Sample records for 2sesub 4sub 4sesub

  1. Thermodynamic Model for the Solubility of Ba(SeO4sub>, SO4sub>) Precipitates

    SciTech Connect

    Rai, D.; Felmy, Andrew R.; Moore, Dean A.; Kitamura, Akira; Yoshikawa, Hideki; Doi, Reisuke; Yoshida, Yasushi


    The solubility of Ba(SeO4sub>, SO4sub>) precipitates was determined as a function of the BaSeO4sub> mole fractions, ranging from 0.0015 to 0.3830, and time with an equilibration period extending to as long as 302 days. Equilibrium/steady state conditions in this system are reached in ≤ 65 days. Pitzer’s ion interaction model was used to calculate solid and aqueous phase activity coefficients. Thermodynamic analyses showed that the data do not satisfy Gibbs-Duhem equation, thereby demonstrating that a single-solid solution phase does not control both the selenate and sulfate concentrations. Our extensive data with log 10 [Ba] ranging from -3.6 to -5.9 mol kg-1, log 10 [SeO4sub>] rangingfrom-3.6 to -5.2 mol kg-1, and log 10 [SO4sub>] ranging from-4.0 to -5.3 mol kg-1 can be explained with the formation of an ideal BaSeO4sub> solid solution phase that controls the selenium concentrations and a slightly disordered/less-crystalline BaSO4sub>(s) (log 10Κ°sp = -9.5 instead of -10.05 for barite) that controls the sulfate concentrations. In these experiments the BaSO4sub> component of the solid solution phase never reaches thermodynamic equilibrium with the aqueous phase. Thermodynamic interpretations of the data show that both the ideal BaSeO4sub> solid solution phase and less-crystalline BaSO4sub> (s) phase are in equilibrium with each other in the entire range of BaSeO4sub> mole fractions investigated in this study.

  2. Solvate Structures and Computational/Spectroscopic Characterization of LiBF4sub> Electrolytes

    SciTech Connect

    Seo, D. M.; Boyle, Paul D.; Allen, Joshua L.; Han, Sang D.; Jonsson, Erlendur; Johansson, Patrik; Henderson, Wesley A.


    Crystal structures have been determined for both LiBF4sub> and HBF4sub> solvates—(acetonitrile)2:LiBF4sub>, (ethylene glycol diethyl ether)1:LiBF4sub>, (diethylene glycol diethyl ether)1:LiBF4sub>, (tetrahydrofuran)1:LiBF4, (methyl methoxyacetate)1:LiBF4sub>, (suc-cinonitrile)1:LiBF4sub>, (N,N,N',N",N"-pentamethyldiethylenetriamine)1:HBF4sub>, (N,N,N',N'-tetramethylethylenediamine)3/2:HBF4sub> and (phenanthroline)2:HBF4sub>. These, as well as other known LiBF4sub> solvate structures, have been characterized by Raman vibrational spectroscopy to unambiguously assign the anion Raman band positions to specific forms of BF4sub>-...Li+ cation coordination. In addition, complementary DFT calculations of BF4sub>-...Li+ cation complexes have provided additional insight into the challenges associated with accurately interpreting the anion interactions from experimental Raman spectra. This information provides a crucial tool for the characterization of the ionic association interactions within electrolytes.

  3. Solution-processable glass LiI-Li4sub>SnS4sub> superionic conductors for all-solid-state Li-ion batteries

    SciTech Connect

    Kern Ho Park; Oh, Dae Yang; Choi, Young Eun; Nam, Young Jin; Han, Lili; Kim, Ju -Young; Xin, Huolin; Lin, Feng; Oh, Seung M.; Jung, Yoon Seok


    The new, highly conductive (4.1 × 10–4 S cm–1 at 30 °C), highly deformable, and dry-air-stable glass 0.4LiI-0.6Li4sub>SnS4sub> is prepared using a homogeneous methanol solution. Furthermore, the solution process enables the wetting of any exposed surface of the active materials with highly conductive solidified electrolytes (0.4LiI-0.6Li4sub>SnS4sub>), resulting in considerable improvements in electrochemical performances of these electrodes over conventional mixture electrodes.

  4. U(v) in metal uranates: A combined experimental and theoretical study of MgUO4sub>, CrUO4sub>, and FeUO4sub>

    SciTech Connect

    Guo, Xiaofeng; Tiferet, Eitan; Qi, Liang; Solomon, Jonathan M.; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Kukkadapu, Ravi K.; Wu, Di; Ilton, Eugene S.; Asta, Mark; Sutton, Stephen R.; Xu, Hongwu; Navrotsky, Alexandra


    Although pentavalent uranium can exist in aqueous solution, its presence in the solid state is uncommon. Metal monouranates, MgUO4sub>, CrUO4sub> and FeUO4sub> were synthesized for detailed structural and energetic investigations. Structural characteristics of these uranates used powder X-ray diffraction, synchrotron X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and 57Fe-Mossbauer spectroscopy. Enthalpies of formation were measured by high temperature oxide melt solution calorimetry. Density functional theory (DFT) calculations provided both structural and energetic information. The measured structural and thermodynamic properties show good consistency with those predicted from DFT. The presence of U5+ has been solidly confirmed in CrUO4sub> and FeUO4sub>, which are thermodynamically stable compounds, and the origin and stability of U5+ in the system was elaborated by DFT. Lastly, the structural and thermodynamic behaviour of U5+ elucidated in this work is relevant to fundamental actinide redox chemistry and to applications in the nuclear industry and radioactive waste disposal.

  5. The novel phase transition of NaBi(WO{sub 4}){sub 2} under high pressure

    SciTech Connect

    Ma, Chunli; Cui, Hang; Li, Fangfei; Wang, Jingshu; Wu, Xiaoxin; Zhang, Jian; Zhou, Qiang; Liu, Jinghe; Cui, Qiliang


    The Raman and synchrotron angle-dispersive X-ray diffraction studies have been performed on NaBi(WO{sub 4}){sub 2} under high pressure up to 30.7 and 36.2 GPa, respectively, at room temperature. With pressure increases to ∼7.0 GPa, the structure of NaBi(WO{sub 4}){sub 2} begins to transform from tetragonal (I4{sub 1}/a) into monoclinic (P2/m), and the phase transition completes around 13 GPa. With pressure higher than 29.0 GPa, the NaBi(WO{sub 4}){sub 2} turns into amorphous state. The random arrangement of Na{sup +} and Bi{sup 3+} in short-range ordered scheelite NaBi(WO{sub 4}){sub 2} results in the tetragonal to monoclinic phase transition, which is different from that observed in AWO{sub 4} tungstates and AMoO{sub 4} molybdates (A=Ca, Sr, Ba, Pb, Eu, Cd). - Graphical abstract: The NaBi(WO{sub 4}){sub 2} transforms from tetragonal into monoclinic, which starts around 7 GPa and completes at about 13 GPa. With pressure higher than 29 GPa, the NaBi(WO{sub 4}){sub 2} turns into amorphous state. Highlights: ► Raman and X-ray diffraction studies performed on NaBi(WO{sub 4}){sub 2} up to 30.7 and 36.2 GPa, respectively. ► The tetragonal (I4{sub 1}/a) into monoclinic (P2/m) phase transition is determined. ► With pressure higher than 29 GPa, the NaBi(WO{sub 4}){sub 2} ultimately turns into amorphous state. ► The ambient pressure bulk modulus and volume of tetragonal and monoclinic phases are obtained.

  6. Aqueous Sulfate Separation by Sequestration of [(SO4sub>)2(H2O)4sub>]4sub> Clusters within Highly Insoluble Imine-Linked Bis-Guanidinium Crystals

    SciTech Connect

    Custelcean, Radu; Williams, Neil J.; Seipp, Charles A.; Ivanov, Aleksandr; Bryantsev, Vyacheslav


    Quantitative removal of sulfate from seawater was achieved by selective crystallization of the anion with a bis(guanidinium) ligand self-assembled in situ through imine condensation of simple components. The resulting crystalline salt has an exceptionally low aqueous solubility, on a par with BaSO4sub>. Single-crystal X-ray diffraction analysis revealed pairs of sulfate anions clustered together with four water molecules within the crystals.

  7. Native defects in Tl6SI4sub>: Density functional calculations

    SciTech Connect

    Shi, Hongliang; Du, Mao -Hua


    In this study, Tl6SI4sub> is a promising room-temperature semiconductor radiation detection material. Here, we report density functional calculations of native defects and dielectric properties of Tl6SI4sub>. Formation energies and defect levels of native point defects and defect complexes are calculated. Donor-acceptor defect complexes are shown to be abundant in Tl6SI4sub>. High resistivity can be obtained by Fermi level pinning by native donor and acceptor defects. Deep donors that are detrimental to electron transport are identified and methods to mitigate such problem are discussed. Furthermore, we show that mixed ionic-covalent character of Tl6SI4sub> gives rise to enhanced Born effective charges and large static dielectric constant, which provides effective screening of charged defects and impurities.

  8. Origin of modulated phases and magnetic hysteresis in TmB4sub>

    SciTech Connect

    Wierschem, Keola; Sunku, Sai Swaroop; Kong, Tai; Ito, Toshimitsu; Canfield, Paul C.; Panagopoulos, Christos; Sengupta, Pinaki


    In this study, we investigate the low-temperature magnetic phases in TmB4sub>, a metallic quantum magnet on the geometrically frustrated Shastry-Sutherland lattice, using coordinated experimental and theoretical studies. Our results provide an explanation for the appearance of the intriguing fractional plateau in TmB4sub> and accompanying magnetic hysteresis. Together with observation of the bump in the half plateau, our results support the picture that the magnetization plateau structure in TmB4sub> is strongly influenced by the zero-field modulated phases. We present a phenomenological model to explain the appearance of the modulated phases and a microscopic Hamiltonian that captures the complete magnetic behavior of TmB4sub>.

  9. The hydrogen permeability of Pd4sub>S

    SciTech Connect

    O’Brien, Casey P.; Gellman, Andrew J.; Morreale, Bryan D.; Miller, James B.


    Hydrogen permeates rapidly through pure Pd membranes, but H2S, a common minor component in hydrogencontaining streams, produces a Pd4sub>S film on the Pd surface that severely retards hydrogen permeation. Hydrogen still permeates through the bi-layered Pd4sub>S/Pd structure, indicating that the Pd4sub>S surface is active for H2 dissociation; the low hydrogen permeability of the Pd4sub>S film is responsible for the decreased rate of hydrogen transport. In this work, the hydrogen permeability of Pd4sub>S was determined experimentally in the 623-773 K temperature range. Bi-layered Pd4sub>S/Pd foils were produced by exposing pure Pd foils to H2S. H2 fluxes through the bi-layered Pd4sub>S/Pd foils were measured during exposure to both pure H2 and a 1000 ppm H2S in H2 gas mixture. Our results show that H2S slows hydrogen permeation through Pd mainly by producing a Pd4S film on the Pd surface that is roughly an order-of-magnitude less permeable to hydrogen (kPd4S = 10-7.5 exp(-0.22 eV/kBT)molH2/m/s/Pa-1/2) than pure Pd. The presence of H2S in the gas stream results in greater inhibition of hydrogen transport than can be explained by the very low permeability of Pd4sub>S. H2S may block H2 dissociation sites at the Pd4sub>S surface.

  10. The role of carbonic anhydrase in C4sub> photosynthesis

    SciTech Connect

    Studer, Anthony


    Current pressures on the global food supply have accelerated the urgency for a second green revolution using novel and sustainable approaches to increase crop yield and efficiency. This proposal outlines experiments to address fundamental questions regarding the biology of C4sub> photosynthesis, the method of carbon fixation utilized by the most productive food, feed and bioenergy crops. Carbonic anhydrase (CA) has been implicated in multiple cellular functions including nitrogen metabolism, water use efficiency, and photosynthesis. CA catalyzes the first dedicated step in C4sub> photosynthesis, the hydration of CO2 into bicarbonate, and is potentially rate limiting in C4sub> grasses. Using insertional mutagenesis, we have generated CA mutants in maize, and propose the characterization of these mutants using phenotypic, physiological, and transcriptomic profiling to assay the plant’s response to altered CA activity. In addition, florescent protein tagging experiments will be employed to study the subcellular localization of CA paralogs, providing critical data for modeling carbon fixation in C4sub> plants. Finally, I propose parallel experiments in Setaria viridis to explore its relevance as model C4sub> grass. Using a multifaceted approach, this proposal addresses important questions in basic biology, as well as the need for translation research in response to looming global food challenges.

  11. Investigations On Stoichiometry And Melting Behavior Of NaY(WO{sub 4}){sub 2}

    SciTech Connect

    Salunke, R. G.; Gosavi, S. W.; Singh, S. G.; Singh, A. K.; Desai, D. G.; Chauhan, A. K.; Gadkari, S. C.


    Differential thermal analysis (DTA) and X-ray diffraction (XRD) studies were carried out to understand the melting behavior of the NaY(WO{sub 4}){sub 2}, an important functional material used for the laser production. It has been observed that the stoichiometric NaY(WO{sub 4}){sub 2} composition forms a solution with another phase of the Na{sub 2}WO{sub 4}-Y{sub 2}(WO{sub 4}){sub 3} pseudo-binary system. This is found to be detrimental for the growth of single crystals of the material. Therefore, molar fraction in the starting charge was suitably altered to successfully restrict the formation of the undesired phase in the melt. A composition is suggested for the favorable crystal growth of this material.

  12. Integrated Data Collection Analysis (IDCA) Program - KClO4sub>/Aluminum Mixture

    SciTech Connect

    Sandstrom, Mary M.; Brown, Geoffrey W.; Preston, Daniel N.; Pollard, Colin J.; Warner, Kirstin F.; Sorensen, Daniel N.; Remmers, Daniel L.; Whinnery, LeRoy L.; Shelley, Timothy J.; Reyes, Jose A.; Hsu, Peter C.; Reynolds, John G.


    The Integrated Data Collection Analysis (IDCA) program is conducting a Proficiency Test for Small-Scale Safety and Thermal (SSST) testing of homemade explosives (HMEs). Described here are the results for impact, friction, electrostatic discharge, and differential scanning calorimetry analysis of a mixture of KClO4sub> and aluminum—KClO4sub>/Al mixture. This material was selected because of the challenge of performing SSST testing of a mixture of two solids. The mixture was found to be: 1) much less sensitive to impact than RDX, (LLNL being the exception) and PETN, 2) more sensitive to friction than RDX and PETN, and 3) extremely sensitive to spark. The thermal analysis showed little or no exothermic character. One prominent endothermic feature was observed in the temperature range studied and identified as a phase transition of KClO4sub>.

  13. Magnetic moment of the 4/sub 1//sup +/ state in /sup 20/Ne

    SciTech Connect

    Bright, T.; Ballon, D.; Saxena, R.J.; Niv, Y.; Benczer-Koller, a.N.


    The magnetic moment of the 4/sub 1//sup +/ state in /sup 20/Ne was measured by the transient field technique, and the transient field was calibrated in a simultaneous measurement on the 2/sub 1//sup +/ state. The resulting g(4/sub 1//sup +/) = 0.49 +- 0.34 is in agreement with the shell model description of /sup 20/Ne. The magnitude of the transient field measured in previous experiments on O, Ne, and Mg ions traversing iron foils was reexamined and appears to be in good agreement with the results of this experiment.

  14. Novel Solution Process for Fabricating Ultra-Thin-Film Absorber Layers in Fe2SiS4sub> and Fe2GeS4sub> Photovoltaics

    SciTech Connect

    Orefuwa, Samuel A.; Lai, Cheng-Yu; Dobson, Kevin D.; Ni, Chaoying; Radu, Daniela R.


    Fe2SiS4sub> and Fe2GeS4sub> crystalline materials posses direct bandgaps of ~1.55 and ~1.4 eV respectively and an absorption coefficient larger than 10^5 cm–1; their theoretical potential as solar photovoltaic absorbers has been demonstrated. However, no solar devices that employ either Fe2SiS4sub> or Fe2GeS4sub> have been reported to date. In the presented work, nanoprecursors to Fe2SiS4sub> and Fe2GeS4sub> have been fabricated and employed to build ultra-thin-film layers via spray coating and rod coating methods. Temperature-dependent X-Ray diffraction analyses of nanoprecursors coatings show an unprecedented low temperature for forming crystalline Fe2SiS4sub> and Fe2GeS4sub>. Fabricating of ultra-thin-film photovoltaic devices utilizing Fe2SiS4sub> and Fe2GeS4sub> as solar absorber material is presented.

  15. Negative thermal expansion in Th{sub 2}O(PO{sub 4}){sub 2}

    SciTech Connect

    Wallez, Gilles; Clavier, Nicolas; Dacheux, Nicolas


    Highlights: {yields} Dithorium oxide phosphate shows a continuous negative thermal expansion over a 600 {sup o}C range. {yields} Negative expansion arises from oxygen rocking and cations repulsions. {yields} Big and high-charge thorium IV appears ideal for generating negative expansion. -- Abstract: High temperature X ray diffraction performed on recently discovered orthorhombic Th{sub 2}O(PO{sub 4}){sub 2} shows a continuous linear thermal contraction (-1.6 x 10{sup -6} {sup o}C{sup -1}) in 20-600 {sup o}C range and a near-zero expansion at higher temperatures resulting from a dual structural deformation involving oxygen oscillations and inter-cations repulsions. Although similar mechanisms were observed in isotypic Zr{sub 2}O(PO{sub 4}){sub 2} (+1.5 x 10{sup -6} {sup o}C{sup -1}) and U{sub 2}O(PO{sub 4}){sub 2} (-1.4 x 10{sup -6} {sup o}C{sup -1}), those observed in Th{sub 2}O(PO{sub 4}){sub 2} are particularly intense because of the high ionic radius of tetravalent thorium.

  16. The superionic phase transitions in (NH{sub 4}){sub 3}H(SeO{sub 4}){sub 2} under hydrostatic pressure up to 400 MPa

    SciTech Connect

    Lindner, Ł.; Zdanowska-Frączek, M. Pawłowski, A.; Frączek, Z. J.


    The effect of hydrostatic pressure on proton conductivity of (NH{sub 4}){sub 3}H(SeO{sub 4}){sub 2} superionic crystal was studied in a wide temperature range and different isobaric conditions by means of impedance spectroscopy method. The measurements were performed along the trigonal c axis of the crystal, i.e., along the direction perpendicular to the plane in which, in the superionic phases, a dynamically disordered H-bond network is formed. The obtained pressure-temperature phase diagram is linear with increasing pressure. The triple point, which is the point of coexistence of the three phases: ferroelastic phase IV, ferroelastic phase III, and superionic phase II was found at p = 116.3 MPa and T = 287.3 K. High pressure leads to increase in the temperature range of stability of both superionic phases and to a drastic decrease in the temperature width of the ferroelastic phase III. With increasing pressure, the range of the superionic phase II expands at the expense of the range of the ferroelastic phase III, which is unstable and vanishes at the triple point.

  17. The crystal structure of Yb{sub 2}(SO{sub 4}){sub 3}.3H{sub 2}O and its decomposition product, {beta}-Yb{sub 2}(SO{sub 4}){sub 3}

    SciTech Connect

    Mills, Stuart J.; Petricek, Vaclav; Kampf, Anthony R.; Herbst-Imer, Regine; Raudsepp, Mati


    Yb{sub 2}(SO{sub 4}){sub 3}.3H{sub 2}O, synthesised by hydrothermal methods at 220(2) deg. C, has been investigated by single crystal X-ray diffraction. Yb{sub 2}(SO{sub 4}){sub 3}.3H{sub 2}O crystallises in space group Cmc2{sub 1} and is isostructural with Lu{sub 2}(SO{sub 4}){sub 3}.3H{sub 2}O. The crystal structure has been refined to R{sub 1}=0.0145 for 3412 reflections [F{sub o}>3{sigma}(F)], and 0.0150 for all 3472 reflections. The structure of Yb{sub 2}(SO{sub 4}){sub 3}.3H{sub 2}O is a complex framework of YbO{sub 6} octahedra, YbO{sub 8} and YbO{sub 5}(H{sub 2}O){sub 3} polyhedra and SO{sub 4} tetrahedra. Thermal data shows that Yb{sub 2}(SO{sub 4}){sub 3}.3H{sub 2}O decomposes between 120 and 190 deg. C to form {beta}-Yb{sub 2}(SO{sub 4}){sub 3}. The structure of a twinned crystal of {beta}-Yb{sub 2}(SO{sub 4}){sub 3} was solved and refined using an amplimode refinement in R3c with an R{sub 1}=0.0755 for 8944 reflections [F{sub o}>3{sigma}(F)], and 0.1483 for all 16,361 reflections. {beta}-Yb{sub 2}(SO{sub 4}){sub 3} has a unique structural topology based on a 3D network of pinwheels. - Graphical abstract: Octahedral-tetrahedral linkages found in Y{sub 2}(SO{sub 4}){sub 3} [and Er{sub 2}(SO{sub 4}){sub 3}] and ss-Yb{sub 2}(SO{sub 4}){sub 3}. Highlights: > The crystal structure and decomposition reactions of Yb{sub 2}(SO{sub 4}){sub 3}.3H{sub 2}O. > The crystal structure of a twinned crystal of {beta}-Yb{sub 2}(SO{sub 4}){sub 3}. > Comparison of the structures of {beta}-Yb{sub 2}(SO{sub 4}){sub 3} and Y{sub 2}(SO{sub 4}){sub 3}.

  18. Shape resonances in the photoionization of CF4sub>

    SciTech Connect

    Stephens, J. A.; Dill, Dan; Dehmer, Joseph L.


    Calculations of photoionization cross sections and photoelectron angular distributions have been performed for all occupied orbitals of CF4sub> using the multiple-scattering model. Results are compared with very recent experiments which employ synchrotron radiation to measure these quantities, namely the measurements of Truesdale e t a l. for the carbonK shell, and measurements of Carlson e t a l. and Novak e t a l. for the five outermost valence levels. The calculations predict intense shape resonances below 3 eV in continua of a1 and t2 final state symmetry. Qualitative agreement is attained on comparing much of the theory with experiment, notably the five outer valence levels, which serves to establish a one-electron picture of the photoionization dynamics of CF4sub>.

  19. Sub-nanosecond Yb:KLu(WO4sub>)2 microchip laser.


    Loiko, P; Serres, J M; Mateos, X; Yumashev, K; Yasukevich, A; Petrov, V; Griebner, U; Aguiló, M; Díaz, F


    A diode-pumped Yb:KLu(WO4sub>)2 microchip laser passively Q-switched by a Cr4+:YAG saturable absorber generated a maximum average output power of 590 mW at 1031 nm with a slope efficiency of 55%. The pulse characteristics were 690 ps/47.6 μJ at a pulse repetition frequency of 12.4 kHz. The output beam had an excellent circular profile with M2<1.05. Yb:KLu(WO4sub>)2 is very promising for ultrathin sub-ns microchip lasers. PMID:27244429

  20. Thermal decomposition behavior of the rare-earth ammonium sulfate R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4}

    SciTech Connect

    Nagai, Tsukasa; Tamura, Shinji; Imanaka, Nobuhito


    Rare-earth ammonium sulfate octahydrates of R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4}.8H{sub 2}O (R=Pr, Nd, Sm, and Eu) were synthesized by a wet process, and the stable temperature region for the anhydrous R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} form was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Detailed characterization of these double salts demonstrated that the thermal stability of anhydrous R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} is different between the Pr, Nd salts and the Sm, Eu salts, and the thermal decomposition behavior of these salts was quite different from the previous reports. - Graphical abstract: Stable temperature range of anhydrous rare-earth ammonium sulfate R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Since the previous reports were based only on thermal analysis, the present work has more accurately determined the exact thermal stability of rare-earth ammonium sulfate solids.

  1. Crystal Chemistry of Electrochemically and Chemically Lithiated Layered αI-LiVOPO4sub>

    SciTech Connect

    He, Guang; Bridges, Craig A.; Manthiram, Arumugam


    LiVOPO4sub> is an attractive cathode for lithium-ion batteries with a high operating voltage and the potential to achieve the reversible insertion of two lithium ions between VOPO4sub> and Li2VOPO4sub>. Among the three known forms of LiVOPO4sub> (α, β, and αI), the αI-LiVOPO4sub> has a layered structure that could promote better ionic mobility and reversibility than others. However, a comprehensive study of its lithiated product is not available as αI-LiVOPO4sub> is metastable and difficult to prepare by conventional approaches. We present here a facile synthesis of highly crystalline αI-LiVOPO4sub> and αI-LiVOPO4sub>/rGO nanocomposite by a microwave-assisted solvothermal method and its electrochemical/chemical lithiation. The LiVOPO4sub>/rGO cathodes exhibit a high reversible capacity of 225 mAh g–1, indicating the insertion of more than one lithium into VOPO4sub>. Both electrochemical and chemical lithiation imply a solid-solution reaction mechanism on inserting the second lithium into αI-LiVOPO4sub>, but a two-phase reaction feature could also occur under certain conditions such as insufficient time for equilibration of Li+ diffusion in the structure. The fully lithiated new αI-Li2VOPO4sub> phase was characterized by combined Rietveld refinement of neutron diffraction and X-ray diffraction data and by bond-valence sum maps. The results suggest that αI-Li2VOPO4sub> retains the tetragonal P4/nmm symmetry of the parent αI-LiVOPO4sub> structure, where the second lithium ions are located in the lithium layers rather than in the VOPO4sub> layers

  2. Integrated Data Collection Analysis (IDCA) Program - KClO4sub>/Carbon Mixture

    SciTech Connect

    Sandstrom, Mary M.; Brown, Geoffrey W.; Preston, Daniel N.; Pollard, Colin J.; Warner, Kirstin F.; Sorensen, Daniel N.; Remmers, Daniel L.; Shelley, Timothy J.; Reyes, Jose A.; Hsu, Peter C.; Reynolds, John G.


    The Integrated Data Collection Analysis (IDCA) program is conducting a proficiency study for Small- Scale Safety and Thermal (SSST) testing of homemade explosives (HMEs). Described here are the results for impact, friction, electrostatic discharge, and differential scanning calorimetry analysis of a mixture of KClO4sub> and activated carbon—KClO4sub>/C mixture. This material was selected because of the challenge of performing SSST testing of a mixture of two solids. The mixture was found to be insensitive to impact, friction, and thermal stimulus, and somewhat sensitive to spark discharge. This effort, funded by the Department of Homeland Security (DHS), ultimately will put the issues of safe handling of these materials in perspective with standard military explosives. The study is adding SSST testing results for a broad suite of different HMEs to the literature. Ultimately the study has the potential to suggest new guidelines and methods and possibly establish the SSST testing accuracies needed to develop safe handling practices for HMEs. Each participating testing laboratory uses identical test materials and preparation methods wherever possible. Note, however, the test procedures differ among the laboratories. The results are compared among the laboratories and then compared to historical data from various sources. The testing performers involved for the KClO4sub>/carbon mixture are Lawrence Livermore National Laboratory (LLNL), Los Alamos National Laboratory (LANL), Indian Head Division, Naval Surface Warfare Center, (NSWC IHD), and Air Force Research Laboratory (AFRL/RXQL). These tests are conducted as a proficiency study in order to establish some consistency in test protocols, procedures, and experiments and to understand how to compare results when these testing variables cannot be made consistent.

  3. Discovery of a metastable Al20Sm4sub> phase

    SciTech Connect

    Ye, Z.; Zhang, F.; Sun, Y.; Mendelev, M. I.; Ott, R. T.; Park, E.; Besser, M. F.; Kramer, M. J.; Ding, Z.; Wang, C. -Z.; Ho, K. -M.


    In this study, we present an efficient genetic algorithm, integrated with experimental diffraction data, to solve a nanoscale metastable Al20Sm4sub> phase that evolves during crystallization of an amorphous magnetron sputtered Al90Sm10 alloy. The excellent match between calculated and experimental X-ray diffraction patterns confirms an accurate description of this metastable phase. Molecular dynamic simulations of crystal growth from the liquid phase predict the formation of disordered defects in the devitrified crystal.

  4. SU(4){sub L}xU(1){sub X} models with little Higgs mechanism

    SciTech Connect

    Nam, Soo-hyeon; Lee, Kang Young; Keum, Yong-Yeon


    We study the aspects of the fermion and gauge boson sectors in SU(4){sub L}xU(1){sub X} models with a little Higgs mechanism. We introduce a new setup of fermions, which ensures the cancellation of gauge anomaly and the cancellation of one-loop quadratic divergence to the Higgs mass for all fermion multiplets and gauge bosons. We explicitly present the interactions between the standard model fermions and the heavy gauge bosons to discuss the phenomenological implications of extra Z{sup '} and Z{sup ''} gauge bosons based on recent experimental data.

  5. Integrated Data Collection Analysis (IDCA) program--KClO4sub>/Dodecane Mixture

    SciTech Connect

    Sandstrom, Mary M.; Brown, Geoffrey W.; Preston, Daniel N.; Pollard, Colin J.; Warner, Kirstin F.; Sorensen, Daniel N.; Remmers, Daniel L.; Shelley, Timothy J.; Reyes, Jose A.; Hsu, Peter C.; Reynolds, John G.


    The Integrated Data Collection Analysis (IDCA) program is conducting a proficiency study for Small- Scale Safety and Thermal (SSST) testing of homemade explosives (HMEs). Described here are the results for impact, friction, electrostatic discharge, and differential scanning calorimetry analysis of a mixture of KClO4sub> and dodecane—KClO4sub>/dodecane mixture. This material was selected because of the challenge of performing SSST testing of a mixture of solid and liquid materials. The mixture was found to: 1) be less sensitive to impact than RDX, and PETN, 2) less sensitive to friction than RDX and PETN, and 3) less sensitive to spark than RDX and PETN. The thermal analysis showed little or no exothermic features suggesting that the dodecane volatilized at low temperatures. A prominent endothermic feature was observed and assigned to a phase transition of KClO4sub>. This effort, funded by the Department of Homeland Security (DHS), ultimately will put the issues of safe handling of these materials in perspective with standard military explosives. The study is adding SSST testing results for a broad suite of different HMEs to the literature. Ultimately the study has the potential to suggest new guidelines and methods and possibly establish the SSST testing accuracies needed to develop safe handling practices for HMEs. Each participating testing laboratory uses identical test materials and preparation methods wherever possible. Note, however, the test procedures differ among the laboratories. The results are compared among the laboratories and then compared to historical data from various sources. The testing performers involved for the KClO4sub>/dodecane mixture are Lawrence Livermore National Laboratory (LLNL), Los Alamos National Laboratory (LANL), Indian Head Division, Naval Surface Warfare Center, (NSWC IHD), and Air Force Research Laboratory (AFRL/RXQL). These tests are conducted as a proficiency study in order to establish some

  6. Neutrino masses in SU(4){sub L}⊗U(1){sub X} gauge models

    SciTech Connect

    Palcu, Adrian


    Neutrino masses are obtained within SU(4){sub L}⊗U(1){sub X} electroweak gauge models with spontaneous symmetry breaking by simply exploiting the tree level realization of certain dimension-five effective operators. The scalar sector needs not to be enlarged, since these operators are constructed as direct products among scalar multiplets already existing in the model. There is a unique generic matrix for Yukawa couplings in the neutrino sector, while the charged leptons are already in their diagonal basis. The experimentally observed phenomenology in the neutrino sector is obtained as a natural consequence of this particular approach.

  7. A dispersive treatment of Kl4sub> decays

    SciTech Connect

    Colangelo, Gilberto; Passemar, Emilie; Stoffer, Peter


    Kl4sub> decays offer several reasons of interest: they allow an accurate measurement of ππ-scattering lengths; they provide the best source for the determination of some low-energy constants of xPT; one form factor is directly related to the chiral anomaly, which can be measured here. We present a dispersive treatment of Kl4sub> decays that provides a resummation of ππ- and Kπ-rescattering effects. In addition, the free parameters of the dispersion relation are fitted to the data of the high-statistics experiments E865 and NA48/2. The matching toxPT at NLO and NNLO enables us to determine the LECs Lr1, Lr2 and Lr3. With recently published data from NA48/2, the LEC Lr9 can be determined as well. In contrast to a pure chiral treatment, the dispersion relation describes the observed curvature of one of the form factors, which we understand as a rescattering effect beyond NNLO.

  8. Synthesis, structure, and optical properties of CsU{sub 2}(PO{sub 4}){sub 3}

    SciTech Connect

    Oh, George N.; Ringe, Emilie; Van Duyne, Richard P.; Ibers, James A.


    CsU{sub 2}(PO{sub 4}){sub 3} was synthesized in highest yield by the reaction in a fused-silica tube of U, P, and Se in a CsCl flux at 1273 K. It crystallizes with four formula units in space group P2{sub 1}/n of the monoclinic system in a new structure type. The structure of CsU{sub 2}(PO{sub 4}){sub 3} is composed of U and Cs atoms coordinated by PO{sub 4}{sup 3-} units in distorted octahedral arrangements. Each U atom corner shares with six PO{sub 4}{sup 3-} units. Each Cs atom face shares with one, edge shares with two, and corner shares with three PO{sub 4}{sup 3-} units. The structure shares some features with the sodium zirconium phosphate structure type. X-ray powder diffraction results demonstrate that the present CsU{sub 2}(PO{sub 4}){sub 3} compound crystallizes in a structure different from the previously reported {beta} Prime - and {gamma}-CsU{sub 2}(PO{sub 4}){sub 3} compounds. CsU{sub 2}(PO{sub 4}){sub 3} is highly pleochroic, as demonstrated by single-crystal optical absorption measurements. - Graphical abstract: Stacking of the layers in CsU{sub 2}(PO{sub 4}){sub 3}, viewed along [100]. Highlights: Black-Right-Pointing-Pointer Compound CsU{sub 2}(PO{sub 4}){sub 3} crystallizes in a new structure type. Black-Right-Pointing-Pointer Structure shares some features with the sodium zirconium phosphate structure type. Black-Right-Pointing-Pointer CsU{sub 2}(PO{sub 4}){sub 3} is highly pleochroic, as demonstrated by single-crystal optical absorption measurements.

  9. Magnetic properties of the superconducting polymers (SN)/sub x/ and (SNBr/sub 0. 4/)/sub x/

    SciTech Connect

    Dee, R.H.; Carolan, J.F.; Turrell, B.G.; Greene, R.L.


    The magnetizations of the superconducting sulfur nitrogen polymer (SN)/sub x/ and its brominated modification, (SNBr/sub 0.4/)/sub x/, have been studied as a function of magnetic field and temperature. There is anisotropy in the magnetization observed in both materials. However, (SNBr/sub 0.4/)/sub x/ behaves more like a bulk superconductor than (SN)/sub x/ does, indicating stronger interfiber coupling in the former.

  10. Heat capacity and neutron diffraction studies on the frustrated magnetic Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1] solid solution

    SciTech Connect

    Pedro, I. de; Rojo, J.M.; Rodriguez Fernandez, J.; Sanchez Marcos, J.; Fernandez-Diaz, M.T.; Rojo, T.


    The Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1] solid solution exhibits a complex magnetic behaviour due to the bond-frustration in its magnetic structure. Heat capacity measurements of the (x=0.1-0.5) phases show a three-dimensional magnetic ordering ({lambda} anomaly) that shifts to lower temperatures and becomes broader as the AsO{sub 4}{sup 3-} content increases. For x=0.75, no significant feature was observed whereas for higher arsenate ion content, x=0.9 and 1, a small maximum was detected. The magnetic structures of solid solution are consistent with the existence of predominant antiferromagnetic superexchange interactions through the |OH| and |XO{sub 4}| (X=P and As) groups between the Co{sup +2} ions. The substitution of PO{sub 4}{sup 3-} by AsO{sub 4}{sup 3-} anions by more than 90% substantially modifies the magnetic exchange pathways in the solid solution, leading to an incommensurate antiferromagnetic structure in Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [x=0.9 and 1] phases. - Graphical abstract: Magnetic structures of Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1]. The ordering of the magnetic moments of Co{sup 2+} is in c direction for the two crystallographic positions (dimers and chains) in all compounds. The unit cell is surrounded by a red line. Highlights: Black-Right-Pointing-Pointer Synthesis of a new adamite-type compounds, Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} (0.1, 0.25, 0.5, 0.75, 0.9) phases. Black-Right-Pointing-Pointer Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} (0-1) solid solution; magnetic frustrated system. Black-Right-Pointing-Pointer High resolution neutron powder diffraction to determine the crystal structures. Black-Right-Pointing-Pointer Incommensurate magnetic structures at low temperature. Black-Right-Pointing-Pointer Magnetostructural correlations in cobalt-based Co{sub 2}(OH)XO{sub 4} (X=P and As) insulation compounds.

  11. Pressure-induced phase transitions in multiferroic RbFe(MoO{sub 4}){sub 2}-Raman scattering study

    SciTech Connect

    Maczka, M.; Ptak, M.; Luz-Lima, C.; Freire, P.T.C.; Paraguassu, W.; Guerini, S.; Hanuza, J.


    High pressure Raman scattering experiments were performed on RbFe(MoO{sub 4}){sub 2}. These experiments revealed that two phase transitions take place in RbFe(MoO{sub 4}){sub 2} at very low pressures, i.e. between ambient pressure and 0.2 GPa and between 0.4 and 0.7 GPa. Raman results showed that at the first phase transition the room temperature P3-bar m1 phase transforms into the P3-bar phase, which is also observed at ambient pressure below 190 K. The second pressure-induced phase transition occurs into a low symmetry phase of unknown symmetry. The performed lattice dynamics calculations for the P3-bar m1 phase and ab initio calculation of the structural changes under hydrostatic pressure helped us to get better insights into the mechanism of the observed phase transitions. - Graphical abstract: Raman spectra of RbFe(MoO{sub 4}){sub 2} crystal in the high wavenumber region recorded at different pressures during compression experiment. Highlights: > RbFe(MoO{sub 4}){sub 2} exhibits two pressure-induced phase transitions below 0.7 GPa. > First phase transition is from the P3-bar m1 into P3-bar structure. > Phase transitions in RbFe(MoO{sub 4}){sub 2} are similar as in KFe(MoO{sub 4}){sub 2}. > Transitions' pressures are much lower for the rubidium compound.

  12. Second harmonic generation of diamond-blade diced KTiOPO4sub> ridge waveguides.


    Chen, Chen; Rüter, Christian E; Volk, Martin F; Chen, Cheng; Shang, Zhen; Lu, Qingming; Akhmadaliev, Shavkat; Zhou, Shengqiang; Chen, Feng; Kip, Detlef


    We report on the fabrication of ridge waveguides in KTiOPO4sub> nonlinear optical crystals through carbon ion irradiation followed by precise diamond blade dicing. The diced side-walls have low roughness, which allows for low propagation loss of ~1dB/cm in fabricated of ridges. The waveguide property investigation has been performed at 1064 nm as well as 532 nm, showing good guidance at both TE and TM polarizations. Based on type II phase matching configuration, efficient second harmonic generation of green light at room temperature has been realized. High conversion efficiencies of ~1.12%W-1 and ~12.4% have been obtained for frequency doubling under the pump of continuous-wave (CW) and pulsed fundamental waves at 1064 nm, respectively. PMID:27464095

  13. Preparation and crystal structure of Na sub 3 SbO(PO sub 4 ) sub 2

    SciTech Connect

    Guyomard, D.; Pagnoux, C.; Verbaere, A.; Piffard, Y. ); Zah Letho, J.J. )


    The single phase compound Na{sub 3}SbO(PO{sub 4}){sub 2} was prepared by a solid state reaction. It crystallizes in the orthorhombic system, space group P2{sub 1}2{sub 1}2{sub 1} with a = 6.964(1) {angstrom}, b = 9.284(2) {angstrom}, c = 12.425(2) {angstrom}, Z = 4. The structure was determined from 968 reflections collected on a Nonius CAD4 automatic diffractometer with MoK{alpha} radiation. The final R index and weighted R{sub w} index are 0.031 and 0.039, respectively. The structure is built up from strings of corner-sharing SbO{sub 6} octahedra to which phosphate groups are linked by two of their vertices. These chains, running parallel to the a-axis, are separated from each other by sodium atoms.

  14. Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO4sub>

    SciTech Connect

    Toft-Petersen, Rasmus; Reehuis, Manfred; Jensen, Thomas B. S.; Andersen, Niels H.; Li, Jiying; Le, Manh Duc; Laver, Mark; Niedermayer, Christof; Klemke, Bastian; Lefmann, Kim; Vaknin, David


    We report significant details of the magnetic structure and spin dynamics of LiFePO4sub> obtained by single-crystal neutron scattering. Our results confirm a previously reported collinear rotation of the spins away from the principal b axis, and they determine that the rotation is toward the a axis. In addition, we find a significant spin-canting component along c. Furthermore, the possible causes of these components are discussed, and their significance for the magnetoelectric effect is analyzed. Inelastic neutron scattering along the three principal directions reveals a highly anisotropic hard plane consistent with earlier susceptibility measurements. While using a spin Hamiltonian, we show that the spin dimensionality is intermediate between XY- and Ising-like, with an easy b axis and a hard c axis. As a result, it is shown that both next-nearest neighbor exchange couplings in the bc plane are in competition with the strongest nearest neighbor coupling.

  15. Predicted energies and structures of {beta}-Ca{sub 3}(PO{sub 4}){sub 2}

    SciTech Connect

    Jay, E.E.; Michie, E.M.; Parfitt, D.; Rushton, M.J.D.; Fong, S.K.; Mallinson, P.M.; Metcalfe, B.L.; Grimes, R.W.


    One of the 6a cation sites of the {beta}-Ca{sub 3}(PO{sub 4}){sub 2} structure has previously been described as half occupied. Here, classical static lattice techniques are used to model the different configurations that the Ca ions can exhibit over these Ca(4) 6a sites. All possible configurations in the single primitive unit cell and a hexagonal supercell 3{sub h}x1x1 have been generated, along with configurationally averaged structures, that exhibit the experimentally reported R 3c symmetry. The lowest energy configuration of the primitive cell exhibits R 3 symmetry. Conversely, the lowest energy configurations derived from the hexagonal supercell, which are considerably more stable, exhibit P 3{sub 1} and P 3{sub 2} symmetries, which are isomorphic supergroups of R 3c. The implication of these simulations are discussed in terms of refined structural models of the material. - Graphical Abstract: One of the 6a cation sites of the {beta}-Ca{sub 3}(PO{sub 4}){sub 2} structure has previously been described as half occupied. Here, classical static lattice techniques are used to model the different configurations that the Ca ions can exhibit over these Ca(4) 6a sites. All possible configurations in the single primitive unit cell and a hexagonal supercell (3{sub h}x1x1) have been generated, along with configurationally averaged structures, that exhibits experimentally reported R 3c symmetry. The lowest energy configuration of the primitive cell exhibits R 3 symmetry. Conversely, the lowest energy configurations derived from the hexagonal supercell cell, which are considerably more stable, exhibit P 3{sub 1} and P 3{sub 2} symmetries, which are isomorphic supergroups of R 3c. The implication of these simulations are discussed in terms of refined structural models of the material.

  16. Luminescence properties of phosphate phosphor Ba{sub 3}Y(PO{sub 4}){sub 3}:Sm{sup 3+}

    SciTech Connect

    Yang, Fu; Liu, Yufeng; Tian, Xiaodong; Dong, Guoyi; Yu, Quanmao


    A series of reddish orange-emitting phosphate phosphors Ba{sub 3}Y{sub 1−x}(PO{sub 4}){sub 3}:xSm{sup 3+}(0.01≤x≤0.20) were synthesized by solid-state reaction. X-ray diffraction and photoluminescence spectra were utilized to characterize the structure and luminescence properties of as-synthesized phosphors. The optimized phosphors Ba{sub 3}Y{sub 0.95}(PO{sub 4}){sub 3}:0.05Sm{sup 3+} present several excitation bands from 300 to 500 nm, and exhibit intense reddish orange-emitting properties. The energy transfer type between Sm{sup 3+} ions was confirmed as d–d interaction by using Van Uitert model. The chromatic properties of the typical sample Ba{sub 3}Y(PO{sub 4}){sub 3}:0.05Sm{sup 3+} phosphor have been found to have chromaticity coordinates of (0.583, 0.405), which are located in reddish orange region under the excitation of 401 nm. These results indicated that Ba{sub 3}Y(PO{sub 4}){sub 3}:Sm{sup 3+} phosphors have potential applications in the field of lighting and display due to their effective excitation in the near-ultraviolet range. - Graphical abstract: The color coordinates for 5 mol% Sm{sup 3+} doped Ba{sub 3}Y(PO{sub 4}){sub 3} phosphor were calculated to be (0.583, 0.405), which are located in reddish orange region under the excitation of 401 nm. The peaks of Ba{sub 3}Y{sub 0.95}(PO{sub 4}){sub 3}:0.05Sm{sup 3+} phosphor with the highest emission intensity at 600 nm are broader than those of Y{sub 2}O{sub 3}:Eu{sup 3+} and Y{sub 2}O{sub 2}S:Eu{sup 3+} phosphors. All these characteristics suggest that Ba{sub 3}Y(PO{sub 4}){sub 3}:Sm{sup 3+} phosphors are suitable for near-UV (370–410 nm) excitation and can be applicable to near UV-based WLEDs. ▪ - Highlights: • Different concentration Sm{sup 3+}-doped Ba{sub 3}Y(PO{sub 4}){sub 3} phosphors were fabricated by solid state method. • The optimized phosphors present the several excitation bands from 300 to 500 nm. • The Ba{sub 3}Y(PO{sub 4}){sub 3}:Sm{sup 3+} shows bright reddish orange

  17. New insight in the structure-luminescence relationships of Ca{sub 9}Eu(PO{sub 4}){sub 7}

    SciTech Connect

    Benhamou, Rajia Ait; Bessiere, Aurelie; Wallez, Gilles; Viana, Bruno; Elaatmani, Mohamed; Daoud, Mohamed; Zegzouti, Abdelwahed


    The double phosphate Ca{sub 9}Eu(PO{sub 4}){sub 7}, obtained by solid state reaction, was found to be isotypic with Ca{sub 3}(PO{sub 4}){sub 2}, with space group R3c and unit cell parameters a=10.4546(1) A, c=37.4050(3) A, V=3540.67(9) A{sup 3}, Z=6. The structure parameters refined using the Rietveld method showed that europium shares positions M1, M2 and M3 with calcium, contradicting previously published Moessbauer results. Low temperature luminescence under selective excitation of Eu{sup 3+} in Ca{sub 9}Y{sub 1-x}Eu{sub x}(PO{sub 4}){sub 7} and in Ca{sub 9}Eu(PO{sub 4}){sub 7} samples was studied, confirming the Eu{sup 3+} distribution into these sites. At 10 K, {sup 5}D{sub 0}->{sup 7}F{sub 0} emission lines of Eu{sup 3+} were observed at 578.5, 579.5, 580.1 nm for the M3, M1 and M2 sites, respectively. High temperature X-ray powder diffraction evidenced a second-order phase transition around 573 deg. C. - Graphical Abstract: Emission spectra of Ca{sub 9}Eu(PO{sub 4}){sub 7} recorded at 10 K evidencing the three different sites for Eu{sup 3+} dopant cation.

  18. Insights into the structure of mixed CO2/CH4sub> in gas hydrates

    SciTech Connect

    Everett, S. Michelle; Rawn, Claudia J.; Chakoumakos, Bryan C.; Keffer, David J.; Huq, Ashfia; Phelps, Tommy J.


    The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH4sub> for energy production while simultaneously sequestering CO2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH4sub>)1-x(CO2)x·5.75H2O provides a model system to study how the distinct bonding and shapes of CH4sub> and CO2 influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO2/CH4sub> gas hydrates. CO2-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO2 molecule interacting with H2O molecules that form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH4sub>/CO2 gas hydrate.

  19. Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of Snl4sub>

    SciTech Connect

    Liu, Hanyu; Tse, John S.; Hu, Michael Y.; Bi, Wenli; Zhao, Jiyong; Alp, E. Ercan; Pasternak, Moshe; Taylor, R. Dean; Lashley, Jason C.


    The pressure-induced amorphization and subsequent recrystallization of SnI4sub> have been investigated using first principles molecular dynamics calculations together with high-pressure 119Sn nuclear resonant inelastic x-ray scattering measurements. Above ~8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ~64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI4sub> under ambient conditions. Although high pressure structures of SnI4sub> were thought to be determined by random packing of equal-sized spheres, we detected electron charge transfer in each phase. As a result, this charge transfer results in a crystal structure packing determined by larger than expected iodine atoms. (C) 2015 AIP Publishing LLC.

  20. Crystal structure of the high-temperature modification of ytterbium perrhenate Yb(ReO{sub 4}){sub 3}

    SciTech Connect

    Khrustalev, V.N.; Varfolomeev, M.B.; Shamrai, N.B.; Struchkov, Yu.T.; Pisarevskii, A.P. |


    Yb(ReO{sub 4}){sub 3} obtained by the slow crystallization of its melt in air is investigated by X-ray diffraction (298 K, 329 reflections, R = 0.083, R{sub w} = 0.102). Crystals are hexagonal, a = 9.999(4) {angstrom}, c = 6.070(2) {angstrom}, Z = 2, space group P6{sub 3}/m. The structure is related to the CdTh(MoO{sub 4}){sub 3} type and consists of columns of Yb polyhedra (three-cap trigonal prisms) and of Re tetrahedra. The correlation of the structures of Yb(ReO{sub 4}){sub 3} and apatite is discussed.

  1. Spin Hall magnetoresistance in CoFe2O4sub>/Pt films

    SciTech Connect

    Wu, Hao; Qintong, Zhang; Caihua, Wan; Ali, Syed Shahbaz; Yuan, Zhonghui; You, Lu; Wang, Junling; Choi, Yongseong; Han, Xiufeng


    Pulse laser deposition and magnetron sputtering techniques have been employed to prepare MgO(001)//CoFe2O4sub>/Pt samples. Cross section transmission electron microscope results prove that the CoFe2O4sub> film epitaxially grew along (001) direction. X-ray magnetic circular dichroism results show that magnetic proximity effect in this sample is negligible. Magnetoresistance (MR) properties confirm that spin Hall MR (SMR) dominates in this system. Spin Hall effect-induced anomalous Hall voltage was also observed in this sample. Lastly, these results not only demonstrate the universality of SMR effect but also demonstrate the utility in spintronics of CoFe2O4sub> as a new type of magnetic insulator.

  2. Biodiesel production using lipase immobilized on epoxychloropropane-modified Fe3O4 sub-microspheres.


    Zhang, Qian; Zheng, Zhong; Liu, Changxia; Liu, Chunqiao; Tan, Tianwei


    Superparamagnetic Fe3O4 sub-microspheres with diameters of approximately 200 nm were prepared via a solvothermal method, and then modified with epoxychloropropane. Lipase was immobilized on the modified sub-microspheres. The immobilized lipase was used in the production of biodiesel fatty acid methyl esters (FAMEs) from acidified waste cooking oil (AWCO). The effects of the reaction conditions on the biodiesel yield were investigated using a combination of response surface methodology and three-level/three-factor Box-Behnken design (BBD). The optimum synthetic conditions, which were identified using Ridge max analysis, were as follows: immobilized lipase:AWCO mass ratio 0.02:1, fatty acid:methanol molar ratio 1:1.10, hexane:AWCO ratio 1.33:1 (mL/g), and temperature 40 °C. A 97.11% yield was obtained under these conditions. The BBD and experimental data showed that the immobilized lipase could generate biodiesel over a wide temperature range, from 0 to 40 °C. Consistently high FAME yields, in excess of 80%, were obtained when the immobilized lipase was reused in six replicate trials at 10 and 20 °C. PMID:26803008

  3. A high performance hybrid battery based on aluminum anode and LiFePO4sub> cathode

    SciTech Connect

    Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Bridges, Craig A.; Paranthaman, Mariappan Parans; Dai, Sheng; Brown, Gilbert M.


    A unique battery hybrid utilizes an aluminum anode, a LiFePO4sub> cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl4sub> is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g-1 at a current rate of C/5. It also shows good rate capability and cycling performance.

  4. Theoretical Study of the Molecular and Electronic Structures of TiO4sub>H4sub>, Ti2O7H6, and Ti2O6H4sub>

    SciTech Connect

    Tsuchiya, Takashi; Whitten, Jerry L.


    State-of-the-art multistate configuration interaction (CI) calculations were performed for a series of titanium complexes, namely, TiO4sub>H4sub>, Ti2O7H6, and Ti2O6H4sub>, which were chosen to identify features present in titanium oxide nanoclusters and titanium dioxide surfaces. All electrons were included in the calculations, and transformation methods were employed to achieve high accuracy for the excitations of interest. The electronic structures of the ground and excited states are discussed, and excitation energies are reported for different molecular conformations. Of particular interest is the extent of localization of the electron-hole pair formed upon excitation from the oxygen 2p molecular orbitals. Singlet and triplet excited states were resolved, and energies of electronic states are reported as a function of molecular geometry.

  5. Solvothermal indium fluoride chemistry: Syntheses and crystal structures of K{sub 5}In{sub 3}F{sub 14}, beta-(NH{sub 4}){sub 3}InF{sub 6} and [NH{sub 4}]{sub 3}[C{sub 6}H{sub 21}N{sub 4}]{sub 2}[In{sub 4}F{sub 21}

    SciTech Connect

    Jayasundera, Anil C.A.; Goff, Richard J.; Li Yang; Finch, Adrian A.; Lightfoot, Philip


    The solvothermal syntheses and crystal structures of three indium fluorides are presented. K{sub 5}In{sub 3}F{sub 14} (1) and beta-(NH{sub 4}){sub 3}InF{sub 6} (2) are variants on known inorganic structure types chiolite and cryolite, respectively, with the latter exhibiting a complex and apparently novel structural distortion. [NH{sub 4}]{sub 3}[C{sub 6}H{sub 21}N{sub 4}]{sub 2}[In{sub 4}F{sub 21}] (3) represents a new hybrid composition displaying a unique trimeric metal fluoride building unit. - Graphical abstract: Solvothermal synthesis has been used to prepare three indium fluorides, including a novel hybrid material containing a unique [In{sub 3}F{sub 15}] trimer templated by tren.

  6. Structural and conductivity studies of CsK(SO{sub 4}){sub 0.32}(SeO{sub 4}){sub 0.68}Te(OH){sub 6}

    SciTech Connect

    Djemel, M.; Abdelhedi, M.; Dammak, M.; Kolsi, A.W.


    The compound CsK(SO{sub 4}){sub 0.32}(SeO{sub 4}){sub 0.68}Te(OH){sub 6} crystallizes in the monoclinic P2{sub 1}/n space group. It was analyzed, at room temperature, using X-ray diffractometer data. The main feature of these atomic arrangements is the coexistence of three and different anions (SO{sub 4}{sup 2-}, SeO{sub 4}{sup 2-} and TeO{sub 6}{sup 6-}groups) in the unit cell, connected by hydrogen bonds which make the building of the crystal. The thermal analysis of the title compound shows three distinct endothermal peaks at 435, 460 and 475 K. Complex impedance measurements are performed on this material as a function of both temperature and frequency. The electric conduction has been studied. The temperature dependence on the conductivity indicates that the sample became an ionic conductor at high temperature. - Graphical abstract: Projection of crystal structure CsK(SO{sub 4}){sub 0.32}(SeO{sub 4}){sub 0.68}Te(OH){sub 6} on the ab plane. Highlights: Black-Right-Pointing-Pointer We have studied the results of the crystal structure of the new mixed compound. Black-Right-Pointing-Pointer We have characterized the phase transition observed in DSC curve. Black-Right-Pointing-Pointer The protonic conduction in our material is probably due to a hopping mechanism.

  7. Electron paramagnetic resonance spectra and structures of Cu(C sub 2 H sub 4 ), Cu(C sub 2 H sub 4 ) sub 2 , and Cu(C sub 2 H sub 4 ) sub 3 in hydrocarbon matrices

    SciTech Connect

    Howard, J.A.; Joly, H.A.; Mile, B. )


    Two mononuclear {pi}-complexes, Cu(C{sub 2}H{sub 4}) and Cu(C{sub 2}H{sub 4}){sub 2}, have been positively identified by EPR spectroscopy from reaction of Cu atoms and ethylene at 77 K in inert hydrocarbon matrices on a rotating cryostat. The spectra of these copper(O) complexes are consistent with dative bonding for both species and with a C{sub 2v} structure for Cu(C{sub 2}H{sub 4}) and a D{sub 2h} structure for Cu(C{sub 2}H{sub 4}){sub 2}. Spectra of Cu({sup 13}CH{sub 2}CH{sub 2}) and Cu({sup 13}CH{sub 2}CH{sub 2}){sub 2} are consistent with these assignments. A third complex is formed in both adamantane and cyclohexane that could be Cu(C{sub 2}H{sub 4}){sub 2} with a structure other than D{sub 2h} but is more likely to be the mononuclear trisligand complex Cu(C{sub 2}H{sub 4}){sub 3} with a D{sub 3h} structure. In the absence of a well-resolved isotropic spectrum of Cu({sup 13}CH{sub 2}CH{sub 2}){sub 3}, this assignment must however be taken as tentative.

  8. A new three-dimensional cobalt phosphate: Co{sub 5}(OH{sub 2}){sub 4}(HPO{sub 4}){sub 2}(PO{sub 4}){sub 2}

    SciTech Connect

    Han Zhangang . E-mail:; Tian Aixiang; Peng Jun . E-mail:; Zhai Xueliang


    A three-dimensional (3D) cobalt phosphate: Co{sub 5}(OH{sub 2})PO{sub 4}){sub 2}(PO{sub 4}){sub 2} (1), has been synthesized by hydrothermal reaction and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic techniques. The title compound is a template free cobalt phosphate. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO{sub 6} and PO{sub 4} polyhedra. The magnetic susceptibility measurements indicated that the title compound obeys Curie-Weiss behavior down to a temperature of 17 K at which an antiferromagnetic phase transition occurs. - Graphical abstract: A 3D cobalt phosphate with a neutral framework: Co{sub 5}(OH{sub 2}){sub 4}(HPO{sub 4}){sub 2}(PO{sub 4}){sub 2} (1), has been synthesized and characterized. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO{sub 6} and PO{sub 4} polyhedra. Its magnetic property was researched.

  9. A facile solvothermal synthesis of octahedral Fe3O4sub> nanoparticles

    SciTech Connect

    DuChene, Joseph S.; Qiu, Jingjing; Graham, Jeremy O.; Engelhard, Mark H.; Cao, Guixin; Gai, Zheng; Wei, Wei David; Ooi, Frances


    Anisotropic Fe3O4sub> octahedrons are obtained via a simple solvothermal synthesis with appropriate sizes for various technological applications. Here, a complete suite of materials characterization methods confirms the magnetite phase for these structures, which exhibit substantial saturation magnetization and intriguing morphologies for a wide range of applications.

  10. New mixed-valence chromium structure type: NH{sub 4}Cr(CrO{sub 4}){sub 2}

    SciTech Connect

    Casari, Barbara M. . E-mail:; Wingstrand, Erica; Langer, Vratislav


    Synthesis and crystal structure of a new structure type of mixed Cr(III)/Cr(VI) chromates is reported. NH{sub 4}Cr(CrO{sub 4}){sub 2} was prepared from CrO{sub 3} in the presence of (NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 6}. Since this is the first preparation of mixed valence ternary chromium oxides from aqueous solution, a reaction pathway for this synthesis is suggested. The crystal structure of NH{sub 4}Cr(CrO{sub 4}){sub 2} has been determined from three-dimensional X-ray data collected at low temperature, 173K. The structure belongs to the orthorhombic space group Pnma, with a=14.5206(10), b=5.4826(4), c=8.7041(7)A and Z=4. The title compound consists of corner-sharing chromium(III) octahedra and chromium(VI) tetrahedra forming a three-dimensional network with the composition [Cr(CrO{sub 4}){sub 2}]{sub n}{sup n-}, containing channels in which zigzag rows of ammonium ions balance the net charge.


    SciTech Connect

    McCauley, Patrick I.; Mangum, Jeffrey G.; Wootten, Alwyn


    We present Green Bank Telescope observations of the 3{sub 12}-3{sub 13} (29 GHz) and 4{sub 13}-4{sub 14} (48 GHz) transitions of the H{sub 2}CO molecule toward a sample of 23 well-studied star-forming regions. Analysis of the relative intensities of these transitions can be used to reliably measure the densities of molecular cores. Adopting kinetic temperatures from the literature, we have employed a large velocity gradient (LVG) model to derive the average hydrogen number density (n(H{sub 2})) within a 16'' beam toward each source. Densities in the range of 10{sup 5.5}-10{sup 6.5} cm{sup -3} and ortho-formaldehyde column densities per unit line width between 10{sup 13.5} and 10{sup 14.5} cm{sup -2} (km s{sup -1}){sup -1} are found for most objects, in general agreement with existing measurements. A detailed analysis of the advantages and limitations to this densitometry technique is also presented. We find that H{sub 2}CO 3{sub 12}-3{sub 13}/4{sub 13}-4{sub 14} densitometry proves to be best suited to objects with T{sub K} {approx}> 100 K, above which the H{sub 2}CO LVG models become relatively independent of kinetic temperature. This study represents the first detection of these H{sub 2}CO K-doublet transitions in all but one object in our sample. The ease with which these transitions were detected, coupled with their unique sensitivity to spatial density, makes them excellent monitors of density in molecular clouds for future experiments. We also report the detection of the 9{sub 2}-8{sub 1} A {sup -} (29 GHz) transition of CH{sub 3}OH toward six sources.

  12. Synthesis and conductivities of sulfate/selenate phases related to nasicon: Na[sub x]M[prime](III)[sub 2[minus]x](SO[sub 4])[sub 3[minus]y](SeO[sub 4])[sub y

    SciTech Connect

    Slater, P.R.; Greaves, C. )


    The synthesis of Na containing Nasicon-type phases of the form Na[sub x]M[prime](II)[sub x]M[double prime](III)[sub 2[minus]x](SO[sub 4])[sub 3[minus]y](SeO[sub 4])[sub y] (M[prime] = Mg, Zn, Cd, Mn; M[double prime] = Al, Cr, Fe, In, Yb; 0 [le] x [le] 1.75; 0 [le] y [le] 3) is reported. The conductivities of a range of samples have been measured, with the highest value observed at 200[degrees]C being 2 x 10[sup [minus]4] [Omega][sup [minus]1] cm[sup [minus]1] for Na[sub 1.75]Mg[sub 1.75]Cr[sub 0.25](SO[sub 4])[sub 3]. The range of x for which single phase samples are observed depends on the nature of M[prime] and M[double prime], and on the value of y. Attempts to increase the Na content, and so increase the conductivity, by partially substituting the (S, Se)O[sub 4] groups by PO[sub 4] or SiO[sub 4] have proven unsuccessful.

  13. Magnetic structure of the antiferromagnetic Kondo lattice compounds CeRhAl4sub>Si2 and CeIrAl4sub>Si2

    SciTech Connect

    Ghimire, N. J.; Calder, S.; Janoschek, M.; Bauer, E. D.


    In this article, we have investigated the magnetic ground state of the antiferromagnetic Kondo-lattice compounds CeMAl4sub>Si2(M = Rh, Ir) using neutron powder diffraction. Although both of these compounds show two magnetic transitions TN1 and TN2 in the bulk properties measurements, evidence for magnetic long-range order was only found below the lower transition TN2. Analysis of the diffraction profiles reveals a commensurate antiferromagnetic structure with a propagation vector k = (0, 0, 1/2). The magnetic moment in the ordered state of CeRhAl4sub>Si2 and CeIrAl4sub>Si2 were determined to be 1.14(2) and 1.41(3) μB/Ce, respectively, and are parallel to the crystallographic c-axis in agreement with magnetic susceptibility measurements.

  14. Single crystal growth of Yb doped NaGd(WO{sub 4}){sub 2} and structural and spectroscopic studies

    SciTech Connect

    Singh, S. G.; Singh, A. K.; Desai, D. G.; Tiwari, B.; Tyagi, M.


    High quality single crystals of NaGd(WO{sub 4}){sub 2} doped with 5 mol % Yb and oriented along <001> have been grown by the Czochralski technique in Ar atmosphere. The tetragonal space group I41/a accounts for all the reflections observed in the powder X-ray diffraction analysis. Polarized optical spectroscopy at room temperature revealed a direction dependence of absorption at different wavelength. As a novel uniaxial laser host for Yb{sup 3+}, NaGd(WO{sub 4}){sub 2} is characterized with respect to its transparency and band-edge. The emission spectrum of Yb{sup 3+} (excitation: 980-990 nm diode laser) was also recorded.

  15. Investigation of room temperature ferromagnetic nanoparticles of Gd5Si4sub>

    SciTech Connect

    Hadimani, R. L.; Gupta, S.; Harstad, S. M.; Pecharsky, V. K.; Jiles, D. C.


    Gd5(SixGe1-x)4sub> compounds undergo first-order phase transitions close to room temperature when x ~ = 0.5, which are accompanied by extreme changes of properties. We report the fabrication of the nanoparticles of one of the parent compounds-Gd5Si4sub>-using high-energy ball milling. Crystal structure, microstructure, and magnetic properties have been investigated. Particles agglomerate at long milling times, and the particles that are milled >20 min lose crystallinity and no longer undergo magnetic phase transition close to 340 K, which is present in a bulk material. The samples milled for >20 min exhibit a slightly increased coercivity. As a result, magnetization at a high temperature of 275K decreases with the increase in the milling time.

  16. Effects of Nickel Doping on the Multiferroic and Magnetic Phases of MnWO 4sub>

    SciTech Connect

    Poudel, N.; Lorenz, B.; Lv, B.; Wang, Y. Q.; Ye, F.; Wang, Jinchen; Fernandez-baca, J. A.; Chu, C. W.


    There are various orders in multiferroic materials with a frustrated spiral spin modulation inducing a ferroelectric state are extremely sensitive to small perturbations such as magnetic and electric fields, external pressure, or chemical substitutions. A classical multiferroic, the mineral Hubnerite with chemical formula MnWO4sub>, shows three different magnetic phases at low temperature. The intermediate phase between 7.5K < T < 12.7K is multiferroic and ferroelectricity is induced by an inversion symmetry breaking spiral Mn-spin order and strong spin-lattice interactions. Furthermore, the substitution of Ni2+ (spin 1) for Mn2+ (spin 5/2) in MnWO4sub> and its effects on the magnetic and multiferroic phases are studied. The ferroelectric phase is stabilized for low Ni content (up to 10%). Upon further Ni doping, the polarization in the ferroelectric phase is quickly suppressed while a collinear and commensurate magnetic phase, characteristic of the magnetic structure in NiWO4sub>, appears first at higher temperature, gradually extends to lower temperature, and becomes the ground state above 30% doping. Between 10% and 30%, the multiferroic phase coexists with the collinear commensurate phase. In this concentration region, the spin spiral plane is close to the a-b plane which explains the drop of the ferroelectric polarization. Finally, the phase diagram of Mn1-xNixWO4sub> is derived by a combination of magnetic susceptibility, specific heat, electric polarization, and neutron scattering measurements.

  17. Fermions and gauge bosons in SU(4){sub L}xU(1){sub X} models with little Higgs

    SciTech Connect

    Nam, Soo-hyeon


    We discuss the aspects of the little Higgs model with the SU(4){sub L}xU(1){sub X} electroweak gauge group as an alternative solution to the naturalness and fine-tuning issues. We introduce anomaly-free fermion spectra, and present their interactions with the physical gauge bosons. We also discuss some phenomenological implications of these fermions and the extra gauge bosons based on recent experimental results.

  18. Crystal chemistry of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} double monophosphates

    SciTech Connect

    Bregiroux, Damien; Popa, Karin; Wallez, Gilles


    M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds have been extensively studied for several decades for their potential applications in the field of several domains such as matrices for actinides conditioning, phosphors etc. In this paper, the relationships between composition and crystal structure of these compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. M{sup II}M′{sup IV}(PO{sub 4}){sub 2} structures stem from two different archetypes: the cheralite and the yavapaiite structures, with some exceptions that are also described in this article. The ratio of the cations radii appears to be the most relevant parameter. The high ratio between the ionic radii of the divalent and tetravalent cations in yavapaiite derivates results in the ordering of these cations into well-differentiated polyhedra whereas cheralite is the only non-ordered structure encountered for M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds. - Graphical abstract: In this paper, the relationships between composition and crystal structure of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. - Highlights: • Crystal structure–composition relationships of MIIM′IV(PO4)2 compounds. • Review of the various processes used for the synthesis of these compounds. • Their most reported properties are described and discussed.

  19. High-temperature phase transformation and topochemical nature in ferroelastic (NH{sub 4}){sub 2}SO{sub 4}

    SciTech Connect

    Lee, Kwang-Sei; Oh, In-Hwan; Ko, Jae-Hyeon


    The electrical conductivity of ferroelastic ammonium sulfate (NH{sub 4}){sub 2}SO{sub 4} revealed an anomaly at around 130 °C (=403 K, T{sub P}) on heating with large and irreversible thermal hysteresis through thermal cycle. Ferroelastic domain walls and surface morphology of (NH{sub 4}){sub 2}SO{sub 4} were investigated by hot-stage polarizing microscopy. Structural phase transition from an orthorhombic ferroelastic phase to a hexagonal paraelastic phase was not identified at T{sub P} upon heating. On further heating above T{sub P}, microscopic spots appeared and grew on the crystal surface, suggesting that the high-temperature anomaly at T{sub P} was an indication of an onset of thermal decomposition controlled by topochemical factors. The increase of electrical conductivity above T{sub P} was attributed to proton migration. - Graphical abstract: Surface morphology of the (100) face of (NH{sub 4}){sub 2}SO{sub 4} on heating, showing chemical reaction at the surface. - Highlights: • We investigate the high-temperature phase transformation of ammonium sulfate. • The increasing conductivity upon heating is attributed to proton migration. • Structural phase transition from orthorhombic to hexagonal phase is not confirmed. • High-temperature anomaly is related to an onset of thermal decomposition. • The nature of the high-temperature anomaly is topochemical controlled by defects.

  20. Hydrothermal synthesis and luminescent properties of NaLa(MoO{sub 4}){sub 2}:Dy{sup 3+} phosphor

    SciTech Connect

    Li Linlin; Zi Wenwen; Li Guanghuan; Lan Shi; Ji Guijuan; Gan Shucai; Zou Haifeng; Xu Xuechun


    Pompon-like NaLa(MoO{sub 4}){sub 2}:Dy{sup 3+} phosphors have been successfully prepared via a hydrothermal method using ammonia as pH value regulator. The hydrothermal process was carried out under aqueous condition without the use of any organic solvent, surfactant, and catalyst. The experimental results demonstrate that the obtained NaLa(MoO{sub 4}){sub 2}:Dy{sup 3+} phosphor powders are single-phase scheelite structure with tetragonal symmetry. Moreover, the phosphor under the excitation of 390 and 456 nm exhibited blue emission (486 nm) and yellow emission (574 nm), corresponding to the {sup 4}F{sub 9/2}{yields}{sup 6}H{sub 15/2} transition and {sup 4}F{sub 9/2}{yields}{sup 6}H{sub 13/2} transition of Dy{sup 3+} ions, respectively. In addition, the yellow-to-blue emission intensity ratio (Y/B) can be changed with the doped concentration of Dy{sup 3+} ions. All chromaticity coordinates of the obtained NaLa(MoO{sub 4}){sub 2}:Dy{sup 3+} phosphors are located in the white-light region. The results indicate that this kind of phosphor may has potential applications in the fields of near UV-excited and blue-excited white LEDs. - Graphical abstract: It can be seen from the SEM images that a pompon-like shape was obtained with an average diameter of about 1 {mu}m, and it is composed of many nanoflakes. Highlights: Black-Right-Pointing-Pointer Pompon-like NaLa(MoO{sub 4}){sub 2}:Dy{sup 3+} phosphors have been successfully prepared via a hydrothermal method. Black-Right-Pointing-Pointer Blue emission at 486 nm and yellow emission at 574 nm were obtained from the samples. Black-Right-Pointing-Pointer The yellow-to-blue emission intensity ratio (Y/B) can be changed with the doped concentration of Dy{sup 3+} ions. Black-Right-Pointing-Pointer NaLa(MoO{sub 4}){sub 2}:Dy{sup 3+} can be efficiently excited by the blue light and the near ultraviolet light.

  1. 1.1 MW peak power in doubly QML composite Nd:YVO4sub>/Nd:YVO4sub>/Nd:YVO4sub>/KTP sub-nanosecond green laser with EO and Bi-GaAs.


    Li, Shixia; Li, Dechun; Zhao, Shengzhi; Li, Guiqiu; Li, Xiangyang; Qiao, Hui


    By simultaneously employing electro-optic (EO) modulator and Bi-doped GaAs, dual-loss-modulated Q-switched and mode-locked (QML) multi-segment composite Nd:YVO4sub>/Nd:YVO4sub>/Nd:YVO4sub>/KTP sub-nanosecond green laser is demonstrated with low repetition rate and high peak power. When the incident pump power is up to 6.93 W, only one mode-locking pulse underneath a Q-switching envelope is generated with sub-nanosecond pulse duration at one kilohertz repetition rate. An average output power of 445 mW and a pulse duration of 399 ps are obtained with the incident pump power of 11.13 W, corresponding to a peak power of 1.115 MW which is the highest one in doubly QML sub-nanosecond green laser by now. The laser characteristics are better than those obtained with EO and GaAs. The experimental results indicate that Bi-GaAs is a promising saturable absorber for dual-loss-modulated QML laser. PMID:26907054

  2. New open-framework in the uranyl vanadates A{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O (A=Li, Ag) with intergrowth structure between A(UO{sub 2}){sub 4}(VO{sub 4}){sub 3} and A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O

    SciTech Connect

    Obbade, S. Renard, C.; Abraham, F.


    New uranyl vanadates A{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O (M=Li (1), Na (2), Ag (3)) have been synthesized by solid-state reaction and their structures determined from single-crystal X-ray diffraction data for 1 and 3. The tetragonal structure results of an alternation of two types of sheets denoted S for {sub {infinity}}{sup 2}[UO{sub 2}(VO{sub 4}){sub 2}]{sup 4-} and D for {sub {infinity}}{sup 2}[(UO{sub 2}){sub 2}(VO{sub 4}){sub 3}]{sup 5-} built from UO{sub 6} square bipyramids and connected through VO{sub 4} tetrahedra to {sub {infinity}}{sup 1}[U(3)O{sub 5}-U(4)O{sub 5}]{sup 8-} infinite chains of edge-shared U(3)O{sub 7} and U(4)O{sub 7} pentagonal bipyramids alternatively parallel to a- and b-axis to construct a three-dimensional uranyl vanadate arrangement. It is noticeable that similar {sub {infinity}}[UO{sub 5}]{sup 4-} chains are connected only by S-type sheets in A{sub 2}(UO{sub 2}){sub 3}(VO{sub 4}){sub 2}O and by D-type sheets in A(UO{sub 2}){sub 4}(VO{sub 4}){sub 3}, thus A{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O appears as an intergrowth structure between the two previously reported series. The mobility of the monovalent ion in the mutually perpendicular channels created in the three-dimensional arrangement is correlated to the occupation rate of the sites and by the geometry of the different sites occupied by either Na, Ag or Li. Crystallographic data: 293 K, Bruker X8-APEX2 X-ray diffractometer equipped with a 4 K CCD detector, MoK{alpha}, {lambda}=0.71073 A, tetragonal symmetry, space group P4-bar m2, Z=1, full-matrix least-squares refinement on the basis of F{sup 2}; 1,a=7.2794(9) A, c=14.514(4) A, R1=0.021 and wR2=0.048 for 62 parameters with 782 independent reflections with I{>=}2{sigma}(I); 3, a=7.2373(3) A, c=14.7973(15) A, R1=0.041 and wR2=0.085 for 60 parameters with 1066 independent reflections with I{>=}2{sigma}(I). - Abstract: A view of the three-dimensional structure of Li{sub 3}(UO{sub 2}){sub 7}(VO{sub 4}){sub 5}O

  3. Supramolecular Chemistry with Uranyl Tetrahalide ([UO2X4sub>]2-) Anions

    SciTech Connect

    Deifel, Nicholas P.; Cahill, Christopher L.


    Five compounds containing the uranyl tetrabromide anion ([UO2Br4sub>2-) have been synthesized through room temperature reactions of uranium (VI) oxyacetate with several pyridinium cations in highly acidic solutions containing Br- anions. The resulting compounds have been characterized via single-crystal X-ray diffraction and fluorescence spectroscopy. Three of these compounds exhibit both a bifurcated hydrogen bond NH-Br2U and an extended “ribbon motif” of alternating organic and inorganic species.

  4. Synthesis and photoluminescence characteristics of Dy{sup 3+} doped NaY(WO{sub 4}){sub 2} phosphors

    SciTech Connect

    Liu, Xiaohua; Xiang, Wendou; Chen, Fengming; Hu, Zhengfa; Zhang, Wei


    Graphical abstract: The phosphor powders of NaY(WO{sub 4}){sub 2}: Dy{sup 3+} were prepared by solid state reaction. For the different kinds of excitations, the dependence of luminescence intensity on the Tb{sup 3+} concentration was investigated. Display Omitted Highlights: ► We synthesize NaY(WO{sub 4}){sub 2}:Dy{sup 3+} phosphors by the solid-state reaction technique. ► We observe and explain the change of Y/B ratio with Dy{sup 3+} content. ► The I−x curve shows different behavior for different excitations. ► The concentration quenching mechanism is the d–d interaction. -- Abstract: The novel phosphor powders of NaY(WO{sub 4}){sub 2} doped with Dy{sup 3+} were synthesized by solid state reaction. X-ray diffraction analysis showed that the phosphors sintered at 900 °C for 6 h were a pure NaY(WO{sub 4}){sub 2} phase for all the Dy{sup 3+} doping concentrations. The room temperature excitation spectra of the phosphors vary with the Dy{sup 3+} concentration and consist of an intense charge transfer band of WO{sub 4}{sup 2−} groups and weak f–f transition absorption peaks of Dy{sup 3+}. The photoluminescence spectra, excited at the peak wavelength of charge transfer band, exhibit three bands centered at 488, 575 and 662 nm, which originate from the transitions of {sup 4}F{sub 9/2} → {sup 6}H{sub 15/2} (blue), {sup 4}F{sub 9/2} → {sup 6}H{sub 13/2} (yellow) and {sup 4}F{sub 9/2} → {sup 6}H{sub 11/2} (red) of Dy{sup 3+}, respectively. The effects of Dy{sup 3+} concentration on luminescence intensity and the yellow-to-blue intensity ratio of the phosphors were investigated. The different behaviors for the doping concentration dependence of luminescence intensity resulted from the different kinds of excitation was discussed.

  5. trans-K3[TcO2(CN)4sub>

    SciTech Connect

    Chatterjee, Sayandev; Del Negro, Andrew S; Edwards, Matthew K; Twamley, Brendan; Krause, Jeanette A; Bryan, Samuel A


    The dioxotetracyanotechnetate anion, [TcO2(CN)4sub>]3-, of the title complex has octahedral symmetry. The technetium is located on a center of inversion and is bound by two oxygen atoms and four cyano ligands. The Tc=O bond distance of 1.7721 (12) Å is consistent with double bond character. The potassium cations [located on special (1/2,0,1) and general positions] reside in octahedral or tetrahedral environments; interionic K···O and K···N interactions occur in the 2.7877 (19)-2.8598 (15) Å range.

  6. Infrared-to-visible upconversion in thin films of LaEr(MoO{sub 4}){sub 3}

    SciTech Connect

    Bubb, D.M.; Cohen, D.; Qadri, S.B.


    LaEr(MoO{sub 4}){sub 3} thin films have been grown by pulsed laser deposition. The films were characterized by x-ray diffraction, Rutherford backscattering, and fluorescence measurements. The results show that the deposited films were epitaxial with their c axis oriented along the surface normal. Films illuminated with 980 nm laser light show visible emission spectra. This visible emission arises as a result of the Er 4f-4f transitions and their lifetimes. Such so-called 'upconverting phosphors' are important to the development of new chemical and biological sensing applications.

  7. Morphology control of open-framework zinc phosphate Zn{sub 4}(H{sub 3}O)(NH{sub 4}){sub 3}(PO{sub 4}){sub 4} via microwave-assisted technique

    SciTech Connect

    Ding, Ling; Song, Yu; Yang, Wei; Xue, Run-Miao; Zhai, Shang-Ru; An, Qing-Da


    Open-framework zinc phosphates were synthesized by microwave-assisted technique, and it was shown that the morphology of as-prepared materials could be easily tailored by changing synthesis temperature, reaction time and pH value. During the synthesis, when the reaction temperature increases from 130 °C to 220 °C, the products transformed from hexagonal prisms to polyhedron along with the disappearance of the hexagonal prisms vertical plane. Simultaneously, both the reaction time and pH value could promote the nucleation and growth of crystal particles. More interestingly, the target products with different morphologies could be obtained by varying the usage of NaOH or NH{sub 3}·H{sub 2}O at 130 °C during the microwave synthesis process. - Graphical abstract: Zinc phosphates with variable morphologies can be obtained by simply tuning the microwave-heating temperatures. Display Omitted - Highlights: • Synthesis of open-framework Zn{sub 4} (H{sub 3}O) (NH{sub 4}){sub 3}(PO{sub 4}){sub 4} compounds employing microwave technique. • Dependence of morphology on the reaction conditions. • Morphology transformation from hexagonal prisms to polyhedron was observed.

  8. Tailoring the surface properties of LiNi0.4sub>Mn0.4sub>Co0.2O₂ by titanium substitution for improved high voltage cycling performance

    SciTech Connect

    Wolff-Goodrich, Silas; Xin, Huolin L.; Lin, Feng; Markus, Isaac M.; Nordlund, Dennis; Asta, Mark; Doeff, Marca M.


    The present research aims to provide insights into the behavior of LiNi0.4Mn0.4Co0.2O2 (NMC442) and LiNi0.4sub>Mn0.4sub>Co0.2O₂ (NMC442-Ti02) cathode materials under galvanostatic cycling to high potentials, in the context of previous work which predicted that Ti-substituted variants should deliver higher capacities and exhibit better cycling stability than the unsubstituted compounds. It is found that NMC cathodes containing Ti show equivalent capacity fading but greater specific capacity than those without Ti in the same potential range. When repeatedly charged to the same degree of delithiation, NMC cathodes containing Ti showed better capacity retention. Soft x-ray absorption spectroscopy (XAS) spectra for Mn and Co indicated increased reduction in these elements for NMC cathodes without Ti, indicating that the substitution of Ti for Co acts to suppress the formation of a high impedance rock salt phase at the surface of NMC cathode particles. The results of this study validate the adoption of a facile change to existing NMC chemistries to improve cathode capacity retention under high voltage cycling conditions.

  9. Heterogeneous Nature of Relaxation Dynamics of Room-Temperature Ionic Liquids (EMIm)2[Co(NCS)4sub>] and (BMIm)2[Co(NCS)4sub>

    SciTech Connect

    Hensel-Bielowka, Stella; Wojnarowska, Zaneta; Dzida, Marzena; Zorębski, Edward; Zorębski, Michał; Geppert-Rybczyńska, Monika; Peppel, Tim; Grzybowska, Katarzyna; Wang, Yangyang; Sokolov, Alexei P.; Paluch, Marian


    Dynamic crossover above Tg has been recognized as a characteristic feature of molecular dynamics of liquids approaching glass transition. Experimentally, it is manifested as a change in Vogel–Fulcher–Tammann dependence or a breakdown of the Stokes–Einstein and related relations. In this study, we report the exception from this rather general pattern of behavior. By means of dielectric, ultrasonic, rheological, and calorimetric methods, dynamics of two good ionic conductors (BMIm)2[Co(NCS)4sub>] and (EMIm)2[Co(NCS)4sub>] of less common stoichiometry (2:1) was studied in a very broad temperature range. However, none of the mentioned dynamic changes was observed in the entire studied temperature range. On the contrary, the single VFT and the same fractional Walden coefficient were found for conductivity and viscosity changes over 12 decades. Finally and moreover, ultrasonic studies revealed that the data at temperatures which cover the normal liquid region cannot be fitted by a single exponential decay, and the Cole–Cole function should be used instead.

  10. Study of calcium-containing orthophosphates of NaZr{sub 2}(PO{sub 4}){sub 3} structural type by high-temperature X-ray diffraction

    SciTech Connect

    Orlova, A. I.; Kanunov, A. E.; Samoilov, S. G.; Kazakova, A. Yu.; Kazantsev, G. N.


    Orthophosphates Ca{sub 0.5}Ti{sub 2}(PO{sub 4}){sub 3}, Ca{sub 0.5}Zr{sub 2}(PO{sub 4}){sub 3}, Ca{sub 0.75}Zr{sub 2}(SiO{sub 4}){sub 0.5}(PO{sub 4}){sub 2.5}, and CaMg{sub 0.5}Zr{sub 1.5}(PO{sub 4}){sub 3} (structural type NaZr{sub 2}(PO{sub 4}){sub 3}), having different occupancies of interframework positions by calcium, have been prepared by the sol-gel method with the subsequent thermal treatment of dried gels and investigated by IR spectroscopy and X-ray diffraction. The analytical indexing of X-ray diffraction patterns is performed within the sp. gr. R3{sup -}. High-temperature X-ray diffraction was used to investigate the behavior of the orthophosphates upon heating: thermal expansion in the temperature range of 20-610 Degree-Sign C (up to 500 Degree-Sign C for Ca{sub 0.5}Zr{sub 2}(PO{sub 4}){sub 3}). The coefficients of thermal expansion are calculated from the shift of diffraction peaks. The unit-cell parameters of crystals at different temperatures are determined. The dependences of thermal expansion and its anisotropy on the occupancy of cation M positions by calcium are revealed.

  11. M{sup II}Ge(PO{sub 4}){sub 2} (M=Ca, Sr, Ba): Crystal structure, phase transitions and thermal expansion

    SciTech Connect

    Popa, Karin; Wallez, Gilles; Bregiroux, Damien; Loiseau, Pascal


    Three earth alkali-germanium monophosphates M{sup II}Ge(PO{sub 4}){sub 2} (M=Ca, Sr, Ba) were prepared by solid state reaction and their structures, previously unknown, studied by Rietveld analysis. BaGe(PO{sub 4}){sub 2} and high-temperature {beta}-SrGe(PO{sub 4}){sub 2} (space group C2/m, Z=2) are fully isotypic with yavapaiite, whereas CaGe(PO{sub 4}){sub 2} and low-temperature {alpha}-SrGe(PO{sub 4}){sub 2} (C2/c, Z=4) are distorted derivatives. The phase transition between the two forms is observed for the first time. The thermal expansion, resulting from several structural mechanisms, is very anisotropic. - Graphical abstract: The superstructure of SrGe(PO{sub 4}){sub 2} at room temperature ({alpha}) results from the off-centering of cation Sr{sup II}. Highlights: > Crystal structures of yavapaiite-type M{sup II}Ge(PO{sub 4}){sub 2} (M=Ca, Sr, Ba) have been solved. > Distortion and superstructure result from Ca and Sr off-centering. > A global scheme for the polymorphism of yavapaiites is proposed.

  12. Nanocrystalline K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}: Eu for proton beam dosimetry

    SciTech Connect

    Bahl, Shaila; Lochab, S. P.; Pandey, A.; Aleynikov, V. E.; Molokanov, A.; Kumar, Pratik


    This paper investigates the Thermoluminescent response of nanocrystalline K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}: Eu, prepared by Co-precipitation technique to 150 MeV proton beam. The particle size was calculated to be 45 nm by the broadening of the XRD peaks using Scherrer's formula. Samples in the form of pellets were irradiated by 150 MeV proton beam with dose range of 0.1 Gy to 325 Gy. Thermoluminescence (TL) glow curves of the irradiated samples were recorded and studied. It has been found that the phosphor shows a characteristic single peak at around 420 K. The TL response is linear in the range upto 200 Gy and then saturates for higher doses. The wider linear TL response of nanocrystalline K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}: Eu and low fading makes it a superior candidate as a dosimeter to be used for detecting the doses of protons beams for its various applications in the field of space, therapy and research.

  13. First-principles predicted low-energy structures of NaSc(BH{sub 4}){sub 4}

    SciTech Connect

    Tran, Huan Doan Amsler, Maximilian; Goedecker, Stefan; Botti, Silvana; Marques, Miguel A. L.


    According to previous interpretations of experimental data, sodium-scandium double-cation borohydride NaSc(BH{sub 4}){sub 4} crystallizes in the crystallographic space group Cmcm where each sodium (scandium) atom is surrounded by six scandium (sodium) atoms. A careful investigation of this phase based on ab initio calculations indicates that the structure is dynamically unstable and gives rise to an energetically and dynamically more favorable phase with C222{sub 1} symmetry and nearly identical x-ray diffraction pattern. By additionally performing extensive structural searches with the minima-hopping method we discover a class of new low-energy structures exhibiting a novel structural motif in which each sodium (scandium) atom is surrounded by four scandium (sodium) atoms arranged at the corners of either a rectangle with nearly equal sides or a tetrahedron. These new phases are all predicted to be insulators with band gaps of 7.9–8.2 eV. Finally, we estimate the influence of these structures on the hydrogen-storage performance of NaSc(BH{sub 4}){sub 4}.

  14. Photoluminescence performance of thulium doped Li{sub 4}SrCa(SiO{sub 4}){sub 2} under irradiation of ultraviolet and vacuum ultraviolet lights

    SciTech Connect

    Wang, Zhaofeng; Li, Yezhou; Liu, Xiong; Wei, Xingmin; Chen, Yueling; Zhou, Fei; Wang, Yuhua


    Highlights: • A novel blue-emitting phosphor Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} was reported. • Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} exhibited excellent thermal and irradiation stability. • Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} was found to possess high color purity. - Abstract: In this work, we synthesized Tm{sup 3+} doped Li{sub 4}SrCa(SiO{sub 4}){sub 2} phosphors and investigated their photoluminescence properties under the excitation of ultraviolet and vacuum ultraviolet lights. The crystal structure analysis and variation of cell parameters confirm that Tm{sup 3+} ions have been successfully doped in the structure of Li{sub 4}SrCa(SiO{sub 4}){sub 2} host by occupying the sites of Ca{sup 2+} with the coordination number of 6. The luminescence results suggest that Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} is a good blue-emitting phosphor when excited by ultraviolet and vacuum ultraviolet irradiations. In addition, it is observed that there is nearly no degradation for Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} after undergoing thermal and irradiation treatments. Possible mechanisms for the luminescence processes are proposed on the basis of the discussion of excitation and emission spectra. In particular, the emission color of Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} by excitation of 147 and 172 nm irradiations is very close to the standard blue color, suggesting that it could be potentially applied in plasma display panels and mercury-free fluorescence lamps.

  15. Crystal structure, thermally stability and photoluminescence properties of novel Sr{sub 10}(PO{sub 4}){sub 6}O:Eu{sup 2+} phosphors

    SciTech Connect

    Guo, Qingfeng; Liao, Libing Mei, Lefu; Liu, Haikun


    A series of novel luminescent phosphors Sr{sub 10}(PO{sub 4}){sub 6}O:Eu{sup 2+} with apatite structure were synthesized via a high temperature solid-state reaction. The phase structure, photoluminescence (PL) properties, the PL thermal stability, as well as the fluorescence decay curves of the samples were investigated to characterize the resulting samples, and the selected Sr{sub 9.97}(PO{sub 4}){sub 6}O:0.03Eu{sup 2+} phosphor exhibits strong thermal quenching resistance, retaining the luminance of 88.73% at 150 °C. The quenching concentration of Eu{sup 2+} in Sr{sub 10}(PO{sub 4}){sub 6}O was about 0.03 attributing to the dipole–quadrupole interaction. The Sr{sub 10}(PO{sub 4}){sub 6}O:Eu{sup 2+} phosphor exhibited a broad-band blue emission at 439 nm upon excitation at 346 nm. The results indicate that Sr{sub 10}(PO{sub 4}){sub 6}O:Eu{sup 2+} phosphors have potential applications as near UV-convertible phosphors for white-light UV LEDs. - Graphical abstract: Sr{sub 10}(PO{sub 4}){sub 6}O:Eu{sup 2+} phosphors have potential applications as near UV-convertible phosphors for white-light UV LEDs. - Highlights: • Sr{sub 9.97}(PO{sub 4}){sub 6}O:0.03Eu{sup 2+} phosphor exhibits strong thermal quenching resistance. • Two different Eu{sup 2+} emission centers exists in Sr{sub 10}(PO{sub 4}){sub 6}O. • The activation energy was also estimated for the Eu{sup 2+} luminescence center.

  16. Controlled synthesis, characterization and photoluminescence property of olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3}

    SciTech Connect

    Zhang, Youjin; Zheng, Ao; Yang, Xiaozhi; He, Hongmei; Fan, Yun


    Highlights: ► The olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3} was gained with EDTA assisted hydrothermal method. ► The product was characterized by XRD, XPS, FTIR, FESEM, and PL. ► The possible formation mechanism for olive-like α-Nd{sub 2}(MoO{sub 4}){sub 3} was proposed. ► The PL in visible region of the olive-like α-Nd{sub 2}(MoO{sub 4}){sub 3} was studied. -- Abstract: The olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3} was obtained by a convenient and facile complex agent assisted hydrothermal method. The product was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, field-emission scanning electron microscopy (FESEM) and photoluminescence (PL). The possible formation mechanism of the olive-like α-Nd{sub 2}(MoO{sub 4}){sub 3} was proposed. The photoluminescence property in visible region of the olive-like tetragonal α-Nd{sub 2}(MoO{sub 4}){sub 3} was studied.

  17. Investigation of the physical properties of the tetragonal CeMAl4sub>Si2 (M = Rh, Ir, Pt) compounds

    SciTech Connect

    Ghimire, N. J.; Ronning, F.; Williams, D. J.; Scott, B. L.; Luo, Yongkang; Thompson, J. D.; Bauer, E. D.


    The synthesis, crystal structure and physical properties studied by means of x-ray diffraction, magnetic, thermal and transport measurements of CeMAl4sub>Si2 (M = Rh, Ir, Pt) are reported, along with the electronic structure calculations for LaMAl4sub>Si2 (M = Rh, Ir, Pt). These materials adopt a tetragonal crystal structure (space group P4/mmm) comprised of BaAl4sub> blocks, separated by MAl2 units, stacked along the c-axis. Both CeRhAl4sub>Si2 and CeIrAl4sub>Si2 order antiferromagnetically below TN1 = 14 and 16 K, respectively, and undergo a second antiferromagnetic transitition at lower temperature (TN2 = 9 and 14 K, respectively). CePtAl4sub>Si2 orders ferromagnetically below TC = 3 K with an ordered moment of μsat = 0.8 μB for a magnetic field applied perpendicular to the c-axis. Electronic structure calculations reveal quasi-2D character of the Fermi surface.

  18. Gain change by adjusting the pumping wavelength in an end-pumped Nd:YVO4sub> amplifier.


    Nie, Mingming; Liu, Qiang; Ji, Encai; Fu, Xing; Gong, Mali


    In this paper, the performance of an end-pumped laser amplifier was experimentally studied by adjusting the pumping wavelength of a laser diode. An interesting phenomenon was observed: that the gain would decrease with an increase in absorbed pump power. The scaled output power of 0.3 at. % doped 20 mm long Nd:YVO4sub> crystal decreased from 0.48 to 0.2 W when the absorbed pump power increased from 17.5 to 17.8 W. Theoretical analysis was demonstrated according to our previous model. The long crystal length is the main reason for the observed phenomenon. This phenomenon could be utilized to enhance amplifier gain and improve thermal performance, including the maximal temperature and thermal stress of the crystal. PMID:27409123

  19. Morphologically Templated Growth of Aligned Spinel CoFe2O4sub> Nanorods

    SciTech Connect

    Zhang, Zongtao; Rondinone, Adam Justin; Ma, Jianxing; Shen, Jian; Dai, Sheng


    Uniaxially aligned CoFe{sub 2}O{sub 4} nanorods are obtained by coprecipitation of Co{sup 2+}, Fe{sub 2+}, and C{sub 2}O{sub 4}{sup 2-} ions in a microemulsion solution, and subsequent high-temperature decomposition of CoFe{sub 2}(C{sub 2}O{sub 4}){sub 3}. Each nanorod is made up of a 'tectonic' assembly of CoFe{sub 2}O{sub 4} nanocrystals. Magnetization of such SoFe{sub 2}O{sub 4} materials may lead to their use in high-density magnetic recording media and high-performance electromagnetic and spintronic devices.

  20. Megahertz-level, high-power picosecond Nd:LuVO4sub> regenerative amplifier free of period doubling.


    Gao, Peng; Lin, Hua; Li, Jinfeng; Guo, Jie; Yu, Haohai; Zhang, Huaijin; Liang, Xiaoyan


    We report on a high repetition rate, high-power picosecond Nd:LuVO4sub> regenerative amplifier. Period doubling caused energy instability was eliminated at megahertz-level repetition rate with the modified seeding source. A multi-pass cell was used to improve the seed pulse energy to achieve complete suppression of the onset of bifurcation. At a maximum repetition rate of 1.43 MHz, the system produced 7.0-ps-long pulses with an average output power of 25.1 W, corresponding to a pulse energy of 17.6 μJ. At 100 kHz, the pulse energy increased to 205 μJ with an average power of 20.5 W. Moreover, the injected pulses with pulse duration of 5.1 ps broadened to 8.9 ps because of gain narrowing in the amplifier. PMID:27410559

  1. New measurement of the {sup 68}Zn(4{sub 1}{sup +}) g factor combined with a reanalysis of previous data

    SciTech Connect

    Moschner, K.; Bernards, C.; Bettermann, L.; Speidel, K.-H.; Leske, J.; Bauer, C.; Moeller, T.; Honma, M.; Maier-Komor, P.; Muecher, D.


    We have remeasured and have redetermined the g factor for the 4{sub 1}{sup +} state in {sup 68}Zn following inconsistencies between earlier measurements and a recent result. We have reanalyzed several former measurements by applying an alternative analysis procedure, which allows for determining the precession effect separately for each gamma detector implying less uncertainties in the background subtraction for the relevant spectra. In addition, all measured g-factor and B(E2) data for the first 2{sup +} and 4{sup +} states in all stable even-A Zn isotopes and the radioactive {sup 62}Zn, are compared with new large-scale shell model calculations based on the most advanced effective interaction in the fpg-shell model space.

  2. Neutron diffraction study on the two-dimensional Ising system KEr(MoO{sub 4}){sub 2}

    SciTech Connect

    Mat'as, Slavomir; Dudzik, Esther; Feyerherm, Ralf; Gerischer, Sebastian; Klemke, Sebastian; Prokes, Karel; Orendacova, Alzbeta


    The magnetic properties of the two-dimensional Ising antiferromagnet KEr(MoO{sub 4}){sub 2} have been investigated below and above transition temperature T{sub N}{approx}0.95 K in zero field and in fields up to 6.5 T by means of elastic neutron-diffraction, heat-capacity, and magnetization measurements. The low-temperature signal recorded at 0.34 K by neutron diffraction is explained within a noncollinear magnetic structure model. However, additional contribution is also present when applying the external magnetic field along the c axis even at temperatures well above the magnetic transition temperature T{sub N}. Various explanations are discussed.

  3. Enhanced Thermoelectric Properties of Cu2ZnSnSe4sub> with Ga-doping

    SciTech Connect

    Wei, Kaya; Beauchemin, Laura; Wang, Hsin; Porter, Wallace D.; Martin, Joshua; Nolas, George S.


    Gallium doped Cu2ZnSnSe4sub> quaternary chalcogenides with and without excess Cu were synthesized by elemental reaction and densified using hot pressing in order to investigate their high temperature thermoelectric properties. The resistivity, , and Seebeck coefficient, S, for these materials decrease with increased Ga-doping while both mobility and effective mass increase with Ga doping. The power factor (S2/ρ) therefore increases with Ga-doping. The highest thermoelectric figure of merit (ZT = 0.39 at 700 K) was obtained for the composition that had the lowest thermal conductivity. Our results suggest an approach to achieving optimized thermoelectric properties and are part of the continuing effort to explore different quaternary chalcogenide compositions and structure types, as this class of materials continues to be of interest for thermoelectrics applications.

  4. Ionic liquid assisted microwave synthesis route towards color-tunable luminescence of lanthanide- doped BiPO4sub>

    SciTech Connect

    Cybinska, Joanna; Lorbeer, Chantal; Mudring, Anja -Verena


    Ln3+-doped (Ln=Sm, Eu, Tb, Dy) nanoparticles of BiPO4sub> with a particle size below 10 nm were synthesized in a straightforward manner from the appropriate mixture of the respective metal acetates and the task-specific ionic liquids choline or butylammonium dihydrogen-phosphate by conversion in a laboratory microwave (120 °C, 10 min). The ionic liquid acts not only as a solvent and microwave susceptor, but also as the reaction partner and nanoparticle stabilizer. The materials were thoroughly characterized not only with respect to their optical properties but also by PXRD, FT-IR, TEM techniques. Furthermore, depending on the lanthanide, the nanomaterial shows intense luminescence of different colors such as: orange (Sm3+), red (Eu3+), green (Tb3+) or even white (Dy3+).

  5. Luminescent and lasing characteristics of heavily doped Yb{sup 3+}:KY(WO{sub 4}){sub 2} crystals

    SciTech Connect

    Kisel', V E; Troshin, A E; Shcherbitskii, V G; Kuleshov, N V; Pavlyuk, A A; Brunner, F; Paschotta, R; Morier-Genoud, F; Keller, U


    The luminescence decay times are measured taking into account reabsorption for KY(WO{sub 4}){sub 2}:Yb(KYW:Yb) crystals with atomic concentrations of active ions from 0.2% to 30%. The radiative lifetime of Yb{sup 3+} ions was measured to be 233 {mu}s. The cw output power of 1.46 and 1.62 W was achieved with the slope efficiency 52% and 47% for Yb:KYW lasers with the atomic concentration of Yb{sup 3+} ions equal to 10% and 30%, respectively. Using a semiconductor mirror with a saturable absorber (SESAM) in the passive mode-locking regime, pulses of duration 194 and 180 fs were obtained at wavelengths of 1042 and 1039 nm for crystals with Yb{sup 3+} concentrations equal to 10% and 30%, respectively, the average output power being 0.63 and 0.75 W. (lasers and amplifiers)

  6. Syntheses, crystal structures and vibrational spectra of KLn(SO{sub 4}){sub 2}.H{sub 2}O (Ln=La, Nd, Sm, Eu, Gd, Dy)

    SciTech Connect

    Kazmierczak, Karolina; Hoeppe, Henning A.


    The potassium lanthanide double sulphates KLn(SO{sub 4}){sub 2}.H{sub 2}O (Ln=La, Nd, Sm, Eu, Gd, Dy) were obtained by evaporation of aqueous reaction mixtures of rare earth (III) sulphates and potassium thiocyanate at 298 K. X-ray single-crystal investigations show that KLn(SO{sub 4}){sub 2}.H{sub 2}O (Ln=Nd, Sm, Eu, Gd, Dy) crystallise monoclinically (Ln=Sm: P2{sub 1}/c, Z=4, a=10.047(1), b=8.4555(1), c=10.349(1) A, wR2=0.060, R1=0.024, 945 reflections, 125 parameters) while KLa(SO{sub 4}){sub 2}.H{sub 2}O adopts space group P3{sub 2}21 (Z=3, a=7.1490(5), c=13.2439(12) A, wR2=0.038, R1=0.017, 695 reflections, 65 parameters). The coordination environment of the lanthanide ions in KLn(SO{sub 4}){sub 2}.H{sub 2}O is different in the case of the Nd/Sm/Gd and the Eu/Dy compounds, respectively. In the first case the Ln atoms are nine-fold coordinated in contrast to the latter where the Ln ions are eight-fold coordinated by oxygen atoms. The vibrational spectra of KLn(SO{sub 4}){sub 2}.H{sub 2}O and the UV-vis reflection spectra of KEu(SO{sub 4}){sub 2}.H{sub 2}O and KNd(SO{sub 4}){sub 2}.H{sub 2}O are also reported. - Graphical abstract: The lanthanide potassium double sulphates exhibit an unexpected change in the coordination mode by a simple rotation of sulphate tetrahedron 2.

  7. Synthesis, structural and spectroscopic properties of acentric triple molybdate Cs{sub 2}NaBi(MoO{sub 4}){sub 3}

    SciTech Connect

    Savina, A.A.; Atuchin, V.V.; Solodovnikov, S.F.; Solodovnikova, Z.A.; Krylov, A.S.; Maximovskiy, E.A.; Molokeev, M.S.; Oreshonkov, A.S; Pugachev, A.M.; and others


    New ternary molybdate Cs{sub 2}NaBi(MoO{sub 4}){sub 3} is synthesized in the system Na{sub 2}MoO{sub 4}–Cs{sub 2}MoO{sub 4}–Bi{sub 2}(MoO{sub 4}){sub 3}. The structure of Cs{sub 2}NaBi(MoO{sub 4}){sub 3} of a new type is determined in noncentrosymmetric space group R3c, a=10.6435(2), c=40.9524(7) Å, V=4017.71(13) Å{sup 3}, Z=12 in anisotropic approximation for all atoms taking into account racemic twinning. The structure is completely ordered, Mo atoms are tetrahedrally coordinated, Bi(1) and Bi(2) atoms are in octahedra, and Na(1) and Na(2) atoms have a distorted trigonal prismatic coordination. The Cs(1) and Cs(2) atoms are in the framework cavities with coordination numbers 12 and 10, respectively. No phase transitions were found in Cs{sub 2}NaBi(MoO{sub 4}){sub 3} up to the melting point at 826 K. The compound shows an SHG signal, I{sub 2w}/I{sub 2w}(SiO{sub 2})=5 estimated by the powder method. The vibrational properties are evaluated by Raman spectroscopy, and 26 narrow lines are measured. - Graphical abstract: - Highlights: • The crystal structure of Cs{sub 2}NaBi(MoO{sub 4}){sub 3} is defined. • The molybdate Cs{sub 2}NaBi(MoO{sub 4}){sub 3} is stable up to melting point at 826 K. • Vibrational properties of Cs{sub 2}NaBi(MoO{sub 4}){sub 3} are evaluated by Raman spectroscopy.

  8. Synthesis, structures and properties of the new lithium cobalt(II) phosphate Li{sub 4}Co(PO{sub 4}){sub 2}

    SciTech Connect

    Glaum, R.; Gerber, K.; Schulz-Dobrick, M.


    {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} has been synthesized and crystallized by solid-state reactions. The new phosphate crystallizes in the monoclinic system (P2{sub 1}/a, Z=4, a=8.117(3) Angstrom-Sign , b=10.303(8) Angstrom-Sign , c=8.118(8) Angstrom-Sign , {beta}=104.36(8) Angstrom-Sign ) and is isotypic to {alpha}-Li{sub 4}Zn(PO{sub 4}){sub 2}. The structure of {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} has been determined from single-crystal X-ray diffraction data {l_brace}R{sub 1}=0.040, wR{sub 2}=0.135, 2278 unique reflections with F{sub o}>4{sigma}(F{sub o}){r_brace}. The crystal structure, which might be regarded as a superstructure of the wurtzite structure type, is build of layers of regular CoO{sub 4}, PO{sub 4} and Li1O{sub 4} tetrahedra. Lithium atoms Li2, Li3 and Li4 are located between these layers. Thermal investigations by in-situ XRPD, DTA/TG and quenching experiments suggest decomposition followed by formation and phase transformation of Li{sub 4}Co(PO{sub 4}){sub 2}: {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} Long-Rightwards-Double-Arrow {sup 442 Degree-Sign C}{beta}-Li{sub 3}PO{sub 4}+LiCoPO{sub 4} Rightwards-Harpoon-Over-Leftwards-Harpoon {sup 773 Degree-Sign C}{beta}-Li{sub 4}Co(PO{sub 4}){sub 2} Long-Rightwards-Double-Arrow {sup quenchingto25 Degree-Sign C}{alpha}-Li{sub 4} Co(PO{sub 4}){sub 2} According to HT-XRPD at {theta}=850 Degree-Sign C{beta}-Li{sub 4}Co(PO{sub 4}){sub 2} (Pnma, Z=2, 10.3341(8) A, b=6.5829(5) A, c=5.0428(3) Angstrom-Sign ) is isostructural to {gamma}-Li{sub 3}PO{sub 4}. The powder reflectance spectrum of {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} shows the typical absorption bands for the tetrahedral chromophore [Co{sup II}O{sub 4}]. - Graphical abstract: The complex formation and decomposition behavior of Li{sub 4}Co(PO{sub 4}){sub 2} with temperature has been elucidated. The crystal structure of its {alpha}-phase was determined from single crystal data, HT-XRPD allowed derivation of a structure model for the {beta}-phase. Both

  9. Three-dimensional frameworks of cubic (NH{sub 4}){sub 5}Ga{sub 4}SbS{sub 10}, (NH{sub 4}){sub 4}Ga{sub 4}SbS{sub 9}(OH) {small _bullet} H{sub 2}O, and (NH{sub 4}){sub 3}Ga{sub 4}SbS{sub 9}(OH{sub 2}) {small_bullet} 2H{sub 2}O.

    SciTech Connect

    Mertz, J. L.; Ding, N.; Kanatzidis, M. G.


    Three new isostructural open-framework sulfides, (NH{sub 4}){sub 5}Ga{sub 4}SbS{sub 10} (1), (NH{sub 4}){sub 4}Ga{sub 4}SbS{sub 9}(OH) {sm_bullet} H{sub 2}O (2a), and (NH{sub 4}){sub 3}Ga{sub 4}SbS{sub 9}(H{sub 2}O) {sm_bullet} 2H{sub 2}O (2b), were synthesized under basic hydrothermal conditions using ammonium hydroxide as the structure-directing agent. The structures feature a three-dimensional open framework comprised of adamantane [Ga{sub 4}Q{sub 10}]{sup 8-} clusters linked with Sb{sup 3+} centers. The compounds are wide gap semiconductors, crystallize in the chiral space group P2{sub 1}3, and represent a new structure type. They exhibit nonlinear optical properties.

  10. Exchange bias effect in Au-Fe3O4sub> dumbbell nanoparticles induced by the charge transfer from gold

    SciTech Connect

    Feygenson, Mikhail; Bauer, John C; Gai, Zheng; Marques, Carlos; Aronson, Meigan C.; Teng, Xiaowei; Su, Dong; Stanic, Vesna; Urban, Volker S; Kevin, Beyer; Dai, Sheng


    We have studied the origin of the exchange bias effect in the Au-Fe3O4sub> dumbbell nanoparticles in two samples with different sizes of the Au seed nanoparticles (4.1 and 2.7 nm) and same size of Fe3O4sub> nanoparticles (9.8 nm). The magnetization, small-angle neutron scattering, synchrotron x-ray diffraction and scanning transmission electron microscope measurements determined the antiferromagnetic FeO wüstite phase within Fe3O4sub> nanoparticles, originating at the interface with the Au nanoparticles. The interface between antiferromagnetic FeO and ferrimagnetic Fe3O4sub> is giving rise to the exchange bias effect. The strength of the exchange bias fields depends on the interfacial area and lattice mismatch between both phases. We propose that the charge transfer from the Au nanoparticles is responsible for a partial reduction of the Fe3O4sub> into FeO phase at the interface with Au nanoparticles. The Au-O bonds are formed across the interface to accommodate an excess of oxygen released during the reduction of magnetite.

  11. CuCo2O4sub> ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

    SciTech Connect

    Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; Matanovic, Ivana; Artyushkova, Kateryna; Atanassov, Plamen


    A series of CuCo2O4sub> catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo2O4sub> and it was found that CuCo2O4 sub>can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It was found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo2O4sub>. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E1/2) of CuCo2O4sub>-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.

  12. Microwave-assisted preparation of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C composite with high-rate capacity

    SciTech Connect

    Yan, Ji; Mao, Wen-feng; Xie, Hui; Tang, Zhi-yuan; Yuan, Wei; Chen, Xue-cheng; Xu, Qiang; Ma, Li


    Highlights: ► High-rate Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C is firstly reported via a microwave-assisted method. ► The reduced particle size is responsible for the improved high-rate performance. ► A discharge capacity of 100 mAh g{sup −1} is obtained at 20 C charge–discharge rate. -- Abstract: A fast sol–gel assisted microwave heating approach has been developed for the synthesis of high-rate Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathode material. This approach can synthesize Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C particles with high purity and good crystallinity in 12 min at a low microwave power of 320 W. In the voltage range of 3.0–4.3 V, the obtained Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C delivers a reversible discharge capacity of 100 mAh g{sup −1} after 100 cycles at 20 °C, exhibiting excellent rate capability and cycling performance. The rate-recovery performance also suggests that the Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C material possesses excellent structure stability after high-rate cycles, presenting excellent application value in high-power lithium ion batteries.

  13. Structural features of AgCaCdMg{sub 2}(PO{sub 4}){sub 3} and AgCd{sub 2}Mg{sub 2}(PO{sub 4}){sub 3}, two new compounds with the alluaudite-type structure, and their catalytic activity in butan-2-ol conversion

    SciTech Connect

    Kacimi, Mohammed; Ziyad, Mahfoud; Hatert, Frederic . E-mail:


    AgCaCdMg{sub 2}(PO{sub 4}){sub 3} and AgCd{sub 2}Mg{sub 2}(PO{sub 4}){sub 3}, two new compounds with the alluaudite-type structure, were synthesized by a solid state reaction in air at 750 deg. C. The X-ray powder diffraction pattern of AgCaCdMg{sub 2}(PO{sub 4}){sub 3} indicates the presence of small amounts of (Ca, Mg){sub 3}(PO{sub 4}){sub 2} with the whitlockite structure, as impurity, whereas AgCd{sub 2}Mg{sub 2}(PO{sub 4}){sub 3} is constituted by pure alluaudite. The Rietveld refinements of the X-ray powder diffraction patterns indicate an ordered cationic distribution for AgCd{sub 2}Mg{sub 2}(PO{sub 4}){sub 3}, with Ag on A(2)', Cd on A(1) and M(1), and Mg on M(2), whereas a disordered distribution of Cd and Ca between the A(1) and M(1) sites is observed for AgCaCdMg{sub 2}(PO{sub 4}){sub 3}. The catalytic properties of these compounds has been measured in reaction of butan-2-ol dehydrogenation. In the absence of oxygen, both samples exhibit poor dehydrogenation activity. All samples displayed no dehydration activity. Introduction of oxygen into the feed changed totally the catalytic behavior of the catalysts. The production of methyl ethyl ketone increases with time on stream and the reaction temperature. AgCaCdMg{sub 2}(PO{sub 4}){sub 3} is more efficient than AgCd{sub 2}Mg{sub 2}(PO{sub 4}){sub 3}.

  14. X-ray and Neutron Diffraction Studies of Rb{sub 4}LiH{sub 3}(XO{sub 4}){sub 4} (X = S, Se) Single Crystals

    SciTech Connect

    Troyanov, S.I.; Snigireva, E.M.; Ling, C.D.


    Rb{sub 4}LiH{sub 3}(SeO{sub 4}){sub 4} single crystals (1) are studied by the X-ray diffraction method at 180 K and Rb{sub 4}LiH{sub 3}(SO{sub 4}){sub 4} single crystals (2a-2c) are studied by the neutron diffraction method at 298 K (2a and 2b) and 480 K (2c). It is established that isostructural single crystals 1 and 2 (sp. gr. P4{sub 1}) have analogous systems of hydrogen bonds: chains of four XO{sub 4} tetrahedra linked by three H bonds with the central bond (2.49 A) being somewhat shorter than the terminal ones (2.52-2.54 A). In the high-temperature 2c phase, the amplitudes of atomic thermal vibrations and the degree of proton disorder in the central hydrogen bond have somewhat elevated values.

  15. Mechanism of the low thermal expansion in {alpha}-Hf{sub 2}O(PO{sub 4}){sub 2} and its zirconium analog

    SciTech Connect

    Wallez, Gilles Bregiroux, Damien; Quarton, Michel


    The thermal expansion of recently characterized {alpha}-Zr{sub 2}O(PO{sub 4}){sub 2} and {alpha}-Hf{sub 2}O(PO{sub 4}){sub 2} is found to be very low (respectively 2.6 and 2.9x10{sup -6} K{sup -1}, 20-900 deg. C). High-temperature X-ray diffraction and Rietveld analysis allowed to identify a dual contraction mechanism, involving a classical ring deformation and the rocking of bridging oxygens. - Graphical abstract: Compared to other zirconium phosphates, {alpha}-Zr{sub 2}O(PO{sub 4}){sub 2} shows a remarkable low thermal expansion of 2.6x10{sup -6} K{sup -1}.

  16. Nonperturbative tests for asymptotic freedom in the PT-symmetric (-{phi}{sup 4}){sub 3+1} theory

    SciTech Connect

    Shalaby, Abouzeid; Al-Thoyaib, Suleiman S.


    In the literature, the asymptotic freedom property of the (-{phi}{sup 4}) theory is always concluded from real-line calculations while the theory is known to be a non-real-line one. In this article, we test the existence of the asymptotic freedom in the (-{phi}{sup 4}){sub 3+1} theory using the mean field approach. In this approach and contrary to the original Hamiltonian, the obtained effective Hamiltonian is rather a real-line one. Accordingly, this work resembles the first reasonable analysis for the existence of the asymptotic freedom property in the PT-symmetric (-{phi}{sup 4}) theory. In this respect, we calculated three different amplitudes of different positive dimensions (in mass units) and find that all of them go to very small values at high energy scales (small coupling) in agreement with the spirit of the asymptotic freedom property of the theory. To test the validity of our calculations, we obtained the asymptotic behavior of the vacuum condensate in terms of the coupling, analytically, and found that the controlling factor {Lambda} has the value ((4{pi}){sup 2}/6)=26.319 compared to the result {Lambda}=26.3209 from the literature, which was obtained via numerical predictions. We assert that the nonblowup of the massive quantities at high energy scales predicted in this work strongly suggests the possibility of the solution of the famous hierarchy puzzle in a standard model with the PT-symmetric Higgs mechanism.

  17. Spectral properties of Tm{sup 3+}:NaGd(MoO{sub 4}){sub 2} crystal

    SciTech Connect

    Wang Zujian; Li Xiuzhi; Wei Qian; Long Xifa


    The Tm{sup 3+}:NaGd(MoO{sub 4}){sub 2} crystal with dimensions of {phi} 15 x 38 mm{sup 2} was grown by Czochralski method. Polarized absorption and fluorescence spectra at room temperature were investigated. The absorption bands attributed to {sup 3}H{sub 6} {yields} {sup 3}H{sub 4} transition have large absorption cross-sections, which are 3.99 x 10{sup -20} and 2.36 x 10{sup -20} cm{sup 2} for {sigma}- and {pi}-polarization, respectively. The emission bands corresponding to the {sup 3}H{sub 4} {yields} {sup 3}H{sub 6} transition are strong and broad with emission cross-sections of 1.33 x 10{sup -20} and 1.20 x 10{sup -20} cm{sup 2} for {sigma}- and {pi}-polarization, respectively. The correlative full widths at half maximum are 35 nm for {sigma}-polarization and 36 nm for {pi}-polarization. The fluorescence lifetime for the {sup 3}H{sub 4} {yields} {sup 3}F{sub 4} transition is 146 {mu}s and the luminescent quantum efficiency is 76.8%.

  18. SU(4){sub L} x U(1){sub X} three-family model for the electroweak interaction

    SciTech Connect

    Sanchez, Luis A.; Wills-Toro, Luis A.; Zuluaga, Jorge I.


    An extension of the gauge group SU(2){sub L} x U(1){sub Y} of the standard model to the symmetry group SU(4){sub L} x U(1){sub X} (3-4-1 for short) is presented. The model does not contain exotic electric charges and anomaly cancellation is achieved with a family of quarks transforming differently from the other two, thus leading to FCNC. By introducing a discrete Z{sub 2} symmetry we obtain a consistent fermion mass spectrum, and avoid unitarity violation of the Cabibbo-Kobayashi-Maskawa mixing matrix arising from the mixing of ordinary and exotic quarks. The neutral currents coupled to all neutral vector bosons are studied, and by using CERN LEP and SLAC Linear Collider data at Z-pole and atomic parity violation data, we bound parameters of the model related to tree-level Z-Z{sup '} mixing. These parameters are further constrained by using experimental input from neutral meson mixing in the analysis of sources of FCNC present in the model. Constraints coming from the contribution of exotic particles to the one-loop oblique electroweak parameters S, T and U are also briefly discussed. Finally, a comparison is done of the predictions of different classes of 3-4-1 models without exotic electric charges.

  19. Compact KGd(WO4sub>)2 picosecond pulse-train synchronously pumped broadband Raman laser.


    Gao, Xiao Qiang; Long, Ming Liang; Meng, Chen


    We demonstrate an efficient approach to realizing an extra-cavity, synchronously pumped, stimulated Raman cascaded process under low repetition frequency (1 kHz) pump conditions. We also construct a compact KGd(WO4sub>)2 (KGW) crystal picosecond Raman laser that has been configured as the developed method. A pulse-train green laser pumped the corresponding 70 mm long KGW crystal Raman cavity. The pulse train contains six pulses, about 800 ps separated, for every millisecond; thus, it can realize synchronous pumping between pump pulse and the pumped Raman cavity. The investigated system produced a collinear Raman laser output that includes six laser lines covering the 532 to 800 nm spectra. This is the first report on an all-solid-state, high-average-power picosecond collinear multi-wavelength (more than three laser components) laser to our knowledge. This method has never been reported on before in the synchronously pumped stimulated Raman scattering (SRS) realm. PMID:27556971

  20. Magnetic susceptibility, specific heat and magnetic structure of CuNi{sub 2}(PO{sub 4}){sub 2}

    SciTech Connect

    Escobal, Jaione; Pizarro, Jose L.; Mesa, Jose L. . E-mail:; Larranaga, Aitor; Fernandez, Jesus Rodriguez; Arriortua, Maria I.; Rojo, Teofilo


    CuNi{sub 2}(PO{sub 4}){sub 2} phosphate has been synthesized by the ceramic method at 800 deg. C in air. The crystal structure consists of a three-dimensional skeleton constructed from MO{sub 4} (M{sup II} =Cu and Ni) planar squares and M{sub 2}O{sub 8} dimers with square pyramidal geometry, which are interconnected by (PO{sub 4}){sup 3-} oxoanions with tetrahedral geometry. The magnetic behavior has been studied on powdered sample by using susceptibility, specific heat and neutron diffraction data. The bimetallic copper(II)-nickel(II) orthophosphate exhibits a three-dimensional magnetic ordering at, approximately, 29.8 K. However, its complex crystal structure hampers any parametrization of the J-exchange parameter. The specific heat measurements exhibit a three-dimensional magnetic ordering ({lambda}-type) peak at 29.5 K. The magnetic structure of this phosphate shows ferromagnetic interactions inside the Ni{sub 2}O{sub 8} dimers, whereas the sublattice of Cu(II) ions presents antiferromagnetic couplings along the y-axis. The change of the sign in the magnetic unit-cell, due to the [1/2, 0, 1/2] propagation vector determines a purely antiferromagnetic structure. - Graphical abstract: Magnetic structure of CuNi2(PO4)2.

  1. Controllable synthesis and down-conversion properties of flower-like NaY(MoO{sub 4}){sub 2} microcrystals via polyvinylpyrrolidone-mediated

    SciTech Connect

    Lin, Han; Yan, Xiaohong; Wang, Xiangfu


    Double alkaline rare-earth molybdates NaY(MoO{sub 4}){sub 2} with multilayered flower-like architectures have been successfully synthesized via hydrothermal method in polyvinylpyrrolidone (PVP)-modified processes. The crystal structure and morphology of the obtained products were characterized by X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that reaction time and the amount of PVP have crucial influences on the morphology of the resulting novel microstructures. Under 450 nm excitation, Ho{sup 3+}/Yb{sup 3+} co-doped NaY(MoO{sub 4}){sub 2} samples exhibit 539 nm green emission and 960–1200 nm broadband near-infrared emission, corresponding to the characteristic lines of Ho{sup 3+} and Yb{sup 3+}, respectively. Moreover, increasing Yb{sup 3+} doping enhances the energy transfer efficiency from Ho{sup 3+} to Yb{sup 3+}. - Graphical abstract: Low and high-magnification SEM images demonstrate the perfect flower-like NaY(MoO{sub 4}){sub 2} prepared in the presence of PVP; Detailed TEM and HRTEM images further manifest the single-crystalline feature. Highlights: • NaY(MoO{sub 4}){sub 2} flower-like microstructures were synthesized by hydrothermal method using polyvinylpyrrolidone. • Polyvinylpyrrolidone induces the growth of the NaY(MoO{sub 4}){sub 2} to form multilayered architectures. • Flowerlike NaY(MoO{sub 4}){sub 2}: Ho{sup 3+}, Yb{sup 3+} phosphors were investigated as a downconversion layer candidate.

  2. Oxygen trapped by rare earth tetrahedral clusters in Nd4sub>FeOS6: Crystal structure, electronic structure, and magnetic properties

    SciTech Connect

    Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; Wood, Max; Drtina, Thomas; Bud’ko, Sergey L.; Canfield, Paul C.; Miller, Gordon J.


    Single crystals of Nd4sub>FeOS6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd4sub>MnOSe6-type structure (P63mc, a = 9.2693(1) Å, c = 6.6650(1) Å, V = 495.94(1) Å3, Z = 2), featuring parallel chains of face-sharing [FeS6x1/2]4- trigonal antiprisms and interlinked [Nd4sub>OS3]4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd4 clusters in the [Nd4OS3]4+ chains. Structural differences among Nd4sub>MnOSe6-type Nd4sub>FeOS6 and the related La3CuSiS7- and Pr8CoGa3-type structures have been described. Magnetic susceptibility measurements on Nd4sub>FeOS6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.

  3. High power, diffraction limited picosecond oscillator based on Nd:GdVO4sub> bulk crystal with σ polarized in-band pumping.


    Lin, Hua; Guo, Jie; Gao, Peng; Yu, Hai; Liang, Xiaoyan


    We report on a high power passively mode-locked picosecond oscillator based on Nd:GdVO4sub> crystal with σ polarized in-band pumping. Thermal gradient and thermal aberration was greatly decreased with proposed configuration. Maximum output power of 37 W at 81 MHz repetition rate with 19.3 ps pulse duration was achieved directly from Nd:GdVO4sub> oscillator, corresponding to 51% optical efficiency. The oscillator maintained diffraction limited beam quality of M2 < 1.05 at different output coupling with pulse duration between 11.2 ps to 19.3 ps. PMID:27410558

  4. Photoluminescence and thermoluminescence properties of Tb{sup 3+} doped K{sub 3}Gd(PO{sub 4}){sub 2} nanophosphor

    SciTech Connect

    Gupta, Palvi; Bedyal, A.K.; Kumar, Vinay; Khajuria, Y.; Lochab, S.P.; Pitale, S.S.; Ntwaeaborwa, O.M.; Swart, H.C.


    Energy level diagram of Tb{sup 3+} ion in the K{sub 3}Gd(PO{sub 4}){sub 2} host lattice. - Highlights: • First time, a detailed TL and PL study on undoped and Tb{sup 3+} doped K{sub 3}Gd(PO{sub 4}){sub 2} nanophosphor. • Combustion method was employed to synthesize the Tb{sup 3+} doped K{sub 3}Gd(PO{sub 4}){sub 2} nanophosphor. • Mechanism of excitation and emission in undoped and Tb{sup 3+} doped K{sub 3}Gd(PO{sub 4}){sub 2} nanophosphor was given. - Abstract: Tb{sup 3+} doped nanoparticulate K{sub 3}Gd(PO{sub 4}){sub 2} phosphor was prepared by combustion method using urea as a fuel. The structure, optical and luminescent properties of the phosphor were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and thermoluminescence (TL) spectroscopy. In undoped K{sub 3}Gd(PO{sub 4}){sub 2}, the excitation and emission peaks at 273 nm and 323 nm belongs to the {sup 8}S{sub 7/2} → {sup 6}I{sub J(J=7/2)} and {sup 6}P{sub J(J=7/2)} → {sup 8} S{sub 7/2} transitions of Gd{sup 3+} while green emission was observed in the Tb{sup 3+} doped K{sub 3}Gd(PO{sub 4}){sub 2}. TL study was carried out after exposing the samples to γ-radiations (0.1–5 kGy) in the K{sub 3}Gd(PO{sub 4}){sub 2}:Tb{sup 3+} (1.5 mol%). The calculated kinetic parameters were compared with different methods. The band gap of the phosphor was estimated as 5.80 eV. The green shade of the Tb{sup 3+} ion with the CIE coordinates (x, y) as (0.29, 0.54) was in good agreement with the well known green phosphors.

  5. Calculation of enthalpies of formation of compounds of the type M/sub 5/R(EO/sub 4/)/sub 4/

    SciTech Connect

    Kaganyuk, D.S.; Perepelitsa, A.P.


    Enthalpies of formation were determined for compounds of the M/sub 5/R(EO/sub 4/)/sub 4/ type, where M = Li, Na, K, Rb, Cs, Fr, Tl, Ag, Cu; R = the rare earth elements, y, Bi; and E = Mo, W. Values of 0/, either experimentally determined or estimated by any quantum-chemical methods, are absent in the literature for these compounds. The obtained values of lambdaHf/sup 0/ for M/sub 5/R(EO/sub 4/)/sub 4/ are presented.

  6. Synthesis, crystal structure and spectroscopy properties of Na{sub 3} AZr(PO{sub 4}){sub 3} (A=Mg, Ni) and Li{sub 2.6}Na{sub 0.4}NiZr(PO{sub 4}){sub 3} phosphates

    SciTech Connect

    Chakir, M. . E-mail:; El Jazouli, A.; Waal, D. de


    Na{sub 3} AZr(PO{sub 4}){sub 3} (A=Mg, Ni) phosphates were prepared at 750 deg. C by coprecipitation route. Their crystal structures have been refined at room temperature from X-ray powder diffraction data using Rietveld method. Li{sub 2.6}Na{sub 0.4}NiZr(PO{sub 4}){sub 3} was synthesized through ion exchange from the sodium analog. These materials belong to the Nasicon-type structure. Raman spectra of Na{sub 3} AZr(PO{sub 4}){sub 3} (A=Mg, Ni) phosphates present broad peaks in favor of the statistical distribution in the sites around PO{sub 4} tetrahedra. Diffuse reflectance spectra indicate the presence of octahedrally coordinated Ni{sup 2+} ions. - Graphical abstract: Structure of Na{sub 3} AZr(PO{sub 4}){sub 3} (A=Mg, Ni) phosphates. Display Omitted.

  7. Magnetic structures of R5Ni2In4sub> and R11Ni4sub>In9 ( R = Tb and Ho): Strong hierarchy in the temperature dependence of the magnetic ordering in the multiple rare-earth sublattices

    SciTech Connect

    Ritter, C.; Provino, A.; Manfrinetti, P.; Pecharsky, V. K.; Gschneidner, Jr., K. A.; Dhar, S. K.


    In this study, the magnetic properties and magnetic structures of the R5Ni2In4sub> and the microfibrous R 11Ni4sub>In9 compounds with R = Tb and Ho have been examined using magnetization, heat capacity, and neutron diffraction data. Rare earth atoms occupy three and five symmetrically inequivalent rare earth sites in R5Ni2In4sub> and R 11Ni4sub>In9 compounds, respectively. As a result of the intra- and inter-magnetic sublattice interactions, the magnetic exchange interactions are different for various rare earth sites; this leads to a cascade of magnetic transitions with a strong hierarchy in the temperature dependence of the magnetic orderings.

  8. Phase transition and multicolor luminescence of Eu{sup 2+}/Mn{sup 2+}-activated Ca{sub 3}(PO{sub 4}){sub 2} phosphors

    SciTech Connect

    Li, Kai; Chen, Daqin; Xu, Ju; Zhang, Rui; Yu, Yunlong; Wang, Yuansheng


    Graphical abstract: We have synthesized Eu{sup 2+} doped and Eu{sup 2+}/Mn{sup 2+} co-doped Ca{sub 3}(PO{sub 4}){sub 2} phosphors. The emitting color varies from blue to green with increasing of Eu{sup 2+} content for the Eu{sup 2+}-doped phosphor, and the quantum yield of the 0.05Eu{sup 2+}: Ca{sub 2.95}(PO{sub 4}){sub 2} sample reaches 56.7%. Interestingly, Mn{sup 2+} co-doping into Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} leads to its phase transition from orthorhombic to rhombohedral, and subsequently generates tunable multi-color luminescence from green to red via Eu{sup 2+} → Mn{sup 2+} energy transfer. - Highlights: • A series of novel Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} phosphors were successfully synthesized. • Phase transition of Ca{sub 3}(PO{sub 4}){sub 2} from orthorhombic to rhombohedral occurred when Mn{sup 2+} ions were doped. • The phosphors exhibited tunable multi-color luminescence. • The quantum yield of 0.05Eu{sup 2+}: Ca{sub 2.95}(PO{sub 4}){sub 2} phosphor can reach 56.7%. • The analyses of phosphors were carried out by many measurements. - Abstract: Intense blue-green-emitting Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} and tunable multicolor-emitting Eu{sup 2+}/Mn{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} phosphors are prepared via a solid-state reaction route. Eu{sup 2+}-doped orthorhombic Ca{sub 3}(PO{sub 4}){sub 2} phosphor exhibits a broad emission band in the wavelength range of 400–700 nm with a maximum quantum yield of 56.7%, and the emission peak red-shifts gradually from 479 to 520 nm with increase of Eu{sup 2+} doping content. Broad excitation spectrum (250–420 nm) of Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} matches well with the near-ultraviolet LED chip, indicating its potential applications as tri-color phosphors in white LEDs. Interestingly, Mn{sup 2+} co-doping into Eu{sup 2+}: Ca{sub 3}(PO{sub 4}){sub 2} leads to its phase transition from orthorhombic to rhombohedral, and subsequently generates tunable multi

  9. Trivalent aluminum ion conducting characteristics in Al{sub 2}(WO{sub 4}){sub 3} single crystals

    SciTech Connect

    Imanaka, N.; Tamura, S.; Hiraiwa, M.; Adachi, G.; Dabkowska, H.; Dabkowski, A.; Greedan, J.E.


    Single crystals of the trivalent Al{sup 3+} ion conductor Al{sub 2}(WO{sub 4}){sub 3} were grown by the Czochralski (CZ) method. The ionic conductivity in the a-, b-, and c-axis directions was determined and Al{sup 3+} ion conduction in the direction of the b-axis was concluded to be the most suitable pathway for ion migration in the tungstate grains. The ionic conductivities in the a- and c-axis directions were 0.3 and 10{sup {minus}2} times lower than the conductivity in the b-axis. Consistent with this observation, the lowest activation energy (E{sub a}) for Al{sup 3+} ion migration was obtained for the b-axis direction. The E{sub a} of the conductivity in the direction of the c-axis was almost comparable to that of the polycrystalline samples and the E{sub a} of the Al{sup 3+} ionic conduction in the grains of this material was explicitly verified to be controlled by the Al{sup 3+} ionic migration in the c-axis direction. The Al{sup 3+} ion conductivity of the polycrystalline sample was higher in the higher temperature region, indicating that the conductivity in the grain boundaries enhances the total Al{sup 3+} ion conductivity to a considerable extent. From the oxygen pressure dependencies of the electrical conductivity and the polarization behavior, the single crystals were demonstrated to be pure Al{sup 3+} ionic conductors showing an anisotropic ion conducting behavior.

  10. Highly Selective Colorimetric and Luminescence Response of a Square-Planar Platinum(II) Terpyridyl Complex to Aqueous TcO4sub>-

    SciTech Connect

    Chatterjee, Sayandev; Norton, Amie E.; Edwards, Matthew K.; Peterson, James M.; Taylor, Stephen D.; Bryan, Samuel A.; Andersen, Amity; Govind, Niranjan; Albrecht-Schmitt, Thomas E.; Connick, William; Levitskaia, Tatiana G.


    In an effort to address the need for a rapid, selective and economical detection technique for aqueous pertechnetate (TcO4sub>-) anion based on recognition at the molecular level, simple salts of transition metal complexes that undergo a distinct spectroscopic change upon exposure to aqueous anions were explored. The Pt(II) complex [Pt(tpy)Br]SbF6 (tpy=2,2';6',2"-terpyridine) undergoes a dramatic color change and intense luminescence response upon TcO4sub>- uptake due to concomitant enhancement of Pt•••Pt interactions. The spectroscopic response was highly selective and quantitative for aqueous TcO4sub>- among other competing anions. Complimentary Raman spectroscopy and microscopy techniques, structural determination and theoretical methods were employed to achieve molecular-level understanding of the mechanism of the response to aqueous TcO4sub>-.

  11. Low Temperature Propane Oxidation over Co3O4sub> based Nano-array Catalysts. Ni Dopant Effect, Reaction Mechanism and Structural Stability

    SciTech Connect

    Ren, Zheng; Wu, Zili; Gao, Puxian; Song, Wenqiao; Xiao, Wen; Guo, Yanbing; Ding, Jun; Suib, Steven L.; Gao, Pu-Xian


    Low temperature propane oxidation has been achieved by Co3O4sub>-based nano-array catalysts featuring low catalytic materials loading. The Ni doping into the Co3O4sub> lattice has led to enhanced reaction kinetics at low temperature by promoting the surface lattice oxygen activity. In situ DRIFTS investigation in tandem with isotopic oxygen exchange reveals that the propane oxidation proceeds via Mars-van Krevelen mechanism where surface lattice oxygen acts as the active site whereas O2 in the reaction feed does not directly participate in CO2 formation. The Ni doping promotes the formation of less stable carbonates on the surface to facilitate the CO2 desorption. The thermal stability of Ni doped Co3O4sub> decreases with increased Ni concentration while catalytic activity increases. A balance between enhanced activity and compromised thermal stability shall be considered in the Ni doped Co3O4sub> nano-array catalysts for low temperature hydrocarbon oxidation. This study provides useful and timely guidance for rational catalyst design toward low temperature catalytic oxidation.

  12. Ionic conductivity and the formation of cubic CaH{sub 2} in the LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composite

    SciTech Connect

    Sveinbjörnsson, Dadi; Blanchard, Didier; Myrdal, Jon Steinar Gardarsson; Younesi, Reza; Viskinde, Rasmus; Riktor, Marit Dalseth; Norby, Poul; Vegge, Tejs


    LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composites were prepared by ball milling. Their crystal structures and phase composition were investigated using synchrotron X-ray diffraction and Rietveld refinement, and their ionic conductivity was measured using impedance spectroscopy. The materials were found to form a physical mixture. The composites were composed of α-Ca(BH{sub 4}){sub 2}, γ-Ca(BH{sub 4}){sub 2} and orthorhombic LiBH{sub 4}, and the relative phase quantities of the Ca(BH{sub 4}){sub 2} polymorphs varied significantly with LiBH{sub 4} content. The formation of small amounts of orthorhombic CaH{sub 2} and cubic CaH{sub 2} in a CaF{sub 2}-like structure was observed upon heat treatment. Concurrent formation of elemental boron may also occur. The ionic conductivity of the composites was measured using impedance spectroscopy, and was found to be lower than that of ball milled LiBH{sub 4}. Electronic band structure calculations indicate that cubic CaH{sub 2} with hydrogen defects is electronically conducting. Its formation along with the possible precipitation of boron therefore has an effect on the measured conductivity of the LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composites and may increase the risk of an internal short-circuit in the cells. -- Graphical abstract: An Arrhenius plot of the ionic conductivity of the LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composites (red, blue, green). The ionic conductivity of ball milled (gray) and non-milled (black) LiBH{sub 4} is shown for comparison. The filled symbols are measured during heating runs and the empty symbols are measured during subsequent cooling runs. The conductivity of the composites is in all cases higher during cooling, most probably due to the formation of an electronically conducting layer containing defect-rich cubic CaH{sub 2}. Such layer formation could eventually lead to a short circuit in the cell and reveals a general issue of chemical stability that should be attended to in the development of solid

  13. A novel red long lasting phosphorescent (LLP) material {beta}-Zn{sub 3}(PO{sub 4}){sub 2}:Mn{sup 2+}, Sm{sup 3+}

    SciTech Connect

    Wang Jing; Su Qiang . E-mail:; Wang Shubin


    A novel red long lasting phosphorescent materials {beta}-Zn{sub 3}(PO{sub 4}){sub 2}:Mn{sup 2+},Sm{sup 3+} is firstly synthesized by high-temperature solid-state reaction. The influence of Sm{sup 3+} ions on luminescence and long lasting phosphorescence properties of Mn{sup 2+} in phosphor {beta}-Zn{sub 3}(PO{sub 4}){sub 2}:Mn{sup 2+},Sm{sup 3+} are systematically investigated. It is found that the red phosphorescence ({lambda} = 616 nm) performance of Mn{sup 2+} ion such as brightness and duration is largely improved when Sm{sup 3+} ion is co-doped into the matrix in which Mn{sup 2+} ion acts as luminescent center and Sm{sup 3+} ion plays an important role of electron trap. Thermoluminescence spectrums show that there exists one peak in {beta}-Zn{sub 3}(PO{sub 4}){sub 2}:Mn{sup 2+},Sm{sup 3+}, the depth of which is 0.33 eV, and that there are three peaks in {beta}-Zn{sub 3}(PO{sub 4}){sub 2}:Mn{sup 2+}, among which the depth of the lowest temperature peak in {beta}-Zn{sub 3}(PO{sub 4}){sub 2}:Mn{sup 2+} is 0.37 eV. Such differences in the trap depth result in the improvement of red long lasting phosphorescence of Mn{sup 2+} in present matrix.

  14. Syntheses, crystal structures and optical spectroscopy of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O

    SciTech Connect

    Kazmierczak, Karolina; Hoeppe, Henning A.


    The lanthanide sulphate octahydrates Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and the respective tetrahydrate Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a{sub Ho}=13.4421(4) A, b{sub Ho}=6.6745(2) A, c{sub Ho}=18.1642(5) A, {beta}{sub Ho}=102.006(1) A{sup 3} and a{sub Tm}=13.4118(14) A, b{sub Tm}=6.6402(6) A, c{sub Tm}=18.1040(16) A, {beta}{sub Tm}=101.980(8) A{sup 3}), Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O adopts space group P2{sub 1}/n (a=13.051(3) A, b=7.2047(14) A, c=13.316(3) A, {beta}=92.55(3) A{sup 3}). The vibrational and optical spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O are also reported. -- Graphical abstract: In the lanthanide sulphate octahydrates the cations form slightly undulated layers. Between the layers are voids in which sulphate tetrahedra and water molecules are located. The holmium compound exhibits an Alexandrite effect. Display Omitted Highlights: {yields} Determination of the optimum conditions for the growth of single-crystals of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O. {yields} Single-crystal structure elucidation of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) including hydrogen bonds. {yields} Single-crystal structure determination of Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O including hydrogen bonds. {yields} UV-vis spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted: Assignation of bands and clarification of the Alexandrite effect of the Ho compound. {yields} IR and Raman spectra of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted.

  15. Structural study and physical properties of a new phosphate KCuFe(PO{sub 4}){sub 2}

    SciTech Connect

    Badri, Abdessalem; Hidouri, Mourad; Lopez, Maria Luisa; Pico, Carlos; Wattiaux, Alain; Ben Amara, Mongi


    Single crystals of a new phosphate KCuFe(PO{sub 4}){sub 2} have been prepared by the flux method and its structural and physical properties have been investigated. This compound crystallizes in the monoclinic system with the space group P2{sub 1}/n and its parameters are: a=7.958(3) A, b=9.931(2) A, c=9.039(2) A, {beta}=115.59(3){sup o} and Z=4. Its structure consists of FeO{sub 6} octahedra sharing corners with Cu{sub 2}O{sub 8} units of edge-sharing CuO{sub 5} polyhedra to form undulating chains extending infinitely along the b-axis. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the K{sup +} ions are located. The Moessbauer spectroscopy results confirm the exclusive presence of octahedral Fe{sup 3+} ions. The magnetic measurements show the compound to be antiferromagnetic with C{sub m}=5.71 emu K/mol and {theta}=-156.5 K. The derived experimental effective moment {mu}{sub ex}=6.76{mu}{sub B} is somewhat higher than the theoretical one of {mu}{sub th}=6.16{mu}{sub B}, calculated taking only into account the spin contribution for Fe{sup 3+} and Cu{sup 2+} cations. Electrical measurements allow us to obtain the activation energy (1.22 eV) and the conductivity measurements suggest that the charge carriers through the structure are the potassium cations. -- Graphical abstract: A projection along the [101] direction of the structure showing the six-edged tunnels, occupied by the K{sup +} ions. Display Omitted Highlights: {yields} The reported structure is of a new type. {yields} The structural model is supported by a Moessbauer spectroscopy study. {yields} The magnetic susceptibility results are reported. {yields} The electrical properties are discussed.

  16. Combustion synthesized nanocrystalline Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathode for lithium-ion batteries

    SciTech Connect

    Nathiya, K.; Bhuvaneswari, D.; Gangulibabu; Kalaiselvi, N.


    Graphical abstract: Nanocrystalline Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C compound has been synthesized using a novel corn assisted combustion (CAC) method, wherein the composite prepared at 850 °C is found to exhibit superior physical and electrochemical properties than the one synthesized at 800 °C (Fig. 1). Despite the charge disproportionation of V{sup 4+} and a possible solid solution behavior of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} cathode upon insertion and de-insertion of Li{sup +} ions, the structural stability of the same is appreciable, even with the extraction of third lithium at 4.6 V (Fig. 2). An appreciable specific capacity of 174 mAh g{sup −1} with an excellent columbic efficiency (99%) and better capacity retention upon high rate applications have been exhibited by Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathode, thus demonstrating the feasibility of CAC method in preparing the title compound to best suit with the needs of lithium battery applications. Display Omitted Highlights: ► Novel corn assisted combustion method has been used to synthesize Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C. ► Corn is a cheap and eco benign combustible fuel to facilitate CAC synthesis. ► Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C exhibits an appreciable specific capacity of 174 mAh g{sup −1} (C/10 rate). ► Currently observed columbic efficiency of 99% is better than the reported behavior. ► Suitability of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathode up to 10C rate is demonstrated. -- Abstract: Nanocrystalline Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C composite synthesized using a novel corn assisted combustion method at 850 °C exhibits superior physical and electrochemical properties than the one synthesized at 800 °C. Despite the charge disproportionation of V{sup 4+} and a possible solid solution behavior of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} cathode upon insertion and extraction of Li{sup +} ions, the structural stability of the same is appreciable, even with

  17. Structural, energetic and thermodynamic analyses of Ca(BH{sub 4}){sub 2}{center_dot}2NH{sub 3} from first principles calculations

    SciTech Connect

    Yuan Pengfei; Wang Fei; Sun Qiang; Jia Yu; Guo Zhengxiao


    Ca(BH{sub 4}){sub 2}{center_dot}2NH{sub 3} is a relatively new compound with potential application in hydrogen storage. Here the fundamental properties of the compound, such as electronic structure, energetic and thermodynamic properties, were comprehensively studied using first-principles calculations. Results from electronic density of states (DOS) and electron localization function (ELF) indicate the covalent bond nature of the N-H bond and the B-H bond. Charge density analyses show weak ionic interactions between the Ca atom and the NH{sub 3} complexes or the (BH{sub 4}){sup -} complexes. The calculated vibration frequencies of B-H and N-H are in good agreement with other theoretical and experimental results. Furthermore, we calculated the reaction enthalpy and reaction Gibbs free energy at a range of temperature 0-700 K. Our results are in good agreement with experimental results in literature. Possible reaction mechanism of the decomposition reaction is proposed. - Graphical Abstract: The crystal structure of this compound and the calculated decomposition reaction free energy for two different reactions: Reac(2):Ca(BH{sub 4}){sub 2} Dot-Operator 2NH{sub 3} Long-Rightwards-Arrow {sup 162 Degree-Sign C}Ca(BH{sub 4}){sub 2} Dot-Operator NH{sub 3}+NH{sub 3} Long-Rightwards-Arrow {sup 230 Degree-Sign C}Ca(BH{sub 4}){sub 2}+2NH{sub 3} Reac(3):Ca(BH{sub 4}){sub 2} Dot-Operator 2NH{sub 3} Long-Rightwards-Arrow {sup 190 Degree-Sign C}1/4Ca(BH{sub 4}){sub 2}+1/4Ca{sub 3}(BN{sub 2}){sub 2}+BN+6H{sub 2}. Highlights: Black-Right-Pointing-Pointer Crystal structure of this compound was studied in detail. Black-Right-Pointing-Pointer Electronic properties were calculated for the first time. Black-Right-Pointing-Pointer Phonon density of states and reaction free energy at different temperatures were first calculated. Black-Right-Pointing-Pointer Possible decomposition mechanism was presented.

  18. Structure symmetry determination and magnetic evolution in Sr2Ir1–xRhxO4sub>

    SciTech Connect

    Ye, Feng; Wang, Xiaoping; Hoffmann, Christina; Wang, Jinchen; Chi, Songxue; Matsuda, Masaaki; Chakoumakos, Bryan C.; Fernandez-Baca, Jaime A.; Cao, Gang


    We use single-crystal neutron diffraction to determine the crystal structure symmetry and to study the magnetic evolution in the rhodium doped iridates Sr2Ir1–xRhxO4sub> (0 ≤ x ≤ 0.16). Throughout this doping range, the crystal structure retains a tetragonal symmetry (space group I4<sub>1/a) with two distinct magnetic Ir sites in the unit cell forming staggered IrO6 rotation. Upon Rh doping, the magnetic order is suppressed and the magnetic moment of Ir4+ is reduced from 0.21 μB/Ir for x = 0 to 0.18 μB/Ir for x = 0.12. As a result, the magnetic structure at x = 0.12 is different from that of the parent compound while the moments remain in the basal plane.

  19. Neutron scattering studies of the H2a-H2b and (H3-H4)/sub 2/ histone complexes

    SciTech Connect

    Carlson, R.D.


    Neutron scattering experiments have shown that both the (H3-H4)/sub 2/ and H2a-H2b histone complexes are quite asymmetric in solution. The (H3-H4)/sub 2/ tetramer is an oblate or flattened structure, with a radius of gyration almost as large as that of the core octamer. If the tetramer is primarily globular, it must have an axial ratio of about 1:5. It is more likely, however, that this asymmetry results in part from N-terminal arms that extend outward approximately within the major plane of the particle. If this is the case, less asymmetric models for the globular part of the tetramer, including a dislocated disk, can be made consistent with the scattering data. The H2a-H2b dimer, on the other hand, is an elongated structure. 48 references, 12 figures, 1 table.

  20. Stabilization of heterogeneous silicon lasers using Pound-Drever-Hall locking to Si3N4sub> ring resonators.


    Spencer, Daryl T; Davenport, Michael L; Komljenovic, Tin; Srinivasan, Sudharsanan; Bowers, John E


    Recent results on heterogeneous Si/III-V lasers and ultra-high Q Si3N4sub> resonators are implemented in a Pound-Drever-Hall frequency stabilization system to yield narrow linewidth characteristics for a stable on-chip laser reference. The high frequency filtering is performed with Si resonant mirrors in the laser cavity. To suppress close in noise and frequency walk off, the laser is locked to an ultra-high Q Si3N4sub> resonator with a 30 million quality factor. The laser shows high frequency noise levels of 60 × 103 Hz2/Hz corresponding to 160 kHz linewidth, and the low frequency noise is suppressed 33 dB to 103 Hz2/Hz with the PDH system. PMID:27410367

  1. Structurally induced magnetization in a La2/3Sr4/3MnO4sub> superlattice

    SciTech Connect

    Shah, Amish B.; Nelson-Cheeseman, Brittany B.; Subramanian, Ganesh; Bhattacharya, Anand; Spence, John C.H.


    A structural transition has been observed in a digital superlattice of La2/3Sr4/3MnO4sub>, which is correlated to a magnetization enhancement upon cooling the sample. The artificial superlattices were grown layer-by-layer using ozone-assisted molecular beam epitaxy (MBE). Electron diffraction experiments show a phase transition below 150K in nanopatches of the superlattice, which coincides with an enhanced magnetization starting below 110K. Furthermore, atomic scale electron energy loss spectroscopy (EELS) shows changes in the Mn L2,3 and O K edges, which are related to valence, strain, and the atomic coordination within nanopatches. Atomic resolution image and EELS showing variations of oxygen and lanthanum signature edges in a La2/3Sr4/3MnO4sub> supperlattice.

  2. Theoretical Assessment on the Phase Transformation Kinetic Pathways of Multi-component Ti Alloys: Application to Ti-6Al-4sub>V

    SciTech Connect

    Ji, Yanzhou; Heo, Tae Wook; Zhang, Fan; Chen, Long-Qing


    Here we present our theoretical assessment of the kinetic pathways during phase transformations of multi-component Ti alloys. Employing the graphical thermodynamic approach and an integrated free energy function based on the realistic thermodynamic database and assuming that a displacive structural transformation occurs much faster than long-range diffusional processes, we analyze the phase stabilities of Ti-6Al-4sub>V (Ti-6wt.%Al-4sub>wt.%V). Our systematic analyses predict a variety of possible kinetic pathways for β to (α + β) transformations leading to different types of microstructures under various heat treatment conditions. In addition, the possibility of unconventional kinetic pathways is discussed. Lastly, we also briefly discuss the application of our approach to general multicomponent/multiphase alloy systems.

  3. Magnetic properties of (FeIn{sub 2}S{sub 4}){sub 1-x}(In{sub 2}S{sub 3}){sub x} alloy single crystals

    SciTech Connect

    Bodnar, I. V. Novikova, M. A.; Trukhanov, S. V.


    (FeIn{sub 2}S{sub 4}){sub 1-x}(In{sub 2}S{sub 3}){sub x} alloy single crystals are grown by oriented crystallization in the entire range of component concentrations. For the single crystals, studies of the magnetic properties are carried out in the temperature range 4-300 K and the magnetic-field range 0-14 T. It is established that almost all of the alloys are paramagnetic materials at temperatures down to the lowest achievable temperatures ({approx}4 K). It is shown that the ground magnetic phase state of the alloys is the spin-glass state with the freezing temperature steadily increasing with increasing Fe{sup 2+} cation content. The most probable causes and mechanism of formation of the magnetic state of the (FeIn{sub 2}S{sub 4}){sub 1-x}(In{sub 2}S{sub 3}){sub x} crystals are discussed.

  4. Electric-field-induced linear birefringence in TmAl3(BO3)4sub>.


    Pashchenko, M I; Bedarev, V A; Merenkov, D N; Gnatchenko, S L; Bezmaternykh, L N; Sukhachev, A L; Temerov, V L


    The linear birefringence induced by the electric field was first detected in a TmAl3(BO3)4sub> single crystal. The electric field dependence of the birefringence was investigated. The estimation of the electro-optical coefficient of the material gives ≈1.5×10-10  cm/V for a wavelength 632.8 nm. PMID:27140114

  5. Phase-matching directions and refined Sellmeier equations of the monoclinic acentric crystal BaGa4sub>Se7.


    Boursier, Elodie; Segonds, Patricia; Ménaert, Bertrand; Badikov, Valeriy; Panyutin, Vladimir; Badikov, Dmitrii; Petrov, Valentin; Boulanger, Benoît


    We directly measured the phase-matching directions of second-harmonic and difference frequency generation in the principal planes of the biaxial BaGa4sub>Se7 (BGSe) crystal using the sphere method. The simultaneous fit of the data allowed us to refine the Sellmeier equations of the three principal refractive indices of BGSe, and to calculate the tuning curves for infrared optical parametric generation. PMID:27304275

  6. Multi-wavelength Yb:YAG/Nd3+:YVO4sub> continuous-wave microchip Raman laser.


    Wang, Xiao-Lei; Dong, Jun; Wang, Xiao-Jie; Xu, Jie; Ueda, Ken-Ichi; Kaminskii, Alexander A


    Multi-wavelength continuous-wave (CW) Raman lasers in a laser diode pumped Yb:YAG/Nd3+:YVO4sub> microchip Raman laser have been demonstrated for the first time to our best knowledge. The multi-wavelength laser of the first Stokes radiation around 1.08 μm has been achieved with a Raman shift of 261  cm-1 for a-cut Nd:YVO4sub> crystal corresponding to the fundamental wavelength at 1.05 μm. Multi-wavelength laser operation simultaneously around 1.05 and 1.08 μm has been achieved under the incident pump power between 1.5 and 1.7 W. Multi-wavelength Raman laser with frequency separation of 1 THz around 1.08 μm has been obtained when the incident pump power is higher than 1.7 W. The maximum Raman laser output power of 260 mW at 1.08 μm is obtained and the corresponding optical-to-optical conversion efficiency is 4.2%. Elliptically polarized fundamental laser and linearly polarized Raman laser were observed in an Yb:YAG/Nd:YVO4sub> CW microchip Raman laser. The experimental results of linearly polarized, multi-wavelength Yb:YAG/Nd:YVO4sub> CW microchip Raman laser with adjustable frequency separation provide a novel approach for developing potential compact laser sources for Terahertz generation. PMID:27472618

  7. New insulating antiferromagnetic quaternary iridates MLa10Ir4sub>O24 (M=Sr, Ba)

    SciTech Connect

    Zhao, Qingbiao; Han, Fei; Stoumpos, Constantinos C.; Han, Tian -Heng; Li, Hao; Mitchell, J. F.


    Recently, oxides of Ir4+ have received renewed attention in the condensed matter physics community, as it has been reported that certain iridates have a strongly spin-orbital coupled (SOC) electronic state, Jeff = ½, that defines the electronic and magnetic properties. The canonical example is the Ruddlesden-Popper compound Sr2IrO4sub>, which has been suggested as a potential route to a new class of high temperature superconductor due to the formal analogy between Jeff = ½ and the S = ½ state of the cuprate superconductors. The quest for other iridium oxides that present tests of the underlying SOC physics is underway. In this spirit, here we report the synthesis and physical properties of two new quaternary tetravalent iridates, MLa10Ir4sub>O24 (M = Sr, Ba). The crystal structure of both compounds features isolated IrO6 octahedra in which the electronic configuration of Ir is d5. As a result, both compounds order antiferromagnetically despite the lack of obvious superexchange pathways, and resistivity measurement shows that SrLa10Ir4sub>O24 is an insulator.

  8. Correlation of anisotropy and directional conduction in β-Li3PS4sub> fast Li+ conductor

    SciTech Connect

    Chen, Yan; Cai, Lu; Liu, Zengcai; dela Cruz, Clarina R.; Liang, Chengdu; An, Ke


    Our letter reports the correlation of anisotropy and directional conduction in the fast Li+ conductor β-Li3PS4sub>, one of the low-symmetry crystalline electrolyte candidates. The material has both high conductivity and good stability that serves well for the large-scale energy storage applications of all-solid-state lithium ion batteries. The anisotropic physical properties, demonstrated here by the thermal expansion coefficients, are crucial for compatibility in the solid-state system and battery performance. Neutron and X-ray powder diffraction measurements were done to determine the crystal structure and thermal stability. Moreover, the crystallographic b-axis was revealed as a fast expansion direction, while negligible thermal expansion was observed along the a-axis around the battery operating temperatures. The anisotropic behavior has its structural origin from the Li+ conduction channels with incomplete Li occupancy and a flexible connection of LiS4sub> and PS4sub> tetrahedra within the framework. This indicates a strong correlation in the direction of the ionic transport in the low-symmetry Li+ conductor.

  9. Synthesis, crystal growth, structural and magnetic characterization of NH4sub>MCl2(HCOO), M=(Fe, Co, Ni)

    SciTech Connect

    Greenfield, Joshua T.; Ovidiu Garlea, V.; Kamali, Saeed; Chen, Michael; Kovnir, Kirill


    In this paper, an ambient-pressure solution route and an improved solvothermal synthetic method have been developed to produce polycrystalline powders and large single crystals of NH4sub>MCl2(HCOO) (M=Fe, Co, Ni). The magnetic structure of the 1D linear chain compound NH4sub>FeCl2(HCOO) has been determined by low-temperature neutron powder diffraction, revealing ferromagnetic intra-chain interactions and antiferromagnetic inter-chain interactions. Finally, the newly-reported Co and Ni analogs are isostructural with NH4sub>FeCl2(HCOO), but there are significant differences in the magnetic properties of each compound; the Ni analog behaves similarly to the Fe compound but with stronger magnetic coupling, exhibiting antiferromagnetic ordering (TN=8.5 K) and a broad metamagnetic transition between 2 and 5 T, while the Co analog does not order magnetically above 2 K, despite strong antiferromagnetic nearest-neighbor interactions.

  10. Organogold oligomers: Exploiting iClick and aurophilic cluster formation to prepare solution stable Au4sub> repeating units

    SciTech Connect

    Yang, Xi; Wang, Shanshan; Ghiviriga, Ion; Abboud, Khalil A.; Veige, Adam S.


    A novel synthetic method to create gold based metallo–oligomers/polymers via the combination of inorganic click (iClick) with intermolecular aurophilic interactions is demonstrated. Complexes [PEt3Au]4sub>(μ-N3C2C6H5) (1) and [PPhMe2Au]4sub (μ-N3C2C6H5) (2) and {[PEt3Au]4sub>[(μ-N3C2)2-9,9-dihexyl-9H-fluorene]}n (8) have been synthesized via iClick. The tetranuclear structures of 1 and 2, induced by aurophilic bonding, are confirmed in the solid state through single crystal X-ray diffraction experiments and in solution via variable temperature NMR spectroscopy. The extended 1D structure of 8 is constructed by aurophilic induced self-assembly. 1H DOSY NMR analysis reveals that the aurophilic bonds in 1, 2, and 8 are retained in the solution phase. The degree of polymerization within complex 8 is temperature and concentration dependent, as determined by 1H DOSY NMR. The complex 8 is a rare example of a solution stable higher ordered structure linked by aurophilic interactions.

  11. Magnetic excitations in the spin-1/2 triangular-lattice antiferromagnet Cs2CuBr4sub>

    SciTech Connect

    Zvyagin, S. A.; Ozerov, M.; Kamenskyi, D.; Wosnitza, J.; Krzystek, J.; Yoshizawa, D.; Hagiwara, M.; Hu, Rongwei; Ryu, Hyejin; Petrovic, C.; Zhitomirsky, M. E.


    We present on high- field electron spin resonance (ESR) studies of magnetic excitations in the spin- 1/2 triangular-lattice antiferromagnet Cs2CuBr4sub>. Frequency- field diagrams of ESR excitations are measured for different orientations of magnetic fields up to 25 T. We show that the substantial zero- field energy gap, Δ ≈ 9.5 K, observed in the low-temperature excitation spectrum of Cs2CuBr4sub> [Zvyagin et al:, Phys. Rev. Lett. 112, 077206 (2014)], is present well above TN. Noticeably, the transition into the long-range magnetically ordered phase does not significantly affect the size of the gap, suggesting that even below TN the high-energy spin dynamics in Cs2CuBr4sub> is determined by short-range-order spin correlations. The experimental data are compared with results of model spin-wave-theory calculations for spin-1/2 triangle-lattice antiferromagnet.

  12. Graphene oxide wrapped Ag{sub 3}PO{sub 4} sub-microparticles with highly enhanced photocatalytic activity and stability under visible light irradiation

    SciTech Connect

    Xiu, Zhiliang; Wu, Yongzhong; Hao, Xiaopeng; Lu, Qifang; Liu, Suwen


    Highlights: • Graphene oxide wrapped Ag{sub 3}PO{sub 4} sub-microparticles were prepared. • The photocatalytic activity of Ag{sub 3}PO{sub 4} is increased by 6 times by GO wrapping. • The hybrid photocatalysts exhibited excellent stability. - Abstract: Graphene oxide (GO) wrapped Ag{sub 3}PO{sub 4} sub-microparticles were prepared by in situ deposition–precipitation method. By hybridization of Ag{sub 3}PO{sub 4} with GO nanosheets, a 6-fold enhancement in the photodegradation rate toward orange methyl (MO) under visible light irradiation (λ ≥ 420 nm) was observed compared with the pure Ag{sub 3}PO{sub 4} sub-microsparticles. The hybrid photocatalysts also exhibited excellent stability in the successive MO degradation experiments. The highly enhanced photocatalytic activity and stability were mainly attributed to the quick transfer of the photogenerated electrons from Ag{sub 3}PO{sub 4} to GO nanosheets, which could effectively suppress the electron–hole pairs recombination and thus inhibit the photocorrosion of Ag{sub 3}PO{sub 4}. These high-efficient and stable hybrid photocatalysts were expected to show considerable potential applications in wastewater treatment and water splitting.

  13. Crystal structure, IR and Mössbauer spectroscopy and magnetic properties of KZnFe(PO{sub 4}){sub 2} related to the zeolite-ABW-like compounds

    SciTech Connect

    Badri, Abdessalem; Hidouri, Mourad; Wattiaux, Alain; López, María Luisa; Veiga, María Luisa; Amara, Mongi Ben


    Highlights: • The reported structure of KZnFe(PO{sub 4}){sub 2} is closely related to the zeolite ABW-type. • The structure is described in detail. • The IR and Mössbauer spectroscopy results are reported. • The magnetic properties are developed. - Abstract: The new iron phosphate KZnFe(PO{sub 4}){sub 2} has been synthesized by flux method and solid state reaction, and characterized by X-ray diffraction, IR, Mössbauer spectroscopy and magnetic susceptibility. This compound crystallizes in the monoclinic space group C2/c with the cell parameters: a = 13.514(4) Å, b = 13.273(6) Å, c = 8.742(3) Å and β = 100.07(2)°. It displays strong similarities with the phosphates KCoAl(PO{sub 4}){sub 2} and NaCoPO{sub 4} and features some analogies with the zeolite-ABW structural type. 3D framework is built up by a corner-sharing between MO{sub 4} (M = 0.5 Zn + 0.5 Fe) and PO{sub 4} tetrahedra. The K{sup +} ions are found within crossing tunnels perpendicular to the (1 0 0), (0 1 0) and (0 0 1) planes, delimited by this framework. A Mössbauer study confirmed the presence of Fe{sup 3+} ions in a tetrahedral environment. Magnetic measurements revealed an antiferromagnetic behavior with T{sub N} = 8.5 K.

  14. Color tunable and thermally stable luminescence of Tb{sup 3+} doped Li{sub 4}SrCa(SiO{sub 4}){sub 2} phosphors

    SciTech Connect

    Zhang, Xinmin; Seo, Hyo Jin


    Highlights: ► Lowest spin-allowed and spin-forbidden f–d transitions locate at 250 and 280 nm. ► Cross relaxation shortens lifetime of {sup 5}D{sub 3} level, while that of {sup 5}D{sub 4} are unaffected. ► Cross-relaxation can explain concentration quenching of the {sup 5}D{sub 3} emission. ► Dipole–quadrupole interaction is responsible for the non-radiative relaxation. ► Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tb{sup 3+} is thermally stable and color tunable phosphor. -- Abstract: Tb{sup 3+} ions activated Li{sub 4}SrCa(SiO{sub 4}){sub 2} phosphors were synthesized using a solid state reaction method. The phase impurity was checked by XRD. The photoluminescence (PL) excitation spectrum, emission spectra at room and high temperature, decay curves of samples with different Tb{sup 3+} ions concentration were studied in detail. Cross-relaxation and the Inokuti–Hirayama model were used to analyze the experimental results. Li{sub 4}SrCa(SiO{sub 4}){sub 2}:xTb{sup 3+} are thermally stable and color tunable phosphors.

  15. On the role of the VO(H{sub 2}PO{sub 4}){sub 2} precursor for n-butane oxidation into maleic anhydride

    SciTech Connect

    Sananes, M.T. |; Hutchings, G.J.; Volta, J.C.


    The catalytic role of VO(H{sub 2}PO{sub 4}){sub 2}, the precursor of the VO(PO{sub 3}){sub 2} phase, has been studied for N-butane oxidation to maleic anhydride. By comparison with the activated VPO catalyst, derived from the VOHPO{sub 4} {center_dot} 0.5H{sub 2}O precursor phase, VO(H{sub 2}PO{sub 4}){sub 2} gives a highly selective final catalyst. The total oxidation products CO and CO{sub 2} are not observed under any of the conditions examined, a result confirmed by extensive catalyst testing and carbon mass balances. The final catalyst derived from VO(H{sub 2}PO{sub 4}){sub 2} has a low surface area, ca. 1 m{sup 2}/g, and consequently demonstrates low specific activity on the basis of n-butane conversion per unit mass. However, the intrinsic activity (activity per unit surface area) is found to be higher than that for catalysts derived from VOHPO{sub 4}{center_dot}0.5H{sub 2}O. Since some VO(H{sub 2}PO{sub 4}){sub 2} is present in VOHPO{sub 4}{center_dot}0.5H{sub 2}O, which is the precursor of the industrial catalyst, the results of this study complicate the simple model in which the (VO){sub 2}O{sub 7} phase derived from VOHPO{sub 4} {center_dot}0.5H{sub 2}O is responsible for the selective oxidation of n-butane. The observation that the precursor VO(H{sub 2}PO{sub 4}){sub 2} can generate catalysts of high specific activity and of total selectivity to partial oxidation products might provide a useful insight into the design of a new series of high activity and high selectivity partial oxidation catalysts. 36 refs., 12 figs., 2 tabs.

  16. Structural, electronic and thermodynamic properties of britholites Ca{sub 10−x}La{sub x}(PO{sub 4}){sub 6−x}(SiO{sub 4}){sub x}F{sub 2} (0 ≤ x ≤ 6): Experiment and theory

    SciTech Connect

    Njema, H.; Debbichi, M.; Boughzala, K.; Said, M.; Bouzouita, K.


    Highlights: • The structural and electronic properties of apatites with the general formula Ca{sub 10−x}La{sub x}(PO{sub 4}){sub 6−x}(SiO{sub 4}){sub x}F{sub 2} (0 ≤ x ≤ 6) have been investigated by means of the density functional theory. • The calculated enthalpy of formation of the compounds increased with the substitution degree. • The decrease in stability is probably due to the disorder induced in the Ca/LaO{sub 6}F polyhedron, following the substitution. - Abstract: The apatite-type compounds Ca{sub 10−x}La{sub x}(PO{sub 4}){sub 6−x}(SiO{sub 4}){sub x}F{sub 2} with 0 ≤ x ≤ 6 were prepared using a high temperature solid state reaction and were characterized by X-ray diffraction. The crystal structure, chemical bonding, electronic structure and formation energy of all relaxed structures were analyzed by density functional theory (DFT). The calculated results show that the predicted geometry can well reproduce the structural parameters. The incorporation of La{sup 3+} into the fluorapatite (FA) structure induced especially at the level of the S(2) sites a certain disorder which is responsible for the weakening in the stability with x. Excellent agreement were obtained between the calculated and experimental results. Moreover, the band structure indicates that despite the reduction of the band gap with x content all materials remain insulating.

  17. Crystal structures of alkali-metal indium (III) phosphates of [M{sub 3}In(PO{sub 4}){sub 2}]{sub n} (M=K, n=10; M=Rb, n=2) compounds, and band structures and chemical bond properties of [Rb{sub 3}In(PO{sub 4}){sub 2}]{sub 2} crystal

    SciTech Connect

    Zhang Yongchun; Cheng Wendan . E-mail:; Wu Dongsheng


    Ternary indium (III) phosphates with three-dimensional frameworks, [M{sub 3}In(PO{sub 4}){sub 2}]{sub n} (M=K, n=10; M=Rb, n=2), are found and firstly reported in this paper. These compounds have been obtained by high temperature solid-state reactions and their crystal structures have been determined by single crystal X-ray diffraction analysis. The title compounds, which crystallize in monoclinic system, possess the same [In(PO{sub 4}){sub 2}]{sub n}{sup 3n-} anionic frameworks built up from interconnected InO{sub 6} octahedra and PO{sub 4} tetrahedra and have an interesting tunnel structure where M{sup +} cations are located. Optical and bonding properties of [Rb{sub 3}In(PO{sub 4}){sub 2}]{sub 2} are investigated in terms of measured absorption and emission spectra, and calculated band structures and density of states. The crystal band structures obtained by the DFT method show that the solid compound of [Rb{sub 3}In(PO{sub 4}){sub 2}]{sub 2} is an insulator with direct band gap, and the P-O covalent bond characters are larger than the In-O ones in this compound.

  18. Infrared and Raman spectra of Na{sub 2}Cu(SO{sub 4}){sub 2}{center_dot}2H{sub 2}O and (CH{sub 3}NH{sub 3}){sub 2}M(II)(SO{sub 4}){sub 2}{center_dot}6H{sub 2}O with M(II) = Cu, Zn, and Ni

    SciTech Connect

    Pillai, V.P.M.; Nayar, V.U.; Jordanovska, V.B.


    FTIR and Raman spectra of Na{sub 2}Cu(SO{sub 4}){sub 2}{center_dot}2H{sub 2}O and (CH{sub 3}NH{sub 3}){sub 2}M(II) (SO{sub 4}){sub 2}{center_dot}6H{sub 2}O with M(II) = Cu, Zn, and Ni are recorded and analyzed. Bands are assigned on the basis of SO{sub 4}{sup 2-}, CH{sub 3}NH{sub 3}{sup +}, and H{sub 2}O vibrations. The lifting of degeneracies of {nu}{sub 2}, {nu}{sub 3} and v{sub 4} modes and the appearance of {nu}{sub 1} and {nu}{sub 2} modes in the IR spectra confirm the lowering of symmetry of the SO{sub 4}{sup 2-} ion from T{sub d} to C{sub 1} in all of the title compounds. Bands obtained indicate that the distoration of the SO{sub 4}{sup 2-} ion in the four crystals are in the order, (CH{sub 3}NH{sub 3})Cu(SO{sub 4}){sub 2}{center_dot}6H{sub 2}O > (CH{sub 3}NH{sub 3}){sub 2}Ni(SO{sub 4}){sub 2}{center_dot}6H{sub 2}O > (CH{sub 3}NH{sub 3}){sub 2}Zn(SO{sub 4}){sub 2}{center_dot}6H{sub 2}O > Na{sub 2}Cu(SO{sub 4}){sub 2}{center_dot} 2H{sub 2}O. The appearance of NH{sub 3} stretching modes at wavenumbers lower than the values obtained for the free ion indicates the presence of hydrogen bonds between NH{sub 3} and SO{sub 4}{sup 2-} groups. The appearance of multiple bands in the blending and rocking mode regions and the broad nature of stretching modes show the existence of at least two symmetrically inequivalent water molecules in Na{sub 2}Cu(SO{sub 4}){sub 2}{center_dot}2H{sub 2}O. The shifting of stretching modes to lower wavenumbers and bending modes to higher wavenumbers of water molecules confirms the existence of strong hydrogen bonds in the crystal which is in agreement with the X-ray data. Bands indicate the presence of strong hydrogen bonds involving water molecules in (CH{sub 3}NH{sub 3}){sub 2}Cu(SO{sub 4}){sub 2}{center_dot}6H{sub 2}O and (CH{sub 3}NH{sub 3}){sub 2} Zn(SO{sub 4}){sub 2}{center_dot}6H{sub 2}O and of lesser strength in (CH{sub 3}NH{sub 3}){sub 2}Ni(SO{sub 4}){sub 2}{center_dot}6H{sub 2}O.

  19. Superconductivity in the presence of disorder in skutterudite-related La3Co4sub>Sn13 and La3Ru4sub>Sn13 compounds: Electrical transport and magnetic studies

    SciTech Connect

    Slebarski, A.; Maska, M. M.; Fijalkowski, M.; McElroy, C. A.; Maple, M. B.


    La3Co4sub>Sn13 and La3Ru4sub>Sn13 were categorized as BCS superconductors. In a plot of the critical field Hc2 vs T, La3Ru4sub>Sn13 displays a second superconducting phase at the higher critical temperature Tc*, characteristic of inhomogeneous superconductors, while La3Co4sub>Sn13 shows bulk superconductivity below Tc. We observe a decrease in critical temperatures with external pressure and magnetic field for both compounds. Additionally, for La3Ru4sub>Sn13 we find that Tc*/dP>dTc/dP. The pressure dependences of Tc are interpreted according to the McMillan theory and understood to be a consequence of lattice stiffening. The investigation of the superconducting state of La3CoxRu4–xSn13 shows a Tc* that is larger then Tc for x < 4. Furthermore, this unique and unexpected observation is discussed as a result of the local disorder and/or the effect of chemical pressure when Ru atoms are partially replaced by smaller Co atoms.

  20. Study of phase relationships in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system. Phase diagram and thermal characteristics of phases

    SciTech Connect

    Matraszek, Aleksandra


    A diagram representing phase relationships in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} phosphate system has been developed on the basis of results obtained by thermal analysis (DTA/DSC/TGA) and X-ray diffraction (XRD) methods. One intermediate compound with the formula Sr{sub 3}Ce(PO{sub 4}){sub 3} occurs in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system at temperatures exceeding 1045 °C. The compound has a eulytite structure with the following structural parameters: a=b=c=10.1655(8) Å, α=β=γ=90.00°, V=1050.46(6) Å{sup 3}. It's melting point exceeds 1950 °C. A limited solid solution exists in the system, which possesses the structure of a low-temperature form of Sr{sub 3}(PO{sub 4}){sub 2}. At 1000 °C the maximal concentration of CePO{sub 4} in the solid solution is below 20 mol%. The solid solution phase field narrows with increased temperature. There is a eutectic point in the (Sr{sub 3}(PO{sub 4}){sub 2}+Sr{sub 3}Ce(PO{sub 4}){sub 3}) phase field at 1765 °C and 15 mol% of CePO{sub 4}. The melting temperature of Sr{sub 3}(PO{sub 4}){sub 2} is 1882±15 °C. - Graphical abstract: The phase diagram of Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system showing the stability ranges of limited solid solution and Sr{sub 3}Ce(PO{sub 4}){sub 3} phases. - Highlights: • Sr{sub 3}(PO{sub 4}){sub 2} melts at 1882 °C. • Phase diagram of Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system has been proposed. • Limited solid solution of CePO{sub 4} in Sr{sub 3}(PO{sub 4}){sub 2} forms in the system. • The Sr{sub 3}Ce(PO{sub 4}){sub 2} phosphate is stable at temperatures above 1045 °C.

  1. Crystal structures of lazulite-type oxidephosphates Ti{sup III}Ti{sup IV}{sub 3}O{sub 3}(PO{sub 4}){sub 3} and M{sup III}{sub 4}Ti{sup IV}{sub 27}O{sub 24}(PO{sub 4}){sub 24} (M{sup III}=Ti, Cr, Fe)

    SciTech Connect

    Schoeneborn, M.; Glaum, R. Reinauer, F.


    Single crystals of the oxidephosphates Ti{sup III}Ti{sup IV}{sub 3}O{sub 3}(PO{sub 4}){sub 3} (black), Cr{sup III}{sub 4}Ti{sup IV}{sub 27}O{sub 24}(PO{sub 4}){sub 24} (red-brown, transparent), and Fe{sup III}{sub 4}Ti{sup IV}{sub 27}O{sub 24}(PO{sub 4}){sub 24} (brown) with edge-lengths up to 0.3 mm were grown by chemical vapour transport. The crystal structures of these orthorhombic members (space group F2dd ) of the lazulite/lipscombite structure family were refined from single-crystal data [Ti{sup III}Ti{sup IV}{sub 3}O{sub 3}(PO{sub 4}){sub 3}: Z=24, a=7.3261(9) A, b=22.166(5) A, c=39.239(8) A, R{sub 1}=0.029, wR{sub 2}=0.084, 6055 independent reflections, 301 variables; Cr{sup III}{sub 4}Ti{sup IV}{sub 27}O{sub 24}(PO{sub 4}){sub 24}: Z=1, a=7.419(3) A, b=21.640(5) A, c=13.057(4) A, R{sub 1}=0.037, wR{sub 2}=0.097, 1524 independent reflections, 111 variables; Fe{sup III}{sub 4}Ti{sup IV}{sub 27}O{sub 24}(PO{sub 4}){sub 24}: Z=1, a=7.4001(9) A, b=21.7503(2) A, c=12.775(3) A, R{sub 1}=0.049, wR{sub 2}=0.140, 1240 independent reflections, 112 variables). For Ti{sup III}Ti{sup IV}O{sub 3}(PO{sub 4}){sub 3} a well-ordered structure built from dimers [Ti{sup III,IV}{sub 2}O{sub 9}] and [Ti{sup IV,IV}{sub 2}O{sub 9}] and phosphate tetrahedra is found. The metal sites in the crystal structures of Cr{sub 4}Ti{sub 27}O{sub 24}(PO{sub 4}){sub 24} and Fe{sub 4}Ti{sub 27}O{sub 24}(PO{sub 4}){sub 24}, consisting of dimers [M{sup III}Ti{sup IV}O{sub 9}] and [Ti{sup IV,IV}{sub 2}O{sub 9}], monomeric [Ti{sup IV}O{sub 6}] octahedra, and phosphate tetrahedra, are heavily disordered. Site disorder, leading to partial occupancy of all octahedral voids of the parent lipscombite/lazulite structure, as well as splitting of the metal positions is observed. According to Guinier photographs Ti{sup III}{sub 4}Ti{sup IV}{sub 27}O{sub 24}(PO{sub 4}){sub 24} (a=7.418(2) A, b=21.933(6) A, c=12.948(7) A) is isotypic to the oxidephosphates M{sup III}{sub 4}Ti{sup IV}{sub 27}O{sub 24}(PO{sub 4

  2. Preparation and crystal structure of a new bismuth vanadate, Bi{sub 3.33}(VO{sub 4}){sub 2}O{sub 2}

    SciTech Connect

    Kumada, N.; Takei, T.; Haramoto, R.; Yonesaki, Y.; Dong, Q.; Kinomura, N.; Nishimoto, S.; Kameshima, Y.; Miyake, M.


    Graphical abstract: Crystal structure of Bi{sub 3.33}(VO{sub 4}){sub 2}O{sub 2}. Solid lines indicate the unit cell. Highlights: {yields} We can prepare a new bismuth vanadate, Bi{sub 3.33}(VO{sub 4}){sub 2}O{sub 2} by hydrothermal reaction using a hydrated sodium bismuthate. {yields} We clarify that the crystal structure is composed by four bismuth atoms with the coordination number of 6 or 8 and two VO{sub 4} tetrahedra. {yields} This compound exhibited photocatalytic behavior for decomposition of phenol under visible light irradiation. -- Abstract: Single crystals of a new bismuth vanadate, Bi{sub 3.33}(VO{sub 4}){sub 2}O{sub 2} was prepared by hydrothermal reaction using a hydrated sodium bismuthate, NaBiO{sub 3}.nH{sub 2}O as one of the starting compounds. The crystal structure was determined by using single crystal X-ray diffraction data. This compound crystallizes in the triclinic space group P1{sup -bar} (no. 2) with a = 7.114(1), b = 7.844(2), c = 9.372(2) A, {alpha} = 106.090(7), {beta} = 94.468(7) and {gamma} = 112.506(8){sup o}, Z = 2 and the final R factors are R1 = 0.052 and wR2 = 0.14 for 2085 unique reflections. The crystal structure is composed by four bismuth atoms with the coordination number of 6 or 8 and two VO{sub 4} tetrahedra, and one of four bismuth atoms is statistically distributed in the splitting sites with the distance of 0.83 A. This compound exhibited photocatalytic behavior for decomposition of phenol under visible light irradiation and its activity was less than that of monoclinic BiVO{sub 4}.

  3. Writing of nonlinear optical Sm{sub 2}(MoO{sub 4}){sub 3} crystal lines at the surface of glass by samarium atom heat processing

    SciTech Connect

    Abe, M.; Benino, Y.; Fujiwara, T.; Komatsu, T.; Sato, R.


    Some glasses such as 21.25Sm{sub 2}O{sub 3}.63.75MoO{sub 3}.15B{sub 2}O{sub 3} (mol %) giving the formation of nonlinear optical Sm{sub 2}(MoO{sub 4}){sub 3} crystals through conventional crystallization in an electric furnace and through continuous-wave Nd: yttrium aluminum garnet (YAG) laser (wavelength: 1064 nm) irradiation (samarium atom heat processing) have been developed. It is proposed from x-ray diffraction analyses, micro-Raman-scattering spectra, and second-harmonic generation measurements that the crystal structure of Sm{sub 2}(MoO{sub 4}){sub 3} formed by the crystallization is the {beta}{sup '}-phase structure with an orthorhombic (noncentrosymmetric) symmetry. The lines consisting of nonlinear optical {beta}{sup '}-Sm{sub 2}(MoO{sub 4}){sub 3} crystals are written at the surface of glasses by YAG laser irradiation (laser power: P=0.4 W, laser scanning speed: S=1-10 {mu}m/s), and, in particular, homogeneous crystal lines are formed at the laser scanning speed of 1 {mu}m/s. Refractive index changes (not crystallization) are also induced by YAG laser irradiation of P=0.4 W and a high laser scanning speed of S=25 {mu}m/s. The crystallization mechanism in the laser-irradiated region has been proposed. The present study demonstrates that the samarium atom heat processing is a technique for the writing of rare earth containing optical nonlinear/ferroelectric crystal lines in glass.

  4. Vacuum ultraviolet spectroscopic properties of rare earth (RE=Ce,Tb,Eu,Tm,Sm)-doped hexagonal KCaGd(PO{sub 4}){sub 2} phosphate

    SciTech Connect

    Zhang, Z. J.; Yuan, J. L.; Duan, C. J.; Xiong, D. B.; Chen, H. H.; Zhao, J. T.; Zhang, G. B.; Shi, C. S.


    Hexagonal KCaGd(PO{sub 4}){sub 2}:RE{sup 3+} (RE=Ce,Tb,Eu,Tm,Sm) were synthesized by coprecipitation method and their vacuum ultraviolet-ultraviolet (VUV-UV) spectroscopic properties were investigated. The bands at about 165 nm in the VUV excitation spectra are attributed to the host lattice absorptions. For Ce{sup 3+}-doped samples, the bands at 207, 256, 275, and 320 nm are assigned to the 4f-5d transitions of Ce{sup 3+} in KCaGd(PO{sub 4}){sub 2}. For Tb{sup 3+}-doped sample, the bands at 203 and 222 nm are related to the 4f-5d spin-allowed transitions. For Eu{sup 3+}-doped sample, the O{sup 2-}-Eu{sup 3+} charge-transfer band (CTB) at 229 nm is observed, and the fine emission spectrum of Eu{sup 3+} indicates that Eu{sup 3+} ions prefer to occupy Gd{sup 3+} or Ca{sup 2+} sites in the host lattice. For Tm{sup 3+}- and Sm{sup 3+}-doped samples, the O{sup 2-}-Tm{sup 3+} and O{sup 2-}-Sm{sup 3+} CTBs are observed to be at 176 and 186 nm, respectively. From the standpoints of the absorption band, color purity, and luminescent intensity, Tb{sup 3+}-doped KCaGd(PO{sub 4}){sub 2} is a potential candidate for 172 nm excited green plasma display phosphors.

  5. Mixed tetrahedral anionic framework in the K{sub 3}Ga{sub 2}(PO{sub 4}){sub 3} crystal structure

    SciTech Connect

    Yakubovich, O. V.; Steele, I.; Kireev, V. V.


    The crystal structure of a new synthetic potassium gallophosphate K{sub 3}Ga{sub 2}(PO{sub 4}){sub 3} grown from a solution in the melt of a mixture of GaPO{sub 4} and K{sub 2}MoO{sub 4} is determined using X-ray diffraction (Bruker Smart diffractometer, 2{theta}{sub max}= 56.6{sup o}, R = 0.044 for 2931 reflections, T = 100 K). The main crystal data are as follows: a = 8.661(2) A, b = 17.002(4) A, c = 8.386(2) A, space group Pna2{sub 1}, Z= 4, and {rho}{sub calcd} = 2.91 g/cm{sup 3}. The synthesized crystals represent the third phase in the structure type previously established for the K{sub 3}Al{sub 2}[(As,P)O{sub 4}]{sub 3} compound. It is shown that the structure consists of a three-dimensional anionic microporous tetrahedral framework of the mixed type, which is formed by PO{sub 4} and GaO{sub 4} tetrahedra shared by vertices. Large-sized cations K{sup +} occupy channels of the zeolite-like framework. The crystal chemical features of the formation of structure types of compounds with mixed frameworks described by the general formula A{sub 3}{sup +}M{sub 2}{sup 3+}(TO{sub 4}){sub 3} (where A = K, Rb, (NH{sub 4}), Tl; M = Al, Ga, Fe, Sc, Yb; T = P, As) are analyzed.

  6. High efficiency passively mode-locked Nd:YVO4sub> laser with direct in-band pumping at 914 nm.


    Waritanant, Tanant; Major, Arkady


    We report on the performance of a semiconductor saturable absorber mirror passively mode-locked Nd:YVO4sub> laser with in-band pumping at 914 nm and with the highest slope efficiency to date among the mode-locked Nd-lasers. The laser produced 6.7 W of output power with repetition rate of 87 MHz and pulse duration of 16 ps. The slope efficiency of 77.1% and the optical-to-optical efficiency of 60.7% were achieved. PMID:27410304

  7. Improved synthesis and crystal structure of the flexible pillared layer porous coordination polymer: Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN)4sub>

    SciTech Connect

    Wong-Ng, W.; Culp, J. T.; Chen, Y. S.; Zavalij, P.; Espinal, L.; Siderius, D. W.; Allen, A. J.; Scheins, S.; Matranga, C.


    This paper reports our synthesis of flexible coordination polymer, Ni(L)[Ni(CN)4sub>], (L = 1,2-bis(4-pyridyl)ethylene (nicknamed bpene)), and its structural characterization using synchrotron single crystal X-ray diffraction. The structure of the purplish crystals has been determined to be monoclinic, space group P21/m, a = 13.5941(12) Å, b = 14.3621(12) Å, c = 14.2561(12) Å, β = 96.141(2)°, V = 2767.4(4) Å3, Z = 4, Dc = 1.46 g cm-1. Ni(bpene)[Ni(CN)4sub>] assumes a pillared layer structure with layers defined by Ni[Ni(CN)4sub>]n nets and bpene ligands acting as pillars. With the present crystallization technique which involves the use of concentrated ammonium hydroxide solution and dimethyl sulfoxide (DMSO), disordered free bpene ligands and solvents of crystallization (DMSO and water molecules) occupy the pores, resulting in a formula of Ni(bpene)[Ni(CN)4sub>](1/2)bpene∙DMSO2H2O, or Ni2N7C24H25SO3. Without the inclusion of free bpene ligands and solvent molecules, the free volume is approximately 61% of the total volume; this free volume fraction is reduced to 50% with the free ligands present. Pores without the free ligands were found to have a local diameter of 5.7 Å and a main aperture of 3.5 Å. Based on the successful crystal synthesis, we also devised a new bulk synthetic technique which yielded a polycrystalline material with a significantly improved CO2 uptake as compared to the originally reported powder material. The improved synthetic technique yielded a polycrystalline material with 40% higher CO2 uptake compared to the previously reported powder material. An estimated 14.4 molecules of CO2 per unit cell was obtained.

  8. Quantum oscillations in a novel organic quasi-two-dimensional (BEDO-TTF){sub 5}[RbHg(SCN){sub 4}]{sub 2} metal

    SciTech Connect

    Lyubovskii, R. B.; Pesotskii, S. I. Perenboom, J. A. A. J.; Zhilyaeva, E. I.; Bogdanova, O. A.; Lyubovskaya, R. N.


    Quantum magnetization and magnetoresistance oscillations are detected in the quasi-two-dimensional organic metal (BEDO-TTF){sub 5}[RbHg(SCN){sub 4}]{sub 2} for the first time. The magnetization oscillation spectrum corresponds to a calculated Fermi surface provided that a magnetic breakdown is realized. The magnetoresistance oscillation spectrum contains additional frequencies, one of which can unambiguously be related to quantum interference. An analysis of the angular dependence of the magnetoresistance oscillation amplitude indicates that the many-body interactions in this metal are weak.

  9. Integrated chip-scale Si3N4sub> wavemeter with narrow free spectral range and high stability.


    Xiang, Chao; Tran, Minh A; Komljenovic, Tin; Hulme, Jared; Davenport, Michael; Baney, Doug; Szafraniec, Bogdan; Bowers, John E


    We designed, fabricated, and characterized an integrated chip-scale wavemeter based on an unbalanced Mach-Zehnder interferometer with 300 MHz free spectral range. The wavemeter is realized in the Si3N4sub> platform, allowing for low loss with ∼62  cm of on-chip delay. We also integrated an optical hybrid to provide phase information. The main benefit of a fully integrated wavemeter, beside its small dimensions, is increased robustness to vibrations and temperature variations and much improved stability over fiber-based solutions. PMID:27420522

  10. Widely tunable in the mid-IR BaGa4sub>Se7 optical parametric oscillator pumped at 1064  nm.


    Kostyukova, Nadezhda Y; Boyko, Andrey A; Badikov, Valeriy; Badikov, Dmitrii; Shevyrdyaeva, Galina; Panyutin, Vladimir; Marchev, Georgi M; Kolker, Dmitry B; Petrov, Valentin


    A BaGa4sub>Se7 nanosecond optical parametric oscillator (OPO) shows extremely wide idler tunability in the mid-IR (2.7-17 μm) under 1.064 μm pumping. The ∼10  ns pulses at ∼7.2  μm have an energy of 3.7 mJ at 10 Hz. The pump-to-idler conversion efficiency for this wavelength reaches 5.9% with a slope of 6.5% corresponding to a quantum conversion efficiency or pump depletion of 40%. PMID:27472645

  11. Unique edge-sharing sulfate-transition metal coordination in Na{sub 2}M(SO{sub 4}){sub 2} (M=Ni and Co)

    SciTech Connect

    Fry, Allyson M.; Sweeney, Owen T.; Adam Phelan, W.; Drichko, Natalia; Siegler, Maxime A.; McQueen, Tyrel M.


    Two compounds, Na{sub 2}Ni(SO{sub 4}){sub 2} and Na{sub 2}Co(SO{sub 4}){sub 2}, were synthesized and their structure and properties were characterized. They adopt a structure that contains a bidentate coordination of sulfate to the transition metal center, which was determined via single crystal X-ray diffraction combined with model refinements to both laboratory X-ray and time-of-flight neutron powder diffraction data. The compounds were both found to crystallize in the C2/c space group with Z=24 and a unit cell of a=23.3461(3) Å, b=10.3004(1) Å, c=17.4115(2) Å, β=98.8659(9)°, and V=4136.99(8) Å{sup 3} for the cobalt analog and a=23.2253(1) Å, b=10.26155(6) Å, c=17.3353(1) Å, β=99.0376(5)°, and V=4080.20(5) Å{sup 3} for the nickel analog. Magnetization measurements show that the transition metal centers have negligible interactions with neighboring sites. Infrared and Raman spectroscopies were used to further probe the unique sulfate-transition metal coordination, and confirm the bidentate binding motif. The resulting pseudo-trigonal bipyramidal coordination produces vivid violet, Na{sub 2}Co(SO{sub 4}){sub 2}, and yellow, Na{sub 2}Ni(SO{sub 4}){sub 2}, colors that were probed by diffuse reflectance. - Graphical abstract: Two blue distorted transition metal octahedra (oxygen in red) bridged by two sulfate tetrahedra are shown here. Each bridging sulfate tetrahedra shares an edge with one octahedron and a corner with the other. All of the remaining corners of the octahedra are corner sharing with four tetrahedra forming a polyhedral network. - Highlights: • Structure of Na2Ni(SO4)2 and Na2Co(SO4)2 is determined. • Unique sulfate-transition metal binding observed in the new structure. • Combined diffraction and spectroscopic techniques were used. • Magnetization measurements show negligible interactions between sites.

  12. Investigation of the structure of Cs{sub 3}(HSO{sub 4}){sub 2}(H{sub 2}PO{sub 4}) single crystals

    SciTech Connect

    Makarova, I. P. Grebenev, V. V.; Vasiliev, I. I.; Dmitricheva, E. V.; Komornikov, V. A.; Dolbinina, V. V.


    Cs{sub 3}(HSO{sub 4}){sub 2}(H{sub 2}PO{sub 4}) single crystals, obtained for the first time based on a systematic study of the phase diagram of the CsH{sub 2}PO{sub 4}–CsHSO{sub 4}–H{sub 2}O ternary system, have been studied by X-ray diffraction. The atomic structure of the crystals at room temperature is determined, and their structural features are analyzed.

  13. Reducing ultra-low thermal expansion of {beta}-Zr{sub 2}O(PO{sub 4}){sub 2} by substitutions?

    SciTech Connect

    Barreteau, Celine; Bregiroux, Damien; Laurent, Guillaume; Wallez, Gilles


    The ultra-low thermal expansion of {beta}-Zr{sub 2}O(PO{sub 4}){sub 2} could still be reduced by chemical modifications, according to previous works on uranium and thorium IV homologues that evidenced a contracting effect of big cations. However, the present study shows that the only isovalent cations likely to substitute for Zr{sup IV} or P{sup V} are either harmful, or unstable, chemically or thermally. Furthermore, aliovalent modifications seem to be forbidden by the crystal structure of the material, leaving probably very few perspectives of improvement. Vanadium however improves significantly the crystallinity of the material and lowers the {alpha}-{beta} transition temperature.

  14. Luminescent properties of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} and its luminescence improvement by incorporating A{sup +} (A=Li, Na, and K)

    SciTech Connect

    Li, Panlai Wang, Zhijun Yang, Zhiping; Guo, Qinglin


    A novel green phosphor SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} is synthesized by a high temperature solid-state method, and its luminescent property is investigated. X-ray diffraction patterns of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} indicate a similarity crystalline phase to SrZn{sub 2}(PO{sub 4}){sub 2}. SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} shows green emission under 369 nm excitation, and the prominent luminescence in green (544 nm) due to {sup 5}D{sub 4}–{sup 7}F{sub 5} transition of Tb{sup 3+}. For the 544 nm emission, excitation spectrum has several excitation band from 200 nm to 400 nm. Emission intensity of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} is influenced by Tb{sup 3+} concentration, and concentration quenching effect of Tb{sup 3+} in SrZn{sub 2}(PO{sub 4}){sub 2} is also observed. With incorporating A{sup +} (A=Li, Na, and K) as compensator charge, the emission intensity of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} can be obviously enhanced. CIE color coordinates of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} locate in the green region. The results indicate this phosphor may be a potential application in white LEDs. - Graphical abstract: SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} can produce green emission under near-UV excitation, and its luminescent properties can be improved by incorporating A{sup +} (A=Li, Na, and K). - Highlights: • SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} can produce green emission under near-UV excitation. • Concentration quenching effect of Tb{sup 3+} in SrZn{sub 2}(PO{sub 4}){sub 2} is observed. • Emission intensities of SrZn{sub 2}(PO{sub 4}){sub 2}:Tb{sup 3+} are enhanced by codoped A{sup +} (A=Li, Na, K)

  15. Synthesis and crystal structure of a new open-framework iron phosphate (NH{sub 4}){sub 4}Fe{sub 3}(OH){sub 2}F{sub 2}[H{sub 3}(PO{sub 4}){sub 4}]: Novel linear trimer of corner-sharing Fe(III) octahedra

    SciTech Connect

    Mi, Jin-Xiao; Wang, Cheng-Xin; Chen, Ning; Li, Rong; Pan, Yuanming


    A new iron phosphate (NH{sub 4}){sub 4}Fe{sub 3}(OH){sub 2}F{sub 2}[H{sub 3}(PO{sub 4}){sub 4}] has been synthesized hydrothermally at HF concentrations from 0.5 to 1.2 mL. Single-crystal X-ray diffraction analysis reveals its three-dimensional open-framework structure (monoclinic, space group P2{sub 1}/n (No. 14), a=6.2614(13) A, b=9.844(2) A, c=14.271(3) A, {beta}=92.11(1){sup o}, V=879.0(3) A{sup 3}). This structure is built from isolated linear trimers of corner-sharing Fe(III) octahedra, which are linked by (PO{sub 4}) groups to form ten-membered-ring channels along [1 0 0]. This isolated, linear trimer of corner-sharing Fe(III) octahedra, [(FeO{sub 4}){sub 3}(OH){sub 2}F{sub 2}], is new and adds to the diverse linkages of Fe polyhedra as secondary building units in iron phosphates. The trivalent iron at octahedral sites for the title compound has been confirmed by synchrotron Fe K-edge XANES spectra and magnetic measurements. Magnetic measurements also show that this compound exhibit a strong antiferromagnetic exchange below T{sub N}=17 K, consistent with superexchange interactions expected for the linear trimer of ferric octahedra with the Fe-F-Fe angle of 132.5{sup o}. -- Graphical abstract: The three-dimensional open-framework structure of (NH{sub 4}){sub 4}Fe{sub 3}(OH){sub 2}F{sub 2}[H{sub 3}(PO{sub 4}){sub 4}] is built from a novel isolated, linear (FeO{sub 4}){sub 3}(OH){sub 2}F{sub 2} trimer of corner-sharing Fe(III) octahedra linked by PO{sub 4} tetrahedra. Display Omitted

  16. Magnetic excitations from an S=1/2 diamond-shaped tetramer compound Cu2PO4sub>OH

    SciTech Connect

    Matsuda, Masaaki; Dissanayake, Sachith E.; Abernathy, Douglas L.; Totsuka, K.; Belik, A. A.


    Inelastic neutron scattering experiments have been carried out on a powder sample of Cu2PO4sub>OH, which consists of diamond-shaped tetramer spin units with S=1/2. We have observed two nearly dispersionless magnetic excitations at E1 ~2 and E2 ~0 meV, whose energy width are broader than the instrumental resolution. The simplest square tetramer model with one dominant interaction, which predicts two sharp excitation peaks at E1 and E2(=2E1), does not explain the experimental result. We found that two diagonal intratetramer interactions compete with the main interaction and weak intertetramer interactions connect the tetramers. The main intratetramer interaction is found to split into two inequivalent ones due to a structural distortion below 160 K. Cu2PO4sub>OH is considered to be a good material to study the S=1/2 Heisenberg tetramer system.

  17. Metastability in the MgAl2O4sub>-Al2O3 System

    SciTech Connect

    Wilkerson, Kelley R.; Smith, Jeffrey D.; Hemrick, James G.


    Aluminum oxide must take a spinel form ( γ-Al2O3) at elevated temperatures in order for extensive solid solution to form between MgAl2O4sub> and α-Al2O3. The solvus line between MgAl2O4sub> and Al2O3 has been defined at 79.6 wt% Al2O3 at 1500°C, 83.0 wt% Al2O3 at 1600°C, and 86.5 wt% Al2O3 at 1700°C. A metastable region has been defined at temperatures up to 1700°C which could have significant implications for material processing and properties. Additionally, initial processing could have major implications on final chemistry. The spinel solid solution region has been extended to form an infinite solid solution with Al2O3 at elevated temperatures. A minimum in melting at 1975°C and a chemistry of 96 wt% Al2O3 rather than a eutectic is present, resulting in no eutectic crystal formation during solidification.

  18. Thermodynamic Properties of α-Fe2O3 and Fe3O4sub> Nanoparticles

    SciTech Connect

    Spencer, Elinor C.; Ross, Nancy L.; Olsen, Rebecca E.; Huang, Baiyu; Kolesnikov, Alexander I.; Woodfield, Brian F.


    Here we comprehansively assessed the thermodynamic properties of hydrated α-Fe2O3 (hematite) and Fe3O4sub> (magnetite) nanoparticles. In addition to 9 nm Fe3O4sub>, three α-e2O3nanoparticles samples of different sizes (11, 14, and 25 nm) and bulk α-e2O3 have been evaluated by inelastic neutron scattering methods. The contribution of the two-level magnetic spin flip transition to the heat capacity of the α-e2O3 particles has been determined. The isochoric heat capacity of the water confined on the surface of these two types of iron oxide particles have been calculated from their INS spectra, and is affected by the chemical composition of the underlying particle. Furthermore, the heat capacity and dynamics of the particle hydration layers appear to be influenced by a complex array of factors including particle size, water coverage, and possibly the magnetic state of the particle itself.

  19. Structural instability of the CoO4sub> tetrahedral chain in SrCoO3-δ thin films

    SciTech Connect

    Glamazda, A.; Choi, Kwang-yong; Lemmens, P.; Choi, Woo Seok; Jeen, Hyoungjeen; Meyer, Tricia L.; Lee, Ho Nyung


    Raman scattering experiments together with detailed lattice dynamic calculations are performed to elucidate crystallographic and electronic peculiarities of SrCoO3-δ films. We observe that the 85 cm-1 phonon mode involving the rotation of a CoO4sub> tetrahedron undergoes a hardening by 21 cm-1 when the temperature is decreased. In addition, new phonon modes appear at 651.5 and 697.6 cm-1 . The latter modes are attributed to the Jahn-Teller activated modes. Upon cooling from room temperature, all phonons exhibit an exponential-like increase of intensity with a characteristic energy of about 103–107 K. We attribute this phenomenon to an instability of the CoO4sub> tetrahedral chain structure, which constitutes a key ingredient to understand the electronic and structural properties of the brownmillerite SrCoO2.5.

  20. Disorder from order among anisotropic next-nearest-neighbor Ising spin chains in SrHo2O4sub>

    SciTech Connect

    Wen, J. -J.; Tian, W.; Garlea, V. O.; Koohpayeh, S. M.; McQueen, T. M.; Li, H. -F.; Yan, J. -Q.; Rodriguez-Rivera, J. A.; Vaknin, D.; Broholm, C. L.


    In this study, we describe why Ising spin chains with competing interactions in SrHo2O4sub> segregate into ordered and disordered ensembles at low temperatures (T). Using elastic neutron scattering, magnetization, and specific heat measurements, the two distinct spin chains are inferred to have Néel (↑↓↑↓) and double-Néel (↑↑↓↓) ground states, respectively. Below TN = 0.68(2)K, the Néel chains develop three-dimensional long range order (LRO), which arrests further thermal equilibration of the double-Néel chains so they remain in a disordered incommensurate state for T below TS = 0.52(2)K. SrHo2O4sub> distills an important feature of incommensurate low dimensional magnetism: kinetically trapped topological defects in a quasi–d–dimensional spin system can preclude order in d + 1 dimensions.

  1. Crystal structure and electrical properties of K/sub 3/Bi/sub 2/(VO/sub 4/)/sub 3/, a new potassium bismuth vanadate

    SciTech Connect

    Debreuille-Gresse, M.F.; Abraham, F.


    K/sub 3/Bi/sub 2/(VO/sub 4/)/sub 3/ crystallizes in the space group C2/c, a = 13.957(4), b = 13.858(4), c = 7.095(2) A, ..beta.. = 112.80(3)/sup 0/, Z = 4. The crystal structure was determined from single-crystal intensity data obtained by means of an automated four-circle diffractometer and refined to the conventional values R = 0.050 and R/sub w/ = 0.059 for 1498 observed reflections. The structure is characterized by a three-dimensional network of Bi/sub 2/O/sub 10/ units and VO/sub 4/ tetrahedra. A Bi/sub 2/O/sub 10/ unit is formed by two BiO/sub 6/ octahedra sharing an edge. K/sup +/ ions occupy three different crystallographic sites. One of them has a high thermal vibration which could reflect ionic mobility. The ionic conductivity highly increases at 790 K. DSC measurements show a reversible transition at this temperature. One K atom, and only one, can be substituted by one Na atom to give NaK/sub 2/Bi/sub 2/(VO/sub 4/)/sub 3/; this substitution improves the conductivity.

  2. Magnetic order in the S=1/2 two-dimensional molecular antiferromagnet, copper pyrazine perchlorate Cu(Pz){sub 2}(ClO{sub 4}){sub 2}.

    SciTech Connect

    Lancaster, T.; Blundell, S. J.; Brooks, M. L.; Baker, P. J.; Pratt, F. L.; Manson, J. L.; Connor, M. M.; Xiao, F.; Landee, C. P.; Chaves, F. A.; Soriano, S.; Novak, M. A.; Papageorgiou, T.; Bianchi, A.; Wosnitza, J.; Schlueter, J. A.; Materials Science Division; Oxford Univ.; Rutherford Appleton Lab.; Eastern Washington Univ.; Clark Univ.; Inst. de Fisica, UFRJ; Hochfeld-Magnetlabor Dresden


    We present an investigation of magnetic ordering in the two-dimensional S=1/2 quantum magnet Cu(Pz){sub 2}(ClO{sub 4}){sub 2} using specific heat and zero-field muon-spin relaxation ({mu}{sup +}SR). The magnetic contribution to the specific heat is consistent with an exchange strength of 17.7(3) K. We find unambiguous evidence for a transition to a state of three-dimensional long-range order below a critical temperature T{sub N} = 4.21(1) K using {mu}{sup +} SR even though there is no feature in the specific heat at that temperature. The absence of a specific heat anomaly at T{sub N} is consistent with recent theoretical predictions. The ratio of T{sub N}/J=0.24 corresponds to a ratio of intralayer to interlayer exchange constants of |J{prime}/J| = 6.8 x 10{sup -4}, indicative of excellent two-dimensional isolation. The scaled magnetic specific heat of [Cu(Pz){sub 2}(HF{sub 2})]BF{sub 4}, a compound with an analogous structure, is very similar to that of Cu(Pz){sub 2}(ClO{sub 4}){sub 2} although both differ slightly from the predicted value for an ideal 2D S=1/2 Heisenberg antiferromagnet.

  3. In situ studies of surface of NiFe2O4sub> catalyst during complete oxidation of methane

    SciTech Connect

    Zhang, Shiran; Shan, Junjun; Nie, Longhui; Nguyen, Luan; Wu, Zili; Tao, Franklin


    Here, NiFe2O4sub> with an inverse spinel structure exhibits high activity for a complete oxidation of methane at 400 °C–425 °C and a higher temperature. The surface of the catalyst and its adsorbates were well characterized with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ infrared spectroscopy (IR). In situ studies of the surface of NiFe2O4sub> using AP-XPS suggest the formation of methoxy-like and formate-like intermediates at a temperature lower than 200 °C, supported by the observed vibrational signatures in in situ IR studies. Evolutions of C1s photoemission features and the nominal atomic ratios of C/(Ni + Fe) of the catalyst surface suggest that the formate-like intermediate is transformed to product molecules CO2 and H2O in the temperature range of 250–300 °C. In situ studies suggest the formation of a spectator, – Olattice – CH2 – Olattice –. It strongly bonds to surface through C–O bonds and cannot be activated even at 400 °C.

  4. Monodispersed Li4sub>Ti5O12 with Controlled Morphology as High Power Lithium Ion Battery Anodes

    SciTech Connect

    Li, Yunchao; Fu, Guoyi; Watson, Mark; Harrison, Stephen; Paranthaman, M Parans


    Monodispersed Li4sub>Ti5O12 (LTO) nanoparticles with controlled microstructure were successfully synthesized by a combination of hydrolysis and hydrothermal method followed by a post-annealing process. The scanning electron microscopy images showed that particles with a size of 30-40 nm were precisely controlled throughout the synthesis process. The electrochemical tests of the as-prepared LTO electrodes in a half-cell proved its high rate performance and outstanding cyclability which benefits from the preserved well-controlled nanoparticle size and morphology. LTO electrodes were also tested in a full cell configuration in pairing with LiFePO4sub> cathodes, which demonstrated a capacity of 147.3 mAh g-1. In addition, we have also demonstrated that LTO materials prepared using lithium salts separated from geothermal brine solutions had good cyclability. These demonstrations provide a promising way for making low-cost, large-scale LTO electrode materials for energy storage applications.

  5. Conduction below 100 °C in nominal Li6ZnNb4sub>O14

    SciTech Connect

    Li, Yunchao; Paranthaman, Mariappan Parans; Gill, Lance W.; Edward W. Hagaman; Wang, Yangyang; Sokolov, Alexei P.; Dai, Sheng; Ma, Cheng; Chi, Miaofang; Veith, Gabriel M.; Manthiram, Arumugam; Goodenough, John B.


    The increasing demand for a safe rechargeable battery with a high energy density per cell is driving a search for a novel solid electrolyte with a high Li+ or Na+ conductivity that is chemically stable in a working Li-ion or Na-ion battery. Li6ZnNb4sub>O14 has been reported to exhibit a σ Li > 10-2 S cm-1 at 250 °C, but to disproportionate into multiple phases on cooling from 850 °C to room temperature. An investigation of the room-temperature Li-ion conductivity in a porous pellet of a multiphase product of a nominal Li6ZnNb4sub>O14 composition is shown to have bulk σ Li 3.3 x 10-5 S cm-1 at room temperature that increases to 1.4 x 10-4 S cm-1 by 50 °C. 7Li MAS NMR spectra were fitted to two Lorentzian lines, one of which showed a dramatic increase with increasing temperature. As a result, a test for water stability indicates that Li+ may move to the particle and grain surfaces to react with adsorbed water as occurs in the garnet Li+ conductors.

  6. Hydrothermal syntheses, structures, and properties of two new potassium vanadium phosphates: K[sub 3](VO)(V[sub 2]O[sub 3])(PO[sub 4])[sub 2](HPO[sub 4]) and K[sub 3](VO)(HV[sub 2]O[sub 3])(PO[sub 4])[sub 2](HPO[sub 4])

    SciTech Connect

    Vaughey, J.T.; Harrison, T.A.; Jacobson, A.J. )


    Two new potassium vanadium phosphates have been prepared and their structures have been determined from analysis of single crystal X-ray data. The two compounds, K[sub 3](VO)(V[sub 2]O[sub 3])(PO[sub 4])[sub 2](HPO[sub 4]) and K[sub 3](VO)(HV[sub 2]O[sub 3])(PO[sub 4])[sub 2](HPO[sub 4]), are isostructural, except for the incorporation of an extra hydrogen atom into the nearly identical frameworks. The structures consist of a three-dimensional network of [VO][sub n] chains connected through phosphate groups to a [V[sub 2]O[sub 3

  7. Electrochemically influenced cation inter-diffusion and Co3O4sub> formation on La0.6Sr0.4sub>CoO3 infiltrated into SOFC cathodes

    SciTech Connect

    Song, Xueyan; Lee, Shiwoo; Chen, Yun; Gerdes, Kirk


    Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm2O3-doped CeO2 (SDC) and La0.6Sr0.4sub>Co0.2Fe0.8O3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La0.6Sr0.4sub>CoO3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibit comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from the LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co3O4sub> nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co3O4sub> forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.

  8. Phosphorus-bridged ansa-metallocene complexes of titanium, zirconium, and hafnium: The syntheses and structures of [PhP(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} and [Ph(E)P(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} (E = O, S, Se) derivatives

    SciTech Connect

    Shin, J.H.; Hascall, T.; Parkin, G.


    A series of phosphorus-bridged ansa-metallocene complexes of titanium, zirconium, and hafnium, [PhP(XC{sub 5}Me{sub 4}){sub 2}]MX{sub 2} and [Ph(E)P(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} (X = Cl, Me, CO, (Se{sub 3}){sub 0.5}; E = O, S, Se), has been synthesized. Structural characterization by X-ray diffraction indicates that, in comparison to their non-ansa counterparts (C{sub 5}Me{sub 5}){sub 2}MX{sub 2}, the cyclopentadienyl groups in phosphorus-bridged complexes are displaced from symmetric {eta}{sup 5}-coordination toward {eta}{sup 3}-coordination. Such {eta}{sup 3},{eta}{sup 3}-coordination creates more electrophilic metal centers than those in their permethylcyclopentadienyl counterparts, as judged by the {nu}(CO) stretching frequencies of the zirconium dicarbonyl complexes Cp{sup *}{sub 2}Zr(CO){sub 2} (1946 and 1853 cm{sup {minus}1}) and [PhP(C{sub 5}Me{sub 4}){sub 2}]Zr(CO){sub 2} (1959 and 1874 cm{sup {minus}1}).

  9. Crystal structure and magnetic properties of NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl

    SciTech Connect

    Jin Tengteng; Liu Wei; Chen Shuang; Prots, Yurii; Schnelle, Walter; Zhao Jingtai; Kniep, Ruediger; Hoffmann, Stefan


    A new copper(II) oxide phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], has been synthesized by flux synthesis. Single-crystal X-ray diffraction data show that the title compound crystallizes in the monoclinic system, space group P2{sub 1}/c (No. 14), with lattice parameters a=8.392(2) A, b=6.3960(10) A, c=16.670(2) A, {beta}=109.470(10) Degree-Sign , V=843.6(3) A{sup 3}, Z=4. The crystal structure is characterized by a complex chain of copper-centered polyhedra running along [0 1 0] which are connected by phosphate tetrahedra. The resulting three-dimensional polyhedra framework exhibits channels filled by additional copper and sodium atoms. Field and temperature dependent measurements of the specific heat and the magnetic susceptibility reveal low-dimensional magnetic behavior. The compound starts to decompose at 700 K under release of oxygen and evaporation of Cu{sup I}Cl as shown by simultaneous thermogravimetry and mass spectrometry. - Graphical abstract: The crystal structure of the new copper(II) phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], exhibits linear chains of copper tetrahedra which show low-dimensional magnetic behavior proven by specific heat and magnetic susceptibility measurements. Highlights: Black-Right-Pointing-Pointer A new copper(II) oxide phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], has been synthesized by flux synthesis. Black-Right-Pointing-Pointer The crystal structure comprises chains of Cu{sub 4}O tetrahedra. Black-Right-Pointing-Pointer Low-dimensional behavior has been proven by magnetic and specific heat measurements. Black-Right-Pointing-Pointer On heating, Cu{sup I}Cl and oxygen are released shown by simultaneous thermogravimetry and mass spectrometry.

  10. 119Sn-NMR investigations on superconducting Ca3Ir4sub>Sn13: Evidence for multigap superconductivity

    SciTech Connect

    Sarkar, R.; Petrovic, C.; Bruckner, F.; Gunther, M.; Wang, Kefeng; Biswas, P. K.; Luetkens, H.; Morenzoni, E.; Amato, A.; Klauss, H. -H.


    In this study, we report bulk superconductivity (SC) in Ca3Ir4sub>Sn13 by means of 119Sn nuclear magnetic resonance (NMR) experiments. Two classical signatures of BCS superconductivity in spin-lattice relaxation rate (1/T1), namely the Hebel–Slichter coherence peak just below the Tc, and the exponential decay in the superconducting phase, are evident. The noticeable decrease of 119Sn Knight shift below Tc indicates spin-singlet superconductivity. The temperature dependence of the spin-lattice relaxation rate 119(1/T1) is convincingly described by the multigap isotropic superconducting gap. NMR experiments do not witness any sign of enhanced spin fluctuations.

  11. Theoretical crystal chemistry of M{sub x}(TO{sub 4}){sub y} sulfates and selenates: Topological analysis and classification of suprapolyhedral invariants

    SciTech Connect

    Ilyushin, G. D. Blatov, V. A.


    A geometric topological analysis of orthotetrahedral phases M{sub x}(TO{sub 4}){sub y} (T = S or Se) is performed for 46 sulfates and 17 selenates with the TOPOS 3.2 software package. The values of coordination sequences {l_brace}N{sub k}{r_brace} of T atoms are used as classification parameters of topologically different MTO nets. The crystal structures are analyzed within 12 coordination spheres of T sites and assigned to 26 topological types. It is established that only 7 types are common for the structures of sulfates and selenates, 16 types include only sulfates, and 3 types include only selenates. The average values of the bond lengths are determined: = 1.48(2) A and = 1.63(2) A. The hierarchical ordering of the crystal structure is performed using the concept of a polyhedral microensemble of the structure.

  12. Multiband Te p Based Superconductivity of Ta4sub>Pd3Te16

    SciTech Connect

    Singh, David J.


    We recently discovered that Ta4sub>Pd3Te16 is a superconductor that has been suggested to be an unconventional superconductor near magnetism. Here, we report electronic structure calculations showing that despite the layered crystal structure the material is an anisotropic three-dimensional (3D) metal. The Fermi surface contains prominent one-dimensional (1D) and two-dimensional (2D) features, including nested 1D sheets, a 2D cylindrical section, and a 3D sheet. Moreover, the electronic states that make up the Fermi surface are mostly derived from Te p states with small Ta d and Pd d contributions. This places the compound far from magnetic instabilities. The results are discussed in terms of multiband superconductivity.

  13. Beam quality management by periodic reproduction of wavefront aberrations in end-pumped Nd:YVO4sub> laser amplifiers.


    Liu, Bin; Liu, Chong; Shen, Lifeng; Wang, Chunhua; Ye, Zhibin; Liu, Dong; Xiang, Zhen


    A method for beam quality management is presented in a master oscillator power amplifier (MOPA) using Nd:YVO4sub> as the gain medium by extra-cavity periodic reproduction of wavefront aberrations. The wavefront aberration evolution of the intra-cavity beams is investigated for both symmetrical and asymmetrical resonators. The wavefront aberration reproduction process is successfully realized outside the cavity in four-stage amplifiers. In the MOPA with a symmetrical oscillator, the laser power increases linearly and the beam quality hardly changes. In the MOPA with an asymmetrical oscillator, the beam quality is deteriorated after the odd-stage amplifier and is improved after the even-stage amplifier. The wavefront aberration reproduction during the extra-cavity beam propagation in the amplifiers is equivalent to that during the intra-cavity propagation. This solution helps to achieve the effective beam quality management in laser amplifier chains. PMID:27137329

  14. Optical modeling and optimizations of Cu2ZnSnSe4sub> solar cells using the modified transfer matrix method.


    Cozza, Dario; Ruiz, Carmen M; Duché, David; Giraldo, Sergio; Saucedo, Edgardo; Simon, Jean Jacques; Escoubas, Ludovic


    The fast and computationally inexpensive Modified Transfer Matrix Method (MTM) is employed to simulate the optical response of kesterite Cu2ZnSnSe4sub> solar cells. This method can partially take into account the scattering effects due to roughness at the interfaces between the layers of the stack. We analyzed the optical behavior of the whole cell structure by varying the thickness of the TCO layer (iZnO + ITO) between 50 and 1200 nm and the buffer CdS layer between 0 and 100 nm. We propose optimal combinations of the TCO/CdS thicknesses that can locally maximize the device photocurrent. We provide experimental data that qualitatively confirm our theoretical predictions. PMID:27607723

  15. New insights into the thermodynamic behavior of 2LiBH4sub>-MgH2 composite for hydrogen storage

    SciTech Connect

    Cova, Federico; Ronnebro, Ewa; Choi, Yong-Joon; Gennari, Fabiana; Larochette, Pierre


    The composite 2LiBH4sub>:MgH2 has been studied as a possible hydrogen storage material due to its high storage capacity. The present work is directed towards the clarification of the thermodynamic behavior of the system, especially in the temperature region above 400°C. We reveal different reaction paths during hydrogen absorption and desorption at various temperatures which has important implication for applications. At temperatures higher than 413°C, the observation of two different absorption pressure plateaus indicates that two different reactions occur, however, below this temperature there is only one plateau present in the system. During desorption, the double plateau can be observed at temperatures as low as 375°C.

  16. Nanoparticles of K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}:Eu as effective detectors for swift heavy ions

    SciTech Connect

    Salah, Numan; Lochab, S. P.; Kanjilal, D.; Ranjan, Ranju; Habib, Sami S.; Rupasov, A. A.; Aleynikov, V. E.


    The modification of thermoluminescence (TL) and photoluminescence (PL) properties of K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}:Eu nanoparticles by swift heavy ions (SHI), irradiation is studied. Pellets form of the nanomaterials were irradiated by 48 MeV Li{sup 3+}, 75 MeV C{sup 6+}, and 90 MeV O{sup 7+} ion beams. The fluence range is 1x10{sup 9}-1x10{sup 13} ions/cm{sup 2}. The modification in TL glow curves of the nanomaterials irradiated by Li{sup 3+}, C{sup 6+}, and O{sup 7+} ion beams are essentially similar to those induced by {gamma}-ray irradiation. These glow curves have single peaks at around 427 K with a small variation in their positions by around {+-}3 K. The TL intensity of the ion beams irradiated nanomaterials is found to decease, while going from low to high atomic number (Z) ions (i.e., Li{sup 3+}{yields}O{sup 7+}). The TL response curve of the pellets irradiated by Li{sup 3+} ions is linear in the whole range of studied fluences. The curves for C{sup 6+} and O{sup 7+} irradiated samples are linear at lower fluences (1x10{sup 9}-1x10{sup 12} ion/cm{sup 2}) and then saturate at higher fluence. These results for the nanomaterials are much better than that of the corresponding microcrystalline samples irradiated with a Li{sup 3+} ion. The curves were linear up to the fluence 1x10{sup 11} ion/cm{sup 2} and then become sublinear at higher fluences. The TL efficiency values of K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}:Eu nanoparticles irradiated by 48 MeV Li{sup 3+}, 75 MeV C{sup 6+}, and 90 MeV O{sup 7+} ion beams have been measured relative to {gamma} rays of {sup 60}Co and are found to be 0.515, 0.069, and 0.019, respectively. This value for the Li{sup 3+} ion (0.515) is much higher than that of the corresponding microcrystalline material (0.0014). These superiorities for the nanomaterials make K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}:Eu nanophosphor a suitable candidate for detecting the doses of swift heavy ions. PL studies on the ion beams irradiated and

  17. Thermal expansion of NaTi/sub 2/(PO/sub 4/)/sub 3/ studied by Rietveld method from x-ray diffraction data

    SciTech Connect

    Rodrigo, J.L.; Carrasco, P.; Alamo, J. )


    Previous disagreement about the thermal expansion of the rhombohedral compound, NZP-type, NaTi/sub 2/(PO/sub 4/)/sub 3/ is clarified. It is shown that thermal stresses affect the thermal expansion, but they relax after some time of storage. Its anisotropic thermal expansion, has been calculate from high temperature X-ray diffraction, and it is linear in the range from room temperature up to 800{sup 0}C. The predictability of thermal expansion and the tailoring of the composition of NZP ceramics require checking whether the thermal effect on the rotations and distortions of the atomic polyhedra in this structure is the responsible for the high anisotropy in the thermal expansion. This effect has been determined experimentally by solving the chemical structure at five different temperatures, applying the Rietveld method to deconvolute the powder X-ray diffraction profiles.

  18. Temperature, Oxygen, and Soot-Volume-Fraction Measurements in a Turbulent C2H4sub>-Fueled Jet Flame

    SciTech Connect

    Kearney, Sean P.; Guildenbecher, Daniel Robert; Winters, Caroline; Farias, Paul Abraham; Grasser, Thomas W.; Hewson, John C.


    We present a detailed set of measurements from a piloted, sooting, turbulent C 2 H 4 sub>- fueled diffusion flame. Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (CARS) is used to monitor temperature and oxygen, while laser-induced incandescence (LII) is applied for imaging of the soot volume fraction in the challenging jet-flame environment at Reynolds number, Re = 20,000. Single-laser shot results are used to map the mean and rms statistics, as well as probability densities. LII data from the soot-growth region of the flame are used to benchmark the soot source term for one-dimensional turbulence (ODT) modeling of this turbulent flame. The ODT code is then used to predict temperature and oxygen fluctuations higher in the soot oxidation region higher in the flame.

  19. Negative to positive magnetoresistance and magnetocaloric effect in Pr0.6Er0.4sub>Al2

    SciTech Connect

    Pathak, Arjun K.; Gschneidner, Jr., K. A.; Pecharsky, V. K.


    We report on the magnetic, magnetocaloric and magnetotransport properties of Pr0.6Er0.4sub>Al2. The title compound exhibits a large positive magnetoresistance (MR) for H ≥ 40 kOe and a small but non negligible negative MR for H ≤ 30 kOe. The maximum positive MR reaches 13% at H = 80 kOe. The magnetic entropy and adiabatic temperature changes as functions of temperature each show two anomalies: a broad dome-like maximum below 20 K and a relatively sharp peak at higher temperature. As a result, observed behaviors are unique among other binary and mixed lanthanide compounds.

  20. Calorimetric, spectroscopic and structural investigations of phase polymorphism in [Ru(NH{sub 3}){sub 6}](BF{sub 4}){sub 3}. Part I

    SciTech Connect

    Dolega, Diana; Mikuli, Edward; Inaba, Akira; Gorska, Natalia; Holderna-Natkaniec, Krystyna; Nitek, Wojciech


    Four crystalline phases of the coordination compound [Ru(NH{sub 3}){sub 6}](BF{sub 4}){sub 3} are identified by adiabatic calorimetry. Three phase transitions, one at T{sub C3}(IV{yields}III)=30.7 K, the second at T{sub C2}(III{yields}II)=91.7 K (both accompanied by comparable entropy changes 3.0 and 3.1 J K{sup -1} mol{sup -1}, respectively) and the third at T{sub C1}(II{yields}I)=241.6 K (accompanied by an entropy change of 8.1 J K{sup -1} mol{sup -1}) were discovered. X-ray single crystal diffraction (at 293 K) demonstrates that phase I is a highly dynamic disordered cubic phase (Fm3{sup Macron }m, No. 225) with two types of BF{sub 4}{sup -} anions differing in a degree of disorder. In phase II (at 170 K) the structure remains cubic (Ia3{sup Macron }, No. 206), with two different types of cations and four different types of anions. Splitting of certain IR bands connected with NH{sub 3} ligands at the observed phase transitions suggests a lowering of the symmetry of the [Ru(NH{sub 3}){sub 6}]{sup 3+} complex cation. Both NH{sub 3} ligands and BF{sub 4}{sup -} anions perform fast reorientations ({tau}{sub R} Almost-Equal-To 10{sup -12} s), which are significantly slowed down below the phase transition at T{sub C3}. {sup 1}H NMR studies led to estimate the values of the activation energy of NH{sub 3} ligands reorientation in the phases II and I as equal to {approx}8 kJ mol{sup -1}. In phase I the whole hexammineruthenium(III) cations reorientation as a tumbling process can be noticed. The activation energy value of this motion is {approx}24 kJ mol{sup -1}. {sup 19}F NMR studies give the values of the activation energy of BF{sub 4}{sup -} anions reorientation as {approx}6 kJ mol{sup -1}. Above the phase transition temperature half of BF{sub 4}{sup -} anions perform a tumbling motion with E{sub a} Almost-Equal-To 8 kJ mol{sup -1}. - Graphical abstract: A series of complementary methods, such as Adiabatic Calorimetry, Differential Scanning Calorimetry, Fourier

  1. One Dimensional(1D)-to-2D Crossover of Spin Correlations in the 3D Magnet ZnMn2O4sub>

    SciTech Connect

    Disseler, S. M.; Chen, Y.; Yeo, S.; Gasparovic, G.; Piccoli, P. M. B.; Schultz, A. J.; Qiu, Y.; Huang, Q.; Cheong, S. -W.; Ratcliff, W.


    In this paper we report on the intriguing evolution of the dynamical spin correlations of the frustrated spinel ZnMn2O4sub>. Inelastic neutron scattering and magnetization studies reveal that the dynamical correlations at high temperatures are 1D. At lower temperature, these dynamical correlations become 2D. Surprisingly, the dynamical correlations condense into a quasi 2D Ising-like ordered state, making this a rare observation of two dimensional order on the spinel lattice. Remarkably, 3D ordering is not observed down to temperatures as low as 300 mK. This unprecedented dimensional crossover stems from frustrated exchange couplings due to the huge Jahn-Teller distortions around Mn3+ ions on the spinel lattice.

  2. Generation of 30  fs pulses from a diode-pumped graphene mode-locked Yb:CaYAlO4sub> laser.


    Ma, Jie; Huang, Haitao; Ning, Kaijie; Xu, Xiaodong; Xie, Guoqiang; Qian, Liejia; Loh, Kian Ping; Tang, Dingyuan


    Stable 30 fs pulses centered at 1068 nm (less than 10 optical cycles) are demonstrated in a diode pumped Yb:CaYAlO4sub> laser by using high-quality chemical vapor deposited monolayer graphene as the saturable absorber. The mode-locked 8.43 optical-cycle pulses have a spectral bandwidth of ∼50  nm and a pulse repetition frequency of ∼113.5  MHz. To the best of our knowledge, this is the shortest pulse ever reported for graphene mode-locked lasers and mode-locked Yb-doped bulk lasers. Our experimental results demonstrate that graphene mode locking is a very promising practical technique for directly generating few-cycle optical pulses from a laser oscillator. PMID:26974072

  3. The behavior of thermal conductivity in the chaotic phase of [N(CH{sub 3}){sub 4}]{sub 2}ZnCl{sub 4} crystal

    SciTech Connect

    Sveleba, S. A. Karpa, I. V.; Kunyo, I. M.; Semotyuk, O. V.; Katerynchuk, I. M.; Phitsych, E. I.; Pankivskyi, Yu. I.


    A thermal investigation of the modulated structure dynamics at the transition between metastable states in the incommensurate phase of [N(CH{sub 3}){sub 4}]{sub 2}ZnCl{sub 4} crystal have been performed. It is established that the anomalous behavior of the thermal conductivity in the absence of a defect-density wave is due to the inelastic scattering of thermal phonons from critical phonons of the soft optical branch. In the presence of a defect-density wave, the anomalous increase in thermal conductivity is caused by the existence of a chaotic phase and is related to the contribution that soft optical phonons make to the heat transfer due to the increase in their group velocity.

  4. Enhanced ferromagnetic order in Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} featuring canted [MnO{sub 4}]{sub ∞} spin chains of mixed-valent Mn(III)/Mn(IV). Aliovalent substitution of the Sr{sub 4−x}Ln{sub x}Mn{sup III}{sub 2+x}Mn{sup IV}{sub 1−x}O{sub 3}(GeO{sub 4}){sub 3} solid-solution

    SciTech Connect

    West, J. Palmer; Sulejmanovic, Dino; Becht, Gregory; He, Jian; Hitchcock, Dale; Yan, Yonggao; Hwu, Shiou-Jyh


    Crystals of Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0; x∼0.15 for Ln=La, Pr, Nd, Sm. Eu, Gd, Dy; x∼0.3 for Ln=Gd) were isolated upon using high-temperature, solid-state methods in molten-salt media. These compounds are isostructural with the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} (Ln=La, Sm, Gd) series that contains the same [MnO{sub 4}]{sub ∞} spin chains. The synthesis of the Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0) phase was carried out by a double aliovalent substitution with respect to the Sr{sup 2+} and Ge{sup 4+} ions that replace Na{sup +}/Ln{sup 3+} and As{sup 5+} in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, respectively. The title series contains mixed-valent Mn(III)/Mn(IV) and shows a limited range of solid solution, both of which were not observed in the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series. To form the Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} solid solution, one of the Sr{sup 2+} sites, i.e., the original Ln-site in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, is partially substituted by Ln{sup 3+} in a statistical disorder of Sr{sub 1−x}/Ln{sub x}. Initial magnetic investigations of selected derivatives reveal higher ferromagnetic ordering temperatures than those reported for the Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series, presumably attributed to a lesser degree of canting as a result of introducing non-Jahn–Teller Mn{sup 4+} ions. Also intriguing is the observation of multiple anomalies at low temperatures which appear to be of electronic origins. - Graphical abstract: Sr{sub 4−x}Ln{sub x}Mn(III){sub 2+x}Mn(IV){sub 1−x}O{sub 3}(GeO{sub 4}){sub 3}. Display Omitted - Highlights: • Double aliovalent substitution: Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} with respect to Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}. • Solid solution with respect to statistical disorder of Sr{sub 1

  5. Decoupling of the antiferromagnetic and insulating states in Tb-doped Sr2IrO4sub>

    SciTech Connect

    Wang, J. C.; Aswartham, S.; Ye, Feng; Terzic, J.; Zheng, H.; Haskel, Daniel; Chikara, Shalinee; Choi, Yong; Schlottmann, P.; Custelcean, Radu; Yuan, S. J.; Cao, G.


    Sr2IrO4sub> is a spin-orbit coupled insulator with an antiferromagnetic (AFM) transition at TN = 240 K. We report results of a comprehensive study of single-crystal Sr2Ir1-xTbxO4sub> (0≤x≤0.03). This study found that mere 3% (x=0.03) tetravalent Tb4+(4f7) substituting for Ir4+ (rather than Sr2+) completely suppresses the long-range collinear AFM transition but retains the insulating state, leading to a phase diagram featuring a decoupling of magnetic interactions and charge gap. The insulating state at x = 0.03 is characterized by an unusually large specific heat at low temperatures and an incommensurate magnetic state having magnetic peaks at (0.95, 0, 0) and (0, 0.95, 0) in the neutron diffraction, suggesting a spiral or spin density wave order. It is apparent that Tb doping effectively changes the relative strength of the SOI and the tetragonal CEF and enhances the Hund’s rule coupling that competes with the SOI, and destabilizes the AFM state. However, the disappearance of the AFM accompanies no metallic state chiefly because an energy level mismatch for the Ir and Tb sites weakens charge carrier hopping and renders a persistent insulating state. Furthermore, this work highlights an unconventional correlation between the AFM and insulating states in which the magnetic transition plays no critical role in the formation of the charge gap in the iridate.

  6. Complex conductance of ultrathin La2-xSrxCuO4sub> films and heterostructures

    SciTech Connect

    V. A. Gasparov; Bozovic, I.


    We used atomic-layer molecular beam epitaxy to synthesize bilayers of a cuprate metal (La1.55Sr0.45CuO4sub>) and a cuprate insulator (La2CuO4sub>), in which each layer is just one unit cells thick. We have studied the magnetic field and temperature dependence of the complex sheet conductance, σ(ω), of these films. Experiments have been carried out at frequencies between 2 and 50 MHz using the single-spiral coil technique. We found that: (i) the inductive response starts at ΔT = 3 K lower temperatures than Re σ(T), which in turn is characterized by a peak close to the transition, (ii) this shift is almost constant with magnetic field up to 14 mT; (iii) ΔT increases sharply up to 4 K at larger fields and becomes constant up to 8 T; (iv) the vortexdiffusion constant D(T) is not linear with T at low temperatures as in the case of free vortices, but is rather exponential due to pinning of vortex cores, and (v) the dynamic Berezinski–Kosterlitz–Thouless (BKT) transition temperature occurs at the point where Y=(lω/ξ+)2 = 1. As a result, our experimental results can be described well by the extended dynamic theory of the BKT transition and dynamics of bound vortex–antivortex pairs with short separation lengths.

  7. Self-powdering and nonlinear optical domain structures in ferroelastic beta'-Gd{sub 2}(MoO{sub 4}){sub 3} crystals formed in glass

    SciTech Connect

    Tsukada, Y.; Honma, T.; Komatsu, T.


    Ferroelastic beta'-Gd{sub 2}(MoO{sub 4}){sub 3}, (GMO), crystals are formed through the crystallization of 21.25Gd{sub 2}O{sub 3}-63.75MoO{sub 3}-15B{sub 2}O{sub 3} glass (mol%), and two scientific curious phenomena are observed. (1) GMO crystals formed in the crystallization break into small pieces with a triangular prism or pyramid shape having a length of 50-500 {mu}m spontaneously during the crystallizations in the inside of an electric furnace, not during the cooling in air after the crystallization. This phenomenon is called 'self-powdering phenomenon during crystallization' in this paper. (2) Each self-powdered GMO crystal grain shows a periodic domain structure with different refractive indices, and a spatially periodic second harmonic generation (SHG) depending on the domain structure is observed. It is proposed from polarized micro-Raman scattering spectra and the azimuthal dependence of second harmonic intensities that GMO crystals are oriented in each crystal grain and the orientation of (MoO{sub 4}){sup 2-} tetrahedra in GMO crystals changes periodically due to spontaneous strains in ferroelastic GMO crystals. - Graphical abstract: This figure shows the polarized optical photograph at room temperature for a particle (piece) obtained by a heat treatment of the glass at 590 deg. C for 2 h in an electric furnace in air. This particle was obtained through the self-powdering behavior in the crystallization of glass. The periodic domain structure is observed. Ferroelastic beta'-Gd{sub 2}(MoO{sub 4}){sub 3} crystals are formed in the particle, and second harmonic generations are detected, depending on the domain structure.

  8. Lithium diffusion in Li4sub>Ti5O12 at high temperatures

    SciTech Connect

    Vijayakumar, M.; Kerisit, Sebastien; Rosso, Kevin M.; Burton, Sarah D.; Sears, Jesse A.; Yang, Zhenguo; Graff, Gordon L.; Liu, Jun; Hu, Jianzhi


    Synthesis of the spinel lithium titanate Li4sub>Ti5O12 by an alkoxide-free sol–gel method is described. This method yields highly pure and crystalline Li4sub>Ti5O12 samples at relatively low temperature (850 °C) and via short thermal treatment (2 h). 6Li magic angle spinning nuclear magnetic resonance (MAS NMR) measurements on these samples were carried out at high magnetic field (21.1 T) and over a wide temperature range (295–680 K). The temperature dependence of the chemical shifts and integral intensities of the three 6Li resonances demonstrates the migration of lithium ions from the tetrahedral 8a to the octahedral 16c sites and the progressive phase transition from a spinel to a defective NaCl-type structure. This defective structure has an increased number of vacancies at the 8a site, which facilitate lithium diffusion through 16c → 8a → 16c pathways, hence providing an explanation for the reported increase in conductivity at high temperatures. Molecular dynamics simulations of the spinel oxides Li4+xTi5O12, with 0 ≤ x ≤ 3, were also performed with a potential shell model in the temperature range 300–700 K. Finally, the simulations support the conclusions drawn from the NMR measurements and show a significant timescale separation between lithium diffusion through 8a and 16c sites and that out of the 16d sites.

  9. Enhanced thermoelectric performance driven by high-temperature phase transition in the phase change material Ge4sub>SbTe5

    SciTech Connect

    Williams, Jared B.; Lara-Curzio, Edgar; Cakmak, Ercan; Watkins, Thomas R.; Morelli, Donald T.


    Phase change materials are identified for their ability to rapidly alternate between amorphous and crystalline phases and have large contrast in the optical/electrical properties of the respective phases. The materials are primarily used in memory storage applications, but recently they have also been identified as potential thermoelectric materials. Many of the phase change materials researched today can be found on the pseudo-binary (GeTe)1-x(Sb2Te3)x tie-line. While many compounds on this tie-line have been recognized as thermoelectric materials, here we focus on Ge4sub>SbTe5, a single phase compound just off of the (GeTe)1-x(Sb2Te3)x tie-line, that forms in a stable rocksalt crystal structure at room temperature. We find that stoichiometric and undoped Ge4sub>SbTe5 exhibits a thermal conductivity of ~1.2 W/m-K at high temperature and a large Seebeck coefficient of ~250 μV/K. The resistivity decreases dramatically at 623 K due to a structural phase transition which lends to a large enhancement in both thermoelectric power factor and thermoelectric figure of merit at 823 K. In a more general sense the research presents evidence that phase change materials can potentially provide a new route to highly efficient thermoelectric materials for power generation at high temperature.

  10. Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. II. Tubular fragments and cation-cation interactions in the 3D framework structures of Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})], Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})], Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O

    SciTech Connect

    Alekseev, Evgeny V.; Krivovichev, Sergey V.; Depmeier, Wulf


    Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 for 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4

  11. Synthesis of MoS2/g-C3N4sub> nanocomposites with enhanced visible-light photocatalytic activity for the removal of nitric oxide (NO).


    Wen, M Q; Xiong, T; Zang, Z G; Wei, W; Tang, X S; Dong, F


    Molybdenum disulfide and graphitic carbon nitride (MoS2-g-C3N4sub>) nanocomposites with visible-light induced photocatalytic activity were successfully synthesized by a facile ultrasonic dispersion method. The crystalline structure and morphology of the MoS2-g-C3N4sub> nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microcopy (TEM), high-resolution TEM (HRTEM) and scanning electron microscopy (SEM). The optical property of the as-prepared nanocomposites was studied by ultraviolet visible diffusion reflection (UV-vis) and photoluminescence(PL) spectrum. It could be observed from the TEM image that the MoS2 nanosheets and g-C3N4sub> nanoparticles were well combined together. Moreover, the photocatalytic activity of MoS2-g-C3N4sub> composites was evaluated by the removal of nitric oxide under visible light irradiation (>400nm). The experimental results demonstrated that the nanocomposites with the MoS2 content of 1.5 wt% exhibited optimal photocatalytic activity and the corresponding removal rate of NO achieved 51.67%, higher than that of pure g-C3N4sub> nanoparticles. A possible photocatalytic mechanism for the MoS2-g-C3N4sub> nanocomposites with enhanced photocatalytic activity could be ascribed to the hetero-structure of MoS2 and g-C3N4sub>. PMID:27409846

  12. Electronic Structure and Optical Properties of Cu2ZnGeSe4sub>. First-Principles Calculations and Vacuum-Ultraviolet Spectroscopic Ellipsometric Studies

    SciTech Connect

    Choi, Sukgeun; Park, Ji-Sang; Donohue, Andrea; Christensen, Steven T.; To, Bobby; Beall, Carolyn; Wei, Su-Huai; Repins, Ingid L.


    Cu2ZnGeSe4sub> is of interest for the development of next-generation thin-film photovoltaic technologies. To understand its electronic structure and related fundamental optical properties, we perform first-principles calculations for three structural variations: kesterite, stannite, and primitive-mixed CuAu phases. The calculated data are compared with the room-temperature dielectric functionϵ=ϵ1+iϵ2 spectrum of polycrystalline Cu2ZnGeSe4sub> determined by vacuum-ultraviolet spectroscopic ellipsometry in the photon-energy range of 0.7 to 9.0 eV. Ellipsometric data are modeled with the sum of eight Tauc-Lorentz oscillators, and the best-fit model yields the band-gap and Tauc-gap energies of 1.25 and 1.19 eV, respectively. A comparison of overall peak shapes and relative intensities between experimental spectra and the calculated ϵ data for three structural variations suggests that the sample may not have a pure (ordered) kesterite phase. We found that the complex refractive index N=n+ik, normal-incidence reflectivity R, and absorption coefficients α are calculated from the modeled ϵ spectrum, which are also compared with those of Cu2ZnSnSe4sub> . The spectral features for Cu2ZnGeSe4sub> appear to be weaker and broader than those for Cu2ZnSnSe4sub> , which is possibly due to more structural imperfections presented in Cu2ZnGeSe4sub> than Cu2ZnSnSe4sub> .

  13. Crystal structure of Cs/sup +/((XeOF/sub 4/)/sub 3/F)/sup -/ and vibrational study of the /sup 18/O-enriched (XeOF/sub 5/)/sup -/ and ((XeOF/sub 4/)/sub 3/F)/sup -/ anions

    SciTech Connect

    Holloway, J.H.; Kaucic, V.; Martin-Rovet, D.; Russell, D.R.; Schrobilgen, G.J.; Selig, H.


    The cesium salts of the anions (XeOF/sub 5/)/sup -/ and ((XeOF/sub 4/)/sub 3/F)/sup -/ have been prepared and characterized. The Raman spectra of Xe/sup 16/OF/sub 5//sup -/ and Xe/sup 18/OF/sub 5//sup -/ are consistent with a stereochemically active lone pair in the xenon valence shell that results in a distorted octahedral arrangement of five fluorine and one oxygen around xenon to give C/sub s/ symmetry. The X-ray structure of Cs/sup +/((XeOF/sub 4/)/sub 3/F)/sup -/ has been obtained. Crystals are cubic, space group Pa3 with a = 13.993 (7) A and Z = 8. The structure was solved by means of Patterson and Fourier synthesis and refined by the least-squares method to R = 0.0969 and R/sub w/ = 0.0960 for 355 reflections. The anion possesses C/sub 3/ symmetry and consists of octahedra of O=XeF/sub 4/E (E = lone electron pair; mean XeF = 1.90 (3) A; Xe=O = 1.70 (5) A) linked through three fluorine bridges with the trigonally bonded fluorine positioned 0.49 A above the plane defined by the three xenon atoms. The Raman spectra of the /sup 16/O//sup 18/O isotopic isomers of (XeOF/sub 4/)/sub 3/F)/sup -/ and their associated coupling patterns have been interpreted on the basis of the X-ray structure. 33 references, 6 figures, 5 tables.

  14. Insight into the Atomic Structure of High-Voltage Spinel LiNi0.5Mn1.5O4sub> Cathode Material in the First Cycle

    SciTech Connect

    Huang, Xuejie; Yu, Xiqian; Lin, Mingxiang; Ben, Liubin; Sun, Yang; Wang, Hao; Yang, Zhenzhong; Gu, Lin; Yang, Xiao -Qing; Zhao, Haofei; Yu, Richeng; Armand, Michel


    Application of high-voltage spinel LiNi0.5Mn1.5O4sub> cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi0.5Mn1.5O4sub> cathode material. Although it is well-known that the structure of LiNi0.5Mn1.5O4sub> into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood. Here, we report detailed investigations of local atomic-level and average structure of LiNi0.5Mn1.5O4sub> during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi0.5Mn1.5O4sub>//Li half-cell during first charge via an aberration-corrected scanning transmission electron microscopy (STEM). Surface regions (~2 nm) of the cycled LiNi0.5Mn1.5O4sub> particles show migration of TM ions into tetrahedral Li sites to form a Mn3O4sub>-like structure. However, subsurface regions of the cycled particles exhibit migration of TM ions into empty octahedral sites to form a rocksalt-like structure. The migration of these TM ions are closely related to dissolution of Ni/Mn ions and building-up of charge transfer impedance, which contribute significantly to the capacity degradation and the poor first-cycle Coulombic efficiency of spinel LiNi0.5Mn1.5O4sub> cathode material. Accordingly, we provide suggestions of effective stabilization of LiNi0.5

  15. Crystal structure and thermal expansion of the low- and high-temperature forms of BaM{sup IV}(PO{sub 4}){sub 2} compounds (M=Ti, Zr, Hf and Sn)

    SciTech Connect

    Bregiroux, D.; Popa, K.; Jardin, R.; Raison, P.E.; Wallez, G.; Quarton, M.; Brunelli, M.; Ferrero, C.; Caciuffo, R.


    The crystal structure of beta-BaZr(PO{sub 4}){sub 2}, archetype of the high-temperature forms of BaM(PO{sub 4}){sub 2} phosphates (with M=Ti, Zr, Hf and Sn), has been solved ab initio by Rietveld analysis from synchrotron X-ray powder diffraction data. The phase transition appears as a topotactic modification of the monoclinic (S.G. C2/m) lamellar alpha-structure into a trigonal one (S.G. P3-barm1) through a simple mechanism involving the unfolding of the [Zr(PO{sub 4}){sub 2}]{sub n}{sup 2-} layers. The thermal expansion is very anisotropic (e.g., -4.14}){sub 2}) and quite different in the two forms, as a consequence of symmetry. It stems from a complex combination of several mechanisms, involving bridging oxygen rocking in M-O-P linkages, and 'bond thermal expansion'. - Graphical abstract: The layered high-temperature form of BaM(PO{sub 4}){sub 2}, only expands along the c-axis.

  16. Temperature-dependent framework–template interaction of |Na{sub 6}(H{sub 2}O){sub 8}|[ZnPO{sub 4}]{sub 6} sodalite

    SciTech Connect

    Robben, Lars Gesing, Thorsten M.


    The partial dehydration followed by the decomposition of sodium-zincophosphate-hydrosodalite caused by the total water loss was examined by temperature-dependent X-ray powder diffraction, Fourier transform infrared (FTIR) and Raman spectroscopy as well as thermogravimetry combined with difference thermoanalysis. The dehydration causing the decomposition of this sodalite could be described in a two step-process. Initially two water molecules per unit-cell were lost, changing the interaction between the zincophosphate framework and the remaining water molecules as well as sodium cations as non-framework constituents. In this stage a 3+3 coordination of water molecules and sodium cations in the sodalite cage is observed. Using the autocorrelation function (AC) for the evaluation of the temperature-dependent FTIR spectra of sodalites is reported here for the first time. Calculating the changes in the AC broadness, structural features could well be analyzed due to its correlation with respective structural parameters. Temperature dependent Raman data was used to give a band assignment of bands at Raman shifts below 300 cm{sup −1}. - Graphical abstract: The thermal decomposition of |Na{sub 6}(H{sub 2}O){sub 8}|[ZnPO{sub 4}]{sub 6} sodalite is a two-step process with an initial loss of two water molecules at 400 K, intermediately stabilizing the highly stressed framework. Further heating leads to a subsequent loss of the remaining six water molecules and a breakup of the sodalite framework. A beryllonite-type NaZnPO{sub 4} is the final product of this process. Display Omitted - Highlights: • The decomposition of |Na{sub 6}(H{sub 2}O){sub 8}|[ZnPO{sub 4}]{sub 6} sodalite is a two-step process. • Initial loss of two water molecule at 400 K stabilizes the sodalite (step 1). • Further heating leads to complete loss of water and structural breakdown. • Autocorrelation of temperature dependent FTIR-spectra gives structural information.

  17. Effects of quark family nonuniversality in SU(3){sub c} x SU(4){sub L} x U(1){sub X} models

    SciTech Connect

    Nisperuza, Jorge L.; Sanchez, Luis A.


    Flavor changing neutral currents arise in the SU(3){sub c} x SU(4){sub L} x U(1){sub X} extension of the standard model because anomaly cancellation among the fermion families requires one generation of quarks to transform differently from the other two under the gauge group. In the weak basis the distinction between quark families is meaningless. However, in the mass eigenstates basis, the Cabibbo-Kobayashi-Maskawa mixing matrix motivates us to classify left-handed quarks in families. In this sense there are, in principle, three different assignments of quark weak eigenstates into mass eigenstates. In this work, by using measurements at the Z pole, atomic parity violation data, and experimental input from neutral meson mixing, we examine two different models without exotic electric charges based on the 3-4-1 symmetry, and address the effects of quark family nonuniversality on the bounds on the mixing angle between two of the neutral currents present in the models and on the mass scales M{sub Z{sub 2}} and M{sub Z{sub 3}} of the new neutral gauge bosons predicted by the theory. The heaviest family of quarks must transform differently in order to keep lower bounds on M{sub Z{sub 2}} and M{sub Z{sub 3}} as low as possible without violating experimental constraints.

  18. Stable platinum nanoparticles on specific MgAl2O4sub> spinel facets at high temperatures in oxidizing atmospheres

    SciTech Connect

    Li, Wei-Zhen; Kovarik, Libor; Mei, Donghai; Liu, Jun; Wang, Yong; Peden, Charles H. F.


    The development of thermally stable, nanometer-sized precious metal-based catalysts remains a daunting challenge. Such materials, especially those based on the use of costly platinum metal, are essential and, to date, non-replaceable for a large number of industrially important catalytic processes. Here we report a well-defined cuboctahedral MgAl2O4sub> spinel support material that is capable of stabilizing platinum particles in the range of 1–3 nm on its relatively abundant {111} facets during extremely severe aging at 800 °C in air for 1 week. The aged catalysts retain platinum dispersions of 15.9% with catalytic activities for methanol oxidation being ~80% of that of fresh ones, whereas a conventional Pt/γ-Al2O3 catalyst is severely sintered and nearly inactive. Finally, we reveal the origin of the markedly superior ability of spinel {111} facets, resulting from strong interactions between spinel surface oxygens and epitaxial platinum {111} facets, inspiring the rational design of anti-sintering supported platinum group catalysts.

  19. Band alignment of atomic layer deposited (HfZrO{sub 4}){sub 1−x}(SiO{sub 2}){sub x} gate dielectrics on Si (100)

    SciTech Connect

    Heo, Sung; Tahir, Dahlang; Chung, Jae Gwan; Lee, Jae Cheol; Kim, KiHong; Lee, Junho; Lee, Hyung-Ik; Park, Gyeong Su; Oh, Suhk Kun; Kang, Hee Jae; Choi, Pyungho; Choi, Byoung-Deog


    The band alignment of atomic layer deposited (HfZrO{sub 4}){sub 1−x}(SiO{sub 2}){sub x} (x = 0, 0.10, 0.15, and 0.20) gate dielectric thin films grown on Si (100) was obtained by using X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. The band gap, valence band offset, and conduction band offset values for HfZrO{sub 4} silicate increased from 5.4 eV to 5.8 eV, from 2.5 eV to 2.75 eV, and from 1.78 eV to 1.93 eV, respectively, as the mole fraction (x) of SiO{sub 2} increased from 0.1 to 0.2. This increase in the conduction band and valence band offsets, as a function of increasing SiO{sub 2} mole fraction, decreased the gate leakage current density. As a result, HfZrO{sub 4} silicate thin films were found to be better for advanced gate stack applications because they had adequate band gaps to ensure sufficient conduction band offsets and valence band offsets to Si.

  20. Structure and conductivity of the NASICON analog Na/sub 3/SC/sub 2/(PO/sub 4/)/sub 3/

    SciTech Connect

    Susman, S.; Delbecq, C.J.; Brun, T.O.; Prince, E.


    Neutron and x-ray diffraction data of Na/sub 3/SC/sub 2/(PO/sub 4/)/sub 3/ are presented that show the transition from an ordinary-conducting, high temperature phase to a still higher temperature, superionic conducting phase. There are at least four polymorphic modifications. At room temperature, the refined neutron diffraction data confirm the Cc space group reported by Efremov and Kalinin but with a = 16.0449(24), b = 8.9225(15), c = 9.0656(13)A, ..beta.. = 126.918(21), R/sub weighted pattern/ = 17.5%, and R/sub expected/ = 7%. Between 25/sup 0/C and 64/sup 0/C, a second polymorph appears. The structure is monoclinic but has not yet been refined. At 64/sup 0/C, a third polymorph C appears. It is rhombohedral R3c. Using hexagonal axes, a = 8.9273(2), c = 22.3668A, R/sub wp/ = 6.28% and R/sub e/ = 3.83% at 100/sup 0/C. At 166/sup 0/C, the high temperature polymorph D appears. It is the superconducting phase of NASICON(Sc). It, too, is rhombohedral R3c with a = 8.9274(1), c = 22.5493(6)A, R/sub wp/ = 5.81% and R/sub e/ = 3.87% at 225/sup 0/C. The diffraction data are correlated with ionic conductivity measurements as a function of temperature.

  1. New localized/delocalized emitting state of Eu2+ in orange-emitting hexagonal EuAl2O4sub>

    SciTech Connect

    Liu, Feng; Meltzer, Richard S.; Li, Xufan; Budai, John D.; Chen, Yu -Sheng; Pan, Zhengwei


    Eu2+-activated phosphors are being widely used in illuminations and displays. Some of these phosphors feature an extremely broad and red-shifted Eu2+ emission band; however, convincing explanation of this phenomenon is lacking. Here we report a new localized/delocalized emitting state of Eu2+ ions in a new hexagonal EuAl2O4sub> phosphor whose Eu2+ luminescence exhibits a very large bandwidth and an extremely large Stokes shift. At 77 K, two luminescent sites responsible for 550 nm and 645 nm broadband emissions are recognized, while at room temperature only the 645 nm emission band emits. The 645 nm emission exhibits a typical radiative lifetime of 1.27 μs and an unusually large Stokes shift of 0.92 eV. We identify the 645 nm emission as originating from a new type of emitting state whose composition is predominantly that of localized 4f65d character but which also contains a complementary component with delocalized conduction-band-like character. This investigation gives new insights into a unique type of Eu2+ luminescence in solids whose emission exhibits both a very large bandwidth and an extremely large Stokes shift.

  2. Anisotropic lattice thermal expansion of PbFeBO4sub>: A study by X-ray and neutron diffraction, Raman spectroscopy and DFT calculations

    SciTech Connect

    Murshed, M. Mangir; Mendive, Cecilia B.; Curti, Mariano; Nénert, Gwilherm; Kalita, Patricia E.; Lipinska, Kris; Cornelius, Andrew L.; Huq, Ashfia; Gesing, Thorsten M.


    We present the lattice thermal expansion of mullite-type PbFeBO4sub> in this study. The thermal expansion coefficients of the metric parameters were obtained from composite data collected from temperature-dependent neutron and X-ray powder diffraction between 10 K and 700 K. The volume thermal expansion was modeled using extended Grüneisen first-order approximation to the zero-pressure equation of state. The additive frame of the model includes harmonic, quasi-harmonic and intrinsic anharmonic potentials to describe the change of the internal energy as a function of temperature. Moreover, the unit-cell volume at zero-pressure and 0 K was optimized during the DFT simulations. Harmonic frequencies of the optical Raman modes at the Γ-point of the Brillouin zone at 0 K were also calculated by DFT, which help to assign and crosscheck the experimental frequencies. The low-temperature Raman spectra showed significant anomaly in the antiferromagnetic regions, leading to softening or hardening of some phonons. Selected modes were analyzed using a modified Klemens model. The shift of the frequencies and the broadening of the line-widths helped to understand the anharmonic vibrational behaviors of the PbO4, FeO6 and BO3 polyhedra as a function of temperature.

  3. X-ray absorption spectroscopy of LiBF 4sub> in propylene carbonate. A model lithium ion battery electrolyte

    SciTech Connect

    Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; Shih, Orion; Rizzuto, Anthony M.; Borodin, Oleg; Harris, Stephen J.; Prendergast, David; Saykally, Richard J.


    Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF4sub> in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li+ ion in this model electrolyte. By generating linear combinations of the computed spectra of Li+-associating and free PC molecules and comparing to the experimental spectrum, we find a Li+–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.

  4. Optical gain in capillary light guides filled with NaYF4sub>: Yb3+, Er3+ nanocolloids.


    Patel, Darayas N; Sarkisov, Sergey S; Darwish, Abdalla M; Ballato, John


    A capillary light guide optical amplifier using nanocolloids of Yb3+-Er3+ co-doped NaYF4sub> as a filler was successfully demonstrated. A 7-cm-long and 150-micron-inner-diameter capillary light guide was capable to amplify a pulsed optical signal at 1550 nm with a gain coefficient of 0.15 cm-1 at a pump power of 4 mW (980-nm wavelength). The nanocolloid gain medium was prepared by pulverizing the phosphor powder with a high-speed planetary ball mill. Ball milling of the powder in water produced nanoparticles with a size of approximately 130 nm that after drying were transferred to a liquid with high refractive index (1.551 at 1550 nm) required to maintain light confinement within the fused silica capillary light guide. The results show that RE-doped colloids of nanocrystals can be potentially used as liquid gain media fillers in capillary light guide lasers and amplifiers with high photostability and low toxicity. PMID:27607717

  5. Synthesis of nanostructured LiTi{sub 2}(PO{sub 4}){sub 3} powder by a Pechini-type polymerizable complex method

    SciTech Connect

    Mariappan, C.R.; Galven, C.; Crosnier-Lopez, M.-P.; Le Berre, F.; Bohnke, O. . E-mail:


    The nanostructured NASICON-type LiTi{sub 2}(PO{sub 4}){sub 3} (LTP) material has been synthesized by Pechini-type polymerizable complex method. The use of water-soluble ammonium citratoperoxotitanate (IV) metal complex instead of alkoxides as precursor allows to prepare monophase material. Thermal analyses have been carried out on the powder precursor to check the weight loss and synthesis temperature. X-ray powder diffraction analysis (XRD) has been performed on the LTP powder obtained after heating the powder precursor over a temperature range from 550 to 1050 deg. C for 2 h. By varying the molar ratio of citric acid to metal ion (CA/Ti) and citric acid to ethylene glycol (CA/EG), the grain size of the LTP powder could be modified. The formation of small and well-crystalline grains, in the order of 50-125 nm in size, has been determined from the XRD patterns and confirmed by transmission electron microscopy.

  6. An air-stable Na3SbS4sub> superionic conductor prepared by a rapid and economic synthetic procedure

    SciTech Connect

    Wang, Hui; Chen, Yan; Hood, Zachary D.; Samuthira Pandian, Amaresh; Keum, Jong Kahk; An, Ke; Sahu, Gayatri; Liang, Chengdu


    All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na3SbS4sub>, a novel Na superionic conductor that needs much lower processing temperature below 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm-1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.

  7. Passive Q-switching of a Tm,Ho:KLu(WO4sub>)2 microchip laser by a Cr:ZnS saturable absorber.


    Serres, J M; Loiko, P; Mateos, X; Jambunathan, V; Yasukevich, A S; Yumashev, K V; Petrov, V; Griebner, U; Aguiló, M; Díaz, F


    A diode-pumped Tm,Ho:KLu(WO4sub>)2 microchip laser passively Q-switched with a Cr:ZnS saturable absorber generated an average output power of 131 mW at 2063.6 nm with a slope efficiency of 11% and a Q-switching conversion efficiency of 58%. The pulse characteristics were 14  ns/9  μJ at a pulse repetition frequency of 14.5 kHz. With higher modulation depth of the saturable absorber, 9  ns/10.4  μJ/8.2  kHz pulses were generated at 2061.1 nm, corresponding to a record peak power extracted from a passively Q-switched Tm,Ho laser of 1.15 kW. A theoretical model is presented, predicting the pulse energy and duration. The simulations are in good agreement with the experimental results. PMID:27168288

  8. Hydrothermal synthesis, structural and physico-chemical characterizations of two Nasicon phosphates: M{sub 0.50}{sup II}Ti{sub 2}(PO{sub 4}){sub 3} (M = Mn, Co)

    SciTech Connect

    Essehli, Rachid; Bali, Brahim El; Benmokhtar, S.; Fejfarova, Karla; Dusek, Michal


    The family of titanium Nasicon-phosphates of generic formula M{sub 0.5}{sup II}Ti{sub 2}(PO{sub 4}){sub 3} has been revisited using hydrothermal techniques. Two phases have been synthesized: Mn{sub 0.5}{sup II}Ti{sub 2}(PO{sub 4}){sub 3} (MnTiP) and Co{sub 0.5}{sup II}Ti{sub 2}(PO{sub 4}){sub 3} (CoTiP). Single crystal diffraction studies show that they exhibit two different structural types. Mn{sub 0.5}{sup II}Ti{sub 2}(PO{sub 4}){sub 3} phosphate crystallizes in the R-3 space group, with the cell parameters a = 8.51300(10) A and c = 21.0083(3) A (V = 1318.52(3) A{sup 3} and Z = 6). The Co{sub 0.5}{sup II}Ti{sub 2}(PO{sub 4}){sub 3} phosphate crystallizes in the R-3c space group, with a = 8.4608(9) A and c = 21.174(2) A (V = 1312.7(2) A{sup 3} and Z = 6). These two compounds are clearly related to the parent Nasicon-type rhombohedral structure, which can be described using [Ti{sub 2}(PO{sub 4}){sub 3}] framework composed of two [TiO{sub 6}] octahedral interlinked via three [PO{sub 4}] tetrahedra. {sup 31}P magic-angle spinning nuclear magnetic resonance (MAS-NMR) data are presented as supporting data. Curie-Weiss-type behavior is observed in the magnetic susceptibility. The phases are also characterized by IR spectroscopy and UV-visible.

  9. Near-infrared quantum-cutting luminescence and energy transfer properties of Ca{sub 3}(PO{sub 4}){sub 2}:Tm{sup 3+},Ce{sup 3+} phosphors

    SciTech Connect

    Dong, S. L.; Lin, H. H. E-mail:; Yu, T.; Zhang, Q. Y. E-mail:


    The phosphors Ca{sub 3}(PO{sub 4}){sub 2}:Tm{sup 3+} by co-doping Ce{sup 3+} have been synthesized by conventional high-temperature solid-state reaction method. Their spectroscopic properties in the UV-VIS-NIR range have been investigated. The first 5d crystal field level location and stokes shift have been determined from the UV excitation and emission spectra of Ca{sub 3}(PO{sub 4}){sub 2}:Ce{sup 3+}. The three-photon NIR quantum-cutting luminescence of Tm{sup 3+} assigned to the electronic transitions of {sup 1}G{sub 4}→{sup 3}H{sub 4}, {sup 3}H{sub 4}→{sup 3}F{sub 4} and {sup 3}F{sub 4}→{sup 3}H{sub 6} is observed, whether in Ca{sub 3}(PO{sub 4}){sub 2}:Tm{sup 3+} or Ca{sub 3}(PO{sub 4}){sub 2}:Tm{sup 3+},Ce{sup 3+}. The energy transfer from Ce{sup 3+} to Tm{sup 3+} takes place with energy-transfer efficiency up to 34.5% for the Ca{sub 3}(PO{sub 4}){sub 2}:Tm{sup 3+},Ce{sup 3+}. A cross relaxation scheme using the 5d states of Ce{sup 3+} and f-f transition of Tm{sup 3+} is proposed. The mechanism is revealed from energy level and decay measurements. The results show that the broadband absorption of Ce{sup 3+} sensitizer not only extends the spectrum conversion in UV region but also greatly enhances the photoluminescence intensities of the three-photon quantum cutting luminescence of Tm{sup 3+} doped Ca{sub 3}(PO{sub 4}){sub 2}.

  10. Synthesis and photoluminescence properties of Ca{sub 19}Mg{sub 2}(PO{sub 4}){sub 14}:Sm{sup 3+} red phosphor for white light emitting diodes

    SciTech Connect

    Zhu, Ge; Ci, Zhipeng; Shi, Yurong; Wang, Yuhua


    Highlights: • A novel red phosphor Ca{sub 19}Mg{sub 2}(PO{sub 4}){sub 14}:Sm{sup 3+} was synthesized and investigated firstly. • The structure and characteristic luminescence properties are discussed. • The excellent thermal stability was found and investigated. • It has good color saturation, the CIE is close to that of commercial Y{sub 2}O{sub 3}:Eu{sup 3+}. - Abstract: A series of Sm{sup 3+} doped Ca{sub 19}Mg{sub 2}(PO{sub 4}){sub 14} red phosphors were successfully synthesized. X-ray diffraction analysis indicates that all the samples are single phased. The luminescence property is investigated in detail by measuring their photoluminescence excitation and emission spectra. Ca{sub 19}Mg{sub 2}(PO{sub 4}){sub 14}:Sm{sup 3+} phosphors show strong absorption in 400–410 nm region, which is suitable for application in LEDs. When excited at 403 nm, Ca{sub 19}Mg{sub 2}(PO{sub 4}){sub 14}:Sm{sup 3+} phosphor can emit red emission with CIE chromaticity coordinates (0.615, 0.384). The optimal doping concentration of Sm{sup 3+} doped Ca{sub 19}Mg{sub 2}(PO{sub 4}){sub 14} is measured to be 0.02. The thermal quenching property is also measured and compared with the commercial red phosphor Y{sub 2}O{sub 3}:Eu{sup 3+} (Topstar, TXC-RIA). The results indicate Ca{sub 19}Mg{sub 2}(PO{sub 4}){sub 14}:Sm{sup 3+} phosphors have potential to serve as a red phosphor for white LEDs.

  11. Scintillation properties of Eu2+-doped KBa2I5 and K2BaI4sub>

    SciTech Connect

    Stand, L.; Zhuravleva, M.; Chakoumakos, Bryan C.; Johnson, J.; Lindsey, Adam; Melcher, Charles L.


    We report two new ternary metal halide scintillators, KBa2I5 and K2BaI4sub>, activated with divalent europium. Single crystal X-ray diffraction measurements confirmed that KBa2I5 has a monoclinic structure (P21/c) and that K2BaI4sub> has a rhombohedral structure (R3c). Differential scanning calorimetry showed singular melting and crystallization points, making these compounds viable candidates for melt growth. We grew 13 mm diameter single crystals of KBa2I5:Eu2+ and K2BaI4sub>:Eu2+ in evacuated quartz ampoules via the vertical Bridgman technique. The optimal Eu2+ concentration was 4% for KBa2I5 and 7% for K2BaI4sub>. The X-ray excited emissions at 444 nm for KBa2I5:Eu 4% and 448 nm for K2BaI4sub>:Eu 7% arise from the 5d-4f radiative transition in Eu2+. KBa2I5:Eu 4% has a light yield of 90,000 photons/MeV, with an energy resolution of 2.4% and K2BaI4sub>:Eu 7% has a light yield of 63,000 ph/MeV, with an energy resolution of 2.9% at 662 keV. Both crystals have an excellent proportional response to a wide range of gamma-ray energies.


    SciTech Connect

    Neufeld, David A.; Wu, Yuanwei; Kraus, Alex; Menten, Karl M.; Tolls, Volker; Melnick, Gary J.; Nagy, Zsofia


    Using the Herschel Space Observatory's Heterodyne Instrument for the Far-Infrared, we have performed mapping observations of the 620.701 GHz 5{sub 32}-4{sub 41} transition of ortho-H{sub 2}O within a {approx}1.'5 Multiplication-Sign 1.'5 region encompassing the Kleinmann-Low nebula in Orion (Orion-KL), and pointed observations of that transition toward the Orion South condensation and the W49N region of high-mass star formation. Using the Effelsberg 100 m radio telescope, we obtained ancillary observations of the 22.23508 GHz 6{sub 16}-5{sub 23} water maser transition; in the case of Orion-KL, the 621 GHz and 22 GHz observations were carried out within 10 days of each other. The 621 GHz water line emission shows clear evidence for strong maser amplification in all three sources, exhibiting narrow ({approx}1 km s{sup -1} FWHM) emission features that are coincident (kinematically and/or spatially) with observed 22 GHz features. Moreover, in the case of W49N-for which observations were available at three epochs spanning a 2 yr period-the spectra exhibited variability. The observed 621 GHz/22 GHz line ratios are consistent with a maser pumping model in which the population inversions arise from the combined effects of collisional excitation and spontaneous radiative decay, and the inferred physical conditions can plausibly arise in gas heated by either dissociative or non-dissociative shocks. The collisional excitation model also predicts that the 22 GHz population inversion will be quenched at higher densities than that of the 621 GHz transition, providing a natural explanation for the observational fact that 22 GHz maser emission appears to be a necessary but insufficient condition for 621 GHz maser emission.

  13. Origin of Active Oxygen in a Ternary CuOx /Co3O4sub>–CeO 2 Catalyst for CO Oxidation

    SciTech Connect

    Liu, Zhigang; Wu, Zili; Peng, Xihong; Binder, Andrew; Chai, Songhai; Dai, Sheng


    In this paper, we have studied CO oxidation over a ternary CuOx/Co3O4sub>-CeO2 catalyst and employed the techniques of N2 adsorption/desporption, XRD, TPR, TEM, in situ DRIFTS and QMS (Quadrupole mass spectrometer) to explore the origin of active oxygen. DRIFTS-QMS results with labeled 18O2 indicate that the origin of active oxygens in CuOx/Co3O4sub>-CeO2 obeys a model, called as queue mechanism. Namely gas-phase molecular oxygens are dissociated to atomic oxygens and then incorporate in oxygen vacancies located at the interface of Co3O4sub>-CeO2 to form active crystalline oxygens, and these active oxygens diffuse to the CO-Cu+ sites thanks to the oxygen vacancy concentration magnitude and react with the activated CO to form CO2. This process, obeying a queue rule, provides active oxygens to form CO2 from gas-phase O2 via oxygen vacancies and crystalline oxygen at the interface of Co3O4sub>-CeO2.

  14. Syntheses and crystal structures of two novel alkaline uranyl chromates A{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2} (A=Rb, Cs) with bidentate coordination mode of uranyl ions by chromate anions

    SciTech Connect

    Siidra, Oleg I.


    Single crystals of Cs{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2} and Rb{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2} were prepared by solid state reactions. The structures are based upon the [(UO{sub 2})(CrO{sub 4}){sub 2}]{sup 2-} chains. Within the chains, UrO{sub 5} pentagonal bipyramids (Ur=uranyl) form Ur{sub 2}O{sub 8} dimers, which are linked via CrO{sub 4} tetrahedra into one-dimensional chains. The CrO{sub 4} tetrahedra coordinate uranyl ions in both mono- and bidentate fashion, which is unusual for uranyl chromates. The bidentate coordination has a strong influence upon geometrical parameters of both U and Cr coordination polyhedra. The conformation of the chains in 1 and 2 is different due to the different size of the Cs{sup +} and Rb{sup +} cations. - Graphical abstract: Uranyl chromate chain with monodentate and bidentate coordination mode of uranyl cations by CrO{sub 4} tetrahedra in Cs{sub 2}(UO{sub 2})(CrO{sub 4}){sub 2}. Highlights: Black-Right-Pointing-Pointer Single crystals of novel uranyl chromates were prepared by solid state reactions. Black-Right-Pointing-Pointer The CrO{sub 4} tetrahedra coordinate uranyl ions in both mono- and bidentate fashion. Black-Right-Pointing-Pointer The bidentate coordination has a strong influence upon geometrical parameters.

  15. Polyselenide chemistry of indium and thallium in dimethylformamide, acetonitrile, and water. Syntheses, structures, and properties of the new complexes [In[sub 2](Se[sub 4])[sub 4](Se[sub 5])][sup 4[minus

    SciTech Connect

    Dhingra, S.S.; Kanatzidis, M.G. )


    The reaction of InCl[sub 3] with Na[sub 2]Se[sub 5] in dimethylformamide (DMF) in the presence of Ph[sub 4]PCl gave (Ph[sub 4]P)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (I) in 75% yield. Under the same conditions, InCl[sub 3] reacted with Na[sub 2]Se[sub 5] in the presence of Pr[sub 4]NBr or Et[sub 4]NBr and afforded (Pr[sub 4]N)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (II) in 65% yield and (Et[sub 4]N)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (III) in 72% yield, respectively. Single-crystal X-ray diffraction studies show that (I), (II), and (III) contain the same anion, [In[sub 2](Se[sub 4])[sub 4](Se[sub 5])][sup 4[minus

  16. Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4sub>-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions. Quarterly Report.

    SciTech Connect

    Wang, Yifeng


    This project focuses on the systematic study of CH4sub>-CO2-H2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.

  17. In situ determination of the spinel-post-spinel transition in Fe3O4sub> at high pressure and temperature by synchrotron X-ray diffraction

    SciTech Connect

    Schollenbruch, K; Woodland, A B; Frost, D J; Wang, Y; Sanehira, T; Langenhorst, F


    The position of the spinel-post-spinel phase transition in Fe3O4sub> has been determined in pressure-temperature space by in situ measurements using a multi-anvil press combined with white synchrotron radiation. Pressure measurement using the equation of state for MgO permitted pressure changes to be monitored at high temperature. The phase boundary was determined by the first appearance of diffraction peaks of the high-pressure polymorph (h-Fe3O4sub>) during pressure increase and the disappearance of these peaks on pressure decrease along several isotherms. We intersected the phase boundary over the temperature interval of 700-1400 ºC. The boundary is linear and nearly isobaric, with a slightly positive slope. Post-experiment investigation by TEM confirms that the reverse reaction from h-Fe 3O4sub> to magnetite during decompression leads to the formation of microtwins on the (311) plane in the newly formed magnetite. Observations made during the phase transition suggest that the transition has a pseudomartensitic character, explaining in part why magnetite persists at conditions well within the stability field of h-Fe3O4sub>, even at high temperatures. This study emphasizes the utility of studying phase transitions in situ at simultaneously high temperatures and pressures since the reaction kinetics may not be favorable at room temperature.

  18. Photoelectron Spectroscopy of Anions at 118.2 nm. Observation of High Electron Binding Energies in Superhalogens MCI4sub>- (M=Sc, Y, La)

    SciTech Connect

    Yang, Jie; Wang, Xue B.; Xing, Xiaopeng; Wang, Lai S.


    High energy photon is needed for photoelectron spectroscopy (PES) of anions with high electron binding energies, such as superhalogens and O-rich metal oxide clusters. The highest energy photon used for anion PES in the laboratory has been 157 nm (7.866 eV) from F2 eximer lasers. Here, we report an anion PES experiment using coherent vacuum ultraviolet radiation at 118.2 nm (10.488 eV) by tripling the third harmonic output (355 nm) of a Nd:YAG laser in a Xe/Ar cell. Our study focuses on a set of superhalogen species, MCI4sub>- (M=Sc, Y, La), which were expected to possess very high electron binding energies. While the 157 nm photon can only access the ground state detachment features for these species, more transitions to the excited states at binding energies higher than 8 eV are observed at 118.2 nm. The adiabatic detachment energies are shown to be, 6.84, 7.02, and 7.03 eV for ScCl4sub>-, YCl4sub>-, and LaCl4sub>- eV, respectively, whereas their corresponding vertical detachment energies are measured to be 7.14, 7.31, and 7.38 eV.

  19. Magnetic field, frequency and temperature dependence of complex conductance of ultrathin La1.65Sr0.45CuO4sub>/La2CuO4sub> films and the organic superconductors κ-(BEDT-TTF)2Cu[N(CN)2]Br

    SciTech Connect

    V. A. Gasparov; Bozovic, I.; He, Xi; Dubuis, G.; Pavuna, D.; Kushch, N. D.; Yagubskii, E. B.; Schlueter, J. A.


    In this study, we used atomic-layer molecular beam epitaxy (ALL-MBE) to synthesize bilayer films of a cuprate metal (La1.65Sr0.45CuO4sub>) and a cuprate insulator (La2CuO4sub>), in which interface superconductivity occurs in a layer that is just one-half unit cell thick. We have studied the magnetic field and temperature dependence of the complex sheet conductance, σ(ω), of these films, and compared them to κκ-(BEDT-TTF)2Cu[N(CN)2]Br single crystals. The magnetic field H was applied both parallel and perpendicular to the 2D conducting layers. Experiments have been carried out at frequencies between 23 kHz and 50 MHz using either two-coil mutual inductance technique, or the LC resonators with spiral or rectangular coils. The real and the imaginary parts of the mutual-inductance M(T,ω) between the coil and the sample were measured and converted to complex conductivity. For H perpendicular to the conducting layers, we observed almost identical behavior in both films and κ-Br single crystals: (i) the transition onset in the inductive response, Lk–1(T) occurs at a temperature lower by 2 K than in Re σ(T), (ii) this shift is almost constant with magnetic field up to 8 T; (iii) the vortex diffusion constant D(T) is exponential due to pinning of vortex cores. These results can be described by the extended dynamic theory of the Berezinski–Kosterlitz–Thouless (BKT) transition and dynamics of bound vortex–antivortex pairs with short separation lengths.

  20. NaLa(MoO{sub 4}){sub 2}: RE{sup 3+} (RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}, Er{sup 3+}/Yb{sup 3+}) microspheres: the synthesis and optical properties

    SciTech Connect

    Gao, Zhiyi; Wang, Zhiying; Fu, Linlin; Yang, Xingxing; Fu, Zuoling; Wu, Zhijian; Jeong, Jung Hyun


    The strong green upconversion (UC) emission were observed in various Er{sup 3+}, Yb{sup 3+} co-doped NaLa(MoO{sub 4}){sub 2} samples synthesized via a hydrothermal route. The UC intensity depends on the dopant concentration, and the optimal UC emission was obtained in NaLa(MoO{sub 4}){sub 2}: 0.02Er{sup 3+}/0.10 Yb{sup 3+}. - Highlights: • The NaLa(MoO{sub 4}){sub 2} microspheres doped with Eu{sup 3+}, Sm{sup 3+} and Er{sup 3+}/Yb{sup 3+} were synthesized by a hydrothermal method. • The effects of the EDTA in the initial solution crystal phase and morphology were studied. • The down-conversion luminescence properties of NaLa(MoO{sub 4}){sub 2}: RE{sup 3+} (RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}) were investigated. • The UC luminescence properties and mechanism of Er{sup 3+}/Yb{sup 3+} co-doped NaLa(MoO{sub 4}){sub 2} was discussed. - Abstract: NaLa(MoO{sub 4}){sub 2}: RE{sup 3+} (RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}) microspheres have been synthesized at 180 °C via a facile EDTA-mediated hydrothermal route. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) spectra were employed to characterize the samples. It was found that the amount of EDTA in the initial solution was responsible for crystal phase and shape determination. The effect of Eu{sup 3+} and Sm{sup 3+} doping concentrations on the luminescent intensity was also investigated in details. Furthermore, the up-conversion (UC) emissions have been observed in a series of Er{sup 3+}/Yb{sup 3+} co-doped NaLa(MoO{sub 4}){sub 2} samples. Concentration dependent studies revealed that the optimal composition was realized for a 2% Er{sup 3+} and 10% Yb{sup 3+}-doping concentration.

  1. A study of room-temperature LixMn1.5Ni0.5O4sub> solid solutions

    SciTech Connect

    Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; Chen, Guoying


    Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature LixMn1.5Ni0.5O4sub> solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of LixMn1.5Ni0.5O4sub> (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn1.5Ni0.5O4sub> (Phase I), Li0.5Mn1.5Ni0.5O4sub> (Phase II) and Mn1.5Ni0.5O4sub> (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. In conclusion, the work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance.

  2. NMR relaxation study of the phase transitions and relaxation mechanisms of the alums MCr(SO{sub 4}){sub 2}.12H{sub 2}O (M=Rb and Cs) single crystals

    SciTech Connect

    Lim, Ae Ran; Paik, Younkee; Lim, Kye-Young


    The physical properties and phase transition mechanisms of MCr(SO{sub 4}){sub 2}.12H{sub 2}O (M=Rb and Cs) single crystals have been investigated. The phase transition temperatures, NMR spectra, and the spin-lattice relaxation times T{sub 1} of the {sup 87}Rb and {sup 133}Cs nuclei in the two crystals were determined using DSC and FT NMR spectroscopy. The resonance lines and relaxation times of the {sup 87}Rb and {sup 133}Cs nuclei undergo significant changes at the phase transition temperatures. The sudden changes in the splitting of the Rb and Cs resonance lines are attributed to changes in the local symmetry of their sites, and the changes in the temperature dependences of T{sub 1} are related to variations in the symmetry of the octahedra of water molecules surrounding Rb{sup +} and Cs{sup +}. We also compared these {sup 87}Rb and {sup 133}Cs NMR results with those obtained for the trivalent cations Cr and Al in MCr(SO{sub 4}){sub 2}.12H{sub 2}O and MAl(SO{sub 4}){sub 2}.12H{sub 2}O crystals. - Graphical Abstract: The physical properties and phase transition mechanisms of MCr(SO{sub 4}){sub 2}.12H{sub 2}O (M=Rb, Cs, and NH{sub 4}) single crystals have been investigated. Highlights: > The physical properties and phase transition mechanisms of MCr(SO{sub 4}){sub 2}.12H{sub 2}O (M=Rb and Cs) crystals {yields} The NMR spectra and the spin-lattice relaxation times T{sub 1} of the {sup 87}Rb and {sup 133}Cs nuclei in the two crystals {yields} The variations in the symmetry of the octahedra of water molecules surrounding Rb{sup +} and Cs{sup +}.

  3. Micro-Raman and Micro-Infrared Spectroscopic Studies of Pb- and Au-Irradiated ZrSiO4sub>. Optical Properties, Structural Damage and Amorphization

    SciTech Connect

    Zhang, Ming; Boatner, Lynn A.; Salje, Ekhard; Ewing, Rodney C.; Daniel, Philippe; Weber, William J; Zhang, Yanwen; Farnan, Ian E.


    The optical properties of damaged, periodic and aperiodic domains created by Pb+ (280 keV) and Au4+ (10 MeV) implantation of zircon were studied using micro-infrared (IR) and micro-Raman spectroscopy. The Pb+ and Au4+ irradiations caused a dramatic decrease in the IR reflectivity similar to that observed for metamict natural zircon. The irradiation with 10 MeV Au4+ ions (to fluences of 1x1015 Au4+ ions/cm2) also results in the formation of an amorphized phase similar to that observed in metamict zircon. These results show that high-energy, heavy-ion irradiations provide a good simulation of the ballistic effects of the recoil nucleus of an alpha-decay event, and in both cases, the result is the creation of aperiodic domains. Additional IR and Raman features were recorded in samples irradiated with 280 keV Pb+ ions (to fluences of 1x1014 and 1x1015 Pb+ ions/cm2), indicating the formation of an irradiation-induced new phase(s). The frequencies of the features are consistent with lead silicates, ZrO2 and SiO2. The results show that spectral features of the Au4+ and Pb+ irradiated zircon are different from those of quenched ZrSiO4sub> melts, and the finding further confirms that the amorphous state produced by high-energy ion irradiations is structurally different from the glassy state that results from quenching a high temperature melt. In contrast to significant changes in the frequency and width of the Raman v3 band observed in metamict zircon, the Pb+ and Au4+ irradiations do not cause similar variations, indicating that the remaining zircon crystalline domains in irradiated samples have a crystalline structure with fewer defects than those of metamict zircon.

  4. Thermal expansion of phosphates with the NaZr{sub 2}(PO{sub 4}){sub 3} structure containing lanthanides and zirconium: R{sub 0.33}Zr{sub 2}(PO{sub 4}){sub 3} (R = Nd, Eu, Er) and Er{sub 0.33(1–x)} Zr{sub 0.25x}Zr{sub 2}(PO{sub 4}){sup 3}

    SciTech Connect

    Volgutov, V. Yu. Orlova, A. I.


    Phosphates R{sub 0.33}Zr{sub 2}(PO{sub 4}){sub 3} (R = Nd, Eu, or Er) and Er{sub 0.33(1–x)}Zr{sub 0.25}Zr{sub 2}(PO{sub 4}){sub 3} (x = 0, 0.25, 0.5, 0.75, 1.0) of the NaZr{sub 2}(PO{sub 4}){sub 3} family have been synthesized and investigated by high-temperature X-ray diffraction. The crystallochemical approach is used to obtain compounds with expected small and controllable thermal-expansion parameters. Phosphates with close-to-zero thermal-expansion parameters, including those with low thermal-expansion anisotropy, have been obtained: Nd{sub 0.33}Zr{sub 2}(PO{sub 4}){sub 3} with α{sub a} =–2.21 × 10{sup −6} °C{sup −1}, α{sub c} = 0.81 × 10{sup −6} °C{sup −1}, and Δα = 3.02 × 10{sup −6} °C{sup –1} and Er{sub 0.08}Zr{sub 0.19}Zr{sub 2}(PO{sub 4}){sub 3} with α{sub a} =–1.86 × 10{sup −6} °C{sup −1}, α{sub c} = 1.73 × 10{sup −6} °C{sup −1}, and Δα = 3.58 × 10{sup −6} °C{sup −1}.

  5. From {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} to {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite chains in A{sub 6}U{sub 2}Mo{sub 4}O{sub 21} (A=Na, K, Rb, Cs) compounds: Synthesis and crystal structure of Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})

    SciTech Connect

    Yagoubi, S.; Obbade, S.; Saad, S.; Abraham, F.


    A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry with space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610 {sup o

  6. Dual Phase Li4sub>Ti5O12–TiO2 Nanowire Arrays As Integrated Anodes For High-rate Lithium-ion Batteries

    SciTech Connect

    Liao, Jin; Chabot, Victor; Gu, Meng; Wang, Chong M.; Xiao, Xingcheng; Chen, Zhongwei


    Lithium titanate (Li4sub>Ti5O12) is well known as a zero strain material inherently, which provides excellent long cycle stability as a negative electrode for lithium ion batteries. However, the low specific capacity (175 mA h g-1) limits it to power batteries although the low electrical conductivity is another intrinsic issue need to be solved. In this work, we developed a facile hydrothermal and ion-exchange route to synthesize the self-supported dual-phase Li4sub>Ti5O12–TiO2 nanowire arrays to further improve its capacity as well as rate capability. The ratio of Li4sub>Ti5O12 to TiO2 in the dual phase Li4sub>Ti5O12–TiO2 nanowire is around 2:1. The introduction of TiO2 into Li4sub>Ti5O12 increases the specific capacity. More importantly, by interface design, it creates a dual-phase nanostructure with high grain boundary density that facilitates both electron and Li ion transport. Compared with phase-pure nanowire Li4sub>Ti5O12 and TiO2 nanaowire arrays, the dual-phase nanowire electrode yielded superior rate capability (135.5 at 5 C, 129.4 at 10 C, 120.2 at 20 C and 115.5 mA h g-1 at 30 C). In-situ transmission electron microscope clearly shows the near zero deformation of the dual phase structure, which explains its excellent cycle stability.

  7. Selective Metal Exsolution in BaFe2-yMy(PO4sub>)2 (M = Co2+, Ni2+) Solid Solutions

    SciTech Connect

    Alcover, Ignacio Blazquez; Daviero-Minaud, Sylvie; David, Rénald; Filimonov, Dmitry; Huvé, Marielle; Attfield, J. Paul; Kabbour, Houria; Mentré, Olivier


    The 2D-Ising ferromagnetic phase BaFe2+2(PO4sub>)2 shows exsolution of up to one-third of its iron content (giving BaFe3+1.33(PO4sub>)2) under mild oxidation conditions, leading to nanosized Fe2O3 exsolved clusters. Here we have prepared BaFe2–yMy(PO4sub>)2 (M = Co2+, Ni2+; y = 0, 0.5, 1, 1.5) solid solutions to investigate the feasibility and selectivity of metal exsolution in these mixed metallic systems. For all the compounds, after 600 °C thermal treatment in air, a complete oxidation of Fe2+ to Fe3+ leaves stable M2+ ions, as verified by 57Fe Mössbauer spectroscopy, TGA, TEM, microprobe, and XANES. Furthermore, the size of the nanometric α-Fe2O3clusters coating the main phase strongly depends on the yM metal concentration. For M-rich phases the iron diffusion is hampered so that a significant fraction of superparamagnetic α-Fe2O3 particles (100% for BaFe0.5–xCo1.5(PO4sub>)2) was detected even at 78 K. Although Ni2+and Co2+ ions tend to block Fe diffusion, the crystal structure of BaFe0.67Co1(PO4sub>)2demonstrates a fully ordered rearrangement of Fe3+ and Co2+ ions after Fe exsolution. We found that the magnetic behaviors of the Fe-depleted materials are mostly dominated by antiferromagnetic exchange, while Co2+-rich compounds show metamagnetic transitions reminiscent of the BaCo2(PO4sub>)2 soft helicoidal magnet.

  8. [H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3}]{sub 2}[Al{sub 4}(C{sub 2}O{sub 4})(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 4}].4[H{sub 2}O]: A new layered aluminum phosphate-oxalate

    SciTech Connect

    Peng Li; Li Jiyang; Yu Jihong . E-mail:; Li Guanghua; Fang Qianrong; Xu Ruren . E-mail:


    A new layered inorganic-organic hybrid aluminum phosphate-oxalate [H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3}]{sub 2}[Al{sub 4}(C{sub 2}O{sub 4})(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 4}].4[H{sub 2}O](AlPO-CJ25) has been synthesized hydrothermally, by using 1,4-diaminobutane (DAB) as structure-directing agent. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by IR, {sup 31}P MAS NMR, TG-DTA as well as compositional analyses. Crystal data: the triclinic space group P-1, a=8.0484(7) A, b=8.8608(8) A, c=13.2224(11) A, {alpha}=80.830(6) deg. , {beta}=74.965(5) deg. , {gamma}=78.782(6) deg. , Z=2, R {sub 1[} {sub I} {sub >2} {sub {sigma}} {sub (} {sub I} {sub )]}=0.0511 and wR {sub 2(alldata)}=0.1423. The alternation of AlO{sub 4} tetrahedra and PO{sub 4} tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO{sub 6} octahedra to form the layered structure with 4,6-net sheet. Interestingly, oxalate ions are bis-bidentately bonded by participating in the coordination of AlO{sub 6}, and bridging the adjacent AlO{sub 6} octahedra. The layers are held with each other through strong H-bondings between the terminal oxygens. The organic ammonium cations and water molecules are located in the large cavities between the interlayer regions. -- Graphical abstract: The alternation of AlO{sub 4} tetrahedra and PO{sub 4} tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO{sub 6} octahedra to form the layered structure with 4,6-net sheet. Oxalate ions are bis-bidentately boned by participating in the coordination of AlO{sub 6}, and bridging the adjacent AlO{sub 6} octahedra.

  9. Crystal structure of the binary complex of cobalt and zinc chlorides with carbamide [Co(OCN{sub 2}H{sub 4}){sub 5}(H{sub 2}O)][ZnCl{sub 4}

    SciTech Connect

    Furmanova, N. G. Chernaya, T. S.; Resnyanskii, V. F. Sulaimankulov, K. S.


    Mixed single crystals of [Co(OCN{sub 2}H{sub 4}){sub 5}(H{sub 2}O)][ZnCl{sub 4}] were grown by the isothermal evaporation of an aqueous solution. The crystal structure of this complex was established by X-ray diffraction (R = 0.052 based on 7003 reflections). The crystals consist of [Co(OCN{sub 2}H{sub 4}){sub 5}(H{sub 2}O)]{sup 2+} cations containing Co atoms in an octahedral coordination and [ZnCl{sub 4}]{sup 2-}] anions containing Zn atoms in a tetrahedral coordination. The carbamide molecules are involved in both intramolecular and interionic hydrogen bonds. The H{sub 2}O molecule forms hydrogen bonds with the anions.

  10. Phase-matching properties of yellow color HgGa2S4sub> for SHG and SFG in the 0.944-10.5910  μm range.


    Kato, Kiyoshi; Petrov, Valentin; Umemura, Nobuhiro


    We report new experimental results on the phase-matching properties of yellow color HgGa2S4sub> crystals for harmonic generation of an Nd:YAG laser-pumped KTiOPO4sub> (KTP) optical parametric oscillator (OPO) and CO2 lasers in the 0.944-10.5910 μm range. In addition, we present new Sellmeier equations that provide a good reproduction of the present experimental results as well as the published data points for second-harmonic generation of CO2 laser radiation at 9.2197-9.6392 μm and Nd:YAG laser-pumped OPOs at 1.205-1.725 μm and 2.77-9.10 μm that were achieved with the orange and yellow color crystals. PMID:27140080

  11. Synthesis of Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} through a reactive flux method and its visible-light photocatalytic performances

    SciTech Connect

    Zhu, Xianglin; Wang, Zeyan E-mail:; Huang, Baibiao E-mail:; Zhang, Xiaoyang; Qin, Xiaoyan; Wei, Wei; Dai, Ying


    Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} was prepared by a reactive flux method. The structures, morphologies, and light absorption properties were investigated. Owing to the polar crystal structure, an internal electric field can be formed inside the material, which can facilitate the photogenerated charge separation during the photocatalytic process. Based on both the wide light absorption spectra and high charge separation efficiency originated from the polarized internal electric field, Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} exhibit higher efficiency over Ag{sub 3}PO{sub 4} during the degradation of organic dyes under visible light irradiation, which is expected to be a potential material for solar energy harvest and conversion.

  12. Neutron-scattering evidence for a periodically modulated superconducting phase in the underdoped cuprate La1.905Ba0.095CuO4sub>

    SciTech Connect

    Xu, Zhijun; Stock, C.; Chi, Songxue; Kolesnikov, A. I.; Xu, Guangyong I.; Gu, Genda; Tranquada, J. M.


    The role of antiferromagnetic spin correlations in high-temperature superconductors remains a matter of debate. We present inelastic neutron-scattering evidence that gapless spin fluctuations coexist with superconductivity in La1.905Ba0.095CuO4sub>. Furthermore, we observe that both the low-energy magnetic spectral weight and the spin incommensurability are enhanced with the onset of superconducting correlations. We propose that the coexistence occurs through intertwining of spatial modulations of the pair wave function and the antiferromagnetic correlations. This proposal is also directly relevant to sufficiently underdoped La2-xSrxCuO4sub> and YBa2Cu3O6+x.

  13. Strain-relaxation and critical thickness of epitaxial La1.85Sr0.15CuO4sub> films

    SciTech Connect

    Meyer, Tricia L; Jiang, Lu; Park, Sungkyun; Egami, Takeshi; Lee, Ho Nyung


    We report the thickness-dependent strain-relaxation behavior and the associated impacts upon the superconductivity in epitaxial La1.85Sr0.15CuO4sub> films grown on different substrates, which provide a range of strain. We have found that the critical thickness for the onset of superconductivity in La1.85Sr0.15CuO4sub> films is associated with the finite thickness effect and epitaxial strain. In particular, thin films with tensile strain greater than ~0.25% revealed no superconductivity. We attribute this phenomenon to the inherent formation of oxygen vacancies that can be minimized via strain relaxation.

  14. Growth of the (In{sub 2}S{sub 3}){sub x}(FeIn{sub 2}S{sub 4}){sub 1-x} single crystals and properties of photoelectric structures on their basis

    SciTech Connect

    Bodnar, I. V.; Rud, V. Yu.; Rud, Yu. V.; Terukov, E. I.


    Complete mutual solubility in the (In{sub 2}S{sub 3}){sub x}(FeIn{sub 2}S{sub 4}){sub 1-x} system is established. The technology is developed, and single crystals of the continuous series of the (In{sub 2}S{sub 3}){sub x}(FeIn{sub 2}S{sub 4}){sub 1-x} solid solutions are grown for the first time. The linear dependence of the unit cell parameter of single crystals with a cubic spinel lattice on the solid solution composition is found. First, photosensitive Schottky barriers are fabricated, and then, based on studies of their photosensitivity, the character of band-to-band transition is discussed and the values of the band gap depending on the atomic composition are estimated. The possibility of using the obtained solid solutions as broadband photoconverters of optical radiation is revealed.

  15. Eye-safe 1.55  μm passively Q-switched Er,Yb:GdAl3(BO3)4sub> diode-pumped laser.


    Gorbachenya, K N; Kisel, V E; Yasukevich, A S; Maltsev, V V; Leonyuk, N I; Kuleshov, N V


    We report for the first time, to the best of our knowledge, on a diode-pumped passively Q-switched Er,Yb:GdAl3(BO3)4sub> laser. By using a Co2+:MgAl2O4sub> crystal as a saturable absorber, Q-switched laser pulses with a duration of 12 ns and a maximum energy of 18.7 μJ at a repetition rate of 32 kHz corresponding to an average output power of 0.6 W were obtained at 1550 nm under continuous-wave pumping. In the burst mode of operation, Q-switched laser pulses with the highest energy up to 44 μJ were realized with a pulse repetition rate of 6.5 kHz. PMID:26974080

  16. Structure electronic and ionic conductivity study versus Ca content in Ca{sub 10-x}Sr{sub x}(PO{sub 4}){sub 6}F{sub 2} apatites

    SciTech Connect

    Sghir, B.; Hlil, E.K.; Laghzizil, A.; Boujrhal, F.Z.; Cherkaoui El Moursli, R.; Fruchart, D.


    Substitution effect on the crystallographic structure in Ca{sub 10-x}Sr{sub x}(PO{sub 4}){sub 6}F{sub 2} solid solution are studied by X-ray diffraction patterns and Rietveld refinements. Full potential electronic structure calculations based on LCAO (linear combination atomic orbital) are also performed using the obtained crystallographic parameters. DOS modification and the charge transfer are estimated versus the calcium content. According to the complex impedance method, ionic conductivity changes are explained.

  17. Single-Step Synthesis of FeSO4sub>F1-yOHy (0 ≤ y ≤ 1) Positive Electrodes for Li-Based Batteries

    SciTech Connect

    Ati, M; Sougrati, M-T; Rousse, G; Recham, N; Doublet, M-L; Jumas, J-C; Tarascon, J-M


    The recent discovery of electrochemical activity at 3.6 V vs Li+/Li0 in LiFeSO4sub>F has generated widespread research activity in this new family of fluorosulfate electrode materials aiming at either increasing the Fe3+/Fe2+ redox potential, searching for new active members, or extending this family to hydroxyl-fluorosulfates. Here we present a new low temperature single step synthesis of FeSO4sub>F1-yOHy phases using FeF3 and Fe2(SO4sub>)3 ∙ nH2O as precursors. Using thorough chemical analytical techniques to test for F- content in conjunction with Moessbauer measurements, we demonstrate the existence of a limited solid solution (0.35 < y < 1) within this system. Members pertaining to this solid solution have a redox activity ranging from 3.2 to 3.6 V vs Li+/Li0 and show sustained reversible capacity retention of 130 mAh/g which makes them potentially interesting for Li-based polymer batteries. We demonstrate that the Li-insertion-deinsertion mechanism depends markedly on the sample F- content by using joint in situ XRD and Moessbauer spectroscopy. Moreover, we show the versatility of our synthetic approach by extending it to the elaboration of Fe1-zMzSO4sub>F1-yOHy phases with M = Ti and V.

  18. Synthetic and spectroscopic studies of vanadate glaserites II: Photoluminescence studies of Ln:K{sub 3}Y(VO{sub 4}){sub 2} (Ln=Eu, Er, Sm, Ho, or Tm)

    SciTech Connect

    Kimani, Martin M. McMillen, Colin D. Kolis, Joseph W.


    Glaserite-type potassium yttrium double vanadates (K{sub 3}Y(VO{sub 4}){sub 2}) doped with Eu{sup 3+}, Er{sup 3+}, Sm{sup 3+}, Ho{sup 3+}, or Tm{sup 3+} have been synthesized by solid state reactions at 1000 °C for 48 h and their photoluminescence properties investigated. Efficient energy transfer from the vanadate group to the rare earth ion has been established by photoluminescence investigation. Ultraviolet excitation into the metal to ligand charge transfer band of the vanadate groups results in orange-red, blue and green emissions from Eu{sup 3+} (592 nm), Sm{sup 3+} (602 nm), Tm{sup 3+} (475 nm), Er{sup 3+} (553 nm), and Ho{sup 3+} (541–551 nm) dopant ions. The emission intensities of the lanthanide-doped K{sub 3}Y(VO{sub 4}){sub 2} powders were studied as a function of dopant ion concentrations. Over the concentration ranges studied, no emission quenching was observed for Eu{sup 3+} or Ho{sup 3+} dopants, while Er{sup 3+}, Sm{sup 3+} and Tm{sup 3+} dopants did exhibit such effects for dopant ion concentrations greater than 5%, probably due to cross relaxation processes. - Graphical abstract: Synthesis and photoluminescence in vanadate glaserites. - Highlights: • K{sub 3}Y(VO{sub 4}){sub 2} doped with Eu, Er, Tm, Sm, or Ho were synthesized via solid-state reactions. • Photoluminescence properties are investigated. • The lanthanide doped K{sub 3}Y(VO{sub 4}){sub 2} compounds revealed efficient energy transfer from the vanadate group to the rare earth ions. • The presented compounds are promising materials for light display systems, lasers, and optoelectronic devices.

  19. A limited role for carbonic anhydrase in C4sub> photosynthesis as revealed by a ca1ca2 double mutant in maize.

    SciTech Connect

    Studer, Anthony J.; Gandin, Anthony; Kolbe, Allison R.; Wang, Lin; Cousins, Asaph B.; Brutnell, Thomas P.


    Carbonic anhydrase (CA) catalyzes the first biochemical step of the carbon concentrating mechanism of C4sub> plants, and in C4sub> monocots, it has been suggested that CA activity is near limiting for photosynthesis. Here, we test this hypothesis through the characterization of transposon induced mutant alleles of Ca1 and Ca2 in Zea mays. In addition, these two isoforms account for more than 85% of the CA transcript pool. A significant change in isotopic discrimination is observed in mutant plants, which have as little as 3% of wild-type CA activity, but surprisingly, photosynthesis is not reduced under current or elevated pCO2. However, growth and rates of photosynthesis under sub-ambient pCO2 are significantly impaired in the mutants. These findings suggest, that while CA is not limiting for C4sub> photosynthesis in Z. mays at current pCO2, it likely maintains high rates of photosynthesis when CO2 availability is reduced. Current atmospheric CO2 levels now exceed 400 ppm (~40.53 Pa) and contrast the low CO2 partial pressure (pCO2) conditions under which C4sub> plants expanded their range ~10 million years ago when the global atmospheric CO2 was below 300 ppm (~30.40 Pa). Thus, as CO2 levels continue to rise, selective pressures for high levels of CA may be limited to arid climates where stomatal closure reduces CO2 availability to the leaf.

  20. Temperature dependence of the luminescence of calcium-magnesium phosphate Ca{sub 3}Mg{sub 3}(PO{sub 4}){sub 4}:Eu{sup 2+}, a blue-emitting material for white light-emitting diodes

    SciTech Connect

    Zhang, Xinmin; Pan, Qi; Kim, Sun Il; Yu, Young Moon; Seo, Hyo Jin


    Graphical abstract: - Highlights: • Emission spectrum at 20 K confirms that Eu{sup 2+} ions occupy three sites. • Decay curves of three types of Eu{sup 2+} reflect the characteristics of energy transfer. • The Eu(I) emission is thermally quenched at 323 K. • Ca{sub 3}Mg{sub 3}(PO{sub 4}){sub 4}:Eu{sup 2+} has good thermal stability. • Ca{sub 3}Mg{sub 3}(PO{sub 4}){sub 4}:Eu{sup 2+} is a promising phosphor for near UV excited white LEDs. - Abstract: A blue-emitting phosphor Ca{sub 3}Mg{sub 3}(PO{sub 4}){sub 4}:Eu{sup 2+} peaking at 450 nm was synthesized by a solid state reaction. The XRD patterns, luminescence properties, decay curves of samples as well as their thermal quenching and comparing the luminescence properties with that of commercial material were investigated. At 20 K, the emission spectrum exhibiting two distinct bands peaking at 437 and 473 nm with a shoulder peak at 510 nm can be attributed to the overlap of Eu(I), Eu(II) and Eu(III) emission bands. At 423 K the PL intensity decreases to 80% of the value at room temperature, and the emission wavelength shifts toward high energy. The derived activation energy indicates that the lowest energy level of the Eu{sup 2+} 4f{sup 6}5d{sup 1} state is well isolated from the host lattice conduction band. The PL spectra and chromaticity coordinates are close to those of BAM. Ca{sub 3}Mg{sub 3}(PO{sub 4}){sub 4}:Eu{sup 2+} could be a potential candidate for near-UV excited white LEDs.

  1. Electrical and physical characterization of the Al{sub 2}O{sub 3}/p-GaSb interface for 1%, 5%, 10%, and 22% (NH{sub 4}){sub 2}S surface treatments

    SciTech Connect

    Peralagu, Uthayasankaran Thayne, Iain G.; Povey, Ian M.; Carolan, Patrick; Lin, Jun; Hurley, Paul K.; Contreras-Guerrero, Rocio; Droopad, Ravi


    In this work, the impact of ammonium sulfide ((NH{sub 4}){sub 2}S) surface treatment on the electrical passivation of the Al{sub 2}O{sub 3}/p-GaSb interface is studied for varying sulfide concentrations. Prior to atomic layer deposition of Al{sub 2}O{sub 3}, GaSb surfaces were treated in 1%, 5%, 10%, and 22% (NH{sub 4}){sub 2}S solutions for 10 min at 295 K. The smallest stretch-out and flatband voltage shifts coupled with the largest capacitance swing, as indicated by capacitance-voltage (CV) measurements, were obtained for the 1% treatment. The resulting interface defect trap density (D{sub it}) distribution showed a minimum value of 4 × 10{sup 12 }cm{sup −2}eV{sup −1} at E{sub v} + 0.27 eV. Transmission electron microscopy and atomic force microscopy examination revealed the formation of interfacial layers and increased roughness at the Al{sub 2}O{sub 3}/p-GaSb interface of samples treated with 10% and 22% (NH{sub 4}){sub 2}S. In combination, these effects degrade the interface quality as reflected in the CV characteristics.

  2. Luminescence properties of Ca{sub 14}Mg{sub 2}(SiO{sub 4}){sub 8}:Eu{sup 2+} from various Eu{sup 2+} sites for white-light-emitting diodes

    SciTech Connect

    Zhang, Jia Jiang, Cheng


    Ca{sub 14}Mg{sub 2}(SiO{sub 4}){sub 8}:Eu{sup 2+} phosphors were synthesized by solid-state reaction method, and their luminescence properties were investigated. In the emission spectra, several overlapping emission bands originating from various Eu{sup 2+} sites were found. Eu{sup 2+} in Ca{sub 14}Mg{sub 2}(SiO{sub 4}){sub 8} exhibits green emission around 506 nm, and the sample doped with 0.1 mol% Eu{sup 2+} shows the strongest brightness under 365 nm excitation with the quantum efficiency of 63.6%. In the excitation spectra, strong and broad excitation bands from 250 to 450 nm were observed, which could well match with the emission wavelength of the light-emitting diode chip. The fabrication test on the InGaN chip indicates the Ca{sub 14}Mg{sub 2}(SiO{sub 4}){sub 8}:Eu{sup 2+} phosphor could be promising candidate for white light-emitting diodes.

  3. Temperature-induced changes in the single-crystal structure of K{sub 9}H{sub 7}(SO{sub 4}){sub 8} {center_dot} H{sub 2}O

    SciTech Connect

    Makarova, I. P. Grebenev, V. V.; Chernaya, T. S.; Verin, I. A.; Dolbinina, V. V.; Chernyshov, D. Yu.; Koval'chuk, M. V.


    Interest in superprotonic crystals of M{sub m}H{sub n}(XO{sub 4}){sub (m+n)/2} is associated with the solution to the fundamental problem of modern condensed matter physics: investigations of structural phase transitions and the stabilization of phases with high proton conductivity with the aim of designing new functional materials. The available data suggest that changes in the physical properties in these crystals can occur through different structural mechanisms. To reveal the structural conditionality for anomalies in the physical properties, the crystals of K{sub 9}H{sub 7}(SO{sub 4}){sub 8} {center_dot} H{sub 2}O were studied by X-ray diffraction in the temperature range of 25-463 K, and the crystal structure of the high-temperature phase was determined at 418 K (sp. gr. Pcan). The results of the study indicate that the occurrence of high conductivity in K{sub 9}H{sub 7}(SO{sub 4}){sub 8} {center_dot} H{sub 2}O crystals at high temperatures is associated with the diffusion of water of crystallization, the hydrogen-bond network rearrangement, and the motion of K ions. The hydrogen-bond rearrangement and the hindered back diffusion of water to the crystal stabilize the high-temperature phase and ensure its supercooling to low temperatures.

  4. Consequences of Optimal Bond Valence on Structural Rigidity and Improved Luminescence Properties in SrxBa2-xSiO4sub>:Eu2+ Orthosilicate Phosphors

    SciTech Connect

    Denault, Kristin A.; Brgoch, Jakoah; Gaultois, Michael W.; Mikhailovsky, Alexander; Petry, Ralf; Winkler, Holger; DenBaars, Steven P.; Seshadri, Ram


    The orthosilicate phosphors SrxBa2–xSiO4sub>:Eu2+ have now been known for over four decades and have found extensive recent use in solid-state white lighting. It is well-recognized in the literature and in practice that intermediate compositions in the solid-solutions between the orthosilicates Sr2SiO4sub> and Ba2SiO4sub> yield the best phosphor hosts when the thermal stability of luminescence is considered. We employ a combination of synchrotron X-ray diffraction, total scattering measurements, density functional theory calculations, and low-temperature heat capacity measurements, in conjunction with detailed temperature- and time-resolved studies of luminescence properties to understand the origins of the improved luminescence properties. We observe that in the intermediate compositions, the two cation sites in the crystal structure are optimally bonded as determined from bond valence sum calculations. Optimal bonding results in a more rigid lattice, as established by the intermediate compositions possessing the highest Debye temperature, which are determined experimentally from low-temperature heat capacity measurements. Greater rigidity in turn results in the highest luminescence efficiency for intermediate compositions at elevated temperatures.

  5. Influence of Ga-concentration on the electrical and magnetic properties of magnetoelectric CoGaxFe2–xO4sub>/BaTiO3 composite

    SciTech Connect

    Ni, Yan; Zhang, Zhen; Nlebedim, Cajetan I.; Jiles, David C.


    Multiferroic materials exhibit magnetoelectric (ME) coupling and promise new device applications including magnetic sensors, generators, and filters. An effective method for developing ME materials with enhanced ME effect is achieved by the coupling through the interfacial strain between piezoelectric and magnetostrictive materials. In this study, the electrical and magnetic properties of Ga doped magnetoelectric CoGaxFe2–xO4sub>/BaTiO3 composite are studied systematically. It is found that Ga doping improves the sensitivity of magnetoelastic response and stabilizes the magnetic phase of the composites. More importantly, Ga doping reduces the electrical conductivity of composite, as well as the dielectric loss. An enhancement of the electrostrain with doping Ga is also observed. Quantitative estimation indicates that magnetoelectric coupling is enhanced for Ga-doped CoGaxFe2–xO4sub>/BaTiO3 composites. As a result, the present work is beneficial to the practical application of composite CoFe2O4sub>/BaTiO3-based multiferroic materials.

  6. Site and local structure of activator Eu{sup 2+} in phosphor Ca{sub 10−x}(PO{sub 4}){sub 6}Cl{sub 2}:xEu{sup 2+}

    SciTech Connect

    Wang, Chun-Hai; Gui, Dong-Yun; Qin, Rui; Yang, Feng-Li; Jing, Xi-Ping; Tian, Guang-Shan; Zhu, Wenjun


    The site and local structure of activator Eu{sup 2+} in phosphor Ca{sub 10−x}(PO{sub 4}){sub 6}Cl{sub 2}:xEu{sup 2+} is investigated by experiment measurements, first-principle calculations and XAFS simulations. From first-principle calculations, the “local” structure [bond length L(M–O)≤R(M{sup 2+})+R(O{sup 2−})] of host shows a significant deformation (expansion) when Ca{sup 2+} is substituted by Eu{sup 2+}, and Eu{sup 2+} should prefer 6h site to 4f site in the host. The d→f emission of Eu{sup 2+} at 4f site should show a longer wavelength than that of Eu{sup 2+} at 6h site. The XAFS measurement and simulations suggest that the Eu{sup 2+} in our Ca{sub 9.9}(PO{sub 4}){sub 6}Cl{sub 2}:0.1Eu{sup 2+} sample mainly locates at 6h site. In the emission spectrum, two emission profiles of Ca{sub 9.9}(PO{sub 4}){sub 6}Cl{sub 2}:0.1Eu{sup 2+} sample are obtained and assigned. The major one (2.71 eV≈456 nm) should be the emission of Eu{sup 2+} at 6h site. The minor one (2.61 eV≈465 nm) should be that of Eu{sup 2+} at 4f site. - Graphical abstract: The d→f emission of Eu{sup 2+} in Ca{sub 9.9}(PO{sub 4}){sub 6}Cl{sub 2}:0.1Eu{sup 2+} can be assigned as: emission profile at 2.71 eV and 2.61 eV are Eu{sup 2+} at 6h and 4f site, respectively. Display Omitted - Highlights: • Eu{sup 2+} in Ca{sub 10−x}(PO{sub 4}){sub 6}Cl{sub 2}:xEu{sup 2+} causes deformation to “local” structure. • Eu{sup 2+} should prefer 6h site to 4f site in the host from energy aspect. • Emission at 2.71 eV and 2.61 eV should be Eu{sup 2+} at 6h and 4f site.

  7. Ground-based, integrated path differential absorption LIDAR measurement of CO2, CH4sub>, and H2O near 1.6  μm.


    Wagner, Gerd A; Plusquellic, David F


    A ground-based, integrated path, differential absorption light detection and ranging (IPDA LIDAR) system is described and characterized for a series of nighttime studies of CO2, CH4sub>, and H2O. The transmitter is based on an actively stabilized, continuous-wave, single-frequency external-cavity diode laser (ECDL) operating from 1.60 to 1.65 μm. The fixed frequency output of the ECDL is microwave sideband tuned using an electro-optical phase modulator driven by an arbitrary waveform generator and filtered using a confocal cavity to generate a sequence of 123 frequencies separated by 300 MHz. The scan sequence of single sideband frequencies of 600 ns duration covers a 37 GHz region at a spectral scan rate of 10 kHz (100 μs per scan). Simultaneously, an eye-safe backscatter LIDAR system at 1.064 μm is used to monitor the atmospheric boundary layer. IPDA LIDAR measurements of the CO2 and CH4sub> dry air mixing ratios are presented in comparison with those from a commercial cavity ring-down (CRD) instrument. Differences between the IPDA LIDAR and CRD concentrations in several cases appear to be well correlated with the atmospheric aerosol structure from the backscatter LIDAR measurements. IPDA LIDAR dry air mixing ratios of CO2 and CH4sub> are determined with fit uncertainties of 2.8 μmol/mol (ppm) for CO2 and 22 nmol/mol (ppb) for CH4sub> over 30 s measurement periods. For longer averaging times (up to 1200 s), improvements in these detection limits by up to 3-fold are estimated from Allan variance analyses. Two sources of systematic error are identified and methods to remove them are discussed, including speckle interference from wavelength decorrelation and the seed power dependence of amplified spontaneous emission. Accuracies in the dry air retrievals of CO2 and CH4sub> in a 30 s measurement period are estimated at 4 μmol/mol (1% of ambient levels) and 50

  8. Investigation of structural and luminescent properties of Ce{sup 3+}/Mn{sup 2+} ions-doped Ca{sub 5}(PO{sub 4}){sub 3}F

    SciTech Connect

    Zhang, Lei; Fu, Zuoling; Wu, Zhijian; Wang, Yuan; Fu, Xihong; Cui, Tian


    Graphical abstract: The structural and luminescent properties FAP: Ce{sup 3+} and FAP: Ce{sup 3+}, Mn{sup 2+} were investigated in detail by the spectral measurement and theoretical calculation. The emission of Ce{sup 3+} is fitted by two Gaussian functions dashed lines in wavenumber to further confirm the Ce{sup 3+} ion simultaneously occupy the 4f and 6h sites Ca{sub 5}(PO{sub 4})F host. - Highlights: • A simple hydrothermal method has been used to prepare Ca{sub 5}(PO{sub 4}){sub 3}F: Ce{sup 3+}, Mn{sup 2+} powders with structural and luminescent analysis. • The emission of Ce{sup 3+} is fitted by two Gaussian functions to confirm the Ce{sup 3+} ion simultaneously to occupy the 4f and 6h sites in Ca{sub 5}(PO{sub 4}){sub 3}F host. • Due to an efficient energy transfer, the existence of Ce{sup 3+} (sensitizer) can dramatically enhance the green emission of Mn{sup 2+} (activator) in co-doped samples. - Abstract: Ce{sup 3+}/Mn{sup 2+} ions-doped oxyapatite calcium fluorapatite [Ca{sub 5}(PO{sub 4}){sub 3}F, FAP] has been successfully synthesized by a facile one-step hydrothermal method. The luminescent properties of Ce{sup 3+}- and Ce{sup 3+}/Mn{sup 2+}- activated FAP phosphors were investigated using the photoluminescence (PL) and photoluminescence excitation (PLE) spectra. The emission of Ce{sup 3+} was fitted by two Gaussian functions with dashed lines in wavenumber to confirm the Ce{sup 3+} ion simultaneously to occupy the 4f and 6h sites in Ca{sub 5}(PO{sub 4}){sub 3}F host, which was consistent with the calculated results of crystal field based on chemical bond theory. In addition, the existence of Ce{sup 3+} (sensitizer) can dramatically enhance the green emission of Mn{sup 2+} (activator) in Ce{sup 3+}/Mn{sup 2+} ions co-doped samples due to an efficient energy transfer from Ce{sup 3+} to Mn{sup 2+}. All of these results could help us understand the site assignments and optical properties of the rare earth ions doped in hexagonal Ca{sub 5}(PO{sub 4

  9. Synthesis, crystal structure and properties of alluaudite-like triple molybdate Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24}

    SciTech Connect

    Savina, Aleksandra A.; Solodovnikov, Sergey F.; Belov, Dmitry A.; Basovich, Olga M.; Solodovnikova, Zoya A.; Pokholok, Konstantin V.; Stefanovich, Sergey Yu.; Lazoryak, Bogdan I.; Khaikina, Elena G.


    A new triple molybdate Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} were obtained and its structure was solved (the space group P1{sup ¯}, a=12.5814(5), b=13.8989(5), c=28.4386(9) Å, α=90.108(2), β=90.064(2), γ=90.020(2)°, V=4973.0(3) Å{sup 3}, Z=2, R=0.0440). Characteristic features of the structure are polyhedral layers composed of pairs of edge-shared FeO{sub 6} and (Fe, Na)O{sub 6} octahedra, which are connected by bridging MoO{sub 4} tetrahedra. The layers share common vertices with bridging MoO{sub 4} tetrahedra to form an open 3D framework with the cavities occupied by the Cs{sup +} and Na{sup +} cations. The compound undergoes first-order phase transformation at 642 K and above this phase transition, electrical conductivity reaches 10{sup −3}–10{sup −2} S cm{sup −1}. Thus, Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} may be considered as a promising compound for developing new materials with high ionic conductivity. - Graphical abstract: A new triple molybdate Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} was synthesized and structurally characterized, its physicochemical properties were studied. - Highlights: • New compound Na{sub 25}Cs{sub 8}Fe{sub 5}(MoO{sub 4}){sub 24} was synthesized. • Physicochemical properties of the compound were studied. • The first-order phase transformation is observed. • Electrical conductivity above 642 K is (10{sup −2}–10{sup −3}) S cm{sup −1}. • New compound may be considered as promising object with high ionic conductivity.

  10. Vacuum ultraviolet and near-infrared excited luminescence properties of Ca{sub 3}(PO{sub 4}){sub 2}:RE{sup 3+}, Na{sup +} (RE=Tb, Yb, Er, Tm, and Ho)

    SciTech Connect

    Zhang Jia; Wang Yuhua; Guo Linna; Zhang Feng; Wen Yan; Liu Bitao; Huang Yan


    Tb{sup 3+}, Yb{sup 3+}, Tm{sup 3+}, Er{sup 3+}, and Ho{sup 3+} doped Ca{sub 3}(PO{sub 4}){sub 2} were synthesized by solid-state reaction, and their luminescence properties were studied by spectra techniques. Tb{sup 3+}-doped samples can exhibit intense green emission under VUV excitation, and the brightness for the optimal Tb{sup 3+} content is comparable with that of the commercial Zn{sub 2}SiO{sub 4}:Mn{sup 2+} green phosphor. Under near-infrared laser excitation, the upconversion luminescence spectra of Yb{sup 3+}, Tm{sup 3+}, Er{sup 3+}, and Ho{sup 3+} doped samples demonstrate that the red, green, and blue tricolored fluorescence could be obtained by codoping Yb{sup 3+}-Ho{sup 3+}, Yb{sup 3+}-Er{sup 3+}, and Yb{sup 3+}-Tm{sup 3+} in Ca{sub 3}(PO{sub 4}){sub 2}, respectively. Good white upconversion emission with CIE chromaticity coordinates (0.358, 0.362) is achieved by quadri-doping Yb{sup 3+}-Tm{sup 3+}-Er{sup 3+}-Ho{sup 3+} in Ca{sub 3}(PO{sub 4}){sub 2}, in which the cross-relaxation process between Er{sup 3+} and Tm{sup 3+}, producing the {sup 1}D{sub 2}-{sup 3}F{sub 4} transition of Tm{sup 3+}, is found. The upconversion mechanisms are elucidated through the laser power dependence of the upconverted emissions and the energy level diagrams. - Graphical abstract: The CPO:0.25Tb{sup 3+}, 0.25Na{sup +} exhibits a comparable brightness to the commercial Zn{sub 2}SiO{sub 4}:Mn{sup 2+} upon 147 nm excitation. Good white light color is achieved in CPO:Yb{sup 3+}-Tm{sup 3+}-Er{sup 3+}-Ho{sup 3+} under 980 nm excitation. Highlights: > Ca{sub 3}(PO{sub 4}){sub 2}:Tb{sup 3+},Na{sup +} exhibits a comparable brightness with commercial Zn{sub 2}SiO{sub 4}:Mn{sup 2+}. > Red, green and blue colors are achieved in Yb{sup 3+}, Ho{sup 3+}, Er{sup 3+}, Tm{sup 3+} doped Ca{sub 3}(PO{sub 4}){sub 2}. > Good white emission is obtained in Yb{sup 3+}-Ho{sup 3+}-Er{sup 3+}-Tm{sup 3+} quadri-doped Ca{sub 3}(PO{sub 4}){sub 2}. > Ca{sub 3}(PO{sub 4}){sub 2}:Tb{sup 3+}, Yb{sup 3+}, Ho

  11. Microwave sol–gel synthesis and upconversion photoluminescence properties of CaGd{sub 2}(WO{sub 4}){sub 4}:Er{sup 3+}/Yb{sup 3+} phosphors with incommensurately modulated structure

    SciTech Connect

    Lim, Chang Sung; Aleksandrovsky, Aleksandr; Molokeev, Maxim; Oreshonkov, Aleksandr; Atuchin, Victor


    CaGd{sub 2−x}(WO{sub 4}){sub 4}:Er{sup 3+}/Yb{sup 3+} phosphors with the doping concentrations of Er{sup 3+} and Yb{sup 3+} (x=Er{sup 3+}+Yb{sup 3+}, Er{sup 3+}=0.05, 0.1, 0.2 and Yb{sup 3+}=0.2, 0.45) have been successfully synthesized by the microwave sol–gel method. The crystal structure of CaGd{sub 2−x}(WO{sub 4}){sub 4}:Er{sup 3+}/Yb{sup 3+} tungstates have been refined, and upconversion photoluminescence properties have been investigated. The synthesized particles, being formed after the heat-treatment at 900 °C for 16 h, showed a well crystallized morphology. Under the excitation at 980 nm, CaGd{sub 2}(WO{sub 4}){sub 4}:Er{sup 3+}/Yb{sup 3+} particles exhibited a strong 525-nm and a weak 550-nm emission bands in the green region and a very weak 655-nm emission band in the red region. The Raman spectrum of undoped CaGd{sub 2}(WO{sub 4}){sub 4} revealed about 12 narrow lines. The strongest band observed at 903 cm{sup −1} was assigned to the ν{sub 1} symmetric stretching vibration of WO{sub 4} tetrahedrons. The spectra of the samples doped with Er and Yb obtained under the 514.5 nm excitation were dominated by Er{sup 3+} luminescence preventing the recording of these samples Raman spectra. Concentration quenching of the erbium luminescence at {sup 2}H{sub 11/2}→{sup 4}I{sub 15/2} transition is weak in the range of erbium doping level x{sub Er}=0.05–0.2, while, for transition {sup 4}S{sub 3/2}→{sup 4}I{sub 15/2}, the signs of concentration quenching become pronounced at x{sub Er}=0.2. - Graphical abstract: CaGd{sub 2−x}(WO{sub 4}){sub 4}:Er{sup 3+}/Yb{sup 3+} phosphors with the doping concentrations of Er{sup 3+} and Yb{sup 3+} (x=Er{sup 3+}+Yb{sup 3+}, Er{sup 3+}=0.05, 0.1, 0.2 and Yb{sup 3+}=0.2, 0.45) have been successfully synthesized by the microwave sol–gel method and the crystal structure refinement, and upconversion photoluminescence properties have been investigated. - Highlights: • CaGd{sub 2−x}(WO{sub 4}){sub 4}:Er{sup 3+}/Yb

  12. Thermoluminescence response of K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3} nanophosphor Co-doped with Eu and Ce for gamma ray dosimetry

    SciTech Connect

    Patil, B. J.; Bhadane, Mahesh S.; Dahiwale, S. S.; Bhoraskar, V. N.; Dhole, S. D.; Mandlik, N. T.; Kulkarni, M. S.; Bhatt, B. C.


    K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3} nanophosphors co-doped with Eu and Ce were synthesized by the chemical co-precipitation method. These samples were further annealed at 700 °C structural reformation. The structural and morphological characteristics were studied using XRD and TEM techniques. The particle size calculated from XRD spectra was around 35 nm. The as synthesized sample shows cubic structure annealed at 700 °C. The as synthesized and annealed sample of K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}: EuCe were irradiated with Co{sup 60} gamma rays for the doses from 2Gy to 1kGy. The TL characteristic sample of co-doped were studied for the dosimetric application by gamma radiation. The TL spectrum of annealed sample has single peaked at 160 °C. The Eu doped sample has a high TL sensitivity than Ce doped sample. But after co-doping with Eu and Ce, TL intensity observed to be decreased. The decrees in TL peak intensity of the phosphor on co-doping of Eu and Ce gives an insight into the emission mechanism of the phosphor which involves energy transfer from Eu to Ce. The TL response of all the samples were found to be linear for the dose from 2 Gy to 1 KGy. Therefore, K{sub 2}Ca{sub 2}(SO{sub 4}){sub 3}: EuCe nanophosphor can be used for the measurement of high dose of gamma radiation.

  13. Fluorocarbon assisted atomic layer etching of SiO2 and Si using cyclic Ar/C4sub>F8 and Ar/CHF3 plasma

    SciTech Connect

    Metzler, Dominik; Li, Chen; Engelmann, Sebastian; Bruce, Robert L.; Joseph, Eric A.; Oehrlein, Gottlieb S.


    The need for atomic layer etching (ALE) is steadily increasing as smaller critical dimensions and pitches are required in device patterning. A flux-control based cyclic Ar/C4sub>F8 ALE based on steady-state Ar plasma in conjunction with periodic, precise C4sub>F8 injection and synchronized plasma-based low energy Ar+ ion bombardment has been established for SiO2.1 In this work, the cyclic process is further characterized and extended to ALE of silicon under similar process conditions. The use of CHF3 as a precursor is examined and compared to C4sub>F8. CHF3 is shown to enable selective SiO2/Si etching using a fluorocarbon (FC) film build up. Other critical process parameters investigated are the FC film thickness deposited per cycle, the ion energy, and the etch step length. Etching behavior and mechanisms are studied using in situ real time ellipsometry and X-ray photoelectron spectroscopy. Silicon ALE shows less self-limitation than silicon oxide due to higher physical sputtering rates for the maximum ion energies used in this work, ranged from 20 to 30 eV. The surface chemistry is found to contain fluorinated silicon oxide during the etching of silicon. As a result, plasma parameters during ALE are studied using a Langmuir probe and establish the impact of precursor addition on plasma properties.

  14. Photo- and cathodoluminescence of hydrothermally synthesized Y{sub 3}Al{sub 5}O{sub 12}:Tb and NaY(WO{sub 4}){sub 2}:Tb

    SciTech Connect

    Phillips, M.L.F.; Potter, B.G. Jr.


    Cathodoluminescent (CL) phosphors with improved low-voltage characteristics are needed for use in emissive flat panel displays. Conventional high-temperature methods for phosphor synthesis yield large polycrystalline grains that must be pulverized prior to screen deposition. Grinding has been implicated in reducing phosphor efficiency by causing surface contamination and defects. Hydrothermal synthesis has been used to improve the quality of ceramic powders by producing fine, well-formed crystallites without grinding. Two green-emitting phosphors, Y{sub 3}Al{sub 5}O{sub 12}:Tb (YAG:Tb) and NaY(WO{sub 4}){sub 2}:Tb, were used to test the effects of hydrothermal. synthesis on grain size and morphology, and on low-voltage CL properties. YAG:Th prepared hydrothermally consisted of submicron crystallites with a typical garnet habit. The CL efficiency of hydrothermally synthesized YAG:Tb (3 lm/W at 800 V) was comparable to that of equivalent YAG:Tb compositions prepared via high-temperature solid state reaction. In comparison, CL intensities of Gd{sub 3}Ga{sub 5}O{sub l2}:Tb were slightly better (3.5 lm/W at 800 V), while those of NaY(WO{sub 4}){sub 2}:Tb were approximately 1/100th that of YAG:Tb. Both CL and photoluminescence data show that the difference in the cathodoluminescence of YAG and NaY(WO{sub 4}){sub 2} can be understood in terms of differences in the mechanism of activation.

  15. Effects of Mg doping on the remarkably enhanced electrochemical performance of Na3V2(PO4sub>)3 cathode materials for sodium ion batteries

    SciTech Connect

    Li, Hui; Yu, Xiqian; Bai, Ying; Wu, Feng; Wu, Chuan; Liu, Liang-Yu; Yang, Xiao-Qing


    Na3V2-xMgx(PO4sub>)3/C composites with different Mg2+ doping contents (x=0, 0.01, 0.03, 0.05, 0.07 and 0.1) were prepared by a facile sol-gel method. The doping effects on the crystal structure were investigated by XRD, XPS and EXAFS. The results show that low dose doping Mg2+ does not alter the structure of the material, and magnesium is successfully substituted for vanadium site. The Mg doped Na3V2-xMgx(PO4sub>)3/C composites exhibit significant improvements on the electrochemistry performances in terms of the rate capability and cycle performance, especially for the Na3V1.95Mg0.05(PO4sub>)3/C. For example, when the current density increased from 1 C to 30 C, the specific capacity only decreased from 112.5 mAh g-1 to 94.2 mAh g-1 showing very good rate capability. Moreover, even cycling at a high rate of 20 C, an excellent capacity retention of 81% is maintained from the initial value of 106.4 mAh g-1 to 86.2 mAh g-1 at the 50th cycle. Enhanced rate capability and cycle performance can be attributed to the optimized particle size, structural stability and enhanced ionic and electronic conductivity induced by Mg doping.

  16. Mild hydrothermal synthesis, crystal structure, thermal behaviour, spectroscopic and magnetic properties of (NH{sub 4}){sub 0.80}Li{sub 0.20}[Fe(AsO{sub 4})F

    SciTech Connect

    Berrocal, Teresa


    The (NH{sub 4}){sub 0.80}Li{sub 0.20}[Fe(AsO{sub 4})F] compound has been synthesized under mild hydrothermal conditions. The compound crystallize in the orthorhombic Pna2{sub 1} space group, with cell parameters a=13.352(9), b=6.7049(9), c=10.943(2) A and Z=8. The compound belongs to the KTiO(PO{sub 4}) structure type, with chains alternating FeO{sub 4}F{sub 2} octahedra and AsO{sub 4} tetrahedra, respectively, running along the 'a' and 'b' crystallographic axes. The diffuse reflectance spectrum in the visible region shows the forbidden electronic transitions characteristic of the Fe(III) d{sup 5}-high spin cation in slightly distorted octahedral geometry. The Moessbauer spectrum at room temperature is characteristic of iron (III) cations. The ESR spectra, carried out from room temperature to 200 K, remain isotropic with variation in temperature; the g-value being 1.99(1). Magnetic measurements indicate the predominance of strong antiferromagnetic interactions. - Graphical Abstract: Three-dimensional structure of (NH{sub 4}){sub 0.80}Li{sub 0.20}[Fe(AsO{sub 4})F], a fluoroarsenate containing lithium and ammonium in the structural cavities. Highlights: > (NH{sub 4}){sub 0.80}Li{sub 0.20}[Fe(AsO{sub 4})F] has been synthesized by mild hydrothermal technique. > The compound exhibits a three-dimensional structure. > Moessbauer spectrum indicates the existence of Fe(III) cations. > Visible spectroscopy confirms the hexacoordination of Fe(III). > Magnetic measurements indicate the existence of a global antiferromagnetic ordering.

  17. CW EC-QCL-based sensor for simultaneous detection of H2O, HDO, N2O and CH4sub> using multi-pass absorption spectroscopy.


    Yu, Yajun; Sanchez, Nancy P; Griffin, Robert J; Tittel, Frank K


    A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H2O, HDO, N2O and CH4sub> using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm-1 operating at ~7.8 µm was scanned covering four neighboring absorption lines, for H2O at 1281.161 cm-1, HDO at 1281.455 cm-1, N2O at 1281.53 cm-1 and CH4sub> at 1281.61 cm-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H2O, 3.92 ppbv for HDO, 1.43 ppbv for N2O, and 2.2 ppbv for CH4sub> were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. Experimental measurements of ambient air are also reported. PMID:27409863

  18. New process of preparation, structure, and physicochemical investigations of the new titanyl phosphate Ti{sub 2}O(H{sub 2}O)(PO{sub 4}){sub 2}

    SciTech Connect

    Benmokhtar, S. El jazouli, A.; Chaminade, J.P.; Gravereau, P.; Menetrier, M.; Bouree, F.


    New titanyl phosphate Ti{sub 2}O(H{sub 2}O)(PO{sub 4}){sub 2} has been prepared and characterized by X-ray and neutron diffraction, nuclear magnetic resonance, infrared and Raman spectroscopies and thermogravimetric analysis. The crystal structure has been solved from neutron powder diffraction data at 300 K by Rietveld method in P2{sub 1} space group. The refinement led to satisfactory profile factors (R{sub p}=2.7%, R{sub wp}=3.2%) and crystal structure model indicators (R{sub B}=5.8%, R{sub F}=3.2%). The cell is monoclinic with a=7.3735 A, b=7.0405 A, c=7.6609 A and {beta}=121.48{sup o}, Z=4. The structure can be described as a three-dimensional framework built up by chains of [TiO{sub 5}(OH{sub 2})] octahedra with alternative short bonds [Ti{sub (1)}-O{sub (12)}; Ti{sub (2)}-O{sub (12)}, 1.88-1.84 A] and long ones [Ti{sub (1)}-O{sub W}; Ti{sub (2)}-O{sub W}, 2.25-2.23 A] along c-axis and connected via [PO{sub 4}] tetrahedra. Oxygen atom denoted O{sub (12)} is only linked to two titanium atoms and Oxygen atom denoted O{sub W} is linked to two titanium atoms and two hydrogen atoms. O{sub (12)} and O{sub W} are not linked to P atoms and justify the titanyl phosphate formulation Ti{sub 2}O(H{sub 2}O)(PO{sub 4}){sub 2}. The infrared and Raman spectra presents peaks due to vibrations of Ti-O, P-O and O-H bonds. The {sup 31}P MAS NMR spectrum reveals two {sup 31}P resonance lines, in agreement with the structure which showed two crystallographic sites for phosphorus. The thermogravimetric analysis show that Ti{sub 2}O(H{sub 2}O)(PO{sub 4}){sub 2} is thermally stable until 400 deg. C. Above this temperature, it losses water and decomposes to Ti{sub 5}O{sub 4}(PO{sub 4}){sub 4} and TiP{sub 2}O{sub 7}. - Graphical abstract: The structure of TiHP can be described as a TiOPO{sub 4} framework constituted by chains of tilted corner-sharing [TiO{sub 6}] octahedra and cross linked by [PO{sub 4}] tetrahedra with empty cavities in the framework.

  19. Structure and microwave dielectric properties of Ba{sub 3}(VO{sub 4}){sub 2}–Zn{sub 2−x}SiO{sub 4−x} ceramic composites

    SciTech Connect

    Lv, Yang; Zuo, Ruzhong; Yue, Zhenxing


    Highlights: ► New Ba{sub 3}(VO{sub 4}){sub 2}–Zn{sub 1.87}SiO{sub 3.87} microwave dielectric composite ceramic was reported. ► The single-phase willemite was obtained by controlling of ZnO deficiency. ► The composite with 40 wt% Zn{sub 1.87}SiO{sub 3.87} exhibited excellent τ{sub f} value of 0.4 ppm/°C. - Abstract: Microwave dielectric ceramic composites with compositions of (1 − y)Ba{sub 3}(VO{sub 4}){sub 2}–yZn{sub 2−x}SiO{sub 4−x} (y = 0.4–0.6, x = 0.13) have been prepared by firing mixtures of Ba{sub 3}(VO{sub 4}){sub 2} and Zn{sub 1.87}SiO{sub 3.87}. The X-ray diffraction (XRD) analysis revealed that Zn{sub 2}SiO{sub 4} with a willemite phase can be obtained by appropriately controlling the ZnO deficiency. The starting Zn{sub 1.87}SiO{sub 3.87} powder should be thus composed of the ZnSiO{sub 4} crystal phase and redundant SiO{sub 2} amorphous phase at room temperature. The scanning electron microscopy studies demonstrated the coexistence of Zn{sub 2}SiO{sub 4} and Ba{sub 3}(VO{sub 4}){sub 2} phases in the sintered bodies, as further confirmed by the XRD and Raman results. The near-zero temperature coefficients of the resonant frequency (τ{sub f}) could be achieved by adjusting the relative content of the two phases owing to their opposite τ{sub f} values. The existence of a slight amount of secondary phases, element interdiffusion and non-stoichiometry such as Zn deficiency altogether made the predicted property values deviate from the experimentally measured ones. The composite ceramics with 40 wt% Zn{sub 1.87}SiO{sub 3.87} sintered at 1100 °C exhibited desirable microwave dielectric properties of the quality factor Q × f ∼ 23,000 GHz, dielectric constant ε{sub r} ∼ 9.3, and τ{sub f} ∼ 0.4 ppm/°C.

  20. Two-micron lasing in NaLa{sub 1/2}Gd{sub 1/2}(WO{sub 4}){sub 2} crystals doped with Tm{sup 3+} ions

    SciTech Connect

    Bolshchikov, F A; Ryabochkina, P A; Zharikov, Evgeny V; Lis, Denis A; Subbotin, Kirill A; Zakharov, N G; Antipov, Oleg L


    Lasing on the {sup 3}F{sub 4{yields}}{sup 3}H{sub 6} transition of Tm{sup 3+} ions in Tm{sup 3+}:NaLa{sub 1/2}Gd{sub 1/2}(WO{sub 4}){sub 2} crystals pumped by a diode laser is obtained for the first time. The {pi}- and {sigma}-polarised laser radiation at wavelengths of 1908 and 1918 nm was generated with a slope efficiency of 28% and 25%, respectively. (lasers)

  1. Tunable photoluminescence properties of Ca{sub 8}NaLa(PO{sub 4}){sub 6}F{sub 2}:Eu{sup 2+},Mn{sup 2+} phosphor under UV excitation

    SciTech Connect

    Zhang, Fen; Lan, Tong; Tang, Wanjun


    Highlights: • Ca{sub 8}NaLa(PO{sub 4}){sub 6}F{sub 2}:Eu{sup 2+},Mn{sup 2+} was prepared by a combustion-assisted synthesis method. • The phosphor presents blue and yellow double color emissions. • Efficient energy transfer from Eu{sup 2+} to Mn{sup 2+} in this phosphor is observed obviously. • White emitting was realized in Ca{sub 8}NaGd(PO{sub 4}){sub 6}F{sub 2}:0.10Eu{sup 2+},0.32Mn{sup 2+},0.10B phosphor. - Abstract: A series of Eu{sup 2+} and Mn{sup 2+} coactivated Ca{sub 8}NaLa(PO{sub 4}){sub 6}F{sub 2} (CNLF) phosphors have been synthesized by a combustion-assisted synthesis method. The investigation revealed that Ca{sub 8}NaLa(PO{sub 4}){sub 6}F{sub 2} crystallized in a hexagonal crystal system with the space group P6{sub 3}/m (176). The Eu{sup 2+} activated phosphors can be efficiently excited in the range of 270–400 nm and give intense blue emission peaking at 451 nm. By codoping the Eu{sup 2+} and Mn{sup 2+} ions into the CNLF host and singly varying the doping content of the Mn{sup 2+} ion, tunable colors from blue to white and eventually to yellow are obtained in CNLF:Eu{sup 2+},Mn{sup 2+} phosphors under the irradiation of 330 nm. The energy transfer from Eu{sup 2+} to Mn{sup 2+} in CNLF:Eu{sup 2+},Mn{sup 2+} has been demonstrated to be a resonant type via a dipole–dipole mechanism and the critical distance of energy transfer from Eu{sup 2+} to Mn{sup 2+} was estimated to be about 11.9 Å. The investigation indicates that the obtained samples might have potential application in white LEDs.

  2. North American terrestrial CO2 uptake largely offset by CH4sub> and N2O emissions: toward a full accounting of the greenhouse gas budget

    SciTech Connect

    Tian, Hanqin; Chen, Guangsheng; Lu, Chaoqun; Xu, Xiaofeng; Hayes, Daniel J.; Ren, Wei; Pan, Shufen; Huntzinger, Deborah N.; Wofsy, Steven C.


    The terrestrial ecosystems of North America have been identified as a sink of atmospheric CO2 though there is no consensus on the magnitude. However, the emissions of non-CO2 greenhouse gases (CH4sub> and N2O) may offset or even overturn the climate cooling effect induced by the CO2 sink. Using a coupled biogeochemical model, in this study, we have estimated the combined global warming potentials (GWP) of CO2, CH4sub> and N2O fluxes in North American terrestrial ecosystems and quantified the relative contributions of environmental factors to the GWP changes during 1979–2010. The uncertainty range for contemporary global warming potential has been quantified by synthesizing the existing estimates from inventory, forward modeling, and inverse modeling approaches. Our “best estimate” of net GWP for CO2, CH4sub> and N2O fluxes was₋0.50 ± 0.27 Pg CO2 eq/year (1 Pg=1015 g) in North American terrestrial ecosystems during 2001–2010. The emissions of CH4sub> and N2O from terrestrial ecosystems had offset about two thirds (73% ± 14%) of the land CO2 sink in the North American continent, showing large differences across the three countries, with offset ratios of 57% ± 8% in US, 83% ± 17 % in Canada and 329% ± 119 % in Mexico. Climate change and elevated tropospheric ozone concentration have contributed the most to GWP increase, while elevated atmospheric CO2 concentration have contributed the most to GWP reduction. Extreme drought events over certain periods could result in a positive GWP. By integrating the existing estimates, we have found a wide range of uncertainty for the combined GWP. In conclusion, from both climate change science and policy perspectives, it is necessary to integrate ground and satellite observations with models for a more accurate accounting of these three greenhouse gases in

  3. Rietveld refinement and ionic conductivity of Ca{sub 8.4}Bi{sub 1.6}(PO{sub 4}){sub 6}O{sub 1.8}

    SciTech Connect

    Tmar Trabelsi, I.; Madani, A.; Mercier, A.M.; Toumi, M.


    The structure of Ca{sub 8.4}Bi{sub 1.6}(PO{sub 4}){sub 6}O{sub 1.8}, isostructural with Fluoroapatite, was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed that the formula of this compound is [Ca{sub 4}]{sup 4f}[Ca{sub 4.4}Bi{sub 1.6}]{sup 6h}(PO{sub 4}){sub 6}[O{sub 1.8}]{sup 2a}, space group P63/m (a=9.468 (3) A, c=6.957 (3) A). A total substitution of Bi{sup 3+} ions in the (6h) sites was related particularly to the high polarizability of the Bi{sup 3+} ion compared to Ca{sup 2+}. The observed frequencies in the Raman and infrared spectra were explained and discussed on the basis of unit-cell group analyses and in comparison with Fluoroapatite and other oxyapatites. The ionic conductivity over a wide range of temperature was investigated according to the complex impedance method. The highest overall conductivity values were found at {sigma}{sub 700 Degree-Sign C} =5.03 Multiplication-Sign 10{sup -7} S cm{sup -1} and E{sub a}=0.50 eV. - Graphical abstract: The final Rietveld refinement plot of the Ca{sub 8.4}Bi{sub 1.6} (PO{sub 4}){sub 6}O{sub 1.8}. Highlights: Black-Right-Pointing-Pointer The Rietveld refinement revealed that the formula of this compound is Ca{sub 8.4}Bi{sub 1.6}(PO{sub 4}){sub 6}O{sub 1.8}. Black-Right-Pointing-Pointer Vibrational spectroscopy supports the high symmetry P63/m space group for this apatite. Black-Right-Pointing-Pointer This apatite contained channels where oxygen ions were located in 2a sites. Black-Right-Pointing-Pointer The possibility of anionic conduction along these channels was considered.

  4. High-energy passively Q-switched laser operation of Yb:Ca3La2(BO3)4sub> disordered crystal.


    Wang, Lisha; Han, Wenjuan; Pan, Zhongben; Xu, Honghao; Chen, Xiaowen; Liu, Junhai; Yu, Haohai; Zhang, Huaijin


    Efficient high-energy passively Q-switched laser operation was demonstrated with Yb:Ca3La2(BO3)4sub> disordered crystal, producing an average output power of 3.0 W at 1018.7 nm, at a pulse repetition frequency of 5.0 kHz; the resulting pulse energy, duration, and peak power were 600 μJ, 5.3 ns, and 113.2 kW, respectively. PMID:27140354

  5. The excited state dynamics of KLa(MoO{sub 4}){sub 2}:Pr{sup 3+}: From a case study to the determination of the energy levels of rare earth impurities relative to the bandgap in oxidising host lattices

    SciTech Connect

    Cavalli, Enrico Boutinaud, Philippe; Bettinelli, Marco; Dorenbos, Pieter


    The luminescence properties of KLa(MoO{sub 4}){sub 2} (KLM) single crystals doped with Pr{sup 3+} have been measured in the 10-600 K temperature range in order to investigate the mechanisms involved in the radiationless processes. At variance with previously studied scheelite-like molybdates activated with Pr{sup 3+}, no effects attributed to the formation of intervalence charge transfer states have been observed. The model proposed in order to account for this behaviour allows the determination of the energy of the Pr{sup 3+} levels relative to the valence and conduction bands of the host. This model has firstly been confirmed for Tb{sup 3+}-doped KLM, for which suitable experimental data are available, and then extended to the other rare earth ions on the basis of the systematic nature of the lanthanide energy levels properties. The obtained conclusions are finally supported in the light of the comparison with some other representative cases. - Graphical abstract: The study of the excited state dynamics of KLa(MoO{sub 4}){sub 2} single crystals doped with Pr{sup 3+} allows to determine the energies of the levels of the active ion relative to the valence and conduction bands of the host. This model has then been extended to the other rare earth ions on the basis of the systematic nature of the lanthanide energy levels properties.

  6. An in-situ phosphorus source for the synthesis of Cu3P and the subsequent conversion to Cu3PS4sub> nanoparticle clusters

    SciTech Connect

    Sheets, Erik J.; Stach, Eric A.; Yang, Wei -Chang; Balow, Robert B.; Wang, Yunjie; Walker, Bryce C.; Agrawal, Rakesh


    The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I-V-VI chalcogenides including copper phosphide (Cu3P) and copper thiophosphate (Cu3PS4sub>). Herein, we report a one-pot, solution-based synthesis of Cu3P nanocrystals utilizing an in-situ phosphorus source: phosphorus pentasulfide (P2S5) in trioctylphosphine (TOP). By injecting this phosphorus source into a copper solution in oleylamine (OLA), uniform and size controlled Cu3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cu3P nanocrystals with decomposing thiourea forms nanoscale Cu3PS4sub> particles having p-type conductivity and an effective optical band gap of 2.36 eV.

  7. Crystal structure and properties of K{sub 2}[OsO{sub 2}(C{sub 2}O{sub 4}){sub 2}] . 2H{sub 2}O

    SciTech Connect

    Burvikova, Yu. N. Lin'ko, I. V.; Venskovskii, N. U.; Rybakov, V. B.


    The synthesis and X-ray diffraction study of the compound K{sub 2}[OsO{sub 2}(C{sub 2}O{sub 4}){sub 2}] . 2H{sub 2}O are performed. The compound crystallizes in the triclinic crystal system, space group P1-bar, a = 6.545(1) A, b = 6.835(2) A, c = 7.595(2) A, {alpha} = 85.76(2) deg., {beta} = 65.33(2) deg., {gamma} = 71.14(2) deg., and Z = 1. The osmium atom is located at the center of symmetry and has a distorted octahedral coordination formed by oxygen atoms: two oxygen atoms of the osmyl group occupy the apical positions [Os-O, 1.730(2) A], and four oxygen atoms of the oxalate ions lie in the equatorial plane. The K{sup +} cation is surrounded by ten oxygen atoms located at different K-O distances in the range from 2.787(2) to 3.158(2) A. The assignment of the absorption bands in the IR spectrum of K{sub 2}[OsO{sub 2}(C{sub 2}O{sub 4}){sub 2}] . 2H{sub 2}O is performed. The electronic absorption spectra of the compound are recorded in different solvents, and the thermal behavior in air is studied.

  8. Evolution of competing magnetic order in the Jeff=1/2 insulating state of Sr2Ir1-xRuxO4sub>

    SciTech Connect

    Calder, Stuart A.; Kim, Jong-Woo; Cao, Guixin; Cantoni, Claudia; May, Andrew F; Cao, Huibo B.; Aczel, Adam A.; Matsuda, Masaaki; Choi, Yongseong; Haskel, Daniel; Sales, B. C.; Mandrus, David; Lumsden, Mark D.; Christianson, Andrew D.


    We investigate the magnetic properties of the series Sr2Ir1-xRuxO4sub> with neutron, resonant x-ray and magnetization measurements. The results indicate an evolution and coexistence of magnetic structures via a spin flop transition from ab-plane to c-axis collinear order as the 5d Ir4+ ions are replaced with an increasing concentration of 4d Ru4+ ions. The magnetic structures within the ordered regime of the phase diagram (x<0.3) are reported. Despite the changes in magnetic structure no alteration of the Jeff=1/2 ground state is observed. This behavior of Sr2Ir1-xRuxO4sub> is consistent with electronic phase separation and diverges from a standard scenario of hole doping. The role of lattice alterations with doping on the magnetic and insulating behavior is considered. Our results presented here provide insight into the magnetic insulating states in strong spin-orbit coupled materials and the role perturbations play in altering the behavior.

  9. Hydrothermal synthesis, characterization and magnetic properties of (N{sub 4}C{sub 6}H{sub 21}).(Co(H{sub 2}PO{sub 4})(HPO{sub 4}){sub 2})

    SciTech Connect

    Dakhlaoui, A.; Smiri, L.S. . E-mail:


    The title compound (N{sub 4}C{sub 6}H{sub 21}).(Co(H{sub 2}PO{sub 4})(HPO{sub 4}){sub 2}), was prepared hydrothermally (473 K, 10 days, autogenous pressure), in the presence of the tris(2-aminoethyl)amine as organic template. Its structure is built up from a network of four membered-rings, formed by the vertex linkages between [CoO{sub 4}] and [H{sub 2}PO{sub 4}] tetrahedra with [HPO{sub 4}] moieties hanging from the Co center. Hydrogen bonds involving the cobalt phosphate units and the triply protonated amine molecule, contribute to the stability of the structure. The IR spectrum shows bands characteristic of the (N{sub 4}C{sub 6}H{sub 21}){sup 3+} cations and the (H{sub 2}PO{sub 4}){sup -} and (HPO{sub 4}){sup 2-} phosphate anions. The UV-Visible-NIR spectrum confirms the tetrahedral coordination of Co{sup 2+} ions. The TGA analysis indicates that the dehydration of (N{sub 4}C{sub 6}H{sub 21}).(Co(H{sub 2}PO{sub 4})(HPO{sub 4}){sub 2}) occurs in one step. Magnetic measurements from 4.5 to 305 K show a weak antiferromagnetic character of this compound.

  10. Toward understanding the lithiation/delithiation process in Fe0.5TiOPO4sub>/C electrode material for lithium-ion batteries

    SciTech Connect

    Lasri, Karima; Mahmoud, Abdelfattah; Saadoune, Ismael; Sougrati, Moulay Tahar; Stievano, Lorenzo; Lippens, Pierre-Emmanuel; Hermann, Raphaël Pierre; Ehrenberg, Helmut


    We used Fe0.5TiOPO4sub>/C composite as anode material for LIB and exhibits excellent cycling performance when the electrode is cycled in two different voltage ranges [3.0-1.3V] and [3.0- 0.02V] where different insertion mechanisms were involved. Based on in situ X-ray diffraction, in situ XANES spectroscopy results, and various electrochemical analyses at high and low voltage cut-off, we found that Fe0.5TiOPO4sub>/C electrode materials still maintains its structure crystallinity after cycling between [3.0-1.3V] showing formation of new phase at the end of first discharge, with a reversible capacity of 100 mAhg-1 after 50 cycles at C/5 rate. Moreover, at highly lithiated states, [3.0-0.02V] voltage range, a reduction decomposition reaction highlights the Li-insertion/extraction behaviors, and low phase crystallinity is observed during cycling, in addition an excellent rate behavior and a reversible capacity of 250 mAhg- 1 can still be maintained after 50 cycles at high cycling rate 5C.

  11. Magnetic and structural transitions in La0.4sub>Na0.6Fe2As2 single crystals

    SciTech Connect

    Yan, Jiaqiang; Nandi, S.; Saparov, Bayrammurad I.; Cermak, P.; Xiao, Y.; Su, Y.; Jin, W. T.; Schneidewind, A.; Bruckel, Th.; McCallum, R. W.; Lograsso, Thomas A.; Sales, B. C.; Mandrus, D. G.


    La0.4sub>Na0.6Fe2As2 single crystals have been grown out of an NaAs flux in an alumina crucible and characterized by measuring magnetic susceptibility, electrical resistivity, specific heat, as well as single-crystal x-ray and neutron diffraction. La0.4sub>Na0.6Fe2As2 single crystals show a structural phase transition from a high-temperature tetragonal phase to a low-temperature orthorhombic phase at Ts=125 K. This structural transition is accompanied by an anomaly in the temperature dependence of electrical resistivity, anisotropic magnetic susceptibility, and specific heat. Concomitant with the structural phase transition, the Fe moments order along the a direction with an ordered moment of 0.7(1) μB at T=5 K. Finally, the low-temperature stripe antiferromagnetic structure is the same as that in other AFe2As2 (A = Ca, Sr, Ba) compounds. La0.5₋xNa0.5+xFe2As2 provides a material platform for the study of iron-based superconductors where the electron-hole asymmetry could be studied by simply varying the La/Na ratio.

  12. High-power actively Q-switched single-mode 1342 nm Nd:YVO4sub> ring laser, injection-locked by a cw single-frequency microchip laser.


    Koch, Peter; Bartschke, Juergen; L'huillier, Johannes A


    In this paper we report on the realization of a single-mode Q-switched Nd:YVO4sub> ring laser at 1342 nm. Unidirectional and single-mode operation of the ring laser is achieved by injection-locking with a continuous wave Nd:YVO4sub> microchip laser, emitting a single-frequency power of up to 40 mW. The ring laser provides a single-mode power of 13.9 W at 10 kHz pulse repetition frequency with a pulse duration of 18.2 ns and an excellent beam quality (M2 < 1.05). By frequency doubling of the fundamental 1342 nm laser, a power of 8.7 W at 671 nm with a pulse duration of 14.8 ns and a beam propagation factor of M2 < 1.1 is obtained. The 671 nm radiation features a long-term spectral width of 75 MHz. PMID:26698762

  13. [NH{sub 3}(CH{sub 2}){sub 2}NH{sub 3}][Co(SO{sub 4}){sub 2}(H{sub 2}O){sub 4}]: Chemical preparation, crystal structure, thermal decomposition and magnetic properties

    SciTech Connect

    Rekik, Walid; Naili, Houcine; Mhiri, Tahar; Bataille, Thierry


    Cobalt ethylenediammonium bis(sulfate) tetrahydrate, [NH{sub 3}(CH{sub 2}){sub 2}NH{sub 3}][Co(SO{sub 4}){sub 2}(H{sub 2}O){sub 4}], has been synthesised by slow evaporation at room temperature. It crystallises in the triclinic system, space group P1-bar, with the unit cell parameters: a = 6.8033(2), b 7.0705(2), c = 7.2192(3) A, {alpha} = 74.909(2){sup o}, {beta} = 72.291(2){sup o}, {gamma} = 79.167(2){sup o}, Z = 1 and V = 317.16(2) A{sup 3}. The Co(II) atom is octahedrally coordinated by four water molecules and two sulfate tetrahedra leading to trimeric units [Co(SO{sub 4}){sub 2}(H{sub 2}O){sub 4}]. These units are linked to each other and to the ethylenediammonium cations through OW-H...O and N-H...O hydrogen bonds, respectively. The zero-dimensional structure is described as an alternation between cationic and anionic layers along the crystallographic b-axis. The dehydration of the precursor proceeds through three stages leading to crystalline intermediary hydrate phases and an anhydrous compound. The magnetic measurements show that the title compound is predominantly paramagnetic with weak antiferromagnetic interactions.

  14. Solid-state reaction preparation and photoluminescence properties of Na{sub 2}Ba{sub 6}(Si{sub 2}O{sub 7})(SiO{sub 4}){sub 2}:Eu{sup 2+} phosphors

    SciTech Connect

    Shi, Pinglu; Xia, Zhiguo


    Graphical abstract: - Highlights: • Green-emitting phosphor powder Na{sub 2}Ba{sub 6}(Si{sub 2}O{sub 7})(SiO{sub 4}){sub 2}:Eu{sup 2+} was synthesized. • Two different emission centers occupied by Eu{sup 2+} were investigated. • The concentration quenching mechanism was studied. - Abstract: A kind of novel green-emitting phosphor Na{sub 2}Ba{sub 6}(Si{sub 2}O{sub 7})(SiO{sub 4}){sub 2}:Eu{sup 2+} was synthesized by a solid-state reaction. The phase formation of as-prepared sample was investigated by X-ray powder diffraction. The photoluminescence emission (PL) and excitation (PLE) spectra results indicated that the phosphor could be efficiently excited by ultraviolet (UV) light from 240 to 400 nm, and presented a broad green emission band with two-band profile suggesting two different emission centers occupied by Eu{sup 2+}. The critical quenching concentration of Eu{sup 2+} was determined to be 0.01 mol and the concentration quenching mechanism was also investigated.

  15. Magnetic ordering in the frustrated J1 - J2 Ising chain candidate BaNd2O4sub>

    SciTech Connect

    Aczel, Adam A.; Li, Ling; Garlea, Vasile O.; Yan, Jiaqiang; Weickert, Franziska; Jaime, M.; Maiorov, B.; Movshovich, R.; Civale, L.; Keppens, V.; Mandrus, D.


    The AR2O4sub> family (R = rare earth) has recently been attracting interest as a new series of frustrated magnets, with the magnetic R atoms forming zigzag chains running along the c axis. In this paper, we have investigated polycrystalline BaNd2O4sub> with a combination of magnetization, heat-capacity, and neutron powder diffraction measurements. Magnetic Bragg peaks are observed below TN = 1.7 K, and they can be indexed with a propagation vector of k = (0,1/2,1/2). The signal from magnetic diffraction is well described by long-range ordering of only one of the two types of Nd zigzag chains, with collinear up-up-down-down intrachain spin configurations (double Néel state). Furthermore, low-temperature magnetization and heat-capacity measurements reveal two magnetic-field-induced spin transitions at 2.75 and 4 T for T = 0.46 K. The high-field phase is paramagnetic, while the intermediate-field state may arise from a spin transition of the long-range ordered Nd chains. Finally, one possible candidate for the field-induced ordered state corresponds to an up-up-down intrachain spin configuration, as predicted for a classical J1-J2 Ising chain with a double Néel ground state in zero field.

  16. 1.6  MW peak power, 90  ps all-solid-state laser from an aberration self-compensated double-passing end-pumped Nd:YVO4sub> rod amplifier.


    Wang, Chunhua; Liu, Chong; Shen, Lifeng; Zhao, Zhiliang; Liu, Bin; Jiang, Hongbo


    In this paper a delicately designed double-passing end-pumped Nd:YVO4sub> rod amplifier is reported that produces 10.2 W average laser output when seeded by a 6 mW Nd:YVO4sub> microchip laser at a repetition rate of 70 kHz with pulse duration of 90 ps. A pulse peak power of ∼1.6  MW and pulse energy of ∼143  μJ is achieved. The beam quality is well preserved by a double-passing configuration for spherical-aberration compensation. The laser-beam size in the amplifier is optimized to prevent the unwanted damage from the high pulse peak-power density. This study provides a simple and robust picosecond all-solid-state master oscillator power amplifier system with both high peak power and high beam quality, which shows great potential in the micromachining. PMID:27140580

  17. Hydrothermal synthesis and crystal structure of a new inorganic/organic hybrid of scandium sulfate: (H{sub 2}en)Sc{sub 2}(SO{sub 4}){sub 4}.(H{sub 2}O){sub 0.72}

    SciTech Connect

    Lu Jianjiang . E-mail:; Schlueter, John A.; Geiser, Urs


    The first organically templated layered structure of scandium sulfate, (H{sub 2}en)Sc{sub 2}(SO{sub 4}){sub 4}.(H{sub 2}O){sub 0.72}, (en=ethylenediamine) was synthesized by a hydrothermal method and characterized by single crystal X-ray diffraction. In the title compound, scandium ions are bridged by sulfate groups with a ratio of 1:2 into a 4{sub 3}{sup 6} layer structure. These layers are parallel packed and separated from each other by ethylenediammonium dications and water molecules. The title compound crystallizes in the monoclinic space group P2/c, with cell parameters a=8.5966(13)A, b=5.1068(8)A, c=18.847(3)A, {beta}=91.210(3){sup o}, V=827.2(2)A{sup 3} and Z=2. Refinement gave R{sub 1}[I>2{sigma}(I)]=0.0354 and wR{sub 2}[I>2{sigma}(I)]=0.0878. Thermogravimetric analysis indicates that this material is thermally stable to above 400 deg. C.

  18. Discovery of the (In{sub 2}S{sub 3}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} solid solutions and fabrication of photosensitive structures based on them

    SciTech Connect

    Rud, V. Yu.; Rud, Yu. V.; Osipova, M. A.; Bodnar, I. V.


    A technology of growing single crystals of (In{sub 2}S{sub 3}){sub x}(MnIn{sub 2}S{sub 4}){sub 1-x} solid solutions that provides control over their atomic composition in the entire concentration range 0 {<=} x {<=} 1 is developed. It is shown that, in the range x = 0-1, the single crystals have the cubic spinel structure and the unit cell parameter a follows the linear dependence on x. The exponential character of the temperature dependence of resistivity of solid solutions, on which the first photosensitive Cu/(In{sub 2}S{sub 3})x(MnIn{sub 2}S{sub 4}){sub 1-x} structures are obtained, is revealed. The first photosensitivity spectra of these structures are obtained, and, based on these spectra, dependences of energy of the direct and indirect band-to-band transitions on the composition x are determined. The possibility of applying these structures in broad-band photoconverters of optical radiation is concluded.

  19. Novel Dy{sup 3+}-doped Ca{sub 2}Gd{sub 8}(SiO{sub 4}){sub 6}O{sub 2} white light phosphors for Hg-free lamps application

    SciTech Connect

    Wang, Yuhua; Wen, Yan; Zhang, Feng


    The luminescent properties of Ca{sub 2}Gd{sub 8(1-x)}(SiO{sub 4}){sub 6}O{sub 2}:xDy{sup 3+} (1% {<=} x {<=} 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O{sup 2-} {yields} Gd{sup 3+}, and O{sup 2-} {yields} Dy{sup 3+} charge transfer band respectively, which is consistent with the theoretical calculated value using J{phi}rgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy{sup 3+} in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca{sub 2}Gd{sub 8}(SiO{sub 4}){sub 6}O{sub 2}:Dy{sup 3+} phosphor could be considered as a potential candidate for Hg-free lamps application.

  20. Influence of electron doping on the ground state of (Sr1-xLax)2IrO4sub>

    SciTech Connect

    Chen, Xiang; Hogan, Tom; Walkup, D.; Zhou, Wenwen; Pokharel, M.; Yao, Mengliang; Tian, Wei; Ward, Thomas Zac; Zhao, Y.; Parshall, Dr. D.; Opeil, C.; Lynn, J. W.; Madhavan, Vidya; Wilson, Stephen


    The evolution of the electronic properties of electron-doped (Sr1-xLax)2IrO4sub> is experimentally explored as the doping limit of La is approached. As electrons are introduced, the electronic ground state transitions from a spin-orbit Mott phase into an electronically phase separated state, where long-range magnetic order vanishes beyond x = 0:02 and charge transport remains percolative up to the limit of La substitution (x =0:06). In particular, the electronic ground state remains inhomogeneous even beyond the collapse of the parent state's long-range antiferromagnetic order, while persistent short-range magnetism survives up to the highest La-substitution levels. Furthermore, as electrons are doped into Sr2IrO4sub>, we observe the appearance of a low temperature magnetic glass-like state intermediate to the complete suppression of antiferromagnetic order. Universalities and di erences in the electron-doped phase diagrams of single layer and bilayer Ruddlesden-Popper strontium iridates are discussed.

  1. High-pressure phase transitions of Fe3-xTixO4sub> solid solution up to 60 GPa correlated with electronic spin transition

    SciTech Connect

    Yamanaka, Takamitsu; Kyono, Atsushi; Nakamoto, Yuki; Meng, Yue; Kharlamova, Svetlana; Struzhkin, Victor V.; Mao, Ho-kwang


    The structural phase transition of the titanomagnetite (Fe3–xTixO4sub>) solid solution under pressures up to 60 GPa has been clarified by single-crystal and powder diffraction studies using synchrotron radiation and a diamond-anvil cell. Present Rietveld structure refinements of the solid solution prove that the prefered cation distribution is based on the crystal field preference rather than the magnetic spin ordering in the solid solution. The Ti-rich phases in 0.734 ≤ x ≤1.0 undergo a phase transformation from the cubic spinel of Fd3m to the tetragonal spinel structure of I4<sub>1/amd with c/a < 1.0. The transition is driven by a Jahn-Teller effect of IVFe2+ (3d6) on the tetrahedral site. The c/a < 1 ratio is induced by lifting of the degeneracy of the e orbitals by raising the dx2-y2 orbital below the energy of the dz2 orbital. The distortion characterized by c/a < 1 is more pronounced with increasing Ti content in the Fe3–xTixO4sub> solid solutions and with increasing pressure. An X-ray emission experiment of Fe2TiO4sub> at high pressures confirms the spin transition of FeKβ from high spin to intermediate spin (IS) state. The high spin (HS)-to-low spin (LS) transition starts at 14 GPa and the IS state gradually increases with compression. The VIFe2+ in the octahedral site is more prone for the HS-to-LS transition, compared with Fe2+ in the fourfold- or eightfold-coordinated site. The transition to the orthorhombic post-spinel structure with space group Cmcm has been confirmed in the whole compositional range of Fe3–xTixO4sub>. The transition pressure decreases from 25 GPa (x = 0.0) to 15 GPa (x = 1.0) with increasing Ti content. There are two cation sites in the orthorhombic phase: M1 and M2 sites of eightfold and sixfold coordination, respectively. Fe

  2. Origin of periodic domain structure in Er{sup 3+}-doped beta'-(Sm,Gd){sub 2}(MoO{sub 4}){sub 3} crystal lines patterned by laser irradiations in glasses

    SciTech Connect

    Suzuki, Futoshi; Honma, Tsuyoshi; Komatsu, Takayuki


    Er{sup 3+}-doped beta'-(Sm,Gd){sub 2}(MoO{sub 4}){sub 3} crystal lines are patterned on the surface of Er{sub 2}O{sub 3}-Gd{sub 2}O{sub 3}-Sm{sub 2}O{sub 3}-MoO{sub 3}-B{sub 2}O{sub 3} glasses by continuous-wave Yb:YVO{sub 4} laser irradiations (wavelength: 1080 nm, power: 1.3 W, scanning speeds: 5 {mu}m/s), and the origin of the periodicity of self-organized domain structures with high and low refractive index regions in crystal lines is examined from polarized optical microscope (POM) observations, micro-Raman scattering spectrum, and photoluminescence spectrum measurements. It is found that the periodicity of domain structures changes largely depending on Er{sub 2}O{sub 3} content, i.e., the length of high (bright color in POM observations) and low (dark color) refractive index regions increases with increasing Er{sub 2}O{sub 3} content and homogeneous crystal lines with no periodic domain structures are patterned in Er{sub 2}O{sub 3}-Sm{sub 2}O{sub 3}-MoO{sub 3}-B{sub 2}O{sub 3} glass with no Gd{sub 2}O{sub 3}. Considering that the degree of ferroelasticities in beta'-(Sm,Gd){sub 2}(MoO{sub 4}){sub 3} crystals decreases due to the incorporation of Er{sup 3+} ions, it is demonstrated that the origin of periodic domain structures in laser-patterned lines is due to spontaneous strains in ferroelastic beta'-(Sm,Gd){sub 2}(MoO{sub 4}){sub 3} crystals. - Graphical abstract: This figure shows the polarized optical photographs (top view) for the lines patterned by laser irradiations with the power of P=1.3 W and the scanning speed of S=5 {mu}m/s in xEr{sub 2}O{sub 3}-(18.25-x)Gd{sub 2}O{sub 3}-3Sm{sub 2}O{sub 3}-63.75MoO{sub 3}-15B{sub 2}O{sub 3} (mol%) glasses. This figure indicates that the periodicity of domain structures in beta'-(Sm,Gd){sub 2}(MoO{sub 4}){sub 3} crystal lines, i.e., the lengths of bright (high refractive index) and dark (low refractive index) color regions, changes depending on the amount of Er{sub 2}O{sub 3} addition. It is demonstrated that the

  3. Neutron diffraction and thermoelectric properties of indium filled In x Co 4sub> Sb 12 ( x=0.05, 0.2) and indium cerium filled Ce 0.05 In 0.1 Co 4sub> Sb 12 skutterudites: Neutron diffraction and thermoelectric properties of In/Ce skutterudites

    SciTech Connect

    Sesselmann, Andreas; Klobes, Benedikt; Dasgupta, Titas; Gourdon, Olivier; Hermann, Raphael; Mueller, Eckhard


    The thermoelectric properties on polycrystalline single (In) and double filled (Ce, In) skutterudites are characterized between 300 and 700 K. Powder neutron diffraction measurements of the skutterudite compositions InxCo4sub>Sb12 (x= 0.05, 0.2) and Ce0.05In0.1Co4sub>Sb12 as a function of temperature (12- 300 K) were carried out, which gives more insight into the structural data of single and double-filled skutterudites. Our results show that due to the annealing treatment, a Sb deficiency is detectable and thus verifies defects at the Sb lattice site of the skutterudite. Furthermore, we show by electron microprobe analysis that a considerable amount of indium is lost during synthesis and post-processing for the single indium filled samples, but not for the double cerium and indium skutterudite sample. The double-filled skutterudite is superior to the single-filled skutterudite composition due to a higher charge carrier density, a comparable lattice thermal resistivity, and a higher density of states effective mass in our experiment. Finally, we obtained a significantly higher Einstein temperature for the double-filled skutterudite composition in comparison to the single-filled species, which reflects the high sensitivity due to filling of the void lattice position within the skutterudite crystal.

  4. The red-emitting phosphors of Eu{sup 3+}-activated MR{sub 2}(MoO{sub 4}){sub 4} (M = Ba, Sr, Ca; R = La{sup 3+}, Gd{sup 3+}, Y{sup 3+}) for light emitting diodes

    SciTech Connect

    Qin, Lin; Huang, Yanlin; Tsuboi, Taiju; Seo, Hyo Jin


    Graphical abstract: The luminescence quantum efficiencies of Eu{sup 3+}-doped MY{sub 2−x}Eu{sub x}(MoO{sub 4}){sub 4} show the dependence on the Eu{sup 3+} doping (x) for M = Ca (a), Sr (b), Ba (c). Display Omitted Highlights: ► Eu{sup 3+}-activated MY{sub 2}(MoO{sub 4}){sub 4} (M = Ba, Sr, Ca) were firstly prepared. ► Comprehensive investigations of QEs and thermal stabilities of Eu{sup 3+}-activated MR{sub 2}(MoO{sub 4}){sub 4} (M = Ba, Sr, Ca; R = La, Gd). ► BaYEu(MoO{sub 4}){sub 4}, SrY0.6Eu1.4(MoO{sub 4}){sub 4} and CaEu{sub 2}(MoO{sub 4}){sub 4} are the best choice for solid state lighting because of high QEs and thermal stabilities. -- Abstract: A series of red-emitting phosphors of MR{sub 2}(MoO{sub 4}){sub 4}:Eu{sup 3+} (M = Ba, Sr, Ca; R = La{sup 3+}, Gd{sup 3+}, Y{sup 3+}) were prepared by solid-state reaction. The photoluminescence excitation and emission spectra were investigated. The phosphors can be efficiently excited by the near UV light and exhibit a red luminescence corresponding to the electric dipole transition {sup 5}D{sub 0} → {sup 7}F{sub 2} at 615 nm. The optimum doping in MY{sub 2−x}Eu{sub x}(MoO{sub 4}){sub 4} (M = Ba, Sr, Ca) were investigated by the dependence of luminescence quantum efficiency (QE) on the Eu{sup 3+} concentrations. The absolute luminescence quantum efficiencies were measured for all the samples. The luminescence thermal satiability was checked by measuring the temperature-dependent luminescence intensities in temperature region of 10–450 K. The results indicate that the three phosphors of BaYEu(MoO{sub 4}){sub 4}, SrY{sub 0.6}Eu{sub 1.4}(MoO{sub 4}){sub 4} and CaEu{sub 2}(MoO{sub 4}){sub 4} are the best choice for white-LEDs to be used for lighting. This was evaluated in details by taking into account of the properties such as the excitation spectra, the luminescence QEs, the red color coordinates, the luminescence quenching of Eu{sup 3+}-doping concentrations and the thermal stability.

  5. Intrinsic Nanostructure in Zr2-xFe4sub>Si16-y(x=0.81, y=6.06)

    SciTech Connect

    Smith, G J; Simonson, J W; Orvis, T; Marques, C; Grose, J E; Kistner-Morris, J J; Wu, L; Cho, Kyuil; Kim, Hyong june; Tanatar, Makariy A; Garlea, V O; Prozorov, Ruslan; Zhu, Y; Aronson, M C


    We present a study of the crystal structure and physical properties of single crystals of a new Fe-based ternary compound, Zr2-xFe4sub>Si16-y(x=0.81,y=6.06). Zr1.19Fe4sub>Si9.94 is a layered compound, where stoichiometric β-FeSi2-derived slabs are separated by Zr-Si planes with substantial numbers of vacancies. High resolution transmission electron microscopy (HRTEM) experiments show that these Zr-Si layers consist of 3.5nm domains where the Zrand Si vacancies are ordered within a supercell sixteen times the volume of the stoichiometric cell. Within these domains, the occupancies of the Zr and Si sites obey symmetry rules that permit only certain compositions, none of which by themselves reproduce the average composition found in x-ray diffraction experiments. Magnetic susceptibility and magnetization measurements reveal a small but appreciable number of magnetic moments that remain freely fluctuating to 1.8K, while neutron diffraction confirms the absence of bulk magnetic order with a moment of 0.2μB or larger down to 1.5K. Electrical resistivity measurements find that Zr1.19Fe4sub>Si9.94 is metallic, and the modest value of the Sommerfeld coefficient of the specific heat γ = C/T suggests that quasi-particle masses are not particularly strongly enhanced. The onset of superconductivity at Tc ≃ 6K results in a partial resistive transition and a small Meissner signal, although a bulk-like transition is found in the specific heat. Sharp peaks in the ac susceptibility signal the interplay of the normal skin depth and the London penetration depth, typical of a system in which nano-sized superconducting grains are separated by a on-superconducting host. Ultra low field differential magnetic susceptibility measurements reveal the presence of a surprisingly large number of trace magnetic and superconducting phases, suggesting that the Zr-Fe-Si ternary system

  6. A study of spin canting in Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 3} with Mössbauer spectroscopy under 5 T

    SciTech Connect

    Kim, Hee Seung; Kim, Chul Sung


    Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 3} has been actively studied as a Lithium ion battery cathode material for the next-generation energy storage application. Here, we have investigated the changes of magnetic coupling between two different magnetic sub-lattices in Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 3} with x-ray diffraction (XRD), superconducting quantum interference device (SQUID), and Mössbauer spectroscopy measurements. The experimental XRD pattern was analyzed using Rietveld refinement, confirming single phase. In order to investigate the magnetic property, the SQUID measurement under applied field of 5 T was performed between 4.2 and 295 K. From the temperature-dependent zero-field-cooled and field-cooled magnetization curves, we observed the magnetization decreasing with increasing temperature up to T{sub min} = 13 K, at which the magnetization showed a minimum value. With continuing increase in temperature, the magnetization starts increasing with a maximum value at T{sub max} = 28 K and beyond T{sub max}, the magnetization decreases with the further increase in temperature. Based on the experimentally measured Mössbauer spectra, we identified that the ratios of first and sixth to second and fifth absorption lines were identical around T{sub min}, while with increasing temperature the area of second and fifth absorption line rapidly decreased up to T{sub max}. Our study suggests that the spin canting angle between the applied field and hyperfine field of Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 3} is constant up to T{sub min}. However, the spin canting angle starts decreasing with increasing temperature, reaching a minimum value at T{sub max}, and beyond T{sub max} it is increasing. We expect that around T{sub max}, the ferrimagnetically coupled spin arrangement is appeared to be collinear along the applied field direction under applied field of 5 T.

  7. Synthetic and spectroscopic studies of vanadate glaserites I: Upconversion studies of doubly co-doped (Er, Tm, or Ho):Yb:K{sub 3}Y(VO{sub 4}){sub 2}

    SciTech Connect

    Kimani, Martin M. Chen, Hongyu McMillen, Colin D. Anker, Jeffery N. Kolis, Joseph W.


    The synthesis and upconversion properties of trigonal glaserite-type K{sub 3}Y(VO{sub 4}){sub 2} co-doped with Er{sup 3+}/Yb{sup 3+}, Ho{sup 3+}/Yb{sup 3+}, or Tm{sup 3+}/Yb{sup 3+} were studied. Powder samples were synthesized by solid state reactions at 1000 °C for 48 h, while well-formed hexagonal single crystals of the same were grown hydrothermally using 10 M K{sub 2}CO{sub 3} at 560–650 °C. Infrared-to-visible upconversion by Er{sup 3+}/Yb{sup 3+}, Ho{sup 3+}/Yb{sup 3+}, or Tm{sup 3+}/Yb{sup 3+} codoped-K{sub 3}Y(VO{sub 4}){sub 2} glaserite powder and single crystals was observed, and the upconversion spectral properties were studied as a function of different Er{sup 3+}, Tm{sup 3+}, Ho{sup 3+}, and Yb{sup 3+} ion concentrations. The process is observed under 980 nm laser diode excitation and leads to strong green (552 nm) and red (659 nm) emission for Er{sup 3+}/Yb{sup 3+}, green (549 nm) and red (664 nm) emission for Ho{sup 3+}/Yb{sup 3+}, and blue (475 nm) and red (647 nm) emission for Tm{sup 3+}/Yb{sup 3+}. The main mechanism that allows for up-conversion is attributed the energy transfer among Yb{sup 3+} and the various Er{sup 3+}/Ho{sup 3+}/Tm{sup 3+} ions in excited states. These results illustrate the large potential of co-doped alkali double vanadates for photonic applications involving optoelectronics devices. - Graphical abstract: Synthesis and upconversion in vanadate glaserites. - Highlights: • K{sub 3}Y(VO{sub 4}){sub 2} codoped with Er, Tm, or Ho:Yb were synthesized via solid-state and hydrothermal routes. • Upconversion properties are investigated. • The codoped compounds revealed efficient infrared-to-visible upconversion. • The presented compounds are potential host for solid state lighting.

  8. Preparation and spectroscopic properties of rare-earth (RE) (RE = Sm, Eu, Tb, Dy, Tm)-activated K{sub 2}LnZr(PO{sub 4}){sub 3} (Ln = Y, La, Gd and Lu) phosphate in vacuum ultraviolet region

    SciTech Connect

    Zhang, Zhi-Jun; Lin, Xiao; Zhao, Jing-Tai; Zhang, Guo-Bin


    Graphical abstract: Display Omitted Highlights: ► We report the VUV spectroscopic properties of rare-earth ions in K{sub 2}LnZr(PO{sub 4}){sub 3}. ► The O{sup 2−}-Eu{sup 3+} charge transfer bands at about 220 nm have been observed. ► The 4f–5d spin-allowed and spin-forbidden transitions of Tb{sup 3+} have been observed. ► There is energy transfer between the host and rare-earth activators. -- Abstract: Rare earth (RE = Sm, Eu, Tb, Dy and Tm)-activated K{sub 2}LnZr(PO{sub 4}){sub 3} (Ln = Y, La, Gd and Lu) have been synthesized by solid-state reaction method, and their vacuum ultraviolet (VUV) excitation luminescent characteristics have been investigated. The band in the wavelength range of 130–157 nm and the other one range from 155 to 216 nm with the maximum at about 187 nm in the VUV excitation spectra of these compounds are attributed to the host lattice absorption and O–Zr charge transfer transition, respectively. The charge transfer bands (CTB) of O{sup 2−}-Sm{sup 3+}, O{sup 2−}-Dy{sup 3+} and O{sup 2−}-Tm{sup 3+}, in Sm{sup 3+}, Dy{sup 3+} and Tm{sup 3+}-activated samples, have not been obviously observed probably because the 2p electrons of oxygen are tightly bound to the zirconium ion in the host lattice. For Eu{sup 3+}-activated samples, the relatively weak O{sup 2−}-Eu{sup 3+} CTB at about 220 nm is observed. And for Tb{sup 3+}-activated samples, the bands at 223 and 258 nm are related to the 4f-5d spin-allowed and spin-forbidden transitions of Tb{sup 3+}, respectively. It is observed that there is energy transfer between the host lattice and the luminescent activators (e.g. Eu{sup 3+}, Tb{sup 3+}). From the standpoint of luminescent efficiency, color purity and chemical stability, K{sub 2}GdZr(PO{sub 4}){sub 3}:Sm{sup 3+}, Eu{sup 3+}, Tb{sup 3+} are attractive candidates for novel yellow, red, green-emitting PDP phosphors.

  9. Wavelength-dependent optical enhancement of superconducting interlayer coupling in La1.885Ba0.115CuO4sub>

    SciTech Connect

    Casandruc, E.; Nicoletti, D.; Rajasekaran, S.; Laplace, Y.; Khanna, V.; Gu, G.; Hill, J. P.; Cavalleri, A.


    We analyze the pump wavelength dependence for the photo-induced enhancement of interlayer coupling in La1.885Ba0.115CuO4sub>, which is promoted by optical melting of the stripe order. In the equilibrium superconducting state (T < TC = 13 K), in which stripes and superconductivity coexist, time-domain THz spectroscopy reveals a photo-induced blue-shift of the Josephson Plasma Resonance after excitation with optical pulses polarized perpendicular to the CuO2 planes. In the striped, non-superconducting state (TC < T < TSO ≃ 40 K) a transient plasma resonance similar to that seen below TC appears from a featureless equilibrium reflectivity. Most strikingly, both these effects become stronger upon tuning of the pump wavelength from the mid-infrared to the visible, underscoring an unconventional competition between stripe order and superconductivity, which occurs on energy scales far above the ordering temperature.

  10. Preservation of fluorescence and Raman gain in the buried channel waveguides in neodymium-doped KGd(WO{sub 4}){sub 2}(Nd:KGW) by femtosecond laser writing

    SciTech Connect

    Liu Xiaoyu; Qu Shiliang; Tan Yang; Chen Feng


    We report on the preservation of fluorescence and Raman gain in low-repetition-rate femtosecond laser written buried channel waveguides in neodymium-doped KGd(WO{sub 4}){sub 2}. The propagation loss index, profile reconstruction, and calculation of the modal intensity distribution by the beam propagation method of the waveguide are presented. Microluminescence spectra of the waveguides show that the fluorescence properties of Nd{sup 3+} ions are not significantly affected by the waveguide formation processing, which indicates a fairly good potential for further laser actions in a compact device. Micro-Raman spectra are also performed to reveal the preservation of the characteristic 768 and 901 cm{sup -1} Raman mode intensities in the guiding regions.

  11. High-pressure synthesis and single-crystal structure refinement of gadolinium holmium silicate hydroxyapatite Gd{sub 4.33}Ho{sub 4.33}(SiO{sub 4}){sub 6}(OH){sub 2}

    SciTech Connect

    Wang Chao; Liu Xiaoyang . E-mail:; Fleet, M.E.; Feng, Shouhua; Xu Ruren


    Single crystals of gadolinium holmium silicate hydroxyapatite Gd{sub 4.33}Ho{sub 4.33}(SiO{sub 4}){sub 6}(OH){sub 2} have been synthesized at 2.0GPa and 1450 deg. C using a piston-cylinder-type high-pressure apparatus. The crystal symmetry by single-crystal X-ray diffraction analysis is hexagonal, space group P6{sub 3}/m (No. 176), with a=9.3142(5)A, c=6.7010(4)A, Z=1. Gadolinium and Ho are disordered over the two large cation positions, A(1) and A(2), and charge balance in this silicate apatite is maintained by cation vacancies in A(1). Two other apatite-structure crystals investigated have P3-bar and Imma symmetry, and represent either partially ordered Gd-Ho distributions or crystal strain induced during quenching.

  12. (Ca{sub 1-x},Mg{sub x})Zr{sub 4}(PO{sub 4}){sub 6} and ZrP{sub 2}O{sub 7} coatings and foams

    SciTech Connect

    Li, T.K.; Hirschfeld, D.A.; Brown, J.J.


    (Ca{sub 1-x},Mg{sub x})Zr{sub 4}(PO{sub 4}){sub 6} and ZrP{sub 2}O{sub 7} ceramic foams and coatings have been made by sol-gel techniques on alumina, silicon nitride, silicon carbide substrates. The ceramic foams have small average pore diameters below 140 {mu}m and high unit porosity up to 97.7%, and stable pore sizes and porosity with increasing temperature due to their near zero thermal expansion. A homogeneous, crack-free coatings were formed on both the outer surface and the interior sections of pore walls of above substrates. The CMZP coatings on silicon nitride and silicon carbide exhibit good thermal shock resistance, and greatly improve the alkali corrosion resistance of silicon nitride and silicon carbide.

  13. Highly efficient Tm:CaYAlO4sub> laser in-band pumped by a Raman fiber laser at 1.7  μm.


    Yao, Weichao; Wu, Fan; Zhao, Yongguang; Chen, Hao; Xu, Xiaodong; Shen, Deyuan


    This paper discusses the high power, efficient operation of a Tm:CaYAlO4sub> (Tm:CYA) laser in-band pumped by a Raman fiber laser at 1.7 μm. We have investigated and compared laser characteristics of 4.0 at. % and 6.0 at. % doped Tm:CYA samples with both a-cut and c-cut configurations. Up to 6.8 W of output power has been generated at 1968.3 nm using a 6.0 at. % doped and a-cut Tm:CYA crystal, corresponding to a slope efficiency with respect to incident pump power of 52.3%. Laser output from both a- and c-cut samples are nearly linearly polarized with the polarization extinction ratio (PER) reaching 24 dB for the a-cut sample. PMID:27168283

  14. Mechanochemical transformation of mixtures of Ca(OH){sub 2} and (NH{sub 4}){sub 2}HPO{sub 4} or P{sub 2}O{sub 5}

    SciTech Connect

    Gonzalez, G. . E-mail:; Sagarzazu, A.; Villalba, R.


    A detailed comparative study of the mechanochemical transformation of two mixtures: Ca(OH){sub 2}-(NH{sub 4}){sub 2}HPO{sub 4} and Ca(OH){sub 2}-P{sub 2}O{sub 5}, milled in a mortar dry grinder for different periods of time was carried out. The phase transformations obtained at each milling stage were studied by X-ray diffraction, infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry and thermogravimetric analysis. The transformations taking place during the first periods of milling are very different for both mixtures. However, prolonged milling, over nearly the same period, causes amorphization of both mixtures. DSC analysis of the milled powders showed the temperature of crystallization of hydroxyapatite and tricalcium phosphate ({beta}-TCP). Calcinations of all the different milled powders at 800 deg. C for 2 h, results in the formation of hydroxyapatite and {beta}-TCP.

  15. High power, tunable mid-infrared BaGa4sub>Se7 optical parametric oscillator pumped by a 2.1 μm Ho:YAG laser.


    Yuan, Jin-He; Li, Chao; Yao, Bao-Quan; Yao, Ji-Yong; Duan, Xiao-Ming; Li, Ying-Yi; Shen, Ying-Jie; Wu, Yi-Cheng; Cui, Zheng; Dai, Tong-Yu


    We, for the first time, demonstrate a tunable mid-infrared BaGa4sub>Se7-based optical parametric oscillator pumped by a acousto-optical Q-switched Ho:YAG laser at 2090.6 nm. Up to 1.55 W of average power was generated in the 3-5 μm range, corresponding to an optical-to-optical conversion efficiency of 14.4% and a slope efficiency of 19.9%. The mid-IR radiation spectra were also seriously researched at different phase-matched angles. The tunable range was 3.49-4.13 μm for the signal, and 5.19-4.34 μm for the idler. PMID:27136802

  16. Sub-80 femtosecond pulses generation from a diode-pumped mode-locked Nd:Ca3La2(BO3)4sub> disordered crystal laser.


    Ma, Jie; Pan, Zhongben; Cai, Huaqiang; Yu, Haohai; Zhang, Huaijin; Shen, Deyuan; Tang, Dingyuan


    We experimentally demonstrated a diode-pumped sub-80 fs Nd:Ca3La2(BO3)4sub> disordered crystal laser. Pumping by an 808 nm fiber coupled laser diode, stable continuous-wave mode-locked pulses as short as 79 fs were achieved with a semiconductor saturable absorber mirror (SESAM). The ultrashort pulses had a repetition rate of ∼98.9  MHz at the central wavelength of about 1068 nm. To the best of our knowledge, this is the first demonstration of sub-100 fs pulses and the shortest mode-locked pulses generated from the Nd3+-doped crystal lasers. PMID:27192242

  17. Laser-induced excited-state crossover and spectral variation of Cr3+ in the high-crystal-field environment of CaGa2O4sub>.


    Rai, M; Singh, S K; Morthekai, P


    We have studied a wide-bandgap oxide semiconductor, CaGa1.99Cr0.01O4sub>, which possesses high crystal field strength and develops deep traps. These traps efficiently store electric charges after excitation with ultraviolet light. Stimulation of trap charges using infrared radiation (both coherent and incoherent) gives wideband emission of Cr3+ in the red-infrared region, which is similar to the photon upconversion process in lanthanides. Under laser excitation, high photon density and local heating pronounce the coupling of E2 and T24 states and causes an excited state crossover of the population from the E2 to T24 state. This expands the emission band-width of Cr3+ up to 900 nm. PMID:27472637

  18. High-Pressure Single-Crystal Neutron Scattering Study of Magnetic and Fe Vacancy Orders in (Tl,Rb)2 Fe4sub> Se5 Superconductor

    SciTech Connect

    Ye, Feng; Bao, Wei; Chi, Song-Xue; Santos, Antonio M. dos; Molaison, Jamie J.; Fang, Ming-Hu; Wang, Hang-Dong; Mao, Qian-Hui; Wang, Jin-Chen; Liu, Juan-Juan; Sheng, Jie-Ming


    We investigate the magnetic and iron vacancy orders in superconducting (Tl,Rb)2Fe4sub>Se5 single-crystals by using a high-pressure neutron diffraction technique. Similar to the temperature effect, the block antiferromagnetic order gradually decreases upon increasing pressure while the Fe vacancy superstructural order remains intact before its precipitous disappearance at the critical pressure Pc = 8.3 GPa. Combined with previously determined Pc for superconductivity, our phase diagram under pressure reveals the concurrence of the block AFM order, the √5 × √5 iron vacancy order and superconductivity for the 245 superconductor. Lastly, a synthesis of current experimental data in a coherent physical picture is attempted.

  19. Synthesis, structure and characterisation of Fe{sub 0.50}Ti{sub 2}(PO{sub 4}){sub 3}: A new material with Nasicon-like structure

    SciTech Connect

    Benmokhtar, S. El Jazouli, A.; Aatiq, A.; Chaminade, J.P.; Gravereau, P.; Wattiaux, A.; Fournes, L.; Grenier, J.C.


    A new iron titanyl phosphate Fe{sub 0.50}Ti{sub 2}(PO{sub 4}){sub 3} was synthesized by both solid-state reaction and Cu{sup 2+}-Fe{sup 2+} ion exchange method. The material was then characterized by X-ray diffraction, Mossbauer, magnetic susceptibility measurements and optical absorption. The crystal structure of the compound was refined, using X-ray powder diffraction data, by the Rietveld profile method; it crystallizes in the rhombohedral system, space group R3-bar, with a=8.511(1)A and c=20.985(3)A, V=1316.45(3)A{sup 3} and Z=6. The structure, which is compared to that of Mn{sub 0.50}Ti{sub 2}(PO{sub 4}){sub 3} is built up from [TiO{sub 6}] octahedra and [PO{sub 4}] tetrahedra which are linked by corner sharing along the c-axis. Fe{sup 2+} cations are located in half of the antiprism M{sub I} sites and are orderly distributed with vacancies within the two possible positions of the M{sub I} sites of R3-bar. These results were supported by the Mossbauer studies that showed the presence of one Fe{sup 2+} site in the high spin state (t{sub 2g}{sup 4}e{sub g}{sup 2}). The Curie-Weiss-type behavior is observed in the magnetic susceptibility. Diffuse reflectance spectrum indicates the presence of octahedrally coordinated Fe{sup 2+} ions.

  20. Role of ytterbium-erbium co-doped gadolinium molybdate (Gd2(MoO4sub>)3:Yb/Er) nanophosphors in solar cells.


    Jin, Xiao; Li, Haiyang; Li, Dongyu; Zhang, Qin; Li, Feng; Sun, Weifu; Chen, Zihan; Li, Qinghua


    Insufficient harvest of solar light energy is one of the obstacles for current photovoltaic devices to achieve high performance. Especially, conventional organic/inorganic hybrid solar cells (HSCs) based on PTB7 as p-type semiconductor can only utilize 400-800 nm solar spectrum. One effective strategy to overcome this obstacle is the introduction of up-conversion nanophosphors (NPs), in the virtue of utilizing the near infrared region (NIR) of solar radiation. Up-conversion can convert low-energy photons to high-energy ones through multi-photon processes, by which the solar spectrum is tailored to well match the absorptive domain of the absorber. Herein we incorporate erbium-ytterbium co-doped gadolinium molybdate (Gd2(MoO4sub>)3, GMO), denoted as GMO:Yb/Er, into TiO2 acceptor film in HSCs to enhance the light harvest. Here Er3+ acts as activator while Yb-MoO4sub> 2- is the joint sensitizer. Facts proved that the GMO:Yb/Er single crystal NPs are capable of turning NIR photons to visible photons that can be easily captured by PTB7. Studies on time-resolved photoluminescence demonstrate that electron transfer rate at the interface increases sharply from 0.65 to 1.42 × 109 s-1. As a result, the photoelectric conversion efficiency of the GMO:Yb/Er doped TiO2/PTB7 HSCs reach 3.67%, which is increased by around 25% compared to their neat PTB7/TiO2 counterparts (2.94%). This work may open a hopeful way to take the advantage of those conversional rare-earth ion doped oxides that function in tailoring solar light spectrum for optoelectronic applications. PMID:27607730

  1. Visible quantum cutting through downconversion in GdPO{sub 4}:Tb{sup 3+} and Sr{sub 3}Gd(PO{sub 4}){sub 3}:Tb{sup 3+}

    SciTech Connect

    Wang Deyin; Kodama, Nobuhiro


    Visible quantum cutting has been observed in GdPO{sub 4}:Tb{sup 3+} upon Tb{sup 3+} 4f{sup 8}-4f{sup 7}5d{sup 1} excitation and host excitation, and in Sr{sub 3}Gd(PO{sub 4}){sub 3}:Tb{sup 3+} upon Tb{sup 3+} 4f{sup 8}-4f{sup 7}5d{sup 1} excitation. In the quantum cutting process, Tb{sup 3+} acts as a quantum cutter, which converts one short wavelength ultraviolet photon or one vacuum ultraviolet photon into more than one visible photon. The quantum cutting involves a cross-relaxation process between two neighboring Tb{sup 3+} and direct energy transfer between Tb{sup 3+} and Tb{sup 3+} or Tb{sup 3+} and Gd{sup 3+}, depending on the excitation wavelength. The quantum efficiency variation of GdPO{sub 4}:xTb{sup 3+} and Sr{sub 3}Gd(PO{sub 4}){sub 3}:xTb{sup 3+} shows a growing trend with increasing of Tb{sup 3+} content from x=1.5% to 13%. - Graphical abstract: The ratio of emission from {sup 5}D{sub 4} level to that attributed to {sup 5}D{sub 3} of Tb{sup 3+} and {sup 6}P{sub J} of Gd{sup 3+} under 210,196 and 157 nm excitations are much stronger than that under 273 nm excitation, indicating visible quantum cutting has occurred in GdPO{sub 4}:Tb{sup 3+} upon Tb{sup 3+} 4f{sup 8}-4f{sup 7}5d{sup 1} excitation and host excitation.

  2. Effect of Spin-Crossover-Induced Pore Contraction on CO2–Host Interactions in the Porous Coordination Polymers [Fe(pyrazine)M(CN)4sub>] (M = Ni, Pt)

    SciTech Connect

    Culp, Jeffrey T; Chen, De-Li; Liu, Jinchen; Chirdon, Danielle; Kauffman, Kristi; Goodman, Angela; Johnson, J Karl


    Variable-temperature in situ ATR-FTIR spectra are presented for the porous spin-crossover compounds [Fe(pyrazine)Ni(CN)4sub>] and [Fe(pyrazine)Pt(CN)4sub>] under CO2 pressures of up to 8 bar. Significant shifts in the ν3 and ν2 IR absorption bands of adsorbed CO2 are observed as the host materials undergo transition between low- and high-spin states. Computational models used to determine the packing arrangement of CO2 within the pore structures show a preferred orientation of one of the adsorbed CO2 molecules with close O=C=O···H contacts with the pyrazine pillar ligands. The interaction is a consequence of the commensurate distance of the inter-pyrazine separations and the length of the CO2 molecule, which allows the adsorbed CO2 to effectively bridge the pyrazine pillars in the structure. The models were used to assign the distinct shifts in the IR absorption bands of the adsorbed CO2 that arise from changes in the O=C=O···H contacts that strengthen and weaken in correlation with changes in the Fe–N bond lengths as the spin state of Fe changes. The results indicate that spin-crossover compounds can function as a unique type of flexible sorbent in which the pore contractions associated with spin transition can affect the strength of CO2–host interactions.

  3. Influence of 6s{sup 2} lone pair electrons of Bi{sup 3+} on its preferential site occupancy in fluorapatite, NaCa{sub 3}Bi(PO{sub 4}){sub 3}F – An insight from Eu{sup 3+} luminescent probe

    SciTech Connect

    Lakshminarasimhan, N. Varadaraju, U.V.


    Graphical abstract: Eu{sup 3+} structural probe – difference in Eu{sup 3+} PL emission in (a) NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and (b) NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F suggests Bi{sup 3+} with preferential site occupancy at M(II) site directing Eu{sup 3+} to M(I) site. - Highlights: • Eu{sup 3+} luminescent probe used for establishing the role of 6s{sup 2} lone pair electrons of Bi{sup 3+} in fluorapatite. • Difference in Eu{sup 3+} PL emission spectral features in NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F. • Preferential site occupancy of Bi{sup 3+} in M(II) site directs Eu{sup 3+} to M(I) site in NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F. - Abstract: Eu{sup 3+} luminescence was used as a structural probe in understanding the preferential site occupancy of lone pair cation, Bi{sup 3+}, in fluorapatite by comparing the photoluminescence (PL) emission spectral features with that of in analogous La{sup 3+} based fluorapatite. The fluorapatites, NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F, were synthesized by conventional high temperature solid state reaction method and characterized by powder X-ray diffraction (XRD) and FT-IR spectroscopy. The Eu{sup 3+} PL results revealed a difference in the emission spectral features in NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F. This difference in Eu{sup 3+} PL emission can be attributed to the difference in its site occupancy in the studied fluorapatites.

  4. High-energy magnetic excitations in overdoped La2-xSrxCuO4sub> studied by neutron and resonant inelastic X-ray scattering

    SciTech Connect

    Wakimoto, S.; Ishii, K.; Kimura, H.; Fujita, M.; Dellea, G.; Kummer, K.; Braicovich, L.; Ghiringhelli, G.; Debeer-Schmitt, Lisa M.; Granroth, Garrett E.


    We have performed neutron inelastic scattering and resonant inelastic x-ray scattering (RIXS) at the Cu-L3 edge to study high-energy magnetic excitations at energy transfers of more than 100 meV for overdoped La2₋xSrxCuO4sub> with x=0.25 (Tc=15 K) and x=0.30 (nonsuperconducting) using identical single-crystal samples for the two techniques. From constant-energy slices of neutron-scattering cross sections, we have identified magnetic excitations up to ~250 meV for x=0.25. Although the width in the momentum direction is large, the peak positions along the (π,π) direction agree with the dispersion relation of the spin wave in the nondoped La2CuO4sub> (LCO), which is consistent with the previous RIXS results of cuprate superconductors. Using RIXS at the Cu-L3 edge, we have measured the dispersion relations of the so-called paramagnon mode along both (π,π) and (π,0) directions. Although in both directions the neutron and RIXS data connect with each other and the paramagnon along (π,0) agrees well with the LCO spin-wave dispersion, the paramagnon in the (π,π) direction probed by RIXS appears to be less dispersive and the excitation energy is lower than the spin wave of LCO near (π/2,π/2). Thus, our results indicate consistency between neutron inelastic scattering and RIXS, and elucidate the entire magnetic excitation in the (π,π) direction by the complementary use of two probes. The polarization dependence of the RIXS profiles indicates that appreciable charge excitations exist in the same energy range of magnetic excitations, reflecting the itinerant character of the overdoped sample. Lastly, we find a possible anisotropy in the charge excitation intensity might explain the apparent differences in the paramagnon dispersion in the (π,π) direction as detected by the x-ray scattering.

  5. Tetrahedrally coordinated disordered Cu2SnS3-Cu2ZnSnS4sub>-ZnS alloys with tunable optical and electronic properties

    SciTech Connect

    Erslev, Peter T.; Young, Matthew R.; Li, Jian V.; Siah, Sin Cheng; Chakraborty, Rupak; Du, Hui; Lad, Robert J.; Buonassisi, Tonio; Teeter, Glenn


    A key requirement for large-scale deployment of photovoltaic technologies is the development of highly functional materials with controllable opto-electronic properties. In this work, we report on the room-temperature synthesis of disordered alloys of the Earth-abundant, tetrahedrally coordinated semiconductors Cu2SnS3, Cu2ZnSnS4sub> (CZTS), and ZnS as (Cu2SnS3)1-x(ZnS)x. The resulting disordered semiconductors are found to have continuously and independently tunable optical and electronic properties. Quasi-isovalent alloying on the cation sublattice allows the optical band gap to be varied continuously from 1.1 eV to 2.8 eV. Aliovalent alloying leads to independent control of carrier concentration over at least three orders of magnitude. A conceptual framework describing these disordered materials is presented, in which the structural disorder, constrained by local tetrahedral coordination of both anions and cations, leads to the observed high degree of tunability of the opto-electronic properties. These materials are not only independently interesting, but the developed framework also applies to the opto-electronic properties of kesterite CZTS materials as well as provides a basis for the development of new semiconductors.

  6. Bulk modulus of basic sodalite, Na{sub 8}[AlSiO{sub 4}]{sub 6}(OH){sub 2}.2H{sub 2}O, a possible zeolitic precursor in coal-fly-ash-based geopolymers

    SciTech Connect

    Oh, Jae Eun; Moon, Juhyuk; Mancio, Mauricio; Clark, Simon M.; Monteiro, Paulo J.M.


    Synthetic basic sodalite, Na{sub 8}[AlSiO{sub 4}]{sub 6}(OH){sub 2}.2H{sub 2}O, cubic, P43n, (also known as hydroxysodalite hydrate) was prepared by the alkaline activation of amorphous aluminosilicate glass, obtained from the phase separation of Class F fly ash. The sample was subjected to a process similar to geopolymerization, using high concentrations of a NaOH solution at 90 {sup o}C for 24 hours. Basic sodalite was chosen as a representative analogue of the zeolite precursor existing in Na-based Class F fly ash geopolymers. To determine its bulk modulus, high-pressure synchrotron X-ray powder diffraction was applied using a diamond anvil cell (DAC) up to a pressure of 4.5 GPa. A curve-fit with a truncated third-order Birch-Murnaghan equation of state with a fixed K'{sub o} = 4 to pressure-normalized volume data yielded the isothermal bulk modulus, K{sub o} = 43 {+-} 4 GPa, indicating that basic sodalite is more compressible than sodalite, possibly due to a difference in interactions between the framework host and the guest molecules.

  7. Magnetocaloric effect in gadolinium-oxalate framework Gd{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}⋅(0{sub ⋅}6H{sub 2}O)

    SciTech Connect

    Sibille, Romain Didelot, Emilie; Mazet, Thomas; Malaman, Bernard; François, Michel


    Magnetic refrigerants incorporating Gd{sup 3+} ions and light organic ligands offer a good balance between isolation of the magnetic centers and their density. We synthesized the framework material Gd{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}⋅0.6H{sub 2}O by a hydrothermal route and characterized its structure. The honeycomb lattice of Gd{sup 3+} ions interlinked by oxalate ligands in the (a,c) plane ensures their decoupling in terms of magnetic exchange interactions. This is corroborated by magnetic measurements indicating negligible interactions between the Gd{sup 3+} ions in this material. The magnetocaloric effect was evaluated from isothermal magnetization measurements. The maximum entropy change −ΔS{sub M}{sup max} reaches 75.9 mJ cm{sup −3} K{sup −1} (around 2 K) for a moderate field change (2 T)

  8. O3-type layered transition metal oxide Na(NiCoFeTi)1/4sub>O2 as a high rate and long cycle life cathode material for sodium ion batteries

    SciTech Connect

    Yue, Ji -Li; Yang, Xiao -Qing; Zhou, Yong -Ning; Yu, Xiqian; Bak, Seong -Min; Fu, Zheng -Wen


    High rate capability and long cycle life are challenging goals for the development of room temperature sodium-ion batteries. Here we report a new single phase quaternary O3-type layer-structured transition metal oxide Na(NiCoFeTi)1/4sub>O2 synthesized by a simple solid-state reaction as a new cathode material for sodium-ion batteries. It can deliver a reversible capacity of 90.6 mA h g–1 at a rate as high as 20C. At 5C, 75.0% of the initial specific capacity can be retained after 400 cycles with a capacity-decay rate of 0.07% per cycle, demonstrating a superior long-term cyclability at high current density. X-ray diffraction and absorption characterization revealed reversible phase transformations and electronic structural changes during the Na+ deintercalation/intercalation process. Ni, Co and Fe ions contribute to charge compensation during charge and discharge. Although Ti ions do not contribute to the charge transfer, they play a very important role in stabilizing the structure during charge and discharge by suppressing the Fe migration. Additionally, Ti substitution can also smooth the charge–discharge plateaus effectively, which provides a potential advantage for the commercialization of this material for room temperature sodium-ion batteries.

  9. Magnetic field induced anisotropy of 139La spin-lattice relaxation rates in stripe ordered La1.875Ba0.125CuO4sub>

    SciTech Connect

    S. -H. Baek; Gu, G. D.; Utz, Y.; Hucker, M.; Buchner, B.; Grafe, H. -J.


    We report 139La nuclear magnetic resonance studies performed on a La1.875Ba0.125CuO4sub> single crystal. The data show that the structural phase transitions (high-temperature tetragonal → low-temperature orthorhombic → low-temperature tetragonal phase) are of the displacive type in this material. The 139La spin-lattice relaxation rate T–11 sharply upturns at the charge-ordering temperature TCO = 54 K, indicating that charge order triggers the slowing down of spin fluctuations. Detailed temperature and field dependencies of the T–11 below the spin-ordering temperature TSO=40 K reveal the development of enhanced spin fluctuations in the spin-ordered state for H ∥ [001], which are completely suppressed for large fields along the CuO2 planes. Lastly, our results shed light on the unusual spin fluctuations in the charge and spin stripe ordered lanthanum cuprates.

  10. Neutron Diffraction Study of Parasitic Nd-Moment Order in the Checkerboard-Type Phase Nd1.3Sr0.7NiO4sub>

    SciTech Connect

    Kobayashi, Riki; Yoshizawa, Hideki; Matsuda, Masaaki; Kajimoto, Ryoichi; Ishizaka, Kyoko; Tokura, Yoshinori


    In this paper, the Nd-moment order in the layered nickelate Nd2-xSrxNiO4sub> (x = 0.7) has been investigated by performing a neutron diffraction experiment using a single crystal sample. First, the checkerboard (CB)-type charge order was confirmed by observing the temperature dependence of the nuclear superlattice peak at Q=(5,0,0) between 1.9 and 300 K, which indicates that the transition temperature of the CB-type charge order is above 300 K. Magnetic superlattice peaks with the propagation vector k=(1-ε,0,1) appear below 67 K, and the value of ε was determined to be 0.455 in good agreement with previous studies. The intensity of the magnetic superlattice peaks appearing below 67 K shows a sharp increase below ≈20 K. This behavior indicates that the Nd moments freeze under the influence of the Ni ordering. The CB-type antiferromagnetic (AFM) Ni order in the NiO2 layers is stacked antiferromagnetically in the c-axis direction, while the Nd moments in the Nd/SrO2 layers are coupled antiferromagnetically with the Ni moments. Finally, the Nd moments are parallel to the c-axis, while the Ni moments are canted towards the c-axis direction from the basal ab-plane at low temperatures where the Nd moments are well ordered.

  11. Bipolar resistive switching performance of the nonvolatile memory cells based on (AgI){sub 0.2}(Ag{sub 2}MoO{sub 4}){sub 0.8} solid electrolyte films

    SciTech Connect

    Yan, X. B.; Guo, H. X.; Su, Y.; Xu, B.; Li, H. T.; Xia, Y. D.; Liu, Z. G.; Yin, J.; Yan, D. W.


    Resistive switching memory cells with polycrystalline (AgI){sub 0.2}(Ag{sub 2}MoO{sub 4}){sub 0.8} (AIMO) solid electrolyte films as storage medium were fabricated on SiO{sub 2}/Pt/Ti/Si substrates by using pulse laser deposition technique and focused ion beam lithography. X-ray diffraction, scanning electron microscopy, and energy dispersive x-ray analysis have been employed to investigate the structure, the surface morphology, and the composition of AIMO thin films. The Ag/AIMO/Pt memory cells with sandwich structure exhibit stable, reproducible, and reliable resistive switching characteristics. The ratio of resistance between high resistance states and low resistance states can reach approx10{sup 5}. Moreover, the low resistance is approx500 OMEGA at a compliance current of 0.5 mA, which is favorable to reduce the power dissipation of the entire circuit. The switching-on mechanism has been discussed and the metallic conduction characteristic has also been verified. The fast response speed and the good retention properties further indicate that polycrystalline AIMO thin film is a potential candidate for the next generation nonvolatile memory.

  12. Strain tuning of electronic structure in Bi4sub>Ti3O12-LaCoO3 epitaxial thin films

    SciTech Connect

    Choi, Woo Seok; Lee, Ho Nyung


    In this study, we investigated the crystal and electronic structures of ferroelectric Bi4sub>Ti3O12 single-crystalline thin films site-specifically substituted with LaCoO3 (LCO). The epitaxial films were grown by pulsed laser epitaxy on NdGaO3 and SrTiO3 substrates to vary the degree of strain. With increasing the LCO substitution, we observed a systematic increase in the c-axis lattice constant of the Aurivillius phase related with the modification of pseudo-orthorhombic unit cells. These compositional and structural changes resulted in a systematic decrease in the band gap, i.e., the optical transition energy between the oxygen 2p and transition-metal 3d states, based on a spectroscopic ellipsometry study. In particular, the Co 3d state seems to largely overlap with the Ti t2g state, decreasing the band gap. Interestingly, the applied tensile strain facilitates the band-gap narrowing, demonstrating that epitaxial strain is a useful tool to tune the electronic structure of ferroelectric transition-metal oxides.

  13. Persistent luminescence in Ba{sub 5}(PO{sub 4}){sub 3}Cl:Eu{sup 2+},R{sup 3+} (R = Y, La, Ce, Gd, Tb and Lu)

    SciTech Connect

    Ju, Guifang; Hu, Yihua Chen, Li; Wang, Xiaojuan; Mu, Zhongfei


    Graphical abstract: - Highlights: • The persistent luminescence in Ba{sub 5}(PO{sub 4}){sub 3}Cl:Eu{sup 2+},R{sup 3+} was reported. • The influences of auxiliary codopants was discussed. • The concentration quenching of persistent luminescence was discussed. - Abstract: We investigated the persistent luminescence in europium-doped barium chloroapatite upon codoping with auxiliary rare earth ions. Luminescence properties of the phosphors, including photoluminescence, luminescence decay, and thermoluminescence are systematically studied. We formulated a model of persistent luminescence on the basis of the experimental results. In our model, some Eu{sup 2+} ions are oxidized to Eu{sup 3+} under short UV excitation, and the released electrons are trapped at the positive defect. The persistent luminescence arises from the recombination of these trapped electrons with the photo-ionized Eu{sup 3+} ions. The influence of auxiliary codopants was discussed in terms of ionic potential and ionic radius. Eventually, the concentration quenching of persistent luminescence was reported and discussed.

  14. Evidence for phase transitions and pseudospin phonon coupling in K{sub 0.9}(NH{sub 4}){sub 0.1}H{sub 2}AsO{sub 4}

    SciTech Connect

    Kumar, Pradeep; Ramesh, K. P.; Muthu, D. V. S.


    This work reports a detailed temperature dependent Raman study on the mixed crystals of K{sub 0.9}(NH{sub 4}){sub 0.1}H{sub 2}AsO{sub 4} (KADA) from 5K to 300K in the spectral range of 60-1200cm{sup −1}, covering tetragonal to orthorhombic structural phase transition accompanied by paraelectric to ferroelectric transition at T{sub c}{sup *} ∼ 60K. Multiple phase transitions below transition temperature (T{sub c}{sup *} ∼ 60K) are marked by the appearance of new modes, splitting of existing ones as well as anomalies in the self-energy parameters (i.e. mode frequencies and damping coefficient) of the phonon modes. Temperature independent behaviour of damping coefficient and abrupt jump in the mode frequency of some of the internal vibrations of AsO{sub 4} tetrahedra as well as external vibrations clearly signal long range ferroelectric ordering and proton ordering below T{sub c}{sup *}. In addition, we observed that temperature dependence of many prominent phonon modes diverges significantly from their normal anharmonic behaviour below T{sub c}{sup *} suggesting potential coupling between pseudospins and phonons.

  15. Synthesis of ternary potassium, magnesium, and zirconium molybdates. The crystal structure of K{sub 5}(Mg{sub 0.5}Zr{sub 1.5}){center_dot}(MoO{sub 4}){sub 6}

    SciTech Connect

    Klevtsova, R.F.; Bazarova, Z.G.; Glinskaya, L.A.


    Three (5:1:3, 1:1:1, and 2:1:6) ternary phases were discovered in the K{sub 2}MoO{sub 4}-AMoO{sub 4}-Zr(MoO{sub 4}){sub 2} system, where A is Mg or Mn. For A = Mg, the authors have synthesized 5:1:3 single crystals and determined their crystal structure from X-ray diffraction data (a CAD-4 automatic diffractometer, MoK{sub a} radiation, 1166 F(hkl), and R = 0.026). The compound crystallizes in the trigonal system with space group R3c, a = 10.576(1), c = 37.511(3) {Angstrom}, Z = 6, d{sub calc} = 3.576, and d{sub msd} = 3.54 g/cm{sup 3}. The structure is a three-dimensional composite framework of alternating Mo tetrahedra and (Mg, Zr) octahedra, which are linked via the common {Omicron} vertices. Potassium atoms of three kinds are located in large framework cavities. Their polyhedra (ten-vertex polyhedra and a cubeoctahedron) are linked together by common faces and edges to form infinite zigzag columns of a large section. When solving the structure, the authors refined the composition of the crystals and the distribution of Mg{sup 2+} and Zr{sup 4+} cations in the M(1) and M(2) positions resulting in the formula above.

  16. Structure tracking aided design and synthesis of Li3V2(PO4sub>)3 nanocrystals as high-power cathodes for lithium ion batteries

    SciTech Connect

    Wang, Liping; Bai, Jianming; Gao, Peng; Wang, Xiaoya; Looney, J. Patrick; Wang, Feng


    In this study, preparing new electrode materials with synthetic control of phases and electrochemical properties is desirable for battery applications but hardly achievable without knowing how the synthesis reaction proceeds. Herein, we report on structure tracking-aided design and synthesis of single-crystalline Li3V2(PO4sub>)3 (LVP) nanoparticles with extremely high rate capability. A comprehensive investigation was made to the local structural orderings of the involved phases and their evolution toward forming LVP phase using in situ/ex situ synchrotron X-ray and electron-beam diffraction, spectroscopy, and imaging techniques. The results shed light on the thermodynamics and kinetics of synthesis reactions and enabled the design of a cost-efficient synthesis protocol to make nanocrystalline LVP, wherein solvothermal treatment is a crucial step leading to an amorphous intermediate with local structural ordering resembling that of LVP, which, upon calcination at moderate temperatures, rapidly transforms into the desired LVP phase. The obtained LVP particles are about 50 nm, coated with a thin layer of amorphous carbon and featured with excellent cycling stability and rate capability – 95% capacity retention after 200 cycles and 66% theoretical capacity even at a current rate of 10 C. The structure tracking based method we developed in this work offers a new way of designing battery electrodes with synthetic control of material phases and properties.

  17. Structural characterization and AC conductivity of bis tetrapropylammonium hexachlorado-dicadmate, [N(C{sub 3}H{sub 7}){sub 4}]{sub 2}Cd{sub 2}Cl{sub 6}

    SciTech Connect

    Hannachi, N.; Guidara, K.; Bulou, A.; Hlel, F.


    Synthesis, crystal structure, vibrational study, {sup 13}C, {sup 111}Cd CP-MAS-NMR analysis and electrical properties of the compound [N(C{sub 3}H{sub 7}){sub 4}]{sub 2}Cd{sub 2}Cl{sub 6}, are reported. The latter crystallizes in the triclinic system (space group P1-bar, Z = 2) with the following unit cell dimensions: a = 9.530(1) A, b = 11.744(1) A, c = 17.433(1) A, {alpha} = 79.31(1){sup o}, {beta} = 84.00(1){sup o} and {gamma} = 80.32(1){sup o}. Besides, its structure was solved using 6445 independent reflections down to R = 0.037. The atomic arrangement can be described by alternating organic and inorganic layers parallel to the (11-bar 0) plan, made up of tetrapropylammonium groups and Cd{sub 2}Cl{sub 6} dimers, respectively. In crystal structure, the inorganic layer, built up by Cd{sub 2}Cl{sub 6} dimers, is connected to the organic ones through van der Waals interaction in order to build cation-anion-cation cohesion. Impedance spectroscopy study, reported in the sample, reveals that the conduction in the material is due to a hopping process. The temperature and frequency dependence of dielectric constants of the single crystal sample has been investigated to determine some related parameters to the dielectric relaxation.

  18. Refinement of the crystal structure of the high-temperature phase G{sub 0} in (NH{sub 4}){sub 2}WO{sub 2}F{sub 4} (powder, X-ray, and neutron scattering)

    SciTech Connect

    Novak, D. M. Smirnov, L. S.; Kolesnikov, A. I.; Voronin, V. I.; Berger, I. F.; Laptash, N. M.; Vasil'ev, A. D.; Flerov, I. N.


    The (NH{sub 4}){sub 2}WO{sub 2}F{sub 4} compound undergoes a series of phase transitions: G{sub 0} {yields} 201, K {yields} G{sub 1} {yields} 160, and K {yields} G{sub 2}, with a significant change in entropy ({Delta}S{sub 1} {approx} Rln10 at the G{sub 0} {yields} G{sub 1} transition), which indicates significant orientational disordering in the G{sub 0} phase and the order-disorder type of the phase transition. X-ray diffraction is used to identify the crystal structure of the G{sub 0} phase as rhombohedral (sp. gr. Cmcm, Z = 4), determine the lattice parameters and the positions of all atoms (except hydrogen), and show that [WO{sub 2}F{sub 4}]{sup 2-} ions can form a superposition of dynamic and static orientational disorders in the anionic sublattice. A determination of the orientational position of [NH{sub 4}]{sup +} ions calls for the combined method of elastic and inelastic neutron scattering. Inelastic neutron scattering is used to determine the state of hindered rotation for ammonium ions in the G{sub 0} phase. Powder neutron diffraction shows that the orientational disorder of NH{sub 4} ions can adequately be described within the free-rotation approximation.

  19. Structure of the VO/sub 2/F/sub 4//sup 3 -/ ion: crystal structure of (NH/sub 4/)/sub 3/VO/sub 2/F/sub 4/

    SciTech Connect

    Leimkuehler, M.; Mattes, R.


    The VO/sub 2/F/sub 4//sup 3 -/ ion has a cis octahedral structure, as is shown by single crystal structure analysis of the title compound. The unit cell of (NH/sub 4/)/sub 3/ VO/sub 2/F/sub 4/ (space group Immm or I222, a = 912.6(2), b = 1881.8(4), c = 626.4(1) pm, Z = 6) contains two symmetrically independent anions. One is rotationally disordered. Oxo and fluoro ligands cannot be distinguished. But the second one has a distorted cis octahedral structure with the lengths 170.0(4), 186.1(4), and 202.3(4) pm for the V-O, V-F (axial), and V-F (equatorial)bonds. Infrared and Raman spectra as well as theoretical considerations support the crystallographic results. The phase transitions at 418 and 215 K were confirmed by variable temperature X-ray powder diffraction. Above 418 K the cubic cryolite type structure is adopted with a = 902.6(2) pm. Plausible mechanisms for the phase transitions are suggested.

  20. Saturable absorber: transparent glass-ceramics based on a mixture of Co:β-Zn2SiO4sub> and Co:ZnO nanocrystals.


    Loiko, P; Dymshits, O S; Vitkin, V V; Skoptsov, N A; Zhilin, A A; Shemchuk, D V; Tsenter, M Ya; Bogdanov, K; Malyarevich, A M; Glazunov, I V; Mateos, X; Yumashev, K V


    We report on the development of novel saturable absorbers for erbium lasers based on transparent glass-ceramics (GCs) containing a mixture of cobalt-doped β-willemite, Co2+:β-Zn2SiO4sub>, and zinc oxide, Co2+:ZnO, nanosized (10-14 nm) crystals. The structure of the parent glass and GCs is studied by x-ray diffraction, differential scanning calorimetry, transmission electron microscopy, and Raman spectroscopy. Variations of absorption spectra with heat-treatment reveal that Co2+ ions from the parent glass enter the crystals of ZnO and β-willemite. GCs are characterized by a broad absorption band due to the A24(F4)→T14(F4) transition of Co2+ ions in tetrahedral sites spanning up to ∼1.74  μm, relatively low saturation fluence, FS=0.75  J/cm2 at 1.54 μm, short recovery time, τ=830  ns, and high laser damage threshold, ∼14  J/cm2. By using the developed GCs in a diode-side-pumped Er, Yb:glass laser, 0.77 mJ/45 ns pulses are generated. PMID:27463897

  1. Quasi-two-dimensional spin and phonon excitations in La1.965Ba0.035CuO4sub>

    SciTech Connect

    Wagman, J. J.; Parshall, D.; Stone, Matthew B.; Savici, Andrei T.; Zhao, Yang; Dabkowska, H. A.; Gaulin, B. D.


    Here, we present time-of-fight inelastic neutron scattering measurements of La1.965Ba0.035CuO4sub> (LBCO), a lightly doped member of the high temperature superconducting La-based cuprate family. By using time-of-flight neutron instrumentation coupled with single crystal sample rotation we obtain a four-dimensional data set (three Q and one energy) that is both comprehensive and spans a large region of reciprocal space. Our measurements identify rich structure in the energy dependence of the highly dispersive spin excitations, which are centered at equivalent (1/2, 1/2, L) wave-vectors. These structures correlate strongly with several crossings of the spin excitations with the lightly dispersive phonons found in this system. These eects are signicant and account for on the order of 25% of the total inelastic scattering for energies between ≈5 and 40meV at low |Q|. Interestingly, this scattering also presents little or no L-dependence. As the phonons and dispersive spin excitations centred at equivalent (1/2, 1/2, L) wave-vectors are common to all members of La-based 214 copper oxides, we conclude such strong quasi-two dimensional scattering enhancements are likely to occur in all such 214 families of materials, including those concentrations corresponding to superconducting ground states. Such a phenomenon appears to be a fundamental characteristic of these materials and is potentially related to superconducting pairing.

  2. Application of a ring cavity surface emitting quantum cascade laser (RCSE-QCL) on the measurement of H2S in a CH4sub> matrix for process analytics.


    Moser, Harald; Genner, Andreas; Ofner, Johannes; Schwarzer, C; Strasser, Gottfried; Lendl, Bernhard


    The present work reports on the first application of a ring-cavity-surface-emitting quantum-cascade laser (RCSE-QCL) for sensitive gas measurements. RCSE-QCLs are promising candidates for optical gas-sensing due to their single-mode, mode-hop-free and narrow-band emission characteristics along with their broad spectral coverage. The time resolved down-chirp of the RCSE-QCL in the 1227-1236 cm-1 (8.15-8.09 µm) spectral range was investigated using a step-scan FT-IR spectrometer (Bruker Vertex 80v) with 2 ns time and 0.1 cm-1 spectral resolution. The pulse repetition rate was set between 20 and 200 kHz and the laser device was cooled to 15-17°C. Employing 300 ns pulses a spectrum of ~1.5 cm-1 could be recorded. Under these laser operation conditions and a gas pressure of 1000 mbar a limit of detection (3σ) of 1.5 ppmv for hydrogen sulfide (H2S) in nitrogen was achieved using a 100 m Herriott cell and a thermoelectric cooled MCT detector for absorption measurements. Using 3 µs long pulses enabled to further extend the spectral bandwidth to 8.5 cm-1. Based on this increased spectral coverage and employing reduced pressure conditions (50 mbar) multiple peaks of the target analyte H2S as well as methane (CH4sub>) could be examined within one single pulse. PMID:27136847

  3. Hydrothermal synthesis and the crystal structure of borate cancrinite (Na,Ca){sub 2}[Na{sub 6}(AlSiO{sub 4}){sub 6}](BO{sub 3}) . 2H{sub 2}O

    SciTech Connect

    Shirinova, A. F. Khrustalev, V. N.; Samedov, H. R.; Chiragov, M. I.


    Transparent prismatic single crystals of borate cancrinite (Na,Ca){sub 2}[Na{sub 6}(AlSiO{sub 4}){sub 6}](BO{sub 3}) . 2H{sub 2}O are prepared through hydrothermal crystallization. The parameters of the hexagonal unit cell and intensities of 10806 reflections are measured on an Enraf-Nonius CAD4 automated diffractometer. The compound crystallizes in the hexagonal crystal system with the unit cell parameters a = 12.745(4) A, c = 5.180(2) A, V = 728.6(4) A{sup 3}, and space group P6{sub 3}. The structure is determined by direct methods and refined using the full-matrix least-squares procedure in the anisotropic approximation for the non-hydrogen atoms. The refinement of the structure is performed to the final discrepancy factor R{sub 1} = 0.027 for 2889 unique reflections with I > 2 {sigma} (I). In the structure of the borate cancrinite, the AlO{sub 4} and SiO{sub 4} tetrahedra form a zeolite-like framework in which twelve-membered hexagonal channels are occupied by sodium atoms and BO{sub 3} groups, whereas six-membered channels are filled with sodium and calcium atoms and water molecules. The mean interatomic distances are found to be as follows: (Si-O){sub mean} = 1.614 A and (Al-O){sub mean} = 1.741 A in the AlO{sub 4} and SiO{sub 4} tetrahedra, (Na-O){sub mean} = 2.542 A in the seven-vertex sodium polyhedra, and [(Na,Ca)-O]{sub mean} = 2.589 A in the ditrigonal bipyramids.

  4. Structural features of the reactives sites in {alpha}-M(DPO{sub 4}){sub 2}{center_dot}D{sub 2}O (M = Ti, Zr, Pb): Hydrogen-bond network and framework

    SciTech Connect

    Losilla, E.R.; Aranda, M.A.G.; Bruque, S.


    Three crystalline layered metal (IV) acid phosphates {alpha}-M(DPO{sub 4}){sub 2}{center_dot}D{sub 2}O, {alpha}-MP, (M = Zr, Ti, Pb) have been hydrothermally synthesized and the size and shape of the microparticles have been analyzed by the Scherrer method. The crystal structures of {alpha}-ZrP and {alpha}-TiP have been refined from a combined X-ray and neutron powder diffraction study by the Rietveld method. These hydrogen phosphates are isomorphous and belong to the {alpha}-ZrP-type structure. However, this precise powder diffraction study has shown that the frameworks and hydrogen-bond networks of these materials are slightly different. The unit cell volume of {alpha}-ZrP is larger than that of {alpha}-TiP because the layers in {alpha}-ZrP are less corrugated than those in {alpha}-TiP. The H-bond network is also slightly different, as in {alpha}-ZrP there is not H bonding between the layers, the shortest contact being O(7) {hor_ellipsis} D(4) of 2.56(3) {angstrom}. For {alpha}-TiP this contact is much shorter, 2.33(2) {angstrom}, which may indicate a small but not negligible H-bond interaction between layers. Moreover, the intralayer H bonds are weaker in {alpha}-ZrP than in {alpha}-TiP as evidenced in the O(4) {hor_ellipsis} D(3) interactions of 2.41(3) and 2.16(2) {angstrom} respectively.

  5. Structural, thermal, magnetic and electrical studies of the iron oxophosphate Rb{sub 7}Fe{sub 7}(PO{sub 4}){sub 8}O{sub 2}.2H{sub 2}O

    SciTech Connect

    Hidouri, Mourad; Lajmi, Besma; Gmati, Nadia; Wattiaux, Alain; Nenert, Gwilherm; Ritter, Clemens; Fournes, Leopold; Darriet, Jacques; Lopez, Maria Luisa; Pico, Carlos; Amara, Mongi B.


    A new iron oxophosphate of composition Rb{sub 7}Fe{sub 7}(PO{sub 4}){sub 8}O{sub 2}.2H{sub 2}O has been synthesized and studied by X-ray diffraction, TG and DTA analysis, magnetic susceptibility, neutron diffraction, Moessbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic system with the P2{sub 1}/c space group and the unit cell parameters a = 8.224(8) A, b = 22.162(6) A, c = 9.962(6) A and {beta} = 109.41(8){sup o}. Its structure is built up from Fe{sub 7}O{sub 32} clusters of edge- and corner-sharing FeO{sub 5} and FeO{sub 6} polyhedra. Neighboring clusters are connected by the phosphate tetrahedra to form a three-dimensional framework. The Rb{sup +} cations and the water molecules are occupying intersecting tunnels parallel to a and c. The presence of water molecules was confirmed by TG and DTA analysis. The magnetic susceptibility measurements have shown the existence of antiferromagnetic ordering below 22 K with a weak ferromagnetic component. Additionally, these measurements show evidence for a strong magnetic frustration characterized by |{theta}/T{sub N}| {approx} 12. Powder neutron diffraction study confirms the presence of a long range antiferromagnetic order coupled to a weak ferromagnetic component along the b-axis. The strongly reduced magnetic moments extracted from the refinement support the existence of a magnetically frustrated ground state. The Moessbauer spectroscopy results confirmed the presence of only Fe{sup 3+} ions in both five and six coordination. The ionic conductivity measurements led to activation energy of 0.81 eV, a value that agrees with the obtained for other rubidium phosphates.

  6. Improved electrochemical performance of spinel LiMn1.5Ni0.5O4sub> through MgF2 nano-coating

    SciTech Connect

    Wu, Qing; Zhang, Xiaoping; Sun, Shuwei; Wan, Ning; Pan, Du; Bai, Ying; Zhu, Huiyuan; Hu, Yong-Sheng; Dai, Sheng


    In this paper, a spinel LiMn1.5Ni0.5O4sub> (LMNO) cathode material synthesized by a sol–gel method is modified by MgF2 nano-coating via a wet coating strategy. The results of X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM) showed that the MgF2 nano-coating layers do not physically change the bulk structure of the pristine material. Compared with the pristine compound, the MgF2-coated LMNO electrodes display enhanced cycling stabilities. Particularly, the 5 wt% MgF2-coated LMNO demonstrates the best reversibility, with a capacity retention of 89.9% after 100 cycles, much higher than that of the pristine material, 69.3%. The dQ/dV analysis and apparent Li+ diffusion coefficient calculation prove that the kinetic properties are enhanced after MgF2 surface modification, which partly explains the improved electrochemical performances. Electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FTIR) data confirm that the MgF2 coating layer helps in suppressing the fast growth of the solid electrolyte interface (SEI) film in repeated cycling, which effectively stabilizes the spinel structure. Finally and additionally, differential scanning calorimetry (DSC) tests show that the MgF2 nano-coating layer also helps in enhancing the thermal stability of the LMNO cathode.

  7. Competitive chain transfer by [beta]-hydrogen and [beta]-methyl elimination for the model Ziegler-Natta olefin polymerization system [Me[sub 2]Si([eta][sup 5]-C[sub 5]Me[sub 4])[sub 2

    SciTech Connect

    Hajela, S.; Bercaw, J.E. )


    The reaction of OpSc(H)(PMe[sub 3]) (Op = (([eta][sup 5]-C[sub 6]Me[sub 4])[sub 2]SiMe[sub 2])) with isobutene produces OpSc(CH[sub 3])(PMe[sub 3]) along with isobutene, 2-methylpentane, isobutene, 2-methyl-1-pentene, propane, and n-pentane. These products arise from a series of reactions involving olefin insertion, [beta]-CH[sub 3] and (faster) [beta]-H elimination which proceed until only the 2-methyl-1-alkenes (C[sub 4]H[sub 8], C[sub 6]H[sub 12], etc.) and the predominant organoscandium product OpSc(CH[sub 3])(PMe[sub 3]) remain. A transient observed in the reaction sequence has been unambiguously characterized as OpSc(CH[sub 2]CH[sub 2]CH[sub 3])(PMe[sub a]). Slower [sigma] bond metathesis involving the methyl C-H bonds of PMe[sub 3] and the Sc-C bonds of the scandium alkyls accounts for the observation of saturated alkanes 2-methylalkanes (C[sub 4]H[sub 10], C[sub 6]H[sub 14], etc.), normal alkanes (C[sub 3]H[sub 8],C[sub 5]H[sub 12], etc.), and a minor organoscandium product OpScCh[sub 2]Pme[sub 2] in the product mixture. [beta]-Ethylmigration is not observed for the closely related 2-ethylbutyl derivative, OpSc(CH[sub 2]CH(C[sub 2]H[sub 5])CH[sub 2]CH[sub 3])(PMe[sub 3]), obtained from reaction of 2-ethyl-1-butene with OpSc(H)(PMe[sub 3]). 28 refs., 2 figs., 1 tab.

  8. Microstructure study of the rare-earth intermetallic compounds R5(SixGe1-x)4sub> and R5(SixGe1-x)3

    SciTech Connect

    Cao, Qing


    The unique combination of magnetic properties and structural transitions exhibited by many members of the R5(SixGe1-x)4sub> family (R = rare earths, 0 ≤ x ≤ 1) presents numerous opportunities for these materials in advanced energy transformation applications. Past research has proven that the crystal structure and magnetic ordering of the R5(SixGe1-x)4sub> compounds can be altered by temperature, magnetic field, pressure and the Si/Ge ratio. Results of this thesis study on the crystal structure of the Er5Si4sub> compound have for the first time shown that the application of mechanical forces (i.e. shear stress introduced during the mechanical grinding) can also result in a structural transition from Gd5Si4sub>-type orthorhombic to Gd5Si2Ge2-type monoclinic. This structural transition is reversible, moving in the opposite direction when the material is subjected to low-temperature annealing at 500 °C.

  9. Phase transitions and molecular motions in [Cd(H{sub 2}O){sub 6}](BF{sub 4}){sub 2} studied by DSC, {sup 1}H and {sup 19}F NMR and FT-MIR

    SciTech Connect

    Mikuli, E. . E-mail:; Grad, B.; Medycki, W.; Holderna-Natkaniec, K.


    Two solid phase transitions of [Cd(H{sub 2}O){sub 6}](BF{sub 4}){sub 2} occurring on heating at T{sub C2}=183.3K and T{sub C1}=325.3K, with 2K and 5K hysteresis, respectively, were detected by differential scanning calorimetry (DSC). High value of entropy changes indicated large orientational disorder of the high temperature and intermediate phase. Nuclear magnetic resonance ({sup 1}H NMR and {sup 19}F NMR) relaxation measurements revealed that the phase transitions at T{sub C1} and T{sub C2} were associated with a drastic and small change, respectively, of the both spin-lattice relaxation times: T{sub 1}({sup 1}H) and T{sub 1}({sup 19}F). These relaxation processes were connected with the 'tumbling' motions of the [Cd(H{sub 2}O){sub 6}]{sup 2+}, reorientational motions of the H{sub 2}O ligands, and with the iso- and anisotropic reorientation of the BF{sub 4}{sup -} anions. The cross-relaxation effect was observed in phase III. The line width and the second moment of the {sup 1}H and {sup 19}F NMR line measurements revealed that the H{sub 2}O reorientate in all three phases of the title compound. On heating the onset of the reorientation of 3 H{sub 2}O in the [Cd(H{sub 2}O){sub 6}]{sup +2}, around the three-fold symmetry axis of these octahedron, causes the isotropic reorientation of the whole cation. The BF{sub 4}{sup -} reorientate isotropically in the phases I and II, but in the phase III they perform slow reorientation only about three- or two-fold axes. A small distortion in the structure of BF{sub 4}{sup -} as well as of [Cd(H{sub 2}O){sub 6}]{sup 2+} is postulated. The temperature dependence of the bandwidth of the O-H stretching mode measured by Fourier transform middle infrared spectroscopy (FT-MIR) indicated that the activation energy for the reorientation of the H{sub 2}O did not change much at the T{sub C2} phase transition.

  10. Thermal expansion of lanthanum silicate oxyapatite (La{sub 9.33+2x}(SiO{sub 4}){sub 6}O{sub 2+3x}), lanthanum oxyorthosilicate (La{sub 2}SiO{sub 5}) and lanthanum sorosilicate (La{sub 2}Si{sub 2}O{sub 7})

    SciTech Connect

    Fukuda, Koichiro; Asaka, Toru; Uchida, Tomohiro


    Four types of powder specimens of La{sub 9.33}(SiO{sub 4}){sub 6}O{sub 2} (space group P6{sub 3}/m and Z=1), La{sub 9.33+2x}(SiO{sub 4}){sub 6}O{sub 2+3x} with 0.06{<=}x{<=}0.13 (P6{sub 3}/m and Z=1), La{sub 2}SiO{sub 5} (P2{sub 1}/c and Z=4) and La{sub 2}Si{sub 2}O{sub 7} (P2{sub 1}/c and Z=4) were examined by high-temperature X-ray powder diffractometry to determine the changes in unit-cell dimensions up to 1473 K. The anisotropy of thermal expansion was demonstrated for the former two crystals to clarify the thermal behaviors of the highly c-axis-oriented polycrystals. With La{sub 9.33}(SiO{sub 4}){sub 6}O{sub 2}, the linear expansion coefficient of the a-axis ({alpha}{sub a}) was 4.8 Multiplication-Sign 10{sup -6} K{sup -1} and that of the c-axis ({alpha}{sub c}) was 1.8 Multiplication-Sign 10{sup -6} K{sup -1} in the temperature range from 298 to 1473 K. The {alpha}{sub a}- and {alpha}{sub c}-values of La{sub 9.33+2x}(SiO{sub 4}){sub 6}O{sub 2+3x} (0.06{<=}x{<=}0.13) were, respectively, 5.9 Multiplication-Sign 10{sup -6} K{sup -1} and 2.3 Multiplication-Sign 10{sup -6} K{sup -1}. The coefficients of mean linear thermal expansion were 4.9 Multiplication-Sign 10{sup -6} K{sup -1} for La{sub 2}SiO{sub 5} and 6.0 Multiplication-Sign 10{sup -6} K{sup -1} for La{sub 2}Si{sub 2}O{sub 7}, which describe the thermal expansion behaviors of the randomly grain-oriented polycrystalline materials. - Graphical abstarct: Temperature dependence of the coefficients of thermal expansion (CTE). The linear CTE along the a-axes for La{sub 9.33}(SiO{sub 4}){sub 6}O{sub 2} and La{sub 9.33+2x}(SiO{sub 4}){sub 6}O{sub 2+3x} with 0.06{<=}x{<=}0.13. The mean linear CTE for La{sub 2}SiO{sub 5} and La{sub 2}Si{sub 2}O{sub 7}. Highlights: Black-Right-Pointing-Pointer We examined the thermal expansion of La{sub 9.33+2x}(SiO{sub 4}){sub 6}O{sub 2+3x} (x=0 and 0.06{<=}x{<=}0.13), La{sub 2}SiO{sub 5} and La{sub 2}Si{sub 2}O{sub 7} Black-Right-Pointing-Pointer Unit-cell dimensions were

  11. Second order phase transition temperature of single crystals of Gd5Si1.3Ge2.7 and Gd5Si1.4sub>Ge2.6

    SciTech Connect

    Hadimani, R. L.; Melikhov, Y.; Schlagel, D. L.; Lograsso, T. A.; Dennis, K. W.; McCallum, R. W.; Jiles, D. C.


    Gd5(SixGe1–x)4sub> has mixed phases in the composition range 0.32 < x < 0.41, which have not been widely studied. In this paper, we have synthesized and indexed single crystal samples of Gd5Si1.3Ge2.7 and Gd5Si1.4sub>Ge2.6. In this study, we have investigated the first order and second order phase transition temperatures of these samples using magnetic moment vs. temperature and magnetic moment vs. magnetic field at different temperatures. We have used a modified Arrott plot technique that was developed and reported by us previously to determine the “hidden” second order phase transition temperature of the orthorhombic II phase.

  12. Color-tunable photoluminescence phosphors of Ce{sup 3+} and Tb{sup 3+} co-doped Sr{sub 2}La{sub 8}(SiO{sub 4}){sub 6}O{sub 2} for UV w-LEDs

    SciTech Connect

    Guo, Qingfeng; Liao, Libing Mei, Lefu; Liu, Haikun; Hai, Yun


    A series of new luminescent emission-tunable phosphors Sr{sub 2}La{sub 8}(SiO{sub 4}){sub 6}O{sub 2}:Ce{sup 3+}, Tb{sup 3+} with apatite structure have been synthesized by a high temperature solid-state reaction. The phase structure, photoluminescence emission and excitation spectra, lifetime, as well as the effect of Tb{sup 3+} concentration are investigated to characterize the resulting samples. The critical distance was calculated to be 8.26 Å by using the concentration quenching method. The intense green emission was observed in the Sr{sub 2}La{sub 8}(SiO{sub 4}){sub 6}O{sub 2}:Ce{sup 3+}, Tb{sup 3+} phosphors on the basis of the efficient energy transfer from Ce{sup 3+} to Tb{sup 3+} with an efficiency of 68.55%. And a possible mechanism of the energy-transfer from Ce{sup 3+} to Tb{sup 3+} ion is also proposed. The results indicate that Sr{sub 2}La{sub 8}(SiO{sub 4}){sub 6}O{sub 2}:Ce{sup 3+}, Tb{sup 3+} phosphors have potential applications to be used as near UV-convertible phosphors for white light-emitting diodes because of the broad excitation in the near-ultraviolet range and the efficient green emission light. - Graphical abstract: Crystal structure and luminescence properties of Sr{sub 2}La{sub 8}(SiO{sub 4}){sub 6}O{sub 2}:Ce{sup 3+},Tb{sup 3+} phosphors have been discussed. - Highlights: • Ce{sup 3+} and Tb{sup 3+} ions entered both La sites in SLSO. • The energy transfer efficiency can reach at 68.55%. • The emitting color of SLSO phosphors shifted from the blue to green region.

  13. Phase relations in the system K{sub 2}MoO{sub 4}-KPO{sub 3}-MoO{sub 3}-Bi{sub 2}O{sub 3}: A new phosphate K{sub 3}Bi{sub 5}(PO{sub 4}){sub 6}

    SciTech Connect

    Terebilenko, Kateryna V.; Zatovsky, Igor V. Slobodyanik, Nikolay S.; Domasevitch, Konstantin V.; Pushkin, Denis V.; Baumer, Vyacheslav N.; Sudavtsova, Valentina S.


    Phase equilibrium in the pseudo-quaternary system K{sub 2}O-MoO{sub 3}-P{sub 2}O{sub 5}-Bi{sub 2}O{sub 3} was studied as three-component solvent K{sub 2}MoO{sub 4}-KPO{sub 3}-MoO{sub 3} containing 15 mol% Bi{sub 2}O{sub 3} during slow cooling and spontaneous crystallization. The results of the investigation were shown on a composition diagram, which indicates the crystallization fields of K{sub 2}Bi(PO{sub 4})(MoO{sub 4}), K{sub 5}Bi(MoO{sub 4}){sub 4}, BiPO{sub 4} and K{sub 3}Bi{sub 5}(PO{sub 4}){sub 6}. New phosphate K{sub 3}Bi{sub 5}(PO{sub 4}){sub 6} was characterized by single-crystal X-ray diffraction (space group C2/c, a=17.680(4), b=6.9370(14), c=18.700(4) A, {beta}=113.79(3){sup o}) and FTIR spectroscopy. The possibility of lone electron pair stereoactivity of bismuth was suggested using the calculations of characteristics of the Voronoi-Dirichlet polyhedra for K{sub 3}Bi{sub 5}(PO{sub 4}){sub 6} and K{sub 2}Bi(PO{sub 4})(MoO{sub 4}). - Graphical abstract: Composition diagram of the K{sub 2}MoO{sub 4}-KPO{sub 3}-MoO{sub 3} system containing 15 mol% Bi{sub 2}O{sub 3} with approximate fields of phase formation bismuth phosphates, molybdate and phosphate-molybdate.

  14. Influence of composition modification on Ca{sub 0.5−x}Mg{sub x}Ti{sub 2}(PO{sub 4}){sub 3} (0.0 ≤ x ≤ 0.5) nanoparticles as electrodes for lithium batteries

    SciTech Connect

    Vidal-Abarca, C. Aragón, M.J.; Lavela, P.; Tirado, J.L.


    Graphical abstract: - Highlights: • Cation mixing was determined in the Ca{sub 0.5−x}Mg{sub x}Ti{sub 2}(PO{sub 4}){sub 3} biphasic series. • Nanometric Ca{sub 0.15}Mg{sub 0.35}Ti{sub 2}(PO{sub 4}){sub 3} delivered 138 mAh/g at C/20 in lithium cells. • Low content of Ca{sup 2+} increases cell volume favoring Li{sup +} insertion in R-3c framework. • Diminution of R{sub SEI} and R{sub CT} for Ca{sub 0.15}Mg{sub 0.35}Ti{sub 2}(PO{sub 4}){sub 3} discharged electrodes. • Fast electrode response for x = 0.35. - Abstract: The Ca{sub 0.5−x}Mg{sub x}Ti{sub 2}(PO{sub 4}){sub 3} series (0.0 ≤ x ≤ 0.5) was prepared by a sol–gel method. X-ray diffraction patterns showed two rhombohedral phases which coexist for intermediate compositions. Despite of the absence of a solid solution mechanism for the whole stoichiometry range, an appreciable cation mixing was observed in both phases. {sup 31}P MAS NMR spectroscopy revealed that low magnesium contents are incorporated to the calcium compound inducing changes in the ordering of the alkaline earth cations in M{sub 1} sites. Derivative plots of the voltage–capacity curves revealed two reversible regions ascribed to the reduction of Ti{sup 4+} to Ti{sup 3+}, ascribable to the subsequent insertion of lithium ions into M{sub 1} and M{sub 2} vacant sites. Capacity values as high as 138 mAh/g after the first discharge were monitored for nanometric Ca{sub 0.15}Mg{sub 0.35}Ti{sub 2}(PO{sub 4}){sub 3} at C/20. Cell cycling under successive kinetic rates revealed a good capacity retention for samples with x = 0.15 and 0.25. Impedance spectra were recorded in lithium cells discharged after different number of cycles at different C rates. The increase in charge transfer resistance was shown to be an important factor determining the electrode behavior on extended cycling.

  15. Electronic, Structural, and Electrochemical Properties of LiNixCuyMn2-x-yO4sub> (0 < x < 0.5, 0 < y < 0.5) High-Voltage Spinel Materials

    SciTech Connect

    Yang, Ming-Che; Xu, Bo; Cheng, Ju-Hsiang; Pan, Chun-Jern; Hwang, Bing-Joe; Meng, Ying S


    First principles computation is carried out for investigating the electronic, structural, and electrochemical properties of LiM1/2Mn3/2O4sub> (M = Ti, V, Cr, Fe, Co, Ni, and Cu). The computation results suggest that doping with Co or Cu can potentially lower Li diffusion barrier as compared to Ni doping. Our experimental research has focused on LiNixCuyMn2-x-yO4sub> (0 < x < 0.5, 0 < y < 0.5), and we found that the amount of Cu will affect the lattice parameters, the cation disorder in the spinel lattice, the particle morphology, as well as the electrochemical properties. Crystal structures, electronic structures, and electrochemical properties of LiNixCuyMn2-x-6O4sub> (0 < x < 0.5, 0 < y < 0.5) are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray absorption spectroscopy (XAS), and electrochemical measurements including potentiostatic intermittent titration technique (PITT). With detailed electrochemical measurements and in situ XAS experiments of LiNi0.25Cu0.25Mn1.50O4sub>, the proposed explanation of the voltage profile by the first principles computation was proven, a second plateau at 4.2 V originates from the oxidation of Cu2+ to Cu3+, and the plateau at 4.95 V may originate from extra electrons provided by oxygen ions. Although the reversible discharge capacity decreases with increasing Cu amount, optimized composition such as LiCu0.25Ni0.25Mn1.5O4sub>exhibits high capacities at high rates.

  16. Hydrothermal synthesis, crystal structure, and characterization of a new pseudo-two-dimensional uranyl oxyfluoride, [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}

    SciTech Connect

    Ok, Kang Min; O'Hare, Dermot


    A new uranyl oxyfluoride, [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] has been synthesized by a hydrothermal reaction technique using (C{sub 2}H{sub 5}){sub 4}NBr, UO{sub 2}(OCOCH{sub 3}){sub 2}.2H{sub 2}O, and HF as reagents. The structure of [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] has been determined by a single-crystal X-ray diffraction technique. [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] crystallizes in the monoclinic space group P2{sub 1}/n (No. 14), with a=13.852(3)A, b=15.532(3)A, c=16.481(3)A, {beta}=98.88(3){sup o}, V=3503.4(12)A{sup 3}, and Z=4. [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] reveals a novel pseudo-two-dimensional crystal structure that is composed of UO{sub 2}F{sub 5}, UO{sub 3}F{sub 4}, and UO{sub 4}F{sub 3} pentagonal bipyramids. Each uranyl pentagonal bipyramid shares edges and corners through F atoms to form a six-membered ring. The rings are further interconnected to generate infinite strips running along the b-axis. [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}[(UO{sub 2}){sub 4}(OH{sub 2}){sub 3}F{sub 10}] has been further characterized by elemental analysis, bond valence calculations, Infrared and Raman spectroscopy, and thermogravimetric analysis.

  17. High-pressure high-temperature synthesis and crystal structure of the isotypic rare earth (RE)-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu)

    SciTech Connect

    Borna, Marija; Hunger, Jens; Ormeci, Alim; Zahn, Dirk; Burkhardt, Ulrich; Carrillo-Cabrera, Wilder; Cardoso-Gil, Raul; Kniep, Ruediger


    Application of high-pressure high-temperature conditions (3.5 GPa at 1673 K for 5 h) to mixtures of the elements (RE:B:S=1:3:6) yielded crystalline samples of the isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu), which crystallize in space group P6{sub 3} (Z=2/3) and adopt the Ce{sub 6}Al{sub 3.33}S{sub 14} structure type. The crystal structures were refined from X-ray powder diffraction data by applying the Rietveld method. Dy: a=9.4044(2) A, c=5.8855(3) A; Ho: a=9.3703(1) A, c=5.8826(1) A; Er: a=9.3279(12) A, c=5.8793(8) A; Tm: a=9.2869(3) A, c=5.8781(3) A; Yb: a=9.2514(5) A, c=5.8805(6) A; Lu: a=9.2162(3) A, c=5.8911(3) A. The crystal structure is characterized by the presence of two isolated complex ions [BS{sub 3}]{sup 3-} and [BS{sub 4}]{sup 5-} as well as [{open_square}(S{sup 2-}){sub 3}] units. -- Graphical abstract: Isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) were prepared by application of high-pressure high-temperature conditions to mixtures of the elements. Their crystal structures are characterized by presence of the two isolated complex ions [BS{sub 3}]{sup 3-} and [BS{sub 4}]{sup 5-} as well as [{open_square}(S{sup 2-}){sub 3}] units. Quantum mechanical calculations revealed the arrangement of the intrinsic vacancies. Display Omitted Research Highlights: {yields} Application of high-pressure high-temperature conditions to mixtures of the elements yields crystalline samples of the isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu). {yields} RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) crystallize in space group P6{sub 3} (Z=2/3) and adopt the Ce{sub 6}Al{sub 3.33}S{sub 14} structure type. {yields} The crystal structure of RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) is characterized by the presence of two isolated complex ions [BS{sub 3

  18. Structural study of (N{sub 2}H{sub 5},H){sub 2.9}U{sub 1.1}Ce{sub 0.9}(C{sub 2}O{sub 4}){sub 5}·10H{sub 2}O from a conventional X-ray diffraction diagram obtained on a powder synthesized by a fast vortex process

    SciTech Connect

    Brackx, E.; Laval, J.P.; Dugne, O.; Feraud, J.P.; Arab-Chapelet, B.


    In the context of research on U/minor actinides for nuclear fuel reprocessing in the transmutation process, developments are first studied with surrogates containing uranium and lanthanides to facilitate testing. The tests consist of precipitating and calcining a hydrazinium uranium/cerium oxalate. The structure of this oxalate had not been previously determined, but was necessary to validate the physicochemical mechanisms involved. The present study, firstly demonstrates the structural similarity of the U/Ce oxalate phase (N{sub 2}H{sub 5},H){sub 2.9}U{sub 1.1}Ce{sub 0.9}(C{sub 2}O{sub 4}){sub 5}·10H{sub 2}O, synthesized using a vortex precipitator for continuous synthesis of actinide oxalates, with previously known oxalates, crystallizing in P6{sub 3}/mmc symmetry, obtained by more classical methods. This fast precipitation process induces massive nucleation of fine powders. Their structural and microstructural determination confirms that the raw and dried phases belong to the same structural family as (NH{sub 4}){sub 2}U{sub 2}(C{sub 2}O{sub 4}){sub 5}·0.7H{sub 2}O whose structure was described by Chapelet-Arab in P6{sub 3}/mmc symmetry, using single crystal data. However, they present an extended disorder inside the tunnels of the structure, even after drying at 100 °C, between water and hydrazinium ions. This disorder is directly related to the fast vortex method. This structure determination can be used as a basis for further semi-quantitative analysis on the U/minor actinides products formed under various experimental conditions. - Highlights: • Uranium cerium oxalate precipitate characterization by X-ray powder diffraction. • Morphology characterization by SEM analysis. • Structure determination by unit cell Rietveld refinement.

  19. Hole defects in the crystal structure of synthetic lipscombite (Fe{sub 4.7}{sup 3+}Fe{sub 2.3}{sup 2+})[PO{sub 4}]{sub 4}O{sub 2.7}(OH){sub 1.3} and genetic crystal chemistry of minerals of the lipscombite-barbosalite series

    SciTech Connect

    Yakubovich, O. V. Steele, I. M.; Rusakov, V. S.; Urusov, V. S.


    The crystal structure of a synthetic analog of the mineral lipscombite (Fe{sub 2.3}{sup 2+}Fe{sub 4.7}{sup 3+})[PO{sub 4}]{sub 4}O{sub 2.7}(OH){sub 1.3} obtained under hydrothermal conditions in the LiF-Fe{sub 2}O{sub 3}-(NH{sub 4}){sub 2}HPO{sub 4}-H{sub 2}O system is resolved (R = 0.040) by X-ray diffraction analysis (Bruker Smart diffractometer with a highly sensitive CCD detector, MoK{sub {alpha}} radiation): a = 14.776(3) A, b = 14.959(3) A, c = 7.394(1) A, {beta} = 119.188(4) deg., sp. gr. C2/c, Z = 4, {rho}{sub exp} = 3.8 g/cm{sup 3}, {rho}{sub calcd} = 3.9 g/cm{sup 3}. Fe{sup 2+} and Fe{sup 3+} cations are statistically distributed in each of four crystallographically independent positions, while occupying the corresponding octahedra with probabilities of 60, 90, 100, and 91%. The ratio Fe{sup 2+}/Fe{sup 3+} in the composition of the crystals was established by Moessbauer spectroscopy. Lipscombite is interpreted as a mineral of variable composition described by the formula (Fe{sub x}{sup 2+}Fe{sub n-x}{sup 3+})[PO{sub 4}]{sub 4}O{sub y}(OH){sub 4-y}. The field of stability is determined as a function of the iron content and the ratio Fe{sup 2+}/Fe{sup 3+}. It is shown that at n = 6 iron cations are ordered in octahedra and barbosalite structure is formed. An interpretation of genetically and structurally related members of the lipscombite family within a unified polysomatic series is proposed.

  20. Pressure-induced isostructural phase transition of a metal-organic framework Co2(4,4'-bpy)3(NO3)4sub>·xH2O

    SciTech Connect

    Zhou, Mi; Wang, Kai; Men, Zhiwei; Sun, Chenglin; Li, Zhanlong; Liu, Bingbing; Zou, Guangtian; Zou, Bo


    Based on the 4,4'-bipyridine organic linker, metal–organic frameworks of Co2(4,4'-bpy)3(NO3)4sub>·xH2O (CB-MOF) have been prepared. The pressure-dependent structure evolution of CB-MOF has been investigated up to 11 GPa. An isostructural phase transition was observed at about 6 GPa followed by negative compressibility along the b axis.

  1. Acoustic emission during the ferroelectric transition Pm3{sup ¯}m to P4mm in BaTiO{sub 3} and the ferroelastic transition R3{sup ¯}m-C2/c in Pb{sub 3}(PO{sub 4}){sub 2}

    SciTech Connect

    Salje, E. K. H.; Dul'kin, E.; Roth, M.


    Acoustic emission (AE) spectroscopy without frequency filtering (∼broadband AE) and moderate time integration is shown to be sensitive enough to allow the investigation of subtle nano-structural changes in ferroelectric BaTiO{sub 3} and ferroelastic Pb{sub 3}(PO{sub 4}){sub 2}. AE signals during weak phase transitions are compatible with avalanche statistics as observed previously in large-strain systems. While the data are too sparse to determine avalanche exponents, they are well suited to determine other thermodynamic parameters such as transition temperatures and critical stresses.

  2. A Straight Forward Route for the Development of Metal-Organic Frameworks Functionalized with Aromatic -OH Groups: Synthesis, Characterization, and Gas (N2, Ar, H2, CO2, CH4sub>, NH3) Sorption Properties

    SciTech Connect

    Spanopoulos, Ioannis; Xydias, Pantelis; Malliakas, Christos D; Trikalitis, Pantelis N


    A facile and general methodology for the development of metal–organic frameworks (MOFs) functionalized with pendant, aromatic hydroxyl (-OH) groups is presented. Extensive gas-sorption studies in representative and important MOFs functionalized with free aromatic -OH groups such as the IRMOF-8 and DUT-6 (or MOF-205), denoted here as 1 and 2, revealed a high CO2/CH4sub> selectivity for 1 (13.6 at 273 K and 1 bar) and a high NH3 uptake of 16.4 mol kg–1 at 298 K and 1 bar for 2.

  3. Electronic and Electrochemical Properties of Li 1–x Mn 1.5 Ni 0.5 O 4sub> Spinel Cathodes As a Function of Lithium Content and Cation Ordering

    SciTech Connect

    Moorhead-Rosenberg, Zach; Huq, Ashfia; Goodenough, John B.; Manthiram, Arumugam


    The electronic and electrochemical properties of the high-voltage spinel LiMn1.5Ni0.5O4sub> as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni2+/3+. and Ni3+/4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 in Li Li1-xMn1.5Ni0.5O4sub>. Furthermore, maximum electronic conductivity is found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn1.5Ni0.5O4sub> to Li0.5Mn1.5Ni0.5O4sub>. The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.

  4. Preparation and microwave dielectric properties of Li{sub 3}(Mg{sub 0.92}Zn{sub 0.08}){sub 2}NbO{sub 6}–Ba{sub 3}(VO{sub 4}){sub 2} composite ceramics for LTCC applications

    SciTech Connect

    Zhang, Tianwen; Zuo, Ruzhong Zhang, Chen


    Highlights: • Microwave properties of ϵ{sub r} ∼ 16.3, Q × f ∼ 50,084 GHz and τ{sub f} ∼ 1.5 ppm/°C are achieved. • The τ{sub f} value of the LMZN ceramic can be adjusted to near zero by adding BV. • The LMZN–BV composite ceramic can be well sintered at a relatively low temperature. • The composite ceramic has a good chemical compatibility with Ag electrode. - Abstract: In this work, the (1 − x)Li{sub 3}(Mg{sub 0.92}Zn{sub 0.08}){sub 2}NbO{sub 6}–xBa{sub 3}(VO{sub 4}){sub 2} (x = 0.1–0.35) ceramics were prepared via a conventional solid state reaction route. The phase composition, microstructure and microwave dielectric properties were investigated by an X-ray diffractometer (XRD), a scanning electron microscope and a network analyzer. The XRD results indicated that the Li{sub 3}(Mg{sub 0.92}Zn{sub 0.08}){sub 2}NbO{sub 6} and Ba{sub 3}(VO{sub 4}){sub 2} phases could well coexist without forming any secondary phases. The dielectric constant (ϵ{sub r}) and quality factor (Q × f) values of the Li{sub 3}(Mg{sub 0.92}Zn{sub 0.08}){sub 2}NbO{sub 6} ceramic decreased with the addition of Ba{sub 3}(VO{sub 4}){sub 2} phase, however its temperature coefficient of resonant frequency (τ{sub f}) value was improved significantly. Excellent microwave dielectric properties of ϵ{sub r} ∼ 16.3, Q × f ∼ 50,084 GHz (at 8.64 GHz) and τ{sub f} ∼ 1.5 ppm/°C were achieved for the x = 0.3 sample when sintered at 950 °C for 4 h. The chemical compatibility with Ag electrode indicated that the 0.7Li{sub 3}(Mg{sub 0.92}Zn{sub 0.08}){sub 2}NbO{sub 6}–0.3Ba{sub 3}(VO{sub 4}){sub 2} composite ceramic would be a promising material for the low temperature cofired ceramic applications.

  5. Thermal Reactions of Uranium Metal, UO2, U3O8, UF4sub>, and UO2F2 with NF3 to Produce UF6

    SciTech Connect

    McNamara, Bruce K; Scheele, Randall D; Kozelisky, Anne E; Edwards, Matthew K


    The objective of this paper is to demonstrate that NF3 fluorinates uranium metal, UO2, UF4sub>, UO3, U3O8, and UO2F2•2H2O to produce the volatile UF6 at temperatures between 100 and 500ºC. Thermogravimetric reaction profiles are described that reflect changes in the uranium oxidation state and discrete chemical speciation. Differences in the onset temperatures for each system indicate that NF3-substrate interactions are important for the temperature at which NF3 reacts: U metal > UO3 > UO2 > UO2F2 > UF4sub> and in fact may indicate different fluorination mechanisms for these various substrates. These studies demonstrate that NF3 is a potential replacement fluorinating agent in the existing nuclear fuel cycle and in oft-proposed actinide volatility reprocessing.

  6. {open_quotes}Nb{sub 2-x}P{sub 3-y}O{sub 12},{close_quotes} a novel Nb{sup v} oxophosphate with disordered cation vacancies in a Sc{sub 2}(WO{sub 4}){sub 3}-type structure

    SciTech Connect

    Zah-Letho, J.J.; Verbaere, A.; Jouanneaux, A.


    The title compound was prepared at 360{degrees}C, starting from Nb{sub 2}O{sub 5} and NH{sub 4}H{sub 2}PO{sub 4}. The orthorhombic unit-cell parameters were determined by electron and X-ray diffractions: a = 12.0819 (2) {angstrom}, b = 8.6848 (1) {angstrom}, c = 8.7452 (1) {angstrom}, space group Pbcn. Reitveld refinements from X-ray powder diffraction data, chemical analyses, and the measured density show that the basic structure consists of a three-dimensional framework of the Sc{sub 2}(WO{sub 4}){sub 3} structure type, with NbO{sub 6} octahedra and PO{sub 4} tetrahedra sharing corners, and that both Nb and P vacancies occur. The actual formula is close to Nb{sub 2-x}P{sub 3-y}O{sub 12}. Comparative spectroscopic studies of the title compound and of Nb{sub 3}(NbO){sub 2}(PO{sub 4}){sub 7} confirm the occurrence of the vacancies, and thus an important local variation of the bond lengths near the defect sites. The presence of small amounts of H and N in the structure is discussed. Upon heating in air, the structure is preserved up to 900{degrees}C. The so-called {epsilon}-NbOPO{sub 4} has the same basic structure, and its existence seems questionable.

  7. New yellow Ba0.93Eu0.07Al2O4sub> phosphor for warm-white light-emitting diodes through single-emitting-center conversion

    SciTech Connect

    Li, Xufan; Budai, John D.; Liu, Feng; Howe, Jane Y.; Zhang, Jiahua; Wang, Xiao-Jun; Gu, Zhanjun; Sun, Chengjun; Meltzer, Richard S.; Pan, Zhengwei


    Phosphor-converted white light-emitting diodes for indoor illumination need to be warm-white (i.e., correlated color temperature <4000 K) with good color rendition (i.e., color rendering index >80). However, no single-phosphor, single-emitting-center-converted white light-emitting diodes can simultaneously satisfy the color temperature and rendition requirements due to the lack of sufficient red spectral component in the phosphors’ emission spectrum. Here, we report a new yellow Ba0.93Eu0.07Al2O4sub> phosphor that has a new orthorhombic lattice structure and exhibits a broad yellow photoluminescence band with sufficient red spectral component. Warm-white emissions with correlated color temperature <4000 K and color rendering index >80 were readily achieved when combining the Ba0.93Eu0.07Al2O4sub> phosphor with a blue light-emitting diode (440–470 nm). This study demonstrates that warm-white light-emitting diodes with high color rendition (i.e., color rendering index >80) can be achieved based on single-phosphor, single-emitting-center conversion.

  8. Performance improvement of Li-rich layer-structured Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 by integration with spinel LiNi 0.5 Mn 1.5 O 4sub>

    SciTech Connect

    Feng, Xin; Yang, Zhenzhong; Tang, Daichun; Kong, Qingyu; Gu, Lin; Wang, Zhaoxiang; Chen, Liquan


    Li-rich layered Li1+xMnyM1-x-yO2 (or denoted xLi2MnO3center dot1-xLiMO2, M = Ni, Co, Mn, etc.) are promising cathode materials for high energy-density Li-ion batteries. However, their commercial applications suffer from problems such as a drop in the capacity and discharge voltage during cycling. In this work, the cycling performance of a layered oxide Li1.2Ni0.13Co0.13Mn0.54O2 is improved by integration with spinel LiNi0.5Mn1.5O4sub> to obtain a layered-spinel composite. Characterization by powder X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) as well as cyclic voltammetry (CV) indicates that delayed degradation of layered Li2MnO3 and the suppressed growth of LiMn2O4sub>-like spinel are responsible for the performance improvement.

  9. From the ternary Eu(Au/In)2 and EuAu4sub>(Au/In)2 with remarkable Au/In distributions to a new structure type: The gold-rich Eu5Au16(Au/In)6 structure

    SciTech Connect

    Steinberg, Simon; Card, Nathan; Mudring, Anja -Verena


    The ternary Eu(Au/In)2 (EuAu0.46In1.54(2)) (I), EuAu4sub>(Au/In)2 (EuAu4+xIn2–x with x = 0.75(2) (II), 0.93(2), and 1.03(2)), and Eu5Au16(Au/In)6 (Eu5Au17.29In4.71(3)) (III) have been synthesized, and their structures were characterized by single-crystal X-ray diffraction. I and II crystallize with the CeCu2-type (Pearson Symbol oI12; Imma; Z = 4; a = 4.9018(4) Å; b = 7.8237(5) Å; c = 8.4457(5) Å) and the YbAl4sub>Mo2-type (tI14; I4/mmm; Z = 2; a = 7.1612(7) Å; c = 5.5268(7) Å) and exhibit significant Au/In disorder. I is composed of an Au/In-mixed diamond-related host lattice encapsulating Eu atoms, while the structure of II features ribbons of distorted, squared Au8 prisms enclosing Eu, Au, and In atoms. Combination of these structural motifs leads to a new structure type as observed for Eu5Au16(Au/In)6 (Eu5Au17.29In4.71(3)) (oS108; Cmcm; Z = 4; a = 7.2283(4) Å; b = 9.0499(6) Å; c = 34.619(2) Å), which formally represents a one-dimensional intergrowth of the series EuAu2–“EuAu4sub>In2”. The site preferences of the disordered Au/In positions in II were investigated for different hypothetical “EuAu4sub>(Au/In)2” models using the projector-augmented wave method and indicate that these structures attempt to optimize the frequencies of the heteroatomic Au–In contacts. Furthermore, a chemical bonding analysis on two “EuAu5In” and “EuAu4sub>In2” models employed the TB-LMTO-ASA method and reveals that the subtle interplay between the local atomic environments and the bond energies determines the structural and site preferences for these systems.

  10. Crystal and molecular structure of four copper(II) ethylenediaminedisuccinates, [Cu{sub 2}(RR,SS-Edds)] . 6H{sub 2}O, Ba{sub 2}[Cu(RR,SS-Edds)](ClO{sub 4}){sub 2} . 8H{sub 2}O, Ba[Cu(SS-HEdds)]ClO{sub 4} . 2H{sub 2}O, and Ba{sub 3}[Cu{sub 2}(RR,SS-Edds){sub 2}](ClO{sub 4}){sub 2} . 6H{sub 2}O

    SciTech Connect

    Polyakova, I. N.; Poznyak, A. L.; Sergienko, V. S.


    Four Cu(II) complexes with the RR,SS-Edds{sup 4-} and SS-HEdds{sup 3-} anions are synthesized, and their crystal structures are studied. In the compounds [Cu2(RR,SS-Edds)] . 6H{sub 2}O (I) and Ba2[Cu(RR,SS-Edds)](ClO{sub 4}){sub 2} . 8H{sub 2}O (II), the ligand forms hexacoordinate chelate [Cu(Edds)]{sup 2-} complexes with the N atoms and O atoms of the propionate groups in the equatorial positions and the O atoms of the acetate groups in the axial vertices. In the compounds Ba[Cu(SS-HEdds)]ClO{sub 4} . 2H{sub 2}O (III) and Ba3[Cu2(RR,SS-Edds){sub 2}](ClO{sub 4}){sub 2} . 6H{sub 2}O (IV), one of the propionate arms, the protonated arm in III and the deprotonated arm in IV, does not enter into the coordination sphere of the Cu atom. An acetate arm moves to its position in the equatorial plane, and the free axial vertex is occupied by an O atom of the perchlorate ion. In I-IV, the lengths of the equatorial Cu-N and Cu-O bonds fall in the ranges 1.970-2.014 and 1.921-1.970 A, respectively. The axial Cu-O bonds with the acetate groups and ClO{sub 4}{sup -} anions are elongated to 2.293-2.500 and 2.727-2.992 A, respectively. In structure I, the second Cu atom acts as a counterion forming bonds with the O atoms of two water molecules and three O atoms of the Edds ligands. In II-IV, the Ba{sup 2+} cations are hydrated and bound to the O atoms of the anionic complexes and (except for one of the cations in IV) ClO{sub 4}{sup -} anions. The coordination number of the Ba cations is nine. The structural units in I-IV are connected into layers. In I, an extended system of hydrogen bonds links the layers into a framework. In II and III, the layers are linked only by weak hydrogen bonds, one bond per structural unit. In IV, ClO{sub 4}{sup -} anions are bound to the Ba and Cu atoms of neighboring layers, thus serving as bridges between the layers.

  11. [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}], crystal structure and comparison with uranium minerals with U{sub 3}O{sub 8}-type sheets

    SciTech Connect

    Rivenet, Murielle; Vigier, Nicolas; Roussel, Pascal; Abraham, Francis


    The new U(VI) compound, [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}], was synthesized by mild hydrothermal reaction of uranyl and nickel nitrates. The crystal-structure was solved in the P-1 space group, a=8.627(2), b=10.566(2), c=12.091(4) A and alpha=110.59(1), beta=102.96(2), gamma=105.50(1){sup o}, R=0.0539 and wR=0.0464 from 3441 unique observed reflections and 151 parameters. The structure of the title compound is built from sheets of uranium polyhedra closely related to that in beta-U{sub 3}O{sub 8}. Within the sheets [(UO{sub 2})(OH)O{sub 4}] pentagonal bipyramids share equatorial edges to form chains, which are cross-linked by [(UO{sub 2})O{sub 4}] and [UO{sub 4}(H{sub 2}O)(OH)] square bipyramids and through hydroxyl groups shared between [(UO{sub 2})(OH)O{sub 4}] pentagonal bipyramids. The sheets are pillared by sharing the apical oxygen atoms of the [(UO{sub 2})(OH)O{sub 4}] pentagonal bipyramids with the oxygen atoms of [NiO{sub 2}(H{sub 2}O){sub 4}] octahedral units. That builds a three-dimensional framework with water molecules pointing towards the channels. On heating [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}] decomposes into NiU{sub 3}O{sub 10}. - Graphical abstract: The framework of [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}] built from uranium polyhedra sheets pillared by Ni-centered octahedra.

  12. Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal {beta} Double-Prime -(BEDT-TTF){sub 4}H{sub 3}O[Fe(C{sub 2}O{sub 4}){sub 3}] {center_dot} C{sub 6}H{sub 4}Cl{sub 2}

    SciTech Connect

    Zorina, L. V.; Prokhorova, T. G.; Simonov, S. V. Khasanov, S. S.; Shibaeva, R. P.; Manakov, A. I.; Zverev, V. N.; Buravov, L. I.; Yagubskii, E. B.


    The {beta} Double-Prime -(BEDT-TTF){sub 4}A{sup I}[M{sup III}(C{sub 2}O{sub 4}){sub 3}] {center_dot} G(A{sup I}=NH{sub 4}{sup +}, H{sub 3}O{sup +}, K{sup +}, Rb{sup +}; M{sup III}=Fe, Cr; G = 'guest' solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C{sub 6}H{sub 4}Cl{sub 2})-containing conductor of this family, namely, {beta} Double-Prime -(BEDT-TTF){sub 4}H{sub 3}O[Fe(C{sub 2}O{sub 4}){sub 3}] {center_dot} C{sub 6}H{sub 4}Cl{sub 2}, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) A, b= 19.991(2) A, c= 35.441(3) A, {beta} = 92.87(1) Degree-Sign , V= 7374(1) A{sup 3}, space groupC2/c, and Z = 4. In the temperature range 0.5 and 2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the {beta} Double-Prime -(BEDT-TTF){sub 4}A{sup I}[M{sup III}(C{sub 2}O{sub 4}){sub 3}] {center_dot} G crystals are analyzed.

  13. Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal {beta}''-(BEDT-TTF){sub 4}H{sub 3}O[Fe(C{sub 2}O{sub 4}){sub 3}] . C{sub 6}H{sub 4}Cl{sub 2}

    SciTech Connect

    Zorina, L. V. Prokhorova, T. G.; Simonov, S. V. Khasanov, S. S.; Shibaeva, R. P.; Manakov, A. I.; Zverev, V. N.; Buravov, L. I.; Yagubskii, E. B.


    The {beta}''-(BEDT-TTF){sub 4}A{sup I}[M{sup III}(C{sub 2}O{sub 4}){sub 3}] . G(A{sup I}=NH{sub 4}{sup +}, H{sub 3}O{sup +}, K{sup +}, Rb{sup +}; M{sup III}=Fe, Cr; G = 'guest' solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C{sub 6}H{sub 4}Cl{sub 2})-containing conductor of this family, namely, {beta}''-(BEDT-TTF){sub 4}H{sub 3}O[Fe(C{sub 2}O{sub 4}){sub 3}] . C{sub 6}H{sub 4}Cl{sub 2}, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) A, b= 19.991(2) A, c= 35.441(3) A, {beta} = 92.87(1){sup o}, V= 7374(1) A{sup 3}, space groupC2/c, and Z = 4. In the temperature range 0.5 and 2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the {beta}''-(BEDT-TTF){sub 4}A{sup I}[M{sup III}(C{sub 2}O{sub 4}){sub 3}] . G crystals are analyzed.

  14. Impact of a Mixed Oxide’s Surface Composition and Structure on Its Adsorptive Properties: Case of the (Fe,Cr)3O4sub>(111) Termination of the α-(Fe,Cr)2O3(0001) Surface

    SciTech Connect

    Henderson, Michael A.; Engelhard, Mark H.


    Characterization of an α-(Fe0.75,Cr0.25)2O3(0001) mixed oxide single crystal surface was conducted using x-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD). After sputter/anneal cleaning in ultra-high vacuum (UHV), the mixed oxide surface became terminated with a magnetite-(111) structure based on the presence of (2x2) spots in LEED and Fe2+ in XPS. The composition of the surface was close to that of M3O4sub> based on XPS, with the metal (M) content of Fe2+/3+ and Cr3+ being close to 1.4:1, despite the fact that the film’s bulk was 3:1 with respect to the metal cations. The enrichment of the surface with Cr was not altered by high temperature oxidation in UHV, but could be returned to that of the bulk film composition by exposure to the ambient. Adsorption of various probe molecules (NO, O2, CO2 and H2O) was used to identify the active cation sites present in the (Fe,Cr)3O4sub>(111) terminated surface. Although XPS and SIMS both indicated that the near-surface region was enriched in Cr3+, no adsorption states typically associated with Cr3+ sites on α-Cr2O3 single crystal surfaces were detected. Instead, the TPD behaviors of O2 and CO2 pointed toward the main active sites being Fe2+ and Fe3+, with O2 preferentially adsorbing at the former and CO2 at the latter. NO was observed to bind at both Fe2+ and Fe3+ sites, and H2O TPD looked nearly identical to that for H2O on the Fe3O4sub>(111) surface. Competition for adsorption sites between coadsorbed combinations of CO2, O2, H2O and NO corroborated these

  15. Synthesis and structure of a heterometallic cluster with a novel layered structure: (W(CO)/sub 5/SnClFe(CO)/sub 4/)/sub 2/(Na/sub 2/((C/sub 2/H/sub 5/)/sub 2/O)/sub 4/(C/sub 4/H/sub 8/O/sub 2/))

    SciTech Connect

    Balch, A.L.; Olmstead, M.M.; Oram, D.P.


    In an attempt to create an example of substituent-free complex derived from Sn(II), the reaction between (OC)/sub 5/WSnCl/sub 2/(tetrahydrofuran) and Fe(CO)/sub 4//sup /minus/2/ was studied. Instead of the expected compound (OC)/sub 5/WSn=Fe(CO)/sub 4/, the dimer (W(CO)/sub 5/SnClFe(CO)/sub 4/)/sub 2/Na/sub 2/(C/sub 2/H/sub 5/)O/sub 4/(C/sub 4/H/sub 8/O/sub 2/) was the product formed. The properties and structure of this dimer are reported herein. 17 refs., 3 figs., 3 tabs.

  16. In Situ Foaming of Porous (La 0.6 Sr 0.4sub> ) 0.98 (Co 0.2 Fe 0.8 ) O 3−δ (LSCF) Cathodes for Solid Oxide Fuel Cell Applications

    SciTech Connect

    Gandavarapu, Sodith; Sabolsky, Edward; Sabolsky, Katarzyna; Gerdes, Kirk


    A binder system containing polyurethane precursors was used to in situ foam (direct foam) a (La{sub 0.6}Sr{sub 0.4}){sub 0.98} (Co{sub 0.2} Fe{sub 0.8}) O{sub 3-{ delta}} (LSCF) composition for solid oxide fuel cell (SOFC) cathode applications. The relation between in situ foaming parameters on the final microstructure and electrochemical properties was characterized by microscopy and electrochemical impedance spectroscopy (EIS), respectively. The optimal porous cathode architecture was formed with a 70 vol% solids loading within a polymer precursor composition with a volume ratio of 8:4:1 (isocyanate: PEG: surfactant) in a terpineol-based ink vehicle. The resultant microstructure displayed a broad pore size distribution with highly elongated pore structure.

  17. Hydrothermal synthesis, crystal structure, and magnetic properties of Cs[(V[sub 2]O[sub 3])(HPO[sub 4])[sub 2](H[sub 2]O)], a mixed-valence vanadium (IV, V) hydrogen phosphate with a one-dimensional (-V[sup IV]-O-V[sup V]-O-) chain of corner-sharing VO[sub 6] octahedra

    SciTech Connect

    Haushalter, R.C. ); Wang, Z. Princeton Univ., Princeton, NJ ); Thompson, M.E. ); Zubieta, J. ); O'Connor, C.J. )


    The hydrothermal reaction of Cs[sub 4]V[sub 2]O[sub 7], V, H[sub 3]PO[sub 4], H[sub 2]O, and Bu[sub 4]NBr in the molar ratio 4.5:1:41:3150:1 at 200[degrees]C for 48 hr yielded the red-brown cesium vanadium phosphate Cs[(V[sub 2]O[sub 3])(HPO[sub 4])[sub 2](H[sub 2]O)], a mixed-valence V(IV, V) species. The structure contains corner-sharing vanadium octahedra and phosphorus tetrahedra with unusual 1-D (-V[sup IV]-O-V[sup v]-O-)[infinity] chains formed from VO[sub 6] octahedra sharing opposite corners. These chains are connected through tridentate bridging (HPO[sub 4])[sup 2[minus

  18. Reversible Exsolution of Nanometric Fe2O3 Particles in BaFe2-x(PO4sub>)2 (0 ≤ x ≤ 2/3):The Logic of Vacancy Ordering in Novel Metal-Depleted Two-Dimensional Lattices

    SciTech Connect

    Alcover, Ignacio Blazquez; David, Rénald; Daviero-Minaud, Sylvie; Filimonov, Dmitry; Huvé, Marielle; Roussel, Pascal; Kabbour, Houria; Mentré, Olivier


    We show here that the exsolution of Fe2+ ions out of two-dimensional (2D) honeycomb layers of BaFe2(PO4sub>)2 into iron-deficient BaFe2–x(PO4sub>)2 phases and nanometric α-Fe2O3 (typically 50 nm diameter at the grain surface) is efficient and reversible until x = 2/3 in mild oxidizing/reducing conditions. It corresponds to the renewable conversion of 12 wt % of the initial mass into iron oxide. After analyzing single crystal X-ray diffraction data of intermediate members x = 2/7, x = 1/3, x = 1/2 and the ultimate Fe-depleted x = 2/3 term, we then observed a systematic full ordering between Fe ions and vacancies (VFe) that denote unprecedented easy in-plane metal diffusion driven by the Fe2+/Fe3+ redox. Besides the discovery of a diversity of original depleted triangular {Fe2/3+2–xO6} topologies, we propose a unified model correlating the x Fe-removal and the experimental Fe/VFe ordering into periodic one-dimensional motifs paving the layers, gaining insights into predictive crystahemistry of complex low dimensional oxides. When we increased the x values it led to a progressive change of the materials from 2D ferromagnets (Fe2+) to 2D ferrimagnets (Fe2/3+) to antiferromagnets for x = 2/3 (Fe3+).

  19. Defect-Tolerant Diffusion Channels for Mg2+ Ions in Ribbon-Type Borates: Structural Insights into Potential Battery Cathodes MgVBO4sub> and Mgx Fe2–xB2O5

    SciTech Connect

    Bo, Shou-Hang; Grey, Clare P.; Khalifah, Peter G.


    The reversible room temperature intercalation of Mg2+ ions is difficult to achieve, but may offer substantial advantages in the design of next-generation batteries if this electrochemical process can be successfully realized. Two types of quadruple ribbon-type transition metal borates (MgxFe2-xB2O5 and MgVBO4sub>) with high theoretical capacities (186 mAh/g and 360 mAh/g) have been synthesized and structurally characterized through the combined Rietveld refinement of synchrotron and time-of-flight neutron diffraction data. Neither MgVBO4 sub> nor MgxFe2-xB2O5 can be chemically oxidized at room temperature, though Mg can be dynamically removed from the latter phase at elevated temperatures (approximately 200 - 500 °C). Findings show that Mg diffusion in the MgxFe2-xB2O5 structure is more facile for the inner two octahedral sites than for the two outer octahedral sites in the ribbons, a result supported by both the refined site occupancies after Mg removal and by bond valence sum difference map calculations of diffusion paths in the pristine material. Mg diffusion in this pyroborate MgxFe2-xB2O5 framework is also found to be tolerant to the presence of Mg/Fe disorder since Mg ions can diffuse through interstitial channels which bypass Fe-containing sites.

  20. Eu3Ir2In15: A mixed-valent and vacancy-filled variant of the Sc5Co4sub>Si10 structure type with anomalous magnetic properties

    SciTech Connect

    Sarkar, Sumanta; Jana, Rajkumar; Siva, Ramesh; Banerjee, Swastika; Pati, Swapan K.; Balasubramanian, Mahalingam; Peter, Sebastian C.


    Here, a new compound, Eu3Ir2In15 has been synthesized using indium as an active metal flux. The compound crystallizes in tetragonal P4/mbm space group with lattice parameters, a = 14.8580(4) Å, b = 14.8580(4) Å, c = 4.3901(2) Å. It was further characterized by SEM-EDX studies. The temperature dependent magnetic susceptibility suggests that Eu in this compound is exclusively in divalent state. The effective magnetic moment (μeff) of this compound is 7.35 μB/Eu ion with paramagnetic Curie temperature (θp) of -28 K suggesting antiferromagnetic interaction. The mixed valent nature of Eu observed in magnetic measurements was confirmed by XANES measurements. The compound undergoes demagnetization at a low magnetic field (10 Oe), which is quite unusual for Eu based intermetallic compounds. Temperature dependent resistivity studies reveal that the compound is metallic in nature. A comparative study was made between Eu3Ir2In15 and hypothetical vacancy variant Eu5Ir4sub>In10 which also crystallizes in the same crystal structure However our computational studies along with control experiments suggest that the latter is thermodynamically less feasible compared to the former and hence we proposed that it is highly unlikely that a RE5T4sub>X10 would exist with X as a group 13 elements.

  1. Chemical bond parameters and photoluminescence of a natural-white-light Ca{sub 9}La(VO{sub 4}){sub 7}:Tm{sup 3+},Eu{sup 3+} with one O{sup 2−}→V{sup 5+} charge transfer and dual f-f transition emission centers

    SciTech Connect

    Li, Ling; Liu, Xiao Guang; Noh, Hyeon Mi; Jeong, Jung Hyun


    The relationship between the photoluminescence properties and the crystal structure of undoped, Eu{sup 3+} or/ and Tm{sup 3+} singly or codoped Ca{sub 9}La(VO{sub 4}){sub 7} (CLaVO) samples was discussed. Under the excitation of UV light, CLaVO:Tm{sup 3+}, CLaVO, and CLaVO:Eu{sup 3+} exhibit the characteristic emissions of Tm{sup 3+} ({sup 1}G{sub 4}→{sup 3}H{sub 6}, blue), O{sup 2−}→V{sup 5+} charge transfer (CT), and Eu{sup 3+} ({sup 5}D{sub 0}→{sup 7}F{sub 2}, red), respectively. By adjusting the doping concentration of Tm{sup 3+} and Eu{sup 3+} ions in CLaVO, a natural white emission in a single composition with the color temperature at 6181 K was obtained. Based on the dielectric theory of complex crystal, the chemical bond parameters of La-O and V-O bonds were quantitatively calculated. The standard deviation of environmental factor of every bond (EFSD), which can be expressed as σ(h{sub e{sub i}})=√((1/N)∑{sub i=1}{sup N}(h{sub e{sub i}}−μ){sup 2}) (h{sub e{sub i}}=(f{sub c{sub i}}α{sub b{sub i}}){sup 1/2}Q{sub B{sub i}} and μ=(1/N)∑{sub i=1}{sup N}h{sub e{sub i}}), was proposed to quantitatively express the distortion degree of VO{sub 4}{sup 3−} from that of an ideal tetrahedron. The maximum change of EFSD comes from the [VO{sub 4}]{sup −} tetrahedra in CLaVO sample by comparison with that of EFSD of isostructural Ca{sub 9}Gd(VO{sub 4}){sub 7}. This is possible the key reason that the undoped CLaVO sample has self-activated emission while the self-activated emission of its isostructural Ca{sub 9}Gd(VO{sub 4}){sub 7} sample cannot be found. The quantitative calculation also demonstrated that the broad excitation bands at 319 nm in CLaVO:Tm and at 335 nm in CLaVO:Eu were due to the O-V2 and O-V3 (overlap with O-V2) CT, not the CT energy of O{sup 2−}-Eu1{sup 3+} (O{sup 2−}-Tm1{sup 3+}), O{sup 2−}-Eu2{sup 3+} (O{sup 2−}-Tm2{sup 3+}), and O{sup 2−}-Eu3{sup 3+} (O{sup 2−}-Tm3{sup 3+}). The environmental factors surrounding the

  2. Sodium doping effect on physicochemical properties of K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1) for the determination of mercury(II): Application in seawater samples

    SciTech Connect

    Lahrich, Sara; Manoun, Bouchaib; Mhammedi, Moulay Abderrahim El


    Highlights: • The apatite, K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1), was synthesized using reaction solid. • The obtained apatite was used to determine mercury in seawater samples from Morocco. • The effect of doping sodium into apatite on physic-chemical parameters was studied. • The influence of the electrochemical variables was investigated to determine mercury. - Abstract: A new chemically modified electrode was synthesized for the determination of mercury(II) using differential pulse anodic stripping voltammetry (DPASV). The electrode was modified by lacunar apatite K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1) synthesized using solid reaction. These powders were crystallized in the hexagonal system, space group P6{sub 3}/m. The effect of sodium content on structural, thermodynamic and electrochemical properties of prepared apatite has been studied. Therefore, the best results was obtained using NaCaPb{sub 3}(PO{sub 4}){sub 3} (x = 1) as modifier of carbon paste electrode for the electrochemical detection of mercury(II). The later ions were preconcentrated on the surface of the modified electrode and oxidized at 0.06 V vs. Ag/AgCl. The electroanalytical procedure comprises of two steps: the chemical accumulation of the analyte under open-circuit conditions followed by the electrochemical detection of the preconcentrated species using differential pulse voltammetry. The different parameters that govern the two steps were optimized. A linear response was obtained in the concentration range from 1.0 mol L{sup −1} × 10{sup −4} mol L{sup −1} to 2.0 mol L{sup −1} × 10{sup −7} mol L{sup −1} Hg(II) after activation of the electrode surface under the optimized conditions. The standard deviation was evaluated in a high and low concentration of mercury(II). The values ​​obtained for seven consecutive measurements were 1.24% and 5.07% of 1.0 mol L{sup −1} × 10{sup −4} mol L{sup −1} and 5.0 mol

  3. Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln==Sm, Eu, Gd) and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln==Tb, Dy, Ho)

    SciTech Connect

    Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian


    Solvothermal reactions of Ln{sub 2}O{sub 3}, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln{sub 2}O{sub 3} oxides were converted to [Ln(dien){sub 2}]{sup 3+} complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS{sub 4} unit. In 1−3, the AsS{sub 4} units interconnect the [Ln(dien){sub 2}]{sup 3+} cations via Ln−S bonds as tridentate μ-1κ,2κ{sup 2}-AsS{sub 4} bridging ligands, resulting in the neutral coordination polymers [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln1). In 4−6, the AsS{sub 4} units coordinate with the Ln{sup 3+} ion of [Ln(dien){sub 2}]{sup 3+} as 1κ{sup 2}-AsS{sub 4} chelating ligands to form neutral coordination compounds [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln2). The Ln{sup 3+} ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln{sup 3+} ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] were prepared by solvothermal methods and the soft Lewis basic AsS{sub 4}{sup 3–} ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS{sub 4} ligand coordinate Ln{sup 3+} ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors

  4. X-ray powder diffraction, vibration and thermal studies of [A{sub 0.92}(NH{sub 4}){sub 0.08}]{sub 2}TeCl{sub 4}Br{sub 2} with A = Cs, Rb: Influence of mixed cationic and anionic substitutions

    SciTech Connect

    Aribia, W. Ben; Abdelmouleh, M.; Kabadou, A.; Van Der Lee, A.


    Graphical abstract: The structures of [A{sub 0.92}(NH{sub 4}){sub 0.08}]{sub 2}TeCl{sub 4}Br{sub 2} with A = Cs, Rb belong to the tetragonal {beta}-K{sub 2}SnCl{sub 6} structure type. Highlights: Black-Right-Pointing-Pointer The two new compound crystallises in P4/mnc tetragonal space group. Black-Right-Pointing-Pointer The structure is considered as isolated octahedred TeCl{sub 4}Br{sup 2-}. Black-Right-Pointing-Pointer The octahedra connected by ionic and hydrogen bonding through the Cs/Rb or N atoms. Black-Right-Pointing-Pointer A DTA/TGA experiment reveals one endothermic peak at 780 K for these compounds. Black-Right-Pointing-Pointer One endothermic peak is detected at around 213 K by DSC experiment. -- Abstract: The crystal structures of [A{sub 0.92}(NH{sub 4}){sub 0.08}]{sub 2}TeCl{sub 4}Br{sub 2} with A = Cs, Rb have been determined using X-ray powder diffraction techniques. The two compounds crystallize in the tetragonal space group P4/mnc, with the unit cell parameters: a = 7.452(1) Angstrom-Sign , c = 10.544(3) Angstrom-Sign , Z = 2 and a = 7.315(2) Angstrom-Sign , c = 10.354(4) Angstrom-Sign , Z = 2 in the presence of Cs and Rb, respectively. These two compounds have an antifluorite-type arrangement of NH{sub 4}{sup +}/Rb{sup +}/Cs{sup +} and octahedral TeCl{sub 4}Br{sub 2}{sup 2-} anions. The stability of these structure is by ionic and hydrogen bonding contacts: A Midline-Horizontal-Ellipsis Cl, A Midline-Horizontal-Ellipsis Br and N-H Midline-Horizontal-Ellipsis Cl, N-H Midline-Horizontal-Ellipsis Br. The different vibrational modes of these powders were analysed by FTIR and Raman spectroscopic studies. A DTA/TGA experiment reveals one endothermic peak at 780 K implicating the decomposition of the sample. At low temperature, one endothermic peak in thermal behavior is detected at around 213 K by DSC experiment. This transition was confirmed by dielectric measurements.

  5. Synthesis, crystal structures, phase transition characterization and thermal decomposition of a new dabcodiium hexaaquairon(II) bis(sulfate): (C{sub 6}H{sub 14}N{sub 2})[Fe(H{sub 2}O){sub 6}](SO{sub 4}){sub 2}

    SciTech Connect

    Yahyaoui, Samia; Rekik, Walid; Naili, Houcine; Mhiri, Tahar; Bataille, Thierry


    The crystal structures of 1,4-diazabicyclo[2.2.2]octane (dabco)-templated iron sulfate, (C{sub 6}H{sub 14}N{sub 2})[Fe(H{sub 2}O){sub 6}](SO{sub 4}){sub 2}, were determined at room temperature and at -173 deg. C from single-crystal X-ray diffraction. At 20 deg. C, it crystallises in the monoclinic symmetry, centrosymmetric space group P2{sub 1}/n, Z=2, a=7.964(5), b=9.100(5), c=12.065(5) A, {beta}=95.426(5) deg. and V=870.5(8) A{sup 3}. The structure consists of [Fe(H{sub 2}O){sub 6}]{sup 2+} and disordered (C{sub 6}H{sub 14}N{sub 2}){sup 2+} cations and (SO{sub 4}){sup 2-} anions connected together by an extensive three-dimensional H-bond network. The title compound undergoes a reversible phase transition of the first-order at -2.3 deg. C, characterized by DSC, dielectric measurement and optical observations, that suggests a relaxor-ferroelectric behavior. Below the transition temperature, the compound crystallizes in the monoclinic system, non-centrosymmetric space group Cc, with eight times the volume of the ambient phase: a=15.883(3), b=36.409(7), c=13.747(3) A, {beta}=120.2304(8){sup o}, Z=16 and V=6868.7(2) A{sup 3}. The organic moiety is then fully ordered within a supramolecular structure. Thermodiffractometry and thermogravimetric analyses indicate that its decomposition proceeds through three stages giving rise to the iron oxide. - Graphical abstract: The new dabcodiium hexaaquairon(II) bis(sulfate), (C{sub 6}H{sub 14}N{sub 2})[Fe(H{sub 2}O){sub 6}](SO{sub 4}){sub 2}, was prepared and characterized. It exhibits a supramolecular structure and undergoes a reversible order-disorder phase transition at -2.3 deg. C.

  6. Interfacial charge-mediated non-volatile magnetoelectric coupling in Co0.3Fe0.7/Ba0.6Sr0.4sub>TiO3/Nb:SrTiO3 multiferroic heterostructures

    SciTech Connect

    Zhou, Ziyao; Howe, Brandon M.; Liu, Ming; Nan, Tianxiang; Chen, Xing; Mahalingam, Krishnamurthy; Sun, Nian X.; Brown, Gail J.


    The central challenge in realizing non-volatile, E-field manipulation of magnetism lies in finding an energy efficient means to switch between the distinct magnetic states in a stable and reversible manner. In this work, we demonstrate using electrical polarization-induced charge screening to change the ground state of magnetic ordering in order to non-volatilely tune magnetic properties in ultra-thin Co0.3Fe0.7/Ba0.6Sr0.4sub>TiO3/Nb:SrTiO3 (001) multiferroic heterostructures. A robust, voltage-induced, non-volatile manipulation of out-of-plane magnetic anisotropy up to 40 Oe is demonstrated and confirmed by ferromagnetic resonance measurements. This discovery provides a framework for realizing charge-sensitive order parameter tuning in ultra-thin multiferroic heterostructures, demonstrating great potential for delivering compact, lightweight, reconfigurable, and energy-efficient electronic devices.

  7. Localization of conduction electrons and the magnetic properties of the molecular metals {beta}''-(BEDT-TTF){sub 4}NH{sub 4}[M(C{sub 2}O{sub 4}){sub 3}] . DMF (M = Cr{sup 3+}, Fe{sup 3+})

    SciTech Connect

    Morgunov, R. B. Shibaeva, R. P.; Yagubskii, E. B.; Kato, T.; Tanimoto, Y


    Quasi-two-dimensional organic metals {beta}''-(BEDT-TTF){sub 4}NH{sub 4}[M(C{sub 2}O{sub 4}){sub 3}] . DMF containing the oxalate complexes of Cr{sup 3+} or Fe{sup 3+} ions between the conducting organic layers of the BEDT-TTF molecules are studied by EPR spectroscopy, and the contributions of these metallic complexes, conduction electrons, and non-equilibrium lattice defects to the magnetic susceptibility are determined. An analysis of the temperature dependence of the magnetic susceptibility and the EPR line shape has revealed partial localization of conduction electrons at T < 20 K in the crystals with Cr{sup 3+} ions. The size of the localization region is close to the size of an individual BEDT-TTF molecule. The localization effect weakens as nonequilibrium defects disappear during long-term storage at room temperature. The localization of conduction electrons is found to be accompanied by the appearance of weak antiferromagnetic interaction between the Cr{sup 3+} ions at T < 20 K, which disappears when Fe{sup 3+} ions substitute for Cr{sup 3+} ions.

  8. Solid solution between Al-ettringite and Fe-ettringite (Ca{sub 6}[Al{sub 1-x}Fe{sub x}(OH){sub 6}]{sub 2}(SO{sub 4}){sub 3}.26H{sub 2}O)

    SciTech Connect

    Moeschner, Goeril Lothenbach, Barbara; Winnefeld, Frank; Ulrich, Andrea; Figi, Renato; Kretzschmar, Ruben


    The solid solution between Al- and Fe-ettringite Ca{sub 6}[Al{sub 1-x}Fe{sub x}(OH){sub 6}]{sub 2}(SO{sub 4}){sub 3}.26H{sub 2}O was investigated. Ettringite phases were synthesized at different Al/(Al + Fe)-ratios (= X{sub Al,total}), so that X{sub Al} increased from 0.0 to 1.0 in 0.1 unit steps. After 8 months of equilibration, the solid phases were analyzed by X-ray diffraction (XRD) and thermogravimetric analysis (TGA), while the aqueous solutions were analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). XRD analyses of the solid phases indicated the existence of a miscibility gap between X{sub Al,total} = 0.3-0.6. Some of the XRD reflections showed two overlapping peaks at these molar ratios. The composition of the aqueous solutions, however, would have been in agreement with both, the existence of a miscibility gap or a continuous solid solution between Al- and Fe-ettringite, based on thermodynamic modeling, simulating the experimental conditions.

  9. Itinerant ferromagnetism in the As 4p conduction band of Ba0.6K0.4sub>Mn2As2 identified by x-ray magnetic circular dichroism

    SciTech Connect

    Ueland, B. G.; Pandey, Abhishek; Lee, Y.; Sapkota, A.; Choi, Y.; Haskel, D.; Rosenberg, R. A.; Lang, J. C.; Harmon, B. N.; Johnston, D. C.; Kreyssig, A.; Goldman, A. I.


    In this study, x-ray magnetic circular dichroism (XMCD) measurements on single-crystal and powder samples of Ba0.6K0.4sub>Mn2As2 show that the ferromagnetism below TC ≈ 100 K arises in the As 4p conduction band. No XMCD signal is observed at the Mn x-ray absorption edges. Below TC, however, a clear XMCD signal is found at the As K edge which increases with decreasing temperature. The XMCD signal is absent in data taken with the beam directed parallel to the crystallographic c axis indicating that the orbital magnetic moment lies in the basal plane of the tetragonal lattice. These results show that the previously reported itinerant ferromagnetism is associated with the As 4p conduction band and that distinct local-moment antiferromagnetism and itinerant ferromagnetism with perpendicular easy axes coexist in this compound at low temperature.

  10. Enhanced magnetic behavior, exchange bias effect, and dielectric property of BiFeO{sub 3} incorporated in (BiFeO{sub 3}){sub 0.50} (Co{sub 0.4}Zn{sub 0.4}Cu{sub 0.2} Fe{sub 2}O{sub 4}){sub 0.5} nanocomposite

    SciTech Connect

    Mukhopadhyay, K.; Mahapatra, A. S.; Sutradhar, S.; Chakrabarti, P. K.


    Nanoparticles of BiFeO{sub 3} (BFO) are incorporated in the nanocomposite of (BiFeO{sub 3}){sub 0.50} (Co{sub 0.4}Zn{sub 0.4}Cu{sub 0.2} Fe{sub 2}O{sub 4}){sub 0.5}, (BFO-CZCF) and these are prepared by chemical route. The formation of pure crystallographic phase of each component (BFO and CZCF) in the nanocomposite of BFO-CZCF has been confirmed by Rietveld analysis of the X-ray diffractograms using FULLPROF program. Morphology, average particle size and its distribution, crystallographic phase etc. are obtained from the high-resolution transmission electron microscopy of BFO-CZCF. Magnetic measurements of BFO-CZCF have been carried out to explore the modulation of magnetic behavior of BFO in BFO-CZCF. Interestingly, magnetization of BFO-CZCF has been drastically enhanced compared to that of the pristine BFO. An exchange bias effect is also observed in the M vs. H loops of BFO-CZCF recorded in field cooled and zero field cooled conditions, which suggest that nanoparticles of BFO (AFM) are encapsulated by nanoparticles of CZCF (FM) in BFO-CZCF. Thermal variation of dielectric constant of BFO-CZCF is recorded in the range of 300 to 1073 K and a ferroelectric to paraelectric transition is observed at ∼728 K. Enhanced magnetic property of BFO would quite interesting for this important multiferroic.

  11. Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–y Mn y O 4sub> (0.4 ≤ y ≤ 1)

    SciTech Connect

    Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam


    The thermal conversion of chemically delithiated layered Li0.5Ni1-yMnyO2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi2-yMnyO4sub> (0.4 ≤ y ≤ 1) has been systematically investigated. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. The study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.

  12. Energetics of phosphate frameworks containing zinc and cobalt: NaZnPO{sub 4}, NaH(ZnPO{sub 4}){sub 2}, NaZnPO{sub 4}.H{sub 2}O, NaZnPO{sub 4}.4/3 H{sub 2}O, and NaCo{sub x}Zn{sub 1-x}PO{sub 4}.4/3 H{sub 2}O

    SciTech Connect

    Le, So-Nhu; Navrotsky, Alexandra


    Differential scanning calorimetry and high temperature oxide melt solution calorimetry were used to study the enthalpy of the {alpha}-{beta} phase transformation of NaZnPO{sub 4} and enthalpies of formation of {alpha}-NaZnPO{sub 4}, NaH(ZnPO{sub 4}){sub 2}, NaZnPO{sub 4}.H{sub 2}O, and NaCo{sub x}Zn{sub 1-x}PO{sub 4}.4/3 H{sub 2}O (x=0, 0.1, 0.2, 0.3). The enthalpies of formation from the oxides of cobalt substituted in NaZnPO{sub 4}.4/3 H{sub 2}O do not depend on cobalt content, confirming similar acid-base interactions for Zn-PO{sub 4} and Co-PO{sub 4}. While water molecules stabilize zinc phosphate frameworks through solvating a cation or forming extra hydrogen bonds, the partial substitution of water for sodium oxide to form NaH(ZnPO{sub 4}){sub 2} represents the formation of an acidic compound with weaker acid-base interactions and less exothermic enthalpy of formation from oxides than Na{sub 2}(ZnPO{sub 4}){sub 2}. - Graphical abstract: Relative stability of NaZnPO{sub 4} dense phases, open frameworks, and hydrated frameworks. Enthalpy of interaction between water and NaZnPO{sub 4} frameworks is presented by reaction: NaZnPO{sub 4} (cr, open framework) + nH{sub 2}O (l) {yields} NaZnPO{sub 4}.nH{sub 2}O (cr, hydrated framework)

  13. Synthesis of titanium, zirconium, and hafnium complexes that contain diamido donor ligands of the type [(t-BuN-o-C{sub 6}H{sub 4}){sub 2}O]{sup 2{minus}} and an evaluation of activated versions for the polymerization of 1-hexene

    SciTech Connect

    Schrock, R.R.; Baumann, R.; Reid, S.M.; Goodman, J.T.; Stumpf, R.; Davis, W.M.


    Titanium, zirconium, and hafnium dialkyl complexes that contain the [(t-Bu-d{sub 6}-N-o-C{sub 6}H{sub 4}){sub 2}O]{sup 2{minus}} ([t-BuNON]{sup 2{minus}}) ligand have been prepared. Only [T-BuNON]TiMe{sub 2} could be isolated, but [t-BuNON]ZrR{sub 2} and [t-BuNON]HfR{sub 2} complexes could be isolated in which (for example) R = Me, Et, or i-Bu. X-ray studies showed [t-BuNON]MMe{sub 2} structures (M = Tk or Zr) to be of the twisted fac variety in which two amido nitrogens occupy equatorial positions in a distorted trigonal bypyramid. However, in solution all such species show equivalent alkyl groups on the NMR time scale as a consequence of formation of an intermediate mer structure that contains a planar oxygen donor. In analogous complexes that contain the {l_brace}[Me(CD{sub 3}){sub 2}CNC{sub 6}H{sub 4}][Me(CD{sub 3}){sub 2}CN-2,4-Me{sub 2}C{sub 6}H{sub 2}]O{r_brace}{sup 2{minus}} or {l_brace}[Me(CD{sub 3}){sub 2}CNC{sub 6}H{sub 4}][Me(CD{sub 3}){sub 2}-N-2-EtC{sub 6}H{sub 3}]O{r_brace}{sup 2{minus}} ligand the two metal alkyl groups are inequivalent on the NMR time scale. Addition of trimethylphosphine to [t-BuNON]Zr(CH{sub 2}CH{sub 3}){sub 2} yields structurally characterized pseudooctahedral [t-BuNON]Zr({eta}{sup 2}-C{sub 2}H{sub 4})(PMe{sub 3}){sub 2}. Addition of B(C{sub 6}F{sub 5}){sub 3} to [t-BuNON]ZrMe{sub 2} yields structurally characterized {l_brace}[t-BuNON]ZrMe{r_brace}[MeB(C{sub 6}F{sub 5}){sub 3}], while addition of [PhNMe{sub 2}H]-[B(C{sub 6}F{sub 4}){sub 4}] to [t-BuNON]ZrMe{sub 2} in bromobenzene-d{sub 5} generates {l_brace}[t-BuNON]ZrMe(PhNMe{sub 2}){r_brace}-[B(C{sub 6}F{sub 5}){sub 4}], which is an active catalyst for the polymerization of up to 500 equiv of 1-hexene in a living manner at 0 C. The analogous hafnium systems are not as well behaved, since the dimethylaniline is insufficiently labile. No polymerization activity is observed for activated titanium dialkyl complexes. Polymerization activity is quenched upon addition of THF or

  14. Performances of YBaCo1.4sub>Cu0.6O5+δ–Ce0.8Sm0.2O1.9 composite cathodes for intermediate-temperature solid oxide fuel cells

    SciTech Connect

    Wang, Lizhong; Peng, Lu; Hu, Michael Z.; Lü, Shiquan; Meng, Xiangwei; Yu, Bo; Wei, Maobin; Fan, Hougang; Yang, Lili


    In this paper, the electrochemical properties of YBaCo1.4sub>Cu0.6O5+δ–xCe0.8Sm0.2O1.9 (YBCC–xSDC, x=20, 30, 40, 50 wt%) have been investigated for the potential application in intermediate-temperature solid oxide fuel cells (IT-SOFCs). No chemical reactions between YBCC cathode and SDC electrolyte, and YBCC and La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) occur. The thermal expansion coefficient (TEC) of YBCC cathode decreases with SDC addition. The TEC of YBCC–30SDC cathode is 13.60×10–6 K-1 from 30 to 850 °C in air and it exhibits the best electrochemical performance among the YBCC–xSDC cathodes. The polarization resistance (Rp) of YBCC–30SDC is 0.027 Ω cm2 at 850 °C, 0.044 Ω cm2 at 800 °C and 0.075 Ω cm2 at 750 °C. The maximum power density value of electrolyte-based cell with YBCC–30SDC cathode is 662, 483 and 319 mW cm-2 at 850, 800 and 750 °C, respectively. Finally, preliminary results indicate that YBCC–30SDC is especially promising as a cathode for IT-SOFCs.

  15. Characterization and electrochemical performance of (Ba{sub 0.6}Sr{sub 0.4}){sub 1-x}La{sub x}Co{sub 0.6}Fe{sub 0.4}O{sub 3-{delta}} (x = 0, 0.1) cathode for intermediate temperature solid oxide fuel cells

    SciTech Connect

    Ding, Xifeng; Kong, Xin; Jiang, Jinguo; Cui, Chong; Guo, Xinxin


    La-doped Ba{sub 0.6}Sr{sub 0.4}Co{sub 0.6}Fe{sub 0.4}O{sub 3-{delta}} perovskites were synthesized and investigated as new cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). The structural characteristics, thermal expansion coefficient (TEC), electrical conductivity and electrochemical properties were characterized by X-ray diffraction (XRD), dilatometry, DC four-terminal method, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The TEC of (Ba{sub 0.6}Sr{sub 0.4}){sub 0.9}La{sub 0.1}Co{sub 0.4}Fe{sub 0.6}O{sub 3-{delta}} (BSLCF) was 14.9 x 10{sup -6} K{sup -1} at 30-800 {sup o}C, lower than Ba{sub 0.6}Sr{sub 0.4}Co{sub 0.4}Fe{sub 0.6}O{sub 3-{delta}} (BSCF) of 15.6 x 10{sup -6} K{sup -1}. The electrical conductivity of BSCF was improved by La-doping, e.g. a value of 122 S cm{sup -1} for BSLCF vs. 52 S cm{sup -1} for BSCF at 500{sup o}C, respectively. In addition, La-doping enhanced the electrochemical activity for oxygen reduction reaction. The polarization resistance of BSLCF was 0.18 {Omega} cm{sup 2} at 700 {sup o}C, about a quarter lower than that of BSCF. The improved electrochemical performance of BSLCF should be ascribed to the higher conductivity as well as the improved oxygen adsorption/desorption and oxygen ions diffusion processes.

  16. Synthesis and structure of a new family of 3d-4f heterometallic compounds Rb{sub 7}LnFe{sub 6}O{sub 2}(PO{sub 4}){sub 8} (Ln=Sm, Eu, Gd, Dy): Magnetic properties of the Sm-, Gd-, Dy-derivatives

    SciTech Connect

    Sanjeewa, Liurukara D.; Palmer West, J.; Hwu, Shiou-Jyh


    A new family of mixed lanthanide(III) and iron(III) oxo-phosphate phases, Rb{sub 7}LnFe{sub 6}O{sub 2}(PO{sub 4}){sub 8} (Ln=Sm 1, Eu 2, Gd 3, Dy 4), was isolated by using a high-temperature, solid-state method in molten-salt media. The X-ray single-crystal structure analysis shows that these isomorphic derivatives crystallize in a triclinic space group P-1 (no. 2); Z=1. The 3-D framework of these 3d-4f oxo-phosphates are comprised of LnO{sub 6} octahedral, FeO{sub 5} trigonal bipyramidal (tbp), and {mu}{sub 3}-oxo [Fe{sub 4}O{sub 18}] tetrameric units interconnected through PO{sub 4} tetrahedra. The preliminary results of the temperature-dependent magnetic susceptibility measurements for selected compounds (1, 3, 4) reveal antiferromagnetic-like behavior. 1 shows a weak antiferromagnetric ordering at T{sub N}={approx}7 K while others show little evidence of long-range magnetic order down to 2 K. All three compounds have measured magnetic moments significantly smaller than the expected values. - Graphical abstract: The extended framework is described by the connectivity of three distinct types of paramagnetic units. The temperature-dependent, lower than expected effective magnetic moments are reported. Highlights: Black-Right-Pointing-Pointer A new family of mixed lanthanide(III) and iron(III) oxo-phosphates is isolated. Black-Right-Pointing-Pointer Features PO{sub 4}-linked paramagnetic units of LnO{sub 6}, FeO{sub 5}, and {mu}{sub 3}-oxo [Fe{sub 4}O{sub 18}]. Black-Right-Pointing-Pointer Sm-derivative orders at T{sub N}{approx}7 K while Gd- and Dy-derivatives show absence of order.

  17. Influence of Microstructure and Surface Activation of Dual-Phase Membrane Ce 0.8 Gd 0.2 O 2-δ -FeCo 2 O 4sub> on Oxygen Permeation

    SciTech Connect

    Ramasamy, Madhumidha; Baumann, Stefan; Palisaitis, Justinas; Schulze-Küppers, Falk; Balaguer, Maria; Kim, Daejin; Meulenberg, Wilhelm A.; Mayer, Jochim; Bhave, Ramesh; Guillon, Olivier; Bram, Martin; Stevenson, J.


    In dual-phase oxygen transport membranes we noticed that there is fast-growing interest in research for oxyfuel combustion process application. One such potential candidate is CGO-FCO (60wt% Ce0.8Gd0.2O2-δ-40wt% FeCo2O4) identified to provide good oxygen permeation flux with substantial stability in harsh atmosphere. Dense CGO-FCO membranes of 1mm thickness were fabricated by sintering dry pellets pressed from powders synthesized by one-pot method (modified Pechini process) at 1200 degrees C for 10h. Microstructure analysis indicates presence of a third orthorhombic perovskite phase in the sintered composite. We also identified that the spinel phase tends to form an oxygen deficient phase at the grain boundary of spinel and CGO phases. Surface exchange limitation of the membranes was overcome by La0.6Sr0.4sub>Co0.2Fe0.8O3-δ (LSCF) porous layer coating over the composite. Moreover, the oxygen permeation flux of the CGO-FCO screen printed with a porous layer of 10mthick LSCF is 0.11mL/cm2 per minute at 850 degrees C with argon as sweep and air as feed gas at the rates of 50 and 250mL/min.

  18. Removal of Ca2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn4sub>O5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

    SciTech Connect

    Lohmiller, Thomas; Shelby, Megan L.; Long, Xi; Yachandra, Vittal K.; Yano, Junko


    We studied Ca2+ -depleted and Ca2+ -reconstituted spinach photosystem II using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca2+ ion in the Mn4sub>O5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca2+ -depleted S1 (S1') and S2 (S2') states, the S2'YZ• state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca2+ -reconstituted S1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S1 and S2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca2+ removal are discussed, attributing to the Ca2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to YZ• (D1-Tyr161).

  19. Structure and dynamics of complexes of the uranyl ion with nonamethylimidodiphosphoramide (NIPA). 2. NMR studies of complexes (UO/sub 2/(NIPA)/sub 2/X)(CIO/sub 4/)/sub 2/ with X = H/sub 2/O, MeOH, EtOH, or Me/sub 2/CO

    SciTech Connect

    Rodehueser, L.; Rubini, P.R.; Bokolo, K.; Delpuech, J.J.


    The /sup 31/P and /sup 1/H spectra at -90/sup 0/C of the title uranyl complex ions (prepared as solutions of the solid perchlorates in inert anhydrous organic solvents (CH/sub 3/NO/sub 2/, CH/sub 2/Cl/sub 2/)) reveal a pentacoordinated arrangement of two symmetrically doubly bonded NIPA molecules and one solvent molecule about the uranyl group. In the case of (UO/sub 2/(NIPA)/sub 2/(EtOH))(ClO/sub 4/)/sub 2/, an intermolecular exchange between bound and free ethanol molecules is observed above -75/sup 0/C upon addition of ethanol to a solution of the complex. The observed rate law, k/sub inter/ = kK(EtOH)/(1 + K(EtOH) is accounted for by the existence of an outer-sphere complex (UO/sub 2//sup 2 +/(NIPA)/sub 2/(EtOH))EtOH in fast equilibrium (K) with the initial complex and free ethanol. The rate-determining step (k) consists of an outer-sphere to inner-sphere interchange of ethanol molecules. The thermodynamic and kinetic parameters are K(25/sup 0/C) = 15.8 dm/sup 3/ mol/sup -1/, k(25/sup 0/C) = 1.0 x 10/sup 4/s/sup -1/, and inter//sup + +/ = -4.8 and 7.6 kcal mol/sup -1/, and and inter//sup + +/ = 10.7 and -14.7 eu. A second exchange takes place at higher temperatures (above -30/sup 0/C) yielding full dynamic equivalence of the phosphorus nuclei of the coordinated NIPA molecules. The observed rate law k/sub intra/ = k/sub ex/(1 + K(EtOH)) reveals that the internal rearrangement of NIPA molecules occurs on the complex ion (UO/sub 2/(NIPA)/sub 2/(EtOH))/sup 2 +/ but not on the outer-sphere complex: k/sub ex/(25/sup 0/C) = 0.91 x 10/sup 3/s/sup -1/, intra//sup + +/ = 10.6 kcal mol/sup -1/ and intra//sup + +/ = -9.4 eu. Possible mechanisms for this exchange are discussed. 5 figures, 2 tables.

  20. Ultra-flexible framework breathing in response to dehydration in liskeardite, [(Al,Fe){sub 16}(AsO{sub 4}){sub 9}(OH){sub 21}(H{sub 2}O){sub 11}]·26H{sub 2}O, a natural open-framework compound

    SciTech Connect

    Grey, Ian. E.; Brand, Helen E.A.; Rumsey, Michael S.; Gozukara, Yesim


    Dehydration of the natural open-framework compound, liskeardite, [(Al,Fe){sub 16}(AsO{sub 4}){sub 9}(OH){sub 21}(H{sub 2}O){sub 11}]·26H{sub 2}O, is accompanied by a change in the sign of the thermal expansion from positive to negative above room temperature, and at ~100 °C the structure undergoes a dramatic 2D contraction by co-operative rotation of heteropolyhedral columns that constitute the framework walls. Monoclinic liskeardite, I112 with a≈b≈24.7 Å, c ≈7.8 Å and β≈90° is transformed to a tetragonal phase, I-4 with a≈20.6 Å, c ≈7.7 Å. The associated 30% decrease in volume is unprecedented in inorganic microporous compounds. The flexibility of the contraction is related to the double-hinged nature of the column rotations about [001]. Octahedra in adjacent columns are interconnected by corner-sharing with the two pairs of anions forming opposing edges of AsO{sub 4} tetrahedra, so a double-hinged rotation mechanism operates. Thermal analysis and mass spectroscopic results for liskeardite show that the phase transition at ~100 °C is related to removal of the channel water. The tetragonal phase shows exceptionally large NTE behaviour. Over the temperature range 148–178 the NTE along a and b is close to linear with a magnitude of the order of −900×10{sup −6} °C{sup −1}. The contraction along the channel direction is smaller but still appreciable at −200×10{sup −6} °C{sup −1}. - Graphical abstract: Structure of the collapsed liskeardite framework, formed on dehydration above 100 °C. - Highlights: • The thermal expansion of the mineral liskeardite changes + to − above ambient. • Dehydration at 100 °C results in a record reversible 30% volume reduction. • In situ synchrotron XRD has led to a structural model for the dehydrated phase. • Framework breathing flexibility is attributed to a double-hinge rotation mechanism. • The dehydrated phase shows unprecedented -ve expansion for inorganic materials.

  1. Local structure of Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot}2H{sub 2}O by the modeling of X-ray diffuse scattering - from average-structure to microdomain model

    SciTech Connect

    Komornicka, Dorota; Wolcyrz, Marek; Pietraszko, Adam


    Local structure of dirubidium tetralithium tris(selenate(VI)) dihydrate - Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot} 2H{sub 2}O has been determined basing on the modeling of X-ray diffuse scattering. The origin of observed structured diffuse streaks is SeO{sub 4} tetrahedra switching between two alternative positions in two quasi-planar layers existing in each unit cell and formation of domains with specific SeO{sub 4} tetrahedra configuration locally fulfilling condition for C-centering in the 2a Multiplication-Sign 2b Multiplication-Sign c superstructure cell. The local structure solution is characterized by a uniform distribution of rather large domains (ca. thousand of unit cells) in two layers, but also monodomains can be taken into account. Inside a single domain SeO{sub 4} tetrahedra are ordered along ab-diagonal forming two-string ribbons. Inside the ribbons SeO{sub 4} and LiO{sub 4} tetrahedra share the oxygen corners, whereas ribbons are bound to each other by a net of hydrogen bonds and fastened by corner sharing SeO{sub 4} tetrahedra of the neighboring layers. - Graphical abstract: Experimental sections of the reciprocal space showing diffraction effects observed for RLSO. Bragg spots are visible on sections with integer indices (1 kl section - on the left), streaks - on sections with fractional ones (1.5 kl section - on the right). At the center: resulting local structure of the A package modeled as a microdomain: two-string ribbons of ordered oxygen-corners-sharing SeO{sub 4} and LiO{sub 4} terahedra extended along ab-diagonal are seen; ribbons are bound by hydrogen bonds (shown in pink); the multiplied 2a Multiplication-Sign 2b unit cell is shown. Highlights: Black-Right-Pointing-Pointer X-ray diffuse scattering in RLSO was registered and modeled. Black-Right-Pointing-Pointer The origin of diffuse streaks is SeO{sub 4} tetrahedra switching in two structure layers. Black-Right-Pointing-Pointer The local structure is characterized by a uniform

  2. Centrosymmetric [N(CH{sub 3}){sub 4}]{sub 2}TiF{sub 6} vs. noncentrosymmetric polar [C(NH{sub 2}){sub 3}]{sub 2}TiF{sub 6}: A hydrogen-bonding effect on the out-of-center distortion of TiF{sub 6} octahedra

    SciTech Connect

    Kim, Eun-ah; Lee, Dong Woo; Ok, Kang Min


    The syntheses, structures, and characterization of organically templated zero-dimensional titanium fluoride materials, A{sub 2}TiF{sub 6} (A=[N(CH{sub 3}){sub 4}] or [C(NH{sub 2}){sub 3}]), are reported. Phase pure samples of A{sub 2}TiF{sub 6} were synthesized by either solvothermal reaction method or a simple mixing method. While [N(CH{sub 3}){sub 4}]{sub 2}TiF{sub 6} crystallizes in a centrosymmetric space group, R-3, [C(NH{sub 2}){sub 3}]{sub 2}TiF{sub 6} crystallizes in a noncentrosymmetric polar space group, Cm. The asymmetric out-of-center distortion of TiF{sub 6} octahedra in polar [C(NH{sub 2}){sub 3}]{sub 2}TiF{sub 6} are attributable to the hydrogen-bonding interactions between the fluorine atoms in TiF{sub 6} octahedra and the nitrogen atoms in the [C(NH{sub 2}){sub 3}]{sup +} cation. Powder second-harmonic generation (SHG) measurements on the [C(NH{sub 2}){sub 3}]{sub 2}TiF{sub 6}, using 1064 nm radiation, indicate the material has SHG efficiency of 25 Multiplication-Sign that of {alpha}-SiO{sub 2}, which indicates an average nonlinear optical susceptibility, Left-Pointing-Angle-Bracket d{sub eff} Right-Pointing-Angle-Bracket {sub exp} of 2.8 pm/V. Additional SHG measurements reveal that the material is not phase-matchable (Type 1). The magnitudes of out-of-center distortions and dipole moment calculations for TiF{sub 6} octahedra will be also reported. - Graphical abstract: The out-of-center distortion of TiF{sub 6} octahedron in the polar noncentrosymmetric [C(NH{sub 2}){sub 3}]{sub 2}TiF{sub 6} is attributable to the hydrogen-bonding interactions between the F in TiF{sub 6} octahedron and the H-N in the [C(NH{sub 2}){sub 3}]{sup +}. Highlights: Black-Right-Pointing-Pointer Two titanium fluorides materials have been synthesized in high yields. Black-Right-Pointing-Pointer Hydrogen-bonds are crucial for the out-of-center distortion of TiF{sub 6} octahedra. Black-Right-Pointing-Pointer [C(NH{sub 2}){sub 3}]{sub 2}TiF{sub 6} has a SHG efficiency of 25

  3. High temperature redox reactions with uranium: Synthesis and characterization of Cs(UO{sub 2})Cl(SeO{sub 3}), Rb{sub 2}(UO{sub 2}){sub 3}O{sub 2}(SeO{sub 3}){sub 2}, and RbNa{sub 5}U{sub 2}(SO{sub 4}){sub 7}

    SciTech Connect

    Babo, Jean-Marie; Albrecht-Schmitt, Thomas E.


    Cs(UO{sub 2})Cl(SeO{sub 3}) (1), Rb{sub 2}(UO{sub 2}){sub 3}O{sub 2}(SeO{sub 3}){sub 3} (2), and RbNa{sub 5}U{sub 2}(SO{sub 4}){sub 7} (3) single crystals were synthesized using CsCl, RbCl, and a CuCl/NaCl eutectic mixture as fluxes, respectively. Their lattice parameters and space groups are as follows: P2{sub 1}/n (a=6.548(1) Å, b=11.052(2) Å, c=10.666(2) Å and β=93.897(3)°), P1{sup ¯} (a=7.051(2) Å, b=7.198(2) Å, c=8.314(2) Å, α=107.897(3)°, β=102.687(3)° and γ=100.564(3)°) and C2/c (a=17.862(4) Å, b=6.931(1) Å, c=20.133(4) Å and β=109.737(6)°. The small anionic building units found in these compounds are SeO{sub 3}{sup 2−} and SO{sub 4}{sup 2−} tetrahedra, oxide, and chloride. The crystal structure of the first compound is composed of [(UO{sub 2}){sub 2}Cl{sub 2}(SeO{sub 3}){sub 2}]{sup 2−} chains separated by Cs{sup +} cations. The structure of (2) is constructed from [(UO{sub 2}){sub 3}O{sub 11}]{sup 16−} chains further connected through selenite units into layers stacked perpendicularly to the [0 1 0] direction, with Rb{sup +} cations intercalating between them. The structure of compound (3) is made of uranyl sulfate layers formed by edge and vertex connections between dimeric [U{sub 2}O{sub 16}] and [SO{sub 4}] polyhedra. These layers contain unusual sulfate–metal connectivity as well as large voids. - Graphical abstract: A new family of uranyl selenites and sulfates has been prepared by high-temperature redox reactions. This compounds display new bonding motifs. Display Omitted - Highlights: • Low-dimensional Uranyl Oxoanion compounds. • Conversion of U(IV) to U(VI) at high temperatures. • Dimensional reduction by both halides and stereochemically active lone-pairs.

  4. Thermodynamic Model for the Solubility of NdF3(cr) in the Na+-NH4sub>+ – Nd3+–F-–H2O System at 25 °C

    SciTech Connect

    Rai, Dhanpat; Yui, Mikazu; Kitamura, Akira; Yoshikawa, Hideki; Felmy, A. R.


    The objectives of this study were to develop a reliable thermodynamic model for the Nd-F system based on critical review and experimental studies. The SIT model was used to convert concentration constants reported in the literature to constants at zero ionic strengths for cross comparison and selection of reliable values. The critically evaluated thermodynamic constants for the formation of NdF2+ and NdF2+ were then used to interpret the extensive NdF3(cr) solubility data in NaF and NH4sub>F solutions, ranging in concentrations from extremely low values to as high as 1.0, equilibrated for different periods ranging up to as long as 72 days. These efforts have resulted in log βn0 for the reaction [Nd3+ + nF- = NdFn3-n] of (3.81 ± 0.10), (5.89 ± 0.77), and <12.48 for n of 1 through 3, respectively. The log10 Ksp0 for the solubility of NdF3(cr) (NdF3(cr) = Nd3+ + 3F-) was determined to be -(20.49 ± 0.37). Because 1) Nd is an excellent analog for trivalent actinides -- An(III) (e.i., Pu(III), Am(III), and Cm(III)) -- and 2) the available data for the An(III)-F system, especially the solubility products of AnF3(cr), are of extremely poor quality, the critical literature review in combination with the experimental Nd-F system data have been used to assign thermodynamic constants for the An(III)-F reactions until good quality specific data for them becomes available.

  5. The relationship between reorientational molecular motions and phase transitions in [Mg(H{sub 2}O){sub 6}](BF{sub 4}){sub 2}, studied with the use of {sup 1}H and {sup 19}F NMR and FT-MIR

    SciTech Connect

    Mikuli, Edward Hetmańczyk, Joanna; Grad, Bartłomiej; Kozak, Asja; Wąsicki, Jan W.; Bilski, Paweł; Hołderna-Natkaniec, Krystyna; Medycki, Wojciech


    A {sup 1}H and {sup 19}F nuclear magnetic resonance study of [Mg(H{sub 2}O){sub 6}](BF{sub 4}){sub 2} has confirmed the existence of two phase transitions at T{sub c1} ≈ 257 K and T{sub c2} ≈ 142 K, detected earlier by the DSC method. These transitions were reflected by changes in the temperature dependences of both proton and fluorine of second moments M{sub 2}{sup H} and M{sub 2}{sup F} and of spin-lattice relaxation times T{sub 1}{sup H} and T{sub 1}{sup F}. The study revealed anisotropic reorientations of whole [Mg(H{sub 2}O){sub 6}]{sup 2+} cations, reorientations by 180° jumps of H{sub 2}O ligands, and aniso- and isotropic reorientations of BF{sub 4}{sup −} anions. The activation parameters for these motions were obtained. It was found that the phase transition at T{sub c1} is associated with the reorientation of the cation as a whole unit around the C{sub 3} axis and that at T{sub c2} with isotropic reorientation of the BF{sub 4}{sup −} anions. The temperature dependence of the full width at half maximum value of the infrared band of ρ{sub t}(H{sub 2}O) mode (at ∼596 cm{sup −1}) indicated that in phases I and II, all H{sub 2}O ligands in [Mg(H{sub 2}O){sub 6}]{sup 2+} perform fast reorientational motions (180° jumps) with a mean value of activation energy equal to ca 10 kJ mole{sup −1}, what is fully consistent with NMR results. The phase transition at T{sub c1} is associated with a sudden change of speed of fast (τ{sub R} ≈ 10{sup −12} s) reorientational motions of H{sub 2}O ligands. Below T{sub c2} (in phase III), the reorientations of certain part of the H{sub 2}O ligands significantly slow down, while others continue their fast reorientation with an activation energy of ca 2 kJ mole{sup −1}. This fast reorientation cannot be evidenced in NMR relaxation experiments. Splitting of certain IR bands connected with H{sub 2}O ligands at the observed phase transitions suggests a reduction of the symmetry of the octahedral [Mg(H{sub 2}O

  6. Phase equilibria in the quasi-ternary system Ag{sub 2}Se–Ga{sub 2}Se{sub 3}–In{sub 2}Se{sub 3} and physical properties of (Ga{sub 0.6}In{sub 0.4}){sub 2}Se{sub 3}, (Ga{sub 0.594}In{sub 0.396}Er{sub 0.01}){sub 2}Se{sub 3} single crystals

    SciTech Connect

    Ivashchenko, I.A.; Danyliuk, I.V.; Olekseyuk, I.D.; Halyan, V.V.


    The quasi-ternary system Ag{sub 2}Se–Ga{sub 2}Se{sub 3}–In{sub 2}Se{sub 3} was investigated by differential thermal, X-ray phase, X-ray structure, microstructure analysis and microhardness measurements. Five quasi-binary phase diagrams, six polythermal sections, isothermal section at 820 K and the liquidus surface projection were constructed. The character and temperature of the invariant processes were determined. The specific resistance of the single crystals (Ga{sub 0.6}In{sub 0.4}){sub 2}Se{sub 3}, (Ga{sub 0.594}In{sub 0.396}Er{sub 0.01}){sub 2}Se{sub 3} was measured, 7.5×10{sup 5} and 3.15×10{sup 5} Ω m, respectively, optical absorption spectra in the 600–1050 nm range were recorded at room temperature, and the band gap energy was estimated which is 1.95±0. 01 eV for both samples. - Graphical abstract: The article reports for the first time the investigated liquidus surface projection of the Ag{sub 2}Se–Ga{sub 2}Se{sub 3}–In{sub 2}Se{sub 3} system and isothermal section at 820 K of the system. Five phase diagrams, six polythermal sections, isothermal section at 820 K and the liquidus surface projection were built at the first time. The existence of the large region of the solid solutions based on AgIn{sub 5}Se{sub 8}, Ga{sub 2}Se{sub 3} and AgGa{sub 1−x}In{sub x}Se{sub 2} was investigated. The existence of two ternary phases was established in the Ga{sub 2}Se{sub 3}–In{sub 2}Se{sub 3} system. Two single crystals (Ga{sub 0.6}In{sub 0.4}){sub 2}Se{sub 3}, (Ga{sub 0.594}In{sub 0.396}Er{sub 0.01}){sub 2}Se{sub 3} were grown and some of optical properties of them were studied at first time. Display Omitted - Highlights: • Liquidus surface projection was built for Ag{sub 2}Se–Ga{sub 2}Se{sub 3}–In{sub 2}Se{sub 3} system. • Solid solution ranges of AgIn{sub 5}Se{sub 8}, Ga{sub 2}Se{sub 3} and AgGa{sub 1−x}In{sub x}Se{sub 2} were investigated. • Two single crystals (Ga{sub 0.6}In{sub 0.4}){sub 2}Se{sub 3}, (Ga{sub 0.594}In{sub 0.396}Er

  7. Hydrothermal synthesis and structural analysis of new mixed oxyanion borates: Ba{sub 11}B{sub 26}O{sub 44}(PO{sub 4}){sub 2}(OH){sub 6}, Li{sub 9}BaB{sub 15}O{sub 27}(CO{sub 3}) and Ba{sub 3}Si{sub 2}B{sub 6}O{sub 16}

    SciTech Connect

    Heyward, Carla McMillen, Colin D. Kolis, Joseph


    Several new borate compounds, Ba{sub 11}B{sub 26}O{sub 44}(PO{sub 4}){sub 2}(OH){sub 6} (1), Li{sub 9}BaB{sub 15}O{sub 27}(CO{sub 3}) (2), and Ba{sub 3}Si{sub 2}B{sub 6}O{sub 16} (3) were synthesized containing other hetero-oxyanion building blocks in addition to the borate frameworks. They were all prepared under hydrothermal conditions and characterized by single crystal and powder X-ray diffraction, and IR spectroscopy. Crystal data: For 1; space group P2{sub 1}/c, a=6.8909 (14) Å, b=13.629 (3) Å, c=25.851 (5) Å, β=90.04 (3)°; For 2; space group P-31c, a=8.8599 (13) Å, c=15.148 (3) Å; For 3; space group P-1, a=5.0414 (10) Å, b=7.5602 (15) Å, c=8.5374 (17) Å, α=77.15 (3)°, β=77.84 (3)°, γ=87.41 (3)° for 3. Compounds 1 and 2 contain isolated oxyanions [PO{sub 4}]{sup 3−} and [CO{sub 3}]{sup 2−} respectively, sitting in channels created by the borate framework, while structure 3 has the [SiO{sub 4}]{sup 4−} groups directly bonded to the borate groups creating a B–O–Si framework. - Highlights: • Hydrothermal syntheses of three new mixed oxyanion borates are presented. • Ba{sub 11}B{sub 26}O{sub 44}(PO{sub 4}){sub 2}(OH){sub 6} contains isolated [PO{sub 4}]{sup 3−} in voids of the borate framework. • Li{sub 9}BaB{sub 15}O{sub 27}(CO{sub 3}) contains isolated [CO{sub 3}]{sup 2−} in channels created by the framework. • Ba{sub 3}Si{sub 2}B{sub 6}O{sub 16} has direct bonding of [SiO{sub 4}]{sup 4−} and borates creating a B–O–Si framework.

  8. Synthesis, structure, and physical properties of [Sm(C{sub 6}NO{sub 2}H{sub 5}){sub 3}(H{sub 2}O){sub 2}]{sub 2n}.(H{sub 5}O{sub 2}){sub n}(ZnCl{sub 5}){sub n}(ZnCl{sub 4}){sub 2n}.(H{sub 2}O){sub 2n} with unprecedented ZnCl{sub 5}{sup 3-} species

    SciTech Connect

    Xie Yiming Chen Wentong; Wu Jihuai


    A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Sm(C{sub 6}NO{sub 2}H{sub 5}){sub 3}(H{sub 2}O){sub 2}]{sub 2n}.(H{sub 5}O{sub 2}){sub n}(ZnCl{sub 5}){sub n}(ZnCl{sub 4}){sub 2n}.(H{sub 2}O){sub 2n} (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure and unprecedented ZnCl{sub 5}{sup 3-} species. Photoluminescent investigation reveals that the title complex displays interesting emissions in a wide region. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.59 eV. - Graphical abstract: A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex was synthesized. It is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in a wide region. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap.

  9. Syntheses, crystal structures and Raman spectra of Ba(BF{sub 4})(PF{sub 6}), Ba(BF{sub 4})(AsF{sub 6}) and Ba{sub 2}(BF{sub 4}){sub 2}(AsF{sub 6})(H{sub 3}F{sub 4}); the first examples of metal salts containing simultaneously tetrahedral BF{sub 4}{sup -} and octahedral AF{sub 6}{sup -} anions

    SciTech Connect

    Lozinsek, Matic; Bunic, Tina; Goreshnik, Evgeny; Meden, Anton; Tramsek, Melita; Tavcar, Gasper; Zemva, Boris


    In the system BaF{sub 2}/BF{sub 3}/PF{sub 5}/anhydrous hydrogen fluoride (aHF) a compound Ba(BF{sub 4})(PF{sub 6}) was isolated and characterized by Raman spectroscopy and X-ray diffraction on the single crystal. Ba(BF{sub 4})(PF{sub 6}) crystallizes in a hexagonal P6-bar2m space group with a=10.2251(4) A, c=6.1535(4) A, V=557.17(5) A{sup 3} at 200 K, and Z=3. Both crystallographically independent Ba atoms possess coordination polyhedra in the shape of tri-capped trigonal prisms, which include F atoms from BF{sub 4}{sup -} and PF{sub 6}{sup -} anions. In the analogous system with AsF{sub 5} instead of PF{sub 5} the compound Ba(BF{sub 4})(AsF{sub 6}) was isolated and characterized. It crystallizes in an orthorhombic Pnma space group with a=10.415(2) A, b=6.325(3) A, c=11.8297(17) A, V=779.3(4) A{sup 3} at 200 K, and Z=4. The coordination around Ba atom is in the shape of slightly distorted tri-capped trigonal prism which includes five F atoms from AsF{sub 6}{sup -} and four F atoms from BF{sub 4}{sup -} anions. When the system BaF{sub 2}/BF{sub 3}/AsF{sub 5}/aHF is made basic with an extra addition of BaF{sub 2}, the compound Ba{sub 2}(BF{sub 4}){sub 2}(AsF{sub 6})(H{sub 3}F{sub 4}) was obtained. It crystallizes in a hexagonal P6{sub 3}/mmc space group with a=6.8709(9) A, c=17.327(8) A, V=708.4(4) A{sup 3} at 200 K, and Z=2. The barium environment in the shape of tetra-capped distorted trigonal prism involves 10 F atoms from four BF{sub 4}{sup -}, three AsF{sub 6}{sup -} and three H{sub 3}F{sub 4}{sup -} anions. All F atoms, except the central atom in H{sub 3}F{sub 4} moiety, act as mu{sub 2}-bridges yielding a complex 3-D structural network. - Graphical abstract: The first three compounds, containing simultaneously tetrahedral BF{sub 4}{sup -} and octahedral AF{sub 6}{sup -} (A=P, As) anions have been synthesized and characterized by Raman spectroscopy and X-ray single crystal diffraction. In the system BaF{sub 2}/BF{sub 3}/PF{sub 5}/anhydrous hydrogen fluoride (a

  10. Mild hydrothermal synthesis, crystal structure, spectroscopic and magnetic properties of the [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup V}O{sub 4}){sub 2-y}F; M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds

    SciTech Connect

    Orive, Joseba


    The [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup V}O{sub 4}){sub 2-y}F; M=Fe (1), x=2.08, y=1.58; M=Co (2), x=2.5, y=2; Ni (3), x=2.5, y=2] compounds have been synthesized using mild hydrothermal conditions at 170 deg. C during five days. Single-crystals of (1) and (2), and polycrystalline sample of (3) were obtained. These isostructural compounds crystallize in the orthorhombic system, space group Aba2, with a=9.9598(2), b=18.8149(4) and c=8.5751(2) A for (1), a=9.9142(7), b=18.570(1) and c=8.4920(5) A for (2) and a=9.8038(2), b=18.2453(2) and c=8.4106(1) A for (3), with Z=8 in the three phases. An X-ray diffraction study reveals that the crystal structure is composed of a three-dimensional skeleton formed by [MO{sub 5}F] and [MO{sub 4}F{sub 2}] (M=Fe, Co and Ni) octahedra and [HPO{sub 3}] tetrahedra, partially substituted by [PO{sub 4}] tetrahedra in phase (1). The IR spectra show the vibrational modes of the water molecules and those of the (HPO{sub 3}){sup 2-} tetrahedral oxoanions. The thermal study indicates that the limit of thermal stability of these phases is 195 deg. C for (1) and 315 deg. C for (2) and (3). The electronic absorption spectroscopy shows the characteristic bands of the Fe(II), Co(II) and Ni(II) high-spin cations in slightly distorted octahedral geometry. Magnetic measurements indicate the existence of global antiferromagnetic interactions between the metallic centers with a ferromagnetic transition in the three compounds at 28, 14 and 21 K for (1), (2) and (3), respectively. Compound (1) exhibits a hysteresis loop with remnant magnetization and coercive field values of 0.72 emu/mol and 880 Oe, respectively. - Abstract: Polyhedral view of the crystal structure of the [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup IV}O{sub 4}){sub 2-y}F; M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds showing the sheets along the [001] direction.

  11. Enhancement of La0.6Sr0.4sub>Co0.2Fe0.8O3-δ Durability and Surface Electro-catalytic Activity by La0.85Sr0.15MnO3-δ Investigated using a New Test Electrode Platform

    SciTech Connect

    Lynch, Matthew; Yang, Lei; Qin, Wentao; Choi, Jongjin; Liu, Mingfei; Blinn, Kevin; Liu, Meilin


    A carefully designed test cell platform with a new electrode structure is utilized to determine the intrinsic surface catalytic properties of an electrode. With this design, the electrocatalytic activity and stability of an La0.6Sr0.4sub>Co0.2Fe0.8O3-δ (LSCF) cathode is enhanced by a dense thin La0.85Sr0.15MnO3±δ (LSM) coating, suggesting that an efficient electrode architecture has been demonstrated that can make effective use of desirable properties of two different materials: fast ionic and electronic transport in the backbone (LSCF) and facile surface kinetics on the thin-film coating (LSM). Theoretical analyses suggest that the enhanced electrocatalytic activity of LSM-coated LSCF is attributed possibly to surface activation under cathodic polarization due to the promotion of oxygen adsorption and/or dissociation by the surface layer and the dramatically increased oxygen vacancy population in the surface film. Further, the observed time-dependent activation over a few hundreds of hours and durability are likely associated with the formation of a favorable hybrid surface phase intermediate between LSM and LSCF. This efficient electrode architecture was successfully applied to the state-of-the-art LSCF-based cathodes by a simple solution infiltration process, achieving reduced interfacial resistance and improved stability under fuel cell operating conditions.

  12. Sr2IrO4sub>: Gateway to cuprate superconductivity?

    SciTech Connect

    Mitchell, J. F.


    High temperature superconductivity in cuprates remains a defining challenge in condensed matter physics. Recently, a new set of related compounds based on Ir rather than Cu has been discovered that may be on the verge of superconductivity themselves or be able to shed new light on the underlying interactions responsible for superconductivity in the cuprates.

  13. Metastable Tetragonal CdWO4sub> Nanoparticles Synthesized with a Solvothermal Method

    SciTech Connect

    Rondinone, Adam Justin; Travaglini, Dustin H; Pawel, Michelle D; Mahurin, Shannon Mark; Dai, Sheng


    CdWO{sub 4} has only previously been reported in the monoclinic, or wolframite, phase. Here we report the first metastable, tetragonal or scheelite, CdWO4 nanopowder. The tetragonal CdWO{sub 4} was synthesized by a propylene glycol solvothermal method. The scheelite phase is stabilized by a combination of high surface area and surface complexation by the propylene glycol. The CdWO{sub 4} is stable at 1 bar to 300 C, and converts back to the monoclinic wolframite phase between 300 and 500 C. The nanopowder exhibits cubic morphology and the average particle size of the nanopowder is around 50 nm.

  14. Enthalpies of Formation of Rare-Earth Orthovanadates, REVO4sub>

    SciTech Connect

    Dorogova, M.; Navrotsky, Alexandra; Boatner, Lynn A


    Rare earth orthovanadates, REVO4, having the zircon structure, form a series of materials interesting for magnetic, optical, sensor, and electronic applications. Enthalpies of formation of REVO4 compounds (RE=Sc, Y, Ce Nd, Sm Tm, Lu) were determined by oxide melt solution calorimetry in lead borate (2PbO {center_dot} 2B2O3) solvent at 1075 K. The enthalpies of formation from oxide components become more negative with increasing RE ionic radius. This trend is similar to that obtained for the rare earth phosphates.

  15. Thermoelectric properties of rhodates: layered beta SrRh2O4sub> and spinel ZnRh2O4sub>

    SciTech Connect

    Wilson-Short, Gareth B; Singh, David J; Fornari, M.; Suewattana, Malliga


    Density functional calculations are used to obtain the electronic structure of {beta}-SrRh{sub 2}O{sub 4} in comparison with spinel ZnRh{sub 2}O{sub 4}. Both materials are band insulators, with substantial crystal field induced band gaps, reflecting strong transition-metal-O hybridization. However, due to the bonding topology in these materials, the valence bands are very narrow. This leads to high thermopowers within standard Boltzmann transport theory, and indicates that they can be the basis of good thermoelectric materials provided that they can be doped into metallic states with reasonable carrier mobility. In the case of {beta}-SrRh{sub 2}O{sub 4}, scattering due to Sr disorder is important. Also, again in {beta}-SrRh{sub 2}O{sub 4}, the band gap may be large enough to be of interest for photoelectrochemical H{sub 2} production.

  16. Theoretical Studies on the Photoelectron and Absorption Spectra of MnO 4sub> and TcO 4sub>

    SciTech Connect

    Su, Jing; Xu, Wen-Hua; Xu, Chao-Fei; Schwarz, W. H. E.; Li, Jun


    The tetraoxo pertechnetate anion (TcO4-) is of great interest for nuclear waste management and radiopharmceuticals. To elucidate its electronic structure and to compare with that of its lighter congener MnO4-, the photoelectron and electronic absorption spectra of MnO4 - and TcO4 - are investigated with density functional theory (DFT) and ab initio wave function theory (WFT). The vertical electron detachment energies (VDEs) of MnO4 - obtained with the CR-EOM-CCSD(T) method are in good agreement with the lowest two experimental VDEs; the differences are less than 0.1 eV, representing a significant improvement over the IP-EOMCCSD(T) result in the literature. Combining our CCSD(T) and CR-EOMCCSD( T) results, the first five VDEs of TcO4 - are estimated between 5 and 10 eV with an estimated accuracy of about ±0.2 eV. The vertical excitation energies are determined by using TD-DFT, CR-EOM-CCSD(T), and RASPT2 methods. The excitation energies and the assignments of the spectra are analyzed and partly improved. They are compared with reported SAC-CI results and available experimental data. Both dynamic and nondynamic electron correlations are important in the ground and excited states of MnO4 - and TcO4 -. Nondynamical correlations are particularly relevant in TcO4 - for reliable prediction of excitation energies. In TcO4 - one Rydberg state interlaces but does not mix with the valence excited states, and it disappears in the condensed phase.

  17. The Ground State of (CS) 4sub> Is Different from That of (CO) 4sub> : An Experimental Test of a Computational Prediction by Negative Ion Photoelectron Spectroscopy

    SciTech Connect

    Zhang, Jian; Hrovat, David A.; Sun, Zhenrong; Bao, Xiaoguang; Borden, Weston Thatcher; Wang, Xue-Bin


    Cyclobutane-1,2,3,4-tetrathione, (CS)4, has recently been calculated to have a singlet ground state, 1A1g, in which the highest b2g MO is doubly occupied and the lowest a2u MO is empty. Thus, (CS)4 is predicted to have a different ground state than its lighter congener, (CO)4, which has a triplet ground state, 3B1u, in which these two MOs are each singly occupied. Here we report the results of a negative ion photoelectron spectroscopy (NIPES) study of the radical anion (CS)4∙-, designed to test the prediction that (CS)4 has a singlet ground state. The NIPE spectrum reveals that (CS)4 does, indeed, have a singlet ground state with electron affinity (EA) = 3.75 eV. The lowest triplet state is found to lie 0.31 eV higher in energy than the ground state, and the open-shell singlet is 0.14 eV higher in energy than the triplet state. Calculations at the (U)CCSD(T)/aug-cc-pVTZ//(U)B3LYP/6-311+G(2df) level support the spectral assignments, giving EA = 3.71 eV, EST = 0.44 eV. These calculated values are, respectively, 0.04 eV (0.9 kcal/mol) smaller, and 0.13 eV (3.0 kcal/mol) larger than the corresponding experimental values. In addition, RASPT2 calculations with various active spaces converge on a 1B1u-3B1u energy gap of 0.137 eV, in excellent agreement with the 0.14 eV energy difference obtained from the NIPE spectrum. Finally, calculations of the Franck-Condon factors for transitions from the ground state of (CS)4∙- to the ground (1A1g) and two excited states (3B1u, 1B1u) of (CS)4 account for all of the major spectral peaks, and nicely reproduce vibrational structure observed in each electronic transition. The close correspondence between the calculated and the observed features in the NIPE spectrum of (CS)4∙- provides unequivocal proof that (CS)4, unlike (CO)4, has a singlet ground state.

  18. Asymmetric cation non-stoichiometry in spinels: site occupancy in Co2ZnO4sub> and Rh2ZnO4sub>

    SciTech Connect

    Paudel, Tula; Lany, Stephan; d'Avezac, Mayeul; Zunger, Alex; Perry, Nicola H.; Nagaraja, Arpun R.; Mason, Thomas O.; Bettinger, Joanna S.; Shi, Yezhou; Toney, Michael F.


    Two cations A and B in A₂BO₄ spinels appear in precise 2:1 Daltonian ratio ("line compounds") only at very low temperature. More typically, at finite temperature, they tend to become either A rich or B rich. Here we survey the experimentally observed stoichiometry asymmetries and describe the first-principles framework for calculating these. Defect calculations based on first principles are used to calculate the enthalpies of substitution of A atom ΔH(ATd) and B atom ΔH(BOh) and determine their site occupancies leading to (non)-stoichiometry. In Co₂ZnO₄, the result of the calculation for site occupancy compares well with that measured via anomalous x-ray diffraction. Further, the calculated phase boundary also compares well with that measured via Rietveld refinement of x-ray diffraction data on bulk ceramic sintered samples of Co₂ZnO₄ and Rh₂ZnO₄. These results show that Co₂ZnO₄ is heavily Co nonstoichiometric above 500 °C, whereas Rh₂ZnO₄ is slightly Zn nonstoichiometric. We found that, in general, the calculated ΔH(ATd) is smaller than ΔH(BOh), if the A-rich competing phase is isostructural with the A₂BO₄ host, for example, A₂AO₄, whereas B-rich competing phase is not, for example, BO. This observation is used to qualitatively explain nonstoichiometry and solid solutions observed in other spinels.

  19. Electrical properties of methane hydrate + sediment mixtures: The σ of CH4sub> Hydrate + Sediment

    SciTech Connect

    Du Frane, Wyatt L.; Stern, Laura A.; Constable, Steven; Weitemeyer, Karen A.; Smith, Megan M.; Roberts, Jeffery J.


    Knowledge of the electrical properties of multicomponent systems with gas hydrate, sediments, and pore water is needed to help relate electromagnetic (EM) measurements to specific gas hydrate concentration and distribution patterns in nature. We built a pressure cell capable of measuring in situ electrical properties of multicomponent systems such that the effects of individual components and mixing relations can be assessed. We first established the temperature-dependent electrical conductivity (σ) of pure, single-phase methane hydrate to be ~5 orders of magnitude lower than seawater, a substantial contrast that can help differentiate hydrate deposits from significantly more conductive water-saturated sediments in EM field surveys. We report σ measurements of two-component systems in which methane hydrate is mixed with variable amounts of quartz sand or glass beads. Sand by itself has low σ but is found to increase the overall σ of mixtures with well-connected methane hydrate. Alternatively, the overall σ decreases when sand concentrations are high enough to cause gas hydrate to be poorly connected, indicating that hydrate grains provide the primary conduction path. Our measurements suggest that impurities from sand induce chemical interactions and/or doping effects that result in higher electrical conductivity with lower temperature dependence. Finally, these results can be used in the modeling of massive or two-phase gas-hydrate-bearing systems devoid of conductive pore water. Further experiments that include a free water phase are the necessary next steps toward developing complex models relevant to most natural systems.

  20. Fermi Surface and Quasiparticle Excitations of Sr2RhO4sub>

    SciTech Connect

    Baumberger, F.; Ingle, N. J. C.; Meevasana, W.; Lu, D. H.; Perry, R. S.; Mackenzie, A. P.; Hussain, Z; Singh, David J; Shen, Z. X.


    The electronic structure of the layered 4d transition metal oxide Sr2RhO4 is investigated by angle resolved photoemission. We find well-defined quasiparticle excitations with a highly anisotropic dispersion, suggesting a quasi-two-dimensional Fermi-liquid-like ground state. Markedly different from the isostructural Sr2RuO4, only two bands with dominant Rh 4dxz;zy character contribute to the Fermi surface. A quantitative analysis of the photoemission quasiparticle band structure is in excellent agreement with bulk data. In contrast, it is found that state-of-the-art density functional calculations in the local density approximation differ significantly from the experimental findings.

  1. Numerical methods for studying anharmonic oscillator approximations to the phi super 4 sub 2 quantum field theory

    NASA Technical Reports Server (NTRS)

    Isaacson, D.; Marchesin, D.; Paes-Leme, P. J.


    This paper is an expanded version of a talk given at the 1979 T.I.C.O.M. conference. It is a self-contained introduction, for applied mathematicians and numerical analysts, to quantum mechanics and quantum field theory. It also contains a brief description of the authors' numerical approach to the problems of quantum field theory, which may best be summarized by the question; Can we compute the eigenvalues and eigenfunctions of Schrodinger operators in infinitely many variables.

  2. Development of a He3-He4 sub Kelvin active magnetic regenerative refrigerator (AMRR) with no moving parts

    NASA Astrophysics Data System (ADS)

    Jahromi, A. E.; Miller, F. K.


    Current state of the art particle and photon detectors such as Transition Edge Sensors (TES) and Microwave Kinetic Inductance Detectors (MKID) use large arrays of sensors or detectors for space science missions. As the size of these space science detectors increases, future astrophysics missions will require sub-Kelvin cooling over larger areas. This leads to not only increased cooling power requirements, but also a requirement for distributed sub-Kelvin cooling. We propose an active Magnetic Regenerative Refrigerator (AMRR) that uses a Superfluid Magnetic Pump (SMP) to circulate liquid He3-He4 through a magnetic regenerator to provide the necessary cooling at sub-Kelvin temperatures. Such system will be capable of distributing the cooling load to a relatively large array of objects. One advantage of using a fluid for heat transfer in such systems is to isolate components such as the superconducting magnets from detectors that are sensitive to magnetic fields. Another advantage of the proposed tandem AMRR is that it does not need Gas Gap Heat Switches (GGHS) to transfer heat during various stages of the magnetic cooling. Our proposed system consists of four superconducting magnets, one superleak, and three heat exchangers. It will operate continuously with no moving parts and it will be capable of providing the necessary cooling at sub-Kelvin temperatures for future space science applications.

  3. La2-xSrxCuO4sub> superconductor nanowire devices

    SciTech Connect

    Litombe, N. E.; Bollinger, A. T.; Hoffman, J. E.; Božović, I.


    La2-xSrxCuO₄ nanowire devices have been fabricated and characterized using electrical transport measurements. In addition, nanowires with widths down to 80 nm are patterned using high-resolution electron beam lithography. However, the narrowest nanowires show incomplete superconducting transitions with some residual resistance at T = 4 K. Here, we report on refinement of the fabrication process to achieve narrower nanowire devices with complete superconducting transitions, opening the path to the study of novel physics arising from dimension-limited superconductivity on the nanoscale.

  4. Zintl-phase compounds with SnSb4sub> tetrahedral anions. Electronic structure and thermoelectric properties

    SciTech Connect

    Zhang, Lijun; Du, Mao-Hua; Singh, David J.


    We report the investigation of Zintl-phase Na(K){sub 8}SnSb{sub 4} and related compounds that contain SnSb{sub 4} tetrahedral anions using first principles electronic structure, Boltzmann transport, and density functional phonon calculations. We find that these compounds are narrow-gap semiconductors and there is a combination of heavy and light bands at valence band edge, which may lead to a combination of high thermopower and reasonable conductivity. High values of the thermopower are found for p-type doping within the Boltzmann transport theory. Furthermore, these materials are expected to have low thermal conductivity due to their structures that consist of a network of weakly coupled SnSb{sub 4} clusters, which leads to low phonon frequencies. In particular, we find low-frequency optical phonons that should effectively scatter the heat-carrying acoustic phonons. These results are discussed in terms of the structure, which consists of anionic clusters. Based on the results, it is suggested that such compounds may represent a useful paradigm for finding new thermoelectric materials.

  5. Efficient 2-μm laser oscillation of 5% Tm{sup 3+} : KLu(WO{sub 4}){sub 2} disks and 5% Tm{sup 3+} : KLu(WO{sub 4}){sub 2}/KLu(WO{sub 4}){sub 2} composite structures

    SciTech Connect

    Vatnik, S M; Vedin, I A; Kurbatov, P F; Pavlyuk, A A


    The spectral and lasing characteristics of active disk elements made of double potassium – lutetium tungstates 5% Tm : KLuW and 5% Tm : KLuW/KLuW composite structures are comparatively studied. Laser power of about 5 W in the cw regime at a wavelength of 1.85 μm was achieved in a composite sample with the active layer thickness of 250 μm. Under quasi-cw pumping, the slope efficiency of all the studied samples exceeded 50%. It is experimentally shown that the internal stresses in the composite structures strongly affect the spectral characteristics of the laser radiation. (lasers)

  6. Solubility of (UO2)3(PO4sub>)2.4sub>H2O in H+-Na+-OH--H2PO-4sub>-HPO2-4sub>-PO3-4sub>-H2O and its Comparison to the Analogous PuO2+2 System

    SciTech Connect

    Rai, Dhanpat; Xia, Yuanxian; Rao, Linfeng; Hess, Nancy J; Felmy, Andrew R; Moore, Dean A; McCready, David E


    ABSTRACT-The objectives of this study were to address uncertainties in the solubility product of (UO₂)₃(PO₄)₂ · 4H₂O(c) and in the phosphate complexes of U(VI), and more importantly to develop needed thermodynamic data for the Pu(VI)-phosphate system in order to ascertain the extent to which U(VI) and Pu(VI) behave in an analogous fashion. Thus studies were conducted on (UO₂)₃(PO₄)₂ · 4H₂O(c) and (PuO₂)₃(PO₄)₂ · 4H₂O(lc) solubilities for long equilibration periods (up to 870 days) in a wide range of pH values (2.5 to 10.5) at fixed phosphate concentrations of 0.001 and 0.01 M, and in a range of phosphate concentrations (0.0001 to 1.0 M) at fixed pH values of about 3.5. A combination of techniques (XRD, DTA/TG, XAS, and thermodynamic analyses) was used to characterize the reaction products...

  7. OH species, U ions, and CO/CO2 in thermally annealed metamict zircon (ZrSiO4sub>)

    SciTech Connect

    Zhang, J. Ming; Salje, Ekhard K.H.; Ewing, Rodney C.


    Metamict zircon crystals have been thermally annealed between 500 and 1800 K and analyzed using infrared and optical spectroscopy in the spectral region of 1400–7000 cm-1. Recrystallization and dehydroxylation via complex proton/OH diffusion, redistribution, and incorporations of additional hydrogen-related species within the crystal structure of zircon occur at temperatures above 700 K in partially metamict zircon and above 1200 K in heavily amorphized material. Thermally induced changes in O-H stretching spectra are different between E || c and E ⊥ c in weakly metamict zircon. The O-H stretching band near 3342 cm-1 (with E ⊥ c) in an untreated sample shifts to 3277 cm-1 at 1200 K, where the frequency of O-H stretching bands with E || c increases. Conversions of hydrogen-related species were observed and extra OH bands were found at temperatures between 1200 and 1600 K. A dramatic change of OH spectra was recorded between 1600 and 1800 K in partially metamict crystals, resulting in additional absorption features (near 3098 and 2998 cm-1 along E ⊥ c). U4+ and U5+ related spectra are also affected by high-temperature annealing. For highly metamict zircon, the U4+ band near 4830 cm-1 shows an increase in intensity above 1200 K. Additional IR bands at 2146 and 2344 cm-1 appear in the spectra of metamict zircon annealed at high temperatures. Their frequencies are consistent with stretching vibrations of CO and CO2.

  8. An Engineered Disulfide Bond Reversibly Traps the IgE-Fc3-4sub> in a Closed, Nonreceptor Binding Conformation

    SciTech Connect

    Wurzburg, Beth A.; Kim, Beomkyu; Tarchevskaya, Svetlana S.; Eggel, Alexander; Vogel, Monique; Jardetzky, Theodore S.


    IgE antibodies interact with the high affinity IgE Fc receptor, FcϵRI, and activate inflammatory pathways associated with the allergic response. The IgE-Fc region, comprising the C-terminal domains of the IgE heavy chain, binds FcϵRI and can adopt different conformations ranging from a closed form incompatible with receptor binding to an open, receptor-bound state. A number of intermediate states are also observed in different IgE-Fc crystal forms. To further explore this apparent IgE-Fc conformational flexibility and to potentially trap a closed, inactive state, we generated a series of disulfide bond mutants. Here we describe the structure and biochemical properties of an IgE-Fc mutant that is trapped in the closed, non-receptor binding state via an engineered disulfide at residue 335 (Cys-335). Reduction of the disulfide at Cys-335 restores the ability of IgE-Fc to bind to its high affinity receptor, FcϵRIα. The structure of the Cys-335 mutant shows that its conformation is within the range of previously observed, closed form IgE-Fc structures and that it retains the hydrophobic pocket found in the hinge region of the closed conformation. Locking the IgE-Fc into the closed state with the Cys-335 mutation does not affect binding of two other IgE-Fc ligands, omalizumab and DARPin E2_79, demonstrating selective blocking of the high affinity receptor binding.

  9. Room temperature metathetic synthesis and characterization of {alpha}-hopeite, Zn{sub 3}(PO{sub 4}){sub 2}.4H{sub 2}O

    SciTech Connect

    Parhi, Purnendu; Manivannan, V. Kohli, Sandeep; McCurdy, Patrick


    The synthesis of crystalline zinc phosphates ({alpha}-hopeite phase) through the metathetic pathway has been investigated. The reaction has been carried out by room-temperature grinding. High lattice energy of the by-product NaCl has driven the reaction in the forward direction, and as a result, stable phosphate phases have been synthesized. Reaction of a different phosphorus source (like Na{sub 3}PO{sub 4}, Na{sub 2}HPO{sub 4}, NaH{sub 2}PO{sub 4}, and K{sub 2}HPO{sub 4}) with ZnCl{sub 2} has been attempted. The structural, vibrational, thermal, optical, and chemical properties of synthesized powders are determined by powder X-ray diffraction (XRD), scanning electron microscope (SEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and diffused reflectance spectra (DR) in the UV-vis range. The direct band gap of the title compound was determined to be 3.6 {+-} 0.2 eV.

  10. Reactivity of Chemisorbed Oxygen Atoms and Their Catalytic Consequences during CH 4sub> –O 2 Catalysis on Supported Pt Clusters

    SciTech Connect

    Chin, Ya-Huei; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique


    Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH4 oxidation reactions using O2, H2O, or CO2 as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O2 pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption–desorption equilibrium was maintained. The virtual O2 pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C–H and O=O activation steps. O* coverages and virtual pressures depend on O2 pressure when O2 activation is equilibrated and on O2/CH4 ratios when this step becomes irreversible as a result of fast scavenging of O* by CH4-derived intermediates. In three of these kinetic regimes, C–H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen–oxygen (O*–O*), to oxygen–oxygen vacancy (O*–*), and to vacancy–vacancy (*–*) site pairs as O* coverages decrease.

  11. Development of a He{sup 3}−He{sup 4} sub Kelvin active magnetic regenerative refrigerator (AMRR) with no moving parts

    SciTech Connect

    Jahromi, A. E.; Miller, F. K.


    Current state of the art particle and photon detectors such as Transition Edge Sensors (TES) and Microwave Kinetic Inductance Detectors (MKID) use large arrays of sensors or detectors for space science missions. As the size of these space science detectors increases, future astrophysics missions will require sub-Kelvin cooling over larger areas. This leads to not only increased cooling power requirements, but also a requirement for distributed sub-Kelvin cooling. We propose an active Magnetic Regenerative Refrigerator (AMRR) that uses a Superfluid Magnetic Pump (SMP) to circulate liquid He{sup 3}−He{sup 4} through a magnetic regenerator to provide the necessary cooling at sub-Kelvin temperatures. Such system will be capable of distributing the cooling load to a relatively large array of objects. One advantage of using a fluid for heat transfer in such systems is to isolate components such as the superconducting magnets from detectors that are sensitive to magnetic fields. Another advantage of the proposed tandem AMRR is that it does not need Gas Gap Heat Switches (GGHS) to transfer heat during various stages of the magnetic cooling. Our proposed system consists of four superconducting magnets, one superleak, and three heat exchangers. It will operate continuously with no moving parts and it will be capable of providing the necessary cooling at sub-Kelvin temperatures for future space science applications.

  12. High pressure, high temperature equation of state for Fe2SiO4sub> ringwoodite and implications for the Earth's transition zone

    SciTech Connect

    Armentrout, Matthew; Kavner, Abby


    We measured the density of iron-ringwoodite and its pressure and temperature dependence at conditions of the mantle transition zone using the laser-heated diamond anvil cell in conjunction with X-ray diffraction. Our new data combined with previous measurements constrain the thermoelastic properties of ringwoodite as a function of pressure and temperature throughout the transition zone. Our best fit Mie-Grueneisen-Debye equation of state parameters for Fe end-member ringwoodite are V0 = 42.03 cm3/mol, K0 = 202 (4) GPa, K' = 4, γ0 = 1.08 (6), q = 2, and θD = 685 K. This new equation of state revises calculated densities of the Fe end-member at transition zone conditions upwards by ~0.6% compared with previous formulations. We combine our data with equation of state parameters across the Mg-Fe compositional range to quantify the effect of iron and temperature on the density and bulk sound velocity of ringwoodite at pressure and temperature conditions of the Earth's transition zone. The results show that variations in iron content and temperature have opposing effects on density and bulk sound velocity, suggesting that compositional (iron content) and temperature variations in the transition zone may be distinguished using seismic observables.

  13. Low temperature synthesis of {tau}-zirconium hydrogenophosphate [{tau}-Zr(HPO{sub 4}){sub 2}] and a new sodic form obtained by ion exchange

    SciTech Connect

    Fernandez-Valverde, Suilma M.; Contreras-Ramirez, Aida; Ordonez-Regil, Eduardo; Fernandez-Garcia, M. Eufemia; Perez-Alvarez, Mario


    A new method for the synthesis of 3-D {tau}-zirconium hydrogenophosphate (TZP) was developed using solid-state reactions at low temperature and atmospheric pressure in a nitrogen atmosphere in a two-hour reaction time. The characterization of the compound was performed using X-ray diffraction, infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, differential scanning calorimetric, thermochemical analysis and X-ray photoelectron spectroscopy. A sodic form of the compound obtained by the immersion of TZP in a sodium hydroxide solution was characterized using the same techniques along with neutron activation analysis. The XPS spectra confirm the binding energy value for sodium-oxygen, and the XRD diffraction reveals the formation of a new sodium compound. - Graphical abstract: DRX, XPS and MEB of {tau}-zirconium hydrogenophosphate and its sodic form on the surface of TZP. Highlights: Black-Right-Pointing-Pointer New method for the syntheses of 3-D {tau}-zirconium hydrogenophosphate (TZP). Black-Right-Pointing-Pointer A sodic form of the TZP was obtained by the immersion of TZP in a sodium hydroxide. Black-Right-Pointing-Pointer The sodium compound is only formed on the TZP surface.

  14. Plasmonic enhancement of second harmonic generation from nonlinear RbTiOPO4sub> crystals by aggregates of silver nanostructures.


    Sánchez-García, Laura; Tserkezis, Christos; Ramírez, Mariola O; Molina, Pablo; Carvajal, Joan J; Aguiló, Magdalena; Díaz, Francesc; Aizpurua, Javier; Bausá, Luisa E


    We demonstrate a 60-fold enhancement of the second harmonic generation (SHG) response at the nanoscale in a hybrid metal-dielectric system. By using complex silver nanostructures photochemically deposited on the polar surface of a ferroelectric crystal, we tune the plasmonic resonances from the visible to the near-infrared (NIR) spectral region, matching either the SH or the fundamental frequency. In both cases the SHG signal at the metal-dielectric interface is enhanced, although with substantially different enhancement values: around 5 times when the plasmonic resonance is at the SH frequency or up to 60 times when it matches the fundamental NIR radiation. The results are consistent with the more spatially-extended near-field response of complex metallic nanostructures and can be well explained by taking into account the quadratic character of the SHG process. The work points out the potential of aggregates of silver nanostructures for enhancing optical nonlinearities at the nanoscale and provides an alternative approach for the development of nanometric nonlinear photonic devices in a scalable way. PMID:27137287

  15. Influence of Adsorption Site and Wavelength on the Photodesorption of NO from the (Fe,Cr) 3 O 4sub> (111) Mixed Oxide Surface

    SciTech Connect

    Henderson, M. A.


    The photochemical properties of nitric oxide on a mixed oxide single crystal surface was examined in ultrahigh vacuum (UHV) using temperature programmed desorption (TPD), photon stimulated desorption (PSD) and low energy electron diffraction (LEED). The mixed oxide was a 75% Fe and 25% Cr corundum (0001) oxide film prepared on an α-Al2O3(0001) crystal, however its surface became terminated with a magnetite-like (111) structure after sputter/anneal cleaning, leading to a surface designated of (Fe,Cr)3O4(111). TPD of NO from the (Fe,Cr)3O4(111) surface revealed three chemisorbed states at 220, ~315 and 370 K assigned to NO binding at Fe3+, Cr3+ and Fe2+ sites, respectively. No significant thermal chemistry of NO was detected. NO photodesorption, the primary photochemical pathway in UHV, was sensitive to the adsorption site, with rates at the three adsorption sites following the trend: Fe3+ > Fe2+ > Cr3+. Multiexponential rate behavior seen in the overall NO PSD spectra was linked directly to site heterogeneity being manifested as a convolution of the individual NO photodesorption rates at the three types of surface sites. The photodesorption rate with UV light (365 nm) was ~10 times greater than that in the visible, but the per-photon rates across the visible spectrum (from 460 to 630 nm) were independent of the wavelength, which is suggestive of localized photon absorption at the adsorption site. Results in this study demonstrate that the adsorption site plays a critical role in determining photochemical rates on complex oxide surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi-program national laboratory operated for DOE by Battelle. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  16. Impedance spectroscopy study with Ca(UO{sub 2}PO{sub 4}){sub 2}10.5H{sub 2}O films

    SciTech Connect

    Ramos-Barrado, J.R.; Benavente, J.; Bruque, S.; Martinez, M.


    Calcium uranyl phosphate (CaUP) films were prepared and characterized both chemically and structurally. The electrical behavior of the films, as a solid phase (dry film) and in contact with aqueous solutions of electrolytes containing the generating ions (wet film), was studied by impedance spectroscopy. These last measurements made it possible to determine the contribution of both the bulk film and film/electrolyte interface. For both dry and wet films, the equivalent circuits are a parallel combination of resistance and a nonideal capacitor. Temperature dependence of the impedance of the CAUP solid films was considered, while concentration dependence of the film resistance when it is in contact with the electrolyte solutions was determined. In this case, the contribution of both the bulk film and electrolyte/film interface to the total impedance was also studied.

  17. Structure of cerium potassium sulfate 2K/sub 2/SO/sub 4/. Ce(SO/sub 4/)/sub 2/. 2H/sub 2/O

    SciTech Connect

    Dikareva, L.M.; Kuznetsov, V.Y.; Porai-Koshits, M.A.; Rogachev, D.L.


    Out of 4036 independent reflections, 3828 with I > 2 sigma were used in structural calculations effected by the program ''Syntex XTL'' on a Nova 1200 minicomputer and by the program ''Struktura'' on an ES-1022 computer. The heavy-atom method was used to make the final refinement to R = 0.037, taking account of the anisotropy of the thermal vibrations of the atoms. The atomic coordinates are listed in a table.

  18. Observation, identification and characterization of strong self-reduction process in a orthophosphate phosphor CaZr{sub 4}(PO{sub 4}){sub 6}:Eu

    SciTech Connect

    Zhu, Ge; Shi, Yurong; Mikami, Masayoshi; Shimomura, Yasuo; Wang, Yuhua


    Highlights: • CaZr{sub 4}P{sub 4}O{sub 24}:Eu was synthesized by solid state reaction in air. • Relationship between the structure and luminescence properties was discussed. • Strong self-reduction process was found in CaZr{sub 4}P{sub 4}O{sub 24}:Eu prepared in air. • Oxidation states of Eu were identified by muti-method approaches. • The self-reduction mechanism was investigated. - Abstract: CaZr{sub 4}P{sub 4}O{sub 24}:Eu orthophosphate phosphor was synthesized by traditional solid state reaction in air atmosphere. The relationship between the host structure and the characteristic luminescence properties was discussed detailedly. When irradiate the sample under 365 nm UV lamp, intense green emission was observed due to the strong self-reduction process of Eu ions. The oxidation states of Eu ions were identified by muti-method approaches, including photoluminescence spectra, fluorescence lifetimes, Electron spin resonance (ESR) spectroscopy and X-ray photoelectron spectroscopy analysis (XPS). The self-reduction process was controlled by adding the charge compensator Li{sub 2}CO{sub 3} and the self-reduction mechanism was further investigated.

  19. High-temperature corrosion of UNS N10003 in molten Li2BeF4sub> (FLiBe) salt

    SciTech Connect

    Zheng, Guiqiu; Kelleher, Brian; He, Lingfeng; Cao, Guoping; Anderson, Mark; Allen, Todd; Sridharan, Kumar


    Here, corrosion testing of Hastelloy N in molten fluoride salt was performed in purified molten 27LiF-BeF2 (66-34mol%) (FLiBe) salt at 700°C for 1000 hours, in pure nickel and graphite capsules. In the nickel capsule tests, the near-surface region of the alloy exhibited an about 200 nm porous structure, an approximately 3.5 μm chromium depleted region, and MoSi2 precipitates. In tests performed in graphite capsules, the alloy samples gained weight due to the formation of a variety of Cr3C2, Cr7C3, Mo2C and Cr23C6, carbide phases on the surface and in the subsurface regions of the alloy. A Cr depleted region was observed in the near-surface region where Mo thermally diffused toward either surface or grain boundary, which induced approximately 1.4 μm Ni3Fe alloy layer in this region. The carbide containing layer extended to about 7 μm underneath the Ni3Fe layer. The presence of graphite dramatically changes the mechanisms of corrosion attack in Hastelloy N in molten FLiBe salt. Evaluated by in terms of the depth of attack, graphite clearly accelerates corrosion, but the results appear to indicate that the formation of Cr23C6 phase might stabilize the Cr and mitigate its dissolution in molten FLiBe salt.

  20. Individual response speed is modulated by variants of the gene encoding the alpha 4 sub-unit of the nicotinic acetylcholine receptor (CHRNA4).


    Schneider, Katja Kerstin; Schote, Andrea B; Meyer, Jobst; Markett, Sebastian; Reuter, Martin; Frings, Christian


    Acetylcholine (ACh) is a known modulator of several domains of cognition, among them attention, memory and learning. The neurotransmitter also influences the speed of information processing, particularly the detection of targets and the selection of suitable responses. We examined the effect of the rs1044396 (C/T) polymorphism of the gene encoding the nicotinic acetylcholine receptor α4-subunit (CHRNA4) on response speed and selective visual attention. To this end, we administered a Stroop task, a Negative priming task and an exogenous Posner-Cuing task to healthy participants (n = 157). We found that the CHRNA4 rs1044396 polymorphism modulated the average reaction times (RTs) across all three tasks. Dependent on the C allele dosage, the RTs linearly increased. Homozygous T allele carriers were always fastest, while homozygous C allele carriers were always slowest. We did not observe effects of this polymorphism on selective attention. In sum, we conclude that naturally occurring variations within the cholinergic system influence an important factor of information processing. This effect might possibly be produced by the neuromodulator system rather than the deterministic system of cortical ACh. PMID:25639542

  1. High Pressure Resistivity and Thermoelectric Power in Yb14sub>MnSb11

    SciTech Connect

    Akrap, A.; Barisic, N.; Forro, Laszlo; Mandrus, David; Sales, Brian C


    We report the electrical transport properties of Yb{sub 14}MnSb{sub 11}, resistivity and thermoelectric power under pressures up to 2.3 GPa. In both transport coefficients we can follow the ferromagnetic transition, which shows a shift from the ambient pressure value of 52 K to lower temperatures and eventually saturation at 49 K for p > 2.0 GPa. The high values of thermopower and its linear temperature dependence down to 100 K demonstrate that the system is a bad metal. Anomalies in the thermopower below the ferromagnetic transition are rather sensitive to pressure. Our experimental observations are consistent with the model of an underscreened Kondo lattice.

  2. Dopant-Induced Nanoscale Electronic Inhomogeneities in Ca2-xSrxRuO4sub>

    SciTech Connect

    Zhang, Jiandi; Ismail, #; Moore, R. G.; Wang, S. -C.; Ding, H.; Jin, Rongying; Mandrus, David; Plummer, E Ward


    Ca{sub 2-x}Sr{sub x}RuO{sub 4} single crystals with 0.1 {le} x {le} 2.0 have been studied systematically using scanning tunneling microscopy (STM) and spectroscopy, low-energy electron diffraction, and angle resolved photoelectron spectroscopy (ARPES). In contrast with the well-ordered lattice structure, the local density of states at the surface clearly shows a strong doping dependent nanoscale electronic inhomogeneity, regardless of the fact of isovalent substitution. Remarkably, the surface electronic roughness measured by STM and the inverse spectral weight of quasiparticle states determined by ARPES are found to vary with x in the same manner as the bulk in-plane residual resistivity, following the Nordheim rule. For the first time, the surface measurements - especially those with STM - are shown to be in good agreement with the bulk transport results, all clearly indicating a doping-induced electronic disorder in the system.

  3. A PbWO4sub>-based Neutral Particle Spectrometer in Hall C at 12 GeV JLab

    SciTech Connect

    Horn, Tanja


    The Neutral Particle Spectrometer is a standalone electromagnetic calorimeter capable of detecting high energy photons from, for instance, DVCS or π0 decay with good energy and spatial resolution in a high rate environment. It can be used together with the Hall C high-momentum spectrometers for a suite of experiments with the underlying scientific objective of studying quark dynamics through exclusive and semi-inclusive reactions.

  4. Free Energy Landscapes for S-H Bonds in (Cp2Mo2S4sub>)-Mo-star Complexes

    SciTech Connect

    Appel, Aaron M.; Lee, Suh-Jane; Franz, James A.; DuBois, Daniel L.; Rakowski DuBois, Mary


    Extensive thermochemical data have been determined for a series of complexes derived from Cp*Mo(μ S)2(μ SMe)(μ SH)MoCp* and Cp*Mo(μ S)2(μ SH)2MoCp*. These data include electrochemical potentials, pKa values, homolytic solution bond dissociation free energies (SBDFEs), and hydride donor abilities in acetonitrile. Thermochemical data ranged from +0.6 to -2.0 V vs FeCp2+/o for electrochemical potentials, 5 to 31 for pKa values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride donor abilities. The observed values for these thermodynamic parameters are comparable to those of many transition metal hydrides, which is consistent with the many parallels in the chemistry of these two classes of compounds. The wealth of thermochemical data are presented in free energy landscapes as a useful approach to visualizing and understanding the relative stabilities of all of the species under specified conditions. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  5. Neutron diffraction study of magnetic field induced behavior in the heavy Fermion Ce3Co4sub>Sn13

    SciTech Connect

    Christianson, Andrew D; Goremychkin, E. A.; Gardner, J. S.; Kang, H. J.; Chung, J.-H.; Manuel, P.; Thompson, J. D.; Sarrao, J. L.; Lawrence, J. M.


    The specific heat of Ce3Co4Sn13 exhibits a crossover from heavy Fermion behavior with antiferromagnetic correlations at low field to single impurity Kondo behavior above 2 T. We have performed neutron diffraction measurements in magnetic fields up to 6 Tesla on single crystal samples. The (001) position shows a dramatic increase in intensity in field which appears to arise from static polarization of the 4f level and which at 0.14 K also exhibits an anomaly near 2T reflecting the crossover to single impurity behavior.

  6. Thermodynamic modeling of solid solutions between monosulfate and monochromate 3CaO Bullet Al{sub 2}O{sub 3} Bullet Ca[(CrO{sub 4}){sub x}(SO{sub 4}){sub 1-x}] Bullet nH{sub 2}O

    SciTech Connect

    Leisinger, Sabine M.; Lothenbach, Barbara; Le Saout, Gwenn; Johnson, C. Annette


    In hydrated cement paste AFm-phases are regarded to play an important role in the binding of the toxic contaminant chromate through isomorphic substitution with sulfate. Solid solutions formation can lower the solubility of the solids, thus reducing chromate leaching concentrations. Solid solutions between monosulfate and monochromate were synthesized and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Based on the measured ion concentrations in solution total solubility products of the solid solution series were determined. For pure monochromate a logK = - 28.4 {+-} 0.7 was determined. Results from solid and solution analysis showed that limited solid solutions exist. Based on XRD diffractograms a solid solution with a miscibility gap 0.15 < Crx < 0.85 with a dimensionless Guggenheim parameter of 2.43 was proposed.

  7. Synthesis of Compositionally Defined Single-Crystalline Eu 3+ -Activated Molybdate–Tungstate Solid-Solution Composite Nanowires and Observation of Charge Transfer in a Novel Class of 1D CaMoO 4sub> –CaWO 4sub> :Eu 3+ –0D CdS/CdSe QD Nanoscale Heterostructures

    SciTech Connect

    Han, Jinkyu; McBean, Coray; Wang, Lei; Jaye, Cherno; Liu, Haiqing; Fischer, Daniel A.; Wong, Stanislaus S.


    As a first step, we have synthesized and optically characterized a systematic series of one-dimensional (1D) single-crystalline Eu³⁺-activated alkaline-earth metal tungstate/molybdate solid solution composite CaW₁₋xMoxO₄ (0 ≤ ‘x’ ≤ 1) nanowires of controllable chemical composition using a modified template-directed methodology under ambient room-temperature conditions. Extensive characterization of the resulting nanowires has been performed using X-ray diffraction, electron microscopy, and optical spectroscopy. The crystallite size and single crystallinity of as-prepared 1D CaW₁₋xMoxO₄: Eu³⁺ (0 ≤ ‘x’ ≤ 1) solid solution composite nanowires increase with increasing Mo component (‘x’). We note a clear dependence of luminescence output upon nanowire chemical composition with our 1D CaW₁₋xMoxO₄: Eu³⁺ (0 ≤ ‘x’ ≤ 1) evincing the highest photoluminescence (PL) output at ‘x’ = 0.8, amongst samples tested. Subsequently, coupled with either zero-dimensional (0D) CdS or CdSe quantum dots (QDs), we successfully synthesized and observed charge transfer processes in 1D CaW1-xMoxO4: Eu3+ (‘x’ = 0.8) – 0D QD composite nanoscale heterostructures. Our results show that CaW₁₋xMoxO₄: Eu³⁺ (‘x’ = 0.8) nanowires give rise to PL quenching when CdSe QDs and CdS QDs are anchored onto the surfaces of 1D CaW₁₋xMoxO₄: Eu³⁺ nanowires. The observed PL quenching is especially pronounced in CaW₁₋xMoxO₄: Eu³⁺ (‘x’ = 0.8) – 0D CdSe QD heterostructures. Conversely, the PL output and lifetimes of CdSe and CdS QDs within these heterostructures are not noticeably altered as compared with unbound CdSe and CdS QDs. The difference in optical behavior between 1D Eu³⁺ activated tungstate and molybdate solid solution nanowires and the semiconducting 0D QDs within our heterostructures can be correlated with the relative positions of their conduction and valence energy band levels. We propose that the PL quenching can be attributed to a photo-induced electron transfer process from CaW₁₋xMoxO₄: Eu³⁺ (‘x’ = 0.8) to both CdSe and CdS QDs, an assertion supported by complementary NEXAFS measurements.

  8. Extended Scattering Continua Characteristic of Spin Fractionalization in the Two-dimensional Frustrated Quantum Magnet Cs2CuCl4sub>Observed by Neutron Scattering

    SciTech Connect

    Coldea, Radu; Tennant, D. A.; Tyleczynski, Z.


    The magnetic excitations of the quasi-2D spin-1/2 frustrated Heisenberg antiferromagnet Cs{sub 2}CuCl{sub 4} are explored throughout the 2D Brillouin zone using high-resolution time-of-flight inelastic neutron scattering. Measurements are made both in the magnetically ordered phase, stabilized at low temperatures by the weak interlayer couplings, as well as in the spin liquid phase above the ordering temperature T{sub N}, when the 2D magnetic layers are decoupled. In the spin liquid phase the dynamical correlations are dominated by highly dispersive excitation continua, a characteristic signature of fractionalization of S = 1 spin waves into pairs of deconfined S = 1/2 spinons and the hallmark of a resonating-valence-bond (RVB) state. The boundaries of the excitation continua have strong 2D-modulated incommensurate dispersion relations. Upon cooling below T{sub N} magnetic order in an incommensurate spiral forms due to the 2D frustrated couplings. In this phase sharp magnons carrying a small part of the total scattering weight are observed at low energies, but the dominant continuum scattering which occurs at medium to high energies is essentially unchanged compared to the spin liquid phase. Linear spin-wave theory including one- and two-magnon processes can describe the sharp magnon excitation, but not the dominant continuum scattering, which instead is well described by a parametrized two-spinon cross section. Those results suggest a crossover in the nature of the excitations from S = 1 spin waves at low energies to deconfined S = 1/2 spinons at medium to high energies, which could be understood if Cs{sub 2}CuCl{sub 4} was in the close proximity of transition between a fractional RVB spin liquid and a magnetically ordered state. A large renormalization factor of the excitation energies [R = 1.63(5)], indicating strong quantum fluctuations in the ground state, is obtained using the exchange couplings determined from saturation-field measurements. We provide an independent consistency check of this quantum renormalization factor using measurements of the second moment of the paramagnetic scattering.

  9. Investigation of sodium insertion–extraction in olivine Na x FePO 4sub> (0 ≤ x ≤ 1) using first-principles calculations

    SciTech Connect

    Saracibar, A.; Carrasco, J.; Saurel, D.; Galceran, M.; Acebedo, B.; Anne, H.; Lepoitevin, M.; Rojo, T.; Casas Cabanas, M.


    Olivine NaFePO4 has recently attracted the attention of the scientific community as a promising cathode material for Na-ion batteries. In this work we combine density functional theory (DFT) calculations and high resolution synchrotron X-ray diffraction (HRXRD) experiments to study the phase stability of NaxFePO4 along the whole range of sodium compositions (0 ≤ x ≤ 1). DFT calculations reveal the existence of two intermediate structures governing the phase stability at x = 2/3 and x = 5/6. This is in contrast to isostructural LiFePO4, which is a broadly used cathode in Li-ion batteries. Na2/3FePO4 and Na5/6FePO4 ground states both align vacancies diagonally within the ab plane, coupled to a Fe2+/Fe3+ alignment. HRXRD data for NaxFePO4 (2/3 < x < 1) materials show common superstructure reflections up to x = 5/6 within the studied compositions. The computed intercalation voltage profile shows a voltage difference of 0.16 V between NaFePO4 and Na2/3FePO4 in agreement with the voltage discontinuity observed experimentally during electrochemical insertion.

  10. Resonance in the Electron-doped High-Tc Superconductor Pr0.88LaCe0.12CuO4-?sub>

    SciTech Connect

    Wilson, Stephen D.; Dai, Pengcheng; Li, Shiliang; Chi, Songxue; Kang, H. J.; Lynn, J. W.


    In conventional superconductors, the interaction that pairs the electrons to form the superconducting state is mediated by lattice vibrations (phonons). In high-transition-temperature (high-T{sub c}) copper oxides, it is generally believed that magnetic excitations might play a fundamental role in the superconducting mechanism because superconductivity occurs when mobile 'electrons' or 'holes' are doped into the antiferromagnetic parent compounds. Indeed, a sharp magnetic excitation termed 'resonance' has been observed by neutron scattering in a number of hole-doped materials. The resonance is intimately related to superconductivity, and its interaction with charged quasi-particles observed by photoemission, optical conductivity, and tunnelling suggests that it might play a part similar to that of phonons in conventional superconductors. The relevance of the resonance to high-T{sub c} superconductivity, however, has been in doubt because so far it has been found only in hole-doped materials. Here we report the discovery of the resonance in electron-doped superconducting Pr{sub 0.88}LaCe{sub 0.12}CuO{sub 4-{delta}} (T{sub c} = 24 K). We find that the resonance energy (E{sub r}) is proportional to T{sub c} via E{sub r} {approx} 5.8k{sub B}T{sub c} for all high-T{sub c} superconductors irrespective of electron- or hole-doping. Our results demonstrate that the resonance is a fundamental property of the superconducting copper oxides and therefore must be essential in the mechanism of superconductivity.

  11. Reconciliation of local and long-range tilt correlations in underdoped La2-xBaxCuO4sub>(0 ≤ x ≤ 0.155)

    SciTech Connect

    Bozin, Emil S.; Zhong, Ruidan; Knox, Kevin R.; Gu, Genda; Hill, John P.; Tranquada, John M.; Billinge, Simon J. L.


    A long standing puzzle regarding the disparity of local and long range CuO₆ octahedral tilt correlations in the underdoped regime of La₂₋xBaxCuO₄ is addressed by utilizing complementary neutron powder diffraction and inelastic neutron scattering (INS) approaches. Long-range and static CuO₆ tilt order with orthogonally inequivalent Cu-O bonds in the CuO₂ planes in the low temperature tetragonal (LTT) phase is succeeded on warming through the low-temperature transition by one with orthogonally equivalent bonds in the low temperature orthorhombic (LTO) phase. In contrast, the signatures of LTT-type tilts in the instantaneous local atomic structure persist on heating throughout the LTO crystallographic phase on the nanoscale, although becoming weaker as temperature increases. Analysis of the INS spectra for the x = 1/8 composition reveals the dynamic nature of the LTT-like tilt fluctuations within the LTO phase and their 3D character. The doping dependence of relevant structural parameters indicates that the magnitude of the Cu-O bond anisotropy has a maximum at x = 1/8 doping where bulk superconductivity is most strongly suppressed, suggesting that the structural anisotropy might be influenced by electron-phonon coupling and the particular stability of the stripe-ordered phase at this composition. The bond-length modulation that pins stripe order is found to be remarkably subtle, with no anomalous bond length disorder at low temperature, placing an upper limit on any in-plane Cu-O bondlength anisotropy. The results further reveal that although appreciable octahedral tilts persist through the high-temperature transition and into the high temperature tetragonal (HTT) phase, there is no significant preference between different tilt directions in the HTT regime. As a result, this study also exemplifies the importance of a systematic approach using complementary techniques when investigating systems exhibiting a large degree of complexity and subtle structural responses.

  12. Forsterite [Mg 2 SiO 4sub> )] Carbonation in Wet Supercritical CO 2 : An in Situ High-Pressure X-ray Diffraction Study

    SciTech Connect

    Todd Schaef, Herbert; McGrail, Bernard P.; Loring, John L.; Bowden, Mark E.; Arey, Bruce W.; Rosso, Kevin M.


    Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring with forsterite (Mg2SiO4) exposed to wet supercritical CO2. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks and has been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Transformation reactions were examined by in situ high pressure x-ray diffraction in the presence of supercritical carbon dioxide (scCO2) containing dissolved water at conditions relevant to carbon sequestration. Under modest pressures (90 bar) and temperatures (50°C), scCO2 saturated with water was found to convert >70 wt% forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO3 •3H2O) and magnesite (MgCO3), after 72 hours of reaction. However, comparable tests with scCO2 at only partial water saturation (82%) showed a significantly slower carbonation rate with only ~30-39 wt% conversion to nesquehonite and no evidence of the anhydrous form (MgCO3). Further decreases in water content of the scCO2 continued to reduce the extent of carbonation, until a critical moisture threshold (~30%) was crossed where forsterite no longer reacted in the presence of the wet scCO2 to form crystalline carbonates. Increasing the temperature to 75°C produced anhydrous magnesium carbonate, magnesite (MgCO3), preceded by the intermediate phase, hydromagnesite [Mg(CO3)4(OH)2 •4H2O]. Measurements conducted during in situ IR experiments at 50°C and 30% saturation identified the presence of an amorphous carbonate phase as well as the formation of a thin liquid-like water layer on the forsterite surface. The presence of this water film appears to be critical for the mineral carbonation of forsterite exposed to water bearing scCO2. In contrast, our prior studies with the mineral brucite [Mg(OH)2] showed extensive carbonation in the absence of a condensed water layer on the mineral surface. The contrasts in reaction rate and products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to help enable better predictions of the long term fate of geologically stored CO2.

  13. Effect of epitaxial strain on small-polaron hopping conduction in Pr{sub 0.7}(Ca{sub 0.6}Sr{sub 0.4}){sub 0.3}MnO{sub 3} thin films

    SciTech Connect

    Wang, Jing Hu, Feng-xia; Zhao, Ying-ying; Liu, Yao; Wu, Rong-rong; Sun, Ji-rong; Shen, Bao-gen


    We investigated the epitaxial strain effect on the small-polaron hopping conduction properties in Pr{sub 0.7}(Ca,Sr){sub 0.3}MnO{sub 3} (PCSMO) films. An increase in the carrier localization, as evidenced by the enhancement of the small-polaron activation energy E{sub A} in the high temperature region, was obtained by increasing the epitaxial lattice strain in either the tensile or compressive strained film. Furthermore, it was found that the magnitude of E{sub A}, and thus the carrier localization, strongly depends on the sign of the lattice strain, which explains the diverse percolative transport behaviors in PCSMO films with different types of strains. Meanwhile, similar dependencies on the strain of the films were also obtained for the electron-phonon interaction, characterized by the calculated small-polaron coupling constant. Our results reveal that the type of lattice strain plays a crucial role in determining the degree of localization of charge carriers and the electron-phonon coupling strength, which is important for understanding the lattice strain-induced various novel properties related to phase separation and percolation behaviors.

  14. TEM Characterization of Nanostructured MgAl2O4sub> Synthesized by a Direct Conversion Process from gamma-Al2O3

    SciTech Connect

    Al-Sharab, J.F.; Cosandey, F.; Singhal, Amit; Skandan, Ganesh; Bentley, James


    Nanostructured MgAl{sub 2}O{sub 4} spinel was synthesized by a direct conversion process from cubic ?-Al2O3. The effect of post-annealing temperature (300C, 500C, and 800C) on MgAl2O4 phase formation was investigated using transmission electron microscopy, selected area electron diffraction (SAED), electron energy loss spectroscopy (EELS), and energy-dispersive spectroscopy (EDS). Relative diffraction intensities as well as lattice parameter measurements from SAED revealed that MgAl2O4 spinel structure starts forming at temperatures as low as 300C. EELS and EDS spectrum images also revealed an increase in elemental homogeneity with increasing annealing temperature. The degree of ordering of Mg and Al between octahedral and tetrahedral sites has been determined from relative diffraction intensities. Results show that annealing to 800C leads to a spinel phase with an order parameter of 0.78.

  15. Ultrafast direct laser writing of cladding waveguides in the 0.8CaSiO{sub 3}-0.2Ca{sub 3}(PO{sub 4}){sub 2} eutectic glass doped with Nd{sup 3+} ions

    SciTech Connect

    Martínez de Mendívil, J. Lifante, G.; Sola, D.; Peña, J. I.; Vázquez de Aldana, J. R.; Aza, A. H. de; Pena, P.


    We report on tubular cladding optical waveguides fabricated in Neodymium doped Wollastonite-Tricalcium Phosphate glass in the eutectic composition. The glass samples were prepared by melting the eutectic powder mixture in a Pt-Rh crucible at 1600 °C and pouring it in a preheated brass mould. Afterwards, the glass was annealed to relieve the inner stresses. Cladding waveguides were fabricated by focusing beneath the sample surface using a pulsed Ti:sapphire laser with a pulsewidth of 120 fs working at 1 kHz. The optical properties of these waveguides have been assessed in terms of near-field intensity distribution and transmitted power, and these results have been compared to previously reported waveguides with double-line configuration. Optical properties have also been studied as function of the temperature. Heat treatments up to 700 °C were carried out to diminish colour centre losses where waveguide's modes and transmitted power were compared in order to establish the annealing temperature at which the optimal optical properties were reached. Laser experiments are in progress to evaluate the ability of the waveguides for 1064 nm laser light generation under 800 nm optical pumping.

  16. Eu2+-doped M2SiO4sub> (M = Ca, Ba) phosphors prepared by a rapid microwave-assisted sol-gel method: Phase formation and optical properties

    SciTech Connect

    Birkel, Alexander; DeCino, Nicholas A; George, Nathan C; Hazelton, Katherine A; Hong, Byung-Chul; Seshadri, Ram


    We present a rapid microwave-assisted approach for the preparation of Eu2+-doped orthosilicate phosphors. The preparation method relies on a citrate based sol–gel reaction with subsequent combustion in a domestic microwave oven, in contrast to more conventional solid-state methods. This sol–gel pathway yields phase pure, high quality orthosilicates, in less than 25 min of final heating time. In addition, superior morphology control is achieved employing the sol–gel method compared to solid-state preparations. In order to understand the formation process of the final products, thermogravimetric analyses and temperature-dependent X-ray diffraction data were acquired and compared to the conventional solid-state preparation. The morphology and elemental composition of the obtained luminescent materials were investigated using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The optical properties were elucidated by measuring room-temperature emission and excitation spectra, and the application and efficiency of the obtained phosphors in LED devices was studied.

  17. Post-Synthetic Modification of Porphyrin-Encapsulating Metal-Organic Materials by Cooperative Addition of Inorganic Salts to Enhance CO2/CH4sub> Selectivity

    SciTech Connect

    Zhang, Zhenjie; Gao, Wen-Yang; Wojtas, Lukasz; Ma, Shengqian; Eddaoudi, Mohamed; Zaworotko, Michael J


    Keeping MOM: Reaction of biphenyl-3,4',5-tricarboxylate and Cd(NO3)2 in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate afforded porph@MOM-11, a microporous metal–organic material (MOM) that encapsulates cationic porphyrins and solvent in alternating open channels. Porph@MOM-11 has cation and anion binding sites that facilitate cooperative addition of inorganic salts (such as M+Cl-) in a stoichiometric fashion.

  18. Crystal structure of the (Mg,Fe)[UO{sub 2}(P,As)O{sub 4}]{sub 2} . 10H{sub 2}O solid solution-A novel mineral variety of saleeite

    SciTech Connect

    Yakubovich, O. V.; Steele, I. M.; Atencio, D.; Menezes, L. A.; Chukanov, N. V.


    The crystal structure of a novel variety {l_brace}[(Mg{sub 0.81}Fe{sub 0.19})(H{sub 2}O){sub 6}](H{sub 2}O){sub 4}{r_brace}{l_brace}(UO{sub 2})[(P{sub 0.67}As{sub 0.33})O{sub 4}]{r_brace}{sub 2} of the mineral saleeite is determined using X-ray diffraction (Bruker Smart diffractometer, {lambda}MoK{sub {alpha}}, graphite monochromator, 2{theta}{sub max} = 56.62{sup o}, R = 0.0321 for 2317 reflections, T = 100 K). The main crystal data are as follows: a = 6.952(6) A, b = 19.865(5) A, c = 6.969(2) A, {beta} = 90.806(4){sup o}, space group P12{sub 1}/n1, Z = 2, and {rho}{sub calcd} = 3.34 g/cm{sup 3}. It is shown that the structure is formed by alternating (along the [010] direction) anionic layers, which are composed of uranium bipyramids and T(P,As) tetrahedra, and cation layers consisting of M(Mg,Fe) octahedra and water molecules, which are joined through a system of asymmetric hydrogen bonds. The hydrogen atoms are located, the scheme of hydrogen bonds is established, and their geometric characteristics are calculated.

  19. Removal of Rb(62P) by H2, CH4sub>, and C2H6.


    Azyazov, V N; Bresler, S M; Torbin, A P; Mebel, A M; Heaven, M C


    The saturated hydrocarbons methane and ethane are often used as collisional energy transfer agents in diode-pumped alkali vapor lasers (DPALs). Problems are encountered because the hydrocarbons eventually react with the optically pumped alkali atoms, resulting in the contamination of the gas lasing medium and damage of the gas cell windows. The reactions require excitation of the more highly excited states of the alkali atoms, which can be generated in DPAL systems by energy pooling processes. Knowledge of the production and loss rates for the higher excited states is needed for a quantitative understanding of the photochemistry. In the present study, we have used experimental and theoretical techniques to characterize the removal of Rb(6P2) by hydrogen, methane, and ethane. PMID:26872159

  20. Chalcogenide chemistry in ionic liquids: nonlinear optical wave-mixing properties of the double-cubane compound [Sb{sub 7}S{sub 8}Br{sub 2}](AlCl{sub 4}){sub 3}.

    SciTech Connect

    Zhang, Q.; Chung, I.; Jang, J. I.; Ketterson, J. B.; Kanatzidis, M. G.


    The new cation [Sb{sub 7}S{sub 8}Br{sub 2}]{sup 3+} has a double-cubane structure and forms as the [AlCl{sub 4}]{sup -} salt from the ionic liquid EMIMBr-AlCl{sub 3} (EMIM = 1-ethyl-3-methylimidazolium) at 165 C. The compound is noncentrosymmetric with space group P2{sub 1}2{sub 1}2{sub 1} and exhibits second-harmonic and difference-frequency nonlinear optical response across a wide range of the visible and near-infrared regions.

  1. nomalous Interface and Surface Strontium Segregation in (La1-ySry)2CoO4 sub>/La1-xSrxCoO3- Heterostructured Thin Films

    SciTech Connect

    Feng, Zhenxing; Yacoby, Yuzhak; Gadre, Milind; Lee, Yueh-Lin; Hong, W.; Zhou, Hua; Biegalski, Michael D; Christen, Hans M; Adler, Stuart; Morgan, Dane; Shao-Horn, Yang


    Heterostructured materials have shown unusual physiochemical properties at the interfaces such as two dimensional electron gas systems, high-temperature superconductivity, and enhanced catalysis. Here we report the first atomic-scale evidence of the microscopic structure of a perovskite/Ruddlesden-Popper heterostructure (having La1-xSrxCoO3- /(La1-ySry)2CoO4 ), and anomalous strontium segregation at the interface and in the Ruddlesden-Popper structure using direct X-ray methods combined with ab initio calculations. The remarkably enhanced activity of such heterostructured surfaces relative to bulk perovskite and Ruddlesden-Popper oxides previously shown for oxygen electrocatalysis at elevated temperatures can be attributed to reduced thermodynamic penalty of oxygen vacancies in the oxide structure associated with Sr segregation observed in the heterostructure. Our findings provide insights for the design of highly active catalysts for energy conversion and storage applications.

  2. Spectroscopy and kinetics of the population of monoclinic KYb{sub 0.5}Y{sub 0.43}Tm{sub 0.07}(WO{sub 4}){sub 2} crystals pumped by a pulsed Nd:YAG laser

    SciTech Connect

    Vatnik, S M; Maiorov, A P; Plakushchev, D V; Pavlyuk, A A


    The kinetics of pump radiation absorption and luminescence of monoclinic crystals of potassium-yttrium-ytterbium tungstate doped with thulium are studied. It is shown theoretically and experimentally that due to the 'excitation multiplication' caused by absorption of pump radiation from metastable states of thulium ions accompanied by cross-relaxation, above 50 % of a total number of thulium ions can occupy the {sup 3}F{sub 4} level. The cross sections of stimulated transitions in the spectral region from 1600 to 2100 nm are calculated from luminescence spectra, and the gain in the crystal is estimated. The prospects of practical applications of the results obtained in the paper are discussed. (active media)

  3. Alpha self-irradiation effects in ternary oxides of actinides elements: The zircon-like phases Am{sup III}VO{sub 4} and A{sup II}Np{sup IV}(VO{sub 4}){sub 2} (A=Sr, Pb)

    SciTech Connect

    Goubard, F. . E-mail:; Griesmar, P.; Tabuteau, A.


    We report the experimental studies of irradiation damage from alpha decay in neptunium and americium vanadates versus cumulative dose. The isotopes used were the transuranium {alpha}-emitter {sup 237}Np and the {alpha},{gamma}-emitter {sup 241}Am. Neptunium and americium vanadates self-irradiation was studied by X-ray diffraction method (XRD). The comparison of the powder diffraction patterns reveal that the irradiation has no apparent effect on the neptunium phases while the americium vanadate swells and becomes metamict as a function of cumulative dose.

  4. Multifunctional, Phase-Separated, BaTiO3 + CoFe2O4sub> Cap Buffer Layers for Improved Flux-Pinning in YBa2Cu3O7- Based Coated Conductors

    SciTech Connect

    Wee, Sung Hun; Shin, Junsoo; Cantoni, Claudia; Zuev, Yuri L; Cook, Sylvester W; Goyal, Amit


    Phase separated, epitaxial, nanostructured film comprised of BaTiO{sub 3} (BTO) and CoFe{sub 2}O{sub 4} (CFO) composite has been developed as a potential multifunctional cap buffer layer for improved flux-pinning in YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} (YBCO) films. All films were deposited by pulsed laser deposition on SrTiO{sub 3} (STO) (100) single crystal substrates. The CFO fraction and growth temperature were identified as key factors for determining the areal number density and mean diameter of the CFO nanocolumns. Compared to the reference sample grown on a pure BTO cap layer, the YBCO films grown on BTO+CFO cap layers show a remarkable improvement in isotropic flux-pinning and, consequently, J{sub c} over the entire field and angle ranges. Transmission electron microscopy analysis confirmed the presence of a very defective YBCO layer containing a high density of randomly distributed defects at the interface area, induced by nanostructural modulation on the surface of the BTO+CFO composite cap layer.


    EPA Science Inventory

    The reactivity of Cc4sub> with pyrite was investigated by measuring the CC14sub> transformation rates and products under aerobic and anaerobic conditions. Under all reaction conditions, >90% of the CC14sub> was transformed within 12- 36 days in the presence o...


    EPA Science Inventory

    Studies were done to assess the effects of soil moisture manipulations on CH4sub> oxidation in soils from a dry alpine tundra site. When water was added to these soils there was a stimulation of CH4sub> oxidation. This stimulation of CH4sub> oxidation took ti...

  7. Frequency doubled operation of a ground state depleted laser using the Nd(3+)(4)F(sub 3/2)-(4)I(sub 9/2) transition in Y2SiO5

    NASA Astrophysics Data System (ADS)

    Beach, R.; Albrecht, G.; Mitchell, S.; Comaskey, B.; Solarz, R.; Krupke, William F.; Brandle, C.; Berkstresser, G.


    A ground state depleted (GSD) laser has been demonstrated at 912 nm in the form of a Q-switched oscillator operating on the Nd(3+) F-4(sub 3/2) - I-4(sub 9/2) transition in Y2SiO5. Samarium scandium gallium garnet has been demonstrated effective at selectively suppressing the competing and much stronger F-4(sub 3/2) - I-4(sub 11/2) lasing transition. Efficient harmonic generation has been demonstrated using non-critically phase matched KNbO3.


    EPA Science Inventory

    The spatial and temporal variability of ambient air concentrations of SO2, SO4SUB>2-, NO3, HNO3, and NH4SUB>+ obtained from EPA's CASTNet was examined using an objective, statistically based technique...


    EPA Science Inventory

    The effects of NH4SUB>Cl and KNO3 on biodegradation of light Arabian crude oil by an oil-degrading enrichment culture were studied in respirometers. In poorly buffered sea salts medium, the pH decreased dramatically in cultures that contained NH4SUB>Cl, b...

  10. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    SciTech Connect

    Weydert, M.


    Compounds (RC{sub 5}H{sub 4}){sub 3}U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC{sub 5}H{sub 4}){sub 3}UCl with t-BuLi (R = t-Bu, Me{sub 3}Si). Reactions of (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC{sub 5}H{sub 4}){sub 3}ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC{sub 5}H{sub 4}){sub 4}U compounds is next considered. Reaction of the trivalent (RC{sub 5}H{sub 4}){sub 3}U with (RC{sub 5}H{sub 4}){sub 2}Hg results in formation of (RC{sub 5}H{sub 4}){sub 4}U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

  11. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    SciTech Connect

    Weydert, M.


    Compounds (RC[sub 5]H[sub 4])[sub 3]U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC[sub 5]H[sub 4])[sub 3]UCl with t-BuLi (R = t-Bu, Me[sub 3]Si). Reactions of (MeC[sub 5]H[sub 4])[sub 3]U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC[sub 5]H[sub 4])[sub 3]ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC[sub 5]H[sub 4])[sub 4]U compounds is next considered. Reaction of the trivalent (RC[sub 5]H[sub 4])[sub 3]U with (RC[sub 5]H[sub 4])[sub 2]Hg results in formation of (RC[sub 5]H[sub 4])[sub 4]U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)


    EPA Science Inventory

    In this study, first, we evaluate the Eta-CMAQ forecast model performance for the chemical components (SO4SUB>2-, NO3-, and NH4SUB>+) of PM2.5 with the observational data from aircraft flights during the 2004 In...


    EPA Science Inventory

    All titanium is produced by the Kroll process, which is a batch process for the magnesium (Mg) reduction of titanium tetrachloride (TiCl4sub>). Separate operations are required to produce the toxic and very corrosive TiCl4sub>, which must be stored and transporte...

  14. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

    SciTech Connect

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; Johnston, Murray V.


    Quantum chemical calculations were employed to model the interactions of the [(NH4sub>+)4sub>(HSO4sub>-)4sub>] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH4sub>+)4sub>(SO4sub>-)4sub>] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.


    EPA Science Inventory

    The Aerosol Inorganics Model (AIM) is widely used to calculate gas/liquid/solid phase equilibrium in aerosol systems containing the species H+-NH4SUB>+-SO4SUB>2--NO3--H2O over a range of tropospheric ...

  16. Crystallization and preliminary X-ray crystallographic studies of the ArsI C–As lyase from Thermomonospora curvata

    SciTech Connect

    Nadar, S. Venkadesh; Yoshinaga, Masafumi; Kandavelu, Palani; Sankaran, Banumathi; Rosen, Barry P.


    The ArsI C-As lyase from Thermomonospora curvata was expressed, purified and crystallized. The crystals diffracted to 1.46 Å and belong to space group P4{sub 3}2{sub 1}2 or its enantiomer P4{sub 1}2{sub 1}2.

  17. Structural Interactions within Lithium Salt Solvates. Acyclic Carbonates and Esters

    SciTech Connect

    Afroz, Taliman; Seo, D. M.; Han, Sang D.; Boyle, Paul D.; Henderson, Wesley A.


    Solvate crystal structures serve as useful models for the molecular-level interactions within the diverse solvates present in liquid electrolytes. Although acyclic carbonate solvents are widely used for Li-ion battery electrolytes, only three solvate crystal structures with lithium salts are known for these and related solvents. The present work, therefore, reports six lithium salt solvate structures with dimethyl and diethyl carbonate: (DMC)2:LiPF6, (DMC)1:LiCF3SO3, (DMC)1/4sub>:LiBF4sub>, (DEC)2:LiClO4sub>, (DEC)1:LiClO4sub> and (DEC)1:LiCF3SO3 and four with the structurally related methyl and ethyl acetate: (MA)2:LiClO4sub>, (MA)1:LiBF4sub>, (EA)1:LiClO4sub> and (EA)1:LiBF4sub>.

  18. Pathways and transformations of dissolved methane and dissolved inorganic carbon in Arctic tundra watersheds: Evidence from analysis of stable isotopes

    SciTech Connect

    Throckmorton, Heather M.; Heikoop, Jeffrey M.; Newman, Brent D.; Altmann, Garrett L.; Conrad, Mark S.; Muss, Jordan D.; Perkins, George B.; Smith, Lydia J.; Torn, Margaret S.; Wullschleger, Stan D.; Wilson, Cathy J.


    Arctic soils contain a large pool of terrestrial C and are of interest due to their potential for releasing significant carbon dioxide (CO2) and methane (CH4sub>) to the atmosphere. Due to substantial landscape heterogeneity, predicting ecosystem-scale CH4sub> and CO2 production is challenging. This study assessed dissolved inorganic carbon (DIC = Σ (total) dissolved CO2) and CH4sub> in watershed drainages in Barrow, Alaska as critical convergent zones of regional geochemistry, substrates, and nutrients. In July and September of 2013, surface waters and saturated subsurface pore waters were collected from 17 drainages. Based on simultaneous DIC and CH4sub> cycling, we synthesized isotopic and geochemical methods to develop a subsurface CH4sub> and DIC balance by estimating mechanisms of CH4sub> and DIC production and transport pathways and oxidation of subsurface CH4sub>. We observed a shift from acetoclastic (July) toward hydrogenotropic (September) methanogenesis at sites located toward the end of major freshwater drainages, adjacent to salty estuarine waters, suggesting an interesting landscape-scale effect on CH4sub> production mechanism. The majority of subsurface CH4sub> was transported upward by plant-mediated transport and ebullition, predominantly bypassing the potential for CH4sub> oxidation. Thus, surprisingly, CH4sub> oxidation only consumed approximately 2.51± 0.82% (July) and 0.79 ± 0.79% (September) of CH4sub> produced at the frost table, contributing to <0.1% of DIC production. DIC was primarily produced from respiration, with iron and organic matter serving as likely e- acceptors. Furthermore, this work highlights the importance of spatial and temporal variability of CH4sub> production at the watershed scale and suggests broad scale investigations are required to build better regional or pan-Arctic representations of CH

  19. A β-VOPO4/ε-VOPO4 composite Li-ion battery cathode

    SciTech Connect

    Chen, Zehua; Chen, Qiyuan; Wang, Haiyan; Zhang, Ruibo; Zhou, Hui; Chen, Liquan; Whittingham, M. Stanley


    VOPO4sub> is an example of a Li-ion battery cathode that can achieve over 300 Ah/kg when two Li-ions are intercalated. A two phase β-VOPO4sub>/ε-VOPO4sub> composite was found to improve the cycling capacity of ε-VOPO4sub> from tetragonal H2VOPO4sub>, particularly as the rate is increased. In the potential range of 2.0–4.5 V, this composite showed an initial electrochemical capacity of 208 mAh/g at 0.08 mA/cm2, 190 mAh/g at 0.16 mA/cm2, and 160 mAh/g at 0.41 mA/cm2.

  20. Top-down methane emissions estimates for the San Francisco Bay Area from 1990 to 2012

    SciTech Connect

    Fairley, David; Fischer, Marc L.


    Methane is a potent greenhouse gas (GHG) that is now included in both California State and San Francisco Bay Area (SFBA) bottom-up emission inventories as part of California's effort to reduce anthropogenic GHG emissions. Here we provide a top-down estimate of methane (CH4sub>) emissions from the SFBA by combining atmospheric measurements with the comparatively better estimated emission inventory for carbon monoxide (CO). Local enhancements of CH4sub> and CO are estimated using measurements from 14 air quality sites in the SFBA combined together with global background measurements. Mean annual CH4sub> emissions are estimated from the product of Bay Area Air Quality Management District (BAAQMD) emission inventory CO and the slope of ambient local CH4sub> to CO. The resulting top-down estimates of CH4sub> emissions are found to decrease slightly from 1990 to 2012, with a mean value of 240 ± 60 GgCH4sub> yr⁻¹ (at 95% confidence) in the most recent (2009–2012) period, and correspond to reasonably a constant factor of 1.5–2.0 (at 95% confidence) times larger than the BAAQMD CH4sub> emission inventory. However, we note that uncertainty in these emission estimates is dominated by the variation in CH4sub>:CO enhancement ratios across the observing sites and we expect the estimates could represent a lower-limit on CH4sub> emissions because BAAQMD monitoring sites focus on urban air quality and may be biased toward CO rather than CH4sub> sources.

  1. A microbial functional group-based module for simulating methane production and consumption: Application to an incubated permafrost soil

    SciTech Connect

    Xu, Xiaofeng; Elias, Dwayne A.; Graham, David E.; Phelps, Tommy J.; Carroll, Sue L.; Wullschleger, Stan D.; Thornton, Peter E.


    In this study, accurately estimating methane (CH4sub>) flux is critically important for investigating and predicting the biogeochemistry-climate feedback. Better simulating CH4sub> flux requires explicit representations of microbial processes on CH4sub> dynamics because all processes for CH4sub> production and consumption are actually carried out by microbes. A microbial functional group based module was developed and tested against an incubation experiment. The module considers four key mechanisms for CH4sub> production and consumption: methanogenesis from acetate or single-carbon compounds and CH4sub> oxidation using molecular oxygen or other inorganic electron acceptors. These four processes were carried out by four microbial functional groups: acetoclastic methanogens, hydrogenotrophic methanogens, aerobic methanotrophs, and anaerobic methanotrophs. This module was then linked with the decomposition subroutine of the Community Land Model, and was further used to simulate dynamics of carbon dioxide (CO2) and CH4sub> concentrations from an incubation experiment with permafrost soils. The results show that the model could capture the dynamics of CO2 and CH4sub> concentrations in microcosms with top soils, mineral layer soils and permafrost soils under natural and saturated moisture conditions and a temperature gradient of -2°C, 3°C, and 5°C. Sensitivity analysis confirmed the importance of acetic acid's direct contribution as substrate and indirect effects through pH feedback on CO2 and CH4sub> production and consumption. This study suggests that representing the microbial mechanisms is critical for modeling CH4sub> production and consumption; it is urgent to incorporate microbial mechanisms into Earth system models for better predicting the behavior of the climate system.

  2. Structural disorder, octahedral coordination and two-dimensional ferromagnetism in anhydrous alums

    SciTech Connect

    West, D.V. Huang, Q.; Zandbergen, H.W.; McQueen, T.M.; Cava, R.J.


    The crystal structures of the triangular lattice, layered anhydrous alums KCr(SO{sub 4}){sub 2}, RbCr(SO{sub 4}){sub 2} and KAl(SO{sub 4}){sub 2} are characterized by X-ray and neutron powder diffraction (NPD) at temperatures between 1.4 and 773 K. The compounds all crystallize in the space group P3-bar, with octahedral coordination of the trivalent cations. In all cases, small amounts of disorder in the stacking of the triangular layers of corner sharing MO{sub 6} octahedra and SO{sub 4} tetrahedra is seen, with the MO{sub 6}-SO{sub 4} network rotated in opposite directions between layers. The electron diffraction study of KCr(SO{sub 4}){sub 2} supports this model, which on an average can be taken to imply trigonal prismatic coordination for the M{sup 3+} ions; as was previously reported for the prototype anhydrous alum, KAl(SO{sub 4}){sub 2}. The temperature-dependent magnetic susceptibilities for ACr(SO{sub 4}){sub 2} (A=K, Rb, Cs) indicate the presence of predominantly ferromagnetic interactions. Low-temperature powder neutron diffraction reveals that the magnetic ordering is ferromagnetic in-plane, with antiferromagnetic ordering between planes below 3 K. - Graphical abstract: The anhydrous alums KCr(SO{sub 4}){sub 2}, RbCr(SO{sub 4}){sub 2} and KAl(SO{sub 4}){sub 2} are characterized by X-ray and neutron powder diffraction and TEM diffraction. All compounds have octahedral coordination of the trivalent cations. Stacking disorder is observed, with the MO{sub 6}-SO{sub 4} network of polyhedra rotated in opposite directions between layers. Low-temperature NPD reveals ferromagnetic in-plane ordering, with antiferromagnetic ordering between planes below 3 K.

  3. Synthesis and crystallochemical study of hydrates of trichromatodiuranylates of ammonium, potassium, and rubidium

    SciTech Connect

    Kuchumova, N.V.; Serezhkina, L.B.; Serezhkin, V.N.


    We have synthesized and studied thermographically some hydrates of trichromatodiuranylates (NH/sub 4/)/sub 2/(UO/sub 2/)/sub 2/(CrO/sub 4/)/sub 3//centered dot/5H/sub 2/O and R/sub 2/(UO/sub 2/)/sub 2/(CrO/sub 4/)/sub 3//centered dot/6H/sub 2/O (R=K, Rb). We present the crystallographic characteristics of the compounds and discuss hypotheses concerning their structure. X-ray phase, x-ray diffraction, differential thermal, thermogravimetric, and chemical analyses were conducted.

  4. Synthesis, characterization and electrical properties of a lead sodium vanadate apatite

    SciTech Connect

    Chakroun-Ouadhour, E.; Ternane, R. Hassen-Chehimi, D. Ben; Trabelsi-Ayadi, M.


    The lacunary lead sodium vanadate apatite Pb{sub 8}Na{sub 2}(VO{sub 4}){sub 6} was synthesized by the solid-state reaction method. The compound was characterized by X-ray powder diffraction, infrared (IR) absorption spectroscopy and Raman scattering spectroscopy. By comparing the effect of vanadate and phosphate ions on electrical properties, it was concluded that Pb{sub 8}Na{sub 2}(VO{sub 4}){sub 6} apatite is better conductor than Pb{sub 8}Na{sub 2}(PO{sub 4}){sub 6} apatite.

  5. Estimating U.S. Methane Emissions from the Natural Gas Supply Chain. Approaches, Uncertainties, Current Estimates, and Future Studies

    SciTech Connect

    Heath, Garvin; Warner, Ethan; Steinberg, Daniel; Brandt, Adam


    A growing number of studies have raised questions regarding uncertainties in our understanding of methane (CH4sub>) emissions from fugitives and venting along the natural gas (NG) supply chain. In particular, a number of measurement studies have suggested that actual levels of CH4sub> emissions may be higher than estimated by EPA" tm s U.S. GHG Emission Inventory. We reviewed the literature to identify the growing number of studies that have raised questions regarding uncertainties in our understanding of methane (CH4sub>) emissions from fugitives and venting along the natural gas (NG) supply chain.


    EPA Science Inventory

    Toxicological interactions of chemicals can affect metabolism, often decreasing overall associated metabolic rates; and changes in metabolism can be evaluated through the use of mathematical models. Trichloroethylene (TCE) and carbon tetrachloride (CCl4SUB>) are common co...


    EPA Science Inventory

    1-Butyl-3-methylimidazolium tetrachlorogallate, [bmim][GaCl4SUB>], prepared via microwave-assisted protocol, is found to be an active catalyst for the efficient acetalization of aldehydes under mild conditions.

  8. New Fluorinated Polymers

    NASA Technical Reports Server (NTRS)

    Fitch, John W., III


    This report summarizes progress during 1996 in our research effort along with a description of additional results associated with a TAG supplement to this grant (items 2 and 5 below). Progress is reported in five areas: 1) Polyamides Derived from [(p-HOOCC6H4)](sub 2)C(CF3)X (X= -CF3, OCH3, Cl); 2) Phosphorus-containing '12F-PEK' - Effect of Systematic Replacement of [(p-FC6H4COC6H4)](sub 2)C[(CF3)](sub 2) Monomer by [(p-FC6H4)](sub 2)(C6H5)PO; 3) Poly(ether ketone)s Derived from [(p-FC6H4COC6H4)](sub 2)(C6H5)PO; 4) New CF3-containing Organosilane Monomers and; 5) New Monomers for 12F-PEK Analogues with Improved Processability and Solubility.

  9. Synthesis and characterization of strontium-lanthanum apatites

    SciTech Connect

    Boughzala, K.; Salem, E. Ben; Chrifa, A. Ben; Gaudin, E.; Bouzouita, K. . E-mail:


    Two series of strontium-lanthanum apatites, Sr{sub 10-x}La {sub x}(PO{sub 4}){sub 6-x}(SiO{sub 4}) {sub x}F{sub 2} and Sr{sub 10-x}La {sub x}(PO{sub 4}){sub 6-x}(SiO{sub 4}) {sub x}O with 0 {<=} x {<=} 6, were synthesized by solid state reaction in the temperature range of 1200-1400 deg. C. The obtained materials were characterized by powder X-ray diffraction, infrared absorption spectroscopy and solid {sup 31}P Nuclear Magnetic Resonance. Pure solid solutions were obtained within a limited range of unsubstituted phosphate and silicate apatites. A variation of the lattice parameters was observed, with an increase of a and a decrease of c parameters, related to the radius of the corresponding substituted ions.

  10. Probing the failure mechanism of nanoscale LiFePO₄ for Li-ion batteries

    SciTech Connect

    Gu, Meng; Shi, Wei; Zheng, Jianming; Yan, Pengfei; Zhang, Ji-guang; Wang, Chongmin


    LiFePO4sub> is a high power rate cathode material for lithium ion battery and shows remarkable capacity retention, featuring a 91% capacity retention after 3300 cycles. In this work, we use high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectroscopy (EDS), and electron energy loss spectroscopy (EELS) to study the gradual capacity fading mechanism of LiFePO4sub> materials. We found that upon prolonged electrochemical cycling of the battery, the LiFePO4sub> cathode shows surface amorphization and loss of oxygen species, which directly contribute to the gradual capacity fading of the battery. The finding is of great importance for the design and improvement of new LiFePO4sub> cathode for high-energy and high-power rechargeable battery for electric transportation.


    SciTech Connect

    Nelson, A; Laurence, T; Conway, A; Behymer, E; Sturm, B; Voss, L; Nikolic, R; Payne, S; Mertiri, A; Pabst, G; Mandal, K; Burger, A


    The surface of the layered III-VI chalcogenide semiconductor GaSeTe was treated with (NH{sub 4}){sub 2}S at 60 C to modify the surface chemistry and determine the effect on transport properties. Room temperature photoluminescence (PL) measurements were used to assess the effect of the (NH{sub 4}){sub 2}S treatment on surface defect states. Evaluation of the subsequent surface chemistry was performed with high-resolution core-level photoemission measurements. Metal overlayers were deposited on the (NH{sub 4}){sub 2}S treated surfaces and the I-V characteristics were measured. The measurements were correlated to understand the effect of (NH{sub 4}){sub 2}S modification of the interfacial electronic structure with the goal of optimizing the metal/GaSeTe interface for radiation detector devices.

  12. Chromium (V) compounds as cathode material in electrochemical power sources


    Delnick, Frank M.; Guidotti, Ronald A.; McCarthy, David K.


    A cathode for use in a thermal battery, comprising a chromium (V) compound. The preferred materials for this use are Ca.sub.5 (CrO.sub.4).sub.3 Cl, Ca.sub.5 (CrO.sub.4).sub.3 OH, and Cr.sub.2 O.sub.5. The chromium (V) compound can be employed as a cathode material in ambient temperature batteries when blended with a suitably conductive filler, preferably carbon black.

  13. Reactive belite stabilization mechanisms by boron-bearing dopants

    SciTech Connect

    Cuesta, Ana; Losilla, Enrique R.; Aranda, Miguel A.G.; Sanz, Jesus; De la Torre, Angeles G.


    Belite-rich cements hold promise for reduced energy consumption and CO{sub 2} emissions, but their use is hindered by the slow hydration rates of ordinary belites. This drawback may be overcome by activation of belite by doping. Here, the doping mechanism of B and Na/B in belites is reported. For B-doping, three solid solutions have been tested: Ca{sub 2-x/2{open_square}x/2}(SiO{sub 4}){sub 1-x}(BO{sub 3}){sub x}, Ca{sub 2}(SiO{sub 4}){sub 1-x}(BO{sub 3}){sub x}O{sub x/2} and Ca{sub 2-x}B{sub x}(SiO{sub 4}){sub 1-x}(BO{sub 4}){sub x}. The experimental results support the substitution of silicate groups by tetrahedral borate groups with the concomitant substitution of calcium by boron for charge compensation, Ca{sub 2-x}B{sub x}(SiO{sub 4}){sub 1-x}(BO{sub 4}){sub x}. Otherwise, the coupled Na/B-doping of belite has also been investigated and Ca{sub 2-x}Na{sub x}(SiO{sub 4}){sub 1-x}(BO{sub 3}){sub x} series is confirmed to exist for a large range of x values. Along this series, {alpha}'{sub H}-C{sub 2}S is the main phase (for x {>=} 0.10) and is single phase for x = 0.25. Finally, a new structural description for borax doping in belite has been developed for {alpha}'{sub H}-Ca{sub 1.85}Na{sub 0.15}(SiO{sub 4}){sub 0.85}(BO{sub 3}){sub 0.15}, which fits better borax activated belite cements in Rietveld mineralogical analysis.


    EPA Science Inventory

    In this study, we present approximately two years (January 1999–December 2000) of atmospheric NH3, NH4SUB>+, HCl, Cl-, HNO3, NO3-, SO2, and SO4SUB>= concentrations measured by t...


    EPA Science Inventory

    Effective dechlorination of chloroaromatics, such as C6H5Cl, 1,2-C6H4sub>Cl2, 1,3-C6H4sub>Cl2 and 1,2,4-C6H3Cl3, using catalytic steam reforming has been confirmed ...

  16. Photocatalytic activity of glass ceramics containing Nasicon-type crystals

    SciTech Connect

    Fu, Jie


    Graphical abstract: Display Omitted Highlights: ► Glass ceramics containing Nasicon-type crystals were prepared. ► The glass ceramics showed photocatalytic activity under UV irradiation. ► Higher activity was observed in the MgTi{sub 4}(PO{sub 4}){sub 6}- and CaTi{sub 4}(PO{sub 4}){sub 6}-containing glass ceramics. -- Abstract: Glass ceramics were prepared by heat-treating MO–TiO{sub 2}–P{sub 2}O{sub 5} (M = Mg, Ca, Sr and Ba) and R{sub 2}O–TiO{sub 2}–P{sub 2}O{sub 5}–SiO{sub 2} (R = Li, Na and K) glasses, and their photocatalytic activity was investigated. The crystalline phases precipitated in the glasses were only Nasicon-type crystals, MTi{sub 4}(PO{sub 4}){sub 6} or RTi{sub 2}(PO{sub 4}){sub 3}. Decomposition experiments of both methylene blue (MB) and acetaldehyde showed that the glass ceramics exhibited effective photocatalytic activity. The activity did not depend on the radius of the M{sup 2+} or R{sup +} ion, and higher activity was observed in the MgTi{sub 4}(PO{sub 4}){sub 6} and CaTi{sub 4}(PO{sub 4}){sub 6} precipitated glass ceramics.

  17. Analyzing source apportioned methane in northern California during Discover-AQ-CA using airborne measurements and model simulations

    SciTech Connect

    Johnson, Matthew S.; Yates, Emma L.; Iraci, Laura T.; Loewenstein, Max; Tadić, Jovan M.; Wecht, Kevin J.; Jeong, Seongeun; Fischer, Marc L.


    This study analyzes source apportioned methane (CH4sub>) emissions and atmospheric mixing ratios in northern California during the Discover-AQ-CA field campaign using airborne measurement data and model simulations. Source apportioned CH4sub> emissions from the Emissions Database for Global Atmospheric Research (EDGAR) version 4.2 were applied in the 3-D chemical transport model GEOS-Chem and analyzed using airborne measurements taken as part of the Alpha Jet Atmospheric eXperiment over the San Francisco Bay Area (SFBA) and northern San Joaquin Valley (SJV). During the time period of the Discover-AQ-CA field campaign EDGAR inventory CH4sub> emissions were ~5.30 Gg day –1 (Gg = 1.0 × 109 g) (equating to ~1.90 × 103 Gg yr–1) for all of California. According to EDGAR, the SFBA and northern SJV region contributes ~30% of total CH4sub> emissions from California. Source apportionment analysis during this study shows that CH4sub> mixing ratios over this area of northern California are largely influenced by global emissions from wetlands and local/global emissions from gas and oil production and distribution, waste treatment processes, and livestock management. Model simulations, using EDGAR emissions, suggest that the model under-estimates CH4sub> mixing ratios in northern California (average normalized mean bias (NMB) = –5.2% and linear regression slope = 0.20). The largest negative biases in the model were calculated on days when large amounts of CH4sub> were measured over local emission sources and atmospheric CH4sub> mixing ratios reached values >2.5 parts per million. Sensitivity emission studies conducted during this research suggest that local emissions of CH4sub> from livestock management processes are likely the primary source of the negative model bias. These results indicate that a variety, and larger quantity, of measurement data needs to be

  18. Hydrothermal Synthesis and Structural Characterization of Organically Templated Uranyl Diphosphonates

    SciTech Connect

    Adelani, Pius O.; Oliver, Allen G.; Albrecht-Schmitt, Thomas E.


    The hydrothermal treatment of uranyl nitrate and 1,4-benzenebisphosphonic acid with a variety of aliphatic amines (tetramethylammonium hydroxide, tetraethylammonium hydroxide, and diethyldimethylammonium hydroxide) and small quantities of hydrofluoric acid at 200 °C results in the crystallization of a series of layered uranyl diphosphonate compounds, [(CH3)4sub>N][(UO2)3(O3PC6H4sub>PO3H)2F(H2O)]·0.5H2O (Me4sub>Ubbp), [(CH3CH2)4sub>N](UO2)[C6H4sub>(PO3H)(PO3H1.5)]2(H2O) (Et4sub>Ubbp), and [(CH3CH2)2N(CH3)2][(UO2)3(O3PC6H4sub>PO3H)2F(H2O)] (Et2Me2Ubbp). All these new compounds have layered structures, but the structures of Me4sub>Ubbp and Et2Me2Ubbp are similar in that they both contain UO6F and UO7 pentagonal bipyramids within dimers that are bridged by the phosphonate into a three-dimensional structure. The structure of Et4sub>Ubbp contains a single crystallographically unique UO7 unit. The edge-sharing pentagonal bipyramids are linked into chains formulated as (UO2)[C6H4sub>(PO3H)(PO3H1.5)]2(H2O)1-. The voids in these structures are filled with the organic templates so that the overall charge balance is maintained. Intense fluorescence was observed from these compounds at room temperature.

  19. Searching for “LiCr{sup II}PO{sub 4}”

    SciTech Connect

    Mosymow, E.; Glaum, R.; Kremer, R.K.


    The two new phosphates LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} and Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} are discovered as equilibrium phases (ϑ=800 °C) in the quarternary system Li/Cr/P/O. Their crystal structures have been determined from single-crystal X-ray diffraction data (LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}: violet-blue, Pnma (no. 62), Z=4, a=6.175(1) Å, b=14.316(3) Å, c=10.277(2) Å, 100 parameters, R{sub 1}=0.028, wR{sub 2}=0.08, 2060 unique reflections with F{sub o}>4σ(F{sub o}); Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4}: greyish-green, P1{sup ¯} (no. 2), Z=1, a=4.9379(7) Å, b=7.917(2) Å, c=8.426(2) Å, α=109.98(2)°, β=90.71(1)°, γ=104.91(1)°, 131 parameters, R{sub 1}=0.022, wR{sub 2}=0.067, 1594 unique reflections with F{sub o}>4σ(F{sub o})). Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} adopts an hitherto unknown structure type. The crystal structure of LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} is isotypic to that of NaCd{sup II}{sub 4}(PO{sub 4}){sub 3} and related to that of the mineral silicocarnotite Ca{sub 5}(PO{sub 4}){sub 2}(SiO{sub 4}). Significant disorder between Li{sup +} and Cr{sup 2+} is observed for both crystal structures. The oxidation states assigned to chromium in these two phosphates are in agreement with UV/vis/NIR absorption spectra and magnetic susceptibility data recorded for both compounds. Instead of “LiCr{sup II}PO{sub 4}” mixtures of LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}, Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4}, Cr{sub 2}O{sub 3}, and CrP are observed at equilibrium. Instead of “Li{sub 2}Cr{sup II}P{sub 2}O{sub 7}” four-phase mixtures consisting of Li{sub 9}Cr{sup III}{sub 3}(P{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2}, Li{sub 3}Cr{sup III}{sub 2}(PO{sub 4}){sub 3}, LiCrP{sub 2}O{sub 7}, and CrP were obtained. - Graphical abstract: Investigations on the equilibrium relations in the system Li/Cr/P/O revealed the two hitherto unknown phosphates Li{sub 5

  20. Determination of S-H Bond Strengths in Dimolybdenum Tetrasulfide Complexes

    SciTech Connect

    Appel, Aaron M.; Lee, Suh-Jane; Franz, James A.; DuBois, Daniel L.; Rakowski DuBois, Mary; Twamley, Brendan


    Homolytic solution bond dissociation free energies (sBDFE’s) for S-H bonds have been determined for soluble dimolybdenum tetrasulfide complexes through thermochemical cycles using electrochemical potentials and pKa values, all measured in acetonitrile. For [Cp*Mo(μ S)(μ SMe)2(μ SH)MoCp*]+ (S4sub>Me2H+), [Cp*Mo(μ S)(μ SMe)(μ SH)2MoCp*]+ (S4sub>MeH2+), and [Cp*Mo(μ S)(μ SH)3MoCp*]+ (S4sub>H3+), the pKa values were determined to be 5.6 ± 0.4, 5.3 ± 0.3, and 4.9 ± 0.3, respectively. The E1/2 values for S4sub>Me2•+/o, S4sub>MeH•+/o, and S4sub>H2•+/o were measured to be -0.02 ± 0.02, +0.04 ± 0.05, and +0.07 ± 0.07 V vs FeCp2+/o, respectively. Using these experimental values, the homolytic S-H sBDFE for each S4sub>RR’H+ to S4sub>RR’•+ reaction was determined to be 60.8 ± 1.0, 61.8 ± 1.6, and 61.9 ± 2.0 kcal/mol for S4sub>Me2H+, S4sub>MeH2+, and S4sub>H3+ respectively. These sBDFE values can be used to estimate gas phase bond dissociation enthalpies of 65.6, 66.6, and 66.7 kcal/mol, respectively. The gas phase bond dissociation enthalpy for the analogous complex, Cp2Mo2S4sub>Me2H+ was determined to be 64.9 kcal/mol by electronic structure calculations. Solid state structures are presented for S4sub>MeH and S4sub>H2. The Pacific Northwest National Laboratory is operated y Battelle for the U.S. Department of Energy.

  1. Speciation of technetium peroxo complexes in sulfuric acid revisited

    SciTech Connect

    Poineau, Frederic; German, Konstantin E.; Burton-Pye, Benjamin P.; Weck, Philippe F.; Kim, Eunja; Kriyzhovets, Olga; Safonov, Aleksey; Ilin, Viktor; Francesconi, Lynn C.; Sattelberger, Alfred P.; Czerwinski, Kenneth R.


    We found that the reaction of Tc(+7) with H2O2 has been studied in H2SO4sub> and the speciation of technetium performed by UV–visible and 99-Tc NMR spectroscopy. UV–visible measurements show that for H2SO4sub> ≥ 9 M and H2O2 = 0.17 M, TcO3(OH)(H2O)2 reacts immediately and blue solutions are obtained, while no reaction occurs for H2SO4sub < 9 M. The spectra of the blue solutions exhibit bands centered around 520 and 650 nm which are attributed to Tc(+7) peroxo species. Furthermore, our studies in 6 M H2SO4sub show that TcO4sub> - begins to react for H2O2 = 2.12 M and red solutions are obtained. The UV–visible spectra of the red species are identical to the one obtained from the reaction of TcO4sub> - with H2O2 in HNO3 and consistent with the presence of TcO(O2)2(H2O)(OH). The 99-Tc NMR spectrum of the red solution exhibits a broad signal centered at +5.5 ppm vs TcO4sub> - and is consistent with the presence of a low symmetry Tc(+7) molecule.

  2. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    SciTech Connect

    Rosen, R.K.


    The trivalent uranium compound, (MeC{sub 5}H{sub 4}){sub 3}U(thf), serves as a one- or two-electron reducing agent towards azides, RN{sub 3}. These reactions produce either the uranium(IV) azide, (MeC{sub 5}H{sub 4}){sub 3}UN{sub 3}, or uranium(V) imides, (MeC{sub 5}H{sub 4}){sub 3}UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me{sub 3}XN{sub 3}, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph{sub 3}XN{sub 3}, the azide is produced when X = C or Sn. For Ph{sub 3-x}CH{sub 3}N{sub 3}, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC{sub 6}H{sub 4}N{sub 3}, only the imides are produced. The magnetic properties of uranium diimides, ((MeC{sub 5}H{sub 4}){sub 3}U){sub 2}({mu}-NRN), were investigated. Several uranium(III) amines, (MeC{sub 5}H{sub 4}){sub 3}U(NH{sub 2}R), were produced from (MeC{sub 5}H{sub 4}){sub 3}U(thf) and RNH{sub 2}, and NH{sub 3} was found to be a better ligand towards (MeC{sub 5}H{sub 4}){sub 3}U than is PMe{sub 3}.

  3. A multitower measurement network estimate of California's methane emissions

    SciTech Connect

    Jeong, Seongeun; Hsu, Ying-Kuang; Andrews, Arlyn E.; Bianco, Laura; Vaca, Patrick; Wilczak, James M.; Fischer, Marc L.


    In this paper, we present an analysis of methane (CH4sub>) emissions using atmospheric observations from five sites in California's Central Valley across different seasons (September 2010 to June 2011). CH4sub> emissions for spatial regions and source sectors are estimated by comparing measured CH4sub> mixing ratios with transport model (Weather Research and Forecasting and Stochastic Time-Inverted Lagrangian Transport) predictions based on two 0.1° CH4sub> (seasonally varying “California-specific” (California Greenhouse Gas Emission Measurements, CALGEM) and a static global (Emission Database for Global Atmospheric Research, release version 42, EDGAR42)) prior emission models. Region-specific Bayesian analyses indicate that for California's Central Valley, the CALGEM- and EDGAR42-based inversions provide consistent annual total CH4sub> emissions (32.87 ± 2.09 versus 31.60 ± 2.17 Tg CO2eq yr-1; 68% confidence interval (CI), assuming uncorrelated errors between regions). Summing across all regions of California, optimized CH4sub> emissions are only marginally consistent between CALGEM- and EDGAR42-based inversions (48.35 ± 6.47 versus 64.97 ± 11.85 Tg CO2eq), because emissions from coastal urban regions (where landfill and natural gas emissions are much higher in EDGAR than CALGEM) are not strongly constrained by the measurements. Combining our results with those from a recent study of the South Coast Air Basin narrows the range of estimates to 43–57 Tg CO2eq yr-1 (1.3–1.8 times higher than the current state inventory). Finally, these results suggest that the combination of rural and urban measurements will be necessary to verify future changes in California's total CH4sub> emissions.

  4. Thermal expansion of solid solutions in apatite binary systems

    SciTech Connect

    Knyazev, Alexander V.; Bulanov, Evgeny N. Korokin, Vitaly Zh.


    Graphical abstract: Thermal dependencies of volume thermal expansion parameter for with thermal expansion diagrams for Pb{sub 5}(PO{sub 4}){sub 3}F{sub x}Cl{sub 1−x}. - Highlights: • Solid solutions in three apatitic binary systems were investigated via HT-XRD. • Thermal expansion coefficients of solid solutions in the systems were calculated. • Features of the thermal deformation of the apatites were described. • Termoroentgenography is a sensitive method for the investigation of isomorphism. - Abstract: High-temperature insitu X-ray diffraction was used to investigate isomorphism and the thermal expansion of apatite-structured compounds in three binary systems in the entire temperature range of the existence of its hexagonal modifications. Most of the studied compounds are highly expandable (α{sub l} > 8 × 10{sup 6} (K{sup −1})). In Pb{sub 5}(PO{sub 4}){sub 3}F–Pb{sub 5}(PO{sub 4}){sub 3}Cl system, volume thermal expansion coefficient is independence from the composition at 573 K. In Pb{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(VO{sub 4}){sub 3}Cl, the compound with equimolar ratio of substituted atoms has constant volume thermal expansion coefficient in temperature range 298–973 K. Ca{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(PO{sub 4}){sub 3}Cl system is characterized by the most thermal sensitive composition, in which there is an equal ratio of isomorphic substituted atoms.

  5. The chemistry of the phosphates of barium and tetravalent cations in the 1:1 stoichiometry

    SciTech Connect

    Popa, Karin Bregiroux, Damien; Konings, Rudy J.M.; Gouder, Thomas; Popa, Aurelian F.; Geisler, Thorsten; Raison, Philippe E.


    The chemistry of phosphates of barium and tetravalent cations [BaM{sup IV}(PO{sub 4}){sub 2}] is reviewed. Such phosphates crystallise in the C2/m space group for M{sup IV}=Ti, Zr, Hf, Ge, Sn, and Mo, and in the P2{sub 1}/n space group for BaTh(PO{sub 4}){sub 2}. The existence of BaM{sup IV}(PO{sub 4}){sub 2} in which M{sup IV}=Pb, Ce, and U is further evaluated. Several aspects, such as phase transitions in the compounds with yavapaiite structure, solid solutions of BaM{sup IV}(PO{sub 4}){sub 2} compounds and practical applications are briefly discussed. - Graphical abstract: Graphical representation of the variation of the unit-cell volume of BaM{sup IV}(PO{sub 4}){sub 2} as a function of the ionic radii of M{sup IV} cations. Such phosphates crystallise in the C2/m space group for M{sup IV}=Ti, Zr, Hf, Ge, Sn, and Mo, and in the P2{sub 1}/n space group for BaTh(PO{sub 4}){sub 2}. The 'BaCe(PO{sub 4}){sub 2}' phosphate previously reported does not exist, as demonstrated in the present paper. Taking into account the present evidence, it can be concluded at this stage that the existence of other Ce(IV) phosphates obtained at high temperature and reported into the literature becomes doubtful. Display Omitted.

  6. Tetrahedral-Network Organo-Zincophosphates: Syntheses and Structures of (N(2)C(6)H(14)).Zn(HPO(4))(2).H(2)O, H(3)N(CH(2))(3)NH(3).Zn(2)(HPO(4))(3) and (N(2)C(6)H(14)).Zn(3)(HPO(4))(4)

    SciTech Connect

    Chavez, Alejandra V.; Hannooman, Lakshitha; Harrison, William T.A.; Nenoff, Tina M.


    The solution-mediated syntheses and single crystal structures of (N2C6H14)·Zn(HPO4sub>)2·H2O (I), H3N(CH2)3NH3·Zn2(HPO4sub>)3 (II), and (N2C6H14)·Zn3(HPO4sub>)4sub> (III) are described. These phases contain vertex-sharing Zn04sub> and HP04sub> tetrahedra, accompanied by doubly- protonated organic cations. Despite their formal chemical relationship, as members of the series of t·Znn(HP04sub>)n+1 (t= template, n = 1-3), these phases adopt fimdamentally different crystal structures, as one-dimensional, two-dimensional, and three-dimensional Zn04sub>/HP04sub> networks, for I, II, and III respectively. Similarities and differences to some other zinc phosphates are briefly discussed. Crystal data: (N2C6H14)·Zn(HP04sub>)2·H20, Mr = 389.54, monoclinic, space group P21/n (No. 14), a = 9.864 (4) Å, b = 8.679 (4) Å, c = 15.780 (3) Å, β = 106.86 (2)°, V= 1294.2 (8) Å3, Z = 4, R(F) = 4.58%, RW(F) = 5.28% [1055 reflections with I >3σ(I)]. H3N(CH2)3NH3·Zn2(HP04sub>)3, Mr = 494.84, monoclinic, space group P21/c (No. 14), a= 8.593 (2)Å, b= 9.602 (2)Å, c= 17.001 (3)Å, β= 93.571 (8)°, V = 1400.0 (5) Å3, Z = 4, R(F) = 4.09%, RW(F) = 4.81% [2794 reflections with I > 3σ (I)]. (N2C6H14)·Zn3(HP04sub>)4sub>, Mr= 694.25, monoclinic, space group P21/n (No. 14), a = 9.535 (2) Å, b = 23.246 (4)Å, c= 9.587 (2)Å, β= 117.74 (2)°, V= 1880.8 (8) Å3, Z = 4, R(F) = 3.23%, RW(F) = 3.89% [4255 reflections with

  7. Top-down estimate of methane emissions in California using a mesoscale inverse modeling technique: The South Coast Air Basin

    SciTech Connect

    Cui, Yu Yan; Brioude, Jerome; McKeen, Stuart A.; Angevine, Wayne M.; Kim, Si -Wan; Frost, Gregory J.; Ahmadov, Ravan; Peischl, Jeff; Bousserez, Nicolas; Liu, Zhen; Ryerson, Thomas B.; Wofsy, Steve C.; Santoni, Gregory W.; Kort, Eric A.; Fischer, Marc L.; Trainer, Michael


    Methane (CH4sub>) is the primary component of natural gas and has a larger global warming potential than CO2. Some recent top-down studies based on observations showed CH4sub> emissions in California's South Coast Air Basin (SoCAB) were greater than those expected from population-apportioned bottom-up state inventories. In this study, we quantify CH4 sub>emissions with an advanced mesoscale inverse modeling system at a resolution of 8 km × 8 km, using aircraft measurements in the SoCAB during the 2010 Nexus of Air Quality and Climate Change campaign to constrain the inversion. To simulate atmospheric transport, we use the FLEXible PARTicle-Weather Research and Forecasting (FLEXPART-WRF) Lagrangian particle dispersion model driven by three configurations of the Weather Research and Forecasting (WRF) mesoscale model. We determine surface fluxes of CH4sub> using a Bayesian least squares method in a four-dimensional inversion. Simulated CH4 concentrations with the posterior emission inventory achieve much better correlations with the measurements (R2 = 0.7) than using the prior inventory (U.S. Environmental Protection Agency's National Emission Inventory 2005, R2 = 0.5). The emission estimates for CH4sub> in the posterior, 46.3 ± 9.2 Mg CH4sub>/h, are consistent with published observation-based estimates. Changes in the spatial distribution of CH4sub> emissions in the SoCAB between the prior and posterior inventories are discussed. Missing or underestimated emissions from dairies, the oil/gas system, and landfills in the SoCAB seem to explain the differences between the prior and posterior inventories. Furthermore, we estimate that dairies contributed 5.9 ± 1.7 Mg CH4sub>/h and the two sectors of oil and gas industries (production and downstream) and landfills together contributed 39.6 ± 8.1 Mg CH4sub>/h in the SoCAB.

  8. On the synthesis, characterization and magnetic properties of two new phases discovered in the PbO–Fe{sub 2}O{sub 3}–P{sub 2}O{sub 5} system

    SciTech Connect

    El Hafid, Hassan; Velázquez, Matias; Pérez, Olivier; Pautrat, Alain; Véron, Emmanuel; Viraphong, Oudomsack; Delmas, Claude


    The PbFe{sub 3}O(PO{sub 4}){sub 3} powder compound was studied by means of X-ray diffraction (XRD) from 300 to 6 K, electron-probe microanalysis (EPMA) coupled with wavelength dispersion spectroscopy (WDS), calorimetric (DSC and specific heat) and magnetic properties measurements. Magnetization, magnetic susceptibility and specific heat measurements carried out on PbFe{sub 3}O(PO{sub 4}){sub 3} powders firmly establish a series of three ferromagnetic (FM)-like second order phase transitions spanned over the 32–8 K temperature range. Discrepancies between magnetization and specific heat data obtained in PbFe{sub 3}O(PO{sub 4}){sub 3} powders and single crystals are highlighted. A first extraction of the critical exponents (β,γ,δ) was performed by ac magnetic susceptibility in both PbFe{sub 3}O(PO{sub 4}){sub 3} powders and single crystals and the values were found to be consistent with mean-field theory. Further exploration of the PbO–Fe{sub 2}O{sub 3}–P{sub 2}O{sub 5} system led to the discovery of a new langbeinite phase, Pb{sub 1.5}Fe{sub 2}(PO{sub 4}){sub 3}, the crystal structure of which was solved by room temperature single crystal XRD (P2{sub 1}3, Z=4, a=9.7831(2) Å). This phase does not undergo any structural phase transition down to 6 K nor any kind of long range ordering down to 2 K. - Graphical abstract: Three ferromagnetic-like phase transitions discovered in the new compound PbFe{sub 3}O(PO{sub 4}){sub 3} by specific heat and ZFC/FC magnetization measurements. - Highlights: • Three FM-like second order phase transitions in PbFe{sub 3}O(PO{sub 4}){sub 3} powders. • Critical exponents (β,γ,δ) in PbFe{sub 3}O(PO{sub 4}){sub 3} consistent with mean-field behavior. • Discovery of a new langbeinite phase, Pb{sub 1.5}Fe{sub 2}(PO{sub 4}){sub 3}.

  9. Microstructure and hydriding studies of AB/sub 5/ hydrogen storage compounds. Final report

    SciTech Connect

    Goodell, P.D.; Sandrock, G.D.; Huston, E.L.


    New data on the microstructure, pressure-composition-temperature, and absorption/desorption kinetics of AB/sub 5/ metal hydrides are presented. The most significant result to emerge from the investigation is that many of the AB/sub 5/ metal hydrides, especially the LaNi/sub 5/ related materials, show instantaneous absorption and desorption response in proportion to the amount of cooling or heating which is provided. Eight categories of materials were studied: reference alloys (LaNi/sub 5/, LaNi/sub 4/ /sub 9/Al/sub 0/ /sub 1/, LaNi/sub 3/Co/sub 2/); Ni second phase particles (LaNi/sub 5/ /sub 67/, LaNi/sub 7/, LaNi/sub 11/ /sub 3/); eutectoid microstructure (SmCo/sub 5/); other second phases (LaNi/sub 3/ /sub 8/Fe/sub 1/ /sub 2/, LaNi/sub 3/ /sub 5/Cr/sub 1/ /sub 5/, LaNi/sub 4/Cr, LaNi/sub 4/Si; LaNi/sub 4/Sn, MNi/sub 4/Sn, MNi/sub 4/ /sub 3/Al/sub 0/ /sub 7/); substitutional elements (LaNi/sub 4/Cu, LaNi/sub 4/ /sub 5/Pd/sub 0/ /sub 5/, LaNi/sub 4/ /sub 7/Sn/sub 0/ /sub 3/, LaNi/sub 4/ /sub 8/C/sub 0/ /sub 2/, MNi/sub 4/ /sub 3/Mn/sub 0/ /sub 7/); surface active elements (LaNi/sub 4/ /sub 8/B/sub 0/ /sub 2/, LaNi/sub 4/ /sub 9/S/sub 0/ /sub 1/, LaNi/sub 4/ /sub 9/Se/sub 0/ /sub 1/); large diameter atom substitutions (Mg/sub 0/ /sub 1/La/sub 0/ /sub 9/Ni/sub 5/, Ca/sub 0/ /sub 2/La/sub 0/ /sub 8/Ni/sub 5/, Sr/sub 0/ /sub 2/La/sub 0/ /sub 8/Ni/sub 5/, Ba/sub 0/ /sub 2/La/sub 0/ /sub 8/Ni/sub 5/); other compositions (LaNi/sub 3/); and Pd plating (electroless plated samples and mechanically alloyed specimens).

  10. Fulvalene- and polyarene-transition metal-carborane complexes as building blocks for multilevel arrays. Stepwise synthesis and structural characterization of polymetallic linked sandwiches

    SciTech Connect

    Davis, J.H. Jr.; Sinn, E.; Grimes, R.N. )


    The designed synthesis and structural elucidation of a series of linked double-decker and triple-decker arene-metal carborane complexes, in which the sandwich moieties are linked either directly or via bridging phenylene or biphenylene groups, are reported. The reaction of fulvalenide dianion ((C{sub 5}H{sub 4}){sub 2}{sup 2{minus}}) with CoCl{sub 2} and the Et{sub 2}C{sub 2}B{sub 4}H{sub 5}{sup {minus}} ion generated ((Et{sub 2}C{sub 2}B{sub 4}H{sub 4})Co(C{sub 5}H{sub 4})){sub 2} (1), the first known fulvalene-metal-carborane sandwich species, as air-stable orange crystals. Double-decapitation (removal of the apex BH units) of 1 gave yellow air-stable ((Et{sub 2}C{sub 2}B{sub 3}H{sub 5})Co(C{sub 5}H{sub 4})){sub 2} (3). The interaction of the 1,4-bis(tetramethylcyclopentadienyl)phenylene dianion (Me{sub 4}C{sub 5}-C{sub 6}H{sub 4}-C{sub 5}Me{sub 4}){sup 2{minus}} with CoCl{sub 2} and the carborane ion produced orange ((Et{sub 2}C{sub 2}B{sub 4}H{sub 4})Co(C{sub 5}Me{sub 4})){sub 2}C{sub 6}H{sub 4} (4), which on double-decapitation gave yellow ((Et{sub 2}C{sub 2}B{sub 3}H{sub 5})Co(C{sub 5}Me{sub 4})){sub 2}C{sub 6}H{sub 4} (6), both compounds isolated as air-stable crystals. Similar treatment of the (Me{sub 4}C{sub 5}-(C{sub 6}H{sub 4}){sub 2}-C{sub 5}Me{sub 4}){sup 2{minus}} dianion gave orange crystals of ((Et{sub 2}C{sub 2}B{sub 4}H{sub 4})Co(C{sub 5}Me{sub 4})){sub 2} (7), which was decapitated to generate yellow ((Et{sub 2}C{sub 2}B{sub 3}H{sub 5})Co(C{sub 5}Me{sub 4})){sub 2}(C{sub 6}H{sub 4}){sub 2} (9); again both species are air-stable.

  11. Self-assembled light lanthanide oxalate architecture with controlled morphology, characterization, growing mechanism and optical property

    SciTech Connect

    He, Hongmei; Zhang, Youjin; Zhu, Wei; Zheng, Ao


    Highlights: {yields} Flower-like Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}.10H{sub 2}O was gained with Na{sub 3}Cit assisted precipitation method. {yields} The mechanism of the flower-like Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}.10H{sub 2}O formation was proposed. {yields} The Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}.10H{sub 2}O and Sm{sub 2}O{sub 3} samples exhibited obviously different PL spectra. {yields} Ln{sub 2}(C{sub 2}O{sub 4}){sub 3}.nH{sub 2}O (Ln = Gd, Dy, Lu, Y) also were achieved by the simple method. -- Abstract: Flower-like Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}.10H{sub 2}O had been synthesized by a facile complex agent assisted precipitation method. The flower-like Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}.10H{sub 2}O was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, thermogravimetry-differential thermal analysis and photoluminescence. The possible growth mechanism of the flower-like Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}.10H{sub 2}O was proposed. To extend this method, other Ln{sub 2}(C{sub 2}O{sub 4}){sub 3}.nH{sub 2}O (Ln = Gd, Dy, Lu, Y) with different morphologies also had been prepared by adjusting different rare earth precursors. Further studies revealed that besides the reaction conditions and the additive amount of complex agents, the morphologies of the as-synthesised lanthanide oxalates were also determined by the rare earth ions. The Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}.10H{sub 2}O and Sm{sub 2}O{sub 3} samples exhibited different photoluminescence spectra, which was relevant to Sm{sup 3+} energy level structure of 4f electrons. The method may be applied in the synthesis of other lanthanide compounds, and the work could explore the potential optical materials.

  12. Yttrium-succinates coordination polymers: Hydrothermal synthesis, crystal structure and thermal decomposition

    SciTech Connect

    Amghouz, Zakariae; Roces, Laura; Garcia-Granda, Santiago; Garcia, Jose R.; Souhail, Badredine; Mafra, Luis; Shi, Fa-nian; Rocha, Joao


    New polymeric yttrium-succinates, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}, have been synthesized, and their structures (solved by single crystal XRD) are compared with that of Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.H{sub 2}O. Three compounds were obtained as single phases, and their thermal behaviour is described. - Graphical abstract: In the field of coordination polymers or MOF's, few studies report on the polymorphs of Ln(III)-succinic acid. Here, we describe the hydrothermal synthesis and structural characterization of two novel yttrium-succinates coordination polymers, respectively 2D and 3D, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.

  13. Atmospheric corrosion of zinc in the presence of ammonium sulfate particles

    SciTech Connect

    Lobnig, R.E.; Siconolfi, D.J.; Psota-Kelty, L.; Frankenthal, R.P.; Sinclair, J.D.; Grundmeier, G.; Stratmann, M.


    The atmospheric corrosion of zinc in the presence of (NH{sub 4}){sub 2}SO{sub 4} particles has been investigated at 300 and 373 K in air-water vapor mixtures. The development of corrosion products was followed by several in situ techniques, including Fourier transform infrared-spectroscopy, X-ray diffraction, pH measurements, and scanning Kelvin probe measurements. Unlike earlier work on copper and aluminum, zinc reacts with the particles below the critical relative humidity (CRH) of (NH{sub 4}){sub 2}SO{sub 4}. At 300 K reaction was observed at 65% relative humidity (RH), but not at 60% /RH. This is attributed to the presence of basic zinc carbonate on the surface, which absorbs sufficient water at this low RH to make electrochemical reactions possible. At and above the CRH of (NH{sub 4}){sub 2}SO{sub 4}, zinc reacts with (NH{sub 4}){sub 2}SO{sub 4} forming mixed ammonium zinc sulfate and later on basic zinc sulfate, and at 373 K additionally zincite (ZnO). Above the CRH of (NH{sub 4}){sub 2}SO{sub 4}, the corrosion potential decreases directly after formation of droplets surrounding the particles and zinc becomes active. Corrosion mechanisms are proposed to explain the observations.

  14. Interpenetrating Diruthenium Tetraformate Monocation, [RuII/III2(O2CH)4]+, Based 3-D Molecule-based Magnets

    SciTech Connect

    Kennon, B.; Stone, K; Stephens, P; Miller, J


    Synthesis of [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[MIII(CN){sub 6}] (M = Co, Fe) possessing an interpenetrating body center cubic (bcc) lattices was investigated utilizing several synthetic methods. The targeted interpenetrating bcc [a = 12.6621(3) {angstrom}] structure was obtained for [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[Co(CN){sub 6}], and it exhibits {chi}T(T) that is fit to a model which includes zero field splitting. Cyanide abstraction from [Cr(CN){sub 6}]{sup 3-} occurs thwarting the formation of [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[M(CN){sub 6}]. [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[Fe(CN){sub 6}] also exhibits the desired bcc structure [12.7071(3) {angstrom}], and its 13.4 K T{sub c} is a 6-fold enhancement with respect to that observed for [Ru{sub 2}(O{sub 2}CMe){sub 4}]{sub 3}[Fe(CN){sub 6}].