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Sample records for hydride transfer catalyzed

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

    Science.gov (United States)

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

    2017-03-14

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

  2. Stereo-specificity for pro-(R) hydrogen of NAD(P)H during enzyme-catalyzed hydride transfer to CL-20

    International Nuclear Information System (INIS)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2005-01-01

    A dehydrogenase from Clostridium sp. EDB2 and a diaphorase from Clostridium kluyveri were reacted with CL-20 to gain insights into the enzyme-catalyzed hydride transfer to CL-20, and the enzyme's stereo-specificity for either pro-R or pro-S hydrogens of NAD(P)H. Both enzymes biotransformed CL-20 at rates of 18.5 and 24 nmol/h/mg protein, using NADH and NADPH as hydride-source, respectively, to produce a N-denitrohydrogenated product with a molecular weight of 393 Da. In enzyme kinetics studies using reduced deuterated pyridine nucleotides, we found a kinetic deuterium isotopic effect of 2-fold on CL-20 biotransformation rate using dehydrogenase enzyme against (R)NADD as a hydride-source compared to either (S)NADD or NADH. Whereas, in case of diaphorase, the kinetic deuterium isotopic effect of about 1.5-fold was observed on CL-20 biotransformation rate using (R)NADPD as hydride-source. In a comparative study with LC-MS, using deuterated and non-deuterated NAD(P)H, we found a positive mass-shift of 1 Da in the N-denitrohydrogenated product suggesting the involvement of a deuteride (D - ) transfer from NAD(P)D. The present study thus revealed that both dehydrogenase and diaphorase enzymes from the two Clostridium species catalyzed a hydride transfer to CL-20 and showed stereo-specificity for pro-R hydrogen of NAD(P)H

  3. C-H Bond Functionalization via Hydride Transfer: Direct Coupling of Unactivated Alkynes and sp3 C-H Bonds Catalyzed by Platinum Tetraiodide

    Science.gov (United States)

    Vadola, Paul A.; Sames, Dalibor

    2010-01-01

    We report a catalytic intramolecular coupling between terminal unactivated alkynes and sp3 C-H bonds via the through-space hydride transfer (HT-cyclization of alkynes). This method enables one-step preparation of complex heterocyclic compounds by α-alkenylation of readily available cyclic ethers and amines. We show that PtI4 is an effective Lewis acid catalyst for the activation of terminal alkynes for the hydride attack and subsequent C-C bond formation. In addition, we have shown that the activity of neutral platinum salts (PtXn) can be modulated by the halide ligands. This modulation in turn allows for fine-tuning of the platinum center reactivity to match the reactivity and stability of selected substrates and products. PMID:19852462

  4. Cyclopentadiene-mediated hydride transfer from rhodium complexes.

    Science.gov (United States)

    Pitman, C L; Finster, O N L; Miller, A J M

    2016-07-12

    Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+).

  5. Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy.

    Science.gov (United States)

    Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

    2018-01-25

    We propose a method to approximate the kinetic properties of hydride donor species by relating the nucleophilicity (N) of a hydride to the activation free energy ΔG ⧧ of its corresponding hydride transfer reaction. N is a kinetic parameter related to the hydride transfer rate constant that quantifies a nucleophilic hydridic species' tendency to donate. Our method estimates N using quantum chemical calculations to compute ΔG ⧧ for hydride transfers from hydride donors to CO 2 in solution. A linear correlation for each class of hydrides is then established between experimentally determined N values and the computationally predicted ΔG ⧧ ; this relationship can then be used to predict nucleophilicity for different hydride donors within each class. This approach is employed to determine N for four different classes of hydride donors: two organic (carbon-based and benzimidazole-based) and two inorganic (boron and silicon) hydride classes. We argue that silicon and boron hydrides are driven by the formation of the more stable Si-O or B-O bond. In contrast, the carbon-based hydrides considered herein are driven by the stability acquired upon rearomatization, a feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled.

  6. Hydride Transfer versus Deprotonation Kinetics in the Isobutane–Propene Alkylation Reaction: A Computational Study

    Science.gov (United States)

    2017-01-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C–C bond formation between a tert-butyl fragment and an additional olefin, or via deprotonation of the tert-butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle. PMID:29226012

  7. Hydride Transfer versus Deprotonation Kinetics in the Isobutane-Propene Alkylation Reaction: A Computational Study.

    Science.gov (United States)

    Liu, Chong; van Santen, Rutger A; Poursaeidesfahani, Ali; Vlugt, Thijs J H; Pidko, Evgeny A; Hensen, Emiel J M

    2017-12-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane-propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C-C bond formation between a tert -butyl fragment and an additional olefin, or via deprotonation of the tert -butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle.

  8. Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

    Science.gov (United States)

    You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

    2017-02-03

    A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

  9. Cytochrome P450BM-3 reduces aldehydes to alcohols through a direct hydride transfer

    Energy Technology Data Exchange (ETDEWEB)

    Kaspera, Ruediger; Sahele, Tariku; Lakatos, Kyle [Department of Medicinal Chemistry, University of Washington, Box 357610, Seattle, WA 98195-7610 (United States); Totah, Rheem A., E-mail: rtotah@u.washington.edu [Department of Medicinal Chemistry, University of Washington, Box 357610, Seattle, WA 98195-7610 (United States)

    2012-02-17

    Highlights: Black-Right-Pointing-Pointer Cytochrome P450BM-3 reduced aldehydes to alcohols efficiently (k{sub cat} {approx} 25 min{sup -1}). Black-Right-Pointing-Pointer Reduction is a direct hydride transfer from R-NADP{sup 2}H to the carbonyl moiety. Black-Right-Pointing-Pointer P450 domain variants enhance reduction through potential allosteric/redox interactions. Black-Right-Pointing-Pointer Novel reaction will have implications for metabolism of xenobiotics. -- Abstract: Cytochrome P450BM-3 catalyzed the reduction of lipophilic aldehydes to alcohols efficiently. A k{sub cat} of {approx}25 min{sup -1} was obtained for the reduction of methoxy benzaldehyde with wild type P450BM-3 protein which was higher than in the isolated reductase domain (BMR) alone and increased in specific P450-domain variants. The reduction was caused by a direct hydride transfer from preferentially R-NADP{sup 2}H to the carbonyl moiety of the substrate. Weak substrate-P450-binding of the aldehyde, turnover with the reductase domain alone, a deuterium incorporation in the product from NADP{sup 2}H but not D{sub 2}O, and no inhibition by imidazole suggests the reductase domain of P450BM-3 as the potential catalytic site. However, increased aldehyde reduction by P450 domain variants (P450BM-3 F87A T268A) may involve allosteric or redox mechanistic interactions between heme and reductase domains. This is a novel reduction of aldehydes by P450BM-3 involving a direct hydride transfer and could have implications for the metabolism of endogenous substrates or xenobiotics.

  10. Cytochrome P450BM-3 reduces aldehydes to alcohols through a direct hydride transfer

    International Nuclear Information System (INIS)

    Kaspera, Rüdiger; Sahele, Tariku; Lakatos, Kyle; Totah, Rheem A.

    2012-01-01

    Highlights: ► Cytochrome P450BM-3 reduced aldehydes to alcohols efficiently (k cat ∼ 25 min −1 ). ► Reduction is a direct hydride transfer from R-NADP 2 H to the carbonyl moiety. ► P450 domain variants enhance reduction through potential allosteric/redox interactions. ► Novel reaction will have implications for metabolism of xenobiotics. -- Abstract: Cytochrome P450BM-3 catalyzed the reduction of lipophilic aldehydes to alcohols efficiently. A k cat of ∼25 min −1 was obtained for the reduction of methoxy benzaldehyde with wild type P450BM-3 protein which was higher than in the isolated reductase domain (BMR) alone and increased in specific P450-domain variants. The reduction was caused by a direct hydride transfer from preferentially R-NADP 2 H to the carbonyl moiety of the substrate. Weak substrate-P450-binding of the aldehyde, turnover with the reductase domain alone, a deuterium incorporation in the product from NADP 2 H but not D 2 O, and no inhibition by imidazole suggests the reductase domain of P450BM-3 as the potential catalytic site. However, increased aldehyde reduction by P450 domain variants (P450BM-3 F87A T268A) may involve allosteric or redox mechanistic interactions between heme and reductase domains. This is a novel reduction of aldehydes by P450BM-3 involving a direct hydride transfer and could have implications for the metabolism of endogenous substrates or xenobiotics.

  11. Another Look at the Mechanisms of Hydride Transfer Enzymes with Quantum and Classical Transition Path Sampling.

    Science.gov (United States)

    Dzierlenga, Michael W; Antoniou, Dimitri; Schwartz, Steven D

    2015-04-02

    The mechanisms involved in enzymatic hydride transfer have been studied for years, but questions remain due, in part, to the difficulty of probing the effects of protein motion and hydrogen tunneling. In this study, we use transition path sampling (TPS) with normal mode centroid molecular dynamics (CMD) to calculate the barrier to hydride transfer in yeast alcohol dehydrogenase (YADH) and human heart lactate dehydrogenase (LDH). Calculation of the work applied to the hydride allowed for observation of the change in barrier height upon inclusion of quantum dynamics. Similar calculations were performed using deuterium as the transferring particle in order to approximate kinetic isotope effects (KIEs). The change in barrier height in YADH is indicative of a zero-point energy (ZPE) contribution and is evidence that catalysis occurs via a protein compression that mediates a near-barrierless hydride transfer. Calculation of the KIE using the difference in barrier height between the hydride and deuteride agreed well with experimental results.

  12. Quantum-chemical study of hydride transfer in catalytic transformation of paraffins on zeolites

    NARCIS (Netherlands)

    Kazansky, V.B.; Frash, M.V.; Santen, van R.A.; Chon, H.; Ihm, S.-K.; Uh, Y.S.

    1997-01-01

    Ab initio quantum-chemical cluster calculations demonstrate that the activated complexes of hydride transfer reaction in catalytic transformation of paraffins on zeolites very much resembles adsorbed nonclassical carbonium ions. The calculated activation energies for reactions involving propane and

  13. Insight into the stereospecificity of short-chain thermus thermophilus alcohol dehydrogenase showing pro-S hydride transfer and prelog enantioselectivity.

    Science.gov (United States)

    Pennacchio, Angela; Giordano, Assunta; Esposito, Luciana; Langella, Emma; Rossi, Mosè; Raia, Carlo A

    2010-04-01

    The stereochemistry of the hydride transfer in reactions catalyzed by NAD(H)-dependent alcohol dehydrogenase from Thermus thermophilus HB27 was determined by means of (1)H-NMR spectroscopy. The enzyme transfers the pro-S hydrogen of [4R-(2)H]NADH and exhibits Prelog specificity. Enzyme-substrate docking calculations provided structural details about the enantioselectivity of this thermophilic enzyme. These results give additional insights into the diverse active site architectures of the largely versatile short-chain dehydrogenase superfamily enzymes. A feasible protocol for the synthesis of [4R-(2)H]NADH with high yield was also set up by enzymatic oxidation of 2-propanol-d(8) catalyzed by Bacillus stearothermophilus alcohol dehydrogenase.

  14. Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

    KAUST Repository

    Brzozowska, Aleksandra; Azofra, Luis Miguel; Zubar, Viktoriia; Atodiresei, Iuliana; Cavallo, Luigi; Rueping, Magnus; El-Sepelgy, Osama

    2018-01-01

    The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

  15. Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

    KAUST Repository

    Brzozowska, Aleksandra

    2018-03-30

    The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

  16. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian

    2016-04-10

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.

  17. Ruthenium Hydride/Brønsted Acid-Catalyzed Tandem Isomerization/N-Acyliminium Cyclization Sequence for the Synthesis of Tetrahydro-β-carbolines

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke; Clausen, Janie Regitse Waël; Ohm, Ragnhild Gaard

    2013-01-01

    This paper describes an efficient tandem sequence for the synthesis of 1,2,3,4-tetrahydro-β-carbolines (THBCs) relying on a ruthenium hydride/Brønsted acid- catalyzed isomerization of allylic amides to N-acyliminium ion intermediates which are trapped by a tethered indolenucleophile. The methodol...... the Suzuki cross-coupling reaction to the isomerization/N-acyliminium cyclization sequence. Finally, diastereo- and enantioselective versions of the title reaction have been examined using substrate control (with dr >15: 1) and asymmetric catalysis (ee up to 57%), respectively...

  18. Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

    Science.gov (United States)

    Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

    2015-05-27

    The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

  19. Determination of hydride transfer stereospecificity of NADH-dependent alcohol-aldehyde/ketone oxidoreductase from Sulfolobus solfataricus.

    Science.gov (United States)

    Trincone, A; Lama, L; Rella, R; D'Auria, S; Raia, C A; Nicolaus, B

    1990-10-18

    This paper describes the determination of stereospecificity of hydride transfer reaction of an alcohol dehydrogenase isolated from the archaebacterium Sulfolobus solfataricus. The 1H-NMR and EI-MS data indicate that the enzyme transfers the pro-R hydrogen from coenzyme to substrate and is therefore an A-specific dehydrogenase.

  20. Reversible dihydrogen activation and hydride transfer by a uranium nitride complex

    Energy Technology Data Exchange (ETDEWEB)

    Falcone, Marta; Poon, Lok Nga; Fadaei Tirani, Farzaneh; Mazzanti, Marinella [Institut des Sciences et Ingenierie Chimiques, Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne (Switzerland)

    2018-03-26

    Cleavage of dihydrogen is an important step in the industrial and enzymatic transformation of N{sub 2} into ammonia. The reversible cleavage of dihydrogen was achieved under mild conditions (room temperature and 1 atmosphere of H{sub 2}) by the molecular uranium nitride complex, [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-N)], leading to a rare hydride-imide bridged diuranium(IV) complex, [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-H)(μ-NH)], that slowly releases H{sub 2} under vacuum. This complex is highly reactive and quickly transfers hydride to acetonitrile and carbon dioxide at room temperature, affording the ketimide- and formate-bridged U{sup IV} species [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-NH)(μ-CH{sub 3}CHN)] and [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-HCOO)(μ-NHCOO)]. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Stereochemical course of enzyme-catalyzed aminopropyl transfer: spermidine synthase

    International Nuclear Information System (INIS)

    Kullberg, D.W.; Orr, G.R.; Coward, J.K.

    1986-01-01

    The R and S enantionmers of S-adenosyl-3-[ 2 H]3-(methylthio)-1-propylamine (decarboxylated S-adenosylmethionine), previously synthesized in this laboratory, were incubated with [1,4- 2 H 4 ]-putrescine in the presence of spermidine synthase from E. coli. The resulting chiral [ 2 H 5 ]spermidines were isolated and converted to their N 1 ,N 7 -dibocspermidine-N 4 -(1S,4R)-camphanamides. The derivatives were analyzed by 500 MHz 1 H-NMR and the configuration of the chiral center assigned by correlation with the spectra of synthetic chiral [ 2 H 3 ]dibocspermidine camphanamide standards. The enzyme-catalyzed aminopropyl transfer was shown to occur with net retention of configuration, indicative of a double-displacement mechanism. This result concurs with that of a previous steady-state kinetics study of spermidine synthase isolated from E. coli, but contradicts the single-displacement mechanism suggested by a stereochemical analysis of chiral spermidines biosynthesized in E. coli treated with chirally deuterated methionines. It also indicates that this aminopropyltransferase is mechanistically distinct from the methyltransferases, which have been shown to act via a single-displacement mechanism (net inversion at -CH 3 ) in all cases studied to date

  2. Efficient, crosswise catalytic promiscuity among enzymes that catalyze phosphoryl transfer.

    Science.gov (United States)

    Mohamed, Mark F; Hollfelder, Florian

    2013-01-01

    The observation that one enzyme can accelerate several chemically distinct reactions was at one time surprising because the enormous efficiency of catalysis was often seen as inextricably linked to specialization for one reaction. Originally underreported, and considered a quirk rather than a fundamental property, enzyme promiscuity is now understood to be important as a springboard for adaptive evolution. Owing to the large number of promiscuous enzymes that have been identified over the last decade, and the increased appreciation for promiscuity's evolutionary importance, the focus of research has shifted to developing a better understanding of the mechanistic basis for promiscuity and the origins of tolerant or restrictive specificity. We review the evidence for widespread crosswise promiscuity amongst enzymes that catalyze phosphoryl transfer, including several members of the alkaline phosphatase superfamily, where large rate accelerations between 10(6) and 10(17) are observed for both native and multiple promiscuous reactions. This article is part of a Special Issue entitled: Chemistry and mechanism of phosphatases, diesterases and triesterases. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Phospholipid transfer from vesicles to high density lipoproteins, catalyzed by human plasma phospholipid transfer protein

    International Nuclear Information System (INIS)

    Sweeny, S.A.

    1985-01-01

    Human plasma phospholipid transfer protein (PLTP) catalyzes the mass transfer of phosphatidylcholine (PC). Partial purification of PLTP yielded proteins with apparent M/sub r/ = 59,000 and 40,000 by SDS-PAGE. PLTP activity was measured by transfer of [ 14 C]L-α-dipalmitoyl PC from egg-PC vesicles to HDL. Activity was enhanced at low pH (4.5) upon addition of β-mercaptoethanol while Ca +2 and Na + had no effect. E/sub act/ for facilitated PC transfer was 18.2 +/- 2 kcal/mol. The donor specificity of PLTP was examined using vesicles containing egg-PC plus cholesterol or sphingomyelin. The fluidity of the donor membrane (measured by fluorescence polarization of diphenylhexatriene) correlated strongly with a decrease in PLTP activity. Phosphatidic acid did not affect activity. Increase in vesicle size reduced activity. The acceptor specificity of PLTP was examined using chemically modified HDL. PLTP activity increased up to 1.7-fold with an initial increase in negative charge and then decreased upon extensive modification. A mechanism is proposed where PLTP binds to vesicls and enhances the diffusion of PC into the medium where it is adsorbed by HDL

  4. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls.

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D; Krische, Michael J

    2015-10-14

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo-, and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k, and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k, and 6m, respectively. Primary alcohols 2a, 2l, and 2p were converted to the siloxy-crotylation products 3a, 3l, and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l, and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes.

  5. Influence of zeolite pore structure on product selectivities for protolysis and hydride transfer reactions in the cracking of n-pentane.

    Science.gov (United States)

    Miyaji, Akimitsu; Iwase, Yasuyoshi; Nishitoba, Toshiki; Long, Nguyen Quang; Motokura, Ken; Baba, Toshihide

    2015-02-21

    The conversion of n-pentane was carried out to examine the effects of reaction conditions on changes in product selectivities at 823 K, using zeolites with 10- and 12-membered rings. We also investigated the influence of the pore structure of these zeolites on their catalytic activities for both protolysis and hydride transfer reactions. In the first half of this work, we examined the influence of acidic proton concentration and n-pentane pressure on the reaction rates for protolysis and hydride transfer reactions using ZSM-5 zeolites. The rates of hydride transfer reactions were more influenced by pentane pressure compared to protolysis reactions, and were proportional to the square of n-pentane pressure and the concentration of acidic protons. In the second half of this work, the influence of the zeolite pore structure on changes in product selectivities with n-pentane conversion and that on the rates of protolysis and the hydride transfer reactions were revealed using various zeolites with 10- and 12-membered rings. The catalytic activities of zeolites for the protolysis and hydride transfer reactions were influenced more by the spatial volume of the zeolite cavity than the acid strength of protons on the zeolite.

  6. Ag-catalyzed InAs nanowires grown on transferable graphite flakes

    DEFF Research Database (Denmark)

    Meyer-Holdt, Jakob; Kanne, Thomas; Sestoft, Joachim E.

    2016-01-01

    on exfoliated graphite flakes by molecular beam epitaxy. Ag catalyzes the InAs nanowire growth selectively on the graphite flakes and not on the underlying InAs substrates. This allows for easy transfer of the flexible graphite flakes with as-grown nanowire ensembles to arbitrary substrates by a micro...

  7. Evidence for tunneling in base-catalyzed isomerization of glyceraldehyde to dihydroxyacetone by hydride shift under formose conditions.

    Science.gov (United States)

    Cheng, Liang; Doubleday, Charles; Breslow, Ronald

    2015-04-07

    Hydrogen atom transfer reactions between the aldose and ketose are key mechanistic features in formose chemistry by which formaldehyde is converted to higher sugars under credible prebiotic conditions. For one of these transformations, we have investigated whether hydrogen tunneling makes a significant contribution to the mechanism by examining the deuterium kinetic isotope effect associated with the hydrogen transfer during the isomerization of glyceraldehyde to the corresponding dihydroxyacetone. To do this, we developed a quantitative HPLC assay that allowed us to measure the apparent large intrinsic kinetic isotope effect. From the Arrhenius plot of the kinetic isotope effect, the ratio of the preexponential factors AH/AD was 0.28 and the difference in activation energies Ea(D) - Ea(H) was 9.1 kJ·mol(-1). All these results imply a significant quantum-mechanical tunneling component in the isomerization mechanism. This is supported by multidimensional tunneling calculations using POLYRATE with small curvature tunneling.

  8. Insight into solid-liquid phase transfer catalyzed synthesis of ...

    Indian Academy of Sciences (India)

    Ganapati D Yadav

    2017-11-16

    Nov 16, 2017 ... Mecoprop ester using K2CO3 as base and development of new kinetic model ... acid family.1 Several salts and esters of Mecoprop are used as active ..... Influence of mass transfer was determined by varying the stirring speed ...

  9. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  10. Domino reactions initiated by intramolecular hydride transfers from tri(di)arylmethane fragments to ketenimine and carbodiimide functions.

    Science.gov (United States)

    Alajarin, Mateo; Bonillo, Baltasar; Ortin, Maria-Mar; Sanchez-Andrada, Pilar; Vidal, Angel; Orenes, Raul-Angel

    2010-10-21

    The ability of triarylmethane and diarylmethane fragments to behave as hydride donors participating in thermal [1,5]-H shift/6π-ERC tandem processes involving ketenimine and carbodiimide functions is disclosed. C-Alkyl-C-phenyl ketenimines N-substituted by a triarylmethane substructure convert into a variety of 3,3,4,4-tetrasubstituted-3,4-dihydroquinolines, as structurally related carbodiimides transform into 3,4,4-trisubstituted-3,4-dihydroquinazolines via transient ortho-azaxylylenes. The first step of these one-pot conversions, the [1,5]-H shift, is considered to be a hydride migration on the basis of the known hydricity of the tri(di)arylmethane fragment and the electrophilicity of the central heterocumulenic carbon atom, whereas the final electrocyclization involves the formation of a sterically congested C-C or C-N bond. In the cases of C,C-diphenyl substituted triarylmethane-ketenimines the usual 6π-ERC becomes prohibited by the presence of two phenyl rings at each end of the azatrienic system. This situation opens new reaction channels: (a) following the initial hydride shift, the tandem sequence continues with an alternative electrocyclization mode to give 9,10-dihydroacridines, (b) the full sequence is initiated by a rare 1,5 migration of an electron-rich aryl group, followed by a 6π-ERC which leads to 2-aryl-3,4-dihydroquinolines, or (c) a different [1,5]-H shift/6π-ERC sequence involving the initial migration of a hydrogen atom from a methyl group at the ortho position to the nitrogen atom of the ketenimine function. Diarylmethane-ketenimines bearing a methyl group at the benzylic carbon atom experience a tandem double [1,5]-H shift, the first one being the usual benzylic hydride transfer whereas the second one involves the methyl group at the initial benzylic carbon atom, the reaction products being 2-aminostyrenes. Diarylmethane-ketenimines lacking such a methyl group convert into 3,4-dihydroquinolines by the habitual tandem [1,5]-H shift/6

  11. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

    2016-01-01

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel

  12. Hydride Transfer versus Deprotonation Kinetics in the Isobutane–Propene Alkylation Reaction: A Computational Study

    OpenAIRE

    Liu, Chong; van Santen, Rutger A.; Poursaeidesfahani, Ali; Vlugt, Thijs J. H.; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2017-01-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate o...

  13. Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies.

    Science.gov (United States)

    Dolan, Nicholas S; Scamp, Ryan J; Yang, Tzuhsiung; Berry, John F; Schomaker, Jennifer M

    2016-11-09

    The development of new catalysts for selective nitrene transfer is a continuing area of interest. In particular, the ability to control the chemoselectivity of intermolecular reactions in the presence of multiple reactive sites has been a long-standing challenge in the field. In this paper, we demonstrate examples of silver-catalyzed, nondirected, intermolecular nitrene transfer reactions that are both chemoselective and flexible for aziridination or C-H insertion, depending on the choice of ligand. Experimental probes present a puzzling picture of the mechanistic details of the pathways mediated by [( t Bu 3 tpy)AgOTf] 2 and (tpa)AgOTf. Computational studies elucidate these subtleties and provide guidance for the future development of new catalysts exhibiting improved tunability in group transfer reactions.

  14. Hydrogen transfer reduction of polyketones catalyzed by iridium complexes: a novel route towards more biocompatible materials.

    Science.gov (United States)

    Milani, Barbara; Crottib, Corrado; Farnetti, Erica

    2008-09-14

    Transfer hydrogenation from 2-propanol to CO/4-methylstyrene and CO/styrene polyketones was catalyzed by [Ir(diene)(N-N)X] (N-N = nitrogen chelating ligand; X = halogen) in the presence of a basic cocatalyst. The reactions were performed using dioxane as cosolvent, in order to overcome problems due to low polyketone solubility. The polyalcohols were obtained in yields up to 95%, the conversions being markedly dependent on the nature of the ligands coordinated to iridium as well as on the experimental conditions.

  15. Investigation of transition metal-catalyzed nitrene transfer reactions in water.

    Science.gov (United States)

    Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

    2018-04-11

    Transition metal-catalyzed nitrene transfer is a powerful method for incorporating new CN bonds into relatively unfunctionalized scaffolds. In this communication, we report the first examples of site- and chemoselective CH bond amination reactions in aqueous media. The unexpected ability to employ water as the solvent in these reactions is advantageous in that it eliminates toxic solvent use and enables reactions to be run at increased concentrations with lower oxidant loadings. Using water as the reaction medium has potential to expand the scope of nitrene transfer to encompass a variety of biomolecules and highly polar substrates, as well as enable pH control over the site-selectivity of CH bond amination. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. A role of proton transfer in peroxidase-catalyzed process elucidated by substrates docking calculations

    Directory of Open Access Journals (Sweden)

    Ziemys Arturas

    2001-08-01

    Full Text Available Abstract Background Previous kinetic investigations of fungal-peroxidase catalyzed oxidation of N-aryl hydroxamic acids (AHAs and N-aryl-N-hydroxy urethanes (AHUs revealed that the rate of reaction was independent of the formal redox potential of substrates. Moreover, the oxidation rate was 3–5 orders of magnitude less than for oxidation of physiological phenol substrates, though the redox potential was similar. Results To explain the unexpectedly low reactivity of AHAs and AHUs we made ab initio calculations of the molecular structure of the substrates following in silico docking in the active center of the enzyme. Conclusions AHAs and AHUs were docked at the distal side of heme in the sites formed by hydrophobic amino acid residues that retarded a proton transfer and finally the oxidation rate. The analogous phenol substrates were docked at different sites permitting fast proton transfer in the relay of distal His and water that helped fast substrate oxidation.

  17. QM/MM MD and Free Energy Simulation Study of Methyl Transfer Processes Catalyzed by PKMTs and PRMTs.

    Science.gov (United States)

    Chu, Yuzhuo; Guo, Hong

    2015-09-01

    Methyl transfer processes catalyzed by protein lysine methyltransferases (PKMTs) and protein arginine methyltransferases (PRMTs) control important biological events including transcriptional regulation and cell signaling. One important property of these enzymes is that different PKMTs and PRMTs catalyze the formation of different methylated product (product specificity). These different methylation states lead to different biological outcomes. Here, we review the results of quantum mechanics/molecular mechanics molecular dynamics and free energy simulations that have been performed to study the reaction mechanism of PKMTs and PRMTs and the mechanism underlying the product specificity of the methyl transfer processes.

  18. A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Cammarota, Ryan C. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Vollmer, Matthew V. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Xie, Jing [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Ye, Jingyun [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Linehan, John C. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Burgess, Samantha A. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Appel, Aaron M. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Gagliardi, Laura [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Lu, Connie C. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States

    2017-09-28

    Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centred catalysts. The Lewis acidic Ga(III) ion plays a pivotal role by stabilizing reactive catalytic intermediates, including a rare anionic d10 Ni hydride. The structure of this reactive intermediate shows a terminal Ni-H, for which the hydride donor strength rivals those of precious metal-hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis. The work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award DE-SC0012702. R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation Graduate Research Fellowship programs, respectively. J.C.L., S.A.B., and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  19. Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

    Science.gov (United States)

    Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

    2018-03-01

    A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Direct hydride shift mechanism and stereoselectivity of P450nor confirmed by QM/MM calculations.

    Science.gov (United States)

    Krámos, Balázs; Menyhárd, Dóra K; Oláh, Julianna

    2012-01-19

    Nitric oxide reductase (P450(nor)) found in Fusarium oxysporum catalyzes the reduction of nitric oxide to N(2)O in a multistep process. The reducing agent, NADH, is bound in the distal pocket of the enzyme, and direct hydride transfer occurs from NADH to the nitric oxide bound heme enzyme, forming intermediate I. Here we studied the possibility of hydride transfer from NADH to both the nitrogen and oxygen of the heme-bound nitric oxide, using quantum chemical and combined quantum mechanics/molecular mechanics (QM/MM) calculations, on two different protein models, representing both possible stereochemistries, a syn- and an anti-NADH arrangement. All calculations clearly favor hydride transfer to the nitrogen of nitric oxide, and the QM-only barrier and kinetic isotope effects are good agreement with the experimental values of intermediate I formation. We obtained higher barriers in the QM/MM calculations for both pathways, but hydride transfer to the nitrogen of nitric oxide is still clearly favored. The barriers obtained for the syn, Pro-R conformation of NADH are lower and show significantly less variation than the barriers obtained in the case of anti conformation. The effect of basis set and wide range of functionals on the obtained results are also discussed.

  1. Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

    Science.gov (United States)

    Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

    2016-06-30

    We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate.

  2. Efficient transfer hydrogenation reaction Catalyzed by a dearomatized PN 3P ruthenium pincer complex under base-free Conditions

    KAUST Repository

    He, Lipeng

    2012-03-01

    A dearomatized complex [RuH(PN 3P)(CO)] (PN 3PN, N′-bis(di-tert-butylphosphino)-2,6-diaminopyridine) (3) was prepared by reaction of the aromatic complex [RuH(Cl)(PN 3P)(CO)] (2) with t-BuOK in THF. Further treatment of 3 with formic acid led to the formation of a rearomatized complex (4). These new complexes were fully characterized and the molecular structure of complex 4 was further confirmed by X-ray crystallography. In complex 4, a distorted square-pyramidal geometry around the ruthenium center was observed, with the CO ligand trans to the pyridinic nitrogen atom and the hydride located in the apical position. The dearomatized complex 3 displays efficient catalytic activity for hydrogen transfer of ketones in isopropanol. © 2011 Elsevier B.V. All rights reserved.

  3. Atom transfer radical polymerization of n-butyl acrylate catalyzed by atom transfer radical polymerization of n-butyl acrylate catalyzed by

    NARCIS (Netherlands)

    Zhang, H.; Linde, van der R.

    2002-01-01

    The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]0/[M]) versus the reaction time for the ATRP systems in different

  4. Attempts To Catalyze the Electrochemical CO2-to-Methanol Conversion by Biomimetic 2e(-) + 2H(+) Transferring Molecules.

    Science.gov (United States)

    Saveant, Jean-Michel; Tard, Cédric

    2016-01-27

    In the context of the electrochemical and photochemical conversion of CO2 to liquid fuels, one of the most important issues of contemporary energy and environmental issues, the possibility of pushing the reduction beyond the CO and formate level and catalytically generate products such as methanol is particularly attractive. Biomimetic 2e(-) + 2H(+) is often viewed as a potential hydride donor. This has been the object of a recent interesting attempt (J. Am. Chem. Soc. 2014, 136, 14007) in which 6,7-dimethyl-4-hydroxy-2-mercaptopteridine was reported as a catalyst of the electrochemical conversion of CO2 to methanol and formate, based on cyclic voltammetric, (13)C NMR, IR, and GC analyses. After checking electrolysis at the reported potential and at a more negative potential to speed up the reaction, it appears, on (1)H NMR and gas chromatographic grounds, that there is neither catalysis nor methanol and nor formate production. (1)H NMR (with H2O presaturation) brings about an unambiguous answer to the eventual production of methanol and formate, much more so than (13)C NMR, which can even be misleading when no internal standard is used as in the above-mentioned paper. IR analysis is even less conclusive. Use of a GC technique with sufficient sensitivity confirmed the lack of methanol formation. The direct or indirect hydride transfer electrochemical reduction of CO2 to formate and to methanol remains an open question. Original ideas and efforts such as those discussed here are certainly worth tempting. However, in view of the importance of the stakes, it appears necessary to carefully check reports in this area.

  5. γ-Sultam-cored N,N-ligands in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation of aryl ketones.

    Science.gov (United States)

    Rast, Slavko; Modec, Barbara; Stephan, Michel; Mohar, Barbara

    2016-02-14

    The synthesis of new enantiopure syn- and anti-3-(α-aminobenzyl)-benzo-γ-sultam ligands 6 and their application in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation (ATH) of ketones using formic acid/triethylamine is described. In particular, benzo-fused cyclic ketones afforded excellent enantioselectivities in reasonable time employing a low loading of the syn ligand-containing catalyst. A never-before-seen dynamic kinetic resolution (DKR) during reduction of a γ-keto carboxylic ester (S7) derivative of 1-indanone is realized leading as well to excellent induction.

  6. Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation.

    Science.gov (United States)

    Pappas, Iraklis; Chirik, Paul J

    2016-10-03

    The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η 5 -C 5 Me 5 )(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η 5 -C 5 R 5 )(CO) 3 Cr-H ([Cr] R -H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H 2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH 3 by proton coupled electron transfer at a well-defined transition metal center.

  7. Z-H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution.

    Science.gov (United States)

    Belkova, Natalia V; Filippov, Oleg A; Shubina, Elena S

    2018-02-01

    The ability of neutral transition-metal hydrides to serve as a source of hydride ion H - or proton H + is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-H δ- ⋅⋅⋅ δ+ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-H δ+ ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metal hydrides based high energy density thermal battery

    International Nuclear Information System (INIS)

    Fang, Zhigang Zak; Zhou, Chengshang; Fan, Peng; Udell, Kent S.; Bowman, Robert C.; Vajo, John J.; Purewal, Justin J.; Kekelia, Bidzina

    2015-01-01

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH 2 and TiMnV as a working pair. • High energy density can be achieved by the use of MgH 2 to store thermal energy. - Abstract: A concept of thermal battery based on advanced metal hydrides was studied for heating and cooling of cabins in electric vehicles. The system utilized a pair of thermodynamically matched metal hydrides as energy storage media. The pair of hydrides that was identified and developed was: (1) catalyzed MgH 2 as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV 0.62 Mn 1.5 alloy as the matching low temperature hydride. Further, a proof-of-concept prototype was built and tested, demonstrating the potential of the system as HVAC for transportation vehicles

  9. Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

    Science.gov (United States)

    Corbin, Joshua R; Schomaker, Jennifer M

    2017-04-13

    Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

  10. Complementary Strategies for Directed C(sp3 )-H Functionalization: A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer.

    Science.gov (United States)

    Chu, John C K; Rovis, Tomislav

    2018-01-02

    The functionalization of C(sp 3 )-H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C-H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition-metal-catalyzed C-H activation, 1,n-hydrogen atom transfer, and transition-metal-catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp 3 )-H bonds. For each strategy, the scope, the reactivity of different C-H bonds, the position of the reacting C-H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C-H functionalization reactions and inspire future research in this area. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Microbial activity catalyzes oxygen transfer in membrane-aerated nitritating biofilm reactors

    DEFF Research Database (Denmark)

    Pellicer i Nàcher, Carles; Domingo Felez, Carlos; Lackner, Susanne

    2013-01-01

    The remarkable oxygen transfer efficiencies attainable in membrane-aerated biofilm reactors (MABRs) are expected to favor their prompt industrial implementation. However, tests in clean water, currently used for the estimation of their oxygen transfer potential, lead to wrong estimates once biofilm...... is present, significantly complicating reactor modelling and control. This study shows for the first time the factors affecting oxygen mass transfer across membranes during clean water tests and reactor operation via undisturbed microelectrode inspection and bulk measurements. The mass transfer resistance...... of the liquid boundary layer developed at the membrane-liquid interface during clean water tests accounted for two thirds of the total mass transfer resistance, suggesting a strong underestimation of the oxygen transfer rates when it is absent (e.g. after biofilm growth). Reactor operation to attain partial...

  12. Hydride heat pump with heat regenerator

    Science.gov (United States)

    Jones, Jack A. (Inventor)

    1991-01-01

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

  13. Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+ with Methane under Ambient Conditions.

    Science.gov (United States)

    Li, Jilai; Zhou, Shaodong; Schlangen, Maria; Weiske, Thomas; Schwarz, Helmut

    2016-10-10

    The reactivity of the cationic gold carbide [AuC] + (bearing an electrophilic carbon atom) towards methane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The product pairs generated, that is, Au + /C 2 H 4 , [Au(C 2 H 2 )] + /H 2 , and [C 2 H 3 ] + /AuH, point to the breaking and making of C-H, C-C, and H-H bonds under single-collision conditions. The mechanisms of these rather efficient reactions have been elucidated by high-level quantum-chemical calculations. As a major result, based on molecular orbital and NBO-based charge analysis, an unprecedented hydride transfer from methane to the carbon atom of [AuC] + has been identified as a key step. Also, the origin of this novel mechanistic scenario has been addressed. The mechanistic insights derived from this study may provide guidance for the rational design of carbon-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Hydrogen-deuterium exchange of the anionic group 6B transition-metal hydrides. Convenient, in-situ-deuterium transfer reagents

    International Nuclear Information System (INIS)

    Gaus, P.L.; Kao, S.C.; Darensbourg, M.Y.; Arndt, L.W.

    1984-01-01

    The facile exchange of hydrogen for detuerium in the anionic group 6B carbonyl hydrides HM(CO) 4 L - (M = Cr, W; L = CO P(OMe) 3 ) has been studied in THF 4 (tetrahydrofuran) with CH 3 OD, D 2 O, and CH 3 CO 2 D. This has provided a synthesis of the deuterides, DM(CO) 4 L - , as well as a convenient in situ source of deuteride reducing reagents for organic halides. A number of such reductions are described, using 2 H NMR to demonstrate both selectivity and stereospecificity for certain systems. The carbonyl region of the infrared spectra of the hydrides is not affected by deuteration of the hydrides, suggesting that the M-H or M-D vibrational modes are not coupled significantly to CO vibrations in these hydrides. The mechanism of the H/D exchange and of a related H 2 elimination reaction is discussed

  15. Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

    Science.gov (United States)

    Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

    2017-08-30

    Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

  16. Pd0-Catalyzed Methyl Transfer on Nucleosides and Oligonucleotides, Envisaged as a PET Tracer

    Directory of Open Access Journals (Sweden)

    Eric Fouquet

    2013-11-01

    Full Text Available The methyl transfer reaction from activated monomethyltin, via a modified Stille coupling reaction, was studied under “ligandless” conditions on fully deprotected 5'-modified nucleosides and one dinucleotide. The reaction was optimized to proceed in a few minutes and quantitative yield, even under dilute conditions, thus affording a rapid and efficient new method for oligonucleotide labelling with carbon-11.

  17. On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

    2013-01-01

    The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

  18. Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C–H Bond Activation

    Science.gov (United States)

    Yi, Chae S.; Lee, Do W.

    2010-01-01

    Summary The cationic ruthenium-hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly effective catalyst for the intermolecular olefination reaction of arylketones with cycloalkenes. The preliminary mechanistic analysis revealed that electrophilic ruthenium-vinyl complex is the key species for mediating both vinyl C–H bond activation and the dehydrative olefination steps of the coupling reaction. PMID:20567607

  19. Intermolecular hydrogen transfer catalyzed by a flavodehydrogenase, bakers' yeast flavocytochrome b2

    International Nuclear Information System (INIS)

    Urban, P.; Lederer, F.

    1985-01-01

    Bakers yeast flavocytochrome b2 is a flavin-dependent L-2-hydroxy acid dehydrogenase which also exhibits transhydrogenase activity. When a reaction takes place between [2- 3 H]lactate and a halogenopyruvate, tritium is found in water and at the halogenolactate C2 position. When the halogenopyruvate undergoes halide ion elimination, tritium is also found at the C3 position of the resulting pyruvate. The amount tau of this intermolecular tritium transfer depends on the initial keto acid-acceptor concentration. At infinite acceptor concentration, extrapolation yields a maximal transfer of 97 +/- 11%. This indicates that the hydroxy acid-derived hydrogen resides transiently on enzyme monoprotic heteroatoms and that exchange with bulk solvent occurs only at the level of free reduced enzyme. Using a minimal kinetic scheme, the rate constant for hydrogen exchange between Ered and solvent is calculated to be on the order of 10(2) M-1 S-1, which leads to an estimated pK approximately equal to 15 for the ionization of the substrate-derived proton while on the enzyme. It is suggested that this hydrogen could be shared between the active site base and Flred N5 anion. It is furthermore shown that some tritium is incorporated into the products when the transhydrogenation is carried out in tritiated water. Finally, with [2-2H]lactate-reduced enzyme, a deuterium isotope effect is observed on the rate of bromopyruvate disappearance. Extrapolation to infinite bromopyruvate concentration yields DV = 4.4. An apparent inverse isotope effect is determined for bromide ion elimination. These results strengthen the idea that oxidoreduction and elimination pathways involve a common carbanionic intermediate

  20. An iterative glycosyltransferase EntS catalyzes transfer and extension of O- and S-linked monosaccharide in enterocin 96.

    Science.gov (United States)

    Nagar, Rupa; Rao, Alka

    2017-05-12

    Glycosyltransferases are essential tools for in vitro-glycoengineering. Bacteria harbor an unexplored variety of protein glycosyltransferases. Here, we describe a peptide glycosyltransferase (EntS) encoded by ORF0417 of Enterococcus faecalis TX0104. EntS di-glycosylates linear peptide of enterocin 96- a known antibacterial, in vitro. It is capable of transferring as well as extending the glycan onto the peptide in an iterative sequential dissociative manner. It can catalyze multiple linkages: Glc/Gal(-O)Ser/Thr, Glc/Gal(-S)Cys and Glc/Gal(β)Glc/Gal(-O/S)Ser/Thr/Cys, in one pot. Using EntS generated glycovariants of enterocin 96 peptide, size and identity of the glycan are found to influence bioactivity of the peptide. The study identifies EntS as an enzyme worth pursuing, for in vitro peptide glycoengineering. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  1. Phosphoryl transfer is not rate-limiting for the ROCK I-catalyzed kinase reaction.

    Science.gov (United States)

    Futer, Olga; Saadat, Ahmad R; Doran, John D; Raybuck, Scott A; Pazhanisamy, S

    2006-06-27

    Rho-associated coiled-coil kinase, ROCK, is implicated in Rho-mediated cell adhesion and smooth muscle contraction. Animal models suggest that the inhibition of ROCK can ameliorate conditions, such as vasospasm, hypertension, and inflammation. As part of our effort to design novel inhibitors of ROCK, we investigated the kinetic mechanism of ROCK I. Steady-state bisubstrate kinetics, inhibition kinetics, isotope partition analysis, viscosity effects, and presteady-state kinetics were used to explore the kinetic mechanism. Plots of reciprocals of initial rates obtained in the presence of nonhydrolyzable ATP analogues and the small molecule inhibitor of ROCK, Y-27632, against the reciprocals of the peptide concentrations yielded parallel lines (uncompetitive pattern). This pattern is indicative of an ordered binding mechanism, with the peptide adding first. The staurosporine analogue K252a, however, gave a noncompetitive pattern. When a pulse of (33)P-gamma-ATP mixed with ROCK was chased with excess unlabeled ATP and peptide, 0.66 enzyme equivalent of (33)P-phosphate was incorporated into the product in the first turnover. The presence of ATPase activity coupled with the isotope partition data is a clear evidence for the existence of a viable [E-ATP] complex in the kinase reaction and implicates a random binding mechanism. The k(cat)/K(m) parameters were fully sensitive to viscosity (viscosity effects of 1.4 +/- 0.2 and 0.9 +/- 0.3 for ATP and peptide 5, respectively), and therefore, the barriers to dissociation of either substrate are higher than the barrier for the phosphoryl transfer step. As a consequence, not all the binding steps are at fast equilibrium. The observation of a burst in presteady-state kinetics (k(b) = 10.2 +/- 2.1 s(-)(1)) and the viscosity effect on k(cat) of 1.3 +/- 0.2 characterize the phosphoryl transfer step to be fast and the release of product and/or the enzyme isomerization step accompanying it as rate-limiting at V(max) conditions. From

  2. Inverting Steric Effects: Using "Attractive" Noncovalent Interactions To Direct Silver-Catalyzed Nitrene Transfer.

    Science.gov (United States)

    Huang, Minxue; Yang, Tzuhsiung; Paretsky, Jonathan D; Berry, John F; Schomaker, Jennifer M

    2017-12-06

    Nitrene transfer (NT) reactions represent powerful and direct methods to convert C-H bonds into amine groups that are prevalent in many commodity chemicals and pharmaceuticals. The importance of the C-N bond has stimulated the development of numerous transition-metal complexes to effect chemo-, regio-, and diastereoselective NT. An ongoing challenge is to understand how subtle interactions between catalyst and substrate influence the site-selectivity of the C-H amination event. In this work, we explore the underlying reasons why Ag(tpa)OTf (tpa = tris(pyridylmethyl)amine) prefers to activate α-conjugated C-H bonds over 3° alkyl C(sp 3 )-H bonds and apply these insights to reaction optimization and catalyst design. Experimental results suggest possible roles of noncovalent interactions (NCIs) in directing the NT; computational studies support the involvement of π···π and Ag···π interactions between catalyst and substrate, primarily by lowering the energy of the directed transition state and reaction conformers. A simple Hess's law relationship can be employed to predict selectivities for new substrates containing competing NCIs. The insights presented herein are poised to inspire the design of other catalyst-controlled C-H functionalization reactions.

  3. C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

    OpenAIRE

    Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

    2012-01-01

    We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexib...

  4. Novel Oxidative Desulfurization of a Model Fuel with H2O2 Catalyzed by AlPMo12O40 under Phase Transfer Catalyst-Free Conditions

    OpenAIRE

    José da Silva, Márcio; Faria dos Santos, Lidiane

    2013-01-01

    A novel process was developed for oxidative desulfurization (ODS) in the absence of a phase transfer catalyst (PTC) using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT) as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by ace...

  5. Preparation of beryllium hydride

    International Nuclear Information System (INIS)

    Roberts, C.B.

    1975-01-01

    A process is described for preparing beryllium hydride by the direct reaction of beryllium borohydride and aluminum hydride trimethylamine adduct. Volatile by-products and unreacted reactants are readily removed from the product mass by sublimation and/or evaporation. (U.S.)

  6. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

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

  7. Alkali metal hydride formation

    International Nuclear Information System (INIS)

    1976-01-01

    The present invention relates to a method of producing alkali metal hydrides by absorbing hydrogen gas under pressure into a mixture of lower alkyl mono amines and alkali metal alkyl amides selected from sodium and potassium amides formed from said amines. The present invention also includes purification of a mixture of the amines and amides which contain impurities, such as is used as a catalytic exchange liquid in the enrichment of deuterium, involving the formation of the alkali metal hydride

  8. Blistering and hydride embrittlement

    International Nuclear Information System (INIS)

    Louthan, M.R. Jr.

    1975-01-01

    The effects of hydrogen on the mechanical properties of metals have been categorized into several groups. Two of the groups, hydrogen blistering and hydride embrittlement, are reasonably well understood, and problems relating to their occurrence may be avoided if that understanding is used as a basis for selecting alloys for hydrogen service. Blistering and hydride embrittlement are described along with several techniques of materials selection and used to minimize their adverse effects. (U.S.)

  9. Metal hydrides based high energy density thermal battery

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Zhigang Zak, E-mail: zak.fang@utah.edu [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Zhou, Chengshang; Fan, Peng [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Udell, Kent S. [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States); Bowman, Robert C. [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Vajo, John J.; Purewal, Justin J. [HRL Laboratories, LLC, 3011 Malibu Canyon Road, Malibu, CA 90265 (United States); Kekelia, Bidzina [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States)

    2015-10-05

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH{sub 2} and TiMnV as a working pair. • High energy density can be achieved by the use of MgH{sub 2} to store thermal energy. - Abstract: A concept of thermal battery based on advanced metal hydrides was studied for heating and cooling of cabins in electric vehicles. The system utilized a pair of thermodynamically matched metal hydrides as energy storage media. The pair of hydrides that was identified and developed was: (1) catalyzed MgH{sub 2} as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV{sub 0.62}Mn{sub 1.5} alloy as the matching low temperature hydride. Further, a proof-of-concept prototype was built and tested, demonstrating the potential of the system as HVAC for transportation vehicles.

  10. Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation

    Science.gov (United States)

    Patman, Ryan L.; Chaulagain, Mani Raj; Williams, Vanessa M.; Krische, Michael J.

    2011-01-01

    Under the conditions of ruthenium catalyzed transfer hydrogenation, 2-butyne couples to benzylic and aliphatic alcohols 1a–1i to furnish allylic alcohols 2a–2i, constituting a direct C-H vinylation of alcohols employing alkynes as vinyl donors. Under related transfer hydrogenation conditions employing formic acid as terminal reductant, 2-butyne couples to aldehydes 4a, 4b, and 4e to furnish identical products of carbonyl vinylation 2a, 2b, and 2e. Thus, carbonyl vinylation is achieved from the alcohol or the aldehyde oxidation level in the absence of any stoichiometric metallic reagents. Nonsymmetric alkynes 6a–6c couple efficiently to aldehyde 4b to provide allylic alcohols 2m–2o as single regioisomers. Acetylenic aldehyde 7a engages in efficient intramolecular coupling to deliver cyclic allylic alcohol 8a. PMID:19173651

  11. Conference 'Chemistry of hydrides' Proceedings

    International Nuclear Information System (INIS)

    1991-07-01

    This collection of thesis of conference of Chemistry hydrides presents the results of investigations concerning of base questions of chemistry of nonorganic hydrides, including synthesis questions, studying of physical and chemical properties, thermodynamics, analytical chemistry, investigation of structure, equilibriums in the systems of metal-hydrogen, behaviour of nonorganic hydrides in non-water mediums and applying investigations in the chemistry area and technology of nonorganic hydrides

  12. Preparation of beryllium hydride

    International Nuclear Information System (INIS)

    Lowrance, B.R.

    1975-01-01

    A process is described for the preparation of beryllium hydride which comprises pyrolyzing, while in solution in a solvent inert under the reaction conditions, with respect to reactants and products and at a temperature in the range of about 100 0 to about 200 0 C, sufficient to result in the formation of beryllium hydride, a di-t-alkyl beryllium etherate wherein each tertiary alkyl radical contains from 4 to 20 carbon atoms. The pyrolysis is carried out under an atmosphere inert under the reaction conditions, with respect to reactants and products. (U.S.)

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

    KAUST Repository

    Werghi, Baraa

    2016-09-26

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

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

    KAUST Repository

    Werghi, Baraa; Bendjeriou-Sedjerari, Anissa; Jedidi, Abdesslem; Abou-Hamad, Edy; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

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

  15. Artificial exomuscle investigations for applications-metal hydride

    International Nuclear Information System (INIS)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bedard, Stephane

    2007-01-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software. (review article)

  16. Electrolytic hydriding and hydride distribution in zircaloy-4

    International Nuclear Information System (INIS)

    Gomes, M.H.L.

    1974-01-01

    A study has been made of the electrolytic hydriding of zircaloy-4 in the range 20-80 0 C, for reaction times from 5 to 30 hours, and the effect of potential, pH and dissolved oxygen has been investigated. The hydriding reaction was more sensitive to time and temperature conditions than to the electrochemical variables. It has been shown that a controlled introduction of hydrides in zircaloy is feasible. Hydrides were found to be plate like shaped and distributed mainly along grain-boundaries. It has been shown that hydriding kinetics do not follow a simple law but may be described by a Johnson-Mehl empirical equation. On the basis of this equation an activation energy of 9.400 cal/mol has been determined, which is close to the activation energy for diffusion of hydrogen in the hydride. (author)

  17. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    current. For applications involving the utilisation of high currents, the activation to the required level could be as high as 100 cycles, whereas for low current applications, 5-10 activation cycles could be sufficient when the same current was used for the activation (pretreatment of the alloy might enhance the activation considerably). When an electrode made of an alloy with a relatively high hydrogen equilibrium (plateau) pressure was cycled under a moderate external inert gas pressure, a new activation process was observed when the pressure was increased. This indicated that the activated state was dependent on several factors, which indicated the need of examining each factor individually as well as combined in order to gain a complete understanding of the process. The characterization of metal hydride electrodes by means of electrochemical impedance spectroscopy, showed that this technique when used properly and in combination with other characterization techniques can be very useful in determining the significance of the different sub-processes in the overall process. The impedance response for different laboratory metal hydride electrodes were successfully modelled and fitted to experimental data for both AB{sub 5} type alloys and a MgNi type electrode. The following sub processes were found to be significant for the overall reaction rate: charge transfer resistance, double layer capacitance and impedance resulting from hydrogen diffusion within the metal lattice. The diffusion process was best modelled when using a spherical diffusion geometry. To fit the experimental data, equations describing the current distribution in porous electrodes were required. To account for possible parallel hydrogen evolution during charging, it was necessary to include this step in the model for electrodes having a more negative open circuit potential than the reversible hydrogen evolution potential. Indications of one or more parallel reduction/oxidation processes competing with

  18. Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

    Science.gov (United States)

    Souillart, Laetitia; Cramer, Nicolai

    2014-09-01

    The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Some new techniques in tritium gas handling as applied to metal hydride synthesis

    International Nuclear Information System (INIS)

    Nasise, J.E.

    1988-01-01

    A state-of-the-art tritium Hydriding Synthesis System (HSS) was designed and built to replace the existing system within the Tritium Salt Facility (TSF) at the Los Alamos National Laboratory. This new hydriding system utilizes unique fast-cycling 7.9 mole uranium beds (47.5g of T at 100% loading) and novel gas circulating hydriding furnaces. Tritium system components discussed include fast-cycling uranium beds, circulating gas hydriding furnaces, valves, storage volumes, manifolds, gas transfer pumps, and graphic display and control consoles. Many of the tritium handling and processing techniques incorporated into this system are directly applicable to today's fusion fuel loops. 12 refs., 7 figs

  20. Preparation of beryllium hydride

    International Nuclear Information System (INIS)

    Bergeron, C.R.; Baker, R.W.

    1975-01-01

    Beryllium hydride of high bulk density, suitable for use as a component of high-energy fuels, is prepared by the pyrolysis, in solution in an inert solvent, of a ditertiary-alkyl beryllium. An agitator introduces mechanical energy into the reaction system, during the pyrolysis, at the rate of 0.002 to 0.30 horsepower per gallon of reaction mixture. (U.S.)

  1. Air and metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-31

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

  2. Hydriding of metallic thorium

    International Nuclear Information System (INIS)

    Miyake, Masanobu; Katsura, Masahiro; Matsuki, Yuichi; Uno, Masayoshi

    1983-01-01

    Powdered thorium is usually prepared through a combination of hydriding and dehydriding processes of metallic thorium in massive form, in which the hydriding process consists of two steps: the formation of ThH 2 , and the formation of Th 4 H 15 . However, little has yet been known as to on what stage of hydriding process the pulverization takes place. It is found in the present study that the formation of Th 4 H 15 by the reaction of ThH 2 with H 2 is responsible for pulverization. Temperature of 70 deg C adopted in this work for the reaction of formation Th 4 H 15 seems to be much more effective for production of powdered thorium than 200 - 300 deg C in the literature. The pressure-composition-temperature relationships for Th-H system are determined at 200, 300, 350, and 800 deg C. From these results, a tentative equilibrium phase diagram for the Th-H system is proposed, attention being focused on the two-phase region of ThH 2 and Th 4 H 15 . Pulverization process is discussed in terms of the tentative phase diagram. (author)

  3. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

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

    2002-01-01

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

  4. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion

    2010-07-01

    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  5. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    International Nuclear Information System (INIS)

    Montalvo-Gonzalez, Ruben; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy

    2010-01-01

    Two C 2 -symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh III (Cp * ) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  6. Hydrogen Outgassing from Lithium Hydride

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-04-20

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

  7. Studies on the Mechanism of Electron Bifurcation Catalyzed by Electron Transferring Flavoprotein (Etf) and Butyryl-CoA Dehydrogenase (Bcd) of Acidaminococcus fermentans*

    Science.gov (United States)

    Chowdhury, Nilanjan Pal; Mowafy, Amr M.; Demmer, Julius K.; Upadhyay, Vikrant; Koelzer, Sebastian; Jayamani, Elamparithi; Kahnt, Joerg; Hornung, Marco; Demmer, Ulrike; Ermler, Ulrich; Buckel, Wolfgang

    2014-01-01

    Electron bifurcation is a fundamental strategy of energy coupling originally discovered in the Q-cycle of many organisms. Recently a flavin-based electron bifurcation has been detected in anaerobes, first in clostridia and later in acetogens and methanogens. It enables anaerobic bacteria and archaea to reduce the low-potential [4Fe-4S] clusters of ferredoxin, which increases the efficiency of the substrate level and electron transport phosphorylations. Here we characterize the bifurcating electron transferring flavoprotein (EtfAf) and butyryl-CoA dehydrogenase (BcdAf) of Acidaminococcus fermentans, which couple the exergonic reduction of crotonyl-CoA to butyryl-CoA to the endergonic reduction of ferredoxin both with NADH. EtfAf contains one FAD (α-FAD) in subunit α and a second FAD (β-FAD) in subunit β. The distance between the two isoalloxazine rings is 18 Å. The EtfAf-NAD+ complex structure revealed β-FAD as acceptor of the hydride of NADH. The formed β-FADH− is considered as the bifurcating electron donor. As a result of a domain movement, α-FAD is able to approach β-FADH− by about 4 Å and to take up one electron yielding a stable anionic semiquinone, α-FAD⨪, which donates this electron further to Dh-FAD of BcdAf after a second domain movement. The remaining non-stabilized neutral semiquinone, β-FADH•, immediately reduces ferredoxin. Repetition of this process affords a second reduced ferredoxin and Dh-FADH− that converts crotonyl-CoA to butyryl-CoA. PMID:24379410

  8. Studies on the mechanism of electron bifurcation catalyzed by electron transferring flavoprotein (Etf) and butyryl-CoA dehydrogenase (Bcd) of Acidaminococcus fermentans.

    Science.gov (United States)

    Chowdhury, Nilanjan Pal; Mowafy, Amr M; Demmer, Julius K; Upadhyay, Vikrant; Koelzer, Sebastian; Jayamani, Elamparithi; Kahnt, Joerg; Hornung, Marco; Demmer, Ulrike; Ermler, Ulrich; Buckel, Wolfgang

    2014-02-21

    Electron bifurcation is a fundamental strategy of energy coupling originally discovered in the Q-cycle of many organisms. Recently a flavin-based electron bifurcation has been detected in anaerobes, first in clostridia and later in acetogens and methanogens. It enables anaerobic bacteria and archaea to reduce the low-potential [4Fe-4S] clusters of ferredoxin, which increases the efficiency of the substrate level and electron transport phosphorylations. Here we characterize the bifurcating electron transferring flavoprotein (EtfAf) and butyryl-CoA dehydrogenase (BcdAf) of Acidaminococcus fermentans, which couple the exergonic reduction of crotonyl-CoA to butyryl-CoA to the endergonic reduction of ferredoxin both with NADH. EtfAf contains one FAD (α-FAD) in subunit α and a second FAD (β-FAD) in subunit β. The distance between the two isoalloxazine rings is 18 Å. The EtfAf-NAD(+) complex structure revealed β-FAD as acceptor of the hydride of NADH. The formed β-FADH(-) is considered as the bifurcating electron donor. As a result of a domain movement, α-FAD is able to approach β-FADH(-) by about 4 Å and to take up one electron yielding a stable anionic semiquinone, α-FAD, which donates this electron further to Dh-FAD of BcdAf after a second domain movement. The remaining non-stabilized neutral semiquinone, β-FADH(•), immediately reduces ferredoxin. Repetition of this process affords a second reduced ferredoxin and Dh-FADH(-) that converts crotonyl-CoA to butyryl-CoA.

  9. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir

    2015-11-28

    This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.

  10. A highly sensitive fluorescence resonance energy transfer aptasensor for staphylococcal enterotoxin B detection based on exonuclease-catalyzed target recycling strategy

    International Nuclear Information System (INIS)

    Wu, Shijia; Duan, Nuo; Ma, Xiaoyuan; Xia, Yu; Wang, Hongxin; Wang, Zhouping

    2013-01-01

    Graphical abstract: -- Highlights: •An ultrasensitive FRET aptasensor was developed for staphylococcal enterotoxin B determination. •SEB was recognized by SEB aptamer with high affinity and specificity. •The Mn 2+ doped NaYF 4 :Yb/Er UCNPs used as donor to quencher dye (BHQ 3 ) in new FRET. •The fluorescence intensity was prominently amplified using an exonuclease-catalyzed target recycling strategy. -- Abstract: An ultrasensitive fluorescence resonance energy transfer (FRET) bioassay was developed to detect staphylococcal enterotoxin B (SEB), a low molecular exotoxin, using an aptamer-affinity method coupled with upconversion nanoparticles (UCNPs)-sensing, and the fluorescence intensity was prominently enhanced using an exonuclease-catalyzed target recycling strategy. To construct this aptasensor, both fluorescence donor probes (complementary DNA 1 –UCNPs) and fluorescence quencher probes (complementary DNA 2 –Black Hole Quencher 3 (BHQ 3 )) were hybridized to an SEB aptamer, and double-strand oligonucleotides were fabricated, which quenched the fluorescence of the UCNPs via FRET. The formation of an aptamer–SEB complex in the presence of the SEB analyte resulted in not only the dissociation of aptamer from the double-strand DNA but also both the disruption of the FRET system and the restoration of the UCNPs fluorescence. In addition, the SEB was liberated from the aptamer–SEB complex using exonuclease I, an exonuclease specific to single-stranded DNA, for analyte recycling by selectively digesting a particular DNA (SEB aptamer). Based on this exonuclease-catalyzed target recycling strategy, an amplified fluorescence intensity could be produced using different SEB concentrations. Using optimized experimental conditions produced an ultrasensitive aptasensor for the detection of SEB, with a wide linear range of 0.001–1 ng mL −1 and a lower detection limit (LOD) of 0.3 pg mL −1 SEB (at 3σ). The fabricated aptasensor was used to measure SEB in a

  11. Electronic structure, bonding and chemisorption in metallic hydrides

    International Nuclear Information System (INIS)

    Ward, J.W.

    1980-01-01

    Problems that can arise during the cycling steps for a hydride storage system usually involve events at surfaces. Chemisorption and reaction processes can be affected by small amounts of contaminants that may act as catalytic poisons. The nature of the poisoning process can vary greatly for the different metals and alloys that form hydrides. A unifying concept is offered, which satisfactorily correlates many of the properties of transition-metal, rare-earth and actinide hydrides. The metallic hydrides can be differentiated on the basis of electronegativity, metallic radius (valence) and electronic structure. For those systems where there are d (transition metals) or f (early actinides) electrons near the Fermi level a broad range of chemical and catalytic behaviors are found, depending on bandwidth and energy. The more electropositive metals (rare-earths, actinides, transition metals with d > 5) dissolve hydrogen and form hydrides by an electronically somewhat different process, and as a class tend to adsorb electrophobic molecules. The net charge-transfer in either situation is subtle; however, the small differences are responsible for many of the observed structural, chemical, and catalytic properties in these hydride systems

  12. A novel mechanism of sulfur transfer catalyzed by O-acetylhomoserine sulfhydrylase in the methionine-biosynthetic pathway of Wolinella succinogenes

    Energy Technology Data Exchange (ETDEWEB)

    Tran, Timothy H. [Cornell University, Ithaca, New York 14853-1301 (United States); Krishnamoorthy, Kalyanaraman; Begley, Tadhg P., E-mail: begley@tamu.edu [Texas A& M University, College Station, TX 77842 (United States); Ealick, Steven E., E-mail: begley@tamu.edu [Cornell University, Ithaca, New York 14853-1301 (United States)

    2011-10-01

    MetY is the first reported structure of an O-acetylhomoserine sulfhydrylase that utilizes a protein thiocarboxylate intermediate as the sulfur source in a novel methionine-biosynthetic pathway instead of catalyzing a direct sulfhydrylation reaction. O-Acetylhomoserine sulfhydrylase (OAHS) is a pyridoxal 5′-phosphate (PLP) dependent sulfide-utilizing enzyme in the l-cysteine and l-methionine biosynthetic pathways of various enteric bacteria and fungi. OAHS catalyzes the conversion of O-acetylhomoserine to homocysteine using sulfide in a process known as direct sulfhydrylation. However, the source of the sulfur has not been identified and no structures of OAHS have been reported in the literature. Here, the crystal structure of Wolinella succinogenes OAHS (MetY) determined at 2.2 Å resolution is reported. MetY crystallized in space group C2 with two monomers in the asymmetric unit. Size-exclusion chromatography, dynamic light scattering and crystal packing indicate that the biological unit is a tetramer in solution. This is further supported by the crystal structure, in which a tetramer is formed using a combination of noncrystallographic and crystallographic twofold axes. A search for structurally homologous proteins revealed that MetY has the same fold as cystathionine γ-lyase and methionine γ-lyase. The active sites of these enzymes, which are also PLP-dependent, share a high degree of structural similarity, suggesting that MetY belongs to the γ-elimination subclass of the Cys/Met metabolism PLP-dependent family of enzymes. The structure of MetY, together with biochemical data, provides insight into the mechanism of sulfur transfer to a small molecule via a protein thiocarboxylate intermediate.

  13. Zircaloy-4 hydridation

    International Nuclear Information System (INIS)

    Vizcaino, Pablo

    1997-01-01

    The objectives of this work can be summarized as: 1) To reproduce, by heat treatments, matrix microstructures and hydride morphologies similar to those observed in structural components of the CNA-1 and CNE nuclear power plants; 2) To study the evolution of the mechanical properties of the original material with different hydrogen concentrations, such as microhardness, and its capacity to distinguish these materials; 3) To find parameters that allow to estimate the hydrogen content of a material by quantitative metallographic techniques, to be used as complementary in the study of the radioactive materials from reactors

  14. Enantioselective Alkylation of 2-Oxindoles Catalyzed by a Bifunctional Phase-Transfer Catalyst: Synthesis of (-)-Debromoflustramine B.

    Science.gov (United States)

    Craig, Ryan; Sorrentino, Emiliano; Connon, Stephen J

    2018-03-26

    A new bifunctional phase-transfer catalyst that employs hydrogen bonding as a control element was developed to promote efficient enantioselective S N 2 reactions for the construction all-carbon quaternary stereocenters in high yield and excellent enantioselectivity (up to 97 % ee) utilizing the alkylation of a malleable oxindole substrate. The utility of the methodology was demonstrated through a concise and highly enantioselective synthesis of (-)-debromoflustramine B. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Hydride embrittlement in zircaloy components

    Energy Technology Data Exchange (ETDEWEB)

    Lobo, Raquel M.; Andrade, Arnaldo H.P.; Castagnet, Mariano, E-mail: rmlobo@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2011-07-01

    Zirconium alloys are used in nuclear reactor cores under high-temperature water environment. During service, hydrogen is generated by corrosion processes, and it is readily absorbed by these materials. When hydrogen concentration exceeds the terminal solid solubility, the excess hydrogen precipitates as zirconium hydride (ZrH{sub 2}) platelets or needles. Zirconium alloys components can fail by hydride cracking if they contain large flaws and are highly stressed. Zirconium alloys are susceptible to a mechanism for crack initiation and propagation termed delayed hydride cracking (DHC). The presence of brittle hydrides, with a K{sub Ic} fracture toughness of only a few MPa{radical}m, results in a severe loss in ductility and toughness when platelet normal is oriented parallel to the applied stress. In plate or tubing, hydrides tend to form perpendicular to the thickness direction due to the texture developed during fabrication. Hydrides in this orientation do not generally cause structural problems because applied stresses in the through-thickness direction are very low. However, the high mobility of hydrogen in a zirconium lattice enables redistribution of hydrides normal to the applied stress direction, which can result in localized embrittlement. When a platelet reaches a critical length it ruptures. If the tensile stress is sufficiently great, crack initiation starts at some of these hydrides. Crack propagation occurs by repeating the same process at the crack tip. Delayed hydride cracking can degrade the structural integrity of zirconium alloys during reactor service. The paper focuses on the fracture mechanics and fractographic aspects of hydride material. (author)

  16. Thermal enhancement cartridge heater modified tritium hydride bed development, Part 2 - Experimental validation of key conceptual design features

    Energy Technology Data Exchange (ETDEWEB)

    Heroux, K.J.; Morgan, G.A. [Savannah River Laboratory, Aiken, SC (United States)

    2015-03-15

    The Thermal Enhancement Cartridge Heater Modified (TECH Mod) tritium hydride bed is an interim replacement for the first generation (Gen1) process hydride beds currently in service in the Savannah River Site (SRS) Tritium Facilities. 3 new features are implemented in the TECH Mod hydride bed prototype: internal electric cartridge heaters, porous divider plates, and copper foam discs. These modifications will enhance bed performance and reduce costs by improving bed activation and installation processes, in-bed accountability measurements, end-of-life bed removal, and He-3 recovery. A full-scale hydride bed test station was constructed at the Savannah River National Laboratory (SRNL) in order to evaluate the performance of the prototype TECH Mod hydride bed. Controlled hydrogen (H{sub 2}) absorption/ desorption experiments were conducted to validate that the conceptual design changes have no adverse effects on the gas transfer kinetics or H{sub 2} storage/release properties compared to those of the Gen1 bed. Inert gas expansions before, during, and after H{sub 2} flow tests were used to monitor changes in gas transfer rates with repeated hydriding/de-hydriding of the hydride material. The gas flow rates significantly decreased after initial hydriding of the material; however, minimal changes were observed after repeated cycling. The data presented herein confirm that the TECH Mod hydride bed would be a suitable replacement for the Gen1 bed with the added enhancements expected from the advanced design features. (authors)

  17. Modeling of electrochemical hydrogen storage in metal hydride electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2010-01-01

    The recently presented Electrochemical Kinetic Model (EKM), describing the electrochemical hydrogen storage in hydride-forming materials, has been extended by the description of the solid/electrolyte interface, i.e. the charge transfer kinetics and electrical double layer charging. A complete set of

  18. Modeling of electrochemical hydrogen storage in metal hydride electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2010-01-01

    The recently presented electrochemical kinetic model, describing the electrochemical hydrogen storage in hydride-forming materials, was extended by the description of the solid/electrolyte interface, i.e., the charge-transfer kinetics and electrical double-layer charging. A complete set of equations

  19. Silyl Ketene Acetals/B(C6F53 Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers

    Directory of Open Access Journals (Sweden)

    Lu Hu

    2018-03-01

    Full Text Available This work reveals the silyl ketene acetal (SKA/B(C6F53 Lewis pair-catalyzed room-temperature group transfer polymerization (GTP of polar acrylic monomers, including methyl linear methacrylate (MMA, and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL and α-methylene-γ-butyrolactone (MBL as well. The in situ NMR monitored reaction of SKA with B(C6F53 indicated the formation of Frustrated Lewis Pairs (FLPs, although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C6F53-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C6F53-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C6F53 is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS. Moreover, using this method, we have successfully synthesized well-defined PMMBL-b-PMBL, PMMBL-b-PMBL-b-PMMBL and random copolymers with the predicated molecular weights (Mn and narrow molecular weight distribution (MWD.

  20. Efficient Synthesis of Functionalized 1-oxo-1-phenyl-2-acetic Acids through Ru(II)-catalyzed Transfer Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaowei; Gong, Binwei; Meng, Yanqiu [Shenyang Univ. of Chemical Technology, Shenyang (Korea, Republic of); Yan, Yunnan [Gannan Medical Univ., Ganzhou (Korea, Republic of); Tang, Xiaobo; Eric Xu, H.; Yi, Wei [Chinese Academy of Sciences, Shanghai (China); Li, Qiu [Univ. of Science and Technology of China, Suzhou (China)

    2013-10-15

    A new and alternative method for the efficient synthesis of indanylacetic acid 2 has been developed. The methodology used RuCl(p-cymene)[(R,R)-TsDPEN] as the catalyst and formic acid-triethylamine as the hydrogen source at room temperature under solvent-free conditions, and the reactions have excellent chemoselectivity and good compatibility of substrates. Used our developed method as the starting step, gram scale synthesis of GR24 was achieved smoothly with an overall yield of 72%. All the results suggested that further development of such methodology may be of interest. Further work to establish the mechanistic reasons for selectivity and to further explore the synthetic scope of this mode of transfer hydrogenation is in progress. The synthetic SL analog, GR24 is a very potent germination stimulant, which is widely used in parasitic weed research to stimulate germination and as a standard for comparison of new germinating agents. Owing to the prevalence of GR24, its total synthesis constitutes a hot area of research. So far all known synthetic routes of GR24 used indanylacetic acid 2 as a key intermediate, for which very few methods of building compound 2 have been reported.

  1. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today......’s hydride batteries, but a much poorer stability towards repeated charge/discharge cycling. The aim was to see if the cycleability of CaNi5 could be enhanced enough by modifications to make the compound a suitable electrode material. An alloying method based on mechanical alloying in a planetary ball mill...

  2. Metal Hydride Compression

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-07-01

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

  3. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

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

  4. Complex Hydrides for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Rate-controlling two-proton transfer coupled with heavy-atom motion in the 2-pyridinone-catalyzed mutarotation of tetramethylglucose. Experimental and calculated deuterium isotope effects

    International Nuclear Information System (INIS)

    Engdahl, K.A.; Bivehed, H.; Ahlberg, P.; Saunders, W.H. Jr.

    1983-01-01

    Primary and secondary deuterium isotope effects have been measured by polarimetry, and primary isotope effects have been calculated for the classical bifunctional catalysis: 2-pyridinone-catalyzed mutarotation of 2,3,4,6-tetra-O-methyl-α-D-glucopyranose (α-TMG) in benzene. From the positively curved plot of the specific rate of epimerization vs. the mole fraction of 2 H in the ''pool'' of OH and NH hydrogens, the isotope effects k/sub HH//k/sub DD/ = 3.66 +/- 0.09, k/sub HH//k/sub DH/ = 1.5, and k/sub HH//k/sub HD/ = 2.4 have been calculated. A secondary isotope effect of 1.14 +/- 0.02 has been measured by using α-TMG and (1- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(l- 2 H)-α-TMG], the synthesis of which is described in detail, together with those for (N- 2 H)-2-pyridinone and (1-O- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(1-O- 2 H)-α-TMG]. The rate data obtained have also been analyzed by fractionation theory, yielding approximately equal fractionation factors (0.5). The interpretation of the results has been assisted by calculations of the primary deuterium isotope effects using the BEBOVIB IV program. Two models involving small and considerable coupling, respectively, of the transferring protons to heavy-atom motion have been considered. In the favored structure for the transition state of the rate-limiting step, two protons are in transit, and their motion is governed either by a potential with a barrier or by one without. Their motion is considerably coupled to the heavy-atom motion (i.e., the breakage of the ring C-O bond), and tunnel corrections to the isotope effects are found to be negligible

  6. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    hydrogen. Further evaluation and development of this concept will be performed as follow-on work under another project. However, since the cost of reducing magnesium from magnesium oxide makes up 85% of the cost of the slurry, if hydrogen can be stored many times in the slurry, then the cost of storing hydrogen can be spread over many units of hydrogen and can be significantly reduced from the costs of a chemical hydride system. This may be the most important finding of this project. If the slurry is used to carry a rechargeable hydride, the slurry can be stored in a conventional liquid fuel tank and delivered to a release system as hydrogen is needed. The release system will contain only the hydride needed to produce the hydrogen desired. This is in contrast to conventional designs proposed for other rechargeable hydride systems that store all the hydride in a large and heavy pressure and heat transfer vessel.

  7. Hydriding failure in water reactor fuel elements

    International Nuclear Information System (INIS)

    Sah, D.N.; Ramadasan, E.; Unnikrishnan, K.

    1980-01-01

    Hydriding of the zircaloy cladding has been one of the important causes of failure in water reactor fuel elements. This report reviews the causes, the mechanisms and the methods for prevention of hydriding failure in zircaloy clad water reactor fuel elements. The different types of hydriding of zircaloy cladding have been classified. Various factors influencing zircaloy hydriding from internal and external sources in an operating fuel element have been brought out. The findings of post-irradiation examination of fuel elements from Indian reactors, with respect to clad hydriding and features of hydriding failure are included. (author)

  8. Mechanical properties and fracture of titanium hydrides

    International Nuclear Information System (INIS)

    Koketsu, Hideyuki; Taniyama, Yoshihiro; Yonezu, Akio; Cho, Hideo; Ogawa, Takeshi; Takemoto, Mikio; Nakayama, Gen

    2006-01-01

    Titanium hydrides tend to suffer fracture when their thicknesses reach a critical thickness. Morphology and mechanical property of the hydrides are, however, not well known. The study aims to reveal the hydride morphology and fracture types of the hydrides. Chevron shaped plate hydrides were found to be produced on the surface of pure titanium (Grade 1) and Grade 7 titanium absorbing hydrogen. There were tree types of fracture of the hydrides, i.e., crack in hydride layer, exfoliation of the layer and shear-type fracture of the hydride plates, during the growth of the hydrides and deformation. We next estimated the true stress-strain curves of the hydrides on Grade 1 and 7 titanium using the dual Vickers indentation method, and the critical strain causing the Mode-I fine crack by indentation. Fracture strength and strain of the hydrides in Grade 1 titanium were estimated as 566 MPa and 4.5%, respectively. Those of the hydride in Grade 7 titanium were 498 MPa and 16%. Though the fracture strains estimated from the plastic instability of true stress-strain curves were approximately the half of those estimated by finite element method, the titanium hydrides were estimated to possess some extent of toughness or plastic deformation capability. (author)

  9. Design and integration of a hydrogen storage on metallic hydrides

    International Nuclear Information System (INIS)

    Botzung, M.

    2008-01-01

    This work presents a hydrogen storage system using metal hydrides for a Combined Heat and Power (CHP) system. Hydride storage technology has been chosen due to project specifications: high volumetric capacity, low pressures (≤ 3.5 bar) and low temperatures (≤ 75 C: fuel cell temperature). During absorption, heat from hydride generation is dissipated by fluid circulation. An integrated plate-fin type heat exchanger has been designed to obtain good compactness and to reach high absorption/desorption rates. At first, the storage system has been tested in accordance with project specifications (absorption 3.5 bar, desorption 1.5 bar). Then, the hydrogen charge/discharge times have been decreased to reach system limits. System design has been used to simulate thermal and mass comportment of the storage tank. The model is based on the software Fluent. We take in consideration heat and mass transfers in the porous media during absorption/desorption. The hydride thermal and mass behaviour has been integrated in the software. The heat and mass transfers experimentally obtained have been compared to results calculated by the model. The influence of experimental and numerical parameters on the model behaviour has also been explored. (author) [fr

  10. Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.

    Science.gov (United States)

    Zhou, Bing; Chen, Zhaoqiang; Yang, Yaxi; Ai, Wen; Tang, Huanyu; Wu, Yunxiang; Zhu, Weiliang; Li, Yuanchao

    2015-10-05

    An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. High-pressure hydriding of Zircaloy

    International Nuclear Information System (INIS)

    Kim, Y.S.

    1996-01-01

    The hydriding characteristics of Zircaloy-2(Zry), sponge zirconium (as a liner on Zry plate), and crystal-bar zirconium exposed to pure H 2 at 0.1 MPa or 7 MPa and 400 C were determined in a thermogravimetric apparatus. The morphology of the hydrided specimens was also examined by optical microscopy. For all specimen types, the rate of hydriding in 7 MPa H 2 was two orders of magnitude greater than in 0.1 MPa H 2 . For Zry, uniform bulk hydriding was revealed by hydride precipitates at room temperature and on one occasion, a sunburst hydride. In addition, all specimen types exhibited a hydride surface layer. In a duplex Zry/sponge-Zr specimen, Zry is more heavily hydrided than the sponge Zr layer. (orig.)

  12. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

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

  13. Metal hydride compositions and lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Young, Kwo; Nei, Jean

    2018-04-24

    Heterogeneous metal hydride (MH) compositions comprising a main region comprising a first metal hydride and a secondary region comprising one or more additional components selected from the group consisting of second metal hydrides, metals, metal alloys and further metal compounds are suitable as anode materials for lithium ion cells. The first metal hydride is for example MgH.sub.2. Methods for preparing the composition include coating, mechanical grinding, sintering, heat treatment and quenching techniques.

  14. Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

    Science.gov (United States)

    Patki, Gauri Dilip

    mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

  15. O-alkylation of disodium salt of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate with 1,2-dichloroethane catalyzed by ionic type phase transfer catalyst and potassium iodide

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Huasheng; Yin, Hengbo; Wang, Aili; Shen, Jun; Yan, Xiaobo; Liu, Yumin; Zhang, Changhua [Jiangsu University, Zhenjiang (China)

    2014-01-15

    Diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate was efficiently synthesized via the O-alkylation of disodium salt of diethyl 3,4-dihydroxy thiophene-2,5-dicarboxylate with 1,2-dichloroethane over ionic type phase transfer catalysts, such as tetrabutyl ammonium bromide and benzyl triethyl ammonium chloride. The ionic type phase transfer catalysts showed higher catalytic activities than the nonionic type phase transfer catalysts, such as triethylamine, pyridine, 18-crown-6, and polyethylene glycol 400/600, in the O-alkylation reaction. The conversion of the disodium salt of more than 97% and the selectivity of diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate of more than 98% were achieved when the O-alkylation reaction was synergistically catalyzed by tetrabutyl ammonium bromide and potassium iodide.

  16. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir; Atiqullah, Muhammad; Malaibari, Zuhair O.; Al-Harthi, Mamdouh A.; Emwas, Abdul-Hamid M.; Ul-Hamid, Anwar

    2015-01-01

    -catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion

  17. Modeling of hydrogen isotopes separation in a metal hydride bed

    International Nuclear Information System (INIS)

    Charton, S.; Corriou, J.P.; Schweich, D.

    1999-01-01

    A predictive model for hydrogen isotopes separation in a non-isothermal bed of unsupported palladium hydride particles is derived. It accounts for the non-linear adsorption-dissociation equilibrium, hydrodynamic dispersion, pressure drop, mass transfer kinetics, heat of sorption and heat losses at the bed wall. Using parameters from the literature or estimated with classical correlations, the model gives simulated curves in agreement with previously published experiments without any parameter fit. The non-isothermal behavior is shown to be responsible for drastic changes of the mass transfer rate which is controlled by diffusion in the solid-phase lattice. For a feed at 300 K and atmospheric pressure, the endothermic hydride-to-deuteride exchange is kinetically controlled, whereas the reverse exothermic exchange is nearly at equilibrium. Finally, a simple and efficient thermodynamic model for the dissociative equilibrium between a metal and a diatomic gas is proposed. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  18. Study on an innovative fast reactor utilizing hydride neutron absorber - Final report of phase I study

    International Nuclear Information System (INIS)

    Konashi, K.; Iwasaki, T.; Itoh, K.; Hirai, M.; Sato, J.; Kurosaki, K.; Suzuki, A.; Matsumura, Y.; Abe, S.

    2010-01-01

    These days, the demand to use nuclear resources efficiently is growing for long-term energy supply and also for solving the green house problem. It is indispensable to develop technologies to reduce environmental load with the nuclear energy supply for sustainable development of human beings. In this regard, the development of the fast breeder reactor (FBR) is preferable to utilize nuclear resources effectively and also to burn minor actinides which possess very long toxicity for more than thousands years if they are not extinguished. As one of the FBR developing works in Japan this phase I study started in 2006 to introduce hafnium (Hf) hydride and Gadolinium-Zirconium (Gd-Zr) hydride as new control materials in FBR. By adopting them, the FBR core control technology is improved by two ways. One is extension of control rod life time by using long life Hf hydride which leads to reduce the fabrication and disposal cost and the other is reduction of the excess reactivity by adopting Gd-Zr hydride which leads to reduce the number of control rods and simplifies the core upper structure. This three year study was successfully completed and the following results were obtained. The core design was performed to examine the applicability of the Hf hydride absorber to Japanese Sodium Fast Reactor (JSFR) and it is clarified that the control rod life time can be prolonged to 6 years by adopting Hf hydride and the excess reactivity of the beginning of the core cycle can be reduced to half and the number of the control rods is also reduced to half by using the Gd-Zr hydride burnable poison. The safety analyses also certified that the core safety can be maintained with the same reliability of JSFR Hf hydride and Gd-Zr hydride pellets were fabricated in good manner and their basic features for design use were measured by using the latest devices such as SEM-EDX. In order to reduce the hydrogen transfer through the stainless steel cladding a new technique which shares calorizing

  19. The Study of NADPH-Dependent Flavoenzyme-Catalyzed Reduction of Benzo[1,2-c]1,2,5-oxadiazole N-Oxides (Benzofuroxans

    Directory of Open Access Journals (Sweden)

    Jonas Šarlauskas

    2014-12-01

    Full Text Available The enzymatic reactivity of a series of benzo[1,2-c]1,2,5-oxadiazole N-oxides (benzofuroxans; BFXs towards mammalian single-electron transferring NADPH:cytochrome P-450 reductase (P-450R and two-electron (hydride transferring NAD(PH:quinone oxidoreductase (NQO1 was examined in this work. Since the =N+ (→OO− moiety of furoxan fragments of BFXs bears some similarity to the aromatic nitro-group, the reactivity of BFXs was compared to that of nitro-aromatic compounds (NACs whose reduction mechanisms by these and other related flavoenzymes have been extensively investigated. The reduction of BFXs by both P-450R and NQO1 was accompanied by O2 uptake, which was much lower than the NADPH oxidation rate; except for annelated BFXs, whose reduction was followed by the production of peroxide. In order to analyze the possible quantitative structure-activity relationships (QSARs of the enzymatic reactivity of the compounds, their electron-accepting potency and other reactivity indices were assessed by quantum mechanical methods. In P-450R-catalyzed reactions, both BFXs and NACs showed the same reactivity dependence on their electron-accepting potency which might be consistent with an “outer sphere” electron transfer mechanism. In NQO1-catalyzed two-electron (hydride transferring reactions, BFXs acted as more efficient substrates than NACs, and the reduction efficacy of BFXs by NQO1 was in general higher than by single-electron transferring P-450R. In NQO1-catalyzed reactions, QSARs obtained showed that the reduction efficacy of BFXs, as well as that of NACs, was determined by their electron-accepting potency and could be influenced by their binding mode in the active center of NQO1 and by their global softness as their electronic characteristic. The reductive conversion of benzofuroxan by both flavoenzymes yielded the same reduction product of benzofuroxan, 2,3-diaminophenazine, with the formation of o-benzoquinone dioxime as a putative primary

  20. Structural characterization of tartrate dehydrogenase: a versatile enzyme catalyzing multiple reactions

    International Nuclear Information System (INIS)

    Malik, Radhika; Viola, Ronald E.

    2010-01-01

    The first structure of an NAD-dependent tartrate dehydrogenase (TDH) has been solved to 2 (angstrom) resolution by single anomalous diffraction (SAD) phasing as a complex with the intermediate analog oxalate, Mg 2+ and NADH. This TDH structure from Pseudomonas putida has a similar overall fold and domain organization to other structurally characterized members of the hydroxy-acid dehydrogenase family. However, there are considerable differences between TDH and these functionally related enzymes in the regions connecting the core secondary structure and in the relative positioning of important loops and helices. The active site in these complexes is highly ordered, allowing the identification of the substrate-binding and cofactor-binding groups and the ligands to the metal ions. Residues from the adjacent subunit are involved in both the substrate and divalent metal ion binding sites, establishing a dimer as the functional unit and providing structural support for an alternating-site reaction mechanism. The divalent metal ion plays a prominent role in substrate binding and orientation, together with several active-site arginines. Functional groups from both subunits form the cofactor-binding site and the ammonium ion aids in the orientation of the nicotinamide ring of the cofactor. A lysyl amino group (Lys192) is the base responsible for the water-mediated proton abstraction from the C2 hydroxyl group of the substrate that begins the catalytic reaction, followed by hydride transfer to NAD. A tyrosyl hydroxyl group (Tyr141) functions as a general acid to protonate the enolate intermediate. Each substrate undergoes the initial hydride transfer, but differences in substrate orientation are proposed to account for the different reactions catalyzed by TDH.

  1. Tritium processing using metal hydrides

    International Nuclear Information System (INIS)

    Mallett, M.W.

    1986-01-01

    E.I. duPont de Nemours and Company is commissioned by the US Department of Energy to operate the Savannah River Plant and Laboratory. The primary purpose of the plant is to produce radioactive materials for national defense. In keeping with current technology, new processes for the production of tritium are being developed. Three main objectives of this new technology are to ease the processing of, ease the storage of, and to reduce the operating costs of the tritium production facility. Research has indicated that the use of metal hydrides offers a viable solution towards satisfying these objectives. The Hydrogen and Fuels Technology Division has the responsibility to conduct research in support of the tritium production process. Metal hydride technology and its use in the storage and transportation of hydrogen will be reviewed

  2. Hydride Molecules towards Nearby Galaxies

    Science.gov (United States)

    Monje, Raquel R.; La, Ngoc; Goldsmith, Paul

    2018-06-01

    Observations carried out by the Herschel Space Observatory revealed strong spectroscopic signatures from light hydride molecules within the Milky Way and nearby active galaxies. To better understand the chemical and physical conditions of the interstellar medium, we conducted the first comprehensive survey of hydrogen fluoride (HF) and water molecular lines observed through the SPIRE Fourier Transform Spectrometer. By collecting and analyzing the sub-millimeter spectra of over two hundred sources, we found that the HF J = 1 - 0 rotational transition which occurs at approximately 1232 GHz was detected in a total of 39 nearby galaxies both in absorption and emission. The analysis will determine the main excitation mechanism of HF in nearby galaxies and provide steady templates of the chemistry and physical conditions of the ISM to be used in the early universe, where observations of hydrides are more scarce.

  3. Rechargeable metal hydrides for spacecraft application

    Science.gov (United States)

    Perry, J. L.

    1988-01-01

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

  4. Complex hydrides for hydrogen storage

    Science.gov (United States)

    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.

  5. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

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

  6. Use of reversible hydrides for hydrogen storage

    Science.gov (United States)

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

    1980-01-01

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

  7. NMR study of hydride systems

    International Nuclear Information System (INIS)

    Peretz, M.

    1980-02-01

    The hydrides of thorium (ThH 2 , Th 4 H 15 and Th 4 D 15 ) and the intermetallic compound system (Zr(Vsub(1-x)Cosub(x)) 2 and its hydrides were investigated using the nuclear magnetic resonance (NMR) technique. From the results for the thorium hydride samples it was concluded that the density of states at the Fermi level n(Esub(f)) is higher in Th 4 H 15 than in ThH 2 ; there is an indirect reaction between the protons and the d electrons belonging to the Th atoms in Th 4 H 15 ; n(E) has a sharp structure near Esub(f). It was also found that the hydrogen diffusion mechanism changes with temperature. From the results for the intermetallic compound system conclusions were drawn concerning variations in the electronic structure, which explain the behavior of the system. In hydrogen diffusion studies in several samples it was found that Co atoms slow the diffusion rate. Quadrupole spectra obtained at low temperatures show that the H atoms preferably occupy tetrahedral sites formed by three V atoms and one Z atom. (H.K.)

  8. Reactivity patterns of transition metal hydrides and alkyls

    International Nuclear Information System (INIS)

    Jones, W.D. II.

    1979-05-01

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

  9. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

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

  10. Fundamental experiments on hydride reorientation in zircaloy

    Science.gov (United States)

    Colas, Kimberly B.

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

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

    Science.gov (United States)

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

    2013-09-01

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

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  13. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek

    2011-02-18

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek; Thivolle-Cazat, Jean; Taoufik, Mostafa; Stoffelbach, Franç ois; Norsic, Sé bastien; Basset, Jean-Marie

    2011-01-01

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Catalyzed Nano-Framework Stablized High Density Reversible Hydrogen Storage Systems

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xia [value too long for type character varying(50); Opalka, Susanne M.; Mosher, Daniel A; Laube, Bruce L; Brown, Ronald J; Vanderspurt, Thomas H; Arsenault, Sarah; Wu, Robert; Strickler, Jamie; Ronnebro, Ewa; Boyle, Tim; Cordaro, Joseph

    2010-06-30

    A wide range of high capacity on-board rechargeable material candidates have exhibited non-ideal behavior related to irreversible hydrogen discharge / recharge behavior, and kinetic instability or retardation. This project addresses these issues by incorporating solvated and other forms of complex metal hydrides, with an emphasis on borohydrides, into nano-scale frameworks of low density, high surface area skeleton materials to stabilize, catalyze, and control desorption product formation associated with such complex metal hydrides. A variety of framework chemistries and hydride / framework combinations were investigated to make a relatively broad assessment of the method's potential. In this project, the hydride / framework interactions were tuned to decrease desorption temperatures for highly stable compounds or increase desorption temperatures for unstable high capacity compounds, and to influence desorption product formation for improved reversibility. First principle modeling was used to explore heterogeneous catalysis of hydride reversibility by modeling H2 dissociation, hydrogen migration, and rehydrogenation. Atomic modeling also demonstrated enhanced NaTi(BH4)4 stabilization at nano-framework surfaces modified with multi-functional agents. Amine multi-functional agents were found to have more balanced interactions with nano-framework and hydride clusters than other functional groups investigated. Experimentation demonstrated that incorporation of Ca(BH4)2 and Mg(BH4)2 in aerogels enhanced hydride desorption kinetics. Carbon aerogels were identified as the most suitable nano-frameworks for hydride kinetic enhancement and high hydride loading. High loading of NaTi(BH4)4 ligand complex in SiO2 aerogel was achieved and hydride stability was improved with the aerogel. Although improvements of desorption kinetics was observed, the incorporation of

  16. Manufacture of titanium and zirconium hydrides

    International Nuclear Information System (INIS)

    Mares, F.; Hanslik, T.

    1973-01-01

    A method is described of manufacturing titanium and zirconium hydrides by hydrogenation of said metals characterized by the reaction temperature ranging between 250 to 500 degC, hydrogen pressure of 20 to 300 atm and possibly by the presence of a hydride of the respective metal. (V.V.)

  17. Hydride effect on crack instability of Zircaloy cladding

    Energy Technology Data Exchange (ETDEWEB)

    Tseng, Che-Chung, E-mail: cctseng@iner.gov.tw [Institute of Nuclear Energy Research, No. 1000, Wunhua Road, Jiaan Village, Lungtan, Township, Taoyuan County 32546, Taiwan (China); Sun, Ming-Hung [Institute of Nuclear Energy Research, No. 1000, Wunhua Road, Jiaan Village, Lungtan, Township, Taoyuan County 32546, Taiwan (China); Chao, Ching-Kong [Department of Mechanical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106, Taiwan (China)

    2014-04-01

    Highlights: • Radial hydrides near the crack tip had a significant effect on crack propagation. • For radial hydrides off the crack line vertically, the effect on crack propagation was notably reduced. • The longer hydride platelet resulted in a remarkable effect on crack propagation. • A long split in the radial hydride precipitate would enhance crack propagation. • The presence of circumferential hydride among radial hydrides may play an important role in crack propagation. - Abstract: A methodology was proposed to investigate the effect of hydride on the crack propagation in fuel cladding. The analysis was modeled based on an outside-in crack with radial hydrides located near its crack tip. The finite element method was used in the calculation; both stress intensity factor K{sub I} and J integral were applied to evaluate the crack stability. The parameters employed in the analysis included the location of radial hydride, hydride dimensions, number of hydrides, and the presence of circumferential hydride, etc. According to our study, the effective distance between a radial hydride and the assumed cladding surface crack for the enhancement of crack propagation proved to be no greater than 0.06 mm. For a hydride not on the crack line, it would induce a relatively minor effect on crack propagation if the vertical distance was beyond 0.05 mm. However, a longer hydride precipitate as well as double radial hydrides could have a remarkable effect on crack propagation. A combined effect of radial and circumferential hydrides was also discussed.

  18. Obtaining zircaloy powder through hydriding

    International Nuclear Information System (INIS)

    Dupim, Ivaldete da Silva; Moreira, Joao M.L.

    2009-01-01

    Zirconium alloys are good options for the metal matrix in dispersion fuels for power reactors due to their low thermal neutron absorption cross-section, good corrosion resistance, good mechanical strength and high thermal conductivity. A necessary step for obtaining such fuels is producing Zr alloy powder for the metal matrix composite material. This article presents results from the Zircaloy-4 hydrogenation tests with the purpose to embrittle the alloy as a first step for comminuting. Several hydrogenation tests were performed and studied through thermogravimetric analysis. They included H 2 pressures of 25 and 50 kPa and temperatures ranging between from 20 to 670 deg C. X-ray diffraction analysis showed in the hydrogenated samples the predominant presence of ZrH 2 and some ZrO 2 . Some kinetics parameters for the Zircaloy-4 hydrogenation reaction were obtained: the time required to reach the equilibrium state at the dwell temperature was about 100 minutes; the hydrogenation rate during the heating process from 20 to 670 deg C was about 21 mg/h, and at constant temperature of 670 deg C, the hydride rate was about 1.15 mg/h. The hydrogenation rate is largest during the heating process and most of it occurs during this period. After hydrogenated, the samples could easily be comminuted indicating that this is a possible technology to obtain Zircaloy powder. The results show that only few minutes of hydrogenation are necessary to reach the hydride levels required for comminuting the Zircaloy. The final hydride stoichiometry was between 2.7 and 2.8 H for each Zr atom in the sample (author)

  19. Hydrogen Storage using Metal Hydrides in a Stationary Cogeneration System

    International Nuclear Information System (INIS)

    Botzung, Maxime; Chaudourne, Serge; Perret, Christian; Latroche, Michel; Percheron-Guegan, Annick; Marty Philippe

    2006-01-01

    In the frame of the development of a hydrogen production and storage unit to supply a 40 kW stationary fuel cell, a metal hydride storage tank was chosen according to its reliability and high energetic efficiency. The study of AB5 compounds led to the development of a composition adapted to the project needs. The absorption/desorption pressures of the hydride at 75 C (2 / 1.85 bar) are the most adapted to the specifications. The reversible storage capacity (0.95 %wt) has been optimized to our work conditions and chemical kinetics is fast. The design of the Combined Heat and Power CHP system requires 5 kg hydrogen storage but in a first phase, only a 0.1 kg prototype has been realised and tested. Rectangular design has been chosen to obtain good compactness with an integrated plate fin type heat exchanger designed to reach high absorption/desorption rates. In this paper, heat and mass transfer characteristics of the Metal Hydride tank (MH tank) during absorption/desorption cycles are given. (authors)

  20. Zirconium hydride containing explosive composition

    Science.gov (United States)

    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.

  1. THE DECEPTIVELY SIMPLE THERMOLYSIS OF TRIVALENT PERMETHYLTITANOCENE DERIVATIVES (ETA-5-C5ME5)2TIR - FORMATION OF A TETRAMETHYLFULVENE TITANIUM COMPOUND (ETA-6-C5ME4CH2)(ETA-5-C5ME5)TI AND RH, CATALYZED BY PERMETHYLTITANOCENE HYDRIDE, (ETA-5-C5ME5)2TIH

    NARCIS (Netherlands)

    LUINSTRA, GA; TEUBEN, JH

    1992-01-01

    The complexes Cp*2TiR (Cp* = eta-5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = eta-6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by

  2. The Deceptively Simple Thermolysis of Trivalent Permethyltitanocene Derivatives (η5-C5Me5)2TiR. Formation of a Tetramethylfulvene Titanium Compound (η6-C5Me4CH2)(η5-C5Me5)Ti and RH, Catalyzed by Permethyltitanocene Hydride, (η5-C5Me5)2TiH

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.

    1992-01-01

    The complexes Cp*2TiR (Cp* = η5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = η6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by

  3. Hydrogen-storing hydride complexes

    Science.gov (United States)

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

    2012-04-10

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

  4. Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

    Science.gov (United States)

    Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

    2017-10-17

    The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Activated aluminum hydride hydrogen storage compositions and uses thereof

    Science.gov (United States)

    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.

  6. Hydrogen adsorption on palladium and palladium hydride at 1 bar

    DEFF Research Database (Denmark)

    Johansson, Martin; Skulason, Egill; Nielsen, Gunver

    2010-01-01

    strongly to Pd hydride than to Pd. The activation barrier for desorption at a H coverage of one mono layer is slightly lower on Pd hydride, whereas the activation energy for adsorption is similar on Pd and Pd hydride. It is concluded that the higher sticking probability on Pd hydride is most likely caused...

  7. Quinone-Catalyzed Selective Oxidation of Organic Molecules

    Science.gov (United States)

    Wendlandt, Alison E.

    2016-01-01

    Lead In Quinones are common stoichiometric reagents in organic chemistry. High potential para-quinones, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in Copper Amine Oxidases and mediate efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed via electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and have important implications for the development of new quinone reagents and quinone-catalyzed transformations. PMID:26530485

  8. Identification and characterization of a new Zirconium hydride

    International Nuclear Information System (INIS)

    Zhao, Z.

    2007-01-01

    In order to control the integrity of the fuel clad, alloy of zirconium, it is necessary to predict the behavior of zirconium hydrides in the environment (temperature, stress...), at a microscopic scale. A characterization study by TEM of hydrides has been realized. It shows little hydrides about 500 nm, in hydride Zircaloy 4. Then a more detailed study identified a new hydride phase presented in this paper. (A.L.B.)

  9. Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

    DEFF Research Database (Denmark)

    Eriksen, J.; Monsted, L.; Monsted, O.

    2010-01-01

    The mechanism of the catalytic HID exchange in primary alcohol substrates derived from aldopentoses, promoted by a macrocyclic rhodium(III) complex, has been shown to occur by a reversible redox reaction that gives aldehyde and a rhodium hydride complex. Hydride exchange in the latter complex...... promotes the introduction of solvent hydrogen in the primary alcohol formed by the reverse reaction. The hydride complex has been crystallographically characterized as a trifluoromethanesulfonate salt that contains the trans-[Rh(cycb)(H)(OH2)](2+) (cycb = rac-5,5,7,12,12,14-hexamethyl-1......,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

  10. A procedure for preparing alkali metal hydrides

    International Nuclear Information System (INIS)

    Lemieux, R.U.; Sanford, C.E.; Prescott, J.F.

    1976-01-01

    A plain low cost, procedure for the continuous, low temperature preparation of sodium or potassium hydrides using cheap reagents is presented. Said invention is especially concerned with a process of purifying of a catalytic exchange liquid used for deuterium enrichment, in which an alkali metal hydride is produced as intermediate product. The procedure for producing the sodium and potassium hydrides consists in causing high pressure hydrogen to be absorbed by a mixture of at least a lower monoalkylamine and an alkylamide of an alkali metal from at least one of said amines [fr

  11. Hydride observations using the neutrography technique

    International Nuclear Information System (INIS)

    Meyer, G.; Baruj, A.; Borzone, E.M.; Cardenas, R.; Szames, E.; Somoza, J.; Rivas, S.; Sanchez, F.A.; Marin, J.

    2012-01-01

    Neutron radiography observations were performed at the RA-6 experimental nuclear facility in Bariloche. Images from a prototype of a hydride-based hydrogen storage device have been obtained. The technique allows visualizing the inner hydride space distribution. The hydride appeared compacted at the lower part of the prototype after several cycles of hydrogen charge and discharge. The technique has also been applied to the study of Zr/ZrH 2 samples. There is a linear relation between the sample width/hydrogen concentration and the photograph grey scale. This information could be useful for the study of nuclear engineering materials and to determine their possible degradation by hydrogen pick up (author)

  12. Decomposition kinetics of plutonium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, J.M.; Stakebake, J.L.

    1979-01-01

    Kinetic data for decomposition of PuH/sub 1/ /sub 95/ provides insight into a possible mechanism for the hydriding and dehydriding reactions of plutonium. The fact that the rate of the hydriding reaction, K/sub H/, is proportional to P/sup 1/2/ and the rate of the dehydriding process, K/sub D/, is inversely proportional to P/sup 1/2/ suggests that the forward and reverse reactions proceed by opposite paths of the same mechanism. The P/sup 1/2/ dependence of hydrogen solubility in metals is characteristic of the dissociative absorption of hydrogen; i.e., the reactive species is atomic hydrogen. It is reasonable to assume that the rates of the forward and reverse reactions are controlled by the surface concentration of atomic hydrogen, (H/sub s/), that K/sub H/ = c'(H/sub s/), and that K/sub D/ = c/(H/sub s/), where c' and c are proportionality constants. For this surface model, the pressure dependence of K/sub D/ is related to (H/sub s/) by the reaction (H/sub s/) reversible 1/2H/sub 2/(g) and by its equilibrium constant K/sub e/ = (H/sub 2/)/sup 1/2//(H/sub s/). In the pressure range of ideal gas behavior, (H/sub s/) = K/sub e//sup -1/(RT)/sup -1/2/ and the decomposition rate is given by K/sub D/ = cK/sub e/(RT)/sup -1/2/P/sup 1/2/. For an analogous treatment of the hydriding process with this model, it can be readily shown that K/sub H/ = c'K/sub e//sup -1/(RT)/sup -1/2/P/sup 1/2/. The inverse pressure dependence and direct temperature dependence of the decomposition rate are correctly predicted by this mechanism which is most consistent with the observed behavior of the Pu--H system.

  13. [Phase transfer catalyzed bioconversion of penicillin G to 6-APA by immobilized penicillin acylase in recyclable aqueous two-phase systems with light/pH sensitive copolymers].

    Science.gov (United States)

    Jin, Ke-ming; Cao, Xue-jun; Su, Jin; Ma, Li; Zhuang, Ying-ping; Chu, Ju; Zhang, Si-liang

    2008-03-01

    Immobilized penicillin acylase was used for bioconversion of penicillin PG into 6-APA in aqueous two-phase systems consisting of a light-sensitive polymer PNBC and a pH-sensitive polymer PADB. Partition coefficients of 6-APA was found to be about 5.78 in the presence of 1% NaCl. Enzyme kinetics showed that the reaction reached equilibrium at roughly 7 h. The 6-APA mole yields were 85.3% (pH 7.8, 20 degrees C), with about 20% increment as compared with the reaction of single aqueous phase buffer. The partition coefficient of PG (Na) varied scarcely, while that of the product, 6-APA and phenylacetic acid (PA) significantly varied due to Donnan effect of the phase systems and hydrophobicity of the products. The variation of the partition coefficients of the products also affected the bioconversion yield of the products. In the aqueous two-phase systems, the substrate, PG, the products of 6-APA and PA were biased in the top phase, while immobilized penicillin acylase at completely partitioned at the bottom. The substrate and PG entered the bottom phase, where it was catalyzed into 6-APA and PA and entered the top phase. Inhibition of the substrate and products was removed to result in improvement of the product yield, and the immobilized enzyme showed higher efficiency than the immobilized cells and occupied smaller volume. Compared with the free enzyme, immobilized enzyme had greater stability, longer life-time, and was completely partitioned in the bottom phase and recycle. Bioconversion in two-phase systems using immobilized penicillin acylase showed outstanding advantage. The light-sensitive copolymer forming aqueous two-phase systems could be recovered by laser radiation at 488 nm or filtered 450 nm light, while pH-sensitive polymer PADB could be recovered at the isoelectric point (pH 4.1). The recovery of the two copolymers was between 95% and 99%.

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

    Science.gov (United States)

    2016-01-04

    AFRL-AFOSR-VA-TR-2016-0075 The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters KIT BOWEN JOHNS HOPKINS UNIV BALTIMORE MD...2. REPORT TYPE Final Performance 3. DATES COVERED (From - To) 30-09-2014 to 29-09-2015 4. TITLE AND SUBTITLE The Oxidation Products of Aluminum ...Hydride and Boron Aluminum Hydride Clusters 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0324 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) KIT

  15. Tritium removal using vanadium hydride

    International Nuclear Information System (INIS)

    Hill, F.B.; Wong, Y.W.; Chan, Y.N.

    1978-01-01

    The results of an initial examination of the feasibility of separation of tritium from gaseous protium-tritium mixtures using vanadium hydride in cyclic processes is reported. Interest was drawn to the vanadium-hydrogen system because of the so-called inverse isotope effect exhibited by this system. Thus the tritide is more stable than the protide, a fact which makes the system attractive for removal of tritium from a mixture in which the light isotope predominates. The initial results of three phases of the research program are reported, dealing with studies of the equilibrium and kinetics properties of isotope exchange, development of an equilibrium theory of isotope separation via heatless adsorption, and experiments on the performance of a single heatless adsorption stage. In the equilibrium and kinetics studies, measurements were made of pressure-composition isotherms, the HT--H 2 separation factors and rates of HT--H 2 exchange. This information was used to evaluate constants in the theory and to understand the performance of the heatless adsorption experiments. A recently developed equilibrium theory of heatless adsorption was applied to the HT--H 2 separation using vanadium hydride. Using the theory it was predicted that no separation would occur by pressure cycling wholly within the β phase but that separation would occur by cycling between the β and γ phases and using high purge-to-feed ratios. Heatless adsorption experiments conducted within the β phase led to inverse separations rather than no separation. A kinetic isotope effect may be responsible. Cycling between the β and γ phases led to separation but not to the predicted complete removal of HT from the product stream, possibly because of finite rates of exchange. Further experimental and theoretical work is suggested which may ultimately make possible assessment of the feasibility and practicability of hydrogen isotope separation by this approach

  16. Thermal coupling of a high temperature PEM fuel cell with a complex hydride tank

    DEFF Research Database (Denmark)

    Pfeifer, P.; Wall, C.; Jensen, Jens Oluf

    2009-01-01

    the possibilities of a thermal coupling of a high temperature PEM fuel cell operating at 160-200 degrees C. The starting temperatures and temperature hold-times before starting fuel cell operation, the heat transfer characteristics of the hydride storage tanks, system temperature, fuel cell electrical power......Sodium alanate doped with cerium catalyst has been proven to have fast kinetics for hydrogen ab- and de-sorption as well as a high gravimetric storage density around 5 wt%. The kinetics of hydrogen sorption can be improved by preparing the alanate as nanocrystalline material. However, the second...... decomposition step, i.e. the decomposition of the hexahydride to sodium hydride and aluminium which refers to 1.8 wt% hydrogen is supposed to happen above 110 degrees C. The discharge of the material is thus limited by the level of heat supplied to the hydride storage tank. Therefore, we evaluated...

  17. Kinetic behaviour of low-Co AB5-type metal hydride electrodes

    International Nuclear Information System (INIS)

    Tliha, M.; Boussami, S.; Mathlouthi, H.; Lamloumi, J.; Percheron-Guegan, A.

    2010-01-01

    The kinetic behaviour of the LaNi 3.55 Mn 0.4 Al 0.3 Co 0.4 Fe 0.35 metal hydride, used as a negative electrode in the nickel/metal hydride (Ni/MH) batteries, was investigated using electrochemical impedance spectroscopy (EIS) at different state of charge (SOC). Impedance measurements were performed in the frequency range from 50 kHz to 1 mHz. Electrochemical impedance spectrum of the metal hydride electrode was interpreted by an equivalent circuit including the different electrochemical processes taking place on the interface between the MH electrode and the electrolyte. Electrochemical kinetic parameters such as the charge-transfer resistance R tc , the exchange current density I 0 and the hydrogen diffusion coefficient D H were determined at different state of charge. The results of EIS measurements indicate that the electrochemical reaction activity of the LaNi 3.55 Mn 0.4 Al 0.3 Co 0.4 Fe 0.35 metal hydride electrode was markedly improved with increasing state of charge (SOC). The transformation α-β is probably a limiting step in the mechanisms of hydrogenation of metal hydride electrode.

  18. Determination of antimony by using a quartz atom trap and electrochemical hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Menemenlioglu, Ipek; Korkmaz, Deniz [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Ataman, O. Yavuz [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey)], E-mail: ataman@metu.edu.tr

    2007-01-15

    The analytical performance of a miniature quartz trap coupled with electrochemical hydride generator for antimony determination is described. A portion of the inlet arm of the conventional quartz tube atomizer was used as an integrated trap medium for on-line preconcentration of electrochemically generated hydrides. This configuration minimizes transfer lines and connections. A thin-layer of electrochemical flow through cell was constructed. Lead and platinum foils were employed as cathode and anode materials, respectively. Experimental operation conditions for hydride generation as well as the collection and revolatilization conditions for the generated hydrides in the inlet arm of the quartz tube atomizer were optimized. Interferences of copper, nickel, iron, cobalt, arsenic, selenium, lead and tin were examined both with and without the trap. 3{sigma} limit of detection was estimated as 0.053 {mu}g l{sup -1} for a sample size of 6.0 ml collected in 120 s. The trap has provided 18 fold sensitivity improvement as compared to electrochemical hydride generation alone. The accuracy of the proposed technique was evaluated with two standard reference materials; Trace Metals in Drinking Water, Cat CRM-TMDW and Metals on Soil/Sediment 4, IRM-008.

  19. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Rozhkov, Roman Vladimirovich [Iowa State Univ., Ames, IA (United States)

    2004-01-01

    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a β-hydrogen in the vinylic halide results in β-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the α-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  20. Disposal of tritium-exposed metal hydrides

    International Nuclear Information System (INIS)

    Nobile, A.; Motyka, T.

    1991-01-01

    A plan has been established for disposal of tritium-exposed metal hydrides used in Savannah River Site (SRS) tritium production or Materials Test Facility (MTF) R ampersand D operations. The recommended plan assumes that the first tritium-exposed metal hydrides will be disposed of after startup of the Solid Waste Disposal Facility (SWDF) Expansion Project in 1992, and thus the plan is consistent with the new disposal requiremkents that will be in effect for the SWDF Expansion Project. Process beds containing tritium-exposed metal hydride powder will be disposed of without removal of the powder from the bed; however, disposal of tritium-exposed metal hydride powder that has been removed from its process vessel is also addressed

  1. Method of making alkali metal hydrides

    Science.gov (United States)

    Pecharsky, Vitalij K.; Gupta, Shalabh; Pruski, Marek; Hlova, Ihor; Castle, Andra

    2017-05-30

    A method is provided for making alkali metal hydrides by mechanochemically reacting alkali metal and hydrogen gas under mild temperature (e.g room temperature) and hydrogen pressure conditions without the need for catalyst, solvent, and intentional heating or cooling.

  2. Predicting formation enthalpies of metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Andreasen, A.

    2004-12-01

    In order for the hydrogen based society viz. a society in which hydrogen is the primary energy carrier to become realizable an efficient way of storing hydrogen is required. For this purpose metal hydrides are serious candidates. Metal hydrides are formed by chemical reaction between hydrogen and metal and for the stable hydrides this is associated with release of heat ({delta}H{sub f} ). The more thermodynamically stable the hydride, the larger {delta}H{sub f}, and the higher temperature is needed in order to desorp hydrogen (reverse reaction) and vice versa. For practical application the temperature needed for desorption should not be too high i.e. {delta}H{sub f} should not be too large. If hydrogen desorption is to be possible below 100 deg C (which is the ultimate goal if hydrogen storage in metal hydrides should be used in conjunction with a PEM fuel cell), {delta}H{sub f} should not exceed -48 kJ/mol. Until recently only intermetallic metal hydrides with a storage capacity less than 2 wt.% H{sub 2} have met this criterion. However, discovering reversible hydrogen storage in complex metal hydrides such as NaAlH{sub 4} (5.5 wt. % reversible hydrogen capacity) have revealed a new group of potential candiates. However, still many combination of elements from the periodic table are yet to be explored. Since experimental determination of thermodynamic properties of the vast combinations of elements is tedious it may be advantagous to have a predictive tool for this task. In this report different ways of predicting {delta}H{sub f} for binary and ternary metal hydrides are reviewed. Main focus will be on how well these methods perform numerically i.e. how well experimental results are resembled by the model. The theoretical background of the different methods is only briefly reviewed. (au)

  3. Dependency of Delayed Hydride Crack Velocity on the Direction of an Approach to Test Temperatures in Zirconium Alloys

    International Nuclear Information System (INIS)

    Kim, Young Suk; Kim, Kang Soo; Im, Kyung Soo; Ahn, Sang Bok; Cheong, Yong Moo

    2005-01-01

    crack tip, leading to the transfer of hydrogen from the bulk region to the crack tip. In short, this is the driving force for the DHC of zirconium alloys upon an approach to the test temperature by a heating. It should be noted that Kim's proposition that the terminal solid solubility for dissolution (TSSD) of the γ-hydride is higher than that of the δ-hydride is based on the experimental results reported by Cann and Mishra. The objective of this study is to demonstrate if the water-quenched Zr-2.5Nb will have the DHC crack growth even at the temperatures above 180 .deg. C where the furnace-cooled Zr-2.5Nb will not. This experiment will provide supportive evidence that the TSSD of γ- hydrides is higher than that of δ-hydrides and furthermore, it will confirm the feasibility of Kim's DHC model

  4. Dependency of Delayed Hydride Crack Velocity on the Direction of an Approach to Test Temperatures in Zirconium Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kim, Kang Soo; Im, Kyung Soo; Ahn, Sang Bok; Cheong, Yong Moo [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2005-07-01

    hydrogen concentration or .C between the bulk and the crack tip, leading to the transfer of hydrogen from the bulk region to the crack tip. In short, this is the driving force for the DHC of zirconium alloys upon an approach to the test temperature by a heating. It should be noted that Kim's proposition that the terminal solid solubility for dissolution (TSSD) of the {gamma}-hydride is higher than that of the {delta}-hydride is based on the experimental results reported by Cann and Mishra. The objective of this study is to demonstrate if the water-quenched Zr-2.5Nb will have the DHC crack growth even at the temperatures above 180 .deg. C where the furnace-cooled Zr-2.5Nb will not. This experiment will provide supportive evidence that the TSSD of {gamma}- hydrides is higher than that of {delta}-hydrides and furthermore, it will confirm the feasibility of Kim's DHC model.

  5. Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions.

    Science.gov (United States)

    Cui, Li-Qian; Liu, Kai; Zhang, Chi

    2011-04-07

    Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu(4)NHSO(4) could be applied to the effective oxidation of alkanes as well.

  6. Influence of hydrides orientation on strain, damage and failure of hydrided zircaloy-4

    International Nuclear Information System (INIS)

    Racine, A.

    2005-09-01

    In pressurized water reactors of nuclear power plants, fuel pellets are contained in cladding tubes, made of Zirconium alloy, for instance Zircaloy-4. During their life in the primary water of the reactor (155 bars, 300 C), cladding tubes are oxidized and consequently hydrided. A part of the hydrogen given off precipitates as Zirconium hydrides in the bulk material and embrittles the material. This embrittlement depends on many parameters, among which hydrogen content and orientation of hydrides with respect to the applied stress. This investigation is devoted to the influence of the orientation of hydrides with respect to the applied stress on strain, damage and failure mechanisms. Macroscopic and SEM in-situ ring tensile tests are performed on cladding tube material (unirradiated cold worked stress-relieved Zircaloy-4) hydrided with about 200 and 500 wppm hydrogen, and with different main hydrides orientation: either parallel or perpendicular to the circumferential tensile direction. We get the mechanical response of the material as a function of hydride orientation and hydrogen content and we investigate the deformation, damage and failure mechanisms. In both cases, digital image correlation techniques are used to estimate local and global strain distributions. Neither the tensile stress-strain response nor the global and local strain modes are significantly affected by hydrogen content or hydride orientation, but the failure modes are strongly modified. Indeed, only 200 wppm radial hydrides embrittle Zy-4: sample fail in the elastic domain at about 350 MPa before strain bands could develop; whereas in other cases sample reach at least 750 MPa before necking and final failure, in ductile or brittle mode. To model this particular heterogeneous material behavior, a non-coupled damage approach which takes into account the anisotropic distribution of the hydrides is proposed. Its parameters are identified from the macroscopic strain field measurements and a

  7. Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

    Energy Technology Data Exchange (ETDEWEB)

    Khadka, Nimesh [Department of Chemistry; Milton, Ross D. [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States; Shaw, Sudipta [Department of Chemistry; Lukoyanov, Dmitriy [Department; Dean, Dennis R. [Department of Biochemistry, Virginia Tech, Blacksburg, Virginia 24061, United States; Minteer, Shelley D. [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States; Raugei, Simone [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Hoffman, Brian M. [Department; Seefeldt, Lance C. [Department of Chemistry

    2017-09-15

    Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio, revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.

  8. Transfer

    DEFF Research Database (Denmark)

    Wahlgren, Bjarne; Aarkrog, Vibe

    Bogen er den første samlede indføring i transfer på dansk. Transfer kan anvendes som praksis-filosofikum. Den giver en systematisk indsigt til den studerende, der spørger: Hvordan kan teoretisk viden bruges til at reflektere over handlinger i situationer, der passer til min fremtidige arbejdsplads?...

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

    DEFF Research Database (Denmark)

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

    1975-01-01

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

  10. The mitochondrial outer membrane protein mitoNEET is a redox enzyme catalyzing electron transfer from FMNH2 to oxygen or ubiquinone.

    Science.gov (United States)

    Wang, Yiming; Landry, Aaron P; Ding, Huangen

    2017-06-16

    Increasing evidence suggests that mitoNEET, a target of the type II diabetes drug pioglitazone, is a key regulator of energy metabolism in mitochondria. MitoNEET is anchored to the mitochondrial outer membrane via its N-terminal α helix domain and hosts a redox-active [2Fe-2S] cluster in its C-terminal cytosolic region. The mechanism by which mitoNEET regulates energy metabolism in mitochondria, however, is not fully understood. Previous studies have shown that mitoNEET specifically interacts with the reduced flavin mononucleotide (FMNH 2 ) and that FMNH 2 can quickly reduce the mitoNEET [2Fe-2S] clusters. Here we report that the reduced mitoNEET [2Fe-2S] clusters can be readily oxidized by oxygen. In the presence of FMN, NADH, and flavin reductase, which reduces FMN to FMNH 2 using NADH as the electron donor, mitoNEET mediates oxidation of NADH with a concomitant reduction of oxygen. Ubiquinone-2, an analog of ubiquinone-10, can also oxidize the reduced mitoNEET [2Fe-2S] clusters under anaerobic or aerobic conditions. Compared with oxygen, ubiquinone-2 is more efficient in oxidizing the mitoNEET [2Fe-2S] clusters, suggesting that ubiquinone could be an intrinsic electron acceptor of the reduced mitoNEET [2Fe-2S] clusters in mitochondria. Pioglitazone or its analog NL-1 appears to inhibit the electron transfer activity of mitoNEET by forming a unique complex with mitoNEET and FMNH 2 The results suggest that mitoNEET is a redox enzyme that may promote oxidation of NADH to facilitate enhanced glycolysis in the cytosol and that pioglitazone may regulate energy metabolism in mitochondria by inhibiting the electron transfer activity of mitoNEET. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

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

    CERN Document Server

    Puls, Manfred P

    2012-01-01

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

  12. CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane.

    Science.gov (United States)

    Khadka, Nimesh; Dean, Dennis R; Smith, Dayle; Hoffman, Brian M; Raugei, Simone; Seefeldt, Lance C

    2016-09-06

    The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild-type nitrogenase and a nitrogenase with amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by two or eight electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by two electrons/protons to formate (HCOO(-)) at rates >10 times higher than rates of CO2 reduction to CO and CH4. Quantum mechanical calculations on the doubly reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride ("direct hydride transfer" reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride ("associative" reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. MoFe proteins with amino acid substitutions near FeMo-cofactor (α-70(Val→Ala), α-195(His→Gln)) are found to significantly alter the distribution of products between formate and CO/CH4.

  13. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  14. Synthesis of Nano-Light Magnesium Hydride for Hydrogen Storage ...

    African Journals Online (AJOL)

    Abstract. Nano-light magnesium hydride that has the capability for hydrogen storage was synthesized from treatment of magnesium ribbon with hydrogen peroxide. The optimum time for complete hydrogenation of the magnesium hydride was 5 hours.

  15. High H⁻ ionic conductivity in barium hydride.

    Science.gov (United States)

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

    2015-01-01

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

  16. Economic analysis of hydride fueled BWR

    International Nuclear Information System (INIS)

    Ganda, F.; Shuffler, C.; Greenspan, E.; Todreas, N.

    2009-01-01

    The economic implications of designing BWR cores with hydride fuels instead of conventional oxide fuels are analyzed. The economic analysis methodology adopted is based on the lifetime levelized cost of electricity (COE). Bracketing values (1970 and 3010 $/kWe) are used for the overnight construction costs and for the power scaling factors (0.4 and 0.8) that correlate between a change in the capital cost to a change in the power level. It is concluded that a newly constructed BWR reactor could substantially benefit from the use of 10 x 10 hydride fuel bundles instead of 10 x 10 oxide fuel bundles design presently in use. The cost saving would depend on the core pressure drop constraint that can be implemented in newly constructed BWRs - it is between 2% and 3% for a core pressure drop constraint as of the reference BWR, between 9% and 15% for a 50% higher core pressure drop, and between 12% and 21% higher for close to 100% core pressure. The attainable cost reduction was found insensitive to the specific construction cost but strongly dependent on the power scaling factor. The cost advantage of hydride fuelled cores as compared to that of the oxide reference core depends only weakly on the uranium and SWU prices, on the 'per volume base' fabrication cost of hydride fuels, and on the discount rate used. To be economically competitive, the uranium enrichment required for the hydride fuelled core needs to be around 10%.

  17. Experimental investigation of strain, damage and failure of hydrided zircaloy-4 with various hydride orientations

    International Nuclear Information System (INIS)

    Racine, A; Catherine, C.S.; Cappelaere, C.; Bornert, M.; Caldemaison, D.

    2005-01-01

    This experimental investigation is devoted to the influence of the orientation of hydrides on the mechanical response of Zircaloy-4. Ring tensile tests are performed on unirradiated CWSR Zircaloy-4, charged with about 200 or 500wppm hydrogen. Hydrides are oriented either parallel ('tangential'), or perpendicular ('radial') to the circumferential tensile direction. Tangential hydrides are usually observed in cladding tubes, however, hydrides can be reoriented after cooling under stress to become radial and then trigger brittle behavior. In this investigation, we perform, 'macroscopic' or SEM in-situ tensile tests on smooth rings, at room temperature. We get the mechanical response of the material as a function of hydride orientation and hydrogen content and we investigate the deformation, damage and failure mechanisms. In both cases, digital image correlation techniques are used to estimate local and global strain distributions. The results lead to the following conclusions: neither the tensile stress-strain response nor the strain modes are affected by hydrogen content or hydride orientation, but the failure modes are. Indeed, only 200wppm radial hydrides embrittle Zy-4: sample fails in the elastic domain at about 350 MPa before strain bands could develop; whereas in other cases samples reach at least 750 MPa before failure, with ductile or brittle mode. (authors)

  18. Hydrogen storage in complex hydrides

    International Nuclear Information System (INIS)

    Lupu, D.; Biris, A. R.; Misan, I.

    2005-01-01

    Full text: Hydrogen storage is a key enabling technology for the advancement of hydrogen and fuel cell power technologies in mobile and stationary applications. A relevant role of the fuel cell powered vehicles on the market of the transportation systems will be achieved only if the research and development of on-board vehicular hydrogen storage are able to allow a driving range of at least 500 km. The on-board hydrogen storage systems are more challenging due to the space, weight and cost limitations. This range of autonomy between refueling requires materials able to store at least 6.5% weight hydrogen, available at moderate pressures, at the working temperature of the fuel cells and with acceptable cycling stability. The intensive research on the hydrogen storage in alloys and intermetallic of the LaNi 5 , FeTi or Laves phase type compounds, which started more than three decades ago did not resulted in materials of more than about 3% H storage capacities. The 7.5% H content of the Mg hydride is still of attracting interest but though the absorption has been achieved at lower temperatures by ball milling magnesium with various amounts of nickel, the desorption can not be attained at 1 bar H 2 below 280 deg. C and the kinetics of the process is too slow. In the last decade, the attention is focused on another class of compounds, the complex hydrides of aluminum with alkali metals (alanates), due to their high hydrogen content. It was found that doping with Ti-based catalysts improve the hydrogenation/dehydrogenation conditions of NaAlH 4 . Later on, it was shown that ball milling with solid state catalysts greatly improve the hydrogen desorption kinetics of NaAlH 4 , and this also helps to the rehydriding process. The hydrogen desorption from NaAlH 4 occurs in three steps, it shows a reversible storage capacity of 5.5% H and this led to further research work for a better knowledge of its application relating properties. In this work, ball milling experiments on Na

  19. The growth of crystals of erbium hydride

    International Nuclear Information System (INIS)

    Grimshaw, J.A.; Spooner, F.J.; Wilson, C.G.; McQuillan, A.D.

    1981-01-01

    Crystals of the rare-earth hydride ErH 2 have been produced with face areas greater than a square millimetre and corresponding volumes exceeding those of earlier crystals by orders of magnitude. The hydride, which was produced in bulk polycrystalline form by hydriding erbium metal at 950 0 C, has been examined by optical and X-ray techniques. For material of composition ErH 2 and ErHsub(1.8) the size of the grains and their degree of strain appears to depend more on oxygen contamination during formation and on the subsequent cooling procedure, than on the size of erbium metal crystals in the starting material. (author)

  20. TRANSFER

    African Journals Online (AJOL)

    This paper reports on further studies on long range energy transfer between curcumine as donor and another thiazine dye, thionine, which is closely related to methylene blue as energy harvester (Figure 1). Since thionine is known to have a higher quantum yield of singlet oxygen sensitization than methylene blue [8], it is ...

  1. Stress induced reorientation of vanadium hydride

    International Nuclear Information System (INIS)

    Beardsley, M.B.

    1977-10-01

    The critical stress for the reorientation of vanadium hydride was determined for the temperature range 180 0 to 280 0 K using flat tensile samples containing 50 to 500 ppM hydrogen by weight. The critical stress was observed to vary from a half to a third of the macroscopic yield stress of pure vanadium over the temperature range. The vanadium hydride could not be stress induced to precipitate above its stress-free precipitation temperature by uniaxial tensile stresses or triaxial tensile stresses induced by a notch

  2. In situ hydride formation in titanium during focused ion milling.

    Science.gov (United States)

    Ding, Rengen; Jones, Ian P

    2011-01-01

    It is well known that titanium and its alloys are sensitive to electrolytes and thus hydrides are commonly observed in electropolished foils. In this study, focused ion beam (FIB) milling was used to prepare thin foils of titanium and its alloys for transmission electron microscopy. The results show the following: (i) titanium hydrides were observed in pure titanium, (ii) the preparation of a bulk sample in water or acid solution resulted in the formation of more hydrides and (iii) FIB milling aids the precipitation of hydrides, but there were never any hydrides in Ti64 and Ti5553.

  3. Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

    Science.gov (United States)

    Dubey, Pooja; Gupta, Sonu; Singh, Ajai K

    2018-03-12

    The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

  4. Effects of δ-hydride precipitation at a crack tip on crack propagation in delayed hydride cracking of Zircaloy-2

    Energy Technology Data Exchange (ETDEWEB)

    Kubo, T., E-mail: kubo@nfd.co.jp [Nippon Nuclear Fuel Development Co., Ltd., 2163 Narita-cho, Oarai-machi, Ibaraki 311-1313 (Japan); Kobayashi, Y. [M.O.X. Co., Ltd., 1828-520 Hirasu-cho, Mito, Ibaraki 311-0853 (Japan)

    2013-08-15

    Highlights: • Steady state crack velocity of delayed hydride cracking in Zircaloy-2 was analyzed. • A large stress peak is induced at an end of hydride by volume expansion of hydride. • Hydrogen diffuses to the stress peak, thereby accelerating steady hydride growth. • Crack velocity was estimated from the calculated hydrogen flux into the stress peak. • There was good agreement between calculation results and experimental data. -- Abstract: Delayed hydride cracking (DHC) of Zircaloy-2 is one possible mechanism for the failure of boiling water reactor fuel rods in ramp tests at high burnup. Analyses were made for hydrogen diffusion around a crack tip to estimate the crack velocity of DHC in zirconium alloys, placing importance on effects of precipitation of δ-hydride. The stress distribution around the crack tip is significantly altered by precipitation of hydride, which was strictly analyzed using a finite element computer code. Then, stress-driven hydrogen diffusion under the altered stress distribution was analyzed by a differential method. Overlapping of external stress and hydride precipitation at a crack tip induces two stress peaks; one at a crack tip and the other at the front end of the hydride precipitate. Since the latter is larger than the former, more hydrogen diffuses to the front end of the hydride precipitate, thereby accelerating hydride growth compared with that in the absence of the hydride. These results indicated that, after hydride was formed in front of the crack tip, it grew almost steadily accompanying the interaction of hydrogen diffusion, hydride growth and the stress alteration by hydride precipitation. Finally, crack velocity was estimated from the calculated hydrogen flux into the crack tip as a function of temperature, stress intensity factor and material strength. There was qualitatively good agreement between calculation results and experimental data.

  5. Metal hydrides for hydrogen storage in nickel hydrogen batteries

    International Nuclear Information System (INIS)

    Bittner, H.F.; Badcock, C.C.; Quinzio, M.V.

    1984-01-01

    Metal hydride hydrogen storage in nickel hydrogen (Ni/H 2 ) batteries has been shown to increase battery energy density and improve battery heat management capabilities. However the properties of metal hydrides in a Ni/H 2 battery environment, which contains water vapor and oxygen in addition to the hydrogen, have not been well characterized. This work evaluates the use of hydrides in Ni/H 2 batteries by fundamental characterization of metal hydride properties in a Ni/H 2 cell environment. Hydrogen sorption properties of various hydrides have been measured in a Ni/H 2 cell environment. Results of detailed thermodynamic and kinetic studies of hydrogen sorption in LaNi 5 in a Ni/H 2 cell environment are presented. Long-term cycling studies indicate that degradation of the hydride can be minimized by cycling between certain pressure limits. A model describing the mechanism of hydride degradation is presented

  6. Characterisation of hydrides in a zirconium alloy, by EBSD

    International Nuclear Information System (INIS)

    Ubhi, H.S.; Larsen, K.

    2012-01-01

    Zirconium alloys are used in nuclear reactors owing to their low capture cross-section for thermal neutrons and good mechanical and corrosion properties. However, they do suffer from delayed hydrogen cracking (DHC) due to formation of hydride particles. This study shows how the electron back-scatter diffraction (EBSD) technique can be used to characterise hydrides and their orientation relationship with the matrix. Hydrided EB weld specimens were prepared by electro-polishing, characterised using Oxford instruments AZtecHKL EBSD apparatus and software attached to a FEG SEM. Hydrides were found to exist as fine intra granular plates and having the Blackburn orientation relationship, i.e. (0002)Zr//(111)hydride and (1120)Zr//(1-10)hydride. The hydrides were also found to contain sigma 3 boundaries as well as local misorientations. (author)

  7. Hydride formation on deformation twin in zirconium alloy

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ju-Seong [Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Kim, Sung-Dae [Korea Institute of Material Science (KIMS), 797 Changwondaero, Changwon, Gyeongnam, 642-831 (Korea, Republic of); Yoon, Jonghun, E-mail: yooncsmd@gmail.com [Department of Mechanical Engineering, Hanyang University, 1271 Sa3-dong, Sangrok-gu, Ansan-si, Gyeonggi-do, 426-791 (Korea, Republic of)

    2016-12-15

    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.

  8. Arrested α-hydride migration activates a phosphido ligand for C–H insertion

    Energy Technology Data Exchange (ETDEWEB)

    Hickey, Anne K. [Indiana Univ., Bloomington, IN (United States); Muñoz, Salvador B. [Indiana Univ., Bloomington, IN (United States); Lutz, Sean A. [Indiana Univ., Bloomington, IN (United States); Pink, Maren [Indiana Univ., Bloomington, IN (United States); Chen, Chun-Hsing [Indiana Univ., Bloomington, IN (United States); Smith, Jeremy M. [Indiana Univ., Bloomington, IN (United States)

    2016-12-05

    Bulky tris(carbene)borate ligands provide access to high spin iron(II) phosphido complexes. The complex PhB(MesIm)3FeP(H)Ph is thermally unstable, and we observed [PPh] group insertion into a C–H bond of the supporting ligand. An arrested α-hydride migration mechanism suggests increased nucleophilicity of the phosphorus atom facilitates [PPh] group transfer reactivity.

  9. A Study on the Radial Hydride Assisted Delayed Hydride Cracking of Zircaloy

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Jin-Ho; Lee, Ji-Min; Kim, Yong-Soo [Hanyang University, Seoul (Korea, Republic of)

    2015-05-15

    Extensive studies have been done on understanding of DHC(Delayed hydride cracking) phenomenon since several zirconium alloy pressure tubes failed in nuclear reactor in the 1970s. Recently, long-term dry storage strategy has been considered seriously in order to manage spent nuclear fuel in Korea and other countries around the world. Consequentially, many researches have been investigated the degradation mechanisms which will threaten the spent fuel integrity during dry storage and showed that hydrogen related phenomenon such as hydride reorientation and DHC are the critical factors. Especially, DHC is the direct cracking mechanism which can cause not only a through-wall defect but also a radiation leak to the environment. In addition, DHC can be enhanced by radial hydride as reported by Kim who demonstrate that radial hydrides clearly act as crack linkage path. This phenomenon is known as the radial hydride assisted DHC (RHA-DHC). Therefore, study on DHC is essential to ensure the safety of spent fuel. Finite element analysis will be carried out for the stress gradient evaluation around notch tip. A variation in thermal cycle which leads to change in hydrogen solid solution trajectory may be required. If the radial hydride precipitates at notch tip, we will investigate what conditions should be met. Ultimately, we will suggest the regulation criteria for long-term dry storage of spent nuclear fuel.

  10. Method for preparation of uranium hydride

    International Nuclear Information System (INIS)

    Gorski, M.S.; Goncalves, Miriam; Mirage, A.; Lima, W. de.

    1985-01-01

    A method for preparation of Uranium Hydride starting from Hidrogen and Uranium is described. In the temperature range of 250 0 up to 350 0 C, and pressures above 10torr, Hydrogen reacts smoothly with Uranium turnings forming a fine black or dark gray powder (UH 3 ). Samples containing a significant amount of oxides show a delay before the reaction begging. (Author) [pt

  11. Hydrogen isotope exchange in metal hydride columns

    International Nuclear Information System (INIS)

    Wiswall, R.; Reilly, J.; Bloch, F.; Wirsing, E.

    1977-01-01

    Several metal hydrides were shown to act as chromatographic media for hydrogen isotopes. The procedure was to equilibrate a column of hydride with flowing hydrogen, inject a small quantity of tritium tracer, and observe its elution behavior. Characteristic retention times were found. From these and the extent of widening of the tritium band, the heights equivalent to a theoretical plate could be calculated. Values of around 1 cm were obtained. The following are the metals whose hydrides were studied, together with the temperature ranges in which chromatographic behavior was observed: vanadium, 0 to 70 0 C; zirconium, 500 to 600 0 C; LaNi 5 , -78 to +30 0 C; Mg 2 Ni, 300 to 375 0 C; palladium, 0 to 70 0 C. A dual-temperature isotope separation process based on hydride chromatography was demonstrated. In this, a column was caused to cycle between two temperatures while being supplied with a constant stream of tritium-traced hydrogen. Each half-cycle was continued until ''breakthrough,'' i.e., until the tritium concentration in the effluent was the same as that in the feed. Up to that point, the effluent was enriched or depleted in tritium, by up to 20%

  12. Magnesium hydrides and their phase transitions

    Czech Academy of Sciences Publication Activity Database

    Paidar, Václav

    2016-01-01

    Roč. 41, č. 23 (2016), s. 9769-9773 ISSN 0360-3199 R&D Projects: GA MŠk(CZ) LD13069 Institutional support: RVO:68378271 Keywords : hydrogen * magnesium and transition metal hydrides * crystal structure stability * displacive phase transformations Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.582, year: 2016

  13. Are RENiAl hydrides metallic?

    Czech Academy of Sciences Publication Activity Database

    Eichinger, K.; Havela, L.; Prokleška, J.; Stelmakhovych, O.; Daniš, S.; Šantavá, Eva; Miliyanchuk, K.

    2009-01-01

    Roč. 100, č. 9 (2009), s. 1200-1202 ISSN 1862-5282 Grant - others:GA ČR(CZ) GA202/07/0418 Institutional research plan: CEZ:AV0Z10100520 Keywords : rare earth metals * magnetism * hydrides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.862, year: 2009

  14. Lithium hydride hydrolysis: experimental and kinetic study

    International Nuclear Information System (INIS)

    Charton, S.; Maupoix, C.; Brevet, A.; Delaunay, F.; Heintz, O.; Saviot, L.

    2006-01-01

    In this work has been studied the contribution of various analyses techniques in the framework, on the one hand of revealing the mechanisms implied in lithium hydride hydrolysis, and on the other hand of studying the kinetics of hydrogen production. Among the methods recently investigated, Raman spectroscopy, XPS and SIMS seem to be particularly attractive. (O.M.)

  15. Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

    International Nuclear Information System (INIS)

    Lee, Hyung Soo; Lee, Gab Yong

    2005-01-01

    The isomerization of olefins occurs either by a metal hydride addition-elimination or by a π-allyl metal hydride intermediate. HCo(CO) 4 , [(C 2 H 4 ) 2 RhCl] 2 , Ni[P(OEt) 3 ] 4 , and PtCl 2 (PPh 3 ) 2 -SnCl 2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechanism, 3,4 and Fe 3 (CO) 12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN) 2 PdCl 2 occur via a π-allyl metal hydride mechanism. The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh 3 ) 3 has also been investigated. The skeletal isomerization of olefins catalyzed by (R 3 P) 2 NiCl 2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene. Titanium complexes serve as an effective catalysts for a variety of reactions such as hydroalumination, hydroboration, and hydrogenation of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydrocarbons by using titanium and zirconium compounds. The reagent system composed of LiAlH 4 /Cp 2 TiCl 2 ≤ 2 in the molar ratio promotes the isomerization of 1-octene, but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp 2 TiCl 2 (Cp=cyclopentadienyl) and LiAlH 4

  16. Rhodium Catalyzed Decarbonylation

    DEFF Research Database (Denmark)

    Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders

    2017-01-01

    Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...

  17. Highly efficient and diastereoselective gold(I)-catalyzed synthesis of tertiary amines from secondary amines and alkynes: substrate scope and mechanistic insights.

    Science.gov (United States)

    Liu, Xin-Yuan; Guo, Zhen; Dong, Sijia S; Li, Xiao-Hua; Che, Chi-Ming

    2011-11-11

    An efficient method for the synthesis of tertiary amines through a gold(I)-catalyzed tandem reaction of alkynes with secondary amines has been developed. In the presence of ethyl Hantzsch ester and [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %), a variety of secondary amines bearing electron-deficient and electron-rich substituents and a wide range of alkynes, including terminal and internal aryl alkynes, aliphatic alkynes, and electron-deficient alkynes, underwent a tandem reaction to afford the corresponding tertiary amines in up to 99 % yield. For indolines bearing a preexisting chiral center, their reactions with alkynes in the presence of ethyl Hantzsch ester catalyzed by [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %) afforded tertiary amines in excellent yields and with good to excellent diastereoselectivity. All of these organic transformations can be conducted as a one-pot reaction from simple and readily available starting materials without the need of isolation of air/moisture-sensitive enamine intermediates, and under mild reaction conditions (mostly room temperature and mild reducing agents). Mechanistic studies by NMR spectroscopy, ESI-MS, isotope labeling studies, and DFT calculations on this gold(I)-catalyzed tandem reaction reveal that the first step involving a monomeric cationic gold(I)-alkyne intermediate is more likely than a gold(I)-amine intermediate, a three-coordinate gold(I) intermediate, or a dinuclear gold(I)-alkyne intermediate. These studies also support the proposed reaction pathway, which involves a gold(I)-coordinated enamine complex as a key intermediate for the subsequent transfer hydrogenation with a hydride source, and reveal the intrinsic stereospecific nature of these transformations observed in the experiments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Manganese-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as a Sustainable C1 Building Block.

    Science.gov (United States)

    Mastalir, Matthias; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl

    2017-07-05

    This study represents the first example of a manganese-catalyzed environmentally benign, practical three-component aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes in combination with amines and MeOH as a C1 source. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps which give rise to selective C-C and C-N bond formations, thereby releasing hydrogen and water. A well-defined hydride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way, and a total of 28 different aminomethylated products were synthesized and isolated yields of up to 91%. In a preliminary study, a related Fe(II) PNP pincer complex was shown to catalyze the methylation of 2-naphtol rather than its aminomethylation displaying again the divergent behavior of isoelectronic Mn(I) and Fe(II) PNP pincer systems.

  19. Impacts of external convection on release rates in metal hydride storage tanks. Paper no. IGEC-1-080

    International Nuclear Information System (INIS)

    MacDonald, B.; Rowe, A.; Tomlinson, J.; Ho, J.

    2005-01-01

    Reversible metal hydrides can be used to store hydrogen at relatively low pressures, with very high volumetric density. The rate hydrogen can be drawn from a given tank is strongly influenced by the rate heat can be transferred to the reaction zone. Because of this, enhancing and controlling heat transfer is a key area of research in the development of metal hydride storage tanks. In this work, the impacts of external convection resistance on hydrogen release rates are examined. A one-dimensional resistive analysis determines the thermal resistances in the system based on one case where no external heat transfer enhancements are used, and a second case where external fins are used. A two-dimensional, transient model, developed in FEMLAB, is used to determine the impact of the external fins on the mass flow rate of hydrogen in more detail. For the particular metal hydride alloy (LaNi 4.8 Sn 0.2 ) and tank geometry studied, it was found that the fins have a large impact on the hydrogen flow rate during the initial stages of desorption. The flow rate with no fins is only 20% of the flow rate with fins for a full tank, 57% when the tank is 33% full, and 74% when the tank is 5% full. As the reaction proceeds, the resistance of the metal hydride alloy within the tank increases and becomes dominant. Therefore, the impact of the fins becomes less significant as the tank empties. (author)

  20. Hydrogen storage in metallic hydrides: the hydrides of magnesium-nickel alloys

    International Nuclear Information System (INIS)

    Silva, E.P. da.

    1981-01-01

    The massive and common use of hydrogen as an energy carrier requires an adequate solution to the problem of storing it. High pressure or low temperatures are not entirely satisfactory, having each a limited range of applications. Reversible metal hydrides cover a range of applications intermediate to high pressure gas and low temperature liquid hydrogen, retaining very favorable safety and energy density characteristics, both for mobile and stationary applications. This work demonstrates the technical viability of storing hydrogen in metal hydrides of magnesium-nickel alloys. Also, it shows that technology, a product of science, can be generated within an academic environment, of the goal is clear, the demand outstanding and the means available. We review briefly theoretical models relating to metal hydride properties, specially the thermodynamics properties relevant to this work. We report our experimental results on hydrides of magnesium-nickel alloys of various compositions including data on structure, hydrogen storage capacities, reaction kinetics, pressure-composition isotherms. We selected a promising alloy for mass production, built and tested a modular storage tank based on the hydrides of the alloy, with a capacity for storing 10 Nm sup(3) of hydrogen of 1 atm and 20 sup(0)C. The tank weighs 46,3 Kg and has a volume of 21 l. (author)

  1. SYNTHESIS AND STRUCTURE OF BIS(PHENYLTETRAMETHYLCYCLOPENTADIENYL)TITANIUM(III) HYDRIDE - THE FIRST MONOMERIC BIS(CYCLOPENTADIENYL)TITANIUM(III) HYDRIDE : The First Monomeric Bis(cyclopentadienyl)titanium(III) Hydride

    NARCIS (Netherlands)

    de Wolf, J.M.; Meetsma, A.; Teuben, J.H

    1995-01-01

    The first structurally characterized monomeric bis(cyclopentadienyl)titanium(III) hydride, (C(5)PhMe(4))(2)TiH (4), was synthesized by hydrogenolysis of (C(5)PhMe(4))(2)TiMe (5). Hydride 4 was found to be a monomeric bent sandwich by X-ray diffraction methods, and the pentamethylcyclopentadienyl

  2. Nickel-Catalyzed C sp2 –C sp3 Cross-Coupling via C–O Bond Activation

    KAUST Repository

    Guo, Lin

    2016-06-13

    A new and efficient nickel-catalyzed alkylation of CAr-O electrophiles with B-alkyl-9-BBNs is described. The transformation is characterized by its functional group tolerance and provides a practical and versatile access to various Csp2-Csp3 bonds through Csp2-O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C-O bond activation process. © 2016 American Chemical Society.

  3. TEM analysis of the microstructure in TiF3-catalyzed and pure MgH2 during the hydrogen storage cycling

    International Nuclear Information System (INIS)

    Danaie, Mohsen; Mitlin, David

    2012-01-01

    We utilized transmission electron microscopy (TEM) analysis, with a cryogenically cooled sample stage, to detail the microstructure of partially transformed pure and titanium fluoride-catalyzed magnesium hydride powder during hydrogenation cycling. The TiF 3 -catalyzed MgH 2 powder demonstrated excellent hydrogen storage kinetics at various temperatures, whereas the uncatalyzed MgH 2 showed significant degradation in both kinetics and capacity. TEM analysis on the partially hydrogen absorbed and partially desorbed pure Mg(MgH 2 ) revealed a large fraction of particles that were either not transformed at all or were completely transformed. On the other hand, in the MgH 2 +TiF 3 system it was much easier to identify regions with both the hydride and the metal phase coexisting in the same particle. This enabled us to establish the metal hydride orientation relationship (OR) during hydrogen absorption. The OR was determined to be (1 1 0)MgH 2 || (−1 1 0 −1)Mg and [−1 1 1]MgH 2 || [0 1 −1 1]Mg. During absorption the number density of the hydride nuclei does not show a dramatic increase due the presence of TiF 3 . Conversely, during desorption the TiF 3 catalyst substantially increases the number of the newly formed Mg crystallites, which display a strong texture correlation with respect to the parent MgH 2 phase. Titanium fluoride also promotes extensive twinning in the hydride phase.

  4. Hydridation of Ti-6Al-4V

    International Nuclear Information System (INIS)

    Domizzi, G; Luppo, M.I; Ortiz, M; Vigna, G

    2004-01-01

    The production of Ti pieces or their alloys through powder metallurgy is an economical alternative that replaces the costly methods commonly used. The Ti-6AI-4V alloy is widely used in the aerospace, chemical and medical industries. The use of powder from the alloy instead of using more pure alloyed titanium powders, further simplifies the production process. The presence of V allows the phase β to stabilize at very low temperatures and both alloys alter the Ti-H equilibrium diagram. This work analyzes to what degree these effects influence the obtaining of powders from this alloy from that of hydridation and dehydridation. Although it has slower kinetics, powders can be produced in times similar to those found for grade 2 Ti since the distribution of hydrides in the sample is uniform and the material is fragile enough for concentrations of approximately 0.7 H/Ti (CW)

  5. Mechanism of n-butane hydrogenolysis promoted by Ta-hydrides supported on silica

    KAUST Repository

    Pasha, Farhan Ahmad

    2014-06-06

    The mechanism of hydrogenolysis of alkanes, promoted by Ta-hydrides supported on silica via 2 ≡ Si-O- bonds, has been studied with a density functional theory (DFT) approach. Our study suggests that the initial monohydride (≡ Si-O-)2Ta(III)H is rapidly trapped by molecular hydrogen to form the more stable tris-hydride (≡ Si-O-) 2Ta(V)H3. Loading of n-butane to the Ta-center occurs through C-H activation concerted with elimination of molecular hydrogen (σ-bond metathesis). Once the Ta-alkyl species is formed, the C-C activation step corresponds to a β-alkyl transfer to the metal with elimination of an olefin. According to these calculations, an α-alkyl transfer to the metal to form a Ta-carbene species is of higher energy. The olefins formed during the C-C activation step can be rapidly hydrogenated by both mono- and tris-Ta-hydride species, making the overall process of alkane cracking thermodynamically favored. © 2014 American Chemical Society.

  6. Ultrapure hydrogen thermal compressor based on metal hydrides for fuel cells and hybrid vehicles

    International Nuclear Information System (INIS)

    Almasan, V.; Biris, A.; Coldea, I.; Lupu, D.; Misan, I.; Popeneciu, G.; Ardelean, O.

    2007-01-01

    Full text: In hydrogen economy, efficient compressors are indispensable elements in the storage, transport and distribution of the produced hydrogen. Energetic efficient technologies can contribute to H 2 pipelines transport to the point of use and to distribute H 2 by refuelling stations. Characteristic for metal hydrides systems is the wide area of possibilities to absorb hydrogen at low pressure from any source of hydrogen, to store and deliver it hydrogen at high pressure (compression ratio more than 30). On the basis of innovative concepts and advanced materials for H 2 storage/compression (and fast thermal transfer), a fast mass (H 2 ) and heat transfer unit will be developed suitable to be integrated in a 3 stage thermal compressor. Metal hydrides used for a three stage hydrogen compression system must have different equilibrium pressures, namely: for stage 1, low pressure H 2 absorption and resistant to poisoning with impurities of hydrogen, for stage 2, medium pressure H 2 absorption and for stage 3, high pressure hydrogen delivery (120 bar). In the case of compression device based on metallic hydrides the most important properties are the hydrogen absorption/desorption rate, a smaller process enthalpy and a great structural stability on long term hydrogen absorption/desorption cycling. These properties require metal hydrides with large differences between the hydrogen absorption and desorption pressures at equilibrium, within a rather small temperature range. The main goal of this work is to search and develop metal hydride integrated systems for hydrogen purification, storage and compression. After a careful screening three hydrogen absorbing alloys will be selected. After selection, the work up of the alloys composition on the bases of detailed solid state studies, new multi-component alloys will be developed, with suitable thermodynamic and kinetic properties for a hydrogen compressor. The results of the study are the following: new types of hydrogen

  7. Hydrides and Borohydrides of Light Elements

    Science.gov (United States)

    1947-12-04

    Troy, Attn: Inst. of Naval Science (30) Solar Aircraft Cu,, San Diego, Attn: Dr. M. A. Williamson " (31) INSMAT. N. J. for Itandard Oil Co., Esso Lab...with the other# iLD F.Re p. 8 ilt -ms" #61ggSotod that.. ir addition to thc impurity in the t~y..thr, an impurkty, prosumably aluminum hydride, in

  8. Facile Synthesis of Permethyl Yttrocene Hydride

    NARCIS (Netherlands)

    Haan, Klaas H. den; Teuben, Jan H.

    1984-01-01

    A convenient three step synthesis of (Cp*2YH)n (Cp* = C5Me5) is described starting with YCl3.3thf, in which Cp*2YCl.thf and Cp*2YCH(SiMe3)2 are intermediates, which could be isolated and characterized. The hydride is active in the activation of sp2 and sp3 C-H bonds as was demonstrated by the H-D

  9. HYDRIDE-RELATED DEGRADATION OF SNF CLADDING UNDER REPOSITORY CONDITIONS

    International Nuclear Information System (INIS)

    McCoy, K.

    2000-01-01

    The purpose and scope of this analysis/model report is to analyze the degradation of commercial spent nuclear fuel (CSNF) cladding under repository conditions by the hydride-related metallurgical processes, such as delayed hydride cracking (DHC), hydride reorientation and hydrogen embrittlement, thereby providing a better understanding of the degradation process and clarifying which aspects of the process are known and which need further evaluation and investigation. The intended use is as an input to a more general analysis of cladding degradation

  10. Hydrogen storage systems based on magnesium hydride: from laboratory tests to fuel cell integration

    Science.gov (United States)

    de Rango, P.; Marty, P.; Fruchart, D.

    2016-02-01

    The paper reviews the state of the art of hydrogen storage systems based on magnesium hydride, emphasizing the role of thermal management, whose effectiveness depends on the effective thermal conductivity of the hydride, but also depends of other limiting factors such as wall contact resistance and convective exchanges with the heat transfer fluid. For daily cycles, the use of phase change material to store the heat of reaction appears to be the most effective solution. The integration with fuel cells (1 kWe proton exchange membrane fuel cell and solid oxide fuel cell) highlights the dynamic behaviour of these systems, which is related to the thermodynamic properties of MgH2. This allows for "self-adaptive" systems that do not require control of the hydrogen flow rate at the inlet of the fuel cell.

  11. Spectrophotometric determination of volautile inorganic hydrides in binary gaseous mixtures

    International Nuclear Information System (INIS)

    Rezchikov, V.G.; Skachkova, I.N.; Kuznetsova, T.S.; Khrushcheva, V.V.

    1985-01-01

    A study was made on possibility of single and continuons analysis of binary mixtures (hydride-gas) for the content of volatile inorganic hydrides (VIH) from absorption spectra in the 185-280 nm band. Dependences of the percentage of VIH transmission on the wavelength are presented. It is shown that the maximum of their absorption depends on the element-hydrogen the bond length and binding energy. Detection limit for boron hydride was established to be n x 10 -3 % vol at 185-190 nm wavelength. Technique for spectrophotometric hydride determination in binary mixtures with hydrogen, argon, helium was developed. The technique provides the continuous control of gaseous mixture composition

  12. Identification of the zirconium hydrides metallography in zircaloy-2

    International Nuclear Information System (INIS)

    Garcia Gonzalez, F.

    1968-01-01

    Technique for the Identification of the zirconium hydrides in metallographic specimens have been developed. Microhardness, quantitative estimation and relative orientation of the present hydrides as well as grain size determination of the different Zircaloy-2 tube specimens have also been made. The specimens used were corrosion- tested in water during various periods of time at 300 degree castrating, prior to the metallographic examination. Reference specimens, as received, and heavily hydride specimens in a hydrogen atmosphere at 800 degree centigrees, have been used in the previous stages of the work. No difficulties have been met in this early stage of acquaintanceship with the zirconium hydrides. (Author) 5 refs

  13. Initiation of delayed hydride cracking in zirconium-2.5 wt% niobium

    International Nuclear Information System (INIS)

    Shalabi, A.F.; Meneley, D.A.

    1990-01-01

    Delayed hydride cracking in zirconium alloys is caused by the repeated precipitation and cracking of brittle hydrides. The growth kinetic of the hydrides have been measured to evaluate the critical hydride length for crack initiation. Hydride growth leading to crack initiation follows an approximate (time) 1/3 law on the average; crack propagation proceeds in a stepwise fashion. The critical length of hydride for crack initiation increases with stress and temperature. The fracture criterion for crack initiation predicts the critical hydride length at a give stress level and temperature. The fracture initiation mechanism of the hydride confirms the temperature effects for heating and cooling cycles under services loads. (orig.)

  14. Caffeine-catalyzed gels.

    Science.gov (United States)

    DiCiccio, Angela M; Lee, Young-Ah Lucy; Glettig, Dean L; Walton, Elizabeth S E; de la Serna, Eva L; Montgomery, Veronica A; Grant, Tyler M; Langer, Robert; Traverso, Giovanni

    2018-07-01

    Covalently cross-linked gels are utilized in a broad range of biomedical applications though their synthesis often compromises easy implementation. Cross-linking reactions commonly utilize catalysts or conditions that can damage biologics and sensitive compounds, producing materials that require extensive post processing to achieve acceptable biocompatibility. As an alternative, we report a batch synthesis platform to produce covalently cross-linked materials appropriate for direct biomedical application enabled by green chemistry and commonly available food grade ingredients. Using caffeine, a mild base, to catalyze anhydrous carboxylate ring-opening of diglycidyl-ether functionalized monomers with citric acid as a tri-functional crosslinking agent we introduce a novel poly(ester-ether) gel synthesis platform. We demonstrate that biocompatible Caffeine Catalyzed Gels (CCGs) exhibit dynamic physical, chemical, and mechanical properties, which can be tailored in shape, surface texture, solvent response, cargo release, shear and tensile strength, among other potential attributes. The demonstrated versatility, low cost and facile synthesis of these CCGs renders them appropriate for a broad range of customized engineering applications including drug delivery constructs, tissue engineering scaffolds, and medical devices. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  15. Hydrogen storage in the form of metal hydrides

    Science.gov (United States)

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

    1984-01-01

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

  16. Pyrophoric behaviour of uranium hydride and uranium powders

    Science.gov (United States)

    Le Guyadec, F.; Génin, X.; Bayle, J. P.; Dugne, O.; Duhart-Barone, A.; Ablitzer, C.

    2010-01-01

    Thermal stability and spontaneous ignition conditions of uranium hydride and uranium metal fine powders have been studied and observed in an original and dedicated experimental device placed inside a glove box under flowing pure argon. Pure uranium hydride powder with low amount of oxide (Oxidation mechanisms are proposed.

  17. Electrocatalytic hydride-forming compounds for rechageable batteries

    NARCIS (Netherlands)

    Notten, P.H.L.; Einerhand, R.E.F.

    1991-01-01

    Non-toxic intermetallic hydride-forming compounds are attractive alternatives to cadmium as the negative electrode materials in the new generation of Ni/metal hydride rechargeable batteries. High exchange currents and discharge efficiencies even at low temperatures can be achieved using highly

  18. Ultra-sonic observation in niobium hydride precipitation

    International Nuclear Information System (INIS)

    Florencio, O.; Pinatti, Dyonisio G.

    1982-01-01

    The hidrogen embrittlement of exothermic ocluders, had been considered as due to applied stress induced hydride precipitates leading to brittle fracture. The results of simultaneous measurements of macroscopic deformation and elastic change due to hydride precipitation, using the ultrasonic pulse-echo technique are showed. THen it was tested the possibility of kinectis precipitation parameters evoluation. (Author) [pt

  19. Creating nanoshell on the surface of titanium hydride bead

    Directory of Open Access Journals (Sweden)

    PAVLENKO Vyacheslav Ivanovich

    2016-12-01

    Full Text Available The article presents data on the modification of titanium hydride bead by creating titanium nanoshell on its surface by ion-plasma vacuum magnetron sputtering. To apply titanium nanoshell on the titanium hydride bead vacuum coating plant of multifunctional nanocomposite coatings QVADRA 500 located in the center of high technology was used. Analysis of the micrographs of the original surface of titanium hydride bead showed that the microstructure of the surface is flat, smooth, in addition the analysis of the microstructure of material surface showed the presence of small porosity, roughness, mainly cavities, as well as shallow longitudinal cracks. The presence of oxide film in titanium hydride prevents the free release of hydrogen and fills some micro-cracks on the surface. Differential thermal analysis of both samples was conducted to determine the thermal stability of the initial titanium hydride bead and bead with applied titanium nanoshell. Hydrogen thermal desorption spectra of the samples of the initial titanium hydride bead and bead with applied titanium nanoshell show different thermal stability of compared materials in the temperature range from 550 to 860о C. Titanium nanoshells applied in this way allows increasing the heat resistance of titanium hydride bead – the temperature of starting decomposition is 695о C and temperature when decomposition finishes is more than 1000о C. Modified in this way titanium hydride bead can be used as a filler in the radiation protective materials used in the construction or upgrading biological protection of nuclear power plants.

  20. Preferred hydride growth orientations on oxide-coated gadolinium surfaces

    International Nuclear Information System (INIS)

    Benamar, G.M.; Schweke, D.; Kimmel, G.; Mintz, M.H.

    2012-01-01

    Highlights: ► The preferred hydride growth orientations on gadolinium metal coated by a thin oxide layer are presented. ► A preferred growth of the (1 0 0) h plane of the face centered cubic (FCC) GdH 2 is observed for the hydride spots forming below the oxidation layer. ► A change to the (1 1 1) h plane of the cubic hydride dominates for the hydride's Growth Centers. ► The texture change is attributed to the surface normal compressive stress component exerted by the oxidation layer on the developing hydride. - Abstract: The initial development of hydrides on polycrystalline gadolinium (Gd), as on some other hydride forming metals, is characterized by two sequential steps. The first step involves the rapid formation of a dense pattern of small hydride spots (referred to as the “small family” of hydrides) below the native oxidation layer. The second stage takes place when some of the “small family” nucleants (referred to as “growth centers”, GCs) break the oxide layer, leading to their rapid growth and finally to the massive hydriding of the sample. In the present study, the texture of the two hydride families was studied, by combining X-ray diffraction (XRD) analysis with a microscopic analysis of the hydride, using scanning electron microscopy (SEM) and atomic force microscopy (AFM). It has been observed that for the “small family”, a preferred growth of the (1 0 0) h plane of the cubic GdH 2 takes place, whereas for the GCs, a change to the (1 1 1) h plane of the cubic hydride dominates. These preferred growth orientations were analyzed by their structure relation with the (0 0 .1) m basal plane of the Gd metal. It has been concluded that the above texture change is due to the surface normal compressive stress component exerted by the oxidation overlayer on the developing hydride, preventing the (0 0 .1) m ||(1 1 1) h growth orientation. This stress is relieved upon the rupture of that overlayer and the development of the GCs, leading to

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-14

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

  2. Growth and decomposition of Lithium and Lithium hydride on Nickel

    DEFF Research Database (Denmark)

    Engbæk, Jakob; Nielsen, Gunver; Nielsen, Jane Hvolbæk

    2006-01-01

    In this paper we have investigated the deposition, structure and decomposition of lithium and lithium-hydride films on a nickel substrate. Using surface sensitive techniques it was possible to quantify the deposited Li amount, and to optimize the deposition procedure for synthesizing lithium......-hydride films. By only making thin films of LiH it is possible to study the stability of these hydride layers and compare it directly with the stability of pure Li without having any transport phenomena or adsorbed oxygen to obscure the results. The desorption of metallic lithium takes place at a lower...... temperature than the decomposition of the lithium-hydride, confirming the high stability and sintering problems of lithium-hydride making the storage potential a challenge. (c) 2006 Elsevier B.V. All rights reserved....

  3. Minimizing hydride cracking in zirconium alloys

    International Nuclear Information System (INIS)

    Coleman, C.E.; Cheadle, B.A.; Ambler, J.F.R.; Eadie, R.L.

    1985-01-01

    Zirconium alloy components can fail by hydride cracking if they contain large flaws and are highly stressed. If cracking in such components is suspected, crack growth can be minimized by following two simple operating rules: components should be heated up from at least 30K below any operating temperature above 450K, and when the component requires cooling to room temperature from a high temperature, any tensile stress should be reduced as much and as quickly as is practical during cooling. This paper describes the physical basis for these rules

  4. Tritium immobilization and packaging using metal hydrides

    International Nuclear Information System (INIS)

    Holtslander, W.J.; Yaraskavitch, J.M.

    1981-04-01

    Tritium recovered from CANDU heavy water reactors will have to be packaged and stored in a safe manner. Tritium will be recovered in the elemental form, T 2 . Metal tritides are effective compounds in which to immobilize the tritium as a stable non-reactive solid with a high tritium capacity. The technology necessary to prepare hydrides of suitable metals, such as titanium and zirconium, have been developed and the properties of the prepared materials evaluated. Conceptual designs of packages for containing metal tritides suitable for transportation and long-term storage have been made and initial testing started. (author)

  5. Low-frequency excitations in zirconium hydrides

    International Nuclear Information System (INIS)

    Radulescu, A.; Padureanu, I.; Rapeanu, S.N.; Beldiman, A.; Kozlov, Zh.A.; Semenov, V.A.

    1999-01-01

    The slow inelastic neutron scattering (INS) on ZrH x systems (x = 0.38, 0.52) revealed new excitations located within the energy range 2-10 MeV. Besides the acoustic vibrations specific to α-HCP Zr and γ-FCO Zr hydride the fine structure of these excitations is clearly observed. The origin of the new observed peaks is not very clear but a proton tunneling or a resonance effect in α-Zr lattice could be taken into account

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  7. Lactam hydrolysis catalyzed by mononuclear metallo-ß-bactamases

    DEFF Research Database (Denmark)

    Olsen, Lars; Antony, J; Ryde, U

    2003-01-01

    Two central steps in the hydrolysis of lactam antibiotics catalyzed by mononuclear metallo-beta-lactamases, formation of the tetrahedral intermediate and its breakdown by proton transfer, are studied for model systems using the density functional B3LYP method. Metallo-beta-lactamases have two metal...

  8. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved......, the networks of environmental professionals that work in the environmental organisation, in consulting and regulatory enforcement, and dominating business cultures. These have previously been identified in the literature as individually significant in relation to the evolving environmental agendas...... they are implemented in and how the changing context is reflected in the environmental objectives that are established and prioritised. Our argument is, that the ability of the standard to achieve an impact is dependant on the constitution of ’coherent’ environmental issues in the context, where the management system...

  9. Application of acoustic emission to hydride cracking

    International Nuclear Information System (INIS)

    Sagat, S.; Ambler, J.F.R.; Coleman, C.E.

    1986-07-01

    Acoustic emission has been used for over a decade to study delayed hydride cracking (DHC) in zirconium alloys. At first acoustic emission was used primarily to detect the onset of DHC. This was possible because DHC was accompanied by very little plastic deformation of the material and furthermore the amplitudes of the acoustic pulses produced during cracking of the brittle hydride phase were much larger than those from dislocation motion and twinning. Acoustic emission was also used for measuring crack growth when it was found that for a suitable amplitude threshold, the total number of acoustic emission counts was linearly related to the cracked area. Once the proportionality constant was established, the acoustic counts could be converted to the crack length. Now the proportionality between the count rate and the crack growth rate is used to provide feedback between the crack length and the applied load, using computer technology. In such a system, the stress at the crack tip can be maintained constant during the test by adjusting the applied load as the crack progresses, or it can be changed in a predetermined manner, for example, to measure the threshold stress for cracking

  10. NATO Advanced Study Institute on Metal Hydrides

    CERN Document Server

    1981-01-01

    In the last five years, the study of metal hydrides has ex­ panded enormously due to the potential technological importance of this class of materials in hydrogen based energy conversion schemes. The scope of this activity has been worldwide among the industrially advanced nations. There has been a consensus among researchers in both fundamental and applied areas that a more basic understanding of the properties of metal/hydrogen syster;,s is required in order to provide a rational basis for the selection of materials for specific applications. The current worldwide need for and interest in research in metal hydrides indicated the timeliness of an Advanced Study Insti­ tute to provide an in-depth view of the field for those active in its various aspects. The inclusion of speakers from non-NATO coun­ tries provided the opportunity for cross-fertilization of ideas for future research. While the emphasis of the Institute was on basic properties, there was a conscious effort to stimulate interest in the applic...

  11. AB/sub 5/-catalyzed hydrogen evolution cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Hall, D E; Sawada, T; Shepard, V R; Tsujikawa, Y

    1984-01-01

    The AB/sub 5/ metal compounds are highly efficient hydrogen evolution electrocatalysts in alkaline electrolyte. Three types of AB/sub 5/-catalyzed cathode structures were made, using the hydride-forming AB/sub 5/ compounds in particulate form. Plastic-bonded cathodes containing >90 w/o AB/sub 5/ (finished-weight basis) were the most efficient, giving hydrogen evolution overpotentials (/eta/ /SUB H2/ ) of about 0.05 V at 200 mA cm/sup -2/. However, they tended to swell and shed material during electrolysis. Pressed, sintered cathodes containing 40-70 w/o catalyst in a nickel binder gave /eta/ /SUB H2/ about0.08 V; catalyst retention was excellent. Porous, sintered cathode coatings were made with 30-70 w/o AB/sub 5/ catalyst loadings. Their overpotentials were similar to those of the pressed, sintered cathodes. However, at catalyst loadings below about 40 w/o, high overpotentials characteristic of the nickel binder were observed. The structural and electrochemical properties of the three AB/sub 5/-catalyzed cathodes are discussed.

  12. Isotope exchange between gaseous hydrogen and uranium hydride powder

    International Nuclear Information System (INIS)

    Shugard, Andrew D.; Buffleben, George M.; Johnson, Terry A.; Robinson, David B.

    2014-01-01

    Highlights: • Isotope exchange between hydrogen gas and uranium hydride powder can be rapid and reversible. • Gas–solid exchange rate is controlled by transport within ∼0.7 μm hydride particles. • Gas chromatographic separation of hydrogen isotopes using uranium hydride is feasible. - Abstract: Isotope exchange between gaseous hydrogen and solid uranium hydride has been studied by flowing hydrogen (deuterium) gas through packed powder beds of uranium deuteride (hydride). We used a residual gas analyzer system to perform real-time analysis of the effluent gas composition. We also developed an exchange and transport model and, by fitting it to the experimental data, extracted kinetic parameters for the isotope exchange reaction. Our results suggest that, from approximately 70 to 700 kPa and 25 to 400 °C, the gas-to-solid exchange rate is controlled by hydrogen and deuterium transport within the ∼0.7 μm diameter uranium hydride particles. We use our kinetic parameters to show that gas chromatographic separation of hydrogen and deuterium using uranium hydride could be feasible

  13. A study of stress reorientation of hydrides in zircaloy

    Energy Technology Data Exchange (ETDEWEB)

    Yourong, Jiang; Bangxin, Zhou [Nuclear Power Inst. of China, Chengdu, SC (China)

    1994-10-01

    Under the conditions of circumferential tensile stress from 70 to 180 MPa for Zircaloy tubes or the tensile stress from 55 to 180 MPa for Zircaloy-4 plates and temperature cycling between 150 and 400 degree C, the effects of stress and the number of temperature cycling on hydride reorientation in Zircaloy-4 tubes and plates and Zircaloy-2 tubes containing about 220 {mu}g/g hydrogen have been investigated. With the increase of stress and/or the number of temperature cycling, the level of hydride reorientation increases. When hydride reorientation takes place, there is a threshold stress concerned with the number of temperature cycling. Below the threshold stress, hydride reorientation is not obvious. When applied stress is higher than the threshold stress, the level of hydride reorientation increases with the increase of stress and the number of temperature cycling. Hydride reorientation in Zircaloy-4 tubes develops gradually from the outer surface to inner surface. It might be related to the difference of texture between outer surface and inner surface. The threshold stress is affected by both the texture and the value of B. So controlling texture could still restrict hydride reorientation under tensile stress.

  14. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  15. Complex metal hydrides for hydrogen, thermal and electrochemical energy storage

    DEFF Research Database (Denmark)

    Møller, Kasper T.; Sheppard, Drew; Ravnsbæk, Dorthe B.

    2017-01-01

    field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...... how complex metal hydrides may act in an integrated setup with a fuel cell. This review focuses on the unique properties of light element complex metal hydrides mainly based on boron, nitrogen and aluminum, e.g., metal borohydrides and metal alanates. Our hope is that this review can provide new...

  16. Finite difference program for calculating hydride bed wall temperature profiles

    International Nuclear Information System (INIS)

    Klein, J.E.

    1992-01-01

    A QuickBASIC finite difference program was written for calculating one dimensional temperature profiles in up to two media with flat, cylindrical, or spherical geometries. The development of the program was motivated by the need to calculate maximum temperature differences across the walls of the Tritium metal hydrides beds for thermal fatigue analysis. The purpose of this report is to document the equations and the computer program used to calculate transient wall temperatures in stainless steel hydride vessels. The development of the computer code was motivated by the need to calculate maximum temperature differences across the walls of the hydrides beds in the Tritium Facility for thermal fatigue analysis

  17. Investigation process of alcoholysis of hydride aluminium-adobe

    International Nuclear Information System (INIS)

    Numanov, M.I.; Normatov, I.Sh.; Mirsaidov, U.M.

    2001-01-01

    Considering of that process of acid treatment of aluminium-adobe hydride realizes in the ethyl alcohol media it was necessary study the process of alcoholysis of AlH 3 and aluminium additives. In the end of article authors became to conclusion that deficiency of spontaneous alcoholysis of AlH 3 in adobe caused by protective action of fiber; solvate ability of LiCl and alkoxy aluminium hydride of lithium-LiCl·CO 2 H 5 OH, Li Al(OC 2 H 5 ) 4 ·nC 2 H 5 OH decreasing the expectancy of responding of alcohol with aluminium hydride

  18. Cholera toxin can catalyze ADP-ribosylation of cytoskeletal proteins

    International Nuclear Information System (INIS)

    Kaslow, H.R.; Groppi, V.E.; Abood, M.E.; Bourne, H.R.

    1981-01-01

    Cholera toxin catalyzes transfer of radiolabel from [ 32 P]NAD + to several peptides in particulate preparations of human foreskin fibroblasts. Resolution of these peptides by two-dimensional gel electrophoresis allowed identification of two peptides of M/sub r/ = 42,000 and 52,000 as peptide subunits of a regulatory component of adenylate cyclase. The radiolabeling of another group of peptides (M/sub r/ = 50,000 to 65,000) suggested that cholera toxin could catalyze ADP-ribosylation of cytoskeletal proteins. This suggestion was confirmed by showing that incubation with cholera toxin and [ 32 P]NAD + caused radiolabeling of purified microtubule and intermediate filament proteins

  19. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  20. Determination of hydrogen in zirconium hydride and uranium-zirconium hydride by inert gas exraction-gravimetric method

    International Nuclear Information System (INIS)

    Hoshino, Akira; Iso, Shuichi

    1976-01-01

    An inert gas extraction-gravimetric method has been applied to the determination of hydrogen in zirconium hydride and uranium-zirconium hydride which are used as neutron moderator and fuel of nuclear safety research reactor (NSRR), respectively. The sample in a graphite-enclosed quartz crucible is heated inductively to 1200 0 C for 20 min in a helium stream. Hydrogen liberated from the sample is oxidized to water by copper(I) oxide-copper(II) oxide at 400 0 C, and the water is determined gravimetrically by absorption in anhydrone. The extraction curves of hydrogen for zirconium hydride and uranium-zirconium hydride samples are shown in Figs. 2 and 3. Hydrogen in the samples is extracted quantitatively by heating at (1000 -- 1250) 0 C for (10 -- 40) min. Recoveries of hydrogen in the case of zirconium hydride were examined as follows: a weighed zirconium rod (5 phi x 6 mm, hydrogen -5 Torr. After the chamber was filled with purified hydrogen to 200 Torr, the rod was heated to 400 0 C for 15 h, and again weighed to determine the increase in weight. Hydrogen in the rod was then determined by the proposed method. The results are in excellent agreement with the increase in weight as shown in Table 1. Analytical results of hydrogen in zirconium hydride samples and an uranium-zirconium hydride sample are shown in Table 2. (auth.)

  1. Delayed hydride cracking of zirconium alloy fuel cladding

    International Nuclear Information System (INIS)

    2010-10-01

    This report describes the work performed in a coordinated research project on Hydrogen and Hydride Degradation of the Mechanical and Physical Properties of Zirconium Alloys. It is the second in the series. In 2005-2009 that work was extended within a new CRP called Delayed Hydride Cracking in Zirconium Alloy Fuel Cladding. The project consisted of adding hydrogen to samples of Zircaloy-4 claddings representing light water reactors (LWRs), CANDU and Atucha, and measuring the rates of delayed hydride cracking (DHC) under specified conditions. The project was overseen by a supervisory group of experts in the field who provided advice and assistance to participants as required. All of the research work undertaken as part of the CRP is described in this report, which includes details of the experimental procedures that led to a consistent set of data for LWR cladding. The participants and many of their co-workers in the laboratories involved in the CRP contributed results and material used in this report, which compiles the results, their analysis, discussions of their interpretation and conclusions and recommendations for future work. The research was coordinated by an advisor and by representatives in three laboratories in industrialized Member States. Besides the basic goal to transfer the technology of the testing technique from an experienced laboratory to those unfamiliar with the methods, the CRP was set up to harmonize the experimental procedures to produce consistent sets of data, both within a single laboratory and between different laboratories. From the first part of this project it was demonstrated that by following a standard set of experimental protocols, consistent results could be obtained. Thus, experimental vagaries were minimized by careful attention to detail of microstructure, temperature history and stress state in the samples. The underlying idea for the test programme was set out at the end of the first part of the project on pressure tubes. The

  2. Process for production of a metal hydride

    Science.gov (United States)

    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.

  3. Boron hydride analogues of the fullerenes

    International Nuclear Information System (INIS)

    Quong, A.A.; Pederson, M.R.; Broughton, J.Q.

    1994-01-01

    The BH moiety is isoelectronic with C. We have studied the stability of the (BH) 60 analogue of the C 60 fullerene as well as the dual-structure (BH) 32 icosahedron, both of them being putative structures, by performing local-density-functional electronic calculations. To aid in our analysis, we have also studied other homologues of these systems. We find that the latter, i.e., the dual structure, is the more stable although the former is as stable as one of the latter's lower homologues. Boron hydrides, it seems, naturally form the dual structures used in algorithmic optimization of complex fullerene systems. Fully relaxed geometries are reported as well as electron affinities and effective Hubbard U parameters. These systems form very stable anions and we conclude that a search for BH analogues of the C 60 alkali-metal supeconductors might prove very fruitful

  4. Hydrogen storage properties of metallic hydrides

    International Nuclear Information System (INIS)

    Latroche, M.; Percheron-Guegan, A.

    2005-01-01

    Nowadays, energy needs are mainly covered by fossil energies leading to pollutant emissions mostly responsible for global warming. Among the different possible solutions for greenhouse effect reduction, hydrogen has been proposed for energy transportation. Indeed, H 2 can be seen as a clean and efficient energy carrier. However, beside the difficulties related to hydrogen production, efficient high capacity storage means are still to be developed. Many metals and alloys are able to store large amounts of hydrogen. This latter solution is of interest in terms of safety, global yield and long term storage. However, to be suitable for applications, such compounds must present high capacity, good reversibility, fast reactivity and sustainability. In this paper, we will review the structural and thermodynamic properties of metallic hydrides. (authors)

  5. Catalyzed deuterium fueled tokamak reactors

    International Nuclear Information System (INIS)

    Southworth, F.H.

    1977-01-01

    Catalyzed deuterium fuel presents several advantages relative to D-T. These are, freedom from tritium breeding, high charged particle power fraction and lowered neutron energy deposition in the blanket. Higher temperature operation, lower power densities and increased confinement are simultaneously required. However, the present study has developed designs which have capitalized upon the advantages of catalyzed deuterium to overcome the difficulties associated with the fuel while obtaining high efficiency

  6. Hydrogen storage in sodium aluminum hydride.

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-11-01

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

  7. Technical and economic evaluation of hydrogen storage systems based on light metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jepsen, Julian

    2014-07-01

    Novel developments regarding materials for solid-state hydrogen storage show promising prospects. These complex hydrides exhibit high mass-related storage capacities and thus great technical potential to store hydrogen in an efficient and safe way. However, a comprehensive evaluation of economic competitiveness is still lacking, especially in the case of the LiBH4 / MgH2 storage material. In this study, an assessment with respect to the economic feasibility of implementing complex hydrides as hydrogen storage materials is presented. The cost structure of hydrogen storage systems based on NaAlH4 and LiBH4 / MgH2 is discussed and compared with the conventional high pressure (700 bar) and liquid storage systems. Furthermore, the properties of LiBH4 / MgH2, so-called Li-RHC (Reactive Hydride Composite), are scientifically compared and evaluated on the lab and pilot plant scale. To enhance the reaction rate, the addition of TiCl3 is investigated and high energy ball milling is evaluated as processing technique. The effect of the additive in combination with the processing technique is described in detail. Finally, an optimum set of processing parameters and additive content are identified and can be applied for scaled-up production of the material based on simple models considering energy input during processing. Furthermore, thermodynamic, heat transfer and kinetic properties are experimentally determined by different techniques and analysed as a basis for modelling and designing scaled-up storage systems. The results are analysed and discussed with respect to the reaction mechanisms and reversibility of the system. Heat transfer properties are assessed with respect to the scale-up for larger hydrogen storage systems. Further improvements of the heat transfer were achieved by compacting the material. In this regard, the influence of the compaction pressure on the apparent density, thermal conductivity and sorption behaviour, was investigated in detail. Finally, scaled

  8. Ductile zirconium powder by hydride-dehydride process

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, T S [BHABHA ATOMIC RESEARCH CENTRE, BOMBAY (INDIA); CHAUDHARY, S [NUCLEAR FUEL COMPLEX, HYDERABAD (INDIA)

    1976-09-01

    The preparation of ductile zirconium powder by the hydride-dehydride process has been described. In this process massive zirconium obtained from Kroll reduction of ZrCl/sub 4/ is first rendered brittle by hydrogenation and the hydride crushed and ground in a ball mill to the required particle size. Hydrogen is then hot vacuum extracted to yield the metal powder. The process has been successfully employed for the production of zirconium powders with low oxygen content and having hardness values in the range of 115-130 BHN, starting from a zirconium sponge of 100-120 BHN hardness. Influence of surface characteristics of the starting metal on its hydriding behaviour has been studied and the optimum hydriding-dehydriding conditions established.

  9. Electrochemical modeling of hydrogen storage in hydride-forming electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2009-01-01

    An electrochemical kinetic model (EKM) is developed, describing the electrochemical hydrogen storage in hydride-forming materials under equilibrium conditions. This model is based on first principles of electrochemical reaction kinetics and statistical thermodynamics and describes the complex,

  10. Development of zirconium hydride highly effective moderator materials

    International Nuclear Information System (INIS)

    Yin Changgeng

    2005-10-01

    The zirconium hydride with highly content of hydrogen and low density is new efficient moderator material for space nuclear power reactor. Russia has researched it to use as new highly moderator and radiation protection materials. Japanese has located it between the top of pressure vessel and the main protection as a shelter, the work temperature is rach to 220 degree C. The zirconium hydride moderator blocks are main parts of space nuclear power reactor. Development of zirconium hydride moderator materials have strength research and apply value. Nuclear Power Research and Design Instituteoh China (NPIC) has sep up the hydrogenation device and inspect systems, and accumurate a large of experience about zirconium hydride, also set up a strict system of QA and QC. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  12. Delayed Hydride Cracking in Zr-2.5Nb Tubes with the Direction of An Approach to Temperature

    International Nuclear Information System (INIS)

    Kim, Young Suk; Im, Kyung Soo; Kim, Kang Soo; Ahn, Sang Bok; Cheong, Yong Moo

    2006-01-01

    One of the unique features of delayed hydride cracking (DHC) of zirconium alloys is that the DHC velocity (DHCV) of zirconium alloys strongly depends on the path to the test temperature. Ambler reported that the DHCV of Zr-2.5Nb tubes at temperatures above 180 .deg. C depended upon the direction of an approach to the test temperatures, and reported on a presence of the DHC arrest temperature or TDAT above which the DHCV decreased upon an approach to the test temperature by a heating. Ambler proposed a hydrogen transfer from the bulk to the crack tip assuming that the hydrides formed at the crack tip and in the bulk region are fully constrained and partially constrained at the crack tip, respectively. In other words, the terminal solid solubility (TSS) of hydrogen would be governed by elastic strain energy induced by the precipitating hydrides, leading to a higher TSS in the bulk region than that at the crack tip. In a sense, his assumption that the hydrogen concentration is higher in the bulk region than that at the crack tip due to a higher TSS in the bulk region is, in a way, similar to Kim's DHC model. Even though Ambler assumed a different strain energy of the matrix hydrides with the direction of an approach to the test temperature, the peak temperature, hydrogen concentration and the hydride phase, a feasible rationale for this assumption is yet to be given. In this study, a path dependence of DHC velocity of Zr-2.5Nb tubes will be investigated using Kim's DHC model where a driving force for DHC is the supersaturated hydrogen concentration between the crack tip and the bulk region. To this ends, the furnace cooled and water-quenched Zr-2.5Nb specimens were subjected to DHC tests at different test temperatures that were approached by a heating or by a cooling. Kim's DHC model predicts that the water-quenched Zr- 2.5Nb will have DHC crack growth even at temperatures above 180 .deg. C where the furnace-cooled Zr-2.5Nb will not. This experiment will provide

  13. Delayed Hydride Cracking in Zr-2.5Nb Tubes with the Direction of An Approach to Temperature

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Im, Kyung Soo; Kim, Kang Soo; Ahn, Sang Bok; Cheong, Yong Moo [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2006-07-01

    One of the unique features of delayed hydride cracking (DHC) of zirconium alloys is that the DHC velocity (DHCV) of zirconium alloys strongly depends on the path to the test temperature. Ambler reported that the DHCV of Zr-2.5Nb tubes at temperatures above 180 .deg. C depended upon the direction of an approach to the test temperatures, and reported on a presence of the DHC arrest temperature or TDAT above which the DHCV decreased upon an approach to the test temperature by a heating. Ambler proposed a hydrogen transfer from the bulk to the crack tip assuming that the hydrides formed at the crack tip and in the bulk region are fully constrained and partially constrained at the crack tip, respectively. In other words, the terminal solid solubility (TSS) of hydrogen would be governed by elastic strain energy induced by the precipitating hydrides, leading to a higher TSS in the bulk region than that at the crack tip. In a sense, his assumption that the hydrogen concentration is higher in the bulk region than that at the crack tip due to a higher TSS in the bulk region is, in a way, similar to Kim's DHC model. Even though Ambler assumed a different strain energy of the matrix hydrides with the direction of an approach to the test temperature, the peak temperature, hydrogen concentration and the hydride phase, a feasible rationale for this assumption is yet to be given. In this study, a path dependence of DHC velocity of Zr-2.5Nb tubes will be investigated using Kim's DHC model where a driving force for DHC is the supersaturated hydrogen concentration between the crack tip and the bulk region. To this ends, the furnace cooled and water-quenched Zr-2.5Nb specimens were subjected to DHC tests at different test temperatures that were approached by a heating or by a cooling. Kim's DHC model predicts that the water-quenched Zr- 2.5Nb will have DHC crack growth even at temperatures above 180 .deg. C where the furnace-cooled Zr-2.5Nb will not. This experiment

  14. Reactions of zinc hydride and magnesium hydride with pyridine; synthesis and characterization of 1,4-dihydro-1-pyridylzinc and -magnesium complexes

    NARCIS (Netherlands)

    Koning, A.J. de; Boersma, J.; Kerk, G.J.M. van der

    1980-01-01

    The synthesis and characterization of 1,4-dihydro-1-pyridylzinc and -magnesium complexes are described. Zinc hydride and magnesium hydride dissolve in and react with pyridine, and the reaction has been studied in detail in the case of zinc hydride. Evaporation of the solvent after 1–2 hours at 0°C

  15. Electronic structure of ternary hydrides based on light elements

    Energy Technology Data Exchange (ETDEWEB)

    Orgaz, E. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)]. E-mail: orgaz@eros.pquim.unam.mx; Membrillo, A. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Castaneda, R. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Aburto, A. [Departamento de Fisica, Facultad de Ciencias, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)

    2005-12-08

    Ternary hydrides based on light elements are interesting owing to the high available energy density. In this work we focused into the electronic structure of a series of known systems having the general formula AMH{sub 4}(A=Li,Na,M=B,Al). We computed the energy bands and the total and partial density of states using the linear-augmented plane waves method. In this report, we discuss the chemical bonding in this series of complex hydrides.

  16. Spectroscopy of helium hydride and triatomic hydrogen molecules

    International Nuclear Information System (INIS)

    Ketterle, W.

    1986-07-01

    Helium hydride and triatomic hydrogen has been produced by charge exchange between fast mass selected beams of molecular ions and alkali vapor. Using this method, the first discrete spectra of helium hydride were obtained. Fine electronic transitions with resolved rotational structure were observed in the visible and near infrared. Four isotopic mixtures were studied. Furthermore the first lifetime measurement of triatomic hydrogen states were performed and compared to theoretical predictions. (orig.)

  17. Proton location in metal hydrides using electron spin resonance

    International Nuclear Information System (INIS)

    Venturini, E.L.

    1979-01-01

    Electron spin resonance (ESR) of dilute paramagnetic ions establishes the site symmetry of these ions. In the case of metal hydrides the site symmetry is determined by the number and location of neighboring protons. Typical ESR spectra for trivalent erbium in scandium and yttrium hydrides are presented and analyzed, and this technique is shown to be a versatile microscopic probe of the location, net charge and occupation probability of nearby protons

  18. The Production of Uranium Metal by Metal Hydrides Incorporated

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, P. P.

    1943-01-01

    Metal Hydrides Incorporated was a pioneer in the production of uranium metal on a commercial scale and supplied it to all the laboratories interested in the original research, before other methods for its production were developed. Metal Hydrides Inc. supplied the major part of the metal for the construction of the first experimental pile which, on December 2, 1942, demonstrated the feasibility of the self-sustaining chain reaction and the release of atomic energy.

  19. Successive heterolytic cleavages of H2 achieve N2 splitting on silica-supported tantalum hydrides: A DFT proposed mechanism

    KAUST Repository

    Soláns, Xavier Luis

    2012-07-02

    DFT(B3PW91) calculations have been carried out to propose a pathway for the N2 cleavage by H2 in the presence of silica-supported tantalum hydride complexes [(≡ SiO)2TaHx] that forms [(≡SiO)2Ta(NH)(NH2)] (Science2007, 317, 1056). The calculations, performed on the cluster models {μ-O[(HO)2SiO] 2}TaH1 and {μ-O[(HO)2SiO] 2}TaH3, labelled as (≡SiO)2TaH x (x = 1, 3), show that the direct hydride transfers to coordinated N-based ligands in (≡SiO)2TaH(η2-N2) and (≡SiO)2TaH(η2-HNNH) have high energy barrier barriers. These high energy barriers are due in part to a lack of energetically accessible empty orbitals in the negatively charged N-based ligands. It is shown that a succession of proton transfers and reduction steps (hydride transfer or 2 electron reduction by way of dihydride reductive coupling) to the nitrogen-based ligands leads to more energetically accessible pathways. These proton transfers, which occur by way of heterolytic activation of H2, increase the electrophilicity of the resulting ligand (diazenido, N 2H-, and hydrazido, NHNH2-, respectively) that can thus accept a hydride with a moderate energy barrier. In the case of (≡SiO)2TaH(η2-HNNH), the H 2 molecule that is adding across the Ta-N bond is released after the hydride transfer step by heterolytic elimination from (≡SiO) 2TaH(NH2)2, suggesting that dihydrogen has a key role in assisting the final steps of the reaction without itself being consumed in the process. This partly accounts for the experimental observation that the addition of H2 is needed to convert an intermediate, identified as a diazenido complex [(≡SiO)2TaH(η 2-HNNH)] from its ν(N-H) stretching frequency of 3400 cm -1, to the final product. Throughout the proposed mechanism, the tantalum remains in its preferred high oxidation state and avoids redox-type reactions, which are more energetically demanding. © 2012 American Chemical Society.

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

    International Nuclear Information System (INIS)

    Wronski, Z.; Varin, R.A.; Chiu, C.; Czujko, T.; Calka, A.

    2007-01-01

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

  1. The use of metal hydrides in fuel cell applications

    Directory of Open Access Journals (Sweden)

    Mykhaylo V. Lototskyy

    2017-02-01

    Full Text Available This paper reviews state-of-the-art developments in hydrogen energy systems which integrate fuel cells with metal hydride-based hydrogen storage. The 187 reference papers included in this review provide an overview of all major publications in the field, as well as recent work by several of the authors of the review. The review contains four parts. The first part gives an overview of the existing types of fuel cells and outlines the potential of using metal hydride stores as a source of hydrogen fuel. The second part of the review considers the suitability and optimisation of different metal hydrides based on their energy efficient thermal integration with fuel cells. The performances of metal hydrides are considered from the viewpoint of the reversible heat driven interaction of the metal hydrides with gaseous H2. Efficiencies of hydrogen and heat exchange in hydrogen stores to control H2 charge/discharge flow rates are the focus of the third section of the review and are considered together with metal hydride – fuel cell system integration issues and the corresponding engineering solutions. Finally, the last section of the review describes specific hydrogen-fuelled systems presented in the available reference data.

  2. U-8 wt %Mo and 7 wt %Mo alloys powder obtained by an hydride-de hydride process

    International Nuclear Information System (INIS)

    Balart, Silvia N.; Bruzzoni, Pablo; Granovsky, Marta S.; Gribaudo, Luis M. J.; Hermida, Jorge D.; Ovejero, Jose; Rubiolo, Gerardo H.; Vicente, Eduardo E.

    2000-01-01

    Uranium-molybdenum alloys are been tested as a component in high-density LEU dispersion fuels with very good performances. These alloys need to be transformed to powder due to the manufacturing requirements of the fuels. One method to convert ductile alloys into powder is the hydride-de hydride process, which takes advantage of the ability of the U-α phase to transform to UH 3 : a brittle and relatively low-density compound. U-Mo alloys around 7 and 8 wt % Mo were melted and heat treated at different temperature ranges in order to partially convert γ -phase to α -phase. Subsequent hydriding transforms this α -phase to UH 3 . The volume change associated to the hydride formation embrittled the material which ends up in a powdered alloy. Results of the optical metallography, scanning electron microscopy, X-ray diffraction during different steps of the process are shown. (author)

  3. Structure and Mechanism of Styrene Monooxygenase Reductase: New Insight into the FAD–Transfer Reaction†

    Science.gov (United States)

    Morrison, Eliot; Kantz, Auric; Gassner, George T.; Sazinsky, Matthew H.

    2013-01-01

    The two–component flavoprotein styrene monooxygenase (SMO) from Pseudomonas putida S12 catalyzes the NADH– and FAD–dependent epoxidation of styrene to styrene oxide. In this study we investigate the mechanism of flavin reduction and transfer from the reductase (SMOB) to epoxidase (NSMOA) component and report our findings in light of the 2.2–Å crystal structure of SMOB. Upon rapidly mixing with NADH, SMOB forms an NADH→FADox charge–transfer intermediate and catalyzes a hydride–transfer reaction from NADH to FAD, with a rate constant of 49.1 ± 1.4 s−1, in a step that is coupled to the rapid dissociation of NAD+. Electrochemical and equilibrium–binding studies indicate that NSMOA binds FADhq ~13–times more tightly than SMOB, which supports a vectoral transfer of FADhq from the reductase to the epoxidase. After binding to NSMOA, FADhq rapidly reacts with molecular oxygen to form a stable C(4a)–hydroperoxide intermediate. The half–life of apoSMOB generated in the FAD–transfer reaction is increased ~21–fold, supporting the model of a protein–protein interaction between apoSMOB and NSMOA with the peroxide intermediate. The mechanisms of FAD–dissociation and transport from SMOB to NSMOA were probed by monitoring the competitive reduction of cytochrome c in the presence and absence of pyridine nucleotides. Based on these studies, we propose a model in which reduced FAD binds to SMOB in equilibrium between an unreactive, sequestered state (S–state) and more reactive, transfer state (T–state). Dissociation of NAD+ after the hydride transfer–reaction transiently populates the T–state, promoting the transfer of FADhq to NSMOA. The binding of pyridine nucleotides to SMOB–FADhq shifts the FADhq–binding equilibrium from the T–state to the S–state. Additionally, the 2.2–Å crystal structure of SMOB–FADox reported in this work is discussed in light of the pyridine nucleotide–gated flavin–transfer and electron–transfer

  4. Manganese Catalyzed C–H Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Groves, John T.

    2015-06-16

    The remarkable aliphatic C–H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon–halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C–H bonds to C–Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L–MnV$=$O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn–F fluorine source, effecting carbon–fluorine bond

  5. Effect of electronegativity on the mechanical properties of metal hydrides with a fluorite structure

    International Nuclear Information System (INIS)

    Ito, Masato; Setoyama, Daigo; Matsunaga, Junji; Muta, Hiroaki; Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke

    2006-01-01

    Bulk titanium, yttrium, and zirconium hydrides, which have the same structure as that of fluorite-type fcc C 1, were produced and their mechanical properties were investigated. With an increase in the hydrogen content, the lattice parameters of titanium and zirconium hydrides increased, whereas those of yttrium hydride decreased. The elastic moduli of titanium and zirconium hydrides decreased by hydrogen addition, whereas those of yttrium hydride increased. There are linear relations between the electronegativities and hydrogen content dependence of the properties. Therefore, the mechanical properties of the metal hydrides are considered to be determined by a common rule based on the electronegativity

  6. Fullerene hydride - A potential hydrogen storage material

    International Nuclear Information System (INIS)

    Nai Xing Wang; Jun Ping Zhang; An Guang Yu; Yun Xu Yang; Wu Wei Wang; Rui long Sheng; Jia Zhao

    2005-01-01

    Hydrogen, as a clean, convenient, versatile fuel source, is considered to be an ideal energy carrier in the foreseeable future. Hydrogen storage must be solved in using of hydrogen energy. To date, much effort has been put into storage of hydrogen including physical storage via compression or liquefaction, chemical storage in hydrogen carriers, metal hydrides and gas-on-solid adsorption. But no one satisfies all of the efficiency, size, weight, cost and safety requirements for transportation or utility use. C 60 H 36 , firstly synthesized by the method of the Birch reduction, was loaded with 4.8 wt% hydrogen indicating [60]fullerene might be as a potential hydrogen storage material. If a 100% conversion of C 60 H 36 is achieved, 18 moles of H 2 gas would be liberated from each mole of fullerene hydride. Pure C 60 H 36 is very stable below 500 C under nitrogen atmosphere and it releases hydrogen accompanying by other hydrocarbons under high temperature. But C 60 H 36 can be decomposed to generate H 2 under effective catalyst. We have reported that hydrogen can be produced catalytically from C 60 H 36 by Vasks's compound (IrCl(CO)(PPh 3 ) 2 ) under mild conditions. (RhCl(CO)(PPh 3 ) 2 ) having similar structure to (IrCl(CO)(PPh 3 ) 2 ), was also examined for thermal dehydrogenation of C 60 H 36 ; but it showed low catalytic activity. To search better catalyst, palladium carbon (Pd/C) and platinum carbon (Pt/C) catalysts, which were known for catalytic hydrogenation of aromatic compounds, were tried and good results were obtained. A very big peak of hydrogen appeared at δ=5.2 ppm in 1 H NMR spectrum based on Evans'work (fig 1) at 100 C over a Pd/C catalyst for 16 hours. It is shown that hydrogen can be produced from C 60 H 36 using a catalytic amount of Pd/C. Comparing with Pd/C, Pt/C catalyst showed lower activity. The high cost and limited availability of Vaska's compounds, Pd and Pt make it advantageous to develop less expensive catalysts for our process based on

  7. Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes.

    Science.gov (United States)

    Price, Jeffrey S; Emslie, David J H; Britten, James F

    2017-05-22

    Reaction of the ethylene hydride complex trans-[(dmpe) 2 MnH(C 2 H 4 )] (1) with Et 2 SiH 2 at 20 °C afforded the silylene hydride [(dmpe) 2 MnH(=SiEt 2 )] (2 a) as the trans-isomer. By contrast, reaction of 1 with Ph 2 SiH 2 at 60 °C afforded [(dmpe) 2 MnH(=SiPh 2 )] (2 b) as a mixture of the cis (major) and trans (minor) isomers, featuring a Mn-H-Si interaction in the former. The reaction to form 2 b also yielded [(dmpe) 2 MnH 2 (SiHPh 2 )] (3 b); [(dmpe) 2 MnH 2 (SiHR 2 )] (R=Et (3 a) and Ph (3 b)) were accessed cleanly by reaction of 2 a and 2 b with H 2 , and the analogous reactions with D 2 afforded [(dmpe) 2 MnD 2 (SiHR 2 )] exclusively. Both 2 a and 2 b engaged in unique reactivity with ethylene, generating the silene hydride complexes cis-[(dmpe) 2 MnH(R 2 Si=CHMe)] (R=Et (4 a), Ph (4 b)). Compounds trans-2 a, cis-2 b, 3 b, and 4 b were crystallographically characterized, and bonding in 2 a, 2 b, 4 a, and 4 b was probed computationally. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Heat exchanger selection and design analyses for metal hydride heat pump systems

    DEFF Research Database (Denmark)

    Mazzucco, Andrea; Voskuilen, Tyler G.; Waters, Essene L.

    2016-01-01

    This study presents a design analysis for the development of highly efficient heat exchangers within stationary metal hydride heat pumps. The design constraints and selected performance criteria are applied to three representative heat exchangers. The proposed thermal model can be applied to select...... the most efficient heat exchanger design and provides outcomes generally valid in a pre-design stage. Heat transfer effectiveness is the principal performance parameter guiding the selection analysis, the results of which appear to be mildly (up to 13%) affected by the specific Nusselt correlation used....... The thermo-physical properties of the heat transfer medium and geometrical parameters are varied in the sensitivity analysis, suggesting that the length of independent tubes is the physical parameter that influences the performance of the heat exchangers the most. The practical operative regions for each...

  9. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  10. Solubility of hydrogen isotopes in stressed hydride-forming metals

    International Nuclear Information System (INIS)

    Coleman, C.E.; Ambler, J.F.R.

    1983-01-01

    Components made from hydride-forming metals can be brittle when particles of hydride are present. The solid solubility limit of hydrogen in these metals needs to be known so that fracture resistance can be properly assessed. Stress affects the solubility of hydrogen in metals. As hydrogen dissolves the metal volume increases, an applied hydrostatic tensile stress supplies work to increase the solubility. Precipitation of hydrides increases the volume further. A hydrostatic tensile stress promotes the formation of hydrides and tends to reduce the terminal solubility. For materials containing hydrogen in solution in equilibrium with hydrides, the effect of stress on the terminal solubility is given. Hydrogen migrates up tensile stress gradients because of the effect of stress on the solubility and solubility limit. Consequently, hydrogen concentrates at flaws. When hydrides are present in the metal matrix, those remote from the flaw tip will preferentially dissolve in favor of those precipitated at the flaw. If the stress is large enough, at some critical condition the hydrides at the flaw will crack. This is delayed hydrogen cracking. Notched and fatigue-cracked cantilever beam specimens (6) (38 x 4 x 3 mm) were machined from the circumferential direction of several cold-worked Zr-2.5 at. % Nb pressure tubes. The chemical compositions had the ranges (in atomic %) Nb - 2.5 to 2.7; O - 0.58 to 0.71; H - 0.018 to 0.18. The effect of test temperature is for a specimen containing 0.13 at. % protium and 0.29 at .% deuterium. Between 505 K and 530 K was less than 1 hr, between 530 K and 537 K it increased to 25.8 h, while at 538 K no cracking was observed up to the 54 h

  11. Influence of uranium hydride oxidation on uranium metal behaviour

    International Nuclear Information System (INIS)

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

    2013-01-01

    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)

  12. Influence of uranium hydride oxidation on uranium metal behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Patel, N.; Hambley, D. [National Nuclear Laboratory (United Kingdom); Clarke, S.A. [Sellafield Ltd (United Kingdom); 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)

  13. Developments in delayed hydride cracking in zirconium alloys

    International Nuclear Information System (INIS)

    Puls, Manfred P.

    2008-01-01

    Delayed hydride cracking (DHC) is a process of diffusion assisted localized hydride embrittlement at flaws or regions of high stress. Models of DHC propagation and initiation have been developed that capture the essential elements of this phenomenon in terms of parameters describing processes occurring at the micro-scale. The models and their predictions of experimental results applied to Zr alloys are assessed. The propagation model allows rationalization of the effect of direction of approach to temperature and of the effect of the state and morphology of the beta phase in Zr-2.5Nb on DHC velocity. The K I dependence of the DHC velocity can only be approximately rationalized by the propagation models. This is thought to be because these models approximate the DHC velocity by a constant and shape-invariant rate of growth of the hydride at the flaw and have not incorporated a coupling between the applied stress field due to the flaw alone and the precipitated hydrides that would result in a variation of the shape and density of the hydrided region with K I . Separately, models have been developed for DHC initiation at cracks and blunt flaws. Expressions are obtained for the threshold stress intensity factor, K IH , for DHC initiation at a crack. A model for K IH has been used to rationalize the experimental result that DHC initiation is not possible above a certain temperature, even when hydrides can form at the crack tip. For blunt flaws with root radii in the μm range, and engineering process zone procedure has been derived to determine the initiation conditions requiring that both a critical stress and a critical flaw tip displacement must be achieved for hydride fracture. The engineering process zone procedure takes account of the dependence of DHC initiation on the flaw's root radius. Although all of the foregoing models are capable of describing the essential features of DHC, they are highly idealized and in need of further refinement. (author)

  14. Multidimensional simulations of hydrides during fuel rod lifecycle

    International Nuclear Information System (INIS)

    Stafford, D.S.

    2015-01-01

    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. - Highlights: • We extend BISON fuel performance code to simulate lifecycle of fuel rods. • We model hydrogen evolution in cladding from reactor through dry storage. • We validate 1D simulations of hydrogen evolution against experiments. • We show results of 2D axisymmetric simulations predicting hydride formation. • We show how our model predicts formation of a hydride rim in the cladding.

  15. Permeation rates for RTF metal hydride vessels

    International Nuclear Information System (INIS)

    Klein, J.E.

    1992-01-01

    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 x 10 -3 μCi/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

  16. Hydriding and neutron irradiation in zircaloy-4

    International Nuclear Information System (INIS)

    Ramos, Ruben Fortunato; Martin, Juan Ezequiel; Orellano, Pablo; Dorao, Carlos; Analia Soldati; Ghilarducci, Ada Albertina; Corso, Hugo Luis; Peretti, Hernan Americo; Bolcich, Juan Carlos

    2003-01-01

    The composition of Zircaloy-4 for nuclear applications is specified by the ASTM B350 Standard, that fixes the amount of alloying elements (Sn, Fe, Cr) and impurities (Ni, Hf, O, N, C, among others) to optimize good corrosion and mechanical behavior.The recycling of zircaloy-4 scrap and chips resulting from cladding tube fabrication is an interesting issue.However, changes in the final composition of the recycled material may occur due to contamination with tool pieces, stainless steel chips, turnings, etc. while scrap is stored and handled. Since the main components of the possible contaminants are Fe, Cr and Ni, it arises the interest in studying up to what limit the Fe, Ni and Cr contents could be exceeded beyond the standard specification without affecting significantly the alloy properties.Zircaloy-4 alloys elaborated with Fe, Cr and Ni additions and others of standard composition in use in nuclear plants are studied by tensile tests, SEM observations and EDS microanalysis.Some samples are tested in the initial condition and others after hydriding treatments and neutron irradiation in the RA6

  17. Optical and photoemission studies of lanthanum hydrides

    International Nuclear Information System (INIS)

    Peterman, D.J.; Peterson, D.T.; Weaver, J.H.

    1980-01-01

    The results of optical absorptivity and photoemission measurements on lanthanum hydrides, LaH/sub x/ (1.98 less than or equal to x less than or equal to 2.89) are reported. The low energy (hν less than or equal to 0.5 eV) optical features in LaH/sub x/ are attributed to the filling of octahedral sites. Higher energy interband absorption involves states within the d-band complex, analogous to other dihydrides. As x increases above 2.0, the optical features change rapidly due to the increase in the number of occupied octahedral sites. Various band structure studies suggest that LaH 3 might be a semiconductor. Photoemission results show that as x increases, the d-derived states at E/sub F/ are drawn down and that for LaH 2 89 only very weak valence band emission is observed. The hydrogen-derived bonding bands are shown centered approx. 5 eV below E/sub F/. Observed chemical shifts in the La 5p/sub 1/2 3/2/ cores are discussed for 1.98 less than or equal to x less than or equal to 2.89

  18. Theoretical survey of muon catalyzed fusion

    International Nuclear Information System (INIS)

    Leon, M.

    1988-01-01

    The main steps in the muon-catalyzed d-t fusion cycle are given in this report. Most of the stages are very fast, and therefore do not contribute significantly to the cycling time. Thus at liquid H 2 densities (/phi/ = 1 in the standard convention) the time for stopping the negative muon, its subsequent capture and deexcitation to the ground state is estimated to be /approximately/ 10/sup/minus/11/ sec. 1 The muon spends essentially all of its time in either the (dμ) ground state, waiting for transfer to a (tμ) ground state to occur, or in the (tμ) ground state, writing for molecular formation to occur. Following the formation of this ''mesomolecule'' (actually a muonic molecular ion), deexcitation and fusion are again fast. Then the muon is (usually) liberated to go around again. We will discuss these steps in some detail. 5 refs., 3 figs

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

    Energy Technology Data Exchange (ETDEWEB)

    Argabright, T.A.

    1982-02-01

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

  20. Synthesis of New Silicon-linked Lanthanocene Complexes and Their High Catalytic Activity for Methyl Methacrylate Polymerization with Nanometric Sodium Hydride as Co-catalyst

    Institute of Scientific and Technical Information of China (English)

    谢小敏; 黄吉玲

    2005-01-01

    The synthesis and characterization of four new silicon-linked lanthanocene complexes with pendant phenyl groups on cyclopentadiene were reported. Based on the data of elemental analyses, MS and IR, the complexes were presumed to be unsolvated and dimeric complexes [Me2Si(C5H3CMe2C6H5)2LnC1]2 [Ln=Er (1), Gd (2), Sm (3), Dy (4)]. In conjunction with AlEt3 or sodium hydride as the co-catalyst, these complexes could efficiently catalyze the polymerization of methyl methacrylate (MMA). When the nanometric sodium hydride was used as a co-catalyst, the complexes were highly effective for the polymerization of MMA. At low temperature and in short time, in [MeESi(C5H3CMe2C6H5)2LnC1]2/NaH (nanometric) system, the polymer was obtained in more than 80% yield and the molecular weight was greater than 105. The activity reached that of organolanthanide hydride as a single-component catalyst. In ]MeESi(C5H3CMe2C6H5)2ErC1]2/Nail (nanometric) system, the effects of the molar ratio of MMA/catalyst and catalyst/co-catalyst, and the temperature on polymerization were studied.

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

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

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

  2. The effect of stress state on zirconium hydride reorientation

    Science.gov (United States)

    Cinbiz, Mahmut Nedim

    Prior to storage in a dry-cask facility, spent nuclear fuel must undergo a vacuum drying cycle during which the spent fuel rods are heated up to elevated temperatures of ≤ 400°C to remove moisture the canisters within the cask. As temperature increases during heating, some of the hydride particles within the cladding dissolve while the internal gas pressure in fuel rods increases generating multi-axial hoop and axial stresses in the closed-end thin-walled cladding tubes. As cool-down starts, the hydrogen in solid solution precipitates as hydride platelets, and if the multiaxial stresses are sufficiently large, the precipitating hydrides reorient from their initial circumferential orientation to radial orientation. Radial hydrides can severely embrittle the spent nuclear fuel cladding at low temperature in response to hoop stress loading. Because the cladding can experience a range of stress states during the thermo-mechanical treatment induced during vacuum drying, this study has investigated the effect of stress state on the process of hydride reorientation during controlled thermo-mechanical treatments utilizing the combination of in situ X-ray diffraction and novel mechanical testing analyzed by the combination of metallography and finite element analysis. The study used cold worked and stress relieved Zircaloy-4 sheet containing approx. 180 wt. ppm hydrogen as its material basis. The failure behavior of this material containing radial hydrides was also studied over a range of temperatures. Finally, samples from reactor-irradiated cladding tubes were examined by X-ray diffraction using synchrotron radiation. To reveal the stress state effect on hydride reorientation, the critical threshold stress to reorient hydrides was determined by designing novel mechanical test samples which produce a range of stress states from uniaxial to "near-equibiaxial" tension when a load is applied. The threshold stress was determined after thermo-mechanical treatments by

  3. Precipitation of γ-zirconium hydride in zirconium

    International Nuclear Information System (INIS)

    Carpenter, G.J.C.

    1978-01-01

    A mechanism for the precipitation of γ-zirconium hydride in zirconium is presented which does not require the diffusion of zirconium. The transformation is completed by shears caused by 1/3 (10 anti 10) Shockley partial dislocations on alternate zirconium basal planes, either by homogeneous nucleation or at lattice imperfections. Homogeneous nucleation is considered least likely in view of the large nucleation barrier involved. Hydrides may form at dislocations by the generation of partials by means of either a pole or ratchet mechanism. The former requires dislocations with a component of Burgers vector along the c-axis, but contrast experiments show that these are not normally observed in annealed zirconium. It is therefore most likely that intragranular hydrides form at the regular 1/3 (11 anti 20) dislocations, possibly by means of a ratchet mechanism. Contrast experiments in the electron microscope show that the precipitates have a shear character consistent with the mechanism suggested. The possibility that the shear dislocations associated with the hydrides are emissary dislocations is considered and a model suggested in which this function is satisfied together with the partial relief of misfit stresses. The large shear strains associated with the precipitation mechanism may play an important role in the preferential orientation of hydrides under stress

  4. Sodium-based hydrides for thermal energy applications

    Science.gov (United States)

    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.

  5. Mechanisms of hydrogen induced delayed cracking in hydride forming materials

    International Nuclear Information System (INIS)

    Dutton, R.; Nuttall, K.; Puls, M.P.; Simpson, L.A.

    1977-01-01

    Mechanisms which have been formulated to describe delayed hydrogen cracking in hydride-forming metals are reviewed and discussed. Particular emphasis is placed on the commercial alloy Zr--2.5% Nb (Cb) which is extensively used in nuclear reactor core components. A quantitative model for hydrogen cracking in this material is presented and compared with available experimental data. The kinetics of crack propagation are controlled by the growth of hydrides at the stressed crack tip by the diffusive ingress of hydrogen into this region. The driving force for the diffusion flux is provided by the local stress gradient which interacts with both hydrogen atoms in solution and hydrogen atoms being dissolved and reprecipitated at the crack tip. The model is developed using concepts of elastoplastic fracture mechanics. Stage I crack growth is controlled by hydrides growing in the elastic stress gradient, while Stage II is controlled by hydride growth in the plastic zone at the crack tip. Recent experimental observations are presented which indicate that the process occurs in an intermittent fashion; hydride clusters accumulate at the crack tip followed by unstable crack advance and subsequent crack arrest in repeated cycles

  6. Mechanisms of hydrogen induced delayed cracking in hydride forming materials

    International Nuclear Information System (INIS)

    Dutton, R.; Nuttall, K.; Puls, M.P.; Simpson, L.A.

    1977-01-01

    Mechanisms which have been formulated to describe delayed hydrogen cracking in hydride-forming metals are reviewed and discussed. Particular emphasis is placed on the commercial alloy Zr-2.5 pct Nb which is extensively used in nuclear reactor core components. A quantitative model for hydrogen cracking in this material is presented and compared with available experimental data. The kinetics of crack propagation are controlled by the growth of hydrides at the stressed crack tip by the diffusive ingress of hydrogen into this region. The driving force for the diffusion flux is provided by the local stress gradient which interacts with both hydrogen atoms in solution and hydrogen atoms being dissolved and reprecipitated at the crack tip. The model is developed using concepts of elastoplastic fracture mechanics. Stage I crack growth is controlled by hydrides growing in the elastic stress gradient, while Stage II is controlled by hydride growth in the plastic zone at the crack tip. Recent experimental observations are presented which indicate that the process occurs in an intermittent fashion; hydride clusters accumulate at the crack tip followed by unstable crack advance and subsequent crack arrest in repeated cycles. 55 refs., 6 figs

  7. Enhancing the muon-catalyzed fusion yield

    International Nuclear Information System (INIS)

    Jones, S.E.

    1987-01-01

    Much has been learned about muon-catalyzed fusion since the last conference on emerging nuclear energy systems. Here the authors consider what they have learned about enhancing the muon-catalyzed fusion energy yield

  8. Study of coupled heat and mass transfer during absorption of ...

    Indian Academy of Sciences (India)

    (iii) The gas phase is ideal from thermodynamic point of view. (iv) Only mass transfer and no heat transfer takes place through the porous filter. (v) The thermal conductivity and specific heat of the hydride bed are assumed to be constant. This assumption underestimates the bed performance slightly, because in actual case ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-09-15

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

  10. Infrared diode laser spectroscopy of lithium hydride

    International Nuclear Information System (INIS)

    Yamada, C.; Hirota, E.

    1988-01-01

    The fundamental and hot bands of the vibration--rotation transitions of 6 LiH, 7 LiH, 6 LiD, and 7 LiD were observed by infrared diode laser spectroscopy at Doppler-limited resolution. Lithium hydride molecules were produced by the reaction of the Li vapor with hydrogen at elevated temperatures. Some 40 transitions were observed and, after combined with submillimeter-wave spectra reported by G. M. Plummer et al. [J. Chem. Phys. 81, 4893 (1984)], were analyzed to yield Dunham-type constants with accuracies more than an order of magnitude higher than those published in the literature. It was clearly demonstrated that the Born--Oppenheimer approximation did not hold, and some parameters representing the breakdown were evaluated. The Born--Oppenheimer internuclear distance r/sup BO//sub e/ was derived to be 1.594 914 26 (59) A, where a new value of Planck's constant recommended by CODATA was employed. The relative intensity of absorption lines was measured to determine the ratio of the permanent dipole moment to its first derivative with respect to the internuclear distance: μ/sub e/ [(partialμpartialr)/sub e/ r/sub e/ ] = 1.743(86). The pressure broadening parameter Δν/sub p/ P was determined to be 6.40 (22) MHzTorr by measuring the linewidth dependence on the pressure of hydrogen, which was about four times larger than the value for the dipole--quadrupole interaction estimated by Kiefer and Bushkovitch's theory

  11. A fractographic distinction between hydride cracking and stress corrosion cracking in zircaloys

    International Nuclear Information System (INIS)

    Cox, B.

    1978-06-01

    The fractographic details of SCC and delayed hydride failures are compared by scanning and replica electron microscopy. It is shown that there are distinct features ascribable to the fracture of hydride platelets which are absent from SCC fractures and which distinguish them from fractures produced by delayed hydride cracking. (author)

  12. Use of triammonium salt of aurin tricarboxylic acid as risk mitigant for aluminum hydride

    Science.gov (United States)

    Cortes-Concepcion, Jose A.; Anton, Donald L.

    2017-08-08

    A process and a resulting product by process of an aluminum hydride which is modified with by physically combining in a ball milling process an aluminum hydride with a triammonium salt of aurin tricarboxylic acid. The resulting product is an aluminum hydride which is resistant to air, ambient moisture, and liquid water while maintaining useful hydrogen storage and release kinetics.

  13. A computer model for hydride blister growth in zirconium alloys

    International Nuclear Information System (INIS)

    White, A.J.; Sawatzky, A.; Woo, C.H.

    1985-06-01

    The failure of a Zircaloy-2 pressure tube in the Pickering unit 2 reactor started at a series of zirconium hydride blisters on the outside of the pressure tube. These blisters resulted from the thermal diffusion of hydrogen to the cooler regions of the pressure tube. In this report the physics of thermal diffusion of hydrogen in zirconium is reviewed and a computer model for blister growth in two-dimensional Cartesian geometry is described. The model is used to show that the blister-growth rate in a two-phase zirconium/zirconium-hydride region does not depend on the initial hydrogen concentration nor on the hydrogen pick-up rate, and that for a fixed far-field temperature there is an optimum pressure-type/calandria-tube contact temperature for growing blisters. The model described here can also be used to study large-scale effects, such as hydrogen-depletion zones around hydride blisters

  14. Hydrides and deuterides of lithium and sodium. Pt. 1

    International Nuclear Information System (INIS)

    Haque, E.

    1990-01-01

    An interionic potential model is developed for lighter and heavier alkali hydrides and deuterides. The method uses a combination of theoretical techniques, empirical fit, and a few plausible assumptions. An assessment of the derived potentials is made by calculating the lattice statics and dynamics of the crystals and by comparing both with experiment (where available) and with other calculations. The potentials are found to describe the elastic and dielectric properties reasonably well. The phonon dispersion curves of hydride and deuteride of sodium are compared with the calculations of Dyck and Jex based on force constant model approach and the results are discussed. The need for further experiments on heavier hydrides and deuterides is stressed. (author)

  15. Research in Nickel/Metal Hydride Batteries 2017

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2018-02-01

    Full Text Available Continuing from a special issue in Batteries in 2016, nineteen new papers focusing on recent research activities in the field of nickel/metal hydride (Ni/MH batteries have been selected for the 2017 Special Issue of Ni/MH Batteries. These papers summarize the international joint-efforts in Ni/MH battery research from BASF, Wayne State University, Michigan State University, FDK Corp. (Japan, Institute for Energy Technology (Norway, Central South University (China, University of Science and Technology Beijing (China, Zhengzhou University of Light Industry (China, Inner Mongolia University of Science and Technology (China, Shenzhen Highpower (China, and University of the Witwatersrand (South Africa from 2016–2017 through reviews of AB2 metal hydride alloys, Chinese and EU Patent Applications, as well as descriptions of research results in metal hydride alloys, nickel hydroxide, electrolyte, and new cell type, comparison work, and projections of future works.

  16. New ternary hydride formation in U-Ti-H system

    International Nuclear Information System (INIS)

    Yamamoto, Takuya; Kayano, Hideo; Yamawaki, Michio.

    1991-01-01

    Hydrogen absorption properties of two titanium-rich uranium alloys, UTi 2 and UTi 4 , were studied in order to prepare and identify the recently found ternary hydride. They slowly reacted with hydrogen of the initial pressure of 10 5 Pa at 873K to form the ternary hydride. The hydrogenated specimen mainly consisted of the pursued ternary hydride but contained also U(or UO 2 ), TiH x , and some transient phases. X-ray powder diffraction and Electron Probe Micro Analysis proved that it was the UTi 2 H x with the expected MgCu 2 structure, though all the X-ray peaks were broad probably because of inhomogeneity. This compound had extremely high resistance to powdering on its formation, which showed high potential utilities for a non-powdering tritium storage system or for other purposes. (author)

  17. Hydrogen bonding between hydrides of the upper-right part of the periodic table

    Science.gov (United States)

    Simončič, Matjaž; Urbic, Tomaz

    2018-05-01

    One of the most important electrostatic interactions between molecules is most definitely the hydrogen bond. Understanding the basis of this interaction may offer us the insight needed to understand its effect on the macroscopic scale. Hydrogen bonding is for example the reason for anomalous properties in compounds like water and naturally life as we know it. The strength of the bond depends on numerous factors, among them the electronegativity of participating atoms. In this work we calculated the strength of hydrogen bonds between hydrides of the upper-right part of the periodic table (C, N, O, F, P, S, Cl, As, Se, Br) using quantum-chemical methods. The aim was to determine what influences the strength of strong and weak hydrogen bonds in simple hydrides. Various relationships were checked. A relation between the strength of the bond and the electronegativity of the participating atoms was found. We also observed a correlation between the strength of hydrogen bonds and the inter-atomic distances, along with the dependence on the charge transfer on the atom of the donor. We also report characteristic geometries of different dimers.

  18. Complex Metal Hydrides for Hydrogen, Thermal and Electrochemical Energy Storage

    DEFF Research Database (Denmark)

    Moller, Kasper T.; Sheppard, Drew; Ravnsbaek, Dorthe B.

    2017-01-01

    Hydrogen has a very diverse chemistry and reacts with most other elements to form compounds, which have fascinating structures, compositions and properties. Complex metal hydrides are a rapidly expanding class of materials, approaching multi-functionality, in particular within the energy storage...... inspiration to solve the great challenge of our time: efficient conversion and large-scale storage of renewable energy....... field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...

  19. Microcapsulated rare earth - nickel hydride-forming materials

    International Nuclear Information System (INIS)

    Ishikawa, H.; Oguro, K.; Kato, A.; Suzuki, H.; Ishii, E.

    1985-01-01

    Fine particles of hydride-forming alloys such as LaNi/sub 5/ and MmNi/sub 4.5/Mn/sub 0.5/ (MM : mischmetal) were coated with metallic copper thin layer by chemical plating method. Hydrogen storage capacities of alloys were not appreciably affected by the plating treatment. The capsulated alloy powders were easily pressed into pellets. The pellets obtained had high thermal conductivity and porosity enough to permeate hydrogen, leading to fast reaction kinetics. These were able to withstand more than 5,000 repeated hydriding-dehydriding cycles without disintegrating

  20. Hydriding and dehydriding properties of CaSi

    International Nuclear Information System (INIS)

    Aoki, Masakazu; Ohba, Nobuko; Noritake, Tatsuo; Towata, Shin-ichi

    2005-01-01

    The hydriding and dehydriding properties of CaSi were investigated both theoretically and experimentally. First-principles calculations suggested that CaSiH n is thermodynamically stable. Experimentally, the p -c isotherms clearly demonstrated plateau pressures in a temperature range of 473-573 K and the maximum hydrogen content was 1.9 weight % (wt.%) under a hydrogen pressure of 9 MPa at 473 K. The structure of CaSiH n is different from those of ZrNi hydrides, although CaSi has the CrB-type structure as well as ZrNi

  1. Thermophysical properties of solid lithium hydride and its isotopic modifications

    International Nuclear Information System (INIS)

    Mel'nikova, T.N.

    1981-01-01

    The theory of the anharmonic lattice is used to calculate the thermophysical properties (thermal expansivity, lattice constant, compressibility, and elastic moduli) of all the isotopic modifications of solid lithium hydride sup(6,7)Li(H,D,T) at temperatures up to the melting point. A general analysis of isotopic effects is carried out; in particular the reverse isotopic effect in the lattice constant is explained and the isotopic effect in melting is discussed. The results of the calculations agree with available experimental data and can be used for those isotopic modifications of lithium hydride for which there exist no experimental results. (author)

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

    KAUST Repository

    Werghi, Baraa; Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Jedidi, Abdesslem; Abou-Hamad, Edy; Cavallo, Luigi; Basset, Jean-Marie

    2015-01-01

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

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

    KAUST Repository

    Werghi, Baraa

    2015-07-17

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

  4. Fluorinated cobalt for catalyzing hydrogen generation from sodium borohydride

    Energy Technology Data Exchange (ETDEWEB)

    Akdim, O.; Demirci, U.B.; Brioude, A.; Miele, P. [Laboratoire des Multimateriaux et Interfaces, UMR 5615 CNRS Universite Lyon 1, Universite de Lyon, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne (France)

    2009-07-15

    The present paper reports preliminary results relating to a search for durable cobalt-based catalyst intended to catalyze the hydrolysis of sodium borohydride (NaBH{sub 4}). Fluorination of Co [Suda S, Sun YM, Liu BH, Zhou Y, Morimitsu S, Arai K, et al. Catalytic generation of hydrogen by applying fluorinated-metal hydrides as catalysts. Appl Phys A 2001; 72: 209-12.] has attracted our attention whereas the fluorination of Co boride has never been envisaged so far. Our first objective was to compare the reactivity of fluorinated Co with that of Co boride. We focused our attention on the formation of Co boride from fluorinated Co. Our second objective was to show the fluorination effect on the reactivity of Co. Our third objective was to find an efficient, durable Co catalyst. It was observed a limited stabilization of the Co surface by virtue of the fluorination, which made the formation of surface Co boride more difficult while the catalytic activity was unaltered. The fluorination did not affect the number of surface active sites. Nevertheless, it did not prevent the formation of Co boride. The fluorination of Co boride was inefficient. Hence, fluorination is a way to gain in stabilization of the catalytic surface but it is quite inefficient to hinder the boride formation. Accordingly, it did not permit to compare the reactivity of Co boride with that of Co. (author)

  5. Theoretical insights into the sites and mechanisms for base catalyzed esterification and aldol condensation reactions over Cu.

    Science.gov (United States)

    Neurock, Matthew; Tao, Zhiyuan; Chemburkar, Ashwin; Hibbitts, David D; Iglesia, Enrique

    2017-04-28

    Condensation and esterification are important catalytic routes in the conversion of polyols and oxygenates derived from biomass to fuels and chemical intermediates. Previous experimental studies show that alkanal, alkanol and hydrogen mixtures equilibrate over Cu/SiO 2 and form surface alkoxides and alkanals that subsequently promote condensation and esterification reactions. First-principle density functional theory (DFT) calculations were carried out herein to elucidate the elementary paths and the corresponding energetics for the interconversion of propanal + H 2 to propanol and the subsequent C-C and C-O bond formation paths involved in aldol condensation and esterification of these mixtures over model Cu surfaces. Propanal and hydrogen readily equilibrate with propanol via C-H and O-H addition steps to form surface propoxide intermediates and equilibrated propanal/propanol mixtures. Surface propoxides readily form via low energy paths involving a hydrogen addition to the electrophilic carbon center of the carbonyl of propanal or via a proton transfer from an adsorbed propanol to a vicinal propanal. The resulting propoxide withdraws electron density from the surface and behaves as a base catalyzing the activation of propanal and subsequent esterification and condensation reactions. These basic propoxides can readily abstract the acidic C α -H of propanal to produce the CH 3 CH (-) CH 2 O* enolate, thus initiating aldol condensation. The enolate can subsequently react with a second adsorbed propanal to form a C-C bond and a β-alkoxide alkanal intermediate. The β-alkoxide alkanal can subsequently undergo facile hydride transfer to form the 2-formyl-3-pentanone intermediate that decarbonylates to give the 3-pentanone product. Cu is unique in that it rapidly catalyzes the decarbonylation of the C 2n intermediates to form C 2n-1 3-pentanone as the major product with very small yields of C 2n products. This is likely due to the absence of Brønsted acid sites

  6. Observations on Hydride Structures at the Tip of Arrested Cracks Grown under Conditions of Delayed Hydride Cracking

    International Nuclear Information System (INIS)

    Pettersson, Kjell; Oskarsson, Magnus; Bergqvist, Hans

    2003-04-01

    One sample of Zr2.5%Nb and one sample of cold worked and stress relieved Zircaloy-4 which have been tested for hydrogen induced crack growth have been examined in the crack tip region with the aim of determining the mechanism behind the growth of cracks. The proposed mechanisms are brittle failure of a crack tip hydride and hydrogen enhanced localized shear. The examinations were done by TEM and SEM. However attempts to produce a TEM specimen with a thinned region at the tip of the crack were unsuccessful in both samples. One feature observed in the Zr2.5%Nb material may however be an indication of intense shear deformation at the tip of the crack. On the other hand all observations on the Zircaloy-4 sample indicate precipitation of hydrides ahead of the crack tip and the presence of hydrides on the crack flanks

  7. A comparison of the smeared-dislocation and super-dislocation description of a hydrided region in the context of modelling delayed hydride cracking initiation

    International Nuclear Information System (INIS)

    Smith, E.

    1994-01-01

    In quantifying the stress distribution within a hydrided region in the context of modelling delayed hydride cracking (DHC) initiation in zirconium alloys, this paper highlights the desirability of accounting for image effects, i.e. the interaction between the hydrided region and any free surface, for example a sharp crack, blunt notch or planar surface. The super-dislocation representation of a finite thickness hydrided region is ideal for accounting for image effects. It also adequately accounts for the finite thickness, t, of a hydrided region provided, as is the case in practice, we are concerned with the stress value within the hydride at distances ≥ 0.25 t from an end of the region. (Author)

  8. Delayed hydride cracking in zirconium alloys in pressure tube nuclear reactors. Final report of a coordinated research project 1998-2002

    International Nuclear Information System (INIS)

    2004-10-01

    This report describes all of the research work undertaken as part of the IAEA coordinated research project on hydrogen and hydride induced degradation of the mechanical and physical properties of zirconium based alloys, and includes a review of the state of the art in understanding crack propagation by Delayed Hydride Cracking (DHC), and details of the experimental procedures that have produced the most consistent set of DHC rates reported in an international round-robin exercise to this date. It was concluded that 1) the techniques for performing measurements of the rate of delayed hydride cracking in zirconium alloys have been transferred from the host laboratory to other countries; 2) by following a strict procedure, a very consistent set of values of crack velocity were obtained by both individual laboratories and between the different laboratories; 3) the results over a wide range of test temperatures from materials with various microstructures fitted into the current theoretical framework for delayed hydride cracking; 4) an inter-laboratory comparison of hydrogen analysis revealed the importance of calibration and led to improvements in measurement in the participating laboratories and 5) the success of the CRP in achieving its goals has led to the initiation of some national programmes

  9. cis-Stilbene and (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)benzene as mechanistic probes in the Mn(III)(salen)-catalyzed epoxidation: influence of the oxygen source and the counterion on the diastereoselectivity of the competitive concerted and radical-type oxygen transfer.

    Science.gov (United States)

    Adam, Waldemar; Roschmann, Konrad J; Saha-Möller, Chantu R; Seebach, Dieter

    2002-05-08

    cis-Stilbene (1) has been epoxidized by a set of diverse oxygen donors [OxD], catalyzed by the Mn(III)(salen)X complexes 3 (X = Cl, PF(6)), to afford a mixture of cis- and trans-epoxides 2. The cis/trans ratios range from 29:71 (extensive isomerization) to 92:8, which depends both on the oxygen source [OxD] and on the counterion X of the catalyst. When (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)-benzene (4) is used as substrate, a mechanistic probe which differentiates between radical and cationic intermediates, no cationic ring-opening products are found in this epoxidation reaction; thus, isomerized epoxide product arises from intermediary radicals. The dependence of the diastereoselectivity on the oxygen source is rationalized in terms of a bifurcation step in the catalytic cycle, in which concerted Lewis-acid-activated oxygen transfer competes with stepwise epoxidation by the established Mn(V)(oxo) species. The experimental counterion effect is attributed to the computationally assessed ligand-dependent reaction profiles and stereoselectivities of the singlet, triplet, and quintet spin states available to the manganese species.

  10. Characteristics of hydride precipitation and reorientation in spent-fuel cladding

    International Nuclear Information System (INIS)

    Chung, H.M.; Daum, R.S.; Hiller, J.M.; Billone, M.C.

    2002-01-01

    Transmission electron microscopy (TEM) was used to examine Zircaloy fuel cladding, either discharged from several PWRs and a BWR after irradiation to fluence levels of 3.3 to 8.6 X 10 21 n cm -2 (E > 1 MeV) or hydrogen-charged and heat-treated under stress to produce radial hydrides; the goal was to determine the microstructural and crystallographic characteristics of hydride precipitation. Morphologies, distributions, and habit planes of various types of hydrides were determined by stereo-TEM. In addition to the normal macroscopic hydrides commonly observed by optical microscopy, small 'microscopic' hydrides are present in spent-fuel cladding in number densities at least a few orders of magnitude greater than that of macroscopic hydrides. The microscopic hydrides, observed to be stable at least up to 333 deg C, precipitate in association with -type dislocations. While the habit plane of macroscopic tangential hydrides in the spent-fuel cladding is essentially the same as that of unirradiated unstressed Zircaloys, i.e., the [107] Zr plane, the habit plane of tangential hydrides that precipitate under high tangential stress is the [104] Zr plane. The habit plane of radial hydrides that precipitate under tangential stress is the [011] Zr pyramidal plane, a naturally preferred plane for a cladding that has 30 basal-pole texture. Effects of texture on the habit plane and the threshold stress for hydride reorientation are also discussed. (authors)

  11. In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

    Energy Technology Data Exchange (ETDEWEB)

    Cinbiz, Mahmut N., E-mail: cinbizmn@ornl.gov [Department of Mechanical and Nuclear Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Koss, Donald A., E-mail: koss@ems.psu.edu [Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Motta, Arthur T., E-mail: atm2@psu.edu [Department of Mechanical and Nuclear Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Park, Jun-Sang, E-mail: parkjs@aps.anl.gov [Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439 (United States); Almer, Jonathan D., E-mail: almer@aps.anl.gov [Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439 (United States)

    2017-04-15

    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. - Highlights: •The δ{111} d-spacings aligned with the hydride plate edges exhibit a bi-linear thermal expansion. •Stress state reversal is predicted with the onset of hydride dissolution. •During dissolution, the δ{111} planes oriented parallel to the hydride plate face initially contract upon heating. •Hydride d-spacings indicate that both in-plane (circumferential) and out-of-plane (radial) hydrides are in the same strain-state and likely in the same stress state as well.

  12. Quantifying the stress fields due to a delta-hydride precipitate in alpha-Zr matrix

    Energy Technology Data Exchange (ETDEWEB)

    Tummala, Hareesh [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Capolungo, Laurent [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tome, Carlos N. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-10-19

    This report is a preliminary study on δ-hydride precipitate in zirconium alloy performed using 3D discrete dislocation dynamics simulations. The ability of dislocations in modifying the largely anisotropic stress fields developed by the hydride particle in a matrix phase is addressed for a specific dimension of the hydride. The influential role of probable dislocation nucleation at the hydride-matrix interface is reported. Dislocation nucleation around a hydride was found to decrease the shear stress (S13) and also increase the normal stresses inside the hydride. We derive conclusions on the formation of stacks of hydrides in zirconium alloys. The contribution of mechanical fields due to dislocations was found to have a non-negligible effect on such process.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-04-01

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

  14. Internal friction study of hydrides in zirconium at low hydrogen contents

    International Nuclear Information System (INIS)

    Peretti, H.A.; Corso, H.L.; Gonzalez, O.A.; Fernandez, L.; Ghilarducci, A.A.; Salva, H.R.

    1999-01-01

    Full text: Internal friction and shear modulus measurements were carried out on crystal bar zirconium in the as received and hydride conditions using an inverted forced pendulum. Hydriding was achieved in two ways: inside and out of the pendulum. The final hydrogen content determined by fusion analysis in the 'in situ' hydride sample was of 36 ppm. Another sample was hydride by the cathodic charge method with 25 ppm. The thermal solid solubility (TSS) phase boundary presents hysteresis between the precipitation (TSSP) and the dissolution (TSSD) temperatures for the zirconium hydrides. During the first thermal cycling the anelastic effects could be attributed to the δ, ε and metastable γ zirconium hydrides. After 'in situ' annealing at 490 K, these peaks completely disappear in the electrolytically charged sample, while in the 'in situ' hydride, the peaks remain with decreasing intensity. This effect can be understood in terms of the different surface conditions of the samples. (author)

  15. Dislocation/hydrogen interaction mechanisms in hydrided nanocrystalline palladium films

    International Nuclear Information System (INIS)

    Amin-Ahmadi, Behnam; Connétable, Damien; Fivel, Marc; Tanguy, Döme; Delmelle, Renaud; Turner, Stuart; Malet, Loic; Godet, Stephane; Pardoen, Thomas; Proost, Joris; Schryvers, Dominique

    2016-01-01

    The nanoscale plasticity mechanisms activated during hydriding cycles in sputtered nanocrystalline Pd films have been investigated ex-situ using advanced transmission electron microscopy techniques. The internal stress developing within the films during hydriding has been monitored in-situ. Results showed that in Pd films hydrided to β-phase, local plasticity was mainly controlled by dislocation activity in spite of the small grain size. Changes of the grain size distribution and the crystallographic texture have not been observed. In contrast, significant microstructural changes were not observed in Pd films hydrided to α-phase. Moreover, the effect of hydrogen loading on the nature and density of dislocations has been investigated using aberration-corrected TEM. Surprisingly, a high density of shear type stacking faults has been observed after dehydriding, indicating a significant effect of hydrogen on the nucleation energy barriers of Shockley partial dislocations. Ab-initio calculations of the effect of hydrogen on the intrinsic stable and unstable stacking fault energies of palladium confirm the experimental observations.

  16. A system of hydrogen powered vehicles with liquid organic hydrides

    International Nuclear Information System (INIS)

    Taube, M.

    1981-07-01

    A motor car system based on the hydrogen produced by nuclear power stations during the night in the summer, and coupled with organic liquid hydride seems to be a feasible system in the near future. Such a system is discussed and the cost is compared with gasoline. (Auth.)

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

    Science.gov (United States)

    Congdon, James W [Aiken, SC

    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.

  18. Hydrogen storage alloys for nickel/metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Kuriyama, Nobuhiro; Sakai, Tetsuo; Myamura, Hiroshi; Tanaka, Hideaki; Ishikawa, Hiroshi; Uehara, Itsuki [Osaka National Research Inst. (Japan)

    1996-06-01

    Efforts to improve performance of metal hydride electrodes such as substitution of alloy components, heat treatment, and surface treatment intended to change surface and bulk structure of hydrogen storage alloys, mainly LaNi{sub 5} based alloys, are reviewed. The importance of control of morphology is emphasized. (author)

  19. Cascades for hydrogen isotope separation using metal hydrides

    International Nuclear Information System (INIS)

    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

  20. Deiodination reactions using tributyltin hydride for potential labelling experiments

    International Nuclear Information System (INIS)

    Zippi, E.M.; Plourde, G.W. II; Satyamurthy, N.

    1995-01-01

    2,6-Dinitro-1-iodobenzene and 2,4-dinitro-1-iodobenzene were deiodinated with tributylin hydride at different temperatures using various addition modes. The product ratios of 1,3-dinitrobenzene and the corresponding tributylstannyldinitrobenzene compounds were determined by NMR in order to evaluate the optimum conditions for impending tritiation experiments. (Author)

  1. Metal Hydride assited contamination on Ru/Si surfaces

    NARCIS (Netherlands)

    Pachecka, Malgorzata; Lee, Christopher James; Sturm, Jacobus Marinus; Bijkerk, Frederik

    2013-01-01

    In extreme ultraviolet lithography (EUVL) residual tin, in the form of particles, ions, and atoms, can be deposited on nearby EUV optics. During the EUV pulse, a reactive hydrogen plasma is formed, which may be able to react with metal contaminants, creating volatile and unstable metal hydrides that

  2. Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

    OpenAIRE

    Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Jr., Cláudio; Victor, Maurício M.; Silveira, Leandro G. da

    2008-01-01

    Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride®) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring.

  3. Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

    International Nuclear Information System (INIS)

    Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Junior, Claudio; Victor, Mauricio M.; Silveira, Leandro G. da

    2008-01-01

    Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride R ) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring. (author)

  4. Fractal analysis of electrolytically-deposited palladium hydride dendrites

    International Nuclear Information System (INIS)

    Bursill, L.A.; Julin, Peng; Xudong, Fan.

    1990-01-01

    The fractal scaling characteristics of the surface profile of electrolytically-deposited palladium hydride dendritic structures have been obtained using conventional and high resolution transmission electron microscopy. The results are in remarkable agreement with the modified diffusion-limited aggregation model. 19 refs., 3 tabs., 13 figs

  5. Development of transmutation technologies of radioactive waste by actinoid hydride

    International Nuclear Information System (INIS)

    Konashi, Kenji; Matsui, Hideki; Yamawaki, Michio

    2001-01-01

    Two waste treatment methods, geological disposal and transmutation, have been studied. The transmutation method changes long-lived radioactive nuclides to short-lived one or stabilizes them by nuclear transformation. The transmutation by actinoid hydride is exactly alike that transformation method from actinoid disposal waste to Pu fuel. For this object, OMEGA project is processing now. The transmutation is difficult by two causes such as large amount of long-lived radioactive nuclides and not enough development of control technologies of nuclear reaction except atomic reactor. The transmutation using actinoid hydride has merits that the amount of actinoid charged in the target increases and the effect of thermal neutrons on fuel decreases depending on homogeneous transmutation velocity in the target. Development of stable actinoid hydride under the conditions of reactor temperature and irradiation environment is important. The experimental results of U-ZrH 1.6 are shown in this paper. The irradiation experiment using Th hydride has been proceeding. (S.Y.)

  6. Hydrogen and dihydrogen bonding of transition metal hydrides

    International Nuclear Information System (INIS)

    Jacobsen, Heiko

    2008-01-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2 NO(PH 3 ) 2 and a small proton donor H 2 O 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

  7. Hydrogen and dihydrogen bonding of transition metal hydrides

    Science.gov (United States)

    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.

  8. Hydrogen and dihydrogen bonding of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jacobsen, Heiko [KemKom, Libellenweg 2, 25917 Leck, Nordfriesland (Germany)], E-mail: jacobsen@kemkom.com

    2008-04-03

    Intermolecular interactions between a prototypical transition metal hydride WH(CO){sub 2}NO(PH{sub 3}){sub 2} and a small proton donor H{sub 2}O 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.

  9. Cascades for hydrogen isotope separation using metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Hill, F B; Grzetic, V [Brookhaven National Lab., Upton, NY (USA)

    1983-02-01

    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.

  10. Diffusion model of delayed hydride cracking in zirconium alloys

    NARCIS (Netherlands)

    Shmakov, AA; Kalin, BA; Matvienko, YG; Singh, RN; De, PK

    2004-01-01

    We develop a method for the evaluation of the rate of delayed hydride cracking in zirconium alloys. The model is based on the stationary solution of the phenomenological diffusion equation and the detailed analysis of the distribution of hydrostatic stresses in the plane of a sharp tensile crack.

  11. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen

  12. The Properties of Some Simple Covalent Hydrides: An Ab Initio ...

    African Journals Online (AJOL)

    Some properties of the monomeric binary hydrides of the elements of the first two rows of the periodic table have been determined using ab initio molecular orbital theory. The properties in question are the energetic, structural, electronic, topological and vibrational characteristics. In general, a gradual convergence towards ...

  13. Synthesis, properties, and assimilation methods of aluminium hydride

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.

    2013-01-01

    We have discovered a new source of aluminium hydride-conversion of tetrahydrofurane under influence of halogenous alkyls. We have proposed the chlorbenzene method of synthesis of AlH 3 , which excludes adhesion and ensure high quality of the product with respect to its purity, thermal stability, habits of crystals (round shape), and granulometric composition. We determined capability of benzyl chloride to fix AlH 4 -groups by the way of complexes formation. This allows increasing efficient concentration of AlH 3 solutions and their productivity. We have carried out 'direct' crystallization of aluminium hydride in one stage using interaction of binary metal hydride with aluminium chloride in the medium of ether-toluene at 60-100 d ig C a nd using solvent distillation. In the reaction of Li H with AlCl 3 , we achieved output of pure crystal AlH 3 of hexagonal modification, which was close to quantitative. We have discovered the assimilation methods of aluminium hydride in carrying out of solid-phase chemical reactions. (author)

  14. Activation and discharge kinetics of metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, Stein Egil

    2003-07-01

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

  15. Exploring possible reaction pathways for the o-atom transfer reactions to unsaturated substrates catalyzed by a [Ni-NO2 ] ↔ [Ni-NO] redox couple using DFT methods.

    Science.gov (United States)

    Tsipis, Athanassios C

    2017-07-15

    The (nitro)(N-methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex catalyses efficiently the O-atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] ↔ Ni(NO 2 )(S 2 CNHMe)(PMe 3 ) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five-member metallacycle intermediate, via a [3 + 2] cyclo-addition reaction of HC≡CH to the Ni-N = O moiety of the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex, followed by a β H-atom migration toward the C α carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( κN1-NO 2 )(S 2 CNHMe)(PMe 3 )] ⇌ [Ni( κO,O2-ONO)(S 2 CNHMe)(PMe 3 )] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  16. Experimental and Theoretical Mechanistic Investigation of the Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Singh, Thishana; Harris, Pernille

    2015-01-01

    The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving...... cycles. One carbon monoxide ligand was shown to remain coordinated to iridium throughout the reaction, and release of carbon monoxide was suggested to occur from a dicarbonyl complex. IrH2Cl(CO)(rac-BINAP) was also synthesized and detected in the dehydrogenation of benzyl alcohol. In the same experiment......, IrHCl2(CO)(rac-BINAP) was detected from the release of HCl in the dehydrogenation and subsequent reaction with IrCl(CO)(rac-BINAP). This indicated a substitution of chloride with the alcohol to form a square planar iridium alkoxo complex that could undergo a beta-hydride elimination. A KIE of 1...

  17. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  18. Hydride redistribution and crack growth in Zr-2.5 wt.% Nb stressed in torsion

    International Nuclear Information System (INIS)

    Puls, M.P.; Rogowski, A.J.

    1980-11-01

    The effect of applied shear stresses on zirconium hydride solubility in a zirconium alloy was investigated. Recent studies have shown that zirconium hydride precipiates probably nucleate and grow by means of a shear transformation mechanism. It is postulated that these transformation shear strains can interact with applied shear stress gradients in the same way that the dilatational strains can interact with a dilatational stress gradient, providing a driving force for hydride accumulation, hydride embrittlement and crack propagation. To test this proposition, crack growth experiments were carried out under torsional loading conditions on hydrided, round notched bar specimens of cold-worked Zr-2.5 wt.% Nb cut from Pickering-type pressure tube material. Postmortem metallographic examination of the hydride distribution in these samples showed that, in many cases, the hydrides appeared to have reoriented in response to the applied shear stress and that hydride accumulation at the notch tip had occurred. However, except in a few cases, the rate of accumulation of reoriented hydrides at the notch tip due to applied shear stresses was much less than the rate due to corresponding applied uniaxial stresss. Moreover, the process in shear appears to be more sensitive to the inital hydride size. Attempts to elucidate the fracture mechanism by fractographic examination using scanning and replica transmission electron microscopy proved to be inconclusive because of smearing of the fracture face. (auth)

  19. High pressure hydriding of sponge-Zr in steam-hydrogen mixtures

    International Nuclear Information System (INIS)

    Kim, Y.S.

    1997-01-01

    Hydriding kinetics of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk has been studied by thermogravimetry in the temperature range 350-400 C in 7 MPa hydrogen-steam mixtures. Some specimens were prefilmed with a thin oxide layer prior to exposure to the reactant gas; all were coated with a thin layer of gold to avoid premature reaction at edges. Two types of hydriding were observed in prefilmed specimens, viz., a slow hydrogen absorption process that precedes an accelerated (massive) hydriding. At 7 MPa total pressure, the critical ratio of H 2 /H 2 O above which massive hydriding occurs at 400 C is ∝200. The critical H 2 /H 2 O ratio is shifted to ∝2.5 x 10 3 at 350 C. The slow hydriding process occurs only when conditions for hydriding and oxidation are approximately equally favorable. Based on maximum weight gain, the specimen is completely converted to δ-ZrH 2 by massive hydriding in ∝5 h at a hydriding rate of ∝10 -6 mol H/cm 2 s. Incubation times of 10-20 h prior to the onset of massive hydriding increases with prefilm oxide thickness in the range of 0-10 μm. By changing to a steam-enriched gas, massive hydriding that initially started in a steam-starved condition was arrested by re-formation of a protective oxide scale. (orig.)

  20. Novel big-bang element synthesis catalyzed by supersymmetric particle stau

    International Nuclear Information System (INIS)

    Kamimura, Masayasu; Kino, Yasushi; Hiyama, Emiko

    2010-01-01

    The extremely low isotope ratio of 6 Li had remained as a drawback of the Big-Bang Nucleosynthesis (BBN) until Pospelov proposed the 6 Li synthesis reaction catalyzed by negatively charged electroweak-scale particle X - in 2006. He remarked the catalytic enhancement of 6 Li production by about 10 8 times, as well as the life and initial abundance of X - . The present authors classified BBN catalyzed reaction into six types, i.e. (1) non-resonant transfer, (2) resonant transfer, (3) non-resonant radiative capture, (4) resonant radiative capture, (5) three-body breakup and (6) charge transfer reactions to predict absolute values of cross sections which cannot be observed experimentally. Starting from the three-body treatment for those reactions, 6 Li problems, the life-time and abundance of stau are discussed. Large change of element composition at 'late-time' big bang, generation of 9 Be by stau catalyzed reaction, 7 Li problem and stau catalyzed reactions are also discussed. Finally their relations with the supersymmetry theory and dark matter are mentioned. The basic nuclear calculations are providing quantitative base for the 'effect of nuclear reactions catalyzed by the supersymmetric particle stau on big bang nucleosynthesis'. (S. Funahashi)

  1. Sodium hydride precipitation in sodium cold traps

    International Nuclear Information System (INIS)

    McPheeters, C.C.; Raue, D.J.

    1980-06-01

    A series of experiments have been performed to test a calculational model for precipitation of NaH in sodium cold traps. The calculational model, called ACTMODEL, is a computer simulation that uses the system geometry and operating conditions as input to calculate a mass-transfer coefficient and the distribution of NaH in a cold trap. The ACTMODEL was tested using an analytical cold trap (ACT) that is simple and essentially one-dimensional. The ACT flow and temperature profile can be controlled at any desired condition. The ACT was analyzed destructively after each test to measure the actual NaH distribution. Excellent agreement was obtained between the ACTMODEL simulations and the experiments. Mass-transfer coefficients ranging upward from 6 x 10 -5 m/s were measured in both packless and packed traps. As much as a fourfold increase in precipitation surface area was observed with increasing amount of NaH deposited. 11 figures, 2 tables

  2. Catalytic effect of halide additives ball milled with magnesium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Malka, I.E.; Bystrzycki, J. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); Czujko, T. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); CanmetENERGY, Hydrogen Fuel Cells and Transportation Energy, Natural Resources (Canada)

    2010-02-15

    The influence of various halide additives milled with magnesium hydride (MgH{sub 2}) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated. The MgH{sub 2} decomposition temperature and energy of activation reduction were measured by temperature programmed desorption (TPD) and differential scanning calorimetry (DSC). The difference in catalytic efficiency between chlorides and fluorides of the various metals studied is presented. The effects of oxidation state, valence and position in the periodic table for selected halides on MgH{sub 2} decomposition temperature were also studied. The best catalysts, from the halides studied, for magnesium hydride decomposition were ZrF{sub 4}, TaF{sub 5}, NbF{sub 5}, VCl{sub 3} and TiCl{sub 3}. (author)

  3. Irradiation effects on thermal properties of LWR hydride fuel

    Energy Technology Data Exchange (ETDEWEB)

    Terrani, Kurt, E-mail: terrani@berkeley.edu [University of California, 4155 Etcheverry Hall, M.C. 1730, Berkeley, CA 94720-1730 (United States); Balooch, Mehdi [University of California, 4155 Etcheverry Hall, M.C. 1730, Berkeley, CA 94720-1730 (United States); Carpenter, David; Kohse, Gordon [Massachusetts Institute of Technology, 138 Albany St., Cambridge, MA 02139 (United States); Keiser, Dennis; Meyer, Mitchell [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Olander, Donald [University of California, 4155 Etcheverry Hall, M.C. 1730, Berkeley, CA 94720-1730 (United States)

    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%)ZrH{sub 1.6}) 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.

  4. Positronium hydride defects in thermochemically reduced alkaline-Earth oxides

    International Nuclear Information System (INIS)

    Monge, M.A.; Pareja, R.; Gonzalez, R.; Chen, Y.

    1997-01-01

    Thermochemical reduction of both hydrogen-doped MgO and CaO single crystals results in large concentrations of hydride (H - ) ions. In MgO crystals, positron lifetime and Doppler broadening experiments show that positrons are trapped at H - centers forming positronium hydride molecules [e + - H - ]. A value of 640 ps is obtained for the lifetime of the PsH states located in an anion vacancy In MgO positrons are also trapped at H 2- sites at low temperatures. The H 2- ions were induced in the crystals by blue light illumination. The formation of PsH states in CaO could not be conclusively established. (orig.)

  5. FEASIBILITY OF RECYCLING PLUTONIUM AND MINOR ACTINIDES IN LIGHT WATER REACTORS USING HYDRIDE FUEL

    International Nuclear Information System (INIS)

    Greenspan, Ehud; Todreas, Neil; Taiwo, Temitope

    2009-01-01

    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; and (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

  6. Neutron scattering study of the phase transformation of LaNi3 induced by hydriding

    International Nuclear Information System (INIS)

    Ruan Jinghui; Zeng Xiangxin; Niu Shiwen

    1994-01-01

    The phase transformation of LaNi 3 induced by hydriding and de-hydriding is investigated using the neutron diffraction and the neutron inelastic scattering. The results show that the hydriding sample, LaNi 3 H x , is transformed from crystalline state of the LaNi 3 into amorphous state with a microcrystalline characteristic of LaNi 5 , and the de-hydriding sample produced by LaNi 3 H x dehydrated at 600 degree C is decomposed into new crystalline states composed by LaNi 5 -and La-hydrides. The procedure of phase transformation is that the result of the transformation of LaNi 3 induced by hydriding shows the properties of LaNi 5 -H 2 system

  7. FEASIBILITY OF RECYCLING PLUTONIUM AND MINOR ACTINIDES IN LIGHT WATER REACTORS USING HYDRIDE FUEL

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Thermomechanics of hydrogen storage in metallic hydrides: modeling and analysis

    Czech Academy of Sciences Publication Activity Database

    Roubíček, Tomáš; Tomassetti, G.

    2014-01-01

    Roč. 19, č. 7 (2014), s. 2313-2333 ISSN 1531-3492 R&D Projects: GA ČR GA201/09/0917 Institutional support: RVO:61388998 Keywords : metal-hydrid phase transformation * hydrogen diffusion * swelling Subject RIV: BA - General Mathematics Impact factor: 0.768, year: 2014 http://aimsciences.org/journals/pdfs.jsp?paperID=10195&mode=full

  9. Magnetization study of UNiSi and its hydride

    Czech Academy of Sciences Publication Activity Database

    Šebek, Josef; Andreev, Alexander V.; Honda, F.; Kolomiets, A. V.; Havela, L.; Sechovský, V.

    2003-01-01

    Roč. 34, č. 2 (2003), s. 1457-1460 ISSN 0587-4254. [International Conference on Strongly Correlated Electron Systems (SCES 02). Cracow, 10.07.2002-13.07.2002] R&D Projects: GA ČR GA202/02/0739 Institutional research plan: CEZ:AV0Z1010914; CEZ:MSM 113200002 Keywords : UNiSi * magnetic measurements * hydride Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.752, year: 2003

  10. Instrinsic defect energies of lithium hydride and lithium deuteride crystals

    International Nuclear Information System (INIS)

    Pandey, R.; Stoneham, A.M.

    1985-01-01

    A theoretical study has been made of the defect structure of lithium hydride and lithium deuteride. A potential model is obtained describing the statics and dynamics of these crystals. Intrinsic defect energies are calculated using the Harwell HADES program which is based on a generalised Mott-Littleton method. The results are in good agreement with the experimental data, and suggest that the vacancy and interstitial migration mechanisms of anions and cations are all comparable in their contribution to ionic conduction. (author)

  11. Equilibrium dissociation pressures of lithium hydride and lithium deuteride

    International Nuclear Information System (INIS)

    Smith, H.M.; Webb, R.E.

    1977-12-01

    The equilibrium dissociation pressures of plateau composition lithium hydride and lithium deuteride have been measured from 450 to 750 0 C. These data were used to derive the relationship of dissociation pressure with temperature over this range and to calculate several thermodynamic properties of these materials. Thermodynamic properties determined included the enthalpy, entropy, and free energy of formation; the enthalpy and entropy of fusion; and the melting points

  12. Dendritic surface morphology of palladium hydride produced by electrolytic deposition

    International Nuclear Information System (INIS)

    Julin, Peng; Bursill, L.A.

    1990-01-01

    Conventional and high-resolution electron microscopic studies of electrolytically-deposited palladium hydride reveal a fascinating variety of surface profile morphologies. The observations provide direct information concerning the surface structure of palladium electrodes and the mechanism of electrolytic deposition of palladium black. Both classical electrochemical mechanisms and recent 'modified diffusion-limited-aggregation' computer simulations are discussed in comparison with the experimental results. 13 refs., 9 figs

  13. Secondary hydriding of defected zircaloy-clad fuel rods

    International Nuclear Information System (INIS)

    Olander, D.R.; Vaknin, S.

    1993-01-01

    The phenomenon of secondary hydriding in LWR fuel rods is critically reviewed. The current understanding of the process is summarized with emphasis on the sources of hydrogen in the rod provided by chemical reaction of water (steam) introduced via a primary defect in the cladding. As often noted in the literature, the role of hydrogen peroxide produced by steam radiolysis is to provide sources of hydrogen by cladding and fuel oxidation that are absent without fission-fragment irradiation of the gas. Quantitative description of the evolution of the chemical state inside the fuel rod is achieved by combining the chemical kinetics of the reactions between the gas and the fuel and cladding with the transport by diffusion of components of the gas in the gap. The chemistry-gas transport model provides the framework into which therate constants of the reactions between the gases in the gap and the fuel and cladding are incorporated. The output of the model calculation is the H 2 0/H 2 ratio in the gas and the degree of claddingand fuel oxidation as functions of distance from the primary defect. This output, when combined with a criterion for the onset of massive hydriding of the cladding, can provide a prediction of the time and location of a potential secondary hydriding failure. The chemistry-gas transport model is the starting point for mechanical and H-in-Zr migration analyses intended to determine the nature of the cladding failure caused by the development of the massive hydride on the inner wall

  14. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  15. Powder production of U-Mo alloy, HMD process (Hydriding- Milling- Dehydriding)

    Energy Technology Data Exchange (ETDEWEB)

    Pasqualini, E. E.; Garcia, J.H.; Lopez, M.; Cabanillas, E.; Adelfang, P. [Dept. Combustibles Nucleares. Comision Nacional de Energia Atomica, Av. Gral. Paz 1499, 1650 Buenos Aires (Argentina)

    2002-07-01

    Uranium-molybdenum (U-Mo) alloys can be hydrided massively in metastable {gamma} (gamma) phase. The brittle hydride can be milled and dehydrided to acquire the desired size distributions needed for dispersion nuclear fuels. The developments of the different steps of this process called hydriding-milling- dehydriding (HMD Process) are described. Powder production scales for industrial fabrication is easily achieved with conventional equipment, small man-power and low investment. (author)

  16. Powder production of U-Mo alloy, HMD process (Hydriding- Milling- Dehydriding)

    International Nuclear Information System (INIS)

    Pasqualini, E. E.; Garcia, J.H.; Lopez, M.; Cabanillas, E.; Adelfang, P.

    2002-01-01

    Uranium-molybdenum (U-Mo) alloys can be hydrided massively in metastable γ (gamma) phase. The brittle hydride can be milled and dehydrided to acquire the desired size distributions needed for dispersion nuclear fuels. The developments of the different steps of this process called hydriding-milling- dehydriding (HMD Process) are described. Powder production scales for industrial fabrication is easily achieved with conventional equipment, small man-power and low investment. (author)

  17. First principles characterisation of brittle transgranular fracture of titanium hydrides

    International Nuclear Information System (INIS)

    Olsson, Pär A.T.; Mrovec, Matous; Kroon, Martin

    2016-01-01

    In this work we have studied transgranular cleavage and the fracture toughness of titanium hydrides by means of quantum mechanical calculations based on density functional theory. The calculations show that the surface energy decreases and the unstable stacking fault energy increases with increasing hydrogen content. This is consistent with experimental findings of brittle behaviour of titanium hydrides at low temperatures. Based on Griffith-Irwin theory we estimate the fracture toughness of the hydrides to be of the order of 1 MPa⋅m"1"/"2, which concurs well with experimental data. To investigate the cleavage energetics, we analyse the decohesion at various crystallographic planes and determine the traction-separation laws based on the Rose's extended universal binding energy relation. The calculations predict that the peak stresses do not depend on the hydrogen content of the phases, but it is rather dependent on the crystallographic cleavage direction. However, it is found that the work of fracture decreases with increasing hydrogen content, which is an indication of hydrogen induced bond weakening in the material.

  18. The effect of sample preparation on uranium hydriding

    International Nuclear Information System (INIS)

    Banos, A.; Stitt, C.A.; Scott, T.B.

    2016-01-01

    Highlights: • Distinct differences in uranium hydride growth rates and characteristics between different surface preparation methods. • The primary difference between the categories of sample preparations is the level of strain present in the surface. • Greater surface-strain, leads to higher nucleation number density, implying a preferred attack of strained vs unstrained metal. • As strain is reduced, surface features such as carbides and grain boundaries become more important in controlling the UH3 location. - Abstract: The influence of sample cleaning preparation on the early stages of uranium hydriding has been examined, by using four identical samples but concurrently prepared using four different methods. The samples were reacted together in the same corrosion cell to ensure identical exposure conditions. From the analysis, it was found that the hydride nucleation rate was proportional to the level of strain exhibiting higher number density for the more strained surfaces. Additionally, microstructure of the metal plays a secondary role regarding initial hydrogen attack on the highly strained surfaces yet starts to dominate the system while moving to more pristine samples.

  19. Metal hydride-based thermal energy storage systems

    Science.gov (United States)

    Vajo, John J.; Fang, Zhigang

    2017-10-03

    The invention provides a thermal energy storage system comprising a metal-containing first material with a thermal energy storage density of about 1300 kJ/kg to about 2200 kJ/kg based on hydrogenation; a metal-containing second material with a thermal energy storage density of about 200 kJ/kg to about 1000 kJ/kg based on hydrogenation; and a hydrogen conduit for reversibly transporting hydrogen between the first material and the second material. At a temperature of 20.degree. C. and in 1 hour, at least 90% of the metal is converted to the hydride. At a temperature of 0.degree. C. and in 1 hour, at least 90% of the metal hydride is converted to the metal and hydrogen. The disclosed metal hydride materials have a combination of thermodynamic energy storage densities and kinetic power capabilities that previously have not been demonstrated. This performance enables practical use of thermal energy storage systems for electric vehicle heating and cooling.

  20. A thermal neutron scattering law for yttrium hydride

    Science.gov (United States)

    Zerkle, Michael; Holmes, Jesse

    2017-09-01

    Yttrium hydride (YH2) is of interest as a high temperature moderator material because of its superior ability to retain hydrogen at elevated temperatures. Thermal neutron scattering laws for hydrogen bound in yttrium hydride (H-YH2) and yttrium bound in yttrium hydride (Y-YH2) prepared using the ab initio approach are presented. Density functional theory, incorporating the generalized gradient approximation (GGA) for the exchange-correlation energy, is used to simulate the face-centered cubic structure of YH2 and calculate the interatomic Hellmann-Feynman forces for a 2 × 2 × 2 supercell containing 96 atoms. Lattice dynamics calculations using PHONON are then used to determine the phonon dispersion relations and density of states. The calculated phonon density of states for H and Y in YH2 are used to prepare H-YH2 and Y-YH2 thermal scattering laws using the LEAPR module of NJOY2012. Analysis of the resulting integral and differential scattering cross sections demonstrates adequate resolution of the S(α,β) function. Comparison of experimental lattice constant, heat capacity, inelastic neutron scattering spectra and total scattering cross section measurements to calculated values are used to validate the thermal scattering laws.

  1. Evaluation of Neutron shielding efficiency of Metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Sang Hwan; Chae, San; Kim, Yong Soo [Hanyang University, Seoul (Korea, Republic of)

    2012-05-15

    Neutron shielding is achieved of interaction with material by moderation and absorption. Material that contains large amounts hydrogen atoms which are almost same neutron atomic weight is suited for fast neutron shielding material. Therefore, polymers containing high density hydrogen atom are being used for fast neutron shielding. On the other hand, composite materials containing high thermal neutron absorption cross section atom (Li, B, etc) are being used for thermal neutron shielding. However, these materials have low fast neutron absorption cross section. Therefore, these materials are not suited for fast neutron shielding. Hydrogen which has outstanding neutron energy reduction ability has very low thermal neutron absorption cross section, almost cannot be used for thermal neutron shielding. In this case, a large atomic number material (Pb, U, etc.) has been used. Thus, metal hydrides are considered as complement to concrete shielding material. Because metal hydrides contain high hydrogen density and elements with high atomic number. In this research neutron shielding performance and characteristic of nuclear about metal hydrides ((TiH{sub 2}, ZrH{sub 2}, HfH{sub 2}) is evaluated by experiment and MCNPX using {sup 252}Cf neutron source as purpose development shielding material to developed shielding material

  2. Oxidation kinetics of hydride-bearing uranium metal corrosion products

    Science.gov (United States)

    Totemeier, Terry C.; Pahl, Robert G.; Frank, Steven M.

    The oxidation behavior of hydride-bearing uranium metal corrosion products from Zero Power Physics Reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2, Ar-9%O 2, and Ar-20%O 2. Ignition of corrosion product samples from two moderately corroded plates was observed between 125°C and 150°C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride.

  3. Oxidation kinetics of hydride-bearing uranium metal corrosion products

    International Nuclear Information System (INIS)

    Totemeier, T.C.; Pahl, R.G.; Frank, S.M.

    1998-01-01

    The oxidation behavior of hydride-bearing uranium metal corrosion products from zero power physics reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2 , Ar-9%O 2 , and Ar-20%O 2 . Ignition of corrosion product samples from two moderately corroded plates was observed between 125 C and 150 C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride. (orig.)

  4. Performance study of a hydrogen powered metal hydride actuator

    International Nuclear Information System (INIS)

    Bhuiya, Md Mainul Hossain; Kim, Kwang J

    2016-01-01

    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 LaNi 5 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. (paper)

  5. Rh-catalyzed linear hydroformylation of styrene

    NARCIS (Netherlands)

    Boymans, E.H.; Janssen, M.C.C.; Mueller, C.; Lutz, M.; Vogt, D.

    2012-01-01

    Usually the Rh-catalyzed hydroformylation of styrene predominantly yields the branched, chiral aldehyde. An inversion of regioselectivity can be achieved using strong p-acceptor ligands. Binaphthol-based diphosphite and bis(dipyrrolyl-phosphorodiamidite) ligands were applied in the Rh-catalyzed

  6. Nickel-Catalyzed Alkoxy-Alkyl Interconversion with Alkylborane Reagents through C−O Bond Activation of Aryl and Enol Ethers

    KAUST Repository

    Guo, Lin

    2016-11-07

    A nickel-catalyzed alkylation of polycyclic aromatic methyl ethers as well as methyl enol ethers with B-alkyl 9-BBN and trialkylborane reagents that involves the cleavage of stable C(sp2)−OMe bonds is described. The transformation has a wide substrate scope and good chemoselectivity profile while proceeding under mild reaction conditions; it provides a versatile way to form C(sp2)−C(sp3) bonds that does not suffer from β-hydride elimination. Furthermore, a selective and sequential alkylation process by cleavage of inert C−O bonds is presented to demonstrate the advantage of this method.

  7. Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C-O bond into a rhodacycle intermediate.

    Science.gov (United States)

    Oonishi, Yoshihiro; Yokoe, Takayuki; Hosotani, Akihito; Sato, Yoshihiro

    2014-01-20

    Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2) )-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while β-hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Effect of the hydrogen content and cooling velocity in the hydrides precipitation in α-zirconium

    International Nuclear Information System (INIS)

    Ramanathan, L.V.

    1983-01-01

    Zirconium specimens containing 50-300 ppm hydrogen have been cooled from the hydrogen solution treatment temperature at different rates by furnace cooling, air cooling and oil quenching. Optical and electron microscopical investigations have revealed grain boundary Δ - hydrides in slowly cooled specimens. At higher cooling rates γ and Δ hydrides have been found precipitated both intergranularly and intragranularly. Grain boundary Δ hydrides have been also observed in oil quenched specimens with 300 ppm hydrogen. Quenched specimens have revealed Widmanstatten and parallel plate type hydride morphologies. (Author) [pt

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

    Energy Technology Data Exchange (ETDEWEB)

    Idrees, Y.; Yao, Z. [Department of Mechanical and Materials Engineering, Queen' s University, Kingston, ON, Canada, K7L 3N6 (Canada); Cui, J.; Shek, G.K. [Kinetrics, Mississauga, ON (Canada); Daymond, M.R., E-mail: daymond@queensu.ca [Department of Mechanical and Materials Engineering, Queen' s University, Kingston, ON, Canada, K7L 3N6 (Canada)

    2016-11-15

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

  10. Lactam hydrolysis catalyzed by mononuclear metallo-beta-lactamases: A density functional study

    DEFF Research Database (Denmark)

    Hemmingsen, Lars Bo Stegeager; Olsen, L.; Antony, J.

    2003-01-01

    Two central steps in the hydrolysis of lactam antibiotics catalyzed by mononuclear metallo-beta-lactamases, formation of the tetrahedral intermediate and its breakdown by proton transfer, are studied for model systems using the density functional B3LYP method. Metallo-beta-lactamases have two metal...

  11. Sodium hydride precipitation in sodium cold traps

    International Nuclear Information System (INIS)

    McPheeters, C.C.; Raue, D.J.

    1979-10-01

    A series of experiments have been performed to test a calculational model for precipitation of NaH in sodium cold traps. The calculational model, called ACTMODEL, is a computer simulation that uses the system geometry and operating conditions as input to calculate a mass transfer coefficient and the distribution of NaH in a cold trap. The ACTMODEL was tested using an analytical cold trap (ACT) that is simple and essentially one-dimensional. The ACT flow and temperature profile may be controlled at any desired condition. The ACT was analyzed destructively after each test to measure the actual NaH distribution. Excellent agreement was obtained between the ACTMODEL simulations and the experiments

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

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

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

  13. COPPER(I)-CATALYZED ATOM TRANSFER RADICAL POLYMERIZATIONS. (R826735)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  14. TRANSITION METAL CATALYZED ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  15. Mechanistic Study of Oxygen Atom Transfer Catalyzed by Rhenium Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Xiaopeng [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    Two ionic and one neutral methyl(oxo)rhenium(V) compounds were synthesized and structurally characterized. They were compared in reactivity towards the ligands triphenylphosphane, pyridines, pyridine N-oxides. Assistance from Broensted bases was found on ligand displacement of ionic rhenium compounds as well as nucleophile assistance on oxidation of all compounds. From the kinetic data, crystal structures, and an analysis of the intermediates, a structural formula of PicH+3- and mechanisms of ligand displacement and oxidation were proposed.

  16. Plasma-plasmonics synergy in the Ga-catalyzed growth of Si-nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Bianco, Giuseppe Valerio, E-mail: giuseppevalerio.bianco@cnr.it [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Giangregorio, Maria M.; Capezzuto, Pio [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Losurdo, Maria [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Department of Electrical and Computer Engineering, Duke University, Durham, NC 27708 (United States); Kim, Tong-Ho; Brown, April S. [Department of Electrical and Computer Engineering, Duke University, Durham, NC 27708 (United States); Bruno, Giovanni, E-mail: giovanni.bruno@ba.imip.cnr.it [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy)

    2012-06-05

    This paper reports on the growth of Si nanowires (NWs) by SiH{sub 4}/H{sub 2} plasmas using the non-noble Ga-nanoparticles (NPs) catalysts. A comparative investigation of conventional Si-NWs vapour-liquid-solid (VLS) growth catalyzed by Au NPs is also reported. We investigate the use of a hydrogen plasma and of a SiH{sub 4}/H{sub 2} plasma for removing Ga oxide shell and for enhancing the Si dissolution into the catalyst, respectively. By exploiting the Ga NPs surface plasmon resonance (SPR) sensitivity to their surface chemistry, the SPR characteristic of Ga NPs has been monitored by real time spectroscopic ellipsometry in order to control the hydrogen plasma/Ga NPs interaction and the involved processes (oxide removal and NPs dissolution by volatile gallium hydride). Using in situ laser reflectance interferometry the metal catalyzed Si NWs growth process has been investigated to find the effect of the plasma activation on the growth kinetics. The role of atomic hydrogen in the NWs growth mechanism and, in particular, in the SiH{sub 4} dissolution into the catalysts, is discussed. We show that while Au catalysts because of the re-aggregation of NPs yields NWs that do not correspond to the original size of the Au NPs catalyst, the NWs grown by the Ga catalyst retains the diameter dictated by the size of the Ga NPs. Therefore, the advantage of Ga NPs as catalysts for controlling NWs diameter is demonstrated.

  17. Understanding hydride formation in Zr-1Nb alloy through microstructural characterization

    International Nuclear Information System (INIS)

    Neogy, S.; Srivastava, D.; Tewari, R.; Singh, R.N.; Dey, G.K.; De, P.K.; Banerjee, S.

    2003-07-01

    In this study the experimental results of hydride formation and their microstructure evolution in Zr-1Nb alloy is presented. This Zr-1Nb binary alloy and other Zr-1 Nb based ternary and quaternary alloys are being used as fuel tube materials and have the potential for meeting the requirement of high burn up fuel. Hydriding of Zr-1Nb alloy having a microstructure comprising equiaxed α grains and a uniform distribution of spherical particles of the β phase has been carried out in this study. The specimens have been hydrided by gaseous charging method to different hydrogen levels. The microstructures of hydrided samples were examined as a function of hydrogen content. The formation of δ hydride in slow cooled specimens and formation of γ hydride in rapidly cooled specimens has been studied with their morphology, habit plane and orientation relationship with the α matrix in view. The habit planes of either type of hydride phase has been determined and compared with those observed in other Zr-Nb alloys. The orientation relationship between the α matrix and the δ hydride was found to be the following: (0001) α // (111) δ and [1120] α // [110] δ . The orientation relationship between the α matrix and the γ hydride was of the following type: (0001) α // (111) γ and [1120] α // [110] γ . The internal structure of both types of hydride has been examined. The effect of the presence of the spherical β phase particles in the a matrix on the growth of the hydride plates has been investigated. (author)

  18. Low-Cost Metal Hydride Thermal Energy Storage System for Concentrating Solar Power Systems

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hardy, B. J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Corgnale, C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Teprovich, J. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Ward, P. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Motyka, Ted [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    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.

  19. Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

    KAUST Repository

    Saggio, Guillaume; Taoufik, Mostafa; Basset, Jean-Marie; Thivolle-Cazat, Jean

    2010-01-01

    Only 50% of the silica-supported tantalum hydride sites are active in the metathesis of propane. Indeed, more than 45% of the tantalum hydride can be eliminated by a selective oxygen poisoning of inactive sites with no significant decrease

  20. Electrochemical reduction of oxygen catalyzed by Pseudomonas aeruginosa

    Energy Technology Data Exchange (ETDEWEB)

    Cournet, Amandine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France)] [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Berge, Mathieu; Roques, Christine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France); Bergel, Alain [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Delia, Marie-Line, E-mail: marieline.delia@ensiacet.f [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France)

    2010-07-01

    Pseudomonas aeruginosa has already been shown to catalyze oxidation processes in the anode compartment of a microbial fuel cell. The present study focuses on the reverse capacity of the bacterium, i.e. reduction catalysis. Here we show that P. aeruginosa is able to catalyze the electrochemical reduction of oxygen. The use of cyclic voltammetry showed that, for a given range of potential values, the current generated in the presence of bacteria could reach up to four times the current obtained without bacteria. The adhesion of bacteria to the working electrode was necessary for the catalysis to be observed but was not sufficient. The electron transfer between the working electrode and the bacteria did not involve mediator metabolites like phenazines. The transfer was by direct contact. The catalysis required a certain contact duration between electrodes and live bacteria but after this delay, the metabolic activity of cells was no longer necessary. Membrane-bound proteins, like catalase, may be involved. Various strains of P. aeruginosa, including clinical isolates, were tested and all of them, even catalase-defective mutants, presented the same catalytic property. P. aeruginosa offers a new model for the analysis of reduction catalysis and the protocol designed here may provide a basis for developing an interesting tool in the field of bacterial adhesion.

  1. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand

    2015-01-01

    illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin......-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin...

  2. Combined on-board hydride slurry storage and reactor system and process for hydrogen-powered vehicles and devices

    Science.gov (United States)

    Brooks, Kriston P; Holladay, Jamelyn D; Simmons, Kevin L; Herling, Darrell R

    2014-11-18

    An on-board hydride storage system and process are described. The system includes a slurry storage system that includes a slurry reactor and a variable concentration slurry. In one preferred configuration, the storage system stores a slurry containing a hydride storage material in a carrier fluid at a first concentration of hydride solids. The slurry reactor receives the slurry containing a second concentration of the hydride storage material and releases hydrogen as a fuel to hydrogen-power devices and vehicles.

  3. Nitroreductase catalyzed biotransformation of CL-20

    International Nuclear Information System (INIS)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2004-01-01

    Previously, we reported that a salicylate 1-monooxygenase from Pseudomonas sp. ATCC 29352 biotransformed CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane) (C 6 H 6 N 12 O 12 ) and produced a key metabolite with mol. wt. 346Da corresponding to an empirical formula of C 6 H 6 N 10 O 8 which spontaneously decomposed in aqueous medium to produce N 2 O, NH4+, and HCOOH [Appl. Environ. Microbiol. (2004)]. In the present study, we found that nitroreductase from Escherichia coli catalyzed a one-electron transfer to CL-20 to form a radical anion (CL-20 - ) which upon initial N-denitration also produced metabolite C 6 H 6 N 10 O 8 . The latter was tentatively identified as 1,4,5,8-tetranitro-1,3a,4,4a,5,7a,8,8a-octahydro-diimidazo[4,5-b:4',5'-e] pyrazine [IUPAC] which decomposed spontaneously in water to produce glyoxal (OHCCHO) and formic acid (HCOOH). The rates of CL-20 biotransformation under anaerobic and aerobic conditions were 3.4+/-0.2 and 0.25+/-0.01nmolmin -1 mg of protein -1 , respectively. The product stoichiometry showed that each reacted CL-20 molecule produced about 1.8 nitrite ions, 3.3 molecules of nitrous oxide, 1.6 molecules of formic acid, 1.0 molecule of glyoxal, and 1.3 ammonium ions. Carbon and nitrogen products gave mass-balances of 60% and 81%, respectively. A comparative study between native-, deflavo-, and reconstituted-nitroreductase showed that FMN-site was possibly involved in the biotransformation of CL-20

  4. Hydrogen desorption kinetics from zirconium hydride and zirconium metal in vacuum

    International Nuclear Information System (INIS)

    Hu, Xunxiang; Terrani, Kurt A.; Wirth, Brian D.

    2014-01-01

    The kinetics of hydrogen desorption from zirconium hydride is important in many nuclear design and safety applications. In this paper, a coordinated experimental and modeling study has been used to explicitly demonstrate the applicability of existing kinetic theories for hydrogen desorption from zirconium hydride and α-zirconium. A static synthesis method was used to produce δ-zirconium hydride, and the crystallographic phases of the zirconium hydride were confirmed by X-ray diffraction (XRD). Three obvious stages, involving δ-zirconium hydride, a two-phase region, and α-zirconium, were observed in the hydrogen desorption spectra of two zirconium hydride specimens with H/Zr ratios of 1.62 and 1.64, respectively, which were obtained using thermal desorption spectroscopy (TDS). A continuous, one-dimensional, two-phase moving boundary model, coupled with the zero- and second-order kinetics of hydrogen desorption from δ-zirconium hydride and α-zirconium, respectively, has been developed to reproduce the TDS experimental results. A comparison of the modeling predictions with the experimental results indicates that a zero-order kinetic model is valid for description of hydrogen flux away from the δ-hydride phase, and that a second-order kinetic model works well for hydrogen desorption from α-Zr if the activation energy of desorption is optimized to be 70% of the value reported in the literature

  5. Pore-Confined Light Metal Hydrides for Energy Storage and Catalysis

    NARCIS (Netherlands)

    Bramwell, P.L.|info:eu-repo/dai/nl/371685117

    2017-01-01

    Light metal hydrides have enjoyed several decades of attention in the field of hydrogen storage, but their applications have recently begun to diversify more and more into the broader field of energy storage. For example, light metal hydrides have shown great promise as battery materials, in sensors

  6. Hydride precipitation crack propagation in zircaloy cladding during a decreasing temperature history

    International Nuclear Information System (INIS)

    Stout, R.B.

    2001-01-01

    An assessment of safety, design, and cost tradeoff issues for short (ten to fifty years) and longer (fifty to hundreds of years) interim dry storage of spent nuclear fuel in Zircaloy rods shall address potential failures of the Zircaloy cladding caused by the precipitation response of zirconium hydride platelets. To perform such assessment analyses rigorously and conservatively will be necessarily complex and difficult. For Zircaloy cladding, a model for zirconium hydride induced crack propagation velocity was developed for a decreasing temperature field and for hydrogen, temperature, and stress dependent diffusive transport of hydrogen to a generic hydride platelet at a crack tip. The development of the quasi-steady model is based on extensions of existing models for hydride precipitation kinetics for an isolated hydride platelet at a crack tip. An instability analysis model of hydride-crack growth was developed using existing concepts in a kinematic equation for crack propagation at a constant thermodynamic crack potential subject to brittle fracture conditions. At the time an instability is initiated, the crack propagation is no longer limited by hydride growth rate kinetics, but is then limited by stress rates. The model for slow hydride-crack growth will be further evaluated using existing available data. (authors)

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

    DEFF Research Database (Denmark)

    Poulsen, F.W.

    2001-01-01

    The chemical and physical nature of the hydride ion is briefly treated. Several reactions of the hydride ion in oxides or oxygen atmosphere are given, A number of perovskites and inverse perovskites are listed. which contain the H- ion on the oxygen or B-anion sites in the archetype ABO(3) System...

  8. Hydride precipitation crack propagation in zircaloy cladding during a decreasing temperature history

    Energy Technology Data Exchange (ETDEWEB)

    Stout, R.B. [California Univ., Livermore, CA (United States). Lawrence Livermore National Lab

    2001-07-01

    An assessment of safety, design, and cost tradeoff issues for short (ten to fifty years) and longer (fifty to hundreds of years) interim dry storage of spent nuclear fuel in Zircaloy rods shall address potential failures of the Zircaloy cladding caused by the precipitation response of zirconium hydride platelets. To perform such assessment analyses rigorously and conservatively will be necessarily complex and difficult. For Zircaloy cladding, a model for zirconium hydride induced crack propagation velocity was developed for a decreasing temperature field and for hydrogen, temperature, and stress dependent diffusive transport of hydrogen to a generic hydride platelet at a crack tip. The development of the quasi-steady model is based on extensions of existing models for hydride precipitation kinetics for an isolated hydride platelet at a crack tip. An instability analysis model of hydride-crack growth was developed using existing concepts in a kinematic equation for crack propagation at a constant thermodynamic crack potential subject to brittle fracture conditions. At the time an instability is initiated, the crack propagation is no longer limited by hydride growth rate kinetics, but is then limited by stress rates. The model for slow hydride-crack growth will be further evaluated using existing available data. (authors)

  9. In-situ X-ray diffraction : a useful tool to investigate hydride-formation reactions

    NARCIS (Netherlands)

    Notten, P.H.L.; Daams, J.L.C.; Veirman, de A.E.M.; Staals, A.A.

    1994-01-01

    A high-pressure X-ray diffraction (XRD) cell has been designed which allowed us to study simultaneously hydrogen absorption/desorption isotherms and XRD powder diffraction patterns on (de)hydrided intermetallic compounds. The hydride formation reaction was investigated in the case of LaNi5 under

  10. Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

    2008-06-10

    A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

  11. Hydride-induced degradation of hoop ductility in textured zirconium-alloy tubes: A theoretical analysis

    International Nuclear Information System (INIS)

    Qin, W.; Szpunar, J.A.; Kozinski, J.

    2012-01-01

    Hydride-induced degradation of hoop ductility in Zr-alloy tubular components has been studied for many years because of its importance in the nuclear industry. In this paper the role of intergranular and intragranular δ-hydrides in the degradation of ductility of the textured Zr-alloy tubes is investigated. The correlation among hydride distribution, orientation and morphology in the tubes is formulated based on thermodynamic modeling, and then analyzed. The results show that the applied stress, the crystallographic texture of α-Zr matrix, the grain-boundary structure, and the morphology and size of Zr grains simultaneously govern the site preference and the orientation of hydrides. A criterion is proposed to determine the threshold stress of hydride reorientation. The hoop ductility of the hydrided Zr tubes is discussed using the concept of macroscopic fracture strain. It is shown that the intergranular hydrides may be more deleterious to ductility than the intragranular ones. This work defines a general framework for understanding the relation of the microstructure of hydride-forming materials to embrittlement.

  12. Mechanisms of chemical generation of volatile hydrides for trace element determination (IUPAC Technical Report)

    Czech Academy of Sciences Publication Activity Database

    D'Ulivo, A.; Dědina, Jiří; Mester, Z.; Sturgeon, R. E.; Wang, Q.; Welz, B.

    2011-01-01

    Roč. 83, č. 6 (2011), s. 1283-1340 ISSN 0033-4545 Institutional research plan: CEZ:AV0Z40310501 Keywords : borane complexes * chemical generation of volatile hydrides (CHG) * volatile hydrides Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.789, year: 2011

  13. Muon-catalyzed fusion revisited

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1984-12-15

    A negative muon can induce nuclear fusion in the reaction of deuteron and triton nuclei giving a helium nucleus, a neutron and an emerging negative muon. The muon forms a tightlybound deuteron-triton-muon molecule and fusion follows in about 10{sup -12}s. Then the muon is free again to induce further reactions. Thus the muon can serve as a catalyst for nuclear fusion, which can proceed without the need for the high temperatures which are needed in the confinement and inertial fusion schemes. At room temperature, up to 80 fusions per muon have recently been observed at the LAMPF machine at Los Alamos, and it is clear that this number can be exceeded. These and other results were presented at a summer Workshop on Muon-Catalyzed Fusion held in Jackson, Wyoming. Approximately fifty scientists attended from Austria, Canada, India, Italy, Japan, South Africa, West Germany, and the United States. The Workshop itself is symbolic of the revival of interest in this subject.

  14. Trapping interference effects of arsenic, antimony and bismuth hydrides in collection of selenium hydride within iridium-modified transversally-heated graphite tube atomizer

    Energy Technology Data Exchange (ETDEWEB)

    Furdikova, Zuzana [Department of Environmental Chemistry and Technology, Faculty of Chemistry, Brno University of Technology, Purkynova 118, CZ-61200 Brno (Czech Republic); Institute of Analytical Chemistry of the Academy of Sciences of the Czech Republic v.v.i., Veveri 97, CZ-60200, Brno (Czech Republic); Docekal, Bohumil [Institute of Analytical Chemistry of the Academy of Sciences of the Czech Republic v.v.i., Veveri 97, CZ-60200, Brno (Czech Republic)], E-mail: docekal@iach.cz

    2009-04-15

    Interference effects of co-generated hydrides of arsenic, antimony and bismuth on trapping behavior of selenium hydride (analyte) within an iridium-modified, transversely heated graphite tube atomizer (THGA) were investigated. A twin-channel hydride generation system was used for independent separate generation and introduction of analyte and interferent hydrides, i.e. in a simultaneous and/or sequential analyte-interferent and interferent-analyte mode of operation. The influence of the analyte and modifier mass, interferent amount, trapping temperature and composition of the gaseous phase was studied. A simple approach for the elimination of mutual interference effects by modification of the gaseous phase with oxygen in a substoichiometric ratio to chemically generated hydrogen is proposed and the suppression of these interference effects is demonstrated. A hypothesis on the mechanism of trapping and mutual interference effects is drawn.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-09-01

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

  16. Iron Catalyzed Cycloaddition of Alkynenitriles and Alkynes

    Science.gov (United States)

    D’Souza, Brendan R.; Lane, Timothy K.

    2011-01-01

    The combination of Fe(OAc)2 and an electron-donating, sterically-hindered pyridyl bisimine ligand catalyzes the cycloaddition of alkynenitriles and alkynes. A variety of substituted pyridines were obtained in good yields. PMID:21557582

  17. Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

    KAUST Repository

    Maity, Niladri; Barman, Samir; Callens, Emmanuel; Samantaray, Manoja K.; Abou-Hamad, Edy; Minenkov, Yury; D'Elia, Valerio; Hoffman, Adam S.; Widdifield, Cory M.; Cavallo, Luigi; Gates, Bruce C.; Basset, Jean-Marie

    2015-01-01

    The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

  18. Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

    KAUST Repository

    Maity, Niladri

    2015-11-30

    The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

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

    International Nuclear Information System (INIS)

    Gruen, D.M.

    1981-01-01

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

  20. The status and immediate problems of the chemistry of transition metal hydrides

    International Nuclear Information System (INIS)

    Meikheeva, V.I.

    1978-01-01

    The state of the art and perspectives of the chemistry transition metal hydrides are reviewed, the hydrides being essentially compounds with interstitial hydrogen in the crystal lattice of the metals. The possibilities of hydrogenation of transition metals are considered along with that of compounds of rare earth elements with metals of the iron family. It is shown that the products of hydrogenation of many alloys are unstable and disintegrate forming simpler hydrides. The phase diagram of La-Ni-H system resembles the isotherm of a ternary metal system with the difference that no continuous series of solid solutions is formed. Most hydrogenation products across LaHsub(2-3)-NiH are X-ray amorphous. The nature of hydrogen in hydrides is discussed along with the possibilities of synthesis of new hydrides of transition metals

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

    International Nuclear Information System (INIS)

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

    2000-09-01

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

  2. Roles of texture in controlling oxidation, hydrogen ingress and hydride formation in Zr alloys

    International Nuclear Information System (INIS)

    Szpunar, Jerzy A.; Qin, Wen; Li, Hualong; Kumar, Kiran

    2011-01-01

    Experimental observations shows that the oxide formed on Zr alloys are strongly textured. The texture and grain-boundary characteristics of oxide are dependent on the texture of metal substrate. Computer simulation and thermodynamic modeling clarify the effect of metal substrate on structure of oxide film, and intrinsic factors affecting the microstructure. Models of diffusion process of hydrogen atoms and oxygen diffusion through oxide are presented. Both intra-granular and inter-granular hydrides were found following (0001) α-Zr //(111) δ-ZrH1.5 relationship. The through-thickness texture inhomogeneity in cladding tubes, the effects of hoop stress on the hydride orientation and the formation of interlinked hydride structure were studied. A thermodynamic model was developed to analyze the nucleation and the stress-induced reorientation of intergranular hydrides. These works provide a framework for understanding the oxidation, the hydrogen ingress and the hydride formation in Zr alloys. (author)

  3. Analytical and numerical models of uranium ignition assisted by hydride formation

    International Nuclear Information System (INIS)

    Totemeier, T.C.; Hayes, S.L.

    1996-01-01

    Analytical and numerical models of uranium ignition assisted by the oxidation of uranium hydride are described. The models were developed to demonstrate that ignition of large uranium ingots could not occur as a result of possible hydride formation during storage. The thermodynamics-based analytical model predicted an overall 17 C temperature rise of the ingot due to hydride oxidation upon opening of the storage can in air. The numerical model predicted locally higher temperature increases at the surface; the transient temperature increase quickly dissipated. The numerical model was further used to determine conditions for which hydride oxidation does lead to ignition of uranium metal. Room temperature ignition only occurs for high hydride fractions in the nominally oxide reaction product and high specific surface areas of the uranium metal

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2000-09-01

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

  5. Stress analysis of hydride bed vessels used for tritium storage

    International Nuclear Information System (INIS)

    McKillip, S.T.; Bannister, C.E.; Clark, E.A.

    1991-01-01

    A prototype hydride storage bed, using LaNi 4.25 Al 0.75 as the storage material, was fitted with strain gages to measure strains occurring in the stainless steel bed vessel caused by expansion of the storage powder upon uptake of hydrogen. The strain remained low in the bed as hydrogen was added, up to a bed loading of about 0.5 hydrogen to metal atom ratio (H/M). The strain then increased with increasing hydrogen loading (∼ 0.8 H/M). Different locations exhibited greatly different levels of maximum strain. In no case was the design stress of the vessel exceeded

  6. Prevention of delayed hydride cracking in zirconium alloys

    International Nuclear Information System (INIS)

    Cheadle, B.A.; Coleman, C.E.; Ambler, J.F.R.

    1987-01-01

    Zirconium alloys are susceptible to a mechanism for crack initiation and propagation called delayed hydride cracking. From a review of component failures and experimental results, we have developed the requirements for preventing this cracking. The important parameters for cracking are hydrogen concentration, flaws, and stress; each should be minimized. At the design and construction stages hydrogen pickup has to be controlled, quality assurance needs to be at a high enough level to ensure the absence of flaws, and residual stresses must be eliminated by careful fabrication and heat treatment

  7. Hydrogen isotope exchange in a metal hydride tube

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, David B. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2014-09-01

    This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

  8. Modification of the hydriding of uranium using ion implantation

    International Nuclear Information System (INIS)

    Musket, R.G.; Robinson-Weis, G.; Patterson, R.G.

    1983-01-01

    The hydriding of depleted uranium at 76 Torr hydrogen and 130 0 C has been significantly reduced by implantation of oxygen ions. The high-dose implanted specimens had incubation times for the initiation of the reaction after exposure to hydrogen that exceeded those of the nonimplanted specimens by more than a factor of eight. Furthermore, the nonimplanted specimens consumed enough hydrogen to cause macroscopic flaking of essentially the entire surface in times much less than the incubation time for the high-dose implanted specimens. In contrast, the ion-implanted specimens reacted only at isolated spots with the major fraction of the surface area unaffected by the hydrogen exposure

  9. Research in Nickel/Metal Hydride Batteries 2016

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2016-10-01

    Full Text Available Nineteen papers focusing on recent research investigations in the field of nickel/metal hydride (Ni/MH batteries have been selected for this Special Issue of Batteries. These papers summarize the joint efforts in Ni/MH battery research from BASF, Wayne State University, the National Institute of Standards and Technology, Michigan State University, and FDK during 2015–2016 through reviews of basic operational concepts, previous academic publications, issued US Patent and filed Japan Patent Applications, descriptions of current research results in advanced components and cell constructions, and projections of future works.

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

    International Nuclear Information System (INIS)

    Zou Lexi; Sun Ying; Xue Weidong; Zhu Zhenghe; Wang Rong; Luo Deli

    2002-01-01

    There are six independent constituents with 4 chemical elements, i.e. PuH 2.7 (s), PuN(s), Pu 2 O 3 (s), N 2 , O 2 and H 2 , therefore, the system described involves of 2 independent reactions, both ΔG 0 <<0. The calculated equilibrium compositions are in agreement with those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The author has briefly discussed the simultaneous reactions and its thermodynamic coupling effect

  11. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin

    2014-04-02

    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  12. Delayed hydride cracking behavior for zircaloy-2 plate

    International Nuclear Information System (INIS)

    Mills, J.W.; Huang, F.H.

    1991-01-01

    The delayed hydride cracking (DHC) behaviour for Zircaloy-2 plate was characterized at temperatures ranging from 300 to 550 o F. Specimens with a longitudinal (T-L) orientation exhibited a classic two-stage DHC response. At K values slightly above the threshold level (K th ), crack-growth rates increased dramatically with increasing K values (stage I). The K th value was found to be 11 and 14 ksi√ in at 400 and 500 o F. At high K values (stage II), cracking rates were relatively insensitive to applied K levels. Stage II crack growth was a thermally activated process described by an Arrhenius-type relationship with an activation energy of 65 kJ/mol. This energy level agreed with the theoretical activation energy for hydrogen diffusion into the triaxial stress field ahead of a crack. Above a critical temperature (300 o F), an overtemperature cycle was required to initiate DHC. The magnitude of the thermal excursion required to initiate cracking was found to increase at higher test temperatures. Specimens with a transverse(L-T) orientation showed a very low sensitivity to DHC because of an unfavorable crystallographic orientation for hydride reorientation. Metallographic and fractographic examinations were performed to understand the DHC mechanism. (author)

  13. Production of hydrogen gas from novel chemical hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Aiello, R.; Matthews, M.A. [South Carolina Univ., Chemical Engineering Dept., Columbia, SC (United States); Reger, D.L.; Collins, J.E. [South Carolina Univ., Chemistry and Biochemistry Dept., Columbia, SC (United States)

    1998-12-01

    Six ligand-stabilized complexes have been synthesized and tested for use as hydrogen storage media for portable fuel cell applications. The new hydrides are: [HC(3,5-Me{sub 2}pz){sub 3}]LiBH{sub 4} (1), [[H{sub 2}C(3,5-Me{sub 2}pz){sub 2}]LiBH{sub 4})]{sub 2} (2) (pz = pyrazolyl), [(TMEDA)Li(BH{sub 4})]{sub 2} (3) (TMEDA (CH{sub 3}){sub 2}NCH{sub 2}CH{sub 2}N(CH{sub 3}){sub 2}), [HC(pz){sub 3}]LiBH{sub 4} (4), [[H{sub 2}C(pz){sub 2}]Li(BH{sub 4})]{sub 2} (5) and Mg(BH{sub 4}){sub 2}3THF (6) (THF = tetrahydrofuran). Hydrolysis reactions of the compounds liberate hydrogen in quantities which range from 56 to 104 ({+-}5%) of the theoretical yield. Gas chromatographic analysis of the product gases from these reactions indicate that hydrogen is the only gas produced. Thermally initiated reactions of the novel compounds with NH{sub 4}Cl were unsuccessful. Although the amount of hydrogen energy which can be theoretically obtained per unit weight is lower than that of the classical hydrides such as LiBH{sub 4} and NaBH{sub 4}, the reactions are less violent and hydrolysis of compounds 1, 2, 4, 5 and 6 releases less heat per mole of hydrogen generated. (Author)

  14. Electron and nuclear magnetic resonances in compounds and metallic hydrides

    International Nuclear Information System (INIS)

    Brasil Filho, N.

    1985-11-01

    Proton pulsed Nuclear Magnetic Resonance measurements were performed on the metallic hydrides ZrCr 2 H x (x = 2, 3, 4) and ZrV 2 H y (y = 2, 3, 4, 5) as a function of temperature between 180 and 400K. The ultimate aim was the investigation of the relaxation mechanisms in these systems by means of the measurement of both the proton ( 1 H) spin-lattice (T 1 ) and spin-spin (T 2 ) relaxation times and to use these data to obtain information about the diffusive motion of the hydrogen atoms. The diffusional activation energies, the jump frequencies and the Korringa constant, C k , related with the conduction electron contribution to the 1 H relaxation were determined for the above hydrides as a function of hydrogen concentration. Our results were analysed in terms of the relaxation models described by Bloembergen, Purcell and Pound (BPP model) and by Torrey. The Korringa type relaxation due to the conduction electrons in metallic systems was also used to interpret the experimental results. We also present the Electron Paramagnetic Ressonance (EPR) study of Gd 3+ , Nd 3+ and Er 3+ ions as impurities in several AB 3 intermetallic compounds where A = LA, Ce, Y, Sc, Th, Zr and B = Rh, Ir, Pt. The results were analysed in terms of the multiband model previously suggested to explain the behaviour of the resonance parameter in AB 2 Laves Phase compounds. (author) [pt

  15. Theoretical study of hydrogen storage in metal hydrides.

    Science.gov (United States)

    Oliveira, Alyson C M; Pavão, A C

    2018-05-04

    Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

  16. A low tritium hydride bed inventory estimation technique

    Energy Technology Data Exchange (ETDEWEB)

    Klein, J.E.; Shanahan, K.L.; Baker, R.A. [Savannah River National Laboratory, Aiken, SC (United States); Foster, P.J. [Savannah River Nuclear Solutions, Aiken, SC (United States)

    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.

  17. Gas desorption properties of ammonia borane and metal hydride composites

    International Nuclear Information System (INIS)

    Matin, M.R.

    2009-01-01

    'Full text': Ammonia borane (NH 3 BH 3 ) has been of great interest owing to its ideal combination of low molecular weight and high H 2 storage capacity of 19.6 mass %, which exceeds the current capacity of gasoline. DOE's year 2015 targets involve gravimetric as well as volumetric energy densities. In this work, we have investigated thermal decomposition of ammonia borane and calcium hydride composites at different molar ratio. The samples were prepared by planetary ball milling under hydrogen gas atmosphere pressure of 1Mpa at room temperature for 2, and 10 hours. The gas desorption properties were examined by thermal desorption mass spectroscopy (TDMS). The identification of phases was carried out by X-ray diffraction. The results obtain were shown in fig (a),(b),and (c). Hydrogen desorption properties were observed at all molar ratios, but the desorption temperature is significantly lower at around 70 o C at molar ratio 1:1 as shown in fig (c), and unwanted gas (ammonia) emissions were remarkably suppressed by mixing with the calcium hydride. (author)

  18. Electronic structure of the palladium hydride studied by compton scattering

    CERN Document Server

    Mizusaki, S; Yamaguchi, M; Hiraoka, N; Itou, M; Sakurai, Y

    2003-01-01

    The hydrogen-induced changes in the electronic structure of Pd have been investigated by Compton scattering experiments associated with theoretical calculations. Compton profiles (CPs) of single crystal of Pd and beta phase hydride PdH sub x (x=0.62-0.74) have been measured along the [100], [110] and [111] directions with a momentum resolution of 0.14-0.17 atomic units using 115 keV x-rays. The theoretical Compton profiles have been calculated from the wavefunctions obtained utilizing the full potential linearized augmented plane wave method within the local density approximation for Pd and stoichiometric PdH. The experimental and the theoretical results agreed well with respect to the difference in the CPs between PdH sub x and Pd, and the anisotropy in the CPs of Pd or PdH sub x. This study provides lines of evidence that upon hydride formation the lowest valance band of Pd is largely modified due to hybridization with H 1s-orbitals and the Fermi energy is raised into the sp-band. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-18

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

  20. The effect of hydrides on the growth of zirconia

    International Nuclear Information System (INIS)

    Ekbom, L.R.

    1982-01-01

    The purpose of the present experiment has been to verify a hypothesis that accelerated corrosion of hydride containin Zircaloy is caused by small pores formed in the oxide by the evolution of hydrogen during oxidation of hydrides. The work has been divided into two parts: specimen preparation and microscopy. ZrO 2 is difficult to work with because of the high compressive stress which exists in the oxide. The most interesting area to study if any hydrogen pores exist, is the metal-oxide interface. Both transmission and scanning electron microscopy were used in the study. Neither of these methods gave any useful information with regard to the original hypothesis. However, a few interesting observations were made on the structure of the oxide at the metal-oxide interface. When the metal had been removed by electropolishing it was seen that the inner surface of the oxide consisted of 0,2-0.3 μ long and 0.1 μ thick wormlike protuberances of oxide. These features could not be seen when the metal had been removed by chemical etching. An attempt to determine whether or not this structure is an artefact introduced by electropolishing was inconclusive but indicated that the structure probably is real. (Author)

  1. Microchip power compensated calorimetry applied to metal hydride characterization

    Energy Technology Data Exchange (ETDEWEB)

    Sepulveda, A.; Lopeandia, A.F.; Domenech-Ferrer, R.; Garcia, G.; Pi, F.; Rodriguez-Viejo, J. [Nanomaterials and Microsystems Group, Physics Department, Universitat Autonoma de Barcelona, 08193 Bellaterra (Spain); Munoz, F.J. [Instituto de Microelectronica de Barcelona, Centro Nacional de Microelectronica, Campus UAB, 08193 Bellaterra (Spain)

    2008-06-15

    In this work, we show the suitability of the thin film membrane-based calorimetric technique to measure kinetically limited phase transitions such as the dehydrogenation of metallic hydrides. Different compounds such as Mg, Mg/Al and Mg{sub 80}Ti{sub 20} have been deposited over the active area of the microchip by electron beam evaporation. After several hydrogenation treatments at different temperatures to induce the hydride formation, calorimetric measurements on the dehydrogenation process of those thin films, either in vacuum or in air, are performed at a heating rate of 10 C/min. We observe a significant reduction in the onset of dehydrogenation for Mg{sub 80}Ti{sub 20} compared with pure Mg or Mg/Al layers, which confirms the beneficial effect of Ti on dehydrogenation. We also show the suitability of the membrane-based nanocalorimeters to be used in parallel with optical methods. Quantification of the energy released during hydrogen desorption remains elusive due to the semi-insulating to metallic transition of the film which affects the calorimetric trace. (author)

  2. A quantitative phase field model for hydride precipitation in zirconium alloys: Part I. Development of quantitative free energy functional

    International Nuclear Information System (INIS)

    Shi, San-Qiang; Xiao, Zhihua

    2015-01-01

    A temperature dependent, quantitative free energy functional was developed for the modeling of hydride precipitation in zirconium alloys within a phase field scheme. The model takes into account crystallographic variants of hydrides, interfacial energy between hydride and matrix, interfacial energy between hydrides, elastoplastic hydride precipitation and interaction with externally applied stress. The model is fully quantitative in real time and real length scale, and simulation results were compared with limited experimental data available in the literature with a reasonable agreement. The work calls for experimental and/or theoretical investigations of some of the key material properties that are not yet available in the literature

  3. Multi-scale characterization of nanostructured sodium aluminum hydride

    Science.gov (United States)

    NaraseGowda, Shathabish

    Complex metal hydrides are the most promising candidate materials for onboard hydrogen storage. The practicality of this class of materials is counter-poised on three critical attributes: reversible hydrogen storage capacity, high hydrogen uptake/release kinetics, and favorable hydrogen uptake/release thermodynamics. While a majority of modern metallic hydrides that are being considered are those that meet the criteria of high theoretical storage capacity, the challenges lie in addressing poor kinetics, thermodynamics, and reversibility. One emerging strategy to resolve these issues is via nanostructuring or nano-confinement of complex hydrides. By down-sizing and scaffolding them to retain their nano-dimensions, these materials are expected to improve in performance and reversibility. This area of research has garnered immense interest lately and there is active research being pursued to address various aspects of nanostructured complex hydrides. The research effort documented here is focused on a detailed investigation of the effects of nano-confinement on aspects such as the long range atomic hydrogen diffusivities, localized hydrogen dynamics, microstructure, and dehydrogenation mechanism of sodium alanate. A wide variety of microporous and mesoporous materials (metal organic frameworks, porous silica and alumina) were investigated as scaffolds and the synthesis routes to achieve maximum pore-loading are discussed. Wet solution infiltration technique was adopted using tetrahydrofuran as the medium and the precursor concentrations were found to have a major role in achieving maximum pore loading. These concentrations were optimized for each scaffold with varying pore sizes and confinement was quantitatively characterized by measuring the loss in specific surface area. This work is also aimed at utilizing neutron and synchrotron x-ray characterization techniques to study and correlate multi-scale material properties and phenomena. Some of the most advanced

  4. Hydrogen energy technology development conference. From production of hydrogen to application of utilization technologies and metal hydrides, and examples; Suiso energy gijutsu kaihatsu kaigi. Suiso no seizo kara riyo gijutsu kinzoku suisokabutsu no oyo to jirei

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1984-02-14

    The hydrogen energy technology development conference was held on February 14 to 17, 1984 in Tokyo. For hydrogen energy systems and production of hydrogen from water, 6 papers were presented for, e.g., the future of hydrogen energy, current state and future of hydrogen production processes, and current state of thermochemical hydrogen technology development. For hydrogen production, 6 papers were presented for, e.g., production of hydrogen from steel mill gas, coal and methanol. For metal hydrides and their applications, 6 papers were presented for, e.g., current state of development of hydrogen-occluding alloy materials, analysis of heat transfer in metal hydride layers modified with an organic compound and its simulation, and development of a large-size hydrogen storage system for industrial purposes. For hydrogen utilization technologies, 8 papers were presented for, e.g., combustion technologies, engines incorporating metal hydrides, safety of metal hydrides, hydrogen embrittlement of system materials, development trends of phosphate type fuel cells, and alkali and other low-temperature type fuel cells. (NEDO)

  5. A deformation and thermodynamic model for hydride precipitation kinetics in spent fuel cladding

    International Nuclear Information System (INIS)

    Stout, R.B.

    1989-10-01

    Hydrogen is contained in the Zircaloy cladding of spent fuel rods from nuclear reactors. All the spent fuel rods placed in a nuclear waste repository will have a temperature history that decreases toward ambient; and as a result, most all of the hydrogen in the Zircaloy will eventually precipitate as zirconium hydride platelets. A model for the density of hydride platelets is a necessary sub-part for predicting Zircaloy cladding failure rate in a nuclear waste repository. A model is developed to describe statistically the hydride platelet density, and the density function includes the orientation as a physical attribute. The model applies concepts from statistical mechanics to derive probable deformation and thermodynamic functionals for cladding material response that depend explicitly on the hydride platelet density function. From this model, hydride precipitation kinetics depend on a thermodynamic potential for hydride density change and on the inner product of a stress tensor and a tensor measure for the incremental volume change due to hydride platelets. The development of a failure response model for Zircaloy cladding exposed to the expected conditions in a nuclear waste repository is supported by the US DOE Yucca Mountain Project. 19 refs., 3 figs

  6. Influence of hydride microstructure on through-thickness crack growth in zircaloy-4 sheet

    International Nuclear Information System (INIS)

    Raynaud, P.A.; Meholic, M.J.; Koss, D.A.; Motta, A.T.; Chan, K.S.

    2007-01-01

    The fracture toughness of cold-worked and stress-relieved Zircaloy-4 sheet subject to through-thickness crack growth within a 'sunburst' hydride microstructure was determined at 25 o C. The results were obtained utilizing a novel testing procedure in which a narrow linear strip of hydride blister was fractured at small loads under bending to create a well-defined sharp pre-crack that arrested at the blister-substrate interface. The hydriding procedure also forms 'sunburst' hydrides emanating from the blister that were aligned both in the plane of the crack and in the crack growth direction. Subsequent tensile loading caused crack growth initiation into the field of 'sunburst' hydrides. Specimen failure occurred under near-linear elastic behavior, and the fracture toughness for crack growth initiation into sunburst hydrides was in the range K Q ∼10-15 MPa√m. These results, when combined with those of a previous study, indicate that the through-thickness crack growth initiation toughness at 25 o C is very sensitive to the hydride microstructure. (author)

  7. FY1995 study of aid system for the elderly and the disabled using metal hydride alloy actuators; 1995 nendo suiso kyuzo gokingata actuator ni yoru kaijo shien system no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

    Purpose of the project is to develop a transfer aid system for the elderly who need assistance in moving from a bed or a chair. It can make up insufficiency of assistant persons and can help to comfortably move the elderly. It has the highest demand in rehabilitation centers or hospitals. We have been designing an actuator using a metal hydride alloy for more than ten years and have confirmed that the actuator is very useful for developing the transfer. Furthermore, we have designed the transfer from a view point of human interfaces. This research was done under the above background. 1. We studied a comfortable posture for the elderly at an initial phase of standing to design the optimal knee pad using a life-size model of a transfer. Especially, we managed to lighten the burden imposed on the elderly by referring electromyographic signals at lower limbs and ground reaction forces. 2. Since the tactile sensation of the bottom of elderly person's foot gets dull, we designed a foot stage to prevent the elderly from the dull. 3. We determined the optimal mixture rate of a metal hydride alloy and developed an elastic bellows in order to design the actuator used for the transfer aid. 4. We determined the optimal compliance to prevent the elderly from a mechanical shock and designed a mechanism so that the transfer aid can work well. 5. Based on the above results, we developed the transfer aid using the metal hydride actuator. It was ascertained that it can lift a elderly person with 80kg weight by using only 40g alloy. Furthermore, it is proved that the transfer is not heavy (about 20g weight), small, silent, and moves smoothly by a battery on the market. (NEDO)

  8. Screening of metal hydride pairs for closed thermal energy storage systems

    International Nuclear Information System (INIS)

    Aswin, N.; Dutta, Pradip; Murthy, S. Srinivasa

    2016-01-01

    Thermal energy storage systems based on metal/hydrides usually are closed systems composed of two beds of metal/alloy – one meant for energy storage and the other for hydrogen storage. It can be shown that a feasible operating cycle for such a system using a pair of metals/alloys operating between specified temperature values can be ensured if the equilibrium hydrogen intake characteristics satisfy certain criteria. In addition, application of first law of thermodynamics to an idealized operating cycle can provide the upper bounds of selected performance indices, namely volumetric energy storage density, energy storage efficiency and peak discharge temperature. This is demonstrated for a representative system composed of LaNi 4.7 Al 0.3 –LaNi 5 operating between 353 K and 303 K which gave values of about 56 kW h m −3 for volumetric storage density, about 85% for energy storage efficiency and 343 K for peak discharge temperature. A system level heat and mass transfer study considering the reaction kinetics, hydrogen flow between the beds and heat exchanger models is presented which gave second level estimates of about 40 kW h m −3 for volumetric energy storage density, 73% for energy storage efficiency and 334 K for peak temperature for the representative system. The results from such studies lead to identifying metal/alloy pairs which can be shortlisted for detailed studies.

  9. Accumulating the hydride state in the catalytic cycle of [FeFe]-hydrogenases

    Science.gov (United States)

    Winkler, Martin; Senger, Moritz; Duan, Jifu; Esselborn, Julian; Wittkamp, Florian; Hofmann, Eckhard; Apfel, Ulf-Peter; Stripp, Sven Timo; Happe, Thomas

    2017-07-01

    H2 turnover at the [FeFe]-hydrogenase cofactor (H-cluster) is assumed to follow a reversible heterolytic mechanism, first yielding a proton and a hydrido-species which again is double-oxidized to release another proton. Three of the four presumed catalytic intermediates (Hox, Hred/Hred and Hsred) were characterized, using various spectroscopic techniques. However, in catalytically active enzyme, the state containing the hydrido-species, which is eponymous for the proposed heterolytic mechanism, has yet only been speculated about. We use different strategies to trap and spectroscopically characterize this transient hydride state (Hhyd) for three wild-type [FeFe]-hydrogenases. Applying a novel set-up for real-time attenuated total-reflection Fourier-transform infrared spectroscopy, we monitor compositional changes in the state-specific infrared signatures of [FeFe]-hydrogenases, varying buffer pH and gas composition. We selectively enrich the equilibrium concentration of Hhyd, applying Le Chatelier's principle by simultaneously increasing substrate and product concentrations (H2/H+). Site-directed manipulation, targeting either the proton-transfer pathway or the adt ligand, significantly enhances Hhyd accumulation independent of pH.

  10. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    Science.gov (United States)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-06-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g-1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

  11. Evaluation of delayed hydride cracking and fracture toughness in zirconium alloys

    International Nuclear Information System (INIS)

    Oh, Je Yong

    2000-02-01

    The tensile, fracture toughness, and delayed hydride cracking (DHC) test were carried at various temperatures to understand the effect of hydrides on zirconium alloys. And the effects of yield stress and texture on the DHC velocity were discussed. The tensile properties of alloy A were the highest, and the difference between directions in alloy C was small due to texture. The fracture toughness at room temperature decreased sharply when hydrided. Although the alignment of hydride plates was parallel to loading direction, the hydrides were fractured due to the triaxiality at the crack tip region. The fracture toughness over 200 .deg. C was similar regardless of the hydride existence, because the triaxiality region was lost due to the decrease of yield stress with temperature. As the yield stress decreased, the threshold stress intensity factor and the striation spacing increased in alloy A, and the fracture surfaces and striations were affected by microstructures in all alloys. To evaluate the effect of the yield stress on DHC velocity, a normalization method was proposed. When the DHC velocity was normalized with dividing by the terminal solid solubility and the diffusion coefficient of hydrogen, the relationship between the yield stress and the DHC velocity was representable on one master curve. The equation from the master curve was able to explain the difference between the theoretical activation energy and the experimental activation energy in DHC. The difference was found to be ascribed to the decrease of yield stress with temperature. texture affected the delayed hydride cracking velocity by yield stress and by hydride reprecipitation. The relationship between the yield stress and the DHC velocity was expressed as an exponential function, and the relationship between the reprecipitation of hydride and the DHC velocity was expressed as a linear function

  12. Influence of temperature on δ-hydride habit plane in α-Zirconium

    International Nuclear Information System (INIS)

    Singh, R. N.; Stahle, P.; Banerjee, S.; Ristmanaa, Matti; Sauramd, K.

    2008-01-01

    Dilute Zr-alloy with hcp α-Zr as major phase is used as pressure boundary for hot coolant in CANDU, PHWR and RBMK reactors. Hydrogen / deuterium ingress during service makes the pressure boundary components like pressure tubes of the aforementioned reactors susceptible to hydride embrittlement. Hydride acquires plate shaped morphology and the broad face of the hydride plate coincides with certain crystallographic plane of α-Zr crystal, which is called habit plane. Hydride plate oriented normal to tensile stress significantly increases the degree of embrittlement. Thus key to mitigating the damage due to hydride embrittlement is to avoid the formation of hydride plates normal to tensile stress. Two different theoretical approaches are used to determine the habit plane of precipitates viz., geometrical and solid mechanics. For the geometrical approach invariant plane and invariant-line criteria have been applied successfully and for the solid mechanics approach strain energy minimization criteria have been used successfully. Solid mechanics approach using strain energy computed by FEM technique has been applied to hydride precipitation in Zr-alloys, but the emphasis has been to understand the solvus hysteresis. The objective of the present investigation is to predict the habit plane of δ-hydride precipitating in α-Zr at 25, 300, 400 and 450 .deg. C. using strain energy minimization technique. The δ-hydride phase is modeled to undergo isotropic elastic and plastic deformation. The α-Zr phase was modeled to undergo transverse isotropic elastic deformation. Both isotropic plastic and transverse isotropic plastic deformations of α-Zr were considered. Further, both perfect and linear work-hardening plastic behaviors were considered. Accommodation strain energy of δ-hydrides forming in α-Zr crystal was computed using initial strain method as a function of hydride nuclei orientation. Hydride was modeled as disk with circular edge. The simulation was carried out

  13. Study on the scattering law and scattering kernel of hydrogen in zirconium hydride

    International Nuclear Information System (INIS)

    Jiang Xinbiao; Chen Wei; Chen Da; Yin Banghua; Xie Zhongsheng

    1999-01-01

    The nuclear analytical model of calculating scattering law and scattering kernel for the uranium zirconium hybrid reactor is described. In the light of the acoustic and optic model of zirconium hydride, its frequency distribution function f(ω) is given and the scattering law of hydrogen in zirconium hydride is obtained by GASKET. The scattering kernel σ l (E 0 →E) of hydrogen bound in zirconium hydride is provided by the SMP code in the standard WIMS cross section library. Along with this library, WIMS is used to calculate the thermal neutron energy spectrum of fuel cell. The results are satisfied

  14. Simultaneous analysis of arsenic, antimony, selenium and tellurium in environmental samples using hydride generation ICPMS

    International Nuclear Information System (INIS)

    Jankowski, L.M.; Breidenbach, R.; Bakker, I.J.I.; Epema, O.J.

    2009-01-01

    Full text: A quantitative method for simultaneous analysis of arsenic, antimony, selenium and tellurium in environmental samples is being developed using hydride generation ICPMS. These elements must be first transformed into hydride-forming oxidation states. This is particularly challenging for selenium and antimony because selenium is susceptible to reduction to the non-hydride-forming elemental state and antimony requires strong reducing conditions. The effectiveness of three reducing agents (KI, thiourea, cysteine) is studied. A comparison is made between addition of reducing agent to the sample and addition of KI to the NaBH 4 solution. Best results were obtained with the latter approach. (author)

  15. Quantification and characterization of zirconium hydrides in Zircaloy-4 by the image analysis method

    International Nuclear Information System (INIS)

    Zhang, J.H.; Groos, M.; Bredel, T.; Trotabas, M.; Combette, P.

    1992-01-01

    The image analysis method is used to determine the hydrogen content in specimens of Zircaloy-4. Two parameters, surface density of hydride, S v , and degree of orientation, Ω, are defined to represent separately the hydrogen content and the orientation of hydrides. By analysing the stress-relieved Zircaloy-4 specimens with known hydrogen content from 100 to 1000 ppm, a relationship is established between the parameter S v and the hydrogen content when the magnifications of the optical microscope are 1000 and 250. The degree of orientation for the hydride in the stress-relieved Zircaloy-4 cladding is about 0.3. (orig.)

  16. Study of factors affecting a combustion method for determining carbon in lithium hydride

    International Nuclear Information System (INIS)

    Barringer, R.E.; Thornton, R.E.

    1975-09-01

    An investigation has been made of the factors affecting a combustion method for the determination of low levels (300 to 15,000 micrograms/gram) of carbon in highly reactive lithium hydride. Optimization of the procedure with available equipment yielded recoveries of 90 percent, with a limit of error (0.95) of +-39 percent relative for aliquants containing 35 to 55 micrograms of carbon (500 to 800 micrograms of carbon per gram of lithium hydride sample). Sample preparation, thermal decomposition of the hydride, final ignition of the carbon, and carbon-measurement steps were studied, and a detailed procedure was developed. (auth)

  17. Thermodynamics and statistical mechanics of some hydrides of the lanthanides and actinides

    International Nuclear Information System (INIS)

    Mintz, M.H.

    1976-06-01

    This work deals mainly with the thermodynamic and physical properties of the hydrides of the lanthanides and actinides. In addition, statistical models have been developed and applied to metal-hydrogen systems. A kinetic study of the uranium-hydrogen system was performed. The thermodynamic properties of the hydrides of neptunium, thorium, praseodymium, neodymium, samarium and europium were determined. In addition the samarium-europium-hydrogen ternary system was investigated. Moessbauer effect measurements of cubic neptunium hydrides were interpreted according to a model presented. A comparison. (author)

  18. Peculiarities of formation of zirconium aluminides in hydride cycle mode

    International Nuclear Information System (INIS)

    Muradyan, G.N.

    2016-01-01

    The zirconium aluminides are promising structural materials in aerospace, mechanical engineering, chemical industry, etc. They are promising for manufacturing of heat-resistant wires, that will improve the reliability and efficiency of electrical networks. In the present work, the results of study of zirconium aluminides formation in the Hydride Cycle (HC) mode, developed in the Laboratory of high-temperature synthesis of the Institute of Chemical Physics of NAS RA, are described. The formation of zirconium aluminides in HC proceeded according to the reaction xZrH_2+(1-x)Al → alloy Zr_xAl(1-x)+H_2↑. The samples were certified using: chemical analysis to determine the content of hydrogen (pyrolysis method); differential thermal analysis (DTA, derivatograph Q-1500, T_heating = 1000°C, rate 20°C/min); X-ray analysis (XRD, diffractometer DRON-0.5). The influences of the ratio of powders ZrH_2/Al in the reaction mixture, compacting pressure, temperature and heating velocity on the characteristics of the synthesized aluminides were determined. In HC, the solid solutions of Al in Zr, single phase ZrAl_2 and ZrAl_3 aluminides and Zr_3AlH_4.49 hydride were synthesized. Formation of aluminides in HC mode took place by the solid-phase mechanism, without melting of aluminum. During processing, the heating of the initial charge up to 540°C resulted in the decomposition of zirconium hydride (ZrH_2) to HCC ZrH_1.5, that interacted with aluminum at 630°C forming FCC alumohydride of zirconium. Further increase of the temperature up to 800°C led to complete decomposition of the formed alumohydride of zirconium. The final formation of the zirconium aluminide occurred at 1000-1100°C in the end of HC process. Conclusion: in the synthesis of zirconium aluminides, the HC mode has several significant advantages over the conventional modes: lower operating temperatures (1000°C instead of 1800°C); shorter duration (1.5-2 hours instead of tens of hours); the availability of

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-05-31

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

  20. Comparison of delayed hydride cracking behavior of two zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Ponzoni, L.M.E. [CNEA – Centro Atómico Constituyentes, Hidrógeno en Materiales, Av. Gral. Paz 1499, San Martín (B1650KNA), Bs. As. (Argentina); Mieza, J.I. [CNEA – Centro Atómico Constituyentes, Hidrógeno en Materiales, Av. Gral. Paz 1499, San Martín (B1650KNA), Bs. As. (Argentina); Instituto Sabato, UNSAM–CNEA, Av. Gral. Paz 1499, San Martín (B1650KNA), Bs. As. (Argentina); De Las Heras, E. [CNEA – Centro Atómico Constituyentes, Hidrógeno en Materiales, Av. Gral. Paz 1499, San Martín (B1650KNA), Bs. As. (Argentina); Domizzi, G., E-mail: domizzi@cnea.gov.ar [CNEA – Centro Atómico Constituyentes, Hidrógeno en Materiales, Av. Gral. Paz 1499, San Martín (B1650KNA), Bs. As. (Argentina); Instituto Sabato, UNSAM–CNEA, Av. Gral. Paz 1499, San Martín (B1650KNA), Bs. As. (Argentina)

    2013-08-15

    Delayed hydride cracking (DHC) is an important failure mechanism that may occur in Zr alloys during service in water-cooled reactors. Two conditions must be attained to initiate DHC from a crack: the stress intensity factor must be higher than a threshold value called K{sub IH} and, hydrogen concentration must exceed a critical value. Currently the pressure tubes for CANDU reactor are fabricated from Zr–2.5Nb. In this paper the critical hydrogen concentration for DHC and the crack velocity of a developmental pressure tube, Excel, was evaluated and compared with that of Zr–2.5Nb. The DHC velocity values measured in Excel were higher than usually reported in Zr–2.5Nb. Due to the higher hydrogen solubility limits in Excel, its critical hydrogen concentration for DHC initiation is 10–50 wppm over that of Zr–2.5Nb in the range of 150–300 °C.

  1. Hydride transport vessel vibration and shock test report

    Energy Technology Data Exchange (ETDEWEB)

    Tipton, D.G.

    1998-06-01

    Sandia National Laboratories performed vibration and shock testing on a Savannah River Hydride Transport Vessel (HTV) which is used for bulk shipments of tritium. This testing is required to qualify the HTV for transport in the H1616 shipping container. The main requirement for shipment in the H1616 is that the contents (in this case the HTV) have a tritium leak rate of less than 1x10{sup {minus}7} cc/sec after being subjected to shock and vibration normally incident to transport. Helium leak tests performed before and after the vibration and shock testing showed that the HTV remained leaktight under the specified conditions. This report documents the tests performed and the test results.

  2. Delayed hydride cracking: theoretical model testing to predict cracking velocity

    International Nuclear Information System (INIS)

    Mieza, Juan I.; Vigna, Gustavo L.; Domizzi, Gladys

    2009-01-01

    Pressure tubes from Candu nuclear reactors as any other component manufactured with Zr alloys are prone to delayed hydride cracking. That is why it is important to be able to predict the cracking velocity during the component lifetime from parameters easy to be measured, such as: hydrogen concentration, mechanical and microstructural properties. Two of the theoretical models reported in literature to calculate the DHC velocity were chosen and combined, and using the appropriate variables allowed a comparison with experimental results of samples from Zr-2.5 Nb tubes with different mechanical and structural properties. In addition, velocities measured by other authors in irradiated materials could be reproduced using the model described above. (author)

  3. Modeling of hydride precipitation and re-orientation

    Energy Technology Data Exchange (ETDEWEB)

    Tikare, Veena [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Weck, Philippe F. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Mitchell, John Anthony [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2015-09-18

    In this report, we present a thermodynamic-­based model of hydride precipitation in Zr-based claddings. The model considers the state of the cladding immediately following drying, after removal from cooling-pools, and presents the evolution of precipitate formation upon cooling as follows: The pilgering process used to form Zr-based cladding imparts strong crystallographic and grain shape texture, with the basal plane of the hexagonal α-Zr grains being strongly aligned in the rolling-­direction and the grains are elongated with grain size being approximately twice as long parallel to the rolling direction, which is also the long axis of the tubular cladding, as it is in the orthogonal directions.

  4. Density of trapped gas in heavily-irradiated lithium hydride

    International Nuclear Information System (INIS)

    Bowman, R.C. Jr.; Attalla, A.; Souers, P.C.; Folkers, C.L.; McCreary, T.; Snider, G.D.; Vanderhoofven, F.; Tsugawa, R.T.

    1988-01-01

    We review old gamma-irradiated lithium hydride data and also display much new bulk and gas-displacement density and nuclear magnetic resonance data on Li(D, T) and LiT at 296 to 373 K. We find that: (1) Li(D, T) swells because of the formation of internal D-T and 3 He gas bubbles, but probably not because of the precipitation of lithium metal; (2) the gas bubbles are at densities of at least 3 to 4x10 4 mol/m 3 , i.e. thousands of atmospheres; (3) outgassing may be largely the result of bubbles rupturing, although diffusion of 3 He as atoms may occur at long times. (orig.)

  5. Pressure-induced transformations of molecular boron hydride

    International Nuclear Information System (INIS)

    Nakano, Satoshi; Hemley, Russell J; Gregoryanz, Eugene A; Goncharov, Alexander F; Mao, Ho-kwang

    2002-01-01

    Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV

  6. Final report for the DOE Metal Hydride Center of Excellence.

    Energy Technology Data Exchange (ETDEWEB)

    Keller, Jay O.; Klebanoff, Leonard E.

    2012-01-01

    This report summarizes the R&D activities within the U.S. Department of Energy Metal Hydride Center of Excellence (MHCoE) from March 2005 to June 2010. The purpose of the MHCoE has been to conduct highly collaborative and multi-disciplinary applied R&D to develop new reversible hydrogen storage materials that meet or exceed DOE 2010 and 2015 system goals for hydrogen storage materials. The MHCoE combines three broad areas: mechanisms and modeling (which provide a theoretically driven basis for pursuing new materials), materials development (in which new materials are synthesized and characterized) and system design and engineering (which allow these new materials to be realized as practical automotive hydrogen storage systems). This Final Report summarizes the organization and execution of the 5-year research program to develop practical hydrogen storage materials for light duty vehicles. Major results from the MHCoE are summarized, along with suggestions for future research areas.

  7. Pressure-induced transformations of molecular boron hydride

    CERN Document Server

    Nakano, S; Gregoryanz, E A; Goncharov, A F; Mao Ho Kwang

    2002-01-01

    Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV.

  8. Hydride transport vessel vibration and shock test report

    International Nuclear Information System (INIS)

    Tipton, D.G.

    1998-06-01

    Sandia National Laboratories performed vibration and shock testing on a Savannah River Hydride Transport Vessel (HTV) which is used for bulk shipments of tritium. This testing is required to qualify the HTV for transport in the H1616 shipping container. The main requirement for shipment in the H1616 is that the contents (in this case the HTV) have a tritium leak rate of less than 1x10 -7 cc/sec after being subjected to shock and vibration normally incident to transport. Helium leak tests performed before and after the vibration and shock testing showed that the HTV remained leaktight under the specified conditions. This report documents the tests performed and the test results

  9. First principle calculations of alkali hydride electronic structures

    International Nuclear Information System (INIS)

    Novakovic, N; Radisavljevic, I; Colognesi, D; Ostojic, S; Ivanovic, N

    2007-01-01

    Electronic structure, volume optimization, bulk moduli, elastic constants, and frequencies of the transversal optical vibrations in LiH, NaH, KH, RbH, and CsH are calculated using the full potential augmented plane wave method, extended with local orbitals, and the full potential linearized augmented plane wave method. The obtained results show some common features in the electronic structure of these compounds, but also clear differences, which cannot be explained using simple empirical trends. The differences are particularly prominent in the electronic distributions and interactions in various crystallographic planes. In the light of these findings we have elaborated some selected experimental results and discussed several theoretical approaches frequently used for the description of various alkali hydride properties

  10. Metal hydride hydrogen compression: recent advances and future prospects

    Science.gov (United States)

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

    2016-04-01

    Metal hydride (MH) thermal sorption compression is one of the more important applications of the MHs. 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 modelling of a two-stage compressor aimed at describing the performance of the experimentally studied systems, 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 MH compression in the overall development of the hydrogen-driven energy systems. The work is based on the analysis of the development of the technology in Europe, USA and South Africa.

  11. Interface Enthalpy-Entropy Competition in Nanoscale Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Nicola Patelli

    2018-01-01

    Full Text Available We analyzed the effect of the interfacial free energy on the thermodynamics of hydrogen sorption in nano-scaled materials. When the enthalpy and entropy terms are the same for all interfaces, as in an isotropic bi-phasic system, one obtains a compensation temperature, which does not depend on the system size nor on the relative phase abundance. The situation is different and more complex in a system with three or more phases, where the interfaces have different enthalpy and entropy. We also consider the possible effect of elastic strains on the stability of the hydride phase and on hysteresis. We compare a simple model with experimental data obtained on two different systems: (1 bi-phasic nanocomposites where ultrafine TiH2 crystallite are dispersed within a Mg nanoparticle and (2 Mg nanodots encapsulated by different phases.

  12. Work function in niobium, tantalum and vanadium hydrides

    International Nuclear Information System (INIS)

    Kucherov, Ya.R.; Markin, V.Ya.; Savin, V.I.; Topil'skij, N.D.

    1978-01-01

    The concentration dependences of the work function of electrons in hydrides of Nb, Ta and V are presented. The work function of electrons was studied at room temperature by the contact Kelvin potential difference method to an accuracy of +-0.02 eV. The effect of hydrogen on the work function variations in the systems investigated has been analyzed. It is shown that a higher hydrogen concentration in solid solutions based on the Nb-H and Ta-H systems increases the effective total positive dipole moment, whereby the work function decreases. The abnormal changes in the work function in the region of solid solutions of hydrogen in vanadium seem to be due to the specific electronic structure of vanadium and its interaction with hydrogen

  13. Modelling zirconium hydrides using the special quasirandom structure approach

    KAUST Repository

    Wang, Hao; Chroneos, Alexander I.; Jiang, Chao; Schwingenschlö gl, Udo

    2013-01-01

    The study of the structure and properties of zirconium hydrides is important for understanding the embrittlement of zirconium alloys used as cladding in light water nuclear reactors. Simulation of the defect processes is complicated due to the random distribution of the hydrogen atoms. We propose the use of the special quasirandom structure approach as a computationally efficient way to describe this random distribution. We have generated six special quasirandom structure cells based on face centered cubic and face centered tetragonal unit cells to describe ZrH2-x (x = 0.25-0.5). Using density functional theory calculations we investigate the mechanical properties, stability, and electronic structure of the alloys. © the Owner Societies 2013.

  14. Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

    Science.gov (United States)

    Ju, Minsoo; Weatherly, Cale D; Guzei, Ilia A; Schomaker, Jennifer M

    2017-08-07

    Asymmetric nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Reactions of ethyl diazoacetate catalyzed by methylrhenium trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Z.; Espenson, H. [Iowa State Univ., Ames, IA (United States)

    1995-11-03

    Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) has found wise use in catalysis, including the epoxidation and metathesis of olefins, aldehyde olefination, and oxygen transfer. Extensive reports have now appeared in the area of MTO-catalyzed substrate oxidations with hydrogen peroxide. Certain catalytic applications of MTO for organic reactions that do not utilize peroxide have now been realized. In particular, a catalytic amount of MTO with ethyl diazoacetate (EDA) will convert aromatic imines to aziridines and convert aldehydes and ketones to epoxides. The aziridine preparation proceeds in high yields under anaerobic conditions more conveniently than with existing methods. Compounds with a three-membered heterocyclic ring can be obtained with the EDA/MTO catalytic system. Aromatic imines undergo cycloaddition reactions to give aziridines under mild conditions.

  16. Hydride phase dissolution enthalpy in neutron irradiated Zircaloy-4

    International Nuclear Information System (INIS)

    Vizcaino, Pablo; Banchik, Abraham D.

    2003-01-01

    The differential calorimetric technique has been applied to measure the dissolution enthalpy, ΔH irrad δ→α , of zirconium hydrides precipitated in structural components removed from the Argentine Atucha 1 PHWR nuclear power plant after 10.3 EFPY. An average value of ΔH irrad δ→α = 5 kJ/mol H was obtained after the first calorimetric run. That value is seven times lower than the value of ΔH δ→α = 37.7 kJ/mol H recently determined in Zircaloy-4 specimens taken from similar unirradiated structural components using the same calorimetric technique, [1]. Post-irradiation thermal treatments gradually increase that low value towards the unirradiated value with increasing annealing temperature similar to that observed for TSSd irrad . Therefore the same H atom trapping mechanism during reactor operation already proposed to explain the evolution of TSSd irrad is also valid for Q irrad δ→α . As the ratio Q/ΔH is proportional to the number N H of H atoms precipitated as hydrides, the increment of Q irrad δ→α with the thermal treatment indicates that the value of N H also grows with the annealing reaching the value corresponding to the bulk H concentration when ΔH irrad δ→α ≅ 37 kJ/mol H. That is a direct indication that the post-irradiation thermal treatment releases the H atoms from their traps increasing the number of H atoms available to precipitate at the end of each calorimetric run and/or isothermal treatment. (author)

  17. Neutron diffraction studies of transition metal hydride complexes

    International Nuclear Information System (INIS)

    Koetzle, T.F.; Bau, R.

    1976-01-01

    Investigations of H 3 Ta(C 5 H 5 ) 2 (III), HW 2 (CO) 9 (NO) (IV), and HW 2 (CO) 8 (NO) (P(OCH 3 ) 3 ) (V) have been completed. Preliminary results are available for HFeCo 3 (CO) 9 [P(OCH 3 ) 3 ] 3 (VII). This work, together with studies of HMo 2 (C 5 H 5 ) 2 (CO) 4 (P(CH 3 ) 2 ) (VI) and [(C 2 H 5 ) 4 N] + [HCr 2 (CO) 10 ] - carried out at Argonne has led to some general observations on the geometry and the nature of bonding in these compounds. For example, in the structures of IV and V, both of which have bent W--H--W linkages (less than W--H--W in the range 125-130 0 ), there is conclusive evidence for the existence of a closed three-center W--H--W bond with significant metal-metal interaction. Such is the case, because extensions of the axial W--C and W--N bonds trans to the hydride intersect at a point near the center of the W--H--W triangle. The geometry of VI, which also contains a bent M--H--M bond, is consistent with that of IV and V. Bridging M--H bonds in these second- and third-row hydrides range in length from 1.85 to 1.89 A, compared to 1.75 A in the first-row polynuclear complex VII. For metals of corresponding rows, bridging M--H bonds are about 0.1 A longer than terminal bonds, which are classified as single covalent bonds

  18. Solutions to commercializing metal hydride hydrogen storage products

    International Nuclear Information System (INIS)

    Tomlinson, J.J.; Belanger, R.

    2004-01-01

    'Full text:' Whilst the concept of a Hydrogen economy in the broad sense may for some analysts and Fuel Cell technology developers be an ever moving target the use of hydrogen exists and is growing in other markets today. The use of hydrogen is increasing. Who are the users? What are their unique needs? How can they better be served? As the use of hydrogen increases there are things we can do to improve the perception and handling of hydrogen as an industrial gas that will impact the future issues of hydrogen as a fuel thereby assisting the mainstream availability of hydrogen fuel a reality. Factors that will induce change in the way hydrogen is used, handled, transported and stored are the factors to concentrate development efforts on. Other factors include: cost; availability; safety; codes and standards; and regulatory authorities acceptance of new codes and standards. New methods of storage and new devices in which the hydrogen is stored will influence and bring about change and increased use. New innovative products based on Metal Hydride hydrogen storage will address some of the barriers to widely distributed hydrogen as a fuel or energy carrier to which successful fuel cell product commercialization is subject. Palcan has developed innovative products based on it's Rare Earth Metal Hydride alloy. Some of these innovations will aid the distribution of hydrogen as a fuel and offer alternatives to the existing hydrogen user and to the Fuel Cell product developer. An overview of the products and how these products will affect the distribution and use of hydrogen as an industrial gas and fuel is presented. (author)

  19. Hydride reorientation in Zircaloy-4 examined by in situ synchrotron X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Weekes, H.E. [Department of Materials, Royal School of Mines, Imperial College London, Prince Consort Road, London SW7 2BP (United Kingdom); Jones, N.G. [Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS (United Kingdom); Lindley, T.C. [Department of Materials, Royal School of Mines, Imperial College London, Prince Consort Road, London SW7 2BP (United Kingdom); Dye, D., E-mail: david.dye@imperial.ac.uk [Department of Materials, Royal School of Mines, Imperial College London, Prince Consort Road, London SW7 2BP (United Kingdom)

    2016-09-15

    The phenomenon of stress-reorientation has been investigated using in situ X-ray diffraction during the thermomechanical cycling of hydrided Zircaloy-4 tensile specimens. Results have shown that loading along a sample’s transverse direction (TD) leads to a greater degree of hydride reorientation when compared to rolling direction (RD)-aligned samples. The elastic lattice micro-strains associated with radially oriented hydrides have been revealed to be greater than those oriented circumferentially, a consequence of strain accommodation. Evidence of hydride redistribution after cycling, to α-Zr grains oriented in a more favourable orientation when under an applied stress, has also been observed and its behaviour has been found to be highly dependent on the loading axis. Finally, thermomechanical loading across multiple cycles has been shown to reduce the difference in terminal solid solubility of hydrogen during dissolution (TSS{sub D,H}) and precipitation (TSS{sub P,H}).

  20. Corrosion behavior of Zircaloy 4 cladding material. Evaluation of the hydriding effect

    International Nuclear Information System (INIS)

    Blat, M.

    1997-04-01

    In this work, particular attention has been paid to the hydriding effect in PIE and laboratory test to validate a detrimental hydrogen contribution on Zircaloy 4 corrosion behavior at high burnup. Laboratory corrosion tests results confirm that hydrides have a detrimental role on corrosion kinetics. This effect is particularly significant for cathodic charged samples with a massive hydride outer layer before corrosion test. PIE show that at high burnup a hydride layer is formed underneath the metal/oxide interface. The results of the metallurgical examinations are discussed with respect to the possible mechanisms involved in this detrimental effect of hydrogen. Therefore, according to the laboratory tests results and PIE, hydrogen could be a strong contributor to explain the increase in corrosion rate at high burnup. (author)

  1. Hydrogen metal hydride storage with integrated catalytic recombiner for mobile application

    Energy Technology Data Exchange (ETDEWEB)

    Marinescu-Pasoi, L.; Behrens, U.; Langer, G.; Gramatte, W.; Rastogi, A.K.; Schmitt, R.E. (Battelle-Institut e.V., Frankfurt am Main (DE). Dept. of Energy Technology)

    1991-01-01

    A novel, thermodynamically efficient device is under development at Battelle in Frankfurt, by which the range of hydrogen-driven cars with a metal hydride tank might be roughly doubled. The device makes use of the properties of metal hydrides, combined with catalytic combustion. Its development is funded by the Hessian Ministry of Economic Affairs and Technology; it is to be completed by the end of 1990. High-temperature hydrides (HTH) have about three times the storage capacity of low temperature hydrides (LTH), but require relatively large amounts of heat at high temperatures to release the hydrogen. The exhaust heat from combustion-engine-driven vehicles is insufficient for this, and vehicles with electric (fuel cell) drive produce practically no exhaust heat at all. The Battelle-developed device is a combination of an HTH storage cell, an LTH storage cell and a catalyst. (author).

  2. Unexpected formation of hydrides in heavy rare earth containing magnesium alloys

    Directory of Open Access Journals (Sweden)

    Yuanding Huang

    2016-09-01

    Full Text Available Mg–RE (Dy, Gd, Y alloys show promising for being developed as biodegradable medical applications. It is found that the hydride REH2 could be formed on the surface of samples during their preparations with water cleaning. The amount of formed hydrides in Mg–RE alloys is affected by the content of RE and heat treatments. It increases with the increment of RE content. On the surface of the alloy with T4 treatment the amount of formed hydride REH2 is higher. In contrast, the amount of REH2 is lower on the surfaces of as-cast and T6-treated alloys. Their formation mechanism is attributed to the surface reaction of Mg–RE alloys with water. The part of RE in solid solution in Mg matrix plays an important role in influencing the formation of hydrides.

  3. The uranium zirconium hydride research reactor and its applications in research and education

    Energy Technology Data Exchange (ETDEWEB)

    Chen Wei; Wang Daohua; Jiang Xinbiao; A Jinyan; Yang Jun; Chen Da [Northwest Institute of Nuclear Technology, Xi' an (China)

    2003-03-01

    This paper describes briefly the performance, the configuration and the prospects of extensive applications in science, technology and education of the Uranium Zirconium Hydride research reactor in China. (author)

  4. The uranium zirconium hydride research reactor and its applications in research and education

    International Nuclear Information System (INIS)

    Chen Wei; Wang Daohua; Jiang Xinbiao; A Jinyan; Yang Jun; Chen Da

    2003-01-01

    This paper describes briefly the performance, the configuration and the prospects of extensive applications in science, technology and education of the Uranium Zirconium Hydride research reactor in China. (author)

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

    KAUST Repository

    Shaikh Ali, Anaam; Jedidi, Abdesslem; Cavallo, Luigi; Takanabe, Kazuhiro

    2015-01-01

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report

  6. Theoretical study of the chemical properties of cesium hydride; Teoreticke studium chemickych vlastnosti hydridu cezia

    Energy Technology Data Exchange (ETDEWEB)

    Skoviera, J [Univerzita Komenskeho v Bratislave, Prirodovedecka fakulta, Katedra fyzikalnej a teoretickej chemie, 84215 Bratislava (Slovakia)

    2012-04-25

    A theoretical study of radiofrequency source of hydrogen ions in the International Thermonuclear Experimental Reactor (ITER) used a cesium grid as a source of electrons for ionization of hydrogen. In the process of ionization of hydrogen, however, there is a weathering of cesium grid, resulting into a group of undesired products - cesium hydrides and materials derived from cesium hydride. We calculated the potential curves of cesium hydride and of its anion and cation, their spectroscopic properties and partly their electrical properties. To make electrical properties comparable with the experiment, we calculated for all also the vibration corrections. Lack of convergence in RASSCF step caused, that the electrical properties of excited states are still an open question of chemical properties of cesium hydride. (authors)

  7. Characteristics of hydrogen evolution and oxidation catalyzed by Desulfovibrio caledoniensis biofilm on pyrolytic graphite electrode

    International Nuclear Information System (INIS)

    Yu Lin; Duan Jizhou; Zhao Wei; Huang Yanliang; Hou Baorong

    2011-01-01

    Highlights: → The sulphate-reducing bacteria (SRB) have the ability to catalyze the hydrogen evolution and oxidation on pyrolytic graphite electrode. → The SRB biofilm decreases the overpotential and electron transfer resistance by the CV and EIS detection. → The SRB biofilm can transfer electrons to the 0.24 V polarized pyrolytic graphite electrode and the maximum current is 0.035 mA, which is attributed to SRB catalyzed hydrogen oxidation. → The SRB biofilm also can obtain electron from the -0.61 V polarized PGE to catalyze the hydrogen evolution. - Abstract: Hydrogenase, an important electroactive enzyme of sulphate-reducing bacteria (SRB), has been discovered having the capacity to connect its activity to solid electrodes by catalyzing hydrogen evolution and oxidation. However, little attention has been paid to similar electroactive characteristics of SRB. In this study, the electroactivities of pyrolytic graphite electrode (PGE) coated with SRB biofilm were investigated. Two corresponding redox peaks were observed by cyclic voltammetry detection, which were related to the hydrogen evolution and oxidation. Moreover, the overpotential for the reactions decreased by about 0.2 V in the presence of the SRB biofilm. When the PGE coated with the SRB biofilm was polarized at 0.24 V (vs. SHE), an oxidation current related to the hydrogen oxidation was found. The SRB biofilm was able to obtain electrons from the -0.61 V (vs. SHE) polarized PGE to form hydrogen, and the electron transfer resistance also decreased with the formation of SRB biofilm, as measured by the non-destructive electrochemical impendence spectroscopy detection. It was concluded that the hydrogen evolution and oxidation was an important way for the electron transfer between SRB biofilm and solid electrode in anaerobic environment.

  8. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  9. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    KAUST Repository

    Fava, Eleonora

    2016-07-21

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

  10. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    KAUST Repository

    Fava, Eleonora; Nakajima, Masaki; Nguyen, Anh L. P.; Rueping, Magnus

    2016-01-01

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

  11. The formation and characteristics of hydride blisters in c.w. Zircaloy-2 pressure tubes

    Energy Technology Data Exchange (ETDEWEB)

    Price, E G [ed.

    1994-09-01

    Under the auspices of the IAEA, a consultants` meeting was arranged in Vienna, 1994 July 25-29, at which a Canadian delegation, consisting of AECL and Ontario Hydro Technologies personnel, presented information on their knowledge of the behaviour of hydride blisters in Zircaloy-2 pressure tubes. This document contains the 10 papers presented by the Canadian delegation to the meeting. It is believed that they represent a good reference document on hydride blister phenomena.

  12. Trapping of antimony and bismuth hydrides on a molybdenum-foil strip

    Czech Academy of Sciences Publication Activity Database

    Krejčí, Pavel; Dočekal, Bohumil

    2005-01-01

    Roč. 99, S (2005), s148-s149 ISSN 0009-2770. [Meeting on Chemistry and Life /3./. Brno, 20.09.2005-22.09.2005] R&D Projects: GA AV ČR IAA400310507 Institutional research plan: CEZ:AV0Z40310501 Keywords : hydride generation * hydride trapping * molybdenum-foil strip device Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 0.445, year: 2005

  13. A review of uranium corrosion by hydrogen and the formation of uranium hydride

    OpenAIRE

    Banos, A.; Harker, N. J.; Scott, T. B.

    2018-01-01

    Uranium hydride (UH3) is the direct product of the reaction between uranium metal and gaseous hydrogen. In the context of uranium storage, this corrosion reaction is considered deleterious, not just because the structure of the metal may become significantly degraded but also because the resulting hydride is pyrophoric and therefore potentially flammable in air if present in significant quantity. The current review draws from the literature surrounding the uranium-hydrogen system accrued over...

  14. An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages

    OpenAIRE

    Stitt , C. A.; Harker , N. J.; Hallam , K. R.; Paraskevoulakos , C.; Banos , A.; Rennie , S.; Jowsey , J.; Scott , T. B.

    2015-01-01

    International audience; Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reacta...

  15. PAC and μSr investigations of light interstitial diffusion in intermetallic hydrides

    International Nuclear Information System (INIS)

    Boyer, P.; Baudry, A.

    1988-01-01

    Specific aspects of the Perturbed Angular Correlation (PAC) of gamma rays concerning its application to the study of atomic diffusion in solids are presented. PAC results recently obtained on the 181 Ta probe in several crystalline and amorphous phases of Zr 2 Ni hydrides are briefly summarized. Preliminary μSR results relative to these intermetallic hydrides are presented and compared to the PAC data

  16. Synthesis of intermetallic hydrides of Zr-Ni system in the burning regime

    Energy Technology Data Exchange (ETDEWEB)

    Akopyan, A.G.; Dolukhanyan, S.K.; Karapetyan, A.K.; Merzhanov, A.G.

    1983-06-01

    Conditions for production of intermetallides in the Zr-Ni system and their hydrides in the burning regime are studied. Burning regularities of Zr/sub 2/Ni and ZrNi intermetallides in hydrogen are studied, the burning mechanism is found. It is shown that burning proceeds at abnormally low temperatures. Optimum synthesis conditions for Zr/sub 2/NiH/sub 5/ and ZrNiH/sub 3/ hydrides are determined.

  17. Delayed hydride cracking in Zr-2.5Nb pressure tubes

    International Nuclear Information System (INIS)

    Mieza, Juan I.; Domizzi, Gladys; Vigna, Gustavo L.

    2007-01-01

    Zr-2.5 Nb alloy from CANDU pressure tubes are prone to failure by hydrogen intake. One of the degradation mechanisms is delayed hydride cracking, which is characterized by the velocity of cracking. In this work, we study the effect of beta zirconium phase transformation over delayed hydride cracking velocity in Zr-2.5 Nb alloy from pressure tubes. Acoustic emission technique was used for cracking detection. (author) [es

  18. An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

    Science.gov (United States)

    DeKorver, Kyle A; Hsung, Richard P; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C

    2012-06-15

    A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

  19. Sulfonium Salts as Alkylating Agents for Palladium-Catalyzed Direct Ortho Alkylation of Anilides and Aromatic Ureas.

    Science.gov (United States)

    Simkó, Dániel Cs; Elekes, Péter; Pázmándi, Vivien; Novák, Zoltán

    2018-02-02

    A novel method for the ortho alkylation of acetanilide and aromatic urea derivatives via C-H activation was developed. Alkyl dibenzothiophenium salts are considered to be new reagents for the palladium-catalyzed C-H activation reaction, which enables the transfer of methyl and other alkyl groups from the sulfonium salt to the aniline derivatives under mild catalytic conditions.

  20. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    Science.gov (United States)

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

    2009-01-01

    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  1. Muon catalyzed fusion under compressive conditions

    International Nuclear Information System (INIS)

    Cripps, G.; Goel, B.; Harms, A.A.

    1991-01-01

    The viability of a symbiotic combination of Muon Catalyzed Fusion (μCF) and high density generation processes has been investigated. The muon catalyzed fusion reaction rates are formulated in the temperature and density range found under moderate compressive conditions. Simplified energy gain and power balance calculations indicate that significant energy gain occurs only if standard type deuterium-tritium (dt) fusion is ignited. A computer simulation of the hydrodynamics and fusion kinetics of a spherical deuterium-tritium pellet implosion including muons is performed. Using the muon catalyzed fusion reaction rates formulated and under ideal conditions, the pellet ignites (and thus has a significant energy gain) only if the initial muon concentration is approximately 10 17 cm -3 . The muons need to be delivered to the pellet within a very short-time (≅ 1 ns). The muon pulse required in order to make the high density and temperature muon catalyzed fusion scheme viable is beyond the present technology for muon production. (orig.) [de

  2. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  3. Enzyme-Catalyzed Transetherification of Alkoxysilanes

    Directory of Open Access Journals (Sweden)

    Peter G. Taylor

    2013-01-01

    Full Text Available We report the first evidence of an enzyme-catalyzed transetherification of model alkoxysilanes. During an extensive enzymatic screening in the search for new biocatalysts for silicon-oxygen bond formation, we found that certain enzymes promoted the transetherification of alkoxysilanes when tert-butanol or 1-octanol were used as the reaction solvents.

  4. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.

    2005-01-01

    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  5. Experimental study of a metal hydride driven braided artificial pneumatic muscle

    Science.gov (United States)

    Vanderhoff, Alexandra; Kim, Kwang J.

    2009-12-01

    This paper reports the experimental study of a new actuation system that couples a braided artificial pneumatic muscle (BAPM) with a metal hydride driven hydrogen compressor to create a compact, lightweight, noiseless system capable of high forces and smooth actuation. The results indicate that the metal hydride-BAPM system has relatively good second law efficiency average of 30% over the desorption cycle. The thermal efficiency is low, due mainly to the highly endothermic chemical reaction that releases the stored hydrogen gas from the metal hydride. The force to metal hydride weight is very high (~14 000 NForce/kgMH) considering that this system has not been optimized to use the minimum amount of metal hydride required for a full actuation stroke of the fluidic muscle. Also, a thermodynamic model for the complete system is developed. The analysis is restricted in some aspects concerning the complexity of the hydriding/dehydriding chemical process of the system and the three-dimensional geometry of the reactor, but it provides a useful comparison to other actuation devices and clearly reveals the parameters necessary for optimization of the actuation system in future work. The system shows comparable work output and has the benefits of biological muscle-like properties for potential use in robotic systems.

  6. A NOVEL METHOD OF THE HYDRIDE SEPARATION FOR THE DETERMINATION OF ARSENIC AND ANTIMONY BY AAS

    Directory of Open Access Journals (Sweden)

    Ganden Supriyanto

    2010-06-01

    Full Text Available A novel method is proposed for the hydride separation when determinining of arsenic and antimony by AAS. A chromatomembrane cell was used as preconcentration-, extraction- and separation-manifold instead of the U-tube phase separator, which is normally fitted in continuous flow vapour systems generating conventionaly the hydrides. The absorbances of the hydrides produced were measured by an atomic absorption spectrophotometer at 193.7 nm and 217.6 nm. Under optimized analytical conditions, the calibration plot for arsenic was linear from 50 to 500 ng.mL-1 (r2 = 0.9982. The precision for three subsequent measurements of 500 ng.mL-1 arsenic gave rise to a relative standard deviation of 0.4%. The detection limit was 15 ng.mL-1, which is much lower compared with that of the conventional hydride system (2000 ng.mL-1. A similar result was observed in case of antimony: the detection limit was 8 ng.mL-1 when the proposed method was applied. Consequently, the sensitivity of the novel method surpasses systems with conventional hydride generation, i.e. the precision and the acuracy increase whereas the standard deviation and the detection limit decrease. The proposed method was applied in pharmacheutial analysis and the certified As-content of a commercial product was very sufficiently confirmed.   Keywords: Chromatomembrane Cell, Hydride separation, Arsenic detection, Antimony detection, AAS

  7. Hydrogen charging, hydrogen content analysis and metallographic examination of hydride in zirconium alloys

    International Nuclear Information System (INIS)

    Singh, R.N.; Kishore, R.; Mukherjee, S.; Roychowdhury, S.; Srivastava, D.; Sinha, T.K.; De, P.K.; Banerjee, S.; Gopalan, B.; Kameswaran, R.; Sheelvantra, Smita S.

    2003-12-01

    Gaseous and electrolytic hydrogen charging techniques for introducing controlled amount of hydrogen in zirconium alloy is described. Zr-1wt%Nb fuel tube, zircaloy-2 pressure tube and Zr-2.5Nb pressure tube samples were charged with up to 1000 ppm of hydrogen by weight using one of the aforementioned methods. These hydrogen charged Zr-alloy samples were analyzed for estimating the total hydrogen content using inert gas fusion technique. Influence of sample surface preparation on the estimated hydrogen content is also discussed. In zirconium alloys, hydrogen in excess of the terminal solid solubility precipitates out as brittle hydride phase, which acquire platelet shaped morphology due to its accommodation in the matrix and can make the host matrix brittle. The F N number, which represents susceptibility of Zr-alloy tubes to hydride embrittlement was measured from the metallographs. The volume fraction of the hydride phase, platelet size, distribution, interplatelet spacing and orientation were examined metallographically using samples sliced along the radial-axial and radial-circumferential plane of the tubes. It was observed that hydride platelet length increases with increase in hydrogen content. Considering the metallographs generated by Materials Science Division as standard, metallographs prepared by the IAEA round robin participants for different hydrogen concentration was compared. It is felt that hydride micrographs can be used to estimate not only that approximate hydrogen concentration of the sample but also its size, distribution and orientation which significantly affect the susceptibility to hydride embrittlement of these alloys. (author)

  8. Modelling the gas transport and chemical processes related to clad oxidation and hydriding

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, R O; Rashid, Y R [ANATECH Research Corp., San Diego, CA (United States)

    1997-08-01

    Models are developed for the gas transport and chemical processes associated with the ingress of steam into a LWR fuel rod through a small defect. These models are used to determine the cladding regions in a defective fuel rod which are susceptible to massive hydriding and the creation of sunburst hydrides. The brittle nature of zirconium hydrides (ZrH{sub 2}) in these susceptible regions produces weak spots in the cladding which can act as initiation sites for cladding cracks under certain cladding stress conditions caused by fuel cladding mechanical interaction. The modeling of the axial gas transport is based on gaseous bimolar diffusion coupled with convective mass transport using the mass continuity equation. Hydrogen production is considered from steam reaction with cladding inner surface, fission products and internal components. Eventually, the production of hydrogen and its diffusion along the length results in high hydrogen concentration in locations remote from the primary defect. Under these conditions, the hydrogen can attack the cladding inner surface and breakdown the protective ZrO{sub 2} layer locally, initiating massive localized hydriding leading to sunburst hydride. The developed hydrogen evolution model is combined with a general purpose fuel behavior program to integrate the effects of power and burnup into the hydriding kinetics. Only in this manner can the behavior of a defected fuel rod be modeled to determine the conditions the result in fuel rod degradation. (author). 14 refs, 6 figs.

  9. The effect of texture on delayed hydride cracking in Zr-2.5Nb alloy

    Energy Technology Data Exchange (ETDEWEB)

    Resta Levi, R.; Sagat, S

    1999-09-01

    Pressure tubes for CANDU reactors are made of Zr-2.5Nb alloy. They are produced by hot extrusion followed by cold work, which results in a material with a pronounced crystallographic texture with basal plane normals of its hexagonal structure around the circumferential direction. Under certain conditions, this material is susceptible to a cracking mechanism called delayed hydride cracking (DHC). Our work investigated the susceptibility of Zr-2.5Nb alloy pressure tube to DHC in this pressure tube material, in terms of crystallographic texture and grain shape. The results are presented in terms of crack velocity obtained on different planes and directions of the pressure tube. The results show that it is more difficult for a crack to propagate at right angles to crystallographic basal planes (which are close to the precipitation habit plane of hydrides) than for it to propagate parallel to the basal plane. However, if the cracking plane is oriented parallel to preexisting hydrides (hydrides formed as a result of the manufacturing process), the crack propagates along these hydrides easily, even if the hydride habit planes are not oriented favourably. (author)

  10. Investigation of the effect of hydride and iodine on the mechanical behaviour of the zircaloy-4

    International Nuclear Information System (INIS)

    Soares, M.I.

    1981-12-01

    To investigate the effect of hydride and iodine on the mechanical behaviour of the zircaloy-4 tubes, deformation tests under pressure of samples hydrided in autoclave and of samples containing iodine were carried out, in order to simulate the fission product. The same tests were carried out in samples without hydride and iodine contents that were used as reference samples in the temperature range of 650 0 C-950 0 C. The hydrided samples and the samples containing iodine tested at 650 0 C and 750 0 C showed a higher ductility than the samples of reference. The hydrided samples tested at 850 0 C and 950 0 C showed a higher embritlement than the samples of reference and than the samples containing iodine tested at the same temperatures. A mechanical test has been developed to investigate the effect of hydride and iodine on the mechanical behaviour of the zircaloy-4 tubes. The mechanical test were carried out at room temperature. At room temperature the hydrition decreased the ductility of zircaloy-4. At room temperature the sample containing iodine showed a higher ductility than the sample without iodine. The combined action of hydrogen and iodine at room temperature enhanced the embrittlment of the samples zircaloy-4. (Author) [pt

  11. Investigation of Lithium Metal Hydride Materials for Mitigation of Deep Space Radiation

    Science.gov (United States)

    Rojdev, Kristina; Atwell, William

    2016-01-01

    Radiation exposure to crew, electronics, and non-metallic materials is one of many concerns with long-term, deep space travel. Mitigating this exposure is approached via a multi-faceted methodology focusing on multi-functional materials, vehicle configuration, and operational or mission constraints. In this set of research, we are focusing on new multi-functional materials that may have advantages over traditional shielding materials, such as polyethylene. Metal hydride materials are of particular interest for deep space radiation shielding due to their ability to store hydrogen, a low-Z material known to be an excellent radiation mitigator and a potential fuel source. We have previously investigated 41 different metal hydrides for their radiation mitigation potential. Of these metal hydrides, we found a set of lithium hydrides to be of particular interest due to their excellent shielding of galactic cosmic radiation. Given these results, we will continue our investigation of lithium hydrides by expanding our data set to include dose equivalent and to further understand why these materials outperformed polyethylene in a heavy ion environment. For this study, we used HZETRN 2010, a one-dimensional transport code developed by NASA Langley Research Center, to simulate radiation transport through the lithium hydrides. We focused on the 1977 solar minimum Galactic Cosmic Radiation environment and thicknesses of 1, 5, 10, 20, 30, 50, and 100 g/cm2 to stay consistent with our previous studies. The details of this work and the subsequent results will be discussed in this paper.

  12. Criteria for fracture initiation at hydrides in zirconium alloys. Pt. 1

    International Nuclear Information System (INIS)

    Shi, S.Q.; Puls, M.P.

    1994-01-01

    A theoretical framework for the initiation of delayed hydride cracking (DHC) in zirconium is proposed for two different types of initiating sites, i.e., a sharp crack tip (considered in this part) and a shallow notch (considered in part II). In the present part I, an expression for K IH is derived which shows that K IH depends on the size and shape of the hydride precipitated at the crack tip, the yield stress and elastic moduli of the material and the fracture stress of the hydride. If the hydride at the crack tip extends in length at constant thickness, then K IH increases as the square root of the hydride thickness. Thus a microstructure favouring the formation of thicker hydrides at the crack tip would result in an increased K IH . K IH increases slightly with temperature up to a temperature at which there is a more rapid increase. The temperature at which there is a more rapid increase in K IH will increase as the yield stress increases. The model also predicts that an increase in yield stress due to irradiation will cause an overall slight decrease in K IH compared to unirradiated material. There is good agreement between the overall predictions of the theory and experimental results. It is suggested that more careful evaluations of some key parameters are required to improve on the theoretical estimates. (orig.)

  13. Morphology study on the depleted uranium as hydriding/dehydriding cycles

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Dong-you, E-mail: dongyou@nfri.re.kr [National Fusion Research Institute, Daejeon (Korea, Republic of); Yun, Sei-Hun; Kang, Hyun-Goo; Chang, Min Ho; Oh, Yun Hee [National Fusion Research Institute, Daejeon (Korea, Republic of); Kang, Kweon Ho; Woo, Yoon Myung [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2016-11-01

    Depleted Uranium (DU) is one of the strongest candidates as a getter material of hydrogen isotopes in the nuclear fusion reactor. In this work, small DU lump specimen with 99.8% purity was prepared for observation of morphology variation as hydriding/dehydriding cycles. Hydriding/dehydriding of DU was carried out more than 10 cycles for powder preparation. The pulverized DU specimen was safely handled in the glove box under Argon gas condition to minimize contact with oxygen and humidity. The morphology change according to hydriding/dehydriding cycles was observed by visual cell reactor, optical microscope and scanning electron microscope. The first hydriding of the small DU sample has progressed slowly with surface enlargement and volume expansion as time passes. After third hydriding/dehydriding cycles, most of DU was pulverized. The powder fineness of DU developed as hydriding/dehydriding cycle progresses. But the agglomerates of fine DU particles were observed. It was confirmed that the DU particles exist as porous agglomerates. And the particle agglomerate shows poor fluidity and even has the cohesive force.

  14. Synthesis, spectroscopy, and hydrogen/deuterium exchange in high-spin iron(II) hydride complexes.

    Science.gov (United States)

    Dugan, Thomas R; Bill, Eckhard; MacLeod, K Cory; Brennessel, William W; Holland, Patrick L

    2014-03-03

    Very few hydride complexes are known in which the metals have a high-spin electronic configuration. We describe the characterization of several high-spin iron(II) hydride/deuteride isotopologues and their exchange reactions with one another and with H2/D2. Though the hydride/deuteride signal is not observable in NMR spectra, the choice of isotope has an influence on the chemical shifts of distant protons in the dimers through the paramagnetic isotope effect on chemical shift. This provides the first way to monitor the exchange of H and D in the bridging positions of these hydride complexes. The rate of exchange depends on the size of the supporting ligand, and this is consistent with the idea that H2/D2 exchange into the hydrides occurs through the dimeric complexes rather than through a transient monomer. The understanding of H/D exchange mechanisms in these high-spin iron hydride complexes may be relevant to postulated nitrogenase mechanisms.

  15. ON THE CHEMISTRY OF HYDRIDES OF N ATOMS AND O{sup +} IONS

    Energy Technology Data Exchange (ETDEWEB)

    Awad, Zainab [Astronomy, Space Science, and Meteorology Department, Faculty of Science, Cairo University, Giza (Egypt); Viti, Serena; Williams, David A., E-mail: zma@sci.cu.edu.eg [Physics and Astronomy Department, University College London, Gower Street, London WC1E 6BT (United Kingdom)

    2016-08-01

    Previous work by various authors has suggested that the detection by Herschel /HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H{sub 2} formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O{sup +} ions detected by Herschel /HIFI that are present along many sight lines in the Galaxy. The O{sup +} hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion–molecule reactions.

  16. On the Chemistry of Hydrides of N Atoms and O+ Ions

    Science.gov (United States)

    Awad, Zainab; Viti, Serena; Williams, David A.

    2016-08-01

    Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H2 formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O+ ions detected by Herschel/HIFI that are present along many sight lines in the Galaxy. The O+ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

  17. Influence of Zircaloy cladding composition on hydride formation during aqueous hydrogen charging

    Energy Technology Data Exchange (ETDEWEB)

    Rajasekhara, S. [Intel Corporation, 2501 NW 229th Av., Hillsboro, OR 97124 (United States); Kotula, P.G.; Enos, D.G.; Doyle, B.L. [Sandia National Laboratories, Albuquerque, NM, 87185 (United States); Clark, B.G., E-mail: blyclar@sandia.gov [Sandia National Laboratories, Albuquerque, NM, 87185 (United States)

    2017-06-15

    Although hydrogen uptake in Zirconium (Zr) based claddings has been a topic of many studies, hydrogen uptake as a function of alloy composition has received little attention. In this work, commercial Zr-based cladding alloys (Zircaloy-2, Zircaloy-4 and ZIRLO™), differing in composition but with similar initial textures, grain sizes, and surface roughness, were aqueously charged with hydrogen for 100, 300, and 1000 s at nominally 90 °C to produce hydride layers of varying thicknesses. Transmission electron microscope characterization following aqueous charging showed hydride phase and orientation relationship were identical in all three alloys. However, elastic recoil detection measurements confirmed that surface hydride layers in Zircaloy-2 and Zircaloy-4 were an order of magnitude thicker relative to ZIRLO™. - Highlights: •Aqueous charging was performed to produce a layer of zirconium hydride for three different Zr-alloy claddings. •Hydride thicknesses were analyzed by elastic recoil detection and transmission electron microscopy. •Zircaloy-2 and Zircaloy-4 formed thicker hydride layers than ZIRLO™ for the same charging durations.

  18. Effects of Boron-Incorporation in a V-Containing Zr-Based AB2 Metal Hydride Alloy

    Directory of Open Access Journals (Sweden)

    Shiuan Chang

    2017-11-01

    Full Text Available In this study, boron, a metalloid element commonly used in semiconductor applications, was added in a V-containing Zr-based AB2 metal hydride alloy. In general, as the boron content in the alloy increased, the high-rate dischargeability, surface exchange current, and double-layer capacitance first decreased and then increased whereas charge-transfer resistance and dot product of charge-transfer resistance and double-layer capacitance changed in the opposite direction. Electrochemical and gaseous phase characteristics of two boron-containing alloys, with the same boron content detected by the inductively coupled plasma optical emission spectrometer, showed significant variations in performances due to the difference in phase abundance of a newly formed tetragonal V3B2 phase. This new phase contributes to the increases in electrochemical high-rate dischargeability, surface exchange current, charge-transfer resistances at room, and low temperatures. However, the V3B2 phase does not contribute to the hydrogen storage capacities in either gaseous phase and electrochemical environment.

  19. Kinetics of aggregation growth with competition between catalyzed birth and catalyzed death

    International Nuclear Information System (INIS)

    Wang Haifeng; Gao Yan; Lin Zhenquan

    2008-01-01

    An aggregation growth model of three species A, B and C with the competition between catalyzed birth and catalyzed death is proposed. Irreversible aggregation occurs between any two aggregates of the like species with the constant rate kernels I n (n = 1,2,3). Meanwhile, a monomer birth of an A species aggregate of size k occurs under the catalysis of a B species aggregate of size j with the catalyzed birth rate kernel K(k,j) = Kkj v and a monomer death of an A species aggregate of size k occurs under the catalysis of a C species aggregate of size j with the catalyzed death rate kernel L(k,j)=Lkj v , where v is a parameter reflecting the dependence of the catalysis reaction rates of birth and death on the size of catalyst aggregate. The kinetic evolution behaviours of the three species are investigated by the rate equation approach based on the mean-field theory. The form of the aggregate size distribution of A species a k (t) is found to be dependent crucially on the competition between the catalyzed birth and death of A species, as well as the irreversible aggregation processes of the three species: (1) In the v k (t) satisfies the conventional scaling form; (2) In the v ≥ 0 case, the competition between the catalyzed birth and death dominates the process. When the catalyzed birth controls the process, a k (t) takes the conventional or generalized scaling form. While the catalyzed death controls the process, the scaling description of the aggregate size distribution breaks down completely

  20. Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-02-18

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