Science.gov

Sample records for iridium hydrides

  1. Activation of C-H bonds in nitrones leads to iridium hydrides with antitumor activity.

    PubMed

    Song, Xiaoda; Qian, Yong; Ben, Rong; Lu, Xiang; Zhu, Hai-Liang; Chao, Hui; Zhao, Jing

    2013-08-22

    We report the design and synthesis of a series of new cyclometalated iridium hydrides derived from the C-H bond activation of aromatic nitrones and the biological evaluation of these iridium hydrides as antitumor agents. The nitrone ligands are based on the structure of a popular antioxidant, α-phenyl-N-tert-butylnitrone (PBN). Compared to cisplatin, the iridium hydrides exhibit excellent antitumor activity on HepG2 cells. The metal-coordinated compound with the most potent anticancer activity, 2f, was selected for further analysis because of its ability to induce apoptosis and interact with DNA. During in vitro studies and in vivo efficacy analysis with tumor xenograft models in Institute of Cancer Research (ICR) mice, complex 2f exhibited antitumor activity that was markedly superior to that of cisplatin. Our results suggest, for the first time, that metal hydrides could be a new type of metal-based antitumor agent.

  2. The diastereoselective synthesis of octahedral cationic iridium hydride complexes with a stereogenic metal centre.

    PubMed

    Humbert, Nicolas; Mazet, Clément

    2016-08-23

    We report herein the highly diastereoselective synthesis of octahedral cationic Ir(iii) hydride complexes with a stereogenic metal centre following various strategies. The configurational stability of these compounds has also been investigated.

  3. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics.

    PubMed

    Bhagan, Salome; Wayland, Bradford B

    2011-11-07

    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  4. Diastereoselective formation of chiral iridium hydrides containing the chiral P,N-chelate ligand (4S)-2-(2-(diphenylphosphino)phenyl)-4-isopropyl-1,3-oxazoline.

    PubMed

    Carmona, Daniel; Ferrer, Joaquina; Lorenzo, Mónica; Santander, Manuel; Ponz, Sergio; Lahoz, Fernando J; López, José A; Oro, Luis A

    2002-04-21

    The iridium complex [Ir(mu-Cl)(PN)(PPh3)]2 (1) reacts with H2 affording only the kinetic isomer OC-6-55-C of the dihydride [IrClH2(PN)(PPh3)] (2) and with methanol yielding, also exclusively, the thermodynamic isomer OC-6-53-C (2b) of the same dihydride; complex 2b has been characterised by X-ray diffractometric methods.

  5. Role of coordination geometry in dictating the barrier to hydride migration in d6 square-pyramidal iridium and rhodium pincer complexes.

    PubMed

    Findlater, Michael; Cartwright-Sykes, Alison; White, Peter S; Schauer, Cynthia K; Brookhart, Maurice

    2011-08-10

    Syntheses of the olefin hydride complexes [(POCOP)M(H)(olefin)][BAr(f)(4)] (6a-M, M = Ir or Rh, olefin = C(2)H(4); 6b-M, M = Ir or Rh, olefin = C(3)H(6); POCOP = 2,6-bis(di-tert-butylphosphinito)benzene; BAr(f) = tetrakis(3,5-trifluoromethylphenyl)borate) are reported. A single-crystal X-ray structure determination of 6b-Ir shows a square-pyramidal coordination geometry for Ir, with the hydride ligand occupying the apical position. Dynamic NMR techniques were used to characterize these complexes. The rates of site exchange between the hydride and the olefinic hydrogens yielded ΔG(++) = 15.6 (6a-Ir), 16.8 (6b-Ir), 12.0 (6a-Rh), and 13.7 (6b-Rh) kcal/mol. The NMR exchange data also established that hydride migration in the propylene complexes yields exclusively the primary alkyl intermediate arising from 1,2-insertion. Unexpectedly, no averaging of the top and bottom faces of the square-pyramidal complexes is observed in the NMR spectra at high temperatures, indicating that the barrier for facial equilibration is >20 kcal/mol for both the Ir and Rh complexes. A DFT computational study was used to characterize the free energy surface for the hydride migration reactions. The classical terminal hydride complexes, [M(POCOP)(olefin)H](+), are calculated to be the global minima for both Rh and Ir, in accord with experimental results. In both the Rh ethylene and propylene complexes, the transition state for hydride migration (TS1) to form the agostic species is higher on the energy surface than the transition state for in-place rotation of the coordinated C-H bond (TS2), while for Ir, TS2 is the high point on the energy surface. Therefore, only for the case of the Rh complexes is the NMR exchange rate a direct measure of the hydride migration barrier. The trends in the experimental barriers as a function of M and olefin are in good agreement with the trends in the calculated exchange barriers. The calculated barriers for the hydride migration reaction in the Rh complexes

  6. Iridium in natural waters

    SciTech Connect

    Anbar, A.D.; Wasserburg, G.J.; Papanastassiou, D.A.

    1996-09-13

    Iridium, commonly used as a tracer of extraterrestrial material, was measured in rivers, oceans, and an estuarine environment. The concentration of iridium in the oceans ranges from 3.0 ({+-}1.3) x 10{sup 8} to 5.7 ({+-}0.8) x 10{sup 8} atoms per kilogram. Rivers contain from 17.4 ({+-}0.9) x 10{sup 8} to 92.9 ({+-}2.2) x 10{sup 8} atoms per kilogram and supply more dissolved iridium to the oceans than do extraterrestrial sources. In the Baltic Sea, {approximately}75% of riverine iridium is removed from solution. Iron-manganese oxyhydroxides scavenge iridium under oxidizing conditions, but anoxic environments are not a major sink for iridium. The ocean residence time of iridium is between 2 x 10{sup 3} and 2 x 10{sup 4} years. 32 refs., 3 figs., 1 tab.

  7. Hydriding process

    DOEpatents

    Raymond, J.W.; Taketani, H.

    1973-12-01

    BS>A method is described for hydriding a body of a Group IV-B metal, preferably zirconium, to produce a crack-free metal-hydride bedy of high hydrogen content by cooling the body at the beta to beta + delta boundary, without further addition of hydrogen, to precipitate a fine-grained delta-phase metal hydride in the beta + delta phase region and then resuming the hydriding, preferably preceded by a reheating step. (Official Gazette)

  8. Processing of Iridium and Iridium Alloys

    SciTech Connect

    Ohriner, Evan Keith

    2008-01-01

    Iridium and its alloys have been considered to be difficult to fabricate due to their high melting temperatures, limited ductility, sensitivity to impurity content, and chemical properties. The variety of processing methods used for iridium and its alloys are reviewed, including purification, melting, forming, joining, and powder metallurgy techniques. Also included are coating and forming by the methods of electroplating, chemical and physical vapor deposition, and melt particle deposition.

  9. Sealed aerospace metal-hydride batteries

    NASA Technical Reports Server (NTRS)

    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.

  10. Iridium Interfacial Stack (IRIS)

    NASA Technical Reports Server (NTRS)

    Spry, David James (Inventor)

    2015-01-01

    An iridium interfacial stack ("IrIS") and a method for producing the same are provided. The IrIS may include ordered layers of TaSi.sub.2, platinum, iridium, and platinum, and may be placed on top of a titanium layer and a silicon carbide layer. The IrIS may prevent, reduce, or mitigate against diffusion of elements such as oxygen, platinum, and gold through at least some of its layers.

  11. Hydride compositions

    DOEpatents

    Lee, Myung, W.

    1994-01-01

    Disclosed are a composition for use in storing hydrogen and a method for making the composition. The composition comprises a mixture of two or more hydrides, each hydride having a different series of hydrogen sorption isotherms that contribute to the overall isotherms of the mixture. The hydrides are chosen so that the isotherms of the mixture have regions wherein the H equilibrium pressure increases with increasing hydrogen, preferably linearly. The isotherms of the mixture can be adjusted by selecting hydrides with different isotherms and by varying the amounts of the individual hydrides, or both. Preferably, the mixture is made up of hydrides that have isotherms with substantially flat plateaus and in nearly equimolar amounts. The composition is activated by degassing, exposing to H, and then heating below the softening temperature of any of the constituents. When the composition is used to store hydrogen, its hydrogen content can be found simply by measuring P{sub H}{sub 2} and determining H/M from the isothermic function of the composition.

  12. Hydride compositions

    DOEpatents

    Lee, Myung W.

    1995-01-01

    A composition for use in storing hydrogen, and a method for making the composition. The composition comprises a mixture of two or more hydrides, each hydride having a different series of hydrogen sorption isotherms that contribute to the overall isotherms of the mixture. The hydrides are chosen so that the isotherms of the mixture have regions wherein the hydrogen equilibrium pressure increases with increasing hydrogen, preferably linearly. The isotherms of the mixture can be adjusted by selecting hydrides with different isotherms and by varying the amounts of the individual hydrides, or both. Preferably, the mixture is made up of hydrides that have isotherms with substantially flat plateaus and in nearly equimolar amounts. The composition is activated by degassing, exposing to hydrogen and then heating at a temperature below the softening temperature of any of the. constituents so that their chemical and structural integrity is preserved. When the composition is used to store hydrogen, its hydrogen content can be found simply by measuring P.sub.H.sbsb.2 and determining H/M from the isothermic function of the composition.

  13. Chiral N-heterocyclic carbene/pyridine ligands for the iridium-catalyzed asymmetric hydrogenation of olefins.

    PubMed

    Schumacher, Andreas; Bernasconi, Maurizio; Pfaltz, Andreas

    2013-07-15

    Swapping N,P for C,N: Iridium complexes of bidentate pyridine-based C,N ligands with an N-heterocylic carbene (NHC) unit proved to be efficient and highly enantioselective hydrogenation catalysts. As a result of the lower acidity of iridium hydride intermediates produced from NHC-based complexes, these catalysts are much better suited than analogous N,P-ligand complexes for the hydrogenation of acid-sensitive substrates.

  14. Iridium: failures & successes

    NASA Astrophysics Data System (ADS)

    Christensen, CarissaBryce; Beard, Suzette

    2001-03-01

    This paper will provide an overview of the Iridium business venture in terms of the challenges faced, the successes achieved, and the causes of the ultimate failure of the venture — bankruptcy and system de-orbit. The paper will address technical, business, and policy issues. The intent of the paper is to provide a balanced and accurate overview of the Iridium experience, to aid future decision-making by policy makers, the business community, and technical experts. Key topics will include the history of the program, the objectives and decision-making of Motorola, the market research and analysis conducted, partnering strategies and their impact, consumer equipment availability, and technical issues — target performance, performance achieved, technical accomplishments, and expected and unexpected technical challenges. The paper will use as sources trade media and business articles on the Iridium program, technical papers and conference presentations, Wall Street analyst's reports, and, where possible, interviews with participants and close observers.

  15. Mononuclear iridium dinitrogen complexes bonded to zeolite HY

    SciTech Connect

    Yang, Dong; Chen, Mingyang; Martinez-Macias, Claudia; Dixon, David A.; Gates, Bruce C.

    2014-11-07

    In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.

  16. Hydridomethyl iridium complex

    SciTech Connect

    Bergman, R.G; Buchanan, J.M.; Stryker, J.M.; Wax, M.J.

    1989-07-18

    This patent describes a hydridomethyl complex of the formula: CpIr(P(R{sub 1}){sub 3})HMe. Cp represents a cyclopentadienyl or alkyl cyclopentadienyl radical; Ir represents an iridium atom; P represents a phosphorus atom; R{sub 1} represents an alkyl group; and Me represents a methyl group.

  17. Luminogenic iridium azide complexes

    PubMed Central

    Ohata, Jun; Vohidov, Farrukh; Aliyan, Amirhossein; Huang, Kewei; Martí, Angel A.

    2015-01-01

    The synthesis and characterization of luminogenic, bioorthogonal iridium probes is described. These probes exhibit long fluorescent lifetimes amenable to time-resolved applications. A simple, modular synthesis via 5-azidophenanthroline allows structural variation and allows optimization of cell labeling. PMID:26325066

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

    PubMed

    Zhu, Ye; Fan, Yubo; Burgess, Kevin

    2010-05-05

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

  19. Method for refining contaminated iridium

    DOEpatents

    Heshmatpour, B.; Heestand, R.L.

    1982-08-31

    Contaminated iridium is refined by alloying it with an alloying agent selected from the group consisting of manganese and an alloy of manganese and copper, and then dissolving the alloying agent from the formed alloy to provide a purified iridium powder.

  20. Method for refining contaminated iridium

    DOEpatents

    Heshmatpour, Bahman; Heestand, Richard L.

    1983-01-01

    Contaminated iridium is refined by alloying it with an alloying agent selected from the group consisting of manganese and an alloy of manganese and copper, and then dissolving the alloying agent from the formed alloy to provide a purified iridium powder.

  1. Electrochemical deposition of iridium and iridium-nickel-alloys

    NASA Astrophysics Data System (ADS)

    Näther, J.; Köster, F.; Freudenberger, R.; Schöberl, C.; Lampke, T.

    2017-03-01

    To develop durable and reliable electronic contacts, precious metals are still very important for finish plating of contact surfaces. The lesser-known iridium might be an interesting alternative to substitute gold alloys, platinum or rhodium for applications with highest demands to wear and corrosion resistance such as sliding and plug contacts. As matters stand there is no commercial electrolyte for iridium plating. Initial investigation screened the parameter range for different iridium compounds when an iridium layer occurred on the substrates. This approach showed that the oxidation state of iridium is crucial to reach contenting deposits. Best results came from Ir(IV) electrolyte with high bromine concentration coming from the starting compound, while electrolytes made from Ir(III) compounds gave very poor deposits. In subsequent experiments different organic compounds were added to the electrolytes to improve plating efficiency and stability of the solutions. So found electrolytes gave crack-free deposits up to two microns with a micro-hardness of 600 HV. To reduce the iridium content in the layer, iridium-nickel-alloys were investigated, finding that a nickel-content of 10 wt% raised the layer hardness to more than 900 HV.

  2. Hydride compressor

    DOEpatents

    Powell, James R.; Salzano, Francis J.

    1978-01-01

    Method of producing high energy pressurized gas working fluid power from a low energy, low temperature heat source, wherein the compression energy is gained by using the low energy heat source to desorb hydrogen gas from a metal hydride bed and the desorbed hydrogen for producing power is recycled to the bed, where it is re-adsorbed, with the recycling being powered by the low energy heat source. In one embodiment, the adsorption-desorption cycle provides a chemical compressor that is powered by the low energy heat source, and the compressor is connected to a regenerative gas turbine having a high energy, high temperature heat source with the recycling being powered by the low energy heat source.

  3. Mononuclear iridium dinitrogen complexes bonded to zeolite HY

    DOE PAGES

    Yang, Dong; Chen, Mingyang; Martinez-Macias, Claudia; ...

    2014-11-07

    In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridiummore » hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.« less

  4. Iridium at Kilauea

    NASA Astrophysics Data System (ADS)

    Bell, Peter M.

    Trace-element anomalies observed in rocks located stratigraphically at the Cretaceous-Tertiary boundary are considered significant evidence that the boundary is a record of a large meteorite impact (Science, 208, 1095-1108, 1980). In particular, trace metals, including iridium and other members of the platinum metals group, are thought to be enriched in rocks alien to the earth's surface. These elements are indeed enriched in meteorites relative to earth crustal rocks, but new evidence from analyses of the January 1983 eruption of Kilauea suggest that the analogy may be invalid. W.H. Zoller, J.R. Parrington, and J.M. Phelan Kotra reported neutron activation analyses of airborne particulate matter collected at the Mauna Loa Observatory and found “strikingly” large concentrations of iridium in addition to element concentrations expected from volcanic emissions (Science, 222, 1118, 1983). The only other platinum-group trace metal analyzed was gold, which was also found to be anomalously high. They concede that they need more data of other platinum group elements and more data on other volcanos, but the implication is that the Cretacious-Tertiary boundary may well be volcanic, not due to a large meteorite impact.

  5. Iridium Satellite Signal Exploitation

    NASA Astrophysics Data System (ADS)

    McDonough, Peter

    2010-03-01

    The Iridium Satellite constellation is unique to satellite communication networks in that it allows for transmission of data between satellites instead of relying on transmission by the bent pipe methodology. As such, this network is far more secure than other satellite communication networks, and forces interception to occur within the locale of the transmission from modem to satellite or within the locale of the downlink from the satellite other modem. The purpose of this project was to demonstrate the security weaknesses within the Iridium protocol, showing that it was possible to track one of these satellites with a high gain antenna, resulting in the ability to anticipate transmission, to acquire the location of that transmission, and to uncover the content of that transmission. This project was completed as part of the summer student program at the Southwest Research Institute. The presentation will demonstrate the thought process used in chronological order, essentially demonstrating how I achieved the result from my point of view as the summer progressed.

  6. Hydridomethyl iridium complex

    DOEpatents

    Bergman, Robert G.; Buchanan, J. Michael; Stryker, Jeffrey M.; Wax, Michael J.

    1989-01-01

    A process for functionalizing methane comprising: (a) reacting methane with a hydridoalkyl metal complex of the formula: CpIr[P(R.sub.1).sub.3 ]H(R.sub.2) wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical having from 1 to 5 carbon atoms; Ir represents an iridium atom; P represents a phosphorus atom; R.sub.1 represents an alkyl group; R.sub.2 represents an alkyl group having at least two carbon atoms; and H represents a hydrogen atom, in the presence of a liquid alkane R.sub.3 H having at least three carbon atoms to form a hydridomethyl complex of the formula: CpIr[P(R.sub.1).sub.3 ]HMe where Me represents a methyl radical. (b) reacting said hydridomethyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X"X'"X"" or CHX'X"X'"; wherein X', X", X"', and X"" represent halogens selected from bromine, iodine and chlorine, to halomethyl complex of step (a) having the formula: CpIr[P(R.sub.1).sub.3 ]MeX: (c) reacting said halomethyl complex with a mercuric halide of the formula HgX.sub.2 to form a methyl mercuric halide of the formula HgMeX; and (d) reacting said methyl mercuric halide with a molecular halogen of the formula X.sub.2 to form methyl halide.

  7. Iridium in sea-water.

    PubMed

    Fresco, J; Weiss, H V; Phillips, R B; Askeland, R A

    1985-08-01

    Iridium in sea-water has been measured (after isolation from the saline matrix by reduction with magnesium) by neutron bombardment, radiochemical purification and high-resolution gamma-ray spectroscopy. The concentration obtained in a Pacific coastal water was 1.02 +/- 0.26 x 10(-14) g per g of sea-water. At such extremely low concentrations, seawater is an extremely unlikely source for anomalously high iridium concentrations measured in the Cretaceous-Tertiary boundary layer of deep-sea sediments.

  8. Synthesis of ruthenium hydride

    NASA Astrophysics Data System (ADS)

    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.

  9. The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines.

    PubMed

    Stirling, Matthew J; Sweeney, Gemma; MacRory, Kerry; Blacker, A John; Page, Michael I

    2016-04-14

    The iridium complex of pentamethylcyclopentadiene and (S,S)-1,2-diphenyl-N'-tosylethane-1,2-diamine is an effective catalyst for the asymmetric transfer hydrogenation of imine substrates under acidic conditions. Using the Ir catalyst and a 5 : 2 ratio of formic acid : triethylamine as the hydride source for the asymmetric transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline and its 6,7-dimethoxy substituted derivative, in either acetonitrile or dichloromethane, shows unusual enantiomeric excess (ee) profiles for the product amines. The reactions initially give predominantly the (R) enantiomer of the chiral amine products with >90% ee but which then decreases significantly during the reaction. The decrease in ee is not due to racemisation of the product amine, but because the rate of formation of the (R)-enantiomer follows first-order kinetics whereas that for the (S)-enantiomer is zero-order. This difference in reaction order explains the change in selectivity as the reaction proceeds - the rate formation of the (R)-enantiomer decreases exponentially with time while that for the (S)-enantiomer remains constant. A reaction scheme is proposed which requires rate-limiting hydride transfer from the iridium hydride to the iminium ion for the first-order rate of formation of the (R)-enantiomer amine and rate-limiting dissociation of the product for the zero-order rate of formation of the (S)-enantiomer.

  10. Iridium-Catalyzed Allylic Substitution

    NASA Astrophysics Data System (ADS)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.

  11. Hysteresis in Metal Hydrides.

    ERIC Educational Resources Information Center

    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)

  12. IRIDIUM LINER FOR NASA 5 LBF CLASS MATERIAL TEST CHAMBER IRIDIUM LINER FOR ATLANTIC RESEARCH CORPORA

    NASA Technical Reports Server (NTRS)

    1995-01-01

    IRIDIUM LINER FOR NASA 5 LBF CLASS MATERIAL TEST CHAMBER IRIDIUM LINER FOR ATLANTIC RESEARCH CORPORATION 5 LBF CLASS ROCKET CHAMBER 25 LBF CLASS 75 HFC 25 TAC CERAMIC COMPOSITE ROCKET CHAMBER FROM REFRACTURY COMPOSITES INC. PURCHASE ORDER C-551941-

  13. Experimental characterization of the hydride 1H shielding tensors for HIrX2(PR3)2 and HRhCl2(PR3)2: extremely shielded hydride protons with unusually large magnetic shielding anisotropies.

    PubMed

    Garbacz, Piotr; Terskikh, Victor V; Ferguson, Michael J; Bernard, Guy M; Kędziorek, Mariusz; Wasylishen, Roderick E

    2014-02-20

    The hydride proton magnetic shielding tensors for a series of iridium(III) and rhodium(III) complexes are determined. Although it has long been known that hydridic protons for transition-metal hydrides are often extremely shielded, this is the first experimental determination of the shielding tensors for such complexes. Isolating the (1)H NMR signal for a hydride proton requires careful experimental strategies because the spectra are generally dominated by ligand (1)H signals. We show that this can be accomplished for complexes containing as many as 66 ligand protons by substituting the latter with deuterium and by using hyperbolic secant pulses to selectively irradiate the hydride proton signal. We also demonstrate that the quality of the results is improved by performing experiments at the highest practical magnetic field (21.14 T for the work presented here). The hydride protons for iridium hydride complexes HIrX2(PR3)2 (X = Cl, Br, or I; R = isopropyl, cyclohexyl) are highly shielded with isotropic chemical shifts of approximately -50 ppm and are also highly anisotropic, with spans (=δ11 - δ33) ranging from 85.1 to 110.7 ppm. The hydridic protons for related rhodium complexes HRhCl2(PR3)2 also have unusual magnetic shielding properties with chemical shifts and spans of approximately -32 and 85 ppm, respectively. Relativistic density functional theory computations were performed to determine the orientation of the principal components of the hydride proton shielding tensors and to provide insights into the origin of these highly anisotropic shielding tensors. The results of our computations agree well with experiment, and our conclusions concerning the importance of relativistic effects support those recently reported by Kaupp and co-workers.

  14. Iridium-Catalyzed C-C Coupling of a Simple Propargyl Ether with Primary Alcohols: Enantioselective Homoaldol Addition via Redox-Triggered (Z)-Siloxyallylation.

    PubMed

    Liang, Tao; Zhang, Wandi; Krische, Michael J

    2015-12-30

    A chiral iridium complex formed in situ from [Ir(cod)Cl]2 and (R)-H8-BINAP is found to catalyze the direct enantioselective C-C coupling of a simple propargyl ether, TIPSOCH2C≡CH, with primary alcohols to form γ-hydroxy (Z)-enol silanes with uniformly high enantioselectivity and complete alkene (Z)-stereoselectivity. As corroborated by deuterium labeling studies, these studies represent the first examples of 1,2-hydride shift-enabled π-allyl formation in the context of iridium catalysis.

  15. Chemistry of intermetallic hydrides

    SciTech Connect

    Reilly, J.J.

    1991-01-01

    Certain intermetallic hydrides are safe, convenient and inexpensive hydrogen storage compounds. A particular advantage of such compounds is the ease with which their properties can be modified by small changes in alloy composition or preparation. This quality can be exploited to optimize their storage properties for particular applications, e.g. as intermetallic hydride electrodes in batteries. We will be concerned herein with the more important aspects of the thermodynamic and structural principles which regulate the behavior of intermetallic hydrogen systems and then illustrate their application using the archetype hydrides of LaNi5, FeTi and Mg alloys. The practical utility of these classes of materials will be briefly noted.

  16. Regenerative Hydride Heat Pump

    NASA Technical Reports Server (NTRS)

    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.

  17. Hydride heat pump

    DOEpatents

    Cottingham, James G.

    1977-01-01

    Method and apparatus for the use of hydrides to exhaust heat from one temperature source and deliver the thermal energy extracted for use at a higher temperature, thereby acting as a heat pump. For this purpose there are employed a pair of hydridable metal compounds having different characteristics working together in a closed pressure system employing a high temperature source to upgrade the heat supplied from a low temperature source.

  18. Iridium material for hydrothermal oxidation environments

    DOEpatents

    Hong, Glenn T.; Zilberstein, Vladimir A.

    1996-01-01

    A process for hydrothermal oxidation of combustible materials in which, during at least a part of the oxidation, corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises iridium, iridium oxide, an iridium alloy, or a base metal overlaid with an iridium coating. Iridium has been found to be highly resistant to environments encountered in the process of hydrothermal oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 800.degree. C.

  19. Lightweight hydride storage materials

    SciTech Connect

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.

    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.

  20. TCP Performance Enhancement Over Iridium

    NASA Technical Reports Server (NTRS)

    Torgerson, Leigh; Hutcherson, Joseph; McKelvey, James

    2007-01-01

    In support of iNET maturation, NASA-JPL has collaborated with NASA-Dryden to develop, test and demonstrate an over-the-horizon vehicle-to-ground networking capability, using Iridium as the vehicle-to-ground communications link for relaying critical vehicle telemetry. To ensure reliability concerns are met, the Space Communications Protocol Standards (SCPS) transport protocol was investigated for its performance characteristics in this environment. In particular, the SCPS-TP software performance was compared to that of the standard Transmission Control Protocol (TCP) over the Internet Protocol (IP). This paper will report on the results of this work.

  1. Formic acid dehydrogenation with bioinspired iridium complexes: a kinetic isotope effect study and mechanistic insight.

    PubMed

    Wang, Wan-Hui; Xu, Shaoan; Manaka, Yuichi; Suna, Yuki; Kambayashi, Hide; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

    2014-07-01

    Highly efficient hydrogen generation from dehydrogenation of formic acid is achieved by using bioinspired iridium complexes that have hydroxyl groups at the ortho positions of the bipyridine or bipyrimidine ligand (i.e., OH in the second coordination sphere of the metal center). In particular, [Ir(Cp*)(TH4BPM)(H2 O)]SO4 (TH4BPM: 2,2',6,6'-tetrahydroxyl-4,4'-bipyrimidine; Cp*: pentamethylcyclopentadienyl) has a high turnover frequency of 39 500 h(-1) at 80 °C in a 1 M aqueous solution of HCO2 H/HCO2 Na and produces hydrogen and carbon dioxide without carbon monoxide contamination. The deuterium kinetic isotope effect study clearly indicates a different rate-determining step for complexes with hydroxyl groups at different positions of the ligands. The rate-limiting step is β-hydrogen elimination from the iridium-formate intermediate for complexes with hydroxyl groups at ortho positions, owing to a proton relay (i.e., pendent-base effect), which lowers the energy barrier of hydrogen generation. In contrast, the reaction of iridium hydride with a proton to liberate hydrogen is demonstrated to be the rate-determining step for complexes that do not have hydroxyl groups at the ortho positions.

  2. The kinetics and mechanism of the organo-iridium catalysed racemisation of amines.

    PubMed

    Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I

    2016-08-07

    The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

  3. On the dissolution of iridium by aluminum.

    SciTech Connect

    Hewson, John C.

    2009-08-01

    The potential for liquid aluminum to dissolve an iridium solid is examined. Substantial uncertainties exist in material properties, and the available data for the iridium solubility and iridium diffusivity are discussed. The dissolution rate is expressed in terms of the regression velocity of the solid iridium when exposed to the solvent (aluminum). The temperature has the strongest influence in the dissolution rate. This dependence comes primarily from the solubility of iridium in aluminum and secondarily from the temperature dependence of the diffusion coefficient. This dissolution mass flux is geometry dependent and results are provided for simplified geometries at constant temperatures. For situations where there is negligible convective flow, simple time-dependent diffusion solutions are provided. Correlations for mass transfer are also given for natural convection and forced convection. These estimates suggest that dissolution of iridium can be significant for temperatures well below the melting temperature of iridium, but the uncertainties in actual rates are large because of uncertainties in the physical parameters and in the details of the relevant geometries.

  4. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  5. Determining the Altitude of Iridium Flares

    NASA Technical Reports Server (NTRS)

    Foster, James; Owe, Manfred

    1999-01-01

    Iridium flares have nothing to do with the element iridium. Iridium is also the name of a telecommunications company that has been launching satellites into low orbits around the Earth. These satellites are being used for a new type of wireless phone and paging service. Flares have been observed coming from these satellites. These flares have the potential, especially when the full fleet of satellites is in orbit, to disrupt astronomical observations. The paper reviews using simple trigonometry how to calculate the altitude of one of these satellites.

  6. Enantioselective, iridium-catalyzed monoallylation of ammonia.

    PubMed

    Pouy, Mark J; Stanley, Levi M; Hartwig, John F

    2009-08-19

    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.

  7. Enantioselective, Iridium-Catalyzed Monoallylation of Ammonia

    PubMed Central

    Pouy, Mark J.; Stanley, Levi M.; Hartwig, John F.

    2009-01-01

    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations. PMID:19722644

  8. Boron hydride polymer coated substrates

    DOEpatents

    Pearson, R.K.; Bystroff, R.I.; Miller, D.E.

    1986-08-27

    A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

  9. Boron hydride polymer coated substrates

    DOEpatents

    Pearson, Richard K.; Bystroff, Roman I.; Miller, Dale E.

    1987-01-01

    A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

  10. Method for preparing porous metal hydride compacts

    DOEpatents

    Ron, Moshe; Gruen, Dieter M.; Mendelsohn, Marshall H.; Sheft, Irving

    1981-01-01

    A method for preparing porous metallic-matrix hydride compacts which can be repeatedly hydrided and dehydrided without disintegration. A mixture of a finely divided metal hydride and a finely divided matrix metal is contacted with a poison which prevents the metal hydride from dehydriding at room temperature and atmospheric pressure. The mixture of matrix metal and poisoned metal hydride is then compacted under pressure at room temperature to form porous metallic-matrix hydride compacts.

  11. Method for preparing porous metal hydride compacts

    DOEpatents

    Ron, M.; Gruen, D.M.; Mendelsohn, M.H.; Sheft, I.

    1980-01-21

    A method for preparing porous metallic-matrix hydride compacts which can be repeatedly hydrided and dehydrided without disintegration. A mixture of a finely divided metal hydride and a finely divided matrix metal is contacted with a poison which prevents the metal hydride from dehydriding at room temperature and atmospheric pressure. The mixture of matrix metal and poisoned metal hydride is then compacted under pressure at room temperature to form porous metallic-matrix hydride compacts.

  12. Materials engineering of metal hydrides

    SciTech Connect

    Gruen, D.M.; Mendelsohn, M.H.

    1981-01-01

    Intermetallic hydrides of the AB/sub 5/ type have enthalpies in the range valid for chemical heat pumps. A scheme for manufacturing hydrides with optimal properties for a chemical heat pump is described, using LaNi/sub 5-x/Al/sub x/ and ZrV/sub 2x/Cr/sub x as examples. The Laves-phase ternary hydrides appear to be good candidates for gettering hydrogen in the Tokamak Fusion Test Reactor. (DLC)

  13. Superstoichiometric hydride of zirconium

    SciTech Connect

    Kupryazhkin, A.Ya.; Shchepetkin, A.A.; Zabolotskaya, E.V.; Pletnev, R.N.; Alyamovskii, S.I.; Kitaev, G.A.

    1987-12-01

    Superstoichiometric hydrides of zirconium have been obtained all the way up to the composition ZrH/sub 2.4/ by additional hydrogenation of ZrH/sub 2/ as a result of redistribution of hydrogen atoms between t- and o-positions. In the preparation of the hydrides the authors used zirconium iodide with an impurity content no greater than 10/sup -2/ to 10/sup -2/ mole %; the hydrogen and helium used in this work had a minimum purity of 99.95%. The content of hydrogen in the specimens was determined by a volumetric method. The x-ray diffraction analysis was performed in a DRON-2.0 unit (CuK/sub ..cap alpha../ radiation). PMR spectra were recorded in a broad-line spectrometer in the temperature interval 150-450 K.

  14. Hydrogen Outgassing from Lithium Hydride

    SciTech Connect

    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.

  15. IRIDIUM (R): A Lockheed transition to commercial space

    NASA Technical Reports Server (NTRS)

    Tadano, Thomas N.

    1995-01-01

    At Lockheed Missiles & Space Company, the IRIDIUM commercial space program is dramatically revolutionizing spacecraft development and manufacturing processes to reduce cost while maintaining quality and reliability. This report includes the following sections: an overview of the IRIDIUM system, the Lockheed IRIDIUM project and challenges; cycle-time reduction through production reorganization; and design for manufacturing and quality.

  16. Laser Spectroscopy of Iridium Monochloride

    NASA Astrophysics Data System (ADS)

    Linton, Colan; Adam, Allan G.; Foran, Samantha; Ma, Tongmei; Steimle, Timothy

    2016-06-01

    Iridium monochloride (IrCl) molecules have been produced in the gas phase using laser ablation sources at the University of New Brunswick (UNB) and Arizona State University (ASU). Low resolution laser induced fluorescence (LIF) spectra, obtained at UNB using a pulsed dye laser, showed three bands at 557, 545 and 534 nm which appeared to form an upper state vibrational progression. Dispersed fluorescence (DF) spectra, obtained by exciting each band at its band head frequency, showed a ground state vibrational progression extending from v=0 to 6. High resolution spectra (FWHM=0.006 wn), taken using a cw ring dye laser, showed resolved rotational lines, broadened by unresolved Ir (I=3/2) hyperfine structure, in both the 193Ir35Cl and 191Ir35Cl isotopologues. Vibrational assignments of 0-0, 1-0 and 2-0 for the three bands were determined from the isotope structure and the rotational analysis showed the transition to be ^3Φ_4 - ^3Φ_4, similar to that previously observed in IrF. Higher resolution spectra (FWHM=0.001 wn) of the 1-0 band, obtained at ASU, showed resolved hyperfine structure from which the magnetic and quadrupole hyperfine parameters in the ground and excited states were determined. The interpretation of the hyperfine parameters in terms of the electron configurations will be presented along with a comparison of the properties of IrCl and IrF.

  17. 17. VIEW OF HYDRIDING SYSTEM IN BUILDING 881. THE HYDRIDING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    17. VIEW OF HYDRIDING SYSTEM IN BUILDING 881. THE HYDRIDING SYSTEM WAS PART OF THE FAST ENRICHED URANIUM RECOVERY PROCESS. (11/11/59) - Rocky Flats Plant, General Manufacturing, Support, Records-Central Computing, Southern portion of Plant, Golden, Jefferson County, CO

  18. In vitro study of iridium electrodes for neural stimulation.

    PubMed

    Aryan, Naser Pour; Brendler, Christian; Rieger, Viola; Schleehauf, Sebastian; Heusel, Gerhard; Rothermel, Albrecht

    2012-01-01

    Iridium is one of the main electrode materials for applications like neural stimulation. Iridium has a higher charge injection capacity when activated and transformed into AIROF (activated iridium oxide film) using specific electrical signals. Activation is not possible in stimulating devices, if they do not include the necessary circuitry for activation. We introduce a method for iridium electrode activation requiring minimum additional on-chip hardware. In the main part, the lifetime behavior of iridium electrodes is investigated. These results may be interesting for applications not including on-chip activation hardware, and also because activation has drawbacks such as worse mechanical properties and reproducibility of AIROF.

  19. Hydrogenation using hydrides and acid

    DOEpatents

    Bullock, R. Morris

    1990-10-30

    A process for the non-catalytic hydrogenation of organic compounds, which contain at least one reducible functional group, which comprises reacting the organic compound, a hydride complex, preferably a transition metal hydride complex or an organosilane, and a strong acid in a liquid phase.

  20. Annealing Increases Stability Of Iridium Thermocouples

    NASA Technical Reports Server (NTRS)

    Germain, Edward F.; Daryabeigi, Kamran; Alderfer, David W.; Wright, Robert E.; Ahmed, Shaffiq

    1989-01-01

    Metallurgical studies carried out on samples of iridium versus iridium/40-percent rhodium thermocouples in condition received from manufacturer. Metallurgical studies included x-ray, macroscopic, resistance, and metallographic studies. Revealed large amount of internal stress caused by cold-working during manufacturing, and large number of segregations and inhomogeneities. Samples annealed in furnace at temperatures from 1,000 to 2,000 degree C for intervals up to 1 h to study effects of heat treatment. Wire annealed by this procedure found to be ductile.

  1. Dimensionally stable metallic hydride composition

    DOEpatents

    Heung, Leung K.

    1994-01-01

    A stable, metallic hydride composition and a process for making such a composition. The composition comprises a uniformly blended mixture of a metal hydride, kieselguhr, and a ballast metal, all in the form of particles. The composition is made by subjecting a metal hydride to one or more hydrogen absorption/desorption cycles to disintegrate the hydride particles to less than approximately 100 microns in size. The particles are partly oxidized, then blended with the ballast metal and the kieselguhr to form a uniform mixture. The mixture is compressed into pellets and calcined. Preferably, the mixture includes approximately 10 vol. % or more kieselguhr and approximately 50 vol. % or more ballast. Metal hydrides that can be used in the composition include Zr, Ti, V, Nb, Pd, as well as binary, tertiary, and more complex alloys of La, Al, Cu, Ti, Co, Ni, Fe, Zr, Mg, Ca, Mn, and mixtures and other combinations thereof. Ballast metals include Al, Cu and Ni.

  2. Iridium emissions from Hawaiian volcanoes

    NASA Technical Reports Server (NTRS)

    Finnegan, D. L.; Zoller, W. H.; Miller, T. M.

    1988-01-01

    Particle and gas samples were collected at Mauna Loa volcano during and after its eruption in March and April, 1984 and at Kilauea volcano in 1983, 1984, and 1985 during various phases of its ongoing activity. In the last two Kilauea sampling missions, samples were collected during eruptive activity. The samples were collected using a filterpack system consisting of a Teflon particle filter followed by a series of 4 base-treated Whatman filters. The samples were analyzed by INAA for over 40 elements. As previously reported in the literature, Ir was first detected on particle filters at the Mauna Loa Observatory and later from non-erupting high temperature vents at Kilauea. Since that time Ir was found in samples collected at Kilauea and Mauna Loa during fountaining activity as well as after eruptive activity. Enrichment factors for Ir in the volcanic fumes range from 10,000 to 100,000 relative to BHVO. Charcoal impregnated filters following a particle filter were collected to see if a significant amount of the Ir was in the gas phase during sample collection. Iridium was found on charcoal filters collected close to the vent, no Ir was found on the charcoal filters. This indicates that all of the Ir is in particulate form very soon after its release. Ratios of Ir to F and Cl were calculated for the samples from Mauna Loa and Kilauea collected during fountaining activity. The implications for the KT Ir anomaly are still unclear though as Ir was not found at volcanoes other than those at Hawaii. Further investigations are needed at other volcanoes to ascertain if basaltic volcanoes other than hot spots have Ir enrichments in their fumes.

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

    PubMed

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

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

  4. Osmium-191/iridium-191m radionuclide

    DOEpatents

    Knapp, Jr., Furn F.; Butler, Thomas A.; Brihaye, Claude

    1987-01-01

    A generator system to provide iridium-191m for clinical imaging applications comprises an activated carbon adsorbent loaded with a compound containing the parent nuclide, osmium-191. The generator, which has a shelf-life in excess of two weeks and does not require a scavenger column, can be eluted with physiologically compatible saline.

  5. Osmium-191/iridium-191m radionuclide

    DOEpatents

    Knapp, F.F. Jr.; Butler, T.A.; Brihaye, C.

    1985-08-26

    A generator system to provide iridium-191m for clinical imaging applications comprises an activated carbon adsorbent loaded with a compound containing the parent nuclide, osmium-191. The generator, which has a shelf-life in excess of two weeks and does not require a scavenger column, can be eluted with physiologically compatible saline. 4 figs. 3 tabs.

  6. Iridium-Coated Rhenium Combustion Chamber

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Tuffias, Robert H.; Rosenberg, Sanders D.

    1994-01-01

    Iridium-coated rhenium combustion chamber withstands operating temperatures up to 2,200 degrees C. Chamber designed to replace older silicide-coated combustion chamber in small rocket engine. Modified versions of newer chamber could be designed for use on Earth in gas turbines, ramjets, and scramjets.

  7. Iridium-192 Production for Cancer Treatment

    SciTech Connect

    Rostelato, M.E.C.M.; Silva, C.P.G.; Rela, P.R.; Zeituni, C.A.; Lepki, V.; Feher, A.

    2004-10-05

    The purpose of this work is to settle a laboratory for Iridium -192 sources production, that is, to determine a wire activation method and to build a hot cell for the wires manipulation, quality control and packaging. The paper relates, mainly, the wire activation method and its quality control. The wire activation is carried out in our nuclear reactor, IEA- R1m.

  8. Solvent-Dependent Thermochemistry of an Iridium/Ruthenium H2 Evolution Catalyst.

    PubMed

    Brereton, Kelsey R; Pitman, Catherine L; Cundari, Thomas R; Miller, Alexander J M

    2016-11-21

    The hydricity of the heterobimetallic iridium/ruthenium catalyst [Cp*Ir(H)(μ-bpm)Ru(bpy)2](3+) (1, where Cp* = η(5)-pentamethylcyclopentadienyl, bpm = 2,2'-bipyrimidine, and bpy = 2,2'-bipyridine) has been determined in both acetonitrile (63.1 kcal mol(-1)) and water (29.7 kcal mol(-1)). Hydride 1 features a large increase in the hydride donor ability when the solvent is changed from acetonitrile to water. The acidity of 1, in contrast, is essentially solvent-independent because 1 remains strongly acidic in both solvents. On the basis of an X-ray crystallographic study, spectroscopic analysis, and time-dependent density functional theory calculations, the disparate reactivity trends are ascribed to substantial delocalization of the electron density onto both the bpm and bpy ligands in the conjugate base of 1, [Cp*Ir(μ-bpm)Ru(bpy)2](2+) (3). The H2 evolution tendencies of 1 are considered in the context of thermodynamic parameters.

  9. Hydride development for hydrogen storage

    SciTech Connect

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.; Yang, N.Y.C.; Sandrock, G.

    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.

  10. Complex Hydrides for Hydrogen Storage

    SciTech Connect

    Slattery, Darlene; Hampton, Michael

    2003-03-10

    This report describes research into the use of complex hydrides for hydrogen storage. The synthesis of a number of alanates, (AIH4) compounds, was investigated. Both wet chemical and mechano-chemical methods were studied.

  11. Application of the Iridium Satellite System to Aeronautical Communications

    NASA Technical Reports Server (NTRS)

    Kerczewski, Robert J.; Meza, Mike; Gupta, Om

    2008-01-01

    The next generation air transportation system will require greater air-ground communications capacity to accommodate more air traffic with increased safety and efficiency. Communications will remain primarily terrestrially based, but satellite communications will have an increased role. Inmarsat s aeronautical services have been approved and are in use for aeronautical safety communications provided by geostationary satellites. More recently the approval process for the Iridium low earth orbit constellation is nearing completion. The current Iridium system will be able to provide basic air traffic services communications suitable for oceanic, remote and polar regions. The planned second generation of the Iridium system, called Iridium NEXT, will provide enhanced capabilities and enable a greater role in the future of aeronautical communications. This paper will review the potential role of satellite communications in the future of air transportation, the Iridium approval process and relevant system testing, and the potential role of Iridium NEXT.

  12. Low density metal hydride foams

    DOEpatents

    Maienschein, Jon L.; Barry, Patrick E.

    1991-01-01

    Disclosed is a low density foam having a porosity of from 0 to 98% and a density less than about 0.67 gm/cc, prepared by heating a mixture of powered lithium hydride and beryllium hydride in an inert atmosphere at a temperature ranging from about 455 to about 490 K for a period of time sufficient to cause foaming of said mixture, and cooling the foam thus produced. Also disclosed is the process of making the foam.

  13. Iridium and Radio Astronomy in Europe

    NASA Astrophysics Data System (ADS)

    Cohen, R. J.

    2004-06-01

    An account is given of the coordination of the Iridium mobile satellite system with the radio astronomy service in Europe, from the initial exploratory discussions at Jodrell Bank in 1991 to the signing of the so-called ``Interim Agreement'' in Paris in 1999. The technical issue of unwanted emissions from the Iridium downlink into the frequency band 1610.6-1613.8 MHz was not resolved, so the coordination agreement amounts to time sharing, albeit on more favourable terms for radio astronomy than agreements negotiated elsewhere. The European agreement fully recognizes the heavy use of the frequency band in European radio astronomy, and carries the promise that ``from 1 January 2006, European radioastronomers shall be able to collect measurement data consistent with the recommendation ITU-R RA.769-1.'' Some personal observations on the events are offered.

  14. Iridium-coated rhenium thrusters by CVD

    NASA Technical Reports Server (NTRS)

    Harding, John T.; Kazaroff, John M.; Appel, Marshall A.

    1988-01-01

    Operation of spacecraft thrusters at increased temperature reduces propellant requirements. Inasmuch as propellant comprises the bulk of a satellite's mass, even a small percentage reduction makes possible a significant enhancement of the mission in terms of increased payload. Because of its excellent high temperature strength, rhenium is often the structural material of choice. It can be fabricated into free-standing shapes by chemical vapor deposition (CVD) onto an expendable mandrel. What rhenium lacks is oxidation resistance, but this can be provided by a coating of iridium, also by CVD. This paper describes the process used by Ultramet to fabricate 22-N (5-lbf) and, more recently, 445-N (100-lbf) Ir/Re thrusters; characterizes the CVD-deposited materials; and summarizes the materials effects of firing these thrusters. Optimal propellant mixture ratios can be employed because the materials withstand an oxidizing environment up to the meltimg temperature of iridium, 2400 C (4350 F).

  15. Iridium-coated rhenium thrusters by CVD

    NASA Technical Reports Server (NTRS)

    Harding, J. T.; Kazaroff, J. M.; Appel, M. A.

    1989-01-01

    Operation of spacecraft thrusters at increased temperature reduces propellant requirements. Inasmuch as propellant comprises the bulk of a satellite's mass, even a small percentage reduction makes possible a significant enhancement of the mission in terms of increased payload. Because of its excellent high temperature strength, rhenium is often the structural material of choice. It can be fabricated into free-standing shapes by chemical vapor deposition (CVD) onto an expendable mandrel. What rhenium lacks is oxidation resistance, but this can be provided by a coating of iridium, also by CVD. This paper describes the process used by Ultramet to fabricate 22-N (5-lbf) and, more recently, 445-N (100-lbf) Ir/Re thrusters; characterizes the CVD-deposited materials; and summarizes the materials effects of firing these thrusters. Optimal propellant mixture ratios can be employed because the materials withstand an oxidizing environment up to the melting temperature of iridium, 2400 C (4350 F).

  16. Iridium versus Iridium: Nanocluster and Monometallic Catalysts Carrying the Same Ligand Behave Differently.

    PubMed

    Cano, Israel; Martínez-Prieto, Luis M; Chaudret, Bruno; van Leeuwen, Piet W N M

    2017-01-26

    A specific secondary phosphine oxide (SPO) ligand (tert-butyl(phenyl)phosphine oxide) was employed to generate two iridium catalysts, an Ir-SPO complex and IrNPs (iridium nanoparticles) ligated with SPO ligands, which were compared mutually and with several supported iridium catalysts with the aim to establish the differences in their catalytic properties. The Ir-SPO-based catalysts showed totally different activities and selectivities in the hydrogenation of various substituted aldehydes, in which H2 is likely cleaved by a metal-ligand cooperation, that is, the SPO ligand and a neighboring metal centre operate in tandem to activate the hydrogen molecule. In addition, the supported IrNPs behave very differently from both Ir-SPO catalysts. This study exemplifies perfectly the advantages and disadvantages related to the use of the main types of catalysts, and thus the dissimilarities between them.

  17. The Chemical Vapor Deposition of Iridium.

    DTIC Science & Technology

    1981-07-01

    accepted types are made of porous tungsten impregnated with barium calcium aluminates (Levi, 1955; Brodie and Jenkins, 1956). The emission capability of the...not only does the chemical composition of the pore ends and the bulk material undergo alteration, but the crystal structure of the tungsten (Maloney... hexafluoride to iridium metal or IrF 6 species. In our work, IrF 6 was prepared and stored in fluorine-passivated apparatus, and between runs maintained at

  18. Sputtered iridium oxide for stimulation electrode coatings.

    PubMed

    Mokwa, Wilfried; Wessling, Boerge; Schnakenberg, Uwe

    2007-01-01

    This work deals with the reactive RF-powered sputter deposition of iridium oxide for use as the active stimulation layer in functional medical implants. The oxygen gettered by the growing films is determined by an approach based on generic curves. Films deposited at different stages of oxygen integration show strong differences in electrochemical behaviour, caused by different morphologies. The dependence of electrochemical activity on morphology is further illustrated by RF sputtering onto heated substrates, as well as DC sputtering onto cold substrates.

  19. Benzo annulated cycloheptatriene PCP pincer iridium complexes.

    PubMed

    Leis, Wolfgang; Wernitz, Sophie; Reichart, Benedikt; Ruckerbauer, David; Wielandt, Johannes Wolfram; Mayer, Hermann A

    2014-08-28

    The benzo annulated cycloheptatriene PCP pincer ligand was prepared in five steps. Treatment of with Ir(CO)3Cl gave the meridional cyclometalated chlorohydrido carbonyl iridium complexes which differ in their arrangement of the H, Cl, and CO ligands around iridium. Storing in THF led to isomerization processes. Hydrogen shifts from the sp(3)-CH carbon bound to iridium into the ligand backbone produced the three isomers . Reductive elimination of HCl from these complexes resulted in the square planar Ir(i) carbonyl complexes . Abstraction of the hydrogen from the sp(3)-CH-Ir fragment could be achieved either by treatment of with Ph3CBF4 or by the elimination of H2 which is initiated by CF3SO3H. The mass spectrometric characterisation of using fast atom bombardment reveals a complex fragmentation pattern. These different "fragment" ions were further investigated by electro-spray ionisation (tandem) mass spectrometry in high and low resolution. The identified compounds were attributed to structures by DFT calculations.

  20. Complex and liquid hydrides for energy storage

    NASA Astrophysics Data System (ADS)

    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

    2016-04-01

    The research on complex hydrides for hydrogen storage was initiated 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 regarding the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant portion of the research groups active in the field of complex hydrides is collaborators in the International Energy Agreement Task 32. This paper reports about the important issues in the field of complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides, 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 is an excellent summary of the recent achievements.

  1. Complex and liquid hydrides for energy storage

    SciTech Connect

    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.

  2. A new route to metal hydrides

    SciTech Connect

    Murphy, D.W.; Zahurak, S.M.; Vyas, B.; Thomas, M.; Badding, M.E.; Fang, W.C. )

    1993-06-01

    Aqueous borohydride is shown to be an effective reagent for hydriding metals and intermetallics. It is the hydriding equivalent of 20-30 atm of H[sub 2]. The reaction is a convenient way to screen materials for hydride formation and possible utility in applications such as nickel-metal hydride batteries. The reaction is also a convenient alternative to decrepitation for the production of free flowing powders. 16 refs., 1 fig., 1 tab.

  3. Gas-phase acidities of binary hydrides.

    NASA Technical Reports Server (NTRS)

    Brauman, J. I.; Eyler, J. R.; Blair, L. K.; White, M. J.; Comisarow, M. B.; Smyth, K. C.

    1971-01-01

    The preferred direction of proton transfer in a reaction between a hydride molecule and a hydride ion was studied in order to determine the relative acidities of some binary hydrides. Sufficient data are presented to make clear the periodic trends in acidities and the underlying trends in other fundamental thermochemical quantities which influence acidity. The bond dissociation energies and electron affinities of the hydrides considered are listed in a table.

  4. Photochemistry of Transition Metal Hydrides.

    PubMed

    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.

  5. Hydrogen, lithium, and lithium hydride production

    DOEpatents

    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.

  6. Vanadium hydride deuterium-tritium generator

    DOEpatents

    Christensen, Leslie D.

    1982-01-01

    A pressure controlled vanadium hydride gas generator to provide deuterium-tritium gas in a series of pressure increments. A high pressure chamber filled with vanadium-deuterium-tritium hydride is surrounded by a heater which controls the hydride temperature. The heater is actuated by a power controller which responds to the difference signal between the actual pressure signal and a programmed pressure signal.

  7. Method of producing a chemical hydride

    DOEpatents

    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.

  8. Synthesis of benzimidazoles via iridium-catalyzed acceptorless dehydrogenative coupling.

    PubMed

    Sun, Xiang; Lv, Xiao-Hui; Ye, Lin-Miao; Hu, Yu; Chen, Yan-Yan; Zhang, Xue-Jing; Yan, Ming

    2015-07-21

    Iridium-catalyzed acceptorless dehydrogenative coupling of tertiary amines and arylamines has been developed. A number of benzimidazoles were prepared in good yields. An iridium-mediated C-H activation mechanism is suggested. This finding represents a novel strategy for the synthesis of benzimidazoles.

  9. Variation of iridium in a differentiated tholeiitic dolerite

    USGS Publications Warehouse

    Greenland, L.P.

    1971-01-01

    Iridium has been determined in a drill core from the Great Lake (Tasmania) dolerite sheet. Iridium decreases systematically from the mafic dolerites (0.25 ppb) to the granophyres (0.006 ppb). The trend with differentiation closely parallels that of chromium. ?? 1971.

  10. Iridium enrichment in airborne particles from kilauea volcano: january 1983.

    PubMed

    Zoller, W H; Parrington, J R; Kotra, J M

    1983-12-09

    Airborne particulate matter from the January 1983 eruption of Kilauea volcano was inadvertently collected on air filters at Mauna Loa Observatory at a sampling station used to observe particles in global circulation. Analyses of affected samples revealed unusually large concentrations of selenium, arsenic, indium, gold, and sulfur, as expected for volcanic emissions. Strikingly large concentrations of iridium were also observed, the ratio of iridium to aluminum being 17,000 times its value in Hawaiian basalt. Since iridium enrichments have not previously been observed in volcanic emissions, the results for Kilauea suggest that it is part of an unusual volcanic system which may be fed by magma from the mantle. The iridium enrichment appears to be linked with the high fluorine content of the volcanic gases, which suggests that the iridium is released as a volatile IrF(6).

  11. Characteristics and Applications of Metal Hydrides

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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

  13. Iridium Interfacial Stack - IrIS

    NASA Technical Reports Server (NTRS)

    Spry, David

    2012-01-01

    Iridium Interfacial Stack (IrIS) is the sputter deposition of high-purity tantalum silicide (TaSi2-400 nm)/platinum (Pt-200 nm)/iridium (Ir-200 nm)/platinum (Pt-200 nm) in an ultra-high vacuum system followed by a 600 C anneal in nitrogen for 30 minutes. IrIS simultaneously acts as both a bond metal and a diffusion barrier. This bondable metallization that also acts as a diffusion barrier can prevent oxygen from air and gold from the wire-bond from infiltrating silicon carbide (SiC) monolithically integrated circuits (ICs) operating above 500 C in air for over 1,000 hours. This TaSi2/Pt/Ir/Pt metallization is easily bonded for electrical connection to off-chip circuitry and does not require extra anneals or masking steps. There are two ways that IrIS can be used in SiC ICs for applications above 500 C: it can be put directly on a SiC ohmic contact metal, such as Ti, or be used as a bond metal residing on top of an interconnect metal. For simplicity, only the use as a bond metal is discussed. The layer thickness ratio of TaSi2 to the first Pt layer deposited thereon should be 2:1. This will allow Si from the TaSi2 to react with the Pt to form Pt2Si during the 600 C anneal carried out after all layers have been deposited. The Ir layer does not readily form a silicide at 600 C, and thereby prevents the Si from migrating into the top-most Pt layer during future anneals and high-temperature IC operation. The second (i.e., top-most) deposited Pt layer needs to be about 200 nm to enable easy wire bonding. The thickness of 200 nm for Ir was chosen for initial experiments; further optimization of the Ir layer thickness may be possible via further experimentation. Ir itself is not easily wire-bonded because of its hardness and much higher melting point than Pt. Below the iridium layer, the TaSi2 and Pt react and form desired Pt2Si during the post-deposition anneal while above the iridium layer remains pure Pt as desired to facilitate easy and strong wire-bonding to the Si

  14. Iridium Film For Charge-Coupled Device

    NASA Technical Reports Server (NTRS)

    Hecht, Michael H.

    1990-01-01

    Usability extended to different environments. Application of thin film of iridium to back surface of back-surface-illuminated charge-coupled device expected to increase and stabilize quantum efficiency at wavelengths less than 4,500 Angstrom. Enhances quantum efficiency according to principle discussed in "Metal Film Increases CCD Output" (NPO-16815). Does not react with hydrogen, so device need not be kept in oxygen: Advantage where high absorption of ultraviolet light by oxygen undesirable; for example, when device used to make astronomical observations from high altitudes.

  15. Iridium/Rhenium Parts For Rocket Engines

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Harding, John T.; Wooten, John R.

    1991-01-01

    Oxidation/corrosion of metals at high temperatures primary life-limiting mechanism of parts in rocket engines. Combination of metals greatly increases operating temperature and longevity of these parts. Consists of two transition-element metals - iridium and rhenium - that melt at extremely high temperatures. Maximum operating temperature increased to 2,200 degrees C from 1,400 degrees C. Increases operating lifetimes of small rocket engines by more than factor of 10. Possible to make hotter-operating, longer-lasting components for turbines and other heat engines.

  16. Cheaper Hydride-Forming Cathodes

    NASA Technical Reports Server (NTRS)

    Jones, Jack A.; Blue, Gary

    1990-01-01

    Hydride-forming cathodes for electrochemical experiments made of materials or combinations of materials cheaper and more abundant than pure palladium, according to proposal. Concept prompted by needs of experimenters in now-discredited concept of electrochemical nuclear fusion, cathodes useful in other electrochemical applications involving generation or storage of hydrogen, deuterium, or tritium.

  17. Properties of nanoscale metal hydrides.

    PubMed

    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.

  18. Structural, kinetic, and thermodynamic study of the reversible thermal C-H activation/reductive elimination of alkanes at iridium

    SciTech Connect

    Buchanan, J.M.; Stryker, J.M.; Bergman, R.G.

    1986-04-02

    The hydrido alkyl iridium complex Cp*(PMe/sub 3/)Ir(Cy)(H) (1, Cp* = eta/sup 5/-C/sub 5/; Cy = cyclohexyl) has been isolated by air-free chromatography at -80/sup 0/C, and its molecular structure has been determined by X-ray diffraction. Thermolysis of 1 in benzene cleanly produces cyclohexane and Cp*(PMe/sub 3/)Ir(Ph)(H) (2). The rate of reaction is first-order in 1, zero-order in benzene, and inhibited by cyclohexane; its activation parameters are ..delta..H/sup + +/ = 35.6 +/- 0.5 kcal/mol and ..delta..S/sup + +/ = +10 +/- 2 eu. An inverse isotope effect, kappa/sub h/kappa/sub d/ = 0.7 +/- 0.1, is calculated from rates of cyclohexane and cyclohexane-d/sub 12/ reductive elimination at 130/sup 0/C, and deuterium scrambling between the hydride and ..cap alpha..-cyclohexyl positions is observed to occur competitively with reductive elimination. A mechanism is proposed in which cyclohexane loss from 1 is reversible and produces (Cp*(PMe/sub 3/)Ir), which oxidatively adds to a C-H bond in a benzene solvent molecule to form 2. Evidence is also presented for the possible intermediacy of a cyclohexane/(Cp*(PMe/sub 3/)Ir) sigma-complex, which is formed before free (Cp*(PMe/sub 3/)Ir) is released. Equilibrium constants for the equilibration of several pairs of alkanes and their corresponding iridium(III) hydrido alkyl complexes have been determined and imply the following trend in solution phase iridium-carbon bond dissociation enthalpies: phenyl >> n-pentyl > 2,3-dimethylbutyl > cyclopentyl approx. cyclohexyl > neopentyl.

  19. Diminiode thermionic conversion with 111-iridium electrodes

    NASA Technical Reports Server (NTRS)

    Koeger, E. W.; Bair, V. L.; Morris, J. F.

    1976-01-01

    Preliminary data indicating thermionic-conversion potentialities for a 111-iridium emitter and collector spaced 0.2 mm apart are presented. These results comprise output densities of current and of power as functions of voltage for three sets of emitter, collector, and reservoir temperatures: 1553, 944, 561 K; 1605, 898, 533 K; and 1656, 1028, 586 K. For the 1605 K evaluation, estimates produced work-function values of 2.22 eV for the emitter and 1.63 eV for the collector with a 2.0-eV barrier index (collector work function plus interelectrode voltage drop) corresponding to the maximum output of 5.5 W/sq cm at 0.24 volt. The current, voltage curve for the 1656 K 111-iridium diminiode yields a 6.2 W/sq cm maximum at 0.25 volt and is comparable with the 1700 K envelope for a diode with an etched-rhenium emitter and a 0.025-mm electrode gap made by TECO and evaluated by NASA.

  20. Ab initio phase diagram of iridium

    NASA Astrophysics Data System (ADS)

    Burakovsky, L.; Burakovsky, N.; Cawkwell, M. J.; Preston, D. L.; Errandonea, D.; Simak, S. I.

    2016-09-01

    The phase diagram of iridium is investigated using the Z methodology. The Z methodology is a technique for phase diagram studies that combines the direct Z method for the computation of melting curves and the inverse Z method for the calculation of solid-solid phase boundaries. In the direct Z method, the solid phases along the melting curve are determined by comparing the solid-liquid equilibrium boundaries of candidate crystal structures. The inverse Z method involves quenching the liquid into the most stable solid phase at various temperatures and pressures to locate a solid-solid boundary. Although excellent agreement with the available experimental data (to ≲65 GPa) is found for the equation of state (EOS) of Ir, it is the third-order Birch-Murnaghan EOS with B0'=5 rather than the more widely accepted B0'=4 that describes our ab initio data to higher pressure (P ) . Our results suggest the existence of a random-stacking hexagonal close-packed structure of iridium at high P . We offer an explanation for the 14-layer hexagonal structure observed in experiments by Cerenius and Dubrovinsky.

  1. Iridium wire grid polarizer fabricated using atomic layer deposition.

    PubMed

    Weber, Thomas; Käsebier, Thomas; Szeghalmi, Adriana; Knez, Mato; Kley, Ernst-Bernhard; Tünnermann, Andreas

    2011-10-25

    In this work, an effective multistep process toward fabrication of an iridium wire grid polarizer for UV applications involving a frequency doubling process based on ultrafast electron beam lithography and atomic layer deposition is presented. The choice of iridium as grating material is based on its good optical properties and a superior oxidation resistance. Furthermore, atomic layer deposition of iridium allows a precise adjustment of the structural parameters of the grating much better than other deposition techniques like sputtering for example. At the target wavelength of 250 nm, a transmission of about 45% and an extinction ratio of 87 are achieved.

  2. Microstructure of surface cerium hydride growth sites

    SciTech Connect

    Brierley, Martin; Knowles, John; Montgomery, Neil; Preuss, Michael

    2014-05-15

    Samples of cerium were exposed to hydrogen under controlled conditions causing cerium hydride sites to nucleate and grow on the surface. The hydriding rate was measured in situ, and the hydrides were characterised using secondary ion mass spectrometry, scanning electron microscopy, and optical microscopy. The results show that the hydriding rate proceeded more quickly than earlier studies. Characterisation confirmed that the hydrogen is confined to the sites. The morphology of the hydrides was confirmed to be oblate, and stressed material was observed surrounding the hydride, in a number of cases lathlike features were observed surrounding the hydride sites laterally with cracking in the surface oxide above them. It is proposed that during growth the increased lattice parameter of the CeH{sub 2} induces a lateral compressive stress around the hydride, which relieves by the ca. 16% volume collapse of the γ-Ce to α-Ce pressure induced phase transition. Cracking of the surface oxide above the laths reduces the diffusion barrier to hydrogen reaching the metal/oxide interface surrounding the hydride site and contributes to the anisotropic growth of the hydrides.

  3. Phase control of iridium and iridium oxide thin films in atomic layer deposition

    SciTech Connect

    Kim, Sung-Wook; Kwon, Se-Hun; Kwak, Dong-Kee; Kang, Sang-Won

    2008-01-15

    The atomic layer deposition of iridium (Ir) and iridium oxide (IrO{sub 2}) films was investigated using an alternating supply of (ethylcyclopentadienyl)(1,5-cyclooctadiene) iridium and oxygen gas at temperatures between 230 and 290 deg. C. The phase transition between Ir and IrO{sub 2} occurred at the critical oxygen partial pressure during the oxygen injection pulse. The oxygen partial pressure was controlled by the O{sub 2}/(Ar+O{sub 2}) ratio or deposition pressures. The resistivity of the deposited Ir and IrO{sub 2} films was about 9 and 120 {mu}{omega} cm, respectively. In addition, the critical oxygen partial pressure for the phase transition between Ir and IrO{sub 2} was increased with increasing the deposition temperature. Thus, the phase of the deposited film, either Ir or IrO{sub 2}, was controlled by the oxygen partial pressure and the deposition temperature. However, the formation of a thin Ir layer was detected between the IrO{sub 2} and SiO{sub 2} substrate. To remove this interfacial layer, the oxygen partial pressure is increased to a severe condition. And the impurity contents were below the detection limit of Auger electron spectroscopy in both Ir and IrO{sub 2} films.

  4. The renaissance of hydrides as energy materials

    NASA Astrophysics Data System (ADS)

    Mohtadi, Rana; Orimo, Shin-Ichi

    2016-12-01

    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.

  5. Rechargeable metal hydrides for spacecraft application

    NASA Astrophysics Data System (ADS)

    Perry, J. L.

    1988-09-01

    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.

  6. Rechargeable metal hydrides for spacecraft application

    NASA Technical Reports Server (NTRS)

    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.

  7. Monoalkylation of acetonitrile by primary alcohols catalyzed by iridium complexes.

    PubMed

    Anxionnat, Bruno; Pardo, Domingo Gomez; Ricci, Gino; Cossy, Janine

    2011-08-05

    The monoalkylation of acetonitrile by primary alcohols was achieved in a one-pot sequence in the presence of iridium catalysts. A diversity of nitriles has been obtained from aryl- and alkyl-methanols in excellent yield.

  8. Acute radiodermatitis from occupational exposure to iridium 192

    SciTech Connect

    Becker, J.; Rosen, T. )

    1989-12-01

    Industrial radiography using the man-made radioisotope iridium 192 is commonplace in the southern states. Despite established procedures and safeguards, accidental exposure may result in typical acute radiodermatitis. We have presented a clinical example of this phenomenon.9 references.

  9. Use of reversible hydrides for hydrogen storage

    NASA Technical Reports Server (NTRS)

    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.

  10. Hydrogen /Hydride/-air secondary battery

    NASA Technical Reports Server (NTRS)

    Sarradin, J.; Bronoel, G.; Percheron-Guegan, A.; Achard, J. C.

    1979-01-01

    The use of metal hydrides as negative electrodes in a hydrogen-air secondary battery seems promising. However, in an unpressurized cell, more stable hydrides that LaNi5H6 must be selected. Partial substitutions of nickel by aluminium or manganese increase the stability of hydrides. Combined with an air reversible electrode, a specific energy close to 100 Wh/kg can be expected.

  11. Inhibited solid propellant composition containing beryllium hydride

    NASA Technical Reports Server (NTRS)

    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.

  12. Multi-stage hydride-hydrogen compressor

    NASA Astrophysics Data System (ADS)

    Golben, P. M.

    A 4-stage metal hydride/hydrogen compressor that uses low temperature hot water (75 C) as its energy source has been built and tested. The compressor utilizes a new hydride heat exchanger technique that has achieved fast cycling time (with 20 C cooling water) on the order of 1 min. This refinement substantially decreases the size, weight and cost of the unit when compared to previous hydride compressors or even conventional mechanical diaphragm compressors.

  13. Vanadium hydride deuterium-tritium generator

    DOEpatents

    Christensen, L.D.

    1980-03-13

    A pressure controlled vanadium hydride gas generator was designed to provide deuterium-tritium gas in a series of pressure increments. A high pressure chamber filled with vanadium-deuterium-tritium hydride is surrounded by a heater which controls the hydride temperature. The heater is actuated by a power controller which responds to the difference signal between the actual pressure signal and a programmed pressure signal.

  14. GPS/GNSS Interference from Iridium Data Transmitters

    NASA Astrophysics Data System (ADS)

    Berglund, H. T.; Blume, F.; Estey, L.; White, S.

    2011-12-01

    The Iridium satellite communication system broadcasts in the 1610 to 1626.5 MHz band. The L1 frequencies broadcast by GPS, Galileo and GLONASS satellites are 1575.42 MHz, 1575.42 MHz and 1602 MHz + n × 0.5625 MHz, respectively (each GLONASS satellite uses a unique frequency). The proximity of the Iridium frequency band with the L1 frequencies of the GPS, Galileo and GLONASS systems leaves GNSS receivers susceptible to interference from Iridium data transmissions. Interference from Iridium transmissions can cause cycle slips and loss of lock on the carrier and code phases, thereby degrading the quality of GNSS observations and position estimates. In 2008, UNAVCO staff members observed that the percent of slips vs. the number of observations increased as the distance between a GPS choke ring antenna (TRM29659.00) and an Iridium antenna decreased. From those observations they suggested that Iridium antennas and GPS antennas should be separated by >30 m to minimize cycle slips caused by the interference from Iridium data transmissions. A second test conducted in 2009 using a newer Trimble GNSS choke ring antenna (TRM59800.00) showed similar results to the previous test despite the wider frequency range of the newer antenna. More recent testing conducted to investigate the response of new receiver models to iridium transmissions has shown that many GNSS enabled models, when combined with GNSS enabled antennas, have increased sensitivity to interference when compared to older GPS-only models. The broader frequency spectrum of the Low Noise Amplifiers (LNA) installed in many newer GNSS antennas can increase the impact of near-band RF interference on tracking performance. Our testing has shown that the quality of data collected at sites collocated with iridium communications is highly degraded for antenna separations exceeding 100m. Using older GPS antenna models (e.g. TRM29659.00) with newer GNSS enabled receivers can reduce this effect. To mitigate the effects that

  15. Synthesis and characterization of nitrides of iridium and palladiums

    SciTech Connect

    Crowhurst, Jonathan C.; Goncharov, Alexander F.; Sadigh, B.; Zaug, J.M.; Aberg, D.; Meng, Yue; Prakapenka, Vitali B.

    2008-08-14

    We describe the synthesis of nitrides of iridium and palladium using the laser-heated diamond anvil cell. We have used the in situ techniques of x-ray powder diffraction and Raman scattering to characterize these compounds and have compared our experimental findings where possible to the results of first-principles theoretical calculations. We suggest that palladium nitride is isostructural with pyrite, while iridium nitride has a monoclinic symmetry and is isostructural with baddeleyite.

  16. Iridium{reg_sign} worldwide personal communication system

    SciTech Connect

    Helm, J.

    1997-01-01

    The IRIDIUM system is a personal worldwide communication system designed to support portable, low power subscriber units through the use of a constellation of satellites in low earth polar orbit. The satellites are networked together to form a system which provides continuous line-of-sight communications between the IRIDIUM system and any point within 30 km of the earth{close_quote}s surface. The system architecture and operation are described. {copyright} {ital 1997 American Institute of Physics.}

  17. Ten degree Kelvin hydride refrigerator

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1987-01-01

    A compact hydride absorption refrigeration system with few moving parts for 10 Kelvin operation is disclosed and comprises liquid hydrogen producing means in combination with means for solidifying and subliming the liquid hydrogen produced. The liquid hydrogen is sublimed at about 10 Kelvin. By using a symmetrical all hydrogen redundant loop system, a 10 Kelvin refrigeration system can be operated for many years with only a fraction of the power required for prior art systems.

  18. Complex hydrides for hydrogen storage

    DOEpatents

    Zidan, Ragaiy

    2006-08-22

    A hydrogen storage material and process of forming the material is provided in which complex hydrides are combined under conditions of elevated temperatures and/or elevated temperature and pressure with a titanium metal such as titanium butoxide. The resulting fused product exhibits hydrogen desorption kinetics having a first hydrogen release point which occurs at normal atmospheres and at a temperature between 50.degree. C. and 90.degree. C.

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

    PubMed

    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.

  20. Thermodynamic Hydricity of Transition Metal Hydrides.

    PubMed

    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.

  1. Laser Induced Fluorescence Spectrum of Iridium Monophosphide

    NASA Astrophysics Data System (ADS)

    Pang, H. F.; Liu, Anwen; Cheung, A. S.-C.

    2009-06-01

    Laser induced fluorescence spectrum of IrP in the spectral region between 380-600 nm has been studied. Reacting laser ablated iridium atoms with 1% PH_3 seeded in argon produced the IrP molecule. A few vibronic transitions have been recorded. Preliminary analysis of the rotational structure indicated that these vibronic bands are with Ω^' = 0 and Ω^'' = 0 and is likely to be ^{1}Σ - X ^{1}Σ transition. Vibrational separation of the excited state is estimated to be about 442 cm^{-1}. The ground state bond length is determined to be 1.766 Å. This work represents the first experimental investigation of the spectra of IrP.

  2. Solventless synthesis of iridium(0) nanoparticles

    NASA Astrophysics Data System (ADS)

    Redón, R.; Ramírez-Crescencio, F.; Fernández-Osorio, A. L.

    2011-11-01

    In this article, we present the results of a solvent-free synthesis of iridium(0) nanoparticles, both water washed and unwashed. IrCl3 and NaBH4, as starting materials, are mixed using an agate mortar and milled for 15 min until a black powder is obtained, which is heated in a nitrogen-controlled atmosphere oven at 200 °C for 2 h. If the product of the reaction is not washed before heating, NaBH4 and IrO2 impurities are observed. On the other hand, if the reaction product is washed before the heating, the obtained powder is free of impurities. We study the effect of the variation in reducing agent concentration and the annealing temperature used after the reaction. In all cases, the calculated particle size is less than 10 nm.

  3. On the Extreme Oxidation States of Iridium.

    PubMed

    Pyykkö, Pekka; Xu, Wen-Hua

    2015-06-22

    It has recently been suggested that the oxidation states of Ir run from the putative -III in the synthesized solid Na3 [Ir(CO)3 ] to the well-documented +IX in the species IrO4 (+) . Furthermore, [Ir(CO)3 ](3-) was identified as an 18-electron species. A closer DFT study now finds support for this picture: The orbitals spanned by the 6s,6p,5d orbitals of the iridium are all occupied. Although some have considerable ligand character, the deviations from 18 e leave the orbital symmetries unchanged. The isoelectronic systems from Os(-IV) to Au(-I) behave similarly, suggesting further possible species. To paraphrase Richard P. Feynmann "there is plenty of room at the bottom".

  4. PURIFICATION OF IRIDIUM BY ELECTRON BEAM MELTING

    SciTech Connect

    Ohriner, Evan Keith

    2008-01-01

    The purification of iridium metal by electron beam melting has been characterized for 48 impurity elements. Chemical analysis was performed by glow discharge mass spectrographic (GDMS) analysis for all elements except carbon, which was analyzed by combustion. The average levels of individual elemental impurities in the starting powder varied from 37 g/g to 0.02 g/g. The impurity elements Li, Na, Mg, P, S, Cl, K, Ca, Mn, Co, Ni, Cu, Zn, As, Pd, Ag, Cd, Sn, Sb, Te, Ba, Ce, Tl, Pb, and Bi were not detectable following the purification. No significant change in concentration of the elements Ti, V, Zr, Nb, Mo, and Re was found. The elements B, C, Al, Si, Cr, Fe, Ru, Rh, and Pt were partially removed by vaporization during electron beam melting. Langmuir's equation for ideal vaporization into a vacuum was used to calculate for each impurity element the expected ratio of impurity content after melting to that before melting. Equilibrium vapor pressures were calculated using Henry's law, with activity coefficients obtained from published data for the elements Fe, Ti, and Pt. Activity coefficients were estimated from enthalpy data for Al, Si, V, Cr, Mn, Co, Ni, Zr, Nb, Mo, and Hf and an ideal solution model was used for the remaining elements. The melt temperature was determined from measured iridium weight loss. Excellent agreement was found between measured and calculated impurity ratios for all impurity elements. The results are consistent with some localized heating of the melt pool due to rastering of the electron beam, with an average vaporization temperature of 3100 K as compared to a temperature of 2965 K calculated for uniform heating of the melt pool. The results are also consistent with ideal mixing in the melt pool.

  5. Fundamental experiments on hydride reorientation in zircaloy

    NASA Astrophysics Data System (ADS)

    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

  6. DETERMINATION OF HETEROGENEOUS ELECTRON TRANSFER RATE CONSTANTS AT MICROFABRICATED IRIDIUM ELECTRODES. (R825511C022)

    EPA Science Inventory

    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  7. Iridium complexes demonstrating broadband emission through controlled geometric distortion and applications thereof

    SciTech Connect

    Li, Jian; Turner, Eric

    2016-04-12

    Iridium compounds and their uses are disclosed herein. For example, carbazole containing iridium compounds are disclosed. The compounds are useful in many devices, including, but not limited to, electroluminescent devices.

  8. Erbium hydride thermal desorption : controlling kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2007-08-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report show that hydride film processing parameters directly impact thermal stability. Issues to be addressed include desorption kinetics for dihydrides and trihydrides, and the effect of film growth parameters, loading parameters, and substrate selection on desorption kinetics.

  9. Direct synthesis of catalyzed hydride compounds

    DOEpatents

    Gross, Karl J.; Majzoub, Eric

    2004-09-21

    A method is disclosed for directly preparing alkali metal aluminum hydrides such as NaAlH.sub.4 and Na.sub.3 AlH.sub.6 from either the alkali metal or its hydride, and aluminum. The hydride thus prepared is doped with a small portion of a transition metal catalyst compound, such as TiCl.sub.3, TiF.sub.3, or a mixture of these materials, in order to render them reversibly hydridable. The process provides for mechanically mixing the dry reagents under an inert atmosphere followed by charging the mixed materials with high pressure hydrogen while heating the mixture to about 125.degree. C. The method is relatively simple and inexpensive and provides reversible hydride compounds which are free of the usual contamination introduced by prior art wet chemical methods.

  10. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    SciTech Connect

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady; Sadow, Aaron D

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

  11. Zirconium hydride containing explosive composition

    DOEpatents

    Walker, Franklin E.; Wasley, Richard J.

    1981-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising a non-explosive compound or mixture of non-explosive compounds which when subjected to an energy fluence of 1000 calories/cm.sup.2 or less is capable of releasing free radicals each having a molecular weight between 1 and 120. Exemplary donor additives are dibasic acids, polyamines and metal hydrides.

  12. Activated aluminum hydride hydrogen storage compositions and uses thereof

    DOEpatents

    Sandrock, Gary; Reilly, James; Graetz, Jason; Wegrzyn, James E.

    2010-11-23

    In one aspect, the invention relates to activated aluminum hydride hydrogen storage compositions containing aluminum hydride in the presence of, or absence of, hydrogen desorption stimulants. The invention particularly relates to such compositions having one or more hydrogen desorption stimulants selected from metal hydrides and metal aluminum hydrides. In another aspect, the invention relates to methods for generating hydrogen from such hydrogen storage compositions.

  13. Highly fluorescent and biocompatible iridium nanoclusters for cellular imaging.

    PubMed

    Vankayala, Raviraj; Gollavelli, Ganesh; Mandal, Badal Kumar

    2013-08-01

    Highly fluorescent iridium nanoclusters were synthesized and investigated its application as a potential intracellular marker. The iridium nanoclusters were prepared with an average size of ~2 nm. Further, these nanoclusters were refluxed with aromatic ligands, such as 2,2'-binaphthol (BINOL) in order to obtain fluorescence properties. The photophysical properties of these bluish-green emitting iridium nanoclusters were well characterized by using UV-Visible, fluorescence and lifetime decay measurements. The emission spectrum for these nanoclusters exhibit three characteristic peaks at 449, 480 and 515 nm. The fluorescence quantum yield of BINOL-Ir NCs were estimated to be 0.36 and the molar extinction co-efficients were in the order of 10(6) M(-1)cm(-1). In vitro cytotoxicity studies in HeLa cells reveal that iridium nanoclusters exhibited good biocompatibility with an IC50 value of ~100 μg/ml and also showed excellent co-localization and distribution throughout the cytoplasm region without entering into the nucleus. This research has opened a new window in developing the iridium nanoparticle based intracellular fluorescent markers and has wide scope to act as biomedical nanocarrier to carry many biological molecules and anticancer drugs.

  14. SO2 adsorption on silica supported iridium

    NASA Astrophysics Data System (ADS)

    Bounechada, Djamela; Anderson, David P.; Skoglundh, Magnus; Carlsson, Per-Anders

    2017-02-01

    The interaction of SO2 with Ir/SiO2 was studied by simultaneous in situ diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry, exposing the sample to different SO2 concentrations ranging from 10 to 50 ppm in the temperature interval 200-400 °C. Evidences of adsorption of sulfur species in both absence and presence of oxygen are found. For a pre-reduced sample in the absence of oxygen, SO2 disproportionates such that the iridium surface is rapidly saturated with adsorbed S while minor amounts of formed SO3 may adsorb on SiO2. Adding oxygen to the feed leads to the oxidation of sulfide species that either (i) desorb as SO2 and/or SO3, (ii) remain at metal sites in the form of adsorbed SO2, or (iii) spillover to the oxide support and form sulfates (SO42-). Notably, significant formation of sulfates on silica is possible only in the presence of both SO2 and O2, suggesting that SO2 oxidation to SO3 is a necessary first step in the mechanism of formation of sulfates on silica. During the formation of sulfates, a concomitant removal/rearrangement of surface silanol groups is observed. Finally, the interaction of SO2 with Ir/SiO2 depends primarily on the temperature and type of gas components but only to a minor extent on the inlet SO2 concentration.

  15. Hydrogen-storing hydride complexes

    DOEpatents

    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.

  16. Liquid suspensions of reversible metal hydrides

    DOEpatents

    Reilly, J.J.; Grohse, E.W.; Winsche, W.E.

    1983-12-08

    The reversibility of the process M + x/2 H/sub 2/ ..-->.. MH/sub x/, where M is a metal hydride former that forms a hydride MH/sub x/ in the presence of H/sub 2/, generally used to store and recall H/sub 2/, is found to proceed under a liquid, thereby to reduce contamination, provide better temperature control and provide in situ mobility of the reactants. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to temperature and pressure controlled atmosphere containing H/sub 2/, to store hydrogen (at high pressures) and to release (at low pressures) previously stored hydrogen. The direction of the flow of the H/sub 2/ through the liquid is dependent upon the H/sub 2/ pressure in the gas phase at a given temperature. When the former is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particle. When the H/sub 2/ pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

  17. Experimental determination of the solubility of iridium in silicate melts: Preliminary results

    NASA Technical Reports Server (NTRS)

    Borisov, Alexander; Dingwell, Donald B.; Oneill, Hugh ST.C.; Palme, Herbert

    1992-01-01

    Little is known of the geochemical behavior of iridium. Normally this element is taken to be chalcophile and/or siderophile so that during planetary differentiation processes, e.g., core formation, iridium is extracted from silicate phases into metallic phases. Experimental determination of the metal/silicate partition coefficient of iridium is difficult simply because it is so large. Also there are no data on the solubility behavior of iridium in silicate melts. With information on the solubility of iridium in silicate melts it is possible, in combination with experimental data for Fe-Ir alloys, to calculate the partition coefficient between a metallic phase and a silicate melt.

  18. Hydride heat pump with heat regenerator

    NASA Technical Reports Server (NTRS)

    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.

  19. High-pressure synthesis of lithium hydride

    NASA Astrophysics Data System (ADS)

    Howie, Ross T.; Narygina, Olga; Guillaume, Christophe L.; Evans, Shaun; Gregoryanz, Eugene

    2012-08-01

    By compressing elemental lithium and hydrogen in a diamond anvil cell, we have synthesized lithium hydride (LiH) at pressures as low as 50 MPa at room temperature. Combined Raman spectroscopy and synchrotron x-ray diffraction measurements reveal that, once synthesized, LiH remains stable at 300 K up to 160 GPa in the presence of molecular hydrogen. The mixture of lithium hydride and molecular hydrogen and application of pressure alone cannot form a higher H2 content hydride (LiHx, x>1) as was suggested from the theoretical ab initio calculations and therefore, cannot be considered as a route to low-pressure hydrogen rich material metallization.

  20. Computational Modeling of Uranium Hydriding and Complexes

    SciTech Connect

    Balasubramanian, K; Siekhaus, W J; McLean, W

    2003-02-03

    Uranium hydriding is one of the most important processes that has received considerable attention over many years. Although many experimental and modeling studies have been carried out concerning thermochemistry, diffusion kinetics and mechanisms of U-hydriding, very little is known about the electronic structure and electronic features that govern the U-hydriding process. Yet it is the electronic feature that controls the activation barrier and thus the rate of hydriding. Moreover the role of impurities and the role of the product UH{sub 3} on hydriding rating are not fully understood. An early study by Condon and Larson concerns with the kinetics of U-hydrogen system and a mathematical model for the U-hydriding process. They proposed that diffusion in the reactant phase by hydrogen before nucleation to form hydride phase and that the reaction is first order for hydriding and zero order for dehydriding. Condon has also calculated and measures the reaction rates of U-hydriding and proposed a diffusion model for the U-hydriding. This model was found to be in excellent agreement with the experimental reaction rates. From the slopes of the Arrhenius plot the activation energy was calculated as 6.35 kcal/mole. In a subsequent study Kirkpatrick formulated a close-form for approximate solution to Condon's equation. Bloch and Mintz have proposed the kinetics and mechanism for the U-H reaction over a wide range of pressures and temperatures. They have discussed their results through two models, one, which considers hydrogen diffusion through a protective UH{sub 3} product layer, and the second where hydride growth occurs at the hydride-metal interface. These authors obtained two-dimensional fits of experimental data to the pressure-temperature reactions. Kirkpatrick and Condon have obtained a linear solution to hydriding of uranium. These authors showed that the calculated reaction rates compared quite well with the experimental data at a hydrogen pressure of 1 atm. Powell

  1. Field desorption of Na and Cs from graphene on iridium

    NASA Astrophysics Data System (ADS)

    Bernatskii, D. P.; Pavlov, V. G.

    2015-08-01

    Field electron and desorption microscopy has been used to study specific features of the field desorption of sodium and cesium ions adsorbed on the surface of iridium with graphene. It was found that adsorbed sodium atoms most strongly reduce the work function on graphene islands situated over densely packed faces of iridium. A strong electric field qualitatively similarly affects the sodium and cesium desorption processes from a field emitter to give two desorption phases and has no noticeable effect on the disintegration of the graphene layer.

  2. Corrosion-resistant iridium-platinum anode material for high polarization application in corrosive acids

    SciTech Connect

    Farmer, J.; Summers, L.; Lewis, P.

    1993-09-08

    The present invention relates to highly corrosion resistant components for use in an electrochemical cell. Specifically, these components are resistant to corrosion under very extreme conditions such as exposure to aqua regia in the presence of a constant current density of 100mA/m{sup 2}. The components are comprised of an iridium-platinum alloy that comprises less than 30% iridium. In a preferred embodiment of the present invention, the iridium-platinum alloy comprises 15-20% iridium. In another preferred embodiment of the present invention, the iridium-platinum alloy is deposited on the surface of an electrochemical cell component by magnetron sputtering. The present invention also relates to a method for conducting an electrochemical reaction in the presence of highly corrosive acids under a high degree of polarization wherein the electrochemical cell comprises a component, preferably the anode, containing an iridium-platinum alloy that comprises less than 30% iridium.

  3. Homogeneous and heterogenized iridium water oxidation catalysts

    NASA Astrophysics Data System (ADS)

    Macchioni, Alceo

    2014-10-01

    The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.

  4. Method of forming metal hydride films

    NASA Technical Reports Server (NTRS)

    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.

  5. A classical but new kinetic equation for hydride transfer reactions.

    PubMed

    Zhu, Xiao-Qing; Deng, Fei-Huang; Yang, Jin-Dong; Li, Xiu-Tao; Chen, Qiang; Lei, Nan-Ping; Meng, Fan-Kun; Zhao, Xiao-Peng; Han, Su-Hui; Hao, Er-Jun; Mu, Yuan-Yuan

    2013-09-28

    A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions.

  6. Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

    SciTech Connect

    Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.; Pivovar, Bryan S.

    2016-06-02

    Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparative studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.

  7. Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

    DOE PAGES

    Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.; ...

    2016-06-02

    Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less

  8. Metastable Metal Hydrides for Hydrogen Storage

    DOE PAGES

    Graetz, Jason

    2012-01-01

    The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However, a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however, many of the high capacity “reversible” hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. Onmore » the other hand, the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid, low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However, a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.« less

  9. Achieving Zero Stress in Iridium, Chromium, and Nickle Thin Films

    NASA Technical Reports Server (NTRS)

    Broadway, David M.; Weimer, Jeffrey; Gurgew, Danielle; Lis, Tomasz; Ramsey, Brian D.; O'Dell, Stephen L.; Ames, A.; Bruni, R.

    2015-01-01

    We examine a method for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The examination of the stress in these materials is motivated by efforts to advance the optical performance of light-weight x-ray space telescopes into the regime of sub-arc second resolution that rely on control of the film stress to values within 10-100 MPa. A characteristic feature of the intrinsic stress behavior in chromium and nickel is their sensitivity to the magnitude and sign of the intrinsic stress with argon gas pressure, including the existence of a critical pressure that results in zero film stress. This critical pressure scales linearly with the film's density. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we have discovered a similar behavior for iridium. Additionally, we have identified zero stress in iridium shortly after island coalescence. This feature of film growth is used for achieving a total internal stress of -2.89 MPa for a 15.8 nm thick iridium film. The surface roughness of this low-stress film was examined using scanning probe microscopy (SPM) and x-ray reflectivity (XRR) at CuKa and these results presented and discussed.

  10. The Marine Geochemistry of Rhenium, Iridium and Platinum

    DTIC Science & Technology

    1991-09-01

    fields ( Koeberl 1989). Iridium enrichment factors, defined reiaiive to Hawaiian basalt (and relative to Sc) range from 104 to 105. The transport of Ir in...and M. B. McElroy. (1984). "Changes in atmospheric C02: influence of marine biota at high latitudes." J. Geoohys. Res. 89: 4629-4637. Koeberl , C

  11. Electrodeposited iridium oxide for neural stimulation and recording electrodes.

    PubMed

    Meyer, R D; Cogan, S F; Nguyen, T H; Rauh, R D

    2001-03-01

    Iridium oxide films formed by electrodeposition onto noniridium metal substrates are compared with activated iridium oxide films (AIROFs) as a low impedance, high charge capacity coating for neural stimulation and recording electrodes. The electrodeposited iridium oxide films (EIROFs) were deposited on Au, Pt, PtIr, and 316 LVM stainless steel substrates from a solution of IrCl4, oxalic acid, and K2CO3. A deposition protocol involving 50 potential sweeps at 50 mV/s between limits of 0.0 V and 0.55 V (versus Ag AgCl) followed by potential pulsing between the same limits produced adherent films with a charge storage capacity of >25 mC/cm2. Characterization by cyclic voltammetry and impedance spectroscopy revealed no differences in the electrochemical behavior of EIROF on non-Ir substrates and AIROF. The mechanical stability of the oxides was evaluated by ultrasonication in distilled water followed by dehydration and rehydration. Stability under charge injection was evaluated using 200 micros, 5.9 A/cm2 (1.2 mC/cm2) cathodal pulses. Loss of iridium oxide charge capacity was comparable for AIROFs and the EIROFs, ranging from 1% to 8% of the capacity immediately after activation or deposition. The EIROFs were deposited and evaluated on silicon microprobe electrodes and on metallized polyimide electrodes being developed for neural recording and stimulation applications.

  12. Discovery of tantalum, rhenium, osmium, and iridium isotopes

    SciTech Connect

    Robinson, R.; Thoennessen, M.

    2012-09-15

    Currently, thirty-eight tantalum, thirty-eight rhenium, thirty-nine osmium, and thirty-eight iridium isotopes have been observed and the discovery of these isotopes is described here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.

  13. Remote Sensing Missions for Earth Observation on Iridium NEXT

    NASA Astrophysics Data System (ADS)

    Gupta, O. P.

    2009-12-01

    A unique opportunity exists to host up to 66 earth observation sensors on Iridium’s proposed NEXT LEO constellation in a manner that can revolutionize earth observation and weather predictions. A constellation approach to sensing, using the real-time communications backbone of Iridium, will enable unprecedented geospatial and temporal sampling for now-casting of weather on a global basis as well as global climate monitoring. The NEXT constellation, which, like Iridium’s current LEO constellation, is expected to consist of 66 interconnected satellites in 6 near polar orbiting planes, provides a unique platform for hosting a variety of earth observation missions. Several remote sensing missions were recommended by Group on Earth Observations (GEO), NASA, NOAA, and ESA for consideration by Iridium during 2008. These include GPS radio occultation sensors, earth radiation budget measurements, altimetry, ocean and land imaging, and troposphere and stratospheric winds measurements including polar winds measurements. These missions are also considered high priority climate missions by the Decadal Survey. Study teams consisting of Iridium, NASA/JPL and multiple industrial partners of Iridium have conducted detailed studies of these missions for compatibility with NEXT. These studies have established technical feasibility, unique benefits from a constellation approach, and cost effectiveness for these solutions on NEXT.

  14. The Iridium (tm) system: Personal communications anytime, anyplace

    NASA Astrophysics Data System (ADS)

    Hatlelid, John E.; Casey, Larry

    The Iridium system is designed to provide handheld personal communications between diverse locations around the world at any time and without prior knowledge of the location of the personal units. This paper provides an overview of the system, the services it provides, its operation, and an overview of the commercial practices and relatively high volume satellite production techniques which will make the system cost effective. A constellation of 66 satellites will provide an orbiting, spherical-shell, infrastructure for this global calling capability. The satellites act as tall cellular towers and allow convenient operation for portable handheld telephones. The system will provide a full range of services including voice, paging, data, geolocation, and fax capabilities. Motorola is a world leader in the production of high volume, high quality, reliable telecommunications hardware. One of Iridium's goals is to apply these production techniques to high reliability space hardware. Concurrent engineering, high performance work teams, advanced manufacturing technologies, and improved assembly and test methods are some of the techniques that will keep the Iridium system cost effective. Mobile, global, flexible personal communications are coming that will allow anyone to call or receive a call from/to anyplace at anytime. The Iridium system will provide communications where none exist today. This connectivity will allow increased information transfer, open new markets for various business endeavors, and in general increase productivity and development.

  15. Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution.

    PubMed

    Madrahimov, Sherzod T; Li, Qian; Sharma, Ankit; Hartwig, John F

    2015-12-02

    Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)3 was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from [Ir(COD)Cl]2 and P(OPh)3 by cyclometalation of the phenyl group on the ligand and have shown such species to be the resting state of the catalyst. A series of allyliridium complexes ligated by the resulting P,C ligand have been generated and shown to be competent intermediates in the catalytic system. We have assessed the potential impact of charge, metal-iridium bond length, and stability of terminal vs internal alkenes generated by attack at the branched and terminal positions of the allyl ligand, respectively. These factors do not distinguish the regioselectivity for attack on allyliridium complexes from that for attack on allylpalladium complexes. Instead, detailed computational studies suggest that a series of weak, attractive, noncovalent interactions, including interactions of H-bond acceptors with a vinyl C-H bond of the alkene ligand, favor formation of the branched product with the iridium catalyst. This conclusion underscores the importance of considering attractive interactions, as well as repulsive steric interactions, when seeking to rationalize selectivities.

  16. Iridium Aluminide Coats For Protection Against Ox idation

    NASA Technical Reports Server (NTRS)

    Kaplan, Richard B.; Tuffias, Robert H.; La Ferla, Raffaele; Jang, Qin

    1996-01-01

    Iridium aluminide coats investigated for use in protecting some metallic substrates against oxidation at high temperatures. Investigation prompted by need for cost-effective anti-oxidation coats for walls of combustion chambers in rocket engines. Also useful in special terrestrial applications like laboratory combustion chambers and some chemical-processing chambers.

  17. Iridium alloy Clad Vent Set manufacturing qualification studies

    NASA Astrophysics Data System (ADS)

    Ulrich, George B.

    Metallurgical qualification studies to demonstrate the manufacturing readiness of the iridium alloy Clad Vent Set (CVS) for the General Purpose Heat Source program at the Oak Ridge Y-12 Plant are described. Microstructural data for various materials/test conditions are presented.

  18. The Iridium (tm) system: Personal communications anytime, anyplace

    NASA Technical Reports Server (NTRS)

    Hatlelid, John E.; Casey, Larry

    1993-01-01

    The Iridium system is designed to provide handheld personal communications between diverse locations around the world at any time and without prior knowledge of the location of the personal units. This paper provides an overview of the system, the services it provides, its operation, and an overview of the commercial practices and relatively high volume satellite production techniques which will make the system cost effective. A constellation of 66 satellites will provide an orbiting, spherical-shell, infrastructure for this global calling capability. The satellites act as tall cellular towers and allow convenient operation for portable handheld telephones. The system will provide a full range of services including voice, paging, data, geolocation, and fax capabilities. Motorola is a world leader in the production of high volume, high quality, reliable telecommunications hardware. One of Iridium's goals is to apply these production techniques to high reliability space hardware. Concurrent engineering, high performance work teams, advanced manufacturing technologies, and improved assembly and test methods are some of the techniques that will keep the Iridium system cost effective. Mobile, global, flexible personal communications are coming that will allow anyone to call or receive a call from/to anyplace at anytime. The Iridium system will provide communications where none exist today. This connectivity will allow increased information transfer, open new markets for various business endeavors, and in general increase productivity and development.

  19. Utilization of Low Bandwidth Iridium Modems for Polar Seismology

    NASA Astrophysics Data System (ADS)

    Parker, T.

    2012-12-01

    Transmission of realtime seismic data is a desirable goal when a rapid response is needed. However, for many science applications sample waveform data, system state of health, and the ability to command and control the seismic station are operationally adequate. Determining the optimal telemetry requirements for a remote polar seismic experiment requires balancing science objective against the expensive, over-subscribed support available in the polar environments? For example there is a significant difference in the resources needed for a permanent "monitoring" effort versus a short-term experiment. We will describe IRIS/PASSCAL's successful approach to utilizing Iridium telemetry for short-term seismic experiments and suggest viable use of an Iridium RUDICs system for higher data-rate, permanent seismic stations such as a monitoring scenario. Most seismic stations are configured to record at a rate that exceeds twice the data rate of a single Iridium Internet modem. The power requirement to run continuous Iridium telemetry better than doubles that of a standalone seismic station. Doubling station power roughly doubles station logistics by requiring an increased number of support flights for installation and service. The tradeoffs between desirable and adequate telemetry requirements and the ramifications these requirements have on support services must be considered for a successful seismic station. We describe two Iridium telemetry systems, developed by the IRIS/PASSCAL Polar Program, for use with seismic stations in Antarctica and the Arctic. The first system uses an inexpensive Iridium 9602 modem based device and short burst data (SBD) transmission to monitor station performance, provide some command and control, and return a small amount of representative seismic data. Power requirements for this SBD system are approximately 10Ah per year for a daily message. The second system uses an Iridium 9522b modem based device the DOD RUDICs system for a 2400 Baud

  20. Hydride fuel behavior in LWRs

    NASA Astrophysics Data System (ADS)

    Olander, Donald R.; Ng, Marowen

    2005-11-01

    The U-Zr hydride U 0.31ZrH 1.6 offers a number of advantages over oxide fuel for light-water reactors. Fission-gas release appears to be very small (release fraction ˜10 -4) up to 600 °C, which is close to the maximum fuel temperature. Initial irradiation-induced swelling can be as large as 5% for temperatures exceeding 650 °C. Hydrogen redistributes due to the non-uniform temperature in the fuel from the as-fabricated H/Zr of 1.6 to one that is higher at the pellet periphery than at the centerline. Radial redistribution produces 'hydrogen' stresses in the pellet which add to the usual thermal stresses. In a helium-bonded fuel rod, the total stresses are less than the fracture stress; in a liquid-metal-bonded fuel rod, the fracture stress is exceeded in the central portion of the pellet, but the surface remains in compression. Axial redistribution moves substantial quantities of hydrogen from the middle portion of the fuel stack to the ends. The neutronic effect of this displacement of the moderator is unknown.

  1. Thin-film metal hydrides.

    PubMed

    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.

  2. Simulation of dose distribution for iridium-192 brachytherapy source type-H01 using MCNPX

    SciTech Connect

    Purwaningsih, Anik

    2014-09-30

    Dosimetric data for a brachytherapy source should be known before it used for clinical treatment. Iridium-192 source type H01 was manufactured by PRR-BATAN aimed to brachytherapy is not yet known its dosimetric data. Radial dose function and anisotropic dose distribution are some primary keys in brachytherapy source. Dose distribution for Iridium-192 source type H01 was obtained from the dose calculation formalism recommended in the AAPM TG-43U1 report using MCNPX 2.6.0 Monte Carlo simulation code. To know the effect of cavity on Iridium-192 type H01 caused by manufacturing process, also calculated on Iridium-192 type H01 if without cavity. The result of calculation of radial dose function and anisotropic dose distribution for Iridium-192 source type H01 were compared with another model of Iridium-192 source.

  3. Simulation of dose distribution for iridium-192 brachytherapy source type-H01 using MCNPX

    NASA Astrophysics Data System (ADS)

    Purwaningsih, Anik

    2014-09-01

    Dosimetric data for a brachytherapy source should be known before it used for clinical treatment. Iridium-192 source type H01 was manufactured by PRR-BATAN aimed to brachytherapy is not yet known its dosimetric data. Radial dose function and anisotropic dose distribution are some primary keys in brachytherapy source. Dose distribution for Iridium-192 source type H01 was obtained from the dose calculation formalism recommended in the AAPM TG-43U1 report using MCNPX 2.6.0 Monte Carlo simulation code. To know the effect of cavity on Iridium-192 type H01 caused by manufacturing process, also calculated on Iridium-192 type H01 if without cavity. The result of calculation of radial dose function and anisotropic dose distribution for Iridium-192 source type H01 were compared with another model of Iridium-192 source.

  4. Metal Hydride Heat Storage Technology for Directed Energy Weapon Systems

    DTIC Science & Technology

    2007-11-16

    over time after the pulse operation. A compressor -driven metal hydride heat storage system was developed for efficient, compact heat storage and...principle and heat storage performance results of the compressor -driven metal hydride heat storage system through system modeling and prototype testing. The...hyd/m³] Subscripts A Metal hydride reactor B Hydrogen container C Hydrogen compressor s Hydrogen solid phase in hydride f Hydrogen fluid phase

  5. High H- ionic conductivity in barium hydride

    NASA Astrophysics Data System (ADS)

    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.

  6. Reactivity of yttrium carboxylates toward alkylaluminum hydrides.

    PubMed

    Schädle, Christoph; Fischbach, Andreas; Herdtweck, Eberhardt; Törnroos, Karl W; Anwander, Reiner

    2013-11-25

    Yttrocene-carboxylate complex [Cp*2Y(OOCAr(Me))] (Cp*=C5Me5, Ar(Me) =C6H2Me3-2,4,6) was synthesized as a spectroscopically versatile model system for investigating the reactivity of alkylaluminum hydrides towards rare-earth-metal carboxylates. Equimolar reactions with bis-neosilylaluminum hydride and dimethylaluminum hydride gave adduct complexes of the general formula [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] (R=CH2SiMe3, Me). The use of an excess of the respective aluminum hydride led to the formation of product mixtures, from which the yttrium-aluminum-hydride complex [{Cp*2Y(μ-H)AlMe2(μ-H)AlMe2(μ-CH3)}2] could be isolated, which features a 12-membered-ring structure. The adduct complexes [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] display identical (1)J(Y,H) coupling constants of 24.5 Hz for the bridging hydrido ligands and similar (89)Y NMR shifts of δ=-88.1 ppm (R=CH2SiMe3) and δ=-86.3 ppm (R=Me) in the (89)Y DEPT45 NMR experiments.

  7. 49 CFR 173.311 - Metal hydride storage systems.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Metal hydride storage systems. 173.311 Section 173... REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.311 Metal hydride storage systems. The following packing instruction is applicable to transportable UN Metal hydride storage...

  8. 49 CFR 173.311 - Metal hydride storage systems.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Metal hydride storage systems. 173.311 Section 173... REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.311 Metal hydride storage systems. The following packing instruction is applicable to transportable UN Metal hydride storage...

  9. 49 CFR 173.311 - Metal hydride storage systems.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Metal hydride storage systems. 173.311 Section 173... REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.311 Metal hydride storage systems. The following packing instruction is applicable to transportable UN Metal hydride storage...

  10. 49 CFR 173.311 - Metal hydride storage systems.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Metal hydride storage systems. 173.311 Section 173... REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.311 Metal hydride storage systems. The following packing instruction is applicable to transportable UN Metal hydride storage...

  11. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    PubMed

    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.

  12. Network flexibility of the IRIDIUM (R) Global Mobile Satellite System

    NASA Technical Reports Server (NTRS)

    Hutcheson, Jonathan; Laurin, Mala

    1995-01-01

    The IRIDIUM system is a global personal communications system supported by a constellation of 66 low earth orbit (LEO) satellites and a collection of earth-based 'gateway' switching installations. Like traditional wireless cellular systems, coverage is achieved by a grid of cells in which bandwidth is reused for spectral efficiency. Unlike any cellular system ever built, the moving cells can be shared by multiple switching facilities. Noteworthy features of the IRIDIUM system include inter-satellite links, a GSM-based telephony architecture, and a geographically controlled system access process. These features, working in concert, permit flexible and reliable administration of the worldwide service area by gateway operators. This paper will explore this unique concept.

  13. Iridium alloy clad vent set manufacturing qualification studies

    NASA Astrophysics Data System (ADS)

    Ulrich, George B.

    1991-01-01

    Qualification studies have been successfully conducted to demonstrate iridium alloy Clad Vent Set (CVS) manufacturing readiness for the General Purpose Heat Source (GPHS) program at the Oak Ridge Y-12 Plant. These studies were joint comparison evaluations of both the Y-12 Plant and EG&G Mound G-MAT) products. Note: EG&G-MAT formerly manufactured the iridium alloy CVS. The comparison evaluations involved work in a number of areas; however, only the CVS cup metallurgical evalution will be presented here. The initial metallurgical comparisons in conjunction with follow-up metallurgical work showed the Y-12 Plant CVS product to be comparable to the fully qualified (for Galileo and Ulysses missions) EG&G-MAT product. This allowed the Y-12 Plant to commence pilot production of CVS components for potential use in the CRAF and CASSINI missions.

  14. Iridium-Catalyzed Asymmetric Hydrogenation of Unsaturated Carboxylic Acids.

    PubMed

    Zhu, Shou-Fei; Zhou, Qi-Lin

    2017-04-04

    Chiral carboxylic acid moieties are widely found in pharmaceuticals, agrochemicals, flavors, fragrances, and health supplements. Although they can be synthesized straightforwardly by transition-metal-catalyzed enantioselective hydrogenation of unsaturated carboxylic acids, because the existing chiral catalysts have various disadvantages, the development of new chiral catalysts with high activity and enantioselectivity is an important, long-standing challenge. Ruthenium complexes with chiral diphosphine ligands and rhodium complexes with chiral monodentate or bidentate phosphorus ligands have been the predominant catalysts for asymmetric hydrogenation of unsaturated acids. However, the efficiency of these catalysts is highly substrate-dependent, and most of the reported catalysts require a high loading, high hydrogen pressure, or long reaction time for satisfactory results. Our recent studies have revealed that chiral iridium complexes with chiral spiro-phosphine-oxazoline ligands and chiral spiro-phosphine-benzylamine ligands exhibit excellent activity and enantioselectivity in the hydrogenation of α,β-unsaturated carboxylic acids, including α,β-disubstituted acrylic acids, trisubstituted acrylic acids, α-substituted acrylic acids, and heterocyclic α,β-unsaturated acids. On the basis of an understanding of the role of the carboxy group in iridium-catalyzed asymmetric hydrogenation reactions, we developed a carboxy-group-directed strategy for asymmetric hydrogenation of olefins. Using this strategy, we hydrogenated several challenging olefin substrates, such as β,γ-unsaturated carboxylic acids, 1,1-diarylethenes, 1,1-dialkylethenes, and 1-alkyl styrenes in high yield and with excellent enantioselectivity. All these iridium-catalyzed asymmetric hydrogenation reactions feature high turnover numbers (up to 10000) and turnover frequencies (up to 6000 h(-1)), excellent enantioselectivities (greater than 95% ee with few exceptions), low hydrogen pressure (<12 atm

  15. Blistering during the atomic layer deposition of iridium

    SciTech Connect

    Genevée, Pascal E-mail: a.szeghalmi@uni-jena.de; Ahiavi, Ernest; Janunts, Norik; Pertsch, Thomas; Kley, Ernst-Bernhard; Szeghalmi, Adriana E-mail: a.szeghalmi@uni-jena.de; Oliva, Maria

    2016-01-15

    The authors report on the formation of blisters during the atomic layer deposition of iridium using iridium acetylacetonate and oxygen precursors. Films deposited on fused silica substrates led to sparsely distributed large blisters while in the case of silicon with native oxide additional small blisters with a high density was observed. It is found that the formation of blisters is favored by a higher deposition temperature and a larger layer thickness. Postdeposition annealing did not have a significant effect on the formation of blisters. Finally, changing purge duration during the film growth allowed us to avoid blistering and evidenced that impurities released from the film in gas phase were responsible for the formation of blisters.

  16. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

    2011-01-01

    NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

  17. 1. VIEW OF A PORTION OF THE HYDRIDE PROCESSING LABORATORY. ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. VIEW OF A PORTION OF THE HYDRIDE PROCESSING LABORATORY. OPERATIONS IN THE GLOVE BOX IN THE BACKGROUND OF THE PHOTOGRAPH INCLUDED HYDRIDING OF PLUTONIUM AND HYDRIDE SEPARATION. IN THE FOREGROUND, THE VACUUM MONITOR CONTROL PANEL MEASURED TEMPERATURES WITHIN THE GLOVEBOX. THE CENTER CONTROL PANEL REGULATED THE FURNACE INSIDE THE GLOVE BOX USED IN THE HYDRIDING PROCESSES. THIS EQUIPMENT WAS ESSENTIAL TO THE HYDRIDING PROCESS, AS WELL AS OTHER GLOVE BOX OPERATIONS. - Rocky Flats Plant, Plutonium Laboratory, North-central section of industrial area at 79 Drive, Golden, Jefferson County, CO

  18. Sputtered iridium oxide films (SIROFs) for neural stimulation electrodes

    PubMed Central

    Cogan, Stuart F.; Ehrlich, Julia; Plante, Timothy D.; Smirnov, Anton; Shire, Douglas B.; Gingerich, Marcus; Rizzo, Joseph F.

    2009-01-01

    Sputtered iridium oxide films (SIROFs) deposited by DC reactive sputtering from an iridium metal target have been characterized in vitro for their potential as neural recording and stimulation electrodes. SIROFs were deposited over gold metallization on flexible multielectrode arrays fabricated on thin (15 µm) polyimide substrates. SIROF thickness and electrode areas of 200–1300 nm and 1960–125600 µm2, respectively, were investigated. The charge-injection capacities of the SIROFs were evaluated in an inorganic interstitial fluid model in response to charge-balanced, cathodal-first current pulses. Charge injection capacities were measured as a function of cathodal pulse width (0.2 – 1 ms) and potential bias in the interpulse period (0.0 to 0.7 V vs. Ag|AgCl). Depending on the pulse parameters and electrode area, charge-injection capacities ranged from 1–9 mC/cm2, comparable with activated iridium oxide films (AIROFs) pulsed under similar conditions. Other parameters relevant to the use of SIROF on nerve electrodes, including the thickness dependence of impedance (0.05–105 Hz) and the current necessary to maintain a bias in the interpulse region were also determined. PMID:17271216

  19. Mono- and bis-tolylterpyridine iridium(III) complexes

    SciTech Connect

    Hinkle, Lindsay M.; Young, Jr., Victor G.; Mann, Kent R.

    2012-01-20

    The first structure report of trichlorido[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl{sub 3}(C{sub 22}H{sub 17}N{sub 3})] {center_dot} C{sub 2}H{sub 6}OS, (I), is presented, along with a higher-symmetry setting of previously reported bis[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) tris(hexafluoridophosphate) acetonitrile disolvate, [Ir(C{sub 22}H{sub 17}N{sub 3})2](PF{sub 6}){sub 3} {center_dot} 2C{sub 2}H{sub 3}N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007). Eur. J. Inorg. Chem. pp. 1911-1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent molecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group. The iridium complex and one PF{sub 6}{sup -} anion lie on twofold axes in this structure, making half of the molecule unique.

  20. Hydride formation on deformation twin in zirconium alloy

    NASA Astrophysics Data System (ADS)

    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.

  1. Evaluation of Molybdenum as a Surrogate for Iridium in the GPHS Weld Development

    SciTech Connect

    Stine, Andrew Martin; Pierce, Stanley W.; Moniz, Paul F.

    2015-10-17

    The welding equipment used for welding iridium containers (clads) at Los Alamos National Laboratory is twenty five years old and is undergoing an upgrade. With the upgrade, there is a requirement for requalification of the welding process, and the opportunity for process improvement. Testing of the new system and requalification will require several welds on iridium test parts and clads, and any efforts to improve the process will add to the need for iridium parts. The extreme high cost of iridium imposes a severe limitation on the extent of test welding that can be done. The 2 inch diameter, 0.027 inch thick, iridium blank disc that the clad cup is formed from, is useful for initial weld trials, but it costs $5000. The development clad sets needed for final tests and requalification cost $15,000 per set. A solution to iridium cost issue would be to do the majority of the weld development on a less expensive surrogate metal with similar weld characteristics. One such metal is molybdenum. Since its melting index (melting temperature x thermal conductivity) is closest to iridium, welds on molybdenum should be similar in size for a given weld power level. Molybdenum is inexpensive; a single 2 inch molybdenum disc costs only $9. In order to evaluate molybdenum as a surrogate for iridium, GTA welds were first developed to provide full penetration on 0.030 inch thick molybdenum discs at speeds of 20, 25, and 30 inches per minute (ipm). These weld parameters were then repeated on the standard 0.027 inch thick iridium blanks. The top surface and bottom surface (root) width and grain structure of the molybdenum and iridium welds were compared, and similarities were evident between the two metals. Due to material and thickness differences, the iridium welds were approximately 35% wider than the molybdenum welds. A reduction in iridium weld current of 35% produce welds slightly smaller than the molybdenum welds yet showed that current could be scaled according to molybdenum/iridium

  2. Hydridable material for the negative electrode in a nickel-metal hydride storage battery

    DOEpatents

    Knosp, Bernard; Bouet, Jacques; Jordy, Christian; Mimoun, Michel; Gicquel, Daniel

    1997-01-01

    A monophase hydridable material for the negative electrode of a nickel-metal hydride storage battery with a "Lave's phase" structure of hexagonal C14 type (MgZn.sub.2) has the general formula: Zr.sub.1-x Ti.sub.x Ni.sub.a Mn.sub.b Al.sub.c Co.sub.d V.sub.e where ##EQU1##

  3. Rockot Launch Vehicle Commercial Operations for Grace and Iridium Program

    NASA Astrophysics Data System (ADS)

    Viertel, Y.; Kinnersley, M.; Schumacher, I.

    2002-01-01

    The GRACE mission and the IRIDIUM mission on ROCKOT launch vehicle are presented. Two identical GRACE satellites to measure in tandem the gravitational field of the earth with previously unattainable accuracy - it's called the Gravity Research and Climate Experiment, or and is a joint project of the U.S. space agency, NASA and the German Centre for Aeronautics and Space Flight, DLR. In order to send the GRACE twins into a 500x500 km , 89deg. orbit, the Rockot launch vehicle was selected. A dual launch of two Iridium satellites was scheduled for June 2002 using the ROCKOT launch vehicle from Plesetsk Cosmodrome in Northern Russia. This launch will inject two replacement satellites into a low earth orbit (LEO) to support the maintenance of the Iridium constellation. In September 2001, Eurockot successfully carried out a "Pathfinder Campaign" to simulate the entire Iridium mission cycle at Plesetsk. The campaign comprised the transport of simulators and related equipment to the Russian port-of-entry and launch site and also included the integration and encapsulation of the simulators with the actual Rockot launch vehicle at Eurockot's dedicated launch facilities at Plesetsk Cosmodrome. The pathfinder campaign lasted four weeks and was carried out by a joint team that also included Khrunichev, Russian Space Forces and Eurockot personnel on the contractors' side. The pathfinder mission confirmed the capability of Eurockot Launch Services to perform the Iridium launch on cost and on schedule at Plesetsk following Eurockot's major investment in international standard preparation, integration and launch facilities including customer facilities and a new hotel. In 2003, Eurockot will also launch the Japanese SERVI'S-1 satellite for USEF. The ROCKOT launch vehicle is a 3 stage liquid fuel rocket whose first 2 stages have been adapted from the Russian SS-19. A third stage, called "Breeze", can be repeatedly ignited and is extraordinarily capable of manoeuvre. Rockot can place

  4. Ductility Evaluation of As-Hydrided and Hydride Reoriented Zircaloy-4 Cladding under Simulated Dry-Storage Condition

    SciTech Connect

    Yan, Yong; Plummer, Lee K; Ray, Holly B; Cook, Tyler S; Bilheux, Hassina Z

    2014-01-01

    Pre-storage drying-transfer operations and early stage storage expose cladding to higher temperatures and much higher pressure-induced tensile hoop stresses relative to normal operation in-reactor and pool storage under these conditions. Radial hydrides could precipitate during slow cooling and provide an additional embrittlement mechanism as the cladding temperature decreases below the ductile-to-brittle transition temperature. As a means of simulating this behavior, unirradiated hydrided Zircaloy-4 samples were fabricated by a gas charging method to levels that encompass the range of hydrogen concentrations observed in current used fuel. Mechanical testing was carried out by the ring compression test (RCT) method at various temperatures to evaluate the sample s ductility for both as-hydrided and post-hydride reorientation treated specimens. As-hydrided samples with higher hydrogen concentration (>800 ppm) resulted in lower strain before fracture and reduced maximum load. Increasing RCT temperatures resulted in increased ductility of the as-hydrided cladding. A systematic radial hydride treatment was conducted at various pressures and temperatures for the hydrided samples with H content around 200 ppm. Following the radial hydride treatment, RCTs on the hydride reoriented samples were conducted and exhibited lower ductility compared to as-hydrided samples.

  5. A thermokinetically driven metal-hydride actuator

    NASA Astrophysics Data System (ADS)

    Jung, Kwangmok; Kim, Kwang J.

    2008-03-01

    The purpose of this study is to develop a novel thermokinetically-driven actuator technology based on the physics of metal hydrides (MH's). A metal hydride absorbs and desorbs hydrogen due to the imposed temperature swing(s). The MH can also work as an effective thermally-driven hydrogen compressor producing more than 5,000 psia net pressure swing. The MH actuation system can be built in a simple structure, exhibits high power, produces soft actuating, and is essentially noiseless. Moreover, it is much more powerful and compact than conventional pneumatic systems that require bulky auxiliary systems. It is our belief that the MH actuators are useful for many emerging industrial, biorobotic, and civil structural applications. In this paper, we report the recent preliminary experimental results for a laboratory-prototyped MH actuation system. In particular, the dynamic response characteristics, enhanced controllability, thermodynamic performances, and reliability of the metal hydride actuator were studied in order to estimate the actuation capability of the MH actuator. A unique design of the MH actuator was created. It encases a so-called "porous metal hydride (PMH)" in the reactor to effectively achieve desirable performance by improving overall thermal conductance.

  6. X-Ray Topography of Hydride Domains.

    DTIC Science & Technology

    1983-04-01

    boundaries between hydride (deuteride) domains, and the irregular boundaries correspond to incoherent twin boundaries . Trace analysis of the coherent...topographs of the NbHo.78 and NbO 0 .75 crystals. As discussed by Schober and Linke (1976b), the straight boundaries correspond to coherent twin

  7. Metal hydride fuel storage and method thereof

    DOEpatents

    Morse, Jeffrey D.; Jankowski, Alan F.; Yu, Conrad

    2006-10-17

    Disclosed herein is a metal hydride fuel storage cartridge having integrated resistive heaters that can be used in conjunction with fuel cells such as MEMS-based fuel cells. The cartridge is fabricated using micromachining methods and thin/thick film materials synthesis techniques.

  8. Metal hydride fuel storage and method thereof

    DOEpatents

    Morse, Jeffrey D [Martinez, CA; Jankowski, Alan F [Livermore, CA; Yu, Conrad [Antioch, CA

    2009-05-05

    Disclosed herein is a metal hydride fuel storage cartridge having integrated resistive heaters that can be used in conjunction with fuel cells such as MEMS-based fuel cells. The cartridge is fabricated using micromachining methods and thin/thick film materials synthesis techniques.

  9. Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

    NASA Technical Reports Server (NTRS)

    Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

    2010-01-01

    Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

  10. Real-Time Characterization of Formation and Breakup of Iridium Clusters in Highly Dealuminated Zeolite Y

    SciTech Connect

    Uzun, Alper; Gates, Bruce C.

    2009-01-15

    The chemistry of formation of iridium clusters from mononuclear iridium diethylene complexes anchored in dealuminated Y zeolite, and their subsequent breakup -- all including changes in the metal-metal, metal-support, and metal-ligand interactions -- is demonstrated by time-resolved EXAFS, XANES, and IR spectroscopy.

  11. Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

    NASA Technical Reports Server (NTRS)

    Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

    2010-01-01

    Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

  12. Sensitized near-infrared emission from ytterbium(III) via direct energy transfer from iridium(III) in a heterometallic neutral complex.

    PubMed

    Mehlstäubl, Marita; Kottas, Gregg S; Colella, Silvia; De Cola, Luisa

    2008-05-14

    A tetrametallic iridium-ytterbium complex has been synthesised that shows sensitized near-infrared emission (lambda(max) = 976 nm) upon excitation of the iridium unit in the visible region (400 nm) due to efficient energy transfer from the iridium units to the Yb(III) ion. The iridium phosphorescence is quenched nearly quantitatively while the ytterbium ion emits brightly in the NIR.

  13. Sputtered iridium oxide films (SIROFs) for low-impedance neural stimulation and recording electrodes.

    PubMed

    Cogan, S F; Plante, T D; Ehrlich, J

    2004-01-01

    Iridium oxide films formed by electrochemical activation of iridium metal (AIROF) or by electrochemical deposition (EIROF) are being evaluated as low-impedance charge-injection coatings for neural stimulation and recording. Iridium oxide may also be deposited by reactive sputtering from iridium metal in an oxidizing plasma. The characterization of sputtered iridium oxide films (SIROFs) as coatings for nerve electrodes is reported. SIROFs were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and potential transient measurements during charge-injection. The surface morphology of the SIROF transitions from smooth to highly nodular with increasing film thickness from 80 nm to 4600 nm. Charge-injection capacities exceed 0.75 mC/cm(2) with 0.75 ms current pulses in thicker films. The SIROF was deposited on both planar and non-planar substrates and photolithographically patterned by lift-off.

  14. Iridium-based double perovskites for efficient water oxidation in acid media

    NASA Astrophysics Data System (ADS)

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-08-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2.

  15. Iridium-based double perovskites for efficient water oxidation in acid media

    PubMed Central

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-01-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2. PMID:27498694

  16. Iridium: Global OTH data communications for high altitude scientific ballooning

    NASA Astrophysics Data System (ADS)

    Denney, A.

    beneficial points provided by the Iridium platform include pure global accessibility (as well as polar), cost effectiveness because it is available as a COTS (Commercially Off The Shelf) technology, reliability in that the equipment must operate in extreme conditions (near space), integration and development time into current systems must be minimized. As a bonus Motorola and NAL Research Corporation are developing SBD (Short Burst Data) into the Iridium network. This may lead the way to a global IP (Internet Protocol) node based ballooning platform. The Iridium satellite data modems employ the Iridium Low-Earth Orbit (LEO) satellite network. The scope of this paper is to introduce an OTH communications alternative, albeit not necessarily a primary one, to existing ballooning platforms using COTS based emerging technologies. Design aspects, characteristics, actual flight testing statistics, principles of the Iridium modems and communication paths are described including payload and support instrumentation interfacing. Not limited to high altitude ballooning, the Iridium communications platform opens a new era in remote commanding and data retrieval.

  17. Arsenic in marine tissues — The challenging problems to electrothermal and hydride generation atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Karadjova, Irina B.; Petrov, Panayot K.; Serafimovski, Ivan; Stafilov, Trajče; Tsalev, Dimiter L.

    2007-03-01

    Analytical problems in determination of arsenic in marine tissues are addressed. Procedures for the determination of total As in solubilized or extracted tissues with tetramethylammonium hydroxide and methanol have been elaborated. Several typical lyophilized tissues were used: NIST SRM 1566a 'Oyster Tissue', BCR-60 CRM 'Trace Elements in an Aquatic Plant ( Lagarosiphon major)', BCR-627 'Forms of As in Tuna Fish Tissue', IAEA-140/TM 'Sea Plant Homogenate', NRCC DOLT-1 'Dogfish Liver' and two representatives of the Black Sea biota, Mediterranean mussel ( Mytilus galloprovincialis) and Brown algae ( Cystoseira barbata). Tissues (nominal 0.3 g) were extracted in tetramethylammonium hydroxide (TMAH) 1 ml of 25% m/v TMAH and 2 ml of water) or 5 ml of aqueous 80% v/v methanol (MeOH) in closed vessels in a microwave oven at 50 °C for 30 min. Arsenic in solubilized or extracted tissues was determined by electrothermal atomic absorption spectrometry (ETAAS) after appropriate dilution (nominally to 25 ml, with further dilution as required) under optimal instrumental parameters (pyrolysis temperature 900 °C and atomization temperature 2100 °C) with 1.5 μg Pd as modifier on Zr-Ir treated platform. Platforms have been pre-treated with 2.7 μmol of zirconium and then with 0.10 μmol of iridium which served as a permanent chemical modifier in direct ETAAS measurements and as an efficient hydride sequestration medium in flow injection hydride generation (FI-HG)-ETAAS. TMAH and methanol extract 96-108% and 51-100% of As from CRMs. Various calibration approaches have been considered and critically evaluated. The effect of species-dependent slope of calibration graph or standard additions plot for total As determination in a sample comprising of several individual As species with different ETAAS behavior has been considered as a kind of 'intrinsic element speciation interference' that cannot be completely overcome by standard additions technique. Calibration by means of CRMs has

  18. METHOD OF FABRICATING A URANIUM-ZIRCONIUM HYDRIDE REACTOR CORE

    DOEpatents

    Weeks, I.F.; Goeddel, W.V.

    1960-03-22

    A method is described of evenly dispersing uranlum metal in a zirconium hydride moderator to produce a fuel element for nuclear reactors. According to the invention enriched uranium hydride and zirconium hydride powders of 200 mesh particle size are thoroughly admixed to form a mixture containing 0.1 to 3% by weight of U/sup 235/ hydride. The mixed powders are placed in a die and pressed at 100 tons per square inch at room temperature. The resultant compacts are heated in a vacuum to 300 deg C, whereby the uranium hydride deoomposes into uranium metal and hydrogen gas. The escaping hydrogen gas forms a porous matrix of zirconium hydride, with uramum metal evenly dispersed therethrough. The advantage of the invention is that the porosity and uranium distribution of the final fuel element can be more closely determined and controlled than was possible using prior methods of producing such fuel ele- ments.

  19. Bias-enhanced nucleation of diamond on iridium: A comprehensive study of the first stages by sequential surface analysis

    NASA Astrophysics Data System (ADS)

    Chavanne, A.; Arnault, J.-C.; Barjon, J.; Arabski, J.

    2011-03-01

    The chemical evolution of the iridium surface along the successive steps of BEN was investigated using electron spectroscopy techniques (XPS, AES). To this end, a sequential study was carried out in an UHV analysis chamber connected to a MPCVD reactor. First, experimental results were obtained on iridium surfaces exposed to a methane plasma without bias. They show a sp 2 carbon layer formation on iridium, probably due to the segregation during cooling of carbon solubilized at high temperature in iridium. In this scenario, the iridium surface would be uncovered by carbon as BEN starts. Then, the consequences of BEN were observed: (i) formation of a thicker carbon layer at the iridium surface due to carbon segregation and sub-implantation (ii) chemical modification of iridium neighboring within the first nanometers; (iii) diamond nucleation.

  20. Luminescent iridium(III) complexes as novel protein staining agents.

    PubMed

    Jia, Junli; Fei, Hao; Zhou, Ming

    2012-05-01

    This article reports a new class of luminescent metal complexes, biscyclometalated iridium(III) complexes with an ancillary bathophenanthroline disulfonate ligand, for staining protein bands that are separated by electrophoresis. The performances of these novel staining agents have been studied in comparison with tris(bathophenanthroline disulfonate) ruthenium(II) tetrasodium salt (i.e. RuBPS) using a commercially available imaging system. The staining agents showed different limits of detection, linear dynamic ranges, and protein-to-protein variations. The overall performances of all three stains were found to be better than or equivalent to RuBPS under the experimental conditions.

  1. Broadband iridium wire grid polarizer for UV applications.

    PubMed

    Weber, Thomas; Käsebier, Thomas; Kley, Ernst-Bernhard; Tünnermann, Andreas

    2011-02-15

    In this Letter, we present an iridium wire grid polarizer with a large spectral working range from IR down to the UV spectral region. The required grating period of 100 nm for an application below a wavelength of 300 nm was realized using a spatial frequency doubling technique based on ultrafast electron beam writing. The optical performance of the polarizer at a wavelength of 300 nm is a transmittance of almost 60% and an extinction ratio of about 30 (15 dB). Furthermore, the oxidation resistance is discussed.

  2. Determination of iridium in mafic rocks by atomic absorption

    USGS Publications Warehouse

    Grimaldi, F.S.; Schnepfe, M.M.

    1970-01-01

    Iridium is determined in mineralized mafic rocks by atomic absorption after fire-assay concentration into a gold bead. Interelement interferences in the atomic-absorption determination are removed and Ir sensitivity is increased by buffering the solutions with a mixture of copper and sodium sulphates. Substantial amounts of Ag, Al, Au, Bi, Ca, Cd, Co, Cr, Fe, Ho, Hg, K, La, Mg, Mn, Mo, Ni, Pb, Te, Ti, V, Y, Zn and platinum metals can be tolerated in the atomic-absorption determination. The sensitivity and detection limits are 3.2 and 0.25 ppm of Ir, respectively. ?? 1970.

  3. Luminescent cyclometallated iridium(III) complexes having acetylide ligands

    DOEpatents

    Thompson, Mark E.; Bossi, Alberto; Djurovich, Peter Ivan

    2014-09-02

    The present invention relates to phosphorescent (triplet-emitting) organometallic materials. The phosphorescent materials of the present invention comprise Ir(III)cyclometallated alkynyl complexes for use as triplet light-emitting materials. The Ir(III)cyclometallated alkynyl complexes comprise at least one cyclometallating ligand and at least one alkynyl ligand bonded to the iridium. Also provided is an organic light emitting device comprising an anode, a cathode and an emissive layer between the anode and the cathode, wherein the emissive layer comprises a Ir(III)cyclometallated alkynyl complex as a triplet emitting material.

  4. Iridium-catalyzed reductive nitro-Mannich cyclization.

    PubMed

    Gregory, Alex W; Chambers, Alan; Hawkins, Alison; Jakubec, Pavol; Dixon, Darren J

    2015-01-02

    A new chemoselective reductive nitro-Mannich cyclization reaction sequence of nitroalkyl-tethered lactams has been developed. Relying on the rapid and chemoselective iridium(I)-catalyzed reduction of lactams to the corresponding enamine, subsequent nitro-Mannich cyclization of tethered nitroalkyl functionality provides direct access to important alkaloid natural-product-like structures in yields up to 81 % and in diastereoselectivities that are typically good to excellent. An in-depth understanding of the reaction mechanism has been gained through NMR studies and characterization of reaction intermediates. The new methodology has been applied to the total synthesis of (±)-epi-epiquinamide in four steps.

  5. The solubility of hydrogen in rhodium, ruthenium, iridium and nickel.

    NASA Technical Reports Server (NTRS)

    Mclellan, R. B.; Oates, W. A.

    1973-01-01

    The temperature variation of the solubility of hydrogen in rhodium, ruthenium, iridium, and nickel in equilibrium with H2 gas at 1 atm pressure has been measured by a technique involving saturating the solvent metal with hydrogen, quenching, and analyzing in resultant solid solutions. The solubilities determined are small (atom fraction of H is in the range from 0.0005 to 0.00001, and the results are consistent with the simple quasi-regular model for dilute interstitial solid solutions. The relative partial enthalpy and excess entropy of the dissolved hydrogen atoms have been calculated from the solubility data and compared with well-known correlations between these quantities.

  6. Measurements of the hard-x-ray reflectivity of iridium

    SciTech Connect

    Romaine, S.; Bruni, R.; Gorenstein, P.; Zhong, Z

    2007-01-10

    In connection with the design of a hard-x-ray telescope for the Constellation X-Ray Observatory we measured the reflectivity of an iridium-coated zerodur substrate as a function of angle at 55, 60, 70, and 80 keV at the National Synchrotron Light Source of Brookhaven National Laboratory. The optical constants were derived from the reflectivity data. The real component of the index of refraction is in excellent agreement with theoretical values at all four energies. However, the imaginary component, which is related to the mass attenuation coefficient, is 50% to 70% larger at 55, 60, and 70 keV than theoretical values.

  7. Methanol dehydrogenation by iridium N-heterocyclic carbene complexes.

    PubMed

    Campos, Jesús; Sharninghausen, Liam S; Manas, Michael G; Crabtree, Robert H

    2015-06-01

    A series of homogeneous iridium bis(N-heterocyclic carbene) catalysts are active for three transformations involving dehydrogenative methanol activation: acceptorless dehydrogenation, transfer hydrogenation, and amine monoalkylation. The acceptorless dehydrogenation reaction requires base, yielding formate and carbonate, as well as 2-3 equivalents of H2. Of the few homogeneous systems known for this reaction, our catalysts tolerate air and employ simple ligands. Transfer hydrogenation of ketones and imines from methanol is also possible. Finally, N-monomethylation of anilines occurs through a "borrowing hydrogen" reaction. Notably, this reaction is highly selective for the monomethylated product.

  8. Synthesis and properties of platinum hydride

    NASA Astrophysics Data System (ADS)

    Scheler, Thomas; Degtyareva, Olga; Marqués, Miriam; Guillaume, Christophe L.; Proctor, John E.; Evans, Shaun; Gregoryanz, Eugene

    2011-06-01

    Synchrotron x-ray diffraction experiments on compressed platinum-hydrogen mixtures reveal the formation of platinum hydride at a pressure of 27(1) GPa at room temperature. This compound exhibits two phases, PtH-I and PtH-II, coexisting up to the pressure of 42 GPa, above which the single phase of PtH-II is observed. Pt atoms in the PtH-II phase are shown to form a hexagonal closed-packed structure. This phase exhibits a high bulk modulus of 310 (10) GPa and is stable up to at least 53 GPa. Ab initio calculations show that PtH-II is superconducting with Tc = 12 K at 90 GPa, the highest temperature of superconducting transition among any known metal hydride.

  9. Unoccupied electronic states in cerium hydrides

    NASA Astrophysics Data System (ADS)

    Osterwalder, J.; Schlapbach, L.

    1985-05-01

    We present UV isochromat spectra of polycrystalline CeH 2.1 and CeH 2.9. The intensity at EF is small in CeH 2.1 and vanishes in CeH 2.9 as it is expected from XPS, UPS and conductivity data. In both hydrides broad features (≈2 eV FWHM) appear between 4 and 5 eV above EF. This is in qualitative agreement with bandstructure calculations.

  10. Dissipative hydride precipitates in superconducting niobium cavities

    SciTech Connect

    Romanenko, A.; Cooley, L.D.; Ciovati, G.; Wu, G.; /Argonne

    2011-10-01

    We report the first direct observation of the microstructural features exhibiting RF losses at high surface magnetic fields of above 100 mT in field emission free superconducting niobium cavities. The lossy areas were identified by advanced thermometry. Surface investigations using different techniques were carried out on cutout samples from lossy areas and showed the presence of dendritic niobium hydrides. This finding has possible implications to the mechanisms of RF losses in superconducting niobium at all field levels.

  11. Nickel metal hydride LEO cycle testing

    NASA Technical Reports Server (NTRS)

    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.

  12. Materials compatibility of hydride storage materials with austenitic stainless steels

    SciTech Connect

    Clark, E.A.

    1992-09-21

    This task evaluated the materials compatibility of LaNi[sub 5-x]Al[sub x] (x= 0.3, 0.75) hydrides and palladium coated kieselguhr with austenitic stainless steel in hydrogen and tritium process environments. Based on observations of retired prototype hydride storage beds and materials exposure testing samples designed for this study, no materials compatibility problem was indicated. Scanning electron microscopy observations of features on stainless steel surfaces after exposure to hydrides are also commonly found on as-received materials before hydriding. These features are caused by either normal heat treating and acid cleaning of stainless steel or reflect the final machining operation.

  13. Materials compatibility of hydride storage materials with austenitic stainless steels

    SciTech Connect

    Clark, E.A.

    1992-09-21

    This task evaluated the materials compatibility of LaNi{sub 5-x}Al{sub x} (x= 0.3, 0.75) hydrides and palladium coated kieselguhr with austenitic stainless steel in hydrogen and tritium process environments. Based on observations of retired prototype hydride storage beds and materials exposure testing samples designed for this study, no materials compatibility problem was indicated. Scanning electron microscopy observations of features on stainless steel surfaces after exposure to hydrides are also commonly found on as-received materials before hydriding. These features are caused by either normal heat treating and acid cleaning of stainless steel or reflect the final machining operation.

  14. Storing hydrogen in the form of light alloy hydrides

    NASA Technical Reports Server (NTRS)

    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.

  15. METHOD AND APPARATUS FOR MAKING URANIUM-HYDRIDE COMPACTS

    DOEpatents

    Wellborn, W.; Armstrong, J.R.

    1959-03-10

    A method and apparatus are presented for making compacts of pyrophoric hydrides in a continuous operation out of contact with air. It is particularly useful for the preparation of a canned compact of uranium hydride possessing high density and purity. The metallic uranium is enclosed in a container, positioned in a die body evacuated and nvert the uranium to the hydride is admitted and the container sealed. Heat is applied to bring about the formation of the hydride, following which compression is used to form the compact sealed in a container ready for use.

  16. Dynamic high-temperature characterization of an iridium alloy in tension

    SciTech Connect

    Song, Bo; Nelson, Kevin; Jin, Helena; Lipinski, Ronald J.; Bignell, John; Ulrich, G. B.; George, E. P.

    2015-09-01

    Iridium alloys have been utilized as structural materials for certain high-temperature applications, due to their superior strength and ductility at elevated temperatures. The mechanical properties, including failure response at high strain rates and elevated temperatures of the iridium alloys need to be characterized to better understand high-speed impacts at elevated temperatures. A DOP-26 iridium alloy has been dynamically characterized in compression at elevated temperatures with high-temperature Kolsky compression bar techniques. However, the dynamic high-temperature compression tests were not able to provide sufficient dynamic high-temperature failure information of the iridium alloy. In this study, we modified current room-temperature Kolsky tension bar techniques for obtaining dynamic tensile stress-strain curves of the DOP-26 iridium alloy at two different strain rates (~1000 and ~3000 s-1) and temperatures (~750°C and ~1030°C). The effects of strain rate and temperature on the tensile stress-strain response of the iridium alloy were determined. The DOP-26 iridium alloy exhibited high ductility in stress-strain response that strongly depended on both strain rate and temperature.

  17. METAL HYDRIDE HYDROGEN COMPRESSORS: A REVIEW

    SciTech Connect

    Bowman Jr, Robert C; Yartys, Dr. Volodymyr A.; Lototskyy, Dr. Michael V; Pollet, Dr. B.G.

    2014-01-01

    Metal hydride (MH) thermal sorption compression is an efficient and reliable method allowing a conversion of energy from heat into a compressed hydrogen gas. The most important component of such a thermal engine the metal hydride material itself should possess several material features in order to achieve an efficient performance in the hydrogen compression. Apart from the hydrogen storage characteristics important for every solid H storage material (e.g. gravimetric and volumetric efficiency of H storage, hydrogen sorption kinetics and effective thermal conductivity), the thermodynamics of the metal-hydrogen systems is of primary importance resulting in a temperature dependence of the absorption/desorption pressures). Several specific features should be optimized to govern the performance of the MH-compressors including synchronisation of the pressure plateaus for multi-stage compressors, reduction of slope of the isotherms and hysteresis, increase of cycling stability and life time, together with challenges in system design associated with volume expansion of the metal matrix during the hydrogenation. The present review summarises numerous papers and patent literature dealing with MH hydrogen compression technology. The review considers (a) fundamental aspects of materials development with a focus on structure and phase equilibria in the metal-hydrogen systems suitable for the hydrogen compression; and (b) applied aspects, including their consideration from the applied thermodynamic viewpoint, system design features and performances of the metal hydride compressors and major applications.

  18. Plasmonic hydrogen sensing with nanostructured metal hydrides.

    PubMed

    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.

  19. Synthesis, structure, and reactivity of rhodium and iridium complexes of the chelating bis-sulfoxide tBuSOC2H4SOtBu. Selective O-H activation of 2-hydroxy-isopropyl-pyridine.

    PubMed

    Schaub, Thomas; Diskin-Posner, Yael; Radius, Udo; Milstein, David

    2008-07-21

    The chloro-bridged rhodium and iridium complexes [M2(BTSE)2Cl2] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC2H4SOtBu (BTSE) were prepared by the reaction of [M2(COE)4Cl2] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)2][PF6] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the iridium(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy- isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] 7, with no competition from the six properly oriented C-H bonds. The cationic rhodium(I) and iridium(I) compounds [M(BTSE)(2-aminomethyl-pyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy- isopropyl-pyridine)][X] 9(stabilized by intramolecular hydrogen bonding), [Ir(BTSE)(pyridine)2][PF6] 12, [Ir(BTSE)(alpha-picoline)2][PF6] 13, and [Rh(BTSE)(1,10-phenanthroline)][PF6] 14 were prepared either by chloride abstraction from the dimeric precursors or by replacement of the labile oxygen bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by pi-pi stacking of the phenanthroline ligands.

  20. Analysis and Consequences of the Iridium 33-Cosmos 2251 Collision

    NASA Technical Reports Server (NTRS)

    Anz-Meador, P. D.; Liou, Jer-Chi

    2010-01-01

    The collision of Iridium 33 and Cosmos 2251, on 10 February 2009, was the first known unintentional hypervelocity collision in space of intact satellites. Iridium 33 was an active commercial telecommunications satellite, while Cosmos 2251 was a derelict communication satellite of the Strela-2M class. The collision occurred at a relative velocity of 11.6 km/s at an altitude of approximately 790 km over the Great Siberian Plain and near the northern apex of Cosmos 2251 s orbit. This paper describes the physical and orbital characteristics of the relevant spacecraft classes and reports upon our analysis of the resulting debris clouds size, mass, area-to-mass ratio, and relative velocity/directionality distributions. We compare these distributions to those predicted by the NASA breakup model and notable recent fragmentation events; in particular, we compare the area-to-mass ratio distribution for each spacecraft to that exhibited by the FY-1C debris cloud for the purpose of assessing the relative contribution of modern aerospace materials to debris clouds resulting from energetic collisions. In addition, we examine the long-term consequences of this event for the low Earth orbit (LEO) environment. Finally, we discuss "lessons learned", which may be incorporated into NASA s environmental models.

  1. Analysis of Abrasive Blasting of DOP-26 Iridium Alloy

    SciTech Connect

    Ohriner, Evan Keith; Zhang, Wei; Ulrich, George B

    2012-01-01

    The effects of abrasive blasting on the surface geometry and microstructure of DOP-26 iridium alloy (Ir-0.3% W-0.006% Th 0.005% Al) have been investigated. Abrasive blasting has been used to control emissivity of components operating at elevated temperature. The effects of abrasive blasting conditions on surface morphology were investigated both experimentally and by numerical modeling. The simplified model, based on finite element analysis of a single angular particle impacting on Ir alloy disk, calculates the surface deformation and residual strain distribution. The experimental results and modeling results both indicate that the surface geometry is not sensitive to the abrasive blast process conditions of nozzle pressure and standoff distance considered in this study. On the other hand, the modeling results suggest that the angularity of the abrasive particle has an important role in determining surface geometry, which in turn, affects the emissivity. Abrasive blasting causes localized surface strains and localized recrystallization, but it does not affect grain size following extended exposure at elevated temperature. The dependence of emissivity of the DOP-26 alloy on mean surface slope follows a similar trend to that reported for pure iridium.

  2. Testing of Wrought Iridium/Chemical Vapor Deposition Rhenium Rocket

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.; Schneider, Steven J.

    1996-01-01

    A 22-N class, iridium/rhenium (Ir/Re) rocket chamber, composed of a thick (418 miocrometer) wrought iridium (Ir) liner and a rhenium substrate deposited via chemical vapor deposition, was tested over an extended period on gaseous oxygen/gaseous hydrogen (GO2/GH2) propellants. The test conditions were designed to produce species concentrations similar to those expected in an Earth-storable propellant combustion environment. Temperatures attained in testing were significantly higher than those expected with Earth-storable propellants, both because of the inherently higher combustion temperature of GO2/GH2 propellants and because the exterior surface of the rocket was not treated with a high-emissivity coating that would be applied to flight class rockets. Thus the test conditions were thought to represent a more severe case than for typical operational applications. The chamber successfully completed testing (over 11 hr accumulated in 44 firings), and post-test inspections showed little degradation of the Ir liner. The results indicate that use of a thick, wrought Ir liner is a viable alternative to the Ir coatings currently used for Ir/Re rockets.

  3. Microindentation hardness evaluation of iridium alloy clad vent set cups

    NASA Astrophysics Data System (ADS)

    Ulrich, George B.; DeRoos, Larry F.; Stinnette, Samuel E.

    1993-01-01

    An iridium alloy, DOP-26, is used as cladding for 238PuO2 fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  4. Microindentation hardness evaluation of iridium alloy clad vent set cups

    SciTech Connect

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E. )

    1993-01-15

    An iridium alloy, DOP-26, is used as cladding for [sup 238]PuO[sub 2] fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  5. Microindentation hardness evaluation of iridium alloy clad vent set cups

    SciTech Connect

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E.

    1992-05-15

    An iridium alloy, DOP-26, is used as cladding for {sup 238}PuO{sup 2} fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration`s Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  6. Microindentation hardness evaluation of iridium alloy clad vent set cups

    SciTech Connect

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E.

    1992-05-15

    An iridium alloy, DOP-26, is used as cladding for {sup 238}PuO{sup 2} fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors.

  7. Hydride phase formation in carbon supported palladium hydride nanoparticles by in situ EXAFS and XRD

    NASA Astrophysics Data System (ADS)

    Bugaev, A. L.; Guda, A. A.; Lomachenko, K. A.; Lazzarini, A.; Srabionyan, V. V.; Vitillo, J. G.; Piovano, A.; Groppo, E.; Bugaev, L. A.; Soldatov, A. V.; Dmitriev, V. P.; Pellegrini, R.; van Bokhoven, J. A.; Lamberti, C.

    2016-05-01

    In the current work we present a detailed analysis of the hydride phase formation in industrial Pd/C nanocatalysts by means of combined in situ X-ray absorption spectroscopy (EXAFS), X-ray diffraction (XRD) and volumetric measurements for the temperatures from - 10 to 50 °C in the hydrogen pressure range from 0 to 1000 mbar. α- and β- hydride phases are clearly distinguished in XRD. For the first time, H/Pd atomic ratio were obtained by theoretical fitting of the near-edge region of the absorption spectra (XANES) and compared with volumetric measurements.

  8. Iridium anomaly in the Cretaceous section of the Eastern Kamchatka

    NASA Astrophysics Data System (ADS)

    Savelyev, Dmitry; Savelyeva, Olga

    2010-05-01

    The origin of iridium anomalies is widely discussed with regard to massive fauna and flora extinction at several geologic boundaries. Two hypotheses are most popular, cosmogenic and volcanogenic. Anomalies of iridium are known at many stratigraphic levels, both at the geologic series borders and within geologic series. Our studies revealed increased content of iridium in a section of Cretaceous oceanic deposits on the Kamchatsky Mys Peninsula (Eastern Kamchatka, Russia). The investigated section (56°03.353´N, 163°00.376´E) includes interbedded jaspers and siliceous limestones overlaying pillow-basalts. These deposits belong to the Smagin Formation of the Albian-Cenomanian age. In the middle and upper parts of the section two beds of black carbonaceous rocks with sapropelic organic matter were observed. Their formation marked likely episodes of oxygen depletion of oceanic intermediate water (oceanic anoxic events). Our geochemical studies revealed an enrichment of the carbonaceous beds in a number of major and trace elements (Al2O3, TiO2, FeO, MgO, K2O, P2O5, Cu, Zn, Ni, Cr, V, Mo, Ba, Y, Zr, Nb, REE, U, Au, Pt etc.) in comparison with associating jaspers and limestones. There are likely different sources which contributed to the enrichment. It is possible however to correlate the excess of Al, Ti, Zr, Nb with volcanogenic admixture, which is absent in limestones and jaspers. A possible source of the volcanogenic material was local volcanism as suggested by the close association of the investigated section with volcanic rocks (basaltic lavas and hyaloclastites). The basalts of the Smagin Formation were previously proposed to originate during Cretaceous activity of the Hawaiian mantle plume (Portnyagin et al., Geology, 2008). Neutron activation analysis indicated increased up to 9 ppb concentration of Ir at the bottom of the lower carbonaceous bed (inorganic part of the sample was analyzed comprising 46% of the bulk rock). In other samples Ir content was below

  9. Phosphorescent Neutral Iridium (III) Complexes for Organic Light-Emitting Diodes.

    PubMed

    Bin Mohd Yusoff, Abd Rashid; Huckaba, Aron J; Nazeeruddin, Mohammad Khaja

    2017-04-01

    The development of transition metal complexes for application in light-emitting devices is currently attracting significant research interest. Among phosphorescent emitters, those involving iridium (III) complexes have proven to be exceedingly useful due to their relatively short triplet lifetime and high phosphorescence quantum yields. The emission wavelength of iridium (III) complexes significantly depends on the ligands, and changing the electronic nature and the position of the ligand substituents can control the properties of the ligands. In this chapter, we discuss recent developments of phosphorescent transition metal complexes for organic light-emitting diode applications focusing solely on the development of iridium metal complexes.

  10. A preliminary study of factors affecting the calibration stability of the iridium versus iridium-40 percent rhodium thermocouple

    NASA Technical Reports Server (NTRS)

    Ahmed, Shaffiq; Germain, Edward F.; Daryabeigi, Kamran; Alderfer, David W.; Wright, Robert E.

    1987-01-01

    An iridium versus iridium-40% rhodium thermocouple was studied. Problems associated with the use of this thermocouple for high temperature applications (up to 2000 C) were investigated. The metallurgical studies included X-ray, macroscopic, resistance, and metallographic studies. The thermocouples in the as-received condition from the manufacturer revealed large amounts of internal stress caused by cold working during manufacturing. The thermocouples also contained a large amount of inhomogeneities and segregations. No phase transformations were observed in the alloy up to 1100 C. It was found that annealing the thermocouple at 1800 C for two hours, and then at 1400 C for 2 to 3 hours yielded a fine grain structure, relieving some of the strains, and making the wire more ductile. It was also found that the above annealing procedure stabilized the thermal emf behavior of the thermocouple for application below 1800 C (an improvement from + or - 1% to + or - 0.02% within the range of the test parameters used).

  11. Metal Hydrides for High-Temperature Power Generation

    DOE PAGES

    Ronnebro, Ewa; Whyatt, Greg A.; Powell, Michael R.; ...

    2015-08-10

    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 a need to produce electricity, such as during night time, a cloudy day, ormore » during peak hours. We proceeded from selecting a high-energy density, low-cost HT-hydride based on performance characterization on gram size samples, to scale-up to kilogram quantities and design, fabrication and testing of a 1.5kWh, 200kWh/m3 bench-scale TES prototype based on a HT-bed of titanium hydride and a hydrogen gas storage instead of a LT-hydride. 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 bench-scale prototype was designed and fabricated and we successfully showed feasibility to meet or exceed all performance targets.« less

  12. Metal-hydride energy-technological processing of hydrogen

    NASA Astrophysics Data System (ADS)

    Solovei, V. V.

    1983-03-01

    The external and internal irreversibility of the thermochemical hydrogen compression cycle is analyzed in relation to the efficiency of heat utilization in a metal-hydride energy system. The properties of the working fluid and the design of the metal-hydride elements are shown to have a considerable effect on the thermodynamic performance of a heat-utilizing installation for hydrogen processing.

  13. Hydrogen storage in the form of metal hydrides

    NASA Technical Reports Server (NTRS)

    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.

  14. Method of making crack-free zirconium hydride

    DOEpatents

    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. Metal Hydrides for High-Temperature Power Generation

    SciTech Connect

    Ronnebro, Ewa; Whyatt, Greg A.; Powell, Michael R.; Westman, Matthew P.; Zheng, Feng; Fang, Zhigang Zak

    2015-08-10

    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 a need to produce electricity, such as during night time, a cloudy day, or during peak hours. We proceeded from selecting a high-energy density, low-cost HT-hydride based on performance characterization on gram size samples, to scale-up to kilogram quantities and design, fabrication and testing of a 1.5kWh, 200kWh/m3 bench-scale TES prototype based on a HT-bed of titanium hydride and a hydrogen gas storage instead of a LT-hydride. 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 bench-scale prototype was designed and fabricated and we successfully showed feasibility to meet or exceed all performance targets.

  16. High energy density battery based on complex hydrides

    DOEpatents

    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.

  17. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    NASA Astrophysics Data System (ADS)

    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.

  18. Analysis and Implications of the Iridium 33-Cosmos 2251 Collision

    NASA Astrophysics Data System (ADS)

    Kelso, T. S.

    On 2009 February 10, Iridium 33--an operational US communications satellite in low-Earth orbit--was struck and destroyed by Cosmos 2251--a long-defunct Russian communications satellite. This is the first time since the dawn of the Space Age that two satellites have collided in orbit. To better understand the circumstances of this event and the ramifications for avoiding similar events in the future, this paper provides a detailed analysis of the predictions leading up to the collision, using various data sources, and looks in detail at the collision, the evolution of the debris clouds, and the long-term implications for satellite operations. The only publicly available system available to satellite operators for screening for close approaches, SOCRATES, did predict this close approach, but it certainly wasn't the closest approach predicted for the week of February 10. In fact, at the time of the collision, SOCRATES ranked this close approach 152 of the 11,428 within 5 km of any payload. A detailed breakdown is provided to help understand the limitations of screening for close approaches using the two-line orbital element sets. Information is also provided specifically for the Iridium constellation to provide an understanding of how these limitations affect decision making for satellite operators. Post-event analysis using high-accuracy orbital data sources will be presented to show how that information might have been used to prevent this collision, had it been available and used. Analysis of the collision event, along with the distribution of the debris relative to the original orbits, will be presented to help develop an understanding of the geometry of the collision and the near-term evolution of the resulting debris clouds. Additional analysis will be presented to show the long-term evolution of the debris clouds, including orbital lifetimes, and estimate the increased risk for operations conducted by Iridium and other satellite operators in the low-Earth orbit

  19. ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

    SciTech Connect

    Wang, Jy-An John; Yan, Yong; Wang, Hong

    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

  20. Iridium-catalyzed hydrogen transfer: synthesis of substituted benzofurans, benzothiophenes, and indoles from benzyl alcohols.

    PubMed

    Anxionnat, Bruno; Gomez Pardo, Domingo; Ricci, Gino; Rossen, Kai; Cossy, Janine

    2013-08-02

    An iridium-catalyzed hydrogen transfer has been developed in the presence of p-benzoquinone, allowing the synthesis of a diversity of substituted benzofurans, benzothiophenes, and indoles from substituted benzylic alcohols.

  1. Synthesis and luminescence properties of iridium(III) azide- and triazole-bisterpyridine complexes.

    PubMed

    Goldstein, Daniel C; Peterson, Joshua R; Cheng, Yuen Yap; Clady, Raphael G C; Schmidt, Timothy W; Thordarson, Pall

    2013-07-26

    We describe here the synthesis of azide-functionalised iridium(III) bisterpyridines using the "chemistry on the complex" strategy. The resulting azide-complexes are then used in the copper(I)-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition "click chemistry" reaction to from the corresponding triazole-functionalised iridium(III) bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III) bisterpyridines, but this effect can be reversed by the addition of copper(II) sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III) bisterpyridines can be functionalized for use in "click chemistry" facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  2. Iridium-catalyst-based autonomous bubble-propelled graphene micromotors with ultralow catalyst loading.

    PubMed

    Wang, Hong; Sofer, Zdeněk; Eng, Alex Yong Sheng; Pumera, Martin

    2014-11-10

    A novel concept of an iridium-based bubble-propelled Janus-particle-type graphene micromotor with very high surface area and with very low catalyst loading is described. The low loading of Ir catalyst (0.54 at %) allows for fast motion of graphene microparticles with high surface area of 316.2 m(2)  g(-1). The micromotor was prepared with a simple and scalable method by thermal exfoliation of iridium-doped graphite oxide precursor composite in hydrogen atmosphere. Oxygen bubbles generated from the decomposition of hydrogen peroxide at the iridium catalytic sites provide robust propulsion thrust for the graphene micromotor. The high surface area and low iridium catalyst loading of the bubble-propelled graphene motors offer great possibilities for dramatically enhanced cargo delivery.

  3. A novel plating process for microencapsulating metal hydrides

    SciTech Connect

    Law, H.H.; Vyas, B.; Zahurak, S.M.; Kammlott, G.W.

    1996-08-01

    One approach to increasing the lifetime of the metal hydride electrode has been the use of conventional electroless plating to produce a coating of copper or nickel on the surface of the metal hydride powders. In this paper, a novel method for microencapsulating the active electrode powders is presented. This new plating technique takes advantage of the reducing power of hydrogen already stored inside the metal hydride to plate a variety of metals onto metal hydride materials. This method greatly simplifies electroless plating for these powders, eliminating the need for stabilizers and additives typically required for conventional electroless plating solutions. Metals that can be electrolessly plated with stored hydrogen have been identified based on thermodynamic considerations. Experimentally, micrometers thick coatings of copper, silver, and nickel have been plated on several metal hydrides.

  4. Porous metal hydride composite and preparation and uses thereof

    DOEpatents

    Steyert, William A.; Olsen, Clayton E.

    1982-01-01

    A composite formed from large pieces of aggregate formed from (1) metal hydride (or hydride-former) powder and (2) either metal powder or plastic powder or both is prepared. The composite has large macroscopic interconnected pores (much larger than the sizes of the powders which are used) and will have a very fast heat transfer rate and low windage loss. It will be useful, for example, in heat engines, hydrogen storage devices, and refrigerator components which depend for their utility upon both a fast rate of hydriding and dehydriding. Additionally, a method of preparing the composite and a method of increasing the rates of hydriding and dehydriding of metal hydrides are also given.

  5. Porous metal hydride composite and preparation and uses thereof

    DOEpatents

    Steyert, W.A.; Olsen, C.E.

    1980-03-12

    A composite formed from large pieces of aggregate formed from (1) metal hydride (or hydride-former) powder and (2) either metal powder or plastic powder or both is prepared. The composite has large macroscopic interconnected pores (much larger than the sizes of the powders which are used) and will have a very fast heat transfer rate and low windage loss. It will be useful, for example, in heat engines, hydrogen storage devices, and refrigerator components which depend for their utility upon both a fast rate of hydriding and dehydriding. Additionally, a method of preparing the composite and a method of increasing the rates of hydriding and dehydriding of metal hydrides are also given.

  6. Metal hydrides for concentrating solar thermal power energy storage

    NASA Astrophysics Data System (ADS)

    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.

  7. Recent advances in metal hydrides for clean energy applications

    SciTech Connect

    Ronnebro, Ewa; Majzoub, Eric H.

    2013-06-01

    Metal hydrides are a fascinating class of materials that can be utilized for a surprising variety of clean energy applications, including smart solar collectors, smart windows, sensors, thermal energy storage, and batteries, in addition to their traditional application for hydrogen storage. Over the past decade, research on metal hydrides for hydrogen storage increased due to global governmental incentives and an increased focus on hydrogen storage research for polymer electrolyte membrane fuel cell operation. Tremendous progress has been made in so-called complex metal hydrides for hydrogen storage applications with the discovery of many new hydrides containing covalently bound complex anions. Many of these materials have applications beyond hydrogen storage and are being investigated for lithium-ion battery separator and anode materials. In this issue of MRS Bulletin , we present the state of the art of key evolving metal-hydride-based clean energy technologies with an outlook toward future needs.

  8. Helium trapping at erbium oxide precipitates in erbium hydride

    SciTech Connect

    Foiles, Stephen M.; Battaile, Corbett Chandler

    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.

  9. Concepts for Cost-Effective Enhanced Cryosat Continuity: Opportunity in the Iridium PRIME Context

    NASA Astrophysics Data System (ADS)

    Le Roy, Y.; Caubet, E.; Silverstrin, P.; Legrand, C.

    2016-08-01

    The Iridium-PRIME offer, recently initiated by the Iridium company, consists in hosting payloads on customized low cost Iridium-NEXT platforms on which the main telecom mission antenna (L-band) is removed. This leaves significant resources in terms of mass, volume and power consumption to host up to three payloads on these customized platforms. The Iridium-PRIME satellites will be inserted in the Iridium-NEXT constellation to take benefit of the low cost operation service (command, control and data telemetry through the life time of the Iridium-PRIME mission). Given the synergy between schedules of the Iridium-PRIME program (launches starting around 2020) and of a possible CryoSat Follow-On (FO) mission (launch around 2022) and the adequacy of the available on-board resources for such a mission, ESA tasked Thales Alenia Space, as responsible for the SIRAL radar instrument of the currently in-orbit CryoSat mission, to study the feasibility of a concept for enhanced continuity of CryoSat on an Iridium- PRIME satellite as potential low-cost fast-track solution. The study aimed to define a cost-effective topographic payload including not only the SIRAL radar but also the necessary sub-systems to retrieve the SIRAL antenna baseline attitude (star trackers) with high accuracy and to perform a Precise Orbit Determination (POD). All these aspects are presented in this paper. In addition, possible evolutions/improvements of the Ku-band radar instrument were analysed and are presented: adding a Ka-band nadir measurement capability and a Ku-band or Ka-band wide swath mode measurement capability. The transmission issue for the SIRAL science data is also discussed in the paper.

  10. Novel Quadrifilar Helix Antenna Combining GNSS, Iridium, and a UHF Communications Monopole

    DTIC Science & Technology

    2012-04-01

    R. J. Davis; “ Ferrite Loaded UHF Sleeve Monopole Integrated with a GPS Patch Antenna for a Handset”. Submitted for publication in “ Microwave and...Novel Quadrifilar Helix Antenna Combining GNSS, Iridium, and a UHF Communications Monopole P. G. Elliot, E. N. Rosario, R. J. Davis The MITRE...Corporation, Bedford, MA 01730 Abstract- A GPS/GNSS/Iridium antenna co-located with a UHF communications monopole on a handset was developed to

  11. Multidirectional Synthesis of Substituted Indazoles via Iridium-Catalyzed C-H Borylation.

    PubMed

    Sadler, Scott A; Hones, Andrew C; Roberts, Bryan; Blakemore, David; Marder, Todd B; Steel, Patrick G

    2015-05-15

    In the absence of a steric directing group, iridium-catalyzed C-H borylation of N-protected indazoles occurs rapidly and selectively at C-3 and the resulting boronate esters can be utilized in a range of downstream conversions. The functional group tolerance of the iridium-catalyzed C-H borylation reaction enables simple and efficient multidirectional syntheses of substituted indazoles to be realized.

  12. Inhibition of Beta-Amyloid Fibrillation by Luminescent Iridium(III) Complex Probes.

    PubMed

    Lu, Lihua; Zhong, Hai-Jing; Wang, Modi; Ho, See-Lok; Li, Hung-Wing; Leung, Chung-Hang; Ma, Dik-Lung

    2015-09-30

    We report herein the application of kinetically inert luminescent iridium(III) complexes as dual inhibitors and probes of beta-amyloid fibrillogenesis. These iridium(III) complexes inhibited Aβ1-40 peptide aggregation in vitro, and protected against Aβ-induced cytotoxicity in neuronal cells. Furthermore, the complexes differentiated between the aggregated and unaggregated forms of Aβ1-40 peptide on the basis of their emission response.

  13. Inhibition of Beta-Amyloid Fibrillation by Luminescent Iridium(III) Complex Probes

    PubMed Central

    Lu, Lihua; Zhong, Hai-Jing; Wang, Modi; Ho, See-Lok; Li, Hung-Wing; Leung, Chung-Hang; Ma, Dik-Lung

    2015-01-01

    We report herein the application of kinetically inert luminescent iridium(III) complexes as dual inhibitors and probes of beta-amyloid fibrillogenesis. These iridium(III) complexes inhibited Aβ1–40 peptide aggregation in vitro, and protected against Aβ-induced cytotoxicity in neuronal cells. Furthermore, the complexes differentiated between the aggregated and unaggregated forms of Aβ1–40 peptide on the basis of their emission response. PMID:26419607

  14. Inhibition of Beta-Amyloid Fibrillation by Luminescent Iridium(III) Complex Probes

    NASA Astrophysics Data System (ADS)

    Lu, Lihua; Zhong, Hai-Jing; Wang, Modi; Ho, See-Lok; Li, Hung-Wing; Leung, Chung-Hang; Ma, Dik-Lung

    2015-09-01

    We report herein the application of kinetically inert luminescent iridium(III) complexes as dual inhibitors and probes of beta-amyloid fibrillogenesis. These iridium(III) complexes inhibited Aβ1-40 peptide aggregation in vitro, and protected against Aβ-induced cytotoxicity in neuronal cells. Furthermore, the complexes differentiated between the aggregated and unaggregated forms of Aβ1-40 peptide on the basis of their emission response.

  15. Results of NDE Technique Evaluation of Clad Hydrides

    SciTech Connect

    Kunerth, Dennis C.

    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

  16. Highly Concentrated Palladium Hydrides/Deuterides; Theory

    SciTech Connect

    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

  17. Lithium hydride - A space age shielding material

    NASA Technical Reports Server (NTRS)

    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.

  18. Metal hydride fuel storage and method thereof

    DOEpatents

    Morse, Jeffrey D.; Jankowski, Alan F.; Yu, Conrad

    2010-08-10

    An apparatus having a first substrate having (1) a cavity, (2) one or more resistive heaters, and (3) one or more coatings forming a diffusion barrier to hydrogen; a second substrate having (1) an outlet valve comprising a pressure relief structure and (2) one or more coatings forming a diffusion barrier to hydrogen, wherein said second substrate is coupled to said first substrate forming a sealed volume in said cavity; a metal hydride material contained within said cavity; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure. Additional apparatuses and methods are also disclosed.

  19. Development of nickel-metal hydride cell

    NASA Technical Reports Server (NTRS)

    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.

  20. Iridium-alloy processing experience in FY 1989

    SciTech Connect

    Ohriner, E.K.

    1990-11-01

    Iridium-alloy blanks and foil are produced at the Oak Ridge National Laboratory for use as fuel cladding material in radioisotope thermoelectric generators for space power sources. Until 1984, the material was produced from small 500-g drop castings. A new process has been developed in which consumable electrodes of about 10 kg are arc melted, extruded, and then rolled to produce the sheet products. The work performed during FY 1989 included the arc melting of three electrodes and the extruding and rolling to sheet of three billets. Significant improvements have been made in the extruding and arc-melting processes. Preliminary results show that these improvements have had an important effect in increasing the rate of blank acceptance in nondestructive evaluations. 4 refs., 33 figs., 11 tabs.

  1. Iridium abundance maxima in the Upper Cenomanian extinction interval

    NASA Technical Reports Server (NTRS)

    Orth, C. J.; Attrep, M., Jr.; Mao, X. Y.; Kauffman, E. G.; Diner, R.

    1988-01-01

    Two iridium abundance peaks, both 0.11 ppb (whole-rock basis) over a local background of 0.017 ppb, have been found in Middle Cretaceous marine rocks near Pueblo, Colorado. They occur just below the 92-million-year-old Cenomanian-Turonian (C-T) stage boundary. No other peaks were found in 45 meters of strata (about 2.5 million years of deposition) above and below the boundary interval. The broad lower peak straddles the first in a series of extinctions of benthic and nektonic macrobiota which comprise the C-T extinction event. The sharp upper peak occurs stratigraphically about 1.2 meters above the lower peak. The excess Ir might be from meteoroid impacts.

  2. Comparative modelling of chemical ordering in palladium-iridium nanoalloys

    SciTech Connect

    Davis, Jack B. A.; Johnston, Roy L.; Rubinovich, Leonid; Polak, Micha

    2014-12-14

    Chemical ordering in “magic-number” palladium-iridium nanoalloys has been studied by means of density functional theory (DFT) computations, and compared to those obtained by the Free Energy Concentration Expansion Method (FCEM) using derived coordination dependent bond energy variations (CBEV), and by the Birmingham Cluster Genetic Algorithm using the Gupta potential. Several compositions have been studied for 38- and 79-atom particles as well as the site preference for a single Ir dopant atom in the 201-atom truncated octahedron (TO). The 79- and 38-atom nanoalloy homotops predicted for the TO by the FCEM/CBEV are shown to be, respectively, the global minima and competitive low energy minima. Significant reordering of minima predicted by the Gupta potential is seen after reoptimisation at the DFT level.

  3. Intercalation of graphene on iridium with samarium atoms

    NASA Astrophysics Data System (ADS)

    Afanas'eva, E. Yu.; Rut'kov, E. V.; Gall, N. R.

    2016-07-01

    Intercalation of graphene on Ir (111) with Sm atoms is studied by methods of thermal desorption spectroscopy and thermionic emission. It is shown that adsorption of samarium at T = 300 K on graphene to concentrations of N ≤ 6 × 1014 atoms cm-2 followed by heating of the substrate leads to practically complete escape of adsorbate underneath the graphene layer. At N > 6 × 1014 atoms cm-2 and increasing temperature, a fraction of adsorbate remains on graphene in the form of two-dimensional "gas" and samarium islands and are desorbed in the range of temperatures of 1000-1200 K. Samarium remaining under the graphene is desorbed from the surface in the temperature range 1200-2150 K. Model conceptions for the samarium-graphene-iridium system in a wide temperature range are developed.

  4. Large Deformation Change in Iridium Isotopes from Laser Spectroscopy

    SciTech Connect

    D. Verney; L. Cabaret; J. Crawford; H.T. Duong; J. Genevey; G. Hubert; F. Ibrahim; M. Krieg; F. Le Blanc; J.K.P. Lee; G. Le Scornet; D. Lunney; J. Obert; J. Oms; J. Pinard; J.C. Putaux; B. Roussiere; J. Sauvage; V. Sebastian

    1999-12-31

    Laser spectroscopy measurements have been performed on neutron-deficient iridium isotopes. The hyperfine structure and isotope shift of the optical Ir I transition 5d{sup 7}6s{sup 2} {sup 4}F{sub 9/2} {yields}5d{sup 7}6s6p {sup 6}F{sub 11/2} have been studied for the {sup 182-189}Ir, {sup 186}Ir{sup m} and {sup 191,193}Ir isotopes. The nuclear magnetic and quadrupole moments were obtained from the hyperfine splitting measurements and the changes of the mean square charge radii from the isotope shift measurements. A large deformation change between {sup 187}Ir and {sup 186}Ir and between {sup 186}Ir{sup m} and {sup 186}Ir{sup g} has been observed.

  5. Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods.

    PubMed

    Kalisman, Philip; Nakibli, Yifat; Amirav, Lilac

    2016-02-11

    We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide (CdSe@CdS) nanorod photocatalysts. Seeded rods are grown using a colloidal hot-injection method and then moved to an aqueous medium by ligand exchange. CdSe@CdS nanorods, an iridium precursor and other salts are mixed and illuminated. The deposition process is initiated by absorption of photons by the semiconductor particle, which results with formation of charge carriers that are used to promote redox reactions. To insure photochemical oxidative growth we used an electron scavenger. The photogenerated holes oxidize the iridium precursor, apparently in a mediated oxidative pathway. This results in the growth of high quality crystalline iridium oxide particles, ranging from 0.5 nm to about 3 nm, along the surface of the rod. Iridium oxide grown on CdSe@CdS heterostructures was studied by a variety of characterization methods, in order to evaluate its characteristics and quality. We explored means for control over particle size, crystallinity, deposition location on the CdS rod, and composition. Illumination time and excitation wavelength were found to be key parameters for such control. The influence of different growth conditions and the characterization of these heterostructures are described alongside a detailed description of their synthesis. Of significance is the fact that the addition of iridium oxide afforded the rods astounding photochemical stability under prolonged illumination in pure water (alleviating the requirement for hole scavengers).

  6. Dynamic High-Temperature Characterization of an Iridium Alloy in Compression at High Strain Rates

    SciTech Connect

    Song, Bo; Nelson, Kevin; Lipinski, Ronald J.; Bignell, John L.; Ulrich, G. B.; George, E. P.

    2014-06-01

    Iridium alloys have superior strength and ductility at elevated temperatures, making them useful as structural materials for certain high-temperature applications. However, experimental data on their high-temperature high-strain-rate performance are needed for understanding high-speed impacts in severe elevated-temperature environments. Kolsky bars (also called split Hopkinson bars) have been extensively employed for high-strain-rate characterization of materials at room temperature, but it has been challenging to adapt them for the measurement of dynamic properties at high temperatures. Current high-temperature Kolsky compression bar techniques are not capable of obtaining satisfactory high-temperature high-strain-rate stress-strain response of thin iridium specimens investigated in this study. We analyzed the difficulties encountered in high-temperature Kolsky compression bar testing of thin iridium alloy specimens. Appropriate modifications were made to the current high-temperature Kolsky compression bar technique to obtain reliable compressive stress-strain response of an iridium alloy at high strain rates (300 – 10000 s-1) and temperatures (750°C and 1030°C). Uncertainties in such high-temperature high-strain-rate experiments on thin iridium specimens were also analyzed. The compressive stress-strain response of the iridium alloy showed significant sensitivity to strain rate and temperature.

  7. Iridium NEXT partnership for Earth observation: exploiting global satellite constellations for new remote sensing capabilities

    NASA Astrophysics Data System (ADS)

    Gupta, Om P.

    2008-08-01

    A unique opportunity exists to host up to 66 earth observation sensors on the Iridium NEXT LEO constellation in a manner that can revolutionize earth observation and weather predictions. A constellation approach to sensing, using the real-time communications backbone of Iridium, will enable unprecedented geospatial and temporal sampling for now-casting of weather on a global basis as well as global climate monitoring. The Iridium NEXT constellation, with 66 interconnected satellites in 6 near polar orbiting planes, provides a unique platform for hosting a variety of earth observation missions. The opportunity is proposed as a Public-Private Partnership (PPP) allowing for the sharing of infrastructure by government agencies. This has the potential to augment current and planned climate and weather observation programs in a very cost effective manner not achievable in any other way. Iridium, with the assistance of the Group on Earth Observations (GEO), NASA, NOAA, and ESA, has evaluated a number of sensing missions that would be a good fit to the Iridium NEXT constellation. These include GPS radio occultation sensors, earth radiation budget measurements, radio altimetry, tropospheric and stratospheric winds measurements including polar winds measurements, and atmospheric chemistry. Iridium NEXT launches start in 2013 and constellation operational life will extend beyond 2030. Detailed feasibility studies on specific missions are planned to begin later this year.

  8. Catalytic Transfer of Magnetism using a Neutral Iridium Phenoxide Complex

    PubMed Central

    Ruddlesden, Amy J.; Mewis, Ryan E.; Green, Gary G. R.; Whitwood, Adrian C.; Duckett, Simon B.

    2016-01-01

    A novel neutral iridium carbene complex Ir(κC,O-L1)(COD) (1) [where COD = cyclooctadiene and L1 = 3-(2-methylene-4-nitrophenolate)-1-(2,4,6-trimethylphenyl) imidazolylidene] with a pendant alkoxide ligand has been prepared and characterized. It contains a strong Ir-O bond and X-ray analysis reveals a distorted square planar structure. NMR spectroscopy reveals dynamic solution state behavior commensurate with rapid seven-membered ring flipping. In CD2Cl2 solution, under hydrogen at low temperature, this complex dominates although it exists in equilibrium with a reactive iridium dihydride cyclooctadiene complex. 1 reacts with pyridine and H2 to form neutral Ir(H)2(κC,O-L1)(py)2 which also exists in two conformers that differ according to the orientation of the seven-membered metallocycle and whilst its Ir-O bond remains intact, the complex undergoes both pyridine and H2 exchange. As a consequence, when placed under parahydrogen, efficient polarization transfer catalysis (PTC) is observed via the Signal Amplification By Reversible Exchange (SABRE) approach. Due to the neutral character of this catalyst, good hyperpolarization activity is shown in a wide range of solvents for a number of substrates. These observations reflect a dramatic improvement in solvent tolerance of SABRE over that reported for the best PTC precursor IrCl(IMes)(COD). For THF, the associated 1H NMR signal enhancement for the ortho proton signal of pyridine shows an increase of 600-fold at 298 K. The level of signal enhancement can be increased further through warming or varying the magnetic field experienced by the sample at the point of catalytic magnetization transfer.

  9. New yellow-emitting phosphorescent cyclometalated iridium(III) complex

    NASA Astrophysics Data System (ADS)

    Ivanov, P.; Tomova, R.; Petrova, P.; Stanimirov, S.; Petkov, I.

    2012-12-01

    We have synthesized a new yellow iridium complex Iridium(III) bis[2-phenylbenzothiazolato-N,C2']-(1-phenylicosane-1,3-dionate) (bt)2Ir(bsm), based on the benzothiazole derivative. The synthesized molecule was identified by 1H NMR and elemental analysis. The UV-Visible absorption and photoluminescence (PL) spectra of (bt)Ir2(bsm) in CH2Cl2 solution were found at 273 nm and 559 nm, respectively. The complex was used as a dopant into a hole-transporting layer (HTL) in a multilayered organic light emitting device (OLED) structure: ITO/doped-HTL/EL/ETL/M. ITO was a transparent anode of In2O3:SnO2, M- a metallic Al cathode, HTL- 4,4'-bis(9H-carbazol-9-yl)biphenyl (CBP) incorporated in poly(N-vinylcarbazole) (PVK) matrix, EL- electroluminescent layer of bis(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)aluminum (BAlq) and ETL- electron-transporting layer of tris(8-hydroxyquinolinato)aluminum (Alq3). The electroluminescent (EL) spectra of OLEDs were basically the sum of the emissions of BAlq at 496 nm and the emission of (bt)2Ir(bsm) at 559 nm. With increasing (bt)2Ir(bsm) concentration, the relative electroluminescent intensity of greenish-blue emission (at 496 nm) decreased, while the yellow (at 559 nm) - increased and CIE coordinates of the device shifted from (0.21, 0.33) at 0 wt % to (0.40, 0.48) at 8 wt % of the dopant. It was found that OLED with 0.5 wt % (bt)2Ir(bsm) had the best performance and stable color chromaticity at various voltages.

  10. Iridium-Coated Rhenium Radiation-Cooled Rockets

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.; Biaglow, James A.; Schneider, Steven J.

    1997-01-01

    Radiation-cooled rockets are used for a range of low-thrust propulsion functions, including apogee insertion, attitude control, and repositioning of satellites, reaction control of launch vehicles, and primary propulsion for planetary space- craft. The key to high performance and long lifetimes for radiation-cooled rockets is the chamber temperature capability. The material system that is currently used for radiation-cooled rockets, a niobium alloy (C103) with a fused silica coating, has a maximum operating temperature of 1370 C. Temperature limitations of C103 rockets force the use of fuel film cooling, which degrades rocket performance and, in some cases, imposes a plume contamination issue from unburned fuel. A material system composed of a rhenium (Re) substrate and an iridium (Ir) coating has demonstrated operation at high temperatures (2200 C) and for long lifetimes (hours). The added thermal margin afforded by iridium-coated rhenium (Ir/Re) allows reduction or elimination of fuel film cooling. This, in turn, leads to higher performance and cleaner spacecraft environments. There are ongoing government- and industry-sponsored efforts to develop flight Ir/ Re engines, with the primary focus on 440-N, apogee insertion engines. Complementing these Ir/Re engine development efforts is a program to address specific concerns and fundamental characterization of the Ir/Re material system, including (1) development of Ir/Re rocket fabrication methods, (2) establishment of critical Re mechanical properly data, (3) development of reliable joining methods, and (4) characterization of Ir/Re life-limiting mechanisms.

  11. The Electric Dipole Moment of Iridium Monosilicide, IrSi

    NASA Astrophysics Data System (ADS)

    Le, Anh; Steimle, Timothy C.; Cheng, Lan; Stanton, John F.

    2013-06-01

    The optical spectrum of iridium monosilicide (IrSi) was recently observed using REMPI spectroscopy in the range 17200 to 23850 cm^{-1}. The observation was supported by an ab initio calculation which predicted a X^{2}Δ_{5/2} state. Here, we report on the analysis of the optical Stark effect for the X^{2}Δ_{5/2} and [16.0]1.5 (v=6) states. The (6,0)[16.0]1.5 - X^{2}Δ_{5/2} and the (7,0)[16.0]3.5- X^{2}Δ_{5/2} bands of IrSi have been recorded using high-resolution laser-induced fluorescence spectroscopy. The observed optical Stark shifts for the ^{193}IrSi and ^{191}IrSi isotopologues were analyzed to produce the electric dipole moments of -0.4139(64)D and 0.7821(63)D for the X^{2}Δ_{5/2} and [16.0]1.5 (v=6) states, respectively. The negative sign of electric dipole moment of the X^{2}Δ_{5/2} state is supported by high-level quantum-chemical calculations employing all-electron scalar-relativistic CCSD(T) method augmented with spin-orbit corrections as well as corrections due to full triple excitations. In particular, electron-correlation effects have been shown to be essential in the prediction of the negative sign of the dipole moment. A comparison with other iridium containing molecules will be made. Maria A. Garcia, Carolin Vietz, Fernando Ruipérez, Michael D. Morse, and Ivan Infante, Kimika Fakultatea, Euskal Herriko. J. Chem. Phys., (submitted)

  12. Cytotoxic activity and protein binding through an unusual oxidative mechanism by an iridium(I)-NHC complex.

    PubMed

    Gothe, Y; Marzo, T; Messori, L; Metzler-Nolte, N

    2015-02-21

    A new NHC iridium(I) complex (1) showing significant antiproliferative properties in vitro is described here. Its crystal structure, solution behaviour and interactions with the model proteins cytochrome c (cyt c) and lysozyme were investigated. High resolution ESI-MS measurements suggest that this iridium(i) complex acts as a prodrug and binds cyt c tightly through an unusual "oxidative" mechanism. Eventually, an iridium(III)-NHC fragment is found associated to the protein.

  13. Feasibility Analysis on the Utilization of the Iridium Satellite Communications Network for Resident Space Objects in Low Earth Orbit

    DTIC Science & Technology

    2013-03-21

    turquoise -colored plane (containing Iridium_68) and orange-colored plane (containing Iridium_40) compared to the spacing between the turquoise -colored...plane and the white-colored plane (containing Iridium_11). The turquoise -colored and orange-colored planes can be thought of as planes one and six...United States, the turquoise - colored plane is descending, or transiting north to south, and the orange-colored plane is ascending, or transiting

  14. Pressure-stabilized superconductive yttrium hydrides

    NASA Astrophysics Data System (ADS)

    Li, Yinwei; Hao, Jian; Liu, Hanyu; Tse, John S.; Wang, Yanchao; Ma, Yanming

    2015-05-01

    The search for high-temperature superconductors has been focused on compounds containing a large fraction of hydrogen, such as SiH4(H2)2, CaH6 and KH6. Through a systematic investigation of yttrium hydrides at different hydrogen contents using an structure prediction method based on the particle swarm optimization algorithm, we have predicted two new yttrium hydrides (YH4 andYH6), which are stable above 110 GPa. Three types of hydrogen species with increased H contents were found, monatomic H in YH3, monatomic H+molecular “H2” in YH4 and hexagonal “H6” unit in YH6. Interestingly, H atoms in YH6 form sodalite-like cage sublattice with centered Y atom. Electron-phonon calculations revealed the superconductive potential of YH4 and YH6 with estimated transition temperatures (Tc) of 84-95 K and 251-264 K at 120 GPa, respectively. These values are higher than the predicted maximal Tc of 40 K in YH3.

  15. Pressure-stabilized superconductive yttrium hydrides.

    PubMed

    Li, Yinwei; Hao, Jian; Liu, Hanyu; Tse, John S; Wang, Yanchao; Ma, Yanming

    2015-05-05

    The search for high-temperature superconductors has been focused on compounds containing a large fraction of hydrogen, such as SiH4(H2)2, CaH6 and KH6. Through a systematic investigation of yttrium hydrides at different hydrogen contents using an structure prediction method based on the particle swarm optimization algorithm, we have predicted two new yttrium hydrides (YH4 andYH6), which are stable above 110 GPa. Three types of hydrogen species with increased H contents were found, monatomic H in YH3, monatomic H+molecular "H2" in YH4 and hexagonal "H6" unit in YH6. Interestingly, H atoms in YH6 form sodalite-like cage sublattice with centered Y atom. Electron-phonon calculations revealed the superconductive potential of YH4 and YH6 with estimated transition temperatures (Tc) of 84-95 K and 251-264 K at 120 GPa, respectively. These values are higher than the predicted maximal Tc of 40 K in YH3.

  16. Pressure-stabilized superconductive yttrium hydrides

    PubMed Central

    Li, Yinwei; Hao, Jian; Liu, Hanyu; Tse, John S.; Wang, Yanchao; Ma, Yanming

    2015-01-01

    The search for high-temperature superconductors has been focused on compounds containing a large fraction of hydrogen, such as SiH4(H2)2, CaH6 and KH6. Through a systematic investigation of yttrium hydrides at different hydrogen contents using an structure prediction method based on the particle swarm optimization algorithm, we have predicted two new yttrium hydrides (YH4 andYH6), which are stable above 110 GPa. Three types of hydrogen species with increased H contents were found, monatomic H in YH3, monatomic H+molecular “H2” in YH4 and hexagonal “H6” unit in YH6. Interestingly, H atoms in YH6 form sodalite-like cage sublattice with centered Y atom. Electron-phonon calculations revealed the superconductive potential of YH4 and YH6 with estimated transition temperatures (Tc) of 84–95 K and 251–264 K at 120 GPa, respectively. These values are higher than the predicted maximal Tc of 40 K in YH3. PMID:25942452

  17. Metal hydrides for lithium-ion batteries.

    PubMed

    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.

  18. Regeneration of Aluminum Hydride Using Trimethylamine

    SciTech Connect

    D Lacina; J Reilly; Y Celebi; J Wegrzyn; J Johnson; J Graetz

    2011-12-31

    Aluminum hydride is an attractive reducing agent and energy storage compound possessing a low decomposition temperature and a high gravimetric and volumetric hydrogen density. However, it is thermodynamically unstable at room temperature and requires extremely high pressures to form the hydride from aluminum and hydrogen gas. Here, we describe an alternate method of synthesizing AlH{sub 3} using Ti-catalyzed Al powder, H{sub 2}, and trimethylamine (TMA) to form an alane adduct. The formation of trimethylamine alane occurs at modest hydrogen pressures ({approx}100 bar), forming the 2:1 bis complex (2 trimethylamine/AlH{sub 3}). Along with the hydrogenation product, mono (1:1) and bis (2:1) standards of TMA-AlH{sub 3} were prepared and characterized using X-ray diffraction and Raman spectroscopy. X-ray absorption spectroscopy of the reaction products showed that the Ti catalyst remains with the unreacted Al powder after hydrogenation and is not present in the alane adduct. We also demonstrate that TMA can be transaminated with triethylamine to form triethylamine alane, which can easily be separated to recover AlH{sub 3}.

  19. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    PubMed

    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.

  20. The development of metal hydrides using as concentrating solar thermal storage materials

    NASA Astrophysics Data System (ADS)

    Qu, Xuanhui; Li, Yang; Li, Ping; Wan, Qi; Zhai, Fuqiang

    2015-12-01

    Metal hydrides high temperature thermal heat storage technique has great promising future prospects in solar power generation, industrial waste heat utilization and peak load regulating of power system. This article introduces basic principle of metal hydrides for thermal storage, and summarizes developments in advanced metal hydrides high-temperature thermal storage materials, numerical simulation and thermodynamic calculation in thermal storage systems, and metal hydrides thermal storage prototypes. Finally, the future metal hydrides high temperature thermal heat storage technique is been looked ahead.

  1. A study of hydriding kinetics of metal hydrides using a physically based model

    NASA Astrophysics Data System (ADS)

    Voskuilen, Tyler G.

    The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. The stored hydrogen can be used to produce energy through combustion, reaction in a fuel cell, or electrochemically in metal hydride batteries. The high enthalpy of the metal-hydrogen reaction can also be used for rapid heat removal or delivery. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. In this work, a 700 bar Sievert system was developed at the Purdue Hydrogen Systems Laboratory to study the kinetic and thermodynamic behavior of high pressure hydrogen absorption under near-ambient temperatures. This system was used to determine the kinetic and thermodynamic properties of TiCrMn, an intermetallic metal hydride of interest due to its ambient temperature performance for vehicular applications. A commonly studied intermetallic hydride, LaNi5, was also characterized as a base case for the phase field model. The analysis of the data obtained from such a system necessitate the use of specialized techniques to decouple the measured reaction rates from experimental conditions. These techniques were also developed as a part of this work. Finally, a phase field model of metal hydride formation in mass-transport limited interstitial solute reactions based on the regular solution model was developed and compared with measured kinetics of LaNi5 and TiCrMn. This model aided in the identification of key reaction features and was used to verify the proposed technique for the analysis of gas-solid reaction rates determined volumetrically. Additionally, the phase field model provided detailed quantitative predictions of the

  2. Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds.

    PubMed

    Mock, Michael T; Potter, Robert G; O'Hagan, Molly J; Camaioni, Donald M; Dougherty, William G; Kassel, W Scott; DuBois, Daniel L

    2011-12-05

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H(2) gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)(2) (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX(3) compounds having a hydride affinity (HA) greater than or equal to the HA of BEt(3). This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)(2) and [HNi(dmpe)(2)](+), to form B-H bonds. The hydride donor abilities (ΔG(H(-))°) of HCo(dmpe)(2) and [HNi(dmpe)(2)](+) were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX(3) compounds. The collective data guided our selection of BX(3) compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)(2) was observed to transfer H(-) to BX(3) compounds with X = H, OC(6)F(5), and SPh. The reaction with B(SPh)(3) is accompanied by the formation of dmpe-(BH(3))(2) and dmpe-(BH(2)(SPh))(2) products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)(2) and B(SPh)(3) in the presence of triethylamine result in the formation of Et(3)N-BH(2)SPh and Et(3)N-BH(3) with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)(2)](+) with B(SPh)(3) under analogous conditions give Et(3)N-BH(2)SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)(2)(SPh)](+). The synthesis and characterization of HCo(dedpe)(2) (dedpe = Et(2)PCH(2)CH(2)PPh(2)) from H(2) and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)(2)Co(dedpe)(2)][BF(4)].

  3. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX₃ Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. Scott; DuBois, Daniel L.

    2011-10-31

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H₂ gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)₂ (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX₃ compounds having a hydride affinity (HA) greater than or equal to the HA of BEt₃. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)₂ and [HNi(dmpe)₂]+, to form B–H bonds. The hydride donor abilities (ΔGH °) of HCo(dmpe)₂ and [HNi(dmpe)₂]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX₃ compounds. The collective data guided our selection of BX₃ compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)₂ was observed to transfer H to BX₃ compounds with X = H, OC₆F₅, and SPh. The reaction with B(SPh)₃ is accompanied by the formation of dmpe-(BH₃)₂ and dmpe-(BH₂(SPh))₂ products that follow from a reduction of multiple B–SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)₂ and B(SPh)₃ in the presence of triethylamine result in the formation of Et₃N–BH₂SPh and Et₃N–BH₃ with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)₂]+ with B(SPh)₃ under analogous conditions give Et₃N–BH₂SPh as the final product along with the nickel–thiolate complex [Ni(dmpe)₂(SPh)]+. The synthesis and characterization of HCo(dedpe)₂ (dedpe = Et₂PCH₂CH₂PPh₂) from H₂ and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)₂Co(dedpe)₂][BF₄].

  4. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly J.; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.

    2011-12-05

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H{sub 2} gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe){sub 2}, dmpe = 1,2-bis(dimethylphosphinoethane) was capable of reducing a variety of BX{sub 3} compounds having hydride affinity (HA) greater than or equal to HA of BEt{sub 3}. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, (HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +}), to form B-H bonds. The hydride donor abilities ({Delta}G{sub H{sup -}}{sup o}) of HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +} were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX{sub 3} compounds. The collective data guided our selection of BX{sub 3} compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe){sub 2} was observed to transfer H{sup -} to BX{sub 3} compounds with X = H, OC{sub 6}F{sub 5} and SPh. The reaction with B(SPh){sub 3} is accompanied by formation of (BH{sub 3}){sub 2}-dmpe and (BH{sub 2}SPh){sub 2}-dmpe products that follow from reduction of multiple BSPh bonds and loss of a dmpe ligand from Co. Reactions between HCo(dmpe){sub 2} and B(SPh){sub 3} in the presence of triethylamine result in formation of Et{sub 3}N-BH{sub 2}SPh and Et{sub 3}N-BH{sub 3} with no loss of dmpe ligand. Reactions of the cationic complex [HNi(dmpe){sub 2}]{sup +} with B(SPh){sub 3} under analogous conditions give Et{sub 3}N-BH{sub 2}SPh as the final product along with the nickel-thiolate complex [Ni(dmpe){sub 2}(SPh)]{sup +}. The synthesis and characterization of HCo(dedpe){sub 2} (dedpe = diethyldiphenyl(phosphino)ethane) from H{sub 2} and a base is also discussed; including the formation of an uncommon trans

  5. Hot temperatures line lists for metal hydrides

    NASA Astrophysics Data System (ADS)

    Gorman, M.; Lodi, L.; Leyland, P. pC; Hill, C.; Yurchenko, S. N.; Tennyson, J.

    2013-09-01

    The ExoMol project is an ERC funded project set up with the purpose of calculating high quality theoretical molecular line list data to facilitate the emerging field of exoplanet and cool star atmospheric haracterisation [1]. Metal hydrides are important building blocks of interstellar physical chemistry. For molecular identification and characterisation in astrophysical sources, one requires accurate and complete spectroscopic data including transitional frequencies and intensities in the form of a line list. The ab initio methods offer the best opportunity for detailed theoretical studies of free diatomic metal hydrides and other simple hydride molecules. In this contribution we present progress on theoretical line lists for AlH, CrH, MgH, NiH, NaH and TiH obtained from first principles, applicable for a large range of temperatures up to 3500 K. Among the hydrides, AlH is of special interest because of a relatively high cosmic abundance of aluminium. The presence of AlH has been detected in the spectra of M-type and S-type stars as well as in sunspots (See [2] and references therein). CrH is a molecule of astrophysical interest; under the classification scheme developed by Kirkpatrick et al [3], CrH is of importance in distinguishing L type brown dwarfs. It has been proposed that theoretical line-lists of CrH and CrD could be used to facilitate a 'Deuterium test' for use in distinguishing planets, brown dwarfs and stars [5] and also it has been speculated that CrH exists in sunspots [4] but a higherquality hot-temperature line-list is needed to confirm this finding. The presence of MgH in stellar spectra is well documented through observation of the A2 ! X 2+ and B0 2+ ! X 2+ transitions. Different spectral features of MgH have been used as an indicator for the magnesium isotope abundances in the atmospheres of different stars from giants to dwarfs including the Sun, to measure the temperature of stars, surface gravity, stars' metal abundance, gravitational, as

  6. Synthesis and some reactions of dibutyltin (S)- and (R)-camphorsulfonyl hydrides.

    PubMed

    Kinart, Wojciech J; Kinart, Cezary M; Kozak, Monika; Kinart, Andrzej; Sendecki, Marcin; Matczak, Piotr

    2009-08-01

    The synthesis and physical properties of dibutyltin (S)-camphorsulfonyl hydride (1) and dibutyltin (R)-camphorsulfonyl hydride (2), and diphenyltin (S)-camphorsulfonyl hydride (3) as well as that of their organotin precursors are described. Their reactivity with different amines as triethylamine, morpholine and pyridine has been compared with other mixed hydrides as dibutyltin chloride hydride, dibutyltin acetate hydride and dibutyltin dihydride. It has been studied also the possibility of using of dibutyltin (R)- or (S)-camphorsulfonyl hydrides for the stereoselective reduction of different ketones as acetophenone, menthon, camphor and cyclopropyl-(4-metoxyphenyl)-methanone. The reduction of acetophenone with studied camphorsulfonyl hydrides carried out in benzene at room temperature afforded 1-phenylethanol with relatively low enantioselectivity. Addition of 10 equiv. of MnCl(2)*4H(2)O or ZnCl(2) to the reduction mixture involving dibutyltin (S)-camphorsulfonyl hydride (1) and acetophenone and carried out in methanol and tetrahydrofuran, respectively, resulted in remarkable increase in enantioselectivity. The comparative kinetic studies of reduction of acetophenone by different hydrides proved that dibutyltin camphorsulfonyl hydride is significantly more reactive in comparison with dibutyltin chloro hydride and dibutyltin acetate hydride. Analogous results have been obtained from kinetic studies for different tin hydrides with chosen amines. The outcome of these studies supported by theoretical calculations led to the conclusion that the order of reactivity of the studied hydrides correlates with the rate of their homolytic decomposition at room temperature.

  7. Technical and economic aspects of hydrogen storage in metal hydrides

    NASA Technical Reports Server (NTRS)

    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.

  8. Structural Characterization of Metal Hydrides for Energy Applications

    NASA Astrophysics Data System (ADS)

    George, Lyci

    Hydrogen can be an unlimited source of clean energy for future because of its very high energy density compared to the conventional fuels like gasoline. An efficient and safer way of storing hydrogen is in metals and alloys as hydrides. Light metal hydrides, alanates and borohydrides have very good hydrogen storage capacity, but high operation temperatures hinder their application. Improvement of thermodynamic properties of these hydrides is important for their commercial use as a source of energy. Application of pressure on materials can have influence on their properties favoring hydrogen storage. Hydrogen desorption in many complex hydrides occurs above the transition temperature. Therefore, it is important to study the physical properties of the hydride compounds at ambient and high pressure and/or high temperature conditions, which can assist in the design of suitable storage materials with desired thermodynamic properties. The high pressure-temperature phase diagram, thermal expansion and compressibility have only been evaluated for a limited number of hydrides so far. This situation serves as a main motivation for studying such properties of a number of technologically important hydrides. Focus of this dissertation was on X-ray diffraction and Raman spectroscopy studies of Mg2FeH6, Ca(BH4) 2, Mg(BH4)2, NaBH4, NaAlH4, LiAlH4, LiNH2BH3 and mixture of MgH 2 with AlH3 or Si, at different conditions of pressure and temperature, to obtain their bulk modulus and thermal expansion coefficient. These data are potential source of information regarding inter-atomic forces and also serve as a basis for developing theoretical models. Some high pressure phases were identified for the complex hydrides in this study which may have better hydrogen storage properties than the ambient phase. The results showed that the highly compressible B-H or Al-H bonds and the associated bond disordering under pressure is responsible for phase transitions observed in brorohydrides or

  9. The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

    DTIC Science & Technology

    2016-01-04

    a solid with six crystalline phases. In principle, alane is a promising propellant . The specific impulse of an AP/HTPB propellant mixed with alane...Distribution approved for public release. 2     Introduction Boranes (boron hydrides) were once thought to be promising propellants .1-14 The reasons...diborane, hydrogen, and a white solid . Whatley et al.8 studied the products of diborane oxidation. Roth and co-workers9 found HOBO to be the main

  10. ENVIRONMENTAL REACTIVITY OF SOLID STATE HYDRIDE MATERIALS

    SciTech Connect

    Gray, J; Donald Anton, D

    2009-04-23

    In searching for high gravimetric and volumetric density hydrogen storage systems, it is inevitable that higher energy density materials will be used. In order to make safe and commercially acceptable condensed phase hydrogen storage systems, it is important to understand quantitatively the risks involved in using and handling these materials and to develop appropriate mitigation strategies to handle potential material exposure events. A crucial aspect of the development of risk identification and mitigation strategies is the development of rigorous environmental reactivity testing standards and procedures. This will allow for the identification of potential risks and implementation of risk mitigation strategies. Modified testing procedures for shipping air and/or water sensitive materials, as codified by the United Nations, have been used to evaluate two potential hydrogen storage materials, 2LiBH{sub 4} {center_dot} MgH{sub 2} and NH{sub 3}BH{sub 3}. The modified U.N. procedures include identification of self-reactive substances, pyrophoric substances, and gas-emitting substances with water contact. The results of these tests for air and water contact sensitivity will be compared to the pure material components where appropriate (e.g. LiBH{sub 4} and MgH{sub 2}). The water contact tests are divided into two scenarios dependent on the hydride to water mole ratio and heat transport characteristics. Air contact tests were run to determine whether a substance will spontaneously react with air in a packed or dispersed form. In the case of the 2LiBH{sub 4} {center_dot} MgH{sub 2} material, the results from the hydride mixture compared to the pure materials results showed the MgH{sub 2} to be the least reactive component and LiBH{sub 4} the more reactive. The combined 2LiBH{sub 4} {center_dot} MgH{sub 2} resulted in a material having environmental reactivity between these two materials. Relative to 2LiBH{sub 4} {center_dot} MgH{sub 2}, the chemical hydride NH{sub 3}BH

  11. Evaluation of oxide-coated iridium-rhenium chambers

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.

    1994-01-01

    Iridium-coated rhenium (Ir-Re) provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase Ir-Re rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated Ir-Re, 22-N rocket chambers were tested with gaseous hydrogen/gaseous oxygen (GHz/G02) propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia (HfO2) or zirconia (ZrO2). Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of ZrO2 infiltrated with sol gel HfO2. The other chamber had a coating composed of an Ir-oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. Testing the Ir-oxide composite-coated chamber included over 29 min at mixture ratio 16. The thicker walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner walled coatings did not experience the macrocracking and chipping of the chambers that was seen with the thick, monolithic coatings. However, burn-throughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stoichiometric. The burn-throughs were probably the result of oxygen diffusion through the oxide coating that allowed the underlying Ir and Re layers to be oxidized. The results of this test program indicated that the thin-walled oxide

  12. Relativistic effects on sixth group hydrides

    NASA Astrophysics Data System (ADS)

    Pisani, L.; Clementi, E.

    1994-08-01

    Dirac-Fock (DF) and Hartree-Fock (HF) calculations have been performed for the ground state configuration of the H2O, H2S, H2Se, H2Te, and H2Po molecules. Equilibrium geometries, atomization energies, and molecular orbitals energies are evaluated with both methods, compared and discussed with the help of population analysis and atomic orbital energies. Particular attention has been given to a qualitative understanding of the relativistic effects. Molecular spin-orbits corrections appear to be essential to a description of some in the sixth group hydrides set. A description of the relativistic computer program is presented elsewhere [L. Pisani and E. Clementi, J. Comput. Chem. (in press)].

  13. Zirconium Hydride Space Power Reactor design.

    NASA Technical Reports Server (NTRS)

    Asquith, J. G.; Mason, D. G.; Stamp, S.

    1972-01-01

    The Zirconium Hydride Space Power Reactor being designed and fabricated at Atomics International is intended for a wide range of potential applications. Throughout the program a series of reactor designs have been evaluated to establish the unique requirements imposed by coupling with various power conversion systems and for specific applications. Current design and development emphasis is upon a 100 kilowatt thermal reactor for application in a 5 kwe thermoelectric space power generating system, which is scheduled to be fabricated and ground tested in the mid 70s. The reactor design considerations reviewed in this paper will be discussed in the context of this 100 kwt reactor and a 300 kwt reactor previously designed for larger power demand applications.

  14. Far-infrared spectrum of sodium hydride

    NASA Astrophysics Data System (ADS)

    Leopold, K. R.; Zink, L. R.; Evenson, K. M.; Jennings, D. A.

    1987-03-01

    Rotational spectra in the v = 0, 1, 2, and 3 levels of the ground ( 1Σ) state of sodium hydride have been observed using tunable far-infrared radiation generated from the difference frequency between two CO 2 lasers. The Dunham coefficients, which have been determined without the use of optical data or isotopic scaling relations, are Y01 = 146 999.138(38) MHz, Y02 = -10.29481(54) MHz, Y03 = 6.243(49) × 10 -4 MHz, Y11 = -4109.912(68) MHz, Y12 = 0.14695(68) MHz, Y21 = 33.341(34) MHz, Y22 = -2.69(20) × 10 -3 MHz, and Y31 = -1.0517(55) MHz. The constants are typically an order of magnitude more accurate than the best values previously available, and where comparison is possible, agreement is found to be excellent.

  15. Ni/metal hydride secondary element

    DOEpatents

    Bauerlein, Peter

    2005-04-19

    A Ni/metal hydride secondary element having a positive nickel hydroxide electrode, a negative electrode having a hydrogen storage alloy, and an alkaline electrolyte, the positive electrode, provided with a three-dimensional metallic conductive structure, also contains an aluminum compound which is soluble in the electrolyte, in addition to nickel hydroxide and cobalt oxide. The aluminum compound is aluminum hydroxide and/or aluminum oxide, and the mass of the aluminum compound which is present in the positive bulk material mixture is 0.1 to 2% by weight relative to the mass of the nickel hydroxide which is present. In combination with aluminum hydroxide or aluminum oxide, the positive electrode further contains lanthanoid oxidic compounds Y.sub.2 O.sub.3, La.sub.2 O.sub.3 and Ca(OH).sub.2, as well as mixtures of these compounds.

  16. Process for production of a metal hydride

    SciTech Connect

    Allen, Nathan Tait; Butterick, III, Robert; Chin, Arthur Achhing; Millar, Dean Michael; Molzahn, David Craig

    2014-08-12

    A process for production of a metal hydride compound MH.sub.x, wherein x is one or two and M is an alkali metal, Be or Mg. The process comprises combining a compound of formula (R.sup.1O).sub.xM with aluminum, hydrogen and at least one metal selected from among titanium, zirconium, hafnium, niobium, vanadium, tantalum and iron to produce a compound of formula MH.sub.x. R.sup.1 is phenyl or phenyl substituted by at least one alkyl or alkoxy group. A mole ratio of aluminum to (R.sup.1O).sub.xM is from 0.1:1 to 1:1. The catalyst is present at a level of at least 200 ppm based on weight of aluminum.

  17. Self-Consistent-Field Calculation on Lithium Hydride for Undergraduates.

    ERIC Educational Resources Information Center

    Rioux, Frank; Harriss, Donald K.

    1980-01-01

    Describes a self-consistent-field-linear combination of atomic orbitals-molecular orbital calculation on the valence electrons of lithium hydride using the method of Roothaan. This description is intended for undergraduate physics students.

  18. Thermally unstable hydrides of titanium aluminide Ti3Al

    NASA Astrophysics Data System (ADS)

    Kazantseva, N. V.; Popov, A. G.; Mushnikov, N. V.; Skripov, A. V.; Soloninin, A. V.; Aleksashin, B. A.; Novozhenov, V. I.; Sazonova, V. A.; Kharisova, A. G.

    2011-04-01

    The hydrogen capacity of (Ti, Nb)3Al titanium aluminides subjected to mechanical activation in a hydrogen atmosphere has been studied. It has been shown that the application of this procedure allows one to prepare thermally unstable titanium aluminide (Ti3Al) hydrides with a high hydrogen content (to 2.6 wt %) at room temperature and normal pressure; in this case, no special requirements for the hydrogen purity are placed. The thermally unstable nanostructured Ti3Al hydrides were found to exhibit a higher hydrogen mobility as compared to that of the microcrystalline hydrides. Low niobium additions (to 2.1 at %) have been found to decrease the hydrogen capacity. Experiments on the preparation of bulk samples from the hydride powders obtained were performed.

  19. Life test results of hydride compressors for cryogenic refrigerators

    NASA Astrophysics Data System (ADS)

    Jones, J. A.; Golben, P. M.

    1984-01-01

    A development status assessment is made, from the viewpoint of system durability, for the hydride compressors used in such cryogenic refrigerators as that of the JPL, which has operated at 29 K for 500 hours and at lower temperatures for over 1000. Attention is given to a novel hydride compressor unit which has operated through 35,000 cycles and exhibits negligible degradation of check valves, hydride particle size, and expansion valves. The power requirement for liquid hydrogen cooling can be halved through the use of recuperative hot water heating methods, making this system comparable in power use to liquid hydrogen refrigeration systems operating on electricity. Due to the lack of moving parts in hydride refrigerator designs, potential service lifetimes of many years, and perhaps decades, are being projected.

  20. High-pressure synthesis of noble metal hydrides

    NASA Astrophysics Data System (ADS)

    Donnerer, Christian; Scheler, Thomas; Gregoryanz, Eugene

    2013-04-01

    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.

  1. The development of lightweight hydride alloys based on magnesium

    SciTech Connect

    Guthrie, S.E.; Thomas, G.J.; Yang, N.Y.C.; Bauer, W.

    1996-02-01

    The development of a magnesium based hydride material is explored for use as a lightweight hydrogen storage medium. It is found that the vapor transport of magnesium during hydrogen uptake greatly influences the surface and hydride reactions in these alloys. This is exploited by purposely forming near-surface phases of Mg{sub 2}Ni on bulk Mg-Al-Zn alloys which result in improved hydrogen adsorption and desorption behavior. Conditions were found where these near-surface reactions yielded a complex and heterogeneous microstructure that coincided with excellent bulk hydride behavior. A Mg-Al alloy hydride is reported with near atmospheric plateau pressures at temperatures below 200{degrees}C. Additionally, a scheme is described for low temperature in-situ fabrication of Mg{sub 2}Ni single phase alloys utilizing the high vapor pressure of Mg.

  2. Metal hydrides as negative electrode materials for Ni- MH batteries

    NASA Astrophysics Data System (ADS)

    Yartys, V.; Noreus, D.; Latroche, M.

    2016-01-01

    Structural, thermodynamical and electrochemical properties of metallic hydrides belonging to the pseudo-binary family A-Mg-Ni ( A: rare earths) are reviewed and compared. Technology aspects of bipolar cells are also discussed.

  3. Nonaqueous actinide hydride dissolution and production of actinide $beta$- diketonates

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a hydride of the actinide material in a mixture of carbon tetrachloride and methanol. (auth)

  4. Artificial exomuscle investigations for applications--metal hydride.

    PubMed

    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.

  5. Bipolar Nickel-Metal Hydride Battery Being Developed

    NASA Technical Reports Server (NTRS)

    Manzo, Michelle A.

    1998-01-01

    The NASA Lewis Research Center has contracted with Electro Energy, Inc., to develop a bipolar nickel-metal hydride battery design for energy storage on low-Earth-orbit satellites. The objective of the bipolar nickel-metal hydride battery development program is to approach advanced battery development from a systems level while incorporating technology advances from the lightweight nickel electrode field, hydride development, and design developments from nickel-hydrogen systems. This will result in a low-volume, simplified, less-expensive battery system that is ideal for small spacecraft applications. The goals of the program are to develop a 1-kilowatt, 28-volt (V), bipolar nickel-metal hydride battery with a specific energy of 100 watt-hours per kilogram (W-hr/kg), an energy density of 250 W-hr/liter and a 5-year life in low Earth orbit at 40-percent depth-of-discharge.

  6. High-pressure synthesis of noble metal hydrides.

    PubMed

    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.

  7. Precipitation of hydrides in high purity niobium after different treatments

    SciTech Connect

    Barkov, F.; Romanenko, A.; Trenikhina, Y.; Grassellino, A.

    2013-01-01

    Precipitation of lossy non-superconducting niobium hydrides represents a known problem for high purity niobium in superconducting applications. Using cryogenic optical and laser confocal scanning microscopy we have directly observed surface precipitation and evolution of niobium hydrides in samples after different treatments used for superconducting RF cavities for particle acceleration. Precipitation is shown to occur throughout the sample volume, and the growth of hydrides is well described by the fast diffusion-controlled process in which almost all hydrogen is precipitated at $T=140$~K within $\\sim30$~min. 120$^{\\circ}$C baking and mechanical deformation are found to affect hydride precipitation through their influence on the number of nucleation and trapping centers.

  8. Process for massively hydriding zirconium--uranium fuel elements

    DOEpatents

    Katz, N.H.

    1973-12-01

    A method is described of hydriding uranium-zirconium alloy by heating the alloy in a vacuum, introducing hydrogen and maintaining an elevated temperature until occurrence of the beta--delta phase transformation and isobarically cooling the composition. (Official Gazette)

  9. Hydrogen storage in sodium aluminum hydride.

    SciTech Connect

    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.

  10. Peptide-functionalized luminescent iridium complexes for lifetime imaging of CXCR4 expression.

    PubMed

    Kuil, Joeri; Steunenberg, Peter; Chin, Patrick T K; Oldenburg, Joppe; Jalink, Kees; Velders, Aldrik H; van Leeuwen, Fijs W B

    2011-08-16

    The chemokine receptor 4 (CXCR4) is over-expressed in 23 types of cancer in which it plays a role in, among others, the metastatic spread. For this reason it is a potential biomarker for the field of diagnostic oncology. The antagonistic Ac-TZ14011 peptide, which binds to CXCR4, has been conjugated to luminescent iridium dyes to allow for CXCR4 visualization. The iridium dyes are cyclometalated octahedral iridium(III) 2-phenylpyridine complexes that can be functionalized with one, two or three targeting Ac-TZ14011 peptides. Confocal microscopy and fluorescence lifetime imaging microscopy (FLIM) showed that the peptide-iridium complex conjugates can be used to visualize CXCR4 expression in tumor cells. The CXCR4 receptor affinity and specific cell binding of the mono-, di- and trimeric peptide derivatives were assessed by using flow cytometry. The three derivatives possessed nanomolar receptor affinity and could distinguish between cell lines with different CXCR4 expression levels. This yields the first example of a neutral iridium(III) complex functionalized with peptides for FLIM-based visualization of a cancer associated membrane receptor.

  11. Electrodeposition of platinum-iridium alloy nanowires for hermetic packaging of microelectronics.

    PubMed

    Petrossians, Artin; Whalen, John J; Weiland, James D; Mansfeld, Florian

    2012-01-01

    An electrodeposition technique was applied for fabrication of dense platinum-iridium alloy nanowires as interconnect structures in hermetic microelectronic packaging to be used in implantable devices. Vertically aligned arrays of platinum-iridium alloy nanowires with controllable length and a diameter of about 200 nm were fabricated using a cyclic potential technique from a novel electrodeposition bath in nanoporous aluminum oxide templates. Ti/Au thin films were sputter deposited on one side of the alumina membranes to form a base material for electrodeposition. Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) were used to characterize the morphology and the chemical composition of the nanowires, respectively. SEM micrographs revealed that the electrodeposited nanowires have dense and compact structures. EDS analysis showed a 60:40% platinum-iridium nanowire composition. Deposition rates were estimated by determining nanowire length as a function of deposition time. High Resolution Transmission Electron Microscopy (HRTEM) images revealed that the nanowires have a nanocrystalline structure with grain sizes ranging from 3 nm to 5 nm. Helium leak tests performed using a helium leak detector showed leak rates as low as 1 × 10(-11) mbar L s(-1) indicating that dense nanowires were electrodeposited inside the nanoporous membranes. Comparison of electrical measurements on platinum and platinum-iridium nanowires revealed that platinum-iridium nanowires have improved electrical conductivity.

  12. Luminescent Iridium(III) Complex Labeled DNA for Graphene Oxide-Based Biosensors.

    PubMed

    Zhao, Qingcheng; Zhou, Yuyang; Li, Yingying; Gu, Wei; Zhang, Qi; Liu, Jian

    2016-02-02

    There has been growing interest in utilizing highly photostable iridium(III) complexes as new luminescent probes for biotechnology and life science. Herein, iridium(III) complex with carboxyl group was synthesized and activated with N-hydroxysuccinimide, followed by tagging to the amino terminate of single-stranded DNA (ssDNA). The Ir-ssDNA probe was further combined with graphene oxide (GO) nanosheets to develop a GO-based biosensor for target ssDNA detection. The quenching efficiency of GO, and the photostability of iridium(III) complex and GO-Ir-ssDNA biosensor, were also investigated. On the basis of the high luminescence quenching efficiency of GO toward iridium(III) complex, the GO-Ir-ssDNA biosensor exhibited minimal background signals, while strong emission was observed when Ir-ssDNA desorbed from GO nanosheets and formed a double helix with the specific target, leading to a high signal-to-background ratio. Moreover, it was found that luminescent intensities of iridium(III) complex and GO-Ir-ssDNA biosensor were around 15 and 3 times higher than those of the traditional carboxyl fluorescein (FAM) dye and the GO-FAM-ssDNA biosensor after UV irradiation, respectively. Our study suggested the sensitive and selective Ir-ssDNA probe was suitable for the development of highly photostable GO-based detection platforms, showing promise for application beyond the OLED (organic light emitting diode) area.

  13. Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

    NASA Technical Reports Server (NTRS)

    Jang, Q.; Tuffias, R. H.; Laferla, R.; Ghoniem, N. M.

    1993-01-01

    Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

  14. Meteoric smoke fallout over the Holocene epoch revealed by iridium and platinum in Greenland ice.

    PubMed

    Gabrielli, Paolo; Barbante, Carlo; Plane, John M C; Varga, Anita; Hong, Sungmin; Cozzi, Giulio; Gaspari, Vania; Planchon, Frédéric A M; Cairns, Warren; Ferrari, Christophe; Crutzen, Paul; Cescon, Paolo; Boutron, Claude F

    2004-12-23

    An iridium anomaly at the Cretaceous/Tertiary boundary layer has been attributed to an extraterrestrial body that struck the Earth some 65 million years ago. It has been suggested that, during this event, the carrier of iridium was probably a micrometre-sized silicate-enclosed aggregate or the nanophase material of the vaporized impactor. But the fate of platinum-group elements (such as iridium) that regularly enter the atmosphere via ablating meteoroids remains largely unknown. Here we report a record of iridium and platinum fluxes on a climatic-cycle timescale, back to 128,000 years ago, from a Greenland ice core. We find that unexpectedly constant fallout of extraterrestrial matter to Greenland occurred during the Holocene, whereas a greatly enhanced input of terrestrial iridium and platinum masked the cosmic flux in the dust-laden atmosphere of the last glacial age. We suggest that nanometre-sized meteoric smoke particles, formed from the recondensation of ablated meteoroids in the atmosphere at altitudes >70 kilometres, are transported into the winter polar vortices by the mesospheric meridional circulation and are preferentially deposited in the polar ice caps. This implies an average global fallout of 14 +/- 5 kilotons per year of meteoric smoke during the Holocene.

  15. Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

    NASA Astrophysics Data System (ADS)

    Jang, Q.; Tuffias, R. H.; Laferla, R.; Ghoniem, N. M.

    1993-11-01

    Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

  16. Ab-Initio Study of the Group 2 Hydride Anions

    NASA Astrophysics Data System (ADS)

    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)

  17. Method of selective reduction of polyhalosilanes with alkyltin hydrides

    DOEpatents

    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.

  18. Development of the Low-Pressure Hydride/Dehydride Process

    SciTech Connect

    Rueben L. Gutierrez

    2001-04-01

    The low-pressure hydride/dehydride process was developed from the need to recover thin-film coatings of plutonium metal from the inner walls of an isotope separation chamber located at Los Alamos and to improve the safety operation of a hydride recovery process using hydrogen at a pressure of 0.7 atm at Rocky Flats. This process is now the heart of the Advanced Recovery and Integrated Extraction System (ARIES) project.

  19. Efficient asymmetric transfer hydrogenation of ketones in ethanol with chiral iridium complexes of spiroPAP ligands as catalysts.

    PubMed

    Liu, Wei-Peng; Yuan, Ming-Lei; Yang, Xiao-Hui; Li, Ke; Xie, Jian-Hua; Zhou, Qi-Lin

    2015-04-11

    Highly efficient iridium catalyzed asymmetric transfer hydrogenation of simple ketones with ethanol as a hydrogen donor has been developed. By using chiral spiro iridium catalysts (S)- a series of alkyl aryl ketones were hydrogenated to chiral alcohols with up to 98% ee.

  20. Tellurium Hydrides at High Pressures: High-Temperature Superconductors

    NASA Astrophysics Data System (ADS)

    Zhong, Xin; Wang, Hui; Zhang, Jurong; Liu, Hanyu; Zhang, Shoutao; Song, Hai-Feng; Yang, Guochun; Zhang, Lijun; Ma, Yanming

    2016-02-01

    Observation of high-temperature superconductivity in compressed sulfur hydrides has generated an irresistible wave of searches for new hydrogen-containing superconductors. We herein report the prediction of high-Tc superconductivity in tellurium hydrides stabilized at megabar pressures identified by first-principles calculations in combination with a swarm structure search. Although tellurium is isoelectronic to sulfur or selenium, its heavier atomic mass and weaker electronegativity makes tellurium hydrides fundamentally distinct from sulfur or selenium hydrides in stoichiometries, structures, and chemical bondings. We identify three metallic stoichiometries of H4Te , H5Te2 , and HTe3 , which are not predicted or known stable structures for sulfur or selenium hydrides. The two hydrogen-rich H4Te and H5Te2 phases are primarily ionic and contain exotic quasimolecular H2 and linear H3 units, respectively. Their high-Tc (e.g., 104 K for H4Te at 170 GPa) superconductivity originates from the strong electron-phonon couplings associated with intermediate-frequency H-derived wagging and bending modes, a superconducting mechanism which differs substantially with those in sulfur or selenium hydrides where the high-frequency H-stretching vibrations make considerable contributions.

  1. Novel fuel cell stack with coupled metal hydride containers

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    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

  3. Effect of niobium additions on initial hydriding kinetics of uranium

    NASA Astrophysics Data System (ADS)

    Li, Ruiwen; Wang, Xiaolin

    2014-06-01

    To study the behavior of hydrogen corrosion at the surface of U, U-2.5 wt%Nb alloy and U-5.7 wt%Nb, a gas-solid reaction system with an in situ microscope was designed. The nucleation and growth of the hydride of the alloy were continuously observed and recorded by a computer. The different characteristics of the hydrides on U metal and U-2.5 wt%Nb showed that the later alloy is more susceptible to hydrogen corrosion than the former. The growth rate of hydride of U-2.5 wt%Nb, calculated by measuring the perimeter of the hydride spots recorded by the in situ microscope, exhibited a reaction temperature dependency in the range of 40-160 °C, for pressure of 0.8 × 105 Pa. An Arrhenius plot for growth rate versus temperature yielded activation energy of 24.34 kJ/mol for the hydriding of U-2.5 wt%Nb alloy. The maximum hydriding rate was obtained at 125 °C, whose thermodynamics reason was discussed.

  4. High Strain Rate Tensile Testing of DOP-26 Iridium

    SciTech Connect

    Schneibel, Joachim H; Carmichael Jr, Cecil Albert; George, Easo P

    2007-11-01

    The iridium alloy DOP-26 was developed through the Radioisotope Power Systems Program in the Office of Nuclear Energy of the Department of Energy. It is used for clad vent set cups containing radioactive fuel in radioisotope thermoelectric generator (RTG) heat sources which provide electric power for spacecraft. This report describes mechanical testing results for DOP-26. Specimens were given a vacuum recrystallization anneal of 1 hour at 1375 C and tested in tension in orientations parallel and perpendicular to the rolling direction of the sheet from which they were fabricated. The tests were performed at temperatures ranging from room temperature to 1090 C and strain rates ranging from 1 x 10{sup -3} to 50 s{sup -1}. Room temperature testing was performed in air, while testing at elevated temperatures was performed in a vacuum better than 1 x 10{sup -4} Torr. The yield stress (YS) and the ultimate tensile stress (UTS) decreased with increasing temperature and increased with increasing strain rate. Between 600 and 1090 C, the ductility showed a slight increase with increasing temperature. Within the scatter of the data, the ductility did not depend on the strain rate. The reduction in area (RA), on the other hand, decreased with increasing strain rate. The YS and UTS values did not differ significantly for the longitudinal and transverse specimens. The ductility and RA values of the transverse specimens were marginally lower than those of the longitudinal specimens.

  5. Phosphorescent sensor for phosphorylated peptides based on an iridium complex.

    PubMed

    Kang, Jung Hyun; Kim, Hee Jin; Kwon, Tae-Hyuk; Hong, Jong-In

    2014-07-03

    A bis[(4,6-difluorophenyl)pyridinato-N,C(2')]iridium(III) picolinate (FIrpic) derivative coupled with bis(Zn(2+)-dipicolylamine) (ZnDPA) was developed as a sensor (1) for phosphorylated peptides, which are related to many cellular mechanisms. As a control, a fluorescent sensor (2) based on anthracene coupled to ZnDPA was also prepared. When the total negative charge on the phosphorylated peptides was changed to -2, -4, and -6, the emission intensity of sensor 1 gradually increased by factors of up to 7, 11, and 16, respectively. In contrast, there was little change in the emission intensity of sensor 1 upon the addition of a neutral phosphorylated peptide, non-phosphorylated peptides, or various anions such as CO3(2-), NO3(-), SO4(2-), phosphate, azide, and pyrophosphate. Furthermore, sensor 1 could be used to visually discriminate between phosphorylated peptides and adenosine triphosphate in aqueous solution under a UV-vis lamp, unlike fluorescent sensor 2. This enhanced luminance of phosphorescent sensor 1 upon binding to a phosphorylated peptide is attributed to a reduction in the repulsion between the Zn(2+) ions due to the phenoxy anion, its strong metal-to-ligand charge transfer character, and a reduction in self-quenching.

  6. High-Temperature Oxidation Behavior of Iridium-Rhenium Alloys

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.

    1995-01-01

    The life-limiting mechanism for radiation-cooled rockets made from iridium-coated rhenium (Ir/Re) is the diffusion of Re into the Ir layer and the subsequent oxidation of the resulting Ir-Re alloy from the inner surface. In a previous study, a life model for Ir/Re rockets was developed. It incorporated Ir-Re diffusion and oxidation data to predict chamber lifetimes as a function of temperature and oxygen partial pressure. Oxidation testing at 1540 deg C suggested that a 20-wt percent Re concentration at the inner wall surface should be established as the failure criterion. The present study was performed to better define Ir-oxidation behavior as a function of Re concentration and to supplement the data base for the life model. Samples ranging from pure Ir to Ir-40 wt percent Re (Ir-40Re) were tested at 1500 deg C, in two different oxygen environments. There were indications that the oxidation rate of the Ir-Re alloy increased significantly when it went from a single-phase solid solution to a two-phase mixture, as was suggested in previous work. However, because of testing anomalies in this study, there were not enough dependable oxidation data to definitively raise the Ir/Re rocket failure criterion from 20-wt percent Re to a Re concentration corresponding to entry into the two-phase region.

  7. Iridium profiles and delivery across the Cretaceous/Paleogene boundary

    NASA Astrophysics Data System (ADS)

    Esmeray-Senlet, Selen; Miller, Kenneth G.; Sherrell, Robert M.; Senlet, Turgay; Vellekoop, Johan; Brinkhuis, Henk

    2017-01-01

    We examined iridium (Ir) anomalies at the Cretaceous/Paleogene (K/Pg) boundary in siliciclastic shallow marine cores of the New Jersey Coastal Plain, USA, that were deposited at an intermediate distance (∼2500 km) from the Chicxulub, Mexico crater. Although closely spaced and generally biostratigraphically complete, the cores show heterogeneity in terms of preservation of the ejecta layers, maximum concentration of Ir measured (∼0.1-2.4 ppb), and total thickness of the Ir-enriched interval (11-119 cm). We analyzed the shape of the Ir profiles with a Lagrangian particle-tracking model of sediment mixing. Fits between the mixing model and measured Ir profiles, as well as visible burrows in the cores, show that the shape of the Ir profiles was determined primarily by sediment mixing via bioturbation. In contrast, Tighe Park 1 and Bass River cores show post-depositional remobilization of Ir by geochemical processes. There is a strong inverse relationship between the maximum concentration of Ir measured and the thickness of the sediments over which Ir is spread. We show that the depth-integrated Ir inventory is similar in the majority of the cores, indicating that the total Ir delivery at time of the K/Pg event was spatially homogeneous over this region. Though delivered through a near-instantaneous source, stratospheric dispersal, and settling, our study shows that non-uniform Ir profiles develop due to changes in the regional delivery and post-depositional modification by bioturbation and geochemical processes.

  8. Earth's Radiation Imbalance from a Constellation of 66 Iridium Satellites

    NASA Astrophysics Data System (ADS)

    Chiu, J. C.; Wiscombe, W. J.

    2012-04-01

    The Earth Radiation Imbalance (ERI) at the top of the atmosphere is the primary driving force for climate change. If ERI is not zero, then Earth's temperature, both oceanic and atmospheric, will change gradually over time, tending toward a new steady state. The best estimates of current ERI from climate models range from 0.4 to 0.9 W/m2 (the imbalance being caused mainly by increasing CO2), but current satellite systems do not have the accuracy to measure ERI to even one significant digit. In this paper, we will describe a proposed constellation of 66 Earth radiation budget instruments, to be hosted on Iridium satellites. This system represents a quantum leap over current systems in several ways, in particular in providing ERI to at least one significant digit, thus enabling a crucial test of climate models. Because of its 24/7 coverage, the system will also provide ERI at three-hourly time scales without requiring extrapolations from narrowband geostationary instruments. This would allow studies of ERI's response to fast-evolving phenomena like dust storms and hurricanes. This offers a new, synoptic view of Earth radiation budget that will transform it from a monthly average into a dynamical variable alongside standard meteorological variables like temperature and pressure.

  9. Mono- and dinuclear cationic iridium(III) complexes bearing a 2,5-dipyridylpyrazine (2,5-dpp) ligand.

    PubMed

    Donato, Loïc; McCusker, Catherine E; Castellano, Felix N; Zysman-Colman, Eli

    2013-08-05

    The synthesis, X-ray structures, photophysical, and electrochemical characterization of mono- (1) and dinuclear (2) cationic iridium(III) complexes bearing a 2,5-dipyridylpyrazine (2,5-dpp) ancillary ligand are reported. Upon the complexation of a first equivalent of iridium, the photoluminescence shifts markedly into the deep red (λem = 710 nm, ΦPL = 0.9%) compared to other cationic iridium complexes such as [Ir(ppy)2(bpy)]PF6. With the coordination of a second equivalent of iridium, room temperature luminescence is completely quenched. Both 1 and 2 are luminescent at low temperatures but with distinct excited state decay kinetics; the emission of 2 is significantly red-shifted compared to 1. Emission both at 298 and 77 K results from a mixed charge-transfer state. Density functional theory (DFT) calculations and electrochemical behavior point to an electronic communication between the two iridium complexes.

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

    PubMed

    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.

  11. Reforming catalyst of separate platinum-containing and iridium-containing particles

    SciTech Connect

    Schoennagel, H.J.

    1981-04-21

    Catalyst compositions are provided comprising a refractory support, about 0.1 to about 2 percent by weight of platinum, about 0.1 to about 2 percent by weight of iridium and about 0.1 to about 5 weight percent of halogen where the platinum and iridium are contained on separate particles of said support. The relative weight ratio of the particles containing platinum and those containing iridium is between about 10:1 to about 1:10. The compositions are useful as hydrocarbon conversion catalysts and are especially applicable for use in catalyzing the reforming of naphtha petroleum fractions. There is also disclosed a reforming process conducted in the presence of hydrogen, under reforming conditions, in the presence of the above catalyst.

  12. Properties of mixed molybdenum oxide iridium oxide thin films synthesized by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Patil, P. S.; Kawar, R. K.; Sadale, S. B.; Inamdar, A. I.; Deshmukh, H. P.

    2006-09-01

    Molybdenum-doped iridium oxide thin films have been deposited onto corning glass- and fluorine-doped tin oxide coated corning glass substrates at 350 °C by using a pneumatic spray pyrolysis technique. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride solution in different volume proportions and the resultant solution was used as a precursor solution for spraying. The as-deposited samples were annealed at 600 °C in air medium for 1 h. The structural, electrical and optical properties of as-deposited and annealed Mo-doped iridium oxide were studied and values of room temperature electrical resistivity, and thermoelectric power were estimated. The as-deposited samples with 2% Mo doping exhibit more pronounced electrochromism than other samples, including pristine Ir oxide.

  13. Identification of an iridium(III) complex with anti-bacterial and anti-cancer activity.

    PubMed

    Lu, Lihua; Liu, Li-juan; Chao, Wei-chieh; Zhong, Hai-Jing; Wang, Modi; Chen, Xiu-Ping; Lu, Jin-Jian; Li, Ruei-nian; Ma, Dik-Lung; Leung, Chung-Hang

    2015-09-29

    Group 9 transition metal complexes have been widely explored as therapeutic agents due to their unique geometry, their propensity to undergo ligand exchanges with biomolecules and their diverse steric and electronic properties. These metal complexes can offer distinct modes of action in living organisms compared to carbon-based molecules. In this study, we investigated the antimicrobial and anti-proliferative abilities of a series of cyclometallated iridium(III) complexes. The iridium(III) complex 1 inhibited the growth of S. aureus with MIC and MBC values of 3.60 and 7.19 μM, respectively, indicating its potent bactericidal activity. Moreover, complex 1 also exhibited cytotoxicity against a number of cancer cell lines, with particular potency against ovarian, cervical and melanoma cells. This cyclometallated iridium(III) complex is the first example of a substitutionally-inert, Group 9 organometallic compound utilized as a direct and selective inhibitor of S. aureus.

  14. Heterogeneous Catalysis for Water Oxidation by an Iridium Complex Immobilized on Bipyridine-Periodic Mesoporous Organosilica.

    PubMed

    Liu, Xiao; Maegawa, Yoshifumi; Goto, Yasutomo; Hara, Kenji; Inagaki, Shinji

    2016-07-04

    Heterogenization of metal-complex catalysts for water oxidation without loss of their catalytic activity is important for the development of devices simulating photosynthesis. In this study, efficient heterogeneous iridium complexes for water oxidation were prepared using bipyridine-bridged periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand. The BPy-PMO-based iridium catalysts (Ir-BPy-PMO) were prepared by postsynthetic metalation of BPy-PMO and characterized through physicochemical analyses. The Ir-BPy-PMOs showed high catalytic activity for water oxidation. The turnover frequency (TOF) values for Ir-BPy-PMOs were one order of magnitude higher than those of conventional heterogeneous iridium catalysts. The reusability and stability of Ir-BPy-PMO were also examined, and detailed characterization was conducted using powder X-ray diffraction, nitrogen adsorption, (13) C DD MAS NMR spectroscopy, TEM, and XAFS methods.

  15. Preparation of iridium targets by electrodeposition for neutron capture cross section measurements

    DOE PAGES

    Bond, Evelyn M.; Moody, W. Allen; Arnold, Charles; ...

    2016-03-01

    Here, the preparation of 191Ir and 193Ir electrodeposits for neutron capture cross-section measurements at the detector for advanced neutron capture experiments located at the at Los Alamos Neutron Science Center is described. The electrodeposition of iridium in the desired thickness of 0.4–1 mg/cm2 is challenging. Better yields and thicknesses were obtained using electrodeposition from isopropyl alcohol solutions than from ammonium sulfate solutions. 191Ir and 193Ir targets were initially prepared using the standard single-sided electrodeposition cell. Iridium electrodepositions using a double-sided electrodeposition cell were developed and were optimized, resulting in thick, uniform iridium deposits. LA UR 15-22475.

  16. Preparation of iridium targets by electrodeposition for neutron capture cross section measurements

    SciTech Connect

    Bond, Evelyn M.; Moody, W. Allen; Arnold, Charles; Bredeweg, Todd A.; Jandel, Marian; Rusev, Gencho Y.

    2016-03-01

    Here, the preparation of 191Ir and 193Ir electrodeposits for neutron capture cross-section measurements at the detector for advanced neutron capture experiments located at the at Los Alamos Neutron Science Center is described. The electrodeposition of iridium in the desired thickness of 0.4–1 mg/cm2 is challenging. Better yields and thicknesses were obtained using electrodeposition from isopropyl alcohol solutions than from ammonium sulfate solutions. 191Ir and 193Ir targets were initially prepared using the standard single-sided electrodeposition cell. Iridium electrodepositions using a double-sided electrodeposition cell were developed and were optimized, resulting in thick, uniform iridium deposits. LA UR 15-22475.

  17. Identification of an iridium(III) complex with anti-bacterial and anti-cancer activity

    PubMed Central

    Lu, Lihua; Liu, Li-Juan; Chao, Wei-chieh; Zhong, Hai-Jing; Wang, Modi; Chen, Xiu-Ping; Lu, Jin-Jian; Li, Ruei-nian; Ma, Dik-Lung; Leung, Chung-Hang

    2015-01-01

    Group 9 transition metal complexes have been widely explored as therapeutic agents due to their unique geometry, their propensity to undergo ligand exchanges with biomolecules and their diverse steric and electronic properties. These metal complexes can offer distinct modes of action in living organisms compared to carbon-based molecules. In this study, we investigated the antimicrobial and anti-proliferative abilities of a series of cyclometallated iridium(III) complexes. The iridium(III) complex 1 inhibited the growth of S. aureus with MIC and MBC values of 3.60 and 7.19 μM, respectively, indicating its potent bactericidal activity. Moreover, complex 1 also exhibited cytotoxicity against a number of cancer cell lines, with particular potency against ovarian, cervical and melanoma cells. This cyclometallated iridium(III) complex is the first example of a substitutionally-inert, Group 9 organometallic compound utilized as a direct and selective inhibitor of S. aureus. PMID:26416333

  18. Oxygen atom transfer to a half-sandwich iridium complex: clean oxidation yielding a molecular product.

    PubMed

    Turlington, Christopher R; White, Peter S; Brookhart, Maurice; Templeton, Joseph L

    2014-03-12

    The oxidation of [Ir(Cp*)(phpy)(NCAr(F))][B(Ar(F))4] (1; Cp* = η(5)-pentamethylcyclopentadienyl, phpy = 2-phenylene-κC(1')-pyridine-κN, NCAr(F) = 3,5-bis(trifluoromethyl)benzonitrile, B(Ar(F))4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) with the oxygen atom transfer (OAT) reagent 2-tert-butylsulfonyliodosobenzene (sPhIO) yielded a single, molecular product at -40 °C. New Ir(Cp*) complexes with bidentate ligands derived by oxidation of phpy were synthesized to model possible products resulting from oxygen atom insertion into the iridium-carbon and/or iridium-nitrogen bonds of phpy. These new ligands were either cleaved from iridium by water or formed unreactive, phenoxide-bridged iridium dimers. The reactivity of these molecules suggested possible decomposition pathways of Ir(Cp*)-based water oxidation catalysts with bidentate ligands that are susceptible to oxidation. Monitoring the [Ir(Cp*)(phpy)(NCAr(F))](+) oxidation reaction by low-temperature NMR techniques revealed that the reaction involved two separate OAT events. An intermediate was detected, synthesized independently with trapping ligands, and characterized. The first oxidation step involves direct attack of the sPhIO oxidant on the carbon of the coordinated nitrile ligand. Oxygen atom transfer to carbon, followed by insertion into the iridium-carbon bond of phpy, formed a coordinated organic amide. A second oxygen atom transfer generated an unidentified iridium species (the "oxidized complex"). In the presence of triphenylphosphine, the "oxidized complex" proved capable of transferring one oxygen atom to phosphine, generating phosphine oxide and forming an Ir-PPh3 adduct in 92% yield. The final Ir-PPh3 product was fully characterized.

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

    PubMed

    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.

  20. Chemical Hydride Slurry for Hydrogen Production and Storage

    SciTech Connect

    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

  1. Thermocouples of molybdenum and iridium alloys for more stable vacuum-high temperature performance

    NASA Technical Reports Server (NTRS)

    Morris, J. F. (Inventor)

    1978-01-01

    Thermocouples providing stability and performance reliability in systems involving high temperatures and vacuums by employing a bimetallic thermocouple sensor are described. Each metal of the sensor is selected from a group of metals comprising molybdenum and iridium and alloys containing only those two metals. The molybdenum, iridium thermocouple sensor alloys provide bare metal thermocouple sensors having advantageous vapor pressure compatibility and performance characteristics. The compatibility and physical characteristics of the thermocouple sensor alloys result in improved emf, temperature properties and thermocouple hot junction performance.

  2. Selective DNA purine base photooxidation by bis-terdentate iridium(III) polypyridyl and cyclometalated complexes.

    PubMed

    Jacques, Alexandre; Kirsch-De Mesmaeker, Andrée; Elias, Benjamin

    2014-02-03

    Two bis-terdentate iridium(III) complexes with polypyridyl and cyclometalated ligands have been prepared and characterized. Their spectroscopic and electrochemical properties have been studied, and a photophysical scheme addressing their properties is proposed. Different types of excited states have been considered to account for the deactivation processes in each complex. Interestingly, in the presence of mono- or polynucleotides, a photoinduced electron-transfer process from a DNA purine base (i.e., guanine or adenine) to the excited complex is shown through luminescence quenching experiments. For the first time, this work reports evidence for selective DNA purine bases oxidation by excited iridium(III) bis-terdentate complexes.

  3. An Iridium(III) Complex Inhibits JMJD2 Activities and Acts as a Potential Epigenetic Modulator.

    PubMed

    Liu, Li-Juan; Lu, Lihua; Zhong, Hai-Jing; He, Bingyong; Kwong, Daniel W J; Ma, Dik-Lung; Leung, Chung-Hang

    2015-08-27

    A novel iridium(III) complex was synthesized and evaluated for its ability to target JMJD2 enzymatic activity. The iridium(III) complex 1 can inhibit JMJD2 activity and was selective for JMJD2 activity over JARID, JMJD3, and HDAC activities. Moreover, 1 suppressed the trimethylation of the p21 promoter on H3K9me3 and interrupted the JMJD2D-H3K9me3 interactions in human cells, suggesting that it could act as an epigenetic modulator. To our knowledge, 1 represents the first metal-based JMJD2 inhibitor reported in the literature.

  4. New Iridium Complex Coordinated with Tetrathiafulvalene Substituted Triazole-pyridine Ligand: Synthesis, Photophysical and Electrochemical Properties.

    PubMed

    Niu, Zhi-Gang; Xie, Hui; He, Li-Rong; Li, Kai-Xiu; Xia, Qing; Wu, Dong-Min; Li, Gao-Nan

    2016-01-01

    A new iridium(III) complex based on the triazole-pyridine ligand with tetrathiafulvalene unit, [Ir(ppy)2(L)]PF6 (1), has been synthesized and structurally characterized. The absorption spectra, luminescent spectra and electrochemical behaviors of L and 1 have been investigated. Complex 1 is found to be emissive at room temperature with maxima at 481 and 510 nm. The broad and structured emission bands are suggested a mixing of 3LC (3π-π*) and 3CT (3MLCT) excited states. The influence of iridium ion coordination on the redox properties of the TTF has also been investigated by cyclic voltammetry.

  5. High-strain-rate, high-temperature biaxial testing of DOP-26 iridium

    SciTech Connect

    George, T.G.

    1988-05-01

    High-strain-rate biaxial punch tests were performed on DOP-26 (Ir-0.3 wt.% tungsten) iridium-alloy disc given annealing and aging heat treatments. Test temperatures ranged between 600 and 1440/degree/C, and punch velocity was held constant at 45 m/s. Three types of samples were evaluated: Z-batch old-process discs, B-batch old-process discs, and B-batch new-process discs. The results indicate that batch-to-batch variations in ductility are significant and that new-process iridium is slightly more ductile than old-process material. 12 refs., 43 figs., 26 tabs.

  6. Influence of uranium hydride oxidation on uranium metal behaviour

    SciTech Connect

    Patel, N.; Hambley, D.; Clarke, S.A.; Simpson, K.

    2013-07-01

    This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, if sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)

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

    NASA Technical Reports Server (NTRS)

    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.

  8. Fatigue crack growth in lithium hydride

    SciTech Connect

    Healy, T.E.

    1993-09-01

    Subcritical fatigue crack growth, from cyclic tensile loading, was demonstrated in warm pressed Polycrystalline lithium hydride. Experiments were performed with cyclic tension-tension crack opening (mode I) loads applied to a pre-cracked compact type specimen in an argon environment at a temperature of 21C (70F). The fatigue crack growth was found to occur between 7.56 {times} 10{sup {minus}ll} M/cycle (2.98 {times} l0{sup {minus}9} in/cycle) and 2.35 {times} l0{sup {minus}8} m/cycle (9.24{times}10{sup {minus}7} in/cycle) for a range of stress intensity factors between 1.04 MPa{center_dot}{radical}m (0.95 ksi{center_dot}{radical}in) and 1.49 MPa{center_dot}{radical}m (1.36 ksi{center_dot}{radical}in). The rate of fatigue crack growth from cyclic tensile loading was found to be in excess of crack growth from sustained loading at an equivalent stress intensity factor. Furthermore, a fatigue threshold was not evident from the acquired data.

  9. Permeation rates for RTF metal hydride vessels

    SciTech Connect

    Klein, J.E.

    1992-05-21

    Contamination rates have been estimated for the RTF nitrogen heating and cooling system (NH and CS) due to tritium permeation through the walls of metal hydride vessels. Tritium contamination of the NH and CS will be seen shortly after start-up of the RTF with the majority of it coming from the TCAP units. Contamination rates of the NH and CS are estimated to exceed 400 Ci/year after three years of operation and will elevate tritium concentrations in the NH and CS above 6 {times} 10{sup {minus}3} {mu}Ci/cc. To reduce tritium activity in the NH and CS, a stripper or ``getter`` bed may need to be installed in the NH and CS. Increasing the purge rate of nitrogen from the NH and CS is shown to be an impractical method for reducing tritium activity due to the high purge rates required. Stripping of the NH and CS nitrogen in the glove box stripper system will give a temporary lowering of tritium activity in the NH and CS, but tritium activity will return to its previous level in approximately two weeks.

  10. Transition-Metal Hydride Radical Cations.

    PubMed

    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.

  11. Charging efficiency of metal-hydride electrodes

    NASA Astrophysics Data System (ADS)

    Chen, J.; Dou, S. X.; Bradhurst, D.; Liu, H. K.

    The charging efficiencies of MmNi 5, MmNi 4.5Mn 0.5, MmNi 3.8Co 0.7Mn 0.5, ZrV 0.6Ni 1.4, ZrV 0.6Mn 0.4Ni 1.0, ZrV 0.6Mn 0.4Co 0.2Ni 0.8 allay electrodes (Mm = Mischmetal) are investigated in terms of hydrogen evolution. Experiments are conducted to optimize: (i) elemental composition of the MmNi 5 system and Zr-based Laves-phase hydrogen storage alloys; (ii) additive materials, such as cobalt powder, nickel powder, Teflonized carbons, and acetylene black; (iii) the proportion of the additives in the alloy; (iv) the best percentage of the composite additives in the metal-hydride electrodes. The results show that the electrode activation, charging efficiency and high-rate discharge depend greatly on the active materials, as well as the type and the amount of the additives in the electrodes.

  12. Hydrides in Space: Past, Present, and Future

    NASA Astrophysics Data System (ADS)

    Lis, D. C.; Goldsmith, P. F.; Bergin, E. A.; Falgarone, E.; Gerin, M.; Roueff, E.

    2009-12-01

    One of the central questions of modern astrophysics concerns the life cycle of molecules in the Universe—from the diffuse interstellar medium to planetary systems—and the chemical pathways leading from simple atoms and diatomic molecules to complex organic species. In the past two decades, the Caltech Submillimeter Observatory (CSO) has contributed a number of key discoveries on these topics. Light hydrides are of particular interest for astrochemistry, as the basic building blocks of the chemical networks in both diffuse and dense clouds. Ongoing and planned submillimeter wide-field continuum surveys will yield hundreds of potential galactic targets suitable for detailed spectroscopic follow-ups. Recent advances in detector and digital spectrometer technologies promise to truly revolutionize further the field of high-resolution submillimeter spectroscopy and its application to the study of the life cycle of molecules. This will greatly improve our understanding of astrochemistry, astrobiology, the origin of life on Earth, and allow assessing the possibilities of life in other planetary systems.

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

    PubMed

    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(-).

  14. Multidimensional simulations of hydrides during fuel rod lifecycle

    NASA Astrophysics Data System (ADS)

    Stafford, D. S.

    2015-11-01

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

  15. Sodium-based hydrides for thermal energy applications

    NASA Astrophysics Data System (ADS)

    Sheppard, D. A.; Humphries, T. D.; Buckley, C. E.

    2016-04-01

    Concentrating solar-thermal power (CSP) with thermal energy storage (TES) represents an attractive alternative to conventional fossil fuels for base-load power generation. Sodium alanate (NaAlH4) is a well-known sodium-based complex metal hydride but, more recently, high-temperature sodium-based complex metal hydrides have been considered for TES. This review considers the current state of the art for NaH, NaMgH3- x F x , Na-based transition metal hydrides, NaBH4 and Na3AlH6 for TES and heat pumping applications. These metal hydrides have a number of advantages over other classes of heat storage materials such as high thermal energy storage capacity, low volume, relatively low cost and a wide range of operating temperatures (100 °C to more than 650 °C). Potential safety issues associated with the use of high-temperature sodium-based hydrides are also addressed.

  16. Investigation of metal hydride materials as hydrogen reservoirs for metal-hydrogen batteries

    NASA Technical Reports Server (NTRS)

    ONISCHAK

    1976-01-01

    The performance and suitability of various metal hydride materials were examined for use as possible hydrogen storage reservoirs for secondary metal-hydrogen batteries. Lanthanum pentanickel hydride appears as a probable candidate in terms of stable hydrogen supply under feasible thermal conditions. A kinetic model describing the decomposition rate data of the hydride has been developed.

  17. The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction.

    PubMed

    McSkimming, Alex; Colbran, Stephen B

    2013-06-21

    In biological reduction processes the dihydronicotinamides NAD(P)H often transfer hydride to an unsaturated substrate bound within an enzyme active site. In many cases, metal ions in the active site bind, polarize and thereby activate the substrate to direct attack by hydride from NAD(P)H cofactor. This review looks more widely at the metal coordination chemistry of organic donors of hydride ion--organo-hydrides--such as dihydronicotinamides, other dihydropyridines including Hantzsch's ester and dihydroacridine derivatives, those derived from five-membered heterocycles including the benzimidazolines and benzoxazolines, and all-aliphatic hydride donors such as hexadiene and hexadienyl anion derivatives. The hydride donor properties--hydricities--of organo-hydrides and how these are affected by metal ions are discussed. The coordination chemistry of organo-hydrides is critically surveyed and the use of metal-organo-hydride systems in electrochemically-, photochemically- and chemically-driven reductions of unsaturated organic and inorganic (e.g. carbon dioxide) substrates is highlighted. The sustainable electrocatalytic, photochemical or chemical regeneration of organo-hydrides such as NAD(P)H, including for driving enzyme-catalysed reactions, is summarised and opportunities for development are indicated. Finally, new prospects are identified for metal-organo-hydride systems as catalysts for organic transformations involving 'hydride-borrowing' and for sustainable multi-electron reductions of unsaturated organic and inorganic substrates directly driven by electricity or light or by renewable reductants such as formate/formic acid.

  18. Cleavage of ether, ester, and tosylate C(sp3)-O bonds by an iridium complex, initiated by oxidative addition of C-H bonds. Experimental and computational studies.

    PubMed

    Kundu, Sabuj; Choi, Jongwook; Wang, David Y; Choliy, Yuriy; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

    2013-04-03

    A pincer-ligated iridium complex, (PCP)Ir (PCP = κ(3)-C6H3-2,6-[CH2P(t-Bu)2]2), is found to undergo oxidative addition of C(sp(3))-O bonds of methyl esters (CH3-O2CR'), methyl tosylate (CH3-OTs), and certain electron-poor methyl aryl ethers (CH3-OAr). DFT calculations and mechanistic studies indicate that the reactions proceed via oxidative addition of C-H bonds followed by oxygenate migration, rather than by direct C-O addition. Thus, methyl aryl ethers react via addition of the methoxy C-H bond, followed by α-aryloxide migration to give cis-(PCP)Ir(H)(CH2)(OAr), followed by iridium-to-methylidene hydride migration to give (PCP)Ir(CH3)(OAr). Methyl acetate undergoes C-H bond addition at the carbomethoxy group to give (PCP)Ir(H)[κ(2)-CH2OC(O)Me] which then affords (PCP-CH2)Ir(H)(κ(2)-O2CMe) (6-Me) in which the methoxy C-O bond has been cleaved, and the methylene derived from the methoxy group has migrated into the PCP Cipso-Ir bond. Thermolysis of 6-Me ultimately gives (PCP)Ir(CH3)(κ(2)-O2CR), the net product of methoxy group C-O oxidative addition. Reaction of (PCP)Ir with species of the type ROAr, RO2CMe or ROTs, where R possesses β-C-H bonds (e.g., R = ethyl or isopropyl), results in formation of (PCP)Ir(H)(OAr), (PCP)Ir(H)(O2CMe), or (PCP)Ir(H)(OTs), respectively, along with the corresponding olefin or (PCP)Ir(olefin) complex. Like the C-O bond oxidative additions, these reactions also proceed via initial activation of a C-H bond; in this case, C-H addition at the β-position is followed by β-migration of the aryloxide, carboxylate, or tosylate group. Calculations indicate that the β-migration of the carboxylate group proceeds via an unusual six-membered cyclic transition state in which the alkoxy C-O bond is cleaved with no direct participation by the iridium center.

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

    NASA Astrophysics Data System (ADS)

    Zhou, Chengshang

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

  20. Dynamic High-Temperature Tensile Characterization of an Iridium Alloy with Kolsky Tension Bar Techniques

    SciTech Connect

    Song, Bo; Nelson, Kevin; Lipinski, Ronald; Bignell, John; Ulrich, G. B.; George, Easo P.

    2015-05-29

    In this study, conventional Kolsky tension bar techniques were modified to characterize an iridium alloy in tension at elevated strain rates and temperatures. The specimen was heated to elevated temperatures with an induction coil heater before dynamic loading; whereas, a cooling system was applied to keep the bars at room temperature during heating. A preload system was developed to generate a small pretension load in the bar system during heating in order to compensate for the effect of thermal expansion generated in the high-temperature tensile specimen. A laser system was applied to directly measure the displacements at both ends of the tensile specimen in order to calculate the strain in the specimen. A pair of high-sensitivity semiconductor strain gages was used to measure the weak transmitted force due to the low flow stress in the thin specimen at elevated temperatures. The dynamic high-temperature tensile stress–strain curves of a DOP-26 iridium alloy were experimentally obtained at two different strain rates (~1000 and 3000 s-1) and temperatures (~750 and 1030°C). The effects of strain rate and temperature on the tensile stress–strain response of the iridium alloy were determined. Finally, the iridium alloy exhibited high ductility in stress–strain response that strongly depended on strain-rate and temperature.

  1. Dynamic High-Temperature Tensile Characterization of an Iridium Alloy with Kolsky Tension Bar Techniques

    DOE PAGES

    Song, Bo; Nelson, Kevin; Lipinski, Ronald; ...

    2015-05-29

    In this study, conventional Kolsky tension bar techniques were modified to characterize an iridium alloy in tension at elevated strain rates and temperatures. The specimen was heated to elevated temperatures with an induction coil heater before dynamic loading; whereas, a cooling system was applied to keep the bars at room temperature during heating. A preload system was developed to generate a small pretension load in the bar system during heating in order to compensate for the effect of thermal expansion generated in the high-temperature tensile specimen. A laser system was applied to directly measure the displacements at both ends ofmore » the tensile specimen in order to calculate the strain in the specimen. A pair of high-sensitivity semiconductor strain gages was used to measure the weak transmitted force due to the low flow stress in the thin specimen at elevated temperatures. The dynamic high-temperature tensile stress–strain curves of a DOP-26 iridium alloy were experimentally obtained at two different strain rates (~1000 and 3000 s-1) and temperatures (~750 and 1030°C). The effects of strain rate and temperature on the tensile stress–strain response of the iridium alloy were determined. Finally, the iridium alloy exhibited high ductility in stress–strain response that strongly depended on strain-rate and temperature.« less

  2. Optimization and electrochemical characterization of RF-sputtered iridium oxide microelectrodes for electrical stimulation

    NASA Astrophysics Data System (ADS)

    Kang, Xiaoyang; Liu, Jingquan; Tian, Hongchang; Yang, Bin; NuLi, Yanna; Yang, Chunsheng

    2014-02-01

    A reactively sputtered iridium oxide (IrOx) thin film has been developed as electrochemical modification material for microelectrodes to obtain high stability and charge storage capacity (CSC) in functional electrical stimulation. The effect of the oxygen flow and oxygen to argon ratio during sputtering process on the microstructure and electrochemical properties of the IrOx film is characterized. After optimization, the activated IrOx microelectrode shows the highest CSC of 36.15 mC cm-2 at oxygen flow of 25 sccm and oxygen to argon ratio of (2.5:1). Because the deposition process of the reactively sputtered iridium oxide is an exothermic reaction, it is difficult to form film patterning by the lift-off process. The lift-off process was focused on the partially carbonized photoresist (PR) and normal PR. The higher of the carbonization degree of PR reaches, the longer the immersion duration. However, the patterning process of the iridium oxide film becomes feasible when the sputtering pressure is increasing. The experimental results show that the iridium oxide films forms the pattern with the lowest duration of ultrasonic agitation when the deposition pressure is 4.2 Pa and pressure ratio between O2 and Ar pressure is 3:4.

  3. Acylsilanes in Iridium-Catalyzed Directed Amidation Reactions and Formation of Heterocycles via Siloxycarbenes.

    PubMed

    Becker, Peter; Pirwerdjan, Ramona; Bolm, Carsten

    2015-12-14

    Exposing ortho-amido aroylsilanes to visible light or heat leads to cyclization reactions that provide N-heterocyclic compounds via siloxycarbenes as key intermediates. The previously unreported starting materials have been prepared by directed amidations of aromatic acylsilanes in the presence of an iridium catalyst followed by N-alkylation.

  4. Single orientation graphene synthesized on iridium thin films grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Dangwal Pandey, A.; Krausert, K.; Franz, D.; Grânäs, E.; Shayduk, R.; Müller, P.; Keller, T. F.; Noei, H.; Vonk, V.; Stierle, A.

    2016-08-01

    Heteroepitaxial iridium thin films were deposited on (0001) sapphire substrates by means of molecular beam epitaxy, and subsequently, one monolayer of graphene was synthesized by chemical vapor deposition. The influence of the growth parameters on the quality of the Ir films, as well as of graphene, was investigated systematically by means of low energy electron diffraction, x-ray reflectivity, x-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. Our study reveals (111) oriented iridium films with high crystalline quality and extremely low surface roughness, on which the formation of large-area epitaxial graphene is achieved. The presence of defects, like dislocations, twins, and 30° rotated domains in the iridium films is also discussed. The coverage of graphene was found to be influenced by the presence of 30° rotated domains in the Ir films. Low iridium deposition rates suppress these rotated domains and an almost complete coverage of graphene was obtained. This synthesis route yields inexpensive, air-stable, and large-area graphene with a well-defined orientation, making it accessible to a wider community of researchers for numerous experiments or applications, including those which use destructive analysis techniques or irreversible processes. Moreover, this approach can be used to tune the structural quality of graphene, allowing a systematic study of the influence of defects in various processes like intercalation below graphene.

  5. Total Synthesis of Cryptocaryol A by Enantioselective Iridium-Catalyzed Alcohol C-H Allylation.

    PubMed

    Perez, Felix; Waldeck, Andrew R; Krische, Michael J

    2016-04-11

    The polyketide natural product cryptocaryol A is prepared in 8 steps via iridium catalyzed enantioselective diol double C-H allylation, which directly generates an acetate-based triketide stereodiad. In 4 previously reported total syntheses, 17-28 steps were required.

  6. Catalytic cleavage of ether C-O bonds by pincer iridium complexes.

    PubMed

    Haibach, Michael C; Lease, Nicholas; Goldman, Alan S

    2014-09-15

    The development of efficient catalytic methods to cleave the relatively unreactive C-O bonds of ethers remains an important challenge in catalysis. Building on our group's recent work, we report the dehydroaryloxylation of aryl alkyl ethers using pincer iridium catalysts. This method represents a rare fully atom-economical method for ether C-O bond cleavage.

  7. Comparative assessment of iridium oxide and platinum alloy wires using an in vitro glial scar assay.

    PubMed

    Ereifej, Evon S; Khan, Saida; Newaz, Golam; Zhang, Jinsheng; Auner, Gregory W; VandeVord, Pamela J

    2013-12-01

    The long-term effect of chronically implanted electrodes is the formation of a glial scar. Therefore, it is imperative to assess the biocompatibility of materials before employing them in neural electrode fabrication. Platinum alloy and iridium oxide have been identified as good candidates as neural electrode biomaterials due to their mechanical and electrical properties, however, effect of glial scar formation for these two materials is lacking. In this study, we applied a glial scarring assay to observe the cellular reactivity to platinum alloy and iridium oxide wires in order to assess the biocompatibility based on previously defined characteristics. Through real-time PCR, immunostaining and imaging techniques, we will advance the understanding of the biocompatibility of these materials. Results of this study demonstrate iridium oxide wires exhibited a more significant reactive response as compared to platinum alloy wires. Cells cultured with platinum alloy wires had less GFAP gene expression, lower average GFAP intensity, and smaller glial scar thickness. Collectively, these results indicated that platinum alloy wires were more biocompatible than the iridium oxide wires.

  8. Iridium-catalyzed regio- and enantioselective allylic substitution of silyl dienolates derived from dioxinones.

    PubMed

    Chen, Ming; Hartwig, John F

    2014-11-03

    Reported herein is the iridium-catalyzed regio- and enantioselective allylic substitution reactions of unstabilized silyl dienolates derived from dioxinones. Asymmetric allylic substitution of a variety of allylic trichloroethyl carbonates with these silyl dienolates gave γ-allylated products selectively in 60-84% yield and 90-98% ee.

  9. Synthesis and luminescence properties of iridium complexes chelated with coumarin ligands.

    PubMed

    Park, Hye Rim; Kim, Bo Young; Kim, Young Kwan; Ha, Yunkyoung

    2013-05-01

    According to a recent report, the organic light-emitting diodes (OLEDs) using the iridium complexes of coumarin derivatives as emissive dopants are highly efficient and stable. Unlike the other Ir(III) phopsphorescent dopants, these coumarin-based Ir(III) complexes can effectively trap and transport electrons in the emissive layer. We have prepared a series of phosphorescent cyclometalated Ir(III) complexes containing 3-(2-pyridinyl)coumarin (pc) as an ancillary ligand. The new heteroleptic iridium complexes, Ir(C--N)2(pc) (CAN = 2-(2,4-difluorophenyl)pyridine (F2-ppy), 2-phenylpyridine (ppy) and 2-phenylquinoline (pq)) were characterized by 1H NMR and mass spectrometer. As main ligands, F2-ppy, ppy and pq were employed, which should have the drastically different ligand molecular orbital energy levels. The iridium complexes showed various emission ranges from 560 to 610 nm, depending upon the relative energy levels of their main and ancillary ligands. The photoabsorption, photoluminescence and electroluminescence of the complexes were studied. We also investigated the electrochemical properties of the iridium complexes to compare the HOMO and LUMO energy levels of these phosphorescent materials.

  10. Theoretical study of structure, stability, and the hydrolysis reactions of small iridium oxide nanoclusters.

    PubMed

    Zhou, Xin; Yang, Jingxiu; Li, Can

    2012-10-11

    The geometric structures and relative stabilities of small iridium oxide nanoclusters, Ir(m)O(n) (m = 1-5 and n = 1-2m), have been systematically investigated using density functional theory (DFT) calculations at the B3LYP level. Our results show that the lowest-energy structures of these clusters can be obtained by the sequential oxidation of small "core" iridium clusters. The iridium-monoxide-like clusters have relatively higher stability because of their relatively high binding energy and second difference in energies. On the basis of the optimized lowest-energy structures of neutral and cationic (IrO(2))(n) (n = 1-5), DFT has been used to study the hydrolysis reaction of these clusters with water molecules. The calculated results show that the addition of water molecules to the cationic species is much easier than the neutral ones. The overall hydrolysis reaction energies are more exothermic for the cationic clusters than for the neutral clusters. Our calculations indicate that H(2)O can be more easily split on the cationic iridium oxide clusters than on the neutral clusters.

  11. A pH Sensor Based on a Stainless Steel Electrode Electrodeposited with Iridium Oxide

    ERIC Educational Resources Information Center

    Martinez, C. C. M.; Madrid, R. E.; Felice, C. J.

    2009-01-01

    A simple procedure to make an iridium oxide (IrO[subscript 2]) electrodeposited pH sensor, that can be used in a chemical, biomedical, or materials laboratory, is presented here. Some exercises, based on this sensor, that can be used to teach important concepts in the field of biomedical, biochemical, tissue, or materials engineering, are also…

  12. Iridium-catalyzed selective α-alkylation of unactivated amides with primary alcohols.

    PubMed

    Guo, Le; Liu, Yinghua; Yao, Wubing; Leng, Xuebing; Huang, Zheng

    2013-03-01

    The first α-alkylation of unactivated amides with primary alcohols is described. An effective and robust iridium pincer complex has been developed for selective α-alkylation of tertiary and secondary acetamides involving a "borrowing hydrogen" methodology. The method is compatible with alcohols bearing various functional groups. This presents a convenient and environmentally benign protocol for α-alkylation of amides.

  13. A monolith immobilised iridium Cp* catalyst for hydrogen transfer reactions under flow conditions.

    PubMed

    Rojo, Maria Victoria; Guetzoyan, Lucie; Baxendale, Ian R

    2015-02-14

    An immobilised iridium hydrogen transfer catalyst has been developed for use in flow based processing by incorporation of a ligand into a porous polymeric monolithic flow reactor. The monolithic construct has been used for several redox reductions demonstrating excellent recyclability, good turnover numbers and high chemical stability giving negligible metal leaching over extended periods of use.

  14. The growth of graphite phase on an iridium field electron emitter

    NASA Astrophysics Data System (ADS)

    Bernatskii, D. P.; Pavlov, V. G.

    2016-06-01

    The growth of graphite on the surface of an iridium tip in pyrolysis of benzene to give a ribbed crystal has been found by the methods of field electron and desorption microscopy. The formation of a graphite crystal results in the electric field factor increasing. The adsorption of alkali metals on the surface of graphite is accompanied by the intercalation effect.

  15. Grazing incidence X-ray reflectivity of gold and iridium coated flat mirrors

    NASA Astrophysics Data System (ADS)

    Aschenbach, Bernd; Braeuninger, Heinrich; Burkert, Wolfgang

    In the context of developing high reflectivity coatings for X-ray telescopes highly polished Zerodur and BK-7 glass flats have been coated with either gold or iridium. Grazing incidence reflectivity measurements at various X-ray energies are reported and compared with standard theory prediction.

  16. High temperature reactive ion etching of iridium thin films with aluminum mask in CF4/O2/Ar plasma

    NASA Astrophysics Data System (ADS)

    Yeh, Chia-Pin; Lisker, Marco; Kalkofen, Bodo; Burte, Edmund P.

    2016-08-01

    Reactive ion etching (RIE) technology for iridium with CF4/O2/Ar gas mixtures and aluminum mask at high temperatures up to 350 °C was developed. The influence of various process parameters such as gas mixing ratio and substrate temperature on the etch rate was studied in order to find optimal process conditions. The surface of the samples after etching was found to be clean under SEM inspection. It was also shown that the etch rate of iridium could be enhanced at higher process temperature and, at the same time, very high etching selectivity between aluminum etching mask and iridium could be achieved.

  17. Testing and evaluation of oxide-coated iridium/rhenium chambers

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.

    1993-01-01

    Iridium-coated rhenium provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase iridium/rhenium rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated iridium/rhenium, 22 N rocket chambers were tested on gaseous hydrogen/gaseous oxygen propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia or zirconia. Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of zirconia infiltrated with sol gel hafnia. The other chamber had a coating composed of an iridium/oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. The iridium/oxide composite coated chamber included testing for over 29 minutes at mixture ratio 16. The thicker-walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner-walled coatings did not experience the macrocracking and chipping of the chambers seen with the thick, monolithic coatings. However, burnthroughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stochiometric. The burn-throughs were probably the result of oxygen-diffusion through the oxide coating that allowed the underlying iridium and rhenium layers to be oxidized. The results of this test program indicated that the thin

  18. A nickel metal hydride battery for electric vehicles.

    PubMed

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

    1993-04-09

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

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

    SciTech Connect

    Jacobs, Benjamin W.; Herberg, Julie L.; Highley, Aaron M.; Grossman, Jeffrey; Wagner, Lucas; Bhakta, Raghu; Peaslee, D.; Allendorf, Mark D.; Liu, X.; Behrens, Richard, Jr.; Majzoub, Eric H.

    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

  20. CO2 hydrogenation on a metal hydride surface.

    PubMed

    Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

    2012-04-28

    The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface.

  1. Metal hydride hydrogen compression: Recent advances and future prospects

    DOE PAGES

    Bowman, Jr., Robert C.; Yartys, Volodymyr A.; Lototskyy, Mykhaylo V.; ...

    2016-03-17

    Metal hydride (MH) thermal sorption compression is one of the more important applications of the metal hydrides. The present paper reviews recent advances in the field based on the analysis of the fundamental principles of this technology. The performances when boosting hydrogen pressure, along with two- and three-step compression units are analyzed. The paper includes also a theoretical modeling of a two-stage compressor aimed at both describing the performance of the experimentally studied systems, but, also, on their optimization and design of more advanced MH compressors. Business developments in the field are reviewed for the Norwegian company HYSTORSYS AS andmore » the South African Institute for Advanced Materials Chemistry. Finally, future prospects are outlined presenting the role of the metal hydride compression in the overall development of the hydrogen driven energy systems. Lastly, the work is based on the analysis of the development of the technology in Europe, USA and South Africa.« less

  2. Metal hydride hydrogen compression: Recent advances and future prospects

    SciTech Connect

    Bowman, Jr., Robert C.; Yartys, Volodymyr A.; Lototskyy, Mykhaylo V.; Linkov, Vladimir; Grant, David; Stuart, Alastair; Eriksen, Jon; Denys, Roman

    2016-03-17

    Metal hydride (MH) thermal sorption compression is one of the more important applications of the metal hydrides. The present paper reviews recent advances in the field based on the analysis of the fundamental principles of this technology. The performances when boosting hydrogen pressure, along with two- and three-step compression units are analyzed. The paper includes also a theoretical modeling of a two-stage compressor aimed at both describing the performance of the experimentally studied systems, but, also, on their optimization and design of more advanced MH compressors. Business developments in the field are reviewed for the Norwegian company HYSTORSYS AS and the South African Institute for Advanced Materials Chemistry. Finally, future prospects are outlined presenting the role of the metal hydride compression in the overall development of the hydrogen driven energy systems. Lastly, the work is based on the analysis of the development of the technology in Europe, USA and South Africa.

  3. Luminescent Iridium(III) Complexes Supported by N-Heterocyclic Carbene-based C^C^C-Pincer Ligands and Aromatic Diimines

    PubMed Central

    Chung, Lai-Hon; Lo, Hoi-Shing; Ng, Sze-Wing; Ma, Dik-Lung; Leung, Chung-Hang; Wong, Chun-Yuen

    2015-01-01

    Iridium(III) hydrido complexes containing N-heterocyclic carbene (NHC)-based pincer ligand 1,3-bis(1-butylimidazolin-2-ylidene)phenyl anion (C1^C^C1) or 1,3-bis(3-butylbenzimidazolin-2-ylidene)phenyl anion (C2^C^C2) and aromatic diimine (2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4′-dimethyl-2,2′-bipyridine (Me2bpy), or dipyrido-[3,2-f:2′,3′-h]-quinoxaline (dpq)) in the form of [Ir(C^C^C)(N^N)(H)]+ have been prepared. Crystal structures for these complexes show that the Ir–CNHC distances are 2.043(5)–2.056(5) Å. The hydride chemical shifts for complexes bearing C1^C^C1 (−20.6 to −20.3 ppm) are more upfield than those with C2^C^C2 (−19.5 and −19.2 ppm), revealing that C1^C^C1 is a better electron donor than C2^C^C2. Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations suggest that the lowest-energy electronic transition associated with these complexes (λ = 340–530 nm (ε ≤ 103 dm3 mol−1 cm−1)) originate from a dπ(IrIII) → π*(N^N) metal-to-ligand charge transfer transition, where the dπ(IrIII) level contain significant contribution from the C^C^C ligands. All these complexes are emissive in the yellow-spectral region (553–604 nm in CH3CN and CH2Cl2) upon photo-excitation with quantum yields of 10−3–10−1. PMID:26487542

  4. Chlorido-containing ruthenium(II) and iridium(III) complexes as antimicrobial agents.

    PubMed

    Pandrala, Mallesh; Li, Fangfei; Feterl, Marshall; Mulyana, Yanyan; Warner, Jeffrey M; Wallace, Lynne; Keene, F Richard; Collins, J Grant

    2013-04-07

    A series of polypyridyl-ruthenium(II) and -iridium(III) complexes that contain labile chlorido ligands, [{M(tpy)Cl}(2){μ-bb(n)}](2/4+) {Cl-Mbb(n); where M = Ru or Ir; tpy = 2,2':6',2''-terpyridine; and bb(n) = bis[4(4'-methyl-2,2'-bipyridyl)]-1,n-alkane (n = 7, 12 or 16)} have been synthesised and their potential as antimicrobial agents examined. The minimum inhibitory concentrations (MIC) and minimum bactericidal concentrations (MBC) of the series of metal complexes against four strains of bacteria - Gram positive Staphylococcus aureus (S. aureus) and methicillin-resistant S. aureus (MRSA), and Gram negative Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa) - have been determined. All the ruthenium complexes were highly active and bactericidal. In particular, the Cl-Rubb(12) complex showed excellent activity against all bacterial cell lines with MIC values of 1 μg mL(-1) against the Gram positive bacteria and 2 and 8 μg mL(-1) against E. coli and P. aeruginosa, respectively. The corresponding iridium(III) complexes also showed significant antimicrobial activity in terms of MIC values; however and surprisingly, the iridium complexes were bacteriostatic rather than bactericidal. The inert iridium(III) complex, [{Ir(phen)(2)}(2){μ-bb(12)}](6+) {where phen = 1,10-phenanthroline) exhibited no antimicrobial activity, suggesting that it could not cross the bacterial membrane. The mononuclear model complex, [Ir(tpy)(Me(2)bpy)Cl]Cl(2) (where Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine), was found to aquate very rapidly, with the pK(a) of the iridium-bound water in the corresponding aqua complex determined to be 6.0. This suggests the dinuclear complexes [Ir(tpy)Cl}(2){μ-bb(n)}](4+) aquate and deprotonate rapidly and enter the bacterial cells as 4+ charged hydroxo species.

  5. Water reduction systems associated with homoleptic cyclometalated iridium complexes of various 2-phenylpyridines.

    PubMed

    Yuan, Yong-Jun; Yu, Zhen-Tao; Cai, Jian-Guang; Zheng, Chao; Huang, Wei; Zou, Zhi-Gang

    2013-08-01

    The photoreduction of water to hydrogen represents a promising method for generating sustainable clean fuel. The molecular processes of this photoreduction require an effective light absorber, such as the ruthenium polybipyridine complex, to collect and convert the solar energy into a usable chemical form. In the search for a highly active and stable photosensitizer (PS), iridium complexes are attractive because of their desirable photophysical characteristics. Herein, a series of homoleptic tris-cyclometalated iridium complexes, based on different 2-phenylpyridine ligands, were utilized as PSs in photocatalytic systems for hydrogen production with [Rh(dtb-bpy)3 ](PF6 )3 (dtb-bpy=4,4'-di-tert-butyl-2,2'-dipyridyl) serving as the water reduction catalyst (WRC) and triethanolamine (TEOA) as the electron donor. The photophysical and electrochemical properties of these complexes were systematically investigated. The excited state of neutral iridium complexes (PS*) could not be quenched by using TEOA as an electron donor, but they could be quenched by using [Rh(dtb-bpy)3 ](PF6 )3 as an electron acceptor, indicating that the PS* quenching pathway in catalytic reactions was most likely an oxidative quenching process. A set of long-lived and highly active systems for hydrogen evolution were obtained in Ir(III) -Rh(III) -TEOA systems. These systems maintained their activity for more than 72 h with visible-light irradiation, and the total turnover number was up to 3040. Comparative studies indicated that the photocatalytic performance of these homoleptic tris-cyclometalated iridium compounds was superior to that of the cationic iridium complex [Ir(ppy)2 (bpy)](PF6 ) (ppy=2-phenylpyridine, bpy=2,2'-dipyridyl) (4), which was used as a reference. The significant increase in the photocatalytic efficiencies was in part attributed to the higher photostability of the neutral Ir(III) complexes. This assumption was supported by their different coordination modes, photophysical, and

  6. Iridium and Spherules in Late Eocene Impact Deposits

    NASA Technical Reports Server (NTRS)

    Kyte, F. T.; Liu, S.

    2002-01-01

    We have been independently examining the Ir (FTK) and spherule (SL) contents of recently discovered late Eocene impact deposits from the south Atlantic and western Indian oceans. These include ODP Sites 1090 [14,15], 709 [lo], and 699 [Liu in prep.]. Iridium abundances at these sites are within the typical range reported for late Eocene deposits, with peak concentrations between 100 and 1000 pg/g. In Table 1 we present estimated net Ir fluences (in ng Ir/cm ) for these and nine other sites. Although there are fewer sites than the K/T boundary, the average of 9 ng Ir/cm2 is probably a good estimate of the late Eocene global flux. This is enough Ir for a 6 km comet (assuming 250 ng/g Ir, p=1.5), is sufficient to produce the Popigai or Chesapeake Bay structures, and is 16% of the flux estimated for the K/T boundary (55 ng/cm2 [ 161). Figure 1 shows the relative abundances of Ir, glassy microtektites and cpx-bearing spherules in sediments from Sites 699 and 1090, which are separated by only 3100 km. Although these two sites have similar Ir anomalies, the abundances of spherules are quite different. Site 1090 has well-defined peaks for both types of spherules, with a peak of 562 cpx spheruledg, while Site 699 contains only a few glassy microtektites and no cpx spherules. While the different abundances of spherules may reflect a heterogeneous distribution of spherules on the Earth s surface, an equally likely cause of this difference may be differential preservation of spherules in the sediment. recovered are only a trace residue of the initial impact deposit. Earlier work found 0.22 ng/g Ir in glassy microtektites from Site 689 [17], an insufficient concentration to support 0.16 ng/g in the bulk sediment at this site. We measured 15 ng/g Ir in a group of 95 cpx spherules from Site 1090 with sizes from 63 to -200 pm, a set typical of the size distribution at this site. Although this is a significant concentration it also cannot support the Ir peak. We presently lack

  7. Testing of electroformed deposited iridium/powder metallurgy rhenium rockets

    NASA Technical Reports Server (NTRS)

    Reed, Brian D.; Dickerson, Robert

    1996-01-01

    High-temperature, oxidation-resistant chamber materials offer the thermal margin for high performance and extended lifetimes for radiation-cooled rockets. Rhenium (Re) coated with iridium (Ir) allow hours of operation at 2200 C on Earth-storable propellants. One process for manufacturing Ir/Re rocket chambers is the fabrication of Re substrates by powder metallurgy (PM) and the application of Ir coatings by using electroformed deposition (ED). ED Ir coatings, however, have been found to be porous and poorly adherent. The integrity of ED Ir coatings could be improved by densification after the electroforming process. This report summarizes the testing of two 22-N, ED Ir/PM Re rocket chambers that were subjected to post-deposition treatments in an effort to densify the Ir coating. One chamber was vacuum annealed, while the other chamber was subjected to hot isostatic pressure (HIP). The chambers were tested on gaseous oxygen/gaseous hydrogen propellants, at mixture ratios that simulated the oxidizing environments of Earth-storable propellants. ne annealed ED Ir/PM Re chamber was tested for a total of 24 firings and 4.58 hr at a mixture ratio of 4.2. After only 9 firings, the annealed ED Ir coating began to blister and spall upstream of the throat. The blistering and spalling were similar to what had been experienced with unannealed, as-deposited ED Ir coatings. The HIP ED Ir/PM Re chamber was tested for a total of 91 firings and 11.45 hr at mixture ratios of 3.2 and 4.2. The HIP ED Ir coating remained adherent to the Re substrate throughout testing; there were no visible signs of coating degradation. Metallography revealed, however, thinning of the HIP Ir coating and occasional pores in the Re layer upstream of the throat. Pinholes in the Ir coating may have provided a path for oxidation of the Re substrate at these locations. The HIP ED Ir coating proved to be more effective than vacuum annealed and as-deposited ED Ir. Further densification is still required to

  8. High-Spin Cobalt Hydrides for Catalysis

    SciTech Connect

    Holland, Patrick L.

    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.

  9. Method for preparing hydride configurations and reactive metal surfaces

    DOEpatents

    Silver, G.L.

    1984-05-18

    A method for preparing reactive metal surfaces, particularly uranium surfaces is disclosed, whereby the metal is immediately reactive to hydrogen gas at room temperature and low pressure. The metal surfaces are first pretreated by exposure to an acid which forms an adherent hydride-bearing composition on the metal surface. Subsequent heating of the pretreated metal at a temperature sufficient to decompose the hydride coating in vacuum or inert gas renders the metal surface instantaneously reactive to hydrogen gas at room temperature and low pressure.

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

    SciTech Connect

    Gschneidner, K. A.; Schmidt, F. A.; Frerichs, A. E.; Ament, K. A.

    2013-08-20

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

  11. Hydride formation in core-shell alloyed metal nanoparticles

    NASA Astrophysics Data System (ADS)

    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.

  12. METHOD OF PREPARING SINTERED ZIRCONIUM METAL FROM ITS HYDRIDES

    DOEpatents

    Angier, R.P.

    1958-02-11

    The invention relates to the preparation of metal shapes from zirconium hydride by powder metallurgical techniques. The zirconium hydride powder which is to be used for this purpose can be prepared by rendering massive pieces of crystal bar zirconium friable by heat treatment in purified hydrogen. This any then be ground into powder and powder can be handled in the air without danger of it igniting. It may then be compacted in the normal manner by being piaced in a die. The compact is sintered under vacuum conditions preferably at a temperature ranging from 1200 to 1300 deg C and for periods of one to three hours.

  13. Ab-initio study of transition metal hydrides

    SciTech Connect

    Sharma, Ramesh; Shukla, Seema Dwivedi, Shalini Sharma, Yamini

    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.

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

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Mohammadian-Sabet, Fariba

    2016-06-01

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

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

    SciTech Connect

    Hill, Mary Ann; Richards, Andrew Walter; Holby, Edward F.; Schulze, Roland K.

    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.

  16. Green chemiluminescence from a bis-cyclometalated iridium(III) complex with an ancillary bathophenanthroline disulfonate ligand.

    PubMed

    Zammit, Elizabeth M; Barnett, Neil W; Henderson, Luke C; Dyson, Gail A; Zhou, Ming; Francis, Paul S

    2011-08-07

    The reaction of a fluorinated iridium complex with cerium(IV) and organic reducing agents generates an intense emission with a significant hypsochromic shift compared to contemporary chemically-initiated luminescence from metal complexes.

  17. Determination of surface coverage of catalysts: Temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

    SciTech Connect

    Broek, A.C.M. van den; Grondelle, J. van; Santen, R.A. van

    1999-07-25

    The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity measurements that both catalysts lose activity as a function of time on stream due to inhibition of the surface by reaction intermediates. The used catalysts were studied by XPS and temperature programmed techniques. It was found that the surface of the catalysts had a high coverage of NH and OH and some additional NH{sub 2}. It seems most likely that the reaction mechanism proceeds through a stepwise dehydrogenation of the ammonia molecule. It appears that the last dehydrogenation step (NH by OH to N and water) is the rate determining step. The high selectivity of iridium to nitrogen can be explained by the higher activity of iridium in dissociating NO.

  18. Heat-mass flow enhancement system for a metal hydride assembly

    NASA Astrophysics Data System (ADS)

    Argabright, T. A.

    1985-02-01

    Southern California Gas Company and Solar Turbines Incorporated are cooperating in the development and demonstration of a metal hydride/chemical heat pump (MHHP). In the design of the MHHP, heat transfer was considered to be the key technical study area. The goal of this effort is improved heat transfer and reduced thermal mass in a hydride heat exchanger/containment assembly. Phase 1 resulted in the detailed design of an advanced hydride heat exchanger. Phase 2 consisted of the experimental verification of the hydride alloy design data, fabrication of the hydride heat exchanger module components, heat transfer testing of the single heat exchanger element and preliminary performance testing of the entire module. Phase 3 was devoted to the complete characterization of the hydride heat exchanger modules through further operation and testing. A review of other possible hydride heat transfer concepts was also conducted in Phase 2.

  19. Highly active iridium/iridium-tin/tin oxide heterogeneous nanoparticles as alternative electrocatalysts for the ethanol oxidation reaction.

    PubMed

    Du, Wenxin; Wang, Qi; Saxner, David; Deskins, N Aaron; Su, Dong; Krzanowski, James E; Frenkel, Anatoly I; Teng, Xiaowei

    2011-09-28

    Ethanol is a promising fuel for low-temperature direct fuel cell reactions due to its low toxicity, ease of storage and transportation, high-energy density, and availability from biomass. However, the implementation of ethanol fuel cell technology has been hindered by the lack of low-cost, highly active anode catalysts. In this paper, we have studied Iridium (Ir)-based binary catalysts as low-cost alternative electrocatalysts replacing platinum (Pt)-based catalysts for the direct ethanol fuel cell (DEFC) reaction. We report the synthesis of carbon supported Ir(71)Sn(29) catalysts with an average diameter of 2.7 ± 0.6 nm through a "surfactant-free" wet chemistry approach. The complementary characterization techniques, including aberration-corrected scanning transmission electron microscopy equipped with electron energy loss spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy, are used to identify the "real" heterogeneous structure of Ir(71)Sn(29)/C particles as Ir/Ir-Sn/SnO(2), which consists of an Ir-rich core and an Ir-Sn alloy shell with SnO(2) present on the surface. The Ir(71)Sn(29)/C heterogeneous catalyst exhibited high electrochemical activity toward the ethanol oxidation reaction compared to the commercial Pt/C (ETEK), PtRu/C (Johnson Matthey) as well as PtSn/C catalysts. Electrochemical measurements and density functional theory calculations demonstrate that the superior electro-activity is directly related to the high degree of Ir-Sn alloy formation as well as the existence of nonalloyed SnO(2) on surface. Our cross-disciplinary work, from novel "surfactant-free" synthesis of Ir-Sn catalysts, theoretical simulations, and catalytic measurements to the characterizations of "real" heterogeneous nanostructures, will not only highlight the intriguing structure-property correlations in nanosized catalysts but also have a transformative impact on the commercialization of DEFC technology by replacing Pt with low

  20. Hydride vapor phase epitaxy of aluminum nitride

    NASA Astrophysics Data System (ADS)

    Kamber, Derrick Shane

    AlN is a promising substrate material for AlGaN-based UV optoelectronic devices and high-power, high-frequency electronic devices. Since large-area bulk AlN crystals are not readily available, one approach to prepare AlN substrates is to heteroepitaxially deposit thick (e.g., 10-300+ mum) AlN layers by hydride vapor phase epitaxy. Initial efforts focused on growing AlN layers on sapphire substrates with growth rates up to 75 mum/hr. The resulting layers were colorless, smooth, and specular. Subsurface cracking, attributed to the plastic relief of tensile strain from island coalescence, was observed but did not adversely affect the surface morphology of the AlN layers. The surfaces possessed rms roughnesses as low as 0.316 nm over 5 x 5 mum2 sampling areas, but hexagonal hillock formation was observed for thick films grown at high growth rates. TEM revealed that the threading dislocation (TD) density of the films was 2 x 109 cm-2. The high TD densities for direct growth of AlN films on foreign substrates motivated the development of lateral epitaxial overgrowth approaches for defect reduction. Growth of AlN layers on patterned SiC substrates produced coalesced AlN films possessing TD densities below 8.3 x 106 cm -2 in the laterally grown wing regions, as compared to 1.8 x 109 cm-2 in the seed regions. These films, however, cracked on cooldown due to the difference in thermal expansion coefficients for AlN and SiC. To avoid this cracking, AlN layers were grown on patterned sapphire substrates. Although the films were able to be coalesced and contained few or no cracks, the TDs in these films were not confined to the seed regions. This produced a relatively uniform distribution of TDs over the surfaces of the films, with only a modest reduction in the TD density of 1 x 10 8 cm-2. Selective area growth of AlN was also pursued using Si3N4, SiO2, and Ti masks. Growth selectivity and film coalescence was observed for films grown on each masking material, but none of the

  1. KNH2-KH: a metal amide-hydride solid solution.

    PubMed

    Santoru, Antonio; Pistidda, Claudio; Sørby, Magnus H; Chierotti, Michele R; Garroni, Sebastiano; Pinatel, Eugenio; Karimi, Fahim; Cao, Hujun; Bergemann, Nils; Le, Thi T; Puszkiel, Julián; Gobetto, Roberto; Baricco, Marcello; Hauback, Bjørn C; Klassen, Thomas; Dornheim, Martin

    2016-09-27

    We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2(-) ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

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

    DOEpatents

    Congdon, James W.

    2009-03-17

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

  3. Cascades for hydrogen isotope separation using metal hydrides

    SciTech Connect

    Hill, F.B.; Grzetic, V.

    1982-01-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes.

  4. Electronic Principles of Some Trends in Properties of Metallic Hydrides

    NASA Astrophysics Data System (ADS)

    Ivanović, Nenad; Novaković, Nikola; Colognesi, Daniele; Radisavljević, Ivana; Ostojić, Stanko

    Due to their extensive present, important and versatile potential applications, metal hydrides (MH) are among the most investigated solid-state systems. Theoretical, numerical and experimental studies have provided a considerable knowledge about their structure and properties, but in spite of that, the basic electronic principles of various interactions present in MH have not yet been completely resolved. Even in the simplest MH, i.e. alkali hydrides (Alk-H), some trends in physical properties, and especially their deviations, are not well understood. Similar doubts exist for the alkaline-earth hydride (AlkE-H) series, and are even more pronounced for complex systems, like transition metal-doped AlkE-H, alanates and borohydrides. This work is an attempt of explaining some trends in the physical properties of Alk-H and AlkE-H, employing the Bader analysis of the charge distribution topology evaluated by first-principle all-electron calculations. These results are related to some variables commonly used in the explanation of experimental and calculated results, and are also accompanied by simple tight-binding estimations. Such an approach provides a valuable insight in the characteristics of M-H and H-H interactions in these hydrides, and their possible changes along with external parameters, like temperature, pressure, defect or impurity introduction. The knowledge of these basic interactions and processes taking place in simple MH are essential for the design and optimisation of complex MH-systems interesting for practical hydrogen storage applications.

  5. Hydrogen and dihydrogen bonding of transition metal hydrides

    NASA Astrophysics Data System (ADS)

    Jacobsen, Heiko

    2008-04-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  6. Hydride encapsulation by molecular alkali-metal clusters.

    PubMed

    Haywood, Joanna; Wheatley, Andrew E H

    2008-07-14

    The sequential treatment of group 12 and 13 Lewis acids with alkali-metal organometallics is well established to yield so-called ''ate' complexes, whereby the Lewis-acid metal undergoes nucleophilic attack to give an anion, at least one group 1 metal acting to counter this charge. However, an alternative, less well recognised, reaction pathway involves the Lewis acid abstracting hydride from the organolithium reagent via a beta-elimination mechanism. It has recently been shown that in the presence of N,N'-bidentate ligands this chemistry can be harnessed to yield a new type of molecular main-group metal cluster in which the abstracted LiH is effectively trapped, with the hydride ion occupying an interstitial site in the cluster core. Discussion focuses on the development of this field, detailing advances in our understanding of the roles of Lewis acid, organolithium, and amine substrates in the syntheses of these compounds. Structure-types are discussed, as are efforts to manipulate cluster geometry and composition as well as hydride-coordination. Embryonic mechanistic studies are reported, as well as attempts to generate hydride-encapsulation clusters under catalytic control.

  7. Optimizing Misch-Metal Compositions In Metal Hydride Anodes

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Halpert, Gerald

    1995-01-01

    Electrochemical cells based on metal hydride anodes investigated experimentally in effort to find anode compositions maximizing charge/discharge-cycle performances. Experimental anodes contained misch metal alloyed with various proportions of Ni, Co, Mn, and Al, and experiments directed toward optimization of composition of misch metal.

  8. Well-defined transition metal hydrides in catalytic isomerizations.

    PubMed

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  9. Hydride generation from the Exide load-leveling cells

    NASA Astrophysics Data System (ADS)

    Marr, J. J.; Smaga, J. A.

    1987-05-01

    Stibine and arsine evolution from lead-acid cells in a 36-kWh Exide load-leveling module was measured as this module approached 1900 cycles of operation. A gas-collection apparatus enabled us to determine the maximum and average rates for evolution of both toxic hydrides. Hydride generation began once the cell voltage exceeded 2.4 V. The maximum rate for arsine occurred just above 2.5 V and consistently preceded the peak rate for stibine for each sampled cell. The average rates of hydride generation were found to be 175 g/min for stibine and 12.6 g/min for arsine. The former rate proved to be the critical value in determining safe ventilation requirements for cell off-gases. The minimum airflow requirement was calculated to be 340 L/min per cell. Projections for a hypothetical 1-MWh Exide battery without an abatement system indicated that the normal ventilation capacity in the Battery Energy Storage Test facility provides nearly five times the airflow needed for safe hydride removal.

  10. An Aldol Reaction-Based Iridium(III) Chemosensor for the Visualization of Proline in Living Cells

    NASA Astrophysics Data System (ADS)

    Liu, Jin-Biao; Liu, Li-Juan; Dong, Zhen-Zhen; Yang, Guan-Jun; Leung, Chung-Hang; Ma, Dik-Lung

    2016-11-01

    A long-lived aldol reaction-based iridium(III) chemosensor [Ir(ppy)2(5-CHOphen)]PF6 (1, where ppy = 2-phenylpyridine and 5-CHOphen = 1,10-phenanthroline-5-carbaldehyde) for proline detection has been synthesized. The iridium(III) complex 1, incorporating an aldehyde group in N^N donor ligand, can take part in aldol reaction with acetone mediated by proline. The transformation of the sp2-hybridized carbonyl group into a sp3-hybridized alcohol group influences the metal-to-ligand charge-transfer (MLCT) state of the iridium(III) complex, resulting in a change in luminescence in response to proline. The interaction of the iridium(III) complex 1 with proline was investigated by 1H NMR, HRMS and emission titration experiments. Upon the addition of proline to a solution of iridium(III) complex 1, a maximum 8-fold luminescence enhancement was observed. The luminescence signal of iridium(III) complex 1 could be recognized in strongly fluorescent media using time-resolved emission spectroscopy (TRES). The detection of proline in living cells was also demonstrated.

  11. An Analysis of the FY-1C, Iridium 33, and Cosmos 2251 Fragments

    NASA Technical Reports Server (NTRS)

    Liou, J.-C.

    2014-01-01

    The beginning of the year 2013 marks the sixth anniversary of the destruction of the Fengyun-1C (FY-1C) weather satellite as the result of an anti-satellite test conducted by China in January 2007 and the fourth anniversary of the accidental collision between Cosmos 2251 and the operational Iridium 33 in February 2009. These two events represent the worst satellite breakups in history. A total of 5579 fragments have been cataloged by the U.S. Space Surveillance Network (SSN), and almost 5000 of them were still in orbit in January 2013. In addition to these cataloged objects, hundreds of thousands (or more) of fragments down to the millimeter size regime were also generated during the breakups. These fragments are too small to be tracked by the SSN, but are large enough to be a safety concern for human space activities and robotic missions in low Earth orbit (LEO, the region below 2000 km altitude). Like their cataloged siblings, many of them remain in orbit today. These two breakup events dramatically changed the landscape of the orbital debris environment in LEO. The spatial density of the cataloged population in January 2013 is shown as the top blue curve. The combined FY-1C, Iridium 33, and Cosmos 2251 fragments (black curve) account for about 50 percent of the cataloged population below an altitude of 1000 km. They are also responsible for the concentrations at 770 km and 850 km, altitudes at which the collisions occurred. The effects of the FY-1C, Iridium 33, and Cosmos 2251 fragments will continue to be felt for decades to come. For example, approximately half of the generated FY-1C fragments will remain in orbit 20 years from now. In general, the Iridium 33 and Cosmos 2251 fragments will decay faster than the FY-1C fragments because of their lower altitudes. Of the Iridium 33 and Cosmos 2251 fragments, the former have much shorter orbital lifetimes than the latter, because lightweight composite materials were heavily used in the construction of the Iridium

  12. Hydride Compressor Sorption Cooler and Surface Contamination Issues

    NASA Astrophysics Data System (ADS)

    Bowman, R. C.; Reiter, J. W.; Prina, M.; Kulleck, J. G.; Lanford, W. A.

    2003-07-01

    A continuous-duty hydrogen sorption cryocooler is being developed for the Planck spacecraft, a mission to map the cosmic microwave background beginning in 2007. This cryocooler uses six individual compressor elements (CEs) filled with the hydriding alloy LaNi4.78Sn0.22 to provide high-pressure (50 bar) hydrogen to a Joule-Thomson (J-T) expander and to absorb low-pressure (˜0.3 bar) gas from liquid hydrogen reservoirs cooled to ˜18K. Quadrupole Mass Spectrometry (QMS) showed methane in these hydride beds after cycling during initial operation of laboratory tests of the Planck engineering breadboard (EBB) cooler. These contaminants have caused problems involving plugged J-T expanders. The contaminants probably come from reactions with residual hydrocarbon species on surfaces inside the hydride bed. The hydride bed in each CE is contained in an annular volume called a "gas-gap heat switch," which serves as a reversible, intermittent thermal path to the spacecraft radiator. The gas-gap is either "off" (i.e., its pressure <1.3 Pa), or "on" (i.e., hydrogen gas at ˜4 kPa). The hydrogen pressure is varied with an independent hydride actuator containing ZrNiHx. Early EBB cooler tests showed increasing parasitic heat losses from the inner beds, suggesting residual pressures in the gas gap during its "off" state. The pressure was shown to be due to hydrogen from outgassing from metallic surfaces in the gas gap and hydrogen permeation through the inner sorbent bed wall. This gas accumulation has serious end-of-life implications, as the ZrNi actuator has limited storage capacity and any excess hydrogen would necessarily affect its operation. This paper summarizes experiments on the behavior of hydrogen in the gas gap switch and formation of methane in the CE sorbent beds.

  13. Metal Hydrides as hot carrier cell absorber materials

    NASA Astrophysics Data System (ADS)

    Wang, Pei; Wen, Xiaoming; Shrestha, Santosh; Conibeer, Gavin; Aguey-Zinsou, Kondo-Francois

    2016-09-01

    The hot Carrier Solar Cell (HCSC) allows the photon-induced hot carriers (the carriers with energy larger than the band gap) to be collected before they completely thermalise. The absorber of the HCSC should have a large phononic band gap to supress Klemens Decay, which results in a slow carrier cooling speed. In fact, a large phononic band gap likely exists in a binary compound whose constituent elements have a large mass ratio between each other. Binary hydrides with their overwhelming mass ratio of the constituent elements are important absorber candidates. Study on different types of binary hydrides as potential absorber candidates is presented in this paper. Many binary transition metal hydrides have reported theoretical or experimental phonon dispersion charts which show large phononic band gaps. Among these hydrides, the titanium hydride (TiHX) is outstanding because of its low cost, easy fabrication process and is relatively inert to air and water. A TiHX thin film is fabricated by directly hydrogenating an evaporated titanium thin film. Characterisation shows good crystal quality and the hydrogenation process is believed to be successful. Ultrafast transient absorption (TA) spectroscopy is used to study the electron cooling time of TiHX. The result is very noisy due to the low absorption and transmission of the sample. The evolution of the TA curves has been explained by band to band transition using the calculated band structure of TiH2. Though not reliable due to the high noise, decay time fitting at 700nm and 600nm shows a considerably slow carrier cooling speed of the sample.

  14. Inert blanketing of a hydride bed using typical grade protium

    SciTech Connect

    Klein, J.E.

    2015-03-15

    This paper describes the impact of 500 ppm (0.05%) impurities in protium on the absorption rate of a 9.66 kg LaNi{sub 4.25}Al{sub 0.75} (LANA0.75) metal hydride bed. The presence of 500 ppm or less inerts (i.e. non-hydrogen isotopes) can significantly impact hydrogen bed absorption rates. The impact on reducing absorption rates is significantly greater than predicted assuming uniform temperature, pressure, and compositions throughout the bed. Possible explanations are discussed. One possibility considered was the feed gas contained impurity levels higher than 500 ppm. It was shown that a level of 5000 ppm of inerts would have been necessary to fit the experimental result so this possibility wa dismissed. Another possibility is that the impurities in the protium supply reacted with the hydride material and partially poisoned the hydride. If the hydride were poisoned with CO or another impurity, the removal of the over-pressure gas in the bed would not be expected to allow the hydride loading of the bed to continue as the experimental results showed, so this possibility was also dismissed. The last possibility questions the validity of the calculations. It is assumed in all the calculations that the gas phase composition, temperature, and pressure are uniform throughout the bed. These assumptions are less valid for large beds where there can be large temperature, pressure, and composition gradients throughout the bed. Eventually the impact of 0.05% inerts in protium on bed absorption rate is shown and explained in terms of an increase in inert partial pressure as the bed was loaded.

  15. Hydride transfer during catalysis by dihydrofolate reductase from Thermotoga maritima.

    PubMed Central

    Maglia, Giovanni; Javed, Masood H; Allemann, Rudolf K

    2003-01-01

    DHFR (dihydrofolate reductase) catalyses the metabolically important reduction of 7,8-dihydrofolate by NADPH. DHFR from the hyperthermophilic bacterium Thermotoga maritima (TmDHFR), which shares similarity with DHFR from Escherichia coli, has previously been characterized structurally. Its tertiary structure is similar to that of DHFR from E. coli but it is the only DHFR characterized so far that relies on dimerization for stability. The midpoint of the thermal unfolding of TmDHFR was at approx. 83 degrees C, which was 30 degrees C higher than the melting temperature of DHFR from E. coli. The turnover and the hydride-transfer rates in the kinetic scheme of TmDHFR were derived from measurements of the steady-state and pre-steady-state kinetics using absorbance and stopped-flow fluorescence spectroscopy. The rate constant for hydride transfer was found to depend strongly on the temperature and the pH of the solution. Hydride transfer was slow (0.14 s(-1) at 25 degrees C) and at least partially rate limiting at low temperatures but increased dramatically with temperature. At 80 degrees C the hydride-transfer rate of TmDHFR was 20 times lower than that observed for the E. coli enzyme at its physiological temperature. Hydride transfer depended on ionization of a single group in the active site with a p K(a) of 6.0. While at 30 degrees C, turnover of substrate by TmDHFR was almost two orders of magnitude slower than by DHFR from E. coli; the steady-state rates of the two enzymes differed only 8-fold at their respective working temperatures. PMID:12765545

  16. 5-year review of Metal Hydride Center of Excellence.

    SciTech Connect

    Keller, Jay O.; Klebanoff, Leonard E.

    2010-05-01

    The purpose of the DOE Metal Hydride Center of Excellence (MHCoE) is to develop hydrogen storage materials with engineering properties that allow the use of these materials in a way that satisfies the DOE/FreedomCAR Program system requirements for automotive hydrogen storage. The Center is a multidisciplinary and collaborative effort with technical interactions divided into two broad areas: (1) mechanisms and modeling (which provide a theoretically driven basis for pursuing new materials) and (2) materials development (in which new materials are synthesized and characterized). Driving all of this work are the hydrogen storage system specifications outlined by the FreedomCAR Program for 2010 and 2015. The organization of the MHCoE during the past year is show in Figure 1. During the past year, the technical work was divided into four project areas. The purpose of the project areas is to organize the MHCoE technical work along appropriate and flexible technical lines. The four areas summarized are: (1) Project A - Destabilized Hydrides, The objective of this project is to controllably modify the thermodynamics of hydrogen sorption reactions in light metal hydrides using hydride destabilization strategies; (2) Project B - Complex Anionic Materials, The objective is to predict and synthesize highly promising new anionic hydride materials; (3) Project C - Amides/Imides Storage Materials, The objective of Project C is to assess the viability of amides and imides (inorganic materials containing NH{sub 2} and NH moieties, respectively) for onboard hydrogen storage; and (4) Project D - Alane, AlH{sub 3}, The objective of Project D is to understand the sorption and regeneration properties of AlH{sub 3} for hydrogen storage.

  17. Excimer laser deinsulation of Parylene-C on iridium for use in an activated iridium oxide film-coated Utah electrode array.

    PubMed

    Yoo, Je-Min; Negi, Sandeep; Tathireddy, Prashant; Solzbacher, Florian; Song, Jong-In; Rieth, Loren W

    2013-04-30

    Implantable microelectrodes provide a measure to electrically stimulate neurons in the brain and spinal cord and record their electrophysiological activity. A material with a high charge capacity such as activated or sputter-deposited iridium oxide film (AIROF or SIROF) is used as an interface. The Utah electrode array (UEA) uses SIROF for its interface material with neural tissue and oxygen plasma etching (OPE) with an aluminium foil mask to expose the active area, where the interface between the electrode and neural tissue is formed. However, deinsulation of Parylene-C using OPE has limitations, including the lack of uniformity in the exposed area and reproducibility. While the deinsulation of Parylene-C using an excimer laser is proven to be an alternative for overcoming the limitations, the iridium oxide (IrOx) suffers from fracture when high laser fluence (>1000 mJ/cm2) is used. Iridium (Ir), which has a much higher fracture resistance than IrOx, can be deposited before excimer laser deinsulation and then the exposed Ir film area can be activated by electrochemical treatment to acquire the AIROF. Characterisation of the laser-ablated Ir film and AIROF by surface analysis (X-ray photoelectron spectroscopy, scanning electron microscope, and atomic force microscope) and electrochemical analysis (electrochemical impedance spectroscopy, and cyclic voltammetry) shows that the damage on the Ir film induced by laser irradiation is significantly less than that on SIROF, and the AIROF has a high charge storage capacity. The results show the potential of the laser deinsulation technique for use in high performance AIROF-coated UEA fabrication.

  18. Hydriding performances and modeling of a small-scale ZrCo bed

    SciTech Connect

    Koo, D.; Lee, J.; Park, J.; Paek, S.; Chung, H.; Chang, M.H.; Yun, S.H.; Cho, S.; Jung, K.J.

    2015-03-15

    In order to evaluate the performance of the hydriding of a ZrCo bed, a small-scale getter bed of ZrCo was designed and fabricated. The results show that the hydriding time at room temperature was somewhat shorter than that at higher temperatures of ZrCo and that the performance of hydriding at low temperatures of ZrCo was better than that at high temperatures of ZrCo. The experimental results of the hydrogen pressure of hydriding (ZrCoH{sub 2.8}) at different temperatures were in agreement with the computed values using a numerical modeling equation but with a small difference during the first 10 minutes of the hydriding of ZrCo. The model is based on the Kozeny-Carman equation. The effect of a helium blanket on hydriding was measured and analyzed. The hydriding with no helium blanket in the primary vessel of ZrCo is much faster than that with a helium blanket. The hydriding at a helium concentration of 8% is slower than that at 0%. As the helium concentration increases, the hydriding of ZrCo decreases. The experimental results of the hydriding with 0 %, 4%, and 8% of helium concentration are in agreement with the calculated values but with minimal differences during the first 10 minutes.

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  20. Preliminary design studies for an iridium rod target at the BNL-AGS

    SciTech Connect

    Ludewig, H.; Hastings, J.; Montanez, P.; Todosow, M.

    1998-12-31

    The BNL-AGS is an intense source of 24 GeV protons. It is proposed to explore the potential to use these protons as the driver for a Pulsed Spallation Neutron Source target. The proposed target design is based on an edge cooled iridium rod concept--similar to the anti-proton production target which operated reliably at CERN under similar conditions. Lead, lead fluoride, and beryllium are investigated as possible reflector materials, and ambient temperature light water and 80 K light water ice are proposed as initial moderator materials. Both moderators are decoupled by cadmium containing moderator chamber walls. The small size of the target has the advantage that the moderators can be placed close to the target (resulting in a bright source), and since a large fraction of the radioactive inventory is contained in the iridium rod, removal and disposition of this inventory should be relatively simple and inexpensive.

  1. First Applications of DoD Iridium RUDICS in the NSF Polar Programs

    NASA Astrophysics Data System (ADS)

    Valentic, T.; Stehle, R.

    2008-12-01

    We will present the first deployment and application of the new Iridium RUDICS service to remote instrumentation projects within the National Science Foundation's polar programs. The rise of automated observing networks has increased the demand for real-time connectivity to remote instruments, not only for immediate access to data, but to also interrogate health and status. Communicating with field sites in the polar regions is complicated by the remoteness from existing infrastructure, low temperatures and limited connection options. Sites located above 78° latitude are not able to see geostationary satellites, leaving the Iridium constellation as the only one that provide a direct connection. Some others, such as Orbcomm, only provide a store-and-forward service. Iridium is often used as a dial up modem to establish a PPP connection to the Internet with data files transferred via FTP. On low-bandwidth, high-latency networks like Iridium (2400bps with ping times of seconds), this approach is time consuming and inefficient. The dial up time alone takes upwards of a minute, and standard TCP/IP and FTP protocols are hampered by the long latencies. Minimizing transmission time is important for reducing battery usage and connection costs. The new Iridium RUDICS service can be used for more efficient transfers. RUDICS is an acronym for "Router-based Unstructured Digital Inter-working Connectivity Solution" and provides a direct connection between an instrument in the field and a server on the Internet. After dialing into the Iridium gateway, a socket connection is opened to a registered port on a user's server. Bytes sent to or from the modem appear at the server's socket. The connection time is reduced to about 10 seconds because the modem training and PPP negotiation stages are eliminated. The remote device does not need to have a full TCP/IP stack, allowing smaller instruments such as data loggers to directly handle the data transmission. Alternative protocols can

  2. Iridium-catalyzed H/D exchange: ligand complexes with improved efficiency and scope.

    PubMed

    Parmentier, Michael; Hartung, Thomas; Pfaltz, Andreas; Muri, Dieter

    2014-09-01

    Hydrogen isotope exchange (HIE) is one of the most attractive tools for the introduction of deuterium or tritium to an organic compound. Herein, iridium complexes with N,P-ligands, highly active catalysts for asymmetric double bond reductions, have been tested for their HIE capabilities. Electron-rich ligands, containing dicyclohexylphosphines or phosphinites, have been identified as excellent ligands for efficient deuterium incorporation. Substrates with strong directing groups, that is, pyridines, ketones, and amides, as well as weak ligating units, such as, nitro, sulfones, and sulfonamides, could be labeled efficiently. With the addition of tris(pentafluorophenyl) borane to the reaction mixture, also highly deactivating nitrile substituents were well tolerated in the reaction. Based on the excellent results obtained with the chiral ThrePhox ligand, a structurally simpler, achiral ligand was developed. The iridium complex containing this ligand, proved to be a powerful catalyst for HIE reactions.

  3. The treatment of malignant diseases in Romania using stainless steel encapsulated iridium-192 sources

    NASA Astrophysics Data System (ADS)

    Stanef, I.; Matache, G.; Ciocǎltei, V.; Gheorghiev, G.

    1994-01-01

    Iridium-192 sources supplied by the Institute for Nuclear Physics and Engineering have been used in Romanian radiotherapy clinics since 1980. The source assembly is sealed in a protective stainless steel sheath which satisfies the requirements of international standards. Since this sheath acts as a filter to change the characteristic spectrum it has been necessary to determine experimentally an accurate value of the specific gamma-ray constant. Some clinical aspects of the complex treatment of carcinomas with iridium-192 are reviewed. Results of the calculation of the dose distribution around single and multiple sources are given for different applications in the treatment of carcinomas of the vaginal and uterine cervix, oral cavity, rectum and vagina.

  4. Conferring Phosphorogenic Properties on Iridium(III)-Based Bioorthogonal Probes through Modification with a Nitrone Unit.

    PubMed

    Lee, Lawrence Cho-Cheung; Lau, Jonathan Chun-Wai; Liu, Hua-Wei; Lo, Kenneth Kam-Wing

    2016-01-18

    The use of bioorthogonal probes that display fluorogenic or phosphorogenic properties is advantageous to the labeling and imaging of biomolecules in live cells and organisms. Herein we present the design of three iridium(III) complexes containing a nitrone moiety as novel phosphorogenic bioorthogonal probes. These probes were non-emissive owing to isomerization of the C=N group but showed significant emission enhancement upon cycloaddition reaction with strained cyclooctynes. Interestingly, the connection of the nitrone ligand to the cationic iridium(III) center led to accelerated reaction kinetics. These nitrone complexes were also identified as phosphorogenic bioorthogonal labels and imaging reagents for cyclooctyne-modified proteins. These findings contribute to the development of phosphorogenic bioorthogonal probes and imaging reagents.

  5. An inconvenient influence of iridium(III) isomer on OLED efficiency.

    PubMed

    Baranoff, Etienne; Bolink, Henk J; De Angelis, Filippo; Fantacci, Simona; Di Censo, Davide; Djellab, Karim; Grätzel, Michael; Nazeeruddin, Md Khaja

    2010-10-14

    The recently reported heteroleptic cyclometallated iridium(III) complex [Ir(2-phenylpyridine)(2)(2-carboxy-4-dimethylaminopyridine)] N984 and its isomer N984b have been studied more in detail. While photo- and electrochemical properties are very similar, DFT/TDDFT calculations show that the two isomers have different HOMO orbital characteristics. As a consequence, solution processed OLEDs made using a mixture of N984 and isomer N984b similar to vacuum processed devices show that the isomer has a dramatic detrimental effect on the performances of the device. In addition, commonly used thermogravimetric analysis is not suitable for showing the isomerization process. The isomer could impact performances of vacuum processed OLEDs using heteroleptic cyclometallated iridium(III) complexes as dopant.

  6. Research of remote control for Chinese Antarctica Telescope based on iridium satellite communication

    NASA Astrophysics Data System (ADS)

    Xu, Lingzhe; Yang, Shihai

    2010-07-01

    Astronomers are ever dreaming of sites with best seeing on the Earth surface for celestial observation, and the Antarctica is one of a few such sites only left owing to the global air pollution. However, Antarctica region is largely unaccessible for human being due to lacking of fundamental living conditions, travel facilities and effective ways of communication. Worst of all, the popular internet source as a general way of communication scarcely exists there. Facing such a dilemma and as a solution remote control and data transmission for telescopes through iridium satellite communication has been put forward for the Chinese network Antarctic Schmidt Telescopes 3 (AST3), which is currently under all round research and development. This paper presents iridium satellite-based remote control application adapted to telescope control. The pioneer work in China involves hardware and software configuration utilizing techniques for reliable and secure communication, which is outlined in the paper too.

  7. Strongly improved electrochemical cycling durability by adding iridium to electrochromic nickel oxide films.

    PubMed

    Wen, Rui-Tao; Niklasson, Gunnar A; Granqvist, Claes G

    2015-05-13

    Anodically colored nickel oxide (NiO) thin films are of much interest as counter electrodes in tungsten oxide based electrochromic devices such as "smart windows" for energy-efficient buildings. However, NiO films are prone to suffering severe charge density degradation upon prolonged electrochemical cycling, which can lead to insufficient device lifetime. Therefore, a means to improve the durability of NiO-based films is an important challenge at present. Here we report that the incorporation of a modest amount of iridium into NiO films [Ir/(Ir + Ni) = 7.6 atom %] leads to remarkable durability, exceeding 10000 cycles in a lithium-conducting electrolyte, along with significantly improved optical modulation during extended cycling. Structure characterization showed that the face-centered-cubic-type NiO structure remained after iridium addition. Moreover, the crystallinity of these films was enhanced upon electrochemical cycling.

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

    PubMed

    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.

  9. Localization matters: a nuclear targeting two-photon absorption iridium complex in photodynamic therapy.

    PubMed

    Tian, Xiaohe; Zhu, Yingzhong; Zhang, Mingzhu; Luo, Lei; Wu, Jieying; Zhou, Hongping; Guan, Lijuan; Battaglia, Giuseppe; Tian, Yupeng

    2017-03-16

    We present a two-photon (2P, 800 nm) PDT cyclometalated Iridium(iii) complex (Ir-Es) that targets the intracellular nucleus. The complex is capable of migrating sequentially from the nucleus to mitochondria and inducing dual-damage under light exposure. This study suggests that with minor modification of the terminal moieties of complexes, their final intracellular destinations and PDT efficiency can be significantly impacted.

  10. A Cascade Isomerization/Prins Strategy through Iridium(III)/Brønsted Acid Cooperative Catalysis**

    PubMed Central

    Lombardo, Vince M.; Thomas, Christopher D.; Scheidt, Karl A.

    2014-01-01

    A mild and efficient isomerization/protonation sequence involving an appropriately functionalized indole precursor to generate a wide variety of pyran-fused indoles utilizing cooperative catalysis between cationic iridium (III) and bismuth triflate has been developed. Three distinct cyclization manifolds lead to bioactive scaffolds that can be obtained in good yields. In addition, N-substituted indoles can be synthesized enantioselectively via an oxocarbenium• chiral phosphate counterion strategy. PMID:24218144

  11. Transformation of a Cp*-iridium(III) precatalyst for water oxidation when exposed to oxidative stress.

    PubMed

    Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bortolini, Olga; Bucci, Alberto; Savini, Arianna; Macchioni, Alceo

    2014-03-17

    The reaction of [Cp*Ir(bzpy)NO3 ] (1; bzpy=2-benzoylpyridine, Cp*=pentamethylcyclopentadienyl anion), a competent water-oxidation catalyst, with several oxidants (H2 O2 , NaIO4 , cerium ammonium nitrate (CAN)) was studied to intercept and characterize possible intermediates of the oxidative transformation. NMR spectroscopy and ESI-MS techniques provided evidence for the formation of many species that all had the intact Ir-bzpy moiety and a gradually more oxidized Cp* ligand. Initially, an oxygen atom is trapped in between two carbon atoms of Cp* and iridium, which gives an oxygen-Ir coordinated epoxide, whereas the remaining three carbon atoms of Cp* are involved in a η(3) interaction with iridium (2 a). Formal addition of H2 O to 2 a or H2 O2 to 1 leads to 2 b, in which a double MeCOH functionalization of Cp* is present with one MeCOH engaged in an interaction with iridium. The structure of 2 b was unambiguously determined in the solid state and in solution by X-ray single-crystal diffractometry and advanced NMR spectroscopic techniques, respectively. Further oxidation led to the opening of Cp* and transformation of the diol into a diketone with one carbonyl coordinated at the metal (2 c). A η(3) interaction between the three non-oxygenated carbons of "ex-Cp*" and iridium is also present in both 2 b and 2 c. Isolated 2 b and mixtures of 2 a-c species were tested in water-oxidation catalysis by using CAN as sacrificial oxidant. They showed substantially the same activity than 1 (turnover frequency values ranged from 9 to 14 min(-1) ).

  12. An iridium abundance anomaly at the palynological Cretaceous-Tertiary boundary in northern New Mexico

    USGS Publications Warehouse

    Orth, C.J.; Gilmore, J.S.; Knight, J.D.; Pillmore, C.L.; Tschudy, R.H.; Fassett, J.E.

    1981-01-01

    An iridium abundance anomaly, with concentrations up to 5000 parts per trillion over a background level of 4 to 20 parts per trillion, has been located in sedimentary rocks laid down under freshwater swamp conditions in the Raton Basin of northeastern New Mexico. The anomaly occurs at the base of a coal bed, at the same stratigraphic position at which several well-known species of Cretaceous-age pollen became extinct. Copyright ?? 1981 AAAS.

  13. A mild dihydrobenzooxaphosphole oxazoline/iridium catalytic system for asymmetric hydrogenation of unfunctionalized dialins.

    PubMed

    Qu, Bo; Samankumara, Lalith P; Ma, Shengli; Fandrick, Keith R; Desrosiers, Jean-Nicolas; Rodriguez, Sonia; Li, Zhibin; Haddad, Nizar; Han, Zhengxu S; McKellop, Keith; Pennino, Scott; Grinberg, Nelu; Gonnella, Nina C; Song, Jinhua J; Senanayake, Chris H

    2014-12-22

    Air-stable P-chiral dihydrobenzooxaphosphole oxazoline ligands were designed and synthesized. When they were used in the iridium-catalyzed asymmetric hydrogenation of unfunctionalized 1-aryl-3,4-dihydronaphthalenes under one atmosphere pressure of H2 , up to 99:1 e.r. was obtained. High enantioselectivities were also observed in the reduction of the exocyclic imine derivatives of 1-tetralones.

  14. The laser welding of iridium-platinum tips to spark plug electrodes

    NASA Astrophysics Data System (ADS)

    Antoszewski, Bogdan; Tofil, Szymon

    2016-12-01

    The paper presents selected results of model and technological experiments of welding iridium-platinum tips to spark plug electrodes. Variants of welding technology included different ways of preparing materials and the use of different Nd: YAG lasers (Rofin BLS 720 and Rofin Integral). The results of technological tests were verified by the metallographic evaluation of joints. Performance tests when powered by biogas were conducted for selected variants of welding.

  15. Diastereo- and Enantioselective Iridium Catalyzed Carbonyl (α-Cyclopropyl)allylation via Transfer Hydrogenation.

    PubMed

    Tsutsumi, Ryosuke; Hong, Suckchang; Krische, Michael J

    2015-09-07

    The first examples of diastereo- and enantioselective carbonyl α-(cyclopropyl)allylation are reported. Under the conditions of iridium catalyzed transfer hydrogenation using the chiral precatalyst (R)-Ir-I modified by SEGPHOS, carbonyl α-(cyclopropyl)allylation may be achieved with equal facility from alcohol or aldehyde oxidation levels. This methodology provides a conduit to hitherto inaccessible inaccessible enantiomerically enriched cyclopropane-containing architectures.

  16. Branch-Selective Alkene Hydroarylation by Cooperative Destabilization: Iridium-Catalyzed ortho-Alkylation of Acetanilides

    PubMed Central

    Crisenza, Giacomo E M; Sokolova, Olga O; Bower, John F

    2015-01-01

    An iridium(I) catalyst system, modified with the wide-bite-angle and electron-deficient bisphosphine dFppb (1,4-bis(di(pentafluorophenyl)phosphino)butane) promotes highly branch-selective hydroarylation reactions between diverse acetanilides and aryl- or alkyl-substituted alkenes. This provides direct and ortho-selective access to synthetically challenging anilines, and addresses long-standing issues associated with related Friedel–Crafts alkylations. PMID:26490739

  17. Biocompatibility and durability of Teflon-coated platinum-iridium wires implanted in the vitreous cavity.

    PubMed

    Nishida, Kentaro; Sakaguchi, Hirokazu; Xie, Ping; Terasawa, Yasuo; Ozawa, Motoki; Kamei, Motohiro; Nishida, Kohji

    2011-12-01

    Teflon-coated platinum-iridium wires are placed in the vitreous as electrodes in artificial vision systems. The purpose of this study was to determine whether these wires have toxicity in the vitreous cavity, and to examine the durability of their coating when grasped by forceps. Rabbits were implanted with platinum-iridium wires that were 50 μm in diameter and coated with Teflon to a total diameter of 68 or 100 μm. To examine the biocompatibility, electroretinograms (ERGs) and fluorescein angiography (FA) were performed before and 1 week, 1, 3, and 6 months after the implantation of the electrode. After 6 months, the eyes were histologically examined with light microscopy. To check the durability, the surface of a coated wire was examined with scanning electron microscopy after grasping with different types of forceps. At all times after the implantation the amplitudes and implicit times of the ERGs recorded were not significantly different from those recorded before the implantation (P > 0.05). FA showed no notable change during the follow-up periods. Histological studies showed that the retinas were intact after 6 months of implantation. There was no damage to the Teflon-coated wire after grasping the wire with forceps with silicon-coated tips, while surface damage of the Teflon that did not extend to the platinum-iridium wire was found when grasped by vitreoretinal forceps. We conclude that Teflon-coated platinum-iridium wire is highly biocompatible in the vitreous for at least 6 months. Wires should be handled with vitreoretinal forceps with silicone-coated tips in order to avoid causing damage during wire manipulation.

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

    SciTech Connect

    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

  19. Octahedral Chiral-at-Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions.

    PubMed

    Shen, Xiaodong; Huo, Haohua; Wang, Chuanyong; Zhang, Bo; Harms, Klaus; Meggers, Eric

    2015-06-26

    Octahedral iridium(III) complexes containing two bidentate cyclometalating 5-tert-butyl-2-phenylbenzoxazole (IrO) or 5-tert-butyl-2-phenylbenzothiazole (IrS) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5-5.0 mol % catalyst loading) for a variety of reactions with α,β-unsaturated carbonyl compounds, namely Friedel-Crafts alkylations (94-99% ee), Michael additions with CH-acidic compounds (81-97% ee), and a variety of cycloadditions (92-99% ee with high d.r.). Mechanistic investigations and crystal structures of an iridium-coordinated substrates and iridium-coordinated products are consistent with a mechanistic picture in which the α,β-unsaturated carbonyl compounds are activated by two-point binding (bidentate coordination) to the chiral Lewis acid.

  20. Neutron activation determination of iridium, gold, platinum, and silver in geologic samples

    USGS Publications Warehouse

    Millard, H.T.

    1987-01-01

    Low-level methods for the determination of iridium and other noble metals have become increasingly important in recent years due to interest in locating abundance anomalies associated with the Cretaceous and Tertiary (K-T) boundary. Typical iridium anomalies are in the range of 1 to 100 ??g/kg (ppb). Thus methods with detection limits near 0.1 ??g/kg should be adequate to detect K-T boundary anomalies. Radiochemical neutron activation analysis methods continue to be required although instrumental neutron activation analysis techniques employing elaborate gamma-counters are under development. In the procedure developed in this study samples irradiated in the epithermal neutron facility of the U. S. Geological Survey TRIGA Reactor (Denver, Colorado) are treated with a mini-fire assay technique. The iridium, gold, and silver are collected in a 1-gram metallic lead button. Primary contaminants at this stage are arsenic and antimony. These can be removed by heating the button with a mixture of sodium perioxide and sodium hydroxide. The resulting 0.2-gram lead bead is counted in a Compton suppression spectrometer. Carrier yields are determined by reirradiation of the lead beads. This procedure has been applied to the U.S.G.S. Standard Rock PCC-1 and samples from K-T boundary sites in the Western Interior of North America. ?? 1987 Akade??miai Kiado??.

  1. Synthesis, characterisation and application of iridium(III) photosensitisers for catalytic water reduction.

    PubMed

    Gärtner, Felix; Cozzula, Daniela; Losse, Sebastian; Boddien, Albert; Anilkumar, Gopinatan; Junge, Henrik; Schulz, Thomas; Marquet, Nicolas; Spannenberg, Anke; Gladiali, Serafino; Beller, Matthias

    2011-06-14

    The synthesis of novel, monocationic iridium(III) photosensitisers (Ir-PSs) with the general formula [Ir(III)(C^N)(2)(N^N)](+) (C^N: cyclometallating phenylpyridine ligand, N^N: neutral bidentate ligand) is described. The structures obtained were examined by cyclic voltammetry, UV/Vis and photoluminescence spectroscopy and X-ray analysis. All iridium complexes were tested for their ability as photosensitisers to promote homogeneously catalysed hydrogen generation from water. In the presence of [HNEt(3)][HFe(3)(CO)(11)] as a water-reduction catalyst (WRC) and triethylamine as a sacrificial reductant (SR), seven of the new iridium complexes showed activity. [Ir(6-iPr-bpy)(ppy)(2)]PF(6) (bpy: 2,2'-bipyridine, ppy: 2-phenylpyridine) turned out to be the most efficient photosensitiser. This complex was also tested in combination with other WRCs based on rhodium, platinum, cobalt and manganese. In all cases, significant hydrogen evolution took place. Maximum turnover numbers of 4550 for this Ir-PS and 2770 for the Fe WRC generated in situ from [HNEt(3)][HFe(3)(CO)(11)] and tris[3,5-bis(trifluoromethyl)phenyl]phosphine was obtained. These are the highest overall efficiencies for any Ir/Fe water-reduction system reported to date. The incident photon to hydrogen yield reaches 16.4% with the best system.

  2. Consumable arc-melting, extruding, and rolling process for iridium sheet

    SciTech Connect

    Heestand, R.L.; Copeland, G.L.; Martin, M.M.

    1986-06-01

    An iridium alloy has been used as cladding for the /sup 238/PuO/sub 2/ fuel in radioisotope thermoelectric generators (RTGs) for recent interplanetary spacecraft such as Voyagers 1 and 2 and will be used for the Galileo and Ulysses spacecraft. The iridium alloy sheet for the fuel cladding used on these missions was fabricated by hot and cold rolling of arc-melted and drop-cast 0.5-kg ingots. Upon completion of production for these spacecraft, an opportunity was taken to conduct process improvement studies that would increase processing batch sizes, develop a more uniform product, decrease rejections due to internal delaminations and surface defects, and reduce costs. The studies to scale up and improve the fabrication process are described. In the new process, iridium is electron beam melted, alloyed by arc melting, and then consumable arc melted to form a cylindrical ingot of approximately 7 kg for extrusion. The ingot is extruded to sheet bar and hot and cold rooled into sheet. Sheet evaluated from the first two ingots showed 100% acceptance with no defects on inspection. An improved uniformity of microstructure was obtained, and chemistry was controlled within specification limits.

  3. Green Phosphorescence and Electroluminescence of Sulfur Pentafluoride-Functionalized Cationic Iridium(III) Complexes.

    PubMed

    Shavaleev, Nail M; Xie, Guohua; Varghese, Shinto; Cordes, David B; Slawin, Alexandra M Z; Momblona, Cristina; Ortí, Enrique; Bolink, Henk J; Samuel, Ifor D W; Zysman-Colman, Eli

    2015-06-15

    We report on four cationic iridium(III) complexes [Ir(C^N)2(dtBubpy)](PF6) that have sulfur pentafluoride-modified 1-phenylpyrazole and 2-phenylpyridine cyclometalating (C^N) ligands (dtBubpy = 4,4'-di-tert-butyl-2,2'-bipyridyl). Three of the complexes were characterized by single-crystal X-ray structure analysis. In cyclic voltammetry, the complexes undergo reversible oxidation of iridium(III) and irreversible reduction of the SF5 group. They emit bright green phosphorescence in acetonitrile solution and in thin films at room temperature, with emission maxima in the range of 482-519 nm and photoluminescence quantum yields of up to 79%. The electron-withdrawing sulfur pentafluoride group on the cyclometalating ligands increases the oxidation potential and the redox gap and blue-shifts the phosphorescence of the iridium complexes more so than the commonly employed fluoro and trifluoromethyl groups. The irreversible reduction of the SF5 group may be a problem in organic electronics; for example, the complexes do not exhibit electroluminescence in light-emitting electrochemical cells (LEECs). Nevertheless, the complexes exhibit green to yellow-green electroluminescence in doped multilayer organic light-emitting diodes (OLEDs) with emission maxima ranging from 501 nm to 520 nm and with an external quantum efficiency (EQE) of up to 1.7% in solution-processed devices.

  4. Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands

    SciTech Connect

    Lu, Jing; Serna, Pedro; Aydin, Cerem; Browning, Nigel D.; Gates, Bruce C.

    2012-02-07

    The performance of a supported catalyst is influenced by the size and structure of the metal species, the ligands bonded to the metal, and the support. Resolution of these effects has been lacking because of the lack of investigations of catalysts with uniform and systematically varied catalytic sites. We now demonstrate that the performance for ethene hydrogenation of isostructural iridium species on supports with contrasting properties as ligands (electron-donating MgO and electron-withdrawing HY zeolite) can be elucidated on the basis of molecular concepts. Spectra of the working catalysts show that the catalytic reaction rate is determined by the dissociation of H{sub 2} when the iridium, either as mono- or tetra-nuclear species, is supported on MgO and is not when the support is the zeolite. The neighboring iridium sites in clusters are crucial for activation of both H{sub 2} and C{sub 2}H{sub 4} when the support is MgO but not when it is the zeolite, because the electron-withdrawing properties of the zeolite support enable even single site-isolated Ir atoms to bond to both C{sub 2}H{sub 4} and H{sub 2} and facilitate the catalysis.

  5. A Novel Efficient Red Emitting Iridium Complex for Polymer Light Emitting Diodes

    NASA Astrophysics Data System (ADS)

    Hu, Zheng-Yong; Yang, Jian-Kui; Luo, Jing; Liang, Min; Wang, Jing

    2012-12-01

    Photo-physical properties of iridium complexes bis(1-(2',4'-difluorobiphenyl -4-yl)isoquinoline)iridium(III)(5-(4-(bis(4-methoxyphenyl)amino)phenyl)picolinic acid) used as phosphorescent dopant in polymer light-emitting devices with a blend ofpoly(9,9-dioctylfluorene) and 2-tert-butyl-phenyl-5-biphenyl-1,3,4-oxadiazole as a host matrix are investigated. The iridium complex exhibits distinct UV-vis absorption bands around 300-450 nm and intense red photoluminescent emissions peaked at around 618 nm in dichloromethane. The devices display a maximum external quantum efficiency of 4.8% and luminous efficiency of 3.1 cd·A-1 at current density of 3.2 mA·cm-2 with a dominant red emission peak around 620 nm and a shoulder around 660 nm. At 100 mA·cm-2, the devices still display a maximum external quantum efficiency as high as 3.9%.

  6. SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS..

    EPA Science Inventory

    Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride ...

  7. SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS...

    EPA Science Inventory

    Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride s...

  8. Effect of thermo-mechanical cycling on zirconium hydride reorientation studied in situ with synchrotron X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Colas, Kimberly B.; Motta, Arthur T.; Daymond, Mark R.; Almer, Jonathan D.

    2013-09-01

    The circumferential hydrides normally present in nuclear reactor fuel cladding after reactor exposure may dissolve during drying for dry storage and re-precipitate when cooled under load into a more radial orientation, which could embrittle the fuel cladding. It is necessary to study the rates and conditions under which hydride reorientation may happen in order to assess fuel integrity in dry storage. The objective of this work is to study the effect of applied stress and thermal cycling on the hydride morphology in cold-worked stress-relieved Zircaloy-4 by combining conventional metallography and in situ X-ray diffraction techniques. Metallography is used to study the evolution of hydride morphology after several thermo-mechanical cycles. In situ X-ray diffraction performed at the Advanced Photon Source synchrotron provides real-time information on the process of hydride dissolution and precipitation under stress during several thermal cycles. The detailed study of diffracted intensity, peak position and full-width at half-maximum provides information on precipitation kinetics, elastic strains and other characteristics of the hydride precipitation process. The results show that thermo-mechanical cycling significantly increases the radial hydride fraction as well as the hydride length and connectivity. The radial hydrides are observed to precipitate at a lower temperature than circumferential hydrides. Variations in the magnitude and range of hydride strains due to reorientation and cycling have also been observed. These results are discussed in light of existing models and experiments on hydride reorientation. The study of hydride elastic strains during precipitation shows marked differences between circumferential and radial hydrides, which can be used to investigate the reorientation process. Cycling under stress above the threshold stress for reorientation drastically increases both the reoriented hydride fraction and the hydride size. The reoriented hydride

  9. FEASIBILITY OF RECYCLING PLUTONIUM AND MINOR ACTINIDES IN LIGHT WATER REACTORS USING HYDRIDE FUEL

    SciTech Connect

    Greenspan, Ehud; Todreas, Neil; Taiwo, Temitope

    2009-03-10

    The objective of this DOE NERI program sponsored project was to assess the feasibility of improving the plutonium (Pu) and minor actinide (MA) recycling capabilities of pressurized water reactors (PWRs) by using hydride instead of oxide fuels. There are four general parts to this assessment: 1) Identifying promising hydride fuel assembly designs for recycling Pu and MAs in PWRs 2) Performing a comprehensive systems analysis that compares the fuel cycle characteristics of Pu and MA recycling in PWRs using the promising hydride fuel assembly designs identified in Part 1 versus using oxide fuel assembly designs 3) Conducting a safety analysis to assess the likelihood of licensing hydride fuel assembly designs 4) Assessing the compatibility of hydride fuel with cladding materials and water under typical PWR operating conditions Hydride fuel was found to offer promising transmutation characteristics and is recommended for further examination as a possible preferred option for recycling plutonium in PWRs.

  10. The free-energy barrier to hydride transfer across a dipalladium complex.

    PubMed

    Vanston, C R; Kearley, G J; Edwards, A J; Darwish, T A; de Souza, N R; Ramirez-Cuesta, A J; Gardiner, M G

    2015-01-01

    We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)2CH2}2Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.

  11. The free-energy barrier to hydride transfer across a dipalladium complex

    SciTech Connect

    Ramirez-Cuesta, Anibal J

    2015-01-01

    We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)(2)CH2}(2)Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.

  12. In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

    NASA Astrophysics Data System (ADS)

    Cinbiz, Mahmut N.; Koss, Donald A.; Motta, Arthur T.; Park, Jun-Sang; Almer, Jonathan D.

    2017-04-01

    The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. These experimental results can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix.

  13. The free-energy barrier to hydride transfer across a dipalladium complex

    DOE PAGES

    Ramirez-Cuesta, Anibal J

    2015-01-01

    We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)(2)CH2}(2)Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model formore » the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.« less

  14. Heat transfer analysis of metal hydrides in metal-hydrogen secondary batteries

    NASA Technical Reports Server (NTRS)

    Onischak, M.; Dharia, D.; Gidaspow, D.

    1976-01-01

    The heat transfer between a metal-hydrogen secondary battery and a hydrogen-storing metal hydride was studied. Temperature profiles of the endothermic metal hydrides and the metal-hydrogen battery were obtained during discharging of the batteries assuming an adiabatic system. Two hydride materials were considered in two physical arrangements within the battery system. In one case the hydride is positioned in a thin annular region about the battery stack; in the other the hydride is held in a tube down the center of the stack. The results show that for a typical 20 ampere-hour battery system with lanthanum pentanickel hydride as the hydrogen reservoir the system could perform successfully.

  15. Molecular early main group metal hydrides: synthetic challenge, structures and applications.

    PubMed

    Harder, Sjoerd

    2012-11-25

    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](∞) and [MH(2)](∞) salts are high, the synthesis of well-defined soluble hydride complexes is an obvious challenge. Access to molecular early main group metal hydrides, however, is rewarding: these hydrocarbon-soluble metal hydrides are highly reactive, have found use in early main group metal catalysis and are potentially also valuable molecular model systems for polar metal hydrides as a hydrogen storage material. The article focusses specifically on alkali and alkaline-earth metal hydride complexes and discusses the synthetic challenge, molecular structures, reactivity and applications.

  16. Effect of hydride orientation on fracture toughness of Zircaloy-4 cladding

    NASA Astrophysics Data System (ADS)

    Hsu, Hsiao-Hung; Tsay, Leu-Wen

    2011-01-01

    Hydrogen embrittlement is one of the major degradation mechanisms for high burnup fuel cladding during reactor service and spent fuel dry storage, which is related to the hydrogen concentration, morphology and orientation of zirconium hydrides. In this work, the J-integral values for X-specimens with different hydride orientations are measured to evaluate the fracture toughness of Zircaloy-4 (Zry-4) cladding. The toughness values for Zry-4 cladding with various percentages of radial hydrides are much smaller than those with circumferential hydrides only in the same hydrogen content level at 25 °C. The fractograghic features reveal that the crack path is influenced by the orientation of zirconium hydride. Moreover, the fracture toughness measurements for X-specimens at 300 °C are not sensitive to a variation in hydride orientation but to hydrogen concentration.

  17. Orbital-like motion of hydride ligands around low-coordinate metal centers.

    PubMed

    Ortuño, Manuel A; Vidossich, Pietro; Conejero, Salvador; Lledós, Agustí

    2014-12-15

    Hydrogen atoms in the coordination sphere of a transition metal are highly mobile ligands. Here, a new type of dynamic process involving hydrides has been characterized by computational means. This dynamic event consists of an orbital-like motion of hydride ligands around low-coordinate metal centers containing N-heterocyclic carbenes. The hydride movement around the carbene-metal-carbene axis is the lowest energy mode connecting energy equivalent isomers. This understanding provides crucial information for the interpretation of NMR spectra.

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

    PubMed

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

    2015-03-25

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

  19. High temperature metal hydrides as heat storage materials for solar and related applications.

    PubMed

    Felderhoff, Michael; Bogdanović, Borislav

    2009-01-01

    For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 degrees C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

  20. Thermodynamic studies and hydride transfer reactions from a rhodium complex to BX3 compounds.

    PubMed

    Mock, Michael T; Potter, Robert G; Camaioni, Donald M; Li, Jun; Dougherty, William G; Kassel, W Scott; Twamley, Brendan; DuBois, Daniel L

    2009-10-14

    This study examines the use of transition-metal hydride complexes that can be generated by the heterolytic cleavage of H(2) gas to form B-H bonds. Specifically, these studies are focused on providing a reliable and quantitative method for determining when hydride transfer from transition-metal hydrides to three-coordinate BX(3) (X = OR, SPh, F, H; R = Ph, p-C(6)H(4)OMe, C(6)F(5), (t)Bu, Si(Me)(3)) compounds will be favorable. This involves both experimental and theoretical determinations of hydride transfer abilities. Thermodynamic hydride donor abilities (DeltaG(o)(H(-))) were determined for HRh(dmpe)(2) and HRh(depe)(2), where dmpe = 1,2-bis(dimethylphosphinoethane) and depe = 1,2-bis(diethylphosphinoethane), on a previously established scale in acetonitrile. This hydride donor ability was used to determine the hydride donor ability of [HBEt(3)](-) on this scale. Isodesmic reactions between [HBEt(3)](-) and selected BX(3) compounds to form BEt(3) and [HBX(3)](-) were examined computationally to determine their relative hydride affinities. The use of these scales of hydride donor abilities and hydride affinities for transition-metal hydrides and BX(3) compounds is illustrated with a few selected reactions relevant to the regeneration of ammonia borane. Our findings indicate that it is possible to form B-H bonds from B-X bonds, and the extent to which BX(3) compounds are reduced by transition-metal hydride complexes forming species containing multiple B-H bonds depends on the heterolytic B-X bond energy. An example is the reduction of B(SPh)(3) using HRh(dmpe)(2) in the presence of triethylamine to form Et(3)N-BH(3) in high yields.

  1. High Temperature Metal Hydrides as Heat Storage Materials for Solar and Related Applications

    PubMed Central

    Felderhoff, Michael; Bogdanović, Borislav

    2009-01-01

    For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described. PMID:19333448

  2. Isolable zirconium hydride species in the reaction of amido complexes with amine-boranes.

    PubMed

    Greño, Maider; Mena, Miguel; Pérez-Redondo, Adrián; Yélamos, Carlos

    2017-03-22

    Mono-, di- and trinuclear zirconium hydride species have been isolated in the treatment of amido complexes [Zr(η(5)-C5Me5)(NMe2)nCl3-n] (n = 3, 1) with amine-borane adducts NHR2BH3 (R2 = Me2, HtBu). The reactions involve the formation of amidoborane ligands with ZrH-B interactions which readily undergo β-hydride elimination to give hydride functions.

  3. Detecting low concentrations of plutonium hydride with magnetization measurements

    SciTech Connect

    Kim, Jae Wook; Mun, E. D.; Baiardo, J. P.; Zapf, V. S.; Mielke, C. H.; Smith, A. I.; Richmond, S.; Mitchell, J.; Schwartz, D.

    2015-02-07

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

  4. Tribochemical Decomposition of Light Ionic Hydrides at Room Temperature.

    PubMed

    Nevshupa, Roman; Ares, Jose Ramón; Fernández, Jose Francisco; Del Campo, Adolfo; Roman, Elisa

    2015-07-16

    Tribochemical decomposition of magnesium hydride (MgH2) induced by deformation at room temperature was studied on a micrometric scale, in situ and in real time. During deformation, a near-full depletion of hydrogen in the micrometric affected zone is observed through an instantaneous (t < 1 s) and huge release of hydrogen (3-50 nmol/s). H release is related to a nonthermal decomposition process. After deformation, the remaining hydride is thermally decomposed at room temperature, exhibiting a much slower rate than during deformation. Confocal-microRaman spectroscopy of the mechanically affected zone was used to characterize the decomposition products. Decomposition was enhanced through the formation of the distorted structure of MgH2 with reduced crystal size by mechanical deformation.

  5. A low tritium hydride bed inventory estimation technique

    SciTech Connect

    Klein, J.E.; Shanahan, K.L.; Baker, R.A.; Foster, P.J.

    2015-03-15

    Low tritium hydride beds were developed and deployed into tritium service in Savannah River Site. Process beds to be used for low concentration tritium gas were not fitted with instrumentation to perform the steady-state, flowing gas calorimetric inventory measurement method. Low tritium beds contain less than the detection limit of the IBA (In-Bed Accountability) technique used for tritium inventory. This paper describes two techniques for estimating tritium content and uncertainty for low tritium content beds to be used in the facility's physical inventory (PI). PI are performed periodically to assess the quantity of nuclear material used in a facility. The first approach (Mid-point approximation method - MPA) assumes the bed is half-full and uses a gas composition measurement to estimate the tritium inventory and uncertainty. The second approach utilizes the bed's hydride material pressure-composition-temperature (PCT) properties and a gas composition measurement to reduce the uncertainty in the calculated bed inventory.

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

    SciTech Connect

    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.

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

    PubMed

    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.

  8. Structural isotope effects in metal hydrides and deuterides.

    PubMed

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

    2010-03-07

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

  9. Reversible metal-hydride phase transformation in epitaxial films

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    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.

  10. Irradiation effects on thermal properties of LWR hydride fuel

    NASA Astrophysics Data System (ADS)

    Terrani, Kurt; Balooch, Mehdi; Carpenter, David; Kohse, Gordon; Keiser, Dennis; Meyer, Mitchell; Olander, Donald

    2017-04-01

    Three hydride mini-fuel rods were fabricated and irradiated at the MIT nuclear reactor with a maximum burnup of 0.31% FIMA or ∼5 MWd/kgU equivalent oxide fuel burnup. Fuel rods consisted of uranium-zirconium hydride (U (30 wt%)ZrH1.6) pellets clad inside a LWR Zircaloy-2 tubing. The gap between the fuel and the cladding was filled with lead-bismuth eutectic alloy to eliminate the gas gap and the large temperature drop across it. Each mini-fuel rod was instrumented with two thermocouples with tips that are axially located halfway through the fuel centerline and cladding surface. In-pile temperature measurements enabled calculation of thermal conductivity in this fuel as a function of temperature and burnup. In-pile thermal conductivity at the beginning of test agreed well with out-of-pile measurements on unirradiated fuel and decreased rapidly with burnup.

  11. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  12. Microscopic calculation of the compressibility of hydrides of alkaline metals

    NASA Astrophysics Data System (ADS)

    Krymov, V. A.; Fuks, D. L.

    1987-09-01

    Isotherms have been constructed and compressibilities and sound velocities have been calculated for the hydrides of alkaline metals on the basis of the functional theory of the local electron density, within the framework of the pseudopotential method. The expression obtained for the electron density distribution allows one to perform the analysis of the character of the binding forces and to determine the dependence of the degree of ionization on pressure in these compounds.

  13. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions.

    PubMed

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

    2016-10-21

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

  14. Gas chromatographic separation of hydrogen isotopes using metal hydrides

    SciTech Connect

    Aldridge, F.T.

    1984-05-09

    A study was made of the properties of metal hydrides which may be suitable for use in chromatographic separation of hydrogen isotopes. Sixty-five alloys were measured, with the best having a hydrogen-deuterium separation factor of 1.35 at 60/sup 0/C. Chromatographic columns using these alloys produced deuterium enrichments of up to 3.6 in a single pass, using natural abundance hydrogen as starting material. 25 references, 16 figures, 4 tables.

  15. Low-pressure Structural Modification of Aluminum Hydride

    DTIC Science & Technology

    2011-02-01

    pressure release. 15. SUBJECT TERMS High - pressure , Diamond anvil cell, aluminum hydride 16. SECURITY CLASSIFICATION OF...loaded into the diamond anvil cell using a specialized high - pressure gas loading system (18). The in-situ pressure within the diamond anvil cell was...Visible Absorption Study of AlH3. Journal of Physics: Conference Series 2010, 215, 012047. 18. Jayaraman, A. Diamond Anvil Cell and High -

  16. METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

    DOEpatents

    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)

  17. Measurement and modeling of strain fields in zirconium hydrides precipitated at a stress concentration

    SciTech Connect

    Allen, Gregory B.; Kerr, Matthew; Daymond, Mark R.

    2012-10-23

    Hydrogen adsorption into zirconium, as a result of corrosion in aqueous environments, leads to the precipitation of a secondary brittle hydride phase. These hydrides tend to first form at stress concentrations such as fretting flaws or cracks in engineering components, potentially degrading the structural integrity of the component. One mechanism for component failure is a slow crack growth mechanism known as Delayed Hydride Cracking (DHC), where hydride fracture occurs followed by crack arrest in the ductile zirconium matrix. The current work employs both an experimental and a modeling approach to better characterize the effects and behavior of hydride precipitation at such stress concentrations. Strains around stress concentrations containing hydrides were mapped using High Energy X-ray Diffraction (HEXRD). These studies highlighted important differences in the behavior of the hydride phase and the surrounding zirconium matrix, as well as the strain associated with the precipitation of the hydride. A finite element model was also developed and compared to the X-ray strain mapping results. This model provided greater insight into details that could not be obtained directly from the experimental approaches, as well as providing a framework for future modeling to predict the effects of hydride precipitation under varied conditions.

  18. Visualization of Zn²⁺ ions in live zebrafish using a luminescent iridium(III) chemosensor.

    PubMed

    Ma, Dik-Lung; He, Hong-Zhang; Zhong, Hai-Jing; Lin, Sheng; Chan, Daniel Shiu-Hin; Wang, Liang; Lee, Simon Ming-Yuen; Leung, Chung-Hang; Wong, Chun-Yuen

    2014-08-27

    A novel luminescent cyclometalated iridium(III) complex-based chemosensor (1) bearing a zinc-specific receptor, tris(2-pyridylmethyl)amine, and the 3-phenyl-1H-pyrazole ligand has been designed and synthesized. Upon the addition of Zn(2+) ions to a solution of iridium(III) complex 1, a pronounced luminescence color change from blue to green can be observed, which may be attributed to the suppression of photoinduced electron transfer upon complexation of complex 1 with Zn(2+) ions. The interaction of iridium(III) complex 1 with Zn(2+) ions was investigated by UV-vis absorption titration, emission titration, and (1)H NMR titration. Furthermore, the iridium(III) complex 1 exhibited good selectivity for Zn(2+) over 13 other common metal ions, including K(+), Ag(+), Na(+), Ni(2+), Fe(3+), Hg(2+), Cd(2+), Mg(2+), Ca(2+), Cu(2+), Mn(2+), Co(2+), and Pb(2+) ions. The practical application of the iridium(III) complex 1 in visualizing intracellular Zn(2+) distribution in live zebrafish was also demonstrated.

  19. Synthesis, photophysical and electroluminescent properties of novel iridium (III) complexes based on 5-methyl-2-phenylbenzo[d]oxazole derivatives

    NASA Astrophysics Data System (ADS)

    Li, Xiao; Chi, Hai-Jun; Dong, Yan; Xiao, Guo-Yong; Lei, Peng; Zhang, Dong-Yu; Cui, Zheng

    2013-12-01

    A new series of phosphorescent iridium (III) complexes based on 5-methyl-2-phenylbenzo[d]oxazole derivatives as main ligands, i.e. bis(5-methyl-2- phenylbenzo[d]oxazole-N,C2‧)iridium(acetylacetonate) [(mpbo)2Ir(acac)], bis(2-(4-fluorophenyl)-5-methylbenzo[d]oxazole-N,C2‧)iridium(acetylacetonate) [(fmbo)2Ir(acac)] and bis(5-methyl-2-p-tolylbenzo[d]oxazole-N,C2‧) iridium(acetylacetonate) [(mtbo)2Ir(acac)], were synthesized for organic light-emitting diodes (OLEDs), and their photophysical, electroluminescent properties were investigated. All complexes have high thermal stability and emit intense phosphorescence from green to yellow at room temperature with high quantum efficiencies and relatively short lifetimes. The OLED based on (fmbo)2Ir(acac) as dopant emitter showed very high luminance of 26,004 cd m-2 and luminance efficiency of 18.5 cd A-1. The evidences indicated that this series of iridium (III) complexes were potential candidates for applications in organic electroluminescent devices.

  20. Iridium contents in the Late Cretaceous-Early Tertiary clays in relation to the K/T boundary, North Jordan

    NASA Astrophysics Data System (ADS)

    Abboud, Iyad Ahmed

    2016-06-01

    The mineralogy, lithology, and geochemistry of five discrete laminations across the K/T boundary of clayey shale at the Yarmouk River area, Jordan, were examined. There were no marked changes in the mineralogy of the clayey shale within the K/T boundary. This outcrop consists of more than 100 m of Maastrichtian oil shale overlying about 20 m limestone. Marly limestone included many clay laminations from organic and volcanic origins, which are considered an evidence of the K/T boundary through detected iridium anomalies. Any of these particular lamellae range from 2 mm to 5 mm in thickness. Smectite was the predominant clay mineral in smectitic shale laminations. It was located at eight meters above the K/T boundary and includes some anomalous concentrations of iridium and traces of other elements. The analysis of geochemical platinum group at the K/T boundary clays showed anomalous enrichments of iridium, compared with other carbonate rocks as a result of weathering processes of oil shale, or through concentration from weathering of basalt flows, but not pointing to an impact process. The clays in late Maastrichtian have Ir-Sc prevailed anomalies and synchronize with increasing of terrigenous and volcanogenic traced elements. Kaolin, smectite, and volkonskoite were the dominant clay minerals at the K/T boundary with high concentrations of iridium. The concentration levels of iridium in some laminations of the Yarmouk sediments ranged between 1.6 and 7.8 ppb.

  1. A Convenient Approach To Synthesize o-Carborane-Functionalized Phosphorescent Iridium(III) Complexes for Endocellular Hypoxia Imaging.

    PubMed

    Li, Xiang; Tong, Xiao; Yan, Hong; Lu, Changsheng; Zhao, Qiang; Huang, Wei

    2016-11-21

    The structure-property relationship of carborane-modified iridium(III) complexes was investigated. Firstly, an efficient approach for the synthesis of o-carborane-containing pyridine ligands a-f in high yields was developed by utilizing stable and cheap B10 H10 (Et4 N)2 as the starting material. By using these ligands, iridium(III) complexes I-VII were efficiently prepared. In combination with DFT calculations, the photophysical and electrochemical properties of these complexes were studied. The hydrophilic nido-o-carborane-based iridium(III) complex VII showed the highest phosphorescence efficiency (abs. ϕP =0.48) among known water-soluble homoleptic cyclometalated iridium(III) complexes and long emission lifetime (τ=1.24 μs) in aqueous solution. Both of them are sensitive to O2 , and thus endocellular hypoxia imaging of complex VII was realized by time-resolved luminescence imaging (TRLI). This is the first example of applying TRLI in endocellular oxygen detection with a water-soluble nido-carborane functionalized iridium(III) complex.

  2. Performance study of a hydrogen powered metal hydride actuator

    NASA Astrophysics Data System (ADS)

    Mainul Hossain Bhuiya, Md; Kim, Kwang J.

    2016-04-01

    A thermally driven hydrogen powered actuator integrating metal hydride hydrogen storage reactor, which is compact, noiseless, and able to generate smooth actuation, is presented in this article. To test the plausibility of a thermally driven actuator, a conventional piston type actuator was integrated with LaNi5 based hydrogen storage system. Copper encapsulation followed by compaction of particles into pellets, were adopted to improve overall thermal conductivity of the reactor. The operation of the actuator was thoroughly investigated for an array of operating temperature ranges. Temperature swing of the hydride reactor triggering smooth and noiseless actuation over several operating temperature ranges were monitored for quantification of actuator efficiency. Overall, the actuator generated smooth and consistent strokes during repeated cycles of operation. The efficiency of the actuator was found to be as high as 13.36% for operating a temperature range of 20 °C-50 °C. Stress-strain characteristics, actuation hysteresis etc were studied experimentally. Comparison of stress-strain characteristics of the proposed actuator with traditional actuators, artificial muscles and so on was made. The study suggests that design modification and use of high pressure hydride may enhance the performance and broaden the application horizon of the proposed actuator in future.

  3. Superconductivity of novel tin hydrides (SnnHm) under pressure

    PubMed Central

    Mahdi Davari Esfahani, M.; Wang, Zhenhai; Oganov, Artem R.; Dong, Huafeng; Zhu, Qiang; Wang, Shengnan; Rakitin, Maksim S.; Zhou, Xiang-Feng

    2016-01-01

    With the motivation of discovering high-temperature superconductors, evolutionary algorithm USPEX is employed to search for all stable compounds in the Sn-H system. In addition to the traditional SnH4, new hydrides SnH8, SnH12 and SnH14 are found to be thermodynamically stable at high pressure. Dynamical stability and superconductivity of tin hydrides are systematically investigated. Im2-SnH8, C2/m-SnH12 and C2/m-SnH14 exhibit higher superconducting transition temperatures of 81, 93 and 97 K compared to the traditional compound SnH4 with Tc of 52 K at 200 GPa. An interesting bent H3–group in Im2-SnH8 and novel linear H in C2/m-SnH12 are observed. All the new tin hydrides remain metallic over their predicted range of stability. The intermediate-frequency wagging and bending vibrations have more contribution to electron-phonon coupling parameter than high-frequency stretching vibrations of H2 and H3. PMID:26964636

  4. Superconductive sodalite-like clathrate calcium hydride at high pressures.

    PubMed

    Wang, Hui; Tse, John S; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-04-24

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H(2) fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH(6) a body-centered cubic structure with hydrogen that forms unusual "sodalite" cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H(2) of electrons donated by Ca forming an "H(4)" unit as the building block in the construction of the three-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone center. The resultant dynamic Jahn-Teller effect helps to enhance electron-phonon coupling and leads to superconductivity of CaH(6). A superconducting critical temperature (T(c)) of 220-235 K at 150 GPa obtained from the solution of the Eliashberg equations is the highest among all hydrides studied thus far.

  5. Superconductive sodalite-like clathrate calcium hydride at high pressures

    PubMed Central

    Wang, Hui; Tse, John S.; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-01-01

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H2 fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH6 a body-centered cubic structure with hydrogen that forms unusual “sodalite” cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H2 of electrons donated by Ca forming an “H4” unit as the building block in the construction of the three-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone center. The resultant dynamic Jahn–Teller effect helps to enhance electron–phonon coupling and leads to superconductivity of CaH6. A superconducting critical temperature (Tc) of 220–235 K at 150 GPa obtained from the solution of the Eliashberg equations is the highest among all hydrides studied thus far. PMID:22492976

  6. Hydrogen storage and generation using light metal hydrides

    SciTech Connect

    Lynch, F.; Mork, B.J.; Wilkes, J.S.

    1998-07-01

    The storage of hydrogen for use in fuel cells employed as portable electric power sources is important. For many applications pressurized gas or cryogenic liquid storage is not acceptable from weight or safety standpoints. This is particularly true for moderate power systems in the 50--200 watt range. A potentially attractive technology for providing hydrogen for moderately sized fuel cell-based electric power supplies is chemical hydrides. In general, chemical hydrides are materials that store hydrogen that may be released by chemical reactions. The authors report here the use of light metal hydrides, such as lithium aluminum tetrahydride and trilithium aluminum hexahydride to store hydrogen in a very dense form; about four times the density of liquid hydrogen. The hydrogen can be released by reaction with simple chemical reagents, such as water or ammonia, at approximately atmospheric pressure and at modest temperatures. The reaction rate may be controlled to provide hydrogen at a rate appropriate to that needed by a fuel cell operating at the power levels mentioned above. Usually hydrogen is the sole gaseous product, along with several solid products.

  7. Investigation of long term stability in metal hydrides

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  9. Diffusional exchange of isotopes in a metal hydride sphere.

    SciTech Connect

    Wolfer, Wilhelm G.; Hamilton, John C.; James, Scott Carlton

    2011-04-01

    This report describes the Spherical Particle Exchange Model (SPEM), which simulates exchange of one hydrogen isotope by another hydrogen isotope in a spherical metal hydride particle. This is one of the fundamental physical processes during isotope exchange in a bed of spherical metal particles and is thus one of the key components in any comprehensive physics-based model of exchange. There are two important physical processes in the model. One is the entropy of mixing between the two isotopes; the entropy of mixing is increased by having both isotopes randomly placed at interstitial sites on the lattice and thus impedes the exchange process. The other physical process is the elastic interaction between isotope atoms on the lattice. The elastic interaction is the cause for {beta}-phase formation and is independent of the isotope species. In this report the coupled diffusion equations for two isotopes in the {beta}-phase hydride are solved. A key concept is that the diffusion of one isotope depends not only on its concentration gradient, but also on the concentration gradient of the other isotope. Diffusion rate constants and the chemical potentials for deuterium and hydrogen in the {beta}-phase hydride are reviewed because these quantities are essential for an accurate model of the diffusion process. Finally, a summary of some of the predictions from the SPEM model are provided.

  10. Electronic structure of ternary rhodium hydrides with lithium and magnesium.

    PubMed

    Becker, Jonas Nils; Bauer, Jessica; Giehr, Andreas; Chu, Pui Ieng; Kunkel, Nathalie; Springborg, Michael; Kohlmann, Holger

    2014-01-21

    Chemical bonding in and electronic structure of lithium and magnesium rhodium hydrides are studied theoretically using DFT methods. For Li3RhH4 with planar complex RhH4 structural units, Crystal Orbital Hamilton Populations reveal significant Rh−Rh interactions within infinite one-dimensional ∞ 1 [RhH4] stacks in addition to strong rhodium−hydrogen bonding. These metal−metal interactions are considerably weaker in the hypothetical, heavier homologue Na3RhH4. Both compounds are small-band gap semiconductors. The electronic structures of Li3RhH6 and Na3RhH6 with rhodium surrounded octahedrally by hydrogen, on the other hand, are compatible with a classical complex hydride model according to the limiting ionic formula (M+)3[RhH6]3− without any metal−metal interaction between the 18-electron hydridorhodate complexes. In MgRhH, building blocks of the composition (RhH2)4 are formed with strong rhodium−hydrogen and significant rhodium−rhodium bonding (bond lengths of 298 pm within Rh4 squares). These units are linked together to infinite two-dimensional layers ∞ 2 [(RhH2/2)4] via common hydrogen atoms. Li3RhH4 and MgRhH are accordingly examples for border cases of chemical bonding where the classical picture of hydridometalate complexes in complex hydrides is not sufficient to properly describe the chemical bonding situation.

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

    PubMed Central

    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

  12. Superconductivity of novel tin hydrides (SnnHm) under pressure

    NASA Astrophysics Data System (ADS)

    Mahdi Davari Esfahani, M.; Wang, Zhenhai; Oganov, Artem R.; Dong, Huafeng; Zhu, Qiang; Wang, Shengnan; Rakitin, Maksim S.; Zhou, Xiang-Feng

    2016-03-01

    With the motivation of discovering high-temperature superconductors, evolutionary algorithm USPEX is employed to search for all stable compounds in the Sn-H system. In addition to the traditional SnH4, new hydrides SnH8, SnH12 and SnH14 are found to be thermodynamically stable at high pressure. Dynamical stability and superconductivity of tin hydrides are systematically investigated. Im2-SnH8, C2/m-SnH12 and C2/m-SnH14 exhibit higher superconducting transition temperatures of 81, 93 and 97 K compared to the traditional compound SnH4 with Tc of 52 K at 200 GPa. An interesting bent H3–group in Im2-SnH8 and novel linear H in C2/m-SnH12 are observed. All the new tin hydrides remain metallic over their predicted range of stability. The intermediate-frequency wagging and bending vibrations have more contribution to electron-phonon coupling parameter than high-frequency stretching vibrations of H2 and H3.

  13. Metal hydride/chemical heat pump development project

    NASA Astrophysics Data System (ADS)

    Madariaga, H. A.; Rohy, D. A.

    1982-02-01

    A mental hydride heat pump (MHHP) is a chemical heat pump containing two different hydrides and using hydrogen as a working fluid 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 cooling or temperature upgrading over a wide range of input and ambient temperatures. This system can be used with a variety of heat sources including industrial waste heat, solar energy or a fossil fuel. Temperature as low as 130 F can drive the MHHP when a suitable sink is provided. A project is currently underway to develop this unique heat pump for a specific application. The goals of the project include the development of cost effective hydride containers with high heat transfer and low mass; design and fabrication of a laboratory evaluation model; and design and fabrication of a demonstration unit. Extensive component and system test will provide the data for the design processes.

  14. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water

    PubMed Central

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-01-01

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m2 g−1) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates. PMID:26912370

  15. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water

    NASA Astrophysics Data System (ADS)

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-02-01

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m2 g‑1) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates.

  16. Iridium nanoparticles supported on hierarchical porous N-doped carbon: an efficient water-tolerant catalyst for bio-alcohol condensation in water.

    PubMed

    Liu, Di; Chen, Xiufang; Xu, Guoqiang; Guan, Jing; Cao, Quan; Dong, Bo; Qi, Yunfei; Li, Chunhu; Mu, Xindong

    2016-02-25

    Nitrogen-doped hierarchical porous carbons were synthesized successfully by a controllable one-pot method using glucose and dicyandiamide as carbon source and nitrogen source via hydrothermal carbonization process. The nitrogen-doped materials, possessing high nitrogen content (up to 7 wt%), large surface area (>320 m(2) g(-1)) and excellent hierarchical nanostructure, were employed as catalyst supports for immobilization of iridium nanoparticles for bio-alcohol condensation in water. The introduction of nitrogen atoms into the carbon framework significantly improved iridium nanoparticles dispersion and stabilization. The novel iridium catalysts exhibited superior catalytic activity in the aqueous phase condensation of butanol, offering high butanol conversion of 45% with impressive 2-ethylhexanol selectivity of 97%. The heterogeneous catalysts had great advantages of easy recovery and high catalytic stability. The outstanding catalytic performance could be attributed to excellent dispersion of iridium nanoparticles, stronger iridium-support interactions and interaction of nitrogen species with alcohol substrates.

  17. Thermodynamic and kinetic hydricity of ruthenium(II) hydride complexes.

    PubMed

    Matsubara, Yasuo; Fujita, Etsuko; Doherty, Mark D; Muckerman, James T; Creutz, Carol

    2012-09-26

    Despite the fundamental importance of the hydricity of a transition metal hydride (ΔG(H–)°(MH) for the reaction M–H → M+ + H–) in a range of reactions important in catalysis and solar energy storage, ours (J. Am. Chem. Soc.2009, 131, 2794) are the only values reported for water solvent, and there has been no basis for comparison of these with the wider range already determined for acetonitrile solvent, in particular. Accordingly, we have used a variety of approaches to determine hydricity values in acetonitrile of Ru(II) hydride complexes previously studied in water. For [Ru(η(6)-C6Me6)(bpy)H]+ (bpy = 2,2′-bipyridine), we used a thermodynamic cycle based on evaluation of the acidity of [Ru(η(6)-C6Me6)(bpy)H]+ pKa = 22.5 ± 0.1 and the [Ru(η(6)-C6Me6)(bpy)(NCCH3)(1/0)](2+/0) electrochemical potential (−1.22 V vs Fc+/Fc). For [Ru(tpy)(bpy)H]+ (tpy = 2,2′:6′,2″-terpyridine) we utilized organic hydride ion acceptors (A+) of characterized hydricity derived from imidazolium cations and pyridinium cations, and determined K for the hydride transfer reaction, S + MH+ + A+ → M(S)2+ + AH (S = CD3CN, MH+ = [Ru(tpy)(bpy)H]+), by 1H NMR measurements. Equilibration of initially 7 mM solutions was slow--on the time scale of a day or more. When E°(H+/H–) is taken as 79.6 kcal/mol vs Fc+/Fc as a reference, the hydricities of [Ru(η(6)-C6Me6)(bpy)H]+ and [Ru(tpy)(bpy)H]+ were estimated as 54 ± 2 and 39 ± 3 kcal/mol, respectively, in acetonitrile to be compared with the values 31 and 22 kcal/mol, respectively, found for aqueous media. The pKa estimated for [Ru(tpy)(bpy)H]+ in acetonitrile is 32 ± 3. UV–vis spectroscopic studies of [Ru(η(6)-C6Me6)(bpy)]0 and [Ru(tpy)(bpy)]0 indicate that they contain reduced bpy and tpy ligands, respectively. These conclusions are supported by DFT electronic structure results. Comparison of the hydricity values for acetonitrile and water reveals a flattening or compression of the hydricity range upon transferring the

  18. Synthesis of Highly Active Mg-BASED Hydrides Using Hydriding Combustion Synthesis and NbF5 Additives

    NASA Astrophysics Data System (ADS)

    Chourashiya, M. G.; Park, C. N.; Park, C. J.

    2012-09-01

    Superiority of the hydriding combustion (HC) technique over conventional metallurgical approach to the synthesis of cost-effective Mg based hydrides, which show promise as hydrogen storage materials, is well known. In the present research, we report further improvements in HC prepared Mg-based materials, achieved by optimizing the preparative parameters of HC and by catalytic addition. Mg90-Ni60-C40 composites prepared using optimized processing parameters were ball-milled with NbF5 (10 h) and characterized for their micro-structural and hydriding properties. The ball-milled/catalyzed powder showed decreased crystallinity with CNTs on its surfaces. Surface area of the ball-milled powder decreased to almost half of the as-HC powder, while TG analysis revealed a four-fold decrease in the desorption temperature of the milled powder compared to that of the as-HC prepared powder. Activated samples achieved the maximum absorption/desorption limits (5.3 wt.%) at as low as 100°C, underlining the possibility of the use of these materials in portable hydrogen storage devices.

  19. Comparison of hydrogen elimination from molecular zinc and magnesium hydride clusters.

    PubMed

    Intemann, Julia; Sirsch, Peter; Harder, Sjoerd

    2014-08-25

    In analogy to the previously reported tetranuclear magnesium hydride cluster with a bridged dianionic bis-β-diketiminate ligand, a related zinc hydride cluster has been prepared. The crystal structures of these magnesium and zinc hydride complexes are similar: the metal atoms are situated at the corners of a tetrahedron in which the vertices are bridged either by dianionic bis-β-diketiminate ligands or hydride ions. Both structures are retained in solution and show examples of H(-)⋅⋅⋅H(-) NMR coupling (Mg: 8.5 Hz; Zn: 16.0 Hz). The zinc hydride cluster [NN-(ZnH)2]2 thermally decomposes at 90 °C and releases 1.8 equivalents of H2 . In contrast to magnesium hydride clusters, there is no apparent relationship between cluster size and thermal decomposition temperature for the zinc hydrides. DFT calculations reproduced the structure of the zinc hydride cluster reasonably well and charge density analysis showed no bond paths between the hydride ions. This contrasts with calculations on the analogous magnesium hydride cluster in which a counter-intuitive H(-)⋅⋅⋅H(-) bond path was observed. Forcing a reduced H(-)⋅⋅⋅H(-) distance in the zinc hydride cluster, however, gave rise to a H(-)⋅⋅⋅H(-) bond path. Such weak interactions could play a role in H2 desorption. The presumed molecular product after H2 release, a Zn(I) cluster, could not be characterized experimentally but DFT calculations predicted a cluster with two localized Zn-Zn bonds.

  20. Low-Cost Metal Hydride Thermal Energy Storage System for Concentrating Solar Power Systems

    SciTech Connect

    Zidan, Ragaiy; Hardy, B. J.; Corgnale, C.; Teprovich, J. A.; Ward, P.; Motyka, Ted

    2016-01-31

    The objective of this research was to evaluate and demonstrate a metal hydride-based TES system for use with a CSP system. A unique approach has been applied to this project that combines our modeling experience with the extensive material knowledge and expertise at both SRNL and Curtin University (CU). Because of their high energy capacity and reasonable kinetics many metal hydride systems can be charged rapidly. Metal hydrides for vehicle applications have demonstrated charging rates in minutes and tens of minutes as opposed to hours. This coupled with high heat of reaction allows metal hydride TES systems to produce very high thermal power rates (approx. 1kW per 6-8 kg of material). A major objective of this work is to evaluate some of the new metal hydride materials that have recently become available. A problem with metal hydride TES systems in the past has been selecting a suitable high capacity low temperature metal hydride material to pair with the high temperature material. A unique aspect of metal hydride TES systems is that many of these systems can be located on or near dish/engine collectors due to their high thermal capacity and small size. The primary objective of this work is to develop a high enthalpy metal hydride that is capable of reversibly storing hydrogen at high temperatures (> 650 °C) and that can be paired with a suitable low enthalpy metal hydride with low cost materials. Furthermore, a demonstration of hydrogen cycling between the two hydride beds is desired.