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Sample records for hydride phases formed

  1. Method of forming metal hydride films

    Science.gov (United States)

    Steinberg, R.; Alger, D. L.; Cooper, D. W. (Inventor)

    1977-01-01

    The substrate to be coated (which may be of metal, glass or the like) is cleaned, both chemically and by off-sputtering in a vacuum chamber. In an ultra-high vacuum system, vapor deposition by a sublimator or vaporizer coats a cooled shroud disposed around the substrate with a thin film of hydride forming metal which getters any contaminant gas molecules. A shutter is then opened to allow hydride forming metal to be deposited as a film or coating on the substrate. After the hydride forming metal coating is formed, deuterium or other hydrogen isotopes are bled into the vacuum system and diffused into the metal film or coating to form a hydride of metal film. Higher substrate temperatures and pressures may be used if various parameters are appropriately adjusted.

  2. Hydrogen, lithium, and lithium hydride production

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

    2017-06-20

    A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

  3. Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

    Energy Technology Data Exchange (ETDEWEB)

    Auer, Henry; Guehne, Robin; Bertmer, Marko; Weber, Sebastian; Wenderoth, Patrick; Hansen, Thomas Christian; Haase, Jürgen; Kohlmann, Holger

    2017-01-18

    Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD4/3–x and BaSnD4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms with d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae4 tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.

  4. Phase I. Lanthanum-based Start Materials for Hydride Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Gschneidner, K. A. [Ames Lab., Ames, IA (United States); Schmidt, F. A. [Ames Lab., Ames, IA (United States); Frerichs, A. E. [Ames Lab., Ames, IA (United States); Ament, K. A. [Ames Lab., Ames, IA (United States)

    2013-08-20

    The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La1-xRx)(Ni1-yMy)(Siz), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

  5. Reversible metal-hydride phase transformation in epitaxial films.

    Science.gov (United States)

    Roytburd, Alexander L; Boyerinas, Brad M; Bruck, Hugh A

    2015-03-11

    Metal-hydride phase transformations in solids commonly proceed with hysteresis. The extrinsic component of hysteresis is the result of the dissipation of energy of internal stress due to plastic deformation and fracture. It can be mitigated on the nanoscale, where plastic deformation and fracture are suppressed and the transformation proceeds through formation and evolution of coherent phases. However, the phase coherency introduces intrinsic thermodynamic hysteresis, preventing reversible transformation. In this paper, it is shown that thermodynamic hysteresis of coherent metal-hydride transformation can be eliminated in epitaxial film due to substrate constraint. Film-substrate interaction leads to formation of heterophase polydomain nanostructure with variable phase fraction which can change reversibly by varying temperature in a closed system or chemical potential in an open system.

  6. Dual-mode chemical vapor generation for simultaneous determination of hydride-forming and non-hydride-forming elements by atomic fluorescence spectrometry.

    Science.gov (United States)

    Wang, Yu; Xu, Kailai; Jiang, Xiaoming; Hou, Xiandeng; Zheng, Chengbin

    2014-05-21

    A dual-mode chemical vapor generation integrating hydride generation and photochemical vapor generation was developed for simultaneous multi-element analysis of hydride-forming and non-hydride-forming elements by atomic fluorescence spectrometry. Four elements were selected as model elements of hydride-forming (As, Cd) and non-hydride-forming (Ni, Fe) elements to validate this proposed method. Standard or sample solutions were separately pumped to mix with tetrahydroborate, and concentrated formic acid and ammonia, and then directed to a hydride generator and a photochemical reactor to realize simultaneous hydride generation and photochemical vapor generation, respectively. Optimum conditions for dual-mode chemical vapor generation were carefully investigated. Under the optimized conditions, limits of detection of 0.05, 0.008, 0.8 and 0.1 μg L(-1) were obtained for As, Cd, Fe and Ni, respectively. The precisions were 5.0, 5.5, 4.3 and 4.5% (n = 6, RSDs) for 2 μg L(-1) of As, 1 μg L(-1) of Cd, 50 μg L(-1) of Fe and 10 μg L(-1) of Ni, respectively. This method was validated for accuracy with three certified reference water samples and applied to the simultaneous determination of these elements in a tap water sample with spike recoveries in the range of 95-99%.

  7. Simultaneous determination of hydride and non-hydride forming elements by inductively coupled plasma optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Benzo, Z. [Instituto Venezolano de Investigaciones Cientificas, IVIC, Altos de Pipe, Caracas (Venezuela, Bolivarian Republic of); Matos-Reyes, M.N.; Cervera, M.L.; Guardia, M. de la, E-mail: m.luisa.cervera@uv.es [Department of Analytical Chemistry, University of Valencia, Valencia (Spain)

    2011-09-15

    The operating characteristics of a dual nebulization system were studied including instrumental and chemical conditions for the hydride generation and analytical figures of merit for both, hydride and non hydride forming elements. Analytical performance of the nebulization system was characterized by detection limits from 0.002 to 0.0026 {mu}g mL{sup -1} for the hydride forming elements and between 0.0034 and 0.0121 {mu}g mL{sup -1} for the non-hydride forming elements, relative standard deviation for 10 replicate measurements at 0.25 mg L{sup -1} level and recovery percentages between 97 and 103%. The feasibility of the system was demonstrated in the simultaneous determination of Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Zn, As, Bi, Sb, Se, and Te in the NIST 1549 (non-fat milk powder), NIST 1570a (spinach leaves), DORM-2 (dogfish muscle) and TORT-2 (lobster hepatopancreas) certified samples for trace elements. Results found were in good agreement with the certified ones. (author)

  8. Storing hydrogen in the form of light alloy hydrides

    Science.gov (United States)

    Freund, E.; Gillerm, C.

    1981-01-01

    Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.

  9. Kinetics of Liquid-Phase Hydrogenation of Benzene in a Metal Hydride Slurry System Formed by M1Ni5 and Benzene

    Institute of Scientific and Technical Information of China (English)

    代世耀; 徐国华; 安越; 陈长聘; 陈立新; 王启东

    2003-01-01

    The kinetics of liquid-phase hydrogenation of benzene in misch metal nickel-five (M1Ni5) and benzene slurry system was studied by investigating the influences of the reaction temperature, pressure, alloy concentration and stirring speed on the mass transfer-reaction processes inside the slurry. The results show that the whole process is controlled by the reaction at the surface of the catalyst. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particles are negligible. The apparent reaction rate is zero order for benzene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model obtained fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of M1Ni5-C6H6 slurry system is 42.16 kJ·mo1-1.

  10. Micro-scale fracture experiments on zirconium hydrides and phase boundaries

    Science.gov (United States)

    Chan, H.; Roberts, S. G.; Gong, J.

    2016-07-01

    Fracture properties of micro-scale zirconium hydrides and phase boundaries were studied using microcantilever testing methods. FIB-machined microcantilevers were milled on cross-sectional surfaces of hydrided samples, with the most highly-stressed regions within the δ-hydride film, within the α-Zr or along the Zr-hydride interface. Cantilevers were notched using the FIB and then tested in bending using a nanoindenter. Load-displacement results show that three types of cantilevers have distinct deformation properties. Zr cantilevers deformed plastically. Hydride cantilevers fractured after a small amount of plastic flow; the fracture toughness of the δ-hydride was found to be 3.3 ± 0.4 MPam1/2 and SEM examination showed transgranular cleavage on the fracture surfaces. Cantilevers notched at the Zr-hydride interface developed interfacial voids during loading, at loads considerably lower than that which initiate brittle fracture of hydrides.

  11. Hydrogen storage in the form of metal hydrides

    Science.gov (United States)

    Zwanziger, M. G.; Santana, C. C.; Santos, S. C.

    1984-01-01

    Reversible reactions between hydrogen and such materials as iron/titanium and magnesium/ nickel alloy may provide a means for storing hydrogen fuel. A demonstration model of an iron/titanium hydride storage bed is described. Hydrogen from the hydride storage bed powers a converted gasoline electric generator.

  12. A quantitative phase field model for hydride precipitation in zirconium alloys: Part II. Modeling of temperature dependent hydride precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Zhihua [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); PolyU Base (Shenzhen) Limited, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Hao, Mingjun [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Guo, Xianghua [State Key Laboratory of Explosion and Safety Science, Beijing Institute of Technology, Beijing 100081 (China); Tang, Guoyi [Advanced Materials Institute, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Shi, San-Qiang, E-mail: mmsqshi@polyu.edu.hk [The Hong Kong Polytechnic University, Shenzhen Research Institute, Shenzhen (China); PolyU Base (Shenzhen) Limited, Shenzhen (China); Department of Mechanical Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China)

    2015-04-15

    A quantitative free energy functional developed in Part I (Shi and Xiao, 2014 [1]) was applied to model temperature dependent δ-hydride precipitation in zirconium in real time and real length scale. At first, the effect of external tensile load on reorientation of δ-hydrides was calibrated against experimental observations, which provides a modification factor for the strain energy in free energy formulation. Then, two types of temperature-related problems were investigated. In the first type, the effect of temperature transient was studied by cooling the Zr–H system at different cooling rates from high temperature while an external tensile stress was maintained. At the end of temperature transients, the average hydride size as a function of cooling rate was compared to experimental data. In the second type, the effect of temperature gradients was studied in a one or two dimensional temperature field. Different boundary conditions were applied. The results show that the hydride precipitation concentrated in low temperature regions and that it eventually led to the formation of hydride blisters in zirconium. A brief discussion on how to implement the hysteresis of hydrogen solid solubility on hydride precipitation and dissolution in the developed phase field scheme is also presented.

  13. Modeling of Gallium Nitride Hydride Vapor Phase Epitaxy

    Science.gov (United States)

    Meyyappan, Meyya; Arnold, James O. (Technical Monitor)

    1997-01-01

    A reactor model for the hydride vapor phase epitaxy of GaN is presented. The governing flow, energy, and species conservation equations are solved in two dimensions to examine the growth characteristics as a function of process variables and reactor geometry. The growth rate varies with GaCl composition but independent of NH3 and H2 flow rates. A change in carrier gas for Ga source from H2 to N2 affects the growth rate and uniformity for a fixed reactor configuration. The model predictions are in general agreement with observed experimental behavior.

  14. Gallium Nitride Nanowires Grown by Hydride Vapor Phase Epitaxy

    Institute of Scientific and Technical Information of China (English)

    LIU Zhan-Hui; XIU Xiang-Qan; YAN Huai-Yue; ZHANG Rong; XIE Zi-Li; HAN Ping; SHI Yi; ZHENG You-Dou

    2011-01-01

    @@ GaN nanowires are grown by hydride vapor phase epitaxy using nickel as a catalyst.The properties of the obtained GaN nanowires are characterized by scanning and transmission electron microscopy,electron diffraction,roomtemperature photoluminescence and energy dispersive spectroscopy.The results show that the nanowires are wurtzite single crystals growing along the[0001]direction and a redshift in the photoluminescence is observed due to a superposition of several effects.The Raman spectra are close to those of the bulk GaN and the significantly broadening of those modes indicates the phonon confinement effects associated with the nanoscale dimensions of the system.%GaN nanowires are grown by hydride vapor phase epitaxy using nickel as a catalyst. The properties of the obtained GaN nanowires are characterized by scanning and transmission electron microscopy, electron diffraction, room-temperature photoluminescence and energy dispersive spectroscopy. The results show that the nanowires are wurtzite single crystals growing along the [0001] direction and a redshift in the photoluminescence is observed due to a superposition of several effects. The Raman spectra are close to those of the bulk GaN and the significantly broadening of those modes indicates the phonon confinement effects associated with the nanoscale dimensions of the system.

  15. Crystal structure of the superconducting phase of sulfur hydride

    Science.gov (United States)

    Einaga, Mari; Sakata, Masafumi; Ishikawa, Takahiro; Shimizu, Katsuya; Eremets, Mikhail I.; Drozdov, Alexander P.; Troyan, Ivan A.; Hirao, Naohisa; Ohishi, Yasuo

    2016-09-01

    A superconducting critical temperature above 200 K has recently been discovered in H2S (or D2S) under high hydrostatic pressure. These measurements were interpreted in terms of a decomposition of these materials into elemental sulfur and a hydrogen-rich hydride that is responsible for the superconductivity, although direct experimental evidence for this mechanism has so far been lacking. Here we report the crystal structure of the superconducting phase of hydrogen sulfide (and deuterium sulfide) in the normal and superconducting states obtained by means of synchrotron X-ray diffraction measurements, combined with electrical resistance measurements at both room and low temperatures. We find that the superconducting phase is mostly in good agreement with the theoretically predicted body-centred cubic (bcc) structure for H3S. The presence of elemental sulfur is also manifest in the X-ray diffraction patterns, thus proving the decomposition mechanism of H2S to H3S + S under pressure.

  16. Process of forming a sol-gel/metal hydride composite

    Science.gov (United States)

    Congdon, James W.

    2009-03-17

    An external gelation process is described which produces granules of metal hydride particles contained within a sol-gel matrix. The resulting granules are dimensionally stable and are useful for applications such as hydrogen separation and hydrogen purification. An additional coating technique for strengthening the granules is also provided.

  17. Hydrogen, lithium, and lithium hydride production

    Science.gov (United States)

    Brown, Sam W; Spencer, Larry S; Phillips, Michael R; Powell, G. Louis; Campbell, Peggy J

    2014-03-25

    A method of producing high purity lithium metal is provided, where gaseous-phase lithium metal is extracted from lithium hydride and condensed to form solid high purity lithium metal. The high purity lithium metal may be hydrided to provide high purity lithium hydride.

  18. On the thermodynamics of phase transitions in metal hydrides

    Science.gov (United States)

    Vita, Andrea

    2012-02-01

    Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiHx, which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

  19. Metal hydrides form halogen bonds: measurement of energetics of binding.

    Science.gov (United States)

    Smith, Dan A; Brammer, Lee; Hunter, Christopher A; Perutz, Robin N

    2014-01-29

    The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η(5)-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η(5)-cyclopentadienyl) is demonstrated by (1)H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = -10.9 ± 0.4 and -11.8 ± 0.3 kJ/mol; ΔS° = -38 ± 2 and -34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH° = -7.3 ± 0.1 kJ/mol, ΔS° = -24 ± 1 J/(mol·K)). For the more reactive complexes 2-5, measurements are limited to determination of their low-temperature (212 K) association constants with C6F5I as 2.9 ± 0.2, 2.5 ± 0.1, <1.5, and 12.5 ± 0.3 M(-1), respectively.

  20. Probing the cerium/cerium hydride interface using nanoindentation

    Energy Technology Data Exchange (ETDEWEB)

    Brierley, Martin, E-mail: martin.brierley@awe.co.uk [Atomic Weapons Establishment, Aldermaston, Berkshire RG7 4PR (United Kingdom); University of Manchester, Manchester M13 9PL (United Kingdom); Knowles, John, E-mail: john.knowles@awe.co.uk [Atomic Weapons Establishment, Aldermaston, Berkshire RG7 4PR (United Kingdom)

    2015-10-05

    Highlights: • A disparity exists between the minimum energy and actual shape of a cerium hydride. • Cerium hydride is found to be harder than cerium metal by a ratio of 1.7:1. • A zone of material under compressive stress was identified surrounding the hydride. • No distribution of hardness was apparent within the hydride. - Abstract: A cerium hydride site was sectioned and the mechanical properties of the exposed phases (cerium metal, cerium hydride, oxidised cerium hydride) were measured using nanoindentation. An interfacial region under compressive stress was observed in the cerium metal surrounding a surface hydride that formed as a consequence of strain energy generated by the volume expansion associated with precipitation of the hydride phase.

  1. Kinetics of hydride front in Zircaloy-2 and H release from a fractional hydrided surface

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, M.; Gonzalez-Gonzalez, A.; Moya, J. S.; Remartinez, B.; Perez, S.; Sacedon, J. L. [Instituto de Ciencia de Materiales de Madrid (CSIC), Sor Juana Ines de la Cruz 3, Cantoblanco, 28049 Madrid (Spain); Iberdrola, Tomas Redondo 3, 28033 Madrid (Spain); Instituto de Ciencia de Materiales de Madrid (CSIC), Sor Juana Ines de la Cruz 3, Cantoblanco, 28049 Madrid (Spain)

    2009-07-15

    The authors study the hydriding process on commercial nuclear fuel claddings from their inner surface using an ultrahigh vacuum method. The method allows determining the incubation and failure times of the fuel claddings, as well as the dissipated energy and the partial pressure of the desorbed H{sub 2} from the outer surface of fuel claddings during the hydriding process. The correlation between the hydriding dissipated energy and the amount of zirconium hydride (formed at different stages of the hydriding process) leads to a near t{sup 1/2} potential law corresponding to the time scaling of the reaction for the majority of the tested samples. The calibrated relation between energy and hydride thickness allows one to calculate the enthalpy of the {delta}-ZrH{sub 1.5} phase. The measured H{sub 2} desorption from the external surface is in agreement with a proposed kinetic desorption model from the hydrides precipitated at the surface.

  2. Hydride phase formation in LaMg{sub 2}Ni during H{sub 2} absorption

    Energy Technology Data Exchange (ETDEWEB)

    Di Chio, M.; Baricco, M. [Dipartimento di Chimica IFM and NIS/CNISM/INSTM, Universita di Torino, Via P.Giuria, 9 10125 Torino (Italy); Schiffini, L.; Enzo, S.; Cocco, G. [Dipartimento di Chimica and INSTM, Universita di Sassari, Via Vienna, 2 07100 Sassari (Italy)

    2008-02-15

    Hydrogen absorption and desorption properties in nanocrystalline LaMg{sub 2}Ni are presented. Nanostructured phases have been obtained by milling grain coarse ingot and by mechanically alloying the parent elements. The structural and hydriding properties were examined by X-ray diffraction, thermal analysis and thermal desorption measurements. Ball milling and mechanical alloying give a significant refinement of the microstructure. Reactive milling has been used for hydrogen absorption experiments. Hydrogenation by means of reactive milling at 300 K under a pressure of 0.4 MPa leads to the formation of a stable La-hydride phase together with an amorphous phase. Thermal desorption up to 983 K of hydrogenated samples leads again to parent LaMg{sub 2}Ni phase. (author)

  3. Laser rapid forming of low cost hydride-dehydride titanium alloy powder

    Institute of Scientific and Technical Information of China (English)

    CHEN Jing; ZHANG Feng-ying; LIN Xin; TAN Hua; HUANG Wei-dong

    2006-01-01

    Low cost hydride-dehydride (HDH) Ti-6Al-4V (Ti-64) alloy powder was employed to investigate the metallurgical quality and mechanical properties of laser formed samples. With appropriate control of the laser forming processing parameters and the loose density of HDH powder, two kinds of defect, i.e. porosity and ill-bonding, can be avoided. Rare earth Nd powder was added to HDH Ti-64 powder to purify laser formed alloy. The results show that with a few additive of Nd, the microstructure of laser formed alloy changes from Widmanst-tten morphology to a basket weave microstructure. Accordingly an appropriate addition of Nd is effective to improve both the strength and ductility of laser formed HDH Ti-64 alloy. The values of tensile test meet the wrought specification with the content of Nd ranging from 0.1%-0.2%(mass fraction).

  4. Neutral and Ionized Hydrides in Star-forming Regions -- Observations with Herschel/HIFI

    CERN Document Server

    Benz, Arnold O; van Dishoeck, Ewine F; Staeuber, Pascal; Wampfler, Susanne F

    2013-01-01

    The cosmic abundance of hydrides depends critically on high-energy UV, X-ray, and particle irradiation. Here we study hydrides in star-forming regions where irradiation by the young stellar object can be substantial, and density and temperature can be much enhanced over interstellar values. Lines of OH, CH, NH, SH and their ions OH+, CH+, NH+, SH+, H2O+, and H3O+ were observed in star-forming regions by the HIFI spectrometer onboard the Herschel Space Observatory. Molecular column densities are derived from observed ground-state lines, models, or rotational diagrams. We report here on two prototypical high-mass regions, AFGL 2591 and W3 IRS5, and compare them to chemical calculations making assumptions on the high-energy irradiation. A model assuming no ionizing protostellar emission is compared with (i) a model assuming strong protostellar X-ray emission and (ii) a two-dimensional (2D) model including emission in the far UV (FUV, 6 -- 13.6 eV) irradiating the outflow walls that separate the outflowing gas an...

  5. Possible "Magnéli" Phases and Self-Alloying in the Superconducting Sulfur Hydride

    Science.gov (United States)

    Akashi, Ryosuke; Sano, Wataru; Arita, Ryotaro; Tsuneyuki, Shinji

    2016-08-01

    We theoretically give an infinite number of metastable crystal structures for the superconducting sulfur hydride HxS under pressure. Previously predicted crystalline phases of H2S and H3S have been thought to have important roles for experimentally observed low and high Tc, respectively. The newly found structures are long-period modulated crystals where slablike H2S and H3S regions intergrow on a microscopic scale. The extremely small formation enthalpy for the H2S -H3S boundary indicated by first-principles calculations suggests possible alloying of these phases through the formation of local H3S regions. The modulated structures and gradual alloying transformations between them not only explain the peculiar pressure dependence of Tc in sulfur hydride observed experimentally, but also could prevail in the experimental samples under various compression schemes.

  6. Catalitic effect of Co on hydrogen desorption form nanostucturated magnesium hydride

    Directory of Open Access Journals (Sweden)

    Matović Ljiljana Lj.

    2008-01-01

    Full Text Available To study the influence of 3d transition metal addition on desorption kinetics of MgH2 ball milling of MgH2-Co blends was performed under Ar. Microstructural and morphological characterization, performed by XRD and SEM, show a huge correlation with thermal stability and hydrogen desorption properties investigated by DSC. A complex desorption behavior is correlated with the dispersion of the metal additive particles on hydride matrix. The activation energy for H2 desorption from MgH2-Co composite was calculated from both non-isothermal and isothermal methods to be 130 kJ/mol which means that mutually diffusion and nucleation and growth of new phase control the dehydration process.

  7. Ca2LiC3H: a new complex carbide hydride phase grown in metal flux.

    Science.gov (United States)

    Lang, David A; Zaikina, Julia V; Lovingood, Derek D; Gedris, Thomas E; Latturner, Susan E

    2010-12-15

    The reaction of carbon and CaH2 in a calcium/lithium flux mixture produces crystals of the new compound Ca2LiC3H. This phase forms with a new structure type in tetragonal space group P4/mbm (a = 6.8236(1) Å, c = 3.7518(1) Å, Z = 2, R1 = 0.0151). This is a stuffed variant of the Cs2(NH2)N3 structure, containing hydride anions in octahedral sites; the structure determination by single-crystal X-ray diffraction surprisingly allowed the hydrogen to be detected. The Ca2LiC3H structure also features the rarely seen C3(4-) carbide anion; the protolysis reaction of this compound with ammonium chloride produces C3H4. The electronic properties of Ca2LiC3H were studied by quantum-chemical calculations including band structure and electron localization function (ELF) analysis; the phase is a charge-balanced semiconductor with a calculated band gap of 0.48 eV. This is in agreement with (7)Li, (13)C, and (1)H MAS NMR data, which show resonances in the ionic region instead of the Knight shifted region. ELF analysis of the theoretical nonhydrided Ca2LiC3 structure confirms the ability of these calculations to properly locate hydrides and supports the structural model based on X-ray diffraction data.

  8. Multiphysics phase field modeling of hydrogen diffusion and delta-hydride precipitation in alpha-zirconium

    Science.gov (United States)

    Jokisaari, Andrea M.

    Hydride precipitation in zirconium is a significant factor limiting the lifetime of nuclear fuel cladding, because hydride microstructures play a key role in the degradation of fuel cladding. However, the behavior of hydrogen in zirconium has typically been modeled using mean field approaches, which do not consider microstructural evolution. This thesis describes a quantitative microstructural evolution model for the alpha-zirconium/delta-hydride system and the associated numerical methods and algorithms that were developed. The multiphysics, phase field-based model incorporates CALPHAD free energy descriptions, linear elastic solid mechanics, and classical nucleation theory. A flexible simulation software implementing the model, Hyrax, is built on the Multiphysics Object Oriented Simulation Environment (MOOSE) finite element framework. Hyrax is open-source and freely available; moreover, the numerical methods and algorithms that have been developed are generalizable to other systems. The algorithms are described in detail, and verification studies for each are discussed. In addition, analyses of the sensitivity of the simulation results to the choice of numerical parameters are presented. For example, threshold values for the CALPHAD free energy algorithm and the use of mesh and time adaptivity when employing the nucleation algorithm are studied. Furthermore, preliminary insights into the nucleation behavior of delta-hydrides are described. These include a) the sensitivities of the nucleation rate to temperature, interfacial energy, composition and elastic energy, b) the spatial variation of the nucleation rate around a single precipitate, and c) the effect of interfacial energy and nucleation rate on the precipitate microstructure. Finally, several avenues for future work are discussed. Topics encompass the terminal solid solubility hysteresis of hydrogen in zirconium and the effects of the alpha/delta interfacial energy, as well as thermodiffusion, plasticity

  9. Correlations between the zeta potentials of silica hydride-based stationary phases, analyte retention behaviour and their ionic interaction descriptors.

    Science.gov (United States)

    Kulsing, Chadin; Yang, Yuanzhong; Munera, Caesar; Tse, Colby; Matyska, Maria T; Pesek, Joseph J; Boysen, Reinhard I; Hearn, Milton T W

    2014-03-19

    In this study, the zeta potentials of type-B silica, bare silica hydride, the so-called Diamond Hydride™ and phenyl substituted silica hydride stationary phases have been measured in aqueous-organic media and correction procedures developed to account for the more negative zeta potential values in media containing different acetonitrile contents. Retention studies of 16 basic, acidic and neutral compounds were also performed with these four stationary phases with mobile phases containing 0.1% (v/v) formic acid and various acetonitrile-water compositions ranging from 0-90% (v/v) acetonitrile. The retention properties of these analytes were correlated to the corrected stationary phase zeta potentials measured under these different mobile phase conditions with R(2) values ranging from 0.01 to 1.00, depending on the stationary phase and analyte type. Using linear solvation energy relationships, stationary phase descriptors for each stationary phase have been developed for the different mobile phase conditions. Very high correlations of the zeta potentials with the ionic interaction descriptors were obtained for the type-B silica and the Diamond Hydride™ phases and good correlation with bare silica hydride material whilst there was no correlation observed for the phenyl substituted silica hydride phase. The nature of the retention mechanisms which gives rise to these different observations is discussed. The described methods represent a useful new approach to characterize and assess the retention properties of silica-hydride based chromatographic stationary phases of varying bonded-phase coverage and chemistries, as would be broadly applicable to other types of stationary phase used in the separation sciences.

  10. Structural, electrical and luminescent characteristics of ultraviolet light emitting structures grown by hydride vapor phase epitaxy

    Directory of Open Access Journals (Sweden)

    A.Y. Polyakov

    2017-03-01

    Full Text Available Electrical and luminescent properties of near-UV light emitting diode structures (LEDs prepared by hydride vapor phase epitaxy (HVPE were studied. Variations in photoluminescence and electroluminescence efficiency observed for LEDs grown under nominally similar conditions could be attributed to the difference in the structural quality (dislocation density, density of dislocations agglomerates of the GaN active layers, to the difference in strain relaxation achieved by growth of AlGaN/AlGaN superlattice and to the presence of current leakage channels in current confining AlGaN layers of the double heterostructure.

  11. The storage of hydrogen in the form of metal hydrides: An application to thermal engines

    Science.gov (United States)

    Gales, C.; Perroud, P.

    1981-01-01

    The possibility of using LaNi56, FeTiH2, or MgH2 as metal hydride storage sytems for hydrogen fueled automobile engines is discussed. Magnesium copper and magnesium nickel hydrides studies indicate that they provide more stable storage systems than pure magnesium hydrides. Several test engines employing hydrogen fuel have been developed: a single cylinder motor originally designed for use with air gasoline mixture; a four-cylinder engine modified to run on an air hydrogen mixture; and a gas turbine.

  12. Verification and Validation Strategy for Implementation of Hybrid Potts-Phase Field Hydride Modeling Capability in MBM

    Energy Technology Data Exchange (ETDEWEB)

    Jason D. Hales; Veena Tikare

    2014-04-01

    The Used Fuel Disposition (UFD) program has initiated a project to develop a hydride formation modeling tool using a hybrid Potts­phase field approach. The Potts model is incorporated in the SPPARKS code from Sandia National Laboratories. The phase field model is provided through MARMOT from Idaho National Laboratory.

  13. The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components Delayed Hydride Cracking

    CERN Document Server

    Puls, Manfred P

    2012-01-01

    By drawing together the current theoretical and experimental understanding of the phenomena of delayed hydride cracking (DHC) in zirconium alloys, The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components: Delayed Hydride Cracking provides a detailed explanation focusing on the properties of hydrogen and hydrides in these alloys. Whilst the focus lies on zirconium alloys, the combination of both the empirical and mechanistic approaches creates a solid understanding that can also be applied to other hydride forming metals.   This up-to-date reference focuses on documented research surrounding DHC, including current methodologies for design and assessment of the results of periodic in-service inspections of pressure tubes in nuclear reactors. Emphasis is placed on showing that our understanding of DHC is supported by progress across a broad range of fields. These include hysteresis associated with first-order phase transformations; phase relationships in coherent crystalline metallic...

  14. Predicting impurity gases and phases during hydrogen evolution from complex metal hydrides using free energy minimization enabled by first-principles calculations.

    Science.gov (United States)

    Kim, Ki Chul; Allendorf, Mark D; Stavila, Vitalie; Sholl, David S

    2010-09-07

    First-principles calculations represent a potent tool for screening metal hydride mixtures that can reversibly store hydrogen. A number of promising new hydride systems with high hydrogen capacity and favorable thermodynamics have been predicted this way. An important limitation of these studies, however, is the assumption that H(2) is the only gas-phase product of the reaction, which is not always the case. This paper summarizes new theoretical and numerical approaches that can be used to predict thermodynamic equilibria in complex metal hydride systems with competing reaction pathways. We report thermochemical equilibrium calculations using data obtained from density functional theory (DFT) computations to describe the possible occurrence of gas-phase products other than H(2) in three complex hydrides, LiNH(2), LiBH(4), and Mg(BH(4))(2), and mixtures of these with the destabilizing compounds LiH, MgH(2), and C. The systems under investigation contain N, C, and/or B and thus have the potential to evolve N(2), NH(3), hydrocarbons, and/or boranes as well as H(2). Equilibria as a function of both temperature and total pressure are predicted. The results indicate that significant amounts of these species can form under some conditions. In particular, the thermodynamic model predicts formation of N(2) and NH(3) as products of LiNH(2) decomposition. Comparison with published experimental data indicates that N(2) formation must be kinetically limited. Our examination of C-containing systems indicates that methane is the stable gas-phase species at low temperatures, not H(2). On the other hand, very low amounts of boranes (primarily BH(3)) are predicted to form in B-containing systems.

  15. Metal hydride/chemical heat-pump development project. Phase I. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Argabright, T.A.

    1982-02-01

    The metal hydride/chemical heat pump (MHHP) is a chemical heat pump containing two hydrides for the storage and/or recovery of thermal energy. It utilizes the heat of reaction of hydrogen with specific metal alloys. The MHHP design can be tailored to provide heating and/or cooling or temperature upgrading over a wide range of input and ambient temperatures. The system can thus be used with a variety of heat sources including waste heat, solar energy or a fossil fuel. The conceptual design of the MHHP was developed. A national market survey including a study of applications and market sectors was conducted. The technical tasks including conceptual development, thermal and mechanical design, laboratory verification of design and material performance, cost analysis and the detailed design of the Engineering Development Test Unit (EDTU) were performed. As a result of the market study, the temperature upgrade cycle of the MHHP was chosen for development. Operating temperature ranges for the upgrader were selected to be from 70 to 110/sup 0/C (160 to 230/sup 0/F) for the source heat and 140 to 190/sup 0/C (280 to 375/sup 0/F) for the product heat. These ranges are applicable to many processes in industries such as food, textile, paper and pulp, and chemical. The hydride pair well suited for these temperatures is LaNi/sub 5//LaNi/sub 4/ /sub 5/Al/sub 0/ /sub 5/. The EDTU was designed for the upgrade cycle. It is a compact finned tube arrangement enclosed in a pressure vessel. This design incorporates high heat transfer and low thermal mass in a system which maximizes the coefficient of performance (COP). It will be constructed in Phase II. Continuation of this effort is recommended.

  16. CRADA (AL-C-2009-02) Final Report: Phase I. Lanthanum-based Start Materials for Hydride Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Gschneidner, Jr., Karl [Ames Laboratory; Schmidt, Frederick [Ames Laboratory; Frerichs, A. E. [Ames Laboratory; Ament, Katherine A. [Ames Laboratory

    2013-05-01

    The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La{sub 1-x}R{sub x})(Ni{sub 1-y}M{sub y})(Si{sub z}), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

  17. Ab initio study of H and He migrations in β-phase Sc, Y, and Er hydrides

    Institute of Scientific and Technical Information of China (English)

    Chen Ru-Cheng; Yang Li; Dai Yun-Ya; Zhu Zi-Qiang; Peng Shu-Ming; Long Xing-Gui; Gao Fei; Zu Xiao-Tao

    2012-01-01

    Ab initio calculations based on the density functional theory have been performed to investigate the migrations of hydrogen(H)and helium(He)atoms in β-phase scandium(Sc),yttrium(Y),and erbium(Er)hydrides with three different ratios of H to metal.The results show that the migration mechanisms of H and He atoms mainly depend on the crystal structures of hydrides,but their energy barriers are affected by the host-lattice in metal hydrides.The formation energies of octahedral-occupancy H(Hoct)and tetrahedral vacancy(Vtet)pairs are almost the same(about 1.2 eV).It is of interest to note that the migration barriers of H increase with increasing host-lattice atomic number.In addition,the results show that the favorable migration mechanism of He depends slightly on the Vtet in the Sc hydride,but strongly on that in the Y and Er hydrides,which may account for different behaviours of initial He release from ScT2 and ErT2.

  18. Hydride vapor phase epitaxy growth of GaN, InGaN, ScN, and ScAIN

    NARCIS (Netherlands)

    Bohnen, T.

    2010-01-01

    Chemical vapor deposition (CVD); hydride vapor phase epitaxy (HVPE); gallium nitride (GaN); indium gallium nitride (InGaN); scandium nitride (ScN); scandium aluminum nitride (ScAlN); semiconductors; thin films; nanowires; III nitrides; crystal growth - We studied the HVPE growth of different III ni

  19. Crystal structure of 200 K-superconducting phase in sulfur hydride system

    Energy Technology Data Exchange (ETDEWEB)

    Einaga, Mari; Sakata, Masafumi; Ishikawa, Takahiro; Shimizu, Katsuya [KYOKUGEN, Graduate School of Engineering Science, Osaka Univ. (Japan); Eremets, Mikhail; Drozdov, Alexander; Troyan, Ivan [Max Planck Institut fuer Chemie, Mainz (Germany); Hirao, Naohisa; Ohishi, Yasuo [JASRI/SPring-8, Hyogo (Japan)

    2016-07-01

    Superconductivity with the critical temperature T{sub c} above 200 K has been recently discovered by compression of H{sub 2}S (or D{sub 2}S) under extreme pressure. It was proposed that these materials decompose under high pressure to elemental sulfur and hydride with higher content of hydrogen which is responsible for the high temperature superconductivity. In this study, we have investigated that the crystal structure of the superconducting compressed H{sub 2}S and D{sub 2}S by synchrotron x-ray diffraction measurements combined with electrical resistance measurements at room and low temperatures. We found that the superconducting phase is in good agreement with theoretically predicted body-centered cubic structure, and coexists with elemental sulfur, which claims that the formation of 3H{sub 2}S → 2H{sub 3}S + S is occured under high pressure.

  20. Characterization of the whiskerlike products formed by hydriding magnesium metal powders

    DEFF Research Database (Denmark)

    Herley, P. J.; Jones, W.; Vigeholm, Bjørn

    1985-01-01

    The structure of filamentary crystals produced during the hydriding of magnesium powder has been studies in detail. The needles of small dimensions (typically 0.5 μm in diameter) have been identified by electron analytical techniques to be oriented microcrystals of metallic magnesium...

  1. Synthesis of ruthenium hydride

    Science.gov (United States)

    Kuzovnikov, M. A.; Tkacz, M.

    2016-02-01

    Ruthenium hydride was synthesized at a hydrogen pressure of about 14 GPa in a diamond-anvil cell. Energy-dispersive x-ray diffraction was used to monitor the ruthenium crystal structure as a function of hydrogen pressure up to 30 GPa. The hydride formation was accompanied by phase transition from the original hcp structure of the pristine metal to the fcc structure. Our results confirmed the theoretical prediction of ruthenium hydride formation under hydrogen pressure. The standard Gibbs free energy of the ruthenium hydride formation reaction was calculated assuming the pressure of decomposition as the equilibrium pressure.

  2. Clean Grain Boundary Found in C14/Body-Center-Cubic Multi-Phase Metal Hydride Alloys

    Directory of Open Access Journals (Sweden)

    Hao-Ting Shen

    2016-06-01

    Full Text Available The grain boundaries of three Laves phase-related body-center-cubic (bcc solid-solution, metal hydride (MH alloys with different phase abundances were closely examined by scanning electron microscopy (SEM, transmission electron microscopy (TEM, and more importantly, electron backscatter diffraction (EBSD techniques. By using EBSD, we were able to identify the alignment of the crystallographic orientations of the three major phases in the alloys (C14, bcc, and B2 structures. This finding confirms the presence of crystallographically sharp interfaces between neighboring phases, which is a basic assumption for synergetic effects in a multi-phase MH system.

  3. Hysteresis in Metal Hydrides.

    Science.gov (United States)

    Flanagan, Ted B., And Others

    1987-01-01

    This paper describes a reproducible process where the irreversibility can be readily evaluated and provides a thermodynamic description of the important phenomenon of hysteresis. A metal hydride is used because hysteresis is observed during the formation and decomposition of the hydride phase. (RH)

  4. A Kinetic Model for GaAs Growth by Hydride Vapor Phase Epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Schulte, Kevin L.; Simon, John; Jain, Nikhil; Young, David L.; Ptak, Aaron J.

    2016-11-21

    Precise control of the growth of III-V materials by hydride vapor phase epitaxy (HVPE) is complicated by the fact that the growth rate depends on the concentrations of nearly all inputs to the reactor and also the reaction temperature. This behavior is in contrast to metalorganic vapor phase epitaxy (MOVPE), which in common practice operates in a mass transport limited regime where growth rate and alloy composition are controlled almost exclusively by flow of the Group III precursor. In HVPE, the growth rate and alloy compositions are very sensitive to temperature and reactant concentrations, which are strong functions of the reactor geometry. HVPE growth, particularly the growth of large area materials and devices, will benefit from the development of a growth model that can eventually be coupled with a computational fluid dynamics (CFD) model of a specific reactor geometry. In this work, we develop a growth rate law using a Langmuir-Hinshelwood (L-H) analysis, fitting unknown parameters to growth rate data from the literature that captures the relevant kinetic and thermodynamic phenomena of the HVPE process. We compare the L-H rate law to growth rate data from our custom HVPE reactor, and develop quantitative insight into reactor performance, demonstrating the utility of the growth model.

  5. Simultaneous separation of hydrophobic and hydrophilic peptides with a silica hydride stationary phase using aqueous normal phase conditions.

    Science.gov (United States)

    Boysen, Reinhard I; Yang, Yuanzhong; Chowdhury, Jamil; Matyska, Maria T; Pesek, Joseph J; Hearn, Milton T W

    2011-11-04

    The application of a silica hydride modified stationary phase with low organic loading has been investigated as a new type of chromatographic material suitable for the separation and analysis of peptides with electrospray ionization mass spectrometric detection. Retention maps were established to delineate the chromatographic characteristics of a series of peptides with physical properties ranging from strongly hydrophobic to very hydrophilic and encompassing a broad range of pI values (pI 5.5-9.4). The effects of low concentrations of two additives (formic acid and acetic acid) in the mobile phase were also investigated with respect to their contribution to separation selectivity and retention under comparable conditions. Significantly, strong retention of both the hydrophobic and the hydrophilic peptides was observed when high-organic low-aqueous mobile phases were employed, thus providing a new avenue to achieve high resolution peptide separations. For example, simultaneous separation of hydrophobic and hydrophilic peptides was achieved under aqueous normal phase (ANP) chromatographic conditions with linear gradient elution procedures in a single run, whilst further gradient optimization enabled improved peak efficiencies of the more strongly retained hydrophobic and hydrophilic peptides.

  6. Determination of arsenic and selenium by hydride generation and headspace solid phase microextraction coupled with optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tyburska, Anna; Jankowski, Krzysztof, E-mail: kj@ch.pw.edu.pl; Rodzik, Agnieszka

    2011-07-15

    A hydride generation headspace solid phase microextraction technique has been developed in combination with optical emission spectrometry for determination of total arsenic and selenium. Hydrides were generated in a 10 mL volume septum-sealed vial and subsequently collected onto a polydimethylsiloxane/Carboxen solid phase microextraction fiber from the headspace of sample solution. After completion of the sorption, the fiber was transferred into a thermal desorption unit and the analytes were vaporized and directly introduced into argon inductively coupled plasma or helium microwave induced plasma radiation source. Experimental conditions of hydride formation reaction as well as sorption and desorption of analytes have been optimized showing the significant effect of the type of the solid phase microextraction fiber coating, the sorption time and hydrochloric acid concentration of the sample solution on analytical characteristics of the method developed. The limits of detection of arsenic and selenium were 0.1 and 0.8 ng mL{sup -1}, respectively. The limit of detection of selenium could be improved further using biosorption with baker's yeast Saccharomyces cerevisiae for analyte preconcentration. The technique was applied for the determination of total As and Se in real samples.

  7. Epitaxial growth of three dimensionally structured III-V photonic crystal via hydride vapor phase epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Qiye; Kim, Honggyu; Zhang, Runyu; Zuo, Jianmin; Braun, Paul V., E-mail: pbraun@illinois.edu [Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Sardela, Mauro [Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Balaji, Manavaimaran; Lourdudoss, Sebastian; Sun, Yan-Ting [Laboratory of Semiconductor Materials, Department of Materials and Nano Physics, Royal Institute of Technology (KTH), Electrum 229, 164 40 Kista (Sweden)

    2015-12-14

    Three-dimensional (3D) photonic crystals are one class of materials where epitaxy, and the resultant attractive electronic properties, would enable new functionalities for optoelectronic devices. Here we utilize self-assembled colloidal templates to fabricate epitaxially grown single crystal 3D mesostructured Ga{sub x}In{sub 1−x}P (GaInP) semiconductor photonic crystals using hydride vapor phase epitaxy (HVPE). The epitaxial relationship between the 3D GaInP and the substrate is preserved during the growth through the complex geometry of the template as confirmed by X-ray diffraction (XRD) and high resolution transmission electron microscopy. XRD reciprocal space mapping of the 3D epitaxial layer further demonstrates the film to be nearly fully relaxed with a negligible strain gradient. Fourier transform infrared spectroscopy reflection measurement indicates the optical properties of the photonic crystal which agree with finite difference time domain simulations. This work extends the scope of the very few known methods for the fabrication of epitaxial III-V 3D mesostructured materials to the well-developed HVPE technique.

  8. Identification and characterization of a new zirconium hydride; Identification et caracterisation d'un nouvel hydrure de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhao; Morniroli, J.P.; Legris, A.; Thuinet, L. [Universite des Sciences et Technologies de Lille, USTL, ENSCL, CNRS, 59 - Villeneuve d' Ascq (France); Zhao, Zhao; Blat-Yrieix, M.; Ambard, A.; Legras, L. [Electricite de France (EDF/RD), Centre des Renardieres, 77 - Moret sur Loing (France); Kihn, Y. [CEMES-CNRS, 31 - Toulouse (France)

    2007-07-01

    A study of hydrides characterization has been carried out in using the transmission electron microscopy technique. It has revealed the presence of small hydrides of acicular form whose length does not exceed 500 nm, among the zircaloy-4 samples hydrided by cathodic way. The electronic diffraction has shown that these small hydrides have a crystallographic structure different of those of the hydrides phases already index in literature. A more complete identification study has then been carried out. In combining the different electronic microscopy techniques (precession electronic micro diffraction and EELS) with ab initio calculations, a new hydride phase has been identified. It is called hydride {zeta}, is of trigonal structure with lattice parameters a{sub {zeta}} = a{sub {alpha}}{sub Zr} = 0.33 nm and c{sub {zeta}} 2c{sub {alpha}}{sub Zr} = 1.029 nm, its spatial group being P3m1. (O.M.)

  9. A phase-field model to study the effects of temperature change on shape evolution of γ-hydrides in zirconium

    Science.gov (United States)

    Bair, Jacob; Asle Zaeem, Mohsen; Tonks, Michael

    2016-10-01

    A temperature-dependent phase-field model is developed to study the effects of temperature change on shape evolution of γ-hydrides in an α-zirconium matrix. To construct the temperature-dependent free energy functional of the phase-field model, Gibbs free energies of formation from previous experiments are employed, and one conserved and three non-conserved phase-field variables are used for hydrogen concentration and hydride orientations, respectively. The mixed order evolution equations of phase-field variables coupled with mechanical equilibrium equations are solved in a finite element framework. Results from isothermal simulations of seeded and random nucleation in single crystal α-zirconium matrix show that the thickness of non-equilibrium hydrides varies with temperature during evolution, and the hydrides are more rod-like (thinner) at higher temperatures and thicker at lower temperatures. Quench simulations with random nucleation indicate that the majority of precipitation occurs at early stages of quenching, but the size and shape of hydrides change as the temperature decreases. Simulations from random nucleation of hydrides in a polycrystalline α-zirconium matrix show a higher concentration of precipitates along high angle grain boundaries.

  10. Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound.

    Science.gov (United States)

    Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian

    2015-10-16

    In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time.

  11. Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound

    Science.gov (United States)

    Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian

    2015-10-01

    In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time.

  12. Are cyclopentadienylberyllium, magnesium and calcium hydrides carbon or metal acids in the gas phase?

    Science.gov (United States)

    Hurtado, Marcela; Lamsabhi, Al-Mokhtar; Mó, Otilia; Yáñez, Manuel; Guillemin, Jean-Claude

    2010-05-21

    The structure and bonding of cyclopentadienylberyllium (CpBeH), magnesium (CpMgH), and calcium (CpCaH) hydrides as well as those of their deprotonated species have been investigated by means of B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) and B3LYP/6-311+G(3df,2p)//QCISD/6-311+G(d,p) density functional theory (DFT) calculations. The three compounds exhibit C(5v) equilibrium conformations in their ground states. For CpBeH the agreement between the calculated geometry and that determined by MW spectroscopy is excellent. CpMgH and CpCaH can be viewed almost as the result of the interaction between a C₅H₅⁻ anion and a XH(+) (X = Mg, Ca) cation. Conversely, for CpBeH the interaction between the C₅H₅ and the BeH subunits is significantly covalent. These compounds exhibit a significant aromaticity, usually named three-dimension aromaticity, in contrast with the unsubstituted cyclopentadiene compound. The CpBeH derivative behaves as a C acid in the gas phase and is less acidic than cyclopentadiene. More importantly, CpMgH and CpCaH, in spite of the X(+δ)H(-δ) polarity exhibited by the X-H bond in the neutral systems, are predicted to be metal acids in the gas phase. Also surprisingly, both the Mg and the Ca derivatives are stronger acids than the Be analogue, and only slightly weaker acids than cyclopentadiene. This somewhat unexpected result is the consequence of two concomitant facts: the lower dissociation energy of the X-H (X = Mg, Ca) bonds with respect to the C-H bonds, and the significantly high electron affinity of the C₅H₅X* (X = Mg, Ca) radicals.

  13. Flow injection on-line solid phase extraction for ultra-trace lead screening with hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Wan, Zhuo; Xu, Zhangrun; Wang, Jianhua

    2006-01-01

    A flow injection (FI) on-line solid phase extraction (SPE) procedure for ultra-trace lead separation and preconcentration was developed, followed by hydride generation and atomic fluorescence spectrometric (AFS) detection. Lead is retained on an iminodiacetate chelating resin packed microcolumn, and is afterward eluted with 2.5% (v/v) hydrochloric acid to facilitate the hydride generation by reaction with alkaline tetrahydroborate solution with 1% (m/v) potassium ferricyanide as an oxidizing (or sensitizing) reagent. The hydride was separated from the reaction medium in the gas-liquid separator and swept into the atomizer for quantification. The chemical variables and the FI flow parameters were carefully optimized. With a sample loading volume of 4.8 ml, quantitative retention of lead was obtained, along with an enrichment factor of 11.3 and a sampling frequency of 50 h(-1). A detection limit of 4 ng l(-1), defined as 3 times the blank standard deviation (3 sigma), was achieved along with a RSD value of 1.6% at the 0.4 microg l(-1) level. The procedure was validated by determining lead contents in two certified reference materials, and its practical applicability was further demonstrated by analysing a variety of biological and environmental samples.

  14. Multivariate optimization and simultaneous determination of hydride and non-hydride-forming elements in samples of a wide pH range using dual-mode sample introduction with plasma techniques: application on leachates from cement mortar material.

    Science.gov (United States)

    Mulugeta, Mesay; Wibetoe, Grethe; Engelsen, Christian J; Asfaw, Alemayehu

    2009-02-01

    Analytical methods have been developed for the simultaneous determination of hydride-forming (As, Sb) and non-hydride-forming (Cr, Mo, V) elements in aqueous samples of a wide pH range (pH 3-13). The methods used dual-mode (DM) sample introduction with ICP-AES and ICP-MS instruments. The effect of selected experimental variables, i.e., sample pH and concentrations of HNO(3), thiourea, and NaBH(4), were studied in a multivariate way using face-centered central composite design (FC-CCD). Compromised optimum values of the experimental parameters were identified using a response optimizer. The statistically found optimum values were verified experimentally. The methods provided improved sensitivities for the hydride-forming elements compared with the respective conventional nebulization (Neb) systems by factors of 67 (As) and 64 (Sb) for ICP-AES and 36 (As) and 54 (Sb) for ICP-MS. Slight sensitivity improvements were also observed for the non-hydride-forming elements. The limits of detection (LOD) of As and Sb were lowered, respectively, to 0.8 and 0.9 microg L(-1) with the DM-ICP-AES system and to 0.01 and 0.02 microg L(-1) with the DM-ICP-MS system. The short-term stabilities of both methods were between 2.1 and 5.4%. The methods were applied for the analysis of leachates of a cement mortar material prepared in the pH range 3-13. The elemental concentration of the leachates determined by the two DM methods were statistically compared with the values obtained from Neb-ICP-MS analysis; the values showed good agreement at the 95% confidence level. Quantitative spike recoveries were obtained for the analytes from most of the leachates using both DM methods.

  15. Polycrystalline indium phosphide on silicon by indium assisted growth in hydride vapor phase epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Metaferia, Wondwosen; Sun, Yan-Ting, E-mail: yasun@kth.se; Lourdudoss, Sebastian [Laboratory of Semiconductor Materials, Department of Materials and Nano Physics, KTH—Royal Institute of Technology, Electrum 229, 164 40 Kista (Sweden); Pietralunga, Silvia M. [CNR-Institute for Photonics and Nanotechnologies, P. Leonardo da Vinci, 32 20133 Milano (Italy); Zani, Maurizio; Tagliaferri, Alberto [Department of Physics Politecnico di Milano, P. Leonardo da Vinci, 32 20133 Milano (Italy)

    2014-07-21

    Polycrystalline InP was grown on Si(001) and Si(111) substrates by using indium (In) metal as a starting material in hydride vapor phase epitaxy (HVPE) reactor. In metal was deposited on silicon substrates by thermal evaporation technique. The deposited In resulted in islands of different size and was found to be polycrystalline in nature. Different growth experiments of growing InP were performed, and the growth mechanism was investigated. Atomic force microscopy and scanning electron microscopy for morphological investigation, Scanning Auger microscopy for surface and compositional analyses, powder X-ray diffraction for crystallinity, and micro photoluminescence for optical quality assessment were conducted. It is shown that the growth starts first by phosphidisation of the In islands to InP followed by subsequent selective deposition of InP in HVPE regardless of the Si substrate orientation. Polycrystalline InP of large grain size is achieved and the growth rate as high as 21 μm/h is obtained on both substrates. Sulfur doping of the polycrystalline InP was investigated by growing alternating layers of sulfur doped and unintentionally doped InP for equal interval of time. These layers could be delineated by stain etching showing that enough amount of sulfur can be incorporated. Grains of large lateral dimension up to 3 μm polycrystalline InP on Si with good morphological and optical quality is obtained. The process is generic and it can also be applied for the growth of other polycrystalline III–V semiconductor layers on low cost and flexible substrates for solar cell applications.

  16. Planarization and Processing of Metamorphic Buffer Layers Grown by Hydride Vapor-Phase Epitaxy

    Science.gov (United States)

    Zutter, Brian T.; Schulte, Kevin L.; Kim, Tae Wan; Mawst, Luke J.; Kuech, T. F.; Foran, Brendan; Sin, Yongkun

    2014-04-01

    Hydride vapor-phase epitaxy (HVPE) is a high-growth-rate, cost-effective means to grow epitaxial semiconductor material. Thick HVPE-based metamorphic buffer layers (MBLs) can serve as "pseudosubstrates" with controllable lattice parameter. In our structures, the indium content in In x Ga1- x As is gradually increased from zero to the final composition corresponding to the desired lattice constant, and then a thick (˜10 μm) constant-composition capping layer is grown. This thick capping layer promotes maximum strain relaxation while permitting use of polishing procedures to achieve surface planarity. Lattice-mismatched growth of MBLs invariably results in rough, cross-hatched surface morphology exhibiting up to 200 nm peak-to-valley roughness. This roughness can be eliminated by chemical mechanical planarization, thus creating a suitable surface for subsequent regrowth. Polishing of In x Ga1- x As is complicated by the sensitivity of the surface layer to the polishing parameters, particularly the applied pressure. Polishing at high applied pressure (12 psi) results in the formation of circular asperities hundreds of nanometers high and tens of microns in diameter. When lower applied pressure (4 psi) was used, the cross-hatching height of MBLs was lowered from 200 nm to <10 nm over a 350 μm lateral scale. The successfully planarized In0.20Ga0.80As MBLs were used as a substrate for a superlattice (SL) structure such as that used in quantum cascade lasers. Use of planarization before regrowth of the SL resulted in a reduction of the high-resolution x-ray diffraction peak full-width at half-maximum from 389″ to 159″.

  17. InGaAsP Solar Cells Grown by Hydride Vapor Phase Epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Nikhil; Simon, John; Schulte, Kevin L.; Dippo, Patricia; Young, Michelle; Young, David L.; Ptak, Aaron J.

    2016-11-21

    Hydride vapor phase epitaxy (HVPE) has recently reemerged as a low-cost, high-throughput alternative to metalorganic chemical vapor deposition (MOCVD) for the growth of high-efficiency III-V solar cells. Quaternary InGaAsP solar cells in the bandgap range of ~1.7-1.8 eV are promising top-cell candidates for integration in Ill-V/Si tandem cells with projected one-sun efficiencies exceeding 30%. In this work, we report on the development of lattice-matched InGaAsP solar cells grown on GaAs substrates via HVPE at very high growth rates of ~0.7 um/min. We demonstrate prototype 1.7 eV InGaAsP solar cells with an open-circuit voltage of 1.11 V. The short-circuit current is limited by the lack of a window layer in these early stage devices. The photo response of 1.7 InGaAsP solar cell with ~1.1 um thick base layer is found to be nearly insensitive to variation in p-type base doping concentration in the range from Na - 4x1016 to - 1x1017 cm-3, indicating an effective carrier collection length on the order of - 1.1 um or higher in our devices. These initial InGaAsP cell results are encouraging and highlight the viability of HVPE to produce mixed arsenide-phosphide solar cells grown lattice-matched on GaAs.

  18. Electrochemical and Optical Properties of Magnesium-Alloy Hydrides Reviewed

    Directory of Open Access Journals (Sweden)

    Thirugnasambandam G. Manivasagam

    2012-10-01

    Full Text Available As potential hydrogen storage media, magnesium based hydrides have been systematically studied in order to improve reversibility, storage capacity, kinetics and thermodynamics. The present article deals with the electrochemical and optical properties of Mg alloy hydrides. Electrochemical hydrogenation, compared to conventional gas phase hydrogen loading, provides precise control with only moderate reaction conditions. Interestingly, the alloy composition determines the crystallographic nature of the metal-hydride: a structural change is induced from rutile to fluorite at 80 at.% of Mg in Mg-TM alloy, with ensuing improved hydrogen mobility and storage capacity. So far, 6 wt.% (equivalent to 1600 mAh/g of reversibly stored hydrogen in MgyTM(1-yHx (TM: Sc, Ti has been reported. Thin film forms of these metal-hydrides reveal interesting electrochromic properties as a function of hydrogen content. Optical switching occurs during (dehydrogenation between the reflective metal and the transparent metal hydride states. The chronological sequence of the optical improvements in optically active metal hydrides starts with the rare earth systems (YHx, followed by Mg rare earth alloy hydrides (MgyGd(1-yHx and concludes with Mg transition metal hydrides (MgyTM(1-yHx. In-situ optical characterization of gradient thin films during (dehydrogenation, denoted as hydrogenography, enables the monitoring of alloy composition gradients simultaneously.

  19. Results of NDE Technique Evaluation of Clad Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kunerth, Dennis C. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-09-01

    This report fulfills the M4 milestone, M4FT-14IN0805023, Results of NDE Technique Evaluation of Clad Hydrides, under Work Package Number FT-14IN080502. During service, zirconium alloy fuel cladding will degrade via corrosion/oxidation. Hydrogen, a byproduct of the oxidation process, will be absorbed into the cladding and eventually form hydrides due to low hydrogen solubility limits. The hydride phase is detrimental to the mechanical properties of the cladding and therefore it is important to be able to detect and characterize the presence of this constituent within the cladding. Presently, hydrides are evaluated using destructive examination. If nondestructive evaluation techniques can be used to detect and characterize the hydrides, the potential exists to significantly increase test sample coverage while reducing evaluation time and cost. To demonstrate the viability this approach, an initial evaluation of eddy current and ultrasonic techniques were performed to demonstrate the basic ability to these techniques to detect hydrides or their effects on the microstructure. Conventional continuous wave eddy current techniques were applied to zirconium based cladding test samples thermally processed with hydrogen gas to promote the absorption of hydrogen and subsequent formation of hydrides. The results of the evaluation demonstrate that eddy current inspection approaches have the potential to detect both the physical damage induced by hydrides, e.g. blisters and cracking, as well as the combined effects of absorbed hydrogen and hydride precipitates on the electrical properties of the zirconium alloy. Similarly, measurements of ultrasonic wave velocities indicate changes in the elastic properties resulting from the combined effects of absorbed hydrogen and hydride precipitates as well as changes in geometry in regions of severe degradation. However, for both approaches, the signal responses intended to make the desired measurement incorporate a number of contributing

  20. First Principles Study of Titanium Hydrides, TiHn: n = 1, 2, 3; Energetics and Phase Transition

    Directory of Open Access Journals (Sweden)

    Shunmugam KANAGAPRABHA

    2014-06-01

    Full Text Available The electronic structure and structural phase transition of TiHn (n = 1, 2 and 3 are investigated using the Tight-Binding Linear Muffin-Tin Orbital (TB-LMTO method with Local density approximation (LDA and Atomic sphere approximation (ASA. The equilibrium geometries, the electronic band structure, and the total and partial Density of States (DOS are obtained under various pressures, and are analyzed in comparison with the available experimental and theoretical data. It is predicted that the most stable structure of Titanium hydride is a cubic structure at normal pressure. Both TiH and TiH2 undergo a structural phase transition from a cubic to a hexagonal phase under high pressure. The stability of TiM2H and TiMH2 is analyzed.

  1. YNi and its hydrides: Phase stabilities, electronic structures and chemical bonding properties from first principles

    Energy Technology Data Exchange (ETDEWEB)

    Matar, S.F., E-mail: matar@icmcb-bordeaux.cnrs.fr [CNRS, Universite de Bordeaux, ICMCB, 87 avenue du Docteur Albert Schweitzer, F-33608 Pessac (France); Nakhl, M. [Universite Libanaise, Laboratoire de Chimie-Physique des Materiaux LCPM, Fanar (Lebanon); Al Alam, A.F.; Ouaini, N. [Universite Saint-Esprit de Kaslik, Faculte des Sciences et de Genie Informatique, Jounieh (Lebanon); Chevalier, B. [CNRS, Universite de Bordeaux, ICMCB, 87 avenue du Docteur Albert Schweitzer, F-33608 Pessac (France)

    2010-11-25

    Graphical abstract: Base centered orthorhombic YNiH{sub X} structure. For x = 3, only H1 and H2 are present. Highest hydrogen content YNiH{sub 4} is obtained when H3 are added. - Abstract: Within density functional theory, establishing the equations of states of YNi in two different controversial structures in the literature, leads to determine the orthorhombic FeB-type as the ground state one with small energy difference. For YNiH{sub 3} and YNiH{sub 4} hydrides crystallizing in the orthorhombic CrB-type structure the geometry optimization and the ab initio determination of the H atomic positions show that the stability of hydrogen decreases from the tri- to the tetra- hydride. New states brought by hydrogen within the valence band lead to its broadening and to enhanced localization of metal density of states. The chemical bonding analysis shows a preferential Ni-H bonding versus Y-H.

  2. High H- ionic conductivity in barium hydride

    Science.gov (United States)

    Verbraeken, Maarten C.; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T. S.

    2015-01-01

    With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H-) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm-1 at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

  3. Zirconium hydrides and Fe redistribution in Zr-2.5%Nb alloy under ion irradiation

    Science.gov (United States)

    Idrees, Y.; Yao, Z.; Cui, J.; Shek, G. K.; Daymond, M. R.

    2016-11-01

    Zr-2.5%Nb alloy is used to fabricate the pressure tubes of the CANDU reactor. The pressure tube is the primary pressure boundary for coolant in the CANDU design and is susceptible to delayed hydride cracking, reduction in fracture toughness upon hydride precipitation and potentially hydride blister formation. The morphology and nature of hydrides in Zr-2.5%Nb with 100 wppm hydrogen has been investigated using transmission electron microscopy. The effect of hydrides on heavy ion irradiation induced decomposition of the β phase has been reported. STEM-EDX mapping was employed to investigate the distribution of alloying elements. The results show that hydrides are present in the form of stacks of different sizes, with length scales from nano- to micro-meters. Heavy ion irradiation experiments at 250 °C on as-received and hydrided Zr-2.5%Nb alloy, show interesting effects of hydrogen on the irradiation induced redistribution of Fe. It was found that Fe is widely redistributed from the β phase into the α phase in the as-received material, however, the loss of Fe from the β phase and subsequent precipitation is retarded in the hydrided material. This preliminary work will further the current understanding of microstructural evolution of Zr based alloys in the presence of hydrogen.

  4. Mechanochemical synthesis of nanostructured chemical hydrides in hydrogen alloying mills

    Energy Technology Data Exchange (ETDEWEB)

    Wronski, Z. [CANMET' s Materials Technology Laboratory, Natural Resources Canada, Ottawa (Canada) and Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada)]. E-mail: zwronski@nrcan.gc.ca; Varin, R.A. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Chiu, C. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Czujko, T. [Department of Mechanical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1 (Canada); Calka, A. [Department of Materials Science and Engineering, University of Wollongong, NSW 2518 (Australia)

    2007-05-31

    Mechanical alloying of magnesium metal powders with hydrogen in specialized hydrogen ball mills can be used as a direct route for mechanochemical synthesis of emerging chemical hydrides and hydride mixtures for advanced solid-state hydrogen storage. In the 2Mg-Fe system, we have successfully synthesized the ternary complex hydride Mg{sub 2}FeH{sub 6} in a mixture with nanometric Fe particles. The mixture of complex magnesium-iron hydride and nano-iron released 3-4 wt.%H{sub 2} in a thermally programmed desorption experiment at the range 285-295 {sup o}C. Milling of the Mg-2Al powder mixture revealed a strong competition between formation of the Al(Mg) solid solution and the {beta}-MgH{sub 2} hydride. The former decomposes upon longer milling as the Mg atoms react with hydrogen to form the hydride phase, and drive the Al out of the solid solution. The mixture of magnesium dihydride and nano-aluminum released 2.1 wt.%H{sub 2} in the temperature range 329-340 {sup o}C in the differential scanning calorimetry experiment. The formation of MgH{sub 2} was suppressed in the Mg-B system; instead, a hydrogenated amorphous phase (Mg,B)H {sub x}, was formed in a mixture with nanometric MgB{sub 2}. Annealing of the hydrogen-stabilized amorphous mixture produced crystalline MgB{sub 2}.

  5. Phase transformation in magnesium hydride induced by ball milling; Changement de phase induit par broyage mecanique dans l'hydrure de magnesium

    Energy Technology Data Exchange (ETDEWEB)

    Huot, J. [Universite du Quebec a Trois-Rivieres, Institut de Recherche sur l' Hydrogene, Quebec (Canada); Swainson, I. [Canadian Neutron Beam Centre, National Research Council Canada, Chalk River Lab. (Canada); Schulz, R. [Institut de Recherche d' Hydro-Quebec, Expertise Chimie et Materiaux, Quebec (Canada)

    2006-01-15

    The synthesis of magnesium hydride by reactive ball milling leads to the formation of a metastable orthorhombic {gamma}-MgH{sub 2} phase along with tetragonal {beta}-MgH{sub 2}. The structures of the {beta}-MgD{sub 2} and {gamma}-MgD{sub 2} phases of ball milled nanocrystalline MgD{sub 2} were studied by neutron powder diffraction. The ball-milled {beta}-MgD{sub 2} and {gamma}-MgD{sub 2} structures are distorted compared to the same phases synthesized by high-pressure and high temperature. Two Mg-D bond lengths are significantly distorted in {beta}-MgD{sub 2} while in the {gamma}-MgD{sub 2} phase, only one bond length is largely affected. The micro-stress associated with the strain fields and deformations caused by the ball milling is most likely the driving force of this phase transformation. (authors)

  6. Hydrogen Outgassing from Lithium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L N; Schildbach, M A; Smith, R A; Balazs1, B; McLean II, W

    2006-04-20

    Lithium hydride is a nuclear material with a great affinity for moisture. As a result of exposure to water vapor during machining, transportation, storage and assembly, a corrosion layer (oxide and/or hydroxide) always forms on the surface of lithium hydride resulting in the release of hydrogen gas. Thermodynamically, lithium hydride, lithium oxide and lithium hydroxide are all stable. However, lithium hydroxides formed near the lithium hydride substrate (interface hydroxide) and near the sample/vacuum interface (surface hydroxide) are much less thermally stable than their bulk counterpart. In a dry environment, the interface/surface hydroxides slowly degenerate over many years/decades at room temperature into lithium oxide, releasing water vapor and ultimately hydrogen gas through reaction of the water vapor with the lithium hydride substrate. This outgassing can potentially cause metal hydriding and/or compatibility issues elsewhere in the device. In this chapter, the morphology and the chemistry of the corrosion layer grown on lithium hydride (and in some cases, its isotopic cousin, lithium deuteride) as a result of exposure to moisture are investigated. The hydrogen outgassing processes associated with the formation and subsequent degeneration of this corrosion layer are described. Experimental techniques to measure the hydrogen outgassing kinetics from lithium hydride and methods employing the measured kinetics to predict hydrogen outgassing as a function of time and temperature are presented. Finally, practical procedures to mitigate the problem of hydrogen outgassing from lithium hydride are discussed.

  7. Neutron scattering studies on the vibrational excitations and the structure of ordered niobium hydrides: the {lambda} phases

    Energy Technology Data Exchange (ETDEWEB)

    Hauer, B [Institut fuer Festkoerperforschung, Forschungszentrum Juelich, D-52425 Juelich (Germany); Hempelmann, R [Physikalische Chemie, Universitaet des Saarlandes, D-66041 Saarbruecken (Germany); Udovic, T J [National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Rush, J J [National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Kockelmann, W [Mineralogisches Institut der Universitaet Bonn, Aussenstelle Juelich, D-52425 Juelich (Germany); Schaefer, W [Mineralogisches Institut der Universitaet Bonn, Aussenstelle Juelich, D-52425 Juelich (Germany); Jansen, E [Mineralogisches Institut der Universitaet Bonn, Aussenstelle Juelich, D-52425 Juelich (Germany); Richter, D [Institut fuer Festkoerperforschung, Forschungszentrum Juelich, D-52425 Juelich (Germany)

    2004-07-28

    Neutron vibrational spectroscopy and neutron diffraction have been used to study the optical hydrogen vibrations in and the structure of ordered niobium hydrides NbH{sub x} and deuterides NbD{sub x} in the concentration range 0.73phase. Neutron diffraction data collected in the regime of the {lambda} phases (T<200 K, 0.73phase structure. Neutron vibrational spectra display up to three families of peaks that can be assigned to three different hydrogen sites: an undisturbed tetrahedral site within the microdomains and two strongly disturbed tetrahedral sites within two different kinds of microdomain boundaries. Incommensurately modulated phases probably exist in this concentration range. For hydrogen concentrations around x {approx}0.85 there is evidence for a change of symmetry of the basic cell as well as a change of the modulation at even higher concentrations. In the range of the {gamma} phase at x {approx} 0.9, strong isotopic effects occur. The results give new insights into the phase diagram.

  8. Lightweight hydride storage materials

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W. [Sandia National Labs., Livermore, CA (United States)

    1995-09-01

    The need for lightweight hydrides in vehicular applications has prompted considerable research into the use of magnesium and its alloys. Although this earlier work has provided some improved performance in operating temperature and pressure, substantial improvements are needed before these materials will significantly enhance the performance of an engineered system on a vehicle. We are extending the work of previous investigators on Mg alloys to reduce the operating temperature and hydride heat of formation in light weight materials. Two important results will be discussed in this paper: (1) a promising new alloy hydride was found which has better pressure-temperature characteristics than any previous Mg alloy and, (2) a new fabrication process for existing Mg alloys was developed and demonstrated. The new alloy hydride is composed of magnesium, aluminum and nickel. It has an equilibrium hydrogen overpressure of 1.3 atm. at 200{degrees}C and a storage capacity between 3 and 4 wt.% hydrogen. A hydrogen release rate of approximately 5 x 10{sup -4} moles-H{sub 2}/gm-min was measured at 200{degrees}C. The hydride heat of formation was found to be 13.5 - 14 kcal/mole-H{sub 2}, somewhat lower than Mg{sub 2}Ni. The new fabrication method takes advantage of the high vapor transport of magnesium. It was found that Mg{sub 2}Ni produced by our low temperature process was better than conventional materials because it was single phase (no Mg phase) and could be fabricated with very small particle sizes. Hydride measurements on this material showed faster kinetic response than conventional material. The technique could potentially be applied to in-situ hydride bed fabrication with improved packing density, release kinetics, thermal properties and mechanical stability.

  9. Spontaneous formation of GaN/AlN core-shell nanowires on sapphire by hydride vapor phase epitaxy

    Science.gov (United States)

    Trassoudaine, Agnès; Roche, Elissa; Bougerol, Catherine; André, Yamina; Avit, Geoffrey; Monier, Guillaume; Ramdani, Mohammed Réda; Gil, Evelyne; Castelluci, Dominique; Dubrovskii, Vladimir G.

    2016-11-01

    Spontaneous GaN/AlN core-shell nanowires with high crystal quality were synthesized on sapphire substrates by vapor-liquid-solid hydride vapor phase epitaxy (VLS-HVPE) without any voluntary aluminum source. Deposition of aluminum is difficult to achieve in this growth technique which uses metal-chloride gaseous precursors: the strong interaction between the AlCl gaseous molecules and the quartz reactor yields a huge parasitic nucleation on the walls of the reactor upstream the substrate. We open up an innovative method to produce GaN/AlN structures by HVPE, thanks to aluminum etching from the sapphire substrate followed by redeposition onto the sidewalls of the GaN core. The paper presents the structural characterization of GaN/AlN core-shell nanowires, speculates on the growth mechanism and discusses a model which describes this unexpected behavior.

  10. Characteristics of stimulated emission from optically pumped freestanding GaN grown by hydride vapor-phase epitaxy

    CERN Document Server

    Lee, M H; Kim, S T; Chung, S H; Moon, D C

    1999-01-01

    In this study, we observed optically pumped stimulated emission at room temperature in quasi-bulk GaN prepared from thick-film GaN grown on a sapphire substrate by using hydride vapor-phase epitaxy and subsequent mechanical removal of the sapphire substrate. The stimulated emission from the surface and 1-mm-wide-cleaved cavity of the GaN was red-shifted compared to the spontaneous emission by increasing the optical pumping-power density, and the full width at half maximum (FWHM) of the peak decreased. The stimulated emission was demonstrated to have a highly TE-mode polarized nature, and the super-linear dependence of the integrated emission intensity on the excitation power indicated a threshold pump-power density of I sub t sub h = 2 MW/cm sup 2 for one set of stimulated emissions.

  11. Highly resistive C-doped hydride vapor phase epitaxy-GaN grown on ammonothermally crystallized GaN seeds

    Science.gov (United States)

    Iwinska, Malgorzata; Piotrzkowski, Ryszard; Litwin-Staszewska, Elzbieta; Sochacki, Tomasz; Amilusik, Mikolaj; Fijalkowski, Michal; Lucznik, Boleslaw; Bockowski, Michal

    2017-01-01

    GaN crystals were grown by hydride vapor phase epitaxy (HVPE) and doped with C. The seeds were high-structural-quality ammonothermally crystallized GaN. The grown crystals were highly resistive at 296 K and of high structural quality. High-temperature Hall effect measurements revealed p-type conductivity and a deep acceptor level in the material with an activation energy of 1 eV. This is in good agreement with density functional theory calculations based on hybrid functionals as presented by the Van de Walle group. They obtained an ionization energy of 0.9 eV when C was substituted for N in GaN and acted as a deep acceptor.

  12. Preparation of Freestanding GaN Wafers by Hydride Vapor Phase Epitaxy with Void-Assisted Separation

    Science.gov (United States)

    Oshima, Yuichi; Eri, Takeshi; Shibata, Masatomo; Sunakawa, Haruo; Kobayashi, Kenji; Ichihashi, Toshinari; Usui, Akira

    2003-01-01

    We have developed a novel technique for preparing large-scale freestanding GaN wafers. Hydride vapor phase epitaxy (HVPE) growth of thick GaN layer was performed on a GaN template with a thin TiN film on the top. After the cooling process of the HVPE growth, the thick GaN layer was easily separated from the template by the assistance of many voids generated around the TiN film. As a result, a freestanding GaN wafer was obtained. The wafer obtained had a diameter of 45 mm, and a mirror-like surface. The-full-width-at-half-maximum (FWHM) of (0002) and (10\\bar{1}0) peaks in the X-ray rocking curve profile were 60 and 92 arcsec, respectively. The dislocation density was evaluated at 5× 106 cm-3 by etch pit density measurement.

  13. Method of producing a chemical hydride

    Science.gov (United States)

    Klingler, Kerry M.; Zollinger, William T.; Wilding, Bruce M.; Bingham, Dennis N.; Wendt, Kraig M.

    2007-11-13

    A method of producing a chemical hydride is described and which includes selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of a hydrocarbon; and reacting the composition with the source of the hydrocarbon to generate a chemical hydride.

  14. Complex and liquid hydrides for energy storage

    Energy Technology Data Exchange (ETDEWEB)

    Callini, Elsa; Atakli, Zuleyha Özlem Kocabas; Hauback, Bjørn C.; Orimo, Shin-ichi; Jensen, Craig; Dornheim, Martin; Grant, David; Cho, Young Whan; Chen, Ping; Hjörvarsson, Bjørgvin; de Jongh, Petra; Weidenthaler, Claudia; Baricco, Marcello; Paskevicius, Mark; Jensen, Torben R.; Bowden, Mark E.; Autrey, Thomas S.; Züttel, Andreas

    2016-03-10

    The research on complex hydrides for hydrogen storage was imitated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized and the knowledge on the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant part of the research groups active in the field of complex hydrides are collaborators in the IEA task 32. This paper reports about the important issues in the field of the complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides and their thermodynamic properties, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and excellent summary of the recent achievements.

  15. Metal Hydride Compression

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Bowman, Robert [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Smith, Barton [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Anovitz, Lawrence [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jensen, Craig [Hawaii Hydrogen Carriers LLC, Honolulu, HI (United States)

    2017-07-01

    Conventional hydrogen compressors often contribute over half of the cost of hydrogen stations, have poor reliability, and have insufficient flow rates for a mature FCEV market. Fatigue associated with their moving parts including cracking of diaphragms and failure of seal leads to failure in conventional compressors, which is exacerbated by the repeated starts and stops expected at fueling stations. Furthermore, the conventional lubrication of these compressors with oil is generally unacceptable at fueling stations due to potential fuel contamination. Metal hydride (MH) technology offers a very good alternative to both conventional (mechanical) and newly developed (electrochemical, ionic liquid pistons) methods of hydrogen compression. Advantages of MH compression include simplicity in design and operation, absence of moving parts, compactness, safety and reliability, and the possibility to utilize waste industrial heat to power the compressor. Beyond conventional H2 supplies of pipelines or tanker trucks, another attractive scenario is the on-site generating, pressuring and delivering pure H2 at pressure (≥ 875 bar) for refueling vehicles at electrolysis, wind, or solar generating production facilities in distributed locations that are too remote or widely distributed for cost effective bulk transport. MH hydrogen compression utilizes a reversible heat-driven interaction of a hydride-forming metal alloy with hydrogen gas to form the MH phase and is a promising process for hydrogen energy applications [1,2]. To deliver hydrogen continuously, each stage of the compressor must consist of multiple MH beds with synchronized hydrogenation & dehydrogenation cycles. Multistage pressurization allows achievement of greater compression ratios using reduced temperature swings compared to single stage compressors. The objectives of this project are to investigate and demonstrate on a laboratory scale a two-stage MH hydrogen (H2) gas compressor with a

  16. Formation and physical properties of uranium hydride under conditions relevant to metallic fuel and nuclear waste storage

    Science.gov (United States)

    Orr, Robin; Godfrey, Hugh; Broan, Chris; Goddard, Dave; Woodhouse, Guy; Durham, Peter; Diggle, Andrew; Bradshaw, John

    2016-08-01

    The formation of uranium hydride is recognised as a hazard during the storage of uranium metal owing to its potentially pyrophoric properties. This study has assessed the influence of water vapour on the potential for uranium hydride to form at low temperatures and shows that it increases the duration of the induction period but does not necessarily prevent uranium hydride formation and also does not significantly change the reaction rate with hydrogen. It is further shown that the α-UH3 fraction in the uranium hydride gradually increases at decreasing temperatures and is likely to be the dominant phase formed under typical storage conditions. Particle morphology and specific surface area of uranium hydride prepared between 30 °C and 200 °C have also been characterised but show only modest variation compared with the phase composition.

  17. Prediction of the zeta potentials and ionic descriptors of a silica hydride stationary phase with mobile phases of different pH and ionic strength.

    Science.gov (United States)

    Kulsing, Chadin; Yang, Yuanzhong; Matyska, Maria T; Pesek, Joseph J; Boysen, Reinhard I; Hearn, Milton T W

    2015-02-15

    In this study, the zeta potentials of a silica hydride stationary phase (Diamond Hydride™) in the presence of different water-acetonitrile mixtures (from 0-80% (v/v) acetonitrile) of different ionic strengths (from 0-40mM) and pH values (from pH 3.0-7.0) have been investigated. Debye-Hückel theory was applied to explain the effect of changes in the pH and ionic strength of these aqueous media on the negative zeta potential of this stationary phase. The experimental zeta potentials of the Diamond Hydride™ particles as a function of acetonitrile content up to 50% (v/v) correlated (R(2)=0.998) with the predicted zeta potential values based on this established theory, when the values of the dissociation constant of all related species, as well as viscosity, dielectric constant and refractive index of the aqueous medium were taken into consideration. Further, the retention behavior of basic, acidic and neutral analytes was investigated under mobile phase conditions of higher pH and lower ionic strength. Under these conditions, the Diamond Hydride™ stationary phase surface became more negative, as assessed from the increasingly more negative zeta potentials, resulting in the ion exchange characteristics becoming more dominant and the basic analytes showing increasing retention. Ionic descriptors were derived from these chromatographic experiments based on the assumption that linear solvation energy relationships prevail. The results were compared with predicted ionic descriptors based on the different calculated zeta potential values resulting in an overall correlation of R(2)=0.888. These studies provide fundamental insights into the impact on the separation performance of changes in the zeta potential of the Diamond Hydride™ surface with the results relevant to other silica hydride and, potentially, to other types of stationary phase materials.

  18. Determination of trace selenium in high purity tellurium by hydride generation atomic fluorescence spectrometry after solid phase extraction of a diaminobenzidine-selenium chelate

    Science.gov (United States)

    Tong, Wang; Ying, Zeng; Jinyong, Xu

    2016-09-01

    Macroporous adsorption resin was used as the sorbent for solid phase extraction and determination of the trace Se content in high purity tellurium prior to hydride generation atomic fluorescence spectrometry analysis. Selenium was converted into an organic Se chelate using 3,3‧-diaminobenzidine and was separated from the tellurium matrix by solid phase extraction. The resin was packed as a column for solid phase extraction. Under optimum conditions, trace Se can be quantitatively extracted and the tellurium matrix can be removed. The Se in the eluate was determined by hydride generation atomic fluorescence spectrometry. The limit of detection (3σ) of this method was 0.22 ng g- 1 and the relative standard deviation (RSD, n = 5) ranged from 2.0 to 2.5% for the three investigated tellurium samples. The proposed method was successfully applied for the determination of the trace Se content in high purity tellurium samples.

  19. Influence of the V/III ratio in the gas phase on thin epitaxial AlN layers grown on (0001) sapphire by high temperature hydride vapor phase epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Claudel, A., E-mail: arnaud.claudel@grenoble-inp.org [ACERDE, 354 Voie Magellan — Alpespace, 73800 Ste Hélène du Lac (France); Fellmann, V. [ACERDE, 354 Voie Magellan — Alpespace, 73800 Ste Hélène du Lac (France); Science et Ingénierie des Matériaux et des Procédés, Grenoble INP-CNRS-UJF, BP 75, 38402 Saint Martin d' Hères (France); Gélard, I. [ACERDE, 354 Voie Magellan — Alpespace, 73800 Ste Hélène du Lac (France); Coudurier, N. [ACERDE, 354 Voie Magellan — Alpespace, 73800 Ste Hélène du Lac (France); Science et Ingénierie des Matériaux et des Procédés, Grenoble INP-CNRS-UJF, BP 75, 38402 Saint Martin d' Hères (France); Sauvage, D. [ACERDE, 354 Voie Magellan — Alpespace, 73800 Ste Hélène du Lac (France); Balaji, M. [ACERDE, 354 Voie Magellan — Alpespace, 73800 Ste Hélène du Lac (France); Science et Ingénierie des Matériaux et des Procédés, Grenoble INP-CNRS-UJF, BP 75, 38402 Saint Martin d' Hères (France); Crystal Growth Center, Anna University, Chennai 600025 (India); and others

    2014-12-31

    Thin (0001) epitaxial aluminum nitride (AlN) layers were grown on c-plane sapphire using high temperature hydride vapor phase epitaxy. The experimental set-up consists of a vertical cold-wall quartz reactor working at low pressure in which the reactions take place on a susceptor heated by induction. The reactants used are ammonia and aluminum chlorides in situ formed via hydrogen chloride reaction with high purity aluminum pellets. As-grown AlN layers have been characterized by scanning electron microscopy, atomic force microscopy, X-ray diffraction, transmission electron microscopy, photoluminescence and Raman spectroscopies. The influence of the V/III ratio in the gas phase, from 1.5 to 15, on growth rate, surface morphology, roughness and crystalline quality is investigated in order to increase the quality of thin epitaxial AlN layers grown at high temperature. Typical growth rates of around 0.45 μm/h were obtained for such thin epitaxial AlN layers. The growth rate was unaffected by the V/III ratio. An optimum for roughness, crystalline quality and optical properties seems to exist at V/III = 7.5. As a matter of fact, for a V/III ratio of 7.5, best root mean square roughness and crystalline quality — measured on 0002 symmetric reflection — as low as 6.9 nm and 898 arcsec were obtained, respectively. - Highlights: • Growth of thin epitaxial AlN layers by high temperature hydride vapor phase epitaxy • Influence of V/III ratio on growth rate, morphology and crystalline quality • The effect of surface morphology on strain state and crystal quality is established.

  20. Characteristics and Applications of Metal Hydrides

    Science.gov (United States)

    Egan, G. J.; Lynch, F. E.

    1987-01-01

    Report discusses engineering principles of uses of metal hydrides in spacecraft. Metal hydrides absorb, store, pump, compress, and expand hydrogen gas. Additionally, they release or absorb sizeable amounts of heat as they form and decompose - property adapted for thermal-energy management or for propulsion. Describes efforts to: Identify heat sources and sinks suitable for driving metal hydride thermal cycles in spacecraft; develop concepts for hydride subsystems employing available heating and cooling methods; and produce data base on estimated sizes, masses, and performances of hydride devices for spacecraft.

  1. Upright and Inverted Single-Junction GaAs Solar Cells Grown by Hydride Vapor Phase Epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Simon, John; Schulte, Kevin L.; Jain, Nikhil; Johnston, Steve; Young, Michelle; Young, Matthew R.; Young, David L.; Ptak, Aaron J.

    2017-01-01

    Hydride vapor phase epitaxy (HVPE) is a low-cost alternative to conventional metal-organic vapor phase epitaxy (MOVPE) growth of III-V solar cells. In this work, we show continued improvement of the performance of HVPE-grown single-junction GaAs solar cells. We show over an order of magnitude improvement in the interface recombination velocity between GaAs and GaInP layers through the elimination of growth interrupts, leading to increased short-circuit current density and open-circuit voltage compared with cells with interrupts. One-sun conversion efficiencies as high as 20.6% were achieved with this improved growth process. Solar cells grown in an inverted configuration that were removed from the substrate showed nearly identical performance to on-wafer cells, demonstrating the viability of HVPE to be used together with conventional wafer reuse techniques for further cost reduction. These devices utilized multiple heterointerfaces, showing the potential of HVPE for the growth of complex and high-quality III-V devices.

  2. Investigation of cracks in GaN films grown by combined hydride and metal organic vapor-phase epitaxial method

    Directory of Open Access Journals (Sweden)

    Yang Tieying

    2011-01-01

    Full Text Available Abstract Cracks appeared in GaN epitaxial layers which were grown by a novel method combining metal organic vapor-phase epitaxy (MOCVD and hydride vapor-phase epitaxy (HVPE in one chamber. The origin of cracks in a 22-μm thick GaN film was fully investigated by high-resolution X-ray diffraction (XRD, micro-Raman spectra, and scanning electron microscopy (SEM. Many cracks under the surface were first observed by SEM after etching for 10 min. By investigating the cross section of the sample with high-resolution micro-Raman spectra, the distribution of the stress along the depth was determined. From the interface of the film/substrate to the top surface of the film, several turnings were found. A large compressive stress existed at the interface. The stress went down as the detecting area was moved up from the interface to the overlayer, and it was maintained at a large value for a long depth area. Then it went down again, and it finally increased near the top surface. The cross-section of the film was observed after cleaving and etching for 2 min. It was found that the crystal quality of the healed part was nearly the same as the uncracked region. This indicated that cracking occurred in the growth, when the tensile stress accumulated and reached the critical value. Moreover, the cracks would heal because of high lateral growth rate.

  3. Density functional theory study on LaNi4.5Al0.5 hydride phase: electronic properties and sites occupation

    Institute of Scientific and Technical Information of China (English)

    Chen Dong; Yu Ben-Hai; Wang Chun-Lei; Gao Tao

    2007-01-01

    In this paper the crystal structure, electronic structure and hydrogen site occupation of LaNi4.5Al0.5Hy hydride phase (y=5.0, 6.0) have been investigated by using full-potential linearized augmented plane wave method. The hydrogen atoms were found to prefer the 6m, 12o and 12n sites, while no 4h sites were occupied. A narrowed Ni-d band is found due to the lattice expansion, the total density of states at EF increases with y, which indicates that the compounds become less stable. The interaction between Al and Ni, H plays a dominant role in the stability of LaNi4.sAl0.5Hy hydride phase. The smaller the shift of EF towards the higher energy region, the more stable the compounds will be. The obtained results are compared with experimental data and discussed in the light of previous works.

  4. Preparation of Porous GaN Buffer and Its Influence on the Residual Stress of GaN Epilayers Grown by Hydride Vapor Phase Epitaxy

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The preparation of porous structure on the molecular beam epitaxy (MBE)-grown mixed-polarity GaN epilayers was reported by using the wet chemical etching method. The effect of this porous structure on the residual stress of subsequent-growth GaN epilayers was studied by Raman and photoluminescence (PL) spectrum.Substantial decrease in the biaxial stresse can be achieved by employing the porous buffers in the hydride vapour phase epitaxy (HVPE) epilayer growth.

  5. Direct hydride derivatization of methyl- and ethylmercury chlorides in aqueous solution with KBH4

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A convenient hydride derivatization procedure of methyl-and ethylmercury chlorides to volatile hydrides was reported. In sealed vials methylmercury and ethylmercury compounds in acidic aqueous solutions were converted into their volatile forms by the reaction with potassium tetrahydroborate(KBH4) and elvolved to the headspace of the vials. The gaseous analytes in the headspace were extracted and concentrated by solid phase microextraction(SPME) and injected into gas chromatography (GC) for separation and identified by mass selective detector(MS).

  6. Hydride development for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.; Yang, N.Y.C. [Sandia National Lab., Livermore, CA (United States); Sandrock, G. [SunaTech, Inc., Ringwood, NJ (United States)

    1996-10-01

    The purpose of this project is to develop and demonstrate improved hydride materials for hydrogen storage. The work currently is organized into four tasks: hydride development, bed fabrication, materials support for engineering systems, and IEA Annex 12 activities. At the present time, hydride development is focused on Mg alloys. These materials generally have higher weight densities for storing hydrogen than rare earth or transition metal alloys, but suffer from high operating temperatures, slow kinetic behavior and material stability. The authors approach is to study bulk alloy additions which increase equilibrium overpressure, in combination with stable surface alloy modification and particle size control to improve kinetic properties. This work attempts to build on the considerable previous research in this area, but examines specific alloy systems in greater detail, with attention to known phase properties and structures. The authors have found that specific phases can be produced which have significantly improved hydride properties compared to previous studies.

  7. ZrNi5-based hydrogenated phases formed under high hydrogen pressure conditions

    Energy Technology Data Exchange (ETDEWEB)

    Filipek, Stanislaw M., E-mail: sfilipek@ichf.edu.pl [Institute of Physical Chemistry PAS, ul. Kasprzaka 44, 01-224 Warsaw (Poland); Paul-Boncour, Valerie [Laboratoire de Chimie Metallurgique des Terres Rares, CNRS, 2-8 rue H. Dunant, 94320 Thiais (France); Liu, Ru-Shi [Department of Chemistry, National Taiwan University, Taipei, Taiwan (China)

    2011-07-15

    Formation of novel hydrides from ZrNi{sub 5} alloy has been confirmed experimentally. After exposure of ZrNi{sub 5} at 0.9 GPa(H{sub 2}) and 100 {sup o}C for 6 days the alloy transformed into two hydrogenated phases {alpha} and {beta} containing initially more than 0.38 and 0.86 hydrogen atoms per formula unit respectively. At ambient conditions both hydrides were extremely unstable. Major part of hydrogen desorbed within few minutes. During this desorption the lattice parameters of both hydrides were continuously reduced what confirms their solid solution character.

  8. Synthesis of nanocrystalline MgH{sub 2} powder by gas-phase condensation and in situ hydridation: TEM, XPS and XRD study

    Energy Technology Data Exchange (ETDEWEB)

    Friedrichs, O. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain)]. E-mail: veroil@icmse.csic.es; Kolodziejczyk, L. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain); Sanchez-Lopez, J.C. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain); Lopez-Cartes, C. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain); Fernandez, A. [Instituto de Ciencia de Materiales de Sevilla, CSIC-Universidad de Sevilla, Isla de la Cartuja, Avda. Americo Vespucio 49, 41092 Sevilla (Spain)

    2007-05-31

    In this work, a two-step method for the preparation of nanocrystalline MgH{sub 2} is presented, where the first step consists of synthesis of nanocrystalline Mg powder by the gas-phase condensation method (GPC) and the second of in situ hydridation leading to the formation of MgH{sub 2} nanoparticles. By transmission electron microscopy (TEM) and electron diffraction (ED), crystalline Mg nanoparticles from GPC were found to have mean size within the range of 30-50 nm, while in the case of MgH{sub 2} nanoparticles these values increase approximately 2-3 times mainly due to particles growth during the hydridation step. The X-ray diffraction (XRD) analysis shows the high conversion into the MgH{sub 2} phase after hydridation. By X-ray photoelectron spectroscopy (XPS) metallic magnesium was detected below a magnesium oxide layer of 3-4 nm for the Mg sample prepared by GPC, which shows the efficiency of a novel sample transfer system without air exposure between N{sub 2}-glove-box, preparation chamber and experimental apparatus.

  9. Spray Forming Aluminum - Final Report (Phase II)

    Energy Technology Data Exchange (ETDEWEB)

    D. D. Leon

    1999-07-08

    The U.S. Department of Energy - Office of Industrial Technology (DOE) has an objective to increase energy efficient and enhance competitiveness of American metals industries. To support this objective, ALCOA Inc. entered into a cooperative program to develop spray forming technology for aluminum. This Phase II of the DOE Spray Forming Program would translate bench scale spray forming technology into a cost effective world class process for commercialization. Developments under DOE Cooperative Agreement No. DE-FC07-94ID13238 occurred during two time periods due to budgetary constraints; April 1994 through September 1996 and October 1997 and December 1998. During these periods, ALCOA Inc developed a linear spray forming nozzle and specific support processes capable of scale-up for commercial production of aluminum sheet alloy products. Emphasis was given to alloys 3003 and 6111, both being commercially significant alloys used in the automotive industry. The report reviews research performed in the following areas: Nozzel Development, Fabrication, Deposition, Metal Characterization, Computer Simulation and Economics. With the formation of a Holding Company, all intellectual property developed in Phases I and II of the Project have been documented under separate cover for licensing to domestic producers.

  10. Preliminary development of flaw evaluation procedures for delayed hydride cracking initiation under hydride non-ratcheting conditions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, S.; Cui, J.; Kawa, D.; Shek, G.K.; Scarth, D.A. [Kinectrics Inc., Toronto, Ontario (Canada)

    2006-07-01

    The flaw evaluation procedure for Delayed Hydride Cracking (DHC) initiation currently provided in the CSA Standard N285.8 was developed for hydride ratcheting conditions, in which flaw-tip hydrides do not completely dissolve at peak temperature. Test results have shown that hydrided regions formed under non-ratcheting conditions, in which flaw-tip hydrides completely dissolve at peak temperature, have significantly higher resistance to cracking than those formed under ratcheting conditions. This paper presents some preliminary work on the development of a procedure for the evaluation of DHC initiation for flaws under hydride non-ratcheting conditions. (author)

  11. First-principles studies of phase stability and the structural and dynamical properties of metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Chou, M.Y.

    1992-04-01

    This report discusses the following topics: calculation of the Structural Properties of Yttrium; dynamical and pairing properties of {alpha}-YH{chi}; electronic and structural properties of YH{sub 2} and YH{sub 3}; phase diagram of hydrogen on Ru(000); peierls distortion in hexagonal YH{sub 3}; and study of hydrogen in niobium and palladium.

  12. Smectic Phase Formed by DNA Dimers

    Science.gov (United States)

    Salamonczyk, Miroslaw; Gleeson, James; Jakli, Antal; Sprunt, Samuel; Dhont, Jan; Stiakakis, Emmanuel

    The rapidly expanding bio market is driving the development and characterization of new multifunctional materials. In particular, nucleic acids are under intense study for gene therapy, drug delivery and other bio-safe applications [1,2,3]. DNA is well-known to form a cholesteric nematic liquid crystal in its native form; however, much recent research has focused on self-assembly and mesomorphic behavior in concentrated solutions of short DNA helices [4]. Our work focuses on DNA dimers, consisting of 48 base-pair double-stranded helices connected by a 5 to 20 base flexible single strand, and suspended in a natural buffer. Depending on temperature, concentration and length of the flexible spacer, polarizing optical microscopy and small angle x-ray scattering reveal cholesteric nematic and, remarkably, smectic liquid crystalline phases. A model for smectic phase formation in this system will be presented. 1] J.-L. Lim et al., Int. J. of. Pharm. 490 (2015) 2652] D.-H. Kim et al., Nature Biotech. 23 (2005) 2223] K. Liu et al., Chem. Eur. J. 21 (2015) 48984] M. Nakata et al., Science 318 (2007) 1276 NSF DMR 1307674.

  13. Research on Metal Hydride Compressor System

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Ti-Zr series Laves phase hydrogen storage alloys with good hydrogen storage properties, such as large hydrogen capacity, rapid hydriding and dehydriding rate, high compression ratio, gentle plateau, small hysteresis, easily being activated and long cyclic stability etc. for metal hydride compressor have been investigated. In addition, a hydride compressor with special characteristics, namely, advanced filling method, good heat transfer effect and reasonable structural design etc. has also been constructed. A hydride compressor cryogenic system has been assembled coupling the compressor with a J-T micro-throttling refrigeration device and its cooling capacity can reach 0.4 W at 25 K.

  14. LiCa₃As₂H and Ca₁₄As₆X₇ (X = C, H, N): two new arsenide hydride phases grown from Ca/Li metal flux.

    Science.gov (United States)

    Blankenship, Trevor V; Wang, Xiaoping; Hoffmann, Christina; Latturner, Susan E

    2014-10-06

    The reaction of arsenic with sources of light elements in a Ca/Li melt leads to the formation of two new arsenide hydride phases. The predominant phase Ca14As6X7 (X = C(4-), N(3-), H(-)) exhibits a new tetragonal structure type in the space group P4/mbm (a = 15.749(1) Å, c = 9.1062(9) Å, Z = 4, R1 = 0.0150). The minor phase LiCa3As2H also has a new structure type in the orthorhombic space group Pnma (a = 11.4064(7) Å, b = 4.2702(3) Å, c = 11.8762(8)Å, Z = 4, R1 = 0.0135). Both phases feature hydride and arsenide anions separated by calcium cations. The red color of these compounds indicates they should be charge-balanced. DOS calculations on LiCa3As2H confirm a band gap of 1.4 eV; UV-vis spectroscopy on Ca14As6X7 shows a band gap of 1.6 eV. Single-crystal neutron diffraction studies were necessary to determine the mixed occupancy of carbon, nitrogen, and hydrogen anions on the six light-element sites in Ca14As6X7; these data indicated an overall stoichiometry of Ca14As6C(0.445)N(1.135)H(4.915).

  15. Hyphenating multisyringe flow injection lab-on-valve analysis with atomic fluorescence spectrometry for on-line bead-injection preconcentration and determination of trace levels of hydride-forming elements in environmental samples

    DEFF Research Database (Denmark)

    Long, Xiangbao; Miró, Manuel; Hansen, Elo Harald;

    2006-01-01

    of the functional moieties, so that maximum benefit can be taken from the application of the bead renewal strategy. The proposed procedure is characterized by a high tolerance to metal species and interfering hydride forming elements. In fact, ratios of Se(IV) to As ≤ 5000 and Sb(V) to As ≤ 500 are tolerated...... feasible by interfacing the micromachined LOV-module with AFS by a multisyringe flowing stream network for on-line post column derivatization of the eluate aimed at the generation of hydride species. The potential of this new hyphenated technique for environmental assays was ascertained via...

  16. Hyphenating multisyringe flow injection lab-on-valve analysis with atomic fluorescence spectrometry for on-line bead-injection preconcentration and determination of trace levels of hydride-forming elements in environmental samples

    DEFF Research Database (Denmark)

    Long, Xiangbao; Miró, Manuel; Hansen, Elo Harald

    2006-01-01

    of the functional moieties, so that maximum benefit can be taken from the application of the bead renewal strategy. The proposed procedure is characterized by a high tolerance to metal species and interfering hydride forming elements. In fact, ratios of Se(IV) to As ≤ 5000 and Sb(V) to As ≤ 500 are tolerated...

  17. First Evidence of Rh Nano-Hydride Formation at Low Pressure.

    Science.gov (United States)

    Zlotea, Claudia; Oumellal, Yassine; Msakni, Mariem; Bourgon, Julie; Bastide, Stéphane; Cachet-Vivier, Christine; Latroche, Michel

    2015-07-08

    Rh-based nanoparticles supported on a porous carbon host were prepared with tunable average sizes ranging from 1.3 to 3.0 nm. Depending on the vacuum or hydrogen environment during thermal treatment, either Rh metal or hydride is formed at nanoscale, respectively. In contrast to bulk Rh that can form a hydride phase under 4 GPa pressure, the metallic Rh nanoparticles (∼2.3 nm) absorb hydrogen and form a hydride phase at pressure below 0.1 MPa, as evidenced by the presence of a plateau pressure in the pressure-composition isotherm curves at room temperature. Larger metal nanoparticles (∼3.0 nm) form only a solid solution with hydrogen under similar conditions. This suggests a nanoscale effect that drastically changes the Rh-H thermodynamics. The nanosized Rh hydride phase is stable at room temperature and only desorbs hydrogen above 175 °C. Within the present hydride particle size range (1.3-2.3 nm), the hydrogen desorption is size-dependent, as proven by different thermal analysis techniques.

  18. Boron Hydrides

    Science.gov (United States)

    1946-07-01

    of direct interest could be b.P.4d. ’Thus the discovory of a now proj.ect, since silano is probably too readily infla-zmablo for practical usc’ this...devoted, ho specc4fie compounds vhitih a’-ould be tocdte at prescnt arc: nron tiy * silano , %;2.SiFi3 , diothyl sila~no, (C2 115 )2 Si112, mono r.-rop; ! (n...Bcrohydrido or Li h.... I .A-4A- The prepuation of Silano med of Stannane by the interaction or lithium aluzirun hydride v-ithl silicon tetrtchiorido and

  19. Thermodynamic Hydricity of Transition Metal Hydrides.

    Science.gov (United States)

    Wiedner, Eric S; Chambers, Matthew B; Pitman, Catherine L; Bullock, R Morris; Miller, Alexander J M; Appel, Aaron M

    2016-08-10

    Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bond-breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H(-)). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.

  20. Fracture mechanism of TiAl intermetallics caused by hydride and atomic hydrogen

    Institute of Scientific and Technical Information of China (English)

    高克玮; 王燕斌; 林志; 乔利杰; 褚武扬

    1999-01-01

    Hydrogen embrittlement (HE) of TiAl intermetallics was studied at room temperature. The results showed that there were two forms of HE in TiAl intermetallics, i.e. hydride HE and atomic HE. Most of hydrogen in TiAl intermetallics was transformed into hydrides at room temperature. The hydride exists as (TiAl)Hx for a low hydrogen concentration while it exists in several forms for a higher hydrogen concentration. Stress intensity factor KIC decreased with increase in hydride concentration. KIC decreased further when TiAl intermetallics were charged cathodically with hydrogen in 1 mol/L H2SO4 solution. Stress intensity factor during hydrogen charging KIH was about 50% KIC. 20% of the decrease was caused by hydrides while 30% was caused by atomic hydrogen. Mechanism of HE caused hydrides was the same as any other second phase in nature. Delayed fracture caused by atomic hydrogen resulted from hydrogen induced local plastic deformation.

  1. Physics of hydride fueled PWR

    Science.gov (United States)

    Ganda, Francesco

    The first part of the work presents the neutronic results of a detailed and comprehensive study of the feasibility of using hydride fuel in pressurized water reactors (PWR). The primary hydride fuel examined is U-ZrH1.6 having 45w/o uranium: two acceptable design approaches were identified: (1) use of erbium as a burnable poison; (2) replacement of a fraction of the ZrH1.6 by thorium hydride along with addition of some IFBA. The replacement of 25 v/o of ZrH 1.6 by ThH2 along with use of IFBA was identified as the preferred design approach as it gives a slight cycle length gain whereas use of erbium burnable poison results in a cycle length penalty. The feasibility of a single recycling plutonium in PWR in the form of U-PuH2-ZrH1.6 has also been assessed. This fuel was found superior to MOX in terms of the TRU fractional transmutation---53% for U-PuH2-ZrH1.6 versus 29% for MOX---and proliferation resistance. A thorough investigation of physics characteristics of hydride fuels has been performed to understand the reasons of the trends in the reactivity coefficients. The second part of this work assessed the feasibility of multi-recycling plutonium in PWR using hydride fuel. It was found that the fertile-free hydride fuel PuH2-ZrH1.6, enables multi-recycling of Pu in PWR an unlimited number of times. This unique feature of hydride fuels is due to the incorporation of a significant fraction of the hydrogen moderator in the fuel, thereby mitigating the effect of spectrum hardening due to coolant voiding accidents. An equivalent oxide fuel PuO2-ZrO2 was investigated as well and found to enable up to 10 recycles. The feasibility of recycling Pu and all the TRU using hydride fuels were investigated as well. It was found that hydride fuels allow recycling of Pu+Np at least 6 times. If it was desired to recycle all the TRU in PWR using hydrides, the number of possible recycles is limited to 3; the limit is imposed by positive large void reactivity feedback.

  2. Hydride-induced embrittlement of Zircaloy-4 cladding under plane-strain tension

    Science.gov (United States)

    Daum, Robert S.

    The mechanical response of high-burnup Zircaloy-4 fuel cladding subjected to a postulated reactivity initiated accident (referred to as a rod ejection accident (REA) in a pressurized water reactor) can be affected by hydrogen embrittlement. This study addresses the hydrogen embrittlement of non-irradiated, stress-relieved Zircaloy-4 cladding under conditions (state of stress and temperature) relevant to those of a reactivity initiated accident. Specifically, the study has investigated the effects of a concentrated density of hydride particles (in the form of a rim at the outer surface of the cladding tube introduced by gas-charging) on the cladding ductility when tested under a near-plane-strain tension at 25, 300, and 375°C. The influence of the hydride-rim thickness and local hydrogen contents on cladding ductility is studied as a function of temperature and correlated with the hydride microstructure. Using synchrotron x-ray diffraction, this study has found that the delta-hydride phase (i.e., ZrHx, where x ≈ 1.66) is the predominant hydride phase to precipitate in stress-relieved Zircaloy-4 cladding for hydrogen contents up to 1250 wt ppm. At hydrogen contents above 2700 wt ppm, although delta-hydride is still the majority phase, both gamma- and epsilon-hydride phases are also observed. The volume fraction of hydrides was estimated as a function of hydrogen content, using the diffracted x-ray intensities. These estimated values agree well with calculated values assuming hydride precipitates are delta-hydride. Under near-plane-strain hoop tension, the ductility and fracture of the cladding is highly dependent on both the hydride-rim thickness and the testing temperature. At room temperature, due to a high density of hydride particles within the rim, a Mode I crack is injected shortly after yielding. This limits cladding ductility, such that it decreases with increasing thickness of the hydride rim. Cladding containing hydride rims with a thickness of ≥100

  3. Determination of As(III) and total inorganic As in water samples using an on-line solid phase extraction and flow injection hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Sigrist, Mirna, E-mail: msigrist@fiq.unl.edu.ar [Laboratorio Central, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2654-Piso 6, (3000) Santa Fe (Argentina); Albertengo, Antonela; Beldomenico, Horacio [Laboratorio Central, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2654-Piso 6, (3000) Santa Fe (Argentina); Tudino, Mabel [Laboratorio de Analisis de Trazas, Departamento de Quimica Inorganica, Analitica y Quimica Fisica/INQUIMAE, Facultad de Ciencias Exactas y Naturales, Pabellon II, Ciudad Universitaria (1428), Buenos Aires (Argentina)

    2011-04-15

    A simple and robust on-line sequential injection system based on solid phase extraction (SPE) coupled to a flow injection hydride generation atomic absorption spectrometer (FI-HGAAS) with a heated quartz tube atomizer (QTA) was developed and optimized for the determination of As(III) in groundwater without any kind of sample pretreatment. The method was based on the selective retention of inorganic As(V) that was carried out by passing the filtered original sample through a cartridge containing a chloride-form strong anion exchanger. Thus the most toxic form, inorganic As(III), was determined fast and directly by AsH{sub 3} generation using 3.5 mol L{sup -1} HCl as carrier solution and 0.35% (m/v) NaBH{sub 4} in 0.025% NaOH as the reductant. Since the uptake of As(V) should be interfered by several anions of natural occurrence in waters, the effect of Cl{sup -}, SO{sub 4}{sup 2-}, NO{sub 3}{sup -}, HPO{sub 4}{sup 2-}, HCO{sub 3}{sup -} on retention was evaluated and discussed. The total soluble inorganic arsenic concentration was determined on aliquots of filtered samples acidified with concentrated HCl and pre-reduced with 5% KI-5% C{sub 6}H{sub 8}O{sub 6} solution. The concentration of As(V) was calculated by difference between the total soluble inorganic arsenic and As(III) concentrations. Detection limits (LODs) of 0.5 {mu}g L{sup -1} and 0.6 {mu}g L{sup -1} for As(III) and inorganic total As, respectively, were obtained for a 500 {mu}L sample volume. The obtained limits of detection allowed testing the water quality according to the national and international regulations. The analytical recovery for water samples spiked with As(III) ranged between 98% and 106%. The sampling throughput for As(III) determination was 60 samples h{sup -1}. The device for groundwater sampling was especially designed for the authors. Metallic components were avoided and the contact between the sample and the atmospheric oxygen was carried to a minimum. On-field arsenic species

  4. Real-time measurement of desorption temperature and kinetics of magnesium hydride powder sample based on optical reflection

    Energy Technology Data Exchange (ETDEWEB)

    Poh, Chung-Kiak [Institute for Superconducting and Electronic Materials, University of Wollongong, Innovation Campus, Squires Way, Fairy Meadow, NSW 2519 (Australia); Guo, Zaiping; Liu, Hua-Kun [Institute for Superconducting and Electronic Materials, University of Wollongong, Innovation Campus, Squires Way, Fairy Meadow, NSW 2519 (Australia); CSIRO National Hydrogen Materials Alliance, CSIRO Energy Centre, 10 Murray Dwyer Circuit, Steel River Estate, Mayfield West, NSW 2304 (Australia)

    2009-11-15

    We demonstrate the proof-of-principle that interaction between visible light and a magnesium hydride sample in reflective mode can be used to determine the desorption temperature and kinetics of magnesium hydride in powder form. The demonstrated optical technique requires only milligrams of sample and can potentially be used to measure the de/absorption temperature and kinetics of magnesium nanostructures, which are often fabricated via the physical vapor deposition method inside an optically transparent quartz tube. This would help to eliminate the common problem of oxidation associated with removal and transport of the freshly fabricated nanostructures into an inert protective environment. This optical technique could be applied to any hydrogen-storage material in the form of powder which shows a significant difference in its optical absorption between the hydride and the non-hydride phase. (author)

  5. GaAs Solar Cells Grown by Hydride Vapor-Phase Epitaxy and the Development of GaInP Cladding Layers

    Energy Technology Data Exchange (ETDEWEB)

    Simon, John; Schulte, Kevin L.; Young, David L.; Haegel, Nancy M.; Ptak, Aaron J.

    2016-01-01

    The high cost of high-efficiency III-V photovoltaic devices currently limits them to niche markets. Hydride vapor-phase epitaxy (HVPE) growth of III-V materials recently reemerged as a low-cost, high-throughput alternative to conventional metal- organic vapor-phase epitaxy (MOVPE) growth of high-efficiency solar cells. Previously, we demonstrated unpassivated HVPEgrown GaAs p-n junctions with good quantum efficiency and high open-circuit voltage (Voc). In this work, we demonstrate the growth of GaInPby HVPE for use as a high-quality surface passivation layer to GaAs solar cells. Solar cells grown with GaInP window layers show significantly improved quantum efficiency compared with unpassivated cells, increasing the short-circuit current (JSC) of these low-cost devices. These results show the potential of low-cost HVPE for the growth of high-quality III-V devices.

  6. Thick orientation-patterned growth of GaP on wafer-fused GaAs templates by hydride vapor phase epitaxy for frequency conversion

    Science.gov (United States)

    Vangala, Shivashankar; Kimani, Martin; Peterson, Rita; Stites, Ron; Snure, Michael; Tassev, Vladimir

    2016-10-01

    Quasi-phase-matched (QPM) GaP layers up to 300 μm thick have been produced by low-pressure hydride vapor phase epitaxy (LP-HVPE) overgrowth on orientation-patterned GaAs (OPGaAs) templates fabricated using a wafer-fusion bonding technique. The growth on the OPGaAs templates resulted in up to 200 μm thick vertically propagating domains, with a total GaP thickness of 300 μm. The successful thick growth on OPGaAs templates is the first step towards solving the material problems associated with unreliable material quality of commercially available GaP wafers and making the whole process of designing QPM frequency conversion devices molecular beam epitaxy free and more cost-effective.

  7. Comminution by hydriding-dehydriding process of the U-Zr-Nb alloys stabilized at different phases by aging heat treatment

    Energy Technology Data Exchange (ETDEWEB)

    Cantagalli, Natalia Mattar; Pais, Rafael Witter Dias; Braga, Daniel Martins; Santos, Ana Maria Matildes dos; Ferraz, Wilmar Barbosa, E-mail: ferrazw@cdtn.b [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG) Belo Horizonte, MG (Brazil)

    2011-07-01

    Powders of the U-Zr-Nb alloys are raw materials for obtaining plate-type dispersion fuel of high density and medium enrichment for research and test reactors as well as small power reactors. U-2.5Zr-7.5Nb and U-3Zr-9Nb (wt%) alloys, initially homogenized at high temperatures, were transformed at different phases by means aging heat treatments, and then comminuted by hydriding-dehydriding process to powder production. The phases transformations were obtained by the homogenization of the U-2.5Zr-7.5Nb and U-3Zr-9Nb alloys at high temperatures (1000 deg C for 1 and 16 h), followed by aging heat treatment at 600 deg C, in times of 0.5 h, 3.0 h and 24h, and subsequently quenched in water to stabilize the desired phase. The comminution process was performed at 200 deg C for different times ranging from 20 minutes to 4 hours. The powders were then characterized by scanning electron microscopy, X-ray diffraction and determination of particle size distribution by means of laser equipment CILAS. One of the main objectives of this study was to verify the influence of the different phases in the characteristics of the obtained powders. It was found that alloys stabilized in gamma phase produced powders with smaller particles sizes than those with cellular structure of the {alpha} and {gamma} phases. Regardless of retained phases, the produced powders consist of agglomerates with irregular morphology. (author)

  8. Phase evolution of Li{sub 2}ND, LiD and LiND{sub 2} in hydriding/dehydriding of Li{sub 3}N

    Energy Technology Data Exchange (ETDEWEB)

    Chien, W.-M.; Lamb, Joshua [Metallurgical Materials Engineering, MS 388, University of Nevada, Reno, NV 89557 (United States); Chandra, Dhanesh [Metallurgical Materials Engineering, MS 388, University of Nevada, Reno, NV 89557 (United States)], E-mail: dchandra@unr.edu; Huq, Ashfia [Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Richardson, James; Maxey, Evan [Intense Pulsed Neutron Source, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2007-10-31

    Neutron and synchrotron studies have been performed on in situ hydriding of Li{sub 3}N. Commercial Li{sub 3}N is composed of {alpha} phase ({approx}70 wt.%) and {beta} phase ({approx}30 wt.%). We have performed experiments to convert {beta} {yields} {alpha}, and studied in situ deuteration using neutron diffraction experiments. We found concurrent phase evolution of Li{sub 2}ND, LiD, and LiND{sub 2}. Mass percentages of the phases evolved as a function of time and temperature have been quantified using General Structure Analysis System (GSAS) refinement of the neutron diffraction data. The problem of formation of the stable LiD is discussed in light of decreasing of the amount of LiD phase when the temperature is increased from 200 to 320 deg. C during dehydriding, and in addition the concentration of Li{sub 2}ND phase increased at this temperature. Lattice parameters, volume changes, phase evolutions in wt.% as a function of temperature and time are presented.

  9. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today......’s hydride batteries, but a much poorer stability towards repeated charge/discharge cycling. The aim was to see if the cycleability of CaNi5 could be enhanced enough by modifications to make the compound a suitable electrode material. An alloying method based on mechanical alloying in a planetary ball mill...... by annealing at 700°C for 12 hours. The alloys appeared to be nanocrystalline with an average crystallite size around 10 nm before annealing. Special steel containers was developed for the annealing of the metal powders in inert atmosphere. The use of various annealing temperatures was investigated...

  10. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-01-01

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, cold,'' process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility's metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

  11. Advanced Hydride Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T.

    1989-12-31

    Metal hydrides have been used at the Savannah River Tritium Facilities since 1984. However, the most extensive application of metal hydride technology at the Savannah River Site is being planned for the Replacement Tritium Facility, a $140 million facility schedules for completion in 1990 and startup in 1991. In the new facility, metal hydride technology will be used to store, separate, isotopically purify, pump, and compress hydrogen isotopes. In support of the Replacement Tritium Facility, a $3.2 million, ``cold,`` process demonstration facility, the Advanced Hydride Laboratory began operation in November of 1987. The purpose of the Advanced Hydride Laboratory is to demonstrate the Replacement Tritium Facility`s metal hydride technology by integrating the various unit operations into an overall process. This paper will describe the Advanced Hydride Laboratory, its role and its impact on the application of metal hydride technology to tritium handling.

  12. High performance liquid chromatography coupled to atomic fluorescence spectrometry for the speciation of the hydride and chemical vapour-forming elements As, Se, Sb and Hg: A critical review

    Energy Technology Data Exchange (ETDEWEB)

    Chen Yuwei [Department of Chemistry and Biochemistry, Laurentian University, Ramsey Lake Road, Sudbury P3E 2C6 (Canada); Belzile, Nelson, E-mail: nbelzile@laurentian.ca [Department of Chemistry and Biochemistry, Laurentian University, Ramsey Lake Road, Sudbury P3E 2C6 (Canada); Cooperative Freshwater Ecology Unit, Laurentian University, Ramsey Lake Road, Sudbury P3E 2C6 (Canada)

    2010-06-25

    We present the most recent applications of high performance liquid chromatography (HPLC) hyphenated to hydride generation or chemical vapour generation and atomic fluorescence spectrometry (HG/CVG-AFS), for the determination and speciation of the selected hydride-forming elements arsenic (As), selenium (Se) and antimony (Sb) and the chemical vapour-forming metal Hg. The review focuses on sample preparation, post-column treatments and on the applications of this technique to various liquid and solid samples. This review also intends to discuss some limitations associated to HPLC-HG/CVG-AFS due to the necessity on post-column treatments, including the oxidation of organo-element compounds and the pre-reduction to a suitable valence. Nevertheless, the hyphenated technique HPLC-HG/CVG-AFS remains an efficient, sensitive and affordable approach to perform speciation of the four studied elements as shown by the variety of applications presented and discussed in this review.

  13. On-line electrochemically controlled in-tube solid phase microextraction of inorganic selenium followed by hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Asiabi, Hamid [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Yamini, Yadollah, E-mail: yyamini@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Seidi, Shahram [Department of Analytical Chemistry, Faculty of Chemistry, K.N. Toosi University of Technology, Tehran (Iran, Islamic Republic of); Shamsayei, Maryam; Safari, Meysam; Rezaei, Fatemeh [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2016-05-30

    In this work, for the first time, a rapid, simple and sensitive microextraction procedure is demonstrated for the matrix separation, preconcentration and determination of inorganic selenium species in water samples using an electrochemically controlled in-tube solid phase microextraction (EC-in-tube SPME) followed by hydride generation atomic absorption spectrometry (HG-AAS). In this approach, in which EC-in-tube SPME and HG-AAS system were combined, the total analysis time, was decreased and the accuracy, repeatability and sensitivity were increased. In addition, to increases extraction efficiency, a novel nanostructured composite coating consisting of polypyrrole (PPy) doped with ethyleneglycol dimethacrylate (EGDMA) was prepared on the inner surface of a stainless-steel tube by a facile electrodeposition method. To evaluate the offered setup and the new PPy-EGDMA coating, it was used to extract inorganic selenium species in water samples. Extraction of inorganic selenium species was carried out by applying a positive potential through the inner surface of coated in-tube under flow conditions. Under the optimized conditions, selenium was detected in amounts as small as 4.0 parts per trillion. The method showed good linearity in the range of 0.012–200 ng mL{sup −1}, with coefficients of determination better than 0.9996. The intra- and inter-assay precisions (RSD%, n = 5) were in the range of 2.0–2.5% and 2.7–3.2%, respectively. The validated method was successfully applied for the analysis of inorganic selenium species in some water samples and satisfactory results were obtained. - Graphical abstract: An electrochemically controlled in-tube solid phase microextraction followed by hydride generation atomic absorption spectrometry was developed for extraction and determination ultra-trace amounts of Se in aqueous solutions. - Highlights: • A nanostructured composite coating consisting of PPy doped with EGDMA was prepared. • The coating was

  14. Mechanism of light emission and manufacturing process of vertical-type light-emitting diode grown by hydride vapor phase epitaxy

    Science.gov (United States)

    Lee, Gang Seok; Jeon, Hunsoo; Ahn, Hyung Soo; Yang, Min; Yi, Sam Nyung; Yu, Young Moon; Lee, Sang Chil; Honda, Yoshio; Sawaki, Nobuhiko; Kim, Suck-Whan

    2017-01-01

    We developed a vertical-type light-emitting diode (LED) in which the substrate is removed using a hydride vapor phase epitaxy (HVPE) apparatus consisting of a multi-graphite boat filled with a mixed source and a high-temperature (T ≈ 900 °C) RF heating coil outside the source zone. The new chip-growth process with a significant reduction in the number of production steps is completed in only four steps, namely, photolithography, epitaxial layer growth, sorting, and metallization. We analyze the emission mechanism of these lights from measurement results to validate the characteristics of the light emitted from these vertical-type blue LEDs and white LEDs (WLEDs) without substrates, and propose that this mixed-source HVPE method may be a promising production technique for LEDs.

  15. Low temperature planar regrowth of semi-insulating InP by low pressure hydride vapour phase epitaxy for device application

    Science.gov (United States)

    Alexandre, F.; Parillaud, O.; Nguyen, D. C.; Azoulay, R.; Quillec, M.; Bouchoule, S.; Le Mestreallan, G.; Juhel, M.; Le Roux, G.; Rao, E. V. K.

    1998-05-01

    The growth of both undoped and iron doped InP on planar as well as non-planar (0 0 1)InP substrates has been explored using low pressure hydride vapour phase epitaxy (LP-HVPE) in the temperature range of 500-620°C. Secondary ion mass spectroscopy (SIMS), X-ray diffraction and photoluminescence measurements have shown no drastic degradation in the crystal quality with decreasing growth temperature. The Fe incorporation in the layers is found to be independent of the substrate temperature ( Ts) and in all experiments semi-insulating InP : Fe layers with resistivities close to 10 9 Ω cm have been obtained. A perfect growth selectivity with no deposition on masked areas and a good planarized regrowth on mesas has been demonstrated even at low Ts.

  16. Syntheses and properties of several metastable and stable hydrides derived from intermetallic compounds under high hydrogen pressure

    Science.gov (United States)

    Filipek, S. M.; Paul-Boncour, V.; Liu, R. S.; Jacob, I.; Tsutaoka, T.; Budziak, A.; Morawski, A.; Sugiura, H.; Zachariasz, P.; Dybko, K.; Diduszko, R.

    2016-12-01

    Brief summary of our former work on high hydrogen pressure syntheses of novel hydrides and studies of their properties is supplemented with new results. Syntheses and properties of a number of hydrides (unstable, metastable or stable in ambient conditions) derived under high hydrogen pressure from intermetallic compounds, like MeT2, MeNi5, Me7T3, Y6Mn23 and YMn12 (where Me = zirconium, yttrium or rare earth; T = transition metal) are presented. Stabilization of ZrFe2H4 due to surface phenomena was revealed. Unusual role of manganese in hydride forming processes is pointed out. Hydrogen induced phase transitions, suppression of magnetism, antiferromagnetic-ferromagnetic and metal-insulator or semimetal-metal transitions are described. Equations of state (EOS) of hydrides submitted to hydrostatic pressures up to 30 GPa are presented and discussed.

  17. Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8.

    Science.gov (United States)

    Wu, Xiao-Nan; Zhao, Hai-Tao; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2014-12-28

    The thermal reactions of [Zn(OH)](+) with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C-H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)](+) serves as active site in the hydride transfer to generate [i-C3H7](+) as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C-H bond results mainly in the formation of water and [Zn(C3,H7)](+). According to computational work, this ionic product corresponds to [HZn(CH3CH=CH2)](+). Attack of the zinc center at a secondary C-H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7](+); (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2=CH2 occurs to produce [HZn(H2O)](+). Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)](+). The combined experimental/computational gas-phase study of C-H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays.

  18. Aerosol generation of As and Se hydrides using a new Flow Blurring® multiple nebulizer for sample introduction in inductively coupled plasma optical emission spectrometry

    OpenAIRE

    Pereira, Catarinie D.; Aguirre Pastor, Miguel Ángel; NÓBREGA, Joaquim A.; Hidalgo Núñez, Montserrat; Canals Hernández, Antonio

    2014-01-01

    A new Flow Blurring® multiple nebulizer (FBMN) has been used for the efficient generation of As and Se hydrides directly into the aerosol formed inside the spray chamber before detection by inductively coupled plasma optical emission spectrometry (ICP OES). The FBMN allowed the hydride generation directly into the spray chamber without using any additional device either for solution and gas control or for gas phase separation. Synthetic solutions containing As and Se plus Ca, Mg and K were us...

  19. Hydride formation on deformation twin in zirconium alloy

    Science.gov (United States)

    Kim, Ju-Seong; Kim, Sung-Dae; Yoon, Jonghun

    2016-12-01

    Hydrides deteriorate the mechanical properties of zirconium (Zr) alloys used in nuclear reactors. Intergranular hydrides that form along grain boundaries have been extensively studied due to their detrimental effects on cracking. However, it has been little concerns on formation of Zr hydrides correlated with deformation twins which is distinctive heterogeneous nucleation site in hexagonal close-packed metals. In this paper, the heterogeneous precipitation of Zr hydrides at the twin boundaries was visualized using transmission electron microscopy. It demonstrates that intragranular hydrides in the twinned region precipitates on the rotated habit plane by the twinning and intergranular hydrides precipitate along the coherent low energy twin boundaries independent of the conventional habit planes. Interestingly, dislocations around the twin boundaries play a substantial role in the nucleation of Zr hydrides by reducing the misfit strain energy.

  20. Growth of polar and non-polar nitride semiconductor quasi-substrates by hydride vapor phase epitaxy for the development of optoelectronic devices by molecular beam epitaxy

    Science.gov (United States)

    Moldawer, Adam Lyle

    The family of nitride semiconductors has had a profound influence on the development of optoelectronics for a large variety of applications. However, as of yet there are no native substrates commercially available that are grown by liquid phase methods as with Si and GaAs. As a result, the majority of electronic and optoelectronic devices are grown heteroepitaxially on sapphire and SiC. This PhD research addresses both the development of polar and non-polar GaN and AIN templates by Hydride Vapor Phase Epitaxy (HVPE) on sapphire and SiC substrates, as well as the growth and characterization of optoelectronic devices on these templates by molecular beam epitaxy (MBE). Polar and non-polar GaN templates have been grown in a vertical HVPE reactor on the C- and R-planes of sapphire respectively. The growth conditions have been optimized to allow the formation for thick (50um) GaN templates without cracks. These templates were characterized structurally by studying their surface morphologies by SEM and AFM, and their structure through XRD and TEM. The polar C-plane GaN templates were found to be atomically smooth. However, the surface morphology of the non-polar GaN films grown on the R-plane of sapphire were found to have a facetted surface morphology, with the facets intersecting at 120° angles. This surface morphology reflects an equilibrium growth, since the A-plane of GaN grows faster than the M-planes of GaN due to the lower atomic density of the plane. For the development of deep-UV optoelectronics, it is required to grow AIGaN quantum wells on AIN templates. However, since AIN is a high melting point material, such templates have to be grown at higher temperatures, close to half the melting point of the material (1500 °C). As these temperatures cannot be easily obtained by traditional furnace heating, an HVPE reactor has been designed to heat the substrate inductively to these temperatures. This apparatus has been used to grow high-quality, transparent AIN films

  1. Properties of nanoscale metal hydrides.

    Science.gov (United States)

    Fichtner, Maximilian

    2009-05-20

    Nanoscale hydride particles may exhibit chemical stabilities which differ from those of a macroscopic system. The stabilities are mainly influenced by a surface energy term which contains size-dependent values of the surface tension, the molar volume and an additional term which takes into account a potential reduction of the excess surface energy. Thus, the equilibrium of a nanoparticular hydride system may be shifted to the hydrogenated or to the dehydrogenated side, depending on the size and on the prefix of the surface energy term of the hydrogenated and dehydrogenated material. Additional complexity appears when solid-state reactions of complex hydrides are considered and phase segregation has to be taken into account. In such a case the reversibility of complex hydrides may be reduced if the nanoparticles are free standing on a surface. However, it may be enhanced if the system is enclosed by a nanoscale void which prevents the reaction partners on the dehydrogenated side from diffusing away from each other. Moreover, the generally enhanced diffusivity in nanocrystalline systems may lower the kinetic barriers for the material's transformation and, thus, facilitate hydrogen absorption and desorption.

  2. Characterization of hydrides and delayed hydride cracking in zirconium alloys

    Science.gov (United States)

    Fang, Qiang

    This thesis tries to fill some of the missing gaps in the study of zirconium hydrides with state-of-art experiments, cutting edge tomographical technique, and a novel numerical algorithm. A new hydriding procedure is proposed. The new anode material and solution combination overcomes many drawbacks of the AECLRTM hydriding method and leads to superior hydriding result compared to the AECL RTM hydriding procedure. The DHC crack growth velocity of as-received Excel alloy and Zr-2.5Nb alloy together with several different heat treated Excel alloy samples are measured. While it already known that the DHC crack growth velocity increases with the increase of base metal strength, the finding that the transverse plane is the weaker plane for fatigue crack growth despite having higher resistance to DHC crack growth was unexpected. The morphologies of hydrides in a coarse grained Zircally-2 sample have been studied using synchrotron x-rays at ESRF with a new technique called Diffraction Contrast Tomography that uses simultaneous collection of tomographic data and diffraction data to determine the crystallographic orientation of crystallites (grains) in 3D. It has been previously limited to light metals such as Al or Mg (due to the use of low energy x-rays). Here we show the first DCT measurements using high energy x-rays (60 keV), allowing measurements in zirconium. A new algorithm of a computationally effcient way to characterize distributions of hydrides - in particular their orientation and/or connectivity - has been proposed. It is a modification of the standard Hough transform, which is an extension of the Hough transform widely used in the line detection of EBSD patterns. Finally, a basic model of hydrogen migration is built using ABAQUS RTM, which is a mature finite element package with tested modeling modules of a variety of physical laws. The coupling of hydrogen diffusion, lattice expansion, matrix deformation and phase transformation is investigated under

  3. Destabilization of magnesium hydride through interface engineering

    OpenAIRE

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesium hydride is very stable, which means that hydrogen is released only at elevated temperature. Furthermore, the kinetics of hydrogen sorption is slow, which further hampers the practical use of this...

  4. Understanding of hydriding mechanisms of zircaloy-4 alloy during corrosion in PWR simulated conditions and influence of zirconium hydrides on zircaloy-4 corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Bisor-Melloul, C.; Tupin, M.; Bossis, P. [DEN/DANS/DMN/SEMI, CEA/Saclay, 91191 Gif-sur-Yvette (France); Chene, J. [DEN/DANS/DPC/SCCME, CEA/Saclay, 91191 Gif-sur-Yvette (France); Bechade, J.L. [DEN/DANS/DMN/SRMA, CEA/Saclay, 91191 Gif-sur-Yvette (France); Motta, A. [Mechanical and Nuclear Engineering Department, Penn State University, 227 Reber Building, University Park, PA 16802 (United States)

    2010-07-01

    Zirconium alloys are widely used as fuel claddings in Power Water Reactors. As they represent the first containment barrier to fission products, their mechanical integrity is essential for nuclear safety. During their corrosion in primary water, some of the hydrogen involved in the oxidation reaction with water ingresses into the alloy through the oxide layer. In the metallic matrix, once the solid solution limit is reached at the irradiation temperature, hydrogen precipitates as Zr hydrides mainly located just under the metal/oxide interface due to the thermal gradient across the cladding. As these hydrides may contribute to a larger oxide thickness and to a more fragile behaviour of the cladding, the minimization of hydrogen pick-up is required. Accordingly, since the Zircaloy-4 (Zr-1.3Sn-0.2Fe-0.1Cr) alloy is known to be sensitive to this phenomenon, the understanding of its hydriding mechanism and of the influence of zirconium hydrides on its corrosion behaviour is needed. Regarding the study of the hydriding mechanism, isotopic exchanges were carried out in D{sub 2}O environment at 360 deg. C and led to the localization, in the oxide scales, of the limiting step for the hydrogen diffusion. To estimate an apparent diffusion coefficient of hydrogen in the oxide formed on Zircaloy-4, we firstly based on SIMS profiles and penetration depth of deuterium in the dense part of the oxide film. Secondly, ERDA estimation of the hydrogen content in zirconia and fusion measurements of the hydrogen content in both metal and oxide were used to estimate a hydrogen flux absorbed by the alloy and hence to deduce an apparent diffusion coefficient. Finally, these two methods lead to quite similar values (between 2.10{sup -14} cm{sup 2}/s and 6.10{sup -14} cm{sup 2}/s) which are in accordance with bibliography. Concerning the impact of hydrides on the corrosion of Zircaloy-4, several pre-hydrided and reference samples were corroded simultaneously in primary water at 360 deg. C

  5. Activation and discharge kinetics of metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, Stein Egil

    2003-07-01

    Potential step chronoamperometry and Electrochemical Impedance Spectroscopy (eis) measurements were performed on single metal hydride particles. For the {alpha}-phase, the bulk diffusion coefficient and the absorption/adsorption rate parameters were determined. Materials produced by atomisation, melt spinning and conventional casting were investigated. The melt spun and conventional cast materials were identical and the atomised material similar in composition. The particles from the cast and the melt spun material were shaped like parallelepipeds. A corresponding equation, for this geometry, for diffusion coupled to an absorption/adsorption reaction was developed. It was found that materials produced by melt spinning exhibited lower bulk diffusion (1.7E-14 m2/s) and absorption/adsorption reaction rate (1.0E-8 m/s), compared to materials produced by conventionally casting (1.1E-13 m2/s and 5.5E-8 m/s respectively). In addition, the influence of particle active surface and relative diffusion length were discussed. It was concluded that there are uncertainties connected to these properties, which may explain the large distribution in the kinetic parameters measured on metal hydride particles. Activation of metal hydride forming materials has been studied and an activation procedure, for porous electrodes, was investigated. Cathodic polarisation of the electrode during a hot alkaline surface treatment gave the maximum discharge capacity on the first discharge of the electrode. The studied materials were produced by gas atomisation and the spherical shape was retained during the activation. Both an AB{sub 5} and an AB{sub 2} alloy was successfully activated and discharge rate properties determined. The AB{sub 2} material showed a higher maximum discharge capacity, but poor rate properties, compared to the AB{sub 5} material. Reduction of surface oxides, and at the same time protection against corrosion of active metallic nickel, can explain the satisfying results of

  6. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    by annealing at 700°C for 12 hours. The alloys appeared to be nanocrystalline with an average crystallite size around 10 nm before annealing. Special steel containers was developed for the annealing of the metal powders in inert atmosphere. The use of various annealing temperatures was investigated......This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today...... was developed. The parameters milling time, milling intensity, number of balls and form of the alloying metals were investigated. Based on this a final alloying technique for the subsequent preparation of electrode materials was established. The technique comprises milling for 4 hours twice possibly followed...

  7. Phase Retrieval Algorithm for Form Testing Metrology in Production Environment

    Directory of Open Access Journals (Sweden)

    Stephan Stuerwald

    2010-08-01

    Full Text Available Form testing interferometry permits a fast, non-tactile and full- field quantitative phase imaging of components in ultra precise manufacturing. To reduce the influence of vibrations under manufacturing conditions, it is most common to use the FT- based spatial carrier phase measurement technique (SCPM which requires only a single interferogram recording. The utilization of a generalized, relatively new spatial phase-shifting method operating in the position space opens up prospects for reduced phase noise and less reconstruction errors of the calculated phase-map under production conditions. Therefore this phase-shifting technique is investigated for applicability in machine integrated interferometric form testing of optical lenses. A characterization of the algorithm and a comparison with the commonly used FT-based algorithm is performed. As a reference, measurements are carried out with a coordinate measuring machine with nanometre accuracy.

  8. Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.

    Science.gov (United States)

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2011-01-01

    Trialkylborane additives promote reduction of CO(2) to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO(2) to give a formate-borane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO(2) reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formate-borane adduct.

  9. Reversible storage of the hydrogen by nano structured magnesium hydride; Stockage reversible de l'hydrogene sous forme d'hydrure de magnesium nano-structure

    Energy Technology Data Exchange (ETDEWEB)

    Rango, P. de; Chaise, A.; Fruchart, D.; Miraglia, S. [Institut Neel et CRETA, CNRS - UJF, 38 - Grenoble (France); Marty, P. [LEGI - INPG, 38 - Grenoble (France)

    2007-07-01

    The magnesium hydride MgH{sub 2} is an excellent hydrogen storage element: low cost, abundant, high mass storage capacity up to 7,6% by weight. Meanwhile it presents slow absorption-desorption kinetics and too high thermodynamical stability. Many studies have been realized to improve these kinetics by co-milling with a transition metal. The author presents the metal transition mechanism of this process and the transfer of the production in the industry. (A.L.B.)

  10. Formation and physical properties of uranium hydride under conditions relevant to metallic fuel and nuclear waste storage

    Energy Technology Data Exchange (ETDEWEB)

    Orr, Robin, E-mail: robin.orr@nnl.co.uk [National Nuclear Laboratory, Central Laboratory, Sellafield, Seascale, Cumbria, CA20 1PG (United Kingdom); Godfrey, Hugh [National Nuclear Laboratory, Workington Laboratory, Havelock Road, Derwent Howe, Workington, Cumbria, CA14 3YQ (United Kingdom); Broan, Chris; Goddard, Dave; Woodhouse, Guy; Durham, Peter [National Nuclear Laboratory, Preston Laboratory, Springfields, Salwick, Preston, Lancashire, PR4 0XJ (United Kingdom); Diggle, Andrew [Sellafield Ltd., Sellafield, Seascale, Cumbria, CA20 1PG (United Kingdom); Bradshaw, John [Sellafield Ltd., Hinton House, Risley, Warrington, WA3 6GR (United Kingdom)

    2016-08-15

    The formation of uranium hydride is recognised as a hazard during the storage of uranium metal owing to its potentially pyrophoric properties. This study has assessed the influence of water vapour on the potential for uranium hydride to form at low temperatures and shows that it increases the duration of the induction period but does not necessarily prevent uranium hydride formation and also does not significantly change the reaction rate with hydrogen. It is further shown that the α-UH{sub 3} fraction in the uranium hydride gradually increases at decreasing temperatures and is likely to be the dominant phase formed under typical storage conditions. Particle morphology and specific surface area of uranium hydride prepared between 30 °C and 200 °C have also been characterised but show only modest variation compared with the phase composition. - Highlights: • The reaction of uranium in dry hydrogen and hydrogen/water vapour has been measured between 30 and 200 °C. • Water vapour extends the induction period but does not necessarily prevent UH{sub 3} formation or affect the reaction rate. • X-ray diffraction analysis shows a gradual increase in α-UH{sub 3} and reduction in β-UH{sub 3} with decreasing preparation temperature. • Particle morphology and specific surface area show only a modest variation with temperature.

  11. AlN and AlGaN layers grown on Si(111) substrate by mixed-source hydride vapor phase epitaxy method

    Science.gov (United States)

    Jeon, Hunsoo; Jeon, Injun; Lee, Gang Seok; Bae, Sung Geun; Ahn, Hyung Soo; Yang, Min; Yi, Sam Nyung; Yu, Young Moon; Honda, Yoshio; Sawaki, Nobuhiko; Kim, Suck-Whan

    2017-01-01

    High Al-composition AlGaN and AlN epilayers were grown directly on Si(111) substrate by a hydride vapor phase epitaxy (HVPE) method with a melted mixed source in a graphite boat set in a source zone with high temperatures of T = 700 and 800 °C, respectively. The presence of the Ga material in the mixed source of Ga and Al promoted the growth of AlN and AlGaN epilayers in the growth zone. When the temperature in the source zone was 800 °C, the crystalline quality of the AlN and AlGaN epilayers increased as the ratio of Ga to Al increased, and the optimum mix ratio of Ga to Al for the growth of AlN epilayers was approximately 0.35-0.42, obtained from a numerical fitting analysis of the X-ray diffraction (XRD) data for these epilayers. It appears that they can be grown directly by our melted-mixed-source HVPE method in a high-temperature source zone.

  12. Nuclear magnetic resonance studies of hydrogen motion in nanostructured Laves-phase hydrides ZrCr(2)H(x) and TaV(2)H(x).

    Science.gov (United States)

    Soloninin, A V; Buzlukov, A L; Skripov, A V; Aleksashin, B A; Tankeyev, A P; Yermakov, A Ye; Mushnikov, N V; Uimin, M A; Gaviko, V S

    2008-07-09

    In order to study the mobility of hydrogen in nanostructured Laves-phase hydrides, we have measured the proton nuclear magnetic resonance (NMR) spectra and the proton spin-lattice and spin-spin relaxation rates in two nanostructured systems prepared by ball milling: ZrCr(2)H(3) and TaV(2)H(1+δ). The proton NMR measurements have been performed at the resonance frequencies of 14, 23.8 and 90 MHz over the temperature ranges 11-424 K (for coarse-grained samples) and 11-384 K (for nanostructured samples). Hydrogen mobility in the ball-milled ZrCr(2)H(3) is found to decrease strongly with increasing milling time. The experimental data suggest that this effect is related to the growth of the fraction of highly distorted intergrain regions where H mobility is much lower than in the crystalline grains. For the nanostructured TaV(2)H(1+δ) system, the ball milling is found to lead to a slight decrease in the long-range H mobility and to a suppression of the fast localized H motion in the crystalline grains.

  13. Hydride-vapor-phase epitaxial growth of highly pure GaN layers with smooth as-grown surfaces on freestanding GaN substrates

    Science.gov (United States)

    Fujikura, Hajime; Konno, Taichiro; Yoshida, Takehiro; Horikiri, Fumimasa

    2017-08-01

    Thick (20-30 µm) layers of highly pure GaN with device-quality smooth as-grown surfaces were prepared on freestanding GaN substrates by using our advanced hydride-vapor-phase epitaxy (HVPE) system. Removal of quartz parts from the HVPE system markedly reduced concentrations of residual impurities to below the limits of detection by secondary-ion mass spectrometry. Appropriate gas-flow management in the HVPE system realized device-quality, smooth, as-grown surfaces with an excellent uniformity of thickness. The undoped GaN layer showed insulating properties. By Si doping, the electron concentration could be controlled over a wide range, down to 2 × 1014 cm-3, with a maximum mobility of 1150 cm2·V-1·s-1. The concentration of residual deep levels in lightly Si-doped layers was in the 1014 cm-3 range or less throughout the entire 2-in. wafer surface. These achievements clearly demonstrate the potential of HVPE as a tool for epitaxial growth of power-device structures.

  14. Pole figure measurement of the initial growth of GaN nanoneedles on GaN/Si(111) by using hydride vapor phase epitaxy

    Science.gov (United States)

    Jeon, Injun; Lee, Ha Young; Noh, Ji-Yeon; Ahn, Hyung Soo; Yi, Sam Nyung; Jeon, Hunsoo; Shin, Min Jeong; Yu, Young Moon; Ha, Dong Han

    2016-09-01

    We report on crystallographic analyses of one-dimensional GaN nanoneedles grown on a n-GaN epilayer by using hydride vapor phase epitaxy. The nanoneedles were grown with a HCl:NH3 gas flow ratio of 1:38 at 600 °C. The growth time of the GaN nanoneedles affected their morphologies. As time progressed, GaN dots nucleated and then evolved as nanoneedles. The vertical growth rate of GaN nanoneedles was higher than the lateral growth rate under optimized growth conditions. X-ray pole figure measurements were carried out using a four-axis diffractometer. For the sample grown for 20 min, we obtained discrete patterns with six strong dots and weak dough-nut and cotton swab patterns, indicating that most of the nanoneedles were grown ideally, but partially, in the x- y plane with an azimuthal rotation angle ϕ = 15 ~ 45° rotated to the substrate, and a few GaN nanoneedles were tilted by ±4° or by more than 32° from the vertical c-axis.

  15. Naturally occurring crystalline phases: analogues for radioactive waste forms

    Energy Technology Data Exchange (ETDEWEB)

    Haaker, R.F.; Ewing, R.C.

    1981-01-01

    Naturally occurring mineral analogues to crystalline phases that are constituents of crystalline radioactive waste forms provide a basis for comparison by which the long-term stability of these phases may be estimated. The crystal structures and the crystal chemistry of the following natural analogues are presented: baddeleyite, hematite, nepheline; pollucite, scheelite;sodalite, spinel, apatite, monazite, uraninite, hollandite-priderite, perovskite, and zirconolite. For each phase in geochemistry, occurrence, alteration and radiation effects are described. A selected bibliography for each phase is included.

  16. Structural and hydrogen storage capacity evolution of Mg2FeH6 hydride synthesized by reactive mechanical alloying

    Institute of Scientific and Technical Information of China (English)

    LI Song-lin(李松林); R.A.Varin

    2004-01-01

    Mg-based metal hydrides are promising as hydrogen storage materials for fuel cell application. In this work, Mg2 FeH6 complex hydride phase was synthesized by controlled reactive ball milling of 2Mg-Fe (atomic ratio)powder mixture in H2. Mg2 FeH6 is confirmed to be formed via the following three stages: formation of MgH2 via the reaction of Mg with H2, incubation stage and formation of Mg2 FeH6 by reaction of fully refined MgH2 and Fe.The incubation stage is characterized by no traces of Mg or hydride crystalline phase by XRD. On the other hand,Mg is observed uniformly distributed in the milled powder by SEM-EDS. Also, almost the same amount of H2 as the first stage is detected stored in the powders of the second stage by DSC and TGA.

  17. Preparation of a sample with a single MgH2 phase by horizontal ball milling and the first hydriding reaction of 90 wt% Mg-10 wt% MgH2

    Science.gov (United States)

    Hong, Seong-Hyeon; Song, Myoung Youp

    2015-03-01

    In order to prepare an additive-free sample with a single MgH2 phase, 90 wt% Mg-10 wt% MgH2 (named 90Mg-10MgH2) was milled under a hydrogen atmosphere in a horizontal ball mill, and then hydrided. The hydrogen absorption and desorption properties of the prepared samples were investigated, and compared with those of milled pure Mg and purchased MgH2. X-ray diffraction analysis, measurement of specific BET surface areas, and observation of the prepared samples by scanning electron microscope were performed. The 90Mg-10MgH2 sample after hydriding-dehydriding cycling had small and large particles with fine particles on their surfaces, and had much finer particles and more defects than the milled pure Mg sample after hydridingdehydriding cycling. The specific BET surface areas of the milled Mg and 90Mg-10MgH2 were measured as 7.81 and 99.81 m2/g, respectively. A sample that had almost a single MgH2 phase could be prepared by horizontal ball milling and the first hydriding reaction of 90Mg-10MgH2. 90Mg-10MgH2 released 5.82 wt% H for about 70 min, while unmilled MgH2 (Aldrich) released 6.04 wt% H for about 100 min, at 648 K.

  18. Simultaneous determination of hydride (Se) and non-hydride-forming (Ca, Mg, K, P, S and Zn) elements in various beverages (beer, coffee, and milk), with minimum sample preparation, by ICP-AES and use of a dual-mode sample-introduction system

    Energy Technology Data Exchange (ETDEWEB)

    Asfaw, Alemayehu; Wibetoe, Grethe [University of Oslo, Department of Chemistry, Blindern (Norway)

    2005-05-01

    A method has been developed enabling direct analysis (i.e. after dilution only) of beer, instant coffee, milk, and milk powder by ICP-AES. Analysis of the beverages after dilution with a low concentration of HNO{sub 3} was used for accurate determination of essential minor and trace elements (Ca, Mg, K, P, S, and Zn). Selenium, introduced as the hydride, was determined simultaneously with the other non-hydride-forming elements using the commercial multi-mode sample-introduction system (MSIS). To obtain accurate results, however, some simple pre-treatment was needed. Analysis was also performed after microwave-assisted decomposition of the samples. Three different modes of sample-preparation, i.e. dilution only, partial decomposition (aqua regia treatment), and complete decomposition were compared. The results obtained by use of the three different sample-preparation methods were in very good agreement. Results from analysis of certified reference material (SRM 1459 non-fat milk powder) also verified the accuracy of the methods. The limit of detection obtained for Se using dual-mode sample introduction was 0.5 ng mL{sup -1}, which corresponds to approximately 2 ng g{sup -1} in beer and approximately 4 ng g{sup -1} in coffee and milk when using the recommended procedure. (orig.)

  19. Atom probe analysis of titanium hydride precipitates.

    Science.gov (United States)

    Takahashi, J; Kawakami, K; Otsuka, H; Fujii, H

    2009-04-01

    It is expected that the three-dimensional atom probe (3DAP) will be used as a tool to visualize the atomic scale of hydrogen atoms in steel is expected, due to its high spatial resolution and very low detection limit. In this paper, the first 3DAP analysis of titanium hydride precipitates in metal titanium is reported in terms of the quantitative detection of hydrogen. FIB fabrication techniques using the lift-out method have enabled the production of needle tips of hydride precipitates, of several tens of microns in size, within a titanium matrix. The hydrogen concentration estimated from 3DAP analysis was slightly smaller than that of the hydride phase predicted from the phase diagram. We discuss the origin of the difference between the experimental and predicted values and the performance of 3DAP for the quantitative detection of hydrogen.

  20. Reversible hydrogen storage in nano-structured magnesium hydride; Stockage reversible de l'hydrogene sous forme d'hydrure de magnesium nano-structure

    Energy Technology Data Exchange (ETDEWEB)

    Rango, P. de; Chaise, A.; Fruchart, D.; Miraglia, S. [Grenoble-1 Univ. Joseph-Fourier, Institut Neel / CRETA, CNRS, 38 (France); Marty, P. [Institut National Polytechnique (INPG-LEGI), 38 - Grenoble (France)

    2007-07-01

    Magnesium hydride MgH{sub 2} is an excellent potential material for hydrogen storage: abundant and cheap, it presents a high gravimetric density (7.6% in mass of hydrogen). Nevertheless, it presents both very slow absorption/desorption kinetics and a too important thermodynamic stability leading to absorption/desorption temperatures of about 300 C. A lot of studies have been carried out to improve the reaction kinetics by co-grinding with a transition metal. The aim of this work is to explain particularly the role of the transition metal. Experimental results are presented and analyzed. (O.M.)

  1. Studies of phase transitions in the aripiprazole solid dosage form.

    Science.gov (United States)

    Łaszcz, Marta; Witkowska, Anna

    2016-01-05

    Studies of the phase transitions in an active substance contained in a solid dosage form are very complicated but essential, especially if an active substance is classified as a BCS Class IV drug. The purpose of this work was the development of sensitive methods for the detection of the phase transitions in the aripiprazole tablets containing initially its form III. Aripiprazole exhibits polymorphism and pseudopolymorphism. Powder diffraction, Raman spectroscopy and differential scanning calorimetry methods were developed for the detection of the polymorphic transition between forms III and I as well as the phase transition of form III into aripiprazole monohydrate in tablets. The study involved the initial 10 mg and 30 mg tablets, as well as those stored in Al/Al blisters, a triplex blister pack and HDPE bottles (with and without desiccant) under accelerated and long term conditions. The polymorphic transition was not observed in the initial and stored tablets but it was visible on the DSC curve of the Abilify(®) 10 mg reference tablets. The formation of the monohydrate was observed in the diffractograms and Raman spectra in the tablets stored under accelerated conditions. The monohydrate phase was not detected in the tablets stored in the Al/Al blisters under long term conditions. The results showed that the Al/Al blisters can be recommended as the packaging of the aripiprazole tablets containing form III.

  2. Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4 (L(Ph) = bis(diphenylphosphino)methane).

    Science.gov (United States)

    Zavras, Athanasios; Ariafard, Alireza; Khairallah, George N; White, Jonathan M; Mulder, Roger J; Canty, Allan J; O'Hair, Richard A J

    2015-11-21

    Borohydrides react with silver salts to give products that span multiple scales ranging from discrete mononuclear compounds through to silver nanoparticles and colloids. The cluster cations [Ag3(H)(BH4)L3](+) are observed upon electrospray ionization mass spectrometry of solutions containing sodium borohydride, silver(I) tetrafluoroborate and bis(dimethylphosphino)methane (L(Me)) or bis(diphenylphosphino)methane (L(Ph)). By adding NaBH4 to an acetonitrile solution of AgBF4 and L(Ph), cooled to ca. -10 °C, we have been able to isolate the first mixed silver hydride borohydride nanocluster, [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4, and structurally characterise it via X-ray crystallography. Combined gas-phase experiments (L(Me) and L(Ph)) and DFT calculations (L(Me)) reveal how loss of a ligand from the cationic complexes [Ag3(H)(BH4)L3](+) provides a change in geometry that facilitates subsequent loss of BH3 to produce the dihydride clusters, [Ag3(H)2Ln](+) (n = 1 and 2). Together with the results of previous studies (Girod et al., Chem. - Eur. J., 2014, 20, 16626), this provides a direct link between mixed silver hydride/borohydride nanoclusters, silver hydride nanoclusters, and silver nanoclusters.

  3. Hydriding and microstructure nanocrystallization of ZK60 Mg alloy by reaction milling in hydrogen

    Institute of Scientific and Technical Information of China (English)

    YUAN Yuan; WANG Heng; HU Lian-xi; SUN Hong-fei; FANG Wen-bin

    2009-01-01

    The hydriding of as-cast Mg-5.5%Zn-0.6%Zr (ZK60 Mg) (mass fraction) alloy was achieved by room-temperature reaction milling in hydrogen, with the mechanical energy serving as the driving force for the process. The hydriding progress during milling was examined by hydrogen absorption measurement, and the microstructure change was characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The results show that, by room-temperature reaction milling in hydrogen, the as-cast ZK60 Mg alloy can be fully hydrided to form a nanocrystalline MgH2 single-phase microstructure. In particular, the average grain size of the MgH2 phase obtained by room-temperature reaction milling in hydrogen for 16.2 h is about 8-10 nm, and the average particle size of the as-milled hydrided powders is 2-3 μm.

  4. Critical issues for homoepitaxial GaN growth by molecular beam epitaxy on hydride vapor-phase epitaxy-grown GaN substrates

    Science.gov (United States)

    Storm, D. F.; Hardy, M. T.; Katzer, D. S.; Nepal, N.; Downey, B. P.; Meyer, D. J.; McConkie, Thomas O.; Zhou, Lin; Smith, David J.

    2016-12-01

    While the heteroepitaxial growth of gallium nitride-based materials and devices on substrates such as SiC, sapphire, and Si has been well-documented, the lack of a cost-effective source of bulk GaN crystals has hindered similar progress on homoepitaxy. Nevertheless, freestanding GaN wafers are becoming more widely available, and there is great interest in growing GaN films and devices on bulk GaN substrates, in order to take advantage of the greatly reduced density of threading dislocations, particularly for vertical devices. However, homoepitaxial GaN growth is far from a trivial task due to the reactivity and different chemical sensitivities of N-polar (000_1) and Ga-polar (0001) GaN surfaces, which can affect the microstructure and concentrations of impurities in homoepitaxial GaN layers. In order to achieve high quality, high purity homoepitaxial GaN, it is necessary to investigate the effect of the ex situ wet chemical clean, the use of in situ cleaning procedures, the sensitivity of the GaN surface to thermal decomposition, and the effect of growth temperature. We review the current understanding of these issues with a focus on homoepitaxial growth of GaN by molecular beam epitaxy (MBE) on c-plane surfaces of freestanding GaN substrates grown by hydride vapor phase epitaxy (HVPE), as HVPE-grown substrates are most widely available. We demonstrate methods for obtaining homoepitaxial GaN layers by plasma-assisted MBE in which no additional threading dislocations are generated from the regrowth interface and impurity concentrations are greatly reduced.

  5. Hydride generation coupled to microfunnel-assisted headspace liquid-phase microextraction for the determination of arsenic with UV-Vis spectrophotometry.

    Science.gov (United States)

    Hashemniaye-Torshizi, Reihaneh; Ashraf, Narges; Arbab-Zavar, Mohammad Hossein

    2014-12-01

    In this research, a microfunnel-assisted headspace liquid-phase microextraction technique has been used in combination with hydride generation to determine arsenic (As) by UV-Vis spectrophotometry. The method is based on the reduction of As to arsine (AsH3) in acidic media by sodium tetrahydroborate (NaBH4) followed by its subsequent reaction with silver diethyldithiocarbamate (AgDDC) to give an absorbing complex at 510 nm. The complexing reagent (AgDDC) has been dissolved in a 1:1 (by the volume ratio) mixture of chloroform/chlorobenzene microdroplet and exposed to the generated gaseous arsine via a reversed microfunnel in the headspace of the sample solution. Several operating parameters affecting the performance of the method have been examined and optimized. Acetonitrile solvent has been added to the working samples as a sensitivity enhancement agent. Under the optimized operating conditions, the detection limit has been measured to be 0.2 ng mL(-1) (based on 3sb/m criterion, n b = 8), and the calibration curve was linear in the range of 0.5-12 ng mL(-1). The relative standard deviation for eight replicate measurements was 1.9 %. Also, the effects of several potential interferences have been studied. The accuracy of the method was validated through the analysis of JR-1 geological standard reference material. The method has been successfully applied for the determination of arsenic in raw and spiked soft drink and water samples with the recoveries that ranged from 91 to 106 %.

  6. Compression and phase diagram of lithium hydrides at elevated pressures and temperatures by first-principles calculations

    CERN Document Server

    Chen, Yang M; Wu, Qiang; Geng, Hua Y; Yan, Xiao Z; Wang, Yi X; Wang, Zi W

    2016-01-01

    High pressure and high temperature properties of AB (A = $^6$Li, $^7$Li; B = H, D, T) are investigated with first-principles method comprehensively. It is found that the H$^{-}$ sublattice features in the low-pressure electronic structure near the Fermi level of LiH are shifted to that dominated by the Li$^{+}$ sublattice in compression. The lattice dynamics is studied in quasi-harmonic approximation, from which the phonon contribution to the free energy and the isotopic effects are accurately modelled with the aid of a parameterized double-Debye model. The obtained equation of state (EOS) matches perfectly with available static experimental data. The calculated principal Hugoniot is also in accordance with that derived from shock wave experiments. Using the calculated principal Hugoniot and the previous theoretical melting curve, we predict a shock melting point at 56 GPa and 1923 K. In order to establish the phase diagram for LiH, the phase boundaries between the B1 and B2 solid phases are explored. The B1-...

  7. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

    Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

  8. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

    Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

  9. Phases formed during rapid quenching of liquid carbon

    Science.gov (United States)

    Basharin, A. Yu.; Dozhdikov, V. S.; Dubinchuk, V. T.; Kirillin, A. V.; Lysenko, I. Yu.; Turchaninov, M. A.

    2009-05-01

    Pulsed laser action upon a sample of highly oriented pyrolytic graphite (HOPG) in a gasostat filled with helium at a pressure above that corresponding to the triple point of carbon, followed by rapid quenching of the liquid phase at a rate of about 106 K/s leads to the formation of a crater with a periodic spatial structure at the surface. The composition and structure of nongraphite carbon phases in the near-surface region of the crater have been studied using the Raman scattering spectroscopy, electron microdiffraction, and energy-dispersive X-ray analysis. It is established that rapidly quenched carbon possesses predominantly a hybrid structure of glassy carbon formed as a result of the high-temperature treatment, with inclusions of crystalline carbyne, chaoite, and a hybrid cubic phase of ultradense carbon (C8). The hybrid phases of glassy carbon and C8 had not been reported until now as possible products of solidification of liquid carbon.

  10. ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jy-An John [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Yan, Yong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Wang, Hong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-10-28

    A systematic study of H. B. Robinson (HBR) high burnup spent nuclear fuel (SNF) vibration integrity was performed in Phase I project under simulated transportation environments, using the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) hot cell testing technology developed at Oak Ridge National Laboratory in 2013–14. The data analysis on the as-irradiated HBR SNF rods demonstrated that the load amplitude is the dominant factor that controls the fatigue life of bending rods. However, previous studies have shown that the hydrogen content and hydride morphology has an important effect on zirconium alloy mechanical properties. To address the effect of radial hydrides in SNF rods, in Phase II a test procedure was developed to simulate the effects of elevated temperatures, pressures, and stresses during transfer-drying operations. Pressurized and sealed fuel segments were heated to the target temperature for a preset hold time and slow-cooled at a controlled rate. The procedure was applied to both non-irradiated/prehydrided and high-burnup Zircaloy-4 fueled cladding segments using the Nuclear Regulatory Commission-recommended 400°C maximum temperature limit at various cooling rates. Before testing high-burnup cladding, four out-of-cell tests were conducted to optimize the hydride reorientation (R) test condition with pre-hydride Zircaloy-4 cladding, which has the same geometry as the high burnup fuel samples. Test HR-HBR#1 was conducted at the maximum hoop stress of 145 MPa, at a 400°C maximum temperature and a 5°C/h cooling rate. On the other hand, thermal cycling was performed for tests HR-HBR#2, HR-HBR#3, and HR-HBR#4 to generate more radial hydrides. It is clear that thermal cycling increases the ratio of the radial hydride to circumferential hydrides. The internal pressure also has a significant effect on the radial hydride morphology. This report describes a procedure and experimental results of the four out-of-cell hydride reorientation tests of

  11. Gas Phase Hydration of Methyl Glyoxal to Form the Gemdiol

    Science.gov (United States)

    Kroll, Jay A.; Axson, Jessica L.; Vaida, Veronica

    2016-06-01

    Methylglyoxal is a known oxidation product of volatile organic compounds (VOCs) in Earth's atmosphere. While the gas phase chemistry of methylglyoxal is fairly well understood, its modeled concentration and role in the formation of secondary organic aerosol (SOA) continues to be controversial. The gas phase hydration of methylglyoxal to form a gemdiol has not been widely considered for water-restricted environments such as the atmosphere. However, this process may have important consequences for the atmospheric processing of VOCs. We will report on spectroscopic work done in the Vaida laboratory studying the hydration of methylglyoxal and discuss the implications for understanding the atmospheric processing and fate of methylglyoxal and similar molecules.

  12. Fabrication of large flat gallium nitride templates with extremely low dislocation densities in the 106 cm-2 range by novel two-side hydride vapor-phase epitaxial growth

    Science.gov (United States)

    Fujikura, Hajime; Konno, Taichiro

    2017-10-01

    Large GaN templates with high flatness (i.e., negligible wafer bowing and smooth as-grown surfaces) and low threading dislocation densities (TTDs) were fabricated by a novel two-side hydride vapor-phase epitaxial (HVPE) growth, beginning with deposition of polycrystalline GaN on the rear side of the wafer. Appropriate gas-flow management realized by our homemade HVPE system permitted the growth of a GaN layer with a smooth as-grown surface and excellent thickness uniformity on the front surfaces of 4- or 6-inch patterned sapphire substrates (PSSs). However, when the grown thickness exceeded 20 μm, single-side HVPE-growth induced fractures in GaN crystals. The fracture resistance of the GaN increased markedly when it was in a cleavage-resistant polycrystalline form (poly-GaN), permitting its growth to a thickness of 100 μm. In the presence of a back-side poly-GaN layer, extremely thick GaN crystal layers could be grown on the front side without fractures. An 80-μm-thick GaN template fabricated by two-side growth on a 4-inch PSS had a device-quality surface, negligible bowing, and low TDD (7 × 106 cm-2). Issues of high fabrication costs, unavailability of large-size wafers, and large off-angle variations associated with native GaN wafers could be overcome by using our high-quality GaN templates as alternative substrates.

  13. Microscopic characterization of crystalline phases in waste forms

    Energy Technology Data Exchange (ETDEWEB)

    Buck, E.C.; Dietz, N.L.; Wronkiewicz, D.J.; Bates, J.K. [Argonne National Lab., IL (United States); Millar, A. [Purdue Univ., West Lafayette, IN (United States)

    1995-07-01

    Transmission electron microscopy (TEM) has been used to determine the microstructure of crystalline phases present in zirconium- and titanium-bearing glass crystalline composite (GCC) waste forms. The GCC materials were found to contain spinels (maghemite), zirconolites, perovskites (CaTiO{sub 3}) and plagiociase feldspar (anorthite) mineral phases. The structure of the uranium and cerium-bearing monoclinic zirconolite was characterized by medium resolution TEM imaging and electron and X-ray diffraction (XRD). The phase was found to contain high levels of iron in comparison to Synroc-type zirconolites. Excess zirconium in zirconolite has resulted in martensitic baddeleyite (ZrO{sub 2}) formation. Anorthite (CaAl{sub 2}Si{sub 2}O{sub 8}) was present as elongated crystallites within a calcium-rich aluminosilicate glass. Lead and iron-bearing anorthite lying along distinct precipitates were occasionally observed within the an crystallographic planes.

  14. Synthesis and structural study of Ti-rich Mg-Ti hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Asano, Kohta; Kim, Hyunjeong; Sakaki, Kouji; Page, Katharine; Hayashi, Shigenobu; Nakamura, Yumiko; Akiba, Etsuo [NIAIST; (LANL); (Kyushu)

    2014-02-26

    MgxTi1-x (x = 0.15, 0.25, 0.35) alloys were synthesized by means of ball milling. Under a hydrogen pressure of 8 MPa at 423 K these Mg–Ti alloys formed a hydride phase with a face centered cubic (FCC) structure. The hydride for x = 0.25 consisted of single Mg0.25Ti0.75H1.62 FCC phase but TiH2 and MgH2 phases were also formed in the hydrides for x = 0.15 and 0.35, respectively. X-ray diffraction patterns and the atomic pair distribution function indicated that numbers of stacking faults were introduced. There was no sign of segregation between Mg and Ti in Mg0.25Ti0.75H1.62. Electronic structure of Mg0.25Ti0.75H1.62 was different from those of MgH2 and TiH2, which was demonstrated by 1H nuclear magnetic resonance. This strongly suggested that stable Mg–Ti hydride phase was formed in the metal composition of Mg0.25Ti0.75 without disproportion into MgH2 and TiH2.

  15. On the optical absorption coefficient of Gd hydride thin films: coexistence of the Gd (GdH{sub 2}) and GdH{sub x} (GdH{sub 2+y}) phases

    Energy Technology Data Exchange (ETDEWEB)

    Vargas, W E; Azofeifa, D E; Clark, N [Centro de Investigacion en Ciencias e IngenierIa de Materiales and Escuela de Fisica, Universidad de Costa Rica, 2060 San Jose (Costa Rica)], E-mail: william.vargascastro@ucr.ac.cr

    2009-01-07

    Electron beam evaporated Pd-capped Gd thin films were deposited on quartz substrates and subsequently hydrided. Transmittance spectra of these bilayer systems, under unpolarized normal illumination, were obtained and used in an inversion approach from which the spectral dependence of the effective optical constants is obtained. The optical absorption coefficient of the {beta}-phase GdH{sub x} (with 1 < x {<=} 2) is reported. The semiconductor GdH{sub 2+y} state (with 0 < y {<=} 1) is characterized in terms of the optical absorption coefficient and the optical gap. By assuming a granular morphology of the films, with some of the grains in the metal GdH{sub 2} phase and other grains covered with a transition layer containing the semiconducting GdH{sub 2+y} phase, the hydrogen concentration dependence of the optical gap is shown and the optical absorption edge of the stoichiometric {gamma}-phase GdH{sub 3} is reported.

  16. Nanoindentation measurements of the mechanical properties of zirconium matrix and hydrides in unirradiated pre-hydrided nuclear fuel cladding

    Science.gov (United States)

    Rico, A.; Martin-Rengel, M. A.; Ruiz-Hervias, J.; Rodriguez, J.; Gomez-Sanchez, F. J.

    2014-09-01

    It is well known that the mechanical properties of the nuclear fuel cladding may be affected by the presence of hydrides. The average mechanical properties of hydrided cladding have been extensively investigated from a macroscopic point of view. In addition, the mechanical and fracture properties of bulk hydride samples fabricated from zirconium plates have also been reported. In this paper, Young's modulus, hardness and yield stress are measured for each phase, namely zirconium hydrides and matrix, of pre-hydrided nuclear fuel cladding. To this end, nanoindentation tests were performed on ZIRLO samples in as-received state, on a hydride blister and in samples with 150 and 1200 ppm of hydrogen homogeneously distributed along the hoop direction of the cladding. The results show that the measured mechanical properties of the zirconium hydrides and ZIRLO matrix (Young's modulus, hardness and yield stress) are rather similar. From the experimental data, the hydride volume fraction in the cladding samples with 150 and 1200 ppm was estimated and the average mechanical properties were calculated by means of the rule of mixtures. These values were compared with those obtained from ring compression tests. Good agreement between the results obtained by both methods was found.

  17. Nanoindentation measurements of the mechanical properties of zirconium matrix and hydrides in unirradiated pre-hydrided nuclear fuel cladding

    Energy Technology Data Exchange (ETDEWEB)

    Rico, A., E-mail: alvaro.rico@urjc.es [DIMME, Departamento de Tecnología Mecánica, Universidad Rey Juan Carlos, c/Tulipán s/n, E-28933 Móstoles, Madrid (Spain); Martin-Rengel, M.A., E-mail: mamartin@mater.upm.es [Departamento de Ciencia de los Materiales, UPM, E.T.S.I. Caminos, Canales y Puertos, Profesor Aranguren SN, E-28040 Madrid (Spain); Ruiz-Hervias, J., E-mail: jesus.ruiz@upm.es [Departamento de Ciencia de los Materiales, UPM, E.T.S.I. Caminos, Canales y Puertos, Profesor Aranguren SN, E-28040 Madrid (Spain); Rodriguez, J. [DIMME, Departamento de Tecnología Mecánica, Universidad Rey Juan Carlos, c/Tulipán s/n, E-28933 Móstoles, Madrid (Spain); Gomez-Sanchez, F.J., E-mail: javier.gomez@amsimulation.com [Advanced Material Simulation, S.L, Madrid (Spain)

    2014-09-15

    It is well known that the mechanical properties of the nuclear fuel cladding may be affected by the presence of hydrides. The average mechanical properties of hydrided cladding have been extensively investigated from a macroscopic point of view. In addition, the mechanical and fracture properties of bulk hydride samples fabricated from zirconium plates have also been reported. In this paper, Young’s modulus, hardness and yield stress are measured for each phase, namely zirconium hydrides and matrix, of pre-hydrided nuclear fuel cladding. To this end, nanoindentation tests were performed on ZIRLO samples in as-received state, on a hydride blister and in samples with 150 and 1200 ppm of hydrogen homogeneously distributed along the hoop direction of the cladding. The results show that the measured mechanical properties of the zirconium hydrides and ZIRLO matrix (Young’s modulus, hardness and yield stress) are rather similar. From the experimental data, the hydride volume fraction in the cladding samples with 150 and 1200 ppm was estimated and the average mechanical properties were calculated by means of the rule of mixtures. These values were compared with those obtained from ring compression tests. Good agreement between the results obtained by both methods was found.

  18. The influence of hydride on fracture toughness of recrystallized Zircaloy-4 cladding

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Hsiao-Hung, E-mail: 175877@mail.csc.com.tw [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China); China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chiang, Ming-Feng [China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chen, Yen-Chen [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China)

    2014-04-01

    In this work, RXA cladding tubes were hydrogen-charged to target hydrogen content levels between 150 and 800 wppm (part per million by weight). The strings of zirconium hydrides observed in the cross sections are mostly oriented in the circumferential direction. The fracture toughness of hydrided RXA Zircaloy-4 cladding was measured to evaluate its hydride embrittlement susceptibility. With increasing hydrogen content, the fracture toughness of hydrided RXA cladding decreases at both 25 °C and 300 °C. Moreover, highly localized hydrides (forming a hydride rim) aggravate the degradation of the fracture properties of RXA Zircaloy-4 cladding at both 25 °C and 300 °C. Brittle features in the form of quasi-cleavages and secondary cracks were observed on the fracture surface of the hydride rim, even for RXA cladding tested at 300 °C.

  19. Uranium Hydride Nucleation and Growth Model FY'16 ESC Annual Report

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Mary Ann [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Richards, Andrew Walter [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Schulze, Roland K. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-12-20

    Uranium hydride corrosion is of great interest to the nuclear industry. Uranium reacts with water and/or hydrogen to form uranium hydride which adversely affects material performance. Hydride nucleation is influenced by thermal history, mechanical defects, oxide thickness, and chemical defects. Information has been gathered from past hydride experiments to formulate a uranium hydride model to be used in a Canned Subassembly (CSA) lifetime prediction model. This multi-scale computer modeling effort started in FY’13, and the fourth generation model is now complete. Additional high-resolution experiments will be run to further test the model.

  20. Study on Kinetics of Hydrogen Absorption by Metal Hydride Slurries Ⅰ. Absorption of Hydrogen by Hydrogen Storage Alloy MlNi5 Suspended in Benzene

    Institute of Scientific and Technical Information of China (English)

    安越; 陈长聘; 徐国华; 蔡官明; 王启东

    2002-01-01

    The absorption of hydrogen was studied in metal hydride slurry, which is formed by benzene and hydrogen storage alloy powder. The influence of temperature on the rate of absorption was discussed using three-phase mass transfer model. It is also concluded that the suitable absorption temperature is 313 K.

  1. High-pressure synthesis of noble metal hydrides.

    Science.gov (United States)

    Donnerer, Christian; Scheler, Thomas; Gregoryanz, Eugene

    2013-04-07

    The formation of hydride phases in the noble metals copper, silver, and gold was investigated by in situ x-ray diffraction at high hydrogen pressures. In the case of copper, a novel hexagonal hydride phase, Cu2H, was synthesised at pressures above 18.6 GPa. This compound exhibits an anti-CdI2-type structure, where hydrogen atoms occupy every second layer of octahedral interstitial sites. In contrast to chemically produced CuH, this phase does not show a change in compressibility compared to pure copper. Furthermore, repeated compression (after decomposition of Cu2H) led to the formation of cubic copper hydride at 12.5 GPa, a phenomenon attributed to an alteration of the microstructure during dehydrogenation. No hydrides of silver (up to 87 GPa) or gold (up to 113 GPa) were found at both room and high temperatures.

  2. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form,

  3. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  4. Destabilization of magnesium hydride through interface engineering

    NARCIS (Netherlands)

    Mooij, L.P.A.

    2013-01-01

    The aim of this thesis is to study the thermodynamics of hydrogenation of nanoconfined magnesium within a thin film multilayer model system. Magnesium hydride is a potential material for hydrogen storage, which is a key component in a renewable energy system based on hydrogen. In bulk form, magnesiu

  5. Development of gallium nitride-based ultraviolet and visible light-emitting diodes using hydride vapor-phase epitaxy and molecular beam epitaxy

    Science.gov (United States)

    Cabalu, Jasper Sicat

    Much of the work done on ultraviolet (UV) and visible III-Nitrides-based light emitting diodes (LEDs) involves growth by metal-organic chemical vapor deposition (MOCVD). In this dissertation, the growth, development, and fabrication of III-Nitrides-based UV and visible LEDs with very high photon conversion and extraction efficiencies using hydride vapor-phase epitaxy (HVPE) and radio frequency (rf) plasma-assisted molecular beam epitaxy (PAMBE) is presented. High-power electrically-pumped UV-LEDs based on GaN/AlGaN multiple quantum wells (MQWs) emitting at 340 nm and 350 nm have been fabricated in a flip-chip configuration and evaluated. Under pulsed operation, UV-LEDs emitting at 340 nm have output powers that saturate, due to device heating, at approximately 3 mW. Devices emitting at 350 nm show DC operation output powers as high as 4.5 mW under 200 mA drive current. These results were found to be equivalent with those of UV-LEDs produced by the MOCVD and HVPE methods. The concept of using textured MQWs on UV-LED structures was tested by optical pumping of GaN/AlGaN MQWs grown on textured GaN templates. Results show highly enhanced (>700 times) blue-shifted photoluminescence (PL) at 360 nm compared to similarly produced MQWs on smooth GaN templates whose PL emission is red-shifted. These results are attributed partly to enhancement in light extraction efficiency (LEE) and partly to enhancement in internal quantum efficiency (IQE). The origin of the increase in IQE is partly due to reduction of the quantum-confined Stark effect (QCSE) on QW-planes not perpendicular to the polarization direction and partly due to charge redistribution in the QWs caused by the polarization component parallel to the planes of the QWs. Similar studies have been done for visible LEDs using InGaN/GaN MQWs. Growth of LED structures on textured GaN templates employing textured MQW-active regions resulted in the production of dichromatic (430 nm and 530 nm) phosphorless white LEDs with

  6. Effects of AlN nucleation layers on the growth of AlN films using high temperature hydride vapor phase epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Balaji, M. [Science et Ingenierie des Materiaux et des Procedes, Grenoble INP-CNRS-UJF, BP 75, 38402 Saint Martin d' Heres (France); ACERDE, 452 rue des sources, 38920 Crolles (France); Crystal Growth Centre, Anna University-Chennai, Chennai 600025 (India); Claudel, A. [ACERDE, 452 rue des sources, 38920 Crolles (France); Fellmann, V. [Science et Ingenierie des Materiaux et des Procedes, Grenoble INP-CNRS-UJF, BP 75, 38402 Saint Martin d' Heres (France); Gelard, I. [ACERDE, 452 rue des sources, 38920 Crolles (France); Blanquet, E., E-mail: elisabeth.blanquet@simap.grenoble-inp.fr [Science et Ingenierie des Materiaux et des Procedes, Grenoble INP-CNRS-UJF, BP 75, 38402 Saint Martin d' Heres (France); Boichot, R. [Science et Ingenierie des Materiaux et des Procedes, Grenoble INP-CNRS-UJF, BP 75, 38402 Saint Martin d' Heres (France); Pierret, A. [Departement de Mesures Physiques, ONERA, Chemin de la Huniere, 91761 Palaiseau Cedex (France); CEA-CNRS Group ' NanoPhysique et SemiConducteurs' , INAC/SP2M/NPSC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble, Cedex 9 (France); and others

    2012-06-15

    Highlights: Black-Right-Pointing-Pointer Growth of AlN Nucleation layers and its effect on high temperature AlN films quality were investigated. Black-Right-Pointing-Pointer AlN nucleation layers stabilizes the epitaxial growth of AlN and improves the surface morphology of AlN films. Black-Right-Pointing-Pointer Increasing growth temperature of AlN NLs as well as AlN films improves the structural quality and limits the formation of cracks. - Abstract: AlN layers were grown on c-plane sapphire substrates with AlN nucleation layers (NLs) using high temperature hydride vapor phase epitaxy (HT-HVPE). Insertion of low temperature NLs, as those typically used in MOVPE process, prior to the high temperature AlN (HT-AlN) layers has been investigated. The NLs surface morphology was studied by atomic force microscopy (AFM) and NLs thickness was measured by X-ray reflectivity. Increasing nucleation layer deposition temperature from 650 to 850 Degree-Sign C has been found to promote the growth of c-oriented epitaxial HT-AlN layers instead of polycrystalline layers. The growth of polycrystalline layers has been related to the formation of dis-oriented crystallites. The density of such disoriented crystallites has been found to decrease while increasing NLs deposition temperature. The HT-AlN layers have been characterized by X-ray diffraction {theta} - 2{theta} scan and (0 0 0 2) rocking curve measurement, Raman and photoluminescence spectroscopies, AFM and field emission scanning electron microscopy. Increasing the growth temperature of HT-AlN layers from 1200 to 1400 Degree-Sign C using a NL grown at 850 Degree-Sign C improves the structural quality as well as the surface morphology. As a matter of fact, full-width at half-maximum (FWHM) of 0 0 0 2 reflections was improved from 1900 to 864 arcsec for 1200 Degree-Sign C and 1400 Degree-Sign C, respectively. Related RMS roughness also found to decrease from 10 to 5.6 nm.

  7. Chemistry in a Forming Protoplanetary Disk: Main Accretion Phase

    Science.gov (United States)

    Yoneda, Haruaki; Tsukamoto, Yusuke; Furuya, Kenji; Aikawa, Yuri

    2016-12-01

    We investigate the chemistry in a radiation-hydrodynamics model of a star-forming core that evolves from a cold (˜10 K) prestellar core to the main accretion phase in ˜105 years. A rotationally supported gravitationally unstable disk is formed around a protostar. We extract the temporal variation of physical parameters in ˜1.5 × 103 SPH particles that end up in the disk, and perform post-processing calculations of the gas-grain chemistry adopting a three-phase model. Inside the disk, the SPH particles migrate both inward and outward. Since a significant fraction of volatiles such as CO can be trapped in the water-dominant ice in the three-phase model, the ice mantle composition depends not only on the current position in the disk, but also on whether the dust grain has ever experienced higher temperatures than the water sublimation temperature. Stable molecules such as H2O, CH4, NH3, and CH3OH are already abundant at the onset of gravitational collapse and are simply sublimated as the fluid parcels migrate inside the water snow line. On the other hand, various molecules such as carbon chains and complex organic molecules (COMs) are formed in the disk. The COMs abundance sensitively depends on the outcomes of photodissociation and diffusion rates of photofragments in bulk ice mantle. As for S-bearing species, H2S ice is abundant in the collapse phase. In the warm regions in the disk, H2S is sublimated to be destroyed, while SO, H2CS, OCS, and SO2 become abundant.

  8. Understanding of Hydriding Mechanisms of Zircaloy-4 Alloy during Corrosion in PWR Simulated Conditions and Influence of Zirconium Hydrides on Zircaloy-4 Corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Bisor-Melloul, C.; Tupin, M.; Bossis, P.; Chene, J.; Bechade, J.L. [CEA Saclay, 91 - Gif sur Yvette (France); Motta, A. [Pennsylvania State Univ. (United States)

    2011-03-15

    Zirconium alloys represent the first containment barrier to fission products, their mechanical integrity is essential for nuclear safety in PWR. During their corrosion in primary water, some of the hydrogen involved in the oxidation reaction with water ingresses into the alloy through the oxide layer. In the metallic matrix, once the solid solution limit is reached at the irradiation temperature, hydrogen precipitates as Zr hydrides mainly located just under the metal/oxide interface due to the thermal gradient across the cladding. As these hydrides may contribute to a larger oxide thickness and to a more fragile behaviour of the cladding, the minimization of hydrogen pick-up is required. Accordingly, since the Zircaloy-4 (Zr-1.3Sn-0.2Fe-0.1Cr) alloy is known to be sensitive to this phenomenon, the understanding of its hydriding mechanism, isotopic exchanges were carried out in D{sub 2}O environment at 360 C and led to the localization, in the oxide scales, of the limiting step for the hydrogen diffusion. To estimate an apparent diffusion coefficient of hydrogen in the oxide formed on Zircaloy-4, we based on SIMS profiles and penetration depth of deuterium in the dense part of the oxide film. Then ERDA estimation of the hydrogen content in zirconia and fusion measurement of the hydrogen content in both metal and oxide were used to estimate a hydrogen flux absorbed by the alloy and hence to deduce an apparent diffusion coefficient. Finally, these 2 methods lead to quite similar values (between 1.10{sup -14} cm{sup 2}/s and 6.10{sup -14} cm{sup 2}/s) which are in accordance with bibliography. Concerning the impact of hydrides on the corrosion of Zircaloy-4, several pre-hydrided and reference samples were corroded simultaneously at 360 C. The characterization of the pre-hydrided samples revealed some changes, as the presence of the Zr{sub 3}O sub-oxide at the inner metal/oxide interface, a lower fraction of -ZrO{sub 2} in the oxide and a faster diffusion of oxygen

  9. Submillimeter Spectroscopy of Hydride Molecules

    Science.gov (United States)

    Phillips, T. G.

    1998-05-01

    Simple hydride molecules are of great importance in astrophysics and astrochemistry. Physically they dominate the cooling of dense, warm phases of the ISM, such as the cores and disks of YSOs. Chemically they are often stable end points of chemical reactions, or may represent important intermediate stages of the reaction chains, which can be used to test the validity of the process. Through the efforts of astronomers, physicists, chemists, and laboratory spectroscopists we have an approximate knowledge of the abundance of some of the important species, but a great deal of new effort will be required to achieve the comprehensive and accurate data set needed to determine the energy balance and firmly establish the chemical pathways. Due to the low moment of inertia, the hydrides rotate rapidly and so have their fundamental spectral lines in the submillimeter. Depending on the cloud geometry and temperature profile they may be observed in emission or absorption. Species such as HCl, HF, OH, CH, CH(+) , NH_2, NH_3, H_2O, H_2S, H_3O(+) and even H_3(+) have been detected, but this is just a fraction of the available set. Also, most deduced abundances are not nearly sufficiently well known to draw definitive conclusions about the chemical processes. For example, the most important coolant for many regions, H_2O, has a possible range of deduced abundance of a factor of 1000. The very low submillimeter opacity at the South Pole site will be a significant factor in providing a new capabilty for interstellar hydride spectroscopy. The new species and lines made available in this way will be discussed.

  10. Chemistry in a forming protoplanetary disk: main accretion phase

    CERN Document Server

    Yoneda, Haruaki; Furuya, Kenji; Aikawa, Yuri

    2016-01-01

    We investigate the chemistry in a radiation-hydrodynamics model of star-forming core which evolves from a cold ($\\sim 10$ K) prestellar core to the main accretion phase in $\\sim 10^5$ yr. A rotationally-supported gravitationally unstable disk is formed around a protostar. We extract the temporal variation of physical parameters in $\\sim 1.5 \\times 10^3$ SPH particles which end up in the disk, and perform post-processing calculations of the gas-grain chemistry adopting a three-phase model. Inside the disk, the SPH particles migrate both inward and outward. Since a significant fraction of volatiles such as CO can be trapped in the water-dominant ice in the three-phase model, the ice mantle composition depends not only on the current position in the disk but also on whether the dust grain has ever experienced higher temperatures than the water sublimation temperature. Stable molecules such as H$_2$O, CH$_4$, NH$_3$ and CH$_3$OH are already abundant at the onset of gravitational collapse and simply sublimated as ...

  11. Filiform-mode hydride corrosion of uranium surfaces

    Science.gov (United States)

    Hill, M. A.; Schulze, R. K.; Bingert, J. F.; Field, R. D.; McCabe, R. J.; Papin, P. A.

    2013-11-01

    Hydride nucleation and growth has previously been studied in uranium with an air-formed oxide. Preferred directional growth of uranium hydride has not been observed, presumably due to the constraint of the oxide layer and/or the presence of a surface layer distorted by mechanical grinding and polishing. Instead, hydrides typically first form as subsurface blisters that do not exhibit preferred growth directionality. By eliminating the strained surface layer through electropolishing, removing the natural oxide through ion sputtering, avoiding exposure of the uranium to air, and then exposing uranium to high purity hydrogen in an environmental cell, hydride growth patterns emerge that correspond to defect structures within the microstructure. These hydride growth patterns are similar to filiform corrosion, a type of corrosion that frequently forms under thin protective films. This work describes the first reported observation of filiform-like corrosion in uranium. The uranium hydride initiates at defects, but grows into filaments up to 20 μm wide, and tends to form in straight lines, largely propagating along twin boundaries. Propagation is driven by hydrogen reaction at the filament head, promoted by more efficient delivery of reactant. However, this phenomenon does not involve an electrochemical process associated with conventional filiform corrosion and is therefore described as filiform-like. Hydride growth was observed using optical microscopy for a period of nearly three years. Sample characterization included automated electron backscatter diffraction (EBSD) measurements to determine growth directions. Observation of this anomalous hydride growth provides clues as to the mechanisms operating in uranium hydriding for more conventionally prepared sample surfaces.

  12. Relationship between H2 sorption properties and aqueous corrosion mechanisms in A2Ni7 hydride forming alloys (A = Y, Gd or Sm)

    Science.gov (United States)

    Charbonnier, Véronique; Monnier, Judith; Zhang, Junxian; Paul-Boncour, Valérie; Joiret, Suzanne; Puga, Beatriz; Goubault, Lionel; Bernard, Patrick; Latroche, Michel

    2016-09-01

    Intermetallic compounds A2B7 (A = rare earth, B = transition metal) are of interest for Ni-MH batteries. Indeed they are able to absorb hydrogen reversibly and exhibit good specific capacity in electrochemical route. To understand the effect of rare earth on properties of interest such as thermodynamic, cycling stability and corrosion, we synthesized and studied three compounds: Y2Ni7, Gd2Ni7 and Sm2Ni7. Using Sieverts' method, we plot P-c-isotherms up to 10 MPa and study hydride stability upon solid-gas cycling. Electrochemical cycling was also performed, as well as calendar and cycling corrosion study. Corrosion products were characterized by means of X-ray diffraction, electron diffraction, Raman micro-spectroscopy and scanning and transmission electron microscopies. Magnetic measurements were also performed to calculate corrosion rates. A corrosion mechanism, based on the nature of corrosion products, is proposed. By combining results from solid-gas cycling, electrochemical cycling and corrosion study, we attribute the loss in capacity either to corrosion or loss of crystallinity.

  13. Water in star-forming regions with Herschel (WISH). VI. Constraints on UV and X-ray irradiation from a survey of hydrides in low- to high-mass young stellar objects

    NARCIS (Netherlands)

    Benz, A. O.; Bruderer, S.; van Dishoeck, E. F.; Melchior, M.; Wampfler, S. F.; van der Tak, F.; Goicoechea, J. R.; Indriolo, N.; Kristensen, L. E.; Lis, D. C.; Mottram, J. C.; Bergin, E. A.; Caselli, P.; Herpin, F.; Hogerheijde, M. R.; Johnstone, D.; Liseau, R.; Nisini, B.; Tafalla, M.; Visser, R.; Wyrowski, F.

    2016-01-01

    Context. Hydrides are simple compounds containing one or a few hydrogen atoms bonded to a heavier atom. They are fundamental precursor molecules in cosmic chemistry and many hydride ions have become observable in high quality for the first time thanks to the Herschel Space Observatory. Ionized hydri

  14. Preliminary results on the determination of ultratrace amounts of cadmium in tea samples using a flow injection on-line solid phase extraction separation and preconcentration technique to couple with a sequential injection hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Duan, Taicheng; Song, Xuejie; Jin, Dan; Li, Hongfei; Xu, Jingwei; Chen, Hangting

    2005-10-31

    In this work, a method was developed for determination of ultra-trace levels of Cd in tea samples by atomic fluorescence spectrometry (AFS). A flow injection solid phase extraction (FI-SPE) separation and preconcentration technique, to on-line couple with a sequential injection hydride generation (SI-HG) technique is employed in this study. Cd was preconcentrated on the SPE column, which was made from a neutral extractant named Cyanex 923, while other matrix ions or interfering ions were completely or mostly separated off. Conditions for the SPE separation and preconcentration, as well as conditions for the HG technique, were studied. Due to the separation of interfering elements, Cd hydride generation efficiency could be greatly enhanced with the sole presence of Co(2+) with a concentration of 200mugL(-1), which is much lower than those in other works previously reported. Interferences on both the Cd separation and preconcentration, and Cd hydride generation (HG) were investigated; it showed that both the separation and preconcentration system, and the HG system had a strong anti-interference ability. The SPE column could be repeatedly used at least 400 times, a R.S.D. of 0.97% was obtained for 6 measurements of Cd with 0.2mugL(-1) and a correlation coefficiency of 1.0000 was obtained for the measurement of a series of solutions with Cd concentrations from 0.1 to 2mugL(-1). The method has a low detection limit of 10.8ngL(-1) for a 25mL solution and was successfully validated by using two tea standard reference materials (GBW08513 and GBW07605).

  15. Hydride structures in Ti-aluminides subjected to high temperature and hydrogen pressure charging conditions

    Science.gov (United States)

    Legzdina, D.; Robertson, I. M.; Birnbaum, H. K.

    1991-01-01

    The distribution and chemistry of hydrides produced in single and dual phase alloys with a composition near TiAl have been investigated by using a combination of TEM and X-ray diffraction techniques. The alloys were exposed at 650 C to 13.8 MPa of gaseous H2 for 100 h. In the single-phase gamma alloy, large hydrides preferentially nucleated on the grain boundaries and matrix dislocations and a population of small hydrides was distributed throughout the matrix. X-ray and electron diffraction patterns from these hydrides indicated that they have an fcc structure with a lattice parameter of 0.45 nm. EDAX analysis of the hydrides showed that they were enriched in Ti. The hydrides were mostly removed by vacuum annealing at 800 C for 24 h. On dissolution of the hydrides, the chemistry of hydride-free regions of the grain boundary returned to the matrix composition, suggesting that Ti segregation accompanied the hydride formation rather than Ti enrichment causing the formation of the hydride.

  16. Suppression of the critical temperature in binary vanadium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Dolan, M.D., E-mail: michael.dolan@csiro.au [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); McLennan, K.G. [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); Chandra, D. [Department of Chemical and Materials Engineering, University of Nevada, Reno, Reno, NV 89557 (United States); Kochanek, M.A. [CSIRO Energy Technology, 1 Technology Court, Pullenvale, QLD 4069 (Australia); Song, G. [CSIRO Process Science and Engineering, Gate 4, Normanby Rd, Clayton, VIC 3168 (Australia)

    2014-02-15

    Highlights: • Addition of 10 mol% Cr to V increases the β-hydride T{sub C} to >200 °C. • Addition of 10 mol% Ni to V increases the β-hydride T{sub C} to >400 °C. • Addition of 10 mol% Al to V decreases the β-hydride T{sub C} to <30 °C. • V{sub 90}Al{sub 10} membrane can be cycled to <30 °C under H{sub 2} without β-hydride formation. -- Abstract: The tendency of vanadium-based alloy membranes to embrittle is the biggest commercialisation barrier for this hydrogen separation technology. Excessive hydrogen absorption and the α → β hydride transition both contribute to brittle failure of these membranes. Alloying is known to reduce absorption, but the influence of alloying on hydride phase formation under conditions relevant to membrane operation has not been studied in great detail previously. Here, the effect of Cr, Ni, and Al alloying additions on V–H phase equilibrium has been studied using hydrogen absorption measurements and in situ X-ray diffraction studies. The addition of 10 mol% Ni increases the critical temperature for α + β hydride formation to greater than 400 °C, compared to 170 °C for V. Cr also increases the critical temperature, to between 200 and 300 °C. The addition of 10 mol% Al, however, suppresses the critical temperature to less than 30 °C, thereby enabling this material to be cycled thermally and hydrostatically while precluding formation of the β-hydride phase. This is despite Al also decreasing hydrogen absorption. The implication of this finding is that one of the mechanisms of brittle failure in vanadium-based hydrogen-selective membranes has been eliminated, thereby increasing the robustness of this material relative to V.

  17. High Energy Rate Forming Induced Phase Transition in Austenitic Steel

    Science.gov (United States)

    Kovacs, T.; Kuzsella, L.

    2017-02-01

    In this study, the effects of explosion hardening on the microstructure and the hardness of austenitic stainless steel have been studied. The optimum explosion hardening technology of austenitic stainless steel was researched. In case of the explosive hardening used new idea means indirect hardening setup. Austenitic stainless steels have high plasticity and can be cold formed easily. However, during cold processing the hardening phenomena always occurs. Upon the explosion impact, the deformation mechanism indicates a plastic deformation and this deformation induces a phase transformation (martensite). The explosion hardening enhances the mechanical properties of the material, includes the wear resistance and hardness [1]. In case of indirect hardening as function of the setup parameters specifically the flayer plate position the hardening increased differently. It was find a relationship between the explosion hardening setup and the hardening level.

  18. Oxidation of Alumina-Forming MAX Phases in Turbine Environments

    Science.gov (United States)

    Smialek, James; Garg, Anita; Harder, Bryan; Nesbitt, James; Gabb, Timothy; Gray, SImon

    2017-01-01

    Protective coatings for high temperature turbine components are based on YSZ thermal barriers and oxidation resistant, alumina-forming NiAl or NiCoCrAlY bond coats. Ti2AlC and Cr2AlC MAX phases are thus of special interest because of good oxidation resistance and CTE that can match Al2O3 and YSZ. Their alumina scales grow according to cubic kinetics due to grain growth in the scale, with initial heating dominated by fast TiO2 growth. Protective cubic kinetics are also found in high pressure burner rig tests of MAXthal 211 Ti2AlC, but with reduced rates due to volatile TiO(OH)2 formation in water vapor. YSZ-coatings on bulk Ti2AlC exhibit remarkable durability up to 1300C in furnace tests and at least a 25x life advantage compared to superalloys. At another extreme, Cr2AlC is resistant to low temperature Na2SO4 hot corrosion and exhibits thermal cycling stability bonded to a superalloy disk material. Accordingly, sputtered Cr2AlC coatings on disk specimens prevented hot corrosion detriments on LCF. Breakaway oxidation (Ti2AlC), scale spallation (Cr2AlC), interdiffusion, and processing as coatings still present serious challenges. However the basic properties of MAX phases provide some unusual opportunities for use in high temperature turbines.

  19. Structural stability of complex hydrides LiBH4 revisited

    DEFF Research Database (Denmark)

    Lodziana, Zbigniew; Vegge, Tejs

    2004-01-01

    A systematic approach to study the phase stability of LiBH4 based on ab initio calculations is presented. Three thermodynamically stable phases are identified and a new phase of Cc symmetry is proposed for the first time for a complex hydride. The x-ray diffraction pattern and vibrational spectra...

  20. Materials science of Mg-Ni-based new hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Orimo, S.; Fujii, H. [Hiroshima Univ. (Japan). Faculty of Integrated Arts and Sciences

    2001-02-01

    One of the advantageous functional properties of Mg alloys (or compounds) is to exhibit the reversible hydriding reaction. In this paper, we present our systematic studies regarding the relationship between nanometer- or atomistic-scale structures and the specific hydriding properties of the Mg-Ni binary system, such as(1) nanostructured (n)-Mg{sub 2}Ni, (2) a mixture of n-Mg{sub 2}Ni and amorphous (a)-MgNi,(3) pure a-MgNi, and(4) n-MgNi{sub 2}. Further studies on(5) an a-MgNi-based system for clarifying the effect of the short-range ordering on the structural and hydriding properties and(6) a MgNi{sub 2}-based system for synthesizing the new Laves phase structure are also presented. The materials science of Mg-Ni-based new hydrides will provide indispensable knowledge for practically developing the Mg alloys as hydrogen-storage materials. (orig.)

  1. Hydrogenation of cyclohexene with LaNi5−xAlxHn metal hydrides suspended in cyclohexane or ethanol

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, W.P.M. van

    1993-01-01

    The hydrogenation of cyclohexene on the metal hydride forming alloys LaNi4.8Al0.2, LaNi4.9Al0.1 and LaNi5, all suspended in cyclohexane and LaNi5 suspended in ethanol, has been investigated. Two sources for hydrogen are recognized: hydrogen supplied by the gas phase and hydrogen which is available i

  2. Hydrogenation of cyclohexene with LaNi5-xAlxHn metal hydrides, suspended in cyclohexane or ethanol

    NARCIS (Netherlands)

    Snijder, E.D.; Versteeg, G.F.; Swaaij, van W.P.M.

    1993-01-01

    The hydrogenation of cyclohexene on the metal hydride forming alloys LaNi4.8Al0.2, LaNi4.9Al0.1 and LaNi5, all suspended in cyclohexane and LaNi5 suspended in ethanol, has been investigated. Two sources for hydrogen are recognized: hydrogen supplied by the gas phase and hydrogen which is available i

  3. Air and metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Lampinen, M.; Noponen, T. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Applied Thermodynamics

    1998-12-31

    The main goal of the air and metal hydride battery project was to enhance the performance and manufacturing technology of both electrodes to such a degree that an air-metal hydride battery could become a commercially and technically competitive power source for electric vehicles. By the end of the project it was possible to demonstrate the very first prototype of the air-metal hydride battery at EV scale, achieving all the required design parameters. (orig.)

  4. Interstellar chemistry of nitrogen hydrides in dark clouds

    CERN Document Server

    Gal, Romane Le; Faure, Alexandre; Forêts, Guillaume Pineau des; Rist, Claire; Maret, Sébastien

    2013-01-01

    The aim of the present work is to perform a comprehensive analysis of the interstellar chemistry of nitrogen, focussing on the gas-phase formation of the smallest polyatomic species and in particular nitrogen hydrides. We present a new chemical network in which the kinetic rates of critical reactions have been updated based on recent experimental and theoretical studies, including nuclear spin branching ratios. Our network thus treats the different spin symmetries of the nitrogen hydrides self-consistently together with the ortho and para forms of molecular hydrogen. This new network is used to model the time evolution of the chemical abundances in dark cloud conditions. The steady-state results are analysed, with special emphasis on the influence of the overall amounts of carbon, oxygen, and sulphur. Our calculations are also compared with Herschel/HIFI observations of NH, NH$_2$, and NH$_3$ detected towards the external envelope of the protostar IRAS 16293-2422. The observed abundances and abundance ratios ...

  5. Direct observation of hydrides formation in cavity-grade niobium

    Directory of Open Access Journals (Sweden)

    F. Barkov

    2012-12-01

    Full Text Available Niobium is an important technological superconductor used to make radio frequency cavities for particle accelerators. Using laser confocal microscopy we have directly investigated hydride precipitates formation in cavity-grade niobium at 77 and 140 K. We have found that large hydrides were usually formed after chemical or mechanical treatments, which are known to lead to a strong degradation of the quality factor known as Q disease. From our experiments we can conclude that hydrides causing Q disease are islands with a characteristic thickness of ≳100  nm and in-plane dimensions 1–10  μm. Our results show that mechanical polishing uploads a lot of hydrogen into bulk niobium while electropolishing leads to a mild contamination. Vacuum treatments at 600–800°C are demonstrated to preclude large hydride formation in line with the absence of Q disease in similarly treated cavities.

  6. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    Science.gov (United States)

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  7. Hydrogen storage of a novel combined system of LiNH2-NaMgH3: synergistic effects of in situ formed alkali and alkaline-earth metal hydrides.

    Science.gov (United States)

    Li, Yongtao; Fang, Fang; Song, Yun; Li, Yuesheng; Sun, Dalin; Zheng, Shiyou; Bendersky, Leonid A; Zhang, Qingan; Ouyang, Liuzhang; Zhu, Min

    2013-02-07

    Bimetallic hydride NaMgH(3) is used for the first time as a vehicle to enhance hydrogen release and uptake from LiNH(2). The combination of NaMgH(3) with LiNH(2) at a molar ratio of 1 : 2 can release about 4.0 wt% of hydrogen without detectable NH(3) emission in the temperature range of 45 °C to 325 °C and exhibiting superior dehydrogenation as compared to individual NaH and/or MgH(2) combined with LiNH(2). A high capacity retention of about 75% resulting from the introduction of NaMgH(3) is also achieved in LiNH(2) as well as re-hydrogenation under milder conditions of 180 °C and 5 MPa H(2) pressure. These significant improvements are attributed to synergistic effects of in situ formed NaH and MgH(2)via the decomposition of NaMgH(3) where a succession of competing reactions from the cyclic consumption/recovery of NaH are involved and serve as a "carrier" for the ultra-rapid conveyance of the N-containing species between the [NH(2)](-) amide and the resulting [NH](2-) imide complexes.

  8. High ramp rate thermogravimetric analysis of zirconium(II) hydride and titanium(II) hydride

    Energy Technology Data Exchange (ETDEWEB)

    Licavoli, Joseph J., E-mail: jjlicavo@mtu.edu; Sanders, Paul G., E-mail: sanders@mtu.edu

    2015-09-20

    Highlights: • A unique arc image device has been proposed for high ramp rate thermogravimetry. • Powder oxidation influences decomposition kinetics at temperatures below 933 K. • Particle size has a negligible effect on TiH{sub 2} decomposition behavior. • Improvements to the device are required to conduct accurate kinetic analysis. - Abstract: Zirconium and titanium hydride are utilized in liquid phase metal foam processing techniques. This application results in immediate exposure to molten metal and almost immediate decomposition at high temperatures. Most decomposition characterization techniques utilize slow heating rates and are unable to capture the decomposition behavior of hydrides under foam processing conditions. In order to address this issue a specialized high ramp rate thermogravimetric analyzer was created from a xenon arc image refiner. In addition to thermogravimetry, complimentary techniques including X-ray diffraction and scanning electron microscopy were used to characterize hydride decomposition and compare the results to literature. Hydrides were partially oxidized and separated into particles size ranges to evaluate the influence of these factors on decomposition. Oxidizing treatments were found to decrease decomposition rate only at temperatures below 933 K (660 °C) while particle size effects appeared to be negligible. Several improvements to the unique TGA apparatus presented in the current work are suggested to allow reliable kinetic modeling and analysis.

  9. Optimization of Hydride Rim Formation in Unirradiated Zr 4 Cladding

    Energy Technology Data Exchange (ETDEWEB)

    Shimskey, Rick W.; Hanson, Brady D.; MacFarlan, Paul J.

    2013-09-30

    The purpose of this work is to build on the results reported in the M2 milestone M2FT 13PN0805051, document number FCRD-USED-2013-000151 (Hanson, 2013). In that work, it was demonstrated that unirradiated samples of zircaloy-4 cladding could be pre-hydrided at temperatures below 400°C in pure hydrogen gas and that the growth of hydrides on the surface could be controlled by changing the surface condition of the samples and form a desired hydride rim on the outside diameter of the cladding. The work performed at Pacific Northwest National Laboratory since the issuing of the M2 milestone has focused its efforts to optimize the formation of a hydride rim on available zircaloy-4 cladding samples by controlling temperature variation and gas flow control during pre-hydriding treatments. Surface conditioning of the outside surface was also examined as a variable. The results of test indicate that much of the variability in the hydride thickness is due to temperature variation occurring in the furnaces as well as how hydrogen gas flows across the sample surface. Efforts to examine other alloys, gas concentrations, and different surface conditioning plan to be pursed in the next FY as more cladding samples become available

  10. Novel fuel cell stack with coupled metal hydride containers

    Science.gov (United States)

    Liu, Zhixiang; Li, Yan; Bu, Qingyuan; Guzy, Christopher J.; Li, Qi; Chen, Weirong; Wang, Cheng

    2016-10-01

    Air-cooled, self-humidifying hydrogen fuel cells are often used for backup and portable power sources, with a metal hydride used as the hydrogen storage material. To provide a stable hydrogen flow to the fuel cell stack, heat must be provided to the metal hydride. Conventionally, the heat released from the exothermic reaction of hydrogen and oxygen in the fuel cell stack to the exhaust air is used to heat a separate metal hydride container. In this case, the heat is only partially used instead of being more closely coupled because of the heat transfer resistances in the system. To achieve better heat integration, a novel scheme is proposed whereby hydrogen storage and single fuel cells are more closely coupled. Based on this idea, metal hydride containers in the form of cooling plates were assembled between each pair of cells in the stack so that the heat could be directly transferred to a metal hydride container of much larger surface-to-volume ratio than conventional separate containers. A heat coupled fuel cell portable power source with 10 cells and 11 metal hydride containers was constructed and the experimental results show that this scheme is beneficial for the heat management of fuel cell stack.

  11. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

    Valøen, Lars Ole; Lasia, Andrzej; Jensen, Jens Oluf

    2002-01-01

    The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC......, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical...... hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were...

  12. Phase equilibria in model surfactants forming Langmuir monolayers.

    Science.gov (United States)

    Ramírez, E; Santana, A; Cruz, A; López, G E

    2007-12-14

    The study of Langmuir monolayers has generated the attention of researchers because of their unique properties and their not well understood phase equilibrium. These monolayers exhibit interesting phase diagrams where the unusual liquid-liquid equilibrium can be observed for a single component monolayer. Monte Carlo computer simulations in the virtual Gibbs ensemble were used to obtain the phase diagram of Langmuir monolayers. The liquid-vapor and liquid-liquid phase equilibria were considered by constructing the Cailletet-Mathias phase diagrams. By using the Ising model and the rectilinear approximations the identification of the critical properties for both equilibria was determined. These critical parameters were calculated as a function of the strength of the interaction between the surfactant molecules and the aqueous subphase. As a result, we have identified the coexistence between a liquid expanded state (LES)-vapor and the liquid condensed state-LES, in agreement with experimental and theoretical evidence in the literature. We obtained a clear separation of phases and a strong dependence on the strength of the solvent used. Namely, as the interaction between the solvent and the head of the surfactant increases, the critical properties also increase. Equilibrium states were characterized by computing thermodynamic quantities as a function of temperature and solvent strength.

  13. In Situ Investigation of Hydride Precipitation and Growth in Zircaloy-4 by Transmission Electron Microscopy%Zr-4合金中氢化物析出长大的透射电镜原位研究

    Institute of Scientific and Technical Information of China (English)

    彭剑超; 李强; 刘仁多; 姚美意; 周邦新

    2011-01-01

    用透射电子显微镜拉伸试样台原位研究了应力、电子束辐照以及第二相对Zr-4合金中氢化物析出和长大的影响.结果表明,在拉应力作用下,裂纹易于沿氢化物扩展,并在裂尖垂直于拉应力方向析出新的氢化物.氢化物在拉应力诱发下的析出、开裂、再析出……过程,导致了氢致延迟开裂.在较强的会聚电子束辐照下,Zr-4合金中的氢化物会分解,新的氢化物会围绕着附近的Zr(Fe,Cr)2第二相粒子析出,新析出的氢化物为面心立方结构的δ相.%The effects of stress, electron beam irradiation and second phase particles on zirconium hydride precipitation and growth in Zircaloy-4 were investigated using in-situ transmission electron microscope observation. Results show that with the tensile stress the cracks are likely to propagate along hydrides and new hydrides are formed at the crack tip along the vertical direction of the applied stress. A process of precipitation, cracking, re-precipitation and so on, induced by tensile stress, causes delayed hydride cracking (DHC). Under the high irradiation of converged electron beam, the hydrides decompose in the Zircaloy-4, and new hydrides prefer to precipitate around the unoxidized Zr(Fe, Cr>2 particles, and the re-precipitated hydrides are fcc-structure 8 phase.

  14. Multidimensional simulations of hydrides during fuel rod lifecycle

    Science.gov (United States)

    Stafford, D. S.

    2015-11-01

    In light water reactor fuel rods, waterside corrosion of zirconium-alloy cladding introduces hydrogen into the cladding, where it is slightly soluble. When the solubility limit is reached, the hydrogen precipitates into crystals of zirconium hydride which decrease the ductility of the cladding and may lead to cladding failure during dry storage or transportation events. The distribution of the hydride phase and the orientation of the crystals depend on the history of the spatial temperature and stress profiles in the cladding. In this work, we have expanded the existing hydride modeling capability in the BISON fuel performance code with the goal of predicting both global and local effects on the radial, azimuthal and axial distribution of the hydride phase. We compare results from 1D simulations to published experimental data. We demonstrate the new capability by simulating in 2D a fuel rod throughout a lifecycle that includes irradiation, short-term storage in the spent fuel pool, drying, and interim storage in a dry cask. Using the 2D simulations, we present qualitative predictions of the effects of the inter-pellet gap and the drying conditions on the growth of a hydride rim.

  15. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  16. Metal hydride air conditioner

    Institute of Scientific and Technical Information of China (English)

    YANG; Ke; DU; Ping; LU; Man-qi

    2005-01-01

    The relationship among the hydrogen storage properties, cycling characteristics and thermal parameters of the metal hydride air conditioning systems was investigated. Based on a new alloy selection model, three pairs of hydrogen storage alloys, LaNi4.4 Mn0.26 Al0.34 / La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1, LaNi4.61Mn0. 26 Al0.13/La0.6 Nd0.4 Ni4.8 Mn0.2 Cu0. 1 and LaNi4.61 Mn0.26 Al0.13/La0.6 Y0.4 Ni4.8 Mn0. 2, were selected as the working materials for the metal hydride air conditioning system. Studies on the factors affecting the COP of the system showed that higher COP and available hydrogen content need the proper operating temperature and cycling time,large hydrogen storage capacity, flat plateau and small hysterisis of hydrogen alloys, proper original input hydrogen content and mass ratio of the pair of alloys. It also needs small conditioning system was established by using LaNi4.61 Mn0.26 Al0. 13/La0.6 Y0.4 Ni4.8 Mn0.2 alloys as the working materials, which showed that under the operating temperature of 180℃/40℃, a low temperature of 13℃ was reached, with COP =0.38 and Wnet =0.09 kW/kg.

  17. Geoneutrino and Hydridic Earth model

    CERN Document Server

    Bezrukov, Leonid

    2013-01-01

    Uranium, Thorium and Potassium-40 abundances in the Earth were calculated in the frame of Hydridic Earth model. Terrestrial heat producton from U, Th and K40 decays was calculated also. We must admit the existance of Earth expansion process to understand the obtained large value of terrestrial heat producton. The geoneutrino detector with volume more than 5 kT (LENA type) must be constructed to definitely separate between Bulk Silicat Earth model and Hydridic Earth model.

  18. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  19. A nickel metal hydride battery for electric vehicles.

    Science.gov (United States)

    Ovshinsky, S R; Fetcenko, M A; Ross, J

    1993-04-09

    Widespread use of electric vehicles can have significant impact on urban air quality, national energy independence, and international balance of trade. An efficient battery is the key technological element to the development of practical electric vehicles. The science and technology of a nickel metal hydride battery, which stores hydrogen in the solid hydride phase and has high energy density, high power, long life, tolerance to abuse, a wide range of operating temperature, quick-charge capability, and totally sealed maintenance-free operation, is described. A broad range of multi-element metal hydride materials that use structural and compositional disorder on several scales of length has been engineered for use as the negative electrode in this battery. The battery operates at ambient temperature, is made of nontoxic materials, and is recyclable. Demonstration of the manufacturing technology has been achieved.

  20. Optical tweezers formed by pure phase pupil filter

    Science.gov (United States)

    Lv, Wei; You, Chenglong; Wang, Mei; Yun, Maojin

    2013-09-01

    The focusing properties of vector beams have attracted great attention and quickly became the subject of extensive worldwide research due to their applications in lithography, optical storage, microscopy, material processing, and optical trapping. Focusing properties of the radially polarized beam and generalized cylindrical vector beams in high numerical aperture system with designed pure phase filter are analyzed in detail by using vector Debye diffraction theory. By utilizing diffractive optical element to partly change the polarization of vector beams, the energy density of light field in the vicinity of focus is studied by the numerical analysis. Numerical simulation result shows that optical bubbles can be obtained by changing the composition and polarization of the incident beams. At last, optical tweezers are constituted by two optical bubbles around the focus.

  1. Nanostructured Magnesium Hydride for Reversible Hydrogen Storage

    Science.gov (United States)

    de Rango, P.; Chaise, A.; Fruchart, D.; Miraglia, S.; Marty, Ph.

    2013-05-01

    The aim of this work was to develop suitable materials to store hydrogen in a solid state. A systematic investigation of the co-milling process of magnesium hydride with a transition metal was undertaken in order to produce nanostructured and highly reactive powders. The initiating role of the transition metal was evidenced by in situ neutron diffraction experiments. High performances in terms of thermal and mechanical behavior were achieved introducing expanded graphite and compacting the mixture to form composite materials. Absorption and desorption kinetics have been measured versus temperature and H2 pressure.

  2. Complex rare-earth aluminum hydrides: mechanochemical preparation, crystal structure and potential for hydrogen storage.

    Science.gov (United States)

    Weidenthaler, Claudia; Pommerin, André; Felderhoff, Michael; Sun, Wenhao; Wolverton, Christopher; Bogdanović, Borislav; Schüth, Ferdi

    2009-11-25

    A novel type of complex rare-earth aluminum hydride was prepared by mechanochemical preparation. The crystal structure of the REAlH(6) (with RE = La, Ce, Pr, Nd) compounds was calculated by DFT methods and confirmed by preliminary structure refinements. The trigonal crystal structure consists of isolated [AlH(6)](3-) octahedra bridged via [12] coordinated RE cations. The investigation of the rare-earth aluminum hydrides during thermolysis shows a decrease of thermal stability with increasing atomic number of the RE element. Rare-earth hydrides (REH(x)) are formed as primary dehydrogenation products; the final products are RE-aluminum alloys. The calculated decomposition enthalpies of the rare-earth aluminum hydrides are at the lower end for reversible hydrogenation under moderate conditions. Even though these materials may require somewhat higher pressures and/or lower temperatures for rehydrogenation, they are interesting examples of low-temperature metal hydrides for which reversibility might be reached.

  3. Evaluation of hydride blisters in zirconium pressure tube in CANDU reactor

    Energy Technology Data Exchange (ETDEWEB)

    Cheong, Y. M.; Kim, Y. S.; Gong, U. S.; Kwon, S. C.; Kim, S. S.; Choo, K.N

    2000-09-01

    When the garter springs for maintaining the gap between the pressure tube and the calandria tube are displaced in the CANDU reactor, the sagging of pressure tube results in a contact to the calandria tube. This causes a temperature difference between the inner and outer surface of the pressure tube. The hydride can be formed at the cold spot of outer surface and the volume expansion by hydride dormation causes the blistering in the zirconium alloys. An incident of pressure tube rupture due to the hydride blisters had happened in the Canadian CANDU reactor. This report describes the theoretical development and models on the formation and growth of hydride blister and some experimental results. The evaluation methodology and non-destructive testing for hydride blister in operating reactors are also described.

  4. Hydride formation in core-shell alloyed metal nanoparticles

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2016-07-01

    The model and analysis presented are focused on hydride formation in nanoparticles with a Pd shell and a core formed by another metal. The arrangement of metal atoms is assumed to be coherent (no dislocations). The lattice strain distribution, elastic energy, and chemical potential of hydrogen atoms are scrutinized. The slope of the chemical potential (as a function of hydrogen uptake) is demonstrated to decrease with increasing the core volume, and accordingly the critical temperature for hydride formation and the corresponding hysteresis loops are predicted to decrease as well.

  5. A New Reducing Regent: Dichloroindium Hydride

    Institute of Scientific and Technical Information of China (English)

    A. BABA; I. SHIBATA; N. HAYASHI

    2005-01-01

    @@ 1Introduction Among the hydride derivatives of group 13 elements, various types of aluminum hydrides and boron hydrides have been employed as powerful reduction tools. Indium hydrides have not received much attention,whereas the synthesis of indium trihydride (InH3) was reported several decades ago[1]. There have been no precedents for monometallic indium hydrides having practical reactivity, while activated hydrides such as an ate complex LiPhn InH4-n (n = 0- 2) and phosphine-coordinated indium hydrides readily reduce carbonyl compounds. In view of this background, we focused on the development of dichloroindium hydrides (Cl2InH) as novel reducing agents that bear characteristic features in both ionic and radical reactions.

  6. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

    This thesis describes investigations on low-valent tantalum and niobium hydride and alkyl complexes, particularly the dicyclopentadienyl tantalum hydride olefin complexes Cp2Ta(H)L (L=olefin). ... Zie: Summary

  7. Iron Hydride Detection and Intramolecular Hydride Transfer in a Synthetic Model of Mono-Iron Hydrogenase with a CNS Chelate.

    Science.gov (United States)

    Durgaprasad, Gummadi; Xie, Zhu-Lin; Rose, Michael J

    2016-01-19

    We report the identification and reactivity of an iron hydride species in a synthetic model complex of monoiron hydrogenase. The hydride complex is derived from a phosphine-free CNS chelate that includes a Fe-C(NH)(═O) bond (carbamoyl) as a mimic of the active site iron acyl. The reaction of [((O═)C(HN)N(py)S(Me))Fe(CO)2(Br)] (1) with NaHBEt3 generates the iron hydride intermediate [((O═)C(HN)N(py)S(Me))Fe(H)(CO)2] (2; δFe-H = -5.08 ppm). Above -40 °C, the hydride species extrudes CH3S(-) via intramolecular hydride transfer, which is stoichiometrically trapped in the structurally characterized dimer μ2-(CH3S)2-[((O═)C(HN)N(Ph))Fe(CO)2]2 (3). Alternately, when activated by base ((t)BuOK), 1 undergoes desulfurization to form a cyclometalated species, [((O═)C(NH)NC(Ph))Fe(CO)2] (5); derivatization of 5 with PPh3 affords the structurally characterized species [((O═)C(NH)NC)Fe(CO)(PPh3)2] (6), indicating complex 6 as the common intermediate along each pathway of desulfurization.

  8. First-principles calculations of niobium hydride formation in superconducting radio-frequency cavities

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Denise C.; Cooley, Lance D.; Seidman, David N.

    2013-09-01

    Niobium hydride is suspected to be a major contributor to degradation of the quality factor of niobium superconducting radio-frequency (SRF) cavities. In this study, we connect the fundamental properties of hydrogen in niobium to SRF cavity performance and processing. We modeled several of the niobium hydride phases relevant to SRF cavities and present their thermodynamic, electronic, and geometric properties determined from calculations based on density-functional theory. We find that the absorption of hydrogen from the gas phase into niobium is exothermic and hydrogen becomes somewhat anionic. The absorption of hydrogen by niobium lattice vacancies is strongly preferred over absorption into interstitial sites. A single vacancy can accommodate six hydrogen atoms in the symmetrically equivalent lowest-energy sites and additional hydrogen in the nearby interstitial sites affected by the strain field: this indicates that a vacancy can serve as a nucleation center for hydride phase formation. Small hydride precipitates may then occur near lattice vacancies upon cooling. Vacancy clusters and extended defects should also be enriched in hydrogen, potentially resulting in extended hydride phase regions upon cooling. We also assess the phase changes in the niobium-hydrogen system based on charge transfer between niobium and hydrogen, the strain field associated with interstitial hydrogen, and the geometry of the hydride phases. The results of this study stress the importance of not only the hydrogen content in niobium, but also the recovery state of niobium for the performance of SRF cavities.

  9. Experimental comparison on heat transfer-enhancing component of metal hydride bed

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Hyun-goo, E-mail: hgkang@nfri.re.kr; Chung, Dong-you; Oh, Yun Hee; Chang, Min Ho; Yun, Sei-Hun

    2016-11-01

    Highlights: • Two small ZrCo metal hydride beds were developed. • Copper foam or fin as heat transfer-enhancing component are experimentally compared. • Copper foam bed is more efficient for uniform and rapid heating of metal hydride. • Copper foam bed is more efficient in removal of reaction heat during absorption. - Abstract: Metal hydride bed will be one of the key components for safe handling of tritium in fusion fuel cycle. In case of normal or emergency shutdown of fuel cycle, metal hydride bed installed in storage and delivery system (SDS) of tritium plant will absorb tritium gas in the system as soon as possible. Supply of hydrogen isotope gas to fueling system of fusion reactor will start from the metal hydride beds. Rapid delivery, rapid recovery including rapid heating and cooling are key issues. For better performance of metal hydride bed, various forms of heat transfer enhancing component or design can be applied. This study aims to help the selection of heat transfer enhancing component. Two small ZrCo beds with copper foam and copper fin were developed and experimented with hydrogen gas. Recovery and delivery performance, heating and cooling performance are compared. Experimental results show metal hydride bed with copper foam has improved performance. Uniform heating of metal hydride during desorption and removal of reaction heat during absorption are more efficient with copper foam bed than copper fin bed.

  10. Luminescent properties of aluminum hydride

    Energy Technology Data Exchange (ETDEWEB)

    Baraban, A.P.; Gabis, I.E.; Dmitriev, V.A. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Dobrotvorskii, M.A., E-mail: mstislavd@gmail.com [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Kuznetsov, V.G. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation); Matveeva, O.P. [National Mineral Resources University, Saint Petersburg 199106 (Russian Federation); Titov, S.A. [Petersburg State University of Railway Transport, Saint-Petersburg 190031 (Russian Federation); Voyt, A.P.; Elets, D.I. [Saint-Petersburg State University, Department of Physics, Saint-Petersburg 198504 (Russian Federation)

    2015-10-15

    We studied cathodoluminescence and photoluminescence of α-AlH{sub 3}– a likely candidate for use as possible hydrogen carrier in hydrogen-fueled vehicles. Luminescence properties of original α-AlH{sub 3} and α-AlH{sub 3} irradiated with ultraviolet were compared. The latter procedure leads to activation of thermal decomposition of α-AlH{sub 3} and thus has a practical implementation. We showed that the original and UV-modified aluminum hydride contain luminescence centers ‐ structural defects of the same type, presumably hydrogen vacancies, characterized by a single set of characteristic bands of radiation. The observed luminescence is the result of radiative intracenter relaxation of the luminescence center (hydrogen vacancy) excited by electrons or photons, and its intensity is defined by the concentration of vacancies, and the area of their possible excitation. UV-activation of the dehydrogenation process of aluminum hydride leads to changes in the spatial distribution of the luminescence centers. For short times of exposure their concentration increases mainly in the surface regions of the crystals. At high exposures, this process extends to the bulk of the aluminum hydride and ends with a decrease in concentration of luminescence centers in the surface region. - Highlights: • Aluminum hydride contains hydrogen vacancies which serve as luminescence centers. • The luminescence is the result of radiative relaxation of excited centers. • Hydride UV-irradiation alters distribution and concentration of luminescence centers.

  11. Photochemistry of Transition Metal Hydrides.

    Science.gov (United States)

    Perutz, Robin N; Procacci, Barbara

    2016-08-10

    Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

  12. Exploring "aerogen-hydride" interactions between ZOF2 (Z = Kr, Xe) and metal hydrides: An ab initio study

    Science.gov (United States)

    Esrafili, Mehdi D.; Mohammadian-Sabet, Fariba

    2016-06-01

    In this work, a new σ-hole interaction formed between ZOF2 (Z = Kr and Xe) as the Lewis acid and a series of metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CN, CH3) is reported. The nature of this interaction, called "aerogen-hydride" interaction, is unveiled by molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. Our results indicate that the aerogen-hydride interactions are quite strong and can be comparable in strength to other σ-hole bonds. An important charge-transfer interaction is also associated with the formation of OF2Z⋯HMX complexes.

  13. Simultaneous speciation of inorganic arsenic and antimony in water samples by hydride generation-double channel atomic fluorescence spectrometry with on-line solid-phase extraction using single-walled carbon nanotubes micro-column

    Energy Technology Data Exchange (ETDEWEB)

    Wu Hong, E-mail: wuhong1968@hotmail.com; Wang Xuecui; Liu Bing; Liu Yueling; Li Shanshan; Lu Jusheng; Tian Jiuying; Zhao Wenfeng; Yang Zonghui

    2011-01-15

    A new method was developed for the simultaneous speciation of inorganic arsenic and antimony in water by on-line solid-phase extraction coupled with hydride generation-double channel atomic fluorescence spectrometry (HG-DC-AFS). The speciation scheme involved the on-line formation and retention of the ammonium pyrrolidine dithiocarbamate complexes of As(III) and Sb(III) on a single-walled carbon nanotubes packed micro-column, followed by on-line elution and simultaneous detection of As(III) and Sb(III) by HG-DC-AFS; the total As and total Sb were determined by the same protocol after As(V) and Sb(V) were reduced by thiourea, with As(V) and Sb(V) concentrations obtained by subtraction. Various experimental parameters affecting the on-line solid-phase extraction and determination of the analytes species have been investigated in detail. With 180 s preconcentration time, the enrichment factors were found to be 25.4 for As(III) and 24.6 for Sb(III), with the limits of detection (LODs) of 3.8 ng L{sup -1} for As(III) and 2.1 ng L{sup -1} for Sb(III). The precisions (RSD) for five replicate measurements of 0.5 {mu}g L{sup -1} of As(III) and 0.2 {mu}g L{sup -1} of Sb(III) were 4.2 and 4.8%, respectively. The developed method was validated by the analysis of standard reference materials (NIST SRM 1640a), and was applied to the speciation of inorganic As and Sb in natural water samples.

  14. A study of advanced magnesium-based hydride and development of a metal hydride thermal battery system

    Science.gov (United States)

    Zhou, Chengshang

    Metal hydrides are a group of important materials known as energy carriers for renewable energy and thermal energy storage. A concept of thermal battery based on advanced metal hydrides is studied for heating and cooling of cabins in electric vehicles. The system utilizes a pair of thermodynamically matched metal hydrides as energy storage media. The hot hydride that is identified and developed is catalyzed MgH2 due to its high energy density and enhanced kinetics. TiV0.62Mn1.5, TiMn2, and LaNi5 alloys are selected as the matching cold hydride. A systematic experimental survey is carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. The results show that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Solid solution alloys of magnesium are exploited as a way to destabilize magnesium hydride thermodynamically. Various elements are alloyed with magnesium to form solid solutions, including indium and aluminum. Thermodynamic properties of the reactions between the magnesium solid solution alloys and hydrogen are investigated, showing that all the solid solution alloys that are investigated in this work have higher equilibrium hydrogen pressures than that of pure magnesium. Cyclic stability of catalyzed MgH2 is characterized and analyzed using a PCT Sievert-type apparatus. Three systems, including MgH2-TiH 2, MgH2-TiMn2, and MgH2-VTiCr, are examined. The hydrogenating and dehydrogenating kinetics at 300°C are stable after 100 cycles. However, the low temperature (25°C to 150°C) hydrogenation kinetics suffer a severe degradation during hydrogen cycling. Further experiments confirm that the low temperature kinetic degradation can be mainly related the extended hydrogenation-dehydrogenation reactions. Proof

  15. The effect of stress state on zirconium hydride reorientation

    Science.gov (United States)

    Cinbiz, Mahmut Nedim

    correlating the finite element stress-state results with the spatial distribution of hydride microstructures observed within the optical micrographs for each sample. Experiments showed that the hydride reorientation was enhanced as the stress biaxiality increased. The threshold stress decreased from 150 MPa to 80 MPa when stress biaxiality ratio increased from uniaxial tension to near-equibiaxial tension. This behavior was also predicted by classical nucleation theory based on the Gibbs free energy of transformation being assisted by the far-field stress. An analysis of in situ X-ray diffraction data obtained during a thermo-mechanical cycle typical of vacuum drying showed a complex lattice-spacing behavior of the hydride phase during the dissolution and precipitation. The in-plane hydrides showed bilinear lattice expansion during heating with the intrinsic thermal expansion rate of the hydrides being observed only at elevated temperatures as they dissolve. For radial hydrides that precipitate during cooling under stress, the spacing of the close-packed {111} planes oriented normal to the maximum applied stress was permanently higher than the corresponding {111} plane spacing in the other directions. This behavior is believed to be a result of a complex stress state within the precipitating plate-like hydrides that induces a strain component within the hydrides normal to its "plate" face (i.e., the applied stress direction) that exceeds the lattice spacing strains in the other directions. During heat-up, the lattice spacing of these same "plate" planes actually contract due to the reversion of the stress state within the plate-like hydrides as they dissolve. The presence of radial hydrides and their connectivity with in-plane hydrides was shown to increase the ductile-to-brittle transition temperature during tensile testing. This behavior can be understood in terms of the role of radial hydrides in promoting the initiation of a long crack that subsequently propagates under

  16. Superconductivity and unexpected chemistry of germanium hydrides under pressure

    Science.gov (United States)

    Davari Esfahani, M. Mahdi; Oganov, Artem R.; Niu, Haiyang; Zhang, Jin

    2017-04-01

    Following the idea that hydrogen-rich compounds might be high-Tc superconductors at high pressures, and the very recent breakthrough in predicting and synthesizing hydrogen sulfide with record-high Tc=203 K , an ab initio evolutionary algorithm for crystal structure prediction was employed to find stable germanium hydrides. In addition to the earlier structure of germane with space group Ama2, we propose a C2/m structure, which is energetically more favorable at pressures above 278 GPa (with inclusion of zero-point energy). Our calculations indicate that the C2/m phase of germane is a superconductor with Tc=67 K at 280 GPa. Germane is found to become thermodynamically unstable to decomposition to hydrogen and the compound Ge3H11 at pressures above 300 GPa. Ge3H11 with space group I 4 ¯m 2 is found to become stable at above 285 GPa with Tc=43 K . We find that the pressure-induced phase stability of germanium hydrides is distinct from analogous isoelectronic systems, e.g., Si hydrides and Sn hydrides. Superconductivity stems from large electron-phonon coupling associated with the wagging, bending, and stretching intermediate-frequency modes derived mainly from hydrogen.

  17. Development of a used fuel cladding damage model incorporating circumferential and radial hydride responses

    Science.gov (United States)

    Chen, Qiushi; Ostien, Jakob T.; Hansen, Glen

    2014-04-01

    At the completion of the fuel drying process, used fuel Zry4 cladding typically exhibits a significant population of δ-hydride inclusions. These inclusions are in the form of small platelets that are generally oriented both circumferentially and radially within the cladding material. There is concern that radially-oriented hydride inclusions may weaken the cladding material and lead to issues during used fuel storage and transportation processes. A high fidelity model of the mechanical behavior of hydrides has utility in both designing fuel cladding to be more resistant to this hydride-induced weakening and also in suggesting modifications to drying, storage, and transport operations to reduce the impact of hydride formation and/or the avoidance of loading scenarios that could overly stress the radial inclusions. We develop a mechanical model for the Zry4-hydride system that, given a particular morphology of hydride inclusions, allows the calculation of the response of the hydrided cladding under various loading scenarios. The model treats the Zry4 matrix material as J2 elastoplastic, and treats the hydrides as platelets oriented in predefined directions (e.g., circumferentially and radially). The model is hosted by the Albany analysis framework, where a finite element approximation of the weak form of the cladding boundary value problem is solved using a preconditioned Newton-Krylov approach. Instead of forming the required system Jacobian operator directly or approximating its action with a differencing operation, Albany leverages the Trilinos Sacado package to form the Jacobian via automatic differentiation. We present results that describe the performance of the model in comparison with as-fabricated Zry4 as well as HB Robinson fuel cladding. Further, we also present performance results that demonstrate the efficacy of the overall solution method employed to host the model.

  18. Development of a used fuel cladding damage model incorporating circumferential and radial hydride responses

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Qiushi, E-mail: qiushi@clemson.edu [Glenn Department of Civil Engineering, Clemson University, Clemson, SC 29634 (United States); Ostien, Jakob T., E-mail: jtostie@sandia.gov [Mechanics of Materials Dept. 8256, Sandia National Laboratories, P.O. Box 969, Livermore, CA 94551-0969 (United States); Hansen, Glen, E-mail: gahanse@sandia.gov [Computational Multiphysics Dept. 1443, Sandia National Laboratories, P.O. Box 5800, Albuquerque, NM 87185-1321 (United States)

    2014-04-01

    At the completion of the fuel drying process, used fuel Zry4 cladding typically exhibits a significant population of δ-hydride inclusions. These inclusions are in the form of small platelets that are generally oriented both circumferentially and radially within the cladding material. There is concern that radially-oriented hydride inclusions may weaken the cladding material and lead to issues during used fuel storage and transportation processes. A high fidelity model of the mechanical behavior of hydrides has utility in both designing fuel cladding to be more resistant to this hydride-induced weakening and also in suggesting modifications to drying, storage, and transport operations to reduce the impact of hydride formation and/or the avoidance of loading scenarios that could overly stress the radial inclusions. We develop a mechanical model for the Zry4-hydride system that, given a particular morphology of hydride inclusions, allows the calculation of the response of the hydrided cladding under various loading scenarios. The model treats the Zry4 matrix material as J{sub 2} elastoplastic, and treats the hydrides as platelets oriented in predefined directions (e.g., circumferentially and radially). The model is hosted by the Albany analysis framework, where a finite element approximation of the weak form of the cladding boundary value problem is solved using a preconditioned Newton–Krylov approach. Instead of forming the required system Jacobian operator directly or approximating its action with a differencing operation, Albany leverages the Trilinos Sacado package to form the Jacobian via automatic differentiation. We present results that describe the performance of the model in comparison with as-fabricated Zry4 as well as HB Robinson fuel cladding. Further, we also present performance results that demonstrate the efficacy of the overall solution method employed to host the model.

  19. Hydrogen Storage in Metal Hydrides

    Science.gov (United States)

    1990-08-01

    Hydrogen Storage Capacity Hydride by weight (%) [1) by volume (g/ml) [2] MgH2 7.00 0.101 Mg2NiH4 3.84 0,081 Mg2CuH4 2.04 - - 27 ...Include Security Classification) Hydrogen Storage in Metal Hydrides (U) 12. PERSONAL AUTHOR(S) DelaRosa, Mark J. 13a. TYPE OF REPORT 13b. TIME...objective of this program was to develop an economical process for pr-ducing a lightweight hydrogen storage medium by the chemical vapor infiltration

  20. Crystallography of shear transformations in zirconium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Cassidy, Michael Philip [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1978-01-01

    The crystallography and substructure of the transformations which have been hypothesized as involving a martensitic shear, and which occur between zirconium hydrides were investigated. Specifically, the formation of gamma zirconium hydride from delta hydride and the delta hydride to epsilon hydride transformation were studied. The habit planes, orientation relationships, lattice invariant shears, and interface structures were determined by transmission electron microscopy and diffraction. Surface tilts were observed and measured with an interference microscope. The direction and magnitude of the shape strain produced by the formation of gamma were determined by the measurement of fiducial scratch displacements. These results were compared with the phenomenological crystallographic theory of martensitic transformations.

  1. Examination of parameters affecting overload fracture behavior of flaw-tip hydrides in Zr-2.5Nb pressure tubes in Candu reactors

    Energy Technology Data Exchange (ETDEWEB)

    Cui, J.; Shek, G.K. [Kinectrics Inc., Toronto, Ontario (Canada); Wang, Z.R. [Toronto Univ., Dept. of Materials Science and Engineering, Toronto, Ontario (Canada)

    2007-07-01

    Service-induced flaws in Zr-2.5Nb alloy pressure tubes in Candu (Canada Deuterium Uranium Reactors) nuclear reactors are susceptible to a crack initiation and growth mechanism known as Delayed Hydride Cracking (DHC), which is a repetitive process that involves hydrogen diffusion, hydride precipitation, growth and fracture of a hydride region at the flaw-tip under a constant load. Crack initiation may also occur under another loading condition when the hydride region is subjected to an overload. An overload occurs when the hydride region at the flaw tip is loaded to a stress higher than that at which this region is formed such as when the reactor experiences a transient pressure higher than the normal operating pressure where the hydride region is formed. Flaw disposition requires justification that the hydride region overload will not fracture the hydride region, and initiate DHC. In this work, monotonically increasing load experiments were performed on unirradiated Zr-2.5Nb pressure tube specimens containing simulated debris frets (V-notch) and bearing pad frets (BPF, U-shape notch) to examine overload fracture behavior of flaw-tip hydrides formed under hydride ratcheting conditions. Hydride cracking in the overload tests was detected by the acoustic emission technique and confirmed by post-test metallurgical examination. Test results indicate that the resistance to overload fracture is affected by a number of parameters including hydride formation stress, flaw shape (V-notch vs. BPF) and flaw radius (0.015 mm vs. 0.1 mm). The notch-tip hydride morphologies were examined by optical microscopy and scanning electron microscopy (SEM) which show that they are affected by the hydride formation conditions, resulting in different overload fracture resistance. Finite element stress analyses were also performed to obtain flaw-tip stress distributions for interpretation of the test results. (authors)

  2. First-principles studies of phase stability and the structural and dynamical properties of metal hydrides. Progress report, September 15, 1991--September 14, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Chou, M.Y.

    1992-04-01

    This report discusses the following topics: calculation of the Structural Properties of Yttrium; dynamical and pairing properties of {alpha}-YH{chi}; electronic and structural properties of YH{sub 2} and YH{sub 3}; phase diagram of hydrogen on Ru(000); peierls distortion in hexagonal YH{sub 3}; and study of hydrogen in niobium and palladium.

  3. Effect of high heating rate on thermal decomposition behaviour of titanium hydride (TiH2) powder in air

    Indian Academy of Sciences (India)

    A Rasooli; M A Boutorabi; M Divandari; A Azarniya

    2013-04-01

    DTA and TGA curves of titanium hydride powder were determined in air at different heating rates. Also the thermal decomposition behaviour of the aforementioned powder at high heating rates was taken into consideration. A great breakthrough of the practical interest in the research was the depiction of the H2-time curves of TiH2 powder at various temperatures in air. In accordance with the results, an increase in heating rate to higher degrees does not change the process of releasing hydrogen from titanium hydride powder, while switching it from internal diffusion to chemical reaction. At temperatures lower than 600 °C, following the diffusion of hydrogen and oxygen atoms in titanium lattice, thin layers TiH phase and oxides form on the powder surface, controlling the process. On the contrary, from 700 °C later on, the process is controlled by oxidation of titanium hydride powder. In fact, the powder oxidation starts around 650 °C and may escalate following an increase in the heating rate too.

  4. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    Science.gov (United States)

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future.

  5. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Benjamin W.; Herberg, Julie L. (Lawrence Livermore National Laboratory, Livermore, CA); Highley, Aaron M.; Grossman, Jeffrey (MIT, Cambridge, MA); Wagner, Lucas (MIT, Cambridge, MA); Bhakta, Raghu; Peaslee, D. (University of Missouri, St. Louis, MO); Allendorf, Mark D.; Liu, X. (University of Missouri, St. Louis, MO); Behrens, Richard, Jr.; Majzoub, Eric H. (University of Missouri, St. Louis, MO)

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  6. Noether-Form Invariance of Nonholonomic Controllable Mechanical Systems in Phase Space

    Institute of Scientific and Technical Information of China (English)

    XIA Li-Li; LI Yuan-Cheng

    2007-01-01

    In this paper, we study the Noether-form invariance of nonholonomic mechanical controllable systems in phase space. Equations of motion of the controllable mechanical systems in phase space are presented. The definition and the criterion for this system are presented. A new conserved quantity and the Noether conserved quantity deduced from the Noether-form invariance are obtained. An example is given to illustrate the application of the results.

  7. Crystallization and Characterization of Galdieria sulphuraria RUBISCO in Two Crystal Forms: Structural Phase Transition Observed in P21 Crystal Form

    Directory of Open Access Journals (Sweden)

    Boguslaw Stec

    2007-10-01

    Full Text Available We have isolated ribulose-1,5-bisphosphate-carboxylase/oxygenase (RUBISCOfrom the red algae Galdieria Sulphuraria. The protein crystallized in two different crystalforms, the I422 crystal form being obtained from high salt and the P21 crystal form beingobtained from lower concentration of salt and PEG. We report here the crystallization,preliminary stages of structure determination and the detection of the structural phasetransition in the P21 crystal form of G. sulphuraria RUBISCO. This red algae enzymebelongs to the hexadecameric class (L8S8 with an approximate molecular weight 0.6MDa.The phase transition in G. sulphuraria RUBISCO leads from two hexadecamers to a singlehexadecamer per asymmetric unit. The preservation of diffraction power in a phasetransition for such a large macromolecule is rare.

  8. Determination of the mechanical properties of the hydrides of zirconium by nano indentation techniques; Determinacion de las propiedades mecanicas de los hidruros de circonio mediante tecnicas de nanoindentacion

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz Hervias, J.; Rico, A.; Martin Rengel, M. A.

    2013-07-01

    The mechanical properties of nuclear fuel cladding may be affected by the presence of hydrides. In most studies until now, the average mechanical properties of the zirconium matrix and the hydrides have been measured. In this paper, nano indentation techniques were used to assess the mechanical properties of both phases, namely the zirconium hydrides and matrix, separately. To this end, pre-hydrided cladding samples with 150 and 1200 ppm hydrogen were employed, and the elastic modulus, hardness and yield stress were obtained for both phases.

  9. Optimization of o-phtaldialdehyde/2-mercaptoethanol postcolumn reaction for the hydrophilic interaction liquid chromatography determination of memantine utilizing a silica hydride stationary phase.

    Science.gov (United States)

    Douša, Michal; Pivoňková, Veronika; Sýkora, David

    2016-08-01

    A rapid procedure for the determination of memantine based on hydrophilic interaction chromatography with fluorescence detection was developed. Fluorescence detection after postcolumn derivatization with o-phtaldialdehyde/2-mercaptoethanol was performed at excitation and emission wavelengths of 345 and 450 nm, respectively. The postcolumn reaction conditions such as reaction temperature, derivatization reagent flow rate, and reagents concentration were studied due to steric hindrance of amino group of memantine. The derivatization reaction was applied for the hydrophilic interaction liquid chromatography method which was based on Cogent Silica-C stationary phase with a mobile phase consisting of a mixture of 10 mmol/L citric acid and 10 mmol/L o-phosphoric acid (pH 6.0) with acetonitrile using an isocratic composition of 2:8 v/v. The benefit of the reported approach consists in a simple sample pretreatment and a quick and sensitive hydrophilic interaction chromatography method. The developed method was validated in terms of linearity, accuracy, precision, and selectivity according to the International Conference on Harmonisation guidelines. The developed method was successfully applied for the analysis of commercial memantine tablets.

  10. On the chemistry of hydrides of N atoms and O$^+$ ions

    CERN Document Server

    Awad, Zainab; Williams, David A

    2016-01-01

    Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low density lines of sight towards G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H$_2$ formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O$^+$ ions detected by Herschel/HIFI present along many sight lines in the Galaxy. The O$^+$ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic ray fluxes or in somewhat denser diffuse clouds with high cosmic ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

  11. Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity

    Energy Technology Data Exchange (ETDEWEB)

    Mosher, Daniel A.; Opalka, Susanne M.; Tang, Xia; Laube, Bruce L.; Brown, Ronald J.; Vanderspurt, Thomas H.; Arsenault, Sarah; Wu, Robert; Strickler, Jamie; Anton, Donald L.; Zidan, Ragaiy; Berseth, Polly

    2008-02-18

    between alkaline metal hydrides (AmH), Alkaline earth metal hydrides (AeH2), alane (AlH3), transition metal (Tm) hydrides (TmHz, where z=1-3) and molecular hydrogen (H2). The effort started first with variations of known alanates and subsequently extended the search to unknown compounds. In this stage, the FPM techniques were developed and validated on known alanate materials such as NaAlH4 and Na2LiAlH6. The coupled predictive methodologies were used to survey over 200 proposed phases in six quaternary spaces, formed from various combinations of Na, Li Mg and/or Ti with Al and H. A wide range of alanate compounds was examined using SSP having additions of Ti, Cr, Co, Ni and Fe. A number of compositions and reaction paths were identified having H weight fractions up to 5.6 wt %, but none meeting the 7.5 wt%H reversible goal. Similarly, MSP of alanates produced a number of interesting compounds and general conclusions regarding reaction behavior of mixtures during processing, but no alanate based candidates meeting the 7.5 wt% goal. A novel alanate, LiMg(AlH4)3, was synthesized using SBP that demonstrated a 7.0 wt% capacity with a desorption temperature of 150°C. The deuteride form was synthesized and characterized by the Institute for Energy (IFE) in Norway to determine its crystalline structure for related FPM studies. However, the reaction exhibited exothermicity and therefore was not reversible under acceptable hydrogen gas pressures for on-board recharging. After the extensive studies of alanates, the material class of emphasis was shifted to borohydrides. Through SBP, several ligand-stabilized Mg(BH4)2 complexes were synthesized. The Mg(BH4)2*2NH3 complex was found to change behavior with slightly different synthesis conditions and/or aging. One of the two mechanisms was an amine-borane (NH3BH3) like dissociation reaction which released up to 16 wt %H and more conservatively 9 wt%H when not including H2 released from the NH3. From FPM, the stability of the Mg(BH4

  12. Formation of palladium hydrides in low temperature Ar/H{sub 2}-plasma

    Energy Technology Data Exchange (ETDEWEB)

    Wulff, H., E-mail: wulff@uni-greifswald.de [University of Greifswald, Institute of Physics, Felix-Hausdorff-Straße 6, 17487 Greifswald (Germany); Quaas, M. [LITEC-LP, Brandteichstraße 20, 17489 Greifswald (Germany); Deutsch, H.; Ahrens, H. [University of Greifswald, Institute of Physics, Felix-Hausdorff-Straße 6, 17487 Greifswald (Germany); Fröhlich, M. [Leibniz Institute for Plasma Science and Technology e.V., Felix-Hausdorff-Straße 2 (Germany); Helm, C.A. [University of Greifswald, Institute of Physics, Felix-Hausdorff-Straße 6, 17487 Greifswald (Germany)

    2015-12-01

    20 nm thick Pd coatings deposited on Si substrates with 800 nm SiO{sub 2} and 1 nm Cr buffer layers were treated in a 2.45 GHz microwave plasma source at 700 W plasma power and 40 Pa working pressure without substrate heating. For obtaining information on the effect of energy influx due to ion energy on the palladium films the substrate potential was varied from U{sub sub} = 0 V to − 150 V at constant gas flow corresponding to mean ion energies E{sub i} from 0.22 eV ∙ cm{sup −2} ∙ s{sup −1} to 1.28 eV ∙ cm{sup −2} ∙ s{sup −1}. In contrast to high pressure reactions with metallic Pd, under plasma exposure we do not observe solid solutions over a wide range of hydrogen concentration. The hydrogen incorporation in Pd films takes place discontinuously. At 0 V substrate voltage palladium hydride is formed in two steps to PdH{sub 0.14} and PdH{sub 0.57}. At − 50 V substrate voltage PdH{sub 0.57} is formed directly. However, substrate voltages of − 100 V and − 150 V cause shrinking of the unit cell. We postulate the formation of two fcc vacancy palladium hydride clusters PdH{sub Vac}(I) and PdH{sub Vac}(II). Under longtime plasma exposure the fcc PdH{sub Vac}(II) phase forms cubic PdH{sub 1.33}. The fcc PdH{sub 0.57} phase decomposes at temperatures > 300 °C to form metallic fcc Pd. The hydrogen removal causes a decrease of lattice defects. In situ high temperature diffractometry measurements also confirm the existence of PdH{sub Vac}(II) as a palladium hydride phase. Stoichiometric relationship between cubic PdH{sub 1.33} and fcc PdH{sub Vac}(II) becomes evident from XR measurements and structure considerations. We assume both phases have the chemical composition Pd{sub 3}H{sub 4}. Up to 700 °C we observe phase transformation between both the fcc PdH{sub Vac}(II) and cubic PdH{sub 1.33} phases. These phase transformations could be explained analog to a Bain distortion by displacive solid state structural changes. - Highlights: • Thin Pd films

  13. Phase diagram of one-patch colloids forming tubes and lamellae.

    Science.gov (United States)

    Preisler, Zdenek; Vissers, Teun; Smallenburg, Frank; Munaò, Gianmarco; Sciortino, Francesco

    2013-08-15

    We numerically calculate the equilibrium phase diagram of one-patch particles with 30% patch coverage. It has been previously shown that in the fluid phase these particles organize into extremely long tubelike aggregates (G. Munaò et al. Soft Matter 2013, 9, 2652). Here, we demonstrate by means of free-energy calculations that such a disordered tube phase, despite forming spontaneously from the fluid phase below a density-dependent temperature, is always metastable against a lamellar crystal. We also show that a crystal of infinitely long packed tubes is thermodynamically stable, but only at high pressure. The full phase diagram of the model, beside the fluid phase, displays four different stable crystals. A gas-liquid critical point, and hence a liquid phase, is not detected.

  14. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  15. Method of forming a chemical composition

    Science.gov (United States)

    Bingham, Dennis N.; Wilding, Bruce M.; Klingler, Kerry M.; Zollinger, William T.; Wendt, Kraig M.

    2007-10-09

    A method of forming a chemical composition such as a chemical hydride is described and which includes the steps of selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of hydrogen; and exposing the selected composition to an amount of ionizing radiation to encourage the changing of the chemical bonds of the selected composition, and chemically reacting the selected composition with the source of hydrogen to facilitate the formation of a chemical hydride.

  16. The renaissance of hydrides as energy materials

    Science.gov (United States)

    Mohtadi, Rana; Orimo, Shin-Ichi

    2017-02-01

    Materials based on hydrides have been the linchpin in the development of several practical energy storage technologies, of which the most prominent example is nickel-metal hydride batteries. Motivated by the need to meet the future's energy demand, the past decade has witnessed substantial advancements in the research and development of hydrides as media for hydrogen energy storage. More recently, new and rapidly evolving discoveries have positioned hydrides as highly promising materials for future electrochemical energy storage, such as electrolytes for mono- and divalent batteries, and anodes for lithium-ion batteries. In addition, the potential of hydrides in efficient power transmission has been recently revealed. In this Review, we highlight key advances and illustrate how the versatility of hydrides has not only yielded a meaningful past, but also ensures a very bright future.

  17. Rechargeable metal hydrides for spacecraft application

    Science.gov (United States)

    Perry, J. L.

    1988-01-01

    Storing hydrogen on board the Space Station presents both safety and logistics problems. Conventional storage using pressurized bottles requires large masses, pressures, and volumes to handle the hydrogen to be used in experiments in the U.S. Laboratory Module and residual hydrogen generated by the ECLSS. Rechargeable metal hydrides may be competitive with conventional storage techniques. The basic theory of hydride behavior is presented and the engineering properties of LaNi5 are discussed to gain a clear understanding of the potential of metal hydrides for handling spacecraft hydrogen resources. Applications to Space Station and the safety of metal hydrides are presented and compared to conventional hydride storage. This comparison indicates that metal hydrides may be safer and require lower pressures, less volume, and less mass to store an equivalent mass of hydrogen.

  18. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions

    Science.gov (United States)

    Zhang, Xinxing; Wang, Haopeng; Ganteför, Gerd; Eichhorn, Bryan W.; Kiran, Boggavarapu; Bowen, Kit H.

    2016-10-01

    Numerous previously unknown carbon aluminum hydride cluster anions were generated in the gas phase, identified by time-of-flight mass spectrometry and characterized by anion photoelectron spectroscopy, revealing their electronic structure. Density functional theory calculations on the CAl5-9H- and CAl5-7H2- found that several of them possess unusually high carbon atom coordination numbers. These cluster compositions have potential as the basis for new energetic materials.

  19. Aluminum Hydride as a Fuel Supplement to NanoThermites

    Science.gov (United States)

    2014-01-01

    explosives and as a hydrogen storage medium. There are as many as six crystalline phases of alane, of which α-alane is themost stable and is also the...a pure nanoaluminum-corresponding metal oxide thermite. As Fig. 2 shows, the addition ofmicron-scale aluminum hydride to a nanoaluminum–copper-oxide... hydrogen does not participate in the thermite reaction. It is quite possible that the hydrogen may react with oxygen and or the metal oxide as an

  20. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

    Full Text Available Complex hydride systems for hydrogen (H2 generation for supplying fuel cells are being reviewed. In the first group, the hydride systems that are capable of generating H2 through a mechanical dehydrogenation phenomenon at the ambient temperature are discussed. There are few quite diverse systems in this group such as lithium alanate (LiAlH4 with the following additives: nanoiron (n-Fe, lithium amide (LiNH2 (a hydride/hydride system and manganese chloride MnCl2 (a hydride/halide system. Another hydride/hydride system consists of lithium amide (LiNH2 and magnesium hydride (MgH2, and finally, there is a LiBH4-FeCl2 (hydride/halide system. These hydride systems are capable of releasing from ~4 to 7 wt.% H2 at the ambient temperature during a reasonably short duration of ball milling. The second group encompasses systems that generate H2 at slightly elevated temperature (up to 100 °C. In this group lithium alanate (LiAlH4 ball milled with the nano-Fe and nano-TiN/TiC/ZrC additives is a prominent system that can relatively quickly generate up to 7 wt.% H2 at 100 °C. The other hydride is manganese borohydride (Mn(BH42 obtained by mechano-chemical activation synthesis (MCAS. In a ball milled (2LiBH4 + MnCl2 nanocomposite, Mn(BH42 co-existing with LiCl can desorb ~4.5 wt.% H2 at 100 °C within a reasonable duration of dehydrogenation. Practical application aspects of hydride systems for H2 generation/storage are also briefly discussed.

  1. Use of reversible hydrides for hydrogen storage

    Science.gov (United States)

    Darriet, B.; Pezat, M.; Hagenmuller, P.

    1980-01-01

    The addition of metals or alloys whose hydrides have a high dissociation pressure allows a considerable increase in the hydrogenation rate of magnesium. The influence of temperature and hydrogen pressure on the reaction rate were studied. Results concerning the hydriding of magnesium rich alloys such as Mg2Ca, La2Mg17 and CeMg12 are presented. The hydriding mechanism of La2Mg17 and CeMg12 alloys is given.

  2. Inhibited solid propellant composition containing beryllium hydride

    Science.gov (United States)

    Thompson, W. W. (Inventor)

    1978-01-01

    An object of this invention is to provide a composition of beryllium hydride and carboxy-terminated polybutadiene which is stable. Another object of this invention is to provide a method for inhibiting the reactivity of beryllium hydride toward carboxy-terminated polybutadiene. It was found that a small amount of lecithin inhibits the reaction of beryllium hydride with the acid groups in carboxy terminated polybutadiene.

  3. Thin-film metal hydrides for solar energy applications

    Energy Technology Data Exchange (ETDEWEB)

    Mongstad, Trygve Tveiteraas

    2012-11-01

    Thin-film metal hydrides may become important solar energy materials in the future. This thesis demonstrates interesting material properties of metal hydride films, relevant for applications as semiconducting materials for photovoltaic (PV) solar cells and for regulation of light using smart window technology.The work presented here has comprised an experimental study, focusing on three different materials: Magnesium hydride (MgH2), magnesium nickel hydride (Mg2NiH4) and yttrium hydride (YHx). Reactive sputter deposition was used to prepare the metal hydride film samples.This synthesis method is relatively uncommon for metal hydrides. Here,the first demonstration of reactive sputtering synthesis for YHx and Mg2NiH4 is given. Different challenges in forming singlephase, pure metal hydrides were identified: MgH2 could not be deposited without 3-16% metallic Mg present in the films, and YHx was found to react strong-ly to oxygen (O) during the deposition process. On the other hand, Mg2NiH4 films formed easily and apparently without major metallic clusters and with low O content.Mg2NiH4 is a semiconductor with an optical band gap that is suitable for PV solar cells. This study has showed that films with promising electrical and optical properties can be synthesized using reactive cosputtering of Mg and Ni. Using optical methods, the band gap for the as deposited samples was estimated to 1.54-1.76 eV, depending on the Mg-Ni composition. The asdeposited films were amorphous or nano-crystalline, but could be crystallized into the high-temperature fcc structure of Mg2NiH4 using heat treatment at 523 K. The band gap of the crystalline films was 2.1-2.2 eV, depending on the composition.A pronounced photochromic reaction to visible and UV light was observed for transparent yttrium hydride (T-YHx) samples. The optical transmission was reduced when the samples were illuminated, and the original optical transmission was restored when the samples were kept under dark conditions

  4. Synthesis and Hydrogen Desorption Properties of Aluminum Hydrides.

    Science.gov (United States)

    Jeong, Wanseop; Lee, Sang-Hwa; Kim, Jaeyong

    2016-03-01

    Aluminum hydride (AlH3 or alane) is known to store maximum 10.1 wt.% of hydrogen at relatively low temperature (hydrogen desorption are still not clear. To understand the desorption properties of hydrogen in alane, thermodynamically stable α-AlH3 was synthesized by employing an ethereal reaction method. The dependence of pathways on phase formation and the properties of hydrogen evolution were investigated, and the results were compared with the ones for γ-AlH3. It was found that γ-AlH3 requires 10 degrees C higher than that of γ-AlH3 to form, and its decomposition rate demonstrated enhanced endothermic stabilities. For desorption, all hydrogen atoms of alane evolved under an isothermal condition at 138 degrees C in less than 1 hour, and the sample completely transformed to pure aluminum. Our results show that the total amount of desorbed hydrogen from α-AlH3 exceeded 9.05 wt.%, with a possibility of further increase. Easy synthesis, thermal stability, and a large amount of hydrogen desorption of alane fulfill the requirements for light-weight hydrogen storage materials once the pathway of hydrogen cycling is provided.

  5. Predicting formation enthalpies of metal hydrides

    DEFF Research Database (Denmark)

    Andreasen, A.

    2004-01-01

    In order for the hydrogen based society viz. a society in which hydrogen is the primary energy carrier to become realizable an efficient way of storing hydrogen is required. For this purpose metal hydrides are serious candidates. Metal hydrides are formedby chemical reaction between hydrogen...... and metal and for the stable hydrides this is associated with release of heat (#DELTA#H_f ). The more thermodynamically stable the hydride, the larger DHf, and the higher temperature is needed in order to desorphydrogen (reverse reaction) and vice versa. For practical application the temperature needed...

  6. Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity.

    Science.gov (United States)

    Jordan, Abraham J; Lalic, Gojko; Sadighi, Joseph P

    2016-08-10

    Hydride complexes of copper, silver, and gold encompass a broad array of structures, and their distinctive reactivity has enabled dramatic recent advances in synthesis and catalysis. This Review summarizes the synthesis, characterization, and key stoichiometric reactions of isolable or observable coinage metal hydrides. It discusses catalytic processes in which coinage metal hydrides are known or probable intermediates, and presents mechanistic studies of selected catalytic reactions. The purpose of this Review is to convey how developments in coinage metal hydride chemistry have led to new organic transformations, and how developments in catalysis have in turn inspired the synthesis of reactive new complexes.

  7. Synthesis of hydrides by interaction of intermetallic compounds with ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Tarasov, Boris P., E-mail: tarasov@icp.ac.ru [Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Chernogolovka 142432 (Russian Federation); Fokin, Valentin N.; Fokina, Evelina E. [Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Chernogolovka 142432 (Russian Federation); Yartys, Volodymyr A., E-mail: volodymyr.yartys@ife.no [Institute for Energy Technology, Kjeller NO 2027 (Norway); Department of Materials Science and Engineering, Norwegian University of Science and Technology, Trondheim NO 7491 (Norway)

    2015-10-05

    Highlights: • Interaction of the intermetallics A{sub 2}B, AB, AB{sub 2}, AB{sub 5} and A{sub 2}B{sub 17} with NH{sub 3} was studied. • The mechanism of interaction of the alloys with ammonia is temperature-dependent. • Hydrides, hydridonitrides, disproportionation products or metal–N–H compounds are formed. • NH{sub 4}Cl was used as an activator of the reaction between ammonia and intermetallics. • Interaction with ammonia results in the synthesis of the nanopowders. - Abstract: Interaction of intermetallic compounds with ammonia was studied as a processing route to synthesize hydrides and hydridonitrides of intermetallic compounds having various stoichiometries and types of crystal structures, including A{sub 2}B, AB, AB{sub 2}, AB{sub 5} and A{sub 2}B{sub 17} (A = Mg, Ti, Zr, Sc, Nd, Sm; B = transition metals, including Fe, Co, Ni, Ti and nontransition elements, Al and B). In presence of NH{sub 4}Cl used as an activator of the reaction between ammonia and intermetallic alloys, their interaction proceeds at rather mild P–T conditions, at temperatures 100–200 °C and at pressures of 0.6–0.8 MPa. The mechanism of interaction of the alloys with ammonia appears to be temperature-dependent and, following a rise of the interaction temperature, it leads to the formation of interstitial hydrides; interstitial hydridonitrides; disproportionation products (binary hydride; new intermetallic hydrides and binary nitrides) or new metal–nitrogen–hydrogen compounds like magnesium amide Mg(NH{sub 2}){sub 2}. The interaction results in the synthesis of the nanopowders where hydrogen and nitrogen atoms become incorporated into the crystal lattices of the intermetallic alloys. The nitrogenated materials have the smallest particle size, down to 40 nm, and a specific surface area close to 20 m{sup 2}/g.

  8. On the polymorphism of benzocaine; a low-temperature structural phase transition for form (II).

    Science.gov (United States)

    Chan, Eric J; Rae, A David; Welberry, T Richard

    2009-08-01

    A low-temperature structural phase transition has been observed for form (II) of benzocaine (BZC). Lowering the temperature doubles the b-axis repeat and changes the space group from P2(1)2(1)2(1) to P112(1) with gamma now 99.37 degrees. The structure is twinned, the twin rule corresponding to a 2(1) screw rotation parallel to a. The phase transition is associated with a sequential displacement parallel to a of zigzag bi-layers of ribbons perpendicular to b*. No similar phase transition was observed for form (I) and this was attributed to the different packing symmetries of the two room-temperature polymorphic forms.

  9. Crystal structure of gold hydride

    Energy Technology Data Exchange (ETDEWEB)

    Degtyareva, Valentina F., E-mail: degtyar@issp.ac.ru

    2015-10-05

    Highlights: • Volume expansion of metal hydrides is due to the increase in the s-band filling. • AuH structure is similar to that of Hg having one more s electron compared to Au. • Structure stability of both Hg and AuH is governed by the Hume-Rothery rule. - Abstract: A number of transition metal hydrides with close-packed metal sublattices of fcc or hcp structures with hydrogen in octahedral interstitial positions were obtained by the high-pressure-hydrogen technique described by Ponyatovskii et al. (1982). In this paper we consider volume increase of metals by hydrogenation and possible crystal structure of gold hydride in relation with the structure of mercury, the nearest neighbor of Au in the Periodic table. Suggested structure of AuH has a basic tetragonal body-centered cell that is very similar to the mercury structure Hg-t I 2. The reasons of stability for this structure are discussed within the model of Fermi sphere–Brillouin zone interactions.

  10. Computing phase diagrams for a quasicrystal-forming patchy-particle system.

    Science.gov (United States)

    Reinhardt, Aleks; Romano, Flavio; Doye, Jonathan P K

    2013-06-21

    We introduce an approach to computing the free energy of quasicrystals, which we use to calculate phase diagrams for systems of two-dimensional patchy particles with five regularly arranged patches that have previously been shown to form dodecagonal quasicrystals. We find that the quasicrystal is a thermodynamically stable phase for a wide range of conditions and remains a robust feature of the system as the potential's parameters are varied. We also demonstrate that the quasicrystal is entropically stabilized over its crystalline approximants.

  11. Final waste forms project: Performance criteria for phase I treatability studies

    Energy Technology Data Exchange (ETDEWEB)

    Gilliam, T.M. [Oak Ridge National Lab., TN (United States); Hutchins, D.A. [Martin Marietta Energy Systems, Inc., Oak Ridge, TN (United States); Chodak, P. III [Massachusetts Institute of Technology (United States)

    1994-06-01

    This document defines the product performance criteria to be used in Phase I of the Final Waste Forms Project. In Phase I, treatability studies will be performed to provide {open_quotes}proof-of-principle{close_quotes} data to establish the viability of stabilization/solidification (S/S) technologies. This information is required by March 1995. In Phase II, further treatability studies, some at the pilot scale, will be performed to provide sufficient data to allow treatment alternatives identified in Phase I to be more fully developed and evaluated, as well as to reduce performance uncertainties for those methods chosen to treat a specific waste. Three main factors influence the development and selection of an optimum waste form formulation and hence affect selection of performance criteria. These factors are regulatory, process-specific, and site-specific waste form standards or requirements. Clearly, the optimum waste form formulation will require consideration of performance criteria constraints from each of the three categories. Phase I will focus only on the regulatory criteria. These criteria may be considered the minimum criteria for an acceptable waste form. In other words, a S/S technology is considered viable only if it meet applicable regulatory criteria. The criteria to be utilized in the Phase I treatability studies were primarily taken from Environmental Protection Agency regulations addressed in 40 CFR 260 through 265 and 268; and Nuclear Regulatory Commission regulations addressed in 10 CFR 61. Thus the majority of the identified criteria are independent of waste form matrix composition (i.e., applicable to cement, glass, organic binders etc.).

  12. Fundamental experiments on hydride reorientation in zircaloy

    Science.gov (United States)

    Colas, Kimberly B.

    In the current study, an in-situ X-ray diffraction technique using synchrotron radiation was used to follow directly the kinetics of hydride dissolution and precipitation during thermomechanical cycles. This technique was combined with conventional microscopy (optical, SEM and TEM) to gain an overall understanding of the process of hydride reorientation. Thus this part of the study emphasized the time-dependent nature of the process, studying large volume of hydrides in the material. In addition, a micro-diffraction technique was also used to study the spatial distribution of hydrides near stress concentrations. This part of the study emphasized the spatial variation of hydride characteristics such as strain and morphology. Hydrided samples in the shape of tensile dog-bones were used in the time-dependent part of the study. Compact tension specimens were used during the spatial dependence part of the study. The hydride elastic strains from peak shift and size and strain broadening were studied as a function of time for precipitating hydrides. The hydrides precipitate in a very compressed state of stress, as measured by the shift in lattice spacing. As precipitation proceeds the average shift decreases, indicating average stress is reduced, likely due to plastic deformation and morphology changes. When nucleation ends the hydrides follow the zirconium matrix thermal contraction. When stress is applied below the threshold stress for reorientation, hydrides first nucleate in a very compressed state similar to that of unstressed hydrides. After reducing the average strain similarly to unstressed hydrides, the average hydride strain reaches a constant value during cool-down to room temperature. This could be due to a greater ease of deforming the matrix due to the applied far-field strain which would compensate for the strains due to thermal contraction. Finally when hydrides reorient, the average hydride strains become tensile during the first precipitation regime and

  13. Detecting low concentrations of plutonium hydride with magnetization measurements

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jae Wook; Mun, E. D.; Baiardo, J. P.; Zapf, V. S.; Mielke, C. H. [National High Magnetic Field Laboratory, MPA-CMMS, Los Alamos National Laboratory (LANL), Los Alamos, New Mexico 87545 (United States); Smith, A. I.; Richmond, S.; Mitchell, J.; Schwartz, D. [Nuclear Material Science Group, MST-16, LANL, Los Alamos, New Mexico 87545 (United States)

    2015-02-07

    We report the formation of plutonium hydride in 2 at. % Ga-stabilized δ-Pu, with 1 at. % H charging. We show that magnetization measurements are a sensitive, quantitative measure of ferromagnetic plutonium hydride against the nonmagnetic background of plutonium. It was previously shown that at low hydrogen concentrations, hydrogen forms super-abundant vacancy complexes with plutonium, resulting in a bulk lattice contraction. Here, we use magnetization, X-ray, and neutron diffraction measurements to show that in addition to forming vacancy complexes, at least 30% of the H atoms bond with Pu to precipitate PuH{sub x} on the surface of the sample with x ∼ 1.9. We observe magnetic hysteresis loops below 40 K with magnetic remanence, consistent with ferromagnetic PuH{sub 1.9}.

  14. Aqueous Two-Phase Systems formed by Biocompatible and Biodegradable Polysaccharides and Acetonitrile.

    Science.gov (United States)

    de Brito Cardoso, Gustavo; Souza, Isabela Nascimento; Pereira, Matheus M; Freire, Mara G; Soares, Cleide Mara Faria; Lima, Álvaro Silva

    2014-11-05

    In this work, it is shown that novel aqueous two-phase systems can be formed by the combination of acetonitrile and polysaccharides, namely dextran. Several ternary phase diagrams were determined at 25 °C for the systems composed of water + acetonitrile + dextran. The effect of the dextran molecular weight (6,000, 40,000 and 100,000 g.mol(-1)) was ascertained toward their ability to undergo liquid-liquid demixing. An increase in the dextran molecular weight favors the phase separation. Furthermore, the effect of temperature (25, 35 and 45 °C) was evaluated for the system constituted by the dextran of higher molecular weight. Lower temperatures are favorable for phase separation since lower amounts of dextran and acetonitrile are required for the creation of aqueous two-phase systems. In general, acetonitrile is enriched in the top phase while dextran is majorly concentrated in the bottom phase. The applicability of this new type of two-phase systems as liquid-liquid extraction approaches was also evaluated by the study of the partition behavior of a well-known antioxidant - vanillin - and used here as a model biomolecule. The optimized conditions led to an extraction efficiency of vanillin of 95% at the acetonitrile-rich phase.

  15. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    Rechargeable battery systems are paramount in the power supply of modern electronic and electromechanical equipment. For the time being, the most promising secondary battery systems for the future are the lithium-ion and the nickel metal hydride (NiMH) batteries. In this thesis, metal hydrides and their properties are described with the aim of characterizing and improving those. The thesis has a special focus on the AB{sub 5} type hydrogen storage alloys, where A is a rare earth metal like lanthanum, or more commonly misch metal, which is a mixture of rare earth metals, mainly lanthanum, cerium, neodymium and praseodymium. B is a transition metal, mainly nickel, commonly with additions of aluminium, cobalt, and manganese. The misch metal composition was found to be very important for the geometry of the unit cell in AB{sub 5} type alloys, and consequently the equilibrium pressure of hydrogen in these types of alloys. The A site substitution of lanthanum by misch metal did not decrease the surface catalytic properties of AB{sub 5} type alloys. B-site substitution of nickel with other transition elements, however, substantially reduced the catalytic activity of the alloy. If the internal pressure within the electrochemical test cell was increased using inert argon gas, a considerable increase in the high rate charge/discharge performance of LaNi{sub 5} was observed. An increased internal pressure would enable the utilisation of alloys with a high hydrogen equivalent pressure in batteries. Such alloys often have favourable kinetics and high hydrogen diffusion rates and thus have a potential for improving the high current discharge rates in metal hydride batteries. The kinetic properties of metal hydride electrodes were found to improve throughout their lifetime. The activation properties were found highly dependent on the charge/discharge current. Fewer charge/discharge cycles were needed to activate the electrodes if a small current was used instead of a higher

  16. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    Rechargeable battery systems are paramount in the power supply of modern electronic and electromechanical equipment. For the time being, the most promising secondary battery systems for the future are the lithium-ion and the nickel metal hydride (NiMH) batteries. In this thesis, metal hydrides and their properties are described with the aim of characterizing and improving those. The thesis has a special focus on the AB{sub 5} type hydrogen storage alloys, where A is a rare earth metal like lanthanum, or more commonly misch metal, which is a mixture of rare earth metals, mainly lanthanum, cerium, neodymium and praseodymium. B is a transition metal, mainly nickel, commonly with additions of aluminium, cobalt, and manganese. The misch metal composition was found to be very important for the geometry of the unit cell in AB{sub 5} type alloys, and consequently the equilibrium pressure of hydrogen in these types of alloys. The A site substitution of lanthanum by misch metal did not decrease the surface catalytic properties of AB{sub 5} type alloys. B-site substitution of nickel with other transition elements, however, substantially reduced the catalytic activity of the alloy. If the internal pressure within the electrochemical test cell was increased using inert argon gas, a considerable increase in the high rate charge/discharge performance of LaNi{sub 5} was observed. An increased internal pressure would enable the utilisation of alloys with a high hydrogen equivalent pressure in batteries. Such alloys often have favourable kinetics and high hydrogen diffusion rates and thus have a potential for improving the high current discharge rates in metal hydride batteries. The kinetic properties of metal hydride electrodes were found to improve throughout their lifetime. The activation properties were found highly dependent on the charge/discharge current. Fewer charge/discharge cycles were needed to activate the electrodes if a small current was used instead of a higher

  17. METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

    Science.gov (United States)

    Vetrano, J.B.

    1962-01-23

    A method is given for preparing large, sound bodies of delta zirconium hydride. The method includes the steps of heating a zirconium body to a temperature of not less than l000 deg C, providing a hydrogen atmosphere for the zirconium body at a pressure not greater than one atmosphere, reducing the temperature slowly to 800 deg C at such a rate that cracks do not form while maintaining the hydrogen pressure substantially constant, and cooling in an atmosphere of hydrogen. (AEC)

  18. Beam Forming HF Radar Beam Pattern Measurements and Phase Offset Calibration Using a UAV

    Science.gov (United States)

    Cahl, D.; Voulgaris, G.

    2016-12-01

    It has been shown that measuring antenna patterns for direction finding radars improves surface current measurements. For beam forming radars, the beam pattern of the receive array is assumed to be similar to that derived using theoretical calculations. However, local environmental conditions may lead to deviations (i.e., larger sidelobes and beamwidth) from this idealized beam pattern. This becomes particularly important for wave measurements that are sensitive to interference from sidelobes. Common techniques for beam forming HF radar phase calibration include "cross calibration", using a secondary beam forming site as the signal source, or calibration using a ship. The former method is limited to only one direction; on straight coastlines this is often at a large angle from the radar bore site where the beam width and uncertainty in phase calibration might be large. The latter technique requires chartering a ship with an appropriate reflector or transmitter, or the identification of ships of opportunity. Recent advances in UAV technology combined with an easement of FAA restrictions (Part 107) allows phase calibrations and beam pattern measurements to be completed on an HF radar site using a small transmitter attached to a UAV. This presentation describes the use of a UAV and the development of a method for beam forming phase calibration and beam pattern measurements. This method uses the UAV as a moving signal source to provide true sidelobe and beamwidth measurements. Results are shown from a calibration carried out at a beam forming (WERA) radar site (8.3 MHz) located in Georgetown, SC and are compared with results from a cross calibration. Phase calibrations acquired by the UAV showed a dependence on azimuthal angle from the radar bore site. Also, the beam patterns obtained were found to be narrower than those derived using the stationary source method. The effect of the new phase values derived using this method on the accuracy of radial velocities will be

  19. Influence of Milling Conditions on the Hydriding Properties of Mg-C Nanocomposites

    Directory of Open Access Journals (Sweden)

    Hristina Stoyadinova

    2015-01-01

    Full Text Available Mg75 at.%, CB25 at.% (CB: carbon black composites were synthesized at different ball milling conditions (milling energy, milling duration, and environment and their hydriding properties were characterized by high-pressure DSC. The SEM observations revealed that the samples consist of 5–15 μm Mg particles, surrounded and in some cases coated by carbon particles. X-ray diffraction analysis showed that the Mg phase of all as-obtained composite powders is nanocrystalline with average crystallite size in the range 20–30 nm, depending on the milling conditions. The best hydriding properties, expressed in low-temperature hydriding (below 150°C and improved cycle life, showed the composites milled at dry conditions. This is obviously due mainly to the successful Mg surface protection by the carbon. Additional decrease of the hydriding temperature (<100°C was achieved applying higher-energy milling, but at the same time the cycling stability deteriorated, due to the extremely fine particles and microstructure achieved under these conditions. The composites milled in the presence of heptane showed rapid capacity decline during cycling as well. The observed difference in the hydriding behavior of the Mg-CB composites is attributed to the different coating efficiency of the carbon milled under different conditions with Mg, which is supposed to protect magnesium from oxidation and plays a catalytic role for the hydriding reaction.

  20. Looking for phase-space structures in star-forming regions: an MST-based methodology

    Science.gov (United States)

    Alfaro, Emilio J.; González, Marta

    2016-03-01

    We present a method for analysing the phase space of star-forming regions. In particular we are searching for clumpy structures in the 3D sub-space formed by two position coordinates and radial velocity. The aim of the method is the detection of kinematic segregated radial velocity groups, that is, radial velocity intervals whose associated stars are spatially concentrated. To this end we define a kinematic segregation index, tilde{Λ }(RV), based on the Minimum Spanning Tree graph algorithm, which is estimated for a set of radial velocity intervals in the region. When tilde{Λ }(RV) is significantly greater than 1 we consider that this bin represents a grouping in the phase space. We split a star-forming region into radial velocity bins and calculate the kinematic segregation index for each bin, and then we obtain the spectrum of kinematic groupings, which enables a quick visualization of the kinematic behaviour of the region under study. We carried out numerical models of different configurations in the sub-space of the phase space formed by the coordinates and the that various case studies illustrate. The analysis of the test cases demonstrates the potential of the new methodology for detecting different kind of groupings in phase space.

  1. Design of a ring resonator-based optical beam forming network for phased array receive antennas

    NARCIS (Netherlands)

    Klooster, van 't J.W.; Roeloffzen, C.G.H.; Meijerink, A.; Zhuang, L.; Marpaung, D.A.I.; Etten, van W.C.; Heideman, R.G.; Leinse, A.; Schippers, H.; Verpoorte, J.; Wintels, M.

    2008-01-01

    A novel squint-free ring resonator-based optical beam forming network (OBFN) for phased array antennas (PAA) is proposed. It is intended to provide broadband connectivity to airborne platforms via geostationary satellites. In this paper, we present the design of the OBFN and its control system. Our

  2. Ionic conduction of lithium hydride single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Pilipenko, G.I.; Oparin, D.V.; Zhuravlev, N.A.; Gavrilov, F.F.

    1987-09-01

    Using the electrical-conductivity- and NMR-measurement- methods, the ionic-conduction mechanism is established in stoichiometric lithium hydride single crystals. The activation energies of migration of anion- and cation-vacancies and the formation of Schottky-pair defects are determined. They assume that the mechanisms of self-diffusion and conductivity are different in lithium hydride.

  3. Residue formations of phosphorus hydride polymers and phosphorus oxyacids during phosphine gas fumigations of stored products.

    Science.gov (United States)

    Flora, Jason W; Byers, Loran E; Plunkett, Susan E; Faustini, Daryl L

    2006-01-11

    With the extent of international usage and the critical role phosphine gas (PH3) plays in commercial pest control, identification of the residual components deposited during fumigation is mandatory. It has been postulated that these infrequent residues are primarily composed of phosphoric acid or reduced forms of phosphoric acid [hypophosphorous acid (H3PO2) and phosphorous acid (H3PO3)], due to the oxidative degradation of phosphine. Using environmental scanning electron microscopy, gas phase Fourier transform infrared spectroscopy, and X-ray fluorescence spectroscopy, the structural elucidation and formation mechanism of the yellow amorphous polyhydric phosphorus polymers (P(x)H(y)) that occur in addition to the lower oxyacids of phosphorus in residues deposited during PH3 fumigations of select tobacco commodities are explored. This research determined that nitric oxide gas (or nitrogen dioxide) initiates residue formation of phosphorus hydride polymers and phosphorus oxyacids during PH3 fumigations of stored products.

  4. Atoms and Nanoparticles of Transition Metals as Catalysts for Hydrogen Desorption from Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    N. Bazzanella

    2011-01-01

    Full Text Available The hydrogen desorption kinetics of composite materials made of magnesium hydride with transition metal additives (TM: Nb, Fe, and Zr was studied by several experimental techniques showing that (i a few TM at.% concentrations catalyse the H2 desorption process, (ii the H2 desorption kinetics results stabilized after a few H2 sorption cycles when TM atoms aggregate by forming nanoclusters; (iii the catalytic process occurs also at TM concentration as low as 0.06 at.% when TM atoms clustering is negligible, and (iv mixed Fe and Zr additives produce faster H2 desorption kinetics than single additive. The improved H2 desorption kinetics of the composite materials can be explained by assuming that the interfaces between the MgH2 matrix and the TM nanoclusters act as heterogeneous sites for the nucleation of the Mg phase in the MgH2 matrix and promote the formation of fast diffusion channels for H migrating atoms.

  5. Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

    Energy Technology Data Exchange (ETDEWEB)

    Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.; Dedrick, Daniel E.; Reeder, Craig L.

    2012-02-01

    under simulated usage and accident conditions. Mitigating the hazards associated with reactive metal hydrides during an accident while finding a way to keep the original capability of the active material intact during normal use has been the focus of this work. These composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride, in this case a prepared sodium alanate (chosen as a representative reactive metal hydride). It was found that the polymerization of styrene and divinyl benzene could be initiated using AIBN in toluene at 70 degC. The resulting composite materials can be either hard or brittle solids depending on the cross-linking density. Thermal decomposition of these styrene-based composite materials is lower than neat polystyrene indicating that the chemical nature of the polymer is affected by the formation of the composite. The char-forming nature of cross-linked polystyrene is low and therefore, not an ideal polymer for hazard mitigation. To obtain composite materials containing a polymer with higher char-forming potential, siloxane-based monomers were investigated. Four vinyl-containing siloxane oligomers were polymerized with and without added styrene and divinyl benzene. Like the styrene materials, these composite materials exhibited thermal decomposition behavior significantly different than the neat polymers. Specifically, the thermal decomposition temperature was shifted approximately 100 degC lower than the neat polymer signifying a major chemical change to the polymer network. Thermal analysis of the cycled samples was performed on the siloxane-based composite materials. It was found that after 30 cycles the siloxane-containing polymer composite material has similar TGA/DSC-MS traces as the virgin composite material indicating that the polymer is physically intact upon cycling. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride in the form

  6. Hydrogen storage in sodium aluminum hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Ozolins, Vidvuds; Herberg, J.L. (Lawrence Livermore National Laboratories, Livermore, CA); McCarty, Kevin F.; Maxwell, Robert S. (Lawrence Livermore National Laboratories, Livermore, CA); Stumpf, Roland Rudolph; Majzoub, Eric H.

    2005-11-01

    Sodium aluminum hydride, NaAlH{sub 4}, has been studied for use as a hydrogen storage material. The effect of Ti, as a few mol. % dopant in the system to increase kinetics of hydrogen sorption, is studied with respect to changes in lattice structure of the crystal. No Ti substitution is found in the crystal lattice. Electronic structure calculations indicate that the NaAlH{sub 4} and Na{sub 3}AlH{sub 6} structures are complex-ionic hydrides with Na{sup +} cations and AlH{sub 4}{sup -} and AlH{sub 6}{sup 3-} anions, respectively. Compound formation studies indicate the primary Ti-compound formed when doping the material at 33 at. % is TiAl{sub 3} , and likely Ti-Al compounds at lower doping rates. A general study of sorption kinetics of NaAlH{sub 4}, when doped with a variety of Ti-halide compounds, indicates a uniform response with the kinetics similar for all dopants. NMR multiple quantum studies of solution-doped samples indicate solvent interaction with the doped alanate. Raman spectroscopy was used to study the lattice dynamics of NaAlH{sub 4}, and illustrated the molecular ionic nature of the lattice as a separation of vibrational modes between the AlH{sub 4}{sup -} anion-modes and lattice-modes. In-situ Raman measurements indicate a stable AlH{sub 4}{sup -} anion that is stable at the melting temperature of NaAlH{sub 4}, indicating that Ti-dopants must affect the Al-H bond strength.

  7. Discovery of a Frank-Kasper sigma phase in sphere-forming block copolymer melts.

    Science.gov (United States)

    Lee, Sangwoo; Bluemle, Michael J; Bates, Frank S

    2010-10-15

    Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma (σ) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the σ phase in undiluted linear block copolymers (and certain branched dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.

  8. A New, More Stable Polymorphic Form of Otilonium Bromide: Solubility, Crystal Structure, and Phase Transformation.

    Science.gov (United States)

    Vega, Daniel R; Halac, Emilia; Segovia, Luciano; Baggio, Ricardo

    2016-10-01

    A new polymorphic form of otilonium bromide is presented (Form I), and a thorough analysis of its crystal and molecular structure is performed. The compound suffers a temperature-driven first-order phase transition at about 396 K, which transforms it into the polymorph reported by Dapporto P and Sega A (Acta Cryst. 1986;C42:474-478) (Form II). Through thermal analysis and solubility experiments the relative stability of both crystal modifications were determined, confirming that at room temperature this new Form I is the more stable one, Form II existing just in a metastable state. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  9. ALUMINUM HYDRIDE: A REVERSIBLE STORAGE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    One of the challenges of implementing the hydrogen economy is finding a suitable solid H{sub 2} storage material. Aluminium (alane, AlH{sub 3}) hydride has been examined as a potential hydrogen storage material because of its high weight capacity, low discharge temperature, and volumetric density. Recycling the dehydride material has however precluded AlH{sub 3} from being implemented due to the large pressures required (>10{sup 5} bar H{sub 2} at 25 C) and the thermodynamic expense of chemical synthesis. A reversible cycle to form alane electrochemically using NaAlH{sub 4} in THF been successfully demonstrated. Alane is isolated as the triethylamine (TEA) adduct and converted to unsolvated alane by heating under vacuum. To complete the cycle, the starting alanate can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride (NaH) This novel reversible cycle opens the door for alane to fuel the hydrogen economy.

  10. Structural isotope effects in metal hydrides and deuterides.

    Science.gov (United States)

    Ting, Valeska P; Henry, Paul F; Kohlmann, Holger; Wilson, Chick C; Weller, Mark T

    2010-03-07

    Historically the extraction of high-quality crystallographic information from inorganic samples having high hydrogen contents, such as metal hydrides, has involved preparing deuterated samples prior to study using neutron powder diffraction. We demonstrate, through direct comparison of the crystal structure refinements of the binary hydrides SrH(2) and BaH(2) with their deuteride analogues at 2 K and as a function of temperature, that precise and accurate structural information can be obtained from rapid data collections from samples containing in excess of 60 at.% hydrogen using modern high-flux, medium resolution, continuous wavelength neutron powder diffraction instruments. Furthermore, observed isotope-effects in the extracted lattice parameters and atomic positions illustrate the importance of investigating compounds in their natural hydrogenous form whenever possible.

  11. Hydrides of CeNi/sub 5/, MmNi/sub 5/, Ca/sub 0/ /sub 2/(Ce/sub 0/ /sub 65/Mm/sub 0/ /sub 35/)/sub 0/ /sub 8/Ni/sub 5/, Ca/sub 0/ /sub 2/Ce/sub 0/ /sub 8/Ni/sub 5/, Ca/sub 0/ /sub 2/Mm/sub 0/ /sub 8/Ni/sub 5/, and mixed CeNi/sub 5//MmNi/sub 5/

    Energy Technology Data Exchange (ETDEWEB)

    Lakner, J.F.; Chow, T.S.

    1982-09-01

    Six intermetallic alloys (CeNi/sub 5/, MmNi/sub 5/, Ca/sub 0/ /sub 2/(Ce/sub 0/ /sub 65/Mm/sub 0/ /sub 35/)/sub 0/ /sub 8/Ni/sub 5/, Ca/sub 0/ /sub 2/Ce/sub 0/ /sub 8/Ni/sub 5/, Ca/sub 0/ /sub 2/Mm/sub 0/ /sub 8/Ni/sub 5/, and a mixed alloy, CeNi/sub 5//MmNi/sub 5/) were investigated with respect to their suitability to provide high hydrogen capacity and their potential for use in providing substantial hydrogen pressure at both low and high temperatures. A second phase of our investigation dealt with ball-milling and hydriding and dehydriding cycles to produce fine particles for use in hydride powder transfer studies. A summary of several Van't Hoff plots is also included for hydride-forming alloys.

  12. Metal hydrides: an innovative and challenging conversion reaction anode for lithium-ion batteries

    Directory of Open Access Journals (Sweden)

    Luc Aymard

    2015-08-01

    Full Text Available The state of the art of conversion reactions of metal hydrides (MH with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g−1 at a suitable potential (0.5 V vs Li+/Li0 and the lowest electrode polarization (2, TiH2, complex hydrides Mg2MHx and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MHx + xLi+ + xe− in equilibrium with M + xLiH. Other reaction paths—involving solid solutions, metastable distorted phases, and phases with low hydrogen content—were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to address these drawbacks. The development of high-capacity hydride anodes should be inspired by the emergent

  13. Metal hydrides: an innovative and challenging conversion reaction anode for lithium-ion batteries.

    Science.gov (United States)

    Aymard, Luc; Oumellal, Yassine; Bonnet, Jean-Pierre

    2015-01-01

    The state of the art of conversion reactions of metal hydrides (MH) with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g(-1) at a suitable potential (0.5 V vs Li(+)/Li(0)) and the lowest electrode polarization (hydrides Mg2MH x and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MH x + xLi(+) + xe(-) in equilibrium with M + xLiH. Other reaction paths-involving solid solutions, metastable distorted phases, and phases with low hydrogen content-were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to address these drawbacks. The development of high-capacity hydride anodes should be inspired by the emergent nano-research prospects which

  14. First-principles screening of complex transition metal hydrides for high temperature applications.

    Science.gov (United States)

    Nicholson, Kelly M; Sholl, David S

    2014-11-17

    Metal hydrides with enhanced thermodynamic stability with respect to the associated binary hydrides are useful for high temperature applications in which highly stable materials with low hydrogen overpressures are desired. Though several examples of complex transition metal hydrides (CTMHs) with such enhanced stability are known, little thermodynamic or phase stability information is available for this materials class. In this work, we use semiautomated thermodynamic and phase diagram calculations based on density functional theory (DFT) and grand canonical linear programming (GCLP) methods to screen 102 ternary and quaternary CTMHs and 26 ternary saline hydrides in a library of over 260 metals, intermetallics, binary, and higher hydrides to identify materials that release hydrogen at higher temperatures than the associated binary hydrides and at elevated temperatures, T > 1000 K, for 1 bar H2 overpressure. For computational efficiency, we employ a tiered screening approach based first on solid phase ground state energies with temperature effects controlled via H2 gas alone and second on the inclusion of phonon calculations that correct solid phase free energies for temperature-dependent vibrational contributions. We successfully identified 13 candidate CTMHs including Eu2RuH6, Yb2RuH6, Ca2RuH6, Ca2OsH6, Ba2RuH6, Ba3Ir2H12, Li4RhH4, NaPd3H2, Cs2PtH4, K2PtH4, Cs3PtH5, Cs3PdH3, and Rb2PtH4. The most stable CTMHs tend to crystallize in the Sr2RuH6 cubic prototype structure and decompose to the pure elements and hydrogen rather than to intermetallic phases.

  15. Spin Forming Aluminum Crew Module (CM) Metallic Aft Pressure Vessel Bulkhead (APVBH) - Phase II

    Science.gov (United States)

    Hoffman, Eric K.; Domack, Marcia S.; Torres, Pablo D.; McGill, Preston B.; Tayon, Wesley A.; Bennett, Jay E.; Murphy, Joseph T.

    2015-01-01

    The principal focus of this project was to assist the Multi-Purpose Crew Vehicle (MPCV) Program in developing a spin forming fabrication process for manufacture of the Orion crew module (CM) aft pressure vessel bulkhead. The spin forming process will enable a single piece aluminum (Al) alloy 2219 aft bulkhead resulting in the elimination of the current multiple piece welded construction, simplify CM fabrication, and lead to an enhanced design. Phase I (NASA TM-2014-218163 (1)) of this assessment explored spin forming the single-piece CM forward pressure vessel bulkhead. The Orion MPCV Program and Lockheed Martin (LM) recently made two critical decisions relative to the NESC Phase I work scope: (1) LM selected the spin forming process to manufacture a single-piece aft bulkhead for the Orion CM, and (2) the aft bulkhead will be manufactured from Al 2219. Based on the Program's new emphasis related to the spin forming process, the NESC was asked to conduct a Phase II assessment to assist in the LM manufacture of the aft bulkhead and to conduct a feasibility study into spin forming the Orion CM cone. This activity was approved on June 19, 2013. Dr. Robert Piascik, NASA Technical Fellow for Materials at the Langley Research Center (LaRC), was selected to lead this assessment. The project plan was approved by the NASA Engineering and Safety Center (NESC) Review Board (NRB) on July 18, 2013. The primary stakeholders for this assessment were the NASA and LM MPCV Program offices. Additional benefactors are commercial launch providers developing CM concepts.

  16. Carbene-metal hydrides can be much less acidic than phosphine-metal hydrides: significance in hydrogenations.

    Science.gov (United States)

    Zhu, Ye; Fan, Yubo; Burgess, Kevin

    2010-05-05

    Acidities of iridium hydride intermediates were shown to be critical in some transformations mediated by the chiral analogues of Crabtree's catalyst, 1-3. To do this, several experiments were undertaken to investigate the acidities of hydrogenation mixtures formed using these iridium-oxazoline complexes. DFT calculations indicated that the acidity difference for Ir-H intermediates in these hydrogenations were astounding; iridium hydride from the N-heterocyclic carbene catalyst 1 was calculated to be around seven pK(a) units less acidic than those from the P-based complexes 2 and 3. Consistent with this, the carbene complex 1 was shown to be more effective for hydrogenations of acid-sensitive substrates. In deuteration experiments, less "abnormal" deuteration was observed, corresponding to fewer complications from acid-mediated alkene isomerization preceding the D(2)-addition step. Finally, simple tests with pH indicators provided visual evidence that phosphine-based catalyst precursors give significantly more acidic reaction mixtures than the corresponding N-heterocyclic carbene ones. These observations indicate carbene-for-phosphine (and similar) ligand substitutions may impact the outcome of catalytic reactions by modifying the acidities of the metal hydrides formed.

  17. Pressure-driven formation and stabilization of superconductive chromium hydrides

    Science.gov (United States)

    Yu, Shuyin; Jia, Xiaojing; Frapper, Gilles; Li, Duan; Oganov, Artem R.; Zeng, Qingfeng; Zhang, Litong

    2015-01-01

    Chromium hydride is a prototype stoichiometric transition metal hydride. The phase diagram of Cr-H system at high pressures remains largely unexplored due to the challenges in dealing with the high activation barriers and complications in handing hydrogen under pressure. We have performed an extensive structural study on Cr-H system at pressure range 0 ∼ 300 GPa using an unbiased structure prediction method based on evolutionary algorithm. Upon compression, a number of hydrides are predicted to become stable in the excess hydrogen environment and these have compositions of Cr2Hn (n = 2–4, 6, 8, 16). Cr2H3, CrH2 and Cr2H5 structures are versions of the perfect anti-NiAs-type CrH with ordered tetrahedral interstitial sites filled by H atoms. CrH3 and CrH4 exhibit host-guest structural characteristics. In CrH8, H2 units are also identified. Our study unravels that CrH is a superconductor at atmospheric pressure with an estimated transition temperature (T c) of 10.6 K, and superconductivity in CrH3 is enhanced by the metallic hydrogen sublattice with T c of 37.1 K at 81 GPa, very similar to the extensively studied MgB2. PMID:26626579

  18. Hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S [Tampa, FL; Niemann, Michael U [Venice, FL; Goswami, D Yogi [Tampa, FL; Stefanakos, Elias K [Tampa, FL

    2012-04-10

    A ternary hydrogen storage system having a constant stoichiometric molar ratio of LiNH.sub.2:MgH.sub.2:LiBH.sub.4 of 2:1:1. It was found that the incorporation of MgH.sub.2 particles of approximately 10 nm to 20 nm exhibit a lower initial hydrogen release temperature of 150.degree. C. Furthermore, it is observed that the particle size of LiBNH quaternary hydride has a significant effect on the hydrogen sorption concentration with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160.degree. C. and the other around 300.degree. C., with the main hydrogen release temperature reduced from 310.degree. C. to 270.degree. C., while hydrogen is first reversibly released at temperatures as low as 150.degree. C. with a total hydrogen capacity of 6 wt. % to 8 wt. %. Detailed thermal, capacity, structural and microstructural properties have been demonstrated and correlated with the activation energies of these materials.

  19. A DFT based investigation into the electronic structure and properties of hydride rich rhodium clusters.

    Science.gov (United States)

    Brayshaw, Simon K; Green, Jennifer C; Hazari, Nilay; Weller, Andrew S

    2007-05-14

    , and, in general, good agreement was observed between experimental and theoretical results. The electronic reasons for selected steps in the cycle were investigated. The 12-hydride cluster [Rh(6)(PH(3))(6)H(12)](2+) readily picks up two molecules of H(2) to form [Rh(6)(PH(3))(6)H(16)](2+) because it has a small HOMO-LUMO gap (0.50 eV) and a degenerate pair of LUMO orbitals available for the uptake of four electrons (which are provided by two molecules of H(2)). The reverse process, the spontaneous release of a molecule of H(2) from [Rh(6)(PH(3))(6)H(16)](+) to form [Rh(6)(PH(3))(6)H(14)](+) occurs because the energy gap between the anti-bonding SOMO and the next highest energy occupied orbital in [Rh(6)(PH(3))(6)H(16)](+) is 0.9 eV, whereas in [Rh(6)(PH(3))(6)H(14)](+) the energy gap between the anti-bonding SOMO and the next highest energy occupied orbital is only 0.3 eV. At this stage the factors driving the conversion of [Rh(6)(PH(3))(6)H(14)](+) to [Rh(6)(PH(3))(6)H(12)](2+) are still unclear.

  20. Elements of style: consent form language and the therapeutic misconception in phase 1 gene transfer trials.

    Science.gov (United States)

    Kimmelman, Jonathan; Levenstadt, Aaron

    2005-04-01

    The therapeutic misconception arises wherever human subjects misinterpret the primary purpose of a clinical trial as therapeutic. Such misconceptions are particularly prevalent in trials involving severely ill subjects or novel and well-publicized investigational agents. In order to identify possible sources of the therapeutic misconception in gene transfer trials, 286 phase 1 human gene transfer consent documents were analyzed for their description of purpose, alternatives, and their use of the term gene transfer. We report that 20% of trials fail to explain their purpose as safety and dosage, only 41% of oncology trials identify comfort care as an alternative to participation, and that the term gene therapy is used with twice the frequency of the term gene transfer. Trends and coherence in consent form language were analyzed as well. Our results indicate that consent forms used in gene transfer phase 1 trials often contain language that promotes, or does little to deter, therapeutic misconceptions.

  1. Unified constitutive modelling for two-phase lamellar titanium alloys at hot forming conditions

    Directory of Open Access Journals (Sweden)

    Yang Lei

    2016-01-01

    Full Text Available In this paper, a set of mechanism based unified viscoplastic constitutive equations have been established for two-phase titanium alloys with initial lamellar microstructure, which models the softening mechanisms of the alloys in hot forming conditions. The dislocation density, rotation and globularization of lamellar α-phase and their effects on flow behaviour can also be modelled. The values of material constants in the equation set have been calibrated, according to stress-strain curves and globularization fractions of lamellar α-phase obtained from compression tests at a range of temperatures and strain rates, using a genetic algorithm (GA based optimisation method. Based on the determined constitutive equations, flow stress and globularization evolution of Ti-17 and TA15 alloys at different temperatures and strain rates were predicted. Good agreements between the experimental and computed results were obtained.

  2. Design and Implementation of a Beam Forming Network for a Phased Array Antenna

    Directory of Open Access Journals (Sweden)

    S. Devimeena

    2015-03-01

    Full Text Available This dissertation presents a beam forming network (BFN for phased array antenna-based on coherently radiating periodic structure (CORPS. The elements of CORPS are selected in such a way to obtain broad band characteristics, good return loss and good isolation between the radiating elements. These elements were arranged in such a way that the BFN naturally produces Gaussian amplitude. This methodology reduces the complexity of the conventional phased array design making it more flexible and minimizing the loss of energy inside the structure. A phase shifter design is proposed for the CORPS. The entire BFN’s sub-blocks have been designed for the frequency band of 5.925 GHz to 6.425 GHz, which find applications in communication satellite, fixed wireless systems.Defence Science Journal, Vol. 65, No. 1, January 2015, pp.46-52, DOI:http://dx.doi.org/10.14429/dsj.65.6940

  3. Microstructure-Property Correlation in Magnesium-based Hydrogen Storage Systems: The Case for Ball-milled Magnesium Hydride Powder and Magnesium-based Multilayered Composites

    Science.gov (United States)

    Danaie, Mohsen

    The main focus of this thesis is the characterization of defects and microstructure in high-energy ball milled magnesium hydride powder and magnesium-based multilayered composites. Enhancement in kinetics of hydrogen cycling in magnesium can be achieved by applying severe plastic deformation. A literature survey reveals that, due to extreme instability of alpha-MgH 2 in transmission electron microscope (TEM), the physical parameters that researchers have studied are limited to particle size and grain size. By utilizing a cryogenic TEM sample holder, we extended the stability time of the hydride phase during TEM characterization. Milling for only 30 minutes resulted in a significant enhancement in desorption kinetics. A subsequent annealing cycle under pressurized hydrogen reverted the kinetics to its initial sluggish state. Cryo-TEM analysis of the milled hydride revealed that mechanical milling induces deformation twinning in the hydride microstructure. Milling did not alter the thermodynamics of desorption. Twins can enhance the kinetics by acting as preferential locations for the heterogeneous nucleation of metallic magnesium. We also looked at the phase transformation characteristics of desorption in MgH2. By using energy-filtered TEM, we investigated the morphology of the phases in a partially desorbed state. Our observations prove that desorption phase transformation in MgH2 is of "nucleation and growth" type, with a substantial energy barrier for nucleation. This is contrary to the generally assumed "core-shell" structure in most of the simulation models for this system. We also tested the hydrogen storage cycling behavior of bulk centimeter-scale Mg-Ti and Mg-SS multilayer composites synthesized by accumulative roll-bonding. Addition of either phase (Ti or SS) allows the reversible hydrogen sorption at 350°C, whereas identically roll-bonded pure magnesium cannot be absorbed. In the composites the first cycle of absorption (also called "activation

  4. Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

    Science.gov (United States)

    Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rogers, J. R.; Robinson, M. B.; Rathz, T. J.; Krishnan, S.; Curreri, Peter A. (Technical Monitor)

    2002-01-01

    The local atomic structures of undercooled liquid metals are presumed to be icosahedral; this order is incompatible with translational periodicity, constituting a barrier to the nucleation of the crystal phase. The extended atomic structure of the icosahedral quasicrystal (i-phase) is similar to that presumed in the undercooled liquid. Therefore, a comparison of the maximum undercooling in alloys that form the i-phase with those that form crystal phases provides a probe of the liquid structure.

  5. Phase-space structures and stellar populations in the star-forming region NGC 2264

    Science.gov (United States)

    González, Marta; Alfaro, Emilio J.

    2017-02-01

    In this work, we analyse the structure of a subspace of the phase space of the star-forming region NGC 2264 using the spectrum of kinematic groupings (SKG). We show that the SKG can be used to process a collection of star data to find substructure at different scales. We have found structure associated with the NGC 2264 region and also with the background area. In the NGC 2264 region, a hierarchical analysis shows substructure compatible with that found in previous specific studies of the area but with an objective, compact methodology that allows us to homogeneously compare the structure of different clusters and star-forming regions. Moreover, this structure is compatible with the different ages of the main NGC 2264 star-forming populations. The structure found in the field can be roughly associated with giant stars far in the background, dynamically decoupled from NGC 2264, which could be related either with the Outer Arm or Monoceros Ring. The results in this paper confirm the relationship between structure in the radial velocity phase-space subspace and different kinds of populations, defined by other variables not necessarily analysed with the SKG, such as age or distance, showing the importance of detecting phase-space substructure in order to trace stellar populations in the broadest sense of the word.

  6. The Mechanism of kIH in Delayed Hydride Cracking of Zr-2.5wt% Nb at 150 ℃

    Institute of Scientific and Technical Information of China (English)

    D.YAN; R.L.EADIE

    2000-01-01

    This work studies the KIH mechanism of delayed hydride cracking (DHC) in Zr-2.5wt% Nb alloys. A modified experimental method was developed, in which specimens are fatigued between consecutive experiments, and a constant load instead of a decreasing load is used in each experiment. The hydride clusters formed and fractured at the crack tip during different experiments are thus separated and studied individually. A new R-curve phenomenon that characterizes the resistance to DHC was observed. KIH is thus more rigorously defined. Based on the measurement of the critical hydride cluster length at different K1, the threshold phenomenon of KIH is explained.

  7. Formation and characterization of hydride blisters in Zircaloy-4 cladding tubes

    Energy Technology Data Exchange (ETDEWEB)

    Hellouin de Menibus, Arthur, E-mail: arthur.hellouin-de-menibus@cea.fr [French Atomic Energy Comission - CEA Saclay/DEN/DANS/DMN/SRMA, 91191 Gif-sur-Yvette (France); Mines ParisTech/Centre des matériaux, CNRS UMR 7633, 91003 Evry (France); Auzoux, Quentin; Dieye, Ousmane [French Atomic Energy Comission - CEA Saclay/DEN/DANS/DMN/SEMI, 91191 Gif-sur-Yvette (France); Berger, Pascal [French Atomic Energy Comission - CEA Saclay/DSM/IRAMIS/SIS2M, 91191 Gif-sur-Yvette (France); CNRS UMR 3299, CEA-Saclay, 91191 Gif-sur-Yvette (France); Bosonnet, Sophie [French Atomic Energy Comission - CEA Saclay/DEN/DANS/DMN/SRMA, 91191 Gif-sur-Yvette (France); Foy, Eddy [French Atomic Energy Comission - CEA Saclay/DSM/IRAMIS/SIS2M, 91191 Gif-sur-Yvette (France); CNRS UMR 3299, CEA-Saclay, 91191 Gif-sur-Yvette (France); Macdonald, Vincent [French Atomic Energy Comission - CEA Saclay/DEN/DANS/DMN/SEMI, 91191 Gif-sur-Yvette (France); Besson, Jacques; Crépin, Jerome [Mines ParisTech/Centre des matériaux, CNRS UMR 7633, 91003 Evry (France)

    2014-06-01

    This article is focused on the formation of hydride blisters in zirconium alloys an experimental and theoretical standpoint, and their characterization in terms of morphology, hydrides crystallographic phases, hardness and hydrogen concentration. An experimental setup was developed to grow hydride blisters on pre-hydrided Zircaloy-4 cladding tubes by thermo-diffusion. The thermal conditions were optimized based on thermo-diffusion calculations, that take into account the hysteresis in the hydrogen solubility limit, to obtain a high blister growth rate. Micro-X-ray Diffraction (XRD), nano-hardness and Elastic Recoil Detection Analysis (ERDA) showed that the blisters contain a hydrogen gradient, with pure δ-hydride phase close to the external surface over one third of the blister depth. Thermo-diffusion calculations showed these half thickness blisters should grow in only a few days in PWR conditions. Eventually, the Diffusion Equilibrium Threshold (DET) was defined as a criterion that limits the blister growth, and emphasizes that the hysteresis in the hydrogen solubility limit in zirconium must be taken into account to model hydrogen thermo-diffusion in zirconium alloys.

  8. Hydride heat pump with heat regenerator

    Science.gov (United States)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative hydride heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system. A series of at least four canisters containing a lower temperature performing hydride and a series of at least four canisters containing a higher temperature performing hydride is provided. Each canister contains a heat conductive passageway through which a heat transfer fluid is circulated so that sensible heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  9. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  10. Investigation of long term stability in metal hydrides

    Science.gov (United States)

    Marmaro, Roger W.; Lynch, Franklin E.; Chandra, Dhanesh; Lambert, Steve; Sharma, Archana

    1991-01-01

    It is apparent from the literature and the results of this study that cyclic degradation of AB(5) type metal hydrides varies widely according to the details of how the specimens are cycled. The Rapid Cycle Apparatus (RCA) used produced less degradation in 5000 to 10000 cycles than earlier work with a Slow Cycle Apparatus (SCA) produced in 1500 cycles. Evidence is presented that the 453 K (356 F) Thermal Aging (TA) time spent in the saturated condition causes hydride degradation. But increasing the cooling (saturation) period in the RCA did not greatly increase the rate of degradation. It appears that TA type degradation is secondary at low temperatures to another degradation mechanism. If rapid cycles are less damaging than slow cycles when the saturation time is equal, the rate of hydriding/dehydriding may be an important factor. The peak temperatures in the RCA were about 30 C lower than the SCA. The difference in peak cycle temperatures (125 C in the SCA, 95 C in RCA) cannot explain the differences in degradation. TA type degradation is similar to cyclic degradation in that nickel peaks and line broadening are observed in X ray diffraction patterns after either form of degradation.

  11. Phase Composition and the Effect of Thermal Cycling for VH(sub x) V(sub 0.995) C(sub 0.005)H(sub x) and V(sub 0.975)Zr(sub 0.020)C(sub 0.005)H(sub x)

    Science.gov (United States)

    Cantrell, J.; Bowman, R.

    1999-01-01

    X-ray diffraction (XRD) studies were performed on hydride phases formed by vanadium and its carbon substituted alloys. It was previously found that thermal cycling of VHx across the B-y mixed phase region changed the reversible hydrogen storage capacity and other properties.

  12. INVESTIGATION OF THE THERMODYNAMICS GOVERNING METAL HYDRIDE SYNTHESIS IN THE MOLTEN STATE PROCESS.

    Energy Technology Data Exchange (ETDEWEB)

    Stowe, A; Polly Berseth, P; Ragaiy Zidan, R; Donald Anton, D

    2007-08-23

    Complex metal hydrides have been synthesized for hydrogen storage through a new synthetic technique utilizing high hydrogen overpressure at elevated temperatures (molten state processing). This synthesis technique holds the potential of fusing different complex hydrides at elevated temperatures and pressures to form new species with enhanced hydrogen storage properties. Formation of these compounds is driven by thermodynamic and kinetic considerations. We report on investigations of the thermodynamics. Novel synthetic complexes were formed, structurally characterized, and their hydrogen desorption properties investigated. The effectiveness of the molten state process is compared with mechanicosynthetic ball milling.

  13. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, R; Christopher Fewox, C; Brenda Garcia-Diaz, B; Joshua Gray, J

    2009-01-09

    Hydrogen storage is one of the challenges to be overcome for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods. The direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali metal alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  14. ALUMINUM HYDRIDE: A REVERSIBLE MATERIAL FOR HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Fewox, C; Ragaiy Zidan, R; Brenda Garcia-Diaz, B

    2008-12-31

    Hydrogen storage is one of the greatest challenges for implementing the ever sought hydrogen economy. Here we report a novel cycle to reversibly form high density hydrogen storage materials such as aluminium hydride. Aluminium hydride (AlH{sub 3}, alane) has a hydrogen storage capacity of 10.1 wt% H{sub 2}, 149 kg H{sub 2}/m{sup 3} volumetric density and can be discharged at low temperatures (< 100 C). However, alane has been precluded from use in hydrogen storage systems because of the lack of practical regeneration methods; the direct hydrogenation of aluminium to form AlH{sub 3} requires over 10{sup 5} bars of hydrogen pressure at room temperature and there are no cost effective synthetic means. Here we show an unprecedented reversible cycle to form alane electrochemically, using alkali alanates (e.g. NaAlH{sub 4}, LiAlH{sub 4}) in aprotic solvents. To complete the cycle, the starting alanates can be regenerated by direct hydrogenation of the dehydrided alane and the alkali hydride being the other compound formed in the electrochemical cell. The process of forming NaAlH{sub 4} from NaH and Al is well established in both solid state and solution reactions. The use of adducting Lewis bases is an essential part of this cycle, in the isolation of alane from the mixtures of the electrochemical cell. Alane is isolated as the triethylamine (TEA) adduct and converted to pure, unsolvated alane by heating under vacuum.

  15. Hydrogen storage in complex metal hydrides

    National Research Council Canada - National Science Library

    Bogdanovic, Borislav; Felderhoff, Michael; Streukens, Guido

    2009-01-01

    ...) are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides...

  16. Sealed aerospace metal-hydride batteries

    Science.gov (United States)

    Coates, Dwaine

    1992-01-01

    Nickel metal hydride and silver metal hydride batteries are being developed for aerospace applications. There is a growing market for smaller, lower cost satellites which require higher energy density power sources than aerospace nickel-cadmium at a lower cost than space nickel-hydrogen. These include small LEO satellites, tactical military satellites and satellite constellation programs such as Iridium and Brilliant Pebbles. Small satellites typically do not have the spacecraft volume or the budget required for nickel-hydrogen batteries. NiCd's do not have adequate energy density as well as other problems such as overcharge capability and memory effort. Metal hydride batteries provide the ideal solution for these applications. Metal hydride batteries offer a number of advantages over other aerospace battery systems.

  17. Atom Probe Analysis of Ex Situ Gas-Charged Stable Hydrides.

    Science.gov (United States)

    Haley, Daniel; Bagot, Paul A J; Moody, Michael P

    2017-01-30

    In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200-500 kPa (2-5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide-metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

  18. Looking for phase-space structures in star-forming regions: An MST-based methodology

    CERN Document Server

    Alfaro, Emilio J

    2015-01-01

    We present a method for analysing the phase space of star-forming regions. In particular we are searching for clumpy structures in the 3D subspace formed by two position coordinates and radial velocity. The aim of the method is the detection of kinematic segregated radial velocity groups, that is, radial velocity intervals whose associated stars are spatially concentrated. To this end we define a kinematic segregation index, $\\tilde{\\Lambda}$(RV), based on the Minimum Spanning Tree (MST) graph algorithm, which is estimated for a set of radial velocity intervals in the region. When $\\tilde{\\Lambda}$(RV) is significantly greater than 1 we consider that this bin represents a grouping in the phase space. We split a star-forming region into radial velocity bins and calculate the kinematic segregation index for each bin, and then we obtain the spectrum of kinematic groupings, which enables a quick visualization of the kinematic behaviour of the region under study. We carried out numerical models of different config...

  19. REVERSE PHASE HIGH PERFORMANCE LIQUID CHROMATOGRAPHIC METHOD FOR THE ANALYSIS OF GLIPIZIDE IN PHARMACEUTICAL DOSAGE FORMS

    Directory of Open Access Journals (Sweden)

    Sheikh Rahila

    2010-12-01

    Full Text Available A rapid and sensitive reverse phase high performance liquid chromatographic methods depicted for the qualitative and quantitative assay of glipizide in pharmaceutical dosage forms. Glipizide was chromatographed on reverse phase C18 column with mobile phase consisting of 0.05 M Potassium Dihydrogen Orthophosphate: Methanol [15: 85 %v/v, pH 7.0 ± 0.05, adjusted with 1% Triethylamine]. The mobile phase was pumped at a flow rate 1 mL/min. Quantification was achieved by monitoring the ultraviolet absorbance at 225 ηm. The average retention time for Glipizide was found to be 3.21 ± 0.07. With this method, linearity was observed in the range of 10 – 2000 ηg/ml. The LOD and LOQ were found to be 5 ηg/ml and 15 ηg/ml respectively. The method was applicable for the analysis of drug in tablet formulation. The results of analysis were validated statistically.

  20. Iron oxyhydroxide nanoparticles formed by forced hydrolysis: dependence of phase composition on solution concentration.

    Science.gov (United States)

    Fu, Dong; Keech, Peter G; Sun, Xueliang; Wren, J Clara

    2011-11-07

    Nanoparticles of single-phase lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) have been synthesized by forced hydrolysis of ferric nitrate with no other additives, and the particles have been characterized by XRD, FT-IR and TEM. At low Fe(NO(3))(3) concentrations the hydrolysis product is predominantly γ-FeOOH, while at high concentrations it is α-FeOOH. These particles are nanometers in size and fall within narrow particle size distributions. The dependence of the oxyhydoxide phase on ferric nitrate concentration is attributed to two thermodynamic factors, the enthalpy of formation and the surface enthalpy of hydration at the oxide-water interface (which is a function of surface area). Two potential mechanisms for the phase-specific growth are proposed that explain the solution concentration dependence of the phase formed. Three other common nanoscale particles (α-Fe(2)O(3), Fe(3)O(4) and γ-Fe(2)O(3)) have also been prepared by relatively simple thermal/chemical treatment of the γ-FeOOH nanoparticles.

  1. Study on polyethylene glycol/epoxy resin composite as a form-stable phase change material

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Yutang; Kang, Huiying; Wang, Weilong; Liu, Hong; Gao, Xuenong [The Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, South China University of Technology, Guangzhou 510640 (China)

    2010-12-15

    Form-stable polyethylene glycol (PEG)/epoxy resin (EP) composite as a novel phase change material (PCM) was prepared using casting molding method. In this new material, PEG acts as the latent heat storage material and EP polymer serves as the supporting material, which provides structural strength and prevents the leakage of the melted PEG. The structure and morphology of the novel composite were observed using Fourier transformation infrared spectroscope (FTIR) and scanning electronic microscope (SEM). The thermo-mechanical property and transition behavior were characterized by polarizing optical microscope (POM), static thermo-mechanical analysis (TMA) and differential scanning calorimeter (DSC). The experimental results show that, as a result of the physical tangled function of the epoxy resin carrier to the PEG segment, the composite macroscopically presents the solid-solid phase change characteristic. (author)

  2. Study on polyethylene glycol/epoxy resin composite as a form-stable phase change material

    Energy Technology Data Exchange (ETDEWEB)

    Fang Yutang, E-mail: ppytfang@scut.edu.c [Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, South China University of Technology, Guangzhou 510640 (China); Kang Huiying; Wang Weilong; Liu Hong; Gao Xuenong [Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, South China University of Technology, Guangzhou 510640 (China)

    2010-12-15

    Form-stable polyethylene glycol (PEG)/epoxy resin (EP) composite as a novel phase change material (PCM) was prepared using casting molding method. In this new material, PEG acts as the latent heat storage material and EP polymer serves as the supporting material, which provides structural strength and prevents the leakage of the melted PEG. The structure and morphology of the novel composite were observed using Fourier transformation infrared spectroscope (FTIR) and scanning electronic microscope (SEM). The thermo-mechanical property and transition behavior were characterized by polarizing optical microscope (POM), static thermo-mechanical analysis (TMA) and differential scanning calorimeter (DSC). The experimental results show that, as a result of the physical tangled function of the epoxy resin carrier to the PEG segment, the composite macroscopically presents the solid-solid phase change characteristic.

  3. Corrosion properties of S-phase layers formed on medical grade austenitic stainless steel.

    Science.gov (United States)

    Buhagiar, Joseph; Dong, Hanshan

    2012-02-01

    The corrosion properties of S-phase surface layers formed in AISI 316LVM (ASTM F138) and High-N (ASTM F1586) medical grade austenitic stainless steels by plasma surface alloying with nitrogen (at 430°C), carbon (at 500°C) and both carbon and nitrogen (at 430°C) has been investigated. The corrosion behaviour of the S-phase layers in Ringer's solutions was evaluated using potentiodynamic and immersion corrosion tests. The corrosion damage was evaluated using microscopy, hardness testing, inductive coupled plasma mass spectroscopy and X-ray diffraction. The experimental results have demonstrated that low-temperature nitriding, carburising and carbonitriding can improve the localised corrosion resistance of both industrial and medical grade austenitic stainless steels as long as the threshold sensitisation temperature is not reached. Carburising at 500°C has proved to be the best hardening treatment with the least effect on the corrosion resistance of the parent alloy.

  4. Effects of Ca additions on some Mg-alloy hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Lupu, D.; Biris, A.; Indrea, E.; Bucur, R.V.

    1983-01-01

    The hydrogenation of the alloy of composition CaMg/sub 1/ /sub 8/Ni/sub 0/ /sub 5/ containing CaMg/sub 2/ and MgNi/sub 2/ shows fast activation kinetics. The Mg/sub 2/Ni phase is observed in the dehydrided samples. The three plateaus on the hydrogen desorption isotherms correspond to the most stable magnesium hydrides observed up to now in Mg-alloy (..delta.. H = 20 to 24 kcal/mol H/sub 2/). The effects of Ca additions on the hydrogen storage capacity and desorption rates of some Mg-rich alloys have been studied. 16 references, 3 figures, 1 table.

  5. Multislice simulations for in-situ HRTEM studies of nanostructured magnesium hydride at ambient hydrogen pressure.

    Science.gov (United States)

    Surrey, Alexander; Schultz, Ludwig; Rellinghaus, Bernd

    2017-01-31

    The use of transmission electron microscopy (TEM) for the structural characterization of many nanostructured hydrides, which are relevant for solid state hydrogen storage, is hindered due to a rapid decomposition of the specimen upon irradiation with the electron beam. Environmental TEM allows to stabilize the hydrides by applying a hydrogen back pressure of up to 4.5 bar in a windowed environmental cell. The feasibility of high-resolution TEM (HRTEM) investigations of light weight metals and metal hydrides in such a "nanoreactor" is studied theoretically by means of multislice HRTEM contrast simulations using Mg and its hydride phase, MgH2, as model system. Such a setup provides the general opportunity to study dehydrogenation and hydrogenation reactions at the nanoscale under technological application conditions. We analyze the dependence of both the spatial resolution and the HRTEM image contrast on parameters such as the defocus, the metal/hydride thickness, and the hydrogen pressure in order to explore the possibilities and limitations of in-situ experiments with windowed environmental cells. Such simulations may be highly valuable to pre-evaluate future experimental studies.

  6. Subsolutions of Elliptic Operators in Divergence Form and Application to Two-Phase Free Boundary Problems

    Directory of Open Access Journals (Sweden)

    Sandro Salsa

    2006-12-01

    Full Text Available Let L be a divergence form operator with Lipschitz continuous coefficients in a domain Ω, and let u be a continuous weak solution of Lu=0 in {u≠0}. In this paper, we show that if φ satisfies a suitable differential inequality, then vφ(x=supBφ(x(xu is a subsolution of Lu=0 away from its zero set. We apply this result to prove C1,γ regularity of Lipschitz free boundaries in two-phase problems.

  7. Phenolic composition of pomegranate peel extracts using an LC-MS approach with silica hydride columns

    Science.gov (United States)

    The peels of different pomegranate cultivars (Molla Nepes, Parfianka, Purple Heart, Wonderful and Vkunsyi) were compared in terms of phenolic composition and total phenolics. Analyses were performed on two silica hydride-based stationary phases: phenyl and undecenoic acid columns. Quantitation was ...

  8. Properties of hydrogen permeation barrier on the surface of zirconium hydride

    Institute of Scientific and Technical Information of China (English)

    CHEN Weidong; WANG Lijun; HAN Lin; CHEN Song

    2008-01-01

    A hydrogen permeation barrier was manufactured by the in situ reaction of zirconium hydride with oxygen.A reduction in the hydrogen permeation of the oxide films was detected by measuring the mass difference of the zirconium hydride samples after the dehydrogenation experiment.The reaction of zirconium hydride with oxygen occurs only under the condition that the temperature is higher than 673 K in the oxygen partial pressure of 0.1 MPa.The oxide film is composed of two layers,a permeable oxide layer and a dense oxide layer,and the main phase of the oxide film is ZrO2 with baddeleyite structure.The XPS analysis shows that O-H bonds exist in the oxide film,which are helpful for resisting hydrogen diffusion through the oxide film.

  9. Raman Spectroscopy as a Probe of Surface Oxides and Hydrides on Niobium

    Energy Technology Data Exchange (ETDEWEB)

    J. Zasadzinski, B. Albee, S. Bishnoi, C. Cao, G. Ciovati, L.D. Cooley, D.C. Ford, Th. Proslier

    2011-07-01

    Raman microscopy/spectroscopy has been used in conjunction with AFM, tunneling and magnetic susceptibility to identify surface oxides and hydrides on annealed, recrystallized foils of high purity Nb and on single crystals of cavity grade Nb. Cold worked regions of the Nb foil as well as rough regions near grain boundaries showed clear evidence of ordered hydride phases which were identified by VASP phonon calculations. Cold worked regions also displayed enhanced surface paramagnetism. Surface enhanced Raman spectra have also been obtained using 1.0 nm Au depositon. The SERS spectra reveal hydride molecular species which are not observable by conventional Raman. These results indicate that Raman is a useful probe of Nb surfaces relevant for cavity performance

  10. Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape.

    Science.gov (United States)

    Syrenova, Svetlana; Wadell, Carl; Nugroho, Ferry A A; Gschneidtner, Tina A; Diaz Fernandez, Yuri A; Nalin, Giammarco; Świtlik, Dominika; Westerlund, Fredrik; Antosiewicz, Tomasz J; Zhdanov, Vladimir P; Moth-Poulsen, Kasper; Langhammer, Christoph

    2015-12-01

    Physicochemical properties of nanoparticles may depend on their size and shape and are traditionally assessed in ensemble-level experiments, which accordingly may be plagued by averaging effects. These effects can be eliminated in single-nanoparticle experiments. Using plasmonic nanospectroscopy, we present a comprehensive study of hydride formation thermodynamics in individual Pd nanocrystals of different size and shape, and find corresponding enthalpies and entropies to be nearly size- and shape-independent. The hysteresis observed is significantly wider than in bulk, with details depending on the specifics of individual nanoparticles. Generally, the absorption branch of the hysteresis loop is size-dependent in the sub-30 nm regime, whereas desorption is size- and shape-independent. The former is consistent with a coherent phase transition during hydride formation, influenced kinetically by the specifics of nucleation, whereas the latter implies that hydride decomposition either occurs incoherently or via different kinetic pathways.

  11. gamma-Zr-Hydride Precipitate in Irradiated Massive delta- Zr-Hydride

    DEFF Research Database (Denmark)

    Warren, M. R.; Bhattacharya, D. K.

    1975-01-01

    During examination of A Zircaloy-2-clad fuel pin, which had been part of a test fuel assembly in a boiling water reactor, several regions of severe internal hydriding were noticed in the upper-plenum end of the pin. Examination of similar fuel pins has shown that hydride of this type is caused...

  12. Development of a direct hydride generation nebulizer for the determination of selenium by inductively coupled plasma optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Carrion, Nereida E-mail: ncarrion@strix.ciens.ucv.ve; Murillo, Miguel; Montiel, Edie; Diaz, Dorfe

    2003-08-15

    A study was conducted to evaluate the performance of a new direct hydride generation nebulizer system for determination of hydride forming elements by inductively coupled plasma optical emission spectroscopy. This system was designed and optimized to obtain the highest sensitivity. Several experimental designs were used for these purposes. To optimize the individual parameters of the system, and to study the interaction between these parameters for both direct hydride generation nebulizers, a central composite orthogonal design with eight factors was set up. Significant behavioral differences were observed in the two direct hydride generation nebulizers studied. Finally, a 70 {mu}m gas orifice nebulizer exhibits a better detection limit than the 120 {mu}m nebulizer. Generally, for determination of selenium, this new direct hydride generation nebulizer system exhibits a linear dynamic range and detection limit (3{sigma}b) of 3 orders of magnitude and 0.2 {mu}g l{sup -1} for selenium, respectively. This new hydride generator is much simpler system that conventional hydride generation systems, which does not need to be changed to work in normal mode with the inductively coupled plasma, since this system may be used for hydride forming elements and those that do not form them. It produces a rapid response with low memory effect. It reduces the interference level of Ni, Co and Cu to 600, 500 and 5 mg l{sup -1}, respectively. The accuracy of the system was verified by the determination of selenium in several standard reference materials of ambient, food and clinical sample matrices. No statistically significant differences (95 confidence level) were obtained between our method and the reference values.

  13. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  14. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  15. First-principles study of structural stability and elastic properties of MgPd3 and its hydride

    Directory of Open Access Journals (Sweden)

    Dong-Hai Wu

    2014-06-01

    Full Text Available Theoretical study of structural stability and elastic properties of α- and β-MgPd3 intermetallic compounds as well as their hydrides have been carried out based on density functional theory. The results indicate α-MgPd3 is more stable than β phase with increased stability in their hydrides. The calculated elastic constants of α-MgPd3 are overall larger than β phase. After hydrogenation, the elastic constants are enlarged. And the elastic moduli exhibit similar tendency. The anisotropy of α-MgPd3 is larger than β phase, and the hydrides demonstrate larger anisotropy. Their ductility follows the order of α-MgPd3H0.5 < α-MgPd3 < β-MgPd3H < β-MgPd3. Compared with β phase, higher Debye temperature of α-MgPd3 implies stronger covalent interaction, and the Debye temperature of hydrides increases slightly. The electronic structures demonstrate that the Pd–Pd interaction is stronger than Pd–Mg, and Pd–H bonds play a significant role in the phase stability and elastic properties of hydrides.

  16. Transition-Metal Hydride Radical Cations.

    Science.gov (United States)

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

    2016-08-10

    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  17. A structural study of lamellar phases formed by nucleoside-functionalized lipids

    CERN Document Server

    Berti, D; Baglioni, P; Dante, S; Hauss, T

    2002-01-01

    We report a neutron-scattering investigation of lamellar phases formed by novel phospholipids bearing nucleosides at the polar-head-group region. These nucleolipids can interact through stacking and H-bond interactions, following a pattern that resembles base-base coupling in natural nucleic acids (DNA, RNA), i.e. they have similar recognition properties. Bilayer stacks formed of DPP-adenosine, DPP-uridine and their 1:1 mixture were investigated after equilibration in a 98% relative humidity atmosphere. The DPP-adenosine spectrum can be accounted for (in analogy to DPPC) by a lamellar phase with a smectic period of about 60 A. DPP-uridine displays a not so straightforward behavior that we have tentatively ascribed to the coexistence of lamellae with different smectic periods. In the 1:1 mixture the lamellar mesophase of DPP-uridine is retained, suggesting a specific interaction of the uridine polar-head group with the adenosine moiety of DPP-adenosine. It should be stressed that this behavior can be considere...

  18. The GM1 Ganglioside Forms GM1-Rich Gel Phase Microdomains within Lipid Rafts

    Directory of Open Access Journals (Sweden)

    Lucia Becucci

    2014-07-01

    Full Text Available Mercury-supported, self-assembled monolayers (SAMs of the sole dioleoylphosphatidylcholine (DOPC and of a raft-forming mixture of DOPC, cholesterol (Chol and palmitoylsphingomyelin (PSM of (59:26:15 mol% composition, were investigated by electrochemical impedance spectroscopy (EIS, both in the absence and in the presence of the monosialoganglioside GM1. The impedance spectra of these four SAMs were fitted by a series of parallel combinations of a resistance and a capacitance (RC meshes and displayed on plots of ωZ′ against −ωZ″, where Z′ and Z″ are the in-phase and quadrature components of the impedance and ω is the angular frequency. A comparison among these different impedance spectra points to the formation of GM1-rich gel phase microdomains within the lipid rafts of the DOPC/Chol/PSM mixture, thanks to the unique molecular-level smooth support provided by mercury, which allows EIS to detect the protruding gel phase microdomains by averaging them over a macroscopically large area.

  19. Well-Defined Silica Supported Aluminum Hydride: Another Step Towards the Utopian Single Site Dream?

    KAUST Repository

    Werghi, Baraa

    2015-07-17

    Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(≡SiO)2Al-CH2CH(CH3)2] 1a, silicon isobutyl [≡Si-CH2CH(CH3)2] 1b and a silicon hydride [≡Si-H] 1c. Their structural identity was characterized by FT-IR and advance solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [≡SiO-Al-[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: Transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, ≡Si-O-Si≡ but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O-Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a ß-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al-H bond and a O-Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10-5 mbar) generates Al-H through a ß-H elimination of isobutyl fragment. These supported well-defined Al-H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.

  20. Laser assisted conical spin forming of dual phase automotive steel. Experimental demonstration of work hardening reduction and forming limit extension

    Science.gov (United States)

    Romero, P.; Otero, N.; Cabrera, J. M.; Masagué, D.

    Laser Assisted Spin Forming is investigated for improving the poor formability of Advanced High Strength Steel DP-800 and Aeronautic Grade Titanium alloy, with minor or no change in microstructure, final properties improvements and no damage to coating, thanks to controlled energy input and fast thermal cycles. IR imaging and force-torque monitoring are used to characterise the forming process. Residual stress measurement, microstructure, microhardness and EBSD are used to study the formed parts under the combined action of laser and mechanical force. A micromechanism of laser assisted spinning is proposed, as well as advantages and limitations of the technique.

  1. Fourier-Domain Analysis of Hydriding Kinetics Using Pneumato-Chemical Impedance Spectroscopy

    Directory of Open Access Journals (Sweden)

    P. Millet

    2007-10-01

    Full Text Available Analysis of phase transformation processes observed in hydrogen absorbing materials (pure metals, alloys, or compounds is still a matter of active research. Using pneumato-chemical impedance spectroscopy (PIS, it is now possible to analyze the mechanism of hydriding reactions induced by the gas phase. Experimental impedance diagrams, measured on activated LaNi5 in single- and two-phase domains, are reported in this paper. It is shown that their shape is mostly affected by the slope of the isotherm at the measurement point. By considering the details of the multistep reaction paths involved in the hydriding reaction, model impedance equations have been derived for single- and two-phase domains, and fitted to experimental impedance diagrams. The possibility of separately measuring surface and phase transformation resistances, hydrogen diffusion coefficient, and hydrogen solubility in each composition domain is discussed.

  2. Potential energy curves and electronic structure of 3d transition metal hydrides and their cations.

    Science.gov (United States)

    Goel, Satyender; Masunov, Artëm E

    2008-12-07

    We investigate gas-phase neutral and cationic hydrides formed by 3d transition metals from Sc to Cu with density functional theory (DFT) methods. The performance of two exchange-correlation functionals, Boese-Martin for kinetics (BMK) and Tao-Perdew-Staroverov-Scuseria (TPSS), in predicting bond lengths and energetics, electronic structures, dipole moments, and ionization potentials is evaluated in comparison with available experimental data. To ensure a unique self-consistent field (SCF) solution, we use stability analysis, Fermi smearing, and continuity analysis of the potential energy curves. Broken-symmetry approach was adapted in order to get the qualitatively correct description of the bond dissociation. We found that on average BMK predicted values of dissociation energies and ionization potentials are closer to experiment than those obtained with high level wave function theory methods. This agreement deteriorates quickly when the fraction of the Hartree-Fock exchange in DFT functional is decreased. Natural bond orbital (NBO) population analysis was used to describe the details of chemical bonding in the systems studied. The multireference character in the wave function description of the hydrides is reproduced in broken-symmetry DFT description, as evidenced by NBO analysis. We also propose a new scheme to correct for spin contamination arising in broken-symmetry DFT approach. Unlike conventional schemes, our spin correction is introduced for each spin-polarized electron pair individually and therefore is expected to yield more accurate energy values. We derive an expression to extract the energy of the pure singlet state from the energy of the broken-symmetry DFT description of the low spin state and the energies of the high spin states (pentuplet and two spin-contaminated triplets in the case of two spin-polarized electron pairs). The high spin states are build with canonical natural orbitals and do not require SCF convergence.

  3. Development of physics based analytical interatomic potential for palladium-hydride.

    Science.gov (United States)

    Park, Young Ho; Hijazi, Iyad

    2017-04-01

    Palladium hydrides (Pd-H) research is an important topic in materials research with many practical industrial applications. The complex behavior of the Pd-H alloy system such as phase miscibility gap, however, presents a huge challenge for developing reliable computational models. The embedded atom method (EAM) offers an advantage of computational efficiency and being suited to the metal-hydride system. We propose a new EAM interatomic potential for the complete mathematical modeling of palladium hydride. The present interatomic potential well predicts the lattice constant, cohesive energy, bulk modulus, other elastic constants, and stable alloy crystal structures during molecular dynamics simulations. The phase miscibility gap is also accurately predicted for the Pd-H system using the present potential. To our knowledge, only two Pd-H EAM potentials were used for predicting the phase miscibility gap for the PdH system. The predicted values from these works, however, considerably deviated from the experimental result, which hinders further application to the palladium hydride system. The present potential is reliably accurate and can be used to study the Pd-H system with its compete description of the mathematical formalism.

  4. The Origin of the Catalytic Activity of a Metal Hydride in CO2 Reduction.

    Science.gov (United States)

    Kato, Shunsuke; Matam, Santhosh Kumar; Kerger, Philipp; Bernard, Laetitia; Battaglia, Corsin; Vogel, Dirk; Rohwerder, Michael; Züttel, Andreas

    2016-05-10

    Atomic hydrogen on the surface of a metal with high hydrogen solubility is of particular interest for the hydrogenation of carbon dioxide. In a mixture of hydrogen and carbon dioxide, methane was markedly formed on the metal hydride ZrCoHx in the course of the hydrogen desorption and not on the pristine intermetallic. The surface analysis was performed by means of time-of-flight secondary ion mass spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy, for the in situ analysis. The aim was to elucidate the origin of the catalytic activity of the metal hydride. Since at the initial stage the dissociation of impinging hydrogen molecules is hindered by a high activation barrier of the oxidised surface, the atomic hydrogen flux from the metal hydride is crucial for the reduction of carbon dioxide and surface oxides at interfacial sites.

  5. Phase-space structures and stellar populations in the star-forming region NGC~ 2264

    CERN Document Server

    Gonzalez, Marta

    2016-01-01

    In this work we analyse the structure of a subspace of the phase space of the star-forming region NGC~ 2264 using the Spectrum of Kinematic Groupings (SKG). We show that the SKG can be used to process a collection of star data to find substructure at different scales. We have found structure associated with the NGC~ 2264 region and also with the background area. In the NGC~ 2264 region, a hierarchical analysis shows substructure compatible with that found in previous specific studies of the area but with an objective, compact methodology that allows us to homogeneously compare the structure of different clusters and star-forming regions. Moreover, this structure is compatible with the different ages of the main NGC~ 2264 star-forming populations. The structure found in the field can be roughly associated with giant stars far in the background, dynamically decoupled from NGC~ 2264, which could be related either with the Outer Arm or Monoceros Ring. The results in this paper confirm the relationship between str...

  6. Angle-dependent hard X-ray photoemission study of Nb hydride formation in high-pressure supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Soda, Kazuo, E-mail: j45880a@cc.nagoya-u.ac.jp [Department of Quantum Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kondo, Hiroki; Yamaguchi, Kanta; Kato, Masahiko [Department of Quantum Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Shiraki, Tatsuhito; Niwa, Ken; Kusaba, Keiji; Hasegawa, Masashi [Department of Crystalline Materials Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Xeniya, Kozina; Ikenaga, Eiji [Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan)

    2015-09-15

    Highlights: • Nb hydrides in 10-GPa supercritical water are studied by photoelectron spectroscopy. • The hydride components of the Nb 3d core-level spectra are increased with the depth. • The bulk valence-band spectrum shows a split band due to the Nb–H bond formation. • The hydrides are formed in the bulk and their surfaces are covered with Nb oxides. - Abstract: Nb hydrides formation in 10-GPa supercritical water has been investigated by angle-dependent micro-beam hard X-ray photoemission spectroscopy. In the Nb 3d core-level spectra, Nb hydride components are found in the slightly high binding energy side of the metallic components, and the oxide ones are observed even though little oxides are recognized in X-ray diffraction patterns. Obtained emission-angle dependence of the Nb 3d core-level spectra of Nb hydride specimens shows that the Nb hydride components increase with the emission angle decreased i.e. the sampling depth increased, while the oxide ones decrease. The bulk valence-band spectrum is obtained by decomposing the measured valence-band spectra into a bulk and surface components with use of the emission-angle dependence of the core-level and valence-band spectra; it consists of two bands. This implies the Nb–H chemical bond formation and Nb in an oxidation state, consistent with reported band structure calculations and the observed core-level chemical shifts. Thus it is confirmed by valence-band and core-level photoelectron spectroscopy that the Nb hydrides are formed inside the specimen, irrespective to the well-known high oxidation ability of supercritical water.

  7. Influence of coupling with calculation of phase diagrams on microsegregation forming simulation of Al-4.5%Cu alloy

    Institute of Scientific and Technical Information of China (English)

    LIU Yong-gang; CHEN Guang; SUN Guo-xiong

    2006-01-01

    The effect of coupling with calculation of phase diagrams on microsegregation forming simulation was investigated. The traditional simplified phase diagram and calculated phase diagram were introduced into the numerical models respectively and simulation on microsegregation forming of the Al-4.5%Cu alloy ingot was also presented. The simulation results were both compared with the experiment results. The results show that the calculated sencondary arm spacing with these two kinds of phase diagram are almost the same because relationship between the coarsening model and the information of phase diagram is not close. The calculated eutectic phase volume fractions of different locations in the ingot coupled with different phase diagrams are discrepant. The calculated volume fractions are consistent with the experiment results when calculated phase diagram couples, but are far from the experiment results and obviously inacceptable when traditional simplified phase diagram couples. So, coupling with accurate calculated phase diagrams is very significant for microsegregation forming simulation since much information of the phase diagram is used in the models and it can improve the precision of simulation results.

  8. Hydrogen Storage Engineering Center of Excellence Metal Hydride Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Motyka, T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2014-05-31

    The Hydrogen Storage Engineering Center of Excellence (HSECoE) was established in 2009 by the U.S. Department of Energy (DOE) to advance the development of materials-based hydrogen storage systems for hydrogen-fueled light-duty vehicles. The overall objective of the HSECoE is to develop complete, integrated system concepts that utilize reversible metal hydrides, adsorbents, and chemical hydrogen storage materials through the use of advanced engineering concepts and designs that can simultaneously meet or exceed all the DOE targets. This report describes the activities and accomplishments during Phase 1 of the reversible metal hydride portion of the HSECoE, which lasted 30 months from February 2009 to August 2011. A complete list of all the HSECoE partners can be found later in this report but for the reversible metal hydride portion of the HSECoE work the major contributing organizations to this effort were the United Technology Research Center (UTRC), General Motors (GM), Pacific Northwest National Laboratory (PNNL), the National Renewable Energy Laboratory (NREL) and the Savannah River National Laboratory (SRNL). Specific individuals from these and other institutions that supported this effort and the writing of this report are included in the list of contributors and in the acknowledgement sections of this report. The efforts of the HSECoE are organized into three phases each approximately 2 years in duration. In Phase I, comprehensive system engineering analyses and assessments were made of the three classes of storage media that included development of system level transport and thermal models of alternative conceptual storage configurations to permit detailed comparisons against the DOE performance targets for light-duty vehicles. Phase 1 tasks also included identification and technical justifications for candidate storage media and configurations that should be capable of reaching or exceeding the DOE targets. Phase 2 involved bench-level testing and

  9. In-situ X-ray diffraction study on MlNi3.75 Co0.75 Mn0.3 Al0.2 during electrochemical hydriding-dehydriding process

    Institute of Scientific and Technical Information of China (English)

    袁志庆; 吕光烈; 顾建明; 屠小燕; 王新喜

    2004-01-01

    Phase transformations and lattice expansions of M1Ni3.75 Co0.75 Mn0.3 Al0.2 during the electrochemical hydriding-dehydriding process were investigated using in-situ X-ray diffraction. An intermediate hydride γ phase between the hydrogen solid solution a phase and fully hydrided β phase can be observed during the cycling. The formation of γ phase is related to the diffusion of hydrogen in the crystal grains. The lower the charge rate is, the higher the content of γ phase is. The phase transformations during the hydriding-dehydriding process can be described as α(→←)α+γ+β(→←)β(→←)γ+α(→←)α. The lattice expansion from a toβ is discrete, while that from γ to β is continuous. The formation of γ phase can reduce the discrete lattice expansion from a toβ by 30 %.

  10. Thin-film metal hydrides.

    Science.gov (United States)

    Remhof, Arndt; Borgschulte, Andreas

    2008-12-01

    The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

  11. Investigation of the hydrogen neutrals in a discharge source used for production of metal hydrides

    Science.gov (United States)

    Bozhinova, I.; Iordanova, S.; Pashov, A.

    2016-03-01

    The paper discusses the possible mechanisms for production of metal hydrides (MH) in a DC discharge source. The results of different experiments suggest that the molecules are sputtered directly from the surface of the cathode, where they are formed after adsorption of atomic hydrogen. This hypothesis allows one to understand the operation of the source studied and to optimize its working conditions.

  12. Can Pearlite form Outside of the Hultgren Extrapolation of the Ae3 and Acm Phase Boundaries?

    Science.gov (United States)

    Aranda, M. M.; Rementeria, R.; Capdevila, C.; Hackenberg, R. E.

    2016-02-01

    It is usually assumed that ferrous pearlite can form only when the average austenite carbon concentration C 0 lies between the extrapolated Ae3 ( γ/ α) and Acm ( γ/ θ) phase boundaries (the "Hultgren extrapolation"). This "mutual supersaturation" criterion for cooperative lamellar nucleation and growth is critically examined from a historical perspective and in light of recent experiments on coarse-grained hypoeutectoid steels which show pearlite formation outside the Hultgren extrapolation. This criterion, at least as interpreted in terms of the average austenite composition, is shown to be unnecessarily restrictive. The carbon fluxes evaluated from Brandt's solution are sufficient to allow pearlite growth both inside and outside the Hultgren Extrapolation. As for the feasibility of the nucleation events leading to pearlite, the only criterion is that there are some local regions of austenite inside the Hultgren Extrapolation, even if the average austenite composition is outside.

  13. Double-bilayer: a new phase formed by lysophospholipids and the corresponding fatty acid

    Directory of Open Access Journals (Sweden)

    Sérgio S. Funari

    2009-01-01

    Full Text Available The product of catalytic activity of the enzyme phospholipase A2, which resembles the core unit of animal toxins, on phospholipids is a 1:1 mixture of lysolipid and fatty acid. This mixture was studied by time-resolved simultaneous small- and wide angle x-ray diffraction over the temperature range from 23 to 53.5ºC. An unusually large lamellar structure was observed, with d = 11 nm, contradicting the complex functional dimer model between lysolipid and fatty acid. It can be explained by formation of a "double-bilayer", a new phase consisting of two different bilayers, one formed by lysophospholipid and other by fatty acid, bound together by head group interactions. Its strucutre was confirmed by simulations of the X-ray scattering pattern.

  14. Coarse-grained models of stripe forming systems: phase diagrams, anomalies, and scaling hypothesis.

    Science.gov (United States)

    Mendoza-Coto, Alejandro; Stariolo, Daniel A

    2012-11-01

    Two coarse-grained models which capture some universal characteristics of stripe forming systems are studied. At high temperatures, the structure factors of both models attain their maxima on a circle in reciprocal space, as a consequence of generic isotropic competing interactions. Although this is known to lead to some universal properties, we show that the phase diagrams have important differences, which are a consequence of the particular k dependence of the fluctuation spectrum in each model. The phase diagrams are computed in a mean field approximation and also after inclusion of small fluctuations, which are shown to modify drastically the mean field behavior. Observables like the modulation length and magnetization profiles are computed for the whole temperature range accessible to both models and some important differences in behavior are observed. A stripe compression modulus is computed, showing an anomalous behavior with temperature as recently reported in related models. Also, a recently proposed scaling hypothesis for modulated systems is tested and found to be valid for both models studied.

  15. Draft of M2 Report on Integration of the Hybrid Hydride Model into INL's MBM Framework for Review

    Energy Technology Data Exchange (ETDEWEB)

    Tikare, Veena; Weck, Philippe F.; Schultz, Peter Andrew; Clark, Blythe; Glazoff, Michael V.; Homer, Eric R.

    2014-07-01

    This report documents the development, demonstration and validation of a mesoscale, microstructural evolution model for simulation of zirconium hydride {delta}-ZrH{sub 1.5} precipitation in the cladding of used nuclear fuels that may occur during long-term dry storage. While the Zr-based claddings are manufactured free of any hydrogen, they absorb hydrogen during service, in the reactor by a process commonly termed ‘hydrogen pick-up’. The precipitation and growth of zirconium hydrides during dry storage is one of the most likely fuel rod integrity failure mechanisms either by embrittlement or delayed hydride cracking of the cladding. While the phenomenon is well documented and identified as a potential key failure mechanism during long-term dry storage (NUREG/CR-7116), the ability to actually predict the formation of hydrides is poor. The model being documented in this work is a computational capability for the prediction of hydride formation in different claddings of used nuclear fuels. This work supports the Used Fuel Disposition Research and Development Campaign in assessing the structural engineering performance of the cladding during and after long-term dry storage. This document demonstrates a basic hydride precipitation model that is built on a recently developed hybrid Potts-phase field model that combines elements of Potts-Monte Carlo and the phase-field models. The model capabilities are demonstrated along with the incorporation of the starting microstructure, thermodynamics of the Zr-H system and the hydride formation mechanism.

  16. Mathematical modeling of the nickel/metal hydride battery system

    Energy Technology Data Exchange (ETDEWEB)

    Paxton, Blaine Kermit [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering

    1995-09-01

    A group of compounds referred to as metal hydrides, when used as electrode materials, is a less toxic alternative to the cadmium hydroxide electrode found in nickel/cadmium secondary battery systems. For this and other reasons, the nickel/metal hydride battery system is becoming a popular rechargeable battery for electric vehicle and consumer electronics applications. A model of this battery system is presented. Specifically the metal hydride material, LaNi{sub 5}H{sub 6}, is chosen for investigation due to the wealth of information available in the literature on this compound. The model results are compared to experiments found in the literature. Fundamental analyses as well as engineering optimizations are performed from the results of the battery model. In order to examine diffusion limitations in the nickel oxide electrode, a ``pseudo 2-D model`` is developed. This model allows for the theoretical examination of the effects of a diffusion coefficient that is a function of the state of charge of the active material. It is found using present data from the literature that diffusion in the solid phase is usually not an important limitation in the nickel oxide electrode. This finding is contrary to the conclusions reached by other authors. Although diffusion in the nickel oxide active material is treated rigorously with the pseudo 2-D model, a general methodology is presented for determining the best constant diffusion coefficient to use in a standard one-dimensional battery model. The diffusion coefficients determined by this method are shown to be able to partially capture the behavior that results from a diffusion coefficient that varies with the state of charge of the active material.

  17. Structural and kinetic studies of metal hydride hydrogen storage materials using thin film deposition and characterization techniques

    Science.gov (United States)

    Kelly, Stephen Thomas

    Hydrogen makes an attractive energy carrier for many reasons. It is an abundant chemical fuel that can be produced from a wide variety of sources and stored for very long periods of time. When used in a fuel cell, hydrogen emits only water at the point of use, making it very attractive for mobile applications such as in an automobile. Metal hydrides are promising candidates for on-board reversible hydrogen storage in mobile applications due to their very high volumetric storage capacities---in most cases exceeding even that of liquid hydrogen. The United States Department of Energy (DOE) has set fuel system targets for an automotive hydrogen storage system, but as of yet no single material meets all the requirements. In particular, slow reaction kinetics and/or inappropriate thermodynamics plague many metal hydride hydrogen storage materials. In order to engineer a practical material that meets the DOE targets, we need a detailed understanding of the kinetic and thermodynamic properties of these materials during the phase change. In this work I employed sputter deposited thin films as a platform to study materials with highly controlled chemistry, microstructure and catalyst placement using thin film characterization techniques such as in situ x-ray diffraction (XRD) and neutron reflectivity. I observed kinetic limitations in the destabilized Mg2Si system due to the slow diffusion of the host Mg and Si atoms while forming separate MgH2 and Si phases. Conversely, I observed that the presence of Al in the Mg/Al system inhibits hydrogen diffusion while the host Mg and Al atoms interdiffuse readily, allowing the material to fall into a kinetic and/or thermodynamic trap by forming intermetallic compounds such as Mg17Al 12. By using in situ XRD to analyze epitaxial Mg films grown on (001) oriented Al2O3 substrates I observed hydride growth consistent with a model of a planar hydride layer growing into an existing metal layer. Subsequent film cycling changes the hydrogen

  18. Lattice contraction in photochromic yttrium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter, E-mail: jepe@ife.no; Mongstad, Trygve T.; You, Chang Chuan; Karazhanov, Smagul

    2013-12-15

    Highlights: •Photochromic yttrium hydride films (YH:O) were prepared by reactive sputtering. •Black and transparent YH:O films were studied by time-resolved synchrotron XRD. •Both YH:O samples showed a lattice contraction upon illumination. •Also exposure to the X-ray beam itself results in a lattice contraction. -- Abstract: A strong photochromic effect was recently discovered in thin films of oxygen-containing yttrium hydride taking place at room temperature and reacting to ultraviolet and visible light. In this paper, we report on a lattice contraction upon illumination observed for thin-film samples of photochromic yttrium hydride, recorded by time-resolved X-ray diffraction using synchrotron radiation. The time dependence of the lattice contraction is consistent with the observed photochromic response of the samples.

  19. Hydrogen storage in complex metal hydrides

    Directory of Open Access Journals (Sweden)

    BORISLAV BOGDANOVIĆ

    2009-02-01

    Full Text Available Complex metal hydrides such as sodium aluminohydride (NaAlH4 and sodium borohydride (NaBH4 are solid-state hydrogen-storage materials with high hydrogen capacities. They can be used in combination with fuel cells as a hydrogen source thus enabling longer operation times compared with classical metal hydrides. The most important point for a wide application of these materials is the reversibility under moderate technical conditions. At present, only NaAlH4 has favourable thermodynamic properties and can be employed as a thermally reversible means of hydrogen storage. By contrast, NaBH4 is a typical non- -reversible complex metal hydride; it reacts with water to produce hydrogen.

  20. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    Science.gov (United States)

    Morris, Robert H

    2016-12-01

    This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.

  1. Isomers and conformational barriers of gas phase nicotine, nornicotine and their protonated forms

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, Tomoki; Farone, William A.; Xantheas, Sotiris S.

    2014-07-17

    We report extensive conformational searches of the neutral nicotine, nornicotine and their protonated analogs that are based on ab-initio second order Møller-Plesset perturbation (MP2) electronic structure calculations. Initial searches were performed with the 6-31G(d,p) and the energetics of the most important structures were further refined from geometry optimizations with the aug-cc-pVTZ basis set. Based on the calculated free energies at T=298 K for the gas phase molecules, neutral nicotine has two dominant trans conformers, whereas neutral nornicotine is a mixture of several conformers. For nicotine, the protonation on both the pyridine and the pyrrolidine sites is energetically competitive, whereas nornicotine prefers protonation on the pyridine nitrogen. The protonated form of nicotine is mainly a mixture of two pyridine-protonated trans conformers and two pyrrolidine-protonated trans conformers, whereas the protonated form of nornicotine is a mixture of four pyridine-protonated trans conformers. Nornicotine is conformationally more flexible than nicotine, however it is less protonated at the biologically important pyrrolidine nitrogen site. The lowest energy isomers for each case were found to interconvert via low (< 6 kcal/mol) rotational barriers around the pyridine-pyrrolidine bond.

  2. Removal of pyridine from liquid and gas phase by copper forms of natural and synthetic zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Rehakova, Maria, E-mail: maria.rehakova@upjs.sk [Institute of Chemistry, Faculty of Science, P.J. Safarik University, 041 54 Kosice (Slovakia); Fortunova, Lubica [Institute of Chemistry, Faculty of Science, P.J. Safarik University, 041 54 Kosice (Slovakia); Bastl, Zdenek [J. Heyrovsky Institute of Physical Chemistry, ASCR, v.v.i., 18223 Prague 8 (Czech Republic); Nagyova, Stanislava [Department of Physics, Electrotechnical Faculty, Technical University, 042 00 Kosice (Slovakia); Dolinska, Silvia [Institute of Geotechnics, Slovak Academy of Sciences, 043 53 Kosice (Slovakia); Jorik, Vladimir [Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, 81237 Bratislava (Slovakia); Jona, Eugen [Department of Chemistry and Technology of Inorganic Materials, Faculty of Industrial Technologies, Trencin University of Alexander Dubcek, 02032 Puchov (Slovakia)

    2011-02-15

    Zeoadsorbents on the basis of copper forms of synthetic zeolite ZSM5 and natural zeolite of the clinoptilolite type (CT) have been studied taking into account their environmental application in removing harmful pyridine (py) from liquid and gas phase. Sorption of pyridine by copper forms of zeolites (Cu-ZSM5 and Cu-CT) has been studied by CHN, X-ray photoelectron spectroscopy, X-ray powder diffractometry, FTIR spectroscopy, thermal analysis (TG, DTA and DTG) and analysis of the surface areas and the pore volumes by low-temperature adsorption of nitrogen. The results of thermal analyses of Cu-ZSM5, Cu-(py){sub x}ZSM5, Cu-CT and Cu-(py){sub x}CT zeolitic products with different composition (x depends on the experimental conditions of sorption of pyridine) clearly confirmed their different thermal properties as well as the sorption of pyridine. In the zeolitic pyridine containing samples the main part of the pyridine release process occurs at considerably higher temperatures than is the boiling point of pyridine, which proves strong bond and irreversibility of py-zeolite interaction. FTIR spectra of Cu-(py){sub x}zeolite samples showed well resolved bands of pyridine. The results of thermal analysis and FTIR spectroscopy are in a good agreement with the results of other used methods.

  3. Removal of pyridine from liquid and gas phase by copper forms of natural and synthetic zeolites.

    Science.gov (United States)

    Reháková, Mária; Fortunová, Lubica; Bastl, Zdeněk; Nagyová, Stanislava; Dolinská, Silvia; Jorík, Vladimír; Jóna, Eugen

    2011-02-15

    Zeoadsorbents on the basis of copper forms of synthetic zeolite ZSM5 and natural zeolite of the clinoptilolite type (CT) have been studied taking into account their environmental application in removing harmful pyridine (py) from liquid and gas phase. Sorption of pyridine by copper forms of zeolites (Cu-ZSM5 and Cu-CT) has been studied by CHN, X-ray photoelectron spectroscopy, X-ray powder diffractometry, FTIR spectroscopy, thermal analysis (TG, DTA and DTG) and analysis of the surface areas and the pore volumes by low-temperature adsorption of nitrogen. The results of thermal analyses of Cu-ZSM5, Cu-(py)(x)ZSM5, Cu-CT and Cu-(py)(x)CT zeolitic products with different composition (x depends on the experimental conditions of sorption of pyridine) clearly confirmed their different thermal properties as well as the sorption of pyridine. In the zeolitic pyridine containing samples the main part of the pyridine release process occurs at considerably higher temperatures than is the boiling point of pyridine, which proves strong bond and irreversibility of py-zeolite interaction. FTIR spectra of Cu-(py)(x)zeolite samples showed well resolved bands of pyridine. The results of thermal analysis and FTIR spectroscopy are in a good agreement with the results of other used methods.

  4. First-principles prediction of new complex transition metal hydrides for high temperature applications.

    Science.gov (United States)

    Nicholson, Kelly M; Sholl, David S

    2014-11-17

    Metal hydrides with high thermodynamic stability are desirable for high-temperature applications, such as those that require high hydrogen release temperatures or low hydrogen overpressures. First-principles calculations have been used previously to identify complex transition metal hydrides (CTMHs) for high temperature use by screening materials with experimentally known structures. Here, we extend our previous screening of CTMHs with a library of 149 proposed materials based on known prototype structures and charge balancing rules. These proposed materials are typically related to known materials by cation substitution. Our semiautomated, high-throughput screening uses density functional theory (DFT) and grand canonical linear programming (GCLP) methods to compute thermodynamic properties and phase diagrams: 81 of the 149 materials are found to be thermodynamically stable. We identified seven proposed materials that release hydrogen at higher temperatures than the associated binary hydrides and at high temperature, T > 1000 K, for 1 bar H2 overpressure. Our results indicate that there are many novel CTMH compounds that are thermodynamically stable, and the computed thermodynamic data and phase diagrams should be useful for selecting materials and operating parameters for high temperature metal hydride applications.

  5. Laboratory Rotational Spectroscopy of the Interstellar Diatomic Hydride Ion SH+ (X 3Σ-)

    Science.gov (United States)

    Halfen, DeWayne; Ziurys, Lucy M.

    2016-06-01

    Diatomic hydride are among the most common molecular species in the interstellar medium (ISM). The low molecular mass and thus moments of inertia cause their rotational spectra to lie principally in the submillimeter and far-infrared regions. Diatomic hydrides, both neutral (MH) and ionic (MH+) forms, are also basic building blocks of interstellar chemistry. In ionic form, they may be the “hidden” carriers of refractory elements in dense gas. They are therefore extremely good targets for space-borne and airborne platforms such as Herschel, SOFIA, and SAFIR. However, in order to detect these species in the ISM, their rotational spectra must first be measured in the laboratory. To date, there is very little high resolution data available for many hydride species, in particular the ionic form. Using submillimeter/THz direct absorption methods in the Ziurys laboratory, spectra of the interstellar diatomic hydride SH+ (X 3Σ-) have been recorded. Recent work has concerned measurement of all three fine structure components of the fundamental rotational transition N = 1 ← 0 in the range 345 - 683 GHz. SH+ was generated from H2S and argon in an AC discharge. The data have been analyzed, and spectroscopic constants for this species have been refined. SH+ is found in Photon Dominated Regions (PDRs) and X-ray Dominated Regions (XDRs) and is thought to trace energetic processes in the ISM. These current measurements confirm recent observations of this species at submillimeter/THz wavelengths with ALMA and other ground-based telescopes.

  6. Phase transformations and hydrogen-storage characteristics of Mg-transition metal-oxide alloys

    Science.gov (United States)

    Song, Myoung Youp; Baek, Sung Hwan; Bobet, Jean-Loius; Park, Hye Ryoung

    2013-03-01

    Samples with the compositions of 76.5 wt%Mg-23.5 wt%Ni (Mg-Ni), 71.5 wt%Mg-23.5 wt%Ni-5 wt% Fe2O3 (Mg-Ni-Fe2O3) and 71.5 wt%Mg-23.5 wt%Ni-5 wt% Fe2O3 (spray conversion) (Mg-Ni-scFe2O3), 71.5 wt%Mg-23.5 wt%Ni-5 wt% Fe (Mg-Ni-Fe) and 80 wt%Mg-13.33 wt%Ni-6.67 wt%Fe (Mg-13Ni-7Fe) were prepared by reactive mechanical grinding. Mg-13Ni-7Fe has the highest hydriding and dehydriding rates. After hydriding-dehydriding cycling, all the samples contain the Mg2Ni phase. The samples with Fe2O3 and Fe2O3(spray conversion) as starting materials contain the Mg(OH)2 phase after hydriding-dehydriding cycling as well as after reactive mechanical grinding. Mg-Ni-Fe and Mg-13Ni-7Fe contain the MgH2 phase after reactive mechanical grinding. Phases, space groups, cell parameters, contents and crystallite sizes were analyzed by Full Pattern Matching Refinement program, one of the Rietveld analysis programs, from the XRD powder patterns of Mg-Ni-scFe2O3 after reactive mechanical grinding and after hydriding-dehydriding cycling. The MgH2 phase formed in the Mg-Ni-Fe and Mg-13Ni-7Fe mixtures after reactive mechanical grinding is considered to help the pulverization of the materials during reactive mechanical grinding, leading to the high hydriding and dehydriding rates of these mixtures.

  7. Structural and magnetic transformations in NdMn{sub 2}H{sub x} hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Budziak, A., E-mail: andrzej.budziak@ifj.edu.pl [H. Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Zachariasz, P. [Faculty of Physics and Applied Computer Science, AGH, University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow (Poland); Pelka, R. [The H. Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Figiel, H.; Zukrowski, J.; Woch, M.W. [Faculty of Physics and Applied Computer Science, AGH, University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow (Poland)

    2012-06-05

    Highlights: Black-Right-Pointing-Pointer Full structural phase diagram is presented for the NdMn{sub 2}H{sub x} (2.0 {<=} x {<=} 4.0) hydrides in the temperature range of 70-385 K. Black-Right-Pointing-Pointer For samples x = 2.0, 2.5, and 4.0 a splitting into two phases with different hydrogen concentrations are observed. Black-Right-Pointing-Pointer Only for samples with x = 3.0 and 3.5 no spinodal decompositions are detected. Black-Right-Pointing-Pointer The effects of hydrogen absorption on structural properties are shown to be reflected in magnetic behavior. Black-Right-Pointing-Pointer A huge jump of magnetic ordering temperatures from {approx}104 K for host NdMn{sub 2} to above 200 K for its hydrides is observed or anticipated. - Abstract: X-ray powder diffraction and bulk magnetization measurements were used to study structural and magnetic properties of hydrides NdMn{sub 2}H{sub x} (2.0 {<=} x {<=} 4.0). The X-ray investigations performed in the temperature range 70-385 K have revealed many structural transformations at low temperatures. In particular, a transformation from the hexagonal to the monoclinic phase and spinodal decompositions were observed. The magnetic behavior of the hydrides is correlated with the structural transitions. A tentative structural diagram is presented. The obtained results are compared with the properties of other cubic and hexagonal RMn{sub 2}H{sub x} hydrides.

  8. Superconductive "sodalite"-like clathrate calcium hydride at high pressures

    CERN Document Server

    Wang, Hui; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-01-01

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H2 fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH6 a body-centred cubic structure with hydrogen that forms unusual "sodalite" cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H2 of electrons donated by Ca forming a "H4" unit as the building block in the construction of the 3-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone centre. The resultant dynamic Jahn-Teller effect helps to enhance electron-phonon coupling and leads to superconductivity of CaH6. A superconducting critical temperature (Tc) of 220-235 K at 150 GPa obtained...

  9. Evidence of stress-induced hydrogen ordering in zirconium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Steuwer, A. [FaME38 at the ESRF-ILL, 6 rue J Horowitz, 38042 Grenoble (France); ESS Scandinavia, University of Lund, Stora Algatan 4, 22350 Lund (Sweden)], E-mail: steuwer@ill.fr; Santisteban, J.R. [Centro Atomico Bariloche, CNEA, San Carlos de Bariloche (Argentina); Preuss, M. [University of Manchester, Grosvenor Street, Manchester M1 7HS (United Kingdom); Peel, M.J.; Buslaps, T. [European Synchrotron Radiation Facility, 6 rue J Horowitz, 38042 Grenoble (France); Harada, M. [R and D Section, Chofu-Kita Plant, Kobe Special Tube Co, Shimonoseki 752-0953 (Japan)

    2009-01-15

    The formation of hydrides in zirconium alloys significantly affects their mechanical properties and is considered to play a critical role in their failure mechanisms, yet relatively little is known about the micromechanical behavior of hydrides in the bulk. This paper presents the result of in situ uniaxial mechanical tensioning experiments on hydrided zircaloy-2 and zircaloy-4 specimens using energy-dispersive synchrotron X-ray diffraction, which suggests that a stress-induced transformation of the {delta}-hydride to {gamma}-hydride via ordering of the hydrogen atoms occurs, akin to a Snoek-type relaxation. Subsequent annealing was found to reverse the ordering phenomenon.

  10. Structure of olefin-imidacloprid and gas-phase fragmentation chemistry of its protonated form.

    Science.gov (United States)

    Fusetto, Roberto; White, Jonathan M; Hutton, Craig A; O'Hair, Richard A J

    2016-02-01

    One of the major insect metabolites of the widely used neonicotinoid insecticide imidacloprid, 1 (1-[(6-chloro-3-pyridinyl)methyl]-N-nitro-1H-imidazol-2-amine), is the olefin 2. To better understand how the structure of olefin 2 relates to the gas-phase fragmentation of its protonated form, 2H(+), X-ray crystallography, tandem mass spectrometry experiments and DFT calculations were carried out. Olefin 2 was found to be in a tautomeric form where the proton is on the N(1) position of the imidazole ring and forms a hydrogen bond to one of the oxygen atoms of the coplanar nitroamine group. Under conditions of low-energy collision-induced dissociation (CID) in a linear ion trap, 2H(+), formed via electrospray ionization (ESI), fragments via a major loss of water, together with minor competing losses of HNO2 and NO2•.This contrasts with 1H+, which mainly undergoes bond homolysis via NO2• loss. Thus, installation of the double bond in 2 plays a key role in facilitating the loss of water. DFT calculations, carried out using the B3LYP/6-311G++(d,p) level of theory, revealed that loss of water was energetically more favourable compared to HNO2 and NO2• loss. Three multistep, energetically accessible mechanisms were identified for loss of water from 2H(+), and these have the following barriers: (I) direct proton transfer from N(5) of the pyridine to O(1) on the NO2 group (119 kJ mol(-1)); (II) rotation of the N(2)-N(4) bond (117 kJ mol(-1)); (III) 1,3-intramolecular proton transfer between the two oxygen atoms of the NO2 group (145 kJ mol(-1)). Given that the lowest barrier for the losses of HNO2 and NO2• is 156 kJ mol(-1), it is likely that all three water loss mechanisms occur concurrently.

  11. Pressure-induced transformations of molecular boron hydride

    CERN Document Server

    Nakano, S; Gregoryanz, E A; Goncharov, A F; Mao Ho Kwang

    2002-01-01

    Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV.

  12. Nature of the chemical bond in complex hydrides, NaAlH{sub 4}, LiAlH{sub 4}, LiBH{sub 4} and LiNH{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Yoshino, M. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan)]. E-mail: yoshino@silky.numse.nagoya-u.ac.jp; Komiya, K. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan); Takahashi, Y. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan); Shinzato, Y. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan); Yukawa, H. [Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan); Morinaga, M. [Department of Materials Science and Engineering, Graduate School of Engineering, Institute for Advanced Research, Nagoya University, Chikusa-Ku, Nagoya 464-8603 (Japan)

    2005-12-08

    The most stable crystal structures of complex hydrides, MXH{sub n} (NaAlH{sub 4}, LiAlH{sub 4}, LiBH{sub 4} and LiNH{sub 2}) were simulated by the plane-wave pseudopotential method. The local chemical bonds between constituent ions were simulated using the DV-X{alpha} molecular orbital method. As a result, it was found that the covalent interaction is operating between X and H ions to form a XH{sub n} ion in MXH{sub n}. In addition, the ionic interaction is operating between M and XH{sub n} ions through the charge transfer from M to XH{sub n} ions. On the basis of this understanding of the nature of the chemical bond between ions, a phase stability diagram of complex hydrides was proposed using two parameters. One is the bond energy of XH diatomic molecules and the other is electronegativity difference, {delta}{phi}{sub X-M}, between M and X ions. The calculated stability change by doping into NaAlH{sub 4} could by explained qualitatively following this diagram. This diagram will provide us a clue to the modification of hydrides to lower the hydrogen decomposition temperature.

  13. Organic solvents vapor pressure and relative humidity effects on the phase transition rate of α and β forms of tegafur.

    Science.gov (United States)

    Petkune, Sanita; Bobrovs, Raitis; Actiņš, Andris

    2012-01-01

    The objective of this work was to investigate the relative humidity (RH) and solvent vapor pressure effects on the phase transition dynamics between tegafur polymorphic forms that do not form hydrates and solvates. The commercially available α and β modifications of 5-fluoro-1-(tetrahydro-2-furyl)-uracil, known as the antitumor agent tegafur, were used as model materials for this study. While investigating the phase transitions of α and β tegafur under various partial pressures of methanol, n-propanol, n-butanol, and water vapor, it was determined that the phase transition rate increased in the presence of solvent vapors, even though no solvates were formed. By increasing the relative air humidity from 20% to 80%, the phase transition rate constant of α and β tegafur was increased about 60 times. After increasing the partial pressure of methanol, n-propanol, or n-butanol vapor, the phase transition rate constant did not change, but the extent of phase transformation was increased. In the homologous row of n-alcohols, the phase transition rate constant decreased with increasing carbon chain length. The dependence of phase transformation extent versus the RH corresponded to the polymolecular adsorption isotherm with a possible capillary condensation effect.

  14. Preparation of porous microsphere-scaffolds by electrohydrodynamic forming and thermally induced phase separation

    Energy Technology Data Exchange (ETDEWEB)

    Ghanbar, Hanif; Luo, C.J.; Bakhshi, Poonam [Department of Mechanical Engineering, University College London, Torrington Place, London, WC1E 7JE (United Kingdom); Day, Richard [Division of Medicine, University College London, Rockefeller Building, 21 University Street, London, WC1E 6JJ (United Kingdom); Edirisinghe, Mohan, E-mail: m.edirisinghe@ucl.ac.uk [Department of Mechanical Engineering, University College London, Torrington Place, London, WC1E 7JE (United Kingdom)

    2013-07-01

    The availability of forming technologies able to mass produce porous polymeric microspheres with diameters ranging from 150 to 300 μm is significant for some biomedical applications where tissue augmentation is required. Moreover, appropriate assembly of microspheres into scaffolds is an important challenge to enable direct usage of the as-formed structures in treatments. This work reports the production of poly (glycolic-co-lactic acid) and poly (ε-caprolactone) microspheres under ambient conditions using one-step electrohydrodynamic jetting (traditionally known as atomisation) and thermally induced phase separation (TIPS). To ensure robust production for practical uses, this work presents 12 comprehensive parametric mode mappings of the diameter distribution profiles of the microspheres obtained over a broad range of key processing parameters and correlating of this with the material parameters of 5 different polymer solutions of various concentrations. Poly (glycolic-co-lactic acid) (PLGA) in Dimethyl carbonate (DMC), a low toxicity solvent with moderate conductivity and low dielectric constant, generated microspheres within the targeted diameter range of 150–300 μm. The fabrication of the microspheres suitable for formation of the scaffold structure is achieved by changing the collection method from distilled water to liquid nitrogen and lyophilisation in a freeze dryer. Highlights: ► EHDA is a unique method for production of the desired size of microspheres. ► Polymer solution properties are used to tailor the size distribution of spheres. ► Process control parameters (flow rate and applied voltage) are key in size control. ► Combination of EHDA with TIPS provides porous microspheres for assembly of scaffold.

  15. Thermodynamic properties of the cubic plutonium hydride solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, J M

    1981-12-01

    Pressure, temperature, and composition data for the cubic solid solution plutonium hydride phase, PuH/sub x/, have been measured by microbalance methods. Integral enthalpies and entropies of formation have been evaluated for the composition range 1.90 less than or equal to X less than or equal to 3.00. At 550/sup 0/K, ..delta..H/sup 0/ /sub f/(PuH/sub x/(s)) varies linearly from approximately (-38 +- 1) kcal mol/sup -1/ at PuH/sub 190/ to (-50 +- 1 kcal mol/sup -1/) at PuH/sub 3/ /sub 00/. Thermochemical values obtained by reevaluating tensimetric data from the literature are in excellent agreement with these results. Isotopic effects have been quantified by comparing the results for hydride and deuteride, and equations are presented for predicting ..delta..H/sup 0/ /sub f/ and ..delta..S/sup 0/ /sub f/ values for PuH/sub x/(s) and PuD/sub x/(s).

  16. Electronic structure of the palladium hydride studied by compton scattering

    CERN Document Server

    Mizusaki, S; Yamaguchi, M; Hiraoka, N; Itou, M; Sakurai, Y

    2003-01-01

    The hydrogen-induced changes in the electronic structure of Pd have been investigated by Compton scattering experiments associated with theoretical calculations. Compton profiles (CPs) of single crystal of Pd and beta phase hydride PdH sub x (x=0.62-0.74) have been measured along the [100], [110] and [111] directions with a momentum resolution of 0.14-0.17 atomic units using 115 keV x-rays. The theoretical Compton profiles have been calculated from the wavefunctions obtained utilizing the full potential linearized augmented plane wave method within the local density approximation for Pd and stoichiometric PdH. The experimental and the theoretical results agreed well with respect to the difference in the CPs between PdH sub x and Pd, and the anisotropy in the CPs of Pd or PdH sub x. This study provides lines of evidence that upon hydride formation the lowest valance band of Pd is largely modified due to hybridization with H 1s-orbitals and the Fermi energy is raised into the sp-band. (author)

  17. Crystal structure and switchable optical properties of yttrium hydride films covered by palladium layer

    Institute of Scientific and Technical Information of China (English)

    张文魁; 甘永平; 杨晓光; 黄辉; 余厉阳

    2003-01-01

    The palladium/yttrium films were prepared using magnetron sputtering technique.The changes of crystal structure,morphology and optical properties of the films during the hydrogen absorption/desorption process were investigated.The results of SEM and AFM analysis show that yttrium films have columnar structure,and the Pd cover layers on the surface of the yttrium films are composed of nanometer-sized Pd particles,which contain a large amount of smaller crystalline grains.During the gas hydrogen absorption/desorption process,YH3 and YH2 hydrides form on the sites of Pd grains contacting with Y grains.Upon hydrogenation,YH3 hydride forms and the switchable optical properties can be observed.The light transparency of the films increases with the increasing of hydrogen loading time and the light wavelength,and the absorption limitation occurs at λ=400 nm.Upon dehydrogenation,YH3 hydride dissociates into YH2 hydride,and the maximum transparency occurs at λ=689 nm.

  18. MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO2 INDUCED PHASE SEPARATION

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the similar"sponge-like"and asymmetric structure when different solvent was used.As the mutual affinity between solvent and supercritical CO2 decreased,the membrane porosity and the average pore diameter increased.The PVDF-HFP membrane with porosity at 88% and pore size at 10 μm were successfully prepared.The uptake of electrolyte solution and lithium ionic conductivity could reach 487 wt% and 3.09×10-3 S/cm respectively for obtained membrane.

  19. Study of the mechanical behavior of the hydride blister/rim structure in Zircaloy-4 using in-situ synchrotron X-ray diffraction

    Science.gov (United States)

    Lin, Jun-li; Han, Xiaochun; Heuser, Brent J.; Almer, Jonathan D.

    2016-04-01

    High-energy synchrotron X-ray diffraction was utilized to study the mechanical response of the f.c.c δ hydride phase, the intermetallic precipitation with hexagonal C14 lave phase and the α-Zr phase in the Zircaloy-4 materials with a hydride rim/blister structure near one surface of the material during in-situ uniaxial tension experiment at 200 °C. The f.c.c δ was the only hydride phase observed in the rim/blister structure. The conventional Rietveld refinement was applied to measure the macro-strain equivalent response of the three phases. Two regions were delineated in the applied load versus lattice strain measurement: a linear elastic strain region and region that exhibited load partitioning. Load partitioning was quantified by von Mises analysis. The three phases were observed to have similar elastic modulus at 200 °C.

  20. Study of the mechanical behavior of the hydride blister/rim structure in Zircaloy-4 using in-situ synchrotron X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Jun-li; Han, Xiaochun; Heuser, Brent J.; Almer, Jonathan D.

    2016-04-01

    High-energy synchrotron X-ray diffraction was utilized to study the mechanical response of the f.c.c delta hydride phase, the intermetallic precipitation with hexagonal C14 lave phase and the alpha-Zr phase in the Zircaloy-4 materials with a hydride rim/blister structure near one surface of the material during in-situ uniaxial tension experiment at 200 degrees C. The f.c.c delta was the only hydride phase observed in the rim/blister structure. The conventional Rietveld refinement was applied to measure the macro-strain equivalent response of the three phases. Two regions were delineated in the applied load versus lattice strain measurement: a linear elastic strain region and region that exhibited load partitioning. Load partitioning was quantified by von Mises analysis. The three phases were observed to have similar elastic modulus at 200 degrees C.

  1. Study of the mechanical behavior of the hydride blister/rim structure in Zircaloy-4 using in-situ synchrotron X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Jun-li; Han, Xiaochun [Department of Nuclear, Plasma, and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL (United States); Heuser, Brent J., E-mail: bheuser@illinois.edu [Department of Nuclear, Plasma, and Radiological Engineering, University of Illinois at Urbana-Champaign, Urbana, IL (United States); Almer, Jonathan D. [Advanced Photon Source, Argonne National Laboratory, Argonne, IL (United States)

    2016-04-01

    High-energy synchrotron X-ray diffraction was utilized to study the mechanical response of the f.c.c δ hydride phase, the intermetallic precipitation with hexagonal C14 lave phase and the α-Zr phase in the Zircaloy-4 materials with a hydride rim/blister structure near one surface of the material during in-situ uniaxial tension experiment at 200 °C. The f.c.c δ was the only hydride phase observed in the rim/blister structure. The conventional Rietveld refinement was applied to measure the macro-strain equivalent response of the three phases. Two regions were delineated in the applied load versus lattice strain measurement: a linear elastic strain region and region that exhibited load partitioning. Load partitioning was quantified by von Mises analysis. The three phases were observed to have similar elastic modulus at 200 °C.

  2. DEVELOPMENT OF A FABRICATION PROCESS FOR SOL-GEL/METAL HYDRIDE COMPOSITE GRANULES

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, E; Eric Frickey, E; Leung Heung, L

    2004-02-23

    An external gelation process was developed to produce spherical granules that contain metal hydride particles in a sol-gel matrix. Dimensionally stable granules containing metal hydrides are needed for applications such as hydrogen separation and hydrogen purification that require columns containing metal hydrides. Gases must readily flow through the metal hydride beds in the columns. Metal hydrides reversibly absorb and desorb hydrogen and hydrogen isotopes. This is accompanied by significant volume changes that cause the metal hydride to break apart or decrepitate. Repeated cycling results in very fine metal hydride particles that are difficult to handle and contain. Fine particles tend to settle and pack making it more difficult to flow gases through a metal hydride bed. Furthermore, the metal hydrides can exert a significant force on the containment vessel as they expand. These problems associated with metal hydrides can be eliminated with the granulation process described in this report. Small agglomerates of metal hydride particles and abietic acid (a pore former) were produced and dispersed in a colloidal silica/water suspension to form the feed slurry. Fumed silica was added to increase the viscosity of the feed slurry which helped to keep the agglomerates in suspension. Drops of the feed slurry were injected into a 27-foot tall column of hot ({approx}70 C), medium viscosity ({approx}3000 centistokes) silicone oil. Water was slowly evaporated from the drops as they settled. The drops gelled and eventually solidified to form spherical granules. This process is referred to as external gelation. Testing was completed to optimize the design of the column, the feed system, the feed slurry composition, and the operating parameters of the column. The critical process parameters can be controlled resulting in a reproducible fabrication technique. The residual silicone oil on the surface of the granules was removed by washing in mineral spirits. The granules were

  3. Catalyzed light hydride nanomaterials embedded in a micro-channels hydrogen storage container.

    Science.gov (United States)

    Dehouche, Zahir; Peretti, Hernán A; Yoo, Yeong; Belkacemi, Khaled; Goyette, Jacques

    2009-01-01

    Activated alloys synthesized by arc-melting were examined as catalysts for improving the hydrogen sorption characteristics of nanostructured magnesium hydride, proposed as a reversible hydrogen storage material. The MgH(2)-catalyst absorbing materials were prepared by ball milling of pure MgH(2) with hydrided Zr(47)Ni(53), Zr(9)Ni(11), and other alloys investigated. The nanostructured MgH(2)-intermetallic systems were tested at 250 degrees C and catalyst addition of eutectoid Zr(47)Ni(53) resulted in the fastest desorption time and highest initial desorption rate. The catalyzed Mg-hydride with activated Zr(9)Ni(11) and Zr(7)Ni(10) phases showed fast desorption kinetics. Moreover, the results demonstrated that the composition of dispersed Zr(x)Ni(y)catalysts has a strong influence on the amount of accumulated hydrogen and desorption rate of Mg-nanocomposite. Part two covers advanced micro-channels hydrogen storage module design based on the results of semi-empirical computer simulations of heat and mass transfers in the container. The micro-channels reservoir concept offers many advantages over the conventional metal hydride hydrogen storage system. It is a micro-structured system that can pack a lot of power into a small space and dissipate effectively the heat of the sorption reactions. This review summarizes recent patents related to CNTS.

  4. Benzocaine polymorphism: pressure-temperature phase diagram involving forms II and III.

    Science.gov (United States)

    Gana, Inès; Barrio, Maria; Do, Bernard; Tamarit, Josep-Lluís; Céolin, René; Rietveld, Ivo B

    2013-11-18

    Understanding the phase behavior of an active pharmaceutical ingredient in a drug formulation is required to avoid the occurrence of sudden phase changes resulting in decrease of bioavailability in a marketed product. Benzocaine is known to possess three crystalline polymorphs, but their stability hierarchy has so far not been determined. A topological method and direct calorimetric measurements under pressure have been used to construct the topological pressure-temperature diagram of the phase relationships between the solid phases II and III, the liquid, and the vapor phase. In the process, the transition temperature between solid phases III and II and its enthalpy change have been determined. Solid phase II, which has the highest melting point, is the more stable phase under ambient conditions in this phase diagram. Surprisingly, solid phase I has not been observed during the study, even though the scarce literature data on its thermal behavior appear to indicate that it might be the most stable one of the three solid phases.

  5. Boron-nitrogen based hydrides and reactive composites for hydrogen storage

    DEFF Research Database (Denmark)

    Jepsen, Lars H.; Ley, Morten B.; Lee, Young-Su;

    2014-01-01

    Hydrogen forms chemical compounds with most other elements and forms a variety of different chemical bonds. This fascinating chemistry of hydrogen has continuously provided new materials and composites with new prospects for rational design and the tailoring of properties. This review highlights ...... a range of new boron and nitrogen based hydrides and illustrates how hydrogen release and uptake properties can be improved. © 2014 Elsevier Ltd....

  6. Studies of hydrogen absorption and desorption processes in advanced intermetallic hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Masashi

    2005-07-01

    This work is a part of the research program performed in the Department of Energy Systems, Institute for Energy Technology (Kjeller, Norway), which is focused on the development of the advanced hydrogen storage materials. The activities are aimed on studies of the mechanisms of hydrogen interactions with intermetallic alloys with focus on establishing an interrelation between the crystal structure, thermodynamics and kinetics of the processes in the metal-hydrogen systems, on the one hand, and hydrogen storage properties (capacity, rates of desorption, hysteresis). Many of the materials under investigation have potential to be applied in applications, whereas some already have been commercialised in the world market. A number of metals take up considerable amounts of hydrogen and form chemical compounds with H, metal hydrides. Unfortunately, binary hydrides are either very stable (e.g. for the rare earth metals [RE], Zr, Ti, Mg: metal R) or are formed at very high applied pressures of hydrogen gas (e.g. for the transition metals, Ni, Co, Fe, etc.: Metal T). However, hydrogenation process becomes easily reversible at very convenient from practical point of view conditions, around room temperature and at H2 pressures below 1 MPa for the two-component intermetallic alloys R{sub x}T{sub y}. This raised and maintains further interest to the intermetallic hydrides as solid H storage materials. Materials science research of this thesis is focused on studies of the reasons staying behind the beneficial effect of two non-transition elements M(i.e., In and Sn) contributing to the formation of the ternary intermetallic alloys R{sub x}T{sub y}M{sub 2}., on the hydrogen storage behaviours. Particular focus is on two aspects where the remarkable improvement of ordinary metal hydrides is achieved via introduction of In and Sn: a) Increase of the volume density of stored hydrogen in solid materials to the record high level. b) Improvement of the kinetics of hydrogen charge and

  7. Mössbauer study of oxide phase distributions in rust formed on steel constructions near the Black Sea in Sochi

    Energy Technology Data Exchange (ETDEWEB)

    Filippov, V. P., E-mail: vpfilippov@mephi.ru; Lauer, Yu. A. [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) (Russian Federation); Goloborodko, P. G.; Polyakov, A. M. [Sanatorium “Progress” (Russian Federation)

    2016-12-15

    The phase composition of the intermediate oxide layers formed on elements of steel structures at different positions relative to the sea water of the Black Sea near Sochi are investigated. The differences of the phase composition of these oxide layers are shown, depending on the location of the design details in relation to the sea and the abundancies of certain types of oxides in the studied layers are discussed.

  8. Mulled coal: A beneficiated coal form for use as a fuel or fuel intermediate. Phase 3, Final report

    Energy Technology Data Exchange (ETDEWEB)

    1993-08-01

    Energy International Corporation (El) was awarded a contract to evaluate a new concept for utilization of the fine coal wetcake produced by many of the physical beneficiation processes now under development. EI proposed development of a stabilized wetcake with properties that would facilitate storage, handling, transport, and subsequent conversion of the material into Coal-Water Fuel (CWF) at the point of use. The effort was performed in three phases. Phase I established the technical feasibility of stabilizing the fine coal ``wetcake`` in a form that can be readily handled and converted into a desired fuel form at the combustion site. The preferred form of stabilized ``wetcake`` was a granular free flowing material with the moisture encapsulated with the fine coal particles. The product was termed Mulled Coal. Phase I results indicated that the Mulled Coal was not only suitable as a CWF intermediate, but also had potential as a solid fuel. Phase II demonstrated the utilization of the Mulled Coal process to store and move fine coal products as a stable ``wetcake.`` Tasks in this phase tested components of the various systems required for storage, handling and combustion of the fine coals. Phase III expanded the technology by: 1. Evaluating Mulled Coal from representative coals from all producing regions in the US. 2. Development of bench-scale tests. 3. Design, construction, and operation of a 1 ton/hr continuous processing unit. 4. Evaluation of the effects of beneficiation. and 5. Developing an estimate of capital and operating costs for commercial units.

  9. Facile synthesis of nanosized sodium magnesium hydride, NaMgH3

    Institute of Scientific and Technical Information of China (English)

    Hazel Reardon; Natalia Mazur; Duncan H.Gregory

    2013-01-01

    The ternary magnesium hydride NaMgH3 has been synthesised via reactive milling techniques. The method employed neither a reactive H2 atmosphere nor high pressure sintering or other post-treatment processes. The formation of the ternary hydride was studied as a function of milling time and ball:powder ratio. High purity NaMgH3 powder (orthorhombic space group Pnma, a ¼ 5.437(2) Å, b ¼ 7.705(5) Å, c ¼ 5.477(2) Å;Z ¼ 4) was prepared in 5 h at high ball:powder ratios and characterised by powder X-ray diffraction (PXD), Raman spectroscopy and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX). The products formed sub-micron scale (typically 200-400 nm in size) crystallites that were approximately isotropic in shape. The dehydrogenation behaviour of the ternary hydride was investigated by temperature programmed desorption (TPD). The nanostructured hydride releases hydrogen in two steps with an onset temperature for the first step of 513 K.

  10. The cephalic phase insulin response to nutritive and low-calorie sweeteners in solid and beverage form.

    Science.gov (United States)

    Dhillon, Jaapna; Lee, Janice Y; Mattes, Richard D

    2017-09-09

    The purpose of the study was to examine the role of the cephalic phase insulin response (CPIR) following exposure to nutritive and low-calorie sweeteners in solid and beverage form in overweight and obese adults. In addition, the role of learning on the CPIR to nutritive and low-calorie sweetener exposure was tested. Sixty-four overweight and obese adults (age: 18-50years, BMI: 24-37kg/m(2), body fat percentage>25% for men and >32% for women) were sham-fed (at 2-minute intervals for 14min) a randomly assigned test load comprised of a nutritive (sucrose) or low calorie sweetener (sucralose) in beverage or solid form in phase 1 of the study. A 2-3ml blood sample was collected before and 2, 6, 10, 14, 61, 91 and 121min after oral exposure for serum insulin and glucose analysis. During phase 2, participants underwent a 2-week training period to facilitate associative learning between the sensory properties of test loads and their post-ingestive effects. In phase 3, participants were retested for their cephalic phase responses as in phase 1. Participants were classified as responders if they demonstrated a positive insulin response (rise of serum insulin above baseline i.e. Δ insulin) 2min post-stimulus in phase 1. Among responders exposed to the same sweetener in Phases 1 and 3, the proportion of participants that displayed a rise of insulin with oral exposure to sucralose was significantly greater when the stimulus was in the solid form compared to the beverage form. Sucralose and sucrose exposure elicited similarly significant increases in serum insulin 2min after exposure and significant decreases after 2min in responders in both food forms. The solid food form elicited greater CPIR over 2, 6 and 10min than the beverage form. There was no effect of learning on insulin responses after training. The results indicate the presence of a significant CPIR in a subset of individuals with overweight or obesity after oral exposure to sucralose, especially when present in

  11. Suppressed Release of Clarithromycin from Tablets by Crystalline Phase Transition of Metastable Polymorph Form I.

    Science.gov (United States)

    Fujiki, Sadahiro; Watanabe, Narumi; Iwao, Yasunori; Noguchi, Shuji; Mizoguchi, Midori; Iwamura, Takeru; Itai, Shigeru

    2015-08-01

    The pharmaceutical properties of clarithromycin (CAM) tablets containing the metastable form I of crystalline CAM were investigated. Although the dissolution rate of form I was higher than that of stable form II, the release of CAM from form I tablet was delayed. Disintegration test and liquid penetration test showed that the disintegration of the tablet delayed because of the slow penetration of an external solution into form I tablet. Investigation by scanning electron microscopy revealed that the surface of form I tablet was covered with fine needle-shaped crystals following an exposure to the external solution. These crystals were identified as form IV crystals by powder X-ray diffraction. The phenomenon that CAM releases from tablet was inhibited by fine crystals spontaneously formed on the tablet surface could be applied to the design of sustained-release formulation systems with high CAM contents by minimizing the amount of functional excipients. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  12. Niche applications of metal hydrides and related thermal management issues

    Energy Technology Data Exchange (ETDEWEB)

    Lototskyy, M., E-mail: mlototskyy@uwc.ac.za [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa); Satya Sekhar, B. [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa); Muthukumar, P. [Mechanical Department, Indian Institute of Technology Guwahati, Guwahati 781039 (India); Linkov, V.; Pollet, B.G. [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa)

    2015-10-05

    Highlights: • MH H{sub 2} storage, compression & heat management: developments/thermal management. • Thermodynamic criteria for proper selection of MH for different gas phase applications. • Factors influencing on H{sub 2} charge/discharge dynamic performance and energy efficiency. • The improvement of MH heat transfer characteristics is crucial. • Ways of improvement of heat transfer in the MH systems. - Abstract: This short review highlights and discusses the recent developments and thermal management issues related to metal hydride (MH) systems for hydrogen storage, hydrogen compression and heat management (refrigeration, pump and upgrade, etc.). Special attention is paid to aligning the system features with the requirements of the specific application. The considered system features include the MH material, the MH bed on the basis of its corresponding MH container, as well as the layout of the integrated system.

  13. Preparation and Properties of Zirconium Hydride on the Surface of MCM-41 Mesoporous Molecular Sieves

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Zirconium monohydride bonded to the framework oxygen of MCM-41 surface was prepared by the reaction of tetraneopentyl zirconium with MCM-41 surface hydroxyl groups, followed by the hydrogenolysis of the resulted product. The surface hydride was characterized by using infrared spectroscopy, solid-state NMR, elemental analysis, gas-phase chromatography and chemical probing reaction. It was shown that this surface species is stable below 150 ℃ and can catalytically crack alkanes into methane and ethane at 100 ℃.

  14. Microstructural studies and crystallographic orientation of different zones and δ-hydrides in resistance welded Zircaloy-4 sheets

    Science.gov (United States)

    Kiran Kumar, N. A. P.; Szpunar, Jerzy. A.; He, Zhang

    2011-07-01

    The cold worked stress relieved (CWSR) Zircaloy-4 sheet used as endplate in nuclear fuel bundle is resistance welded with an endcap in argon environment. Later the welded sample is hydrided in a gaseous atmosphere at 400 °C. Optical microscopy (OM), electron backscatter diffraction (EBSD) and X-ray diffraction (XRD) were used to examine the morphology and crystal orientation of the hydrides. The microstructural changes in different areas of the weld zone, heat affected zone (HAZ) and the as-received zone were analyzed using EBSD technique. Optical examination showed complete random morphological orientation of hydrides and predominantly basket-weave structure in the weld zone, with very few colonies of parallel plate structures. Variant selection for α-phase formation inside prior β-grains was identified at the weld centre. As we move from the weld centre to the as-received zone, the variant selection is found to be less probable. The δ-hydride platelets at the weld zone were always found to be growing perpendicular to the α-colonies having angular difference of 60-63° and follow (0 0 0 1) α-Zr//{1 1 1}δ-ZrH 1.5 orientation relationship with the zirconium matrix. Proposed description of complex distribution of hydrides and alloy microstructure at the weld and heat affected zone will contribute to a better understanding of mechanisms of failure of fuel cladding in various types of nuclear reactors.

  15. Electrochemical cell comprising stable hydride-forming material

    Energy Technology Data Exchange (ETDEWEB)

    Willems, J. J. G. S. A.; van Beek, J. R. G. C. M.; Buschow, K. H. J.

    1984-12-11

    An electrochemical cell having a negative electrode comprising a compound derived from LaNi/sub 5/, in which La is optionally substituted by a plateau pressure-increasing element and in which Ni is substituted entirely or partly by a plateau pressure-reducing element, for example, Co and/or Cu, with the object of considerably reducing volume steps and hence crack formation of the intermetallic compound during charging and discharging. Moreover, the corrosion of the intermetallic compound is counteracted by adding small quantities of Al, Cr and/or Si, Which metals enhance the formation of a protecting oxide layer.

  16. First-leaflet phase effect on properties of phospholipid bilayer formed through vesicle adsorption on LB monolayer.

    Science.gov (United States)

    Park, Jin-Won

    2010-10-01

    Phospholipid bilayers were formed on mica using the Langmuir-Blodgett technique and liposome fusion, as a model system for biomembranes. Nanometer-scale surface physical properties of the bilayers were quantitatively characterized upon the different phases of the first leaflets. Lower hydration/steric forces on the bilayers were observed at the liquid phase of the first leaflet than at the solid phase. The forces appear to be related to the low mechanical stability of the lipid bilayer, which was affected by the first leaflet phase. The first leaflet phase also influenced the long-range repulsive forces over the second leaflet. Surface forces, measured using a modified probe with an atomic force microscope, showed that lower long-range repulsive forces were also found at the liquid phase of the first leaflet. Force measurements were performed at 300 mM sodium chloride solution so that the effect of the phase on the long-range repulsive forces could be investigated by reducing the effect of the repulsion between the second-leaflet lipid headgroups on the long-range repulsive forces. Forces were analyzed using the Derjaguin-Landau-Verwey-Overbeek theory so that the surface potential and surface charge density of the lipid bilayers were quantitatively acquired for each phase of the first leaflet.

  17. Numerical study of a magnesium hydride tank

    Science.gov (United States)

    Delhomme, Baptiste; de Rango, Patricia; Marty, Philippe

    2012-11-01

    Hydrogen storage in metal hydride tanks (MHT) is a very promising solution. Several experimental tanks, studied by different teams, have already proved the feasibility and the interesting performances of this solution. However, in much cases, an optimization of tank geometry is still needed in order to perform fast hydrogen loading. The development of efficient numerical tools is a key issue for MHT design and optimization. We propose a simple model representing a metal hydride tank exchanging its heat of reaction with a thermal fluid flow. In this model, the radial and axial discretisations have been decoupled by using Matlab® one-dimensional tools. Calculations are compared to experimental results obtained in a previous study. A good agreement is found for the loading case. The discharging case shows some discrepancies, which are discussed in this paper.

  18. Nickel metal hydride LEO cycle testing

    Science.gov (United States)

    Lowery, Eric

    1995-01-01

    The George C. Marshall Space Flight Center is working to characterize aerospace AB5 Nickel Metal Hydride (NiMH) cells. The cells are being evaluated in terms of storage, low earth orbit (LEO) cycling, and response to parametric testing (high rate charge and discharge, charge retention, pulse current ability, etc.). Cells manufactured by Eagle Picher are the subjects of the evaluation. There is speculation that NiMH cells may become direct replacements for current Nickel Cadmium cells in the near future.

  19. Rules and trends of metal cation driven hydride-transfer mechanisms in metal amidoboranes.

    Science.gov (United States)

    Kim, Dong Young; Lee, Han Myoung; Seo, Jongcheol; Shin, Seung Koo; Kim, Kwang S

    2010-01-01

    Group I and II metal amidoboranes have been identified as one of the promising families of materials for efficient H(2) storage. However, the underlying mechanism of the dehydrogenation of these materials is not well understood. Thus, the mechanisms and kinetics of H(2) release in metal amidoboranes are investigated using high level ab initio calculations and kinetic simulations. The metal plays the role of catalyst for the hydride transfer with formation of a metal hydride intermediate towards the dehydrogenation. In this process, with increasing ionic character of the metal hydride bond in the intermediate, the stability of the intermediate decreases, while the dehydrogenation process involving ionic recombination of the hydridic H with the protic H proceeds with a reduced barrier. Such correlations lead directly to a U-shaped relationship between the activation energy barrier for H(2) elimination and the ionicity of metal hydride bond. Oligomerized intermediates are formed by the chain reaction of the size-driven catalytic effects of metals, competing with the non-oligomerization pathway. The kinetic rates at low temperatures are determined by the maximum barrier height in the pathway (a Lambda-shaped relation), while those at moderately high temperatures are determined by most of multiple-barriers. This requires kinetic simulations. At the operating temperatures of proton exchange membrane fuel cells, the metal amidoboranes with lithium and sodium release H(2) along both oligomerization and non-oligomerization paths. The sodium amidoboranes show the most accelerated rates, while others release H(2) at similar rates. In addition, we predict that the novel metal amidoborane-based adducts and mixtures would release H(2) with accelerated rates as well as with enhanced reversibility. This comprehensive study is useful for further developments of active metal-based better hydrogen storage materials.

  20. Plasmonic hydrogen sensing with nanostructured metal hydrides.

    Science.gov (United States)

    Wadell, Carl; Syrenova, Svetlana; Langhammer, Christoph

    2014-12-23

    In this review, we discuss the evolution of localized surface plasmon resonance and surface plasmon resonance hydrogen sensors based on nanostructured metal hydrides, which has accelerated significantly during the past 5 years. We put particular focus on how, conceptually, plasmonic resonances can be used to study metal-hydrogen interactions at the nanoscale, both at the ensemble and at the single-nanoparticle level. Such efforts are motivated by a fundamental interest in understanding the role of nanosizing on metal hydride formation processes in the quest to develop efficient solid-state hydrogen storage materials with fast response times, reasonable thermodynamics, and acceptable long-term stability. Therefore, a brief introduction to the thermodynamics of metal hydride formation is also given. However, plasmonic hydrogen sensors not only are of academic interest as research tool in materials science but also are predicted to find more practical use as all-optical gas detectors in industrial and medical applications, as well as in a future hydrogen economy, where hydrogen is used as a carbon free energy carrier. Therefore, the wide range of different plasmonic hydrogen sensor designs already available is reviewed together with theoretical efforts to understand their fundamentals and optimize their performance in terms of sensitivity. In this context, we also highlight important challenges to be addressed in the future to take plasmonic hydrogen sensors from the laboratory to real applications in devices, including poisoning/deactivation of the active materials, sensor lifetime, and cross-sensitivity toward other gas species.

  1. Crystallization of metastable beta glycine from gas phase via the sublimation of alpha or gamma form in vacuum.

    Science.gov (United States)

    Liu, Zhimin; Zhong, Lin; Ying, Pinliang; Feng, Zhaochi; Li, Can

    2008-01-01

    It is found that beta glycine, the metastable polymorph of glycine, can be rapidly formed from gas phase via the sublimation of its stable alpha or gamma form in vacuum. The transformation process was monitored by infrared spectroscopy and the crystal structure of the sublimate was identified by X-ray diffraction techniques. It is the first report about the transformation of stable alpha or gamma glycine into metastable beta form in "one-step" (heating then cool down spontaneously). Crystallization of beta glycine from gas phase is very different from other methods that require additives in solution. The hydrogen-bonding interaction and self-assembling of amino acid were discussed based on the observations.

  2. Role of interface in forming non-equilibrium hcp phase by ion mixing in an immiscible Au-Co system

    CERN Document Server

    Yan, H F; Liu, B X

    2003-01-01

    In an equilibrium immiscible Au-Co system characterized by a positive heat of formation of +11 kJ mol sup - sup 1 , a non-equilibrium Au-Co phase of hcp structure was formed by 200 keV xenon ion mixing at 77 K in the Au sub 5 sub 0 Co sub 5 sub 0 multilayered films. Based on the free energy calculation, the excess interfacial free energy stored in the Au-Co multilayered films could provide adequate thermodynamic driving force for alloying between Au and Co and forming the non-equilibrium Au-Co hcp phase. Besides, the average magnetic moment per Co atom in the newly formed hcp structure was reduced by 22% of its equilibrium value, within a measuring error of 8%.

  3. Modeling of hydride precipitation and re-orientation

    Energy Technology Data Exchange (ETDEWEB)

    Tikare, Veena [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Weck, Philippe F. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Mitchell, John Anthony [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2015-09-18

    In this report, we present a thermodynamic-­based model of hydride precipitation in Zr-based claddings. The model considers the state of the cladding immediately following drying, after removal from cooling-pools, and presents the evolution of precipitate formation upon cooling as follows: The pilgering process used to form Zr-based cladding imparts strong crystallographic and grain shape texture, with the basal plane of the hexagonal α-Zr grains being strongly aligned in the rolling-­direction and the grains are elongated with grain size being approximately twice as long parallel to the rolling direction, which is also the long axis of the tubular cladding, as it is in the orthogonal directions.

  4. Separation of chiral primary amino compounds by forming a sandwiched complex in reversed-phase high performance liquid chromatography.

    Science.gov (United States)

    Zhang, Chen; Huang, Wei X; Chen, Zhi; Rustum, Abu M

    2010-07-23

    Separation of chiral primary amino compounds was efficiently achieved under reversed-phase high performance liquid chromatography (RP-HPLC) conditions using a mixture of non-chiral crown ether (18-crown-6) and dimethyl-beta-cyclodextrin (DM-beta-CD) in the mobile phase. Under these conditions, the amino group of the chiral compound was protonated in a low pH mobile phase, and then interacted with 18-crown-6 and DM-beta-CD to form a sandwiched complex [18-crown-6+amine+CD]. Enantiomers of the compound in the sandwiched complex were separated with good enantioselectivity. Formation of the sandwiched complex among the chiral compound and additives in the mobile phase is a key step of the chiral separation. Four different chiral amino compounds namely, 1-aminoindan (AI), 1,2,3,4-tetrahydro-1-naphthylamine (THNA), tyrosine (Tyr), and phenylalanine (Phe), were selected to demonstrate the separation using the sandwiched complex mechanism in RP-HPLC.

  5. Studies of Nucleation, Growth, Specific Heat, and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

    Science.gov (United States)

    Kelton, K. F.; Croat, T. K.; Gangopadhyay, A.; Holland-Moritz, D.; Hyers, Robert W.; Rathz, Thomas J.; Robinson, Michael B.; Rogers, Jan R.

    2001-01-01

    Undercooling experiments and thermal physical property measurements of metallic alloys on the International Space Station (ISS) are planned. This recently-funded research focuses on fundamental issues of the formation and structure of highly-ordered non-crystallographic phases (quasicrystals) and related crystal phases (crystal approximants), and the connections between the atomic structures of these phases and those of liquids and glasses. It extends studies made previously by us of the composition dependence of crystal nucleation processes in silicate and metallic glasses, to the case of nucleation from the liquid phase. Motivating results from rf-levitation and drop-tube measurements of the undercooling of Ti/Zr-based liquids that form quasicrystals and crystal approximants are discussed. Preliminary measurements by electrostatic levitation (ESL) are presented.

  6. Matched-filtering generalized phase contrast using LCoS pico-projectors for beam-forming

    DEFF Research Database (Denmark)

    Bañas, Andrew Rafael; Palima, Darwin; Glückstad, Jesper

    2012-01-01

    We report on a new beam-forming system for generating high intensity programmable optical spikes using so-called matched-filtering Generalized Phase Contrast (mGPC) applying two consumer handheld pico-projectors. Such a system presents a low-cost alternative for optical trapping and manipulation......, optical lattices and other beam-shaping applications usually implemented with high-end spatial light modulators. Portable pico-projectors based on liquid crystal on silicon (LCoS) devices are used as binary phase-only spatial light modulators by carefully setting the appropriate polarization of the laser...... patterns suited for different requirements. Despite imperfections in these consumer pico-projectors, the mGPC approach tolerates phase aberrations that would have otherwise been hard to overcome by standard phase projection....

  7. Metastable Phases of Dross Particles Formed in a Molten Zinc Bath and Prediction of Soluble Aluminum During Galvannealing Processes

    Science.gov (United States)

    Paik, Doo-Jin; Hong, Moon-Hi; Huh, Yoon; Park, Joo Hyun; Chae, Hong-Kook; Park, Seok-Ho; Choun, Si-Youl

    2012-06-01

    The morphology, chemistry, and crystallographic characteristics of metastable dross particles were identified. These particles are formed during the initial stage of precipitation. The particles had aluminum concentrations of 15 to 80 mass pct, with values that decreased gradually as particle size increased. These metastable dross particles were a mixture of the crystalline phase of FeZn10, which is called the "delta phase," and the high-aluminum amorphous phase, which covered the surface of the crystalline phase. The new "meta Q" concept was proposed to predict the amount of soluble aluminum in the zinc bath by considering nucleation kinetics and particle growth. The results calculated using the "meta Q" concept were compared with the values measured by the aluminum sensor, which were taken during the same period at the commercial galvanizing line. The mean of the absolute values of the differences between the calculated and measured values was 9.7 ppm.

  8. Mechanism of n-butane hydrogenolysis promoted by Ta-hydrides supported on silica

    KAUST Repository

    Pasha, Farhan Ahmad

    2014-06-06

    The mechanism of hydrogenolysis of alkanes, promoted by Ta-hydrides supported on silica via 2 ≡ Si-O- bonds, has been studied with a density functional theory (DFT) approach. Our study suggests that the initial monohydride (≡ Si-O-)2Ta(III)H is rapidly trapped by molecular hydrogen to form the more stable tris-hydride (≡ Si-O-) 2Ta(V)H3. Loading of n-butane to the Ta-center occurs through C-H activation concerted with elimination of molecular hydrogen (σ-bond metathesis). Once the Ta-alkyl species is formed, the C-C activation step corresponds to a β-alkyl transfer to the metal with elimination of an olefin. According to these calculations, an α-alkyl transfer to the metal to form a Ta-carbene species is of higher energy. The olefins formed during the C-C activation step can be rapidly hydrogenated by both mono- and tris-Ta-hydride species, making the overall process of alkane cracking thermodynamically favored. © 2014 American Chemical Society.

  9. Topotactic Solid-State Metal Hydride Reductions of Sr2MnO4.

    Science.gov (United States)

    Hernden, Bradley C; Lussier, Joey A; Bieringer, Mario

    2015-05-04

    We report novel details regarding the reactivity and mechanism of the solid-state topotactic reduction of Sr2MnO4 using a series of solid-state metal hydrides. Comprehensive details describing the active reducing species are reported and comments on the reductive mechanism are provided, where it is shown that more than one electron is being donated by H(-). Commonly used solid-state hydrides LiH, NaH, and CaH2, were characterized in terms of reducing power. In addition the unexplored solid-state hydrides MgH2, SrH2, and BaH2 are evaluated as potential solid-state reductants and characterized in terms of their reductive reactivities. These 6 group I and II metal hydrides show the following trend in terms of reactivity: MgH2 metal electronegativity and bond strengths. NaH and the novel use of SrH2 allowed for targeted synthesis of reduced Sr2MnO(4-x) (0 ≤ x ≤ 0.37) phases. The enhanced control during synthesis demonstrated by this soft chemistry approach has allowed for a more comprehensive and systematic evaluation of Sr2MnO(4-x) phases than previously reported phases prepared by high temperature methods. Sr2MnO3.63(1) has for the first time been shown to be monoclinic by powder X-ray diffraction and the oxidative monoclinic to tetragonal transition occurs at 450 °C.

  10. Preparation and Characterization of Membranes Formed by Nonsolvent Induced Phase Separation: A Review

    KAUST Repository

    Guillen, Gregory R.

    2011-04-06

    The methods and mechanisms of nonsolvent induced phase separation have been studied for more than fifty years. Today, phase inversion membranes are widely used in numerous chemical industries, biotechnology, and environmental separation processes. The body of knowledge has grown exponentially in the past fifty years, which suggests the need for a critical review of the literature. Here we present a review of nonsolvent induced phase separation membrane preparation and characterization for many commonly used membrane polymers. The key factors in membrane preparation discussed include the solvent type, polymer type and concentration, nonsolvent system type and composition, additives to the polymer solution, and film casting conditions. A brief introduction to membrane characterization is also given, which includes membrane porosity and pore size distribution characterization, membrane physical and chemical properties characterization, and thermodynamic and kinetic evaluation of the phase inversion process. One aim of this review is to lay out the basics for selecting polymer solvent nonsolvent systems with appropriate film casting conditions to produce membranes with the desired performance, morphology, and stability, and to choose the proper way to characterize these properties of nonsolvent induced phase inversion membranes. © 2011 American Chemical Society.

  11. Using magnetization measurements to detect small amounts of plutonium hydride formation in plutonium metal

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jae Wook [Rutgers Univ., New Brunswick, NJ (United States); Mielke, Charles H. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Zapf, Vivien [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Baiardo, Joseph P. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mitchell, Jeremy N. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Richmond, Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Schwartz, Daniel S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mun, Eun D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Smith, Alice Iulia [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2014-10-20

    We report the formation of plutonium hydride in 2 at % Ga-stabilized δ-Pu, with 1 atomic % H charging. We show that magnetization measurements are a sensitive, quantitative measure of ferromagnetic plutonium hydride against the nonmagnetic background of plutonium. It was previously shown that at low hydrogen concentrations, hydrogen forms super-abundant vacancy complexes with plutonium, resulting in a bulk lattice contraction. Here we use magnetization, X-ray and neutron diffraction measurements to show that in addition to forming vacancy complexes, at least 30% of the H atoms bond with Pu to precipitate PuHx, largely on the surface of the sample with x ~ 1.9. We observe magnetic hysteresis loops below 40 K with magnetic remanence, consistent with precipitates of ferromagnetic PuH1.9.

  12. Light metal hydrides and complex hydrides for hydrogen storage.

    Science.gov (United States)

    Schüth, F; Bogdanović, B; Felderhoff, M

    2004-10-21

    The availability of feasible methods for hydrogen storage is one of the key-maybe the key-requirements for the large scale application of PEM fuel cells in cars. There are in principle four different approaches, i.e. cryostorage in liquid form, high pressure storage, storage in the form of a chemical compound which is converted to hydrogen by on-board reforming, or reversible chemical storage in different kinds of storage materials. New developments in the field of chemical storage make such systems attractive compared to the other options. This review will discuss the different possibilities for chemical storage of hydrogen and the focus on the presently most advanced system with respect to storage capacity and kinetics, i.e. catalyzed alanates, especially NaAlH(4).

  13. Predicted energy densitites for nickel-hydrogen and silver-hydrogen cells embodying metallic hydrides for hydrogen storage

    Science.gov (United States)

    Easter, R. W.

    1974-01-01

    Simplified design concepts were used to estimate gravimetric and volumetric energy densities for metal hydrogen battery cells for assessing the characteristics of cells containing metal hydrides as compared to gaseous storage cells, and for comparing nickel cathode and silver cathode systems. The silver cathode was found to yield superior energy densities in all cases considered. The inclusion of hydride forming materials yields cells with very high volumetric energy densities that also retain gravimetric energy densities nearly as high as those of gaseous storage cells.

  14. Nickel/metal hydride technology for consumer and electric vehicle batteries—a review and up-date

    Science.gov (United States)

    Dhar, S. K.; Ovshínsky, S. R.; Gifford, P. R.; Corrigan, D. A.; Fetcenko, M. A.; Venkatesan, S.

    Nickel/metal hydride batteries today represent the fastest growing market segment for rechargeable batteries due to the high energy density and more environmentally acceptable chemistry offered by this technology. The high energy density of nickel/metal hydride batteries coupled with high power density and long cycle life make this battery chemistry a key enabling technology for practical electric vehicles, including cars, vans, trucks, and other forms of transportation such as scooters, bicycles, and three-wheelers. This paper provides a review of Ovonic technology and up-dates recent developments in materials and cell development for both consumer electronic and EV applications, and highlights areas for future development.

  15. Solubility, dissolution rate and phase transition studies of ranitidine hydrochloride tautomeric forms.

    Science.gov (United States)

    Mirmehrabi, M; Rohani, S; Murthy, K S K; Radatus, B

    2004-09-10

    Understanding the polymorphic behavior of pharmaceutical solids during the crystallization process and further in post-processing units is crucial to meet medical and legal requirements. In this study, an analytical technique was developed for determining the composition of two solid forms of ranitidine hydrochloride using two peaks of Fourier transform infrared (FTIR) spectra without the need to grind the samples. Solubility studies of ranitidine hydrochloride showed that Form 2 has a higher solubility than Form 1. Solution-mediated transformation is very slow and occurs from Form 2 to Form 1 and not the reverse. No solid-solid transformation was observed due to grinding or compressing the pure samples of either forms and of a 50/50 wt.% mixture. Grinding was found to be a proper technique for increasing the bulk solid density of the ranitidine hydrochloride without the risk of solid-solid transformation. Dissolution rate found to be equally fast for both forms. The solubility data were modeled using the group contribution parameters and UNIversal QUAsi-Chemical (UNIQUAC) theory. There was a good agreement between the experimental solubility data of ranitidine hydrochloride and the results of UNIQUAC equation.

  16. Triblock polyphiles through click chemistry: self-assembled thermotropic cubic phases formed by micellar and monolayer vesicular aggregates.

    Science.gov (United States)

    Tan, Xiaoping; Kong, Leiyang; Dai, Heng; Cheng, Xiaohong; Liu, Feng; Tschierske, Carsten

    2013-11-25

    Three series of triblock polyphiles consisting of a rigid 4-phenyl-1,2,3-triazole or 1,4-diphenyl-1,2,3-triazole core with three lipophilic and flexible alkoxyl chains at one end and a polar glycerol group at the opposite end were synthesized by copper-catalyzed azide-alkyne click reactions. Their mesophase behavior was studied by polarizing optical microscopy, differential scanning calorimetry, and XRD. Depending on alkyl chain length and core length, a transition from hexagonal columnar to Pm3n-type cubic phases was observed. In the cubic phases, the molecules are organized as spherical objects. Remarkably, compounds with a longer core unit have a higher tendency to form these cubic phases, and their stability is strongly enhanced over those of the compounds with a shorter core, despite longer cores having a smaller cone angle and therefore being expected to disfavor the formation of spherical objects. There is a large difference in the number of molecules involved in the spherical aggregates formed by compounds with long and short cores. Whereas the aggregates in the cubic phases of the compounds with short rod units are small and could be regarded as micellar, the long-core compounds form much larger aggregates which are regarded as a kind of monolayer vesicular aggregate.

  17. Swelling equilibrium of dentin adhesive polymers formed on the water-adhesive phase boundary: Experiments and micromechanical model

    Science.gov (United States)

    Misra, Anil; Parthasarathy, Ranganathan; Ye, Qiang; Singh, Viraj; Spencer, Paulette

    2013-01-01

    During their application to the wet, oral environment, dentin adhesives can experience phase separation and composition change which can compromise the quality of the hybrid layer formed at the dentin-adhesive interface. The chemical composition of polymer phases formed in the hybrid layer can be represented using a ternary water-adhesive phase diagram. In this paper, these polymer phases have been characterized using a suite of mechanical tests and swelling experiments. The experimental results were evaluated using granular micromechanics based model that incorporates poro-mechanical effects and polymer-solvent thermodynamics. The variation of the model parameters and model-predicted polymer properties has been studied as a function of composition along the phase boundary. The resulting structure-property correlations provide insight into interactions occurring at the molecular level in the saturated polymer system. These correlations can be used for modeling the mechanical behavior of hybrid layer, and are expected to aid in the design and improvement of water-compatible dentin adhesive polymers. PMID:24076070

  18. Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system.

    Science.gov (United States)

    Drozdov, A P; Eremets, M I; Troyan, I A; Ksenofontov, V; Shylin, S I

    2015-09-03

    A superconductor is a material that can conduct electricity without resistance below a superconducting transition temperature, Tc. The highest Tc that has been achieved to date is in the copper oxide system: 133 kelvin at ambient pressure and 164 kelvin at high pressures. As the nature of superconductivity in these materials is still not fully understood (they are not conventional superconductors), the prospects for achieving still higher transition temperatures by this route are not clear. In contrast, the Bardeen-Cooper-Schrieffer theory of conventional superconductivity gives a guide for achieving high Tc with no theoretical upper bound--all that is needed is a favourable combination of high-frequency phonons, strong electron-phonon coupling, and a high density of states. These conditions can in principle be fulfilled for metallic hydrogen and covalent compounds dominated by hydrogen, as hydrogen atoms provide the necessary high-frequency phonon modes as well as the strong electron-phonon coupling. Numerous calculations support this idea and have predicted transition temperatures in the range 50-235 kelvin for many hydrides, but only a moderate Tc of 17 kelvin has been observed experimentally. Here we investigate sulfur hydride, where a Tc of 80 kelvin has been predicted. We find that this system transforms to a metal at a pressure of approximately 90 gigapascals. On cooling, we see signatures of superconductivity: a sharp drop of the resistivity to zero and a decrease of the transition temperature with magnetic field, with magnetic susceptibility measurements confirming a Tc of 203 kelvin. Moreover, a pronounced isotope shift of Tc in sulfur deuteride is suggestive of an electron-phonon mechanism of superconductivity that is consistent with the Bardeen-Cooper-Schrieffer scenario. We argue that the phase responsible for high-Tc superconductivity in this system is likely to be H3S, formed from H2S by decomposition under pressure. These findings raise hope for the

  19. Calibration of Thermal Desorption System (TDS) Response to Hydrogen for Analysis of Titanium Subhydride and Titanium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Mills, Bernice E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2013-07-01

    The equipment and method for and results of calibration of the Sandia/CA TDS system for hydrogen quantification is presented. This technique for calibration can be used to quantify the hydrogen content titanium subhydride, titanium hydride, and any other hydrogen-containing material that desorbs its hydrogen in the form of molecular hydrogen below 1450°C.

  20. Dopant-vacancy binding effects in Li-doped magnesium hydride

    Science.gov (United States)

    Smith, Kyle C.; Fisher, Timothy S.; Waghmare, Umesh V.; Grau-Crespo, Ricardo

    2010-10-01

    We use a combination of ab initio calculations and statistical mechanics to investigate the substitution of Li+ for Mg2+ in magnesium hydride (MgH2) accompanied by the formation of hydrogen vacancies with positive charge (with respect to the original ion at the site). We show that the binding energy between dopants and vacancy defects leads to a significant fraction of trapped vacancies and therefore a dramatic reduction in the number of free vacancies available for diffusion. The concentration of free vacancies initially increases with dopant concentration but reaches a maximum at around 1mol% Li doping and slowly decreases with further doping. At the optimal level of doping, the corresponding concentration of free vacancies is much higher than the equilibrium concentrations of charged and neutral vacancies in pure MgH2 at typical hydrogen storage conditions. We also show that Li-doped MgH2 is thermodynamically metastable with respect to phase separation into pure magnesium and lithium hydrides at any significant Li concentration, even after considering the stabilization provided by dopant-vacancy interactions and configurational entropic effects. Our results suggest that lithium doping may enhance hydrogen diffusion hydride but only to a limited extent determined by an optimal dopant concentration and conditioned to the stability of the doped phase.

  1. Rapid Microwave Synthesis, Characterization and Reactivity of Lithium Nitride Hydride, Li4NH

    Directory of Open Access Journals (Sweden)

    Nuria Tapia-Ruiz

    2013-11-01

    Full Text Available Lithium nitride hydride, Li4NH, was synthesised from lithium nitride and lithium hydride over minute timescales, using microwave synthesis methods in the solid state for the first time. The structure of the microwave-synthesised powders was confirmed by powder X-ray diffraction [tetragonal space group I41/a; a = 4.8864(1 Å, c = 9.9183(2 Å] and the nitride hydride reacts with moist air under ambient conditions to produce lithium hydroxide and subsequently lithium carbonate. Li4NH undergoes no dehydrogenation or decomposition [under Ar(g] below 773 K. A tetragonal–cubic phase transition, however, occurs for the compound at ca. 770 K. The new high temperature (HT phase adopts an anti-fluorite structure (space group Fm 3̅ m; a = 4.9462(3 Å with N3− and H− ions disordered on the 4a sites. Thermal treatment of Li4NH under nitrogen yields a stoichiometric mixture of lithium nitride and lithium imide (Li3N and Li2NH respectively.

  2. Hydrogen storage systems based on magnesium hydride: from laboratory tests to fuel cell integration

    Science.gov (United States)

    de Rango, P.; Marty, P.; Fruchart, D.

    2016-02-01

    The paper reviews the state of the art of hydrogen storage systems based on magnesium hydride, emphasizing the role of thermal management, whose effectiveness depends on the effective thermal conductivity of the hydride, but also depends of other limiting factors such as wall contact resistance and convective exchanges with the heat transfer fluid. For daily cycles, the use of phase change material to store the heat of reaction appears to be the most effective solution. The integration with fuel cells (1 kWe proton exchange membrane fuel cell and solid oxide fuel cell) highlights the dynamic behaviour of these systems, which is related to the thermodynamic properties of MgH2. This allows for "self-adaptive" systems that do not require control of the hydrogen flow rate at the inlet of the fuel cell.

  3. A model to describe the mechanical behavior and the ductile failure of hydrided Zircaloy-4 fuel claddings between 25 °C and 480 °C

    Science.gov (United States)

    Le Saux, M.; Besson, J.; Carassou, S.

    2015-11-01

    A model is proposed to describe the mechanical behavior and the ductile failure at 25, 350 and 480 °C of Zircaloy-4 cladding tubes, as-received and hydrided up to 1200 wt. ppm (circumferential hydrides). The model is based on the Gurson-Tvergaard-Needleman model extended to account for plastic anisotropy and viscoplasticity. The model considers damage nucleation by both hydride cracking and debonding of the interface between the Laves phase precipitates and the matrix. The damage nucleation rate due to hydride cracking is directly deduced from quantitative microstructural observations. The other model parameters are identified from several experimental tests. Finite element simulations of axial tension, hoop tension, expansion due to compression and hoop plane strain tension experiments are performed to assess the model prediction capability. The calibrated model satisfactorily reproduces the effects of hydrogen and temperature on both the viscoplastic and the failure properties of the material. The results suggest that damage is anisotropic and influenced by the stress state for the non-hydrided or moderately hydrided material and becomes more isotropic for high hydrogen contents.

  4. Matched-filtering generalized phase contrast using LCoS pico-projectors for beam-forming.

    Science.gov (United States)

    Bañas, Andrew; Palima, Darwin; Glückstad, Jesper

    2012-04-23

    We report on a new beam-forming system for generating high intensity programmable optical spikes using so-called matched-filtering Generalized Phase Contrast (mGPC) applying two consumer handheld pico-projectors. Such a system presents a low-cost alternative for optical trapping and manipulation, optical lattices and other beam-shaping applications usually implemented with high-end spatial light modulators. Portable pico-projectors based on liquid crystal on silicon (LCoS) devices are used as binary phase-only spatial light modulators by carefully setting the appropriate polarization of the laser illumination. The devices are subsequently placed into the object and Fourier plane of a standard 4f-setup according to the mGPC spatial filtering configuration. Having a reconfigurable spatial phase filter, instead of a fixed and fabricated one, allows the beam shaper to adapt to different input phase patterns suited for different requirements. Despite imperfections in these consumer pico-projectors, the mGPC approach tolerates phase aberrations that would have otherwise been hard to overcome by standard phase projection.

  5. Effect of Cycle Duration and Phasing on Thermomechanical Fatigue of Dog-Bone Specimens Made form Steel

    Directory of Open Access Journals (Sweden)

    Achegaf Zineb

    2010-01-01

    Full Text Available Problem statement: Lifetime of standard dog-bone specimens made form steel as affected by phasing between thermal cycles and strains cycles and by cycle duration in thermomechanical fatigue is assessed under various conditions of loading. Approach: The methodology used was based on finite element post-processing analysis by specialized fatigue software package that takes into account coupling of damage from three primary sources: Fatigue, oxidation and creep. Results: A parametric study has been conducted for various thermomechanical loadings and effects of phasing and cycle duration on lifetime have been evaluated. The associated percentages of damage mechanisms due to fatigue, oxidation and creep have been determined. Conclusion: It has been shown that both phasing and cycle duration have considerable effect on lifetime. In the range of parameters investigated, the in-phase cycles were found to reduce considerably damage in the specimen for low pressures and low temperatures. The results have shown also that there was no way of unique comparison of the various phasing configurations, since there exists always a case of thermomechanical loading for which one phasing configuration yields higher damage than any another configuration.

  6. Effect of Gaseous Impurities on Long-Term Thermal Cycling and Aging Properties of Complex Hydrides for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, Dhanesh [Primary Contact; Lamb, Joshua; Chien, Wen-Ming; Talekar, Anjali; and Pal, Narendra

    2011-03-28

    stored in the material after the first desorption. The activation energy was found to be 51 kJ/mol, as compared to 81 kJ/mol for pure lithium alanate. It is proposed that based on the data obtained and CALPHAD modeling that the improvement in cycling is due to the formation of pure lithium (liquid at 255°C), which is able to react with nitrogen specifically forming Li3N. The presence of nitrogen in the 80/20 molar mixtures in a hydride bed along with hydrogen causes Li to form Li3N rather than LiH, and subsequently regenerates the Li2NH phase and yields a ~10 wt.%H reversibly.

  7. Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystals and Polytetrehedral-Phase-Forming Alloys

    Science.gov (United States)

    2003-01-01

    By investigating the properties of quasicrystals and quasicrystal-forming liquid alloys, we may determine the role of ordering of the liquid phase in the formation of quasicrystals, leading to a better fundamental understanding of both the quasicrystal and the liquid. A quasicrystal is solid characterized by a symmetric but non-periodic arrangement of atoms, usually in the form of an icosahedron (12 atoms, 20 triangular faces). It is theorized that the short-range order in liquids takes this same form. The degree of ordering depends on the temperature of the liquid, and affects many of the liquid s properties, including specific heat, viscosity, and electrical resistivity. The MSFC role in this project includes solidification studies, phase diagram determination, and thermophysical property measurements on the liquid quasicrystal-forming alloys, all by electrostatic levitation (ESL). The viscosity of liquid quasicrystal-forming alloys is measured by the oscillating drop method, both in the stable and undercooled liquid state. The specific heat of solid, undercooled liquid, and stable liquid are measured by the radiative cooling rate of the droplets.

  8. Method of making crack-free zirconium hydride

    Science.gov (United States)

    Sullivan, Richard W.

    1980-01-01

    Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

  9. Creating nanoshell on the surface of titanium hydride bead

    Directory of Open Access Journals (Sweden)

    PAVLENKO Vyacheslav Ivanovich

    2016-12-01

    Full Text Available The article presents data on the modification of titanium hydride bead by creating titanium nanoshell on its surface by ion-plasma vacuum magnetron sputtering. To apply titanium nanoshell on the titanium hydride bead vacuum coating plant of multifunctional nanocomposite coatings QVADRA 500 located in the center of high technology was used. Analysis of the micrographs of the original surface of titanium hydride bead showed that the microstructure of the surface is flat, smooth, in addition the analysis of the microstructure of material surface showed the presence of small porosity, roughness, mainly cavities, as well as shallow longitudinal cracks. The presence of oxide film in titanium hydride prevents the free release of hydrogen and fills some micro-cracks on the surface. Differential thermal analysis of both samples was conducted to determine the thermal stability of the initial titanium hydride bead and bead with applied titanium nanoshell. Hydrogen thermal desorption spectra of the samples of the initial titanium hydride bead and bead with applied titanium nanoshell show different thermal stability of compared materials in the temperature range from 550 to 860о C. Titanium nanoshells applied in this way allows increasing the heat resistance of titanium hydride bead – the temperature of starting decomposition is 695о C and temperature when decomposition finishes is more than 1000о C. Modified in this way titanium hydride bead can be used as a filler in the radiation protective materials used in the construction or upgrading biological protection of nuclear power plants.

  10. High energy density battery based on complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  11. High energy density battery based on complex hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  12. Synthesis, characterization and properties of some organozinc hydride complexes

    NARCIS (Netherlands)

    Koning, A.J. de; Boersma, J.; Kerk, G.J.M. van der

    1980-01-01

    The synthesis and characterization of the monopyridine complexes of ethylzinc hydride and phenylzinc hydride are described. On treatment with TMED these complexes are converted into R2Zn3H4. TMED species through a combination of ligand-exchange and disproportionation. The formation of organozinc hyd

  13. Inclusion complexes of ionic liquids and cyclodextrins: are they formed in the gas phase?

    Science.gov (United States)

    Fernandes, Ana M; Schröder, Bernd; Barata, Tânia; Freire, Mara G; Coutinho, João A P

    2014-05-01

    The interaction of imidazolium-based ionic liquids with α- and β-cyclodextrins was investigated by electrospray ionization mass spectrometry with variable collision induced dissociation energy and quantum chemical gas-phase calculations. The center-of-mass energy at which 50% of a precursor ion decomposes (Ecm,1/2) was determined for the isolated [cyclodextrin + cation](+) or [cyclodextrin + anion](-) adduct ions of imidazolium-based ionic liquids with different alkyl chain lengths combined with a large set of anions, such as chloride, bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, dicyanamide, and hydrogensulfate. Moreover, both symmetric and asymmetric imidazolium cationic cores were evaluated. The relative interaction energies in the adduct ions were interpreted in terms of the influence of cation/anion structures and their inherent properties, such as hydrophobicity and hydrogen bond accepting ability, in the complexation process with the cyclodextrins. The trends observed in the mass spectral data together with quantum-chemical calculations suggest that in the gas phase, cations and anions will preferentially interact with the lower or upper rim of the cyclodextrin, respectively, as opposed to what has been reported in condensed phase where the formation of an inclusion complex between ionic liquid and cyclodextrin is assumed.

  14. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    Energy Technology Data Exchange (ETDEWEB)

    Shek, G.K. [Ontario Hydro Technol., Ont. (Canada). Mater. Technol. Unit; Jovanovic, M.T. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Seahra, H. [Ontario Hydro Technol., Ont. (Canada). Mater. Technol. Unit; Ma, Y. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Li, D. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering; Eadie, R.L. [Alberta Univ., Edmonton, AB (Canada). Dept. of Mining, Metallurgical and Petroleum Engineering

    1996-08-01

    These experiments were designed to study hydride formation at the crack tip, acoustic emission (AE), potential drop (PD) and striation formation during DHC (delayed hydride cracking) in Zr-2.5% Nb. The test material was taken from an especially extruded pressure tube, which showed similar strength properties to normal pressure tube material but somewhat coarser microstructure. In testing at K{sub I} below 12 MPa {radical}m at both 200 and 250 C very large striations (>40 {mu}m at 200 and >50 {mu}m at 250 C) were produced. In simultaneous monitoring with acoustic emission and potential drop, both AE and PD jumps were shown to be monolithic. The number of striations on the fracture surface corresponded to the number of monolithic AE/PD jumps. Tapered shaped hydrides with the thick end adjacent to the crack tip were observed. These hydrides grew in size during the incubation period until they reached the striation length and then fractured monolithically. However, when K{sub I} was increased beyond about 12 MPa {radical}m for these same specimens, the striation spacing decreased below 30 {mu}m, the monolithic jumping dissolved into more continuous changes in signals, although the smaller striations were still visible on the fracture surface. (orig.).

  15. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    Science.gov (United States)

    Shek, G. K.; Jovanoviċ, M. T.; Seahra, H.; Ma, Y.; Li, D.; Eadie, R. L.

    1996-08-01

    These experiments were designed to study hydride formation at the crack tip, acoustic emission (AE), potential drop (PD) and striation formation during DHC (delayed hydride cracking) in Zr-2.5% Nb. The test material was taken from an especially extrude pressure tube, which showed similar strength properties to normal pressure tube material but somewhat coarser microstructure. In testing at KI below 12 MPa √m at both 200 and 250°C very large striations (> 40 μ at 200 and >50 μm at 250°C) were produced. In simultaneous monitoring with acoustic emission and potential drop, both AE and PD jumps were shown to be monolithic. The number of striations on the fracture surface corresponded to the number of monolithic AE/PD jumps. Tapered shaped hydrides with the thick end adjacent to the crack tip were observed. These hydrides grew in size during the incubation period until they reached the striation length and then fractured monolithically. However, when KI was increased beyond about 12 MPa √m for these same specimens, the striation spacing decreased below 30 μ, the monolithic jumping dissolved into more continuous changes in signals, although the smaller striations were still visible on the fracture surface.

  16. Rad52 forms DMA repair and recombination centers during S phase

    DEFF Research Database (Denmark)

    Lisby, M.; Rothstein, R.; Mortensen, Uffe Hasbro

    2001-01-01

    fluorescent protein (GFP) is fully functional in DNA repair and recombination. After induction of DNA double-strand breaks by gamma -irradiation, meiosis, or the HO endonuclease, Rad52-GFP relocalizes from a diffuse nuclear distribution to distinct foci. Interestingly, Rad52 foci are formed almost exclusively...

  17. Simple determination of ranitidine in dosage forms by in-phase selective AC polarography.

    Science.gov (United States)

    Squella, J A; Zuñiga, L A; Lemus, I; Nuñez-Vergara, L J

    1988-01-01

    A new AC polarographic method for the determination of pharmaceutical forms of ranitidine is proposed, based on the electroactivity of the ranitidine nitro group. Individual and composite assays as well as recovery studies are described. Results show adequate precision and accuracy. Sample preparation is easy and no excipient separation is required.

  18. Structure of the carbon nanofilaments formed by liquid phase carbonization in porous anodic alumina template

    Energy Technology Data Exchange (ETDEWEB)

    Habazaki, H. [Graduate School of Engineering, Hokkaido University, N13-W8, Sapporo 060-8628 (Japan)], E-mail: habazaki@eng.hokudai.ac.jp; Kiriu, M.; Hayashi, M.; Konno, H. [Graduate School of Engineering, Hokkaido University, N13-W8, Sapporo 060-8628 (Japan)

    2007-10-15

    Platelet structure carbon nanofilaments of {approx}30 nm in diameter have been prepared by heating a mixture of porous anodic alumina template and poly(vinyl)chloride (PVC) powders in an argon atmosphere, and the change in their structure and morphology with heat treatment temperature, ranging from 600 to 2800 deg. C, has been examined using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen gas adsorption measurements. The diameter of the carbon nanofilaments formed does not change with heat treatment temperature, being in agreement with the pore diameter of the template, while their length is reduced with the temperature. The platelet-type orientation of graphene layers is evident even at 600 deg. C with the layer structure further developing with increasing heat treatment temperature. The carbon nanofilaments formed at lower temperatures have micropores, while those formed at higher temperatures do not have porosity. Highly graphitized carbon nanofilaments have been obtained after heat treatment at 2800 deg. C, with another characteristic structural feature being presence of loops at the edge of graphene layers formed at 2800 deg. C.

  19. Distributed beam forming with phase-only control for green cognitive radio networks

    NARCIS (Netherlands)

    Lian, X.; Nikookar, H.; Ligthart, L.P.

    2012-01-01

    Cognitive radio (CR) is an intelligent radio system and is able to share the spectrum with licensed users (LU). By adopting adaptive beam forming techniques, CR can reuse the spectrum with LU via directing main beams towards CR users while displaying nulls towards LU. In this article, we present a n

  20. The oxidation and hydriding of zircaloy fuel cladding in high temperature aqueous solutions

    Science.gov (United States)

    Chen, Yingzi

    Nearly 90% of today's fission reactors use Zr based fuel cladding materials. The Boiling Water Reactors (BWRs) and Pressurized Water Reactors (PWRs) are the two most common water-cooled nuclear reactors. Corrosion is the principal threat to the failure of the fuel in these reactors, resulting in the release of fission products to the coolant and hence to the establishment of radiation fields in out-of-core regions of the coolant circuit (e.g., steam generators in PWRs and turbines in BWRs). As is well known, corrosion is an electrochemical phenomenon; however, electrochemical effects are often neglected in corrosion studies on zirconium and its alloys, because of the difficulty in performing well-defined experiments under the appropriate conditions (high temperatures and pressures). In-situ studies have been carried out to examine the electrochemistry of passive zirconium under simulated BWR and PWR coolant conditions by using a controlled hydrodynamic, high temperature/high pressure test cell. The oxidation/hydriding mechanisms are elucidated by measuring the current, impedance, and capacitance of passive zirconium as a function of formation potential. The data are interpreted in terms of a modified point defect model (PDM) that recognize the existence of a passive film comprising a thick oxide outer layer over a thin barrier layer. From the composition of the zirconium passive film and thermodynamic analysis, it is postulated that a hydride barrier layer forms under PWR coolant conditions whereas an oxide barrier layer forms under BWR primary coolant conditions. Transients in current density and the thickness of the passive film formed on zirconium, when stepping the potential in either the positive or negative directions, have confirmed that the rate law afforded by the PDM adequately describes the growth and thinning of the passive film at high temperatures. The experimental results demonstrate that the kinetics of either oxygen or hydrogen vacancy generation

  1. Stabilization of NaCl-containing cuttings wastes in cement concrete by in situ formed mineral phases.

    Science.gov (United States)

    Filippov, Lev; Thomas, Fabien; Filippova, Inna; Yvon, Jacques; Morillon-Jeanmaire, Anne

    2009-11-15

    Disposal of NaCl-containing cuttings is a major environmental concern due to the high solubility of chlorides. The present work aims at reducing the solubility of chloride by encapsulation in low permeability matrix as well as lowering its solubility by trapping into low-solubility phases. Both the studied materials were cuttings from an oil-based mud in oil drillings containing about 50% of halite, and cuttings in water-based mud from gas drilling containing 90% of halite. A reduction in the amount of dissolved salt from 41 to 19% according to normalized leaching tests was obtained by addition of potassium ortho-phosphate in the mortar formula of oil-based cuttings, while the aluminium dihydrogeno-phosphate is even more efficient for the stabilization of water-based cuttings with a NaCl content of 90%. Addition of ortho-phosphate leads to form a continuous and weakly soluble network in the cement matrix, which reduces the release of salt. The formed mineralogical phases were apatite and hydrocalumite. These phases encapsulate the salt grains within a network, thus lowering its interaction with water or/and trap chloride into low-solubility phases. The tested approaches allow to develop a confinement process of NaCl-containing waste of various compositions that can be applied to wastes, whatever the salt content and the nature of the drilling fluids (water or oil).

  2. Growth and decomposition of Lithium and Lithium hydride on Nickel

    DEFF Research Database (Denmark)

    Engbæk, Jakob; Nielsen, Gunver; Nielsen, Jane Hvolbæk

    2006-01-01

    In this paper we have investigated the deposition, structure and decomposition of lithium and lithium-hydride films on a nickel substrate. Using surface sensitive techniques it was possible to quantify the deposited Li amount, and to optimize the deposition procedure for synthesizing lithium......-hydride films. By only making thin films of LiH it is possible to study the stability of these hydride layers and compare it directly with the stability of pure Li without having any transport phenomena or adsorbed oxygen to obscure the results. The desorption of metallic lithium takes place at a lower...... temperature than the decomposition of the lithium-hydride, confirming the high stability and sintering problems of lithium-hydride making the storage potential a challenge. (c) 2006 Elsevier B.V. All rights reserved....

  3. Helium trapping at erbium oxide precipitates in erbium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Foiles, Stephen M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Battaile, Corbett Chandler [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-02-01

    The formation of He bubbles in erbium tritides is a significant process in the aging of these materials. Due to the long-standing uncertainty about the initial nucleation process of these bubbles, there is interest in mechanisms that can lead to the localization of He in erbium hydrides. Previous work has been unable to identify nucleation sites in homogeneous erbium hydride. This work builds on the experimental observation that erbium hydrides have nano- scale erbium oxide precipitates due to the high thermodynamic stability of erbium oxide and the ubiquitous presence of oxygen during materials processing. Fundamental DFT calculations indicate that the He is energetically favored in the oxide relative to the bulk hydride. Activation energies for the motion of He in the oxide and at the oxide-hydride interface indicate that trapping is kinetically feasible. A simple kinetic Monte Carlo model is developed that demonstrates the degree of trapping of He as a function of temperature and oxide fraction.

  4. Photochromism of rare-earth metal-oxy-hydrides

    Science.gov (United States)

    Nafezarefi, F.; Schreuders, H.; Dam, B.; Cornelius, S.

    2017-09-01

    Recently, thin films of yttrium oxy-hydride (YOxHy) were reported to show an unusual color-neutral photochromic effect promising for application in smart windows. Our present work demonstrates that also oxy-hydrides based on Gd, Dy, and Er have photochromic properties and crystal structures similar to YOxHy. Compared to YOxHy, the optical bandgaps of the lanthanide based oxy-hydrides are smaller while photochromic contrast and kinetics show large variation among different cations. Based on these findings, we propose that cation alloying is a viable pathway to tailor the photochromic properties of oxy-hydride materials. Furthermore, we predict that the oxy-hydrides of the other lanthanides are also potentially photochromic.

  5. Metal hydrides for concentrating solar thermal power energy storage

    Science.gov (United States)

    Sheppard, D. A.; Paskevicius, M.; Humphries, T. D.; Felderhoff, M.; Capurso, G.; Bellosta von Colbe, J.; Dornheim, M.; Klassen, T.; Ward, P. A.; Teprovich, J. A.; Corgnale, C.; Zidan, R.; Grant, D. M.; Buckley, C. E.

    2016-04-01

    The development of alternative methods for thermal energy storage is important for improving the efficiency and decreasing the cost of concentrating solar thermal power. We focus on the underlying technology that allows metal hydrides to function as thermal energy storage (TES) systems and highlight the current state-of-the-art materials that can operate at temperatures as low as room temperature and as high as 1100 °C. The potential of metal hydrides for thermal storage is explored, while current knowledge gaps about hydride properties, such as hydride thermodynamics, intrinsic kinetics and cyclic stability, are identified. The engineering challenges associated with utilising metal hydrides for high-temperature TES are also addressed.

  6. Role of Pyridine as a Biomimetic Organo-Hydride for Homogeneous Reduction of CO2 to Methanol

    CERN Document Server

    Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

    2014-01-01

    We use quantum chemical calculations to elucidate a viable homogeneous mechanism for pyridine-catalyzed reduction of CO2 to methanol. In the first component of the catalytic cycle, pyridine (Py) undergoes a H+ transfer (PT) to form pyridinium (PyH+) followed by an e- transfer (ET) to produce pyridinium radical (PyH0). Examples of systems to effect this ET to populate the LUMO of PyH+(E0calc ~ -1.3V vs. SCE) to form the solution phase PyH0 via highly reducing electrons include the photo-electrochemical p-GaP system (ECBM ~ -1.5V vs. SCE at pH= 5) and the photochemical [Ru(phen)3]2+/ascorbate system. We predict that PyH0 undergoes further PT-ET steps to form the key closed-shell, dearomatized 1,2-dihydropyridine (PyH2) species. Our proposed sequential PT-ET-PT-ET mechanism transforming Py into PyH2 is consistent with the mechanism described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics the ...

  7. Development of low angle grain boundaries in lightly deformed superconducting niobium and their influence on hydride distribution and flux perturbation

    Science.gov (United States)

    Sung, Z.-H.; Wang, M.; Polyanskii, A. A.; Santosh, C.; Balachandran, S.; Compton, C.; Larbalestier, D. C.; Bieler, T. R.; Lee, P. J.

    2017-05-01

    This study shows that low angle grain boundaries (LAGBs) can be created by small 5% strains in high purity (residual resistivity ratio ≥ 200) superconducting radio frequency (SRF)-grade single crystalline niobium (Nb) and that these boundaries act as hydrogen traps as indicated by the distribution of niobium hydrides (Nb1-xHx). Nb1-xHx is detrimental to SRF Nb cavities due to its normal conducting properties at cavity operating temperatures. By designing a single crystal tensile sample extracted from a large grain (>5 cm) Nb ingot slice for preferred slip on one slip plane, LAGBs and dense dislocation boundaries developed. With chemical surface treatments following standard SRF cavity fabrication practice, Nb1-xHx phases were densely precipitated at the LAGBs upon cryogenic cooling (8-10 K/min). Micro-crystallographic analysis confirmed heterogeneous hydride precipitation, which included significant hydrogen atom accumulation in LAGBs. Magneto-optical imaging analysis showed that these sites can then act as sites for both premature flux penetration and eventually flux trapping. However, this hydrogen related degradation at LAGBs did not completely disappear even after an 800 °C/2 h anneal typically used for hydrogen removal in SRF Nb cavities. These findings suggest that hydride precipitation at an LAGB is facilitated by a non-equilibrium concentration of vacancy-hydrogen (H) complexes aided by mechanical deformation and the hydride phase interferes with the recovery process under 800 °C annealing.

  8. Investigation of the direct hydride generation nebulizer for the determination of arsenic, antimony and selenium in inductively coupled plasma optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Rojas, Illiana; Murillo, Miguel; Carrion, Nereida; Chirinos, Jose [Centro de Quimica Analitica, Escuela de Quimica, Facultad de Ciencias, Universidad Central de Venezuela, P.O. Box 47102, 1041a, Caracas (Venezuela)

    2003-05-01

    A direct hydride generation nebulizer (DHGN) was explored for introduction of the sample in inductively coupled plasma-optical emission spectrometry (ICP-OES) using radially viewed mode. This simple hydride generation system was constructed in our laboratory and requires similar plasma operating conditions to conventional nebulizer-spray-chamber arrangements. This work was focused on the optimization of the operating conditions for hydride generation and evaluation of the main analytical figures of merit for the determination of As, Sb and Se. The excitation conditions of the ICP-OES instrument operated with the DHGN were also explored. Results showed that the analytical performance of the new system for the determination of As, Sb and Se was superior to that of conventional nebulization systems. The DHGN also enabled the determination of elements that do not form volatile hydrides, but with less sensitivity than conventional nebulization systems. Evaluation of the plasma robustness showed that gases generated in hydride generation do not significantly affects the plasma discharge. Similar to conventional hydride generation techniques, analysis with DHGN was susceptible to non-spectroscopic interferences produced by transition metals. Finally, the utility of the DHGN in practical ICP-OES studies was demonstrated in the determination of trace elements in an oyster tissue standard reference material. (orig.)

  9. Synthesis and investigation of [Cp(PMe(3))Rh(H)(H(2))](+) and its partially deuterated and tritiated isotopomers: evidence for a hydride/dihydrogen structure.

    Science.gov (United States)

    Taw, Felicia L; Mellows, Heather; White, Peter S; Hollander, Frederick J; Bergman, Robert G; Brookhart, Maurice; Heinekey, D Michael

    2002-05-08

    Hydrogenolysis of [Cp(PMe(3))Rh(Me)(CH(2)Cl(2))](+)BAr'(4)(-) (4, Ar' = 3,5-C(6)H(3)(CF(3))(2)) in dichloromethane afforded the nonclassical polyhydride complex [Cp*PMe(3))Rh(H)(H(2))](+)BAr'(4)(-) (1), which exhibits a single hydride resonance at all accessible temperatures in the (1)H NMR spectrum. Exposure of solutions of 1 to D(2) or T(2) gas resulted in partial isotopic substitution in the hydride sites. Formulation of 1 as a hydride/dihydrogen complex was based upon T(1) (T(1)(min) = 23 ms at 150 K, 500 MHz), J(H-D) (ca. 10 Hz), and J(H-T) (ca. 70 Hz) measurements. The barrier (Delta G(++)) to exchange of hydride with dihydrogen sites was determined to be less than ca. 5 kcal/mol. Protonation of Cp(PMe(3))Rh(H)(2) (2) using H(OEt(2))(2)BAr'(4) resulted in binuclear species [(Cp(PMe(3))Rh(H))(2)(mu-H)](+)BAr'(4)(-) (3), which is formed in a reaction involving 1 as an intermediate. Complex 3 contains two terminal hydrides and one bridging hydride ligand which exchange with a barrier of 9.1 kcal/mol as observed by (1)H NMR spectroscopy. Additionally, the structures of 3 and 4, determined by X-ray diffraction, are reported.

  10. First detection of gas-phase ammonia in a planet-forming disk

    CERN Document Server

    Salinas, Vachail N; Bergin, Edwin A; Cleeves, L Ilsedore; Brinch, Christian; Blake, Geoffrey A; Lis, Dariusz C; Melnick, Gary J; Panić, Olja; Pearson, John C; Kristensen, Lars; Yıldız, Umut A; van Dishoeck, Ewine F

    2016-01-01

    Nitrogen chemistry in protoplanetary disks and the freeze-out on dust particles is key to understand the formation of nitrogen bearing species in early solar system analogs. So far, ammonia has not been detected beyond the snowline in protoplanetary disks. We aim to find gas-phase ammonia in a protoplanetary disk and characterize its abundance with respect to water vapor. Using HIFI on the Herschel Space Observatory we detect, for the first time, the ground-state rotational emission of ortho-NH$_3$ in a protoplanetary disk, around TW Hya. We use detailed models of the disk's physical structure and the chemistry of ammonia and water to infer the amounts of gas-phase molecules of these species. We explore two radial distributions ( confined to $<$60 au like the millimeter-sized grains) and two vertical distributions (near the midplane where water is expected to photodesorb off icy grains) to describe the (unknown) location of the molecules. These distributions capture the effects of radial drift and vertical...

  11. New milarite/osumilite-type phase formed during ancient glazing of an Egyptian scarab

    Science.gov (United States)

    Artioli, G.; Angelini, I.; Nestola, F.

    2013-02-01

    A scarab found in grave 25 of the Monte Prama necropolis, near Cabras, Oristano, Sardinia, is of special importance for the archaeological interpretation and dating of this important archaeological site. The object has been misinterpreted in the past as composed by bone: recent archaeometric analyses showed that it is a glazed steatite of Egyptian origin and that the altered surface contains interesting phases crystallized during the high-temperature interaction of the Mg-rich talc core with the alkali-rich glass used for glazing. A novel single crystal X-ray diffraction analysis of one of the phases indicates that it is a new compound having the milarite-osumilite structure type, with a peculiar composition close to (Na1.52K0.12□0.36)(Mg3)(Mg1.72Cu0.16Fe0.12)(Si11.4Al0.6)O30, not reported for naturally occurring minerals. The structural and crystal chemical features of the compound, together with the known high-temperature stability of the series, allow a complete interpretation of the glazing process and conditions, based on direct application of the glaze on the steatite core with subsequent treatment at temperatures above 1000 °C.

  12. Lithium hydride - A space age shielding material

    Science.gov (United States)

    Welch, F. H.

    1974-01-01

    Men and materials performing in the environment of an operating nuclear reactor require shielding from the escaping neutron particles and gamma rays. For efficient shielding from gamma rays, dense, high atomic number elements such as iron, lead, or tungsten are required, whereas light, low atomic number elements such as hydrogen, lithium, or beryllium are required for efficient neutron shielding. The use of lithium hydride (LiH) as a highly efficient neutron-shielding material is considered. It contains, combined into a single, stable compound, two of the elements most effective in attenuating and absorbing neutrons.

  13. Highly Concentrated Palladium Hydrides/Deuterides; Theory

    Energy Technology Data Exchange (ETDEWEB)

    Papaconstantopoulos, Dimitrios

    2013-11-26

    Accomplishments are reported in these areas: tight-binding molecular dynamics study of palladium; First-principles calculations and tight-binding molecular dynamics simulations of the palladium-hydrogen system; tight-binding studies of bulk properties and hydrogen vacancies in KBH{sub 4}; tight-binding study of boron structures; development of angular dependent potentials for Pd-H; and density functional and tight-binding calculations for the light-hydrides NaAlH4 and NaBH4

  14. Development of nickel-metal hydride cell

    Science.gov (United States)

    Kuwajima, Saburo; Kamimori, Nolimits; Nakatani, Kensuke; Yano, Yoshiaki

    1993-01-01

    National Space Development Agency of Japan (NASDA) has conducted the research and development (R&D) of battery cells for space use. A new R&D program about a Nickel-Metal Hydride (Ni-MH) cell for space use from this year, based on good results in evaluations of commercial Ni-MH cells in Tsukuba Space Center (TKSC), was started. The results of those commercial Ni-MH cell's evaluations and recent status about the development of Ni-MH cells for space use are described.

  15. Crack growth through the thickness of thin-sheet Hydrided Zircaloy-4

    Science.gov (United States)

    Raynaud, Patrick A. C.

    In recent years, the limits on fuel burnup have been increased to allow an increase in the amount of energy produced by a nuclear fuel assembly thus reducing waste volume and allowing greater capacity factors. As a result, it is paramount to ensure safety after longer reactor exposure times in the case of design-basis accidents, such as reactivity-initiated accidents (RIA). Previously proposed failure criteria do not directly address the particular cladding failure mechanism during a RIA, in which crack initiation in brittle outer-layers is immediately followed by crack growth through the thickness of the thin-wall tubing. In such a case, the fracture toughness of hydrided thin-wall cladding material must be known for the conditions of through-thickness crack growth in order to predict the failure of high-burnup cladding. The fracture toughness of hydrided Zircaloy-4 in the form of thin-sheet has been examined for the condition of through-thickness crack growth as a function of hydride content and distribution at 25°C, 300°C, and 375°C. To achieve this goal, an experimental procedure was developed in which a linear hydride blister formed across the width of a four-point bend specimen was used to inject a sharp crack that was subsequently extended by fatigue pre-cracking. The electrical potential drop method was used to monitor the crack length during fracture toughness testing, thus allowing for correlation of the load-displacement record with the crack length. Elastic-plastic fracture mechanics were used to interpret the experimental test results in terms of fracture toughness, and J-R crack growth resistance curves were generated. Finite element modeling was performed to adapt the classic theories of fracture mechanics applicable to thick-plate specimens to the case of through-thickness crack growth in thin-sheet materials, and to account for non-uniform crack fronts. Finally, the hydride microstructure was characterized in the vicinity of the crack tip by

  16. Form-stable crystalline polymer pellets for thermal energy storage. Phase 1

    Energy Technology Data Exchange (ETDEWEB)

    Botham, R.A.; Jenkins, G.H.; Ball, G.L. III; Salyer, I.O.

    1977-07-01

    The objective of this project was to develop a form-stable, crystalline polymer pellet TES bed material, useful in the 120 to 140/sup 0/C temperature range suitable for solar absorption air conditioning applications. This objective was achieved with a Si-O-Si crosslinked HDPE pellet material, demonstrated to have a high heat of fusion value (46 cal/g, approximately 98% of the HDPE's heat of fusion value prior to crosslinking). Further, on melt/freeze cycling of these TES pellets through 400 cycles in ethylene glycol, they retained nearly 100% of their initial heat of fusion value, and had excellent form-stability characteristics, with little or no inter-particle adhesion. Appropriate testing of this TES pellet material, from analytical (DSC) to a one gallon lab-scale TES unit, and finally to a 60 gallon prototype TES demonstration unit, consistently verified these results. C-C crosslinked PE products, which were slightly inferior to the Si-O-Si crosslinked PE in terms of good heat of fusion and form-stability properties, were also developed and are potential alternatives to the prime PE TES product.

  17. Matrix infrared spectra and density functional calculations of transition metal hydrides and dihydrogen complexes.

    Science.gov (United States)

    Andrews, Lester

    2004-02-20

    Metal hydrides are of considerable importance in chemical synthesis as intermediates in catalytic hydrogenation reactions. Transition metal atoms react with dihydrogen to produce metal dihydrides or dihydrogen complexes and these may be trapped in solid matrix samples for infrared spectroscopic study. The MH(2) or M(H(2)) molecules so formed react further to form higher MH(4), (H(2))MH(2), or M(H(2))(2), and MH(6), (H(2))(2)MH(2), or M(H(2))(3) hydrides or complexes depending on the metal. In this critical review these transition metal and dihydrogen reaction products are surveyed for Groups 3 though 12 and the contrasting behaviour in Groups 6 and 10 is discussed. Minimum energy structures and vibrational frequencies predicted by Density Functional Theory agree with the experimental results, strongly supporting the identification of novel binary transition metal hydride species, which the matrix-isolation method is well-suited to investigate. 104 references are cited.

  18. Heavy hydrides: H2Te ultraviolet photochemistry

    Science.gov (United States)

    Underwood, J.; Chastaing, D.; Lee, S.; Wittig, C.

    2005-08-01

    The room-temperature ultraviolet absorption spectrum of H2Te has been recorded. Unlike other group-6 hydrides, it displays a long-wavelength tail that extends to 400 nm. Dissociation dynamics have been examined at photolysis wavelengths of 266 nm (which lies in the main absorption feature) and 355 nm (which lies in the long-wavelength tail) by using high-n Rydberg time-of-flight spectroscopy to obtain center-of-mass translational energy distributions for the channels that yield H atoms. Photodissociation at 355 nm yields TeH(Π1/22) selectively relative to the TeH(Π3/22) ground state. This is attributed to the role of the 3A' state, which has a shallow well at large RH-TeH and correlates to H +TeH(Π1/22). Note that the Π1/22 state is analogous to the P1/22 spin-orbit excited state of atomic iodine, which is isoelectronic with TeH. The 3A' state is crossed at large R only by 2A″, with which it does not interact. The character of 3A' at large R is influenced by a strong spin-orbit interaction in the TeH product. Namely, Π1/22 has a higher degree of spherical symmetry than does Π3/22 (recall that I(P1/22) is spherically symmetric), and consequently Π1/22 is not inclined to form either strongly bonding or antibonding orbitals with the H atom. The 3A'←X transition dipole moment dominates in the long-wavelength region and increases with R. Structure observed in the absorption spectrum in the 380-400 nm region is attributed to vibrations on 3A'. The main absorption feature that is peaked at ˜240nm might arise from several excited surfaces. On the basis of the high degree of laboratory system spatial anisotropy of the fragments from 266 nm photolysis, as well as high-level theoretical studies, the main contribution is believed to be due to the 4A″ surface. The 4A″←X transition dipole moment dominates in the Franck-Condon region, and its polarization is in accord with the experimental observations. An extensive secondary photolysis (i.e., of nascent TeH) is

  19. Structural and magnetic transformations in the GdMn{sub 2}H{sub x} hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Zukrowski, J.; Figiel, H. E-mail: figiel@uci.agh.edu.pl; Budziak, A.; Zachariasz, P.; Fischer, G.; Dormann, E

    2002-01-01

    Powder samples of GdMn{sub 2}H{sub x} hydrides, with 0{<=}x{<=}4.3, have been characterized by X-ray analysis and SQUID magnetometry for temperatures ranging between 4 and 375 K. The observed phase transformations as a function of temperature and hydrogen concentration are discussed and explained. The correlated changes of magnetization and susceptibility have been analyzed and the temperature dependent development of magnetic ordering of Mn and Gd atoms as a function of temperature and hydrogen content has been discussed. The structural and magnetic phase diagrams have been proposed.

  20. Structure and microdomain structure of ordered niobium hydrides and deuterides by means of neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Hauer, B. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Festkoerperforschung]|[Physikalische Chemie, Universitaet des Saarlandes, 66123, Saarbruecken (Germany); Hempelmann, R. [Physikalische Chemie, Universitaet des Saarlandes, 66123, Saarbruecken (Germany); Udovic, T.J.; Rush, J.J. [National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Kockelmann, W.; Jansen, E.; Schaefer, W. [Institut fuer Mineralogie der Universitaet Bonn, Aussenstelle Juelich, 52425, Juelich (Germany); Richter, D. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Festkoerperforschung

    1997-05-20

    Extensive high-resolution vibrational density of states measurements have been performed on ordered niobium hydrides and deuterides by means of neutron vibrational spectroscopy (NVS). The investigations show a splitting of the hydrogen vibrational modes into a two-peak system in the case of the {epsilon}-phase and a three-peak system in the case of the {lambda}-phase. These different peak systems can be assigned to different hydrogen sites, which is further confirmed by neutron diffraction (ND) data. (orig.) 5 refs.

  1. Pressure-induced hydrogen-dominant metallic state in aluminum hydride.

    Science.gov (United States)

    Goncharenko, Igor; Eremets, M I; Hanfland, M; Tse, J S; Amboage, M; Yao, Y; Trojan, I A

    2008-02-01

    Two structural transitions in covalent aluminum hydride AlH3 were characterized at high pressure. A metallic phase stable above 100 GPa is found to have a remarkably simple cubic structure with shortest first-neighbor H-H distances ever measured except in H2 molecule. Although the high-pressure phase is predicted to be superconductive, this was not observed experimentally down to 4 K over the pressure range 120-164 GPa. The results indicate that the superconducting behavior may be more complex than anticipated.

  2. Defect structure of erbium-doped <1 1 1> silicon layers formed by solid phase epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Kyutt, R.N.; Sobolev, Nikolai A. E-mail: nick@sobolev.ioffe.rssi.ru; Nikolaev, Yu. A.; Vdovin, V.I

    2001-01-01

    Erbium-doped layers have been produced on <1 1 1>-oriented silicon wafers using high-energy amorphizing Er implants and solid phase epitaxy (SPE). Transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques, used to study the microstructure of these layers, revealed the presence of microtwins and dislocations. The twins were found to be platelets with lateral dimensions of 15-30 nm and a thickness of about 2-9 nm, and their density throughout the regrown layer was nonuniform. The dislocation densities observed in the regrown layers were very high with densities exceeding 10{sup 10} cm{sup -2}. Within the implant fluence range studied, between 1x10{sup 14} and 9x10{sup 14} Er cm{sup -2}, the twin and dislocation densities were observed to increase with fluence, while the twin dimensions were found to decrease.

  3. Triphosphine-Ligated Copper Hydrides for CO2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies.

    Science.gov (United States)

    Zall, Christopher M; Linehan, John C; Appel, Aaron M

    2016-08-10

    The copper(I) triphosphine complex LCu(MeCN)PF6 (L = 1,1,1-tris(diphenylphosphinomethyl)ethane), which we recently demonstrated is an active catalyst precursor for hydrogenation of CO2 to formate, reacts with H2 in the presence of a base to form a cationic dicopper hydride, [(LCu)2H]PF6. [(LCu)2H](+) is also an active precursor for catalytic CO2 hydrogenation, with equivalent activity to that of LCu(MeCN)(+), and therefore may be a relevant catalytic intermediate. The thermodynamic hydricity of [(LCu)2H](+) was determined to be 41.0 kcal/mol by measuring the equilibrium constant for this reaction using three different bases. [(LCu)2H](+) and the previously reported dimer (LCuH)2 can be synthesized by the reaction of LCu(MeCN)(+) with 0.5 and 1 equiv of KB(O(i)Pr)3H, respectively. The solid-state structure of [(LCu)2H](+) shows threefold symmetry about a linear Cu-H-Cu axis and significant steric strain imposed by bringing two LCu(+) units together around the small hydride ligand. [(LCu)2H](+) reacts stoichiometrically with CO2 to generate the formate complex LCuO2CH and the solvento complex LCu(MeCN)(+). The rate of the stoichiometric reaction between [(LCu)2H](+) and CO2 is dramatically increased in the presence of bases that coordinate strongly to the copper center, e.g. DBU and TMG. In the absence of CO2, the addition of a large excess of DBU to [(LCu)2H](+) results in an equilibrium that forms LCu(DBU)(+) and also presumably the mononuclear hydride LCuH, which is not directly observed. Due to the significantly enhanced CO2 reactivity of [(LCu)2H](+) under these catalytically relevant conditions, LCuH is proposed to be the catalytically active metal hydride.

  4. Sintering activation of 316L powder using a liquid phase forming powder

    Directory of Open Access Journals (Sweden)

    Nattaya Tosangthum

    2010-03-01

    Full Text Available It was found that the addition of a liquid forming powder (up to 6 wt.% of a gas-atomized tin powder to 316L powdercould activate the sintering process. Sintering activation could be observed by an increase of the sintered density and selected mechanical properties. When optimized tin powder content was used, shorter sintering time and lower sintering temperaturecould produce sintered 316L+tin materials with excellent mechanical properties. Electron dispersive spectroscopy analyses across 316L-tin-316L grains indicated that Ni transportation during the sintering process was enhanced by the presence of liquid tin.

  5. Radionuclide Retention Mechanisms in Secondary Waste-Form Testing: Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Um, Wooyong; Valenta, Michelle M.; Chung, Chul-Woo; Yang, Jungseok; Engelhard, Mark H.; Serne, R. Jeffrey; Parker, Kent E.; Wang, Guohui; Cantrell, Kirk J.; Westsik, Joseph H.

    2011-09-26

    This report describes the results from laboratory tests performed at Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions (WRPS) to evaluate candidate stabilization technologies that have the potential to successfully treat liquid secondary waste stream effluents produced by the Hanford Tank Waste Treatment and Immobilization Plant (WTP). WRPS is considering the design and construction of a Solidification Treatment Unit (STU) for the Effluent Treatment Facility (ETF) at Hanford. The ETF, a multi-waste, treatment-and-storage unit that has been permitted under the Resource Conservation and Recovery Act (RCRA), can accept dangerous, low-level, and mixed wastewaters for treatment. The STU needs to be operational by 2018 to receive secondary liquid waste generated during operation of the WTP. The STU will provide the additional capacity needed for ETF to process the increased volume of secondary waste expected to be produced by WTP. This report on radionuclide retention mechanisms describes the testing and characterization results that improve understanding of radionuclide retention mechanisms, especially for pertechnetate, {sup 99}TcO{sub 4}{sup -} in four different waste forms: Cast Stone, DuraLith alkali aluminosilicate geopolymer, encapsulated fluidized bed steam reforming (FBSR) product, and Ceramicrete phosphate bonded ceramic. These data and results will be used to fill existing data gaps on the candidate technologies to support a decision-making process that will identify a subset of the candidate waste forms that are most promising and should undergo further performance testing.

  6. Structural and magnetic properties of C15 HoMn{sub 2} hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Budziak, A., E-mail: andrzej.budziak@ifj.edu.pl [H.Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Zachariasz, P. [Institute of Atomic Energy POLATOM, 05-400 Otwock-Swierk (Poland); Kolwicz-Chodak, L.; Figiel, H. [Faculty of Physics and Applied Computer Science, University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow (Poland); Pacyna, A. [H.Niewodniczanski Institute of Nuclear Physics PAN, ul. Radzikowskiego 152, 31-342 Krakow (Poland); Zukrowski, J. [Faculty of Physics and Applied Computer Science, University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow (Poland)

    2011-02-03

    Research highlights: > Full structural and magnetic phase diagrams are presented for the HoMn{sub 2}H{sub x}(0 < x {<=} 4.3) hydrides, where x = 4.3 is a typical maximal hydrogen concentration obtained for RMn{sub 2}H{sub x} (R: rare earth) under low pressure of H{sub 2} (ca {approx} 1 bar). > For x < {approx} 1.6: (1) The spinodal decompositions into two structurally different phases are observed. The lattice parameters of one of them correspond to those of the pure host HoMn{sub 2} material, while the lattice parameters of the other phase correspond to those of HoMn{sub 2}H{sub 1.6}. (2) Abundances of both phases change with hydrogen concentration x. (3) No intermediate phase appears, which is typical for other hydrides based on the C15 Laves phase type compounds (e.g. (Tb, Gd)Mn{sub 2}). Instead of that, structural transformations to monoclinic structures are observed. > For x = 2.5 splitting into two phases with different hydrogen concentrations x (x{sub 1} {approx} 2.3 and x{sub 2} {approx} 2.8) appears again, which was observed only for hydrides based on the C14 Laves phase type compounds (e.g. in (Sm, Er, Nd)Mn{sub 2}H{sub x}) in the range 2 < x < 3. > For samples with 2 < x < 2.2 no structural transformations are detected. > The effects of hydrogen absorption on structural properties are shown to be reflected in magnetic behavior. > A huge jump of magnetic ordering temperatures from {approx}24 K for HoMn{sub 2} to {approx} (200-380) K for its hydrides is observed. - Abstract: Powder samples of cubic HoMn{sub 2}H{sub x} hydrides, with 0 {<=} x {<=} 4.3, have been investigated by X-ray diffraction and AC/DC magnetometry as a function of temperature and external magnetic field. Hydrogen is demonstrated to strongly modify structural and magnetic properties. X-ray studies revealed many structural transformations placed at low temperatures. In particular, a transformation from the cubic to the monoclinic structure was detected, which so far has not been reported

  7. A generic statistical model of hydride formation in a random alloy

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2016-09-01

    Hydride formation in metals (e.g. in Pd), accompanied by a hysteresis loop in the absorption isotherms, is one of the generic examples of first-order phase transitions (FOPTs). During the last decade, the corresponding experimental studies, driven by applications related to hydrogen storage, have shifted towards metal particles sized from a few nanometers to micrometers in general and to alloyed particles of these sizes in particular. The understanding of hydride formation in alloys is, however, still far from complete. Herein, a statistical model of hydride formation in a random alloy is presented. The model is focused on the situation when this process is favorable in metal 1 (e.g. Pd) and shows what may happen when atoms of metal 2 make it less favorable due to decrease of the hydrogen binding energy and/or attractive hydrogen-hydrogen (H-H) interaction. Random distribution of metal atoms is taken explicitly into account. The attractive H-H interaction, including its dependence on fraction of metal 2 in the alloy, is described at the mean-field level. With increasing fraction of the latter metal, the critical temperature is found to decrease linearly or nonlinearly depending on the values of the model parameters. If the decrease of the hydrogen binding energy with increasing number of nearest-neighbor (nn) atoms of metal 2 is appreciable, the model predicts up to three hysteresis loops.

  8. The Planck Sorption Cooler: Using Metal Hydrides to Produce 20 K

    Science.gov (United States)

    Pearson, David P.; Bowman, R.; Prina, M.; Wilson, P.

    2006-01-01

    The Jet Propulsion Laboratory has built and delivered two continuous closed cycle hydrogen Joule-Thomson (JT) cryocoolers for the ESA Planck mission, which will measure the anisotropy in the cosmic microwave background. The metal hydride compressor consists of six sorbent beds containing LaNi4.78Sn0.22 alloy and a low pressure storage bed of the same material. Each sorbent bed contains a separate gas-gap heat switch that couples or isolates the bed with radiators during the compressor operating cycle. ZrNiHx hydride is used in this heat switch. The Planck compressor produces hydrogen gas at a pressure of 48 Bar by heating the hydride to approx.450 K. This gas passes through a cryogenic cold end consisting of a tube-in-tube heat exchanger, three pre-cooling stages to bring the gas to nominally 52 K, a JT value to expand the gas into the two-phase regime at approx.20 K, and two liquid - vapor heat exchangers that must remove 190 and 646 mW of heat respectively.

  9. Review of crystalline structures of some selected homologous series of rod-like molecules capable of forming liquid crystalline phases.

    Science.gov (United States)

    Zugenmaier, Peter

    2011-01-01

    The crystal structures of four homologous series of rod-like molecules are reviewed, two of which form hydrogen bonds and two with a symmetric chemical constitution. Many of the compounds investigated turn into liquid crystalline phases upon temperature increase. It is of valuable interest to know possible conformations and possible packing arrangements as prerequisites to model liquid crystalline structures. The hydrogen bonds of homologous series of pure 4-(ω-hydroxyalkyloxy)-4'-hydroxybiphenyl (HnHBP, n the alkyloxy tail length) are realized through head to tail arrangements of the hydroxyl groups and crystallize except one compound in chiral space groups without the molecules containing any asymmetric carbon. The hydrogen bonds of the homologous series of 4-substituted benzoic acids with various lengths of the tail provide dimers through strong polar bonding of adjacent carboxyl groups and thus provide the stiff part of a mesogenic unit prerequisite for liquid crystalline phases. The homologous series of dialkanoyloxybiphenyls (BP-n, n = 1, 19), of which nine compounds could be crystallized, show liquid crystalline behavior for longer alkane chain lengths, despite the high mobility of the alkane chain ends already detectable in the crystal phase. A single molecule, half a molecule or two half molecules form the asymmetric unit in a centrosymmetric space group. The homologous series of 1,4-terephthalidene-bis-N-(4'-n-alkylaniline) (TBAA-n) exhibit a large variety of packing arrangements in the crystalline state, with or without relying on the symmetry center within the molecules.

  10. NATO Advanced Study Institute on Metal Hydrides

    CERN Document Server

    1981-01-01

    In the last five years, the study of metal hydrides has ex­ panded enormously due to the potential technological importance of this class of materials in hydrogen based energy conversion schemes. The scope of this activity has been worldwide among the industrially advanced nations. There has been a consensus among researchers in both fundamental and applied areas that a more basic understanding of the properties of metal/hydrogen syster;,s is required in order to provide a rational basis for the selection of materials for specific applications. The current worldwide need for and interest in research in metal hydrides indicated the timeliness of an Advanced Study Insti­ tute to provide an in-depth view of the field for those active in its various aspects. The inclusion of speakers from non-NATO coun­ tries provided the opportunity for cross-fertilization of ideas for future research. While the emphasis of the Institute was on basic properties, there was a conscious effort to stimulate interest in the applic...

  11. From permanent magnets to rechargeable hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Willems, J.J.G.; Buschow, K.H.J.

    1987-02-15

    A brief historical survey is given of how the study of coercitivity mechanisms in SmCo/sub 5/ permanent-magnet materials eventually led to the discovery of the favourable hydrogen sorption properties of the compound LaNi/sub 5/. It is shown how continued research by many investigators dealing with a variety of different physical and chemical properties has resulted in an advanced understanding of some of the principles that govern hydrogen absorption and which are responsible for the changes in physical properties that accompany it. The problems associated with various applications of LaNi/sub 5/-based hydrogen-storage materials are also briefly discussed. A large part of this paper is devoted to the applicability of LaNi/sub 5/-type materials in batteries. Research in this area has resulted in the development of a new type of rechargeable battery: the nickel-hydride cell. This battery can be charged and discharged at high rates and is relatively insensitive to overcharging and overdischarging. Special attention is given to the nature of the electrode degradation process and the effect of composition variations in LaNi/sub 5/-related materials on the lifetime of the corresponding hydride electrodes when subjected to severe electrochemical charge-discharge cycles.

  12. Metal hydrides for lithium-ion batteries.

    Science.gov (United States)

    Oumellal, Y; Rougier, A; Nazri, G A; Tarascon, J-M; Aymard, L

    2008-11-01

    Classical electrodes for Li-ion technology operate via an insertion/de-insertion process. Recently, conversion electrodes have shown the capability of greater capacity, but have so far suffered from a marked hysteresis in voltage between charge and discharge, leading to poor energy efficiency and voltages. Here, we present the electrochemical reactivity of MgH(2) with Li that constitutes the first use of a metal-hydride electrode for Li-ion batteries. The MgH(2) electrode shows a large, reversible capacity of 1,480 mAh g(-1) at an average voltage of 0.5 V versus Li(+)/Li(o) which is suitable for the negative electrode. In addition, it shows the lowest polarization for conversion electrodes. The electrochemical reaction results in formation of a composite containing Mg embedded in a LiH matrix, which on charging converts back to MgH(2). Furthermore, the reaction is not specific to MgH(2), as other metal or intermetallic hydrides show similar reactivity towards Li. Equally promising, the reaction produces nanosized Mg and MgH(2), which show enhanced hydrogen sorption/desorption kinetics. We hope that such findings can pave the way for designing nanoscale active metal elements with applications in hydrogen storage and lithium-ion batteries.

  13. Chemical characterization of the main secondary organic aerosol (SOA products formed through aqueous-phase photonitration of guaiacol

    Directory of Open Access Journals (Sweden)

    Z. Kitanovski

    2014-04-01

    Full Text Available Guaiacol (2-methoxyphenol and its derivatives can be emitted into the atmosphere by thermal degradation (i.e. burning of wood lignins. Due to its volatility, guaiacol is predominantly distributed in the atmospheric gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA in the atmosphere. The main objectives of the present study were to chemically characterize the low-volatility SOA products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of H2O2 and nitrite. The formed guaiacol reaction products were concentrated by using solid-phase extraction (SPE and then purified by means of semi-preparative high-performance liquid chromatography (HPLC. The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state 1H, 13C and 2D nuclear magnetic resonance (NMR spectroscopy and direct infusion negative ion electrospray ionization tandem mass spectrometry ((–ESI-MS/MS. The NMR and product ion (MS2 spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG, 6-nitroguaiacol (6NG, and 4,6-dinitroguaiacol (4,6DNG. Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia by means of HPLC/(–ESI-MS/MS. Owing to the strong absorption of UV and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  14. Kinetics of thermal decomposition of titanium hydride powder using in situ high-temperature X-ray diffraction (HTXRD

    Directory of Open Access Journals (Sweden)

    Hugo Ricardo Zschommler Sandim

    2005-09-01

    Full Text Available The thermal decomposition of titanium hydride powder (delta-phase to titanium (alpha-phase was investigated by means of thermogravimetric analysis (TGA and high-temperature X-ray diffraction (HTXRD in high vacuum. The delta-to-alpha phase transformation was followed in situ by HTXRD at temperatures varying from room temperature up to 1000 °C. The transformation was also analyzed as a function of time at isothermal conditions from 450 to 650 °C. The results of TGA show that the decomposition of the titanium hydride becomes significant at about 450 °C. Above 500 °C the decomposition is completed in times shorter than 50 minutes. The apparent activation energy for hydrogen desorption was found to be 63 ± 6 kJ.mol-1.

  15. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    Science.gov (United States)

    Fegler, Waldemar; Venugopal, Ajay; Kramer, Mathias; Okuda, Jun

    2015-02-02

    Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

  16. Spray forming -- Aluminum: Third annual report (Phase 2). Technical progress -- Summary

    Energy Technology Data Exchange (ETDEWEB)

    Kozarek, R.L.

    1998-04-20

    Commercial production of aluminum sheet and plate by spray atomization and deposition is a potentially attractive manufacturing alternative to conventional ingot metallurgy/hot-milling and to continuous casting processes because of reduced energy requirements and reduced cost. To realize the full potential of the technology, the Aluminum Company of America (Alcoa), under contract by the US Department of Energy, is investigating currently available state-of-the-art atomization devices to develop nozzle design concepts whose spray characteristics are tailored for continuous sheet production. This third technical progress report will summarize research and development work conducted during the period 1997 October through 1998 March. Included are the latest optimization work on the Alcoa III nozzle, results of spray forming runs with 6111 aluminum alloy and preliminary rolling trials of 6111 deposits.

  17. Properties of Zr-Ti-V-Mn-Ni hydride alloy

    Institute of Scientific and Technical Information of China (English)

    文明芬; 翟玉春; 王新海; 陈廉

    2002-01-01

    Six kinds of Zr-based hydride alloy were designed. XRD analyses show that the main phase of Zr1-xTix-(NiCoMnV)2.1 alloy is Laves C15 when x is between 0 and 0.5,but the more the content of Ti, the more the Laves C14 phases. The amount of Laves C14 can be up to the amount of Laves C15 after substituted V and Fe by V-Fe alloy in Zr0.6-Ti0.4(NiCoMnVFeCr)1.7 alloy. The electrochemical measurements show that the discharge capacity of Zr0.9Ti0.1-(NiCoMnV)2.1 electrode is about 340mA * h/g at 60mA/g, but with increasing the amount of Ti, the discharge capacity of alloy electrode abruptly decreases; at 300mA/g current density, its Kr can be up to 91%. The discharge capacity of Zr0.6-Ti0.4-(NiCoMn(V-Fe)Cr)1.62 alloy electrode is about 200mA * h/g at first cycle, the maximum capacity is more than that of the electrode with pure V, and about 315mA * h/g.

  18. Alloys for hydrogen storage in nickel/hydrogen and nickel/metal hydride batteries

    Science.gov (United States)

    Anani, Anaba; Visintin, Arnaldo; Petrov, Konstantin; Srinivasan, Supramaniam; Reilly, James J.; Johnson, John R.; Schwarz, Ricardo B.; Desch, Paul B.

    1993-01-01

    Since 1990, there has been an ongoing collaboration among the authors in the three laboratories to (1) prepare alloys of the AB(sub 5) and AB(sub 2) types, using arc-melting/annealing and mechanical alloying/annealing techniques; (2) examine their physico-chemical characteristics (morphology, composition); (3) determine the hydrogen absorption/desorption behavior (pressure-composition isotherms as a function of temperature); and (4) evaluate their performance characteristics as hydride electrodes (charge/discharge, capacity retention, cycle life, high rate capability). The work carried out on representative AB(sub 5) and AB(sub 2) type modified alloys (by partial substitution or with small additives of other elements) is presented. The purpose of the modification was to optimize the thermodynamics and kinetics of the hydriding/dehydriding reactions and enhance the stabilities of the alloys for the desired battery applications. The results of our collaboration, to date, demonstrate that (1) alloys prepared by arc melting/annealing and mechanical alloying/annealing techniques exhibit similar morphology, composition and hydriding/dehydriding characteristics; (2) alloys with the appropriate small amounts of substituent or additive elements: (1) retain the single phase structure, (2) improve the hydriding/dehydriding reactions for the battery applications, and (3) enhance the stability in the battery environment; and (3) the AB(sub 2) type alloys exhibit higher energy densities than the AB(sub 5) type alloys but the state-of-the-art, commercialized batteries are predominantly manufactured using Ab(sub 5) type alloys.

  19. First-Principles Point Defect Models for Zr7Ni10 and Zr2Ni7 Phases

    Directory of Open Access Journals (Sweden)

    Diana F. Wong

    2016-06-01

    Full Text Available Synergetic effects in multi-phased AB2 Laves-phase-based metal hydride (MH alloys enable the access of high hydrogen storage secondary phases, despite the lower absorption/desorption kinetics found in nickel/metal hydride (Ni/MH batteries. Alloy design strategies to further tune the electrochemical properties of these secondary phases include the use of additives and processing techniques to manipulate the chemical nature and the microstructure of these materials. It is also of particular interest to observe the engineering of constitutional point defects and how they may affect electrochemical properties and performance. The Zr7Ni10 phase appears particularly prone to point defects, and we use density functional theory (DFT calculations coupled with a statistical mechanics model to study the theoretical point defects. The Zr2Ni7 phase appears less prone to point defects, and we use the Zr2Ni7 point defect model, as well as experimental lattice parameters, with Zr7Ni10 phases from X-ray diffraction (XRD as points of comparison. The point defect models indicate that anti-site defects tend to form in the Zr7Ni10 phase, and that these defects form more easily in the Zr7Ni10 phase than the Zr2Ni7 phase, as expected.

  20. Electron beam-formed ferromagnetic defects on MoS2 surface along 1 T phase transition

    Science.gov (United States)

    Han, Sang Wook; Park, Youngsin; Hwang, Young Hun; Jekal, Soyoung; Kang, Manil; Lee, Wang G.; Yang, Woochul; Lee, Gun-Do; Hong, Soon Cheol

    2016-12-01

    1 T phase incorporation into 2H-MoS2 via an optimal electron irradiation leads to induce a weak ferromagnetic state at room temperature, together with the improved transport property. In addition to the 1T-like defects, the electron irradiation on the cleaved MoS2 surface forms the concentric circle-type defects that are caused by the 2 H/1 T phase transition and the vacancies of the nearby S atoms of the Mo atoms. The electron irradiation-reduced bandgap is promising in vanishing the Schottky barrier to attaining spintronics device. The simple method to control and improve the magnetic and electrical properties on the MoS2 surface provides suitable ways for the low-dimensional device applications.

  1. Early Phases Of Galaxy Assembly Revealed By Young Star-Forming Dwarfs At Z 3

    Science.gov (United States)

    Amorín, Ricardo; VUDS Collaboration

    2017-06-01

    Studying lower-redshift analogs of the first galaxies is essential to scrutinize the details of galaxy formation and cosmic reionization, paving the way for a better interpretation of observations of primeval galaxies with the James Webb Space Telescope. In this talk I will present a thorough study of a recently discovered population of small, sub-L* star-forming galaxies at redshift z 2-4 that exhibit all the rest-frame properties expected for early galaxies in their first epoch of assembling and chemical enrichment. Selected by their strong nebular emission in the UV (including emission lines such as CIII]1908, CIV1550 and OIII]1664) from thousands of galaxies in the VIMOS Ultra Deep Survey, these young low mass systems are extremely metal-deficient galaxies that are likely experiencing their first significant starburst episode. I will discuss their rest-frame properties, hard radiations fields, strong Lyman-alpha emission, HST morphologies and strongly sub-solar chemical abundances. Finally, I will compare their properties with that of galaxies observed at the edge of the reionization epoch, which pose interesting prospects for JWST studies.

  2. CO observations of massive star forming regions at different evolutionary phases

    Institute of Scientific and Technical Information of China (English)

    CHEN; Xi; XU; Ye; SHEN; Zhiqiang; LI; Jingjing

    2006-01-01

    The 12CO (J=1-0), 13CO (J=1-0) and C18O (J=1-0) emissions in 9 massive star forming regions, which are believed to be at different stages of massive star formation,were mapped with the 13.7 m millimeter wave telescope at Qinghai Station of Purple Mountain Observatory. Of the observed 9 sources, 13CO cores were detected in seven of them, and C18O cores in five of them. And only two sources associated with C18O cores and H2O masers showed the extended structures and strong outflows. This is the first detection of outflow associated with IRAS 22566+5828 in the observing field of S152/S153.The physical parameters of cores and outflows for these sources, derived from Local Thermal Equilibrium (LTE) analysis, are presented. These observing results suggest that the C18O cores will only appear when the gas density is high enough and the probability to have an outflow is very high when the clumps show the C18O and H2O maser simultaneously.

  3. Technical and economic aspects of hydrogen storage in metal hydrides

    Science.gov (United States)

    Schmitt, R.

    1981-01-01

    The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

  4. PIE techniques for hydride reorientation test at NDC

    Energy Technology Data Exchange (ETDEWEB)

    Tsuda, Tomohiro; Shinohara, Yasunari; Yamaguchi, Yoichiro [Nuclear Development Corporation, Ibaraki (Japan)

    2008-11-15

    Dry storage of spent fuels in the interim storage facility is being planned in Japan. However, the gradual deterioration of the mechanical property of fuel cladding due to internal pressure and temperature during the storage term is known. Therefore, the integrity of stored fuel rods should be confirmed before the start of dry storage. For the last several years, NDC had a lot of experiences on the hydride reorientation test. The specimen preparation techniques on the hydride reorientation test and the mechanical testing techniques after the hydride reorientation are shown in this paper.

  5. Recent progress in understanding the hot and warm gas phases in the halos of star-forming galaxies

    CERN Document Server

    Strickland, D K; Colbert, E J M; Hoopes, C G; Weaver, K A

    2002-01-01

    In this contribution we present a few selected examples of how the latest generation of space-based instrumentation -- NASA's Chandra X-ray Observatory and the Far-Ultraviolet Spectroscopic Explorer (FUSE) -- are finally answering old questions about the influence of massive star feedback on the warm and hot phases of the ISM and IGM. In particular, we discuss the physical origin of the soft thermal X-ray emission in the halos of star-forming and starburst galaxies, its relationship to extra-planar H-alpha emission, and plasma diagnostics using FUSE observations of O VI absorption and emission.

  6. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  7. EVALUATION OF THOR MINERALIZED WASTE FORMS FOR THE DOE ADVANCED REMEDIATION TECHNOLOGIES PHASE 2 PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, C.; Jantzen, C.

    2012-02-02

    The U.S. Department of Energy's (DOE) Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford's tank waste. Currently there are approximately 56 million gallons of highly radioactive mixed wastes awaiting treatment. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in the time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Therefore, Supplemental Treatment is required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP's LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). In addition, the WTP LAW Vitrification facility off-gas condensate known as WTP Secondary Waste (WTP-SW) will be generated and enriched in volatile components such as Cs-137, I-129, Tc-99, Cl, F, and SO{sub 4} that volatilize at the vitrification temperature of 1150 C in the absence of a continuous cold cap. The current waste disposal path for the WTP-SW is to recycle it to the supplemental LAW treatment to avoid a large steady state accumulation in the pretreatment-vitrification loop. Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750 C) continuous method by which LAW and/or WTP-SW wastes can be processed irrespective of whether they contain organics, nitrates

  8. EVALUATION OF THOR MINERALIZED WASTE FORMS FOR THE DOE ADVANCED REMEDIATION TECHNOLOGIES PHASE 2 PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, C.; Jantzen, C.

    2012-02-02

    The U.S. Department of Energy's (DOE) Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford's tank waste. Currently there are approximately 56 million gallons of highly radioactive mixed wastes awaiting treatment. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in the time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Therefore, Supplemental Treatment is required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP's LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). In addition, the WTP LAW Vitrification facility off-gas condensate known as WTP Secondary Waste (WTP-SW) will be generated and enriched in volatile components such as Cs-137, I-129, Tc-99, Cl, F, and SO{sub 4} that volatilize at the vitrification temperature of 1150 C in the absence of a continuous cold cap. The current waste disposal path for the WTP-SW is to recycle it to the supplemental LAW treatment to avoid a large steady state accumulation in the pretreatment-vitrification loop. Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750 C) continuous method by which LAW and/or WTP-SW wastes can be processed irrespective of whether they contain organics, nitrates

  9. Empirical and physics based mathematical models of uranium hydride decomposition kinetics with quantified uncertainties.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Gharagozloo, Patricia E.

    2013-10-01

    Metal particle beds have recently become a major technique for hydrogen storage. In order to extract hydrogen from such beds, it is crucial to understand the decomposition kinetics of the metal hydride. We are interested in obtaining a a better understanding of the uranium hydride (UH3) decomposition kinetics. We first developed an empirical model by fitting data compiled from different experimental studies in the literature and quantified the uncertainty resulting from the scattered data. We found that the decomposition time range predicted by the obtained kinetics was in a good agreement with published experimental results. Secondly, we developed a physics based mathematical model to simulate the rate of hydrogen diffusion in a hydride particle during the decomposition. We used this model to simulate the decomposition of the particles for temperatures ranging from 300K to 1000K while propagating parametric uncertainty and evaluated the kinetics from the results. We compared the kinetics parameters derived from the empirical and physics based models and found that the uncertainty in the kinetics predicted by the physics based model covers the scattered experimental data. Finally, we used the physics-based kinetics parameters to simulate the effects of boundary resistances and powder morphological changes during decomposition in a continuum level model. We found that the species change within the bed occurring during the decomposition accelerates the hydrogen flow by increasing the bed permeability, while the pressure buildup and the thermal barrier forming at the wall significantly impede the hydrogen extraction.

  10. Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO2.

    Science.gov (United States)

    Brown, Neil J; Harris, Jonathon E; Yin, Xinning; Silverwood, Ian; White, Andrew J P; Kazarian, Sergei G; Hellgardt, Klaus; Shaffer, Milo S P; Williams, Charlotte K

    2014-03-10

    The synthesis, characterization, and zinc coordination chemistry of the three proligands 2-tert-butyl-4-[tert-butyl (1)/methoxy (2)/nitro (3)]-6-{[(2'-dimethylaminoethyl)methylamino]methyl}phenol are described. Each of the ligands was reacted with diethylzinc to yield zinc ethyl complexes 4-6; these complexes were subsequently reacted with phenylsilanol to yield zinc siloxide complexes 7-9. Finally, the zinc siloxide complexes were reacted with phenylsilane to produce the three new zinc hydride complexes 10-12. The new complexes 4-12 have been fully characterized by NMR spectroscopy, mass spectrometry, and elemental analyses. The structures of the zinc hydride complexes have been probed using VT-NMR spectroscopy and X-ray diffraction experiments. These data indicate that the complexes exhibit mononuclear structures at 298 K, both in the solid state and in solution (d8-toluene). At 203 K, the NMR signals broaden, consistent with an equilibrium between the mononuclear and dinuclear bis(μ-hydrido) complexes. All three zinc hydride complexes react rapidly and quantitatively with carbon dioxide, at 298 K and 1 bar of pressure over 20 min, to form the new zinc formate complexes 13-15. The zinc formate complexes have been analyzed by NMR spectroscopy and VT-NMR studies, which reveal a temperature-dependent monomer-dimer equilibrium that is dominated by the mononuclear species at 298 K.

  11. Standardized hydrogen storage module with high utilization factor based on metal hydride-graphite composites

    Science.gov (United States)

    Bürger, Inga; Dieterich, Mila; Pohlmann, Carsten; Röntzsch, Lars; Linder, Marc

    2017-02-01

    In view of hydrogen based backup power systems or small-scale power2gas units, hydrogen storages based on metal hydrides offer a safe and reliable solution. By using Hydralloy C5 as suitable hydride forming alloy, the present tank design guarantees very simple operating conditions: pressures between 4 bar and 30 bar, temperatures between 15 °C and 40 °C and minimal efforts for thermal management in combination with fast and constant charging and discharging capabilities. The modular tank consists of 4 layers with 5 reactor tubes each that are filled with metal hydride-graphite composites of a diameter of 21 mm. Experiments show that each layer of this tank is able to desorb the desired amount of hydrogen for a fuel cell operation at electrical power of 160 Wel for 100 min reaching a utilization factor of 93% of the stored hydrogen at RC. Furthermore, the experimental results of modularity, increasing loads and the electric air ventilation are presented.

  12. True boundary for the formation of homoleptic transition-metal hydride complexes.

    Science.gov (United States)

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Aoki, Katsutoshi; Orimo, Shin-ichi

    2015-05-04

    Despite many exploratory studies over the past several decades, the presently known transition metals that form homoleptic transition-metal hydride complexes are limited to the Groups 7-12. Here we present evidence for the formation of Mg3 CrH8 , containing the first Group 6 hydride complex [CrH7 ](5-) . Our theoretical calculations reveal that pentagonal-bipyramidal H coordination allows the formation of σ-bonds between H and Cr. The results are strongly supported by neutron diffraction and IR spectroscopic measurements. Given that the Group 3-5 elements favor ionic/metallic bonding with H, along with the current results, the true boundary for the formation of homoleptic transition-metal hydride complexes should be between Group 5 and 6. As the H coordination number generally tends to increase with decreasing atomic number of transition metals, the revised boundary suggests high potential for further discovery of hydrogen-rich materials that are of both technological and fundamental interest.

  13. Hydriding and Dehydriding Characteristics of Mechanically Alloyed LaMg17Ni Composite Material

    Institute of Scientific and Technical Information of China (English)

    李谦; 蒋利军; 林勤; 周国治; 詹峰; 郑强; 魏秀英

    2003-01-01

    A composite material with the nominal composition LaMg17Ni was synthesized by mechanical alloying and the hydriding/dehydriding (H/D) behaviors of this material were studied at several temperatures. This material has a hydrogen storage capacity (5.76% H2, mass fraction) lower than conventionally alloyed La2Mg17 (6.63% H2, mass fraction) without activation but shows a superior hydriding/dehydriding kinetic property. At 523 K it absorbed 4.97% (mass fraction) in less than 1 min, approximately 100 times faster than La2Mg17 alloy under the same conditions. This attractive kinetic property of the alloy can be ascribed to the catalytic action of Mg2Ni, LaH2 and La as well as the multiphase structure formed in the preparation processes. The relationships between the equilibrium plateau pressure and the temperature can be expressed as lgpeq=-2797/T+4.267 (553 K≤T≤623 K) for hydriding and lgpeq=-3957/T+6.063(553 K≤T≤623 K) for dehydriding.

  14. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    Science.gov (United States)

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

  15. Development of delayed hydride cracking resistant-pressure tube

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kwon, Sang Chul; Kim, S. S.; Yim, K. S

    2000-10-01

    For the first time, we demonstrate that the pattern of nucleation and growth of a DHC crack is governed by the precipitation of hydrides so that the DHC velocity and K{sub IH} are determined by an angle of the cracking plane and the hydride habit plane 10.7. Since texture controls the distribution of the 10.7 habit plane in Zr-2.5Nb pressure tube, we draw a conclusion that a textural change in Zr-2.5Nb tube from a strong tangential texture to the radial texture shall increase the threshold stress intensity factor, K{sub IH}, and decrease the delayed hydride cracking velocity. This conclusion is also verified by a complimentary experiment showing a linear dependence of DHCV and K{sub IH} with an increase in the basal component in the cracking plane. On the basis of the study on the DHC mechanism and the effect of manufacturing processes on the properties of Zr-2.5Nb tube, we have established a manufacturing procedure to make pressure tubes with improved DHC resistance. The main features of the established manufacturing process consist in the two step-cold pilgering process and the intermediate heat treatment in the {alpha} + {beta} phase for Zr-2.5Nb alloy and in the {alpha} phase for Zr-1Nb-1.2Sn-0.4Fe alloy. The manufacturing of DHC resistant-pressure tubes of Zr-2.5Nb and Zr-1N-1.2Sn-0.4Fe was made in the ChMP zirconium plant in Russia under a joint research with Drs. Nikulina and Markelov in VNIINM (Russia). Zr-2.5Nb pressure tube made with the established manufacturing process has met all the specification requirements put by KAERI. Chracterization tests have been jointly conducted by VNIINM and KAERI. As expected, the Zr-2.5Nb tube made with the established procedure has improved DHC resistance compared to that of CANDU Zr-2.5Nb pressure tube used currently. The measured DHC velocity of the Zr-2.5Nb tube meets the target value (DHCV <5x10{sup -8} m/s) and its other properties also were equivalent to those of the CANDU Zr-2.5Nb tube used currently. The Zr-1Nb-1

  16. A variety of electrostatic interactions and adducts can activate NAD(P) cofactors for hydride transfer.

    Science.gov (United States)

    Meijers, Rob; Cedergren-Zeppezauer, Eila

    2009-03-16

    In NAD(P)-dependent enzymes the coenzyme gives or takes a hydride ion, but how the nicotinamide ring is activated to form the transition state for hydride transfer is not clear. On the basis of ultra-high resolution X-ray crystal structures of liver alcohol dehydrogenase (LADH) in complex with NADH and a number of substrate analogues we proposed that the activation of NADH is an integral part of the enzyme mechanism of aldehyde reduction [R. Meijers, R.J. Morris, H.W. Adolph, A. Merli, V.S. Lamzin, E.S. Cedergren-Zeppezauer, On the enzymatic activation of NADH, The Journal of Biological Chemistry 276(12) (2001) 9316-9321, %U http://www.ncbi.nlm.nih.gov/pubmed/11134046; R. Meijers, H.-W. Adolph, Z. Dauter, K.S. Wilson, V.S. Lamzin, E.S. Cedergren-Zeppezauer, Structural evidence for a ligand coordination switch in liver alcohol dehydrogenase, Biochemistry 46(18) (2007) 5446-5454, %U http://www.ncbi.nlm.nih.gov/pubmed/17429946]. We observed a nicotinamide with a severely distorted pyridine ring and a water molecule in close proximity to the ring. Quantum chemical calculations indicated that (de)protonation of the water molecule can be directly coupled to activation of NADH for hydride transfer. A systematic search of the Protein Data Bank (PDB) for atoms that come within van der Waals distance of the pyridine ring of the nicotinamide reveals that a large number of NAD(P)-containing protein complexes are involved in electrostatic interactions with the enzymatic environment. Using the deposited diffraction data to analyze the cofactor and its surroundings, we observe several adducts between protein atoms and the pyridine ring that were not previously reported. This further indicates that the enzymatic activation of NAD(P) induced by electrostatic interactions is an essential part of the hydride transfer mechanism.

  17. Metal hydrides as electrode/catalyst materials for oxygen evolution/reduction in electrochemical devices

    Science.gov (United States)

    Bugga, Ratnakumar V. (Inventor); Halpert, Gerald (Inventor); Fultz, Brent (Inventor); Witham, Charles K. (Inventor); Bowman, Robert C. (Inventor); Hightower, Adrian (Inventor)

    1997-01-01

    An at least ternary metal alloy of the formula, AB.sub.(5-Y)X(.sub.y), is claimed. In this formula, A is selected from the rare earth elements, B is selected from the elements of groups 8, 9, and 10 of the periodic table of the elements, and X includes at least one of the following: antimony, arsenic, and bismuth. Ternary or higher-order substitutions, to the base AB.sub.5 alloys, that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption.

  18. Review of Crystalline Structures of Some Selected Homologous Series of Rod-Like Molecules Capable of Forming Liquid Crystalline Phases

    Directory of Open Access Journals (Sweden)

    Peter Zugenmaier

    2011-10-01

    Full Text Available The crystal structures of four homologous series of rod-like molecules are reviewed, two of which form hydrogen bonds and two with a symmetric chemical constitution. Many of the compounds investigated turn into liquid crystalline phases upon temperature increase. It is of valuable interest to know possible conformations and possible packing arrangements as prerequisites to model liquid crystalline structures. The hydrogen bonds of homologous series of pure 4-(ω-hydroxyalkyloxy-4′-hydroxybiphenyl (HnHBP, n the alkyloxy tail length are realized through head to tail arrangements of the hydroxyl groups and crystallize except one compound in chiral space groups without the molecules containing any asymmetric carbon. The hydrogen bonds of the homologous series of 4-substituted benzoic acids with various lengths of the tail provide dimers through strong polar bonding of adjacent carboxyl groups and thus provide the stiff part of a mesogenic unit prerequisite for liquid crystalline phases. The homologous series of dialkanoyloxybiphenyls (BP-n, n = 1, 19, of which nine compounds could be crystallized, show liquid crystalline behavior for longer alkane chain lengths, despite the high mobility of the alkane chain ends already detectable in the crystal phase. A single molecule, half a molecule or two half molecules form the asymmetric unit in a centrosymmetric space group. The homologous series of 1,4-terephthalidene-bis-N-(4′-n-alkylaniline (TBAA-n exhibit a large variety of packing arrangements in the crystalline state, with or without relying on the symmetry center within the molecules.

  19. Acute arsenious hydride intoxication. Four cases

    Energy Technology Data Exchange (ETDEWEB)

    Gosselin, B.; Mathieu, D.; Desprez-Nolf, M.; Cosson, A.; Goudemand, J.; Haguenoer, J.M.; Wattel, F.

    1982-02-06

    While engaged in the repair of a zinc furnace, 4 workers were accidentally exposed to arsenious hydride (AsH3) fumes. Acute intravascular haemolysis developed within a few hours. On admission, the patients immediately underwent exsanguino-transfusion; 8.2 to 10.2 l of blood were exchanged through a continuous perfusion pump at the rate of 1 l/hour. Two patients resumed diuresis during transfusion, but the other two required repeated haemodialysis. Between the 10th and 30th days, while renal function was gradually returning to normal, mildly megaloblastic anaemia developed. This was followed during the 3rd month by clinical and electric signs of polyneuritis of the lower and upper limbs, which subsequently regressed. Regular measurements of arsenic levels in the blood and urine were performed between and during exsanguino-transfusion and haemodialysis.

  20. Hydrogen desorption from nanostructured magnesium hydride composites

    Directory of Open Access Journals (Sweden)

    Brdarić Tanja P.

    2007-01-01

    Full Text Available The influence of 3d transition metal addition (Fe, Co and Ni on the desorption properties of magnesium hydride were studied. The ball milling of MgH2-3d metal blends was performed under Ar. Microstructural and morphological characterization were performed by XRD and SEM analysis, while the hydrogen desorption properties were investigated by DSC. The results show a strong correlation between the morphology and thermal stability of the composites. The complex desorption behavior (the existence of more than one desorption peak was correlated with the dispersion of the metal additive particles that appear to play the main role in the desorption. The desorption temperature can be reduced by more than 100 degrees if Fe is added as additive. The activation energy for H2 desorption from the MgH2-Fe composite is 120 kJ/mol, implying that diffusion controls the dehydration process.

  1. Review of magnesium hydride-based materials: development and optimisation

    NARCIS (Netherlands)

    Crivello, J. -C.; Dam, B.; Denys, R. V.; Dornheim, M.; Grant, D. M.; Huot, J.; Jensen, T. R.; de Jongh, P.|info:eu-repo/dai/nl/186125372; Latroche, M.; Milanese, C.; Milcius, D.; Walker, G. S.; Webb, C. J.; Zlotea, C.; Yartys, V. A.

    Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the

  2. Structure and bonding of second-row hydrides

    OpenAIRE

    Blinder, S. M.

    2014-01-01

    The atomic orbitals, hybridization and chemical bonding of the most common hydrides of boron, carbon, nitrogen and oxygen are described. This can be very instructive for beginning students in chemistry and chemical physics.

  3. Artificial exomuscle investigations for applications--metal hydride.

    Science.gov (United States)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bédard, Stéphane

    2007-03-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software.

  4. DETERMINATION OF METAL HYDRIDE SYSTEMS CHARACTERISTICS WHILE HEATING

    Directory of Open Access Journals (Sweden)

    Yu. Kluchka

    2012-01-01

    Full Text Available Experimental dependence of the pressure of hydrogen in the hydride cartridge when it is heated is obtained. Experimental data prove the theoretical values with an accuracy of ≈ 6%.

  5. Bipolar Nickel-Metal Hydride Battery Being Developed

    Science.gov (United States)

    Manzo, Michelle A.

    1998-01-01

    The NASA Lewis Research Center has contracted with Electro Energy, Inc., to develop a bipolar nickel-metal hydride battery design for energy storage on low-Earth-orbit satellites. The objective of the bipolar nickel-metal hydride battery development program is to approach advanced battery development from a systems level while incorporating technology advances from the lightweight nickel electrode field, hydride development, and design developments from nickel-hydrogen systems. This will result in a low-volume, simplified, less-expensive battery system that is ideal for small spacecraft applications. The goals of the program are to develop a 1-kilowatt, 28-volt (V), bipolar nickel-metal hydride battery with a specific energy of 100 watt-hours per kilogram (W-hr/kg), an energy density of 250 W-hr/liter and a 5-year life in low Earth orbit at 40-percent depth-of-discharge.

  6. Artificial exomuscle investigations for applications-metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bedard, Stephane [Victhom Human Bionics Inc., Saint-Augustin-de-Desmaures, QC (Canada)

    2007-03-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software. (review article)

  7. Out-of-pile accelerated hydriding of Zircaloy fasteners

    Energy Technology Data Exchange (ETDEWEB)

    Clayton, J.C.

    1979-10-01

    Mechanical joints between Zircaloy and nickel-bearing alloys, mainly the Zircaloy-4/Inconel-600 combination, were exposed to water at 450/sup 0/F and 520/sup 0/F to study hydriding of Zircaloy in contact with a dissimilar metal. Accelerated hydriding of the Zircaloy occurred at both temperatures. At 450/sup 0/F the dissolved hydrogen level of the water was over ten times that at 520/sup 0/F. At 520/sup 0/F the initially high hydrogen ingress rate decreased rapidly as exposure time increased and was effectively shut off in about 25 days. Severely hydrided Zircaloy components successfully withstood thermal cycling and mechanical testing. Chromium plating of the nickel-bearing parts was found to be an effective and practical barrier in preventing nickel-alloy smearing and accelerated hydriding of Zircaloy.

  8. Preparation and thermal energy storage properties of paraffin/calcined diatomite composites as form-stable phase change materials

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Zhiming [School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing 100083 (China); Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Zhang, Yuzhong [School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing 100083 (China); Zheng, Shuilin, E-mail: shuilinzh@yahoo.com.cn [School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing 100083 (China); Park, Yuri [Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Frost, Ray L., E-mail: r.frost@qut.edu.au [Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001 (Australia)

    2013-04-20

    Highlights: ► Composite phase change material (PCM) was prepared by blending composite paraffin and calcined diatomite. ► The optimum mixed proportion was obtained through differential scanning calorimetry. ► Thermal energy storage properties of the composite PCMs were determined by DSC. ► Thermal cycling test showed that the prepared PCMs are thermally reliable and chemically stable. - Abstract: A composite paraffin-based phase change material (PCM) was prepared by blending composite paraffin and calcined diatomite through the fusion adsorption method. In this study, raw diatomite was purified by thermal treatment in order to improve the adsorption capacity of diatomite, which acted as a carrier material to prepare shape-stabilized PCMs. Two forms of paraffin (paraffin waxes and liquid paraffin) with different melting points were blended together by the fusion method, and the optimum mixed proportion with a suitable phase-transition temperature was obtained through differential scanning calorimetry (DSC) analysis. Then the prepared composite paraffin was adsorbed in calcined diatomite. The prepared paraffin/calcined diatomite composites were characterized by the scanning electron microscope (SEM) and Fourier transformation infrared (FT-IR) analysis techniques. Thermal energy storage properties of the composite PCMs were determined by DSC method. DSC results showed that there was an optimum adsorption ratio between composite paraffin and calcined diatomite and the phase-transition temperature and the latent heat of the composite PCMs were 33.04 °C and 89.54 J/g, respectively. Thermal cycling test of composite PCMs showed that the prepared material is thermally reliable and chemically stable. The obtained paraffin/calcined diatomite composites have proper latent heat and melting temperatures, and show practical significance and good potential application value.

  9. INFLUENCE OF TEMPERATURE AND PRESSURE ON THE KINETICS OF Mg-6mol%LaNi PREPARED BY HYDRIDING COMBUSTION SYNTHESIS

    Institute of Scientific and Technical Information of China (English)

    Q. Li; K.C. Chou; K.D. Xu; L.J. Jiang; J.Y. Zhang; X.G. Lu

    2006-01-01

    A new model to study the hydriding/dehydriding (H/D) kinetic mechanism has been applied in the two-phase (α-β) region of the Mg-6mol%LaNi composite at temperature and pressure ranging from 523 to 623K and 0.256 to 0.992MPa H2, respectively. The coincidence of the theoretical calculation with the experimental data indicates that the rate-limiting step is hydrogen diffusion in the β phase for hydriding process and the diffusion of hydrogen in the α solid solution for hydrogen desorption with activation energies 89500 and 87900J/mol H2 for H/D processes, respectively, which were much smaller than those of MgH2 and can be attributed to the La and Ni additions.

  10. Electronic structure of ternary hydrides based on light elements

    Energy Technology Data Exchange (ETDEWEB)

    Orgaz, E. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)]. E-mail: orgaz@eros.pquim.unam.mx; Membrillo, A. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Castaneda, R. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Aburto, A. [Departamento de Fisica, Facultad de Ciencias, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)

    2005-12-08

    Ternary hydrides based on light elements are interesting owing to the high available energy density. In this work we focused into the electronic structure of a series of known systems having the general formula AMH{sub 4}(A=Li,Na,M=B,Al). We computed the energy bands and the total and partial density of states using the linear-augmented plane waves method. In this report, we discuss the chemical bonding in this series of complex hydrides.

  11. Ab-Initio Study of the Group 2 Hydride Anions

    Science.gov (United States)

    Harris, Joe P.; Wright, Timothy G.; Manship, Daniel R.

    2013-06-01

    The beryllium hydride (BeH)- dimer has recently been shown to be surprisingly strongly bound, with an electronic structure which is highly dependent on internuclear separation. At the equilibrium distance, the negative charge is to be found on the beryllium atom, despite the higher electronegativity of the hydrogen. The current study expands this investigation to the other Group 2 hydrides, and attempts to explain these effects. M. Verdicchio, G. L. Bendazzoli, S. Evangelisti, T. Leininger J. Phys. Chem. A, 117, 192, (2013)

  12. Method of selective reduction of polyhalosilanes with alkyltin hydrides

    Science.gov (United States)

    Sharp, Kenneth G.; D'Errico, John J.

    1989-01-01

    The invention relates to the selective and stepwise reduction of polyhalosilanes by reacting at room temperature or below with alkyltin hydrides without the use of free radical intermediates. Alkyltin hydrides selectively and stepwise reduce the Si--Br, Si--Cl, or Si--I bonds while leaving intact any Si--F bonds. When two or more different halogens are present on the polyhalosilane, the halogen with the highest atomic weight is preferentially reduced.

  13. Method of selective reduction of halodisilanes with alkyltin hydrides

    Science.gov (United States)

    D'Errico, John J.; Sharp, Kenneth G.

    1989-01-01

    The invention relates to the selective and sequential reduction of halodisilanes by reacting these compounds at room temperature or below with trialkyltin hydrides or dialkyltin dihydrides without the use of free radical intermediates. The alkyltin hydrides selectively and sequentially reduce the Si-Cl, Si-Br or Si-I bonds while leaving intact the Si-Si and Si-F bonds present.

  14. Electronic structure and optical properties of lightweight metal hydrides

    NARCIS (Netherlands)

    Setten, van M.J.; Popa, V.A.; Wijs, de G.A.; Brocks, G.

    2007-01-01

    We study the dielectric functions of the series of simple hydrides LiH, NaH, MgH2, and AlH3, and of the complex hydrides Li3AlH6, Na3AlH6, LiAlH4, NaAlH4, and Mg(AlH4)2, using first-principles density-functional theory and GW calculations. All compounds are large gap insulators with GW single-partic

  15. Atomistic simulation of hydrogen dynamics near dislocations in vanadium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Hiroshi, E-mail: h.ogawa@aist.go.jp

    2015-10-05

    Highlights: • Hydrogen–dislocation interaction was simulated by molecular dynamics method. • Different distribution of H atoms were observed at edge and screw dislocation. • Planner distribution of hydrogen may be caused by partialized edge dislocation. • Hydrogen diffusivity was reduced in both edge and screw dislocation models. • Pipe diffusion was observed for edge dislocation but not for screw dislocation. - Abstract: Kinetics of interstitial hydrogen atoms near dislocation cores were analyzed by atomistic simulation. Classical molecular dynamics method was applied to model structures of edge and screw dislocations in α-phase vanadium hydride. Simulation showed that hydrogen atoms aggregate near dislocation cores. The spatial distribution of hydrogen has a planner shape at edge dislocation due to dislocation partialization, and a cylindrical shape at screw dislocation. Simulated self-diffusion coefficients of hydrogen atoms in dislocation models were a half- to one-order lower than that of dislocation-free model. Arrhenius plot of self-diffusivity showed slightly different activation energies for edge and screw dislocations. Directional dependency of hydrogen diffusion near dislocation showed high and low diffusivity along edge and screw dislocation lines, respectively, hence so called ‘pipe diffusion’ possibly occur at edge dislocation but does not at screw dislocation.

  16. Molecular and atomic line surveys of galaxies I: the dense, star-forming phase as a beacon

    CERN Document Server

    Geach, James E

    2012-01-01

    We predict the space density of molecular gas reservoirs in the Universe, and place a lower limit on the number counts of carbon monoxide (CO), hydrogen cyanide (HCN) molecular and [CII] atomic emission lines in blind redshift surveys in the submillimeter-centimeter spectral regime. Our model uses: (a) recently available HCN Spectral Line Energy Distributions (SLEDs) of local Luminous Infrared Galaxies (LIRGs, L_IR>10^11 L_sun), (b) a value for epsilon=SFR/M_dense(H_2) provided by new developments in the study of star formation feedback on the interstellar medium and (c) a model for the evolution of the infrared luminosity density. Minimal 'emergent' CO SLEDs from the dense gas reservoirs expected in all star-forming systems in the Universe are then computed from the HCN SLEDs since warm, HCN-bright gas will necessarily be CO-bright, with the dense star-forming gas phase setting an obvious minimum to the total molecular gas mass of any star-forming galaxy. We include [CII] as the most important of the far-inf...

  17. Metal Hydrides for High-Temperature Power Generation

    Directory of Open Access Journals (Sweden)

    Ewa C. E. Rönnebro

    2015-08-01

    Full Text Available Metal hydrides can be utilized for hydrogen storage and for thermal energy storage (TES applications. By using TES with solar technologies, heat can be stored from sun energy to be used later, which enables continuous power generation. We are developing a TES technology based on a dual-bed metal hydride system, which has a high-temperature (HT metal hydride operating reversibly at 600–800 °C to generate heat, as well as a low-temperature (LT hydride near room temperature that is used for hydrogen storage during sun hours until there is the need to produce electricity, such as during night time, a cloudy day or during peak hours. We proceeded from selecting a high-energy density HT-hydride based on performance characterization on gram-sized samples scaled up to kilogram quantities with retained performance. COMSOL Multiphysics was used to make performance predictions for cylindrical hydride beds with varying diameters and thermal conductivities. Based on experimental and modeling results, a ~200-kWh/m3 bench-scale prototype was designed and fabricated, and we demonstrated the ability to meet or exceed all performance targets.

  18. The use of metal hydrides in fuel cell applications

    Directory of Open Access Journals (Sweden)

    Mykhaylo V. Lototskyy

    2017-02-01

    Full Text Available This paper reviews state-of-the-art developments in hydrogen energy systems which integrate fuel cells with metal hydride-based hydrogen storage. The 187 reference papers included in this review provide an overview of all major publications in the field, as well as recent work by several of the authors of the review. The review contains four parts. The first part gives an overview of the existing types of fuel cells and outlines the potential of using metal hydride stores as a source of hydrogen fuel. The second part of the review considers the suitability and optimisation of different metal hydrides based on their energy efficient thermal integration with fuel cells. The performances of metal hydrides are considered from the viewpoint of the reversible heat driven interaction of the metal hydrides with gaseous H2. Efficiencies of hydrogen and heat exchange in hydrogen stores to control H2 charge/discharge flow rates are the focus of the third section of the review and are considered together with metal hydride – fuel cell system integration issues and the corresponding engineering solutions. Finally, the last section of the review describes specific hydrogen-fuelled systems presented in the available reference data.

  19. Metal hydrides based high energy density thermal battery

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Zhigang Zak, E-mail: zak.fang@utah.edu [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Zhou, Chengshang; Fan, Peng [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Udell, Kent S. [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States); Bowman, Robert C. [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Vajo, John J.; Purewal, Justin J. [HRL Laboratories, LLC, 3011 Malibu Canyon Road, Malibu, CA 90265 (United States); Kekelia, Bidzina [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States)

    2015-10-05

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH{sub 2} and TiMnV as a working pair. • High energy density can be achieved by the use of MgH{sub 2} to store thermal energy. - Abstract: A concept of thermal battery based on advanced metal hydrides was studied for heating and cooling of cabins in electric vehicles. The system utilized a pair of thermodynamically matched metal hydrides as energy storage media. The pair of hydrides that was identified and developed was: (1) catalyzed MgH{sub 2} as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV{sub 0.62}Mn{sub 1.5} alloy as the matching low temperature hydride. Further, a proof-of-concept prototype was built and tested, demonstrating the potential of the system as HVAC for transportation vehicles.

  20. Correlation between band structure and hydride formation in dilute palladium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Bucur, R.V.; Lupu, D.

    1982-01-01

    Data on the free energy change /DELTA/G, following solution of hydrogen in dilute Pd-alloys Pd/sub 1-x/M/sub x/ are reviewed for different concentrations of M (M = Au, Ag, Pt, Ir, Rh, V, Cu, Ni, Pb, Sn and Ti) in both the /alpha/ and /beta/ phases. It is found that the dependence of /DELTA/G values upon the nature of the substituents (transition metals) is consistently explained within the framework of a metal-hydrogen bonding mechanisn in the hydrides. 23 refs.