrochlore-like CAA structure. The materials were characterized by infrared and Raman spectroscopy, X-ray diffraction, cyclic voltammetry, CHN elemental analysis and electronic paramagnetic resonance spectroscopy. The results showed that both polymers were formed in their oxidized form, with the CAA structure acting as a counter anion.

  3. Dynamical instability, strong anharmonicity and electron-phonon coupling in KOs2O6: First-principles calculations

    Science.gov (United States)

    Wang, Wei; Sun, Jiafa; Li, Bin; He, Junqi

    2017-09-01

    First-principles pseudopotential calculations on phonon and electronic properties of β -pyrochlore superconductor KOs2O6 are performed. The imaginary soft-phonon modes with a special double-well potential for the lowest Eu(1) mode and the second lowest T1u(1) mode are reported, which indicates the dynamical instability in KOs2O6. However, the double wells are too small to induce a structural phase transformation in KOs2O6. The strong anharmonicity especially for K T2g(1) phonon mode is got, which is approved to be from the strong electron-phonon coupling that supports the superconductivity in KOs2O6.

  4. Mesoporous tertiary oxides via a novel amphiphilic approach

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, Natasha; Hall, Simon R., E-mail: simon.hall@bristol.ac.uk, E-mail: Annela.Seddon@bristol.ac.uk [Bristol Centre for Functional Nanomaterials, Centre for Nanoscience and Quantum Information, Tyndall Avenue, Bristol BS8 1FD, United Kingdom and Complex Functional Materials Group, School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Seddon, Annela M., E-mail: simon.hall@bristol.ac.uk, E-mail: Annela.Seddon@bristol.ac.uk; Hallett, James E. [H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Kockelmann, Winfried [STFC Rutherford Appleton Laboratory, Chilton OX11 0QX (United Kingdom); Ting, Valeska P. [Department of Chemical Engineering, University of Bath, Bath BA2 7AY (United Kingdom); Sadasivan, Sajanikumari; Tooze, Robert P. [Sasol Technology (UK) Ltd, Purdie Building, North Haugh, St Andrews, Fife KY16 9ST (United Kingdom)

    2016-01-01

    We report a facile biomimetic sol-gel synthesis using the sponge phase formed by the lipid monoolein as a structure-directing template, resulting in high phase purity, mesoporous dysprosium- and gadolinium titanates. The stability of monoolein in a 1,4-butanediol and water mixture complements the use of a simple sol-gel metal oxide synthesis route. By judicious control of the lipid/solvent concentration, the sponge phase of monoolein can be directly realised in the pyrochlore material, leading to a porous metal oxide network with an average pore diameter of 10 nm.

  5. Optimization of parameters in the synthesis of 0.90Pb(Zn1/3Nb2/3)O3–0.10PbTiO3 (PZN-10PT) powders obtained by the mixed oxides method

    Energy Technology Data Exchange (ETDEWEB)

    Raigoza, C.F.V.; Garcia, D.; Eiras, J.A.; Kiminami, R.H.G.A.

    2017-07-01

    Preventing the formation of the pyrochlore phase in the synthesis of PZN-PT powders requires controlling calcination parameters such as temperature, soaking time and atmosphere. These parameters were examined extensively to determine the time and temperature at which the perovskite phase is the majority phase, as well as the atmosphere that facilitates the formation of this phase. A maximum of 74% of perovskite phase was obtained under the following conditions: 1000°C, 4h in nitrogen atmosphere. In this work, we studied the influence of these parameters, which were optimized, on the formation the perovskite phase in PZN-10PT powders synthesized by the conventional solid state method. (Author)

  6. Corrosion behavior of pyroclore-rich titanate ceramics for plutonium disposition; impurity effects

    International Nuclear Information System (INIS)

    Bakel, A. J.

    1999-01-01

    The baseline ceramic contains Ti, U, Ca, Hf, Gd, and Ce, and is made up of only four phases, pyrochlore, zirconolite, rutile, and brannerite. The impurities present in the three other ceramics represent impurities expected in the feed, and result in different phase distributions. The results from 3 day, 90 C MCC-1 tests with impurity ceramics were significantly different than the results from tests with the baseline ceramic. Overall, the addition of impurities to these titanate ceramics alters the phase distributions, which in turn, affects the corrosion behavior

  7. Key insights on the structural characterization of textured Er2O3–ZrO2 nano-oxides prepared by a surfactant-free solvothermal route

    International Nuclear Information System (INIS)

    Julián-López, Beatriz; Luz, Verónica de la; Gonell, Francisco; Cordoncillo, Eloisa; López-Haro, Miguel; Calvino, Jose J.; Escribano, Purificación

    2012-01-01

    Highlights: ► Structural resolution of fluorite vs. pyrochlore in small nanocrystals. ► Simple template-free solvothermal synthesis of Er 2 O 3 –ZrO 2 nanooxides. ► Good control over size, morphology and surface properties (280 m 2 g −1 ). - Abstract: Zirconia-mixed oxides can exhibit cubic fluorite and pyrochlore structure. Their discrimination is not easy in nanooxides with a crystal size close to that of a few unit cells. In this work, high resolution transmission electron microscopy (HRTEM) has been employed to provide key insights on the structural characterization of a nanometric and porous mixed Er 2 O 3 –ZrO 2 oxide. The material was prepared by a simple template-free solvothermal route that provided nanocrystalline powders at low temperature (170 °C) with spherical morphology, and high surface area (∼280 m 2 g −1 ). The porosity was mainly originated from the assembling of organic complexing agents used in the synthesis to limit the crystal growth and to control hydrolysis and condensation reaction rates. The samples were characterized by thermal analysis, X-ray diffraction, scanning electron microscopy and N 2 adsorption measurements. A detailed study by HRTEM was conducted on microtomed samples. It was observed that the material was made of nanocrystals packed into spherical agglomerates. HRTEM simulations indicated that it is not possible to identify the pyrochlore phase in nanoparticles with diameter below 2 nm. In our samples, the analysis of the HRTEM lattice images by means of fast Fourier transform (FFT) techniques revealed well defined spots that can be assigned to different planes of a cubic fluorite-type phase, even in the raw material. Raman spectroscopy was also a powerful technique to elucidate the crystalline phase of the materials with the smallest nanoparticles. HREM and Raman results evidenced that the material is constituted, irrespective of the temperature of the final calcination step, by an ensemble of randomly

  8. Ionic conductivity of Ca and Mg doped NdGdZr1.95Sc0.05O7

    International Nuclear Information System (INIS)

    Anithakumari, P.; Mandal, B.P.; Grover, V.; Tyagi, A.K.; Mishra, A.K.

    2014-01-01

    The ionic conductivity of pyrochlore based materials makes them promising candidates for fuel-cell applications where high ionic conductivity and low activation energy are desired. Earlier it has been reported that 5%Sc doped GdNdZr 2 O 7 shows highest ionic conductivity. In this present work, an attempt has been made to further increase the oxygen vacancy concentration by the incorporation of Ca 2+ and Mg 2+ ions at A site of NdGdZr 1.95 Sc 0.05 O 7 (NGZS)

  9. EXAFS and XANES analysis of plutonium and cerium edges from titanate ceramics for fissile materials disposal

    International Nuclear Information System (INIS)

    Fortner, J. A.; Kropf, A. J.; Bakel, A. J.; Hash, M. C.; Aase, S. B.; Buck, E. C.; Chamerlain, D. B.

    1999-01-01

    We report x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) spectra from the plutonium L III edge and XANES from the cerium L II edge in prototype titanate ceramic hosts. The titanate ceramics studied are based upon the hafnium-pyrochlore and zirconolite mineral structures and will serve as an immobilization host for surplus fissile materials, containing as much as 10 weight % fissile plutonium and 20 weight % (natural or depleted) uranium. Three ceramic formulations were studied: one employed cerium as a ''surrogate'' element, replacing both plutonium and uranium in the ceramic matrix, another formulation contained plutonium in a ''baseline'' ceramic formulation, and a third contained plutonium in a formulation representing a high-impurity plutonium stream. The cerium XANES from the surrogate ceramic clearly indicates a mixed III-IV oxidation state for the cerium. In contrast, XANES analysis of the two plutonium-bearing ceramics shows that the plutonium is present almost entirely as Pu(IV) and occupies the calcium site in the zirconolite and pyrochlore phases. The plutonium EXAFS real-space structure shows a strong second-shell peak, clearly distinct from that of PuO 2 , with remarkably little difference in the plutonium crystal chemistry indicated between the baseline and high-impurity formulations

  10. Deposition of highly (111)-oriented PZT thin films by using metal organic chemical deposition

    CERN Document Server

    Bu, K H; Choi, D K; Seong, W K; Kim, J D

    1999-01-01

    Lead zirconate titanate (PZT) thin films have been grown on Pt/Ta/SiNx/Si substrates by using metal organic chemical vapor deposition with Pb(C sub 2 H sub 5) sub 4 , Zr(O-t-C sub 4 H sub 9) sub 4 , and Ti(O-i-C sub 3 H sub 7) sub 4 as source materials and O sub 2 as an oxidizing gas. The Zr fraction in the thin films was controlled by varying the flow rate of the Zr source material. The crystal structure and the electrical properties were investigated as functions of the composition. X-ray diffraction analysis showed that at a certain range of Zr fraction, highly (111)-oriented PZT thin films with no pyrochlore phases were deposited. On the other hand, at low Zr fractions, there were peaks from Pb-oxide phases. At high Zr fractions, peaks from pyrochlore phase were seen. The films also showed good electrical properties, such as a high dielectric constant of more than 1200 and a low coercive voltage of 1.35 V.

  11. Luminescence studies on Sb3+ co-doped Y2Sn2O7: Tb nanoparticles

    International Nuclear Information System (INIS)

    Nigam, Sandeep; Sudarsan, V.; Vatsa, R.K.

    2008-01-01

    Pyrochlore-type oxides (A 2 B 2 O 7 ) have emerged as important host matrices for lanthanide doped luminescent materials due to their good thermal stability. Due to the higher symmetry around the A and B cations in the lattice lanthanide ions like Eu 3+ and Tb 3+ when incorporated at the A or B sites give very poor luminescence. One way to circumvent this problem is to incorporate ions like Sb 3+ or Bi 3+ in the lattice so that the lattice get distorted and luminescent intensity from the lanthanide ions increases. The present study deals with the synthesis and characterisation of Sb 3+ co-doped Y 2 Sn 2 O 7 :Tb nanoparticles prepared by the hydrolysis of Y 3+ , Sn 4+ , Tb 3+ and Sb 3+ in ethylene glycol medium followed by heating at 700 deg C for 4 hours. From XRD studies it is confirmed that as prepared sample is amorphous and heat treatment at 700 deg C results in the formation of highly crystalline Y 2 Sn 2 O 7 phase having pyrochlore structure

  12. Competing Spin Liquids and Hidden Spin-Nematic Order in Spin Ice with Frustrated Transverse Exchange

    Directory of Open Access Journals (Sweden)

    Mathieu Taillefumier

    2017-12-01

    Full Text Available Frustration in magnetic interactions can give rise to disordered ground states with subtle and beautiful properties. The spin ices Ho_{2}Ti_{2}O_{7} and Dy_{2}Ti_{2}O_{7} exemplify this phenomenon, displaying a classical spin-liquid state, with fractionalized magnetic-monopole excitations. Recently, there has been great interest in closely related “quantum spin-ice” materials, following the realization that anisotropic exchange interactions could convert spin ice into a massively entangled, quantum spin liquid, where magnetic monopoles become the charges of an emergent quantum electrodynamics. Here we show that even the simplest model of a quantum spin ice, the XXZ model on the pyrochlore lattice, can realize a still-richer scenario. Using a combination of classical Monte Carlo simulation, semiclassical molecular-dynamics simulation, and analytic field theory, we explore the properties of this model for frustrated transverse exchange. We find not one, but three competing forms of spin liquid, as well as a phase with hidden, spin-nematic order. We explore the experimental signatures of each of these different states, making explicit predictions for inelastic neutron scattering. These results show an intriguing similarity to experiments on a range of pyrochlore oxides.

  13. Safe management of actinides in the nuclear fuel cycle: Role of mineralogy; La gestion des actinides dans le cycle du combustible nucleaire: le role de la mineralogie

    Energy Technology Data Exchange (ETDEWEB)

    Ewing, R.C. [Department of Nuclear Engineering and Radiological Sciences, Department of Geological Sciences, Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109-1005 (United States)

    2011-02-15

    During the past 60 years, more than 1800 metric tonnes of Pu, and substantial quantities of the 'minor' actinides, such as Np, Am and Cm, have been generated in nuclear reactors. Some of these transuranium elements can be a source of energy in fission reactions (e.g., {sup 239}Pu), a source of fissile material for nuclear weapons (e.g., {sup 239}Pu and {sup 237}Np), and of environmental concern because of their long-half lives and radiotoxicity (e.g., {sup 239}Pu and {sup 237}Np). There are two basic strategies for the disposition of these heavy elements: (1) to 'burn' or transmute the actinides using nuclear reactors or accelerators; (2) to 'sequester' the actinides in chemically durable, radiation-resistant materials that are suitable for geologic disposal. There has been substantial interest in the use of actinide-bearing minerals, especially isometric pyrochlore, A{sub 2}B{sub 2}O{sub 7} (A rare earths; B = Ti, Zr, Sn, Hf), for the immobilization of actinides, particularly plutonium, both as inert matrix fuels and nuclear waste forms. Systematic studies of rare-earth pyrochlores have led to the discovery that certain compositions (B = Zr, Hf) are stable to very high doses of alpha-decay event damage. Recent developments in our understanding of the properties of heavy element solids have opened up new possibilities for the design of advanced nuclear fuels and waste forms. (author)

  14. Safe management of actinides in the nuclear fuel cycle: Role of mineralogy

    International Nuclear Information System (INIS)

    Ewing, R.C.

    2011-01-01

    During the past 60 years, more than 1800 metric tonnes of Pu, and substantial quantities of the 'minor' actinides, such as Np, Am and Cm, have been generated in nuclear reactors. Some of these transuranium elements can be a source of energy in fission reactions (e.g., 239 Pu), a source of fissile material for nuclear weapons (e.g., 239 Pu and 237 Np), and of environmental concern because of their long-half lives and radiotoxicity (e.g., 239 Pu and 237 Np). There are two basic strategies for the disposition of these heavy elements: (1) to 'burn' or transmute the actinides using nuclear reactors or accelerators; (2) to 'sequester' the actinides in chemically durable, radiation-resistant materials that are suitable for geologic disposal. There has been substantial interest in the use of actinide-bearing minerals, especially isometric pyrochlore, A 2 B 2 O 7 (A rare earths; B = Ti, Zr, Sn, Hf), for the immobilization of actinides, particularly plutonium, both as inert matrix fuels and nuclear waste forms. Systematic studies of rare-earth pyrochlores have led to the discovery that certain compositions (B = Zr, Hf) are stable to very high doses of alpha-decay event damage. Recent developments in our understanding of the properties of heavy element solids have opened up new possibilities for the design of advanced nuclear fuels and waste forms. (author)

  15. Orientation of rapid thermally annealed lead zirconate titanate thin films on (111) Pt substrate

    International Nuclear Information System (INIS)

    Brooks, K.G.; Reaney, I.M.; Klissurska, R.; Huang, Y.; Bursill, L.A.; Setter, N.

    1994-01-01

    The nucleation, growth and orientation of lead zirconate titanate thin films prepared from organometallic precursor solutions by spin coating on (111) oriented platinum substrates and crystallized by rapid thermal annealing was investigated. The effects of pyrolysis temperature, post-pyrolysis thermal treatments, excess lead addition, and Nb dopant substitution are reported. The use of post pyrolysis oxygen anneals at temperatures in the regime of 350-450 deg C was found to strongly effect the kinetics of subsequent amorphous-pyrochlore perovskite crystallization by rapid thermal annealing. It has also allowed films of reproducible microstructure and textures (both (100) and (111)) to be prepared by rapid thermal annealing. It is suggested that such anneals and pyrolysis temperature affect the oxygen concentration/average Pb valence in the amorphous films prior to annealing. The changes in Pb valence state then affect the stability of the transient pyrochlore phase and thus the kinetics of perovskite crystallization. Nb dopant was also found to influence the crystallization kinetics. 28 refs., 18 figs

  16. Crystallization of sol-gel derived lead zirconate titanate thin films in argon and oxygen atmospheres

    International Nuclear Information System (INIS)

    Bursill, L.A.

    1994-01-01

    Electron diffraction and high-resolution electron microscopic techniques are applied to reveal the mechanisms of crystallization of 75 nm thin films of ferroelectric lead-zirconate-titanate (PZT). Sol-gel methods, followed by pyrolysis at 350 deg C, were used to provide a common starting point after which a variety of rapid-thermal annealing (RTA) experiments in the temperature range 400-700 deg C were made in argon, oxygen and nitrogen/hydrogen atmospheres. The results are interpreted in terms of the crystal chemical analysis, which points out that partial pressure of oxygen and heating rate are important experimental parameters which must be controlled if ferroelectric perovskite-type Pb 2 ZrTiO 6 , rather than pyrochlore-type Pb 2 ZrTiO 6+x , where O < X < 1 or -1 < X < O, is to be obtained after the RTA step. Thus significant improvements in the crystallization of perovskite-type PZT were clearly demonstrated by using argon atmospheres for the RTA step. The results have significance for the production of high-quality ferroelectric thin films, with improved switching and fatigue characteristics, since even small amounts of the pyrochlore phase prove detrimental for these properties. 18 refs., 1 tab., 10 figs

  17. Crystallization of sol-gel derived lead zirconate titanate thin films in argon and oxygen atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Bursill, L A [Melbourne Univ., Parkville, VIC (Australia). School of Physics; Brooks, K G [Ecole Polytechnique Federale, Lausanne (Switzerland)

    1994-12-31

    Electron diffraction and high-resolution electron microscopic techniques are applied to reveal the mechanisms of crystallization of 75 nm thin films of ferroelectric lead-zirconate-titanate (PZT). Sol-gel methods, followed by pyrolysis at 350 deg C, were used to provide a common starting point after which a variety of rapid-thermal annealing (RTA) experiments in the temperature range 400-700 deg C were made in argon, oxygen and nitrogen/hydrogen atmospheres. The results are interpreted in terms of the crystal chemical analysis, which points out that partial pressure of oxygen and heating rate are important experimental parameters which must be controlled if ferroelectric perovskite-type Pb{sub 2}ZrTiO{sub 6}, rather than pyrochlore-type Pb{sub 2}ZrTiO{sub 6+x}, where O < X < 1 or -1 < X < O, is to be obtained after the RTA step. Thus significant improvements in the crystallization of perovskite-type PZT were clearly demonstrated by using argon atmospheres for the RTA step. The results have significance for the production of high-quality ferroelectric thin films, with improved switching and fatigue characteristics, since even small amounts of the pyrochlore phase prove detrimental for these properties. 18 refs., 1 tab., 10 figs.

  18. Fundamental thermodynamics of actinide-bearing mineral waste forms. 1998 annual progress report

    International Nuclear Information System (INIS)

    Ebbinghaus, B.B.; Williamson, M.A.

    1998-01-01

    'The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly, understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpy of formation of actinide substituted zircon, zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stability of these materials. This report summarizes work after eight months of a three year project.'

  19. A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction.

    Science.gov (United States)

    Kuriki, Ryo; Ichibha, Tom; Hongo, Kenta; Lu, Daling; Maezono, Ryo; Kageyama, Hiroshi; Ishitani, Osamu; Oka, Kengo; Maeda, Kazuhiko

    2018-05-16

    Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N 3- , S 2- ) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb 2 Ti 2 O 5.4 F 1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb 2 Ti 2 O 5.4 F 1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb 2 Ti 2 O 5.4 F 1.2 worked as a stable photocatalyst for visible-light-driven H 2 evolution and CO 2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb 2 Ti 2 O 5.4 F 1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

  20. Orange-red emitting Gd2Zr2O7:Sm3+: Structure-property correlation, optical properties and defect spectroscopy

    Science.gov (United States)

    Gupta, Santosh K.; Reghukumar, C.; Sudarshan, K.; Ghosh, P. S.; Pathak, Nimai; Kadam, R. M.

    2018-05-01

    Local structure analysis of dopant ion, understanding host to dopant energy transfer dynamics and defects characterization in a doped material which plays an important role in the designing a highly efficient opto-electronic material. In this connection a new Sm3+ doped Gd2Zr2O7 pyrochlore material was synthesized using gel-combustion technique and was characterized systematically using X-ray diffraction (XRD), time resolved photoluminescence spectroscopy (TRPLS), positron annihilation lifetime spectroscopy (PALS) and density functional theory (DFT) based ab-initio calculation. Based on DFT site selective energetics calculation and luminescence decay measurement, it was observed that the Sm3+ was distributed at both Gd3+ and Zr4+ site with higher Sm3+ fraction at the Gd3+ site. PALS was used to probe the presence of defects in the phosphor. In this work intense orange-red emission is realized through manipulating the energy transfer from host defect emission (oxygen vacancies) to Sm3+ which allows color emission from green in undoped to orange-red in doped samples. Effect of dopant concentration and annealing temperature was probed using TRPLS and PALS. These all information is highly important for researcher looking to achieve pyrochlore based phosphor materials with high quantum yield.

  1. Fundamental Thermodynamics of Actinide-Bearing Mineral Waste Forms - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Williamson, Mark A.; Ebbinghaus, Bartley B.; Navrotsky, Alexandra

    2001-03-01

    The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpies of formation of actinide substituted zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stabilities of these materials.

  2. Fundamental Thermodynamics of Actinide-Bearing Mineral Waste Forms - Final Report

    International Nuclear Information System (INIS)

    Williamson, Mark A.; Ebbinghaus, Bartley B.; Navrotsky, Alexandra

    2001-01-01

    The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpies of formation of actinide substituted zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stabilities of these materials

  3. Effects of the sintering temperature on the diffused phase transition and the spin-glassy behavior in Pb0.95La0.05(Fe2/3W1/3)0.65Ti0.35O3 ceramics

    International Nuclear Information System (INIS)

    Hong, Cheng-Shong; Chu, Sheng-Yuan; Hsu, Chi-Cheng

    2010-01-01

    In this paper, the effect of the sintering temperature on the low-field dielectric behavior of nonstoichiometric Pb 0.95 La 0.05 (Fe 2/3 W 1/3 ) 0.65 Ti 0.35 O 3 relaxor ferroelectrics is investigated. The x-ray patterns and the scanning electron microscope images are used to detect the pyrochlore phase and the perovskite structure. The electric properties of the resistivity, the space charge polarization, the temperature-dependent dielectric constant and dielectric loss are discussed. The diffused phase transition and the ordering state are fitted and discussed by using the empirical law and two ordering models. Furthermore, the glassy behavior is determined by using the Curie-Weiss law and the spin-glass model. According to the experimental data and fitting results, the dielectric picture is changed from the short range order relaxorlike behavior to the long range order normal ferroelectric state as increasing the sintering temperature and the glassy behavior is weakened at the lowest and highest sintering temperature at which the pyrochlore phase PWO 4 is induced. Therefore, it is suggested that the 1:1 ordered domain is enhanced by increasing the sintering temperature and the glassy behavior is related to not only the ordering degree also the polar defect pairs. For more ordering degree and polar defect pairs, the glassy is weakened and the correlation of neighboring polar microregions is enhanced.

  4. Relaxation path of metastable nanoclusters in oxide dispersion strengthened materials

    Energy Technology Data Exchange (ETDEWEB)

    Ribis, J., E-mail: joel.ribis@cea.fr [DEN-Service de Recherches Métallurgiques Appliquées, CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Thual, M.A. [LLB, CEA, CNRS, Université Paris-Saclay, CEA Saclay, 91191, Gif-sur-Yvette (France); Guilbert, T.; Carlan, Y. de [DEN-Service de Recherches Métallurgiques Appliquées, CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Legris, A. [UMET, CNRS/UMR 8207, Bât. C6, Univ. Lille 1, 59655 Villeneuve d’Ascq (France)

    2017-02-15

    ODS steels are a promising class of structural materials for sodium cooled fast reactor application. The ultra-high density of the strengthening nanoclusters dispersed within the ferritic matrix is responsible of the excellent creep properties of the alloy. Fine characterization of the nanoclusters has been conducted on a Fe-14Cr-0.3Ti-0.3Y{sub 2}O{sub 3} ODS material using High Resolution and Energy Filtered Transmission Electron Microscopy. The nanoclusters exhibit a cubic symmetry possibly identified as f.c.c and display a non-equilibrium YTiCrO chemical composition thought to be stabilized by a vacancy supersaturation. These nanoclusters undergo relaxation towards the Y{sub 2}Ti{sub 2}O{sub 7}-like state as they grow. A Cr shell is observed around the relaxed nano-oxides, this size-dependent shell may form after the release of Cr by the particles. The relaxation energy barrier appears to be higher for the smaller particles probably owing to a volume/surface ratio effect in reason to the full coherency of the nanoclusters. - Highlights: • The nanoclusters display a f.c.c. cubic symmetry and a non-equilibrium YTiCrO chemical composition. • During thermal annealing the coherent nanocluster transform into semi-coherent pyrochlore particles. • A Cr ring is observed around the relaxed pyrochlore type particles.

  5. Computational Design of Flat-Band Material

    Science.gov (United States)

    Hase, I.; Yanagisawa, T.; Kawashima, K.

    2018-02-01

    Quantum mechanics states that hopping integral between local orbitals makes the energy band dispersive. However, in some special cases, there are bands with no dispersion due to quantum interference. These bands are called as flat band. Many models having flat band have been proposed, and many interesting physical properties are predicted. However, no real compound having flat band has been found yet despite the 25 years of vigorous researches. We have found that some pyrochlore oxides have quasi-flat band just below the Fermi level by first principles calculation. Moreover, their valence bands are well described by a tight-binding model of pyrochlore lattice with isotropic nearest neighbor hopping integral. This model belongs to a class of Mielke model, whose ground state is known to be ferromagnetic with appropriate carrier doping and on-site repulsive Coulomb interaction. We have also performed a spin-polarized band calculation for the hole-doped system from first principles and found that the ground state is ferromagnetic for some doping region. Interestingly, these compounds do not include magnetic element, such as transition metal and rare-earth elements.

  6. Geochemical prospecting techniques for ore deposits in periglacial regions

    International Nuclear Information System (INIS)

    Pitul'ko, V.M.

    1977-01-01

    Necessity and prospects of the implementation of geochemical methods of search in periglacial regions are discussed. The behaviour of chemical elements under the conditions of oxide and sulphate cryogenic topographies whose development has common regularities is analyzed. According to the specificity of migration the observed elements have been divided into four groups: active, mobile, low-mobile and inert migrants. Uranium which is present in ores in the form of pitchblende in oxide zones of the oxidation is actively redistributed. In zones of the oxidation of rare metal metasomatites connected with alkalic ultrabasic rocks only that part of U is mobile which being released from pyrochlore forms the regenerated uranium black and the partial enrichment of the iron gossan. Th like other elements of the 4-th group in all oxidation zones is observed to accumulate in minerals - concentrators: thorite, pyrochlore and so on. A diagram is plotted which characterizes the migration of elements whithin aureole landscapes as well as in automonous and dependent topographies of ore-free areas. The complex nature of secondary aureoles displays the most complete anomalous spectrum of elements - indicators of mineralization. The table of the most typical elements - indicators of the secondary scattering of some endogenic deposits of the cryolitic zone is given

  7. Raman effect in ferroelectric Cd2Nb2O7 and in other crystals with pyrochlorine-type structure

    International Nuclear Information System (INIS)

    Pisarev, R.V.; Sinij, I.G.; Kuz'minov, E.G.; Myl'nikova, I.E.

    1976-01-01

    Vibrational structure of cadmium and lead pyroniobates and a number of other crystals with a pyrochlore structure has been investigated by Raman scattering. The scattering has been studied using a double monochromator, HeNe laser, and a photons counter. In the Raman spectrum of cadmium and lead pyroniobates three frequency band1 can be distinguished. In the spectrum of rhombohedral lead pyroniobate the band structure in resolved much better than in the spectrum of cubic cadmium pyroniobate. The spectrum of lead pyroniobate crystals doped with magnesium and zinc ions has a medium (in the sense of complexity) structure, because big lead ions deteriorate the pyrochlore structure but doping of lead pyroniobate with Mg 2+ and Zn 2+ ions improves it. More than six bands in the Raman spectrum is associated with the presence of impurities in cubic cadmium pyroniobate that deteriorate its cubic structure. The decrease of temperature leads to a big change of the Cd 2 Nb 2 O 7 spectrum. However, the spectrum of Pb 2 Nb 2 O 7 -Zn cubic crystal measured ar temperatures below 100 deg K remais unchanged. The chages of the Cd 2 Nb 2 O 7 spectrum are associated with phase transitions at 200 and 85 K and also with ferroelectric transition at 185 K

  8. Lower-Conductivity Ceramic Materials for Thermal-Barrier Coatings

    Science.gov (United States)

    Bansal, Narottam P.; Zhu, Dongming

    2006-01-01

    Doped pyrochlore oxides of a type described below are under consideration as alternative materials for high-temperature thermal-barrier coatings (TBCs). In comparison with partially-yttria-stabilized zirconia (YSZ), which is the state-of-the-art TBC material now in commercial use, these doped pyrochlore oxides exhibit lower thermal conductivities, which could be exploited to obtain the following advantages: For a given difference in temperature between an outer coating surface and the coating/substrate interface, the coating could be thinner. Reductions in coating thicknesses could translate to reductions in weight of hot-section components of turbine engines (e.g., combustor liners, blades, and vanes) to which TBCs are typically applied. For a given coating thickness, the difference in temperature between the outer coating surface and the coating/substrate interface could be greater. For turbine engines, this could translate to higher operating temperatures, with consequent increases in efficiency and reductions in polluting emissions. TBCs are needed because the temperatures in some turbine-engine hot sections exceed the maximum temperatures that the substrate materials (superalloys, Si-based ceramics, and others) can withstand. YSZ TBCs are applied to engine components as thin layers by plasma spraying or electron-beam physical vapor deposition. During operation at higher temperatures, YSZ layers undergo sintering, which increases their thermal conductivities and thereby renders them less effective as TBCs. Moreover, the sintered YSZ TBCs are less tolerant of stress and strain and, hence, are less durable.

  9. Mechanism of formation of perovskite phase and dielectric properties of Pb(Zn,Mg)1/3Nb2/3O3 ceramics prepared by columbite precursor routes

    International Nuclear Information System (INIS)

    Jang, H.M.; Cho, S.R.; Lee, K.M.

    1995-01-01

    The mechanism of formation of the perovskite phase and the dielectric properties of Pb(Zn,Mg) 1/3 Nb 2/3 O 3 (PZMN) ceramics were examined using two different types of columbite precursors, (Mg,Zn)Nb 2 O 6 (MZN) and MgNb 2 O 6 + ZnNb 2 O 6 (MN + ZN). The formation of perovskite phase in the PbO + MN + ZN system is characterized by an initial rapid formation of Mg-rich perovskite phase, followed by a sluggish formation of Zn-rich perovskite phase. On the other hand, due to the formation of pyrochlore phase of mixed divalent cations Pb 2-x (Zn,Mg) y Nb 2-y O 7-x-3y/2 , the pyrochlore/perovskite transformation in the PbO + MZN system proceeded uniformly with a spatial homogeneity. Further analysis suggested that the formation of perovskite phase is a diffusion-controlled process. The degree of diffuseness of the rhombohedral/cubic phase transition (DPT) is higher in the PbO + MN + ZN system than in the PbO + MZN specimen for T > T max (temperature of the dielectric permittivity maximum), indicating a broadened compositional distribution of the B-site cations in the PbO + MN + ZN system

  10. Synthesis, structural and luminescence properties of Bi3+ co-doped Y2Sn2O7:Tb nanoparticles

    International Nuclear Information System (INIS)

    Nigam, S.; Sudarsan, V.; Vatsa, R.K.

    2010-01-01

    Full text: In recent years, advanced materials derived from Pyrochlore-type oxides (A 2 B 2 O 7 ) have been of extensive scientific and technological interest. Chemical substitution of A or B sites of pyrochlore oxide by rare earth ions is a widely used approach to prepare thermally stable, lanthanide ion doped luminescent materials. Due to the higher symmetry around the A and B sites in the lattice lanthanide ions like Eu 3+ and Tb 3+ when incorporated at the A or B sites give very poor luminescence. This problem can be avoided by incorporating other ions like Bi 3+ in the lattice so that the lattice gets distorted and luminescent intensity from the lanthanide ions increases. The present study deals with the synthesis and characterization of Bi 3+ co-doped Y 2 Sn 2 O 7 :Tb nanoparticles. For the preparation of Tb 3+ and Bi 3+ doped Y 2 Sn 2 O 7 nano-materials, Sn metal, Bi(NO 3 ) 3 , Tb 4 O 7 , Y 2 CO 3 , were used as starting materials. The solution containing Y 3+ , Sn 4+ ,and Bi 3+ -Tb 3+ in ethylene glycol medium was slowly heated up to 120 deg C and then subjected to urea hydrolysis. The obtained precipitate after washing was heated to 700 deg C. As prepared samples are amorphous in nature and 700 deg C heated sample showed well crystalline pyrochlore structure as revealed by the XRD studies. Average particles size is calculated from the width of the X-ray diffraction peaks and found to be ∼ 5 nm. TEM images of the nanoparticles obtained at 700 deg C shows very fine spherical particles having a diameter in the range of 2-5 nm. Luminescence measurements were carried out for as prepared and 700 deg C heated samples of 2.5%Tb doped Y 2 Sn 2 O 7 nanoparticles. Green emission characteristic 5 D 4 7 F 5 transition of Tb 3+ has been observed from as prepared sample but on heating to 700 deg C the emission characteristic of Tb 3+ ions got completely removed . However, there is a significant improvement in Tb 3+ emission from 2.5% Bi 3+ co-doped Y 2 Sn 2 O 7 :Tb 3

  11. Structural, photoluminescence and radioluminescence properties of Eu{sup 3+} doped La{sub 2}Hf{sub 2}O{sub 7} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Wahid, Kareem; Pokhrel, Madhab; Mao, Yuanbing, E-mail: yuanbing.mao@utrgv.edu

    2017-01-15

    This study presents the structural, optical, and radioluminescent characterization of newly synthesized europium-doped lanthanum hafnate (La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+}, x=0 to 35) nanoparticles (NPs) for use as phosphors and scintillation materials. Samples prepared through a combined co-precipitation and molten salt synthetic process were found to crystalize in the pyrochlore phase, a radiation tolerant structure related to the fluorite structure. These samples exhibit red luminescence under ultraviolet and X-ray excitation. Under these excitations, the optical intensity and quantum yield of the La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+} NPs depend on the Eu{sup 3+} concentration and are maximized at 5%. It is proposed that there is a trade-off between the quenching due to defect states/cross-relaxation and dopant concentration. An optimal dopant concentration allows the La{sub 2}Hf{sub 2}O{sub 7}:5 mol%Eu{sup 3+} NPs to show the best luminescent properties of all the samples. - Graphical abstract: Incident X-ray and UV photons interact with La{sub 2}Hf{sub 2}O{sub 7}: xmol%Eu{sup 3+}(x=1–35) nanoparticles (NPs) to yield strong red luminescence centered at 612 nm. Colored spheres inside NP diagram represent pyrochlore coordination environment of La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+}. Blue, red, yellow, green and black spheres represent hafnium(IV) atoms, lanthanum(III)/europium(III) atoms, oxygen atoms at 48f site, oxygen atoms at 8b site and oxygen vacancies, respectively. - Highlights: • La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+} (x=0–35) nanoparticles with weakly-ordered pyrochlore structures were synthesized. • Optically and X-ray excited emission spectra showed strong luminescence centered at 612 nm. • Photoluminescence quantum yield increases with doping concentration up to 5% and decreases at higher concentrations.

  12. Design of medium band gap Ag-Bi-Nb-O and Ag-Bi-Ta-O semiconductors for driving direct water splitting with visible light.

    Science.gov (United States)

    Wang, Limin; Cao, Bingfei; Kang, Wei; Hybertsen, Mark; Maeda, Kazuhiko; Domen, Kazunari; Khalifah, Peter G

    2013-08-19

    Two new metal oxide semiconductors belonging to the Ag-Bi-M-O (M = Nb, Ta) chemical systems have been synthesized as candidate compounds for driving overall water splitting with visible light on the basis of cosubstitution of Ag and Bi on the A-site position of known Ca2M2O7 pyrochlores. The low-valence band edge energies of typical oxide semiconductors prevents direct water splitting in compounds with band gaps below 3.0 eV, a limitation which these compounds are designed to overcome through the incorporation of low-lying Ag 4d(10) and Bi 6s(2) states into compounds of nominal composition "AgBiM2O7". It was found that the "AgBiTa2O7" pyrochlores are in fact a solid solution with an approximate range of Ag(x)Bi(5/6)Ta2O(6.25+x/2) with 0.5 semiconductors with the onset of strong direct absorption at 2.72 and 2.96 eV, respectively. Electronic structure calculations for an ordered AgBiNb2O7 structure show that the band gap reduction and the elevation of the valence band primarily result from hybridized Ag d(10)-O 2p orbitals that lie at higher energy than the normal O 2p states in typical pyrochlore oxides. While the minimum energy gap is direct in the band structure, the lowest energy dipole allowed optical transitions start about 0.2 eV higher in energy than the minimum energy transition and involve different bands. This suggests that the minimum electronic band gap in these materials is slightly smaller than the onset energy for strong absorption in the optical measurements. The elevated valence band energies of the niobate and tantalate compounds are experimentally confirmed by the ability of these compounds to reduce 2 H(+) to H2 gas when illuminated after functionalization with a Pt cocatalyst.

  13. Radioactive ores from Agostinho field, Pocos de Caldas (MG), Brazil

    International Nuclear Information System (INIS)

    Fujimori, K.

    1974-01-01

    Aiming to characterize the radioactive minerals of Campo Agostinho, Pocos de Caldas - Brazil, the survey of all natural radiactive elements and their geochemical behaviors, decays and radioactive equilibrium was done. Several models of radioactive instability of the minerals or the radioactive samples were proposed to characterize the geochemistry and the mineralization of radioactive elements. The complete isotopic analysis of the elements was done by high resolution gamma spectrometry, using a Ge(Li) detector, at the temperature of liquid nitrogen, coupled to a multichannel analyser. The sample in radioactive equilibrium of Atomic Energy Comission of United States - A.S. n.6, NBL - New Brunswick Laboratory, was considered as standard sample. Fluorite, zircons, pirite, molibinite, rutile, anatase, niobophyllite, and in small ratio (bellow 0.1%) uranothorianite, coffinite, pyrochlore, monazite and apatite. (M.C.K.) [pt

  14. Phase evolution and microwave dielectric properties of A5M5O17-type ceramics

    Directory of Open Access Journals (Sweden)

    Ali Murad

    2017-07-01

    Full Text Available A number of A5M5O17 (A = Na, Ca, Sr, La, Nd, Sm, Gd, Dy, Yb; B = Ti, Nb, Ta type compounds were prepared by a solid-state sintering route and characterized in terms of structure, microstructure and microwave dielectric properties. The compatibility of rare earths with mixed niobate/tantalate and titanate phases was investigated. The larger ionic radii mismatch resulted in the formation of pyrochlore and/or mixed phases while in other cases, pure A5M5O17 phase was formed. The samples exhibited relative permittivity in the range of 35 to 82, quality factor (Q × fo = 897 GHz to 11946 GHz and temperature coefficient of resonance frequency (τf = -120 ppm/°C to 318 ppm/°C.

  15. High temperature phase transition of Tm2Ti2O7

    International Nuclear Information System (INIS)

    Shlyakhtina, A.V.; Shcherbakova, L.G.; Knot'ko, A.V.; Larina, L.L.; Borichev, S.A.

    2004-01-01

    A high temperature phase transition type order-disorder is investigated in Tm 2 Ti 2 O 7 at t>1600 Deg C. It is shown that this transformation is irreversible. Ion conductivity of synthesized at 1670 Deg C nanocrystalline Tm 2 Ti 2 O 7 constitutes 2x10 -3 S/cm at 740 Deg C and remains constant after heat treatment at 860 Deg C for 240 h in the air. It is revealed that the conductivity of specimens (grain size of 20-30 nm) on the basis of Tm 2 Ti 2 O 7 high temperature modification with a structure of disordered pyrochlore is independent of grain size [ru

  16. Thermal cycling behaviour of lanthanum zirconate as EB-PVD thermal barrier coating

    International Nuclear Information System (INIS)

    Bobzin, K.; Lugscheider, E.; Bagcivan, N.

    2006-01-01

    Thermal cycling tests with two different EB-PVD thermal barrier coatings (TBC) were performed in a furnace cycle test. The results of these tests showed an increase of endurable cycle number when pyrochloric La 2 Zr 2 O 7 was used as TBC. 1865 cycles were reached with La 2 Zr 2 O 7 and 1380 cycles with 7 weigth-% yttria stabilised zirconia (YSZ) EB-PVD TBC. Additional investigation was made with scanning electron microscope (SEM) to investigate morphology and to determine chemical composition by electron dispersive x-ray spectroscopy (EDS) analysis. X-Ray diffraction was performed to analyze structural constitution of deposited coatings. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  17. Nature of the tensor order in Cd2Re2O7

    Science.gov (United States)

    Di Matteo, S.; Norman, M. R.

    2017-09-01

    The pyrochlore metal Cd2Re2O7 has been recently investigated by second-harmonic generation (SHG) reflectivity. In this paper, we develop a general formalism that allows for the identification of the relevant tensor components of the SHG from azimuthal scans. We demonstrate that the secondary order parameter identified by SHG at the structural phase transition is the x2-y2 component of the axial toroidal quadrupole. This differs from the 3 z2-r2 symmetry of the atomic displacements associated with the I 4 ¯m 2 crystal structure that was previously thought to be its origin. Within the same formalism, we suggest that the primary order parameter detected in the SHG experiment is the 3 z2-r2 component of the magnetic quadrupole. We discuss the general mechanism driving the phase transition in our proposed framework, and suggest experiments, particularly resonant x-ray scattering ones, that could clarify this issue.

  18. Bioleaching of UO22+ ions from a Romanian poor uranium ore

    International Nuclear Information System (INIS)

    Cecal, Al.; Popa, K.; Moraru, R.T.; Patachia, S.

    2002-01-01

    An experimental study on the bioleaching of a poor uranium ore by means of hydrophytic plants Lemna minor and Riccia fluitans, under various operating conditions is discussed. The maximum degree of bioleaching (42%) of the reduced uranium species to U(VI) has been attained for the ore-Lemna minor-alkaline carbonate solution system. The UO 2 2+ ions amount accumulated in the plants is negligible as compared to the dissolved quantity, owing to the ionic competition between uranyl ions and the cations necessary to the mineral nutrition. The X-ray diffraction patterns prove that the uranium species in pyrochlore mineral are completely oxidized to U(VI), while thucolite is only partially turned into UO 2 2+ ions, in the presence of living plants. (author)

  19. Spin-phonon induced magnetic order in magnetized Spin Ice systems

    International Nuclear Information System (INIS)

    Albarracín, F A Gómez; Cabra, D C; Rosales, H D; Rossini, G L

    2014-01-01

    We study the behavior of spin ice pyrochlore systems above the well known [111] 1/3 plateau, under slight deviations of the direction of the external field. We model the relevant degrees of freedom by Ising spins on the kagome lattice. We propose the inclusion of lattice deformations, which imply phononic degrees of freedom in the adiabatic limit. We use analytical calculations to estimate how these new degrees of freedom affect the short and long range spin interactions in the presence of an external magnetic field. We then obtain the magnetization curves, explore the phases and the ground states of this system in the presence of magnetic field by Monte Carlo simulations. We discuss comparisons with experimental results

  20. Features of dielectric response in PMN-PT ferroelectric ceramics

    International Nuclear Information System (INIS)

    Guerra, J D S; Araujo, E B; Guarany, C A; Reis, R N; Lima, E C

    2008-01-01

    In this paper, electrical and structural properties were reported for pyrochlore free (1 - x)[Pb(Mg 1/3 Nb 2/3 )O 3 ] - xPbTiO 3 (PMN-PT) (with 35 mol% PbTiO 3 ) ceramics obtained from fine powders. Dielectric studies were focused on the investigation of the complex dielectric permittivity (ε' - iε'') as a function of frequency and temperature. The effects of the dc applied electric field on dielectric response were also investigated. Results revealed a field dependence dielectric anomaly in the dielectric permittivity curves (ε(T)) in the low dc electric field region, which in turn prevails in the whole analysed frequency interval. To the best of our knowledge, these properties for the PMN-PT ceramic system have not been reported before as in this work. The results were analysed within the framework of the current models found in the literature.

  1. Load-partitioning in an oxide dispersion-strengthened 310 steel at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Yinbin; Mo, Kun; Zhou, Zhangjian; Liu, Xiang; Lan, Kuan-Che; Zhang, Guangming; Park, Jun-Sang; Almer, Jonathan; Stubbins, James F.

    2016-12-01

    Here the high temperature tensile performance of an oxide dispersion-strengthened (ODS) 310 steel is reported upon. The microstructure of the steel was examined through both transmission electron microscopy (TEM) and synchrotron scattering. In situ synchrotron tensile investigation was performed at a variety of temperatures, from room temperature up to 800°C. Pyrochlore structure yttrium titanate and sodium chloride structure titanium nitride phases were identified in the steel along with an austenite matrix and marginal residual α’-martensite. The inclusion phases strengthen the steel by taking extra load through particle-dislocation interaction during plastic deformation or dislocation creep procedures. As temperature rises, the load partitioning effect of conventional precipitate phases starts to diminish, whereas those ultra-fine oxygen-enriched nanoparticles continue to bear a considerable amount of extra load. Introduction of oxygen-enriched nanoparticles in austenitic steel proves to improve the high temperature performance, making austenitic ODS steels promising for advanced nuclear applications.

  2. Realizing three-dimensional artificial spin ice by stacking planar nano-arrays

    International Nuclear Information System (INIS)

    Chern, Gia-Wei; Reichhardt, Charles; Nisoli, Cristiano

    2014-01-01

    Artificial spin ice is a frustrated magnetic two-dimensional nano-material, recently employed to study variety of tailor-designed unusual collective behaviours. Recently proposed extensions to three dimensions are based on self-assembly techniques and allow little control over geometry and disorder. We present a viable design for the realization of a three-dimensional artificial spin ice with the same level of precision and control allowed by lithographic nano-fabrication of the popular two-dimensional case. Our geometry is based on layering already available two-dimensional artificial spin ice and leads to an arrangement of ice-rule-frustrated units, which is topologically equivalent to that of the tetrahedra in a pyrochlore lattice. Consequently, we show, it exhibits a genuine ice phase and its excitations are, as in natural spin ice materials, magnetic monopoles interacting via Coulomb law

  3. Ceramics: Durability and radiation effects

    Energy Technology Data Exchange (ETDEWEB)

    Ewing, R.C.; Lutze, W. [Univ. of New Mexico, Albuquerque, NM (United States); Weber, W.J. [Pacific Northwest National Lab., Richland, WA (United States)

    1996-05-01

    At present, there are three seriously considered options for the disposition of excess weapons plutonium: (1) incorporation, partial burn-up and direct disposal of MOX-fuel; (2) vitrification with defense waste and disposal as glass {open_quotes}logs{close_quotes}; (3) deep borehole disposal. The first two options provide a safeguard due to the high activity of fission products in the irradiated fuel and the defense waste. The latter option has only been examined in a preliminary manner, and the exact form of the plutonium has not been identified. In this paper, we review the potential for the immobilization of plutonium in highly durable crystalline ceramics apatite, pyrochlore, zirconolite, monazite and zircon. Based on available data, we propose zircon as the preferred crystalline ceramic for the permanent disposition of excess weapons plutonium.

  4. Cold crucible induction melter test for crystalline ceramic waste form fabrication: A feasibility assessment

    Energy Technology Data Exchange (ETDEWEB)

    Amoroso, Jake W., E-mail: jake.amoroso@srnl.doe.gov [Savannah River National Laboratory, Aiken, SC 29808 (United States); Marra, James; Dandeneau, Christopher S. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Brinkman, Kyle; Xu, Yun [Clemson University, Clemson, SC 29634 (United States); Tang, Ming [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Maio, Vince [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Webb, Samuel M. [Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94086 (United States); Chiu, Wilson K.S. [University of Connecticut, Storrs, Connecticut 06269-3139 (United States)

    2017-04-01

    The first scaled proof-of-principle cold crucible induction melter (CCIM) test to process a multiphase ceramic waste form from a simulated combined (Cs/Sr, lanthanide and transition metal fission products) commercial used nuclear fuel waste stream was recently conducted in the United States. X-ray diffraction, 2-D X-ray absorption near edge structure (XANES), electron microscopy, inductively coupled plasma-atomic emission spectroscopy (and inductively coupled plasma-mass spectroscopy for Cs), and product consistency tests were used to characterize the fabricated CCIM material. Characterization analyses confirmed that a crystalline ceramic with a desirable phase assemblage was produced from a melt using a CCIM. Primary hollandite, pyrochlore/zirconolite, and perovskite phases were identified in addition to minor phases rich in Fe, Al, or Cs. The material produced in the CCIM was chemically homogeneous and displayed a uniform phase assemblage with acceptable aqueous chemical durability.

  5. The XPS study of the structure of uranium-containing ceramics

    Directory of Open Access Journals (Sweden)

    Teterin Anton Yu.

    2010-01-01

    Full Text Available The samples of the (Ca0.5GdU0.5Zr2O7 and (Ca0.5GdU0.5(ZrTiO7 ceramics with the fluorite and pyrochlore structures used as matrixes for the long-lived high-level radioactive waste disposal were studied with the X-ray photoelectron spectroscopy method. On the basis of the X-ray photoelectron spectroscopy parameters of the outer and core electrons from the binding energy range of 0-1250 eV the oxidation states of the included metal ions were determined, the quantitative elemental and ionic analysis was done, and the orderliness (monophaseness was evaluated. The obtained data agree with the X-ray diffraction and the scanning electron microscopy results.

  6. Fabrication and spectroscopic properties of nanocrystalline La{sub 2}Hf{sub 2}O{sub 7}:Pr

    Energy Technology Data Exchange (ETDEWEB)

    Trojan-Piegza, J., E-mail: jtp@eto.wchuwr.p [Faculty of Chemistry, Wroclaw University, 14 F. Joliot-Curie Street, 50383 Wroclaw (Poland); Zych, E.; Kosinska, M. [Faculty of Chemistry, Wroclaw University, 14 F. Joliot-Curie Street, 50383 Wroclaw (Poland)

    2010-03-15

    La{sub 2}Hf{sub 2}O{sub 7} nanopowders doped with different Pr concentrations (0.05-10 mol.%) were synthesized by the Pechini method. XRD measurements confirmed the single crystalline phase formed already at 800 {sup o}C and the structure was cubic pyrochlore. Luminescence excitation and emission as well as radioluminescence spectra were recorded for the materials. Both optical and X-ray excitation of La{sub 2}Hf{sub 2}O{sub 7}:Pr produced a red emission resulting from the 4f-4f transitions of Pr{sup 3+} ions. Luminescence of materials synthesized at low temperatures was characterized by broadband glass-type emissions, while heat treatment at 1400 {sup o}C led to spectra showing the typical for crystalline hosts narrow and intense 4f-4f transitions of Pr{sup 3+}.

  7. Mixed oxides forming in CdO-OsO2 and PbO-OsO2 systems

    International Nuclear Information System (INIS)

    Shaplygin, I.S.; Lazarev, V.B.

    1978-01-01

    The formation of mixed oxides in systems CdO-OsO 2 and PbO-OsO 2 was studied by derivatography, X-ray phase analysis, and IR spectroscopy. It was established that in the system CdO-OsO 2 cubic phases of Cdsub(2)Ossub(2)Osub(6.7) and Cdsub(2)Ossub(2)Osub(7.2) with a pyrochlor-type structure, as well as new compounds with the structure of rhombic perovskite CdOsO 3 and Cd(Cdsub(0.5)Ossub(0.5))Osub(3) containing osmium in the formal degree of oxidation +4 and +6, respectively, are formed. The thermal stability of the compounds obtained was studied and their electrical properties determined

  8. Detecting Magnetic Monopoles in Spin Ice with NV-magnetometry

    Science.gov (United States)

    Flicker, Felix; Kirschner, Franziska; Yao, Norman; Blundell, Stephen

    2017-04-01

    Magnetic monopoles, isolated north and south poles, appear not to exist as fundamental particles in our universe. Nevertheless, it has been proposed that they may emerge as quasiparticles in certain materials: the geometrically-frustrated `spin ice' pyrochlores dysprosium and holmium titanate. Despite a great deal of experimental and theoretical work, the smoking gun signature of magnetic monopoles in spin ice remains to be discovered. A promising candidate for the detection of individual magnetic monopoles comes in the form of Nitrogen-Vacancy (NV) defects in diamond, which act as very sensitive probes of vector magnetic fields on the nanometre scale. We present the result of Monte Carlo modeling for the precise signals one would expect to see with nanometre-scale probes such as NV-magnetometers or muon spin rotation.

  9. Localized and collectivized behaviour of d-electrons in complicated titanium, vanadium and niobium oxides

    International Nuclear Information System (INIS)

    Bazuev, G.V.; Shvejkin, G.P.

    1980-01-01

    On the basis of investigation of electric and magnetic properties of oxide compounds of transition metals made are the conclusions on the degree of localization and delocalization of d-electrons in them. Generalized are the investigation results of complicated titanium, vanadium, niobium oxide compounds in low degrees of oxidation with rare earth and alkaline earth elements belonging to the two structural types: perovskite and pyrochlore. Presented are the results of investigations of perovskite-like solid solutions and of variable-content phases containing cations of transition metals in two different oxidation degrees: oxide niobium bronzes of two-valent europium and titanium bronzes of rare-earth elements, as well as Lnsub(1-x)Msub(x)Vsub(1-x)sup(3+)Vsub(x)sup(4+)Osub(3), where M is an alkaline earth element

  10. Cesium incorporation in hollandite-rich multiphasic ceramic waste forms

    Energy Technology Data Exchange (ETDEWEB)

    Tumurugoti, P.; Clark, B.M. [Kazuo Inamori School of Engineering, The New York State College of Ceramics, Alfred University, Alfred, NY 14802 (United States); Edwards, D.J. [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Amoroso, Jake [Savannah River National Laboratory, Aiken, SC 29808 (United States); Sundaram, S.K. [Kazuo Inamori School of Engineering, The New York State College of Ceramics, Alfred University, Alfred, NY 14802 (United States)

    2017-02-15

    Hollandite-rich multiphase waste form compositions processed by melt-solidification and spark plasma sintering (SPS) were characterized, compared, and validated for nuclear waste incorporation. Phase identification by x-ray diffraction (XRD) and electron back-scattered diffraction (EBSD) confirmed hollandite as the major phase present in these samples along with perovskite, pyrochlore and zirconolite. Distribution of selected elements observed by wavelength dispersive spectroscopy (WDS) maps indicated that Cs formed a secondary phase during SPS processing, which was considered undesirable. On the other hand, Cs partitioned into the hollandite phase in melt-processed samples. Further analysis of hollandite structure in melt-processed composition by selected area electron diffraction (SAED) revealed ordered arrangement of tunnel ions (Ba/Cs) and vacancies, suggesting efficient Cs incorporation into the lattice.

  11. Relationship between tolerance factor and temperature coefficient of permittivity of temperature-stable high permittivity BaTiO3–Bi(MeO3 compounds

    Directory of Open Access Journals (Sweden)

    Natthaphon Raengthon

    2016-03-01

    Full Text Available The temperature coefficient of permittivity (TCε of BaTiO3–Bi(MeO3 solid solutions were investigated. It was determined that as the tolerance factor was decreased with the addition of Bi(MeO3, the TCε shifted from large negative values to TCε values approaching zero. It is proposed that the different bonding nature of the dopant cation affects the magnitude and temperature stability of the permittivity. This study suggests that the relationship between tolerance factor and TCε can be used as a guide to design new dielectric compounds exhibiting temperature-stable high permittivity characteristics, which is similar to past research on perovskite and pyrochlore-based microwave dielectrics.

  12. Radiophase development in hot-pressed alkoxide-derived titanate ceramics for nuclear waste stabilization

    International Nuclear Information System (INIS)

    Dickson, F.J.; Mitamura, H.; White, T.J.

    1989-01-01

    This paper reports phase development as a function of hot-pressing temperature studied in alkoxide-derived titanate-based ceramics doped with a 10 wt% loading of a sodium-rich (NAR) and a sodium-poor (NAP) simulated high-level waste. Pyrochlore was found to be the most abundant phase in both calcine powders. A pseudobrookite phase existed metastably at hot-pressing temperatures between 890 degrees and 920 degrees C. After hot-pressing at 1100 degrees C, the final phase assemblage for the NAP material consisted of zirconolite, hollandite-type, perovskite, alloy, and reduced rutile (Magneli phases). In addition, NAR samples contained hibonite, freudenbergite, and loveringite. Phase development was driven to completion over a very narrow temperature range (≤50 degrees C), beginning at 870 degrees and 850 degrees C for NAP and NAR, respectively, although full densification was not achieved below 1100 degrees C. Both waste forms exhibited comparable microstructure and aqueous durability

  13. Tantalum(V) impurity extraction by octanol from niobium(V) fluoride solutions

    International Nuclear Information System (INIS)

    Majorov, V.G.; Nikolaev, A.I.; Kopkov, V.K.

    2002-01-01

    The conditions of the niobium and tantalum extraction separation by octanol in the fluoride solutions, depending on the metals and free hydrofluoric acid concentration as well as on the organic and water phases voluminous relation, are studied for the purpose of developing the technology of niobium deep purification from the tantalum impurities. The technological scheme of the niobium solutions(V) extraction purification from the tantalum impurities(V), which provides for obtaining the niobium oxide(V), containing less than 0.005 mass % Ta 2 O 5 , is proposed on the basis of the established optimal separation conditions. The possibility of using the developed technology by the pyrochlore reprocessing is indicated [ru

  14. Transmutation of americium and curium incorporated in zirconia-based host materials

    International Nuclear Information System (INIS)

    Raison, P.E.

    2001-01-01

    Presented are studies involving the incorporation of americium and curium in zirconia-based materials. First explored was the pseudo ternary system AmO 2 -ZrO 2 -Y 2 O 3 . It was determined that selected Y-CSZ materials can incorporate significant quantities of americium oxide and remain cubic single-phase. The cell parameters of these fluorite-type products were established to be linear with the AmO 2 content. The Cm 2 O 3 -ZrO 2 system was also investigated. It was found that at 25 mol% of CmO 1.5 , the Cm(III) stabilized zirconia in its cubic form (a = 5.21 ±0.01 Angstrom). At higher and lower concentrations, diphasic materials were encountered. At 50 mol% of CmO 1.5 , a pyrochlore oxide - Cm 2 Zr 2 O 7 - is formed (a = 10.63 ±0.02 Angstrom). (author)

  15. Crystalline ceramics: Waste forms for the disposal of weapons plutonium

    International Nuclear Information System (INIS)

    Ewing, R.C.; Lutze, W.; Weber, W.J.

    1995-05-01

    At present, there are three seriously considered options for the disposition of excess weapons plutonium: (i) incorporation, partial burn-up and direct disposal of MOX-fuel; (ii) vitrification with defense waste and disposal as glass ''logs''; (iii) deep borehole disposal (National Academy of Sciences Report, 1994). The first two options provide a safeguard due to the high activity of fission products in the irradiated fuel and the defense waste. The latter option has only been examined in a preliminary manner, and the exact form of the plutonium has not been identified. In this paper, we review the potential for the immobilization of plutonium in highly durable crystalline ceramics apatite, pyrochlore, monazite and zircon. Based on available data, we propose zircon as the preferred crystalline ceramic for the permanent disposition of excess weapons plutonium

  16. Progress report - Physical and Environmental Sciences - Physics Division, 1996 January 1 to December 31

    International Nuclear Information System (INIS)

    Powell, B.M.

    1997-04-01

    This document is the last Progress Report for the Neutron and Condensed Matter Science Branch, at Chalk River Labs of Atomic Energy of Canada Limited. The materials science program continued to include measurements of stress as a major component, but the determination of phase diagrams for specific alloys was also a prominent activity. Studies were made of two types of unusual magnetic materials. The magnetic properties of several oxide pyrochlore were investigated and spin waves were measured in the magnetic semiconductor, chalcopyrite. The crystal structures of the deuterated anti fluorite were determined and the reorientation of the ammonium ion was refined in detail. Differential scanning calorimetry measurements were used to investigate whether spontaneous phase separation into chiral domains occurs for mixtures of DPPC of opposite chirality. A new Neutron Velocity Selector was commissioned

  17. Progress report - Physical and Environmental Sciences - Physics Division, 1996 January 1 to December 31

    Energy Technology Data Exchange (ETDEWEB)

    Powell, B.M. (ed.)

    1997-04-01

    This document is the last Progress Report for the Neutron and Condensed Matter Science Branch, at Chalk River Labs of Atomic Energy of Canada Limited. The materials science program continued to include measurements of stress as a major component, but the determination of phase diagrams for specific alloys was also a prominent activity. Studies were made of two types of unusual magnetic materials. The magnetic properties of several oxide pyrochlore were investigated and spin waves were measured in the magnetic semiconductor, chalcopyrite. The crystal structures of the deuterated anti fluorite were determined and the reorientation of the ammonium ion was refined in detail. Differential scanning calorimetry measurements were used to investigate whether spontaneous phase separation into chiral domains occurs for mixtures of DPPC of opposite chirality. A new Neutron Velocity Selector was commissioned.

  18. Prediction of compounds with electric and magnetic ordering

    Energy Technology Data Exchange (ETDEWEB)

    Nikiforov, L G [Rybinskij Aviatsionnyj Tekhnologicheskij Inst. (USSR)

    1979-03-01

    The possibility of polymorphic transformations from the structure of the pyrochlore type into that of the perovskite type for nine lead-containing compounds has been forecast. Some of them (PbTaO/sub 3/, Pb/sub 2/NiTaO/sub 6/, Pb/sub 2/MnTaO/sub 6/, Pb/sub 2/SmTaO/sub 6/) are expected to have, in addition to common for all lead-containing perovskites ferro-or antiferro-electric properties, specific magnetic properties. The periods of elementary cells of new perovskites are forecast. The possibility of considerable reduction of the number of errors when searching thermodynamical parameters of transformation has been shown.

  19. AgLnSb/sub 2/O/sub 7/ compounds with weberite structure

    Energy Technology Data Exchange (ETDEWEB)

    Lopatin, S S; Aver' yanova, L N; Belyaev, I N; Zvyagintsev, B I; Dyatlov, Eh V [Rostovskij-na-Donu Gosudarstvennyj Univ. (USSR)

    1982-11-01

    The interaction between AgSbO/sub 3/ and LnSbO/sub 4/ in the solid phase at 1100-1150 deg C has been investigated. AgLnSb/sub 2/O/sub 7/ compounds with weberite crystal structure are formed in Ln=La, Pr, Nd, Sm cases but in Ln=Eu, Cd, Dy, Er cases the formation of termary oxides of the indicated composition has not been observed. Inasmuch as compounds of the general formula A/sub 2/B/sub 2/O/sub 7/ with average cation radii Rsub(B) >0.60 A and 1.65 <= Rsub(A)/Rsub(B) <= 2.20 can crystallize in weberite, pyrochlore and laminated perovskite-like structurer, conditions of the existence of the above mentioned structures depending on A and B dimensions and electronegativity are discussed.

  20. CTAB-Assisted Hydrothermal Synthesis of Bi2Sn2O7 Photocatalyst and Its Highly Efficient Degradation of Organic Dye under Visible-Light Irradiation

    Directory of Open Access Journals (Sweden)

    Weicheng Xu

    2013-01-01

    Full Text Available Pyrochlore-type Bi2Sn2O7 (BSO nanoparticles have been prepared by a hydrothermal method assisted with a cationic surfactant cetyltrimethylammonium bromide (CTAB. These BSO products were characterized by powder X-ray diffraction (XRD, infrared spectroscopy (IR, scanning electron microscopy (SEM, transmission electron microscopy (TEM, Brunauer-Emmett-Teller (BET, and UV-visible diffuse reflectance spectroscopy (DRS. The results indicated that CTAB alters the surface parameters and the morphology and enhances the photoinduced charge separation rate of BSO. The photocatalytic degradation test using rhodamine B as a model pollutant showed that the photocatalytic activity of the BSO assisted with CTAB was two times that of the reference BSO. Close investigation revealed that the size, the band gap, the structure, and the existence of impurity level played an important role in the photocatalytic activities.

  1. In situ deposition of thallium-containing oxides

    International Nuclear Information System (INIS)

    Myers, K.E.

    1996-01-01

    The number and variety of thallium based materials that can be made by in situ methods have grown consistently since the first report of successful thallium cuprate deposition by Face and Nestlerode in 1992. Processes for the deposition of superconductors, normal metals, and insulators have been developed. Most work to date has been done on the Tl-1212 phases, TlBa 2 CaCu 2 O 7 and (Tl,Pb)Sr 2 CaCu 2 O 7 . Recently however, the in situ thallium technique has been extended to other materials. For example, epitaxial thin films of thallium tantalate, an insulator of the pyrochlore structure and a potential buffer layer for thallium cuprate films, have been grown. Multilayers, important in the fabrication of Josephson junctions, have been demonstrated with the thallium lead cuprates. This paper reviews progress in the area of in situ thallium deposition technology which will make more complex thallium cuprate multilayer structures and devices possible

  2. Linear independence of localized magnon states

    International Nuclear Information System (INIS)

    Schmidt, Heinz-Juergen; Richter, Johannes; Moessner, Roderich

    2006-01-01

    At the magnetic saturation field, certain frustrated lattices have a class of states known as 'localized multi-magnon states' as exact ground states. The number of these states scales exponentially with the number N of spins and hence they have a finite entropy also in the thermodynamic limit N → ∞ provided they are sufficiently linearly independent. In this paper, we present rigorous results concerning the linear dependence or independence of localized magnon states and investigate special examples. For large classes of spin lattices, including what we call the orthogonal type and the isolated type, as well as the kagome, the checkerboard and the star lattice, we have proven linear independence of all localized multi-magnon states. On the other hand, the pyrochlore lattice provides an example of a spin lattice having localized multi-magnon states with considerable linear dependence

  3. Cofiring behavior and interfacial structure of NiCuZn ferrite/PMN ferroelectrics composites for multilayer LC filters

    International Nuclear Information System (INIS)

    Miao Chunlin; Zhou Ji; Cui Xuemin; Wang Xiaohui; Yue Zhenxing; Li Longtu

    2006-01-01

    The cofiring behavior, interfacial structure and cofiring migration between NiCuZn ferrite and lead magnesium niobate (PMN)-based relaxor ferroelectric materials were investigated via thermomechanical analyzer (TMA), X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Mismatched sintering shrinkage between NiCuZn ferrite and PMN was modified by adding an appropriate amount of sintering aids, Bi 2 O 3 , into NiCuZn ferrite. Pyrochlore phase appeared in the mixture of NiCuZn ferrite and PMN, which is detrimental to the final electric properties of LC filters. EDS results indicated that the interdiffusion at the heterogeneous interfaces in the composites, such as Fe, Pb, Zn, existed which can strengthen combinations between ferrite layers and ferroelectrics layers

  4. Negative Longitudinal Magnetoresistance in the Density Wave Phase of Y_{2}Ir_{2}O_{7}.

    Science.gov (United States)

    Juyal, Abhishek; Agarwal, Amit; Mukhopadhyay, Soumik

    2018-03-02

    The ground state of nanowires of single-crystalline pyrochlore Y_{2}Ir_{2}O_{7} is a density wave. The application of a transverse magnetic field increases the threshold electric field for the collective depinning of the density wave state at a low temperature, leading to colossal magnetoresistance for voltages around the depinning threshold. This is in striking contrast to the case where even a vanishingly small longitudinal magnetic field sharply reduces the depinning threshold voltage, resulting in negative magnetoresistance. Ruling out several other possibilities, we argue that this phenomenon is likely to be a consequence of the chiral anomaly in the gapped out Weyl semimetal phase in Y_{2}Ir_{2}O_{7}.

  5. Negative Longitudinal Magnetoresistance in the Density Wave Phase of Y2Ir2O7

    Science.gov (United States)

    Juyal, Abhishek; Agarwal, Amit; Mukhopadhyay, Soumik

    2018-03-01

    The ground state of nanowires of single-crystalline pyrochlore Y2Ir2O7 is a density wave. The application of a transverse magnetic field increases the threshold electric field for the collective depinning of the density wave state at a low temperature, leading to colossal magnetoresistance for voltages around the depinning threshold. This is in striking contrast to the case where even a vanishingly small longitudinal magnetic field sharply reduces the depinning threshold voltage, resulting in negative magnetoresistance. Ruling out several other possibilities, we argue that this phenomenon is likely to be a consequence of the chiral anomaly in the gapped out Weyl semimetal phase in Y2Ir2O7 .

  6. Control of the Effective Free-Energy Landscape in a Frustrated Magnet by a Field Pulse

    Science.gov (United States)

    Wan, Yuan; Moessner, Roderich

    2017-10-01

    Thermal fluctuations can lift the degeneracy of a ground state manifold, producing a free-energy landscape without accidentally degenerate minima. In a process known as order by disorder, a subset of states incorporating symmetry breaking may be selected. Here, we show that such a free-energy landscape can be controlled in a nonequilibrium setting as the slow motion within the ground state manifold is governed by the fast modes out of it. For the paradigmatic case of the classical pyrochlore X Y antiferromagnet, we show that a uniform magnetic field pulse can excite these fast modes to generate a tunable effective free-energy landscape with minima at thermodynamically unstable portions of the ground state manifold.

  7. Ising versus XY anisotropy in frustrated R(2)Ti(2)O(7) compounds as "Seen" by Polarized Neutrons.

    Science.gov (United States)

    Cao, H; Gukasov, A; Mirebeau, I; Bonville, P; Decorse, C; Dhalenne, G

    2009-07-31

    We studied the field induced magnetic order in R(2)Ti(2)O(7) pyrochlore compounds with either uniaxial (R=Ho, Tb) or planar (R=Er, Yb) anisotropy, by polarized neutron diffraction. The determination of the local susceptibility tensor {chi(parallel to),chi(perpendicular)} provides a universal description of the field induced structures in the paramagnetic phase (2-270 K), whatever the field value (1-7 T) and direction. Comparison of the thermal variations of chi(parallel to) and chi(perpendicular) with calculations using the rare earth crystal field shows that exchange and dipolar interactions must be taken into account. We determine the molecular field tensor in each case and show that it can be strongly anisotropic.

  8. Dirac strings and magnetic monopoles in the spin ice Dy2Ti2O7.

    Science.gov (United States)

    Morris, D J P; Tennant, D A; Grigera, S A; Klemke, B; Castelnovo, C; Moessner, R; Czternasty, C; Meissner, M; Rule, K C; Hoffmann, J-U; Kiefer, K; Gerischer, S; Slobinsky, D; Perry, R S

    2009-10-16

    Sources of magnetic fields-magnetic monopoles-have so far proven elusive as elementary particles. Condensed-matter physicists have recently proposed several scenarios of emergent quasiparticles resembling monopoles. A particularly simple proposition pertains to spin ice on the highly frustrated pyrochlore lattice. The spin-ice state is argued to be well described by networks of aligned dipoles resembling solenoidal tubes-classical, and observable, versions of a Dirac string. Where these tubes end, the resulting defects look like magnetic monopoles. We demonstrated, by diffuse neutron scattering, the presence of such strings in the spin ice dysprosium titanate (Dy2Ti2O7). This is achieved by applying a symmetry-breaking magnetic field with which we can manipulate the density and orientation of the strings. In turn, heat capacity is described by a gas of magnetic monopoles interacting via a magnetic Coulomb interaction.

  9. Irradiated three-dimensional Luttinger semimetal: A factory for engineering Weyl semimetals

    Science.gov (United States)

    Ghorashi, Sayed Ali Akbar; Hosur, Pavan; Ting, Chin-Sen

    2018-05-01

    We study the interaction between elliptically polarized light and a three-dimensional Luttinger semimetal with quadratic band touching using Floquet theory. In the absence of light, the touching bands can have the same or the opposite signs of the curvature; in each case, we show that simply tuning the light parameters allows us to create a zoo of Weyl semimetallic phases. In particular, we find that double- and single-Weyl points can coexist at different energies, and they can be tuned to be type I or type II. We also find an unusual phase transition, in which a pair of Weyl nodes form at finite momentum and disappear off to infinity. Considering the broad tunability of light and abundance of materials described by the Luttinger Hamiltonian, such as certain pyrochlore iridates, half-Heuslers, and zinc-blende semiconductors, we believe this work can lay the foundation for creating Weyl semimetals in the laboratory and dynamically tuning between them.

  10. Self-propagating synthesis and aqueous durability of Nd-bearing zirconolite-rich composites using Ca(NO{sub 3}){sub 2} as the oxidant

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kuibao, E-mail: xiaobao320@163.com [State Key Laboratory Cultivation Base for Nonmetal Composite and Functional Materials, Southwest University of Science and Technology, Mianyang, Sichuan 621010 (China); National Defense Key Discipline Lab of Nuclear Waste and Environmental Safety, Southwest University of Science and Technology, Mianyang 621010 (China); He, Shihong [State Nuclear Power Research Institute, Beijing 100029 (China); Yin, Dan; Peng, Le; Wu, Jingjun [State Key Laboratory Cultivation Base for Nonmetal Composite and Functional Materials, Southwest University of Science and Technology, Mianyang, Sichuan 621010 (China)

    2016-09-15

    Synroc is recognized as the second-generation waste form for safety disposal of high-level radioactive waste (HLW). In this study, zirconolite-rich Synroc waste form was readily synthesized by self-propagating high-temperature plus quick pressing (SHS/QP) using Ca(NO{sub 3}){sub 2} as the oxidant and Ti as the reductant. As the surrogate of trivalent actinides, Nd{sub 2}O{sub 3} was introduced to equally substitute the Ca and Zr sites of zirconolite with nominal stoichiometry of Ca{sub 1−x}Zr{sub 1−x}Nd{sub 2x}Ti{sub 2}O{sub 7}. The results demonstrate that zirconolite, perovskite and pyrochlore (Ca{sub 2}Ti{sub 2}O{sub 6}) coexist as the ceramic components after SHS reaction. The introduction of Nd{sub 2}O{sub 3} promotes the formation of perovskite. Nd is mostly incorporated into the Ca sites of these phases. The normalized elemental leaching rates of Ca and Nd are fairly constant in low values of 1.80 × 10{sup −2} g m{sup −2} d{sup −1} and 6.12 × 10{sup −4} g m{sup −2} d{sup −1} after 42 days. - Highlights: • Zirconolite-rich composite was synthesized by SHS using Ca(NO{sub 3}){sub 2} as the oxidant. • Nd{sub 2}O{sub 3} was successfully immobilized into the crystal structure of this waste form. • Nd was mostly incorporated into the Ca sites of zirconolite, perovskite and pyrochlore. • The normalized leaching rates of Ca and Nd are in relatively low values.

  11. Molecular Environmental Science Using Synchrotron Radiation: Chemistry and Physics of Waste Form Materials. Final Report

    International Nuclear Information System (INIS)

    Lindle, Dennis W.

    2011-01-01

    Production of defense-related nuclear materials has generated large volumes of complex chemical wastes containing a mixture of radionuclides. The disposition of these wastes requires conversion of the liquid and solid-phase components into durable, solid forms suitable for long-term immobilization. Specially formulated glass compositions and ceramics such as pyrochlores and apatites are the main candidates for these wastes. An important consideration linked to the durability of waste-form materials is the local structure around the waste components. Equally important is the local structure of constituents of the glass and ceramic host matrix. Knowledge of the structure in the waste-form host matrices is essential, prior to and subsequent to waste incorporation, to evaluate and develop improved waste-form compositions based on scientific considerations. This project used the soft-x-ray synchrotron-radiation-based technique of near-edge x-ray-absorption fine structure (NEXAFS) as a unique method for investigating oxidation states and structures of low-Z elemental constituents forming the backbones of glass and ceramic host matrices for waste-form materials. In addition, light metal ions in ceramic hosts, such as titanium, are also ideal for investigation by NEXAFS in the soft-x-ray region. Thus, one of the main objectives was to understand outstanding issues in waste-form science via NEXAFS investigations and to translate this understanding into better waste-form materials, followed by eventual capability to investigate 'real' waste-form materials by the same methodology. We conducted several detailed structural investigations of both pyrochlore ceramic and borosilicate-glass materials during the project and developed improved capabilities at Beamline 6.3.1 of the Advanced Light Source (ALS) to perform the studies.

  12. The role of processing route on the microstructure of 14YWT nanostructured ferritic alloy

    Energy Technology Data Exchange (ETDEWEB)

    Mazumder, B., E-mail: mazumderb@ornl.gov [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Parish, C.M.; Bei, H. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Miller, M.K. [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

    2015-10-15

    Nanostructured ferritic alloys have outstanding high temperature creep properties and enhanced tolerance to radiation damage over conventional ferritic alloys. To achieve these properties, NFAs are fabricated by mechanical alloying of metallic and yttria powders. Atom probe tomography has demonstrated that milling times of at least 40 h are required to produce a uniform distribution of solutes in the flakes. After milling and hot extrusion, the microstructure consists of α-Fe, high number densities of Ti–Y–O-vacancy-enriched nanoclusters, and coarse Y{sub 2}Ti{sub 2}O{sub 7} and Ti(O,C,N) precipitates on the grain boundaries. In contrast, the as-cast condition consists of α-Fe with 50–100 μm irregularly-shaped Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore precipitates with smaller embedded precipitates with the Y{sub 3}Al{sub 5}O{sub 12} (yttrium–aluminum garnet) crystal structure indicating that this traditional processing route is not a viable approach to achieve the desired microstructure. The nano-hardnesses were also substantially different, i.e., 4 and 8 GPa for the as-cast and as-extruded conditions, respectively. These variances can be explained by the microstructural differences and the effects of the high vacancy content introduced by mechanical alloying, and the strong binding energy of vacancies with O, Ti, and Y atoms that retard diffusion. - Highlights: • Mechanical alloying produces nanostructured ferritic alloy with excellent properties. • Short milling time wastes solutes in low number densities of coarse precipitates. • Milling for 40 h yields UFG alloy with optimum distribution of ultrafine precipitates. • Longer milling times increase cost and increases impurities from attritor mill. • Casting produces undesirable course grain microstructure of α-Fe, YAG and pyrochlore.

  13. Nd{sub 2±x}Zr{sub 2∓x}O{sub 7±x/2} (−0.2≤x≤0.4) complex oxides: Effect of anion disorder on ionic conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Anithakumari, P., E-mail: anithakumari21-02@yahoo.co.in; Grover, V.; Tyagi, A. K. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai, India-400085 (India)

    2016-05-23

    In the present work, a series of Nd{sub 2±x}Zr{sub 2∓x}O{sub 7±x/2} (−0.2≤x≤0.4) was prepared by self assisted gel-combution method followed by high temperature sintering at 1673 K. Thorough structural characterizations were done by X-ray diffraction and Raman spectroscopic techniques. The nominal compositions Nd{sub 1.6}Zr{sub 2.4}O{sub 7.2} and Nd{sub 1.8}Zr{sub 2.2}O{sub 7.1} were found to possess single-phasic pyrochlore structure whereas Nd{sub 2.0}Zr{sub 2.0}O{sub 7} and Nd{sub 2.2}Zr{sub 1.8}O{sub 6.9} consisted of a pyrochlore phase and a small amount of hexagonal Nd{sub 2}O{sub 3} as an impurity phase. Electrical behavior of the samples was examined by AC impedance analysis. Even though the activation energies of all the samples are not very different, a high pre-exponential factor for the Nd{sub 1.6}Zr{sub 2.4}O{sub 7.2} composition resulted in high ionic conductivity (3.37 × 10{sup −3} Scm{sup −1} at 773 K). This high ionic conductivity value makes it a superior candidate as an electrolyte material for SOFC applications.

  14. Integration of epitaxial Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3} films on GaN/AlGaN/GaN/Si(111) substrates using rutile TiO{sub 2} buffer layers

    Energy Technology Data Exchange (ETDEWEB)

    Elibol, K. [MESA + Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE Enschede (Netherlands); Nguyen, M.D. [MESA + Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE Enschede (Netherlands); SolMateS B.V., Drienerlolaan 5, Building 6, 7522NB Enschede (Netherlands); International Training Institute for Materials Science, Hanoi University of Science and Technology, No.1 Dai Co Viet road, Hanoi 10000 (Viet Nam); Hueting, R.J.E. [MESA + Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE Enschede (Netherlands); Gravesteijn, D.J. [MESA + Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE Enschede (Netherlands); NXP Semiconductors Research, High Tech Campus 46, 5656AE Eindhoven (Netherlands); Koster, G., E-mail: g.koster@utwente.nl [MESA + Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE Enschede (Netherlands); Rijnders, G. [MESA + Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE Enschede (Netherlands)

    2015-09-30

    The integration of ferroelectric layers on gallium nitride (GaN) offers a great potential for various applications. Lead zirconate titanate (PZT), in particular Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3}, is an interesting candidate. For that a suitable buffer layer should be grown on GaN in order to prevent the reaction between PZT and GaN, and to obtain PZT with a preferred orientation and phase. Here, we study pulsed laser deposited (100) rutile titanium oxide (R-TiO{sub 2}) as a potential buffer layer candidate for ferroelectric PZT. For this purpose, the growth, morphology and the surface chemical composition of R-TiO{sub 2} films were analyzed by reflection high-energy electron diffraction, atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. We find optimally (100) oriented R-TiO{sub 2} growth on GaN (0002) using a 675 °C growth temperature and 2 Pa O{sub 2} deposition pressure as process conditions. More importantly, the R-TiO{sub 2} buffer layer grown on GaN/Si substrates prevents the unwanted formation of the PZT pyrochlore phase. Finally, the remnant polarization and coercive voltage of the PZT film on TiO{sub 2}/GaN/Si with an interdigitated-electrode structure were found to be 25.6 μC/cm{sup 2} and 8.1 V, respectively. - Highlights: • Epitaxial rutile TiO{sub 2} films were grown on GaN layer buffered Si substrate using pulsed laser deposition. • The rutile-TiO{sub 2} layer suppresses the formation of the pyrochlore phase in the epitaxial PZT film grown on GaN/Si. • An epitaxial PZT film on GaN/Si substrate with rutile TiO{sub 2} buffer layer exhibits good ferroelectric properties.

  15. A 2 TiO 5 (A = Dy, Gd, Er, Yb) at High Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sulgiye [Department of Geological Science, Stanford University, Stanford, California 94305, United States; Rittman, Dylan R. [Department of Geological Science, Stanford University, Stanford, California 94305, United States; Tracy, Cameron L. [Department of Geological Science, Stanford University, Stanford, California 94305, United States; Chapman, Karena W. [X-ray Science Division, Advanced Photon; Zhang, Fuxiang [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States; Park, Changyong [HPCAT, Carnegie Institution of Washington, Argonne, Illinois 60439, United States; Tkachev, Sergey N. [Center for Advanced Radiation Sources, University of Chicago, Chicago, Illinois 60637, United States; O’Quinn, Eric [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States; Shamblin, Jacob [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States; Lang, Maik [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States; Mao, Wendy L. [Department of Geological Science, Stanford University, Stanford, California 94305, United States; Stanford; amp, Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States; Ewing, Rodney C. [Department of Geological Science, Stanford University, Stanford, California 94305, United States

    2018-02-07

    The structural evolution of lanthanide A2TiO5 (A = Dy, Gd, Yb, and Er) at high pressure is investigated using synchrotron X-ray diffraction. The effects of A-site cation size and of the initial structure are systematically examined by varying the composition of the isostructural lanthanide titanates, and the structure of dysprosium titanate polymorphs (orthorhombic, hexagonal and cubic), respectively. All samples undergo irreversible high pressure phase transformations, but with different onset pressures depending on the initial structure. While individual phase exhibits different phase transformation histories, all samples commonly experience a sluggish transformation to a defect cotunnite-like (Pnma) phase for a certain pressure range. Orthorhombic Dy2TiO5 and Gd2TiO5 form P21am at pressures below 9 GPa and Pnma above 13 GPa. Pyrochlore-type Dy2TiO5 and Er2TiO5 as well as defect-fluorite-type Yb2TiO5 form Pnma at ~ 21 GPa, followed by Im-3m. Hexagonal Dy2TiO5 forms Pnma directly, although a small amount of remnants of hexagonal Dy2TiO5 is observed even at the highest pressure (~ 55 GPa) reached, indicating a kinetic limitations in the hexagonal Dy2TiO5 phase transformations at high pressure. Decompression of these materials leads to different metastable phases. Most interestingly, a high pressure cubic X-type phase (Im-3m) is confirmed using highresolution transmission electron microscopy on recovered pyrochlore-type Er2TiO5. The kinetic constraints on this metastable phase yield a mixture of both the X-type phase and amorphous domains upon pressure release. This is the first observation of an X-type phase for an A2BO5 composition at high pressure.

  16. Steering Charge Kinetics of Tin Niobate Photocatalysts: Key Roles of Phase Structure and Electronic Structure.

    Science.gov (United States)

    Huang, Shushu; Wang, Chunyan; Sun, Hao; Wang, Xiaojing; Su, Yiguo

    2018-05-23

    Tin niobate photocatalysts with the phase structures of froodite (SnNb 2 O 6 ) and pyrochlore (Sn 2 Nb 2 O 7 ) were obtained by a facile solvothermal method in order to explore the impact of phase structure and electronic structure on the charge kinetics and photocatalytic performance. By employing tin niobate as a model compound, the effects of phase structure over electronic structure, photocatalytic activity toward methyl orange solution and hydrogen evolution were systematically investigated. It is found that the variation of phase structure from SnNb 2 O 6 to Sn 2 Nb 2 O 7 accompanied with modulation of particle size and band edge potentials that has great consequences on photocatalytic performance. In combination with the electrochemical impedance spectroscopy (EIS), transient photocurrent responses, transient absorption spectroscopy (TAS), and the analysis of the charge-carrier dynamics suggested that variation of electronic structure has great impacts on the charge separation and transfer rate of tin niobate photocatalysts and the subsequent photocatalytic performance. Moreover, the results of the X-ray photoelectron spectroscopy (XPS) indicated that the existent of Sn 4+ species in Sn 2 Nb 2 O 7 could result in a decrease in photocatalytic activity. Photocatalytic test demonstrated that the SnNb 2 O 6 (froodite) catalyst possesses a higher photocatalytic activity toward MO degradation and H 2 evolution compared with the sample of Sn 2 Nb 2 O 7 (pyrochlore). On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated holes, O 2 -• , and OH • active species dominate the photodegradation of methyl orange.

  17. Molecular Environmental Science Using Synchrotron Radiation: Chemistry and Physics of Waste Form Materials

    Energy Technology Data Exchange (ETDEWEB)

    Lindle, Dennis W.

    2011-04-21

    Production of defense-related nuclear materials has generated large volumes of complex chemical wastes containing a mixture of radionuclides. The disposition of these wastes requires conversion of the liquid and solid-phase components into durable, solid forms suitable for long-term immobilization. Specially formulated glass compositions and ceramics such as pyrochlores and apatites are the main candidates for these wastes. An important consideration linked to the durability of waste-form materials is the local structure around the waste components. Equally important is the local structure of constituents of the glass and ceramic host matrix. Knowledge of the structure in the waste-form host matrices is essential, prior to and subsequent to waste incorporation, to evaluate and develop improved waste-form compositions based on scientific considerations. This project used the soft-x-ray synchrotron-radiation-based technique of near-edge x-ray-absorption fine structure (NEXAFS) as a unique method for investigating oxidation states and structures of low-Z elemental constituents forming the backbones of glass and ceramic host matrices for waste-form materials. In addition, light metal ions in ceramic hosts, such as titanium, are also ideal for investigation by NEXAFS in the soft-x-ray region. Thus, one of the main objectives was to understand outstanding issues in waste-form science via NEXAFS investigations and to translate this understanding into better waste-form materials, followed by eventual capability to investigate “real” waste-form materials by the same methodology. We conducted several detailed structural investigations of both pyrochlore ceramic and borosilicate-glass materials during the project and developed improved capabilities at Beamline 6.3.1 of the Advanced Light Source (ALS) to perform the studies.

  18. In-situ high temperature irradiation setup for temperature dependent structural studies of materials under swift heavy ion irradiation

    International Nuclear Information System (INIS)

    Kulriya, P.K.; Kumari, Renu; Kumar, Rajesh; Grover, V.; Shukla, R.; Tyagi, A.K.; Avasthi, D.K.

    2015-01-01

    An in-situ high temperature (1000 K) setup is designed and installed in the materials science beam line of superconducting linear accelerator at the Inter-University Accelerator Centre (IUAC) for temperature dependent ion irradiation studies on the materials exposed with swift heavy ion (SHI) irradiation. The Gd 2 Ti 2 O 7 pyrochlore is irradiated using 120 MeV Au ion at 1000 K using the high temperature irradiation facility and characterized by ex-situ X-ray diffraction (XRD). Another set of Gd 2 Ti 2 O 7 samples are irradiated with the same ion beam parameter at 300 K and simultaneously characterized using in-situ XRD available in same beam line. The XRD studies along with the Raman spectroscopic investigations reveal that the structural modification induced by the ion irradiation is strongly dependent on the temperature of the sample. The Gd 2 Ti 2 O 7 is readily amorphized at an ion fluence 6 × 10 12 ions/cm 2 on irradiation at 300 K, whereas it is transformed to a radiation-resistant anion-deficient fluorite structure on high temperature irradiation, that amorphized at ion fluence higher than 1 × 10 13 ions/cm 2 . The temperature dependent ion irradiation studies showed that the ion fluence required to cause amorphization at 1000 K irradiation is significantly higher than that required at room temperature irradiation. In addition to testing the efficiency of the in-situ high temperature irradiation facility, the present study establishes that the radiation stability of the pyrochlore is enhanced at higher temperatures

  19. The petrology and petrogenesis of the Swaldale region, Motzfeldt Center, South Greenland

    Science.gov (United States)

    Reekie, Callum; Finch, Adrian

    2016-04-01

    Motzfeldt is one of several high-level alkaline plutonic centers that collectively define the mid-Proterozoic Gardar Province of South Greenland. Despite pyrochlore-hosted Ta-enrichment (± Nb-Zr-REE), the petrology, geochemistry and petrogenesis across the center remain to be fully constrained. We present petrological and geochemical data for the Swaldale region, an arcuate band of nepheline syenite and associated intrusives on Motzfeldt's NW margin. Work for this present study was undertaken in collaboration with the license holder, Regency Mines plc. Swaldale comprises two geochemically distinct magmatic members. The largest, the Motzfeldt Sø Formation (MSF; EuN/Eu*N = 0.35), is a suite of diverse syenite variants that show significant petrological and geochemical heterogeneity. These rocks have a relatively restricted SiO2 range (57.4-62.9 wt.%) with concurrent variation in (Na+K)/Al (0.75-0.95), Mg/(Mg+Fe) (2.18-19.82) and ΣREE (595.0-3095.9 ppm), emphasizing their evolved but not peralkaline nature. Fractionation is mirrored by pyroxene geochemistry with evolution from aegirine-augite, aegirine-hedenbergite, to aegirine. Accessory pyrochlore, titanite, and zircon are rare; however, anomalous facies of zircon-rich (~2 wt.%) syenite are observed. Intercumulus fluorite is a common accessory within MSF rocks. Hydrothermal alteration, marked by hematized alkali-feldspar, is pervasive and ubiquitous. Further peraluminous syenite of the Geologfjeld Formation ((Na+K)/Al = 0.74; EuN/Eu*N = 1.60) marks the truncated remnant of an early syenite stock to the north of the MSF. These rocks contain salite, which, in addition to a lower ΣREE and higher Mg/(Mg+Fe) (18.01), demonstrates the less-fractionated nature of this stock in comparison with the MSF. Sheeted intrusions of peralkaline syenite ((Na+K)/Al = 1.1; Ta = 32.4 ppm) truncate the MSF across central Swaldale. On a mineralogical basis, it is hypothesized that such intrusions reflect outward sheeting of the

  20. Properties of zirconium ceramics and film stabilized by yttrium

    International Nuclear Information System (INIS)

    Korobova, N.

    2004-01-01

    various technological regimes and conditions were determined. The model of the heat treatment process for ceramics and thin oxid films has been offered. Qualitative description of the experimental results for the sol-gel transition of thin oxide film has been found. It was known that a pyrochlore phase, Y 2 Zr 2 O 7 , may exist in the Y 2 O 3 -ZrO 2 system. However, since Y 3+ and Zr 4+ have similar scattering factors, the detection of the pyrochlore phase by X-ray techniques would be most difficult. In the present paper, no pyrochlore lines were detected for any of the specimens. The alkoxide-based sol-gel process is one of the most promising methods for synthesizing Y 2 O 3 -ZrO 2 ceramic powders and, especially, films at relatively low-temperatures. Sol-gel process has many advantages, such as easy composition control and fabrication of large area thin films, film homogeneity, low cost, and a simple fabrication cycle. Therefore, it could be practical to make use of sol-gel technique to prepare thin films of desired properties. The choice of precursors can affect the chemical-reaction kinetics, microstructures and properties of the product, so in this report author compared the crystallization behavior of oxide functional films derived from the same precursors, stressing the influence of experiment conditions and where it was possible to obtain the uniform films

  1. Radiation Damage Effects in Candidate Ceramics for Plutonium Immobilization: Final Report

    International Nuclear Information System (INIS)

    Strachan, Denis M.; Scheele, Randall D.; Icenhower, Jonathan P.; Buck, Edgar C.; Kozelisky, Anne E.; Sell, Rachel L.; Elovich, Robert J.; Buchmiller, William C.

    2004-01-01

    In this document, we summarize our study of the effects of radiation induced damage to the titanate ceramics that were to be the immobilization form for surplus weapons-grade Pu. In this study, we made five ceramic materials: pure-phase pyrochlore, pure-phase zirconolite, pyrochlore-rich baseline, zirconolite-rich baseline, and impurity baseline. Two-hundred specimens were made of which 130 contained approximately 10 mass% 238Pu and 70 contained 10 mass% 239Pu. The specimens containing 239Pu served as materials against which the behavior of the 238Pu-bearing specimens could be compared. In our studies, we measured the true density (density exclusive of surface connected porosity), bulk density, crystalline-phase composition with X-ray diffraction (XRD), and dissolution rates as radiation induced damage accumulated in the 238Pu-bearing specimens. We routinely took photographs of the specimens during each characterization period. From our studies, we determined that these materials swell less than 10% and generally less than 5%. As the material swells, some open porosity can be converted to closed porosity, often causing the true density to decrease more rapidly than the bulk density. In general, 3?1018 a/g of damage accumulation were required for the materials to become amorphous as determined with the XRD method. The order in which the phases became amorphous was brannerite, pyrochlore, and zirconolite with brannerite being the most susceptible to radiation induced damage. However, we also show that Pu is not evenly distributed amongst the phases when multiple phases are present. We were unsuccessful in making a pure brannerite to study. Therefore, the brannerite was always present with other phases. For a material containing about 10 mass% 239Pu, 3?1018 a/g represent about 500 years in the geologic repository. At no time in our studies was there evidence for microcracking in these materials, even upon close examination in a scanning-electron microscope . Upon

  2. Evaluation of the Long-Term Performance of Titanate Ceramics for Immobilization of Excess Weapons Plutonium: Results from Pressurized Unsaturated Flow and Single Pass Flow-Through Testing

    International Nuclear Information System (INIS)

    BP McGrail; HT Schaef; JP Icenhower; PF Martin; RD Orr; VL Legore

    1999-01-01

    This report summarizes our findings from pressurized unsaturated flow (PUF) and single-pass flow-through (SPFT) experiments to date. Results from the PUF test of a Pu-bearing ceramic with enclosing surrogate high-level waste glass show that the glass reacts rapidly to alteration products. Glass reaction causes variations in the solution pH in contact with the ceramic materials. We also document variable concentrations of Pu in solution, primarily in colloidal form, which appear to be related to secular variations in solution composition. The apparent dissolution rate of the ceramic waste form, based on Ba concentrations in the effluent, is estimated at le 10 -5 g/(m 2 · d). Pu-bearing colloids were recovered in the size range of 0.2 to 2 microm, but it is not clear that such entities would be transported in a system that is not advective-flow dominated. Results from SPFT experiments give information on the corrosion resistance of two surrogate Pu-ceramics (Ce-pyrochlore and Ce-zirconolite) at 90 C over a pH range of 2 to 12. The two ceramics were doped with minor quantities (approximately0.1 mass%) of MoO 3 , so that concentrations of Mo in the effluent solution could be used to monitor the reaction behavior of the materials. The data obtained thus far from experiments with durations up to 150 d do not conclusively prove that the solid-aqueous solution systems have reached steady-state conditions. Therefore, the dissolution mechanism cannot be determined. Apparent dissolution rates of the two ceramic materials based on Ce, Gd, and Mo concentrations in the effluent solutions from the SPFT are nearly identical and vary between 1.1 to 8.5 x 10 -4 g/(m 2 · d). In addition, the data reveal a slightly amphoteric dissolution behavior, with a minimum apparent rate at pH = 7 to 8, over the pH range examined. Results from two related ceramic samples suggest that radiation damage can have a measurable effect on the dissolution of titanium-based ceramics. The rare earth

  3. NERI FINAL TECHNICAL REPORT, DE-FC07-O5ID14647. OPTIMIZATION OF OXIDE COMPOUNDS FOR ADVANCED INERT MATRIX MATERIALS

    International Nuclear Information System (INIS)

    Nino, Juan C.

    2009-01-01

    In order to reduce the current excesses of plutonium (both weapon grade and reactor grade) and other transuranium elements, a concept of inert matrix fuel (IMF) has been proposed for an uranium free transmutation of fissile actinides which excludes continuous uranium-plutonium conversion in thermal reactors and advanced systems. Magnesium oxide (MgO) is a promising candidate for inert matrix (IM) materials due to its high melting point (2827 C), high thermal conductivity (13 W/K · m at 1000 C), good neutronic properties, and irradiation stability However, MgO reacts with water and hydrates easily, which prevents it from being used in light water reactors (LWRs) as an IM. To improve the hydration resistance of MgO-based inert matrix materials, Medvedev and coworkers have recently investigated the introduction of a secondary phase that acts as a hydration barrier. An MgO-ZrO 2 composite was specifically studied and the results showed that the composite exhibited improved hydration resistance than pure MgO. However, ZrO 2 is insoluble in most acids except HF, which is undesirable for fuel reprocessing. Moreover, the thermal conductivity of ZrO 2 is low and typically less than 3 W · m -1 · K -1 at 1000 C. In search for an alternative composite strategy, Nd 2 Zr 2 O 7 , an oxide compound with pyrochlore structure, has been proposed recently as a corrosion resistant phase, and MgO-Nd 2 Zr 2 O 7 composites have been investigated as potential IM materials. An adequate thermal conductivity of 6 W · m - 1 · K -1 at 1000 C for the MgO-Nd 2 Zr 2 O 7 composite with 90 vol% MgO was recently calculated and reported. Other simulations proposed that the MgO-pyrochlore composites could exhibit higher radiation stability than previously reported. Final optimization of the composite microstructure was performed on the 70 vol% MgO-Nd 2 Zr 2 O 7 composite that burnup calculations had shown to have the closest profile to that of MOX fuel. Theoretical calculations also indicated that

  4. Magmatic evolution and controls on rare metal-enrichment of the Strange Lake A-type peralkaline granitic pluton, Québec-Labrador

    Science.gov (United States)

    Siegel, Karin; Vasyukova, Olga V.; Williams-Jones, Anthony E.

    2018-05-01

    Although it is well known that A-type granites are enriched in the rare earth elements (REE) and other high field strength elements (HFSE), the magmatic processes that concentrate these elements are still poorly understood. The 1.24 Ga Strange Lake pluton in northern Québec-Labrador provides an extraordinary example of hyper-enrichment in the REE, Zr, and Nb in a peralkaline A-type granite. The pluton consists of two hypersolvus granite units (southern and northern) and a transsolvus granite, all of which contain perthitic alkali feldspar as the earliest major mineral; the transsolvus granite also contains separate albite and microcline crystals. Arfvedsonite, a sodic amphibole, occurs exclusively as phenocrysts in the transsolvus granite, whereas in the hypersolvus granite it is present as a late, interstitial phase. The primary HFSE minerals are zircon, monazite-(Ce), gagarinite-(Ce) and the pyrochlore group minerals. Magma evolution was monitored by the alumina content in the bulk rock, which decreases from the southern to the northern hypersolvus granite and is lowest in the transsolvus granite. Alkalinity indices and bulk Si, Fe, Rb, REE, Zr, Nb concentrations show the opposite trend. Alkali feldspar compositions mirror the trend shown by the bulk rock, i.e., decreasing Al contents are accompanied by increasing Si, Fe3+, REE, Zr and Nb contents. The major driving forces for the evolution of the hypersolvus magma prior to emplacement were the early separation of a fluoride melt from the silicate melt and the crystallization of alkali feldspar and HFSE-rich phases (zircon, monazite-(Ce), pyrochlore group). An alkali feldspar-rich crystal-mush containing LREE-fluoride melt droplets was emplaced as the least evolved southern hypersolvus granite. Massive fractionation of alkali feldspar led to a sharp increase in ƒH2O and F- activity in the magma chamber that triggered the crystallization of arfvedsonite and was followed by emplacement of the northern hypersolvus

  5. Geology, market and supply chain of niobium and tantalum—a review

    Science.gov (United States)

    Mackay, Duncan A. R.; Simandl, George J.

    2014-12-01

    Tantalum (Ta) and niobium (Nb) are essential metals in modern society. Their use in corrosion prevention, micro-electronics, specialty alloys and high-strength low-alloy (HSLA) steel earns them a strategic designation in most industrialised countries. The Ta market is unstable due in part to historic influx of `conflict' columbite-tantalite concentrate, or "Coltan," that caused Ta mines in Australia and Canada to be placed on care and maintenance. More recently, the growing appetite of modern society for consumer goods made of `conflict-free' minerals or metals has put pressure on suppliers. Pegmatites, rare-element-enriched granites, related placer deposits and weathered crusts overlying carbonatite and peralkaline complexes account for the majority of Ta production. Several carbonatite-related deposits (e.g. Upper Fir and Crevier, Canada) are being considered for potential co-production of Ta and Nb. Pyrochlore (Nb-Ta), columbite-tantalite (Nb-Ta), wodginite (Ta, Nb and Sn) and microlite (Ta and Nb) are the main ore minerals. Approximately 40 % of Ta used in 2012 came from Ta mines, 30 % from recycling, 20 % from tin slag refining and 10 % from secondary mine concentrates. Due to rapid industrialisation and increased use of Nb in steel making in countries such as China and India, demand for Nb is rising. Weathered crusts overlying carbonatite complexes in Brazil and one hard rock carbonatite deposit in Canada account for about 92 and 7 % of Nb world mine production, respectively. Since the bulk of the production is geographically and politically restricted to a single country, security of supply is considered at risk. Other prospective resources of Nb, beside carbonatites and associated weathered crusts, are peralkaline complexes (e.g. Nechalacho; where Nb is considered as a potential co-product of REE and zirconium). Economically, significant deposits of Ta and Nb contain pyrochlore, columbite-tantalite, fersmite, loparite and strüverite. Assuming continued

  6. PIXE analysis applied to characterized water samples

    International Nuclear Information System (INIS)

    Santos, Maristela S.; Carneiro, Luana Gomes; Medeiros, Geiza; Sampaio, Camilla; Martorell, Ana Beatriz Targino; Gouvea, Stella; Cunha, Kenya Moore Dias da

    2011-01-01

    Araxa, in Brazil, is a naturally high background area located in the State of Minas Gerais with a population of about 93 672 people. Araxa is historical city famous for its mineral water sources and mud from Termas de Araxa spa, which have been used for therapeutic, and recreation purposes. Other important aspect of economy of the city are mining and metallurgic industries. In the Araxa area is located the largest deposit of pyrochlore, a niobium mineral, and also a deposit of apatite, a phosphate mineral both containing Th and U associated to crystal lattice. The minerals are obtained from open pit mines, the minerals are processed in industrial also located in city of Araxa, these plants process the pyrochlore and apatite to obtain the Fe-Nb alloy and the concentrate of phosphate, respectively. Studies were developed in this area to assessment the occupational risk of the workers due to exposure to dust particles during the routine working, however very few studies evaluated the water contamination outside the mines in order to determine the metal (stables elements) concentrations in water and also the concentrations of the radionuclides in water. This paper presents the previous results of a study to identify and determine the concentrations of metals (stables elements) and radionuclides in river around the city. The water from these rivers is used as drinking water and irrigation water. The water samples were collected in different rivers around the Araxa city and the samples were analyzed using PIXE technique. A proton beam of 2 MeV obtained from the van de Graaff electrostatic accelerator was used to induce the characteristic X-rays. S, K, Ca, Cr, Mn, Fe, Ni, Zn, Ba, Pb and U were identified in the mass spectrum of the samples. The elemental mass concentrations were compared using a non-parametric statistical test. The results of the statistical test showed that the elemental mass concentrations did not present the same distribution. These results indicated

  7. Size effects on structural and dielectric properties of PZT thin films at compositions around the morpho tropic phase boundary

    International Nuclear Information System (INIS)

    Lima, Elton Carvalho; Araujo, Eudes Borges; Souza Filho, Antonio Gomes de; Bdikin, Igor

    2011-01-01

    Full text: The demand for portability in consumer electronics has motivated the understanding of size effects on ferroelectric thin films. The actual comprehension of these effects in ferroelectrics is unsatisfactory, since the polarization interacts more strongly than other order parameters such as strain and charge. As a result, extrinsic effects are produced if these variables are uncontrolled and problems such as ferroelectric paraelectric phase transition at nanometers scale remains an unsolved issue. In the present work, the effects of thickness and compositional fractions on the structural and dielectric properties of PbZr 1-x Ti x O 3 (PZT) thin films were studied at a composition around the morphotropic phase boundary (x = 0.50). For this purpose, thin films with different thicknesses and different PbO excess were deposited on Si(100) and Pt=T iO 2 =SiO 2 =Si substrates by a chemical method and crystallized in electric furnace at 700 deg C for 1 hour. The effects of substrate, pyrolysis temperature and excess lead addition in the films are reported. For films with 10 mol% PbO in excess, the pyrolysis in the regime of 300 deg C for 30 minutes was observed to yield PZT pyrochlore free thin films deposited on Pt=T iO 2 =SiO 2 =Si substrate. Out this condition, the transformation from amorphous to the pyrochlore metastable phase is kinetically more favorable that a transformation to the perovskite phase, which is thermodynamically stable. Rietveld refinements based on X-ray diffraction results showed that films present a purely tetragonal phase and that this phase does not change when the film thickness decreases. The dielectric permittivity measurements showed a monoclinic → tetragonal phase transition at 198K. Results showed that the dielectric permittivity (ε) increases continuously from 257 to 463, while the thickness of the PZT films increases from 200 to 710 nm. These results suggests that interface pinning centers can be the responsible mechanism by

  8. Tuning structure in epitaxial Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}–PbTiO{sub 3} thin films by using miscut substrates

    Energy Technology Data Exchange (ETDEWEB)

    Mietschke, M., E-mail: m.mietschke@ifw-dresden.de [IFW Dresden, P.O. Box 270116, D-01171 Dresden (Germany); Dresden University of Technology, Faculty of Mechanical Science and Engineering, D-01062 Dresden (Germany); Oswald, S.; Fähler, S. [IFW Dresden, P.O. Box 270116, D-01171 Dresden (Germany); Schultz, L. [IFW Dresden, P.O. Box 270116, D-01171 Dresden (Germany); Dresden University of Technology, Faculty of Mechanical Science and Engineering, D-01062 Dresden (Germany); Hühne, R. [IFW Dresden, P.O. Box 270116, D-01171 Dresden (Germany)

    2015-08-31

    Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}–PbTiO{sub 3} (PMN–PT) is one of the most promising ferroelectric material for actuator, dielectric and electrocaloric applications. However, oriented and phase pure thin films are essential to use the outstanding properties of these compounds. In this work it is demonstrated that the use of miscut substrates influences the growth mechanism leading to a significantly broader deposition window to achieve the required film quality. Therefore, epitaxial 0.68Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}–0.32PbTiO{sub 3} films were grown by pulsed laser deposition on (001)-oriented single crystalline SrTiO{sub 3} (STO) substrates with a miscut angle between 0 and 15° towards the [100] direction using a conducting La{sub 0.7}Sr{sub 0.3}CoO{sub 3} buffer layer. The influence of the vicinal angle on the PMN–PT structure was studied by high resolution X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. A nearly pure perovskite phase growth with a cube-on-cube epitaxial relationship was obtained on all miscut STO substrates, whereas a significant volume fraction of the pyrochlore phase was present on the standard substrate. Reciprocal space measurements revealed a peak split of the perovskite reflections indicating structural variants of PMN–PT with different c/a ratios. An additional tilting of the PMN–PT planes with respect to the buffer layer was observed on some samples, which might be explained with the incorporation of dislocations according to the Nagai model. Polarization loops were measured in a temperature range between room temperature and 150 °C showing a sharp drop of the remanent polarization above 65 °C on vicinal substrates. - Highlights: • Epitaxial growth of pure perovskite Pb (Mg{sub 1}/{sub 3}Nb{sub 2}/{sub 3})O{sub 3}–PbTiO{sub 3} on miscut SrTiO{sub 3}. • Significant broadening of the deposition window for pyrochlore-free films. • Dependence of the structural parameters

  9. Solubility behaviour of antimony(III) and antimony(V) solids in basic aqueous solutions at 300oC

    International Nuclear Information System (INIS)

    Lemire, R.J.; Tosello, N.B.; Halliday, J.D.

    1999-12-01

    The major contributions of the isotopes 122 Sb and 124 Sb to activity transport in a CANDU reactor primary heat transport system (HTS), have been associated with oxygen ingress during reactor shutdown. As part of a program to minimize the release and redeposition of these isotopes, the solubilities of antimony(III) and (V) oxides and salts have been measured in basic solutions at temperatures from 25 to 300 o C. The results provide information on the charge and the stability as a function of temperature of antimony solution species and, hence, a guide to the trends in the temperature dependence of the solubilities of antimony solids. In solutions in which oxidation of antimony(III) to antimony(V) is minimized, the solubility of Sb 2 O 3 increases by about two orders of magnitude between 25 and 200 o C, and then levels out or decreases slightly. At 250 o C, in oxidizing solutions, Sb 2 O 5 ·xH 2 O and simple sodium antimonate(V) were found to be unstable in sodium hydroxide solutions with respect to the solid, Na 2α [H(H 2 O)] 2-2α Sb 2 O 6 , which has a pyrochlore structure. The solubility of this partially protonated sodium antimonate increases from 25 to 200 o C and decreases at temperatures above 250 o C. These solubility changes for the antimony (V) solids reflect changes in the stability of the anionic antimony solution species (SbO 3 - or Sb(OH) 6 - ), even though the compositions of antimony-containing solids in basic oxidizing solutions are strongly dependent on the cations and their aqueous phase concentrations. All solids used in the present experiments would be expected to generate total solution antimony concentrations ≥ 0.00005 mol·dm -3 in any neutral or basic aqueous solutions (assuming no added sodium salts). Therefore, under HTS conditions, precipitation of any antimony oxides or mixed oxides is unlikely. It cannot be ruled out that hydrated Sb 2 O 5 (especially the pyrochlore form) might be less soluble in near-neutral, low

  10. Solubility behaviour of antimony(III) and antimony(V) solids in basic aqueous solutions at 300{sup o}C

    Energy Technology Data Exchange (ETDEWEB)

    Lemire, R.J.; Tosello, N.B.; Halliday, J.D

    1999-12-01

    The major contributions of the isotopes {sup 122}Sb and {sup 124}Sb to activity transport in a CANDU reactor primary heat transport system (HTS), have been associated with oxygen ingress during reactor shutdown. As part of a program to minimize the release and redeposition of these isotopes, the solubilities of antimony(III) and (V) oxides and salts have been measured in basic solutions at temperatures from 25 to 300{sup o}C. The results provide information on the charge and the stability as a function of temperature of antimony solution species and, hence, a guide to the trends in the temperature dependence of the solubilities of antimony solids. In solutions in which oxidation of antimony(III) to antimony(V) is minimized, the solubility of Sb{sub 2}O{sub 3} increases by about two orders of magnitude between 25 and 200{sup o}C, and then levels out or decreases slightly. At 250{sup o}C, in oxidizing solutions, Sb{sub 2}O{sub 5}{center_dot}xH{sub 2}O and simple sodium antimonate(V) were found to be unstable in sodium hydroxide solutions with respect to the solid, Na{sub 2{alpha}}[H(H{sub 2}O)]{sub 2-2{alpha}}Sb{sub 2}O{sub 6}, which has a pyrochlore structure. The solubility of this partially protonated sodium antimonate increases from 25 to 200{sup o}C and decreases at temperatures above 250{sup o}C. These solubility changes for the antimony (V) solids reflect changes in the stability of the anionic antimony solution species (SbO{sub 3}{sup -} or Sb(OH){sub 6}{sup -}), even though the compositions of antimony-containing solids in basic oxidizing solutions are strongly dependent on the cations and their aqueous phase concentrations. All solids used in the present experiments would be expected to generate total solution antimony concentrations {>=} 0.00005 mol{center_dot}dm{sup -3} in any neutral or basic aqueous solutions (assuming no added sodium salts). Therefore, under HTS conditions, precipitation of any antimony oxides or mixed oxides is unlikely. It cannot be

  11. REE-substituted Ca-free zirconolites

    International Nuclear Information System (INIS)

    Stefanovsky, S.V.; Chernyavskaya, N.E.; Ochkin, A.V.; Yudintsev, S.V.

    2002-01-01

    Previously we found zirconolite with composition (Gd 0.90 La 0.10 )(Zr 0.91 Ce 0.13 ) (Ti 1.20 Al 0.69 )O 7 in one of the ceramics designed for immobilization of REE-actinide HLW fraction. In this work we studied REEZrTiAlO 7 zirconolites with REE = La, Ce, Pr, Nd, Sm, Gd, Tb, and Y. To obtain the samples, the oxide mixtures were milled, compacted into pellets at 200 MPa and sintered at 1450 deg C or melted at 1550 deg C in air. To convert Ce (IV) to Ce (III), one test was performed in reducing conditions (carbon was introduced in batches). The ceramics were examined by X-ray diffraction (XRD) and by scanning and transmission electron microscopy (SEM, TEM). The XRD data revealed that the La-, Ce-, Pr-, and Nd-bearing samples were not single-phase ceramics. The La-bearing sample was composed of a major perovskite-type phase and a minor baddeleyite. The Ce-bearing samples consisted of major pyrochlore, cerianite-zirconia based cubic solid solution as a second in abundance phase, and minor zirconolite. The Pr-bearing ceramic contained major baddeleyite and a perovskite-type phase, and minor pyrochlore. In the Nd-, Sm-, Gd-, Tb-, and Y-bearing samples, zirconolite was predominant. Rare grains of REE-stabilized zirconia (fianite) were found by SEM in the Nd-, Sm, and Y-bearing ceramics. The Gd- and Tb-bearing samples were single phase. The average zirconolite formulas were Sm 1.06 Zr 1.07 Ti 1.00 Al 0.86 O 7 , Gd 1.01 Zr 1.05 Ti 0.98 Al 0.95 O 7 , Tb 0.93 Zr 1.09 Ti 1.08 Al 0.85 O 7 , and Y 1.05 Zr 1.03 Ti 1.03 Al 0.87 O 7 , hence, close to the specified zirconolite formula within the experimental error. XRD patterns of the Tb- and Y-bearing zirconolites are typical of zirconolite-2M variety. XRD patterns of the Nd-, Sm-, and Gd-bearing zirconolites differ from patterns typical of 2M, 3T, and 3O varieties known from reference data. The TEM study revealed a probable tetragonal symmetry of the zirconolite lattice on electron diffraction pattern

  12. NERI FINAL TECHNICAL REPORT, DE-FC07-O5ID14647, OPTIMIZATION OF OXIDE COMPOUNDS FOR ADVANCED INERT MATRIX MATERIALS

    Energy Technology Data Exchange (ETDEWEB)

    PI: JUAN C. NINO, ASSOCIATE PROFESSOR

    2009-01-11

    In order to reduce the current excesses of plutonium (both weapon grade and reactor grade) and other transuranium elements, a concept of inert matrix fuel (IMF) has been proposed for an uranium free transmutation of fissile actinides which excludes continuous uranium-plutonium conversion in thermal reactors and advanced systems. Magnesium oxide (MgO) is a promising candidate for inert matrix (IM) materials due to its high melting point (2827 C), high thermal conductivity (13 W/K {center_dot} m at 1000 C), good neutronic properties, and irradiation stability However, MgO reacts with water and hydrates easily, which prevents it from being used in light water reactors (LWRs) as an IM. To improve the hydration resistance of MgO-based inert matrix materials, Medvedev and coworkers have recently investigated the introduction of a secondary phase that acts as a hydration barrier. An MgO-ZrO{sub 2} composite was specifically studied and the results showed that the composite exhibited improved hydration resistance than pure MgO. However, ZrO{sub 2} is insoluble in most acids except HF, which is undesirable for fuel reprocessing. Moreover, the thermal conductivity of ZrO{sub 2} is low and typically less than 3 W {center_dot} m{sup -1} {center_dot} K{sup -1} at 1000 C. In search for an alternative composite strategy, Nd{sub 2}Zr{sub 2}O{sub 7}, an oxide compound with pyrochlore structure, has been proposed recently as a corrosion resistant phase, and MgO-Nd{sub 2}Zr{sub 2}O{sub 7} composites have been investigated as potential IM materials. An adequate thermal conductivity of 6 W {center_dot} m{sup -} 1 {center_dot} K{sup -1} at 1000 C for the MgO-Nd{sub 2}Zr{sub 2}O{sub 7} composite with 90 vol% MgO was recently calculated and reported. Other simulations proposed that the MgO-pyrochlore composites could exhibit higher radiation stability than previously reported. Final optimization of the composite microstructure was performed on the 70 vol% MgO-Nd{sub 2}Zr{sub 2}O{sub 7

  13. Synthesis, structure and electrical properties of Mg-, Ni-codoped bismuth niobates

    Directory of Open Access Journals (Sweden)

    M. S. Koroleva

    2017-12-01

    Full Text Available Mg-, Ni-codoped bismuth niobates Bi1.6Mg0.8-xNixNb1.6O7-δ (x = 0; 0.2; 0.4; 0.6; 0.8 were obtained by conventional solid-state reaction method. It was shown that the Mg atoms are distributed at the Nb sites while the Ni atoms are distributed over the Bi- and the Nb-sites, according to the results of comparison of pycnometric and X-ray density of the Bi1.6Mg0.4Ni0.4Nb1.6O7-δ pyrochlore. In this case, about 15–20% of the vacancies are formed at the Bi sites. The obtained compounds are stable up to their melting point based on the DSC analysis data. Real dielectric permittivity ε' of the Bi1.6Mg0.8-xNixNb1.6O7-δ samples decreases from 80 to 65 with the temperature decrease from 25 to 700 °C and practically does not depend on frequency in the range of 1–1000 kHz. Oxides Bi1.6Mg0.8-xNixNb1.6O7-δ behave like insulators up to 280 °C, their conductivity increases with temperature (Ea,dc ≈ 1.3 eV, dc and with the Ni content at a given temperature.

  14. Epitaxial growth and structural characterization of Pb(Fe1/2Nb1/2)O3 thin films

    International Nuclear Information System (INIS)

    Peng, W.; Lemee, N.; Holc, J.; Kosec, M.; Blinc, R.; Karkut, M.G.

    2009-01-01

    We have grown lead iron niobate thin films with composition Pb(Fe 1/2 Nb 1/2 )O 3 (PFN) on (0 0 1) SrTiO 3 substrates by pulsed laser deposition. The influence of the deposition conditions on the phase purity was studied. Due to similar thermodynamic stability spaces, a pyrochlore phase often coexists with the PFN perovskite phase. By optimizing the kinetic parameters, we succeeded in identifying a deposition window which resulted in epitaxial perovskite-phase PFN thin films with no identifiable trace of impurity phases appearing in the X-ray diffractograms. PFN films having thicknesses between 20 and 200 nm were smooth and epitaxially oriented with the substrate and as demonstrated by RHEED streaks which were aligned with the substrate axes. X-ray diffraction showed that the films were completely c-axis oriented and of excellent crystalline quality with low mosaicity (X-ray rocking curve FWHM≤0.09 deg.). The surface roughness of thin films was also investigated by atomic force microscopy. The root-mean-square roughness varies between 0.9 nm for 50-nm-thick films to 16 nm for 100-nm-thick films. We also observe a correlation between grain size, surface roughness and film thickness.

  15. Damage evolution of ion irradiated defected-fluorite La 2 Zr 2 O 7 epitaxial thin films

    Energy Technology Data Exchange (ETDEWEB)

    Kaspar, Tiffany C.; Gigax, Jonathan G.; Shao, Lin; Bowden, Mark E.; Varga, Tamas; Shutthanandan, Vaithiyalingam; Spurgeon, Steven R.; Yan, Pengfei; Wang, Chongmin; Ramuhalli, Pradeep; Henager, Charles H.

    2017-05-01

    Pyrochlore-structure oxides, A2B2O7, may exhibit remarkable radiation tolerance due to the ease with which they can accommodate disorder by transitioning to a defected fluorite structure. The mechanism of defect formation was explored by evaluating the radiation damage behavior of high quality epitaxial La2Zr2O7 thin films with the defected fluorite structure, irradiated with 1 MeV Zr+ at doses up to 10 displacements per atom (dpa). The level of film damage was evaluated as a function of dose by Rutherford backscattering spectrometry in the channeling geometry (RBS/c) and scanning transmission electron microscopy (STEM). At lower doses, the surface of the La2Zr2O7 film amorphized, and the amorphous fraction as a function of dose fit well to a stimulated amorphization model. As the dose increased, the surface amorphization slowed, and amorphization appeared at the interface. Even at a dose of 10 dpa, the core of the film remained crystalline, despite the prediction of amorphization from the model. To inform future ab initio simulations of La2Zr2O7, the bandgap of a thick La2Zr2O7 film was measured to be indirect at 4.96 eV, with a direct transition at 5.60 eV.

  16. Uranium luminescence in La2 Zr2 O7 : effect of concentration and annealing temperature.

    Science.gov (United States)

    Mohapatra, M; Rajeswari, B; Hon, N S; Kadam, R M

    2016-12-01

    The speciation of a particular element in any given matrix is a prerequisite to understanding its solubility and leaching properties. In this context, speciation of uranium in lanthanum zirconate pyrochlore (La 2 Zr 2 O 7  = LZO), prepared by a low-temperature combustion route, was carried out using a simple photoluminescence lifetime technique. The LZO matrix is considered to be a potential ceramic host for fixing nuclear and actinide waste products generated during the nuclear fuel cycle. Special emphasis has been given to understanding the dynamics of the uranium species in the host as a function of annealing temperature and concentration. It was found that, in the LZO host, uranium is stabilized as the commonly encountered uranyl species (UO 2 2+ ) up to a heat treatment of 500 °C at the surface. Above 500 °C, the uranyl ion is diffused into the matrix as the more symmetric octahedral uranate species (UO 6 6- ). The uranate ions thus formed replace the six-coordinated 'Zr' atoms at regular lattice positions. Further, it was observed that concentration quenching takes place beyond 5 mol% of uranium doping. The mechanism of the quenching was found to be a multipolar interaction. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  17. Low temperature molten salt synthesis of Y2Sn2O7 anode material for lithium ion batteries

    International Nuclear Information System (INIS)

    Nithyadharseni, P.; Reddy, M.V.; Ozoemena, Kenneth I.; Balakrishna, R. Geetha; Chowdari, B.V.R.

    2015-01-01

    Highlights: • For the first time Y 2 Sn 2 O 7 compound was prepared at very low temperature by molten salt method. • We studied the effect of reheating on electrochemical properties. • All the compounds showed particle size of below 500 nm. • The all compounds showed a stable and good capacity retention during cycling. - Abstract: For the first time, yttrium tin oxide (Y 2 Sn 2 O 7 ) compound is prepared at low temperature (400 °C) with cubic pyrochlore structure via molten salt method using KOH as a flux for their electrochemical applications. The final product is reheated at three different temperatures of 600, 800 and 1000 °C for 6 h in air, are physically and chemically characterized by various techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM) and electrochemical studies of galvanostatic cycling (GC), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Galvanostatic cycling of Y 2 Sn 2 O 7 compounds are carried out with three different current densities of 60, 100 and 250 mA g −1 and the potential range of 0.005–1.0 V vs. Li. The EIS is carried out to study the electrode kinetics during discharge and charge at various voltages and corresponding variation of resistance and capacitance values are discussed.

  18. Crystal structure and Mössbauer effect in multiferroic 0.5BiFeO3-0.5Pb(Fe0.5Ta0.5O3 solid solution

    Directory of Open Access Journals (Sweden)

    Stoch Agata

    2017-06-01

    Full Text Available Multiferroic 0.5BiFeO3-0.5Pb(Fe0.5Ta0.5O3 solid solution is a material that exhibits ferroelectric and antiferromagnetic orderings in ambient temperature. The solid solution was obtained as a result of a conventional reaction in a solid state. The obtained material is a dense, fine-grained sinter whose surface was observed by scanning electron microscopy (SEM and stoichiometry was confirmed by energy dispersive X-ray spectroscopic (EDS analysis. According to the X-ray powder diffraction (XRD measurements, the main phase is R3c space group with admixture of Pm-3m regular phase. Small contribution of pyrochlore-like phase was also observed. Mössbauer spectroscopy suggested random distribution of Fe3+/Ta5+ cations in the B sites of ABO3 compound. Reduction of the magnetic hyperfine field with an increase in the substitution of Ta5+ in Fe3+ neighbourhood was also observed.

  19. Failure Analysis of Multilayered Suspension Plasma-Sprayed Thermal Barrier Coatings for Gas Turbine Applications

    Science.gov (United States)

    Gupta, M.; Markocsan, N.; Rocchio-Heller, R.; Liu, J.; Li, X.-H.; Östergren, L.

    2018-02-01

    Improvement in the performance of thermal barrier coatings (TBCs) is one of the key objectives for further development of gas turbine applications. The material most commonly used as TBC topcoat is yttria-stabilized zirconia (YSZ). However, the usage of YSZ is limited by the operating temperature range which in turn restricts the engine efficiency. Materials such as pyrochlores, perovskites, rare earth garnets are suitable candidates which could replace YSZ as they exhibit lower thermal conductivity and higher phase stability at elevated temperatures. The objective of this work was to investigate different multilayered TBCs consisting of advanced topcoat materials fabricated by suspension plasma spraying (SPS). The investigated topcoat materials were YSZ, dysprosia-stabilized zirconia, gadolinium zirconate, and ceria-yttria-stabilized zirconia. All topcoats were deposited by TriplexPro-210TM plasma spray gun and radial injection of suspension. Lifetime of these samples was examined by thermal cyclic fatigue and thermal shock testing. Microstructure analysis of as-sprayed and failed specimens was performed with scanning electron microscope. The failure mechanisms in each case have been discussed in this article. The results show that SPS could be a promising route to produce multilayered TBCs for high-temperature applications.

  20. Recovery of rare earth minerals, with emphasis on flotation process

    International Nuclear Information System (INIS)

    Houot, R.; Cuif, J.P.; Mottot, Y.; Samama, J.C.

    1991-01-01

    Bastnasite and monazite are the two major minerals used commercially to supply most of the rare earths. Monazite is often a by-product of the concentration of heavy minerals of zirconium and titanium in beach sands. Thus, the methods of concentration are gravity (spirals, Reichert cones and shaking tables), ending with magnetism, electrostatic and in certain cases, flotation. The two main deposits of bastnasite are Mountain Pass (U.S.A.) and Bayan Obo (China). The rock bastnasite content is within 15% and the recovery of rare earth minerals is made through flotation. The flowsheets are complex enough because the existence of accompanying minerals such as quartz, iron components, barite, fluorite, calcite, etc. The conditioning is done by heating and the frequently employed collector is a fatty acid associated with selective agents, as sodium silicate or fluosilicate, lignin sulphonate, sodium carbonate, aluminium salts, etc. Recent studies tempt to introduce the use of phosphoric esters, dicarboxilic, sulphonic and/or sulphosuccinic acids. Concentrates with 60% REO are then treated with acidic solution to eliminate residual calcite. The possibility of obtaining products enriched with rare earths are also noted: these are ores of uranium (Elliot Lake), pyrochlore, apatite, and other complex ores with euxenite, fergusonite or loparite. (author) 10 figs., 6 tabs., 57 refs

  1. Microstructure of HIPed and SPSed 9Cr-ODS steel and its effect on helium bubble formation

    International Nuclear Information System (INIS)

    Lu, Chenyang; Lu, Zheng; Xie, Rui; Liu, Chunming; Wang, Lumin

    2016-01-01

    Two 9Cr-ODS steels with the same nominal composition were consolidated by hot isostatic pressing (HIP, named COS-1) and spark plasma sintering (SPS, named COS-2). Helium ions were implanted into COS-1, COS-2 and non-ODS Eurofer 97 steels up at 673 K. Microstructures before and after helium ion implantations were carefully characterized. The results show a bimodal grain size distribution in COS-2 and a more uniform grain size distribution in COS-1. Nanoscale clusters of GP-zone type Y–Ti–O and Y_2Ti_2O_7 pyrochlore as well as large spinel Mn(Ti)Cr_2O_4 particles are all observed in the two ODS steels. The Y–Ti-enriched nano-oxides in COS-1 exhibit higher number density and smaller size than in COS-2. The Y–Ti-enriched nano-oxides in fine grains of COS-2 show higher number density and smaller size than that in coarse grains of COS-2. Nano-oxides effectively trap helium atoms and lead to the formation of high density and ultra-fine helium bubbles. - Highlights: • The microstructure changes of two ODS steels before and after helium ion implantation have been elucidated. • The mechanism of the microstructures of ODS steels under varied thermal mechanical processing paths have been explored. • The dependence of the size, density and distribution of helium bubbles on the specific microstructure features are explored.

  2. Near infra red light emitting Y2Sn2O7: Yb-Er nanoparticles

    International Nuclear Information System (INIS)

    Nigam, Sandeep; Sudarsan, V.; Vatsa, R.K.

    2011-01-01

    There is an increasing interest in erbium doped nanomaterials host, since they emit in the near-infrared region and are potential candidates for optical telecommunication, high-power and infrared lasers. Further, erbium-ytterbium-co-doped matrices have been particularly investigated as Yb 3+ ions play the role of sensitizers. In the present work, Y 2 Sn 2 O 7 nanoparticles co-doped with lanthanide ions Yb 3+ and Er 3+ were prepared based on the urea hydrolysis of Y 3+ , Sn 4+ , and Ln 3+ in ethylene glycol medium at 150 deg C followed by heating at 700 deg C. As prepared samples are amorphous in nature, and the sample heated at 700 deg C showed well crystalline pyrochlore structure. Based on TEM studies, it has been established that nano-particles are highly crystalline, with size range in the range of 2-5 nm. Luminescence measurements were carried out for the as prepared samples and those heated at 700 deg C. As prepared sampled showed very poor luminescence. However on heating to 700 deg C, strong emission in the NIR region was observed upon UV-excitation as can be seen. The peak observed around 1530 nm has been attributed to 4 I 13/2 → 4 I 15/2 transition of Er 3+ and the peak around 980 nm is due to 2 F 5/2 → 2 F 7/2 transition of Yb 3+ . (author)

  3. Coexistence of spin frozen state and persistent spin dynamics in NaSrCo{sub 2}F{sub 7} as probed by μSR and NMR

    Energy Technology Data Exchange (ETDEWEB)

    Dengre, Shanu; Sarkar, Rajib; Braeuninger, Sascha Albert; Brueckner, Felix; Materne, Philipp; Klauss, Hans-Henning [Institute for Solid State Physics, TU Dresden (Germany); Krizan, Jason W.; Cava, Robert J. [Department of Chemistry, Princeton University, Princeton, NJ (United States); Luetkens, Hubertus; Baines, Chris [Laboratory for Muon-Spin Spectroscopy, Paul Scherrer Institute, Villigen (Switzerland)

    2016-07-01

    {sup 23}Na -and {sup 19}F NMR, and μSR experiments are performed to explore the microscopic properties of NaSrCo{sub 2}F{sub 7}, which is a newly discovered magnetically frustrated pyrochlore with weak bond disorder and with a frustration index of f = 42. While {sup 23}Na and {sup 19}F NMR experiments clearly suggest the presence of quasi static field distribution below ∝3 K as reflected in the huge NMR line broadening and wipe out effect of NMR signal intensity, μSR experiments on the other hand remains passive to this spin frozen state. Both NMR and μSR results indicate the slowing down of the magnetic (spin) fluctuations upon cooling towards the NMR spin frozen state. μSR relaxation rate increases slightly below ∝ 3 K, and remains not only constant down to 20 mK, but also stands independent in longitudinal magnetic field upto 4000 G implying that the spin fluctuations are dynamic. These observations suggest the coexistence of partial spin frozen state and persistent spin dynamics in NaSrCo{sub 2}F{sub 7}.

  4. Effect of atmosphere on the formation of perovskite phase in 0.90Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}-0.10PbTiO{sub 3} (PZN-10PT) powders

    Energy Technology Data Exchange (ETDEWEB)

    Raigoza, C.F.V., E-mail: claudiafercha@gmail.com [Universidad del Cauca, Dpto. de Física, Grupo de Ciencia y Tecnología de Materiales Cerámicos, Popayán (Colombia); Kiminami, R.H.G.A. [Federal University of São Carlos, Department of Materials Engineering, São Carlos, SP, 13565-905 (Brazil); Eiras, J.A.; Garcia, D. [Federal University of São Carlos, Department of Physics, São Carlos, SP, 13565-905 (Brazil)

    2017-04-01

    Lead zinc niobate (PZN) and lead titanate (PT) solid solutions close to the morphotropic phase boundary (MPB) exhibit unusually large dielectric and piezoelectric constants. PZN-PT ceramics with a composition close to the MPB processed by the conventional route yield ceramics with a pyrochlore structure. In the last few decades, attempts to synthesize PZN-PT powders with perovskite structure via traditional ceramic methods and novel chemical processing routes have failed. In the present research, an analysis was made of the effect of the calcination atmosphere on the formation of perovskite phase in PZN-10PT powders. To this end, thermal analyses were carried out in four different atmospheres: oxygen, air, argon and nitrogen. The powders were calcined at the temperatures at which the DTA curves presented peaks, and the resulting phases were identified by X-ray diffraction. - Highlights: • PZN-PT ceramics powders. • Air, oxygen, argon and nitrogen as synthesis atmospheres. • Zinc as essential element in the formation and stabilization of the perovskite phase. • Nitrogen as inhibitor of the decomposition the zinc oxide.

  5. Hydrothermal synthesis of WO{sub 3}·0.5H{sub 2}O microtubes with excellent photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaozhou; Meng, Xiuqing, E-mail: xqmeng@semi.ac.cn; Zhong, Mianzeng; Wu, Fengmin; Li, Jingbo, E-mail: jbli@semi.ac.cn

    2013-10-01

    Pyrochlore WO{sub 3} microtubes were synthesized via a hydrothermal method for the first time. In this process, thiourea was employed to overcome the hydrogen bonds on the rim of WO{sub 3}·0.5H{sub 2}O and hydroxylamine hydrochloride was used as a viscosity regulator. Field-emission scanning electron microscopy and high-resolution transmission electron microscopy observations revealed that large amounts of uniform single-crystal WO{sub 3}·0.5H{sub 2}O microtubes with diameters ranging from 100 to 300 nm and length of tens of micrometers were obtained. The thickness of the tube wall was about 40 nm. A possible rolling mechanism was proposed to explain the formation of the tubular structures, and the influence of thiourea and hydroxylamine hydrochloride on the uniform tubular morphology was discussed. The WO{sub 3}·0.5H{sub 2}O microtubes showed excellent photocatalytic activity toward the degradation of organic molecules such as RhB, which may find potential applications in the fields of photocatalysts, sensors and transistors.

  6. Magnetoelastic properties of the quantum-spin-ice candidate Yb{sub 2}Ti{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Stoeter, T.; Wang, Z.S.; Wosnitza, J. [SFB 1143 (Germany); TUD/IFP, Dresden (Germany); HZDR, Dresden (Germany); Doerr, M.; Granovsky, S. [SFB 1143 (Germany); TUD/IFP, Dresden (Germany); Erfanifam, S.; Green, E. [HZDR, Dresden (Germany); Zherlitsyn, S. [SFB 1143 (Germany); HZDR, Dresden (Germany); Maljuk, A.; Wurmehl, S. [SFB 1143 (Germany); IFW, Dresden (Germany)

    2016-07-01

    Intriguing phenomena such as the occurrence of magnetic monopoles and a wide variety of ground states are associated to magnetic frustration. In a number of cases, elastic effects, e.g. lattice distortions, may result in the lifting of degeneracies or the appearance of new magnetic states. The rare-earth titanate Yb{sub 2}Ti{sub 2}O{sub 7}, where the magnetic Yb{sup 3+} ions form a pyrochlore spin network, is a prime example of a geometrically frustrated material, with numerous field-induced phases and strong ferromagnetic correlations below 170 mK. In order to characterize the magneto-elastic coupling in this material, we have investigated the thermal expansion, magnetostriction, and sound propagation in different dilution refrigerators between 60 mK and 1.5 K and large applied magnetic fields. At around 170 mK we find distinct anomalies in the expansion coefficient, acoustic properties, as well as the specific heat. Lattice anomalies in field hint to additional low temperature phases.

  7. Characterization of Ceramic Material Produced From a Cold Crucible Induction Melter Test

    Energy Technology Data Exchange (ETDEWEB)

    Amoroso, J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Marra, J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-04-30

    This report summarizes the results from characterization of samples from a melt processed surrogate ceramic waste form. Completed in October of 2014, the first scaled proof of principle cold crucible induction melter (CCIM) test was conducted to process a Fe-hollandite-rich titanate ceramic for treatment of high level nuclear waste. X-ray diffraction, electron microscopy, inductively coupled plasma-atomic emission spectroscopy (and inductively coupled plasma-mass spectroscopy for Cs), and product consistency tests were used to characterize the CCIM material produced. Core samples at various radial locations from the center of the CCIM were taken. These samples were also sectioned and analyzed vertically. Together, the various samples were intended to provide an indication of the homogeneity throughout the CCIM with respect to phase assemblage, chemical composition, and chemical durability. Characterization analyses confirmed that a crystalline ceramic with desirable phase assemblage was produced from a melt using a CCIM. Hollandite and zirconolite were identified in addition to possible highly-substituted pyrochlore and perovskite. Minor phases rich in Fe, Al, or Cs were also identified. Remarkably only minor differences were observed vertically or radially in the CCIM material with respect to chemical composition, phase assemblage, and durability. This recent CCIM test and the resulting characterization in conjunction with demonstrated compositional improvements support continuation of CCIM testing with an improved feed composition and improved melter system.

  8. Dipolar Spin Ice States with a Fast Monopole Hopping Rate in CdEr2X4 (X =Se , S)

    Science.gov (United States)

    Gao, Shang; Zaharko, O.; Tsurkan, V.; Prodan, L.; Riordan, E.; Lago, J.; Fâk, B.; Wildes, A. R.; Koza, M. M.; Ritter, C.; Fouquet, P.; Keller, L.; Canévet, E.; Medarde, M.; Blomgren, J.; Johansson, C.; Giblin, S. R.; Vrtnik, S.; Luzar, J.; Loidl, A.; Rüegg, Ch.; Fennell, T.

    2018-03-01

    Excitations in a spin ice behave as magnetic monopoles, and their population and mobility control the dynamics of a spin ice at low temperature. CdEr2 Se4 is reported to have the Pauling entropy characteristic of a spin ice, but its dynamics are three orders of magnitude faster than the canonical spin ice Dy2 Ti2 O7 . In this Letter we use diffuse neutron scattering to show that both CdEr2 Se4 and CdEr2 S4 support a dipolar spin ice state—the host phase for a Coulomb gas of emergent magnetic monopoles. These Coulomb gases have similar parameters to those in Dy2 Ti2 O7 , i.e., dilute and uncorrelated, and so cannot provide three orders faster dynamics through a larger monopole population alone. We investigate the monopole dynamics using ac susceptometry and neutron spin echo spectroscopy, and verify the crystal electric field Hamiltonian of the Er3 + ions using inelastic neutron scattering. A quantitative calculation of the monopole hopping rate using our Coulomb gas and crystal electric field parameters shows that the fast dynamics in CdEr2X4 (X =Se , S) are primarily due to much faster monopole hopping. Our work suggests that CdEr2X4 offer the possibility to study alternative spin ice ground states and dynamics, with equilibration possible at much lower temperatures than the rare earth pyrochlore examples.

  9. PREFACE: Preface

    Science.gov (United States)

    Hotta, Takashi

    2016-02-01

    This volume of Journal of Physics: Conference Series contains both invited and contributed papers presented at the International Symposium on "New Quantum Phases Emerging from Novel Crystal Structure", which was held from 24-25 September 2015 at the Minami-Osawa Campus of Tokyo Metropolitan University (TMU). The Graduate School of Science and Engineering of TMU is now promoting a research project on "New Quantum Phases Emerging from Novel Crystal Structure" with the support of the university. This is the cooperative project involving the electrical and electronic engineering and physics departments to discover new quantum phases in strongly correlated electron systems on novel crystal structures, with geometrically characteristic properties such as cage, layered, and geometrical frustrated structures. In this international symposium, we have mainly picked up BiS2-based layered superconductors, cage-structure materials such as 1-2-20 and filled skutterudites, geometrically frustrated systems such as pyrochlore compounds, and noncentrosymmetric materials. Topics on other materials with exotic crystal structure have been also discussed. I believe that this symposium provides a good opportunity to present recent research results on magnetism and superconductivity in such materials, and to discuss future directions of research on strongly correlated electron systems with novel crystal structure. I would like to give thanks, on behalf of the organizing committee, to all participants of the TMU International Symposium and all members of the Advisory Committee, who have contributed to the success of this symposium. I further thank the TMU Research Organization for the financial support of this symposium.

  10. Radiation damage in nuclear waste materials

    International Nuclear Information System (INIS)

    Jencic, I.

    2000-01-01

    Final disposal of high-level radioactive nuclear waste is usually envisioned in some sort of ceramic material. The physical and chemical properties of host materials for nuclear waste can be altered by internal radiation and consequently their structural integrity can be jeopardized. Assessment of long-term performance of these ceramic materials is therefore vital for a safe and successful disposal. This paper presents an overview of studies on several possible candidate materials for immobilization of fission products and actinides, such as spinel (MgAl 2 O 4 ), perovskite (CaTiO 3 ), zircon (ZrSiO 4 ), and pyrochlore (Gd 2 Ti 2 O 7 and Gd 2 Zr 2 O 7 ). The basic microscopic picture of radiation damage in ceramics consists of atomic displacements and ionization. In many cases these processes result in amorphization (metaminctization) of irradiated material. The evolution of microscopic structure during irradiation leads to various macroscopic radiation effects. The connection between microscopic and macroscopic picture is in most cases at least qualitatively known and studies of radiation induced microscopic changes are therefore an essential step in the design of a reliable nuclear waste host material. The relevance of these technologically important results on our general understanding of radiation damage processes and on current research efforts in Slovenia is also addressed. (author)

  11. Quantum phase transitions and anomalous Hall effect in frustrated Kondo lattices

    Science.gov (United States)

    Paschen, Silke; Grefe, Sarah Elaine; Ding, Wenxin; Si, Qimiao

    Among the pyrochlore iridates, the metallic compound Pr2 Ir2O7 (Pr-227) has shown characteristics of a possible chiral spin liquid state and quantum criticality. An important question surrounding the significant anomalous Hall response observed in Pr-227 is the nature of the f-electron local moments, including their Kondo coupling with the conduction d-electrons. The heavy effective mass and related thermodynamic characteristics indicate the involvement of the Kondo effect in this system's electronic properties. In this work, we study the effects of Kondo coupling on candidate time-reversal-symmetry-breaking spin liquid states on frustrated lattices. Representing the f-moments as slave fermions Kondo-coupled to conduction electrons, we study the competition between Kondo-singlet formation and chiral spin correlations. We derive an effective chiral interaction between the local moments and the conduction electrons and calculate the anomalous Hall response across the quantum phase transition from the Kondo destroyed phase to the Kondo screened phase. We discuss our results' implications for Pr-227 and related frustrated Kondo-lattice systems.

  12. Investigation of chemical bond characteristics, thermal expansion coefficients and bulk moduli of alpha-R2MoO6 and R2Mo2O7 (R = rare earths) by using a dielectric chemical bond method.

    Science.gov (United States)

    Li, Huaiyong; Zhang, Siyuan; Zhou, Shihong; Cao, Xueqiang

    2009-09-01

    Theoretical researches are performed on the alpha-R2MoO6 (R = Y, Gd, Tb Dy, Ho, Er, Tm and Yb) and pyrochlore-type R2Mo2O7 (R = Y, Nd, Sm, Gd, Tb and Dy) rare earth molybdates by using chemical bond theory of dielectric description. The chemical bonding characteristics and their relationship with thermal expansion property and compressibility are explored. The calculated values of linear thermal expansion coefficient (LTEC) and bulk modulus agree well with the available experimental values. The calculations reveal that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the lanthanides: the LTEC decreases from 6.80 to 6.62 10(-6)/K and the bulk modulus increases from 141 to 154 GPa when R goes in the order Gd, Tb Dy, Ho, Er, Tm, and Yb in the alpha-R2MoO6 series; while in the R2Mo2O7 series, the LTEC ranges from 6.80 to 6.61 10(-6)/K and the bulk modulus ranges from 147 to 163 GPa when R varies in the order Nd, Sm, Gd, Tb and Dy. Copyright 2008 Wiley Periodicals, Inc.

  13. Fabrication and properties of La2-xGdxHf2O7 transparent ceramics

    International Nuclear Information System (INIS)

    Wang, Zhengjuan; Zhou, Guohong; Zhang, Fang; Qin, Xianpeng; Ai, Jianping; Wang, Shiwei

    2016-01-01

    La 2-x Gd x Hf 2 O 7 (x=0–2.0) transparent ceramics were fabricated through vacuum sintering from nano-powders synthesized by a simple combustion method. The phase composition of the powders and final ceramics, the in-line transmittance, microstructures and density of the ceramics were investigated. With the increasing of Gd content, the ceramics maintained the cubic pyrochlore structure, and the lattice parameters decreased, whilst the densities increased linearly. All the ceramics were transparent. The highest in-line transmittance was 76.1% at 800 nm (x=1.2). With high density (7.91–8.88 g/cm 3 ) and effective atomic number, some of the La 2-x Gd x Hf 2 O 7 (x=0–2.0) transparent ceramics are promising candidates for scintillator hosts. - Highlights: • A new series of La 2-x Gd x Hf 2 O 7 transparent ceramics were fabricated by vacuum sintering using combustion-synthesized powders. • All the ceramics are transparent and the in-line transmittance can reach to 76.1% at 800 nm when x=1.2. • The Gd content has effects on the crystal structure, in-line transmittance, microstructures and densities of the ceramics. • With high density (7.91~8.88 g/cm3) and effective atomic number, some of the La2-xGdxHf2O7 transparent ceramics are promising candidates for scintillator hosts.

  14. Occurrence and multivariate exploratory analysis of the natural radioactivity anomaly in the south coastal region of Kenya

    Science.gov (United States)

    Kaniu, M. I.; Angeyo, K. H.; Darby, I. G.

    2018-05-01

    Characterized by a variety of rock formations, namely alkaline, igneous and sedimentary that contain significant deposits of monazite and pyrochlore ores, the south coastal region of Kenya may be regarded as highly heterogeneous with regard to its geochemistry, mineralogy as well as geological morphology. The region is one of the several alkaline carbonatite complexes of Kenya that are associated with high natural background radiation and therefore radioactivity anomaly. However, this high background radiation (HBR) anomaly has hardly been systematically assessed and delineated with regard to the spatial, geological, geochemical as well as anthropogenic variability and co-dependencies. We conducted wide-ranging in-situ gamma-ray spectrometric measurements in this area. The goal of the study was to assess the radiation exposure as well as determine the underlying natural radioactivity levels in the region. In this paper we report the occurrence, exploratory analysis and modeling to assess the multivariate geo-dependence and spatial variability of the radioactivity and associated radiation exposure. Unsupervised principal component analysis and ternary plots were utilized in the study. It was observed that areas which exhibit HBR anomalies are located along the south coast paved road and in the Mrima-Kiruku complex. These areas showed a trend towards enhanced levels of 232Th and 238U and low 40K. The spatial variability of the radioactivity anomaly was found to be mainly constrained by anthropogenic activities, underlying geology and geochemical processes in the terrestrial environment.

  15. Pulsed laser deposition of Pb(Zr0.52Ti0.48)O3 thin film on cobalt ferrite nano-seed layered Pt(111)/Si substrate: effect of oxygen pressure

    Science.gov (United States)

    Khodaei, M.; Seyyed Ebrahimi, S. A.; Park, Yong Jun; Song, Seungwoo; Jang, Hyun Myung; Son, Junwoo; Baik, Sunggi

    2014-07-01

    The effect of oxygen pressure during pulsed laser deposition of Pb(Zr0.52Ti0.48)O3 (PZT) thin films on CoFe2O4 nano-seed layered Pt(111)/Si substrate was investigated. The PZT film deposited at oxygen pressure lower than 25 mTorr is identified as both perovskite and pyrochlore phases and the films deposited at high oxygen pressure (50-100 mTorr) show the single-phase perovskite PZT that has a perfect (111)-orientation. In addition, the film deposited at PO2 of 50 mTorr has a uniform surface morphology, whereas the film deposited at PO2 of 100 mTorr has a non-uniform surface morphology and more incompacted columnar cross-section microstructure. The polarization of film deposited at 100 mTorr is higher than that deposited at 50 mTorr, but shift of the hysteresis loop along the electrical field axis in the film deposited at PO2 of 100 mTorr is larger than that of the film deposited at PO2 of 50 mTorr.

  16. Status of plutonium ceramic immobilization processes and immobilization forms

    Energy Technology Data Exchange (ETDEWEB)

    Ebbinghaus, B.B.; Van Konynenburg, R.A. [Lawrence Livermore National Lab., CA (United States); Vance, E.R.; Jostsons, A. [Australian Nuclear Science and Technology Organization, Menai (Australia)] [and others

    1996-05-01

    Immobilization in a ceramic followed by permanent emplacement in a repository or borehole is one of the alternatives currently being considered by the Fissile Materials Disposition Program for the ultimate disposal of excess weapons-grade plutonium. To make Pu recovery more difficult, radioactive cesium may also be incorporated into the immobilization form. Valuable data are already available for ceramics form R&D efforts to immobilize high-level and mixed wastes. Ceramics have a high capacity for actinides, cesium, and some neutron absorbers. A unique characteristic of ceramics is the existence of mineral analogues found in nature that have demonstrated actinide immobilization over geologic time periods. The ceramic form currently being considered for plutonium disposition is a synthetic rock (SYNROC) material composed primarily of zirconolite (CaZrTi{sub 2}O{sub 7}), the desired actinide host phase, with lesser amounts of hollandite (BaAl{sub 2}Ti{sub 6}O{sub 16}) and rutile (TiO{sub 2}). Alternative actinide host phases are also being considered. These include pyrochlore (Gd{sub 2}Ti{sub 2}O{sub 7}), zircon (ZrSiO{sub 4}), and monazite (CePO{sub 4}), to name a few of the most promising. R&D activities to address important technical issues are discussed. Primarily these include moderate scale hot press fabrications with plutonium, direct loading of PuO{sub 2} powder, cold press and sinter fabrication methods, and immobilization form formulation issues.

  17. Self-assembly of three-dimensional open structures using patchy colloidal particles.

    Science.gov (United States)

    Rocklin, D Zeb; Mao, Xiaoming

    2014-10-14

    Open structures can display a number of unusual properties, including a negative Poisson's ratio, negative thermal expansion, and holographic elasticity, and have many interesting applications in engineering. However, it is a grand challenge to self-assemble open structures at the colloidal scale, where short-range interactions and low coordination number can leave them mechanically unstable. In this paper we discuss the self-assembly of three-dimensional open structures using triblock Janus particles, which have two large attractive patches that can form multiple bonds, separated by a band with purely hard-sphere repulsion. Such surface patterning leads to open structures that are stabilized by orientational entropy (in an order-by-disorder effect) and selected over close-packed structures by vibrational entropy. For different patch sizes the particles can form into either tetrahedral or octahedral structural motifs which then compose open lattices, including the pyrochlore, the hexagonal tetrastack and the perovskite lattices. Using an analytic theory, we examine the phase diagrams of these possible open and close-packed structures for triblock Janus particles and characterize the mechanical properties of these structures. Our theory leads to rational designs of particles for the self-assembly of three-dimensional colloidal structures that are possible using current experimental techniques.

  18. Working conditions and health of personnel dealing with ionizing radiation sources

    International Nuclear Information System (INIS)

    Gus'kova, A.K.

    1978-01-01

    Analyzed are the results of investigations dedicated to evaluation of working and health conditions of personnel engaged at powerful charged-particle accelerators, in the production of radionuclides, different stages of mining and enrichment of pyrochlore ore, maintenance of radio engineering and radio-physical equipment, those engaged on geological and geophysical research, operators of control desks and apparatuses at nuclear reactors. Observation of separate people has been carried out in control groups numbering 200-250 people. It has been found that the annual levels of irradiation doses are not in excess of maximum permissible doses (MPD), however in cases of long work service the total dose amounts to 150 rem (for 15-20 years). Changes in personnel health conditions are analyzed as dependent on the total irradiation dose. Apart from irradiation, the personnel health is also affected by other factors, specifically: unfavorable meteofactors, working regime etc. Specialized medical control was found to be inexpedient for people whose irradiation level was 1/3 of MPD. However for people whose irradiation level ranges from 1/3 to 1 MPD it is advisable to keep the current volume of oriented medical observation. A special attention in this case should be given to control systems, bronchopulmonary system and the state of cutaneous covering depending on the character of irradiation effects. Problems requiring further comprehensive studies are enumerated

  19. Split Fermi Surfaces of the Spin-Orbit-Coupled Metal Cd2Re2O7 Probed by de Haas-van Alphen Effect

    Science.gov (United States)

    Matsubayashi, Yasuhito; Sugii, Kaori; Hirose, Hishiro T.; Hirai, Daigorou; Sugiura, Shiori; Terashima, Taichi; Uji, Shinya; Hiroi, Zenji

    2018-05-01

    The superconducting pyrochlore oxide Cd2Re2O7 shows a structural transition with inversion symmetry breaking (ISB) at Ts1 = 200 K. A recent theory [https://doi.org/10.1103/PhysRevLett.115.026401" xlink:type="simple">L. Fu, Phys. Rev. Lett. 115, 026401 (2015)] suggests that the origin is an electronic instability that leads to a multipolar order in the spin-orbit-coupled metal. To observe the Fermi surface of the low-temperature phase of Cd2Re2O7, we perform de Haas-van Alphen effect measurements by means of magnetic torque. In reference to a calculated band structure, the spin-split Fermi surfaces with large cyclotron masses of 5-9m0 are revealed. The splitting is suggested to be due to an antisymmetric spin-orbit coupling induced by ISB, the strength of which is estimated to be approximately 67 K, which is rather smaller than those of typical non-centrosymmetric metals.

  20. Comparison of lead zirconate titanate thin films on ruthenium oxide and platinum electrodes

    International Nuclear Information System (INIS)

    Bursill, L.A.; Reaney, I.M.

    1994-01-01

    High-resolution and bright- and dark-field transmission electron microscopy are used to characterize and compare the interface structures and microstructure of PZT/RuO 2 /SiO 2 /Si and PZT/Pt/Ti/SiO 2 /Si ferroelectric thin films, with a view to understanding the improved fatigue characteristics of PZT thin films with RuO 2 electrodes. The RuO 2 /PZT interface consists of a curved pseudoperiodic minimal surface. The interface is chemically sharp with virtually no intermixing of RuO 2 and PZT, as evidenced by the atomic resolution images as well as energy dispersive X-ray analysis. A nanocrystalline pyrochlore phase Pb 2 ZrTiO 7-x (x ≠ 1) was found on the top surface of the PZT layer. The PZT/Pt/Ti/SiO 2 /Si thin film was well-crystallized and showed sharp interfaces throughout. Possible reasons for the improved fatigue characteristics of PZT/RuO 2 /SiO 2 /Si thin films are discussed. 13 refs; 7 figs

  1. Comparison of lead zirconate titanate thin films on ruthenium oxide and platinum electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Bursill, L A; Reaney, I M

    1994-12-31

    High-resolution and bright- and dark-field transmission electron microscopy are used to characterize and compare the interface structures and microstructure of PZT/RuO{sub 2}/SiO{sub 2}/Si and PZT/Pt/Ti/SiO{sub 2}/Si ferroelectric thin films, with a view to understanding the improved fatigue characteristics of PZT thin films with RuO{sub 2} electrodes. The RuO{sub 2}/PZT interface consists of a curved pseudoperiodic minimal surface. The interface is chemically sharp with virtually no intermixing of RuO{sub 2} and PZT, as evidenced by the atomic resolution images as well as energy dispersive X-ray analysis. A nanocrystalline pyrochlore phase Pb{sub 2}ZrTiO{sub 7-x} (x {ne} 1) was found on the top surface of the PZT layer. The PZT/Pt/Ti/SiO{sub 2}/Si thin film was well-crystallized and showed sharp interfaces throughout. Possible reasons for the improved fatigue characteristics of PZT/RuO{sub 2}/SiO{sub 2}/Si thin films are discussed. 13 refs; 7 figs.

  2. Structure and Thermal Expansion of YSZ and La2Zr2O7 Above 1500°C from Neutron Diffraction on Levitated Samples

    International Nuclear Information System (INIS)

    Ushakov, Sergey V.; Neuefeind, Joerg C.

    2015-01-01

    High-temperature time-of-flight neutron diffraction experiments were performed in this paper on cubic yttria-stabilized zirconia (YSZ, 10 mol% YO 1.5 ) and lanthanum zirconate (LZ) prepared by laser melting. Three spheroids of each composition were aerodynamically levitated and rotated in argon flow and heated with a CO 2 laser. Unit cell, positional and atomic displacement parameters were obtained by Rietveld analysis. Below ~1650°C the mean thermal expansion coefficient (TEC) for YSZ is higher than for LZ (13 ± 1 vs. 10.3 ± 0.6) × 10 -6 /K. From ~1650°C to the onset of melting of LZ at ~2250°C, TEC for YSZ and LZ are similar and within (7 ± 2) × 10 -6 /K. LZ retains the pyrochlore structure up to the melting temperature with Zr coordination becoming closer to perfectly octahedral. Congruently melting LZ is La deficient. The occurrence of thermal disordering of oxygen sublattice (Bredig transition) in defect fluorite structure was deduced from the rise in YSZ TEC to ~25 × 10 -6 /K at 2350°C–2550°C with oxygen displacement parameters (U iso ) reaching 0.1 Å 2 , similar to behavior observed in UO 2 . Acquisition of powder-like high-temperature neutron diffraction data from solid-levitated samples is feasible and possible improvements are outlined. Finally, this methodology should be applicable to a wide range of materials for high-temperature applications.

  3. Gapless topological order, gravity, and black holes

    Science.gov (United States)

    Rasmussen, Alex; Jermyn, Adam S.

    2018-04-01

    In this work we demonstrate that linearized gravity exhibits gapless topological order with an extensive ground state degeneracy. This phenomenon is closely related both to the topological order of the pyrochlore U (1 ) spin liquid and to recent work by Hawking and co-workers, who used the soft-photon and graviton theorems to demonstrate that the vacuum in linearized gravity is not unique. We first consider lattice models whose low-energy behavior is described by electromagnetism and linearized gravity, and then argue that the topological nature of these models carries over into the continuum. We demonstrate that these models can have many ground states without making assumptions about the topology of spacetime or about the high-energy nature of the theory, and show that the infinite family of symmetries described by Hawking and co-workers is simply the different topological sectors. We argue that in this context black holes appear as topological defects in the infrared theory, and that this suggests a potential approach to understanding both the firewall paradox and information encoding in gravitational theories. Finally, we use insights from the soft-boson theorems to make connections between deconfined gauge theories with continuous gauge groups and gapless topological order.

  4. Petrography and chemistry of tungsten-rich oxycalciobetafite in hydrothermal veins of the Adamello contact aureole, northern Italy

    Science.gov (United States)

    Lumpkin, Gregory R.; Gieré, Reto; Williams, C. Terry; McGlinn, Peter J.; Payne, Timothy E.

    2017-09-01

    Tungsten-rich oxycalciobetafite occurs in complex Ti-rich hydrothermal veins emplaced within dolomite marble in the contact aureole of the Adamello batholith, northern Italy, where it occurs as overgrowths on zirconolite. The betafite is weakly zoned and contains 29-34 wt% UO2. In terms of end-members, the betafite contains approximately 50 mol% CaUTi2O7 and is one of the closest known natural compositions to the pyrochlore phase proposed for use in titanate nuclear waste forms. Amorphization and volume expansion of the betafite caused cracks to form in the enclosing silicate mineral grains. Backscattered electron images reveal that betafite was subsequently altered along crystal rims, particularly near the cracks. Electron probe microanalyses reveal little difference in composition between altered and unaltered areas, except for lower totals, suggesting that alteration is primarily due to hydration. Zirconolite contains up to 18 wt% ThO2 and 24 wt% UO2, and exhibits strong compositional zoning, but no internal cracking due to differential (and anisotropic) volume expansion and no visible alteration. The available evidence demonstrates that both oxycalciobetafite and zirconolite retained actinides for approximately 40 million years after the final stage of vein formation. During this time, oxycalciobetafite and zirconolite accumulated a total alpha-decay dose of 3.0-3.6 × 1016 and 0.2-2.0 × 1016 α/mg, respectively.

  5. Synthesis and characterization of lead zirconate titanate powders obtained by the oxidant peroxo method

    Energy Technology Data Exchange (ETDEWEB)

    Camargo, Emerson R. [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Department of Chemistry, UFSCar-Federal University of Sao Carlos, Rod. Washington Luis km 235, CP 676, Sao Carlos SP, 13565-905 (Brazil)], E-mail: camargo@ufscar.br; Leite, Edson R. [LIEC-Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Department of Chemistry, UFSCar-Federal University of Sao Carlos, Rod. Washington Luis km 235, CP 676, Sao Carlos SP, 13565-905 (Brazil)], E-mail: derl@power.ufscar.br; Longo, Elson [Department of Biochemistry, Chemistry Institute of Araraquara, UNESP, Sao Paulo State University Rua Francisco Degni, CP 355 Araraquara SP, 14801-907 Brazil (Brazil)], E-mail: elson@iq.unesp.br

    2009-02-05

    Lead zirconate titanate (PbZr{sub 1-x}Ti{sub x}O{sub 3}) was synthesized by the 'oxidant peroxo method (OPM)' with 'x' between 0.25 and 0.50. Titanium metal was dissolved into a hydrogen peroxide/ammonia aqueous solution, followed by the addition of lead and zirconium nitrate solution. The amorphous precipitated precursor obtained was crystallized by heat treatment between 400 and 1000 deg. C. Images of transmission microscopy showed spherical particles with average diameter between 20 and 60 nm, and the presence of necks between particles treated at 700 deg. C. All of the unpressed powders were characterized by X-ray diffractometry and FT-Raman spectroscopy. Powder samples with 'x' up to 0.35 showed rhombohedral structure when treated at temperatures higher than 500 deg. C, and tetragonal structure when 'x' was higher than 0.40. Analysis of XRD and Raman spectroscopy of the precursor powders showed amorphous-like structures, however powders treated at 400 deg. C showed a structure identified as an intermediate pyrochlore phase, independently of the Zr and Ti mole ratio.

  6. Synthesis and characterization of lead zirconate titanate powders obtained by the oxidant peroxo method

    International Nuclear Information System (INIS)

    Camargo, Emerson R.; Leite, Edson R.; Longo, Elson

    2009-01-01

    Lead zirconate titanate (PbZr 1-x Ti x O 3 ) was synthesized by the 'oxidant peroxo method (OPM)' with 'x' between 0.25 and 0.50. Titanium metal was dissolved into a hydrogen peroxide/ammonia aqueous solution, followed by the addition of lead and zirconium nitrate solution. The amorphous precipitated precursor obtained was crystallized by heat treatment between 400 and 1000 deg. C. Images of transmission microscopy showed spherical particles with average diameter between 20 and 60 nm, and the presence of necks between particles treated at 700 deg. C. All of the unpressed powders were characterized by X-ray diffractometry and FT-Raman spectroscopy. Powder samples with 'x' up to 0.35 showed rhombohedral structure when treated at temperatures higher than 500 deg. C, and tetragonal structure when 'x' was higher than 0.40. Analysis of XRD and Raman spectroscopy of the precursor powders showed amorphous-like structures, however powders treated at 400 deg. C showed a structure identified as an intermediate pyrochlore phase, independently of the Zr and Ti mole ratio

  7. Spin-Ice Thin Films: Large-N Theory and Monte Carlo Simulations

    Science.gov (United States)

    Lantagne-Hurtubise, Étienne; Rau, Jeffrey G.; Gingras, Michel J. P.

    2018-04-01

    We explore the physics of highly frustrated magnets in confined geometries, focusing on the Coulomb phase of pyrochlore spin ices. As a specific example, we investigate thin films of nearest-neighbor spin ice, using a combination of analytic large-N techniques and Monte Carlo simulations. In the simplest film geometry, with surfaces perpendicular to the [001] crystallographic direction, we observe pinch points in the spin-spin correlations characteristic of a two-dimensional Coulomb phase. We then consider the consequences of crystal symmetry breaking on the surfaces of the film through the inclusion of orphan bonds. We find that when these bonds are ferromagnetic, the Coulomb phase is destroyed by the presence of fluctuating surface magnetic charges, leading to a classical Z2 spin liquid. Building on this understanding, we discuss other film geometries with surfaces perpendicular to the [110] or the [111] direction. We generically predict the appearance of surface magnetic charges and discuss their implications for the physics of such films, including the possibility of an unusual Z3 classical spin liquid. Finally, we comment on open questions and promising avenues for future research.

  8. Conventional and two step sintering of PZT-PCN ceramics

    Science.gov (United States)

    Keshavarzi, Mostafa; Rahmani, Hooman; Nemati, Ali; Hashemi, Mahdieh

    2018-02-01

    In this study, PZT-PCN ceramic was made via sol-gel seeding method and effects of conventional sintering (CS) as well as two-step sintering (TSS) were investigated on microstructure, phase formation, density, dielectric and piezoelectric properties. First, high quality powder was achieved by seeding method in which the mixture of Co3O4 and Nb2O5 powder was added to the prepared PZT sol to form PZT-PCN gel. After drying and calcination, pyrochlore free PZT-PCN powder was synthesized. Second, CS and TSS were applied to achieve dense ceramic. The optimum temperature used for 2 h of conventional sintering was obtained at 1150 °C; finally, undesired ZrO2 phase formed in CS procedure was removed successfully with TSS procedure and dielectric and piezoelectric properties were improved compared to the CS procedure. The best electrical properties obtained for the sample sintered by TSS in the initial temperature of T 1 = 1200 °C and secondary temperature of T 2 = 1000 °C for 12 h.

  9. A parity-breaking electronic nematic phase transition in the spin-orbit coupled correlated metal Cd2Re2O7

    Science.gov (United States)

    Harter, J. W.; Zhao, Z. Y.; Yan, J.-Q.; Mandrus, D. G.; Hsieh, D.

    Strong interactions between electrons are known to drive metallic systems toward a variety of well-known symmetry-broken phases, including superconducting, electronic liquid crystalline, and charge- and spin-density wave ordered states. In contrast, the electronic instabilities of correlated metals with strong spin-orbit coupling have only recently begun to be explored. We uncover a novel multipolar nematic phase of matter in the metallic pyrochlore Cd2Re2O7 using spatially-resolved second-harmonic optical anisotropy measurements. Like previously discovered electronic liquid crystalline phases, this multipolar nematic phase spontaneously breaks rotational symmetry while preserving translational invariance. However, it has the distinguishing property of being odd under spatial inversion, which is allowed only in the presence of spin-orbit coupling. By examining the critical behavior of the multipolar nematic order parameter, we show that it drives the thermal phase transition near 200 K in Cd2Re2O7 and induces a parity-breaking lattice distortion as a secondary order parameter.

  10. Europium-Doped Lanthanum Hafnate Nanoparticles: Structure, Photoluminescence, and Radioluminescence

    Science.gov (United States)

    Wahid, Kareem; Pokhrel, Madhab; Mao, Yuanbing

    Due to their novel physical properties, nanostructured phosphors are of interest for radiation-based imaging and therapeutics. Herein, the structural and luminescent properties of europium-doped lanthanum hafnate (La2Hf2O7:xmol%Eu3+, x = 0 - 35) nanoparticles are investigated for use as scintillators. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy confirm samples prepared through a combined co-precipitation and low-temperature molten salt synthetic process homogenously form spherical nanocrystals of 36 nm in the ordered pyrochlore phase. Ultraviolet and X-ray excitation of these samples induce strong red emissions in the 580 - 590 and 612 - 630 nm range corresponding to the 5D0->7 F1 magnetic dipole and 5D0->7 F2 electric dipole transitions of Eu3+. Optical response and quantum yield are optimized at 5% Eu3+; a proposed trade-off between quenching mechanisms (defect-states/cross-relaxation) and dopant concentration is discussed. Owing to their high density, large effective atomic number, and bright luminescence, these La2Hf2O7:xmol%Eu3+ nanoparticles warrant further investigation for scintillator applications. The authors thank the support from the Defense Threat Reduction Agency of the U.S. Department of Defense (award #HDTRA1- 10-1-0114).

  11. Characterisation of lead barium zirconate thin films for utilisation of the electrocaloric effect

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, C.P., E-mail: c.p.shaw@cranfield.ac.uk [Surface Engineering and Nanotechnology Institute, Manufacturing and Materials Department, Cranfield University, Cranfield, Bedfordshire MK43 0AL (United Kingdom); Zhang, Qi, E-mail: q.zhang@cranfield.ac.uk [Surface Engineering and Nanotechnology Institute, Manufacturing and Materials Department, Cranfield University, Cranfield, Bedfordshire MK43 0AL (United Kingdom); Correia, T.M., E-mail: Tatiana.correia@ktn-uk.org [Knowledge Transfer Network (United Kingdom); Weaver, P.M., E-mail: paul.weaver@innotecuk.com [InotekUK (United Kingdom)

    2016-08-01

    Characterisation of a composition of Lead Barium Zirconate thin films deposited by a spin coating sol-gel process onto platinised silicon substrates has been undertaken to investigate a potential application utilising the reported electrocaloric properties of the material. Xray diffraction studies revealed that above 700 °C the presence of pyrochlore phase was replaced by ferroelectric phase but the identification of antiferroelectric phases previously reported could not be identified. Wet etching of the films produced an insoluble residue containing only evidence of zirconium out of the original three metals, which resembled a skeletal structure similar to the original rosette morphology of the annealed films. Elemental analysis of the annealed films using EDX indicated a non-target Pb:Ba:Zr ratio, which suggested a reduced Zr content of the films. “Solution-like” rather than “sol-like” nature of the spin coated sol and phase boundary proximity are proposed for reported observations, and a mechanism is proposed to account for the unusual observed trend in dielectric constant. - Highlights: • Characterisation of sol-gel deposited Lead barium zirconnate films. • Absence of previously reported antiferroelectric phase. • Identification of proposed non-PBZ phase. • Anomalous increase in film capacitance with thickness interpreted.

  12. High-pressure Raman and optical absorption studies on lead pyroniobate (Pb2Nb2O7) and pressure-induced phase transitions

    International Nuclear Information System (INIS)

    Jayaraman, A.; Kourouklis, G.A.; Cooper, A.S.; Espinosa, G.P.

    1990-01-01

    High-pressure Raman scattering and optical absorption studies have been carried out on lead pyroniobate (Pb 2 Nb 2 O 7 ) up to 33 GPa, using a gasketed diamond anvil cell. The Raman study reveals the occurrence of two, possibly three, pressure-induced phase changes; a rather subtle change is indicated near 4.5 GPa. The transition near 13 GPa is attributed to a structural transition from the rhombohedral to the cubic pyrochlore structure. The third phase change occurs near 20 GPa. From the broad Raman feature that is observed at about 800 cm -1 , it is concluded that the system turns amorphous at pressures above 20 GPa. The amorphous phase recrystallizes to the original rhombohedral phase, on release of pressure. The broad Raman peaks of the recrystallized phase indicate a high degree of disorder in the material. Lead pyroniobate turns deep red near 30 GPa, from light yellow at ambient pressure. Semi quantitative absorption measurements show that the energy gap shifts red at a rate of 30 meV/GPa. This shift is attributed to the downward motion of the 5d (es) conduction band of Pb

  13. Radiation-induced microcrystal shape change as a mechanism of wasteform degradation

    Science.gov (United States)

    Ojovan, Michael I.; Burakov, Boris E.; Lee, William E.

    2018-04-01

    Experiments with actinide-containing insulating wasteforms such as devitrified glasses containing 244Cm, Ti-pyrochlore, single-phase La-monazite, Pu-monazite ceramics, Eu-monazite and zircon single crystals containing 238Pu indicate that mechanical self-irradiation-induced destruction may not reveal itself for many years (even decades). The mechanisms causing these slowly-occurring changes remain unknown therefore in addition to known mechanisms of wasteform degradation such as matrix swelling and loss of solid solution we have modelled the damaging effects of electrical fields induced by the decay of radionuclides in clusters embedded in a non-conducting matrix. Three effects were important: (i) electric breakdown; (ii) cluster shape change due to dipole interaction, and (iii) cluster shape change due to polarisation interaction. We reveal a critical size of radioactive clusters in non-conducting matrices so that the matrix material can be damaged if clusters are larger than this critical size. The most important parameters that control the matrix integrity are the radioactive cluster (inhomogeneity) size, specific radioactivity, and effective matrix electrical conductivity. We conclude that the wasteform should be as homogeneous as possible and even electrically conductive to avoid potential damage caused by electrical charges induced by radioactive decay.

  14. Effect of composition on thermal conductivity of MgO–Nd2Zr2O7 composites for inert matrix materials

    International Nuclear Information System (INIS)

    Nelson, A.T.; Giachino, M.M.; Nino, J.C.; McClellan, K.J.

    2014-01-01

    Inert matrix fuels based on magnesium oxide (MgO) as the inert phase have been of historic interest due to its high thermal conductivity. Minor actinide-bearing phases possessing an A 2 B 2 O 7 pyrochlore structure are also believed to contain a range of favorable attributes, suggesting a possible pairing with MgO to yield a high performance inert matrix fuel. The thermal diffusivity, heat capacity, and thermal expansion of MgO–Nd 2 Zr 2 O 7 composites were measured from room temperature to 1273 K, where the MgO phase content was varied from 40 to 70 volume percent. The thermal conductivity of each composition was calculated using these results and then compared to widely employed methods to approximate the thermal conductivity of composite materials based upon the properties of the constituent phases. Results suggest that use of either a rule of mixtures or geometric mean approximation for the thermal conductivity of composite systems such as this one would be subject to significant uncertainties when the constituent properties widely differ. A sigmoidal average of the upper and lower Hashin–Shtrikman bounds was found to be in good agreement with the thermal conductivity of the composites as determined experimentally

  15. Steam regenerative removal of hydrogen sulfide from hot syngas by a novel tin oxide and yttrium oxide sorbent

    International Nuclear Information System (INIS)

    Yang, Yi; Shi, Yixiang; Cai, Ningsheng

    2017-01-01

    A novel H 2 S sorbent based on SnO 2 and Y 2 O 3 is developed by a co-precipitation method for steam regenerative removal of H 2 S from hot syngas at moderate temperatures (400–500 °C). SnO 2 -Y 2 O 3 sorbent is stable in a reducing atmosphere (i.e. 500 °C, 50% H 2 ) and achieves a 99.9% H 2 S removal during successive desulfurization and regeneration cycles. The addition of yttrium to SnO 2 decreases the reduction property of SnO 2 and no metallic Sn exists in the reducing atmosphere due to the formation of a pyrochlore-type compound, Y 2 Sn 2 O 7 . The SnO 2 -Y 2 O 3 sorbent has a desulfurization performance deterioration with the increasing calcination temperature. The newly developed SnO 2 -Y 2 O 3 sorbent can be regenerated by steam at 500 °C. In the eight successive desulfurization and regeneration cycles, SnO 2 -Y 2 O 3 sorbent has a cyclic breakthrough sulfur capacity of 9 mg/g without significant sulfur capacity loss. - Highlights: • Reversible warm gas H 2 S clean up. • Suppressing SnO 2 reduction by formation of Sn 2 Y 2 O 7 . • Sn2Y-700 steam regeneration and cycling characterization.

  16. Doped nanocrystalline ZnO powders for non-linear resistor applications by spray pyrolysis method.

    Science.gov (United States)

    Hembram, Kaliyan; Vijay, R; Rao, Y S; Rao, T N

    2009-07-01

    Homogeneous and doped nanocrystalline ZnO powders (30-200 nm) were synthesized by spray pyrolysis technique. The spray pyrolysed powders were calcined in the temperature range of 500-750 degrees C. Formation of insulating pyrochlore phase started from 700 degrees C during the calcination itself. The calcined powders were compacted and sintered at different temperatures ranging from 900-1200 degrees C for 0.5-4 h. The densification behavior was found to be dependent on calcination temperature of the nanopowder. The resulting discs were found to have density (5.34-5.62 g/cc) in the range of 96-99% of theoretical density. The breakdown voltage value obtained for the nanopowder based non-linear resistor is 10.3 kV/cm with low leakage current density of 0.7 microA/cm2 and coefficient of nonlinearity as high as 193. The activation energy for grain growth of the doped ZnO nanopowder powders is 449.4 +/- 15 kJ/mol.

  17. Unveiling the Role of CNTs on the Phase Formation of 1D Ferroelectrics

    KAUST Repository

    Mahajan, Amit

    2015-05-21

    Carbon nanotubes (CNTs) have the potential to act as templates or bottom electrodes for three dimension (3D) capacitor arrays, which utilise one dimension (1D) ferroelectric nanostructures to increase memory size and density. However, growing a ferroelectric on the surface of CNTs is non-trivial. Here, we demonstrate that multi-walled (MW) CNTs decrease the time and temperature for formation of lead zirconium titanate Pb(Zr1-xTix)O3 (PZT) by ~100 ºC commensurate with a decrease in activation energy from 68±15 kJ/mol to 27±2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 ºC for MWCNTs/PZT whereas for pure PZT traces of pyrochlore were still present at 650 ºC, where PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNT/PZT synthesised at 500 ºC for 1 h was proved. Although further work is required to prove the concept of 3D capacitor arrays, our result suggests that it is feasible to utilise MWCNTs as templates/electrodes for the formation of 1D PZT nano ferroelectrics.

  18. Comparative assessment of the European and Latin American scenarios for NORM/TENORM exposure

    International Nuclear Information System (INIS)

    Steinhaeusler, F.; Paschoa, A.S.

    2002-01-01

    The geological formation of the areas of high natural radioactivity are usually associated with mineral ores commercially important. As a consequence, extracting industries are installed in or near those areas. Several industrial products and byproducts can be obtained from thorium, uranium and potassium rich mineral ores, for example: niobium concentrate from pyrochlore; monazite, ilmenite, rutile and zirconite concentrates from monazite sands; phosphate fertilizers from apatite; tin and lead from cassiterite; gold and copper form a variety of thorium and uranium rich mineral matrices. Other industries like oil- and natural gas production and processing, production of thoriated tungsten lamps, welding, gas mantles and pigments produce non-negligible amounts of wastes containing technologically enhanced naturally occurring radioactive materials (TENORM). In addition, quite frequently unknown amounts of natural radionuclides end up embedded in a variety of consumer products. Thus, naturally occurring radioactive materials (NORM) as well as TENORM in consumer products and/or industrial wastes may be of importance as far as human exposures are concerned. This work will present a comparative assessment of the radiological significance of different NORM/TENORM exposure scenarios in Europe and Latin America. (author)

  19. Effect of Nd Doping on Dielectric and Impedance Properties of PZT Nanoceramics

    Science.gov (United States)

    Kour, P.; Pradhan, S. K.; Kumar, Pawan; Sinha, S. K.; Kar, Manoranjan

    2018-02-01

    Neodymium-doped lead zirconate tianate, i.e. Pb1-x Nd x Zr0.52Ti0.48O3 (PNZT) ceramics, with x = 0-10 mol.% has been prepared by the sol-gel process. X-ray diffraction pattern at room temperature shows the pyrochlore free phase for all samples. The structural analysis suggests the coexistence of both rhombohedral (R3m space group) and tetragonal (P4 mm space group) crystal symmetries. Scanning electron micrographs of the samples show uniform distribution of grain and grain boundaries. Dielectric constant increases with the increase in neodymium concentration in the crystal lattice. Degree of diffuse phase transition increases with the increase in Nd3+ concentration in the sample. Nd3+ incorporation into the lead zirconatetitanate (PZT) lattice enhances the spreading factor. Interaction between neighbouring dipoles decreases with the increase of Nd3+ in PZT lattice. The conduction mechanism of the sample can be attributed to the overlapping large polar tunnelling. Second-order dielectric phase transition has been observed at the Curie temperature. The electrical properties of the sample can be explained by considering grain and grain boundaries contributions. All the samples show the poly-dispersive non-Debye type relaxation.

  20. Synthesis, Characterization and Thermal Diffusivity of Holmium and Praseodymium Zirconates

    Directory of Open Access Journals (Sweden)

    Stopyra M.

    2016-06-01

    Full Text Available A2B2O7 oxides with pyrochlore or defected fluorite structure are among the most promising candidates for insulation layer material in thermal barrier coatings. The present paper presents the procedure of synthesis of holmium zirconate Ho2Zr2O7 and praseodymium zirconate Pr2Zr2O7 via Polymerized-Complex Method (PCM. Thermal analysis of precursor revealed that after calcination at relatively low temperature (700°C fine-crystalline, single-phase material is obtained. Thermal diffusivity was measured in temperature range 25-200°C, Ho2Zr2O7 exhibits lower thermal diffusivity than Pr2Zr2O7. Additionally, PrHoZr2O7 was synthesized. The powder in as-calcined condition is single-phase, but during the sintering decomposition of solid solution took place and Ho-rich phase precipitated. This material exhibited the best insulating properties among the tested ones.

  1. Spin-strain effects in the frustrated magnet Tb{sub 2}Ti{sub 2}O{sub 7} at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Gritsenko, Y.; Wosnitza, J. [HZDR/HLD, Dresden (Germany); TUD/IFP, Dresden (Germany); Zherlitsyn, S. [HZDR/HLD, Dresden (Germany); Ruminy, M.; Fennell, T. [PSI/LNS, 5232 Villigen PSI (Switzerland); Kenzelmann, M. [PSI/LDM, 5232 Villigen PSI (Switzerland)

    2016-07-01

    Geometrically frustrated magnets have attracted much attention, due to their tendency to build unconventional ground states with exotic excitations. Tb{sub 2}Ti{sub 2}O{sub 7} possesses a pyrochlore lattice as building block of the crystallographic structure, providing a basis for geometric frustration. This cubic material features Curie-Weiss temperature of Θ{sub CW} = -19 K, but no long-range magnetic order has been detected down to 50 mK indicating a large frustration. The existence of a spin-liquid state has been suggested for Tb{sub 2}Ti{sub 2}O{sub 7}. Here, we present results of ultrasonic investigations of this material. The magnetic field was applied along the [110] direction at temperatures of 20, 150 and 300 mK. Clear anomalies were found for different acoustic modes. The temperature dependence of the sound velocity shows a softening at about 500 mK and step-like features at about 150 mK suggesting a low-temperature phase transformation. This investigation sheds new light on the role of lattice degrees of freedom and magneto-elastic interactions in this material.

  2. Atomistic simulations of the radiation resistance of oxides

    International Nuclear Information System (INIS)

    Chartier, A.; Van Brutzel, L.; Crocombette, J.-P.

    2012-01-01

    Fluorite compounds such as urania and ceria, or related compounds such as pyrochlores and also spinels show different behaviors under irradiations, which ranges from perfect radiation resistance to crystalline phase change or even complete amorphization depending on their structure and/or their composition. Displacement cascades – dedicated to the understanding of the ballistic regime and performed by empirical potentials molecular dynamics simulations – have revealed that the remaining damages of the above mentioned oxides are reduced to point defects unlike what is observed in zircon and zirconolite, which directly amorphize during the cascade. The variable behavior of these point defects is the key of the various responses of these materials to irradiations. This behavior can be investigated by two specific molecular dynamics methodologies that will be reviewed here: (i) the method of point defects accumulation as a function of temperature that gives access to the dose effects and to the critical doses for amorphization; (ii) the study Frenkel pairs life-time – i.e. their time of recombination as function of temperature – that may be used as a tool to understand the results obtained in displacements cascades or to identify the microscopic mechanisms responsible for the amorphization/re-crystallization during the point defects accumulations.

  3. Review and Perspectives of Aurivillius Structures as a Lead-Free Piezoelectric System

    Directory of Open Access Journals (Sweden)

    Alberto Moure

    2018-01-01

    Full Text Available According to the EU-Directives 2002/95/EC, 2002/96/EC, lead-based piezoceramics must be substituted in the future with more environmentally friendly alternatives, only when a reliable alternative is found. This is why an increasing interest has grown in the research community to find lead free piezoelectric materials that fulfil the requirements for this substitution. Different families of compounds have been shown to be possible candidates for this use, such as bismuth and niobates based perovskites, pyrochlores, etc. However, a material with piezoelectric coefficients similar to those of PZT (lead zirconate titanate, Pb[ZrxTi1-x]O3 has not been yet found. Besides, each of these families has its specific characteristics in terms of remnant polarization, coercive field or application temperature. Thus, the choice of each material should be made according to the specific needs of the application. In this sense, Aurivillius-type structure materials (also known as Bismuth Layered Structure Ferroelectrics, BLSF can take advantage of their specific properties for uses as Lead Free Piezoelectric systems. Some of them have a high Curie temperature, which make them good candidates to be used as high temperature piezoelectrics; high coercive fields, which facilitates their use as actuators; or a high switching fatigue resistance, which can be useful for future applications as Ferroelectric Random Access Memories (FERAM.

  4. Mechanism of mechanochemical synthesis of complex oxides and the peculiarities of their nano-structurization determining sintering

    Directory of Open Access Journals (Sweden)

    Zyryanov V.V.

    2005-01-01

    Full Text Available A mechanism of superfast mechanosynthesis reaction for oxide systems is proposed on the base of a dynamics study. The threshold effect and linear dependence of the chemical response on the effective temperature of the reaction zone are established. Major factors are determined: molecular mass of reagents, enthalpy and difference of reagents in Mohs’s hardness, which also influence the composition of the primary product. Primary acts are characterized by a superfast roller mechanism of mass transfer with the formation of a transient dynamic state (D*. Secondary acts slowly approximate the composition of the product to the composition of the starting mixture by diffusion mass transfer in a deformation mixing regime with a contribution of a rotation (roller mechanism. The list of structure types for complex oxides derived by mechanosynthesis includes perovskites, fluorites, pyrochlors, sheelites, and some other ones. Powders of crystal products display multilevel structurization. In all studied complex oxides strong disordering of the “anti-glass” type was observed. The mechanism of sintering was studied in BaTiO3 powders of different origin and in metastable complex oxides derived by mechanosynthesis. The major contribution in shrinkage belongs to rearrangements of crystalline particles as a whole. Structure transformations accompany, as a rule, sintering of inhomogeneous powders derived by mechanosynthesis.

  5. Ion Irradiation Damage in Zirconate and Titanate Ceramics for Pu Disposition

    International Nuclear Information System (INIS)

    Stewart, Martin W.; Begg, Bruce D.; Finnie, K.; Colella, Michael; Li, H.; McLeod, Terry; Smith, Katherine L.; Zhang, Zhaoming; Weber, William J.; Thevuthasan, Suntharampillai

    2004-01-01

    In this paper, we discuss the effect of ion irradiation on pyrochlore-rich titanate and defect-fluorite zirconate ceramics designed for plutonium immobilization. Samples, with Ce as an analogue for Pu, were made via oxide routes and consolidated by cold-pressing and sintering. Ion irradiation damage was carried out with 2 MeV Au2+ ions to a fluence of 5 ions nm-2 in the accelerator facilities within the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory. Irradiated and non-irradiated samples were examined by x-ray diffraction, scanning and transmission electron microscopy, x-ray photoelectron and infrared spectroscopy, and spectroscopic ellipsometry. Samples underwent accelerated leach testing at pH 1.75 (nitric acid) at 90 C for 28 days. The zirconate samples were more ion-irradiation damage resistant than the titanate samples, showing little change after ion-irradiation whereas the titanate samples formed an amorphous surface layer ∼ 500 nm thick. While all samples had high aqueous durability, the titanate leach rate was ∼ 5 times that of the zirconate. The ion-irradiation increased the leach rate of the titanate without impurities by ∼ 5 times. The difference in the leach rates between irradiated and unirradiated zirconate samples is small. However, the zirconates were less able to incorporate impurities than the titanate ceramics and required higher sintering temperatures, ∼ 1500 C compared to 1350 C for the titanates.

  6. Crystallinity and electrical properties of neodymium-substituted bismuth titanate thin films

    International Nuclear Information System (INIS)

    Chen, Y.-C.; Hsiung, C.-P.; Chen, C.-Y.; Gan, J.-Y.; Sun, Y.-M.; Lin, C.-P.

    2006-01-01

    We report on the properties of Nd-substituted bismuth titanate Bi 4-x Nd x Ti 3 O 12 (BNdT) thin films for ferroelectric non-volatile memory applications. The Nd-substituted bismuth titanate thin films fabricated by modified chemical solution deposition technique showed much improved properties compared to pure bismuth titanate. A pyrochlore free crystalline phase was obtained at a low annealing temperature of 640 deg. C and grain size was found to be considerably increased as the annealing temperature increased. The film properties were found to be strongly dependent on the Nd content and annealing temperatures. The measured dielectric constant of BNdT thin films was in the range 172-130 for Bi 4-x Nd x Ti 3 O 12 with x 0.0-0.75. Ferroelectric properties of Nd-substituted bismuth titanate thin films were significantly improved compared to pure bismuth titanate. For example, the observed 2P r and E c for Bi 3.25 Nd 0.75 Ti 3 O 12 , annealed at 680 deg. C, were 38 μC/cm 2 and 98 kV/cm, respectively. The improved microstructural and ferroelectric properties of BNdT thin films suggest their suitability for high density ferroelectric random access memory applications

  7. Titanate ceramics for immobilisation of uranium-rich radioactive wastes arising from {sup 99}Mo production

    Energy Technology Data Exchange (ETDEWEB)

    Carter, M.L.; Li, H. [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, Sydney, NSW 2232 (Australia); Zhang, Y. [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, Sydney, NSW 2232 (Australia)], E-mail: yzx@ansto.gov.au; Vance, E.R.; Mitchell, D.R.G. [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, Sydney, NSW 2232 (Australia)

    2009-02-28

    Uranium-rich liquid wastes arising from UO{sub 2} targets which have been neutron-irradiated to generate medical radioisotopes such as {sup 99m}Tc require immobilisation. A pyrochlore-rich hot isostatically pressed titanate ceramic can accommodate at least 40 wt% of such waste expressed on an oxide basis. In this paper, the baseline waste form composition (containing 40 wt% UO{sub 2}) was adjusted in two ways: (a) varying the UO{sub 2} loading with constant precursor oxide materials, (b) varying the precursor composition with constant waste loading of UO{sub 2}. This resulted in the samples having a similar phase assemblage but the amounts of each phase varied. The oxidation states of U in selected samples were determined using diffuse reflection spectroscopy (DRS) and electron energy loss spectroscopy (EELS). Leaching studies showed that there was no significant difference in the normalised elemental release rates and the normalised release rates are comparable with those from synroc-C. This demonstrates that waste forms based on titanate ceramics are robust and flexible for the immobilisation of U-rich waste streams from radioisotope processing.

  8. Ba{sub 2.2}Ca{sub 0.8}Mg{sub 4}F{sub 14}, a new ''solid solution stabilized'' matrix for an intense blue phosphor

    Energy Technology Data Exchange (ETDEWEB)

    Kubel, F.; Pantazi, M. [TU Vienna, Inst. of Chemical Technologies and Analytics, Getreidemarkt 9, 164-SC, 1060 Vienna (Austria); Hagemann, H. [Departement de Chimie Physique, Universite de Geneve, 30, quai E.Ansermet, 1211 Geneva 4 (Switzerland)

    2011-09-15

    Barium calcium magnesium fluoride (Ba{sub 2}(Ba{sub x}Ca{sub 1-x})Mg{sub 4}F{sub 14}, x=0.19-0.26) has been synthesized at 850 C from precursors prepared by the solution precipitation method. Single crystals with composition of Ba{sub 2.200(2)}Ca{sub 0.800(2)}Mg{sub 4}F{sub 14}were obtained after prolonged heating. Lattice parameters from single crystal data are a = 12.4203(8) and c = 7.4365(5) A [tetragonal, space group P4{sub 2}/mnm (No. 136)]. They increase with increasing barium concentration within a given stability window. The structure is built of a network of MgF{sub 6} octahedra forming a pyrochlore related channel system and isolated fluorine ions. Within the channels, heavy alkaline earth ions are located. The wide channel is filled with off-center positioned barium ions. The channel with a narrow cross section hosts both ions, Ca{sup 2+}and Ba{sup 2+}. The structure is isotypic with Pb{sub 3}Nb{sub 4}O{sub 12}F{sub 2} but has a different coordination around Ba/Ca and Pb, respectively. Doped with {proportional_to}1% Eu(II), the compound shows intense blue luminescence under UV activation. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  9. Ruthenium(V) oxides from low-temperature hydrothermal synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hiley, Craig I.; Walton, Richard I. [Department of Chemistry, University of Warwick, Coventry (United Kingdom); Lees, Martin R. [Department of Physics, University of Warwick, Coventry (United Kingdom); Fisher, Janet M.; Thompsett, David [Johnson Matthey Technology Centre, Reading (United Kingdom); Agrestini, Stefano [Max-Planck Institut, CPfS, Dresden (Germany); Smith, Ronald I. [ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Harwell Oxford, Didcot (United Kingdom)

    2014-04-22

    Low-temperature (200 C) hydrothermal synthesis of the ruthenium oxides Ca{sub 1.5}Ru{sub 2}O{sub 7}, SrRu{sub 2}O{sub 6}, and Ba{sub 2}Ru{sub 3}O{sub 9}(OH) is reported. Ca{sub 1.5}Ru{sub 2}O{sub 7} is a defective pyrochlore containing Ru{sup V/VI}; SrRu{sub 2}O{sub 6} is a layered Ru{sup V} oxide with a PbSb{sub 2}O{sub 6} structure, whilst Ba{sub 2}Ru{sub 3}O{sub 9}(OH) has a previously unreported structure type with orthorhombic symmetry solved from synchrotron X-ray and neutron powder diffraction. SrRu{sub 2}O{sub 6} exhibits unusually high-temperature magnetic order, with antiferromagnetism persisting to at least 500 K, and refinement using room temperature neutron powder diffraction data provides the magnetic structure. All three ruthenates are metastable and readily collapse to mixtures of other oxides upon heating in air at temperatures around 300-500 C, suggesting they would be difficult, if not impossible, to isolate under conventional high-temperature solid-state synthesis conditions. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Size-dependent characteristics of ultra-fine oxygen-enriched nanoparticles in austenitic steels

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Yinbin, E-mail: ymiao@anl.gov [Argonne National Laboratory, Lemont, IL 60439 (United States); University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Mo, Kun [Argonne National Laboratory, Lemont, IL 60439 (United States); Zhou, Zhangjian [University of Science and Technology Beijing, Beijing 100082 (China); Liu, Xiang; Lan, Kuan-Che [University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Zhang, Guangming [University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); University of Science and Technology Beijing, Beijing 100082 (China); Miller, Michael K.; Powers, Kathy A. [Oak Ridge National Laboratory, Oak Ridge, TN 37830 (United States); Stubbins, James F. [University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, Fukuoka 819-0395 (Japan)

    2016-11-15

    Here, a coordinated investigation of the elemental composition and morphology of ultra-fine-scale nanoparticles as a function of size within a variety of austenitic oxide dispersion-strengthened (ODS) steels is reported. Atom probe tomography was utilized to evaluate the elemental composition of these nanoparticles. Meanwhile, the crystal structures and orientation relationships were determined by high-resolution transmission electron microscopy. The nanoparticles with sufficient size (>4 nm) to maintain a Y{sub 2}Ti{sub 2−x}O{sub 7−2x} stoichiometry were found to have a pyrochlore structure, whereas smaller Y{sub x}Ti{sub y}O{sub z} nanoparticles lacked a well-defined structure. The size-dependent characteristics of the nanoparticles in austenitic ODS steels differ from those in ferritic/martensitic ODS steels. - Highlights: • The structural and chemical characteristics of nanoparticles are revealed. • Nanoparticles' crystal structure and elemental composition are size-dependent. • Characteristics of austenitic ODS steels are compared to that of an F/M ODS steel. • Hypothesis about the formation mechanism of nanoparticles is proposed accordingly.

  11. Characterization of energy conversion of multiferroic PFN and PFN:Mn

    Directory of Open Access Journals (Sweden)

    Lucjan Kozielski

    2013-12-01

    Full Text Available Characterization of energy conversion of multiferroic materials is concerned with multifunctional properties of materials, a topic that is fascinating from the scientific point of view and important for the modern technology. The complex characterization of multiferroic structures suffers at present from lack of a systematic experimental approach and deficiency of multifunctional magnetoelectric properties testing capabilities. Compactness and high frequency energy conversion capacity are the main reasons of invention and improvement of sophisticated materials which are prepared for high-speed computer memories and broadband transducer devices. As a consequence, one can easily notice an intense search for new materials for generation, transformation and amplification of magnetic and electric energies. In this scenario, the combination of excellent piezoelectric and magnetic properties makes lead iron niobate Pb(Fe1/2Nb1/2O3 (PFN an attractive host material for application in integrated magnetoelectric energy conversion applications. PFN multiferroic materials are attractive for commercial electroceramics due to high value of dielectric permittivity and magnetoelectric coefficients as well as relatively easy synthesis process. However, synthesis of PFN ceramics is mostly connected with formation of the secondary unwanted pyrochlore phase associated with dramatic decrease of ferroelectric properties. The authors have successfully reduced this negative phenomenon by Mn doping and finally present high piezoelectric and magnetoelectric energy conversion efficiency in fabricated PMFN ceramics.

  12. Status of plutonium ceramic immobilization processes and immobilization forms

    International Nuclear Information System (INIS)

    Ebbinghaus, B.B.; Van Konynenburg, R.A.; Vance, E.R.; Jostsons, A.

    1996-01-01

    Immobilization in a ceramic followed by permanent emplacement in a repository or borehole is one of the alternatives currently being considered by the Fissile Materials Disposition Program for the ultimate disposal of excess weapons-grade plutonium. To make Pu recovery more difficult, radioactive cesium may also be incorporated into the immobilization form. Valuable data are already available for ceramics form R ampersand D efforts to immobilize high-level and mixed wastes. Ceramics have a high capacity for actinides, cesium, and some neutron absorbers. A unique characteristic of ceramics is the existence of mineral analogues found in nature that have demonstrated actinide immobilization over geologic time periods. The ceramic form currently being considered for plutonium disposition is a synthetic rock (SYNROC) material composed primarily of zirconolite (CaZrTi 2 O 7 ), the desired actinide host phase, with lesser amounts of hollandite (BaAl 2 Ti 6 O 16 ) and rutile (TiO 2 ). Alternative actinide host phases are also being considered. These include pyrochlore (Gd 2 Ti 2 O 7 ), zircon (ZrSiO 4 ), and monazite (CePO 4 ), to name a few of the most promising. R ampersand D activities to address important technical issues are discussed. Primarily these include moderate scale hot press fabrications with plutonium, direct loading of PuO 2 powder, cold press and sinter fabrication methods, and immobilization form formulation issues

  13. Double exchange model on triangular lattice: Non-coplanar spin configuration and phase transition near quarter filling

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, G.P., E-mail: bugubird_zhang@hotmail.com [Department of Physics, Renmin University of China, Beijing 100872 (China); Zhang, Jian [3M Company, 3M Corporate Headquarters, 3M Center, St. Paul, MN 55144-1000 (United States); Zhang, Qi-Li [Data Center for High Energy Density Physics, Institute of Applied Physics and Computational Mathematics, Beijing 100094 (China); Zhou, Jiang-Tao [College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060 (China); Shangguan, M.H. [Department of Physics, Renmin University of China, Beijing 100872 (China)

    2013-05-15

    Unconventional anomalous Hall effect in frustrated pyrochlore oxides is originated from spin chirality of non-coplanar localized spins, which can also be induced by the competition between ferromagnetic (FM) double exchange interaction J{sub H} and antiferromagnetic superexchange interaction J{sub AF}. Here truncated polynomial expansion method and Monte Carlo simulation are adopted to investigate the above model on two-dimensional triangular lattice. We discuss the influence of the range of FM-type spin–spin correlation and strong electron–spin correlation on the truncation error of spin–spin correlation near quarter filling. Two peaks of the probability distribution of spin–spin correlation in non-coplanar spin configuration clearly show that non-coplanar spin configuration is an intermediate phase between FM and 120° spin phase. Near quarter filling, there is a phase transition from FM into non-coplanar and further into 120° spin phase when J{sub AF} continually increases. Finally the effect of temperature on the magnetic structure is discussed.

  14. Ceramics like PZT-PMN

    International Nuclear Information System (INIS)

    Droescher, R.E.; Sousa, V.C.; Bergman, C.P.

    2009-01-01

    The goal of this work was to achieve piezoelectric ceramics referring to the system PZT-PMN Pb(Mg 1 / 3 Nb 2 / 3 Zr 0 , 52 Ti 0 , 48 )O 3 . Have been analysed ceramics like 0,65PZT-0,35PMN ((Pb(Mg 0 , 1167 Nb 0 , 2300 Zr 0 , 3380 Ti 0 , 3120 )O 3 ), 0,75PZT-0,25PMN ((Pb(Mg 0 , 083 Nb 0 . 1675 Zr 0 , 3900 Ti 0 , 3600 )O3) and the 0,85PZT-0,15PMN ((Pb(Mg 0,0500 Nb 0 , 1000 Zr 0 , 4420 Ti 0 , 4080 )O 3 ). The influence of the calcination and concentration of PZT on the lattice phases, microstructure and density was evaluated. Then, the method used was the mixed-oxide method, the samples were taken under different temperatures of calcination before the final sinterizing. The DRX and SEM techniques were used to identify the phases formed and analyse the microstructure, respectively. The main result revealed that, the better way is to realize three burns before the final sinterizing at 1200 o C/4 h . Like that, on obtain for sure the average lattice phases, like: perovskite, pyrochlore and PbO and also tend to densify the samples. (author)

  15. Transmutation of americium and curium incorporated in zirconia-based host materials

    Energy Technology Data Exchange (ETDEWEB)

    Raison, P.E. [CEA Cadarache, 13 - Saint-Paul-lez-Durance (France). Dept. d' Etudes des Combustibles; Haire, R.G. [Oak Ridge National Lab., TN (United States)

    2001-07-01

    Presented are studies involving the incorporation of americium and curium in zirconia-based materials. First explored was the pseudo ternary system AmO{sub 2}-ZrO{sub 2}-Y{sub 2}O{sub 3}. It was determined that selected Y-CSZ materials can incorporate significant quantities of americium oxide and remain cubic single-phase. The cell parameters of these fluorite-type products were established to be linear with the AmO{sub 2} content. The Cm{sub 2}O{sub 3}-ZrO{sub 2} system was also investigated. It was found that at 25 mol% of CmO{sub 1.5}, the Cm(III) stabilized zirconia in its cubic form (a = 5.21 {+-}0.01 Angstrom). At higher and lower concentrations, diphasic materials were encountered. At 50 mol% of CmO{sub 1.5}, a pyrochlore oxide - Cm{sub 2}Zr{sub 2}O{sub 7} - is formed (a = 10.63 {+-}0.02 Angstrom). (author)

  16. Plume-related mantle source of super-large rare metal deposits from the Lovozero and Khibina massifs on the Kola Peninsula, Eastern part of Baltic Shield: Sr, Nd and Hf isotope systematics

    Science.gov (United States)

    Kogarko, L. N.; Lahaye, Y.; Brey, G. P.

    2010-03-01

    The two world’s largest complexes of highly alkaline nepheline syenites and related rare metal loparite and eudialyte deposits, the Khibina and Lovozero massifs, occur in the central part of the Kola Peninsula. We measured for the first time in situ the trace element concentrations and the Sr, Nd and Hf isotope ratios by LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometer) in loparite, eudialyte an in some other pegmatitic minerals. The results are in aggreement with the whole rock Sr and Nd isotope which suggests the formation of these superlarge rare metal deposits in a magmatic closed system. The initial Hf, Sr, Nd isotope ratios are similar to the isotopic signatures of OIB indicating depleted mantle as a source. This leads to the suggestion that the origin of these gigantic alkaline intrusions is connected to a deep seated mantle source—possibly to a lower mantle plume. The required combination of a depleted mantle and high rare metal enrichment in the source can be explained by the input of incompatible elements by metasomatising melts/fluids into the zones of alkaline magma generation shortly before the partial melting event (to avoid ingrowth of radiogenic isotopes). The minerals belovite and pyrochlore from the pegmatites are abnormally high in 87Sr /86Sr ratios. This may be explained by closed system isotope evolution as a result of a significant increase in Rb/Sr during the evolution of the peralkaline magma.

  17. Potential Process for the Decontamination of Pyro-electrometallurgical LiCl-KCl Eutectic Salt Electrolyte

    International Nuclear Information System (INIS)

    Griffith, Christopher S.; Sizgek, Erden; Sizgek, Devlet; Luca, Vittorio

    2008-01-01

    Presented here is a potential option with experimental validation for the decontamination of LiCl-KCl eutectic salt electrolyte from a pyro-electrometallurgical process by employing already developed inorganic ion exchange materials. Adsorbent materials considered include titano-silicates and molybdo- and tungstophosphates for Cs extraction, Si-doped antimony pyrochlore for Sr extraction and hexagonal tungsten bronzes for lanthanide (LN) and minor actinide (MA) polishing. Encouraging results from recent investigations on the removal of target elements (Cs, Sr and LN) from aqueous solutions containing varying concentrations of alkali and alkali metal contaminants which would be akin to a solution formed from the dissolution of spent LiCl-KCl eutectic salt electrolyte are presented. Further investigations have also shown that the saturated adsorbents can be treated at relatively low temperatures to afford potential waste forms for the adsorbed elements. Efficient evaporation and drying of a solution of dissolved LiCl-KCl eutectic salt electrolyte (50 L, 5 L.h -1 ) has been demonstrated using a Microwave-Heated Mechanical Fluidized Bed (MWMFB) apparatus. (authors)

  18. Potential Process for the Decontamination of Pyro-electrometallurgical LiCl-KCl Eutectic Salt Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Griffith, Christopher S.; Sizgek, Erden; Sizgek, Devlet; Luca, Vittorio [Australian Nuclear Science and Technology Organisation (ANSTO), Institute of Materials Engineering, New Illawarra Road, Lucas Heights, New South Wales, 2234 (Australia)

    2008-07-01

    Presented here is a potential option with experimental validation for the decontamination of LiCl-KCl eutectic salt electrolyte from a pyro-electrometallurgical process by employing already developed inorganic ion exchange materials. Adsorbent materials considered include titano-silicates and molybdo- and tungstophosphates for Cs extraction, Si-doped antimony pyrochlore for Sr extraction and hexagonal tungsten bronzes for lanthanide (LN) and minor actinide (MA) polishing. Encouraging results from recent investigations on the removal of target elements (Cs, Sr and LN) from aqueous solutions containing varying concentrations of alkali and alkali metal contaminants which would be akin to a solution formed from the dissolution of spent LiCl-KCl eutectic salt electrolyte are presented. Further investigations have also shown that the saturated adsorbents can be treated at relatively low temperatures to afford potential waste forms for the adsorbed elements. Efficient evaporation and drying of a solution of dissolved LiCl-KCl eutectic salt electrolyte (50 L, 5 L.h{sup -1}) has been demonstrated using a Microwave-Heated Mechanical Fluidized Bed (MWMFB) apparatus. (authors)

  19. Sm2FeTaO7 Photocatalyst for Degradation of Indigo Carmine Dye under Solar Light Irradiation

    Directory of Open Access Journals (Sweden)

    Leticia M. Torres-Martínez

    2012-01-01

    Full Text Available This paper is focused to study Sm2FeTaO7 pyrochlore-type compound as solar photocatalyst for the degradation of indigo carmine dye in aqueous solution. Sm2FeTaO7 was synthesized by using conventional solid state reaction and sol-gel method. X-ray diffraction results indicated that Sm2FeTaO7 exhibit a monoclinic crystal structure. By scanning electron microscopy analysis, it was observed that sol-gel material presents particle size of around 150 nm. The specific surface area and energy bandgap values were 12 m2 g−1 and 2.0 eV, respectively. The photocatalytic results showed that indigo carmine molecule can be degraded under solar light irradiation using the synthesized materials, sol-gel photocatalyst was 8 times more active than solid state. On the other hand, when Sm2FeTaO7 was impregnated with CuO as cocatalyst the photocatalytic activity was increased because CuO acts as electron trap decreasing electron-hole pair recombination rates.

  20. Intermediate magnetization state and competing orders in Dy2Ti2O7 and Ho2Ti2O7

    Science.gov (United States)

    Borzi, R. A.; Gómez Albarracín, F. A.; Rosales, H. D.; Rossini, G. L.; Steppke, A.; Prabhakaran, D.; Mackenzie, A. P.; Cabra, D. C.; Grigera, S. A.

    2016-01-01

    Among the frustrated magnetic materials, spin-ice stands out as a particularly interesting system. Residual entropy, freezing and glassiness, Kasteleyn transitions and fractionalization of excitations in three dimensions all stem from a simple classical Hamiltonian. But is the usual spin-ice Hamiltonian a correct description of the experimental systems? Here we address this issue by measuring magnetic susceptibility in the two most studied spin-ice compounds, Dy2Ti2O7 and Ho2Ti2O7, using a vector magnet. Using these results, and guided by a theoretical analysis of possible distortions to the pyrochlore lattice, we construct an effective Hamiltonian and explore it using Monte Carlo simulations. We show how this Hamiltonian reproduces the experimental results, including the formation of a phase of intermediate polarization, and gives important information about the possible ground state of real spin-ice systems. Our work suggests an unusual situation in which distortions might contribute to the preservation rather than relief of the effects of frustration. PMID:27558021

  1. Microstructural and microchemical characterization of the interface between La0.85Sr0.15MnO3 and Y2O3-stabilized ZrO2

    DEFF Research Database (Denmark)

    Clausen, C.; Bagger, C.; Bilde-Sørensen, Jørgen

    1994-01-01

    La0.85Sr0.15MnO3 and Y2O3-stabilized ZrO2 may be used as cathode and electrolyte materials, respectively, in solid oxide fuel cells. One of the requirements of the cathode-electrolyte interface is that high impedance phases are not formed at the interface during manufacture or operation of the SOFC....... The interfaces of interest were prepared as a diffusion couple and by sintered powder mixtures of La0.85Sr0.15MnO3 and Y2O3-stabilized ZrO2. The structures at the interfaces were examined by transmission electron microscopy. Chemical analyses were made by energy dispersive X-ray spectroscopy. A Zr, La......-based pyrochlore-type crystalline phase has been observed at some of the interfaces between La0.85Sr0.15MnO3 and Y2O3-stabilized ZrO2. In the present paper, changes in element ratios are used to obtain knowledge on how the elements diffuse with respect to each other at the interface. It was found...

  2. Phase relations in the ZrO2-Nd2O3-Y2O3 system. Experimental study and CALPHAD assessment

    International Nuclear Information System (INIS)

    Fabrichnaya, Olga; Savinykh, Galina; Schreiber, Gerhard; Seifert, Hans J.

    2010-01-01

    The thermodynamic parameters of the Nd 2 O 3 Y 2 O 3 system were re-assessed for better reproduction of experimental data. The thermodynamic parameters were combined from binary descriptions to calculate phase diagrams for the ternary system ZrO 2 -Nd 2 O 3 Y 2 O 3 . The calculated phase diagrams were used to select compositions for the experimental studies at 1250, 1400 and 1600 C. The samples were synthesised by co-precipitation and heat treated at 1250-1600 C, investigated by X-ray diffraction and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. It was found that solubility of the Y 2 O 3 in the pyrochlore phase exceeds 10 mol.%. The experimental data obtained for phase equilibria were used to derive thermodynamic parameters for fluorite, Y 2 O 3 cubic phase C, monoclinic B and Nd 2 O 3 hexagonal A phases by CALPHAD method. The isothermal sections and liquidus surface were calculated for the ZrO 2 -Nd 2 O 3 Y 2 O 3 system. (orig.)

  3. Improving yield of PZT piezoelectric devices on glass substrates

    Science.gov (United States)

    Johnson-Wilke, Raegan L.; Wilke, Rudeger H. T.; Cotroneo, Vincenzo; Davis, William N.; Reid, Paul B.; Schwartz, Daniel A.; Trolier-McKinstry, Susan

    2012-10-01

    The proposed SMART-X telescope includes adaptive optics systems that use piezoelectric lead zirconate titanate (PZT) films deposited on flexible glass substrates. Several processing constraints are imposed by current designs: the crystallization temperature must be kept below 550 °C, the total stress in the film must be minimized, and the yield on 1 cm2 actuator elements should be work, RF magnetron sputtering was used to deposit films since chemical solution deposition (CSD) led to warping of large area flexible glass substrates. A PZT 52/48 film that wasdeposited at 4 mTorr and annealed at 550 °C for 24 hours showed no detectable levels of either PbO or pyrochlore second phases. Large area electrodes (1cm x 1 cm) were deposited on 4" glass substrates. Initially, the yield of the devices was low, however, two methods were employed to increase the yield to near 100 %. The first method included a more rigorous cleaning to improve the continuity of the Pt bottom electrode. The second method was to apply 3 V DC across the capacitor structure to burn out regions of defective PZT. The result of this latter method essentially removed conducting filaments in the PZT but left the bulk of the material undamaged. By combining these two methods, the yield on the large area electrodes improved from < 10% to nearly 100%.

  4. Chemistry of surface nanostructures in lead precursor-rich PbZr{sub 0.52}Ti{sub 0.48}O{sub 3} sol–gel films

    Energy Technology Data Exchange (ETDEWEB)

    Gueye, I.; Le Rhun, G.; Gergaud, P.; Renault, O. [Univ. Grenoble Alpes, F-38000 Grenoble (France); CEA, LETI, MINATEC Campus, F-38054 Grenoble (France); Defay, E. [Luxembourg Institute of Science and Technology, Materials Research and Technology Department, 41 Rue du Brill, L-4422 Belvaux (Luxembourg); Barrett, N., E-mail: nick.barrett@cea.fr [SPEC, CEA, CNRS, Université Paris Saclay, F-91191 Gif-sur-Yvette (France)

    2016-02-15

    Highlights: • We have studied the effect of lead excess on the surface of PZT sol–gel films. • For low lead excess (10%) nanostructured surface phase is observed. • X-ray photoelectron spectroscopy shows that the surface phase is Zr oxide. - Abstract: We present a study of the chemistry of the nanostructured phase at the surface of lead zirconium titanate PbZr{sub 0.52}Ti{sub 0.48}O{sub 3} (PZT) films synthesized by sol–gel method. In sol–gel synthesis, excess lead precursor is used to maintain the target stoichiometry. Surface nanostructures appear at 10% excess whereas 30% excess inhibits their formation. Using the surface-sensitive, quantitative X-ray photoelectron spectroscopy and glancing angle X-ray diffraction we have shown that the chemical composition of the nanostructures is ZrO{sub 1.82−1.89} rather than pyrochlore often described in the literature. The presence of a possibly discontinuous layer of wide band gap ZrO{sub 1.82−1.89} could be of importance in determining the electrical properties of PZT-based metal-insulator-metal heterostructures.

  5. Crystal chemistry of six-coordinated silicon: A key to understanding the earth's deep interior

    International Nuclear Information System (INIS)

    Finger, L.W.; Hazen, R.M.

    1991-01-01

    A survey of high-pressure silicates reveals 12 distinct high-density structural topologies with octahedral Si. Seven of these structure types - stishovite, perovskite, ilmenite, hollandite, calcium ferrite, pyrochlore and K 2 NiF 4 type - contain only six-corrdinated silicon. Other high-pressure silicates, including those with the garnet, pyroxene, wadeite, anhydrous phase B and phase B structures, contain both tetrahedral and octahedral Si. Five systematic trends among these dozen structures suggest the existence of other, as yet unobserved, possible mantle Si phases. The criteria are: (1) Structures like rutile, hollandite and calcium ferrite formed from edge-sharing chains of silicon octahedra; (2) germanates synthesized at room pressure with octahedral Ge; (3) isomorphs of room-pressure oxides with 3+ or 4+ transition-metal cations; (4) high-pressure magnesium silicates related to room-pressure aluminates by the substitution 2Al→Mg+Si; and (5) the homologous structures in system Mg-Si-O-H that includes phase B and anhydrous phase B. Each of these criteria can be used to predict other potential octahedral Si phases. Of special interest are predicted structure types that fulfill more than one criterion: Diaspore-type (MgSi)O 2 (OH) 2 , aerugite-type Mg 10 Si 3 O 16 , sphene-type CaSi 2 O 5 , benitoite-type BaSi 4 O 9 , gibbsite-type MgSi(OH) 6 and pseudobrookite-type Fe 2 SiO 5 . (orig.)

  6. Absence of magnetic ordering and field-induced phase diagram in the gadolinium aluminum garnet

    Science.gov (United States)

    Florea, O.; Lhotel, E.; Jacobsen, H.; Knee, C. S.; Deen, P. P.

    2017-12-01

    The robustness of spin liquids with respect to small perturbations, and the way magnetic frustration can be lifted by slight changes in the balance between competing magnetic interactions, remains a rich and open issue. We address this question through the study of the gadolinium aluminum garnet Gd3Al5O12 , a related compound to the extensively studied Gd3Ga5O12 . We report on its magnetic properties at very low temperatures. We show that despite a freezing at about 300 mK, no magnetic transition is observed, suggesting the presence of a spin-liquid state down to the lowest temperatures, similarly to Gd3Ga5O12 , in spite of a larger ratio between exchange and dipolar interactions. Finally, the phase diagram as a function of field and temperature is strongly reminiscent of the one reported in Gd3Ga5O12 . This study reveals the robust nature of the spin-liquid phase for Gd ions on the garnet lattice, in stark contrast to Gd ions on the pyrochlore lattice for which a slight perturbation drives the compound into a range of magnetically ordered states.

  7. Determination of the concentration of 238U, 234U, 232Th, 228Th, 228Ra, 226Ra and 210Pb in the feces of workers from a mining company of niobium and their families

    International Nuclear Information System (INIS)

    Oliveira, Roges de; Lopes, Ricardo T.; Melo, Dunstana R.; Juliao, Ligia M.Q.C.

    2005-01-01

    The object of this study consists of an open mine from which Niobium ore (pyrochlore) is extracted and a metallurgy company, where Fe-Nb alloys are produced for export. For geological reasons, the main ore is associated to natural radionuclides U and Th, and its decay products. The concentration of 234 U, 238 U, 232 Th, 226 Ra and 228 Ra, 228 Th, including 210 Pb in fecal excretion of 12:0 am, 29 workers and 13 family members were determined. The technique employed for the determination of the elements was the sequential method of radiochemical separation, followed by alpha spectrometry and counting α and β in proportional detector. Statistically significant difference was observed in the concentration of 234 U and 238 U, in feces samples, among the group of mining workers and family members; as well as for 232 Th in the feces of workers of crushing and metallurgy groups when compared with the Family Group. No statistically significant difference was detected at a concentration of 226 Ra, 228 Ra and 210 Pb, in feces of any group of workers of the installation in relation to the family group

  8. Growth, Faraday and inverse Faraday characteristics of Tb2Ti2O7 crystal.

    Science.gov (United States)

    Guo, Feiyun; Sun, Yilin; Yang, Xiongsheng; Chen, Xin; Zhao, Bin; Zhuang, Naifeng; Chen, Jianzhong

    2016-03-21

    Tb2Ti2O7 (TTO) single crystal with dimensions of 20 × 20 × 16 mm3 was grown by the Czochralski method. Rietveld structure refinement of X-ray diffraction (XRD) data confirms that the compound crystallizes in the cubic system with pyrochlore structure. Transmission spectra, Magnetic circular dichroism (MCD) spectra, Faraday and inverse Faraday characteristics of TTO crystal have been measured and analyzed in detail. The results demonstrate that TTO crystal has high transmittance at 700-1400 nm waveband and a larger Verdat constant than that of TGG reported. Magnetic circular dichroism (MCD) spectra showed that the 4f→4f transitions of Tb3+ have significant contributions to the magneto-optical activity (MOA). In the time-resolved pump-probe spectroscopy, the rotation signals of the probe beam based on the inverse Faraday effect in magneto-optical crystal were observed at zero time delay, the full width at half maximum of the rotation and ellipticity signals can be as fast as ~500 fs, which indicates that TTO crystal can be a promising material for ultrafast all-optical magnetic switching.

  9. Metallic Interface Emerging at Magnetic Domain Wall of Antiferromagnetic Insulator: Fate of Extinct Weyl Electrons

    Directory of Open Access Journals (Sweden)

    Youhei Yamaji

    2014-05-01

    Full Text Available Topological insulators, in contrast to ordinary semiconductors, accompany protected metallic surfaces described by Dirac-type fermions. Here, we theoretically show that another emergent two-dimensional metal embedded in the bulk insulator is realized at a magnetic domain wall. The domain wall has long been studied as an ingredient of both old-fashioned and leading-edge spintronics. The domain wall here, as an interface of seemingly trivial antiferromagnetic insulators, emergently realizes a functional interface preserved by zero modes with robust two-dimensional Fermi surfaces, where pyrochlore iridium oxides proposed to host the condensed-matter realization of Weyl fermions offer such examples at low temperatures. The existence of in-gap states that are pinned at domain walls, theoretically resembling spin or charge solitons in polyacetylene, and protected as the edges of hidden one-dimensional weak Chern insulators characterized by a zero-dimensional class-A topological invariant, solves experimental puzzles observed in R_{2}Ir_{2}O_{7} with rare-earth elements R. The domain wall realizes a novel quantum confinement of electrons and embosses a net uniform magnetization that enables magnetic control of electronic interface transports beyond the semiconductor paradigm.

  10. High aspect ratio lead zirconate titanate tube structures: I. Template assisted fabrication - vacuum infiltration method

    Directory of Open Access Journals (Sweden)

    Vladimír Kovaľ

    2012-03-01

    Full Text Available Polycrystalline Pb(Zr0.52Ti0.48O3 (PZT microtubes are fabricated by a vacuum infiltration method. The method is based on repeated infiltration of precursor solution into macroporous silicon (Si templates at a sub-atmospheric pressure. The pyrolyzed PZT tubes of a 2-µm outer diameter, extending to over 30 µm in length were released from the template using a selective isotropic-pulsed XeF2 reactive ion etching of silicon. Free-standing microtubes, partially anchored at the bottom of the Si template, were then crystallized in pure oxygen atmosphere at 750 °C for 2 min using a rapid thermal annealer. The perovskite phase of the final PZT tubes was confirmed by X-ray diffraction (XRD analysis. The XRD spectrum also revealed a small amount of the pyrochlore phase in the structure and signs of possible fluoride contamination caused most likely by the XeF2 etching process. The surface morphology was examined using scanning electron microscopy. It was demonstrated that the whole surface of the pore walls was conformally coated during the repeated infiltration of templates, resulting in straight tubes with closed tips formed on the opposite ends as replicas of the pore bottoms. These high aspect ratio ferroelectric structures are suggested as building units for developing miniaturized electronic devices, such as memory storage (DRAM trenched capacitors, piezoelectric scanners and actuators, and are of fundamental value for the theory of ferroelectricity in systems with low dimensionality.

  11. Magnetic cooling close to a quantum phase transition—The case of Er{sub 2}Ti{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Wolf, B.; Tutsch, U.; Dörschug, S.; Krellner, C.; Ritter, F.; Assmus, W.; Lang, M. [Physikalisches Institut, Goethe Universität, SFB-TR49, 60438 Frankfurt (Germany)

    2016-10-14

    Magnetic cooling, first introduced in the late twenties of last century, has regained considerable interest recently as a cost-efficient and easy-to-handle alternative to {sup 3}He-based refrigeration techniques. Especially, adiabatic demagnetization of paramagnets—the standard materials for magnetic refrigeration—has become indispensable for the present space applications. To match the growing demand for increasing the efficiency in these applications, a new concept for magnetic cooling based on many-body effects around a quantum-critical-point has been introduced and successfully tested [B. Wolf et al., Proc. Natl. Acad. Sci. U.S.A. 108, 6862 (2011)]. By extending this concept to three-dimensional magnetic systems, we present here the magnetothermal response of the cubic pyrochlore material Er{sub 2}Ti{sub 2}O{sub 7} in the vicinity of its B-induced quantum-critical point which is located around 1.5 T. We discuss performance characteristics such as the range of operation, the efficiency, and the hold time. These figures are compared with those of state-of-the-art paramagnetic coolants and with other quantum-critical systems which differ by the dimensionality of the magnetic interactions and the degree of frustration.

  12. DEVELOPMENT OF CRYSTALLINE CERAMICS FOR IMMOBILIZATION OF ADVANCED FUEL CYCLE REPROCESSING WASTES

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K.; Brinkman, K.

    2011-09-22

    The Savannah River National Laboratory (SRNL) is developing crystalline ceramic waste forms to incorporate CS/LN/TM high Mo waste streams consisting of perovskite, hollandite, pyrochlore, zirconolite, and powellite phase assemblages. Simple raw materials, including Al{sub 2}O{sub 3}, CaO, and TiO{sub 2} were combined with simulated waste components to produce multiphase crystalline ceramics. Fiscal Year 2011 (FY11) activities included (i) expanding the compositional range by varying waste loading and fabrication of compositions rich in TiO{sub 2}, (ii) exploring the processing parameters of ceramics produced by the melt and crystallize process, (iii) synthesis and characterization of select individual phases of powellite and hollandite that are the target hosts for radionuclides of Mo, Cs, and Rb, and (iv) evaluating the durability and radiation stability of single and multi-phase ceramic waste forms. Two fabrication methods, including melting and crystallizing, and pressing and sintering, were used with the intent of studying phase evolution under various sintering conditions. An analysis of the XRD and SEM/EDS results indicates that the targeted crystalline phases of the FY11 compositions consisting of pyrochlore, perovskite, hollandite, zirconolite, and powellite were formed by both press and sinter and melt and crystallize processing methods. An evaluation of crystalline phase formation versus melt processing conditions revealed that hollandite, perovskite, zirconolite, and residual TiO{sub 2} phases formed regardless of cooling rate, demonstrating the robust nature of this process for crystalline phase development. The multiphase ceramic composition CSLNTM-06 demonstrated good resistance to proton beam irradiation. Electron irradiation studies on the single phase CaMoO{sub 4} (a component of the multiphase waste form) suggested that this material exhibits stability to 1000 years at anticipated self-irradiation doses (2 x 10{sup 10}-2 x 10{sup 11} Gy), but that

  13. Genesis of rare-metal pegmatites and alkaline apatite-fluorite rocks of Burpala massi, Northern Baikal folded zone

    Science.gov (United States)

    Sotnikova, Irina; Vladykin, Nikolai

    2015-04-01

    Burpalinsky rare metal alkaline massif in the Northern Baikal folded zone in southern margin of Siberian Platform, is a of intrusion central type, created 287 Ma covering area of about 250 km2. It is composed of nepheline syenites and pulaskites grading to quartz syenites in the contacts. Veines and dykes are represented by shonkinites, sodalite syenite, leucocratic granophyres, alkali granites and numerous rare metal alkaline syenite pegmatites and two dykes of carbonatites. All rocks except for granites are cut by a large apatite-fluorite dyke rocks with mica and magnetite, which in turn is cut by alaskite granites dyke. The massif has been studied by A.M. Portnov, A.A. Ganzeev et al. (1992) Burpalinsky massif is highly enriched with trace elements, which are concentrated in pegmatite dykes. About 70 rare-metal minerals we found in massif. Zr-silicates: zircon, eudialyte, lovenite, Ti-lovenite, velerite, burpalite, seidozerite, Ca- seidozerite, Rosenbuschite, vlasovite, katapleite, Ca-katapleite, elpidite. Ti- minerals:- sphene, astrophyllite, ramsaite, Mn-neptunite bafertisite, chevkinite, Mn-ilmenite, pirofanite, Sr-perrerit, landauite, rutile, anatase, brookite; TR- minerals - loparite, metaloparite, britolite, rinkolite, melanocerite, bastnesite, parisite, ankilite, monazite, fluocerite, TR-apatite; Nb- minerals - pyrochlore, loparite. Other rare minerals leucophanite, hambergite, pyrochlore, betafite, torite, thorianite, tayniolite, brewsterite, cryolite and others. We have proposed a new scheme massif: shonkinites - nepheline syenites - alkaline syenite - quartz syenites - veined rocks: mariupolites, rare-metal pegmatites, apatite, fluorite rock alyaskite and alkaline granites and carbonatites (Sotnikova, 2009). Apatite-fluorite rocks are found in the central part of massif. This is a large vein body of 2 km length and a 20 m width cutting prevailing pulaskites. Previously, these rocks were regarded as hydrothermal low-temperature phase. New geological and

  14. NOVEL COMPOSITE MEMBRANES FOR HYDROGEN SEPARATION IN GASIFICATION PROCESSES IN VISION 21 ENERGY PLANTS

    Energy Technology Data Exchange (ETDEWEB)

    Michael Schwartz

    2004-12-01

    were obtained during this program. In the area of materials synthesis, novel pyrochlore-based proton conductors were identified, synthesized and characterized. They exhibited conductivity as high as 0.03 S/cm at 900 C. Long-term stability under CO{sub 2} and H{sub 2} atmospheres was also demonstrated. In the area of membrane fabrication by plasma spray processing, the initial results showed that the pyrochlore materials could be processed in a spray torch. Although leak-tight membranes were obtained, cracking, most likely due to differences in thermal expansion, remained a problem. More modeling and experimental work can be used to solve this problem. Finally the techno-economic analyses showed that the ITN ICCM approach for separating H{sub 2} is comparable to conventional pressure swing adsorption (PSA) technology in efficiency and economics. Enhanced membrane flux and lower operating temperatures may make the ICCM approach superior to PSA.

  15. Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

    Energy Technology Data Exchange (ETDEWEB)

    Silyukov, Oleg I., E-mail: olegsilyukov@yandex.ru; Abdulaeva, Liliia D.; Burovikhina, Alena A.; Rodionov, Ivan A.; Zvereva, Irina A.

    2015-03-15

    Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}pyrochlor-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation to layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. Structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}

  16. Evolución microestructural durante la transformación de la estructura pirocloro en perovskita en láminas de (Pb,LaTiO3

    Directory of Open Access Journals (Sweden)

    Calzada, M. L.

    2002-02-01

    Full Text Available A pyrochlore to perovskite transformation is known to occur during the rapid heating of sol-gel prepared La modified lead titanate ferroelectric thin films. This transformation is not inhibited by the Pb deficiency caused by PbO volatilisation at the initial stages of the thermal treatment. The microstructural evolution associated with this transformation occurring in the Pb deficient film has been studied by transmission electron microscopy. Plan view and cross section specimens were prepared from two films at different stages of the transformation. Experiments showed that the pyrochlore phase was homogenously distributed across the film thickness, with a very similar morphology to that of the ferroelectric phase. The combination of microdiffraction and microanalysis allowed identifying single grains that had not the perovskite structure, and were more Pb deficient than the film. Pore growth, grain growth, and growth of local texturing were observed along with the transformation.Es conocido que se produce una transformación de estructura pirocloro a perovskita durante el calentamiento rápido de láminas delgadas ferroeléctricas de titanato de plomo modificadas con La, preparadas por sol-gel. La deficiencia de Pb causada por la volatilización de PbO en los primeros momentos del tratamiento térmico no inhibe la transformación. Se ha estudiado, por microscopía electrónica de transmisión, la evolución microestructural asociada a esta transformación, que ocurre en un medio que en promedio es deficiente en Pb. Con este fin, se prepararon muestras para microscopía, tanto del plano de la lámina como secciones transversales, a partir de dos láminas en las que la transformación se encontraba en estadios diferentes. Los experimentos pusieron de manifiesto que la fase con estructura pirocloro se encontraba homogéneamente distribuida a lo largo del espesor de la lámina, y que su morfología era muy similar a la de la fase ferroel

  17. Mixed conductivity, structural and microstructural characterization of titania-doped yttria tetragonal zirconia polycrystalline/titania-doped yttria stabilized zirconia composite anode matrices

    International Nuclear Information System (INIS)

    Colomer, M.T.; Maczka, M.

    2011-01-01

    Taking advantage of the fact that TiO 2 additions to 8YSZ cause not only the formation of a titania-doped YSZ solid solution but also a titania-doped YTZP solid solution, composite materials based on both solutions were prepared by solid state reaction. In particular, additions of 15 mol% of TiO 2 give rise to composite materials constituted by 0.51 mol fraction titania-doped yttria tetragonal zirconia polycrystalline and 0.49 mol fraction titania-doped yttria stabilized zirconia (0.51TiYTZP/0.49TiYSZ). Furthermore, Y 2 (Ti 1-y Zr y ) 2 O 7 pyrochlore is present as an impurity phase with y close to 1, according to FT-Raman results. Lower and higher additions of titania than that of 15 mol%, i.e., x=0, 5, 10, 20, 25 and 30 mol% were considered to study the evolution of 8YSZ phase as a function of the TiO 2 content. Furthermore, zirconium titanate phase (ZrTiO 4 ) is detected when the titania content is equal or higher than 20 mol% and this phase admits Y 2 O 3 in solid solution according to FE-SEM-EDX. The 0.51TiYTZP/0.49TiYSZ duplex material was selected in this study to establish the mechanism of its electronic conduction under low oxygen partial pressures. In the pO 2 range from 0.21 to 10 -7.5 atm. the conductivity is predominantly ionic and constant over the range and its value is 0.01 S/cm. The ionic plus electronic conductivity is 0.02 S/cm at 1000 o C and 10 -12.3 atm. Furthermore, the onset of electronic conductivity under reducing conditions exhibits a -1/4 pO 2 dependence. Therefore, it is concluded that the n-type electronic conduction in the duplex material can be due to a small polaron-hopping between Ti 3+ and Ti 4+ . -- Graphical abstract: FE-SEM micrograph of a polished and thermal etched surface of a Ti-doped YTZP/Ti-doped YSZ composite material. Display Omitted Research highlights: → Ti-doped YTZP/Ti-doped YSZ composite materials are mixed conductors under low partial pressures. → From 5 mol% of TiO 2 , Y 2 (Ti 1-y ,Zr y ) 2 O 7 pyrochlore is

  18. Lithium intercalation mechanism into FeF3·0.5H2O as a highly stable composite cathode material

    Science.gov (United States)

    Ali, Ghulam; Lee, Ji–Hoon; Chang, Wonyoung; Cho, Byung-Won; Jung, Hun-Gi; Nam, Kyung-Wan; Chung, Kyung Yoon

    2017-02-01

    The growing demand for lithium-ion batteries (LIBs) requires investigation of high-performance electrode materials with the advantages of being environmentally friendly and cost-effective. In this study, a nanocomposite of open-pyrochlore-structured FeF3·0.5H2O and reduced graphene oxide (RGO) is synthesized for use as a high-performance cathode in LIBs, where RGO provides high electrical conductivity to the composite material. The morphology of the composite shows that FeF3·0.5H2O spheres are embedded into RGO layers and high-resolution TEM image shows that those spheres are composed of primary nanoparticles with a size of ~5 nm. The cycling performance indicates that the composite electrode delivers an initial high discharge capacity of 223 mAh g-1 at 0.05 C, a rate capability up to a high C-rate of 10 C (47 mAh g-1) and stable cycle performance at 0.05 C (145 mAh g-1 after 100 cycles) and 0.2 C (93 mAh g-1 after 100 cycles) while maintaining high electrochemical reversibility. Furthermore, the responsible electrochemical reaction is investigated using in-situ XRD and synchrotron-based X-ray absorption spectroscopy (XAS), and the XRD results show that FeF3·0.5H2O transitions to an amorphous-like phase through a lithiation process. However, a reversible oxidation change of Fe3+ ↔ Fe2+ is identified by the XAS results.

  19. Structural and magnetic properties of two branches of the tripod-kagome-lattice family A2R3Sb3O14 (A = Mg, Zn; R = Pr, Nd, Gd, Tb, Dy, Ho, Er, Yb)

    Science.gov (United States)

    Dun, Z. L.; Trinh, J.; Lee, M.; Choi, E. S.; Li, K.; Hu, Y. F.; Wang, Y. X.; Blanc, N.; Ramirez, A. P.; Zhou, H. D.

    2017-03-01

    We present a systematic study of the structural and magnetic properties of two branches of the rare-earth tripod-kagome-lattice (TKL) family A2R3Sb3O14 (A = Mg, Zn; R = Pr, Nd, Gd, Tb, Dy, Ho, Er, Yb; here, we use abbreviation A-R, as in MgPr for Mg2Pr3Sb3O14 ), which complements our previously reported work on MgDy, MgGd, and MgEr [Z. L. Dun et al., Phys. Rev. Lett. 116, 157201 (2016), 10.1103/PhysRevLett.116.157201]. The present susceptibility (χdc, χac) and specific-heat measurements reveal various magnetic ground states, including the nonmagnetic singlet state for MgPr, ZnPr; long-range orderings (LROs) for MgGd, ZnGd, MgNd, ZnNd, and MgYb; a long-range magnetic charge ordered state for MgDy, ZnDy, and potentially for MgHo; possible spin-glass states for ZnEr, ZnHo; the absence of spin ordering down to 80 mK for MgEr, MgTb, ZnTb, and ZnYb compounds. The ground states observed here bear both similarities as well as striking differences from the states found in the parent pyrochlore systems. In particular, while the TKLs display a greater tendency towards LRO, the lack of LRO in MgHo, MgTb, and ZnTb can be viewed from the standpoint of a balance among spin-spin interactions, anisotropies, and non-Kramers nature of single-ion state. While substituting Zn for Mg changes the chemical pressure, and subtly modifies the interaction energies for compounds with larger R ions, this substitution introduces structural disorder and modifies the ground states for compounds with smaller R ions (Ho, Er, Yb).

  20. Magnetic properties of nanoscaled paramelaconite Cu{sub 4}O{sub 3−x} (x=0.0 and 0.5)

    Energy Technology Data Exchange (ETDEWEB)

    Djurek, D., E-mail: danijel.djurek@zg.t-com.hr [A. Volta Applied Ceramics (AVAC), 49247 Zlatar Bistrica, A. Šenoe 14 (Croatia); Prester, M.; Drobac, Dj. [Institute of Physics, 10000 Zagreb, Bijenička c. 46 (Croatia); Ivanda, M.; Vojta, D. [Ruđer Bošković Institute, 10000 Zagreb, Bijenička c. 54 (Croatia)

    2015-01-01

    Pure paramelaconite Cu{sub 4}O{sub 3−x} has been prepared in the form of nanoparticles with 56 nm in diameter. This mixed valency oxide crystallizes in a tetragonal lattice with 4 unit formulae and forms a pyrochlore structure which manifests in two stoichiometric forms; Cu{sub 4}O{sub 3} and Cu{sub 4}O{sub 2.5}, the latter form having two oxygen vacancies per unit cell. Magnetic lattice consists of Cu spin 1/2, and both stoichiometric forms obey transition to the antiferromagnetic state at T{sub N}=45–55 K. Defect free Cu{sub 4}O{sub 3} is indicated by an inversion symmetry and exhibits both antiferromagnetic and ferromagnetic state, where the latter is supposedly due to the superexchange interaction in Cu–O(1n)–Cu bonds. An additional magnetic transition was observed in Cu{sub 4}O{sub 3} at T=120 K, probably as a result of an incommensurate ordering. Absence of an inversion symmetry in the oxygen defect Cu{sub 4}O{sub 2.5} results in a long range Dzyaloshinsky–Moriya interaction accompanied by the strong superparamagnetism. - Highlights: • The first successful preparation of pure paramelaconite Cu{sub 4}O{sub 3−x}. • High resolution AC susceptibility measurements. • Evidence is presented for two stoichiometric forms of paramelaconite; defect free Cu{sub 4}O{sub 3} and Cu{sub 4}O{sub 2.5}. • Additional magnetic transition is observed at T=120 K in the defect free Cu{sub 4}O{sub 3}.

  1. Raman analysis of ancient pigments on a tile from the Citadel of Algiers

    Science.gov (United States)

    Kock, L. D.; De Waal, D.

    2008-12-01

    A micro-Raman spectroscopy study of a multi-coloured (yellow, blue, white, redish-brown and brown-black) tile shard from the Citadel of Algiers was undertaken. XRD and EDX were used as complementary techniques. The study shows that the heterogeneous three-shade yellow pigment on the tile is composed largely of the ancient ternary (Pb-Sn-Sb) pyrochlore oxide with a dominant Pb-O vibration at 127 cm -1 consistent with the Pb 2SnSbO 6.5 structure as verified by XRD. The literature assignment of this band at 132 cm -1 probably comes from a mixture of pigments. The redish-brown and the brown-black pigments are found to be Naples yellow (Pb 2Sb 2O 7) and lead(II) stannate (Pb 2SnO 4), respectively, while cobalt blue (CoAl 2O 4) gives the blue colour and cassiterite (SnO 2) is the origin of the white colour. The bulk of the tile body is composed mainly of hematite (α-Fe 2O 3), maghemite (γ-Fe 2O 3), magnetite (Fe 3O 4) and Quartz (α-SiO 2) with traces of calcite (CaCO 3) and amorphous carbon. Micro-Raman spectroscopy proved to be very useful in the characterization of pigments as well as the tile body. These results further establish Raman spectroscopy as a technique of choice for the analysis of pigments on archaeological artifacts. The results obtained here could be used in the restoration and preservation programme of the Citadel itself which stands today as a symbol of pre-colonial Algerian heritage.

  2. Sintering, microstructure and electrical conductivity of gadolinia-doped ceria with SrO, TiO{sub 2} and SrTiO{sub 3}; Sinterizacao, microestrutura e condutividade eletrica da ceria-gadolinia com adicoes de SrO, TiO{sub 2} e SrTiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Maria Cely Freitas

    2013-07-01

    Ceria containing trivalent rare-earths is a solid electrolyte with higher ionic conductivity than the standard yttria fully-stabilized zirconia ionic conductor. This property turns these ceria-based ionic conductors promising materials for application in solid oxide fuel cells operating at intermediate temperatures (500-700 deg C). One of the most utilized approaches to optimize the electrical conductivity and other properties of these materials is the introduction of a second additive. In this work, ceria-20 mol% gadolinia with additions of 1, 2.5 and 5 mol% of SrO, TiO{sub 2} and SrTiO{sub 3} as co-additives were prepared by solid state reaction. The main purpose was to investigate the effects of the co-additives on densification, microstructure and electrical conductivity of the solid electrolyte. Sintered pellets were characterized by apparent density, X-ray diffraction, Raman spectroscopy, scanning electron microscopy and electrical conductivity by impedance spectroscopy. The additives were found to exert different influences in all studied properties. The way they influence the solid electrolyte properties depends on the type and content of the additive. SrO addition to doped ceria improves the intergranular conductivity, but decreases the apparent density of the pellets. Increase of densification was obtained with TiO{sub 2} addition. This additive promotes increase of the blocking of charge carriers at the grain boundaries due to solute exsolution and formation of the pyrochlore Gd{sub 2}Ti{sub 2}O{sub 7} phase at grain boundaries for contents in excess of the solubility limit. No influence on densification was found for SrTiO{sub 3} additions. (author)

  3. Sintering, microstructure and electrical conductivity of gadolinia-doped ceria with SrO, TiO2 and SrTiO3

    International Nuclear Information System (INIS)

    Dias, Maria Cely Freitas

    2013-01-01

    Ceria containing trivalent rare-earths is a solid electrolyte with higher ionic conductivity than the standard yttria fully-stabilized zirconia ionic conductor. This property turns these ceria-based ionic conductors promising materials for application in solid oxide fuel cells operating at intermediate temperatures (500-700 deg C). One of the most utilized approaches to optimize the electrical conductivity and other properties of these materials is the introduction of a second additive. In this work, ceria-20 mol% gadolinia with additions of 1, 2.5 and 5 mol% of SrO, TiO 2 and SrTiO 3 as co-additives were prepared by solid state reaction. The main purpose was to investigate the effects of the co-additives on densification, microstructure and electrical conductivity of the solid electrolyte. Sintered pellets were characterized by apparent density, X-ray diffraction, Raman spectroscopy, scanning electron microscopy and electrical conductivity by impedance spectroscopy. The additives were found to exert different influences in all studied properties. The way they influence the solid electrolyte properties depends on the type and content of the additive. SrO addition to doped ceria improves the intergranular conductivity, but decreases the apparent density of the pellets. Increase of densification was obtained with TiO 2 addition. This additive promotes increase of the blocking of charge carriers at the grain boundaries due to solute exsolution and formation of the pyrochlore Gd 2 Ti 2 O 7 phase at grain boundaries for contents in excess of the solubility limit. No influence on densification was found for SrTiO 3 additions. (author)

  4. Eudialyte-group minerals from the Monte de Trigo alkaline suite, Brazil: composition and petrological implications

    Directory of Open Access Journals (Sweden)

    Gaston Eduardo Enrich Rojas

    Full Text Available ABSTRACT: The Monte de Trigo alkaline suite is a SiO2-undersaturated syenite-gabbroid association from the Serra do Mar alkaline province. Eudialyte-group minerals (EGMs occur in one nepheline microsyenite dyke, associated with aegirine-augite, wöhlerite, låvenite, magnetite, zircon, titanite, britholite, and pyrochlore. Major compositional variations include Si (25.09- 25.57 apfu , Nb (0.31- 0.76 apfu , Fe (1.40-2.13 apfu , and Mn (1.36- 2.08 apfu . The EGMs also contain relatively high contents of Ca (6.13- 7.10 apfu , moderate enrichment of rare earth elements (0.38-0.67 apfu , and a relatively low Na content (11.02-12.28 apfu , which can be correlated with their transitional agpaitic assemblage. EGM compositions indicate a complex solid solution that includes eudialyte, kentbrooksite, feklichevite, zirsilite-(Ce, georgbarsanovite, and manganoeudialyte components. EGM trace element analyses show low Sr and Ba contents and a negative Eu/Eu* anomaly, which are interpreted as characteristic of the parental magma due to the previous fractionation of plagioclase and/or alkali feldspar. The EGMs from the dyke border have higher contents of Fe, Sr (2,161-2,699 ppm, Mg (1,179-3,582 ppm, and Zn (732- 852 ppm than those at the dyke center. These differences are related to the incorporation of xenoliths and xenocrysts of melatheralitic host rock into the nepheline-syenitic magma followed by crystal-melt diffusive exchange.

  5. The Elk Creek Carbonatite, Southeast Nebraska-An Overview

    International Nuclear Information System (INIS)

    Carlson, M. P.; Treves, S. B.

    2005-01-01

    A framework geophysical program in southeastern Nebraska during 1970 identified a near-circular feature having gravity relief of about 8 mgal and a magnetic anomaly of about 800 gammas. Analysis of the geophysical data provided a model of a cylindrical mass of indefinite length with a radius of 5500 ft (1676 m) and beveled at the basement surface at about 600 ft (183 m). At the approximate depth at which Precambrian rocks were expected, the initial test hole (2-B-71) encountered an iron-rich weathered zone overlying carbonate-rich rock. The carbonate rocks consist essentially of dolomite, calcite, and ankerite and lesser amounts of hematite, chlorite, phlogopite, barite, serpentine, pyrochlore, and quartz and contain barium, strontium, and rare earths. Total REE, P2O5, and 87Sr/86Sr ratios confirm the carbonatite identification. Texturally, the rocks range from fragmental to contorted to massive. Associated with the carbonatite are lesser amounts of basalt, lamprophyre, and syenite. Additional exploratory drilling has provided about 80,000 ft (24,384 m) of rock record and has penetrated about 3400 ft (1038 m) of carbonatite. The carbonatite is overlain by marine sediments of Pennsylvanian (Missourian) age. The surrounding Precambrian basement rocks are low-to medium-grade metamorphic gneiss and schist of island arc origin and granitic plutons. The Elk Creek carbonatite is located near the boundary between the Penokean orogen created at about 1.84 Ga (billion years) and the Dawes terrane (1.78 Ga) of the Central Plains orogen. This boundary strongly influenced the geometry of both the Midcontinent Rift System (1.1 Ga) and the Nemaha uplift (0.3 Ga). It is assumed that the emplacement of the Elk Creek carbonatite (0.5 Ga) was influenced similarly by the pre-existing tectonic sutures

  6. Fabrication and properties of La{sub 2-x}Gd{sub x}Hf{sub 2}O{sub 7} transparent ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhengjuan [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhou, Guohong, E-mail: sic_zhough@mail.sic.ac.cn [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Zhang, Fang; Qin, Xianpeng [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Ai, Jianping [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Wang, Shiwei, E-mail: swwang51@mail.sic.ac.cn [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China)

    2016-01-15

    La{sub 2-x}Gd{sub x}Hf{sub 2}O{sub 7} (x=0–2.0) transparent ceramics were fabricated through vacuum sintering from nano-powders synthesized by a simple combustion method. The phase composition of the powders and final ceramics, the in-line transmittance, microstructures and density of the ceramics were investigated. With the increasing of Gd content, the ceramics maintained the cubic pyrochlore structure, and the lattice parameters decreased, whilst the densities increased linearly. All the ceramics were transparent. The highest in-line transmittance was 76.1% at 800 nm (x=1.2). With high density (7.91–8.88 g/cm{sup 3}) and effective atomic number, some of the La{sub 2-x}Gd{sub x}Hf{sub 2}O{sub 7} (x=0–2.0) transparent ceramics are promising candidates for scintillator hosts. - Highlights: • A new series of La{sub 2-x}Gd{sub x}Hf{sub 2}O{sub 7} transparent ceramics were fabricated by vacuum sintering using combustion-synthesized powders. • All the ceramics are transparent and the in-line transmittance can reach to 76.1% at 800 nm when x=1.2. • The Gd content has effects on the crystal structure, in-line transmittance, microstructures and densities of the ceramics. • With high density (7.91~8.88 g/cm3) and effective atomic number, some of the La2-xGdxHf2O7 transparent ceramics are promising candidates for scintillator hosts.

  7. International Uranium Resources Evaluation Project (IUREP) national favourability studies: Saudi Arabia

    International Nuclear Information System (INIS)

    1977-09-01

    Saudi Arabia occupies most of the Arabian Peninsula and has an area of 872,722 sq miles, or 2,260,350 sq km. The ancient Arabian Shield of igneous and metamorphic rocks comprises most of the western third of the country. The shield contains many extinct volcanoes surrounded by lava beds. Sloping eastwards are the newer sedimentary areas in which rich oil fields are found. In Saudi Arabia oil is paramount and less effort has been put into searching for mineral deposits than in other countries of similar size and geology. Pour aerial radiometric surveys have been undertaken and some of the anomalies discovered in the earlier ones were ground checked by an IAEA expert in 1963-64. Two anomalies warranted more detailed work, these were the Jabal Said anomaly in the Central Shield area and the Al Ghrayyat in Wadi Sawawin about 70 miles from the Jordan border. The Jabal Said anomaly consists of a zone of altered rocks consisting largely of pegmatite and pegmatite granite= Allanite, pyrochlore, cyrtolite, xenotime and monazite are the ore minerals,, The deposit was estimated to have 2.2 million tons of ore grading 0.2 - 0.3 percent Nb 2 O 5 and 0.03 - 0,05% U 3 O 8 . The other occurrence at Al Ghrayyat is similar but with much lower grade uranium content. In view of the huge size of Saudi Arabia, the existence of many geologically favourable rock types and the poor coverage by sophisticated uranium exploration techniques, the Speculative Potential is placed between 10,000 and 50,000 Tonnes uranium. (author)

  8. Thermal conductivity issues of EB-PVD thermal barrier coatings

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, U.; Raetzer-Scheibe, H.J.; Saruhan, B. [DLR - German Aerospace Center, Institute of Materials Research, 51170 Cologne (Germany); Renteria, A.F. [BTU, Physical Metallurgy and Materials Technology, Cottbus (Germany)

    2007-09-15

    The thermal conductivity of electron-beam physical vapor deposited (EB-PVD) thermal barrier coatings (TBCs) was investigated by the Laser Flash technique. Sample type and methodology of data analyses as well as atmosphere during the measurement have some influence on the data. A large variation of the thermal conductivity was found by changes in TBC microstructure. Exposure at high temperature caused sintering of the porous microstructure that finally increased thermal conductivity up to 30 %. EB-PVD TBCs show a distinct thickness dependence of the thermal conductivity due to the anisotropic microstructure in thickness direction. Thin TBCs had a 20 % lower thermal conductivity than thick coatings. New compositions of the ceramic top layer offer the largest potential to lower thermal conductivity. Values down to 0.8W/(mK) have been already demonstrated with virgin coatings of pyrochlore compositions. (Abstract Copyright [2007], Wiley Periodicals, Inc.) [German] Die Waermeleitfaehigkeit von elektronenstrahl-aufgedampften (EB-PVD) Waermedaemmschichten (TBCs) wurde mittels Laser-Flash untersucht. Probentyp, Messmethodik und die Atmosphaere waehrend der Messung haben einen Einfluss auf die Ergebnisse. Aenderungen in der Mikrostruktur der TBC fuehrten zu grossen Unterschieden der Waermeleitfaehigkeit. Eine Hochtemperaturbelastung verursachte Sintervorgaenge in der poroesen Mikrostruktur, was die Waermeleitfaehigkeit um bis zu 30 % ansteigen liess. EB-PVD TBCs zeigen eine deutliche Dickenabhaengigkeit der Waermeleitfaehigkeit durch die Anisotropie der Mikrostruktur in dieser Richtung. Duenne TBCs haben eine um 20 % geringere Waermeleitfaehigkeit als dicke Schichten. Neue Zusammensetzungen der keramischen Deckschicht bieten die groessten Moeglichkeiten fuer eine Reduktion der Waermeleitfaehigkeit. Werte bis zu 0,8 W/(mK) wurden damit bereits erreicht. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  9. Preparation of Lead Magnesium Niobate-Lead Zirconate Titanate Films and Their Crystallization Behaviors

    International Nuclear Information System (INIS)

    Tursiloadi, Silvester

    2002-01-01

    The thin films with composition near morpotropic phase boundary (MPB) of the system xPb(Mg 1 /3, Nb 2 /3) O 3 -yPbTiO 3 -zPbZrO 3 (x = 0-0.35, y = 0.47 and z = 0.53), were prepared by sol-gel method. The starting materials were consisted of Pb(iso-OC 3 H 7 ) 2 , Zr(n-OC 4 H 9 ) 4 , Ti(iso-OC 3 H 7 ) 4 , Mg(CH 3 COO) 2 4H 2 O and Nb(OC 2 H 5 ) 5 . The l-propanol was used as solvent. The concentration of PMN-PT-PZ in coating solution was 0.7 M, and the pH of the solution was 4.5. The thin films were prepared by dip coating and spin coating. The crystallization behaviors of the PMN-PT-PZ thin films showed that the formation of perovskite phase at low temperature becomes difficult with increasing the content of PMN. The amounts of pyrochlore and perovskite phase in PMN-PT-PZ films depended on the heating temperatures, and PMN contents. Single-phase perovskite was found for the coated films containing 0 and 12.5 mol% after calculating at 600 o C, 21 mol% after calculating at 700 o C, and 30 mol% after calculating at 750 o C. Single-phase perovskite of coated films will never be found when the content of PMN was 35 mol%

  10. DEVELOPMENT OF CERAMIC WASTE FORMS FOR AN ADVANCED NUCLEAR FUEL CYCLE

    Energy Technology Data Exchange (ETDEWEB)

    Marra, J.; Billings, A.; Brinkman, K.; Fox, K.

    2010-11-30

    A series of ceramic waste forms were developed and characterized for the immobilization of a Cesium/Lanthanide (CS/LN) waste stream anticipated to result from nuclear fuel reprocessing. Simple raw materials, including Al{sub 2}O{sub 3} and TiO{sub 2} were combined with simulated waste components to produce multiphase ceramics containing hollandite-type phases, perovskites (particularly BaTiO{sub 3}), pyrochlores and other minor metal titanate phases. Three fabrication methodologies were used, including melting and crystallizing, pressing and sintering, and Spark Plasma Sintering (SPS), with the intent of studying phase evolution under various sintering conditions. X-Ray Diffraction (XRD) and Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM/EDS) results showed that the partitioning of the waste elements in the sintered materials was very similar, despite varying stoichiometry of the phases formed. Identification of excess Al{sub 2}O{sub 3} via XRD and SEM/EDS in the first series of compositions led to a Phase II study, with significantly reduced Al{sub 2}O{sub 3} concentrations and increased waste loadings. The Phase II compositions generally contained a reduced amount of unreacted Al{sub 2}O{sub 3} as identified by XRD. Chemical composition measurements showed no significant issues with meeting the target compositions. However, volatilization of Cs and Mo was identified, particularly during melting, since sintering of the pressed pellets and SPS were performed at lower temperatures. Partitioning of some of the waste components was difficult to determine via XRD. SEM/EDS mapping showed that those elements, which were generally present in small concentrations, were well distributed throughout the waste forms.

  11. Investigation of environmental conditions at Sarfartoq 1987-88. Collection of samples for testing, measurement of radon and analyses for polonium-210 and lead-210. [Greenland]. Miljoeundersoegelser ved Sarfartoq 1987-88. Proeveindsamling, radonmaaling og analyser for polonium-210 og bly-210

    Energy Technology Data Exchange (ETDEWEB)

    Aastrup, P; Munk Hansen, M

    1989-01-01

    The sampling of plants and animals is part of environmental base line studies initiated by the Mineral Resources Administration for Greenland in relation to plans for exploration and exploitation of a niobium occurence. Samples have been collected in areas expected to be influenced by mining activities and in reference areas. The collected species of plants include northern willow, Bellard's kobresia, lichen (Cetraria nivalis), and others. Samples of animals include musk oxen, reindeer, alpine hare, ptarmigan, fox, and arctic char. However, 60 samples have been analyzed for polonium-210 and lead-210. The highest concentrations were found in lichen and the lowest in muscle tissue. In many samples systematic differences between the concentrations of the two isotopes were observed indicating that polonium-210 should continue to be part of the base line study program and the monitoring program if mining is started. The observed concentrations pose no health problem. 30 kg bulk samples of the best pyrochlore ore and the rock c. 10 m on both sides of the mineralization (the side rock) were analyzed for niobium, tantalum, some trace elements, and natural radioactive isotopes. The ore sample has concentrations of 33.17% niobium, 0.4% tantalum, 0.77% uranium, and more than 0.37% rare earth elements. The concentrations of all other analyzed elements are low. The ore has very well defined boundaries and there is a very low concentration of radioactive elements in the side rock. The naturally occurring concentrations of radon have been measured at stations on top of the mineralization, within the carbonatite complex and outside the complex. The concentrations generally are very low. However, the concentrations in the complex are significantly higher than outside the complex. This reflects an elevated uranium concentration of the carbonatite complex rocks. (AB).

  12. Radiological Mapping of the Alkaline Intrusive Complex of Jombo, South Coastal Kenya by In-Situ Gamma-Ray Spectrometry

    Science.gov (United States)

    Kaniu, Ian; Darby, Iain G.; Kalambuka Angeyo, Hudson

    2016-04-01

    Carbonatites and alkaline intrusive complexes are rich in a variety of mineral deposits such as rare earth elements (REEs), including Nb, Zr and Mn. These are often associated with U and Th bearing minerals, including monazite, samarskite and pyrochlore. Mining waste resulting from mineral processing activities can be highly radioactive and therefore poses a risk to human health and environment. The Jombo complex located in Kenya's south coastal region is potentially one of the richest sources of Nb and REEs in the world. It consists of the main intrusion at Jombo hill, three associated satellite intrusions at Mrima, Kiruku and Nguluku hills, and several dykes. The complex is highly heterogeneous with regard to its geological formation as it is characterized by alkaline igneous rocks and carbonatites which also influence its radio-ecological dynamics. In-situ gamma spectrometry offers a low-cost, rapid and spatially representative radioactivity estimate across a range of landscapes compared to conventional radiometric techniques. In this work, a wide ranging radiological survey was conducted in the Jombo complex as follow up on previous studies[1,2], to determine radiation exposure levels and source distributions, and perform radiological risk assessments. The in-situ measurements were carried out using a 2.0 l NaI(Tl) PGIS-2 portable detector from Pico Envirotec Inc integrated with GPS, deployed for ground (back-pack) and vehicular gamma-ray spectrometry. Preliminary results of radiological distribution and mapping will be presented. [1] Patel, J. P. (1991). Discovery and Innovation, 3(3): 31-35. [2] Kebwaro, J. M. et. al. (2011). J. Phys. Sci., 6(13): 3105-3110.

  13. Formation of Ag nanoparticles in percolative Ag–PbTiO3 composite thin films through lead-rich Ag–Pb alloy particles formed as transitional phase

    International Nuclear Information System (INIS)

    Hu, Tao; Wang, Zongrong; Su, Yanbo; Tang, Liwen; Shen, Ge; Song, Chenlu; Han, Gaorong; Weng, Wenjian; Ma, Ning; Du, Piyi

    2012-01-01

    The Ag nanoparticle dispersed percolative PbTiO 3 ceramic thin film was prepared in situ by sol–gel method with excess lead introduced into a sol precursor. The influence of excess lead and the heat treatment time on the formation of Ag nanoparticles was investigated by energy dispersive X-ray spectra, scanning electron microscopy, X-ray diffraction, and ultraviolet–visible absorption spectra. Results showed that the excess lead introduced into the sol precursor was in favor of the crystallization of the thin film and in favor of formation of the perovskite phase without the pyrochlore phase. Lead-rich Ag–Pb alloy particles first formed in the thin films and then decomposed to become large numbers of Ag nanoparticles of about 3 nm in size in the thin films when the heat treatment time was longer than 2 min. The content of the Ag nanoparticles increased with increasing the heat treatment time. The percolative behavior appears typically in the Ag nanoparticle dispersed thin films. The dielectric constant of the thin film was about 3 times of that without Ag nanoparticles. - Highlights: ► The Ag nanoparticles formed in the PbTiO 3 percolative ceramic thin film. ► The Ag–Pb alloy particles formed as transitional phase during thin film preparation. ► The lead-rich Ag–Pb alloy particles decomposed to form Ag nanoparticles in the film. ► Permittivity of the thin film is 3 times higher than that without Ag nanoparticles.

  14. The influence of crystal structure on ion-irradiation tolerance in the Sm{sub (x)}Yb{sub (2-x)}TiO{sub 5} series

    Energy Technology Data Exchange (ETDEWEB)

    Aughterson, R.D., E-mail: roa@ansto.gov.au [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234 (Australia); Australian Centre for Microscopy and Microanalysis, The University of Sydney, NSW 2006 (Australia); Lumpkin, G.R.; Reyes, M. de los [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234 (Australia); Gault, B. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Baldo, P.; Ryan, E. [Materials Science Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Whittle, K.R. [Centre for Materials and Structures, School of Engineering, The University of Liverpool, Liverpool L69 3GH UK (United Kingdom); Smith, K.L. [Government International and External Relations, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234 (Australia); Cairney, J.M. [Australian Centre for Microscopy and Microanalysis, The University of Sydney, NSW 2006 (Australia)

    2016-04-01

    This ion-irradiation study covers the four major crystal structure types in the Ln{sub 2}TiO{sub 5} series (Ln = lanthanide), namely orthorhombic Pnma, hexagonal P6{sub 3}/mmc, cubic (pyrochlore-like) Fd-3m and cubic (fluorite-like) Fm-3m. This is the first systematic examination of the complete Ln{sub 2}TiO{sub 5} crystal system and the first reported examination of the hexagonal structure. A series of samples, based on the stoichiometry Sm{sub (x)}Yb{sub (2-x)}TiO{sub 5} (where x = 2, 1.4, 1, 0.6, and 0) have been irradiated using 1 MeV Kr{sup 2+} ions and characterised in-situ using a transmission electron microscope. Two quantities are used to define ion-irradiation tolerance: critical dose of amorphisation (D{sub c}), which is the irradiating ion dose required for a crystalline to amorphous transition, and the critical temperature (T{sub c}), above which the sample cannot be rendered amorphous by ion irradiation. The structure type plus elements of bonding are correlated to ion-irradiation tolerance. The cubic phases, Yb{sub 2}TiO{sub 5} and Sm{sub 0.6}Yb{sub 1.4}TiO{sub 5}, were found to be the most radiation tolerant, with T{sub c} values of 479 and 697 K respectively. The improved radiation tolerance with a change in symmetry to cubic is consistent with previous studies of similar compounds.

  15. Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing

    Science.gov (United States)

    Dandeneau, Christopher S.; Hong, Tao; Brinkman, Kyle S.; Vance, Eric R.; Amoroso, Jake W.

    2018-04-01

    Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba1.0Cs0.3Cr1.0Al0.3Fe1.0Ti5.7O16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayed prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed "islands" rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo was greater in the HIP specimens.

  16. Electrical properties and conduction mechanisms of Ru-based thick-film (cermet) resistors

    International Nuclear Information System (INIS)

    Pike, G.E.; Seager, C.H.

    1977-01-01

    This paper presents an experimental study of the electrical conduction mechanisms in thick-film (cermet) resistor. The resistors were made from one custom and three commercially formulated inks with sheet resistivities ranging from 10 2 to 10 6 Ω/D 7 Alembertian in decade increments. Their microstructure and composition have been examined using optical and scanning electron microscopy, electron microprobe analysis, x-ray diffraction, and various chemical analyses. This portion of our study shows that the resistors are heterogeneous mixtures of metallic metal oxide particles (approx.4 x 10 -5 cm in diameter) and a lead silicate glass. The metal oxide particles are ruthenium containing pyrochlores, and are joined to form a continuous three-dimensional network of chain segments. The principal experimental work reported here is an extensive study of the electrical transport properties of the resistors. The temperature dependence of conductance has been measured from 1.2 to 400 K, and two features common to all resistors are found. There is a pronounced decrease in conductance at low temperatures and a shallow maximum at several hundred Kelvin. Within the same range of temperatures the reversible conductance as a function of electric field from 0 to 28 kV/cm has been studied. The resistors are non-Ohmic at all temperatures, but particularly at cryogenic temperatures for low fields. At higher fields the conductance shows a linear variation with electric field. The thick-film resistors are found to have a small dielectric constant and a (nearly) frequency-independent conductance from dc to 50 MHz. The magnetoresistance to 100 kG, the Hall mobility, and the Seebeck coefficient of most of the resistors have been measured and discovered to be quite small. Many of the electrical transport properties have also been determined for the metal oxide particles which were extracted from the fired resistors

  17. Transparent La{sub 2−x}Gd{sub x}Zr{sub 2}O{sub 7} ceramics obtained by combustion method and vacuum sintering

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhengjuan [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China); Zhou, Guohong, E-mail: sic_zhough@mail.sic.ac.cn [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Qin, Xianpeng; Yang, Yan [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Zhang, Guangjun [SCHOTT Glass Technologies (Suzhou) Co. Ltd., Suzhou 215009 (China); Menke, Yvonne [Schott AG, Corporate Research and Technology Development, Hattenbergstrasse 10, 55122 Mainz (Germany); Wang, Shiwei, E-mail: swwang51@mail.sic.ac.cn [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China)

    2014-02-05

    Highlights: • Combustion method and vacuum sintering were used to fabricate La{sub 2-x}Gd{sub x}Zr{sub 2}O{sub 7}. • The lattice parameters decreased with the increase of Gd{sup 3+} concent(x). • The absorption edge of the transmittance curves shifted to UV region from 0.4-2.0. • All the ceramics have high n (2.08), making them candidate for optical lens. • With the increase of x, the effective atomic number and density increased. -- Abstract: Transparent La{sub 2−x}Gd{sub x}Zr{sub 2}O{sub 7} (x = 0–2.0) ceramics were prepared via vacuum sintering from nanometric powders synthesized by a simple combustion method. The changes of phase composition, morphology and in-line transmittance of the resulting ceramics with Gd{sup 3+} content’s variation were investigated. With the increase of Gd{sup 3+} content, the samples keep the pyrochlore structure, but the X-ray diffraction peaks of the powders and ceramics shift to higher angle as the lattice parameters become smaller. All the ceramics are transparent with high in-line transmittance and high refractive index (2.08 @ 632.8 nm, x = 0.4–1.6). These results indicate that La{sub 2−x}Gd{sub x}Zr{sub 2}O{sub 7} ceramics might be used as optical lens. Moreover, with the increase of Gd{sup 3+} content, the effective atomic number and density of the ceramics increase, therefore making them promising host candidates for scintillators.

  18. Molecular environmental science using synchrotron radiation: Chemistry and physics of waste form materials

    International Nuclear Information System (INIS)

    Lindle, Dennis W.; Shuh, David K.

    2005-01-01

    Production of defense-related nuclear materials has generated large volumes of complex chemical wastes containing a mixture of radionuclides. The disposition of these wastes requires conversion of the liquid and solid-phase components into durable, solid forms suitable for long-term immobilization [1]. Specially formulated glass compositions, many of which have been derived from glass developed for commercial purposes, and ceramics such as pyrochlores and apatites, will be the main recipients for these wastes. The performance characteristics of waste-form glasses and ceramics are largely determined by the loading capacity for the waste constituents (radioactive and non-radioactive) and the resultant chemical and radiation resistance of the waste-form package to leaching (durability). There are unique opportunities for the use of near-edge soft-x-ray absorption fine structure (NEXAFS) spectroscopy to investigate speciation of low-Z elements forming the backbone of waste-form glasses and ceramics. Although nuclear magnetic resonance (NMR) is the primary technique employed to obtain speciation information from low-Z elements in waste forms, NMR is incompatible with the metallic impurities contained in real waste and is thus limited to studies of idealized model systems. In contrast, NEXAFS can yield element-specific speciation information from glass constituents without sensitivity to paramagnetic species. Development and use of NEXAFS for eventual studies of real waste glasses has significant implications, especially for the low-Z elements comprising glass matrices [5-7]. The NEXAFS measurements were performed at Beamline 6.3.1, an entrance-slitless bend-magnet beamline operating from 200 eV to 2000 eV with a Hettrick-Underwood varied-line-space (VLS) grating monochromator, of the Advanced Light Source (ALS) at LBNL. Complete characterization and optimization of this beamline was conducted to enable high-performance measurements

  19. Amorphization of complex ceramics by heavy-particle irradiations

    International Nuclear Information System (INIS)

    Ewing, R.C.; Wang, L.M.

    1994-11-01

    Complex ceramics, for the purpose of this paper, include materials that are generally strongly bonded (mixed ionic and covalent), refractory and frequently good insulators. They are distinguished from simple, compact ceramics (e.g., MgO and UO 2 ) by structural features which include: (1) open network structures, best characterized by a consideration of the shape, size and connectivity of coordination polyhedra; (2) complex compositions which characteristically lead to multiple cation sites and lower symmetry; (3) directional bonding; (4) bond-type variations within the structure. The heavy particle irradiations include ion-beam irradiations and recoil-nucleus damage resulting from a-decay events from constituent actinides. The latter effects are responsible for the radiation-induced transformation to the metamict state in minerals. The responses of these materials to irradiation are complex, as energy may be dissipated ballistically by transfer of kinetic energy from an incident projectile or radiolytically by conversion of radiation-induced electronic excitations into atomic motion. This results in isolated Frenkel defect pairs, defect aggregates, isolated collision cascades or bulk amorphization. Thus, the amorphization process is heterogeneous. Only recently have there been systematic studies of heavy particle irradiations of complex ceramics on a wide variety of structure-types and compositions as a function of dose and temperature. In this paper, we review the conditions for amorphization for the tetragonal orthosilicate, zircon [ZrSiO 4 ]; the hexagonal orthosilicate/phosphate apatite structure-type [X 10 (ZO 4 ) 6 (F,Cl,O) 2 ]; the isometric pyrochlores [A 1-2 B 2 O 6 (O,OH,F) 0-1p H 2 O] and its monoclinic derivative zirconotite [CaZrTi 2 O 7 ]; the olivine (derivative - hcp) structure types, α- VI A 2 IV BO 4 , and spinel (ccp), γ- VI A 2 IV BO 4

  20. Coulombic charge ice

    Science.gov (United States)

    McClarty, P. A.; O'Brien, A.; Pollmann, F.

    2014-05-01

    We consider a classical model of charges ±q on a pyrochlore lattice in the presence of long-range Coulomb interactions. This model first appeared in the early literature on charge order in magnetite [P. W. Anderson, Phys. Rev. 102, 1008 (1956), 10.1103/PhysRev.102.1008]. In the limit where the interactions become short ranged, the model has a ground state with an extensive entropy and dipolar charge-charge correlations. When long-range interactions are introduced, the exact degeneracy is broken. We study the thermodynamics of the model and show the presence of a correlated charge liquid within a temperature window in which the physics is well described as a liquid of screened charged defects. The structure factor in this phase, which has smeared pinch points at the reciprocal lattice points, may be used to detect charge ice experimentally. In addition, the model exhibits fractionally charged excitations ±q/2 which are shown to interact via a 1/r potential. At lower temperatures, the model exhibits a transition to a long-range ordered phase. We are able to treat the Coulombic charge ice model and the dipolar spin ice model on an equal footing by mapping both to a constrained charge model on the diamond lattice. We find that states of the two ice models are related by a staggering field which is reflected in the energetics of these two models. From this perspective, we can understand the origin of the spin ice and charge ice ground states as coming from a dipolar model on a diamond lattice. We study the properties of charge ice in an external electric field, finding that the correlated liquid is robust to the presence of a field in contrast to the case of spin ice in a magnetic field. Finally, we comment on the transport properties of Coulombic charge ice in the correlated liquid phase.

  1. The origin of secondary heavy rare earth element enrichment in carbonatites: Constraints from the evolution of the Huanglongpu district, China

    Science.gov (United States)

    Smith, M.; Kynicky, J.; Xu, Cheng; Song, Wenlei; Spratt, J.; Jeffries, T.; Brtnicky, M.; Kopriva, A.; Cangelosi, D.

    2018-05-01

    The silico‑carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartz-bearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnäsite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnäsite and parisite where replaced by synchysite-(Ce) and röntgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate hydrothermal fluids must have contributed HREE to the mineralisation. The evolution of the fluorcarbonate mineral assemblage requires an increase in aCa2+ and aCO32- in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl-) may account for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferential HREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexation may have been important for preferential HREE transport. Alongside HREE-enriched magmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE

  2. Critical behavior of two- and three-dimensional ferromagnetic and antiferromagnetic spin-ice systems using the effective-field renormalization group technique

    Science.gov (United States)

    Garcia-Adeva, Angel J.; Huber, David L.

    2001-07-01

    In this work we generalize and subsequently apply the effective-field renormalization-group (EFRG) technique to the problem of ferro- and antiferromagnetically coupled Ising spins with local anisotropy axes in geometrically frustrated geometries (kagomé and pyrochlore lattices). In this framework, we calculate the various ground states of these systems and the corresponding critical points. Excellent agreement is found with exact and Monte Carlo results. The effects of frustration are discussed. As pointed out by other authors, it turns out that the spin-ice model can be exactly mapped to the standard Ising model, but with effective interactions of the opposite sign to those in the original Hamiltonian. Therefore, the ferromagnetic spin ice is frustrated and does not order. Antiferromagnetic spin ice (in both two and three dimensions) is found to undergo a transition to a long-range-ordered state. The thermal and magnetic critical exponents for this transition are calculated. It is found that the thermal exponent is that of the Ising universality class, whereas the magnetic critical exponent is different, as expected from the fact that the Zeeman term has a different symmetry in these systems. In addition, the recently introduced generalized constant coupling method is also applied to the calculation of the critical points and ground-state configurations. Again, a very good agreement is found with exact, Monte Carlo, and renormalization-group calculations for the critical points. Incidentally, we show that the generalized constant coupling approach can be regarded as the lowest-order limit of the EFRG technique, in which correlations outside a frustrated unit are neglected, and scaling is substituted by strict equality of the thermodynamic quantities.

  3. The effect of dual complexing agents of lactic and citric acids on the formation of sol-gel derived Ag–PbTiO3 percolative thin film

    International Nuclear Information System (INIS)

    Su, Yanbo; Hu, Tao; Tang, Liwen; Weng, Wenjian; Han, Gaorong; Ma, Ning; Du, Piyi

    2014-01-01

    Controlling the formation of conductive particles to be nano-scale is important for achieving percolation effect in metal dispersed thin film composite to contribute extraordinary dielectric properties required for miniaturization of electronic devices. In this paper, lactic acid (LA) and citric acid (CA) were used as dual complexing agents to prepare a typical Ag nanoparticle dispersed PbTiO 3 (PTO) composite thin film by using a sol-gel method. The phase structure of the thin film and the coordination effect between complexing agent and metallic ions were investigated. It revealed that LA coordinated with Ti 4+ and Pb 2+ and CA coordinated with Ag + . Lead was fixed inside the gel network by LA and restricted to evaporate during heat treatment thus the pyrochlore phase was prevented from forming in the thin film. Ag + was coordinated by CA and the diffusion and thus aggregation of silver during gelation and annealing process were weakened. Silver nanoparticles dispersed in the PTO matrix formed with dual complexing agents of LA and CA introduced during the preparation process. The composite thin film of perfect perovskite phase with silver nanoparticles embedded was obtained at the molar ratio of LA/lead = 0.5 and CA/lead = 0.5. The dielectric constant of the thin film with silver nanoparticles is 5 times higher than that without silver nanoparticles. - Highlights: • Ag nanoparticle–PbTiO 3 percolative film with high dielectric property is prepared. • Evaporation of lead was prevented by coordinating Pb with lactic acid agent. • Dual complexing agents contribute block and pinning effects to form Ag nanoparticles

  4. The influence of CeO2 on the microstructure and electrical behaviour of ZnO-Bi2O3 based varistors

    International Nuclear Information System (INIS)

    Lei Ming; Li Shengtao; Jiao Xiaodong; Li Jianying; Alim, Mohammad A

    2004-01-01

    The processing-microstructure-property relations have been studied in order to understand the role of the addition of CeO 2 (up to 0.9 mole%) in the ZnO-Bi 2 O 3 based varistor recipe. The microstructural investigation suggests that CeO 2 is segregated at the corners of the ZnO grains in addition to the existence of the Zn 7 Sb 2 O 12 spinel phase. However, the α -spinel phase was observed instead of the β -spinel phase that is usually found in most commercial and laboratory ZnO-Bi 2 O 3 based varistors. The α -spinel phase is more stable than the β -spinel phase and does not transform to the pyrochlore phase during the cooling process. The most significant effect of the CeO 2 particles is the ZnO grain refinement owing to the pinning effect of the grain growth. The average grain size decreases from 7.8 to 5.7 μm when compared to the 0.9 mole% CeO 2 -added sample against the CeO 2 -free sample. This grain refinement results in a significantly enhanced breakdown field when compared to the CeO 2 -free sample. The coefficient of nonlinearity of the current-voltage (I-V) characteristics is found to be nearly identical for the CeO 2 added varistor materials. However, when a slower cooling cycle (1 deg. C min -1 instead of 4 deg. C min -1 ) is used in the sintering process, these varistor materials exhibited a high nonlinear coefficient (α = 29 ± 5) as extracted from the I-V behaviour

  5. Universal properties of strongly frustrated quantum magnets in high magnetic fields

    International Nuclear Information System (INIS)

    Richter, J.

    2007-01-01

    For a class of frustrated antiferromagnetic spin systems including e.g. the 1D saw tooth chain, the 2D kagom'e and checkerboard, the 3D pyrochlore lattices exact eigenstates consisting of several independent localized magnons in a ferromagnetic environment can be constructed. Important structural elements of the relevant systems are triangles being attached to polygons or lines. Then the magnons can be trapped on these polygons/lines. If the concentration of localized magnons is small they can be distributed randomly over the lattice. Increasing the number of localized magnons their distribution over the lattice becomes more regular and finally the magnons condensate in a crystal-like state. The physical relevance of these eigenstates emerges in high magnetic fields where they become ground states of the system. The spin systems having localized-magnon eigenstates exhibit universal features at low-temperatures in the vicinity of the saturation field: (i) The ground-state magnetization exhibits a macroscopic jump to saturation. This jump is accompanied by a preceding plateau (ii) The ground state at the saturation field is highly degenerate. The degeneracy grows exponentially with the system size and leads to a low-temperature maximum in the isothermal entropy versus field curve at the saturation field and to an enhanced magnetocaloric effect, which allows efficient magnetic cooling from quite large temperatures down to very low ones. (iii) By mapping the localized magnon spin degrees of freedom on a hard-core lattice gas one can find explicit analytical universal expressions for the low-temperature thermodynamics near saturation field. (iv) The magnetic system may exhibit a field-tuned structural instability in the vicinity of the saturation field. (author)

  6. Microstructure of HIPed and SPSed 9Cr-ODS steel and its effect on helium bubble formation

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Chenyang [Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Material Science and Engineering, Northeastern University, Shenyang 110819, Liaoning (China); Department of Nuclear Engineering and Radiological Science, University of Michigan, Ann Arbor, MI, 48109 (United States); Lu, Zheng, E-mail: luz@atm.neu.edu.cn [Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Material Science and Engineering, Northeastern University, Shenyang 110819, Liaoning (China); Xie, Rui; Liu, Chunming [Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Material Science and Engineering, Northeastern University, Shenyang 110819, Liaoning (China); Wang, Lumin, E-mail: lmwang@umich.edu [Department of Nuclear Engineering and Radiological Science, University of Michigan, Ann Arbor, MI, 48109 (United States)

    2016-06-15

    Two 9Cr-ODS steels with the same nominal composition were consolidated by hot isostatic pressing (HIP, named COS-1) and spark plasma sintering (SPS, named COS-2). Helium ions were implanted into COS-1, COS-2 and non-ODS Eurofer 97 steels up at 673 K. Microstructures before and after helium ion implantations were carefully characterized. The results show a bimodal grain size distribution in COS-2 and a more uniform grain size distribution in COS-1. Nanoscale clusters of GP-zone type Y–Ti–O and Y{sub 2}Ti{sub 2}O{sub 7} pyrochlore as well as large spinel Mn(Ti)Cr{sub 2}O{sub 4} particles are all observed in the two ODS steels. The Y–Ti-enriched nano-oxides in COS-1 exhibit higher number density and smaller size than in COS-2. The Y–Ti-enriched nano-oxides in fine grains of COS-2 show higher number density and smaller size than that in coarse grains of COS-2. Nano-oxides effectively trap helium atoms and lead to the formation of high density and ultra-fine helium bubbles. - Highlights: • The microstructure changes of two ODS steels before and after helium ion implantation have been elucidated. • The mechanism of the microstructures of ODS steels under varied thermal mechanical processing paths have been explored. • The dependence of the size, density and distribution of helium bubbles on the specific microstructure features are explored.

  7. Combined effects of radiation damage and He accumulation on bubble nucleation in Gd{sub 2}Ti{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, Caitlin A., E-mail: ctayl105@vols.utk.edu [Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996 (United States); Patel, Maulik K. [Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996 (United States); Aguiar, Jeffery A. [Fuel Performance and Design Department, Idaho National Laboratory, Idaho Falls, ID 83415-6188 (United States); Material Science Center, National Renewable Energy Laboratory, Golden, CO 80220 (United States); Zhang, Yanwen [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996 (United States); Crespillo, Miguel L. [Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996 (United States); Wen, Juan [School of Nuclear Science and Technology, Lanzhou University, Lanzhou, Gansu 730000 (China); Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Xue, Haizhou [Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996 (United States); Wang, Yongqiang [Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Weber, William J. [Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996 (United States); Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

    2016-10-15

    Pyrochlores have long been considered as host phases for long-term immobilization of radioactive waste nuclides that would undergo α-decay for hundreds of thousands of years. This work utilizes ion-beam irradiations to examine the combined effects of radiation damage and He accumulation on bubble formation in Gd{sub 2}Ti{sub 2}O{sub 7} over relevant waste-form timescales. Helium bubbles are not observed in pre-damaged Gd{sub 2}Ti{sub 2}O{sub 7} implanted with 2 × 10{sup 16} He/cm{sup 2}, even after post-implantation irradiations with 7 MeV Au{sup 3+} at 300, 500, and 700 K. However, He bubbles with average diameters of 1.5 nm and 2.1 nm are observed in pre-damaged (amorphous) Gd{sub 2}Ti{sub 2}O{sub 7} and pristine Gd{sub 2}Ti{sub 2}O{sub 7}, respectively, after implantation of 2 × 10{sup 17} He/cm{sup 2}. The critical He concentration for bubble nucleation in Gd{sub 2}Ti{sub 2}O{sub 7} is estimated to be 6 at.% He. - Highlights: • He bubbles not formed in amorphous Gd{sub 2}Ti{sub 2}O{sub 7} implanted with 2 × 10{sup 16} He/cm{sup 2}, even after additional irradiation at 300 to 700 K. • He bubbles, 1.5 and 2.1 nm diameter, respectively, observed in amorphous and pristine Gd{sub 2}Ti{sub 2}O{sub 7} implanted to 2 × 10{sup 17} He/cm{sup 2}. • The critical He dose for bubble nucleation is estimated to be 6 at.% He.

  8. The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Yinbin, E-mail: miao2@illinois.edu [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Mo, Kun [Nuclear Engineering Division, Argonne National Laboratory, Lemont, IL 60493 (United States); Cui, Bai [Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, Lincoln, NE 68588 (United States); Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Chen, Wei-Ying [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Miller, Michael K.; Powers, Kathy A. [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37830 (United States); McCreary, Virginia; Gross, David [Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Almer, Jonathan [X-ray Science Division, Argonne National Laboratory, Lemont, IL 60493 (United States); Robertson, Ian M. [Department of Material Science and Engineering, University of Wisconsin-Madison, Madison, WA 53706 (United States); Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Stubbins, James F. [Department of Nuclear, Plasma and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)

    2015-03-15

    This work reports comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y{sub 2}O{sub 3}, fluorite Y{sub 2}O{sub 3}–HfO{sub 2} solid solution and pyrochlore (or fluorite) Y{sub 2}(Ti,Hf){sub 2−x}O{sub 7−x}. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Two different coherency relationships along with one axis-parallel relation between the oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. The results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation. - Highlights: • The oxide nanoparticles in a hafnium-containing austenitic ODS were characterized. • The nanoparticles are Y–Hf–Ti–O enriched phases according to APT and STEM–EDS. • Two coherency and an axis-parallel orientation relationships were found by HR-TEM. • Particle size has a prominent effect on the orientation relationship (OR). • Formation mechanism of the oxide nanoparticles was discussed based on the ORs.

  9. Soft-chemical synthesis and catalytic activity of Ni-Al and Co-Al layered double hydroxides (LDHs intercalated with anions with different charge density

    Directory of Open Access Journals (Sweden)

    Takahiro Takei

    2014-09-01

    Full Text Available Co-Al and Ni-Al layered double hydroxides (LDHs intercalated with three types of anionic molecules, dodecylsulfate (C12H25SO4−, DS, di-2-ethylsulfosuccinate ([COOC2H3EtBu]2C2H3SO3−, D2ES, and polytungstate (H2W12O4210−, HWO were prepared by means of ion-exchange and co-precipitation processes. With the use of DS and D2ES as intercalation agents, high crystallinity was maintained after intercalation into the LDHs. In the case of HWO, the intercalated LDHs could be obtained by ion-exchange as well as co-precipitation with a decline in the crystallinity; however, unreacted LDH was detected in the ion-exchange samples, and some unwanted phases such as hydroxide and pyrochlore were generated by the co-precipitation process. The maximum specific surface area and pore volume of the Ni-Al sample with intercalated HWO, prepared by the ion-exchange process were 74 m2/g and 0.174 mL/g, respectively. The occupancies of DS, D2ES, and HWO within the interlayer space were approximately 0.3–0.4, 0.5–0.6, and 0.1–0.2, respectively, in the Co-Al and Ni-Al LDHs. Analysis of the catalytic activity demonstrated that the DS-intercalated Ni-Al LDH sample exhibited relatively good catalytic activity for conversion of cyclohexanol to cyclohexanone.

  10. Computer Simulations and Theoretical Studies of Complex Systems: from complex fluids to frustrated magnets

    Science.gov (United States)

    Choi, Eunsong

    Computer simulations are an integral part of research in modern condensed matter physics; they serve as a direct bridge between theory and experiment by systemactically applying a microscopic model to a collection of particles that effectively imitate a macroscopic system. In this thesis, we study two very differnt condensed systems, namely complex fluids and frustrated magnets, primarily by simulating classical dynamics of each system. In the first part of the thesis, we focus on ionic liquids (ILs) and polymers--the two complementary classes of materials that can be combined to provide various unique properties. The properties of polymers/ILs systems, such as conductivity, viscosity, and miscibility, can be fine tuned by choosing an appropriate combination of cations, anions, and polymers. However, designing a system that meets a specific need requires a concrete understanding of physics and chemistry that dictates a complex interplay between polymers and ionic liquids. In this regard, molecular dynamics (MD) simulation is an efficient tool that provides a molecular level picture of such complex systems. We study the behavior of Poly (ethylene oxide) (PEO) and the imidazolium based ionic liquids, using MD simulations and statistical mechanics. We also discuss our efforts to develop reliable and efficient classical force-fields for PEO and the ionic liquids. The second part is devoted to studies on geometrically frustrated magnets. In particular, a microscopic model, which gives rise to an incommensurate spiral magnetic ordering observed in a pyrochlore antiferromagnet is investigated. The validation of the model is made via a comparison of the spin-wave spectra with the neutron scattering data. Since the standard Holstein-Primakoff method is difficult to employ in such a complex ground state structure with a large unit cell, we carry out classical spin dynamics simulations to compute spin-wave spectra directly from the Fourier transform of spin trajectories. We

  11. Contribution to the development of the MARS beamline to study oxide dispersion strengthened steels (ODS) irradiated with neutrons using synchrotron source: secondary phases evolution under irradiation

    International Nuclear Information System (INIS)

    Menut, Denis

    2016-01-01

    X-Ray Diffraction (XRD) coupled with X-ray Absorption Fine Structure (XAFS) analyses at the MARS beamline of the synchrotron SOLEIL facility were used to study the microstructural evolution of oxides phases found in oxide dispersion strengthened steels (ODS) irradiated in Material Testing Reactors. Two hold generations of ODS steel grades (DY and MA957) irradiated up to high fluencies (∼75 dpa) were studied. These experiments have required specific developments, in particular a dedicated sample holder. An important milestone was overcome integrating the MARS beamline to the nuclearized facilities accessible for CEA. First, XRD analysis provide new results concerning intermediate sizes of precipitates (around 100 nm) essentially from crystallographic point of view, the nano-sized oxides (from 1 to 10 nm) being not detected, due to the material itself, sample preparation as thin foil and experimental set-up calibration. Secondly, XAFS analysis is not a discriminating technique as soon as the absorber atom is involved in the chemical composition of various precipitates found in ODS. Nevertheless, the stability of the Ti with a coordination number of 5 is evidenced whatever the irradiation conditions. As our experimental study was not able to detect the nano-sized oxides, an alternative way is to perform modeling approach of the behavior of massive oxides under irradiation, compared to experimental analyses under ion irradiations. We have shown that the defect fluorite is an intermediate phase of the crystal-to-amorphous phase transition of the pyrochlore oxide structure, whatever the irradiation conditions and the ratio of the cationic radii, the Ti coordination number remaining around 5 in the amorphous state. (author) [fr

  12. Synthesis, properties and host effects of rare-earth doped silica nanopowders for photonic applications

    Science.gov (United States)

    Halpern, Susan B.

    In this study, SiO2/Al2O3/Er2O 3 (SAE) nanopowders were fabricated by the CF-CVC technique with average primary particle sizes ranging from 10--30 nm. Fluorescence and lifetime measurements were made both on as-prepared powders, as well as heat treated powders, with the latter exhibiting significantly higher emission intensities. At ˜1000°C, the SAE became partially devitrified with extremely broad (FWHM ≈ 78 nm) and flat emission spectra, which is highly desirable for Wavelength Division Multiplexing (WDM) in optical amplifiers. The unique optical properties of the powders are attributed to the formation of a metastable phase consisting of an uniform nano-scale dispersion of a metastable intermediate SiO2 (Al,Er)2O3 phase in an amorphous SiO 2 matrix. At higher heat treatments (1400°C), a dual-phase equilibrium structure was formed, consisting of a pyrochlore phase in a crystobalite matrix. The SAE nanopowders were incorporated into various optical hybrid glass hosts for active planar waveguide applications. Host selection was dependent on transparency in the wavelength region of interest (900 nm--1600 nm), index matching (n ˜ 1.5), chemical/thermal stability, and ease of processing. Furthermore, the inorganic-organic glasses were hydrophobic, resulting in a minimal level of residual OH- which can quench fluorescence emission. Four separate groups of host materials were studied: Perfluoro-alkyl Hybrid Glass (n ≈ 1.42), Alumina-Silica Hybrid Glass (n ≈ 1.49), Polyurethane-Silica Hybrid Glass (n ≈ 1.44), and Methyl/Epoxy Group Hybrid Glass (n ≈ 1.48). All hosts showed high spectral transparency, uniform dispersion of the nanopowder in the host, and minimal surface quenching of emission, and therefore represent excellent candidates for fabrication of next generation nanophotonic planar devices.

  13. Thermodynamic and Microstructural Mechanisms in the Corrosion of Advanced Ceramic Tc-bearing Waste Forms and Thermophysical Properties

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, Thomas [Univ. of Nevada, Las Vegas, NV (United States). Dept. of Mechanical Engineering

    2017-09-01

    Technetium-99 (Tc, t1/2 = 2.13x105 years) is a challenge from a nuclear waste perspective and is one of the most abundant, long-lived radioisotopes found in used nuclear fuel (UNF). Within the Hanford Tank Waste Treatment and Immobilization Plant, technetium volatilizes at typical glass melting temperature, is captured in the off-gas treatment system and recycled back into the feed to eventually increase Tc-loadings of the glass. The aim of this NEUP project was to provide an alternative strategy to immobilize fission technetium as durable ceramic waste form and also to avoid the accumulation of volatile technetium within the off gas melter system in the course of vitrifying radioactive effluents in a ceramic melter. During this project our major attention was turned to the fabrication of chemical durable mineral phases where technetium is structurally bond entirely as tetravalent cation. These mineral phases will act as the primary waste form with optimal waste loading and superior resistance against leaching and corrosion. We have been very successful in fabricating phase-pure micro-gram amounts of lanthanide-technetium pyrochlores by dry-chemical synthesis. However, upscaling to a gram-size synthesis route using either dry- or wet-chemical processing was not always successful, but progress can be reported on a variety of aspects. During the course of this 5-year NEUP project (including a 2-year no-cost extension) we have significantly enhanced the existing knowledge on the fabrication and properties of ceramic technetium waste forms.

  14. Radiation damage studies related to nuclear waste forms

    International Nuclear Information System (INIS)

    Gray, W.J.; Wald, J.W.; Turcotte, R.P.

    1981-12-01

    Much of the previously reported work on alpha radiation effects on crystalline phases of importance to nuclear waste forms has been derived from radiation effects studies of composite waste forms. In the present work, two single-phase crystalline materials, Gd 2 Ti 2 O 7 (pyrochlore) and CaZrTi 2 O 7 (zirconolite), of relative importance to current waste forms were studied independently by doping with 244 Cm at the 3 wt % level. Changes in the crystalline structure measured by x-ray diffraction as a function of dose show that damage ingrowth follows an expected exponential relationship of the form ΔV/V 0 = A[1-exp(-BD)]. In both cases, the materials became x-ray amorphous before the estimated saturation value was reached. The predicted magnitudes of the unit cell volume changes at saturation are 5.4% and 3.5%, respectively, for Gd 2 Ti 2 O 7 and CaZrTi 2 O 7 . The later material exhibited anisotropic behavior in which the expansion of the monoclinic cell in the c 0 direction was over five times that of the a 0 direction. The effects of transmutations on the properties of high-level waste solids have not been studied until now because of the long half-lives of the important fission products. This problem was circumvented in the present study by preparing materials containing natural cesium and then irradiating them with neutrons to produce 134 Cs, which has only a 2y half-life. The properties monitored at about one year intervals following irradiation have been density, leach rate and microstructure. A small amount of x-ray diffraction work has also been done. Small changes in density and leach rate have been observed for some of the materials, but they were not large enough to be of any consequence for the final disposal of high level wastes

  15. Ceramic waste forms for fuel-containing masses at Chernobyl

    International Nuclear Information System (INIS)

    Oversby, V.M.

    1994-05-01

    The fuel materials originally in the core of the Chernobyl Unit 4 reactor are now present within the Ukrytie in three major forms: (1) very fine particles of fuel dispersed as dust (about 10 tonnes), (2) fragments of the destroyed core, and (3) lavas containing fuel, cladding, and other materials. All of these materials will need to be immobilized into waste forms suitable for final disposal. We propose a ceramic waste form system that could accommodate all three waste types with a single set of processing equipment. The waste form would include the mineral zirconolite for immobilization of actinide materials (including uranium), perovskite, nepheline, spinel, and other phases as dictated by the chemistry of the lava masses. Waste loadings as high as 50% U can be achieved if pyrochlore, a close relative of zirconolite, is used as the U host. The ceramic immobilization could be achieved with low additions of inert chemicals to minimize the final disposal volume while ensuring a durable product. The sequence of processing would be to collect and immobilize the fuel dust first. This material will require minimal preprocessing and will provide experience in the handling of the fuel materials. Core fragments would be processed next, using a cryogenic crushing stage to reduce the size prior to adding ceramic additives. The lavas would be processed last, which is compatible with the likely sequence of availability of materials and with the complexity of the operations. The lavas will require more adjustment of chemical additive composition than the other streams to ensure that the desired phases are produced in the waste form

  16. Molecular environmental science using synchrotron radiation:Chemistry and physics of waste form materials

    Energy Technology Data Exchange (ETDEWEB)

    Lindle, Dennis W.; Shuh, David K.

    2005-02-28

    Production of defense-related nuclear materials has generated large volumes of complex chemical wastes containing a mixture of radionuclides. The disposition of these wastes requires conversion of the liquid and solid-phase components into durable, solid forms suitable for long-term immobilization [1]. Specially formulated glass compositions, many of which have been derived from glass developed for commercial purposes, and ceramics such as pyrochlores and apatites, will be the main recipients for these wastes. The performance characteristics of waste-form glasses and ceramics are largely determined by the loading capacity for the waste constituents (radioactive and non-radioactive) and the resultant chemical and radiation resistance of the waste-form package to leaching (durability). There are unique opportunities for the use of near-edge soft-x-ray absorption fine structure (NEXAFS) spectroscopy to investigate speciation of low-Z elements forming the backbone of waste-form glasses and ceramics. Although nuclear magnetic resonance (NMR) is the primary technique employed to obtain speciation information from low-Z elements in waste forms, NMR is incompatible with the metallic impurities contained in real waste and is thus limited to studies of idealized model systems. In contrast, NEXAFS can yield element-specific speciation information from glass constituents without sensitivity to paramagnetic species. Development and use of NEXAFS for eventual studies of real waste glasses has significant implications, especially for the low-Z elements comprising glass matrices [5-7]. The NEXAFS measurements were performed at Beamline 6.3.1, an entrance-slitless bend-magnet beamline operating from 200 eV to 2000 eV with a Hettrick-Underwood varied-line-space (VLS) grating monochromator, of the Advanced Light Source (ALS) at LBNL. Complete characterization and optimization of this beamline was conducted to enable high-performance measurements.

  17. The incorporation of neptunium and plutonium in thorutite (ThTi{sub 2}O{sub 6})

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Gregg, Daniel J.; Lumpkin, Gregory R.; Begg, Bruce D.; Jovanovic, Miodrag

    2013-12-25

    Highlights: •The incorporation of neptunium (Np) and plutonium (Pu) in thorutite (ThTi{sub 2}O{sub 6}) has been studied. •The effect of Np/Pu doping on the unit cell parameter changes has been discussed from the structure point of view. •The effect of Y as charge compensator to encourage the formation of higher valences of Np and Pu has been explored. •The resulting Np/Pu doped thorutite samples have been characterised by using XRD, SEM and DRS. -- Abstract: The incorporation of neptunium (Np) and plutonium (Pu) into the brannerite structured lattice was studied using thorutite (ThTi{sub 2}O{sub 6}) 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 ThTi{sub 2}O{sub 6} and Ce{sub 0.975}Ti{sub 2}O{sub 5.95}. 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.

  18. Synthesis, crystal structure, and magnetic properties of novel 2D kagome materials RE{sub 3}Sb{sub 3}Mg{sub 2}O{sub 14} (RE = La, Pr, Sm, Eu, Tb, Ho): Comparison to RE{sub 3}Sb{sub 3}Zn{sub 2}O{sub 14} family

    Energy Technology Data Exchange (ETDEWEB)

    Sanders, M.B.; Baroudi, K.M.; Krizan, J.W.; Mukadam, O.A.; Cava, R.J. [Department of Chemistry, Princeton University, Princeton, NJ (United States)

    2016-10-15

    The crystal structures and magnetic properties of RE{sub 3}Sb{sub 3}Mg{sub 2}O{sub 14} (RE = La, Pr, Sm, Eu, Tb, Ho) with a perfect kagome lattice are presented and compared to RE{sub 3}Sb{sub 3}Zn{sub 2}O{sub 14}. Rietveld structure refinements were performed using X-ray diffraction data, indicating that the layered compounds are fully structurally ordered. The compounds crystallize in a rhombohedral supercell of the cubic pyrochlore structure, in the space group R-3m. Magnetic susceptibility measurements show no signs of magnetic ordering above 2 K. The RE{sub 3}Sb{sub 3}Mg{sub 2}O{sub 14} family is similar to that of RE{sub 3}Sb{sub 3}Zn{sub 2}O{sub 14}; however, the series reported here features a fully ordered distribution of cations in both the nonmagnetic antimony and magnetic rare earth kagome lattices. Unlike the offsite disorder that Zn{sup 2+} experiences in RE{sub 3}Sb{sub 3}Zn{sub 2}O{sub 14}, the magnesium sites in RE{sub 3}Sb{sub 3}Mg{sub 2}O{sub 14} are completely ordered. Here we compare the magnetic properties in both series of kagome compounds to determine how significant Zn{sup 2+}'s positional ordering is within this structure type. The compounds reported here appear to be relatively defect-free and are therefore model systems for investigating magnetic frustration on an ideal 2D rare earth kagome lattice. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Preparation and characterization of 238Pu-ceramics for radiation damage experiments

    International Nuclear Information System (INIS)

    DM Strachan; RD Scheele; WC Buchmiller; JD Vienna; RL Sell; RJ Elovich

    2000-01-01

    As a result of treaty agreements between Russia and the US, portions of their respective plutonium and nuclear weapons stockpiles have been declared excess. In support of the US Department of Energy's 1998 decision to pursue immobilization of a portion of the remaining Pu in a titanate-based ceramic, the authors prepared nearly 200 radiation-damage test specimens of five Pu- and 238 Pu-ceramics containing 10 mass% Pu to determine the effects of irradiation from the contained Pu and U on the ceramic. The five Pu-ceramics were (1) phase-pure pyrochlore [ideally, Ca(U, Pu)Ti 2 O 7 ], (2) pyrochlore-rich baseline, (3) pyrochlore-rich baseline with impurities, (4) phase-pure zirconolite [ideally Ca(U, Pu)Ti 2 O 7 ], and (5) a zirconolite-rich baseline. These ceramics were prepared with either normal weapons-grade Pu, which is predominantly 239 Pu, or 238 Pu. The 238 Pu accelerates the radiation damage relative to the 239 Pu because of its much higher specific activity. The authors were unsuccessful in preparing phase-pure (Pu, U) brannerite, which is the third crystalline phase present in the baseline immobilization form. Since these materials will contain ∼10 mass% Pu and about 20 mass% U, radiation damage to the crystalline structure of these materials will occur overtime. As the material becomes damaged from the decay of the Pu and U, it is possible for the material to swell as both the alpha particles and recoiling atoms rupture chemical bonds within the solid. As the material changes density, cracking, perhaps in the form of microcracks, may occur. If cracking occurs in ceramic that has been placed in a repository, the calculated rate of radionuclide release if the can has corroded would increase proportionately to the increase in surface area. To investigate the effects of radiation damage on the five ceramics prepared, the authors are storing the specimens at 20, 125, and 250 C until the 238 Pu specimens become metamict and the damage saturates. They will

  20. Anomalous Hall effect

    Science.gov (United States)

    Nagaosa, Naoto; Sinova, Jairo; Onoda, Shigeki; MacDonald, A. H.; Ong, N. P.

    2010-04-01

    The anomalous Hall effect (AHE) occurs in solids with broken time-reversal symmetry, typically in a ferromagnetic phase, as a consequence of spin-orbit coupling. Experimental and theoretical studies of the AHE are reviewed, focusing on recent developments that have provided a more complete framework for understanding this subtle phenomenon and have, in many instances, replaced controversy by clarity. Synergy between experimental and theoretical works, both playing a crucial role, has been at the heart of these advances. On the theoretical front, the adoption of the Berry-phase concepts has established a link between the AHE and the topological nature of the Hall currents. On the experimental front, new experimental studies of the AHE in transition metals, transition-metal oxides, spinels, pyrochlores, and metallic dilute magnetic semiconductors have established systematic trends. These two developments, in concert with first-principles electronic structure calculations, strongly favor the dominance of an intrinsic Berry-phase-related AHE mechanism in metallic ferromagnets with moderate conductivity. The intrinsic AHE can be expressed in terms of the Berry-phase curvatures and it is therefore an intrinsic quantum-mechanical property of a perfect crystal. An extrinsic mechanism, skew scattering from disorder, tends to dominate the AHE in highly conductive ferromagnets. The full modern semiclassical treatment of the AHE is reviewed which incorporates an anomalous contribution to wave-packet group velocity due to momentum-space Berry curvatures and correctly combines the roles of intrinsic and extrinsic (skew-scattering and side-jump) scattering-related mechanisms. In addition, more rigorous quantum-mechanical treatments based on the Kubo and Keldysh formalisms are reviewed, taking into account multiband effects, and demonstrate the equivalence of all three linear response theories in the metallic regime. Building on results from recent experiment and theory, a

  1. Reduction and structural modification of zirconolite on He{sup +} ion irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Merry, E-mail: g41merry@gmail.com [Sant Longowal Institute of Engineering and Technology, Longowal, Sangrur, Punjab 148106 (India); Kulriya, P.K. [Inter-University Accelerator Centre, Aruna Asaf Ali Road, New Delhi 110067 (India); Department of Mechanical, Aerospace & Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States); Shukla, Rishabh; Dhaka, R.S. [Novel Materials and Interface Physics Laboratory, Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016 (India); Kumar, Raj [Inter-University Accelerator Centre, Aruna Asaf Ali Road, New Delhi 110067 (India); Ghumman, S.S. [Sant Longowal Institute of Engineering and Technology, Longowal, Sangrur, Punjab 148106 (India)

    2016-07-15

    The immobilization of minor actinides and alkaline-earth metal is a major concern in nuclear industry due to their long-term radioactive contribution to the high level waste (HLW). Materials having zirconolite, pyrochlore, and perovskite structure are promising candidates for immobilization of HLW. The zirconolite which exhibits high radiation stability and corrosion resistance behavior is investigated for its radiation stability against alpha particles in the present study. CaZrTi{sub 2}O{sub 7} pellets prepared using solid state reaction techniques, were irradiated with 30 keV He{sup +} ions for the ion fluence varying from 1 × 10{sup 17} to 1 × 10{sup 21} ions/m{sup 2}. Scanning electron microscopy (SEM) images of the un-irradiated sample exhibited well separated grains with average size of about 6.8 μm. On the ion irradiation, value of the average grains size was about 7.1 μm, and change in the microstructure was insignificant. The X-ray photoelectron spectroscopy (XPS) studies showed a shift in the core level peak position (of Ca 2p, Ti 2p and Zr 3d) towards lower binding energy with respect to pristine sample as well as loss of oxygen was also observed for sample irradiated with the ion fluence of 1 × 10{sup 20} ions/m{sup 2}. These indicate a decrease in co-ordination number and the ionic character of M−O bond. Moreover, core level XPS signal was not detected for sample irradiated with ion fluence of 1 × 10{sup 21} ions/m{sup 2}, suggesting surface damage of the sample at this ion fluence. However, X-ray diffraction (XRD) studies showed that zirconolite was not amorphized even on irradiation up to a fluence order of 1 × 10{sup 21} ion/m{sup 2}. But, significant decrease in peak intensity due to creation of defects and a marginal positive peak shift due to tensile strain induced by irradiation, were observed. Thus, XRD along with XPS investigation suggests that reduction, decrease in co-ordination number, and increase in covalency are responsible for

  2. Age and geochemistry of the Newania dolomite carbonatites, India: implications for the source of primary carbonatite magma

    Science.gov (United States)

    Ray, Jyotiranjan S.; Pande, Kanchan; Bhutani, Rajneesh; Shukla, Anil D.; Rai, Vinai K.; Kumar, Alok; Awasthi, Neeraj; Smitha, R. S.; Panda, Dipak K.

    2013-12-01

    The Newania carbonatite complex of India is one of the few dolomite-dominated carbonatites of the world. Intruding into Archean basement gneisses, the rocks of the complex have undergone limited diversification and are not associated with any alkaline silicate rock. Although the magmatic nature of the complex was generally accepted, its age of emplacement had remained equivocal because of the disturbed nature of radioisotope systems. Many questions about the nature of its mantle source and mode of origin had remained unanswered because of lack of geochemical and isotopic data. Here, we present results of our effort to date the complex using 147Sm-143Nd, 207Pb-206Pb and 40Ar-39Ar dating techniques. We also present mineral chemistry, major and trace element geochemistry and Sr-Nd isotopic ratio data for these carbonatites. Our age data reveal that the complex was emplaced at ~1,473 Ma and parts of it were affected by a thermal event at ~904 Ma. The older 207Pb-206Pb ages reported here (~2.4 Ga) and by one earlier study (~2.3 Ga; Schleicher et al. Chem Geol 140:261-273, 1997) are deemed to be a result of heterogeneous incorporation of crustal Pb during the post-emplacement thermal event. The thermal event had little effect on many magmatic signatures of these rocks, such as its dolomite-magnesite-ankerite-Cr-rich magnetite-magnesio-arfvedsonite-pyrochlore assemblage, mantle like δ13C and δ18O and typical carbonatitic trace element patterns. Newania carbonatites show fractional crystallization trend from high-Mg to high-Fe through high-Ca compositions. The least fractionated dolomite carbonatites of the complex possess very high Mg# (≥80) and have similar major element oxide contents as that of primary carbonatite melts experimentally produced from peridotitic sources. In addition, lower rare earth element (and higher Sr) contents than a typical calcio-carbonatite and mantle like Nb/Ta ratios indicate that the primary magma for the complex was a magnesio

  3. PRELIMINARY STUDY OF CERAMICS FOR IMMOBILIZATION OF ADVANCED FUEL CYCLE REPROCESSING WASTES

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K.; Billings, A.; Brinkman, K.; Marra, J.

    2010-09-22

    The Savannah River National Laboratory (SRNL) developed a series of ceramic waste forms for the immobilization of Cesium/Lanthanide (CS/LN) and Cesium/Lanthanide/Transition Metal (CS/LN/TM) waste streams anticipated to result from nuclear fuel reprocessing. Simple raw materials, including Al{sub 2}O{sub 3}, CaO, and TiO{sub 2} were combined with simulated waste components to produce multiphase ceramics containing hollandite-type phases, perovskites (particularly BaTiO{sub 3}), pyrochlores, zirconolite, and other minor metal titanate phases. Identification of excess Al{sub 2}O{sub 3} via X-ray Diffraction (XRD) and Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM/EDS) in the first series of compositions led to a Phase II study, with significantly reduced Al{sub 2}O{sub 3} concentrations and increased waste loadings. Three fabrication methodologies were used, including melting and crystallizing, pressing and sintering, and Spark Plasma Sintering (SPS), with the intent of studying phase evolution under various sintering conditions. XRD and SEM/EDS results showed that the partitioning of the waste elements in the sintered materials was very similar, despite varying stoichiometry of the phases formed. The Phase II compositions generally contained a reduced amount of unreacted Al{sub 2}O{sub 3} as identified by XRD, and had phase assemblages that were closer to the initial targets. Chemical composition measurements showed no significant issues with meeting the target compositions. However, volatilization of Cs and Mo was identified, particularly during melting, since sintering of the pressed pellets and SPS were performed at lower temperatures. Partitioning of some of the waste components was difficult to determine via XRD. SEM/EDS mapping showed that those elements, which were generally present in small concentrations, were well distributed throughout the waste forms. Initial studies of radiation damage tolerance using ion beam irradiation at Los

  4. 17O solid-state NMR spectroscopy of A2B2O7 oxides: quantitative isotopic enrichment and spectral acquisition?

    Science.gov (United States)

    Fernandes, Arantxa; Moran, Robert F; Sneddon, Scott; Dawson, Daniel M; McKay, David; Bignami, Giulia P M; Blanc, Frédéric; Whittle, Karl R; Ashbrook, Sharon E

    2018-02-13

    The potential of 17 O NMR spectroscopy for the investigation of A 2 B 2 O 7 ceramic oxides important in the encapsulation of radioactive waste is demonstrated, with post-synthetic enrichment by exchange with 17 O 2 gas. For Y 2 Sn 2 O 7 , Y 2 Ti 2 O 7 and La 2 Sn 2 O 7 pyrochlores, enrichment of the two distinct O species is clearly non quantitative at lower temperatures (∼700 °C and below) and at shorter times, despite these being used in prior work, with preferential enrichment of OA 2 B 2 favoured over that of OA 4 . At higher temperatures, the 17 O NMR spectra suggest that quantitative enrichment has been achieved, but the integrated signal intensities do not reflect the crystallographic 1 : 6 (O1 : O2) ratio until corrected for differences in T 1 relaxation rates and, more importantly, the contribution of the satellite transitions. 17 O NMR spectra of Y 2 Zr 2 O 7 and Y 2 Hf 2 O 7 defect fluorites showed little difference with any variation in enrichment temperature or time, although an increase in the absolute level of enrichment (up to ∼7.5%) was observed at higher temperature. DFT calculations show that the six distinct resonances observed cannot be assigned unambiguously, as each has contributions from more than one of the five possible next nearest neighbour environments. For La 2 Ti 2 O 7 , which adopts a layered perovskite-like structure, little difference in the spectral intensities is observed with enrichment time or temperature, although the highest absolute levels of enrichment (∼13%) were obtained at higher temperature. This work demonstrates that 17 O NMR has the potential to be a powerful probe of local structure and disorder in oxides, but that considerable care must be taken both in choosing the conditions for 17 O enrichment and the experimental acquisition parameters if the necessary quantitative measurements are to be obtained for more complex systems.

  5. Fabrication of Y{sub 2}Ti{sub 2}O{sub 7}:Yb{sup 3+},Ho{sup 3+} nanoparticles by a gel-combustion approach and upconverting luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Zhongsheng, E-mail: zhshcheng@ecit.cn [State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Nanchang, Jiangxi 330013 (China); Wang, Min; Wang, Haiqing; Le, Zhanggao; Huang, Guolin; Zou, Lixia; Liu, Zhirong [State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Nanchang, Jiangxi 330013 (China); Wang, Dianyuan; Wang, Qingkai [College of Science, Jiujiang University, Jiujiang, Jiangxi 332005 (China); Gong, Weiping [Electronic Science Department, Huizhou University, Huizhou, Guangdong 516001 (China)

    2014-09-01

    Highlights: • Co-doped (Y{sub 0.99−x}Ho{sub 0.01}Yb{sub x}){sub 2}Ti{sub 2}O{sub 7} nanophosphors were fabricated by gel-combustion method. • The effect of calcination and Yb{sup 3+} doping on upconverting spectra of nanophosphors was studied. • The dependence of upconverting intensity on the excitation power was examined. - Abstract: Yb{sup 3+}, Ho{sup 3+} co-doped pyrochlore-structured (Y{sub 0.99−x}Ho{sub 0.01}Yb{sub x}){sub 2}Ti{sub 2}O{sub 7} (x = 0, 2.5, 5.0, 7.5, 10.0 and 12.5 mol%) nanoparticles (NPs) were successfully fabricated via a gel-combustion approach. The products as-obtained were characterized by various techniques, i.e. X-ray diffraction, transmission electron microscope, Fourier transformed infrared spectra and upconverting spectra. The results indicate that the bright green (∼540 nm) and red (∼660 nm) emissions are observed in Y{sub 2}Ti{sub 2}O{sub 7}:Ho{sup 3+},Yb{sup 3+} NPs under the 980 nm excitation, which is ascribed to the radiative transitions ({sup 5}F{sub 4},{sup 5}S{sub 2}) → {sup 5}I{sub 8} and {sup 5}F{sub 5} → {sup 5}I{sub 8} of Ho{sup 3+} ions, respectively. It is also found that the calcining temperature and Yb{sup 3+} ion doping level have a great influence on the upconverting spectra of (Y{sub 0.99−x}Ho{sub 0.01}Yb{sub x}){sub 2}Ti{sub 2}O{sub 7} NPs. The emission intensities increase initially and then fall down from 800 to 1000 °C. The optimum doping level of Yb{sup 3+} ions is 7.5 mol%, and the intensity of upconverting emissions for (Y{sub 0.915}Ho{sub 0.01}Yb{sub 0.075}){sub 2}Ti{sub 2}O{sub 7} NPs is enhanced by the fold of 32 compared to the Yb{sup 3+}-free samples. The dependence of upconverting intensity on the excitation power reveals the contribution of two photons to both the green and red upconverting process under lower excitation power, and the possible upconverting mechanisms have been proposed accordingly.

  6. Feasible and realiable ab initio atomistic modeling for nuclear waste management

    Energy Technology Data Exchange (ETDEWEB)

    Beridze, George

    2016-07-01

    , successful modeling of the important, from the long-term stability point of view, thermochemical and thermodynamical properties of the prospective nuclear waste forms, such as monazite- and pyrochlore-type ceramics. These include the heat capacities, the excess enthalpies of mixing or thermochemical parameters of phase transitions, to name but a few. The performed here benchmarking and application studies give a solid basis and paths for the quest to find and design computationally feasible ab initio computational methods, which would allow for reliable and meaningful simulations of materials relevant for nuclear waste management.

  7. Evidence for Nb-Ta Occurrences in the Syn-Tectonic Pan-African Mayo Salah Leucogranite (Northern Cameroon: Constraints from Nb-Ta Oxide Mineralogy, Geochemistry and U-Pb LA-ICP-MS Geochronology on Columbite and Monazite

    Directory of Open Access Journals (Sweden)

    Periclex Martial Fosso Tchunte

    2018-04-01

    Full Text Available The Mayo Salah pluton, which is located in the North-Cameroon domain of Central African Bold Belt (CAFB, is emplaced as a laccolith in volcano-sedimentary schists of Poli series, and displays features of Rare-metal Granite (RMG. It is made of two main rock groups: (1 the metaluminous barren muscovite granite (MsG and (2 the Nb-Ta bearing peraluminous leucogranite (MsL which expresses four subtypes. The evolved Rare-element MsL is subalkaline, slightly peraluminous (ASI = 1.01–1.21, and it displays flat REE chondrite-normalized patterns with a strong negative Eu anomaly (Eu/Eu* = 0.02–0.20. It belongs to the peraluminous low phosphorus Rare-element Granites and L-type igneous rocks, as shown by the relatively low Zr/Hf (4.8–14 and Nb/Ta (1.4–9.0 ratios and the positive slope of the Zr-Hf-Nb-Ta profile in spider diagrams. The rare-element-bearing mineral is represented by columbite-group minerals (CGM and other Nb-Ta-oxides (Nb-rutile and pyrochlore supergroup minerals. The CGM is classified as Mn-columbite, with Ta# and Mn# ratios increasing from core to rim. Two stages of mineralization are identified; the earliest stage (CGM-I consists in scattered tabular or prismatic euhedral grains that were related to magmatic fractionation. The latest stage (CGM-II is expressed as a Ta-rich Mn hydrothermal CGM episode represented as rims and/overgrowths around and/or as veinlet crosscutting CGM-I or in cleavage planes of muscovite. The U-Pb dating of columbite and monazite of the Mayo Salah leucogranite indicates a late-Neoproterozoic magmatic-hydrothermal mineralization event from 603.2 ± 5.3 to 581.6 ± 7.2 Ma, as consistent with both late D2 to D3 events that were recorded in the CAFB in Cameroon, and the associated continental collision environment. The Nb-Ta mineralization of the Mayo Salah pluton provides evidence for the presence of RMG in Northern Cameroon of CAFB, and its temporal association with the youngest period of metallogenic epoch

  8. Feasible and realiable ab initio atomistic modeling for nuclear waste management

    International Nuclear Information System (INIS)

    Beridze, George

    2016-01-01

    , successful modeling of the important, from the long-term stability point of view, thermochemical and thermodynamical properties of the prospective nuclear waste forms, such as monazite- and pyrochlore-type ceramics. These include the heat capacities, the excess enthalpies of mixing or thermochemical parameters of phase transitions, to name but a few. The performed here benchmarking and application studies give a solid basis and paths for the quest to find and design computationally feasible ab initio computational methods, which would allow for reliable and meaningful simulations of materials relevant for nuclear waste management.

  9. Fundamental Thermodynamics of Actinide-Bearing Mineral Waste Forms

    International Nuclear Information System (INIS)

    Williamson, Mark A.; Ebbinghaus, Bartley B.; Navrotsky, Alexandria

    1999-01-01

    calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly, understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpies of formation of actinide substituted zircon, zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stabilities of these materials

  10. The nuclear fuel cycle versus the carbon cycle

    International Nuclear Information System (INIS)

    Ewing, R.C.

    2005-01-01

    the production of plutonium in a uranium-based nuclear fuel cycle, with special emphasis on the 'mineralogical solution' for the 'sequestration' of Pu into pyrochlore structure-types. (author)

  11. Wadi Ladid Al-JI,Dan Alkali Feldspar Granites and Associated Pegmatites, North Eastern Eser, Egypt:Geology,Mineralogy and Radioactivity

    International Nuclear Information System (INIS)

    Abu Steet, A.A.; Ayoub, R.R.; Bakhit, A.F.

    2013-01-01

    columbite, pyrochlore, zircon, fluorite as well as iron oxy hydroxides

  12. Characterization of PZT thin films on metal substrates; Charakterisierung von PZT-Duennschichten auf Metallsubstraten

    Energy Technology Data Exchange (ETDEWEB)

    Dutschke, A.

    2008-02-02

    Lead zirconate titanate (PbZr{sub x}Ti{sub 1-x}O{sub 3},PZT) is one of the most applied ceramic materials because of its distinctive piezo- and ferroelectric properties. Prepared as thin films on flexible, metallic substrates it can be used for various applications as strain gauges, key switches, vibration dampers, microactuators and ultrasonic transducers. The aim of this work is to analyze the microstructure and the phase-content of PZT-thin films deposited on temperature- und acid-resistant hastelloy-sheets, to correlate the results with the ferroelectric and dielectric properties. It is demonstrated, that the specific variation of the microstructure can be achieved by different thermal treatments and the selective addition of Neodymium as dopant. Nd-doping leads to a shift of the maximum nucleation rate towards reduced temperatures and a decrease in the rate of growth compared to undoped films. The PZT-films are prepared by a sol-gel-process in fourfold multilayers with a composition near the morphotropic phase boundary, where the tetragonal und rhombohedral perovskite-phases coexist. The crystallisation in Nd-doped and undoped films takes place heterogeneously, preferentially at the interfaces and on the surface of the multilayered films as well as on the inner surface of pores within the films. For the first time, the Zr:Ti fluctuation phenomena emerging in sol-gel derived PZT films is related to the microstructure and the local phase content on a nanometer scale. In this connection it is proved, that long-distance Zr:Ti gradients arise preferentially before and during the crystallisation of the pyrochlore phase. During the following crystallisation of the perovskite phase, the crystallites grow across these gradients without modifying them. It is pointed out that the fluctuation in the Zr:Ti ratio has only minor influence on the amount of the tetragonal or rhombohedral distortion of the crystallites after the transition from the para- to the ferroelectric

  13. Quasiparticle Excitations with Berry Curvature in Insulating Magnets and Weyl Semimetals

    Science.gov (United States)

    Hirschberger, Maximilian Anton

    The concept of the geometric Berry phase of the quantum mechanical wave function has led to a better theoretical understanding of natural phenomena in all fields of fundamental physics research. In condensed matter physics, the impact of this theoretical discovery has been particularly profound: The quantum Hall effect, the anomalous Hall effect, the quantum spin Hall effect, magnetic skyrmions, topological insulators, and topological semimetals are but a few subfields that have witnessed rapid developments over the three decades since Michael Berry's landmark paper. In this thesis, I will present and discuss the results of three experiments where Berry's phase leads to qualitatively new transport behavior of electrons or magnetic spin excitations in solids. We introduce the theoretical framework that leads to the prediction of a thermal Hall effect of magnons in Cu(1,3-bdc), a simple two-dimensional layered ferromagnet on a Kagome net of spin S = 1/2 copper atoms. Combining our experimental results measured down to very low temperatures T = 0.3 K with published data from inelastic neutron scattering, we report a quantitative comparison with the theory. This confirms the expected net Berry curvature of the magnon band dispersion in this material. Secondly, we have studied the thermal Hall effect in the frustrated pyrochlore magnet Tb2Ti2O7, where the thermal Hall effect is large in the absence of long-range magnetic order. We establish the magnetic nature of the thermal Hall effect in Tb2Ti2O7, introducing this material as the first example of a paramagnet with non-trivial low-lying spin excitations. Comparing our results to other materials with zero thermal Hall effect such as the classical spin ice Dy2Ti 2O7 and the non-magnetic analogue Y2Ti2O 7, we carefully discuss the experimental limitations of our setup and rule out spurious background signals. The third and final chapter of this thesis is dedicated to electrical transport and thermopower experiments on the

  14. Mianningite, (□,Pb,Ce,Na) (U{sup 4+},Mn,U{sup 6+}) Fe{sup 3+}{sub 2}(Ti,Fe{sup 3+}){sub 18}O{sub 38}, a new member of the crichtonite group from Maoniuping REE deposit, Mianning county, southwest Sichuan, China

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Xiangkun; Fan, Guang; Chen, Zhangru; Ai, Yujie [Beijing Research Institute of Uranium Geology, Beijing (China); Li, Guowu [China Univ. of Geosciences, Beijing (China). Lab. of Crystal Structure; Shen, Ganfu [Chengdu Institute of Geology and Mineral Resources, Chengdu (China)

    2017-05-15

    Mianningite (IMA 2014-072), ideally (□,Pb,Ce,Na)(U{sup 4+},Mn,U{sup 6+}) Fe{sup 3+}{sub 2}(Ti,Fe{sup 3+}){sub 18}O{sub 38}, is a new member of the crichtonite group from the Maoniuping REE deposit, Mianning county, Sichuan province, China. It was found in fractures of lamprophyre veins and in the contact between lamprophyre and a later quartz-alkali feldspar syenite dyke with REE mineralization, and is named after its type locality. Associated minerals are microcline, albite, quartz, iron-rich phlogopite, augite, muscovite, calcite, baryte, fluorite, epidote, pyrite, magnetite, hematite, galena, hydroxylapatite, titanite, ilmenite, rutile, garnet-group minerals, zircon, allanite-(Ce), monazite-(Ce), bastnaesite-(Ce), parisite-(Ce), maoniupingite-(Ce), thorite, pyrochlore-group minerals and chlorite. Mianningite occurs as opaque subhedral to euhedral tabular crystals, up to 1-2 mm in size, black in color and streak, and with a submetallic luster. Mianningite is brittle, with a conchoidal fracture. Its average micro-indentation hardness is 83.8 kg/mm{sup 2} (load 0.2 kg), which is equivalent to ∝6 on the Mohs hardness scale. Its measured and calculated densities are 4.62 (8) g/cm{sup 3} and 4.77 g/cm{sup 3}, respectively. Under reflected light, mianningite is grayish white, with no internal reflections. It appears isotropic and exhibits neither bireflectance nor pleochroism. The empirical formula, calculated on the basis of 38 O atoms per formula unit (apfu), is [□{sub 0.322}(Pb{sub 0.215}Ba{sub 0.037}Sr{sub 0.036}Ca{sub 0.010}){sub Σ0.298}(Ce{sub 0.128}La{sub 0.077}Nd{sub 0.012}){sub Σ0.217} (Na{sub 0.127}K{sub 0.036}){sub Σ0.163}]{sub Σ01.000}(U{sup 4+}{sub 0.447}Mn{sub 00.293}U{sup 6} {sup +}{sub 0.112}Y{sub 0.091}Zr{sub 0.023}Th{sub 0.011}){sub Σ0.977}(Fe{sup 3+}{sub 1.224}Fe{sup 2+}{sub 0.243}Mg{sub 0.023}P{sub 0.008}Si{sub 0.006} □{sub 0.496}){sub Σ2.000}(Ti{sub 12.464}Fe{sup 3+}{sub 5.292}V{sup 5+}{sub 0.118}Nb{sub 0.083}Al{sub 0.026}Cr{sup 3

  15. Characterization of PZT thin films on metal substrates

    International Nuclear Information System (INIS)

    Dutschke, A.

    2008-01-01

    Lead zirconate titanate (PbZr x Ti 1-x O 3 ,PZT) is one of the most applied ceramic materials because of its distinctive piezo- and ferroelectric properties. Prepared as thin films on flexible, metallic substrates it can be used for various applications as strain gauges, key switches, vibration dampers, microactuators and ultrasonic transducers. The aim of this work is to analyze the microstructure and the phase-content of PZT-thin films deposited on temperature- und acid-resistant hastelloy-sheets, to correlate the results with the ferroelectric and dielectric properties. It is demonstrated, that the specific variation of the microstructure can be achieved by different thermal treatments and the selective addition of Neodymium as dopant. Nd-doping leads to a shift of the maximum nucleation rate towards reduced temperatures and a decrease in the rate of growth compared to undoped films. The PZT-films are prepared by a sol-gel-process in fourfold multilayers with a composition near the morphotropic phase boundary, where the tetragonal und rhombohedral perovskite-phases coexist. The crystallisation in Nd-doped and undoped films takes place heterogeneously, preferentially at the interfaces and on the surface of the multilayered films as well as on the inner surface of pores within the films. For the first time, the Zr:Ti fluctuation phenomena emerging in sol-gel derived PZT films is related to the microstructure and the local phase content on a nanometer scale. In this connection it is proved, that long-distance Zr:Ti gradients arise preferentially before and during the crystallisation of the pyrochlore phase. During the following crystallisation of the perovskite phase, the crystallites grow across these gradients without modifying them. It is pointed out that the fluctuation in the Zr:Ti ratio has only minor influence on the amount of the tetragonal or rhombohedral distortion of the crystallites after the transition from the para- to the ferroelectric state due to

  16. Alternative High-Performance Ceramic Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Sundaram, S. K. [Alfred Univ., NY (United States)

    2017-02-01

    This final report (M5NU-12-NY-AU # 0202-0410) summarizes the results of the project titled “Alternative High-Performance Ceramic Waste Forms,” funded in FY12 by the Nuclear Energy University Program (NEUP Project # 12-3809) being led by Alfred University in collaboration with Savannah River National Laboratory (SRNL). The overall focus of the project is to advance fundamental understanding of crystalline ceramic waste forms and to demonstrate their viability as alternative waste forms to borosilicate glasses. We processed single- and multiphase hollandite waste forms based on simulated waste streams compositions provided by SRNL based on the advanced fuel cycle initiative (AFCI) aqueous separation process developed in the Fuel Cycle Research and Development (FCR&D). For multiphase simulated waste forms, oxide and carbonate precursors were mixed together via ball milling with deionized water using zirconia media in a polyethylene jar for 2 h. The slurry was dried overnight and then separated from the media. The blended powders were then subjected to melting or spark plasma sintering (SPS) processes. Microstructural evolution and phase assemblages of these samples were studied using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion analysis of x-rays (EDAX), wavelength dispersive spectrometry (WDS), transmission electron spectroscopy (TEM), selective area x-ray diffraction (SAXD), and electron backscatter diffraction (EBSD). These results showed that the processing methods have significant effect on the microstructure and thus the performance of these waste forms. The Ce substitution into zirconolite and pyrochlore materials was investigated using a combination of experimental (in situ XRD and x-ray absorption near edge structure (XANES)) and modeling techniques to study these single phases independently. In zirconolite materials, a transition from the 2M to the 4M polymorph was observed with increasing Ce content. The resulting

  17. Synthesis and Characterization of Sn2+- based and Bi3+- based metal oxides for photocatalytic applications

    KAUST Repository

    Noureldine, Dalal

    2016-07-01

    the compound at lower temperature. Next, the optoelectronic properties of α-SnWO4 structure were studied though a combination of experimental and theoretical approach. α-SnWO4 thin films were deposited by RF-sputtering. An interesting low band gap of ~ 1.95 eV was experimentally for direct band gap and 1.7 eV for indirect band gap, high dielectric constants and low electron effective masses in one crystallographic direction were obtained, exhibiting good charge separation and charge carrier transport of the charge carriers. The PEC performance was limited by the oxidation of Sn2+ in the material under applied potential. Finally, pyrochlore SnSb2O6 structure was synthesized utilizing soft hydrothermal method. The crystal structure was studied by Rietveld refinement and the position of Sn2+ was specified. The material showed interesting absorption edge around 700 which is promising for overall water splitting application.

  18. Neutron scattering investigations of frustated magnets

    Science.gov (United States)

    Fennell, Tom

    This thesis describes the experimental investigation of frustrated magnetic systems based on the pyrochlore lattice of corner-sharing tetrahedra. Ho2Ti207 and Dy2Ti207 are examples of spin ices, in which the manifold of disordered magnetic groundstates maps onto that of the proton positions in ice. Using single crystal neutron scattering to measure Bragg and diffuse scattering, the effect of applying magnetic fields along different directions in the crystal was investigated. Different schemes of degeneracy removal were observed for different directions. Long and short range order, and the coexistence of both could be observed by this technique.The field and temperature dependence of magnetic ordering was studied in Ho2Ti207 and Dy2Ti207. Ho2Ti2()7 has been more extensively investigated. The field was applied on [00l], [hh0], [hhh] and [hh2h]. Dy2Ti207 was studied with the field applied on [00l] and [hho] but more detailed information about the evolution of the scattering pattern across a large area of reciprocal space was obtained.With the field applied on [00l] both materials showed complete degeneracy removal. A long range ordered structure was formed. Any magnetic diffuse scattering vanished and was entirely replaced by strong magnetic Bragg scattering. At T =0.05 K both materials show unusual magnetization curves, with a prominent step and hysteresis. This was attributed to the extremely slow dynamics of spin ice materials at this temperature.Both materials were studied in greatest detail with the field applied on [hh0]. The coexistence of long and short range order was observed when the field was raised at T = 0.05 K. The application of a field in this direction separated the spin system into two populations. One could be ordered by the field, and one remained disordered. However, via spin-spin interactions, the field restricted the degeneracy of the disordered spin population. The neutron scattering pattern of Dy2Ti207 shows that the spin system was separated

  19. Origin of heavy REE mineralisation in carbonatites: Constraints form the Huanglongpu Mo-HREE deposit, Qinling, China.

    Science.gov (United States)

    Smith, Martin; Cheng, Xu; Kynicky, Jindrich; Cangelosi, Delia; Wenlei, Song

    2017-04-01

    The carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartz-bearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. Carbonatite monazite (208.9±4.6 Ma to 213.6±4.0; Song et al., 2016) gives a comparable U-Pb radiometric age to molybdenite (220Ma; Stein et al., 1997), confirming interpretations that Mo is derived from the carbonatite, and not a subsequent overprint from regional porphyry-style mineralisation ( 141Ma). The sulphides in the carbonatites have mantle-like 34S ( 1‰) and low δ26Mg values (-1.89 to -1.07‰), similar to sedimentary carbonates, suggesting a recycled sediment contribution in their mantle sources that may be responsible for the Mo and HREE enrichment (Song et al., 2016). The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnäsite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Monazite-(Ce) was subsequently altered to produce apatite, which was in turn replaced by britholite-(Ce), accompanied by the formation of allanite-(Ce). The REE-fluorcarbonates where replaced by synchysite-(Ce) and röntgenite-(Ce). Aeschynite-(Ce) was altered initially to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, through to more silica-rich conditions during the magmatic-hydrothermal transition, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate that the HREE enrichment could not be a passive process, and that hydrothermal fluids must have contributed HREE to the system. The evolution of the fluorcarbonate mineral assemblage requires an increase in aCa2+ and aCO32- in the metasomatic fluid, and so breakdown of HREE-enriched calcite may have been the HREE source

  20. Laachite, (Ca,Mn){sub 2}Zr{sub 2}Nb{sub 2}TiFeO{sub 14}, a new zirconolite-related mineral from the Eifel volcanic region, Germany

    Energy Technology Data Exchange (ETDEWEB)

    Chukanov, Nikita V. [Institute of Problems of Chemical Physics, Chernogolovka (Russian Federation); Krivovichev, Sergey V.; Pakhomova, Anna S. [St. Petersburg State Univ. (Russian Federation). Faculty of Crystallography; Pekov, Igor V.; Vigasina, Marina F. [Moscow State Univ. (Russian Federation). Faculty of Geology; Schaefer, Christof [Suedwestdeutsche Salzwerke AG, Heilbronn (Germany); Van, Konstantin V. [Russian Academy of Sciences, Chernogolovka (Russian Federation). Inst. of Experimental Mineralogy

    2014-02-15

    The new mineral laachite was discovered in a sanidinite specimen from the Laach Lake (Laacher See) volcano, Eifel region, Rheinland-Pfalz, Germany. Associated minerals are sanidine, allanite-(Ce), baddeleyite, hau¨yne, hedenbergite, intermediate members of the jacobsite-magnetite series, phlogopite, rhodonite, spessartine, tephroite, thorite, zircon, and a pyrochlore-group mineral. Laachite is deep brownish-red, has an adamantine lustre, and is translucent; the streak is brownish red. It forms longprismatic crystals up to 0.02 x 0.04 x 0.5 mm, which are present as random intergrowths and twins in cavities within sanidinite. The density calculated from the empirical formula is 5.417 g/cm{sup 3}. The mean refractive index calculated from the Gladstone-Dale relationship is 2.26. The Raman spectrum shows the absence of hydrogen-bearing groups. The chemical composition is (electron microprobe, mean of 5 analyses, wt. %): CaO 4.29, MnO 9.42, FeO 5.73, Y{sub 2}O{sub 3} 2.56, La{sub 2}O{sub 3} 2.00, Ce{sub 2}O{sub 3} 6.37, Nd{sub 2}O{sub 3} 2.22, Al{sub 2}O{sub 3} 0.99, ThO{sub 2} 7.75, TiO{sub 2} 10.98, ZrO{sub 2} 19.39, Nb{sub 2}O{sub 5} 27.82, total 99.52. The empirical formula based on 14 O atoms is: (Ca{sub 0.66}Mn{sub 0.37}Th{sub 0.25}Y{sub 0.20}La{sub 0.11}Ce{sub 0.34}Nd{sub 0.11})(Zr{sub 1.3} {sub 6}Mn{sub 0.64})(Nb{sub 1.81}Ti{sub 1.19})(Fe{sub 0.69}Al{sub 0.17}Mn{sub 0.14})O{sub 14.00}. The simplified formula, taking into account the structural data, is: (Ca,Mn){sub 2}(Zr,Mn){sub 2}Nb{sub 2}TiFeO{sub 14}. Laachite is monoclinic, space group C2/c, a = 7.3119(5), b = 14.1790(10), c = 10.1700(7)Aa, β = 90.072(2), V = 1054.38(1) Aa{sup 3}, Z = 4. The crystal structure was solved using single-crystal X-ray diffraction data. Laachite is a monoclinic analogue of zirconolite-3O, CaZrTi{sub 2}O{sub 7}, with Nb dominant over Ti in the octahedral sites Nb1 and Nb2 and Fe dominant in a site with four-fold coordination. The strongest lines of the powder X-ray diffraction