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Sample records for prsub 6ru octahedra

  1. Tetrahedra, octahedra and cubo-octahedra: integrable geometry of multi-ratios

    Science.gov (United States)

    King, A. D.; Schief, W. K.

    2003-01-01

    Geometric and algebraic aspects of multi-ratios M2N are investigated in detail. Connections with Menelaus' theorem, Clifford configurations and Maxwell's reciprocal quadrangles are utilized to associate the multi-ratios M4, M8 and M8 with tetrahedra, octahedra and cubo-octahedra respectively. Integrable maps defined on face-centred (fcc) lattices and irregular lattices composed of the face centres of simple cubic lattices are constructed and related to the discrete KP and BKP equations and the integrable discrete Darboux system governing conjugate lattices. An interpretation in terms of integrable irregular lattices of slopes on the plane is also given.

  2. Tetrahedra, octahedra and cubo-octahedra integrable geometry of multi-ratios

    CERN Document Server

    King, A D

    2003-01-01

    Geometric and algebraic aspects of multi-ratios M sub 2 sub N are investigated in detail. Connections with Menelaus' theorem, Clifford configurations and Maxwell's reciprocal quadrangles are utilized to associate the multi-ratios M sub 4 , M sub 8 and M sub 8 with tetrahedra, octahedra and cubo-octahedra respectively. Integrable maps defined on face-centred (fcc) lattices and irregular lattices composed of the face centres of simple cubic lattices are constructed and related to the discrete KP and BKP equations and the integrable discrete Darboux system governing conjugate lattices. An interpretation in terms of integrable irregular lattices of slopes on the plane is also given.

  3. Pr{sub 1.33}Pt{sub 4}Ga{sub 10}: Superstructure and magnetism

    Energy Technology Data Exchange (ETDEWEB)

    Doan Nguyen, Sau; Ryan, Kevin [Department of Chemistry and Biochemistry, University of Northern Colorado, Greeley, CO 80639 (United States); Chai, Ping [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306 (United States); Shatruk, Michael [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306 (United States); National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Xin, Yan [National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Chapman, Karena W.; Chupas, Peter J. [X-Ray Science Division, The Advanced Photon Source, Argonne National Laboratory, Lemont, IL 60439 (United States); Fronczek, Frank R. [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Macaluso, Robin T., E-mail: robin.macaluso@unco.edu [Department of Chemistry and Biochemistry, University of Northern Colorado, Greeley, CO 80639 (United States)

    2014-12-15

    Pr{sub 1.33}Pt{sub 4}Ga{sub 10} crystals were prepared by Ga-flux method. The superstructure of this compound was studied by single-crystal X-ray diffraction (XRD), transmission electron microscopy (TEM), and diffuse X-ray scattering. Pr{sub 1.33}Pt{sub 4}Ga{sub 10} adopts the P6{sub 3}/mmc space group with a=b=4.3227(5) Å, c=16.485(3) Å: the structure features Pr{sub 2}Ga{sub 3} layers alternating with Pt{sub 2}Ga{sub 4} layers along the c-axis. TEM studies and pair distribution function (PDF) analysis of X-ray total scattering data show that Pr{sub 2}Ga{sub 3} layers possess an ordered superstructure (of dimension a′=a√(3)) in which Pr vacancies and Ga atoms are ordered within the ab-plane but disordered along the c-direction. PDF analysis also shows temperature-dependent structural features local to the Pr{sup 3+} ion. Magnetic measurements reveal that Pr{sup 3+} ions order ferrimagnetically below 12.5(2) K. - Graphical abstract: Left: Crystal structure of Pr{sub 1.33}Pt{sub 4}Ga{sub 10} showing Pr and Ga vacancies in the Pr{sub 2}Ga{sub 3} plane. Right: Tunneling electron microscopy (TEM) image of Pr{sub 1.33}Pt{sub 4}Ga{sub 10}. These vacancies have been studied using TEM and pair distribution function analysis. Magnetic measurements reveal that Pr{sup 3+} ions order ferrimagnetically below 7.8(2) K. - Highlights: • TEM studies indicate a superstructure from Pr and Ga vacancies. • Pair distribution function analyses may point to structural relaxation of vacancies. • Pr{sub 1.33}Pt{sub 4}Ga{sub 10} behaves as a ferromagnet and exhibits a metamagnetic transition.

  4. Synthesis and characterization of highly efficient and stable Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt ternary hybrid structure

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Jiatao; Liu, Lin; Niu, Tongjun; Sun, Xiaosong, E-mail: sunxs@scu.edu.cn

    2017-05-01

    Highlights: • Visible-light-driven Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt photocatalysts were prepared. • Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt showed highly efficient and stable photocatalystic activity. • The photocatalytic mechanism of Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt composite was given. - Abstract: Ag{sub 3}PO{sub 4} is an excellent photocatalyst with high efficiency and quantum yield, but suffers from the fast recombination of photogenerated electron-hole pairs and photo-corrosion. Hereby, the highly efficient and stable visible-light-driven Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt photocatalyst were prepared via a three-step wet chemical approach. The as-prepared Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt composite was characterized by X-ray diffraction, US-vis diffuse reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectra and transient photocurrent as well. Comparing with single Pr{sub 6}O{sub 11} or Ag{sub 3}PO{sub 4}, the prepared Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt composite exhibited much higher photocatalytic activity and stability for the degradation of Rhodamine B under visible light irradiation (>420 nm). The enhanced photocatalytic performance of Pr{sub 6}O{sub 11}/Ag{sub 3}PO{sub 4}/Pt composite has been attributed to the efficient separation of photo-generated electron-hole pairs through a scheme system composed of Pr{sub 6}O{sub 11,} Ag{sub 3}PO{sub 4} and Pt.

  5. Magnetic characterization of Pr{sub 2}BaCuO{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Saez Puche, R [Departamento de Quimica Inorganica I, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Climent-Pascual, E [Departamento de Quimica Inorganica I, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Paz, J Romero de [Departamento de Quimica Inorganica I, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Fernandez-Diaz, M T [Institut Laue-Langevin, BP 156X, F-38042 Grenoble Cedex (France); Cascales, C [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28094-Madrid (Spain)

    2008-01-30

    The magnetic behaviour of Pr{sub 2}BaCuO{sub 5} oxide has been studied by means of magnetic susceptibility, magnetization, specific heat and neutron powder diffraction at low temperatures. This oxide behaves as an antiferromagnetic with a Neel temperature of 13.7 K and the magnetic structure can be described on the basis of a wavevector k = [0,0,0]. The Cu{sup 2+} magnetic moments are aligned along the c-axis of the crystal structure, while the Pr{sup 3+} magnetic moments lie in the ab-plane with a small component along the c-axis. The experimental values of the ordered moments at 2 K are 0.9(3) and 0.8(3) {mu}{sub B} for copper and praseodymium ions, respectively. The obtained set of crystal field parameters reproduces the paramagnetic susceptibility measurements and justifies the low experimental ordered moment of the Pr{sup 3+} ion.

  6. Direct observation of titanium-centered octahedra in titanium-antimony-tellurium phase-change material.

    Science.gov (United States)

    Rao, Feng; Song, Zhitang; Cheng, Yan; Liu, Xiaosong; Xia, Mengjiao; Li, Wei; Ding, Keyuan; Feng, Xuefei; Zhu, Min; Feng, Songlin

    2015-11-27

    Phase-change memory based on Ti0.4Sb2Te3 material has one order of magnitude faster Set speed and as low as one-fifth of the Reset energy compared with the conventional Ge2Sb2Te5 based device. However, the phase-transition mechanism of the Ti0.4Sb2Te3 material remains inconclusive due to the lack of direct experimental evidence. Here we report a direct atom-by-atom chemical identification of titanium-centered octahedra in crystalline Ti0.4Sb2Te3 material with a state-of-the-art atomic mapping technology. Further, by using soft X-ray absorption spectroscopy and density function theory simulations, we identify in amorphous Ti0.4Sb2Te3 the titanium atoms preferably maintain the octahedral configuration. Our work may pave the way to more thorough understanding and tailoring of the nature of the Ti-Sb-Te material, for promoting the development of dynamic random access memory-like phase-change memory as an emerging storage-class memory to reform current memory hierarchy.

  7. New electrochemiluminescence catalyst: Cu2O semiconductor crystal and the enhanced activity of octahedra synthesized by iodide ions coordination

    Science.gov (United States)

    Zhang, Ling; Qi, Liming; Gao, Wenyue; Niu, Wenxin; Luque, Rafael; Xu, Guobao

    2017-11-01

    Cuprous oxide (Cu2O) crystals are usually used as the photocatalysts of water splittings and carbon monoxide oxidations. Herein, we report the new catalytic properties of Cu2O to the electrochemilumenescence (ECL) reactions of luminol and oxygen. Adjusting the shape of Cu2O microcrystals from cube to octahedra also facilities the improved electrocatalytic acticity, where octahedral Cu2O microcrystals possess higher ECL signal by 25% at  ‑0.6 V (versus Ag/AgCl) at pH 7.4. The octahedral Cu2O microcrystals are synthesized by the coordination of iodide ions to the surface, which alters the crystals shapes from cubes to octahedra. Size-distribution of octahedra is improved with this mehod compared to the previous studies with only hydroxide ions as the coordinates. The catalytic activity of octahedral Cu2O crystals is expected to be compared with the noble metal nanomaterials and constructed the high-efficiency and low-cost ECL biosensors.

  8. Monoclinic superstructure of Pr{sub 3}Rh{sub 4}Ge{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Vosswinkel, Daniel; Hoffmann, Rolf-Dieter; Greiwe, Magnus; Eul, Matthias; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2016-07-01

    Pr{sub 3}Rh{sub 4}Ge{sub 4} was synthesized by melting of the elements in an arc-melting furnace followed by annealing in a sealed tantalum ampoule in a muffle furnace. Structure refinement was based on temperature dependent single-crystal X-ray diffractometer data. At ambient temperature Pr{sub 3}Rh{sub 4}Ge{sub 4} adopts the U{sub 3}Ni{sub 4}Si{sub 4} type structure with strongly enhanced anisotropic displacement parameters for Rh1. Below 230 K additional reflections start to appear and at 110 K the structure could be described with the (3+1)D superspace group I2/m(α0γ)00; α=1/2, γ=1/2; (Z=2). This commensurately modulated structure could be refined with 1448 F{sup 2} values, 39 variables and residuals of wR=0.0417 for the main reflections and wR=0.1520 for the satellites of 1{sup st} order, [a=408.36(2), b=421.12(3) and c=2504.4(2) pm]. The commensurate description could be transformed to a 3D supercell with space group A2/m and Z=4: a=816.72(2), b=421.12(3), c=2537.5(1) pm, β=99.26(1) , 1448 F{sup 2} values, 69 variables and wR=0.0499. The relation of the U{sub 3}Ni{sub 4}Si{sub 4} type structure, the (3+1)D modulated and the 3D supercell is discussed on the basis of a group-subgroup scheme. Temperature dependent magnetic susceptibility data reveal Curie-Weiss paramagnetism with an experimental moment of 3.72(2) μ{sub B}/Pr atom and a Weiss constant of -12.6(5) K. No magnetic ordering is evident down to 3 K.

  9. Neutron spectroscopic study of the crystal field interaction in Pr{sub 1-x}La{sub x}NiO{sub 3} (0{<=}x{<=}0.7)

    Energy Technology Data Exchange (ETDEWEB)

    Rosenkranz, S.; Medarde, M.; Mesot, J.; Zolliker, M.; Furrer, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Lacorre, P. [LeMans, Univ. (France)

    1997-09-01

    The crystal field interaction at the rare earth site in Pr{sub 1-x}La{sub x}NiO{sub 3} has been studied using inelastic neutron scattering. A parametrization consistent over the whole series is obtained and discussed within the point-charge model. (author) 2 figs., 3 refs.

  10. Investigation of diphasic region in the Pr{sub 2}O{sub 3} + Sm{sub 2}O{sub 3} mixed oxide system at various temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Vijayalakshmi, D. [Department of Physics, Kanchi Mamunivar Centre for PG and Research Studies, Govt. of Pondicherry, Lawspet 605008, Pondicherry (India); High Pressure Physics Section, Condensed Matter Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Chandra Shekar, N.V., E-mail: chandru@igcar.gov.i [High Pressure Physics Section, Condensed Matter Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Ramya, S. [Corrosion Science and Technology Division, Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Sahu, P.Ch. [High Pressure Physics Section, Condensed Matter Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Meenakshi, G. [Department of Physics, Kanchi Mamunivar Centre for PG and Research Studies, Govt. of Pondicherry, Lawspet 605008, Pondicherry (India)

    2010-09-03

    X-ray diffraction studies on mixed rare-earth oxides Pr{sub 2}O{sub 3} and Sm{sub 2}O{sub 3} quenched at various temperatures were carried out and their phase relationship was analyzed. Mixtures of Pr{sub 2}O{sub 3} and Sm{sub 2}O{sub 3} at different compositions were heated at various temperatures in the range 500-1200 {sup o}C and then air quenched. The structures of these quenched samples were analyzed using X-ray diffraction and Raman spectroscopy. Pure Pr{sub 2}O{sub 3} and Sm{sub 2}O{sub 3} exhibit C-type cubic phase at NTP. While Pr{sub 2}O{sub 3} retains its cubic phase up to 1200 {sup o}C, the Sm{sub 2}O{sub 3} transformed to B-type monoclinic phase above 800 {sup o}C. However, their mixtures when heated at different temperatures showed interesting structural behaviour. For the mixture up to 40 wt.% of Sm{sub 2}O{sub 3} in Pr{sub 2}O{sub 3}, no significant change was observed at lower temperatures ({approx}800 {sup o}C), and the C-type cubic phase was observed. As the ratio was gradually increased above 40%, a diphasic region in the range 50-70% was observed, with a combination of both C-type cubic and B-type monoclinic phases. When the temperature was raised to 1200 {sup o}C, the 80% of Sm{sub 2}O{sub 3} shows a complete structural transition from cubic to monoclinic phase. Based on the analysis of our results various crystal structures and stability regimes of mixed oxide have been reported.

  11. Thermodynamic analyses of structural phase transition of Pr{sub 2}NiO{sub 4+δ} involving variation of oxygen content

    Energy Technology Data Exchange (ETDEWEB)

    Niwa, Eiki, E-mail: e-niwa@phys.chs.nihon-u.ac.jp [Department of Physics, College of Humanities and Sciences, Nihon University, 3-8-1 Sakurajousui, Setagaya-ku, Tokyo 156-8550 (Japan); Wakai, Kazuya [Department of Integrated Sciences in Physics and Biology, College of Humanities and Sciences, Nihon University, 3-8-1 Sakurajousui, Setagaya-ku, Tokyo 156-8550 (Japan); Hori, Tetsuya; Yashiro, Keiji; Mizusaki, Junichiro [Institute of Multidisciplinary Research for Advance Materials, Tohoku University, Sendai 980-8577 (Japan); Hashimoto, Takuya [Department of Integrated Sciences in Physics and Biology, College of Humanities and Sciences, Nihon University, 3-8-1 Sakurajousui, Setagaya-ku, Tokyo 156-8550 (Japan)

    2014-01-10

    Graphical abstract: - Highlights: • P(O{sub 2}) dependence of phase transition behavior of Pr{sub 2}NiO{sub 4+δ} was investigated. • The structural phase transition was measured by DSC and TG–DTA. • ΔH and ΔS of Pr{sub 2}NiO{sub 4+δ} were confirmed to be almost constant against P(O{sub 2}). • Variation of oxygen content at the phase transition, Δδ changed by P(O{sub 2}). • The origin of different Δδ by P(O{sub 2}) is valence change of Pr ion. - Abstract: Structural phase transition behavior of Pr{sub 2}NiO{sub 4+δ}, which attracts interest as new cathode material for solid oxide fuel cells, was investigated by DSC and TG–DTA under controlled oxygen partial pressure, P(O{sub 2}). It was revealed that the structural phase transition from orthorhombic phase to tetragonal phase involved discrete decrease of oxygen content in Pr{sub 2}NiO{sub 4+δ} and that the phase transition temperature, T{sub p}, decreased with decreasing P(O{sub 2}). Variation of enthalpy, ΔH, and entropy, ΔS, at the phase transition per one molar Pr{sub 2}NiO{sub 4+δ} were calculated from the peak area of DSC and they were independent on P(O{sub 2}) between 1.0 × 10{sup −1} bar and 2.25 × 10{sup −3} bar. From the linear relationships between T{sub p} and RT{sub p}ln P(O{sub 2}) and between 1/T{sub p} and Rln P(O{sub 2}), variation of standard enthalpy, ΔH°, and standard entropy, ΔS°, of the phase transition per one molar O{sub 2} were calculated, showing fair agreement with ΔH and ΔS. The variation of oxygen content at the phase transition, Δδ, increased with decreasing P(O{sub 2}), which can be attributed to valence variation of Pr in tetragonal Pr{sub 2}NiO{sub 4+δ} by P(O{sub 2})

  12. Locking of iridium magnetic moments to the correlated rotation of oxygen octahedra in Sr2IrO4 revealed by x-ray resonant scattering

    DEFF Research Database (Denmark)

    Boseggia, S.; Walker, H. C.; Vale, J.

    2013-01-01

    .8(1)° of the oxygen octahedra that characterizes its distorted layered perovskite structure. Using x-ray resonant scattering at the Ir L3 edge we have measured accurately the intensities of Bragg peaks arising from different components of the magnetic structure. From a careful comparison of integrated intensities...

  13. Enhanced detection of nitrogen dioxide via combined heating and pulsed UV operation of indium oxide nano-octahedra.

    Science.gov (United States)

    Gonzalez, Oriol; Roso, Sergio; Vilanova, Xavier; Llobet, Eduard

    2016-01-01

    We report on the use of combined heating and pulsed UV light activation of indium oxide gas sensors for enhancing their performance in the detection of nitrogen dioxide in air. Indium oxide nano-octahedra were synthesized at high temperature (900 °C) via vapour-phase transport and screen-printed onto alumina transducers that comprised interdigitated electrodes and a heating resistor. Compared to the standard, constant temperature operation of the sensor, mild heating (e.g., 100 °C) together with pulsed UV light irradiation employing a commercially available, 325 nm UV diode (square, 1 min period, 15 mA drive current signal), results in an up to 80-fold enhancement in sensitivity to nitrogen dioxide. Furthermore, this combined operation method allows for making savings in power consumption that range from 35% to over 80%. These results are achieved by exploiting the dynamics of sensor response under pulsed UV light, which convey important information for the quantitative analysis of nitrogen dioxide.

  14. Enhanced detection of nitrogen dioxide via combined heating and pulsed UV operation of indium oxide nano-octahedra

    Directory of Open Access Journals (Sweden)

    Oriol Gonzalez

    2016-10-01

    Full Text Available We report on the use of combined heating and pulsed UV light activation of indium oxide gas sensors for enhancing their performance in the detection of nitrogen dioxide in air. Indium oxide nano-octahedra were synthesized at high temperature (900 °C via vapour-phase transport and screen-printed onto alumina transducers that comprised interdigitated electrodes and a heating resistor. Compared to the standard, constant temperature operation of the sensor, mild heating (e.g., 100 °C together with pulsed UV light irradiation employing a commercially available, 325 nm UV diode (square, 1 min period, 15 mA drive current signal, results in an up to 80-fold enhancement in sensitivity to nitrogen dioxide. Furthermore, this combined operation method allows for making savings in power consumption that range from 35% to over 80%. These results are achieved by exploiting the dynamics of sensor response under pulsed UV light, which convey important information for the quantitative analysis of nitrogen dioxide.

  15. Growth of polycrystalline Pr{sub 2}NiO{sub 4+δ} coating on alumina substrate by RF magnetron co-sputtering from composite targets

    Energy Technology Data Exchange (ETDEWEB)

    Sediri, A., E-mail: amal.sediri@univ-tours.fr [Université François-Rabelais de Tours, GREMAN UMR 7347 CNRS, IUT de Blois 15 rue de la chocolaterie CS 2903, 41029 Blois Cedex (France); Zaghrioui, M.; Barichard, A.; Autret, C.; Negulescu, B. [Université François-Rabelais de Tours, GREMAN UMR 7347 CNRS, IUT de Blois 15 rue de la chocolaterie CS 2903, 41029 Blois Cedex (France); Del Campo, L.; Echegut, P. [CNRS, UPR 3079 CEMHTI, 45071 Orléans Cedex 2 (France); Laffez, P. [Université François-Rabelais de Tours, GREMAN UMR 7347 CNRS, IUT de Blois 15 rue de la chocolaterie CS 2903, 41029 Blois Cedex (France)

    2016-02-01

    Polycrystalline Pr{sub 2}NiO{sub 4+δ} coatings have been deposited on alumina substrates at room temperature by RF magnetron co-sputtering from Pr and Ni metallic composite target. The mixed target's area and the sputtering conditions were optimized to reach an atomic ratio Pr/Ni of 2. A subsequent annealing, at 1050–1100 °C, allowed obtaining Pr{sub 2}NiO{sub 4+δ} phase after in situ high temperature x-ray diffraction study performed on as-deposited film. Microstructural analyses (SEM and AFM) revealed dense and rough microstructure. Normal spectral emittance measurements performed at 794 °C in the spectral range 400–5000 cm{sup -1} showed an emissivity of ε ≈ 0.8. - Highlights: • Pr{sub 2}NiO{sub 4+δ} coatings deposited by RF magnetron co-sputtering • Crystallization kinetic studied by X-ray diffraction versus temperature • SEM and AFM observations showed dense and rough microstructure • Normal spectral emittance reaches to ε = 0.8 at 794 °C in the opaque zone.

  16. Porous MnO/C of composite nanostructure consisting of nanorods and nano-octahedra as anode of lithium ion batteries with enhanced electrochemical performances

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yue-Feng; Xu, Gui-Liang [State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Su, Hang [College of Energy, Xiamen University, Xiamen 361005 (China); Chen, Yuan; Fang, Jun-Chuan; Wang, Qi; Huang, Ling [State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Li, Jun-Tao [College of Energy, Xiamen University, Xiamen 361005 (China); Sun, Shi-Gang, E-mail: sgsun@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2016-08-15

    Porous MnO/C materials of composite nanostructure consisting of nanorods and nano-octahedra (denoted as nRO-MnO/C) were synthesized for the first time through a one-pot hydrothermal procedure followed by thermal annealing using PEG6000 as a soft template. When served as anode of LIBs, the nRO-MnO/C materials could maintain a reversible capacity as high as 861.3 mAh g{sup −1} after 120 cycles at a rate of 0.13 C (1 C = 755.6 mA g{sup −1}), and a stable capacity of 313.5 mAh g{sup −1} at a much higher rate of 4.16 C. Moreover, excellent long cycleability at high rate has been also evidenced by a capacity of 628.9 mAh g{sup −1} measured after 300 cycles at 1.32 C. In comparison with mono-form porous nanorods (nR-MnO/C) and mono-form porous nano-octahedra (nO-MnO/C), the enhanced electrochemical performances of the nRO-MnO/C materials are attributed to the composite nanostructure, in which the nano-octahedra contact effectively with nanorods by laying in the space between them yielding synergy effect that facilitates the electronic transportation on electrode. - Highlights: • Porous MnO/C with composite nanostructure was prepared by hydrothermal reaction. • The composite nanostructure is consisting of nanorods and nano-octahedra. • The nRO-MnO/C delivers a charge capacity of 628.9 mAh g{sup −1} after 300 cycles at 1.32 C. • The superior electrochemical performance should be owed to composite structure.

  17. Nanoscopic characterization of Pr{sub 2}Zr{sub 2}O{sub 7} at Zr sites

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, J.A.; Caracoche, M.C.; Rodriguez, A.M. [Departamento de Fisica, IFLP, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 1900 La Plata (Argentina); Rivas, P.C. [Departamento de Fisica, IFLP, Facultad de Ciencias Exactas y Facultad de Ciencias Agronomicas y Forestales, Universidad Nacional de La Plata, 1900 La Plata (Argentina); Bondioli, F.; Manfredini, T. [Dipartimento di Ingegneria dei Materiali e dell' Ambiente, Facolta di Ingegneria, Universita di Modena e Reggio Emilia, 41100 Modena (Italy); Ferrari, A.M. [Dipartimento di Scienze e Metodi dell' Ingegneria, Facolta di Ingegneria, Universita di Modena e Reggio Emilia, 42100 Reggio Emilia (Italy)

    2005-07-01

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

  18. Between Localization and Delocalization: Ru(cod)(2+) Units in the Zintl Clusters [Bi9 {Ru(cod)}2 ](3-) and [Tl2 Bi6 {Ru(cod)}](2).

    Science.gov (United States)

    Lichtenberger, Niels; Spang, Nils; Eichhöfer, Andreas; Dehnen, Stefanie

    2017-10-16

    Reactions of [K(crypt-222)]2 (TlBi3 )⋅0.5 en (1 b) with [Ru(cod)(H2 CC(Me)CH2 )2 ] (A) in 1,2-diaminoethane (en) led to the formation of two compounds with new bismuth-rich cluster anions, [K(crypt-222)]3 [Bi9 {Ru(cod)}2 ]⋅1.5 en (2) and [K(crypt-222)]2 [Tl2 Bi6 {Ru(cod)}]⋅2 tol (3), alongside the salt of a binary nido cluster, [K(crypt-222)]3 (Tl4 Bi5 )⋅2 en (4). The anions in 2 and 3 are two further examples of rare heterometallic clusters containing Ru atoms. As one cod ligand is retained on each Ru atom in both clusters, the anions may be viewed as intermediates on the way towards larger, ligand-free intermetalloid clusters. Quantum-chemical studies provided insight into the bonding situation in these clusters. According to these studies, the anion of 2 features both electron-precise and electron-deficient parts. Electrospray ionization mass spectrometry analysis indicated that the clusters undergo stepwise fragmentation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Concerning the electronic coupling of MoMo quadruple bonds linked by 4,4'-azodibenzoate and comparison with t2g 6-Ru(II) centers by 4,4'-azodiphenylcyanamido ligands.

    Science.gov (United States)

    Chisholm, Malcolm H; D'Acchioli, Jason S; Hadad, Christopher M; Patmore, Nathan J

    2006-12-25

    From the reactions between Mo2(O2CtBu)4 and each of terephthalic acid and 4,4'-azodibenzoic acid, the compounds [Mo2(O2CtBu)3]2(mu-O2CC6H4CO2) (1) and [Mo2(O2CtBu)3]2(mu-O2CC6H4N2C6H4CO2) (2) have been made and characterized by spectroscopic and electrochemical methods. Their electronic structures have been examined by computations employing density functional theory on model compounds where HCO2 substitutes for tBuCO2. On the basis of these studies, the two Mo2 units are shown to be only weakly coupled and the mixed-valence ions 1+ and 2+ to be valence-trapped and Class II and I, respectively, on the Robin-Day classification scheme for mixed-valence compounds. These results are compared to t2g6-Ru centers linked by 1,4-dicyanamidobenzene and azo-4,4'-diphenylcyanamido bridges for which the mixed-valence ions [Ru-bridge-Ru]5+ have been previously classified as fully delocalized, Class III [Crutchley et al. Inorg. Chem. 2001, 40, 1189; Inorg. Chem. 2004, 43, 1770], and on the basis of results described herein, it is proposed that the latter complex ion is more likely a mixed-valence organic radical where the bridge is oxidized and not the Ru(2+) centers.

  20. Dielectric and ferroelectric characteristics of Ba{sub 4}Pr{sub 2}Fe{sub 2}Nb{sub 8}O{sub 30} tungsten bronze ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Ting Ting; Chen, Wang; Zhu, Xiao Na; Zhu, Xiao Li; Chen, Xiang Ming, E-mail: xmchen59@zju.edu.cn

    2016-09-15

    Ba{sub 4}Pr{sub 2}Fe{sub 2}Nb{sub 8}O{sub 30} tungsten bronze ceramics have been prepared by a standard solid-state sintering method, and the electrical, dielectric and ferroelectric properties have been determined together with the structure. The structure dependence of ferroelectricity has been investigated by comparing the as-sintered, N{sub 2}-annealed and O{sub 2}-annealed samples. The typical relaxor ferroelectric nature is generally indicated in the present ceramics, where the broaden dielectric constant and dielectric loss peaks with strong frequency dispersion feature are observed. The peak temperatures for both dielectric constant and dielectric loss are significantly increased together with the much stronger frequency dispersion by N{sub 2}-annealing, while the O{sub 2}-annealing results in the decreased peak temperatures and the suppressed frequency dispersion. These phenomena are closely related to the valences of Fe and Pr ions. The hopping between Fe{sup 2+} and Fe{sup 3+} inside the grains causes the dielectric relaxation in as-sintered and N{sub 2}-annealed samples. The enhanced ferroelectricity near room temperature is attributed to the increased ion radius difference between A1 and A2 ions because of the “substitution” Pr{sup 4+} for Pr{sup 3+} after N{sub 2}-annealing. - Highlights: • Dielectric and ferroelectric properties of Ba{sub 4}Pr{sub 2}Fe{sub 2}Nb{sub 8}O{sub 30} are investigated. • Ferroelectric hysteresis loop is observed in Ba{sub 4}Pr{sub 2}Fe{sub 2}Nb{sub 8}O{sub 30} ceramics. • The ferroelectric properties are closely related to the valences of Pr ions. • The ferroelectric transition temperature is dominated by the radius difference between A1-and A2-site.

  1. X-ray resonant scattering studies of charge and orbital ordering in Pr{sub 1{minus}z}, Ca{sub x}, MnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    V.ZIMMERMANN,M.; NELSON,C.S.; HILL,J.P.; GIBBS,D.; BLUME,M.; CASA,D.; KEIMER,B.; MURAKAMI,Y.; KAO,C.C.; VENKATARAMAN,C.; GOG,T.; TOMIOKA,Y.; TOKURA,Y.

    2000-08-14

    We present the results of x-ray scattering studies of the charge and orbital ordering in the manganite series Pr{sub 1{minus}z}, Ca{sub x}, MnO{sub 3} with x = 0.25, 0.4 and 0.5. The polarization and azimuthal dependence of the charge and orbital ordering in these compounds is characterized both in the resonant and nonresonant limits, and compared with the predictions of current theories. The results are qualitatively consistent with both cluster and LDA+U calculations of the electronic structure.

  2. Structure of compound Pr{sub 5}Mo{sub 3}O{sub 16+δ} exhibiting mixed electronic—ionic conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Antipin, A. M., E-mail: antipin@physics.msu.ru; Alekseeva, O. A.; Sorokina, N. I.; Kuskova, A. N.; Artemov, V. V. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Murzin, V. Yu. [National Research Center “Kurchatov Institute” (Russian Federation); Kharitonava, E. P.; Orlova, E. A.; Voronkova, V. I. [Moscow State University, Faculty of Physics (Russian Federation)

    2015-09-15

    The structure of Pr{sub 5}Mo{sub 3}O{sub 16+δ} single crystals is studied by X-ray diffraction, EDXS microanalysis, transmission microscopy, and XANES spectroscopy. It is found that in the structure Pr and Mo cations mutually replace each other, atomic positions of oxygen are split into several additional positions, and structural voids accommodate interstitial oxygen atoms (which make the main contribution to the conductivity). The disorder of the oxygen sublattice is responsible for the continuity of the framework of the ways of migration of oxygen ions.

  3. Distortion of MnO{sub 6} octahedra and electrochemical activity of Nstutite-based MnO{sub 2} polymorphs for alkaline electrolytes - an FTIR study

    Energy Technology Data Exchange (ETDEWEB)

    Ananth, M.V.; Pethkar, S.; Dakshinamurthi, K. [Central Electrochemical Research Inst., Madras Unit, CSIR Complex, Chennai (India)

    1998-10-01

    Infrared fourier transform (FTIR) spectroscopic analysis of four commercial manganese dioxides having applications in alkaline batteries is reported. These samples of different alkaline activity have Nstutite or {gamma}-MnO{sub 2} as the major phase. With respect to the interaction of Mn with OH{sup -} and other groups, the development of weak bands around 1363 cm{sup -1} represents the variation in discharge performance. Significant changes are seen in the MnO{sub 6} octahedral arrangement from sample to sample by examining the spectra in low-frequency regions. Distortion of MnO{sub 6} octahedra by the constituent water promotes the electrochemical behaviour. In general, the alkaline electrochemical activity of Nstutite MnO{sub 2} samples can be understood from their infrared spectra. (orig.)

  4. Change of conduction mechanism in the impedance of grain boundaries in Pr{sub 0.4}Ca{sub 0.6}MnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Matiullah [EMMG, Physics Division, PINSTECH, PO Nilore, Islamabad (Pakistan); Department of Chemical and Material Engineering, PIEAS, Islamabad 45650 (Pakistan); Nadeem, M., E-mail: mnadeem@pinstech.org.pk [EMMG, Physics Division, PINSTECH, PO Nilore, Islamabad (Pakistan); Idrees, M. [EMMG, Physics Division, PINSTECH, PO Nilore, Islamabad (Pakistan); Physics Department, COMSATS Institue of Information Technology, Lahore (Pakistan); Atif, M. [Department of Physics, Air University, PAF Complex E-9, Islamabad (Pakistan); Akhtar, M.J. [EMMG, Physics Division, PINSTECH, PO Nilore, Islamabad (Pakistan)

    2013-04-15

    Freshly synthesized polycrystalline Pr{sub 0.4}Ca{sub 0.6}MnO{sub 3} sample has been analyzed by employing X-ray diffraction, magnetization and impedance spectroscopic techniques. Magnetization M(T) showed charge ordering (T{sub CO}) around 268 K and below this temperature variation of magnetic and electric field effects is discussed. With the decrease of temperature, the change in the size and shape of the impedance plane plot is explored in terms of modulation of different relaxation processes. An equivalent circuit model (RQ) is used to determine the electrical parameters of Pr{sub 0.4}Ca{sub 0.6}MnO{sub 3} sample at different temperatures. Impedance of grain boundaries derived from the fitting of experimental data using an equivalent circuit model shows a change in conduction mechanism from small polaron hopping (SPH) to the variable range hopping (VRH) model around 148 K. Activation energies calculated from the SPH model and relaxation frequencies of imaginary part of impedance are compared and discussed. Average normalized change (ANC) deduced from the impedance data illustrates a change in conduction mechanism around 148 K due to the superexchange networks of Mn{sup 3+} and Mn{sup 4+}. - Highlights: ► Different field effects originated below charge ordering temperature. ► A transition around 148 K is established across the grain boundaries. ► Conduction mechanism changes from SPH to the VRH model. ► The Relaxation frequency shows dependent as well as independent regions.

  5. Colossal elastoresistance, electroresistance and magnetoresistance in Pr{sub 0.5}Sr{sub 0.5}MnO{sub 3} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Liping, E-mail: chenliping0003@163.com [Department of Physics, Zhejiang Normal University, Jinhua 321004 (China); Department of Physics, Hong Kong University, Hong Kong (China); Guo, Xuexiang [Department of Physics, Zhejiang Normal University, Jinhua 321004 (China); Gao, J. [Department of Physics, Hong Kong University, Hong Kong (China)

    2016-05-01

    Pr{sub 0.5}Sr{sub 0.5}MnO{sub 3} thin films on substrates of (001)-oriented LaAlO{sub 3} were epitaxially grown by pulsed laser deposition. It was found that a substrate-induced strain of ~1.3% brings a great resistivity change of ~98% at 25 K. We studied the dependence of resistivity on the applied electric current and magnetic field. In the greatly strained films of 60 nm thickness the electroresistance ER=[ρ(I{sub 1} {sub μA})−ρ(I{sub 1000} {sub μA})]/ρ(I{sub 1} {sub μA}) reaches ~70% at T=25 K, much higher than ER~7% in the strain-relaxed films of 400 nm thickness, implying the strain effect on ER. Also the magnetoresistance of the film falls with strain-relaxation. Therefore the electric properties of the film could be efficiently modified by strain, electric current and magnetic field. All of them may be explained by the effect on the percolative phase separation and competition in the half-doped manganite material. The manganite films located at phase boundary are expected to be an ideal compound for providing practical colossal effects of elastoresistance, electroresistance and magnetoresistance due to the multiphase coexistence. - Highlights: • The electric current-induced electroresistance (ER) and magnetoresistance (MR)studies on PLD grown Pr{sub 0.5}Sr{sub 0.5}MnO{sub 3}/(001) LaAlO{sub 3} films were found to be greatly sensitive to the film thickness arising from the strain. • It is shown that, 60 nm film exhibit compressive in-plane strain which leads to phase separation and hence colossal MR and ER. • Our results suggest that the manganites located at phase boundary may be an ideal compound for providing practical colossal effects of elastoresistance, electroresistance and magnetoresistance.

  6. Magnetic and XMCD studies of Pr{sub 1−x}Sr{sub x}MnO{sub 3} manganite films

    Energy Technology Data Exchange (ETDEWEB)

    Samoshkina, Yu.E., E-mail: uliag@iph.krasn.ru [Kirensky Institute of Physics, Federal Research Center KSC SB RAS, Krasnoyarsk 660036 (Russian Federation); Edelman, I.S. [Kirensky Institute of Physics, Federal Research Center KSC SB RAS, Krasnoyarsk 660036 (Russian Federation); Stepanova, E.A.; Neznakhin, D.S. [Ural Federal University, Yekaterinburg 620000 (Russian Federation); Ollefs, K. [European Synchrotron Radiation Facility (ESRF), BP 220, 38043 Grenoble Cedex 9 (France); Andreev, N.V.; Chichkov, V.I. [National University of Science and Technology “MISiS”, Moscow 119049 (Russian Federation)

    2017-04-15

    Magnetic properties of the Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} and Pr{sub 0.6}Sr{sub 0.4}MnO{sub 3} polycrystalline films have been studied using temperature and magnetic field dependences of the static magnetization and X-ray magnetic circular dichroism (XMCD) spectroscopy. For the both compositions, the difference between the temperature dependences of magnetization obtained in the zero fields cooling (ZFC) and field cooling (FC) modes has been revealed. The ZFC curves demonstrate a pronounced maximum at temperature T{sub m}. It is shown that the T{sub m} value dependence on the magnetic field follows the Almeida-Thouless line typical for the classic spin glass, what allows us to assume the possible spin-glass behavior of the films. Effect of the disorder in a direction of the crystallites easy-axis on the difference between FC and ZFC curves has been discussed also. Magnetic field dependences of the sample magnetization are presented by the hysteresis loops with the shape changing upon temperature variation. This behavior has been attributed to the effect of crystallographic anisotropy and Pr ions. The spectra and magnetic field dependences of XMCD at the Pr L{sub 2}- and Mn K-edges have been studied at 90 K. The magnetic field dependences of the XMCD at the Pr L{sub 2}-edge had shown Van Vleck paramagnetism from Pr{sup 3+} ions. - Highlights: • M (T) magnetization behavior indicates the presence of spin glass behavior in the films. • Shape of the hysteresis loops depends on temperature. • Magnetic field dependences of XMCD at T=90 K reveal Van Vleck paramagnetism from Pr{sup 3+} ions.

  7. Crystal-field study of magnetization and specific heat properties of frustrated pyrochlore Pr{sub 2}Zr{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Alam, J.; Jana, Y.M., E-mail: yatramohan@yahoo.com; Biswas, A. Ali

    2016-10-15

    The experimental results of temperature dependent dc magnetic susceptibility, field dependent isothermal magnetization, magnetic specific heat and entropy of the pyrochlore Pr{sub 2}Zr{sub 2}O{sub 7} are simulated and analyzed using appropriate D{sub 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 {sup 3}H{sub 4} multiplet of the Pr{sup 3+} ions are obtained considering intermediate coupling between different Russell-Saunders terms of the 4f{sup 2} electronic configurations of Pr-ion and J-mixing effects. CF analysis shows that the CF ground-state of the Pr{sup 3+} ion in Pr{sub 2}Zr{sub 2}O{sub 7} is a well-isolated doublet, with significant admixtures of terms coming from |M{sub J}=±4〉 and |M{sub 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.

  8. Solid state chemistry of rare earth oxides. Technical progress report, 1975--1976. [Pr/sub 7/O/sub 12/; Pr/sub 10/O/sub 18/; HfO/sub 2/. xEr/sub 2/O/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Eyring, L.; Skarnulis, A.J.; Tuenge, R.T.; Von Dreele, R.B.

    1976-04-15

    It has been demonstrated that electron microscope images obtained at about 3A resolution for Pr/sub 7/O/sub 12/ are in agreement with calculated images based upon known structures. This establishes the efficacy of crystal structure image interpretation in structural terms, including the defect structure and mechanism of phase reactions, for these types of related phases whose structures are as yet beyond conventional means to determine. Further work on the epsilon (Pr/sub 10/O/sub 18/) phase is reported both utilizing electron optical methods and single crystal X-ray techniques. The ternary ceramic system HfO/sub 2/.xEr/sub 2/O/sub 3/ is being examined using electron optical techniques and ordering not hitherto reported is being observed. An interactive crystal structure image calculation system is being developed which will permit the immediate comparison of enhanced images synthesized from trial structures (including defects) and displayed in juxtaposition on a graphics unit. 22 fig. (auth)

  9. Dispersion of CEF levels in Nd{sub 2}CuO{sub 4} and Pr{sub 0.86}Ce{sub 0.14}CuO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Henggeler, W.; Furrer, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Chattopadyay, T.; Roessli, B. [Institut Max von Laue - Paul Langevin, 75 - Paris (France)

    1997-09-01

    We performed inelastic scattering experiments to determine the dispersion of the {Gamma}{sub 6}{sup (1)}-{Gamma}{sub 6}{sup (2)}-Nd crystal field excitation in Nd{sub 2}CuO{sub 4} and of the {Gamma}{sub 4}-{Gamma}{sub 5} Pr CEF excitation in Pr{sub 1.86}Ce{sub 0.14}CuO{sub 4}. Our results can be described within the random phase approximation model. (author) 4 figs.

  10. Knight shift measurements in the superconducting state of Pr{sub 1-x}La{sub x}Os{sub 4}Sb{sub 12}(x=0.4) probed by {mu}SR

    Energy Technology Data Exchange (ETDEWEB)

    Higemoto, W. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan)]. E-mail: higemoto.wataru@jaea.go.jp; Aoki, Y. [Department of Physics, Tokyo Metropolitan University of Hachioji, Tokyo 192-0397 (Japan); Ohishi, K. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Ito, T.U. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Department of Physics, Tokyo Institute of Technology, Meguro, Tokyo 152-8551 (Japan); Heffner, R.H. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Saha, S.R. [Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801 (Japan); Koda, A. [Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801 (Japan); Satoh, K.H. [Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801 (Japan); Kadono, R. [Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801 (Japan); Kikuchi, D. [Department of Physics, Tokyo Metropolitan University of Hachioji, Tokyo 192-0397 (Japan); Sugawara, H. [Department of Mathematical and Natural Sciences, University of Tokushima, Tokushima 770-8502 (Japan); Sato, H. [Department of Physics, Tokyo Metropolitan University of Hachioji, Tokyo 192-0397 (Japan)

    2007-03-15

    We report a muon spin rotation study of a single crystalline sample of the heavy fermion superconductor Pr{sub 1-x}La{sub x}Os{sub 4}Sb{sub 1}2(x=0.4). The muon Knight shift is independent of temperature, passing through T{sub c} down to 20mK, suggesting that the local spin susceptibility does not decrease in the superconducting state.

  11. Temperature-induced spin reorientation and magnetization jump of rare-earth orthoferrite Ho{sub 0.5}Pr{sub 0.5}FeO{sub 3} single crystal

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guohua; Zhao, Weiyao; Cao, Yiming; Kang, Baojuan [Department of Physics, and International Center of Quantum and Molecular Structures, Shanghai University, Shanghai 200444 (China); Zhang, Jincang [Department of Physics, and International Center of Quantum and Molecular Structures, Shanghai University, Shanghai 200444 (China); Materials Genome Institute, Shanghai University, Shanghai 200444 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai University, Shanghai 200444 (China); Ren, Wei, E-mail: renwei@shu.edu.cn [Department of Physics, and International Center of Quantum and Molecular Structures, Shanghai University, Shanghai 200444 (China); Materials Genome Institute, Shanghai University, Shanghai 200444 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai University, Shanghai 200444 (China); Cao, Shixun, E-mail: sxcao@shu.edu.cn [Department of Physics, and International Center of Quantum and Molecular Structures, Shanghai University, Shanghai 200444 (China); Materials Genome Institute, Shanghai University, Shanghai 200444 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai University, Shanghai 200444 (China)

    2016-07-25

    We report temperature-induced spin reorientation and magnetization jump effects in the rare earth (RE) orthoferrite Ho{sub 0.5}Pr{sub 0.5}FeO{sub 3} single crystal. The single crystal of about 6 mm in diameter and 50 mm in length was successfully grown by optical floating zone method. Both X-ray diffraction and Laue photograph confirmed the homogeneity and high quality of the crystal. Magnetic properties of Ho{sub 0.5}Pr{sub 0.5}FeO{sub 3} single crystal are studied over a wide temperature range from 2 to 300 K. Spin reorientation transition from Γ{sub 2} to Γ{sub 4} phase is observed in the temperature range of 75–90 K. At lower temperature, the Ho{sub 0.5}Pr{sub 0.5}FeO{sub 3} shows an abrupt jump of magnetization along the a-axis, which occurs only in the field-cooling process, and is sensitive to external applied magnetic field. By analyzing the jump temperature and magnitude of the magnetization, we conclude that it is caused by the spin reversal of the rare earth ions. The isothermal magnetization versus field hysteresis loop measurements along a axis explain the spin configuration variation from 3 K to 60 K. - Highlights: • Ho{sub 0.5}Pr{sub 0.5}FeO{sub 3} single crystal was grown by optical floating zone method. • It shows an abrupt jump of magnetization along a axis at low temperature. • The jump height and temperature is sensitive to external applied magnetic field. • It is attributed to the spin reversal of the rare earth ions.

  12. Effects of magnetization on hole localization and MnO{sub 6} octahedra disorder in hole-doped lanthanum manganese perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Booth, C.H.; Brosha, E.L.; Kwei, G.H. [Los Alamos National Lab., NM (United States); Bridges, F. [Univ. of California, Santa Cruz, CA (United States). Physics Dept.; Neumeier, J.J. [Florida Atlanta Univ., Boca Raton, FL (United States). Physics Dept.

    1998-12-31

    The authors review the distortions of the MnO{sub 6} octahedra reduced by magnetization in hole-doped lanthanum manganese perovskites. The systems they consider include the colossal magnetoresistance (CMR) samples La{sub 1{minus}x}Ca{sub x}MnO{sub 3} (x = 0.21, 0.25, 0.30), La{sub 0.76}Ba{sub 0.33}MnO{sub 3}, and a poorer quality La{sub 0.76}Pb{sub 0.33}MnO{sub 3} sample. They also report preliminary work on three samples of oxygen-doped LaMnO{sub 3+{delta}} and a lanthanum-deficient La{sub 0.9}MnO{sub 3} sample. They find the same exponential relationship between the removal of the distortion and the sample magnetization in the Ba- and Pb-doped CMR samples as was found previously for the Ca doped samples. The MnO{sub 6} distortion in the oxygen-doped materials is found to slightly reduce below the magnetic transition, although much less so than in the CMR samples. Above T{sub C}, the antiferromagnetic LaMnO{sub 3.006} sample shows a softer temperature dependence of the Mn-O bond length distribution broadening. Surprisingly, even this sample shows deviations from thermal (Debye) behavior near T{sub N}, possibly due to FM coupling within MnO planes.

  13. Fe2+-Ti4+ vs. Fe2+-Fe3+ charge-transfer and short-range order in single chains of face-sharing octahedra: ellenbergerite and dumortierite

    Science.gov (United States)

    Chopin, C.; Langer, K.; Khomenko, V.

    2009-04-01

    In zoned pyrope megacrysts from the Dora-Maira UHP terrane, new, dark-violet colour varieties of the hexagonal, high-pressure silicate ellenbergerite extend the range of known Fe contents for this mineral from 0-0.1 to 0-0.4 atom pfu, for Ti contents commonly in the range 0.2-0.4 pfu. The new varieties show an extremely intense pleochroism, colourless for E perpendicular to c to deep Prussian blue for E//c, as compared to colourless to lilac or reddish purple for classical Fe-poor ellenbergerite. These features were the incentive for an electronic absorption spectroscopic study and a reappraisal of the interpretation of the charge transfers (CT), colour and ordering schemes in this group and the structurally related borosilicate dumortierite. Both structures are characterized by the presence of infinite single chains of face-sharing, partly vacant octahedra along the 6-fold screw axis and pseudo-hexad axis, respectively, in which the Fe and Ti atoms are partitioned. In the spectra of Fe-poor ellenbergerite, the presence of a single Fe2+-Ti4+ CT band near 19000 cm˘1 was taken as evidence for complete short-range ordering of Mg(Fe), Ti and vacancies in the octahedral single chain [1]. The E//c spectra of Fe-rich ellenbergerite show the same absorption band near 19000 cm˘1 but consistently flanked by another CT band near 14000 cm˘1 , the intensity of which increases with total Fe content. The latter is similar to the 12400 cm˘1 CT band observed as the single feature in E//c spectra of the isotructural (Ti-free and Fe-bearing) phosphoellenbergerite, and clearly assigned to Fe2+-Fe3+ CT in the octahedral single chain [1]. The same colour pattern occurs in the dumortierite group, with red Fe-poor, Ti-rich crystals showing a single CT band near 20000 cm˘1, blue Ti-poor crystals showing a single CT band near 16500 cm˘1, and violet Fe- and Ti-rich crystals showing a combination of the two bands [2]. In the light of the new data, we reinterpret the dumortierite colour

  14. Stark and Zeeman effects in Nd{sub 2}Fe{sub 14}B and Pr{sub 2}Fe{sub 14}B intermetallics

    Energy Technology Data Exchange (ETDEWEB)

    Radwanski, R.J. [Institute of Physics and Informatics, Pedagogical University, Cracow (Poland)]|[Center of Soil State Physics, Cracow (Poland); Franse, J.M. [Van der Waals-Zeeman Laboratory, University of Amsterdam, Amsterdam (Netherlands)

    1996-12-31

    The energy level scheme of the Nd{sup 3+} and Pr{sup 3+} ions in ferromagnetic Nd{sub 2}Fe{sub 14}B and Pr{sub 2}Fe{sub 14}B intermetallic compounds was evaluated on the basis of well known experiments. In calculations the effect of charge (Stark effect) and spin-dependent (Zeeman effect) interactions were taken into account by means of the crystal-field and Molecular-field approximation, respectively. The derived energy levels scheme is associated with the removal of the degeneracy of the lowest multiplet given by Hund`s rules, i.e. {sup 4}I{sub 9/2} (Nd{sup 3+}) and {sup 3}H{sub 4} (Pr{sup 3+}). The revealed low-energy electronic structure (< 25 meV = 200 cm{sup -1}) is associated with many electron states of RE{sup 3+} ions. Magnetic and electronic properties resulting from this fine structure are compared with all known experimental results. The localized crystal electric field levels exist also in Nd{sub 2}CuO{sub 4}, and ionic compounds which by doping with Ce becomes high-T{sub c} superconductor, indicating the formation of crystal electric field states independently on the metallic or ionic state. (author) 12 refs, 9 figs

  15. Magnetic properties of polycrystalline Pr{sub x}Y{sub 1-x}Ba{sub 2}Cu{sub 3}O{sub 7-{delta}}

    Energy Technology Data Exchange (ETDEWEB)

    Stari, C. [Grupo de Materiais e Dispositivos-GMD, Departamento de Fisica-UFSCar, Caixa Postal 676, Sao Carlos (Brazil); Instituto de Fisica, Facultad de Ingenieria, UdelaR, Julio Herrera y Reissig 565, C.C. 30, 11000 Montevideo (Uruguay); Rivera, V.A.G. [Grupo de Materiais e Dispositivos-GMD, Departamento de Fisica-UFSCar, Caixa Postal 676, Sao Carlos (Brazil); Lanfredi, A.J.C. [LIEC, Departamento de Quimica, Centro Multidisciplinar para o Desenvolvimento deMateriais Ceramicos, UFSCar, Caixa Postal 676, Sao Carlos, SP (Brazil); Cardoso, C.A. [Grupo de Materiais e Dispositivos-GMD, Departamento de Fisica-UFSCar, Caixa Postal 676, Sao Carlos (Brazil); Leite, E.R. [LIEC, Departamento de Quimica, Centro Multidisciplinar para o Desenvolvimento deMateriais Ceramicos, UFSCar, Caixa Postal 676, Sao Carlos, SP (Brazil); Mombru, A.W. [Laboratorio de Cristalografia, Estado Solido y Materiales, DETEMA, Facultad de Quimica, UdelaR, Gral. Flores 2124, 11800 Montevideo (Uruguay); Araujo-Moreira, F.M. [Grupo de Materiais e Dispositivos-GMD, Departamento de Fisica-UFSCar, Caixa Postal 676, Sao Carlos (Brazil)], E-mail: faraujo@df.ufscar.br

    2008-07-15

    In this work, we report a part of a systematic study of the influence of the synthesis routes on the properties of polycrystalline samples of Pr{sub x}Y{sub 1-x}Ba{sub 2}Cu{sub 3}O{sub 7-{delta}}. We have prepared high-quality samples of this material by following a sol-gel method, associated with heat treatment in both an inert argon and an oxygen atmospheres in order to compare their influence on the formation of the superconducting phase. Magnetic measurement (AC susceptibility) show that the superconducting transition temperature (T{sub C}) increases in samples prepared in argon when compared to those prepared in oxygen, for the same composition and Pr fraction less than 0.5. In addition to this, preliminary results of AC and DC magnetic susceptibility show superconductivity for samples with Pr fraction higher than 0.5 (and up to 0.9) prepared under argon flux, which may indicate the existence of stable superconductivity for all compositions, including pure Pr-123.

  16. Observation of semiconductor to metallic transition and polaron hopping in double perovskite Pr{sub 2}CoTiO{sub 6} ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Mahato, Dev K., E-mail: drdevkumar@yahoo.com [Department of Physics, National Institute of Technology Patna, Patna 800005 (India); Sinha, T.P. [Department of Physics, Bose Institute, 93/1, APC Road, Kolkata 700009 (India)

    2017-05-01

    This paper describes semiconductor to metal transition and polaron conduction in double perovskite Pr{sub 2}CoTiO{sub 6} (PCTO) ceramics. The XRD pattern recorded at room temperature confirmed the pure phase, single crystalline structure. The semicircle arc in the impedance plot at each temperature can be attributed to the grain boundary contribution, indicating one dominating response in the measurement frequency range. The semiconductor to metallic transition was also confirmed by the variation of grain boundary resistance (R{sub gb}) with temperature. The activation energy estimated from the imaginary part of electrical modulus and impedance are found to be the characteristic of polaron conduction in PCTO. Ac conductivity followed power law dependence σ{sub ac} = Bω{sup n}. The observed variation of the exponent ‘n’ with temperature suggests the typical of charge transport assisted by a hopping process. The observed minimum in the temperature dependence of frequency exponent ‘n’ strongly suggests that the large polaron tunneling is the dominant transport process.

  17. Effects of multi-modification of rare earth oxides Pr{sub x}O{sub y} and La{sub x}O{sub y} on microstructure and tensile properties of casting Al-Cu alloy

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Yumei; Bai, Zhihao; Qiu, Feng; Jin, Shenbao [Key Laboratory of Automobile Materials, Ministry of Education, Department of Materials Science and Engineering, Jilin University, Renmin Street no. 5988, Changchun, Jilin Province, 130025 (China); Jiang, Qichuan, E-mail: jqc@jlu.edu.cn [Key Laboratory of Automobile Materials, Ministry of Education, Department of Materials Science and Engineering, Jilin University, Renmin Street no. 5988, Changchun, Jilin Province, 130025 (China)

    2012-12-15

    Through multi-modification with Pr{sub x}O{sub y} and La{sub x}O{sub y}, the tensile strength and elongation of casting Al-Cu alloy can reach to 580 MPa and 10.5%, increased by 26% and 50% respectively than those of the unmodified alloy. Simultaneous increase in the tensile strength and elongation of the multi-modified alloys is suggested to be induced by the refined {alpha}-Al dendrites, the formation of Al-RE intermetallic compounds at the grain boundaries, and the most important, more homogeneously distributed nano-scale {theta} Prime precipitates with higher diameter/thickness ratio.

  18. Structural, electrical and magnetic properties of Sb-doped Pr{sub 2/3}Ba{sub 1/3}MnO{sub 3} perovskite manganites

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Vikram [Superconductivity Division, National Physical Laboratory, Dr. K.S. Krishnan Road, New Delhi 110012 (India); Department of Physics and Astrophysics, University of Delhi, New Delhi 110007 (India); Panwar, Neeraj [Superconductivity Division, National Physical Laboratory, Dr. K.S. Krishnan Road, New Delhi 110012 (India); Bhalla, G.L. [Department of Physics and Astrophysics, University of Delhi, New Delhi 110007 (India); Agarwal, S.K. [Superconductivity Division, National Physical Laboratory, Dr. K.S. Krishnan Road, New Delhi 110012 (India)]. E-mail: agarwal@mail.nplindia.ernet.in

    2007-07-31

    We report here the electrical, magnetic and micro-structural features of the Sb-doped (nominally at Mn-sites) Pr{sub 2/3}Ba{sub 1/3}MnO{sub 3} perovskite manganites. Pristine material shows two insulator-metal (I-M) like transitions in the resistivity-temperature ({rho}-T) behaviour. While the higher temperature transition (T {sub P1}) at {approx}195 K is reminiscent of the usual metal-insulator transition, the lower temperature transition (T {sub P2}) at {approx}160 K has been ascribed to the grain boundary (GB) effects arising out of the ionic size mismatch between the ions present at the rare-earth site (Pr and Ba). With Sb doping at the Mn-site, both the resistivity peaks are seen to shift to lower temperatures. Room temperature resistivity and the peak values are also successively increasing with Sb doping. Scanning electron micrographs of the samples indicate a gradual increase in their grain sizes with Sb which indicates a gradual decrease in the GB density. The higher temperature insulator-metal transition (T {sub P1}) shift is explained on the basis of a competition between double-exchange and super-exchange mechanisms. The observed overall resistivity increase and the shift in the resistivity hump (T {sub P2}) with Sb are found related to the gradually decreasing GB density and the ensuing lattice strain increase at the grain boundaries. The intrinsic MR gets suppressed and the extrinsic MR gets enhanced with Sb doping. The observed low temperature resistivity upturn related to the localization of carriers, is also seen to increase with Sb.

  19. Colossal anisotropic resistivity and oriented magnetic domains in strained La{sub 0.325}Pr{sub 0.3}Ca{sub 0.375}MnO{sub 3} films

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Tao; Yang, Shengwei; Liu, Yukuai; Zhao, Wenbo; Feng, Lei; Li, Xiaoguang, E-mail: lixg@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at Microscale, Department of Physics, University of Science and Technology of China, Hefei 230026 (China); Zhou, Haibiao; Lu, Qingyou [Hefei National Laboratory for Physical Sciences at Microscale, Department of Physics, University of Science and Technology of China, Hefei 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Sciences and University of Science and Technology of China, Hefei 230031 (China); Hou, Yubin [High Magnetic Field Laboratory, Chinese Academy of Sciences and University of Science and Technology of China, Hefei 230031 (China)

    2014-05-19

    Magnetic and resistive anisotropies have been studied for the La{sub 0.325}Pr{sub 0.3}Ca{sub 0.375}MnO{sub 3} films with different thicknesses grown on low symmetric (011)-oriented (LaAlO{sub 3}){sub 0.3}(SrAl{sub 0.5}Ta{sub 0.5}O{sub 3}){sub 0.7} substrates. In the magnetic and electronic phase separation region, a colossal anisotropic resistivity (AR) of ∼10{sup 5}% and an anomalous large anisotropic magnetoresistance can be observed for 30 nm film. However, for 120 nm film, the maximum AR decreases significantly (∼2 × 10{sup 3}%) due to strain relaxation. The colossal AR is strongly associated with the oriented formation of magnetic domains, and the features of the strain effects are believed to be useful for the design of artificial materials and devices.

  20. Investigation of conduction mechanism in Pr{sub 0.67}Sr{sub 0.13}Ag{sub 0.20}MnO{sub 3} manganites

    Energy Technology Data Exchange (ETDEWEB)

    Modi, Anchit, E-mail: sehr.masroor1952@gmail.com; Bhat, Masroor Ahamad; Gaur, N. K. [Department of Physics, Barkatullah University, Bhopal-462026 (India)

    2016-05-23

    We report the electronic conduction mechanism in Pr{sub 0.67}Sr{sub 0.13}Ag{sub 0.20}MnO{sub 3} synthesized successfully by conventional solid state reaction method. The compound under investigation was subjected by X – Ray diffraction using Rietveld refinement which confirms the single phase nature of the sample. The resistivity behavior indicates the semiconducting behavior and reduction in resistivity on the application of magnetic fields. The electronic nature can further been evaluated by using variable range hopping (VRH) model and small polaron hopping model (SPH) showing that the double exchange interaction increases suppress the band gap and enhances carrier delocalization on the application of magnetic fields.

  1. Structural, ferroelectric and leakage current properties of Bi{sub 3.96}Pr{sub 0.04}Ti{sub 2.95}Nb{sub 0.05}O{sub 12} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Kao, Ming-Cheng, E-mail: kmc@mail.hust.edu.tw [Department of Electronic Engineering, Hsiuping University of Science and Technology, Taichung 412, Taiwan (China); Chen, Hone-Zern, E-mail: hzc@mail.hust.edu.tw [Department of Electronic Engineering, Hsiuping University of Science and Technology, Taichung 412, Taiwan (China); Young, San-Lin [Department of Electronic Engineering, Hsiuping University of Science and Technology, Taichung 412, Taiwan (China); Kao, Ming-Hui [Department of Electronic Engineering, Chung Chou University of Science and Technology, Changhua 510, Taiwan (China)

    2014-11-03

    Praseodymium and niobium-substituted bismuth titanate (Bi{sub 3.96}Pr{sub 0.04}Ti{sub 2.95}Nb{sub 0.05}O{sub 12}, BPTNO) thin films were deposited on Pt(111)/Ti/SiO{sub 2}/Si(100) substrates by a sol–gel technology. The effects of annealing temperature (500 ∼ 800 °C) on microstructure and electric properties of thin films were investigated. X-ray diffraction analysis shows that the BPTNO thin films have a bismuth-layered perovskite structure with preferred (117) orientation. The intensities of (117) peak increases with increasing annealing temperature. With the increase of annealing temperature from 500 °C to 800 °C, the grain size of BPTNO thin films increases. The highly (117)-oriented BPTNO thin films exhibits a high remnant polarization (2P{sub r}) of 48 μC/cm{sup 2} and a low coercive field (2E{sub c}) of 110 kV/cm, fatigue free characteristics up to > 10{sup 8} switching cycles. A small leakage current density (J) was 6.23 × 10{sup −8} A/cm{sup 2} at 200 kV/cm. The leakage current mechanisms were controlled by Poole–Frenkel emission in the low electric field region and by Schottky emission in the high field region. - Highlights: • Bi{sub 3.96}Pr{sub 0.04}Ti{sub 2.95}Nb{sub 0.05}O{sub 12} thin films were prepared by sol–gel technology. • Films show preferred (117) orientation. • The Pr and Nb-doping decrease the oxygen vacancy concentration. • The Pr and Nb-doping improved the ferroelectric and leakage current properties.

  2. Small angle neutron scattering study of magnetic clustering in (Pr{sub 0.55}Ca{sub 0.45})(Mn{sub 1-y}Cr{sub y})O{sub 3} manganites

    Energy Technology Data Exchange (ETDEWEB)

    Castellano, C., E-mail: carlo.castellano@unimi.it [Universita degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19, 20133 Milano (Italy); Martinelli, A. [CNR-SPIN, C.so Perrone 24, 16152 Genova (Italy); Ferretti, M. [CNR-SPIN, C.so Perrone 24, 16152 Genova (Italy); Universita degli Studi di Genova, Dipartimento di Chimica e Chimica Industriale, Via Dodecaneso 31, 16146 Genova (Italy); Cimberle, M.R. [CNR-IMEM, Via Dodecaneso 33, 16146 Genova (Italy); Mondelli, C. [CNR-IOM-OGG and TOF at Institut Laue-Langevin, 6 rue Jules Horowitz, 38042 Genoble Cedex 9 (France)

    2012-11-25

    Highlights: Black-Right-Pointing-Pointer Magnetic clusters formation in (Pr{sub 0.55}Ca{sub 0.45})(Mn{sub 1-y}Cr{sub y})O{sub 3} manganites is pointed out. Black-Right-Pointing-Pointer We indicate that magnetic clusters formation is favoured by Mn/Cr substitution. Black-Right-Pointing-Pointer The importance of magnetic polarons in manganites phase behaviour is thus emphasized. Black-Right-Pointing-Pointer We tune by chemical substitution the weight of the different phase components. Black-Right-Pointing-Pointer Magnetic clusters formation in Mn/Cr substituted manganites results to be softened. - Abstract: In the present paper we report a small angle neutron scattering (SANS) study of magnetic clusters formation in (Pr{sub 0.55}Ca{sub 0.45})(Mn{sub 1-y}Cr{sub y})O{sub 3} (y = 0.00, 0.03, 0.06) manganites which was performed by analyzing, above and below the magnetic phase transitions, the momentum transfer q dependence of the SANS intensity on temperature and on the applied magnetic field 0 < H < 5 T. Thermal scans between 5 and 300 K in zero field, 1 and 5 T as well as isothermal field-scans at three different temperatures were collected in the suitable q range on each sample. These measurements allowed us to determine the spatial dimensions, density and distribution of the non-overlapping ferromagnetic clusters before, during and after their formation, both in the insulating high temperature and in the percolating low temperature phases. Our results indicate that the magnetic clusters formation is favoured by Mn/Cr partial substitution, thus emphasizing the importance of magnetic polarons in the natural tendency of manganites to phase separation and the possibility to tune by chemical substitution the relative weight of one phase component with respect to the other one.

  3. Phase separation and magnetocaloric effect in Pr{sub 0.5−x}Gd{sub x} Sr{sub 0.5}MnO{sub 3} system

    Energy Technology Data Exchange (ETDEWEB)

    Bourouina, M. [Laboratoire de Physique des Matériaux, Faculté des Sciences de Sfax, Université de Sfax, B. P. 1171, 3000 Sfax (Tunisia); Krichene, A., E-mail: akramkri@hotmail.fr [Laboratoire de Physique des Matériaux, Faculté des Sciences de Sfax, Université de Sfax, B. P. 1171, 3000 Sfax (Tunisia); Chniba Boudjada, N. [Institut Néel, B.P. 166, 38042 Grenoble Cedex 9 (France); Boujelben, W. [Laboratoire de Physique des Matériaux, Faculté des Sciences de Sfax, Université de Sfax, B. P. 1171, 3000 Sfax (Tunisia)

    2016-09-25

    The magnetic properties and the magnetocaloric effect have been studied in Pr{sub 0.5−x}Gd{sub x}Sr{sub 0.5}MnO{sub 3} (x = 0, 0.05 and 0.1) manganites prepared by the solid state reaction method. Magnetic measurements versus temperature in an applied magnetic field of 0.05 T show that the all samples exhibit a paramagnetic to ferromagnetic transition when temperature decreases. The x = 0.1 sample shows a clear transition, from the ferromagnetic state to the antiferromagnetic one at T{sub N} = 125 K. The Curie temperature decreases gradually with increasing gadolinium content. The absolute values of the maximum of magnetic entropy change |ΔS{sub M}| for an applied magnetic field of 2 T are equal to1.26, 1.25 and 1.02 J kg{sup −1} K{sup −1} for x = 0, 0.05 and 0.1, respectively. The decrease of |ΔS{sub M}| with Gd doping can be attributed to the enhancement of phase separation phenomenon. The magnetic entropy curves follow the universal law corresponding to the second-ordered paramagnetic-ferromagnetic transition. - Highlights: • Gd doping in Pr{sub 0.5−x}Gd{sub x}Sr{sub 0.5}MnO{sub 3} (with x = 0, 0.05 and 0.1) enhances the antiferromagnetic interactions. • The studied samples are characterized by the phase separation phenomenon. • Magnetic properties are in agreement with electrical results.

  4. Cobalt-free perovskite Pr{sub 0.5}Sr{sub 0.5}Fe{sub 1−x}Cu{sub x}O{sub 3−δ} (PSFC) as a cathode material for intermediate temperature solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Moura, Caroline G., E-mail: caroline.materiais@gmail.com [Materials Science and Engineering Postgraduate Program, UFRN, 59078-970, Natal (Brazil); Grilo, João Paulo de F. [Materials Science and Engineering Postgraduate Program, UFRN, 59078-970, Natal (Brazil); Macedo, Daniel A., E-mail: damaced@gmail.com [Materials Science and Engineering Postgraduate Program, UFPB, 58051-900, João Pessoa (Brazil); Cesário, Moisés R.; Fagg, Duncan Paul [Department of Mechanical Engineering, University of Aveiro, 3810-193, Aveiro (Portugal); Nascimento, Rubens M. [Materials Science and Engineering Postgraduate Program, UFRN, 59078-970, Natal (Brazil)

    2016-09-01

    PSFC (Pr{sub 0.5}Sr{sub 0.5}Fe{sub 1−x}Cu{sub x}O{sub 3−δ}) is a new perovskite-type oxide that has gained considerable attention as cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs), due to its high mixed ionic-electronic conductivity below 800 °C. In this work, PSFC (Pr{sub 0.5}Sr{sub 0.5}Fe{sub 1−x}Cu{sub x}O{sub 3−δ}, x = 0.2 and 0.4) powders were synthesized by the citrate method and structurally characterized by X-ray diffractometry. Screen-printed cathodes were sintered at 1050 °C and electrochemically characterized by impedance spectroscopy at 600–800 °C in pure oxygen. The area specific resistances (ASR) of the Pr{sub 0.5}Sr{sub 0.5}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} material are shown to be competitive with typical values reported for cobalt-based cathodes in the measured temperature range, while, importantly, offering a significantly lower activation energy, 0.62 eV. The thermal expansion coefficients of these Co-free cathodes are in the range of 13–15 × 10{sup −6} °C{sup −1}, in a temperature range 200–650 °C, demonstrating a good thermal compatibility with gadolinia doped ceria (CGO) electrolytes. - Highlights: • Cobalt-free Pr{sub 0.5}Sr{sub 0.5}Fe{sub 1−x}Cu{sub x}O{sub 3−δ} (PSFC) cathodes successfully prepared by the citrate method. • PSFC cathodes are thermally compatible with CGO electrolytes. • Pr{sub 0.5}Sr{sub 0.5}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} presents competitive area specific resistances of low activation energy, 0.62 eV.

  5. Effect of hydrostatic pressure on magnetic and magnetocaloric properties in La{sub 0.35}Pr{sub 0.35}Ca{sub 0.3}MnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Thiyagarajan, R. [Centre for High Pressure Research, School of Physics, Bharathidasan University, Tiruchirapalli 620024, Tamil Nadu (India); Esakki Muthu, S. [Centre for High Pressure Research, School of Physics, Bharathidasan University, Tiruchirapalli 620024, Tamil Nadu (India); Univ. Grenoble Alpes and CEA, INAC-SPSMS, F-38000 Grenoble (France); Manikandan, K. [Centre for High Pressure Research, School of Physics, Bharathidasan University, Tiruchirapalli 620024, Tamil Nadu (India); Arumugam, S., E-mail: sarumugam1963@yahoo.com [Centre for High Pressure Research, School of Physics, Bharathidasan University, Tiruchirapalli 620024, Tamil Nadu (India)

    2016-01-15

    Magnetization of polycrystalline La{sub 0.35}Pr{sub 0.35}Ca{sub 0.3}MnO{sub 3} sample has been measured as a function of temperature (T) and magnetic field (H) under various external hydrostatic pressures (P) up to ~1 GPa. At ambient P, the sample exhibits paramagnetic (PM)–ferromagnetic (FM) transition (T{sub C}) at 167 K and 173 K in cooling and warming cycles respectively under the magnetic field (µ{sub 0}.H) of 0.1 T. It also shows a hysteresis during both temperature- and field- dependence of magnetization measurements at ambient P, suggests the presence of a first-order transition. Moreover, the field dependence of magnetization shows S type field-induced metamagnetic transition (FIMMT) over a temperature range below T{sub C} in the FM state. The application of P in M(T) increases T{sub C} at a rate [dT{sub C}/dP] of 13.9 K/GPa, but the thermally-driven first-order transition is not affected by P. However, the applied P suppresses FIMMT and reduces field-driven first-order transition in the magnetization isotherms [M(H)]below T{sub C}. H increases both magnetic entropy change (∆S{sub m}) and Relative Cooling Power (RCP), whereas the P slightly increases ∆S{sub m}{sup max} and no appreciable change in RCP. These results suggest that H and P can be used as a tool to enhance magnetocaloric values in the phase separated manganites. - Highlights: • At ambient P, La{sub 0.35}Pr{sub 0.35}Ca{sub 0.3}MnO{sub 3} sample shows first-order PM–FM transition. • P increases the T{sub C} at a rate of 13.9 K/GPa, thermal hysteresis is not affected. • P diminishes the field-driven first-order PM–FM transition, suppresses FIMMMT. • H increases ∆S{sub m} and RCP. P slightly increases ∆S{sub m}{sup max}, but no change in RCP by P.

  6. Oxygen octahedra distortion induced structural and magnetic phase transitions in Bi{sub 1−x}Ca{sub x}Fe{sub 1−x}Mn{sub x}O{sub 3} ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Pawan; Kar, Manoranjan, E-mail: mano@iitp.ac.in [Department of Physics, Indian Institute of Technology Patna, Patna 800013 (India); Shankhwar, Nisha; Srinivasan, A. [Department of Physics, Indian Institute of Technology Guwahati, Guwahati 781039 (India)

    2015-05-21

    The co-doping of Ca and Mn in respective Bi and Fe-sites of BiFeO{sub 3} lattice leads to structural transition from rhombohedral (R3c space group) to orthorhombic (Pbnm space group) crystal symmetry. The tilt angle for anti-phase rotation of the oxygen octahedra of BiFeO{sub 3} at room temperature is observed to be ∼13.8°. It decreases with the increase in the co-doping percentage which suggests the composition-driven structural phase transition. The remnant magnetization for sample with 15% of co-doping becomes about 16 times that of BiFeO{sub 3}. It may be attributed to the suppression of cycloid spin structure and uncompensated spins at the surface of nanocrystallites. Further increase in co-doping percentage results in the sharp reduction of remnant magnetization due to the dominant contribution from the collinear antiferromagnetic ordering in the Pbnm space group. The Arrott plot analysis clearly indicates the composition-driven crossover from the antiferromagnetic to weak ferromagnetic ordering and vice versa. Electron spin resonance results provide the evidence for the composition-driven phase transitions from an incommensurate spin cycloidal modulated state to one with nearly homogeneous spin order. The band gap (2.17 eV) of BiFeO{sub 3} measured using UV-Vis spectra was supported by the resonance Raman spectra.

  7. Synthesis and crystal structure of a new MOF-type indium pyromellitate (MIL-117) with infinite chains of unusual cis connection of octahedra InO 4(OH) 2

    Science.gov (United States)

    Mazaj, Matjaz; Volkringer, Christophe; Loiseau, Thierry; Kaučič, Venčeslav; Férey, Gérard

    2011-08-01

    A new MOF-type indium pyromellitate (MIL-117) was hydrothermally synthesized at 483 K for 24 h. The structure of MIL-117 with structural formula In 6(OH) 6(btec) 3(H 4btec)·8-14H 2O (btec = 1,2,4,5-benzenetetracarboxylate), orthorhombic ( Pnmm) symmetry and unit cell parameters a = 8.2390(8), b = 22.251(2), c = 37.791(4) Å, V = 6928.2(11) Å 3 was solved from single-crystal diffraction data. The three-dimensional open framework structure consists of infinite chains of unusual cis sharing In-centered octahedra linked to each other through the pyromellitate ligands. The three distinct In(III) cations are coordinated to four oxygen atoms from carboxyl groups and two μ 2-hydroxyl groups in cis positions. The MIL-117 network delimits one-dimensional channels of 7.7 × 8.0 Å running along the a axis, where occluded water molecules are located. Although water species can be easily removed from the pore, no significant N 2 or CO 2 sorption was observed.

  8. Study of complex impedance spectroscopic properties of Na{sub 2}Pb{sub 2}Pr{sub 2}W{sub 2}Ti{sub 4}Nb{sub 4}O{sub 30} Ceramic

    Energy Technology Data Exchange (ETDEWEB)

    Biswal, L.; Das, Piyush R.; Behera, Banarji [Department of Physics, SOT, KIIT University, Bhubaneswar-751 024, Odisha (India) and School of Physics, Sambalpur University, Jyoti Vihar, Burla-768 019, Odisha (India); Department of Physics, ITER, S. O. A. University, Odisha, Bhubaneswar-751 030 (India); School of Physics, Sambalpur University, Jyoti Vihar, Burla-768 019, Odisha (India)

    2012-07-23

    The polycrystalline sample of Na{sub 2}Pb{sub 2}Pr{sub 2}W{sub 2}Ti{sub 4}Nb{sub 4}O{sub 30} was prepared by high temperature solid state reaction technique. The formation of compounds with an orthorhombic structure was confirmed by X-ray diffraction technique. Surface morphology study showed homogenous distribution of plate and rod like grains over the entire surface with less porosity. The study of effect of temperature on impedance parameters in the frequency range 10{sup 2}-10{sup 6} Hz and temperature range 30-500 Degree-Sign C revealed the presence of both bulk and grain boundary effects above 275 Degree-Sign C. The bulk resistance of the material decreased with rise in temperature exhibiting a typical negative temperature coefficient of resistance (NTCR) behavior like a semiconductor. Both the complex impedance and modulus studies suggested the presence of non-Debye type of relaxation in the materials. The ac conductivity spectrum obeys Johnsche's universal power law.

  9. Electrical conductance and complex impedance analysis of La{sub 0.6}Pr{sub 0.1}Ba{sub 0.3}Mn{sub 1-x}Ni{sub x}O{sub 3} nanocrystalline manganites

    Energy Technology Data Exchange (ETDEWEB)

    Hcini, Sobhi; Oumezzine, Elaa; Baazaoui, Mohamed; Oumezzine, Mohamed [Universite de Monastir, Laboratoire de Physico-chimie des Materiaux, Departement de Physique, Faculte des Sciences de Monastir, Monastir (Tunisia); Rahmouni, Hedi; Khirouni, Kamel [Universite de Gabes, Laboratoire de Physique des Materiaux et des Nanomateriaux appliquee a l' Environnement, Faculte des Sciences de Gabes, cite Erriadh, Gabes (Tunisia); Hlil, E.K. [CNRS et Universite Joseph Fourier, Institut Neel, BP 166, Grenoble (France)

    2015-09-15

    We have investigated the electrical properties of La{sub 0.6}Pr{sub 0.1}Ba{sub 0.3}Mn{sub 1-x}Ni{sub x}O{sub 3} (x = 0 and x = 0.1) nanocrystalline manganites using complex impedance spectroscopy technique in 40Hz-10 kHz and 80-320 K, frequency and temperature ranges, respectively. The two samples exhibit a metal-semiconductor transition temperature T{sub MS} which decreases from 160 to 120 K when increasing Ni content from x = 0 to x = 0.1. The total conductance curves for samples are found to obey Jonscher power law G(ω) = G{sub DC} + Aω {sup n}. The Ni content affects the activation energy (E{sub a}) which increases from 37 meV for x = 0 to 48 meV for x = 0.1. The obtained n exponent values for x = 0 are higher than those obtained for x = 0.1. This can be related to the decrease in grain size when Ni content increases. Nyquist plots of impedance show semicircle arcs for samples, and an electrical equivalent circuit has been proposed to explain the impedance results. (orig.)

  10. Influence of electron beam irradiation on electrical, structural, magnetic and thermal properties of Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} manganites

    Energy Technology Data Exchange (ETDEWEB)

    Christopher, Benedict [Department of Physics, Manipal Institute of Technology, Manipal University, Manipal 576104 (India); Rao, Ashok, E-mail: ashokanu_rao@rediffmail.com [Department of Physics, Manipal Institute of Technology, Manipal University, Manipal 576104 (India); Petwal, Vikash Chandra; Verma, Vijay Pal; Dwivedi, Jishnu [Industrial Accelerator Section, PSIAD, Raja Ramanna Centre for Advanced Technology, Indore 452012, M.P. (India); Lin, W.J. [Department of Physics, National Dong Hwa University, Hualien 97401, Taiwan (China); Kuo, Y.-K., E-mail: ykkuo@mail.ndhu.edu.tw [Department of Physics, National Dong Hwa University, Hualien 97401, Taiwan (China)

    2016-12-01

    In this communication, the effect of electron beam (EB) irradiation on the structural, electrical transport and thermal properties of Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} manganites has been investigated. Rietveld refinement of XRD data reveals that all samples are single phased with orthorhombic distorted structure (Pbnm). It is observed that the orthorhombic deformation increases with EB dosage. The Mn–O–Mn bond angle is found to increase with increase in EB dosage, presumably due to strain induced by these irradiations. Analysis on the measured electrical resistivity data indicates that the small polaron hopping model is operative in the high temperature region for pristine as well as EB irradiated samples. The electrical resistivity in the entire temperature region has been successfully fitted with the phenomenological percolation model which is based on phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions. The Seebeck coefficient (S) of the pristine as well as the irradiated samples exhibit positive values, indicating that holes is the dominant charge carriers. The analysis of Seebeck coefficient data confirms that the small polaron hopping mechanism governs the thermoelectric transport in the high temperature region. In addition, Seebeck coefficient data also is well fitted with the phenomenological percolation model. The behavior in thermal conductivity at the transition is ascribed to the local anharmonic distortions associated with small polarons. Specific heat measurement indicates that electron beam irradiation enhances the magnetic inhomogeneity of the system.

  11. Study of electrical and magnetic properties of Pr{sub 0.6−x}Bi{sub x}Sr{sub 0.4}MnO{sub 3} (x=0.20 and 0.25)

    Energy Technology Data Exchange (ETDEWEB)

    Daivajna, Mamatha D. [Department of Physics, Manipal Institute of Technology, Manipal University, Manipal 576104 (India); Rao, Ashok, E-mail: ashokanu_rao@rediffmail.com [Department of Physics, Manipal Institute of Technology, Manipal University, Manipal 576104 (India); Lin, W.J. [Department of Physics, National Dong-Hwa University, Hualien 974, Taiwan (China); Kuo, Y.K., E-mail: ykkuo@mail.ndhu.edu.tw [Department of Physics, National Dong-Hwa University, Hualien 974, Taiwan (China)

    2017-06-01

    We have investigated the electrical and magnetic properties of Pr{sub 0.6-x}Bi{sub x}Sr{sub 0.4}MnO{sub 3} (x=0.20 and 0.25) manganites. XRD data shows that the synthesized samples are single-phase and crystallize in the orthorhombic structure with Pnma space group. Resistivity measurements show that the sample with x=0.25 exhibits a thermally activated behavior for the entire temperature range. The magnetoresistance (MR) for the x=0.25 sample is as high as nearly 100% over a wide range of temperature, demonstrating its important technological application as a material for MR-based devices. From the magnetization measurements, two magnetic transitions viz. paramagnetic insulating to ferromagnetic metallic (PMI-FMM) transition at T{sub C} and the ferromagnetic metallic (FMM) to antiferromagnetic insulating (AFI) transition at Neel temperature T{sub N} were observe in both samples. The Curie temperature decreases with bismuth doping, while T{sub N} increases with Bi content. Most interestingly, the temperature variation of magnetization and resistivity shows hysteresis behavior across the transition for the x=0.20 sample.

  12. Study of magnetic, structural and magnetocaloric properties of La{sub 0.6}Pr{sub 0.4}Mn{sub 2}Si{sub 2} under high pressures and magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Kaštil, J., E-mail: kastil@fzu.cz [Institute of Physics AS CR v.v.i., Na Slovance 2, 182 21 Prague 8 (Czech Republic); Arnold, Z. [Institute of Physics AS CR v.v.i., Na Slovance 2, 182 21 Prague 8 (Czech Republic); Isnard, O. [Centre national de la recherche scientifique (CNRS), Institut Néel, 25 rus des martyrs, F-38042 Grenoble (France); Université Grenoble Alpes, Institut Néel, F-38042 Grenoble (France); Skourski, Y. [Hochfeld-Magnetlabor Dresden (HLD), HZ Dresden-Rossendorf, D-01314 Dresden (Germany); Kamarád, J. [Institute of Physics AS CR v.v.i., Na Slovance 2, 182 21 Prague 8 (Czech Republic); Itié, J.P. [Synchrotron SOLEIL, L' Orme des Merisiers, Saint-Aubin, 91192 Gif-sur-Yvette (France)

    2017-02-15

    The structural, magnetic and magnetocaloric properties of La{sub 0.6}Pr{sub 0.4}Mn{sub 2}Si{sub 2} compound were measured in wide range of temperature, magnetic field and hydrostatic pressure. The structural study up to 10 GPa confirmed the existence of critical Mn-Mn distance 0.2883 nm for the ferromagnetic to antiferromagnetic transition at room temperature. The results demonstrated the crucial role of the volume in the suppression of the ferromagnetic phase above the transition temperature T{sub 1}=168 K under pressure. The huge pressure shift of the transition temperature T{sub 1}, dT{sub 1}/dp=230 K/GPa, was observed. Based on our magnetization measurement the low temperature transition at T{sub 2}=30 K is connected with reorientation of Mn moment and the rare-earth sublattice is not ordered in this case. The direct magnetocaloric measurement showed moderate values of the adiabatic temperature change connected with the magnetic transition at T{sub c} and T{sub 1} and confirmed the first order character of the transition at T{sub 1} and second order character of the transition at T{sub c}. - Highlights: • The huge pressure shift of the transition temperature dT{sub 1}/dp=230 K/GPa was observed. • Ferromagnetic order is suppressed by applying pressure of 1 GPa. • The direct magnetocaloric effect showed moderate values of ΔT{sub ad}.

  13. The zero-field glassy ground state and field-induced ferromagnetic transition in (La{sub 0.4}Pr{sub 0.6}){sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Tackett, R; Lawes, G; Suryanarayanan, R [Department of Physics and Astronomy, Wayne State University, Detroit, MI 48201 (United States); Apostu, M [Faculty of Chemistry, Physical, Theoretical and Materials Chemistry, Alexandru Cuza University, Iasi 700506 (Romania); Revcolevschi, A, E-mail: glawes@wayne.edu [Laboratoire de Physico-Chimie de l' Etat Solide, ICMMO, CNRS-UMR 8182, Universite Paris-Sud, 91405 Orsay (France)

    2011-04-20

    We have investigated glassy magnetic freezing in (La{sub 0.4}Pr{sub 0.6}){sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7} single crystals together with the field-induced transition to a metastable ferromagnetic phase using ac magnetic susceptibility and heat capacity measurements. The magnetization measurements show evidence for the development of a zero-field glassy ground state below 45 K along with a hysteretic, field-induced change in susceptibility associated with the transition to the ferromagnetic phase above 5 T. The heat capacity develops a clear peak at higher temperatures with the application of large magnetic fields, consistent with the development of a ferromagnetic order, while at low temperatures the Sommerfeld coefficient is monotonically reduced by an applied field, suggesting suppression of spin fluctuations. The heat capacity shows hysteretic behaviour, accompanied by a sharp decrease at a critical field, when held at fixed temperature, which does not recover on reducing the field back to zero. These measurements suggest that the zero-field ground state for (La{sub 0.4}Pr{sub 0.6}){sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7} consists of frozen disordered spin clusters, which develop into a metastable ferromagnetic state in modest magnetic fields.

  14. Electronic structure study of wide band gap magnetic semiconductor (La{sub 0.6}Pr{sub 0.4}){sub 0.65}Ca{sub 0.35}MnO{sub 3} nanocrystals in paramagnetic and ferromagnetic phases

    Energy Technology Data Exchange (ETDEWEB)

    Dwivedi, G. D.; Chou, H.; Yang, K. S.; Jhong, D. J.; Chan, W. L. [Department of Physics, National Sun Yat-sen University, Kaohsiung 80424, Taiwan (China); Joshi, Amish G. [CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110012 (India); Kumar, Shiv; Ghosh, A. K. [Department of Physics, Banaras Hindu University, Varanasi 221005 (India); Chatterjee, Sandip, E-mail: schatterji.app@iitbhu.ac.in [Department of Physics, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005 (India)

    2016-04-25

    X-ray circular magnetic dichroism (XMCD), X-ray photoemission spectroscopy (XPS), and ultraviolet photoemission spectroscopy (UPS) techniques were used to study the electronic structure of nanocrystalline (La{sub 0.6}Pr{sub 0.4}){sub 0.65}Ca{sub 0.35}MnO{sub 3} near Fermi-level. XMCD results indicate that Mn{sup 3+} and Mn{sup 4+} spins are aligned parallel to each other at 20 K. The low M-H hysteresis curve measured at 5 K confirms ferromagnetic ordering in the (La{sub 0.6}Pr{sub 0.4}){sub 0.65}Ca{sub 0.35}MnO{sub 3} system. The low temperature valence band XPS indicates that coupling between Mn3d and O2p is enhanced and the electronic states near Fermi-level have been suppressed below T{sub C}. The valence band UPS also confirms the suppression of electronic states near Fermi-level below Curie temperature. UPS near Fermi-edge shows that the electronic states are almost absent below 0.5 eV (at 300 K) and 1 eV (at 115 K). This absence clearly demonstrates the existence of a wide band-gap in the system since, for hole-doped semiconductors, the Fermi-level resides just above the valence band maximum.

  15. Effect of small quantity of chromium on the electrical, magnetic and magnetocaloric properties of Pr{sub 0.7}Ca{sub 0.3}Mn{sub 0.98}Cr{sub 0.02}O{sub 3} manganite

    Energy Technology Data Exchange (ETDEWEB)

    Bettaibi, A.; Rahmouni, H. [Universite de Gabes, Laboratoire de Physique des Materiaux et des Nanomateriaux appliquee a l' Environnement, Faculte des Sciences de Gabes cite Erriadh, Gabes (Tunisia); M' nassri, R. [Kairouan University, Higher Institute of Applied Sciences and Technology of Kasserine, Kasserine (Tunisia); Universite de Monastir, Laboratoire de Physico-Chimie des Materiaux, Departement de Physique, Faculte des Sciences de Monastir, Monastir (Tunisia); Selmi, A.; Cheikhrouhou, A. [Sfax University, Laboratory of Physics of Materials, Faculty of Sciences of Sfax, Sfax (Tunisia); Khirouni, K. [Kairouan University, Higher Institute of Applied Sciences and Technology of Kasserine, Kasserine (Tunisia); Chniba Boudjada, N. [Institut NEEL, Grenoble Cedex 09 (France)

    2016-03-15

    Structural, electrical and thermomagnetic properties of Pr{sub 0.7}Ca{sub 0.3}Mn{sub 0.98}Cr{sub 0.02}O{sub 3} were investigated. Sample was prepared by solid-state reaction method. X-ray diffraction revealed that the sample crystallizes in the orthorhombic system with Pnma space group. Electrical conductivity and complex impedance studies of Pr{sub 0.7}Ca{sub 0.3}Mn{sub 0.98}Cr{sub 0.02}O{sub 3} system are analyzed. The investigated compound exhibits a semiconductor behavior in the whole explored temperature range. From 100 to 206 K, the increase in DC conductance is more than two decade. At higher temperatures, the conductance varies slowly and a saturation region appears. The conduction mechanism is found to be governed by small polaron hopping process which is explained by the short range thermally activated energy. Conductance spectrum is well described by Jonsher law, and the temperature dependence of the frequency exponent confirms that conduction mechanism is governed by hopping process of the localized carriers. Using complex impedance analysis, the compound is modeled by an electrical equivalent circuit. Also, such analysis confirms the contribution of grain boundary to the transport properties. The substitution of Mn by 2 % Cr destroyed the charge order state observed in the parent compound and induced a ferromagnetic phase at low temperatures. For a magnetic field change of 5 T, the material shows a maximum magnetic entropy change ∇S {sup max} = 2.69 J kg{sup -1} K{sup -1} with a full width at half maximum δ {sub TFWHM} = 145 K, and a relative cooling power RCP = 389 J kg{sup -1}. Pr{sub 0.7}Ca{sub 0.3}Mn{sub 0.98}Cr{sub 0.02}O{sub 3} material demonstrates potential proprieties to be used in electronic and thermal devices and as magnetic refrigerant. (orig.)

  16. Evolution and sign control of square-wave-like anisotropic magneto-resistance in spatially confined La{sub 0.3}Pr{sub 0.4}Ca{sub 0.3}MnO{sub 3}/LaAlO{sub 3}(001) manganite thin films

    Energy Technology Data Exchange (ETDEWEB)

    Alagoz, H. S., E-mail: alagoz@ualberta.ca; Jeon, J.; Keating, S.; Chow, K. H., E-mail: khchow@ualberta.ca; Jung, J., E-mail: jjung@ualberta.ca [Department of Physics, University of Alberta, Edmonton, Alberta T6G 2E1 (Canada)

    2016-04-14

    We investigated magneto-transport properties of a compressively strained spatially confined La{sub 0.3}Pr{sub 0.4}Ca{sub 0.3}MnO{sub 3} (LPCMO) thin film micro-bridge deposited on LaAlO{sub 3}. Angular dependence of the magneto-resistance R(θ) of this bridge, where θ is the angle between the magnetic field and the current directions in the film plane, exhibits sharp positive and negative percolation jumps near T{sub MIT}. The sign and the magnitude of these jumps can be tuned using the magnetic field. Such behavior has not been observed in LPCMO micro-bridges subjected to tensile strain, indicating a correlation between the type of the lattice strain, the distribution of electronic domains, and the anisotropic magneto-resistance in spatially confined manganite systems.

  17. Manipulating the ferromagnetism in narrow-bandwidth Pr{sub 1-x}Ca{sub x}MnO{sub 3} (0 ≤ x ≤ 0.6) by means of the Mn-Ru t{sub 2g} ferromagnetic super-exchanges

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Y. L.; Liu, M. F.; Xie, Y. L.; Yan, Z. B. [Laboratory of Solid State Microstructures and Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China); Dong, S. [Department of Physics, Southeast University, Nanjing 211189 (China); Liu, J.-M. [Laboratory of Solid State Microstructures and Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China); Institute for Advanced Materials and Laboratory of Quantum Engineering and Materials, South China Normal University, Guangzhou 510006 (China)

    2015-09-28

    The concurrent ferromagnetic and metal-insulator transitions via the double-exchange route and electronic phase separation scenario represent the core ingredients of the physics of manganites. In this work, a Ca{sup 2+} and Ru{sup 4+} co-substitution of Pr{sup 3+} and Mn{sup 3+} in narrow-bandwidth and insulating PrMnO{sub 3}, namely, Pr{sub 1-x}Ca{sub x}Mn{sub 1-x}Ru{sub x}O{sub 3} (PCMRO, x ≤ 0.6), is carried out in order to investigate an alternative approach to effectively manipulate the ferromagnetism of PrMnO{sub 3}-based manganites. It is revealed that PCMRO over the whole substitution range is homogeneous solid solution with increased lattice distortion. The preference of Ru{sup 4+} valence state and the absence of Mn{sup 4+} valence state disable the Mn{sup 3+}-Mn{sup 4+} e{sub g}-orbital double-exchange, and the random occupation of Ru{sup 4+} in the lattice excludes the charge ordering and electronic phase separation. While all these consequences should favor antiferromagnetic insulating states, nevertheless, a high-temperature ferromagnetic transition is triggered by the co-substitution and the magnetization can reach up to ∼1.0 μ{sub B}/f.u. at x ∼ 0.2–0.3, much bigger than the moment (<0.1 μ{sub B}/f.u.) of Pr{sub 1−x}Ca{sub x}MnO{sub 3} in the weak ferromagnetic insulator state. It is suggested that this strong ferromagnetism is substantially ascribed to the Mn{sup 3+}-Ru{sup 4+} t{sub 2g}-orbital ferromagnetic super-exchange, and a simple geometric network illustration of the magnetism and electrical transport is presented.

  18. Comparative study of perovskite Pr{sub (1-x)}Ca{sub x}CoO{sub 3} e Gd{sub (1-x)}Ca{sub x}CoO{sub 3} (x=0,2) synthesized by gelatin modified route for application in automotive catalysis; Estudo comparativo das perovsquitas Pr{sub (1-x)}Ca{sub x}CoO{sub 3} e Gd{sub (1-x)}Ca{sub x}CoO{sub 3} (x=0,2) sintetizadas pela rota modificada gelatina para aplicacao em catalise automotiva

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, E.M. de; Medeiros, M.R.A.; Paiva, A.K.O.; Borges, F.M.M., E-mail: eduardamedeirosdearaujo@gmail.com [Universidade Federal do Rio Grande do Norte (UFRN), RN (Brazil); Ruiz, J.A.C. [Centro de Tecnologia do Gas e Energias Renovaveis (CTGAS-ER), RN (Brazil)

    2016-07-01

    Increased air pollution intensified the search for materials that could convert pollutant gases into less harmful substances. Thus, mixed oxides with perovskite structure began to be developed for presenting important features for the automotive catalysis. In this study has been compared the chemical composition of the materials with Pr{sub (1-x)}Ca{sub x}CoO{sub 3} and Gd{sub (1-x)}Ca{sub x}CoO{sub 3} (x = 0.2) synthesized by the method gelatine. The samples were characterized by techniques: Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-Ray Diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF) and subjected to the catalytic test in methane combustion reaction. The evaluation of the catalytic activity showed that gadolinium catalyst is more efficient compared with the praseodymium catalyst, although they have similar maximum conversion of methane at high temperature, during the catalytic test the material with gadolinium showed higher catalytic activity and stability. (author)

  19. Critical behavior of resistivity in the pressure-induced first to second order transition in Pr{sub 0.6}Ca{sub 0.4}Mn{sub 0.96}B{sub 0.04}O{sub 3} (B = Co and Cr)

    Energy Technology Data Exchange (ETDEWEB)

    Thiyagarajan, R.; Esakki Muthu, S.; Kalai Selvan, G. [Centre for High Pressure Research, School of Physics, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu (India); Mahendiran, R. [Department of Physics, 2 Science Drive 3, Faculty of Science, National University of Singapore, Singapore 117551 (Singapore); Arumugam, S., E-mail: sarumugam1963@yahoo.com [Centre for High Pressure Research, School of Physics, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu (India)

    2015-01-05

    Highlights: • 1st order PMI–FMM transition at T{sub IM} Pr{sub 0.6}Ca{sub 0.4}Mn{sub 0.96}B{sub 0.04}O{sub 3} (B = Co and Cr) samples. • Crossover from 1st to 2nd order is observed by the application of P on both the samples. • Critical exponents’ are close to the 3D Heisenberg model for the Co doped sample. • Critical exponents’ are close to the Mean field model for the Cr doped sample. - Abstract: We have investigated the hydrostatic pressure (P) dependence of the resistivity on Pr{sub 0.6}Ca{sub 0.4}Mn{sub 0.96}B{sub 0.04}O{sub 3} (B = Co and Cr) polycrystals. At ambient pressure, the temperature dependence of resistivity [ρ(T)] of both the samples show a first order paramagnetic insulator–ferromagnetic metallic transition at T = T{sub IM}. The application of P on both the samples increases the T{sub IM}, reduces the resistivity, and suppresses the hysteresis width, indicating a crossover from first to second order transition. The critical pressure, where the first–second order crossover takes place, are 2.02 and 2.40 GPa for Co and Cr doped samples respectively. The critical property of both systems around second order transition is investigated using Fisher–Langer relation and Suezaki–Mori method. The estimated critical exponents are close to the three-dimensional Heisenberg model for the Co doped sample suggesting short range interaction, and the exponents for the Cr doped sample follow the mean field theory suggesting long range ferromagnetic order. Further, the application of P suppresses the high temperature resistivity by reducing high temperature polarons in the case of the Cr doped sample, but it does not happen for the Co doped sample. The application of P helps to examine the stability of polarons in the high temperature regime.

  20. Absence of the impurity-induced magnetic order in the electron-doped high-T {sub c} cuprates Pr{sub 0.86}LaCe{sub 0.14}Cu{sub 1-y}(Zn, Ni) {sub y}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Risdiana [Department of Applied Physics, Graduate School of Engineering, Tohoku University, 6-6-05, Aoba, Aramaki, Aoba-ku, Sendai 980-8579 (Japan)]. E-mail: risdiana@teion.apph.tohoku.ac.jp; Adachi, T. [Department of Applied Physics, Graduate School of Engineering, Tohoku University, 6-6-05, Aoba, Aramaki, Aoba-ku, Sendai 980-8579 (Japan); Koike, Y. [Department of Applied Physics, Graduate School of Engineering, Tohoku University, 6-6-05, Aoba, Aramaki, Aoba-ku, Sendai 980-8579 (Japan); Watanabe, I. [Advanced Meson Science Laboratory, Institute of Physical and Chemical Research (RIKEN), 2-1 Hirosawa, Wako 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK-IMSS), 1-1 Oho, Tsukuba 305-0801 (Japan)

    2005-10-01

    Zero-field muon-spin-relaxation measurements have been carried out in order to investigate the Zn- and Ni-substitution effects on the Cu-spin dynamics in the electron-doped Pr{sub 0.86}LaCe{sub 0.14}Cu{sub 1-y}(Zn, Ni) {sub y}O{sub 4+{alpha}}{sub -{delta}} with y = 0, 0.01, 0.02, 0.05 and different values of the reduced oxygen content {delta} ({delta} {<=} 0.09). For the samples with y = 0 and very small {delta} values of {delta} < 0.01, a muon-spin precession due to the formation of a long-range antiferromagnetic order has been observed at low temperatures below {approx}5 K. For the moderately oxygen-reduced samples of 0.01 {<=} {delta} {<=} 0.09, on the contrary, no muon-spin precession has been observed and the temperature dependence of the spectra is similar to one another regardless of the y value. That is, no impurity-induced slowing down of the Cu-spin fluctuations has been detected, which is very different from the results of the hole-doped high-T{sub c} cuprates. The reason is discussed.

  1. Chemical insertion in the perovskite solid solutions Pr{sub 0.5+x-y}Li{sub 0.5-3x}Bi{sub y}{open_square}{sub 2x}TiO{sub 3}: Implications on the electrical properties

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Sanchez, M.F., E-mail: rusonil@yahoo.com [Unidad Profesional Interdisciplinaria en Ingenieria y Tecnologias Avanzadas-Instituto Politecnico Nacional (IPN), C.P. 07340, Mexico D.F. (Mexico); Fernandez, N. [Departamento de Quimica Inorganica, Universidad de la Habana, 10400 Ciudad de la Habana (Cuba); Martinez-Sarrion, M.-L.; Mestres, L. [Departament de Quimica Inorganica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Santana, G. [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Coyoacan 04510, Mexico D.F. (Mexico); Lewis, D.W. [Department of Chemistry, University College London, 20 Gordon St., London WC1H 0AJ (United Kingdom); Ruiz-Salvador, A.R. [Instituto de Ciencia y Tecnologia de Materiales, Universidad de La Habana, 10400 Ciudad de la Habana (Cuba)

    2012-05-15

    Highlight: Black-Right-Pointing-Pointer Lithium insertion is related to the number of vacancies and bismuth concentration. Black-Right-Pointing-Pointer The use of Kramers-Kronig relations allows the separation of the electronic conductivities. Black-Right-Pointing-Pointer The insertion changes the samples from ionic conductors to mixed conductors. Black-Right-Pointing-Pointer Electronic conduction is via a polaron mechanism with activation energy of {approx}0.8 eV. - Abstract: Chemical insertion and de-insertion of lithium in pellet samples of the solid solutions Pr{sub 0.5+x-y}Li{sub 0.5-3x}Bi{sub y}{open_square}{sub 2x}TiO{sub 3} were studied. Two regions of the phase diagram are studied: one having constant composition of bismuth and the other of lithium. The amount of inserted lithium depends on both the number of vacancies and the amount of bismuth in the original samples. The conductivity of the samples is directly related to the amount of inserted lithium and the activation energy depends on the unit cell volume. An analysis of the electronic and ionic components of the conductivity reveals that the untreated materials are pure ionic conductors, while after Li-insertion an additional electronic conductivity (t < 10{sup -2}) occurs, due to a polaron mechanism, with an activation energy of 0.8 eV.

  2. A comparative study of magnetic field induced meta-magnetic transition in nanocrystalline and bulk Pr{sub 0.65}(Ca{sub 0.7}Sr{sub 0.3}){sub 0.35}MnO{sub 3} compound

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Suvayan [CMP Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700 064 (India); Center for Research in Nanoscience and Nanotechnology, University of Calcutta, JD-2, Salt Lake City, Kolkata 700098, West Bengal (India); Department of Physics, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India); Das, Kalipada, E-mail: kalipadadasphysics@gmail.com [Department of Materials Science, Indian Association for the Cultivation of Science, 2A and 2B Raja S.C. Mullick Road, Jadavpur, Kolkata 700032 (India); Bandyopadhyay, Sudipta [Center for Research in Nanoscience and Nanotechnology, University of Calcutta, JD-2, Salt Lake City, Kolkata 700098, West Bengal (India); Department of Physics, University of Calcutta, 92 A.P.C. Road, Kolkata 700009 (India); Das, I. [CMP Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700 064 (India)

    2017-06-15

    Highlights: • Field induced sharp meta-magnetic transition appears even in nanocrystalline sample. • Magnetic field for the meta-magnetic transition enhances depending upon the cooling field. • This unusual behavior is addressed by the effect of the interfacial strains. - Abstract: In our present study we highlight the observations of external magnetic field induced sharp meta-magnetic transition in polycrystalline bulk as well as nanocrystalline form of Pr{sub 0.65}(Ca{sub 0.7}Sr{sub 0.7}){sub 0.35}MnO{sub 3} compound. Interestingly, such behavior persists in the nanoparticles regardless of the disorder broadened transition. However, higher magnetic field is required for nanoparticles having average particle size ∼40 nm for such meta-magnetic transition, which differs from the general trends of the pure charge ordered nano materials. The interfacial strain between the different magnetic domains plays the important role in magnetic isothermal properties of nanoparticles, when the samples are cooled down in different cooling field. Additionally, both the bulk and nanoparticle compounds exhibit spontaneous phase separation and significantly large magnetoresistance at the low temperature region due to the melting of charge ordered fraction.

  3. Effect of Ni-doping on critical behavior of La{sub 0.6}Pr{sub 0.1}Ba{sub 0.3}Mn{sub 1−x}Ni{sub x}O{sub 3} nanocrystalline manganites

    Energy Technology Data Exchange (ETDEWEB)

    Oumezzine, Elaa [Laboratoire de Physico-chimie des Matériaux, Faculté des Sciences de Monastir, Département de Physique, Université de Monastir, 5019 Monastir (Tunisia); Hcini, Sobhi, E-mail: hcini_sobhi@yahoo.fr [Laboratoire de Physico-chimie des Matériaux, Faculté des Sciences de Monastir, Département de Physique, Université de Monastir, 5019 Monastir (Tunisia); Hlil, E.K. [Institut Néel, CNRS et Université Joseph Fourier, BP 166, 38042 Gronoble (France); Dhahri, Essebti [Laboratoire de Physique Appliquée, Faculté des Sciences de Sfax, Université de Sfax, B.P. 1171, 3000 Sfax (Tunisia); Oumezzine, Mohamed [Laboratoire de Physico-chimie des Matériaux, Faculté des Sciences de Monastir, Département de Physique, Université de Monastir, 5019 Monastir (Tunisia)

    2015-11-15

    We used Banerjee's criteria, modified Arrott plots and the scaling hypothesis to analyze magnetic-field dependences of magnetization near the ferromagnetic–paramagnetic (FM–PM) phase-transition temperature (T{sub C}) of La{sub 0.6}Pr{sub 0.1}Ba{sub 0.3}Mn{sub 1−x}Ni{sub x}O{sub 3} (0≤x≤0.3) nanocrystalline manganites. Experimental results reveal that all samples undergo a second-order phase transition. The estimated critical exponents obtained for x=0 sample are close to the mean-field model (β=0.503±0.004, γ= 1.024±0.068 and δ=2.821 at T{sub C}=215 K). Whereas for a high amount of Ni, these exponents belong to a different universality class (β=0.599±0.014, γ=0.897±0.013 and δ=2.570 at T{sub C}=162 K for x=0.1 sample) and (β=0.733±0.012, γ=0.753±0.014 and δ=2.320 at T{sub C}=131 K for x=0.3 sample). This is due to the fact that the substitution of Ni ions into the Mn-site leads to the formation of a larger proportion of Mn{sup 4+} with respect to Mn{sup 3+} which reduces the ferromagnetic double exchange interaction of Mn{sup 3+}–Mn{sup 4+} couples. These exponents indicate that the exchange interaction J(r) decreases with distance r slower than r{sup −4.5} for x=0 sample, however it ranges from r{sup −5} and r{sup −4.5} for x=0.1 and 0.3 samples.

  4. Synthesis, characterization and magnetic properties of ultrafine Co3O4 octahedra

    Directory of Open Access Journals (Sweden)

    Y. H. Chen

    2015-08-01

    Full Text Available Octahedral Co3O4 nanoparticles were synthesised in an aqueous ammonia solution using hexagonal β-Co(OH2 nanoplates as starting materials. Electron microscopy analysis indicates that the Co3O4 particles have diameters of 20-40 nm and adopt a well-crystallized cubic spinel structure. The octahedral habit was verified by high angle annular dark field imaging. High resolution electron microscopy results revealed that the long axis of the octahedral Co3O4 nanoparticles coincides with crystallographic direction and the facets are the {111} planes. Magnetization measurements reveal antiferromagnetic ordering below 10 K, with a paramagnetic Curie temperature of 3 K and a paramagnetic susceptibility that is double that expected for high-spin Co2+. The results show that a substantial fraction of the B-site Co3+ in the nanoparticles is in a high-spin state.

  5. Oxygen octahedra picker: A software tool to extract quantitative information from STEM images

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yi, E-mail: y.wang@fkf.mpg.de; Salzberger, Ute; Sigle, Wilfried; Eren Suyolcu, Y.; Aken, Peter A. van

    2016-09-15

    In perovskite oxide based materials and hetero-structures there are often strong correlations between oxygen octahedral distortions and functionality. Thus, atomistic understanding of the octahedral distortion, which requires accurate measurements of atomic column positions, will greatly help to engineer their properties. Here, we report the development of a software tool to extract quantitative information of the lattice and of BO{sub 6} octahedral distortions from STEM images. Center-of-mass and 2D Gaussian fitting methods are implemented to locate positions of individual atom columns. The precision of atomic column distance measurements is evaluated on both simulated and experimental images. The application of the software tool is demonstrated using practical examples. - Highlights: • We report a software tool for mapping atomic positions from HAADF and ABF images. • It enables quantification of both crystal lattice and oxygen octahedral distortions. • We test the measurement accuracy and precision on simulated and experimental images. • It works well for different orientations of perovskite structures and interfaces.

  6. Faceting of Nanocrystals during Chemical Transformation: FromSolid Silver Spheres to Hollow Gold Octahedra

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Yadong; Erdonmez, Can; Alivisatos, A. Paul

    2006-06-23

    Sustained progress in nanocrystal synthesis has enabled recent use of these materials as inorganic, macromolecular precursors that can be chemically transformed into new nanostructures. The literature now contains several cases with chemical transformations being accompanied by varying degrees of modification of properties, including crystal structure and particle shape. As a recent example, we demonstrated that as-synthesized metallic nanocrystals yield, upon oxidation, nanostructures with modified morphologies such as hollow particles. This morphological change derives from directional material flows due to differing diffusivities for the reacting atomic species, in a nanoscale version of the well-known Kirkendall Effect. This general methodology has since been extended by other groups to produce nanostructures with various compositions and shapes. We demonstrate that performing a replacement reaction on single crystalline Ag nanospheres of {approx}10 nm in diameter in an organic solvent produces hollow Au nanocrystals with an octahedral shape. Different from those Au shells made by starting with Ag particles about one order of magnitude larger, which largely reproduce that of the sacrificial Ag counterparts, the hollow nanocrystals obtained in this work show significant changes in the external morphology from the spherical Ag precursors. This evolution of a faceted external morphology during chemical transformation is made possible by the enhanced role of surface effects in our smaller nanocrystals. The competition between the Au atom deposition and Ag atom dissolution on various nanocrystal surfaces is believed to determine the final octahedral shape of the hollow Au nanocrystals. Simultaneous achievement of surface-mediated shape control and a hollow morphology in a one-pot, single-step synthetic procedure in this study promises an avenue to finer tuning of particle morphology, and thus physical properties such as surface plasmon resonance.

  7. Corrosion behavior of magnetron sputter-deposited (Mo/0.6/Ru/0.4/)82B18 and Mo82B18 amorphous metal films

    Science.gov (United States)

    Williams, R. M.; Thakoor, A. P.; Khanna, S. K.; Johnson, W. L.

    1984-01-01

    Amorphous metallic films of Mo49Ru33B18 and Mo82B18 have been prepared by magnetron sputtering, and their corrosion behavior was investigated and compared with amorphous liquid-quenched Mo49Ru33B18 and crystalline Mo i acidic and basic solutions. Sputtered Mo49Ru33B18 showed lower corrosion rates compared with liquid-quenched Mo49Ru33B18, owing to the superior surface smoothness and uniformity of the former. Amorphous Mo82B18 showed low corrosion rates in both acidic and basic aqueous solutions. Comparison of the corrosion properties of Mo49Ru33B18 with Mo82B18 and Mo demonstrates the roles of the alloys' constituents. Ru significantly extends the passive region to high-anodic potentials, but, at less-anodic potentials, Mo82B18 has the lowest corrosion rate.

  8. New electrochemiluminescence catalyst: Cu2O semiconductor crystal and the enhanced activity of octahedra synthesized by iodide ions coordination

    DEFF Research Database (Denmark)

    Zhang, Ling; Qi, Liming; Gao, Wenyue

    2017-01-01

    Cuprous oxide (Cu2O) crystals are usually used as the photocatalysts of water splittings and carbon monoxide oxidations. Herein, we report the new catalytic properties of Cu2O to the electrochemilumenescence (ECL) reactions of luminol and oxygen. Adjusting the shape of Cu2O microcrystals from cub...

  9. Synthesis, spectroscopic characterization, and x-ray structural determination of W(CO)/sub 4/(PR/sub 3/)CNC/sub 6/H/sub 4/(PR/sub 3/ (R = Ph, Et)

    Energy Technology Data Exchange (ETDEWEB)

    Rommel, J.S.; Weinrach, J.B.; Grubisha, D.S.; Bennett, D.W.

    1988-08-24

    Two bimetallic complexes containing 1,4-diisocyanobenzene as a bridging ligand have been prepared and examined by x-ray crystallography and /sup 13/C NMR, /sup 31/P NMR, and infrared spectroscopies. W(CO)/sub 4/(PEt/sub 3/)CNC/sub 6/H/sub 4/NCW(CO)/sub 4/(PEt/sub 3/) (1) and W(CO)/sub 4/(PPh/sub 3/)CNC/sub 6/H/sub 4/NCW(CO)/sub 4/(PPh/sub 3/) (2) both crystallized in the same space group in very similar packing environments. Crystal data: for 1, monoclinic space group P2/sub 1//n,a = 7.780 (2) /angstrom/, b = 15.930 (3) /angstrom/, c = 14.137 (6) /angstrom/, /beta/ = 99.56 (3)/degree/, Z = 2, R = 0.040; for 2, monoclinic space group P2/sub 1//n, a = 11.641 (2) /angstrom/, b = 16.970 (2) /angstrom/, c = 12.463 (2), /angstrom/, /beta/ = 101.24 (1)/degree/, Z = 2, R = 0.047; NMR chemical shifts and vibrational frequencies for CNC/sub 6/H/sub 4/NC experience significant changes upon coordination, and the presence of an organophosphine ligand in the metal coordination sphere causes the diisocyanide to experience in-plane bends of 10.8/degrees/ for 1 and 4.2/degree/ for 2. In spite of strong evidence for the M-CNR back-bonding, the C-N bond length varies only negligibly among 1, 2, and CNC/sub 6/H/sub 4/NC, the free ligand. 20 references, 2 figures, 8 tables.

  10. Facile synthesis of PbTiO3 truncated octahedra via solid-state reaction and their application in low-temperature CO oxidation by loading Pt nanoparticles

    KAUST Repository

    Yin, Simin

    2014-01-01

    Perovskite PbTiO3 (PTO) nanocrystals with a truncated octahedral morphology have been prepared by a facile solid-state reaction. Pt nanoparticles preferentially nucleated on the {111} facet of PTO nanocrystals exhibit a remarkable low-temperature catalytic activity towards CO oxidation from a temperature as low as 30 °C and achieve 100% conversion at ∼50 °C. © 2014 the Partner Organisations.

  11. Surface energy-driven growth of crystalline PbS octahedra and dendrites in the presence of cyclodextrin–surfactant supramolecular complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Pradip, E-mail: pkgangwar84@gmail.com; Kim, Whi Dong; Lee, Seokwon; Lee, Dennis T. [Korea Advanced Institute of Science and Technology (KAIST), Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (Korea, Republic of); Lee, Kangtaek [Yonsei University, Department of Chemical and Biomolecular Engineering (Korea, Republic of); Lee, Doh C., E-mail: dclee@kaist.edu [Korea Advanced Institute of Science and Technology (KAIST), Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (Korea, Republic of)

    2015-02-15

    PbS crystals of cubic, octahedral, and dendritic shapes are synthesized in an aqueous solution that contains supramolecular complexes of β-cyclodextrin (CD) and hexadecyltrimethylammonium bromide (CTAB). The morphology of the PbS crystals depends on the concentration of CD or CTAB in the reaction solution; for example, the branched dendritic structures evolve with an appropriate molar ratio of CD/CTAB supramolecular complexes and reaction time. Regardless of the CD/CTAB molar ratios, octahedral PbS crystals are observed at all compositions of CD/CTAB for the reaction times of 1–5 h, while self-assembled branched/dendritic structures are obtained only for CD/CTAB molar ratios of 0.5, 1, and 2 after a prolonged reaction, e.g., for 24–48 h. Systematic investigation reveals that both reaction time and CD/CTAB molar ratio are responsible for self-assembled branched/dendritic structures of octahedral crystals.

  12. Electronic structure of layered ferroelectric high-k titanate Pr>2Ti2O7

    DEFF Research Database (Denmark)

    Atuchin, V.V.; Gavrilova, T.A.; Grivel, Jean-Claude

    2012-01-01

    The spectroscopic parameters and electronic structure of binary titanate Pr2Ti2O7 have been studied by IR-, Raman and X-ray photoelectron spectroscopy (XPS) for the powder sample prepared by solid state synthesis. The spectral features of valence band and all constituent element core levels have ...... parameters in comparison with those of other titanium- and praseodymium-bearing oxides....

  13. Structures and stabilities of trivalent and tetravalent rare earth ions in sevenfold and eightfold coordination in fluorite-related complex oxides

    Energy Technology Data Exchange (ETDEWEB)

    Morss, L.R.

    1991-12-31

    This paper reports the preparation and characterization of a series of oxides containing 3+ or 4+ lanthanide (M = Ce, Pr, or Tb) ions, with different ionic sizes and varying M{sup 4+}/M{sup 3+} reduction potentials, in nearly cubic coordination. The objective of the study was to demonstrate how oxidation-reduction characteristics and ionic size trends explain the properties of these oxides and to compare the oxidation-reduction stability of M{sup 3+} and M{sup 4+} lanthanide ions in high (CN 7 or 8) coordination in fluorite-related oxides versus low (CN 6) coordination in perovskite oxides. Efficient preparative methods are reported, as well as powder diffraction and thermogravimetric measurements for oxides CaMTi{sub 2}O{sub 7-x} and CaMZr{sub 2}O{sub 7-x}. These oxides were characterized by X-ray powder diffraction and by thermogravimetric analysis. CaCeTi{sub 2}O{sub 7} is a pyrochlore, a = 10.142(4) {Angstrom}, with Ce{sup 4+} much more easily reducible than in the perovskite BaCeO{sub 3}. By contrast, a preparation with the stoichiometry ``CaPbTi{sub 2}O{sub 7-x}`` is a two-phase mixture-of perovskite CaTiCo{sub 3} and a presumably Pr{sup 3+}-rich pyrochlore Pr{sub 2}Ti{sub 2}O{sub 7}(?). CaTbTi{sub 2}O{sub 7-x} appears to be a Tb{sup 3+} pyrochlore, a = 10.149(2) {Angstrom}. CaCeZr{sub 2}O{sub 7} is a pyrochlore, a = 10.524(1) {Angstrom}. A preparation of ``CaPbZr{sub 2}O{sub 7-x}`` also appeared to yield a two-phase mixture, perovskite CaZrO{sub 3} and pyrochlore Pr{sub 2}Zr{sub 2}O{sub 7}. In this paper, the structures, f-element ion sites, and M(4)-M(3) stability trends in the CaMTi{sub 2}O{sub 7-x} and CaMZr{sub 2}O{sub 7-x} oxides are compared with the structural and stability trends in the perovskites BaMO{sub 3} which have M{sup 4+} ions in sixfold (tilted octahedra) coordination.

  14. Effect of Flap Mutations on Structure of HIV-1 Protease and Inhibition by Sanquinavir and Darunavir

    Energy Technology Data Exchange (ETDEWEB)

    Liu, F.; Kovalevsky, A.; Tie, Y.; Ghosh, A.; Harrison, R.; Weber, I. (GSU); (Purdue)

    2008-08-25

    HIV-1 (human immunodeficiency virus type 1) protease (PR) and its mutants are important antiviral drug targets. The PR flap region is critical for binding substrates or inhibitors and catalytic activity. Hence, mutations of flap residues frequently contribute to reduced susceptibility to PR inhibitors in drug-resistant HIV. Structural and kinetic analyses were used to investigate the role of flap residues Gly48, Ile50, and Ile54 in the development of drug resistance. The crystal structure of flap mutants PR{sub I50V} (PR with I50V mutation), PR{sub I54V} (PR with I54V mutation), and PR{sub I54M} (PR with I54M mutation) complexed with saquinavir (SQV) as well as PR{sub G48V} (PR with G48V mutation), PR{sub I54V}, and PR{sub I54M} complexed with darunavir (DRV) were determined at resolutions of 1.05--1.40 {angstrom}. The PR mutants showed changes in flap conformation, interactions with adjacent residues, inhibitor binding, and the conformation of the 80s loop relative to the wild-type PR. The PR contacts with DRV were closer in PR{sub G48V}-DRV than in the wild-type PR-DRV, whereas they were longer in PR{sub I54M}-DRV. The relative inhibition of PR{sub I54V} and that of PR{sub I54M} were similar for SQV and DRV. PR{sub G48V} was about twofold less susceptible to SQV than to DRV, wheres the opposite was observed for PR{sub I50V}. The observed inhibition was in agreement with the association of G48V and I50V with clinical resistance to SQV and DRV, respectively. This analysis of structural and kinetic effects of the mutants will assist in the development of more effective inhibitors for drug-resistant HIV.

  15. Environmental TEM Study of Electron Beam Induced Electrochemistry of Pr>0.64Ca0.36MnO3 Catalysts for Oxygen Evolution

    DEFF Research Database (Denmark)

    Mildner, Stephanie; Beleggia, Marco; Mierwaldt, Daniel

    2015-01-01

    an ETEM study of a Pr0.64Ca0.36MnO3 (PCMO) thin filth electrocatalySt for water splitting and Oxygen evolution in contact with water vapor: We show by means of off-axis electron holography and electrostatic modeling that the electron beam gives rise to a positive electric sample potential due to secondary....... The first reaction is an anodic oxidation of oxygen depleted amorphous PCMO which results in recrystallization of the oxide. The Second reaction is oxygen evolution which can be detected by the oxidation of a silane additive and formation of SiO2-gamma at catalytically active surfaces. The quantification...

  16. The low-temperature magnetostructure and magnetic field response of Pr>0.9Ca0.1MnO3

    DEFF Research Database (Denmark)

    Tikkanen, J.; Frontzek, M.; Hergert, W.

    2016-01-01

    calculations. Particular emphasis was placed on determining the presence of nanoscale magnetic phase separation. Previously published results of a canted A-AFM average ground state were reproduced to a good precision both experimentally and theoretically, and complemented by investigating the effects...... phase separation model of manganites to the material under discussion despite its very low Ca doping level in the context of the model. In the light of the new data, we also conclude that the low temperature magnetic moment of Pr must be ca. 300% larger than previously thought in this material, close...

  17. Amprenavir complexes with HIV-1 protease and its drug-resistant mutants altering hydrophobic clusters

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Chen-Hsiang; Wang, Yuan-Fang; Kovalevsky, Andrey Y.; Harrison, Robert W.; Weber, Irene T. (GSU)

    2010-10-22

    The structural and kinetic effects of amprenavir (APV), a clinical HIV protease (PR) inhibitor, were analyzed with wild-type enzyme and mutants with single substitutions of V32I, I50V, I54V, I54M, I84V and L90M that are common in drug resistance. Crystal structures of the APV complexes at resolutions of 1.02-1.85 {angstrom} reveal the structural changes due to the mutations. Substitution of the larger side chains in PR{sub V32I}, PR{sub I54M} and PR{sub L90M} resulted in the formation of new hydrophobic contacts with flap residues, residues 79 and 80, and Asp25, respectively. Mutation to smaller side chains eliminated hydrophobic interactions in the PR{sub I50V} and PR{sub I54V} structures. The PR{sub I84V}-APV complex had lost hydrophobic contacts with APV, the PR{sub V32I}-APV complex showed increased hydrophobic contacts within the hydrophobic cluster and the PR{sub I50V} complex had weaker polar and hydrophobic interactions with APV. The observed structural changes in PR{sub I84V}-APV, PR{sub V32I}-APV and PR{sub I50V}-APV were related to their reduced inhibition by APV of six-, 10- and 30-fold, respectively, relative to wild-type PR. The APV complexes were compared with the corresponding saquinavir complexes. The PR dimers had distinct rearrangements of the flaps and 80's loops that adapt to the different P1{prime} groups of the inhibitors, while maintaining contacts within the hydrophobic cluster. These small changes in the loops and weak internal interactions produce the different patterns of resistant mutations for the two drugs.

  18. The motley family of polar compounds (MV)[M(X{sub 5-x}X Prime {sub x})] based on anionic chains of trans-connected M{sup (III)}(X,X Prime ){sub 6} octahedra (M=Bi, Sb; X, X Prime =Cl, Br, I) and methylviologen (MV) dications

    Energy Technology Data Exchange (ETDEWEB)

    Leblanc, Nicolas [Laboratoire MOLTECH-Anjou, UMR-CNRS 6200, Universite d' Angers 2 Bd Lavoisier, 49045 Angers (France); Mercier, Nicolas, E-mail: nicolas.mercier@univ-angers.fr [Laboratoire MOLTECH-Anjou, UMR-CNRS 6200, Universite d' Angers 2 Bd Lavoisier, 49045 Angers (France); Allain, Magali; Toma, Oksana [Laboratoire MOLTECH-Anjou, UMR-CNRS 6200, Universite d' Angers 2 Bd Lavoisier, 49045 Angers (France); Auban-Senzier, Pascale; Pasquier, Claude [Laboratoire de Physique des Solides, UMR-CNRS 8502, Bat. 510,Universite Paris Sud, 91405 Orsay (France)

    2012-11-15

    The search for hybrid organic-inorganic materials remains a great challenge in the field of ferroelectrics. Following the discovery of the room temperature ferroelectric material (MV)[BiI{sub 3}Cl{sub 2}] (MV{sup 2+}: methylviologen) exhibiting the highest polarization value in the field of hybrid ferroelectrics, we report here nine new hybrids with the general formulation (MV)[M{sup (III)}X{sub 5-x}X Prime {sub x}] (M=Bi, Sb; X, X Prime =Cl, Br, I): (MV)[BiCl{sub 3.3}Br{sub 1.7}] (1), (MV)[BiCl{sub 1.3}Br{sub 3.7}] (2), (MV)[BiBr{sub 3.2}I{sub 1.8}] (3), (MV)[SbCl{sub 5}] (4), (MV)[SbBr{sub 5}] (5), (MV)[SbCl{sub 3.8}Br{sub 1.2}] (6), (MV)[SbCl{sub 2.4}Br{sub 2.6}] (7), (MV)[SbI{sub 3}Cl{sub 2}] (8) and (MV)[SbBr{sub 3.8}I{sub 1.2}] (9). Depending on the presence of polar chains or not, and on the coupling of polar chains, two types of centrosymmetrical structures [C1] and [C2] and two types of polar structures [P1] and [P2] are defined. (2) undergoes a paraelectric-to-relaxor ferroelectric transition around 100-150 K depending of the frequency showing that the Curie temperature, T{sub C}, of (MV)[BiBr{sub 5}] (243 K) can be modulated by the substitution of Br by Cl. The most interesting family is the [P2] type because the syn coupling of polar chains is in favor of high polarization values, as in (MV)[BiI{sub 3}Cl{sub 2}]. Five of the nine new hybrids, (4), (6-9), which have the [P2] type structure are potential ferroelectrics. - Graphical abstract: The methylviologen haloantimonate (MV)[SbX{sub 5-x}X Prime {sub x}] families (X, X Prime =Cl, Br, I) - [P1] and [P2] are the two kinds of polar structures - and view of the (MV)[SbBr{sub 3.8}I{sub 1.2}] hybrid based on chiral polar chains which are in syn coupling. Highlights: Black-Right-Pointing-Pointer Nine hybrids based on methylviologen and halometalate chains have been discovered. Black-Right-Pointing-Pointer The polar nature of chains is due to the ns{sup 2} stereoactivity of Sb{sup (III)} or Bi{sup (III)}. Black-Right-Pointing-Pointer A syn or anti coupling of polar chains leads to two types of polar structures. Black-Right-Pointing-Pointer Five of the nine hybrids (syn coupling) are potential interesting ferroelectrics. Black-Right-Pointing-Pointer The para-to-ferroelectric T{sub C} depends on the bromide content x of (MV)[BiCl{sub 5-x}Br{sub x}].

  19. Synthesis and reactivity of {Ru(p-cymene)}2+ derivatives of [Nb6O19]8-: a rational approach towards fluxional organometallic derivatives of polyoxometalates.

    Science.gov (United States)

    Laurencin, Danielle; Thouvenot, René; Boubekeur, Kamal; Proust, Anna

    2007-04-07

    Three {Ru(p-cym)}(2+) (p-cym = p-cymene) derivatives of [Nb(6)O(19)](8-)-[Nb(6)O(19){Ru(p-cym)}](6-) (Nb(6)Ru(1)), trans-[Nb(6)O(19){Ru(p-cym)}(2)](4-) (t-Nb6Ru2), and [Nb(6)O(19){Ru(p-cym)}(4)] (Nb(6)Ru(4))--have been synthesized in water by reaction between [Ru(p-cym)Cl(2)](2) and the hexaniobate. In the solid state, Nb(6)Ru(1) and Nb(6)Ru(4) have been characterized by IR and EDX spectroscopies, whereas t-Nb(6)Ru(2) has been characterized by IR spectroscopy and single-crystal X-ray diffraction (crystal data for K(4)-trans-[Nb(6)O(19){Ru(p-cym)}(2)].14H(2)O (K(4)-t-Nb(6)Ru(2).14H(2)O). In solution, all compounds were characterized by (1)H NMR and ESI mass spectrometry analyses, and Nb(6)Ru(1) was also analyzed by (17)O NMR. These studies allowed a comparison of the differences in behaviour of the three complexes in water: Nb(6)Ru(1) is particularly stable, Nb(6)Ru(4) decomposes by loss of {Ru(p-cym)}(2+) fragments, and trans-[Nb(6)O(19){Ru(p-cym)}(2)](4-) isomerizes into cis-[Nb(6)O(19){Ru(p-cym)}(2)](4-). A rational mechanism for the isomerisation of t-Nb(6)Ru(2) is proposed on the basis of a kinetic study.

  20. Estudio comparativo de dos métodos de síntesis para la obtención de polvos cerámicos de ZnO - Pr>2O3 - CoO

    OpenAIRE

    Rodríguez-Páez, J. E.; Caballero, A. C.; Villegas, M.; Cruz, A M; Ávila, H.

    2004-01-01

    Zinc oxide containing rare earth metal and Cobalt oxide are utilized as raw material to make varistors. Some of systems were found to exhibit non-ohmic current-voltaje characteristics and they are applicable not only for low voltaje devices but also for hight voltaje electric power stations. The microstructure of ZnO varistor can be considered as a vehicle thorugh which all of these properties ara manifested. Therefore, a discussion of the microstructure cannot be separated from a discussion ...

  1. Electrical resistivity anomaly, valence shift of Pr ion, and magnetic behavior in epitaxial (Pr.sub.1-y./sub.Y.sub.y./sub.).sub.1-x./sub.Ca.sub.x./sub.CoO.sub.3./sub. thin films under compressive strain

    Czech Academy of Sciences Publication Activity Database

    Fujishiro, H.; Noda, Y.; Akuzawa, K.; Naito, T.; Ito, A.; Goto, T.; Maryško, Miroslav; Jirák, Zdeněk; Hejtmánek, Jiří; Nitta, K.

    2017-01-01

    Roč. 121, č. 11 (2017), s. 1-8, č. článku 115104. ISSN 0021-8979 R&D Projects: GA ČR GA17-04412S Institutional support: RVO:68378271 Keywords : perovskite cobaltites * spin state transition * variable valence * epitaxial strain * XANES Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.068, year: 2016

  2. A study of Pr>0.7Sr0.3Fe1-xNixO3 as a cathode material for SOFCs with intermediate operating temperature

    DEFF Research Database (Denmark)

    Hashimoto, S.I.; Kammer Hansen, K.; Larsen, P.H.

    2005-01-01

    Pr0.7Sr0.3Fe1-xNxO3-δ (PSFN; x=0.2-0.5) compounds were synthesized and characterized by powder X-ray diffraction (XRD), thermal expansion coefficient (TEC) measurements, electrical conductivity and electrochemical impedance spectroscopy on cone-shaped electrodes on a Ce0.9Gd0.1O1.95 (CGO10)...

  3. Mono and dinuclear arene ruthenium(II) triazoles by 1,3-dipolar cycloadditions to a coordinated azide in ruthenium(II) compounds

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Svitlyk, V.; Mozharivskyj, Y.

    reaction of [(η 6 - C 6 Me 6 )Ru(L 2 )Cl] with sodium azide. Notably, as mentioned earlier, a direct reaction of [(η 6 -C 6 Me 6 ) Ru(L 1 )Cl] (1) with NaN 3 in ethanol yielded tetra azido compound of formulation [{(η 6 - C 6 Me 6 )Ru(N 3 )(N 3 )} 2... sodium azide. As a part of our study on arene ruthenium (II) azide compounds, 11 herein, we would like to report, the synthesis of (η 6 -C 6 Me 6 ) ruthenium (II) azido compound 2 and the subsequent 1,3-dipolar cycloaddition reaction of 1 and 2...

  4. Magnetic interactions in new fluorite-related rare earth oxides LnLn’{sub 2}RuO{sub 7} (Ln, Ln’=rare earths)

    Energy Technology Data Exchange (ETDEWEB)

    Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp; Doi, Yoshihiro

    2016-07-15

    New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K, which is considerably lowered compared with that for Pr{sub 3}RuO{sub 7}. Analysis of the magnetic specific heat indicates that the magnetic behavior observed at 27 K for Pr{sub 2}YRuO{sub 7} is predominantly due to the magnetic interactions between Ru ions, and that the interactions between the Pr{sup 3+} and Ru{sup 5+} ions are also important. La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K, which is ascribed to the magnetic ordering between Ru{sup 5+} ions from the analysis of the magnetic specific heat data. - Graphical abstract: New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} show an antiferromagnetic transition at 27 and 9.0 K, respectively. Display Omitted - Highlights: • New fluorite-related quaternary rare earth oxides LnLn’{sub 2}RuO{sub 7} have been prepared. • Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K. • La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K. • Their magnetic exchange mechanism has been elucidated by the magnetic entropy change.

  5. Synthesis and characterization of several molybdenum chloride cluster compounds

    Energy Technology Data Exchange (ETDEWEB)

    Beers, W.W.

    1983-06-01

    Investigation into the direct synthesis of Mo/sub 4/Cl/sub 8/(P(C/sub 2/H/sub 5/)/sub 3/)/sub 4/ from Mo/sub 2/(OAc)/sub 4/ led to a synthetic procedure that produces yields greater than 80%. The single-crystal structure disclosed a planar rectangular cluster of molybdenum atoms. Metal-metal bond distances suggest that the long edges of the rectangular cluster should be considered to be single bonds and the short metal-metal bonds to be triple bonds. This view is reinforced by an extended Hueckel calculation. Attempts to add a metal atom to Mo/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ to form Mo/sub 5/Cl/sub 10/(PR/sub 3/)/sub 3/ led instead to a compound with the composition Mo/sub 8/Cl/sub 16/(PR/sub 3/)/sub 4/. Solution and reflectance uv-visible spectra and x-ray photoelectron spectra suggest that tetranuclear molybdenum units are present. The facile reaction between Mo/sub 8/Cl/sub 16/(PR/sub 3/)/sub 4/ and PR/sub 3/ imply that the linkage between tetrameric units is weak.

  6. A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

    Energy Technology Data Exchange (ETDEWEB)

    John G. Verkade

    1997-08-31

    Remarkably mild conditions have been discovered for quantitative sulfur removal from dibenzothiophene and other organosulfur systems using relatively cheap elemental sodium. The project objectives are: (1) Optimize the coal desulfurization reaction with respect to time, temperature, coal type and the R groups (including R = H), and also on extraction, impregnation and sonication conditions; (2) Optimize the conditions for the HDS reaction (which allows the PR{sub 3} to function as an HDS catalyst for coal) with respect to R group, temperature, pressure, H{sub 2} gas flow rate and inert solvent presence; (3) Determine the product(s) and the pathway of the novel redox reaction that appears to quantitatively remove sulfur from dibenzothiophene (DBT) when R = Bu when FeCl{sub 3} is used as a catalyst; (4) Impregnate sulfur-laden coals with Fe{sup 3+} to ascertain if the PR{sub 3} desulfurization rate increases; (5) Determine the nature of the presently unextractable phosphorus compounds formed in solid coals by PR{sub 3}; (6) Explore the efficacy of PR{sub 3}/Fe{sup 3+} in removing sulfur from petroleum feedstocks, heavy ends (whether solid or liquid), coal tar and discarded tire rubber; (7) Explore the possibility of using water-soluble PR{sub 3} compounds and Fe{sup 3+} to remove sulfur from petroleum feedstocks and heavy ends in order to remove the SPR{sub 3} (and Fe{sup 3+} catalyst) by water extraction (for subsequent HDS of the SPR{sub 3}); and (8) Explore the possibility of using solid-supported PR{sub 3} compounds (plus Fe{sup 3+} catalyst) to remove sulfur from petroleum feedstocks and heavy ends in order to keep the oil and the SPR{sub 3} (formed in the reaction) in easily separable phases.

  7. Facet-dependent and au nanocrystal-enhanced electrical and photocatalytic properties of Au-Cu2O core-shell heterostructures.

    Science.gov (United States)

    Kuo, Chun-Hong; Yang, Yu-Chen; Gwo, Shangjr; Huang, Michael H

    2011-02-02

    We report highly facet-dependent electrical properties of Cu(2)O nanocubes and octahedra and significant enhancement of gold nanocrystal cores to the electrical conductivity of Au-Cu(2)O core-shell octahedra. Cu(2)O nanocubes and octahedra and Au-Cu(2)O core-shell cubes and octahedra were synthesized by following our reported facile procedures at room temperature. Two oxide-free tungsten probes attached to a nanomanipulator installed inside a scanning electron microscope made contacts to a single Cu(2)O nanocrystal for the I-V measurements. Pristine Cu(2)O octahedra bounded by {111} facets are 1100 times more conductive than pristine Cu(2)O cubes enclosed by {100} faces, which are barely conductive. Core-shell cubes are only slightly more conductive than pristine cubes. A 10,000-fold increase in conductivity over a cube has been recorded for an octahedron. Remarkably, core-shell octahedra are far more conductive than pristine octahedra. The same facet-dependent electrical behavior can still be observed on a single nanocrystal exposing both {111} and {100} facets. This new fundamental property may be observable in other semiconductor nanocrystals. We also have shown that both core-shell cubes and octahedra outperform pristine cubes and octahedra in the photodegradation of methyl orange. Efficient photoinduced charge separation is attributed to this enhanced photocatalytic activity. Interestingly, facet-selective etching occurred over the {100} corners of some octahedra and core-shell octahedra during photocatalysis. The successful preparation of Au-Cu(2)O core-shell heterostructures with precise shape control has offered opportunities to discover new and exciting physical and chemical properties of nanocrystals.

  8. New rock salt-related oxides Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Laha, S. [Departamento de Químicas Inorganica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012 (India); Morán, E., E-mail: emoran@quim.ucm.es [Departamento de Químicas Inorganica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Sáez-Puche, R.; Alario-Franco, M.Á.; Dos santos-Garcia, A.J. [Departamento de Químicas Inorganica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Gonzalo, E.; Kuhn, A.; García-Alvarado, F. [Universidad CEU San Pablo, Facultad de Farmacia, Departamento de Química, 28668 Boadilla del Monte, Madrid (Spain); Sivakumar, T.; Tamilarasan, S.; Natarajan, S.; Gopalakrishnan, J. [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012 (India)

    2013-07-15

    found below 10 K while for the analogous Li{sub 3}Ni{sub 2}RuO{sub 6} , Ru oxidation state is 5+ and a ferrimagnetic (FM) behavior with a Curie temperature of 100 K is found. Electrochemical studies correlate well with both magnetic properties and crystal structure. - Highlights: • New Ruthenium rock salt-related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni) were studied. • Structurally different: rhombohedral α-NaFeO{sub 2}-type (Co) and monoclinic Li{sub 2}TiO{sub 3}-type (Ni) • Magnetic behavior is different: the Co sample is AFM while the Ni one is ferrimagnetic. • Ruthenium oxidation states are different: 4+ in the Co sample and 5+ in the Ni one. • Electrochemical studies correlate well with magnetic properties and crystal structures.

  9. Morphology and composition tailoring of Co x Fe3 - x O4 nanoparticles

    Science.gov (United States)

    Fernandes de Medeiros, I. A.; Madigou, V.; Lopes-Moriyama, A. L.; Pereira de Souza, C.; Leroux, Ch.

    2018-01-01

    Nano-octahedra of cobalt ferrite Co x Fe3 - x O4 (1 ≤ x nano-octahedra of cobalt-rich ferrite Co x Fe3 - x O4 ( x = 1.5) were synthesized. The nano-octahedra are crystallized in a normal spinel structure, with tetrahedral sites occupied by Co2+. This specific octahedral shape was obtained with anionic, cationic, and nonionic surfactants. The nature of the surfactant influenced the chemical composition of the powder and the size of the nano-octahedra. The {100} truncation of the octahedra is more pronounced for the small particles. For the first time, single-phased nanoparticles with as much as x = 1.8 cobalt were synthesized with ethylene glycol as solvent. These nanoparticles, around 8 nm in size, have no specific shape and possess a lacunar spinel structure similar to maghemite. The samples were characterized by X-ray diffraction, transmission electron microscopy, and energy-dispersive spectroscopy.

  10. Study of the influence of the temperature in the magnetic properties and in microstructure in the permanent magnets Pr-Fe-B-Nb-Co based obtained by hydrogen; Estudo da influencia da temperatura nas propriedades magneticas e na microestrutura nos imas permanentes a base de Pr-Fe-B-Nb-Co obtidos com hidrogenio

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Suelanny Carvalho da

    2007-07-01

    Fine magnetic powders were produced using the hydrogenation disproportionation desorption and recombination (HDDR) process. The first stage in this work involved an investigation of the effect of the Co content and range of desorption/ recombination temperatures between 800 and 900 deg C with the purpose of optimizing the HDDR treatment for Pr{sub 14}Fe{sub 80}B{sub 6} and Pr{sub 14}Fe{sub bal}Co{sub x}B{sub 6}Nb{sub 0,1} (x= 0, 4, 8, 10, 12, 16) alloys. The cast alloys were annealed at 1100 deg C for 20 hours for homogenization. The processing temperature (desorption/ recombination) affected the microstructure and magnetic properties of the bonded magnets. The alloy with low cobalt content (4 at.%) required the highest reaction temperature (880 deg C) to yield anisotropic bonded magnets. The optimum temperature for alloys with 8 at.% Co and 10 at.% Co were 840 deg C and 820 deg C, respectively. Alloys with high cobalt content (12 at.% and 16 at.%) were processed at 840 deg C. The optimum desorption temperature for achieving high anisotropy for Pr{sub 14}Fe{sub 80}B{sub 6} and Pr{sub 14}Fe{sub 79,9}B{sub 6}Nb{sub 0,1} was 820 deg C. The best remanence (862 mT) was achieved with the Pr{sub 14}Fe{sub 67,9}B{sub 6}Co{sub 12}Nb{sub 0,1} magnet, processed at 840 deg C. Each alloy required an optimum reaction temperature and exhibited a particular microstructure according to the composition. The second stage of the work involved the characterization, for each temperature, of the Pr{sub 14}Fe{sub 80}B{sub 6} HDDR powder processed using X-ray diffraction analysis. The samples of the HDDR material were studied by synchrotron radiation powder diffraction using the Rietveld method for cell refinement, phase quantification and crystallite sizes determination. Scanning electron microscopy has also been employed to reveal the morphology of the HDDR powder. (author)

  11. Bishnu D. Pradhan PhD, FNAE Mumbai

    Indian Academy of Sciences (India)

    RURAL ENVIRONMENT · INSTALLING IN NEPAL NETWORK · UNIT BEING WASHED ON A SUNNY DAY ! Rural Microwave – 6RU10 · CORDECT WLL · Vigyan Ashram in Pabal · PABAL INTERNET SERVICE · Wireless LAN: 802.11b · Regulatory Issues · Technology Customization Example: Internet Access in Rural India.

  12. Quantum Spin Liquid in Frustrated One-Dimensional LiCuSbO4

    DEFF Research Database (Denmark)

    Dutton, S. E.; Kumar, M.; Mourigal, M.

    2012-01-01

    A quantum magnet, LiCuSbO4, with chains of edge-sharing spin-1/2CuO6 octahedra is reported. While short-range order is observed for T2 K data.......A quantum magnet, LiCuSbO4, with chains of edge-sharing spin-1/2CuO6 octahedra is reported. While short-range order is observed for T2 K data....

  13. Page 1 108 S Ayyappan and N Rangavittal Oxygenatoms alternate ...

    Indian Academy of Sciences (India)

    WO, octahedra forming an infinite 3D network of Interconnecting tunnels (figure 5a). The structure with layeredsheetsofWO, octahedrainterleaved with H.O molecules }}}. WO3 H2O changes to a structure with a 3D network of wo, octahedra in Yº: 0.36H2O. The nature of the coordination of water molecule in WO a 0.36H2O ...

  14. Post annealing investigations of thin praseodymia films on Si(111)

    Energy Technology Data Exchange (ETDEWEB)

    Gevers, Sebastian; Bruns, Daniel; Weisemoeller, Thomas; Deiter, Carsten; Wollschlaeger, Joachim [Fachbereich Physik, Universitaet Osnabrueck (Germany)

    2008-07-01

    Due to its large oxygen capacity and oxygen mobility praseodymia is interesting for applications in modern heterogenous catalysis. For instance the selectivity of praseodymia for carbon compounds is advantageous in olefiant gas synthesis. The investigation of annealing processes leads to a better understanding of the oxygen transport in the praseodymia films. In this context thin PrO{sub 2} films were annealed at temperatures from 300 C up to 600 C under UHV conditions before they were analysed with spot analysis profile low electron energy diffraction (SPALEED). The diffraction pattern indicates a phase transition to Pr{sub 2}O{sub 3} at the surface. Furthermore X-ray diffraction experiments (XRD) show a partial subsurface phase transition from PrO{sub 2} into various oxidation states including Pr{sub 2}O{sub 3}.

  15. Excitonic transition in (Pr,Ca)CoO{sub 3} family

    Energy Technology Data Exchange (ETDEWEB)

    Kunes, Jan; Augustinsky, Pavel [Insitute of Physics, AS CR, Prague (Czech Republic)

    2016-07-01

    The members of (Pr{sub 1-y}Y{sub y}){sub 1-x}Ca{sub x}CoO{sub 3} family exhibit a continuous phase transition accompanied by disappearance of the fluctuating moment of Co and increase of resistivity by several decades. Most intriguing feature of the low temperature phase is breaking of the time reversal symmetry without presence of ordered atomic moments. We will argue that the experimental observations are explained by condensation of atomic size excitons, which gives rise to ordered magnetic multipoles. We will present model calculations performed with dynamical-mean field theory, which demonstrate general features of the excitonic condensation. In addition, we will present results of material specific LDA+U calculations which uncover the excitonic order in Pr{sub 0.5}YCa{sub 0.5}CoO{sub 3} and explain its low temperature behavior.

  16. High-field magnetisation measurements on R sub 2 Fe sub 14 B single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Verhoef, R.; Franse, J.J.M.; Menovsky, A.A.; Radwanski, R.J. (Amsterdam Univ. (NL). Natuurkundig Lab.); Song-quan, J.; Fu-ming, Y. (Academia Sinica, Beijing (CN). Inst. of Physics); Li, H.S.; Gavigan, J.P. (Trinity Coll. Dublin (IE). Dept. of Pure and Applied Physics)

    1988-12-01

    High-field magnetisation measurements on single crystalline samples of Pr{sub 2}Fe{sub 14}B, Nd{sub 2}Fe{sub 14}B and Dy{sub 2}Fe{sub 14}B are presented and discussed within a two-sublattice model. Special attention is given to the high-field part of the curves (B{sub o} > 20 T).

  17. Magnetic properties of (Pr, Gd) sub 2 Fe sub 14 B compounds

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Zhi-dong; Sun, X.K.; Chuang, Y.C. (Academia Sinica, Wenhua (CN). Inst. of Metal Research); Boer, F.R. de; Radwanski, R.J. (Amsterdam Univ. (NL). Natuurkundig Lab.)

    1988-12-01

    The magnetization of magnetically-aligned (Pr{sub 1-x}Gd{sub x}){sub 2}Fe{sub 14}B samples with x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 has been measured at 4.2 K in fields up to 35 T and the anisotropy constants have been derived. The dependence of the first-order magnetization process (FOMP) upon Gd substitution has been determined.

  18. Synthesis Mechanism of Low-Voltage Praseodymium Oxide Doped Zinc Oxide Varistor Ceramics Prepared Through Modified Citrate Gel Coating

    Directory of Open Access Journals (Sweden)

    Wan Rafizah Wan Abdullah

    2012-04-01

    Full Text Available High demands on low-voltage electronics have increased the need for zinc oxide (ZnO varistors with fast response, highly non-linear current-voltage characteristics and energy absorption capabilities at low breakdown voltage. However, trade-off between breakdown voltage and grain size poses a critical bottle-neck in the production of low-voltage varistors. The present study highlights the synthesis mechanism for obtaining praseodymium oxide (Pr>6O11 based ZnO varistor ceramics having breakdown voltages of 2.8 to 13.3 V/mm through employment of direct modified citrate gel coating technique. Precursor powder and its ceramics were examined by means of TG/DTG, FTIR, XRD and FESEM analyses. The electrical properties as a function of Pr>6O11 addition were analyzed on the basis of I-V characteristic measurement. The breakdown voltage could be adjusted from 0.01 to 0.06 V per grain boundary by controlling the amount of Pr>6O11 from 0.2 to 0.8 mol%, without alteration of the grain size. The non-linearity coefficient, α, varied from 3.0 to 3.5 and the barrier height ranged from 0.56 to 0.64 eV. Breakdown voltage and α lowering with increasing Pr>6O11 content were associated to reduction in the barrier height caused by variation in O vacancies at grain boundary.

  19. Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Domenech, Antonio, E-mail: antonio.domenech@uv.es [Departament de Quimica Analitica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain); Montoya, Noemi; Alarcon, Javier [Departament de Quimica Inorganica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain)

    2011-08-01

    Highlights: > Electrochemical characterization of Pr centers in praseodymia-doped zircon. > Study of the catalytic effect on the reduction of peroxide radical anion in nonaqueous solvents. > Assessment of non-uniform distribution of Pr centers in the zircon grains. - Abstract: The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4}; y + z = x; 0.02 < x < 0.10) specimens prepared via sol-gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical features denote that most of the Pr centers are originally in its 4+ oxidation state in the parent Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} specimens. The variation of the catalytic performance of such specimens with potential scan rate, water concentration and Pr loading suggests that Pr is not uniformly distributed within the zircon grains, being concentrated in the outer region of such grains.

  20. Promotion effect of cobalt-based catalyst with rare earth for the ethanol steam reforming

    Energy Technology Data Exchange (ETDEWEB)

    Chiou, Josh Y. Z.; Chen, Ya-Ping; Yu, Shen-Wei; Wang, Chen-Bin [Department of Chemical and Materials Engineering, Chung Cheng Institute of Technology, National Defense University, Tahsi, Taoyuan 33509, Taiwan (China)

    2013-12-16

    Catalytic performance of ethanol steam reforming (ESR) was investigated on praseodymium (Pr) modified ceria-supported cobalt oxide catalyst. The ceria-supported cobalt oxide (Ce-Co) catalyst was prepared by co-precipitation-oxidation (CPO) method, and the doped Pr (5 and 10 wt% loading) catalysts (Pr{sub 5}−Ce−Co and Pr{sub 10}−Ce−Co) were prepared by incipient wetness impregnation method. The reduction pretreatment under 250 and 400 °C (H250 and H400) was also studied. All samples were characterized by XRD, TPR and TEM. Catalytic performance of ESR was tested from 250 to 500 °C in a fixed-bed reactor. The doping of Pr into the ceria lattice has significantly promoted the activity and reduced the coke formation. The products distribution also can be influenced by the different reduction pretreatment. The Pr{sub 10}−Ce−Co−H400 sample is a preferential ESR catalyst, where the hydrogen distribution approaches 73% at 475 °C with less amounts (< 2%) of CO and CH{sub 4}.

  1. Chemical bonding of hydrogen molecules to transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kubas, G.J.

    1990-01-01

    The complex W(CO){sub 3}(PR{sub 3}){sub 2}(H{sub 2}) (CO = carbonyl; PR{sub 3} = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H{sub 2} exchanges easily with D{sub 2}. This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H{sub 2} bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H{sub 2})(R{sub 2}PCH{sub 2}CH{sub 2}PR{sub 2}){sub 2} were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig.

  2. Training effects induced by cycling of magnetic field in ferromagnetic rich phase-separated nanocomposite manganites

    Energy Technology Data Exchange (ETDEWEB)

    Das, Kalipada, E-mail: kalipada.das@saha.ac.in; Das, I.

    2015-12-01

    We have carried out an experimental investigation of magneto-transport and magnetic properties of charge-ordered Pr{sub 0.67}Ca{sub 0.33}MnO{sub 3} (PCMO) and ferromagnetic La{sub 0.67}Sr{sub 0.33}MnO{sub 3} (LSMO) nanoparticles along with a nanocomposite consisting of those two types of nanoparticles. From the magneto-transport measurements, clear irreversibility is observed in the field dependence of resistance due to magnetic field cycling in the case of PCMO nanoparticles. The value of resistance increases during such a field cycling. However such an irreversibility is absent in the case of LSMO nanoparticles as well as nanocomposites. On the other hand, the magnetic measurements indicate the gradual growth of antiferromagnetic phases in all samples leading to a decrease in magnetization. These inconsistencies between magneto-transport and magnetic behaviors are attributed to the magnetic training effects. - Highlights: • The resistance value in Pr{sub 0.67}Ca{sub 0.33}MnO{sub 3} nanoparticles is found to increase owing to the magnetic field cycling. • No anomaly in resistance was found in Pr{sub 0.67}Ca{sub 0.33}MnO{sub 3}–La{sub 0.67}Sr{sub 0.33}MnO{sub 3} nanocomposite. • Magnetic measurements indicate the training effect in nanostructure compounds.

  3. Synthesis of octahedral ZnGa2O4 particles and their field-emission properties

    Science.gov (United States)

    Zhang, Xitian; Rao, Yangyan; Liang, Yao; Deng, Rui; Liu, Zhuang; Hark, Suikong; Yuen, Yingkit; Wong, Saipeng

    2008-05-01

    ZnGa2O4 particles that are regular octahedra in shape and uniform in size were synthesized on Si substrates via catalyst-free chemical vapour deposition. The surfaces of the octahedra are bounded by {1 1 1} facets. A model based on surface energy dependent growth rate is proposed for interpreting the appearance of the octahedra. The field-emission (FE) properties of the octahedral particles were measured. The turn-on field required for producing an emission current density of 0.1 µA cm-2 is 11 V µm-1, and the field enhancement factor (β) is about 1256, which is high enough for various FE applications.

  4. Crystal structure and refined formula of garyansellite Mg2Fe3+(PO4)2(OH) · 2H2O

    Science.gov (United States)

    Zubkova, N. V.; Pekov, I. V.; Kasatkin, A. V.; Chukanov, N. V.; Ksenofontov, D. A.; Pushcharovsky, D. Yu.

    2016-03-01

    Single-crystal study of the structure ( R = 0.0268) was performed for garyansellite from Rapid Creek, Yukon, Canada. The mineral is orthorhombic, Pbna, a = 9.44738(18), b = 9.85976(19), c = 8.14154(18) Å, V = 758.38(3) Å3, Z = 4. An idealized formula of garyansellite is Mg2Fe3+(PO4)2(OH) · 2H2O. Structurally the mineral is close to other members of the phosphoferrite-reddingite group. The structure contains layers of chains of M(2)O4(OH)(H2O) octahedra which share edges to form dimers and connected by common edges with isolated from each other M(1)O4(H2O)2 octahedra. The neighboring chains are connected to the layer through the common vertices of M(2) octahedra and octaahedral layers are linked through PO4 tetrahedra.

  5. Study of the influence of zirconium and gallium on the magnetic properties and microstructures of praseodymium-based permanent magnets; Estudo da influencia do zirconio e galio nas propriedades magneticas e na microestrutura dos imas permanentes a base de praseodimio

    Energy Technology Data Exchange (ETDEWEB)

    Fusco, Alexandre Giardini

    2006-07-01

    In this work was studied the influence of the addition of 0.5 at. % of zirconium and gallium on praseodymium-based HD sintered magnets obtained using a mixture of alloys. The alloys used in this study were: Pr{sub 12.6}Fe{sub 68.3}Co{sub 11.6}B{sub 6}Zr{sub 0.5}Ga{sub 1}, Pr{sub 16}Fe{sub 75.5}B{sub 8}Zr{sub 0.5}, Pr{sub 13}Fe{sub 80.5}B{sub 6}Zr{sub 0.5}. The investigation started by measuring the magnetic properties and observing the microstructure of the magnets. After that, the magnets were annealed at 1000 deg C for 2 hours followed by rapid cooling, in a total of 10 hours. This heat treatment was followed by 5 hours at the same temperature up to a total of 35 hours. Changes in the microstructure were compared to the change in the magnetic properties aiming at a proper understanding of the role of each added element in relation to the magnetically hard phase (phase {phi}). It has been shown that gallium and zirconium act as grain refiners of the matrix phase {phi}. Gallium acts in the grain and favoring of the shape stability and improvement of the magnetic properties. For the Pr{sub 14.3}Fe{sub 71.9}Co{sub 5.8}B{sub 7}Zr{sub 0.5}Ga{sub 0.5} sintered magnet the evolution of the magnetic properties after 15 hours heat treatment was: remanence from (1.25{+-}0.02) T to (1.30{+-}0.02) T, intrinsic coercivity from (1.11{+-}0.02) T to (0.87{+-}0.02) T, squareness factor from (0.68{+-}0.02) to (0.82{+-}0.02) and energy product from (285{+-}5) kJ/m{sup 3} to (317{+-}5) kJ/m{sup 3}. Zirconium has two effects on the sintered magnets. Firstly, avoiding random grain growth and enhancing anisotropy. However, by concentrating on the grain boundaries, yield reverse domains and is detrimental to the intrinsic coercivity. For the sintered Pr{sub 14.5}Fe{sub 78}B{sub 7}Zr{sub 0.5} magnet the evolution of the magnetic properties achieved after a heat treatment of 15 hours was: remanence from (1.19{+-}0.02) T to (1.25{+-}0.02) T, coercivity from (0.74{+-}0.02) T to (0

  6. Poly[1,4-bis(ammoniomethylcyclohexane [di-μ-bromido-dibromidoplumbate(II

    Directory of Open Access Journals (Sweden)

    Matthew Kyle Rayner

    2010-06-01

    Full Text Available The title compound, {(C8H20N2[PbBr4]}n, crystallizes as an inorganic–organic hybrid with alternating layers of diammonium cations and two-dimensional corner-sharing PbBr6 octahedra extending parallel to the bc plane, which are eclipsed relative to one another. Both PbBr6 octahedra and the organic cation exhibit overline{1} symmetry. The cations interact via N—H...Br hydrogen bonding in the right-angled halogen sub-type of the terminal halide hydrogen-bonding motif.

  7. K1.65V1.78W0.22O2(AsO42

    Directory of Open Access Journals (Sweden)

    Sabrina Belkhiri

    2009-09-01

    Full Text Available The title potassium vanadium tungsten bis(arsenate oxide was synthesized by a solid-state reaction at 973 K. The crystal structure is isotypic with KVOPO4 and contains a [MVAs2O10]∞ framework built up from single MO6 (M = V+W octahedra sharing corners with single VO6 octahedra and AsO4 tetrahedra. This structure shows the existence of infinite [VAsO8]∞ and [MAsO8]∞ chains running along the a and c directions, respectively. All atoms are located on general positions. The metal position M is statistically occupied by 78% V and 22% W.

  8. Quantum Material Properties of 4d and 5d Transition Metal Oxides and Potential Applications

    Science.gov (United States)

    2015-05-26

    perovskite structure (3C). We measured only the 9R and 4H forms. It was found previously1 that the 4H BaRuO3 shows a metallic resistivity down to the...by perovskite -like corner sharing with the 3 nearly 180-degree Ru-O-Ru bonds. The stacking pattern repeats after 9 octahedra. The 4H form, on the...other hand, consists of units of two octahedra sharing faces connected to each other by perovskite -type corner sharing. The stacking pattern along the

  9. High coercivity in rare-earth lean nanocomposite magnets by grain boundary infiltration

    Energy Technology Data Exchange (ETDEWEB)

    Madugundo, Rajasekhar, E-mail: mraja@udel.edu [Department of Physics and Astronomy, University of Delaware, Newark, DE 19716 (United States); Salazar-Jaramillo, Daniel [BCMaterials, Bizkaia Science and Technology Park, E-48160 Derio (Spain); Manuel Barandiaran, Jose [BCMaterials, Bizkaia Science and Technology Park, E-48160 Derio (Spain); Department of Electricity & Electronics, University of the Basque Country (UPV/EHU), E-48080 Bilbao (Spain); Hadjipanayis, George C., E-mail: hadji@udel.edu [Department of Physics and Astronomy, University of Delaware, Newark, DE 19716 (United States)

    2016-02-15

    A significant enhancement in coercivity was achieved by grain boundary modification through low temperature infiltration of Pr{sub 75}(Cu{sub 0.25}Co{sub 0.75}){sub 25} eutectic alloy in rare-earth lean (Pr/Nd)–Fe–B/α-Fe nanocomposite magnets. The infiltration procedure was carried out on ribbons and hot-deformed magnets at 600–650 °C for different time durations. In Nd{sub 2}Fe{sub 14}B/α-Fe ribbons, the coercivity increased from 5.3 to 23.8 kOe on infiltration for 4 h. The Pr{sub 2}Fe{sub 14}B/α-Fe hot-deformed magnet shows an increase in coercivity from 5.4 to 22 kOe on infiltration for 6 h. The increase in the coercivity comes at the expense of remnant magnetization. X-ray diffraction studies confirm the presence of both the hard Nd{sub 2}Fe{sub 14}B and soft α-Fe phases. A decrease in the soft α-Fe phase content was observed after infiltration. - Highlights: • Enhancement in coercivity was achieved by grain boundary modification. • Coercivity increased from 5.3 to 23.8 kOe in Nd{sub 2}Fe{sub 14}B/α-Fe on infiltration. • Pr{sub 2}Fe{sub 14}B/α-Fe deformed magnet shows an increase in coercivity from 5.4 to 22 kOe. • The increase in the coercivity comes at the expense of remnant magnetization. • A decrease in the soft α-Fe phase content was observed after infiltration.

  10. Phase and structural behaviour of the PrAlO{sub 3}-LaAlO{sub 3} pseudo-binary system

    Energy Technology Data Exchange (ETDEWEB)

    Basyuk, T. [Semiconductor Electronics Department, Lviv Polytechnic National University, 12 Bandera St., 79013 Lviv (Ukraine)], E-mail: tanya.basyuk@gmail.com; Vasylechko, L.; Fadeev, S. [Semiconductor Electronics Department, Lviv Polytechnic National University, 12 Bandera St., 79013 Lviv (Ukraine); Syvorotka, I.I. [SRC ' Carat' , 202 Stryjska St., 79031 Lviv (Ukraine); Trots, D. [Institute for Materials Science, Darmstadt University of Technology, Petersenstrasse 23, 64287 Darmstadt (Germany); Niewa, R. [Department Chemie, Technische Universitaet Muenchen, Lichtenbergstrasse 4, 85747 Garching (Germany)

    2009-10-15

    High-resolution in situ X-ray powder diffraction applying synchrotron radiation has been used to examine the occurring crystal structures and the thermal behaviour of the solid solution Pr{sub 1-x}La{sub x}AlO{sub 3} in a wide temperature range 12-1173 K. At room temperature all studied samples in the whole composition range of the pseudo-binary system PrAlO{sub 3}-LaAlO{sub 3} adopt a rhombohedral perovskite structure. The phases Pr{sub 1-x}La{sub x}AlO{sub 3} with x=0.56 and 0.66 undergo a sequence of three phase transitions I2/m{r_reversible}Imma{r_reversible}R3-bar c{r_reversible}Pm3-bar m. For the sample with x=0.24 a series of four (I4/mcm{r_reversible}I2/m{r_reversible}Imma{r_reversible}R3-bar c{r_reversible}Pm3-bar m) phase transitions has been observed and for x=0.86 two transformations were apparent (I2/m{r_reversible}R3-bar c{r_reversible}Pm3-bar m). Crystal structure parameters for all studied compositions Pr{sub 1-x}La{sub x}AlO{sub 3} have been determined. Based on in situ powder diffraction and DTA/DSC data, the phase diagram of the pseudo-binary system PrAlO{sub 3}-LaAlO{sub 3} has been constructed.

  11. TRANSITING THE SUN. II. THE IMPACT OF STELLAR ACTIVITY ON Lyα TRANSITS

    Energy Technology Data Exchange (ETDEWEB)

    Llama, J.; Shkolnik, E. L., E-mail: joe.llama@lowell.edu [Lowell Observatory, 1400 W Mars Hill Road, Flagstaff, AZ 86001 (United States)

    2016-01-20

    High-energy observations of the Sun provide an opportunity to test the limits of our ability to accurately measure the properties of transiting exoplanets in the presence of stellar activity. Here we insert the transit of a hot Jupiter into continuous disk integrated data of the Sun in Lyα from NASA’s Solar Dynamics Observatory/EVE instrument to assess the impact of stellar activity on the measured planet-to-star radius ratio (R{sub p}/R{sub ⋆}). In 75% of our simulated light curves, we measure the correct radius ratio; however, incorrect values can be measured if there is significant short-term variability in the light curve. The maximum measured value of R{sub p}/R{sub ⋆} is 50% larger than the input value, which is much smaller than the large Lyα transit depths that have been reported in the literature, suggesting that for stars with activity levels comparable to the Sun, stellar activity alone cannot account for these deep transits. We ran simulations without a transit and found that stellar activity cannot mimic the Lyα transit of 55 Cancari b, strengthening the conclusion that this planet has a partially transiting exopshere. We were able to compare our simulations to more active stars by artificially increasing the variability in the Solar Lyα light curve. In the higher variability data, the largest value of R{sub p}/R{sub ⋆} we measured is <3× the input value, which again is not large enough to reproduce the Lyα transit depth reported for the more active stars HD 189733 and GJ 436, supporting the interpretation that these planets have extended atmospheres and possible cometary tails.

  12. Effect of chromium concentration on the structural, magnetic and electrical properties of praseodymium-calcium manganite

    Energy Technology Data Exchange (ETDEWEB)

    Bettaibi, A. [Laboratoire de Physique des Matériaux et des Nanomatériaux appliquée à l' Environnement, Faculté des Sciences de Gabès cité Erriadh, Université de Gabès, 6079 Gabès (Tunisia); M' nassri, R., E-mail: rafik_mnassri@yahoo.fr [Higher Institute of Applied Sciences and Technology of Kasserine, Kairouan University, B.P. 471, 1200 Kasserine (Tunisia); Laboratoire de Physico-Chimie des Matériaux, Département de Physique, Faculté des Sciences de Monastir, Université de Monastir, 5019 Monastir (Tunisia); Selmi, A. [Laboratory of Physics of Materials, Faculty of Sciences of Sfax, Sfax University, B.P.1171, 3000 Sfax (Tunisia); Rahmouni, H. [Laboratoire de Physique des Matériaux et des Nanomatériaux appliquée à l' Environnement, Faculté des Sciences de Gabès cité Erriadh, Université de Gabès, 6079 Gabès (Tunisia); Chniba-Boudjada, N. [Institut NEEL, B.P.166, 38042 Grenoble Cedex 09 (France); Faculté des Sciences de Gabès cité Erriadh, Université de Gabès, 6079 Gabès (Tunisia); and others

    2015-11-25

    The influence of Cr doping on magnetic, magnetocaloric and electrical properties in a polycrystalline sample of Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3} is investigated. Structural studies show that our samples are single phase. The magnetization shows that the Pr{sub 0.7}Ca{sub 0.3}Mn{sub 1−x}Cr{sub x}O{sub 3} ceramics exhibit a paramagnetic–ferromagnetic transition with a large magnetic entropy change. The relative cooling power (RCP) values are comparable to those of other manganite. DC conductance G{sub DC} measurements show that all samples are characterized by a semiconductor behavior. It is found that G{sub DC} decreases by two decades when increasing chromium concentrations. For the parent compound, dc-conductance is characterized by the appearance of a saturation region at a specific temperature (T{sub sat} = 200 K). For the doped compound, T{sub sat} go beyond room temperature. Conduction mechanism is found to be dominated by the small polaron hopping (SPH) process at high temperature and by variable range hopping one (VRH) at low temperature. AC conductance study confirms that the conductivity is governed by hopping process and obeys to the Jonscher universal power law. The exponent ‘n’ variation with temperature is in good agreement with Mott theory. Its variation as a function of chromium content indicates that the material turns from metallic to semi-insulating behavior when chromium composition increases. Impedance analysis proves the presence of electrical relaxation phenomenon in the material and confirms that grain boundaries played a main role in the conduction process. - Highlights: • Pr{sub 0.7}Ca{sub 0.3}Mn{sub 1−x}Cr{sub x}O{sub 3} manganites phases crystallize in an orthorhombic (Pnma) structure. • Pr{sub 0.7}Ca{sub 0.3}Mn{sub 0.95}Cr{sub 0.05}O{sub 3} has the highest relative cooling power. • DC conductivity measurement indicates that samples have a semiconductor character. • Conduction mechanism is well described by hopping

  13. Transient electronic structure of the photoinduced phase of Pr0.7Ca0.3MnO3 probed with soft x-ray pulses

    Energy Technology Data Exchange (ETDEWEB)

    Rini, M.; Zhu, Y.; Wall, S.; Tobey, R. I.; Ehrke, H.; Garl, T.; Freeland, J. W.; Tomioka, Y.; Tokura, Y.; Cavalleri, A.; Schoenlein, R. W.

    2009-04-01

    We use time-resolved x-ray absorption near-edge structure spectroscopy to investigate the electronic dynamics associated with the photoinduced insulator-to-metal phase transition in the colossal magnetoresistive manganite Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3}. Absorption changes at the O K and Mn L edges directly monitor the evolution of the density of unoccupied states in the transient photoinduced phase. We show that the electronic structure of the photoinduced phase is remarkably similar to that of the ferromagnetic metallic phase reached in related manganites upon cooling below the Curie temperature.

  14. Evidence for high ionic conductivity in lithium–lanthanum titanate,

    Indian Academy of Sciences (India)

    ion migration and the number of defects at the Li sites. Recent investigations have been shown that tilting of TiO6 octahedra changes the bottle-neck size, which is directly related to the Li. + conductivity (Latie et al. ∗. Author for correspondence (swamydts@yahoo.co.in). 1984; Inaguma et al 1993, 2002; Fourquet et al 1996; ...

  15. Structure and Magnetic Properties of Cu3Ni2SbO6 and Cu3Co2SbO6 Delafossites with Honeycomb Lattices

    DEFF Research Database (Denmark)

    Roudebush, J. H.; Andersen, Niels Hessel; Ramlau, R.

    2013-01-01

    The crystal structures of two Delafossites, Cu3Ni2SbO6 and Cu3Co2SbO6, are determined by high-resolution synchrotron powder X-ray diffraction. The Ni and Co are ordered with respect to Sb in the layer of edge sharing octahedra, forming magnetic layers with honeycomb geometry. High-resolution elec...

  16. Full article: The Reaction between MoO3 and Molten K2S2O7 forming K2MoO2(SO4)2

    DEFF Research Database (Denmark)

    Nørbygaard, Thomas; Berg, Rolf W.; Nielsen, Kurt

    1998-01-01

    .18 Å) bonds in trans-position to the short ones, and with two bonds of intermediate (ca. 2.01 Å) length, all four bridging oxygens belonging to different sulfato groups. The K+ ions are placed in between strands of Mo06 octahedra, connected along the c-axis by two different kinds of bridging sulfato...

  17. Anomalous behavior of the semiconducting gap in WO3 from first-principles calculations

    NARCIS (Netherlands)

    Wijs, G.A. de; Boer, P.K. de; Groot, R.A. de; Kresse, G.

    1999-01-01

    Several crystal structures of tungsten trioxide have been studied with a first-principles pseudopotential method. The electronic band gap increases significantly with the distortion of the octahedra that are the building blocks of the various crystal structures. Moreover, the tilting of the

  18. Crystal structure of calcium dinickel(II iron(III tris(orthophosphate: CaNi2Fe(PO43

    Directory of Open Access Journals (Sweden)

    Said Ouaatta

    2017-06-01

    Full Text Available The title compound, CaNi2Fe(PO43, was synthesized by solid-state reactions. Its structure is closely related to that of α-CrPO4 in the space group Imma. Except for two O atoms in general positions, all atoms are located in special positions. The three-dimensional framework is built up from two types of sheets extending parallel to (100. The first sheet is made up from two edge-sharing [NiO6] octahedra, leading to the formation of [Ni2O10] double octahedra that are connected to two PO4 tetrahedra through a common edge and corners. The second sheet results from rows of corner-sharing [FeO6] octahedra and PO4 tetrahedra forming an infinite linear chain. These layers are linked together through common corners of PO4 tetrahedra and [FeO6] octahedra, resulting in an open three-dimensional framework that delimits two types of channels parallel to [100] and [010] in which the eightfold-coordinated CaII cations are located.

  19. Dipotassium dialuminium cyclooctaphosphate

    Directory of Open Access Journals (Sweden)

    Abdelghani Oudahmane

    2010-07-01

    Full Text Available Single crystals of the title compound, K2Al2P8O24, were obtained by solid-state reaction. The monoclinic structure is isotypic with that of the GaIII analogue and is built of eight-membered phosphate ring anions P8O248− (2/m symmetry isolated from each other and further linked by isolated AlO6 octahedra (overline{1} symmetry by sharing corners. Each AlO6 octahedron is linked to four P8O248− rings in such a way that two rings are linked through bidentate diphosphate groups attached in the cis positions on two opposite parallel edges of the octahedron. The two other rings are linked via corner-sharing to the two remaining corners in the trans positions of the AlO6 octahedron. Each P8O248− ring anion is linked to eight AlO6 octahedra. More accurately, each ring anion is linked to four AlO6 octahedra through bidentate diphosphate groups attached in the cis positions to the AlO6 octahedron and to the four remaining octahedra by sharing corners. This three-dimensional linkage delimits channels running parallel to [001] in which the ten-coordinated K+ cations (2 symmetry are distributed over two columns. These columns alternate with empty octagonally-shaped channels expanding through the P8O248− ring anions.

  20. Copper scandium zirconium phosphate

    DEFF Research Database (Denmark)

    Bond, Andrew David; Warner, Terence Edwin

    2013-01-01

    components. The [Sc(III)Zr(IV)(PO(4))(3)](2-) framework is composed of corner-sharing Sc/ZrO(6) octahedra and PO(4) tetrahedra. The Sc and Zr atoms are disordered on one atomic site on a crystallographic threefold axis. The P atom of the phosphate group lies on a crystallographic twofold axis. Nonframework...

  1. Page 1 Bull, Mater. Sci., Vol. 2, No. 6, December 1998, pp. 469-474 ...

    Indian Academy of Sciences (India)

    expansion coefficient with increase in the (Li/Nb), ratio is discussed in the light of defect chemistry i.e. the partial replacement of Li' by excess Nb creates additional cation vacancies to attain the electro-neutrality in the crystal. Keywords. Single crystal; thermal expansion; non-stoichiometry; defects; octahedra. 1. Introduction.

  2. Download this PDF file

    African Journals Online (AJOL)

    paper to study the order-disorder relations of the same suite of Mn-Mg olivines .... forsterites, and calcium concentrations up to 2.32 (Smith et al., 1944) and 2.63 ... silicon cations. The major structural feature is the zigzag chains of two occupied octahedra (M 1 & M2) parallel to the c-axis, the M1 octahedron being located.

  3. type phase LaSr2MnCrO7

    Indian Academy of Sciences (India)

    Administrator

    LaSr2MnCrO7; structure; rietveld XRD analysis; magnetoresistance; ferromagnetic. 1. Introduction. The Ruddlesden–Popper (RP) type ... K2NiF4-type structure with only one layer of corner- sharing BO6 octahedra along the c direction. .... ered manganites exhibit I–M transition at low tem- peratures and the Mn. 3+. /Mn. 4+.

  4. Synthesis, crystal structure, thermal analysis and dielectric ...

    Indian Academy of Sciences (India)

    In both the materials, the crystal structure has been determined by X-ray single crystal analysis at room temperature (293 K). The compound structures consist of K + (or NH 4 + ) cations and double chains of CdCl 6 octahedra sharing one edge extending along b -axis. The mixture of KA + /NH 4 + cations are located ...

  5. Magnetism of carbon doped Mn5 Si3 and Mn5 Ge3 films

    Indian Academy of Sciences (India)

    Administrator

    2009-03-03

    Mar 3, 2009 ... center of MnII octahedra. interstitial atom but participates in the chemical bonding to Mn. ... minor antiferromagnetic Mn–Si–C phases in the im- planted film that reduce the total measured magneti- ... samples and to obtain C-doped regions that are em- bedded into the carbon-free host resulting in a lat-.

  6. The crystal structure of bøgvadite (Na2SrBa2Al4F20)

    DEFF Research Database (Denmark)

    Balic Zunic, Tonci

    2014-01-01

    and jørgensenite. However, its structure type is different from the latter two. The fluoridoaluminate framework of bøgvadite consists of infinite zig-zag chains of cis-connected AlF6 coordination octahedra. The 1∞[AlF5] chains are interconnected by infinite chains of Na-F coordination polyhedra which extend...

  7. Theoretical study of the electron paramagnetic resonance ...

    Indian Academy of Sciences (India)

    Abstract. The electron paramagnetic resonance (EPR) parameters (the g factors, hy- perfine structure constants and the superhyperfine parameters) for the tetragonal Ir2+ centre in NaCl are theoretically investigated from the perturbation formulas of these parameters for a 5d7 ion in tetragonally elongated octahedra.

  8. High-pressure Al-rich hexagonal phases-What are their kin?

    DEFF Research Database (Denmark)

    Makovicky, Emil; Olsen, Lars Arnskov

    2008-01-01

    The hexagonal Al-rich high-pressure phases are members of a structural family with the same type of framework composed of double-ribbons of edge-sharing octahedra, but variably occupied trigonal and hexagonal channels. This family includes jaffeite, fluoborite, yeremeyevite, painite, and syntheti...... Ba indates. This kinship broadens the spectrum of elements potentially accommodated by these phases in the mantle....

  9. SV Ganesan Srinivasan Natarajan

    Indian Academy of Sciences (India)

    The anions consist of a ring of five MoO6 distorted octahedra with four edge connections and one corner connection. The phosphate groups cap the pentamolybdate ring anion on either side. The anion is stabilized by strong hydrogen bonds involving the hydrogen atoms of the amine molecules and the oxygen atoms of the ...

  10. Role of hydrogen-bonding and its interplay with octahedral tilting in CH3NH3PbI3.

    Science.gov (United States)

    Lee, Jung-Hoon; Bristowe, Nicholas C; Bristowe, Paul D; Cheetham, Anthony K

    2015-04-14

    First principles calculations on the hybrid perovskite CH3NH3PbI3 predict strong hydrogen-bonding which influences the structure and dynamics of the methylammonium cation and reveal its interaction with the tilting of the PbI6 octahedra. The calculated atomic coordinates are in excellent agreement with neutron diffraction results.

  11. Crystal structure of calcium dinickel(II) iron(III) tris-(orthophosphate): CaNi2Fe(PO4)3.

    Science.gov (United States)

    Ouaatta, Said; Assani, Abderrazzak; Saadi, Mohamed; El Ammari, Lahcen

    2017-06-01

    The title compound, CaNi2Fe(PO4)3, was synthesized by solid-state reactions. Its structure is closely related to that of α-CrPO4 in the space group Imma. Except for two O atoms in general positions, all atoms are located in special positions. The three-dimensional framework is built up from two types of sheets extending parallel to (100). The first sheet is made up from two edge-sharing [NiO6] octa-hedra, leading to the formation of [Ni2O10] double octa-hedra that are connected to two PO4 tetra-hedra through a common edge and corners. The second sheet results from rows of corner-sharing [FeO6] octa-hedra and PO4 tetra-hedra forming an infinite linear chain. These layers are linked together through common corners of PO4 tetra-hedra and [FeO6] octa-hedra, resulting in an open three-dimensional framework that delimits two types of channels parallel to [100] and [010] in which the eightfold-coordinated Ca(II) cations are located.

  12. Magnetism and the absence of superconductivity in the praseodymium–silicon system doped with carbon and boron

    Energy Technology Data Exchange (ETDEWEB)

    Venta, J. de la, E-mail: jdelaventa@physics.ucsd.edu [Department of Physics and Center for Advanced Nanoscience, University of California, La Jolla, San Diego, CA 92093 (United States); Basaran, Ali C. [Department of Physics and Center for Advanced Nanoscience, University of California, La Jolla, San Diego, CA 92093 (United States); Materials Science and Engineering, University of California, La Jolla, San Diego, CA 92093 (United States); Grant, T. [Department of Physics and Astronomy, University of California, Irvine, CA 92697 (United States); Gallardo-Amores, J.M. [Departamento de Quimica Inorganica I, Universidad Complutense, E-28040 Madrid (Spain); Ramirez, J.G. [Department of Physics and Center for Advanced Nanoscience, University of California, La Jolla, San Diego, CA 92093 (United States); Alario-Franco, M.A. [Departamento de Quimica Inorganica I, Universidad Complutense, E-28040 Madrid (Spain); Fisk, Z. [Department of Physics and Astronomy, University of California, Irvine, CA 92697 (United States); Schuller, Ivan K. [Department of Physics and Center for Advanced Nanoscience, University of California, La Jolla, San Diego, CA 92093 (United States)

    2013-08-15

    We searched for new structural, magnetic and superconductivity phases in the Pr–Si system using high-pressure high-temperature and arc melting syntheses. Both high and low Si concentration areas of the phase diagram were explored. Although a similar approach in the La–Si system produced new stable superconducting phases, in the Pr–Si system we did not find any new superconductors. At low Si concentrations, the arc-melted samples were doped with C or B. It was found that addition of C gave rise to multiple previously unknown ferromagnetic phases. Furthermore, X-ray refinement of the undoped samples confirmed the existence of the so far elusive Pr{sub 3}Si{sub 2} phase. - Highlights: • Study of the Pr–Si system using HP–HT or doping with C and B. • New magnetic phases in the Pr–Si system doped with C. • Confirmation of the existence of the Pr{sub 3}Si{sub 2} phase.

  13. Anomalous thermal expansion in rare-earth gallium perovskites: a comprehensive powder diffraction study

    Energy Technology Data Exchange (ETDEWEB)

    Senyshyn, A; Trots, D M; Engel, J M; Ehrenberg, H; Fuess, H [Institute for Materials Science, Darmstadt University of Technology, D-64287 Darmstadt (Germany); Vasylechko, L [Lviv Polytechnic National University, 12 Bandera Street, 79013 Lviv (Ukraine); Hansen, T [Institut Max von Laue-Paul Langevin, 38042 Grenoble Cedex 9 (France); Berkowski, M [Institute of Physics, Polish Academy of Sciences, Aleja Lotnikow 32/46, 02-668 Warsaw (Poland)

    2009-04-08

    Crystal structures of rare-earth gallium perovskites LaGaO{sub 3}, PrGaO{sub 3}, NdGaO{sub 3} and Pr{sub 1-x}Nd{sub x}GaO{sub 3} (x = 0.25, 0.50, 0.75) solid solutions were investigated in the temperature range 12-300 K by high-resolution powder diffraction using synchrotron or neutron radiation. The previously reported negative thermal expansion in the b direction of the PrGaO{sub 3} lattice has been found to be persistent in Pr{sub 1-x}Nd{sub x}GaO{sub 3} solid solutions and its magnitude has been revealed as proportional to the amount of praseodymium. Evaluation of the obtained temperature evolution of cell dimensions indicated a weak anomalous behaviour of the b lattice parameter in NdGaO{sub 3}, and its origin is supposed to be the same as in PrGaO{sub 3}, i.e. a coupling of the crystal electric field levels with phonon excitations of about 23-25 meV energy. The performed bond length analysis revealed an anomalous behaviour of both LnO{sub 12} (Ln-rare-earth) and GaO{sub 6} coordination polyhedra, which can be a structural manifestation of anomalous thermal expansion in the considered compounds.

  14. Valence determination as a function of doping in $PrBa_{2} Cu_{3} O_{7}$

    CERN Document Server

    Staub, U; Wasserman, S R; Conner, A G O; Kramer, M J; Patterson, B D; Shi, M; Knapp, M P

    2000-01-01

    We present results of X-ray absorption near edge spectra (XANES), neutron powder diffraction, and resonant X-ray diffraction on samples of PrBa/sub 2/Cu/sub 3/O/sub 7- delta / and Pr/sub 1-x/Ca/sub x/Ba /sub 2/Cu/sub 3/O/sub 7/. The data are obtained as a function of the doping levels of oxygen and Ca. There are significant changes in the Pr L/sub 3/ XANES spectra with changes in oxygen or Ca concentrations, indicating that the Pr electronic properties are affected by doping. The resonant X-ray scattering experiments show that the changes observed occur on Pr ions incorporated in the PrBa /sub 2/Cu/sub 3/O/sub 7- delta / structure, and are not the result of changes to a Pr-containing impurity phase. A quantitative model, based on literature precedent, is used to extract Pr valences from the data, although the XANES cannot distinguish between models involving charge transfer and those involving hybridization. The results are compared with data obtained from Pb/sub 2/Sr/sub 2/Pr/sub 1-x/Ca/sub x/Cu/sub 3/O/sub ...

  15. X-ray absorption measurements of charge-ordered La{sub 0.5}Sr{sub 1.5}MnO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Saitoh, T.; Villella, P.M.; Dessau, D.S. [Univ. of Colorado, Boulder, CO (United States)] [and others

    1997-04-01

    Perovskite and {open_quotes}layered perovskite{close_quotes}-type manganese oxides show a variety of electronic and magnetic properties such as the colossal magnetoresistance (CMR) or the charge ordering. Among them, La{sub 0.5}Sr{sub 1.5}MnO{sub 4} (K{sub 2}NiF{sub 4} structure) which has 0.5 holes per Mn site (d{sup 3.5}) shows the charge-order transition at {approximately}220 K below which Mn{sup 3+} and Mn{sup 4+} sites are believed to order in the CE-type. Although the charge ordering phenomenon has also been observed in the perovskite manganites Pr{sub 0.5}Sr{sub 1.5}MnO{sub 3} or Pr{sub 0.5}Ca{sub 1.5}MnO{sub 3}, the present system has another advantage that it has a layered structure. This enables the authors to address the issue of the orbital symmetry which should be directly related to the charge ordering. In this report, they present the results of x-ray absorption spectroscopy (XAS) on La{sub 0.5}Sr{sub 1.5}MnO{sub 4}, for two polarization angles and two (above and below the transition temperature T{sub CO}) temperatures.

  16. The Role of Connectivity on Electronic Properties of Lead Iodide Perovskite-Derived Compounds

    Science.gov (United States)

    2017-01-01

    We use a layered solution crystal growth method to synthesize high-quality single crystals of two different benzylammonium lead iodide perovskite-like organic/inorganic hybrids. The well-known (C6H5CH2NH3)2PbI4 phase is obtained in the form of bright orange platelets, with a structure comprised of single ⟨100⟩-terminated sheets of corner-sharing PbI6 octahedra separated by bilayers of the organic cations. The presence of water during synthesis leads to formation of a novel minority phase that crystallizes in the form of nearly transparent, light yellow bar-shaped crystals. This phase adopts the monoclinic space group P21/n and incorporates water molecules, with structural formula (C6H5CH2NH3)4Pb5I14·2H2O. The crystal structure consists of ribbons of edge-sharing PbI6 octahedra separated by the organic cations. Density functional theory calculations including spin–orbit coupling show that these edge-sharing PbI6 octahedra cause the band gap to increase with respect to corner-sharing PbI6 octahedra in (C6H5CH2NH3)2PbI4. To gain systematic insight, we model the effect of the connectivity of PbI6 octahedra on the band gap in idealized lead iodide perovskite-derived compounds. We find that increasing the connectivity from corner-, via edge-, to face-sharing causes a significant increase in the band gap. This provides a new mechanism to tailor the optical properties in organic/inorganic hybrid compounds. PMID:28677956

  17. Crystal structure of strontium dinickel iron orthophosphate

    Directory of Open Access Journals (Sweden)

    Said Ouaatta

    2015-10-01

    Full Text Available The title compound, SrNi2Fe(PO43, synthesized by solid-state reaction, crystallizes in an ordered variant of the α-CrPO4 structure. In the asymmetric unit, two O atoms are in general positions, whereas all others atoms are in special positions of the space group Imma: the Sr cation and one P atom occupy the Wyckoff position 4e (mm2, Fe is on 4b (2/m, Ni and the other P atom are on 8g (2, one O atom is on 8h (m and the other on 8i (m. The three-dimensional framework of the crystal structure is built up by [PO4] tetrahedra, [FeO6] octahedra and [Ni2O10] dimers of edge-sharing octahedra, linked through common corners or edges. This structure comprises two types of layers stacked alternately along the [100] direction. The first layer is formed by edge-sharing octahedra ([Ni2O10] dimer linked to [PO4] tetrahedra via common edges while the second layer is built up from a strontium row followed by infinite chains of alternating [PO4] tetrahedra and FeO6 octahedra sharing apices. The layers are held together through vertices of [PO4] tetrahedra and [FeO6] octahedra, leading to the appearance of two types of tunnels parallel to the a- and b-axis directions in which the Sr cations are located. Each Sr cation is surrounded by eight O atoms.

  18. Praseodymia on non-passivated and passivated Si(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Gevers, Sebastian

    2010-12-15

    In the presented thesis thin praseodymia films on non-passivated and passivated Si(111) substrates were investigated. The first part deals with PDA of praseodymia films with fluorite structure under UHV conditions in the temperature region from RT to 600 C. It is shown that the untreated films, which are oxidized in 1 atm oxygen to obtain fluorite structure, do not exhibit pure PrO{sub 2} stoichiometry as it was assumed before. Instead, they decompose into two laterally coexisting species exhibiting a PrO{sub 2} and a Pr{sub 6}O{sub 11}. oxide phase, respectively. These species are laterally pinned to the lattice parameter of bulk Pr{sub 6}O{sub 11}. Homogeneous oxide films with Pr{sub 6}O{sub 11} phase can be observed after annealing at 100 C and 150 C. If higher annealing temperatures are applied, the film decomposes again into two coexisting species. Finally, after annealing at 300 C, a mixed crystalline film with both Pr{sub 2}O{sub 3} and Pr{sub 2}O{sub 3+{delta}} oxide phases is formed. Again the lateral strain increases due to the tendency of praseodymia phases to increase their lattice parameters during oxygen loss combined with the lateral pinning. This is accompanied by a decrease of crystallite sizes. The increase of the amorphous Pr-silicate interface between Si substrate and oxide at the expense of the crystalline oxide can be observed after annealing at higher temperatures. Furthermore, an increased mosaic spread of the crystallites occurs, which reduces the lateral strain caused by the oxygen loss. Nevertheless, the crystalline structure is stable against further annealing up to temperatures of 600 C. The results obtained from praseodymia films annealed in 1 atm nitrogen show that these films are good candidates to form homogeneous oxide films with pure cub-Pr{sub 2}O{sub 3} structure by subsequent annealing in UHV. Here, a single oxide species is already observed after annealing at 300 C by SPA-LEED measurements. Investigations on oxygen plasma

  19. Differences in the electrochemical behavior of ruthenium and iridium oxide in electrocatalytic coatings of activated titanium anodes prepared by the sol–gel procedure

    Directory of Open Access Journals (Sweden)

    VLADIMIR V. PANIĆ

    2010-10-01

    Full Text Available The electrochemical characteristics of Ti0.6Ir0.4O2/Ti and Ti0.6Ru0.4O2/Ti anodes prepared by the sol–gel procedure from the corresponding oxide sols, obtained by force hydrolysis of the corresponding metal chlorides, were compared. The voltammetric properties in H2SO4 solution indicate that Ti0.6Ir0.4O2/Ti has more pronounced pseudocapacitive characteristics, caused by proton-assisted, solid state surface redox transitions of the oxide. At potentials negative to 0.0 VSCE, this electrode is of poor conductivity and activity, while the voltammetric behavior of the Ti0.6Ru0.4O2/Ti electrode is governed by proton injection/ejection into the oxide structure. The Ti0.6Ir0.4O2/Ti electrode had a higher electrocatalytical activity for oxygen evolution, while the investigated anodes were of similar activity for chlorine evolution. The potential dependence of the impedance characteristics showed that the Ti0.6Ru0.4O2/Ti electrode behaved like a capacitor over a wider potential range than the Ti0.6Ir0.4O2/Ti electrode, with fully-developed pseudocapacitive properties at potentials positive to 0.60 VSCE. However, the impedance characteristics of the Ti0.6Ir0.4O2/Ti electrode changed with increasing potential from resistor-like to capacitor-like behavior.

  20. Mathematical theory of non-equilibrium quantum statistical mechanics

    CERN Document Server

    Jaksic, V

    2001-01-01

    We review and further develop a mathematical framework for non-equilibrium quantum statistical mechanics recently proposed in [JP4, JP5, JP6, Ru3, Ru4, Ru5, Ru6]. In the algebraic formalism of quantum statistical mechanics we introduce notions of non-equilibrium steady states, entropy production and heat fluxes, and study their properties. Our basic paradigm is a model of a small (finite) quantum system coupled to several independent thermal reservoirs. We exhibit examples of such systems which have strictly positive entropy production.

  1. Roles of aromatic side chains and template effects of the hydrophobic cavity of a self-assembled peptide nanoarchitecture for anisotropic growth of gold nanocrystals.

    Science.gov (United States)

    Tomizaki, Kin-ya; Kishioka, Kohei; Kobayashi, Hiroki; Kobayashi, Akitsugu; Yamada, Naoki; Kataoka, Shunsuke; Imai, Takahito; Kasuno, Megumi

    2015-11-15

    Gold nanocrystals are promising as catalysts and for use in sensing/imaging systems, photonic/plasmonic devices, electronics, drug delivery systems, and for photothermal therapy due to their unique physical, chemical, and biocompatible properties. The use of various organic templates allows control of the size, shape, structure, surface modification and topology of gold nanocrystals; in particular, currently the synthesis of gold nanorods requires a cytotoxic surfactant to control morphology. To control the shape of gold nanocrystals, we previously demonstrated the de novo design and synthesis of a β-sheet-forming nonapeptide (RU006: Ac-AIAKAXKIA-NH2, X=L-2-naphthylalanine, Nal) and the fabrication of gold nanocrystals by mixing RU006 and HAuCl4 in water. The reaction afforded ultrathin gold nanoribbons 50-100 nm wide, several nanometers high, and microns long. To understand the mechanism underlying gold nanoribbon formation by the RU006 system, we here report (i) the effects of replacement of the Nal aromatic side chain in the RU006 sequence with other aromatic moieties, (ii) the electrochemical properties of aromatic side chains in the de novo designed template peptides to estimate the redox potential and number of electrons participating in the gold crystallization process, and (iii) the stoichiometry of the RU006 system for gold nanoribbon synthesis. Interestingly, RU006 bearing a naphthalene moiety (oxidation peak potential of 1.50 V vs Ag/Ag(+)) and an analog [Ant(6)]-RU006 bearing a bulky anthracene moiety (oxidation peak potential of 1.05 V vs Ag/Ag(+)) allowed the growth of anisotropic (ribbon-like) and isotropic (round) gold nanocrystals, respectively. This trend in morphology of gold nanocrystals was attributed to spatially-arranged hydrophobic cavities sufficiently large to accommodate the gold precursor and to allow directed crystal growth driven by cross-linking reactions among the naphthalene rings. Support for this mechanism was obtained by

  2. Surface Structure Dependence of SO 2 Interaction with Ceria Nanocrystals with Well-Defined Surface Facets

    Energy Technology Data Exchange (ETDEWEB)

    Tumuluri, Uma; Li, Meijun; Cook, Brandon G.; Sumpter, Bobby; Dai, Sheng; Wu, Zili

    2015-12-31

    The effects of the surface structure of ceria (CeO2) on the nature, strength, and amount of species resulting from SO2 adsorption were studied using in situ IR and Raman spectroscopies coupled with mass spectrometry, along with first-principles calculations based on density functional theory (DFT). CeO2 nanocrystals with different morphologies, namely, rods (representing a defective structure), cubes (100 facet), and octahedra (111 facet), were used to represent different CeO2 surface structures. IR and Raman spectroscopic studies showed that the structure and binding strength of adsorbed species from SO2 depend on the shape of the CeO2 nanocrystals. SO2 adsorbs mainly as surface sulfites and sulfates at room temperature on CeO2 rods, cubes, and octahedra that were either oxidatively or reductively pretreated. The formation of sulfites is more evident on CeO2 octahedra, whereas surface sulfates are more prominent on CeO2 rods and cubes. This is explained by the increasing reducibility of the surface oxygen in the order octahedra < cubes < rods. Bulk sulfites are also formed during SO2 adsorption on reduced CeO2 rods. The formation of surface sulfites and sulfates on CeO2 cubes is in good agreement with our DFT results of SO2 interactions with the CeO2(100) surface. CeO2 rods desorb SO2 at higher temperatures than cubes and octahedra nanocrystals, but bulk sulfates are formed on CeO2 rods and cubes after high-temperature desorption whereas only some surface sulfates/sulfites are left on octahedra. This difference is rationalized by the fact that CeO2 rods have the highest surface basicity and largest amount of defects among the three nanocrystals, so they bind and react with SO2 strongly and are the most degraded after SO2 adsorption cycles. The fundamental understanding obtained in this work on the effects of the surface structure and defects on the interaction of SO2 with CeO2 provides insights for the design of more sulfur-resistant CeO2-based catalysts.

  3. Metal complexes with 1,2-dithione ligands. 3. Dithiooxamides as strong donors or acceptors in molybdenum carbonyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    Dieck, H.T.; Form, M. (Hamburg Univ. (Germany, F.R.))

    1984-08-01

    Starting from substitution labile molybdenum carbonyl complexes L/sub 2/Mo(CO)/sub 4/, L/sub 3/Mo(CO)/sub 3/ and L/sub 2/L'/sub 2/Mo(CO)/sub 2/ several new complex types with the C-C-twisted tetraalkyldithiooxamides (R/sub 4/dto) and the planar N,N'-dialkyldithiooxamide (R/sub 2/H/sub 2/dto) such as (R/sub 4/dto)Mo(CO)/sub 4/, (R/sub 2/H/sub 2/dto)Mo(CO)/sub 4/, (R/sub 2/R'/sub 2/dto)Mo(CO)/sub 3/(P(C/sub 6/H/sub 5/)/sub 3/), (R/sub 2/R'/sub 2/dto)Mo(CO)/sub 2/(PR/sub 3/)/sub 2/ are described and compared with complexes of a cyclic dithiooxamide and analogous complexes with thioamides R/sub 2/NC(S)R'. In Mo(CO)/sub 4/ complexes, dithiooxamides display a rather strong donor character and are thus similar to simple thioamides, but the blue colour of the R/sub 2/H/sub 2/dto complexes indicates already low-lying acceptor levels. When passing from the Mo(CO)/sub 4/ complexes via Mo(CO)/sub 3/(PR/sub 3/) complexes to the very electron rich Mo(CO)/sub 2/(PR/sub 3/)/sub 2/ complexes, the IR and electronic spectra indicate an unexpected and drastic change in ligand character. Dto ligands in the latter complex type turn out to be very strong acceptors, independent of the degree of N-alkylation. A conformational change, with twisted R/sub 2/N-C bonds and a planar S-C-C-S skeleton (as in the dithiolene complexes), can account for all the peculiarities of the (dto)-dicarbonylbis(phosphine) complexes as compared to the 'normal' thioamide complexes. Dithiooxamides can thus control the oxidation state of metals by a remote conformational change and possibly act as an electron reservoir in chemical reactions at the metal center.

  4. Ballistic Electron Emission Microscopy (BEEM) of Au/Pr{sub 2}O{sub 3}/Si structures; Ballistische Elektronen Emissions Mikroskopie (BEEM) an Au/Si und Au/Pr{sub 2}O{sub 3}/Si-Strukturen

    Energy Technology Data Exchange (ETDEWEB)

    Mauch, I.

    2007-05-15

    This thesis describes Ballistic Electron Emission Microscopy (BEEM) measurements of Au/Si(111) and Au/Pr{sub 2}O{sub 3}/Si(111) structures. This technique is based on Scanning Tunnelling Microscopy (STM). It measures the ballistic transport of hot electrons through parts of the sample and across an interface, which provides a potential barrier. One part of this work was to modify the BEEM apparatus and to implement a lock in method, which modulates the tunnel current with a small frequency. In this way it is possible to study samples with very low resistance (as low as 30 k{omega}), which widely enlarges the number of samples which are appropriate for BEEM measurement at room temperature. Both types of samples studied in this thesis had low resistance and were therefore studied using the lock in method. For the classical BEEM system Au/Si(111), we observed a pronounced dependence of the sample resistance of Au/Si(111)-7 x 7 on the preparation temperature. We developed a model for the resistance of thermal prepared Au/Si(111)-7 x 7 samples. The model identifies that the low resistance is due to the surface conductivity of the reconstructed silicon surface. If the surface is prepared at a lower temperature (but still high enough that the surface is cleaned and the silicon dioxide desorbed) rough areas remain on the surface, which reduce the surface conductivity. For BEEM measurements flat areas of the sample surface are selected. The low temperature prepared samples we were able to obtain BEEM spectra as well as images at room temperature using the lock in method. The sesquioxide of praseodymium (Pr{sub 2}O{sub 3}) is currently discussed as a possible candidate for a gate oxide in semiconductor devices, since it has some of the required material properties such as a high dielectric constant, low leakage current and epitaxial growth on Si(100). We have for the first time performed BEEM measurement of praseodymium oxide. Despite a low resistance of the structures we

  5. Spin 1/2 Delafossite Honeycomb Compound Cu5SbO6

    DEFF Research Database (Denmark)

    Climent-Pascual, E.; Norby, Poul; Andersen, Niels Hessel

    2012-01-01

    Cu5SbO6 is found to have a monoclinic, Delafossite-derived structure consisting of alternating layers of O–Cu(I)–O sticks and magnetic layers of Jahn–Teller distorted Cu(II)O6 octahedra in an edge sharing honeycomb arrangement with Sb(V)O6 octahedra. This yields the structural formula Cu(I)3Cu(II)2......Sb(V)O6. Variants with ordered and disordered layer stacking are observed, depending on the synthesis conditions. The spin 1/2 Cu2+ ions form dimers in the honeycomb layer. The magnetic susceptibility measured between 5 and 300 K is characteristic of the presence of a singlet–triplet spin gap of 189...

  6. Structure of TeO2 - LiNbO3 glasses

    Science.gov (United States)

    Shinde, A. B.; Krishna, P. S. R.; Rao, Rekha

    2017-05-01

    Tellurite based lithium niobate glasses with composition (100-x)TeO2-xLiNbO3 (x=0.1,0.2 & 0.3) were prepared by conventional melt quenching method. The microscopic structural investigation of these glasses is carried out by means of neutron diffraction and Raman scattering measurements. It is found that the basic structural units in these glasses are TeO4 trigonal bipyramids(TBP), TeO3 trigonal pyramids(TP) and NbO6 Octahedra depending on the composition. It is evident from Raman studies that TBPs decreases, TPs increases and NbO6 Octahedra increases with increasing x. From Neutron diffraction studies it is found that network is comprised of TBPs and TPs along with TeO3+1 structural units. Distorted NbO6 octahedral units are present and also increase with the increase in x.

  7. Strain Accommodation By Facile WO6 Octahedral Distortion and Tilting During WO3 Heteroepitaxy on SrTiO3(001)

    Energy Technology Data Exchange (ETDEWEB)

    Du, Yingge; Gu, Meng; Varga, Tamas; Wang, Chong M.; Bowden, Mark E.; Chambers, Scott A.

    2014-08-27

    In this paper, we show that compared to other BO6 octahedra in ABO3 structured perovskite oxides, the WO6 octahedra in tungsten trioxide (WO3) can withstand a much larger degree of distortion and tilting to accommodate interfacial strain, which in turn strongly impact the nucleation, structure, and defect formation during the epitaxial growth of WO3 on SrTiO3(001). A meta-stable tetragonal phase can be stabilized by epitaxy and a thickness dependent phase transition (tetragonal to monoclinic) is observed. In contrast to misfit dislocations to accommodate the interfacial stain, the facial WO6 octahedral distortion and tilting give rise to three types of planar defects that affect more than 15 monolayers from the interface. These atomically resolved, unusual interfacial defects may significantly alter the electronic, electrochromic, and mechanical properties of the epitaxial films.

  8. Lutetium(III cyclotetraphosphate

    Directory of Open Access Journals (Sweden)

    Aïcha Mbarek

    2010-06-01

    Full Text Available Single crystals of the title compound, tetralutetium(III tris(cyclotetraphosphate, Lu4(P4O123, were obtained by solid-state reaction. The cubic structure is isotypic with its AlIII and ScIII analogues and is built up from four-membered (P4O124− phosphate ring anions (overline{4} symmetry, isolated from each other and further linked through isolated LuO6 octahedra (.3. symmetry via corner sharing. Each LuO6 octahedron is linked to six (P4O124− rings, while each (P4O124− ring is linked to eight LuO6 octahedra.

  9. Crystal structure of (NH42[FeII5(HPO36], a new open-framework phosphite

    Directory of Open Access Journals (Sweden)

    Teresa Berrocal

    2014-11-01

    Full Text Available Diammonium hexaphosphitopentaferrate(II, (NH42[Fe5(HPO36], was synthesized under mild hydrothermal conditions and autogeneous pressure, yielding twinned crystals. The crystal structure exhibits an [FeII5(HPO36]2− open framework with NH4+ groups as counter-cations. The anionic skeleton is based on (001 sheets of [FeO6] octahedra (one with point-group symmetry 3.. and one with .2. linked along [001] through [HPO3]2− oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octahedra, giving rise to channels with a radius of ca 3.1 Å in which the disordered NH4+ cations are located. The IR spectrum shows vibrational bands typical for phosphite and ammonium groups.

  10. Localized optical absorption in Cs{sub 4}PbBr{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, S.; Amaya, K.; Saito, T. [Research Center for Development of Far-Infrared Region, Fukui University, Bunkyo, Fukui (Japan)

    2002-03-04

    The fundamental optical absorption of Cs{sub 4}PbBr{sub 6} crystals, which are built up of nearly regular Pb{sup 2+}(Br{sup -}){sub 6} octahedra mutually bound by Cs{sup +} ions, exhibits novel features: despite the crystalline entity of Cs{sub 4}PbBr{sub 6}, it shows oscillator-like absorption peaks and a wide window just above the first peak. The Cs{sup +} ions prevent the Pb{sup 2+} 6s and 6p states from taking part in the construction of extended states. These states form a set of localized states confined to within respective octahedra, similar to the case of isolated Pb{sup 2+} ions doped in face-centred cubic alkali halide crystals. (author)

  11. Sodium Ion Transport Mechanisms in Antiperovskite Electrolytes Na3OBr and Na4OI2: An in Situ Neutron Diffraction Study.

    Science.gov (United States)

    Zhu, Jinlong; Wang, Yonggang; Li, Shuai; Howard, John W; Neuefeind, Jörg; Ren, Yang; Wang, Hui; Liang, Chengdu; Yang, Wenge; Zou, Ruqiang; Jin, Changqing; Zhao, Yusheng

    2016-06-20

    Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-state battery. In this work, the sodium ionic transport pathways of the parent compound Na3OBr, as well as the modified layered antiperovskite Na4OI2, were studied and compared through temperature-dependent neutron diffraction combined with the maximum entropy method. In the cubic Na3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions hop within and among oxygen octahedra, and Br(-) ions are not involved. In the tetragonal Na4OI2 antiperovskite, Na ions, which connect octahedra in the ab plane, have the lowest activation energy barrier. The transport of sodium ions along the c axis is assisted by I(-) ions.

  12. Sodium Ion Transport Mechanisms in Antiperovskite Electrolytes Na 3 OBr and Na 4 OI 2 : An in Situ Neutron Diffraction Study

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Jinlong; Wang, Yonggang; Li, Shuai; Howard, John W.; Neuefeind, Jörg; Ren, Yang; Wang, Hui; Liang, Chengdu; Yang, Wenge; Zou, Ruqiang; Jin, Changqing; Zhao, Yusheng

    2016-06-20

    Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-state battery. In this work, the sodium ionic transport pathways of the parent compound Na3OBr, as well as the modified layered antiperovskite Na4OI2, were studied and compared through temperature dependent neutron diffraction combined with the maximum entropy method. In the cubic Na3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions hop within and among oxygen octahedra, and Br- ions are not involved. In the tetragonal Na4OI2 antiperovskite, Na ions, which connect octahedra in the ab plane, have the lowest activation energy barrier. The transport of sodium ions along the c axis is assisted by I- ions.

  13. Mn-Substitution Effect on Thermal Conductivity of Delafossite-Type Oxide CuFeO2

    Science.gov (United States)

    Nozaki, T.; Hayashi, K.; Kajitani, T.

    2010-09-01

    We have prepared the CuFe1- x Mn x O2 solid solution to enhance the thermoelectric performance of CuFeO2 by reducing its thermal conductivity κ. With increasing x above 0.4, the crystal structure changes from delafossite left( {Roverline{3} m} right) to crednerite ( C2/ m). CuFe0.5Mn0.5O2 exhibits the lowest κ value of 2.28 W/m K at the theoretical density, being about one-quarter of that of the end members, CuFeO2 and CuMnO2. We discuss the temperature dependence of κ in terms of a classical phonon transport model, and conclude that local structural modulation due to the mixture of undistorted FeO6 octahedra and distorted MnO6 octahedra in CuFe1- x Mn x O2 leads to the significant reduction of κ.

  14. Poly[bis(phenethylammonium [dibromidoplumbate(II]-di-μ-bromido

    Directory of Open Access Journals (Sweden)

    Kengo Shibuya

    2009-11-01

    Full Text Available Crystals of the title compound, {(C6H5C2H4NH32[PbBr4]}n, were grown at room temperature from a solution in N,N-dimethylformamide (DMF using nitromethane as the poor solvent. This perovskite-type organic–inorganic hybrid compound consists of well ordered sheets of corner-sharing disordered PbBr6 octahedra separated by bilayers of phenethylammonium cations. The octahedra are rotated and tilted due to N—H...Br hydrogen bonds with the ammonium groups, generating a superstructure in the unit cell similar to that of the tetrachloridoplumbate (C6H5C2H4NH32[PbCl4].

  15. Bimetallic MOFs (H3O)x[Cu(MF6)(pyrazine)2]·(4 - x)H2O (M = V4+, x = 0; M = Ga3+, x = 1)

    DEFF Research Database (Denmark)

    Manson, Jamie L.; Schlueter, John A.; Garrett, Kerry E.

    2016-01-01

    The title compounds are bimetallic MOFs containing [Cu(pyz)2]2+ square lattices linked by MF6 n- octahedra. In each, only the Cu2+ spins exhibit long-range magnetic order below 3.5 K (M = V4+) and 2.6 K (M = Ga3+). The V4+ spins remain disordered down to 0.5 K.......The title compounds are bimetallic MOFs containing [Cu(pyz)2]2+ square lattices linked by MF6 n- octahedra. In each, only the Cu2+ spins exhibit long-range magnetic order below 3.5 K (M = V4+) and 2.6 K (M = Ga3+). The V4+ spins remain disordered down to 0.5 K....

  16. Octahedral engineering of orbital polarizations in charge transfer oxides

    Science.gov (United States)

    Cammarata, Antonio; Rondinelli, James M.

    2013-04-01

    Negative charge transfer ABO3 oxides may undergo electronic metal-insulator transitions (MIT) concomitant with a dilation and contraction of nearly rigid octahedra. On both sides of the MIT are in-phase or out-of-phase (or both) rotations of adjacent octahedra that buckle the B-O-B bond angle away from 180∘. Using density functional theory with the PBEsol +U approach, we describe an octahedral engineering avenue to control the B 3d and O 2p orbital polarization through enhancement of the BO6 rotation “sense” rather than solely through conventional changes to the B-O bond lengths, i.e., crystal field distortions. Using CaFeO3 as a prototypical material, we show the flavor of the octahedral rotation pattern when combined with strain-rotation coupling and thin film engineering strategies offers a promising avenue to fine tune orbital polarizations near electronic phase boundaries.

  17. Interesting cationic (Li /Fe /Te ) variations in new rocksalt ordered ...

    Indian Academy of Sciences (India)

    oxides are derived from the rocksalt (NaCl) structure by the ordering of layers formed by the edge-shared .... ture has been noted with the formation of almost reg- ular TeO6 octahedra with Te–O bond lengths ranging ... bond valences for Li+, Fe3+ and Te6+ ions based on their oxidation states (table 2). The verification of ...

  18. Investigations on the local structure and the spin-Hamiltonian ...

    Indian Academy of Sciences (India)

    ... and the required crystal field parameters are obtained using the superposition model and the local structures of the studied [ C u ( H 2 O ) 6 ] 2 + cluster. According to the calculations, the ligand octahedra around C u 2 + suffer relative elongation\\tau{\\sim 0.085 \\AA) along the [0 0 1] (or \\tau{\\sim 0.085 \\AA) along the [0 0 1] ...

  19. RuSr2GdCu2O8 and RuSr2Gd1.5Ce0.5Cu2O10

    Indian Academy of Sciences (India)

    a three-layer fluorite-type block instead of a single oxygen-free R (= rare earth element) layer is inserted between the .... tilting of the RuO6 octahedra and the other along the b direction. Earlier microstructural ... that we get the 'b-direction clean a–b plane' with only RuO6 tilting superstructure in the same sample. Electron ...

  20. Hydrothermal syntheses and characterization of uranyl tungstates with electro-neutral structural units

    Energy Technology Data Exchange (ETDEWEB)

    Balboni, Enrica; Burns, Peter C. [Univ. of Notre Dame, IN (United States). Dept. of Civil and Enviromental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry

    2015-11-01

    Two uranyl tungstates, (UO{sub 2})(W{sub 2}O{sub 7})(H{sub 2}O){sub 3} (1) and (UO{sub 2}){sub 3}(W{sub 2}O{sub 8})F{sub 2}(H{sub 2}O){sub 3} (2), were synthesized under hydrothermal conditions at 220 C and were structurally, chemically, and spectroscopically characterized. 1 Crystallizes in space group Pbcm, a = 6.673(5) Aa, b = 12.601(11) Aa, c = 11.552 Aa; 2 is in C2/m, a = 13.648(1) Aa, b = 16.852(1) Aa, c = 9.832(1) Aa, β = 125.980(1) {sup circle}. In 1 the U(VI) cations are present as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by five oxygen atoms to give pentagonal bipyramids. These share two edges with two tungstate octahedra and single vertices with four additional octahedra, resulting in a sheet with the iriginite-type anion topology. Only water molecules are located in the interlayer. The structural units of 2 consist of (UO{sub 2}){sup 2+} uranyl oxy-fluoride pentagonal bipyramids present as either [UO{sub 2}F{sub 2}O{sub 3}]{sup -6} or [UO{sub 2}FO{sub 4}]{sup -5}, and strongly distorted tungstate octahedra. The linkage of uranyl pentagonal bipyramids and tungstate octahedra gives a unique sheet anion topology consisting of pentagons, squares and triangles. In 2, the uranyl tungstates sheets are connected into a novel electro-neutral three-dimensional framework through dimers of uranyl pentagonal bipyramids. These dimers connecting the sheets share an edge defined by F anions. 2 is the first example of a uranyl tungstate oxy-fluoride, and 1 and 2 are rare examples of uranyl compounds containing electro-neutral structural units.

  1. Structural, thermal behaviour and vibrational study of a new mixed ...

    Indian Academy of Sciences (India)

    These anions show a 4° rotation around the fourfold axis against the cubic arrangement of the K2PtCI6 type structure. The monovalent cations (Cs+/NH 4 + ) are located between the octahedra ensuring the stability of the structure by ionic and hydrogen bonding contacts: Cs…Cl/Br and N-H … … Cl/Br. A DTA/TGA ...

  2. Charge-order driven multiferroic and magneto-dielectric properties ...

    Indian Academy of Sciences (India)

    Administrator

    manganates (figure 4) (Vogt et al 1996; Woodward et al. 1999). For example, the charge-ordered structure of. Nd0⋅5Sr0⋅5MnO3 consists of distorted oxygen octahedra with zigzag chains with alternate long and short Mn–O bonds. In terms of the chemistry, the mean A-site cation radius 〈rA〉 is expected to play an important ...

  3. Applied solid state science advances in materials and device research

    CERN Document Server

    Wolfe, Raymond

    2013-01-01

    Applied Solid State Science: Advances in Materials and Device Research, Volume 4 covers articles on single crystal compound semiconductors and complex polycrystalline materials. The book discusses narrow gap semiconductors and solid state batteries. The text then describes the advantages of hot-pressed microcrystalline compacts of oxygen-octahedra ferroelectrics over single crystal materials, as well as heterostructure junction lasers. Solid state physicists, materials scientists, electrical engineers, and graduate students studying the subjects being discussed will find the book invaluable.

  4. Trapping shape-controlled nanoparticle nucleation and growth stages via continuous-flow chemistry

    KAUST Repository

    LaGrow, Alec P.

    2017-02-06

    Continuous flow chemistry is used to trap the nucleation and growth stages of platinum-nickel nano-octahedra with second time resolution and high throughputs to probe their properties ex situ. The growth starts from poorly crystalline particles (nucleation) at 5 seconds, to crystalline 1.5 nm particles bounded by the {111}-facets at 7.5 seconds, followed by truncation and further growth to octahedral nanoparticles at 20 seconds.

  5. Ultrathin Limit of Exchange Bias Coupling at Oxide Multiferroic/Ferromagnetic Interfaces

    Science.gov (United States)

    2013-07-12

    stabilizers in recording heads based on anisotropic magnetoresistance . [ 11 ] Exchange bias heterostructures based on multiferroic materials...epitaxial layers of LSMO and BFO, which were strained in-plane to the STO (001) substrate. Figure 1 c shows the presence of Kiessig fringes...drastically. This is generally interpreted by considering a strain -induced distortion of MnO 6 octahedra based on the Jahn-Teller distortion theory. [ 39

  6. Manganese-mediated ferromagnetism in La 2 Fe Mn 2 Cr O 6 ...

    Indian Academy of Sciences (India)

    We have investigated the structure and magnetic properties of the perovskite oxides of the formula La2Fe1-Mn2Cr1-O6 (0 < < 1.0). For 0 < ≤ 0.5, the members adopt the orthorhombic (Pbnm) structure, where the transition metal atoms are disordered at the 4b sites and the MO6 (M = Fe, Mn, Cr) octahedra become ...

  7. Synthesis and characterization of novel ternary and quaternary reduced molybdenum oxides

    Energy Technology Data Exchange (ETDEWEB)

    Schimek, George L. [Iowa State Univ., Ames, IA (United States)

    1993-07-01

    This thesis is divided into 8 sections: synthesis and characterization (char.) of Ba3Mo18O28 (an oligomer with four traps edge-sharing Mo octahedra); synthesis and char. of KxMyMo14O22 (M=Sn, Pb, Sr) (oligomers with three traps edge-sharing Mo octahedra); synthesis and char. of K0.19Ba3.81Mo22O34 (an oligomer with five traps edge-sharing Mo octahedra); synthesis and char. of Ti0.31Fe1.69Mo4O7 (a material containing closest-packing of infinite chains of octahedral Mo clusters); synthesis and char. of KxM2-xMo10O16 (M=Ca, Sr, Gd) (oligomers with two traps edge-sharing Mo octahedra); synthesis and char. of the RE4Mo4O11 series; synthesis and char. of Pb0.31WO3 (a tetragonal tungsten bronze containing lead); and examination of superstructure in Fe1.89Mo4.11O7, Sn0.9Mo4O6, InMo4O6, and Mn1.5Mo8O11 by electron microscopy.

  8. Continuous Production of Carbon-Supported Cubic and Octahedral Platinum-Based Catalysts Using Conveyor Transport System.

    Science.gov (United States)

    Tsao, Kai-Chieh; Yang, Hong

    2016-09-01

    A conveyor transport system is developed for the continuous production of carbon-supported uniform Pt nanocubes, and Pt 3 Ni nanocubes and octahedra in a single-reaction system under hot carbon monoxide environment. Oleylamine is critical for the high loading and even the dispersion of Pt nanocubes on a carbon support. The metal catalyst shows high performance in electrocatalytic oxidation of methanol. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. The crystal structure of alpha-K3AlF6: elpasolites and double perovskites with broken corner-sharing connectivity of the octahedral framework.

    Science.gov (United States)

    Abakumov, Artem M; King, Graham; Laurinavichute, Veronika K; Rozova, Marina G; Woodward, Patrick M; Antipov, Evgeny V

    2009-10-05

    The crystal structure of alpha-K(3)AlF(6) was solved and refined from a combination of powder X-ray and neutron diffraction data (a = 18.8385(3)A, c = 33.9644(6)A, S.G. I4(1)/a, Z = 80, R(P)(X-ray) = 0.037, R(P)(neutron) = 0.053). The crystal structure is of the A(2)BB'X(6) elpasolite type with the a = b approximately a(e) square root(5), c = 4a(e) superstructure (a(e), parameter of the elpasolite subcell) and rock-salt-type ordering of the K and Al cations over the B and B' positions, respectively. The remarkable feature of alpha-K(3)AlF(6) is a rotation of 2/5 of the AlF(6) octahedra by approximately pi/4 around one of the crystal axes of the elpasolite subcell, coinciding with the 4-fold symmetry axes of the AlF(6) octahedra. The rotation of the AlF(6) octahedra replaces the corner-sharing between the K and Al polyhedra by edge-sharing, resulting in an increase of coordination numbers of the K cations at the B positions up to 7 and 8. Due to significant deformations of the K polyhedra, the corner-sharing connectivity of the octahedral elpasolite framework is broken and the rotations of the AlF(6) octahedra do not have a cooperative character. Elpasolites and double perovskites with similar structural organization are discussed. The difference in ionic radii of the B and B' cations as well as the tolerance factor are proposed to be the parameters governing the formation of elpasolites and double perovskites with broken corner-sharing connectivity of the octahedral framework.

  10. Absence of a polar phase in perovskite chromite RCrO{sub 3} (R=La and Pr)

    Energy Technology Data Exchange (ETDEWEB)

    Yoshii, Kenji, E-mail: yoshiike@spring8.or.jp [Japan Atomic Energy Agency (JAEA), Sayo, Hyogo 679-5148 (Japan); Ikeda, Naoshi [Okayama University, Okayama 700-8530 (Japan); Shimojo, Yutaka; Ishii, Yoshinobu [Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki 319-1195 (Japan)

    2017-04-01

    Magnetic and dielectric properties have been studied for LaCrO{sub 3}, PrCrO{sub 3}, and their solid solution La{sub 0.5}Pr{sub 0.5}CrO{sub 3}, which belong to a family of the ferroelectric orthochromite series RCrO{sub 3} (R: rare earths). The magnetic measurements confirm that the materials show canted antiferromagnetic ordering at 240–288 K. Neutron diffraction patterns could be fitted with the centrosymmetric Pnma, which is different from the non-centrosymmetric structure proposed for the ferroelectric phase of NdCrO{sub 3}. The large dielectric constants are likely due to the hopping of charge carriers as proposed previously for other chromites. - Highlights: • Magnetic and dielectric properties of the three perovskite chromites. • Neutron diffraction patterns fitted with centrosymmetric Pnma. • Large dielectric constants likely due to the hopping of charge carriers.

  11. Evolution of structural and magnetic properties due to nanocrystallization of mechanically milled amorphous Pr-Co-B powders

    Energy Technology Data Exchange (ETDEWEB)

    Ucar, Huseyin; Parans Paranthaman, M., E-mail: paranthamanm@ornl.gov [Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Nlebedim, Ikenna C.; William McCallum, R. [Ames Laboratory, Ames, Iowa 50011 (United States)

    2014-12-21

    Pr{sub 2}Co{sub 14}B permanent magnet powders were prepared by mechanical milling of an arc-melted ingot. X-ray diffraction analysis revealed the presence of the 2:14:1 phase after 1 h of milling which transformed into an amorphous phase with additional milling time. Increasing the milling time also lowered the intrinsic coercivity while the saturation magnetization increased up to 105 emu/g. Differential scanning calorimetry measurements revealed a crystallization temperature of around 560 °C. Upon annealing 30 h of as-milled amorphous powders between 500 and 900 °C, we observed the precipitation of the 2:14:1 phase. The optimum post-milling annealing temperature was 600 °C with an intrinsic coercivity of 7 kOe and maximum energy product of 6 MGOe.

  12. Magnetism and the absence of superconductivity in the praseodymium–silicon system doped with carbon and boron

    Energy Technology Data Exchange (ETDEWEB)

    de la Venta, J.; Basaran, Ali C.; Grant, T.; Gallardo-Amores, J. M.; Ramirez, J. G.; Alario-Franco, M. A.; Fisk, Z.; Schuller, Ivan K.

    2013-08-01

    We searched for new structural, magnetic and superconductivity phases in the Pr–Si system using high-pressure high-temperature and arc melting syntheses. Both high and low Si concentration areas of the phase diagram were explored. Although a similar approach in the La–Si system produced new stable superconducting phases, in the Pr–Si system we did not find any new superconductors. At low Si concentrations, the arc-melted samples were doped with C or B. It was found that addition of C gave rise to multiple previously unknown ferromagnetic phases. Furthermore, X-ray refinement of the undoped samples confirmed the existence of the so far elusive Pr>3Si2 phase.

  13. Time reversal symmetry breaking in superconducting(Pr,La)Os{sub 4}Sb{sub 12} and Pr(Os,Ru){sub 4}Sb{sub 12}

    Energy Technology Data Exchange (ETDEWEB)

    Shu, L. [Department of Physics, University of California, Riverside, CA 92521 (United States)]. E-mail: lei.shu@email.ucr.edu; Higemoto, W. [Japan Atomic Energy Agency, Tokai-Mura, Ibaraki 319-1195 (Japan); Aoki, Y. [Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397 (Japan); Frederick, N.A. [Department of Physics, University of California, San Diego, La Jolla, CA 92093 (United States); Yuhasz, W.M. [Materials Science and Engineering Program, University of California, San Diego, La Jolla, CA 92093 (United States); Heffner, R.H. [Japan Atomic Energy Agency, Tokai-Mura, Ibaraki 319-1195 (Japan); Ohishi, K. [Japan Atomic Energy Agency, Tokai-Mura, Ibaraki 319-1195 (Japan); Ishida, K. [Department of Physics, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Kadono, R. [Meson Science Laboratory, KEK, Tsukuba, Ibaraki 305-0801 (Japan); Koda, A. [Meson Science Laboratory, KEK, Tsukuba, Ibaraki 305-0801 (Japan); Kikuchi, D. [Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397 (Japan); Sato, H. [Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397 (Japan); Sugawara, H. [Faculty of the Integrated Arts and Sciences, University of Tokushima, Minami-jousanjima-machi 1-1, Tokushima 770-8502 (Japan); Ito, T.U. [Japan Atomic Energy Agency, Tokai-Mura, Ibaraki 319-1195 (Japan); Sanada, S. [Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397 (Japan); Tunashima, Y. [Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397 (Japan); Yonezawa, Y. [Department of Physics, Tokyo Metropolitan University, Tokyo 192-0397 (Japan); Maple, M.B. [Department of Physics, University of California, San Diego, La Jolla, CA 92093 (United States); MacLaughlin, D.E. [Department of Physics, University of California, Riverside, CA 92521 (United States)

    2007-03-15

    Zero-field muon spin relaxation ({mu}SR) experiments have been carried out in the Pr(Os{sub 1-x}Ru{sub x}){sub 4}Sb{sub 12} and Pr{sub 1-y}La{sub y}Os{sub 4}Sb{sub 12} alloy systems to investigate the time-reversal symmetry (TRS) breaking found in an earlier ZF-{mu}SR study of the end compound PrOs{sub 4}Sb{sub 12}. Our results suggest that Ru doping is considerably more efficient than La doping in suppressing TRS-breaking superconducting pairing in PrOs{sub 4}Sb{sub 12}.

  14. Crystal field interactions studied by high-field magnetization

    Energy Technology Data Exchange (ETDEWEB)

    Radwanski, R.J.; Franse, J.J.M. (Van der Waals-Zeeman Lab., Univ. Amsterdam (Netherlands))

    1992-03-01

    The effect of crystalline electric field (CEF) interactions of the 4f ions on the magnetization process is reviewed for some intermetallic compounds. Special emphasis is given to metamagnetic transitions. The transitions in Ho{sub 2}Co{sub 17} are exchange-driven transitions associated with the formation of a non-collinear magnetic structure in contrast to the transition found in DyCo{sub 2}Si{sub 2} that is of a level-crossing type. The transition found in Pr{sub 2}Fe{sub 14}B results from a competition between lower and higher order crystal field terms. The formation of the rare earth moment under the action of CEF and exchange interactions as well as of external fields is analyzed. (orig.).

  15. The effect of surfactant addition on high-energy milling upon the magnetic properties and microstructure of the Pr-Fe-B HDDR magnetic powders; Efeito da adicao de surfactantes nas propriedades e microestrutura de pos magneticos a base de Pr-Fe-B obtidos via HDDR e moagem de alta energia

    Energy Technology Data Exchange (ETDEWEB)

    Santos, P.B.; Silva, S.C.; Faria, R.N.; Takiishia, H., E-mail: pbsantos@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2010-07-01

    Nanomagnetic powders based on the composition Pr{sub 12}Fe{sub 65.9}Co{sub 16}B{sub 6}Nb{sub 0.1} have been obtained from using (a) the hydrogenation, disproportionation, desorption and recombination (HDDR) process; (b) by varying of milling time and (c) with the addition of an oleic acid as a surfactant. The latter has been used to enhance milling condition by preventing the agglomeration of particles and hence to improve the intrinsic coercivity of the material. High-energy mechanical milling has been used to yield magnetic nanoparticles. Powders were characterized magnetically using vibrating sample magnetometer (VSM) and microstructurally by Scanning Electron Microscopy (SEM), Field Emission Gun SEM (FEG-SEM) and X-ray diffraction. (author)

  16. Low temperature diffusion process using rare earth-Cu eutectic alloys for hot-deformed Nd-Fe-B bulk magnets

    Energy Technology Data Exchange (ETDEWEB)

    Akiya, T., E-mail: akiya.takahiro@nims.go.jp; Sepehri-Amin, H.; Ohkubo, T. [Elements Strategy Initiative Center for Magnetic Materials, National Institute for Materials Science, Tsukuba 305-0047 (Japan); Liu, J.; Hono, K. [Elements Strategy Initiative Center for Magnetic Materials, National Institute for Materials Science, Tsukuba 305-0047 (Japan); Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8577 (Japan); Hioki, K.; Hattori, A. [Daido Steel Co., LTD, Nagoya 457-8545 (Japan)

    2014-05-07

    The low temperature grain boundary diffusion process using RE{sub 70}Cu{sub 30} (RE = Pr, Nd) eutectic alloy powders was applied to sintered and hot-deformed Nd-Fe-B bulk magnets. Although only marginal coercivity increase was observed in sintered magnets, a substantial enhancement in coercivity was observed when the process was applied to hot-deformed anisotropic bulk magnets. Using Pr{sub 70}Cu{sub 30} eutectic alloy as a diffusion source, the coercivity was enhanced from 1.65 T to 2.56 T. The hot-deformed sample expanded along c-axis direction only after the diffusion process as RE rich intergranular layers parallel to the broad surface of the Nd{sub 2}Fe{sub 14}B are thickened in the c-axis direction.

  17. Octahedral tilt transitions in the relaxor ferroelectric Na{sub 1/2}Bi{sub 1/2}TiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, Kai-Christian, E-mail: meyer@mm.tu-darmstadt.de; Gröting, Melanie; Albe, Karsten

    2015-07-15

    The kinetics of octahedral tilt transitions in the lead-free relaxor material sodium bismuth titanate Na{sub 1/2}Bi{sub 1/2}TiO{sub 3} (NBT) is investigated by electronic structure calculations within density functional theory. Energy barriers for transitions between tetragonal, rhombohedral and orthorhombic tilts in cation configurations with [001]- and [111]-order on the A-sites are determined by nudged elastic band calculations. By tilting entire layers of octahedra simultaneously we find that the activation energy is lower for structures with 001-order compared to such with 111-order. The energetic coupling between differently tilted layers is, however, negligibly small. By introducing a single octahedral defect we create local tilt disorder and find that the deformation energy of the neighboring octahedra is less in a rhombohedral than in a tetragonal structure. By successively increasing the size of clusters of orthorhombic defects in a rhombohedral matrix with 001-order, we determine a critical cluster size of about 40 Å . Thus groups of about ten octahedra can be considered as nuclei for polar nanoregions, which are the cause of the experimentally observed relaxor behavior of NBT. - Graphical abstract: Nine orthorhombic oxygen octahedral tilt defects in a rhombohedral tilt configuration. - Highlights: • Chemical order influences energy barriers of octahedral tilt transitions. • The octahedral deformation energy is lower in rhombohedral phases. • Tilt defect clusters are more likely in rhombohedral structures. • Tilt defect clusters can act as nuclei for polar nanoregions.

  18. K(MoO24O3(AsO4

    Directory of Open Access Journals (Sweden)

    Raja Jouini

    2013-06-01

    Full Text Available A new compound with a non-centrosymmetric structure, potassium tetrakis[dioxomolybdenum(IV] arsenate trioxide, K(MoO24O3(AsO4, has been synthesized by a solid-state reaction. The [(MoO24O3(AsO4]+ three-dimensional framework consists of single arsenate AsO4 tetrahedra, MoO6 octahedra, MoO5 bipyramids and bioctahedral units of edge-sharing Mo2O10 octahedra. The [Mo2O8]∞ octahedral chains running along the a-axis direction are connected through their corners to the AsO4 tetrahedra, MoO6 octahedra and MoO5 bipyramids, so as to form large tunnels propagating along the a axis in which the K+ cations are located. This structure is compared with compounds containing M2O10 (M = Mo, V, Fe dimers and with those containing M2O8 (M = V chains.

  19. Synthesis of LiTiPO 5 and LiTiAsO 5 with the α-Fe 2PO 5 Structure

    Science.gov (United States)

    Robertson, A.; Fletcher, J. G.; Skakle, J. M. S.; West, A. R.

    1994-03-01

    The new phases LiTiPO 5 and LiTiAsO 5 have been synthesized by solid state reaction. They are essentially isostructural with α-Fe 2PO 5, as confirmed by X-ray Rietveld refinement. The structures are built of chains of edge-sharing LiO 6 octahedra cross-linked by chains of alternate corner-sharing PO 4 tetrahedra and TiO 6 octahedra (each of which shares common faces with two LiO 6 octahedra). Unit cell dimensions: LiTiPO 5, a = 7.4000(5) Å, b = 6.3752(3) Å, c = 7.2347(4) Å; LiTiAsO 5, a = 7.5257(5) Å, b = 6.5786(4) Å, c = 7.4524(5) Å. Space group: Pnma. The phases melt incongruently at ˜1080°C and exhibit very low electrical conductivities, (5-10) × 10 -6 S cm -1 at 400°C with activation energy ˜1 eV. Subsolidus phase diagrams for the systems Li 2O-TiO 2-P 2O 5/As 2O 5 are presented.

  20. Mechanisms controlling renal hemodynamics and electrolyte excretion during amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Woods, L.L.; Mizelle, H.L.; Montani, J.P.; Hall, J.E.

    1986-08-01

    Our purpose was to investigate the mechanisms by which increased plasma amino acids elevate renal blood flow (RBF) and glomerular filtration rate (GFR). Since transport of amino acids and Na is linked in the proximal tubule, the authors hypothesized that increased amino acids might stimulate proximal tubular Na reabsorption (PR/sub Na/) and thus increase RBF and GFR by a macula densa feedback mechanism. A solution of four amino acids (Ala, Ser, Gly, Pro) was infused intravenously into anesthetized dogs with normal kidneys (NK) and with kidneys in which the tubuloglomerular feedback mechanism was blunted by lowering renal artery pressure (LPK) or blocked by making the kidneys nonfiltering (NFK). In NK, RBF and GFR increased by 35 +/- 4% and 30 +/- 7% after 90 min of amino acid infusion, while PR/sub Na/ (estimated from lithium clearance) and O2 consumption increased by 31 +/- 5% and 29 +/- 5% and distal Na delivery remained relatively constant. Autoregulation of RBF and GFR in response to step deceases in renal artery pressure was impaired during amino acids in NK. The hemodynamic responses to amino acids were abolished in LPK and NFK. Infusion of the nonmetabolized -aminoisobutyric acid into NK produced changes in renal hemodynamics that were similar to the responses observed with the four metabolizable amino acids. These data are consistent with the hypothesis that elevation of plasma amino acids increases RBF and GFR by a mechanism that requires an intact macula densa feedback. Metabolism of the amino acids does not appear to be necessary for these changes to occur.

  1. CVD growth of (001) and (111)3C-SiC epilayers and their interface reactivity with pradeodymium oxide dielectric layers

    Energy Technology Data Exchange (ETDEWEB)

    Sohal, R.

    2006-07-24

    In this work, growth and characterisation of 3C-SiC thin films, investigation of oxidation of thus prepared layers and Pr-silicate and AlON based interface with SiC have been studied. Chemical vapor deposition of 3C-SiC thin films on Si(001) and Si(111) substrates has been investigated. Prior to the actual SiC growth, preparation of initial buffer layers of SiC was done. Using such a buffer layer, epitaxial growth of 3C-SiC has been achieved on Si(111) and Si(001) substrates. The temperature of 1100 C and 1150 C has been determined to be the optimal temperature for 3C-SiC growth on Si (111) and Si(001) substrates respectively. The oxidation studies on SiC revealed that a slow oxidation process at moderate temperatures in steps was useful in reducing and suppressing the g-C at the SiO{sub 2}/SiC interface. Clean, graphite-free SiO{sub 2} has been successfully grown on 3C-SiC by silicon evaporation and UHV anneal. For the application of high-k Pr{sub 2}O{sub 3} on silicon carbide, plausible interlayer, Pr-Silicate and AlON, have been investigated. Praseodymium silicate has been prepared successfully completely consuming the SiO2 and simultaneously suppressing the graphitic carbon formation. A comparatively more stable interlayer using AlON has been achieved. This interlayer mainly consists of stable phases of AlN along with some amount of Pr-aluminates and CN. Such layers act as a reaction barrier between Pr{sub 2}O{sub 3} and SiC, and simultaneously provide higher band offsets. (orig.)

  2. Novel chromium doped perovskites A{sub 2}ZnTiO{sub 6} (A = Pr, Gd): Synthesis, crystal structure and photocatalytic activity under simulated solar light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Hekai [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Fang, Minghao, E-mail: fmh@cugb.edu.cn [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Huang, Zhaohui, E-mail: huang118@cugb.edu.cn [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Liu, Yan’gai [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Chen, Kai [National Engineering Research Center for Rare Earth Materials, General Research Institute For Nonferrous Metals, Grirem Advanced Materials Co.,Ltd., Beijing 100088 (China); Guan, Ming; Tang, Chao; Zhang, Lina; Wang, Meng [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China)

    2017-01-30

    Highlights: • Novel Cr doped A{sub 2}ZnTiO{sub 6} (A = Pr, Gd) photocatalysts were successfully synthesized. • The light absorbance and photocatalytic activity are enhanced through Cr doping. • The photocatalytic reaction mechanism of these photocatalyst was investigated. - Abstract: Double perovskite related oxides A{sub 2}ZnTiO{sub 6} (A = Pr, Gd) have been successfully synthesized by solid state reaction and investigated as photocatalysts for the first time. The two layered titanates mainly demonstrate absorbances under UV irradiation, except for several sharp absorption bands above 400 nm for Pr{sub 2}ZnTiO{sub 6}. Therefore, a series of photocatalysts by doping A{sub 2}ZnTiO{sub 6} (A = Pr, Gd) with Cr have been developed in the hope to improve their absorption in the visible light region. The successful incorporation of Cr was detected by XRD and XPS, and the prepared samples have also been characteriazed by SEM, UV–vis DRS and PL. The characterization results suggested that Cr was present mainly in the form of Cr3+, with only a small amount of Cr6+ species. It served as an efficient dopant for the extension of visible light absorbance and improved photocatalytic activities under solar light irradiation. For both Pr{sub 2}ZnTiO{sub 6} and Gd{sub 2}ZnTiO{sub 6}, the valence band (VB) was composed of hybridized states of the Zn 3d, O 2p and the conduction band (CB) has major contribution from Zn 4s, Ti 3d orbitals. For Cr doped samples, the newly formed spin-polarized valence band in the middle of the band gap that primarily arises from Cr 3d orbitals was responsible for the improved optical and photocatalytic properties.

  3. Solid-state transformation of single precursor vanadium complex nanostructures to V₂O₅ and VO₂: catalytic activity of V₂O₅ for oxidative coupling of 2-naphthol.

    Science.gov (United States)

    Pradhan, Mukul; Roy, Anindita; Sinha, Arun Kumar; Sahoo, Ramkrishna; Deb, Dibakar; Pal, Tarasankar

    2015-01-28

    A vanadium complex, [(C5H5N)2V2O3·H2O], of different morphologies has been obtained via a modified hydrothermal procedure using pyridine and VOSO4 salt as the starting material. The evolved [(C5H5N)2V2O3·H2O] nanobelts are of 50-200 nm in width and of a length up to several millimeters. At higher temperatures (600 °C), the solid [(C5H5N)2V2O3·H2O] nanostructures are converted to vanadium pentoxide (V2O5) and vanadium dioxide (VO2) when heated in air and nitrogen atmosphere, respectively. During growth, the mechanism of the evolution of octahedra, truncated octahedra, and hollow truncated octahedra of [(C5H5N)2V2O3·H2O] are reported for the first time. These types of well-structured morphology are also isolated while V2O5 and VO2 are evolved. The as-grown belt-like and octahedral morphologies of [(C5H5N)2V2O3·H2O] are retained during the solid-state transformation, suggesting a route to evolve crystalline nanomaterials. Again, the morphological evolution of the [(C5H5N)2V2O3·H2O] nanostructures has been examined to be pyridine and precursor vanadyl sulfate (VS) concentration dependent. Thus, we are able to isolate truncated octahedra as an intermediate during the formation of [(C5H5N)2V2O3·H2O] nanobelts and nanoflowers with a high pyridine (Py) concentration. Interestingly, longer reaction times successively featured the transformation of truncated octahedra into nanobelts. Nanobelt evolution is not observed at low pyridine concentrations. However, the formation of octahedral morphology takes place at low pyridine concentration. All of the nanostructures were critically examined and characterized thoroughly by various physical techniques to ascertain their purity, structure and composition. An interesting, thermodynamically stable, single crystalline product from DMF soluble [(C5H5N)2V2O3·H2O] has been characterized, which indirectly supports the composition of [(C5H5N)2V2O3·H2O]. Selectively, vanadium pentoxide nanobelts have been found to be an

  4. Hermannjahnite, CuZn(SO4)2, a new mineral with chalcocyanite derivative structure from the Naboko scoria cone of the 2012-2013 fissure eruption at Tolbachik volcano, Kamchatka, Russia

    Science.gov (United States)

    Siidra, Oleg I.; Nazarchuk, Evgeny V.; Agakhanov, Atali A.; Lukina, Evgeniya A.; Zaitsev, Anatoly N.; Turner, Rick; Filatov, Stanislav K.; Pekov, Igor V.; Karpov, Gennady A.; Yapaskurt, Vasiliy O.

    2017-07-01

    A new mineral hermannjahnite, ideally CuZn(SO4)2, was found in the sublimates of Saranchinaitovaya fumarole, Naboko scoria cone, where the recent Fissure Tolbachik Eruption occurred in 2012-2013. The cotype specimen was found in the Arsenatnaya fumarole, on the Second scoria cone of the Great Tolbachik Fissure Eruption (GTFE 1975-1976). The mineral is named in honour of Hermann Arthur Jahn. Jahn-Teller effect is pronounced in the structure of hermannjahnite. The empirical formula of the holotype hermannjahnite, calculated on the basis of 8 O apfu is: Cu1.00(Zn0.43Cu0.31Mg0.25)∑0.99S2.00O8. Hermannjahnite is optically biaxial (+), α = 1.642(2), β = 1.652(2), γ = 1.675(2) (589 nm) with 2 V (calc.) = 67.6°. Hermannjahnite is monoclinic, P21/n, a = 4.8076(2), b = 8.4785(3), c = 6.7648(3) Å, β = 93.041(3) °, V = 275.35(2) Å3, Z = 2, R 1 = 0.047. The eight strongest lines of the X-ray powder diffraction pattern are (I-d-hkl): 31-4.231-(020), 100-4.177-(110), 72-3.630-(11-1), 25-3.486-(111), 29-2.681-(11-2), 69-2.648-(02-2), 29-2.561-(112), 63-2.428-(130). The structure of hermannjahnite is isotypic to that of dravertite, CuMg(SO4)2, and represents a monoclinically distorted chalcocyanite CuSO4 structure. Crystallographic and structural data on a natural sample of chalcocyanite are provided. Zinc is very close in ionic radii to copper, but the Jahn-Teller effect on Cu2+ causes the segregation of these elements over two symmetrically independent crystallographic sites in hermannjahnite. Bond-length distortion parameters (∆oct) were evaluated for 44 different MO6 (M = Cu, Zn) octahedra in Cu, Zn oxysalt minerals containing Cu- or/and Zn-dominated octahedra. In hermannjahnite CuO6 octahedra exhibit a value of ∆oct × 103 = 14.71, whereas ∆oct × 103 = 0.83 is calculated for ZnO6. In chalcocyanite CuO6 octahedra have a value of ∆oct × 103 = 8.25. Relationships between calculated ∆oct parameters and occupancy of MO6 (M = Cu, Zn) octahedra by Cu2+ and Zn2

  5. Strong interlayer exchange coupling and high post-annealing stability in perpendicularly magnetized [Pt/Co]/Ru/[Co/Pt] structures

    Directory of Open Access Journals (Sweden)

    Seok Jin Yun

    2016-02-01

    Full Text Available Strong interlayer exchange coupling (IEC and high post-annealing stability are demonstrated for perpendicular synthetic ferrimagnets (p-SyFs with [Pt/Co]6/Ru/[Co/Pt]3 structures. The observed IEC strength was 2.55 ergs/cm2 for a Ru thickness of 0.35 nm, representing the highest value achieved up to date for similar structures. The IEC remained strong even after annealing at 450oC, for the practically important Ru layer thickness of 0.85 nm. The biquadratic IEC, a parameter quantifying the pinhole effects in SyFs, was confirmed by analyzing the experimental results by using the total energy functional, and its strength increased with decreasing the temperature and Ru layer thickness.

  6. Searching for New Chemotherapies for Tropical Diseases: Ruthenium-Clotrimazole Complexes Display High in vitro Activity Against Leishmania major and Trypanosoma cruzi and Low Toxicity Toward Normal Mammalian Cells

    OpenAIRE

    Martínez, Alberto; Carreon, Teresia; Iniguez, Eva; Anzellotti, Atilio; Sánchez, Antonio; Tyan, Marina; Sattler, Aaron; Herrera, Linda; Maldonado, Rosa A.; Sánchez-Delgado, Roberto A.

    2012-01-01

    Eight new ruthenium complexes of clotrimazole (CTZ) with high antiparasitic activity have been synthesized, cis,fac-[RuIICl2(DMSO)3(CTZ)] (1), cis,cis,trans-[RuIICl2(DMSO)2(CTZ)2] (2), Na[RuIIICl4(DMSO)(CTZ)] (3) and Na[trans-RuIIICl4(CTZ)2] (4), [RuII(η6-p-cymene)Cl2(CTZ)] (5), [RuII(η6-p-cymene)(bipy)(CTZ)][BF4]2 (6), [RuII(η6-p-cymene)(en)(CTZ)][BF4]2 (7) and [RuII(η6-p-cymene)(acac)(CTZ)][BF4] (8) (bipy = bipyridine; en = ethlylenediamine; acac = acetylacetonate). The crystal structures o...

  7. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    Science.gov (United States)

    Waychunas, G. A.; Rea, B. A.; Fuller, C. C.; Davis, J. A.

    1993-05-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 Å) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 Å). Mono-dentate arsenate linkages ( 3.60 ± 0.03 Å) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As/Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 Å. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As/Fe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As/Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As/Fe) indicates ferrihydrite units consisting mainly of Fe

  8. Synthesis of vinyl-terminated Au nanoprisms and nanooctahedra mediated by 3-butenoic acid: direct Au@pNIPAM fabrication with improved SERS capabilities

    Science.gov (United States)

    Casado-Rodriguez, M. A.; Sanchez-Molina, M.; Lucena-Serrano, A.; Lucena-Serrano, C.; Rodriguez-Gonzalez, B.; Algarra, M.; Diaz, A.; Valpuesta, M.; Lopez-Romero, J. M.; Perez-Juste, J.; Contreras-Caceres, R.

    2016-02-01

    Here we describe the first seedless synthesis of vinyl-terminated Au nanotriangular prisms (AuNTPs) and nanooctahedra (AuNOC) in aqueous media. This synthesis is performed by chemical reduction of chloroauric acid (HAuCl4) with 3-butenoic acid (3BA) in the presence of benzyldimethylammonium chloride (BDAC). The principal novelties of the presented method are the use of a mixture of 3BA and BDAC, the synthesis of gold prisms and octahedra with controllable size, and the presence of terminal double bonds on the metal surface. Initially this method produces a mixture of triangular gold nanoprisms and octahedra; however, both morphologies are successfully separated by surfactant micelle induced depletion interaction, reaching percentages up to ~90%. Moreover, the alkene moieties present on the gold surface are exploited for the fabrication of hybrid core@shell particles. Gold octahedra and triangular prisms are easily encapsulated by free radical polymerization of N-isopropylacrylamide (NIPAM). Finally, in order to obtain a gold core with the most number of tips, AuNTP@pNIPAM microgels were subjected to gold core overgrowth, thus resulting in star-shaped nanoparticles (AuSTs@pNIPAM). We use 4-amino-benzenethiol as the model analyte for SERS investigations. As expected, gold cores with tips and high curvature sites produced the highest plasmonic responses.Here we describe the first seedless synthesis of vinyl-terminated Au nanotriangular prisms (AuNTPs) and nanooctahedra (AuNOC) in aqueous media. This synthesis is performed by chemical reduction of chloroauric acid (HAuCl4) with 3-butenoic acid (3BA) in the presence of benzyldimethylammonium chloride (BDAC). The principal novelties of the presented method are the use of a mixture of 3BA and BDAC, the synthesis of gold prisms and octahedra with controllable size, and the presence of terminal double bonds on the metal surface. Initially this method produces a mixture of triangular gold nanoprisms and octahedra; however

  9. Crystal structure of a sodium, zinc and iron(III-based non-stoichiometric phosphate with an alluaudite-like structure: Na1.67Zn1.67Fe1.33(PO43

    Directory of Open Access Journals (Sweden)

    Jamal Khmiyas

    2015-06-01

    Full Text Available The new title compound, disodium dizinc iron(III tris(phosphate, Na1.67Zn1.67Fe1.33(PO43, which belongs to the alluaudite family, has been synthesized by solid-state reactions. In this structure, all atoms are in general positions except for four, which are located on special positions of the C2/c space group. This structure is characterized by cation substitutional disorder at two sites, one situated on the special position 4e (2 and the other on the general position 8f. The 4e site is partially occupied by Na+ [0.332 (3], whereas the 8f site is entirely filled by a mixture of Fe and Zn. The full-occupancy sodium and zinc atoms are located at the Wyckoff positions on the inversion center 4a (-1 and on the twofold rotation axis 4e, respectively. Refinement of the occupancy ratios, bond-valence analysis and the electrical neutrality requirement of the structure lead to the given composition for the title compound. The three-dimensional framework of this structure consists of kinked chains of edge-sharing octahedra stacked parallel to [10-1]. The chains are formed by a succession of trimers based on [ZnO6] octahedra and the mixed-cation FeIII/ZnII [(Fe/ZnO6] octahedra [FeIII:ZnIII ratio 0.668 (3/0.332 (3]. Continuous chains are held together by PO4 phosphate groups, forming polyhedral sheets perpendicular to [010]. The stacked sheets delimit two types of tunnels parallel to the c axis in which the sodium cations are located. Each Na+ cation is coordinated by eight O atoms. The disorder of Na in the tunnel might presage ionic mobility for this material.

  10. The local atomic structure of La{sub 1{minus}x}Sr{sub x}CoO{sub 3}: Effects induced by the spin-state and non-metal to metal transitions

    Energy Technology Data Exchange (ETDEWEB)

    Louca, D.; Sarrao, J.L.; Kwei, G.H.

    1998-03-01

    The pair density function (PDF) used in the analysis of pulsed neutron diffraction data of La{sub 1{minus}x}Sr{sub x}CoO{sub 3} revealed new structural effects which are correlated to the susceptibility and transport transitions. The transition in the spin configuration of the Co ions from the low-spin (LS) to the high-spin (HS) state in the Co perovskite oxides can potentially induce structural distortions due to the coupling of the spin to the lattice and charge. The ground state of the pure compound, LaCoO{sub 3}, is in the LS state and is non-magnetic. A transition occurs to the HS state at {approximately} 50 K as indicated from the susceptibility measurements due to the thermal excitation of electrons to the e{sub g} level. The Co{sub LS}O{sub 6} octahedra associated with the Co ions in the LS configuration are distinguished from the Co{sub HS}O{sub 6} octahedra with the Co in the HS configuration because the Co{sub LS}-O bond length is shorter than the Co{sub HS}-O distance due to the different size of the corresponding Co ions. Such bond lengths are clearly identified in the local structure between 15--300 K. This finding is in contrast to the average structure which shows only one type of bond length in this temperature range but two types of bond lengths are suggested at considerably higher temperatures. This suggests that whereas the LS and HS CoO{sub 6}-octahedra coexist, they are randomly distributed in the crystal lattice at lower temperatures and become ordered at higher temperatures.

  11. Understanding the Thermal Stability of Palladium-Platinum Core-Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory.

    Science.gov (United States)

    Vara, Madeline; Roling, Luke T; Wang, Xue; Elnabawy, Ahmed O; Hood, Zachary D; Chi, Miaofang; Mavrikakis, Manos; Xia, Younan

    2017-05-23

    Core-shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core-shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt4L core-shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability of the core-shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. The opposite trend for alloying of the core-shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.

  12. Synthesis and Crystal Structures of the New Alkaline-Mn(II)-Mn(III) Selenites KMn(II) 4Mn(III)(SeO 3) 6 and Li 5Mn(II) 4Mn(III)(SeO 3) 8

    Science.gov (United States)

    Wildner, M.

    1993-04-01

    Crystals of KMn(II) 4Mn(III)(SeO 3) 6 and Li 5Mn(II) 4Mn(III)(SeO 3) 8 were synthesized under hydrothermal conditions and their structures were determined by single-crystal X-ray diffraction data (KMn (II) 4Mn(III)(SeO 3) 6: monoclinic, space group C 2/ c, Z = 4, a = 17.660(3) Å, b = 10.240(1) Å, c = 9.582(1) Å, β = 91.32(1)°. Rw = 0.038 for 2557 reflections up to 2Θ = 65deg;; Li 5Mn(II) 4Mn(III)(SeO 3) 8: triclinic, space group P1¯ Z = 1, a = 7.505(2) Å, b = 8.350(2) Å, c = 10.413(2) Å, α = 73.84(1)°, β = 88.24(1)°, γ = 64.24(1)°. Rw = 0.028 for 4318 reflections up to 2Θ = 70°). In KMn(II) 4Mn(III)(SeO 3) 6, the coordination octahedra of the Mn(II), Mn(III), and K atoms form pseudotrigonal layers which are connected by pyramidal SeO 3 groups. The structure of Li 5Mn(II) 4Mn(III)(SeO 3) 8 is composed of SeO 3 pyramids, Mn(II)O 6 and Mn(III)O 6 octahedra, LiO 4 tetrahedra, and a trigonal prismatic coordination polyhedron in which the central position is occupied statistically by Mn(II) and Li atoms in the proportion 1:1. In both compounds, the coordination octahedra of Mn(III) atoms exhibit pronounced Jahn-Teller distortions.

  13. Hydrothermal synthesis and crystal structure of a new lithium copper bismuth oxide, LiCuBiO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp [Center for Crystal Science and Technology, University of Yamanashi, Miyamae-cho 7-32, Kofu 400-8511 (Japan); Nakamura, Ayumi [Center for Crystal Science and Technology, University of Yamanashi, Miyamae-cho 7-32, Kofu 400-8511 (Japan); Miura, Akira [Center for Crystal Science and Technology, University of Yamanashi, Miyamae-cho 7-32, Kofu 400-8511 (Japan); Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Takei, Takahiro [Center for Crystal Science and Technology, University of Yamanashi, Miyamae-cho 7-32, Kofu 400-8511 (Japan); Azuma, Masaki; Yamamoto, Hajime [Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku Yokohama, Kanagawa 226-8503 (Japan); Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro [Department of Physical Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, Hiroshima 739-8526 (Japan)

    2017-01-15

    A new lithium copper bismuth oxide, LiCuBiO{sub 4} was prepared by hydrothermal reaction using NaBiO{sub 3}0.1*4H{sub 2}O. The crystal structural model of this compound was refined by using synchrotron X-ray powder diffraction data. This bismuthate has the LiCuSbO{sub 4} related structure with the orthorhombic cell (Space group: Pnma) of a=10.9096(9), b=5.8113(5) and c=5.0073(4) Å, and the final R-factors were R{sub wp}=4.84 and R{sub p}=3.58%. This compound is the first example of a lithium copper bismuthate containing Bi{sup 5+}. An antiferromagnetic ordering of Cu{sup 2+} moment was observed at 6 K. - Graphical abstract: In the crystal structure of LiCuBiO{sub 4} all metal atoms are coordinated octahedrally by six O atoms and LiO{sub 6} and CuO{sub 6} octahedra form the one-dimensional chains by edge-sharing along the b-axis. The LiO{sub 6} and CuO{sub 6} chains form the layer by face-sharing in the bc plane. The Bi atoms are placed in that interlayer and BiO{sub 6} octahedra are edge-sharing with LiO{sub 6} and CuO{sub 6} octahedra. - Highlights: • A new lithium copper bismuth oxide, LiCuBiO{sub 4} is prepared by hydrothermal reaction. • The crystal structure of LiCuBiO{sub 4} is closely related with that of LiCuSbO{sub 4}. • This new compound exhibits an antiferromagnetic ordering of Cu{sup 2+} moment at 6 K.

  14. Synthesis and characterization of O3-Na{sub 3}LiFeSbO{sub 6}: A new honeycomb ordered layered oxide

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Whitney; Berthelot, Romain [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Etienne, Laetitia; Wattiaux, Alain [CNRS, Université de Bordeaux, ICMCB, 87 avenue du Dr. A. Schweitzer, 33608 F-Pessac (France); Subramanian, M.A., E-mail: mas.subramanian@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)

    2014-02-01

    Highlights: • A new honeycomb ordered layered oxide Na{sub 3}LiFeSbO{sub 6} was synthesized. • This compound crystallizes in the C2/c space group. • Disorder in the honeycomb arrangement of Li and Fe is present. - Abstract: A new compound Na{sub 3}LiFeSbO{sub 6} has been synthesized by conventional solid state methods and investigated using X-ray diffraction, DC magnetic susceptibility, {sup 57}Fe Mössbauer spectroscopy and optical measurements. This compound crystallizes in a monoclinic unit cell and is related to a family of honeycomb ordered layered oxide materials where Na{sup +} fills octahedral interlayer sites between Li{sub 1/3}Fe{sub 1/3}Sb{sub 1/3}O{sub 2} slabs of edge sharing octahedra. Each SbO{sub 6} octahedron is surrounded by LiO{sub 6} and FeO{sub 6} octahedra creating a honeycomb arrangement within the slabs. Powder X-ray diffraction indicates the presence of stacking faults. This compound exhibits Curie–Weiss behavior at high temperatures and the effective magnetic moment verifies the presence of high spin Fe{sup 3+}. The {sup 57}Fe Mössbauer spectroscopy confirms Fe{sup 3+} in an octahedral position and indicates disorder in the arrangement of LiO{sub 6} and FeO{sub 6} octahedra in the Li{sub 1/3}Fe{sub 1/3}Sb{sub 1/3}O{sub 2} slabs.

  15. {110}-Layered B-cation ordering in the anion-deficient perovskite Pb2.4Ba2.6Fe2Sc2TiO13 with the crystallographic shear structure.

    Science.gov (United States)

    Tyablikov, O A; Batuk, D; Tsirlin, A A; Batuk, M; Verchenko, V Yu; Filimonov, D S; Pokholok, K V; Sheptyakov, D V; Rozova, M G; Hadermann, J; Antipov, E V; Abakumov, A M

    2015-06-21

    A novel anion-deficient perovskite-based compound, Pb(2.4)Ba(2.6)Fe(2)Sc(2)TiO(13), was synthesized via the citrate-based route. This compound is an n = 5 member of the AnBnO(3n-2) homologous series with unit-cell parameters related to the perovskite subcell a(p)≈ 4.0 Å as a(p)√2 ×a(p)× 5a(p)√2. The crystal structure of Pb(2.4)Ba(2.6)Fe(2)Sc(2)TiO(13) consists of quasi-2D perovskite blocks with a thickness of three octahedral layers separated by the 1/2[110](1[combining macron]01)(p) crystallographic shear (CS) planes, which are parallel to the {110} plane of the perovskite subcell. The CS planes transform the corner-sharing octahedra into chains of edge-sharing distorted tetragonal pyramids. Using a combination of neutron powder diffraction, (57)Fe Mössbauer spectroscopy and atomic resolution electron energy-loss spectroscopy we demonstrate that the B-cations in Pb(2.4)Ba(2.6)Fe(2)Sc(2)TiO(13) are ordered along the {110} perovskite layers with Fe(3+) in distorted tetragonal pyramids along the CS planes, Ti(4+) preferentially in the central octahedra of the perovskite blocks and Sc(3+) in the outer octahedra of the perovskite blocks. Magnetic susceptibility and Mössbauer spectroscopy indicate a broadened magnetic transition around T(N)∼ 45 K and the onset of local magnetic fields at low temperatures. The magnetic order is probably reminiscent of that in other AnBnO(3n-2) homologues, where G-type AFM order within the perovskite blocks has been observed.

  16. New clues to the local atomic structure of short-range ordered ferric arsenate from extended X-ray absorption fine structure spectroscopy.

    Science.gov (United States)

    Mikutta, Christian; Mandaliev, Petar N; Kretzschmar, Ruben

    2013-04-02

    Short-range ordered ferric arsenate (FeAsO4 · xH2O) is a secondary As precipitate frequently encountered in acid mine waste environments. Two distinct structural models have recently been proposed for this phase. The first model is based on the structure of scorodite (FeAsO4 · 2H2O) where isolated FeO6 octahedra share corners with four adjacent arsenate (AsO4) tetrahedra in a three-dimensional framework (framework model). The second model consists of single chains of corner-sharing FeO6 octahedra being bridged by AsO4 bound in a monodentate binuclear (2)C complex (chain model). In order to rigorously test the accuracy of both structural models, we synthesized ferric arsenates and analyzed their local (absorption fine structure (EXAFS) spectroscopy. We found that both As and Fe K-edge EXAFS spectra were most compatible with isolated FeO6 octahedra being bridged by AsO4 tetrahedra (RFe-As = 3.33 ± 0.01 Å). Our shell-fit results further indicated a lack of evidence for single corner-sharing FeO6 linkages in ferric arsenate. Wavelet-transform analyses of the Fe K-edge EXAFS spectra of ferric arsenates complemented by shell fitting confirmed Fe atoms at an average distance of ∼5.3 Å, consistent with crystallographic data of scorodite and in disagreement with the chain model. A scorodite-type local structure of short-range ordered ferric arsenates provides a plausible explanation for their rapid transformation into scorodite in acid mining environments.

  17. Redetermination of the crystal structure of β-zinc molybdate from single-crystal X-ray diffraction data

    Directory of Open Access Journals (Sweden)

    Olfa Mtioui-Sghaier

    2015-07-01

    Full Text Available The crystal structure of the β-polymorph of ZnMoO4 was re-determined on the basis of single-crystal X-ray diffraction data. In comparison with previous powder X-ray diffraction studies [Katikaneani & Arunachalam (2005. Eur. J. Inorg. Chem. pp. 3080–3087; Cavalcante et al. (2013. Polyhedron, 54, 13–25], all atoms were refined with anisotropic displacement parameters, leading to a higher precision with respect to bond lengths and angles. β-ZnMoO4 adopts the wolframite structure type and is composed of distorted ZnO6 and MoO6 octahedra, both with point group symmetry 2. The distortion of the octahedra is reflected by variation of bond lengths and angles from 2.002 (3–2.274 (4 Å, 80.63 (11–108.8 (2° for equatorial and 158.4 (2– 162.81 (14° for axial angles (ZnO6, and of 1.769 (3–2.171 (3 Å, 73.39 (16–104.7 (2, 150.8 (2–164.89 (15° (MoO6, respectively. In the crystal structure, the same type of MO6 octahedra share edges to built up zigzag chains extending parallel to [001]. The two types of chains are condensed by common vertices into a framework structure. The crystal structure can alternatively be described as derived from a distorted hexagonally closed packed arrangement of the O atoms, with Zn and Mo in half of the octahedral voids.

  18. The influence of cation ordering, oxygen vacancy distribution and proton siting on observed properties in ceramic electrolytes: the case of scandium substituted barium titanate.

    Science.gov (United States)

    Torino, Nico; Henry, Paul F; Knee, Christopher S; Bjørheim, Tor Svendsen; Rahman, Seikh M H; Suard, Emma; Giacobbe, Carlotta; Eriksson, Sten G

    2017-07-04

    The origin of the 2-order of magnitude difference in the proton conductivity of the hydrated forms of hexagonal and cubic oxygen deficient BaScxTi1-xO3-δ (x = 0.2 and x = 0.7) was probed using a combination of neutron diffraction and density functional theory techniques to support published X-ray diffraction, conductivity, thermogravimetric and differential scanning calorimetry studies. Cation ordering is found in the 6H structure type (space group P63/mmc) adopted by BaSc0.2Ti0.8O3-δ with scandium preferentially substituting in the vertex sharing octahedra (2a crystallographic site) and avoiding the face-sharing octahedra (4f site). This is coupled with oxygen vacancy ordering in the central plane of the face-sharing octahedra (O1 site). In BaSc0.7Ti0.3O3-δ a simple cubic perovskite (space group Pm3[combining macron]m) best represents the average structure from Rietveld analysis with no evidence of either cation ordering or oxygen vacancy ordering. Significant diffuse scattering is observed, indicative of local order. Hydration in both cases leads to complete filling of the available oxygen vacancies and permits definition of the proton sites. We suggest that the more localised nature of the proton sites in the 6H structure is responsible for the significantly lower proton conduction observed in the literature. Within the 6H structure type final model, proton diffusion requires a 3-step process via higher energy proton sites that are unoccupied at room temperature and is also likely to be anisotropic whereas the highly disordered cubic perovskite proton position allows 3-dimensional diffusion by well-described modes. Finally, we propose how this knowledge can be used to further materials design for ceramic electrolytes for proton conducting fuel cells.

  19. Spectroscopy of Bioactive Manganese(II) and Copper(II) Complexes with Mannich Bases

    Science.gov (United States)

    Harbatsevich, H. I.; Loginova, N. V.; Koval‧chuk, T. V.; Osipovich, N. P.; Gres, A. T.; Azarko, I. I.; Polozov, G. I.

    2015-11-01

    The compositions and geometries of coordination polyhedra in Cu(II) and Mn(II) complexes with Mannich bases were determined using IR, EPR, and electron spectroscopy. It was shown that bidentate ligands were coordinated to the metal ions in these complexes. The coordination polyhedra of mononuclear Cu(II) and Mn(II) complexes consisted of two mono-anionic ligands. Polyhedra of the Mn(II) complexes also contained two water molecules. The Cu(II) complexes had characteristic square-planar [CuN2O2] coordination polyhedra; Mn(II) complexes, [MnN2O4] octahedra.

  20. Octadecabromidobis(dicarbidodecadysprosium, [Dy10Br18(C22

    Directory of Open Access Journals (Sweden)

    Kathrin Daub

    2008-01-01

    Full Text Available Single crystals of [Dy10Br18(C22] were obtained during the reaction of DyBr3 with dysprosium metal and graphite in a sealed tantalum container. In the crystal structure, the Dy atoms form dimers of edge-sharing octahedra, each encapsulating a C2 unit. The metal atoms are surrounded by Br atoms above the cluster edges and vertices, respectively. The dimers are connected to each other by Br atoms, leading to a three-dimensional network. [Dy10Br18(C22] is isotypic with its iodido analogue [Dy10I18(C22].

  1. Holmium dodecaiodidoiron-octahedro-hexaholmium, {FeHo6}I12Ho

    Directory of Open Access Journals (Sweden)

    Gerd Meyer

    2009-02-01

    Full Text Available Single crystals of {FeHo6}I12Ho were obtained during the reaction of HoI3 with metallic holmium and iron in a sealed tantalum container. The crystal structure consists of isolated holmium clusters encapsulating a single Fe atom, {FeHo6} (overline{3} symmetry. The rare earth metal atoms are surrounded by 12 edge-capping and six terminal iodide ligands that either connect the clusters to each other directly or via HoI6 octahedra (overline{3} symmetry.

  2. The synthesis and characterisation of LaCa{sub 2}Fe{sub 2}GaO{sub 8}

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Kun [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, Oxfordshire, OX1 3QR (United Kingdom); Hayward, Michael A., E-mail: michael.hayward@chem.ox.ac.uk [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, Oxfordshire, OX1 3QR (United Kingdom)

    2013-02-15

    The synthesis and characterisation of LaCa{sub 2}Fe{sub 2}GaO{sub 8} is described. Neutron powder diffraction data reveal LaCa{sub 2}Fe{sub 2}GaO{sub 8} adopts an anion-vacancy ordered, 'triple layer' structure consisting of an OOT{sub L}OOT{sub R} stacking sequence of layers of (Fe/Ga)O{sub 6} octahedra (O) and (Fe/Ga)O{sub 4} tetrahedra (T), related to that of the 4-layer brownmillerite structures (a=5.4784(1) A, b=22.6780(4) A, c=5.6007(1) A, space group Pbma). The apex-linked chains of tetrahedra within structure of LaCa{sub 2}Fe{sub 2}GaO{sub 8} exhibit a cooperative twisting distortion which alternates in direction between adjacent layers of tetrahedra, the first time such an arrangement has been seen in a triple-layer phase. Magnetisation and neutron diffraction data reveal that LaCa{sub 2}Fe{sub 2}GaO{sub 8} exhibits two magnetic ordering transitions. On cooling below 550 K the phase adopts a state with short range antiferromagnetic coupling within each double layer of (Fe/Ga)O{sub 6} octahedra, but only weak coupling between layers. On cooling below 470 K full three-dimensional, G-type antiferromagnetic order is observed. - Graphical abstract: LaCa{sub 2}Fe{sub 2}GaO{sub 8} adopts an anion-vacancy ordered, 'triple layer' structure consisting of an OOT{sub L}OOT{sub R} stacking sequence of layers of FeO{sub 6} octahedra (O) and GaO{sub 4} tetrahedra (T), in which the chains of apex-linked tetrahedra exhibit a cooperative twisting distortion which alternates in direction between adjacent layers of tetrahedra. On cooling below 550 K, LaCa{sub 2}Fe{sub 2}GaO{sub 8} adopts a state with strong two-dimensional antiferromagnetic order within each double layer of FeO{sub 6} octahedra, but only weak coupling between layers. On cooling below 470 K full three-dimensional antiferromagnetic order is observed. Highlights: Black-Right-Pointing-Pointer LaCa{sub 2}Fe{sub 2}GaO{sub 8} exhibits a novel anion-vacancy ordered triple-layer structure type

  3. Nickel hexayttrium decaiodide, [NiY6]I10

    Directory of Open Access Journals (Sweden)

    Simon Steinberg

    2014-06-01

    Full Text Available Comproportionation reactions of yttrium triiodide, yttrium and nickel led to the formation of the compound [NiY6]I10, which is isostructural with the prototypical [RuY6]I10. In particular, [NiY6]I10 is composed of isolated nickel centered yttrium octahedra (site symmetry -1 that are further surrounded by iodide ligands to construct a three-dimensional cluster complex framework. Although this compound has been previously detected by powder X-ray diffraction techniques [Payne & Corbett (1990. Inorg. Chem. 29, 2246–2251], details of the crystal structure for triclinic [NiY6]I10 were not provided.

  4. Diethylenetriaminium hexafluoridotitanate(IV fluoride

    Directory of Open Access Journals (Sweden)

    J. Lhoste

    2008-11-01

    Full Text Available The title compound, (C6H21N4[TiF6]F, was synthesized by the reaction of TiO2, tris(2-aminoethylamine, HF and ethanol at 463 K in a microwave oven. The crystal structure consists of two crystallographically independent [TiF6]2− anions, two fluoride anions and two triply-protonated tris(2-aminoethylamine cations. The Ti atoms are coordinated by six F atoms within slightly distorted octahedra. The anions and cations are connected by intermolecular N—H...F hydrogen bonds.

  5. Structures and phases transition in hexylenediammonium pentachlorobismuthate (III) [NH{sub 3}(CH{sub 2}){sub 6}NH{sub 3}]BiCl{sub 5} crystal

    Energy Technology Data Exchange (ETDEWEB)

    Ouasri, A., E-mail: aouasri@yahoo.fr [Equipe de Physico-Chimie des Matériaux Inorganiques, Université Ibn Tofail, Faculté des Sciences, B. P. 133, Kenitra 14000 (Morocco); Département de Physique-Chimie, Centre Régional des Métiers de l' Education, et de la Formation, Souissi Rabat (Morocco); Jeghnou, H.; Rhandour, A. [Equipe de Physico-Chimie des Matériaux Inorganiques, Université Ibn Tofail, Faculté des Sciences, B. P. 133, Kenitra 14000 (Morocco); Roussel, P. [Unité de Catalyse et de Chimie du Solide, CNRS UMR 8181 (Equipe de Chimie du Solide), ENSCL, USTL, VILLENEUVE D' ASCQ Cedex 59655 (France)

    2013-04-15

    The crystal structure of [NH{sub 3}(CH{sub 2}){sub 6}NH{sub 3}]BiCl{sub 5} was determined at: 223 K [P2{sub 1}2{sub 1}2{sub 1} (Z=4), a=7.788(1), b=13.886(2), c=13.972(2) Å], 308 K [P2{sub 1}/n (Z=8), a=19.972(3), b=7.772(2), c=20.166(3) Å, β=92.32(1)°] and 378 K [Pnma (Z=4), a=13911(2), b=7.834(7), c=14.457(2) Å]. It was consisted of isolated (BiCl{sub 5}{sup 2−}){sub n} anionic chains composed by distorted octahedra BiCl{sub 6}{sup 3−} sharing two corners and {sup +}NH{sub 3}(CH{sub 2}){sub 6}NH{sub 3}{sup +} cations placed in the free cavities between anionic chains. In the β phase, there are two crystallographically inequivalent cations and two one-dimensional anionic chains (BiCl{sub 5}{sup 2−}){sub n} in which BiCl{sub 6}{sup 3−} octahedra was doubly tilted and simply tilted. Two structural phase transitions at low and high temperatures α (P2{sub 1}2{sub 1}2{sub 1}, 223 K)↔β (P2{sub 1}/n, 308 K)↔γ (Pnma, 373 K) are observed and discussed. It was crystallographically showed that both anionic and cationic entities contribute to phase transitions mechanisms. The BiCl{sub 6}{sup 3−} octahedra were found to posses significant distortions on decreasing temperature and became more distorted in α (223 K) phase. It is argued that these deformations are caused by weak to moderate N--H···Cl hydrogen bonding. - Graphical abstract: Projection of the crystal structure of [NH{sub 3}(CH{sub 2}){sub 6}NH{sub 3}]BiCl{sub 5} down the a axis at 208 K. Highlights: ► The crystal shows two phase transitions: α(223 K)↔β(308 K)↔γ(373 K). ► A discontinuous transition may be occurred between α and β phases. ► The α↔β and β↔γ phase transitions are of first order. ► Both anionic and cationic motions contribute to phase transition mechanisms. ► The BiCl{sub 6}{sup 3−} octahedra showed significant distortions on decreasing temperature.

  6. Crystal structure of Na2HfSi2O7 by Rietveld refinement

    Directory of Open Access Journals (Sweden)

    Nicolas Massoni

    2016-10-01

    Full Text Available The structure of triclinic disodium hafnium disilicate, Na2HfSi2O7, has been determined by laboratory powder X-ray diffraction and refined by the Rietveld refinement. The structure is a framework made of alternate layers of HfO6 octahedra and SiO4 tetrahedra linked by common O atoms. Sodium atoms are located in the voids of the framework, aligned into tunnels along the [010] direction. Na2HfSi2O7 is isostructural with the parakeldyshite Na2ZrSi2O7 phase.

  7. Atomic-scale structure of biogenic materials by total X-ray diffraction: a study of bacterial and fungal MnOx.

    Science.gov (United States)

    Petkov, V; Ren, Y; Saratovsky, I; Pastén, P; Gurr, S J; Hayward, M A; Poeppelmeier, K R; Gaillard, J-F

    2009-02-24

    Biogenic materials are produced by microorganisms and are typically found in a nanophase state. As such, they are difficult to characterize structurally. In this report, we demonstrate how high-energy X-ray diffraction and atomic pair distribution function analysis can be used to determine the atomic-scale structures of MnO(x) produced by bacteria and fungi. These structures are well-defined, periodic, and species-specific, built of Mn-O(6) octahedra forming birnessite-type layers and todorokite-type tunnels, respectively. The inherent structural diversity of biogenic material may offer opportunities for practical applications.

  8. Homopiperazine-1,4-diium bis[hexaaquacobalt(II] trisulfate

    Directory of Open Access Journals (Sweden)

    Thameur Sahbani

    2011-08-01

    Full Text Available In the title compound, (C5H14N2[Co(H2O6]2(SO43, the cationic framework is built up of mixed organic–inorganic fragments, namely [Co(H2O6]2+ and [C5H14N2]2+. The [Co(H2O6]2+ cations form unconnected octahedra. Sulfate anions intercalated between cationic species connect them via N—H...O and O—H...O hydrogen bonds and electrostatic interactions.

  9. Nearly Monodisperse Insulator Cs 4 PbX 6 (X = Cl, Br, I) Nanocrystals, Their Mixed Halide Compositions, and Their Transformation into CsPbX 3 Nanocrystals

    OpenAIRE

    Akkerman, Quinten A.; Park, Sungwook; Radicchi, Eros; Nunzi, Francesca; Mosconi, Edoardo; De Angelis, Filippo; Brescia, Rosaria; Rastogi, Prachi; Prato, Mirko; Manna, Liberato

    2017-01-01

    We have developed a colloidal synthesis of nearly monodisperse nanocrystals of pure Cs4PbX6 (X = Cl, Br, I) and their mixed halide compositions with sizes ranging from 9 to 37 nm. The optical absorption spectra of these nanocrystals display a sharp, high energy peak due to transitions between states localized in individual PbX6 4? octahedra. These spectral features are insensitive to the size of the particles and in agreement with the features of the corresponding bulk materials. Samples with...

  10. Postsynthesis Transformation of Insulating Cs4PbBr6 Nanocrystals into Bright Perovskite CsPbBr3 through Physical and Chemical Extraction of CsBr

    OpenAIRE

    Palazon, Francisco; Urso, Carmine; De Trizio, Luca; Akkerman, Quinten; Marras, Sergio; Locardi, Federico; Nelli, Ilaria; Ferretti, Maurizio; Prato, Mirko; Manna, Liberato

    2017-01-01

    Perovskite-related Cs4PbBr6 nanocrystals present a “zero-dimensional” crystalline structure where adjacent [PbBr6]4– octahedra do not share any corners. We show in this work that these nanocrystals can be converted into “three-dimensional” CsPbBr3 perovskites by extraction of CsBr. This conversion drastically changes the optoelectronic properties of the nanocrystals that become highly photoluminescent. The extraction of CsBr can be achieved either by thermal annealing (physical approach) or b...

  11. Mo{sub 6}S{sub 4.5}I{sub 4.5} Nanowires: Structure Studies by HRTEM and Aberration Corrected STEM

    Energy Technology Data Exchange (ETDEWEB)

    Nicolosi, Valeria [University of Dublin - Trinity College, Department of Physics, Dublin 2 (Ireland); Nellist, Peter [University of Dublin - Trinity College, Department of Physics, Dublin 2 (Ireland); Sloan, Jeremy [Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR (United Kingdom); Mihailovic, Dragan [Jozef Stefan Institute, Jamova 39, 1000 Ljubljana (Slovenia); Mo6, Teslova 30, 1000 Ljubljana (Slovenia); Green, Malcom [Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR (United Kingdom); Blau, Werner J [University of Dublin - Trinity College, Department of Physics, Dublin 2 (Ireland); Coleman, Jonathan N [University of Dublin - Trinity College, Department of Physics, Dublin 2 (Ireland)

    2006-02-22

    The atomic structure of subnanometer diameter Mo{sub 6}S{sub 4.5}I{sub 4.5} nanowires and their superlattice packing in bundles have been studied by High Resolution Transmission Electron Microscopy (HRTEM) and Aberration Corrected Scanning Transmission Electron Microscopy (STEM). The individual nanowires are best described as one-dimensional Mo-chalcogenidehalide cluster polymers, composed of Mo octahedra, surrounded by iodine atoms and connected by bridging planes of 3 sulfur atoms. The nanowires are weakly bounded together into bundles by Van der Waals forces in a trigonal packing arrangement, with a nanowire to nanowire distance of 0.96 nm.

  12. Electronic and magnetic properties of epitaxial SrRhO3 films

    Energy Technology Data Exchange (ETDEWEB)

    Nichols, John; Yuk, Simuck F.; Sohn, Changhee; Jeen, Hyoungjeen; Freeland, John W.; Cooper, Valentino R.; Lee, Ho Nyung

    2017-06-01

    The strong interplay of fundamental order parameters in complex oxides is known to give rise to exotic physical phenomena. The 4d transition-metal oxide SrRhO3 has generated much interest, but advances have been hindered by difficulties in preparing single-crystalline phases. Here we epitaxially stabilize high-quality single-crystalline SrRhO3 films and investigate their structural, electronic, and magnetic properties. We determine that their properties significantly differ from the paramagnetic metallic ground state that governs bulk samples and are strongly related to rotations of RhO6 octahedra.

  13. Frustrated Soft Modes and Negative Thermal Expansion in ZrW2O8

    Science.gov (United States)

    Cao, D.; Bridges, F.; Kowach, G. R.; Ramirez, A. P.

    2002-11-01

    Negative thermal expansion (NTE) in cubic ZrW2O8 has generated much interest due to its large, isotropic, and temperature independent behavior. Here, x-ray absorption fine structure data are presented for various atom pairs, providing evidence that the low-energy modes causing NTE correspond to the correlated vibrations of a WO4 tetrahedron and its three nearest ZrO6 octahedra. This involves translations of the WO4 as a rigid unit along each of the four axes. The interconnectivity of these modes prevents an anisotropic soft mode from developing, a new geometrical phenomenon that we call the ``frustrated soft mode.''

  14. Synthesis of nanometre-thick MoO3 sheets

    Science.gov (United States)

    Kalantar-Zadeh, Kourosh; Tang, Jianshi; Wang, Minsheng; Wang, Kang L.; Shailos, Alexandros; Galatsis, Kosmas; Kojima, Robert; Strong, Veronica; Lech, Andrew; Wlodarski, Wojtek; Kaner, Richard B.

    2010-03-01

    The formation of MoO3 sheets of nanoscale thickness is described. They are made from several fundamental sheets of orthorhombic α-MoO3, which can be processed in large quantities via a low cost synthesis route that combines thermal evaporation and mechanical exfoliation. These fundamental sheets consist of double-layers of linked distorted MoO6 octahedra. Atomic force microscopy (AFM) measurements show that the minimum resolvable thickness of these sheets is 1.4 nm which is equivalent to the thickness of two double-layers within one unit cell of the α-MoO3 crystal.

  15. The one-dimensional organic–inorganic hybrid: catena-poly[bis[1-(3-ammoniopropyl-1H-imidazolium] [[iodidoplumbate(II]-tri-μ-iodido-plumbate(II-tri-μ-iodido-[iodidoplumbate(II]-di-μ-iodido

    Directory of Open Access Journals (Sweden)

    A. Trigui

    2011-04-01

    Full Text Available The organic–inorganic hybrid, {(C6H13N32[Pb3I10]}n, was obtained by the reaction of 1-(3-ammoniopropylimidazolium triiodide and PbI2 at room temperature. The structure contains one-dimensional {[Pb3I10]4−}n polymeric anions spreading parallel to [001], resulting from face–face–edge association of PbI6 distorted octahedra. One of the PbII cations is imposed at an inversion centre, whereas the second occupies a general position. N—H...I hydrogen bonds connect the organic cations and inorganic anions.

  16. Crystal structure of dichloridobis(methyl isonicotinate-κNcopper(II

    Directory of Open Access Journals (Sweden)

    Elaheh Ahadi

    2015-05-01

    Full Text Available In the title compound, [CuCl2(C7H7NO22], the square-planar-coordinated CuII ion lies on a centre of symmetry and is bonded to two monodentate methylisonicotinate ligands through their N atoms and by two chloride ligands. The molecules pack in a herringbone pattern. Perpendicular to [100] there are weak intermolecular C—H...Cl and C—H...O contacts. Along [100] there are infinite chains of edge-sharing octahedra linked through the chlorido ligands

  17. Anharmonicity and phase stability of antiperovskite Li3OCl

    Science.gov (United States)

    Chen, Min-Hua; Emly, Alexandra; Van der Ven, Anton

    2015-06-01

    A lattice-dynamics study of the cubic Li3OCl antiperovskite, a candidate solid electrolyte in lithium-ion batteries, reveals the presence of dynamical instabilities with respect to rotations of the Li6O octahedra. Calculated energy landscapes in the subspace of unstable octahedral rotational modes are very shallow with at most a 1 meV per formula unit reduction in energy upon breaking the cubic symmetry. While Li3OCl is not stable relative to decomposition into Li2O and LiCl at 0 K, estimates of the vibrational free energy suggest that Li3OCl antiperovskite should become entropically stabilized above approximately 480 K.

  18. Orthorhombic polar Nd-doped BiFeO{sub 3} thin film on MgO substrate

    Energy Technology Data Exchange (ETDEWEB)

    Leontyev, I N; Janolin, P-E; Dkhil, B [Laboratoire Structures, Proprietes et Modelisation des Solides, UMR CNRS-Ecole Centrale Paris, 92295 Chatenay-Malabry Cedex (France); Yuzyuk, Yu I [Faculty of Physics, Southern Federal University, Zorge 5, Rostov-on-Don 344090 (Russian Federation); El-Marssi, M [Laboratoire de Physique de la Matiere Condensee, Universite de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens (France); Chernyshov, D; Dmitriev, V [Swiss-Norwegian Beam Lines at ESRF, Boite Postale 220, F-38043 Grenoble (France); Golovko, Yu I; Mukhortov, V M, E-mail: i.leontiev@rambler.ru [Southern Scientific Center RAS, Rostov-on-Don, 344006 (Russian Federation)

    2011-08-24

    A Nd-doped BiFeO{sub 3} thin film deposited on MgO substrate was studied by synchrotron diffraction. The ferroelectric nature of the film is proven by in-plane remanent polarization measurement. The highest possible symmetry of the film is determined to be orthorhombic, within the Fm2m space group. Such a structure is rotated by 45{sup 0} with respect to the substrate and is consistent with tilts of oxygen octahedra doubling the unit cell. This polar structure presents a rather unusual strain-accommodation mechanism. (fast track communication)

  19. Poly[1,4-bis(ammoniomethylcyclohexane [di-μ-iodido-diiodidoplumbate(II

    Directory of Open Access Journals (Sweden)

    Matthew Kyle Rayner

    2010-06-01

    Full Text Available The title compound, {(C8H20N2[PbI4]}n, is an inorganic–organic hybrid. The structure is composed of alternate layers of two-dimensional corner-sharing PbI6 octahedra (overline{1} symmetry and 1,4-bis(ammoniomethylcyclohexane cations (overline{1} symmetry extending parallel to the bc plane. The cations interact with the inorganic layer via N—H...I hydrogen bonding in the right-angled halogen sub-type of the terminal halide hydrogen-bonding motif.

  20. Microwave-assisted reactive sintering and lithium ion conductivity of Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 solid electrolyte

    OpenAIRE

    Hallopeau, Leopold; Bregiroux, Damien; Rousse, Gwenaëlle; Portehault, David; Stevens, Philippe; Toussaint, Gwenaëlle; Laberty-Robert, Christel

    2018-01-01

    International audience; Li1.3Al0.3Ti1.7(PO4)3 (LATP) materials are made of a three−dimensional framework of TiO6 octahedra and PO4 tetrahedra, which provides several positions for Li+ ions. The resulting high ionic conductivity is promising to yield electrolytes for all-solid-state Li-ion batteries. In order to elaborate dense ceramics, conventional sintering methods often use high temperature (≥1000 °C) with long dwelling times (several hours) to achieve high relative density (∼90%). In this...

  1. Evidence for nano-scale inhomogeneities in bilayer manganites in the Mn\\sp{4+} rich region: $\\bm{0.54 \\leq x \\leq 0.80}$

    OpenAIRE

    Qiu, Xiangyun; Billinge, Simon J. L.; Kmety, Carmen R.; Mitchell, John F.

    2003-01-01

    The atomic pair distribution function (PDF) technique is employed to probe the atomic local structural responses in naturally double layered manganites \\lsmo in the doping range $0.54 \\leq x \\leq 0.80$. Our low temperature neutron powder diffraction measurements suggest the coexistence of two different Jahn-Teller (JT) distorted MnO$_6$ octahedra when its ordered magnetic structure crosses over from type A ($0.54 \\leq x \\leq 0.66$) to type C/C$^*$ ($0.74 \\leq x \\leq 0.90$) ordering. At all do...

  2. Crystal structure of Na2HfSi2O7 by Rietveld refinement.

    Science.gov (United States)

    Massoni, Nicolas; Chevreux, Pierrick

    2016-10-01

    The structure of triclinic disodium hafnium disilicate, Na2HfSi2O7, has been determined by laboratory powder X-ray diffraction and refined by the Rietveld refinement. The structure is a framework made of alternate layers of HfO6 octa-hedra and SiO4 tetra-hedra linked by common O atoms. Sodium atoms are located in the voids of the framework, aligned into tunnels along the [010] direction. Na2HfSi2O7 is isostructural with the parakeldyshite Na2ZrSi2O7 phase.

  3. Half-metallicity in a BiFeO3/La2/3Sr1/3MnO3 superlattice: A first-principles study

    KAUST Repository

    Jiwuer, Jilili

    2013-06-01

    We present first-principles results for the electronic, magnetic, and optical properties of the heterostructure as obtained by spin-polarized calculations using density functional theory. The electronic states of the heterostructure are compared to those of the bulk compounds. Structural relaxation turns out to have only a minor impact on the chemical bonding, even though the oxygen octahedra in develop some distortions due to the interface strain. While a small charge transfer affects the heterointerfaces, our results demonstrate that the half-metallic character of is fully maintained. © EPLA, 2013.

  4. Crystal structures of MBi{sub 2}Br{sub 7} (M = Rb, Cs) - filled variants of AX{sub 7} sphere packing

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Jen-Hui; Wolff, Alexander [Fachrichtung Chemie und Lebensmittelchemie, Technische Universitaet Dresden, 01062 Dresden (Germany); Ruck, Michael [Fachrichtung Chemie und Lebensmittelchemie, Technische Universitaet Dresden, 01062 Dresden (Germany); Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Str. 40, 01187 Dresden (Germany)

    2016-03-15

    The reinvestigation of the pseudo-binary systems MBr-BiBr{sub 3} (M = Rb, Cs) revealed two new phases with composition MBi{sub 2}Br{sub 7}. Both compounds are hygroscopic and show brilliant yellow color. The crystal structures were solved from X-ray single crystal diffraction data. The isostructural compounds adopt a new structure type in the triclinic space group P anti 1. The lattice parameters are a = 755.68(3) pm, b = 952.56(3) pm, c = 1044.00(4) pm, α = 76.400(2) , β = 84.590(2) , γ = 76.652(2) for RbBi{sub 2}Br{sub 7} and a = 758.71(5) pm, b = 958.23(7) pm, c = 1060.24(7) pm, α = 76.194(3) , β = 83.844(4) , γ = 76.338(3) for CsBi{sub 2}Br{sub 7}. The crystal structures consist of M{sup +} cations in anticuboctahedral coordination by bromide ions and bromidobismuthate(III) layers {sup 2}{sub ∞}[Bi{sub 2}Br{sub 7}]{sup -}. The 2D layers comprise pairs of BiBr{sub 6} octahedra sharing a common edge. The Bi{sub 2}Br{sub 10} double octahedra are further connected by common vertices. The bismuth(III) atoms increase their mutual distance in the double octahedra by off-centering so that the BiBr{sub 6} octahedra are distorted. The CsBi{sub 2}Br{sub 7} type can be interpreted as a common hexagonal close sphere packing of M and Br atoms, in which 1/4 of the octahedral voids are filled by Bi atoms. The structure type was systematically analyzed and compared with alternative types of common packings. The existence of a compound with the suggested composition CsBiBr{sub 4} could not be verified experimentally. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Crystal structure of ammonium divanadium(IV,V tellurium(IV heptaoxide

    Directory of Open Access Journals (Sweden)

    William T. A. Harrison

    2014-07-01

    Full Text Available The polyhedral building blocks of the layered inorganic network in the mixed-valence title compound, (NH4(VIVO2(VVO2(TeO3, are vertex-sharing VVO4 tetrahedra, distorted VIVO6 octahedra and TeO3 pyramids, which are linked by V—O—V and V—O—Te bonds, forming double layers lying parallel to (100. The presumed TeIV lone-pairs of electrons appear to be directed inwards into cavities in the double layers. The charge-balancing ammonium cations lie between the layers and probably interact with them via N—H...O hydrogen bonds.

  6. Informatics-aided computational design of functional layered oxides

    Science.gov (United States)

    Balachandran, Prasanna V.; Young, Joshua; Lookman, Turab; Rondinelli, James

    We discuss a data-driven ab initio protocol with predictive capability to design and accelerate the discovery of noncentrosymmetric (NCS) inorganic oxides. Our approach synergistically integrates applied group theory, materials informatics and density functional theory (DFT) to uncover geometry-chemistry-symmetry guidelines for computational design of new NCS materials, specifically oxygen octahedra containing basic building units. Using this approach, we identify new and previously unknown compositions with potential for realizing NCS structures in the bulk n=1 Ruddlesden-Popper (RP) oxides. We then validate our predictions using DFT calculations. Our approach enables rational design and engineering of both crystal structures and functionalities.

  7. Surface Reconstructions of TiO2(110) Driven by Suboxides

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ken T. [University of Tennessee, Knoxville (UTK) & Baylor University, Waco; Pan, Minghu [ORNL; Meunier, Vincent [ORNL; Plummer, E Ward [ORNL

    2006-01-01

    Scanning tunneling microscopy and density functional theory are used to develop a new structural model for surface reconstructions driven by Ti interstitials on TiO{sub 2}(110). Ti interstitials form the edge- or face-sharing octahedra that serve as building blocks for (1 x 1) reconstruction. Thus, contrary to conventional wisdom, the 1 x 1 periodicity is insufficient to establish the correct surface stoichiometry. Furthermore, in our structural and compositional model the reversible oxidation or reduction between (1 x 1) and (1 x 2) is entirely achieved by transfer of the added rows.

  8. Electronic doping of transition metal oxide perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Cammarata, Antonio, E-mail: cammaant@fel.cvut.cz [Department of Control Engineering, Czech Technical University in Prague, Technicka 2, 16627 Prague 6 (Czech Republic); Rondinelli, James M. [Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208 (United States)

    2016-05-23

    CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

  9. Electronic doping of transition metal oxide perovskites

    Science.gov (United States)

    Cammarata, Antonio; Rondinelli, James M.

    2016-05-01

    CaFeO3 is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO3. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

  10. Spectroscopy features of Pr{sup 3+} and Er{sup 3+} ions in Li{sub 2}O-ZrO{sub 2}-SiO{sub 2} glass matrices mixed with some sesquioxides

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasa Rao, Ch. [Department of Physics, Acharya Nagarjuna University - Nuzvid Campus, Nuzvid-521201, A.P. (India); Kityk, I.V., E-mail: iwank74@gmail.com [Electrical Engineering Department, Technical University of Czestochowa, Aleja Armii, Krajowej 17/19, PL-42-201 Czestochowa (Poland); Srikumar, T.; Naga Raju, G.; Ravi Kumar, V.; Gandhi, Y.; Veeraiah, N. [Department of Physics, Acharya Nagarjuna University - Nuzvid Campus, Nuzvid-521201, A.P. (India)

    2011-09-15

    Highlights: > Optical spectra of Pr{sup 3+} and Er{sup 3+} ions in Li{sub 2}O-ZrO{sub 2}-SiO{sub 2}: Pr{sub 2}O{sub 3}/Er{sub 2}O{sub 3} with sesquioxides (viz., Al{sub 2}O{sub 3}, Sc{sub 2}O{sub 3}, Y{sub 2}O{sub 3}) studied. > The highest branching ratios {beta}{sub r} and quantum efficiencies of {sup 3}P{sub 0} {yields} {sup 3}H{sub 4} (Pr{sup 3+}) and {sup 4}S{sub 3/2} {yields} {sup 4}I{sub 15/2} (Er{sup 3+}) emissions have shown principal role of Y{sub 2}O{sub 3}. > Principal role of disorder around rare earth is established. - Abstract: The glasses of the composition Li{sub 2}O-ZrO{sub 2}-SiO{sub 2}: Pr{sub 2}O{sub 3}/Er{sub 2}O{sub 3} mixed with three interesting sesquioxides (viz., Al{sub 2}O{sub 3}, Sc{sub 2}O{sub 3}, Y{sub 2}O{sub 3}) were synthesized. Optical absorption and fluorescence spectra (in the spectral range 350-2100 nm were studied at ambient temperature. The Judd-Ofelt theory was applied to characterize the absorption and luminescence spectra of Pr{sup 3+} and Er{sup 3+} ions in these glasses. Following the luminescence spectra, various radiative properties like transition probability A, branching ratio {beta} and the radiative life time {tau} for different emission levels of two rare earth ions have been evaluated. The radiative life times for the upper levels {sup 3}P{sub 0} (Pr{sup 3+}) and {sup 4}S{sub 3/2} (Er{sup 3+}) have also been measured and quantum efficiencies were estimated. The variations observed in these parameters were discussed in the light of changing environment of rare earth ions due to mixing of different sesquioxides in the glass network.

  11. Structural, magnetic, and crystalline electric-field effects in single crystals of Y{sub 1{minus}{ital x}}Pr{sub {ital x}}Ba{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}

    Energy Technology Data Exchange (ETDEWEB)

    Uma, S.; Sarkar, T.; Sethupathi, K.; Seshasayee, M.; Rangarajan, G. [Department of Physics, Indian Institute of Technology, Madras 600036 (India); Changkang, C.; Yongle, H.; Wanklyn, B.M.; Hodby, J.W. [Department of Physics, University of Oxford, Clarendon Laboratory, Oxford, 0X13PU (England)

    1996-03-01

    We report here structural and directional magnetic susceptibility measurements on single crystals of Y{sub 1{minus}{ital x}}Pr{sub {ital x}}Ba{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} ({ital x}=1.0, {delta}=1, 0.11; {ital x}=0.7, {delta}=0; and {ital x}=0.42, {delta}=0.22). The space group of PrBa{sub 2}Cu{sub 3}O{sub 6} (Pr-O6) and Y{sub 0.58}Pr{sub 0.42}Ba{sub 2}Cu{sub 3}O{sub 6.78} (Pr 0.42-O7) were found to be {ital P}4/{ital mmm} and that of PrBa{sub 2}Cu{sub 3}O{sub 6.89} (Pr-O7) was found to be {ital Pmmm}. Also, Pr-O7 was found to be weakly orthorhombic. Directional, magnetic susceptibility measurements in the temperature range 2{endash}300 K revealed a clear peaking in the paramagnetic anisotropy of Pr-O7 around 17 K, and {chi}{sub {ital c}}{approx_gt}{chi}{sub {ital a},{ital b}} at all temperatures. However for Y{sub 0.3}Pr{sub 0.7}Ba{sub 2}Cu{sub 3}O{sub 7} (Pr0.7-O7) and Pr0.42-O7, {chi}{sub {ital c}}{approx_gt}{chi}{sub {ital a},{ital b}} at room temperature and {chi}{sub {ital c}}{lt}{chi}{sub {ital a},{ital b}} for temperatures below 110 and 60 K, respectively. The magnetic susceptibilities have been analyzed in the light of crystalline electric-field effects considering {ital J} mixing of all the thirteen multiplets. Intermediate coupled wave functions have also been used in the calculations. Crystal-field interaction is found to be stronger in the case of Pr-O7 compared to Pr-O6 which is also evident from a shorter Pr-O bond length in the case of Pr-O7 than in Pr-O6. A best set of eigenvalues and eigenfunctions has been determined and these are discussed and compared with inelastic neutron scattering data. {copyright} {ital 1996 The American Physical Society.}

  12. Effects of surfactant addition and high-speed ball milling on magnetic powders based on Pr-Fe-B obtained by HDDR; Efeitos da adicao de surfactante e moagem de alta velocidade em pos magneticos a base de Pr-Fe-B obtidos via HDDR

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Patricia Brissi

    2011-07-01

    This work verified the effect caused by adding the surfactant in the high speed/energy milling in order to obtain Pr{sub 12}Fe{sub 65.9}Co{sub 16}B{sub 6}Nb{sub 0.1} magnetic nano powders. The first part of this work involved the magnetic powder obtainment through the process of hydrogenation, disproportionation, desorption and recombination (HDDR). The pressure of H2 during the hydrogenation and disproportion steps was 930 mbar and the temperature of desorption and recombination was 840 deg C. Initially, the HDDR powders were subjected a high speed milling process at 900 rpm, with quantity variations of the milling medium (cyclohexane) and without the addition of oleic acid. Then, the HDDR powders were subjected to the milling process with the addition of oleic acid and with milling time variations. After the milling process, heat treatments of the powder were carried out at 700 deg C or 800 deg C for 30 minutes in order to obtain the crystallization of the powder. By performing the procedures, it was verified that the milling efficiency improved with the addition of 6.6 ml of cyclohexane as the milling medium and with the addition of oleic acid. It was determined that for the surfactant additions of 0.02 ml to 0.05 ml, with a milling time of up to 360 minutes, powder agglomeration does not occur in the milling pot and the milling efficiency is higher than 90%. The second stage of this work involved the magnetic powder's characterization obtained by using vibrating sample magnetometer, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. Through the characterizations it was found that the powder's magnetic properties improved when the addition of oleic acid in a high-speed /energy milling occurred. It was also verified that the {alpha}-Fe phase, present in the powder, shows a crystallite size decrease (from 35 nm to {approx} 10 nm) when the time milling variation occurred; meanwhile, the crystallinity degree was lower in

  13. 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.

  14. Crystal structure of bis(propane-1,3-diammonium hexafluoridoaluminate fluoride trihydrate

    Directory of Open Access Journals (Sweden)

    I. Abdi

    2014-09-01

    Full Text Available The title compound, (C3H10N22[AlF6]F·3H2O, was obtained using the solvothermal method with aluminium hydroxide, HF and propane-1,3-diamine as precursors in ethanol as solvent. The structure consists of isolated [AlF6]3− octahedra, diprotonated propane-1,3-diamine cations [(H2dap2+], free fluoride ions and water molecules of solvation. The Al—F bond lengths in the octahedral [AlF6]3− anions range from 1.7690 (19 to 1.8130 (19 Å, with an average value of 1.794 Å. Each [AlF6]3− anion is surrounded by three water molecules and by six diprotonated amine cations. The `free' fluoride ion is hydrogen bonded to four H atoms belonging to four dications and has a distorted tetrahedral geometry. The three water molecules are connected by hydrogen bonds, forming trimers that connect the AlF6 octahedra and dications into a three-dimensional framework.

  15. In situ measurements of thickness changes and mechanical stress upon gasochromic switching of thin MoOx films

    Science.gov (United States)

    Okumu, J.; Koerfer, F.; Salinga, C.; Wuttig, M.

    2004-06-01

    Thin films of MoOx coated with platinum as a catalyst were prepared by dc magnetron sputtering from a molybdenum target in an oxygen and argon atmosphere. The films were colored and bleached by exposure to diluted hydrogen gas and air, respectively. In situ measurements of x-ray reflectance and substrate curvature were performed during switching cycles. Upon hydrogen exposure a remarkable thickness decrease of 11% and a density increase of 6.5% are observed by x-ray reflectance measurements. Corresponding changes in optical transmittance and mechanical stress up to several hundreds of MPa are also observed. These changes are not fully reversible as revealed by measurements of multiple switching cycles. Both the change of thickness and density, as well as the change of optical transmittance and mechanical stress can be explained by the existence of a mixed phase of edge and corner sharing MoO3 octahedra whereupon the first coloration the ratio between edge and corner sharing octahedra is changed.

  16. The crystal structure of Kirkiite, Pb10Bi3As3S19

    DEFF Research Database (Denmark)

    Makovicky, Emil; Balic Zunic, Tonci; Karanovic, Ljiljana

    2006-01-01

    layers parallel to (083) of kirkiite; the slabs are unit-cell-twinned on (010) refl ection planes. The structure contains one split As position, and two additional sites that could accommodate both As and Bi. The As,Bi distribution over these two sites is determined by the trapezoidal distortion......The crystal structure of kirkiite has been solved using single-crystal data (MoKa X-ray diffraction, CCD area detector) to the conventional R-factor R1 = 0.069. It crystallizes in space group P21/m, with a 8.621(4), b 26.03(1), c 8.810(4) Å, ß 119.21(1)° and Z = 2. A crystal-structure determination....... The crystal structure of kirkiite can be described as (010) slabs of octahedra, three octahedra thick and related mutually by a refl ection plane situated in the intervening prismatic layer. In another interpretation, it is composed of slabs based on a transitional PbS-SnS archetype, with tightly bonded...

  17. The synthesis and characterisation of LaCa2Fe2GaO8

    Science.gov (United States)

    Luo, Kun; Hayward, Michael A.

    2013-02-01

    The synthesis and characterisation of LaCa2Fe2GaO8 is described. Neutron powder diffraction data reveal LaCa2Fe2GaO8 adopts an anion-vacancy ordered, 'triple layer' structure consisting of an OOTLOOTR stacking sequence of layers of (Fe/Ga)O6 octahedra (O) and (Fe/Ga)O4 tetrahedra (T), related to that of the 4-layer brownmillerite structures (a=5.4784(1) Å, b=22.6780(4) Å, c=5.6007(1) Å, space group Pbma). The apex-linked chains of tetrahedra within structure of LaCa2Fe2GaO8 exhibit a cooperative twisting distortion which alternates in direction between adjacent layers of tetrahedra, the first time such an arrangement has been seen in a triple-layer phase. Magnetisation and neutron diffraction data reveal that LaCa2Fe2GaO8 exhibits two magnetic ordering transitions. On cooling below 550 K the phase adopts a state with short range antiferromagnetic coupling within each double layer of (Fe/Ga)O6 octahedra, but only weak coupling between layers. On cooling below 470 K full three-dimensional, G-type antiferromagnetic order is observed.

  18. A V(IV) Hydroxyhydrogenomonophosphate with an Intersecting Tunnel Structure: HK 4[V 10O 10(H 2O) 2(OH) 4(PO 4) 7]·9H 2O

    Science.gov (United States)

    Berrah, F.; Guesdon, A.; Leclaire, A.; Borel, M. M.; Provost, J.; Raveau, B.

    1999-12-01

    A V(IV) hydroxyhydrogenomonophosphate HK4[V10O10(H2O)2(OH)4(PO4)7]·9H2O has been obtained, using hydrothermal conditions. Its structure, closely related to that of (CH3)2NH2K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O, differs from the latter by its I41/a space group (instead of P43). This difference corresponds to a "disordering" of the vanadium atoms, with respect to the dimethyl ammonium phase. It is shown that this disorder, which appears in the form of "V5O22" units distributed at random, does not affect the oxygen framework. The analysis of this complex structure shows that it can be described from the stacking along c of [V8P7O38(OH)4(H2O)2]∞ layers interconnected through layers of isolated VO6 octahedra. In this structure, built up of VO6, VO5OH, and VO4(OH)(H2O) octahedra, of VO4OH pyramids, and of PO4 tetrahedra, large "toffee" tunnels and smaller ones with a tulip-shape section are running along a (or b). The first ones are stuffed with H2O molecules forming aquo tubes, where protons are likely "delocalized," whereas the second ones are occupied by K+ cations.

  19. Raman spectroscopy of rare-earth orthoferrites R FeO3 (R =La, Sm, Eu, Gd, Tb, Dy)

    Science.gov (United States)

    Weber, Mads Christof; Guennou, Mael; Zhao, Hong Jian; Íñiguez, Jorge; Vilarinho, Rui; Almeida, Abílio; Moreira, Joaquim Agostinho; Kreisel, Jens

    2016-12-01

    We report a Raman scattering study of six rare-earth orthoferrites R FeO3, with R = La, Sm, Eu, Gd, Tb, Dy. The use of extensive polarized Raman scattering of SmFeO3 and first-principles calculations enable the assignment of the observed phonon modes to vibrational symmetries and atomic displacements. The assignment of the spectra and their comparison throughout the whole series allow correlating the phonon modes with the orthorhombic structural distortions of R FeO3 perovskites. In particular, the positions of two specific A g modes scale linearly with the two FeO6 octahedra tilt angles, allowing the distortion to be tracked throughout the series. At variance with literature, we find that the two octahedra tilt angles scale differently with the vibration frequencies of their respective A g modes. This behavior, as well as the general relations between the tilt angles, the frequencies of the associated modes, and the ionic radii are rationalized in a simple Landau model. The reported Raman spectra and associated phonon-mode assignment provide reference data for structural investigations of the whole series of orthoferrites.

  20. Anomalous Thermal Expansion of HoCo0.5Cr0.5O3 Probed by X-ray Synchrotron Powder Diffraction

    Science.gov (United States)

    Hreb, Vasyl; Vasylechko, Leonid; Mykhalichko, Vitaliya; Prots, Yurii

    2017-07-01

    Mixed holmium cobaltite-chromite HoCo0.5Cr0.5O3 with orthorhombic perovskite structure (structure type GdFeO3, space group Pbnm) was obtained by solid state reaction of corresponding oxides in air at 1373 K. Room- and high-temperature structural parameters were derived from high-resolution X-ray synchrotron powder diffraction data collected in situ in the temperature range of 300-1140 K. Analysis of the results obtained revealed anomalous thermal expansion of HoCo0.5Cr0.5O3, which is reflected in a sigmoidal temperature dependence of the unit cell parameters and in abnormal increase of the thermal expansion coefficients with a broad maxima near 900 K. Pronounced anomalies are also observed for interatomic distances and angles within Co/CrO6 octahedra, tilt angles of octahedra and atomic displacement parameters. The observed anomalies are associated with the changes of spin state of Co3+ ions and insulator-metal transition occurring in HoCo0.5Cr0.5O3.

  1. Shape-dependent electrocatalytic activity of monodispersed palladium nanocrystals toward formic acid oxidation

    Science.gov (United States)

    Zhang, Xuwei; Yin, Huajie; Wang, Jinfeng; Chang, Lin; Gao, Yan; Liu, Wei; Tang, Zhiyong

    2013-08-01

    The catalytic activity of different-shaped and monodispersed palladium nanocrystals, including cubes, octahedra and rhombic dodecahedra, toward the electrochemical oxidation of formic acid has been systematically evaluated in both HClO4 and H2SO4 solutions. Notably, the cubic palladium nanocrystals wholly exposed with {100} facets exhibit the highest activity, while the rhombic dodecahedra with {110} facets show the lowest electrocatalytic performance. Furthermore, compared with HClO4 electrolyte, the catalytic activity is found to be obviously lower in H2SO4 solution likely due to the competitive adsorption of SO42- ions and formic acid on the surface of Pd nanocrystals.The catalytic activity of different-shaped and monodispersed palladium nanocrystals, including cubes, octahedra and rhombic dodecahedra, toward the electrochemical oxidation of formic acid has been systematically evaluated in both HClO4 and H2SO4 solutions. Notably, the cubic palladium nanocrystals wholly exposed with {100} facets exhibit the highest activity, while the rhombic dodecahedra with {110} facets show the lowest electrocatalytic performance. Furthermore, compared with HClO4 electrolyte, the catalytic activity is found to be obviously lower in H2SO4 solution likely due to the competitive adsorption of SO42- ions and formic acid on the surface of Pd nanocrystals. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03100d

  2. Crystal-plane-controlled selectivity of Cu(2)O catalysts in propylene oxidation with molecular oxygen.

    Science.gov (United States)

    Hua, Qing; Cao, Tian; Gu, Xiang-Kui; Lu, Jiqing; Jiang, Zhiquan; Pan, Xiaorong; Luo, Liangfeng; Li, Wei-Xue; Huang, Weixin

    2014-05-05

    The selective oxidation of propylene with O2 to propylene oxide and acrolein is of great interest and importance. We report the crystal-plane-controlled selectivity of uniform capping-ligand-free Cu2 O octahedra, cubes, and rhombic dodecahedra in catalyzing propylene oxidation with O2 : Cu2 O octahedra exposing {111} crystal planes are most selective for acrolein; Cu2 O cubes exposing {100} crystal planes are most selective for CO2 ; Cu2 O rhombic dodecahedra exposing {110} crystal planes are most selective for propylene oxide. One-coordinated Cu on Cu2 O(111), three-coordinated O on Cu2 O(110), and two-coordinated O on Cu2 O(100) were identified as the catalytically active sites for the production of acrolein, propylene oxide, and CO2 , respectively. These results reveal that crystal-plane engineering of oxide catalysts could be a useful strategy for developing selective catalysts and for gaining fundamental understanding of complex heterogeneous catalytic reactions at the molecular level. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Tris(ethylenediammonium bis[(2-aminoethylammonium] bis[bis(μ5-hydrogen phosphatopenta-μ2-oxido-decaoxidopentamolybdenum(VI] decahydrate

    Directory of Open Access Journals (Sweden)

    Jing Lu

    2010-05-01

    Full Text Available The title compound, (C2H10N23(C2H9N22[Mo5(HPO42O15]·10H2O, was prepared under hydrothermal conditions at pH 5.0. The structure contains mono- and diprotonated ethylenediamine cations, [Mo5O15(HPO42]4− anions and uncoordinated water molecules. The [Mo5O15(HPO42]4− heteropolyoxometallate anion is made up of five MoO6 octahedra sharing an edge and forming a ring, which is closed by common corners of the terminal MoO6 octahedron. The ring is topped on both sides by two slightly distorted PO4 tetrahedra, sharing three corners with three MoO6 octahedra. The terminal oxygen atoms of the PO4 units are protonated. Together with the anions, the water molecules and the ethylenediammonium cations are involved in N—H...O and O—H...O hydrogen bonding, forming a three-dimensional supramolecular network.

  4. The alluaudite-type crystal structures of Na2(Fe/Co2Co(VO43 and Ag2(Fe/Co2Co(VO43

    Directory of Open Access Journals (Sweden)

    Mohammed Hadouchi

    2016-07-01

    Full Text Available Single crystals of the title compounds, disodium di(cobalt/iron cobalt tris(orthovanadate, Na2(Fe/Co2Co(VO43, and disilver di(cobalt/iron cobalt tris(orthovanadate, Ag2(Fe/Co2Co(VO43, were grown from a melt consisting of stoichiometric mixtures of three metallic cation precursors and vanadium pentoxide. The difficulty to distinguish between cobalt and iron by using X-ray diffraction alone forced us to explore several models, assuming an oxidation state of +II for Co and +III for Fe and a partial cationic disorder in the Wyckoff site 8f containing a mixture of Co and Fe with a statistical distribution for the Na compound and an occupancy ratio of 0.4875:0.5125 (Co:Fe for the Ag compound. The alluaudite-type structure is made up from [10-1] chains of [(Co,Fe2O10] double octahedra linked by highly distorted [CoO6] octahedra via a common edge. The chains are linked through VO4 tetrahedra, forming polyhedral sheets perpendicular to [010]. The stacking of the sheets defines two types of channels parallel to [001] where the Na+ cations (both with full occupancy or Ag+ cations (one with occupancy 0.97 are located.

  5. Anion–Anion Bonding and Topology in Ternary Iridium Seleno–Stannides

    Energy Technology Data Exchange (ETDEWEB)

    Trump, Benjamin A.; Tutmaher, Jake A.; McQueen, Tyrel M. (JHU)

    2015-12-21

    The synthesis and physical properties of two new and one known Ir–Sn–Se compound are reported. Their crystal structures are elucidated with transmission electron microscopy and powder X-ray diffraction. IrSn0.45Se1.55 is a pyrite phase which consists of tilted corner-sharing IrX6 octahedra with randomly distributed (Sn–Se)4– and (Se–Se)2– dimers. Ir2Sn3Se3 is a known trigonally distorted skutterudite that consists of cooperatively tilted corner-sharing IrSn3Se3 octahedra with ordered (Sn–Se)24– tetramers. Ir2SnSe5 is a layered, distorted β-MnO2 (pyrolusite) structure consisting of a double IrSe6 octrahedral row, corner sharing in the a direction and edge sharing in the b direction. This distorted pyrolusite contains (Se–Se)2– dimers and Se2– anions, and each double row is “capped” with a (Sn–Se)n polymeric chain. Resistivity, specific heat, and magnetization measurements show that all three have insulating and diamagnetic behavior, indicative of low-spin 5d6 Ir3+. Electronic structure calculations on Ir2Sn3Se3 show a single, spherical, nonspin–orbit split valence band and suggest that Ir2Sn3Se3 is topologically nontrivial under tensile strain due to inversion of Ir-d and Se-p states.

  6. Structural properties of lithium borate glasses doped with rare earth ions

    Directory of Open Access Journals (Sweden)

    Thomazini D.

    2001-01-01

    Full Text Available This paper presents the study on lithium triborate glass (LBO in the system (1-x|3B2O3.Li2O| (xNb2O5 yPr3+ zYb3+ wNd3+ with 0 <= x <= 20 mol% (y, z and w in mol%. The samples were studied by Raman spectroscopy, infrared absorption and differential thermal analysis. Pr3+-doped LBO and Pr3+/Yb3+-doped LBO samples show an increase of the glass transition and crystallization temperatures and a decrease of the fusion temperature associated with the increase of the praseodymium concentration in the LBO matrix. For the Nd3+-doped LBO and Pr3+/Yb3+-doped (LBO+Nb2O5 samples, a decrease of the glass transition temperature of the samples was observed. The increase of the rare earth doping leads to an increase of the difference between the glass transition and the crystallization temperatures. From infrared analysis it was possible to identify all the modes associated to the B-O structure. The NbO6 octahedra was also identified by IR spectroscopy for samples with x=5, 10, 15 and 20 mol% and y=0.05, z=1.1 mol%. Raman spectroscopy shows the presence of boroxol rings, tetrahedral and triangular coordination for boron. For samples containing niobium, the Raman spectra show the vibrational mode associated with the Nb-O bond in the niobium octahedra (NbO6.

  7. Landau theory and giant room-temperature barocaloric effect in MF3 metal trifluorides

    Energy Technology Data Exchange (ETDEWEB)

    Corrales-Salazar, A. [Univ. of Costa Rica, San Jose (Costa Rica); Brierley, R. T. [Yale Univ., New Haven, CT (United States); Littlewood, P. B. [Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Guzmán-Verri, G. G. [Univ. of Costa Rica, San Jose (Costa Rica); Argonne National Lab. (ANL), Argonne, IL (United States)

    2017-10-17

    The structural phase transitions of MF3 (M = Al, Cr, V, Fe, Ti, Sc) metal trifluorides are studied within a simple Landau theory consisting of tilts of rigid MF6 octahedra associated with soft antiferrodistortive optic modes that are coupled to long-wavelength strain generating acoustic phonons. We calculate the temperature and pressure dependence of several quantities such as the spontaneous distortions, volume expansion, and shear strains as well as T - P phase diagrams. By contrasting our model to experiments we quantify the deviations from mean-field behavior and find that the tilt fluctuations of the MF6 octahedra increase with metal cation size. We apply our model to predict giant barocaloric effects in Sc-substituted TiF3 of up to about 15 JK-1 kg-1 for modest hydrostatic compressions of 0.2GPa. The effect extends over a wide temperature range of over 140K (including room temperature) due to a large predicted rate, dTc/dP = 723K GPa-1, which exceeds those of typical barocaloric materials. Our results suggest that open lattice frameworks such as the trifluorides are an attractive platform to search for giant barocaloric effects.

  8. Molecular behavior of zero-dimensional perovskites

    KAUST Repository

    Yin, Jun

    2017-12-16

    Low-dimensional perovskites offer a rare opportunity to investigate lattice dynamics and charge carrier behavior in bulk quantum-confined solids, in addition to them being the leading materials in optoelectronic applications. In particular, zero-dimensional (0D) inorganic perovskites of the Cs4PbX6 (X = Cl, Br, or I) kind have crystal structures with isolated lead halide octahedra [PbX6]4− surrounded by Cs+ cations, allowing the 0D crystals to exhibit the intrinsic properties of an individual octahedron. Using both experimental and theoretical approaches, we studied the electronic and optical properties of the prototypical 0D perovskite Cs4PbBr6. Our results underline that this 0D perovskite behaves akin to a molecule, demonstrating low electrical conductivity and mobility as well as large polaron binding energy. Density functional theory calculations and transient absorption measurements of Cs4PbBr6 perovskite films reveal the polaron band absorption and strong polaron localization features of the material. A short polaron lifetime of ~2 ps is observed in femtosecond transient absorption experiments, which can be attributed to the fast lattice relaxation of the octahedra and the weak interactions among them.

  9. Glycine zinc sulfate pentahydrate: redetermination at 10 K from time-of-flight neutron Laue diffraction

    Directory of Open Access Journals (Sweden)

    A. Dominic Fortes

    2016-10-01

    Full Text Available Single crystals of glycine zinc sulfate pentahydrate [systematic name: hexaaquazinc tetraaquadiglycinezinc bis(sulfate], [Zn(H2O6][Zn(C2H5NO22(H2O4](SO42, have been grown by isothermal evaporation from aqueous solution at room temperature and characterized by single-crystal neutron diffraction. The unit cell contains two unique ZnO6 octahedra on sites of symmetry -1 and two SO4 tetrahedra with site symmetry 1; the octahedra comprise one [tetraaqua-diglycine zinc]2+ ion (centred on one Zn atom and one [hexaaquazinc]2+ ion (centred on the other Zn atom; the glycine zwitterion, NH3+CH2COO−, adopts a monodentate coordination to the first Zn atom. All other atoms sit on general positions of site symmetry 1. Glycine forms centrosymmetric closed cyclic dimers due to N—H...O hydrogen bonds between the amine and carboxylate groups of adjacent zwitterions and exhibits torsion angles varying from ideal planarity by no more than 1.2°, the smallest values for any known glycine zwitterion not otherwise constrained by a mirror plane. This work confirms the H-atom locations estimated in three earlier single-crystal X-ray diffraction studies with the addition of independently refined fractional coordinates and Uij parameters, which provide accurate internuclear X—H (X = N, O bond lengths and consequently a more accurate and precise depiction of the hydrogen-bond framework.

  10. Facile synthesis and structure characterization of hexagonal tungsten bronzes crystals

    Science.gov (United States)

    Lee, Jiann-Shing; Liu, Hao-Chuan; Peng, Gao-De; Tseng, Yawteng

    2017-05-01

    A facile molten-salt route was used to synthesize hexagonal Cs0.33WO3, Rb0.33WO3 and K0.30WO3 crystals. The three isostructural compounds were successfully prepared from the reaction of MxWO3 powders (M = Cs, Rb, K) in the CsCl/NaCl, RbCl/NaCl and KCl/NaCl fluxes, respectively. The structure determination and refinement, based on single-crystal X-ray diffraction data, are in agreement with previous works, possessing space group P63/mcm. The a and c parameters vary non-linearly with increasing radii of the M+ cations (rM) that is coordinated to twelve oxygen atoms. Both the volumes of unit-cell and WO6 octahedra vary linearly with rM, which become smaller from Cs0.33WO3 to K0.30WO3. The distortion of WO6 octahedra as well as isotropic displacement parameters increases from Cs0.33WO3 to K0.30WO3. The geometry of the WO6 octahedron becomes more regular with increasing rM. These structural trends arise from the effective size of the M+ cation.

  11. Zirconium coordination change upon the pressure-induced amorphization of cubic ZrW2O8 and ZrMo2O8

    Energy Technology Data Exchange (ETDEWEB)

    Varga, Tamas; Wilkinson, Angus

    2009-06-30

    EXAFS and XANES were used to examine samples cubic ZrW2O8 and cubic ZrMo2O8 that had been pressure amorphized in a multi-anvil press and recovered to ambient conditions. Data were taken at the W LIII- and LI- or Mo K-edges, as well as at the Zr K-edge. These data indicate an increase in the average coordination number of tungsten in ZrW2O8 and a less pronounced increase in that of molybdenum in ZrMo2O8. This is in agreement with previous work. However, the Zr K-edge data indicated a, previously unreported, change in the average Zr-coordination from 6 to ~7 for both compounds. These results demonstrate that both the framework tetrahedra and octahedra distort on amorphization, and in the case of ZrMo2O8, the ZrO6 octahedra are more prone to distortion at the amorphization pressure. A decrease in the photoelectron scattering magnitudes for the metal-metal correlations was seen on amorphization, indicating that these correlations are less well defined in the amorphous material.

  12. EPR study of the Jahn-Teller effect of Cu2+ ions in ZnGa2O4

    Science.gov (United States)

    Vorotynov, A. M.; Petrakovskiĭ, G. A.; Sablina, K. A.; Bovina, A. F.; Vasil'Ev, A. D.

    2010-11-01

    The Jahn-Teller effect in the ZnGa2O4 spinel single crystal has been investigated using electron paramagnetic resonance of Cu2+ ions in the temperature range 110-560 K. It has been shown that copper ions occupy octahedral sites 16 d in the ZnGa2O4 crystal with cubic symmetry O {/h 7} ( Fd-3 m). At T < 560 K, the octahedra undergo tetragonal distortions (predominantly tension) and rotation around the fourfold axes by the angle θ ≈ 2.6°. The parameters of the spin Hamiltonian, which characterize the prolate ( g ‖ = 2.355, g ⊥ = 2.077, A ‖ = 116 Oe, A tp = 12 Oe) and oblate ( g ‖ = 2.018, g ⊥ = 2.246, A ‖ = 75 Oe, A ⊥ = 44 Oe) octahedra, have been determined. At temperatures above 560 K, the static Jahn-Teller effect transforms into the dynamic effect and the spectrum of the magnetic resonance becomes isotropic with g = 2.116 (the experimental frequency corresponds to the X band).

  13. Compressional pathways of α-cristobalite, structure of cristobalite X-I, and towards the understanding of seifertite formation

    Science.gov (United States)

    Černok, Ana; Marquardt, Katharina; Caracas, Razvan; Bykova, Elena; Habler, Gerlinde; Liermann, Hanns-Peter; Hanfland, Michael; Mezouar, Mohamed; Bobocioiu, Ema; Dubrovinsky, Leonid

    2017-06-01

    In various shocked meteorites, low-pressure silica polymorph α-cristobalite is commonly found in close spatial relation with the densest known SiO2 polymorph seifertite, which is stable above ~80 GPa. We demonstrate that under hydrostatic pressure α-cristobalite remains untransformed up to at least 15 GPa. In quasi-hydrostatic experiments, above 11 GPa cristobalite X-I forms--a monoclinic polymorph built out of silicon octahedra; the phase is not quenchable and back-transforms to α-cristobalite on decompression. There are no other known silica polymorphs, which transform to an octahedra-based structure at such low pressures upon compression at room temperature. Further compression in non-hydrostatic conditions of cristobalite X-I eventually leads to the formation of quenchable seifertite-like phase. Our results demonstrate that the presence of α-cristobalite in shocked meteorites or rocks does not exclude that materials experienced high pressure, nor is the presence of seifertite necessarily indicative of extremely high peak shock pressures.

  14. Coherent Nanotwins and Dynamic Disorder in Cesium Lead Halide Perovskite Nanocrystals.

    Science.gov (United States)

    Bertolotti, Federica; Protesescu, Loredana; Kovalenko, Maksym V; Yakunin, Sergii; Cervellino, Antonio; Billinge, Simon J L; Terban, Maxwell W; Pedersen, Jan Skov; Masciocchi, Norberto; Guagliardi, Antonietta

    2017-04-25

    Crystal defects in highy luminescent colloidal nanocrystals (NCs) of CsPbX 3 perovskites (X = Cl, Br, I) are investigated. Here, using X-ray total scattering techniques and the Debye scattering equation (DSE), we provide evidence that the local structure of these NCs always exhibits orthorhombic tilting of PbX 6 octahedra within locally ordered subdomains. These subdomains are hinged through a two-/three-dimensional (2D/3D) network of twin boundaries through which the coherent arrangement of the Pb ions throughout the whole NC is preserved. The density of these twin boundaries determines the size of the subdomains and results in an apparent higher-symmetry structure on average in the high-temperature modification. Dynamic cooperative rotations of PbX 6 octahedra are likely at work at the twin boundaries, causing the rearrangement of the 2D or 3D network, particularly effective in the pseudocubic phases. An orthorhombic, 3D γ-phase, isostructural to that of CsPbBr 3 is found here in as-synthesized CsPbI 3 NCs.

  15. New series of indium formates: hydrothermal synthesis, structure and coordination modes.

    Science.gov (United States)

    Su, Jie; Wang, Yingxia; Yang, Sihai; Li, Guobao; Liao, Fuhui; Lin, Jianhua

    2007-10-01

    Three new indium(III) compounds, In(HCOO)3 (1), In2(HCOO)5(OH) (2), and In(HCOO)2(OH) (3), were synthesized under hydrothermal conditions and characterized by single crystal and powder X-ray diffraction experiments, as well as by IR spectroscopy, elemental analysis, and coupled TG-DSC-MS measurement. All of these compounds adopt 3D framework structures consisting of InO6 octahedra and the 2.11 binding modes of formate with the (syn, syn-; syn, anti-; anti, anti-) configurations. The structural investigation of these indium formates reveals that the gradual introduction of the hydroxyl groups into the structures induces the polymerization of the InO6 octahedra, that is, InO6 is isolated in 1, becomes dimeric in 2, and finally forms 1D chains in 3. In addition, a simple formula that may be used for estimating the overall coordination number of the formate in Ma(HCOO)bLc is proposed.

  16. Cation size effect on the framework structures in a series of new alkali-metal indium selenites, AIn(SeO3)2 (A = Na, K, Rb, and Cs).

    Science.gov (United States)

    Lee, Dong Woo; Kim, Saet Byeol; Ok, Kang Min

    2012-08-06

    A new family of quaternary alkali-metal indium selenites, AIn(SeO(3))(2) (A = Na, K, Rb, and Cs) have been synthesized, as crystals and pure polycrystalline phases through standard solid-state and hydrothermal reactions. The structures of the reported materials have been determined by single-crystal X-ray diffraction. While AIn(SeO(3))(2) (A = Na, K, and Rb) crystallize in the orthorhombic space group, Pnma, with three-dimensional framework structures, CsIn(SeO(3))(2) crystallizes in the trigonal space group, R3m, with a two-dimensional structure. All of the reported materials, however, share a common structural motif, a network of corner-shared InO(6) octahedra and SeO(3) groups. Interestingly, the size of the alkali-metal cations profoundly influences the bonding nature of the SeO(3) group to the InO(6) octahedra. Complete characterizations including infrared spectroscopy, elemental analyses, and thermal analyses for the compounds are also presented, as are dipole moment calculations. A detailed cation size effect on the framework structure is discussed.

  17. Structural reasons for the nonlinear optical properties of KTi{sub 0.96}Zr{sub 0.04}OPO{sub 4} single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Novikova, N. E., E-mail: natnov@ns.crys.ras.ru; Verin, I. A.; Sorokina, N. I.; Alekseeva, O. A. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Agapova, E. I.; Voronkova, V. I. [Moscow State University (Russian Federation)

    2009-03-15

    This paper reports on the results of the precision X-ray structural investigations of KTi{sub 0.96}Zr{sub 0.04}OPO{sub 4} single crystals at room temperature. It is established that the incorporation of zirconium atoms into the structure of KTiOPO{sub 4} (KTP) crystals does not lead to substantial changes in the framework structure and results only in an insignificant decrease in the scatter of the distances in the PO{sub 4} tetrahedra and the formation of more symmetric (TiZr)O{sub 6} octahedra as compared to the TiO{sub 6} octahedra. However, the incorporation of zirconium atoms into the KTP structure is accompanied by the redistribution of the electron density in the crystal as a whole, so that the electron density increases in the region of the positions occupied by the potassium atoms. This changes the nonlinear optical properties of the given series of crystals, which are estimated from the intensity of the second harmonic generation signals.

  18. Graphene oxide and shape-controlled silver nanoparticle hybrids for ultrasensitive single-particle surface-enhanced Raman scattering (SERS) sensing.

    Science.gov (United States)

    Fan, Wei; Lee, Yih Hong; Pedireddy, Srikanth; Zhang, Qi; Liu, Tianxi; Ling, Xing Yi

    2014-05-07

    Graphene oxide (GO) is an emerging material for surface-enhanced Raman scattering (SERS) due to its strong chemical enhancement. Studying the SERS performance of plasmonic nanoparticle/GO hybrid materials at the single particle level is crucial for direct probing of the chemical effect of GO on plasmonic nanoparticles. In this work, we integrate GO and shape-controlled Ag nanoparticles to create hybrid nanomaterials, and the chemical enhancement arising from GO is investigated using single-particle SERS measurements. Ag nanoparticle@GO hybrid nanostructures are prepared by assembling Ag nanoparticles, including spheres, cubes and octahedra with GO sheets. The SERS behaviors of the hybrid nanostructures are characterized, and 2-3 times enhanced SERS intensities are detected from the Ag nanoparticle@GO hybrid nanostructures as compared to pure Ag nanoparticles. Furthermore, we probe the mechanism of SERS enhancement in the hybrid nanostructures by changing the surface coverage of GO on Ag octahedra, by using reduced GO in place of GO as well as by using probe molecules of different electronegativities. This hybrid system is an excellent candidate for single-particle SERS sensors. Sub-nanomolar levels of aromatic molecules are detected using a single Ag/GO hybrid nanomaterial. This as-prepared GO and shape-controlled Ag nanoparticle hybrid is capable of serving as a high performance SERS platform, providing new opportunities for efficient chemical and biological sensing applications.

  19. SrMnII2MnIII(PO43

    Directory of Open Access Journals (Sweden)

    Ghaleb Alhakmi

    2013-09-01

    Full Text Available The title compound, strontium trimanganese tris(orthophosphate, was synthesized under hydrothermal conditions. Its structure is isotypic to that of the lead analogue PbMnII2MnIII(PO43. Two O atoms are in general positions, whereas all others atoms are in special positions. The Sr and one P atom exhibit mm2 symmetry, the MnII atom 2/m symmetry, the MnIII atom and the other P atom .2. symmetry and two O atoms are located on mirror planes. The three-dimensional network of the crystal structure is made up of two types of chains running parallel to [010]. One chain is linear and is composed of alternating MnIIIO6 octahedra and PO4 tetrahedra sharing vertices; the other chain has a zigzag arrangement and is built up from two edge-sharing MnIIO6 octahedra connected to PO4 tetrahedra by edges and vertices. The two types of chains are linked through PO4 tetrahedra, leading to the formation of channels parallel to [100] and [010] in which the SrII ions are located. They are surrounded by eight O atoms in the form of a slightly distorted bicapped trigonal prism.

  20. Structure-microwave dielectric property relations in Sr and Ca titanates

    CERN Document Server

    Wise, P L

    2001-01-01

    induces a structural phase transition involving rotations of the O-octahedra. The behaviour of TC epsilon and therefore TCF as a function of tolerance factor was similar in the (Sr sub x Ca sub 1 sub - sub x) sub 3 Ti sub 2 O sub 7 series to that observed for Ba and Sr based complex perovskites. It was therefore concluded that tilting of the octahedra dominated tuning of TCF. The domain variance associated with structural phase transitions in the solid (Sr sub x Ca sub 1 sub - sub x)TiO sub 3 solid solution series has been investigated using electron diffraction. Only electron diffraction patterns from end member compositions conformed to those simulated using other workers' X-ray diffraction and neutron diffraction refinement data. For compositions where x=0.8, a tetragonal (I4/mcm) antiphase tilt system (a deg a deg c sup -) is predicted. However, comparisons of simulated with experimental single domain patterns suggested that this composition has more than one axis tilted in antiphase. Tuning the temperatu...

  1. Robertsite, Ca2MnIII3O2(PO43·3H2O

    Directory of Open Access Journals (Sweden)

    Marcelo B. Andrade

    2012-10-01

    Full Text Available Robertsite, ideally Ca2Mn3O2(PO43·3H2O [calcium manganese(III tris(orthophosphate trihydrate], can be associated with the arseniosiderite structural group characterized by the general formula Ca2A3O2(TO43·nH2O, with A = Fe, Mn; T = As, P; and n = 2 or 3. In this study, single-crystal X-ray diffraction data were used to determine the robertsite structure from a twinned crystal from the type locality, the Tip Top mine, Custer County, South Dakota, USA, and to refine anisotropic displacement parameters for all atoms. The general structural feature of robertsite resembles that of the other two members of the arseniosiderite group, the structures of which have previously been reported. It is characterized by sheets of [MnO6] octahedra in the form of nine-membered pseudo-trigonal rings. Located at the center of each nine-membered ring is a PO4 tetrahedron, and the other eight PO4 tetrahedra sandwich the Mn–oxide sheets. The six different Ca2+ ions are seven-coordinated in form of distorted pentagonal bipyramids, [CaO5(H2O2], if Ca—O distances less than 2.85 Å are considered. Along with hydrogen bonding involving the water molecules, they hold the manganese–phosphate sheets together. All nine [MnO6] octahedra are distorted by the Jahn–Teller effect.

  2. Spin ½ Delafossite honeycomb compound Cu5SbO6.

    Science.gov (United States)

    Climent-Pascual, E; Norby, P; Andersen, N H; Stephens, P W; Zandbergen, H W; Larsen, J; Cava, R J

    2012-01-02

    Cu(5)SbO(6) is found to have a monoclinic, Delafossite-derived structure consisting of alternating layers of O-Cu(I)-O sticks and magnetic layers of Jahn-Teller distorted Cu(II)O(6) octahedra in an edge sharing honeycomb arrangement with Sb(V)O(6) octahedra. This yields the structural formula Cu(I)(3)Cu(II)(2)Sb(V)O(6). Variants with ordered and disordered layer stacking are observed, depending on the synthesis conditions. The spin ½ Cu(2+) ions form dimers in the honeycomb layer. The magnetic susceptibility measured between 5 and 300 K is characteristic of the presence of a singlet-triplet spin gap of 189 K. High resolution synchrotron X-ray diffraction studies indicate that changes in the intra- or interdimer distances between 300 and 20 K, such as might indicate an increase in strength of the Peierls-like distortion through the spin gap temperature, if present, are very small. A comparison to the NaFeO(2)-type Cu(2+) honeycomb compounds Na(3)Cu(2)SbO(6) and Na(2)Cu(2)TeO(6) is presented.

  3. Crystalline Control of {111} Bounded Pt3Cu Nanocrystals: Multiply-Twinned Pt3Cu Icosahedra with Enhanced Electrocatalytic Properties.

    Science.gov (United States)

    Sun, Xiuhui; Jiang, Kezhu; Zhang, Nan; Guo, Shaojun; Huang, Xiaoqing

    2015-07-28

    Despite that different facets have distinct catalytic behavior, the important role of twin defects on enhancing the catalytic performance of metallic nanocrystals is largely unrevealed. The key challenge in demonstrating the importance of twin defects for catalysis is the extreme difficulties in creating nanostructures with the same exposed facets but tunable twin defects that are suitable for catalytic investigations. Herein, we show an efficient synthetic strategy to selectively synthesize {111}-terminated Pt3Cu nanocrystals with controllable crystalline features. Two distinct {111}-bounded shapes, namely, multiply-twinned Pt3Cu icosahedra and single-crystalline Pt3Cu octahedra, are successfully prepared by simply changing the types of Cu precursors with the other growth parameters unchanged. Electrocatalytic studies show that the {111}-terminated Pt3Cu nanocrystals exhibit the very interesting crystalline nature-dependent electrocatalytic activities toward both the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) with multiply-twinned Pt3Cu icosahedra demonstrating enhanced electrocatalytic activities compared to the single-crystalline Pt3Cu octahedra due to their additional yet important effect of twin defect. As a result, under the multiple tuning conditions (alloy, shape, and twin effects), the multiply-twinned Pt3Cu icosahedra exhibit much enhanced electrocatalytic activities in both ORR and MOR with respect to the Pt black. The present work highlights the importance of twin defects in enhancing electrocatalytic activities of metallic nanocrystals.

  4. Structural and Magnetic Properties of the Osmium Double Perovskites Ba2-xSrxYOsO6.

    Science.gov (United States)

    Kayser, Paula; Injac, Sean; Kennedy, Brendan J; Vogt, Thomas; Avdeev, Maxim; Maynard-Casely, Helen E; Zhang, Zhaoming

    2017-06-05

    The crystal and magnetic structures of double perovskites of the type Ba2-xSrxYOsO6 were studied by synchrotron X-ray and neutron powder diffraction methods, bulk magnetic susceptibility measurements, and X-ray absorption spectroscopy. The structures were refined using combined neutron and synchrotron data sets based on an ordered array of corner-sharing YO6 and OsO6 octahedra, with the Ba/Sr cations being completely disordered. The structure evolves from cubic to monoclinic Fm3̅m (x ≈ 0.6) → I4/m (x ≈ 1.0) → I2/m (x ≈ 1.6) → P21/n as the Sr content is increased, due to the introduction of cooperative tilting of the octahedra. Bulk magnetic susceptibility measurements demonstrate the oxides are all anti-ferromagnets. The decrease in symmetry results in a nonlinear increase in the Neel temperature. Low-temperature neutron diffraction measurements of selected examples show these to be type-I anti-ferromagnets. X-ray absorption spectra collected at the Os L3- and L2-edges confirm the Os is pentavalent in all cases, and there is no detectable change in the covalency of the Os cation as the A-cation changes. Analysis of the L3/L2 branching ratio shows that the spin-orbit coupling is constant and insignificant across the series.

  5. Structural investigations of the two polymorphs of synthetic Fe-cordierite and Raman spectroscopy of hexagonal Fe-cordierite.

    Science.gov (United States)

    Haefeker, Udo; Kaindl, Reinhard; Tropper, Peter; Krüger, Hannes; Kahlenberg, Volker; Orlova, Maria

    The crystal structures of synthetic hexagonal and orthorhombic Fe-cordierite polymorphs with the space groups P6/mcc and Cccm were refined from single-crystal X-ray diffraction data to R1, hex = 3.14 % and R1, ortho = 4.48 %. The substitution of the larger Fe2+ for Mg leads to multiple structural changes and an increase of the unit cell volumes, with a, c (hex) = 9.8801(16) Å, 9.2852(5) Å and a, b, c (ortho) = 17.2306(2) Å, 9.8239(1) Å, 9.2892(1) Å in the end-members. Furthermore Fe incorporation results in an increase of the volumes of the octahedra, although the diameters of the octahedra in direction of the c-axis decrease in both polymorphs. X-ray powder diffraction analysis indicates a high degree of Al/Si ordering in the orthorhombic polymorph, the Miyashiro distortion index is ~0.24. Estimations of site occupancies based on the determined tetrahedral volumes result in the following values for hexagonal Fe-cordierite: ~73 % Al for T1 and ~28 % Al for T2. For the first time Raman spectroscopy was performed on the hexagonal Fe-cordierite polymorph. In the hexagonal Fe-cordierite polymorph most Raman peaks are shifted towards lower wavenumbers when compared with the Mg-end-member.

  6. Crystal structure of the Fe-member of usovite

    Directory of Open Access Journals (Sweden)

    Matthias Weil

    2015-06-01

    Full Text Available Crystals of the title compound, with the idealized composition Ba2CaFeAl2F14, dibarium calcium iron(II dialuminium tetradecafluoride, were obtained serendipitously by reacting a mixture of the binary fluorides BaF2, CaF2 and AlF3 in a leaky steel reactor. The compound crystallizes in the usovite structure type (Ba2CaMgAl2F14, with Fe2+ cations replacing the Mg2+ cations. The principal building units are distorted [CaF8] square-antiprisms (point group symmetry 2, [FeF6] octahedra (point group symmetry -1 and [AlF6] octahedra that are condensed into undulating 2∞[CaFeAl2F14]4− layers parallel (100. The Ba2+ cations separate the layers and exhibit a coordination number of 12. Two crystal structure models with a different treatment of the disordered Fe site [mixed Fe/Ca occupation, model (I, versus underoccupation of Fe, model (II], are discussed, leading to different refined formulae Ba2Ca1.310 (15Fe0.690 (15Al2F14 [model (I] and Ba2CaFe0.90 (1Al2F14 [model (II].

  7. Misfit strain accommodation in epitaxial ABO3 perovskites: lattice distortions and lattice modulations

    Science.gov (United States)

    Vailionis, A.; Boschker, H.; Houwman, E.; Koster, G.; Rijnders, G.; Blank, D. H.

    2010-03-01

    Transition-metal oxides exhibit variety of magnetic, electronic and structural properties due to the presence of strong electron-electron and electron-lattice correlations. For epitaxial ABO3 films substrate-induced biaxial stress is an effective tool to modify the electron-lattice coupling. We present a microstructural study of the lattice effects in SrRuO3 and La0.67Sr0.33MnO3 thin films grown under different tensile and compressive stresses. Due to the symmetry constraints, the ``pseudocubic'' perovskite unit cell does not reveal the diversity of distortions and tilts of BO6 octahedra which play a significant role in magnetic and electronic properties of the ABO3 perovskites. We show that the lattice distortions in perovskite thin films under misfit stress can be quantitatively described by assuming a lower symmetry unit cell: tetragonal, orthorhombic or monoclinic. The results demonstrate that the misfit strain modifies the degree and direction of BO6 octahedra distortions and rotations via structural transitions between tetragonal and orthorhombic unit cells as well as lattice modulations. The coherently strained films exhibit stress relief mechanism that is highly anisotropic along perpendicular in-plane directions. Such anisotropic stress accommodation is believed to affect anisotropic magnetic or electronic properties.

  8. Exploring the coordination change of vanadium and structure transformation of metavanadate MgV2O6 under high pressure

    Science.gov (United States)

    Tang, Ruilian; Li, Yan; Xie, Shengyi; Li, Nana; Chen, Jiuhua; Gao, Chunxiao; Zhu, Pinwen; Wang, Xin

    2016-01-01

    Raman spectroscopy, synchrotron angle-dispersive X-ray diffraction (ADXRD), first-principles calculations, and electrical resistivity measurements were carried out under high pressure to investigate the structural stability and electrical transport properties of metavanadate MgV2O6. The results have revealed the coordination change of vanadium ions (from 5+1 to 6) at around 4 GPa. In addition, a pressure-induced structure transformation from the C2/m phase to the C2 phase in MgV2O6 was detected above 20 GPa, and both phases coexisted up to the highest pressure. This structural phase transition was induced by the enhanced distortions of MgO6 octahedra and VO6 octahedra under high pressure. Furthermore, the electrical resistivity decreased with pressure but exhibited different slope for these two phases, indicating that the pressure-induced structural phase transitions of MgV2O6 was also accompanied by the obvious changes in its electrical transport behavior. PMID:27924843

  9. Pressure-induced structural evolution, optical and electronic transitions of nontoxic organometal halide perovskite-based methylammonium tin chloride

    Science.gov (United States)

    Wang, Lingrui; Ou, Tianji; Wang, Kai; Xiao, Guanjun; Gao, Chunxiao; Zou, Bo

    2017-12-01

    Hybrid solar cells with organometal halide perovskites have already reached a power conversion efficiency exceeding 22.1%, but their toxic lead component remains a serious concern. Hence, the replacement of lead with nontoxic alternatives, such as tin, has attracted increasing interest. This study investigates the structural and optoelectronic properties of nontoxic perovskite methylammonium tin chloride (MASnCl3, MA: CH3NH3) under pressure. The synchrotron X-ray diffraction experiment shows that the sample transforms from the monoclinic to the triclinic phase and then amorphizes. The tilting and distortion of [SnCl6]4- octahedra are mainly responsible for the bandgap decreasing below 1.0 GPa. Upon further compression, an additional optical absorption peak appears, which is ascribed to the conduction band splitting of the triclinic MASnCl3. The high pressure behavior of MA cations indicates that the interaction between MA cations and [SnCl6]4- octahedra is strengthened. The pressure-induced electrical resistance evolution of MASnCl3 coincides with the structural changes. The intrinsic properties and the stability of nontoxic Sn-based hybrid perovskites provide better understanding and insights into their potential applications in photovoltaics.

  10. Ferromagnetic grain boundary signature in die-upset RE-Fe-B magnets

    Energy Technology Data Exchange (ETDEWEB)

    Henderson Lewis, L.; Zhu, Y.; Welch, D.O.

    1994-07-01

    Previous nanostructural and nanocompositional studies performed on the boundaries of deformed grains in two die-upset rare earth magnets with bulk compositions Nd{sub 13.75}Fe{sub 80.25}B{sub 6}, and Pr{sub 13.75}Fe{sub 80.25}B{sub 6} indicate that the intergranular phase in many grain boundaries is enriched in iron relative to the bulk. Preliminary magnetic data are presented that provide further evidence that this grain boundary phase is indeed iron-rich, and in fact appears to be ferromagnetic. Hysteresis loops were performed at 800 K on die-upset magnets with the above compositions. Each sample showed a clear hysteresis with coercivities between 34 and 40 Oe average remanence 4{pi}M{sub R} of 6.8 G for the Nd-based sample and 10.3 G for the Pr-based sample. The ferromagnetic signals measured at high temperature in these magnets are attributed to the iron-rich grain boundary phase. The implications of this conclusion with respect to coercivity are discussed.

  11. Pressure-induced polyamorphism in lanthanide-solute metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Li, Liangliang; Li, Renfeng; Liu, Haozhe [Harbin Institute of Technology, Harbin (China); Center for High Pressure Science Technology Advanced Research, Changchun (China); Wang, Luhong [Harbin Institute of Technology, Harbin (China); Qu, Dongdong [School of Mechanical and Mining Engineering, The University of Queensland, Brisbane, QLD (Australia); Zhao, Haiyan [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL (United States); Center for Advanced Energy Studies, University of Idaho, Idaho Falls, ID (United States); Chapman, Karena W.; Chupas, Peter J. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL (United States)

    2017-06-15

    The electronic structure inheritance of lanthanide-solvent atoms in lanthanide-based metallic glasses has been proposed. Is a polyamorphism possible in lanthanide-solute metallic glasses? So far, polyamorphic phase transitions in metallic glass containing lanthanide have been observed only in lanthanide-solvent metallic glasses. Here, a pressure-induced transition between two distinct amorphous states, accompanied by a 7% volume collapse at ambient pressure, was observed in La{sub 43.4}Pr{sub 18.6}Al{sub 14}Cu{sub 24} metallic glass, with low lanthanide content, by using in situ X-ray total scattering method. The transformation also indicated by changes in short range and medium range order. Thus, it is proposed that the lanthanide-solute metallic glasses also inherit 4f electronic transition from pure lanthanide element in polyamorphic transition. This discovery offers a supplement to research on lanthanide-based metallic glasses, which further provides a new perspective of the polyamorphic transformation in metallic glasses containing lanthanide element. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. FURTHER CONSTRAINTS ON THE OPTICAL TRANSMISSION SPECTRUM OF HAT-P-1b

    Energy Technology Data Exchange (ETDEWEB)

    Montalto, M.; Santos, N. C.; Martins, J. H. C.; Figueira, P.; Alonso, R. [Instituto de Astrofísica e Ciências do Espaço, Universidade do Porto, CAUP, Rua das Estrelas, PT4150-762 Porto (Portugal); Iro, N. [Theoretical Meteorology Group Klimacampus, University of Hamburg Grindelberg 5, D-20144, Hamburg (Germany); Desidera, S., E-mail: Marco.Montalto@astro.up.pt [INAF—Osservatorio Astronomico di Padova, Vicolo dellOsservatorio 5, Padova, I-35122 (Italy)

    2015-09-20

    We report on novel observations of HAT-P-1 aimed at constraining the optical transmission spectrum of the atmosphere of its transiting hot-Jupiter exoplanet. Ground-based differential spectrophotometry was performed over two transit windows using the DOLORES spectrograph at the Telescopio Nazionale Galileo. Our measurements imply an average planet to star radius ratio equal to R{sub p}/R{sub *} = (0.1159 ± 0.0005). This result is consistent with the value obtained from recent near-infrared measurements of this object, but differs from previously reported optical measurements, being lower by around 4.4 exoplanet scale heights. Analyzing the data over five different spectral bins of ∼600 Å wide, we observed a single peaked spectrum (3.7 σ level) with a blue cutoff corresponding to the blue edge of the broad absorption wing of sodium and an increased absorption in the region in-between 6180 and 7400 Å. We also infer that the width of the broad absorption wings due to alkali metals is likely narrower than the one implied by solar abundance clear atmospheric models. We interpret the result as evidence that HAT-P-1b has a partially clear atmosphere at optical wavelengths with a more modest contribution from an optical absorber than previously reported.

  13. The single crystal structure determination of Ln{sub 6}MnSb{sub 15} (Ln=La, Ce), Ln{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} (x∝0.5), and Ln{sub 6}ZnSb{sub 15} (Ln=La-Pr)

    Energy Technology Data Exchange (ETDEWEB)

    Benavides, Katherine A.; McCandless, Gregory T.; Chan, Julia Y. [Texas Univ., Dallas, Richardson, TX (United States). Dept. of Chemistry and Biochemistry

    2017-09-01

    Single crystals of Ln{sub 6}MnSb{sub 15} (Ln=La, Ce), Ln{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} (x∝0.5), and Ln{sub 6}ZnSb{sub 15} (Ln=La-Pr) have been successfully grown and the compounds adopt the orthorhombic Ln{sub 6}MnSb{sub 15} structure type (space group Immm), with a∝4.3 Aa, b∝15 Aa, and c∝19 Aa. This structure is comprised of antimony nets and antimony ribbons which exhibit positional disorder at connecting points between antimony substructures, in addition to two partially occupied transition metal sites. The unit cell volumes of the La analogs displayed a systematic decrease upon Zn substitution. However, for the Ce{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} and Pr{sub 6}Mn{sub 1-x}Zn{sub x}Sb{sub 15} (x∝0.5), the volumes deviate from linearity as observed in the parent compounds.

  14. Superconductivity in Zigzag CuO Chains

    Energy Technology Data Exchange (ETDEWEB)

    Berg, E.

    2010-04-06

    Superconductivity has recently been discovered in Pr{sub 2}Ba{sub 4}Cu{sub 7}O{sub 15-{delta}} with a maximum T{sub c} of about 15K. Since the CuO planes in this material are believed to be insulating, it has been proposed that the superconductivity occurs in the double (or zigzag) CuO chain layer. On phenomenological grounds we propose a theoretical interpretation of the experimental results in terms of a new phase for the zigzag chain, labelled by C{sub 1}S{sub 3/2}. This phase has a gap in the relative charge mode and a partial gap in the relative spin mode. It has gapless uniform charge and spin excitations and can have a divergent superconducting susceptibility, even for repulsive interactions. A microscopic model for the zigzag CuO chain is proposed, and on the basis of density matrix renormalization group (DMRG) and bosonization studies, we adduce evidence that supports our proposal.

  15. Structure and surface properties of praseodymium modified alumina

    Energy Technology Data Exchange (ETDEWEB)

    Tankov, I. [Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Pawelec, B. [Instituto de Catalisis y Petroleoquimica, CSIC, Cantoblanco, 28049 Madrid (Spain); Arishtirova, K. [Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Damyanova, S., E-mail: soniad@ic.bas.bg [Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)

    2011-10-15

    Mixed PrO{sub 2}-Al{sub 2}O{sub 3} oxides with different PrO{sub 2} content (1-20 wt.%) were prepared by wetness impregnation of {gamma}-alumina with aqueous solution of praseodymium nitrate. The samples were characterized by different techniques, using surface adsorption-desorption of N{sub 2} (S{sub BET}), thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), temperature-programmed reduction (TPR) and temperature-programmed desorption of CO{sub 2} (TPD-CO{sub 2}). TGA and XRD showed the presence of small praseodymium oxide species on the alumina surface. XPS and DRS detected electron deficient interaction between deposited praseodymium oxide and alumina. It was observed a lower reduction temperature for supported Pr oxide species compared to that of the bulk Pr{sub 6}O{sub 11}. TPD-CO{sub 2} studies suggested that the deposition of Pr oxide on alumina leaded to increase of the basicity of mixed oxides.

  16. X-ray induced insulator-metal transitions in CMR manganites

    Energy Technology Data Exchange (ETDEWEB)

    Kiryukhin, V.; Casa, D.; Keimer, B. [Princeton Univ., NJ (United States). Dept. of Physics; Hill, J.P.; Vigliante, A. [Brookhaven National Lab., Upton, NY (United States). Dept. of Physics; Tomioka, Y. [Joint Research Center for Atom Technology, Tsukuba, Ibaraki (Japan); Tokura, Y. [Joint Research Center for Atom Technology, Tsukuba, Ibaraki (Japan)]|[Univ. of Tokyo (Japan). Dept. of Applied Physics

    1997-12-01

    In this work the authors report a study of the photoinduced insulator-to-metal transition in manganese oxide perovskites of the formula Pr{sub 1{minus}x}Ca{sub x}MnO{sub 3}. The transition is closely related to the magnetic field induced insulator-to-metal transition (CMR effect) observed in these materials. It is accompanied by a dramatic change in the magnetic properties and lattice structure: the material changes from an insulating charge-ordered canted antiferromagnet to a ferromagnetic metal. The authors present an investigation of the transport and structural properties of these materials over the course of the transition (which usually takes about an hour to complete). The current-voltage characteristics exhibited by the material during the transition are highly nonlinear, indicating a large inhomogeneity of the transitional state. Possible practical applications of this novel type of transition are briefly discussed. They also report a high resolution X-ray diffraction study of the charge ordering in these materials. The temperature dependent charge ordering structure observed in these compounds is more complex than previously reported.

  17. Analysis of electrical and microstructural characteristics of a ZnO-based varistor doped with rare earth oxide; Analise das caracteristicas microestruturais e eletricas de um varistor a base de ZnO dopado com oxidos de terras raras

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, J.M. de; Dias, R.; Furtado, J.G. de M. [Centro de Pesquisas de Energia Eletrica (CEPEL), Rio de Janeiro, RJ (Brazil); Assuncao, F.C.R. [Pontificia Univ. Catolica do Rio de Janeiro (PUC/Rio), RJ (Brazil)

    2010-07-01

    Varistor is a semiconductor device, used in the protection of electrical systems, characterized to have a high no-linear electric resistance. Its properties are directly dependents of its chemical composition and microstructural characteristics. In this work were analyzed microstructural and electrical characteristics of a ZnO-based varistor doped with rare earth oxide, with chemical composition (mol%) 98,5.ZnO - 0,3.Pr{sub 6}O{sub 11} - 0,2.Dy{sub 2}O{sub 3} - 0,9.Co{sub 2}O{sub 3} - 0,1.Cr{sub 2}O{sub 3}. X-ray diffraction for phase characterization, scanning electron microscopy and energy dispersive X-ray spectroscopy were used for microstructural analysis. Measurement of average grain size and electrical and dielectric characteristics complete the characterization. The results show the formation of biphasic microstructure and with high densification, presenting relevant varistors characteristics but that would need improvements.(author)

  18. Measuring bandgap states in individual non-stoichiometric oxide nanoparticles using monochromated STEM EELS: The Praseodymium–ceria case

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, W.J. [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States); March, K. [Laboratoire de Physique des Solides, Université Paris-Sud, CNRS, UMR 8502, 91405 Orsay Cedex (France); Hernandez, C.A. [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States); Crozier, P.A., E-mail: crozier@asu.edu [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States)

    2016-08-15

    We describe a method to perform high spatial resolution measurement of the position and density of inter-band impurity states in non-stoichiometric oxides using ultra-high energy resolution electron energy-loss spectroscopy (EELS). This can be employed to study optical and electronic properties of atomic and nanoscale defects in electrically-conducting and optically-active oxides. We employ a monochromated scanning transmission electron microscope with subnanometer diameter electron probe, making this technique suitable for correlating spectroscopic information with high spatial resolution images from small objects such as nanoparticles, surfaces or interfaces. The specific experimental approach outlined here provides direct measurement of the Pr inter-band impurity states in Pr{sub 0.1}Ce{sub 0.9}O{sub 2−δ} via valence-loss EELS, which is interpreted with valence-loss spectral simulation based on density of states data to determine the energy level and character of the inter-band state. Additionally, observation of optical color change upon chemically-induced oxygen non-stoichiometry indicates that the population of the inter-band state is accompanied by an energy level shift within the bandgap. - Highlights: • Ultra-high energy resolution EELS used to study inter-band states in oxide. • Energy level and character of inter-band state determined from spectral model. • EELS coupled with optical color change indicates energy shift of inter-band state.

  19. Investigation of magnetic and transport properties of PrCa(MnCo)O prepared by solid state process

    Energy Technology Data Exchange (ETDEWEB)

    Khelifi, M. [Laboratoire de Physique des Matériaux et des Nanomatériaux appliquée à l’Environnement, Faculté des Sciences de Gabès cité Erriadh, Université de Gabès, 6079 Gabès (Tunisia); M’nassri, R. [Unité de recherche Matériaux Avancés et Nanotechnologies (URMAN), Institut Supérieur des Sciences Appliquées et de Technologie de Kasserine, Kairouan University, BP 471, Kasserine 1200 (Tunisia); Selmi, A. [Laboratory of Physics of Materials, Faculty of Sciences of Sfax, Sfax University, BP 1171, 3000 Sfax (Tunisia); Rahmouni, H., E-mail: rahmounihedi@yahoo.fr [Unité de recherche Matériaux Avancés et Nanotechnologies (URMAN), Institut Supérieur des Sciences Appliquées et de Technologie de Kasserine, Kairouan University, BP 471, Kasserine 1200 (Tunisia); Khirouni, K. [Laboratoire de Physique des Matériaux et des Nanomatériaux appliquée à l’Environnement, Faculté des Sciences de Gabès cité Erriadh, Université de Gabès, 6079 Gabès (Tunisia); and others

    2017-02-01

    Magnetic, magnetocaloric and electrical properties in distorted orthorhombic system Pr{sub 0.7}Ca{sub 0.3}Mn{sub 0.98}Co{sub 0.02}O{sub 3} has been studied. Complex impedance analysis confirms the contribution of grain boundary on the conduction process. The latter is dominated by thermally activated hopping mechanism. The sample exhibits two relaxations phenomena. Only one process persists at higher temperatures. Conductivity analysis indicates that the investigated compound exhibits a semiconductor behavior. The material reveals a dielectric transition and the experimental results are well fitted by Curie-Weiss law. The magnetic measurements show a clear paramagnetic–ferromagnetic transition with a large magnetic entropy change over a wide range of temperature. Furthermore, Banerjee's criteria and Landau theory of phase transitions are also studied to access magnetic ordering in the sample. A maximum magnetic entropy change increases from 0.5 to 2.18 J kg{sup −1} K{sup −1} when magnetic field rises from 1 T to 5 T. For the higher applied magnetic field, the material exhibits a high relative cooling power RCP=268.14 J/kg with a large temperature full-width at half maximum δ{sub TFWHM}=123 K.

  20. A reactive distillation process for the treatment of LiCl-KCl eutectic waste salt containing rare earth chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Eun, H.C., E-mail: ehc2004@kaeri.re.kr; Choi, J.H.; Kim, N.Y.; Lee, T.K.; Han, S.Y.; Lee, K.R.; Park, H.S.; Ahn, D.H.

    2016-11-15

    The pyrochemical process, which recovers useful resources (U/TRU metals) from used nuclear fuel using an electrochemical method, generates LiCl-KCl eutectic waste salt containing radioactive rare earth chlorides (RECl{sub 3}). It is necessary to develop a simple process for the treatment of LiCl-KCl eutectic waste salt in a hot-cell facility. For this reason, a reactive distillation process using a chemical agent was achieved as a method to separate rare earths from the LiCl-KCl waste salt. Before conducting the reactive distillation, thermodynamic equilibrium behaviors of the reactions between rare earth (Nd, La, Ce, Pr) chlorides and the chemical agent (K{sub 2}CO{sub 3}) were predicted using software. The addition of the chemical agent was determined to separate the rare earth chlorides into an oxide form using these equilibrium results. In the reactive distillation test, the rare earth chlorides in LiCl-KCl eutectic salt were decontaminated at a decontamination factor (DF) of more than 5000, and were mainly converted into oxide (Nd{sub 2}O{sub 3}, CeO{sub 2}, La{sub 2}O{sub 3}, Pr{sub 2}O{sub 3}) or oxychloride (LaOCl, PrOCl) forms. The LiCl-KCl was purified into a form with a very low concentration (<1 ppm) for the rare earth chlorides.

  1. RE{sub 2}B{sub 8}O{sub 15} (RE = La, Pr, Nd). Syntheses of three new rare earth borates isotypic to Ce{sub 2}B{sub 8}O{sub 15}

    Energy Technology Data Exchange (ETDEWEB)

    Glaetzle, Matthias; Hoerder, Gregor J.; Huppertz, Hubert [Innsbruck Univ. (Austria). Inst. fuer Allgemeine, Anorganische und Theoretische Chemie

    2016-08-01

    The rare earth borates RE{sub 2}B{sub 8}O{sub 15} (RE = La, Pr, Nd) were synthesized in a Walker-type multianvil apparatus under conditions of 5.5 GPa and 1100 C. Starting from the corresponding rare earth oxides and boron oxide, the syntheses yielded crystalline products of all new compounds that allowed crystal structure analyses based on single-crystal X-ray diffraction data for La{sub 2}B{sub 8}O{sub 15} and Nd{sub 2}B{sub 8}O{sub 15}. The compound Pr{sub 2}B{sub 8}O{sub 15} could be characterized via X-ray powder diffractometry. The results show that the new compounds crystallize isotypically to Ce{sub 2}B{sub 8}O{sub 15} in the monoclinic space group P2/c. The infrared spectra of RE{sub 2}B{sub 8}O{sub 15} (RE = La, Pr, Nd) have also been studied.

  2. Thermodynamics of spin ice in staggered and direct (along the [111] axis) fields in the cluster approximation

    Energy Technology Data Exchange (ETDEWEB)

    Zinenko, V. I., E-mail: zvi@iph.krasn.ru; Pavlovskii, M. S. [Russian Academy of Sciences, Kirensky Institute of Physics, Siberian Branch (Russian Federation)

    2017-02-15

    We have analyzed the low-temperature thermodynamic properties of spin ice in the staggered and direct (acting along the [111] axis) fields for rare-earth oxides with the chalcolamprite structure and general formula Re{sub 2}{sup 3+}Me{sub 2}{sup 4+}O{sub 7}{sup 2-}. Calculations have been performed in the cluster approximation. The results have been compared with experimental temperature dependences of heat capacity and entropy for Dy{sub 2}Ti{sub 2}O{sub 7} compound for different values of the external field in the [111] direction. The experimental data and calculated results have also been compared for the Pr{sub 2}Ru{sub 2}O{sub 7} compound with the antiferromagnetic ordering of magnetic moments of ruthenium ions, which gives rise to the staggered field acting on the system of rare-earth ions. The calculated temperature dependences of heat capacity and entropy are in good agreement with experimental data.

  3. Structural and electrical properties of T′-type Ln{sub 2}CuO{sub 4} (Ln = Pr, Nd, Sm, Eu and Gd) ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Salame, Paresh Hiralal [Department of Applied Physics, Laxminarayan Institute of Technology, RTM Nagpur University, Nagpur, INDIA paresh.salame@gmail.com (India)

    2016-05-23

    T′-type Ln{sub 2}CuO{sub 4} (Ln = Pr, Nd, Sm, Eu and Gd) were successfully synthesized in phase pure form using conventional solid state reaction and sintering route. For all the Ln{sub 2}CuO{sub 4} samples, the solid state reaction temperature was found to be 950 °C and pure phase was realized only after 2-3 intermediate milling and solid state reaction cycles, irrespective of the lanthanide ion radius. Effect of lanthanide ion contraction on the structural properties was clearly revealed by the powder X-ray diffraction, with the XRD peaks observed to be shifting towards higher 2θ values with the decrease in Ln ionic radii. The optimum sintering temperature of these solid state reacted Ln{sub 2}CuO{sub 4} powder was found to be 1100 °C except for Pr{sub 2}CuO{sub 4} powder. The conductivity of these samples were tested over a wide temperature range (−100 to 150 °C), an anomaly was observed in the conductivity of all the Ln{sub 2}CuO{sub 4} samples near the antiferromagnetic ordering temperature of Cu (~ 30 °C), thus suggesting the bearing of ordering of magnetic moments on the electrical properties.

  4. Dynamic and Thermal Turbulent Time Scale Modelling for Homogeneous Shear Flows

    Science.gov (United States)

    Schwab, John R.; Lakshminarayana, Budugur

    1994-01-01

    A new turbulence model, based upon dynamic and thermal turbulent time scale transport equations, is developed and applied to homogeneous shear flows with constant velocity and temperature gradients. The new model comprises transport equations for k, the turbulent kinetic energy; tau, the dynamic time scale; k(sub theta), the fluctuating temperature variance; and tau(sub theta), the thermal time scale. It offers conceptually parallel modeling of the dynamic and thermal turbulence at the two equation level, and eliminates the customary prescription of an empirical turbulent Prandtl number, Pr(sub t), thus permitting a more generalized prediction capability for turbulent heat transfer in complex flows and geometries. The new model also incorporates constitutive relations, based upon invariant theory, that allow the effects of nonequilibrium to modify the primary coefficients for the turbulent shear stress and heat flux. Predictions of the new model, along with those from two other similar models, are compared with experimental data for decaying homogeneous dynamic and thermal turbulence, homogeneous turbulence with constant temperature gradient, and homogeneous turbulence with constant temperature gradient and constant velocity gradient. The new model offers improvement in agreement with the data for most cases considered in this work, although it was no better than the other models for several cases where all the models performed poorly.

  5. Synthesis and Structural Characterization of Magnesium Based Coordination Networks in Different Solvents

    Energy Technology Data Exchange (ETDEWEB)

    D Banerjee; J Finkelstein; A Smirnov; P Forster; L Borkowski; S Teat; J Parise

    2011-12-31

    Three magnesium based metal-organic frameworks, Mg{sub 3}(3,5-PDC){sub 3}(DMF){sub 3} {center_dot} DMF [1], Mg(3,5-PDC)(H{sub 2}O) {center_dot} (H{sub 2}O) [3], and Mg{sub 4}(3,5-PDC){sub 4}(DMF){sub 2}(H{sub 2}O){sub 2} {center_dot} 2DMF {center_dot} 4.5H{sub 2}O [4], and a 2-D coordination polymer, [Mg(3,5-PDC)(H{sub 2}O){sub 2}] [2] [PDC = pyridinedicarboxylate], were synthesized using a combination of DMF, methanol, ethanol, and water. Compound 1 [space group P2{sub 1}/n, a = 12.3475(5) {angstrom}, b = 11.1929(5) {angstrom}, c = 28.6734(12) {angstrom}, {beta} = 98.8160(10){sup o}, V = 3916.0(3) {angstrom}{sup 3}] consists of a combination of isolated and corner-sharing magnesium octahedra connected by the organic linkers to form a 3-D network with a 12.2 {angstrom} x 4.6 {angstrom} 1-D channel. The channel contains coordinated and free DMF molecules. In compound 2 [space group C2/c, a = 9.964(5) {angstrom}, b = 12.0694(6) {angstrom}, c = 7.2763(4) {angstrom}, {beta} = 106.4970(6){sup o}, V = 836.70(6) {angstrom}{sup 3}], PDC connects isolated seven coordinated magnesium polyhedra into a layered structure. Compound 3 [space group P6{sub 1}22, a = 11.479(1) {angstrom}, c = 14.735(3) {angstrom}, V = 1681.7(4) {angstrom}{sup 3}] (previously reported) contains isolated magnesium octahedra connected by the organic linker with each other forming a 3D network. Compound 4 [space group P2{sub 1}/c, a = 13.7442(14) {angstrom}, b = 14.2887(15) {angstrom}, c = 14.1178(14) {angstrom}, {beta} = 104.912(2){sup o}, V = 2679.2(5) {angstrom}{sup 3}] also exhibits a 3D network based on isolated magnesium octahedra with square cavities containing both disordered DMF and water molecules. The structural topologies originate due to the variable coordination ability of solvent molecules with the metal center. Water molecules coordinate with the magnesium metal centers preferably over other polar solvents (DMF, methanol, ethanol) used to synthesize the coordination networks. Despite

  6. The structure of denisovite, a fibrous nanocrystalline polytypic disordered `very complex' silicate, studied by a synergistic multi-disciplinary approach employing methods of electron crystallography and X-ray powder diffraction

    Directory of Open Access Journals (Sweden)

    Ira V. Rozhdestvenskaya

    2017-05-01

    Full Text Available Denisovite is a rare mineral occurring as aggregates of fibres typically 200–500 nm diameter. It was confirmed as a new mineral in 1984, but important facts about its chemical formula, lattice parameters, symmetry and structure have remained incompletely known since then. Recently obtained results from studies using microprobe analysis, X-ray powder diffraction (XRPD, electron crystallography, modelling and Rietveld refinement will be reported. The electron crystallography methods include transmission electron microscopy (TEM, selected-area electron diffraction (SAED, high-angle annular dark-field imaging (HAADF, high-resolution transmission electron microscopy (HRTEM, precession electron diffraction (PED and electron diffraction tomography (EDT. A structural model of denisovite was developed from HAADF images and later completed on the basis of quasi-kinematic EDT data by ab initio structure solution using direct methods and least-squares refinement. The model was confirmed by Rietveld refinement. The lattice parameters are a = 31.024 (1, b = 19.554 (1 and c = 7.1441 (5 Å, β = 95.99 (3°, V = 4310.1 (5 Å3 and space group P12/a1. The structure consists of three topologically distinct dreier silicate chains, viz. two xonotlite-like dreier double chains, [Si6O17]10−, and a tubular loop-branched dreier triple chain, [Si12O30]12−. The silicate chains occur between three walls of edge-sharing (Ca,Na octahedra. The chains of silicate tetrahedra and the octahedra walls extend parallel to the z axis and form a layer parallel to (100. Water molecules and K+ cations are located at the centre of the tubular silicate chain. The latter also occupy positions close to the centres of eight-membered rings in the silicate chains. The silicate chains are geometrically constrained by neighbouring octahedra walls and present an ambiguity with respect to their z position along these walls, with displacements between neighbouring layers being

  7. Crystal Structure, Defects, Magnetic and Dielectric Properties of the Layered Bi3n+1Ti7Fe3n-3O9n+11 Perovskite-Anatase Intergrowths.

    Science.gov (United States)

    Batuk, Dmitry; Batuk, Maria; Filimonov, Dmitry S; Zakharov, Konstantin V; Volkova, Olga S; Vasiliev, Alexander N; Tyablikov, Oleg A; Hadermann, Joke; Abakumov, Artem M

    2017-01-17

    The Bi3n+1Ti7Fe3n-3O9n+11 materials are built of (001)p plane-parallel perovskite blocks with a thickness of n (Ti,Fe)O6 octahedra, separated by periodic translational interfaces. The interfaces are based on anatase-like chains of edge-sharing (Ti,Fe)O6 octahedra. Together with the octahedra of the perovskite blocks, they create S-shaped tunnels stabilized by lone pair Bi3+ cations. In this work, the structure of the n = 4-6 Bi3n+1Ti7Fe3n-3O9n+11 homologues is analyzed in detail using advanced transmission electron microscopy, powder X-ray diffraction, and Mössbauer spectroscopy. The connectivity of the anatase-like chains to the perovskite blocks results in a 3ap periodicity along the interfaces, so that they can be located either on top of each other or with shifts of ±ap along [100]p. The ordered arrangement of the interfaces gives rise to orthorhombic Immm and monoclinic A2/m polymorphs with the unit cell parameters a = 3ap, b = bp, c = 2(n + 1)cp and a = 3ap, b = bp, c = 2(n + 1)cp - ap, respectively. While the n = 3 compound is orthorhombic, the monoclinic modification is more favorable in higher homologues. The Bi3n+1Ti7Fe3n-3O9n+11 structures demonstrate intricate patterns of atomic displacements in the perovskite blocks, which are supported by the stereochemical activity of the Bi3+ cations. These patterns are coupled to the cationic coordination of the oxygen atoms in the (Ti,Fe)O2 layers at the border of the perovskite blocks. The coupling is strong in the n = 3, 4 homologues, but gradually reduces with the increasing thickness of the perovskite blocks, so that, in the n = 6 compound, the dominant mode of atomic displacements is aligned along the interface planes. The displacements in the adjacent perovskite blocks tend to order antiparallel, resulting in an overall antipolar structure. The Bi3n+1Ti7Fe3n-3O9n+11 materials demonstrate an unusual diversity of structure defects. The n = 4-6 homologues are robust antiferromagnets below TN = 135, 220, and

  8. CsSc{sub 3}F{sub 6}[SeO{sub 3}]{sub 2}. A new rare-earth metal(III) fluoride oxoselenate(IV) with sections of the ReO{sub 3}-type structure

    Energy Technology Data Exchange (ETDEWEB)

    Greiner, Stefan; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart (Germany)

    2017-09-04

    A new representative of rare-earth metal(III) fluoride oxoselenates(IV) derivatized with alkali metals could be synthesized via solid-state reactions. Colorless single crystals of CsSc{sub 3}F{sub 6}[SeO{sub 3}]{sub 2} were obtained through the reaction of Sc{sub 2}O{sub 3}, ScF{sub 3}, and SeO{sub 2} (molar ratio 1:1:3) with CsBr as reactant and fluxing agent. For this purpose, corundum crucibles embedded as liners into evacuated silica ampoules were applied as containers for these reactions at 700 C for seven days. The new quintenary compound crystallizes in the trigonal space group P3m1 with a = 565.34(4) and c = 1069.87(8) pm (c/a = 1.892) for Z = 1. The crystal structure of CsSc{sub 3}F{sub 6}[SeO{sub 3}]{sub 2} contains two crystallographically different Sc{sup 3+} cations. Each (Sc1){sup 3+} is surrounded by six fluoride anions as octahedron, while the octahedra about (Sc2){sup 3+} are formed by three fluoride anions and three oxygen atoms from three terminal [SeO{sub 3}]{sup 2-} anions. The [(Sc1)F{sub 6}]{sup 3-} octahedra link via common F{sup -} vertices to six fac-[(Sc2)F{sub 3}O{sub 3}]{sup 6-} octahedra forming {sup 2}{sub ∞}{[Sc_3F_6O_6]"9"-} layers parallel to (001). These layers are separated by oxygen-coordinated Cs{sup +} cations (C.N. = 12), arranging for the charge compensation, while Se{sup 4+} cations within the layers surrounded by three oxygen atoms as ψ{sup 1}-tetrahedral [SeO{sub 3}]{sup 2-} units complete the structure. EDX measurements confirmed the composition of the title compound and single-crystal Raman studies showed the typical vibrational modes of isolated [SeO{sub 3}]{sup 2-} anions with ideal C{sub 3v} symmetry. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Density-functional computation of 99Ru NMR parameters

    Science.gov (United States)

    Buhl; Gaemers; Elsevier

    2000-09-01

    Gradient-corrected and hybrid variants of density-functional theory are used to compute the geometries and 99Ru chemical shifts of RuO4, [RuCp2], [K4Ru(CN)6], [Ru3(CO)12], [Ru(CO)3X3]- (X=Cl, I), [Ru(CO)2Cl4]2-, [Ru(bipy)3]2+, and [Ru(CO)2(iPr-DAB)(X)(Y)] [XY= Cl2, I2, MeCl, MeI, or (SnMe3)2]. For this set of compounds, substituent effects on delta(99Ru) are somewhat underestimated with the BPW91 pure density functional but are described well by the B3LYP hybrid functional, which can also be used to reproduce empirical trends in electric field gradients (EFGs) at the Ru nucleus qualitatively. In the [Ru(CO)2(iPr-DAB)XY] series, trends in the computed EFGs parallel those in the observed 99Ru NMR linewidths, in accordance with the quadrupolar relaxation mechanism expected for this nucleus. For this series of compounds, the use of X-ray-derived geometries affords a worse correlation between calculated EFGs and experimental linewidths than does the use of optimized geometries.

  10. Fast photoinduced electron transfer through DNA intercalation.

    Science.gov (United States)

    Murphy, C J; Arkin, M R; Ghatlia, N D; Bossmann, S; Turro, N J; Barton, J K

    1994-06-07

    We report evidence for fast photoinduced electron transfer mediated by the DNA helix that requires metal complexes that are avid intercalators of DNA. Here the donor bis(phenanthroline)(dipyridophenazine)ruthenium(II) [Ru(phen)2dppz2+] and acceptor bis(9,10-phenanthrenequinone diimine)(phenanthroline)rhodium(III) [Rh(phi)2phen3+] intercalate into DNA with Kb > 10(6) M-1. Luminescence quenching experiments in the presence of two different lengths of DNA yield upward-curving Stern-Volmer plots and the loss of luminescence intensity far exceeds the change in emission lifetimes. In the presence of a nonintercalative electron acceptor, Ru(NH3)3+(6), Ru(phen)2dppz2+ luminescence is quenched much less efficiently compared to that found for the intercalative Rh(phi)2phen3+ quencher and follows linear Stern-Volmer kinetics; steady-state and time-resolved Stern-Volmer plots are comparable in scale. These experiments are consistent with a model involving fast long-range electron transfer between intercalators through the DNA helix.

  11. Interaction of ferrocene appended Ru(II), Rh(III) and Ir(III) dipyrrinato complexes with DNA/protein, molecular docking and antitumor activity.

    Science.gov (United States)

    Paitandi, Rajendra Prasad; Gupta, Rakesh Kumar; Singh, Roop Shikha; Sharma, Gunjan; Koch, Biplob; Pandey, Daya Shankar

    2014-09-12

    Efficacy of the ferrocene appended piano-stool dipyrrinato complexes [(η(6)-C6H6)RuCl(fcdpm)] (1), [(η(6)-C10H14)RuCl(fcdpm)] (2), [(η(6)-C12H18)RuCl(fcdpm)] (3) [(η(5)-C5Me5)RhCl(fcdpm)] (4) and [(η(5)-C5Me5)IrCl(fcdpm)] (5) [fcdpm = 5-ferrocenyldipyrromethene] toward anticancer activity have been described. Binding of the complexes with calf thymus DNA (CT-DNA) and BSA (bovine serum albumin) have been thoroughly investigated by UV-Vis and fluorescence spectroscopy. Binding constants for 1-5 (range, 10(4)-10(5) M(-1)) validated their efficient binding with CT-DNA. Molecular docking studies revealed interaction through minor groove of the DNA, on the other hand these also interact through hydrophobic residues of the protein, particularly cavity in the subdomain IIA. In vitro anticancer activity have been scrutinized by MTT assay, acridine orange/ethidium bromide (AO/EtBr) fluorescence staining, and DNA ladder (fragmentation) assay against Dalton's Lymphoma (DL) cells. Present study revealed that rhodium complex (4) is more effective relative to ruthenium (1-3) and iridium (5) complexes. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  12. Searching for new chemotherapies for tropical diseases: ruthenium-clotrimazole complexes display high in vitro activity against Leishmania major and Trypanosoma cruzi and low toxicity toward normal mammalian cells.

    Science.gov (United States)

    Martínez, Alberto; Carreon, Teresia; Iniguez, Eva; Anzellotti, Atilio; Sánchez, Antonio; Tyan, Marina; Sattler, Aaron; Herrera, Linda; Maldonado, Rosa A; Sánchez-Delgado, Roberto A

    2012-04-26

    Eight new ruthenium complexes of clotrimazole (CTZ) with high antiparasitic activity have been synthesized, cis,fac-[Ru(II)Cl(2)(DMSO)(3)(CTZ)] (1), cis,cis,trans-[Ru(II)Cl(2)(DMSO)(2)(CTZ)(2)] (2), Na[Ru(III)Cl(4)(DMSO)(CTZ)] (3), Na[trans-Ru(III)Cl(4)(CTZ)(2)] (4), [Ru(II)(η(6)-p-cymene)Cl(2)(CTZ)] (5), [Ru(II)(η(6)-p-cymene)(bipy)(CTZ)][BF(4)](2) (6), [Ru(II)(η(6)-p-cymene)(en)(CTZ)][BF(4)](2) (7), and [Ru(II)(η(6)-p-cymene)(acac)(CTZ)][BF(4)] (8) (bipy = bipyridine; en = ethlylenediamine; acac = acetylacetonate). The crystal structures of compounds 4-8 are described. Complexes 1-8 are active against promastigotes of Leishmania major and epimastigotes of Trypanosoma cruzi. Most notably, complex 5 increases the activity of CTZ by factors of 110 and 58 against L. major and T. cruzi, with no appreciable toxicity to human osteoblasts, resulting in nanomolar and low micromolar lethal doses and therapeutic indexes of 500 and 75, respectively. In a high-content imaging assay on L. major-infected intraperitoneal mice macrophages, complex 5 showed significant inhibition on the proliferation of intracellular amastigotes (IC(70) = 29 nM), while complex 8 displayed some effect at a higher concentration (IC(40) = 1 μM).

  13. Mass spectrometry quantification of hydrogen produced under illumination of p-CuInSe{sub 2} and modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Valverde, S.; Ordonez-Regil, E.; Valencia-Alvarado, R. [Gerencia de Ciencias Basicas, Instituto Nacional de Investigaciones Nucleares, Mexico D.F. (Mexico); Rivera-Noriega, R.; Solorza-Feria, O. [Depto de Quimica, CINVESTAV-IPN, Mexico D.F. (Mexico)

    1997-12-31

    Hydrogen gas obtained from illuminated p-CuInSe{sub 2} (CIS) on 0.5 M sulfuric acid solution was collected in a glass balloon using argon as carrier gas, and quantified with a mass spectrometer. p-CulSe{sub 2} thin films were electrodeposited on SnO{sub 2}-coated glass plates, according to references already reported. Electrochemical deposition of Se and chemical modifications on the semiconducting surfaces with adsorbed ruthenium were also tested for the hydrogen evolution reaction. The E{sub g} and E{sub tb} of the modified p-CulnSe{sub 2} were determined. Atomic absorption spectrometry was used to quantify the chemical compositions of the semiconductors before and after the illumination. The modified semiconductors had a composition of CIS/Se{sub 24} and CIS/Se{sub 6}/ (RuO{sub 4}){sub 0.12}, under illumination at 0.8 V in 0.5 M H{sub 2}SO{sub 4} for 4 min, the volumes of evolved hydrogen were 1 cm{sup 3}, and 2.4cm{sub 4}, respectively. (Author)

  14. X-ray absorption spectroscopy for characterisation of catalysts for PEM fuel cells; Roentgenabsorptionsspektroskopie zur Charakterisierung von Katalysatoren fuer die PEM-Brennstoffzelle

    Energy Technology Data Exchange (ETDEWEB)

    Koehl, G.

    2001-10-01

    The investigation of bimetallic nanoparticles is of great interest for the development of powerful anode catalysts in PEM fuel cells. The determination of their electronic and geometric structure is crucial for the optimization of the activity and selectivity in the fuel cell. Especially carbon supported PtRu particles have shown superior activity as anode catalysts due to their high CO tolerance. To state the reason on an atomic level, X-ray absorption spectroscopy (XAS) with synchrotron radiation has been used to examine several Pt and PtRu nanoparticle systems. They were either prepared on the basis of preformed PtRu alloy colloids stabilized by different surfactants or by chemical reduction of precursors, Na{sub 6}Pt(SO{sub 3}){sub 4} and Na{sub 6}Ru(SO{sub 3}){sub 4}. Although a PtRu interaction was observed in all systems, a nonstatistical distribution of Pt and Ru atoms in the nanoparticles could be verified. In additional investigations the reaction mechanism during the synthesis of an organometallic stabilized Pt colloid was examined. In-situ measurements revealed the formation of an hitherto unknown Pt complex as intermediate state prior to the nucleation of the particles. (orig)

  15. Phase transition in the Ruddlesden-Popper layered perovskite Li 2SrTa 2O 7

    Science.gov (United States)

    Pagnier, T.; Rosman, N.; Galven, C.; Suard, E.; Fourquet, J. L.; Le Berre, F.; Crosnier-Lopez, M. P.

    2009-02-01

    The crystal structure of the Ruddlesden-Popper layered perovskite Li 2SrTa 2O 7 has been characterized at various temperatures between -185 and 300 °C by several techniques: X-ray and neutron powder diffraction, single crystal diffraction, transmission electron microscopy and Raman spectroscopy. The low temperature structure has been confirmed to be orthorhombic Cmcm with a small octahedra antiphase tilting ( ΦΦ0) ( ΦΦ0) inside the perovskite blocks. With temperature, the tilting progressively vanishes leading around 230 °C to a tetragonal symmetry (S.G. I4/ mmm). This reversible phase transition, followed by X-ray and neutron thermodiffraction and thermal Raman measurements, is considered as of second order. An attribution of the Raman bands based on normal mode analysis is proposed.

  16. Dynamics of antiferroelectric phase transition in PbZrO3

    Science.gov (United States)

    Fthenakis, Z. G.; Ponomareva, I.

    2017-11-01

    The dynamics of the phase transition in antiferroelectric PbZrO3 which is the subject of a decades-long debate, is examined using first-principles-based simulations. This is achieved through the development of a computational approach that allows calculations of generalized complex susceptibilities at an arbitrary point of the Brillouin zone. Application of this approach to the case of PbZrO3 predicts the temperature evolution of many of its lattice modes, some of which remain elusive or even "invisible" in experiments. The computational data suggest that two lattice modes are primarily responsible for the antiferroelectric phase transition in this material: the one associated with oxygen octahedra tilts dynamics and the other due to lead ions antipolar vibrations.

  17. Raman spectroscopic studies of lithium manganates with spinel structure

    CERN Document Server

    Julien, C M

    2003-01-01

    Raman scattering spectra of a set of lithium manganospinels Li sub 1 sub - sub x sub + sub z Mn sub 2 sub - sub z O sub 4 with 0 sup<= x sup<= 1 and 0 sup<= z sup<= 0.33 are reported and analysed. Structural changes have been investigated following the evolution of Raman spectra with the concentration of lithium cations. The local structure was characterized as a function of the mean oxidation state of manganese cations. The trigonal distortion of MnO sub 6 octahedra is evidenced by insertion of lithium ions into the [B sub 2]O sub 4 spinel framework. A comparison with tetragonal Mn sub 3 O sub 4 and Fe sub 3 O sub 4 spinels shows the influence of the Jahn-Teller effect on the Raman features for this class of materials.

  18. Cliftonite: A proposed origin, and its bearing on the origin of diamonds in meteorites

    Science.gov (United States)

    Brett, R.; Higgins, G.T.

    1969-01-01

    Cliftonite, a polycrystalline aggregate of graphite with spherulitic structure and cubic morphology, is known in 14 meteorites. Some workers have considered it to be a pseudomorph after diamond, and have used the proposed diamond ancestry as evidence of a meteoritic parent body of at least lunar dimensions. Careful examination of meteoritic samples indicates that cliftonite forms by precipitation within kamacite. We have also demonstrated that graphite with cubic morphology may be synthesized in a Fe-Ni-C alloy annealed in a vacuum. We therefore suggest that a high pressure origin is unnecessary for meteorities which contain cliftonite, and that these meteorities were formed at low pressures. This conclusion is in agreement with other recent evidence. We also suggest that recently discovered cubes and cubo-octahedra of lonsdaleite in the Canyon Diablo meteorite are pseudomorphs after cliftonite, not diamond, as has previously been suggested. ?? 1969.

  19. Trends in (LaMnO3)n/(SrTiO3)m superlattices with varying layer thicknesses

    KAUST Repository

    Jilili, J.

    2015-09-01

    We investigate the thickness dependence of the structural, electronic, and magnetic properties of (LaMnO3)n/(SrTiO3)m (n, m = 2, 4, 6, 8) superlattices using density functional theory. The electronic structure turns out to be highly sensitive to the onsite Coulomb interaction. In contrast to bulk SrTiO3, strongly distorted O octahedra are observed in the SrTiO3 layers with a systematic off centering of the Ti atoms. The systems favour ferromagnetic spin ordering rather than the antiferromagnetic spin ordering of bulk LaMnO3 and all show half-metallicity, while a systematic reduction of the minority spin band gaps as a function of the LaMnO3 and SrTiO3 layer thicknesses originates from modifications of the Ti dxy states.

  20. RbCuFe(PO42

    Directory of Open Access Journals (Sweden)

    Mongi Ben Amara

    2013-08-01

    Full Text Available A new iron phosphate, rubidium copper(II iron(III bis(phosphate, RbCuFe(PO42, has been synthesized as single crystals by the flux method. This compound is isostructural with KCuFe(PO42 [Badri et al. (2011, J. Solid State Chem. 184, 937–944]. Its structure is built up from Cu2O8 units of edge-sharing CuO5 polyhedra, interconnected by FeO6 octahedra through common corners to form undulating chains that extend infinitely along the [011] and [01-1] directions. The linkage of such chains is ensured by the PO4 tetraedra and the resulting three-dimensional framework forms quasi-elliptic tunnels parallel to the [101] direction in which the Rb+ cations are located.

  1. Rietveld refinement of the langbeinite-type mixed-metal phosphate K2Ni0.5Zr1.5(PO43

    Directory of Open Access Journals (Sweden)

    Igor V. Zatovsky

    2014-07-01

    Full Text Available Dipotassium [nickel(II zirconium(IV] tris(orthophosphate was prepared from a self-flux in the system K2O–P2O5–NiO–K2ZrF6. The title compound belongs to the langbeinite family and is built up from two [MO6] octahedra [M = Ni:Zr with mixed occupancy in ratios of 0.21 (4:0.79 (4 and 0.29 (4:0.71 (4, respectively] and [PO4] tetrahedra interlinked via vertices into a 3∞[M2(PO43] framework. Two independent K+ cations are located in large cavities of the framework, with coordination numbers to O2− anions of nine and twelve. The K, Ni, and Zr sites are located on threefold rotation axes.

  2. Untilting BiFeO3: The influence of substrate boundary conditions in ultra-thin BiFeO3 on SrTiO3

    Directory of Open Access Journals (Sweden)

    Yongsoo Yang

    2013-11-01

    Full Text Available We report on the role of oxygen octahedral tilting in the monoclinic-to-tetragonal phase transition in ultra-thin BiFeO3 films grown on (001 SrTiO3 substrates. Reciprocal space maps clearly show the disappearance of the integer-order Bragg peak splitting associated with the monoclinic phase when the film thickness decreases below 20 unit cells. This monoclinic-to-tetragonal transition is accompanied by the evolution of the half-order diffraction peaks, which reflects untilting of the oxygen octahedra around the [110] axis, proving that the octahedral tilting is closely correlated with the transition. This structural change is thickness-dependent, and different from a strain-induced transition in the conventional sense.

  3. Zn(1.86)Cd(0.14)(OH)VO(4).

    Science.gov (United States)

    Dorđević, Tamara; Stojanović, Jovica; Karanović, Ljiljana

    2010-11-10

    The title compound, dizinc cadmium hydroxide tetraoxido-vanadate, Zn(1.86)Cd(0.14)(OH)VO(4), was prepared under low-temperature hydro-thermal conditions. It is isostructural with Zn(2)(OH)VO(4) and Cu(2)(OH)VO(4). In the crystal structure, chains of edge-sharing [ZnO(6)] octahedra are inter-connected by VO(4) tetra-hedra (site symmetries of both V atoms and their coordination polyhedra are .m.) to form a three-dimensional [Zn(OH)VO(4)](2-) framework with channels occupied by Zn and Zn/Cd cations adopting trigonal-bipyramidal and distorted octa-hedral coordinations, respectively. Zn(1.86)Cd(0.14)(OH)VO(4) is topologically related to adamite-type phases, and descloizite- and tsumcorite-type structures.

  4. Rietveld refinement of KLaTiO4 from X-ray powder data

    Directory of Open Access Journals (Sweden)

    Bai-Chuan Zhu

    2011-04-01

    Full Text Available Potassium lanthanum titanate(IV, KLaTiO4, has been synthesized by conventional solid-state reaction. It crystallizes isotypically with the NaLnTiO4 (Ln = La, Pr, Nd, Sm, Eu, Gd, Y and Lu family. Five of the six atoms in the asymmetric unit (one K, one La, one Ti and two O atoms are situated on sites with 4mm symmetry, whereas one O atom has 2mm. site symmetry. The crystal structure can be described as being composed of single layers of distorted corner-sharing TiO6 octahedra extending parallel to (001. The layers are alternately separated by K+ and La3+ cations along [001]. The coordination number of both K+ and La3+ cations is nine, resulting in distorted KO9 and LaO9 polyhedra.

  5. Spectroscopy of La0.5Sr1.5MnO4 orbital ordering: a cluster many-body calculation

    Science.gov (United States)

    Mirone, A.; Dhesi, S. S.; van der Laan, G.

    2006-09-01

    Orbital ordering (OO) in La0.5Sr1.5MnO4 has been studied using soft X-ray resonant diffraction (SXRD) at the Mn L2,3 edges in combination with many-body cluster calculations. The SXRD intensity is modelled in second quantization using a small planar cluster consisting of a central active Mn site with first-neighbour shells comprising O and Mn sites. The effective Hamiltonian includes Slater-Koster parameters and charge transfer and electron correlation energies obtained from previous measurements on manganites. The energy dependence of the SXRD OO peak is calculated using the Jahn-Teller distortions of the oxygen octahedra and in-plane spin correlations as adjustable parameters. These contributions are clearly distinguished above the Néel temperature with a good spectroscopic agreement. The results also suggest a significant charge separation between the Mn sites.

  6. High mobility half-metallicity in the (LaMnO3)2/(SrTiO3)8 superlattice

    Science.gov (United States)

    Cossu, F.; Singh, N.; Schwingenschlögl, U.

    2013-01-01

    First principles calculations have been performed to investigate the LaMnO3/SrTiO3 superlattice. Structural relaxation within the generalized gradient approximation results in no significant tiltings or rotations of oxygen octahedra, but in distinct distortions in the SrTiO3 region. Taking into account the onsite Coulomb interaction, we find that the Mn spins order ferromagnetically, in contrast to the antiferromagnetic state of bulk LaMnO3. Most importantly, the interface strain combined with charge transfer across the interface induces half-metallicity within the MnO2 layers. The superlattice is particulary interesting for spintronics applications because the half-metallic states are characterized by an extraordinary high mobility.

  7. Doping a dipole into an incipient ferroelectric: Route to relaxor ferroelectrics

    Science.gov (United States)

    Chaudhary, N. Vijay Prakash; Sarkar, Sagar; Sharma, Neetika; Kundu, Asish K.; Menon, Krishnakumar S. R.; Das, A.; Mahadevan, Priya; Venimadhav, A.

    2017-07-01

    Ti O2 in the rutile phase is known to be an incipient ferroelectric. Considering Nb-Cr codoping we examine if ferroelectricity can be induced at the low doping limit in T i(1 -x )(Nb0.5Cr0.5 ) xO2 (x =0.05 % , 1%, 5%, and 10%). A relaxor behavior is found in the temperature range 20-120 K which obeys the Vogel-Fulcher relation while pyrocurrent measurements confirm switching of the electric polarization. The spontaneous net polarization is doping dependent with a maximum at 1% and for doping concentrations above 5% is found to be paraelectric. Ab initio density functional theory based calculations suggest that the Nb-Cr pair behaves like a dipole and polarizes the neighboring Ti O6 octahedra, stabilizing a ferroelectric ground state akin to magnetic impurities in dilute magnetic semiconductors. At larger doping concentrations one finds that Nb-Cr clusters result in a vanishing polarization.

  8. Crystal structure of the mixed-metal trisulfide BaCu1/3Ta2/3S3

    Directory of Open Access Journals (Sweden)

    Kejun Bu

    2017-05-01

    Full Text Available The mixed-metal title compound, BaCu1/3Ta2/3S3 [barium copper(II tantalum(V trisulfide], was prepared through solid-state reactions. The crystal structure adopts the BaTaS3 structure type and consists of face-sharing [MS6] (M = Ta,Cu octahedra (point-group symmetry -3m. that are condensed into infinite chains along [001]. Adjacent chains are linked through the barium cations (site symmetry -6m2, which exhibit a coordination number of twelve. The M site is occupied by 2/3 of TaV and 1/3 of CuII, whereby the average M—S distances are slightly longer than those of ordered BaTaS3. The classical charge balance of the title compound can be represented by [Ba2+] [(Ta/Cu4+] [S2−]3.

  9. Cs10Ta29.27O78

    Directory of Open Access Journals (Sweden)

    Wolfgang Schnick

    2009-02-01

    Full Text Available Single crystals of caesium tantalate(V, Cs10Ta29.27O78, were obtained as a serendipitous product in a welded tantalum ampoule by a blank reaction of CsBr and bismuth subnitrate [Bi5O(OH9(NO34] with the container material. The crystal structure of the title compound is made up of a three-dimensional framework constituted by two types of layers, viz. (Ta6O15n and (Ta3O9n, parallel to (001, which are linked together by TaO6 octahedra (3m. symmetry along [001]. This framework has cavities where three independent Cs+ ions (3m. and overline{6}m2 symmetry, respectively are located. The compound reveals a Ta deficiency at one trigonal prismatic coordinated site (overline{6}m2 symmetry. The composition of the title compound was verified by energy-dispersive X-ray analysis of single crystals.

  10. Di-μ-chromato-κ4O:O′-bis[bis(phenanthroline-κ2N,N′cadmium(II] dihydrate

    Directory of Open Access Journals (Sweden)

    Hai-Xing Liu

    2009-04-01

    Full Text Available In the title compound, [Cd2Cr2O8(C12H8N24]·2H2O, which was obtained by hydrothermal reaction of CdCO3 and phenanthroline with K2CrO4 at 393 K, two distorted Cd(N4O2 octahedra are linked through μ2-bridging chromate anions, forming a centrosymmetric tetranuclear eight-membered ring complex. The water molecules link the chromate O atoms via intermolecular O—H...O hydrogen bonds. These aggregates pack to a three-dimensional network through weak intermolecular C—H...O and C—H...π hydrogen-bonding contacts.

  11. Synthesis, characterization, and chemical bonding analysis of the lithium alkaline-earth metal gallide nitrides Li{sub 2}(Ca{sub 3}N){sub 2}[Ga{sub 4}] and Li{sub 2}(Sr{sub 3}N){sub 2}[Ga{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Pathak, Manisha; Bobnar, Matej; Ormeci, Alim; Hoehn, Peter [Chemische Metallkunde, Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Stoiber, Dominik; Niewa, Rainer [Institut fuer Anorganische Chemie, Universitaet Stuttgart (Germany); Ovchinnikov, Alexander [Chemische Metallkunde, Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Department of Chemistry and Biochemistry, University of Delaware, Newark, DE (United States)

    2017-11-17

    Large single crystals of Li{sub 2}(Ca{sub 3}N){sub 2}[Ga{sub 4}] and Li{sub 2}(Sr{sub 3}N){sub 2}[Ga{sub 4}] up to several mm in size were grown from mixtures of the respective elements and binary alkaline-earth metal nitrides in reactive lithium melts employing a modified high-temperature centrifugation-aided filtration (HTCAF) technique. The main structural features of these isotypic phases are stella quadrangula building units [Ga{sub 4}]Li{sub 4/2} and octahedra (Nae{sub 6/2}), which form two independent interpenetrating networks. The phases crystallize in the η-carbide structure and represent diamagnetic small bandgap semiconductors. Real-space chemical bonding analysis indicates predominantly ionic bonding. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Synthesis and single crystal X-ray structure of the tetragonal tungsten bronze Pb{sub 0.91}K{sub 1.72}Li{sub 1.46}Nb{sub 5}O{sub 15}

    Energy Technology Data Exchange (ETDEWEB)

    Capitelli, F. [Institute of Crystallography - CNR, Via Salaria Km 29.300, 00016 Monterotondo Rome (Italy); Rossi, M. [Earth Sciences Department, Federico II University, Via Mezzocannone 8, 80134 Naples (Italy); Elaatmani, M.; Zegzouti, A. [Laboratoire de Chimie du Solide Mineral, Faculte des Sciences Semlalia, Universite Cadi Ayyad, Marrakech (Morocco)

    2010-11-15

    Crystals of Pb{sub 0.91}K{sub 1.72}Li{sub 1.46}Nb{sub 5}O{sub 15}, belonging to tetragonal tungsten bronze materials, were grown by the slow cooling technique, and characterized by means of single crystal X-ray diffraction: the structure was solved in the P4bm tetragonal space group, with the following unit cell parameters: a = 12.548(5), c = 4.042(5)A, V = 636.4(9)A{sup 3}. The three-dimensional framework can be described as a layered structure down crystallographic axis c, with arrays of NbO{sub 6} octahedra, whose corner sharing makes up the formation of tunnels filled up by Li, Pb and K displaying complex cation-oxygen coordinations. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  13. Rietveld refinement of langbeinite-type K2YHf(PO43

    Directory of Open Access Journals (Sweden)

    Nikolay S. Slobodyanik

    2009-08-01

    Full Text Available Potassium yttrium hafnium tris(orthophosphate belongs to the langbeinite-family and is built up from [MO6] octahedra [in which the positions of the two independent M sites are mutually occupied by Y and Hf in a 0.605 (10:0.395 (10 ratio] and [PO4] tetrahedra connected via vertices into a three-dimensional framework. This framework is penetrated by large closed cavities in which the two independent K atoms are located; one of the K atoms is nine-coordinated and the other is 12-coordinated by surrounding O atoms. The K, Y and Hf atoms lie on threefold rotation axes, whereas the P and O atoms are located in general positions.

  14. A double salt of iodobismuthate: cis-aquaiodidobis(1,10-phenanthrolinecobalt(II tris(1,10-phenanthrolinecobalt(II trans-hexa-μ2-iodido-hexaiodidotribismuthate(III

    Directory of Open Access Journals (Sweden)

    Jiongke Chen

    2011-09-01

    Full Text Available In the title complex, [Co(C12H8N23][CoI(C12H8N22(H2O][Bi3I12], conventionally abbreviated [Co(phen3][CoI(phen2(H2O][Bi3I12], where phen is 1,10-phenanthroline, the CoII atom in one cation is coordinated by six N atoms from three phen ligands in an octahedral coordination while the CoII atom in the other cation is coordinated octahedrally by four N atoms from two phen ligands, one water O atom and one I atom. In the anion, three BiIII ions adopt an octahedral coordination constructed by six I− ligands. The three BiI6 octahedra are fused together through trans face-sharing.

  15. Local structure analysis of NaNbO3 and AgNbO3 modified by Li substitution

    Science.gov (United States)

    Yoneda, Yasuhiro; Aoyagi, Rintaro; Fu, Desheng

    2016-10-01

    We analyzed the local structures of NaNbO3 and AgNbO3 by combining the X-ray absorption fine structure (XAFS) and atomic pair-distribution function (PDF) techniques. NaNbO3 is known to be an antiferroelectric material at room temperature. It also undergoes a diffuse phase transition, in which orthorhombic and rhombohedral phases coexist over a wide temperature range. We found a disordered feature in the nearest-neighbor bond distance corresponding to the Nb-O bonds. The disordered bond distribution disappeared when Li was substituted for Na. A similar disorder feature was found in AgNbO3. The disordered site can be specified by combining XAFS and PDF techniques. The sequences of disordered and complex phase transitions are attributable to the competition between the tolerance of the AO12 cage and the tilt of NbO6 octahedra.

  16. Optical properties of Pb2 -based aggregated phases in CsBr Thin film and single crystal matrices

    Science.gov (United States)

    Nikl, M.; Nitsch, K.; Mihokova, E.; Polak, K.; Fabeni, P.; Pazzi, G. P.; Gurioli, M.; Phani, R.; Santucci, S.; Scacco, A.; Somma, F.

    Emission characteristics of CsPbBr3 and Cs4PbBr6 aggregates in CsBr bulk and thin film matrices are reported. The emission of the former aggregated phase is peaking about 520-560 nm. It shows small Stokes shift (50 meV) related to narrow free exciton emission line of sub-nanosecond decay times. Quantum size effect was evidenced for the aggregates of 6-7 nm in diameter. The Cs4PbBr6 aggregates show emission peak at 375 nm and overall emission characteristics are similar to those of KBr: Pb, which is explained by very close local arrangement of emission centres-(PbBr6)4- octahedra-in both structures.

  17. Postsynthesis Transformation of Insulating Cs4PbBr6 Nanocrystals into Bright Perovskite CsPbBr3 through Physical and Chemical Extraction of CsBr

    Science.gov (United States)

    2017-01-01

    Perovskite-related Cs4PbBr6 nanocrystals present a “zero-dimensional” crystalline structure where adjacent [PbBr6]4– octahedra do not share any corners. We show in this work that these nanocrystals can be converted into “three-dimensional” CsPbBr3 perovskites by extraction of CsBr. This conversion drastically changes the optoelectronic properties of the nanocrystals that become highly photoluminescent. The extraction of CsBr can be achieved either by thermal annealing (physical approach) or by chemical reaction with Prussian Blue (chemical approach). The former approach can be simply carried out on a dried film without addition of any chemicals but does not yield a full transformation. Instead, reaction with Prussian Blue in solution achieves a full transformation into the perovskite phase. This transformation was also verified on the iodide counterpart (Cs4PbI6). PMID:29285525

  18. Trends in (LaMnO3)n/(SrTiO3)m superlattices with varying layer thicknesses

    Science.gov (United States)

    Jiwuer, Jilili; Cossu, Fabrizio; Schwingenschlögl, Udo

    2015-03-01

    We investigate the thickness dependence of the structural, electronic, and magnetic properties of (LaMnO3)n/(SrTiO3)m (n, m = 2, 4, 6, 8) superlattices using density functional theory. The structure relaxation turns out to be highly sensitive to the onsite Coulomb interaction. In contrast to bulk SrTiO3, strongly distorted O octahedra are observed in the SrTiO3 layers with a systematic off centering of the Ti atoms. The systems favour ferromagnetic spin ordering rather than the antiferromagnetic spin ordering of bulk LaMnO3 and all show half-metallicity, while a systematic reduction of the minority spin band gaps as a function of the LaMnO3 and SrTiO3 layer thicknesses originates from modifications of the Ti dxy states. Research was supported by the King Abdullah University of Science and Technology (KAUST).

  19. Computer simulation of superionic fluorides

    CERN Document Server

    Castiglione, M

    2000-01-01

    experimentally gives an indication of the correlations between nearby defects is well-reproduced. The most stringent test of simulation model transferability is presented in the studies of lead tin fluoride, in which significant 'covalent' effects are apparent. Other similarly-structured compounds are also investigated, and the reasons behind the adoption of such an unusual layered structure, and the mobility and site occupation of the anions is quantified. In this thesis the nature of ion mobility in cryolite and lead fluoride based compounds is investigated by computer simulation. The phase transition of cryolite is characterised in terms of rotation of AIF sub 6 octahedra, and the conductive properties are shown to result from diffusion of the sodium ions. The two processes appear to be unrelated. Very good agreement with NMR experimental results is found. The Pb sup 2 sup + ion has a very high polarisability, yet treatment of this property in previous simulations has been problematic. In this thesis a mor...

  20. Local Vibrations and Negative Thermal Expansion in ZrW2O8

    Science.gov (United States)

    Bridges, F.; Keiber, T.; Juhas, P.; Billinge, S. J. L.; Sutton, L.; Wilde, J.; Kowach, Glen R.

    2014-01-01

    We present an x-ray pair distribution function (XPDF) analysis and extended x-ray absorption fine structure (EXAFS) data for ZrW2O8 (10-500 K) with a focus on the stiffness of the Zr-O-W linkage. The XPDF is highly sensitive to W-Zr and W-W correlations, but much less so to O-O or W-O correlations. The Zr-W peak in the XPDF data has a weak temperature dependence and, hence, this linkage is relatively stiff and does not permit bending of the Zr-O-W link. We propose that the low energy vibrational modes that lead to negative thermal expansion involve correlated rotations of ZrO6 octahedra that produce large ⟨111⟩ translations of the WO4 tetrahedra, rather than a transverse motion of O atoms that imply a flexible Zr-O-W linkage.

  1. Local structure in ZrW2O8 from neutron total scattering

    Science.gov (United States)

    Tucker, Matthew G.; Keen, David A.; Evans, John S. O.; Dove, Martin T.

    2007-08-01

    The local structure of the low-temperature ordered phase of the negative thermal expansion (NTE) material ZrW2O8 has been investigated by reverse Monte Carlo (RMC) modelling of neutron total scattering data. The local structure is described using the instantaneous distributions of bond lengths and angles obtained from the RMC-derived models which are simultaneously consistent with the average crystal structure. These results, together with their variation with temperature, show that the majority of the mean squared displacements of the atoms are accounted for by rigid unit mode (RUM) motions of the ZrO6 octahedra and WO4 tetrahedra. The detailed structural description presented in this paper further supports the dominance of the basic RUM interpretation of NTE in ZrW2O8 where rigid ZrO6 and WO4 polyhedra are joined by flexible Zr-O-W linkages.

  2. Diaquatetrabromidotin(IV trihydrate

    Directory of Open Access Journals (Sweden)

    Fei Ye

    2012-09-01

    Full Text Available The title compound, [SnBr4(H2O2]·3H2O, forms large colourless crystals in originally sealed samples of tin tetrabromide. It constitutes the first structurally characterized hydrate of SnBr4 and is isostructural with the corresponding hydrate of SnCl4. It is composed of SnIV atoms octahedrally coordinated by four Br atoms and two cis-related water molecules. The octahedra exhibit site symmetry 2. They are arranged into columns along [001] via medium–strong O—H...O hydrogen bonds involving the two lattice water molecules (one situated on a twofold rotation axis while the chains are interconnected via longer O—H...Br hydrogen bonds, forming a three-dimensional network.

  3. Redetermination of the borax structure from laboratory X-ray data at 145 K

    Directory of Open Access Journals (Sweden)

    Caleb Higham

    2008-05-01

    Full Text Available The title compound, sodium tetraborate decahydrate (mineral name: borax, Na2[B4O5(OH4]·8H2O, has been studied previously using X-ray [Morimoto (1956. Miner. J. 2, 1–18] and neutron [Levy & Lisensky (1978. Acta Cryst. B34, 3502–3510] diffraction data. The structure contains tetraborate anions [B4O5(OH4]2− with twofold rotation symmetry, which form hydrogen-bonded chains, and [Na(H2O6] octahedra that form zigzag chains [Na(H2O4/2(H2O2/1]. The O—H bond distances obtained from the present redetermination at 145 K are shorter than those in the neutron study by an average of 0.127 (19 Å.

  4. Diaqua-2κ2O-bis(μ-1-oxido-2-naphthoato-1:2κ3O1,O2:O2′;2:3κ3O2:O1,O2′-bis(1-oxido-2-naphthoato-1κ1O2,O2;3κ2O1,O2-hexapyridine-1κ2N,2κ2N,3κ2N-trimanganese(II/III pyridine disolvate dihydrate

    Directory of Open Access Journals (Sweden)

    Daqi Wang

    2008-12-01

    Full Text Available The title complex, [Mn3(C11H6O34(C5H5N6(H2O2]·2H2O·2C5H5N, is a trinuclear mixed oxidation state complex of overline1 symmetry. The three Mn atoms are six-coordinated in the shape of distorted octahedra, each coordinated with an O4N2 set of donor atoms, where the ligands exhibit mono- and bidentate modes. However, the coordination of the MnII ion located on the inversion centre involves water molecules at two coordination sites, whereas that of the two symmetry-related MnIII ions involves an O4N2 set of donor atoms orginating from the organic ligands. Intramolecular C—H...π interactions between neighbouring pyridine ligands stabilize this arrangement. A two-dimensional network parallel to (001 is formed by intermolecular O—H...O hydrogen bonds.

  5. Synthesis of mullite nanometers microwave from bentonite delaminated; Sintese de mulita nanometrica por microondas a partir bentonitas delaminadas

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, J.; Azevedo, N.A.; Vieira, D.A.; Neves, G.A.; Santana, L.N.L., E-mail: josileido@yahoo.com.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil); Menezes, R.R. [Universidade Federal da Paraiba (UFPB), PB (Brazil)

    2011-07-01

    The smectite clays present as lamellar structure is formed by two layers of silica tetrahedrons and one layer of aluminum octahedra, which can be individually delaminated, reaching a thickness of about 1mm. Mullite is the only thermodynamically stable crystalline phase of SiO{sub 2} and Al2O{sub 3} system and can be synthesized from minerals that exhibit these oxides in its composition. The microwave synthesis offers advantages over conventional methods, the heating is rapid and uniform, avoiding an undesirable grain growth. This study aims to obtain nanometric mullite from bentonites delamined subjected to microwave heating. The samples were initially treated, then rehydrated, frozen and deagglomeration in a ball mill for 4 and 8 hours. Subsequently subjected to centrifugation, drying and microwave heating. The results showed that nano-mullite was obtained for samples subjected to longer heating and dispersions. (author)

  6. Structure solution of the new titanate Li{sub 4}Ti{sub 8}Ni{sub 3}O{sub 21} using precession electron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Gemmi, Mauro [Univ. degli Studi di Milano (Italy). Dipt. di Scienze della Terra ' Ardito Desio' ; Joseph Fourier Univ., 38 - Grenoble (France). Inst. Neel; CNRS, 38 - Grenoble (France); Klein, Holger; Rageau, Amelie; Strobel, Pierre [Joseph Fourier Univ., 38 - Grenoble (France). Inst. Neel; CNRS, 38 - Grenoble (France); Le Cras, Frederic [CEA-Grenoble, 38 (France). DRT/LITEN/LT2N

    2010-02-15

    A sample having stoichiometry Li[Ti{sub 1.5}Ni{sub 0.5}]O{sub 4} has been synthesized to obtain a spinel structure. The resulting crystalline powder revealed a multiphase nature with spinel as the minor phase. The main phase is a new trigonal phase having a=5.05910(1), c=32.5371(1) A. The structure has been solved by direct methods working on a three-dimensional set of intensities obtained from a precession electron-diffraction experiment, and refined on synchrotron powder diffraction data in the space group P anti 3c1. The model consists of hexagonal layers of edge-sharing octahedra occupied either by the heavy cations Ti and Ni, or preferentially by Li. On the basis of cation-site occupancies the stoichiometry becomes Li{sub 4}Ti{sub 8}Ni{sub 3}O{sub 21}, which is compatible with the microanalysis results. (orig.)

  7. Tris(N,N,N′,N′,N′′,N′′-hexaethylguanidinium dodecaiodidotribismuthate(III

    Directory of Open Access Journals (Sweden)

    Ioannis Tiritiris

    2016-03-01

    Full Text Available The asymmetric unit of title compound, (C13H30N33[Bi3I12], comprises one cation and two independent (1/6 fragments of the [Bi3I12]3− ions. The C—N bond lengths in the guanidinium ion range from 1.340 (4 to 1.345 (4 Å, indicating partial double-bond character pointing towards charge delocalization within the NCN planes. The BiIII ions are distorted octahedrally coordinated by six iodide ions, with Bi—I bond lengths ranging from 2.9206 (3 to 3.3507 (3 Å. Three [BiI6]3− octahedra are fused together through face-sharing, forming a trinuclear [Bi3I12]3− unit.

  8. Mechanisms for iron oxide formation under hydrothermal conditions: an in situ total scattering study.

    Science.gov (United States)

    Jensen, Kirsten M Ø; Andersen, Henrik L; Tyrsted, Christoffer; Bøjesen, Espen D; Dippel, Ann-Christin; Lock, Nina; Billinge, Simon J L; Iversen, Bo B; Christensen, Mogens

    2014-10-28

    The formation and growth of maghemite (γ-Fe2O3) nanoparticles from ammonium iron(III) citrate solutions (C(6)O(7)H(6) · xFe(3+) · yNH(4)) in hydrothermal synthesis conditions have been studied by in situ total scattering. The local structure of the precursor in solution is similar to that of the crystalline coordination polymer [Fe(H(2)cit(H2O)](n), where corner-sharing [FeO(6)] octahedra are linked by citrate. As hydrothermal treatment of the solution is initiated, clusters of edge-sharing [FeO(6)] units form (with extent of the structural order particles smaller than 6 nm are highly disordered. The final crystallite size (<10 nm) is dependent on both synthesis temperature and precursor concentration.

  9. Construction of two novel indium phosphites with (3,6)- and (3,5)-connected frameworks: Synthesis, structure and characterization

    Science.gov (United States)

    Li, Huiduan; Zhang, Lirong; Huo, Qisheng; Liu, Yunling

    2013-01-01

    Two novel anionic indium phosphites, formulated as [H3O][In(HPO3)2] (1) and [C4H12N2][In2(HPO3)3(C2O4)] (2), were prepared under hydrothermal conditions by using piperazine (PIP) as a structure-directing agent (SDA). Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 crystallize in the hexagonal space group P63mc (No. 186) and orthorhombic space group Cmcm (No. 63), respectively. Compound 1, constructed from InO6 octahedra and HPO3 pseudo-pyramids, exhibits a rare (3,6)-connected layer structure with kgd (Kagome dual) topology. Compound 2, on the other hand, features a 3D phosphite-oxalate hybrid structure with intersecting 8- and 12-MRs channels. From a topological perspective 2 can be regarded as a (3, 5)-connected binodal net with the Schläfli symbol (42.6)(42.65.83).

  10. Redetermination of the hexagonal struvite analogue Cs[Mg(OH26](PO4

    Directory of Open Access Journals (Sweden)

    Matthias Weil

    2008-08-01

    Full Text Available The structure of the hexagonal modification of caesium hexaaquamagnesium phosphate has been redetermined from single-crystal X-ray data. The previous refinement from photographic data [Ferrari, Calvaca & Nardelli (1955. Gazz. Chim. Ital. 85, 1232–1238] was basically confirmed, but with all H atoms located and with all non H-atoms refined with anisotropic displacement parameters. The structure can be derived from the NiAs structure type: the PO4 tetrahedra (3m. symmetry are on the Ni positions and the complex [Mg(OH26] octahedra (3m. symmetry are on the As positions. The building units are connected to each other by hydrogen bonds. The Cs+ cations (3m. symmetry are located in the voids of this arrangement and exhibit a distorted cuboctahedral 12-coordination by the O atoms of the water molecules.

  11. Lithium vanado(Vmolybdate(VI, Li[VMoO6

    Directory of Open Access Journals (Sweden)

    Safa Ezzine Yahmed

    2013-09-01

    Full Text Available Brannerite-type Li[VMoO6] has been synthesized by a solid state reaction route. The V and Mo atoms statistically occupy the same site with mirror symmetry and are octahedrally surrounded by O atoms. The framework is two-dimensional and is built up from edge-sharing (V,MoO6 octahedra forming (VMoO6∞ layers that run parallel to the (001 plane. Li+ ions are situated in position with symmetry 2/m in the interlayer space. The bond-valence analysis reveals that the Li+ ionic conductivity is along the [010] and [110] directions, and shows that this material may have interesting conduction properties. This simulation proposes a model of the lithium conduction pathways.

  12. Investigation of the La2O3-Nb2O5-WO3 ternary phase diagram: Isolation and crystal structure determination of the original La3NbWO10 material

    KAUST Repository

    Vu, T.D.

    2015-05-23

    In the course of the exploration of the La2O3-WO3-Nb2O5 ternary phase diagram, a new compound with the formula La3NbWO10 was discovered. Its structure was determined from a combination of powder X-ray and neutron diffraction data. It crystallizes in the tetragonal space group P42/nmc (no. 137) with the lattice parameters: a=10.0807(1) Å; c=12.5540(1) Å. The structure is built up from infinite ribbons of octahedra (W/Nb)O5 which are perpendicular to each other, lanthanum ions being distributed around these ribbons. The electrical properties of this compound were investigated on sintered pellets by means of complex impedance spectroscopy. © 2015 Elsevier Inc. All rights reserved.

  13. Electric field manipulation of magnetic and transport properties in SrRuO3/Pb(Mg1/3Nb2/3)O3-PbTiO3 heterostructure

    Science.gov (United States)

    Zhou, W. P.; Li, Q.; Xiong, Y. Q.; Zhang, Q. M.; Wang, D. H.; Cao, Q. Q.; Lv, L. Y.; Du, Y. W.

    2014-01-01

    The electric field manipulation of magnetic properties is currently of great interest for the opportunities provided in low-energy-consuming spintronics devices. Here, we report the effect of electric field on magnetic and transport properties of the ferromagnetic SrRuO3 film which is epitaxially grown on Pb(Mg1/3Nb2/3)O3-PbTiO3 ferroelectric substrate. With the application of electric field on the substrate, the magnetization, Curie temperature and resistivity of SrRuO3 are effectively modified. The mechanism of the electric field manipulation of these properties is ascribed to the rotations of RuO6 oxygen octahedra caused by the electric-field-induced strain, which changes the overlap and hybridization between the Ru 4d orbitals and O 2p orbitals, resulting in the modification of the magnetic and electronic properties. PMID:25384967

  14. Ammonium iron(III phosphate(V fluoride, (NH40.5[(NH40.375K0.125]FePO4F, with ammonium partially substituted by potassium

    Directory of Open Access Journals (Sweden)

    Lei Wang

    2009-01-01

    Full Text Available The title compound, ammonium potassium iron(III phosphate fluoride, (NH40.875K0.125FePO4F, is built from zigzag chains ∞1{[FeO4F2]7−}, with Fe3+ in a distorted octahedral coordination, extending along both the [011] and [0overline{1}1] directions. These chains are made up of alternating trans-[FeO4F2] and cis-[FeO4F2] octahedra via shared F-atom corners, and are linked by PO4 tetrahedra, resulting in an open-framework structure with channels along the [010] and [100] directions. There are two crystallographically independent ammonium sites: one in the [010] channels and the other, partially substituted by K+ ions, in the [100] channels. The ammonium in the [010] channels is fixed to the framework via eight hydrogen bonds (six N—H...O and two N—H...F.

  15. Tetrahedral connection of ε-Keggin-type polyoxometalates to form an all-inorganic octahedral molecular sieve with an intrinsic 3D pore system.

    Science.gov (United States)

    Zhang, Zhenxin; Sadakane, Masahiro; Murayama, Toru; Izumi, Shoko; Yasuda, Nobuhiro; Sakaguchi, Norihito; Ueda, Wataru

    2014-01-21

    A new type of polyoxometalate-based porous material was successfully synthesized. The new material is the first fully inorganic Keggin-type polyoxometalate-based microporous material with intrinsically ordered open micropores and is the third member of the small family of octahedral molecular sieves (OMSs). Twelve MoO6 or VO6 octahedra surround a central VO4 tetrahedron to form ε-Keggin polyoxometalate building blocks (ε-VMo9.4V2.6O40) that are linked by Bi(III) ions to form crystalline Mo-V-Bi oxide with a diamondoid topology. The presence of a tetrahedral shape of the ε-Keggin polyoxometalate building block results in arrangement of microporosity in a tetrahedral fashion which is new in OMSs. Owing to its microporosity, this Mo-V-Bi oxide shows zeolitic-like properties such as ion-exchange and molecule adsorption.

  16. Polar and nonpolar atomic motions in the relaxor ferroelectric Pb1-3x/2LaxZr0.2Ti0.8O3 from dielectric, anelastic, and NMR relaxation

    Science.gov (United States)

    Cordero, F.; Corti, M.; Craciun, F.; Galassi, C.; Piazza, D.; Tabak, F.

    2005-03-01

    Dielectric, anelastic, and La139 NMR relaxation measurements have been made on the relaxor ferroelectric Pb1-3x/2LaxZr0.2Ti0.8O3 (PLZT) with x=0.22 . The dielectric susceptibility exhibits the frequency dispersive maximum due to the freezing of the polar degrees of freedom around T≃250K . The anelastic and especially NMR relaxation, besides this maximum, indicate an intense and broad component at lower temperatures, attributed to rotational modes of the O octahedra, weakly coupled to the polar modes. It is discussed why such short range rotational instabilities, known to occur in the Zr-rich rhombohedral region of the PLZT phase diagram, might appear also in the Ti-rich region.

  17. Distortion-induced scattering due to vacancies in NbC/sub 0. 72/

    Energy Technology Data Exchange (ETDEWEB)

    Ohshima, K.; Harada, J.; Morinaga, M.; Georgopoulos, P.; Cohen, J.B.

    1988-03-01

    The diffuse X-ray (and electron) scattering from NbC/sub 0.72/, previously thought to be due to vacancy octahedra, is shown to be dominated by the scattering due to mean-square atomic displacements with wave vectors near the Brillouin-zone boundary. The atomic displacements are similar to those produced by an optical phonon. On the basis of the sign and amplitude of the displacement parameters a model for the environment around a carbon vacancy is proposed. The Nb nearest neighbors to a vacancy move away from it, whereas the C neighbors move toward it, and this appears to be due to an enhancement of the strength of the Nb-C bond arising from the presence of vacancies on the C sublattice. There is evidence that these vacancies tend to be correlated along 211 vectors.

  18. KInAs2O7, a new diarsenate with the TlInAs2O7 structure type

    Directory of Open Access Journals (Sweden)

    Karolina Schwendtner

    2017-09-01

    Full Text Available Potassium indium diarsenate(V was grown under mild hydrothermal conditions (T = 493 K, 7 d at a pH value of about 1. It adopts the TlInAs2O7 structure type (P-1, Z = 4 and is closely related to the KAlP2O7 (P21/c and RbAlAs2O7 (P-1 structure types. The framework topology of KInAs2O7 is built of two symmetrically non-equivalent As2O7 groups which share corners with InO6 octahedra. The K atoms are located in channels extending along [010].

  19. Crystal structure of iron(III perchlorate nonahydrate

    Directory of Open Access Journals (Sweden)

    Erik Hennings

    2014-12-01

    Full Text Available Since the discovery of perchlorate salts on Mars and the known occurrence of ferric salts in the regolith, there is a distinct possibility that the title compound could form on the surface of Mars. [Fe(H2O6](ClO43·3H2O was crystallized from aqueous solutions at low temperatures according to the solid–liquid phase diagram. It consists of Fe(H2O6 octahedra (point group symmetry -3. and perchlorate anions (point group symmetry .2 as well as non-coordinating water molecules, as part of a second hydrogen-bonded coordination sphere around the cation. The perchlorate appears to be slightly disordered, with major–minor component occupancies of 0.773 (9:0.227 (9.

  20. High-pressure x-ray absorption spectroscopy study of tin tungstates

    Science.gov (United States)

    Kuzmin, A.; Anspoks, A.; Kalinko, A.; Timoshenko, J.; Kalendarev, R.; Nataf, L.; Baudelet, F.; Irifune, T.

    2015-09-01

    Room-temperature pressure-dependent (0-25 GPa) x-ray absorption spectroscopy at the W {L}{1,3}-edges of α-SnWO4 and β-SnWO4 was performed using a dispersive setup and a high-pressure nanodiamond anvil cell. The detailed analysis of experimental x-ray absorption near-edge structure and extended x-ray absorption fine structure data suggests that upon increasing pressure, a displacement of tungsten atoms by about 0.2 Å toward the center of the WO6 octahedra occurs in α-SnWO4, whereas the coordination of tungsten atoms changes from tetrahedral to distorted octahedral in β-SnWO4.

  1. Magnetic and dielectric properties of quasi-two-dimensional manganese oxide Sr7Mn4O15

    Science.gov (United States)

    Gao, S.; Lv, Y. D.; Wang, X. X.; Yang, H. S.; Ruan, K. Q.; Li, X. G.

    2013-02-01

    Using dc magnetic susceptibility, electron spin resonance (ESR) and dielectric spectroscopy techniques, we investigate the magnetic and dielectric properties of Sr7Mn4O15, which has a layered structure with pairs of face-sharing octahedra Mn2O9. Magnetic susceptibility reveals the Néel temperature TN˜70.5 K, above which Sr7Mn4O15 manifests intense short range order. ESR spectra indicate the existence of a transition at about 370 K, confirming the suggested spin pairing in the Mn2O9 units. In the dielectric spectra, a sudden drop of permittivity is observed at TN, revealing the existence of strong spin-lattice coupling in Sr7Mn4O15.

  2. Synthesising methods of layered double hydroxides and its use in the fabrication of dye Sensitised solar cell (DSSC): A short review

    Science.gov (United States)

    George, Giphin; Saravanakumar, M. P.

    2017-11-01

    The layered double hydroxides (LDH) which are anionic clay substances comprising of stacked cationic layers and interlayer anions. The cationic sheets contain octahedral structure consisting the divalent and trivalent ions in the center and hydroxyl bunches in the corners, gathered by three bonding with the neighbouring octahedra on every side of the layer. The ratio between the quantity of cations and OH‑ ions is 2:1, so a positive charge shows up on the layer because of the presence of trivalent cations. The interlayer space gives the compensation anions and water molecules, assuring a balanced out layered structure. The LDH materials were successfully synthesised from magnesium, aluminium, zinc and chromium chloride salts utilizing the co-precipitation technique. A Zn-Al LDH was researched as a potential sorbent material. This article reviews the recent advances in the preparation and intercalation of layered double hydroxides and its application in the fabrication of Dye Sensitized Solar Cell (DSSC).

  3. Cd4As2Br3

    Directory of Open Access Journals (Sweden)

    Mohammed Kars

    2014-03-01

    Full Text Available Single crystals of Cd4As2Br3 (tetracadmium biarsenide tribromide were grown by a chemical transport reaction. The structure is isotypic with the members of the cadmium and mercury pnictidohalides family with general formula M4A2X3 (M = Cd, Hg; A = P, As, Sb; X = Cl, Br, I and contains two independent As atoms on special positions with site symmetry -3 and two independent Cd atoms, of which one is on a special position with site symmetry -3. The Cd4As2Br3 structure consists of AsCd4 tetrahedra sharing vertices with isolated As2Cd6 octahedra that contain As–As dumbbells in the centre of the octahedron. The Br atoms are located in the voids of this three-dimensional arrangement and bridge the different polyhedra through Cd...Br contacts.

  4. Electrical Control of Structural and Physical Properties via Strong Spin-Orbit Interactions in Sr2IrO4

    Science.gov (United States)

    Cao, G.; Terzic, J.; Zhao, H. D.; Zheng, H.; De Long, L. E.; Riseborough, Peter S.

    2018-01-01

    Electrical control of structural and physical properties is a long-sought, but elusive goal of contemporary science and technology. We demonstrate that a combination of strong spin-orbit interactions (SOI) and a canted antiferromagnetic Mott state is sufficient to attain that goal. The antiferromagnetic insulator Sr2IrO4 provides a model system in which strong SOI lock canted Ir magnetic moments to IrO6 octahedra, causing them to rigidly rotate together. A novel coupling between an applied electrical current and the canting angle reduces the Néel temperature and drives a large, nonlinear lattice expansion that closely tracks the magnetization, increases the electron mobility, and precipitates a unique resistive switching effect. Our observations open new avenues for understanding fundamental physics driven by strong SOI in condensed matter, and provide a new paradigm for functional materials and devices.

  5. Structural transition induced by charge-transfer in RbMn[Fe(CN) sub 6]. Investigation by synchrotron-radiation X-ray powder analysis

    CERN Document Server

    Moritomo, Y; Sakata, M; Kato, K; Kuriki, A; Tokoro, H; Ohkoshi, S I; Hashimoto, K

    2002-01-01

    Temperature dependence of atomic coordinates is determined for RbMn[Fe(CN) sub 6] by means of synchrotron-radiation (SR) X-ray powder structural analysis. We observed a structural transition from the cubic (F4-bar3m; Z=4) to the tetragonal (I4-barm2; Z=2) phase at approx. =210K in the cooling run and at approx. =300K in the warming run. In the low-temperature tetragonal phase, we found Jahn-Tellar type distortion of the MnN sub 6 octahedra and compression of the averaged Fe-C bond distance. These structural data suggest that the structural transition is triggered by the inter-metallic charge-transfer from the Mn(II) site to the Fe(III) site.

  6. Structural and vibrational studies of LiNi{sub 1-y}Co{sub y}VO{sub 4} (0{<=}y{<=}1) cathodes materials for Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Julien, C.; Massot, M. [Univ. Pierre et Marie Curie, Paris (France). Lab. des Milieux Desordonnes et Heterogenes; Perez-Vicente, C. [Laboratoire des Agregats Moleculaires et Materiaux Inorganiques, CC-015, Universite de Montpellier II, place Eugene-Bataillon, 34095, Montpellier (France)

    2000-05-15

    The structure and vibrational properties of high voltage cathode materials, namely LiNi{sub 1-y}CO{sub y}VO{sub 4} solid solution with (0{<=}y{<=}1), have been studied using X-ray diffraction, Raman scattering and FTIR measurements. Rietveld refinements show that LiNi{sub 1-y}Co{sub y}VO{sub 4} vanadates belong to the inverse spinel structure with Fd3m(O{sup 7}{sub h}) space group. Analysis of Raman spectra has been carried out in the molecular approximation using a local environment model including VO{sub 4} tetrahedra, (Ni, Co)O{sub 6} and LiO{sub 6} octahedra as vibrational local units. (orig.)

  7. Cobalt segregation in the LiNi 1-yCo yO 2 solid solution: A preliminary 7Li NMR study

    Science.gov (United States)

    Menetrier, M.; Rougier, A.; Delmas, C.

    1994-05-01

    LiNi 1-yCo yO 2 materials exhibit a layered structure built from alternate sheets of (Ni,Co)O 6 and of LiO 6 octahedra sharing edges. They are particularly interesting as positive electrode in rechargeable lithium batteries. Single-pulse 7Li NMR spectra allow to distinguish between the Li + ions with only cobalt as their first 3d neighbors and those with at least one Ni 3+ (LS t 26e 1). The small amount of excess Ni 2+ ions (t 26e 2) known to be present in the materials with small y causes an alteration of the spectra. Li + ions with only cobalt as their first cationic neighbors are detected even for small cobalt contents, which shows the existence of a cobalt segregation while X-rays show that no phase separation occurs.

  8. The crystal chemistry of iron (III monophosphates with mono and divalent metallic cations

    Directory of Open Access Journals (Sweden)

    Badri A.

    2013-09-01

    Full Text Available As a contribution to the study of alkaline iron (III monophosphates, we recently investigated the A3PO4-M3(PO42-FePO4 (A: alkali metal; M: divalent cation using both the flux method and the solid state reaction. This investigation led to the synthesis and structural characterization of twelve new compounds. Their structural analysis showed them to be constructed by PO4 tetrahedra and FeOx polyhedra (x = 6, 5, 4. The Fe polyhedra are either isolated or forming finite units of corner- or edge-sharing, or infinite chains of edge-sharing octahedra. The resulting Fe structural units are linked by the PO4 tetrahedra via corner or edge-sharing, giving rise to mixed covalent frameworks which can be either bi- or three-dimentionnel. The alkali cations occupy the interlayer space or tunnels and cavities.

  9. Intricacies of the Co3 + spin state in Sr2Co0.5Ir0.5O4 : An x-ray absorption and magnetic circular dichroism study

    Science.gov (United States)

    Agrestini, S.; Kuo, C.-Y.; Mikhailova, D.; Chen, K.; Ohresser, P.; Pi, T. W.; Guo, H.; Komarek, A. C.; Tanaka, A.; Hu, Z.; Tjeng, L. H.

    2017-06-01

    We report on a combined soft x-ray absorption and magnetic circular dichroism (XMCD) study at the Co-L3 ,2 edge on the hybrid 3 d /5 d solid state oxide Sr2Co0.5Ir0.5O4 with K2NiF4 structure. Our data indicate unambiguously a pure high spin state (S =2 ) for the Co3 + (3 d6 ) ions with a significant unquenched orbital moment Lz/2 Sz=0.25 despite the sizable elongation of the CoO6 octahedra. Using quantitative model calculations based on parameters consistent with our spectra, we have investigated the stability of this high spin state with respect to the competing low spin and intermediate spin states.

  10. Strain sensitivity of band gaps of Sn-containing semiconductors

    DEFF Research Database (Denmark)

    Li, Hong; Castelli, Ivano Eligio; Thygesen, Kristian Sommer

    2015-01-01

    Tuning of band gaps of semiconductors is a way to optimize materials for applications within photovoltaics or as photocatalysts. One way to achieve this is through applying strain to the materials. We investigate the effect of strain on a range of Sn-containing semiconductors using density...... functional theory and many-body perturbation theory calculations. We find that the band gaps of bulk Sn oxides with SnO6 octahedra are highly sensitive to volumetric strain. By applying a small isotropic strain of 2% (-2%), a decrease (increase) of band gaps as large as 0.8 to 1.0 eV are obtained. We...... attribute the ultrahigh strain sensitivity to the pure Sn s-state character of the conduction-band edges. Other Sn-containing compounds may show both increasing and decreasing gaps under tensile strain and we show that the behavior can be understood by analyzing the role of the Sn s states in both...

  11. Proximate Kitaev quantum spin liquid behavior in α-RuCl{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Nagler, Stephen [Quantum Condensed Matter Division, Oak Ridge National Laboratory (United States)

    2016-07-01

    The magnetic semiconductor α-RuCl{sub 3} is composed of very weakly coupled honeycomb layers of edge-sharing RuCl{sub 6} octahedra. The Ru{sup 3+} ion has 5d electrons in a low spin state, and the system is expected to have an effective J = 1/2 single ion ground state with an interacting spin Hamiltonian containing Kitaev-like terms. Inelastic neutron scattering on powders and single crystals has been used to determine the energy scale of the magnetic interactions and the overall form of the magnetic fluctuations. The results indicate that the Kitaev term is significant. Moreover, detailed measurements of the response show evidence for the fractionalized excitations that are characteristic of the Kitaev Quantum Spin-liquid.

  12. Synthesis and properties of La{sub 1}-x Ca{sub x} Al O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Diafi, M.; Omari, M.

    2012-07-01

    La{sub 1} -x Ca{sub x} Al O{sub 3} (0 {<=} x {<=} 0.6) perovskite-type oxides were prepared by co-precipitation method using metal nitrate salts as cation precursors and NaOH solution as the precipitating agent. Differential thermal analysis (DTA) and thermogravimetric analysis (TGA) results indicate that decomposition of the precursor to the oxide begins at {approx} 800 degree centigrade. Powder X-ray diffraction (XRD) patterns confirm the formation of the perovskite phase. Both undoped and doped lanthanum aluminates show two IR active vibrational modes at 450 and 670 cm{sup -}1 which are assigned to AlO{sub 6} octahedra of the oxide matrix. The microstructure and morphology of the compounds show that the particles are nearly spherical in shape and are agglomerated. Electrochemical measurements indicate that the catalytic activity is strongly influenced by lanthanum doping. The highest electrode performance is achieved with large calcium content. (Author) 27 refs.

  13. An oxysulfate Fe₂O(SO₄)₂ electrode for sustainable Li-based batteries.

    Science.gov (United States)

    Sun, Meiling; Rousse, Gwenaëlle; Abakumov, Artem M; Van Tendeloo, Gustaaf; Sougrati, Moulay-Tahar; Courty, Matthieu; Doublet, Marie-Liesse; Tarascon, Jean-Marie

    2014-09-10

    High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe(3+)/Fe(2+) redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)2, made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li(+)/Li, leading to a sustained reversible capacity of ≈125 mAh/g. The Li insertion-deinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.

  14. The atomic structure and chemistry of Fe-rich steps on antiphase boundaries in Ti-doped Bi0.9Nd0.15FeO3

    Directory of Open Access Journals (Sweden)

    Ian MacLaren

    2014-06-01

    Full Text Available Stepped antiphase boundaries are frequently observed in Ti-doped Bi0.85Nd0.15FeO3, related to the novel planar antiphase boundaries reported recently. The atomic structure and chemistry of these steps are determined by a combination of high angle annular dark field and bright field scanning transmission electron microscopy imaging, together with electron energy loss spectroscopy. The core of these steps is found to consist of 4 edge-sharing FeO6 octahedra. The structure is confirmed by image simulations using a frozen phonon multislice approach. The steps are also found to be negatively charged and, like the planar boundaries studied previously, result in polarisation of the surrounding perovskite matrix.

  15. Crystal structure of [NiHg(SCN4(CH3OH2]n

    Directory of Open Access Journals (Sweden)

    Matthias Weil

    2014-08-01

    Full Text Available The title compound, catena-poly[[bis(methanol-κOnickel(II]-di-μ-thiocyanato-κ4N:S-mercurate(II-di-μ-thiocyanato-κ4N:S], was obtained from a gel-growth method using tetramethoxysilane as gelling agent. The crystal structure is composed of rather regular HgS4 tetrahedra (point group symmetry .2. and trans-NiN4O2 octahedra (point group symmetry 2.. that are linked through thiocyanato bridges into a three-dimensional framework. The methanol molecules coordinate via the O atom to the Ni2+ cations and point into the voids of this arrangement while a weak O—H...S hydrogen bond to an adjacent S atom stabilizes it.

  16. High mobility half-metallicity in the (LaMnO3)2/(SrTiO3)8 superlattice

    KAUST Repository

    Cossu, Fabrizio

    2013-01-28

    First principles calculations have been performed to investigate the LaMnO3/SrTiO3 superlattice. Structural relaxation within the generalized gradient approximation results in no significant tiltings or rotations of oxygen octahedra, but in distinct distortions in the SrTiO3 region. Taking into account the onsite Coulomb interaction, we find that the Mn spins order ferromagnetically, in contrast to the antiferromagnetic state of bulk LaMnO3. Most importantly, the interface strain combined with charge transfer across the interface induces half-metallicity within the MnO2 layers. The superlattice is particulary interesting for spintronics applications because the half-metallic states are characterized by an extraordinary high mobility.

  17. High-Temperature Magnetic Insulating Phase in Ultrathin La0.67Sr0.33MnO3 Films

    Science.gov (United States)

    Boschker, Hans; Kautz, Jaap; Houwman, Evert P.; Siemons, Wolter; Blank, Dave H. A.; Huijben, Mark; Koster, Gertjan; Vailionis, Arturas; Rijnders, Guus

    2012-10-01

    We present a study of the thickness dependence of magnetism and electrical conductivity in ultrathin La0.67Sr0.33MnO3 films grown on SrTiO3 (110) substrates. We found a critical thickness of 10 unit cells below which the conductivity of the films disappeared and simultaneously the Curie temperature increased, indicating a magnetic insulating phase at room temperature. These samples have a Curie temperature of about 560 K with a significant saturation magnetization of 1.2±0.2μB/Mn. The canted antiferromagnetic insulating phase in ultra thin films of n<10 coincides with the occurrence of a higher symmetry structural phase with a different oxygen octahedra rotation pattern. Such a strain engineered phase is an interesting candidate for an insulating tunneling barrier in room temperature spin polarized tunneling devices.

  18. Misfit strain accommodation in epitaxial ABO3 perovskites: Lattice rotations and lattice modulations

    Science.gov (United States)

    Vailionis, A.; Boschker, H.; Siemons, W.; Houwman, E. P.; Blank, D. H. A.; Rijnders, G.; Koster, G.

    2011-02-01

    We present a study of the lattice response to the compressive and tensile biaxial stress in La0.67Sr0.33MnO3 (LSMO) and SrRuO3 (SRO) thin films grown on a variety of single-crystal substrates: SrTiO3, DyScO3, NdGaO3, and (La,Sr)(Al,Ta)O3. The results show that, in thin films under misfit strain, both SRO and LSMO lattices, which in bulk form have orthorhombic (SRO) and rhombohedral (LSMO) structures, assume unit cells that are monoclinic under compressive stress and tetragonal under tensile stress. The applied stress effectively modifies the BO6 octahedra rotations, whose degree and direction can be controlled by the magnitude and sign of the misfit strain. Such lattice distortions change the B-O-B bond angles and therefore are expected to affect magnetic and electronic properties of the ABO3 perovskites.

  19. In-situ studies on the micro-structure evolution of A2W2O7 (A = Li, Na, K) during melting by high temperature Raman spectroscopy and density functional theory

    Science.gov (United States)

    Wang, Jian; You, Jinglin; Wang, Min; Lu, Liming; Wan, Songming; Sobol, A. A.

    2017-10-01

    In-situ high temperature Raman spectroscopic (HTRS) technique in combination with density functional theory (DFT) analysis has been adopted to investigate the micro-structure of solid and molten A2W2O7 (A = Li, Na, K). The [WO6] octahedra were found to be connected to each other by corner and edge sharing in the crystalline Li2W2O7 and K2W2O7 compounds. In the crystal lattice of Na2W2O7, on the other hand, the [WO4] tetrahedra and [WO6] octahedra were found to coexist and paired by corner sharing. Although the structural diversity has clearly led to distinct Raman spectra of the crystalline A2W2O7 compounds, the spectra of their melts tended to be analogous, showing the typical vibration modes of (W2O7)2 - dimer. A mechanism was then proposed to explain the structure evolution occurring during the melting process of A2W2O7. The effect of A+ cation on the Raman bands of (W2O7)2 - dimer in molten A2W2O7 has also been investigated. Both the wavenumber and full width at half-height (FWHH) of the characteristic band assigned to the symmetrical stretching vibration mode of Wsbnd Onb (non-bridging oxygen) in (W2O7)2 - were found to decrease in the sequence of Li+, Na+ and K+, indicating the cation effect on the mean bond length and its distribution range of Wsbnd Onb. In addition, the relative intensity of this band was also influenced by the cation and it was increased in the order of Li2W2O7, Na2W2O7 and K2W2O7, which has been explained by the charge transfer process and confirmed by Mulliken overlap population analysis.

  20. Cationic Site-Preference in the Yb14-xCaxAlSb11 (4.81 ≤ x ≤ 10.57 Series: Theoretical and Experimental Studies

    Directory of Open Access Journals (Sweden)

    Gnu Nam

    2016-07-01

    Full Text Available Four quaternary Zintl phases with mixed-cations in the Yb14-xCaxAlSb11 (4.81 ≤ x ≤ 10.57 series have been synthesized by using the arc-melting and the Sn metal-flux reaction methods, and the isotypic crystal structures of the title compounds have been characterized by both powder and single-crystal X-ray diffraction (PXRD and SXRD analyses. The overall crystal structure adopting the Ca14AlSb11-type can be described as a pack of four different types of the spiral-shaped one-dimensional octahedra chains with various turning radii, each of which is formed by the distorted ((Yb/CaSb6 octahedra. Four symmetrically-independent cationic sites contain mixed occupations of Yb2+ and Ca2+ with different mixing ratios and display a particular site preference by two cationic elements. Two hypothetical structural models of Yb4Ca10AlSb11 with different cationic arrangements were designed and exploited to study the details of site and bond energies. QVAL values provided the rationale for the observed site preference based on the electronegativity of each atom. Density of states (DOS curves indicated a semiconducting property of the title compounds, and crystal orbital Hamilton population (COHP plots explained individual chemical bonding between components. Thermal conductivity measurement was performed for Yb8.42(4Ca5.58AlSb11, and the result was compared to compounds without mixed cations.

  1. Biferroic LuCrO{sub 3}: Structural characterization, magnetic and dielectric properties

    Energy Technology Data Exchange (ETDEWEB)

    Durán, A., E-mail: dural@cnyn.unam.mx [Universidad Nacional Autónoma de México, Centro de Nanociencias y Nanotecnología, Km. 107 Carretera Tijuana-Ensenada, Apartado Postal 14, C.P. 22800 Ensenada, BC (Mexico); Meza F, C.; Morán, E.; Alario-Franco, M.A. [Departamento de Química Inorgánica y Laboratorio Complutense de Altas Presiones, Facultad de Química, Universidad Complutense de Madrid, EU, 28040 Madrid (Spain); Ostos, C., E-mail: ceostoso@gmail.com [Instituto de Química, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín (Colombia)

    2014-02-14

    Multiferroic LuCrO{sub 3} perovskite-type structure (Pbnm) obtained via auto-ignition synthesis was characterized by a combination of X-ray diffraction (XRD) and thermogravimetric (TG) techniques, and through magnetization and permittivity measurements. Results showed that amorphous combustion powders were fully transformed to orthorhombic LuCrO{sub 3} structure at 1200 K after the first LuCrO{sub 4} crystallization at 700 K. The magnetic response displays thermal irreversibility between zero-field-cooling and field-cooling condition which is due to spin canted AF switching at 116 K. Accordingly, a hysteresis loop in the M(H) data confirms weak ferromagnetism in LuCrO{sub 3}. On the other hand, the permittivity measurement shows a broad peak transition typical of relaxor-type ferroelectrics transition at ∼450 K. Electrical conductivity increases as temperature increases showing an anomaly around the diffuse phase transition. The diffuse phase transition and the formation of the charge carriers are discussed in terms of a local distortion around the Lu Site. - Highlights: • Multiferroic LuCrO{sub 3} was successfully obtained via auto-ignition synthesis. • Amorphous powder is transformed first to LuCrO{sub 4} (700 K) and next to LuCrO{sub 3} (1100 K). • The CrO{sub 6} octahedra are tilted away and rotates from the ideal octahedral shape. • LuCrO{sub 3} exhibits a canted AFM transition (116 K) and a relaxor ferroelectric behavior. • Tilting and rotation of CrO{sub 6} octahedra influenced transport properties on LuCrO{sub 3}.

  2. Photovoltaic Rudorffites: Lead-Free Silver Bismuth Halides Alternative to Hybrid Lead Halide Perovskites.

    Science.gov (United States)

    Turkevych, Ivan; Kazaoui, Said; Ito, Eisuke; Urano, Toshiyuki; Yamada, Koji; Tomiyasu, Hiroshi; Yamagishi, Hideo; Kondo, Michio; Aramaki, Shinji

    2017-10-09

    Hybrid CPbX 3 (C: Cs, CH 3 NH 3 ; X: Br, I) perovskites possess excellent photovoltaic properties but are highly toxic, which hinders their practical application. Unfortunately, all Pb-free alternatives based on Sn and Ge are extremely unstable. Although stable and non-toxic C 2 ABX 6 double perovskites based on alternating corner-shared AX 6 and BX 6 octahedra (A=Ag, Cu; B=Bi, Sb) are possible, they have indirect and wide band gaps of over 2 eV. However, is it necessary to keep the corner-shared perovskite structure to retain good photovoltaic properties? Here, we demonstrate another family of photovoltaic halides based on edge-shared AX 6 and BX 6 octahedra with the general formula A a B b X x (x=a+3 b) such as Ag 3 BiI 6 , Ag 2 BiI 5 , AgBiI 4 , AgBi 2 I 7 . As perovskites were named after their prototype oxide CaTiO 3 discovered by Lev Perovski, we propose to name these new ABX halides as rudorffites after Walter Rüdorff, who discovered their prototype oxide NaVO 2 . We studied structural and optoelectronic properties of several highly stable and promising Ag-Bi-I photovoltaic rudorffites that feature direct band gaps in the range of 1.79-1.83 eV and demonstrated a proof-of-concept FTO/c-m-TiO 2 /Ag 3 BiI 6 /PTAA/Au (FTO: fluorine-doped tin oxide, PTAA: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], c: compact, m: mesoporous) solar cell with photoconversion efficiency of 4.3 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. On the polymorphism of CaAl 2O 4—structural investigations of two high pressure modifications

    Science.gov (United States)

    Lazić, B.; Kahlenberg, V.; Konzett, J.; Kaindl, R.

    2006-06-01

    The crystal structures of two high pressure polymorphs have been studied using X-ray diffraction techniques. The compounds were synthesized from ceramic precursors at 1000 °C / 3.5 GPa (phase A) and 1100 °C / 10 GPa (phase B), respectively. In case of phase A, the structure was determined from a single crystal diffraction data set collected at room conditions and refined to a residual R|F|=0.027 for 1319 observed reflections ( I>2σ(I)). The compound crystallises in the monoclinic space group P2/m ( a=5.556(2) Å, b=3.7627(8) Å, c=7.056(3) Å, β=101.36(3)°, V=144.62(8) Å, Z=2, D=3.629 g cm). The crystals were subject to twinning by partial-merohedry which was accounted for during the refinements. Furthermore, a distinct one-dimensional diffuse scattering parallel to c could be observed. Phase A represents a layer structure containing double sheets of edge sharing AlO 6-octahedra, similar to those observed in boehmite (AlO(OH)) or lepidocrocite (FeO(OH)). Linkage between the layers is provided by the Ca cations occupying the interstitial space between the sheets. They are coordinated by seven oxygen ligands. The structure of phase B has been refined from laboratory powder diffraction data using the Rietveld method (space group Pnam, a=8.92004(5) Å, b=10.31550(6) Å, c=2.87129(1) Å, V=264.203(1) Å, Z=4, D=3.973 g cm). The compound is isostructural with monocalcium ferrite (CaFe 2O 4) and contains two crystallographically independent AlO 6-octahedra forming edge-sharing double chains parallel to [001]. Calcium cations are located in the tunnels formed by the linked double chains, being in eightfold coordination.

  4. Crystal structure of K0.75[FeII3.75FeIII1.25(HPO36]·0.5H2O, an open-framework iron phosphite with mixed-valent FeII/FeIII ions

    Directory of Open Access Journals (Sweden)

    Edurne S. Larrea

    2016-01-01

    Full Text Available Single crystals of the title compound, potassium hexaphosphitopentaferrate(II,III hemihydrate, K0.75[FeII3.75FeIII1.25(HPO36]·0.5H2O, were grown under mild hydrothermal conditions. The crystal structure is isotypic with Li1.43[FeII4.43FeIII0.57(HPO36]·1.5H2O and (NH42[FeII5(HPO36] and exhibits a [FeII3.75FeIII1.25(HPO36]0.75− open framework with disordered K+ (occupancy 3/4 as counter-cations. The anionic framework is based on (001 sheets of two [FeO6] octahedra (one with point group symmetry 3.. and one with point group symmetry .2. linked along [001] through [HPO3]2− oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octahedra, giving rise to channels with a radius of ca 3.1 Å where the K+ cations and likewise disordered water molecules (occupancy 1/4 are located. O...O contacts between the water molecule and framework O atoms of 2.864 (5 Å indicate hydrogen-bonding interactions of medium strength. The infrared spectrum of the compound shows vibrational bands typical for phosphite and water groups. The Mössbauer spectrum is in accordance with the presence of FeII and FeIII ions.

  5. One-dimensional infinite chain structures of [Al2(OH)4(H2O)4]X2 (X = I, Br, Cl): an aggregate of Al2 species and a precursor of Al(OH)3.

    Science.gov (United States)

    Sun, Zhong; Wang, Hui; Zhang, Ying; Li, Jingshuang; Zhao, Yang; Jiang, Wuning; Wang, Li

    2013-09-28

    By a combination of the Rietveld full-profile fitting technique based on powder X-ray diffraction data and the single-crystal structure solving and refining method, one-dimensional infinite zigzag chain structures were observed in the structures of [Al2(OH)4(H2O)4]X2 (X = I, Br, Cl). These crystallize in the same monoclinic system and the same C2/c space group with different unit cell parameters from spontaneously hydrolyzed solutions of AlX3. Each chain is composed of a significant number of AlO6 octahedra that fall into two groups with reverse orientations and connect to each other by edge-sharing. Furthermore, the counterions intersperse among the chains forming strong van der Waals interactions. It was also discovered that each chain was an aggregate formed from the further hydrolysis of the Al2 species (Al2(OH)2(H2O)8(4+), a dimer formed by two octahedral Al(H2O)6(3+) monomers sharing an edge) and a building unit for constructing the infinite hexameric ring sheet in nordstrandite and gibbsite. These are three new structures, rarely solved from powder XRD data, of polyaluminum compounds, and they provide the first direct evidence of the aggregation processes of Al2 species and their subsequent evolution into an infinite zigzag chain as well as further evolution into an infinite hexameric ring layer as found in nordstrandite and gibbsite. Furthermore, they also represent the first three examples in which each polyaluminum species possesses a one-dimensional infinite chain structure formed by AlO6 octahedra via edge-sharing only.

  6. Glycine zinc sulfate penta-hydrate: redetermination at 10 K from time-of-flight neutron Laue diffraction.

    Science.gov (United States)

    Fortes, A Dominic; Howard, Christopher M; Wood, Ian G; Gutmann, Matthias J

    2016-10-01

    Single crystals of glycine zinc sulfate penta-hydrate [systematic name: hexa-aqua-zinc tetra-aquadiglycinezinc bis-(sulfate)], [Zn(H2O)6][Zn(C2H5NO2)2(H2O)4](SO4)2, have been grown by isothermal evaporation from aqueous solution at room temperature and characterized by single-crystal neutron diffraction. The unit cell contains two unique ZnO6 octa-hedra on sites of symmetry -1 and two SO4 tetra-hedra with site symmetry 1; the octa-hedra comprise one [tetra-aqua-diglycine zinc]2+ ion (centred on one Zn atom) and one [hexa-aqua-zinc]2+ ion (centred on the other Zn atom); the glycine zwitterion, NH3+CH2COO-, adopts a monodentate coordination to the first Zn atom. All other atoms sit on general positions of site symmetry 1. Glycine forms centrosymmetric closed cyclic dimers due to N-H⋯O hydrogen bonds between the amine and carboxyl-ate groups of adjacent zwitterions and exhibits torsion angles varying from ideal planarity by no more than 1.2°, the smallest values for any known glycine zwitterion not otherwise constrained by a mirror plane. This work confirms the H-atom locations estimated in three earlier single-crystal X-ray diffraction studies with the addition of independently refined fractional coordinates and Uij parameters, which provide accurate inter-nuclear X-H (X = N, O) bond lengths and consequently a more accurate and precise depiction of the hydrogen-bond framework.

  7. Rich Non-centrosymmetry in a Na-U-Te Oxo-System Achieved under Extreme Conditions.

    Science.gov (United States)

    Xiao, Bin; Kegler, Philip; Bosbach, Dirk; Alekseev, Evgeny V

    2016-05-02

    Two new sodium uranyl tellurites and two new sodium uranyl tellurates have been synthesized from high-temperature/high-pressure conditions and structurally characterized. We demonstrated that crystalline phases, forming in a Na-U-Te system under extreme conditions, appear to favorably have non-centrosymmetric structures. Three out of four novel uranyl tellurium compounds, Na[(UO2)Te(IV)2O5(OH)], Na2[(UO2)(Te(VI)2O8)], and Na2[(UO2)Te(VI)O5], crystallize in non-centrosymmetric space groups. The crystal structure of Na[(UO2)Te(IV)2O5(OH)] is based on two-dimensional [UO2Te2O5(OH)](-) corrugated sheets, which are charge balanced by guest Na(+) cations. The structure of Na2[(UO2)Te(VI)2O8] is constructed from [(UO2)2Te2O8](2+) anionic layers composed of UO7 pentagonal bipyramids and TeO6 octahedra. Na2[(UO2)(Te(VI)O5)] is a new type of three-dimensional anionic open framework built from the interconnection of UO7 pentagonal bipyramids and TeO6 octahedra with different types of interlacing channels within the U-Te anionic framework. Na[(UO2)Te(IV)6O13(OH)], as the only centrosymmetric compound isolated in the Na-U-Te family, is crystallized in space group Pa3̅, and its structure is highly related to that of cliffordite (UO2(Te3O7)), which is composed from UO8 hexagonal bipyramids and TeO5 square pyramids. The vibrational modes associated with U-O, Te(IV)-O, and Te(VI)-O bonds are discussed, and the Raman spectra of the four compounds are characterized for signature bands.

  8. An x-ray absorption spectroscopic study of the electronic structure and bonding of rare-earth orthoferrites

    Science.gov (United States)

    Hayes, J. R.; Grosvenor, A. P.

    2011-11-01

    Rare-earth orthoferrites, REFeO3 (RE=rare earth; Y), are tremendously adaptable compounds that are being investigated for use in a wide variety of applications including gas sensors, vehicle catalytic converters, and solid-oxide fuel cells. They also exhibit interesting magnetic properties such as high-temperature antiferromagnetism, making them useful for data storage applications. The compounds adopt a distorted perovskite-type structure where the tilt angle of the octahedra increases (Fe-O-Fe bond angle decreases) as the size of the rare-earth atom decreases. Despite intensive study of the physical properties of these compounds, very few studies have investigated how the bonding and electronic structure of these systems change with substitution of the RE. X-ray absorption near-edge spectroscopy (XANES) is a technique well-suited for such a study, and, in view of this, Fe L-, Fe K- and O K-edge spectra from a series of REFeO3 compounds (RE=La, Pr, Nd, Sm, Eu, Gd, Ho, Yb, Y) have been collected, and are presented here. Fe L-edge spectra show that Fe is octahedrally coordinated and that the Fe-centered octahedra do not appear to distort with changes in the identity of the RE. The Fe K-edge spectra contain an intersite hybrid peak, which is an ill-studied feature that is attributed to non-local transitions of 1s electrons to 3d states on the next-nearest-neighbor atom that are hybridized with 4p states on the absorbing atom through O 2p states. In this study, it is shown that the intensity of this feature is strongly dependent on the Fe-O-Fe bond angle; the lower the Fe-O-Fe bond angle, the less intense the intersite hybrid peak is.

  9. In[IO3](OH)2 - New member of hydrous and anhydrous iodate family with indium

    Science.gov (United States)

    Belokoneva, E. L.; Dimitrova, O. V.; Volkov, A. S.

    2014-08-01

    A new indium iodate hydrate In[IO3](OH)2 was synthesized by the hydrothermal methods. Single crystal X-ray diffraction revealed centrosymmetric Pnma space group. [IO3]-groups have typical umbrella-like configuration: iodine atom and three oxygens with I-O distances ∼1.8 Å. In-octahedra have 4 equatorial OH-groups and 2 apical O-atoms of 2 [IO3]-groups and are connected into the layers via OH-groups. It is found that indium iodate family without any other metals is a regular row of compounds: anhydrous In[IO3]3, one hydrated In[IO3]2(OH)·H2O, new two hydrated In[IO3](OH)2 and “end member” represented by three hydrated hydroxide In(OH)3. Chemical relations are parallel to the structural: In-octahedral framework in In-hydroxide, In-octahedral layer as a fragment of the framework, In-octahedral chain as a fragment of the layer, isolated In-octahedra as a fragment of the chain with no In-octahedral condensation via vertices but only via [IO3]-groups in anhydrous In-iodate. If alkali metals are introduced in anhydrous In-iodates, their influence is different. Large metals as K, Rb, Cs hinder condensation of {In[IO3]6}3- blocks which are isolated in the structures whereas smaller Li, Na metals allows condensation up to bands {In[IO3]4}1-∞. Octahedral chains selected in hydrated In-iodates are similar to chains in nonlinear optical compound TiO[IO3]2. The reasons of polarity or non-polarity and possible elements substitutions promising for properties are discussed.

  10. Synthesis, crystal structure and infrared spectroscopy of a new non-centrosymmetric mixed-anion phosphate Na{sub 4}Mg{sub 3}(PO{sub 4}){sub 2}(P{sub 2}O{sub 7})

    Energy Technology Data Exchange (ETDEWEB)

    Essehli, Rachid, E-mail: essehli_rachid@yahoo.f [Laboratory of Mineral Solid and Analytical Chemistry ' LCSMA' , Department of Chemistry, Faculty of Sciences, University Mohamed I, P.O. Box 717, 60000 Oujda (Morocco); El Bali, Brahim [Laboratory of Mineral Solid and Analytical Chemistry ' LCSMA' , Department of Chemistry, Faculty of Sciences, University Mohamed I, P.O. Box 717, 60000 Oujda (Morocco); Benmokhtar, Said [LCMS, Department of Chemistry, Faculty of Sciences Ben M' SIK, Casablanca (Morocco); Fuess, Hartmut; Svoboda, Ingrid [Materials Science, Darmstadt University of Technology, Petersenstr. 23, D-64287 Darmstadt (Germany); Obbade, Said [Equipe de Chimie du Solide, UCCS - UMR CNRS 8181, USTL-ENSCL, B.P. 90108, 59652 Villeneuve d' Ascq Cedex (France)

    2010-03-18

    The new mixed-anion phosphate Na{sub 4}Mg{sub 3}(PO{sub 4}){sub 2}(P{sub 2}O{sub 7}) has been prepared and its structure has been determined by single crystal X-ray diffraction. The crystal structure was refined to R = 0.0290 (wR = 0.0836) for 1527 independent reflexions. This compound crystallizes in the orthorhombic non-centrosymmetric space group Pn2{sub 1}a with a = 17.985(2) A, b = 6.525(9) A, c = 10.511(1) A, and Z = 4. The framework is built up from [PO{sub 4}] tetrahedra, [P{sub 2}O{sub 7}] groups and [MgO{sub 6}] octahedra. The three dimensional structure consists of [Mg{sub 3}P{sub 2}O{sub 13}]{sub {infinity}} infinite layers parallel to the bc plane. The layers are built up from [MgO{sub 6}] octahedra and [PO{sub 4}] tetrahedral, they are connected along the a axis by O-P-O-P-O bridges of the diphosphate groups. Large tunnels extending along the three main crystallographic directions host four crystallographically distinct sodium cations. The infrared spectrum of Na{sub 4}Mg{sub 3}(PO{sub 4}){sub 2}(P{sub 2}O{sub 7}) is interpreted on the basis of P{sub 2}O{sub 7}{sup 4-} and PO{sub 4}{sup 3-} vibrations. The appearance of {nu}{sub s}P-O-P in the spectrum suggests a bent P-O-P bridge for the P{sub 2}O{sub 7}{sup 4-} ions in the compound, which is in agreement with the X-ray data.

  11. Creation of Cu2O@TiO2 composite photocatalysts with p-n heterojunctions formed on exposed Cu2O facets, their energy band alignment study, and their enhanced photocatalytic activity under illumination with visible light.

    Science.gov (United States)

    Liu, Lingmei; Yang, Weiyi; Sun, Wuzhu; Li, Qi; Shang, Jian Ku

    2015-01-28

    The creation of photocatalysts with controlled facets has become an important approach to enhance their activity. However, how the formation of heterojunctions on exposed facets could affect their photocatalytic performance ranking had not yet been investigated. In this study, Cu2O@TiO2 core-shell structures were created, and Cu2O/TiO2 p-n heterojunctions were formed on various exposed facets of Cu2O cubes, Cu2O cuboctahedra, and Cu2O octahedra, respectively. These Cu2O@TiO2 polyhedra demonstrated an enhanced photocatalytic degradation effect on Methylene Blue (MB) and 4-nitrophenol (4-NP) under visible light illumination, because of the enhanced charge carrier separation by the formation of Cu2O@TiO2 p-n heterojunctions. It was further found that their photocatalytic performance was also facet-dependent as pure Cu2O polyhedra, while the photocatalytic performance ranking of these Cu2O@TiO2 polyhedra was different with that of their corresponding Cu2O polyhedron cores. By the combination of optical property measurement and XPS analysis, the energy band alignments of these Cu2O@TiO2 polyhedra were determined, which demonstrated that Cu2O@TiO2 octahedra had the highest band offset for the separation of charge carriers. Thus, the charge-carrier-separation-driven force in Cu2O@TiO2 polyhedra was different from their corresponding Cu2O polyhedron cores, which resulted in their different surface photovoltage spectrum (SPS) responses and different photocatalytic performance rankings.

  12. Structure and thermodynamic stability of UTa 3 O 10 , a U( v )-bearing compound

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Wu, Di; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu; Burns, Peter C.; Navrotsky, Alexandra

    2016-09-09

    Heating a mixture of uranyl(VI) nitrate and tantalum(V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa3O10. The honey colored to yellow brown crystals of UTa3O10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO6]7- octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO6]7- octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO2]+, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa3O10 from Ta2O5, β-U3O7, and U3O8 has been determined to be 13.1 ± 18.1 kJ mol-1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. The close to zero enthalpy of formation of UTa3O10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM3O10 compounds.

  13. Nature's polyoxometalate chemistry: X-ray structure of the Mo storage protein loaded with discrete polynuclear Mo-O clusters.

    Science.gov (United States)

    Kowalewski, Björn; Poppe, Juliane; Demmer, Ulrike; Warkentin, Eberhard; Dierks, Thomas; Ermler, Ulrich; Schneider, Klaus

    2012-06-13

    Some N(2)-fixing bacteria prolong the functionality of nitrogenase in molybdenum starvation by a special Mo storage protein (MoSto) that can store more than 100 Mo atoms. The presented 1.6 Å X-ray structure of MoSto from Azotobacter vinelandii reveals various discrete polyoxomolybdate clusters, three covalently and three noncovalently bound Mo(8), three Mo(5-7), and one Mo(3) clusters, and several low occupied, so far undefinable clusters, which are embedded in specific pockets inside a locked cage-shaped (αβ)(3) protein complex. The structurally identical Mo(8) clusters (three layers of two, four, and two MoO(n) octahedra) are distinguishable from the [Mo(8)O(26)](4-) cluster formed in acidic solutions by two displaced MoO(n) octahedra implicating three kinetically labile terminal ligands. Stabilization in the covalent Mo(8) cluster is achieved by Mo bonding to Hisα156-N(ε2) and Gluα129-O(ε1). The absence of covalent protein interactions in the noncovalent Mo(8) cluster is compensated by a more extended hydrogen-bond network involving three pronounced histidines. One displaced MoO(n) octahedron might serve as nucleation site for an inhomogeneous Mo(5-7) cluster largely surrounded by bulk solvent. In the Mo(3) cluster located on the 3-fold axis, the three accurately positioned His140-N(ε2) atoms of the α subunits coordinate to the Mo atoms. The formed polyoxomolybdate clusters of MoSto, not detectable in bulk solvent, are the result of an interplay between self- and protein-driven assembly processes that unite inorganic supramolecular and protein chemistry in a host-guest system. Template, nucleation/protection, and catalyst functions of the polypeptide as well as perspectives for designing new clusters are discussed.

  14. Structure and magnetic investigations of Ca1-xYxMnO3 (x=0, 0.1, 0.2, 0.3 and Mn4+/Mn3+ relation analysis

    Directory of Open Access Journals (Sweden)

    Zagorac J.

    2010-01-01

    Full Text Available Structure and magnetic features of nanostructured materials with general formula Ca1-xYxMnO3 (x = 0; 0.1; 0.2; 0.3 were investigated. Goldschmidt tolerance factor, Gt and global instability index, GII were calculated for Ca1-xYxMnO3 (x = 0, 0.25, 0.5, 0.75, 1 using the software SPuDS (Structure Prediction Diagnostic Software. According to these two parameters possibility of forming perovskite structure type for Ca1-xYxMnO3 solid solution was analyzed. Substitution of Y3+ for Ca2+ provokes reduction of equivalent amount Mn4+ into Mn3+, the presence of which is a reason for many interesting magnetic, transport and structural features of doped CaMnO3. Crystal structure refinement was carried out using Rietveld analysis. Ca1-xYxMnO3 (x = 0; 0.1; 0.2; 0.3 has an orthorombic, Pnma space group that, according to Glazer´s classification belongs to a-b+a- tilt system. Influence of Y amount on Mn-O bond angles and distances, tilting of MnO6 octahedra around all three axes and octahedra deformation were analyzed. Bond valence calculations (BVC were performed to determine Mn valence state. Using EPR (electron paramagnetic resonance magnetic measurements were performed and magnetic properties of solid solutions, orthorombicity degree of unit cell, as well as Mn4+/Mn3+ cations ratio in position B were analyzed. Microstructure size-strain analysis was performed and these results are in nanometric range which is confirmed by TEM images.

  15. Anomalous perovskite PbRuO3 stabilized under high pressure

    Science.gov (United States)

    Cheng, J.-G.; Kweon, K. E.; Zhou, J.-S.; Alonso, J. A.; Kong, P.-P.; Liu, Y.; Jin, Changqing; Wu, Junjie; Lin, Jung-Fu; Larregola, S. A.; Yang, Wenge; Shen, Guoyin; MacDonald, A. H.; Manthiram, Arumugam; Hwang, G. S.; Goodenough, John B.

    2013-01-01

    Perovskite oxides ABO3 are important materials used as components in electronic devices. The highly compact crystal structure consists of a framework of corner-shared BO6 octahedra enclosing the A-site cations. Because of these structural features, forming a strong bond between A and B cations is highly unlikely and has not been reported in the literature. Here we report a pressure-induced first-order transition in PbRuO3 from a common orthorhombic phase (Pbnm) to an orthorhombic phase (Pbn21) at 32 GPa by using synchrotron X-ray diffraction. This transition has been further verified with resistivity measurements and Raman spectra under high pressure. In contrast to most well-studied perovskites under high pressure, the Pbn21 phase of PbRuO3 stabilized at high pressure is a polar perovskite. More interestingly, the Pbn21 phase has the most distorted octahedra and a shortest Pb—Ru bond length relative to the average Pb—Ru bond length that has ever been reported in a perovskite structure. We have also simulated the behavior of the PbRuO3 perovskite under high pressure by first principles calculations. The calculated critical pressure for the phase transition and evolution of lattice parameters under pressure match the experimental results quantitatively. Our calculations also reveal that the hybridization between a Ru:t2g orbital and an sp hybrid on Pb increases dramatically in the Pbnm phase under pressure. This pressure-induced change destabilizes the Pbnm phase to give a phase transition to the Pbn21 phase where electrons in the overlapping orbitals form bonding and antibonding states along the shortest Ru—Pb direction at P > Pc. PMID:24277807

  16. Feasibility Test of Commercial CFD Code for Thermal-Hydraulic Analysis of Wire-wrapped Fuel Pin Bundle in SFR

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Chiwoong; Ha, Kwiseok [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Haeyong, Jeong [Sejong Univ., Daejeon (Korea, Republic of)

    2014-05-15

    acceptable values with certain ranges. However, the heat transfer is highly over-estimated especially higher Pe. It is not avoidable to simplify the interface between wire and fuel rod, because this geometrical complexity results in huge computational load. Thus, different wire configurations and a no-wire case were selected as the test geometries to estimate the sensitivity of the wire geometry. Compared to a no-wire case, a wire creates a higher pressure drop and heat transfer due to a swirling flow. However, there is no existing heat transfer correlation with wire design parameters. By reducing the wire contact area, the pressure drop slightly increased, but the heat transfer was reduced. Since a reduced contact area increases the frictional area, the thermal resistance is increased. The wire configuration is more sensitive during the heat transfer. The turbulent Prandtl number (Pr{sub t}) was considered in this study, and existing Pr{sub t} correlations were compared with the numerical results.

  17. Alkali metal bismuth(III) chloride double salts

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, Andrew W. [Department of Chemistry, College of William and Mary, Williamsburg, VA 23187 (United States); Nicholas, Aaron; Ahern, John C. [Department of Chemistry, University of Maine, Orono, ME 04469 (United States); Chan, Benny [Department of Chemistry, College of New Jersey, Ewing, NJ 08628-0718 (United States); Patterson, Howard H. [Department of Chemistry, University of Maine, Orono, ME 04469 (United States); Pike, Robert D., E-mail: rdpike@wm.edu [Department of Chemistry, College of William and Mary, Williamsburg, VA 23187 (United States)

    2016-06-15

    Evaporative co-crystallization of MCl (M = Na, K, Rb, Cs) with BiOCl in aqueous HCl produces double salts: M{sub x}Bi{sub y}Cl{sub (x+3y)}·zH{sub 2}O. The sodium salt, Na{sub 2}BiCl{sub 5}·5H{sub 2}O (monoclinic P2{sub 1}/c, a = 8.6983(7) Å, b = 21.7779(17) Å, c = 7.1831(6) Å, β = 103.0540(10)°, V = 1325.54(19) Å{sup 3}, Z = 4) is composed of zigzag chains of μ{sub 2}-Cl-cis-linked (BiCl{sub 5}){sub n}{sup 2n–} chains. Edge-sharing chains of NaCl{sub n}(OH{sub 2}){sub 6−n} octahedra (n = 0, 2, 3) are linked through μ{sub 3}-Cl to Bi. The potassium salt, K{sub 7}Bi{sub 3}Cl{sub 16} (trigonal R−3c, a = 12.7053(9) Å, b = 12.7053(9) Å, c = 99.794(7) Å, V = 13,951(2) Å{sup 3}, Z = 18) contains (Bi{sub 2}Cl{sub 10}){sup 4–} edge-sharing dimers of octahedra and simple (BiCl{sub 6}){sup 3–} octahedra. The K{sup +} ions are 5- to 8-coordinate and the chlorides are 3-, 4-, or 5-coordinate. The rubidium salt, Rb{sub 3}BiCl{sub 6}·0.5H{sub 2}O (orthorhombic Pnma, a = 12.6778(10) Å, b = 25.326(2) Å, c = 8.1498(7) Å, V = 2616.8(4) Å{sup 3}, Z = 8) contains (BiCl{sub 6}){sup 3–} octahedra. The Rb{sup +} ions are 6-, 8-, and 9-coordinate, and the chlorides are 4- or 5-coordinate. Two cesium salts were formed: Cs{sub 3}BiCl{sub 6} (orthorhombic Pbcm, a = 8.2463(9) Å, b = 12.9980(15) Å, c = 26.481(3) Å, V = 2838.4(6) Å{sup 3}, Z = 8) being comprised of (BiCl{sub 6}){sup 3–} octahedra, 8-coordinate Cs{sup +}, and 3-, 4-, and 5-coordinate Cl{sup −}. In Cs{sub 3}Bi{sub 2}Cl{sub 9} (orthorhombic Pnma, a = 18.4615(15) Å, b = 7.5752(6) Å, c = 13.0807(11) Å, V = 1818.87(11) Å{sup 3}, Z = 4) Bi octahedra are linked by μ{sub 2}-bridged Cl into edge-sharing Bi{sub 4} squares which form zigzag (Bi{sub 2}Cl{sub 9}){sub n}{sup 3n–} ladders. The 12-coordinate Cs{sup +} ions bridge the ladders, and the Cl{sup −} ions are 5- and 6-coordinate. Four of the double salts are weakly photoluminescent at 78 K, each showing a series of three excitation peaks

  18. Magnetic, ferroelectric and leakage current properties of gadolinium doped bismuth ferrite thin films by sol–gel method

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hone-Zern, E-mail: hzc@hust.edu.tw [Department of Electronic Engineering, Hsiuping University of Science and Technology, Taichung, Taiwan (China); Kao, Ming-Cheng, E-mail: kmc@hust.edu.tw [Department of Electronic Engineering, Hsiuping University of Science and Technology, Taichung, Taiwan (China); Young, San-Lin [Department of Electronic Engineering, Hsiuping University of Science and Technology, Taichung, Taiwan (China); Hwang, Jun-Dar [Department of Electrophysics, National Chiayi University, Chiayi, Taiwan (China); Chiang, Jung-Lung [Department of Mobile Technology, Toko University, Chiayi, Taiwan (China); Chen, Po-Yen [Department of Electronic Engineering, Hsiuping University of Science and Technology, Taichung, Taiwan (China)

    2015-05-01

    Bi{sub 0.9}Gd{sub 0.1}FeO{sub 3} (BGFO) thin films were fabricated on Pt(111)/Ti/SiO{sub 2}/Si(100) substrates by using the sol–gel technology. The effects of annealing temperature (400–700 °C) on microstructure and multiferroic properties of thin films were investigated. The X-ray diffraction analysis showed that the BGFO thin films had an orthorhombic structure. The thin films showed ferroelectric and ferromagnetic properties with remanent polarization (2P{sub r}) of 10 μC/cm{sup 2}, remnant magnetization (2M{sub r}) of 2.4 emu/g and saturation magnetization (M{sub s}) of 5.3 emu/g. A small leakage current density (J) was 4.64×10{sup −8} A/cm{sup 2} under applied field 100 kV/cm. It was found that more than one conduction mechanism is involved in the electric field range used in these experiments. The leakage current mechanisms were controlled by Poole–Frenkel emission in the low electric field region and by Schottky emission from the Pt electrode in the high field region. - Highlights: • Bi{sub 3.96}Pr{sub 0.04}Ti{sub 2.95}Nb{sub 0.05}O{sub 12} thin films were prepared by sol–gel technology. • Thin films showed 2P{sub r} of 10 μC/cm{sup 2}, 2M{sub r} of 2.4 emu/g and M{sub s} of 5.3 emu/g. • Leakage current mechanisms were controlled by Poole–Frenkel and Schottky emission.

  19. Thermal and spectroscopic study to investigate p-aminobenzoic acid, sodium p-aminobenzoate and its compounds with some lighter trivalent lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Teixeira, J.A.; Nunes, W.D.G.; Colman, T.A.D.; Nascimento, A.L.C.S do [Instituto de Química, UNESP—Universidade Estadual Paulista, Campus Araraquara, Departamento de Química Analítica, Araraquara 14801-970, SP (Brazil); Caires, F.J. [Faculdade de Ciências, UNESP—Universidade Estadual Paulista, Campus Bauru, Departamento de Química, Bauru 17033-260, SP (Brazil); Campos, F.X. [Instituto de Química, UNESP—Universidade Estadual Paulista, Campus Araraquara, Departamento de Química Analítica, Araraquara 14801-970, SP (Brazil); Instituto Federal de Educação, Ciência e Tecnologia de Mato Grosso, Primavera do Leste 78850-000, MT (Brazil); Gálico, D.A. [Instituto de Química, UNICAMP—Universidade Estadual de Campinas, Campinas 13083-970, SP (Brazil); Ionashiro, M., E-mail: massaoi@yahoo.com.br [Instituto de Química, UNESP—Universidade Estadual Paulista, Campus Araraquara, Departamento de Química Analítica, Araraquara 14801-970, SP (Brazil)

    2016-01-20

    Highlights: • The p-aminobenzoic acid melts followed partial evaporation. • The stoichiometry of compounds was established by TG, EA and complexometry. • The TG–DTA curves provided previously unreported information about thermal behavior. - Abstract: The characterization, thermal stability and thermal decomposition of some lighter trivalent lanthanide p-aminobenzoates, Ln(C{sub 7}H{sub 6}NO{sub 2}){sub 3}·H{sub 2}O (Ln = La, Ce, Pr, Nd, Sm), as well as the thermal behavior and spectroscopic study of p-aminobenzoic acid C{sub 7}H{sub 7}NO{sub 2} and its sodium salt were investigated. The following methods were utilized: simultaneous thermogravimetry and differential thermal analysis (TG–DTA) in dynamic dry air and nitrogen atmospheres; differential scanning calorimetry (DSC); middle (MIR) and near (NIR) infrared region spectroscopy; evolved gas analysis (EGA); elemental analysis; complexometry; X-ray diffraction (XRD); and diffuse reflectance spectroscopy (DR) in the ultraviolet and visible regions. All the compounds were obtained monohydrated and the thermal decomposition occurred in two, three or four steps in an air atmosphere, and three or four steps in N{sub 2} atmosphere. In both atmospheres (air and N{sub 2}) the final residues were CeO{sub 2}, Pr{sub 6}O{sub 11}, Ln{sub 2}O{sub 3} (Ln = La, Nd, Sm). The results also provided information concerning the coordination mode and thermal behavior, as well as the identification of the gaseous products which evolved during the thermal decomposition of these compounds. The DR and NIR spectra provided information about the ligand absorption bands and the f–f transitions of the Nd{sup 3+}, Pr{sup 3+} and Sm{sup 3+} ions.

  20. Active groups for oxidative activation of C-H bond in C{sub 2}-C{sub 5} paraffins on V-P-O catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms by proton abstraction. A comparison of the results on n-butane and butenes oxidation over vanadyl pyrophosphate allowed to conclude that the paraffin oxidation did not take place due to the molecule dehydrogenation process at the first stage of its conversion. Up to now, more than 100 papers related to paraffins oxidation over vanadyl pyrophosphate and the physico-chemical properties of the catalyst have been published. The process of n-butane oxidation is realized in practice. But still, the question about the nature of active sites of the catalyst and the reaction mechanism remains open and provokes further investigations. The present paper deals with our opinion about the problem and the experimental results supporting it. (orig.)

  1. DFT and time-resolved IR investigation of electron transfer between photogenerated 17- and 19-electron organometallic radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James B.; Kling, Matthias F.; Sawyer, Karma R.; Andersen, Lars K.; Harris, Charles B.

    2008-04-30

    The photochemical disproportionation mechanism of [CpW(CO){sub 3}]{sub 2} in the presence of Lewis bases PR{sub 3} was investigated on the nano- and microsecond time-scales with Step-Scan FTIR time-resolved infrared spectroscopy. 532 nm laser excitation was used to homolytically cleave the W-W bond, forming the 17-electron radicals CpW(CO){sub 3} and initiating the reaction. With the Lewis base PPh{sub 3}, disproportionation to form the ionic products CpW(CO){sub 3}PPh{sub 3}{sup +} and CpW(CO){sub 3}{sup -} was directly monitored on the microsecond time-scale. Detailed examination of the kinetics and concentration dependence of this reaction indicates that disproportionation proceeds by electron transfer from the 19-electron species CpW(CO){sub 3}PPh{sub 3} to the 17-electron species CpW(CO){sub 3}. This result is contrary to the currently accepted disproportionation mechanism which predicts electron transfer from the 19-electron species to the dimer [CpW(CO){sub 3}]{sub 2}. With the Lewis base P(OMe){sub 3} on the other hand, ligand substitution to form the product [CpW(CO){sub 2}P(OMe){sub 3}]{sub 2} is the primary reaction on the microsecond time-scale. Density Functional Theory (DFT) calculations support the experimental results and suggest that the differences in the reactivity between P(OMe){sub 3} and PPh{sub 3} are due to steric effects. The results indicate that radical-to-radical electron transfer is a previously unknown but important process for the formation of ionic products with the organometallic dimer [CpW(CO){sub 3}]{sub 2} and may also be applicable to the entire class of organometallic dimers containing a single metal-metal bond.

  2. Synthesis, crystal structure and optical property of three coordination polymer constructed from m-phenylenediacrylate acid

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, YiFan; Wang, TingTing; Zeng, HePing, E-mail: hpzeng@scut.edu.cn

    2015-01-15

    Three new complexes of the wholly deprotonated flexible ligand m-phenylenediacrylate acid (H{sub 2}mpda), namely, [Zn (mpda) (H{sub 2}O)] [1], [Pr{sub 2}(mpda){sub 2}(H{sub 2}O){sub 2}(CHOO){sub 2}] [2], and [Mn{sub 2}(mpda){sub 2} (H{sub 2}O){sub 4}] [3], were synthesized by the solvothermal reaction. The complexes were characterized by IR spectroscopy, thermogravimetric analysis, and X-ray single-crystal diffraction. A mixed sample [Nd(mpda)(H{sub 2}O)(CHOO)·Pr(mpda)(H{sub 2}O)(CHOO)] [2{sup ]} was also synthesized and studied. Compounds [1] and [2] exhibit a selective sensing function with respect to acetone, and they are a potential luminescent sensory material for the selective detection of Zn{sup 2+} and Ni{sup 2+} ions, respectively. Furthermore, the fluorescent changes of compound [1] upon the addition of cations (Fe{sup 3+} and Zn{sup 2+}, Bi{sup 2+} and Zn{sup 2+}) are utilized to construct two logic gates at the molecular level. - Graphical abstract: Three new complexes of flexible ligand m-phenylenedicarboxylic acid were synthesized by solvothermal reaction. Three metal−organic frameworks exhibiting 1D, 2D, 3D structures, respectively. - Highlights: • Three new complexes of m-phenylenedicarboxylic acid were synthesized. • Three metal−organic frameworks exhibiting 1D, 2D, 3D structures, respectively. • [1] and [2] exhibits a very high quenching effect with acetone. • [1] and [2] are a potential luminescent sensory material for Zn{sup 2+}, Ni{sup 2+} ions. • Two logic gates have been constructed using compound [1].

  3. Planetary Candidates Observed by Kepler, III: Analysis of the First 16 Months of Data

    Energy Technology Data Exchange (ETDEWEB)

    Batalha, Natalie M.; /San Jose State U.; Rowe, Jason F.; /NASA, Ames; Bryson, Stephen T.; /NASA, Ames; Barclay, Thomas; /NASA, Ames; Burke, Christopher J.; /NASA, Ames; Caldwell, Douglas A.; /NASA, Ames; Christiansen, Jessie L.; /NASA, Ames; Mullally, Fergal; /NASA, Ames; Thompson, Susan E.; /NASA, Ames; Brown, Timothy M.; /Las Cumbres Observ.; Dupree, Andrea K.; /Harvard-Smithsonian Ctr. Astrophys. /UC, Santa Cruz

    2012-02-01

    New transiting planet candidates are identified in sixteen months (May 2009 - September 2010) of data from the Kepler spacecraft. Nearly five thousand periodic transit-like signals are vetted against astrophysical and instrumental false positives yielding 1091 viable new planet candidates, bringing the total count up to over 2,300. Improved vetting metrics are employed, contributing to higher catalog reliability. Most notable is the noise-weighted robust averaging of multiquarter photo-center offsets derived from difference image analysis which identifies likely background eclipsing binaries. Twenty-two months of photometry are used for the purpose of characterizing each of the new candidates. Ephemerides (transit epoch, T{sub 0}, and orbital period, P) are tabulated as well as the products of light curve modeling: reduced radius (R{sub P}/R{sub {star}}), reduced semi-major axis (d/R{sub {star}}), and impact parameter (b). The largest fractional increases are seen for the smallest planet candidates (197% for candidates smaller than 2R{sub {circle_plus}} compared to 52% for candidates larger than 2R{sub {circle_plus}}) and those at longer orbital periods (123% for candidates outside of 50 day orbits versus 85% for candidates inside of 50 day orbits). The gains are larger than expected from increasing the observing window from thirteen months (Quarter 1 - Quarter 5) to sixteen months (Quarter 1 - Quarter 6). This demonstrates the benefit of continued development of pipeline analysis software. The fraction of all host stars with multiple candidates has grown from 17% to 20%, and the paucity of short-period giant planets in multiple systems is still evident. The progression toward smaller planets at longer orbital periods with each new catalog release suggests that Earth-size planets in the Habitable Zone are forthcoming if, indeed, such planets are abundant.

  4. Synthesis and properties of Pr-substituted MgZn ferrites for core materials and high frequency applications

    Energy Technology Data Exchange (ETDEWEB)

    Mukhtar, Muhammad Waqas; Irfan, Muhammad [Department of Physics, Federal Urdu University of Arts, Science and Technology, Islamabad 44000 (Pakistan); Ahmad, Ishtiaq; Ali, Ihsan [Department of Physics, Bahauddin Zakariya University, Multan 60800 (Pakistan); Akhtar, Majid Niaz [Department of Physics, COMSATS Institute of Information Technology, Lahore (Pakistan); Khan, Muhammad Azhar [Department of Physics, Islamia University, Bahawalpur (Pakistan); Abbas, Ghazanfar [Department of Physics, COMSATS Institute of Information Technology, Islamabad 44000 (Pakistan); Rana, M.U. [Center of Excellence in Solid State Physics, University of the Punjab, Lahore (Pakistan); Ali, Akbar [Department of Basic Sciences, Riphah International University, Islamabad-44000 (Pakistan); Ahmad, Mukhtar, E-mail: ahmadmr25@yahoo.com [Department of Physics, COMSATS Institute of Information Technology, Islamabad 44000 (Pakistan)

    2015-05-01

    A series of single phase spinel ferrites having chemical formula Mg{sub 0.5}Zn{sub 0.5}Pr{sub x}Fe{sub 2−x}O{sub 4} (x=0.00, 0.05, 0.10, 0.15, 0.20, 0.25) were prepared using the sol–gel technique after sintering at 700 °C. The thermal decomposition behavior of an as prepared powder was investigated by means of DTA/TGA analyses. The sintered powders were then characterized by Fourier transform infrared spectroscope, X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscope and vibrating sample magnetometer. X-ray diffraction patterns confirm the single phase spinel structure of prepared ferrites without the presence of any impurity phase. The value of lattice parameter (a) increases with the increase of Pr contents (x) into the spinel lattice. The grain size estimated from electron microscope images is in the range of 2.75–5.4 µm which confirms the spinel crystalline nature of the investigated samples. The saturation magnetization (M{sub s}) decreases whereas coercivity (H{sub c}) increases with the increase of Pr contents (x). The measured parameters suggest that these materials are favorable for high frequency applications and as core materials. - Highlights: • Pr-substituted spinel ferrites synthesized by autocombustion route have been investigated. • The average grain size was in the range of 2.75–5.4 µm estimated by SEM technique. • The (M{sub s}) decreases whereas (H{sub c}) increases with the increase of Pr contents (x). • These parameters are favorable for high frequency applications and as core materials.

  5. Synthesis, structure, and reactivity of (eta/sup 5/-indenyl)tetracarbonylvanadium(I)

    Energy Technology Data Exchange (ETDEWEB)

    Kowaleski, R.M.; Kipp, D.O.; Stauffer, K.J.; Swepston, P.N.; Basolo, F.

    1985-11-06

    The compound (eta/sup 5/-C/sub 9/H/sub 7/)V(CO)/sub 4/ was prepared for the first time and its structure determined by X-ray crystallography. The structure closely resembles that of (eta/sup 5/-C/sub 5/H/sub 5/)V(CO)/sub 4/, with the V(CO)/sub 4/ moiety forming a square pyramid, and a planar indenyl group coordinating to the vanadium through the five-membered ring. The compound crystallizes in the space group Pna2/sub 1/ with a = 22.722 (6) A, b = 6.814 (1) A, c = 7.449 (2) A, and Z = 4. The reaction of (eta/sup 5/-C/sub 9/H/sub 7/)V(CO)/sub 4/ with P(n-Bu)/sub 3/ and with P(OEt)/sub 3/ to form (eta/sup 5/-C/sub 9/H/sub 7/)V(CO)/sub 3/PR/sub 3/ takes place by a dissociative (S/sub N/1) process with kinetic parameters of k(100/sup 0/C) = 3.7 x 10..sqrt../sub 4/ s/sup -1/, ..delta..H = 31.9 +/- 0.3 kcal/mol, and ..delta..S = 10.5 +/- 0.9 cal/(mol K). Again the indenyl effect on dissociative reactions is shown to be much smaller than on associative reactions when compared with the effect for corresponding cyclopentadienyl compounds. 18 references, 1 figure, 4 tables.

  6. Identification and development of nanoscintillators for biotechnology applications

    Energy Technology Data Exchange (ETDEWEB)

    Jung, J.Y. [Materials Science and Engineering Program, University of California—San Diego, 9500 Gilman Dr., La Jolla, CA 92093 (United States); Hirata, G.A. [Centro de Nanociencias y Nanotecnologia UNAM, Km 107 Carretera Tijuana-Ensenada, Ensenada 22860, B.C. (Mexico); Gundiah, G.; Derenzo, S. [Lawrence Berkeley National Laboratory, 1 Cyclotron Rd., Berkeley, CA 94720 (United States); Wrasidlo, W.; Kesari, S.; Makale, M.T. [Translational Neuro-Oncology Laboratories and Department of Neurosciences, University of California, San Diego Moores Cancer Center, 3855 Health Sciences Dr., La Jolla, CA 92093 (United States); McKittrick, J., E-mail: jmckittrick@ucsd.edu [Materials Science and Engineering Program, University of California—San Diego, 9500 Gilman Dr., La Jolla, CA 92093 (United States); Department of Mechanical and Aerospace Engineering, University of California—San Diego, 9500 Gilman Dr., La Jolla, CA 92093 (United States)

    2014-10-15

    The purpose of this work is to investigate the radioluminescence emission properties in the range 300–400 nm of 15 nanoscintillators for potential application in radiation-triggered photodynamic therapy, and compare to those reported for single crystals with same composition. Garnet structures, silicates and an oxide activated with Pr{sup 3+} or Ce{sup 3+} were prepared by combustion synthesis and subsequently annealed at 1200 °C. The (Y{sub 1−x}Pr{sub x}){sub 3}Al{sub 5}O{sub 12} (x=0.0075, 0.01, 0.0125, 0.015, 0.0175) compositions have the highest luminosity, showing concentration behavior for x>0.01. The average particle size of (Y{sub 0.99}Pr{sub 0.01}){sub 3}Al{sub 5}O{sub 12} is 80 nm, which was obtained by post-annealing high power ultrasonic processing. These results demonstrate that (Y{sub 1−x}Pr{sub x}){sub 3}Al{sub 5}O{sub 12} is an excellent candidate for nanoscintillators-based biomedical applications. Comparisons to single crystal data indicate a general trend cannot be established between the radioluminescence emission intensity of nanoscintillators and single crystals with the same composition. - Highlights: • Nanoscintillators were synthesized by combustion reaction with high power ultrasonic processing. • Nanocrystalline (Y{sub 1−x}Pr{sub x}){sub 3}Al{sub 5}O{sub 12} has potential in radiation-triggered photodynamic therapy. • Nanocrystalline scintillators do not follow the same general trend as single crystal scintillators.

  7. The thermochemical of cerias in anodic conditions of fuel cell; A termoquimica de cerias nas condicoes anodicas de pilha a combustivel

    Energy Technology Data Exchange (ETDEWEB)

    Caffarena, Valeska da Rocha; Malta, Luiz Fernando Brum; Ogasawara, Tsuneharu [Universidade Federal, Rio de Janeiro, RJ (Brazil). Coordenacao dos Programas de Pos-graduacao de Engenharia. Programa de Engenharia Metalurgica e de Materiais]. E-mail: valeska@metalmat.ufrj.br; Santos, Jorge Gomes dos [Instituto de Engenharia Nuclear (IEN), Rio de Janeiro, RJ (Brazil)]. E-mail: jg@ien.gov.br

    2003-07-01

    Gibbs' free energies of cerias doped with rare earths estimated from experimental data on hydrothermal synthesis allowed to calculate and construct diagrams of log{sub 10} pH{sub 2}O/pH{sub 2} versus temperature and log{sub 10} pCO{sub 2}/pCO versus temperature, for x = 0.1 and x = 0.01 (where x = fraction of the original ceria converted to Ce{sub 2}O{sub 3}). These diagrams show that cerias doped with rare-earths are more stable than pure ceria, under contact with hydrogen gas or hydrogen-carbon monoxide gaseous mixture which is found in anode region of solid oxide fuel cells operated with pure hydrogen or in situ reformed hydrocarbons. Among doped cerias, the chemical stability increases in the order:: Ce{sub 1.7}Eu{sub .0.}3O{sub 3.85} , Ce{sub 7.47}Sm{sub 1.53}TbO{sub 18.735} , Ce{sub 0.8}La{sub 0.2}O{sub 1.9} e Ce{sub 0.8}Pr{sub 0.4}O{sub 1.8}. In the case of fuel cell operation with CO +H{sub 2} mixture, the Boudouard's equilibrium determines the operational conditions in log{sub 10} pCO{sub 2}/pCO versus temperature domain. (author)

  8. Development of novel CO{sub 2}-stable oxygen permeable dual phase membranes for CO{sub 2} capture in an oxy-fuel process

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Huixia

    2012-07-19

    the cubic perovskite structure, which then becomes unstable. Chapter 3 demonstrated the development of the CO{sub 2}-stable alkaline-earth metals-free dual phase membranes. There novel dual phase membranes ofthe compositions: 40 wt.% NiFe{sub 2}O{sub 4-{delta}} - 60 wt.% Ce{sub 0.9}Gd{sub 0.1}O{sub 2-{delta}} (40NFO-60CGO), 40 wt.% Fe{sub 2}O{sub 3-{delta}} - 60 wt.% Ce{sub 0.9}Gd{sub 0.1}O{sub 2-{delta}} (40FO-60CGO), 40 wt.% Mn{sub 1.5}Co{sub 1.5}O{sub 4-{delta}} - 60 wt.% Ce{sub 0.9}Pr{sub 0.1}O{sub 2-{delta}} (40MCO-60CPO) were developed using different methods, including mixing powder by hand, mixing powder by ball-milling, one-pot single-step sol-gel method. The structures of the dual phase membranes were studied in detail by various analytical techniques such as in-situ XRD, SEM, back-scattered SEM (BSEM), EDXS, STEM and selected-area electron diffraction (SAED). lt was found that all these dual phase membranes show two weil separated phases. Moreover, the in-situ one-pot single-step sol-gel method was found to be the best way to prepare well-distribution dual phase membranes. On the other hand, since our dual phase membranes do not contain alkaline-earth metals, it can be expected that they are C02-stable. The oxygen permeation flux measurements were performed for a few days and no decrease of the oxygen permeation flux was observed, which confirms that these dual phase membranes are CO{sub 2}-stable. However, it is shown that all these materials are not stable in reducing atmosphere, since they contain easily reducible metals oxides of Co, Ni in their compositions. Chapter 4 demonstrated the development of a novel cobalt-free noble metal-free oxygen-permeable 40 wt.% Pr{sub 0.6}Sr{sub 0.4}FeO{sub 3-{delta}} - 60 wt.% Ce{sub 0.9}Pr{sub 0.1}O{sub 2-{delta}} (40PSFO-60CPO) dual phase membrane. The structures of the dual phase membranes were investigated in detail by various analytical techniques such as in-situ XRD, SEM, BSEM and EDXS. ln-situ XRD measurements

  9. Microwave-Assisted Synthesis of Arene Ru(II Complexes Induce Tumor Cell Apoptosis Through Selectively Binding and Stabilizing bcl-2 G-Quadruplex DNA

    Directory of Open Access Journals (Sweden)

    Yanhua Chen

    2016-05-01

    Full Text Available A series of arene Ru(II complexes coordinated with phenanthroimidazole derivatives, [(η6-C6H6Ru(lCl]Cl(1b L = p-ClPIP = 2-(4-Chlorophenylimidazole[4,5f] 1,10-phenanthroline; 2b L = m-ClPIP = 2-(3-Chlorophenylimidazole[4,5f] 1,10-phenanthroline; 3b L = p-NPIP = 2-(4-Nitrophenylimidazole[4,5f] 1,10-phenanthroline; 4b L = m-NPIP = 2-(3-Nitrophenyl imidazole [4,5f] 1,10-phenanthroline were synthesized in yields of 89.9%–92.7% under conditions of microwave irradiation heating for 30 min to liberate four arene Ru(II complexes (1b, 2b, 3b, 4b. The anti-tumor activity of 1b against various tumor cells was evaluated by MTT assay. The results indicated that this complex blocked the growth of human lung adenocarcinoma A549 cells with an IC50 of 16.59 μM. Flow cytometric analysis showed that apoptosis of A549 cells was observed following treatment with 1b. Furthermore, the in vitro DNA-binding behaviors that were confirmed by spectroscopy indicated that 1b could selectively bind and stabilize bcl-2 G-quadruplex DNA to induce apoptosis of A549 cells. Therefore, the synthesized 1b has impressive bcl-2 G-quadruplex DNA-binding and stabilizing activities with potential applications in cancer chemotherapy.

  10. Magnetic resonance enterography in pediatric celiac disease.

    Science.gov (United States)

    Koc, Gonca; Doganay, Selim; Sevinc, Eylem; Deniz, Kemal; Chavhan, Govind; Gorkem, Sureyya B; Karacabey, Neslihan; Dogan, Mehmet S; Coskun, Abdulhakim; Aslan, Duran

    To assess if magnetic resonance enterography is capable of showing evidence/extent of disease in pediatric patients with biopsy-proven celiac disease by comparing with a control group, and to correlate the magnetic resonance enterography findings with anti-endomysial antibody level, which is an indicator of gluten-free dietary compliance. Thirty-one pediatric patients (mean age 11.7±3.1 years) with biopsy-proven celiac disease and 40 pediatric patients as a control group were recruited in the study. The magnetic resonance enterography images of both patients with celiac disease and those of the control group were evaluated by two pediatric radiologists in a blinded manner for the mucosal pattern, presence of wall thickening, luminal distention of the small bowel, and extra-intestinal findings. Patient charts were reviewed to note clinical features and laboratory findings. The histopathologic review of the duodenal biopsies was re-conducted. The mean duration of the disease was 5.6±1.8 years (range: 3-7.2 years). In 24 (77%) of the patients, anti-endomysial antibody levels were elevated (mean 119.2±66.6RU/mL). Magnetic resonance enterography revealed normal fold pattern in all the patients. Ten (32%) patients had enlarged mesenteric lymph nodes. Although a majority of the patients had elevated anti-endomysial antibody levels indicating poor dietary compliance, magnetic resonance enterography did not show any mucosal abnormality associated with the inability of magnetic resonance enterography to detect mild/early changes of celiac disease in children. Therefore, it may not be useful for the follow-up of pediatric celiac disease. Copyright © 2017 Sociedade Brasileira de Pediatria. Published by Elsevier Editora Ltda. All rights reserved.

  11. Non-aqueous route spray pyrolyzed Ru:Co{sub 3}O{sub 4} thin electrodes for supercapacitor application

    Energy Technology Data Exchange (ETDEWEB)

    Ambare, R.C. [School of Physical Sciences, Solapur University, Solapur 413 255, M.S. (India); Bharadwaj, S.R. [Chemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai 400 085, M.S. (India); Lokhande, B.J., E-mail: bjlokhande@yahoo.com [School of Physical Sciences, Solapur University, Solapur 413 255, M.S. (India)

    2015-09-15

    Graphical abstract: - Highlights: • Ru incorporated Co{sub 3}O{sub 4} electrodes were prepared using spray pyrolysis using methanolic media. • XRD shows polycrystalline nature with spherical granular, flowery, porous type morphology. • Ru % incorporation affects the crystallinity, morphology, shape of CV and SC. • 0.6% Ru incorporation shows highest value of SC 628.3 F/g with good stability in 1 M KOH. • Internal resistance observed from Nyquist plot is around 1.05 Ω. - Abstract: Spray pyrolytic deposition of ruthenium incorporated cobalt oxide thin film electrodes was carried out via methanolic route at 623 ± 2 K. Structural, morphological, optical, compositional and electrochemical study was made using XRD, SAED, SEM, TEM, UV–vis, EDX, XPS and electrochemical work station. Deposited samples shows face centered cubic crystal structure for Co{sub 3}O{sub 4} and tetragonal for RuO{sub 2} having crystalline nature was confirmed form SAED. Mixed oxide samples having porous nano-grain morphology and mixed microstructure as observed form SEM and TEM. Cyclic voltammogram study reveals double-pseudo-capacitive nature with optimum specific capacitance (SC) 628.33 F/g at the scan rate 1 mV/s in 1 M KOH with good stability. Charge–discharge behavior was studied to calculate electric parameters such as specific energy (SE), specific power (SP) and columbic efficiency (η). The calculated maximum values are SE 19.94 W h/kg, SP 5.33 kW/kg and η 99.43%. Electrochemical impedance study was made in the frequency range 1 mHz to 1 MHz to see the internal resistance and capacitive behavior of the optimized sample. The randles equivalent circuit and its parameters are reported in the text.

  12. Flux growth in a horizontal configuration: An analog to vapor transport growth

    Science.gov (United States)

    Yan, J.-Q.; Sales, B. C.; Susner, M. A.; McGuire, M. A.

    2017-07-01

    Flux growth of single crystals is normally performed in a vertical configuration with an upright refractory container holding the flux melt. At high temperatures, flux dissolves the charge, forming a homogeneous solution before nucleation and growth of crystals takes place under proper supersaturation generated by cooling or evaporating the flux. In this work, we report flux growth in a horizontal configuration with a temperature gradient along the horizontal axis: a liquid transport growth analogous to the vapor transport technique. In a typical liquid transport growth, the charge is kept at the hot end of the refractory container and the flux melt dissolves the charge and transfers it to the cold end. Once the concentration of charge is above the solubility limit at the cold end, the thermodynamically stable phase nucleates and grows. Compared to the vertical flux growth, the liquid transport growth can provide a large quantity of crystals in a single growth since the charge/flux ratio is not limited by the solubility limit at the growth temperature. This technique is complementary to the vertical flux growth and can be considered when a large amount of crystals is needed but the yield from the conventional vertical flux growth is limited. We applied this technique to the growth of IrSb3, Mo3Sb7 , and MnBi from self-flux, and the growth of FeSe, CrTe3, NiPSe3, FePSe3, CuInP2S6 , RuCl3, and OsCl4 from a halide flux.

  13. In-situ Analysis of Diamonds and Their Mineral Inclusions From the Lynx Kimberlite Dyke Complex, Central Quebec

    Science.gov (United States)

    van Rythoven, A.; McCandless, T. E.; Schulze, D. J.; Bellis, A.; Taylor, L. A.; Liu, Y.

    2009-05-01

    Twenty diamonds from the 522 Ma Lynx kimberlite dyke complex were selected from 442 stones in the 1.47- 3.45mm (+3 to +11 DTC) sieve class on the basis of visible inclusions. The 442 diamonds are part of a larger population of 6598 stones produced from 34 t and 494 t bulk samples taken in 2005 and 2007, respectively. The twenty diamonds all have octahedral primary growth forms. Three macles occur, as does one example of two intergrown octahedra connected along their {111} faces. Two samples are coarse intergrowths of octahedra. Most of the diamonds display a significant degree of resorption and range from octahedra with rounded corners and edges to tetrahexahedroida. Shield and serrate laminae, and hillocks are the most common resorption-related surface features. Nineteen of the samples have light brown to brown colouration. After their external morphology was examined, the diamonds were cut and polished along a single plane to expose included mineral grains for compositional analysis and to image internal structure. Cathodoluminescence imaging reveals deformation lamellae in the majority of the diamonds. A subset of these stones show deformation lamellae truncated by growth/resorption zones and in some cases intersection of planes of different orientation. Oscillatory planar growth patterns are the most common. However, examples of simple homogeneous, complex planar, and complex undulating growth zones occur. Inclusions, particularly olivine, typically occur in core/early growth regions of the diamonds. Of the twenty diamonds, sixteen have primary inclusions. The inclusion suite is largely peridotitic. Seventeen forsteritic olivine inclusions occur in ten diamonds and have molar Mg/(Mg+Fe)= 0.916-0.933. Seven Cr-diopside inclusions occur in one diamond (2.2-2.3 wt. % Cr2O3). Four Cr-pyropes (Cr/(Cr+Al) = 0.28-0.41) occur in three diamonds. Two enstatite inclusions (Mg/(Mg+Fe) = 0.938-0.94) occur in two diamonds. One heterogeneous inclusion of monosulfide solid

  14. Crystal structures and magnetic properties of iron (III)-based phosphates: Na{sub 4}NiFe(PO{sub 4}){sub 3} and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Essehli, Rachid, E-mail: rachid_essehli@yahoo.fr [Laboratory of Mineral Solid and Analytical Chemistry ' LCSMA' , Department of Chemistry, Faculty of Sciences, University Mohamed I, Po. Box 717, 60000 Oujda (Morocco); Bali, Brahim El [Laboratory of Mineral Solid and Analytical Chemistry ' LCSMA' , Department of Chemistry, Faculty of Sciences, University Mohamed I, Po. Box 717, 60000 Oujda (Morocco); Benmokhtar, Said [LCMS, Laboratoire de Chimie des Materiaux Solides, Departement de chimie, Faculte des Sciences Ben M' SIK, Casablanca (Morocco); Bouziane, Khalid [Physics Department, College of Science, Sultan Qaboos University, PO Box 36, Postal Code 123 Al Khod, Sultanate of Oman (Oman); Manoun, Bouchaib [Laboratoire de Physico-Chimie des Materiaux, Departement de Chimie, FST Errachidia, University Moulay Ismail, B.P. 509 Boutalamine, Errachidia (Morocco); Abdalslam, Mouner Ahmed [Materials Science, Technical University Darmstadt, Darmstadt (Germany); Ehrenberg, Helmut [IFW Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany)

    2011-01-28

    Graphical abstract: A perspective view of the Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3} structure along the [0 0 1] direction. Both compounds seem to exibit antiferromagnetic interactions between magnetic entities at low temperature. Display Omitted Research highlights: > Nasicon and Alluaudite compounds, Iron(III)-based phosphates, Crystal structures of Na{sub 4}NiFe(PO{sub 4}){sub 3} and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3}. > Magnetism behaviours of Na{sub 4}NiFe(PO{sub 4}){sub 3} and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3}. > Antiferromagnetism interactions. > Mossbauer spectroscopy. - Abstract: Crystal structures from two new phosphates Na{sub 4}NiFe(PO{sub 4}){sub 3} (I) and Na{sub 2}Ni{sub 2}Fe(PO{sub 4}){sub 3} (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) A, c = 21.643(4) A, R{sub 1} = 0.041, wR{sub 2}=0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) A, b = 12.433(5) A, c = 6.431(2) A, {beta} = 113.66(4){sup o}, R{sub 1} = 0.043, wR{sub 2}=0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O{sub 6}] octahedra and [PO{sub 4}] tetrahedra forming [NiFe(PO{sub 4}){sub 3}]{sup 4+} units which align in chains along the c-axis. The Na{sup +} cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni{sub 2}O{sub 10}] units of edge-sharing [NiO{sub 6}] octahedra, which alternate with [FeO{sub 6}] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na{sup +}. The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Moessbauer measurements performed at 4.2 K. The

  15. Recent advances in technetium halide chemistry.

    Science.gov (United States)

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

  16. Atomic scale investigation of planar defects in 0.95Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–0.05BaTiO{sub 3} thin films on SrTiO{sub 3} (001) substrates

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Xiao-Wei; Lu, Lu [The School of Electronic and Information Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Mi, Shao-Bo, E-mail: shaobo.mi@mail.xjtu.edu.cn [State Key Laboratory for Mechanical Behavior of Materials, Xi' an Jiaotong University, Xi' an 710049 (China); Cheng, Sheng; Liu, Ming [The School of Electronic and Information Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Jia, Chun-Lin [The School of Electronic and Information Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Peter Grünberg Institute and Ernst Ruska Center for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich, D-52425 Jülich (Germany)

    2016-08-15

    Thin films of lead-free piezoelectric 0.95Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}–0.05BaTiO{sub 3} (0.95NBT–0.05BT) are epitaxially grown on single crystalline SrTiO{sub 3} (001) substrates at 800 °C, 850 °C and 900 °C, respectively, by a high-pressure sputtering deposition technique. The microstructure of the thin films is investigated by means of aberration-corrected scanning transmission electron microscopy. Planar defects are observed and the density of the defects increases with the increase of the film-growth temperature. Two types of planar defects in the films are studied at the atomic scale. One consists of groups of edge-sharing TiO{sub 6} octahedra with Bi atoms located between the TiO{sub 6} octahedral groups, and the other exists in the form of Na/Bi(Ba)−O{sub 2}−Na/Bi(Ba) layer parallel to the (010) plane of the films. Based on the structure feature of the planar defects, the propagation of the planar defects related to edge-sharing TiO{sub 6} octahedra within the films and from the film-substrate interface is discussed. Furthermore, the ordering of the planar defects is expected to form new structures. In comparison with the microstructure of 0.95NBT–0.05BT bulk materials, the appearance of the high-density planar defects observed within the films could be considered to be responsible for the difference in the physical properties between the bulk materials and the films. - Highlights: • NBT–BT films have been successfully prepared on SrTiO{sub 3} (001) substrates. • Complex planar defects of zigzag-like and Aurivillius-type have been determined. • The propagation of the planar defects in the films has been characterized. • The intergrowth of planar faults with NBT–BT structure units results in the formation of new structures. • The NBT–BT/SrTiO{sub 3} interface structure has been determined at the atomic scale.

  17. Transformation of Structure, Electrical Conductivity, and Magnetism in AA'Fe2O6-δ, A = Sr, Ca and A' = Sr.

    Science.gov (United States)

    Hona, Ram Krishna; Huq, Ashfia; Mulmi, Suresh; Ramezanipour, Farshid

    2017-08-21

    The ability to control electrical properties and magnetism by varying the crystal structure using the effect of the A-site cation in oxygen-deficient perovskites has been studied in AA'Fe 2 O 6-δ , where A = Sr, Ca and A' = Sr. The structure of Sr 2 Fe 2 O 6-δ , synthesized at 1250 °C in air, contains dimeric units of FeO 5 square pyramids separated by FeO 6 octahedra. Here we show that this ordering scheme can be transformed by changing the A-site cations from Sr to Ca. This leads to a structure where layers of corner-sharing FeO 6 octahedra are separated by chains of FeO 4 tetrahedra. Through systematic variation of the A-site cations, we have determined the average ionic radius required for this conversion to be ∼1.41 Å. We have demonstrated that the magnetic structure is also transformed. The Sr 2 compound has an incommensurate magnetic structure, where magnetic moments are in spin-density wave state, aligning perpendicular to the body diagonal of the unit cell. With the aid of neutron diffraction experiments at 10 and 300 K, we have shown that the magnetic structure is converted into a long-range G-type antiferromagnetic system when one Sr is replaced by Ca. In this G-type ordering scheme, the magnetic moments align in the 001 direction, antiparallel to their nearest neighbors. We have also performed variable-temperature electrical conductivity studies on these materials in the temperature range 298-1073 K. These studies have revealed the transformation of charge transport properties, where the metallic behavior of the Sr 2 compound is converted into semiconductivity in the CaSr material. The trend of conductivity as a function of temperature is reversed upon changing the A-site cation. The conductivity of the Sr 2 compound shows a downturn, while the conductivity of the CaSr material increases as a function of temperature. We have also shown that the CaSr compound exhibits temperature-dependent behavior typical of a mixed ionic-electronic conducting

  18. Structural and magnetic properties of RTiNO{sub 2} (R=Ce, Pr, Nd) perovskite nitride oxides

    Energy Technology Data Exchange (ETDEWEB)

    Porter, Spencer H. [Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong 2522, NSW (Australia); Huang, Zhenguo, E-mail: zhenguo@uow.edu.au [Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong 2522, NSW (Australia); Cheng, Zhenxiang [Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong 2522, NSW (Australia); Avdeev, Maxim [Bragg Institute, Australian Nuclear Science and Technology Organization, Menai 2234, NSW (Australia); Chen, Zhixin; Dou, Shixue [Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong 2522, NSW (Australia); Woodward, Patrick M., E-mail: woodward@chemisty.ohio-state.edu [The Ohio State University, Dept. of Chemistry & Biochemistry, 100 W. 18th Ave, Columbus, OH 43210 (United States)

    2015-03-15

    Neutron powder diffraction indicates that CeTiNO{sub 2} and PrTiNO{sub 2} crystallize with orthorhombic Pnma symmetry (Ce: a=5.5580(5), b=7.8369(7), and c=5.5830(4) Å; Pr: a=5.5468(5), b=7.8142(5), and c=5.5514(5) Å) as a result of a{sup –}b{sup +}a{sup –} tilting of the titanium-centered octahedra. Careful examination of the NPD data, confirms the absence of long range anion order in both compounds, while apparent superstructure reflections seen in electron diffraction patterns provide evidence for short range anion order. Inverse magnetic susceptibility plots reveal that the RTiNO{sub 2} (R=Ce, Pr, Nd) compounds are paramagnetic with Weiss constants that vary from −28 to −42 K. Effective magnetic moments for RTiNO{sub 2} (R=Ce, Pr, Nd) are 2.43 μ{sub B}, 3.63 μ{sub B}, and 3.47 μ{sub B}, respectively, in line with values expected for free rare-earth ions. Deviations from Curie–Weiss behavior that occur below 150 K for CeTiNO{sub 2} and below 30 K for NdTiNO{sub 2} are driven by magnetic anisotropy, spin–orbit coupling, and crystal field effects. - Graphical abstract: The structure and magnetism of the oxide nitride perovskites RTiNO{sub 2} (R=Ce, Pr, Nd) have been explored. The average symmetry is shown to be Pnma with a random distribution of oxide and nitride ions and a{sup −}b{sup +}a{sup −} tilting of the titanium-centered octahedra, but electron diffraction shows evidence for short range anion order. All three compounds are paramagnetic but deviations from the Curie Weiss law are seen below 150 K for R=Ce and below 30 K for R=Nd. - Highlights: • The oxide nitride perovskites RTiNO{sub 2} (R=Ce, Pr) have been prepared and their structures determined. • Diffraction measurements indicate short range cis-order of O and N, but no long range order. • Compounds are paramagnetic with Weiss constants that vary from −28 to −42 K. • CeTiO{sub 2}N and NdTiO{sub 2}N deviate from Curie–Weiss behavior below 150 and 30 K, respectively.

  19. Structure and magnetic properties of Ba{sub 5}Ce{sub 1.25}Mn{sub 3.75}O{sub 15}, a new 10H-polytype in the Ba-Ce-Mn-O system

    Energy Technology Data Exchange (ETDEWEB)

    Macias, Mario A. [Grupo de Investigacion en Quimica Estructural (GIQUE), Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9, Ciudad Universitaria, Bucaramanga (Colombia); Mentre, Olivier [Universite Lille Nord de France, Unite de Catalyse et de Chimie du Solide, Equipe Chimie du Solide, Avenue Dimitri Mendeleieev, Batiment C7, ENSCL/UST Lille 1, BP 90108, 59652 Villeneuve d' Ascq Cedex (France); Colis, Silviu [Institut de Physique et Chimie des Materiaux de Strasbourg (IPCMS), UMR 7504 UDS-CNRS (UDS-ECPM), 23 rue du Loess, BP 43, F-67034 Strasbourg Cedex 2 (France); Cuello, Gabriel J. [Institut Laue Langevin, 6 rue Jules Horowitz BP 156, F-38042 Grenoble cedex 9 (France); Gauthier, Gilles H., E-mail: gilgau@uis.edu.co [Grupo de Investigacion en Quimica Estructural (GIQUE), Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9, Ciudad Universitaria, Bucaramanga (Colombia); CEA, LITEN, Laboratoire d' Innovation Technologique et des Energies Nouvelles, 17 rue des Martyrs, 38054 Grenoble (France)

    2013-02-15

    Based on the peculiar magnetic properties that are observed in pseudo one-dimensional manganites, we decided to synthesize the new Ba{sub 5}Ce{sub 1.25}Mn{sub 3.75}O{sub 15} compound. The preparation was performed by solid state reaction in air at about 1350 Degree-Sign C, for which we found that the compound crystallizes in a hexagonal symmetry with space group P6{sub 3}/mmc (No-194) and cell parameters a=b=5.7861(2) A and c=23.902(1) A. The structural description was correlated with neutron diffraction and bond valence calculations, confirming the presence of Ce{sup 4+} and Mn{sup 4+} segregated in the different crystallographic positions. Ba{sub 5}Ce{sub 1.25}Mn{sub 3.75}O{sub 15} displays evidence for strong AFM couplings already set at room temperature. The main arrangement of Mn{sup 4+} in magnetically isolated tetramers of face-sharing octahedra is responsible for a metamagnetic-like transition around 50 K. - Graphical abstract: The new Ba{sub 5}Ce{sub 1.25}Mn{sub 3.75}O{sub 15} polytype shows strong AFM couplings in magnetically isolated [Ce{sub 0.25}Mn{sub 3.75}O{sub 15}] tetramers of face-sharing octahedral, resulting in a metamagnetic-like transition around 50 K. Highlights: Black-Right-Pointing-Pointer Ba{sub 5}Ce{sub 1.25}Mn{sub 3.75}O{sub 15}, a new 10H polytype, has been prepared in the Ba-Ce-Mn-O system. Black-Right-Pointing-Pointer The compound crystallizes in the P6{sub 3}/mmc space group with (cchhh){sub 2} stacking sequence. Black-Right-Pointing-Pointer [Ce{sub 0.25}Mn{sub 3.75}O{sub 15}] tetramers are separated by [CeO{sub 6}] octahedra in the structure. Black-Right-Pointing-Pointer Instead of robust AFM ordering, a metamagnetic-like transition is found around 50 K.

  20. Crystal structures of two oxygen-deficient perovskite phases in the CaSiO3-CaAlO2.5 join

    Science.gov (United States)

    Kanzaki, Masami; Xue, Xianyu; Wu, Ye; Nie, Shufang

    2017-11-01

    The crystal structures of Ca(Al0.5Si0.5)O2.75 and Ca(Al0.4Si0.6)O2.8 ordered oxygen-deficient perovskite phases are synthesized at 7 and 11 GPa, respectively, and 1500 °C, and were studied using NMR and synchrotron powder X-ray diffraction. 29Si MAS NMR, 27Al MAS and 3Q MAS NMR measurements revealed a single tetrahedral Si and single octahedral Al peak for the Ca(Al0.5Si0.5)O2.75 phase, and a tetrahedral and an octahedral Si peak and a single octahedral Al peak for the Ca(Al0.4Si0.6)O2.8 phase. Using this structural information as constraints, the crystal structures were solved from synchrotron X-ray diffraction data by the structure determination from powder diffraction (SDPD) technique. To double-check the structures, first-principles calculations of NMR parameters (chemical shifts and electric field gradients) were also conducted after relaxing the obtained structures. The calculated NMR parameters of both phases are consistent with the observed NMR spectra. The crystal structures of both phases consist of a perovskite-like layer of (Al,Si)O6 octahedra and a double-layer of SiO4 tetrahedra that are stacked alternatively in the [111] direction of ideal cubic perovskite. The perovskite-like layer is made of a double-layer of Al octahedra for the Ca(Al0.5Si0.5)O2.75 phase, and a triple-layer with a Si octahedral layer sandwiched between two Al octahedral layers for the Ca(Al0.4Si0.6)O2.8 phase. A unique feature common to both structures is that each SiO4 tetrahedron has one terminal oxygen that is not shared by other Si or Al. Homologous relation among these phases and merwinite (Ca3MgSi2O8) in terms of different numbers (1-3) of octahedral layers within the perovskite-like layer is noted.

  1. Crystal structures of KM(AsF{sub 6}){sub 3} (M{sup 2+} = Mg, Co, Mn, Zn), KCu(SbF{sub 6}){sub 3} and [Co(HF){sub 2}]Sr[Sr(HF)]{sub 2}-[Sr(HF){sub 2}]{sub 2}[AsF{sub 6}]{sub 12}

    Energy Technology Data Exchange (ETDEWEB)

    Mazej, Zoran; Goreshnik, Evgeny [Jozef Stefan Institute, Ljubljana (Slovakia). Dept. of Inorganic Chemisrty and Technology

    2015-05-01

    The KM(AsF{sub 6}){sub 3} (M{sup 2+} = Mg, Co, Mn, Zn) and KCu(SbF{sub 6}){sub 3} compounds crystallize isotypically to previously known KNi(AsF{sub 6}){sub 3}. The main features of the structure of these compounds are rings of MF{sub 6} octahedra sharing apexes with AsF{sub 6} octahedra connected into infinite tri-dimensional frameworks. In this arrangement cavities are formed where K{sup +} cations are placed. Single crystals of CoSr{sub 5}(AsF{sub 6}){sub 12}.8HF were obtained as one of the products after the crystallization of 3KF/CoF{sub 2}/SrF{sub 2} mixture in the presence of AsF{sub 5} in anhydrous HF. The CoSr{sub 5}(AsF{sub 6}){sub 12}.8HF is monoclinic, C/2c (No.15), with a = 26.773(5) Aa, b = 10.087(2) Aa, c = 21.141(5) Aa, β = 93.296(13) {sup circle}, V = 5699.9(19) Aa{sup 3} at 200 K, and Z = 4. There are three crystallographically non-equivalent Sr{sup 2+} cations in the crystal structure of CoSr{sub 5}(AsF{sub 6}){sub 12}.8HF. The Sr1 is coordinated by ten fluorine atoms from eight different [AsF{sub 6}]- anions, meanwhile Sr2 and Sr3 are bound to nine fluorine atoms provided by one HF and eight AsF{sub 6} units or by two HF and six AsF{sub 6} units, respectively. The Co{sup 2+} is coordinated distorted-octahedrally by six fluorine atoms from two HF molecules and four different AsF{sub 6} units. All those moieties in the crystal structure of [Co(HF){sub 2}]Sr[Sr(HF)]{sub 2}[Sr(HF){sub 2}]{sub 2}[AsF{sub 6}]{sub 12} are connected into tridimensional framework. The CoSr{sub 5}(AsF{sub 6}){sub 12}.8HF is a unique example of compound where HF molecules are directly bound via fluorine atoms to two different metal centres.

  2. High-temperature order-disorder phase transition in nacaphite, Na2CaPO4F

    Science.gov (United States)

    Avdontceva, Margarita S.; Krzhizhanovskaya, Maria G.; Krivovichev, Sergey V.; Yakovenchuk, Viktor N.

    2015-09-01

    The thermal behavior of nacaphite, Na2CaPO4F, was studied by the powder high-temperature X-ray diffraction method. A monoclinic-to-orthorhombic phase transition has been observed at 330 °C associated with the appearance of the Ca/Na disorder at one of the two crystallographically inequivalent Na sites. At room temperature, nacaphite is monoclinic, P21 /c, a = 13.3185(14), b = 7.0964(8), c = 10.6490(11) Å, β = 113.526(1)°, V = 922.81(17) Å3. The structure is based upon one-dimensional antiperovskite units consisting of face-sharing [FNa4Ca2]7+ anion-centered octahedra running parallel to the c axis. The structure is fully ordered and contains two Ca and four Na sites. The crystal structure of the high-temperature modification [refined by Rietveld method ( R B 0.025) at 400 °C from the powder X-ray diffraction data] is orthorhombic, Pnma, a = 5.4123(1), b = 7.1196(1), c = 12.3171(1) Å, V = 474.62(1) Å3. The structure has one fully occupied Na1 site and one mixed occupied Na2 site, the latter being equally occupied by Na and Ca. The Na1 and Na2 sites are coordinated by two F- and four O2- anions each. The phase transition has an order-disorder character and is associated with the decrease of structural complexity measured as an information content per unit cell (300.235 bits for the low- and 98.117 bits for the high-temperature modifications). Thermal expansion of both modifications has an anisotropic character with the degree of anisotropy increasing from the low- to the high-temperature phase. The direction of the strongest thermal expansion is parallel to the direction of chains of face-sharing anion-centered octahedra that can be explained by the temperature-induced expansion of the F-Na/Ca bonds.

  3. Synthesis, structure and magnetic properties of La{sub 3}Co{sub 2}SbO{sub 9}: A double perovskite with competing antiferromagnetic and ferromagnetic interactions

    Energy Technology Data Exchange (ETDEWEB)

    Franco, D.G.; Fuertes, V.C.; Blanco, M.C. [INFIQC (CONICET), Departamento de Fisicoquimica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Ciudad Universitaria, X5000HUA Cordoba (Argentina); Fernandez-Diaz, M.T. [Institute Laue-Langevin (ILL) 156X, F-38042 Grenoble Cedex 9 (France); Sanchez, R.D., E-mail: rodo@cab.cnea.gov.ar [Centro Atomico Bariloche, CNEA and Instituto Balseiro, Universidad Nacional de Cuyo, Av. Bustillo 9500, 8400 Rio Negro (Argentina); Carbonio, R.E., E-mail: carbonio@fcq.unc.edu.ar [INFIQC (CONICET), Departamento de Fisicoquimica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Ciudad Universitaria, X5000HUA Cordoba (Argentina)

    2012-10-15

    The synthesis, structural characterization, and magnetic properties of La{sub 3}Co{sub 2}SbO{sub 9} double perovskite are reported. The crystal structure has been refined by X-ray and neutron powder diffraction data in the monoclinic space group P2{sub 1}/n. Co{sup 2+} and Sb{sup 5+} have the maximum order allowed for the La{sub 3}Co{sub 2}SbO{sub 9} stoichiometry. Rietveld refinements of powder neutron diffraction data show that at room temperature the cell parameters are a=5.6274(2) A, b=5.6842(2) A, c=7.9748(2) A and {beta}=89.999(3) Degree-Sign . Magnetization measurements indicate the presence of ferromagnetic correlations with T{sub C}=55 K attributed to the exchange interactions for non-linear Co{sup 2+}-O-Sb{sup 5+}-O-Co{sup 2+} paths. The effective magnetic moment obtained experimentally is {mu}{sub exp}=4.38 {mu}{sub B} (per mol Co{sup 2+}), between the theoretical one for spin only (3.87 {mu}{sub B}) and spin-orbit value (6.63 {mu}{sub B}), indicating partially unquenched contribution. The low magnetization value at high magnetic field and low temperature (1 {mu}{sub B}/f.u., 5 T and 5 K) and the difference between ZFC and FC magnetization curves (at 5 kOe) indicate that the ferromagnetism do not reach a long range order and that the material has an important magnetic frustration. - Graphical abstract: Co-O-Co (Yellow octahedra only) rich zones (antiferromagnetic) are in contact with Co-O-Sb-O-Co (Red and yellow octahedra) rich zones (Ferromagnetic) to give the peculiar magnetic properties, as a consequence, a complex hysteresis loop can be observed composed by a main and irreversible curve in all the measured range, superimposed with a ferromagnetic component at low fields. Highlights: Black-Right-Pointing-Pointer La{sub 3}Co{sub 2}SbO{sub 9} has small Goldschmidt Tolerance Factor (t) due to the small size of La{sup 3+}. Black-Right-Pointing-Pointer Small t determines an angle for the path Co{sup 2+}-O-Sb{sup 5+}-O-Co{sup 2+} of 153 Degree-Sign . Black

  4. Syntheses and crystal structures of BaAgTbS{sub 3}, BaCuGdTe{sub 3}, BaCuTbTe{sub 3}, BaAgTbTe{sub 3}, and CsAgUTe{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Prakash, Jai; Beard, Jessica C.; Ibers, James A. [Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (United States); Mesbah, Adel [Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (United States); ICSM-UMR 5257 CNRS/CEA/UM2/ENSCM, Bat 426, BP 17171, 30207 Bagnols/Ceze (France)

    2015-06-15

    Five new quaternary chalcogenides of the 1113 family, namely BaAgTbS{sub 3}, BaCuGdTe{sub 3}, BaCuTbTe{sub 3}, BaAgTbTe{sub 3}, and CsAgUTe{sub 3}, were synthesized by the reactions of the elements at 1173-1273 K. For CsAgUTe{sub 3} CsCl flux was used. Their crystal structures were determined by single-crystal X-ray diffraction studies. The sulfide BaAgTbS{sub 3} crystallizes in the BaAgErS{sub 3} structure type in the monoclinic space group C{sup 3},{sub 2h}-C2/m, whereas the tellurides BaCuGdTe{sub 3}, BaCuTbTe{sub 3}, BaAgTbTe{sub 3}, and CsAgUTe{sub 3} crystallize in the KCuZrS{sub 3} structure type in the orthorhombic space group D{sup 1},{sub 2}{sup 7},{sub h}-Cmcm. The BaAgTbS{sub 3} structure consists of edge-sharing [TbS{sub 6}{sup 9-}] octahedra and [AgS{sub 5}{sup 9-}] trigonal pyramids. The connectivity of these polyhedra creates channels that are occupied by Ba atoms. The telluride structure features {sup 2}{sub ∞}[MLnTe{sub 3}{sup 2-}] layers for BaCuGdTe{sub 3}, BaCuTbTe{sub 3}, BaAgTbTe{sub 3}, and {sup 2}{sub ∞}[AgUTe{sub 3}{sup 1-}] layers for CsAgUTe{sub 3}. These layers comprise [MTe{sub 4}] tetrahedra and [LnTe{sub 6}] or [UTe{sub 6}] octahedra. Ba or Cs atoms separate these layers. As there are no short Q..Q (Q = S or Te) interactions these compounds achieve charge balance as Ba{sup 2+}M{sup +}Ln{sup 3+}(Q{sup 2-}){sub 3} (Q = S and Te) and Cs{sup +}Ag{sup +}U{sup 4+}(Te{sup 2-}){sub 3}. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Structural study of modified Bi{sub 4}V{sub 2}O{sub 10+{delta}} phases ({delta} = 0, 0.5, 1): Influence of antimony contribution

    Energy Technology Data Exchange (ETDEWEB)

    Sorokina, S.; Enjalbert, R.; Baules, P.; Galy, J. [CNRS, Toulouse (France). Centre d`Elaboration de Materiaux et d`Etudes Structurales; Castro, A. [CSIC, Cantoblanco, Madrid (Spain). Inst. de Ciencia de Materiales

    1999-05-01

    Three solid solutions of general composition Bi{sub 4{minus}x}Sb{sub x}V{sub 2}O{sub 10}, Bi{sub 4}V{sub 2{minus}y}{sup 4+}V{sub y}{sup 5+}O{sub 10+y/2}, and Bi{sub 4}V{sub 2{minus}z}Sb{sub z}O{sub 11} have been investigated in the fivefold Bi{sub 2}O{sub 3}-V{sub 2}O{sub 5}-V{sub 2}O{sub 4}-Sb{sub 2}O{sub 3}-Sb{sub 2}O{sub 5} system. These oxides have been characterized by X-ray diffraction and electron microscopy techniques. Single phases have been isolated for values ranging from 0 to x, z = 0.8 and y = 2. Single crystals of Bi{sub 3.2}Sb{sub 0.8}V{sub 2}O{sub 10}, Bi{sub 4}V{sub 2}O{sub 10.5}, and Bi{sub 4}V{sub 1.2}Sb{sub 0.8}O{sub 11} have been grown and their structures determined by X-ray diffraction methods. The three oxides crystallize in the orthorhombic system, space groups F222, Amam, and Fmmm, respectively. Their structures keep the classical two-dimensional array of Aurivillius-like oxides with (Bi, Sb)-O layers interleaved with (V, Sb)-O sheets. It has been found that Sb{sup 3+} is introduced into the bismuth layer, due to its similar sterical behavior, by the presence of a 5s{sup 2} lone pair associated with Sb{sup 3+} and 6s{sup 2} associated with Bi{sup 3+}, whereas Sb{sup 5+} substitutes for the V{sup 5+} cation. All of the substitutions carried out mainly act on the vanadium layer, which can accommodate different coordination polyhedra for cations: tetrahedra for V{sup 5+}, square pyramids and distorted trigonal bipyramids or octahedra for V{sup 4+} and V{sup 5+}, and octahedra for Sb{sup 5+}. This fact can be related to the electrical properties, such as high ionic conduction and ferroelectricity, shown by these types of materials.

  6. Growth and structure of K{sub 2}Ni{sub x}Co{sub (1–x)}(SO{sub 4}){sub 2} · 6H{sub 2}O single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Vasilyeva, N. A., E-mail: Natalie5590@mail.ru; Sorokina, N. I.; Antipin, A. M.; Verin, I. A.; Voloshin, A. E. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2016-01-15

    Single crystals of the K{sub 2}Ni{sub x}Co{sub (1–x)}(SO{sub 4}){sub 2} · 6H{sub 2}O composition are grown by spontaneous flux crystallization. More exact chemical formulas of the single crystals are determined based on the diffraction data as K{sub 2}Co(SO{sub 4}){sub 2} · 6H{sub 2}O (I), K{sub 2}(Co{sub 0.657}Ni{sub 0.343})(SO{sub 4}){sub 2} · 6H{sub 2}O (II), K{sub 2}(Co{sub 0.226}Ni{sub 0.774})(SO{sub 4}){sub 2} · 6H{sub 2}O (III), K{sub 2}(Co{sub 0.216}Ni{sub 0.784})(SO{sub 4}){sub 2} · 6H{sub 2}O (IV), and K{sub 2}Ni(SO{sub 4}){sub 2} · 6H{sub 2}O (V). The substitution of nickel atoms for cobalt atoms in structure I results in a shortening of all (Co,Ni)–O interatomic distances. With increasing Ni concentration, the (Co,Ni)–O2 distance shortens to a lesser degree than the (Co,Ni)–O1 and (Co,Ni)–O3 distances and, as a consequence, the distortion of (Co,Ni)O{sub 6} octahedra decreases. NiO{sub 6} polyhedra are less distorted than CoO{sub 6} octahedra. The analysis of difference syntheses of electron density shows that the number of uninterpretable peaks on the maps of mixed crystals II, III, and IV, as well as on the map of K{sub 2}Co(SO{sub 4}){sub 2} · 6H{sub 2}O, is larger with respect to those of structure K{sub 2}Ni(SO{sub 4}){sub 2} · 6H{sub 2}O.

  7. Order–disorder phase transition in the antiperovskite-type structure of synthetic kogarkoite, Na{sub 3}SO{sub 4}F

    Energy Technology Data Exchange (ETDEWEB)

    Avdontceva, Margarita S.; Zolotarev, Andrey A. [Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Krivovichev, Sergey V., E-mail: s.krivovichev@spbu.ru [Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Institute of Silicate Chemistry, Russian Academy of Sciences, Makarova Emb. 6, 199034 St. Petersburg (Russian Federation)

    2015-11-15

    High-temperature phase transition of synthetic kogarkoite, Na{sub 3}SO{sub 4}F, has been studied by high-temperature X-ray powder and single-crystal diffraction. The temperature of the phase transition can be estimated as 112.5±12.5 °C. The low-temperature phase, α-Na{sub 3}SO{sub 4}F, at 293 K, is monoclinic, P2{sub 1}/m, a=18.065(3), b=6.958(1), c=11.446(1) Å, β=107.711(1)°, Z=12. The structure contains thirteen symmetrically independent Na sites with coordination numbers varying from 6 to 8, and six independent S sites. The high-temperature β-phase at 423 K is rhombohedral, R-3m, a=6.94(1), c=24.58(4) Å, Z=9. The crystal structure of both polymorphs of Na{sub 3}SO{sub 4}F can be described as a 9R antiperovskite polytype based upon triplets of face-sharing [FNa{sub 6}] octahedra linked into a three-dimensional framework by sharing corners. In the α-modification, the SO{sub 4} tetrahedra are completely ordered and located in the framework cavities. In the β-modification, there are only two symmetrically independent Na atoms in the structure. The main difference between the structures of the α- and β-phases is the degree of ordering of the SO{sub 4} tetrahedra: in the α-modification, they are completely ordered, whereas, in the β-modification, the complete disorder is observed, which is manifested in a number of low-occupied O sites around fully occupied S sites. The phase transition is therefore has an order–disorder character and is associated with the decrease of structural complexity measured as an information content per unit cell [577.528 bits for the low- (α) and 154.830 bits for the high- (β) temperature modifications]. - Graphical abstract: High-temperature phase transition of synthetic kogarkoite, Na{sub 3}SO{sub 4}F, revealed the existence of the monoclinic-to-rhombohedral phase transition at 112.5±12.5 °C. The phase transition has an order–disorder character and is associated with the decrease of structural complexity. - Highlights

  8. Different magnetic responses observed in Co, Co and Co-based MOFs.

    Science.gov (United States)

    Zhang, Chao; Liu, Zhong-Yi; Liu, Ning; Zhao, Hong; Yang, En-Cui; Zhao, Xiao-Jun

    2016-07-19

    Four magnetic MOFs with anisotropic Co(II) ions, {[Co5(H2O)2(μ3-OH)2(atz)2(stp)2]·1.5H2O}n (1), {[Co5(H2O)2(μ3-OH)2(trz)2(stp)2]·1.3H2O}n (2), {[Co5(H2O)6(μ3-OH)2(trz)2(stp)2]·2.5CH3OH}n (3) and {[Co3(H2O)4(Hdatrz)2(stp)2]·3H2O}n (4) (stp(3-) = 2-sulfoterephthalate, trz(-) = 1,2,4-triazolate, atz(-) = 3-amino-1,2,4-triazolate and Hdatrz = 3,5-diamino-1,2,4-triazole) were solvothermally isolated by varying the substituent groups appended on the N-heterocyclic triazole and structurally and magnetically characterized. Structural analyses indicate that the former two complexes are crystallographically isostructural, exhibiting pillared-layer frameworks with mixed triazolyl and carboxylate extended Co + Co layers supported by rigid stp(3-) connectors. Complex 3 is built from butterfly-shaped Co cluster-based layers, which are interconnected with single cobalt(ii) octahedra by ditopic stp(3-) bridges. By contrast, complex 4 consists of linear {Co3(μ-N1,N4-Hdatrz)2} subunits, which are extended by 3-connected stp(3-) linkers into a stable 3D framework. Magnetically, 1 exhibits ferromagnetic ordering below 2.7 K due to the well-organized alignment of the non-compensated resultant moment from octahedra and tetrahedral cobalt(ii) carriers, while 3 is in a non-zero paramagnetic state above 2.0 K resulting from the coexistence of intermetallic ferromagnetic and antiferromagnetic interactions. The magnetic competition between weak inter-subunit antiferromagnetic interactions and the external magnetic field makes 4 behave as a field-induced metamagnet with a critical field of 27.5 kOe. These interesting magnetostructural results suggest that the anisotropy of the moment carrier and the interlayer/intersubunit separations significantly dominate the magnetic responses in extended MOFs, providing an informative platform for the further development of interesting magnetic materials, both of academic and industrial interest.

  9. Design and synthesis of nanomaterials for surface-enhanced Raman scattering, fuel cell technology, and photonics

    Science.gov (United States)

    Camargo, Pedro Henrique Cury

    In the first part of my dissertation, I developed two approaches for selectively probing the SERS activities of individual hot spots, i.e., experimentally detect the SERS signals only for the molecules that are trapped within the hot-spot region in individual Ag nanoparticle dimers. Then, I performed a systematic investigation on the SERS activity of individual dimers composed of two closed spaced Ag nanoparticles. By utilizing Ag nanoparticles displaying a variety of well-defined shapes, sizes and orientations to construct the dimers, I were able to precisely correlate the detected SERS signals to the specific geometry of individual hot spots. In the second part of this dissertation, I performed a systematic investigation on the galvanic replacement reaction between PtCl62- and Pd nanocrystals with well-defined shapes including octahedra, nanocubes, and nanorods. The resultant hollow Pd-Pt bimetallic nanostructures were employed as electrocatalysts for the oxygen reduction reaction (ORR). Our results demonstrated that the nanostructures derived from Pd octahedra displayed the highest ORR activity, being 1.7 times more active based on equivalent Pt mass than the commercial Pt/C. I also conducted a mechanistic study on the galvanic replacement reaction between AuCl4- and Pd nanorods. Differently from the Pd-Pt system, a new type of hybrid nanostructure in the tadpole shape consisting of a Au head and a Pd tail was obtained due to a localized galvanic replacement mechanism. As an extension of my work to develop new electrocatalysts for the ORR, a templateengaged reaction was utilized for the synthesis of RuSe2+delta nanotubes. The RuSe2+delta nanotubes were active towards the ORR and displayed no loss in activity in the presence of methanol, as opposed to commercial Pt/C. Finally, the template-engaged reaction was applied to the synthesis of Se MSe (M = Zn, Cd or Pb) colloidal spheres having similar sizes but different compositions. They were utilized as building

  10. Synthesis, crystal structure, and ionic conductivity of a new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung-Chul; Kwak, Hyun-Jung [Department of Energy Systems Research, Ajou University, Suwon 16499 (Korea, Republic of); Yoo, Chung-Yul [Advanced Materials & Devices Laboratory, Korea Institute of Energy Research, Daejeon 34129 (Korea, Republic of); Yun, Hoseop [Department of Energy Systems Research, Ajou University, Suwon 16499 (Korea, Republic of); Kim, Seung-Joo, E-mail: sjookim@ajou.ac.kr [Department of Energy Systems Research, Ajou University, Suwon 16499 (Korea, Republic of)

    2016-11-15

    A new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}, was synthesized in the form of either a single-crystal or polycrystalline powder using the molten hydroxide flux method or a solid-state reaction, respectively. Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} crystallizes to the P2{sub 1}/n (Z=4) monoclinic space group with lattice parameters a≈4.95 Å, b≈22.06 Å, c≈8.63 Å, and β≈91.5°. The structure is composed of stacked [LiSrAl(PO{sub 4}){sub 2}] layers alternating regularly with [LiSrPO{sub 4}] layers. In the [LiSrAl(PO{sub 4}){sub 2}] sublattice, the AlO{sub 6} octahedra and PO{sub 4} tetrahedra are tilted cooperatively to form an anionic, corrugated, two-dimensional [Al(PO{sub 4}){sub 2}]{sup 3−} framework that can be regarded as a “distorted-glaserite” structure. The [LiSrPO{sub 4}] sublattice is that of a layered block containing a six-membered ring formed from alternating linkages of LiO{sub 4} and PO{sub 4} tetrahedra. The six-membered rings show a boat-type arrangement with the up(U) or down(D) pointing sequence, UUDUUD. The interspace between the two sublattices generates a two-dimensional pathway for Li{sup +} ion conduction. The impedance measurement indicated that Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} had a moderate ion conductivity (σ≈1.30×10{sup −4} S cm{sup −1} at 667 K), with an activation energy E{sub a}≈1.02 eV. - Graphical abstract: Polyhedral view of Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}. Li{sup +} ions are represented by green spheres, Sr atoms by white spheres, AlO{sub 6} groups by octahedra, and PO{sub 4} groups by tetrahedra. - Highlights: • New compound Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} is reported. • The crystal structure is investigated by single-crystal XRD analysis. • The structure is formed by the alternate stacking of two different sublattices. • Correlation between the crystal structure and ionic conductivity is discussed.

  11. Synthesis and characterization of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gatimu, Alvin J.; Berthelot, Romain; Muir, Sean; Sleight, Arthur W. [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Subramanian, M.A., E-mail: mas.subramanian@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)

    2012-06-15

    The effects of Ti, Fe and Co substitutions for Ir on the structure and on the physical properties of Sr{sub 2}IrO{sub 4} are investigated. A complete solid solution Sr{sub 2}Ir{sub 1-x}Ti{sub x}O{sub 4} is obtained while both Fe and Co doping are relatively limited. In each case however, the c-axis cell parameter and the initial IrO{sub 6} octahedra tilting decreases with substitution. Doping with Ti, Fe and Co results in a decrease of the magnetic susceptibility and in an increase in the paramagnetic effective moment for Co and Fe doped samples and a suppression of the weak ferromagnetic ordering observed for Sr{sub 2}IrO{sub 4}. - Graphical abstract: Solid solutions of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) have been synthesized and characterized by powder X-ray diffraction, magnetism and electrical measurements. Changes in the a parameter and decreases in both the c-axis cell parameters and the initial IrO{sub 6} octahedra tilting are found to be correlated. Highlights: Black-Right-Pointing-Pointer Solid Solutions of Sr{sub 2}Ir{sub 1-x}M{sub x}O{sub 4} (M=Ti, Fe, Co) are synthesized. Black-Right-Pointing-Pointer The Sr{sub 2}Ir{sub 1-x}Ti{sub x}O{sub 4} solid solution is complete while those of Fe and Co are relatively limited. Black-Right-Pointing-Pointer The change in a cell parameter with substitution is much less than that of the c parameter. Black-Right-Pointing-Pointer Decreased tilting and the smaller size of the M cation contrastingly affect the a parameter. Black-Right-Pointing-Pointer Doping results in a suppression of the weak ferromagnetic ordering in Sr{sub 2}IrO{sub 4}.

  12. Bi(3n+1)Ti7Fe(3n-3)O(9n+11) Homologous Series: Slicing Perovskite Structure with Planar Interfaces Containing Anatase-like Chains.

    Science.gov (United States)

    Batuk, Dmitry; Tsirlin, Alexander A; Filimonov, Dmitry S; Zakharov, Konstantin V; Volkova, Olga S; Vasiliev, Alexander; Hadermann, Joke; Abakumov, Artem M

    2016-02-01

    The n = 3-6 members of a new perovskite-based homologous series Bi(3n+1)Ti7Fe(3n-3)O(9n+11) are reported. The crystal structure of the n = 3 Bi10Ti7Fe6O38 member is refined using a combination of X-ray and neutron powder diffraction data (a = 11.8511(2) Å, b = 3.85076(4) Å, c = 33.0722(6) Å, S.G. Immm), unveiling the partially ordered distribution of Ti(4+) and Fe(3+) cations and indicating the presence of static random displacements of the Bi and O atoms. All Bi(3n+1)Ti7Fe(3n-3)O(9n+11) structures are composed of perovskite blocks separated by translational interfaces parallel to the (001)p perovskite planes. The thickness of the perovskite blocks increases with n, while the atomic arrangement at the interfaces remains the same. The interfaces comprise chains of double edge-sharing (Fe,Ti)O6 octahedra connected to the octahedra of the perovskite blocks by sharing edges and corners. This configuration shifts the adjacent perovskite blocks relative to each other over a vector ½[110]p and creates S-shaped tunnels along the [010] direction. The tunnels accommodate double columns of the Bi(3+) cations, which stabilize the interfaces owing to the stereochemical activity of their lone electron pairs. The Bi(3n+1)Ti7Fe(3n-3)O(9n+11) structures can be formally considered either as intergrowths of perovskite modules and polysynthetically twinned modules of the Bi2Ti4O11 structure or as intergrowths of the 2D perovskite and 1D anatase fragments. Transmission electron microscopy (TEM) on Bi10Ti7Fe6O38 reveals that static atomic displacements of Bi and O inside the perovskite blocks are not completely random; they are cooperative, yet only short-range ordered. According to TEM, the interfaces can be laterally shifted with respect to each other over ±1/3a, introducing an additional degree of disorder. Bi10Ti7Fe6O38 is paramagnetic in the 1.5-1000 K temperature range due to dilution of the magnetic Fe(3+) cations with nonmagnetic Ti(4+). The n = 3, 4 compounds demonstrate a

  13. Synthesis, crystal structure, and properties of Bi{sub 3}TeBO{sub 9} or Bi{sub 3}(TeO{sub 6})(BO{sub 3}): a non-centrosymmetric borate-tellurate(VI) of bismuth

    Energy Technology Data Exchange (ETDEWEB)

    Daub, Michael; Krummer, Michael; Hoffmann, Anke [Institut fuer Anorganische und Analytische Chemie, Albert-Ludwigs-Universitaet, Albertstrasse 21, 79104, Freiburg (Germany); Bayarjargal, Lkhamsuren [Institut fuer Geowissenschaften, Abt. Kristallographie, Goethe-Universitaet, Altenhoeferallee 1, 60438, Frankfurt am Main (Germany); Hillebrecht, Harald [Institut fuer Anorganische und Analytische Chemie, Albert-Ludwigs-Universitaet, Albertstrasse 21, 79104, Freiburg (Germany); Freiburger Materialforschungszentrum FMF, Albert-Ludwigs-Universitaet, Stefan-Meier-Strasse 25, 79104, Freiburg (Germany)

    2017-01-26

    Pale-yellow single crystals of the new borate tellurate(VI) Bi{sub 3}TeBO{sub 9} were obtained by reaction of stoichiometric amounts of Bi{sub 2}O{sub 3}, B{sub 2}O{sub 3}, and Te(OH){sub 6} at 780 C. The non-centrosymmetric crystal structure (P6{sub 3}, Z=2, a=8.7454(16), c=5.8911(11) Aa, 738 refl., 43 param, R1=0.037, wR2=0.093) contains isolated trigonal-planar BO{sub 3} units and nearly undistorted TeO{sub 6} octahedra. The Bi{sup 3+} cations are located in between in octahedral voids. The BiO{sub 6} octahedra are significantly distorted to a [3+3] pattern (2.25/2.50 Aa) due to the ns{sup 2} configuration. According to the structural features, the formula can be written as Bi{sub 3}(TeO{sub 6})(BO{sub 3}). Alternatively, the structure can also be described as hcp of oxygen with Te{sup VI} and Bi{sup III} in octahedral voids and B{sup III} in trigonal- planar voids. The vibrational spectra show the typical features of BO{sub 3} and TeO{sub 6} units with a significant {sup 10}B/{sup 11}B isotopic splitting of the IR-active B-O valence mode (1248 and 1282 cm{sup -1}). The UV/Vis spectrum shows an optical band edge with an onset around 480 nm (2.6 eV). MAS-NMR spectra of {sup 11}B show an anisotropic signal with a quadrupole coupling constant of C{sub Q}=2.55 MHz. and a very small deviation from rotational symmetry (η=0.2). The isotropic chemical shift is 20.1 ppm. The second harmonic generation (SHG) test was positive with an activity comparable to potassium dihydrogen phosphate (KDP). Bi{sub 3}TeBO{sub 9} decomposes in air at 825 C to Bi{sub 2}TeO{sub 5}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Synthesis of bimetallic trifluoroacetates through a crystallochemical investigation of their monometallic counterparts: the case of (A, A')(CF3COO)2·nH2O (A, A' = Mg, Ca, Sr, Ba, Mn).

    Science.gov (United States)

    Dulani Dhanapala, B; Mannino, Natalie A; Mendoza, Laura M; Tauni Dissanayake, K; Martin, Philip D; Suescun, Leopoldo; Rabuffetti, Federico A

    2017-01-31

    Owing to their potential as single-source precursors for compositionally complex materials, there is growing interest in the rational design of multimetallic compounds containing fluorinated ligands. In this work, we show that chemical and structural principles for a materials-by-design approach to bimetallic trifluoroacetates can be established through a systematic investigation of the crystal-chemistry of their monometallic counterparts. A(CF3COO)2·nH2O (A = Mg, Ca, Sr, Ba, Mn) monometallic trifluoroacetates were employed to demonstrate the feasibility of this approach. The crystal-chemistry of monometallic trifluoroacetates was mapped using variable-temperature single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analysis. The evolution with temperature of the previously unknown crystal structure of Mg(CF3COO)2·4H2O was found to be identical to that of Mn(CF3COO)2·4H2O. More important, the flexibility of Mnx(CF3COO)2x·4H2O (x = 1, 3) to adopt two structures, one isostructural to Mg(CF3COO)2·4H2O, the other isostructural to Ca3(CF3COO)6·4H2O, enabled the synthesis of Mg-Mn and Ca-Mn bimetallic trifluoroacetates. Mg0.45Mn0.55(CF3COO)2·4H2O was found to be isostructural to Mg(CF3COO)2·4H2O and exhibited isolated metal-oxygen octahedra with Mg2+ and Mn2+ nearly equally distributed over the metal sites (Mg/Mn: 45/55). Ca1.72Mn1.28(CF3COO)6·4H2O was isostructural to Ca3(CF3COO)6·4H2O and displayed trimers of metal-oxygen corner-sharing octahedra; Ca2+ and Mn2+ were unequally distributed over the central (Ca/Mn: 96/4) and terminal (Ca/Mn: 38/62) octahedral sites.

  15. CFD modelling of supercritical water flow and heat transfer in a 2 × 2 fuel rod bundle

    Energy Technology Data Exchange (ETDEWEB)

    Podila, Krishna, E-mail: krishna.podila@cnl.ca; Rao, Yanfei, E-mail: yanfei.rao@cnl.ca

    2016-05-15

    Highlights: • Bare and wire wrapped 2 × 2 fuel rod bundles were modelled with CFD. • Sensitivity of predictions to SST k–ω, v{sup 2}–f and turbulent Prandtl number was tested. • CFD predictions were assessed with experimentally reported fuel wall temperatures. - Abstract: In the present assessment of the CFD code, two heat transfer experiments using water at supercritical pressures were selected: a 2 × 2 rod bare bundle; and a 2 × 2 rod wire-wrapped bundle. A systematic 3D CFD study of the fluid flow and heat transfer at supercritical pressures for the rod bundle geometries was performed with the key parameter being the fuel rod wall temperature. The sensitivity of the prediction to the steady RANS turbulence models of SST k–ω, v{sup 2}–f and turbulent Prandtl number (Pr{sub t}) was tested to ensure the reliability of the predicted wall temperature obtained for the current analysis. Using the appropriate turbulence model based on the sensitivity analysis, the mesh refinement, or the grid convergence, was performed for the two geometries. Following the above sensitivity analyses and mesh refinements, the recommended CFD model was then assessed against the measurements from the two experiments. It was found that the CFD model adopted in the current work was able to qualitatively capture the trends reported by the experiments but the degree of temperature rise along the heated length was underpredicted. Moreover, the applicability of turbulence models varied case-by-case and the performance evaluation of the turbulence models was primarily based on its ability to predict the experimentally reported fuel wall temperatures. Of the two turbulence models tested, the SST k–ω was found to be better at capturing the measurements at pseudo-critical and supercritical test conditions, whereas the v{sup 2}–f performed better at sub-critical test conditions. Along with the appropriate turbulence model, CFD results were found to be particularly sensitive to

  16. Carbon Dioxide Gas Sensors and Method of Manufacturing and Using Same

    Science.gov (United States)

    Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor)

    2014-01-01

    A gas sensor comprises a substrate layer; a pair of interdigitated metal electrodes, said electrodes include upper surfaces, the electrodes selected from the group consisting of Pt, Pd, Au, Ir, Ag, Ru, Rh, In, Os, and their alloys. A first layer of solid electrolyte staying in between electrode fingers and partially on said upper surfaces of said electrodes, said first layer selected from NASICON, LISICON, KSICON and.beta.''-Alumina. A second layer of metal carbonate(s) as an auxiliary electrolyte engaging said upper surfaces of the electrodes and the first solid electrolyte. The metal carbonates selected from the group consisting of the following ions Na.sup.+, K.sup.+, Li.sup.+, Ag.sup.+, H.sup.+, Pb.sup.2+, Sr.sup.2+, Ba.sup.2+, and any combination thereof. An extra layer of metal oxide selected from the group consisting of SnO.sub.2, In.sub.2O.sub.3, TiO.sub.2, WO.sub.3, ZnO, Fe.sub.2O.sub.3, ITO, CdO, U.sub.3O.sub.8, Ta.sub.2O.sub.5, BaO, MoO.sub.2, MoO.sub.3, V.sub.2O.sub.5, Nb.sub.2O.sub.5, CuO, Cr.sub.2O.sub.3, La.sub.2O.sub.3, RuO.sub.3, RuO.sub.2, ReO.sub.2, ReO.sub.3, Ag.sub.2O, CoO, Cu.sub.2O, SnO, NiO, Pr.sub.2O.sub.3, BaO, PdO.sub.2, HfO.sub.3, HfO.sub.3 or other metal oxide and their mixtures residing above and in engagement with the second electrolyte to improve sensor performance and/or to reduce sensor heating power consumption.

  17. Redox behavior of a low-doped Pr-CeO{sub 2}(111) surface. A DFT+U study

    Energy Technology Data Exchange (ETDEWEB)

    Milberg, Brian [ITHES, UBA-CONICET, Departamento de Ingeniería Química, Pabellón de Industrias, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Juan, Alfredo [Departamento de Física & IFISUR, UNS-CONICET, Avda. Alem 1253, 8000 Bahía Blanca (Argentina); Irigoyen, Beatriz, E-mail: beatriz@di.fcen.uba.ar [ITHES, UBA-CONICET, Departamento de Ingeniería Química, Pabellón de Industrias, Ciudad Universitaria, 1428 Buenos Aires (Argentina)

    2017-04-15

    Highlights: • Pr doping facilitates oxygen donation due to the easy formation of Pr{sup 3+}/Pr{sup 4+} and Ce{sup 3+}/Ce{sup 4+} redox couples. • Pr doping also favors the formation of superoxide (O{sub 2}{sup −}) radicals on surface O-holes. • CO can be oxidized by superoxide radical forming a CO{sub 2} molecule floating on the surface. • CO can also interact on the (O{sub 2}{sup −})/Pr{sup 3+} interphase and forms weakly adsorbed carbonate-type intermediates. - Abstract: In this work, we investigated the redox behavior (donation and replenishing of oxygen) of a low praseodymium (Pr)-doped CeO{sub 2}(111) surface. We considered a 3.7 at.% Pr doping and performed density functional calculations using the GGA formalism with the ‘U’ correction on Ce(4f) and Pr(4f) orbitals. Our results indicate that Pr doping promotes oxygen donation by lowering the energy necessary to form surface anionic vacancies. When the Ce{sub 0.963}Pr{sub 0.037}O{sub 2}(111) surface donates one oxygen, the two excess electrons locate on Pr and Ce cations and reduce them to Pr{sup 3+} and Ce{sup 3+} ones. Praseodymium doping also favors the activation of O{sub 2} molecule on surface O-holes, leading to formation of a superoxide (O{sub 2}{sup −}) radical as well as to reoxidation of the Ce{sup 3+} cation to Ce{sup 4+} one. Additionally, we used the CO molecular adsorption for testing the reactivity of those superoxide species. The calculations expose the ability of these radicals to oxidize CO forming a CO{sub 2} molecule floating on the surface. However, when the superoxide is in the immediate vicinity of Pr dopant a carbonate-type species is formed. Our theoretical results may help to gain insight into redox properties and improved catalytic performance of low-doped Pr-CeO{sub 2} solids.

  18. A NOVEL APPROACH TO CATALYTIC DESULFURIZATION OF COAL

    Energy Technology Data Exchange (ETDEWEB)

    John G. Verkade

    2001-11-01

    Column chromatographic separation of the S=PBu{sub 3}/PBu{sub 3} product mixture followed by weighing the S=PBu{sub 3}, and by vacuum distillation of S=PBu{sub 3}/PBu{sub 3}mixture followed by gas chromatographic analysis are described. Effects of coal mesh size, pre-treatment with methanol Coal (S) + excess PR{sub 3} {yields} Coal + S=PR{sub 3}/PBu{sub 3} and sonication on sulfur removal by PBu{sub 3} revealed that particle size was not observed to affect desulfurization efficiency in a consistent manner. Coal pretreatment with methanol to induce swelling or the addition of a filter aid such as Celite reduced desulfurization efficiency of the PBu{sub 3} and sonication was no more effective than heating. A rationale is put forth for the lack of efficacy of methanol pretreatment of the coal in desulfurization runs with PBu{sub 3}. Coal desulfurization with PBu{sub 3} was not improved in the presence of miniscule beads of molten lithium or sodium as a desulfurizing reagent for SPBu{sub 3} in a strategy aimed at regenerating PBu{sub 3} inside coal pores. Although desulfurization of coals did occur in sodium solutions in liquid ammonia, substantial loss of coal mass was also observed. Of particular concern is the mass balance in the above reaction, a problem which is described in some detail. In an effort to solve this difficulty, a specially designed apparatus is described which we believe can solve this problem reasonably effectively. Elemental sodium was found to remove sulfur quantitatively from a variety of polycyclic organosulfur compounds including dibenzothiophene and benzothiophene under relatively mild conditions (150 C) in a hydrocarbon solvent without requiring the addition of a hydrogen donor. Lithium facilitates the same reaction at a higher temperature (254 C). Mechanistic pathways are proposed for these transformations. Curiously, dibenzothiophene and its corresponding sulfone was virtually quantitatively desulfurized in sodium solutions in liquid

  19. Determination of trace elements in high pure rare earth oxide by double focusing inductively coupled plasma mass spectrometry (HR ICP-MS) and high performance liquid chromatography (HPLC) techniques; Determinacao de impurezas metalicas em oxidos de terras raras de alta pureza pela espectrometria de massa (setor magnetico) com fonte de plasma induzida por argonio (HR ICP-MS) e cromatografia liquida de alto desempenho (HPLC)

    Energy Technology Data Exchange (ETDEWEB)

    Pedreira Filho, Walter dos Reis

    2000-07-01

    Rare earth oxides are used in several technological fields whose applications can be observed in several areas of modern technology, among which are included: lasers, semiconductors semi, high purity materials and metallic alloys. The field of applications of the rare earth elements is quite wide. Several important industrial applications are ceramics, catalysts and metallurgical as well as research areas and high technology sectors. Such applications have been presenting an accentuated growth in the last years. Chemical characterization of rare earth oxides of high purity has been constituting one of the major challenges of analytical chemistry. Several analytical techniques were used for chemical characterization of high purity rare earth the oxides. Even so, those techniques present limitations when one needs to characterize materials of a high level of purity, as in the case of rare earth oxides. Some of those limitations are associated, for example, to spectral interference. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a powerful analytical tool for quantitative analysis of metal impurities in high purity materials. The Instituto de Pesquisas Energeticas e Nucleares (IPEN) has an unit of production and purification of rare earth oxides, with above 99,9% level of purity. In this work, the rare earth impurities were characterized in samples (La{sub 2}O{sub 3}; CeO{sub 2}; Pr{sub 6}O{sub 11}; Nd{sub 2}O{sub 3}; Sm{sub 2}O{sub 3}; Gd{sub 2}O{sub 3}; Y{sub 2}O{sub 3}) produced at the IPEN and certified standard materials produced by Johnson Matthey Chemical (JMC). The technique of high performance liquid chromatography (HPLC) was used in the separation of the impurities. Quantification of metallic impurities was carried out as inductively coupled plasma mass spectrometer (HR-ICP MS). In this work it is presented a new analytical methodology in the chemical characterization of metallic impurities in rare earth oxides of high purity (> 99,9%) with and

  20. Degradation of surfactant-modified montmorillonites in HCl

    Energy Technology Data Exchange (ETDEWEB)

    Madejova, Jana, E-mail: jana.madejova@savba.sk [Institute of Inorganic Chemistry, SAS, Dubravska cesta 9, SK-845 36 Bratislava (Slovakia); Palkova, Helena, E-mail: helena.palkova@savba.sk [Institute of Inorganic Chemistry, SAS, Dubravska cesta 9, SK-845 36 Bratislava (Slovakia); Jankovic, Lubos, E-mail: lubos.jankovic@savba.sk [Institute of Inorganic Chemistry, SAS, Dubravska cesta 9, SK-845 36 Bratislava (Slovakia)

    2012-06-15

    The effect of surfactant size on the extent of montmorillonites decomposition in HCl was investigated. Na-SAz montmorillonite and tetraalkylammonium salts of alkyl-chains length increasing from methyl- Me{sub 4}N to pentyl- Pe{sub 4}N were used for organo-montmorillonites preparation. Decreasing intensity of d{sub 001} diffraction proved destruction of montmorillonite structure connected with gradual surfactant release. A shift of the SiO stretching band to 1097 cm{sup -1} confirmed formation of amorphous silica phase. A new band near 7315 cm{sup -1} corresponding to SiOH overtone revealed creation of protonated silica. This band was observed in the spectra of all acid-treated samples, also in those with minor decomposition of the structure. The size of the cations significantly affected decomposition of montmorillonites in HCl. The less stable were Na-SAz and Me{sub 4}N-SAz in which the content of octahedral atoms dropped to {approx}5% of their original values upon 8 h treatments. Et{sub 4}N-SAz and Pr{sub 4}N-SAz were slightly more resistant mainly at short times. Bu{sub 4}N-SAz and Pe{sub 4}N-SAz showed the least structural modifications, only 50% and 35% of octahedral atoms, respectively, were released into solution within 8 h treatments. This observation proves that bulky alkylammonium cations covering the inner and outer surfaces of montmorillonite prevent effectively the access of protons to the layers protecting the mineral from degradation in the acid. - Highlights: Black-Right-Pointing-Pointer Hybrid materials were prepared from montmorillonite and alkylammonium cations with short alkyl chains. Black-Right-Pointing-Pointer The effect of surfactant on organo-montmorillonites dissolution in HCl was studied. Black-Right-Pointing-Pointer With increasing size of cation the extent of montmorillonite decomposition decreased. Black-Right-Pointing-Pointer Bulky surfactants prevent the access of protons to the layers and thus protect montmorillonite from

  1. LOW TEMPERATURE CATHODE SUPPORTED ELECTROLYTES

    Energy Technology Data Exchange (ETDEWEB)

    Harlan U. Anderson; Fatih Dogan; Vladimir Petrovsky

    2002-03-31

    This project has three main goals: Thin Films Studies, Preparation of Graded Porous Substrates and Basic Electrical Characterization and testing of Planar Single Cells. This period has continued to address the problem of making dense 1/2 to 5 {micro}m thick dense layers on porous substrates (the cathode LSM). Our current status is that we are making structures of 2-5 cm{sup 2} in area, which consist of either dense YSZ or CGO infiltrated into a 2-5 {micro}m thick 50% porous layer made of either nanoncrystalline CGO or YSZ powder. This composite structure coats a macroporous cathode or anode; which serves as the structural element of the bi-layer structure. These structures are being tested as SOFC elements. A number of structures have been evaluated both as symmetrical and as button cell configuration. Results of this testing indicates that the cathodes contribute the most to cell losses for temperatures below 750 C. In this investigation different cathode materials were studied using impedance spectroscopy of symmetric cells and IV characteristics of anode supported fuel cells. Cathode materials studied included La{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (LSCF), La{sub 0.7}Sr{sub 0.2}MnO{sub 3} (LSM), Pr{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}O{sub 3} (PSCF), Sm{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF), and Yb{sub .8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF). A new technique for filtering the Fourier transform of impedance data was used to increase the sensitivity of impedance analysis. By creating a filter specifically for impedance spectroscopy the resolution was increased. The filter was tailored to look for specific circuit elements like R//C, Warburg, or constant phase elements. As many as four peaks can be resolved using the filtering technique on symmetric cells. It may be possible to relate the different peaks to material parameters, like the oxygen exchange coefficient. The cathode grouped in order from lowest to highest ASR is

  2. Crystal structure, hydrogen bonding, and sup 8 sup 1 Br NQR of low-temperature phase of 4-aminopyridinium tetrabromoantimonate (3)

    CERN Document Server

    Hashimoto, M; Fuess, H; Svoboda, I; Ehrenberg, H

    2003-01-01

    The crystal structure of the low-temperature phase (LTP) of the title compound was determined at 220 K (monoclinic, P2 sub 1 sub / sub c). The 4-aminopyridinium cations (4-NH sub 2 C sub 5 H sub 4 NH sup +) were found to be ordered in LTP, while being severely disordered in the room-temperature phase (monoclinic, C2/c). The tetrabromoantimonate anions (SbBr sub 4 sup -) were incorporated into the infinite polyanion chains of irregular SbBr sub 6 octahedra with two-edges sharing. The trans-Br-Sb-Br moiety in the SbBr sub 4 sup - anion was approximately symmetric differing from the asymmetric Br-Sb centre dot centre dot centre dot Br moiety found in LTP of pyridinium tetrabromoantimonate (3). The N-H moieties in both of the pyridine ring and the amino (-NH sub 2) group participate in the formation of N-H centre dot centre dot centre dot Br hydrogen bonds. It was shown that the sup 8 sup 1 Br NQR spectrum of LTP is closely related to the anion structure and the hydrogen bonds. The distinctive anion structures, a...

  3. Phthalocyanine/chitosan-TiO{sub 2} photocatalysts: Characterization and photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Hamdi, A. [University of Sfax-Faculty of Science-LCI-Sfax-Tunisia (Tunisia); Boufi, S. [University of Sfax-Faculty of Science-LMSE-Sfax-Tunisia (Tunisia); Bouattour, S., E-mail: soraa.boufi@yahoo.com [University of Sfax-Faculty of Science-LCI-Sfax-Tunisia (Tunisia)

    2015-06-01

    Graphical abstract: - Highlights: • Hybrid chitosan–phthalocyanine-TiO{sub 2} photocatalyst are elaborated at room temperature without any calcination treatment. • After immersion in water, the alkoxide groups underwent hydrolysis and the (TiO{sub 6}) octahedra started to join together. • The enhanced activity of the hybrid catalyst is attributed to the cooperative role of the three components of the photocatalyst. - Abstract: Chitosan (CS) was used as a template to prepare a hybrid chitosan–phthalocyanine-TiO{sub 2} (PC/CS-TiO{sub 2}) photocatalyst at room temperature without any calcination treatment. The as-prepared hybrid photocatalyst (PC/CS-TiO{sub 2}) was characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and UV–vis diffuse reflectance spectroscopy (DRS). The results of the photodegradation of aniline, used as a model pollutant, revealed that the hybrid photocatalyst (PC/CS-TiO{sub 2}) exhibited a photocatalytic activity under visible-light irradiation. The enhanced activity of the hybrid catalyst is attributed to the cooperative role of the three components of the photocatalyst; chitosan as a template for the immobilization crystalline TiO{sub 2} nanoparticles, phthalocyanine that promote the light absorption in the visible range and TiO{sub 2} acting as an acceptor of electrons generated by the photons absorption to produce superoxide radicals.

  4. A High-Pressure Raman Study of Mixed Perovskites BaCe xZr 1- xO 3 (0≤ x≤1)

    Science.gov (United States)

    Chemarin, C.; Rosman, N.; Pagnier, T.; Lucazeau, G.

    2000-02-01

    A high-pressure Raman study of polycrystalline samples of BaCexZr1-xO3 is performed at room temperature. The evolution of Raman spectra with pressure is compared to the evolution of the Raman spectra of BaZrO3 and BaCeO3. The effect of composition on the pressure-induced phase transitions is monitored from the Raman spectra. Transitions toward lower symmetry phases as pressure increases are evidenced. A phase diagram in the binary system BaZrO3-BaCeO3 based on the Raman spectra characteristic of the different structures of BaCeO3 (Pnma, Imma, Roverline3c, Pm3m) is proposed. The transition pressures toward low-symmetry structures decrease when Ce is replaced for Zr. This study allows us to interpret the BaCexZr1-xO3 (0≤x≤1) Raman spectra at ambient pressure on the basis of nanodomains and nanophases. These objects tend to disappear upon pressure increase. The octahedra to dodecahedra volumes ratio is used as a critical parameter that is able to reproduce qualitatively some of the phase transitions in the mixed perovskites BaCexZr1-xO3. In order to calculate this parameter vs pressure, a derivation of the samples' compressibility based on a polyhedral approach is performed and is found in the range [0.7×10-11-1.0×10-11 Pa-1].

  5. Aqueous Synthesis of Technetium-Doped Titanium Dioxide by Direct Oxidation of Titanium Powder, a Precursor for Ceramic Nuclear Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Lukens, Wayne W. [Chemical; Saslow, Sarah A. [Earth

    2017-11-17

    Technetium-99 (Tc) is a problematic fission product that complicates the long-term disposal of nuclear waste due to its long half-life, high fission yield, and the environmental mobility of pertechnetate, its stable form in aerobic environments. One approach to preventing Tc contamination is through incorporation into durable waste forms based on weathering-resistant minerals such as rutile (titanium dioxide). Here, the incorporation of technetium into titanium dioxide by means of simple, aqueous chemistry is presented. X-ray absorption fine structure spectroscopy and diffuse reflectance spectroscopy indicate that Tc(IV) replaces Ti(IV) within the structure. Rather than being incorporated as isolated Tc(IV) ions, Tc is present as pairs of edge-sharing Tc(IV) octahedra similar to molecular Tc(IV) complexes such as [(H2EDTA)TcIV](u-O)2. Technetium-doped TiO2 was suspended in deionized water under aerobic conditions, and the Tc leached under these conditions was followed for 8 months. The normalized release rate of Tc (LRTc) from the TiO2 particles is low (3×10-6 g m-2 d-1), which illustrates the potential utility of TiO2 as waste form. However, the small size of the as-prepared TiO2 nanoparticles results in estimated retention of Tc for 104 years, which is only a fraction of the half-life of Tc (2×10-5 years).

  6. In-situ time-of-flight neutron diffraction study of the structure evolution of electrode materials in a commercial battery with LiNi0.8Co0.15Al0.05O2 cathode

    Science.gov (United States)

    Bobrikov, I. A.; Samoylova, N. Yu.; Sumnikov, S. V.; Ivanshina, O. Yu.; Vasin, R. N.; Beskrovnyi, A. I.; Balagurov, A. M.

    2017-12-01

    A commercial lithium-ion battery with LiNi0.8Co0.15Al0.05O2 (NCA) cathode has been studied in situ using high-intensity and high-resolution neutron diffraction. Structure and phase composition of the battery electrodes have been probed during charge-discharge in different cycling modes. The dependence of the anode composition on the charge rate has been determined quantitatively. Different kinetics of Li (de)intercalation in the graphite anode during charge/discharge process have been observed. Phase separation of the cathode material has not been detected in whole voltage range. Non-linear dependencies of the unit cell parameters, atomic and layer spacing on the lithium content in the cathode have been observed. Measured dependencies of interatomic spacing and interlayer spacing, and unit cell parameters of the cathode structure on the lithium content could be qualitatively explained by several factors, such as variations of oxidation state of cation in oxygen octahedra, Coulomb repulsion of oxygen layers, changes of average effective charge of oxygen layers and van der Waals interactions between MeO2-layers at high level of the NCA delithiation.

  7. Synthesis and Raman spectroscopy of a layered SiS2 phase at high pressures.

    Science.gov (United States)

    Wang, Yu; Jiang, Shu-Qing; Goncharov, Alexander F; Gorelli, Federico A; Chen, Xiao-Jia; Plašienka, Dušan; Martoňák, Roman; Tosatti, Erio; Santoro, Mario

    2018-01-07

    Dichalcogenides are known to exhibit layered solid phases, at ambient and high pressures, where 2D layers of chemically bonded formula units are held together by van der Waals forces. These materials are of great interest for solid-state sciences and technology, along with other 2D systems such as graphene and phosphorene. SiS2 is an archetypal model system of the most fundamental interest within this ensemble. Recently, high pressure (GPa) phases with Si in octahedral coordination by S have been theoretically predicted and also experimentally found to occur in this compound. At variance with stishovite in SiO2, which is a 3D network of SiO6 octahedra, the phases with octahedral coordination in SiS2 are 2D layered. Very importantly, this type of semiconducting material was theoretically predicted to exhibit continuous bandgap closing with pressure to a poor metallic state at tens of GPa. We synthesized layered SiS2 with octahedral coordination in a diamond anvil cell at 7.5-9 GPa, by laser heating together elemental S and Si at 1300-1700 K. Indeed, Raman spectroscopy up to 64.4 GPa is compatible with continuous bandgap closing in this material with the onset of either weak metallicity or of a narrow bandgap semiconductor state with a large density of defect-induced, intra-gap energy levels, at about 57 GPa. Importantly, our investigation adds up to the fundamental knowledge of layered dichalcogenides.

  8. Dicobalt(II lead(II hydrogenphosphate(V phosphate(V hydroxide monohydrate

    Directory of Open Access Journals (Sweden)

    Lahcen El Ammari

    2012-05-01

    Full Text Available The title compound, Co2Pb(HPO4(PO4OH·H2O, which was synthesized under hydrothermal conditions, crystallizes in a new structure type. Except for two O atoms in general positions and two Co atoms on centres of symmetry, all other atoms in the asymmetric unit (1 Pb, 2 Co, 2 P, 8 O and 4 H are located on mirror planes. The structure is built up from two infinite linear chains, viz. 1∞[CoO2/1(H2O2/2O2/2] and 1∞[CoO2/1(OH2/2O2/2], of edge-sharing CoO6 octahedra running along [010]. Adjacent chains are linked to each other through PO4 and PO3(OH tetrahedra, leading to the formation of layers parallel to (100. The three-dimensional framework is formed by stacking along [100] of adjacent layers that are held together by distorted PbO8 polyhedra. Hydrogen bonds of the type O—H...O involving the water molecule are very strong, while those O atoms involving the OH groups form weak bifurcated and trifurcated hydrogen bonds.

  9. Number series of atoms, interatomic bonds and interface bonds defining zinc-blende nanocrystals as function of size, shape and surface orientation: Analytic tools to interpret solid state spectroscopy data

    Directory of Open Access Journals (Sweden)

    Dirk König

    2016-08-01

    Full Text Available Semiconductor nanocrystals (NCs experience stress and charge transfer by embedding materials or ligands and impurity atoms. In return, the environment of NCs experiences a NC stress response which may lead to matrix deformation and propagated strain. Up to now, there is no universal gauge to evaluate the stress impact on NCs and their response as a function of NC size dNC. I deduce geometrical number series as analytical tools to obtain the number of NC atoms NNC(dNC[i], bonds between NC atoms Nbnd(dNC[i] and interface bonds NIF(dNC[i] for seven high symmetry zinc-blende (zb NCs with low-index faceting: {001} cubes, {111} octahedra, {110} dodecahedra, {001}-{111} pyramids, {111} tetrahedra, {111}-{001} quatrodecahedra and {001}-{111} quadrodecahedra. The fundamental insights into NC structures revealed here allow for major advancements in data interpretation and understanding of zb- and diamond-lattice based nanomaterials. The analytical number series can serve as a standard procedure for stress evaluation in solid state spectroscopy due to their deterministic nature, easy use and general applicability over a wide range of spectroscopy methods as well as NC sizes, forms and materials.

  10. [Diaquasesqui(nitrato-κOhemi(perchlorato-κOcopper(II]-μ-{bis[5-methyl-3-(pyridin-2-yl-1H-pyrazol-4-yl] selenide}-[triaqua(perchlorato-κOcopper(II] nitrate monohydrate

    Directory of Open Access Journals (Sweden)

    Maksym Seredyuk

    2013-06-01

    Full Text Available In the binuclear title complex, [Cu2(ClO41.5(NO31.5(C18H16N6Se(H2O5]NO3·H2O, both CuII ions are hexacoordinated by O and N atoms, thus forming axially elongated CuO4N2 octahedra. The equatorial plane of each octahedron is formed by one chelating pyrazole–pyridine fragment of the organic ligand and two water molecules. The axial positions in one octahedron are occupied by a water molecule and a monodentately coordinated perchlorate anion, while those in the other are occupied by a nitrate anion and a disordered perchlorate/nitrate anion with equal site occupancy. The pyrazole–pyridine units of the organic selenide are trans-oriented to each other with a C—Se—C angle of 96.01 (14°. In the crystal, uncoordinated nitrate anions and the coordinating water molecules are involved in O—H...O and N—H...O hydrogen bonds, forming a bridge between the pyrazole group and the coordinating water molecules. Further O—H...O hydrogen bonds between the complex molecules and a π–π stacking interaction with a centroid–centroid distance of 3.834 (4 Å are also observed.

  11. First determination of the valence band dispersion of CH3NH3PbI3 hybrid organic-inorganic perovskite

    Science.gov (United States)

    Lee, Min-I.; Barragán, Ana; Nair, Maya N.; Jacques, Vincent L. R.; Le Bolloc'h, David; Fertey, Pierre; Jemli, Khaoula; Lédée, Ferdinand; Trippé-Allard, Gaëlle; Deleporte, Emmanuelle; Taleb-Ibrahimi, Amina; Tejeda, Antonio

    2017-07-01

    The family of hybrid organic-inorganic halide perovskites is in the limelight because of their recently discovered high photovoltaic efficiency. These materials combine photovoltaic energy conversion efficiencies exceeding 22% and low-temperature and low-cost processing in solution; a breakthrough in the panorama of renewable energy. Solar cell operation relies on the excitation of the valence band electrons to the conduction band by solar photons. One factor strongly impacting the absorption efficiency is the band dispersion. The band dispersion has been extensively studied theoretically, but no experimental information was available. Herein, we present the first experimental determination of the valence band dispersion of methylammonium lead halide in the tetragonal phase. Our results pave the way for contrasting the electronic hopping or the electron effective masses in different theories by comparing to our experimental bands. We also show a significant broadening of the electronic states, promoting relaxed conditions for photon absorption, and demonstrate that the tetragonal structure associated to the octahedra network distortion below 50 °C induces only a minor modification of the electronic bands, with respect to the cubic phase at high temperature, thus minimizing the impact of the cubic-tetragonal transition on solar cell efficiencies.

  12. Resolving the structure and properties of τ1-Cr-Ni-Al for high temperature protective applications

    Science.gov (United States)

    Simonson, J. W.; Nicasio, J. E.; Ilyas, H.; Pabla, J.; Horvat, K.; Misuraca, J. C.

    Increasing the temperature of the steam in turbine power plants enhances thermal efficiency while reducing CO2 emissions. Exposed steel components, however, must be coated to withstand the harsh environments present in next-generation advanced ultra-supercritical plants. Proposed coating materials must exhibit low density, high hardness, high toughness, excellent oxidation resistance, and low thermal conductivity. With an eye towards satisfying this diverse array of requirements, we report the properties of the so-called τ1 phase of Cr-Ni-Al. We resolve the previously controversial composition and crystal structure of this material. The complex structure is composed of distorted icosahedra and octahedra of Al, with nearest-neighbor transition metal-Al bond lengths as short as 2.4 Å, far shorter than typical distances in Ni-Al and Cr-Al binaries. Accordingly, Vickers hardness is 6 . 88 +/- 0 . 13 GPa, as hard as extra-high-hardness armor plating at only 45% the density. We discuss these properties in light of the result of transport and oxidation resistance measurements. The apparent dependencies of these properties on crystal structure suggests new criteria for materials research. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund, for support of this research under contract 56764-UNI10.

  13. Nickeliferous pyrite tracks pervasive hydrothermal alteration in Martian regolith breccia: A study in NWA 7533

    Science.gov (United States)

    Lorand, Jean-Pierre; Hewins, Roger H.; Remusat, Laurent; Zanda, Brigitte; Pont, Sylvain; Leroux, Hugues; Marinova, Maya; Jacob, Damien; Humayun, Munir; Nemchin, Alexander; Grange, Marion; Kennedy, Allen; Göpel, Christa

    2015-12-01

    Martian regolith breccia NWA 7533 (and the seven paired samples) is unique among Martian meteorites in showing accessory pyrite (up to 1% by weight). Pyrite is a late mineral, crystallized after the final assembly of the breccia. It is present in all of the lithologies, i.e., the fine-grained matrix (ICM), clast-laden impact melt rocks (CLIMR), melt spherules, microbasalts, lithic clasts, and mineral clasts, all lacking magmatic sulfides due to degassing. Pyrite crystals show combinations of cubes, truncated cubes, and octahedra. Polycrystalline clusters can reach 200 μm in maximum dimensions. Regardless of their shape, pyrite crystals display evidence of very weak shock metamorphism such as planar features, fracture networks, and disruption into subgrains. The late fracture systems acted as preferential pathways for partial replacement of pyrite by iron oxyhydroxides interpreted as resulting from hot desert terrestrial alteration. The distribution and shape of pyrite crystals argue for growth at moderate to low growth rate from just-saturated near neutral (6 FMQ + 2 log units. It is inferred from the maximum Ni contents (4.5 wt%) that pyrite started crystallizing at 400-500 °C, during or shortly after a short-duration, relatively low temperature, thermal event that lithified and sintered the regolith breccias, 1.4 Ga ago as deduced from disturbance in several isotope systematics.

  14. Polymorphism in Photoluminescent KNdW2O8: Synthesis, Neutron Diffraction, and Raman Study

    Energy Technology Data Exchange (ETDEWEB)

    S. M. Bhat, Swetha [Materials Science Division, Poornaprajna Institute of Scientific Research, Bidalur Near Devanahalli,; Swain, Diptikanta [CPMU, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bengaluru, Karnataka, India; Feygenson, Mikhail [ORNL; Neuefeind, Joerg C [ORNL; Sundaram, Nalini [Materials Science Division, Poornaprajna Institute of Scientific Research, Bidalur Near Devanahalli,

    2014-01-01

    Polymorphs of KNdW2O8 ( -KNdW2O8 and -KNdW2O8) phosphors were synthesized by an efficient solution combustion technique for the first time. The crystal structure of the polymorphs analyzed from Rietveld refinement of neutron diffraction data confirms that -KNdW2O8 crystallizes in the tetragonal system (space group I4 ), and -KNdW2O8 crystallizes in the monoclinic system (space group C2/m). The local structure of both polymorphs was elucidated using combined neutron pair distribution function (PDF) and Raman scattering techniques. Photoluminescence measurements of the polymorphs showed broadened emission line width and increased intensity for -KNdW2O8 in the visible region compared to -KNdW2O8. This phenomenon is attributed to the increased distortion in the coordination environment of the luminescing Nd3+ ion. Combined PDF, Rietveld, and Raman measurements reveal distortions of the WO6 octahedra and NdO8 polyhedra in -KNdW2O8. This crystal structure photoluminescence study suggests that this class of tungstates can be exploited for visible light emitting devices by tuning the crystal symmetry.

  15. A search for the ground state structure and the phase stability of tantalum pentoxide.

    Science.gov (United States)

    Pérez-Walton, S; Valencia-Balvín, C; Padilha, A C M; Dalpian, G M; Osorio-Guillén, J M

    2016-01-27

    Tantalum pentoxide (Ta2O5) is a wide-gap semiconductor that presents good catalytic and dielectric properties, conferring to this compound promising prospective use in a variety of technological applications. However, there is a lack of understanding regarding the relations among its crystalline phases, as some of them are not even completely characterized and there is currently no agreement about which models better explain the crystallographic data. Additionally, its phase diagram is unknown. In this work we performed first-principles density functional theory calculations to study the structural properties of the different phases and models of Ta2O5, the equation of state and the zone-centered vibrational frequencies. From our results, we conclude that the phases that are built up from only distorted octahedra instead of combinations with pentagonal and/or hexagonal bipyramids are energetically more favorable and dynamically stable. More importantly, this study establishes that, given the pressure range considered, the B-phase is the most favorable structure and there is no a crystallographic phase transition to another phase at high-pressure. Additionally, for the equilibrium volume of the B-phase and the λ-model, the description of the electronic structure and optical properties were performed using semi-local and hybrid functionals.

  16. Synthesis, structure, and electronic properties of LaCa{sub 2}Mn{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Green, M.A.; Neumann, D.A.

    2000-01-01

    Synthesis of the Ruddlesden-Popper phase, LaCa{sub 2}Mn{sub 2}O{sub 7} is presented. The difficulty in obtaining a single-phase material, free from a perovskite impurity, is highlighted. Powder X-ray diffraction indicates an orthorhombic symmetry. Powder neutron diffraction reveals a subtle rotation of the MnO{sub 6} octahedra and reduction of symmetry to a C-centered orthorhombic cell (Cmcm). Cation ordering occurs with the larger La ions adopting the 12-coordinated site within the perovskite block and the smaller Ca ions situated in the 9-coordinated site in the rock salt layer. Magnetization measurements indicate a weak ferromagnetic transition at around 250 K, which is assigned to a perovskite impurity of 11.4%, as determined by neutron diffraction. Low-temperature neutron diffraction measurements confirms ferromagnetic ordering in the perovskite impurity and show no indication of long-range magnetic ordering in the majority Ruddlesden-Popper phase. Magnetotransport measurements show a metal-insulator transition at around 150 K and magnetoresistance up to 320 K. However, the perovskite impurity limits confidence in the assignment of the origin of the magnetoresistance effect.

  17. A closer look into close packing: pentacoordinated silicon in a high-pressure polymorph of danburite

    Directory of Open Access Journals (Sweden)

    Anna Pakhomova

    2017-09-01

    Full Text Available Due to their high technological and geological relevance, silicates are one of the most studied classes of inorganic compounds. Under ambient conditions, the silicon in silicates is almost exclusively coordinated by four oxygen atoms, while high-pressure treatment normally results in an increase in the coordination from four- to sixfold. Reported here is a high-pressure single-crystal X-ray diffraction study of danburite, CaB2Si2O8, the first compound showing a step-wise transition of Si coordination from tetrahedral to octahedral through a trigonal bipyramid. Along the compression, the Si2O7 groups of danburite first transform into chains of vertice-sharing SiO5 trigonal bipyramids (danburite-II and later into chains of edge-sharing SiO6 octahedra (danburite-III. It is suggested that the unusual formation of an SiO5 configuration is a consequence of filling up the pentacoordinated voids in the distorted hexagonal close packing of danburite-II.

  18. Struktur und Bindung in Übergangsmetall-Fluoriden MIIMeIVF6. Neutronenbeugungs-Strukturuntersuchungen an CaSnF6, FeZrF6, und CrZrF6

    Science.gov (United States)

    Mayer, H. W.; Reinen, D.; Heger, G.

    1983-11-01

    Compounds MIIMe IVF 6 requently undergo phase transitions from the cubic ordered ReO 3 to the trigonal LiSbF 6 structure when lowering the temperature. In case of a strongly Jahn-Teller unstable cation in the MII position additional phases may occur. Results of powder neutron-diffraction studies on CaSnF 6, FeZrF 6, and CrZrF 6 at different temperatures are reported. The high-temperature phases have the space group Fm3 m; the F - ligands are either statistically displaced from the MIIMe IV directions or undergo a strong thermal motion perpendicular to these directions ( ∢M II FMe IV: 165-180°). The thermal ellipsoids of the CrF bonds are strongly indicative of a dynamical Jahn-Teller effect in addition. In the low-temperature phases of CaSnF 6 and FeZrF 6 (space group R overline3) the ∢M II FMe IV is more distinctly bent (⋍155-160°). CrZrF 6 undergoes two reversible phase transitions, which are determined to occur at 415 ± 5 K (cubic → tetragonal, dynamic to static Jahn-Teller distortion of CrF 6 octahedra and 150 ± 10 K (tetragonal → (pseudo)monoclinic).

  19. Probing structural distortions in rare earth chromites using Indian synchrotron radiation source

    Science.gov (United States)

    Late, R.; Rai, H. M.; Saxena, S. K.; Kumar, R.; Sagdeo, A.; Sagdeo, P. R.

    2016-12-01

    Effect of R site ionic radius on the structural distortions in RCrO3 (R: La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Y) rare earth perovskite chromites is investigated through synchrotron based X-ray diffraction technique. The said structural distortions are measured in the terms of CrO bond lengths, CrO6 octahedral tilt, tolerance factor ( t) and RO12 polyhedral distortion. It is observed that the lattice parameters (b and c), RO bond length, tolerance factor and Cr-O-Cr bond angle increases with increase in the radius of R site ion; whereas octahedral tilts (along [010] and [101]) and RO12 polyhedral distortion decreases with increase in the radius of R site ion. Further it is observed that the radius of R site cation does not have significant effect on lattice parameter `a' and CrO bond length (hence on the distortion of CrO6 octahedra). A comparison of the crystal structure parameters obtained using refinement of synchrotron powder X-ray data and that estimated theoretically using modern bond valence parameters (SPuDS) has been carried out. A one to one correlation between the experimental and theoretical results has been observed.

  20. Effects of rare-earth size on the electronic structure of La1−xLuxVO3.

    Science.gov (United States)

    Chen, B; Laverock, J; Newby, D; McNulty, J F; Smith, K E; Glans, P-A; Guo, J-H; Qiao, R-M; Yang, W-L; Lees, M R; Tung, L D; Singh, R P; Balakrishnan, G

    2015-03-18

    The electronic structure of La(1-x)Lu(x)VO(3)(x = 0, 0.2, 0.6 and 1) single crystals has been investigated using soft x-ray absorption spectroscopy, soft x-ray emission spectroscopy, and resonant soft x-ray inelastic scattering to study the effects of rare-earth size. The x-ray absorption and emission spectra at the O K-edge present a progressive evolution with R-site cation, in agreement with local spin density approximation calculations. This evolution with R, together with the temperature dependence of the O K-edge spectra, is attributed to changes in the crystal structure of La(1-x)Lu(x)VO(3). The crystal-field dd. excitations probed by resonant inelastic x-ray scattering at the V L(3)-edge exhibit an increase in energy and enhanced intensity with the decrease of R-site ionic radius, which is mainly attributed to the increased tilting magnitude of the VO(6) octahedra. Upon cooling to ~95 K, the dd* excitations are prominently enhanced in relative Intensity, in agreement with the formation of the Jahn.Teller distortion int he orbital ordering phase. Additionally, the dd* transitions of the mixed compounds are noticeably suppressed with respect to those of the pure compounds, possibly owing to the formation of C-type orbital ordering induced by large R-site size variances.

  1. Effect of Arsenic on the Formation and Adsorption Property of Ferric Hydroxide Precipitates in ZVI Treatment

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Xing; Xi, Beidou; Zhao, Ying; Shi, Qiantao; Meng, Xiaoguang; Mao, Xuhui; Jiang, Yonghai; Ma, Zhifei; Tan, Wenbing; Liu, Hongliang; Gong, Bin (Stevens); (Beijing NU); (CRAES); (Wuhan)

    2017-08-14

    Treatment of arsenic by zerovalent iron (ZVI) has been studied extensively. However, the effect of arsenic on the formation of ferric hydroxide precipitates in the ZVI treatment has not been investigated. We discovered that the specific surface area (ca. 187 m2/g) and arsenic content (ca. 67 mg/g) of the suspended solids (As-containing solids) generated in the ZVI treatment of arsenic solutions were much higher than the specific surface area (ca. 37 m2/g) and adsorption capacity (ca.12 mg/g) of the suspended solids (As-free solids) generated in the arsenic-free solutions. Arsenic in the As-containing solids was much more stable than the adsorbed arsenic in As-free solids. XRD, SEM, TEM, and selected area electron diffraction (SAED) analyses showed that the As-containing solids consisted of amorphous nanoparticles, while the As-free solids were composed of micron particles with weak crystallinity. Extended X-ray absorption fine structure (EXAFS) analysis determined that As(V) was adsorbed on the As-containing suspended solids and magnetic solid surfaces through bidentate binuclear complexation; and As(V) formed a mononuclear complex on the As-free suspended solids. The formation of the surface As(V) complexes retarded the bonding of free FeO6 octahedra to the oxygen sites on FeO6 octahedral clusters and prevented the growth of the clusters and their development into 3-dimensional crystalline phases.

  2. Benzen and Ethylene Binding to Copper(I)-Ziconium(IV) Chloride Materials: The Crystal Structure and Solid-State Reactivity of ((bz)2Cu)2Zr2Cl10.bz

    Energy Technology Data Exchange (ETDEWEB)

    Dattelbaum,A.; Martin, J.

    2006-01-01

    The solvothermal reaction of Cu{sub 2}ZrCl{sub 6} and ZrCl{sub 4} in benzene is shown to yield the molecular species ((bz){sub 2}Cu){sub 2}Zr{sub 2}Cl{sub 10} {center_dot} bz(1), which is characterized by single crystal X-ray diffraction. The structure consists of edge-shared dimers of zirconium chloride octahedra whose axial chlorides are bridged by bis-benzene chlorocuprate fragments. The Cu{sub 2}Zr{sub 2} tetramers are linked in the crystal lattice by edge-to-face {pi}-stacking of the coordinated and lattice benzene molecules, as well as benzene-to-chloride hydrogen bonding. Benzene is lost from this material in a stepwise fashion resulting in what are described to be chain, ((bz)Cu){sub 2}Zr{sub 2}Cl{sub 10} (3). The desolvated materials, 2 and 3, reversibly sorb ethylene, as characterized by sorption isotherms, in situ pressure-resolved synchrotron X-ray diffraction and UV/Vis diffuse reflectance spectroscopy.

  3. Temperature dependence of excitonic emission in [(CH3)2NH2]3[BiI6] organic-inorganic natural self assembled bimodal quantum dots

    Science.gov (United States)

    Abid, Haitham; Samet, Amira; Mlayah, Adnen; Boughzala, Habib; Abid, Younes

    2017-11-01

    This paper reports on the optical properties of organic - inorganic natural self assembled bimodal quantum dots (dimetylammonium) hexa-iodobismuthate [(CH3)2NH2]3[BiI6]. The crystal structure consists of isolated BiI6 octahedra, as inorganic ions, surrounded by dimethylamine cations. At room temperature, we investigate the optical properties by: UV/Vis absorption, ellipsometry, diffuse reflectance and photoluminescence. A broad Gaussian-shape luminescence band with a large stokes shift is observed in the red spectral range at 2.15 eV, due to radiative recombination of confined excitons in BiI quantum dots, suggesting that excitons are self trapped. The temperature-dependence of the PL emission is investigated. The observed S-shaped emission behavior is explained by thermal escape occurring at lower temperatures for high-energy dots and carriers being recaptured by dots emitting on the low-energy side of the distribution. A rate equation model, showing agreement with the experimental results, is used to investigate the thermal redistribution of the charge carriers. Exciton binding energies of 149.125 and 295.086 meV were determined from the modified Arrhenius analysis.

  4. Ferromagnetic ordering in the layer-structured Pd(HS(2)O(7))(2).

    Science.gov (United States)

    Bruns, Jörn; Niehaus, Oliver; Pöttgen, Rainer; Wickleder, Mathias S

    2014-01-13

    The reaction of (NO2 )(CF3 SO3 ) and elemental palladium in oleum (65 % SO3 ) leads to violet single crystals of Pd(HS2 O7 )2 (monoclinic, P21 /c, Z=2, a=927.80(9), b=682.58(7), c=920.84(9) pm, β=117.756(2)°, wR2 =0.0439). In the crystal structure, the Pd(2+) ions show an uncommon octahedral coordination of six oxygen atoms belonging to six HS2 O7 (-) ions. The linkage of [PdO6 ] octahedra and the hydrogendisulfate anions leads to a layer structure, and the layers are held together by hydrogen bonds. The unusual coordination of the Pd(2+) ions results in an electronic d(8) high-spin configuration, which leads to the paramagnetic behavior of the compound. Moreover, at low temperature, a ferromagnetic ordering was observed with a Curie temperature of 8 K. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Native SrTiO3 (001) surface layer from resonant Ti L2,3 reflectance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Valvidares, Manuel; Huijben, Mark; Yu, Pu; Ramesh, Ramamoorthy; Kortright, Jeffrey

    2010-11-03

    We quantitatively model resonant Ti L2,3 reflectivity Rs,p(q, hn) from several SrTiO3 (001) single crystals having different initial surface preparations and stored in ambient conditions before and between measurements. All samples exhibit unexpected 300 K Rs(hn) - Rp(hn) anisotropy corresponding to weak linear dichroism and tetragonal distortion of the TiO6 octahedra indicating a surface layer with properties different from cubic SrTiO3. Oscillations in Rs(q) confirm a ubiquitous surface layer 2-3 nm thick that evolves over a range of time scales. Resonant optical constant spectra derived from Rs,p(hn) assuming a uniform sample are refined using a single surface layer to fit measured Rs(q). Differences in surface layer and bulk optical properties indicate that the surface is significantly depleted in Sr and enriched in Ti and O. While consistent with the tendency of SrTiO3 surfaces toward non-stoichiometry, this layer does not conform simply to existing models for the near surface region and apparently forms via room temperature surface reactions with the ambient. This new quantitative spectral modeling approach is generally applicable and has potential to study near-surface properties of a variety of systems with unique chemical and electronic sensitivities.

  6. Sign Reversal of the MN-O Bond Compressibility in La{sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7} Below T{sub C}: Exchange Striction in the Ferromagnetic State

    Science.gov (United States)

    Argyriou, D. N.; Mitchell, J. F.; Chmaissem, O.; Short, S.; Jorgensen, J. D.; Goodenough, J. B.

    1997-03-01

    The crystal structure of the layered perovskite La{sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7} has been studied under hydrostatic pressure up to {approximately} 6 kbar, in the paramagnetic and ferromagnetic states, with neutron powder diffraction. The compressibility of the Mn-O apical bonds in the double layer of MnO{sub 6} octahedra changes sign from the paramagnetic insulator (PI) to the ferromagnetic metal (FM) state; in the Fm state the Mn-O-Mn linkage between MnO{sub 2} planes expands under applied pressure, whereas they contract in the PI state. This counterintuative behavior is interpreted in terms of exchange striction, which reflect the competition between super- and double-exchange. An increase of the Mn-moment with applied pressure in the FM state is consistent with a positive dT{sub C}/dP, as well as a cant angle {theta}{sub 0} between the magnetizations of neighboring MnO{sub 2} sheets that decreases with pressure.

  7. Phenomenological theory of phase transitions in epitaxial BaxSr1-xTiO3 thin films on (111)-oriented cubic substrates

    Science.gov (United States)

    Shirokov, V. B.; Shakhovoy, R. A.; Razumnaya, A. G.; Yuzyuk, Yu. I.

    2015-07-01

    A phenomenological thermodynamic theory of BaxSr1-xTiO3 (BST-x) thin films epitaxially grown on (111)-oriented cubic substrates is developed using the Landau-Devonshire approach. The group-theoretical analysis of the low-symmetry phases was performed taking into account two order parameters: the polarization related to ionic shifts in polar zone-center F1u mode and the out-of-phase rotation of TiO6 octahedra corresponding to the R25 zone-boundary mode in the parent cubic phase P m 3 ¯ m . The eight-order thermodynamic potential for BST-x solid solutions was developed and analyzed. We constructed the "concentration-misfit strain" phase diagram for BST-x thin films at room temperature and found that polar rhombohedral R3m phase with the polarization normal to the substrate is stable for x > 0.72 and negative misfit strains, while ferroelectric monoclinic C2 and Cm phases with in-plane polarization are stable for much smaller x and positive or slightly negative misfit strains. We constructed the "temperature-misfit strain" phase diagrams for several concentrations (x = 1, 0.8, 0.6, 0.4, and 0.2). Systematic changes of the phase transition lines between the paraelectric and ferroelectric phases are discussed. The phase diagrams are useful for practical applications in thin-film engineering.

  8. Quasi-Two-Dimensional Metallic Ground State of Ca3Ru2O7

    Science.gov (United States)

    Yoshida, Yoshiyuki

    2005-03-01

    Ca3Ru2O7 is a three-dimensional antiferromagnetic metal between a first-order metal to nonmetal transition at 48 K and the antiferromagnetic ordering temperature, TN=56 K[1]. The crystal structure is the double layered Ruddlesden-Popper type with the Bb21m space group, which has both the rotation and tiling of RuO6 octahedra. We have succeeded in growing single crystals of Ca3Ru2O7 using a floating-zone method for the first time. The temperature dependence of the electrical resistivity establishes that Ca3Ru2O7 develops a quasi-two-dimensional metallic ground state below 30 K, from which the observed quantum oscillation derives. The specific heat measurement reveals the electronic specific-heat coefficient γ to be as small as 1.7 mJ/Ru mol K^2[2]. From the results of powder neutron diffractions, we proposed the most possible magnetic structure with an antiferromagnetic ordering. The field dependence of the resistivity at the metamagnetic transition around 6 T can be explained by the tunneling magnetoresistance. This work was done in collaboration with S. I. Ikeda, N. Shirakawa, C. H. Lee, M. Kosaka, and S. Katano. [1] G. Cao et al., Phys. Rev. Lett. 78 (1997) 1751. [2] Y. Yoshida et al., Phys. Rev. B 69 (2004) R220411.

  9. Bis(4,4'-bipyridinium) dodeca-tungsto-silicate 4,4'-bipyridine hexa-hydrate.

    Science.gov (United States)

    Ma, Feng-Xia; Zhao, Quan

    2008-09-06

    The title compound, (C(10)H(10)N(2))(2)[SiW(12)O(40)]·C(10)H(8)N(2)·6H(2)O or (4,4'-bipyH(2))(2)[SiW(12)O(40)].(4,4'-bipy)·6H(2)O (4,4'-bipy is 4,4'-bipyridine), was prepared under hydro-thermal conditions. The asymmetric unit contains a discrete Keggin-type [SiW(12)O(40)](4-) anion (located on a twofold axis), one 4,4'-bipy (located on a twofold axis), two (4,4'-bipyH(2))(2+) cations and six uncoordinated water mol-ecules. The polyoxoanion is constructed from a central SiO(4) tetra-hedron which shares its O atoms with four trinuclear W(3)O(13) groups, each of which is made up of three edge-sharing WO(6) octa-hedra. The water mol-ecules and [SiW(12)O(40)](4-) anions are linked through hydrogen bonds.

  10. Pseudocapacitive hausmannite nanoparticles with (101) facets: synthesis, characterization, and charge-transfer mechanism.

    Science.gov (United States)

    Yeager, Matthew P; Du, Wenxin; Wang, Qi; Deskins, N Aaron; Sullivan, Matthew; Bishop, Brendan; Su, Dong; Xu, Wenqian; Senanayake, Sanjaya D; Si, Rui; Hanson, Jonathan; Teng, Xiaowei

    2013-10-01

    Hausmannite Mn3 O4 octahedral nanoparticles of 18.3 ± 7.0 nm with (101) facets have been prepared by an oxygen-mediated growth. The electrochemical properties of the Mn3 O4 particles as pseudocapacitive cathode materials were characterized both in half-cells and in button-cells. The Mn3 O4 nanoparticles exhibited a high mass-specific capacitance of 261 F g(-1), which was calculated from cyclic voltammetry analyses, and a capacitive retention of 78% after 10,000 galvanostatic charge-discharge cycles. The charge-transfer mechanisms of the Mn3 O4 nanoparticles were further studied by using synchrotron-based in situ X-ray absorption near edge spectroscopy and XRD. Both measurements showed concurrently that throughout the potential window of 0-1.2 V (vs. Ag/AgCl), a stable spinel structure of Mn3 O4 remained, and a reversible electrochemical conversion between tetrahedral [Mn(II) O4 ] and octahedral [Mn(III) O6 ] units accounted for the redox activity. Density functional theory calculations further corroborated this mechanism by confirming the enhanced redox stability afforded by the abundant and exposed (101) facets of Mn3 O4 octahedra. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Synthesis and crystal structure of calcium dizinc iron(III tris(orthophosphate, CaZn2Fe(PO43

    Directory of Open Access Journals (Sweden)

    Jamal Khmiyas

    2016-09-01

    Full Text Available Single crystals of the title compound, CaZn2Fe(PO43, were synthesized by conventional solid-state reaction. In the asymmetric unit, all atoms are located in fully occupied general positions of the P21/c space group. The zinc atoms are located on two crystallographically independent sites with tetrahedral and distorted triangular-based bipyramidal geometries. Two edge-sharing triangular bipyramidal ZnO5 units form a dimer, which is linked to slightly deformed FeO6 octahedra via a common edge. The resulting chains are interconnected through PO4 tetrahedra to form a layer perpendicular to the b axis. Moreover, the remaining PO4 and ZnO4 tetrahedra are linked together through common vertices to form tapes parallel to the c axis and surrounding a chain of Ca2+ cations to build a sheet, also perpendicular to the b axis. The stacking of the two layers along the b axis leads to the resulting three-dimensional framework, which defines channels in which the Ca2+ cations are located, each cation being coordinated by seven oxygen atoms.

  12. Crystal structure of a silver-, cobalt- and iron-based phosphate with an alluaudite-like structure: Ag1.655Co1.64Fe1.36(PO43

    Directory of Open Access Journals (Sweden)

    Adam Bouraima

    2017-06-01

    Full Text Available The new silver-, cobalt- and iron-based phosphate, silver cobalt iron tris(orthophosphate, Ag1.655Co1.64Fe1.36(PO43, was synthesized by solid-state reactions. Its structure is isotypic to that of Na2Co2Fe(PO43, and belongs to the alluaudite family, with a partial cationic disorder, the AgI atoms being located on an inversion centre and twofold rotation axis sites (Wyckoff positions 4a and 4e, with partial occupancies of 0.885 (2 and 0.7688 (19, respectively. One of the two P atoms in the asymmetric unit completely fills one 4e site while the Co and Fe atoms fill another 4e site, with partial occupancies of 0.86 (5 and 0.14 (5, respectively. The remaining Co2+ and Fe3+ cations are distributed on a general position, 8f, in a 0.39 (4:0.61 (4 ratio. All O atoms and the other P atoms are in general positions. The structure is built up from zigzag chains of edge-sharing [MO6] (M = Fe/Co octahedra stacked parallel to [101]. These chains are linked together through PO4 tetrahedra, forming polyhedral sheets perpendicular to [010]. The resulting framework displays two types of channels running along [001], in which the AgI atoms (coordination number eight are located.

  13. Preparation, crystal structure, and metal-to-insulator transition of EuNiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, J.A.; Martinez-Lope, M.J.; Rasines, I. [Instituto de Ciencia de Materiales de Madrid (Spain)

    1995-11-15

    Polycrystalline EuNiO{sub 3} has been prepared by a citrate technique and a subsequent thermal treatment at 1000{degrees}C under 200 bar of oxygen pressure. The crystal structure was refined by the Rietveld method from X-ray powder diffraction data. EuNiO{sub 3} is an orthorhombic perovskite with a = 5.2938(1), b = 5.4560(1), c = 7.5359(2) {angstrom}, space group Pbnm, Z = 4. A bond valence study shows that Eu-O/Ni-O bonds which are thought to be in the origin of the metastable character of the structure. The trend of Ni to increase its binding power leads to the observed distortion of the NiO{sub 6} octahedra. The first-order metal-to-insulator (MI) transition was studied by differential scanning calorimetry (T{sub MI} = 463 or 459 K on the heating or cooling runs, respective). The corresponding heat flow is about half the value observed for NdNiO{sub 3}, in which a magnetic transition is associated to the MI transition.

  14. Ba 3 (Cr 0.97(1) Te 0.03(1) ) 2 TeO 9 : in Search of Jahn–Teller Distorted Cr(II) Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Li, Man-Rong; Deng, Zheng; Lapidus, Saul H.; Stephens, Peter W.; Segre, Carlo U.; Croft, Mark; Paria Sena, Robert; Hadermann, Joke; Walker, David; Greenblatt, Martha

    2016-10-17

    A novel 6H - type hexagonal perovskite Ba 3 (Cr 0.97(1) Te 0.03 (1 ) ) 2 TeO 9 was prepared at high pressure (6 GPa) and temperature ( 1 773 K). Both transmission electron microscopy and synchrotron powder x - ray diffraction data demonstrate that Ba 3 (Cr 0.97(1) Te 0.03(1) ) 2 TeO 9 crystallize s in P6 3 / mmc with face - shared (Cr 0.97(1) Te 0.03(1) )O 6 octahedral pairs interconnected with TeO 6 octahedra via corner - sharing. Structure analysis shows a mixed Cr 2+ /Cr 3+ valence state with ~ 10% Cr 2+ . The existence of Cr 2+ in Ba 3 (Cr 2+ 0.10(1) Cr 3+ 0.87(1) Te 6+ 0.03 ) 2 TeO 9 is further evidenced by x - ray absorption near edge spectr oscopy . Magnetic properties measurements show a paramagnetic response down to 4 K and a small glassy - state curvature at low temperature. In this work, the o ctahedral Cr 2+ O 6 component is stabilized in an oxide material for the first time ; the expected Jahn - Teller distortion of high - spin ( d 4 ) Cr 2+ is not found , which is attributed to the small proportion of Cr 2+ (~ 10%) and the face - sharing arrangement of CrO 6 octahedral pairs, that structu rally dis favor axial distortion.

  15. YPd{sub 2}Al and YPd{sub 2}Zn with LiCu{sub 2}Sn type structure

    Energy Technology Data Exchange (ETDEWEB)

    Gerke, Birgit; Rodewald, Ute C.; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany)

    2016-05-15

    The palladium-rich phases YPd{sub 2}Al and YPd{sub 2}Zn were synthesized from the elements; YPd{sub 2}Al by arc-melting and YPd{sub 2}Zn by induction melting in a sealed niobium ampoule. The structure of YPd{sub 2}Al was refined from single-crystal X-ray diffractometer data: LiCu{sub 2}Sn type, P6{sub 3}/mmc, a = 433.9(2), c = 910.5(2) pm, wR{sub 2} = 0.0497, 150 F{sup 2} values, and 9 variables. The lattice parameters of YPd{sub 2}Zn are a = 437.3(1) and c = 891.4(2) pm. The aluminum atoms in YPd{sub 2}Al show strongly flattened octahedral palladium coordination. These AlPd{sub 6} octahedra are condensed via edges, forming layers around z = 0 and z = 1/2, which are condensed in c direction by weak Pd-Pd bonds. The yttrium atoms fill the cavities between these layers. YPd{sub 2}Al and YPd{sub 2}Zn belong to a larger family of 341 compounds with the Wyckoff sequence 194,fca. The distinctly different crystal chemical branches are briefly discussed. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Local Structural Analysis of Half-Metallic Ferromagnet CrO2

    Science.gov (United States)

    Kodama, Katsuaki; Ikeda, Kazutaka; Isobe, Masahiko; Takeda, Hikaru; Itoh, Masayuki; Ueda, Yutaka; Shamoto, Shin-ichi; Otomo, Toshiya

    2016-09-01

    We have performed powder neutron diffraction on the half-metallic ferromagnet CrO2 which has a rutile-type crystal structure with a tetragonal unit cell. Although the powder diffraction pattern can be fitted by the reported crystal structure including a single Cr site, the atomic pair distribution function (PDF) can be fitted by the structural model with an orthorhombic unit cell including two kinds of inequivalent Cr sites. The difference between the valences of the two inequivalent Cr sites, δ of Cr+4±δ, estimated from the local structural parameters is about 0.06. The shapes of the two CrO6 octahedra are slightly different, suggesting the short-range orbital ordering of the Cr 3d orbitals. The lattice distortion and the improvement of the fitting to the PDF obtained using the locally distorted structure model are apparent in the region below about 10 Å, suggesting that the domain size or correlation length of the locally distorted structure is about 10 Å, roughly corresponding to the size of two unit cells.

  17. Ab initio modeling of Bose-Einstein condensation in Pb{sub 2}V{sub 3}O{sub 9}

    Energy Technology Data Exchange (ETDEWEB)

    Tsirlin, Alexander; Rosner, Helge [Max-Planck-Institute, CPfS, Dresden (Germany)

    2011-07-01

    We present the computational approach to the microscopic study of Bose-Einstein condensation (BEC) in quantum magnets. Using density functional theory band structure calculations, we establish the microscopic magnetic model of a BEC compound Pb{sub 2}V{sub 3}O{sub 9}, refine the model by fitting the experimental data, and further simulate the full temperature-vs-field phase diagram. In contrast to previous theoretical descriptions based on the alternating-spin-chain model, we find that Pb{sub 2}V{sub 3}O{sub 9} represents an unfrustrated quasi-two-dimensional spin system of coupled spin dimers. The intradimer coupling is about 30 K, whereas the interdimer couplings are both ferro- and antiferromagnetic. The structural implementation of the model is rather non-trivial, with weaker ferromagnetic couplings along the chains of corner-sharing VO{sub 6} octahedra and stronger antiferromagnetic couplings between the structural chains. Our model leads to remarkable agreement with the available experimental data on the BEC in Pb{sub 2}V{sub 3}O{sub 9} and discloses the role of individual exchange couplings in this compound. While antiferromagnetic couplings alone lead to a one-dimensional spin system, the presence of ferromagnetic couplings and the two-dimensionality are essential for the BEC high-field ground state of Pb{sub 2}V{sub 3}O{sub 9}.

  18. High-Pressure Synthesis and Local Structure of Corundum-Type In[subscript 2−2x]Zn[subscript x]Sn[subscript x]O[subscript 3] (x ≤ 0.7)

    Energy Technology Data Exchange (ETDEWEB)

    Hoel, Cathleen A.; Amores, Jos Manuel Gallardo; Morn, Emilio; Alario-Franco, Miguel Angel; Gaillard, Jean-Franois; Poeppelmeier, Kenneth R. (UCDM); (NWU)

    2010-12-06

    The corundum-type In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} solid solution (cor-ZITO, x {le} 0.7) was synthesized at 1000 C under a high pressure of 70 kbar. cor-ZITO is a high-pressure polymorph of the transparent conducting oxide bixbyite-In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} (x {le} 0.4). Analysis of the extended X-ray absorption fine structure suggests that significant face-sharing of Zn and Sn octahedra occurs, as expected for the corundum structure type. In contrast to the ideal corundum structure, however, Zn and Sn are displaced and form oxygen bonds with lengths that are similar to those observed in high-pressure ZnSnO{sub 3}. Powder X-ray diffraction patterns of cor-ZITO showed the expected unit cell contraction with increased cosubstitution, but no evidence for ilmenite-type ordering of the substituted Zn and Sn. A qualitative second harmonic generation measurement, for the solid solution x = 0.6 and using 1064 nm radiation, showed that Zn and Sn adopt a polar LiNbO{sub 3}-type arrangement.

  19. High-Pressure Synthesis and Local Structure of Corundum-Type In[subscript 2;#8722;2x]Zn[subscript x]Sn[subscript x]O[subscript 3] (x ;#8804; 0.7)

    Energy Technology Data Exchange (ETDEWEB)

    Hoel, Cathleen A.; Amores, Jose Manuel Gallardo; Moran, Emilio; Alario-Franco, Miguel Angel; Gaillard, Jean-Francois; Poeppelmeier, Kenneth R. (UCDM); (NWU)

    2011-08-09

    The corundum-type In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} solid solution (cor-ZITO, x {<=} 0.7) was synthesized at 1000 C under a high pressure of 70 kbar. cor-ZITO is a high-pressure polymorph of the transparent conducting oxide bixbyite-In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} (x {<=} 0.4). Analysis of the extended X-ray absorption fine structure suggests that significant face-sharing of Zn and Sn octahedra occurs, as expected for the corundum structure type. In contrast to the ideal corundum structure, however, Zn and Sn are displaced and form oxygen bonds with lengths that are similar to those observed in high-pressure ZnSnO{sub 3}. Powder X-ray diffraction patterns of cor-ZITO showed the expected unit cell contraction with increased cosubstitution, but no evidence for ilmenite-type ordering of the substituted Zn and Sn. A qualitative second harmonic generation measurement, for the solid solution x = 0.6 and using 1064 nm radiation, showed that Zn and Sn adopt a polar LiNbO{sub 3}-type arrangement.

  20. Pure Cs4PbBr6: Highly Luminescent Zero-Dimensional Perovskite Solids

    KAUST Repository

    Saidaminov, Makhsud I.

    2016-09-26

    So-called zero-dimensional perovskites, such as Cs4PbBr6, promise outstanding emissive properties. However, Cs4PbBr6 is mostly prepared by melting of precursors that usually leads to a coformation of undesired phases. Here, we report a simple low-temperature solution-processed synthesis of pure Cs4PbBr6 with remarkable emission properties. We found that pure Cs4PbBr6 in solid form exhibits a 45% photoluminescence quantum yield (PLQY), in contrast to its three-dimensional counterpart, CsPbBr3, which exhibits more than 2 orders of magnitude lower PLQY. Such a PLQY of Cs4PbBr6 is significantly higher than that of other solid forms of lower-dimensional metal halide perovskite derivatives and perovskite nanocrystals. We attribute this dramatic increase in PL to the high exciton binding energy, which we estimate to be ∼353 meV, likely induced by the unique Bergerhoff–Schmitz–Dumont-type crystal structure of Cs4PbBr6, in which metal-halide-comprised octahedra are spatially confined. Our findings bring this class of perovskite derivatives to the forefront of color-converting and light-emitting applications.

  1. Single-crystal X-ray diffraction study of Fe2SiO4 fayalite up to 31 GPa

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jin S.; Hu, Yi; Shelton, Hannah; Kung, Jennifer; Dera, Przemyslaw

    2016-10-03

    Olivine is widely believed to be the most abundant mineral in the Earth’s upper mantle. Here, we report structural refinement results for the Fe-end-member olivine, Fe2SiO4 fayalite, up to 31 GPa in diamond-anvil cell, using single-crystal synchrotron X-ray diffraction. Unit-cell parameters a, b, c and V, average Si–O Fe–O bond lengths, as well as Si–O Fe–O polyhedral volumes continuously decrease with increasing pressure. The pressure derivative of isothermal bulk modulus K'T0 is determined to be 4.0 (2) using third-order Birch–Murnaghan equation of state with ambient isothermal bulk modulus fixed to 135 GPa on the basis of previous Brillouin measurements. The Si–O tetrahedron is stiffer than the Fe–O octahedra, and the compression mechanism is dominated by Fe–O bond and Fe–O octahedral compression. Densities of olivine along 1600 and 900 K adiabats are calculated based on this study. The existence of metastable olivine inside the cold subduction slab could cause large positive buoyancy force against subduction, slow down the subduction and possibly affect the slab geometry.

  2. Anion order in perovskite oxynitrides.

    Science.gov (United States)

    Yang, Minghui; Oró-Solé, Judith; Rodgers, Jennifer A; Jorge, Ana Belén; Fuertes, Amparo; Attfield, J Paul

    2011-01-01

    Transition-metal oxynitrides with perovskite-type structures are an emerging class of materials with optical, photocatalytic, dielectric and magnetoresistive properties that may be sensitive to oxide-nitride order, but the anion-ordering principles were unclear. Here we report an investigation of the representative compounds SrMO(2)N (M = Nb, Ta) using neutron and electron diffraction. This revealed a robust 1O/2(O(0.5)N(0.5)) partial anion order (up to at least 750 °C in the apparently cubic high-temperature phases) that directs the rotations of MO(4)N(2) octahedra in the room-temperature superstructure. The anion distribution is consistent with local cis-ordering of the two nitrides in each octahedron driven by covalency, which results in disordered zigzag M-N chains in planes within the perovskite lattice. Local structures for the full range of oxynitride perovskites are predicted and a future challenge is to tune properties by controlling the order and dimensionality of the anion chains and networks.

  3. In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO42 during Heating by High Temperature Raman and 27Al NMR Spectroscopies

    Directory of Open Access Journals (Sweden)

    Min Wang

    2017-03-01

    Full Text Available Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO42 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi, lanthanide; MVI = Mo, W. The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO42 have been investigated by in-situ high temperature Raman scattering and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO6] octahedra in both KAl(MoO42 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K+, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.

  4. Atomistic Molecular Dynamic Simulations of Multiferroics

    Science.gov (United States)

    Wang, Dawei; Weerasinghe, Jeevaka; Bellaiche, L.

    2012-08-01

    A first-principles-based approach is developed to simulate dynamical properties, including complex permittivity and permeability in the GHz-THz range, of multiferroics at finite temperatures. It includes both structural degrees of freedom and magnetic moments as dynamic variables in Newtonian and Landau-Lifshitz-Gilbert (LLG) equations within molecular dynamics, respectively, with the couplings between these variables being incorporated. The use of a damping coefficient and of the fluctuation field in the LLG equations is required to obtain equilibrated magnetic properties at any temperature. No electromagnon is found in the spin-canted structure of BiFeO3. On the other hand, two magnons with very different frequencies are predicted via the use of this method. The smallest-in-frequency magnon corresponds to oscillations of the weak ferromagnetic vector in the basal plane being perpendicular to the polarization while the second magnon corresponds to magnetic dipoles going in and out of this basal plane. The large value of the frequency of this second magnon is caused by static couplings between magnetic dipoles with electric dipoles and oxygen octahedra tiltings.

  5. Ti/Zr isomorphism in wadeite: The crystal structure of the titanium-dominant K2(Ti0.55Zr0.45)Si3O9 member of the series

    Science.gov (United States)

    Karimova, O. V.; Yakubovich, O. V.; Ageeva, O. A.; Erofeeva, K. G.

    2017-05-01

    The crystal structure of the titanium-rich mineral wadeite K2(Ti0.55Zr0.45)Si3O9 from rischorrites of the Khibiny Alkaline Massif (Kola Peninsula, Russia) is studied by X-ray diffraction (XCalibur-S diffractometer, R = 0.0459): a = 6.8611(6) Å and c = 10.0611(9) Å; space group P63/ m, Z = 6, D x = 3.03 g/cm3. It is shown that the unit-cell parameters and volume of the mineral of mixed (Ti/Zr) composition are naturally intermediate between those of the terminal members of the isomorphous wadeite-based K2ZrSi3O9-K2(Ti0.55Zr0.45)Si3O9-K2TiSi3O9 series. The expected correlation is due to the ionic radii of Zr4+ and Ti4+ which determine the lengths of Zr/Ti-O bonds in octahedra. The data of field observations and microscopic studies show that the Ti-dominant wadeite is formed on the basis of primary zirconium mineral in the course of a late imposed process under unique geochemical conditions.

  6. Structure, phase transitions, and isotope effects in [(CH3)4N]2PuCl6

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Richard E.

    2015-11-02

    The single crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long standing confusion and speculation regarding the structure of this compound in the literature. A temperature dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd-3c a = 26.012(3) Å. At 360 K, the structure is in space group Fm-3m with a = 13.088(1) Å. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement and the degree of rotation varies with temperature, giving rise to the phase transition from Fm-3m to Fd-3c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition as revealed by a changing transition temperature in the deuterated versus protonated compound indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation.

  7. Synthesis and crystal structure of the new telluric acid adduct (RbCl){sub 3}.Te(OH){sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Mahlmeister, Dirk; Irran, Elisabeth [Technische Univ. Berlin (Germany). Inst. fuer Chemie

    2012-01-15

    The new telluric acid adduct (RbCl){sub 3}.Te(OH){sub 6} was prepared by dissolving RbCl and Te(OH){sub 6} in the molar ratio of 3: 1 in deionized water at r.t. and slow evaporation of the solvent in air. The crystal structure of the colorless crystals was determined with single-crystal X-ray diffraction (trigonal space group: R anti 3c (no.167), a = 14.4392(8), c = 10.4301(16) A, Z = 6). In (RbCl){sub 3}.Te(OH){sub 6}, the rubidium atom is surrounded by five chlorine and four oxygen atoms in form of an irregular tricapped trigonal prism.E ach tellurium atom is octahedrally surrounded by six oxygen atoms. The Te(OH){sub 6} octahedra and the RbCl{sub 5}O{sub 4} polyhedra are linked to a dense three-dimensional network which is additionally strengthened by hydrogen bonds. (orig.)

  8. B3LYP density functional calculations on the ground-state structure, elastic properties, and compression mechanism of α-ZrW2O8

    Science.gov (United States)

    Figueirêdo, C. A.; Perottoni, C. A.

    2007-05-01

    The structure of α-ZrW2O8 was optimized at different pressures and its elastic constants were calculated at the B3LYP density functional level of theory. Overall, the relative stiffnesses of the atomic bonds (and linkages), ranked in terms of bond compressibilities, decrease according to the sequence W-O>Zr⋯W>Zr-O . The tetrahedra around tungsten atoms are found to be much stiffer than the ZrO6 octahedra. These latter are, in fact, more compressible than the α-ZrW2O8 unit cell. The elastic constants calculated in the athermal limit are in excellent agreement with recent experimental results obtained near 0K . The α-ZrW2O8 compression mechanism around W1 and W2 atoms is quite different. While the former can be described essentially in terms of a correlated polyhedral rotation, the latter involves correlated rotation of the first coordination polyhedra and translation of WO4 units downward along the ⟨111⟩ axis. These modes of deformation should bear some resemblance to the low-energy modes responsible for the negative thermal expansion in zirconium tungstate, and thus could give some insight on the microscopic mechanism behind this phenomenon.

  9. Compression mechanism and pressure-induced amorphization of γ-ZrW2O8

    Science.gov (United States)

    Figueirêdo, C. A.; Catafesta, J.; Zorzi, J. E.; Salvador, L.; Baumvol, I. J. R.; Gallas, M. R.; da Jornada, J. A. H.; Perottoni, C. A.

    2007-11-01

    The structure of γ-ZrW2O8 has been optimized at zero pressure and also at V/V0=0.97 by means of density functional theory calculations using the B3LYP functional. As previously found for α-ZrW2O8 , tungsten polyhedra are stiffer than zirconium octahedra in γ-ZrW2O8 . However, contrary to what has been found for α-ZrW2O8 , all first coordination polyhedra in the γ phase are less compressible than the unit cell. Volume reduction in γ-ZrW2O8 is, thus, mainly accomplished by polyhedral tilting. Upon pressure increase, the distance between the terminal oxygen and W atoms from the nearest polyhedra decreases by as much as 3.66% (for the pair O101-W6). Accordingly, a further reduction in the zirconium tungstate molar volume with the high-pressure transition to the amorphous phase should bring several oxygen atoms within the threshold of bond formation to W. O1s photoelectron spectra provide further experimental evidence on the formation of additional W-O bonds in amorphous zirconium tungstate. These new W-O bonds should enable the metastable retention of the amorphous phase upon pressure release.

  10. X-ray Analyses of Lead Adsorption on the (001), (110), and (012) Hematite Surfaces.

    Science.gov (United States)

    Noerpel, Matthew R; Lee, Sang Soo; Lenhart, John J

    2016-11-15

    Predicting the environmental fate of lead relies on a detailed understanding of its coordination to mineral surfaces, which in turn reflects the innate reactivity of the mineral surface. In this research, we investigated fundamental dependencies in lead adsorption to hematite by coupling extended X-ray absorption fine structure (EXAFS) spectroscopy on hematite particles (10 and 50 nm) with resonant anomalous X-ray reflectivity (RAXR) to single crystals expressing the (001), (012), or (110) crystallographic face. The EXAFS showed that lead adsorbed in a bidentate inner-sphere manner in both edge and corner sharing arrangements on the FeO6 octahedra for both particle sizes. The RAXR measurements confirmed these inner-sphere adsorption modes for all three hematite surfaces and additionally revealed outer-sphere adsorption modes not seen in the EXAFS. Lead uptake was larger and pH dependence was greater for the (012) and (110) surfaces, than the (001) surface, due to their expressing singly- and triply coordinated oxygen atoms the (001) surface lacks. In coupling these two techniques we provide a more detailed and nuanced picture of the coordination of lead to hematite while also providing fundamental insight into the reactivity of hematite.

  11. Lead-Free Hybrid Material with an Exceptional Dielectric Phase Transition Induced by a Chair-to-Boat Conformation Change of the Organic Cation.

    Science.gov (United States)

    Han, Shiguo; Zhang, Jing; Sun, Zhihua; Ji, Chengmin; Zhang, Weichuan; Wang, Yuyin; Tao, Kewen; Teng, Bing; Luo, Junhua

    2017-11-06

    Hybrid organic-inorganic perovskite materials have demonstrated great potential in the field of photovoltaics and photoelectronics. On the basis of the high degree of structural flexibility and compatibility, diverse molecular functional materials have been assembled by modifying the length of the organic components and/or dimensionality of the inorganic frameworks. In this paper, we present a chiral lead-free organic-inorganic hybrid, (piperidinium)2SbCl5 (1), which follows the one-dimensional inorganic frameworks of the corner-sharing SbCl6 octahedra. Strikingly, 1 displays a dielectric phase transition at Tc = 338 K, changing from the chiral space group of P212121 to polar Pna21 upon heating. Crystal structure analyses reveal that an unusual thermally activated conformation change of the piperidinium cations affords the driving force to the phase transition of 1. That is, organic piperidinium moieties display a chairlike conformation below Tc, which transforms to a boatlike structure above Tc. Such an unprecedented change is strongly coupled to the dielectric transition along with notable steplike anomalies, which suggest that 1 could be used as a potential switchable dielectric material. Besides, the temperature-dependent conductivity and theoretical analysis of its electronic structure disclose the semiconducting behavior of 1. This study paves the pathway to the design of new lead-free semiconducting perovskites with targeted properties for optoelectronic application.

  12. Number series of atoms, interatomic bonds and interface bonds defining zinc-blende nanocrystals as function of size, shape and surface orientation: Analytic tools to interpret solid state spectroscopy data

    Energy Technology Data Exchange (ETDEWEB)

    König, Dirk, E-mail: dirk.koenig@unsw.edu.au [Integrated Materials Design Centre (IMDC) and School of Photovoltaic and Renewable Energy Engineering (SPREE), University of New South Wales, Sydney (Australia)

    2016-08-15

    Semiconductor nanocrystals (NCs) experience stress and charge transfer by embedding materials or ligands and impurity atoms. In return, the environment of NCs experiences a NC stress response which may lead to matrix deformation and propagated strain. Up to now, there is no universal gauge to evaluate the stress impact on NCs and their response as a function of NC size d{sub NC}. I deduce geometrical number series as analytical tools to obtain the number of NC atoms N{sub NC}(d{sub NC}[i]), bonds between NC atoms N{sub bnd}(d{sub NC}[i]) and interface bonds N{sub IF}(d{sub NC}[i]) for seven high symmetry zinc-blende (zb) NCs with low-index faceting: {001} cubes, {111} octahedra, {110} dodecahedra, {001}-{111} pyramids, {111} tetrahedra, {111}-{001} quatrodecahedra and {001}-{111} quadrodecahedra. The fundamental insights into NC structures revealed here allow for major advancements in data interpretation and understanding of zb- and diamond-lattice based nanomaterials. The analytical number series can serve as a standard procedure for stress evaluation in solid state spectroscopy due to their deterministic nature, easy use and general applicability over a wide range of spectroscopy methods as well as NC sizes, forms and materials.

  13. Trimethylsulfonium Lead Triiodide: An Air-Stable Hybrid Halide Perovskite.

    Science.gov (United States)

    Kaltzoglou, Andreas; Stoumpos, Constantinos C; Kontos, Athanassios G; Manolis, Georgios K; Papadopoulos, Kyriakos; Papadokostaki, Kyriaki G; Psycharis, Vasilis; Tang, Chiu C; Jung, Young-Kwang; Walsh, Aron; Kanatzidis, Mercouri G; Falaras, Polycarpos

    2017-06-05

    We report on the synthesis, characterization, and optoelectronic properties of the novel trimethylsulfonium lead triiodide perovskite, (CH3)3SPbI3. At room temperature, the air-stable compound adopts a hexagonal crystal structure with a 1D network of face-sharing [PbI6] octahedra along the c axis. UV-vis reflectance spectroscopy on a pressed pellet revealed a band gap of 3.1 eV, in agreement with first-principles calculations, which show a small separation between direct and indirect band gaps. Electrical resistivity measurements on single crystals indicated that the compound behaves as a semiconductor. According to multi-temperature single-crystal X-ray diffraction, synchrotron powder X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry, two fully reversible structural phase transitions occur at -5 and ca. -100 °C with reduction of the unit cell symmetry to monoclinic as temperature decreases. The role of the trimethylsulfonium cation regarding the chemical stability and optoelectronic properties of the new compound is discussed in comparison with APbI3 (A = Cs, methylammonium, and formamidinium cation), which are most commonly used in perovskite solar cells.

  14. The molecular structure of the borate mineral inderite Mg(H4B3O7)(OH) · 5H2O--a vibrational spectroscopic study.

    Science.gov (United States)

    Frost, Ray L; López, Andrés; Xi, Yunfei; Lima, Rosa Malena Fernandes; Scholz, Ricardo; Granja, Amanda

    2013-12-01

    We have undertaken a study of the mineral inderite Mg(H4B3O7)(OH) · 5H2O a hydrated hydroxy borate mineral of magnesium using scanning electron microscopy, thermogravimetry and vibrational spectroscopic techniques. The structure consists of [Formula: see text] soroborate groups and Mg(OH)2(H2O)4 octahedra interconnected into discrete molecules by the sharing of two OH groups. Thermogravimetry shows a mass loss of 47.2% at 137.5 °C, proving the mineral is thermally unstable. Raman bands at 954, 1047 and 1116 cm(-1) are assigned to the trigonal symmetric stretching mode. The two bands at 880 and 916 cm(-1) are attributed to the symmetric stretching mode of the tetrahedral boron. Both the Raman and infrared spectra of inderite show complexity. Raman bands are observed at 3052, 3233, 3330, 3392 attributed to water stretching vibrations and 3459 cm(-1) with sharper bands at 3459, 3530 and 3562 cm(-1) assigned to OH stretching vibrations. Vibrational spectroscopy is used to assess the molecular structure of inderite. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Redetermination of eveite, Mn2AsO4(OH, based on single-crystal X-ray diffraction data

    Directory of Open Access Journals (Sweden)

    Yongbo W. Yang

    2011-12-01

    Full Text Available The crystal structure of eveite, ideally Mn2(AsO4(OH [dimanganese(II arsenate(V hydroxide], was refined from a single crystal selected from a co-type sample from Långban, Filipstad, Varmland, Sweden. Eveite, dimorphic with sarkinite, is structurally analogous with the important rock-forming mineral andalusite, Al2OSiO4, and belongs to the libethenite group. Its structure consists of chains of edge-sharing distorted [MnO4(OH2] octahedra (..2 symmetry extending parallel to [001]. These chains are cross-linked by isolated AsO4 tetrahedra (..m symmetry through corner-sharing, forming channels in which dimers of edge-sharing [MnO4(OH] trigonal bipyramids (..m symmetry are located. In contrast to the previous refinement from Weissenberg photographic data [Moore & Smyth (1968. Am. Mineral. 53, 1841–1845], all non-H atoms were refined with anisotropic displacement parameters and the H atom was located. The distance of the donor and acceptor O atoms involved in hydrogen bonding is in agreement with Raman spectroscopic data. Examination of the Raman spectra for arsenate minerals in the libethenite group reveals that the position of the peak originating from the O—H stretching vibration shifts to lower wavenumbers from eveite, to adamite, zincolivenite, and olivenite.

  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. A High Laser Damage Threshold and a Good Second-Harmonic Generation Response in a New Infrared NLO Material: LiSm3SiS7

    Directory of Open Access Journals (Sweden)

    Ni Zhen

    2016-09-01

    Full Text Available A series of new infrared nonlinear optical (IR NLO materials, LiRe3MS7 (Re = Sm, Gd; M = Si, Ge, have been successfully synthesized in vacuum-sealed silica tubes via a high-temperature solid-state method. All of them crystallize in the non-centrosymmetric space group P63 of the hexagonal system. In their structures, LiS6 octahedra connect with each other by sharing common faces to form infinite isolated one-dimensional ∞[LiS3]n chains along the 63 axis. ReS8 polyhedra share edges and corners to construct a three-dimensional tunnel structure with ∞[LiS3]n chains located inside. Remarkably, LiSm3SiS7 shows promising potential as one new IR NLO candidate, including a wide IR transparent region (0.44–21 μm, a high laser damage threshold (LDT (3.7 × benchmark AgGaS2, and a good NLO response (1.5 × AgGaS2 at a particle size between 88 μm and 105 μm. Dipole-moment calculation was also used to analyze the origin of NLO responses for title compounds.

  18. The optical properties of Sr3SiAl10O20 and Sr3SiAl10O20:Mn4+

    Science.gov (United States)

    Jansen, Thomas; Jüstel, Thomas

    2017-11-01

    Mn4+-activated luminescent materials have attracted significant attention recently. In particular, alkaline earth aluminates, such as Sr4Al14O25:Mn4+ and CaAl12O19:Mn4+, emit light in the red region, which can be exploited in phosphor-converted LEDs. We applied a sol-gel precursor followed by a ceramic method to synthesize highly crystalline Mn4+-doped Sr3SiAl10O20. The compound Sr3SiAl10O20:Mn4+ exhibits deep red photoluminescence that peaks at 663 nm, which can be assigned to the 2Eg → 4A2g intraconfigurational transition of Mn4+ ([Ar]3d.3 configuration) within the [MnO6]8- octahedra on the aluminum site in the Sr3SiAl10O20 (Space group C12/m1) host structure. The photoluminescence properties, such as the temperature dependence of the luminescence intensity and luminescence lifetime, are presented. Furthermore, the luminescence intensity as function of the activator concentration was investigated. Additionally, the band structure of the undoped host material was treated with Density Functional Theory (DFT). The theoretical results were evaluated experimentally with diffuse UV reflectance spectroscopy. Finally, the crystal field and Racah parameters were extracted to compare with those reported in the literature.

  19. Surface relaxation and tilting in SrHfO 3 orthorhombic perovskite: Hybrid HF-DFT LCAO calculations

    Science.gov (United States)

    Evarestov, R. A.; Bandura, A. V.; Blokhin, E. N.

    2008-12-01

    HF-DFT LCAO hybrid simulations on (0 0 1) and (1 1 0) surfaces of orthorhombic and (0 0 1) surface of cubic SrHfO 3 perovskite are performed using a single slab model framework. PBE0 exchange-correlation functional is used for this study. The energy and crystal structure of bulk cubic and orthorhombic phases are calculated and compared. It is found that orthorhombic modification is more stable than cubic one by 24 kJ mol -1 per formula unit. Calculated average surface energies and relaxation energies proved to be similar for all orthorhombic surfaces. Atomic displacements along the direction normal to the surface are primarily determined by the type of termination and weakly depend on the surface indices. Without symmetry constraining, cubic surfaces are unstable with respect to reconstruction to corresponding orthorhombic surfaces at T = 0 K. While the upright displacements of the topmost atoms are mainly due to additional distortions of the surface octahedra, the lateral atomic displacements are closely related to changing in surface group tilting. The approach for the analysis of surface octahedron tilting is proposed and applied to the relaxed orthorhombic surfaces of SrHfO 3 perovskites. It is shown that the HfO 5 group on the HfO 2-termianted surfaces undergoes a considerable turn upon relaxation, resulting in alignment of Hf-O-Hf bonds to corresponding pseudo-cubic directions.

  20. New ferromagnetic La{sub 3}Co{sub 2}TaO{sub 9} double perovskite: Structural and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Fuertes, V.C.; Blanco, M.C.; Franco, D.G.; De Paoli, J.M.; Pannunzio Miner, E.V. [INFIQC, Dpto. de Fisicoquimica, Fac. de Ciencias Quimicas, U.N.C., Cordoba 5000 (Argentina); Sanchez, R.D. [Laboratorio de Resonancias Magneticas. Centro Atomico Bariloche, Bariloche 8400, Rio Negro (Argentina); Fernandez-Diaz, M.T. [Institut Max Von Laue Paul Langevin, F-38042, Grenoble Cedex 9 (France); Carbonio, R.E., E-mail: carbonio@mail.fcq.unc.edu.a [INFIQC, Dpto. de Fisicoquimica, Fac. de Ciencias Quimicas, U.N.C., Cordoba 5000 (Argentina)

    2009-10-01

    The new double perovskite La{sub 3}Co{sub 2}TaO{sub 9} has been prepared by a solid-state procedure. The crystal and magnetic structures have been studied from X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD) data. Rietveld refinements were performed in the monoclinic space group P2{sub 1}/n. The structure consists of an ordered array of alternating B'O{sub 6} and B''O{sub 6} octahedra sharing corners, tilted along the three pseudocubic axes according to the Glazer notation a{sup -}b{sup -}c{sup +}. Rietveld refinements show that at RT the cell parameters are a=5.6005(7) A, b=5.6931(7) A, c=7.9429(9) A and beta=89.9539(7){sup o}, and the refined crystallographic formula of this 'double perovskite' can be written as La{sub 2}(Co){sub 2d}(Co{sub 1/3}Ta{sub 2/3}){sub 2c}O{sub 6}. Magnetization measurements and low-temperature NPD data show that the perovskite is a ferromagnet with T{sub C}=72 K. At high T it follows the Curie-Weiss law with an effective magnetic moment of 3.82mu{sub B} per Co ion which is very close to spin only Co{sup 2+} (HS).

  1. First principles investigation of carbon-screw dislocation interactions in body-centered cubic metals

    Science.gov (United States)

    Lüthi, B.; Ventelon, L.; Elsässer, C.; Rodney, D.; Willaime, F.

    2017-12-01

    Using ab initio density functional theory calculations, we investigate the effect of interstitial carbon solutes on 1/2 screw dislocations in non-magnetic body-centered cubic transition metals from group 5 (V, Nb, Ta) and group 6 (Mo, W). The two groups are found to display different solute-dislocation interaction behaviors. Group 6 shows a core reconstruction similar to that previously reported in Fe(C): the dislocation adopts a hard-core configuration with the carbon atoms at the center of regular trigonal prisms formed by the metal atoms. The solute-dislocation interaction energies are strongly attractive, ranging from -1.3 to -1.9 eV depending on the metal and the carbon-carbon distance. By way of contrast, the configuration of lowest energy in group 5 consists of the dislocation in its easy core and the carbon atom in a fifth nearest neighbor octahedral site. The configuration is attractive, but less than in group 6. We show that this group dependence is consistent with the carbon local environment in the stable stoichiometric carbide structures, namely cubic NaCl-type for group 5 and hexagonal WC-type for group 6: in both cases the carbon atoms are at the center of octahedra and prisms respectively.

  2. Electronic phase transitions and magnetoresistance in a new bilayer manganate, Ca{sub 2.5}Sr{sub 0.5}GaMn{sub 2}O{sub 8}

    Energy Technology Data Exchange (ETDEWEB)

    Battle, Peter D [Inorganic Chemistry Laboratory, Department of Chemistry, Oxford University, South Parks Road, Oxford (United Kingdom); Blundell, Stephen J [Clarendon Laboratory, Department of Physics, Oxford University, Parks Road, Oxford (United Kingdom); Santhosh, P N [Inorganic Chemistry Laboratory, Department of Chemistry, Oxford University, South Parks Road, Oxford (United Kingdom); Rosseinsky, Matthew J [Department of Chemistry, University of Liverpool, Liverpool (United Kingdom); Steer, Christopher [Clarendon Laboratory, Department of Physics, Oxford University, Parks Road, Oxford (United Kingdom)

    2002-12-16

    The crystal structure of the anion-deficient perovskite Ca{sub 2.5}Sr{sub 0.5}GaMn{sub 2}O{sub 8} has been studied at 290 and 5 K by neutron diffraction (290 K; space group Pcm2{sub 1}, a=5.4294(1), b=11.3722(3), c=5.2983(1)A). The vacant oxide sites order to create a structure in which perovskite bilayers consisting of MnO{sub 6} octahedra are isolated from each other along [010] by a single layer of GaO{sub 4} tetrahedra. At 5 K the material is antiferromagnetic with an ordered magnetic moment of 3.09(1) {mu}{sub B} per Mn cation. Magnetic susceptibility measurements suggest that short-range magnetic ordering within the bilayers occurs above 200 K, and muon spin relaxation data show that the transition to long-range magnetic order occurs between 150 and 125 K. The resistivity of Ca{sub 2.5}Sr{sub 0.5}GaMn{sub 2}O{sub 8} decreases by an order of magnitude at 125 K, and {approx}50% magnetoresistance is seen in a field of 80 kOe at 110 K.

  3. A multi technique study of a new lithium disilicate glass-ceramic spray-coated on ZrO2 substrate for dental restoration

    Directory of Open Access Journals (Sweden)

    Möncke Doris

    2017-09-01

    Full Text Available An alkali niobate-silicate veneer ceramic for ZrO2-based dental restoration was developed and characterized for its physical properties and structure. The properties were adjusted for dental applications. The new lithium disilicate glass-ceramic VBK (sold as cerafusion or LiSi can easily be applied by spray coating to any individually formed ZrO2-matrix and needs only one final tempering treatment. The surface of the glass-ceramic is very smooth. The color of the already translucent glass-ceramic can be adjusted to that of individual natural teeth. The structure of the glass-ceramicwas studied by XRD and Ramanspectroscopy as a function of heat-treatment and of spatial variations within the material and at its interfaces. ToF SIMS, SEM and thermal analysis techniques were applied to investigate the crystallization behavior and surface-interface reactions. XRD and Raman spectroscopy identified different crystalline phases in the amorphous glass matrix including Li2Si2O5, Li2SiO3, NaxLi(1−xNbO3 and Na3NbO4. The Raman spectrum of the amorphous matrix is dominated by the vibrational activity of the highly polarizable niobate units with a prominent feature at 865 cm−1, assigned to Nb-O stretching in NbO6 octahedra, which have non-bridging oxygen atoms and are connected to the silicate matrix rather than to other niobate polyhedra.

  4. Synthesis and crystal structure of Fe[(Te1.5Se0.5)O5]Cl, the first iron compound with selenate(IV) and tellurate(IV) groups

    Science.gov (United States)

    Akhrorov, Akhmad Yu; Kuznetsova, Elena S.; Aksenov, Sergey M.; Berdonosov, Peter S.; Kuznetsov, Alexey N.; Dolgikh, Valery A.

    2017-12-01

    During the search for selenium analogues of FeTe2O5Cl, the new iron (III) tellurate(IV) selenate(IV) chloride with the composition Fe[(Te1.5Se0.5)O5]Cl was synthesized by chemical vapor transport (CVT) reaction and characterized by TGA-, EDX-,SCXRD-analysis, as well as IR and Raman spectroscopy. It was found that Fe[(Te1.5Se0.5)O5]Cl crystallizes in the monoclinic space group P21/c with unitcell parameters a = 5.183(3) Å, b = 15.521(9) Å, c = 7.128(5) Å and β = 107.16(1)°. The crystal structure of Fe[(Te1.5Se0.5)O5]Cl represents a new structure type and contains electroneutral heteropolyhedral layers formed by dimers of the [FeO5Cl]8- octahedra, linked via common O-O edges, and mixed [Te3SeO10]4- tetramers. Adjacent layers are stacked along the b axis and linked by weak residual bonds. The new compound is stable up to 420 °C. DFT calculations predict Fe[(Te1.5Se0.5)O5]Cl to be a wide-gap semiconductor with the band gap of ca. 2.7 eV.

  5. Temperature-dependent Raman and ultraviolet photoelectron spectroscopy studies on phase transition behavior of VO{sub 2} films with M1 and M2 phases

    Energy Technology Data Exchange (ETDEWEB)

    Okimura, Kunio, E-mail: okifn@keyaki.cc.u-tokai.ac.jp; Hanis Azhan, Nurul [Graduate School of Engineering, Tokai University, Hiratsuka 259-1292 (Japan); Hajiri, Tetsuya [UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585 (Japan); Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan); Kimura, Shin-ichi [UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585 (Japan); Graduate School of Frontier Biosciences, Osaka University, Suita 565-0871 (Japan); Zaghrioui, Mustapha; Sakai, Joe [GREMAN, UMR 7347 CNRS, Université François Rabelais de Tours, Parc de Grandmont, 37200 Tours (France)

    2014-04-21

    Structural and electronic phase transitions behavior of two polycrystalline VO{sub 2} films, one with pure M1 phase and the other with pure M2 phase at room temperature, were investigated by temperature-controlled Raman spectroscopy and ultraviolet photoelectron spectroscopy (UPS). We observed characteristic transient dynamics in which the Raman modes at 195 cm{sup −1} (V-V vibration) and 616 cm{sup −1} (V-O vibration) showed remarkable hardening along the temperature in M1 phase film, indicating the rearrangements of V-V pairs and VO{sub 6} octahedra. It was also shown that the M1 Raman mode frequency approached those of invariant M2 peaks before entering rutile phase. In UPS spectra with high energy resolution of 0.03 eV for the M2 phase film, narrower V{sub 3d} band was observed together with smaller gap compared to those of M1 phase film, supporting the nature of Mott insulator of M2 phase even in the polycrystalline film. Cooperative behavior of lattice rearrangements and electronic phase transition was suggested for M1 phase film.

  6. Explorations of new selenites of the group IIIA and IVA metals

    Science.gov (United States)

    Kong, Fang; Li, Pei-Xin; Zhang, Su-Yun; Mao, Jiang-Gao

    2012-06-01

    Systematic explorations of new phases in the GaIII/InIII/GeIV-SeIV-O systems by hydrothermal syntheses or solid-state reactions at high-temperature led to six new ternary compounds, namely, M2Se2O7 (M=Ga 1, In 2), M(OH)(SeO3) (M=Ga 3, In 4), α-Ge(SeO3)25 and β-Ge(SeO3)26. Ga2Se2O71 displays a 3D open framework composed of 2D gallium oxide layers being further bridged and capped by SeO3 groups. In2Se2O72 features a 3D indium oxide framework formed by corner- and edge- sharing InO6 octahedra with SeO3 groups attached on the cavities and the 8-member ring tunnels of the structure. The isostructural of M(OH)(SeO3) (M=Ga 3, In 4) exhibit a 2D metal selenite layer composed of 1D edge-sharing MO6 octahedral chains that are interconnected by SeO3 groups. α-Ge(SeO3)2 (P21/n) 5 displays a 3D open framework with 1D 8-member ring tunnels along the a-axis while β-Ge(SeO3)2 (Pa-3) 6 exhibits a condensed 3D network.

  7. Rb6(InCo)2(Si9O26): a mixed-metal silicate containing 20-membered-ring silicate single layers with a very low Si:O ratio.

    Science.gov (United States)

    Hung, Ling-I; Wang, Sue-Lein; Chen, Yen-Hung; Lii, Kwang-Hwa

    2006-03-06

    A new cobalt-indium silicate, Rb6(InCo)2(Si9O26), has been synthesized via a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. It crystallizes in the noncentrosymmetric orthorhombic space group Aba2 (No. 41) with a = 20.779(1) A, b = 12.0944(6) A, c = 10.7761(5) A, V =2708.1(2) A(3), and Z = 4. The structure consists of 20-membered-ring silicate single layers of corner-sharing SiO4 tetrahedra interconnected by dimers of edge-sharing CoO4 tetrahedra and InO6 octahedra into a 3D framework. The Si:O ratio for the title compound is the lowest among the known single-layer silicates. Magnetic susceptibility confirms the divalent state of the cobalt ion. The powder sample has a second-harmonic-generation signal, confirming the absence of a center of symmetry in the structure.

  8. Hydrothermal synthesis, crystal structure, and solid-state NMR spectroscopy of a new indium silicate: K2In(OH)(Si4O10).

    Science.gov (United States)

    Hung, Ling-I; Wang, Sue-Lein; Kao, Hsien-Ming; Lii, Kwang-Hwa

    2003-06-30

    A new indium(III) silicate, K(2)In(OH)(Si(4)O(10)), has been synthesized by a high-temperature, high-pressure hydrothermal method. It crystallizes in the monoclinic space group P2(1)/m (No. 11) with a = 11.410(1) A, b = 8.373(1) A, c = 11.611(1) A, beta = 112.201(2) degrees, and Z = 4. The structure, which is analogous to that of K(2)CuSi(4)O(10), consists of unbranched vierer 4-fold chains of corner-sharing SiO(4) tetrahedra running along the b axis linked together via corner sharing by chains of trans-corner-sharing InO(4)(OH)(2) octahedra to form a 3-D framework which delimits 8-ring and 6-ring channels to accommodate K(+) cations. The presence of hydroxyl groups is confirmed by IR spectroscopy. The (29)Si MAS NMR exhibits four resonances at -88.6, -90.1, -97.4, and -98.2 ppm corresponding to four distinct crystallographic Si sites. A (1)H --> (29)Si CP/MAS NMR experiment was performed to assign the four resonances.

  9. Breathing mode distortion and magnetic order in rare-earth nickelates RNiO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Hampel, Alexander; Ederer, Claude [Materials Theory, ETH Zuerich (Switzerland)

    2016-07-01

    Rare-earth nickelate perovskites display a rich and not yet fully understood phase diagram, where all RNiO{sub 3} compounds with R from Sm to Lu undergo a non-magnetic metal-insulator transition (MIT). This transition is connected to a lattice distortion, which can be described as breathing mode of the oxygen octahedra surrounding the Ni cations. Between 100-250 K the RNiO{sub 3} compounds undergo a magnetic transition to an antiferromagnetic (AFM) state, with a wave-vector k= [(1)/(4) (1)/(4) (1)/(4)] relative to the underlying simple cubic perovskite structure. Here, we use density functional theory and its extensions (DFT+U, DFT+DMFT) together with distortion mode analysis to explore the interplay between lattice distortions, magnetic order, and the strength of the local Coulomb interaction U in rare earth nickelates. Our results show a strong dependency of the breathing mode amplitude on the magnetic order, with a much larger breathing mode obtained for the AFM state compared to the ferromagnetic case. Furthermore, we demonstrate that DFT+U is able to capture the correct trends of the lattice distortions across the nickelate series.

  10. Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb)

    Energy Technology Data Exchange (ETDEWEB)

    Bugaris, Daniel E.; Malliakas, Christos D.; Shoemaker, Daniel P.; Do, Dat T.; Chung, Duck Young; Mahanti, Subhendra D.; Kanatzidis, Mercouri G.

    2014-09-15

    Using metal fluxes, crystals of the binary osmium dipnictides OsPn(2) (Pn = P, As, Sb) have been grown for the first time. Single-crystal X-ray diffraction confirms that these compounds crystallize in the marcasite structure type with orthorhombic space group Pnnm. The structure is a three-dimensional framework of corner- and edge-sharing OsPn(6) octahedra, as well as [Pn(2)(-4)] anions. Raman spectroscopy shows the presence of PP single bonds, consistent with the presence of [Pn(2)(-4)] anions and formally Os4+ cations. Optical-band-gap and high-temperature electrical resistivity measurements indicate that these materials are narrow-band-gap semiconductors. The experimentally determined Seebeck coefficients reveal that nominally undoped OsP2 and OsSb2 are n-type semiconductors, whereas OsAs2 is p-type. Electronic band structure using density functional theory calculations shows that these compounds are indirect narrow-band-gap semiconductors. The bonding p orbitals associated with the Pn(2) dimer are below the Fermi energy, and the corresponding antibonding states are above, consistent with a PnPn single bond. Thermopower calculations using Boltzmann transport theory and constant relaxation time approximation show that these materials are potentially good thermoelectrics, in agreement with experiment.

  11. Probing the local structure of doped manganites using the atomic pair distribution function

    Science.gov (United States)

    Proffen, T.; Billinge, S. J. L.

    We have used atomic pair distribution function (PDF) analysis based on neutron powder diffraction data to investigate the local structure of the colossal magnetoresistant manganite La0.75Ca0.25MnO3 as a function of temperature. In the doping range 0.17materials show a metal-to-insulator transition, transforming from a ferromagnetic metal (FM) at low temperature to a paramagnetic insulator (PI). We can probe the charge distribution of the sample using the PDF by searching for evidence of Jahn-Teller (JT) distorted octahedra, implying the presence of Mn3+ ions. A two-phase model based on the local structures of the FM and PI phases was used to refine the experimental PDFs quantitatively. We observe the co-existence of both phases over a wide temperature range: approximately 10% of the localized JT phase (PI) is present even at the lowest temperature (T=20K), whereas at room temperature nearly half of the sample remains in the delocalized (FM) phase.

  12. Piezoelectricity and local structural distortions in (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}Sr{sub x}TiO{sub 3}-Bi{sub 12}TiO{sub 20} flexoelectric-type polar ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Wang, L. H.; Zhao, M. L.; Wang, C. L.; Wang, J.; Kuai, W. J.; Tao, X. T. [School of Physics, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)

    2012-08-06

    We have previously described sintered Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}-Bi{sub 12}TiO{sub 20} composites as flexoelectric-type polar ceramics because they have a net macroscopic flexoelectric polarization. Here, we report on the universal existence of the macroscopic flexoelectric polarization in the (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}Sr{sub x}TiO{sub 3}-Bi{sub 12}TiO{sub 20} system, in which enhanced piezoelectricity is observed. By combining Raman spectroscopy and x-ray photoelectron spectroscopy techniques, we have identified the local flexoelectric polarization as distorted BiO{sub 5} polyhedra and TiO{sub 6} octahedra in the SrTiO{sub 3}-Bi{sub 12}TiO{sub 20} ceramic. The macroscopic polarization may be due to the partial alignment of these distorted units located within the grain boundary amorphous phases. Bi{sub 12}TiO{sub 20} could have an important role in these flexoelectric-type polar ceramics.

  13. Structure of KTiOAsO{sub 4} single crystals at 293 and 30 K

    Energy Technology Data Exchange (ETDEWEB)

    Novikova, N. E., E-mail: natnov@ns.crys.ras.ru; Verin, I. A.; Sorokina, N. I.; Alekseeva, O. A. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Tseitlin, M. [Ariel University Center of Samaria (Israel); Roth, M. [Hebrew University of Jerusalem, Faculty of Science (Israel)

    2010-05-15

    The unit cell parameters of KTiOPO{sub 4} and KTiOAsO{sub 4} single crystals are measured in the temperature range from room temperature to 20 K. It is found that the unit cell volume of the single crystals changes smoothly. With a decrease in temperature, the c parameter remains almost unchanged. In a certain temperature range, the linear temperature dependence of the a and b parameters is violated. An X-ray diffraction study of KTiOAsO{sub 4} single crystals is performed at T = 293 and 30 K. With a decrease in temperature, the electron density in the channels of the structure undergoes a redistribution, suggesting that at room temperature the state of the potassium ions is characterized by the dynamic and static disordering. The nonuniformity of the distribution of the electron density at the junctions of TiO{sub 6} octahedra and AsO{sub 4} tetrahedra is significantly enhanced in relation to that at the corresponding junctions in the KTiOPO{sub 4} structure. It has been experimentally established that the geometry of the tetrahedral anions makes a decisive contribution to the nonlinearity of KTiOAsO{sub 4} single crystals.

  14. Application of symmetry operation measures in structural inorganic chemistry.

    Science.gov (United States)

    Echeverría, Jorge; Alvarez, Santiago

    2008-12-01

    This paper presents an application of the recently proposed symmetry operation measures to the determination of the effective symmetry point group of coordination polyhedra in inorganic solids. Several structure types based on octahedra are found to present distinct distortion patterns each, not strictly attached to the crystallographic site symmetry. These include the (NH4)2[CuCl4], CdI2 (brucite), FeS2 (pyrite), TiO2 (rutile), CaCl2, GdFeO3, PbTiO3,LiNbO3, BiI3, CrCl3, Al2O3, and NiWO4 structures. It is shown that a similar analysis can be applied to the Bailar and tetragonal Jahn-Teller distortions of molecular transition metal complexes, as well as to solids based on tetrahedra, such as the ZnCl2, FeS, BeCl2, SiS2, and KFeS2 structure types.

  15. Antiferromagnetic CsCrF{sub 5} and canted antiferromagnetism in RbCrF{sub 5} and KCrF{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Jagličić, Zvonko, E-mail: zvonko.jaglicic@imfm.si [University of Ljubljana, Faculty of Civil and Geodetic Engineering, and Institute of Mathematics, Physics and Mechanics, Jadranska 19, 1000 Ljubljana (Slovenia); Mazej, Zoran, E-mail: zoran.mazej@ijs.si [Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana (Slovenia)

    2017-07-15

    Highlights: • Cr(IV) ions are antiferromagnetically coupled within chains in ACrF{sub 5} (A = Cs, Rb, K). • Small structural difference causes huge difference in magnetic properties below 10 K. • Canted antiferromagnetism has been observed in RbCrF{sub 5} and KCrF{sub 5} at low temperature. - Abstract: In ACrF{sub 5} (A = Cs, Rb, K), Cr(IV) ions are coordinated by six fluoride ligands where the resulting CrF{sub 6} octahedra share cis vertexes to form infinite chains of ([Cr{sup IV}F{sub 5}]{sup −}){sub n}. The geometry of the latter in Cs compound differs from that in K and Rb compounds. The results of investigations of the magnetic behaviour of these compounds have shown that an antiferromagnetic superexchange interaction is present within the chains with J{sub Cs} = −10.2 cm{sup −1}, J{sub Rb} = −13.3 cm{sup −1}, and J{sub K} = −13.1 cm{sup −1}. Additional ferromagnetic-like long-range ordering has been observed in KCrF{sub 5} and RbCrF{sub 5} below 6 K which can be explained, in a correlation with their crystal structures, as canted antiferromagnetism.

  16. NH4FeCl2(HCOO): synthesis, structure, and magnetism of a novel low-dimensional magnetic material.

    Science.gov (United States)

    Greenfield, Joshua T; Kamali, Saeed; Izquierdo, Nezhueyotl; Chen, Michael; Kovnir, Kirill

    2014-03-17

    Solvothermal synthesis was used to create a low-dimensional iron(II) chloride formate compound, NH4FeCl2(HCOO), that exhibits interesting magnetic properties. NH4FeCl2(HCOO) crystallizes in the monoclinic space group C2/c (No. 15) with a = 7.888(1) Å, b = 11.156(2) Å, c = 6.920(2) Å, and β = 108.066(2)°. The crystal structure consists of infinite zigzag chains of distorted Fe(2+)-centered octahedra linked by μ2-Cl and syn-syn formate bridges, with interchain hydrogen bonding through NH4(+) cations holding the chains together. The unique Fe(2+) site is coordinated by four equatorial chlorides at a distance of 2.50 Å and two axial oxygens at a distance of 2.08 Å. Magnetic measurements performed on powder and oriented single-crystal samples show complex anisotropic magnetic behavior dominated by antiferromagnetic interactions (TN = 6 K) with a small ferromagnetic component in the direction of chain propagation. An anisotropic metamagnetic transition was observed in the ordered state at 2 K in an applied magnetic field of 0.85-3 T. (57)Fe Mössbauer spectroscopy reveals mixed hyperfine interactions below the ordering temperature, with strong electric field gradients and complex noncollinear arrangement of the magnetic moments.

  17. Structure-property relations in Sr, Nb, Ba doped lead zirconate titanate

    CERN Document Server

    Zheng, H

    2001-01-01

    rhombohedral or tetragonal forms or as mixture of the two (MPB), depending on Zi:Ti ratio. Zr:Ti ratio strongly affected d sub 3 sub 3 , which was maximised in the tetragonal phase close to, but not at, the MPB. Sr sup 2 sup + substitution on the A-site promoted tetragonality in PZT, greatly reducing T sub C , and broadening the dielectric maximum. As the Sr sup 2 sup + content was increased, Zr:Ti ratio was adjusted to maximise d sub 3 sub 3 and the optimised d sub 3 sub 3 values increased from 410 pC/N (Sr sup 2 sup + = 0) to 640 pC/N (Sr sup 2 sup + = 0.12), commensurate with a decrease in the T sub C. However, for ceramics where Sr sup 2 sup + > 0.12, optimised d sub 3 sub 3 decreased with respect to the values for ceramics where Sr sup 2 sup + = 0.12 even though T sub C was lowered. Electron diffraction patterns revealed superlattice reflections occurring at 1/2 left brace hkl right brace positions associated with rotations of oxygen octahedra in anti-phase. It was suggested that Sr sup 2 sup + substitut...

  18. Correlation between structural and transport properties of electron beam irradiated PrMnO3 compounds

    Science.gov (United States)

    Christopher, Benedict; Rao, Ashok; Nagaraja, B. S.; Shyam Prasad, K.; Okram, G. S.; Sanjeev, Ganesh; Petwal, Vikash Chandra; Verma, Vijay Pal; Dwivedi, Jishnu; Poornesh, P.

    2018-02-01

    The structural, electrical, magnetic, and thermal properties of electron beam (EB) irradiated PrMnO3 manganites were investigated in the present communication. X-ray diffraction data reveals that all samples are single phased with orthorhombic distorted structure (Pbnm). Furthermore, the diffracted data are analyzed in detail using Rietveld refinement technique. It is observed that the EB dosage feebly disturbs the MnO6 octahedra. The electrical resistivity of all the samples exhibits semiconducting behavior. Small polaron hopping model is conveniently employed to investigate the semiconducting nature of the pristine as well as EB irradiated samples. The Seebeck coefficient (S) of the pristine as well as the irradiated samples exhibit large positive values at lower temperatures, signifying holes as the dominant charge carriers. The analysis of Seebeck coefficient data confirms that the small polaron hopping mechanism assists the thermoelectric transport property in the high temperature region. The magnetic measurements confirm the existence of paramagnetic (PM) to ferromagnetic (FM) behavior for the pristine and irradiated samples. In the lower temperature regime, coexistence of FM clusters and AFM matrix is dominating. Thus, the complex magnetic behavior of the compound has been explained in terms of rearrangement of antiferromagnetically coupled ionic moments.

  19. Crystal structure of ZnWO{sub 4} scintillator material in the range of 3-1423 K

    Energy Technology Data Exchange (ETDEWEB)

    Trots, D M [HASYLAB at DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Senyshyn, A [Technische Universitaet Darmstadt, FB Material- und Geowissenschaften, Fachgebiet Strukturforschung, Petersenstrasse 23, D-64287 Darmstadt (Germany); Vasylechko, L [Lviv Polytechnic National University, Bandera Street 12, 79013 Lviv (Ukraine); Niewa, R [Department Chemie, Technische Universitaet Muenchen, Lichtenbergstrasse 4, 85747 Garching bei Muenchen (Germany); Vad, T [Institut fuer Werkstoffwissenschaft, Technische Universitaet Dresden, Mommsenstrasse 13, 01062 Dresden (Germany); Mikhailik, V B; Kraus, H, E-mail: d_trots@yahoo.co, E-mail: Anatoliy.Senyshyn@frm2.tum.d [Department of Physics, University of Oxford, Oxford OX1 3RH (United Kingdom)

    2009-08-12

    The behaviour of the crystal structure of ZnWO{sub 4} was investigated by means of synchrotron and neutron powder diffraction in the range of 3-300 K. Thermal analysis showed the sample's melting around 1486 K upon heating and subsequent solidification at 1442 K upon cooling. Therefore, the structure was also investigated at 1423 K by means of neutron diffraction. It is found that the compound adopts the wolframite structure type over the whole temperature range investigated. The lattice parameters and volume of ZnWO{sub 4} at low temperatures were parametrized on the basis of the first order Grueneisen approximation and a Debye model for an internal energy. The expansivities along the a- and b-axes adopt similar values and saturate close to 8 x 10{sup -6} K{sup -1}, whereas the expansion along the c-axis is much smaller and shows no saturation up to 300 K. The minimum expansivity corresponds to the direction close to the c-axis where edge-sharing linkages of octahedra occur.

  20. A new oxyfluorinated titanium phosphate anode for a high-energy lithium-ion battery.

    Science.gov (United States)

    Ma, Zhaohui; Sun, Chunwen; Lyu, Yingchun; Wang, Yuesheng; Kim, Youngsik; Chen, Liquan

    2015-01-21

    Na3[Ti2P2O10F] was synthesized by a hydrothermal method. It has an open framework structure consisting of TiFO5 octahedra and PO4 tetrahedra. The feasibility of Na3[Ti2P2O10F] as an anode material for lithium-ion batteries was first studied. Na3[Ti2P2O10F] exhibits a reversible capacity of more than 200 mAh g(-1) at a discharge/charge current rate of 20 mA g(-1) (∼0.1 C) and 105 mA g(-1) at a discharge/charge current rate of 400 mA g(-1) (∼2 C) with a lower intercalation voltage. The result of in situ X-ray diffraction test shows the structural evolution during the first discharge/charge cycle. The structure of Na3[Ti2P2O10F] was kept during discharge/charge with a slight change of the lattice parameters, which indicates a lithium solid solution behavior.