WorldWideScience

Sample records for chemical hydride method

  1. 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.

  2. 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.

  3. 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.

  4. 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%.

  5. 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}.

  6. 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

  7. 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

  8. Best mix of primary energy resources by renewable energy and fossil fuel with CCS in view of security,stability and sustainability——A vision on hydrogen supply chain by organic chemical hydride method

    Institute of Scientific and Technical Information of China (English)

    Junichi; SAKAGUCHI

    2010-01-01

    The best mix scenario by renewable energy and fossil fuel with or without CCS(Carbon Dioxide Capture and Storage) would be a solution to compromise Greenhouse Gases emission issue caused by carbon dioxide(CO2),and depletion of crude oil and natural gas reserves.As fossil fuel with pre-combustion CCS means hydrogen manufacturing and also hydrogen can be produced via electrolysis with renewable energy,it is desirable to establish transportation and storage systems of hydrogen as a clean energy.In this paper a vision on Hydrogen Supply Chain by Organic Chemical Hydride(OCH) Method as well as comparison of CCS configuration are discussed.

  9. Uranium and thorium hydride complexes as multielectron reductants: a combined neutron diffraction and quantum chemical study.

    Science.gov (United States)

    Grant, Daniel J; Stewart, Timothy J; Bau, Robert; Miller, Kevin A; Mason, Sax A; Gutmann, Matthias; McIntyre, Garry J; Gagliardi, Laura; Evans, William J

    2012-03-19

    The unusual uranium reaction system in which uranium(4+) and uranium(3+) hydrides interconvert by formal bimetallic reductive elimination and oxidative addition reactions, [(C(5)Me(5))(2)UH(2)](2) (1) ⇌ [(C(5)Me(5))(2)UH](2) (2) + H(2), was studied by employing multiconfigurational quantum chemical and density functional theory methods. 1 can act as a formal four-electron reductant, releasing H(2) gas as the byproduct of four H(2)/H(-) redox couples. The calculated structures for both reactants and products are in good agreement with the X-ray diffraction data on 2 and 1 and the neutron diffraction data on 1 obtained under H(2) pressure as part of this study. The interconversion of the uranium(4+) and uranium(3+) hydride species was calculated to be near thermoneutral (~-2 kcal/mol). Comparison with the unknown thorium analogue, [(C(5)Me(5))(2)ThH](2), shows that the thorium(4+) to thorium(3+) hydride interconversion reaction is endothermic by 26 kcal/mol.

  10. Titanium compacts produced by the pulvimetallurgical hydride-dehydride method for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Barreiro, M M [Materiales Dentales, Facultad de OdontologIa, Universidad de Buenos Aires, Marcelo T de Alvear 2142 (1122), Buenos Aires (Argentina); Grana, D R; Kokubu, G A [PatologIa I. Escuela de OdontologIa, Facultad de Medicina. Asociacion Odontologica Argentina-Universidad del Salvador, Tucuman 1845 (1050) Buenos Aires (Argentina); Luppo, M I; Mintzer, S; Vigna, G, E-mail: mbarreiro@mater.odon.uba.a, E-mail: dgrana@usal.edu.a, E-mail: luppo@cnea.gov.a, E-mail: vigna@cnea.gov.a [Departamento Materiales, Comision Nacional de Energia Atomica, Gral Paz 1499 (B1650KNA), San MartIn, Buenos Aires (Argentina)

    2010-04-15

    Titanium powder production by the hydride-dehydride method has been developed as a non-expensive process. In this work, commercially pure grade two Ti specimens were hydrogenated. The hydrided material was milled in a planetary mill. The hydrided titanium powder was dehydrided and then sieved to obtain a particle size between 37 and 125{mu}m in order to compare it with a commercial powder produced by chemical reduction with a particle size lower than 150{mu}m. Cylindrical green compacts were obtained by uniaxial pressing of the powders at 343 MPa and sintering in vacuum. The powders and the density of sintered compacts were characterized, the oxygen content was measured and in vivo tests were performed in the tibia bones of Wistar rats in order to evaluate their biocompatibility. No differences were observed between the materials which were produced either with powders obtained by the hydride-dehydride method or with commercial powders produced by chemical reduction regarding modifications in compactation, sintering and biological behaviour.

  11. 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)

  12. High-Frequency (1)H NMR Chemical Shifts of Sn(II) and Pb(II) Hydrides Induced by Relativistic Effects: Quest for Pb(II) Hydrides.

    Science.gov (United States)

    Vícha, Jan; Marek, Radek; Straka, Michal

    2016-10-17

    The role of relativistic effects on (1)H NMR chemical shifts of Sn(II) and Pb(II) hydrides is investigated by using fully relativistic DFT calculations. The stability of possible Pb(II) hydride isomers is studied together with their (1)H NMR chemical shifts, which are predicted in the high-frequency region, up to 90 ppm. These (1)H signals are dictated by sizable relativistic contributions due to spin-orbit coupling at the heavy atom and can be as large as 80 ppm for a hydrogen atom bound to Pb(II). Such high-frequency (1)H NMR chemical shifts of Pb(II) hydride resonances cannot be detected in the (1)H NMR spectra with standard experimental setup. Extended (1)H NMR spectral ranges are thus suggested for studies of Pb(II) compounds. Modulation of spin-orbit relativistic contribution to (1)H NMR chemical shift is found to be important also in the experimentally known Sn(II) hydrides. Because the (1)H NMR chemical shifts were found to be rather sensitive to the changes in the coordination sphere of the central metal in both Sn(II) and Pb(II) hydrides, their application for structural investigation is suggested.

  13. Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

    KAUST Repository

    Shaikh Ali, Anaam

    2015-07-06

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Effect of preparation method of metal hydride electrode on efficiency of hydrogen electrosorption process

    Energy Technology Data Exchange (ETDEWEB)

    Giza, Krystyna [Czestochowa University of Technology (Poland). Faculty of Production Engineering and Materials Technology; Drulis, Henryk [Trzebiatowski Institute of Low Temperatures and Structure Research PAS, Wroclaw (Poland)

    2016-02-15

    The preparation of negative electrodes for nickel-metal hydride batteries using LaNi{sub 4.3}Co{sub 0.4}Al{sub 0.3} alloy is presented. The constant current discharge technique is employed to determine the discharge capacity, the exchange current density and the hydrogen diffusion coefficient of the studied electrodes. The electrochemical performance of metal hydride electrode is strongly affected by preparation conditions. The results are compared and the advantages and disadvantages of preparation methods of the electrodes are also discussed.

  2. Determination of Methyltins by a Hydridization Solvent Extraction Method

    OpenAIRE

    HAMASAKI,TETSUO/SATO,TAKAHIKO/NAGASE,HISAMITSU/KITO,HIDEAKI

    1994-01-01

    Analytical methods for the determination of methyltins in aqueous solutions were investigated. Methyltins ((CH_3)_nSn^) were derived to hydrides ((CH_3)_nSnH_) using sodium borohydride and extracted with benzene. Various factors related to hydridization and extraction were studied, and the optimum analytical conditions were established. Each methyltin in 50 ml of aqueous solution could be detected in the range of 0.5-250 μg as Sn using a gas chromatography-flame photometric detector (tin sele...

  3. 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.

  4. DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides.

    Science.gov (United States)

    del Rosal, I; Maron, L; Poteau, R; Jolibois, F

    2008-08-14

    Transition metal hydrides are of great interest in chemistry because of their reactivity and their potential use as catalysts for hydrogenation. Among other available techniques, structural properties in transition metal (TM) complexes are often probed by NMR spectroscopy. In this paper we will show that it is possible to establish a viable methodological strategy in the context of density functional theory, that allows the determination of 1H NMR chemical shifts of hydride ligands attached to transition metal atoms in mononuclear systems and clusters with good accuracy with respect to experiment. 13C chemical shifts have also been considered in some cases. We have studied mononuclear ruthenium complexes such as Ru(L)(H)(dppm)2 with L = H or Cl, cationic complex [Ru(H)(H2O)(dppm)2]+ and Ru(H)2(dppm)(PPh3)2, in which hydride ligands are characterized by a negative 1H NMR chemical shift. For these complexes all calculations are in relatively good agreement compared to experimental data with errors not exceeding 20% except for the hydrogen atom in Ru(H)2(dppm)(PPh3)2. For this last complex, the relative error increases to 30%, probably owing to the necessity to take into account dynamical effects of phenyl groups. Carbonyl ligands are often encountered in coordination chemistry. Specific issues arise when calculating 1H or 13C NMR chemical shifts in TM carbonyl complexes. Indeed, while errors of 10 to 20% with respect to experiment are often considered good in the framework of density functional theory, this difference in the case of mononuclear carbonyl complexes culminates to 80%: results obtained with all-electron calculations are overall in very satisfactory agreement with experiment, the error in this case does not exceed 11% contrary to effective core potentials (ECPs) calculations which yield errors always larger than 20%. We conclude that for carbonyl groups the use of ECPs is not recommended, although their use could save time for very large systems, for

  5. Atomic-Scale Chemical, Physical and Electronic Properties of the Subsurface Hydride of Palladium

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, Paul

    2014-01-20

    We employed low-temperature, extreme-high vacuum scanning tunneling microscopy (STM) to investigate the roles of subsurface hydride (H) and deuteride (D) in the surface reconstruction and surface reactivity of Pd{110}. Specifically, we gained the ability to tailor the surface structure of Pd{110} both by preparation method and by deposition of deuterium from the gas phase. We observed thiophene at low coverage on Pd{110} to determine its adsorption orientation and electronic structure through scanning tunneling spectroscopy (STS) – namely, conductance spectroscopy and differential conductance imaging. We developed the methods necessary to coadsorb D adatoms with thiophene molecules, and to induce the reaction of individual molecules with predefined subsurface H or D features. In the case of Pd{110}, we found a much more pronounced effect from subsurface D, as it is influenced by the surface directionality. These experiments facilitate an understanding of the role of surface and subsurface H and D in heterogeneous catalytic processes, specifically in the hydrodesulfuization (HDS) of thiophene, an important and ubiquitous component found to be detrimental to petroleum refining.

  6. Advanced chemical hydride-based hydrogen generation/storage system for fuel cell vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Breault, R.W.; Rolfe, J. [Thermo Power Corp., Waltham, MA (United States)

    1998-08-01

    Because of the inherent advantages of high efficiency, environmental acceptability, and high modularity, fuel cells are potentially attractive power supplies. Worldwide concerns over clean environments have revitalized research efforts on developing fuel cell vehicles (FCV). As a result of intensive research efforts, most of the subsystem technology for FCV`s are currently well established. These include: high power density PEM fuel cells, control systems, thermal management technology, and secondary power sources for hybrid operation. For mobile applications, however, supply of hydrogen or fuel for fuel cell operation poses a significant logistic problem. To supply high purity hydrogen for FCV operation, Thermo Power`s Advanced Technology Group is developing an advanced hydrogen storage technology. In this approach, a metal hydride/organic slurry is used as the hydrogen carrier and storage media. At the point of use, high purity hydrogen will be produced by reacting the metal hydride/organic slurry with water. In addition, Thermo Power has conceived the paths for recovery and regeneration of the spent hydride (practically metal hydroxide). The fluid-like nature of the spent hydride/organic slurry will provide a unique opportunity for pumping, transporting, and storing these materials. The final product of the program will be a user-friendly and relatively high energy storage density hydrogen supply system for fuel cell operation. In addition, the spent hydride can relatively easily be collected at the pumping station and regenerated utilizing renewable sources, such as biomass, natural, or coal, at the central processing plants. Therefore, the entire process will be economically favorable and environmentally friendly.

  7. 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.

  8. 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.

  9. On the chemical state and distribution of Zr- and V-based additives in reactive hydride composites

    Science.gov (United States)

    Bösenberg, U.; Vainio, U.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Goerigk, G.; Welter, E.; Dornheim, M.; Schreyer, A.; Bormann, R.

    2009-05-01

    Reactive hydride composites (RHCs) are very promising hydrogen storage materials for future applications due to their reduced reaction enthalpies and high gravimetric capacities. At present, the materials' functionality is limited by the reaction kinetics. A significant positive influence can be observed with addition of transition-metal-based additives. To understand the effect of these additives, the chemical state and changes during the reaction as well as the microstructural distribution were investigated using x-ray absorption near-edge structure (XANES) spectroscopy and anomalous small-angle x-ray scattering (ASAXS). In this work, zirconium- and vanadium-based additives were added to 2LiBH4-MgH2 composites and 2LiH-MgB2 composites and measured in the vicinity of the corresponding absorption edge. The measurements reveal the formation of finely distributed zirconium diboride and vanadium-based nanoparticles. The potential mechanisms for the observed influence on the reaction kinetics are discussed.

  10. Efficient Hydrogenolysis of Alkanes at Low Temperature and Pressure Using Tantalum Hydride on MCM-41, and a Quantum Chemical Study

    KAUST Repository

    Polshettiwar, Vivek

    2012-02-10

    Hydrogenolysis of hydrocarbons is of considerable technological importance for applications such as the hydroprocessing of petrochemical feedstocks to generate high-value and useful chemicals and fuels. We studied the catalytic activity of tantalum hydride supported on MCM-41 for the hydrogenolysis of alkanes at low temperature and low atmospheric pressure in a dynamic reactor. The reactions proceed with good turnover numbers, and the catalyst could be reused for several times, which makes the overall catalytic process sustainable. We derived the plausible mechanism by using DFT calculations and identified the preferred pathways by the analysis of potential energy surface. Our results and the proposed reaction mechanism demonstrate the viability of the "catalyst-by-design" approach. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. On Transition Structures for Hydride Transfer Step in Enzyme Catalysis. A Comparative Study on Models of Glutathione Reductase Derived from Semiempirical, HF, and DFT Methods.

    Science.gov (United States)

    Andrés, Juan; Moliner, Vicente; Safont, Vicent S.; Domingo, Luís R.; Picher, María T.

    1996-11-01

    As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling.

  12. Effect of Preparation Methods on Hydriding Properties of La1.5Mg17 Ni0.5 Composite Materials

    Institute of Scientific and Technical Information of China (English)

    Jiang Lijun; Xiao Fang; Li Qian; Lin Qin; Zhan Feng; Chou Kouchih; Lei Tingquan

    2004-01-01

    La1.5Mg17Ni0.5 hydrogen storage materials were prepared by hydriding combustion synthesis (HCS) and mechanical alloying (MA) method respectively. The experimental results show that the hydrogen absorption properties of La1.5Mg17Nio.5 prepared by MA are better than that by HCS. La1.5Mg17Nio.5 prepared by MA can absorb 6.73 mass% hydrogen at 523 K within 1 min, and 4.92 mass% hydrogen at 423 K. The improvement of hydriding properties of La1.5Mg17Ni0.5alloy prepared by MA can be ascribed to the formation of nano-crystalline and defects during the mechanical alloying.

  13. Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

    Energy Technology Data Exchange (ETDEWEB)

    Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J; Jensen, Craig M; Ozolins, Vidvuds; Siegel, Don; Harmon, Laurel

    2011-02-14

    UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. The assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 LiAlH4Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the

  14. Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

    Energy Technology Data Exchange (ETDEWEB)

    Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J; Jensen, Craig M; Ozolins, Vidvuds; Siegel, Don; Harmon, Laurel

    2011-02-14

    UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. The assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 LiAlH4Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Wireless Chemical Sensing Method

    Science.gov (United States)

    Woodard, Stanley E. (Inventor); Oglesby, Donald M. (Inventor); Taylor, Bryant D. (Inventor)

    2017-01-01

    A wireless chemical sensor includes an electrical conductor and a material separated therefrom by an electric insulator. The electrical conductor is an unconnected open-circuit shaped for storage of an electric field and a magnetic field. In the presence of a time-varying magnetic field, the first electrical conductor resonates to generate harmonic electric and magnetic field responses. The material is positioned at a location lying within at least one of the electric and magnetic field responses so-generated. The material changes in electrical conductivity in the presence of a chemical-of-interest.

  20. DFT modeling of the electronic and magnetic structures and chemical bonding properties of intermetallic hydrides; Modelisation au sein de la DFT des proprietes des structures electronique et magnetique et de liaison chimique des Hydrures d'Intermetalliques

    Energy Technology Data Exchange (ETDEWEB)

    Al Alam, A.F.

    2009-06-15

    This thesis presents an ab initio study of several classes of intermetallics and their hydrides. These compounds are interesting from both a fundamental and an applied points of view. To achieve this aim two complementary methods, constructed within the DFT, were chosen: (i) pseudo potential based VASP for geometry optimization, structural investigations and electron localization mapping (ELF), and (ii) all-electrons ASW method for a detailed description of the electronic structure, chemical bonding properties following different schemes as well as quantities depending on core electrons such as the hyperfine field. A special interest is given with respect to the interplay between magneto-volume and chemical interactions (metal-H) effects within the following hydrided systems: binary Laves (e.g. ScFe{sub 2}) and Haucke (e.g. LaNi{sub 5}) phases on one hand, and ternary cerium based (e.g. CeRhSn) and uranium based (e.g. U{sub 2}Ni{sub 2}Sn) alloys on the other hand. (author)

  1. 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.

  2. Benchmarking Quantum Mechanics/Molecular Mechanics (QM/MM) Methods on the Thymidylate Synthase-Catalyzed Hydride Transfer.

    Science.gov (United States)

    Świderek, Katarzyna; Arafet, Kemel; Kohen, Amnon; Moliner, Vicent

    2017-03-14

    Given the ubiquity of hydride-transfer reactions in enzyme-catalyzed processes, identifying the appropriate computational method for evaluating such biological reactions is crucial to perform theoretical studies of these processes. In this paper, the hydride-transfer step catalyzed by thymidylate synthase (TSase) is studied by examining hybrid quantum mechanics/molecular mechanics (QM/MM) potentials via multiple semiempirical methods and the M06-2X hybrid density functional. Calculations of protium and tritium transfer in these reactions across a range of temperatures allowed calculation of the temperature dependence of kinetic isotope effects (KIE). Dynamics and quantum-tunneling effects are revealed to have little effect on the reaction rate, but are significant in determining the KIEs and their temperature dependence. A good agreement with experiments is found, especially when computed for RM1/MM simulations. The small temperature dependence of quantum tunneling corrections and the quasiclassical contribution term cancel each other, while the recrossing transmission coefficient seems to be temperature-independent over the interval of 5-40 °C.

  3. A composite of complex and chemical hydrides yields the first Al-based amidoborane with improved hydrogen storage properties.

    Science.gov (United States)

    Dovgaliuk, Iurii; Jepsen, Lars H; Safin, Damir A; Łodziana, Zbigniew; Dyadkin, Vadim; Jensen, Torben R; Devillers, Michel; Filinchuk, Yaroslav

    2015-10-05

    The first Al-based amidoborane Na[Al(NH2 BH3 )4 ] was obtained through a mechanochemical treatment of the NaAlH4 -4 AB (AB=NH3 BH3 ) composite releasing 4.5 wt % of pure hydrogen. The same amidoborane was also produced upon heating the composite at 70 °C. The crystal structure of Na[Al(NH2 BH3 )4 ], elucidated from synchrotron X-ray powder diffraction and confirmed by DFT calculations, contains the previously unknown tetrahedral ion [Al(NH2 BH3 )4 ](-) , with every NH2 BH3 (-) ligand coordinated to aluminum through nitrogen atoms. Combination of complex and chemical hydrides in the same compound was possible due to both the lower stability of the AlH bonds compared to the BH ones in borohydride, and due to the strong Lewis acidity of Al(3+) . According to the thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) studies, Na[Al(NH2 BH3 )4 ] releases in two steps 9 wt % of pure hydrogen. As a result of this decomposition, which was also supported by volumetric studies, the formation of NaBH4 and amorphous product(s) of the surmised composition AlN4 B3 H(0-3.6) were observed. Furthermore, volumetric experiments have also shown that the final residue can reversibly absorb about 27 % of the released hydrogen at 250 °C and p(H2 )=150 bar. Hydrogen re-absorption does not regenerate neither Na[Al(NH2 BH3 )4 ] nor starting materials, NaAlH4 and AB, but rather occurs within amorphous product(s). Detailed studies of the latter one(s) can open an avenue for a new family of reversible hydrogen storage materials. Finally, the NaAlH4 -4 AB composite might become a starting point towards a new series of aluminum-based tetraamidoboranes with improved hydrogen storage properties such as hydrogen storage density, hydrogen purity, and reversibility.

  4. Semiclassical Methods in Chemical Physics.

    Science.gov (United States)

    Miller, William H.

    1986-01-01

    Discusses the role of semiclassical theory in chemical physics both as a computational method and conceptual framework for interpreting quantum mechanical experiments and calculations. Topics covered include energy wells and eigenvalues, scattering, statistical mechanics and electronically nonadiabiatic processes. (JM)

  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. Chemical control methods and tools

    Science.gov (United States)

    Steven Manning; James. Miller

    2011-01-01

    After determining the best course of action for control of an invasive plant population, it is important to understand the variety of methods available to the integrated pest management professional. A variety of methods are now widely used in managing invasive plants in natural areas, including chemical, mechanical, and cultural control methods. Once the preferred...

  7. Optimization of chemical and instrumental parameters in hydride generation laser-induced breakdown spectrometry for the determination of arsenic, antimony, lead and germanium in aqueous samples.

    Science.gov (United States)

    Yeşiller, Semira Unal; Yalçın, Serife

    2013-04-03

    A laser induced breakdown spectrometry hyphenated with on-line continuous flow hydride generation sample introduction system, HG-LIBS, has been used for the determination of arsenic, antimony, lead and germanium in aqueous environments. Optimum chemical and instrumental parameters governing chemical hydride generation, laser plasma formation and detection were investigated for each element under argon and nitrogen atmosphere. Arsenic, antimony and germanium have presented strong enhancement in signal strength under argon atmosphere while lead has shown no sensitivity to ambient gas type. Detection limits of 1.1 mg L(-1), 1.0 mg L(-1), 1.3 mg L(-1) and 0.2 mg L(-1) were obtained for As, Sb, Pb and Ge, respectively. Up to 77 times enhancement in detection limit of Pb were obtained, compared to the result obtained from the direct analysis of liquids by LIBS. Applicability of the technique to real water samples was tested through spiking experiments and recoveries higher than 80% were obtained. Results demonstrate that, HG-LIBS approach is suitable for quantitative analysis of toxic elements and sufficiently fast for real time continuous monitoring in aqueous environments.

  8. Chemical microreactor and method thereof

    Science.gov (United States)

    Morse, Jeffrey D.; Jankowski, Alan

    2011-08-09

    A method for forming a chemical microreactor includes forming at least one capillary microchannel in a substrate having at least one inlet and at least one outlet, integrating at least one heater into the chemical microreactor, interfacing the capillary microchannel with a liquid chemical reservoir at the inlet of the capillary microchannel, and interfacing the capillary microchannel with a porous membrane near the outlet of the capillary microchannel, the porous membrane being positioned beyond the outlet of the capillary microchannel, wherein the porous membrane has at least one catalyst material imbedded therein.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Determination of total arsenic in fish by hydride-generation atomic absorption spectrometry: method validation, traceability and uncertainty evaluation

    Science.gov (United States)

    Nugraha, W. C.; Elishian, C.; Ketrin, R.

    2017-03-01

    Fish containing arsenic compound is one of the important indicators of arsenic contamination in water monitoring. The high level of arsenic in fish is due to absorption through food chain and accumulated in their habitat. Hydride generation (HG) coupled with atomic absorption spectrometric (AAS) detection is one of the most popular techniques employed for arsenic determination in a variety of matrices including fish. This study aimed to develop a method for the determination of total arsenic in fish by HG-AAS. The method for sample preparation from American of Analytical Chemistry (AOAC) Method 999.10-2005 was adopted for acid digestion using microwave digestion system and AOAC Method 986.15 - 2005 for dry ashing. The method was developed and validated using Certified Reference Material DORM 3 Fish Protein for trace metals for ensuring the accuracy and the traceability of the results. The sources of uncertainty of the method were also evaluated. By using the method, it was found that the total arsenic concentration in the fish was 45.6 ± 1.22 mg.Kg-1 with a coverage factor of equal to 2 at 95% of confidence level. Evaluation of uncertainty was highly influenced by the calibration curve. This result was also traceable to International Standard System through analysis of Certified Reference Material DORM 3 with 97.5% of recovery. In summary, it showed that method of preparation and HG-AAS technique for total arsenic determination in fish were valid and reliable.

  14. 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.

  15. Determination of total arsenic in coal and wood using oxygen flask combustion method followed by hydride generation atomic absorption spectrometry.

    Science.gov (United States)

    Geng, Wenhua; Furuzono, Takuya; Nakajima, Tsunenori; Takanashi, Hirokazu; Ohki, Akira

    2010-04-15

    A simple and sensitive procedure for the determination of total arsenic in coal and wood was conducted by use of oxygen flask combustion (OFC) followed by hydride generation atomic absorption spectrometry (HGAAS). The effect of various items (composition of absorbent, standing time between the combustion and filtration, particle size and mass of sample) was investigated. Under the optimized conditions of the OFC method, nine certified reference materials were analyzed, and the values of arsenic concentration obtained by this method were in good accordance with the certified values. The limit of detection (LOD) and relative standard deviation (RSD) of the method were 0.29 microg g(-1) and less than 8%, respectively. In addition, eight kinds of coals and four chromated copper arsenate (CCA)-treated wood wastes were analyzed by the present method, and the data were compared to those from the microwave-acid digestion (MW-AD) method. The determination of arsenic in solid samples was discussed in terms of applicable scope and concentration range of arsenic.

  16. 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

  17. 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.

  18. Development of an analytical method for antimony speciation in vegetables by HPLC-hydride generation-atomic fluorescence spectrometry.

    Science.gov (United States)

    Olivares, David; Bravo, Manuel; Feldmann, Jorg; Raab, Andrea; Neaman, Alexander; Quiroz, Waldo

    2012-01-01

    A new method for antimony speciation in terrestrial edible vegetables (spinach, onions, and carrots) was developed using HPLC with hydride generation-atomic fluorescence spectrometry. Mechanical agitation and ultrasound were tested as extraction techniques. Different extraction reagents were evaluated and optimal conditions were determined using experimental design methodology, where EDTA (10 mmol/L, pH 2.5) was selected because this chelate solution produced the highest extraction yield and exhibited the best compatibility with the mobile phase. The results demonstrated that EDTA prevents oxidation of Sb(III) to Sb(V) and maintains the stability of antimony species during the entire analytical process. The LOD and precision (RSD values obtained) for Sb(V), Sb(III), and trimethyl Sb(V) were 0.08, 0.07, and 0.9 microg/L and 5.0, 5.2, and 4.7%, respectively, for a 100 microL sample volume. The application of this method to real samples allowed extraction of 50% of total antimony content from spinach, while antimony extracted from carrots and onion samples ranged between 50 and 60 and 54 and 70%, respectively. Only Sb(V) was detected in three roots (onion and spinach) that represented 60-70% of the total antimony in the extracts.

  19. 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.

  20. Hydride-induced anionic cyclization: an efficient method for the synthesis of 6-H-phenanthridines via a transition-metal-free process.

    Science.gov (United States)

    Chen, Wei-Lin; Chen, Chun-Yuan; Chen, Yan-Fu; Hsieh, Jen-Chieh

    2015-03-20

    A novel procedure for hydride-induced anionic cyclization has been developed. It includes the reduction of a biaryl bromo-nitrile with a nucleophilic aromatic substitution (S(N)Ar). A range of polysubstituted 6-H-phenanthridines were so obtained in moderate to good yield with good substrate tolerance. This method involves a concise transition-metal-free process and was applied to synthesize natural alkaloids.

  1. AN ANALYTICAL METHOD FOR CHEMICAL SPECIATION OF SELENIUM IN SOIL

    Directory of Open Access Journals (Sweden)

    Constantin Luca

    2010-10-01

    Full Text Available Selenium is an essential microelement, sometimes redoubtable, through its beneficial role - risk depending on its concentration in the food chain, at low dose is an important nutrient in the life of humans and animals, contrary at high doses, it becomes toxic. Selenium may be find itself in the environment (soil, sediment, water in many forms (oxidized, reduced, organometallic which determine their mobility and toxicity. Determination of chemical speciation (identification of different chemical forms provides much more complete information for a better understanding of the behavior and the potential impact on the environment. In this work we present the results of methodological research on the extraction of sequential forms of selenium in the soil and the coupling of analytical methods capable of identifying very small amounts of selenium in soils An efficient scheme of sequential extractions forms of selenium (SES consisting in atomic absorption spectrometry coupled with hydride generation (HGAAS has been developed into five experimental steps, detailed in the paper. This operational scheme has been applied to the analysis of chemical speciation in the following areas: the Bărăgan Plain and Central Dobrogea of Romania.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. Relativistic four-component DFT calculations of 1H NMR chemical shifts in transition-metal hydride complexes: unusual high-field shifts beyond the Buckingham-Stephens model.

    Science.gov (United States)

    Hrobárik, Peter; Hrobáriková, Veronika; Meier, Florian; Repiský, Michal; Komorovský, Stanislav; Kaupp, Martin

    2011-06-09

    State-of-the-art relativistic four-component DFT-GIAO-based calculations of (1)H NMR chemical shifts of a series of 3d, 4d, and 5d transition-metal hydrides have revealed significant spin-orbit-induced heavy atom effects on the hydride shifts, in particular for several 4d and 5d complexes. The spin-orbit (SO) effects provide substantial, in some cases even the dominant, contributions to the well-known characteristic high-field hydride shifts of complexes with a partially filled d-shell, and thereby augment the Buckingham-Stephens model of off-center paramagnetic ring currents. In contrast, complexes with a 4d(10) and 5d(10) configuration exhibit large deshielding SO effects on their hydride (1)H NMR shifts. The differences between the two classes of complexes are attributed to the dominance of π-type d-orbitals for the true transition-metal systems compared to σ-type orbitals for the d(10) systems.

  7. 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...

  8. Final Technical Report for GO15052 Intematix: Combinatorial Synthesis and High Throughput Screening of Effective Catalysts for Chemical Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Melman, Jonathan [Intematix Corporation, Fremont, CA (United States)

    2017-02-22

    The objectives of this project are: to discover cost-effective catalysts for release of hydrogen from chemical hydrogen storage systems; and to discover cost-effective catalysts for the regeneration of spent chemical hydrogen storage materials.

  9. Tungsten chemical vapor deposition method

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, Kiichi; Takeda, Nobuo.

    1993-07-13

    A tungsten chemical vapor deposition method is described, comprising: a first step of selectively growing a first thin tungsten film of a predetermined thickness in a desired region on the surface of a silicon substrate by reduction of a WF[sub 6] gas introduced into an atmosphere of a predetermined temperature containing said silicon substrate; and a second step of selectively growing a second tungsten film of a predetermined thickness on said first thin tungsten film by reduction of said WF[sub 6] with a silane gas further introduced into said atmosphere, wherein the surface state of said substrate is monitored by a pyrometer and the switching from said first step to said second step is performed when the emissivity of infrared light from the substrate surfaces reaches a predetermined value.

  10. 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.

  11. 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.

  12. Elemental step thermodynamics of various analogues of indazolium alkaloids to obtaining hydride in acetonitrile.

    Science.gov (United States)

    Lei, Nan-Ping; Fu, Yan-Hua; Zhu, Xiao-Qing

    2015-12-21

    A series of analogues of indazolium alkaloids were designed and synthesized. The thermodynamic driving forces of the 6 elemental steps for the analogues of indazolium alkaloids to obtain hydride in acetonitrile were determined using an isothermal titration calorimeter (ITC) and electrochemical methods, respectively. The effects of molecular structure and substituents on the thermodynamic driving forces of the 6 steps were examined. Meanwhile, the oxidation mechanism of NADH coenzyme by indazolium alkaloids was examined using the chemical mimic method. The result shows that the oxidation of NADH coenzyme by indazolium alkaloids in vivo takes place by one-step concerted hydride transfer mechanism.

  13. Apparatus and methods for detecting chemical permeation

    Science.gov (United States)

    Vo-Dinh, Tuan

    1994-01-01

    Apparatus and methods for detecting the permeation of hazardous or toxic chemicals through protective clothing are disclosed. The hazardous or toxic chemicals of interest do not possess the spectral characteristic of luminescence. The apparatus and methods utilize a spectrochemical modification technique to detect the luminescence quenching of an indicator compound which upon permeation of the chemical through the protective clothing, the indicator is exposed to the chemical, thus indicating chemical permeation.

  14. 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.

  15. Revisiting the method to obtain the mechanical properties of hydrided fuel cladding in the hoop direction

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Rengel, M.A., E-mail: mamartin@mater.upm.es [Departamento de Ciencia de Materiales, UPM, ETSI Caminos, Canales y Puertos, Profesor Aranguren s/n, E-28040 Madrid (Spain); Gomez Sanchez, F.J., E-mail: javier.gomez@amsimulation.com [Advanced Material Simulation, S.L (Spain); Ruiz-Hervias, J.; Caballero, L.; Valiente, A. [Departamento de Ciencia de Materiales, UPM, ETSI Caminos, Canales y Puertos, Profesor Aranguren s/n, E-28040 Madrid (Spain)

    2012-10-15

    The method reported in the literature to calculate the stress-strain curve of nuclear fuel cladding from ring tensile test is revisited in this paper and a new alternative is presented. In the former method, two universal curves are introduced under the assumption of small strain. In this paper it is shown that these curves are not universal, but material-dependent if geometric nonlinearity is taken into account. The new method is valid beyond small strains, takes geometric nonlinearity into consideration and does not need universal curves. The stress-strain curves in the hoop direction are determined by combining numerical calculations with experimental results in a convergent loop. To this end, ring tensile tests were performed in unirradiated hydrogen-charged samples. The agreement among the simulations and the experimental results is excellent for the range of concentrations tested (up to 2000 wppm hydrogen). The calculated stress-strain curves show that the mechanical properties do not depend strongly on the hydrogen concentration, and that no noticeable strain hardening occurs. However, ductility decreases with the hydrogen concentration, especially beyond 500 wppm hydrogen. The fractographic results indicate that as-received samples fail in a ductile fashion, whereas quasicleavage is observed in the hydrogen-charged samples.

  16. 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.

  17. 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

  18. Chemical reaction and separation method

    NARCIS (Netherlands)

    Jansen, J.C.; Kapteijn, F.; Strous, S.A.

    2005-01-01

    The invention is directed to process for performing a chemical reaction in a reaction mixture, which reaction produces water as by-product, wherein the reaction mixture is in contact with a hydroxy sodalite membrane, through which water produced during the reaction is removed from the reaction mixtu

  19. Chemical Safety Alert: Identifying Chemical Reactivity Hazards Preliminary Screening Method

    Science.gov (United States)

    Introduces small-to-medium-sized facilities to a method developed by Center for Chemical Process Safety (CCPS), based on a series of twelve yes-or-no questions to help determine hazards in warehousing, repackaging, blending, mixing, and processing.

  20. 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)

  1. 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.

  2. 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

  3. Chemical Methods for the Production of Proteins

    Energy Technology Data Exchange (ETDEWEB)

    Kent, Stephen B.H.

    2008-09-15

    The goal of this research program was to develop improved methods for chemical peptide and protein synthesis, and to apply these methods to the total synthesis of small proteins (<80 amino acids) & integral membrane proteins.

  4. Numerical simulation and performance test of metal hydride hydrogen storage system

    Directory of Open Access Journals (Sweden)

    Tzu-Hsiang Yen, Bin-Hao Chen, Bao-Dong Chen

    2011-05-01

    Full Text Available Metal hydride reactors are widely used in many industrial applications, such as hydrogen storage, thermal compression, heat pump, etc. According to the research requirement of metal hydride hydrogen storage, the thermal analyses have been implemented in the paper. The metal hydride reaction beds are considered as coupled cylindrical tube modules which combine the chemical absorption and desorption in metal hydride. The model is then used metal hydride LaNi5 as an example to predict the performance of metal hydride hydrogen storage devices, such as the position of hydration front and the thermal flux. Under the different boundary condition the characteristics of heat transfer and mass transfer in metal hydride have influence on the hydrogen absorption and desorption. The researches revealed that the scroll design can improve the temperature distribution in the reactor and the porous tube for directing hydrogen can increase the penetration depth of hydride reaction to decrease the hydrogen absorption time.

  5. 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.

  6. Chemical Tracer Methods: Chapter 7

    Science.gov (United States)

    Healy, Richard W.

    2017-01-01

    Tracers have a wide variety of uses in hydrologic studies: providing quantitative or qualitative estimates of recharge, identifying sources of recharge, providing information on velocities and travel times of water movement, assessing the importance of preferential flow paths, providing information on hydrodynamic dispersion, and providing data for calibration of water flow and solute-transport models (Walker, 1998; Cook and Herczeg, 2000; Scanlon et al., 2002b). Tracers generally are ions, isotopes, or gases that move with water and that can be detected in the atmosphere, in surface waters, and in the subsurface. Heat also is transported by water; therefore, temperatures can be used to trace water movement. This chapter focuses on the use of chemical and isotopic tracers in the subsurface to estimate recharge. Tracer use in surface-water studies to determine groundwater discharge to streams is addressed in Chapter 4; the use of temperature as a tracer is described in Chapter 8.Following the nomenclature of Scanlon et al. (2002b), tracers are grouped into three categories: natural environmental tracers, historical tracers, and applied tracers. Natural environmental tracers are those that are transported to or created within the atmosphere under natural processes; these tracers are carried to the Earth’s surface as wet or dry atmospheric deposition. The most commonly used natural environmental tracer is chloride (Cl) (Allison and Hughes, 1978). Ocean water, through the process of evaporation, is the primary source of atmospheric Cl. Other tracers in this category include chlorine-36 (36Cl) and tritium (3H); these two isotopes are produced naturally in the Earth’s atmosphere; however, there are additional anthropogenic sources of them.

  7. Comparison of Chemical and Physical-chemical Wastewater Discoloring Methods

    Directory of Open Access Journals (Sweden)

    Durašević, V.

    2007-11-01

    Full Text Available Today's chemical and physical-chemical wastewater discoloration methods do not completely meet demands regarding degree of discoloration. In this paper discoloration was performed using Fenton (FeSO4 . 7 H2O + H2O2 + H2SO4 and Fenton-like (FeCl3 . 6 H2O + H2O2 + HCOOH chemical methods and physical-chemical method of coagulation/flocculation (using poly-electrolyte (POEL combining anion active coagulant (modified poly-acrylamides and cationic flocculant (product of nitrogen compounds in combination with adsorption on activated carbon. Suitability of aforementioned methods was investigated on reactive and acid dyes, regarding their most common use in the textile industry. Also, investigations on dyes of different chromogen (anthraquinone, phthalocyanine, azo and xanthene were carried out in order to determine the importance of molecular spatial structure. Oxidative effect of Fenton and Fenton-like reagents resulted in decomposition of colored chromogen and high degree of discoloration. However, the problem is the inability of adding POEL in stechiometrical ratio (also present in physical-chemical methods, when the phenomenon of overdosing coagulants occurs in order to obtain a higher degree of discoloration, creating a potential danger of burdening water with POEL. Input and output water quality was controlled through spectrophotometric measurements and standard biological parameters. In addition, part of the investigations concerned industrial wastewaters obtained from dyeing cotton materials using reactive dye (C. I. Reactive Blue 19, a process that demands the use of vast amounts of electrolytes. Also, investigations of industrial wastewaters was labeled as a crucial step carried out in order to avoid serious misassumptions and false conclusions, which may arise if dyeing processes are only simulated in the laboratory.

  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. 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.

  10. 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.

  11. An improved method for the determination of trace levels of arsenic and antimony in geological materials by automated hydride generation-atomic absorption spectroscopy

    Science.gov (United States)

    Crock, J.G.; Lichte, F.E.

    1982-01-01

    An improved, automated method for the determination of arsenic and antimony in geological materials is described. After digestion of the material in sulfuric, nitric, hydrofluoric and perchloric acids, a hydrochloric acid solution of the sample is automatically mixed with reducing agents, acidified with additional hydrochloric acid, and treated with a sodium tetrahydroborate solution to form arsine and stibine. The hydrides are decomposed in a heated quartz tube in the optical path of an atomic absorption spectrometer. The absorbance peak height for arsenic or antimony is measured. Interferences that exist are minimized to the point where most geological materials including coals, soils, coal ashes, rocks and sediments can be analyzed directly without use of standard additions. The relative standard deviation of the digestion and the instrumental procedure is less than 2% at the 50 ??g l-1 As or Sb level. The reagent-blank detection limit is 0.2 ??g l-1 As or Sb. ?? 1982.

  12. Spectroscopic Chemical Analysis Methods and Apparatus

    Science.gov (United States)

    Hug, William F. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor); Lane, Arthur L. (Inventor)

    2017-01-01

    Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

  13. Development of an analytical method for the determination of arsenic in gasoline samples by hydride generation-graphite furnace atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Becker, Emilene M. [Universidade Federal do Pampa, Bage, RS (Brazil); Universidade Federal de Pelotas, Pelotas, RS (Brazil); Dessuy, Morgana B.; Boschetti, Wiliam [Instituto de Quimica, Universidade Federal do Rio Grande do Sul, Av. Bento Goncalves, 9500, 91501-970 Porto Alegre, RS (Brazil); Vale, Maria Goreti R., E-mail: mgrvale@ufrgs.br [Instituto de Quimica, Universidade Federal do Rio Grande do Sul, Av. Bento Goncalves, 9500, 91501-970 Porto Alegre, RS (Brazil); Instituto Nacional de Ciencia e Tecnologia do CNPq, INCT de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA (Brazil); Ferreira, Sergio L.C. [Instituto Nacional de Ciencia e Tecnologia do CNPq, INCT de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA (Brazil); Instituto de Quimica, Universidade Federal da Bahia, Salvador, BA (Brazil); Welz, Bernhard [Instituto Nacional de Ciencia e Tecnologia do CNPq, INCT de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA (Brazil); Departamento de Quimica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil)

    2012-05-15

    The purpose of the present work was to optimize the conditions for the determination of arsenic in gasoline with hydride generation-graphite furnace atomic absorption spectrometry after acid digestion using a full two-level factorial design with center point. The arsine was generated in a batch system and collected in a graphite tube coated with 150 {mu}g Ir as a permanent modifier. The sample volume, the pre-reduction conditions, the temperature program and modifier mass were kept fixed for all experiments. The estimated main effects were: reducing agent concentration (negative effect), acid concentration (negative effect) and trapping temperature (positive effect). It was observed that there were interactions between the variables. Moreover, the curvature was significant, indicating that the best conditions were at the center point. The optimized parameters for arsine generation were 2.7 mol L{sup -1} hydrochloric acid and 1.6% (w/v) sodium tetrahydroborate. The optimized conditions to collect arsine in the graphite furnace were a trapping temperature of 250 Degree-Sign C and a collection time of 30 s. The limit of detection was 6.4 ng L{sup -1} and the characteristic mass was 24 pg. Two different systems for acid digestion were used: a digester block with cold finger and a microwave oven. The concentration of arsenic found with the proposed method was compared with that obtained using a detergentless microemulsion and direct graphite furnace determination. The results showed that the factorial design is a simple tool that allowed establishing the appropriate conditions for sample preparation and also helped in evaluating the interaction between the factors investigated. - Highlights: Black-Right-Pointing-Pointer We determined As in gasoline using hydride generation-graphite furnace AAS. Black-Right-Pointing-Pointer We compared three sample preparation procedures. Black-Right-Pointing-Pointer A multivariate approach was used to optimize the conditions. Black

  14. 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.

  15. Method And Apparatus For Detecting Chemical Binding

    Energy Technology Data Exchange (ETDEWEB)

    Warner, Benjamin P. (Los Alamos, NM); Havrilla, George J. (Los Alamos, NM); Miller, Thomasin C. (Los Alamos, NM); Wells, Cyndi A. (Los Alamos, NM)

    2005-02-22

    The method for screening binding between a target binder and potential pharmaceutical chemicals involves sending a solution (preferably an aqueous solution) of the target binder through a conduit to a size exclusion filter, the target binder being too large to pass through the size exclusion filter, and then sending a solution of one or more potential pharmaceutical chemicals (preferably an aqueous solution) through the same conduit to the size exclusion filter after target binder has collected on the filter. The potential pharmaceutical chemicals are small enough to pass through the filter. Afterwards, x-rays are sent from an x-ray source to the size exclusion filter, and if the potential pharmaceutical chemicals form a complex with the target binder, the complex produces an x-ray fluorescence signal having an intensity that indicates that a complex has formed.

  16. Method and apparatus for detecting chemical binding

    Energy Technology Data Exchange (ETDEWEB)

    Warner, Benjamin P. (Los Alamos, NM); Havrilla, George J. (Los Alamos, NM); Miller, Thomasin C. (Los Alamos, NM); Wells, Cyndi A. (Los Alamos, NM)

    2007-07-10

    The method for screening binding between a target binder and potential pharmaceutical chemicals involves sending a solution (preferably an aqueous solution) of the target binder through a conduit to a size exclusion filter, the target binder being too large to pass through the size exclusion filter, and then sending a solution of one or more potential pharmaceutical chemicals (preferably an aqueous solution) through the same conduit to the size exclusion filter after target binder has collected on the filter. The potential pharmaceutical chemicals are small enough to pass through the filter. Afterwards, x-rays are sent from an x-ray source to the size exclusion filter, and if the potential pharmaceutical chemicals form a complex with the target binder, the complex produces an x-ray fluorescence signal having an intensity that indicates that a complex has formed.

  17. 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.

  18. Thermodynamic diagnosis of the properties and mechanism of dihydropyridine-type compounds as hydride source in acetonitrile with "Molecule ID Card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Tan, Yue; Cao, Chao-Tun

    2010-02-11

    A series of 45 dihydropyridine-type organic compounds as hydride source were designed and synthesized. The thermodynamic driving forces (defined as enthalpy changes or redox potentials in this work) of the dihydropyridines to release hydride anions, hydrogen atoms (hydrogen for short), and electrons in acetonitrile, the thermodynamic driving forces of the radical cations of the dihydropyridines to release protons and hydrogens in acetonitrile, and the thermodynamic driving forces of the neutral pyridine-type radicals of the dihydropyridines to release electron in acetonitrile were determined by using titration calorimetry and electrochemical methods. The rates and activation parameters of hydride transfer from the dihydropyridines to acridinium perclorate, a well-known hydride acceptor, were determined by using UV-vis absorption spectroscopy technique. The relationship between the thermodynamic driving forces and kinetic rate of the hydride transfer was examined. Thermodynamic characteristic graph (TCG) of the dihydropyridines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose or predict the characteristic chemical properties of the dihydropyridines and their various reaction intermediates. The mechanism of hydride transfer from the dihydropyridines to acridinium perclorate was diagnosed and elucidated by using the determined thermodynamic parameters and the activation parameters.

  19. New methods for chemical protein synthesis.

    Science.gov (United States)

    Guan, Xiaoyang; Chaffey, Patrick K; Zeng, Chen; Tan, Zhongping

    2015-01-01

    Chemical protein synthesis is a useful tool to generate pure proteins which are otherwise difficult to obtain in sufficient amounts for structure and property analysis. Additionally, because of the precise and flexible nature of chemical synthesis, it allows for controllable variation of protein sequences, which is valuable for understanding the relationships between protein structure and function. Despite the usefulness of chemical protein synthesis, it has not been widely adopted as a tool for protein characterization, mainly because of the lack of general and efficient methods for the preparation and coupling of peptide fragments and for the folding of polypeptide chains. To address these issues, many new methods have recently been developed in the areas of solid-phase peptide synthesis, peptide fragment assembly, and protein folding. Here we review these recent technological advances and highlight the gaps needing to be addressed in future research.

  20. 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.

  1. 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.

  2. A practical method for the determination of total selenium in environmental samples using isotope dilution-hydride generation-inductively coupled plasma-mass spectrometry

    Science.gov (United States)

    Kleckner, Amy E.; Kakouros, Evangelos; Stewart, A. Robin

    2017-01-01

    A safe, practical, and accurate method for the determination of selenium (Se) in range of environmental samples was developed. Small sample masses, 5–20 mg, were amended with 82Se enriched isotope for the isotope dilution (ID), preceding a multi-step wet digestion with nitric acid (HNO3) and hydrogen peroxide (H2O2). Samples were incubated in an autoclave for 3 h at 20 psi and 126°C. Digestates were subsequently reduced with concentrated hydrochloric acid to Se(IV) the most favorable valence for hydride generation (HG). The solutions were then analyzed on an ICP-MS equipped with Flow Injection system (FIAS-400). Polyatomic, isobaric, and background interferences were removed through the use of HG and ID with an 82Se enriched isotope spike. Recoveries for certified reference materials were determined and averaged 96% for biological tissues (NRCC DOLT3, DOLT4, DORM2, TORT2, and TORT3, and NIST 2976) and 108% for estuarine sediment (NRCC PACS2) with an average coefficient of variation for replicate measurements of ∼ 3.5%. Limit of detection was 0.13 ng Se g−1 dry weight or 0.19 ng Se L−1. This method can be broadly applied to biological tissues, sediments, suspended particulates, and water samples with minimal modifications making this method highly useful for assessing the ecotoxicology of total Se in aquatic ecosystems.

  3. 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.

  4. 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.

  5. 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.

  6. Hydride Atomic Fluorescence Spectrophotometry Measurement Method of Arsenic and Mercury in Mineral Water%矿泉水中砷和汞的氢化物原子荧光测定法

    Institute of Scientific and Technical Information of China (English)

    韩雪飞

    2016-01-01

    Objective To analyze and determine the hydride atomic fluorescence spectrophotometry measurement method of arsenic and mercury in mineral water. Methods The hydride atomic fluorescence spectrophotometry measurement method was used by means of nitric acid by research staff. Results A certain research showed that the hydride atomic fluorescence spectrophotometry measurement method of arsenic and mercury was conducive to improving the test of materials in mineral water. Conclusion The hydride atomic fluorescence spectrophotometry measurement of arsenic and mercury in mineral water can rapidly conduct a test with relatively accurate results, and it is very suitable for the test work of mineral water, which should be promoted.%目的:分析确定矿泉水中砷和汞的氢化物原子荧光测定的方法。方法研究人员利用化学实验的方法,通过硝酸这个媒介,从而使用氢化物原子荧光测定的形式加以检验的方法。结果通过一定的研究表明,矿泉水中砷和汞的氢化物原子荧光测定法有利于提高对矿泉水中物质的检测。结论矿泉水中砷和汞的氢化物原子荧光测定不仅能够快速地进行检测,而且结果也相对准确,非常适合矿泉水的检验工作,是应该加以推广的方法。

  7. Numerical Methods For Chemically Reacting Flows

    Science.gov (United States)

    Leveque, R. J.; Yee, H. C.

    1990-01-01

    Issues related to numerical stability, accuracy, and resolution discussed. Technical memorandum presents issues in numerical solution of hyperbolic conservation laws containing "stiff" (relatively large and rapidly changing) source terms. Such equations often used to represent chemically reacting flows. Usually solved by finite-difference numerical methods. Source terms generally necessitate use of small time and/or space steps to obtain sufficient resolution, especially at discontinuities, where incorrect mathematical modeling results in unphysical solutions.

  8. Arsenic fractionation in agricultural soil using an automated three-step sequential extraction method coupled to hydride generation-atomic fluorescence spectrometry.

    Science.gov (United States)

    Rosas-Castor, J M; Portugal, L; Ferrer, L; Guzmán-Mar, J L; Hernández-Ramírez, A; Cerdà, V; Hinojosa-Reyes, L

    2015-05-18

    A fully automated modified three-step BCR flow-through sequential extraction method was developed for the fractionation of the arsenic (As) content from agricultural soil based on a multi-syringe flow injection analysis (MSFIA) system coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS). Critical parameters that affect the performance of the automated system were optimized by exploiting a multivariate approach using a Doehlert design. The validation of the flow-based modified-BCR method was carried out by comparison with the conventional BCR method. Thus, the total As content was determined in the following three fractions: fraction 1 (F1), the acid-soluble or interchangeable fraction; fraction 2 (F2), the reducible fraction; and fraction 3 (F3), the oxidizable fraction. The limits of detection (LOD) were 4.0, 3.4, and 23.6 μg L(-1) for F1, F2, and F3, respectively. A wide working concentration range was obtained for the analysis of each fraction, i.e., 0.013-0.800, 0.011-0.900 and 0.079-1.400 mg L(-1) for F1, F2, and F3, respectively. The precision of the automated MSFIA-HG-AFS system, expressed as the relative standard deviation (RSD), was evaluated for a 200 μg L(-1) As standard solution, and RSD values between 5 and 8% were achieved for the three BCR fractions. The new modified three-step BCR flow-based sequential extraction method was satisfactorily applied for arsenic fractionation in real agricultural soil samples from an arsenic-contaminated mining zone to evaluate its extractability. The frequency of analysis of the proposed method was eight times higher than that of the conventional BCR method (6 vs 48 h), and the kinetics of lixiviation were established for each fraction.

  9. 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.

  10. 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.

  11. Valence properties of tellurium in different chemical systems and its determination in refractory environmental samples using hydride generation – Atomic fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu-Wei; Alzahrani, Ali [Department of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario P3E 2C6 (Canada); Deng, Tian-Long [College of Marine Science and Engineering, Tianjin University of Science and Technology, Tianjin (China); Belzile, Nelson, E-mail: nbelzile@laurentian.ca [Department of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario P3E 2C6 (Canada); Cooperative Freshwater Ecology Unit, Laurentian University, Sudbury, Ontario P3E 2C6 (Canada)

    2016-01-28

    Using HG – AFS as a powerful tool to study valence transformations of Te, we found that, in presence of HCl and at high temperature, Te can form volatile species and be lost during sample digestion and pre-reduction steps. It was also noticed that the chemical valences of Te can be modified under different chemical and digestion conditions and even by samples themselves with certain matrices. KBr can reduce Te(VI) to Te(IV) in 3.0 M HCl at 100 °C, but when HNO{sub 3} was >5% (v/v) in solution, Br{sub 2} was formed and caused serious interference to Te measurements. HCl alone can also pre-reduce Te(VI) to Te(IV), only when its concentration was ≥6.0 M (100 °C for 15min). Among 10 studied chemical elements, only Cu{sup 2+} caused severe interference. Thiourea is an effective masking agent only when Cu{sup 2+} concentration is equal or lower than 10 mg/L. Chemical reagents, chemical composition of sample, as well as the modes of digestion can greatly affect Te valences, reagent blanks and analytical precisions. A protocol of 2–step–digestion followed by an elimination of HF is proposed to minimize reagent blank and increase the signal/noise ratios. It is important to perform a preliminary test to confirm whether a pre-reduction step is necessary; this is especially true for samples with complex matrices such as those with high sulfide content. The analytical detection limits of this method in a pure solution and a solid sample were 100 ng/L and 0.10 ± 0.02 μg/g, respectively. - Highlights: • HG–AFS is a powerful tool in studies of chemical valences and forms of Te in different conditions. • Te can be lost in form of volatile species in presence of HCl at high temperature. • Metal ions can be classified into 3 categories of interference; thiourea can effectively mask Cu{sup 2+}. • A 2-step digestion allows to eliminate HF, reduce background and improve analytical precision. • Matrix of sample can strongly influence Te chemical valence

  12. 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.)

  13. Method development and optimization for the determination of selenium in bean and soil samples using hydride generation electrothermal atomic absorption spectrometry.

    Science.gov (United States)

    Shaltout, Abdallah A; Castilho, Ivan N B; Welz, Bernhard; Carasek, Eduardo; Martens, Irland B Gonzaga; Martens, Andreas; Cozzolino, Silvia M F

    2011-09-15

    The present investigation is the first part of an initiative to prepare a regional map of the natural abundance of selenium in various areas of Brazil, based on the analysis of bean and soil samples. Continuous-flow hydride generation electrothermal atomic absorption spectrometry (HG-ET AAS) with in situ trapping on an iridium-coated graphite tube has been chosen because of the high sensitivity and relative simplicity. The microwave-assisted acid digestion for bean and soil samples was tested for complete recovery of inorganic and organic selenium compounds (selenomethionine). The reduction of Se(VI) to Se(IV) was optimized in order to guarantee that there is no back-oxidation, which is of importance when digested samples are not analyzed immediately after the reduction step. The limits of detection and quantification of the method were 30 ng L(-1) Se and 101 ng L(-1) Se, respectively, corresponding to about 3 ng g(-1) and 10 ng g(-1), respectively, in the solid samples, considering a typical dilution factor of 100 for the digestion process. The results obtained for two certified food reference materials (CRM), soybean and rice, and for a soil and sediment CRM confirmed the validity of the investigated method. The selenium content found in a number of selected bean samples varied between 5.5±0.4 ng g(-1) and 1726±55 ng g(-1), and that in soil samples varied between 113±6.5 ng g(-1) and 1692±21 ng g(-1).

  14. Chemical detection system and related methods

    Energy Technology Data Exchange (ETDEWEB)

    Caffrey, Augustine J.; Chichester, David L.; Egger, Ann E.; Krebs, Kenneth M.; Seabury, Edward H.; Van Siclen, Clinton D.; Wharton, C. Jayson; Zabriskie, John M.

    2017-06-27

    A chemical detection system includes a frame, an emitter coupled to the frame, and a detector coupled to the frame proximate the emitter. The system also includes a shielding system coupled to the frame and positioned at least partially between the emitter and the detector, wherein the frame positions a sensing surface of the detector in a direction substantially parallel to a plane extending along a front portion of the frame. A method of analyzing composition of a suspect object includes directing neutrons at the object, detecting gamma rays emitted from the object, and communicating spectrometer information regarding the gamma rays. The method also includes presenting a GUI to a user with a dynamic status of an ongoing neutron spectroscopy process. The dynamic status includes a present confidence for a plurality of compounds being present in the suspect object responsive to changes in the spectrometer information during the ongoing process.

  15. Arsenic fractionation in agricultural soil using an automated three-step sequential extraction method coupled to hydride generation-atomic fluorescence spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Rosas-Castor, J.M. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León, C.P. 66451 Nuevo León (Mexico); Group of Analytical Chemistry, Automation and Environment, University of Balearic Islands, Cra. Valldemossa km 7.5, 07122 Palma de Mallorca (Spain); Portugal, L.; Ferrer, L. [Group of Analytical Chemistry, Automation and Environment, University of Balearic Islands, Cra. Valldemossa km 7.5, 07122 Palma de Mallorca (Spain); Guzmán-Mar, J.L.; Hernández-Ramírez, A. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León, C.P. 66451 Nuevo León (Mexico); Cerdà, V. [Group of Analytical Chemistry, Automation and Environment, University of Balearic Islands, Cra. Valldemossa km 7.5, 07122 Palma de Mallorca (Spain); Hinojosa-Reyes, L., E-mail: laura.hinojosary@uanl.edu.mx [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León, C.P. 66451 Nuevo León (Mexico)

    2015-05-18

    Highlights: • A fully automated flow-based modified-BCR extraction method was developed to evaluate the extractable As of soil. • The MSFIA–HG-AFS system included an UV photo-oxidation step for organic species degradation. • The accuracy and precision of the proposed method were found satisfactory. • The time analysis can be reduced up to eight times by using the proposed flow-based BCR method. • The labile As (F1 + F2) was <50% of total As in soil samples from As-contaminated-mining zones. - Abstract: A fully automated modified three-step BCR flow-through sequential extraction method was developed for the fractionation of the arsenic (As) content from agricultural soil based on a multi-syringe flow injection analysis (MSFIA) system coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS). Critical parameters that affect the performance of the automated system were optimized by exploiting a multivariate approach using a Doehlert design. The validation of the flow-based modified-BCR method was carried out by comparison with the conventional BCR method. Thus, the total As content was determined in the following three fractions: fraction 1 (F1), the acid-soluble or interchangeable fraction; fraction 2 (F2), the reducible fraction; and fraction 3 (F3), the oxidizable fraction. The limits of detection (LOD) were 4.0, 3.4, and 23.6 μg L{sup −1} for F1, F2, and F3, respectively. A wide working concentration range was obtained for the analysis of each fraction, i.e., 0.013–0.800, 0.011–0.900 and 0.079–1.400 mg L{sup −1} for F1, F2, and F3, respectively. The precision of the automated MSFIA–HG-AFS system, expressed as the relative standard deviation (RSD), was evaluated for a 200 μg L{sup −1} As standard solution, and RSD values between 5 and 8% were achieved for the three BCR fractions. The new modified three-step BCR flow-based sequential extraction method was satisfactorily applied for arsenic fractionation in real agricultural

  16. NUMERICAL ANALYSIS FOR HYDRIDING IN METAL HYDRIDE HYDROGEN STORAGE TANK%金属氢化物储氢器吸氢过程的数值分析

    Institute of Scientific and Technical Information of China (English)

    叶建华; 蒋利军; 李志念; 刘晓鹏; 王树茂

    2011-01-01

    Based on the principle of hydride adsorption, a one-dimensional mathematical model for hydriding in a cylindrical metal hydride hydrogen storage tank was established. The heat and mass transfer of metal hydride beds was computed by finite difference method. The variation in temperature and hydrogen concentration at different radial positions of the hydride layer was analyzed during the process of hydriding. The effects of supply pressure, heat convection coefficient and hydride layer radial thickness on the hydriding was studied. It is shown that hydride formation initially takes place uniformly all over the metal hydride layer, but with the process of hydriding, the hydriding rate at the core region is gradually slower than one at surface region. The increase of supply pressure and heat convection coefficient can accelerate the hydriding of the hydrogen storage tank. The effect of hydride layer radial thickness is significant on the hydriding rate, and the thinner hydride layer, the higher the hydriding rate.%基于金属氢化物吸氢基本特性,建立圆柱形金属氢化物储氢器吸氢过程的-维数学物理模型.采用有限差分法对金属氢化物床体的传热传质进行计算.分别研究金属氢化物床体各处温度和氢含量在吸氢过程中的变化以及氢气压力、对流传热系数和金属氢化物床体径向厚度对金属氢化物吸氢过程的影响.计算结果表明:初始阶段金属氢化物床均匀吸氢,但随着氢化过程的进行,其中心区域的吸氢速率逐渐低于边缘区域;增加吸氢压力、提高对流传热系数均可促进储氢器的吸氢;金属氢化物床的径向厚度对吸氢速率影响很大,金属氢化物床越薄,氢化反应的速度越快.

  17. 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.

  18. 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.

  19. Methods in industrial biotechnology for chemical engineers

    CERN Document Server

    Kandasamy, W B Vasantha

    2008-01-01

    In keeping with the definition that biotechnology is really no more than a name given to a set of techniques and processes, the authors apply some set of fuzzy techniques to chemical industry problems such as finding the proper proportion of raw mix to control pollution, to study flow rates, to find out the better quality of products. We use fuzzy control theory, fuzzy neural networks, fuzzy relational equations, genetic algorithms to these problems for solutions. When the solution to the problem can have certain concepts or attributes as indeterminate, the only model that can tackle such a situation is the neutrosophic model. The authors have also used these models in this book to study the use of biotechnology in chemical industries. This book has six chapters. First chapter gives a brief description of biotechnology. Second chapter deals will proper proportion of mix of raw materials in cement industries to minimize pollution using fuzzy control theory. Chapter three gives the method of determination of te...

  20. Fast New Method for Temporary Chemical Passivation

    Directory of Open Access Journals (Sweden)

    Marek Solčanský

    2012-12-01

    Full Text Available The main material parameter of silicon, that influences the effectiveness of photovoltaic cells, is the minority carrier bulk lifetime.It may change in the technological process especially during high temperature operations. Monitoring of the carrier bulk-lifetimeis necessary for modifying the whole technological process of production. For the measurement of the minority carrier bulk-lifetimethe characterization method MW PCD (Microwave Photoconductance Decay is used, where the result of measurement is the effectivecarrier lifetime, which is very dependent on the surface recombination velocity and therefore on the quality of a silicon surfacepassivation.This work deals with an examination of a different solution types for the chemical passivation of a silicon surface. Varioussolutions are tested on silicon wafers for their consequent comparison. The main purpose of this work is to find optimal solution, whichsuits the requirements of a time stability and start-up velocity of passivation, reproducibility of the measurements and a possibilityof a perfect cleaning of a passivating solution remains from a silicon surface. Another purpose of this work is to identify the parametersof other quinhydrone solutions with different concentrations as compared with the quinhydrone solution in methanol witha concentration of 0.07 mol/dm³ marked QM007 (referential solution.The method of an effective chemical passivation with a quinhydrone in methanol solution was suggested. The solution witha concentration of 0.07 mol /dm3 fulfills all required criteria. The work also confirms the influence of increased concentrationquinhydrone on the temporal stability of the passivation layer and the effect for textured silicon wafers. In conclusion, the influenceof an illumination and the temperature on the properties of the passivating solution QM007 is discussed.

  1. Chemical Methods for Peptide and Protein Production

    Directory of Open Access Journals (Sweden)

    Istvan Toth

    2013-04-01

    Full Text Available Since the invention of solid phase synthetic methods by Merrifield in 1963, the number of research groups focusing on peptide synthesis has grown exponentially. However, the original step-by-step synthesis had limitations: the purity of the final product decreased with the number of coupling steps. After the development of Boc and Fmoc protecting groups, novel amino acid protecting groups and new techniques were introduced to provide high quality and quantity peptide products. Fragment condensation was a popular method for peptide production in the 1980s, but unfortunately the rate of racemization and reaction difficulties proved less than ideal. Kent and co-workers revolutionized peptide coupling by introducing the chemoselective reaction of unprotected peptides, called native chemical ligation. Subsequently, research has focused on the development of novel ligating techniques including the famous click reaction, ligation of peptide hydrazides, and the recently reported a-ketoacid-hydroxylamine ligations with 5-oxaproline. Several companies have been formed all over the world to prepare high quality Good Manufacturing Practice peptide products on a multi-kilogram scale. This review describes the advances in peptide chemistry including the variety of synthetic peptide methods currently available and the broad application of peptides in medicinal chemistry.

  2. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of antimony by automated-hydride atomic absorption spectrophotometry

    Science.gov (United States)

    Brown, G.E.; McLain, B.J.

    1994-01-01

    The analysis of natural-water samples for antimony by automated-hydride atomic absorption spectrophotometry is described. Samples are prepared for analysis by addition of potassium and hydrochloric acid followed by an autoclave digestion. After the digestion, potassium iodide and sodium borohydride are added automatically. Antimony hydride (stibine) gas is generated, then swept into a heated quartz cell for determination of antimony by atomic absorption spectrophotometry. Precision and accuracy data are presented. Results obtained on standard reference water samples agree with means established by interlaboratory studies. Spike recoveries for actual samples range from 90 to 114 percent. Replicate analyses of water samples of varying matrices give relative standard deviations from 3 to 10 percent.

  3. GREENSCOPE: A Method for Modeling Chemical Process ...

    Science.gov (United States)

    Current work within the U.S. Environmental Protection Agency’s National Risk Management Research Laboratory is focused on the development of a method for modeling chemical process sustainability. The GREENSCOPE methodology, defined for the four bases of Environment, Economics, Efficiency, and Energy, can evaluate processes with over a hundred different indicators. These indicators provide a means for realizing the principles of green chemistry and green engineering in the context of sustainability. Development of the methodology has centered around three focal points. One is a taxonomy of impacts that describe the indicators and provide absolute scales for their evaluation. The setting of best and worst limits for the indicators allows the user to know the status of the process under study in relation to understood values. Thus, existing or imagined processes can be evaluated according to their relative indicator scores, and process modifications can strive towards realizable targets. A second area of focus is in advancing definitions of data needs for the many indicators of the taxonomy. Each of the indicators has specific data that is necessary for their calculation. Values needed and data sources have been identified. These needs can be mapped according to the information source (e.g., input stream, output stream, external data, etc.) for each of the bases. The user can visualize data-indicator relationships on the way to choosing selected ones for evalua

  4. Chemical Methods for Ugnu Viscous Oils

    Energy Technology Data Exchange (ETDEWEB)

    Kishore Mohanty

    2012-03-31

    The North Slope of Alaska has large (about 20 billion barrels) deposits of viscous oil in Ugnu, West Sak and Shraeder Bluff reservoirs. These shallow reservoirs overlie existing productive reservoirs such as Kuparuk and Milne Point. The viscosity of the Ugnu reservoir on top of Milne Point varies from 200 cp to 10,000 cp and the depth is about 3300 ft. The same reservoir extends to the west on the top of the Kuparuk River Unit and onto the Beaufort Sea. The depth of the reservoir decreases and the viscosity increases towards the west. Currently, the operators are testing cold heavy oil production with sand (CHOPS) in Ugnu, but oil recovery is expected to be low (< 10%). Improved oil recovery techniques must be developed for these reservoirs. The proximity to the permafrost is an issue for thermal methods; thus nonthermal methods must be considered. The objective of this project is to develop chemical methods for the Ugnu reservoir on the top of Milne Point. An alkaline-surfactant-polymer (ASP) formulation was developed for a viscous oil (330 cp) where as an alkaline-surfactant formulation was developed for a heavy oil (10,000 cp). These formulations were tested in one-dimensional and quarter five-spot Ugnu sand packs. Micromodel studies were conducted to determine the mechanisms of high viscosity ratio displacements. Laboratory displacements were modeled and transport parameters (such as relative permeability) were determined that can be used in reservoir simulations. Ugnu oil is suitable for chemical flooding because it is biodegraded and contains some organic acids. The acids react with injected alkali to produce soap. This soap helps in lowering interfacial tension between water and oil which in turn helps in the formation of macro and micro emulsions. A lower amount of synthetic surfactant is needed because of the presence of organic acids in the oil. Tertiary ASP flooding is very effective for the 330 cp viscous oil in 1D sand pack. This chemical formulation

  5. Chemical Methods for Ugnu Viscous Oils

    Energy Technology Data Exchange (ETDEWEB)

    Kishore Mohanty

    2012-03-31

    The North Slope of Alaska has large (about 20 billion barrels) deposits of viscous oil in Ugnu, West Sak and Shraeder Bluff reservoirs. These shallow reservoirs overlie existing productive reservoirs such as Kuparuk and Milne Point. The viscosity of the Ugnu reservoir on top of Milne Point varies from 200 cp to 10,000 cp and the depth is about 3300 ft. The same reservoir extends to the west on the top of the Kuparuk River Unit and onto the Beaufort Sea. The depth of the reservoir decreases and the viscosity increases towards the west. Currently, the operators are testing cold heavy oil production with sand (CHOPS) in Ugnu, but oil recovery is expected to be low (< 10%). Improved oil recovery techniques must be developed for these reservoirs. The proximity to the permafrost is an issue for thermal methods; thus nonthermal methods must be considered. The objective of this project is to develop chemical methods for the Ugnu reservoir on the top of Milne Point. An alkaline-surfactant-polymer (ASP) formulation was developed for a viscous oil (330 cp) where as an alkaline-surfactant formulation was developed for a heavy oil (10,000 cp). These formulations were tested in one-dimensional and quarter five-spot Ugnu sand packs. Micromodel studies were conducted to determine the mechanisms of high viscosity ratio displacements. Laboratory displacements were modeled and transport parameters (such as relative permeability) were determined that can be used in reservoir simulations. Ugnu oil is suitable for chemical flooding because it is biodegraded and contains some organic acids. The acids react with injected alkali to produce soap. This soap helps in lowering interfacial tension between water and oil which in turn helps in the formation of macro and micro emulsions. A lower amount of synthetic surfactant is needed because of the presence of organic acids in the oil. Tertiary ASP flooding is very effective for the 330 cp viscous oil in 1D sand pack. This chemical formulation

  6. Synthesis of Renewable Energy Materials, Sodium Aluminum Hydride by Grignard Reagent of Al

    Directory of Open Access Journals (Sweden)

    Jun-qin Wang

    2015-01-01

    Full Text Available The research on hydrogen generation and application has attracted widespread attention around the world. This paper is to demonstrate that sodium aluminum hydride can be synthesized under simple and mild reaction condition. Being activated through organics, aluminum powder reacts with hydrogen and sodium hydride to produce sodium aluminum hydride under atmospheric pressure. The properties and composition of the sample were characterized by FTIR, XRD, SEM, and so forth. The results showed that the product through this synthesis method is sodium aluminum hydride, and it has higher purity, perfect crystal character, better stability, and good hydrogen storage property. The reaction mechanism is also discussed in detail.

  7. 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.

  8. Chemical Reactivity as Described by Quantum Chemical Methods

    Directory of Open Access Journals (Sweden)

    F. De Proft

    2002-04-01

    Full Text Available Abstract: Density Functional Theory is situated within the evolution of Quantum Chemistry as a facilitator of computations and a provider of new, chemical insights. The importance of the latter branch of DFT, conceptual DFT is highlighted following Parr's dictum "to calculate a molecule is not to understand it". An overview is given of the most important reactivity descriptors and the principles they are couched in. Examples are given on the evolution of the structure-property-wave function triangle which can be considered as the central paradigm of molecular quantum chemistry to (for many purposes a structure-property-density triangle. Both kinetic as well as thermodynamic aspects can be included when further linking reactivity to the property vertex. In the field of organic chemistry, the ab initio calculation of functional group properties and their use in studies on acidity and basicity is discussed together with the use of DFT descriptors to study the kinetics of SN2 reactions and the regioselectivity in Diels Alder reactions. Similarity in reactivity is illustrated via a study on peptide isosteres. In the field of inorganic chemistry non empirical studies of adsorption of small molecules in zeolite cages are discussed providing Henry constants and separation constants, the latter in remarkable good agreement with experiments. Possible refinements in a conceptual DFT context are presented. Finally an example from biochemistry is discussed : the influence of point mutations on the catalytic activity of subtilisin.

  9. 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.

  10. 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.

  11. Single-Site Tetracoordinated Aluminum Hydride Supported on Mesoporous Silica. From Dream to Reality!

    KAUST Repository

    Werghi, Baraa

    2016-09-26

    The reaction of mesoporous silica (SBA15) dehydroxylated at 700 °C with diisobutylaluminum hydride, i-Bu2AlH, gives after thermal treatment a single-site tetrahedral aluminum hydride with high selectivity. The starting aluminum isobutyl and the final aluminum hydride have been fully characterized by FT-IR, advanced SS NMR spectroscopy (1H, 13C, multiple quanta (MQ) 2D 1H-1H, and 27Al), and elemental analysis, while DFT calculations provide a rationalization of the occurring reactivity. Trimeric i-Bu2AlH reacts selectively with surface silanols without affecting the siloxane bridges. Its analogous hydride catalyzes ethylene polymerization. Indeed, catalytic tests show that this single aluminum hydride site is active in the production of a high-density polyethylene (HDPE). © 2016 American Chemical Society.

  12. Getting metal-hydrides to do what you want them to

    Energy Technology Data Exchange (ETDEWEB)

    Gruen, D.M.

    1981-01-01

    With the discovery of AB/sub 5/ compounds, intermetallic hydrides with unusual properties began to be developed (H dissociation pressures of one to several atmospheres, extremely rapid and reversible adsorption/desorption very large amounts of H adsorbed). This paper reviews the factors that must be controlled in order to modify these hydrides to make them useful. The system LaNi/sub 5/ + H/sub 2/ is used as example. Use of AB/sub 5/ hydrides to construct a chemical heat pumps is discussed. Results of a systematic study substituting Al for Ni are reported; the HYCSOS pump is described briefly. Use of hydrides as hydrogen getters (substituted ZrV/sub 2/) is also discussed. Finally, possible developments in intermetallic hydride research in the 1980's and the hydrogen economy are discussed. 10 figures. (DLC)

  13. 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.

  14. 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.

  15. Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Ranmohotti, K.G. Sanjaya; Montasserasadi, M. Dariush; Choi, Jonglak; Yao, Yuan; Mohanty, Debasish; Josepha, Elisha A.; Adireddy, Shiva; Caruntu, Gabriel [Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148-2820 (United States); Wiley, John B., E-mail: jwiley@uno.edu [Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148-2820 (United States)

    2012-06-15

    Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 7} where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H{sub 2}Se{sub (g)} were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.

  16. 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)

  17. 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.

  18. Safety in the Chemical Laboratory: Tested Disposal Methods for Chemical Wastes from Academic Laboratories.

    Science.gov (United States)

    Armour, M. A.; And Others

    1985-01-01

    Describes procedures for disposing of dichromate cleaning solution, picric acid, organic azides, oxalic acid, chemical spills, and hydroperoxides in ethers and alkenes. These methods have been tested under laboratory conditions and are specific for individual chemicals rather than for groups of chemicals. (JN)

  19. Arsenic speciation analysis by HPLC postcolumn hydride generation and detection by atomic fluorescence spectrometry

    OpenAIRE

    Marschner, K; Musil, S. (Stanislav); Rychlovský, P.; Dědina, J. (Jiří)

    2014-01-01

    The aim of this contribution is to present a new method of hydride generation that enables to generate arsines from iAs , iAs , MMA and DMA in a flow injection mode with the same efficiency and in the next step connection of this hydride generator with HPLC column.

  20. Quality Control Guidelines for SAM Chemical Methods

    Science.gov (United States)

    Learn more about quality control guidelines and recommendations for the analysis of samples using the chemistry methods listed in EPA's Selected Analytical Methods for Environmental Remediation and Recovery (SAM).

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. Chemical Analysis Methods for Silicon Carbide

    Institute of Scientific and Technical Information of China (English)

    Shen Keyin

    2006-01-01

    @@ 1 General and Scope This Standard specifies the determination method of silicon dioxide, free silicon, free carbon, total carbon, silicon carbide, ferric sesquioxide in silicon carbide abrasive material.

  7. 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.

  8. A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures

    Science.gov (United States)

    Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

    2014-03-01

    Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.

  9. 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.

  10. Theoretical Estimate of Hydride Affinities of Aromatic Carbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

    AI Teng; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Aromatic carbonyl compounds are one type of the most important organic compounds, and the reductions ofthem by hydride agents such as LiAlH4 or NaBH4 are widely used in organic synthesis. The reactivity of carbonyl compounds generally increases in the following order: ketone < aldehyde, and amide < acid < ester < acid halide, which could be related to their hydride affinities (HA). In the previous paper, Robert[1] calculated the absolute HAof a series of small non-aromatic carbonyl compounds. In this paper, we use DFT method at B3LYP/6-311 + + G (2d, 2p)∥B3LYP/6-31 + G* level to estimate hydride affinities of five groups of aromatic carbonyl compounds. The detailed results are listed in Table 1.

  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. 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.

  13. Chemical ligation methods for the tagging of DNA-encoded chemical libraries.

    Science.gov (United States)

    Keefe, Anthony D; Clark, Matthew A; Hupp, Christopher D; Litovchick, Alexander; Zhang, Ying

    2015-06-01

    The generation of DNA-encoded chemical libraries requires the unimolecular association of multiple encoding oligonucleotides with encoded chemical entities during combinatorial synthesis processes. This has traditionally been achieved using enzymatic ligation. We discuss a range of chemical ligation methods that provide alternatives to enzymatic ligation. These chemical ligation methods include the generation of modified internucleotide linkages that support polymerase translocation and other modified linkages that while not supporting the translocation of polymerases can also be used to generate individual cDNA molecules containing encoded chemical information specifying individual library members. We also describe which of these approaches have been successfully utilized for the preparation of DNA-encoded chemical libraries and those that were subsequently used for the discovery of inhibitors.

  14. Ab-initio study of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Ramesh [Dept. of Physics, Feroze Gandhi Insititute of Engineering and Technology, Raebareli-229001 (India); Shukla, Seema, E-mail: sharma.yamini62@gmail.com; Dwivedi, Shalini, E-mail: sharma.yamini62@gmail.com; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com [Theoretical Condensed Matter Physics Laboratory, Dept. of Physics Feroze Gandhi College, Raebareli-229001 (India)

    2014-04-24

    We have performed ab initio self consistent calculations based on Full potential linearized augmented plane wave (FP-LAPW) method to investigate the optical and thermal properties of yttrium hydrides. From the band structure and density of states, the optical absorption spectra and specific heats have been calculated. The band structure of Yttrium metal changes dramatically due to hybridization of Y sp orbitals with H s orbitals and there is a net charge transfer from metal to hydrogen site. The electrical resistivity and specific heats of yttrium hydrides are lowered but the thermal conductivity is slightly enhanced due to increase in scattering from hydrogen sites.

  15. Investigation of Chemical Equilibrium Kinetics by the Electromigration Method

    CERN Document Server

    Bozhikov, G A; Bontchev, G D; Maslov, O D; Milanov, M V; Dmitriev, S N

    2002-01-01

    Measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the complex formation of Hf(IV) and DTPA is determined.

  16. Hydrogen storage: beyond conventional methods.

    Science.gov (United States)

    Dalebrook, Andrew F; Gan, Weijia; Grasemann, Martin; Moret, Séverine; Laurenczy, Gábor

    2013-10-09

    The efficient storage of hydrogen is one of three major hurdles towards a potential hydrogen economy. This report begins with conventional storage methods for hydrogen and broadly covers new technology, ranging from physical media involving solid adsorbents, to chemical materials including metal hydrides, ammonia borane and liquid precursors such as alcohols and formic acid.

  17. Optical emission spectrometric determination of arsenic and antimony by continuous flow chemical hydride generation and a miniaturized microwave microstrip argon plasma operated inside a capillary channel in a sapphire wafer

    Energy Technology Data Exchange (ETDEWEB)

    Pohl, Pawel; Zapata, Israel Jimenez; Bings, Nicolas H. [Universitaet Hamburg, Institut fuer Anorganische und Angewandte Chemie, Martin-Luther-King-Platz 6, D-20146 Hamburg (Germany); Voges, Edgar [Universitaet Dortmund, Fakultaet fuer Elektrotechnik und Informationstechnik, Friedrich-Woehler-Weg 4, D-44221 Dortmund (Germany); Broekaert, Jose A.C. [Universitaet Hamburg, Institut fuer Anorganische und Angewandte Chemie, Martin-Luther-King-Platz 6, D-20146 Hamburg (Germany)], E-mail: jose.broekaert@chemie.uni-hamburg.de

    2007-05-15

    Continuous flow chemical hydride generation coupled directly to a 40 W, atmospheric pressure, 2.45 GHz microwave microstrip Ar plasma operated inside a capillary channel in a sapphire wafer has been optimized for the emission spectrometric determination of As and Sb. The effect of the NaBH{sub 4} concentration, the concentration of HCl, HNO{sub 3} and H{sub 2}SO{sub 4} used for sample acidification, the Ar flow rate, the reagent flow rates, the liquid volume in the separator as well as the presence of interfering metals such as Fe, Cu, Ni, Co, Zn, Cd, Mn, Pb and Cr, was investigated in detail. A considerable influence of Fe(III) (enhancement of up to 50 %) for As(V) and of Fe(III), Cu(II) and Cr(III) (suppression of up to 75%) as well as of Cd(II) and Mn(II) (suppression by up to 25%) for Sb(III) was found to occur, which did not change by more than a factor of 2 in the concentration range of 2-20 {mu}g ml{sup -1}. The microstrip plasma tolerated the introduction of 4.2 ml min{sup -1} of H{sub 2} in the Ar working gas, which corresponded to an H{sub 2}/Ar ratio of 28%. Under these conditions, the excitation temperature as measured with Ar atom lines and the electron number density as determined from the Stark broadening of the H{sub {beta}} line was of the order of 5500 K and 1.50 . 10{sup 14} cm{sup -3}, respectively. Detection limits (3{sigma}) of 18 ng ml{sup -1} for As and 31 ng ml{sup -1} for Sb were found and the calibration curves were linear over 2 orders of magnitude. With the procedure developed As and Sb could be determined at the 45 and 6.4 {mu}g ml{sup -1} level in a galvanic bath solution containing 2.5% of NiSO{sub 4}. Additionally, As was determined in a coal fly ash reference material (NIST SRM 1633a) with a certified concentration of As of 145 {+-} 15 {mu}g g{sup -1} and a value of 144 {+-} 4 {mu}g g{sup -1} was found.

  18. Odour Detection Methods: Olfactometry and Chemical Sensors

    Directory of Open Access Journals (Sweden)

    Sara Lovascio

    2011-05-01

    Full Text Available The complexity of the odours issue arises from the sensory nature of smell. From the evolutionary point of view olfaction is one of the oldest senses, allowing for seeking food, recognizing danger or communication: human olfaction is a protective sense as it allows the detection of potential illnesses or infections by taking into account the odour pleasantness/unpleasantness. Odours are mixtures of light and small molecules that, coming in contact with various human sensory systems, also at very low concentrations in the inhaled air, are able to stimulate an anatomical response: the experienced perception is the odour. Odour assessment is a key point in some industrial production processes (i.e., food, beverages, etc. and it is acquiring steady importance in unusual technological fields (i.e., indoor air quality; this issue mainly concerns the environmental impact of various industrial activities (i.e., tanneries, refineries, slaughterhouses, distilleries, civil and industrial wastewater treatment plants, landfills and composting plants as sources of olfactory nuisances, the top air pollution complaint. Although the human olfactory system is still regarded as the most important and effective “analytical instrument” for odour evaluation, the demand for more objective analytical methods, along with the discovery of materials with chemo-electronic properties, has boosted the development of sensor-based machine olfaction potentially imitating the biological system. This review examines the state of the art of both human and instrumental sensing currently used for the detection of odours. The olfactometric techniques employing a panel of trained experts are discussed and the strong and weak points of odour assessment through human detection are highlighted. The main features and the working principles of modern electronic noses (E-Noses are then described, focusing on their better performances for environmental analysis. Odour emission monitoring

  19. Monitoring and control of a hydrogen production and storage system consisting of water electrolysis and metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Herranz, V.; Perez-Page, M. [Departamento de Ingenieria Quimica y Nuclear. Universidad Politecnica de Valencia. Camino de Vera S/N, 46022 Valencia (Spain); Beneito, R. [Area de Energia. Departamento de Gestion e Innovacion. Instituto Tecnologico del Juguete (AIJU). Avda. Industria 23, 03440 Ibi, Alicante (Spain)

    2010-02-15

    Renewable energy sources such as wind turbines and solar photovoltaic are energy sources that cannot generate continuous electric power. The seasonal storage of solar or wind energy in the form of hydrogen can provide the basis for a completely renewable energy system. In this way, water electrolysis is a convenient method for converting electrical energy into a chemical form. The power required for hydrogen generation can be supplied through a photovoltaic array. Hydrogen can be stored as metal hydrides and can be converted back into electricity using a fuel cell. The elements of these systems, i.e. the photovoltaic array, electrolyzer, fuel cell and hydrogen storage system in the form of metal hydrides, need a control and monitoring system for optimal operation. This work has been performed within a Research and Development contract on Hydrogen Production granted by Solar Iniciativas Tecnologicas, S.L. (SITEC), to the Politechnic University of Valencia and to the AIJU, and deals with the development of a system to control and monitor the operation parameters of an electrolyzer and a metal hydride storage system that allow to get a continuous production of hydrogen. (author)

  20. Thermal decomposition kinetics of titanium hydride and Al alloy melt foaming process

    Institute of Scientific and Technical Information of China (English)

    YANG; Donghui; HE; Deping; YANG; Shangrun

    2004-01-01

    A temperature programmed decomposition (TPD) apparatus with metal tube structure, in which Ar is used as the carrier gas, is established and the TPD spectrum of titanium hydride is acquired. Using consulting table method (CTM), spectrum superposition method (SSM) and differential spectrum technique, TPD spectrum of titanium hydride is separated and a set of thermal decomposition kinetics equations are acquired. According to these equations, the relationship between decomposition quantity and time for titanium hydride at the temperature of 940 K is obtained and the result well coincides with the Al alloy melt foaming process.

  1. Speculations on the existence of hydride ions in proton conducting oxides

    DEFF Research Database (Denmark)

    Poulsen, F.W.

    2001-01-01

    The chemical and physical nature of the hydride ion is briefly treated. Several reactions of the hydride ion in oxides or oxygen atmosphere are given, A number of perovskites and inverse perovskites are listed. which contain the H- ion on the oxygen or B-anion sites in the archetype ABO(3) System....... H- is stable with respect to oxide and halide anions but, among cations only with respect to oxides and halides of strongly electropositive metals such as alkaline, alkaline-earth and main group III metals. H- is only stable in combination with transition metal ions of certain elements...... in their lowest positive oxidation state. Mixed oxide/hydride containing perovskites may thus exist. Steinsvik et al. have recently suggested a defect model for a perovskite including substitutional hydride ions on the oxygen site, H-O(.), and protons associated with a lattice oxygen, OHO.. The defect equations...

  2. METHODS FOR INVESTIGATION OF CHEMICAL CHARACTERISTICS IN POLYMER MATERIALS

    Directory of Open Access Journals (Sweden)

    V. V. Kuzmich

    2017-01-01

    Full Text Available A method for measuring polymer chemical resistance by dipping specimens in chemical reagents is a standard investigation procedure used in chemical industry (Standards ASTM D543, ISO 155. Such method has been used only for comparative evaluation of chemical resistance for various materials in a number of typical reagents. The results obtained with the help of the method do not provide the possibility directly to estimate application of the given material for this or that products which are used in contact with various chemical environments. It is necessary to take into account such limitations of theused testing results as duration of environmental exposure, temperature and reagent concentration in the medium. If it is as sumed that the method is applied under conditions when a product is continuously contacting with liquid then the results of short-term testings can be used only with the purpose to exclude the least adequate materials. Testing equipment has included a precision chemical balance, a micrometer, a container for immersion medium, a thermostat for setting and maintaining the required temperature and devices for measuring physical properties. Dimensions and type of a test specimen are specified by the shape of material which is used for testing. At least three specimens are needed for testing in every reagent. Changes in dimension and weight are measured for every specimen. The specimen is placed in container for 7 days in standard laboratory atmosphere where it should not touch a bottom or walls of the container.

  3. 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

    In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heat released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested

  4. Chemical Methods to Knock Down the Amyloid Proteins

    Directory of Open Access Journals (Sweden)

    Na Gao

    2017-06-01

    Full Text Available Amyloid proteins are closely related with amyloid diseases and do tremendous harm to human health. However, there is still a lack of effective strategies to treat these amyloid diseases, so it is important to develop novel methods. Accelerating the clearance of amyloid proteins is a favorable method for amyloid disease treatment. Recently, chemical methods for protein reduction have been developed and have attracted much attention. In this review, we focus on the latest progress of chemical methods that knock down amyloid proteins, including the proteolysis-targeting chimera (PROTAC strategy, the “recognition-cleavage” strategy, the chaperone-mediated autophagy (CMA strategy, the selectively light-activatable organic and inorganic molecules strategy and other chemical strategies.

  5. Chemical Modification Methods of Nanoparticles of Silicon Carbide Surface

    OpenAIRE

    Anton S. Yegorov; Vitaly S. Ivanov; Alexey V. Antipov; Alyona I. Wozniak; Kseniia V. Tcarkova.

    2015-01-01

    silicon carbide exhibits exceptional properties: high durability, high thermal conductivity, good heat resistance, low thermal expansion factor and chemical inactivity. Reinforcement with silicon carbide nanoparticles increases polymer’s tensile strength and thermal stability.Chemical methods of modification of the silicon carbide surface by means of variety of reagents from ordinary molecules to macromolecular polymers are reviewed in the review.The structure of silicon carbide surface layer...

  6. Release of hydrogen from nanoconfined hydrides by application of microwaves

    Science.gov (United States)

    Sanz-Moral, Luis Miguel; Navarrete, Alexander; Sturm, Guido; Link, Guido; Rueda, Miriam; Stefanidis, Georgios; Martín, Ángel

    2017-06-01

    The release of hydrogen from solid hydrides by thermolysis can be improved by nanoconfinement of the hydride in a suitable micro/mesoporous support, but the slow heat transfer by conduction through the support can be a limitation. In this work, a C/SiO2 mesoporous material has been synthesized and employed as matrix for nanoconfinement of hydrides. The matrix showed high surface area and pore volume (386 m2/g and 1.41 cm3/g), which enabled the confinement of high concentrations of hydride. Furthermore, by modification of the proportion between C and SiO2, the dielectric properties of the complex could be modified, making it susceptible to microwave heating. As with this heating method the entire sample is heated simultaneously, the heat transfer resistances associated to conduction were eliminated. To demonstrate this possibility, ethane 1,2-diaminoborane (EDAB) was embedded on the C/SiO2 matrix at concentrations ranging from 11 to 31%wt using a wet impregnation method, and a device appropriate for hydrogen release from this material by application of microwaves was designed with the aid of a numerical simulation. Hydrogen liberation tests by conventional heating and microwaves were compared, showing that by microwave heating hydrogen release can be initiated and stopped in shorter times.

  7. 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.

  8. 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.

  9. The reactivity of sodium alanates with O[2], H[2]O, and CO[2] : an investigation of complex metal hydride contamination in the context of automotive systems.

    Energy Technology Data Exchange (ETDEWEB)

    Dedrick, Daniel E.; Bradshaw, Robert W.; Behrens, Richard, Jr.

    2007-08-01

    Safe and efficient hydrogen storage is a significant challenge inhibiting the use of hydrogen as a primary energy carrier. Although energy storage performance properties are critical to the success of solid-state hydrogen storage systems, operator and user safety is of highest importance when designing and implementing consumer products. As researchers are now integrating high energy density solid materials into hydrogen storage systems, quantification of the hazards associated with the operation and handling of these materials becomes imperative. The experimental effort presented in this paper focuses on identifying the hazards associated with producing, storing, and handling sodium alanates, and thus allowing for the development and implementation of hazard mitigation procedures. The chemical changes of sodium alanates associated with exposure to oxygen and water vapor have been characterized by thermal decomposition analysis using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and X-ray diffraction methods. Partial oxidation of sodium alanates, an alkali metal complex hydride, results in destabilization of the remaining hydrogen-containing material. At temperatures below 70 C, reaction of sodium alanate with water generates potentially combustible mixtures of H{sub 2} and O{sub 2}. In addition to identifying the reaction hazards associated with the oxidation of alkali-metal containing complex hydrides, potential treatment methods are identified that chemically stabilize the oxidized material and reduce the hazard associated with handling the contaminated metal hydrides.

  10. Chemical reactor and method for chemically converting a first material into a second material

    Science.gov (United States)

    Kong, Peter C.

    2008-04-08

    A chemical reactor and method for converting a first material into a second material is disclosed and wherein the chemical reactor is provided with a feed stream of a first material which is to be converted into a second material; and wherein the first material is combusted in the chemical reactor to produce a combustion flame, and a resulting gas; and an electrical arc is provided which is passed through or superimposed upon the combustion flame and the resulting gas to facilitate the production of the second material.

  11. Chemical reactor and method for chemically converting a first material into a second material

    Science.gov (United States)

    Kong, Peter C.

    2008-04-08

    A chemical reactor and method for converting a first material into a second material is disclosed and wherein the chemical reactor is provided with a feed stream of a first material which is to be converted into a second material; and wherein the first material is combusted in the chemical reactor to produce a combustion flame, and a resulting gas; and an electrical arc is provided which is passed through or superimposed upon the combustion flame and the resulting gas to facilitate the production of the second material.

  12. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne

    2011-12-02

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

  13. 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.

  14. 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...

  15. [Research on optimization of mathematical model of flow injection-hydride generation-atomic fluorescence spectrometry].

    Science.gov (United States)

    Cui, Jian; Zhao, Xue-Hong; Wang, Yan; Xiao, Ya-Bing; Jiang, Xue-Hui; Dai, Li

    2014-01-01

    Flow injection-hydride generation-atomic fluorescence spectrometry was a widely used method in the industries of health, environmental, geological and metallurgical fields for the merit of high sensitivity, wide measurement range and fast analytical speed. However, optimization of this method was too difficult as there exist so many parameters affecting the sensitivity and broadening. Generally, the optimal conditions were sought through several experiments. The present paper proposed a mathematical model between the parameters and sensitivity/broadening coefficients using the law of conservation of mass according to the characteristics of hydride chemical reaction and the composition of the system, which was proved to be accurate as comparing the theoretical simulation and experimental results through the test of arsanilic acid standard solution. Finally, this paper has put a relation map between the parameters and sensitivity/broadening coefficients, and summarized that GLS volume, carrier solution flow rate and sample loop volume were the most factors affecting sensitivity and broadening coefficients. Optimizing these three factors with this relation map, the relative sensitivity was advanced by 2.9 times and relative broadening was reduced by 0.76 times. This model can provide a theoretical guidance for the optimization of the experimental conditions.

  16. 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.

  17. In situ probing of surface hydrides on hydrogenated amorphous silicon using attenuated total reflection infrared spectroscopy

    CERN Document Server

    Kessels, W M M; Sanden, M C M; Aydil, E S

    2002-01-01

    An in situ method based on attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is presented for detecting surface silicon hydrides on plasma deposited hydrogenated amorphous silicon (a-Si:H) films and for determining their surface concentrations. Surface silicon hydrides are desorbed by exposing the a-Si:H films to low energy ions from a low density Ar plasma and by comparing the infrared spectrum before and after this low energy ion bombardment, the absorptions by surface hydrides can sensitively be separated from absorptions by bulk hydrides incorporated into the film. An experimental comparison with other methods that utilize isotope exchange of the surface hydrogen with deuterium showed good agreement and the advantages and disadvantages of the different methods are discussed. Furthermore, the determination of the composition of the surface hydrogen bondings on the basis of the literature data on hydrogenated crystalline silicon surfaces is presented, and quantification of the h...

  18. 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.

  19. Chemical Decellularization Methods and Its Effects on Extracellular Matrix

    Directory of Open Access Journals (Sweden)

    Amir Hossein Akbari Zahmati

    2017-08-01

    Full Text Available Background:  Extracellular matrix (ECM produced by tissue decellularization processes as a biological scaffold due to its unique properties compared to other scaffolds for migration and implantation of stem cells have been used successfully in the field of tissue engineering and regenerative medicine in the last years. The objective of this manuscript was to provide an overview of the chemical decellularization methods, evaluation of decellularized ECM and the potential effect of the chemical decellularization agents on the biochemical composition. Methods: We searched in Google Scholar, PubMed, Scopus, and Science Direct. The literature search was done by using the following keywords: “ECM, biologic scaffold, decellularization, chemical methods, tissue engineering.” We selected articles have been published from 2000 to 2016, and 15 full texts and 97 abstracts were reviewed. Results:Employing an optimization method to minimize damage to the ECM ultrastructure as for a result of the lack of reduction in mechanical properties and also the preservation of essential proteins such as laminin, fibronectin, Glycosaminoglycans (GAGs, growth factor is required. Various methods include chemical, physical and enzymatic technics were studied. However, on each of these methods can have undesirable effects on ECM. Conclusion: It is suggested that instead of the Sodium dodecyl sulfate (SDS which have high strength degradation, we can use zwitterionic separately or in combination with SDS. Tributyl phosphate (TBP due to its unique properties can be used in decellularization process.

  20. Optimization of Internal Cooling Fins for Metal Hydride Reactors

    Directory of Open Access Journals (Sweden)

    Vamsi Krishna Kukkapalli

    2016-06-01

    Full Text Available Metal hydride alloys are considered as a promising alternative to conventional hydrogen storage cylinders and mechanical hydrogen compressors. Compared to storing in a classic gas tank, metal hydride alloys can store hydrogen at nearly room pressure and use less volume to store the same amount of hydrogen. However, this hydrogen storage method necessitates an effective way to reject the heat released from the exothermic hydriding reaction. In this paper, a finned conductive insert is adopted to improve the heat transfer in the cylindrical reactor. The fins collect the heat that is volumetrically generated in LaNi5 metal hydride alloys and deliver it to the channel located in the center, through which a refrigerant flows. A multiple-physics modeling is performed to analyze the transient heat and mass transfer during the hydrogen absorption process. Fin design is made to identify the optimum shape of the finned insert for the best heat rejection. For the shape optimization, use of a predefined transient heat generation function is proposed. Simulations show that there exists an optimal length for the fin geometry.

  1. 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

  2. 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).

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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

  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

    The United Technologies Research Center (UTRC), in collaboration with major partners Albemarle Corporation (Albemarle) and the Savannah River National Laboratory (SRNL), conducted research to discover new hydride materials for the storage of hydrogen having on-board reversibility and a target gravimetric capacity of ≥ 7.5 weight percent (wt %). When integrated into a system with a reasonable efficiency of 60% (mass of hydride / total mass), this target material would produce a system gravimetric capacity of ≥ 4.5 wt %, consistent with the DOE 2007 target. The approach established for the project combined first principles modeling (FPM - UTRC) with multiple synthesis methods: Solid State Processing (SSP - UTRC), Solution Based Processing (SBP - Albemarle) and Molten State Processing (MSP - SRNL). In the search for novel compounds, each of these methods has advantages and disadvantages; by combining them, the potential for success was increased. During the project, UTRC refined its FPM framework which includes ground state (0 Kelvin) structural determinations, elevated temperature thermodynamic predictions and thermodynamic / phase diagram calculations. This modeling was used both to precede synthesis in a virtual search for new compounds and after initial synthesis to examine reaction details and options for modifications including co-reactant additions. The SSP synthesis method involved high energy ball milling which was simple, efficient for small batches and has proven effective for other storage material compositions. The SBP method produced very homogeneous chemical reactions, some of which cannot be performed via solid state routes, and would be the preferred approach for large scale production. The MSP technique is similar to the SSP method, but involves higher temperature and hydrogen pressure conditions to achieve greater species mobility. During the initial phases of the project, the focus was on higher order alanate complexes in the phase space

  12. Dissociation potential curves of low-lying states in transition metal hydrides. 3. Hydrides of groups 6 and 7.

    Science.gov (United States)

    Koseki, Shiro; Matsushita, Takeshi; Gordon, Mark S

    2006-02-23

    The dissociation curves of low-lying spin-mixed states in monohydrides of groups 6 and 7 were calculated by using an effective core potential (ECP) approach. This approach is based on the multiconfiguration self-consistent field (MCSCF) method, followed by first-order configuration interaction (FOCI) calculations, in which the method employs an ECP basis set proposed by Stevens and co-workers (SBKJC) augmented by a set of polarization functions. Spin-orbit coupling (SOC) effects are estimated within the one-electron approximation by using effective nuclear charges, since SOC splittings obtained with the full Breit-Pauli Hamitonian are underestimated when ECP basis sets are used. The ground states of group 6 hydrides have Omega = (1)/(2)(X(6)Sigma(+)(1/2)), where Omega is the z component of the total angular momentum quantum number. Although the ground states of group 7 hydrides have Omega = 0(+), their main adiabatic components are different; the ground state in MnH originates from the lowest (7)Sigma(+), while in TcH and ReH the main component of the ground state is the lowest (5)Sigma(+). The present paper reports a comprehensive set of theoretical results including the dissociation energies, equilibrium distances, electronic transition energies, harmonic frequencies, anharmonicities, and rotational constants for several low-lying spin-mixed states in these hydrides. Transition dipole moments were also computed among the spin-mixed states and large peak positions of electronic transitions are suggested theoretically for these hydrides. The periodic trends of physical properties of metal hydrides are discussed, based on the results reported in this and other recent studies.

  13. Impact of traditional processing methods on some physico chemical ...

    African Journals Online (AJOL)

    AJB SERVER

    2006-10-16

    Oct 16, 2006 ... was then compared with flour sample prepared in the laboratory ... 'Fufu' samples from the modified method was significantly ... need to educate traditional processors on good manufacturing ... to dust, animals (e.g., lizard, sheep and goats), birds ... before being used for physical and chemical analyses.

  14. Rapid hydrogen gas generation using reactive thermal decomposition of uranium hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Kanouff, Michael P.; Van Blarigan, Peter; Robinson, David B.; Shugard, Andrew D.; Gharagozloo, Patricia E.; Buffleben, George M.; James, Scott Carlton; Mills, Bernice E.

    2011-09-01

    Oxygen gas injection has been studied as one method for rapidly generating hydrogen gas from a uranium hydride storage system. Small scale reactors, 2.9 g UH{sub 3}, were used to study the process experimentally. Complimentary numerical simulations were used to better characterize and understand the strongly coupled chemical and thermal transport processes controlling hydrogen gas liberation. The results indicate that UH{sub 3} and O{sub 2} are sufficiently reactive to enable a well designed system to release gram quantities of hydrogen in {approx} 2 seconds over a broad temperature range. The major system-design challenge appears to be heat management. In addition to the oxidation tests, H/D isotope exchange experiments were performed. The rate limiting step in the overall gas-to-particle exchange process was found to be hydrogen diffusion in the {approx}0.5 {mu}m hydride particles. The experiments generated a set of high quality experimental data; from which effective intra-particle diffusion coefficients can be inferred.

  15. Equilibrium composition for the reaction of plutonium hydride with air

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    There are six independent constituents with 4 chemical elements, i.e. PuH2.7(s), PuN(s), Pu2O3(s), N2, O2 and H2, therefore , the system described involves of 2 independent reactions ,both those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The present paper has briefly discussed the simultaneous reactions and its thermodynamic coupling effect.

  16. Nanoconfined hydrides for energy storage

    Science.gov (United States)

    Nielsen, Thomas K.; Besenbacher, Flemming; Jensen, Torben R.

    2011-05-01

    The world in the 21st century is facing increasing challenges within the development of more environmentally friendly energy systems, sustainable and `green chemistry' solutions for a variety of chemical and catalytic processes. Nanomaterials science is expected to contribute strongly by the development of new nanotools, e.g. for improving the performance of chemical reactions. Nanoconfinement is of increasing interest and may lead to significantly enhanced kinetics, higher degree of stability and/or more favourable thermodynamic properties. Nanoconfined chemical reactions may have a wide range of important applications in the near future, e.g. within the merging area of chemical storage of renewable energy. This review provides selected examples within nanoconfinement of hydrogen storage materials, which may serve as an inspiration for other research fields as well. Selected nanoporous materials, methods for preparation of nanoconfined systems and their hydrogen storage properties are reviewed.The world in the 21st century is facing increasing challenges within the development of more environmentally friendly energy systems, sustainable and `green chemistry' solutions for a variety of chemical and catalytic processes. Nanomaterials science is expected to contribute strongly by the development of new nanotools, e.g. for improving the performance of chemical reactions. Nanoconfinement is of increasing interest and may lead to significantly enhanced kinetics, higher degree of stability and/or more favourable thermodynamic properties. Nanoconfined chemical reactions may have a wide range of important applications in the near future, e.g. within the merging area of chemical storage of renewable energy. This review provides selected examples within nanoconfinement of hydrogen storage materials, which may serve as an inspiration for other research fields as well. Selected nanoporous materials, methods for preparation of nanoconfined systems and their hydrogen storage

  17. Soil chemical sensor and precision agricultural chemical delivery system and method

    Energy Technology Data Exchange (ETDEWEB)

    Colburn, J.W. Jr.

    1991-07-23

    A real time soil chemical sensor and precision agricultural chemical delivery system includes a plurality of ground-engaging tools in association with individual soil sensors which measure soil chemical levels. The system includes the addition of a solvent which rapidly saturates the soil/tool interface to form a conductive solution of chemicals leached from the soil. A multivalent electrode, positioned within a multivalent frame of the ground-engaging tool, applies a voltage or impresses a current between the electrode and the tool frame. A real-time soil chemical sensor and controller senses the electrochemical reaction resulting from the application of the voltage or current to the leachate, measures it by resistivity methods, and compares it against pre-set resistivity levels for substances leached by the solvent. Still greater precision is obtained by calibrating for the secondary current impressed through solvent-less soil. The appropriate concentration is then found and the servo-controlled delivery system applies the appropriate amount of fertilizer or agricultural chemicals substantially in the location from which the soil measurement was taken. 5 figures.

  18. Studies of Trace Gas Chemical Cycles Using Observations, Inverse Methods and Global Chemical Transport Models

    Science.gov (United States)

    Prinn, Ronald G.

    2001-01-01

    For interpreting observational data, and in particular for use in inverse methods, accurate and realistic chemical transport models are essential. Toward this end we have, in recent years, helped develop and utilize a number of three-dimensional models including the Model for Atmospheric Transport and Chemistry (MATCH).

  19. Chemical Modification Methods of Nanoparticles of Silicon Carbide Surface

    Directory of Open Access Journals (Sweden)

    Anton S. Yegorov

    2015-09-01

    Full Text Available silicon carbide exhibits exceptional properties: high durability, high thermal conductivity, good heat resistance, low thermal expansion factor and chemical inactivity. Reinforcement with silicon carbide nanoparticles increases polymer’s tensile strength and thermal stability.Chemical methods of modification of the silicon carbide surface by means of variety of reagents from ordinary molecules to macromolecular polymers are reviewed in the review.The structure of silicon carbide surface layer and the nature of modificator bonding with the surface of SiC particles are reviewed. General examples of surface modification methodologies and composite materials with the addition of modified SiC are given.

  20. Methods and tools for sustainable chemical process design

    DEFF Research Database (Denmark)

    Loureiro da Costa Lira Gargalo, Carina; Chairakwongsa, Siwanat; Quaglia, Alberto;

    2015-01-01

    As the pressure on chemical and biochemical processes to achieve a more sustainable performance increases, the need to define a systematic and holistic way to accomplish this is becoming more urgent. In this chapter, a multilevel computer-aided framework for systematic design of more sustainable...... chemical processes is presented. The framework allows the use of appropriate computer-aided methods and tools in a hierarchical manner according to a developed work flow for a multilevel criteria analysis that helps generate competing and more sustainable process design options. The application...

  1. Kinetics of hydrogen desorption from MgH2 and AlH3 hydrides

    Science.gov (United States)

    Terent'ev, P. B.; Gerasimov, E. G.; Mushnikov, N. V.; Uimin, M. A.; Maikov, V. V.; Gaviko, V. S.; Golovatenko, V. D.

    2015-12-01

    Kinetic parameters of the process of thermal decomposition of the MgH2 hydride (obtained by the method of the mechanoactivation of magnesium in a hydrogen atmosphere) and of the commercial AlH3 hydride have been studied upon the rapid heating in the range of temperatures of 150-510°C at hydrogen pressures of 0-2 atm. The time dependences of the amount of hydrogen released by the metal hydrides at different temperatures and pressures have been determined. It has been shown that the activation energies of the hydrogen desorption are 135 kJ/mol for MgH2 and 107 kJ/mol for AlH3. The maximum rates of hydrogen desorption from the investigated metal hydrides have been established, and the temperatures and initial pressures that ensure the maximum rate and maximum volume of the hydrogen release have been determined.

  2. Chemical and physical solutions for hydrogen storage.

    Science.gov (United States)

    Eberle, Ulrich; Felderhoff, Michael; Schüth, Ferdi

    2009-01-01

    Hydrogen is a promising energy carrier in future energy systems. However, storage of hydrogen is a substantial challenge, especially for applications in vehicles with fuel cells that use proton-exchange membranes (PEMs). Different methods for hydrogen storage are discussed, including high-pressure and cryogenic-liquid storage, adsorptive storage on high-surface-area adsorbents, chemical storage in metal hydrides and complex hydrides, and storage in boranes. For the latter chemical solutions, reversible options and hydrolytic release of hydrogen with off-board regeneration are both possible. Reforming of liquid hydrogen-containing compounds is also a possible means of hydrogen generation. The advantages and disadvantages of the different systems are compared.

  3. Hydrogen transmission/storage with a metal hydride/organic slurry

    Energy Technology Data Exchange (ETDEWEB)

    Breault, R.W.; Rolfe, J.; McClaine, A. [Thermo Power Corp., Waltham, MA (United States)

    1998-08-01

    Thermo Power Corporation has developed a new approach for the production, transmission, and storage of hydrogen. In this approach, a chemical hydride slurry is used as the hydrogen carrier and storage media. The slurry protects the hydride from unanticipated contact with moisture in the air and makes the hydride pumpable. At the point of storage and use, a chemical hydride/water reaction is used to produce high-purity hydrogen. An essential feature of this approach is the recovery and recycle of the spent hydride at centralized processing plants, resulting in an overall low cost for hydrogen. This approach has two clear benefits: it greatly improves energy transmission and storage characteristics of hydrogen as a fuel, and it produces the hydrogen carrier efficiently and economically from a low cost carbon source. The preliminary economic analysis of the process indicates that hydrogen can be produced for $3.85 per million Btu based on a carbon cost of $1.42 per million Btu and a plant sized to serve a million cars per day. This compares to current costs of approximately $9.00 per million Btu to produce hydrogen from $3.00 per million Btu natural gas, and $25 per million Btu to produce hydrogen by electrolysis from $0.05 per Kwh electricity. The present standard for production of hydrogen from renewable energy is photovoltaic-electrolysis at $100 to $150 per million Btu.

  4. Novel selection methods for DNA-encoded chemical libraries.

    Science.gov (United States)

    Chan, Alix I; McGregor, Lynn M; Liu, David R

    2015-06-01

    Driven by the need for new compounds to serve as biological probes and leads for therapeutic development and the growing accessibility of DNA technologies including high-throughput sequencing, many academic and industrial groups have begun to use DNA-encoded chemical libraries as a source of bioactive small molecules. In this review, we describe the technologies that have enabled the selection of compounds with desired activities from these libraries. These methods exploit the sensitivity of in vitro selection coupled with DNA amplification to overcome some of the limitations and costs associated with conventional screening methods. In addition, we highlight newer techniques with the potential to be applied to the high-throughput evaluation of DNA-encoded chemical libraries.

  5. Method for innovative synthesis-design of chemical process flowsheets

    OpenAIRE

    Kumar Tula, Anjan; Gani, Rafiqul

    2015-01-01

    Chemical process synthesis-design involve the identification of the processing route to reach a desired product from a specified set of raw materials, design of the operations involved in the processing route, the calculations of utility requirements, the calculations of waste and emission to the surrounding and many more. Different methods (knowledge-based [1], mathematical programming [2], hybrid, etc.) have been proposed and are also currently employed to solve these synthesis-design probl...

  6. The abnormal lattice contraction of plutonium hydrides studied by first-principles calculations

    Institute of Scientific and Technical Information of China (English)

    Ao Bing-Yun; Shi Peng; Guo Yong; Gao Tao

    2013-01-01

    Pu can be loaded with H forming complicated continuous solid solutions and compounds,and causing remarkable electronic and structural changes.Full potential linearized augmented plane wave methods combined with Hubbard parameter U and the spin-orbit effects are employed to investigate the electronic and structural properties of stoichiometric and non-stoichiometric face-centered cubic Pu hydrides (PuHx,x =2,2.25,2.5,2.75,3).The decreasing trend with increasing x of the calculated lattice parameters is in reasonable agreement with the experimental findings.A comparative analysis of the electronic-structure results for a series of PuHx compositions reveals that the lattice contraction results from the associated effects of the enhanced chemical bonding and the size effects involving the interstitial atoms.We find that the size effects are the driving force for the abnormal lattice contraction.

  7. 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.

  8. 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.

  9. 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.

  10. Fermentation, fractionation and purification of streptokinase by chemical reduction method

    Directory of Open Access Journals (Sweden)

    M Niakan

    2011-05-01

    Full Text Available Background and Objectives: Streptokinase is used clinically as an intravenous thrombolytic agent for the treatment of acute myocardial infarction and is commonly prepared from cultures of Streptococcus equisimilis strain H46A. The objective of the present study was the production of streptokinase from strain H46A and purification by chemical reduction method."nMaterials and Methods: The rate of streptokinase production evaluated under the effect of changes on some fermentation factors. Moreover, due to the specific structure of streptokinase, a chemical reduction method employed for the purification of streptokinase from the fermentation broth. The H46A strain of group C streptococcus, was grown in a fermentor. The proper pH adjusted with NaOH under glucose feeding in an optimum temperature. The supernatant of the fermentation product was sterilized by filtration and concentrated by ultrafiltration. The pH of the concentrate was adjusted, cooled, and precipitated by methanol. Protein solution was reduced with dithiothreitol (DTT. Impurities settled down by aldrithiol-2 and the biological activity of supernatant containing streptokinase was determined."nResults: In the fed -batch culture, the rate of streptokinase production increased over two times as compared with the batch culture and the impurities were effectively separated from streptokinase by reduction method."nConclusion: Improvements in SK production are due to a decrease in lag phase period and increase in the growth rate of logarithmic phase. The methods of purification often result in unacceptable losses of streptokinase, but the chemical reduction method give high yield of streptokinase and is easy to perform it.

  11. Approximate method for stochastic chemical kinetics with two-time scales by chemical Langevin equations

    Science.gov (United States)

    Wu, Fuke; Tian, Tianhai; Rawlings, James B.; Yin, George

    2016-05-01

    The frequently used reduction technique is based on the chemical master equation for stochastic chemical kinetics with two-time scales, which yields the modified stochastic simulation algorithm (SSA). For the chemical reaction processes involving a large number of molecular species and reactions, the collection of slow reactions may still include a large number of molecular species and reactions. Consequently, the SSA is still computationally expensive. Because the chemical Langevin equations (CLEs) can effectively work for a large number of molecular species and reactions, this paper develops a reduction method based on the CLE by the stochastic averaging principle developed in the work of Khasminskii and Yin [SIAM J. Appl. Math. 56, 1766-1793 (1996); ibid. 56, 1794-1819 (1996)] to average out the fast-reacting variables. This reduction method leads to a limit averaging system, which is an approximation of the slow reactions. Because in the stochastic chemical kinetics, the CLE is seen as the approximation of the SSA, the limit averaging system can be treated as the approximation of the slow reactions. As an application, we examine the reduction of computation complexity for the gene regulatory networks with two-time scales driven by intrinsic noise. For linear and nonlinear protein production functions, the simulations show that the sample average (expectation) of the limit averaging system is close to that of the slow-reaction process based on the SSA. It demonstrates that the limit averaging system is an efficient approximation of the slow-reaction process in the sense of the weak convergence.

  12. 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.

  13. Effect of Magnesium Hydride on the Corrosion Behavior of Pure Magnesium in 0.1 M NaCl Solution

    Directory of Open Access Journals (Sweden)

    Shanna Xu

    2010-01-01

    Full Text Available The effect of magnesium hydride on the corrosion behavior of pure magnesium in 0.1 M NaCl solution was investigated using the gas collection method, potentiostatic current decay test, and in situ Raman spectrum. The formation of magnesium hydride (MgH2, Mg2H4 was observed at the cathodic region. Applying anodic potential leads to decomposition of magnesium hydride. Magnesium hydride plays an important role on the negative difference effect (NDE in both the cathodic and anodic regions.

  14. In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes.

    Science.gov (United States)

    Hugenbruch, Stefan; Shafaat, Hannah S; Krämer, Tobias; Delgado-Jaime, Mario Ulises; Weber, Katharina; Neese, Frank; Lubitz, Wolfgang; DeBeer, Serena

    2016-04-28

    Metal hydrides are invoked as important intermediates in both chemical and biological H2 production. In the [NiFe] hydrogenase enzymes, pulsed EPR and high-resolution crystallography have argued that the hydride interacts primarily at the Ni site. In contrast, in [NiFe] hydrogenase model complexes, it is observed that the bridging hydride interacts primarily with the Fe. Herein, we utilize a combination of Ni and Fe X-ray absorption (XAS) and emission (XES) spectroscopies to examine the contribution of the bridging hydride to the observed spectral features in [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)3](+). The corresponding data on (dppe)Ni(μ-pdt)Fe(CO)3 are used as a reference for the changes that occur in the absence of a hydride bridge. For further interpretation of the observed spectral features, all experimental spectra were calculated using a density functional theory (DFT) approach, with excellent agreement between theory and experiment. It is found that the iron valence-to-core (VtC) XES spectra reveal clear signatures for the presence of a Fe-H interaction in the hydride bridged model complex. In contrast, the Ni VtC XES spectrum largely reflects changes in the local Ni geometry and shows little contribution from a Ni-H interaction. A stepwise theoretical analysis of the hydride contribution and the Ni site symmetry provides insights into the factors, which govern the different metal-hydride interactions in both the model complexes and the enzyme. Furthermore, these results establish the utility of two-color XES to reveal important insights into the electronic structure of various metal-hydride species.

  15. Optical studies of neutron-irradiated lithium hydride single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Oparin, D.V.; Pilipenko, G.I.; Tyutyunnik, O.I.; Gavrilov, F.F.; Sulimov, E.M. (Ural' skij Politekhnicheskij Inst., Sverdlovsk (USSR))

    1984-09-01

    Lithium hydride single crystals irradiated with neutrons were studied by the optical method. Wide bands belonging to the large F-aggregate and quasimetallic F-centres and to the metallic lithium colloids were discovered in the absorption spectra at room temperature. The small Fsub(n)-centres and molecular lithium centres were detected at 77 K. From the electron-vibrational structure of the absorption spectra of these centres the energies of acoustic phonons in X, W, L points of the Brillouin zone of lithium hydride have been found out: TA(L)-235 cm/sup -1/, TA(X)-27g cm/sup -1/, TA(W)-327 cm/sup -1/, LA(W)-384 cm/sup -1/, LA(X)-426 cm/sup -1/.

  16. Effects of confinement on the thermodynamics and kinetics of metal hydrides templated in ordered nanoporous frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, M.D.; Bhakta, R.; Behrens, R. Jr. [Sandia National Labs., Livermore, CA (United States); Majzoub, E.H.; Liu, X.; Peaslee, D. [Missouri Univ., St. Louis, MO (United States). Dept. of Physics and Astronomy; Herberg, J.L. [Lawrence Livermore National Labs., Livermore, CA (United States); Wagner, L.K.; Grossman, J.C. [Massachusetts Institute of Technology, Cambridge, MA (United States). Dept. of Materials Science and Engineering

    2010-07-01

    The objective of this work is to use Metal Organic Frameworks (MOFs) and Zeolitic Imidazolate Frameworks (ZIFs) as templates for the synthesis of metal hydride nanoparticles with controlled size and chemical environment to establish the origins of the nanoscale destabilization predicted by theory and reported experimentally. (orig.)

  17. An experimental design method leading to chemical Turing patterns.

    Science.gov (United States)

    Horváth, Judit; Szalai, István; De Kepper, Patrick

    2009-05-08

    Chemical reaction-diffusion patterns often serve as prototypes for pattern formation in living systems, but only two isothermal single-phase reaction systems have produced sustained stationary reaction-diffusion patterns so far. We designed an experimental method to search for additional systems on the basis of three steps: (i) generate spatial bistability by operating autoactivated reactions in open spatial reactors; (ii) use an independent negative-feedback species to produce spatiotemporal oscillations; and (iii) induce a space-scale separation of the activatory and inhibitory processes with a low-mobility complexing agent. We successfully applied this method to a hydrogen-ion autoactivated reaction, the thiourea-iodate-sulfite (TuIS) reaction, and noticeably produced stationary hexagonal arrays of spots and parallel stripes of pH patterns attributed to a Turing bifurcation. This method could be extended to biochemical reactions.

  18. 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...

  19. 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.

  20. Use of ab initio quantum chemical methods in battery technology

    Energy Technology Data Exchange (ETDEWEB)

    Deiss, E. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Ab initio quantum chemistry can nowadays predict physical and chemical properties of molecules and solids. An attempt should be made to use this tool more widely for predicting technologically favourable materials. To demonstrate the use of ab initio quantum chemistry in battery technology, the theoretical energy density (energy per volume of active electrode material) and specific energy (energy per mass of active electrode material) of a rechargeable lithium-ion battery consisting of a graphite electrode and a nickel oxide electrode has been calculated with this method. (author) 1 fig., 1 tab., 7 refs.

  1. Synthesis of Lead Sulfide Nanoparticles by Chemical Precipitation Method

    Science.gov (United States)

    Chongad, L. S.; Sharma, A.; Banerjee, M.; Jain, A.

    2016-10-01

    Lead sulfide (PbS) nanoparticles were prepared by chemical precipitation method (CPM) with the assistance of H2S gas. The microstructure and morphology of the synthesized nanoparticles have been investigated using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the PbS nanoparticles reveal formation of cubic phase. To investigate the quality of prepared nanoparticles, the particles size, lattice constant, strain, dislocation density etc. have been determined using XRD. TEM images reveal formation of cubic nanoparticles and the particle size determined from TEM images agree well with those from XRD.

  2. 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.

  3. Quantification of geopolymers production by chemical methods- A short review

    Science.gov (United States)

    Siyal, Ahmer Ali; Azizli, Khairun Azizi; Ismail, Lukman; Man, Zakaria; Khan, Muhammad Irfan

    2015-07-01

    Inorganic polymers are the aluminosilicate materials possessing properties superior than ordinary Portland cement. In this review paper the chemical techniques used for determining degree of reaction of fly ash or the quantity of geopolymer material produced have been discussed. These methods determine the amount of product formed in percentages. The methods include HCl method, salicylic acid method, and picric acid method. These methods are not only used for fly ash but they are being used for determining the degree of reactions of metakaolin and other pozzolanic materials. The picric acid is an explosive material and its transportation in high concentration is dangerous. During its use in laboratory there is also the risk of fire associated with it. According to the microscopic analysis results the picric acid attack dissolves small amount of fine unreacted fly ash particles also. The salicylic acid is easily available but the residue from its treatment contains unreacted fly ash particles, hydration phases, and certain parts of unreacted OPC. The residue from HCl and salicylic acid attack contains MgO particles which is the part of the hydration product. The HCl method is mostly used due to simple process and lower standard deviation.

  4. Strain evolution during hydride precipitation in Zircaloy-4 observed with synchrotron X-ray diffraction

    Science.gov (United States)

    Blackmur, M. S.; Preuss, M.; Robson, J. D.; Zanellato, O.; Cernik, R. J.; Ribeiro, F.; Andrieux, J.

    2016-06-01

    Synchrotron X-ray diffraction was used to evaluate strain evolution observed in Zircaloy-4 undergoing hydride precipitation during a range of thermal operations. During continuous heating, a change in the constraining effect of the matrix was observed at a temperature of 280 °C, thought to be the result of matrix dilatation from interstitial hydrogen. A deconvolution of the thermal, chemical and mechanical sources of strain during quench and dwell operations identified a non-negligible mechanical effect in the matrix. During these dwells, slow strain rate relaxation of elastic strains was seen in the matrix and hydride, suggesting that time dependent relaxation of misfit stresses may be possible at reactor relevant temperatures. Notable anisotropy was observed between the rolling and transverse directions, identified as being the likely product of a similar anisotropy in the relaxation of the hydride misfit between the α and α matrix directions, owing to the differing coherency of these two interfaces.

  5. 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...

  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. 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

  8. On Chemical Modeling an Alchemical Process: The Use of Combined Chemical Methods in a Historical Study

    Science.gov (United States)

    Rodygin, Mikhail Yu.; Rodygin, Irene V.

    1997-08-01

    Laboratory work is an important component of a course in the History of Chemistry and Alchemy, though it can only be illustrative and not comprehensive. The course should exercise both the cognitive and research abilities of an university student. Therefore methods of modeling are of prime importance at this stage of instruction. Modeling can be both a priori and experimental. The experiment can use the alchemist's materials, or it can reproduce the procedure with modern reagents. A good example for the use of this method is a recipe for the preparation of the Philosopher's Stone attributed to Lullius and cited by J. Ripley in Liber Duodecium Portarum. Thus, the Ripley's recipe is not only considered to be the first indication of the existence of acetone, but it may also indicate the formation of acetyl acetone and its derivatives. Thus, as far as the history of alchemy is concerned, the use of an experimental model not only allows us to solve a number of specific problems such as recipe interpretation and product identification, but it allows also to probe the essence of alchemical work. The combination of empirical and speculative modelings leads to the interaction of the exact methods of chemistry with the broad historico-chemical generalizations, thus introducing some additional dimensions to the definition of historico-chemical practice.

  9. 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

  10. An adaptive stepsize method for the chemical Langevin equation.

    Science.gov (United States)

    Ilie, Silvana; Teslya, Alexandra

    2012-05-14

    Mathematical and computational modeling are key tools in analyzing important biological processes in cells and living organisms. In particular, stochastic models are essential to accurately describe the cellular dynamics, when the assumption of the thermodynamic limit can no longer be applied. However, stochastic models are computationally much more challenging than the traditional deterministic models. Moreover, many biochemical systems arising in applications have multiple time-scales, which lead to mathematical stiffness. In this paper we investigate the numerical solution of a stochastic continuous model of well-stirred biochemical systems, the chemical Langevin equation. The chemical Langevin equation is a stochastic differential equation with multiplicative, non-commutative noise. We propose an adaptive stepsize algorithm for approximating the solution of models of biochemical systems in the Langevin regime, with small noise, based on estimates of the local error. The underlying numerical method is the Milstein scheme. The proposed adaptive method is tested on several examples arising in applications and it is shown to have improved efficiency and accuracy compared to the existing fixed stepsize schemes.

  11. Method for fractional solid-waste sampling and chemical analysis

    DEFF Research Database (Denmark)

    Riber, Christian; Rodushkin, I.; Spliid, Henrik

    2007-01-01

    to repeated particle-size reduction, mixing, and mass reduction until a sufficiently small but representative sample was obtained for digestion prior to chemical analysis. The waste-fraction samples were digested according to their properties for maximum recognition of all the studied substances. By combining...... four subsampling methods and five digestion methods, paying attention to the heterogeneity and the material characteristics of the waste fractions, it was possible to determine 61 substances with low detection limits, reasonable variance, and high accuracy. For most of the substances of environmental...... concern, the waste-sample concentrations were above the detection limit (e.g. Cd gt; 0.001 mg kg-1, Cr gt; 0.01 mg kg-1, Hg gt; 0.002 mg kg-1, Pb gt; 0.005 mg kg-1). The variance was in the range of 5-100%, depending on material fraction and substance as documented by repeated sampling of two highly...

  12. Automated determinations of selenium in thermal power plant wastewater by sequential hydride generation and chemiluminescence detection.

    Science.gov (United States)

    Ezoe, Kentaro; Ohyama, Seiichi; Hashem, Md Abul; Ohira, Shin-Ichi; Toda, Kei

    2016-02-01

    After the Fukushima disaster, power generation from nuclear power plants in Japan was completely stopped and old coal-based power plants were re-commissioned to compensate for the decrease in power generation capacity. Although coal is a relatively inexpensive fuel for power generation, it contains high levels (mgkg(-1)) of selenium, which could contaminate the wastewater from thermal power plants. In this work, an automated selenium monitoring system was developed based on sequential hydride generation and chemiluminescence detection. This method could be applied to control of wastewater contamination. In this method, selenium is vaporized as H2Se, which reacts with ozone to produce chemiluminescence. However, interference from arsenic is of concern because the ozone-induced chemiluminescence intensity of H2Se is much lower than that of AsH3. This problem was successfully addressed by vaporizing arsenic and selenium individually in a sequential procedure using a syringe pump equipped with an eight-port selection valve and hot and cold reactors. Oxidative decomposition of organoselenium compounds and pre-reduction of the selenium were performed in the hot reactor, and vapor generation of arsenic and selenium were performed separately in the cold reactor. Sample transfers between the reactors were carried out by a pneumatic air operation by switching with three-way solenoid valves. The detection limit for selenium was 0.008 mg L(-1) and calibration curve was linear up to 1.0 mg L(-1), which provided suitable performance for controlling selenium in wastewater to around the allowable limit (0.1 mg L(-1)). This system consumes few chemicals and is stable for more than a month without any maintenance. Wastewater samples from thermal power plants were collected, and data obtained by the proposed method were compared with those from batchwise water treatment followed by hydride generation-atomic fluorescence spectrometry.

  13. Thermodynamics of various F420 coenzyme models as sources of electrons, hydride ions, hydrogen atoms and protons in acetonitrile.

    Science.gov (United States)

    Xia, Ke; Shen, Guang-Bin; Zhu, Xiao-Qing

    2015-06-14

    32 F420 coenzyme models with alkylation of the three different N atoms (N1, N3 and N10) in the core structure (XFH(-)) were designed and synthesized and the thermodynamic driving forces (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the 32 XFH(-) releasing hydride ions, hydrogen atoms and electrons, the thermodynamic driving forces of the 32 XFH˙ releasing protons and hydrogen atoms and the thermodynamic driving forces of XF(-)˙ releasing electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The effects of the methyl group at N1, N3 and N10 and a negative charge on N1 and N10 atoms on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were examined; the results show that seating arrangements of the methyl group and the negative charge have remarkably different effects on the thermodynamic properties of the F420 coenzyme models and their related reaction intermediates. The effects of the substituents at C7 and C8 on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were also examined; the results show that the substituents at C7 and C8 have good Hammett linear free energy relationships with the six thermodynamic parameters. Meanwhile, a reasonable determination of possible reactions between members of the F420 family and NADH family in vivo was given according to a thermodynamic analysis platform constructed using the elementary step thermodynamic parameter of F420 coenzyme model 2FH(-) and NADH model MNAH releasing hydride ions in acetonitrile. The information disclosed in this work can not only fill a gap in the chemical thermodynamics of F420 coenzyme models as a class of very important organic sources of electrons, hydride ions, hydrogen atoms and protons, but also strongly promote the fast development of the chemistry and applications of F420 coenzyme.

  14. High-Spin Cobalt Hydrides for Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Patrick L. [Univ. of Rochester, NY (United States)

    2013-08-29

    Organometallic chemists have traditionally used catalysts with strong-field ligands that give low-spin complexes. However, complexes with a weak ligand field have weaker bonds and lower barriers to geometric changes, suggesting that they may lead to more rapid catalytic reactions. Developing our understanding of high-spin complexes requires the use of a broader range of spectroscopic techniques, but has the promise of changing the mechanism and/or selectivity of known catalytic reactions. These changes may enable the more efficient utilization of chemical resources. A special advantage of cobalt and iron catalysts is that the metals are more abundant and cheaper than those currently used for major industrial processes that convert unsaturated organic molecules and biofeedstocks into useful chemicals. This project specifically evaluated the potential of high-spin cobalt complexes for small-molecule reactions for bond rearrangement and cleavage reactions relevant to hydrocarbon transformations. We have learned that many of these reactions proceed through crossing to different spin states: for example, high-spin complexes can flip one electron spin to access a lower-energy reaction pathway for beta-hydride elimination. This reaction enables new, selective olefin isomerization catalysis. The high-spin cobalt complexes also cleave the C-O bond of CO2 and the C-F bonds of fluoroarenes. In each case, the detailed mechanism of the reaction has been determined. Importantly, we have discovered that the cobalt catalysts described here give distinctive selectivities that are better than known catalysts. These selectivities come from a synergy between supporting ligand design and electronic control of the spin-state crossing in the reactions.

  15. 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.

  16. 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...

  17. Hydrogen storage alloys rapidly solidified by the melt-spinning method and their characteristics as metal hydride electrodes. [LaNiAl; LaNiCoAl

    Energy Technology Data Exchange (ETDEWEB)

    Mishima, R. (Mitsubishi Kasei Corp., Research Center, Yokohama (Japan)); Miyamura, H. (Government Industrial Research Inst., Osaka (Japan)); Sakai, T. (Government Industrial Research Inst., Osaka (Japan)); Kuriyama, N. (Government Industrial Research Inst., Osaka (Japan)); Ishikawa, H. (Government Industrial Research Inst., Osaka (Japan)); Uehara, I. (Government Industrial Research Inst., Osaka (Japan))

    1993-02-23

    Rapidly solidified LaNi[sub 5]-based hydrogen storage alloys were prepared by a melt-spinning method. The prepared melt-spun alloy ribbon had very fine crystal grain of below 10 [mu]m. The hydrogen absorption behavior and electrode properties of the alloys were greatly improved. Heat treatment at 400 C which did not cause enlargement of the grain further improved these properties. (orig.)

  18. 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...

  19. Obtention of the constitutive equation of hydride blisters in fuel cladding from nanoindentation tests

    Science.gov (United States)

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

    2017-04-01

    It is well known that the presence of hydrides in nuclear fuel cladding may reduce its mechanical and fracture properties. This situation may be worsened as a consequence of the formation of hydride blisters. These blisters are zones with an extremely high hydrogen concentration and they are usually associated to the oxide spalling which may occur at the outer surface of the cladding. In this work, a method which allows us to reproduce, in a reliable way, hydride blisters in the laboratory has been devised. Depth-sensing indentation tests with a spherical indenter were conducted on a hydride blister produced in the laboratory with the aim of measuring its mechanical behaviour. The plastic stress-strain curve of the hydride blister was calculated for first time by combining depth-sensing indentation tests results with an iterative algorithm using finite element simulations. The algorithm employed reduces, in each iteration, the differences between the numerical and the experimental results by modifying the stress-strain curve. In this way, an almost perfect adjustment of the experimental data was achieved after several iterations. The calculation of the constitutive equation of the blister from nanoindentation tests, may involve a lack of uniqueness. To evaluate it, a method based on the optimization of parameters of analytical equations has been proposed in this paper. An estimation of the error which involves this method is also provided.

  20. 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)

  1. Method of waste stabilization with dewatered chemically bonded phosphate ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Wagh, Arun; Maloney, Martin D.

    2010-06-29

    A method of stabilizing a waste in a chemically bonded phosphate ceramic (CBPC). The method consists of preparing a slurry including the waste, water, an oxide binder, and a phosphate binder. The slurry is then allowed to cure to a solid, hydrated CBPC matrix. Next, bound water within the solid, hydrated CBPC matrix is removed. Typically, the bound water is removed by applying heat to the cured CBPC matrix. Preferably, the quantity of heat applied to the cured CBPC matrix is sufficient to drive off water bound within the hydrated CBPC matrix, but not to volatalize other non-water components of the matrix, such as metals and radioactive components. Typically, a temperature range of between 100.degree. C.-200.degree. C. will be sufficient. In another embodiment of the invention wherein the waste and water have been mixed prior to the preparation of the slurry, a select amount of water may be evaporated from the waste and water mixture prior to preparation of the slurry. Another aspect of the invention is a direct anyhydrous CBPC fabrication method wherein water is removed from the slurry by heating and mixing the slurry while allowing the slurry to cure. Additional aspects of the invention are ceramic matrix waste forms prepared by the methods disclosed above.

  2. Method of waste stabilization with dewatered chemically bonded phosphate ceramics

    Science.gov (United States)

    Wagh, Arun; Maloney, Martin D.

    2010-06-29

    A method of stabilizing a waste in a chemically bonded phosphate ceramic (CBPC). The method consists of preparing a slurry including the waste, water, an oxide binder, and a phosphate binder. The slurry is then allowed to cure to a solid, hydrated CBPC matrix. Next, bound water within the solid, hydrated CBPC matrix is removed. Typically, the bound water is removed by applying heat to the cured CBPC matrix. Preferably, the quantity of heat applied to the cured CBPC matrix is sufficient to drive off water bound within the hydrated CBPC matrix, but not to volatalize other non-water components of the matrix, such as metals and radioactive components. Typically, a temperature range of between 100.degree. C.-200.degree. C. will be sufficient. In another embodiment of the invention wherein the waste and water have been mixed prior to the preparation of the slurry, a select amount of water may be evaporated from the waste and water mixture prior to preparation of the slurry. Another aspect of the invention is a direct anyhydrous CBPC fabrication method wherein water is removed from the slurry by heating and mixing the slurry while allowing the slurry to cure. Additional aspects of the invention are ceramic matrix waste forms prepared by the methods disclosed above.

  3. Chemoinformatics and chemical genomics: potential utility of in silico methods.

    Science.gov (United States)

    Valerio, Luis G; Choudhuri, Supratim

    2012-11-01

    Computational life sciences and informatics are inseparably intertwined and they lie at the heart of modern biology, predictive quantitative modeling and high-performance computing. Two of the applied biological disciplines that are poised to benefit from such progress are pharmacology and toxicology. This review will describe in silico chemoinformatics methods such as (quantitative) structure-activity relationship modeling and will overview how chemoinformatic technologies are considered in applied regulatory research. Given the post-genomics era and large-scale repositories of omics data that are available, this review will also address potential applications of in silico techniques in chemical genomics. Chemical genomics utilizes small molecules to explore the complex biological phenomena that may not be not amenable to straightforward genetic approach. The reader will gain the understanding that chemoinformatics stands at the interface of chemistry and biology with enabling systems for mapping, statistical modeling, pattern recognition, imaging and database tools. The great potential of these technologies to help address complex issues in the toxicological sciences is appreciated with the applied goal of the protection of public health.

  4. Quantum confinement of lead titanate nanocrystals by wet chemical method

    Energy Technology Data Exchange (ETDEWEB)

    Kaviyarasu, K., E-mail: kaviyarasuloyolacollege@gmail.com [UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA), Muckleneuk Ridge, P O Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa); Manikandan, E., E-mail: maniphysics@gmail.com [Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa); Central Research Laboratory, Sree Balaji Medical College & Hospital, Bharath University, Chrompet, Chennai, Tamil Nadu (India); Nuru, Z.Y. [UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA), Muckleneuk Ridge, P O Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa); Maaza, M., E-mail: likmaaz@gmail.com [UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA), Muckleneuk Ridge, P O Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa)

    2015-11-15

    Lead Titanate (PbTiO{sub 3)} is a category of the practical semiconductor metal oxides, which is widely applied in various scientific and industrial fields because of its catalytic, optical, and electrical properties. PbTiO{sub 3} nanocrystalline materials have attracted a wide attention due to their unique properties. PbTiO{sub 3} nanocrystals were investigated by X-ray diffraction (XRD) to identify the PbTiO{sub 3} nanocrystals were composed a tetragonal structure. The diameter of a single sphere was around 20 nm and the diameter reached up to 3 μm. The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS) in detail. - Highlights: • Single crystalline NSs of PbTiO{sub 3} fabricated by wet chemical method. • PbTiO{sub 3} NSs were uniform and continuous along the long axis. • Tetragonal perovskite structure with the diameter 20 nm and length 3 μm. • XPS spectrum was fitted with Lorentzian function respectively. • The size of the images is also 10 μm × 10 μm.

  5. 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.

  6. Proton and hydride affinities in excited states: magnitude reversals in proton and hydride affinities between the lowest singlet and triplet states of annulenyl and benzannulenyl anions and cations

    DEFF Research Database (Denmark)

    Rosenberg, Martin; Ottosson, Henrik; Kilså, Kristine

    2010-01-01

    Aromaticity has importance for proton and hydride affinities in the singlet ground state (S(0)) of annulenyl anions and cations so that, e.g., cyclopentadiene is an acidic hydrocarbon. For the lowest pipi* excited triplet state (T(1)), Baird's rule concludes that annulenes with 4n pi-electrons ar......Aromaticity has importance for proton and hydride affinities in the singlet ground state (S(0)) of annulenyl anions and cations so that, e.g., cyclopentadiene is an acidic hydrocarbon. For the lowest pipi* excited triplet state (T(1)), Baird's rule concludes that annulenes with 4n pi......-electrons are aromatic and those with 4n+2 pi-electrons are antiaromatic, opposite to Huckel's rule for aromaticity in S(0). Our hypothesis is now that the relative magnitudes of proton and hydride affinities of annulenyl anions and cations reverts systematically as one goes from S(0) to T(1) as a result of the opposite...... electron counting rules for aromaticity in the two states. Using quantum chemical calculations at the G3(MP2)//(U)B3LYP/6-311+G(d,p) level we have examined the validity of this hypothesis for eight proton and eight hydride addition reactions of anions and cations, respectively, of annulenyl...

  7. 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 ...

  8. Preparation of calcium stannate by modified wet chemical method

    Institute of Scientific and Technical Information of China (English)

    何则强; 李新海; 刘恩辉; 侯朝辉; 邓凌峰; 胡传跃

    2003-01-01

    A modified wet chemical route for low-temperature synthesis of the calcium stannate CaSnO3, a potentialmaterial for dielectric applications is reported. Firstly, a precursor CaSn(OH)6 was prepared using tin tetrachloride,calcium chloride and sodium hydroxide at room temperature. Then the precursor was annealed at relatively low tem-perature of 600 ℃ to obtain CaSnO3. The phase identification, thermal behavior and surface morphology of the sam-ples were characterized by element analysis, X-ray diffraction (XRD), thermo-gravimetric (TG) analysis and deriva-tive thermo-gravimetric (DTG) analysis, Fourier transform infrared spectroscopy (FTIR) and scanning electron mi-croscopy (SEM) in detail. The results show that CaSnO3 obtained by this method possesses a cubic perovskitestructure with average grain size of 5 μm.

  9. 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....

  10. High Density Hydrogen Storage in Metal Hydride Composites with Air Cooling

    OpenAIRE

    Dieterich, Mila; Bürger, Inga; Linder, Marc

    2015-01-01

    INTRODUCTION In order to combine fluctuating renewable energy sources with the actual demand of electrical energy, storages are essential. The surplus energy can be stored as hydrogen to be used either for mobile use, chemical synthesis or reconversion when needed. One possibility to store the hydrogen gas at high volumetric densities, moderate temperatures and low pressures is based on a chemical reaction with metal hydrides. Such storages must be able to absorb and desorb the hydrogen qu...

  11. Theoretical Chemical Thermometry on Geothermal Waters: Problems and Methods

    Science.gov (United States)

    Pang, Zhong-He; Reed, Mark

    1998-03-01

    Using a synthetic geothermal water, we examine the effect of errors in Al analyses on theoretical chemical geothermometry based on multicomponent chemical equilibrium calculations of mineral equilibria. A new approach named FixAl that entails the construction of a modified Q/K graph eliminates problems with water analyses lacking Al or with erroneous analyses of Al. This is made possible by forcing the water to be at equilibrium with a selected Al-bearing mineral, such as microcline. In a FixAl graph, a modified Q/K value is plotted against temperature for Al-bearing minerals. Saturation indices of nonaluminous minerals are plotted in the same way as in an ordinary Q/K graph. In addition to Al concentration errors, degassing of CO 2 and dilution of reservoir water interfere with computed equilibrium geothermometry. These effects can be distinguished in a Q/K graph by comparing curves for nonaluminous minerals to those of aluminous minerals then correcting for CO 2 loss and dilution by a trial and error method. Example geothermal waters from China, Iceland, and the USA that are used to demonstrate the methods show that errors in Al concentrations are common, and some are severe. The FixAl approach has proved useful for chemical geothermometry for geothermal waters lacking Al analysis and for waters with an incorrect Al analysis. The equilibrium temperatures estimated by the FixAl approach agree well with quartz, chalcedony, and isotopic geothermometers. The best choice of mineral for forced equilibrium depends on pH. For most neutral pH waters, microcline and albite work well; for more acidic waters, kaolinite or illite are good choices. Measured pH plays a critical role in computed equilibria, and we find that the best pH to use is the one to which the reported carbonate also applies. Commonly this is the laboratory pH instead of field pH, but the field pH is still necessary to constrain CO 2 degassing. Calculations on numerous waters in the 80-180°C reservoir

  12. Using nuclear chemical method for synthesizing unknown organic onium compounds

    Energy Technology Data Exchange (ETDEWEB)

    Nefedov, V.D.; Toropova, M.A.; Shchepina, N.Y.; Avrorin, V.V.; Zhuravlev, V.Ye.

    1982-05-01

    While considerable research has been done on organic onium derivatives, a number of compounds, including ones with halogens other than iodine, have not been produced. The authors applied the nuclear chemical method they previously proposed (Soviet patents) in synthesizing tetraphenyl-ammonium and diphenylfuoronium compounds. The method involves directed ion-molecular reactions of tritium-treated phenyl cations obtained in the beta-decomposition of tritium in the framework of tritium-treated benzene with phenyl derivatives of the elements being studied. Ion-molecular reactions were conducted in sealed ampules containing the reactive mass of treated benzene (the phenyl-cation source), phenyl derivatives of nitrogen and fluorine as substrates, and salts of inorganic KBF/sub 4/ or KI. Thin layer chromatography was used to identify the onium compounds obtained. Low yields in earlier tests of the derivative of tetraphenylammonium were apparently due to severe spatial difficulties; these difficulties were reduced in the present method by replacing phenyl groups with methyl groups, and much improved yields resulted. Evidence from chromatography confirms the identical molecular structures of the treated onium derivatives obtained and corresponding onium compounds of analogous phosphorus and bromine.

  13. 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.

  14. Hydride heat pump. Volume I. Users manual for HYCSOS system design program. [HYCSOS code

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, R.; Moritz, P.

    1978-05-01

    A method for the design and costing of a metal hydride heat pump for residential use and a computer program, HYCSOS, which automates that method are described. The system analyzed is one in which a metal hydride heat pump can provide space heating and space cooling powered by energy from solar collectors and electric power generated from solar energy. The principles and basic design of the system are presented, and the computer program is described giving detailed design and performance equations used in the program. The operation of the program is explained, and a sample run is presented. This computer program is part of an effort to design, cost, and evaluate a hydride heat pump for residential use. The computer program is written in standard Fortran IV and was run on a CDC Cyber 74 and Cyber 174 computer. A listing of the program is included as an appendix. This report is Volume 1 of a two-volume document.

  15. Articles of protective clothing adapted for deflecting chemical permeation and methods therefor

    Science.gov (United States)

    Vo-Dinh, Tuan

    1996-01-01

    Apparatus and methods for detecting the permeation of hazardous or toxic chemicals through protective clothing are disclosed. The hazardous or toxic chemicals of interest do not possess the spectral characteristic of luminescence. The apparatus and methods utilize a spectrochemical modification technique to detect the luminescence quenching of an indicator compound which upon permeation of the chemical through the protective clothing, the indicator is exposed to the chemical, thus indicating chemical permeation.

  16. Method and apparatus for hydrogen production from water

    Science.gov (United States)

    Muradov, Nazim Z. (Inventor)

    2012-01-01

    A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

  17. Computational study of sodium magnesium hydride for hydrogen storage applications

    Science.gov (United States)

    Soto Valle, Fernando Antonio

    Hydrogen offers considerable potential benefits as an energy carrier. However, safe and convenient storage of hydrogen is one of the biggest challenges to be resolved in the near future. Sodium magnesium hydride (NaMgH 3) has attracted attention as a hydrogen storage material due to its light weight and high volumetric hydrogen density of 88 kg/m3. Despite the advantages, hydrogen release in this material occurs at approximately 670 K, which is well above the operable range for on-board hydrogen storage applications. In this regard, hydrogen release may be facilitated by substitution doping of transition-metals. This dissertation describes first-principles computational methods that enable an examination of the hydrogen storage properties of NaMgH3. The novel contribution of this dissertation includes a combination of crystal, supercell, and surface slab calculations that provides new and relevant insights about the thermodynamic and kinetic properties of NaMgH3. First-principles calculations on the pristine crystal structure provide a starting reference point for the study of this material as a hydrogen storage material. To the best of our knowledge, it is reported for the first time that a 25% mol doping concentration of Ti, V, Cu, and Zn dopants reduce the reaction enthalpy of hydrogen release for NaMgH3. The largest decrease in the DeltaH(298 K) value corresponds to the Zn-doped model (67.97 kJ/(mol H2)). Based on cohesive energy calculations, it is reported that at the 6.25% mol doping concentration, Ti and Zn dopants are the only transition metals that destabilize the NaMgH3 hydride. In terms of hydrogen removal energy, it is quantified that the energy cost to remove a single H from the Ti-doped supercell model is 0.76 eV, which is lower with respect to the pristine model and other prototypical hydrogen storage materials. From the calculation of electronic properties such as density of states, electron density difference, and charge population analysis

  18. Chemical-potential-based Lattice Boltzmann Method for Nonideal Fluids

    CERN Document Server

    Wen, Binghai; He, Bing; Zhang, Chaoying; Fang, Haiping

    2016-01-01

    Chemical potential is an effective way to drive phase transition or express wettability. In this letter, we present a chemical-potential-based lattice Boltzmann model to simulate multiphase flows. The nonideal force is directly evaluated by a chemical potential. The model theoretically satisfies thermodynamics and Galilean invariance. The computational efficiency is improved owing to avoiding the calculation of pressure tensor. We have derived several chemical potentials of the popular equations of state from the free-energy density function. An effective chemical-potential boundary condition is implemented to investigate the wettability of a solid surface. Remarkably, the numerical results show that the contact angle can be linearly tuned by the surface chemical potential.

  19. 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.

  20. 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.

  1. 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.

  2. 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)

  3. Tailoring Thermodynamics and Kinetics for Hydrogen Storage in Complex Hydrides towards Applications.

    Science.gov (United States)

    Liu, Yongfeng; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge

    2016-02-01

    Solid-state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on-board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high-performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage.

  4. (abstract) Studies on AB(sub 5) Metal Hydride Alloys with Sn Additives

    Science.gov (United States)

    Ratnakumar, B. V.; Surampudi, S.; Stefano, S. Di; Halpert, G.; Witham, C.; Fultz, B.

    1994-01-01

    The use of metal hydrides as negative electrodes in alkaline rechargeable cells is becoming increasingly popular, due to several advantages offered by the metal hydrides over conventional anode materials (such as Zn, Cd) in terms of specific energy environmental cycle life and compatibility. Besides, the similarities in the cell voltage pressure characteristics, and charge control methods of the Ni-MH cells to the commonly used Ni-Cd point to a projected take over of 25% of the Ni-Cd market for consumer electronics by the Ni-MH cells in the next couple of years. Two classes of metal hydrides alloys based on rare earth metals (AB(sub 5)) and titanium (AB(sub 2)) are being currently developed at various laboratories. AB(sub 2) alloys exhibit higher specific energy than the AB(sub 5) alloys but the state of the art commercial Ni-MH cells are predominately manufactured using AB(sub 5) alloys.

  5. Amineborane Based Chemical Hydrogen Storage - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sneddon, Larry G.

    2011-04-21

    The development of efficient and safe methods for hydrogen storage is a major hurdle that must be overcome to enable the use of hydrogen as an alternative energy carrier. The objectives of this project in the DOE Center of Excellence in Chemical Hydride Storage were both to develop new methods for on-demand, low temperature hydrogen release from chemical hydrides and to design high-conversion off-board methods for chemical hydride regeneration. Because of their reactive protic (N-H) and hydridic (B-H) hydrogens and high hydrogen contents, amineboranes such as ammonia borane, NH3BH3 (AB), 19.6-wt% H2, and ammonia triborane NH3B3H7 (AT), 17.7-wt% H2, were initially identified by the Center as promising, high-capacity chemical hydrogen storage materials with the potential to store and deliver molecular hydrogen through dehydrogenation and hydrolysis reactions. In collaboration with other Center partners, the Penn project focused both on new methods to induce amineborane H2-release and on new strategies for the regeneration the amineborane spent-fuel materials. The Penn approach to improving amineborane H2-release focused on the use of ionic liquids, base additives and metal catalysts to activate AB dehydrogenation and these studies successfully demonstrated that in ionic liquids the AB induction period that had been observed in the solid-state was eliminated and both the rate and extent of AB H2-release were significantly increased. These results have clearly shown that, while improvements are still necessary, many of these systems have the potential to achieve DOE hydrogen-storage goals. The high extent of their H2­-release, the tunability of both their H2 materials weight-percents and release rates, and their product control that is attained by either trapping or suppressing unwanted volatile side products, such as borazine, continue to make AB/ionic­-liquid based systems attractive candidates for chemical hydrogen storage applications. These studies also

  6. Determination of arsenic in a nickel alloy by flow injection hydride generation atomic absorption spectrometry

    Science.gov (United States)

    Hanna, C. P.; Tyson, J. F.; Offley, S. G.

    1992-08-01

    The development of a method for the direct determination of trace arsenic quantities in nickel alloy digests, by flow injection hydride generation atomic absorption spectrometry, is described. An optimization study of the manifold and chemical parameters produced system performance, in terms of tolerance of the nickel matrix and sensitivity, such that matrix removal and pre-reduction of As(V) to As (III) prior to arsine generation were eliminated. Full recovery of the As(V) signal from a solution containing 5 ng ml -1 in the presence of 60 μg ml -1 nickel was obtained. Validation of the method was achieved by analyzing a British Chemical Standard (BCS) Certified Reference Material (CRM) #346 IN nickel alloy containing arsenic at a concentration of 50 μg g -1. Following dissolution in nitric and hydrofluoric acids by a microwave assisted procedure, the only subsequent preparation required was dilution by the appropriate factor. Up to 60 injections h -1 may be made, with a detection limit of 0.5 ng ml -1 arsenic (250 pg absolute) as As(V) in a 500 μl sample. The peak height characteristic concentration is 0.46 ng ml -1, with a relative standard deviation of 3.5% for a 10 ng ml -1 As(V) standard ( n = 6).

  7. ACCEPTABILITY ENVELOPE FOR METAL HYDRIDE-BASED HYDROGEN STORAGE SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    Hardy, B.; Corgnale, C.; Tamburello, D.; Garrison, S.; Anton, D.

    2011-07-18

    The design and evaluation of media based hydrogen storage systems requires the use of detailed numerical models and experimental studies, with significant amount of time and monetary investment. Thus a scoping tool, referred to as the Acceptability Envelope, was developed to screen preliminary candidate media and storage vessel designs, identifying the range of chemical, physical and geometrical parameters for the coupled media and storage vessel system that allow it to meet performance targets. The model which underpins the analysis allows simplifying the storage system, thus resulting in one input-one output scheme, by grouping of selected quantities. Two cases have been analyzed and results are presented here. In the first application the DOE technical targets (Year 2010, Year 2015 and Ultimate) are used to determine the range of parameters required for the metal hydride media and storage vessel. In the second case the most promising metal hydrides available are compared, highlighting the potential of storage systems, utilizing them, to achieve 40% of the 2010 DOE technical target. Results show that systems based on Li-Mg media have the best potential to attain these performance targets.

  8. 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.

  9. Control and optimization system and method for chemical looping processes

    Science.gov (United States)

    Lou, Xinsheng; Joshi, Abhinaya; Lei, Hao

    2015-02-17

    A control system for optimizing a chemical loop system includes one or more sensors for measuring one or more parameters in a chemical loop. The sensors are disposed on or in a conduit positioned in the chemical loop. The sensors generate one or more data signals representative of an amount of solids in the conduit. The control system includes a data acquisition system in communication with the sensors and a controller in communication with the data acquisition system. The data acquisition system receives the data signals and the controller generates the control signals. The controller is in communication with one or more valves positioned in the chemical loop. The valves are configured to regulate a flow of the solids through the chemical loop.

  10. Comparison between different reactions of group IV hydride with H

    Institute of Scientific and Technical Information of China (English)

    ZHANG; Shaolong; ZHANG; Xuqiang; ZHANG; Qinggang; ZHANG; Yici

    2006-01-01

    The four-dimensional time-dependent quantum dynamics calculations for reactions of group IV hydride with H are carried out by employing the semirigid vibrating rotor target model and the time-dependent wave packet method. The reaction possibility, cross section and rate constants for reactions (H+SiH4 and H+GeH4) in different initial vibrational and rotational states are obtained. The common feature for such kind of reaction process is summarized. The theoretical result is consistent with available measurement, which indicates the credibility of this theory and the potential energy surface.

  11. Physical-chemical property based sequence motifs and methods regarding same

    Science.gov (United States)

    Braun, Werner [Friendswood, TX; Mathura, Venkatarajan S [Sarasota, FL; Schein, Catherine H [Friendswood, TX

    2008-09-09

    A data analysis system, program, and/or method, e.g., a data mining/data exploration method, using physical-chemical property motifs. For example, a sequence database may be searched for identifying segments thereof having physical-chemical properties similar to the physical-chemical property motifs.

  12. 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.

  13. Ab initio study of magnesium and magnesium hydride nanoclusters and nanocrystals: examining optimal structures and compositions for efficient hydrogen storage.

    Science.gov (United States)

    Koukaras, Emmanuel N; Zdetsis, Aristides D; Sigalas, Michael M

    2012-09-26

    On the basis of the attractive possibility of efficient hydrogen storage in light metal hydrides, we have examined a large variety of Mg(n)H(m) nanoclusters and (MgH(2))(n) nanocrystals (n = 2-216, m = 2-436) using high level coupled cluster, CCSD(T), ab initio methods, and judicially chosen density functional calculations of comparable quality and (near chemical) accuracy. Our calculated desorption energies as a function of size and percentage of hydrogen have pinpointed optimal regions of sizes and concentrations of hydrogen which are in full agreement with recent experimental findings. Furthermore, our results reproduce the experimental desorption energy of 75.5 kJ/mol for the infinite system with remarkable accuracy (76.5 ± 1.5 kJ/mol).

  14. First-principles LDA + U calculations investigating the lattice contraction of face-centered cubic Pu hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Ao, B.Y., E-mail: aobingyun24@yahoo.com.cn [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China); Wang, X.L.; Shi, P.; Chen, P.H.; Ye, X.Q.; Lai, X.C. [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China); Gao, T., E-mail: gaotao@scu.edu.cn [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065 (China)

    2012-05-15

    Plutonium metal can be loaded with hydrogen, which forms complicated solid solutions and compounds, and leads to significant changes in electronic structure. A first-principles pseudopotential plane wave method with added Hubbard parameter U was employed to investigate the electronic and structural properties of face-centered cubic Pu hydrides (PuH{sub x}, x = 2, 2.25, and 3). The decrease in calculated lattice parameters with increasing x is in reasonable agreement with experimental findings. Comparative analysis of the electronic-structure results for a series of PuH{sub x} compositions reveals that lattice contraction occurs due to enhanced chemical bonding and the size effects involving interstitial atoms. We find that the size effects are the driving force for the abnormal lattice contraction.

  15. Effects of Biofertilizer Application Method with Integrated Chemical Fertilizers on Maize Production and Some Chemical Characteristics of Soil

    Directory of Open Access Journals (Sweden)

    F Ebrahimpour

    2012-07-01

    Full Text Available In order to study the effects of integrated application of bio-fertilizer and chemical fertilizers on yield and yield components of corn, an experiment was conducted in 2008 in Dezful city, (Khoozestan province in a factorial arrangement based on complete randomized block design with four replications. Treatments were integrated application of biological and chemical fertilizers in four levels (100% chemical fertilizer, 50% chemical fertilizer+ bio-fertilizer, 25% chemical fertilizer + bio-fertilizer and bio-fertilizer and bio-fertilizer application method in three levels (seed inoculation, fertigation, seed inoculation+fertigation. The results showed that highest and the lowest grain yield was obtained by application of 50% chemical fertilizer+ bio-fertilizer (10.7 t/ha and bio-fertilizer (5.2 t/ha, respectively. The greatest and the lowest harvest indices were recorded in chemical (0.59 and bio-fertilizer (0.45 treatments, respectively. Number of grain per row and row in ear had not significant differences in integrated and chemical treatments. Methods of bio-fertilizer application had not significant effect on maize yield and yield components. The results of soil analysis showed that bio-fertilizers increased P, K as well as other macro elements availability rather than N. The results revealed that although replacing chemical fertilizers by bio-fertilizers reduced maize growth, but integrated application of these sources produced highest grain yield, nitration elements availability and reduced substantially consumption of fertilizer. The results also indicated that non-chemical sources of crop nutrients can be considered as a reliable alternative for chemical fertilization in ecological production of crops in agro-ecosystems of Iran.

  16. A simple and general method for solving detailed chemical evolution with delayed production of iron and other chemical elements

    CERN Document Server

    Vincenzo, Fiorenzo; Spitoni, Emanuele

    2016-01-01

    In this Letter, we present a new theoretical method for solving the chemical evolution of galaxies, by assuming the instantaneous recycling approximation for chemical elements restored by massive stars and the Delay Time Distribution formalism for the delayed chemical enrichment by Type Ia Supernovae. The galaxy gas mass assembly history, together with the assumed stellar yields and initial mass function, represent the starting point of this method. We derive a very simple and general equation which closely relates the Laplace transforms of the galaxy gas accretion and star formation history, which can be used to simplify the problem of retrieving these quantities in most of current galaxy evolution models. We find that - once the galaxy star formation history has been reconstructed from our assumptions - the differential equation for the evolution of the chemical element $X$ can be suitably solved with classical methods. We apply our model to reproduce the $[\\text{O/Fe}]$ and $[\\text{Si/Fe}]$ vs. $[\\text{Fe/...

  17. Interpolation methods for thematic maps of soybean yield and soil chemical attributes

    National Research Council Canada - National Science Library

    Nelson Miguel Betzek; Eduardo Godoy de Souza; Claudio Leones Bazzi; Ricardo Sobjak; Vanderlei Artur Bier; Erivelto Mercante

    2017-01-01

    ...) in the construction of thematic maps of soybean yield and soil chemical attributes. A set of data referred to 55 sampling units for the construction maps of soybean yield and of eight soil chemical attributes, by different interpolation methods...

  18. Novel quantitative methods for characterization of chemical induced functional alteration in developing neuronal cultures

    Science.gov (United States)

    ABSTRACT BODY: Thousands of chemicals lack adequate testing for adverse effects on nervous system development, stimulating research into alternative methods to screen chemicals for potential developmental neurotoxicity. Microelectrode arrays (MEA) collect action potential spiking...

  19. Nondestructive Method for Bulk Chemical Characterization of Barred Olivine Chondrules

    Science.gov (United States)

    Montoya-Perez, M. A.; Cervantes-de la Cruz, K. E.; Ruvalcaba-Sil, J. L.

    2017-02-01

    This work develops a bulk chemical characterization of barred olivine chondrules based on the XRF analysis using a portable equipment at the National Research and Conservation Science Laboratory of Cultural Heritage (LANCIC-IF) in Mexico City.

  20. Nondestructive Method for Bulk Chemical Characterization of Barred Olivine Chondrules

    Science.gov (United States)

    Montoya-Perez, M. A.; Cervantes-de la Cruz, K. E.; Ruvalcaba-Sil, J. L.

    2017-05-01

    This work develops a bulk chemical characterization of barred olivine chondrules based on the XRF analysis using a portable equipment at the National Research and Conservation Science Laboratory of Cultural Heritage (LANCIC-IF) in Mexico City.

  1. 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.

  2. Novel encoding methods for DNA-templated chemical libraries.

    Science.gov (United States)

    Li, Gang; Zheng, Wenlu; Liu, Ying; Li, Xiaoyu

    2015-06-01

    Among various types of DNA-encoded chemical libraries, DNA-templated library takes advantage of the sequence-specificity of DNA hybridization, enabling not only highly effective DNA-templated chemical reactions, but also high fidelity in library encoding. This brief review summarizes recent advances that have been made on the encoding strategies for DNA-templated libraries, and it also highlights their respective advantages and limitations for the preparation of DNA-encoded libraries.

  3. Monodispersive CoPt Nanoparticles Synthesized Using Chemical Reduction Method

    Institute of Scientific and Technical Information of China (English)

    SHEN Cheng-Min; HUI Chao; YANG Tian-Zhong; XIAO Cong-Wen; CHEN Shu-Tang; DING Hao; GAO Hong-Jun

    2008-01-01

    @@ Monodispersive CoPt nanoparticles in sizes of about 2.2 nm are synthesized by superhydride reduction of CoCl2 and PtCl2 in diphenyl ether. The as-prepared nanoparticles show a chemically disordered A1 structure and are superparamagnetic. Thermal annealing transforms the A1 structure into chemically ordered L1o structure and the particles are ferromagnetic at room temperature.

  4. Flow method and apparatus for screening chemicals using micro x-ray fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Warner, Benjamin P. (Los Alamos, NM); Havrilla, George J. (Los Alamos, NM); Miller, Thomasin C. (Bartlesville, OK); Lewis, Cris (Los Alamos, NM); Mahan, Cynthia A. (Los Alamos, NM); Wells, Cyndi A. (Los Alamos, NM)

    2011-04-26

    Method and apparatus for screening chemicals using micro x-ray fluorescence. A method for screening a mixture of potential pharmaceutical chemicals for binding to at least one target binder involves flow separating a solution of chemicals and target binders into separated components, exposing them to an x-ray excitation beam, detecting x-ray fluorescence signals from the components, and determining from the signals whether or not a binding event between a chemical and target binder has occurred.

  5. Flow method and apparatus for screening chemicals using micro x-ray fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Warner, Benjamin P. (Los Alamos, NM); Havrilla, George J. (Los Alamos, NM); Miller, Thomasin C. (Bartlesville, OK); Lewis, Cris (Los Alamos, NM); Mahan, Cynthia A. (Los Alamos, NM); Wells, Cyndi A. (Los Alamos, NM)

    2009-04-14

    Method and apparatus for screening chemicals using micro x-ray fluorescence. A method for screening a mixture of potential pharmaceutical chemicals for binding to at least one target binder involves flow-separating a solution of chemicals and target binders into separated components, exposing them to an x-ray excitation beam, detecting x-ray fluorescence signals from the components, and determining from the signals whether or not a binding event between a chemical and target binder has occurred.

  6. 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,

  7. 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

  8. 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

  9. Evaluation of methods to test chemicals suitability for umbilical applications

    Energy Technology Data Exchange (ETDEWEB)

    Allenson, S. J.; Lindeman, O. E.; Cenegy, L. M.

    2006-03-15

    Offshore deep-water projects are increasingly deploying chemicals to sub-sea wellheads through umbilical lines. There is no margin for error in umbilical chemical treatment programs since any flow blockage in a sub-sea line would result in a multi-million dollar problem. Chemicals for umbilical delivery must also meet strict requirements in their performance and especially their handling properties. Umbilical delivery must be effective at low concentrations in preventing corrosion, scale, hydrates, asphaltenes, paraffin and a host of other problems. Chemical transiting an umbilical can experience pressures as high as 15,000 psi and temperatures ranging from near 0 deg C to greater than 120 deg C. Since some umbilicals are as long as 80 km, a week or more can elapse from the time the chemical is injected at the platform until it reaches the sub-sea well. Therefore, the chemical must not only be stable under all temperature and pressure conditions that it may experience in the umbilical line, it must also be stable under these conditions for a long period of time. Since many umbilical lines actually terminate into sub-sea valves and connectors that are only a few hundred microns in diameter, it is critical that the injected chemical have a low viscosity at sub-sea temperatures and pressures and that it be completely free of particles. These issues present substantial challenges in formulating and manufacturing chemicals for umbilical applications that must be addressed prior to approval of a product for use. Each of these challenges was taken into consideration and a series of tests were developed to assure reliable chemical pump ability through an umbilical line. The tests developed included enhanced formulation stability tests under umbilical temperature and pressure conditions, NAS Class rating, extensive material compatibility testing to include all metals and elastomers that may be used in umbilical injection systems and comprehensive physical property testing

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Dynamic behaviour of tantalum hydride supported on silica or MCM-41 in the metathesis of alkanes

    KAUST Repository

    Soignier, Sophie

    2014-01-01

    The metathesis of ethane and propane catalysed by tantalum hydride supported on silica or MCM-41 was studied under static and dynamic conditions. During the reaction, the rate decreased over time, indicating deactivation of the catalyst. The evolution of the catalytic system and surface species over time was monitored by various physico-chemical methods: FTIR, 13C NMR spectroscopy, elemental analysis and chemical reactivity. A carbonaceous deposit composed of unsaturated hydrocarbyl species was observed by 13C NMR. This deposit was responsible for poisoning of the catalyst. The deactivation of the catalyst proved more severe at higher temperatures and under static rather than dynamic conditions. A partial regeneration of the catalyst could be achieved during a series of repeated runs. Mechanistically, the deconvolution of the products\\' distribution over time indicated the occurrence of hydrogenolysis in the early stages of the reaction, while pure metathesis dominated later on. The hydrogen was supplied by the dehydrogenation of hydrocarbyl surface species involved in the deactivation process. © 2014 The Royal Society of Chemistry.

  15. 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

  16. 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

  17. 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 ℃.

  18. Wireless Chemical Sensor and Sensing Method for Use Therewith

    Science.gov (United States)

    Woodard, Stanley E. (Inventor); Oglesby, Donald M. (Inventor); Taylor, Bryant D. (Inventor)

    2016-01-01

    A wireless chemical sensor includes an electrical conductor and a material separated therefrom by an electric insulator. The electrical conductor is an unconnected open-circuit shaped for storage of an electric field and a magnetic field. In the presence of a time-varying magnetic field, the first electrical conductor resonates to generate harmonic electric and magnetic field responses. The material is positioned at a location lying within at least one of the electric and magnetic field responses so-generated. The material changes in electrical conductivity in the presence of a chemical-of-interest.

  19. Thermodynamic Calculation on the Formation of Titanium Hydride

    Institute of Scientific and Technical Information of China (English)

    Jing-wei Zhao; Hua Ding; Xue-feng Tian; Wen-juan Zhao; Hong-liang Hou

    2008-01-01

    A modified Miedema model, using interrelationship among the basic properties of elements Ti and H, is employed to calculate the standard enthalpy of formation of titanium hydride TiHx (1≤x≤2). Based on Debye theories of solid thermal capacity, the vibrational entropy, as well as electronic entropy, is acquired by quantum mechanics and statistic thermodynamics methods, and a new approach is presented to calculate the standard entropy of formation of Till2. The values of standard enthalpy of formation of TiHx decrease linearly with increase of x. The calculated results of standard enthalpy, entropy, and free energy of forma- tion of Till2 at 298.16 K are -142.39 kJ/mol, -143.0 J/(mol-K) and -99.75 k J/tool, respectively, which is consistent with the previously-reported data obtained by either experimental or theoretical calculation methods. The results show that the thermodynamic model for titanium hydride is reasonable.

  20. Measurement of nuclear fuel pin hydriding utilizing epithermal neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Miller, W.H. [Univ. of Missouri, Columbia, MO (United States); Farkas, D.M.; Lutz, D.R. [General Electric Co., Pleasanton, CA (United States)

    1996-12-31

    The measurement of hydrogen or zirconium hydriding in fuel cladding has long been of interest to the nuclear power industry. The detection of this hydrogen currently requires either destructive analysis (with sensitivities down to 1 {mu}g/g) or nondestructive thermal neutron radiography (with sensitivities on the order of a few weight percent). The detection of hydrogen in metals can also be determined by measuring the slowing down of neutrons as they collide and rapidly lose energy via scattering with hydrogen. This phenomenon is the basis for the {open_quotes}notched neutron spectrum{close_quotes} technique, also referred to as the Hysen method. This technique has been improved with the {open_quotes}modified{close_quotes} notched neutron spectrum technique that has demonstrated detection of hydrogen below 1 {mu}g/g in steel. The technique is nondestructive and can be used on radioactive materials. It is proposed that this technique be applied to the measurement of hydriding in zirconium fuel pins. This paper summarizes a method for such measurements.

  1. Aperture-Tolerant, Chemical-Based Methods to Reduce Channeling

    Energy Technology Data Exchange (ETDEWEB)

    Randall S. Seright

    2007-09-30

    This final technical progress report describes work performed from October 1, 2004, through May 16, 2007, for the project, 'Aperture-Tolerant, Chemical-Based Methods to Reduce Channeling'. We explored the potential of pore-filling gels for reducing excess water production from both fractured and unfractured production wells. Several gel formulations were identified that met the requirements--i.e., providing water residual resistance factors greater than 2,000 and ultimate oil residual resistance factors (F{sub rro}) of 2 or less. Significant oil throughput was required to achieve low F{sub rro} values, suggesting that gelant penetration into porous rock must be small (a few feet or less) for existing pore-filling gels to provide effective disproportionate permeability reduction. Compared with adsorbed polymers and weak gels, strong pore-filling gels can provide greater reliability and behavior that is insensitive to the initial rock permeability. Guidance is provided on where relative-permeability-modification/disproportionate-permeability-reduction treatments can be successfully applied for use in either oil or gas production wells. When properly designed and executed, these treatments can be successfully applied to a limited range of oilfield excessive-water-production problems. We examined whether gel rheology can explain behavior during extrusion through fractures. The rheology behavior of the gels tested showed a strong parallel to the results obtained from previous gel extrusion experiments. However, for a given aperture (fracture width or plate-plate separation), the pressure gradients measured during the gel extrusion experiments were much higher than anticipated from rheology measurements. Extensive experiments established that wall slip and first normal stress difference were not responsible for the pressure gradient discrepancy. To explain the discrepancy, we noted that the aperture for gel flow (for mobile gel wormholing through concentrated

  2. New Method to Acquire Chemomechanical Parameters of Diverse Chemical Reactions

    Science.gov (United States)

    2011-01-30

    a model for reversible and pseudoreversible isothermal photoactuation based on the Carnot -type formalism and used it to estimate the maximum single...reactions offers unique attributes, e.g., potentially fast actuation cycles , high chemical and mechanical stability, flexible device design and

  3. Estimation methods for bioaccumulation in risk assessment of organic chemicals.

    NARCIS (Netherlands)

    Jager, D.T.; Hamers, T.

    1997-01-01

    The methodology for estimating bioaccumulation of organic chemicals is evaluated. This study is limited to three types of organisms: fish, earthworms and plants (leaf crops, root crops and grass). We propose a simple mechanistic model for estimating BCFs which performs well against measured data. To

  4. Estimation methods for bioaccumulation in risk assessment of organic chemicals

    NARCIS (Netherlands)

    Jager DT; Hamers T; ECO

    1997-01-01

    The methodology for estimating bioaccumulation of organic chemicals is evaluated. This study is limited to three types of organisms: fish, earthworms and plants (leaf crops, root crops and grass). We propose a simple mechanistic model for estimating BCFs which performs well against measured data. To

  5. Development and investigation of novel nanostructures and complex hydrides for hydrogen storage

    Science.gov (United States)

    Niemann, Michael Ulrich

    2009-12-01

    Over the past few years, the need for a clean and renewable fuel has sharply risen. This is due to increasing fossil fuel costs and the desire to limit or eliminate harmful byproducts which are created during the burning of these fuels. Hydrogen is the most abundant element in the universe and can be used in either fuel cells or traditional internal combustion engines to produce energy with no harmful emissions. One of the main obstacles facing the implementation of a hydrogen economy is its storage. Classical methods of storage involve either high and unsafe pressures or liquid storage involving a large amount of energy. Two alternative hydrogen storage methods are investigated---physisorption, which is the weak chemical bonding to a material, as well as chemisorption, which is a strong chemical bond of hydrogen to a host material. Polyaniline, a conducting polymer, is investigated in both its bulk form as well as in nanostructured forms, more precisely nanofibers and nanospheres, to store hydrogen via physisorption. It is found the bulk form of polyaniline can store only approximately 0.5wt.% hydrogen, which is far short of the 6wt.% required for practical applications. Nanofibers and nanospheres, however, have been developed, which can store between 4wt.% and 10wt.% of hydrogen at room temperature with varying kinetics. A new complex metal hydride comprised of LiBH4, LiNH 2 and MgH2 has been developed to store hydrogen via chemisorption. While the parent compounds require high temperatures and suffer of slow kinetics for hydrogen sorption, the work performed as part of this dissertation shows that optimized processing conditions reduce the hydrogen release temperature from 250°C to approximately 150°C, while the addition of nano sized materials has been found to increase the kinetics of hydrogen sorption as well as further decrease the hydrogen release temperature, making this one of the first viable hydrogen storage materials available. This is the first time

  6. Device and method for enhanced collection and assay of chemicals with high surface area ceramic

    Energy Technology Data Exchange (ETDEWEB)

    Addleman, Raymond S.; Li, Xiaohong Shari; Chouyyok, Wilaiwan; Cinson, Anthony D.; Bays, John T.; Wallace, Krys

    2016-02-16

    A method and device for enhanced capture of target analytes is disclosed. This invention relates to collection of chemicals for separations and analysis. More specifically, this invention relates to a solid phase microextraction (SPME) device having better capability for chemical collection and analysis. This includes better physical stability, capacity for chemical collection, flexible surface chemistry and high affinity for target analyte.

  7. Minimizing the Free Energy: A Computer Method for Teaching Chemical Equilibrium Concepts.

    Science.gov (United States)

    Heald, Emerson F.

    1978-01-01

    Presents a computer method for teaching chemical equilibrium concepts using material balance conditions and the minimization of the free energy. Method for the calculation of chemical equilibrium, the computer program used to solve equilibrium problems and applications of the method are also included. (HM)

  8. Feasibility study for the recycling of nickel metal hydride electric vehicle batteries. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Sabatini, J.C.; Field, E.L.; Wu, I.C.; Cox, M.R.; Barnett, B.M.; Coleman, J.T. [Little (Arthur D.), Inc., Cambridge, MA (United States)

    1994-01-01

    This feasibility study examined three possible recycling processes for two compositions (AB{sub 2} and AB{sub 5}) of nickel metal hydride electric vehicle batteries to determine possible rotes for recovering battery materials. Analysts examined the processes, estimated the costs for capital equipment and operation, and estimated the value of the reclaimed material. They examined the following three processes: (1) a chemical process that leached battery powders using hydrochloric acid, (2) a pyrometallurical process, and (3) a physical separation/chemical process. The economic analysis revealed that the physical separation/chemical process generated the most revenue.

  9. Consolidation of the formation sand by chemical methods

    Directory of Open Access Journals (Sweden)

    Mariana Mihočová

    2006-10-01

    Full Text Available The sand control by consolidation involves the process of injecting chemicals into the naturally unconsolidated formation to provide an in situ grain-to-grain cementation. The sand consolidation chemicals are available for some 30 years. Several types of consolidating material were tried. Presently available systems utilize solidified plastics to provide the cementation. These systems include phenol resin, phenol-formaldehyde, epoxy, furan and phenolic-furfuryl.The sand consolidation with the steam injection is a novel technique. This process provides a highly alkaline liquid phase and temperatures to 300 °C to geochemically create cements by interacting with the dirty sand.While the formation consolidation has widely applied, our experience has proved a high level of success.

  10. Method for innovative synthesis-design of chemical process flowsheets

    DEFF Research Database (Denmark)

    Kumar Tula, Anjan; Gani, Rafiqul

    of chemical processes, where, chemical process flowsheets could be synthesized in the same way as atoms or groups of atoms are synthesized to form molecules in computer aided molecular design (CAMD) techniques [4]. That, from a library of building blocks (functional process-groups) and a set of rules to join......, the implementation of the computer-aided process-group based flowsheet synthesis-design framework is presented together with an extended library of flowsheet property models to predict the environmental impact, safety factors, product recovery and purity, which are employed to screen the generated alternatives. Also...... flowsheet (the well-known Hydrodealkylation of toluene process) and another for a biochemical process flowsheet (production of ethanol from lignocellulose). In both cases, not only the reported designs are found and matched, but also new innovative designs are found, which is possible because...

  11. Realizing NiO nanocrystals from a simple chemical method

    Indian Academy of Sciences (India)

    Neelabh Srivastava; P C Srivastava

    2010-12-01

    Nanocrystalline NiO has been prepared successfully by a simple chemical route using NiCl2.6H2O and NaOH aqueous solution at a temperature of 70°C. The prepared material has been characterized from XRD, SEM, and M–H characteristics. It has been found that NiO nanocrystals have been formed which shows a superparamagnetic/superantiferromagnetic behaviour.

  12. Chemical and ecological control methods for Epitrix spp.

    OpenAIRE

    A. G. S. Cuthbertson

    2015-01-01

    Very little information exists in regards to the control options available for potato flea beetles, Epitrix spp. This short review covers both chemical and ecological options currently available for control of Epitrix spp. Synthetic pyrethroids are the weapon of choice for the beetles. However, the impetus in integrated pest management is to do timely (early-season) applications with something harsh which will give long-term protection at a time when there are not a lot of beneficials in the ...

  13. Reversible hydrogen storage property and structural analysis for face-centered cubic hydride Mg0.82Zr0.18H2 prepared by gigapascal hydrogen pressure method.

    Science.gov (United States)

    Takasaki, Tomoaki; Kyoi, Daisuke; Kitamura, Naoyuki; Tanase, Shigeo; Sakai, Tetsuo

    2007-12-27

    The face-centered cubic (fcc) type magnesium-zirconium hydride (Mg0.82Zr0.18Hx) was synthesized by means of the ultrahigh pressure (UHP) technique, which could generate 8 GPa of hydrogen pressure. The differential scanning calorimeter (DSC) measurements indicated that the fcc phase exhibited reversible hydrogen releasing and restoring properties under 0.5 MPa of hydrogen pressure. On the pressure-composition isotherms, the released and restored hydrogen capacities were estimated to be 3 approximately 3.5 wt %. The Rietveld analysis for synchrotron X-ray diffraction (XRD) data showed that the fcc phase had around 70 wt % mass fraction and was preserved without decomposition during hydrogen releasing and restoring cycles.

  14. Using deuterated PAH amendments to validate chemical extraction methods to predict PAH bioavailability in soils

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Eyles, Jose L., E-mail: j.l.gomezeyles@reading.ac.uk [University of Reading, School of Human and Environmental Sciences, Soil Research Centre, Reading, RG6 6DW Berkshire (United Kingdom); Collins, Chris D.; Hodson, Mark E. [University of Reading, School of Human and Environmental Sciences, Soil Research Centre, Reading, RG6 6DW Berkshire (United Kingdom)

    2011-04-15

    Validating chemical methods to predict bioavailable fractions of polycyclic aromatic hydrocarbons (PAHs) by comparison with accumulation bioassays is problematic. Concentrations accumulated in soil organisms not only depend on the bioavailable fraction but also on contaminant properties. A historically contaminated soil was freshly spiked with deuterated PAHs (dPAHs). dPAHs have a similar fate to their respective undeuterated analogues, so chemical methods that give good indications of bioavailability should extract the fresh more readily available dPAHs and historic more recalcitrant PAHs in similar proportions to those in which they are accumulated in the tissues of test organisms. Cyclodextrin and butanol extractions predicted the bioavailable fraction for earthworms (Eisenia fetida) and plants (Lolium multiflorum) better than the exhaustive extraction. The PAHs accumulated by earthworms had a larger dPAH:PAH ratio than that predicted by chemical methods. The isotope ratio method described here provides an effective way of evaluating other chemical methods to predict bioavailability. - Research highlights: > Isotope ratios can be used to evaluate chemical methods to predict bioavailability. > Chemical methods predicted bioavailability better than exhaustive extractions. > Bioavailability to earthworms was still far from that predicted by chemical methods. - A novel method using isotope ratios to assess the ability of chemical methods to predict PAH bioavailability to soil biota.

  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. 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. 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...

  19. Chemical and ecological control methods for Epitrix spp.

    Directory of Open Access Journals (Sweden)

    A. G. S. Cuthbertson

    2015-01-01

    Full Text Available Very little information exists in regards to the control options available for potato flea beetles, Epitrix spp. This short review covers both chemical and ecological options currently available for control of Epitrix spp. Synthetic pyrethroids are the weapon of choice for the beetles. However, the impetus in integrated pest management is to do timely (early-season applications with something harsh which will give long-term protection at a time when there are not a lot of beneficials in the field. Finding the balance for control of Epitrix spp. is proving difficult.

  20. Initiation of delayed hydride cracking in zirconium-niobium micro pressure tubes

    Science.gov (United States)

    Sundaramoorthy, Ravi Kumar

    Pressure tubes pick up hydrogen while they are in service within CANDU reactors. Sufficiently high hydrogen concentration can lead to hydride precipitation during reactor shutdown/repair at flaws, resulting in the potential for eventual rupture of the pressure tubes by a process called Delayed Hydride Cracking (DHC). The threshold stress intensity factor (KIH) below which the cracks will not grow by delayed hydride cracking of Zr-2.5Nb micro pressure tubes (MPTs) has been determined using a load increasing mode (LIM) method at different temperatures. MPTs have been used to allow easy study of the impact of properties like texture and grain size on DHC. Previous studies on MPTs have focused on creep and effects of stress on hydride orientation; here the use of MPTs for DHC studies is confirmed for the first time. Micro pressure tube samples were hydrided to a target hydrogen content of 100 ppm using an electrolytic method. For DHC testing, 3 mm thick half ring samples were cut out from the tubes using Electrical Discharge Machining (EDM) with a notch at the center. A sharp notch with a root radius of 15 microm was introduced by broaching to facilitate crack initiation. The direct current potential drop method was used to monitor crack growth during the DHC tests. For the temperature range tested the threshold stress intensity factors for the micro pressure tube used were found to be 6.5--10.5 MPa.m 1/2 with the value increasing with increasing temperature. The average DHC velocities obtained for the three different test temperatures 180, 230 and 250°C were 2.64, 10.87 and 8.45 x 10-8 m/s, respectively. The DHC data obtained from the MPTs are comparable to the data published in the literature for full sized CANDU pressure tubes.

  1. 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.

  2. 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.

  3. 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

  4. Method of operating a thermal engine powered by a chemical reaction

    Science.gov (United States)

    Ross, John; Escher, Claus

    1988-01-01

    The invention involves a novel method of increasing the efficiency of a thermal engine. Heat is generated by a non-linear chemical reaction of reactants, said heat being transferred to a thermal engine such as Rankine cycle power plant. The novel method includes externally perturbing one or more of the thermodynamic variables of said non-linear chemical reaction.

  5. Method of operating a thermal engine powered by a chemical reaction

    Science.gov (United States)

    Ross, J.; Escher, C.

    1988-06-07

    The invention involves a novel method of increasing the efficiency of a thermal engine. Heat is generated by a non-linear chemical reaction of reactants, said heat being transferred to a thermal engine such as Rankine cycle power plant. The novel method includes externally perturbing one or more of the thermodynamic variables of said non-linear chemical reaction. 7 figs.

  6. Chemical methods and phytoremediation of soil contaminated with heavy metals.

    Science.gov (United States)

    Chen, H M; Zheng, C R; Tu, C; Shen, Z G

    2000-07-01

    The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.

  7. 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.

  8. 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.

  9. Internal hydriding in irradiated defected Zircaloy fuel rods: A review (LWBR Development Program)

    Energy Technology Data Exchange (ETDEWEB)

    Clayton, J C

    1987-10-01

    Although not a problem in recent commercial power reactors, including the Shippingport Light Water Breeder Reactor, internal hydriding of Zircaloy cladding was a persistent cause of gross cladding failures during the 1960s. It occurred in the fuel rods of water-cooled nuclear power reactors that had a small cladding defect. This report summarizes the experimental findings, causes, mechanisms, and methods of minimizing internal hydriding in defected Zircaloy-clad fuel rods. Irradiation test data on the different types of defected fuel rods, intentionally fabricated defected and in-pile operationally defected rods, are compared. Significant factors affecting internal hydriding in defected Zircaloy-clad fuel rods (defect hole size, internal and external sources of hydrogen, Zircaloy cladding surface properties, nickel alloy contamination of Zircaloy, the effect of heat flux and fluence) are discussed. Pertinent in-pile and out-of-pile test results from Bettis and other laboratories are used as a data base in constructing a qualitative model which explains hydrogen generation and distribution in Zircaloy cladding of defected water-cooled reactor fuel rods. Techniques for minimizing internal hydride failures in Zircaloy-clad fuel rods are evaluated.

  10. 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.

  11. 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.

  12. 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.

  13. Theoretical investigation on spin-forbidden cooling transitions of gallium hydride.

    Science.gov (United States)

    Zhang, Yun-Guang; Zhang, Hua; Song, Hai-Yang; Yu, You; Wan, Ming-Jie

    2017-09-20

    Herein, the spin-forbidden cooling of a gallium hydride molecule is investigated using ab initio quantum chemistry. The cooling transition and the corresponding potential energy curves including , a(3)Π0(-), a(3)Π0(+), a(3)Π1, a(3)Π2, A(1)Π1, , 1(3)Σ, , , and 2(3)Σ states are simulated based on the multi-reference configuration interaction approach plus Davidson corrections method. By solving the nuclear Schrödinger equation, we calculate the spectroscopic constants of these states, which are in good agreement with the available experimental values. Based on the transition data, there seems to be a theoretical puzzle: highly diagonally distributed Franck-Condon factor f00 for transitions , , and for the gallium hydride molecule but the intervening state A(1)Π1 for transition is prohibitive to laser cooling. In addition, the transition does not have a suitable rate of optical cycling owing to a large radiative lifetime for state. Our theoretical simulation indicates the solution to the puzzle: the transition has a high emission rate, and there is a suitable radiative lifetime for a(3)Π1 state, which can ensure rapid and efficient laser cooling of gallium hydride. The proposed laser drives transition by using three wavelengths (main pump laser λ00; two repumping lasers λ10 and λ21). These results demonstrate the possibility of laser-cooling the gallium hydride molecule, and a sub-microkelvin cool temperature can be reached for this molecule.

  14. Theoretical Standard Model Rates of Proton to Neutron Conversions Near Metallic Hydride Surfaces

    CERN Document Server

    Widom, A

    2006-01-01

    The process of radiation induced electron capture by protons or deuterons producing new ultra low momentum neutrons and neutrinos may be theoretically described within the standard field theoretical model of electroweak interactions. For protons or deuterons in the neighborhoods of surfaces of condensed matter metallic hydride cathodes, such conversions are determined in part by the collective plasma modes of the participating charged particles, e.g. electrons and protons. The radiation energy required for such low energy nuclear reactions may be supplied by the applied voltage required to push a strong charged current across a metallic hydride surface employed as a cathode within a chemical cell. The electroweak rates of the resulting ultra low momentum neutron production are computed from these considerations.

  15. FINITE ELEMENT METHOD AND ANALYSIS FOR CHEMICAL-FLOODING SIMULATION

    Institute of Scientific and Technical Information of China (English)

    YUAN Yirang

    2000-01-01

    This article discusses the enhanced oil recovery numerical simulation of the chemical-flooding (such as surfactants, alcohol, polymers) composed of three-dimensional multicomponent, multiphase and incompressible mixed fluids. The mathematical model can be described as a coupled system of nonlinear partial differential equations with initialboundary value problems. From the actual conditions such as the effect of cross interference and the three-dimensional characteristic of large-scale science-engineering computation, this article puts forward a kind of characteristic finite element fractional step schemes and obtain the optimal order error estimates in L2 norm. Thus we have thoroughly solved the well-known theoretical problem proposed by a famous scientist, R. E. Ewing.

  16. Stochastic linear multistep methods for the simulation of chemical kinetics

    Science.gov (United States)

    Barrio, Manuel; Burrage, Kevin; Burrage, Pamela

    2015-02-01

    In this paper, we introduce the Stochastic Adams-Bashforth (SAB) and Stochastic Adams-Moulton (SAM) methods as an extension of the τ-leaping framework to past information. Using the Θ-trapezoidal τ-leap method of weak order two as a starting procedure, we show that the k-step SAB method with k ≥ 3 is order three in the mean and correlation, while a predictor-corrector implementation of the SAM method is weak order three in the mean but only order one in the correlation. These convergence results have been derived analytically for linear problems and successfully tested numerically for both linear and non-linear systems. A series of additional examples have been implemented in order to demonstrate the efficacy of this approach.

  17. Perovskite type nanopowders and thin films obtained by chemical methods

    Directory of Open Access Journals (Sweden)

    Viktor Fruth

    2010-09-01

    Full Text Available The review presents the contribution of the authors, to the preparation of two types of perovskites, namely BiFeO3 and LaCoO3, by innovative methods. The studied perovskites were obtained as powders, films and sintered bodies. Their complex structural and morphological characterization is also presented. The obtained results have underlined the important influence of the method of preparation on the properties of the synthesized perovskites.

  18. Design Hybrid Methods for Encoding Prior Knowledge in Feedforward Network with Application in Chemical Engineering

    Institute of Scientific and Technical Information of China (English)

    CHENChongwei; CHENDezhao

    2002-01-01

    Three-layer feedforward networks have been widely used in modeling chemical engineering processes and prior-knowledge-based methods have been introduced to improve their performances.In this paper,we propose the methodology of designing better prior-knowledge-based hybrid methods by combining the existing ones. Then according to this methodology,two hybrid methods,interpolation-optimization (IO) method and interpolation penalty-function (IPF) method,are designed as examples.Finally,both methods are applied to modeling two cases in chemical engineering to investigate their effectiveness.Simulation results show that the performances of the hybrid methods are better than those of their parents.

  19. Predictive performance of the Vitrigel-eye irritancy test method using 118 chemicals.

    Science.gov (United States)

    Yamaguchi, Hiroyuki; Kojima, Hajime; Takezawa, Toshiaki

    2016-08-01

    We recently developed a novel Vitrigel-eye irritancy test (EIT) method. The Vitrigel-EIT method is composed of two parts, i.e., the construction of a human corneal epithelium (HCE) model in a collagen vitrigel membrane chamber and the prediction of eye irritancy by analyzing the time-dependent profile of transepithelial electrical resistance values for 3 min after exposing a chemical to the HCE model. In this study, we estimated the predictive performance of Vitrigel-EIT method by testing a total of 118 chemicals. The category determined by the Vitrigel-EIT method in comparison to the globally harmonized system classification revealed that the sensitivity, specificity and accuracy were 90.1%, 65.9% and 80.5%, respectively. Here, five of seven false-negative chemicals were acidic chemicals inducing the irregular rising of transepithelial electrical resistance values. In case of eliminating the test chemical solutions showing pH 5 or lower, the sensitivity, specificity and accuracy were improved to 96.8%, 67.4% and 84.4%, respectively. Meanwhile, nine of 16 false-positive chemicals were classified irritant by the US Environmental Protection Agency. In addition, the disappearance of ZO-1, a tight junction-associated protein and MUC1, a cell membrane-spanning mucin was immunohistologically confirmed in the HCE models after exposing not only eye irritant chemicals but also false-positive chemicals, suggesting that such false-positive chemicals have an eye irritant potential. These data demonstrated that the Vitrigel-EIT method could provide excellent predictive performance to judge the widespread eye irritancy, including very mild irritant chemicals. We hope that the Vitrigel-EIT method contributes to the development of safe commodity chemicals. Copyright © 2015 The Authors. Journal of Applied Toxicology published by John Wiley & Sons Ltd.

  20. A new ultrasonic method to detect chemical additives in branded milk

    Indian Academy of Sciences (India)

    S Mohanan; P G Thomas Panicker; Lilly Iype; M Laila; I Domini; R G Bindu

    2002-09-01

    A new ultrasonic method – thermoacoustic analysis – is reported for the detection of the added chemical preservatives in branded milk. The nature of variation and shift in the thermal response of the acoustic parameters specific acoustic impedance, adiabatic compressibility and Rao’s specific sound velocity for different samples of branded milk as compared to the chemical added pure milk are explained as due to the presence of chemicals in these branded samples.

  1. Estimation methods for bioaccumulation in risk assessment of organic chemicals

    NARCIS (Netherlands)

    Jager DT; Hamers T; ECO

    1997-01-01

    Methodes voor het inschatten van bioaccumulatie van organische stoffen worden ge-evalueerd. Deze studie is beperkt tot drie typen organismen: vis, wormen en planten (bladgewassen, wortelgewassen en gras). We stellen een simpel mechanistisch model voor dat goed presteert t.o.v. gemeten waarden. O

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Evaluating three methods that contribute to the learning of inorganic chemical nomenclature

    Science.gov (United States)

    Chimeno, Joseph Samuel

    The majority of students about to complete a first year chemistry course have a poor working knowledge of inorganic chemical nomenclature (average quiz scores are less than 60% correct). Usually, the chemical nomenclature topic is not emphasized in a first year chemistry class, and a minimum amount of time is devoted to it. The traditional assignment for chemical nomenclature involves having students work practice problems at the end of the chapter. Students are not very receptive to this approach. The minimal exposure to chemical nomenclature in class along with the ineffective approach of a traditional assignment results in students having a poor working knowledge of chemical nomenclature. Studies have claimed that students are more receptive to learning when game playing is combined with the learning activity. Therefore two educational games were created to help students develop a working knowledge of inorganic chemical nomenclature: the Rainbow Wheel and Rainbow Matrix. This study compared the learning of inorganic chemical nomenclature by three different methods; one was the traditional method where students worked problems at the end of a chapter, and the other two methods used a game format to learn chemical nomenclature. The statistical analysis of student performance was evaluated with analysis of variance (ANOVA) and t-tests. The analysis revealed that the game format methods were more effective in helping students develop a working knowledge of chemical nomenclature. The ANOVA test indicate that both the Rainbow Wheel and Rainbow Matrix post-assignment mean scores differ significantly from the traditional group's post-assignment mean scores (p game format groups' mean scores. The results of this study indicate that students will learn chemical nomenclature more effectively when the subject is presented in a game format. The game format methods used in this study encouraged students to visualize the process of writing chemical formulas correctly, while

  9. 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.).

  10. 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.

  11. 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.

  12. Methods for chemical analysis of water and wastes

    Energy Technology Data Exchange (ETDEWEB)

    1979-03-01

    This manual provides test procedures approved for the monitoring of water supplies, waste discharges, and ambient waters, under the Safe Drinking Water Act, the National Pollutant Discharge Elimination System, and Ambient Monitoring Requirements of Section 106 and 208 of Public Law 92-500. The test methods have been selected to meet the needs of federal legislation and to provide guidance to laboratories engaged in the protection of human health and the aquatic environment.

  13. 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

  14. Recycling of poly(ethylene terephthalate – A review focusing on chemical methods

    Directory of Open Access Journals (Sweden)

    B. Geyer

    2016-07-01

    Full Text Available Recycling of poly(ethylene terephthalate (PET is of crucial importance, since worldwide amounts of PETwaste increase rapidly due to its widespread applications. Hence, several methods have been developed, like energetic, material, thermo-mechanical and chemical recycling of PET. Most frequently, PET-waste is incinerated for energy recovery, used as additive in concrete composites or glycolysed to yield mixtures of monomers and undefined oligomers. While energetic and thermo-mechanical recycling entail downcycling of the material, chemical recycling requires considerable amounts of chemicals and demanding processing steps entailing toxic and ecological issues. This review provides a thorough survey of PET-recycling including energetic, material, thermo-mechanical and chemical methods. It focuses on chemical methods describing important reaction parameters and yields of obtained reaction products. While most methods yield monomers, only a few yield undefined low molecular weight oligomers for impaired applications (dispersants or plasticizers. Further, the present work presents an alternative chemical recycling method of PET in comparison to existing chemical methods.

  15. Research on Crude Oil Demulsification Using the Combined Method of Ultrasound and Chemical Demulsifier

    National Research Council Canada - National Science Library

    Mingxu Yi; Jun Huang; Lifeng Wang

    2017-01-01

    In this paper, experiments of crude oil demulsification using ultrasound, chemical demulsifier, and the combined method of ultrasound and chemical demulsifier, respectively, at different temperatures (40°C, 60°C, and 70°C) are carried out...

  16. 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....

  17. 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.

  18. 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.

  19. Largest Common Chemical Feature Subtree as a Virtual Screening Method

    DEFF Research Database (Denmark)

    Kristensen, Thomas Greve; Pedersen, Christian Storm; Thomsen, Rene

    We investigate the effectiveness of using a tree comparison based method to screen for drug candidates. Molecules are represented as trees in which ring systems are reduced to single nodes. These trees are compared to the tree of a selected known binder and the molecules are ranked according...... to the normalized size of their largest common subtree. The nodes of the molecular trees contains information about the atoms or ring systems they represent (e.g. charge and hydrogen donor/acceptor properties). In this way we can restrict which nodes are matched when calculating the size of the largest common...

  20. Review of Physical and Chemical Methods for Characterization of Fuels

    Science.gov (United States)

    1981-12-01

    Naphtha Using Packed Columns," Instituto di Chimica Analitica dell’ Universita’ di Roma, Rome, Italy, Journal of Chromatography, Vol. 160, pp 147-54...Chromatography-New Evaluation Methods of Mathematical Dead Time," Instituto de Quimica Fisica "Rocasolano", Madrid, Spain, Journal of Chromatographic Science...Journal of Japan Petroleum Institute, Vol. 20, No. 7, July 1977. EQU DIS PET P-030. Harris , J.C., Hayes, M.L., Levins, P.L., Lindsay, D.B., "EPA/IERL-RTP

  1. CHEMICALS

    CERN Document Server

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  2. Study of improved methods for predicting chemical equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Lenz, T.G.; Vaughan, J.D.

    1992-06-01

    The objective of our research has been to develop computational methods that have the capability of accurately predicting equilibrium constants of typical organic reactions in gas and liquid solution phases. We have chosen Diels-Alder reactions as prototypic systems for the investigation, chiefly because there are an adequate number of reported equilibrium constants for the candidate reactions in both gas and solution phases, which data provides a suitable basis for tests of the developed computational methods. Our approach has been to calculate the standard enthalpies of formation ({Delta}H{sub f}{sup 0}) at 298.15K and the standard thermodynamic functions (S{sup 0}, Cp{sup 0}, and (H{sup 0}-H{sub 0}{sup 0})/T) for a range of temperatures for reactants and products, and from these properties to calculate standard enthalpies, entropies, Gibbs free energies, and equilibrium constants ({Delta}H{sub T}{sup 0}, {Delta}S{sub T}{sup 0}, and K{sub a}) at various temperatures for the chosen reaction.

  3. Phytotoxicity of Ag nanoparticles prepared by biogenic and chemical methods

    Science.gov (United States)

    Choudhury, Rupasree; Majumder, Manna; Roy, Dijendra Nath; Basumallick, Srijita; Misra, Tarun Kumar

    2016-06-01

    Silver nanoparticles (Ag NPs) are now widely used as antibacterial and antifungal materials in different consumer products. We report here the preparation of Ag NPs by neem leaves extract ( Azadirachta) reduction and trisodium citrate-sodium borohydride reduction methods, and study of their phytotoxicity. The nanoparticles were characterized by UV-Vis spectroscopy, FTIR, and atomic force microscopy (AFM) techniques. Both neem-coated and citrate-coated Ag NPs exhibit surface plasmon around 400 nm, and their average sizes measured by AFM are about 100 and 20 nm, respectively. Antibacterial and antifungal activities of these nanomaterials have been studied by simple pea seed germination and disk diffusion methods. It has been observed from the growth of root and shoot, citrate-coated Ag NPs significantly affect seedling growth, but neem-coated Ag NPs exhibit somehow mild toxicity toward germination process due to the nutrient supplements from neem. On the other hand, antifungal activity of neem-coated Ag NPs has been found much higher than that of citrate-coated Ag NPs due to the combined effects of antifungal activity of neem and Ag NPs. Present research primarily indicates a possible application of neem-coated Ag NPs as a potential fungicide.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. A benchmarking method to measure dietary absorption efficiency of chemicals by fish.

    Science.gov (United States)

    Xiao, Ruiyang; Adolfsson-Erici, Margaretha; Åkerman, Gun; McLachlan, Michael S; MacLeod, Matthew

    2013-12-01

    Understanding the dietary absorption efficiency of chemicals in the gastrointestinal tract of fish is important from both a scientific and a regulatory point of view. However, reported fish absorption efficiencies for well-studied chemicals are highly variable. In the present study, the authors developed and exploited an internal chemical benchmarking method that has the potential to reduce uncertainty and variability and, thus, to improve the precision of measurements of fish absorption efficiency. The authors applied the benchmarking method to measure the gross absorption efficiency for 15 chemicals with a wide range of physicochemical properties and structures. They selected 2,2',5,6'-tetrachlorobiphenyl (PCB53) and decabromodiphenyl ethane as absorbable and nonabsorbable benchmarks, respectively. Quantities of chemicals determined in fish were benchmarked to the fraction of PCB53 recovered in fish, and quantities of chemicals determined in feces were benchmarked to the fraction of decabromodiphenyl ethane recovered in feces. The performance of the benchmarking procedure was evaluated based on the recovery of the test chemicals and precision of absorption efficiency from repeated tests. Benchmarking did not improve the precision of the measurements; after benchmarking, however, the median recovery for 15 chemicals was 106%, and variability of recoveries was reduced compared with before benchmarking, suggesting that benchmarking could account for incomplete extraction of chemical in fish and incomplete collection of feces from different tests. © 2013 SETAC.

  10. Mathematical Modeling of Pneumatic Artificial Muscle Actuation via Hydrogen Driving Metal Hydride-LaNi5

    Institute of Scientific and Technical Information of China (English)

    Thananchai Leephakpreeda

    2012-01-01

    Quantitative understanding of mechanical actuation of intricate Pneumatic Artificial Muscle (PAM) actuators is technically required in control system design for effective real-time implementation.This paper presents mathematical modeling of the PAM driven by hydrogen-gas pressure due to absorption and desorption of metal hydride.Empirical models of both mechanical actuation of industrial PAM and chemical reaction of the metal hydride-LaNi5 are derived systematically where their interactions comply with the continuity principle and energy balance in describing actual dynamic behaviors of the PAM actuator (PAM and hydriding/dehydriding-reaction bed).Simulation studies of mechanical actuation under various loads are conducted so as to present dynamic responses of the PAM actuators.From the promising results,it is intriguing that the heat input for the PAM actuator can be supplied to,or pumped from the reaction bed,in such a way that absorption and desorption of hydrogen gas take place,respectively,in controlling the pressure of hydrogen gas within the PAM actuator.Accordingly,this manipulation results in desired mechanical actuation of the PAM actuator in practical uses.

  11. 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.

  12. Theoretical spectroscopic parameters for the low-lying states of the second-row transition metal hydrides

    Science.gov (United States)

    Langhoff, Stephen R.; Pettersson, Lars G. M.; Bauschlicher, Charles W., Jr.; Partridge, Harry

    1987-01-01

    A systematic analysis of the low-lying states of all of the second-row transition metal (TM) hydrides except CdH is reported. The calculations included the dominant relativistic contributions through the use of the relativistic effective core potentials of Hay and Wadt (1985). Electron correlation was incorporated, using single-plus-double configuration interaction, the coupled pair functional (CPF) formalism of Ahlrichs et al. (1985), and the Chong and Langhoff (1986) modified version of the CPF method. The spectroscopic parameters D(e), r(e), and mu(e) determined for the low-lying states are compared with the available experimental data and previous theoretical results. In contrast to the first-row TM hydrides studied earlier (Chong et al., 1986), the spectroscopic constants for the second-row TM hydrides were found to be much less sensitive to the level of correlation treatment.

  13. Theoretical spectroscopic parameters for the low-lying states of the second-row transition metal hydrides

    Science.gov (United States)

    Langhoff, Stephen R.; Pettersson, Lars G. M.; Bauschlicher, Charles W., Jr.; Partridge, Harry

    1987-01-01

    A systematic analysis of the low-lying states of all of the second-row transition metal (TM) hydrides except CdH is reported. The calculations included the dominant relativistic contributions through the use of the relativistic effective core potentials of Hay and Wadt (1985). Electron correlation was incorporated, using single-plus-double configuration interaction, the coupled pair functional (CPF) formalism of Ahlrichs et al. (1985), and the Chong and Langhoff (1986) modified version of the CPF method. The spectroscopic parameters D(e), r(e), and mu(e) determined for the low-lying states are compared with the available experimental data and previous theoretical results. In contrast to the first-row TM hydrides studied earlier (Chong et al., 1986), the spectroscopic constants for the second-row TM hydrides were found to be much less sensitive to the level of correlation treatment.

  14. Method of effecting expanding chemical anchor/seals for rock cavities

    Energy Technology Data Exchange (ETDEWEB)

    Swanson, D.; Schlump, M.

    1989-06-20

    This method discusses sealing a cavity formed in a rock against the passage of fluids without fracturing the rock; by placing wadding in the cavity and adding a supply of expanding chemical grout; a seal was been developed upon hardening.

  15. Dielectric Properties of Nanostructured PZTSynthesised by Chemical Methods

    Directory of Open Access Journals (Sweden)

    N.S. Gajbhiye

    2007-01-01

    Full Text Available In this study, the dielectric behaviour of smart material, lead zirconate tiatanate (PZT, whichis important for wide industrial applications, has been explored. Two samples of nanostructuredPb(Zr0.52Ti0.48O3 ceramic powders were prepared by hydroxide co-precipitation and aqueoussolution method (water bath technique. The XRD pattern of the  powder exhibited the presenceof major tetragonal and minor rhombohedral crystalline phases indicating the mixed-phasecomposition, which is close to the morphotropic phase boundary (MPB. SEM analysis revealedgood homogeneity of the materials. The plot of real part versus imaginary part of the compleximpedance was observed nearly a semicircle, indicating that the samples are good dielectricmaterials, whose resistance decreases considerably with the increase of temperature. Similar tothe normal ferroelectric materials, the dielectric constant ( of PZT has been found to be increasinggradually with temperature and attains a maxima (max. The detailed analysis for the shift in peaktemperature and dielectric constant were carried out.

  16. An introduction to quantum chemical methods applied to drug design.

    Science.gov (United States)

    Stenta, Marco; Dal Peraro, Matteo

    2011-06-01

    The advent of molecular medicine allowed identifying the malfunctioning of subcellular processes as the source of many diseases. Since then, drugs are not only discovered, but actually designed to fulfill a precise task. Modern computational techniques, based on molecular modeling, play a relevant role both in target identification and drug lead development. By flanking and integrating standard experimental techniques, modeling has proven itself as a powerful tool across the drug design process. The success of computational methods depends on a balance between cost (computation time) and accuracy. Thus, the integration of innovative theories and more powerful hardware architectures allows molecular modeling to be used as a reliable tool for rationalizing the results of experiments and accelerating the development of new drug design strategies. We present an overview of the most common quantum chemistry computational approaches, providing for each one a general theoretical introduction to highlight limitations and strong points. We then discuss recent developments in software and hardware resources, which have allowed state-of-the-art of computational quantum chemistry to be applied to drug development.

  17. Halogen bonded supramolecular capsules: a challenging test case for quantum chemical methods.

    Science.gov (United States)

    Sure, Rebecca; Grimme, Stefan

    2016-08-02

    Recently, Diederich et al. synthesized the first supramolecular capsule with a well-defined four-point halogen bonding interaction [Angew. Chem., Int. Ed., 2015, 54, 12339]. This interesting system comprising about 400 atoms represents a challenging test case for accurate quantum chemical methods. We investigate it with our new density functional based composite method for structures and noncovalent interactions (PBEh-3c) as well as our standard protocol for supramolecular thermochemistry and give predictions for chemical modifications to improve the binding strength.

  18. Determination of rare-earth elements in Luna 16 regolith sample by chemical spectral method

    Science.gov (United States)

    Stroganova, N. S.; Ryabukhin, V. A.; Laktinova, N. V.; Ageyeva, L. V.; Galkina, I. P.; Gatinskaya, N. G.; Yermakov, A. N.; Karyakin, A. V.

    1974-01-01

    An analysis was made of regolith from layer A of the Luna 16 sample for rare earth elements, by a chemical spectral method. Chemical and ion exchange concentrations were used to determine the content of 12 elements and Y at the level 0.001 to 0.0001 percent with 10 to 15 percent reproducibility of the emission determination. Results within the limits of reproducibility agree with data obtained by mass spectra, activation, and X-ray fluorescent methods.

  19. Biomechanical properties of acellular sciatic nerves treated with a modified chemical method

    Institute of Scientific and Technical Information of China (English)

    Xinlong Ma; Zhao Yang; Xiaolei Sun; Jianxiong Ma; Xiulan Li; Zhenzhen Yuan; Yang Zhang; Honggang Guo

    2011-01-01

    Nerve grafts are able to adapt to surrounding biomechanical environments if the nerve graft itself exhibits appropriate biomechanical properties (load, elastic modulus, etc.). The present study was designed to determine the differences in biomechanical properties between fresh and chemically acellularized sciatic nerve grafts. Two different chemical methods were used to establish acellular nerve grafts. The nerve was chemically extracted in the Sondell method with a combination of Triton X-100 (nonionic detergent) and sodium deoxycholate (anionic detergent), and in the modified method with a combination of Triton X-200 (anionic detergent), sulfobetaine-10 (SB-10, amphoteric detergents), and sulfobetaine-16 (SB-16, amphoteric detergents). Following acellularization, hematoxylin-eosin staining and scanning electron microscopy demonstrated that the effect of acellularization via the modified method was similar to the traditional Sondell method. However, effects of demyelination and nerve fiber tube integrity were superior to the traditional Sondell method. Biomechanical testing showed that peripheral nerve graft treated using the chemical method resulted in decreased biomechanical properties (ultimate load, ultimate stress, ultimate strain, and mechanical work to fracture) compared with fresh nerves, but the differences had no statistical significance (P > 0.05). These results demonstrated no significant effect on biomechanical properties of nerves treated using the chemical method. In conclusion, nerve grafts treated via the modified method removed Schwann cells, preserved neural structures, and ensured biomechanical properties of the nerve graft, which could be more appropriate for implantation studies.

  20. 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.

  1. 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.

  2. Plant management in natural areas: balancing chemical, mechanical, and cultural control methods

    Science.gov (United States)

    Steven Manning; James. Miller

    2011-01-01

    After determining the best course of action for control of an invasive plant population, it is important to understand the variety of methods available to the integrated pest management professional. A variety of methods are now widely used in managing invasive plants in natural areas, including chemical, mechanical, and cultural control methods. Once the preferred...

  3. Transition-metal-free coupling reaction of vinylcyclopropanes with aldehydes catalyzed by tin hydride.

    Science.gov (United States)

    Ieki, Ryosuke; Kani, Yuria; Tsunoi, Shinji; Shibata, Ikuya

    2015-04-13

    Donor-acceptor cyclopropanes are useful building blocks for catalytic cycloaddition reactions with a range of electrophiles to give various cyclic products. In contrast, relatively few methods are available for the synthesis of homoallylic alcohols through coupling of vinylcyclopropanes (VCPs) with aldehydes, even with transition-metal catalysts. Here, we report that the hydrostannation of vinylcyclopropanes (VCPs) was effectively promoted by dibutyliodotin hydride (Bu2 SnIH). The resultant allylic tin compounds reacted easily with aldehydes. Furthermore, the use of Bu2 SnIH was effectively catalytic in the presence of hydrosilane as a hydride source, which established a coupling reaction of VCPs with aldehydes for the synthesis of homoallylic alcohols without the use of transition-metal catalysts. In contrast to conventional catalytic reactions of VCPs, the presented method allowed the use of several VCPs in addition to conventional donor-acceptor cyclopropanes.

  4. Positive ions of the first- and second-row transition metal hydrides

    Science.gov (United States)

    Pettersson, Lars G. M.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

    1987-01-01

    Theoretical dissociation energies for the first- and second-row transition metal hydride positive ions are critically compared against recent experimental values obtained from ion beam reactive scattering methods. Theoretical spectroscopic parameters and dipole moments are presented for the ground and several low-lying excited states. The calculations employ large Gaussian basis sets and account for electron correlation using the single-reference single- and double-excitation configuration interaction and coupled-pair-functional methods. The Darwin and mass-velocity contributions to the relativistic energy are included in the all-electron calculations on the first-row systems using first-order perturbation theory, and in the second-row systems using the Hay and Wadt relativistic effective core potentials. The theoretical D(0) values for the second-row transition metal hydride positive ions should provide a critical measure of the experimental values, which are not as refined as many of those in the first transition row.

  5. Field induced gradient simulations: a high throughput method for computing chemical potentials in multicomponent systems.

    Science.gov (United States)

    Mehrotra, Anuja Seth; Puri, Sanjay; Khakhar, D V

    2012-04-07

    We present a simulation method for direct computation of chemical potentials in multicomponent systems. The method involves application of a field to generate spatial gradients in the species number densities at equilibrium, from which the chemical potential of each species is theoretically estimated. A single simulation yields results over a range of thermodynamic states, as in high throughput experiments, and the method remains computationally efficient even at high number densities since it does not involve particle insertion at high densities. We illustrate the method by Monte Carlo simulations of binary hard sphere mixtures of particles with different sizes in a gravitational field. The results of the gradient Monte Carlo method are found to be in good agreement with chemical potentials computed using the classical Widom particle insertion method for spatially uniform systems.

  6. 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...

  7. 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.

  8. Method to reduce chemical background interference in atmospheric pressure ionization liquid chromatography-mass spectrometry using exclusive reactions with the chemical reagent dimethyl disulfide

    NARCIS (Netherlands)

    Guo, Xinghua; Bruins, Andries P.; Covey, Thomas R.

    2007-01-01

    The interference of chemical background ions (chemical noise) has been a problem since the inception of mass spectrometry. We present here a novel method to reduce the chemical noise in LC-MS based on exclusive gas-phase reactions with a reactive collision gas in a triple-quadrupole mass spectromete

  9. 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.

  10. Effect of sodium cation on metallacycle β-hydride elimination in CO2-ethylene coupling to acrylates.

    Science.gov (United States)

    Jin, Dong; Williard, Paul G; Hazari, Nilay; Bernskoetter, Wesley H

    2014-03-10

    The catalytic conversion of carbon dioxide and olefins into acrylates has been a long standing target, because society attempts to synthesize commodity chemicals in a more economical and sustainable fashion. Although nickel complexes have been known to successfully couple CO2 and ethylene for decades, a key β-hydride elimination step has proven a major obstacle to the development of a catalytic process. Recent studies have shown that Lewis acid additives can be used to create a lower-energy pathway for β-hydride elimination and facilitate a low number of catalytic turnovers. However, the exact manner, in which the Lewis acid promotes β-hydride elimination remains to be elucidated. Herein, we describe the kinetic and thermodynamic role that commercially relevant and weakly Lewis acidic sodium salts play in promoting β-hydride elimination from nickelalactones synthesized from CO2 and ethylene. This process is compared to a non-Lewis acid promoted pathway, and DFT calculations were used to identify differences between the two systems. The sodium-free isomerization reaction gave a rare CO2 -derived β-nickelalactone complex, which was structurally characterized.

  11. Identification of a Catalytic Iron-Hydride at the H-Cluster of [FeFe]-Hydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Mulder, David W.; Guo, Yisong; Ratzloff, Michael W.; King, Paul W.

    2017-01-11

    Hydrogenases couple electrochemical potential to the reversible chemical transformation of H2 and protons, yet the reaction mechanism and composition of intermediates are not fully understood. In this Communication we describe the biophysical properties of a hydride-bound state (Hhyd) of the [FeFe]-hydrogenase from Chlamydomonas reinhardtii. The catalytic H-cluster of [FeFe]-hydrogenase consists of a [4Fe-4S] subcluster ([4Fe-4S]H) linked by a cysteine thiol to an azadithiolate-bridged 2Fe subcluster ([2Fe]H) with CO and CN- ligands. Mossbauer analysis and density functional theory (DFT) calculations show that Hhyd consists of a reduced [4Fe-4S]H+ coupled to a diferrous [2Fe]H with a terminally bound Fe-hydride. The existence of the Fe-hydride in Hhyd was demonstrated by an unusually low Mossbauer isomer shift of the distal Fe of the [2Fe]H subcluster. A DFT model of Hhyd shows that the Fe-hydride is part of a H-bonding network with the nearby bridging azadithiolate to facilitate fast proton exchange and catalytic turnover.

  12. 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.

  13. Application of a new TLC chemical method for detection of cyclopeptides in plants

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Cyclopeptides have been investigated phytochemically less often because until now there has not been a special chemical method to detect them. Since we found cyclopeptides in Pseudostellaria heterophylla (Caryophyllaceae) in 1991, we have gradually established a special chemical detection method for detecting cyclopeptides in plants, which induces a new thin layer chromatography (TLC) protosite reaction with ninhydrin reagent. With this method, our group isolated and determined 73 cyclopeptides from 17 plants which belong to 5 families and 14 genuses, they are from dicyclopeptides to undecacyclopeptides, including 68 new ones, and were determined based on spectral, chemical and enzymic methods, especially 2D NMR and FAB-MS. Meantime, with this method cyclopeptides can be distinguished from peptidic amides based on their behaviour in TLC.

  14. 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.

  15. Dealloyed Ruthenium Film Catalysts for Hydrogen Generation from Chemical Hydrides

    Directory of Open Access Journals (Sweden)

    Ramis B. Serin

    2017-07-01

    Full Text Available Thin-film ruthenium (Ru and copper (Cu binary alloys have been prepared on a Teflon™ backing layer by cosputtering of the precious and nonprecious metals, respectively. Alloys were then selectively dealloyed by sulfuric acid as an etchant, and their hydrogen generation catalysts performances were evaluated. Sputtering time and power of Cu atoms have been varied in order to tailor the hydrogen generation performances. Similarly, dealloying time and the sulfuric acid concentration have also been altered to tune the morphologies of the resulted films. A maximum hydrogen generation rate of 35 mL min−1 was achieved when Cu sputtering power and time were 200 W and 60 min and while acid concentration and dealloying time were 18 M and 90 min, respectively. It has also been demonstrated that the Ru content in the alloy after dealloying gradually increased with the increasing the sputtering power of Cu. After 90 min dealloying, the Ru to Cu ratio increased to about 190 times that of bare alloy. This is the key issue for observing higher catalytic activity. Interestingly, we have also presented template-free nanoforest-like structure formation within the context of one-step alloying and dealloying used in this study. Last but not least, the long-time hydrogen generation performances of the catalysts system have also been evaluated along 3600 min. During the first 600 min, the catalytic activity was quite stable, while about 24% of the catalytic activity decayed after 3000 min, which still makes these systems available for the development of robust catalyst systems in the area of hydrogen generation.

  16. 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

  17. 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.

  18. Erroneous Wave Functions of Ciuchi et al for Collective Modes in Neutron Production on Metallic Hydride Cathodes

    CERN Document Server

    Widom, A; Larsen, L

    2012-01-01

    There is a recent comment (Ciuchi et al., 2012) concerning the theory of collective many body effects on the neutron production rates in a chemical battery cathode. Ciuchi et al employ an inverse beta decay expression that contains a two body amplitude. Only one electron and one proton may exist in the Ciuchi et al model initial state wave function. A flaw in their reasoning is that one cannot in reality describe collective many body correlations with only a two particle wave function. One needs very many particles to describe collective effects. In the model wave functions of Ciuchi et al there are no metallic hydrides, there are no cathodes and there are no chemical batteries. Employing a wave function with only one electron and one proton is inadequate for describing collective metallic hydride surface quantum plasma physics in cathodes accurately.

  19. Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

    Science.gov (United States)

    Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

    2013-07-19

    A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

  20. 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.

  1. X-ray photon-in/photon-out methods for chemical imaging

    Energy Technology Data Exchange (ETDEWEB)

    Marcus, Matthew A.

    2010-03-24

    Most interesting materials in nature are heterogeneous, so it is useful to have analytical techniques with spatial resolution sufficient to resolve these heterogeneities.This article presents the basics of X-ray photon-in/photon-out chemical imaging. This family of methods allows one to derive images reflectingthe chemical state of a given element in a complex sample, at micron or deep sub-micron scale. X-ray chemical imaging is relatively non-destructiveand element-selective, and requires minimal sample preparation. The article presents the basic concepts and some considerations of data takingand data analysis, along with some examples.

  2. Influence of particle size and preparation methods on the physical and chemical stability of amorphous simvastatin

    DEFF Research Database (Denmark)

    Zhang, Fang; Aaltonen, Jaakko; Tian, Fang

    2009-01-01

    molecular mobility and higher chemical degradation than CM. Therefore, the current study demonstrated that QC and CM have obvious differences in both physical and chemical properties. It was concluded that care should be taken when choosing preparation methods for making amorphous materials. Furthermore......, particle size, a factor that has often been overlooked when dealing with amorphous materials, was shown to have an influence on physical stability of amorphous simvastatin.......This study investigated the factors influencing the stability of amorphous simvastatin. Quench-cooled amorphous simvastatin in two particle size ranges, 150-180 microm (QC-big) and amorphous simvastatin (CM) were prepared, and their physical and chemical...

  3. Identity method to study chemical fluctuations in relativistic heavy-ion collisions

    CERN Document Server

    Gazdzicki, M; Mackowiak, M; Mrowczynski, St

    2011-01-01

    Event-by-event fluctuations of the chemical composition of the hadronic final state of relativistic heavy-ion collisions carry valuable information on the properties of strongly interacting matter produced in the collisions. However, in experiments incomplete particle identification distorts the observed fluctuation signals. The effect is quantitatively studied and a new technique for measuring chemical fluctuations, the identity method, is proposed. The method fully eliminates the effect of incomplete particle identification. The application of the identity method to experimental data is explained.

  4. Method for Non-Invasive Determination of Chemical Properties of Aqueous Solutions

    Science.gov (United States)

    Todd, Paul W. (Inventor); Jones, Alan (Inventor); Thomas, Nathan A. (Inventor)

    2016-01-01

    A method for non-invasively determining a chemical property of an aqueous solution is provided. The method provides the steps of providing a colored solute having a light absorbance spectrum and transmitting light through the colored solute at two different wavelengths. The method further provides the steps of measuring light absorbance of the colored solute at the two different transmitted light wavelengths, and comparing the light absorbance of the colored solute at the two different wavelengths to determine a chemical property of an aqueous solution.

  5. Methods for conversion of carbohydrates in ionic liquids to value-added chemicals

    Science.gov (United States)

    Zhao, Haibo; Holladay, Johnathan E.

    2011-05-10

    Methods are described for converting carbohydrates including, e.g., monosaccharides, disaccharides, and polysaccharides in ionic liquids to value-added chemicals including furans, useful as chemical intermediates and/or feedstocks. Fructose is converted to 5-hydroxylmethylfurfural (HMF) in the presence of metal halide and acid catalysts. Glucose is effectively converted to HMF in the presence of chromium chloride catalysts. Yields of up to about 70% are achieved with low levels of impurities such as levulinic acid.

  6. A NOVEL METHOD TO SYNTHESIZE N-DOPED CNTs ARRAYS VIA CHEMICAL MODIFYING POROUS ALUMINA MEMBRANE

    OpenAIRE

    CHENGYONG LI; LEI HE

    2014-01-01

    N-doped carbon nanotubes (CNTs) arrays were fabricated via simply chemical modifying porous alumina membrane (PAM) with dopamine. The diameter of N-doped CNTs is about 60–70 nm. The N/C atomic ratio is calculated to be 0.05 and the main functionality is pyridone/pyrrole N. This chemical modifying method can be used to fabricate mass of N-doped CNTs arrays in one step with single raw material.

  7. a Novel Method to Synthesize N-DOPED CNTs Arrays via Chemical Modifying Porous Alumina Membrane

    Science.gov (United States)

    Li, Chengyong; He, Lei

    2014-01-01

    N-doped carbon nanotubes (CNTs) arrays were fabricated via simply chemical modifying porous alumina membrane (PAM) with dopamine. The diameter of N-doped CNTs is about 60-70 nm. The N/C atomic ratio is calculated to be 0.05 and the main functionality is pyridone/pyrrole N. This chemical modifying method can be used to fabricate mass of N-doped CNTs arrays in one step with single raw material.

  8. A Method for Quantitative Analysis of Chemical Mixtures with THz Time Domain Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zeng-Yan; JI Te; YU Xiao-Han; XIAO Ti-Qiao; XU Hong-Jie

    2006-01-01

    @@ A method for analysing chemical mixtures quantitatively with terahertz time domain spectroscopy is proposed.The experimental results demonstrate the feasibility of this technique. Transmission coefficient of THz wave at the sample surface is taken into account to improve the analytic precision. Isomer mixtures are chosen as the experimental samples. Compared to similar techniques, the analytic precision could be improved evidently in this method.

  9. Carbamate Stabilities of Sterically Hindered Amines from Quantum Chemical Methods: Relevance ofr CO2 Capture

    NARCIS (Netherlands)

    Gangarapu, S.; Marcelis, A.T.M.; Zuilhof, H.

    2013-01-01

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled

  10. Carbamate Stabilities of Sterically Hindered Amines from Quantum Chemical Methods: Relevance ofr CO2 Capture

    NARCIS (Netherlands)

    Gangarapu, S.; Marcelis, A.T.M.; Zuilhof, H.

    2013-01-01

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled

  11. Ammonia-Borane and Amine-Borane Dehydrogenation Mediated by Complex Metal Hydrides.

    Science.gov (United States)

    Rossin, Andrea; Peruzzini, Maurizio

    2016-08-10

    This review is a comprehensive survey of the last 10 years of research on ammonia-borane and amine-borane dehydrogenation mediated by complex metal hydrides (CMHs), within the broader context of chemical hydrogen storage. The review also collects those cases where CMHs are the catalyst spent form or its resting state. Highlights on the reaction mechanism (strictly dependent on the CMH of choice) and the catalysts efficiency (in terms of equivalents of H2 produced and relative reaction rates) are provided throughout the discussion.

  12. 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

  13. Photography - Determination of thiosulphate and other residual chemicals in processed photographic films, plates and papers - Methylene blue photometric method and silver sulphide densitometric method

    CERN Document Server

    International Organization for Standardization. Geneva

    1977-01-01

    Photography - Determination of thiosulphate and other residual chemicals in processed photographic films, plates and papers - Methylene blue photometric method and silver sulphide densitometric method

  14. Using different chemical methods for deposition of copper selenide thin films and comparison of their characterization.

    Science.gov (United States)

    Güzeldir, Betül; Sağlam, Mustafa

    2015-11-05

    Different chemical methods such as Successive Ionic Layer Adsorption and Reaction (SILAR), spin coating and spray pyrolysis methods were used to deposite of copper selenide thin films on the glass substrates. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX) spectroscopy and UV-vis spectrophotometry. The XRD and SEM studies showed that all the films exhibit polycrystalline nature and crystallinity of copper selenide thin films prepared with spray pyrolysis greater than spin coating and SILAR methods. From SEM and AFM images, it was observed copper selenide films were uniform on the glass substrates without any visible cracks or pores. The EDX spectra showed that the expected elements exist in the thin films. Optical absorption studies showed that the band gaps of copper selenide thin films were in the range 2.84-2.93 eV depending on different chemical methods. The refractive index (n), optical static and high frequency dielectric constants (ε0, ε∞) values were calculated by using the energy bandgap values for each deposition method. The obtained results from different chemical methods revealed that the spray pyrolysis technique is the best chemical deposition method to fabricate copper selenide thin films. This absolute advantage was lead to play key roles on performance and efficiency electrochromic and photovoltaic devices.

  15. 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.

  16. 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.

  17. 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

  18. 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.)

  19. 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.

  20. 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%.

  1. 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.

  2. 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)

  3. 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.

  4. 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.

  5. Chemical Footprint Method for Improved Communication of Freshwater Ecotoxicity Impacts in the Context of Ecological Limits

    DEFF Research Database (Denmark)

    Bjørn, Anders; Diamond, Miriam; Birkved, Morten

    2014-01-01

    The ecological footprint method has been successful in communicating environmental impacts of anthropogenic activities in the context of ecological limits. We introduce a chemical footprint method that expresses ecotoxicity impacts from anthropogenic chemical emissions as the dilution needed...... to avoid freshwater ecosystem damage. The indicator is based on USEtox characterization factors with a modified toxicity reference point. Chemical footprint results can be compared to the actual dilution capacity within the geographic vicinity receiving the emissions to estimate whether its ecological...... limit has been exceeded and hence whether emissions can be expected to be environmentally sustainable. The footprint method was illustrated using two case studies. The first was all inventoried emissions from European countries and selected metropolitan areas in 2004, which indicated that the dilution...

  6. Chemical Pretreatment Methods for the Production of Cellulosic Ethanol: Technologies and Innovations

    Directory of Open Access Journals (Sweden)

    Edem Cudjoe Bensah

    2013-01-01

    Full Text Available Pretreatment of lignocellulose has received considerable research globally due to its influence on the technical, economic and environmental sustainability of cellulosic ethanol production. Some of the most promising pretreatment methods require the application of chemicals such as acids, alkali, salts, oxidants, and solvents. Thus, advances in research have enabled the development and integration of chemical-based pretreatment into proprietary ethanol production technologies in several pilot and demonstration plants globally, with potential to scale-up to commercial levels. This paper reviews known and emerging chemical pretreatment methods, highlighting recent findings and process innovations developed to offset inherent challenges via a range of interventions, notably, the combination of chemical pretreatment with other methods to improve carbohydrate preservation, reduce formation of degradation products, achieve high sugar yields at mild reaction conditions, reduce solvent loads and enzyme dose, reduce waste generation, and improve recovery of biomass components in pure forms. The use of chemicals such as ionic liquids, NMMO, and sulphite are promising once challenges in solvent recovery are overcome. For developing countries, alkali-based methods are relatively easy to deploy in decentralized, low-tech systems owing to advantages such as the requirement of simple reactors and the ease of operation.

  7. 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)

  8. 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.

  9. 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

  10. Wet-chemical systems and methods for producing black silicon substrates

    Energy Technology Data Exchange (ETDEWEB)

    Yost, Vernon; Yuan, Hao-Chih; Page, Matthew

    2015-05-19

    A wet-chemical method of producing a black silicon substrate. The method comprising soaking single crystalline silicon wafers in a predetermined volume of a diluted inorganic compound solution. The substrate is combined with an etchant solution that forms a uniform noble metal nanoparticle induced Black Etch of the silicon wafer, resulting in a nanoparticle that is kinetically stabilized. The method comprising combining with an etchant solution having equal volumes acetonitrile/acetic acid:hydrofluoric acid:hydrogen peroxide.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. The phase-resolved photoacoustic method to indicate chemical assignments of paracetamol

    Science.gov (United States)

    Camilotti, J. G.; Somer, A.; Costa, G. F.; Ribeiro, M. A.; Bonardi, C.; Cruz, G. K.; Gómez, S. L.; Beltrame, F. L.; Medina, A. N.; Sato, F.; Astrath, N. G. C.; Novatski, A.

    2014-03-01

    In this work, the phase-resolved photoacoustic method was applied to provide specific information on the chemical assignments of paracetamol in the near-infrared region. Two broad bands, centered at 1370 and 1130 nm, were well-resolved using this method, making it possible to assign the peaks centered at 1398, 1355 and 1295 nm to a C-H combination from a CH3 structure and the peak at 1305 nm to a C-H combination from the aromatic ring. This information represents a new finding in chemical studies regarding this medicament.

  17. Theoretical study of the ground-state structures and properties of niobium hydrides under pressure

    Science.gov (United States)

    Gao, Guoying; Hoffmann, Roald; Ashcroft, N. W.; Liu, Hanyu; Bergara, Aitor; Ma, Yanming

    2013-11-01

    As part of a search for enhanced superconductivity, we explore theoretically the ground-state structures and properties of some hydrides of niobium over a range of pressures and particularly those with significant hydrogen content. A primary motivation originates with the observation that under normal conditions niobium is the element with the highest superconducting transition temperature (Tc), and moreover some of its compounds are metals again with very high Tc's. Accordingly, combinations of niobium with hydrogen, with its high dynamic energy scale, are also of considerable interest. This is reinforced further by the suggestion that close to its insulator-metal transition, hydrogen may be induced to enter the metallic state somewhat prematurely by the addition of a relatively small concentration of a suitable transition metal. Here, the methods used correctly reproduce some ground-state structures of niobium hydrides at even higher concentrations of niobium. Interestingly, the particular stoichiometries represented by NbH4 and NbH6 are stabilized at fairly low pressures when proton zero-point energies are included. While no paired H2 units are found in any of the hydrides we have studied up to 400 GPa, we do find complex and interesting networks of hydrogens around the niobiums in high-pressure NbH6. The Nb-Nb separations in NbHn are consistently larger than those found in Nb metal at the respective pressures. The structures found in the ground states of the high hydrides, many of them metallic, suggest that the coordination number of hydrogens around each niobium atom grows approximately as 4n in NbHn (n = 1-4), and is as high as 20 in NbH6. NbH4 is found to be a plausible candidate to become a superconductor at high pressure, with an estimated Tc ˜ 38 K at 300 GPa.

  18. 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.

  19. Stability of alkali-metal hydrides: effects of n-type doping

    Science.gov (United States)

    Olea Amezcua, Monica Araceli; de La Peña Seaman, Omar; Rivas Silva, Juan Francisco; Heid, Rolf; Bohnen, Klaus-Peter

    Metal hydrides could be considered ideal solid-state hydrogen storage systems, they have light weight and high hydrogen volumetric densities, but the hydrogen desorption process requires excessively high temperatures due to their high stability. Efforts have been performed to improve their dehydrogenation properties, based on the introduction of defects, impurities and doping. We present a systematic study of the n-type (electronic) doping effects on the stability of two alkali-metal hydrides: Na1-xMgxH and Li1-xBexH. These systems have been studied within the framework of density functional perturbation theory, using a mixed-basis pseudopotential method and the self-consistent version of the virtual crystal approximation to model the doping. The full-phonon dispersions are analyzed for several doping content, paying special attention to the crystal stability. It is found a doping content threshold for each system, where they are close to dynamical instabilities, which are related to charge redistribution in interstitial zones. Applying the quasiharmonic approximation, the vibrational free energy, the linear thermal expansion and heat capacities are obtained for both hydrides systems and are analyzed as a function of the doping content. This work is partially supported by the VIEP-BUAP 2016 and CONACYT-México (No.221807) projects.

  20. OPTIMIZATION OF INTERNAL HEAT EXCHANGERS FOR HYDROGEN STORAGE TANKS UTILIZING METAL HYDRIDES

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, S.; Tamburello, D.; Hardy, B.; Anton, D.; Gorbounov, M.; Cognale, C.; van Hassel, B.; Mosher, D.

    2011-07-14

    Two detailed, unit-cell models, a transverse fin design and a longitudinal fin design, of a combined hydride bed and heat exchanger are developed in COMSOL{reg_sign} Multiphysics incorporating and accounting for heat transfer and reaction kinetic limitations. MatLab{reg_sign} scripts for autonomous model generation are developed and incorporated into (1) a grid-based and (2) a systematic optimization routine based on the Nelder-Mead downhill simplex method to determine the geometrical parameters that lead to the optimal structure for each fin design that maximizes the hydrogen stored within the hydride. The optimal designs for both the transverse and longitudinal fin designs point toward closely-spaced, small cooling fluid tubes. Under the hydrogen feed conditions studied (50 bar), a 25 times improvement or better in the hydrogen storage kinetics will be required to simultaneously meet the Department of Energy technical targets for gravimetric capacity and fill time. These models and methodology can be rapidly applied to other hydrogen storage materials, such as other metal hydrides or to cryoadsorbents, in future work.

  1. Minimum Entropy Generation Theorem Investigation and Optimization of Metal Hydride Alloy Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Chi-Chang Wang

    2014-05-01

    Full Text Available The main purpose of this paper is to carry out numerical simulation of the hydrogen storage on exothermic reaction of metal hydride LaNi5 alloy container. In addition to accelerating the reaction speed of the internal metal hydride by internal control tube water-cooled mode, analyze via the application of second law of thermodynamics the principle of entropy generation. Use COMSOL Mutilphysics 4.3 a to engage in finite element method value simulation on two-dimensional axisymmetric model. Also on the premise that the internal control tube parameters the radius ri, the flow rate U meet the metal hydride saturation time, observe the reaction process of two parameters on the tank, entropy distribution and the results of the accumulated entropy. And try to find the internal tube parameter values of the minimum entropy, whose purpose is to be able to identify the reaction process and the reaction results of internal tank’s optimum energy conservation.

  2. First-principles study on structural stability of 3d transition metal alloying magnesium hydride

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A first-principles plane-wave pseudopotential method based on the density functional theory was used to investigate the energy and electronic structure of magnesium hydride (MgH2) alloyed by 3d transition metal elements. Through calculations of the negative heat formation of magnesium hydride alloyed by X (X denotes 3d transition metal) element, it is found that when a little X (not including Sc) dissolves into magnesium hydride, the structural stability of alloying systems decreases, which indicates that the dehydrogenation properties of MgH2 can be improved. After comparing the densities of states(DOS) and the charge distribution of MgH2 with or without X alloying, it is found that the improvement for the dehydrogenation properties of MgH2 alloyed by X attributes to the fact that the weakened bonding between magnesium and hydrogen is caused by the stronger interactions between X (not including Cu) and hydrogen. The calculation results of the improvement for the dehydrogenation properties of MgH2-X (X=Ti, V, Mn, Fe, Co,Ni, Cu) systems are in agreement with the experimental results. Hence, the dehydrogenation properties of MgH2 are expected to be improved by addition of Cr, Zn alloying elements.

  3. 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.

  4. Metallographic and fractographic observations of hydrides during delayed hydride cracking in Zr-2.5% Nb alloy

    Energy Technology Data Exchange (ETDEWEB)

    Jovanovic, M.T.; Eadie, R.L. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Chemical and Materials Engineering; Shek, G.K.; Seahra, H. [Ontario Hydro Technologies, Toronto, Ontario (Canada)

    1998-01-01

    Potential drop measurements, optical microscopy, and scanning electron microscopy were performed to study the mechanism of delayed hydride cracking (DHC), the relation of the fracture to the hydride morphology, and the fractography of the DHC mechanism. The material used in this study was taken from modified extrusions of the material used to manufacture Zr-2.5% Nb pressure tubes. The material was electrolytically hydrided to approximately 60 {micro}g/g before testing. Cracking tests were carried out at 250 C with an applied K{sub 1} of 12 MPa {radical}m. The number of potential jumps was strongly correlated to the number of striations on the fracture surface. The results indicate that the DHC process occurs in these samples in an intermittent fashion. Brittle fracture is the operating fracture mechanism for the hydrides that cover most of the fracture surface, but there are some regions of ductile fracture both within the fracture and at the striations.

  5. Raman and photoelectron spectroscopic investigation of high-purity niobium materials: Oxides, hydrides, and hydrocarbons

    Science.gov (United States)

    Singh, Nageshwar; Deo, M. N.; Nand, Mangla; Jha, S. N.; Roy, S. B.

    2016-09-01

    We present investigations of the presence of oxides, hydrides, and hydrocarbons in high-purity (residual resistivity ratio, ˜300) niobium (Nb) materials used in fabrication of superconducting radio frequency (SRF) cavities for particle accelerators. Raman spectroscopy of Nb materials (as-received from the vendor as well as after surface chemical- and thermal processing) revealed numerous peaks, which evidently show the presence of oxides (550 cm-1), hydrides (1277 and 1385 cm-1: ˜80 K temperature), and groups of hydrocarbons (1096, 2330, 2710, 2830, 2868, and 3080 cm-1). The present work provides direct spectroscopic evidence of hydrides in the electropolished Nb materials typically used in SRF cavities. Raman spectroscopy thus can provide vital information about the near-surface chemical species in niobium materials and will help in identifying the cause for the performance degradation of SRF cavities. Furthermore, photoelectron spectroscopy was performed on the Nb samples to complement the Raman spectroscopy study. This study reveals the presence of C and O in the Nb samples. Core level spectra of Nb (doublet 3d5/2 and 3d3/2) show peaks near 206.6 and 209.4 eV, which can be attributed to the Nb5+ oxidation state. The core level spectra of C 1 s of the samples are dominated by graphitic carbon (binding energy, 284.6 eV), while the spectra of O 1 s are asymmetrically peaked near binding energy of ˜529 eV, and that indicates the presence of metal-oxide Nb2O5. The valence-band spectra of the Nb samples are dominated by a broad peak similar to O 2p states, but after sputtering (for 10 min) a peak appears at ˜1 eV, which is a feature of the elemental Nb atom.

  6. 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.

  7. Comparison of the Winograd method and chemical cauterization with 10% sodium hydroxide for treating ingrown toenails

    Directory of Open Access Journals (Sweden)

    Nebahat Demet Akpolat

    2016-09-01

    Full Text Available Background and Design: This study was performed to assess the therapeutic outcomes of the surgical method, described by Winograd and chemical cauterization with sodium hydroxide in patients with Heifetz stage 2 and 3 ingrown toenail (recurrence, complication, improvement and time to regain activity. Materials and Methods: One-hundred patients who presented to the outpatient clinics of orthopedics, general surgery and dermatology with the complaints of pain, redness and discharge in the toenail between January 2010 and January 2012 and who failed to respond to conservative treatment and were diagnosed with Heifetz stage 2 and 3 ingrown toenail. Fifty patients underwent chemical cauterization with sodium hydroxide while 50 underwent Winograd surgery. Results: The patients were followed up for a year at 2-month intervals. While no recurrence was observed in patients who received chemical cauterization, five patients who underwent Winograd surgery had recurrence (p=0.022. Three patients receiving Winograd surgery were found to have superficial wound side infection on postoperative follow-up (p=0.08. Patients, who underwent chemical cauterization with sodium hydroxide, were detected to improve and return to normal activity in a shorter period. Conclusion: Chemical cauterization of the germinal matrix with 10% sodium hydroxide is a convenient method with a low rate of complication and recurrence compared to the Winograd surgery in the treatment of ingrown toenails.

  8. In silico toxicology: computational methods for the prediction of chemical toxicity

    KAUST Repository

    Raies, Arwa B.

    2016-01-06

    Determining the toxicity of chemicals is necessary to identify their harmful effects on humans, animals, plants, or the environment. It is also one of the main steps in drug design. Animal models have been used for a long time for toxicity testing. However, in vivo animal tests are constrained by time, ethical considerations, and financial burden. Therefore, computational methods for estimating the toxicity of chemicals are considered useful. In silico toxicology is one type of toxicity assessment that uses computational methods to analyze, simulate, visualize, or predict the toxicity of chemicals. In silico toxicology aims to complement existing toxicity tests to predict toxicity, prioritize chemicals, guide toxicity tests, and minimize late-stage failures in drugs design. There are various methods for generating models to predict toxicity endpoints. We provide a comprehensive overview, explain, and compare the strengths and weaknesses of the existing modeling methods and algorithms for toxicity prediction with a particular (but not exclusive) emphasis on computational tools that can implement these methods and refer to expert systems that deploy the prediction models. Finally, we briefly review a number of new research directions in in silico toxicology and provide recommendations for designing in silico models.

  9. Surface modification of a proton exchange membrane and hydrogen storage in a metal hydride for fuel cells

    Science.gov (United States)

    Andrews, Lisa

    promising option. Effective hydrogen storage methods must be used as sources of available hydrogen. One possibility is to use hydrogen stored in a solid chemical compound such as magnesium hydride. The kinetics of hydrogen release from the hydrolysis of magnesium hydride with 2 wt% acetic acid was examined. The hydrogen produced was supplied to a fuel cell and the amount of hydrogen consumed by the fuel cell was determined. Carbon nanotubes also can play a role in energy sources and as components in fuel cells. VUV photo-oxidized single walled carbon nanotubes (SWNT) paper was grafted with polyacrylic acid and analyzed using XPS.

  10. Comparison of Parameter Estimation Methods in Stochastic Chemical Kinetic Models: Examples in Systems Biology.

    Science.gov (United States)

    Gupta, Ankur; Rawlings, James B

    2014-04-01

    Stochastic chemical kinetics has become a staple for mechanistically modeling various phenomena in systems biology. These models, even more so than their deterministic counterparts, pose a challenging problem in the estimation of kinetic parameters from experimental data. As a result of the inherent randomness involved in stochastic chemical kinetic models, the estimation methods tend to be statistical in nature. Three classes of estimation methods are implemented and compared in this paper. The first is the exact method, which uses the continuous-time Markov chain representation of stochastic chemical kinetics and is tractable only for a very restricted class of problems. The next class of methods is based on Markov chain Monte Carlo (MCMC) techniques. The third method, termed conditional density importance sampling (CDIS), is a new method introduced in this paper. The use of these methods is demonstrated on two examples taken from systems biology, one of which is a new model of single-cell viral infection. The applicability, strengths and weaknesses of the three classes of estimation methods are discussed. Using simulated data for the two examples, some guidelines are provided on experimental design to obtain more information from a limited number of measurements.

  11. A finite difference method for estimating second order parameter sensitivities of discrete stochastic chemical reaction networks.

    Science.gov (United States)

    Wolf, Elizabeth Skubak; Anderson, David F

    2012-12-14

    We present an efficient finite difference method for the approximation of second derivatives, with respect to system parameters, of expectations for a class of discrete stochastic chemical reaction networks. The method uses a coupling of the perturbed processes that yields a much lower variance than existing methods, thereby drastically lowering the computational complexity required to solve a given problem. Further, the method is simple to implement and will also prove useful in any setting in which continuous time Markov chains are used to model dynamics, such as population processes. We expect the new method to be useful in the context of optimization algorithms that require knowledge of the Hessian.

  12. Grid-based methods for biochemical ab initio quantum chemical applications

    Energy Technology Data Exchange (ETDEWEB)

    Colvin, M.E.; Nelson, J.S.; Mori, E. [and others

    1997-01-01

    A initio quantum chemical methods are seeing increased application in a large variety of real-world problems including biomedical applications ranging from drug design to the understanding of environmental mutagens. The vast majority of these quantum chemical methods are {open_quotes}spectral{close_quotes}, that is they describe the charge distribution around the nuclear framework in terms of a fixed analytic basis set. Despite the additional complexity they bring, methods involving grid representations of the electron or solvent charge can provide more efficient schemes for evaluating spectral operators, inexpensive methods for calculating electron correlation, and methods for treating the electrostatic energy of salvation in polar solvents. The advantage of mixed or {open_quotes}pseudospectral{close_quotes} methods is that they allow individual non-linear operators in the partial differential equations, such as coulomb operators, to be calculated in the most appropriate regime. Moreover, these molecular grids can be used to integrate empirical functionals of the electron density. These so-called density functional methods (DFT) are an extremely promising alternative to conventional post-Hartree Fock quantum chemical methods. The introduction of a grid at the molecular solvent-accessible surface allows a very sophisticated treatment of a polarizable continuum solvent model (PCM). Where most PCM approaches use a truncated expansion of the solute`s electric multipole expansion, e.g. net charge (Born model) or dipole moment (Onsager model), such a grid-based boundary-element method (BEM) yields a nearly exact treatment of the solute`s electric field. This report describes the use of both DFT and BEM methods in several biomedical chemical applications.

  13. Novel Local Calibration Method for Chemical Oxygen Demand Measurements by Using UV-Vis Spectrometry

    Science.gov (United States)

    Yingtian, Hu; Chao, Liu; Xiaoping, Wang

    2017-05-01

    In recent years, ultraviolet-visible spectroscopy has been widely used for chemical oxygen demand (COD) measurements of water. However, chemical compositions of substance in different water samples can cause measurement deviations, so a local calibration is needed. In this study, a novel local calibration method is proposed. The absorption spectra of COD standard solutions and wastewater samples taken from four factories were collected. We analyzed the impact of chemical compositions of substance in different water samples and extracted the morphology features of their absorptive spectra for recognition models. Furthermore, we calculated the local calibration parameters of the four categories of real water samples by specific modification based on the ability of light absorption in various water environments. After the process of local calibration, the root mean square errors (RMSEs) of the predictions were very small, which highlights the potential of this method for improving the accuracy and adaptability of COD measurements based on ultraviolet-visible spectrum.

  14. 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.

  15. Ether-like Si-Ge hydrides for applications in synthesis of nanostructured semiconductors and dielectrics.

    Science.gov (United States)

    Tice, Jesse B; Weng, Change; Tolle, John; D'Costa, Vijay R; Singh, Rachna; Menendez, Jose; Kouvetakis, John; Chizmeshya, Andrew V G

    2009-09-14

    Hydrolysis reactions of silyl-germyl triflates are used to produce ether-like Si-Ge hydride compounds including H(3)SiOSiH(3) and the previously unknown O(SiH(2)GeH(3))(2). The structural, energetic and vibrational properties of the latter were investigated by experimental and quantum chemical simulation methods. A combined Raman, infrared and theoretical analysis indicated that the compound consists of an equal mixture of linear and gauche isomers in analogy to the butane-like H(3)GeSiH(2)SiH(2)GeH(3) with an exceedingly small torsional barrier of approximately 0.2 kcal mol(-1). This is also corroborated by thermochemistry simulations which indicate that the energy difference between the isomers is less than 1 kcal mol(-1). Proof-of-principle depositions of O(SiH(2)GeH(3))(2) at 500 degrees C on Si(100) yielded nearly stoichiometric Si(2)Ge(2)O materials, closely reflecting the composition of the molecular core. A complete characterization of the film by RBS, XTEM, Raman and IR ellipsometry revealed the presence of Si(0.30)Ge(0.70) quantum dots embedded within an amorphous matrix of Si-Ge-O suboxide, as required for the fabrication of high performance nonvolatile memory devices. The use of readily available starting materials coupled with facile purification and high yields also makes the above molecular approach an attractive synthesis route to H(3)SiOSiH(3) with industrial applications in the formation of Si-O-N high-k gate materials in high-mobility SiGe based transistors.

  16. Concentration of 'forgotten' substances using the XAD concentration method. Suitability of the method for hydrophilic chemicals

    NARCIS (Netherlands)

    Collombon MT; LER

    2007-01-01

    Concentration of forgotten substances using the XAD concentration method In the nineties, RIVM developed a method to concentrate toxic substances on XAD (a synthetic resin). Using bioassays, the toxicity can be determined in the concentrate. 'Modern' toxic substances tend to be more polar then 'clas

  17. Chemical stability of extemporaneously compounded omeprazole formulations: a comparison of two methods of compounding.

    Science.gov (United States)

    Garg, Sanjay; Svirskis, Darren; Al-Kabban, Majid; Farhan, Samer; Komeshi, Mohammed; Lee, Jacky; Liu, Quincy; Naidoo, Sacha; Kairuz, Therese

    2009-01-01

    Liquid preparations of omeprazole are compounded extemporaneously for patients who cannot tolerate or have difficulty with tablets or capsules, such as those with a nasogastric tube or jejunal or feeding tube, those with a swallowing disorder, and young children and the elderly. Recommendations for preparation of a liquid from the enteric-coated pellets of omeprazole capsules are available in the literature. The pellets are dissolved in a sodium bicarbonate solution; shaking is recommended to aid dissolution. Apparently some pharmacists crush the pellets to speed up the compounding process. The aim of this study was to investigate the chemical stability of omeprazole in extemporaneously compounded liquids prepared by the grinding and shaking methods. A high-performance liquid chromatographic method was developed for evaluation of chemical stability. Samples were stored at 2 deg C (refrigerated conditions) or 25 deg C/60% relative humidity and assayed for drug concentration at 0, 1, 2, 4, and 8 weeks. The method of preparation affected the chemical stability of omeprazole when stored at 25 deg C/60% relative humidity; it was stable for 4 weeks if prepared by the shaking method, but for only 1 week if prepared by the grinding method. For both methods, the suspension was stable for 8 weks if stored under refrigerated conditions. It is recommended that the shaking method be employed for extemporaneously compounded omeprazole suspensions, and that the prepared suspension be stored in the refrigerator.

  18. Rodent-repellent studies. I. Method for the evaluation of chemical repellents

    Science.gov (United States)

    Bellack, E.; DeWitt, J.B.

    1949-01-01

    A biological assay procedure and a method for the numerical expression of results have been devised for the determination of the repellency to rodents of different chemical compounds. The procedure is based upon the degree of acceptability of foods containing the candidate repellents,. and has been shown. to offer a rapid, reliable measure of repellent activIty.

  19. Structural properties of produced CuO/NiO/glass thin layers Produced by chemical method

    Directory of Open Access Journals (Sweden)

    A. Ramezani

    2016-12-01

    Full Text Available Nickel Oxide and Copper oxide on Nickel Oxide thin layers were produced by chemical bath deposition method. There nano structures were investigated by SEM and EDAX analysis. By producing CuO/NiO/glass sandwich layers nano structure of NiO/glass layer changed and fraction of voids decreases. In sandwich layer physical property of outer layer was dominant

  20. Methods for the Determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition

    Science.gov (United States)

    This NERL-Cincinnati publication, “Methods for the Determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition” was prepared as the continuation of an initiative to gather together under a single cover a compendium of standardized laborato...

  1. Comparison of chemical, electrophoretic and in vitro digestion methods for predicting fish meal nutritive quality

    DEFF Research Database (Denmark)

    Bassompierre, M.; Larsen, K.L.; Zimmermann, W.

    1998-01-01

    Chemical, electrophoretic and in vitro digestion methods were compared with respect to predictions given regarding fish meal (FM) quality. FMs were manufactured by mixing a press-cake, with spray dried stickwater concentrate from the identical raw material, thereby providing samples containing...

  2. Measurement of interfacial areas with the chemical method for a system with alternating dispersed phases

    NARCIS (Netherlands)

    Woezik, van B.A.A.; Westerterp, K.R.

    2000-01-01

    The interfacial area for a liquid–liquid system has been determined by the chemical reaction method. The saponification of butyl formate ester with 8 M sodium hydroxide has been used to this end. A correlation has been derived to describe the mole flux of ester through the interface and the kinetic

  3. Methods for the Determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition

    Science.gov (United States)

    This NERL-Cincinnati publication, “Methods for the Determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition” was prepared as the continuation of an initiative to gather together under a single cover a compendium of standardized laborato...

  4. Heat Recovery from High Temperature Slags: A Review of Chemical Methods

    Directory of Open Access Journals (Sweden)

    Yongqi Sun

    2015-03-01

    Full Text Available Waste heat recovery from high temperature slags represents the latest potential way to remarkably reduce the energy consumption and CO2 emissions of the steel industry. The molten slags, in the temperature range of 1723–1923 K, carry large amounts of high quality energy. However, the heat recovery from slags faces several fundamental challenges, including their low thermal conductivity, inside crystallization, and discontinuous availability. During past decades, various chemical methods have been exploited and performed including methane reforming, coal and biomass gasification, and direct compositional modification and utilization of slags. These methods effectively meet the challenges mentioned before and help integrate the steel industry with other industrial sectors. During the heat recovery using chemical methods, slags can act as not only heat carriers but also as catalysts and reactants, which expands the field of utilization of slags. Fuel gas production using the waste heat accounts for the main R&D trend, through which the thermal heat in the slag could be transformed into high quality chemical energy in the fuel gas. Moreover, these chemical methods should be extended to an industrial scale to realize their commercial application, which is the only way by which the substantial energy in the slags could be extracted, i.e., amounting to 16 million tons of standard coal in China.

  5. Designing metal hydride complexes for water splitting reactions: a molecular electrostatic potential approach.

    Science.gov (United States)

    Sandhya, K S; Suresh, Cherumuttathu H

    2014-08-28

    The hydridic character of octahedral metal hydride complexes of groups VI, VII and VIII has been systematically studied using molecular electrostatic potential (MESP) topography. The absolute minimum of MESP at the hydride ligand (Vmin) and the MESP value at the hydride nucleus (VH) are found to be very good measures of the hydridic character of the hydride ligand. The increasing/decreasing electron donating feature of the ligand environment is clearly reflected in the increasing/decreasing negative character of Vmin and VH. The formation of an outer sphere metal hydride-water complex showing the HH dihydrogen interaction is supported by the location and the value of Vmin near the hydride ligand. A higher negative MESP suggested lower activation energy for H2 elimination. Thus, MESP features provided a way to fine-tune the ligand environment of a metal-hydride complex to achieve high hydridicity for the hydride ligand. The applicability of an MESP based hydridic descriptor in designing water splitting reactions is tested for group VI metal hydride model complexes of tungsten.

  6. Investigation of the chemical composition-antibacterial activity relationship of essential oils by chemometric methods.

    Science.gov (United States)

    Miladinović, Dragoljub L; Ilić, Budimir S; Mihajilov-Krstev, Tatjana M; Nikolić, Nikola D; Miladinović, Ljiljana C; Cvetković, Olga G

    2012-05-01

    The antibacterial effects of Thymus vulgaris (Lamiaceae), Lavandula angustifolia (Lamiaceae), and Calamintha nepeta (Lamiaceae) Savi subsp. nepeta var. subisodonda (Borb.) Hayek essential oils on five different bacteria were estimated. Laboratory control strain and clinical isolates from different pathogenic media were researched by broth microdilution method, with an emphasis on a chemical composition-antibacterial activity relationship. The main constituents of thyme oil were thymol (59.95%) and p-cymene (18.34%). Linalool acetate (38.23%) and β-linalool (35.01%) were main compounds in lavender oil. C. nepeta essential oil was characterized by a high percentage of piperitone oxide (59.07%) and limonene (9.05%). Essential oils have been found to have antimicrobial activity against all tested microorganisms. Classification and comparison of essential oils on the basis of their chemical composition and antibacterial activity were made by utilization of appropriate chemometric methods. The chemical principal component analysis (PCA) and hierachical cluster analysis (HCA) separated essential oils into two groups and two sub-groups. Thyme essential oil forms separate chemical HCA group and exhibits highest antibacterial activity, similar to tetracycline. Essential oils of lavender and C. nepeta in the same chemical HCA group were classified in different groups, within antibacterial PCA and HCA analyses. Lavender oil exhibits higher antibacterial ability in comparison with C. nepeta essential oil, probably based on the concept of synergistic activity of essential oil components.

  7. A modified coupled pair functional approach. [for dipole moment calculation of metal hydride ground states

    Science.gov (United States)

    Chong, D. P.; Langhoff, S. R.

    1986-01-01

    A modified coupled pair functional (CPF) method is presented for the configuration interaction problem that dramatically improves properties for cases where the Hartree-Fock reference configuration is not a good zeroth-order wave function description. It is shown that the tendency for CPF to overestimate the effect of higher excitations arises from the choice of the geometric mean for the partial normalization denominator. The modified method is demonstrated for ground state dipole moment calculations of the NiH, CuH, and ZnH transition metal hydrides, and compared to singles-plus-doubles configuration interaction and the Ahlrichs et al. (1984) CPF method.

  8. Hydriding and Dehydriding Properties of Zinc Borohydride, Nickel, and Titanium-Added Magnesium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Young Jun; Kwon, Sung Nam; Song, Myoung Youp [Chonbuk National University, Jeonju (Korea, Republic of)

    2015-11-15

    A Zn(BH{sub 4}){sub 2} sample was prepared by milling ZnCl{sub 2} and NaBH{sub 4} in a planetary ball mill under Ar gas. This sample contained NaCl. Then, 90 wt% MgH{sub 2}-5 wt% Zn(BH{sub 4}){sub 2}-2.5 wt% Ni-2.5 wt% Ti samples [named 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti] were prepared by milling in a planetary ball mill under H{sub 2} gas. The hydrogen absorption and release properties of the prepared samples were investigated. In particular, the variations of the initial hydriding and dehydriding rates with temperature were examined. SEM micrographs and XRD patterns of 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti after reactive mechanical grinding and after hydriding-dehydriding were also studied. Particle size distributions and BET specific surface areas of 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti after reactive mechanical grinding and after 11 hydriding-dehydriding cycles were analyzed. The 90MgH{sub 2}-5Zn(BH{sub 4}){sub 2}-2.5Ni-2.5Ti had an effective hydrogen storage capacity (the quantity of hydrogen absorbed for 60 min) of near 5 wt% (4.91 wt% at 593 K).

  9. Comparison of the Winograd method and chemical cauterization with 10% sodium hydroxide for treating ingrown toenails

    OpenAIRE

    Nebahat Demet Akpolat; Ahmet Onur Akpolat; Ozan Namdaroğlu; Ayşe Akkuş

    2016-01-01

    Background and Design: This study was performed to assess the therapeutic outcomes of the surgical method, described by Winograd and chemical cauterization with sodium hydroxide in patients with Heifetz stage 2 and 3 ingrown toenail (recurrence, complication, improvement and time to regain activity). Materials and Methods: One-hundred patients who presented to the outpatient clinics of orthopedics, general surgery and dermatology with the complaints of pain, redness and discharge in the to...

  10. A new method to study lattice QCD at finite temperature and chemical potential

    CERN Document Server

    Fodor, Z

    2002-01-01

    Due to the sign problem, it is exponentially difficult to study QCD on the lattice at finite chemical potential. In this letter we propose a method --an overlap ensuring multi-parameter reweighting technique-- to solve the problem. We apply this method and give the phase diagram of four-flavor QCD obtained on lattices 4^4 and 4\\cdot6^3. Our results are based on {\\cal{O}}(10^3-10^4) configurations.

  11. Production of Nanopowders of Platinum Metals Using the Chemical Reduction Method

    Institute of Scientific and Technical Information of China (English)

    PYATAKHINA E. S.; BUSLAYEVA T. M.; VOLCHKOVA E. V.; KHRISTICH E. A.; SERGEYEVA T. Yu.

    2012-01-01

    The literary data on the application of various methods for the production of nanopowders of platinum metals and alloys have been summarized,and the selection of the method of chemical reduction from salt solutions has been substantiated as the simplest and most affordable.The optimum conditions for the production of nanoparticles of metal palladium and platinum/cobalt alloy,using the effect of boranes with various structures,have been selected.

  12. Aging Effects on the Hydrogen Storage Characteristics of Li-Mg-B-N-H Complex Hydrides

    Science.gov (United States)

    Srinivasan, Sesha; Vickers, Eric; Mulharan, James; Darkazalli, Gazi; Goswami, Yogi; Stefanakos, Elias; FLPoly-CERC Collaboration

    2015-03-01

    The aging effects on the hydrogen storage characteristics and chemical formulations of the complex hydrides are discussed in this study. The aging effects due to atmospheric events such as oxygen and moisture coverage and self-decomposition are currently under investigation. The candidate material chosen for this study is Lithium/Magnesium based complex hydride LiBH4/LiNH2/MgH2. These materials were prepared using high energy ball milling under Ar/H2 atmosphere with different milling durations. The chemical, structural and microstructural characteristics of the synthesized and aged materials were compared and investigated using TGA/DSC, FTIR, XRD, BET and SEM analytical tools. Hydrogen storage properties such as hydrogen sorption kinetics, cycle life and pressure-composition isotherm (PCI) was examined via high pressure, high temperature Sievert's type apparatus. This current study will shed light to compare and contrast the above mentioned characteristics for the aged samples practically at the same experimental conditions. Furthermore, we have investigated the relationship between the aging effects with respect to the crystallite sizes of the candidate compounds and their nano-dopant variants. We acknowledge the grant from Florida Energy Systems Consortium and support from Florida Polytechnic University.

  13. 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.

  14. Fluorine substituent effects on dihydrogen bonding of transition metal hydrides.

    Science.gov (United States)

    Jacobsen, Heiko

    2009-09-07

    Hydrogen and dihydrogen bonding of the fluorinated alcohol (CF(3))(2)CHOH with the transition metal complex WH(CO)(2)(NO)(PMe(3))(2) has been explored by a set of four exemplary density functional theory methods that comprises the BP86, PBE, B3LYP and TPSS functionals. The hydride, nitrosyl and carbonyl ligands of the tungsten complex have been considered as sites of protonation. The main effect of fluorination is an increased dihydrogen bond strength by about 15 kJ mol(-1). The [see equation in text] dihydrogen bond is about 10 kJ mol(-1) stronger than the [W]-NOH-OR hydrogen bond. Of the four DFT methods investigated, the BP86 functional provides the most satisfying quantitative as well as qualitative agreement with experiment. The geometry of the [see equation in text] linkage is significantly influenced by secondary dispersive intermolecular bonding. Linear and bent dihydrogen bonds are separated in energy only by about 1 kJ mol(-1), and represent local minima on the corresponding energy hypersurface.

  15. Modified Augmented Lagrange Multiplier Methods for Large-Scale Chemical Process Optimization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Chemical process optimization can be described as large-scale nonlinear constrained minimization. The modified augmented Lagrange multiplier methods (MALMM) for large-scale nonlinear constrained minimization are studied in this paper. The Lagrange function contains the penalty terms on equality and inequality constraints and the methods can be applied to solve a series of bound constrained sub-problems instead of a series of unconstrained sub-problems. The steps of the methods are examined in full detail. Numerical experiments are made for a variety of problems, from small to very large-scale, which show the stability and effectiveness of the methods in large-scale problems.

  16. Cesium Platinide Hydride 4Cs 2 Pt-CsH: An Intermetallic Double Salt Featuring Metal Anions

    Energy Technology Data Exchange (ETDEWEB)

    Smetana, Volodymyr [Ames Laboratory, US Department of Energy, and Critical Materials Institute, Ames Iowa 50011-3020 USA; Mudring, Anja-Verena [Ames Laboratory, US Department of Energy, and Critical Materials Institute, Ames Iowa 50011-3020 USA; Department of Materials Sciences and Engineering, Iowa State University, Ames Iowa 50011-3111 USA

    2016-10-24

    With Cs9Pt4H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs9Pt4H exhibits a complex crystal structure containing Cs+ cations, Pt2- and H- anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the “alloy” cesium–platinum, or better cesium platinide, Cs2Pt, and the salt cesium hydride CsH according to Cs9Pt4H≡4 Cs2Pt∙CsH.

  17. Cesium Platinide Hydride 4Cs2 Pt⋅CsH: An Intermetallic Double Salt Featuring Metal Anions.

    Science.gov (United States)

    Smetana, Volodymyr; Mudring, Anja-Verena

    2016-11-14

    With Cs9 Pt4 H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs9 Pt4 H exhibits a complex crystal structure containing Cs(+) cations, Pt(2-) and H(-) anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the "alloy" cesium-platinum, or better cesium platinide, Cs2 Pt, and the salt cesium hydride CsH according to Cs9 Pt4 H≡4 Cs2 Pt⋅CsH.

  18. Progress towards a process for the recycling of nickel metal hydride electric cells using a deep eutectic solvent

    Directory of Open Access Journals (Sweden)

    Mark R.StJ. Foreman

    2016-12-01

    Full Text Available Solvent extraction experiments relating to the recycling of the transition metals and lanthanides in nickel metal hydride cells are presented. The metal extraction is occurring from a deep eutectic solvent which is formed from chemicals suitable for use in food and related products. While it has been shown that the water content of the DES has a large effect on the extraction of transition metals by a mixture of chloride ionic liquid (Aliquat 336 and an aromatic solvent, the water content has a smaller effect on the solvent extraction of lanthanides with a solution of di(2-ethylhexyl hydrogen phosphate (DEHPA in a saturated aliphatic hydrocarbon. This study suggests that an industrial scale solvent extraction process for the recycling of metals from nickel hydride electrical cells will be feasible.

  19. Cesium platinide hydride 4Cs{sub 2}Pt.CsH: an intermetallic double salt featuring metal anions

    Energy Technology Data Exchange (ETDEWEB)

    Smetana, Volodymyr [Ames Laboratory, US Department of Energy, and Critical Materials Institute, Ames, Iowa, 50011-3020 (United States); Mudring, Anja-Verena [Ames Laboratory, US Department of Energy, and Critical Materials Institute, Ames, Iowa, 50011-3020 (United States); Department of Materials Sciences and Engineering, Iowa State University, Ames, Iowa, 50011-3111 (United States)

    2016-11-14

    With Cs{sub 9}Pt{sub 4}H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs{sub 9}Pt{sub 4}H exhibits a complex crystal structure containing Cs{sup +} cations, Pt{sup 2-} and H{sup -} anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the ''alloy'' cesium-platinum, or better cesium platinide, Cs{sub 2}Pt, and the salt cesium hydride CsH according to Cs{sub 9}Pt{sub 4}H≡4 Cs{sub 2}Pt.CsH. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. In vitro methods for hazard assessment of industrial chemicals – opportunities and challenges

    Directory of Open Access Journals (Sweden)

    Chin Lin eWong

    2015-05-01

    Full Text Available Allergic contact dermatitis (ACD is a delayed-type hypersensitivity immune reaction mediated by T-lymphocytes as a result of repeated exposure of an allergen primarily on skin. ACD accounts for up to 95% of occupational skin diseases (OSDs, with epoxy resins implicated as one of the most common causes of ACD. Efficient high-throughput in vitro screening for accurate identification of compounds and materials that may pose hazardous risks in the workplace is crucial. At present, the murine local lymph node assay (LLNA is the ‘method of choice’ for predicting the sensitizing potency of contact allergens. As the 3Rs principles of reduction, refinement and replacement in animal testing has gained political and economic momentum, several in vitro screening methods have been developed for identifying potential contact allergens. To date, these latter methods have been utilized primarily to assess the skin sensitizing potential of the chemical components of cosmetic products with scant research attention as to the applicability of these methods to industrial chemicals, particularly epoxy resins. Herein we review the currently utilized in vitro methods and identify the knowledge gaps with regard to assessing the generalizability of in vitro screening methods for assessing the skin sensitizing potential of industrial chemicals.

  1. Chemical Oxygen Demand of Seawater Determined with a Microwave Heating Method

    Institute of Scientific and Technical Information of China (English)

    LIU Li; JI Hongwei; LIU Ying; XIN Huizhen

    2005-01-01

    This paper investigates a microwave heating method for the determination of chemical oxygen demand (COD) in seawater. The influences of microwave-power, heating time and standard substances on the results are studied. Using the proposed method, we analyzed the glucose standard solution, the coefficient of variation being less than 2%. Compared with the traditional electric stove heating method, the results of F-test and T-test showed that there was no significant difference between the two methods, but the microwave method had slightly higher precision and reproducibility than the electric stove method. With the microwave heating method, several seawater samples from Jiaozhou Bay and the South Yellow Sea were also analyzed. The recovery was between 97.5% and 104.3%. This new method has the advantages of shortening the heating time, improving the working efficiency and having simple operation and therefore can be used to analyze the COD in seawater.

  2. Analysis and classification of physical and chemical methods of fuel activation

    Directory of Open Access Journals (Sweden)

    Fedorchak Viktoriya

    2015-12-01

    Full Text Available The offered article explores various research studies, developed patents in terms of physical and chemical approaches to the activation of fuel. In this regard, national and foreign researches in the field of fuels activators with different principles of action were analysed, evaluating their pros and cons. The article also intends to classify these methods and compare them regarding diverse desired results and types of fuels used. In terms of physical and chemical influences on fuels and the necessity of making constructive changes in the fuel system of internal combustion engines, an optimal approach was outlined.

  3. Development of an Improved Simulator for Chemical and Microbial EOR Methods

    Energy Technology Data Exchange (ETDEWEB)

    Pope, Gary A.; Sepehrnoori, Kamy; Delshad, Mojdeh

    2000-09-11

    The objective of this research was to extend the capability of an existing simulator (UTCHEM) to improved oil recovery methods that use surfactants, polymers, gels, alkaline chemicals, microorganisms and foam as well as various combinations of these in both conventional and naturally fractured oil reservoirs. Task 1 is the addition of a dual-porosity model for chemical improved of recovery processes in naturally fractured oil reservoirs. Task 2 is the addition of a foam model. Task 3 addresses several numerical and coding enhancements that will greatly improve the versatility and performance of UTCHEM. Task 4 is the enhancements of physical property models.

  4. Increased Surface Roughness in Polydimethylsiloxane Films by Physical and Chemical Methods

    Directory of Open Access Journals (Sweden)

    Jorge Nicolás Cabrera

    2017-08-01

    Full Text Available Two methods, the first physical and the other chemical, were investigated to modify the surface roughness of polydimethylsiloxane (PDMS films. The physical method consisted of dispersing multi-walled carbon nanotubes (MWCNTs and magnetic cobalt ferrites (CoFe2O4 prior to thermal cross-linking, and curing the composite system in the presence of a uniform magnetic field H. The chemical method was based on exposing the films to bromine vapours and then UV-irradiating. The characterizing techniques included scanning electron microscopy (SEM, energy-dispersive spectroscopy (EDS, Fourier transform infrared (FTIR spectroscopy, optical microscopy, atomic force microscopy (AFM and magnetic force microscopy (MFM. The surface roughness was quantitatively analyzed by AFM. In the physical method, the random dispersion of MWCNTs (1% w/w and magnetic nanoparticles (2% w/w generated a roughness increase of about 200% (with respect to PDMS films without any treatment, but that change was 400% for films cured in the presence of H perpendicular to the surface. SEM, AFM and MFM showed that the magnetic particles always remained attached to the carbon nanotubes, and the effect on the roughness was interpreted as being due to a rupture of dispersion randomness and a possible induction of structuring in the direction of H. In the chemical method, the increase in roughness was even greater (1000%. Wells were generated with surface areas that were close to 100 μm2 and depths of up to 500 nm. The observations of AFM images and FTIR spectra were in agreement with the hypothesis of etching by Br radicals generated by UV on the polymer chains. Both methods induced important changes in the surface roughness (the chemical method generated the greatest changes due to the formation of surface wells, which are of great importance in superficial technological processes.

  5. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  6. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  7. A thermodynamic and kinetic study of hydride transfer of a caffeine derivative.

    Science.gov (United States)

    Han, Xiaozhen; Hao, Weifang; Zhu, Xiao-Qing; Parker, Vernon D

    2012-08-03

    One representative type of heterocyclic compound that can release a hydride ion is 7,8-dihydro-9-methylcaffeine (CAFH). The one-electron oxidation potential of CAFH [-0.294 (V vs Fc(+/0))] and the one-electron reduction potential of CAF(+) [-2.120 (V vs Fc(+/0))] were obtained using two different methods, CV and OSWV. Applying titration calorimetry data in thermodynamic cycles, the enthalpies of CAFH releasing a hydride ion [57.6 kcal/mol] and releasing a hydrogen atom [80.3 kcal/mol] and of its radical cation CAFH(•+) releasing a proton [33.0 kcal/mol] and releasing a hydrogen atom [38.4 kcal/mol] have been determined. Several conclusions can be drawn from the thermodynamic results: (1) CAFH is a very good single-electron donor whose single-electron oxidation potential is much less positive than that of NAD(P)H model compound BNAH [E(ox) = 0.219 V vs Fc(+/0)]. (2) The single-electron reduction potential of CAF(+) is much more negative than that of BNA(+) [E(red) = -1.419 V], which means that CAF(+) is not a good electron acceptor. Furthermore, CAFH is a very good hydride donor compared to BNAH. The results of non-steady-state kinetic studies, for the reaction of CAFH and AcrH(+)ClO(4)(-), show that the ratio of t(0.50)/t(0.05) is larger than 13.5 and the ratio of k(init)/k(pfo) is larger than 1. The pseudo-first-order rate constants obtained at different reaction stages decrease with the time, and the kinetic isotope was observed to be small at a short reaction time and slowly increases to 3.72 with the progress of the reaction. These kinetic results clearly display that the hydride transfer of CAFH to AcrH(+) in acetonitrile is not a one-step mechanism, while the thermodynamic results show that CAFH is a very good electron donor. The combination of the kinetic results with the thermodynamics analysis shows that the hydride transfer of the caffeine derivative CAFH takes place by a two-step reversible mechanism and there is an intermediate in the reaction.

  8. Influence of surface contaminations on the hydrogen storage behaviour of metal hydride alloys.

    Science.gov (United States)

    Schülke, Mark; Paulus, Hubert; Lammers, Martin; Kiss, Gábor; Réti, Ferenc; Müller, Karl-Heinz

    2008-03-01

    Hydrogen storage in metal hydrides is a promising alternative to common storage methods. The surface of a metal hydride plays an important part in the absorption of hydrogen, since important partial reaction steps take place here. The development of surface contaminations and their influence on hydrogen absorption is examined by means of absorption experiments and surface analysis, using X-ray photoelectron spectroscopy (XPS), thermal desorption mass spectrometry (TDMS) and secondary neutral mass spectrometry (SNMS), in this work. All investigations were carried out on a modern AB(2) metal hydride alloy, namely Ti(0.96)Zr(0.04)Mn(1.43)V(0.45)Fe(0.08). Surface analysis (SNMS, XPS) shows that long-term air storage (several months) leads to oxide layers about 15 nm thick, with complete oxidation of all main alloy components. By means of in situ oxygen exposure at room temperature and XPS analysis, it can be shown that an oxygen dose of about 100 Langmuirs produces an oxide layer comparable to that after air storage. Manganese enrichment (segregation) is also clearly observed and is theoretically described here. This oxide layer hinders hydrogen absorption, so an activation procedure is necessary in order to use the full capacity of the metal hydride. This procedure consists of heating (T = 120 degrees C) in vacuum and hydrogen flushing at pressures like p = 18 bar. During the activation process the alloy is pulverized to particles of approximately 20 microm through lattice stretches. It is shown that this pulverization of the metal hydride (creating clean surface) during hydrogen flushing is essential for complete activation of the material. Re-activation of powder contaminated by small doses of air (p approximately 0.1 bar) does not lead to full absorption capacity. In ultrahigh vacuum, hydrogen is only taken up by the alloy after sputtering of the surface (which is done in order to remove oxide layers from it), thus creating adsorption sites for the hydrogen. This

  9. Discrete formulation of mixed finite element methods for vapor deposition chemical reaction equations

    Institute of Scientific and Technical Information of China (English)

    LUO Zhen-dong; ZHOU Yan-jie; ZHU Jiang

    2007-01-01

    The vapor deposition chemical reaction processes, which are of extremely extensive applications, can be classified as a mathematical modes by the following governing nonlinear partial differential equations containing velocity vector,temperature field,pressure field,and gas mass field.The mixed finite element(MFE)method is employed to study the system of equations for the vapor deposition chemical reaction processes.The semidiscrete and fully discrete MFE formulations are derived.And the existence and convergence(error estimate)of the semidiscrete and fully discrete MFE solutions are deposition chemical reaction processes,the numerical solutions of the velocity vector,the temperature field,the pressure field,and the gas mass field can be found out simultaneonsly.Thus,these researches are not only of important theoretical means,but also of extremely extensive applied vistas.

  10. Chemical burns revisited: What is the most appropriate method of decontamination?

    Science.gov (United States)

    Tan, Teresa; Wong, David S Y

    2015-06-01

    The purpose of this study is to investigate the efficacy of decontamination by immediate surgical debridement in the acute management of chemical burns as compared to conventional dilutional approaches by irrigation or wetting. A retrospective review of the medical records of patients admitted to the Burns Centre of the Prince of Wales Hospital, Hong Kong, between 2001 and 2012, was performed. The time to recovery as reflected by the hospital stay for patients who had received immediate debridement, continuous irrigation, and wet packs was calculated and compared. A total of 99 patients were admitted for chemical burns (3.3% of total admissions). There were three mortalities. Immediate surgical debridement failed to achieve a faster recovery than irrigation or wet packs. Continuous water irrigation was better than wet packs in achieving earlier recovery. Continuous water irrigation remains the most preferred method of decontamination in acute chemical burn management.

  11. Fast Method for Computing Chemical Potentials and Liquid-Liquid Phase Equilibria of Macromolecular Solutions.

    Science.gov (United States)

    Qin, Sanbo; Zhou, Huan-Xiang

    2016-08-25

    Chemical potential is a fundamental property for determining thermodynamic equilibria involving exchange of molecules, such as between two phases of molecular systems. Previously, we developed the fast Fourier transform (FFT)-based method for Modeling Atomistic Protein-crowder interactions (FMAP) to calculate excess chemical potentials according to the Widom insertion. Intermolecular interaction energies were expressed as correlation functions and evaluated via FFT. Here, we extend this method to calculate liquid-liquid phase equilibria of macromolecular solutions. Chemical potentials are calculated by FMAP over a wide range of molecular densities, and the condition for coexistence of low- and high-density phases is determined by the Maxwell equal-area rule. When benchmarked on Lennard-Jones fluids, our method produces an accurate phase diagram at 18% of the computational cost of the current best method. Importantly, the gain in computational speed increases dramatically as the molecules become more complex, leading to many orders of magnitude in speed up for atomistically represented proteins. We demonstrate the power of FMAP by reporting the first results for the liquid-liquid coexistence curve of γII-crystallin represented at the all-atom level. Our method may thus open the door to accurate determination of phase equilibria for macromolecular mixtures such as protein-protein mixtures and protein-RNA mixtures, that are known to undergo liquid-liquid phase separation, both in vitro and in vivo.

  12. Reprint of "In silico methods in the discovery of endocrine disrupting chemicals".

    Science.gov (United States)

    Vuorinen, Anna; Odermatt, Alex; Schuster, Daniela

    2015-09-01

    The prevalence of sex hormone-dependent cancers, reproductive problems, obesity, and cardiovascular complications has risen especially in the Western world. It has been suggested, that the exposure to various endocrine disrupting chemicals (EDCs) contributes to the development and progression of these diseases. EDCs can interfere with various proteins: nuclear steroid hormone receptors, such as estrogen-, androgen-, glucocorticoid- and mineralocorticoid receptors (ER, AR, GR, MR), and enzymes that are involved in steroid hormone synthesis and metabolism, for example hydroxysteroid dehydrogenases (HSDs). Numerous chemicals are known as endocrine disruptors. However, the mechanism of action for most of these EDCs is still unknown. It is exhaustive and time consuming to test in vitro all chemicals - potential EDCs - used in industry, agriculture or as food preservatives against their effects on the endocrine system. Computational methods, such as virtual screening, quantitative structure activity relationships and docking, are already well recognized and used in drug development. The same methods could also aid the research on EDCs. So far, the computational methods in the search of EDCs have been retrospective. There are, however, some prospective studies reporting the use of in silico methods: five studies reporting the identification of previously unknown 17β-HSD3 inhibitors, MR agonists, and ER antagonists/agonists. This review provides an overview of case studies and in silico methods that are used in the search of EDCs. This article is part of a Special Issue entitled 'CSR 2013'.

  13. DOSE MEASURMENT IN ULTRAVIOLET DISINFECTION OF WATER AND WASTE WATER BY CHEMICAL METHOD

    Directory of Open Access Journals (Sweden)

    F.Vaezi

    1995-06-01

    Full Text Available Chemical methods ( actinometry depend on the measurement of the extent to which a chemical reaction occurs under the influence of UV light. Two chemical actinometers have been used in this research. In one method, the mixtures of potassium peroxidisuiphate butanol solutions were irradiated for various time intervals, and pH-changes were determined. A linear relationship was observed between these changes and UV-dose applied. In another method, the acidic solutions of ammonium molybdate and ethyl alcohol were irradiated and the intensity of blue color developed was determined by titration with potassium permanganate solutions. The volumes of titrant used were then plotted versus the UV-doses. This showed a linear relationship which could be used for dosimeiry. Both of these actometers proved to be reliable. The first is the method of choice with a view to have much accuracy and the second method is preferred because of its feasibility and having advantages of no need to any equipment and non-accessible raw materials.

  14. Calculation of chemical potentials of chain molecules by the incremental gauge cell method

    Science.gov (United States)

    Rasmussen, Christopher J.; Vishnyakov, Aleksey; Neimark, Alexander V.

    2011-12-01

    The gauge cell Monte Carlo method is extended to calculations of the incremental chemical potentials and free energies of linear chain molecules. The method was applied to chains of Lennard-Jones beads with stiff harmonic bonds up to 500 monomers in length. We show that the suggested method quantitatively reproduces the modified Widom particle insertion method of Kumar et al. [S. K. Kumar, I. Szleifer, and A. Z. Panagiotopoulos, Phys. Rev. Lett. 66(22), 2935 (1991)], 10.1103/PhysRevLett.66.2935, and is by an order of magnitude more efficient for long chains in terms of the computational time required for the same accuracy of chemical potential calculations. The chain increment ansatz, which suggests that the incremental chemical potential is independent of the chain length, was tested at different temperatures. We confirmed that the ansatz holds only for coils above the θ temperature. Special attention is paid to the effects of the magnitude of adsorption potential and temperature on the behavior of single chains in confinements that are comparable in size with the free chain radius of gyration. At sufficiently low temperatures, the dependence of the incremental chemical potential on the chain length in wetting pores is superficially similar to a capillary condensation isotherm, reflecting monolayer formation following by pore volume filling, as the chain length increases. We find that the incremental gauge cell method is an accurate and efficient technique for calculations of the free energies of chain molecules in bulk systems and nanoconfinements alike. The suggested method may find practical applications, such as modeling polymer partitioning on porous substrates and dynamics of chain translocation into nanopores.

  15. Investigation of Cracked Lithium Hydride Reactor Vessels

    Energy Technology Data Exchange (ETDEWEB)

    bird, e.l.; mustaleski, t.m.

    1999-06-01

    Visual examination of lithium hydride reactor vessels revealed cracks that were adjacent to welds, most of which were circumferentially located in the bottom portion of the vessels. Sections were cut from the vessels containing these cracks and examined by use of the metallograph, scanning electron microscope, and microprobe to determine the cause of cracking. Most of the cracks originated on the outer surface just outside the weld fusion line in the base material and propagated along grain boundaries. Crack depths of those examined sections ranged from {approximately}300 to 500 {micro}m. Other cracks were reported to have reached a maximum depth of 1/8 in. The primary cause of cracking was the creation of high tensile stresses associated with the differences in the coefficients of thermal expansion between the filler metal and the base metal during operation of the vessel in a thermally cyclic environment. This failure mechanism could be described as creep-type fatigue, whereby crack propagation may have been aided by the presence of brittle chromium carbides along the grain boundaries, which indicates a slightly sensitized microstructure.

  16. Influence of TiB{sub 2} addition upon thermal stability and decomposition temperature of the MgH{sub 2} hydride of a Mg-based mechanical alloy

    Energy Technology Data Exchange (ETDEWEB)

    Dobrovolsky, V.D. [Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky str., UA-03142 Kyiv (Ukraine)], E-mail: dobersh@ipms.kiev.ua; Ershova, O.G.; Solonin, Yu.M.; Khyzhun, O.Yu. [Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky str., UA-03142 Kyiv (Ukraine); Paul-Boncour, V. [Chimie Metallurgique des Terres Rares, Institut de Chimie et des Materiaux de Paris-Est, Centre National de la Recherche Scientifique, 2/8 rue Henri-Dunant, F-94320 Thiais Cedex (France)

    2008-10-06

    Intensive mechanical milling was used to synthesize a MgH{sub 2} (50 wt.%) + TiB{sub 2} (50 wt.%) composite. Thermal stability of the composite versus H-desorption was studied employing the thermodesorption spectroscopy (TDS) method. The TDS data have revealed that TiB{sub 2} addition decreases the dissociation temperature of the MgH{sub 2} hydride by about 50 deg. C. An X-ray photoelectron spectroscopy analysis has shown that TiB{sub 2} addition does not alter the surface chemical state of particles of the MgH{sub 2} hydride, a component of the composite under consideration. The effect of decreasing decomposition temperature of MgH{sub 2} due to addition of TiB{sub 2} has been attributed to catalytic influence of a TiB{sub 2} particle surface on processes of associative hydrogen desorption taking place on the surface of MgH{sub 2} particles, as well as to a higher degree of dispersion of magnesium dihydride provided by the presence of TiB{sub 2}.

  17. A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

    2013-03-01

    Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

  18. Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster.

    Science.gov (United States)

    Kang, Xiaohui; Luo, Gen; Luo, Lun; Hu, Shaowei; Luo, Yi; Hou, Zhaomin

    2016-09-14

    Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics.

  19. Comparison of the interactions in the rare gas hydride and Group 2 metal hydride anions.

    Science.gov (United States)

    Harris, Joe P; Manship, Daniel R; Breckenridge, W H; Wright, Timothy G

    2014-02-28

    We study both the rare gas hydride anions, RG-H(-) (RG = He-Rn) and Group 2 (Group IIa) metal hydride anions, MIIaH(-) (MIIa = Be-Ra), calculating potential energy curves at the CCSD(T) level with augmented quadruple and quintuple basis sets, and extrapolating the results to the basis set limit. We report spectroscopic parameters obtained from these curves; additionally, we study the Be-He complex. While the RG-H(-) and Be-He species are weakly bound, we show that, as with the previously studied BeH(-) and MgH(-) species, the other MIIaH(-) species are strongly bound, despite the interactions nominally also being between two closed shell species: M(ns(2)) and H(-)(1s(2)). We gain insight into the interactions using contour plots of the electron density changes and population analyses. For both series, the calculated dissociation energy is significantly less than the ion/induced-dipole attraction term, confirming that electron repulsion is important in these species; this effect is more dramatic for the MIIaH(-) species than for RG-H(-). Our analyses lead us to conclude that the stronger interaction in the case of the MIIaH(-) species arises from sp and spd hybridization, which allows electron density on the MIIa atom to move away from the incoming H(-).

  20. 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.