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Sample records for undistorted pyrochlore oxide

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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)

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  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. 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....

  20. 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.

  1. Estimation of geometrically undistorted B0 inhomogeneity maps

    International Nuclear Information System (INIS)

    Matakos, A; Balter, J; Cao, Y

    2014-01-01

    Geometric accuracy of MRI is one of the main concerns for its use as a sole image modality in precision radiation therapy (RT) planning. In a state-of-the-art scanner, system level geometric distortions are within acceptable levels for precision RT. However, subject-induced B 0 inhomogeneity may vary substantially, especially in air-tissue interfaces. Recent studies have shown distortion levels of more than 2 mm near the sinus and ear canal are possible due to subject-induced field inhomogeneity. These distortions can be corrected with the use of accurate B 0 inhomogeneity field maps. Most existing methods estimate these field maps from dual gradient-echo (GRE) images acquired at two different echo-times under the assumption that the GRE images are practically undistorted. However distortion that may exist in the GRE images can result in estimated field maps that are distorted in both geometry and intensity, leading to inaccurate correction of clinical images. This work proposes a method for estimating undistorted field maps from GRE acquisitions using an iterative joint estimation technique. The proposed method yields geometrically corrected GRE images and undistorted field maps that can also be used for the correction of images acquired by other sequences. The proposed method is validated through simulation, phantom experiments and applied to patient data. Our simulation results show that our method reduces the root-mean-squared error of the estimated field map from the ground truth by ten-fold compared to the distorted field map. Both the geometric distortion and the intensity corruption (artifact) in the images caused by the B 0 field inhomogeneity are corrected almost completely. Our phantom experiment showed improvement in the geometric correction of approximately 1 mm at an air-water interface using the undistorted field map compared to using a distorted field map. The proposed method for undistorted field map estimation can lead to improved geometric

  2. Estimation of geometrically undistorted B0 inhomogeneity maps

    Science.gov (United States)

    Matakos, A.; Balter, J.; Cao, Y.

    2014-09-01

    Geometric accuracy of MRI is one of the main concerns for its use as a sole image modality in precision radiation therapy (RT) planning. In a state-of-the-art scanner, system level geometric distortions are within acceptable levels for precision RT. However, subject-induced B0 inhomogeneity may vary substantially, especially in air-tissue interfaces. Recent studies have shown distortion levels of more than 2 mm near the sinus and ear canal are possible due to subject-induced field inhomogeneity. These distortions can be corrected with the use of accurate B0 inhomogeneity field maps. Most existing methods estimate these field maps from dual gradient-echo (GRE) images acquired at two different echo-times under the assumption that the GRE images are practically undistorted. However distortion that may exist in the GRE images can result in estimated field maps that are distorted in both geometry and intensity, leading to inaccurate correction of clinical images. This work proposes a method for estimating undistorted field maps from GRE acquisitions using an iterative joint estimation technique. The proposed method yields geometrically corrected GRE images and undistorted field maps that can also be used for the correction of images acquired by other sequences. The proposed method is validated through simulation, phantom experiments and applied to patient data. Our simulation results show that our method reduces the root-mean-squared error of the estimated field map from the ground truth by ten-fold compared to the distorted field map. Both the geometric distortion and the intensity corruption (artifact) in the images caused by the B0 field inhomogeneity are corrected almost completely. Our phantom experiment showed improvement in the geometric correction of approximately 1 mm at an air-water interface using the undistorted field map compared to using a distorted field map. The proposed method for undistorted field map estimation can lead to improved geometric

  3. 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)

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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.

  14. 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

  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. 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

  18. 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.

  19. 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

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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...

  8. 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)

  9. 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

  10. 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.

  11. 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

  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. 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.

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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)

  20. 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.

  1. 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

  2. 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.

  3. Electronic structures of ReS sub 2 , ReSe sub 2 and TcS sub 2 in the real and the hypothetical undistorted structures

    CERN Document Server

    Fang, C M; Haas, C; Groot, R A D

    1997-01-01

    The transition-metal dichalcogenides ReX sub 2 (X = S or Se) and TcS sub 2 with a d sup 3 electron configuration have distorted CdCl sub 2 and Cd(OH) sub 2 structures, respectively, with the Re(Tc) atoms in each layer forming parallelogram-shaped connected clusters (diamond chain). Ab-initio band-structure calculations were performed for ReX sub 2 and TcS sub 2 , and the hypothetical undistorted 1T-TcS sub 2 and 3R-ReX sub 2 structures. The calculations show that ReS sub 2 , ReSe sub 2 and TcS sub 2 are semiconductors with energy gaps of about 1.0 eV, 0.5 eV and 0.7 eV, respectively, while for the undistorted structures the Fermi level is in the partly filled band of d sub x sub sup 2 sub - sub y sub sup 2 and d sub x sub y orbitals of the t sub 2 sub g manifold. X-ray photoemission spectra for the core levels and valence band of ReSe sub 2 and ReS sub 2 are presented. The valence x-ray photoemission spectra showed that ReS sub 2 is a p-type semiconductor with an energy gap of about 1.5 eV, while ReSe sub 2 i...

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  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. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. Geometrically undistorted MRI in the presence of field inhomogeneities using compressed sensing accelerated broadband 3D phase encoded turbo spin-echo imaging

    International Nuclear Information System (INIS)

    Van Gorp, Jetse S; Bakker, Chris J G; Bouwman, Job G; Zijlstra, Frank; Seevinck, Peter R; Smink, Jouke

    2015-01-01

    In this study, we explore the potential of compressed sensing (CS) accelerated broadband 3D phase-encoded turbo spin-echo (3D-PE-TSE) for the purpose of geometrically undistorted imaging in the presence of field inhomogeneities. To achieve this goal 3D-PE-SE and 3D-PE-TSE sequences with broadband rf pulses and dedicated undersampling patterns were implemented on a clinical scanner. Additionally, a 3D multi-spectral spin-echo (ms3D-SE) sequence was implemented for reference purposes. First, we demonstrated the influence of susceptibility induced off-resonance effects on the spatial encoding of broadband 3D-SE, ms3D-SE, 3D-PE-SE and 3D-PE-TSE using a grid phantom containing a titanium implant (Δχ = 182 ppm) with x-ray CT as a gold standard. These experiments showed that the spatial encoding of 3D-PE-(T)SE was unaffected by susceptibility induced off-resonance effects, which caused geometrical distortions and/or signal hyper-intensities in broadband 3D-SE and, to a lesser extent, in ms3D-SE frequency encoded methods. Additionally, an SNR analysis was performed and the temporally resolved signal of 3D-PE-(T)SE sequences was exploited to retrospectively decrease the acquisition bandwidth and obtain field offset maps. The feasibility of CS acceleration was studied retrospectively and prospectively for the 3D-PE-SE sequence using an existing CS algorithm adapted for the reconstruction of 3D data with undersampling in all three phase encoded dimensions. CS was combined with turbo-acceleration by variable density undersampling and spherical stepwise T 2 weighting by randomly sorting consecutive echoes in predefined spherical k-space layers. The CS-TSE combination resulted in an overall acceleration factor of 60, decreasing the original 3D-PE-SE scan time from 7 h to 7 min. Finally, CS accelerated 3D-PE-TSE in vivo images of a titanium screw were obtained within 10 min using a micro-coil demonstrating the feasibility of geometrically undistorted MRI near severe

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. Detection of undistorted continuous wave (CW) electron paramagnetic resonance (EPR) spectra with non-adiabatic rapid sweep (NARS) of the magnetic field

    Science.gov (United States)

    Kittell, Aaron W.; Camenisch, Theodore G.; Ratke, Joseph J.; Sidabras, Jason W.; Hyde, James S.

    2011-01-01

    A continuous wave (CW) electron paramagnetic resonance (EPR) spectrum is typically displayed as the first harmonic response to the application of 100 kHz magnetic field modulation, which is used to enhance sensitivity by reducing the level of 1/f noise. However, magnetic field modulation of any amplitude causes spectral broadening and sacrifices EPR spectral intensity by at least a factor of two. In the work presented here, a CW rapid-scan spectroscopic technique that avoids these compromises and also provides a means of avoiding 1/f noise is developed. This technique, termed non-adiabatic rapid sweep (NARS) EPR, consists of repetitively sweeping the polarizing magnetic field in a linear manner over a spectral fragment with a small coil at a repetition rate that is sufficiently high that receiver noise, microwave phase noise, and environmental microphonics, each of which has 1/f characteristics, are overcome. Nevertheless, the rate of sweep is sufficiently slow that adiabatic responses are avoided and the spin system is always close to thermal equilibrium. The repetitively acquired spectra from the spectral fragment are averaged. Under these conditions, undistorted pure absorption spectra are obtained without broadening or loss of signal intensity. A digital filter such as a moving average is applied to remove high frequency noise, which is approximately equivalent in bandwidth to use of an integrating time constant in conventional field modulation with lock-in detection. Nitroxide spectra at L- and X-band are presented. PMID:21741868

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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)

  9. 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)

  10. 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...

  11. 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

  12. 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.

  13. 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

  14. 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

  15. 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

  16. 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.

  17. 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

  18. 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.

  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. 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.

  10. 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.

  11. 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...

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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 .

  17. 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.

  18. 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.

  19. 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...

  20. 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...

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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)

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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)

  13. 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

  14. 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)

  15. 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.

  16. 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.

  17. 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)

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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...

  5. 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

  6. 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.

  7. 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%.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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 .

  1. 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.)

  2. 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.

  3. 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.

  4. 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...

  5. 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

  6. 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.

  7. 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

  8. 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.

  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. 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.

  11. 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)

  12. 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).

  13. 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.

  14. 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.

  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. 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.

  20. 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.

  1. 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.

  2. Effect of Sintering Temperature on the Properties of Aluminium-Aluminium Oxide Composite Materials

    Directory of Open Access Journals (Sweden)

    Dewan Muhammad Nuruzzaman

    2016-12-01

    Full Text Available In this study, aluminium-aluminium oxide (Al-Al2O3 metal matrix composites of different weight percentage reinforcements of aluminium oxide were processed at different sintering temperatures. In order to prepare these composite specimens, conventional powder metallurgy (PM method was used. Three types specimens of different compositions such as 95%Al+5%Al2O3, 90%Al+10%Al2O3 and 85%Al+15%Al2O3 were prepared under 20 Ton compaction load. Then, all the specimens were sintered in a furnace at two different temperatures 550oC and 580oC. In each sintering process, two different heating cycles were used. After the sintering process, it was observed that undistorted flat specimens were successfully prepared for all the compositions. The effects of sintering temperature and weight fraction of aluminium oxide particulates on the density, hardness and microstructure of Al-Al2O3 composites were observed. It was found that density and hardness of the composite specimens were significantly influenced by sintering temperature and percentage aluminium oxide reinforcement. Furthermore, optical microscopy revealed that almost uniform distribution of aluminium oxide reinforcement within the aluminium matrix was achieved.

  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. 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

  7. 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.

  8. 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

  9. 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

  10. 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)

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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. .

  17. 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.

  18. Catalytic oxidation using nitrous oxide

    Directory of Open Access Journals (Sweden)

    Juan Carlos Beltran-Prieto

    2017-01-01

    Full Text Available Nitrous oxide is a very inert gas used generally as oxidant as it offers some advantage compared with other oxidants such as O2 but a considerably higher temperature (> 526 °C is often required. For particular cases such as the oxidation of sugar alcohols, especially for the oxidation of primary alcohols to aldehydes, N2O has the advantage over O2 of a higher reaction selectivity. In the present paper we present the modelling of oxidation reaction of sugar alcohols using an oxidizing agent in low concentrations, which is important to suppress subsequent oxidation reactions due to the very low residual concentrations of the oxidizing agent. For orientation experiments we chose nitrous oxide generated by thermal decomposition of ammonium nitrate. Kinetic modeling of the reaction was performed after determination of the differential equations that describe the system under study.

  19. 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.

  20. 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.

  1. Oxide ceramics

    International Nuclear Information System (INIS)

    Ryshkewitch, E.; Richerson, D.W.

    1985-01-01

    The book explores single-phase ceramic oxide systems from the standpoint of physical chemistry and technology. This second edition also focuses on advances in technology since publication of the original edition. These include improvements in raw materials and forming and sintering techniques, and the major role that oxide ceramics have had in development of advanced products and processes. The text is divided into five major sections: general fundamentals of oxide ceramics, advances in aluminum oxide technology, advances in zirconia technology, and advances in beryllium oxide technology

  2. Phase-encoded MRI for geometrically undistorted imaging and signal characterization

    NARCIS (Netherlands)

    van Gorp, JS

    2016-01-01

    Magnetic resonance imaging (MRI) is a versatile diagnostic modality that has earned its place in clinical practice all over the world. MRI delivers excellent soft-tissue contrast that can be utilized to detect disease and measure physiological properties in a non-invasive manner. As long as the main

  3. Recommendation on measures to safeguard freedom of expression and undistorted competition in EU trade mark law

    DEFF Research Database (Denmark)

    Minssen, Timo

    2015-01-01

    , University of Oxford, United Kingdom Christophe Geiger Associate Professor, Director General and Director of the Research Department, Centre for International Intellectual Property Studies, University of Strasbourg, France Gustavo Ghidini Professor of Intellectual Property and Competition Law, University...... Institute for Innovation and Competition, Munich, Germany Paul van der Kooij Associate Professor of Intellectual Property Law, Leiden Law School, University of Leiden, The Netherlands Annette Kur Senior Researcher, Max Planck Institute for Innovation and Competition, Munich, and Honorary Professor...... Professor of Commercial Law, University of Parma, Italy Timo Minssen Associate Professor, Centre for Information and Innovation Law, University of Copenhagen, Denmark Ansgar Ohly Professor of Civil Law, Intellectual Property and Competition Law, University of Munich, Germany Alexander Peukert Professor...

  4. Split-ring resonators hyperlens for undistorted sub-wavelength imaging

    DEFF Research Database (Denmark)

    Stefani, Alessio; Hayashi, Juliano Grigoleto; Fleming, Simon

    2017-01-01

    on their geometrical structure and therefore can be used as lenses [2-4]. The drawback of all the proposed hyperlenses is that the hyperbolic dispersion is given by the anisotropy of the permittivity only. This means that in such lenses only one of the propagating polarizations is non-diverging while the other (e...

  5. Towards Best Practice in Ethics Education for Scholarly Practitioners of Leadership: An Undistorted View of Reality

    Science.gov (United States)

    Reardon, R. Martin

    2013-01-01

    While it is reasonable to surmise that the vast majority of leaders, regardless of whether they are educators in the broad sense of that term, exercise their leadership in accord with sound ethical principles, the regular instances of exceptions to this rule highlight the importance of incorporating the study of ethics in leadership programs.…

  6. 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....

  7. 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...

  8. Selective oxidation

    International Nuclear Information System (INIS)

    Cortes Henao, Luis F.; Castro F, Carlos A.

    2000-01-01

    It is presented a revision and discussion about the characteristics and factors that relate activity and selectivity in the catalytic and not catalytic partial oxidation of methane and the effect of variables as the temperature, pressure and others in the methane conversion to methanol. It thinks about the zeolites use modified for the catalytic oxidation of natural gas

  9. Anodic oxidation

    CERN Document Server

    Ross, Sidney D; Rudd, Eric J; Blomquist, Alfred T; Wasserman, Harry H

    2013-01-01

    Anodic Oxidation covers the application of the concept, principles, and methods of electrochemistry to organic reactions. This book is composed of two parts encompassing 12 chapters that consider the mechanism of anodic oxidation. Part I surveys the theory and methods of electrochemistry as applied to organic reactions. These parts also present the mathematical equations to describe the kinetics of electrode reactions using both polarographic and steady-state conditions. Part II examines the anodic oxidation of organic substrates by the functional group initially attacked. This part particular

  10. 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)

  11. Magnesium Oxide

    Science.gov (United States)

    Magnesium is an element your body needs to function normally. Magnesium oxide may be used for different reasons. Some people use it as ... one to four times daily depending on which brand is used and what condition you have. Follow ...

  12. 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.

  13. 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

  14. Oxidative stress

    Directory of Open Access Journals (Sweden)

    Osredkar Joško

    2012-05-01

    Full Text Available The human organism is exposed to the influence of various forms of stress, either physical, psychological or chemical, which all have in common that they may adversely affect our body. A certain amount of stress is always present and somehow directs, promotes or inhibits the functioning of the human body. Unfortunately, we are now too many and too often exposed to excessive stress, which certainly has adverse consequences. This is especially true for a particular type of stress, called oxidative stress. All aerobic organisms are exposed to this type of stress because they produce energy by using oxygen. For this type of stress you could say that it is rather imperceptibly involved in our lives, as it becomes apparent only at the outbreak of certain diseases. Today we are well aware of the adverse impact of radicals, whose surplus is the main cause of oxidative stress. However, the key problem remains the detection of oxidative stress, which would allow us to undertake timely action and prevent outbreak of many diseases of our time. There are many factors that promote oxidative stress, among them are certainly a fast lifestyle and environmental pollution. The increase in oxidative stress can also trigger intense physical activity that is directly associated with an increased oxygen consumption and the resulting formation of free radicals. Considering generally positive attitude to physical activity, this fact may seem at first glance contradictory, but the finding has been confimed by several studies in active athletes. Training of a top athlete daily demands great physical effort, which is also reflected in the oxidative state of the organism. However, it should be noted that the top athletes in comparison with normal individuals have a different defense system, which can counteract the negative effects of oxidative stress. Quite the opposite is true for irregular or excessive physical activity to which the body is not adapted.

  15. Compaction of lanthanide oxide porous microspheres: experimental approach and numerical simulation

    International Nuclear Information System (INIS)

    Parant, Paul

    2016-01-01

    One option envisioned for the future management of high level nuclear waste is the transmutation of minor actinides into short-lived fission products in sodium fast reactor. This route requires the development of pellet fabrication processes to prepare Minor Actinide Bearing Blanket (MABB) for the transmutation of americium. Currently, those ceramic pellets are produced by powder metallurgy processes involving numerous grinding and milling steps that generate very fine and highly contaminating and irradiating particles. a viable option for reducing the amount of those fine particles would be to develop a dustless process by working on much coarser particles. In this context, this study is concerned with the pelletizing of porous and spherical lanthanides oxide precursors (surrogates of actinides). The present work uses both experimental data and numerical simulations to optimize the pelletizing step. The final aim is to obtain, after sintering, homogeneous, dense and undistorted ceramic pellets. Firstly, this study concerns the synthesis and characterization of these oxide microspheres precursors by the Weak acid Resin process, which consists in loading beads of ion exchange resin with lanthanides cations and mineralizing the metal loaded resin leads into sub-millimetric-sized oxide microspheres. Comprehensive characterizations of the microstructure were carried out in function of the synthesis parameters such as calcination temperature, metal nature and diameter size /distribution of the resin beads starting materials to better understand their behaviour into the matrix when producing pellets. Secondly, the mechanical properties of a single microsphere were investigated in order to better understand its behaviour during compaction steps. They were also analysed using multi-scale simulations based on the Discrete Element Method (DEM), which is well suited for such particulate materials. In a second approach, compaction studies were carried out in a three parts die

  16. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  17. 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.

  18. RNA oxidation

    DEFF Research Database (Denmark)

    Kjaer, L. K.; Cejvanovic, V.; Henriken, T.

    2015-01-01

    .9 significant hazard ratio for death compared with the quartile with the lowest 8oxoGuo excretion when adjusted for age, sex, BMI, smoker status, s-HbA1c, urine protein excretion and s-cholesterol. We conclude that it is now established that RNA oxidation is an independent risk factor for death in type 2...

  19. Radiolytic oxidation

    International Nuclear Information System (INIS)

    Burns, W.G.; Ewart, F.T.; Hobley, J.; Smith, A.J.; Walters, W.S.; Williams, S.J.

    1991-01-01

    Work under the Radiolytic Oxidation Contract from 1986 until April 1989 is reported. The effects of alpha- and gamma-irradiation on the chemistries of plutonium, neptunium and technetium, under conditions representative of the near fields of intermediate and high level waste repositories, were investigated. Gamma-radiolysis of Np (IV) results in oxidation in solutions below pH 12. Solutions of Tc (VII) are reduced to Tc (IV) by gamma-irradiation in contact with blast furnace slag/ordinary Portland cement under an inert atmosphere but not when in contact with pulverized fuel ash/ordinary Portland cement. Tc (IV) is shown to be susceptible to oxidation by the products of the alpha-radiolysis of water. The results of 'overall effects' experiments, which combined representative components of typical ILW or HLW near fields, supported these observations and also showed enhanced plutonium concentrations in alpha-irradiated, HLW simulations. Mathematical models of the behaviour of plutonium and neptunium during gamma-radiolysis have been developed and indicate that oxidation to Pu (VI) is possible at dose rates typical of those expected for HLW. Simulations at ILW dose rates have indicated some effect upon the speciation of neptunium. Laboratory studies of the gamma-irradiation of Np (IV) in bentonite-equilibrated water have also been modelled. Computer code used: PHREEQE, 8 Figs.; 48 Tabs.; 38 refs

  20. Oxidative stress

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2012-01-01

    Full Text Available The unceasing need for oxygen is in contradiction to the fact that it is in fact toxic to mammals. Namely, its monovalent reduction can have as a consequence the production of short-living, chemically very active free radicals and certain non-radical agents (nitrogen-oxide, superoxide-anion-radicals, hydroxyl radicals, peroxyl radicals, singlet oxygen, peroxynitrite, hydrogen peroxide, hypochlorous acid, and others. There is no doubt that they have numerous positive roles, but when their production is stepped up to such an extent that the organism cannot eliminate them with its antioxidants (superoxide-dismutase, glutathione-peroxidase, catalase, transferrin, ceruloplasmin, reduced glutathion, and others, a series of disorders is developed that are jointly called „oxidative stress.“ The reactive oxygen species which characterize oxidative stress are capable of attacking all main classes of biological macromolecules, actually proteins, DNA and RNA molecules, and in particular lipids. The free radicals influence lipid peroxidation in cellular membranes, oxidative damage to DNA and RNA molecules, the development of genetic mutations, fragmentation, and the altered function of various protein molecules. All of this results in the following consequences: disrupted permeability of cellular membranes, disrupted cellular signalization and ion homeostasis, reduced or loss of function of damaged proteins, and similar. That is why the free radicals that are released during oxidative stress are considered pathogenic agents of numerous diseases and ageing. The type of damage that will occur, and when it will take place, depends on the nature of the free radicals, their site of action and their source. [Projekat Ministarstva nauke Republike Srbije, br. 173034, br. 175061 i br. 31085

  1. 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

  2. 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

  3. 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

  4. PREFACE: Semiconducting oxides Semiconducting oxides

    Science.gov (United States)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

  5. The oxidation; Okislenie

    Energy Technology Data Exchange (ETDEWEB)

    Nikitin, V I

    1961-07-01

    In this chapter of book author determine that alkylene tetra hydro-{gamma}-piron, oxidated by potassium permanganate in all cases of passed oxidation gave oxidation products, confirmatory their structure.

  6. Thermally exfoliated graphite oxide

    Science.gov (United States)

    Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

    2011-01-01

    A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

  7. The Enzymatic Oxidation of Graphene Oxide

    Science.gov (United States)

    Kotchey, Gregg P.; Allen, Brett L.; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A.; Tyurina, Yulia Y.; Klein-Seetharaman, Judith; Kagan, Valerian E.; Star, Alexander

    2011-01-01

    Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon – the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (~40 µM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, UV-Vis, EPR and FT-IR spectroscopy, TEM, AFM, SDS-PAGE, and GC-MS. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Due to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. PMID:21344859

  8. Tin-antimony oxide oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

    1998-12-15

    Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

  9. Oxidation films morphology

    International Nuclear Information System (INIS)

    Paidassi, J.

    1960-01-01

    After studying the oxidation of several pure polyvalent metals (Fe, Cu, Mn, Ni, U) and of their oxides at high temperature and atmospheric pressure, the author suggests how to modify the usual representation of the oxide film (a piling of different oxide layers, homogeneous on a micrographic scale with a equi-axial crystallisation, free of mechanical tensions, with flat boundary surfaces) to have it nearer to reality. In this first part, the author exposes the study of the real micrographic structure of the oxidation film and gives examples of precipitation in the oxides during the cooling of the oxidised sample. (author) [fr

  10. Internal fuel pin oxidizer

    International Nuclear Information System (INIS)

    Andrews, M.G.

    1978-01-01

    A nuclear fuel pin has positioned within it material which will decompose to release an oxidizing agent which will react with the cladding of the pin and form a protective oxide film on the internal surface of the cladding

  11. Oxidation-resistant cermet

    Science.gov (United States)

    Phillips, W. M.

    1977-01-01

    Chromium metal alloys and chromium oxide ceramic are combined to produce cermets with oxidation-resistant properties. Application of cermets includes use in hot corrosive environments requiring strong resistive materials.

  12. Bridged graphite oxide materials

    Science.gov (United States)

    Herrera-Alonso, Margarita (Inventor); McAllister, Michael J. (Inventor); Aksay, Ilhan A. (Inventor); Prud'homme, Robert K. (Inventor)

    2010-01-01

    Bridged graphite oxide material comprising graphite sheets bridged by at least one diamine bridging group. The bridged graphite oxide material may be incorporated in polymer composites or used in adsorption media.

  13. Oxidative phosphorylation revisited

    DEFF Research Database (Denmark)

    Nath, Sunil; Villadsen, John

    2015-01-01

    The fundamentals of oxidative phosphorylation and photophosphorylation are revisited. New experimental data on the involvement of succinate and malate anions respectively in oxidative phosphorylation and photophosphorylation are presented. These new data offer a novel molecular mechanistic...

  14. Oxidative Stress in Neurodegeneration

    Directory of Open Access Journals (Sweden)

    Varsha Shukla

    2011-01-01

    Full Text Available It has been demonstrated that oxidative stress has a ubiquitous role in neurodegenerative diseases. Major source of oxidative stress due to reactive oxygen species (ROS is related to mitochondria as an endogenous source. Although there is ample evidence from tissues of patients with neurodegenerative disorders of morphological, biochemical, and molecular abnormalities in mitochondria, it is still not very clear whether the oxidative stress itself contributes to the onset of neurodegeneration or it is part of the neurodegenerative process as secondary manifestation. This paper begins with an overview of how oxidative stress occurs, discussing various oxidants and antioxidants, and role of oxidative stress in diseases in general. It highlights the role of oxidative stress in neurodegenerative diseases like Alzheimer's, Parkinson's, and Huntington's diseases and amyotrophic lateral sclerosis. The last part of the paper describes the role of oxidative stress causing deregulation of cyclin-dependent kinase 5 (Cdk5 hyperactivity associated with neurodegeneration.

  15. Zinc oxide overdose

    Science.gov (United States)

    Zinc oxide is an ingredient in many products. Some of these are certain creams and ointments used ... prevent or treat minor skin burns and irritation. Zinc oxide overdose occurs when someone eats one of ...

  16. Oxidative Stress in BPH

    Directory of Open Access Journals (Sweden)

    Murat Savas

    2009-01-01

    The present study has shown that there were not relationship between potency of oxidative stress and BPH. Further well designed studies should be planned to find out whether the oxidative stress-related parameters play role in BPH as an interesting pathology in regard of the etiopathogenesis. Keywords: benign prostatic hyperplasia, oxidative stress, prostate

  17. Sputtered indium oxide films

    International Nuclear Information System (INIS)

    Gillery, F.H.

    1986-01-01

    A method is described for depositing on a substrate multiple layer films comprising at least one primary layer of a metal oxide and at least one primary layer of a metal other than the metal of the oxide layer. The improvement described here comprises improving the adhesion between the metal oxide and metal layers by depositing between the layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers. An article of manufacture is described comprising a nonmetallic substrate, and deposited thereon in any order: a. at least one coating layer of metal; b. at least one coating layer of an oxide of a metal other than the metal of the metal layer; and c. deposited between the metal and metal oxide layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers

  18. Oxidation Resistant Graphite Studies

    Energy Technology Data Exchange (ETDEWEB)

    W. Windes; R. Smith

    2014-07-01

    The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

  19. Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

    Science.gov (United States)

    Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

    2013-09-24

    A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

  20. Direct oxide reducing method

    International Nuclear Information System (INIS)

    Tokiwai, Moriyasu.

    1995-01-01

    Calcium oxides and magnetic oxides as wastes generated upon direct reduction are subjected to molten salt electrolysis, and reduced metallic calcium and magnesium are separated and recovered. Then calcium and magnesium are used recyclically as the reducing agent upon conducting direct oxide reduction. Even calcium oxides and magnesium oxides, which have high melting points and difficult to be melted usually, can be melted in molten salts of mixed fluorides or chlorides by molten-salt electrolysis. Oxides are decomposed by electrolysis, and oxygen is removed in the form of carbon monoxide, while the reduced metallic calcium and magnesium rise above the molten salts on the side of a cathode, and then separated. Since only carbon monoxide is generated as radioactive wastes upon molten salt electrolysis, the amount of radioactive wastes can be greatly reduced, and the amount of the reducing agent used can also be decreased remarkably. (N.H.)

  1. Oxidizer Scoping Studies

    Energy Technology Data Exchange (ETDEWEB)

    Chancellor, Christopher John [Los Alamos National Laboratory

    2016-11-07

    The purpose of this report is to present the results of the acceptable knowledge (AK) review of oxidizers present in active waste streams, provide a technical analysis of the oxidizers, and report the results of the scoping study testing. This report will determine the fastest burning oxidizer to be used in the development of a Test Plan for Preparation and Testing of Sorbents Mixed with Oxidizer found in Transuranic Waste (DWT-TP-001). The companion report, DWT-RPT-002, Sorbent Scoping Studies, contains similar information for sorbents identified during the AK review of TRU waste streams. The results of the oxidizer and sorbent scoping studies will be used to inform the QL1 test plan. The QL1 test results will support the development of a basis of knowledge document that will evaluate oxidizing chemicals and sorbents in TRU waste and provide guidance for treatment.

  2. Review of zircaloy oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Iglesias, F.C. [Royal Military College of Canada, Kingston, Ontario (Canada); Lewis, B.J. [Univ. of Ontario Inst. of Technology, Faculty of Energy Systems and Nuclear Science, Oshawa, Ontario (Canada)

    2013-07-01

    This paper provides an overview of the kinetics for Zircaloy clad oxidation behaviour in steam and air during reactor accident conditions. The generation of chemical heat from metal/water reaction is considered. The effect of internal clad oxidation due to Zircaloy/UO{sub 2} interaction is also discussed. Low-temperature oxidation of Zircaloy due to water-side corrosion is further described. (author)

  3. OXIDATION OF TRANSURANIC ELEMENTS

    Science.gov (United States)

    Moore, R.L.

    1959-02-17

    A method is reported for oxidizing neptunium or plutonium in the presence of cerous values without also oxidizing the cerous values. The method consists in treating an aqueous 1N nitric acid solution, containing such cerous values together with the trivalent transuranic elements, with a quantity of hydrogen peroxide stoichiometrically sufficient to oxidize the transuranic values to the hexavalent state, and digesting the solution at room temperature.

  4. METAL OXIDE NANOPARTICLES

    Energy Technology Data Exchange (ETDEWEB)

    FERNANDEZ-GARCIA,M.; RODGRIGUEZ, J.A.

    2007-10-01

    This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

  5. Oxidation mechanisms occurring in wines

    OpenAIRE

    Oliveira, Carla Maria; Ferreira, António César Silva; Freitas, Victor De; Silva, Artur M. S.

    2011-01-01

    The present review aims to show the state of the art on the oxidation mechanisms occurring in wines, as well as the methods to monitor, classify and diagnose wine oxidation. Wine oxidation can be divided in enzymatic oxidation and non-enzymatic oxidation. Enzymatic oxidation almost entirely occurs in grape must and is largely correlated with the content of hydroxycinnamates, such as caffeoyltartaric acid and paracoumaroyltartaric acid, and flavan-3-ols. Non-enzymatic oxidation, al...

  6. Molecular water oxidation catalysis

    CERN Document Server

    Llobet, Antoni

    2014-01-01

    Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most importan

  7. Isotopes in oxidation reactions

    International Nuclear Information System (INIS)

    Stewart, R.

    1976-01-01

    The use of isotopes in the study of organic oxidation mechanisms is discussed. The help provided by tracer studies to demonstrate the two-equivalent path - hydride transfer, is illustrated by the examples of carbonium oxidants and the Wacker reaction. The role of kinetic isotope effects in the study of the scission of carbon-hydrogen bonds is illustrated by hydride abstraction, hydrogen atom abstraction, proton abstraction and quantum mechanical tunnelling. Isotopic studies on the oxidation of alcohols, carbonyl compounds, amines and hydrocarbons are discussed. The role of isotopes in the study of biochemical oxidation is illustrated with a discussion on nicotinamide and flavin coenzymes. (B.R.H.)

  8. Rare earth oxide doping in oxide cathodes

    International Nuclear Information System (INIS)

    Engelsen, Daniel den; Gaertner, Georg

    2006-01-01

    The effect on life performance and poisoning with O 2 by doping oxide cathodes with rare earth oxides and pseudo rare earth oxides, notably yttria, is qualitatively explained in terms of electrolysis of BaO during emission of electrons. Doped cathodes show less electrolysis and consume therefore less Ba during life: consequently, doped cathodes have a better life performance. However, the lower Ba-production makes doped cathodes more sensitive to oxygen poisoning. The experimentally found relation between conductivity and yttria concentration was the motive to propose a new model for the crystal imperfections in BaO. In this new imperfection model most Y 3+ -ions will combine with barium vacancies, therefore, the increase of the conductivity is modest and also the effect on the position of the Fermi level is modest. By assuming a combination of bulk and surface conductivity, the agreement between experiment and theory can be improved further

  9. Stabilized chromium oxide film

    Science.gov (United States)

    Garwin, Edward L.; Nyaiesh, Ali R.

    1988-01-01

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150.ANG. are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  10. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  11. Reducible oxide based catalysts

    Science.gov (United States)

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  12. Death from Nitrous Oxide.

    Science.gov (United States)

    Bäckström, Björn; Johansson, Bengt; Eriksson, Anders

    2015-11-01

    Nitrous oxide is an inflammable gas that gives no smell or taste. It has a history of abuse as long as its clinical use, and deaths, although rare, have been reported. We describe two cases of accidental deaths related to voluntary inhalation of nitrous oxide, both found dead with a gas mask covering the face. In an attempt to find an explanation to why the victims did not react properly to oncoming hypoxia, we performed experiments where a test person was allowed to breath in a closed system, with or without nitrous oxide added. Vital signs and gas concentrations as well as subjective symptoms were recorded. The experiments indicated that the explanation to the fact that neither of the descendents had reacted to oncoming hypoxia and hypercapnia was due to the inhalation of nitrous oxide. This study raises the question whether nitrous oxide really should be easily, commercially available. © 2015 American Academy of Forensic Sciences.

  13. RNA modifications by oxidation

    DEFF Research Database (Denmark)

    Poulsen, Henrik E; Specht, Elisabeth; Broedbaek, Kasper

    2012-01-01

    to encompass various classes of novel regulatory RNAs, including, e.g., microRNAs. It is well known that DNA is constantly oxidized and repaired by complex genome maintenance mechanisms. Analogously, RNA also undergoes significant oxidation, and there are now convincing data suggesting that oxidation......The past decade has provided exciting insights into a novel class of central (small) RNA molecules intimately involved in gene regulation. Only a small percentage of our DNA is translated into proteins by mRNA, yet 80% or more of the DNA is transcribed into RNA, and this RNA has been found......, and the consequent loss of integrity of RNA, is a mechanism for disease development. Oxidized RNA is found in a large variety of diseases, and interest has been especially devoted to degenerative brain diseases such as Alzheimer disease, in which up to 50-70% of specific mRNA molecules are reported oxidized, whereas...

  14. Engineering complex oxide interfaces for oxide electronics

    NARCIS (Netherlands)

    Roy, Saurabh

    2015-01-01

    A complex interplay of physics and chemistry in transition metal oxides determines their electronic, magnetic, and ferroic properties enabling a wide range of applications of these materials. BiFeO_3, a canonical multiferroic system exhibits the interesting feature of enhanced conductivity on

  15. Protein oxidation in aquatic foods

    DEFF Research Database (Denmark)

    Baron, Caroline P.

    2014-01-01

    The chapter discusses general considerations about protein oxidation and reviews the mechanisms involved in protein oxidation and consequences of protein oxidation on fish proteins. It presents two case studies, the first deals with protein and lipid oxidation in frozen rainbow trout......, and the second with oxidation in salted herring. The mechanisms responsible for initiation of protein oxidation are unclear, but it is generally accepted that free radical species initiating lipid oxidation can also initiate protein oxidation. The chapter focuses on interaction between protein and lipid...... oxidation. The protein carbonyl group measurement is the widely used method for estimating protein oxidation in foods and has been used in fish muscle. The chapter also talks about the impact of protein oxidation on protein functionality, fish muscle texture, and food nutritional value. Protein oxidation...

  16. Oxidation of uraninite

    International Nuclear Information System (INIS)

    Janeczek, J.; Ewing, R.C.

    1993-06-01

    Samples of uraninite and pitchblende annealed at 1200 degrees C in H 2 , and untreated pitchblende were sequentially oxidized in air at 180-190 degrees C, 230 degrees C, and 300 degrees C. Uraninite and untreated pitchblende oxidized to the U 4 O 9 -type oxide, and their x-ray symmetry remained isometric up to 300 degrees C. Reduced pitchblende, after oxidation to UO 2+x and U 4 O 9 -type oxides, transformed into α-U 3 O 8 at 300 degrees C. Two major mechanisms control uraninite and untreated pitchblende stability during oxidation: 1. Th and/or lanthanide elements maintain charge balance and block oxygen interstitials near impurity cations; 2. the uraninite structure saturates with respect to excess and radiation-induced oxygen interstitials. Untreated pitchblende during oxidation behaved similarly to irradiated UO 2 in spent nuclear fuel; whereas, reduced pitchblende resembled non-irradiated UO 2 . An analysis of the data in the literature, as well as our own efforts (XRD, EMPA, SEM, AEM) to identify U 3 O 7 in samples form Cigar Lake, Canada, failed to provide conclusive evidence of the natural occurrence of tetragonal αU 3 O 7 . Most probably, reported occurrences of U 3 O 7 are mixtures of isometric uraninites of slightly different compositions, 45 refs

  17. Recovery of vanadium oxide

    International Nuclear Information System (INIS)

    Bates, C.P.; Clark, N.E.

    1985-01-01

    This invention relates to the recovery of vanadium oxide from molten metal. The invention provides a method for recovering vanadium oxide from molten metal, which includes passing oxygen and at least one coolant gas or shroud into the molten metal by way of at least one elongate lance. The invention also provides an arrangement for the recovery of vanadium oxide from molten metal, which includes at least one elongate lance extending into the molten metal. The lance is provided with at least one elongate bore extending therethrough. Means are provided to allow at least oxygen and at least one coolant gas to pass through the lance and into the molten metal

  18. High Current Oxide Cathodes

    National Research Council Canada - National Science Library

    Luhmann, N

    2000-01-01

    The aim of the AASERT supported research is to develop the plasma deposition/implantation process for coating barium, strontium and calcium oxides on nickel substrates and to perform detailed surface...

  19. Markers of protein oxidation

    DEFF Research Database (Denmark)

    Headlam, Henrietta A; Davies, Michael Jonathan

    2004-01-01

    Exposure of proteins to radicals in the presence of O2 gives both side-chain oxidation and backbone fragmentation. These processes can be interrelated, with initial side-chain oxidation giving rise to backbone damage via transfer reactions. We have shown previously that alkoxyl radicals formed...... of this process depends on the extent of oxidation at C-3 compared with other sites. HO*, generated by gamma radiolysis, gave the highest total carbonyl yield, with protein-bound carbonyls predominating over released. In contrast, metal ion/H2O2 systems, gave more released than bound carbonyls, with this ratio...... modulated by EDTA. This is ascribed to metal ion-protein interactions affecting the sites of initial oxidation. Hypochlorous acid gave low concentrations of released carbonyls, but high yields of protein-bound material. The peroxyl radical generator 2,2'-azobis(2-amidinopropane) hydrochloride...

  20. Oxidizer in phosphoric reactors

    International Nuclear Information System (INIS)

    Santos Benedetto, J. dos

    1985-01-01

    Oxidation during the manufacture of wet-process phosphoric acid affected the distribution of uranium and impurities between phosphoric acid and gypsum, by decreasing the uranium loss to gypsum and the impurities solubilization in phosphoric acid. (Author) [pt

  1. Single sheet iron oxides

    DEFF Research Database (Denmark)

    Yin, Zhou

    profile with reversible reduction and oxidation, suggesting the formation of FeII-OH/O-FeIII clusters as that in GRs were formed on the ITO electrode (trichloroethylene (TCE), tetrachloride (CT) and 4-chlorophenol are used to test...

  2. High Current Oxide Cathodes

    National Research Council Canada - National Science Library

    Luhmann, N

    2000-01-01

    .... The vacuum are plasma deposition gun developed at Lawrence Berkeley National Laboratory (LBNL) has been used to deposit oxides and nitrides with very precise control over deposition rate and composition.

  3. Titanium oxide fever

    International Nuclear Information System (INIS)

    De Jonge, D.; Visser, J.

    2012-01-01

    One measure to improve air quality is to apply photo-catalytic substances that capture NOx onto the road surface or onto baffle boards alongside the roads. The effect of titanium oxide containing clinkers with coating was discussed in the report 'Demonstration project of air-purifying pavement in Hengelo, The Netherlands' that was published in May 2011. This article examines the way in which the effectiveness of this study was determined. Can titanium oxide containing clinkers and coatings indeed capture NOx?. [nl

  4. Metal atom oxidation laser

    International Nuclear Information System (INIS)

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-01-01

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides

  5. Chemistry of phospholipid oxidation.

    Science.gov (United States)

    Reis, Ana; Spickett, Corinne M

    2012-10-01

    The oxidation of lipids has long been a topic of interest in biological and food sciences, and the fundamental principles of non-enzymatic free radical attack on phospholipids are well established, although questions about detail of the mechanisms remain. The number of end products that are formed following the initiation of phospholipid peroxidation is large, and is continually growing as new structures of oxidized phospholipids are elucidated. Common products are phospholipids with esterified isoprostane-like structures and chain-shortened products containing hydroxy, carbonyl or carboxylic acid groups; the carbonyl-containing compounds are reactive and readily form adducts with proteins and other biomolecules. Phospholipids can also be attacked by reactive nitrogen and chlorine species, further expanding the range of products to nitrated and chlorinated phospholipids. Key to understanding the mechanisms of oxidation is the development of advanced and sensitive technologies that enable structural elucidation. Tandem mass spectrometry has proved invaluable in this respect and is generally the method of choice for structural work. A number of studies have investigated whether individual oxidized phospholipid products occur in vivo, and mass spectrometry techniques have been instrumental in detecting a variety of oxidation products in biological samples such as atherosclerotic plaque material, brain tissue, intestinal tissue and plasma, although relatively few have achieved an absolute quantitative analysis. The levels of oxidized phospholipids in vivo is a critical question, as there is now substantial evidence that many of these compounds are bioactive and could contribute to pathology. The challenges for the future will be to adopt lipidomic approaches to map the profile of oxidized phospholipid formation in different biological conditions, and relate this to their effects in vivo. This article is part of a Special Issue entitled: Oxidized phospholipids

  6. Thin zirconium oxides

    International Nuclear Information System (INIS)

    Oviedo, Cristina

    2000-01-01

    Polycrystalline Zr and two pure Zr single-crystal samples, one oriented with the normal to the surface parallel to the c-axis of the hcp structure (Z1) and the other with the normal perpendicular to c (Z2), were oxidised at 10 -8 , 10 -7 and 10 -6 Torr and room temperature. Oxidation kinetics, composition and thicknesses of the oxide films formed in each case were analyzed using XPS (X-ray Photoelectron Spectroscopy) as the main technique. The oxidation kinetics followed logarithmic laws in all cases. The deconvolution of XPS Zr3d peaks indicated the formation of two Zr-O compounds before the formation of ZrO 2 . Varying the photoelectrons take-off angle, the compound distribution inside the oxide films could be established. Thus, it was confirmed that the most external oxide, in contact with the gas, was ZrO 2 . The thickness of the films grown at the different pressures was determined. In the polycrystalline samples, thicknesses between 15 and 19 ± 2Angstroem were obtained for pressures between 10 -8 and 10 -6 Torr, in close coincidence with the determined ones for Z2. The thicknesses measured in Z1 were smaller, reaching 13 ± 2Angstroem for the oxidations performed at 10 -6 Torr. (author)

  7. Does oxidative stress shorten telomeres?

    NARCIS (Netherlands)

    Boonekamp, Jelle J.; Bauch, Christina; Mulder, Ellis; Verhulst, Simon

    Oxidative stress shortens telomeres in cell culture, but whether oxidative stress explains variation in telomere shortening in vivo at physiological oxidative stress levels is not well known. We therefore tested for correlations between six oxidative stress markers and telomere attrition in nestling

  8. Electrochemistry of hydrous oxide films

    International Nuclear Information System (INIS)

    Burke, L.D.; Lyons, M.E.G.

    1986-01-01

    The formation, acid-base properties, structural aspects, and transport processes of hydrous oxide films are discussed. Classical and nonclassical theoretical models of the oxide-solution interface are compared. Monolayer oxidation, behavior, and crystal growth of oxides on platinum, palladium, gold, iridium, rhodium, ruthenium, and some non-noble metals, including tungsten, are reviewed and compared

  9. Porous ceramics out of oxides

    International Nuclear Information System (INIS)

    Bakunov, V.S.; Balkevich, V.L.; Vlasov, A.S.; Guzman, I.Ya.; Lukin, E.S.; Poluboyarinov, D.N.; Poliskij, R.Ya.

    1977-01-01

    A review is made of manufacturing procedures and properties of oxide ceramics intended for high-temperature thermal insulation and thermal protection applications. Presented are structural characteristics of porous oxide refractories and their properties. Strength and thermal conductivity was shown to depend upon porosity. Described is a procedure for manufacturing porous ceramic materials from aluminium oxide, zirconium dioxide, magnesium oxide, beryllium oxide. The thermal resistance of porous ceramics from BeO is considerably greater than that of other high-refractoriness oxides. Listed are areas of application for porous materials based on oxides

  10. Staphylococcal response to oxidative stress

    Directory of Open Access Journals (Sweden)

    Rosmarie eGaupp

    2012-03-01

    Full Text Available Staphylococci are a versatile genus of bacteria that are capable of causing acute and chronic infections in diverse host species. The success of staphylococci as pathogens is due in part to their ability to mitigate endogenous and exogenous oxidative and nitrosative stress. Endogenous oxidative stress is a consequence of life in an aerobic environment; whereas, exogenous oxidative and nitrosative stress are often due to the bacteria’s interaction with host immune systems. To overcome the deleterious effects of oxidative and nitrosative stress, staphylococci have evolved protection, detoxification, and repair mechanisms that are controlled by a network of regulators. In this review, we summarize the cellular targets of oxidative stress, the mechanisms by which staphylococci sense oxidative stress and damage, oxidative stress protection and repair mechanisms, and regulation of the oxidative stress response. When possible, special attention is given to how the oxidative stress defense mechanisms help staphylococci control oxidative stress in the host.

  11. Protein oxidation and peroxidation

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan

    2016-01-01

    Proteins are major targets for radicals and two-electron oxidants in biological systems due to their abundance and high rate constants for reaction. With highly reactive radicals damage occurs at multiple side-chain and backbone sites. Less reactive species show greater selectivity with regard...... to the residues targeted and their spatial location. Modification can result in increased side-chain hydrophilicity, side-chain and backbone fragmentation, aggregation via covalent cross-linking or hydrophobic interactions, protein unfolding and altered conformation, altered interactions with biological partners...... and modified turnover. In the presence of O2, high yields of peroxyl radicals and peroxides (protein peroxidation) are formed; the latter account for up to 70% of the initial oxidant flux. Protein peroxides can oxidize both proteins and other targets. One-electron reduction results in additional radicals...

  12. Bacterium oxidizing carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Kistner, A

    1953-01-01

    Present-day knowledge of the microbiological oxidation of carbon monoxide is based on doubtful observations and imperfect experimental procedures. By making use of shake cultures in contact with gas mixtures containing high concentrations of CO and by employing liquid enrichment media with a low content of organic matter and solid media of the same composition with not more than 1.2% agar, it proved possible to isolate a co-oxidizing bacterium of the genus hydrogenomonas from sewage sludge. For the first time irrefutable proof has been given of the oxidation of carbon monoxide by a pure culture of a bacterium, both in growing cultures and in resting cell suspensions. 12 references.

  13. Zircaloy oxidation studies

    International Nuclear Information System (INIS)

    Prater, J.T.; Beauchamp, R.H.; Saenz, N.T.

    1985-06-01

    The oxidation kinetics of Zircaloy-4 in steam have been determined at 1300-2400 0 C. Growth of the ZrO 2 and α-Zr layers display parabolic behavior over the entire temperature range studied. A discontinuity in the oxidation kinetics at 1510 0 C causes rates to increase above those previously established by the Baker-Just relationship. This increase coincides with the tetragonal-to-cubic phase transformation in ZrO/sub 2-x/. No discontinuity in the oxide growth rate is observed upon melting of Zr(0). The effects of temperature gradients have been taken into account and corrected values representative of near-isothermal conditions have been computed

  14. Oxidative Tritium Decontamination System

    International Nuclear Information System (INIS)

    Gentile, Charles A.; Parker, John J.; Guttadora, Gregory L.; Ciebiera, Lloyd P.

    2002-01-01

    The Princeton Plasma Physics Laboratory, Tritium Systems Group has developed and fabricated an Oxidative Tritium Decontamination System (OTDS), which is designed to reduce tritium surface contamination on various components and items. The system is configured to introduce gaseous ozone into a reaction chamber containing tritiated items that require a reduction in tritium surface contamination. Tritium surface contamination (on components and items in the reaction chamber) is removed by chemically reacting elemental tritium to tritium oxide via oxidation, while purging the reaction chamber effluent to a gas holding tank or negative pressure HVAC system. Implementing specific concentrations of ozone along with catalytic parameters, the system is able to significantly reduce surface tritium contamination on an assortment of expendable and non-expendable items. This paper will present the results of various experimentation involving employment of this system

  15. Krypton oxides under pressure.

    Science.gov (United States)

    Zaleski-Ejgierd, Patryk; Lata, Pawel M

    2016-02-02

    Under high pressure, krypton, one of the most inert elements is predicted to become sufficiently reactive to form a new class of krypton compounds; krypton oxides. Using modern ab-initio evolutionary algorithms in combination with Density Functional Theory, we predict the existence of several thermodynamically stable Kr/O species at elevated pressures. In particular, our calculations indicate that at approx. 300 GPa the monoxide, KrO, should form spontaneously and remain thermo- and dynamically stable with respect to constituent elements and higher oxides. The monoxide is predicted to form non-molecular crystals with short Kr-O contacts, typical for genuine chemical bonds.

  16. Sintering of beryllium oxide

    International Nuclear Information System (INIS)

    Caillat, R.; Pointud, R.

    1955-01-01

    This study had for origin to find a process permitting to manufacture bricks of beryllium oxide of pure nuclear grade, with a density as elevated as possible and with standardized shape. The sintering under load was the technique kept for the manufacture of the bricks. Because of the important toxicity of the beryllium oxide, the general features for the preliminary study of the sintering, have been determined while using alumina. The obtained results will be able to act as general indication for ulterior studies with sintering under load. (M.B.) [fr

  17. Catalytic Oxidation of Cyanogen Chloride over a Monolithic Oxidation Catalyst

    National Research Council Canada - National Science Library

    Campbell, Jeffrey

    1997-01-01

    The catalytic oxidation of cyanogen chloride was evaluated over a monolithic oxidation catalyst at temperatures between 200 and 300 deg C in air employing feed concentrations between 100 and 10,000 ppm...

  18. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-01-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  19. Green oxidations: Titanium dioxide induced tandem oxidation coupling reactions

    OpenAIRE

    Jeena, Vineet; Robinson, Ross S

    2009-01-01

    Summary The application of titanium dioxide as an oxidant in tandem oxidation type processes is described. Under microwave irradiation, quinoxalines have been synthesized in good yields from the corresponding ?-hydroxyketones.

  20. Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

    International Nuclear Information System (INIS)

    Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

    1985-01-01

    Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

  1. Improved Understanding of In Situ Chemical Oxidation Contaminant Oxidation Kinetics

    Science.gov (United States)

    2007-12-01

    natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE perchloroethylene HSO5− peroxymonosulfate PNDA p...properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and stability in the subsurface, and develop a standardized natural...chlorinated ethenes For contaminant oxidation by activated S2O82−, it is more difficult to develop a general description of kobs vs. T because there are

  2. Iron oxides photochemical dissolution

    International Nuclear Information System (INIS)

    Blesa, M.A.; Litter, M.I.

    1987-01-01

    This work was intended to study the light irradiation influence of diverse wave-lengths on iron oxides dissolution in aqueous solutions. The objectives of this work were: the exploration of photochemical processes with the aim of its eventual application in: a) decontamination and chemical cleaning under special conditions; b) materials for solar energy conversion. (Author)

  3. Highly oxidized superconductors

    Science.gov (United States)

    Morris, Donald E.

    1994-01-01

    Novel superconducting materials in the form of compounds, structures or phases are formed by performing otherwise known syntheses in a highly oxidizing atmosphere rather than that created by molecular oxygen at atmospheric pressure or below. This leads to the successful synthesis of novel superconducting compounds which are thermodynamically stable at the conditions under which they are formed.

  4. Oxidative Stress in Myopia

    Directory of Open Access Journals (Sweden)

    Bosch-Morell Francisco

    2015-01-01

    Full Text Available Myopia affected approximately 1.6 billion people worldwide in 2000, and it is expected to increase to 2.5 billion by 2020. Although optical problems can be corrected by optics or surgical procedures, normal myopia and high myopia are still an unsolved medical problem. They frequently predispose people who have them to suffer from other eye pathologies: retinal detachment, glaucoma, macular hemorrhage, cataracts, and so on being one of the main causes of visual deterioration and blindness. Genetic and environmental factors have been associated with myopia. Nevertheless, lack of knowledge in the underlying physiopathological molecular mechanisms has not permitted an adequate diagnosis, prevention, or treatment to be found. Nowadays several pieces of evidence indicate that oxidative stress may help explain the altered regulatory pathways in myopia and the appearance of associated eye diseases. On the one hand, oxidative damage associated with hypoxia myopic can alter the neuromodulation that nitric oxide and dopamine have in eye growth. On the other hand, radical superoxide or peroxynitrite production damage retina, vitreous, lens, and so on contributing to the appearance of retinopathies, retinal detachment, cataracts and so on. The objective of this review is to suggest that oxidative stress is one of the key pieces that can help solve this complex eye problem.

  5. Wet oxidation of quinoline

    DEFF Research Database (Denmark)

    Thomsen, A.B.; Kilen, H.H.

    1998-01-01

    The influence of oxygen pressure (0.4 and 2 MPa). reaction time (30 and 60 min) and temperature (260 and 280 degrees C) on the wet oxidation of quinoline has been studied. The dominant parameters for the decomposition of quinoline were oxygen pressure and reaction temperature. whereas the reactio...

  6. Solid Oxide Fuel Cell

    DEFF Research Database (Denmark)

    2010-01-01

    The solid oxide fuel cell comprising a metallic support material, an active anode layer consisting of a good hydrocarbon cracking catalyst, an electrolyte layer, an active cathode layer, and a transition layer consisting of preferably a mixture of LSM and a ferrite to the cathode current collector...

  7. Dopamine Oxidation and Autophagy

    Directory of Open Access Journals (Sweden)

    Patricia Muñoz

    2012-01-01

    Full Text Available The molecular mechanisms involved in the neurodegenerative process of Parkinson's disease remain unclear. Currently, there is a general agreement that mitochondrial dysfunction, α-synuclein aggregation, oxidative stress, neuroinflammation, and impaired protein degradation are involved in the neurodegeneration of dopaminergic neurons containing neuromelanin in Parkinson's disease. Aminochrome has been proposed to play an essential role in the degeneration of dopaminergic neurons containing neuromelanin by inducing mitochondrial dysfunction, oxidative stress, the formation of neurotoxic α-synuclein protofibrils, and impaired protein degradation. Here, we discuss the relationship between the oxidation of dopamine to aminochrome, the precursor of neuromelanin, autophagy dysfunction in dopaminergic neurons containing neuromelanin, and the role of dopamine oxidation to aminochrome in autophagy dysfunction in dopaminergic neurons. Aminochrome induces the following: (i the formation of α-synuclein protofibrils that inactivate chaperone-mediated autophagy; (ii the formation of adducts with α- and β-tubulin, which induce the aggregation of the microtubules required for the fusion of autophagy vacuoles and lysosomes.

  8. Plutonium oxide dissolution

    International Nuclear Information System (INIS)

    Gray, J.H.

    1992-01-01

    Several processing options for dissolving plutonium oxide (PuO 2 ) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO 2 typically generated by burning plutonium metal and PuO 2 produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO 2 in canyon dissolvers. The options involve solid solution formation of PuO 2 With uranium oxide (UO 2 ) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO 2 with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO 2 materials may warrant further study

  9. Aqueous polyethylene oxide solutions

    International Nuclear Information System (INIS)

    Breen, J.

    1987-01-01

    A number of aspects concerning the reorientation of polymer, water and ion hydration complexes have been studied in aqueous solution of polyethylene oxide (PEO). The polymer dynamics are investigated by 1 H-PEO and 13 C-PEO nuclear relaxation experiments. 162 refs.; 30 figs.; 19 tabs

  10. Nitric oxide: a physiologic messenger.

    Science.gov (United States)

    Lowenstein, C J; Dinerman, J L; Snyder, S H

    1994-02-01

    To review the physiologic role of nitric oxide, an unusual messenger molecule that mediates blood vessel relaxation, neurotransmission, and pathogen suppression. A MEDLINE search of articles published from 1987 to 1993 that addressed nitric oxide and the enzyme that synthesizes it, nitric oxide synthase. Animal and human studies were selected from 3044 articles to analyze the clinical importance of nitric oxide. Descriptions of the structure and function of nitric oxide synthase were selected to show how nitric oxide acts as a biological messenger molecule. Biochemical and physiologic studies were analyzed if the same results were found by three or more independent observers. Two major classes of nitric oxide synthase enzymes produce nitric oxide. The constitutive isoforms found in endothelial cells and neurons release small amounts of nitric oxide for brief periods to signal adjacent cells, whereas the inducible isoform found in macrophages releases large amounts of nitric oxide continuously to eliminate bacteria and parasites. By diffusing into adjacent cells and binding to enzymes that contain iron, nitric oxide plays many important physiologic roles. It regulates blood pressure, transmits signals between neurons, and suppresses pathogens. Excess amounts, however, can damage host cells, causing neurotoxicity during strokes and causing the hypotension associated with sepsis. Nitric oxide is a simple molecule with many physiologic roles in the cardiovascular, neurologic, and immune systems. Although the general principles of nitric oxide synthesis are known, further research is necessary to determine what role it plays in causing disease.

  11. 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.

  12. 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

  13. It has been suggested that oxidative stress, especially oxidative ...

    African Journals Online (AJOL)

    nabipour

    2012-02-14

    Feb 14, 2012 ... 1Department of Clinical Biochemistry, Faculty of Medicine, Bushehr University of Medical Sciences, Bushehr, Iran. 2Department of Cardiology ... oxidative modification of low-density lipoproteins (LDL), may play a causative role in ... the oxidation of lipids in the cell membrane especially the oxidation of LDL.

  14. Oxidative Stress in BPH.

    Science.gov (United States)

    Savas, M; Verit, A; Ciftci, H; Yeni, E; Aktan, E; Topal, U; Erel, O

    2009-01-01

    In the present study, we investigated the relationship between potency of oxidative stress and BPH and this may assist to contribute to the realistic explanation of the ethiopathogenesis of BPH. Seventy four newly diagnosed men with BPH (mean age: 54+/-11.2), who had not undergone any previous treatment for BPH, and 62 healthy volunteers (mean age: 55+/-14) were enrolled in the present study. To determine the antioxidative status of plasma, total antioxidant capacity (TAC) was calculated, and to determine the oxidative status of plasma (TOS) total peroxide levels were measured. The ratio of TAC to total peroxide was accepted as an indicator of oxidative stress (OSI). Data are presented as mean SD +/- unless specified. Student t-test and correlation analyses were used to evaluate the statistical significance differences in the median values recorded for all parameters between BPH and control group. Plasma TAC TOS were found in patients and controls (1.70 +/- 0.32, 1.68 +/- 0.19 micromol Trolox Equiv./L), (12.48 +/- 1.98, 12.40 +/- 1.14 micromol / L) respectively. OSI was calculated as 7.57 +/- 1.91, 7.48 +/- 1.33, respectively. Plasma TAC, TOS and OSI levels were not found to be significantly difference between patients and control subjects (p>0.05, p>0.05, p>0.05). The present study has shown that there were not relationship between potency of oxidative stress and BPH. Further well designed studies should be planned to find out whether the oxidative stress-related parameters play role in BPH as an interesting pathology in regard of the etiopathogenesis.

  15. Staged membrane oxidation reactor system

    Science.gov (United States)

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2012-09-11

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  16. Electrochemical analysis of metal oxides

    Czech Academy of Sciences Publication Activity Database

    Grygar, Tomáš; Bezdička, Petr; Hradil, David; Pikna, L.

    90-91, - (2003), s. 45-50 ISSN 1012-0394 Institutional research plan: CEZ:AV0Z4032918 Keywords : powder electroanalysis * Fe oxides * Mn oxides Subject RIV: CA - Inorganic Chemistry Impact factor: 0.687, year: 2003

  17. Thin film metal-oxides

    CERN Document Server

    Ramanathan, Shriram

    2009-01-01

    Presents an account of the fundamental structure-property relations in oxide thin films. This title discusses the functional properties of thin film oxides in the context of applications in the electronics and renewable energy technologies.

  18. Review Of Plutonium Oxidation Literature

    International Nuclear Information System (INIS)

    Korinko, P.

    2009-01-01

    A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles ( 250 (micro)m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

  19. Oxidative Decarboxylation of Levulinic Acid by Cupric Oxides

    Directory of Open Access Journals (Sweden)

    Lu Lin

    2010-11-01

    Full Text Available In this paper, cupric oxides was found to effectively oxidize levulinic acid (LA and lead to the decarboxylation of levulinic acid to 2-butanone. The effects of cupric oxide dosage, reaction time and initial pH value were investigated in batch experiments and a plausible mechanism was proposed. The results showed that LA decarboxylation over cupric oxides at around 300 °C under acidic conditions produced the highest yield of butanone (67.5%. In order to elucidate the catalytic activity of cupric oxides, XRD, AFM, XPS and H2-TPR techniques was applied to examine their molecular surfaces and their effects on the reaction process.

  20. Self-assembled manganese oxide structures through direct oxidation

    KAUST Repository

    Zhao, Chao; Wang, Qingxiao; Yang, Yang; Zhang, Bei; Zhang, Xixiang

    2012-01-01

    The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

  1. Self-assembled manganese oxide structures through direct oxidation

    KAUST Repository

    Zhao, Chao

    2012-12-01

    The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

  2. The aqueous chemistry of oxides

    CERN Document Server

    Bunker, Bruce C

    2016-01-01

    The Aqueous Chemistry of Oxides is a comprehensive reference volume and special topics textbook that explores all of the major chemical reactions that take place between oxides and aqueous solutions. The book highlights the enormous impact that oxide-water reactions have in advanced technologies, materials science, geochemistry, and environmental science.

  3. Interactions between iron oxides and copper oxides under hydrothermal conditions

    Energy Technology Data Exchange (ETDEWEB)

    McGarvey, G B; Owen, D G

    1995-08-01

    Under hydrothermal conditions, magnetite and hematite have been shown to undergo interconversion reactions, the extent of which is controlled in part by the presence of copper oxides. In oxygenated water, the degree to which magnetite was oxidized to hematite was found to be dependent on the presence of CuO or Cu{sub 2}O. When these materials were absent, the oxidation of magnetite was limited by the dissolved oxygen in the aqueous system. Participation of the copper oxides in the oxidation process was confirmed by more complete conversion of magnetite was also influenced by the presence of the copper oxides. In addition to driving the reduction to completion, the presence of the copper oxides also exerted a strong influence over the morphology of the magnetite that formed. (author). 13 refs., 1 tab., 3 figs.

  4. Iron oxide surfaces

    Science.gov (United States)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  5. Manganese Oxidation by Bacteria: Biogeochemical Aspects

    Digital Repository Service at National Institute of Oceanography (India)

    Sujith, P.P.; LokaBharathi, P.A.

    Manganese is an essential trace metal that is not as readily oxidizable like iron. Several bacterial groups posses the ability to oxidize Mn effectively competing with chemical oxidation. The oxides of Mn are the strongest of the oxidants, next...

  6. Thin Solid Oxide Cell

    DEFF Research Database (Denmark)

    2010-01-01

    The present invention relates to a thin and in principle unsupported solid oxide cell, comprising at least a porous anode layer, an electrolyte layer and a porous cathode layer, wherein the anode layer and the cathode layer comprise an electrolyte material, at least one metal and a catalyst...... material, and wherein the overall thickness of the thin reversible cell is about 150 [mu]m or less, and to a method for producing same. The present invention also relates to a thin and in principle unsupported solid oxide cell, comprising at least a porous anode layer, an electrolyte layer and a porous...... cathode layer, wherein the anode layer and the cathode layer comprise an electrolyte material and a catalyst material, wherein the electrolyte material is doper zirconia, and wherein the overall thickness of the thin reversible cell is about 150 [mu]m or less, and to a method for producing same...

  7. Defects at oxide surfaces

    CERN Document Server

    Thornton, Geoff

    2015-01-01

    This book presents the basics and characterization of defects at oxide surfaces. It provides a state-of-the-art review of the field, containing information to the various types of surface defects, describes analytical methods to study defects, their chemical activity and the catalytic reactivity of oxides. Numerical simulations of defective structures complete the picture developed. Defects on planar surfaces form the focus of much of the book, although the investigation of powder samples also form an important part. The experimental study of planar surfaces opens the possibility of applying the large armoury of techniques that have been developed over the last half-century to study surfaces in ultra-high vacuum. This enables the acquisition of atomic level data under well-controlled conditions, providing a stringent test of theoretical methods. The latter can then be more reliably applied to systems such as nanoparticles for which accurate methods of characterization of structure and electronic properties ha...

  8. Electrorheology of graphene oxide.

    Science.gov (United States)

    Zhang, Wen Ling; Liu, Ying Dan; Choi, Hyoung Jin; Kim, Sang Guk

    2012-04-01

    Novel polarizable graphene oxide (GO) particles with oxidized groups on their edge and basal planes were prepared by a modified Hummers method, and their electro-responsive electrorheological (ER) characteristics when dispersed in silicone oil were examined with and without an electric field applied. The fibrillation phenomenon of this GO-based electro-responsive fluid was also observed via an optical microscope under an applied electric field. Both flow curves and dielectric spectra of the ER fluid were measured using a rotational rheometer and a LCR meter, respectively. Its viscoelastic properties of both storage and loss moduli were also examined using a vertical oscillation rheometer equipped with a high voltage generator, finding that the GO-based smart ER system behaves as a viscoelastic material under an applied electric field.

  9. Mechanochemistry of titanium oxides

    Directory of Open Access Journals (Sweden)

    Veljković Ivana

    2009-01-01

    Full Text Available Mechanochemistry represents an alternative route in synthesis of nanomaterials. Mechanochemical routes are attractive because of their simplicity, flexibility, and ability to prepare materials by solid state reactions at room temperature. The aim of this work is the mechanochemical synthesis of nanostructured titanium oxides of different composition starting from mixtures of Ti and TiO2, TiO and TiO2 or Ti2O3 and TiO2. Emphasis is on the Magneli phases Ti4O7 and Ti5O9 because their mixture is commercially known as EBONEX material. The materials prepared were characterized by XRPD, TG/DTA analysis, SEM and optical microscopy. Titanium monoxide and several Magneli oxides, Ti4O7, Ti5O9 and Ti6O11, are successfully prepared. The results are very interesting because the EBONEX materials were prepared at lower than usual temperature, which would decrease the effective cost of production.

  10. Oxidative metabolism in muscle.

    OpenAIRE

    Ferrari, M; Binzoni, T; Quaresima, V

    1997-01-01

    Oxidative metabolism is the dominant source of energy for skeletal muscle. Near-infrared spectroscopy allows the non-invasive measurement of local oxygenation, blood flow and oxygen consumption. Although several muscle studies have been made using various near-infrared optical techniques, it is still difficult to interpret the local muscle metabolism properly. The main findings of near-infrared spectroscopy muscle studies in human physiology and clinical medicine are summarized. The advantage...

  11. Chemical oxidizers treat wastewater

    International Nuclear Information System (INIS)

    Stephenson, F.A.

    1992-01-01

    Based on the inherent benefits of these original oxidation systems, a second generation of advanced oxidation processes (AOPs) has emerged. These processes combine key features of the first generation technologies with more sophisticated advances in UV technology, such as the new pulsed plasma xenon flash lamp that emits high-energy, high-intensity UV light. Second generation systems can be equipped with a transmittance controller to prevent lamp fouling or scaling. The coupling of the first generation's technology with the new UV sources provides the rapid destruction of chlorinated and nonchlorinated hydrocarbons and humic acids from contaminated water. It also is effective in the treatment of organic laden gases from soil vapor extraction systems. AOPs may promote the oxidation (and subsequent removal) of heavy metals in water, though few data are available to verify the claim. The success of AOPs, including ozonation with UV light, hydrogen peroxide with UV light and advanced photolysis, is linked with their creation of hydroxyl-free radicals (OH·) that are effective in eliminating contaminants such as formaldehyde, chlorinated hydrocarbons and chlorinated solvents. Hydroxyl free-radicals are consumed in microsecond reactions and exhibit little substrate selectivity with the exception of halogenated alkanes such as chloroform. They can act as chain carriers. Given their power, hydroxyl free-radicals react with virtually all organic solutes more quickly (especially in water) than any other oxidants, except fluorine. There are projects that have found the combination of some AOPs to be the most efficient organic destruction techniques for the job. For example, one project successfully remediated groundwater contaminated with gasoline and Number 2 diesel through successive treatments of ozone and hydrogen peroxide with ultraviolet light, followed by granular activated carbon. 5 refs., 2 tabs

  12. Krypton oxides under pressure

    OpenAIRE

    Zaleski-Ejgierd, Patryk; Łata, Paweł

    2015-01-01

    Under high pressure, krypton, one of the most inert elements is predicted to become sufficiently reactive to form a new class of krypton compounds; krypton oxides. Using modern ab-initio evolutionary algorithms in combination with Density Functional Theory, we predict the existence of several thermodynamically stable Kr/O species at elevated pressures. In particular, our calculations indicate that at approx. 300?GPa the monoxide, KrO, should form spontaneously and remain thermo- and dynamical...

  13. Radiolytic graphite oxidation revisited

    International Nuclear Information System (INIS)

    Minshall, P.C.; Sadler, I.A.; Wickham, A.J.

    1996-01-01

    The importance of radiolytic oxidation in graphite-moderated CO 2 -cooled reactors has long been recognised, especially in the Advanced Gas-Cooled Reactors where potential rates are higher because of the higher gas pressure and ratings than the earlier Magnox designs. In all such reactors, the rate of oxidation is partly inhibited by the CO produced in the reaction and, in the AGR, further reduced by the deliberate addition of CH 4 . Significant roles are also played by H 2 and H 2 O. This paper reviews briefly the mechanisms of these processes and the data on which they are based. However, operational experience has demonstrated that these basic principles are unsatisfactory in a number of respects. Gilsocarbon graphites produced by different manufacturers have demonstrated a significant difference in oxidation rate despite a similar specification and apparent equivalence in their pore size and distribution, considered to be the dominant influence on oxidation rate for a given coolant-gas composition. Separately, the inhibiting influence of CH 4 , which for many years had been considered to arise from the formation of a sacrificial deposit on the pore walls, cannot adequately be explained by the actual quantities of such deposits found in monitoring samples which frequently contain far less deposited carbon than do samples from Magnox reactors where the only source of such deposits is the CO. The paper also describes the current status of moderator weight-loss predictions for Magnox and AGR Moderators and the validation of the POGO and DIFFUSE6 codes respectively. 2 refs, 5 figs

  14. Oxidative stability of polyaniline

    Czech Academy of Sciences Publication Activity Database

    Stejskal, Jaroslav; Exnerová, Milena; Morávková, Zuzana; Trchová, Miroslava; Hromádková, Jiřina; Prokeš, J.

    2012-01-01

    Roč. 97, č. 6 (2012), s. 1026-1033 ISSN 0141-3910 R&D Projects: GA ČR GA202/09/1626; GA ČR GAP205/12/0911 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : polyaniline * nanotubes * oxidation stability Subject RIV: BK - Fluid Dynamics Impact factor: 2.770, year: 2012

  15. Electronic structures of ReS2, ReSe2 and TcS2 in the real and the hypothetical undistorted structures

    NARCIS (Netherlands)

    Fang, CM; Wiegers, GA; Haas, C; deGroot, RA

    1997-01-01

    The transition-metal dichalcogenides ReX2 (X = Sor Se) and TcS2 with a d(3) electron configuration have distorted; CdCl2 and Cd(OH)(2) structures, respectively, with the Re(Tc) atoms in each layer forming parallelogram-shaped connected clusters (diamond chain). Ab-initio band-structure calculations

  16. Molecular theory of graphene oxide.

    Science.gov (United States)

    Sheka, Elena F; Popova, Nadezhda A

    2013-08-28

    Applied to graphene oxide, the molecular theory of graphene considers its oxide as a final product in the succession of polyderivatives related to a series of oxidation reactions involving different oxidants. The graphene oxide structure is created in the course of a stepwise computational synthesis of polyoxides of the (5,5) nanographene molecule governed by an algorithm that takes into account the molecule's natural radicalization due to the correlation of its odd electrons, the extremely strong influence of the structure on properties, and a sharp response of the molecule behavior on small actions of external factors. Taking these together, the theory has allowed for a clear, transparent and understandable explanation of the hot points of graphene oxide chemistry and suggesting reliable models of both chemically produced and chemically reduced graphene oxides.

  17. 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.

  18. 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.

  19. The competing oxide and sub-oxide formation in metal-oxide molecular beam epitaxy

    International Nuclear Information System (INIS)

    Vogt, Patrick; Bierwagen, Oliver

    2015-01-01

    The hetero-epitaxial growth of the n-type semiconducting oxides β-Ga 2 O 3 , In 2 O 3 , and SnO 2 on c- and r-plane sapphire was performed by plasma-assisted molecular beam epitaxy. The growth-rate and desorbing flux from the substrate were measured in-situ under various oxygen to metal ratios by laser reflectometry and quadrupole mass spectrometry, respectively. These measurements clarified the role of volatile sub-oxide formation (Ga 2 O, In 2 O, and SnO) during growth, the sub-oxide stoichiometry, and the efficiency of oxide formation for the three oxides. As a result, the formation of the sub-oxides decreased the growth-rate under metal-rich growth conditions and resulted in etching of the oxide film by supplying only metal flux. The flux ratio for the exclusive formation of the sub-oxide (e.g., the p-type semiconductor SnO) was determined, and the efficiency of oxide formation was found to be the highest for SnO 2 , somewhat lower for In 2 O 3 , and the lowest for Ga 2 O 3 . Our findings can be generalized to further oxides that possess related sub-oxides

  20. The oxidative hypothesis of senescence

    Directory of Open Access Journals (Sweden)

    Gilca M

    2007-01-01

    Full Text Available The oxidative hypothesis of senescence, since its origin in 1956, has garnered significant evidence and growing support among scientists for the notion that free radicals play an important role in ageing, either as "damaging" molecules or as signaling molecules. Age-increasing oxidative injuries induced by free radicals, higher susceptibility to oxidative stress in short-lived organisms, genetic manipulations that alter both oxidative resistance and longevity and the anti-ageing effect of caloric restriction and intermittent fasting are a few examples of accepted scientific facts that support the oxidative theory of senescence. Though not completely understood due to the complex "network" of redox regulatory systems, the implication of oxidative stress in the ageing process is now well documented. Moreover, it is compatible with other current ageing theories (e.g., those implicating the mitochondrial damage/mitochondrial-lysosomal axis, stress-induced premature senescence, biological "garbage" accumulation, etc. This review is intended to summarize and critically discuss the redox mechanisms involved during the ageing process: sources of oxidant agents in ageing (mitochondrial -electron transport chain, nitric oxide synthase reaction- and non-mitochondrial- Fenton reaction, microsomal cytochrome P450 enzymes, peroxisomal β -oxidation and respiratory burst of phagocytic cells, antioxidant changes in ageing (enzymatic- superoxide dismutase, glutathione-reductase, glutathion peroxidase, catalase- and non-enzymatic glutathione, ascorbate, urate, bilirubine, melatonin, tocopherols, carotenoids, ubiquinol, alteration of oxidative damage repairing mechanisms and the role of free radicals as signaling molecules in ageing.

  1. Oxidation kinetics of (B6O) boron oxide

    International Nuclear Information System (INIS)

    Makarov, V.S.; Solov'ev, N.E.; Ugaj, Ya.A.

    1987-01-01

    Reactivity of B 6 O to oxygen is investigated. It is shown that the process of B 6 O oxidation in the air in the temperature range 760-1150 K results in the maximum transformation degree equal to 0.35. At the initial stages oxidation proceeds in kinetic regime, at final stages - in diffusion one, and high viscosity of B 2 O 3 probably affects the oxidation process

  2. Partial oxidation process

    International Nuclear Information System (INIS)

    Najjar, M.S.

    1987-01-01

    A process is described for the production of gaseous mixtures comprising H/sub 2/+CO by the partial oxidation of a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel, iron, and vanadium-containing ash or petroleum coke having a nickel, iron, and vanadium-containing ash, or mixtures thereof. The feedstock includes a minimum of 0.5 wt. % of sulfur and the ash includes a minimum of 5.0 wt. % vanadium, a minimum of 0.5 ppm nickel, and a minimum of 0.5 ppm iron. The process comprises: (1) mixing together a copper-containing additive with the fuel feedstock; wherein the weight ratio of copper-containing additive to ash in the fuel feedstock is in the range of about 1.0-10.0, and there is at least 10 parts by weight of copper for each part by weight of vanadium; (2) reacting the mixture from (1) at a temperature in the range of 2200 0 F to 2900 0 F and a pressure in the range of about 5 to 250 atmospheres in a free-flow refactory lined partial oxidation reaction zone with a free-oxygen containing gas in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H/sub 2/+CO and entrained molten slag; and where in the reaction zone and the copper-containing additive combines with at least a portion of the nickel and iron constituents and sulfur found in the feedstock to produce a liquid phase washing agent that collects and transports at least a portion of the vanadium-containing oxide laths and spinels and other ash components and refractory out of the reaction zone; and (3) separating nongaseous materials from the hot raw effluent gas stream

  3. The 2016 oxide electronic materials and oxide interfaces roadmap

    DEFF Research Database (Denmark)

    Lorenz, M.; Rao, M. S. Ramachandra; Venkatesan, T.

    2016-01-01

    of these materials to understand the tunability of their properties and the novel properties that evolve due to their nanostructured nature is another facet of the challenge. The research related to the oxide electronic field is at an impressionable stage, and this has motivated us to contribute with a roadmap......, Pentcheva, and Gegenwart. Finally, Miletto Granozio presents the European action ‘towards oxide-based electronics’ which develops an oxide electronics roadmap with emphasis on future nonvolatile memories and the required technologies.In summary, we do hope that this oxide roadmap appears as an interesting...

  4. Solid oxide fuel cells fueled with reducible oxides

    Science.gov (United States)

    Chuang, Steven S.; Fan, Liang Shih

    2018-01-09

    A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing the solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.

  5. 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

  6. Sputtered tin oxide and titanium oxide thin films as alternative transparent conductive oxides

    Energy Technology Data Exchange (ETDEWEB)

    Boltz, Janika

    2011-12-12

    Alternative transparent conductive oxides to tin doped indium oxide have been investigated. In this work, antimony doped tin oxide and niobium doped titanium oxide have been studied with the aim to prepare transparent and conductive films. Antimony doped tin oxide and niobium doped titanium oxide belong to different groups of oxides; tin oxide is a soft oxide, while titanium oxide is a hard oxide. Both oxides are isolating materials, in case the stoichiometry is SnO{sub 2} and TiO{sub 2}. In order to achieve transparent and conductive films free carriers have to be generated by oxygen vacancies, by metal ions at interstitial positions in the crystal lattice or by cation doping with Sb or Nb, respectively. Antimony doped tin oxide and niobium doped titanium oxide films have been prepared by reactive direct current magnetron sputtering (dc MS) from metallic targets. The process parameters and the doping concentration in the films have been varied. The films have been electrically, optically and structurally analysed in order to analyse the influence of the process parameters and the doping concentration on the film properties. Post-deposition treatments of the films have been performed in order to improve the film properties. For the deposition of transparent and conductive tin oxide, the dominant parameter during the deposition is the oxygen content in the sputtering gas. The Sb incorporation as doping atoms has a minor influence on the electrical, optical and structural properties. Within a narrow oxygen content in the sputtering gas highly transparent and conductive tin oxide films have been prepared. In this study, the lowest resistivity in the as deposited state is 2.9 m{omega} cm for undoped tin oxide without any postdeposition treatment. The minimum resistivity is related to a transition to crystalline films with the stoichiometry of SnO{sub 2}. At higher oxygen content the films turn out to have a higher resistivity due to an oxygen excess. After post

  7. Actinide oxide photodiode and nuclear battery

    Energy Technology Data Exchange (ETDEWEB)

    Sykora, Milan; Usov, Igor

    2017-12-05

    Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxides are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.

  8. Trends in reactivity of oxides

    DEFF Research Database (Denmark)

    Toftelund, Anja

    The results in this thesis are based on Density Functional Theory calculations. The catalytic activity of oxides and other compound materials are investigated. It is found that the adsorption energy of the molecules NH2, NH, OH and SH on transition metal nitride, oxide and sulfide surfaces scales......, and I) and OH on a wide range of rutile oxide surfaces. Furthermore, Brønsted-Evans-Polanyi (BEP) relations are found for the adsorption of a large number of molecules (including Cl, Br and I) on transition metal oxides. In these relations the activation energies scale linearly with the dissociative...... chemisorption energies. It turns out that the BEP relation for rutile oxides is almost coinciding with the dissociation line, i.e. no barrier exists for the reactive surfaces. The heterogeneous catalytic oxidation of hydrogen halides (HCl, HBr, and HI) is investigated. A micro-kinetic model is solved...

  9. Rare Earth Oxide Thin Films

    CERN Document Server

    Fanciulli, Marco

    2007-01-01

    Thin rare earth (RE) oxide films are emerging materials for microelectronic, nanoelectronic, and spintronic applications. The state-of-the-art of thin film deposition techniques as well as the structural, physical, chemical, and electrical properties of thin RE oxide films and of their interface with semiconducting substrates are discussed. The aim is to identify proper methodologies for the development of RE oxides thin films and to evaluate their effectiveness as innovative materials in different applications.

  10. Transparent conducting oxide nanotubes

    Science.gov (United States)

    Alivov, Yahya; Singh, Vivek; Ding, Yuchen; Nagpal, Prashant

    2014-09-01

    Thin film or porous membranes made of hollow, transparent, conducting oxide (TCO) nanotubes, with high chemical stability, functionalized surfaces and large surface areas, can provide an excellent platform for a wide variety of nanostructured photovoltaic, photodetector, photoelectrochemical and photocatalytic devices. While large-bandgap oxide semiconductors offer transparency for incident light (below their nominal bandgap), their low carrier concentration and poor conductivity makes them unsuitable for charge conduction. Moreover, materials with high conductivity have nominally low bandgaps and hence poor light transmittance. Here, we demonstrate thin films and membranes made from TiO2 nanotubes heavily-doped with shallow Niobium (Nb) donors (up to 10%, without phase segregation), using a modified electrochemical anodization process, to fabricate transparent conducting hollow nanotubes. Temperature dependent current-voltage characteristics revealed that TiO2 TCO nanotubes, doped with 10% Nb, show metal-like behavior with resistivity decreasing from 6.5 × 10-4 Ωcm at T = 300 K (compared to 6.5 × 10-1 Ωcm for nominally undoped nanotubes) to 2.2 × 10-4 Ωcm at T = 20 K. Optical properties, studied by reflectance measurements, showed light transmittance up to 90%, within wavelength range 400 nm-1000 nm. Nb doping also improves the field emission properties of TCO nanotubes demonstrating an order of magnitude increase in field-emitter current, compared to undoped samples.

  11. Corrosion of beryllium oxide

    International Nuclear Information System (INIS)

    Elston, J.; Caillat, R.

    1958-01-01

    Data are reported on the volatilization rate of beryllium oxide in moist air depending on temperature and water vapour concentration. They are concerned with powder samples or sintered shapes of various densities. For sintered samples, the volatilization rate is very low under the following conditions: - temperature: 1300 deg. C, - water vapour concentration in moist air: 25 g/m 3 , - flow rate: 12 I/hour corresponding to a speed of 40 m/hour on the surface of the sample. For calcinated powders (1300 deg. C), grain growth has been observed under a stream of moist air at 1100 deg. C. For instance, grain size changes from 0,5 to at least 2 microns after 500 hours of exposure at this temperature. Furthermore, results data are reported on corrosion of sintered beryllium oxide in pressurized water. At 250 deg. C, under a pressure of 40 kg/cm 2 water is very slightly corrosive; however, internal strains are revealed. Finally, some features on the corrosion in liquid sodium are exposed. (author) [fr

  12. Buried oxide layer in silicon

    Science.gov (United States)

    Sadana, Devendra Kumar; Holland, Orin Wayne

    2001-01-01

    A process for forming Silicon-On-Insulator is described incorporating the steps of ion implantation of oxygen into a silicon substrate at elevated temperature, ion implanting oxygen at a temperature below 200.degree. C. at a lower dose to form an amorphous silicon layer, and annealing steps to form a mixture of defective single crystal silicon and polycrystalline silicon or polycrystalline silicon alone and then silicon oxide from the amorphous silicon layer to form a continuous silicon oxide layer below the surface of the silicon substrate to provide an isolated superficial layer of silicon. The invention overcomes the problem of buried isolated islands of silicon oxide forming a discontinuous buried oxide layer.

  13. Continuous lengths of oxide superconductors

    Science.gov (United States)

    Kroeger, Donald M.; List, III, Frederick A.

    2000-01-01

    A layered oxide superconductor prepared by depositing a superconductor precursor powder on a continuous length of a first substrate ribbon. A continuous length of a second substrate ribbon is overlaid on the first substrate ribbon. Sufficient pressure is applied to form a bound layered superconductor precursor powder between the first substrate ribbon and the second substrate ribbon. The layered superconductor precursor is then heat treated to establish the oxide superconducting phase. The layered oxide superconductor has a smooth interface between the substrate and the oxide superconductor.

  14. Crystallization inhibitors for amorphous oxides

    International Nuclear Information System (INIS)

    Reznitskij, L.A.; Filippova, S.E.

    1993-01-01

    Data for the last 10 years, in which experimental results of studying the temperature stabilization of x-ray amorphous oxides (including R 3 Fe 5 O 12 R-rare earths, ZrO 2 , In 2 O 3 , Sc 2 O 3 ) and their solid solution are presented, are generalized. Processes of amorphous oxide crystallization with the production of simple oxides, solid solutions and chemical compounds with different polyhedral structure, are investigated. Energy and crystallochemical criteria for selecting the doping inhibitor-components stabilizing the amorphous state are ascertained, temperatures and enthalpies of amorpous oxide crystallization are determined, examination of certain provisions of iso,orphous miscibility theory is conducted

  15. Oxidation of Ethylene Carbonate on Li Metal Oxide Surfaces

    DEFF Research Database (Denmark)

    Østergaard, Thomas M.; Giordano, Livia; Castelli, Ivano Eligio

    2018-01-01

    Understanding the reactivity of the cathode surface is of key importance to the development of batteries. Here, density functional theory is applied to investigate the oxidative decomposition of the electrolyte component, ethylene carbonate (EC), on layered LixMO(2) oxide surfaces. We compare...

  16. Oxidative desulfurization of benzene fraction on transition metal oxides

    Science.gov (United States)

    Boikov, E. B.; Vishnetskaya, M. V.

    2013-02-01

    It is established that molecular oxygen is able to oxidize thiophene selectively in a mixture with benzene on V2O5 · MoO3. The introduction of thiophene inhibits the oxidation of benzene. It is shown that the conversion of thiophene during operation of the catalyst is reduced at first and then increases until it reaches its initial value.

  17. Thermal oxidation of silicon with two oxidizing species

    International Nuclear Information System (INIS)

    Vild-Maior, A.A.; Filimon, S.

    1979-01-01

    A theoretical model for the thermal oxidation of silicon in wet oxygen is presented. It is shown that the presence of oxygen in the oxidation furnace has an important effect when the water temperature is not too high (less than about 65 deg C). The model is in good agreement with the experimental data. (author)

  18. Mechanisms of electrochemical reduction and oxidation of nitric oxide

    NARCIS (Netherlands)

    Vooys, de A.C.A.; Beltramo, G.L.; Riet, van B.; Veen, van J.A.R.; Koper, M.T.M.

    2004-01-01

    A summary is given of recent work on the reactivity of nitric oxide on various metal electrodes. The significant differences between the reactivity of adsorbed NO and NO in solution are pointed out, both for the reduction and the oxidation reaction(s). Whereas adsorbed NO can be reduced only to

  19. Plutonium oxides and uranium and plutonium mixed oxides. Carbon determination

    International Nuclear Information System (INIS)

    Anon.

    Determination of carbon in plutonium oxides and uranium plutonium mixed oxides, suitable for a carbon content between 20 to 3000 ppm. The sample is roasted in oxygen at 1200 0 C, the carbon dioxide produced by combustion is neutralized by barium hydroxide generated automatically by coulometry [fr

  20. Improved Understanding of In Situ Chemical Oxidation. Technical Objective I: Contaminant Oxidation Kinetics Contaminant Oxidation Kinetics

    Science.gov (United States)

    2009-05-01

    methyl tert butyl ether NAPL non-aqueous phase liquid NOD natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE...and persulfate; and Technical Objective 2, assess how soil properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and...to develop a general description of kobs vs. T because there are many reactions that can contribute to the concentration of the reactive intermediate

  1. Ferromagnet / superconductor oxide superlattices

    Science.gov (United States)

    Santamaria, Jacobo

    2006-03-01

    The growth of heterostructures combining oxide materials is a new strategy to design novel artificial multifunctional materials with interesting behaviors ruled by the interface. With the (re)discovery of colossal magnetoresistance (CMR) materials, there has been renewed interest in heterostructures involving oxide superconductors and CMR ferromagnets where ferromagnetism (F) and superconductivity (S) compete within nanometric distances from the interface. In F/S/F structures involving oxides, interfaces are especially complex and various factors like interface disorder and roughness, epitaxial strain, polarity mismatch etc., are responsible for depressed magnetic and superconducting properties at the interface over nanometer length scales. In this talk I will focus in F/S/F structures made of YBa2Cu3O7 (YBCO) and La0.7Ca0.3MnO3 (LCMO). The high degree of spin polarization of the LCMO conduction band, together with the d-wave superconductivity of the YBCO make this F/S system an adequate candidate for the search of novel spin dependent effects in transport. We show that superconductivity at the interface is depressed by various factors like charge transfer, spin injection or ferromagnetic superconducting proximity effect. I will present experiments to examine the characteristic distances of the various mechanisms of superconductivity depression. In particular, I will discuss that the critical temperature of the superconductor depends on the relative orientation of the magnetization of the F layers, giving rise to a new giant magnetoresistance effect which might be of interest for spintronic applications. Work done in collaboration with V. Peña^1, Z. Sefrioui^1, J. Garcia-Barriocanal^1, C. Visani^1, D. Arias^1, C. Leon^1 , N. Nemes^2, M. Garcia Hernandez^2, S. G. E. te Velthuis^3, A. Hoffmann^3, M. Varela^4, S. J. Pennycook^4. Work supported by MCYT MAT 2005-06024, CAM GR- MAT-0771/2004, UCM PR3/04-12399 Work at Argonne supported by the Department of Energy, Basic

  2. Characterization of tin oxide nanoparticles synthesized via oxidation from metal

    International Nuclear Information System (INIS)

    Abruzzi, R.C.; Dedavid, B.A.; Pires, M.J.R.; Streicher, M.

    2014-01-01

    The tin oxide (SnO_2) is a promising material with great potential for applications such as gas sensors and catalysts. This oxide nanostructures show higher activation efficiency due to its larger effective surface. This paper presents the synthesis and characterization of the tin oxide in different conditions, via oxidation of pure tin with nitric acid. Results obtained from the characterization of SnO_2 powder by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDX), Particle size by Dynamic Light Scattering (DLS) and Infrared Spectroscopy (FTIR) indicated that the conditions were suitable for the synthesis to obtain manometric tin oxide granules with crystalline structure of rutile. (author)

  3. Direct Coal Oxidation in Modified Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Gil, Vanesa; Ippolito, Davide

    2015-01-01

    Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon-carbonate s......Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon......-carbonate slurry or anode layer. The nature of the coal affects both open circuit voltage and power output. Highest OCV and power densities were observed for bituminous coal and by adding manganese oxide or praseodymium-doped ceria to the carbon/carbonate mixture. Comparing the carbon black fueled performance...... bituminous coal (73 mW/cm2). © 2015 ECS - The Electrochemical Society...

  4. Direct Coal Oxidation in Modified Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Gil, Vanesa; Ippolito, Davide

    2017-01-01

    Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon-carbonate s......Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon......-carbonate slurry or anode layer. The nature of the coal affects both open circuit voltage and power output. Highest OCV and power densities were observed for bituminous coal and by adding manganese oxide or praseodymium-doped ceria to the carbon/carbonate mixture. Comparing the carbon black fueled performance...... bituminous coal (73 mW/cm2)....

  5. Hydrogen oxidation in Azospirillum brasilense

    Energy Technology Data Exchange (ETDEWEB)

    Tibelius, K.

    1984-01-01

    Hydrogen oxidation by Azospirillum brasilense Sp7 was studied in N/sub 2/-fixing and NH/sub 4//sup +/-grown batch cultures. The K/sub m/ for H/sub 2/ of O/sub 2/-dependent H/sup 3/H oxidation in whole cells was 9 uM. The rates of H/sup 3/H and H/sub 2/ oxidation were very similar, indicating that the initial H/sub 2/ activation step in the overall H/sub 2/ oxidation reaction was not rate-limiting and that H/sup 3/H oxidation was a valid measure of H/sub 2/-oxidation activity. Hydrogen-oxidation activity was inhibited irreversibly by air. In N-free cultures the O/sub 2/ optima for O/sub 2/-dependent H/sub 2/ oxidation, ranging from 0.5-1.25% O/sub 2/ depending on the phase of growth, were significantly higher than those of C/sub 2/H/sub 2/ reduction, 0.15-0.35%, suggesting that the H/sub 2/-oxidation system may have a limited ability to aid in the protection of nitrogenase against inactivation by O/sub 2/. Oxygen-dependent H/sub 2/ oxidation was inhibited by NO/sub 2//sup +/, NO, CO, and C/sub 2/H/sub 2/ with apparent K/sub 1/ values of 20, 0.4, 28, and 88 uM, respectively. Hydrogen-oxidation activity was 50 to 100 times higher in denitrifying cultures when the terminal electron acceptor for growth was N/sub 2/O rather than NO/sub 3//sup -/, possibly due to the irreversible inhibition of hydrogenase by NO/sub 2//sup -/ and NO in NO/sub 3//sup -/-grown cultures.

  6. Operation of staged membrane oxidation reactor systems

    Science.gov (United States)

    Repasky, John Michael

    2012-10-16

    A method of operating a multi-stage ion transport membrane oxidation system. The method comprises providing a multi-stage ion transport membrane oxidation system with at least a first membrane oxidation stage and a second membrane oxidation stage, operating the ion transport membrane oxidation system at operating conditions including a characteristic temperature of the first membrane oxidation stage and a characteristic temperature of the second membrane oxidation stage; and controlling the production capacity and/or the product quality by changing the characteristic temperature of the first membrane oxidation stage and/or changing the characteristic temperature of the second membrane oxidation stage.

  7. Effects of Oxidation on Oxidation-Resistant Graphite

    Energy Technology Data Exchange (ETDEWEB)

    Windes, William [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Rebecca [Idaho National Lab. (INL), Idaho Falls, ID (United States); Carroll, Mark [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-05-01

    The Advanced Reactor Technology (ART) Graphite Research and Development Program is investigating doped nuclear graphite grades that exhibit oxidation resistance through the formation of protective oxides on the surface of the graphite material. In the unlikely event of an oxygen ingress accident, graphite components within the VHTR core region are anticipated to oxidize so long as the oxygen continues to enter the hot core region and the core temperatures remain above 400°C. For the most serious air-ingress accident which persists over several hours or days the continued oxidation can result in significant structural damage to the core. Reducing the oxidation rate of the graphite core material during any air-ingress accident would mitigate the structural effects and keep the core intact. Previous air oxidation testing of nuclear-grade graphite doped with varying levels of boron-carbide (B4C) at a nominal 739°C was conducted for a limited number of doped specimens demonstrating a dramatic reduction in oxidation rate for the boronated graphite grade. This report summarizes the conclusions from this small scoping study by determining the effects of oxidation on the mechanical strength resulting from oxidation of boronated and unboronated graphite to a 10% mass loss level. While the B4C additive did reduce mechanical strength loss during oxidation, adding B4C dopants to a level of 3.5% or more reduced the as-fabricated compressive strength nearly 50%. This effectively minimized any benefits realized from the protective film formed on the boronated grades. Future work to infuse different graphite grades with silicon- and boron-doped material as a post-machining conditioning step for nuclear components is discussed as a potential solution for these challenges in this report.

  8. High temperature oxidation resistant cermet compositions

    Science.gov (United States)

    Phillips, W. M. (Inventor)

    1976-01-01

    Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

  9. 21 CFR 184.1545 - Nitrous oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Nitrous oxide. 184.1545 Section 184.1545 Food and... Substances Affirmed as GRAS § 184.1545 Nitrous oxide. (a) Nitrous oxide (empirical formula N2O, CAS Reg. No.... Nitrous oxide is manufactured by the thermal decomposition of ammonium nitrate. Higher oxides of nitrogen...

  10. Optical properties and electronic transitions of zinc oxide, ferric oxide, cerium oxide, and samarium oxide in the ultraviolet and extreme ultraviolet

    DEFF Research Database (Denmark)

    Pauly, N; Yubero, F; Espinós, J P

    2017-01-01

    Optical properties and electronic transitions of four oxides, namely zinc oxide, ferric oxide, cerium oxide, and samarium oxide, are determined in the ultraviolet and extreme ultraviolet by reflection electron energy loss spectroscopy using primary electron energies in the range 0.3-2.0 ke...

  11. Uranium oxide recovering method

    International Nuclear Information System (INIS)

    Ota, Kazuaki; Takazawa, Hiroshi; Teramae, Naoki; Onoue, Takeshi.

    1997-01-01

    Nitrates containing uranium nitrate are charged in a molten salt electrolytic vessel, and a heat treatment is applied to prepare molten salts. An anode and a cathode each made of a graphite rod are disposed in the molten salts. AC voltage is applied between the anode and the cathode to conduct electrolysis of the molten salts. Uranium oxides are deposited as a recovered product of uranium, on the surface of the anode. The nitrates containing uranium nitrate are preferably a mixture of one or more nitrates selected from sodium nitrate, potassium nitrate, calcium nitrate and magnesium nitrate with uranium nitrate. The nitrates may be liquid wastes of nitrates. The temperature for the electrolysis of the molten salts is preferably from 150 to 300degC. The voltage for the electrolysis of the molten salts is preferably an AC voltage of from 2 to 6V, more preferably from 4 to 6V. (I.N.)

  12. Solid Oxide Electrolyser Cell

    DEFF Research Database (Denmark)

    Jensen, Søren Højgaard

    Solid oxide fuel cells (SOFCs) produced at Risø National Laboratory was tested as steam electrolysers under various current densities, operating temperatures and steam partial pressures. At 950 °C and a cell voltage of 1.48V the current density was -3.6A/cm2 with app. 30% H2 + 70% H2O in the inlet...... it is possible to achieve a production price of 0.7 US$/kg H2 with an electricity price of 1.3 US¢/kWh. The cell voltage was measured as function of time. In test ofabout two month of duration a long-term degradation was observed. At 850 °C, -0.5 A/cm2 with 50 vol% H2 the degradation rate was app. 20 mV/1000h...

  13. Uranium plutonium oxide fuels

    International Nuclear Information System (INIS)

    Cox, C.M.; Leggett, R.D.; Weber, E.T.

    1981-01-01

    Uranium plutonium oxide is the principal fuel material for liquid metal fast breeder reactors (LMFBR's) throughout the world. Development of this material has been a reasonably straightforward evolution from the UO 2 used routinely in the light water reactor (LWR's); but, because of the lower neutron capture cross sections and much lower coolant pressures in the sodium cooled LMFBR's, the fuel is operated to much higher discharge exposures than that of a LWR. A typical LMFBR fuel assembly is shown. Depending on the required power output and the configuration of the reactor, some 70 to 400 such fuel assemblies are clustered to form the core. There is a wide variation in cross section and length of the assemblies where the increasing size reflects a chronological increase in plant size and power output as well as considerations of decreasing the net fuel cycle cost. Design and performance characteristics are described

  14. Thermal and oxidation effects

    Energy Technology Data Exchange (ETDEWEB)

    Adamcova, J.; Kolaoikova, I. [Prague Univ., Institute of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles (Czech Republic); Adamcova, J. [Czech Geological Survey, Geologicka 6, Prague (Czech Republic); Kaufhold, S.; Dohrmann, R. [BGR, Federal Institute for Geoscience and Natural Resources, Hannover (Germany); Dohrmann, R. [LBEG, State Authority for Mining, Energy, and Geology, Hannover (Germany); Craen, M. de; Van Geet, M.; Honty, M.; Wang, L.; Weetjens, E. [CK-CEN - Belgian Nuclear Research Centre - Environment, Healt and Safety Institute, Mol (Belgium); Van Geet, M. [ONDRAF/NIRAS - Belgian Agency for Radioactive Waste and Enriched Fissile Materials, Brussel (Belgium); Pozzi, J.P.; Janots, D. [Ecole Normale Paris, CNRS Lab. de Geologie, 75 - Paris (France); Aubourg, C. [Universite Cergy Pontoise, CNRS Lab. de Tectonique, 95 (France); Cathelineau, M.; Rousset, D.; Ruck, R. [Nancy-1 Univ. Henri Poincare, CNRS G2R, 54 (France); Clauer, N. [Strasbourg-1 Univ., CNRS CGS, 67 (France); Liewig, N. [Institut Pluridisciplinaire Hubert Curien, CNRS, 67 - Strasbourg (France); Techer, I. [Nimes Univ., CNRS Cerege, 30 (France)

    2007-07-01

    This session gathers 4 articles dealing with: the alteration processes in bentonites: mineralogical and structural changes during long-term and short-term experiments (J. Adamcov, I. Kolarikova); the implications from the lot experiment regarding the selection of an optimum HLRW bentonite (S. Kaufhold, R. Dohrmann); the extent of oxidation in Boom clay as a result of excavation and ventilation of the HADES URF: Experimental and modelling assessments (M. De Craen, M. Van Geet, M. Honty, L. Wang, E. Weetjens); and the magnetic and mineralogical alterations under thermal stress at 95 deg. C of Callovo-Oxfordian clay-stones (Bure, France) and lower Dogger Mont Terri clay-stones, Switzerland (J.P. Pozzi, C. Aubourg, D. Janots, M. Cathelineau, N. Clauer, D. Rousset, R. Ruck, N. Liewig, I. Techer)

  15. Computer simulation of oxides

    International Nuclear Information System (INIS)

    Rowley, A.

    1998-01-01

    An ionic interaction model is developed which accounts for the effects of the ionic environment upon the electron densities of both cations and anions through changes in their size and shape and is transferable between materials. These variations are represented by additional dynamical variables which are handled within the model using the techniques of the Car-Parrinello method. The model parameters are determined as far as possible by input from external ab initio electronic structure calculations directed at examining the individual effects of the ionic environment upon the ions, particularly the oxide ion. Techniques for the evaluation of dipolar and quadrupolar Ewald sums in non-cubic simulation cells and the calculation of the pressure due to the terms in the potential are presented. This model is applied to the description of the perfect crystal properties and phonon dispersion curves of MgO. Consideration of the high symmetry phonon modes allows parameterization of the remaining model parameters in an unambiguous fashion. The same procedure is used to obtain parameters for CaO. These two parameter sets are examined to determine how they may be used to generate the parameters for SrO and simple scaling relationships based on ionic radii and polarizabilities are formulated. The transferability of the model to Cr 2 O 3 is investigated using parameters generated from the alkaline earth oxides. The importance of lower symmetry model terms, particularly quadrupolar interactions, at the low symmetry ion sites in the crystal structure is demonstrated. The correct ground-state crystal structure is predicted and the calculated surface energies and relaxation phenomena are found to agree well with previous ab initio studies. The model is applied to GeO 2 as a strong test of its applicability to ion environments far different from those encountered in MgO. An good description of the crystal structures is obtained and the interplay of dipolar and quadrupolar effects is

  16. Nanoroses of nickel oxides: Synthesis, electron tomography study, and application in CO oxidation and energy storage

    KAUST Repository

    Fihri, Aziz; Sougrat, Rachid; Baby, Rakhi Raghavan; Rahal, Raed; Cha, Dong Kyu; Hedhili, Mohamed N.; Bouhrara, Mohamed; Alshareef, Husam N.; Polshettiwar, Vivek

    2012-01-01

    Nickel oxide and mixed-metal oxide structures were fabricated by using microwave irradiation in pure water. The nickel oxide self-assembled into unique rose-shaped nanostructures. These nickel oxide roses were studied by performing electron

  17. Nitrous oxide and perioperative outcomes.

    Science.gov (United States)

    Ko, Hanjo; Kaye, Alan David; Urman, Richard D

    2014-06-01

    There is emerging evidence related to the effects of nitrous oxide on important perioperative patient outcomes. Proposed mechanisms include metabolic effects linked to elevated homocysteine levels and endothelial dysfunction, inhibition of deoxyribonucleic acid and protein formation, and depression of chemotactic migration by monocytes. Newer large studies point to possible risks associated with the use of nitrous oxide, although data are often equivocal and inconclusive. Cardiovascular outcomes such as stroke or myocardial infarction were shown to be unchanged in previous studies, but the more recent Evaluation of Nitrous Oxide in the Gas Mixture for Anesthesia I trial shows possible associations between nitrous oxide and increased cardiovascular and pulmonary complications. There are also possible effects on postoperative wound infections and neuropsychological function, although the multifactorial nature of these complications should be considered. Teratogenicity linked to nitrous oxide use has not been firmly established. The use of nitrous oxide for routine anesthetic care may be associated with significant costs if complications such as nausea, vomiting, and wound infections are taken into consideration. Overall, definitive data regarding the effect of nitrous oxide on major perioperative outcomes are lacking. There are ongoing prospective studies that may further elucidate its role. The use of nitrous oxide in daily practice should be individualized to each patient's medical conditions and risk factors.

  18. Modern chemistry of nitrous oxide

    International Nuclear Information System (INIS)

    Leont'ev, Aleksandr V; Fomicheva, Ol'ga A; Proskurnina, Marina V; Zefirov, Nikolai S

    2001-01-01

    Modern trends of the chemistry of nitrous oxide are discussed. Data on its structure, physical properties and reactivity are generalised. The effect of N 2 O on the environment and the possibility of its utilisation are considered. Attention is focused on the processes in which the oxidising potential of nitrous oxide can be employed. The bibliography includes 329 references.

  19. on THICKNESS OF COPPER (|) OXIDE

    African Journals Online (AJOL)

    2006-12-20

    Dec 20, 2006 ... known materials to be used as semiconductor devices. The oxide is. Observed to be an attractive starting material for the production of solar cells for low cost terrestrial conversion of solar energy to electricity. Copper (I) oxide is one Of the earliest known photovoltaic materials and the first in which the ...

  20. BRCA1 and Oxidative Stress

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Yong Weon; Kang, Hyo Jin [Department of Oncology, Lombardi Comprehensive Cancer Center, Georgetown University Medical Center, Washington, DC 20057 (United States); Bae, Insoo, E-mail: ib42@georgetown.edu [Department of Oncology, Lombardi Comprehensive Cancer Center, Georgetown University Medical Center, Washington, DC 20057 (United States); Department of Radiation Medicine, Lombardi Comprehensive Cancer Center, Georgetown University Medical Center, Washington, DC 20057 (United States)

    2014-04-03

    The breast cancer susceptibility gene 1 (BRCA1) has been well established as a tumor suppressor and functions primarily by maintaining genome integrity. Genome stability is compromised when cells are exposed to oxidative stress. Increasing evidence suggests that BRCA1 regulates oxidative stress and this may be another mechanism in preventing carcinogenesis in normal cells. Oxidative stress caused by reactive oxygen species (ROS) is implicated in carcinogenesis and is used strategically to treat human cancer. Thus, it is essential to understand the function of BRCA1 in oxidative stress regulation. In this review, we briefly summarize BRCA1’s many binding partners and mechanisms, and discuss data supporting the function of BRCA1 in oxidative stress regulation. Finally, we consider its significance in prevention and/or treatment of BRCA1-related cancers.

  1. Nanotoxicology of Metal Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Amedea B. Seabra

    2015-06-01

    Full Text Available This review discusses recent advances in the synthesis, characterization and toxicity of metal oxide nanoparticles obtained mainly through biogenic (green processes. The in vitro and in vivo toxicities of these oxides are discussed including a consideration of the factors important for safe use of these nanomaterials. The toxicities of different metal oxide nanoparticles are compared. The importance of biogenic synthesized metal oxide nanoparticles has been increasing in recent years; however, more studies aimed at better characterizing the potent toxicity of these nanoparticles are still necessary for nanosafely considerations and environmental perspectives. In this context, this review aims to inspire new research in the design of green approaches to obtain metal oxide nanoparticles for biomedical and technological applications and to highlight the critical need to fully investigate the nanotoxicity of these particles.

  2. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J; Koljonen, T [VTT Energy, Espoo (Finland)

    1997-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  3. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  4. Exploring oxidative modifications of tyrosine

    DEFF Research Database (Denmark)

    Houée-Lévin, C; Bobrowski, K; Horakova, L

    2015-01-01

    residues are oxidised in vivo with impact on cellular homeostasis and redox signalling pathways. A notable example is tyrosine, which can undergo a number of oxidative post-translational modifications to form 3-hydroxy-tyrosine, tyrosine crosslinks, 3-nitrotyrosine and halogenated tyrosine, with different...... effects on cellular functions. Tyrosine oxidation has been studied extensively in vitro, and this has generated detailed information about the molecular mechanisms that may occur in vivo. An important aspect of studying tyrosine oxidation both in vitro and in biological systems is the ability to monitor...... residues modified and the nature of the modification. These approaches have helped understanding of the consequences of tyrosine oxidation in biological systems, especially its effects on cell signalling and cell dysfunction, linking to roles in disease. There is mounting evidence that tyrosine oxidation...

  5. Superparamagnetic iron oxides for MRI

    International Nuclear Information System (INIS)

    Weissleder, R.; Reimer, P.

    1993-01-01

    Pharmaceutical iron oxide preparations have been used as MRI contrast agents for a variety of purposes. These agents predominantly decrease T2 relaxation times and therefore cause a decrease in signal intensity of tissues that contain the agent. After intravenous administration, dextran-coated iron oxides typically accumulate in phagocytic cells in liver and spleen. Clinical trials have shown that iron oxide increases lesion/liver and lesion/spleen contrast, that more lesions can be depicted than on plain MRI or CT, and that the size threshold for lesion detection decreases. Decreased uptake of iron oxides in liver has been observed in hepatitis and cirrhosis, potentially allowing the assessment of organ function. More recently a variety of novel, target-specific monocrystalline iron oxides compounds have been used for receptor and immunospecific images. Future development of targeted MRI contrast agents is critical for organ- or tissue-specific quantitative and functional MRI. (orig.)

  6. Superparamagnetic iron oxides for MRI

    Energy Technology Data Exchange (ETDEWEB)

    Weissleder, R [MGH-NMR Center, Dept. of Radiology, Massachusetts General Hospital and Harvard Medical School, Boston, MA (United States); Reimer, P [MGH-NMR Center, Dept. of Radiology, Massachusetts General Hospital and Harvard Medical School, Boston, MA (United States); [Inst. fuer Klinische Radiologie, Zentrale Roentgendiagnostik, Westfaelische-Wilhelms-Univ., Muenster (Germany)

    1993-06-01

    Pharmaceutical iron oxide preparations have been used as MRI contrast agents for a variety of purposes. These agents predominantly decrease T2 relaxation times and therefore cause a decrease in signal intensity of tissues that contain the agent. After intravenous administration, dextran-coated iron oxides typically accumulate in phagocytic cells in liver and spleen. Clinical trials have shown that iron oxide increases lesion/liver and lesion/spleen contrast, that more lesions can be depicted than on plain MRI or CT, and that the size threshold for lesion detection decreases. Decreased uptake of iron oxides in liver has been observed in hepatitis and cirrhosis, potentially allowing the assessment of organ function. More recently a variety of novel, target-specific monocrystalline iron oxides compounds have been used for receptor and immunospecific images. Future development of targeted MRI contrast agents is critical for organ- or tissue-specific quantitative and functional MRI. (orig.)

  7. Selective carbon monoxide oxidation over Ag-based composite oxides

    Energy Technology Data Exchange (ETDEWEB)

    Guldur, C. [Gazi University, Ankara (Turkey). Chemical Engineering Department; Balikci, F. [Gazi University, Ankara (Turkey). Institute of Science and Technology, Environmental Science Department

    2002-02-01

    We report our results of the synthesis of 1 : 1 molar ratio of the silver cobalt and silver manganese composite oxide catalysts to remove carbon monoxide from hydrogen-rich fuels by the catalytic oxidation reaction. Catalysts were synthesized by the co-precipitation method. XRD, BET, TGA, catalytic activity and catalyst deactivation studies were used to identify active catalysts. Both CO oxidation and selective CO oxidation were carried out in a microreactor using a reaction gas mixture of 1 vol% CO in air and another gas mixture was prepared by mixing 1 vol% CO, 2 vol% O{sub 2}, 84 vol% H{sub 2}, the balance being He. 15 vol% CO{sub 2} was added to the reactant gas mixture in order to determine the effect of CO{sub 2}, reaction gases were passed through the humidifier to determine the effect of the water vapor on the oxidation reaction. It was demonstrated that metal oxide base was decomposed to the metallic phase and surface areas of the catalysts were decreased when the calcination temperature increased from 200{sup o}C to 500{sup o}C. Ag/Co composite oxide catalyst calcined at 200{sup o}C gave good activity at low temperatures and 90% of CO conversion at 180{sup o}C was obtained for the selective CO oxidation reaction. The addition of the impurities (CO{sub 2} or H{sub 2}O) decreased the activity of catalyst for selective CO oxidation in order to get highly rich hydrogen fuels. (author)

  8. Oxide ultrathin films science and technology

    CERN Document Server

    Pacchioni, Gianfranco

    2012-01-01

    A wealth of information in one accessible book. Written by international experts from multidisciplinary fields, this in-depth exploration of oxide ultrathin films covers all aspects of these systems, starting with preparation and characterization, and going on to geometrical and electronic structure, as well as applications in current and future systems and devices. From the Contents: Synthesis and Preparation of Oxide Ultrathin Films Characterization Tools of Oxide Ultrathin Films Ordered Oxide Nanostructures on Metal Surfaces Unusual Properties of Oxides and Other Insulators in the Ultrathin Limit Silica and High-K Dielectrics Thin Films in Microelectronics Oxide Passive Films and Corrosion Protection Oxide Films as Catalytic Materials and as Models of Real Catalysts Oxide Films in Spintronics Oxide Ultrathin Films in Solid Oxide Fuel Cells Transparent Conducting and Chromogenic Oxide Films as Solar Energy Materials Oxide Ultrathin Films in Sensor Applications Ferroelectricity in Ultrathin Film Capacitors T...

  9. Catalyst for Decomposition of Nitrogen Oxides

    Science.gov (United States)

    Schryer, David R. (Inventor); Jordan, Jeffrey D. (Inventor); Akyurtlu, Ates (Inventor); Akyurtlu, Jale (Inventor)

    2015-01-01

    This invention relates generally to a platinized tin oxide-based catalyst. It relates particularly to an improved platinized tin oxide-based catalyst able to decompose nitric oxide to nitrogen and oxygen without the necessity of a reducing gas.

  10. Test Concept for Advanced Oxidation Techniques

    DEFF Research Database (Denmark)

    Bennedsen, Lars Rønn; Søgaard, Erik Gydesen; Mortensen, Lars

    advanced on-site oxidation tests. The remediation techniques included are electrochemical oxidation, photochemical/photocatalytic oxidation, ozone, hydrogen peroxide, permanganate, and persulfate among others. A versatile construction of the mobile test unit makes it possible to combine different...

  11. Treatment of Fatty Acid Oxidation Disorders

    Science.gov (United States)

    ... Treatment of fatty acid oxidation disorders Treatment of fatty acid oxidation disorders E-mail to a friend Please ... this page It's been added to your dashboard . Fatty acid oxidation disorders are rare health conditions that affect ...

  12. Trends for Methane Oxidation at Solid Oxide Fuel Cell Conditions

    DEFF Research Database (Denmark)

    Kleis, Jesper; Jones, Glenn; Abild-Pedersen, Frank

    2009-01-01

    First-principles calculations are used to predict a plausible reaction pathway for the methane oxidation reaction. In turn, this pathway is used to obtain trends in methane oxidation activity at solid oxide fuel cell (SOFC) anode materials. Reaction energetics and barriers for the elementary...... the Ni surfaces to other metals of interest. This allows the reactivity over the different metals to be understood in terms of two reactivity descriptors, namely, the carbon and oxygen adsorption energies. By combining a simple free-energy analysis with microkinetic modeling, activity landscapes of anode...

  13. Electrochemical Thinning for Anodic Aluminum Oxide and Anodic Titanium Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, In Hae; Jo, Yun Kyoung; Kim, Yong Tae; Tak, Yong Sug; Choi, Jin Sub [Inha University, Incheon (Korea, Republic of)

    2012-05-15

    For given electrolytes, different behaviors of anodic aluminum oxide (AAO) and anodic titanium oxide (ATO) during electrochemical thinning are explained by ionic and electronic current modes. Branched structures are unavoidably created in AAO since the switch of ionic to electronic current is slow, whereas the barrier oxide in ATO is thinned without formation of the branched structures. In addition, pore opening can be possible in ATO if chemical etching is performed after the thinning process. The thinning was optimized for complete pore opening in ATO and potential-current behavior is interpreted in terms of ionic current-electronic current switching.

  14. Mesoporous Transition Metal Oxides for Supercapacitors

    OpenAIRE

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are result...

  15. The oxidation and corrosion of ODS alloys

    Science.gov (United States)

    Lowell, Carl E.; Barrett, Charles A.

    1990-01-01

    The oxidation and hot corrosion of high temperature oxide dispersion strengthened (ODS) alloys are reviewed. The environmental resistance of such alloys are classified by oxide growth rate, oxide volatility, oxide spalling, and hot corrosion limitations. Also discussed are environmentally resistant coatings for ODS materials. It is concluded that ODS NiCrAl and FeCrAl alloys are highly oxidation and corrosion resistant and can probably be used uncoated.

  16. Oxidation And Hot Corrosion Of ODS Alloy

    Science.gov (United States)

    Lowell, Carl E.; Barrett, Charles A.

    1993-01-01

    Report reviews oxidation and hot corrosion of oxide-dispersion-strengthened (ODS) alloys, intended for use at high temperatures. Classifies environmental resistances of such alloys by rates of growth of oxides, volatilities of oxides, spalling of oxides, and limitations imposed by hot corrosion. Also discusses environmentally resistant coatings for ODS materials. Concludes ODS NICrAl and FeCrAl alloys highly resistant to oxidation and corrosion and can be used uncoated.

  17. Oxidation kinetics of corium pool

    Energy Technology Data Exchange (ETDEWEB)

    Sulatsky, A.A., E-mail: andrei314@mail.ru [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Smirnov, S.A. [D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St. Petersburg (Russian Federation); Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu. [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Fischer, M.; Hellmann, S. [AREVA NP GmbH, Erlangen (Germany); Tromm, W.; Miassoedov, A. [Forschungzentrum Karlsruhe (FZK), Karlsruhe (Germany); Bottomley, D. [EUROPÄISCHE KOMMISSION, Joint Research Centre Institut für Transurane (ITU), Karlsruhe (Germany); Piluso, P. [CEA Cadarache-DEN/DTN/STRI, St.Paul-lez-Durance (France); Barrachin, M. [Institut de Radioprotection et Sûreté Nucléaire, St.Paul-lez-Durance (France)

    2013-09-15

    Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations.

  18. Oxidation kinetics of corium pool

    International Nuclear Information System (INIS)

    Sulatsky, A.A.; Smirnov, S.A.; Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu.; Fischer, M.; Hellmann, S.; Tromm, W.; Miassoedov, A.; Bottomley, D.; Piluso, P.; Barrachin, M.

    2013-01-01

    Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations

  19. Alumina composites for oxide/oxide fibrous monoliths

    International Nuclear Information System (INIS)

    Cruse, T. A.; Polzin, B. J.; Picciolo, J. J.; Singh, D.; Tsaliagos, R. N.; Goretta, K. C.

    2000-01-01

    Most work on ceramic fibrous monoliths (FMs) has focused on the Si 3 N 4 /BN system. In an effort to develop oxidation-resistant FMs, several oxide systems have recently been examined. Zirconia-toughened alumina and alumina/mullite appear to be good candidates for the cell phase of FMs. These composites offer higher strength and toughness than pure alumina and good high-temperature stability. By combining these oxides, possibly with a weaker high-temperature oxide as the cell-boundary phase, it should be possible to product a strong, resilient FM that exhibits graceful failure. Several material combinations have been examined. Results on FM fabrication and microstructural development are presented

  20. Plutonium oxide shipment report

    International Nuclear Information System (INIS)

    1979-01-01

    While following procedures for unloading shipping containers containing plutonium oxide, SRP personnel experienced problems. While using a pipe cutter to cut through the wall of the inner container, the pipe section fell to the floor. Three empty food cans in the bottom of the inner canister also fell to the floor and a puff of smoke was observed. Personnel were evacuated and contamination was detected in the room. As a result of the investigations conducted by Westinghouse and SRP, thermal effects, food can coatings, and fuel volatiles were eliminated as the cause of the problem. Helium used to leak test the RL070 shipping container seals entered the inner canister through two weld defects resulting in a pressurization of the contents. When the end cap was removed, the inner canister vented rapidly, the food cans did not, thus creating a differential pressure across the food cans. This caused the food cans to swell. It was recommended that a dye penetrant test of all inner container welds be added. Additional unloading procedures were also recommended

  1. Nitric oxide nanoparticles

    Science.gov (United States)

    Schairer, David O.; Martinez, Luis R.; Blecher, Karin; Chouake, Jason S.; Nacharaju, Parimala; Gialanella, Philip; Friedman, Joel M.; Nosanchuk, Joshua D.; Friedman, Adam J.

    2012-01-01

    Nitric oxide (NO) is a critical component of host defense against invading pathogens; however, its therapeutic utility is limited due to a lack of practical delivery systems. Recently, a NO-releasing nanoparticulate platform (NO-np) was shown to have in vitro broad-spectrum antimicrobial activity and in vivo pre-clinical efficacy in a dermal abscess model. To extend these findings, both topical (TP) and intralesional (IL) NO-np administration was evaluated in a MRSA intramuscular murine abscess model and compared with vancomycin. All treatment arms accelerated abscess clearance clinically, histologically, and by microbiological assays on both days 4 and 7 following infection. However, abscesses treated with NO-np via either route demonstrated a more substantial, statistically significant decrease in bacterial survival based on colony forming unit assays and histologically revealed less inflammatory cell infiltration and preserved muscular architecture. These data suggest that the NO-np may be an effective addition to our armament for deep soft tissue infections. PMID:22286699

  2. Nitrous oxide availability.

    Science.gov (United States)

    Murray, M J; Murray, W J

    1980-04-01

    Nitrous oxide (N2O) is marketed as an inhalation anesthetic and as a food ingredient (e.g., whipping cream propellant). In the human, inhalation has been associated with "highs," peripheral nerve damage, mitotic poisoning of bone marrow, psychosis, and mental impairment. Exposure to hypoxemic mixtures has resulted in death. The commercial N2O sources specifically studied were aerosol whipping cream containers (three brands) and 6.5-cm cylinders, or chargers (two brands). The gas content and N2O concentrations of these devices were measured. The aerosol cans, when not shaken, will dispense at least 3 liters of 87 to 90% N2O. Charger misuse may occur when they are substituted for identically designed carbon dioxide (CO2) chargers of a seltzer bottle; 4.3 to 5.0 liters of 93 to 98% N2O is expelled at a controllable rate. The toxicity of these inexpensive N2O products, their high potential for misuse, and the absence of labeling (chargers) argue that their distribution be discontinued.

  3. Oxidative desulfurization: kinetic modelling.

    Science.gov (United States)

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  4. Oxidative desulfurization: Kinetic modelling

    International Nuclear Information System (INIS)

    Dhir, S.; Uppaluri, R.; Purkait, M.K.

    2009-01-01

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H 2 O 2 over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel

  5. Electrochromism in transition metal oxides

    International Nuclear Information System (INIS)

    Estrada, W.

    1993-01-01

    Electrochromism is discussed for transition metal oxides. Particularly tungsten oxide and nickel oxide are reviewed, in order to put forth the different aspects of the field. Since this phenomena has been reviewed by several authors, it is not tried to be comprehensive but rather pedagogical. The basic requirements for a material -in both non-emissive displays and energy efficiency applications- to be electrochromic, a general view of electrochromic mechanism, anodic and cathodic electrochromic materials, and current problems for a electrochromic theory are presented. (author) 45 refs., 8 figs

  6. Obesity, reproduction and oxidative stress

    Directory of Open Access Journals (Sweden)

    Tamara V. Zhuk

    2017-12-01

    Full Text Available The prevalence of obesity and overweight is one of the most pressing problems nowadays. Obesity as a comorbid condition affects all body systems. Obesity has been reported to be a risk factor not only for cardiovascular diseases and oncopathology, but also for fertility problems, many obstetric and perinatal complications worsening the maternal and infant health. The balance between the oxidative and antioxidant system is one of the indicators of the state of human homeostasis. Today it is proved that obesity is associated with an increase in oxidative stress and a decrease in antioxidant protection. This review reveals a close relationship between obesity, oxidative stress and reproductive problems.

  7. Chaperones, but not oxidized proteins, are ubiquitinated after oxidative stress

    DEFF Research Database (Denmark)

    Kästle, Marc; Reeg, Sandra; Rogowska-Wrzesinska, Adelina

    2012-01-01

    of these proteins by MALDI tandem mass spectrometry (MALDI MS/MS). As a result we obtained 24 different proteins which can be categorized into the following groups: chaperones, energy metabolism, cytoskeleton/intermediate filaments, and protein translation/ribosome biogenesis. The special set of identified......, ubiquitinated proteins confirm the thesis that ubiquitination upon oxidative stress is no random process to degrade the mass of oxidized proteins, but concerns a special group of functional proteins....

  8. Oxidation of tritium by hopcalite bed

    Energy Technology Data Exchange (ETDEWEB)

    Nishikawa, Masabumi; Shinnai, Kohsuke; Matsunaga, Sohichi; Kinoshita, Yoshihiko

    1984-08-01

    Oxidation by the catalyst bed with a metal oxide and subsequent adsorption to the porous dehydrative reagents is supposed to be effective process for scavenging tritium from an inert atmosphere. Use of spongy copper oxide or wires of copper oxide is not recommended to use as the metal oxide catalyst from the view point of mass transfer because of sintering and of limited effective surface area. Use of hopcalites and copper oxide-kieselguhr are examined in this study and it is concluded that hopcalites are more suitable as the metal oxide catalyst because they not only remain the oxidation power on hydrogen isotopes even at an ambient temperature, but also show a negligible drop in oxidation performances with repeated regeneration. The effective temperature is about 400/sup 0/C for hopcalites and 300-600/sup 0/C for copper oxide-kieselguhr to use as the oxidation bed of tritium.

  9. Oxidation of tritium by hopcalite bed

    International Nuclear Information System (INIS)

    Nishikawa, Masabumi; Shinnai, Kohsuke; Matsunaga, Sohichi; Kinoshita, Yoshihiko

    1984-01-01

    Oxidation by the catalyst bed with a metal oxide and subsequent adsorption to the porous dehydrative reagents is supposed to be effective process for scavenging tritium from an inert atmosphere. Use of spongy copper oxide or wires of copper oxide is not recommended to use as the metal oxide catalyst from the view point of mass transfer because of sintering and of limited effective surface area. Use of hopcalites and copper oxide-kieselguhr are examined in this study and it is concluded that hopcalites are more suitable as the metal oxide catalyst because they not only remain the oxidation power on hydrogen isotopes even at an ambient temperature, but also show a negligible drop in oxidation performances with repeated regeneration. The effective temperature is about 400 0 C for hopcalites and 300--600 0 C for copper oxide-kieselguhr to use as the oxidation bed of tritium. (author)

  10. Synthesis of vertically aligned metal oxide nanostructures

    KAUST Repository

    Roqan, Iman S.

    2016-03-03

    Metal oxide nanostructure and methods of making metal oxide nanostructures are provided. The metal oxide nanostructures can be 1 -dimensional nanostructures such as nanowires, nanofibers, or nanotubes. The metal oxide nanostructures can be doped or undoped metal oxides. The metal oxide nanostructures can be deposited onto a variety of substrates. The deposition can be performed without high pressures and without the need for seed catalysts on the substrate. The deposition can be performed by laser ablation of a target including a metal oxide and, optionally, a dopant. In some embodiments zinc oxide nanostructures are deposited onto a substrate by pulsed laser deposition of a zinc oxide target using an excimer laser emitting UV radiation. The zinc oxide nanostructure can be doped with a rare earth metal such as gadolinium. The metal oxide nanostructures can be used in many devices including light-emitting diodes and solar cells.

  11. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

    2017-08-15

    Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

  12. Phenol oxidation with hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Ramiez Cortina, R.C.; Hernadez Perez, I. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico); Ortiz Lozoya, C.E. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico)]|[Inst. Mexicano del Petroleo (Mexico); Alonso Gutierrez, M.S. [Inst. National Polytechnique, ENSCT, Lab. of Chimie Agro-Industrielle, Toulouse (France)

    2003-07-01

    In this work the process application of advanced oxidation is investigated with hydrogen peroxide, for the phenol destruction. The experiments were carried out in a glass reactor of 750 mL. Three phenol concentrations were studied (2000, 1000 and 500 ppm) being oxidized with H{sub 2}O{sub 2} (1, 2 and 3 M). The tests of oxidation had a reaction time of 48 h at ambient temperature and pressure. The phenol degradation was determined as COD at different reaction times and intermediate oxidation products were analyzed by chromatography. The results of this study show that it is possible to degrade phenol (1000 ppm) until 90% with H{sub 2}O{sub 2} 2M. Being achieved the best efficiency with a good molar relationship of H{sub 2}O{sub 2}/phenol. Intends a reaction outline in the degradation of the phenol. (orig.)

  13. Diffusion of single oxidation pond

    Directory of Open Access Journals (Sweden)

    Song Ruo-Yuan

    2016-01-01

    Full Text Available The hydraulic characteristic of an oxidation pond was studied by the tracer experiment, and an empirical formula of Peclet number was obtained, which can be well applied to the model of plug flow reactor with longitudinal diffusion.

  14. ENGINEERING BULLETIN: SUPERCRITICAL WATER OXIDATION

    Science.gov (United States)

    This engineering bulletin presents a description and status of supercritical water oxidation technology, a summary of recent performance tests, and the current applicability of this emerging technology. This information is provided to assist remedial project managers, contractors...

  15. Reduction of blue tungsten oxide

    International Nuclear Information System (INIS)

    Wilken, T.; Wert, C.; Woodhouse, J.; Morcom, W.

    1975-01-01

    A significant portion of commercial tungsten is produced by hydrogen reduction of oxides. Although several modes of reduction are possible, hydrogen reduction is used where high purity tungsten is required and where the addition of other elements or compounds is desired for modification of the metal, as is done for filaments in the lamp industry. Although several investigations of the reduction of oxides have been reported (1 to 5), few principles have been developed which can aid in assessment of current commercial practice. The reduction process was examined under conditions approximating commercial practice. The specific objectives were to determine the effects of dopants, of water vapor in the reducing atmosphere, and of reduction temperature upon: (1) the rate of the reaction by which blue tungsten oxide is reduced to tungsten metal, (2) the intermediate oxides associated with reduction, and (3) the morphology of the resulting tungsten powder

  16. Oxidation dynamics of aluminum nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ying [Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Chemical Engineering and Materials Science, Department of Computer Science, University of Southern California, Los Angeles, California 90089-0242 (United States)

    2015-02-23

    Aluminum nanorods (Al-NRs) are promising fuels for pyrotechnics due to the high contact areas with oxidizers, but their oxidation mechanisms are largely unknown. Here, reactive molecular dynamics simulations are performed to study thermally initiated burning of oxide-coated Al-NRs with different diameters (D = 26, 36, and 46 nm) in oxygen environment. We found that thinner Al-NRs burn faster due to the larger surface-to-volume ratio. The reaction initiates with the dissolution of the alumina shell into the molten Al core to generate heat. This is followed by the incorporation of environmental oxygen atoms into the resulting Al-rich shell, thereby accelerating the heat release. These results reveal an unexpectedly active role of the alumina shell as a “nanoreactor” for oxidation.

  17. Aliphatic amine oxides as ligands

    International Nuclear Information System (INIS)

    Garla, L.C.; Betarello, V.H.; Chiericato Junior, G.; De Giovani, W.F.

    1984-01-01

    The reaction between some hydrated lanthanide perchlorates with trimethylamine oxide (TMAO) was studied. Compounds of general formula Ln(Cl 4 ) 3 : . 5,5 TMAO (Ln = La, Pr, Er and Y) were isolated. (Author) [pt

  18. Electrolytic recovery of uranium oxides

    International Nuclear Information System (INIS)

    Gurr, W.R.

    1979-01-01

    A method is described for extracting uranium oxide from a solution of one or more uranium compounds, e.g. leach liquors, comprising subjecting the solution to electrolysis utilizing a high current density, e.g. 500 to 4000 amp/m 2 , whereby uranium oxide is formed at the cathode and is recovered. The method is particularly suited to a continuous process using a rotating cathode cell. (author)

  19. ASSESSMENT OF GALLIUM OXIDE TECHNOLOGY

    Science.gov (United States)

    2017-08-01

    AFRL-RY-WP-TR-2017-0167 ASSESSMENT OF GALLIUM OXIDE TECHNOLOGY Burhan Bayraktaroglu Devices for Sensing Branch Aerospace...TITLE AND SUBTITLE ASSESSMENT OF GALLIUM OXIDE TECHNOLOGY 5a. CONTRACT NUMBER In-house 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER N/A 6...report summarizes the current status of the Ga2O3 technology based on published results on theoretical electronic structure, materials growth, and

  20. Neutron diffraction and oxide research

    International Nuclear Information System (INIS)

    Hunter, B.; Howard, C.J.; Kennedy, B.J.

    1999-01-01

    Oxide compounds form a large class of interesting materials that have a diverse range of mechanical and electronic properties. This diversity and its commercial implications has had a significant impact on physics research. This is particularly evident in the fields of superconductivity magnetoresistivity and ferroelectricity, where discoveries in the last 15 years have given rise to significant shifts in research activities. Historically, oxides have been studied for many years, but it is only recently that significant effort has been diverted to the study of oxide materials for their application to mechanical and electronic devices. An important property of such materials is the atomic structure, for the determination of which diffraction techniques are ideally suited. Recent examples of structure determinations using neutron diffraction in oxide based systems are high temperature superconductors, where oxygen defects are a key factor. Here, neutron diffraction played a major role in determining the effect of oxygen on the superconducting properties. Similarly, neutron diffraction has enjoyed much success in the determination of the structures of the manganate based colossal magnetoresistive (CMR) materials. In both these cases the structure plays a pivotal role in determining theoretical models of the electronic properties. The neutron scattering group at ANSTO has investigated several oxide systems using neutron powder diffraction. Two such systems are presented in this paper; the zirconia-based materials that are used as engineering materials, and the perovskite-based oxides that include the well known cuprate superconductors and the manganate CMR materials

  1. Accelerated oxidation processes is biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Canakci, M.; Monyem, A.; Van Gerpen, J.

    1999-12-01

    Biodiesel is an alternative fuel for diesel engines that can be produced from renewable feedstocks such as vegetable oil and animal fats. These feedstocks are reacted with an alcohol to produce alkyl monoesters that can be used in conventional diesel engines with little or no modification. Biodiesel, especially if produced from highly unsaturated oils, oxidizes more rapidly than diesel fuel. This article reports the results of experiments to track the chemical and physical changes that occur in biodiesel as it oxidizes. These results show the impact of time, oxygen flow rate, temperature, metals, and feedstock type on the rate of oxidation. Blending with diesel fuel and the addition of antioxidants are explored also. The data indicate that without antioxidants, biodiesel will oxidize very quickly at temperatures typical of diesel engines. This oxidation results in increases in peroxide value, acid value, and viscosity. While the peroxide value generally reaches a plateau of about 350 meq/kg ester, the acid value and viscosity increase monotonically as oxidation proceeds.

  2. 46 CFR 154.1725 - Ethylene oxide.

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... space of an ethylene oxide cargo tank for a period of 30 days under the condition of paragraph (e) of...

  3. 49 CFR 172.426 - OXIDIZER label.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false OXIDIZER label. 172.426 Section 172.426... SECURITY PLANS Labeling § 172.426 OXIDIZER label. (a) Except for size and color, the OXIDIZER label must be... OXIDIZER label must be yellow. [Amdt. 172-123, 56 FR 66257, Dec. 20, 1991] ...

  4. 21 CFR 73.2250 - Iron oxides.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron oxides consist of any one or any combination of synthetically prepared iron oxides, including the...

  5. Solid oxide electrolyser cell

    Energy Technology Data Exchange (ETDEWEB)

    Hoejgaard Jensen, S.

    2006-12-15

    Solid oxide fuel cells (SOFCs) produced at Riso National Laboratory was tested as steam electrolysers under various current densities, operating temperatures and steam partial pressures. At 950 deg. C and a cell voltage of 1.48V the current density was -3.6 A/cm{sup 2} with app. 30% H{sub 2} + 70% H{sub 2}O in the inlet gas and a H{sub 2}O utilization of app. 40%. The tested SOECs were also used for CO{sub 2} electrolysis. Economy studies of CO and H2 production show that especially H{sub 2} production can be competitive in areas with cheap electricity. Assuming the above described initial performance and a lifetime of 10 years it is possible to achieve a production price of 0.7 US dollar/kg H{sub 2} with an electricity price of 1.3 US cent/kWh. The cell voltage was measured as function of time. In test of about two month of duration a long-term degradation was observed. At 850 deg. C, -0.5 A/cm{sup 2} with 50 vol% H{sub 2} the degradation rate was app. 20 mV/1000h. It was shown that the degradation happens at Ni/YSZ-electrode. The long term degradation is probably caused by coarsening of the Ni-particles. After onset of electrolysis operation a transient passivation/reactivation phenomena with duration of several days was observed. It was shown that the phenomenon is attributed to the SiO{sub 2} contamination at the Ni/YSZ electrode-electrolyte interface. The SiO{sub 2} arises from the albite glass sealing (NaAlSi{sub 3}O{sub 8}) that surrounds the electrode. Si may enter the Ni/YSZ electrode via the reaction Si(OH){sub 4}(g) {r_reversible} SiO{sub 2}(l)+H{sub 2}O(g). At the active sites of the Ni/YSZ electrode steam is reduced via the reaction H{sub 2}O - 2e {yields} H{sub 2}+O{sup 2-} . This shifts the equilibrium of the first reaction to form SiO{sub 2}(l) at the active sites. After a certain time the sealing crystallizes and the SiO{sub 2}(l) evaporates from the active sites and the cell reactivates. The passivation is shown to relate to a build up of a

  6. Oxidative stress-mediated antibacterial activity of graphene oxide and reduced graphene oxide in Pseudomonas aeruginosa

    OpenAIRE

    Gurunathan, Sangiliyandi; Han,Jae Woong; Abdal Daye,Ahmed; Eppakayala,Vasuki; Kim,Jin-Hoi

    2012-01-01

    Sangiliyandi Gurunathan, Jae Woong Han, Ahmed Abdal Dayem, Vasuki Eppakayala, Jin-Hoi KimDepartment of Animal Biotechnology, Konkuk University, Seoul, South KoreaBackground: Graphene holds great promise for potential use in next-generation electronic and photonic devices due to its unique high carrier mobility, good optical transparency, large surface area, and biocompatibility. The aim of this study was to investigate the antibacterial effects of graphene oxide (GO) and reduced graphene oxid...

  7. Protein oxidation in muscle foods: A review

    DEFF Research Database (Denmark)

    Lund, Marianne; Heinonen, Marina; Baron, Caroline P.

    2011-01-01

    insight into the reactions involved in the oxidative modifications undergone by muscle proteins. Moreover, a variety of products derived from oxidized muscle proteins, including cross-links and carbonyls, have been identified. The impact of oxidation on protein functionality and on specific meat quality...... and consequences of Pox in muscle foods. The efficiency of different anti-oxidant strategies against the oxidation of muscle proteins is also reported.......Protein oxidation in living tissues is known to play an essential role in the pathogenesis of relevant degenerative diseases, whereas the occurrence and impact of protein oxidation (Pox) in food systems have been ignored for decades. Currently, the increasing interest among food scientists...

  8. Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

    International Nuclear Information System (INIS)

    Fossing, H.

    1992-01-01

    Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

  9. Size of oxide vacancies in fluorite and perovskite structured oxides

    DEFF Research Database (Denmark)

    Chatzichristodoulou, Christodoulos; Norby, Poul; Hendriksen, Peter Vang

    2015-01-01

    An analysis of the effective radii of vacancies and the stoichiometric expansion coefficient is performed on metal oxides with fluorite and perovskite structures. Using the hard sphere model with Shannon ion radii we find that the effective radius of the oxide vacancy in fluorites increases...... with increasing ion radius of the host cation and that it is significantly smaller than the radius of the oxide ion in all cases, from 37% smaller for HfO2 to 13 % smaller for ThO2. The perovskite structured LaGaO3 doped with Sr or Mg or both is analyzed in some detail. The results show that the effective radius...... of an oxide vacancy in doped LaGaO3 is only about 6 % smaller than the oxide ion. In spite of this the stoichiometric expansion coefficient (a kind of chemical expansion coefficient) of the similar perovskite, LaCrO3, is significantly smaller than the stoichiometric expansion coefficient of the fluorite...

  10. Diffusion of hydrogen in iron oxides

    International Nuclear Information System (INIS)

    Bruzzoni, P.

    1993-01-01

    The diffusion of hydrogen in transitions metals oxides has been recently studied at room temperature through the permeability electrochemical technique. This work studies thin oxide layers grown in air or in presence of oxidizing atmospheres at temperatures up to 200 deg C. The substrate was pure iron with different superficial treatments. It was observed that these oxides reduce up to three magnitudes orders, the hydrogen stationary flux through membranes of usual thickness in comparison with iron membranes free of oxide. (Author)

  11. Transparent conducting oxides and production thereof

    Science.gov (United States)

    Gessert, Timothy A.; Yoshida, Yuki; Coutts, Timothy J.

    2014-06-10

    Transparent conducting oxides and production thereof are disclosed. An exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target doped with either a high-permittivity oxide or a low-permittivity oxide in a process chamber. The method may also comprise depositing a metal oxide on the target in the process chamber to form a thin film having enhanced optical properties without substantially decreasing electrical quality.

  12. 21 CFR 186.1374 - Iron oxides.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Iron oxides. 186.1374 Section 186.1374 Food and... Substances Affirmed as GRAS § 186.1374 Iron oxides. (a) Iron oxides (oxides of iron, CAS Reg. No. 1332-37-2) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III...

  13. Wet-cupping removes oxidants and decreases oxidative stress.

    Science.gov (United States)

    Tagil, Suleyman Murat; Celik, Huseyin Tugrul; Ciftci, Sefa; Kazanci, Fatmanur Hacievliyagil; Arslan, Muzeyyen; Erdamar, Nazan; Kesik, Yunus; Erdamar, Husamettin; Dane, Senol

    2014-12-01

    Wet-cupping therapy is one of the oldest known medical techniques. Although it is widely used in various conditions such as acute\\chronic inflammation, infectious diseases, and immune system disorders, its mechanism of action is not fully known. In this study, we investigated the oxidative status as the first step to elucidate possible mechanisms of action of wet cupping. Wet cupping therapy is implemented to 31 healthy volunteers. Venous blood samples and Wet cupping blood samples were taken concurrently. Serum nitricoxide, malondialdehyde levels and activity of superoxide dismutase and myeloperoxidase were measured spectrophotometrically. Wet cupping blood had higher activity of myeloperoxidase, lower activity of superoxide dismutase, higher levels of malondialdehyde and nitricoxide compared to the venous blood. Wet cupping removes oxidants and decreases oxidative stress. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Metal oxide nanorod arrays on monolithic substrates

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

    2018-01-02

    A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can include a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.

  15. Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

    Directory of Open Access Journals (Sweden)

    Jacques C. Védrine

    2016-01-01

    Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

  16. Solid oxide electrochemical reactor science.

    Energy Technology Data Exchange (ETDEWEB)

    Sullivan, Neal P. (Colorado School of Mines, Golden, CO); Stechel, Ellen Beth; Moyer, Connor J. (Colorado School of Mines, Golden, CO); Ambrosini, Andrea; Key, Robert J. (Colorado School of Mines, Golden, CO)

    2010-09-01

    Solid-oxide electrochemical cells are an exciting new technology. Development of solid-oxide cells (SOCs) has advanced considerable in recent years and continues to progress rapidly. This thesis studies several aspects of SOCs and contributes useful information to their continued development. This LDRD involved a collaboration between Sandia and the Colorado School of Mines (CSM) ins solid-oxide electrochemical reactors targeted at solid oxide electrolyzer cells (SOEC), which are the reverse of solid-oxide fuel cells (SOFC). SOECs complement Sandia's efforts in thermochemical production of alternative fuels. An SOEC technology would co-electrolyze carbon dioxide (CO{sub 2}) with steam at temperatures around 800 C to form synthesis gas (H{sub 2} and CO), which forms the building blocks for a petrochemical substitutes that can be used to power vehicles or in distributed energy platforms. The effort described here concentrates on research concerning catalytic chemistry, charge-transfer chemistry, and optimal cell-architecture. technical scope included computational modeling, materials development, and experimental evaluation. The project engaged the Colorado Fuel Cell Center at CSM through the support of a graduate student (Connor Moyer) at CSM and his advisors (Profs. Robert Kee and Neal Sullivan) in collaboration with Sandia.

  17. 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.

  18. Anaerobic sulfide-oxidation in marine colorless sulfur-oxidizing bacteria

    Digital Repository Service at National Institute of Oceanography (India)

    LokaBharathi, P.A.; Nair, S.; Chandramohan, D.

    Colorless sulfur-oxidizing bacteria are ubiquitous in Indian waters and have the ability to oxidize sulfide under anaerobic conditions. These bacteria can not only mediate the sulfur cycle oxidatively but also the nitrogen cycle reductively without...

  19. Resveratrol and Endothelial Nitric Oxide

    Directory of Open Access Journals (Sweden)

    Ning Xia

    2014-10-01

    Full Text Available Nitric oxide (NO derived from the endothelial NO synthase (eNOS has antihypertensive, antithrombotic, anti-atherosclerotic and antiobesogenic properties. Resveratrol is a polyphenol phytoalexin with multiple cardiovascular and metabolic effects. Part of the beneficial effects of resveratrol are mediated by eNOS. Resveratrol stimulates NO production from eNOS by a number of mechanisms, including upregulation of eNOS expression, stimulation of eNOS enzymatic activity and reversal of eNOS uncoupling. In addition, by reducing oxidative stress, resveratrol prevents oxidative NO inactivation by superoxide thereby enhancing NO bioavailability. Molecular pathways underlying these effects of resveratrol involve SIRT1, AMPK, Nrf2 and estrogen receptors.

  20. Oxides gets environmentally-friendly

    DEFF Research Database (Denmark)

    Pryds, Nini

    for high temperature oxide thermoelectric (TE) modules to become a viable route for power generation, the overall efficiency of these devices must be improved. While most research currently focuses on the enhancement of the thermoelectric properties of the p- and n-type elements of the module, it is also...... necessary to demonstrate a working oxide module and develop stable interconnects with low contact resistance as well as mechanical and the chemical stability. In this presentation I will also show our latest results on the performance of oxide module made of ZnO doped Al (n-type) and CaCoO 349 (p-type) [1...... in realizing cooling devices with high efficiency and low global warming potentials, which are highly desirable for a broad range of applications. The technology relies on the magnetocaloric effect in a solid refrigerant rather than the temperature change that occurs when a gas is compressed. This talk...

  1. Atmospheric oxidation of selected hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Benter, T.; Olariu, R.I.

    2002-02-01

    This work presents investigations on the gas-phase chemistry of phenol and the cresol isomers performed in a 1080 l quartz glass reactor in Wuppertal and in a large-volume outdoor photoreactor EUPHORE in Valencia, Spain. The studies aimed at clarifying the oxidation mechanisms of the reactions of these compounds with OH and NO{sub 3} radicals. Product investigations on the oxidation of phenol and the cresol isomers initiated by OH radicals were performed in the 1080 l quartz glass reactor with analyses by in situ FT-IR absorption spectroscopy. The primary focus of the investigations was on the determination of product yields. This work represents the first determination and quantification of 1,2-dihydroxybenzenes in the OH oxidation of phenolic compounds. Possible reaction pathways leading to the observed products have been elucidated. (orig.)

  2. CELLULOSE DEGRADATION BY OXIDATIVE ENZYMES

    Directory of Open Access Journals (Sweden)

    Maria Dimarogona

    2012-09-01

    Full Text Available Enzymatic degradation of plant biomass has attracted intensive research interest for the production of economically viable biofuels. Here we present an overview of the recent findings on biocatalysts implicated in the oxidative cleavage of cellulose, including polysaccharide monooxygenases (PMOs or LPMOs which stands for lytic PMOs, cellobiose dehydrogenases (CDHs and members of carbohydrate-binding module family 33 (CBM33. PMOs, a novel class of enzymes previously termed GH61s, boost the efficiency of common cellulases resulting in increased hydrolysis yields while lowering the protein loading needed. They act on the crystalline part of cellulose by generating oxidized and non-oxidized chain ends. An external electron donor is required for boosting the activity of PMOs. We discuss recent findings concerning their mechanism of action and identify issues and questions to be addressed in the future.

  3. Oxidative stability of marine phospholipids

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline Pascale

    Many studies have shown that marine phospholipids (MPL) provide more advantages than fish oil. They have better bioavailability, better resistance towards oxidation and higher content of eicosapentaenoic acids (EPA) and docosahexaenoic acids (DHA) than oily triglycerides (fish oil). The objective...... of this study is to investigate the oxidative and hydrolytic stability of MPL. In addition, this study also investigates the effect of chemical composition of MPL and Maillard reaction (interaction between lipids oxidation products with the residue of amino acids) on MPL emulsions’ stability. Firstly, MPL were...... was further investigated through measurement of secondary volatile compounds by Solid Phase Microextraction at several time intervals. On the other hand, the Maillard reaction was investigated through the measurement of color changes and pyrrole content before and after 32 days storage. Preliminary result...

  4. Graphite oxidation in HTGR atmosphere

    International Nuclear Information System (INIS)

    Growcock, F.B.; Barry, J.J.; Finfrock, C.C.; Rivera, E.; Heiser, J.H. III

    1982-01-01

    On-going and recently completed studies of the effect of thermal oxidation on the structural integrity of HTGR candidate graphites are described, and some results are presented and discussed. This work includes the study of graphite properties which may play decisive roles in the graphites' resistance to oxidation and fracture: pore size distribution, specific surface area and impurity distribution. Studies of strength loss mechanisms in addition to normal oxidation are described. Emphasis is placed on investigations of the gas permeability of HTGR graphites and the surface burnoff phenomenon observed during recent density profile measurements. The recently completed studies of catalytic pitting and the effects of prestress and stress on reactivity and ultimate strength are also discussed

  5. Graphite Oxidation Thermodynamics/Reactions

    International Nuclear Information System (INIS)

    Propp, W.A.

    1998-01-01

    The vulnerability of graphite-matrix spent nuclear fuel to oxidation by the ambient atmosphere if the fuel canister is breached was evaluated. Thermochemical and kinetic data over the anticipated range of storage temperatures (200 to 400 C) were used to calculate the times required for a total carbon mass loss of 1 mgcm-2 from a fuel specimen. At 200 C, the time required to produce even this small loss is large, 900,000 yr. However, at 400 C the time required is only 1.9 yr. The rate of oxidation at 200 C is negligible, and the rate even at 400 C is so small as to be of no practical consequence. Therefore, oxidation of the spent nuclear fuel upon a loss of canister integrity is not anticipated to be a concern based upon the results of this study

  6. Adaptive oxide electronics: A review

    Science.gov (United States)

    Ha, Sieu D.; Ramanathan, Shriram

    2011-10-01

    Novel information processing techniques are being actively explored to overcome fundamental limitations associated with CMOS scaling. A new paradigm of adaptive electronic devices is emerging that may reshape the frontiers of electronics and enable new modalities. Creating systems that can learn and adapt to various inputs has generally been a complex algorithm problem in information science, albeit with wide-ranging and powerful applications from medical diagnosis to control systems. Recent work in oxide electronics suggests that it may be plausible to implement such systems at the device level, thereby drastically increasing computational density and power efficiency and expanding the potential for electronics beyond Boolean computation. Intriguing possibilities of adaptive electronics include fabrication of devices that mimic human brain functionality: the strengthening and weakening of synapses emulated by electrically, magnetically, thermally, or optically tunable properties of materials.In this review, we detail materials and device physics studies on functional metal oxides that may be utilized for adaptive electronics. It has been shown that properties, such as resistivity, polarization, and magnetization, of many oxides can be modified electrically in a non-volatile manner, suggesting that these materials respond to electrical stimulus similarly as a neural synapse. We discuss what device characteristics will likely be relevant for integration into adaptive platforms and then survey a variety of oxides with respect to these properties, such as, but not limited to, TaOx, SrTiO3, and Bi4-xLaxTi3O12. The physical mechanisms in each case are detailed and analyzed within the framework of adaptive electronics. We then review theoretically formulated and current experimentally realized adaptive devices with functional oxides, such as self-programmable logic and neuromorphic circuits. Finally, we speculate on what advances in materials physics and engineering may

  7. On hydrazine oxidation in nitric acid media

    International Nuclear Information System (INIS)

    Zil'berman, B.Ya.; Lelyuk, G.A.; Mashkin, A.N.; Yasnovitskaya, A.L.

    1988-01-01

    Yield of products of radiolytic ( 60 Co gamma radiation) and chemical hydrazine (HZ) oxidation in nitric acid media is studied. Under radiolyte HZ oxidation by nitric acid hydrazoic acid, ammonia and nitrogen appear to be the reaction products. HN 3 yield maximum under HZN oxidation makes up ∼ 0.35 mol per a mol of oxiduzed HZN. Under chemical oxidation HZN is oxidized by HNO 3 according to reaction catalysed by technetium HN 3 yield makes up ∼ 0.35 mol per a mol of oxidized HZN. Radiation-chemical oxidation of HN 3 proceeds up to its complete decomposition, decomposition rate is comparable with HZ oxidation rate. Under the chemical oxidation HN 3 is more stable, it is slowly decomposed after complete HZ decomposition

  8. Method for hot pressing beryllium oxide articles

    Science.gov (United States)

    Ballard, Ambrose H.; Godfrey, Jr., Thomas G.; Mowery, Erb H.

    1988-01-01

    The hot pressing of beryllium oxide powder into high density compacts with little or no density gradients is achieved by employing a homogeneous blend of beryllium oxide powder with a lithium oxide sintering agent. The lithium oxide sintering agent is uniformly dispersed throughout the beryllium oxide powder by mixing lithium hydroxide in an aqueous solution with beryllium oxide powder. The lithium hydroxide is converted in situ to lithium carbonate by contacting or flooding the beryllium oxide-lithium hydroxide blend with a stream of carbon dioxide. The lithium carbonate is converted to lithium oxide while remaining fixed to the beryllium oxide particles during the hot pressing step to assure uniform density throughout the compact.

  9. Dissolving method for nuclear fuel oxide

    International Nuclear Information System (INIS)

    Tomiyasu, Hiroshi; Kataoka, Makoto; Asano, Yuichiro; Hasegawa, Shin-ichi; Takashima, Yoichi; Ikeda, Yasuhisa.

    1996-01-01

    In a method of dissolving oxides of nuclear fuels in an aqueous acid solution, the oxides of the nuclear fuels are dissolved in a state where an oxidizing agent other than the acid is present together in the aqueous acid solution. If chlorate ions (ClO 3 - ) are present together in the aqueous acid solution, the chlorate ions act as a strong oxidizing agent and dissolve nuclear fuels such as UO 2 by oxidation. In addition, a Ce compound which generates Ce(IV) by oxidation is added to the aqueous acid solution, and an ozone (O 3 ) gas is blown thereto to dissolve the oxides of nuclear fuels. Further, the oxides of nuclear fuels are oxidized in a state where ClO 2 is present together in the aqueous acid solution to dissolve the oxides of nuclear fuels. Since oxides of the nuclear fuels are dissolved in a state where the oxidizing agent is present together as described above, the oxides of nuclear fuels can be dissolved even at a room temperature, thereby enabling to use a material such as polytetrafluoroethylene and to dissolve the oxides of nuclear fuels at a reduced cost for dissolution. (T.M.)

  10. Oxidation phase growth diagram of vanadium oxides film fabricated by rapid thermal annealing

    Institute of Scientific and Technical Information of China (English)

    Tamura KOZO; Zheng-cao LI; Yu-quan WANG; Jie NI; Yin HU; Zheng-jun ZHANG

    2009-01-01

    Thermal evaporation deposited vanadium oxide films were annealed in air by rapid thermal annealing (RTP). By adjusting the annealing temperature and time, a series of vanadium oxide films with various oxidation phases and surface morphologies were fabricated, and an oxidation phase growth diagram was established. It was observed that different oxidation phases appear at a limited and continuous annealing condition range, and the morphologic changes are related to the oxidation process.

  11. RESIDUAL RISK ASSESSMENT: ETHYLENE OXIDE ...

    Science.gov (United States)

    This document describes the residual risk assessment for the Ethylene Oxide Commercial Sterilization source category. For stationary sources, section 112 (f) of the Clean Air Act requires EPA to assess risks to human health and the environment following implementation of technology-based control standards. If these technology-based control standards do not provide an ample margin of safety, then EPA is required to promulgate addtional standards. This document describes the methodology and results of the residual risk assessment performed for the Ethylene Oxide Commercial Sterilization source category. The results of this analyiss will assist EPA in determining whether a residual risk rule for this source category is appropriate.

  12. Oxidation of amines by flavoproteins.

    Science.gov (United States)

    Fitzpatrick, Paul F

    2010-01-01

    Many flavoproteins catalyze the oxidation of primary and secondary amines, with the transfer of a hydride equivalent from a carbon-nitrogen bond to the flavin cofactor. Most of these amine oxidases can be classified into two structural families, the D-amino acid oxidase/sarcosine oxidase family and the monoamine oxidase family. This review discusses the present understanding of the mechanisms of amine and amino acid oxidation by flavoproteins, focusing on these two structural families. Copyright 2009 Elsevier Inc. All rights reserved.

  13. Aromatic-radical oxidation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Glassman, I.; Brezinsky, K. [Princeton Univ., NJ (United States)

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  14. Supported versus colloidal zinc oxide for advanced oxidation processes

    Science.gov (United States)

    Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

    2017-07-01

    Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

  15. Graphene oxide and H2 production from bioelectrochemical graphite oxidation.

    Science.gov (United States)

    Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

    2015-11-17

    Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES.

  16. Protective effect of nitric oxide against arsenic-induced oxidative ...

    African Journals Online (AJOL)

    The effects of NO on alleviating arsenic-induced oxidative damage in tall fescue leaves were investigated. Arsenic (25 M) treatment induced significantly accumulation of reactive oxygen species (ROS) and led to serious lipid peroxidation in tall fescue leaves and the application of 100 M SNP before arsenic stress resulted ...

  17. Oxidation of aniline with strong and weak oxidants

    Czech Academy of Sciences Publication Activity Database

    Sapurina, I. Yu.; Stejskal, Jaroslav

    2012-01-01

    Roč. 82, č. 2 (2012), s. 256-275 ISSN 1070-3632 R&D Projects: GA AV ČR IAA400500905 Institutional research plan: CEZ:AV0Z40500505 Keywords : polyaniline * conducting polymer * oxidant Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.432, year: 2012

  18. SELECTIVE OXIDATION IN SUPERCRITICAL CARBON DIOXIDE USING CLEAN OXIDANTS

    Science.gov (United States)

    We have systematically investigated heterogeneous catalytic oxidation of different substrates in supercritical carbon dioxide (SC-CO2). Three types of catagysts: a metal complex, 0.5% platinum g-alumina and 0.5% palladium g-alumina were used at a pressure of 200 bar, temperatures...

  19. Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

    Science.gov (United States)

    Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

    2017-06-01

    The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

  20. New insight of high temperature oxidation on self-exfoliation capability of graphene oxide

    Science.gov (United States)

    Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

    2018-05-01

    The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

  1. [Solidification of volatile oil with graphene oxide].

    Science.gov (United States)

    Yan, Hong-Mei; Jia, Xiao-Bin; Zhang, Zhen-Hai; Sun, E; Xu, Yi-Hao

    2015-02-01

    To evaluate the properties of solidifying volatile oil with graphene oxide, clove oil and zedoary turmeric oil were solidified by graphene oxide. The amount of graphene oxide was optimized with the eugenol yield and curcumol yield as criteria. Curing powder was characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The effects of graphene oxide on dissolution in vitro and thermal stability of active components were studied. The optimum solidification ratio of graphene oxide to volatile oil was 1:1. Dissolution rate of active components had rare influence while their thermal stability improved after volatile oil was solidified. Solidifying herbal volatile oil with graphene oxide deserves further study.

  2. Thermal Oxidation of Structured Silicon Dioxide

    DEFF Research Database (Denmark)

    Christiansen, Thomas Lehrmann; Hansen, Ole; Jensen, Jørgen Arendt

    2014-01-01

    The topography of thermally oxidized, structured silicon dioxide is investigated through simulations, atomic force microscopy, and a proposed analytical model. A 357 nm thick oxide is structured by removing regions of the oxide in a masked etch with either reactive ion etching or hydrofluoric acid....... Subsequent thermal oxidation is performed in both dry and wet ambients in the temperature range 950◦C to 1100◦C growing a 205 ± 12 nm thick oxide in the etched mask windows. Lifting of the original oxide near the edge of the mask in the range 6 nm to 37 nm is seen with increased lifting for increasing...

  3. Metal oxide/polyaniline nanocomposites

    Indian Academy of Sciences (India)

    Nanocomposites of iron oxide with conducting polymer in the form of powders of varying compositions have been studied to understand the effects of particle size, cluster size and magnetic inter-particle interactions. The sizes of the nanoparticles were estimated to be ∼ 10–20 nm from the X-ray diffraction (XRD) and the ...

  4. Ferroelectricity in undoped hafnium oxide

    International Nuclear Information System (INIS)

    Polakowski, Patrick; Müller, Johannes

    2015-01-01

    We report the observation of ferroelectric characteristics in undoped hafnium oxide thin films in a thickness range of 4–20 nm. The undoped films were fabricated using atomic layer deposition (ALD) and embedded into titanium nitride based metal-insulator-metal (MIM) capacitors for electrical evaluation. Structural as well as electrical evidence for the appearance of a ferroelectric phase in pure hafnium oxide was collected with respect to film thickness and thermal budget applied during titanium nitride electrode formation. Using grazing incidence X-Ray diffraction (GIXRD) analysis, we observed an enhanced suppression of the monoclinic phase fraction in favor of an orthorhombic, potentially, ferroelectric phase with decreasing thickness/grain size and for a titanium nitride electrode formation below crystallization temperature. The electrical presence of ferroelectricity was confirmed using polarization measurements. A remanent polarization P r of up to 10 μC cm −2 as well as a read/write endurance of 1.6 × 10 5 cycles was measured for the pure oxide. The experimental results reported here strongly support the intrinsic nature of the ferroelectric phase in hafnium oxide and expand its applicability beyond the doped systems

  5. Plasma electrolytic oxidation of metals

    Directory of Open Access Journals (Sweden)

    Stojadinović Stevan

    2013-01-01

    Full Text Available In this lecture results of the investigation of plasma electrolytic oxidation (PEO process on some metals (aluminum, titanium, tantalum, magnesium, and zirconium were presented. Whole process involves anodizing metals above the dielectric breakdown voltage where numerous micro-discharges are generated continuously over the coating surface. For the characterization of PEO process optical emission spectroscopy and real-time imaging were used. These investigations enabled the determination of electron temperature, electron number density, spatial density of micro-discharges, the active surface covered by micro-discharges, and dimensional distribution of micro-discharges at various stages of PEO process. Special attention was focused on the results of the study of the morphology, chemical, and phase composition of oxide layers obtained by PEO process on aluminum, tantalum, and titanium in electrolytes containing tungsten. Physicochemical methodes: atomic force microscopy (AFM, scanning electron microscopy (SEM-EDS, x-ray diffraction (XRD, x-ray photoelectron spectroscopy (XPS, and Raman spectroscopy served as tools for examining obtained oxide coatings. Also, the application of the obtained oxide coatings, especially the application of TiO2/WO3 coatings in photocatalysis, were discussed.

  6. In-Situ Chemical Oxidation

    Science.gov (United States)

    2006-08-01

    wells at a bioremediation field site (Weisner et al., 1996). Colloidal clay particles mobilized during injec- tion have resulted in permeability losses...phase material. Nevertheless, O3 was readily delivered and transported through unsaturated porous media where phenanthrene and diesel range...tion, but is not currently a well-developed technology. Bioremediation : Sequencing oxidation and reduction reactions may be achieved through

  7. Riboflavin photosensitized oxidation of myoglobin.

    Science.gov (United States)

    Grippa, Juliana M; de Zawadzki, Andressa; Grossi, Alberto B; Skibsted, Leif H; Cardoso, Daniel R

    2014-02-05

    The reaction of the fresh meat pigment oxymyoglobin, MbFe(II)O₂, and its oxidized form metmyoglobin, MbFe(III), with triplet-state riboflavin involves the pigment protein, which is oxidatively cleaved or dimerized as shown by SDS-PAGE and Western blotting. The overall rate constant for oxidation of MbFe(II)O₂ by ³Rib is (3.0 ± 0.5) × 10⁹ L·mol⁻¹·s⁻¹ and (3.1 ± 0.4) × 10⁹ L·mol⁻¹·s⁻¹ for MbFe(III) in phosphate buffer of pH 7.4 at 25 °C as determined by laser flash photolysis. The high rates are rationalized by ground state hydrophobic interactions as detected as static quenching of fluorescence from singlet-excited state riboflavin by myoglobins using time-resolved fluorescence spectroscopy and a Stern-Volmer approach. Binding of riboflavin to MbFe(III) has K(a) = (1.2 ± 0.2) × 10⁴ mol·L⁻¹ with ΔH° = -112 ± 22 kJ·mol⁻¹ and ΔS° = -296 ± 75 J·mol⁻¹·K⁻¹. For meat, riboflavin is concluded to be a photosensitizer for protein oxidation but not for discoloration.

  8. Radiation annealing in cuprous oxide

    DEFF Research Database (Denmark)

    Vajda, P.

    1966-01-01

    Experimental results from high-intensity gamma-irradiation of cuprous oxide are used to investigate the annealing of defects with increasing radiation dose. The results are analysed on the basis of the Balarin and Hauser (1965) statistical model of radiation annealing, giving a square...

  9. Perovskite catalysts for oxidative coupling

    Science.gov (United States)

    Campbell, Kenneth D.

    1991-01-01

    Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  10. Corium Oxidation at Temperatures Above 2000 K

    International Nuclear Information System (INIS)

    Hagrman, Donald L.; Rempe, Joy L.

    2001-01-01

    A mechanistic model, based on a quasi-equilibrium analysis of oxidation reactions, is proposed for predicting high-temperature corium oxidation. The analysis suggests that oxide forming on the surface of corium containing uranium, zirconium, and iron is similar to the oxides formed on zirconium and uranium as long as there is a small percentage of unoxidized zirconium or uranium in the metallic phase. This is because of the higher affinity of zirconium and uranium for oxygen. Hence, oxidation rates and heat production rates are similar to (U,Zr) compounds until nearly all the uranium and zirconium in the corium oxidizes. Oxidation rates after this point are predicted to be similar to those implied by the oxide thickness present when the forming oxide ceases to be protective, and heat generation rates should be similar to those implied by iron oxidation, i.e., ∼4% of the zirconium oxidation heating rate.The maximum atomic ratio of unoxidized iron to unoxidized liquid zirconium plus uranium for the formation of a solid protective oxide below 2800 K is estimated for a temperature, T (in Kelvin), as follows:(unoxidized iron)/(unoxidized zirconium + turanium) = (1/28){5.7/exp[-(147 061 + 12.08T log(T) - 61.03T - 0.000555T 2 /1.986T)]} 1/2 .As long as this limit is not exceeded, either zirconium or uranium metal oxidation rates and heating describe the corium oxidation rate. If this limit is exceeded, diffusion of steam to the corium surface will limit the oxidation rate, and linear time-dependent growth of a nonprotective, mostly FeO, layer will occur below the protective (Zr,U) O 2 scale. When this happens, the oxidation should be at the constant rate given by the thickness of the protective layer. Heat generation should be similar to that of iron oxidation

  11. Corium Oxidation at Temperatures Above 2000 K

    Energy Technology Data Exchange (ETDEWEB)

    Hagrman, Donald Lee; Rempe, Joy Lynn

    2001-02-01

    A mechanistic model, based on a quasi-equilibrium analysis of oxidation reactions, is proposed for predicting high-temperature corium oxidation. The analysis suggests that oxide forming on the surface of corium containing uranium, zirconium, and iron is similar to the oxides formed on zirconium and uranium as long as there is a small percentage of unoxidized zirconium or uranium in the metallic phase. This is because of the higher affinity of zirconium and uranium for oxygen. Hence, oxidation rates and heat production rates are similar to (U,Zr) compounds until nearly all the uranium and zirconium in the corium oxidizes. Oxidation rates after this point are predicted to be similar to those implied by the oxide thickness present when the forming oxide ceases to be protective, and heat generation rates should be similar to those implied by iron oxidation, i.e., ~4% of the zirconium oxidation heating rate. The maximum atomic ratio of unoxidized iron to unoxidized liquid zirconium plus uranium for the formation of a solid protective oxide below 2800 K is estimated for a temperature, T (in Kelvin), as follows: (unoxidized iron)/(unoxidized zirconium + turanium) = (1/28){5.7/exp[-(147 061 + 12.08T log(T) - 61.03T - 0.000555T2/1.986T)]}1/2. As long as this limit is not exceeded, either zirconium or uranium metal oxidation rates and heating describe the corium oxidation rate. If this limit is exceeded, diffusion of steam to the corium surface will limit the oxidation rate, and linear time-dependent growth of a nonprotective, mostly FeO, layer will occur below the protective (Zr,U) O2 scale. When this happens, the oxidation should be at the constant rate given by the thickness of the protective layer. Heat generation should be similar to that of iron oxidation.

  12. Oxidation of pyrite: Consequences and significance

    Directory of Open Access Journals (Sweden)

    Dimitrijević Mile D.

    2002-01-01

    Full Text Available This paper presents the most important studies on the oxidation of pyrite particularly in aqueous solutions. The consequences of pyrite oxidation was examined, as well as its importance, from both the technical-technological and environmental points of view. The oxidation of pyrite was considered in two parts. The spontaneous oxidation of pyrite in nature was described in the first part, with this part comprising pyrite oxidation in deposits depots and mines. It is explained how way natural electrochemical processes lead to the decomposition of pyrite and other minerals associated with pyrite. The oxidation of pyrite occurring during technological processes such as grinding, flotation and leaching, was shown in the second part. Particular emphasis was placed on the oxidation of pyrite during leaching. This part includes the leaching of sulphide and oxide ores, the leaching of pyrite coal and the leaching of refractory gold-bearing ores (pressure oxidation, bacterial oxidation, oxidation by means of strong oxidants and the electrolysis of pyrite suspensions. Various mechanisms of pyrite oxidation and of the galvanic interaction of pyrite with other sulphide minerals are shown.

  13. Selective propene oxidation on mixed metal oxide catalysts

    International Nuclear Information System (INIS)

    James, David William

    2002-01-01

    Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

  14. Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2014-07-28

    Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.

  15. Oxidative stress in cardiovascular diseases

    Directory of Open Access Journals (Sweden)

    Shyamal K Goswami

    2015-01-01

    Full Text Available Oxidative stress caused by various oxygen containing free radicals and reactive species (collectively called "Reactive Oxygen Species" or ROS has long been attributed to cardiovascular diseases. In human body, major oxidizing species are super oxide, hydrogen peroxide, hydroxyl radical, peroxy nitrite etc. ROS are produced from distinct cellular sources, enzymatic and non-enzymatic; have specific physicochemical properties and often have specific cellular targets. Although early studies in nineteen sixties and seventies highlighted the deleterious effects of these species, later it was established that they also act as physiological modulators of cellular functions and diseases occur only when ROS production is deregulated. One of the major sources of cellular ROS is Nicotinamide adenine dinucleotide phosphate oxidases (Noxes that are expressed in almost all cell types. Superoxide and hydrogen peroxide generated from them under various conditions act as signal transducers. Due to their immense importance in cellular physiology, various Nox inhibitors are now being developed as therapeutics. Another free radical of importance in cardiovascular system is nitric oxide (a reactive nitrogen species generated from nitric oxide synthase(s. It plays a critical role in cardiac function and its dysregulated generation along with superoxide leads to the formation of peroxynitrite a highly deleterious agent. Despite overwhelming evidences of association between increased level of ROS and cardiovascular diseases, antioxidant therapies using vitamins and omega 3 fatty acids have largely been unsuccessful till date. Also, there are major discrepancies between studies with laboratory animals and human trials. It thus appears that the biology of ROS is far complex than anticipated before. A comprehensive understanding of the redox biology of diseases is thus needed for developing targeted therapeutics.

  16. The properties of protective oxide scales containing cerium on alloy 800H in oxidizing and oxidizing/sulphidizing environments

    NARCIS (Netherlands)

    Haanappel, V.A.C.; Haanappel, V.A.C.; Fransen, T.; Geerdink, Bert; Gellings, P.J.; Stroosnijder, M.F.

    1991-01-01

    The corrosion protection of oxide scales formed by electrophoretic deposition in a cerium-containing sol on Alloy 800H, a 32Ni-20Cr steel, followed by firing in air at 1123 K was studied in oxidizing and mixed oxidizing/sulphidizing environments at elevated temperatures. In particular, the influence

  17. Experimental investigation and thermodynamic simulation of the uranium oxide-zirconium oxide-iron oxide system in air

    Czech Academy of Sciences Publication Activity Database

    Petrov, Y. B.; Udalov, Y. P.; Šubrt, Jan; Bakardjieva, Snejana; Sázavský, P.; Kiselová, M.; Selucký, P.; Bezdička, Petr; Joumeau, C.; Piluso, P.

    2011-01-01

    Roč. 37, č. 2 (2011), s. 212-229 ISSN 1087-6596 Institutional research plan: CEZ:AV0Z40320502 Keywords : uranium oxide * zirconium oxide * iron oxide * fusibility curve * oxygen partial pressure * crystallization * phase composition Subject RIV: CA - Inorganic Chemistry Impact factor: 0.492, year: 2011

  18. "UCx fission targets oxidation test stand"

    CERN Document Server

    Lacroix, Rachel

    2014-01-01

    "Set up a rig dedicated to the oxidation of UCx and define a procedure for repeatable, reliable and safe method for converting UC2 fission targets into an acceptable uranium carbide oxide waste for subsequent disposal by the Swiss Authorities."

  19. Methods for synthesizing metal oxide nanowires

    Science.gov (United States)

    Sunkara, Mahendra Kumar; Kumar, Vivekanand; Kim, Jeong H.; Clark, Ezra Lee

    2016-08-09

    A method of synthesizing a metal oxide nanowire includes the steps of: combining an amount of a transition metal or a transition metal oxide with an amount of an alkali metal compound to produce a mixture; activating a plasma discharge reactor to create a plasma discharge; exposing the mixture to the plasma discharge for a first predetermined time period such that transition metal oxide nanowires are formed; contacting the transition metal oxide nanowires with an acid solution such that an alkali metal ion is exchanged for a hydrogen ion on each of the transition metal oxide nanowires; and exposing the transition metal oxide nanowires to the plasma discharge for a second predetermined time period to thermally anneal the transition metal oxide nanowires. Transition metal oxide nanowires produced using the synthesis methods described herein are also provided.

  20. Consecutive dynamic resolutions of phosphine oxides

    NARCIS (Netherlands)

    Kortmann, Felix A.; Chang, Mu-Chieh; Otten, Edwin; Couzijn, Erik P. A.; Lutz, Martin; Minnaard, Adriaan J.

    2013-01-01

    A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio-and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides.

  1. Oxidation catalysts and process for preparing same

    International Nuclear Information System (INIS)

    1980-01-01

    Compounds particularly suitable as oxidation catalysis are described, comprising specified amounts of uranium, antimony and tin as oxides. Processes for making and using the catalysts are described. (U.K.)

  2. Transparent Oxide Semiconductors for Emerging Electronics

    KAUST Repository

    Caraveo-Frescas, Jesus Alfonso

    2013-01-01

    Transparent oxide electronics have emerged as promising materials to shape the future of electronics. While several n-type oxides have been already studied and demonstrated feasibility to be used as active materials in thin film transistors, high

  3. Electrochemical, Chemical and Enzymatic Oxidations of Phenothiazines

    NARCIS (Netherlands)

    Blankert, B.; Hayen, H.; van Leeuwen, S.M.; Karst, U.; Bodoki, E.; Lotrean, S.; Sandulescu, R.; Mora Diaz, N.; Dominguez, O.; Arcos, J.; Kauffmann, J.-M.

    2005-01-01

    The oxidation of several phenothiazine drugs (phenothiazine, promethazine hydrochloride, promazine hydrochloride, trimeprazine hydrochloride and ethopropazine hydrochloride) has been carried out in aqueous acidic media by electrochemical, chemical and enzymatic methods. The chemical oxidation was

  4. Nanostructured Thermoelectric Oxides for Energy Harvesting Applications

    KAUST Repository

    Abutaha, Anas I.

    2015-01-01

    of thermoelectrics are still limited to one materials system, namely SiGe, since the traditional thermoelectric materials degrade and oxidize at high temperature. Therefore, oxide thermoelectrics emerge as a promising class of materials since they can operate

  5. Oxidation of boron carbide at high temperatures

    International Nuclear Information System (INIS)

    Steinbrueck, Martin

    2005-01-01

    The oxidation kinetics of various types of boron carbides (pellets, powder) were investigated in the temperature range between 1073 and 1873 K. Oxidation rates were measured in transient and isothermal tests by means of mass spectrometric gas analysis. Oxidation of boron carbide is controlled by the formation of superficial liquid boron oxide and its loss due to the reaction with surplus steam to volatile boric acids and/or direct evaporation at temperatures above 1770 K. The overall reaction kinetics is paralinear. Linear oxidation kinetics established soon after the initiation of oxidation under the test conditions described in this report. Oxidation is strongly influenced by the thermohydraulic boundary conditions and in particular by the steam partial pressure and flow rate. On the other hand, the microstructure of the B 4 C samples has a limited influence on oxidation. Very low amounts of methane were produced in these tests

  6. Solid Oxide Fuel Cell Experimental Laboratory

    Data.gov (United States)

    Federal Laboratory Consortium — NETL’s Solid Oxide Fuel Cell Experimental Laboratory in Morgantown, WV, gives researchers access to models and simulations that predict how solid oxide fuel cells...

  7. Sodium Perborate Oxidation of an Aromatic Amine

    Science.gov (United States)

    Juestis, Laurence

    1977-01-01

    Describes an experiment involving the oxidation of aromatic primary amines to the corresponding azo compound; suggests procedures for studying factors that influence the yield of such a reaction, including the choice of solvent and the oxidant-amine ratio. (MLH)

  8. Clinical Relevance of Biomarkers of Oxidative Stress

    DEFF Research Database (Denmark)

    Frijhoff, Jeroen; Winyard, Paul G; Zarkovic, Neven

    2015-01-01

    SIGNIFICANCE: Oxidative stress is considered to be an important component of various diseases. A vast number of methods have been developed and used in virtually all diseases to measure the extent and nature of oxidative stress, ranging from oxidation of DNA to proteins, lipids, and free amino ac....... The vast diversity in oxidative stress between diseases and conditions has to be taken into account when selecting the most appropriate biomarker.......SIGNIFICANCE: Oxidative stress is considered to be an important component of various diseases. A vast number of methods have been developed and used in virtually all diseases to measure the extent and nature of oxidative stress, ranging from oxidation of DNA to proteins, lipids, and free amino...... acids. RECENT ADVANCES: An increased understanding of the biology behind diseases and redox biology has led to more specific and sensitive tools to measure oxidative stress markers, which are very diverse and sometimes very low in abundance. CRITICAL ISSUES: The literature is very heterogeneous...

  9. Periodontitis and increase in circulating oxidative stress

    OpenAIRE

    Takaaki Tomofuji; Koichiro Irie; Toshihiro Sanbe; Tetsuji Azuma; Daisuke Ekuni; Naofumi Tamaki; Tatsuo Yamamoto; Manabu Morita

    2009-01-01

    Reactive oxygen species (ROS) are products of normal cellular metabolism. However, excessive production of ROS oxidizes DNA, lipids and proteins, inducing tissue damage. Studies have shown that periodontitis induces excessive ROS production in periodontal tissue. When periodontitis develops, ROS produced in the periodontal lesion diffuse into the blood stream, resulting in the oxidation of blood molecules (circulating oxidative stress). Such oxidation may be detrimental to systemic health. Fo...

  10. Diesel soot oxidation under controlled conditions

    OpenAIRE

    Song, Haiwen

    2003-01-01

    This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University, 11/12/2003. In order to improve understanding of diesel soot oxidation, an experimental rig was designed and set up, in which the soot oxidation conditions, such as temperature, oxygen partial pressure, and CO2 partial pressure, could be varied independently of each other. The oxidizing gas flow in the oxidizer was under laminar condition. This test rig comprised a naturally-aspirated single ...

  11. Mechanisms of wet oxidation by hydrogen peroxide

    International Nuclear Information System (INIS)

    Baxter, R.A.

    1987-08-01

    A research programme is currently under way at BNL and MEL to investigate the possible use of Hydrogen Peroxide with metal ion catalysts as a wet oxidation treatment system for CEGB organic radioactive wastes. The published literature relating to the kinetics and mechanism of oxidation and decomposition reactions of hydrogen peroxide is reviewed and the links with practical waste management by wet oxidation are examined. Alternative wet oxidation systems are described and the similarities to the CEGB research effort are noted. (author)

  12. Oxidation of 1-butene over uranium oxide (UO3)-antimony oxide (Sb2O3) catalysts

    NARCIS (Netherlands)

    Simons, T.; Houtman, P.N.; Schuit, G.C.A.

    1971-01-01

    The oxidative dehydrogenation of butene to butadiene over U-Sb catalysts was investigated. The presence of two compds., (UO2)Sb3O7 and Sb3U3O14, reported by Grasselli and Callahan (1969), was confirmed with (UO2)Sb3O7 being the actual catalyst. The reaction is first order in butene and zero order in

  13. Absorption and oxidation of nitrogen oxide in ionic liquids

    DEFF Research Database (Denmark)

    Kunov-Kruse, Andreas Jonas; Thomassen, Peter Langelund; Riisager, Anders

    2016-01-01

    A new strategy for capturing nitrogen oxide, NO, from the gas phase is presented. Dilute NO gas is removed from the gas phase by ionic liquids under ambient conditions. The nitrate anion of the ionic liquid catalyzes the oxidation of NO to nitric acid by atmospheric oxygen in the presence of water....... The nitric acid is absorbed in the ionic liquid up to approximately one mole HNO3 per mole of the ionic liquid due to the formation of hydrogen bonds. The nitric acid can be desorbed by heating, thereby regenerating the ionic liquid with excellent reproducibility. Here, time-resolved in-situ spectroscopic...... investigations of the reaction and products are presented. The procedure reveals a new vision for removing the pollutant NO by absorption into a non-volatile liquid and converting it into a useful bulk chemical, that is, HNO3....

  14. The initial oxidation of magnesium

    Energy Technology Data Exchange (ETDEWEB)

    Kurth, M.

    2004-07-01

    Pure Magnesium samples have been oxidised in an UHV chamber under controlled conditions. Pressure range was 10{sup -10} Torr to 10{sup -7} Torr, temperature range was 273 K to 435 K. The samples have then been investigated with XPS, Ellipsometry and HERDA. Additionally, furnace oxidations at 750 Torr and 673 K have been carried out and investigated with XPS. From the XPS measurements data concerning layer thickness, composition, oxidation state and binding state have been gained. The ellipsometrie measurements yielded additional data concerning layer thickness as well as the size of the band gap of the developing oxide. With the HERDA measurements, the oxygen content within the oxide layer has been determined yielding additional information about composition and layer thickness. The layer thickness as a function of time have then been modelled with a kinetic growth model of Fromhold and Cook. For the refinement of the XPS data concerning layer thickness and composition, the pronounced plasmon excitations that occur in magnesium have been determined with two different procedures which have been developed in the methodical part of this work. The layer thickness and composition values have thus been corrected. Results: Two oxidation stages could be identified: a strong increase for the first few Langmuirs (1L = 1s x 10{sup -6} Torr), followed by a saturation'' region which was about 1.2 nm to 1.5 nm in magnitude. XPS and ellipsometry results have thereby been in very good agreement. The composition of the developing oxide showed a clear deviation from stoichiometric MgO, mainly caused by an oxygen deficiency; this deficiency has also been confirmed with the HERDA measurements. The Mg/O ratio as a function of layer thickness showed a continous decay starting from very high values for the thinnest layers (>{proportional_to}2.5) down to a saturation value of about 1.4, even for larger layer thicknesses gained with the furnace oxidations. The determination of

  15. New oxidation and photo-oxidation products of tryptophan

    International Nuclear Information System (INIS)

    Savige, W.E.

    1975-01-01

    Dye-sensitized photo-oxidation of tryptophan in water gives N'-formylkynurenine and (+-)-3a-hydroxy-1,2,3a,8,8a-hexahydropyrrolo[2,3-b] indole-2-carboxylic acid. The latter rearranges to oxindolyl-3-alanine on irradiation with UV light and reacts with thiols, including cysteine, in warm 20% acetic acid to give the corresponding 2-tryptophyl sulphides. (orig.) [de

  16. Dense high temperature ceramic oxide superconductors

    Science.gov (United States)

    Landingham, Richard L.

    1993-01-01

    Dense superconducting ceramic oxide articles of manufacture and methods for producing these articles are described. Generally these articles are produced by first processing these superconducting oxides by ceramic processing techniques to optimize materials properties, followed by reestablishing the superconducting state in a desired portion of the ceramic oxide composite.

  17. 21 CFR 582.1210 - Calcium oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium oxide. 582.1210 Section 582.1210 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1210 Calcium oxide. (a) Product. Calcium oxide. (b) Conditions of use. This substance is generally...

  18. 21 CFR 582.5210 - Calcium oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium oxide. 582.5210 Section 582.5210 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS... 1 § 582.5210 Calcium oxide. (a) Product. Calcium oxide. (b) Conditions of use. This substance is...

  19. Free energy of hydration of niobium oxide

    International Nuclear Information System (INIS)

    Plodinec, M.J.

    1996-01-01

    Some of the glasses being formulated by SRTC researchers contain niobium oxide. In this report, the free energy of hydration of the oxide is calculated from the free energies of formation of the oxide, the hydroxide, and water. This value can be used in calculations of the free energy of hydration of glasses containing niobium

  20. 29 CFR 1910.105 - Nitrous oxide.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 5 2010-07-01 2010-07-01 false Nitrous oxide. 1910.105 Section 1910.105 Labor Regulations... OCCUPATIONAL SAFETY AND HEALTH STANDARDS Hazardous Materials § 1910.105 Nitrous oxide. The piped systems for the in-plant transfer and distribution of nitrous oxide shall be designed, installed, maintained, and...

  1. Nitrous oxide emissions from estuarine intertidal sediments

    NARCIS (Netherlands)

    Middelburg, J.J.; Klaver, G.; Nieuwenhuize, J.; Markusse, R.M.; Vlug, T.; Nat, F.J.W.A. van der

    1995-01-01

    From September 1990 through December 1991 nitrous oxide flux measurements were made at 9 intertidal mud flat sites in the Scheldt Estuary. Nitrous oxide release rates were highly variable both between sites and over time at any one site. Annual nitrous oxide fluxes vary from about 10 mmol N m-2 at

  2. Separation medium containing thermally exfoliated graphite oxide

    Science.gov (United States)

    Prud'homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Herrera-Alonso, Margarita (Inventor)

    2012-01-01

    A separation medium, such as a chromatography filling or packing, containing a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m.sup.2/g to 2600 m.sup.2/g, wherein the thermally exfoliated graphite oxide has a surface that has been at least partially functionalized.

  3. Air Quality Criteria for Sulfur Oxides.

    Science.gov (United States)

    National Air Pollution Control Administration (DHEW), Washington, DC.

    Included is a literature review which comprehensively discusses knowledge of the sulfur oxides commonly found in the atmosphere. The subject content is represented by the 10 chapter titles: Physical and Chemical Properties and the Atmospheric Reactions of the Oxides of Sulfur; Sources and Methods of Measurements of Sulfur Oxides in the Atmosphere;…

  4. Graphene oxide reduction recipes, spectroscopy, and applications

    CERN Document Server

    Gao, Wei

    2015-01-01

    This book focuses on a group of new materials labeled ""graphene oxides."" It provides a comprehensive overview of graphene oxide-based nanomaterials in terms of their synthesis, structures, properties, and extensive applications in catalysis, separation, filtration, energy storage and conversion. The book also covers emerging research on graphite oxides and the impact of the research on fundamental and applied sciences.

  5. 49 CFR 173.323 - Ethylene oxide.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Ethylene oxide. 173.323 Section 173.323... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.323 Ethylene oxide. (a) For packaging ethylene oxide in non-bulk packagings, silver mercury or any of its alloys or copper may not be used in any...

  6. 29 CFR 1910.1047 - Ethylene oxide.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 6 2010-07-01 2010-07-01 false Ethylene oxide. 1910.1047 Section 1910.1047 Labor... Ethylene oxide. (a) Scope and application. (1) This section applies to all occupational exposures to ethylene oxide (EtO), Chemical Abstracts Service Registry No. 75-21-8, except as provided in paragraph (a...

  7. On chemical activity of heavy metal oxides

    International Nuclear Information System (INIS)

    Mechev, V.V.

    1994-01-01

    Interaction of solid oxides of heavy nonferrous metals with sulfur and carbon is investigated. The results are discussed. Direct dependence of chemical activity of oxides on disordering of their crystal lattice at heating is established. Beginning of interaction in the systems studied is accompanied by change of oxide conductivity type

  8. 21 CFR 582.5431 - Magnesium oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Magnesium oxide. 582.5431 Section 582.5431 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5431 Magnesium oxide. (a) Product. Magnesium oxide. (b) Conditions of use. This substance...

  9. 21 CFR 582.1431 - Magnesium oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Magnesium oxide. 582.1431 Section 582.1431 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1431 Magnesium oxide. (a) Product. Magnesium oxide. (b) Conditions of use. This substance is...

  10. 21 CFR 184.1431 - Magnesium oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium oxide. 184.1431 Section 184.1431 Food and... Substances Affirmed as GRAS § 184.1431 Magnesium oxide. (a) Magnesium oxide (MgO, CAS Reg. No. 1309-48-4... powder (light) or a relatively dense white powder (heavy) by heating magnesium hydroxide or carbonate...

  11. 21 CFR 73.3125 - Iron oxides.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

  12. Synthesis of vertically aligned metal oxide nanostructures

    KAUST Repository

    Roqan, Iman S.; Flemban, Tahani H.

    2016-01-01

    ablation of a target including a metal oxide and, optionally, a dopant. In some embodiments zinc oxide nanostructures are deposited onto a substrate by pulsed laser deposition of a zinc oxide target using an excimer laser emitting UV radiation. The zinc

  13. Structure and catalytic reactivity of Rh oxides

    DEFF Research Database (Denmark)

    Gustafson, J.; Westerström, R.; Resta, A.

    2009-01-01

    Using a combination of experimental and theoretical techniques, we show that a thin RhO2 surface oxide film forms prior to the bulk Rh2O3 corundum oxide on all close-packed single crystal Rh surfaces. Based on previous reports, we argue that the RhO2 surface oxide also forms on vicinal Rh surface...

  14. Limits to the adherence of oxide scales

    International Nuclear Information System (INIS)

    Robertson, J.; Manning, M.I.

    1989-10-01

    Fracture mechanics is used to identify criteria under which uniform oxide scales may be expected to fail due to rapidly applied strains. The most common failure mode occurs when the strain, ε, builds up in the scale until the strain energy density per unit area exceeds the fracture surface energy, γ, of the oxide. This produces spalling when ε > (2γ/hE) 1/2 , where h is the scale thickness and E is the oxide Youngs modulus. In thin scales, as the external strain is applied to the oxide via the metal substrate, it is clear that no further strain can be applied to the oxide if the substrate has itself been strained beyond yield. This gives rise to extended oxide adherence in which the oxide cracks and forms a series of islands but remains attached to the deformed metal. When the oxide thickness is less than its comminution limit, the flaw size necessary for brittle fracture exceeds the oxide thickness and the oxide yields in a ductile manner without cracking. The results are presented as maps of failure strain versus oxide thickness for various oxide systems such as Fe 3 O 4 , Cr 2 O 3 , Al 2 O 3 , SiO 2 and NiO. The observed cases of spalling are found to lie within the predicted regions. (author)

  15. Shocked plate metal atom oxidation laser

    International Nuclear Information System (INIS)

    De Koker, J.G.; Rice, W.W. Jr.; Jensen, R.J.

    1975-01-01

    A method and apparatus for producing metal atom oxidation lasing wherein an explosively shocked grooved metal plate produces metal vapor jets directed through an appropriate gaseous oxidizer are described. Reaction of the metal vapor with the oxidizer produces molecular species having a population inversion therein. (U.S.)

  16. 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

  17. Oxidized Lipoprotein as a Major Vessel Cell Proliferator in Oxidized Human Serum.

    Directory of Open Access Journals (Sweden)

    Yoshiro Saito

    Full Text Available Oxidative stress is correlated with the incidence of several diseases such as atherosclerosis and cancer, and oxidized biomolecules have been determined as biomarkers of oxidative stress; however, the detailed molecular relationship between generated oxidation products and the promotion of diseases has not been fully elucidated. In the present study, to clarify the role of serum oxidation products in vessel cell proliferation, which is related to the incidence of atherosclerosis and cancer, the major vessel cell proliferator in oxidized human serum was investigated. Oxidized human serum was prepared by free radical exposure, separated using gel chromatography, and then each fraction was added to several kinds of vessel cells including endothelial cells and smooth muscle cells. It was found that a high molecular weight fraction in oxidized human serum specifically induced vessel cell proliferation. Oxidized lipids were contained in this high molecular weight fraction, while cell proliferation activity was not observed in oxidized lipoprotein-deficient serum. Oxidized low-density lipoproteins induced vessel cell proliferation in a concentration-dependent manner. Taken together, these results indicate that oxidized lipoproteins containing lipid oxidation products function as a major vessel cell proliferator in oxidized human serum. These findings strongly indicate the relevance of determination of oxidized lipoproteins and lipid oxidation products in the diagnosis of vessel cell proliferation-related diseases such as atherosclerosis and cancer.

  18. Advanced methods for the treatment of organic aqueous wastes: wet air oxidation and wet peroxide oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Debellefontaine, Hubert; Chakchouk, Mehrez; Foussard, Jean Noel [Institut National des Sciences Appliquees (INSA), 31 - Toulouse (France). Dept. de Genie des Procedes Industriels; Tissot, Daniel; Striolo, Phillipe [IDE Environnement S.A., Toulouse (France)

    1993-12-31

    There is a growing concern about the problems of wastes elimination. Various oxidation techniques are suited for elimination of organic aqueous wastes, however, because of the environmental drawbacks of incineration, liquid phase oxidation should be preferred. `Wet Air Oxidation` and `Wet Peroxide Oxidation`are alternative processes which are discussed in this paper. 17 refs., 13 figs., 4 tabs.

  19. Polyaniline: Aniline oxidation with strong and weak oxidants under various acidity

    Energy Technology Data Exchange (ETDEWEB)

    Bláha, Michal, E-mail: blaha@imc.cas.cz [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Trchová, Miroslava; Bober, Patrycja; Morávková, Zuzana [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Prokeš, Jan [Charles University, Faculty of Mathematics and Physics, 180 00 Prague 8 (Czech Republic); Stejskal, Jaroslav [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic)

    2017-06-15

    Aniline was oxidized with three strong inorganic oxidants (ammonium peroxydisulfate, cerium(IV) sulfate, potassium dichromate), two weak inorganic oxidants (iron(III) chloride, silver nitrate), and one organic oxidant (p-benzoquinone) in aqueous solutions of methanesulfonic acid (MSA) of various concentration. Whereas oxidation of aniline with ammonium peroxydisulfate yielded high-molecular-weight conducting polyaniline (PANI) in the whole acidity range, the oxidation with cerium(IV) sulfate led also to a single product close to PANI with considerably lower molecular weight and lower conductivity. Potassium dichromate gave PANI only at high concentration of MSA. The use of iron(III) chloride yielded composite mixtures of PANI and low-molecular-weight aniline oligomers. The oxidation of aniline with silver nitrate led to composites of silver and an organic part, which was constituted either by aniline oligomers or conducting polyaniline or both. p-Benzoquinone as oxidant produced mainly aniline oligomers with poor conductivity and 2,5-dianilino-p-benzoquinone-like structure detected in FTIR and Raman spectra when oxidation proceeded with weak oxidants. A general model of oxidation with strong and weak oxidants was formulated. - Highlights: • Comparison of aniline oxidation with oxidants of different redox potential. • UV–vis, FTIR and Raman spectroscopies combined with size-exclusion chromatography. • The contents of polymer and oligomers were analyzed and discussed. • General model of aniline oxidation with strong and weak oxidants was formulated.

  20. Advanced methods for the treatment of organic aqueous wastes: wet air oxidation and wet peroxide oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Debellefontaine, Hubert; Chakchouk, Mehrez; Foussard, Jean Noel [Institut National des Sciences Appliquees (INSA), 31 - Toulouse (France). Dept. de Genie des Procedes Industriels; Tissot, Daniel; Striolo, Phillipe [IDE Environnement S.A., Toulouse (France)

    1994-12-31

    There is a growing concern about the problems of wastes elimination. Various oxidation techniques are suited for elimination of organic aqueous wastes, however, because of the environmental drawbacks of incineration, liquid phase oxidation should be preferred. `Wet Air Oxidation` and `Wet Peroxide Oxidation`are alternative processes which are discussed in this paper. 17 refs., 13 figs., 4 tabs.